Oxygen- and carbon-isotopes at DSDP Leg 73 Holes

We established a composite oxygen- and carbon-isotope stratigraphy for the Pliocene in the central South Atlantic. Monospecific samples of benthic and planktonic foraminifers from pelagic sediments from DSDP Sites 519, 521, 522, and 523 were analyzed isotopically. The resulting benthic oxygen-isotope stratigraphy allowed three paleoclimatic periods in the Pliocene to be distinguished. During the early Pliocene (5.2-3.3 Ma), low-amplitude climatic changes prevailed in a world that was less glaciated than during the Pleistocene. A net increase in global ice volume is documented in a 0.5 permil positive shift in the average 18O composition of the benthic foraminifers at 3.2 Ma. The middle Pliocene (3.3-2.5 Ma) is not only characterized by a more widespread glaciation of the Southern and Northern hemispheres but also by more drastic isotopic differences between glacial and interglacial times. A minor shift in the average 18O composition of the benthic foraminifers marks the beginning of the late Pliocene-early Pleistocene climatic period (2.5-1.1 Ma). Alternating cold and warm climate is documented in both the oxygen-isotope record and in the pelagic sediments. During cold periods, sediments with a lower CaCO3 content indicate more corrosive bottom-water conditions. More negative 13C signals in the benthic foraminifers from these sediments suggest that the Antarctic Bottom Water current was intensified in glacial times. The oxygen-isotope composition of the measured planktonic foraminifers suggests that the surface water in this part of the South Atlantic remained relatively warm during the growth of the Pliocene glaciers.

Marine and terrigenous lipids in ODP Leg 175 holes

Lipid compositions of sediments recovered during Ocean Drilling Program Leg 175 in the eastern South Atlantic reflect a variety of oceanographic and climatological environments. Most of the identified lipids can be ascribed to marine sources, notably haptophytes, eustigmatophytes, dinoflagellates, archaea, and diatoms. Elevated concentrations of cholesterol suggest zooplankton herbivory, characteristic for sites influenced by upwelling. At these sites, sulfurized highly branched isoprenoids from diatoms are also present in high amounts. Sterols, sterol ethers, hopanoids, and midchain hydroxy fatty acids could also be detected. Terrigenous lipids are n-alkanes, fatty acids, n-alcohols, and triterpenoid compounds like taraxerol and -amyrine. n-Alkanes, fatty acids, and n-alcohols are derived from leaf waxes of higher land plants and transported to the sea by airborne dust or fresh water. Triterpenoid compounds are most probably derived from mangroves and transported solely by rivers. Lipid compositions below the Congo low-salinity plume are strongly influenced by terrigenous material from the Congo River. Elevated organic carbon contents and predominantly marine lipid distributions at the Angola margin may indicate a highly productive plankton population, probably sustained by the Angola Dome. Sedimentary lipids in the Walvis Basin contain an upwelling signal, likely transported by the Benguela Current. Sedimentary lipids off Lüderitz Bay and in the southern Cape Basin are dominated by plankton lipids in high to intermediate amounts, reflecting persistent and seasonal upwelling, respectively.

Products of chlorophyll diagenesis from DSDP Leg 57 Holes

Tetrapyrrole pigments isolated from sediments retrieved during Leg 57 include pheophytin-a, a myriad of chlorins, free-base deoxophylloerythroetioporphyrin (DPEP), as well as copper and nickel porphyrins. Their richness, both qualitatively and quantitatively, in chlorin tetrapyrroles affords a relatively complete study on the early diagenesis of chlorophyll. Our studies, coupled with those in the preceding chapter by Louda et al., point out the influence of pre- and postdepositional environments upon the mode of chlorophyll diagenesis. Formation of tetrapyrroles, collectively called "petroporphyrins," is seen to occur in only a limited set of environmental conditions (see Baker and Palmer, 1978). The more generalized route of chlorophyll diagenesis, at least in the ocean, results in removal of tetrapyrrole pigment, from the fossil record. Late diagenetic products, metalloporphyrins, are found to represent an extremely minor component of the tetrapyrrole assemblage in sediments studied from the Japan Trench. The products of chlorophyll diagenesis isolated from Japan Trench sediments allow expansion of previous diagenetic schemes (Baker and Palmer, 1978; Triebs, 1936) and indicate directions for future studies.

Interstitial water chemistry at DSDP Leg 82 Holes

Interstitial waters were collected at only two sites during Leg 82, Sites 558 and 563. Only very small changes in dissolved calcium and magnesium occur, presumably resulting from reactions in the underlying basement basalts. Dissolved strontium profiles indicate maxima, which can be understood in terms of carbonate recrystallization processes. Data on Sr/Ca in carbonates cannot be used to estimate the extent of recrystallization that has occurred in these sediments.

Analysis of an ancient global warming event, the Paleocene-Eocene thermal maximum, under examination from ODP Holes 113-689B and 113-690B

Spatiotemporal patterns of carbonate dissolution provide a critical constraint on carbon input during an ancient (~55.5 Ma) global warming event known as the Paleocene-Eocene thermal maximum (PETM), yet the magnitude of lysocline shoaling in the Southern Ocean is poorly constrained due to limited spatial coverage in the circum-Antarctic region. This shortcoming is partially addressed by comparing patterns of carbonate sedimentation at the Site 690 PETM reference section to those herein reconstructed for nearby Site 689. Biochemostratigraphic correlation of the two records reveals that the first ~36 ka of the carbon isotope excursion (CIE) signaling PETM conditions is captured by the Site 689 section, while the remainder of the CIE interval and nearly all of the CIE recovery are missing due to a coring gap. A relatively expanded stratigraphy and higher carbonate content at mid-bathyal Site 689 indicate that dissolution was less severe than at Site 690. Thus, the bathymetric transect delimited by these two PETM records indicates that the lysocline shoaled above Site 689 (~1,100 m) while the calcite compensation depth remained below Site 690 (~1,900 m) in the Weddell Sea region. The ensuing recovery of carbonate sedimentation conforms to a bathymetric trend best explained by gradual lysocline deepening as negative feedback mechanisms neutralized ocean acidification. Further, biochemostratigraphic evidence indicates the tail end of the CIE recovery interval at both sites has been truncated by a hiatus most likely related to vigorous production and advection of intermediate waters.

Sediment properties of IODP Holes 303-U1302A and 303-U1305C

Episodes of ice-sheet disintegration and meltwater release over glacial-interglacial cycles are recorded by discrete layers of detrital sediment in the Labrador Sea. The most prominent layers reflect the release of iceberg armadas associated with cold Heinrich events, but the detrital sediment carried by glacial outburst floods from the melting Laurentide Ice Sheet is also preserved. Here we report an extensive layer of red detrital material in the Labrador Sea that was deposited during the early last interglacial period. We trace the layer through sediment cores collected along the Labrador and Greenland margins of the Labrador Sea. Biomarker data, Ca/Sr ratios and d18O measurements link the carbonate contained in the red layer to the Palaeozoic bedrock of the Hudson Bay. We conclude that the debris was carried to the Labrador Sea during a glacial outburst flood through the Hudson Strait, analogous to the final Lake Agassiz outburst flood about 8,400 years ago, probably around the time of a last interglacial cold event in the North Atlantic. We suggest that outburst floods associated with the final collapse of the Laurentide Ice Sheet may have been pervasive features during the early stages of Late Quaternary interglacial periods.

Organic geochemistry of sediments at DSDP Leg 63 Holes

Selected core samples from the California Continental Borderland (Sites 467-469) were analyzed to evaluate the nature and composition of the lipids and kerogens in terms of their genetic origin and geological maturity. The lipids were of a multiple origin. On the basis of the homolog distributions of the n-alkanes and n-fatty acids, with the shape and magnitude of the unresolved branched and cyclic hydrocarbons, and the structural and stereochemical compositions of the molecular markers, these lipids were derived from primary autochthonous marine (microbial), from allochthonous terrigenous (higher plant wax), and from recycled (geologically mature organic matter) sources. The kerogens were composed of principally marine microbial detritus with a minor input of allochthonous terrestrial material. For the most part, the samples had undergone a thermal maturation according to a normal geothermal gradient, except in the proximity of intrusives. Such additional thermal stress was evident for the samples from Site 469 and to some extent for Site 467 at about a sub-bottom depth of 700 to 800 meters.

Composition of hardgrounds and of pore-water parameters in ODP Holes 166-1008 and 166-1009

Mineralogic, petrographic, and geochemical analyses of sediments recovered from two Leg 166 Ocean Drilling Program cores on the western slope of Great Bahama Bank (308 m and 437 m water depth) are used to characterize early marine diagenesis of these shallow-water, periplatform carbonates. The most pronounced diagenetic products are well-lithified intervals found almost exclusively in glacial lowstand deposits and interpreted to have formed at or near the seafloor (i.e., hardgrounds). Hardground cements are composed of high-Mg calcite (~14 mol% MgCO3), and exhibit textures typically associated with seafloor cementation. Geochemically, hardgrounds are characterized by increased d18O and Mg contents and decreased d13C, Sr, and Na contents relative to their less lithified counterparts. Despite being deposited in shallow waters that are supersaturated with the common carbonate minerals, it is clear that these sediments are also undergoing shallow subsurface diagenesis. Calculation of saturation states shows that pore waters become undersaturated with aragonite within the upper 10 m at both sites. Dissolution, and likely recrystallization, of metastable carbonates is manifested by increases in interstitial water Sr and Sr/Ca profiles with depth. We infer that the reduction in mineral saturation states and subsequent dissolution are being driven by the oxidation of organic matter in this Fe-poor carbonate system. Precipitation of burial diagenetic phases is indicated by the down-core appearance of dolomite and corresponding decrease in interstitial water Mg, and the presence of low-Mg calcite cements observed in scanning electron microscope photomicrographs.

Opal concentration of ODP Leg 178 holes

Neogene to Quaternary records of biogenic opal contents and opal accumulation rates are presented for Sites 1095, 1096, and 1101, which were drilled during Ocean Drilling Program Leg 178 in the Bellingshausen Sea, a marginal sea in the eastern Pacific sector of the Southern Ocean. The opal records in the drift sediments on the continental rise west of the Antarctic Peninsula provide signals of paleoproductivity, although they are influenced by dissolution in the water column and the sediment column. Opal contents at Sites 1095, 1096, and 1101 show similar long-term trends through the Neogene and Quaternary, whereas the opal accumulation rates exhibit marked discrepancies, which are caused by local differences in opal preservation linked to local variations of bottom current-induced supply of lithogenic detritus. We used a regression describing the relationship between opal preservation and sedimentation rate to extract the signal of primary opal deposition on the seafloor in the Bellingshausen Sea from the opal accumulation in the drift deposits. On long-term timescales, the reconstructed opal depositional rates show patterns similar to those of the opal contents and a much better coherency between the different locations on the Antarctic Peninsula continental rise. Therefore, the estimated opal depositional rates are suggested to represent a suitable proxy for paleoproductivity in the drift setting of the Bellingshausen Sea. Supposing that the sea-ice coverage within the Antarctic Zone was the main factor controlling biological productivity in the Bellingshausen Sea, and thus the estimated opal depositional rates on the continental rise, we reconstructed paleoceanographic long-term changes during the Neogene and Quaternary considering the climatic control on regional and global scales. Slightly enhanced opal depositional rates during the late Miocene are interpreted to indicate warmer climatic conditions in the vicinity of the Antarctic Peninsula than at present. The contribution of heat from the Northern Component Water (NCW) into the Southern Ocean seems only to have played a subordinate role during that time. High opal depositional rates during the early Pliocene document a strong reduction of sea-ice coverage and relatively warm climatic conditions in the Bellingshausen Sea. The early onset of the Pliocene warmth points to a positive feedback of regional Antarctic climate on the global thermohaline circulation. A decrease of opal deposition between 3.1 and 1.8 Ma likely reflects sea-ice expansion in response to reduced NCW flow, caused by the onset and intensification of Northern Hemisphere glaciation. Throughout the Quaternary, a relatively constant level of opal depositional rates in the Bellingshausen Sea indicates stable climatic conditions in the Antarctic Peninsula area.

Investigations of Cretaceous and Tertiary kerogens in sediments of ODP Leg 113 holes

Seventy-one samples from nine sites were analyzed for total organic carbon (TOC). Fifty-six samples, containing 0.2% or more TOC, were evaluated by Rock-Eval to assess the nature of their kerogen and its petroleum source potential. Visual kerogen studies were carried out. Petroleum potential was encountered only in Valanginian calcareous claystones at Hole 692B close to the margin of Dronning Maud Land. A section of 44.7 m was penetrated. The unit possesses a revised mean TOC of 9.8% and petroleum potential of 43.2 kg/Mg, relatively high values in comparison to other Cretaceous anoxic oceanic sections and the totality of petroleum source rocks. At Sites 689 and 690, extremely low TOC levels, mean 0.07%, preclude kerogen analysis. Kerogens in Eocene to Pliocene sediments of the central and western Weddell Sea (Sites 694, 695, 696, and 697) are similar everywhere, largely comprising brown to black, granular, amorphous material of high rank, and generally possessing several reflectance populations of vitrinite particles. The latter are interpreted as indicative of the recycling of sediments of a variety of levels of thermal maturity.

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.