Geochemistry and stable carbon isotope composition of kerogen of DSDP Site 124-767

Celebes Basin sediments from Ocean Drilling Program Site 767 (Leg 124) containing both marine and terrestrial organic matter have been investigated through palynofacies and geochemical analyses. The main degradation processes affecting or having affected organic matter are recorded in the sedimentary column as shown by ammonium, phosphate and sulfate pore-water profiles, and by petrographic and geochemical analyses of sediments. In the upper part of the sedimentary section (down to 200 mbsf), the decrease of the ratio of total organic carbon to sulfur (TOC/S) with depth, generally related to the sulfate reduction process, is accompanied by an increase of framboidal pyrite content in the marine organic matter, and by an increasing amount of amorphous marine organic matter relative to the total organic matter. However, as the terrestrial organic input also varies with depth, dilution effects are superimposed on diagenesis. This continental supply affects the TOC/S ratio by increasing total organic carbon and decreasing the ability of the bulk organic matter to be metabolized through sulfate reduction. A positive relationship between the TOC/P ratio and the amount of degraded organic matter of marine origin clearly displays the effect of an organic source on the composition of the sediment. Each lithostratigraphic unit possesses its own characteristics in terms of composition and preservation of organic matter. The effects of diagenesis can only be appreciated within a single lithostratigraphic unit and mainly affect the less-resistant marine organic matter.

Stable carbon isotope ratios and the formation of dolomite in ODP Leg 175 sites

We examine the link between organic matter degradation, anaerobic methane oxidation (AMO), and sulfate depletion and explore how these processes potentially influence dolomitization. We determined rates and depths of AMO and dolomite formation for a variety of organic-rich sites along the west African Margin using data from Ocean Drilling Program (ODP) Leg 175. Rates of AMO are calculated from the diffusive fluxes of CH4 and SO4, and rates of dolomite formation are calculated from the diffusive flux of Mg. We find that the rates of dolomite formation are relatively constant regardless of the depth at which it is forming, indicating that the diffusive fluxes of Mg and Ca are not limiting. Based upon the calculated log IAP values, log K(sp) values for dolomite were found to narrowly range between -16.1 and -16.4. Dolomite formation is controlled in part by competition between AMO and methanogenesis, which controls the speciation of dissolved CO2. AMO increases the concentration of CO3[2-] through sulfate reduction, favoring dolomite formation, while methanogenesis increases the pCO2 of the pore waters, inhibiting dolomite formation. By regulating the pCO2 and alkalinity, methanogenesis and AMO can regulate the formation of dolomite in organic-rich marine sediments. In addition to providing a mechanistic link between AMO and dolomite formation, our findings provide a method by which the stability constant of dolomite can be calculated in modern sediments and allow prediction of regions and depth domains in which dolomite may be forming.

Stable oxygen and carbon isotope record of foraminifera of ODP SIte 184-1146

Ocean Drilling Program Site 1146 was drilled within a small rift basin on the midcontinental slope of the northern South China Sea. It is located at 19°27.4'N, 116°16.37'E, in 2092 m water depth. This site was drilled to recover records of Asian monsoon variability into the middle Miocene with temporal resolution sufficient for orbital-scale analyses. Here we present oxygen and carbon isotopic measurements of planktonic foraminifers (Globigerinoides ruber) and benthic foraminifers (Uvigerina peregrina and Cibicides wuellerstorfi) as well as a preliminary age model for the top 185 meters composite depth (mcd).

Oxygen and carbon isotope data for benthic foraminifera from DSDP Site 94-608 and ODP Site 208-1264

Small biserial foraminifera were abundant in the early Miocene (ca. 18.9-17.2 Ma) in the eastern Atlantic and western Indian Oceans, but absent in the western equatorial Atlantic Ocean, Weddell Sea, eastern Indian Ocean, and equatorial Pacific Ocean. They have been assigned to the benthic genus Bolivina, but their high abundances in sediments without evidence for dysoxia could not be explained. Apertural morphology, accumulation rates, and isotopic composition show that they were planktic (genus Streptochilus). Living Streptochilus are common in productive waters with intermittent upwelling. The widespread early Miocene high Streptochilus abundances may reflect vigorous but intermittent upwelling, inducing high phytoplankton growth rates. However, export production (estimated from benthic foraminiferal accumulation rates) was low, possibly due to high regeneration rates in a deep thermocline. The upwelled waters may have been an analog to Subantarctic Mode Waters, carrying nutrients into the eastern Atlantic and western Indian Oceans as the result of the initiation of a deep-reaching Antarctic Circumpolar Current, active Agulhas Leakage, and vigorous vertical mixing in the Southern Oceans.

Oxygen and carbon isotope stratigraphy of ODP Holes 107-653A and 107-654A

Stable isotope analysis of two species (or groups of species) of planktonic foraminifers: Globigerinoides ruber (or G. obliquus and G. obliquus extremus) and Globigerina bulloides (or G. falconensis and G. obesa) from ODP Hole 653A and Site 654 in the Tyrrhenian basin, records the Pliocene-Pleistocene glacial history of the Northern Hemisphere. The overall increase in mean d18O values through the interval 4.6-0.08 Ma is 1.7 per mil for G. bulloides and 1.5 per mil for G. ruber. The time interval 3.1-2.5 Ma corresponds to an important phase of 18O enrichment for planktonic foraminifers. In this interval, glacial d18O values of both species G. bulloides and G. ruber increase by about l per mil, this increase being more progressive for G. ruber than for G. bulloides. The increase of interglacial d18O values is higher for G. bulloides (1.5 per mil) than for the Gruber group (1 per mil). These data suggest a more pronounced seasonal stratification of the water masses during interglacial phases. Large positive d18O fluctuations of increasing magnitude are also recorded at 2.25 and 2.15 Ma by G bulloides and appear to be diachronous with those of Site 606 in the Atlantic Ocean. Other events of increasing d18O values are recorded between 1.55 and 1.3 Ma, at 0.9 Ma, 0.8 Ma, and near 0.34 Ma. In the early Pliocene the d18O variability recorded by the planktonic species G. bulloides was higher in the Mediterranean than in the Atlantic at the same latitude. This suggests that important cyclic variations in the water budget of the Mediterranean occurred since that time. Step increases in the d18O variability are synchronous with those of the open ocean at 0.9 and 0.34 Ma. The higher variability as well as the higher amplitude of the peaks of 18O enrichment may be partly accounted for by increase of dryness over the Mediterranean area. In particular the high amplitude d18O fluctuations recorded between 3.1 and 2.1 Ma are correlated with the onset of a marked seasonal contrast and a summer dryness, revealed by pollen analyses. Strong fluctuations towards d13C values higher than modern ones are recorded by the G. ruber group species before 1.7 Ma and suggest a high production of phytoplankton. When such episodes of high primary production are correlated with episodes of decreasing 13C content of G. bulloides, they are interpreted as the consequence of a higher stratification of the upper water masses resulting itself from a marked seasonality. Such episodes occur between 4.6 and 4.05 Ma, 3.9 and 3.6 Ma, and 3.25 and 2.66 Ma. The interval 2.66-1.65 Ma corresponds to a weakening of the stratification of the upper water layers. This may be related to episodes of cooling and increasing dryness induced by the Northern Hemisphere Glaciations. The Pleistocene may have been a less productive period. The transition from highly productive to less productive surface waters also coincides with a new step increase in dryness and cooling, between 1.5 and 1.3 Ma. The comparison of the 13C records of G ruber and G. bulloides in fact suggests that a high vertical convection became a dominant feature after 2.6 Ma. Increases in the nutrient input and the stratification of the upper water masses may be suspected, however, during short episodes near 0.86 Ma (isotopic stage 25), 0.57-0.59 Ma (isotopic stage 16), 0.49 Ma (isotopic stage 13), 0.4-0.43 Ma (isotopic stage 11), and 0.22 and 0.26 Ma (part of isotopic stage 7 and transition 7/8). In fact, changes in the C02 balance within the different water masses of the Tyrrhenian basin as well as in the local primary production did not follow the general patterns of the open ocean.

Pliocene stable oxygen and carbon isotope record of benthic foraminifera from ODP Site 138-846 in the eastern equatorial Pacific

Oxygen and carbon isotope ratios were measured in benthic foraminifers from the entire Pliocene and latest Miocene sections of Site 846, a 180-m section, at a sampling interval of 10 cm. This provides a temporal resolution of about 2500 yr. The documented continuity of the record is excellent. Using the time scale that was developed on the basis of orbital tuning of GRAPE density records, we observed a fairly constant phase relationship between delta18O and variations in the obliquity of Earth's rotational axis. A new numbering scheme for Pliocene isotope stages is proposed. This high-resolution delta18O record clarifies several interesting aspects of late Neogene climatic evolution, including a "glacial" event that may have caused the final Messinian desiccation of the Mediterranean Sea; one or more "interglacial" events that might have caused refilling of the Mediterranean; a well-resolved couplet of glacial events at about the age of the Sidujfall Subchron; interglacial extremes in the early part of the Gauss that could have resulted from either significant deglaciation on Antarctica or from warming of deep water; and a gradual ramp of increasingly extreme "glacial" events, starting at about the Kaena Subchron and culminating with delta18O stage 100 in the earliest Matuyama.

Stable organic carbon isotope record and total organic carbon content from the Cenomanian-Turonian boundary

Ocean Drilling Program (ODP) Leg 207 recovered expanded sections of organic-carbon-rich laminated shales on Demerara Rise (western tropical Atlantic). High-resolution organic carbon isotope and total organic carbon (TOC) records are presented, which span the Cenomanian-Turonian boundary interval (CTBI), including the Oceanic Anoxic Event (OAE) 2, from four sites oriented along a NW striking depth transect. These records represent the first high-resolution carbon isotope records across OAE 2 from the South American margin of the tropical Atlantic. Due to the scarcity of age significant fossils, the main purpose of this study was to develop a detailed carbon isotope stratigraphy in order to correlate the CTBI across the depth transect and to tie this to biostratigraphically well-defined sections in the Western Interior Basin (Pueblo, USA), boreal shelf seas (Eastbourne, England), and western Tethys (Oued Mellegue, Tunisia). All four sections studied document a 6 per mil increase of d13Corg values at the base of the CTBI, which is followed by an interval of elevated d13Corg values and a subsequent decrease. Our results supply an important stratigraphic base for subsequent paleoceanographic studies on Late Cenomanian to Early Turonian sediments from Demerara Rise and elsewhere.