Molecular and stable isotope composition of headspace and total hydrogencarbon gases of ODP Leg 104 sites

Molecular and isotope compositions of headspace and total (free + sorbed) hydrocarbon gases from drilled cores of the three ODP Leg 104 Sites 642, 643, and 644 of the Voring Plateau are used to characterize the origin and distribution of these gases in Holocene to Eocene sediments. Only minor amounts of methane were found in the headspace (0.1 to < 0.001 vol%). Although methane through propane are present in all of the total gas samples, different origins account for the concentration and composition variations found. Site 643 at the foot of the outer Voring Plateau represents a geological setting with poor hydrocarbon generating potential, (sediments with low TOC and maturity overlying oceanic basement). Correspondingly, the total gas concentrations are low, typical for background gases (yield C1 - 4 = 31 to 232 ppb, C1/C2+ = 0.6 to 4; delta13C(CH4) -22 per mil to -42 per mil) probably of a diagenetic origin. Holocene to Eocene sediments, which overlie volcanic units, were drilled on the outer Vdring Plateau, at Holes 642B and D. Similar to Site 643, these sediments possess a poor hydrocarbon generating potential. The total gas character (yield C1 - 4 = 20 to 410 ppb; C1/C2+ = 1.7 to 13.3; delta13C(CH4) ca. -23 per mil to -40 per mil) again indicates a diagenetic origin, perhaps with the addition of some biogenic gas. The higher geothermal gradient and the underlying volcanics do not appear to have any influence on the gas geochemistry. The free gas (Vacutainer TM) in the sediments at Site 644 are dominated by biogenic gas (C1/C2+ > 104; delta13C(CH4) -77 per mil). Indications, in the total gas, of hydrocarbons with a thermogenic signature (yield C1 - 4 = 121 to 769 ppb, C1/ C2+ = 3 to 8; delta13C(CH4) = -39 per mil to -71 per mil), could not be unequivocally confirmed as such. Alternatively, these gases may represent mixtures of diagenetic and biogenic gases.

Stable isotope record of ODP Sites 108-658 and 108-659

Ocean Drilling Program Site 658, cored below a major upwelling cell offshore Cap Blanc, contains a largely undisturbed hemipelagic sediment section spanning the Brunhes Chron and the early Quaternary and late Pliocene. The companion Site 659 recovered a complete and undisturbed Neogene profile further offshore that serves as a nonupwelling pelagic reference section. Oxygen and carbon isotope ratios in benthic (C. wuellerstorfi and in part Uvigerina sp.) and planktonic foraminifers (G. inflata) provide a climatic record of high resolution for the Brunhes Chron. At Site 658 the record extends back to the early Pleistocene and late Pliocene. The standard oxygen isotope record of the last 730,000 yr is markedly refined by a well-documented high-frequency variation (e.g., by a new "aborted" ice age at stage 13.2 and by Younger-Dryas style climatic setbacks during most terminations). In the late Pliocene, the numerical oxygen isotope stage taxonomy was extended back to stage 137 about 3.3 Ma ago. In comparison with published records, stage 114 at 2.7 Ma represents the first major glaciation event, when 18O was short-term enriched up to a middle Pleistocene glacial d18O level. About 3.17 Ma ago (stage 133), the interglacial oxygen isotope values of C. wuellerstorfi started to increase by 0.5 per mil until 2.7 Ma and then remained largely constant until the Holocene. Based on the d13C difference between C. wuellerstorfi and G. inflata, the dissolved CO2 in the ambient bottom water of Site 658 was dominated by the flux of particulate carbon from the overlying upwelling cell during the last 630,000 yr. In contrast, the advection of (upper) North Atlantic Bottom Water dominated in the control of the local CO2 content during the early Pleistocene and late Pliocene.

Stable isotope (carbonates), organic carbon, calcium carbonate and occurrence of coccoliths at DSDP Hole 71-511

Thin but discrete pelagic limestone beds intercalated among the black mudstones near the top of the extensive Mesozoic black shale sequence of the Falkland Plateau are reminiscent of similar occurrences in the central and North Atlantic and may be cyclic in nature. They have been studied via carbonate, organic carbon, stable isotope, nannofloral, and ultrastructural analysis in an attempt to determine their mode of origin. Nannofossil diversity and preservation suggest that selective dissolution or diagenesis did not produce the interbedded coccolith-rich and coccolith-poor layers, nor did blooms of opportunistic species play a role. Stable isotope measurements of carbonate do not adequately constrain the origin of the cyclicity; however, the d13C data suggest that the more nannofossil-rich intervals may be due to higher nutrient supply and overturn of deeper waters at the site rather than influxes of well-oxygenated waters into an otherwise anoxic environment. Such an explanation is in accord with the nannofloral evidence

Interstitial-water chemistry and stable isotope record of Prydz Bay sediments

Leg 119 of the Ocean Drilling Program (ODP) provided the first opportunity to study the interstitial-water chemistry of the eastern Antarctic continental margin. Five sites were cored in a northwest-southeast transect of Prydz Bay that extended from the top of the continental slope to within 30 km of the coastline. Geological studies of the cores reveal a continental margin that has evolved through terrestrial, glacial, and glacial-marine environments. Chemical and stable isotopic analyses of the interstitial-waters were performed to determine the types of depositional environments and the diagenetic and hydrologic processes that are operating in this unusual marine environment. Highly compacted glacial sediments provide an effective barrier to the vertical diffusion of interstitial-water solutes. Meteoric water from the Antarctic continent appears to be flowing into Prydz Bay sediments through the sequence of terrestrial sediments that lie underneath the glacial sediments. The large amounts of erosion associated with glacial advances appear to have had the effect of limiting the amount of marine organic matter that is incorporated into the sediments on the continental shelf. Although all of the sites cored in Prydz Bay exhibit depletions in dissolved sulfate with increasing depth, the greatest bacterial activity is associated with a thin layer of diatom ooze that coats the seafloor of the inner bay. Results of alkalinity modeling, thermodynamic calculations, and strontium analyses indicate that (1) ocean bottom waters seaward of Site 740 are undersaturated with respect to both calcite and aragonite, (2) interstitial waters at each site become saturated or supersaturated with respect to calcite and aragonite with increasing depth, (3) precipitation of calcium carbonate reduces the alkalinity of the pore waters with increasing depth, and (4) recrystallization of aragonite to calcite accounts for 24% of the pore-water strontium. Weathering of unstable terrestrial debris and cation exchange between clay minerals and pore fluids are the most probable chemical processes affecting interstitial water cation gradients.

Stable isotope record of benthic and planktonic foraminifera from ODP Site 175-1087 in the southern Cape Basin, Atlantic Ocean

High-resolution planktonic and benthic stable isotope records from Ocean Drilling Program Site 1087 off southeast Africa provide the basis for a detailed study of glacial-interglacial (G-IG) cycles during the last 500 k.y. This site is located in the Southern Cape Basin at the boundary of the coastal upwelling of Benguela and close to the gateway between the South Atlantic and the Indian Oceans. It therefore monitors variations of the hydrological fronts associated with the upwelling system and the Atlantic-Indian Ocean interconnections, in relation to global climate change. The coldest period of the last 500 k.y. corresponds to marine isotope Stage (MIS) 12, when surface water temperature was 4°C lower than during the last glacial maximum (LGM) as recorded by the surface-dwelling foraminifer Globigerinoides ruber. The warmest periods occurred during MISs 5 and 11, a situation slightly different to that observed at Site 704, which is close to the Polar Front Zone, where there is no significant difference between the interglacial stages for the past 450 k.y., except the long period of warmth during MIS 11. The planktonic and benthic carbon isotope records do not follow the G-IG cycles but show large oscillations related to major changes in the productivity regime. The largest positive 13C excursion between 260 and 425 ka coincides with the global mid-Brunhes event of carbonate productivity. The oxygen and carbon isotopic gradients between surface and deep waters display long-term changes superimposed on rapid and high-frequency fluctuations that do not follow the regular G-IG pattern; these gradients indicate modifications of the temperature, salinity, and productivity gradients due to changes in the thermocline depth, the position of the hydrological fronts, and the strength of the Benguela Current.

Stable isotope record of DSDP Hole 81-552A in the northeastern Atlantic Ocean

Oxygen and carbon isotope ratios in benthic foraminifers have been determined at 10 cm intervals through the top 59 m of DSDP Hole 552A. This provides a glacial record of remarkable resolution for the late Pliocene and Pleistocene. The major glacial event which marked the onset of Pleistocene-like glacial-interglacial alternations was at about 2.4 m.y. ago. These very high-resolution data do not support the notion of significant Northern Hemisphere glaciation between 3.2 and 2.4 m.y. ago.

Sedimentology and stable isotope record of DSDP Hole 68-503B

Samples from the upper portion of a cyclic pelagic carbonate sediment sequence in Deep-Sea Drilling Project (DSDP) hole 503B (4.0°N, 95.6°W) are the first group to be analyzed for paleoceanographic and paleoclimatic proxy-indicators of ice volume, deep ocean and surface water circulation, and atmospheric circulation in order to resolve the complex origin of the cyclicity. Temporal resolution is taken from the delta18O time scale, most other parameters are calculated in terms of their mass flux to the seafloor. CaCO3 percent in the sediments fluctuates in the well-known Pacific pattern and is higher during glacial times. The fluxes of opal and organic carbon have patterns similar to each other and show a variability of a factor of 2.5 to 4. The longer organic carbon record shows flux maxima during both glacial and interglacial times. The accumulation patterns of both opal and organic carbon suggest that the variability in surface water productivity and/or seafloor preservation of those materials is not simply correlated to glacial or interglacial periods. Eolian dust fluxes are greater during interglacial periods by factors of 2 to 5, indicating that eolian source regions in central and northern South America were more arid during interglacial periods. The record of eolian grain size provides a semiquantitative estimation of the intensity of the transporting winds. The eolian data suggest more intense atmospheric circulation during interglacial periods, opposite to the anticipated results. We interpret this observation as recording the southerly shift of the intertropical convergence zone to the latitude of hole 503B during glaciations.

Size-related stable isotope changes in Late Cretaceous and Recent planktic foraminifera from the western tropical Atlantic

The paleoecology of Cretaceous planktic foraminifera during the Late Cenomanian to Coniacian period (~95-86 Ma) remains controversial since much of the tropical marine record is preserved as chalk and limestone with uncertain geochemical overprints. Here we present delta13C and delta18O data from sieve size fractions of monospecific samples of exceptionally well preserved planktic foraminifera recovered during Ocean Drilling Program Leg 207 (Demerara Rise, western tropical Atlantic). Our results suggest that all species studied (Hedbergella delrioensis, Heterohelix globulosa, Marginotruncana sinuosa, Whiteinella baltica) grew primarily in surface waters and did not change their depth habitat substantially during their life cycle. Comparison of size-related ontogenetic trends in delta13C in Cretaceous and modern foraminifera further suggests that detection of dinoflagellate photosymbiosis using delta13C is confounded by physiological effects during the early stages of foraminifer growth, raising doubts about previous interpretations of photosymbiosis in small foraminifera species. We propose that obligate photosymbiosis involving dinoflagellates may not have evolved until the Campanian or Maastrichtian since our survey of Cenomanian-Coniacian species does not find the delta18O and delta13C size-related trends observed in modern foraminifer-dinoflagellate symbioses.

Stable isotope record of a Bermuda coral

Records of skeletal delta18O in monthly and Sr/Ca ratios in half-yearly resolution were obtained from a Bermuda coral (Diploria labyrinthiformis) for the time period 1520-1603 (+/-15 yr) AD within the Little Ice Age. Annual and decadal averages of both sea-surface temperature proxies indicate temperature variabilities of 0.5°C (standard deviation) and 0.3°C, respectively. Both numbers are close to recent instrumental observations. Approximately 30% of the interannual time series variance of delta18O is concentrated in broad bands centered at periods of ~30, 16, and 7.8 yr, the last two reflecting the influence of the North Atlantic Oscillation. Although this large-scale climate signal is present in the record, there is no correlation with other contemporaneous northern hemisphere proxy data, resulting from spatial differences in climate variability.