Stable oxygen isotope record and relative abundances of planktonic foraminifera of ODP Hole 117-728A

High resolution stratigraphy based on oxygen isotope ratios of the planktonic foraminifers Neogloboquadrina dutertrei (d'Orbigny), Globigeriniodes ruber (d'Orbigny), and Globigerina bulloides (d'Orbigny), magnetic susceptibility, and calcium carbonate content covers the sedimentary record of ODP Hole 728A drilled on the Oman Margin from approximately 10 k.y. to 525 k.y., comprising isotopic stages 1-13. Below stage 13 isotopic stage boundaries cannot be defined with certainty in our data. Sediment accumulation rates were calculated from the isotopic record of N. dutertrei by matching it with the age model SPECMAP curve. During the glacial periods sediment accumulation rates were higher than during the interglacial periods, reflecting increased input from the shelf during low-stands of sea level and increased eolian input. Periodograms for the past 524 k.y. on oxygen isotope records of N. dutertrei, G. ruber, and G. bulloides, on calcium carbonate content, magnetic susceptibility, and on a foraminiferal fragmentation record show powers matching the Milankovitch periodicities. High powers are concentrated around 103 k.y. In the spectra of oxygen isotope ratios of N. dutertrei, magnetic susceptibility, and foraminiferal fragmentation these are significant at the 80% confidence level with respect to a first order autoregressive model. Power concentrations near 43 k.y., matching obliquity, are present but subdued in all spectra. Power concentrations near 23 k.y., matching precession, are significant in the spectra of the oxygen isotope record of N. dutertrei, magnetic susceptibility, and calcium carbonate content record. Fragmentation of planktonic foraminifers increased during the interglacial periods. This is attributed to dissolution of the tests in an expanded oxygen minimum zone (OMZ), where undersaturation of calcium carbonate is caused by enhanced production in the euphotic zone, which would suggest stronger monsoonal induced upwelling during interglacial periods. Extension of the OMZ could also be increased by outflow of low oxygen marginal basin bottom water.

Carbonate properties and oxygen concentrations at time series station DYFAMED

Monthly measurements of pH, alkalinity and oxygen over two years (February 1998-February 2000) at the Dyfamed site in the central zone of the Ligurian-Provençal Basin of the Mediterranean made it possible to assess the vertical distributions (5-2000 m) and the seasonal variations of these properties. Alkalinity varies linearly with salinity between surface water and the Levantine Intermediate Water (marked by a maximum of temperature and salinity). In deep water, total alkalinity is also correlated linearly to salinity, but the slope of the regression line is 15% less. In surface water, the pH at 25°C varies between 7.91 and 8.06 on the total proton scale depending upon the season. The lowest values are observed in winter, the highest in spring and in summer. These variations are primarily due to biological production. The pH goes through a minimum around 150-200 m and a small maximum below the intermediate water. The total dissolved inorganic carbon content (deduced from pH and alkalinity) is variable in surface water (2205-2310 ?mol/kg) and has a maximum in intermediate water, which is related to the salinity maximum. Normalized total inorganic carbon at a constant salinity is strongly negatively correlated with pH at 25°C. The fugacity of CO2, (fCO2) varies between 320 and 430 ?atm in surface water, according to the season. Below the seasonal thermocline, the maximum fCO2 (about 410 ?atm) is located around 150-200 m. The presence of a minimum of oxygen in the intermediate water of this area has been observed for several years, but our measurements made it possible to specify the relationship between oxygen and salinity in deep water. Data from the intense vertical mixing during the winters of 1999 and 2000 were used to calculate the oxygen quantity exchanged with the atmosphere during these periods. The estimated quantity of oxygen entering the Mediterranean Sea exceeds that deduced from exchange coefficients calculated with the formula of Wanninkhof and McGillis. During the vertical mixing in the 1999 winter, fCO2 in surface water was on average below equilibrium with atmospheric fCO2, thus implying that CO2 was entering the sea. However, on this time scale, even with high exchange coefficients, the estimated CO2 uptake had no significant influence on the inorganic carbon content in the water column.

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.

Calcium carbonate, biogenic opal, and organic carbon content and d15N ratios of sediments from the Bering Sea

Millennial-scale paleoceanographic changes in the Bering Sea during the last 71 kyrs were reconstructed using geochemical and isotope proxies (biogenic opal, CaCO3, and total organic carbon (TOC), nitrogen and carbon isotopes of sedimentary organic matters) and microfossil (radiolaria and foraminifera) data from two cores (PC23A and PC24A) which were collected from the northern continental slope area at intermediate water depths. Biogenic opal and TOC contents were generally high with high sedimentation rates during the last deglaciation. Laminated sediment depositions during the Early-Holocene (EH) and Bølling-Allerød (BA) were closely related with the increased primary productivity recorded by high biogenic opal and TOC contents and high d15N values. Enhanced surface-water productivity was attributed to increased nutrient supply from strengthened Bering Slope Current (BSC) and from increased amount of glacial melt-water, resulting in high C/N ratios and low d13C values, and high proportion of Rhizoplegma boreale during the last deglaciation. In contrast, low surface-water productivity during the last glacial period was due to depleted nutrient supply caused by strong stratification and to restricted phytoplankton bloom by extensive sea ice distribution under cold climates. Extensive formation of sea ice produces more oxygen-rich intermediate-water, leading to oxic bottom-water conditions due to active ventilation, which favored good preservation of oxic benthic foraminifera species. Remarkable CaCO3 peaks coeval with high biogenic opal and TOC contents in both cores during MIS 3 to MIS 4 are most likely correlated with Dansgaard-Oeschger (D-O) events. High d15N and d13Corg values during D-O interstadials support increased surface-water productivity resulting from nutrients supplied mainly by intensified BSC. During the EH, BA and D-O interstadials, dominant benthic foraminifera species indicate dysoxic bottom-water conditions as a result of increased surface-water productivity and weak ventilation of intermediate-water with mitigated sea ice development caused by strengthening of the Alaskan Stream. It is of note that the bottom-water conditions and formation of intermediate-water in the Bering Sea during the last glacial period are related to the variation of dissolved oxygen concentration of the bottom-water in the northeastern Pacific and to strong ventilation of intermediate-water in the northwestern Pacific. Thus, the millennial-scale paleoceanographic events in the Bering Sea during the D-O interstadials are closely associated with the intermediate-water ventilation, ultimately leading to weakening of North Pacific Intermediate Water.

(Table 1) Oxygen and carbon isotopes and calcium carbonte of bulk carbonate at DSDP Hole 72-516F

A detailed oxygen and carbon isotope study of the upper Maestrichtian-lower Paleocene section of Hole 516F from the Rio Grande Rise reveals that large isotopic anomalies are clearly associated with the Cretaceous/Tertiary boundary. Across the Cretaceous/Tertiary boundary, the total carbonate content reaches a maximum exceeding 80% before rapidly decreasing in covariance with the carbon isotope record. This strong covariance between d13C and percent CaCO3 suggests either a significant reduction in primary productivity or a rapid shoaling of the calcium carbonate compensation depth. Importantly, the d13C record 2 Ma after the Cretaceous/Tertiary boundary remained depleted in 13C by at least 0.5 per mil compared to the late Maestrichtian.

Middle Eocene bulk sediment, benthic and planktic foraminiferal stable isotope values, and relative weight percent CaCO3 content from ODP Site 207-1260

Major ice sheets were permanently established on Antarctica approximately 34 million years ago, close to the Eocene/ Oligocene boundary, at the same time as a permanent deepening of the calcite compensation depth in the world's oceans. Until recently, it was thought that Northern Hemisphere glaciation began much later, between 11 and 5million years ago. This view has been challenged, however, by records of ice rafting at high northern latitudes during the Eocene epoch and by estimates of global ice volume that exceed the storage capacity of Antarctica at the same time as a temporary deepening of the calcite compensation depth 41.6 million years ago. Here we test the hypothesis that large ice sheets were present in both hemispheres 41.6 million years ago using marine sediment records of oxygen and carbon isotope values and of calcium carbonate content from the equatorial Atlantic Ocean. These records allow, at most, an ice budget that can easily be accommodated on Antarctica, indicating that large ice sheets were not present in the Northern Hemisphere. The records also reveal a brief interval shortly before the temporary deepening of the calcite compensation depth during which the calcite compensation depth shoaled, ocean temperatures increased and carbon isotope values decreased in the equatorial Atlantic. The nature of these changes around 41.6 million years ago implies common links, in terms of carbon cycling, with events at the Eocene/Oligocene boundary and with the 'hyperthermals' of the Early Eocene climate optimum. Our findings help to resolve the apparent discrepancy between the geological records of Northern Hemisphere glaciation and model results that indicate that the threshold for continental glaciation was crossed earlier in the Southern Hemisphere than in the Northern Hemisphere.

Benthic oxygen and nitrogen fluxes at different time series sites in the southern North Sea, 2012 to 2014

Benthic oxygen and nitrogen fluxes were quantified within the years 2012 to 2014 at different time series sites in the southern North Sea with the benthic lander NuSObs (Nutrient and Suspension Observatory). In situ incubations of sediments, in situ bromide tracer studies, sampling of macrofauna and pore water investigations revealed considerable seasonal and spatial variations of oxygen and nitrogen fluxes. Seasonal and spatial variations of oxygen fluxes were observed between two different time series sites, covering different sediment types and/or different benthic macrofaunal communities. On a sediment type with a high content of fine grained particles (<63 µm) oxygen fluxes of -15.5 to -25.1 mmol/m**2/d (June 2012), -2.0 to -8.2 mmol/m**2/d (March 2013), -16.8 to -21.5 mmol/m**2/d (November 2013) and -6.1 mmol/m**2/d (March 2014) were measured. At the same site a highly diverse community of small species of benthic macrofauna was observed. On a sediment type with a low content of fine grained particles (<63 µm) high oxygen fluxes (-33.2 mmol/m**2/d August 2012; -47.2 to -55.1 mmol/m**2/d November 2013; -16.6 mmol/m**2/d March 2014) were observed. On this sediment type a less diverse benthic macrofaunal community, which was dominated by the large bodied suspension feeder Ensis directus, was observed. Average annual rain rates of organic carbon and organic nitrogen to the seafloor of 7.44 mol C/m**2/y and 1.34 mol N/m**2/y were estimated. On average 79% of the organic bound carbon and 95% of the organic bound nitrogen reaching the seafloor are recycled at the sediment-water interface.

Total organic carbon content, methane isotopic composition and hydrocarbon characteristics of ODP Leg 180 sites

The organic geochemistry of Sites 1108 and 1109 of the Woodlark Basin, offshore Papua New Guinea, was studied to determine whether thermally mature hydrocarbons were present in the penetrated section and, if present, whether they are genetically related to the penetrated "coaly" interval. Both the organic carbon and pyrolysis data indicate that there is no significant hydrocarbon source-rock potential at Site 1108. The hydrocarbons encountered during drilling appear to be indigenous and not migrated products or contaminants. In contrast, the coaly interval at Site 1109 contains zones with significant hydrocarbon-generation potential. Several independent lines of evidence indicate that the coaly sequence encountered at Site 1109 is thermally immature. The Site 1108 methane stable-carbon isotope composition does not display a clear trend with depth as would be expected if it was solely reflecting a maturation profile. The measured isotopic composition of methane has most probably been altered by fractionation during sample handling and storage. This fractionation would result in isotopically heavier values than would be obtained on free gas. The organic geochemical data gathered indicate that Site 1108 can be safely revisited and that the organic-rich sediments encountered at Site 1109 were not the source of the gas encountered at Site 1108.

(Table) Bacterial counts and Fe, Mn and SO4 content in sediments and pore waters of two cores from Lake Baikal

Sediments at the bottom of Lake Baikal are mostly oxidized at their surface, and the oxidized sedimentary deposits are enriched in Fe and Mn hydroxides. The thickness of the oxidized zone of the pelagic sediments averages at 5 cm and locally reaches 10-15, occasionally exceeding 20 cm. Both the thickness of the oxidized layer and the degree of its enrichment in iron and manganese hydroxides are controlled by the depth to which oxygen can penetrate into the sedimentary deposits, which is, in turn, closely related to the sedimentation conditions in the lake (which broadly vary). The sedimentation rate far off the shores of Lake Baikal ranges from <0.02 mm/year to 1.5 mm/year, and the content of organic matter buried in the sediments varies from 0.1 to >4%. The variability of the sedimentation process makes Lake Baikal very convenient to study its diagenetic processes related to redox reactions in sediments, first of all, processes responsible for the redistribution of Fe and Mn compounds. Although the diagenetic enrichment of Fe and Ni in bottom sediments is known to be of biogenic character, very scarce information is available so far on the microorganisms involved in the redistribution of these elements in sediments in Lake Baikal, which lately led us to explore this issue in detail. Our research was centered on the role played by the microbial community in the diagenetic transformations of Fe and Mn with reference to sedimentation conditions in Lake Baikal.

Lithology, stratigraphy, organic carbon content, extract and liquid chromatography yields, and Rock-Eval pyrolysis at DSDP Holes 75-530A and 75-532

Seventeen sediment samples of Albian-Cenomanian to early Pliocene age from DSDP Hole 530A in the Angola Basin and six sediment samples of early Pliocene to late Pleistocene age from the Walvis Ridge were investigated by organic geochemical methods, including organic carbon determination, Rock-Eval pyrolysis, gas chromatography and combined gas chromatography/mass spectrometry of extractable hydrocarbons, and kerogen microscopy. The organic matter in all samples is strongly influenced by a terrigenous component from the nearby continent. The amount of marine organic matter present usually increases with the total organic carbon content, which reaches an extreme value of more than 10% in a Cenomanian black shale from Hole 530A. At Site 530 the extent of preservation of organic matter in the deep sea sediments is related to mass transport down the continental slope, whereas the high organic carbon contents in the sediments from Site 532 reflect both high bioproductivity in the Benguela upwelling regime and considerable supply of terrigenous organic matter. The maturation level of the organic matter is low in all samples.

Seawater carbonate chemistry and protein content, respiration, symbiodinium densities, survivorship of Pocillopora damicornis larvae in a laboratory experiment

Efforts to evaluate the response of coral larvae to global climate change (GCC) and ocean acidification (OA) typically employ short experiments of fixed length, yet it is unknown how the response is affected by exposure duration. In this study, we exposed larvae from the brooding coral Pocillopora damicornis to contrasts of temperature (24.00 °C [ambient] versus 30.49 °C) and pCO2 (49.4 Pa versus 86.2 Pa) for varying periods (1-5 days) to test the hypothesis that exposure duration had no effect on larval response as assessed by protein content, respiration, Symbiodinium density, and survivorship; exposure times were ecologically relevant compared to representative pelagic larval durations (PLD) for corals. Larvae differed among days for all response variables, and the effects of the treatment were relatively consistent regardless of exposure duration for three of the four response variables. Protein content and Symbiodinium density were unaffected by temperature and pCO2, but respiration increased with temperature (but not pCO2) with the effect intensifying as incubations lengthened. Survival, however, differed significantly among treatments at the end of the study, and by the 5th day, 78% of the larvae were alive and swimming under ambient temperature and ambient pCO2, but only 55-59% were alive in the other treatments. These results demonstrate that the physiological effects of temperature and pCO2 on coral larvae can reliably be detected within days, but effects on survival require > or = 5 days to detect. The detection of time-dependent effects on larval survivorship suggests that the influence of GCC and OA will be stronger for corals having long PLDs.

Photosynthetically active radiation during the experiment, and lipid content of sub- and intertidal specimens of the endemic Antarctic red alga, Palmaria decipiens

In coastal waters, Antarctic rhodophytes are exposed to harsh environmental conditions throughout the year, like low water temperatures ranging from -1.8°C to 2°C and high light during the summer season. Photosynthetic performance under these conditions may be affected by slowed down enzymatic reactions and the increased generation of reactive oxygen species. The consequence might be a chronic photoinhibition of photosynthetic primary reactions related to increased fragmentation of the D1 reaction centre protein in photosystem II. It is hypothesized that changes in lipid composition of biomembranes may represent an adaptive trait to maintain D1 turnover in response to temperature variation. The interactive effects of high light and low temperature were studied on an endemic Antarctic red alga, Palmaria decipiens, sampled from two shore levels, intertidal and subtidal, and exposed to mesocosm experiments using two levels of natural solar radiation and two different temperature regimes (2-5°C and 5-10°C). During the experimental period of 23 days, maximum quantum yield of photosynthesis decreased in all treatments, with the intertidal specimens exposed at 5-10°C being most affected. On the pigment level, a decreasing ratio of phycobiliproteins to chlorophyll a was found in all treatments. A pronounced decrease in D1 protein concentration occurred in subtidal specimens exposed at 2-5°C. Marked changes in lipid composition, i.e. the ratio of saturated to unsaturated fatty acids, indicated an effective response of specimens to temperature change. Results provide new insights into mechanisms of stress adaptation in this key species of shallow Antarctic benthic communities.

Carbonate and terrigenous content and chemical composition of sediments in the Central Equatorial Pacific

This study addresses changes in the absolute magnitude and spatial geometry of particle flux and export production in a meridional transect across the central equatorial Pacific Ocean's upwelling system during oxygen isotope Stage 11 and Stage 12 and compares these time periods to the current Holocene interglacial system. Temporal and spatial variability in several chemical proxies of export production, and in particular the distributions of Ba, scavenged Al, and P, are studied in a suite of sediment cores gathered along a cross-equator transect at 5°S, 2°S, 0°, 2°N, and 4°N. Because this latitudinal range preserves strong gradients in biogenic particle flux in the modern equatorial Pacific Ocean, we are able to assess variations in the relative magnitude of export production as well as the meridional width of the equatorial system through the late Quaternary glacial/interglacial cycles. During interglacial oxygen isotope Stage 11 the chemical proxies each indicate lower particle flux and export production than during Stage 12. These records are consistent throughout the transect during this time period, but geographic narrowing (during the interglacial) and widening (during the glacial) of the meridional gradient also occurs. Although carbonate concentration varies dramatically through glacial/interglacial cycles at all latitudes studied, the productivity proxies record only minimal glacial/interglacial change at 5°S and 4°N, indicating that the carbonate minima at these latitudes is controlled dominantly by dissolution rather than production. The chemical data indicate that although the spatial geometry of the system during Stages 11 and 12 indicates maximum productivity at the equator during both glacial and interglacial conditions, the absolute magnitude of export production integrated from 5°S to 4°N during Stage 11 was 25-50% less than during Stage 12, and also was 25-50% less than it is now.

Trace element content and coordinates for factors at DSDP Hole 72-516F

This study involves samples of Santonian to Eocene age (Cores 516F-125 to 516F-38) taken from the Rio Grande Rise in the South Atlantic Ocean. These samples are from DSDP Site 516 occupied during Leg 72 of the Glomar Challenger (details given in site chapter, Site 516, this volume). Only Santonian to Paleocene cores have been well sampled, and analyses of the Eocene samples are preliminary results. Results of the trace element analyses (Mg, Sr, Mn, Ni, Fe, Na, K) of the carbonate fraction and CaCO3 percentage for each sample can be found in Renard and others (1983). Whole geochemical data are treated by the statistical method of correspondence analysis. Oxygen and carbon isotopic ratios measured on samples close to the Cretaceous/Tertiary boundary are not used in this study.