(Table 2) Stable carbon and oxygen isotope ratios of foraminifera of DSDP Holes 29-277 and 31-292

Oxygen isotopic studies both of benthic formanifera (Emiliani, 1954, doi:10.1126/science.119.3103.853; Savin et al., 1975, doi:10.1130/0016-7606(1975)86<1499:TMP>2.0.CO;2; Shackleton and Kennett, 1975, doi:10.2973/dsdp.proc.29.117.1975; Savin, 1977, doi:10.1146/annurev.ea.05.050177.001535) and shallow-marine carbonates ( Dorman, 1966; Devereux, 1967; Buchart, 1978, doi:10.1038/275121a0) have provided a useful monitor of marine palaeotemperatures. The Deep Sea Drilling Project (DSDP) has provided cores from many ocean basins to conduct detailed stable isotopic and palaeoceanographic studies of the Cenozoic and late Mesozoic. DSDP Sites 277 and 292, separated by ~60° latitude in Palaeogene times, each record an 18O enrichment in benthic foraminifera of nearly 1 per mil beginning at the Eocene-Oligocene boundary. Planktonic foraminiferal trends are similar to benthic trends in the high latitude southwest Pacific Ocean, but tropical planktonics show only a minor (~0.3 per mil) increase which may reflect a change in seawater composition. These results suggest a sudden cooling of Pacific deep waters and high latitude surface waters forms a useful stratigraphic marker for the Eocene-Oligocene boundary. This boundary is particularly important because of its association with several worldwide palaeo-oceanographic and biogeographic changes. These include a sudden drop in the calcite compensation depth of 1-2 km (van Andel et al., 1975; van Andel, 1975, doi:10.1016/0012-821X(75)90086-2); a decrease in planktonic microfossil diversity (Lipps, 1970, 10.2307/2406711; Kennett, 1978, doi:10.1016/0377-8398(78)90017-8; Sancetta, 1979, doi:10.1016/0377-8398(79)90025-2); a change in planktonic biogeographic patterns (Kennett, 1978, doi:10.1016/0377-8398(78)90017-8; Sancetta, 1979, doi:10.1016/0377-8398(79)90025-2; Haq and Lohmann, 1976, doi:10.1016/0377-8398(76)90008-6); and increased erosion of deep-sea sediments over wide areas (Kennet et al., 1972; Moore et al., 1978).

(Table 3) Oxygen and carbon isotopic record of living (Rose Bengal Stained) benthic foraminifera of North Atlantic surface sediments

Variation of the d13C of living (Rose Bengal stained) deep-sea benthic foraminifera is documented from two deep-water sites (~2430 and ~3010 m) from a northwest Atlantic Ocean study area 275 km south of Nantucket Island. The carbon isotopic data of Hoeglundina elegans and Uvigerina peregrina from five sets of Multicorer and Soutar Box Core samples taken over a 10-month interval (March, May, July, and October 1996 and January 1997) are compared with an 11.5 month time series of organic carbon flux to assess the effect of organic carbon flux on the carbon isotopic composition of dominant taxa. Carbon isotopic data of Hoeglundina elegans at 3010 m show 0.3 per mil lower mean values following an organic carbon flux maximum resulting from a spring phytoplankton bloom. This d13C change following the spring bloom is suggested to be due to the presence of a phytodetritus layer on the seafloor and the subsequent depletion of d13C in the pore waters within the phytodetritus and overlying the sediment surface. Carbon isotopic data of H. elegans from the 2430 m site show an opposite pattern to that found at 3010 m with a d13C enrichment following the spring bloom. This different pattern may be due to spatial variation in phytodetritus deposition and resuspension or to a limited number of specimens recovered from the March 1996 cruise. The d13C of Uvigerina peregrina at 2430 m shows variation over the 10 month interval, but an analysis of variance shows that the variability is more consistent with core and subcore variability than with seasonal changes. The isotopic analyses are grouped into 100 µm size classes on the basis of length measurements of individual specimens to evaluate d13C ontogenetic changes of each species. The data show no consistent patterns between size classes in the d13C of either H. elegans or U. peregrina. These results suggest that variation in organic carbon flux does not preferentially affect particular size classes, nor do d13C ontogenetic changes exist within the >250 to >750 µm size range for these species at this locality. On the basis of the lack of ontogenetic changes a range of sizes of specimens from a sample can be used to reconstruct d13C in paleoceanographic studies. The prediction standard deviation, which is composed of cruise, core, subcore, and residual (replicate) variability, provides an estimate of the magnitude of variability in fossil d13C data; it is 0.27 per mil for H. elegans at 3010 m and 0.4 per mil for U. peregrina at the 2430 m site. Since these standard deviations are based on living specimens, they should be regarded as minimum estimates of variability for fossil data based on single specimen analyses. Most paleoceanographic reconstructions are based on the analysis of multiple specimens, and as a result, the standard error would be expected to be reduced for any particular sample. The reduced standard error resulting from the analysis of multiple specimens would result in the seasonal and spatial variability observed in this study having little impact on carbon isotopic records.

(Table 1) Stable oxygen isotope ratios of interstitial waters from ODP Sites 164-994 and 164-997

The d18O values of interstitial waters from Site 994 and Site 997 sediments, Blake Ridge, western Atlantic, tend to decrease with depth from 0.3 per mil to -0.5 per mil Standard Mean Ocean Water in the upper 200 mbsf, then fluctuate with significant positive spikes of Delta = 0.2 per mil - 0.5 per mil in the gas hydrate zone (200 to 450 mbsf), and finally increase from -0.4 per mil to -0.2 per mil toward 700 mbsf. Positive shifts of d18O IW in the gas hydrate zone are probably caused by the dissociation of gas hydrates originally contained in sediment cores. Gas hydrates recovered from the sites are enriched in 18O, d18O ranging between 2.7 per mil and 3.5 per mil. d18O values of gas hydrates and ambient interstitial waters give an oxygen isotopic fractionation factor of 1.0034-1.0040 at 12°-16°C and ~31 MPa (3 km below sea level). Based on this fractionation and observed isotopic anomalies in the gas hydrate zone, gas hydrates occupy 6% to 12% of pore-space volume within Blake Ridge sediments.

Sedimentology, age models and stable isotope ratios of sediment cores from the equatorial Pacific

Based on detailed reconstructions of global distribution patterns, both paleoproductivity and the benthic d13C record of CO2, which is dissolved in the deep ocean, strongly differed between the Last Glacial Maximum and the Holocene. With the onset of Termination I about 15,000 years ago, the new (export) production of low- and mid-latitude upwelling cells started to decline by more than 2-4 Gt carbon/year. This reduction is regarded as a main factor leading to both the simultaneous rise in atmospheric CO2 as recorded in ice cores and, with a slight delay of more than 1000 years, to a large-scale gradual CO2 depletion of the deep ocean by about 650 Gt C. This estimate is based on an average increase in benthic d13C by 0.4-0.5 per mil. The decrease in new production also matches a clear 13C depletion of organic matter, possibly recording an end of extreme nutrient utilization in upwelling cells. As shown by Sarnthein et al., [1987], the productivity reversal appears to be triggered by a rapid reduction in the strength of meridional trades, which in turn was linked via a shrinking extent of sea ice to a massive increase in high-latitude insolation, i.e., to orbital forcing as primary cause.

In situ d18O and Mg/Ca analyses of ODP Site 143-865 samples

We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.

Stable carbon isotope ratios of carbon dioxide from EDC and Berkner Island ice cores for 40-50 ka BP

The stable carbon isotopic signature of carbon dioxide (d13CO2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric d13CO2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble-clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO2 concentration values, presenting a worst-case test for d13CO2 reconstructions. Even so, the reconstructed atmospheric d13CO2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16 per mil magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of d13CO2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs.

Stable isotope and Mg/Ca record of IODP Site 339-U1385

Although millennial-scale climate variability (<10 ka) has been well studied during the last glacial cycles, little is known about this important aspect of climate in the early Pleistocene, prior to the Middle Pleistocene Transition. Here we present an early Pleistocene climate record at centennial resolution for two representative glacials (marine isotope stages (MIS) 37-41 from approximately 1235 to 1320 ka) during the "41 ka world" at Integrated Ocean Drilling Program Site U1385 (the "Shackleton Site") on the southwest Iberian margin. Millennial-scale climate variability was suppressed during interglacial periods (MIS 37, MIS 39, and MIS 41) and activated during glacial inceptions when benthic d18O exceeded 3.2 per mil. Millennial variability during glacials MIS 38 and MIS 40 closely resembled Dansgaard-Oeschger events from the last glacial (MIS 3) in amplitude, shape, and pacing. The phasing of oxygen and carbon isotope variability is consistent with an active oceanic thermal bipolar see-saw between the Northern and Southern Hemispheres during most of the prominent stadials. Surface cooling was associated with systematic decreases in benthic carbon isotopes, indicating concomitant changes in the meridional overturning circulation. A comparison to other North Atlantic records of ice rafting during the early Pleistocene suggests that freshwater forcing, as proposed for the late Pleistocene, was involved in triggering or amplifying perturbations of the North Atlantic circulation that elicited a bipolar see-saw response. Our findings support similarities in the operation of the climate system occurring on millennial time scales before and after the Middle Pleistocene Transition despite the increases in global ice volume and duration of the glacial cycles.

Oxygen isotope ratios on calcite from the Pià nico lake record

Stable oxygen isotope analyses at annual, 2-, 5-, 10- and 20-varve sample resolutions were carried out on two selected varve intervals from the interglacial sediment record of the Piànico palaeolake. These sediments are particularly suitable for ultra-high-resolution isotope analyses on lacustrine endogenic calcite because of the exceptionally well-preserved varve structure. A bias through detrital contamination can be excluded because microscopically controlled sampling enabled selecting detritus-free samples. The studied sediment intervals comprise 352 and 88 continuous varve series formed during periods of rapid climate change at the onset and end of a marked millennial-scale cool interval during the Piànico Interglacial. The most intriguing result is a pronounced short-term oscillation in the bi-annually resolved isotope record superimposed on the general decreasing and increasing d18O trends at the climatic transitions that is recorded at lower sample resolution. Spectral analyses of the bi-annual time series reveal periodicities indicating solar and NAO controls on the d18O record. Multiple d18O measurements from endogenic calcite of individual varves showed variations of up to 0.6 per mil, thus larger than the observed inter-annual variability and most likely explained by seasonal effects.

(Table 1) Geochemistry of the ETM-2 section from IODP Hole 302-M0004A

During the early Eocene, a series of short-term global warming events ("hyperthermals") occurred in response to the rapid release of carbon into the oceans and atmosphere. In order to investigate the response of ocean redox to global warming, we have determined the molybdenum isotope compositions (d98/95Mo) of samples spanning one such hyperthermal (Eocene Thermal Maximum 2 (ETM-2, 54.1 Ma)), from Integrated Ocean Drilling Program Expedition 302 Site M0004A in the Arctic Ocean. The highest d98/95Mo in our sample set (2.00 ± 0.11 per mil) corresponds to the development of local euxinia at Site M0004A during the peak of ETM-2, which we interpret as recording the global seawater d98/95Mo at that time. The ETM-2 seawater d98/95Mo is indistinguishable from a recent estimate of seawater d98/95Mo from an earlier hyperthermal (Paleocene Eocene Thermal Maximum (PETM, 55.9 Ma), d98/95Mo = 2.08 ± 0.11 per mil). We argue that the similarity in seawater d98/95Mo during ETM-2 and the PETM was caused by the development of transient euxinia in the Arctic Ocean during each hyperthermal that allowed sediments accumulating in this basin to capture the long-term d98/95Mo of early Eocene seawater. Our new data therefore place a minimum constraint on the magnitude of transient global seafloor deoxygenation during early Eocene hyperthermals.

(Table 1) Stable oxygen isotope ratios of benthic foraminifera from Pacific Ocean deep-sea sediments

The thermal structure of the Pacific Ocean between water depths of about 1 and 4.5 kilometers is estimated from the oxygen isotopic ratio of benthonic foraminifera from deep-drilled and piston cores of early Pliocene age (about 3 to 5 million years ago). The ratio of oxygen-18 to oxygen-16 in the early Pliocene at each site varies by an average of only ± 0.12 per mil (1 standard deviation). A plot of the oxygen isotopic ratio against modern bottom-water temperature is adequately fit by a line having a slope of - 0.26 per mil per degree Celsius (the equilibrium temperature dependence of calcite-water fractionation), suggesting that the temperature gradient of the Pacific Ocean during the early Pliocene was similar to that of today.

Measurement results of d18O, Mg/Ca, and Ti/Ca of sediment cores GeoB10042-1 and GeoB10043-3

The advection of relatively fresh Java Sea water through the Sunda Strait is presently responsible for the low-salinity "tongue" in the eastern tropical Indian Ocean with salinities as low as 32 per mil. The evolution of the hydrologic conditions in the eastern tropical Indian Ocean since the last glacial period, when the Sunda shelf was exposed and any advection via the Sunda Strait was cutoff, and the degree to which these conditions were affected by the Sunda Strait opening are not known. Here we have analyzed two sediment cores (GeoB 10042-1 and GeoB 10043-3) collected from the eastern tropical Indian Ocean off the Sunda Strait that cover the past ~40,000?years. We investigate the magnitude of terrigenous supply, sea surface temperature (SST), and seawater d18O (d18Osw) changes related to the sea level-driven opening of the Sunda Strait. Our new spliced records off the Sunda Strait show that during the last glacial, average SST was cooler and d18Osw was higher than elsewhere in the eastern tropical Indian Ocean. Seawater d18O decreased ~0.5 per mil after the opening of the Sunda Strait at ~10 kyr B.P. accompanied by an SST increase of 1.7°C. We suggest that fresher sea surface conditions have persisted ever since due to a continuous transport of low-salinity Java Sea water into the eastern tropical Indian Ocean via the Sunda Strait that additionally increased marine productivity through the concomitant increase in terrigenous supply.

(Table 2) Chlorine geochemistry and mineralogy of altered oceanic crust samples

Bulk chlorine concentrations and chlorine stable isotope compositions were determined for hydrothermally altered basalt (extrusive lavas and sheeted dikes) and gabbro samples (n = 50) from seven DSDP/ODP/IODP drill sites. These altered oceanic crust (AOC) samples span a range of crustal ages, tectonic settings, alteration type, and crustal depth. Bulk chlorine concentrations range from < 0.01 wt.% to 0.09 wt.%. In general, higher chlorine concentrations coincide with an increase in temperature of alteration and amphibole content. d37Cl values of whole rock AOC samples range from -1.4 to +1.8 per mil. High d37Cl values (>=~0.5 per mil) are associated with areas of higher amphibole content. This observation is consistent with theoretical calculations that estimate amphibole should be enriched in 37Cl compared to co-existing fluid. Negative to near zero d37Cl values are found in areas dominated by clay minerals. Chlorine geochemistry is a rough indicator of metamorphic grade and mineralogy. AOC is a major Cl host in the subducting oceanic lithospheric slab. Here we show that bulk chlorine concentrations are ~3 times higher than previous estimates resulting in a greater contribution of Cl to the mantle.

(Table 1) Stable-isotope and eolian grain size data across the Paleocene/Eocene boundary from DSDP Hole 22-215

Deep Sea Drilling Project (DSDP) Site 215 provides an expanded section across the Paleocene/Eocene boundary, the most complete mid-latitude sequence from a Southern Hemisphere location in the Indo-Pacific area. The events of this transition occurred during a span of about 1.2 m.y. Oxygen isotope values derived from benthic foraminiferal calcite decrease by about 1.0 per mil, a decrease most likely related to warming of deep ocean waters. Turnovers of benthic foraminifera accompany d18O changes and culminate in the predominant extinction event at the end of the Paleocene Epoch. Carbon isotope ratios also shift dramatically toward lighter values near the end of the Paleocene, beginning about 0.45 m.y. after oxygen isotope values start to change. The intensity of Southern Hemisphere atmospheric circulation as recorded by grain sizes of eolian particles shows a large and rapid reduction beginning another 0.45 m.y. later. A significant reduction of zonal wind strength at the Paleocene/Eocene boundary, until now observed only at Northern Hemisphere locations, appears to have been a global phenomenon related to decreased latitudinal thermal gradients occasioned by more effective poleward heat transport via the deep ocean.

A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.

n-Alkane analyses from an transect of marine surface sediments off southwest Africa

An isobathic transect of marine surface sediments from 1°N to 28°S off southwest Africa was used to further evaluate the potential of the chain length distribution and carbon stable isotope composition of higher plant n-alkanes as proxies for continental vegetation and climate conditions. We found a strong increase in the n-C29-33 weighted mean average d13C values from -33 per mil near the equator to around -26 per mil further south. Additionally, C25-35n-alkanes reveal a southward trend of increasing average chain length from 30.0 to 30.5. The data reflect the changing contribution of plants employing different photosynthetic pathways (C3 and C4) and/or being differently influenced by the environmental conditions of their habitat. The C4 plant proportions calculated from the data (ca. 20% for rivers draining the rainforest, to ca. 70% at higher latitude) correspond to the C4 plant abundance in continental catchment areas postulated by considering prevailing wind systems and river outflows. Furthermore, the C4 plant contribution to the sediments correlates with the mean annual precipitation and aridity at selected continental locations in the postulated catchment areas, suggesting that the C4 plant fraction in marine sediments can be used to assess these environmental parameters.