Geochemistry of Eocene/Oligocene sediments of ODP Hole 154-925A

Paleoproductivity, nutrient burial, and carbon cycling were investigated across the Eocene/Oligocene (E/O) boundary (begin to end; 36.9-32.7 Ma at ~40 kyr resolution, timescale of Shackleton et al. (1999, doi:10.1098/rsta.1999.0407) at Ocean Drilling Program Site 925 on the Ceara Rise in the western equatorial Atlantic (3040 m present water depth; 748.26-850.70 mbsf). Downcore bulk sediment records of biogenic barium, total reactive phosphorus, biogenic silica, and calcium carbonate are interpreted to represent export production, net nutrient burial, biogenic opal production, and inorganic carbon burial, respectively. The global positive excursion in d13C subsequent to the E/O boundary is recorded at Site 925. Export production appears to have been externally forced by orbital parameters at eccentricity frequencies during the study interval, based on spectral analysis of the biogenic barium and reactive phosphorus records. Biogenic silica production or preservation increased after the Eocene/Oligocene boundary to a higher baseline, although overall productivity and nutrient burial did not increase, based on barium and reactive phosphorus records. Thus, although absolute production did not increase at this site, a shift in relative abundance of siliceous versus carbonate productivity may have resulted in a change in relative organic carbon burial. This may have contributed to the positive excursion in global oceanic d13C subsequent to the Eocene/Oligocene boundary, although the silica maximum persists after the carbon isotope excursion ends.

Sedimentology, organic geochemistry, and stable isotopes of core PS2138-1

We studied variations in terrigenous (TOM) and marine organic matter (MOM) input in a sediment core on the northern Barents Sea margin over the last 30 ka. Using a multiproxy approach, we reconstructed processes controlling organic carbon deposition and investigated their paleoceanographic significance in the North Atlantic-Arctic Gateways. Variations in paleo-surface-water productivity are not documented in amount and composition of organic carbon. The highest level of MOM was deposited during 25-23 ka as a result of scavenging on fine-grained, reworked, and TOM-rich material released by the retreating Svalbard/Barents Sea ice sheet during the late Weichselian. A second peak of MOM is preserved because of sorptive protection by detrital and terrigenous organic matter, higher surface-water productivity due to permanent intrusion of Atlantic water, and high suspension load release by melting sea ice during 15.9-11.2 ka.

Ichthyolith (fish tooth and denticle) counts from DSDP Site 91-596 and ODP Site 145-886

While the history of taxonomic diversification in open ocean lineages of ray-finned fish and elasmobranchs is increasingly known, the evolution of their roles within the open ocean ecosystem remains poorly understood. To assess the relative importance of these groups through time, we measured the accumulation rate of microfossil fish teeth and elasmobranch dermal denticles (ichthyoliths) in deep sea sediment cores from the North and South Pacific gyres over the past 85 million years. We find three distinct and stable open ocean ecosystem structures, each defined by the relative and absolute abundance of elasmobranch and ray-finned fish remains. The Cretaceous Ocean (pre-66 Ma), was characterized by abundant elasmobranch denticles, but low abundances of fish teeth. The Paleogene Ocean (66-20 Ma), initiated by the Cretaceous/Paleogene Mass Extinction, had nearly 4 times the abundance of fish teeth compared to elasmobranch denticles. This Paleogene Ocean structure remained stable during the Eocene greenhouse (50 Ma) and the Eocene-Oligocene glaciation (34 Ma), despite large changes in overall accumulation of both groups during those intervals, suggesting that climate change is not a primary driver of ecosystem structure. Dermal denticles virtually disappeared from open ocean ichthyolith assemblages about 20 Ma, while fish tooth accumulation increased dramatically in variability, marking the beginning of the Modern Ocean. Together, these results suggest that open ocean fish community structure is stable on long timescales, independent of total production and climate change. The timing of the abrupt transitions between these states suggests that the transitions may be due to interactions with other, non-preserved pelagic consumer groups.

Late Eocene to early Oligocene carbonate and barite accumulation rates in the Pacific Basin

The late Eocene through earliest Oligocene (40-32 Ma) spans a major transition from greenhouse to icehouse climate, with net cooling and expansion of Antarctic glaciation shortly after the Eocene/Oligocene (E/O) boundary. We investigated the response of the oceanic biosphere to these changes by reconstructing barite and CaCO3 accumulation rates in sediments from the equatorial and North Pacific Ocean. These data allow us to evaluate temporal and geographical variability in export production and CaCO3 preservation. Barite accumulation rates were on average higher in the warmer late Eocene than in the colder early Oligocene, but cool periods within the Eocene were characterized by peaks in both barite and CaCO3 accumulation in the equatorial region. We infer that climatic changes not only affected deep ocean ventilation and chemistry, but also had profound effects on surface water characteristics influencing export productivity. The ratio of CaCO3 to barite accumulation rates, representing the ratio of particulate inorganic C accumulation to Corg export, increased dramatically at the E/O boundary. This suggests that long-term drawdown of atmospheric CO2 due to organic carbon deposition to the seafloor decreased, potentially offsetting decreasing pCO2 levels and associated cooling. The relatively larger increase in CaCO3 accumulation compared to export production at the E/O suggests that the permanent deepening of the calcite compensation depth (CCD) at that time stems primarily from changes in deep water chemistry and not from increased carbonate production.

Paleoceanography on sediment core MD01-2416

IMAGES core MD01-2416 (51°N, 168°E) provides the first centennial-scale multiproxy record of Holocene variation in North Pacific sea-surface temperature (SST), salinity, and biogenic productivity. Our results reveal a gradual decrease in subarctic SST by 3-5 °C from 11.1 to 4.2 ka and a stepwise long-term decrease in sea surface salinity (SSS) by 2-3 p.s.u. Early Holocene SSS were as high as in the modern subtropical Pacific. The steep halocline and stratification that is characteristic of the present-day subarctic North Pacific surface ocean is a fairly recent feature, developed as a product of mid-Holocene environmental change. High SSS matched a salient productivity maximum of biogenic opal during Bølling-to-Early Holocene times, reaching levels similar to those observed during preglacial times in the warm mid-Pliocene prior to 2.73 Ma. Similar productivity spikes marked every preceding glacial termination of the last 800 ka, indicating recurrent short-term events of mid-Pliocene-style intense upwelling of nutrient-rich Pacific Deepwater in the Pleistocene. Such events led to a repeated exposure of CO2-rich deepwater at the ocean surface facilitating a transient CO2 release to the atmosphere, but the timing and duration of these events repudiate a long-term influence of the subarctic North Pacific on global atmospheric CO2 concentration.

Eolian mass-accumulation rates and grain size at DSDP Sites 86-576 and 86-578

The mass-accumulation rate and grain size of the total eolian component of North Pacific pelagic clays at Deep Sea Drilling Project Sites 576 and 578 have been used to evaluate changes in eolian sedimentation and the intensity of atmospheric circulation that have occurred during the past 70 m.y. Eolian deposition, an indicator of source area aridity, was low in the Paleocene, Eocene, and Oligocene, apparently reflecting the humid environments of that time as well as the lack of glacial erosion products. A general increase in eoiian accumulation in the Miocene apparently reflects the relative increase in global aridity during the latter part of the Cenozoic. A dramatic increase in eolian accumulation rates in the Pliocene reflects the increased aridity and availability of glacial erosion products associated with Northern Hemisphere glaciation 2.5 m.y. ago. Eolian grain size, an indicator of wind intensity, suggests that Late Cretaceous wind strength was comparable to present-day wind strength. A sharp decrease in eolian grain size across the Paleocene/Eocene boundary is not readily interpreted, but may indicate a significant reduction in the intensity of atmospheric circulation at that time. Fine eolian grain size and low accumulation rates in the Eocene and early Oligocene are in agreement with low early Tertiary thermal gradients and less vigorous atmospheric circulation. Large increases in grain size during the Oligocene, mid-to-late Miocene, and Pliocene appear to be a response to steepening thermal gradients resulting from increasing polar isolation.

Chemistry of Late Quaternary sediments and their interstitial waters of sediment cores from the Nort-West African continental margin

In the sediments of the NW African continental margin the mainly biogenic carbonate constituents become increasingly diluted with terrigenous material as one approaches the coast, as indicated by the carbonate-CO2 content, the Al2O3/SiO2-ratios, and the presence of ammonia fixed to alumino-silicates, predominantly to illites. In the norther area of the investigation - off Cape Blanc and Cape Bojador . the terrigenous constituents are mainly quartz from the Sahara Desert, whereas in the south - off Senegal - more alumino-silicates as clay minerals are admixed with the carbonate constituents. The organic carbon content of the continental slope sediments off Senegal is higher than in samples of the continental rise or of the preservation of organic matter as a result of high production and relatively rapid sedimentation. The zone of manganese-oxide enrichment follows the redox potential of + 330 mV from the surface (0-5 cm) into the sediments (20-30 cm deep) at 2000--3000 m and 3700 m of water depths, respectively. At shallower water depths, low redox potentials preclude deposition of manganese oxides and cause their mobilization from the sediments. About 1/3 of the total sedimentary Zn and 1/4 of the Cu is associated with the carbonate mineral fraction, probably in calcium phosphate overgrowths as a result of the mineralization of phosphorus-containing organic matter. Besides the precipitation of calcium phosphate, the mineralization of organic matter mediated by bacterial sulfate reduction also results in calcium carbonate precipitation and the exchange of ammonia for potassium on illites. Because of these simultaneous reactions, the depth distribution of all mineralization constituents in the interstitial water can be determined using the actual molar carbon-to-nitrogen-to phosphorus ratios of the sedimentary organic matter. The amount of sulfide sulfur in this process indicates the predominance of bacterial sulfate reduction in the sediments off NW Africa. This process also preferentially decomposes nitrogen- and phosphorus-containing organic compounds so organic matter deficient in these elements is characteristic for the rapidly accumulating sediments than today, indicating there was increased production of organic carbon compounds and more favorable conditions of their preservations. During the last interglacial times conditions were similar to those to today. This differentiation with time has also been observed in sediments from the Argentine Basin and from slope off South India indicating perhaps world-wide environmental changes throughout Late Quaternary times.

Sedimentology and geochemistry of ODP Site 184-1144

We analyzed sediment from Ocean Drilling Program (ODP) Site 1144 in the northern South China Sea to examine the weathering response of SE Asia to the strengthening of the East Asian Monsoon (EAM) since 14 ka. Our high-resolution record highlights the decoupling between continental chemical weathering, physical erosion and summer monsoon intensity. Mass accumulation rates, Ti/Ca, K/Rb, hematite/goethite and 87Sr/86Sr show sharp excursions from 11 to 8 ka, peaking at 10 ka. Clay minerals show a shorter-lived response with a higher kaolinite/(illite + chlorite) ratio at 10.7-9.5 ka. However, not all proxies show a clear response to environmental changes. Magnetic susceptibility rises sharply between 12 and 11 ka. Grain-size becomes finer from 14 to 10 ka and then coarsens until ~7 ka, but is probably controlled by bottom current flow and sealevel. Sr and Nd isotopes show that material is dominantly eroded from Taiwan with a lesser flux from Luzon, while clay mineralogy suggests that the primary sources during the Early Holocene were reworked via the shelf in the Taiwan Strait, rather than directly from Taiwan. Erosion was enhanced during monsoon strengthening and caused reworking of chemically weathered Pleistocene sediment largely from the now flooded Taiwan Strait, which was transgressed by ~8 ka, cutting off supply to the deep-water slope. None of the proxies shows an erosional response lasting until ~6 ka, when speleothem oxygen isotope records indicate the start of monsoon weakening. Although more weathered sediments were deposited from 11 to 8 ka when the monsoon was strong these are reworked and represent more weathering during the last glacial maximum (LGM) when the summer monsoon was weaker but the shelves were exposed.

Uranium radionuclides and organic biomarkers in sediment core RC27-42

Uranium series radionuclides and organic biomarkers, which represent major groups of planktonic organisms, were measured in western Arabian Sea sediments that span the past 28 ka. Variability in the past strength of the southwest and northeast monsoons and its influence on primary productivity, sea surface temperature (SST), and planktonic community structure were investigated. The average alkenone-derived SST for the last glacial period was ~3°C lower than that measured for the Holocene. Prior to the deglacial, the lowest SSTs coincide with the highest measured fluxes of organic biomarkers, which represent primarily a planktonic suite of diatoms, coccolithophorids, dinoflagellates, and zooplankton. We propose that intensification of winter northeast monsoon winds during the last glacial period resulted in deep convective mixing, cold SSTs and enhanced primary productivity. In contrast, postdeglacial (<17 ka) SSTs are warmer during times in which biomarker fluxes are high. Associated with this transition is a planktonic community structure change, in which the ratio of the average cumulative flux of diatom biomarkers to the cumulative flux of coccolithophorid biomarkers is twice as high during the deglacial and Holocene than the average ratio during the last glacial period. We suggest that this temporal transition represents a shift from a winter northeast monsoon-dominated (pre-17 ka) to a summer southwest monsoon-dominated (post-17 ka) wind system.

Composition and accumulatein rates of bottom sediments from Core PS1599-3, Continental Slope of the Weddell Sea

Genetic sediment types have been identified based on a study of Core PS1599 collected from the eastern continental slope of the Weddell Sea. XRF analysis of 48 samples from this core carried out at the Vernadsky Institute of Geochemistry and Analytical Chemistry (Moscow) yielded the first comprehensive geochemical characteristics of all genetic types. Methods of correlation and factor analyses were used to outline geochemical associations of sediments and examine causes of their formation including the role of grain size composition. The results obtained have revealed fundamental differences between sources, mechanisms, and methods of transportation of sedimentary material for Holocene sediments, on the one hand, and Weichselian sediments, on the other hand.

Sr and Nd composition, stable oxygen isotope record and lithogenic flux in eastern Mediterranean sediments

Isotopic ratios of Sr and Nd from lithogenic components of three isochronous core sections recovered from an east-west transect in the Eastern Mediterranean Sea (EMS) have been analyzed. The data are used for a quantitative estimate of the temporal and spatial variation of detrital flux to the EMS, assuming Saharan dust and Aegean/Nile particulate matter as dominant end members. It was established that the carbonate-free Saharan dust flux during deposition of the nonsapropel layers of marine oxygen isotope stage 5.4 (MIS 5.4) was similar to the present flux. During the deposition of sapropels S5 and S6, however, the Saharan dust input was drastically reduced and was not balanced by a change in the riverine influx at this time. Denser vegetation cover during more humid conditions may have reduced physical erosion and sediment removal in the source area. During marine oxygen isotope stage 6.2 (MIS 6.2) a pronounced increase of Saharan dust and detrital influx from the Aegean region is evident and implies more arid conditions in the southern and northern catchment areas. During this period, intersite variations are interpreted in terms of their geographic location relative to the seaways connecting the Aegean Sea and EMS. The width of the straits and hence the amount of sediment entering the eastern basins may have been affected by a low sea level that impeded interbasin sediment dispersal.

Calcium carbonate in sediments at DSDP Leg 92

The carbonate contents of sediments recovered at Leg 92 Sites 597, 598, and 601 were determined at 5-cm intervals. The long-term record of carbonate variation at Sites 597 and 598 shows the effect of decreasing dilution by hydrothermal phases as the sites moved away from the ridge crest at which they formed. Superimposed on this trend are high-amplitude variations in carbonate content. In the lower portions of Sites 597 and 598 the high-amplitude variations have a duration of a few hundred thousand years. The upper portion of the sediment column at both sites was deposited below the lysocline, and high-amplitude variations in this interval represent 1 to 2 m.y. The data suggest that only very intense carbonate dissolution events can be identified reliably at sites with low accumulation rates. At sites like Site 598, where the sedimentation rate is higher, the details of carbonate variation can be correlated with the carbonate lithostratigraphies developed for sites in the equatorial and North Pacific oceans.

Benthic oxygen isotope and dust flux record from ODP Site 108-659 in the North Atlantic

High-resolution benthic oxygen isotope and dust flux records from Ocean Drilling Program site 659 have been analyzed to extend the astronomically calibrated isotope timescale for the Atlantic from 2.85 Ma back to 5 Ma. Spectral analysis of the delta18O record indicates that the 41-kyr period of Earth's orbital obliquity dominates the Pliocene record. This is shown to be true regardless of fundamental changes in the Earth's climate during the Pliocene. However, the cycles of Sahelian aridity fluctuations indicate a shift in spectral character near 3 Ma. From the early Pliocene to 3 Ma, the periodicities were dominantly precessional (19 and 23 kyr) and remained strong until 1.5 Ma. Subsequent to 3 Ma, the variance at the obliquity period (41 kyr) increased. The timescale tuned to precession suggests that the Pliocene was longer than previously estimated by more than 0.5 m.y. The tuned ages for the magnetic boundaries Gauss/Gilbert and Top Cochiti are about 6-8% older than the ages of the conventional timescale. A major phase of Pliocene northern hemisphere ice growth occurred between 3.15 Ma and 2.5 Ma. This was marked by a gradual increase in glacial Atlantic delta18O values of 1per mil and an increase in amplitude variations by up to 1.5 per mil, much larger than in the Pacific deepwater record (site 846). The first maxima occured in cold stages G6-96 between 2.7 Ma and 2.45 Ma. Prior to 3 Ma, the isotope record is characterized by predominantly low amplitude fluctuations (< 0.7 per mil). When obliquity forcing was at its minimum between 4.15 and 3.6 Ma and during the Kaena interval, delta18O amplitude fluctuations were minimal. From 4.9 to 4.3 Ma, the delta18O values decreased by about 0.5 per mil, reaching a long-term minimum at 4.15 Ma, suggesting higher deepwater temperatures or a deglaciation. Deepwater cooling and/or an increase in ice volume is indicated by a series of short-term delta18O fluctuations between 3.8 and 3.6 Ma.

Sedimentology and stable carbon and oxygen isotope record of the Central Arctic

Stable oxygen and carbon isotope and sedimentological-paleontological investigations supported by accelerator mass spectrometry 14C datings were carried out on cores from north of 85°N in the eastern central Arctic Ocean. Significant changes in accumulation rates, provenance of ice-rafted debris (IRD), and planktic productivity over the past 80,000 years are documented. During peak glacials, i.e., oxygen isotope stages 4 and 2, the Arctic Ocean was covered by sea ice with decreased seasonal variation, limiting planktic productivity and bulk sedimentation rates. In early stage 3 and during Termination I, major deglaciations of the circum-Arctic regions caused lowered salinities and poor oxygenation of central Arctic surface waters. A meltwater spike and an associated IRD peak dated to ~14-12 14C ka can be traced over the southern Eurasian Basin of the Arctic Ocean. This event was associated with the early and rapid deglaciation of the marine-based Barents Sea Ice Sheet. A separate Termination Ib meltwater event is most conspicuous in the central Arctic and is associated with characteristic dolomitic carbonate IRD. This lithology suggests an origin of glacial ice from northern Canada and northern Greenland where lower Paleozoic platform carbonates crop extensively out.

Geochemistry of Neogene sediments of ODP Hole 115-711A

Pelagic sedimentation in the northwest Indian Ocean has been studied using sediments from Hole 711A (the section from 0 to 70.5 mbsf, 0-22 Ma), a deep site (4428 m) drilled during Ocean Drilling Program Leg 115. The clay fraction of the sediments represents poorly developed pelagic deposits with considerably lower contents of Mn, Ba, Cu, Ni, Cr, and Zn than is typical for well-oxidized pelagic sediments formed far from the continents (e.g., in the central Indian or Pacific oceans). Geochemical provenance models, representing conservative mixing models with terrigenous, exhalative-volcanic, and biogenous matter as the only inputs, explain most of the compositional variations in the sediments. The models show that terrigenous matter accounts for about 96%-100% of all SiO2, Al2O3, TiO2, and Zr; about 73%-85% of all Fe2O3, V, and Ni; and about 40%-60% of the Cu and Zn abundances. Exhalative-volcanic matter delivers a large fra tion of Mn (78%-85%), some Fe (15%-219/o), and possibly some Cu (38%-51%). Biogenous deposition is generally of restricted significance; at most 6%-35% of all Cu and Zn may derive from biogenic matter. The exhalative-volcanic matter is slightly more abundant in the oldest deposits, reflecting a plate tectonic drift away from the volcanic Carlsberg Ridge. The Al/Ti ratio reveals that silicic crustal matter plays a somewhat larger role in the upper and lower part of the section studied, whereas the basaltic input is slightly higher in the intermediate levels (age 5-15 m.y.). The sediment abundances of Ba generally exceed those predicted by the models, an anomalous behavior also observed in equatorial Pacific sediments. This is possibly caused by poor knowledge of the input components. Several changes in accumulation rates seem to correlate with climatic changes (onset of monsoon-driven upwellings and sea-level regressions of about 50-100 m at 10, 15-16, and 20-21 Ma). A number of constituents show higher accumulation rates at or shortly after these regressions, suggesting an accelerated removal of fines from shallow oceanic areas. Furthermore, the SiO2/Al2O3 ratio shows a small increase in sediments younger than 10 Ma, implying an increase in biological productivity, particularly after the onset of monsoon-driven upwelling in the northwest Indian Ocean. This trend is paralleled by a general increase in the accumulation rates of Ba and CaCO3. However, these accumulation rates are generally significantly lower than under the biological high-productivity zone in the equatorial Pacific. The onset of these upwelling systems about 10 Ma is probably related to the closing of the gap between India and the main Asiatic continent, preventing free circulation around the Indian subcontinent.