Geochemistry and Hg isotopic composition of mid-Pleistocene sapropel of ODP Hole 161-974C

The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average d202Hg value of -0.91 per mil ± 0.15 per mil (n = 5, 1 SD) and D199Hg value of 0.11 per mil ± 0.03 per mil (n = 5, 1 SD). Background sediments have an average d202Hg of -0.76 per mil ± 0.16 per mil (n = 5, 1 SD) and D199Hg of 0.05 per mil ± 0.01 per mil (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.

Biogenic and terrigeneous components in Pliocene-Pleistocene sediments of the equatorial Atlantic

High-resolution analyses of sediments at equatorial Atlantic Sites 662, 663, and 664 define the accumulation rates of biogenically produced CaC03 and opal and of eolian dust from North Africa over the last 3.7 m.y. The mean flux of opal increased abruptly by 60%-70% near 2.5 Ma (2.65 to 2.3 Ma), reflecting pulses of increased opal productivity along the equator due mainly to increased upwelling. The mean winter-plume dust influx from Sahelian and Saharan Africa also increased at this time by between 35% and 75%, following smaller increases earlier in the late Pliocene. The increased opal flux implies a stronger zonal component of the southern trade winds in Southern Hemisphere winter. Consistent with this wind configuration, the stronger dust flux suggests a weaker southwesterly monsoonal flow into Africa in Northern Hemisphere summer, thus increasing Sahelian aridity and winter-plume dust fluxes. Dust fluxes to the equator may possibly have also been enhanced by stronger Northern Hemisphere winter trade winds and a more southerly position of the Intertropical Convergence Zone over Africa. These late Pliocene biogenic and terrigenous flux changes coincided with the appearance of Northern Hemisphere ice sheets, implying an ultimate causal link. The immediate control on changes in tropical circulation may, however, have been changes in the Atlantic sector of the Southern Ocean. A steady background trend of increasing winter-plume dust flux occurred from the late Pliocene until the middle Pleistocene. This may reflect a progressive, tectonically induced aridification of northern and eastern Africa because of the gradual uplift of the Tibetan Plateau.

Mid-Pleistocene (800-400 ka) records of benthic and planktic foraminfer d18O and d13C, planktic foraminifer based SST, and IRD of IODP Site 306-U1314

Stable carbon and oxygen isotopes from benthic and planktic foraminifers, planktic foraminifer assemblages and ice rafted debris from the North Atlantic Site U1314 (Integrated Ocean Drilling Program Expedition 306) were examined to investigate orbital and millennial-scale climate variability in the North Atlantic and its impact on global circulation focusing on the development of glacial periods during the mid-Pleistocene (ca 800-400 ka). Glacial initiations were characterized by a rapid cooling (6-10 °C in less than 7 kyr) in the mean annual sea surface temperature (SST), increasing benthic d18O values and high benthic d13C values. The continuous increase in benthic d18O suggests a continuous ice sheet growth whereas the positive benthic d13C values indicate that the flow of the Iceland Scotland Overflow water (ISOW) was vigorous. Strong deep water formation in the Norwegian Greenland Sea promoted a high transfer of freshwater from the ocean to the continents. However, low SSTs at Site U1314 suggest a subpolar gyre cooling and freshening that may have reduced deep water formation in the Labrador Sea during glacial initiations. Once the 3.5 per mil threshold in the benthic d18O record was exceeded, ice rafting started and ice sheet growth was punctuated by millennial-scale waning events which returned to the ocean part of the freshwater accumulated on the continents. Ice-rafting events were associated with a rapid reduction in the ISOW (benthic d13C values dropped 0.5-1 per mil) and followed by millennial-scale warmings. The first two millennial-scale warm intervals of each glacial period reached interglacial temperatures and were particularly abrupt (6-10 °C in ~3 kyr). Subsequent millennial-scale warm events were cooler probably because the AMOC was rather reduced as suggested by the low benthic d13C values. These two abrupt warming events that occurred at early glacial periods were also observed in the Antarctic temperature and CO2 records, suggesting a close correlation between both Hemispheres. The comparison of the sea surface proxies with the benthic d18O record (as the Southern sign) indicates the presence of a millennial-scale seesaw pattern similar to that seen during the Last Glacial period.

Growth rates of late Miocene corals from Crete (Greece)

Modern scleractinian corals are classical components of marine shallow warm water ecosystems. Their occurrence and diversity patterns in the geological record have been widely used to infer past climates and environmental conditions. Coral skeletal composition data reflecting the nature of the coral environment are often affected by diagenetic alteration. Ghost structures of annual growth rhythms are, however, often well preserved in the transformed skeleton. We show that these relicts represent a valuable source of information on growth conditions of fossil corals. Annual growth bands were measured in massive hemispherical Porites of late Miocene age from the island of Crete (Greece) that were found in patch reefs and level bottom associations of attached mixed clastic environments as well as isolated carbonate environments. The Miocene corals grew slowly, about 2-4 mm/yr, compatible with present-day Porites from high-latitude reefs. Slow annual growth of the Miocene corals is in good agreement with the position of Crete at the margin of the Miocene reef belt. Within a given time slice, extension rates were lowest in level bottom environments and highest in attached inshore reef systems. Because sea surface temperatures (SSTs) can be expected to be uniform within a time slice, spatial variations in extension rates must reflect local variations in light levels (low in the level bottom communities) and nutrients (high in the attached reef systems). During the late Miocene (Tortonian-early Messinian), maximum linear extension rates remained remarkably constant within seven chronostratigraphic units, and if the relationship of SSTs and annual growth rates observed for modern massive Indo-Pacific Porites spp. applies to the Neogene, minimum (winter) SSTs were 20°-21°C. Although our paleoclimatic record has a low resolution, it fits the trends revealed by global data sets. In the near future we expect this new and easy to use Porites thermometer to add important new information to our understanding of Neogene climate.

Nd isotope composition of fossil fish teeth of ODP Hole 119-738B

We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.

The occurrence and significance of Pleistocene and Upper Pliocene sapropels

Numerous sapropels and sapropelic strata from Upper Pliocene and Pleistocene hemipelagic sediments of the Tyrrhenian Sea show that intermittent anoxia, possibly related to strongly increased biological productivity, was not restricted to the eastern Mediterranean basins and may be a basin-wide result of Late Pliocene-Pleistocene climatic variability. Even though the sapropel assemblage of the Tyrrhenian Sea clearly originates from multiple processes such as deposition under anoxic conditions or during spikes in surface water productivity and lateral transport of organic-rich suspensates, many "pelagic sapropels" have been recognized. Stratigraphic ages calculated for the organic-rich strata recovered during ODP Leg 107 indicate that the frequency of sapropel formation increased from the lowermost Pleistocene to the base of the Jaramillo magnetic event, coinciding with a period when stable isotope records of planktonic foraminifera indicate the onset of climatic cooling in the Mediterranean. A second, very pronounced peak in sapropel formation occurred in the Middle to Late Pleistocene (0.73-0.26 Ma). Formainifers studied in three high-resolution sample sets suggest that changes in surface-water temperature may have been responsible for establishing anoxic conditions, while salinity differences were not noted in the faunal assemblage. However, comparison of sapropel occurrence at Site 653 with the oxygen isotopic record of planktonic foraminifers established by Thunell et al. (1990, doi:10.2973/odp.proc.sr.107.155.1990) indicates that sapropel occurrences coincide with negative d18O excursions in planktonic foraminifers in thirteen of eighteen sapropels recognized in Hole 653A. A variant of the meltwater hypothesis accepted for sapropel formation in the Late Pleistocene eastern Mediterranean may thus be the cause of several "anoxic events" in the Tyrrhenian as well. Model calculations indicate that the amount of oxygen advection from Western Mediterranean Deep Water exerts the dominant control on the oxygen content in deep water of the Tyrrhenian Sea. Inhibition of deep-water formation in the northern Adriatic and the Balearic Basin by increased meltwater discharge and changing storm patterns during climatic amelioration may thus be responsible for sapropel formation in the Tyrrhenian Sea.

(Table 1) Typical trace-fossil occurrences in DSDP Holes 56-436 and 56-435A

Trace fossils are in places abundant in cores from DSDP Leg 56 sites. They are particularly rich in the pelagic-clay sequence at Site 436. Some significant trace fossils, including Zoophycos, Teichichnus, Chondrites, rind and solid burrows, and pellet-armored rods, are described. The ichnofauna, except for pellet-armored rods in diatomaceous mudstone of the landward trench slope, is characterized by cosmopolitan bathyal to abyssal forms.

Carbonate composition of Pliocene-Pleistocene sediments of the Maledives

Ocean Drilling Program (ODP) Leg 115 post-cruise research was focused on two Maldives sites, more precisely on the top 108 m of Hole 716B (water depth, 540 m), equivalent to the past 3.5 m.y., and the top 19.5 m of Hole 714A (water depth, 2195 m), equivalent to the past 0.55 m.y. These sediments consist of mostly unaltered and undisturbed, turbidite-free, periplatform ooze. Results of our research are compared with existing data on Hole 633A (water depth, 1681 m), drilled in the Bahamas during ODP Leg 101, using age/depth models built on the basis of oxygen isotope, nannofossil, and magnetic stratigraphies. Climate-induced, long-term (roughly 0.5 m.y.) aragonite cycles, superposed on short-term (roughly 0.04 and 0.1 m.y.) aragonite cycles, have been established at least during the past 2.0 m.y., in the Maldives and the Bahamas. Our most interesting result is the clear correlation among the aragonite long-term cycles in the Maldives and the Bahamas and the carbonate-preservation, long-term cycles from the open Pacific, Indian, and North Atlantic oceans. The mid-Brunhes dissolution interval, corresponding to the youngest preservation minima of the carbonate-preservation, longterm cycles, is clearly defined by fine aragonite minimum values in the deep periplatform sites, and by maximum fragmentation of pteropod tests in the shallow sites. Aragonite and planktonic d18O records, usually in phase during the late Pleistocene, display, further back in time, discreet intervals where the two records do not match with one another. Major mismatches between both records occur synchronously in the Maldives and Bahamas periplatform sites and seem to correspond to extreme events of either carbonate-preservation or dissolution in the deep pelagic carbonate sites of the equatorial Pacific Ocean. Based on our findings, short- and long-term aragonite cycles can no longer be explained only by variations of aragonite input from the nearby shallow carbonate banks, in response to their alternate flooding and exposure through cyclic sea-level fluctuations. The aragonite long-term cycles in the periplatform environments are interpreted as carbonatepreservation cycles at intermediate-water depths. Their occurrence shows, therefore, that the carbonate chemistry of the entire water column has been influenced by long-term (0.5 m.y.) cyclic variations during the past 2.0 m.y. These major changes of the water-column carbonate chemistry are linked to the climate-induced carbon cycling among the different atmospheric, oceanic, and sedimentary carbon reservoirs.

Calcium isotope fractionation in cultured, modern and fossil scleractinian coral skeleton

The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (d44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the d44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of d44/40Ca ranges from 0.6 to 0.1 per mil, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and d44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by d18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's d44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean.