Neodymium isotopes from fossil fish teeth and detrital sediment, and oxygen isotopes from benthic forams from ODP Hole 119-738 B

Ephemeral polar glaciations during the middle-to-late Eocene (48-34 Ma) have been proposed based on far-field ice volume proxy records and near-field glacigenic sediments, although the scale, timing, and duration of these events are poorly constrained. Here we confirm the existence of a transient cool event within a new high-resolution benthic foraminiferal d18O record at Ocean Drilling Program (ODP) Site 738 (Kerguelen Plateau; Southern Ocean). This event, named the Priabonian oxygen isotope maximum (PrOM) Event, lasted ~140 kyr and is tentatively placed within magnetochron C17n.1n (~37.3 Ma) based on the correlation to ODP Site 689 (Maud Rise, Southern Ocean). A contemporaneous change in the provenance of sediments delivered to the Kerguelen Plateau occurs at the study site, determined from the <63 µm fraction of decarbonated and reductively leached sediment samples. Changes in the mixture of bottom waters, based on fossil fish tooth epsilon-Nd, were less pronounced and slower relative to the benthic d18O and terrigenous epsilon-Nd changes. Terrigenous sediment epsilon-Nd values rapidly shifted to less radiogenic signatures at the onset of the PrOM Event, indicating an abrupt change in provenance favoring ancient sources such as the Paleoproterozoic East Antarctic craton. Bottom water epsilon-Nd reached a minimum value during the PrOM Event, although the shift begins much earlier than the terrigenous epsilon-Nd excursion. The origin of the abrupt change in terrigenous sediment provenance is compatible with a change in Antarctic terrigenous sediment flux and/or source as opposed to a reorganization of ocean currents. A change in terrigenous flux and/or source of Antarctic sediments during the oxygen isotope maximum suggests a combination of cooling and ice growth in East Antarctica during the early late Eocene.

Strontium isotope ratios and concentrations in fossil fish teeth

We analyzed 87Sr/86Sr ratios in foraminifera, pore fluids, and fish teeth for samples ranging in age from Eocene to Pleistocene from four Ocean Drilling Program sites distributed around the globe: Site 1090 in the Cape Basin of the Southern Ocean, Site 757 on the Ninetyeast Ridge in the Indian Ocean, Site 807 on the Ontong-Java Plateau in the western equatorial Pacific, and Site 689 on the Maud Rise in the Southern Ocean. Sr isotopic ratios for dated foraminifera consistently plot on the global seawater Sr isotope curve. For Sites 1090, 757, and 807 Sr isotopic values of the pore fluids are generally less radiogenic than contemporaneous seawater values, as are values for fossil fish teeth. In contrast, pore fluid 87Sr/86Sr values at Site 689 are more radiogenic than contemporaneous seawater, and the corresponding fish teeth also record more radiogenic values. Thus, Sr isotopic values preserved in fossil fish teeth are consistently altered in the direction of the pore fluid values; furthermore, there is a correlation between the magnitude of the offset between the pore fluids and the seawater curve, and the associated offset between the fish teeth and the seawater curve. These data suggest that the hydroxyfluorapatite of the fossil fish teeth continues to recrystallize and exchange Sr with its surroundings during burial and diagenesis. Therefore, Sr chemostratigraphy can be used to determine rough ages for fossil fish teeth in these cores, but cannot be used to fine-tune age models. In contrast to the Sr isotopic system, our Nd concentration data, combined with published isotopic and rare earth element data, suggest that fish teeth acquire Nd during early diagenesis while they are still in direct contact with seawater. The concentrations of Nd acquired at this stage are extremely high relative to the concentrations in surrounding pore fluids. As a result, Nd isotopes are not altered during burial and later diagenesis. Therefore, fossil fish teeth from a variety of marine environments preserve a reliable and robust record of deep seawater Nd isotopic compositions from the time of deposition.

Physical properties and abundance of diatoms of the ANDRILL AND1-1B drill core

In the austral summer of 2006/7 the ANDRILL MIS (ANtarctic geological DRILLing- McMurdo Ice Shelf) project recovered a 1285 m sediment core from beneath the Ross Ice Shelf near Hut Point Peninsula, Ross Island, Antarctica in a flexural moat associated with the volcanic loading of Ross Island. Contained within the upper ~600 m of this core are sediments recording 38 glacial to interglacial cycles of Early Pliocene to Pleistocene time, including 13 discrete diatomite units (DU). The longest of these, DU XI, is ~76 m thick, contains two distinct unconformities marked by layers of volcanic brecciated sands, and has been assigned an Early to Mid-Pliocene age (5-3 Ma). A detailed record (avg. sample spacing of 33 cm) of the siliceous microfossil assemblages have been generated for DU XI and used in conjunction with geochemical and sedimentological data to subdivide DU XI into four discrete subunits of continuous sedimentation. Within each unit, changes in diatom assemblages have been correlated with the d18O record, providing a temporal resolution as high as 600 yr, and allowing for the construction of a detailed age model and calculation of associated sediment accumulation rates within DU XI. Results indicate a productivity-dominated sedimentary record with higher sediment accumulation rates containing a greater proportion of hemipelagic mud occurring during relatively cool periods and reduced accumulation during warmer intervals. This implies that even during periods of substantial warmth, Milankovitch-paced changes in Antarctic ice volume can be linked to ecological changes recorded as shifts in diatom assemblages.

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.

(Tables 2) The bPSi:POC ratio of the total diatom community, and abundance of full, empty, and broken diatom cells compared to heavily silicified diatoms during the EIFEX experiment

During the European Iron Fertilisation Experiment (EIFEX), performed in the Southern Ocean, we investigated the reactions of different phytoplankton size classes to iron fertilization, applying measurements of size fractionated pigments, particulate organic matter, microscopy, and flow cytometry. Chlorophyll a (Chl a) concentrations at 20-m depth increased more than fivefold following fertilization through day 26, while concentrations of particulate organic carbon (POC), nitrogen (PON), and phosphorus (POP) roughly doubled through day 29. Concentrations of Chl a and particulate organic matter decreased toward the end of the experiment, indicating the demise of the iron-induced phytoplankton bloom. Despite a decrease in total diatom biomass at the end of the experiment, biogenic particulate silicate (bPSi) concentrations increased steadily due to a relative increase of heavily silicified diatoms. Although diatoms >10 µm were the main beneficiaries of iron fertilization, the growth of small diatoms (2-8 mm) was also enhanced, leading to a shift from a haptophyte- to a diatom-dominated community in this size fraction. The total biomass had lower than Redfield C : N, N : P, and C : P ratios but did not show significant trends after iron fertilization. This concealed various alterations in the elemental composition of the different size fractions. The microplankton (>20 µm) showed decreasing C : N and increasing N : P and C : P ratios, possibly caused by increased N uptake and the consumption of cellular P pools. The nanoplankton (2-20 µm) showed almost constant C : N and decreasing N : P and C : P ratios. Our results suggest that the latter is caused by a shift in composition of taxonomic groups.

(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.

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.

(Table 2) Details of laminated intervals of ODP Leg 158 holes

Scanning electron microscope (SEM)-based analyses of the laminated diatom oozes encountered during Leg 138 reveal three major laminae types. The first lamina type is composed of multiple layers of ~20-?m-thick diatom mats, which form laminae dominated by assemblages of the pennate diatom, Thalassiothrix longissima. More than one variety/subspecies of T. longissima occurs within these laminae (referred to as the T. longissima Group). The second lamina type is composed of a mixed-assemblage of several species of diatoms (centric and pennate varieties), calcareous nannofossils, and subordinate quantities of radiolarians, silicoflagellates and foraminifers. The third lamina type is dominated by an assemblage of nannofossils and minor amounts of those fossil components mentioned above. This last form of lamination is compositionally similar to the background sediment type, foraminifernannofossil ooze (F-NO). Two lamina associations occur within the laminated intervals; the first comprises alternations of T. longissima Group and mixed-assemblage laminae (average thickness is ~6 mm) and the second is composed of T. longissima and nannofossil-rich laminae (average thickness is ~3.5 mm). The arrangement of laminae probably originates from the deposition of multiple layers of 20-?m-thick mats from one mat-flux episode. The much thinner nannofossil-rich laminae are interpreted to represent periods of more ônormalö deposition between mat-flux episodes. The occurrence of several varieties/subspecies of T. longissima within individual mat layers is consistent with observations of Rhizosolenia diatom mats in the modern world ocean.

Biomagnetostratigraphy of ODP Leg 189 sites

Late Cretaceous (Maastrichtian)-Quaternary summary biostratigraphies are presented for Ocean Drilling Program (ODP) Leg 189 Sites 1168 (West Tasmanian Margin), 1170 and 1171 (South Tasman Rise), and 1172 (East Tasman Plateau). The age models are calibrated to magnetostratigraphy and integrate both calcareous (planktonic foraminifers and nannofossils) and siliceous (diatoms and radiolarians) microfossil groups with organic walled microfossils (organic walled dinoflagellate cysts, or dinocysts). We also incorporate benthic oxygen isotope stratigraphies into the upper Quaternary parts of the age models for further control. The purpose of this paper is to provide a summary age-depth model for all deep-penetrating sites of Leg 189 incorporating updated shipboard biostratigraphic data with new information obtained during the 3 yr since the cruise. In this respect we provide a report of work to November 2003, not a final synthesis of the biomagnetostratigraphy of Leg 189, yet we present the most complete integrated age model for these sites at this time. Detailed information of the stratigraphy of individual fossil groups, paleomagnetism, and isotope data are presented elsewhere. Ongoing efforts aim toward further integration of age information for Leg 189 sites and will include an attempt to correlate zonation schemes for all the major microfossil groups and detailed correlation between all sites.