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.

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.

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.

Nd isotopic composition of fossil fish teeth and debris from ODP Legs 138, 165, and 202

Changes in circulation associated with the shoaling of the Isthmus of Panama and the Caribbean carbonate crash in the Miocene were investigated using Nd isotopes from fossil fish teeth and debris from two sites in the Caribbean Basin (Ocean Drilling Program Sites 998 and 999) and two sites in the eastern equatorial Pacific (Sites 846 and 1241). The total range for e-Nd values measured from 18 to 4.5 Ma in the Caribbean is -7.3 to 0. These values are higher than Atlantic water masses (~-11) and range up to values equivalent to contemporaneous Pacific water masses, confirming that flow into the Caribbean Basin was composed of a mixture of Pacific and Atlantic waters, with an upper limit of almost pure Pacific-sourced waters. Throughout the Caribbean record, particularly during the carbonate crash (10-12 Ma), low carbonate mass accumulation rates (MARs) correlate with more radiogenic e-Nd values, indicating increased flow of corrosive Pacific intermediate water into the Caribbean Basin during intervals of dissolution. This flow pattern agrees with results from general ocean circulation models designed to study the effect of the shoaling of the Central American Seaway. Low carbonate MARs and high e-Nd values also correlate with intervals of increased Northern Component Water production and, therefore, enhanced conveyor circulation, suggesting that the conveyor may respond to changes in circulation associated with shoaling of the Central American Seaway. Reduced Pacific throughflow related to shoaling of the seaway led to a gradual increase in carbonate preservation and more Atlantic-like e-Nd values following the carbonate crash.

(Table 1) Stratigraphic occurrence and fossil content of fossiliferous horizons in southern north Victoria Land

In contrast to the adjacent parts of the Transantarctic Mountains, the Mesozoic macrofossil record of north Victoria Land remains poorly documented. During the Ninth German Antarctic North Victoria Land Expedition (GANOVEX IX 2005/2006) twelve fossil sites in southern north Victoria Land were discovered and sampled. Fossils from the Triassic to Early Jurassic Section Peak Formation were collected from Archambault Ridge, Anderton Glacier, Skinner Ridge, Timber Peak, Vulcan Hills, Runaway Hills, Section Peak and Shafer Peak. These localities have yielded abundant fossil wood and compressions of horsetails, ferns, and seed ferns. In addition, several beetle elytra were found at Timber Peak. Fossil localities of the overlying Shafer Peak Formation and Exposure Hill-type deposits occur at Shafer Peak and in the Mount Carson area, and have yielded various trace fossils, permineralized wood, leaf compressions, and conchostracans. Two newly discovered fossil sites are associated with the late Early Jurassic Kirkpatrick lava flows. Upright-standing tree trunks have been recorded at Suture Bench, and highly fossiliferous sedimentary interbeds occur at the southwestern end of the Mesa Range. Of special interest is the exquisite fossil preservation at some of the sites. Compression fossils from Timber Peak and Shafer Peak contain well-preserved cuticles, which is very rare in the Antarctic. An Early Jurassic permineralized deposit at Mount Carson contains structurally preserved ferns. Furthermore, the arthropod fossils from sedimentary interbeds at the Mesa Range are preserved in minute detail, including antennae and limb spines of a blattid insect.

Stable carbon and oxygen isotope record of planktonic foraminifera across the Paleocene-Eocene boundary

The early Cenozoic marine carbon isotopic record is marked by a long-term shift from high d13C values in the late Paleocene to values that are 2 to 3 lower in the early Eocene. The shift is recorded in fossil carbonates from each ocean basin and represents a large change in the distribution of 12C between the ocean and other carbon reservoirs. Superimposed upon this long-term shift are several distinct carbon isotopic negative excursions that are also recorded globally. These carbon isotopic 'events' near the Paleocene-Eocene boundary provide strati-graphic information that can facilitate intersite correlations between marine and non-marine sequences. Here we present a detailed marine carbon isotopic stratigraphy across the Paleocene-Eocene boundary that is constrained by calcareous nannofossil and planktonic foraminifera bio-stratigraphy and magnetostratigraphy. We show that several distinct carbon isotopic changes are recorded in uppermost Paleocene and lowermost Eocene marine biogenic carbonate sediments. At least one of these isotopic changes in the ocean's carbon isotopic composition was transmitted to terrestrial carbon reservoirs, including plant biomass via atmospheric CO2. As a consequence of this exchange of 12C between the ocean and terrestrial carbon reservoirs, it is possible to use carbon isotope stratigraphy to correlate the uppermost Paleocene and lowermost Eocene non-fossiliferous terrestrial sediments of the Paris Basin with marine sequences.

Vanuatu fossil coral SST reconstruction for 4200 yr BP

We present a 47-year-long record of sea surface temperature (SST) derived from Sr/Ca and U/Ca analysis of a massive Porites coral which grew at ~4150 calendar years before present (B.P.) in Vanuatu (southwest tropical Pacific Ocean). Mean SST is similar in both the modern instrumental record and paleorecord, and both exhibit El Niño-Southern Oscillation (ENSO) frequency SST oscillations. However, several strong decadal-frequency cooling events and a marked modulation of the seasonal SST cycle, with power at both ENSO and decadal frequencies, are observed in the paleorecord, which are unprecedented in the modern record.

(Table 1) Stable carbon isotope record and calculated recycled DIC for sediment core ANDRA_HTM102

The prominent negative stable carbon isotope excursion in both carbonate and organic carbon recorded in organic-rich sediments deposited during the Toarcian oceanic anoxic event (OAE) has commonly been explained by recycling of 13C-depleted CO2 (the so-called Küspert model). More recently, the massive release of 13C-depleted methane or other forms of 13C-depleted carbon was also proposed to account for the observed negative d13C excursions in organic carbon of terrigenous as well as of marine origin. The occurrence of diagenetic products of the carotenoid isorenieratene (isorenieratane and other aryl isoprenoids) in Toarcian black shales has been regarded as supporting evidence for the Küspert hypothesis as they point to strong stratification of the epicontinental seas. A section of a drill core straddling the Toarcian of the Paris Basin (Cirfontaine-en-Ornois) contained intact isorenieratane, providing evidence that photosynthetic green sulphur bacteria were present at the time of deposition, even prior to the OAE. However, the isorenieratane abundances are very low in the section where the negative d13C excursion in organic carbon and phytane, a chemical fossil derived from chlorophyll, occurs. The abundance of the isorenieratene derivatives increases, once the d13C records have shifted to more positive values. The d13C of isorenieratane (generally circa -13.1 ± 0.5 per mil) indicates that the respired CO2 contribution at the chemocline was low and is thus not likely to be the main cause of the prominent up to 7per mil negative d13C shift recorded in Toarcian organic carbon records.

Seawater Nd and Pb isotopic record in central Pacific and Caribbean sediments

The shoaling and final closure of the Central American Seaway (CAS) resulted in a major change of the global ocean circulation and has been suggested as an essential driver for strengthening of Atlantic Meridional Overturning Circulation (AMOC). The exact timing of CAS closure is key to interpreting its importance. Here we present a reconstruction of deep and intermediate water Nd and Pb isotope compositions obtained from fossil fish teeth and the authigenic coatings of planktonic foraminifera in the eastern equatorial Pacific (Ocean Drilling Program (ODP) Site 1241) and the Caribbean (ODP Sites 998, 999, and 1000) covering the final stages of CAS closure between 5.6 and 2.2 Ma. The data for the Pacific site indicate no significant Atlantic/Caribbean influence over this entire period. The Caribbean sites show a continuous trend to less radiogenic Nd isotope compositions during the Pliocene, consistent with an enhancement of Upper North Atlantic Deep Water (UNADW) inflow and a strengthening of the AMOC. Superimposed onto this long-term trend, shorter-term changes of intermediate Caribbean Nd isotope signatures approached more UNADW-like values during intervals when published reconstructions of seawater salinity suggested complete closure of the CAS. The data imply that significant deep water exchange with the Pacific essentially stopped by 7 Ma and that shallow exchange, which still occurred at least periodically until approximately 2.5 Ma, may have been linked to the strength of the AMOC but did not have any direct effect on the intermediate and deep Caribbean Nd isotope signatures through mixing with Pacific waters.

Geochemistry and stable isotope record of black shales and inoceramids from the Demerara Rise

The bulk rock geochemistry and inoceramid isotopic composition from Cenomanian to Santonian, finely laminated, organic-rich black shales, recovered during Ocean Drilling Program Leg 207 on Demerara Rise (western tropical North Atlantic), suggest persistent anoxic (free H2S) conditions within the sediments and short-term variations within a narrow range of anoxic to episodically dysoxic bottom waters over a ~15 Ma time interval. In addition to being organic-rich, the 50-90 m thick sections examined exhibit substantial bulk rock enrichments of Si, P, Ba, Cu, Mo, Ni, and Zn relative to World Average Shale. These observations point to high organic burial fluxes, likely driven by high primary production rates, which led to the establishment of intensely sulfidic pore waters and possibly bottom waters, as well as to the enrichments of Cr, Mo, U, and V in the sediments. At the same time, the irregular presence of benthic inoceramids and foraminifera in this facies demonstrates that the benthic environment could not have been continuously anoxic. The d13C and d15N values of the inoceramid shell organics provide no evidence of chemosymbiosis and are consistent with pelagic rain as being a significant food source. Demerara Rise inoceramids also exhibit well-defined, regularly spaced growth lines that are tracked by d13C and d18O variations in shell carbonate that cannot be simply explained by diagenesis. Instead, productivity variations in surface waters may have paced the growth of the shells during brief oxygenation events suitable for benthic inoceramid settlement. These inferences imply tight benthopelagic coupling and more dynamic benthic conditions than generally portrayed during black shale deposition. By invoking different temporal scales for geochemical and paleontological data, this study resolves recent contradictory conclusions (e.g., sulfidic sedimentary conditions versus dysoxic to suboxic benthic waters) drawn from studies of either sediment geochemistry or fossil distributions alone on Demerara Rise. This variability may be relevant for discussions of black shales in general.

Sedimentary record of the western Amundsen Sea Embayment after the last glacial maximum

Reliable dating of glaciomarine sediments deposited on the Antarctic shelf since the Last Glacial Maximum (LGM) is very challenging because of the general absence of calcareous (micro-) fossils and the recycling of fossil organic matter. As a consequence, radiocarbon (14C) ages of the acid-insoluble organic fraction (AIO) of the sediments bear uncertainties that are very difficult to quantify. In this paper we present the results of three different chronostratigraphic methods to date a sedimentary unit consisting of diatomaceous ooze and diatomaceous mud that was deposited following the last deglaciation at five core sites on the inner shelf in the western Amundsen Sea (West Antarctica). In three cores conventional 14C dating of the AIO in bulk sediment samples yielded age reversals down-core, but at all sites the AIO 14C ages obtained from diatomaceous ooze within the diatom-rich unit yielded similar uncorrected 14C ages ranging from 13,517±56 to 11,543±47 years before present (yr BP). Correction of these ages by subtracting the core-top ages, which are assumed to reflect present-day deposition (as indicated by 21044 Pb dating of the sediment surface at one core site), yielded ages between ca. 10,500 and 8,400 calibrated years before present (cal yr BP). Correction of the AIO ages of the diatomaceous ooze by only subtracting the marine reservoir effect (MRE) of 1,300 years indicated deposition of the diatom-rich sediments between 14,100 and 11,900 cal yr BP. Most of these ages are consistent with age constraints between 13.0 and 8.0 ka BP for the diatom-rich unit, which we obtained by correlating the relative palaeomagnetic intensity (RPI) records of three of the sediment cores with global and regional reference curves for palaeomagnetic intensity. As a third dating technique we applied conventional 53 radiocarbon dating of the AIO included in acid-cleaned diatom hard parts that were extracted from the diatomaceous ooze. This method yielded uncorrected 14C ages of only 5,111±38 and 5,106±38 yr BP, respectively. We reject these young ages, because they are likely to be overprinted by the adsorption of modern atmospheric carbon dioxide onto the surfaces of the extracted diatom hard parts prior to sample graphitisation and combustion for 14C dating. The deposition of the diatom-rich unit in the western Amundsen Sea suggests deglaciation of the inner shelf before ca. 13 ka BP. The deposition of diatomaceous oozes on other parts of the Antarctic shelf around the same time, however, seems to be coincidental rather than directly related.

Sea Surface Temperature (SST) Mg/Ca record for the surface-dwelling planktonic foraminifera Globigerina bulloides

We generated a high-resolution SSTMg/Ca record for the surface-dwelling planktonic foraminifera Globigerina bulloides from the core MD99-2346 collected in the Gulf of Lion, and compared it to that obtained using modern analogue techniques applied to fossil foraminiferal assemblages (SSTMAT). The two temperature records display similar patterns during the last 28,000 years but the SSTMg/Ca estimates are several degrees warmer (~+4 °C) than SSTMAT. The temperature shift between SSTMg/Ca and SSTMAT remained relatively constant over time. This seems to exclude a bias on the Mg/Ca record associated with salinity or secondary Mg-rich calcite encrustation on the foraminiferal tests during early diagenesis. Therefore, anomalously high Mg/Ca suggests either: (1) the empirical equation for G. bulloides of Elderfield and Ganssen (2000) is incorrect; or (2) there is a specific Mediterranean genotypes of G. bulloides for which a specific Mg/Ca-temperature calibration is needed.

(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.