(Table 1) Stable carbon and oxygen isotopes of planktonic and benthic foraminifera in ODP Hole 1006A

During ODP Leg 166, the recovery of cores from a transect of drill sites across the Bahamas margin from marginal to deep basin environments was an essential requirement for the study of the response of the sedimentary systems to sea-level changes. A detailed biostratigraphy based on planktonic foraminifera was performed on ODP Hole 1006A for an accurate stratigraphic control. The investigated late middle Miocene-early Pliocene sequence spans the interval from about 12.5 Ma (Biozone N12) to approximately 4.5 Ma (Biozone N19). Several bioevents calibrated with the time scale of Berggren et al. (1995a,b) were identified. The ODP Site 1006 benthic oxygen isotope stratigraphy can be correlated to the corresponding deep-water benthic oxygen isotope curve from ODP Site 846 in the Eastern Equatorial Pacific (Shackleton et al., 1995. Proc. ODP Sci. Res. 138, 337-356), which was orbitally tuned for the entire Pliocene into the latest Miocene at 6.0 Ma. The approximate stratigraphic match of the isotopic signals from both records between 4.5 and 6.0 Ma implies that the paleoceanographic signal from the Bahamas is not simply a record of regional variations but, indeed, represents glacio-eustatic fluctuations. The ODP Site 1006 oxygen and carbon isotope record, based on benthic and planktonic foraminifera, was used to define paleoceanographic changes on the margin, which could be tied to lithostratigraphic events on the Bahamas carbonate platform using seismic sequence stratigraphy. The oxygen isotope values show a general cooling trend from the middle to late Miocene, which was interrupted by a significant trend towards warmer sea-surface temperatures (SST) and associated sea-level rise with decreased ice volume during the latest Miocene. This trend reached a maximum coincident with the Miocene/Pliocene boundary. An abrupt cooling in the early Pliocene then followed the warming which continued into the earliest Pliocene. The late Miocene paleoceanographic evolution along the Bahamas margin can be observed in the ODP Site 1006 delta13C values, which support other evidence for the beginning of the closure of the Panama gateway at 8 Ma followed by a reduced intermediate water supply of water from the Pacific into the Caribbean at about 5 Ma. A general correlation of lower sedimentation rates with the major seismic sequence boundaries (SSBs) was observed. Additionally, the SSBs are associated with transitions towards more positive oxygen isotope excursions. This observed correspondence implies that the presence of a SSB, representing a density impedance contrast in the sedimentary sequence, may reflect changes in the character of the deposited sediment during highstands versus those during lowstands. However, not all of the recorded oxygen isotope excursions correspond to SSBs. The absence of a SSB in association with an oxygen isotope excursion indicates that not all oxygen isotope sea-level events impact the carbonate margin to the same extent, or maybe even represent equivalent sea-level fluctuations. Thus, it can be tentatively concluded that SSBs produced on carbonate margins do record sea-level fluctuations but not every sea-level fluctuation is represented by a SSB in the sequence stratigraphic record.

Simultaneous high-resolution pH and spectrophotometric recordings of oxygen binding in native blood microvolumes, link to supplementary material

Oxygen equilibrium curves have been widely used to understand oxygen transport in numerous organisms. A major challenge has been to monitor oxygen binding characteristics and concomitant pH changes as they occur in vivo, in limited sample volumes. Here we report a technique allowing highly resolved and simultaneous monitoring of pH and blood pigment saturation in minute blood volumes. We equipped a gas diffusion chamber with a broad range fibre optic spectrophotometer and a micro-pH optode and recorded changes of pigment oxygenation along PO2 and pH gradients to test the setup. Oxygen binding parameters derived from measurements in only 15 µl of haemolymph from the cephalopod Octopus vulgaris showed low instrumental error (0.93%) and good agreement with published data. Broad range spectra, each resolving 2048 data points, provided detailed insight into the complex absorbance characteristics of diverse blood types. After consideration of photobleaching and intrinsic fluorescence, pH optodes yielded accurate recordings and resolved a sigmoidal shift of 0.03 pH units in response to changing PO2 from 0-21 kPa. Highly resolved continuous recordings along pH gradients conformed to stepwise measurements at low rates of pH changes. In this study we showed that a diffusion chamber upgraded with a broad range spectrophotometer and an optical pH sensor accurately characterizes oxygen binding with minimal sample consumption and manipulation. We conclude that the modified diffusion chamber is highly suitable for experimental biologists who demand high flexibility, detailed insight into oxygen binding as well as experimental and biological accuracy combined in a single set up.

Mineralogical, sedimentological and paleontological analyses of ODP Hole 127-797B upper Quarternary sediments

Nearly continuous cores of Quaternary fine-grained sediments with distinct dark-light colored cycles were recovered from Sites 794, 795, and 797 in the basinal parts of the Japan Sea during Leg 127. A comparison of gray value (darkness) profiles supplemented by visual inspection of core photographs between sites indicated that most of the dark and light layers were correlatable between sites, and that two of the dark layers lie close to adjacent marker ash layers. These observations indicate that deposition of dark and light layers resulted from basin-wide synchronous events. In order to understand the origin of these dark-light cycles, petrographical, mineralogical, compositional, and paleontological studies were carried out on closely spaced samples from the upper Quaternary sediments recovered from Site 797. Age model was constructed based on comparison between variation in diatom abundance and the standard oxygen isotope curve of Imbrie et al. (1984), the latter was interpolated between the five age controlled levels established at Site 797. The two curves show similar patterns which enabled us to "tune" the sediment ages to the oxygen isotope stages. We have to use variation in diatom abundance as a substitute for oxygen isotope curve since oxygen isotopic data are not available at the studied sites. Bottom water oxygenation conditions were estimated based on two criteria: (1) the degree of lamina preservation and (2) the ratio of Corg to Stot. The surface water productivity was deduced from the Corg and biogenic silica content. Results suggest that the bottom water oxygenation level and the surface water productivity varied significantly in response to the glacial-interglacial cycles. Glacio-eustatic sea-level changes and subsequent changes in water circulation in the Japan Sea appear to have been responsible for these variations and consequent changes in sediment composition throughout the Quaternary.

Stable isotope, seismic sequence boundaries and bioevents in ODP Hole 166-1006A

During ODP Leg 166, the recovery of cores from a transect of drill sites across the Bahamas margin from marginal to deep basin environments was an essential requirement for the study of the response of the sedimentary systems to sea-level changes. A detailed biostratigraphy based on planktonic foraminifera was performed on ODP Hole 1006A for an accurate stratigraphic control. The investigated late middle Miocene-early Pliocene sequence spans the interval from about 12.5 Ma (Biozone N12) to approximately 4.5 Ma (Biozone N19). Several bioevents calibrated with the time scale of Berggren et al. (1995a,b) were identified. The ODP Site 1006 benthic oxygen isotope stratigraphy can be correlated to the corresponding deep-water benthic oxygen isotope curve from ODP Site 846 in the Eastern Equatorial Pacific (Shackleton et al., 1995. Proc. ODP Sci. Res. 138, 337-356), which was orbitally tuned for the entire Pliocene into the latest Miocene at 6.0 Ma. The approximate stratigraphic match of the isotopic signals from both records between 4.5 and 6.0 Ma implies that the paleoceanographic signal from the Bahamas is not simply a record of regional variations but, indeed, represents glacio-eustatic fluctuations. The ODP Site 1006 oxygen and carbon isotope record, based on benthic and planktonic foraminifera, was used to define paleoceanographic changes on the margin, which could be tied to lithostratigraphic events on the Bahamas carbonate platform using seismic sequence stratigraphy. The oxygen isotope values show a general cooling trend from the middle to late Miocene, which was interrupted by a significant trend towards warmer sea-surface temperatures (SST) and associated sea-level rise with decreased ice volume during the latest Miocene. This trend reached a maximum coincident with the Miocene/Pliocene boundary. An abrupt cooling in the early Pliocene then followed the warming which continued into the earliest Pliocene. The late Miocene paleoceanographic evolution along the Bahamas margin can be observed in the ODP Site 1006 delta13C values, which support other evidence for the beginning of the closure of the Panama gateway at 8 Ma followed by a reduced intermediate water supply of water from the Pacific into the Caribbean at about 5 Ma. A general correlation of lower sedimentation rates with the major seismic sequence boundaries (SSBs) was observed. Additionally, the SSBs are associated with transitions towards more positive oxygen isotope excursions. This observed correspondence implies that the presence of a SSB, representing a density impedance contrast in the sedimentary sequence, may reflect changes in the character of the deposited sediment during highstands versus those during lowstands. However, not all of the recorded oxygen isotope excursions correspond to SSBs. The absence of a SSB in association with an oxygen isotope excursion indicates that not all oxygen isotope sea-level events impact the carbonate margin to the same extent, or maybe even represent equivalent sea-level fluctuations. Thus, it can be tentatively concluded that SSBs produced on carbonate margins do record sea-level fluctuations but not every sea-level fluctuation is represented by a SSB in the sequence stratigraphic record.

Planktonic foraminifera of sediment core T89-40 on the Walvis Ridge, South Atlantic

Core T89-40, eastern Walvis Ridge between the subtropical gyre and Benguela coastal upwelling system, contains three types of levels of abundant left-coiled Neogloboquadrina pachyderma, a cold, eutrophic species, next to subtropical species. Type A peaks (362, 110 and 53-43 ky BP) are accompanied with high percentages of other eutrophic species. They are attributed to intensified upwelling in the Northern Benguela region. Type B peaks (129 and 92 ky BP) are accompanied by moderate (<48%) contributions of other eutrophic species and increased numbers of subtropical species. These suggest intensified upwelling in the Northern Benguela cells and may reflect increased seasonal contrasts between the winter upwelling and the subtropical summer conditions. The highest C-peaks, up to 38%, are associated with strongly reduced percentages of other eutrophic species and with abundant subtropical species (Marine Isotopic Stage 11.3 (401 ky) and 9.3 (326 ky)). The subtropical species preceeded the C-peaks by ca 8 ky. We argue that the C-peaks were not produced by local reproduction but expatriated from the Northern Benguela upwelling cells. Here more nutrient-rich waters may have produced a mono-specific Neogloboquadrina pachyderma (left) fauna during strong polewards shifts of the frontal systems in the South Atlantic, which could have been transported 700 km offshore to the core location, unadmixed with eutrophic species from the surrounding waters. We propose meandering shelf-edge jets, strong contour jets, as a mechanism for the transport. The timing of the C-peaks and associated subtropical peaks agrees with the known precessional cyclicity of the SE Atlantic front movements and zonality of the trade winds, which supports the shelf-edge jet hypothesis.

(Table T1) Ice rafted debris characteristics of ODP Site 177-1092

We have carried out a multiphase analysis of samples from ODP Site 177-1092, Meteor Rise, subantarctic South Atlantic. Samples were analyzed for ice-rafted debris (IRD [see Table T1]) and stable isotopes from benthic foraminifera [see Murphy et al., 2002, doi:10.1016/S0031-0182(01)00495-3]. Both analyses were performed on the same samples. Additional work was performed to identify the paleomagnetic stratigraphy. The analyzed samples range in age from about 2.6(?) Ma to 4.6 Ma, a time span that saw considerable global warmth, but witnessed overall global refrigeration and the transition to truly bipolar glaciations. IRD arrived frequently during the Early and early Late Pliocene, but only as 'background rafting' (occasional grains per sample). The first identifiable IRD above background rafting is associated with marine isotope stage (MIS) KM4 (~3.18 Ma). Successive IRD peaks become larger, the same pattern as noted at nearby Site 114-704. A very large peak near the top of the record, approximately 2.8 Ma, is considered to represent a hiatus. Peaks below 51.3 meters composite depth (mcd) coincide with positive excursions of the oxygen isotopic record, and with negative excursions of the carbon isotopic curve, a pattern also noted at Site 114-704. However, the reasonably large IRD peak at 51 mcd (tentatively identified with MIS G11) coincides with a positive excursion on the carbon isotopic curve and negative excursion on the oxygen isotopic curve. This relationship suggests a northern hemisphere interglacial, rising sea level, destabilization of the Antarctic margin, and delivery of Antarctic icebergs to the Southern Ocean. Such a mechanism has recently been suggested by Kanfoush et al. (2000, doi:10.1126/science.288.5472.1815) for latest Pleistocene stadial/interstadial oscillations. Here we suggest that such a mechanism may have been in place on glacial/interglacial time scales as early as the Late Pliocene.

Middle to Late Quaternary sedimentation and rock-magnetic of ODP Site 105-646

We examine rock-magnetic, carbonate, and planktonic foraminiferal fluxes to identify climatically controlled changes of terrigenous and pelagic sedimentation at Ocean Drilling Program (ODP) Site 646 (the Labrador Sea). Terrigenous sediments are brought to the site principally by bottom currents. We use a rock-magnetic parameter sensitive to changes in magnetic mineral grain size, the ratio of anhysteretic susceptibility to low-field magnetic susceptibility (XARM/X), to monitor changes in bottom-current intensity over time, with large values of XARM/X (finer-grained magnetic minerals) indicating weaker bottom currents. A second rock-magnetic parameter, magnetic mineral accumulation rate (KaT) was used to indicate variations in terrigenous flux. Planktonic foraminiferal and carbonate accumulation rates (Pfar and CaC03ar) are used as indicators of pelagic flux. Absolute age assignments are based on correlation between the planktonic foraminiferal oxygen-isotope variations for Site 646 and the SPECMAP master oxygen-isotope curve. Cross-correlation analyses of the parameters that we studied with respect to the SPECMAP curve suggest that from oxygen-isotope stages 21 to 11, sedimentation rate, KaT, X, CaCO3ar, and Pfar were at their maximums, whereas XARM/X was at its minimum during peak interglacials (i.e., 0 k.y. lag time with respect to minimum ice volume). However, all parameters we examined lag behind minimum ice volume from stages 11 to 1, indicating a change in timing of both pelagic and terrigenous fluxes at approximately 400 k.y. BP. The negative correlation coefficient between XARM/X and the SPECMAP curve further suggest that finer-grained magnetic minerals are deposited during glacial periods, which probably reflects weaker bottom currents. The shift observed in the lag times of parameters examined with respect to the SPECMAP record is attributed to a change in significance of orbital parameters. Spectral results exhibit strong power in eccentricity (about 100 k.y.) throughout the record. Kap X, CaCO3flr, and Pfar show significant power in obliquity (about 41 k.y.), whereas XARM/X shows significant power at 73 k.y. from stages 21 to 11. The 73-k.y. period in XARM/X is near the difference tone of obliquity and eccentricity: 1/43-1/102 = 1/69. Kar and XARM/X show power only in eccentricity from stages 11 to 1. X and Pfar show significant power in precession (about 18 and 22 k.y.) whereas CaC03ar has power at 34 k.y, which could be a combination of precession and obliquity. The shift in power of orbital parameters may by attributed to the effect of the about 413-k.y. signal of eccentricity.

Boron isotope composition and seawater characteristics of cold water scleratinian corals

The boron isotope systematics has been determined for azooxanthellate scleractinian corals from a wide range of both deep-sea and shallow-water environments. The aragonitic coral species, Caryophyllia smithii, Desmophyllum dianthus, Enallopsammia rostrata, Lophelia pertusa, and Madrepora oculata, are all found to have relatively high d11B compositions ranging from 23.2 per mil to 28.7 per mil. These values lie substantially above the pH-dependent inorganic seawater borate equilibrium curve, indicative of strong up-regulation of pH of the internal calcifying fluid (pH(cf)), being elevated by ~0.6-0.8 units (Delta pH) relative to ambient seawater. In contrast, the deep-sea calcitic coral Corallium sp. has a significantly lower d11B composition of 15.5 per mil, with a corresponding lower Delta pH value of ~0.3 units, reflecting the importance of mineralogical control on biological pH up-regulation. The solitary coral D. dianthus was sampled over a wide range of seawater pH(T) and shows an approximate linear correlation with Delta pH(Desmo) = 6.43 - 0.71 pH(T) (r**2 = 0.79). An improved correlation is however found with the closely related parameter of seawater aragonite saturation state, where Delta pH(Desmo) = 1.09 - 0.14 Omega(arag) (r**2 = 0.95), indicating the important control that carbonate saturation state has on calcification. The ability to up-regulate internal pH(cf), and consequently Omega(cf), of the calcifying fluid is therefore a process present in both azooxanthellate and zooxanthellate aragonitic corals, and is attributed to the action of Ca2+ -ATPase in modulating the proton gradient between seawater and the site of calcification. These findings also show that the boron isotopic compositions (d11Bcarb) of aragonitic corals are highly systematic and consistent with direct uptake of the borate species within the biologically controlled extracellular calcifying medium.

Stable oxygen and carbon isotope compositions of Campanian grainstones and rudstones

Petrographic descriptions and stable oxygen and carbon isotope compositions of microsamples of Campanian-age sediment gravity-flow deposits from Northeast Providence Channel, Bahamas, indicate deep-marine cementation of shallow-marine skeletal grains that were transported to the channel during the Late Cretaceous. Shallow-marine components are represented by mollusks, especially rudists, and shallow-water benthic foraminifers as well as sparse echinoderm and algal grains. The sole evidence of diagenesis in shallow-marine environments consists of micrite envelopes around skeletal grains. Shallow-marine skeletal grains have mean stable isotope values of -3.1 per mil d18O and +2.6 per mil d13C. The d18O values are consistent with precipitation in equilibrium with warm (20°-30°C), shallow-marine water. Deep-marine components are represented by equant calcite spar cements and rip-up clasts of slope sediments. Spar cements, exhibiting hexagonal morphology with scalenohedral terminations, most commonly occur as thin isopachous linings in the abundant porosity. Deep-marine cements have mean stable isotope values of - 1.1 per mil d18O and +2.7 per mil d13C. Deep-marine cements are 18O-enriched relative to shallow-marine skeletal grains, consistent with precipitation in equilibrium with colder (10°-20°C), deep-marine waters. The cement .source during lithification appears to have been dissolution of aragonite and high-magnesium calcite skeletal grains, which made up part of the transported sediment. Interbedded periplatform ooze remains uncemented, or poorly cemented, probably because of lower permeability. Equant spar cements that occur in gravity-flow deposits recovered from Hole 634A have stable isotope compositions similar to spars in Lower and mid-Cretaceous shallow-water limestones exposed on the Bahama Escarpment, to Campanian-Paleocene deep-marine hardgrounds recovered during DSDP Leg 15 in the Caribbean, and to spars in Aptian-Albian talus deposits at the base of the Campeche Escarpment recovered during DSDP Leg 77.