Calcium concentrations and isotopic composition in carbonates and porefluids from ODP Hole 130-807A

The calcium isotopic compositions (d44Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (a_s-f) between calcite and dissolved Ca2+ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of a_s-f at equilibrium in the marine sedimentary section is 1.0000+/-0.0001, which is significantly different from the value (0.9987+/-0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ~14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in d44Ca of +0.15? for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.

Sediment composition of ODP Hole 130-803D

Samples obtained in Hole 803D for shipboard determination of index properties were analyzed to determine their microfossil constituents. The resulting data are compared to shipboard-measured physical properties data to assess the relationships between small-scale fluctuations in physical properties and microfossil content and preservation. The establishment of relationships involving index properties of these highly calcareous sediments is difficult because of the role of intraparticle porosity. Relationships were observed between calculated interparticle porosity and microfossil content. Impedance, calculated using bulk density based on interparticle porosity, exhibits an increase with increasing grain size. Variations in the coarse fraction constituents appear to exert more control over physical properties than variations in the fine-fraction constituents, although the fine fraction make up greater than 85% of the samples by weight.

Late Pliocene carbonate mineralogy of ODP Hole 133-818B

Shedding of shallow carbonate material toward the deep slopes and basin floors is clearly tied to the position of the carbonate bank tops relative to the photic zone. The onset of bank shedding in periplatform sediments can record either the flooding of the bank tops within the photic zone during a rise in sea level following a period of exposure, referred to in the literature as the "highstand shedding" scenario, or the reentry of the bank tops into the photic zone during a lowering of sea level following a period of drowning, referred to as the "lowstand shedding" scenario. Results from Leg 133 post-cruise research on the Pliocene sequences, drilled in six sites within different slope settings of the Queensland Plateau, seem to point out that the latter "lowstand shedding" scenario can be applied to this particular carbonate system. At the Queensland Plateau sites, the early Pliocene (5.2-3.5 Ma) and the earliest part of the late Pliocene (3.5-2.9 Ma) age sequences were characterized, especially in the ôdeepö Sites 811 and 817, by pelagic sediments (foraminifers and coccoliths) and by typically pelagic sedimentation rates not exceeding 20 mm/k.y. The earliest part of the late Pliocene age section was characterized by well-developed hardgrounds in the "shallow" Sites 812 and 814 and by normal pelagic sediments mixed with reworked phosphatized planktonic foraminifers in Site 813. Finally, the early part of the late Pliocene (2.9-2.4 Ma) section was characterized by high sedimentation rates, related to the shedding and admixture into the pelagic sediments of bank-derived materials. These bank-derived materials consist of either diagenetically unaltered fine aragonite with traces of dolomite in Site 818 or micritic calcite resulting from seafloor and/or shallow burial alteration in the deepest Sites 817 and 811. The highest sedimentation rates (163 mm/k.y.) were recorded in Site 818, drilled nearest the modern carbonate bank of Tregrosse Reef. The sedimentation rates decrease with increasing distance from Tregrosse Reef - 120 mm/k.y. in Site 817 and 47.5 mm/k.y. in Site 811. The initial appearance of fine aragonite in Site 818, corresponding to the transition from pelagic to periplatform sedimentation rates, has been dated at 2.9 Ma. This Pliocene sediment pattern on the Queensland Plateau is different from the pattern observed in sediments from two earlier ODP legs (i.e., Leg 101 in the Bahamas and in Leg 115 in the Maldives), where aragonite-rich sediments, characterized by high periplatform sedimentation rates, were observed in the lower Pliocene section (5.2-3.5 Ma), whereas the upper Pliocene (3.5-1.6 Ma) sediments are more pelagic in nature and are characterized by low sedimentation rates or major hiatuses. These Pliocene periplatform sequences in the Bahamas and in the Maldives and late Quaternary age periplatform sequences worldwide have pointed out that "highstand shedding" was the typical response of carbonate platforms to fluctuations in sea level, just opposite to a "lowstand shedding" response to sea-level fluctuations, typical of siliciclastic shelves. Assuming that the envelope of Haq et al.'s (1987) sea-level curve, showing a well-defined lowering of sea level between 3.5 and 2.9 Ma, can also be applied to the southwest Pacific Ocean, based on a high-resolution Pliocene d18O record from the Ontong Java Plateau recently published by Jansen et al. (1993, doi:10.2973/odp.proc.sr.130.028.1993), the Pliocene periplatform sequences on the Queensland Plateau would have recorded the reentry of the bank tops into the photic zone during a general lowering of sea level, following an interval characterized by high sea level, during which the shallow carbonate system on the Queensland Plateau was drowned. The early Pliocene age (5.2-3.5 Ma) sediments deposited on the Queensland Plateau, an established interval of eustatic sea-level highstand, are typically pelagic in character. In addition, relatively cold surface temperatures (estimated to have ranged from 18° to 20°C by Isern et al. [this volume]) might have also stressed the reefs during early Pliocene time and contributed to the drowning of the Queensland Plateau carbonate system during the late Miocene and early Pliocene. Differential and relatively high subsidence rates, inferred by variations in paleodepth of water (based upon benthic foraminifer assemblages; Katz and Miller, this volume) may also have influenced the drowning of the carbonate bank tops on the Queensland Plateau during the late Miocene and early Pliocene. The sediments of early late Pliocene age (2.9-2.4 Ma), a well-established interval of lowering of sea level, are clearly periplatform and cyclic in nature. High-frequency (~40 k.y.) aragonite cycles, well-developed between 2.9 and 2.45 Ma, correlate with the planktonic high-resolution Pliocene d18O record from the Ontong Java Plateau, a good sea-level proxy (Jansen et al., in press). Contrary to late Quaternary age aragonite cycles from the Bahamas, the Nicaragua Rise, the Maldives, and the Queensland Plateau, the late Pliocene aragonite cycles in Hole 818B display high levels of aragonite during glacial stages and, therefore, lowstands of sea level. In addition, sediments deposited during the earliest part of the late Pliocene (3.5-2.9 Ma), transition between the early Pliocene highstand and the late Pliocene lowering in sea level, have recorded the first evidence of a fall in sea level, by (1) the occurrence of synchronous submarine hardgrounds in the two shallowest sites (Sites 812 and 814), (2) the deposition of reworked material from the shallower part of the slope into the intermediate Sites 813 and 818, and (3) the deposition of pelagic sediments in the deepest Sites 817 and 817. In summary, contrary to previous findings, the Pliocene periplatform sediments on the Queensland Plateau appear to have recorded a regional shedding of shallow carbonate bank tops during an interval of sea-level lowering, a good illustration of the "carbonate lowstand shedding" scenario, occurring during the reentry of previously drowned carbonate bank tops into the photic zone related to a decrease in sea level.

Strontium and neodymium concentrations and isotope compositions in fossil fish teeth and pore waters at ODP Sites 130-807 and 125-786

We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

(Table 2) Major and trace element content of ODP Leg 130 basalts

Estimated relative errors on major and minor elements are 1%. For trace elements, errors (% standard deviation at levels measured) are estimated at 1 % for Cr, 3% for Ni, 3% for Rb at 30 ppm, and >20% at < 10 ppm; 2% for Sr and V, and 4% for Y and Zr.

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Compaction curves and sediment characteristics of ODP Leg 165 and Leg 130 sites

Compaction curves for 11 samples from the mixed sediments and calcareous chalk with clay from the Caribbean Sites 999 and 1001 are discussed with reference to compaction curves for calcareous ooze and chalk of the Ontong Java Plateau (Leg 130). The burial history is discussed from preconsolidation data and present burial conditions and suggests a removal of ~400 m of sediment at the hiatus 166 meters below seafloor (mbsf) at Site 1001. This interpretation predicts a previous burial to >500 mbsf for depth intervals containing microstylolites, which corresponds to observations at Sites 999 and 807 (Ontong Java Plateau). Thus, data from three sites from two widely separate regions indicate that microstylolites in carbonates form at minimum burial depths deeper than 500 m. No direct link between formation of microstylolites and cementation was found, suggesting that dissolution and precipitation are not necessarily related. Porosity rebound during core retrieval could not be detected for soft sediments, whereas a porosity rebound of ~2% was deduced for deeper, cemented intervals. Comparing the compaction curves, two distinct rates of porosity loss are noted: (1) samples dominated by clay (>45% insoluble residue) compact at a higher rate than samples dominated by fine-grained carbonate and (2) fine-grained carbonate supported samples (with <45% insoluble residue) compact at the same rate irrespective of the content of nonsupporting microfossils or pore-filling clay.