(Table 1) Concentrations of Os, Ir, Pt and 187Os/188Os ratio in ODP Hole 130-806C samples

New osmium (Os) isotope and platinum group element (PGE) concentration data are used in conjunction with published 3He and Th isotope data to determine the relative proportions of lithogenic, extraterrestrial and hydrogenous iridium (Ir) in a Pacific pelagic carbonate sequence from the Ocean Drilling Program (ODP) Site 806 on the Ontong Java Plateau (OJP). These calculations demonstrate that lithogenic and extraterrestrial contributions to sedimentary Ir budget are minor, while hydrogenous Ir accounts for roughly 85% of the total Ir. Application of analogous partitioning calculations to previously reported data from a North Pacific red clay sequence (LL44-GPC3) yields very similar results. Total Ir burial fluxes at Site 806 and LL44-GPC3 are also similar, 45 and 30 pg/cm**2/kyr, respectively. Average Ir/3He and Ir/xs230Th_initial ratios calculated from the entire Site 806 data set are similar to those reported earlier for Pacific sites. In general, down-core profiles of Ir, 3He and xs230Th_initial, are not well correlated with one another. However, all three data sets show similar variance and yield sediment mass accumulation rate estimates that agree within a factor of two. While these results indicate that Ir concentration has potential as a point-paleoflux tracer in pelagic carbonates, Ir-based paleoflux estimates are likely subject to uncertainties that are similar to those associated with Co-based paleoflux estimates. Consequently, local calibration of Ir flux in space and time will be required to fully assess the potential of Ir as a point paleoflux tracer. Measured 187Os/188Os of the OJP sediments are systematically lower than the inferred 187Os/188Os of contemporaneous seawater and a clear glacial-interglacial 187Os/188Os variation is lacking. Mixing calculations suggest Os contributions from lithogenic sources are insufficient to explain the observed 187Os/188Os variations. The difference between the 187Os/188Os of bulk sediment and that of seawater is interpreted in terms of subtle contributions of unradiogenic Os carried by particulate extraterrestrial material. Down-core variations of 187Os/188Os with Pt/Ir and Os/Ir also point to contributions from extraterrestrial particles. Mixing calculations for each set of several triplicate analyses suggest that the unradiogenic Os end member cannot be characterized by primary extraterrestrial particles of chondritic composition. It is noteworthy that in efforts aimed at determining the effect of extraterrestrial contributions, 187Os/188Os of pelagic carbonates has greater potential compared to abundances of PGE. An attempt has been made for the first time to estimate sediment mass accumulation rates based on amount of extraterrestrial Os in the OJP samples and previously reported extraterrestrial Os flux. Throughout most of the OJP record, Os isotope-based paleoflux estimates are within a factor of two of those derived using other constant flux tracers. Meaningful flux estimates cannot be made during glacial maxima because the OJP sediments do not record the low 187Os/188Os reported previously. We speculate that this discrepancy may be related to focusing of extraterrestrial particles at the OJP, as has been suggested to explain down-core 3He variations.

(Table 2) Methane to ethane ratio, and d13C-methane at DSDP Hole 76-533

Natural gas hydrates are clathrates in which water molecules form a crystalline framework that includes and is stabilized by natural gas (mainly methane) at appropriate conditions of high pressures and low temperatures. The conditions for the formation of gas hydrates are met within continental margin sediments below water depths greater than about 500 m where the supply of methane is sufficient to stabilize the gas hydrate. Observations on DSDP Leg 11 suggested the presence of gas hydrates in sediments of the Blake Outer Ridge. Leg 76 coring and sampling confirms that, indeed, gas hydrates are present there. Geochemical evidence for gas hydrates in sediment of the Blake Outer Ridge includes (1) high concentrations of methane, (2) a sediment sample with thin, matlike layers of white crystals that released a volume of gas twenty times greater than its volume of pore fluid, (3) a molecular distribution of hydrocarbon gases that excluded hydrocarbons larger than isobutane, (4) results from pressure core barrel experiments, and (5) pore-fluid chemistry. The molecular composition of the hydrocarbons in these gas hydrates and the isotopic composition of the methane indicate that the gas is derived mainly from microbiological processes operating on the organic matter within the sediment. Although gas hydrates apparently are widespread on the Blake Outer Ridge, they probably are not of great economic significance as a potential, unconventional, energy resource or as an impermeable cap for trapping upwardly migrating gas at Site 533.

(Table 2) Aragonite, high and low magnesium calcite, major elements, bioclast and planktic foraminifera from ODP Hole 133-817A

Investigation of the Middle Miocene-Pleistocene succession in cores at ODP Site 817A (Leg 133), drilled on the slope south of the Queensland Plateau, identified the various material fluxes contributing to sedimentation and has determined thereby the paleogeographic events which occurred close to the studied area and influenced these fluxes. To determine proportions of platform origin and of plankton origin of carbonate mud, two reference sediments were collected: (1) back-reef carbonate mud from the Young Reef area (Great Barrier Reef); and (2) Late Miocene chalk from the Loyalty Basin, off New Caledonia. Through their biofacies and mineralogical and geochemical characters, these reference sediments were used to distinguish the proportions of platform and basin components in carbonate muds of 25 core samples from Hole 817A. Two "origin indexes" (i1 and i2) relate the proportion in platform and basin materials. The relative sedimentation rate is inferred from the high-frequency cycles determined by redox intervals in the cores. Bulk carbonate deposited in each core has been calculated in two ways with close results: (1) from calcimetric data available in the Leg 133 preliminary reports (Davies et al., 1991); and (2) from average magnetic susceptibility of cores, a value negatively correlated to the average carbonate content. Vertical changes in sedimentation rates, in carbonate content, in origin indexes and in "linear fluxes" document the evolution of sediment origins from platform carbonates, planktonic carbonates and insoluble material through time. These data are augmented with the variations in organic-matter content through the 817A succession. The observed changes and their interpretation are not modified by compaction, and are compatible with major paleogeographic events including drowning of the Queensland Plateau (Middle Miocene-Early Pliocene) and the renewal of shallow carbonate production, (1) during the Late Pliocene, and (2) from the Early Pleistocene. The birth and growth of the Great Barrier Reef is also recorded from 0.5 Ma by a strengthening of detrital carbonate deposition and possibly by a lack of clay minerals in the 4 upper cores, a response to trapping of terrigenous material behind this barrier. In addition, a maximum of biological silica production is displayed in the Middle Miocene. These changes constrain the time of events and the sequence-stratigraphy framework some components of which are transgression surface, maximum flooding surface and low-stand turbidites. Sedimentation rates and material fluxes show cycles lasting 1.75 Myr. Whatever their origin (climatic and/or eustatic) these cycles affected the planktonic production primarily. The changes also show that major carbonate variations in the deposits are due to a dilution effect by insoluble material (clay, biogenic silica and volcanic glasses) and that plankton productivity, controlling the major fraction of carbonate sedimentation, depends principally on terrigenous supplies, but also on deep-water upwelling. Accuracy of the method is reduced by redeposition, reworking, and probable occurrence of hiatuses.

Abundance of calcareous nannofossils across the K/T boundary at ODP Hole 113-690C (Table 1)

A biostratigraphically continuous, but intensely bioturbated, Cretaceous/Tertiary boundary sequence was cored during Ocean Drilling Program (ODP) Leg 113 on Maud Rise (65°S) in the Weddell Sea off East Antarctica. This interval is the first recovered by ODP/DSDP in the South Atlantic sector of the Southern Ocean and offers a unique opportunity to study the nannofossil sequences leading up to and beyond the terminal Cretaceous event at a high southern latitude. The K/T boundary lies just within Chron 29R and is placed at ODP Sample 113-690C-15X-4, 41.5 cm. An iridium anomaly was independently noted at about this level as well. Upper Maestrichtian-lower Paleocene sediments consist mostly of light-colored nannofossil chalks. Dark brown sediments at the base of the Danian (Zone CPla) are characterized by an increased clay content attributed to a drop in calcareous microplankton productivity following the terminal Cretaceous event. Although delineation of the boundary is hampered by intense bioturbation, the sharp color contrast between overlying clay-rich, dark brown chalks of the Tertiary and light cream colored chalks of the Cretaceous aids in the selection of the K/T horizon. Several dark colored burrows sampled at intervals as far as 1.3 m below the boundary and within the light colored Cretaceous chalk were found to contain up to 17% Tertiary nannofossils. Calcareous nannofossils from the boundary interval were divided into three groups for quantitative study. The three groups, "Cretaceous," "Tertiary," and "Survivor," exhibit a sequential change across the boundary with the Cretaceous forms giving way to a Survivor-dominated assemblage beginning at the boundary followed shortly thereafter by the appearance of the Tertiary taxa, Cruciplacolithus and Hornibrookina. The species, H. edwardsii, comprises nearly 50% of the assemblage just above the Zone CPla/CPlb boundary, an abundance not reported elsewhere at this level. Calculation of individual species abundances reveals several additional differences between this K/T boundary interval and those studied from middle and low latitude sections. The percentage of Thoracosphaera is much lower at the boundary in this section and a small form, Prediscosphaera stoveri, is extremely abundant in Cretaceous sediments just below the boundary.

Osmium-isotope geochemistry of ODP Site 159-959

Analyses of Re, Os, and Ir concentrations, as well as Os-isotopic compositions, are reported for a suite of sediments from Ocean Drilling Program Site 959. These samples vary in age from late Neogene to Late Cretaceous, and represent a range in depositional oxidation-reduction conditions from suboxic in the Neogene to anoxic in the Late Cretaceous. Age assignments based on shipboard biostratigraphic data are used to calculate initial 187Os/186Os ratios of Neogene nannofossil/foraminifer oozes and Eocene to upper Oligocene laminated diatomites. These calculated initial ratios are in general agreement with published data constraining the Os-isotopic evolution of seawater through time, indicating that the Os-isotopic composition of these sediments is controlled largely by the Os isotopic composition of contemporaneous seawater. Results from analyses of Upper Cretaceous to lower Paleocene claystones do not exhibit elevated Ir concentrations and exhibit Re-Os systematics that are highly consistent with closed-system production of 187Os by in situ 187Re decay. Scatter in both the Cretaceous and Cenozoic data sets is likely the result of the influence of nonhydrogenous Os, carried by clastics, on the bulk sediment Os-isotopic composition, or post-depositional mobility of Re and/or Os.

Osmium isotopic composition and platinum group element concentrations in sediments from ODP Hole 145-886C

Paired analyses of Os isotope composition and concentration of bulk sediment and leachable Os in a metalliferous pelagic clay sequence from the North Pacific, ODP Site 886C, are used to reconstruct the marine Os isotope record and the particulate meteoritic Os flux between 65.5 and 78 Ma. Measured 187Os/188Os of bulk sediments ranges from approximately 0.64 to 0.32 and those of leach analyses are very similar to bulk analyses. Hydrogenous Os dominates the sedimentary Os inventory throughout most of the studied interval. As a result the measured 187Os/188Os of leachable Os approximates that of contemporaneous seawater. The ODP 886C record shows rising 187Os/188Os in the deepest portion of the core, with a local maximum of 0.66 close to 74 Ma. The 67-72 Ma portion of the record is characterized by nearly constant 187Os/188Os ratios close to 0.6. The structure of the marine Os isotope record from ODP 886C differs markedly from the seawater 87Sr/86Sr curve, which rises monotonically throughout the time interval studied here. Calculated particulate meteoritic Os fluxes are between 0.5 and 2 pg/cm**2/kyr throughout most of the studied interval. Two discrete intervals of the core (one of which is within Cretaceous Tertiary, boundary KTB interval) are characterized by higher fluxes of meteoritic Os. Excluding these two intervals, the average background flux of particulate meteoritic Os is roughly half of that estimated from analyses of Cenozoic marine sediments. These are the first Os isotope data to provide evidence of resolvable temporal variations in the background flux of particulate meteoritic material to the Earth.

Carbon and nitrogen content of marine pore waters

We have developed sampling methods and an analytical system to determine the concentration of dissolved organic C (DOC) in marine pore waters. Our analytical approach is a modification of recently developed high-temperature, Pt-catalyzed oxidation methods; it uses Chromatographic trapping of the DOC-derived CO2 followed by reduction to CH4 and flame ionization detection. Sampling experiments with nearshore sediments indicate that pore-water separation by whole-core squeezing causes artificially elevated DOC concentrations, while pore-water recovery by sectioning and centrifugation does not appear to introduce DOC artifacts. Results from a set of northwestern Atlantic continental slope cores suggest that net DOC production accounts for >50% of the organic C that is recycled at the sediment-water interface.

Abundance of calcareous nannofossils in ODP Hole 121-752B (Table 1)

A biostratigraphically complete Cretaceous/Tertiary boundary was recovered during Ocean Drilling Program Leg 121. The boundary, cored in ODP Hole 752B on Broken Ridge, is the most expanded deep-sea section yet recovered by ODP/DSDP. The initial Danian subzone, CP la, spans nearly 5 m and the underlying uppermost Maestrichtian Nephrolithus frequens Zone extends 50 m below the boundary. The paleolatitude of Broken Ridge at Cretaceous/Tertiary time is estimated at 50°-55°S which includes this site among the latest in a series of complete or near complete high southern latitude Cretaceous/Tertiary boundary sections recovered by ODP (Leg 113 Site 690 and Leg 119 Site 738). The boundary at Site 752 lies at the base of a thick (6-6.5 m) volcanic ash unit composed of multiple ash layers which overlies indurated Maestrichtian chalks. Magnetostratigraphy indicates that the boundary lies within Subchron 29R, which is the case for all other known complete sections for which the polarity has been determined. Anomalous abundances of the trace element iridium are present at the boundary. A second iridium peak, 80 cm above the boundary, corresponds to an increase in redeposited Cretaceous nannofossils. The nannofossil succession is similar to that found at previously studied austral high-latitude ODP drill sites with few differences due to the more northerly location of this site. Individual nannofossil species were counted and placed into three categories. A plot of the percent abundance of Cretaceous, Tertiary, and 'survivor' groups illustrates the rapid replacement of the Cretaceous nannoflora by 'survivor' forms beginning at the boundary and the dominance of this latter group through the initial Danian biozone. This 'survivor' or opportunistic assemblage is then rapidly replaced by newly evolved Tertiary taxa. The assemblage of the uppermost Maestrichtian is biased toward dissolution-resistant forms such as Micula decussata. In those few intervals where preservation is good, the dissolution susceptible species, Prediscosphaera stoveri, is more prevalent and overall diversity of the assemblage is higher. The 'survivor' assemblage is dominated by Zygodiscus sigmoides and Thoracosphaera. The Tertiary assemblage consists of rare Biantholithus sparsus, the first of this group to appear. It is followed several meters upsection by Cruciplacolithus primus. Cruciplacolithus tenuis and small Prinsius spp. dominate the assemblage beginning at about 5 m above the boundary.