(Table 1) Oxygen isotopes in minerals at DSDP Hole 83-504B basalts

The D/H, 18O/16O and 87Sr/86Sr ratios of the basaltic basement from the Leg 83 section of DSDP Hole 504B show that in that area the oceanic crust has experienced intensive but not pervasive alteration. Isotope ratios of the basalts are very heterogeneous because of an input of oxygen, hydrogen, and strontium from seawater. The hydrogen isotopic composition of many samples displays the complete thermal history of the water-rock interactions. High-temperature mineral formations (actinolites, epidotes, and chlorites) were overgrown by a mineralization at lower temperatures (mixedlayer smectites, iddingsites, and smectites) during successive stages of cooling of the oceanic crust by cold seawater. From 87Sr/86Sr data bulk water/rock ratios up to 5:1 have been calculated. There is evidence that some primary minerals like high-An plagioclases contain oxygen from altered basalts. We have discussed the probability that there existed a seawater/crust interface, now at a depth of 620 m sub-basement, during the high-temperature water/rock interactions. This interface was covered during later magmatism by thick flows, pillow lavas, and intrusives.

Oxygen isotopes, IRD and SST reconstruction for the interval MIS31-19 of IODP Site 306-U1314

Early and Mid-Pleistocene climate, ocean hydrography and ice sheet dynamics have been reconstructed using a high-resolution data set (planktonic and benthic d18O time series, faunal-based sea surface temperature (SST) reconstructions and ice-rafted debris (IRD)) record from a high-deposition-rate sedimentary succession recovered at the Gardar Drift formation in the subpolar North Atlantic (Integrated Ocean Drilling Program Leg 306, Site U1314). Our sedimentary record spans from late in Marine Isotope Stage (MIS) 31 to MIS 19 (1069-779 ka). Different trends of the benthic and planktonic oxygen isotopes, SST and IRD records before and after MIS 25 (~940 ka) evidence the large increase in Northern Hemisphere ice-volume, linked to the cyclicity change from the 41-kyr to the 100-kyr that occurred during the Mid-Pleistocene Transition (MPT). Beside longer glacial-interglacial (G-IG) variability, millennial-scale fluctuations were a pervasive feature across our study. Negative excursions in the benthic d18O time series observed at the times of IRD events may be related to glacio-eustatic changes due to ice sheets retreats and/or to changes in deep hydrography. Time series analysis on surface water proxies (IRD, SST and planktonic d18O) of the interval between MIS 31 to MIS 26 shows that the timing of these millennial-scale climate changes are related to half-precessional (10 kyr) components of the insolation forcing, which are interpreted as cross-equatorial heat transport toward high latitudes during both equinox insolation maxima at the equator.

Stable oxygen isotopes of calcite veins in ODP Site 146-892

In situ secondary ionization mass spectrometry (SIMS) analyses of oxygen isotopes in authigenic calcite veins were obtained from an active thrust fault system drilled at Ocean Drilling Program (ODP) Site 892 (44°40.4'N, 125°07.1'W) along the Cascadia subduction margin. The average d18OPDB value of all samples is -9.9 per mil and the values are the lowest of any measured in active accretionary prisms. Ranges in individual veins can be as much as 19.6 per mil. There is an isotopic stratigraphy related to the structural stratigraphy. Mean isotope values in the hanging wall, thrust, and footwall are -14.4 per mil, -9.5 per mil, and -5.2 per mil, respectively. Several veins and crosscutting vein sequences show a general trend from lower to higher d18O values over time. Isotopic and textural data indicate several veins formed by a crack-seal mechanism and growth into open fractures. The best explanation for the strong 18O depletions is periodic rapid flow from 2-3 km deeper in the prism. Relatively narrow isotopic ranges for most veins suggest that fluids were derived from a similar source depth for each episode of fluid pulse and calcite crystallization. Structural and mass balance considerations are consistent with a record preserved in the veins of ten to hundreds of thousands of years. The fluid pulses may relate to periodic large earthquake events such as those recognized in the paleoseismicity records from the Cascadia margin.

Planktonic foraminiferal oxygen isotopes of ODP Site 143-865 samples

Cool tropical sea surface temperatures (SSTs) are reported for warm Paleogene greenhouse climates based on the d18O of planktonic foraminiferal tests. These results are difficult to reconcile with models of greenhouse gas-forced climate. It has been suggested that this "cool tropics paradox" arises from postdepositional alteration of foraminiferal calcite, yielding erroneously high d18O values. Recrystallization of foraminiferal tests is cryptic and difficult to quantify, and the compilation of robust d18O records from moderately altered material remains challenging. Scanning electron microscopy of planktonic foraminiferal chamber-wall cross sections reveals that the basal area of muricae, pustular outgrowths on the chamber walls of species belonging to the genus Morozovella, contain no mural pores and may be less susceptible to postdepositional alteration. We analyzed the d18O in muricae bases of morozovellids from the central Pacific (Ocean Drilling Program Site 865) by ion microprobe using 10 ?m pits with an analytical reproducibility of ±0.34 per mil (2 standard deviations). In situ measurements of d18O in these domains yield consistently lower values than those published for conventional multispecimen analyses. Assuming that the original d18O is largely preserved in the basal areas of muricae, this new d18O record indicates Early Paleogene (~49-56 Ma) tropical SSTs in the central Pacific were 4°-8°C higher than inferred from the previously published d18O record and that SSTs reached at least ~33°C during the Paleocene-Eocene thermal maximum. This study demonstrates the utility of ion microprobe analysis for generating more reliable paleoclimate records from moderately altered foraminiferal tests preserved in deep-sea sediments.

Element contents, sulfur and oxygen isotopes, and molecular biomarkers of phosphatic crust samples from the Chimbote Platform of the shelf off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01' S and 10°24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS2) and sphalerite (ZnS). Low d34Spyrite values (average -28.8 per mill) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C15:0, i/ai-C17:0 and 10MeC16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

Stable oxygen isotopes of Globigerinoides ruber and biostratigraphic datums at ODP Site 165-1002

Ocean Drilling Program Site 1002 in the Cariaco Basin was drilled in the final two days of Leg 165 with only a short transit remaining to the final port of San Juan, Puerto Rico. Because of severe time constraints, cores from only the first of the three long replicate holes (Hole 1002C) were opened at sea for visual description, and the shipboard sampling was restricted to the biostratigraphic examination of core catchers. The limited sampling and general scarcity of biostratigraphic datums within the late Quaternary interval covered by this greatly expanded hemipelagic sequence resulted in a very poorly defined age model for Site 1002 as reported in the Leg 165 Initial Reports volume of the Proceedings of the Ocean Drilling Program. Here, we present for the first time a new integrated stratigraphy for Site 1002 based on the standard of late Quaternary oxygen-isotope variations linked to a suite of refined biostratigraphic datums. These new data show that the sediment sequence recovered by Leg 165 in the Cariaco Basin is continuous and spans the time interval from 0 to ~580 ka, with a basal age roughly twice as old as initially suspected from the tentative shipboard identification of a single biostratigraphic datum. Lithologic subunits recognized at Site 1002 are here tied into this new stratigraphic framework, and temporal variations in major sediment components are reported. The biogenic carbonate, opal, and organic carbon contents of sediments in the Cariaco Basin tend to be high during interglacials, whereas the terrigenous contents of the sediments increase during glacials. Glacioeustatic variations in sea level are likely to exert a dominant control on these first-order variations in lithology, with glacial surface productivity and the nutrient content of waters in the Cariaco Basin affected by shoaling glacial sill depths, and glacial terrigenous inputs affected by narrowing of the inner shelf and increased proximity of direct riverine sources during sea-level lowstands.