Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.

10Be content s of late Cenozoic sediments from ODP Leg 117

This paper is a comparative study of the variation in 10Be content of different late Cenozoic sedimentary environments recovered during ODP Leg 117. The Oman Margin site, Hole 728A, with overlying high-productivity cells, the pelagic Owen Ridge site, Hole 722A, and the Indus Fan site, Hole 720A, each display a specific 10Be distribution with time. Differences in scavenging intensity and upwelling in the water column, must account for the variations in the initial 10Be input into the sediments from Holes 728A and 722A, whereas differences in sediment character and sedimentation rate can explain the variances between Holes 722A, 728A, and 720A.

Apatite fission track analytical data for samples from ODP Leg 152

We test a new approach to understanding the tectonic evolution of passive margins by using fission-track analysis on detrital apatites from sediments deposited offshore East Greenland. These apatites have not undergone postdepositional track annealing and therefore reflect provenance. The apatites preserve a component of the source rocks' thermal history that otherwise may not be retained within the present-day outcrop. Fission-track derived denudational histories from samples at Ocean Drilling Program drill sites offshore East Greenland at lat 63°N are compared with data from the onshore Singertat Complex. Previous apatite fission-track studies and geomorphic mapping of the East Greenland coast have shown that locally up to 6 km of denudation may have occurred, implying significant tectonic or magmatic activity starting as much as 30 m.y. after breakup at 56 Ma. In contrast, apatite fission-track data presented here record <2 km of Cenozoic denudation in southeast Greenland, probably driven by magmatic underplating at the time of breakup. Large-magnitude, postrift denudation of East Greenland is restricted to the area around Kangerdlugssuaq (68°N). The timing (<40-50 Ma) and magnitude are in accord with revised plume track models suggesting that the Iceland plume crossed the margin here during the late Eocene.

Foraminifer, coarse fraction and carbonate characteristics of sediments from ODP Leg 198 sites on Shatsky Rise

Holes 1209A and 1211A on Southern High, Shatsky Rise contain expanded, nearly continuous records of carbonate-rich sediment deposited in deep water of the equatorial Pacific Ocean during the Paleocene and Eocene. In this study, we document intervals of carbonate dissolution in these records by examining temporal changes in four parameters: carbonate content, coarse size fraction (>38 µm), benthic foraminiferal abundance, and planktonic foraminiferal fragmentation ratio. Carbonate content is not a sensitive indicator of carbonate dissolution in the studied sections, although rare intervals of low carbonate may reflect times of relatively high dissolution. The proportion of coarse size fraction does not accurately record carbonate dissolution either because the relative abundance of nannofossils largely determines the grain-size distribution. Benthic abundance and fragmentation covary (r**2 = 0.77) and are probably the best indicators for carbonate dissolution. For both holes, records of these parameters indicate two episodes of prominent dissolution. The first of these occurs in the upper Paleocene (~59-58 Ma) and the second in the middle to upper Eocene (~45-33.7 Ma). Other intervals of enhanced carbonate dissolution are located in the upper Paleocene (~56 Ma) and in the upper lower Eocene (~51 Ma). Enhanced preservation of planktonic foraminiferal assemblages marks the start of both the Paleocene and Eocene epochs.

Carbon isotopic composition of dissolved CO2, CO2 gas and methane in sediments from ODP Leg 172 sites

Carbon isotopic data of interstitial dissolved CO2 (CO2), CO2 gas, and methane show that a variety of microbial diagenetic processes produce the observed isotopic trends. Anaerobic methane oxidation (AMO) is an important process near the sulfate-methane interface (SMI) that strongly influences the isotopic composition of CO2 in the sulfate reduction and upper methanogenic zones, which in turn impacts methane isotopic composition. Dissolved CO2 and methane are maximally depleted in 13C near the SMI, where 13C values are as light as -31.8 and -101 PDB for CO2 and methane, respectively. CO2 reduction links the CO2 and methane pools in the methanogenic zone so that the carbon isotopic composition of both pools evolves in concert, generally showing increasing enrichments of 13C with increasing depth. These isotopic trends mirror those within other methane-rich continental rise sediments worldwide.

Geochemistry at DSDP Leg 55 Holes

The tops of the Emperor chain guyots, which were drilled during Leg 55, lie above the carbonate compensation depth (CCD), as well as above the foraminiferal dissolution level, i.e., lysocline. They are therefore the sites of accumulation of pelagic foraminiferal nannofossil ooze, such accumulation having taken place here since the moment of the seamounts' subsidence and the termination of shallow-water carbonate accumulation which was formerly developed on their tops. But the existence of strong bottom currents over the tops and slope scarps limits, and at some places reduces to zero, sedimentation of any pelagic particles. At such areas there are formed thick iron-manganese crusts. The seamounts drilled on Leg 55 are within the northern (Boreal) belt of biogenic silica accumulation, which existed in the northern Pacific throughout the Neogene. This circumstance presupposes a possible enrichment of the relatively fine-grained sediments with biogenic silica - diatoms and radiolarians.

Mineralogy and inorganic geochemistry of sediments at DSDP Leg 65 Holes

During Leg 65, 15 holes were drilled at four sites located on young crust in the mouth of the Gulf of California. Quaternary to upper Pliocene hemipelagic sediments above and interlayered within the young basaltic basement were cored. The influence of hot lava, high temperature gradients, and hydrothermal activity on the mineralogy and geochemistry of the terrigenous sediments near contacts with basalts might therefore be expected. The purpose of the present study was to determine the mineralogy and inorganic geochemistry of these sediments and to analyze the nature and extent of low temperature alteration. To this end we studied the mineralogy and inorganic geochemistry of 75 sediment samples, including those immediately overlying uppermost basalts and those from layers alternating with basalts within the basement. We separated three size fractions - <2 µm (clay), 2-20 µm (intermediate), and >20 µm (coarse) - and applied the following mineralogical determinations: x-ray diffraction (XRD), infrared spectroscopy, transmission and scanning electron microscopy, and optical microscopy (for coarse fractions, using thin sections and smear slides). We calculated the percentages of clay minerals using Biscaye's (1964) method, and used routine wet chemical analyses to determine bulk composition and quantitative spectral analyses for trace elements.

Stable carbon isotope ratios and the formation of dolomite in ODP Leg 175 sites

We examine the link between organic matter degradation, anaerobic methane oxidation (AMO), and sulfate depletion and explore how these processes potentially influence dolomitization. We determined rates and depths of AMO and dolomite formation for a variety of organic-rich sites along the west African Margin using data from Ocean Drilling Program (ODP) Leg 175. Rates of AMO are calculated from the diffusive fluxes of CH4 and SO4, and rates of dolomite formation are calculated from the diffusive flux of Mg. We find that the rates of dolomite formation are relatively constant regardless of the depth at which it is forming, indicating that the diffusive fluxes of Mg and Ca are not limiting. Based upon the calculated log IAP values, log K(sp) values for dolomite were found to narrowly range between -16.1 and -16.4. Dolomite formation is controlled in part by competition between AMO and methanogenesis, which controls the speciation of dissolved CO2. AMO increases the concentration of CO3[2-] through sulfate reduction, favoring dolomite formation, while methanogenesis increases the pCO2 of the pore waters, inhibiting dolomite formation. By regulating the pCO2 and alkalinity, methanogenesis and AMO can regulate the formation of dolomite in organic-rich marine sediments. In addition to providing a mechanistic link between AMO and dolomite formation, our findings provide a method by which the stability constant of dolomite can be calculated in modern sediments and allow prediction of regions and depth domains in which dolomite may be forming.

Geochemistry and mineralogy of ODP Leg 107 basalts

During ODP Leg 107, the basement of the Tyrrhenian Sea was drilled at Site 650, located in the Marsili basin, and at Sites 651 and 655, both located in the Vavilov basin. In addition, a lava flow was drilled at Site 654 on the Sardinia rifted margin. Mineral and whole rock major and trace element chemistry, including rare earth element (REE) and Sr and Nd isotopic ratios, were determined in samples of these rocks. Site 654 lava was sampled within uppermost Pliocene postrift sediments. This lava is a basaltic andesite of intraplate affinity, and is analogous to some Plio-Pleistocene tholeiitic lavas from Sardinia. Site 650 basalts, drilled beneath 1.7-1.9-Ma-old basal sediment, are strongly altered and vesicular suggesting a rapid subsidence of the Marsili basin. Based on incompatible trace elements, these basalts show calc-alkaline affinity like some products of the Marsili Seamount and the Eolian arc. The basement of the two sites drilled within Vavilov basin shows contrasting petrologies. Site 655, located along the Gortani ridge in the western part of the basin, drilled a 116-m-thick sequence of basalt flows beneath 3.4-3.6-Ma-old basal sediments. These basalts are chemically relatively homogeneous and show affinity to transitional MORB. Four units consisting of slightly differentiated basaltic lavas, have been identified. Site 655 basalts are geochemically similar to the high Ti lavas from DSDP Leg 42, Site 373 (Vavilov Basin). The basement at Site 651, overlain by 40 m of metalliferous dolostone covered by fossiliferous sediments with an age of 2 Ma, consists of two basalt units separated by a dolerite-albitite intrusive body; serpentinized harzburgites were drilled for 30 m at the base of the hole. The two basalt units of Site 651 are distinct petrochemically, though both show incompatible elements affinity with high-K calc-alkaline/calc-alkaline magmas from Eolian arc. The cpx chemistry and high K/Na ratio of the lower unit lavas suggest a weak alkaline tendency of potassic lineage. Leg 107 basement rock data, together with data from DSDP Site 373 and from dredged samples, indicate that the deepest basins of the central Tyrrhenian Sea are underlain by a complex back-arc basin crust produced by magmas with incompatible element affinities to transitional MORB (Site 655 and DSDP Site 373), and to calc-alkaline and high-K calc-alkaline converging plate margin basalts (Sites 650 and 651). This petrogenetic complexity is in accordance with the back-arc setting of the Vavilov and Marsili basins. Other back-arc basin basalts, particularly those from ensialic basins such as the Bransfield Strait (Antarctica), show a comparable petrogenetic complexity (cf., Sounders and Tarney, 1984).

Organic geochemical studies of DSDP Leg 64 Holes

Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.

Geochemistry of interstitial gases in sedimentary deposits at DSDP Leg 64 Holes

We analyzed interstitial gases from holes at Sites 474, 477, 478, 479, and 481 in the Gulf of California, using gas chromatography and stable isotope mass spectrometry to evaluate their composition in terms of biogenic and thermogenic sources. The hydrocarbon gas (C1-C5) concentrations were comparable to the shipboard data, and no olefins could be detected. The ?13C data for the CH4 confirmed the effects of thermal stress on the sedimentary organic matter, because the values were typically biogenic near the surface and became more depleted in 12C versus depth in holes at Sites 474, 478, and 481. The CH4 at Site 477 was the heaviest, and in Hole 479 it did not show a dominant hightemperature component. The CO2 at depth in most holes was mostly thermogenic and derived from carbonates. The low concentrations of C2-C5 hydrocarbons in the headspace gas of canned sediments precluded a stable carbon-isotope analysis of their genetic origin.