Isotopic ratios of methane, ethane, carbon dioxide, inorganic carbon and organic matter from ODP Leg 164 sites

The isotopic characteristics of CH4 (d13C values range from -101.3 per mil to -61.1 per mil PDB, and dD values range from -256 per mil to -136 per mil SMOW) collected during Ocean Drilling Program (ODP) Leg 164 indicate that the CH4 was produced by microbial CO2 reduction and that there is not a significant contribution of thermogenic CH4 to the sampled sediment gas from the Blake Ridge. The isotopic values of CO2 (d13C range -20.6 per mil to +1.24 per mil PDB) and dissolved inorganic carbon (DIC; d13C range -37.7 per mil to +10.8 per mil PDB) have parallel profiles with depth, but with an offset of 12.5 per mil. Distinct downhole variations in the carbon isotopic composition of CH4 and CO2 cannot be explained by closed-system fractionation where the CO2 is solely derived from the locally available sedimentary organic matter (d13C -2.0 per mil ± 1.4 per mil PDB) and the CH4 is derived from CO2 reduction. The observed isotopic profiles reflect the combined effects of upwards gas migration and decreased microbial activity with depth.

Geochemistry of tetrapyrrole, tetraterpenoid, and perylene pigments in sediments from the Gulf of California

Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene. Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter. Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Baker and Palmer, 1978; Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature). Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p6. The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected. Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial. Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants. Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene. The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

(Table T1) Pore-water strontium content, and Sr isotope composition and ages of pore waters and sedimentary carbonates of ODP Leg 171B sites

Strontium concentrations and 87Sr/86Sr values were measured on pore-water and sedimentary carbonate samples from sediments recovered at Sites 1049-1053 on the Blake Spur during Ocean Drilling Program Leg 171B. These sites form a 40-km-long depth transect extending along the crest of the Blake Spur from near the upper edge of the Blake Escarpment (a steep cliff composed of Mesozoic carbonates) westward toward the interior of the Blake-Bahama Platform. Although these sites were selected for paleoceanographic purposes, they also form a hydrologic transect across the upper eastern flank of the Blake-Bahama Platform. Here, we use pore-water strontium concentrations and isotopes as a proxy to define patterns of fluid movement through the flanks of this platform. Pore-water strontium concentration increases with depth at all sites implying that strontium has been added during sediment burial and diagenesis. The isotopic values decrease from seawater-like values in the shallow samples (~0.70913) to values as low as 0.707342 in one of the deepest samples (~625 meters below seafloor). The change in pore-water strontium isotopic values is independent of the strontium isotopic compositions predicted from the host sediment age and measured on bulk carbonate in some samples. In most cases the difference between predicted sediment strontium isotopic composition and measured value is less than ±2 about the mean of the measured strontium value. Both the increase in concentration and the decrease in the strontium isotope values with increasing depth indicate that strontium was expelled from older carbonates. The strontium concentration and isotope profiles vary between sites according to their proximity to the Blake-Bahama Platform edge. Profiles from Site 1049 (nearest the platform edge) show the greatest amount of mixing with modern seawater, whereas the site most distal to the platform edge (Site 1052) shows the most significant influence of older, deeper carbonates on the pore-water strontium isotopic composition.