Geochemical composition and atomic formulas of saponites, celadonites and carbonates from ODP Leg 168 sites

With this study, we investigate the mineralogical variations associated with the low-temperature (<100°C) alteration of normal tholeiitic pillow basalts varying in age from 0.8 to 3.5 Ma. Their alteration intensity varies systematically and is related to several factors, including (1) the aging of the igneous crust, (2) the increase of temperatures from the younger to the older sites, measured at the sediment/basement interface, (3) the local and regional variations in lithology and primary porosity, and (4) the degree of pillow fracturing. Fractures represent the most important pathways that allow significant penetration of fluids into the rock and are virtually the only factor controlling the alteration of the glassy rim and the early stages of pillow alteration. Three different alteration stages have been recognized: alteration of glassy margin, oxidizing alteration through fluid circulation in fracture systems, and reducing alteration through diffusion. All the observed mineralogical and chemical variations occurring during the early stages of alteration are interpreted as the result of the rock interaction with "normal," alkaline, and oxidizing seawater, along preferential pathways represented by the concentric and radial crack systems. The chemical composition of the fluid progressively evolves while moving into the basalt, leading to a reducing alteration stage, which is initially responsible for the precipitation of Fe-rich saponite and minor sulfides and subsequently for the widespread formation of carbonates. At the same time, the system evolved from being "water dominated" to being "rock dominated." No alteration effects in pillow basalts were observed that must have occurred at temperatures higher than those measured during Leg 168 at the basement/sediment interface (e.g., between 15° and 64°C).

Ba, Al and SO4 concentrations in sediments and pore fluid of ODP Leg 127/128 samples

The barium distribution in sediments and pore fluids from five sites drilled in the Japan Sea have been used to illustrate the geochemical behavior of this element as it pertains paleoproductivity reconstructions, diagenetic remobilization, and barite precipitation in authigenic fronts. Sites where sulfate is depleted in the pore fluids also show high concentrations of dissolved barium, reflecting dissolution of biogenic barite. The high rate of sedimentation at Sites 798 and 799 results in a rapid sulfate depletion, which in turn leads to barite dissolution and reprecipitation in diagenetic fronts. The dissolved barium distribution at these sites has been used to quantify the rate of barite dissolution; we estimate a first-order rate constant for barite dissolution to be 2*10**-6/s at Site 799 and 2*10**-7/s at Site 798. Authigenic barite has been documented in sediments from Site 799 at 323 meters below seafloor by scanning electron microscopy and X-ray fluorescence analysis. These results indicate barite precipitation in a diagenetic front near the zone of sulfate depletion by upward migration of dissolved barium and downward diffusion of sulfate. Barite precipitation has also been inferred at Sites 796 and 798 based on sedimentary and dissolved barium distributions. Sulfate is not depleted in the pore fluids of Site 794. The lack of diagenetic remobilization of biogenic barium at this site preserves the high barium signal associated with the high-productivity sequences deposited during the late Miocene to Pliocene. Significantly, the organic carbon distribution does not indicate high accumulation rates during the periods of high opal and barium deposition. Instead, higher organic carbon accumulations are recorded in the Quaternary and middle Miocene sequences; intervals that are also characterized by deposition of siliciclastic turbidites. The presence of a terrestrial component in the organic carbon record renders barium a more useful indicator than organic carbon for paleoproductivity reconstructions in this marginal sea.

Chemical and isotope composition of poor fluid from gas-hydrate samples of ODP Site 146-892

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2-19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ~17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperatures of the recovered core ranged from 2 to -1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (delta34S, +27.4?) were released. The delta13C values of the CH4 in the gas hydrate, -64.5 to -67.5? (PDB), together with deltaD values of -197 to -199? (SMOW) indicate a primarily microbial source for the CH4. The delta18O value of the hydrate H2O is +2.9? (SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a >=99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.