Isotopic composition of interstitial fluids and origin of methane at DSDP Leg 84 Holes

CH4 and CO2 species in pore fluids from slope sediments off Guatemala show extreme 13C-enrichment (d13C of -41 and +38 per mil, respectively) compared with the typical degree of 13C-enrichment in pore fluids of DSDP sediments (d13C of - 60 and + 10 per mil). These unusual isotopic compositions are believed to result from microbial decomposition of organic matter, and possibly from additional isotopic fractionation associated with the formation of gas hydrates. In addition to the isotopic fractionation displayed by CH4 and CO2, the pore water exhibits a systematic increase in d18O with decrease in chlorinity. As against seawater d18O values of 0 and chlorinity of 19 per mil, the water collected from decomposed gas hydrate from Hole 570 had a d18O of + 3.0 per mil and chlorinity of 9.5 per mil. The isotopic compositions of pore-fluid constituents change gradually with depth in Hole 568 and discontinuously with depth in Hole 570.

Isotopic composition of various forms of sulfur in barite crusts from the Red Sea rift

Barite crusts were formed by an intermittent hydrothermal vent with output temperature from 85 to 465°C. Principal sources of supply of sulfate sulfur are sea water, evaporites, and tholeiitic basalts of the Red Sea rift. Sulfides and sulfates were formed in conditions of isotope disequilibrium with respect to sulfur because rate of precipitation of sulfur compounds from hydrothermal solution was high compared with rate of isotope exchange.

Relative abundance and isotopic composition of calcite, dolomite and siderite from ODP Leg 164 sites

Authigenic carbonate mineral distributions are compared to pore-water geochemical profiles and used to evaluate diagenesis within sedimentary sections containing gas hydrates on the Blake Ridge (Ocean Drilling Program Sites 994, 995, and 997). Carbonate mineral distributions reveal three distinct diagenetic zones. (1) Carbonate minerals in the upper 20 m are primarily biogenic and show no evidence of diagenesis. The d13C and d18O values of calcite within this zone reflects marine carbonate (~0 per mil Peedee belemnite [PDB]) formed in equilibrium with seawater. (2) Between 20 and 100 mbsf, calcite d13C values are distinctly negative (as low as -7.0 per mil), and authigenic dolomite is common (~2-40 wt%) with d13C values between -3.6 per mil and 13.7 per mil. (3) Below 100 mbsf, dolomite abundance decreases to trace amounts, and disseminated siderite becomes the pervasive (~2-30 wt%) authigenic carbonate. Both siderite textures and stable isotope values indicate direct precipitation from pore fluids rather than dolomite replacement. The d13C and d18O values of siderite vary from 5.0 per mil to 10.9 per mil and 2.9 per mil to 7.6 per mil, respectively. Comparisons between the d13C profiles of dissolved inorganic carbon (DIC) and pore-water concentration gradients, with the d13C and d18O values of authigenic carbonates, delineate a distinct depth zonation for authigenic carbonate mineral formation. Coincidence of the most negative d13CDIC values (<=-38 per mil) and negative d13C values of both calcite and dolomite, with pore-water alkalinity increases, sulfate depletion, and decreases in interstitial Ca2+ and Mg2+ concentrations at and below 20 mbsf, suggests that authigenic calcite and dolomite formation is initiated at the base of the sulfate reduction zone (~21 mbsf) and occurs down to ~100 mbsf. Siderite formation apparently occurs between 120 and 450 mbsf; within, and above, the gas hydrate-bearing section of the sediment column (~200-450 mbsf). Siderite d13C and d18O values are nearly uniform from their shallowest occurrence to the bottom of the sedimentary section. However, present-day pore-water d13CDIC values are only similar to siderite d13C values between ~100 and 450 mbsf. Furthermore, calculated equilibrium d18O values of siderite match the measured 18O values of siderite between 120 and 450 mbsf. This interval is characterized by high alkalinity (40-120 mM) and low Ca2+ and Mg2+ concentrations, conditions that are consistent with siderite formation.