Geochemistry of carbonate cements of ODP Leg 112 samples

The evolution of pore fluids migrating through the forearc basins, continental massif, and accretionary prism of the Peru margin is recorded in the sequence of carbonate cements filling intergranular and fracture porosities. Petrographic, mineralogic, and isotopic analyses were obtained from cemented clastic sediments and tectonic breccias recovered during Leg 112 drilling. Microbial decomposition of the organic-rich upwelling facies occurs during early marine diagenesis, initially by sulfate-reduction mechanisms in the shallow subsurface, succeeded by carbonate reduction at depth. Microcrystalline, authigenic cements formed in the sulfate-reduction zone are 13C-depleted (to -20.1 per mil PDB), and those formed in the carbonate-reduction zone are 13C-enriched (to +19.0 per mil PDB). Calcium-rich dolomites and near-stoichiometric dolomites having uniformly heavy d18O values (+2.7 to +6.6 per mil PDB) are typical organic decomposition products. Quaternary marine dolomites from continental-shelf environments exhibit the strongest sulfate-reduction signatures, suggesting that Pleistocene sea-level fluctuations created a more oxygenated water column, caused periodic winnowing of the sediment floor, and expanded the subsurface penetration of marine sulfate. We have tentatively identified four exotic cement types precipitated from advected fluids and derived from the following diagenetic environments: (1) meteoric recharge, (2) basalt alteration, (3) seafloor venting and (4) hypersaline concentration. Coarsely crystalline, low-magnesium (Lo-Mg) calcite cements having pendant and blocky-spar morphologies, extremely negative d18O values (to -7.5 per mil PDB), and intermediate d13C values (-0.4 per mil to +4.6 per mil PDB) are found in shallow-marine Eocene strata. These cements are evidently products of meteoric diagenesis following subaerial emergence during late Eocene orogenic movements, although the strata have since subsided to greater than 4,000 m below sea level. Lo-Mg calcite cements filling scaly fabrics in the late Miocene accretionary prism sediments are apparently derived from fluids having lowered magnesium/calcium (Mg/Ca) and 18O/16O ratios; such fluids may have reacted with the subducting oceanic crust and ascended through the forearc along shallow-dipping thrust faults. Micritic, high-magnesium (Hi-Mg) calcite cements having extremely depleted d13C values (to -37.3%c PDB), and a benthic fauna of giant clams (Calyptogena sp.) supported by a symbiotic, chemoautotrophic metabolism, provide evidence for venting of methane-charged waters at the seafloor. Enriched d18O values (to +6.6%c PDB) in micritic dolomites from the continental shelf may be derived from hypersaline fluids that were concentrated in restricted lagoons behind an outer-shelf basement ridge, reactivated during late Miocene orogenesis.