Chemical composition of mineral phases of serpentinized and steatized peridotite from the Mid Atlantic Ridge (15°20'N Fracture Zone, ODP Leg209)

Serpentinization of abyssal peridotites is known to produce extremely reducing conditions as a result of dihydrogen (H2,aq) release upon oxidation of ferrous iron in primary phases to ferric iron in secondary minerals by H2O.We have compiled and evaluated thermodynamic data for Fe-Ni-Co-O-S phases and computed phase relations in fO2,g-fS2,g and aH2,aq-aH2S,aq diagrams for temperatures between 150 and 400°C at 50MPa.We use the relations and compositions of Fe-Ni-Co-O-S phases to trace changes in oxygen and sulfur fugacities during progressive serpentinization and steatitization of peridotites from the Mid-Atlantic Ridge in the 15°20'N Fracture Zone area (Ocean Drilling Program Leg 209). Petrographic observations suggest a systematic change from awaruite- magnetite-pentlandite and heazlewoodite-magnetite-pentlandite assemblages forming in the early stages of serpentinization to millerite-pyrite-polydymite-dominated assemblages in steatized rocks. Awaruite is observed in all brucite-bearing partly serpentinized rocks. Apparently, buffering of silica activities to low values by the presence of brucite facilitates the formation of large amounts of hydrogen, which leads to the formation of awaruite. Associated with the prominent desulfurization of pentlandite, sulfide is removed from the rock during the initial stage of serpentinization. In contrast, steatitization indicates increased silica activities and that highsulfur-fugacity sulfides, such as polydymite and pyrite-vaesite solid solution, form as the reducing capacity of the peridotite is exhausted and H2 activities drop. Under these conditions, sulfides will not desulfurize but precipitate and the sulfur content of the rock increases. The co-evolution of fO2,g-fS2,g in the system follows an isopotential of H2S,aq, indicating that H2S in vent fluids is buffered. In contrast, H2 in vent fluids is not buffered by Fe-Ni-Co-O-S phases, which merely monitor the evolution of H2 activities in the fluids in the course of progressive rock alteration.The co-occurrence of pentlandite- awaruite-magnetite indicates H2,aq activities in the interacting fluids near the stability limit of water. The presence of a hydrogen gas phase would add to the catalyzing capacity of awaruite and would facilitate the abiotic formation of organic compounds.

Geochemistry of altered phases, basalts and sediments of ODP Site 136-843

40Ar-39Ar incremental heating experiments on a relatively unaltered basalt from Site 843 yield a crystallization age of 110 ± 2 Ma for the central Pacific Ocean igneous basement near Hawaii. Previous estimates of the age of the basement inferred by indirect methods and from radiometric dates of the South Hawaiian Seamounts are too young by 20-30 m.y. Phyllosilicate alteration minerals from veins in the Site 843 basalts define a Rb/Sr isochron with an age of 94.5 ± 0.5 Ma. The isochron records the last equilibration of the phyllosilicate minerals with a hydrothermal fluid at about 16 m.y. after the formation of the igneous basement. The last event recorded by calcite veins is the sealing of the crust by a sufficient thickness of sediment to impede the free circulation of seawater into the crust. The chemistry of the alteration minerals indicates the rare earth elements in the hydrothermal solutions were derived from alteration of the basalts and, furthermore, were transported in solution as metal species and carbonate complexes. Calcite with approximately seawater 87Sr/86Sr, but Sr contents too low to precipitate directly from seawater, is suggested to have formed at a late stage in the alteration history of the crust by the reaction of seawater with calcite precipitated earlier from basalt-dominated hydrothermal fluids.