Description: At the South Chamorro Seamount in the Mariana subduction zone, geochemical data of pore fluids recovered from Ocean Drilling Program Leg 195 Site 1200 indicate that these fluids evolved from dehydration of the underthrusting Pacific plate and upwelling of fluids to the surface through serpentinite mud volcanoes as cold springs at their summits. Physical conditions of the fluid source at 27 km were inferred to be at 100°-250°C and 0.8 GPa. The upwelling of fluid is more active near the spring in Holes 1200E and 1200A and becomes less so with increasing distance toward Hole 1200D. These pore fluids are depleted in Cl and Br, enriched in F (except in Hole 1200D) and B (up to 3500 µM), have low 11B (16-21), and have lower than seawater Br/Cl ratios. The mixing ratios between seawater and pore fluids is calculated to be ~2:1 at shallow depth. The F, Cl, and Br concentrations, together with B concentrations and B isotope ratios in the serpentinized igneous rocks and serpentine muds that include ultramafic clasts from Holes 1200A, 1200B, 1200D, 1200E, and 1200F, support the conclusion that the fluids involved in serpentinization originated from great depths; the dehydration of sediments and altered basalt at the top of the subducting Pacific plate released Cl, H2O, and B with enriched 10B. Calculation from B concentrations and upwelling rates indicate that B is efficiently recycled through this nonaccretionary subduction zone, as through others, and may contribute the critical missing B of the oceanic cycle.

Description: Chlorine stable isotopes (delta37Cl) and halogen concentrations (e.g. Br/Cl) in 168 pore Fluids and 23 serpentines and other solids from three subduction zones, the Nankai Trough, Costa Rica, and Mariana Forearc, provide critical information on fluid sources, flow paths, and reaction conditions. The delta37Cl values of pore fluids at the Nankai and Costa Rica subduction zones, are significantly more negative (minimum -7.8‰, 2 sigma +/- 0.3‰) than seawater value (0‰). At Nankai Trough, the minimum delta37Cl value is situated below the décollement and evolves laterally from -7.8‰ at the most arcward ODP Site 808, to -7.1‰ at Site 1174, not, vert, similar 2 km seaward from Site 808, and to -5.8‰ at the reference Site 1173. At Costa Rica, along the décollement the minimum delta37Cl value evolves from -5.5‰ at the most arcward ODP Site 1040/1254, to -3.2‰ at Site 1043/1255, ~1 km seaward, and to 0‰ at the reference Site 1039/1253. At both subduction zones, the Br/Cl ratios are higher than the seawater value (1.5 * 10**-3) and also show seaward evolutions. These pore fluids originate from greater depth arcward, at 〉= 250 °C, from hydrous mineral formation that preferentially incorporates 37Cl and excludes Br. In contrast, the delta37Cl values in the pore fluids at the Mariana serpentine mud volcanoes are higher than the seawater value (+ 0.3‰ to + 1.8‰); and the Br/Cl ratios are lower. These pore fluid values and the high Cl concentrations with positive delta37Cl values (+ 1.2 to + 6.0‰) in the serpentines, support that the upwelling pore fluid originates from dehydration of the subducting slab that releases water enriched in 37Cl, into the fluid phase. The constancy of the ocean delta37Cl over the past 200 Ma suggests that the isotopically fractionated chlorine in serpentinites and the Cl exchanged in subduction zones are efficiently recycled back into seawater. If the efficiency is 〈 100%, the residual would be transferred to the mantle, with a maximum Cl flux between 2 to 3 * 10**17 moles/Ma that would lead to an isotopic difference between the mantle and seawater over the age of the earth on the order of a few per mil.

Description: A method for quantifying in situ dissolved methane concentrations in sediment cores that have gas voids is described. The method relies on normalizing methane (CH4) in the gas voids to nitrogen (N2) and/or argon (Ar). The principles of the method are presented. The method was tested during Ocean Drilling Program Leg 201, and preliminary results indicate that it can be used to generate reproducible and accurate dissolved methane values if argon and nitrogen are both measured or if one is measured along with pressure of the gas void.

Description: This study addresses the problem of diagenetic fractionation of d15N in sedimentary organic matter by constructing isotopic mass balances for the sedimentary nitrogen and pore water ammonium at two Ocean Drilling Program (ODP) sites, 1227 and 1230. At Site 1230, ammonium production flux integrated through the sedimentary column indicates that 〉60% of organic matter is lost to decomposition. The d15N of pore water ammonium is 〈0.7 per mil different from that of the sedimentary organic matter, which implies that very little isotopic fractionation is associated with degradation of organic matter at this site. The constant d15N of the solid-phase sedimentary nitrogen through the whole profile supports this conclusion. Atomic C/N ratios (9-12) indicate that organic matter at this site is primarily of marine origin. At Site 1227, the sedimentary organic matter appears to be a mixture of terrestrial and marine components. Ammonium is ~4 heavier than the organic matter. The observed isotopic enrichment of pore water ammonium relative to the sedimentary nitrogen might indicate either the preferential decomposition of isotopically heavier marine fraction of the organic matter, or possibly, a nonsteady-state condition of the ammonium concentration and d15N profiles. Interpretation of the results at Site 1227 is further complicated by the contribution of ammonium with d15N of ~4 per mil that is diffusing upward from Miocene brines.