ALBERT

Description: The distribution of Li isotopes in pore waters to a depth of 1157 m below seafloor is presented for ODP Sites 918 and 919 in the Irminger Basin, offshore Greenland. Lithium isotope data are accompanied by strontium isotope ratios to decipher diagenetic reactions in the sediments which are characterized by the pervasive presence of volcanic material, as well as by very high accumulation rates in the upper section. The lowering of the 87Sr/86Sr ratio below contemporaneous seawater values indicates several zones of volcanic material alteration. The Li isotope profiles are complex suggesting a variety of exchange reactions with the solid phases. These include cation exchange with NH4+ and mobilization from sediments at depth, in addition to the alteration of volcanic matter. Lithium isotopes are, therefore, a sensitive indicator of sediment-water interaction. d6Li values of pore waters at these two sites vary between -42 and -25‰. At shallow depths (〈100 mbsf), rapid decreases in the Li concentration, accompanied by a shift to heavier isotopic compositions, indicate uptake of Li into alteration products. A positive anomaly of d6Li observed at both sites is coincident with the NH4+ maximum produced by organic matter decomposition and may be related to ion exchange of Li from the sediments by NH4+. In the lower sediment column at Site 918, dissolved Li increases with depth and is characterized by enrichment of 6Li. The Li isotopic compositions of both the waters and the solid phase suggest that the enrichment of Li in deep interstitial waters is a result of release from pelagic sediments. The significance of sediment diagenesis and adsorption as sinks of oceanic Li is evaluated. The maximum diffusive flux into the sediment due to volcanic matter alteration can be no more than 5% of the combined inputs from rivers and submarine hydrothermal solutions. Adsorption on to sediments can only account for 5-10% of the total inputs from rivers and submarine hot springs.

Description: A comprehensive experimental study, utilizing a rocking autoclave hydrothermal apparatus with isotope tracers, was applied to evaluate the temperature of squeezing artifacts on B contents and isotopic compositions in pore waters. The partition coefficient (KD) was determined at temperatures from 25 ° to 350 °C, at 800 bars, and this information was applied to reconstruct pore water B and d11B in ODP drill sites, where pH, T, and porosity are known. The partition coefficient of B is a function of temperature, pH, and sediment mineralogy. The solution pH exerts a dominant control at low temperatures; however, KD decreases to a value of essentially zero (compared to that of KD = ~3.5 at 25 °C) at high temperatures indicating no adsorption. Two empirical equations were derived to represent most of the available experimental results. For pelagic clay rich sediments, a KD = -3.84-0.020T + 0.88pH (R = 0.84; 1sigma = 0.25) is established. For sediments that have experienced progressive metamorphism, a KD = -1.38-0.008T + 0.59pH (R = 0.81; 1sigma = 0.37) can be applied. Similarly the effect on pore water d11B can be corrected if the fractionation factors at different temperatures are assumed. The corrected B and d11B in ODP Sites 671, 672, and 808 indicate significant mobilization of bulk B in sediment (exchangeable + lattice bound) at depth, especially near the décollement zone or other potential flow conduits. Tectonically expelled fluids from mud diapirs of Barbados Ridge Complex, hot springs of Rumsey Hills, California, and mud pot waters of the Salton Sea geothermal field, are enriched in B (up to 20 mM) with lower d11B, supporting the argument of B mobilization as a result of fluid expulsion in accretionary prisms.

Description: Circulation of seawater through basaltic basement for several million years after crustal emplacement has been inferred from studies of surface heat flow, and may play a significant role in the exchange of elements between the oceanic crust and seawater. Without direct observation of the fluid chemistry, interpretations regarding the extent and timing of this exchange must be based on the integrated signal of alteration found in sampled basalts. Much interest has thus been expressed in obtaining and analyzing fluids directly from basaltic formations. It has been proposed that open oceanic boreholes can be used as oceanic groundwater wells to obtain fluids that are circulating within the formation. Water samples were collected from the open borehole in Hole 504B prior to drilling operations on Leg 137, with the original intention of collecting formation fluids from the surrounding basaltic rocks. Past results have yielded ambiguous conclusions as to the origin of the fluids recovered-specifically, whether or not the fluids were true formation fluids or merely the result of reaction of seawater in the borehole environment. The chemistry of eight borehole fluid samples collected during Leg 137 is discussed in this paper. Large changes in major, minor, and isotopic compositions relative to unaltered seawater were observed in the borehole fluids. Compositional changes increased with depth in the borehole. The samples exhibit the effect of simple mixing of seawater, throughout the borehole, with a single reacted fluid component. Analysis and interpretation of the results from Leg 137 in light of past results suggest that the chemical signals observed may originate predominantly from reaction with basaltic rubble residing at the bottom of the hole during the interim between drilling legs. Although this endeavor apparently did not recover formation waters, information on the nature of reaction between seawater and basalt at the prevalent temperatures in Hole 504B (〉160°C) has been gained that can be related to reconstruction of the alteration history of the oceanic crust. Isotopic analyses allow calculation of element-specific water/rock mass ratios (Li and Sr) and are related to the extent of chemical exchange between the borehole fluids and basalt.