167 resultados para combinatorial chemistry


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The geochemical implications of thermally driven flow of seawater through oceanic crust on the mid-ocean ridge flank have been examined on a well-studied 80 km transect across the eastern flank of the Juan de Fuca Ridge at 48°N, using porewater and basement fluid samples obtained on ODP Leg 168. Fluid flow is recognised by near-basement reversals in porewater concentration gradients from altered values in the sediment section to seawater-like values in basaltic basement. In general, the basement fluids become more geochemically evolved with distance from the ridge and broadly follow basement temperature which ranges from not, vert, similar16° to 63°C. Although thermal effects of advective heat exchange are only seen within 20 km east of where basement is exposed near the ridge crest, chemical reactivity extends to all sites. Seawater passing through oceanic crust has reacted with basement rocks leading to increases in Ca2+ and decreases in alkalinity, Mg2+, Na+, K+, SO42- and delta18O. Sr isotope exchange between seawater and oceanic crust off axis is unequivocally demonstrated with endmember 87Sr/86Sr ~ 0.707. Evidence of more evolved fluids is seen at sites where rapid upwelling of fluids through sediments occurs. Chlorinities of the basement fluids are consistent with post-glacial seawater and thus a short residence time in the crust. Rates of lateral flow have been by estimated by modelling porewater sulphate gradients, using Cl as a glacial chronometer, and from radiocarbon dating of basal fluids. All three methods reveal fluid flow with 14C ages less than 10,000 yr and particle velocities of ~1-5 m/yr, in agreement with thermally constrained volumetric flow rates through a ~600 m thick permeable layer of ~10% porosity. Delta(element)/Delta(heat) extraction ratios are similar to values for ridge-crest hydrothermal systems.

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Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z > 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.