Description: 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.

Description: Calcites from the basaltic basement at Deep Sea Drilling Project Site 597, containing 3.4 to 4.4 mol % MgCO3, were analyzed for d13C, d18O, 87Sr/86Sr, K, Rb, and Sr concentrations. The d13C values range from 1.9 to 2.4 per mil (relative to PDB) and are typical for calcites from the extrusive layer of the oceanic crust. The d18O values of calcites are very uniform and unusually high (2.33 to 2.77 per mil, PDB), which suggest temperatures of formation of 1.5 to 2.9°C and 0.03 to 1.7°C using the calibrations of O'Neil et al. (1969) and Epstein et al. (1953), respectively (after correction for MgCO3), and assuming - l per mil for the late Oligocene/early Miocene bottom water. Paleogene bottom waters are thought to have been warmer than those of present day, and hence the calibration of Epstein et al. (1953) yields more reasonable temperatures for late Oligocene/early Miocene bottom waters. K and Rb concentrations are very low, which is consistent with their incompatible character. Sr/Ca ratios of calcites from sub-basement depths less than 35 m are typical for calcites precipitated from pure seawater, whereas the lowermost sample, from a sub-basement depth of 78 m, appears to contain substantial amounts of basaltic Ca. The 87Sr/86Sr ratios of seawater calcites range from 0.708192 to 0.708349, suggesting that they precipitated from 20 to 28 Ma seawater, or within 8 m.y. after formation of the oceanic crust at Site 597. Our data for calcites from Site 597, drilled on fast-spreading oceanic crust, are similar to data for carbonates from slowspreading crust, except that the high d18O values of the former suggest low temperatures of formation. The low temperatures of calcite formation apparently indicate that the oceanic crust at Site 597 was unusually permeable, allowing rapid circulation of seawater.

Description: Deep Sea Drilling Hole 245 (31°32'S, 52°18'E) in the southwest Indian Ocean shows pronounced linear concentration-depth gradients in interstitial dissolved Ca, Mg and Sr. Electrical conductivity tests enable us to make the estimate of a constant diffusion coefficient with depth of about 0.000002 cm**2/sec. The shapes of the concentration-depth gradients suggest that the major reaction sites in this hole are situated in the basal sediments and/or underlying basalts. It is proposed that observed interstitial water concentration changes in Ca and Mg are related to alteration of basaltic material, whereas those in Sr are due to calcium carbonate recrystallization processes. Support for the basaltic material alteration hypothesis comes from petrochemical and mineralogical data. Geochemical data also indicate that the high contents in Fe and Mn of the basal sediments can be related to low temperature alteration of basaltic glass and not necessarily to 'hydrothermal' activity.

Description: Discrepancies between predicted and observed interstitial water profiles for sites 322 and 323, Leg 35, Bellingshausen Abyssal Plain, were used to identify sites of reaction for further mineralogical and chemical investigations. Two major reaction sites were identified at site 323: (1) In the silicification zone between 410 and 505 m depth, where dissolution of biogenic (opaline) silica, plagioclase and a few coccoliths and the formation of opal-CT, Mg-rich smectite and K-feldspar are responsible for the observed silica, Ca[2+], Mg[2+], and K[+] interstitial water gradients. Dissolution of biogenic silica provided most of the silica for the porcelanites. (2) In the basalt, weathering of pyroxene and plagioclase and the formation of celadonite, smectite, calcite, and goethite are probably responsible for the observed Ca[2+], Mg[2+], and K[+] interstitial water gradients below the silicification zone. The chemistry of authigenic smectites reflects the composition of their precursor(s).

Description: Particles of red brown to yellow brown semiopaque oxides (RSO) dominate the insoluble residue fraction of the sediments at Site 597. Unlike the X-ray amorphous particles in the Bauer Deep sediments, these particles are composed of mainly goethite; the amount of X-ray amorphous ferric hydroxide and poorly crystalline ferromanganese oxyhydroxides is generally small relative to the amount of goethite. A qualitative goethite crystallinity index was established. The variations observed in the crystallinity of goethite with increasing depth and changes in lithology suggest that aging and long-term exposure to seawater in a high water/sediment regime influence and increase the rate of recrystallization of the Fe-oxyhydroxides of the RSO particles. The percentage of organic carbon is low in these sediments; it varies primarily between 0.2 and 0.4 wt.%. Phillipsite is present throughout the sediment column and is more concentrated in the youngest clay layer and in the oldest basal sediments.