Porewater and particulate geochemistry during Maria S. Merian cruise MSM17/4

We present sedimentary geochemical data and in situ benthic flux measurements of dissolved inorganic nitrogen (DIN: NO3-, NO2-, NH4+) and oxygen (O2) from 7 sites with variable sand content along 18°N offshore Mauritania (NW Africa). Bottom water O2 concentrations at the shallowest station were hypoxic (42 µM) and increased to 125 µM at the deepest site (1113 m). Total oxygen uptake rates were highest on the shelf (-10.3 mmol O2 /m2 d) and decreased quasi-exponentially with water depth to -3.2 mmol O2 /m2 d. Average denitrification rates estimated from a flux balance decreased with water depth from 2.2 to 0.2 mmol N /m2 d. Overall, the sediments acted as net sink for DIN. Observed increases in delta 15NNO3 and delta 18ONO3 in the benthic chamber deployed on the shelf, characterized by muddy sand, were used to calculate apparent benthic nitrate fractionation factors of 8.0 pro mille (15epsilon app) and 14.1 pro mille (18epsilon app). Measurements of delta 15NNO2 further demonstrated that the sediments acted as a source of 15N depleted NO2-. These observations were analyzed using an isotope box model that considered denitrification and nitrification of NH4+ and NO2-. The principal findings were that (i) net benthic 14N/15N fractionation (epsilon DEN) was 12.9 ± 1.7pro mille, (ii) inverse fractionation during nitrite oxidation leads to an efflux of isotopically light NO2- (-22 ± 1.9 pro mille), and (iii) direct coupling between nitrification and denitrification in the sediment is negligible. Previously reported epsilon DEN for fine-grained sediments are much lower (4-8 pro mille). We speculate that high benthic nitrate fractionation is driven by a combination of enhanced porewater-seawater exchange in permeable sediments and the hypoxic, high productivity environment. Although not without uncertainties, the results presented could have important implications for understanding the current state of the marine N cycle.

Geochemistry, minerals, color, rare earth elements and d18O at DSDP Hole 92-504B

Investigations of borehole waters sampled in Hole 504B during Leg 92 revealed changes in major-ion composition similar to changes observed previously (during Leg 83). The uniformity of chloride concentrations with increasing depth suggests efficient downhole mixing processes along density gradients caused by large temperature gradients. Chemical and mineralogical studies of suspended drilling mud (bentonite) suggest that this material has undergone substantial alteration and that CaSO4 (anhydrite/gypsum) has precipitated in the deeper parts of the hole. Rare earth element studies suggest contributions of both the bentonites and the basalts to the REE distributions. Studies of the isotopic composition (87Sr/86Sr) of dissolved strontium indicate a strong contribution of basaltic nonradiogenic strontium, although differences between the Leg 83 and Leg 92 data indicate an influence of bentonite during Leg 92. The oxygen isotope composition of the water does not change appreciably downhole. This uniformity can be understood in terms of high water-rock ratios and suggests that the chemical changes observed are due either to alteration processes involving bentonites and basaltic material from the walls of the hole or to exchange with formation fluids from the surrounding basement, which may have altered in composition at relatively high water-rock ratios.

Interstitial water chemistry at DSDP Leg 79 Holes

Interstitial water analyses of samples collected at Sites 544-547 of DSDP Leg 79 are presented. In Site 547 chloride concentrations increase to almost 80% of the halite saturation values. Gypsum occurrences in the sediments immediately overlying the halite deposit can be explained in terms of migration of Ca**2+ and SO2**2- from the underlying evaporites. At shallower depths sulfate concentrations decrease rapidly as a result of sulfate reduction processes. The same processes lead to the removal of calcium in the form of calcium carbonate. At Site 547, the chloride concentration depth profile suggests a maximum of dissolved chloride which may be the result of advective flow from nearby (abput 6 km) evaporite salt diapirs.

Conversion of ammonium alum to alumina /

"U.S. AEC Contract AT(49-1)-545."

Influence of lattice interactions on the jahn-teller distortion of the [Cu(H2O)(6)](2+) ion: Dependence of the crystal structure of K-2[Cu(H2O)(6)](SO4)(2x)(SeO4)(2-2x) upon the sulfate/selenate ratio

The temperature dependence of the structure of the mixed-anion Tutton salt K-2[Cu(H2O)(6)](SO4)(2x)(SeO4)(2-2x) has been determined for crystals with 0, 17, 25, 68, 78, and 100% sulfate over the temperature range of 85-320 K. In every case, the [Cu(H2O)(6)](2+) ion adopts a tetragonally elongated coordination geometry with an orthorhombic distortion. However, for the compounds with 0, 17, and 25% sulfate, the long and intermediate bonds occur on a different pair of water molecules from those with 68, 78, and 100% sulfate. A thermal equilibrium between the two forms is observed for each crystal, with this developing more readily as the proportions of the two counterions become more similar. Attempts to prepare a crystal with approximately equal amounts of sulfate and selenate were unsuccessful. The temperature dependence of the bond lengths has been analyzed using a model in which the Jahn-Teller potential surface of the [Cu(H2O)(6)](2+) ion is perturbed by a lattice-strain interaction. The magnitude and sign of the orthorhombic component of this strain interaction depends on the proportion of sulfate to selenate. Significant deviations from Boltzmann statistics are observed for those crystals exhibiting a large temperature dependence of the average bond lengths, and this may be explained by cooperative interactions between neighboring complexes.

Geochemical parameters of sediments and waters in areas of ocean barrier zones

Geochemical barrier zones play an important role in determining various physical systems and characteristics of oceans, e.g. hydrodynamics, salinity, temperature and light. In the book each of more than 30 barrier zones are illustrated and defined by physical, chemical and biological parameters. Among the topics discussed are processes of inflow, transformation and precipitation of the sedimentary layer of the open oceans and more restricted areas such as the Baltic, Black and Mediterranean Seas.