Description: Extensive methane hydrate layers are formed in the near-surface sediments of the Cascadia margin. An undissociated section of such a layer was recovered at the base of a gravity core (i.e. at a sediment depth of 120 cm) at the southern summit of Hydrate Ridge. As a result of salt exclusion during methane hydrate formation, the associated pore waters show a highly elevated chloride concentration of 809 mM. In comparison, the average background value is 543 mM. A simple transport-reaction model was developed to reproduce the Cl- observations and quantify processes such as hydrate formation, methane demand, and fluid flow. From this first field observation of a positive Cl- anomaly, high hydrate formation rates (0.15–1.08 mol cm-2 a-1) were calculated. Our model results also suggest that the fluid flow rate at the Cascadia accretionary margin is constrained to 45–300 cm a-1. The amount of methane needed to build up enough methane hydrate to produce the observed chloride enrichment exceeds the methane solubility in pore water. Thus, most of the gas hydrate was most likely formed from ascending methane gas bubbles rather than solely from CH4 dissolved in the pore water.

Description: Stirred flow-through experiments were conducted for the first time with planktonic biogenic silica (BSi). We investigated the dissolution kinetics of uncleaned and chemically cleaned BSi collected in ocean surface water, sediment traps, and sediments from the Norwegian Sea, the Southern Ocean, and the Arabian Sea. The solubility at 2°C is rather constant (1000 to 1200 μM). The dissolution rates are, however, highly variable, declining with water depth, and phytoplankton reactivity is two to three orders of magnitude higher than pure siliceous oozes. The reactivity decrease correlates well with an increase in the integrated peak intensity ratios of Si-O-Si/Si-OH measured by Fourier transform infrared (FTIR) spectroscopy. The removal of organic or inorganic coatings enhance the reactivity by at least an order of magnitude. Atomic Al/Si ratios of 0.03 to 0.08 in sedimentary diatom frustules decrease significantly to 0.02 as a result of removal of inorganic coatings and detritals present. Near equilibrium, the dissolution rates exhibit a linear dependence on the degree of undersaturation. At higher degrees of undersaturation—that is, at low concentrations of dissolved silica—the dissolution rates of uncleaned samples define a nonlinear trend. The nonlinear kinetics imply that the dissolution of natural BSi is strongly accelerated in silica-depleted surface waters. The FTIR results suggest that internal condensation reactions reduce the amount of surface reaction sites and are partly responsible for the reactivity decrease with depth. The high content of Al in sedimentary BSi is likely caused by precipitation of dissolved silica with Al dissolved from minerals in sediment. Nonbiogenic silica as coatings or detritals are partly responsible for the solubility and reactivity decrease of BSi in sediments. One order of magnitude different rate constants measured in Norwegian Sea and Southern Ocean sediment trap material support the so-called opal paradox—that is, high BSi accumulation rates in sediments in spite of low BSi production rates in surface waters of the Southern Ocean.