Geochemistry of pore water and sediments offshore Nicaragua and Costa Rica

Four volcanic ash-bearing marine sediment cores and one ash-free reference core were examined during research cruise RV Meteor 54/2 offshore Nicaragua and Costa Rica to investigate the chemical composition of pore waters related to volcanic ash alteration. Sediments were composed of terrigenous matter derived from the adjacent continent and contained several distinct ash layers. Biogenic opal and carbonate were only minor components. The terrigenous fraction was mainly composed of smectite and other clay minerals while the pore water composition was strongly affected by the anaerobic degradation of particulate organic matter via microbial sulphate reduction. The alteration of volcanic matter showed only a minor effect on major element concentrations in pore waters. This is in contrast to prior studies based on long sediment cores taken during the DSDP, where deep sediments always showed distinct signs of volcanic ash alteration. The missing signal of ash alteration is probably caused by low reaction rates and the high background concentration of major dissolved ions in the seawater-derived pore fluids. Dissolved silica concentrations were, however, significantly enriched in ash-bearing cores and showed no relation to the low but variable contents of biogenic opal. Hence, the data suggest that silica concentrations were enhanced by ash dissolution. Thus, the dissolved silica profile measured in one of the sediment cores was used to derive the in-situ dissolution rate of volcanic glass particles in marine sediments. A non-steady state model was run over a period of 43 kyr applying a constant pH of 7.30 and a dissolved Al concentration of 0.05 ?M. The kinetic constant (AA) was varied systematically to fit the model to the measured dissolved silica-depth profile. The best fit to the data was obtained applying AA = 1.3 * 10**-U9 mol of Si/cm**2/ s. This in-situ rate of ash dissolution at the seafloor is three orders of magnitude smaller than the rate of ash dissolution determined in previous laboratory experiments. Our results therefore imply that field investigations are necessary to accurately predict natural dissolution rates of volcanic glasses in marine sediments.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.