(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.

Age determinations of bottom sediments from the Sea of Okhotsk by different methods

On the base of data on benthic foraminifera and sediment biogeochemistry (contents of total organic carbon, calcium carbonate and biogenic opal) in two cores (1265 and 1312 m water depth) from the southeastern Sakhalin slope and one core (839 m water depth) from the southwestern Kamchatka slope variations of the oxygen minimum zone during the last 50 ka in the Okhotsk Sea are reconstructed. The oxygen minimum zone was less pronounced during cooling in the MIS 2 that is suggested to be caused by maximal expansion of the sea ice cover, decrease of marine productivity and increase of production of oxygenated Okhotsk Sea Intermediate Water (OSIW). Two-step-like strengthening of oxygen minimum zone during warmings in the Terminations 1a and 1b was combined with (1) enhanced oxygen consumption due to decomposition of large amount of organic matter in the water column and bottom sediments due to increased marine productivity and supply of terrigenous material from submerged northern shelves; (2) sea ice cover retreat and reduction of OSIW production; (3) freely inflow of the oxygen-depleted intermediate water mass from the North Pacific.