Description: The chemical composition (alkalinity, pH, NH4+, PO43-, Si, H2S, Cl-, Ca2+,and SO42-) of interstitial water was studied in the sediments of the Sea of Okhotsk at sites of methane emission. Variations in alkalinity were observed in the sediments from a typical seawater value (2.3 mM/kg) to 63 mM/kg. It is demonstrated that they are caused by the processes of sulfate reduction and methane generation. Based on the balance relationships, an equationwas constructed connecting changes in alkalinity with variations of Ca2+, SO42- and NH4+ in interstitial solutions.

Description: Hydrate Ridge is part of the accretionary complex at the Cascadia margin and is an area of widespread carbonate precipitation induced by the expulsion of methane-rich fluids. All carbonates on Hydrate Ridge are related to the methanecarbon pool either through anaerobic methanotrophy or through methanogenesis. Several petrographically distinct lithologies occur in boulder fields or in massive autochtonous chemoherm complexes which include methane-associated diagenetic mudstones and venting-induced breccias. The mudstones result from methane diagenesis in different sediment horizons and geochemical environments related to very slow methane venting. Cemented bioturbation casts occur as fragments, complex framework or as clasts together with bivalve shells as part of intraformational breccias, which are restricted to chemoherm complexes. Here, fluids ascend from the sub-seafloor and support aragonite-dominated carbonate precipitation near or at the sediment surface. Voids within mudclast breccias are either aragonite-rich indicating a formation near the surface at vent sites or are cemented by dolomite, which indicates formation in deeper parts of the sediment column. Brecciation is caused by tectonic or slump processes. In addition, we recognized a direct relationship between gas hydrates and sediment fracturing as well as the oxygen isotope composition of carbonate lithologies. Such gas hydrate-associated carbonates either show layered megapores and veins as relics of the original gas hydrate fabric or consist of aragonite-cemented intraclast breccias formed by growing and decomposing gas hydrate near the sediment surface. Both rock fabrics and the enrichment of 180 in high Mg-calcite demonstrate carbonate-forming mechanisms of gas hydrate.

Description: A geochemical model of the Peru Basin deep-sea floor, based on an extensive set of field data as well as on numerical simulations, is presented. The model takes into account the vertical oscillations of the redox zonation that occur in response to both long-term (glacial/interglacial) and short-term (El Niño Southern Oscillation (ENSO) time scale) variations in the depositional flux of organic matter. Field evidence of reaction between the pore water NO3− and an oxidizable fraction of the structural Fe(II) in the clay mineral content of the deep-sea sediments is provided. The conditions of formation and destruction of reactive clay Fe(II) layers in the sea floor are defined, whereby a new paleo-redox proxy is established. Transitional NO3− profile shapes are explained by periodic contractions and expansions of the oxic zone (ocean bottom respiration) on the ENSO time scale. The near-surface oscillations of the oxic–suboxic boundary constitute a redox pump mechanism of major importance with respect to diagenetic trace metal enrichments and manganese nodule formation, which may account for the particularly high nodule growth rates in this ocean basin. These conditions are due to the similar depth ranges of both the O2 penetration in the sea floor and the bioturbated high reactivity surface layer (HRSL), all against the background of ENSO-related large variations in depositional Corg flux. Removal of the HRSL in the course of deep-sea mining would result in a massive expansion of the oxic surface layer and, thus, the shut down of the near-surface redox pump for centuries, which is demonstrated by numerical modeling.

Description: The methane concentration and pCO2 in surface waters and the overlying marine air were continuously surveyed along the pathway of the Kuroshio, from the eastern coast of Honshu to Taiwan, and then across the eastern part of the East China and South China Seas in September of 1994. Off Honshu, the CH4 content was controlled by the confluence of the relatively CH4-poor waters of the Kuroshio and the Oyashio and the CH4-rich Tsugaru Warm Current, the latter carrying water into the Pacific Ocean with a methane content more than twice the equilibrium value with the atmospheric CH4 partial pressure. Along the Kuroshio, the surface water was supersaturated in methane with respect to the atmosphere by 10–15% and appears considerably enriched relative to open Pacific surface waters at same latitudes. The northeastern part of the South China Sea, part of the deep basin of this marginal sea, showed CH4 concentrations similar to those found in open-ocean waters. In contrast, highly variable oversaturations up to 700% were observed along the northwestern coast of Borneo, most probably related to known seepage from oil and gas deposits in this area. The pCO2 of surface water was higher than the atmospheric pCO2 throughout the area surveyed. However, the ΔpCO2 of the surface waters varied from close to 0 to more than 60 μatm. The observed oversaturation in areas influenced by the Kuroshio confirm that, during a short period in late summer, the surface waters of this current between Taiwan and Japan act as a moderate source for atmospheric CO2.

Description: Organic carbon fluxes through the sediment/water interface in the high-latitude North Atlantic were calculated from oxygen microprofiles. A wire-operated in situ oxygen bottom profiler was deployed, and oxygen profiles were also measured onboard (ex situ). Diffusive oxygen fluxes, obtained by fitting exponential functions to the oxygen profiles, were translated into organic carbon fluxes and organic carbon degradation rates. The mean Corg input to the abyssal plain sediments of the Norwegian and Greenland Seas was found to be 1.9 mg C m−2 d−1. Typical values at the seasonally ice-covered East Greenland continental margin are between 1.3 and 10.9 mg C m−2 d−1 (mean 3.7 mg C m−2 d−1), whereas fluxes on the East Greenland shelf are considerably higher, 9.1–22.5 mg C m−2 d−1. On the Norwegian continental slope Corg fluxes of 3.3–13.9 mg C m−2 d−1 (mean 6.5 mg C m−2 d−1) were found. Fluxes are considerably higher here compared to stations on the East Greenland slope at similar water depths. By repeated occupation of three sites off southern Norway in 1997 the temporal variability of diffusive O2 fluxes was found to be quite low. The seasonal signal of primary and export production from the upper water column appears to be strongly damped at the seafloor. Degradation rates of 0.004–1.1 mg C cm−3 a−1 at the sediment surface were calculated from the oxygen profiles. First-order degradation constants, obtained from Corg degradation rates and sediment organic carbon content, are in the range 0.03–0.6 a−1. Thus, the corresponding mean lifetime of organic carbon lies between 1.7 and 33.2 years, which also suggests that seasonal variations in Corg flux are small. The data presented here characterize the Norwegian and Greenland Seas as oligotrophic and relatively low organic carbon deep-sea environments.

Description: Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1–2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17α(H),21β(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ∼6000 years BP up to present time to about 70 μg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (〈51 μg/g Corg) and even slightly decrease to 36 μg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ∼6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between −31.5 and −39.6‰ PDB after ∼6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic–anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate δ13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at −31.4±1.1‰ PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ∼6000 years BP, diploptene enriched in 13C of up to −26.3‰ PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.