Description: The contribution of organic matter (humic compounds) to the alkaline reserve of seawater in the Sea of Japan, in the Razdol’naya River estuarine waters, and in the interstitial waters of the sediments of the Sea of Okhotsk was characterized using two procedures for alkalinity measurements: the method by Bruevich and that of the sample equilibrium with air. It was found that the surface waters of the Sea of Japan contained about 20 μmol/kg of alkalinity of organic origin, and this value twofold decreased with depth. For most of the actual cases of the calculations of the seawater carbonate system, this value may be neglected. Meanwhile, the contribution of organic alkalinity to the Razdol’naya River waters amounts to nearly 120 μmol/kg. It was shown that, if this value in the calculation of the carbonate system of the Razdol’naya River estuary-Amur Bay is neglected, this may cause gross errors in the values of the partial pressure of carbon dioxide (the error might be over 1500 μatm) and in the dissolved inorganic carbon (an error over 150 μmol/kg). The maximum absolute contribution of the humic matter (over 300 μmol/kg) was found for the interstitial waters in selected sediments of the Sea of Okhotsk. In the interstitial waters of these sediments, humic matter concentrations as high as 300 mg/l were detected. The data obtained show that the determination of the amount of humic matter must be an indispensable condition for an adequate analysis of estuarine carbonate systems and of the interstitial water in reduced marine sediments.

Description: Seven sediment cores were taken in the Sea of Okhotsk in a south-north transect along the slope of Sakhalin Island. The retrieved anoxic sediments and pore fluids were analyzed for particulate organic carbon (POC), total nitrogen, total sulfur, dissolved sulfate, sulfide, methane, ammonium, iodide, bromide, calcium, and total alkalinity. A novel method was developed to derive sedimentation rates from a steady-state nitrogen mass balance. Rates of organic matter degradation, sulfate reduction, methane turnover, and carbonate precipitation were derived from the data applying a steady-state transport-reaction model. A good fit to the data set was obtained using the following new rate law for organic matter degradation in anoxic sediments: View the MathML sourceRPOC=KCC(DIC)+C(CH4)+KC·kx·POC Turn MathJax on The rate of particulate organic carbon degradation (RPOC) was found to depend on the POC concentration, an age-dependent kinetic constant (kx) and the concentration of dissolved metabolites. Rates are inhibited at high dissolved inorganic carbon (DIC) and dissolved methane (CH4) concentrations. The best fit to the data was obtained applying an inhibition constant KC of 35 ± 5 mM. The modeling further showed that bromide and iodide are preferentially released during organic matter degradation in anoxic sediments. Carbonate precipitation is driven by the anaerobic oxidation of methane (AOM) and removes one third of the carbonate alkalinity generated via AOM. The new model of organic matter degradation was further tested and extended to simulate the accumulation of gas hydrates at Blake Ridge. A good fit to the available POC, total nitrogen, dissolved ammonium, bromide, iodide and sulfate data was obtained confirming that the new model can be used to simulate organic matter degradation and methane production over the entire hydrate stability zone (HSZ). The modeling revealed that most of the gas hydrates accumulating in Blake Ridge sediments are neither formed by organic matter degradation within the HSZ nor by dissolved methane transported to the surface by upward fluid flow but rather through the ascent of gas bubbles from deeper sediment layers. The model was further applied to predict rates of hydrate accumulation in Sakhalin slope sediments. It showed that only up to 0.3% of the pore space is occupied by gas hydrates formed via organic matter degradation within the HSZ. Gas bubble ascent may, however, significantly increase the total amount of hydrate in these deposits.

Description: Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50–150 mg dm−3) may promote the dissolution of silicate phases through complexation of Al3+ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4–99.2 mmol CO2 m−2 year−1) are lower than the marine weathering rates calculated from the solid phase data (198–245 mmol CO2 m−2 year−1) suggesting a decrease in marine weathering over time. The production of CO2 through reverse weathering in surface sediments (4.22–15.0 mmol CO2 m−2 year−1) is about one order of magnitude smaller than the weathering-induced CO2 consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO2 consumption through marine silicate weathering estimated here as 5–20 Tmol CO2 year−1 is as high as the global rate of continental silicate weathering.