Description: The weathering of silicate minerals exposed on the continents is the largest sink of atmospheric CO2 on time scales of millions of years. The rate of this process is positively correlated with global mean temperature and atmospheric CO2 concentration, resulting in a negative feedback that stabilizes Earths’ climate (Berner, 2004). Detrital silicates derived from the physical denudation of the continents are a major component of marine sediments (Li and Schoonmaker, 2003). However, their geochemical behaviour is poorly understood and they are considered to be unimportant to the long-term carbon cycle. We show that in organic matter-rich sediments of the Sea of Okhotsk detrital silicates undergo intense weathering. This process is likely favoured by microbial activity, which lowers pore water pH and releases dissolved humic substances, and by the freshness of detrital silicates which originate from the cold, poorly weathered Amur River basin. Numerical simulations of early diagenesis show that submarine weathering rates in our study area are comparable to average continental weathering rates (Gaillardet et al., 1999). Furthermore, silicate weathering seems to be widespread in organic matter-rich sediments of continental margins, suggesting the existence of a significant CO2 sink there. These findings imply a greater efficiency of the silicate weathering engine also at low surface temperatures, resulting in a weakening of the negative feedback between pCO2, climate evolution and silicate weathering.

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: Pore fluids from the Green Canyon Block in the northern Gulf of Mexico show distinct differences with respect to element concentrations and oxygen, hydrogen, and strontium isotope signatures. The shallowest of the three investigated sites (GC185 or Bush Hill at 540 m water depth) is interpreted as a seafloor piercing mud mound and the two deeper areas (GC415 East and West at 950 and 1050 m water depth) as gas vent and oil seep sites. All three locations accommodate near-surface gas hydrates and the sediment surface is populated with chemosynthetic communities. They are characterized by a distinct increase in salinity with depth. However, the origin of this increasing salinity is different for the GC415 sites and Bush Hill and the depth source of the fluids is considerably different for all sites. The more saline fluids of the GC415 sites result from the dissolution of halite by formation water from two different sources. The fluids of GC415 East have most likely a deeper origin (early Cenozoic or even Mesozoic) and experienced elevated temperatures leading to mineral/water reactions including mineral transformations (e.g. smectite to illite transformation) and dissolution (e.g. feldspar dissolution). This process is expressed by the heavier oxygen isotope values and distinct Li, Sr, and Ca enrichments. The fluids of GC415 West have a shallower origin which is expressed by a smaller enrichment in Li, Sr, and Ca and lighter oxygen isotopes. The fluids from Bush Hill are less saline and its fluid signature indicates intensive water/mineral interaction. Oxygen and hydrogen isotope values as well as Na/Cl and Br/Cl molar ratios suggest that the salt enrichment was caused by phase separation under sub-critical conditions. A simple heat flow model simulation suggests that sub-critical phase separation may have occurred at a depth of ∼ 1650 m at ∼ 350 °C.

Description: Porewater data from vent sites of the northeastern shelf off Sakhalin Island, Sea of Okhotsk, exhibit bottom-water concentrations down to a sediment depth of up to 300 cm. Below this depth, solute concentrations rapidly change due to methanogenesis and anaerobic methane oxidation (AMO). The profile shapes suggest an irrigation-like process that mixes on a meter scale. At these sites active gas emanation into the overlying water column and near-surface gas hydrates are commonly observed. We propose that methane gas bubbles rise through the soft surface sediments and cause mixing of the porewater. Mathematically, the bubble-induced irrigation can be described by eddy diffusion enhancing the diffusive transport of solutes by several orders of magnitude. A 3-D numerical transport-reaction model was developed to investigate the parameters defining the mixing process, such as bubble rise velocity, tube size, tube distribution in the sediment, and ebullition frequency. Model consistency with the field data requires eddy diffusivities ⩾1 × 105 cm2/a, tube densities of 〉4 tubes/m2 (equivalent to a tube spacing of 〈40 cm), active gas seepage for more than a few weeks or months, and moderate to low diagenetic reaction rates of solutes. The corresponding methane gas fluxes that are predicted from the results of the model realizations range from 1 × 103–5 × 105 L/(m2 a). Due to bubble mixing, solute fluxes in these sediments are increased by a factor of 3 and the maximum AMO rate by a factor of 7.

Description: Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct–Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C1 through C5) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg− 1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH4. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH4 concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.