Beschreibung: In situ measurement of fluid flow rates from active margins is an important parameter in evaluating dissolved mass fluxes and global geochemical balances as well as tectonic dewatering during developments of accretionary prisms. We have constructed and deployed various devices that allow for the direct measurement of this parameter. An open bottom barrel with an exhaust port at the top and equipped with a mechanical flowmeter was initially used to measure flow rates in the Cascadia accretionary margin during an Alvin dive program in 1988. Sequentially activated water bottles inside the barrel sampled the increase of venting methane in the enclosed body of water. Subsequently, a thermistor flowmeter was developed to measure flow velocities from cold seeps. It can be used to measure velocities between 0.01 and 50 cm s−1, with a response time of 200 ms. It was deployed again by the submersible Alvin in visits to the Cascadia margin seeps (1990) and in conjunction with sequentially activated water bottles inside the barrel. We report the values for the flow rates based on the thermistor flowmeter and estimated from methane flux calculations. These results are then compared with the first measurement at Cascadia margin employing the mechanical flowmeter. The similarity between water flow and methane expulsion rates over more than one order of magnitude at these sites suggests that the mass fluxes obtained by our in situ devices may be reasonably realistic values for accretionary margins. These values also indicate an enormous variability in the rates of fluid expulsion within the same accretionary prism. Finally, during a cruise to the active margin off Peru, another version of the same instrument was deployed via a TV-controlled frame within an acoustic transponder net from a surface ship, the R.V. Sonne. The venting rates obtained with the thermistor flowmeter used in this configuration yielded a value of 4411 m−2 day−1 at an active seep on the Peru slope. The ability for deployment of deep-sea instruments capable of measuring fluid flow rates and dissolved mass fluxes from conventional research vessels will allow easier access to these seep sites and a more widespread collection of the data needed to evaluate geochemical processes resulting from venting at cold seeps on a global basis. Comparison of the in situ flow rates from steady-state compactive dewatering models differ by more than 4 orders of magnitude. This implies that only a small area of the margin is venting and that there must be recharge zones associated with venting at convergent margins

Beschreibung: A widely used degassing method for methane in seawater employing vacuum was tested and subsequently improved. It yielded 62 ± 3.8% of the total dissolved methane, hence a reproducible correction factor was established. The method was then applied to measure CH4 in the sea-air boundary layer and simultaneously in the overlying air along two transects in the eastern Equatorial Pacific off Peru in March of 1992. The results showed surprising small-scale reversals of the methane exchange between ocean and atmosphere in this region. Generally the ocean acted as a source of methane but also methane uptake by the ocean was found. This was mainly a consequence of high CH4 concentrations in the air which deviated considerably from the long-term and large-scale average. If applied to the flux rate calculations, the observed variabilities indicate that both rate and direction of the methane flux through the air-sea interface vary considerably depending on the atmospheric CH4 content. The implications are that even ocean areas with high concentrations of dissolved CH4 can be considerably weaker sources than would be expected on the basis of 1.7 ppmv mean atmospheric methane content. Based on improved simultaneous analyses of both air and water samples, the ocean-atmosphere flux of methane would therefore be more dynamic than previously thought.

Beschreibung: The observed distribution of dissolved magnesium in the pore water of rapidly accumulating sediments shows significant deviations from the seawater value. We have shown that deviations during early diagenesis can be explained by reactions occurring at the surface of sediment particles. In anoxic pore water environments with high levels of dissolved total carbon dioxide the formation of Mg+2·CO3−2 complexes significantly reduces the concentration of the free Mg+2 ion. This decrease in the Mg+2 activity results in desorption of magnesium from the solid surfaces due to the re-equilibration of the adsorbed Mg+2 with the dissolved species. The effect of increasing carbonate complexation of Mg+2 in anoxic environments is initially compensated by the loss of sulfate, which is also a strong Mg+2 ligand. Therefore, significant changes in free Mg+2 concentration and thus in the magnesium desorption from solid surfaces by ligand competition for Mg+2 are more pronounced in sulfate-depleted systems undergoing methanogenesis. Such conditions are characteristic of most continental margin sediments. Another consequence of the decomposition of organic matter in hemipelagic sediments is the accumulation of high levels of ammonium ions which also displace Mg+2 from sediment-particle surfaces by ion exchange. These equilibria in the pore water-sediment systems can be described by empirical parameters, which were experimentally obtained. A computer model was used to determine the equilibrium conditions for solid-solution reactions as a function of changes in the pore-water composition in organicrich hemipelagic environments. This model includes complex formation, competition for Mg+2 between dissolved ligands and exchange sites and Mg+2NH+4 exchange reactions. The relative proportion of desorbed and displaced Mg+2 from the solid surface depends on the characteristics of the sediment and on the ΣCO2:NH+4 regenerative ratio in the pore waters. In sediments from Bransfield Strait, the Gulf of California, and the Peru margin, both release mechanisms for Mg+2—ligand competition and ion exchange with ammonium—were evaluated as part of the complex reaction system in order to explain the observed maxima in the dissolved magnesium profiles. Overlying the Mg+2 maxima, the Bransfield Strait and Gulf of California pore waters show minima in the dissolved magnesium concentration, concurrent with a measured increase in the cation exchange capacity (CEC) of the sediments. By including the observed CEC changes in the multi-component model we show that the negative anomaly in the dissolved Mg+2 profiles is a consequence of changes in the CEC of sediments during the very early stages of anoxic diagenesis.

Beschreibung: Thermogenic hydrocarbons, formed by the thermal alteration of organic matter, are encountered in several piston core stations in the King George Basin, Anatarctica. These hemipelagic sediments are being deposited in an area of active hydrothermalism, associated with the back-arc spreading in the Bransfield Strait. The lateral extent of sediments infiltrated by the hydrothermally influenced interstitial fluids is characterized by basalt diapirix intrusions and is delineated by an acoustically turbid zone in the sediments of the eastern part of the basin. Iron-sulphide-bearing veins and fractures cut across the sediment in several cores; they appear to be conduits for flow of hydrothermally altered fluids. These zones have the highest C2+ and ethene contents. The thermogenic hydrocarbons have molecular C1/(C2 + C3) ratios typically 〈 50 and δ13CH4 values between −38% and −48%, indicating an organic source which has undergone strong thermal stress. Several sediment cores also have mixed gas signatures, which indicate the presence of substantial amounts of bacterial gas, predominantly methane. Hydrocarbon generation in the King George Basin is thought to be a local phenomenon, resulting from submarine volcanism with temperatures in the range 70–150°C. There are no apparent seepages of hydrocarbons into the water column, and it is not believed that significant accumulation of thermogenic hydrocarbons reside in the basin.