A novel time-series station in the Wadden Sea (NW Germany): First results on continuous nutrient and methane measurements

In autumn 2002 a time-series station was installed in the tidal inlet between the Islands of Langeoog and Spiekeroog (Southern North Sea, NW Germany) to continuously measure physical, chemical, and meteorological parameters, even during extreme weather conditions (gale-force storms, drifting ice). Inside the pole of the station sensor tubes are installed in direction of the prevailing tidal currents. The tubes are equipped with hydrographic sensors (pressure, temperature, conductivity) and allow retrieval of water for nutrient analysis by automated instruments located inside the pole. Dissolved methane and the nutrients ammonia, nitrite, nitrate, phosphate, and silicate are measured at the station.     

The hydrogeochemistry of methane: Evidence from English groundwaters

The presence of methane (CH₄) in groundwater is usually only noticed when it rises to high concentrations; to date rather little is known about its production or natural ‘baseline’ conditions. Evidence from a range of non-polluted groundwater environments in England, including water supply aquifers, aquicludes and thermal waters, reveals that CH₄ is almost always detectable, even in aerobic conditions. Measurements of potable waters from Cretaceous, Jurassic and Triassic carbonate and sandstone aquifers reveal CH₄ concentrations of up to 500 μg/l, but a mean value of < 10 μg/l. However, aquiclude and thermal waters from the Carboniferous and Triassic typically contain in excess of 1500 μg/l. Such high concentrations have so far only been found at redox (Eh) potentials below 0 mV, but in general CH₄ concentration and Eh value are poorly correlated. This suggests a lack of thermodynamic equilibrium, which is confirmed by comparing pe values calculated from the redox couple C(4)/C(− 4) with those derived from Eh. Genesis of CH₄ appears to occur on two timescales: a rapid if low rate of production from labile carbon in anaerobic microsites in the soil, and a much longer, millennium scale of production from more refractory carbon. Methane is rarely measured in groundwater; there is no single ionic determinand which acts universally as a proxy, but a combination of high HCO₃ and low SO₄ concentrations, or the reverse, is an indication that high amounts of CH₄ may be present.     

Potential for irradiation of methane to form complex organic molecules in impact craters: Implications for Mars, Titan and Europa

The release of methane from crater sites following meteorite impact is a possible consequence of the thermal alteration of organic matter, or tapping of reservoired gas of biogenic or abiogenic origin. At least the latter is feasible on Mars. Methane and higher hydrocarbons are susceptible to polymerization and precipitation by radioactive minerals. Where such minerals are present in impact target rocks, the craters can be a preferred site for carbon concentration, and the formation of complex organic molecules. On icy bodies, such as Titan and Europa, methane released by impact could be a fuel for prebiotic chemistry involving other forms of irradiation.     

A methane fuse for the Cambrian explosion: carbon cycles and true polar wander

The dramatic diversification of animal groups known as the Cambrian Explosion (evolution's ‘Big Bang’) remains an unsolved puzzle in Earth Science. The Vendian–Cambrian interval is characterized by anomalously high rates of apparent plate motion, interpreted as True Polar Wander (TPW), and by more than a dozen large, high-frequency perturbations in carbon isotopes that dwarf all others observed through the past 65 million years. We suggest that these biological, tectonic, and geochemical events are intimately related in the following fashion. First, tropical continental margins and shelf-slopes which formed during fragmentation of the supercontinent Rodinia accumulated massive quantities of isotopically-light organic carbon during Late Neoproterozoic time, as indicated by strikingly heavy isotope ratios in inorganic carbon during interglacial intervals. Second, an initial phase of Vendian TPW moved these organic-rich deposits to high latitude, where conditions favored trapping biogenic methane in layers of gas hydrate and perhaps permafrost. Continued sedimentation during Late Vendian time added additional hydrate/gas storage volume and stabilized underlying units until the geothermal gradient moved them out of the clathrate stability field, building up deep reservoirs of highly pressurized methane. Finally, a burst of TPW brought these deposits back to the Tropics, where they gradually warmed and were subjected to regional-scale thermohaline eddy variation and related sedimentation regime changes. Responding to the stochastic character of such changes, each reservoir reached a critical failure point independently at times throughout the Cambrian. By analogy with the Late Paleocene Thermal Maximum event, these methane deposits yield transient, greenhouse-induced pulses of global warming when they erupt. Temperature correlates powerfully with biodiversity; the biochemical kinetics of metabolism at higher temperature decrease generation time and maintain relatively rich and dense invertebrate populations. Repeated thermal pulses along with progressive disruption and alteration of global ocean circulation patterns by TPW could cause the increase in diversity that accompanied the radiation of metazoans. We suggest that a methane ‘fuse’ ignited the Cambrian Evolutionary Explosion.     

DEM simulations of methane hydrate exploitation by thermal recovery and depressurization methods

Methane hydrate (MH, also called fiery ice) exists in forms of pore filling, cementing and load-bearing skeleton in the methane hydrate bearing sediment (MHBS) and affects its mechanical behavior greatly. To study the changes of macro-scale and micro-scale mechanical behaviors of MHBS during exploitation by thermal recovery and depressurization methods, a novel 2D thermo-hydro-mechanical bonded contact model was proposed and implemented into a platform of distinct element method (DEM), PFC2D. MHBS samples were first biaxially compressed to different deviator stress levels to model different in-situ stress conditions. With the deviator stress maintained at constant, the temperature was then raised to simulate the thermal recovery process or the pore water pressure (i.e. confining pressure for MH bond) was decreased to simulate the depressurization process. DEM simulation results showed that: during exploitation, the axial strain increased with the increase of temperature (in the thermal recovery method) or decrease of pore water pressure (in the depressurization method); sample collapsed during MH dissociation if the deviator stress applied was larger than the compression strength of a pure host sand sample; sample experienced volume contraction but its void ratio was slightly larger than the pure host sand sample at the same axial strain throughout the test. By comparison with the laboratory test results, the new model was validated to be capable of reproducing the exploitation process by thermal recovery and depressurization methods. In addition, some micro-scale parameters, such as contact distribution, bond distribution, and averaged pure rotation rate, were also analyzed to investigate their relationships with the macroscopic responses.     

Numerical modeling study of mineralization induced by methane cold seep at the sea bottom

In order to investigate the response of authigenic minerals to gas hydrate geo-systems, the biogeochemical processes and its induced mineralization were predicted by employing the comprehensive reactive transport modeling approach. Based on the available data extracted from the northern continental slope area of the South China Sea, a 1-D vertical column model was developed. Three cases with different upward methane flux rates and three cases with different mineral compositions, i.e., a total of six cases were designed to investigate the effects of variations in the depth of sulfate methane transition zone (SMTZ) and in the mineral composition on the formation of authigenic minerals. The simulation results indicate that the SMTZ depth influenced by both the upward methane flux rate and the initial composition played an important role in the formation of authigenic minerals. The AOM reaction is intensive at the interface, and the precipitation amount of calcite is large, which is mainly controlled by AOM. When the methane leakage rate is 20 times higher than the base case, aragonite starts to precipitate. During the simulation, oligoclase, k-feldspar, smectite-Na, smectite-Ca, chlorite dissolved. Our study specific to this area as a starting point may provide a quantitative approach for investigating carbonate and pyrite formation in hydrate-bearing sediments accounting for methane oxidation and sulfate reduction. The method presented here and the model built in this study can be used for other sites with similar conditions. In addition, this study may serve as an indication for the potential natural gas hydrate reservoir in depth, and is also significant for marine carbon and sulfur cycle.     

Controlling factors on the morphology and spatial distribution of methane-related tubular concretions – Case study of an Early Eocene seep system

Up to 10 m in length and >1 m in diameter tubular, calcite-cemented sandstone concretions are hosted by the faulted Dikilitash unconsolidated sands and sandstones. These structures document shallow subsurface pathways of Early Eocene methane seepage in the Balkan Mountains foreland (NE Bulgaria). Their exceptional exposure allowed a unique study of the factors governing the morphology and spatial distribution of such fossilized fluid conduits. The large dimensions and subvertical, cylindrical shape of the most common tube type primarily reflects the buoyancy-driven, vertical path of an ascending gas-bearing fluid through permeable, mainly unconsolidated sandy host sediments. Tube morphology was also influenced by local stratigraphic anisotropies and might as well document differences in former seepage conditions. Mapping of >800 tubular concretions showed the NNW–NNE elongation and alignment of tube clusters and massive cemented sandstone structures. This suggests that Paleogene fault systems played a major role in directing the movement of fluids. However, within a single tube cluster, tubes are preferentially aligned, over distances up to 50 m along directions at an angle between 10° and 36° with respect to the inferred NNW–NNE, cluster parallel fault traces. In addition, cylindrical tubes of analogue dimensions are aligned over distances >100 m along N15° to N25°-oriented directions. It is hypothesized that this spatial geometry of tubular concretions reflects the complex geometry of deformations structures in fault damage zones along which fluids were preferentially channelled.     

Experimental formation of massive hydrate deposits from accumulation of CH4 gas bubbles within synthetic and natural sediments

In order for methane to be economically produced from the seafloor, prediction and detection of massive hydrate deposits will be necessary. In many cases, hydrate samples recovered from seafloor sediments appear as veins or nodules, suggesting that there are strong geologic controls on where hydrate is likely to accumulate. Experiments have been conducted examining massive hydrate accumulation from methane gas bubbles within natural and synthetic sediments in a large volume pressure vessel through temperature and pressure data, as well as visual observations. Observations of hydrate growth suggest that accumulation of gas bubbles within void spaces and at sediment interfaces likely results in the formation of massive hydrate deposits. Methane hydrate was first observed as a thin film forming at the gas/water interface of methane bubbles trapped within sediment void spaces. As bubbles accumulated, massive hydrate growth occurred. These experiments suggest that in systems containing free methane gas, bubble pathways and accumulation points likely control the location and habit of massive hydrate deposits.     

封闭系统中多孔介质甲烷水合物的CT实验研究

阐述了在封闭系统中的查理模型,建立了利用查理定律计算分析甲烷水合物生成和分解的方法。通过实验,对封闭系统中不同含水量多孔介质甲烷水合物生成、发育和分解的实验方法、相平衡条件、生成量关系等进行了探讨。在一定温度差的介质里,水分克服重力向冷端迁移并生成水合物。实验中利用查理数的改变计算水合物的生成量变化,连通性好的含水多孔介质有很好的水—气结合条件,达到平衡条件后迅速生成水合物,在240分钟内完成,含水量线性地影响甲烷水合物的生成量。同时,利用CT扫描方法直接观测含水粗砂在低温—高压环境下的甲烷水合物生成和分解过程,并可以利用CT图像数据计算出多孔介质中水分迁移、区域密度改变和砂体的移动、及分解后介质密度分布变化特征。