Microstructure characteristics during hydrate formation and dissociation revealed by X-ray tomographic microscopy

Despite much progress over the past years in fundamental gas hydrate research, frontiers to the unknown are the early beginning and early decomposition of gas hydrates in their natural, submarine environment: gas bubbles meeting ocean water and forming hydrate, and gas starting to escape from the surface of a hydrate grain. In this paper we report on both of these topics, and present three-dimensional microstructure results obtained by synchrotron radiation X-ray cryo-tomographic microscopy (SRXCTM). Hydrates can precipitate when hydrate-forming molecules such as methane exceed solubility, and combine with water within the gas hydrate stability zone. Here we show hydrate formation on surfaces of bubbles from different gas mixtures and seawater, based on underwater robotic in situ experiments in the deep Monterey Canyon, offshore California. Hydrate begins to form from the surrounding water on the bubble surfaces, and subsequently grows inward into the bubble, evidenced by distinct edges. Over time, the bubbles become smaller while gas is being incorporated into newly formed hydrate. In contrast, current understanding has been that hydrate decomposition starts on the outer surface of hydrate aggregates and grains. It is shown that in an early stage of decomposition, newly found tube structures connect well-preserved gas hydrate patches to areas that are dissociating, demonstrating how dissociating areas in a hydrate grain are linked through hydrate that is still intact and will likely decompose at a later stage.

On the last explosions of carbonatite pipe G3b, Gross Brukkaros, Namibia

 Pipe G3b is part of the Upper Cretaceous carbonatitic Gross Brukkaros Volcanic Field in southern Namibia. The pipe represents the root zone of a diatreme and is located 2800 m west of the rim of Gross Brukkaros, a downsag caldera. The pipe is exposed approximately 550 m below the original Upper Cretaceous land surface. It cuts down into its own feeder dyke, 0.3 m thick. The pipe coalesced from two small pipes and in plan view is 19 m long and 12 m wide. It consists of fragmented Cambrian Nama quartzites and shales of the Fish River subgroup. Despite intensive brecciation, the stratigraphic sequence of the country rocks is almost preserved in the pipe. In addition, the feeder dyke became fragmented too and can be traced in a 2- to 3-m-wide zone full of carbonatite blocks along the southern margin of the pipe. The void space of the breccia is 30–50% in volume. Finally, after the disruption of country rocks and feeder dyke, a little carbonatite magma intruded some of the void space. The breccia of pipe G3b is considered to represent a root zone at the transition from the feeder dyke into a diatreme above. Formation of the breccia required a shock wave thought to have been associated with a last explosion of the diatreme immediately above the present level of exposure. The explosion can be shown to have been phreatomagmatic in origin. Received: 11 October 1996 / Accepted: 6 March 1997     

How to survive a Lunar night

In the frame of the recent worldwide activities of Lunar research, including various studies for surface stations, the aspect of longevity of such stations has been identified as a particular technical challenge. The reason for this lies in the long (about 14 days) and cold Lunar night during which it is non-trivial to keep spacecraft systems alive and sensitive equipment within an acceptable temperature range.The following paper analyzes and compares various concepts to survive Lunar night, both with and without radioisotope heater technology.The latter normally implies the use of highly toxic material (typically plutonium), which is politically problematic and a driver for cost and safety procedures.Concepts without radioisotope heating need to foresee special measures, like extremely efficient thermal insulation or sub-surface positioning of all temperature sensitive components.Special emphasis has been taken on the thermal analysis of a penetrator-type surface station. The relevant issues are discussed and results for day–night cycles are presented, assuming a typical set of engineering parameters. This concept appears to be the easiest to implement from a thermal point of view, if the use of radioisotope heaters has to be avoided.     

The oxygen isotope fractionation behaviour of kyanite in experiment and nature

The oxygen isotope fractionation between kyanite and calcium carbonate has been investigated experimentally at four temperatures in the range between 625 and 775 °C at 13 kbar. Because of low exchange rates, the isotopic reaction was enhanced by polymorphic transformation of andalusite to kyanite. With this experimental modification a close approach to equilibrium was reached in all runs. The temperature dependence of the equilibrium fractionation is described by the equation 1000 ln _ky-cc=−2.62×10⁶/T ². Application of the experimental results to natural quartz-kyanite-garnet assemblages indicates the preservation of the oxygen isotope composition of kyanite acquired during its formation, reflecting its extremely low oxygen diffusivity. This refractory behaviour restricts the use of kyanite for thermometry but opens the possibility to use its O-isotope composition as an indicator for recognition of polymetamorphic rock histories and reconstruction of the prograde evolution of a metamorphic sequence. Received: 8 June 1998 / Accepted: 24 August 1998     

Field experiments yield new insights into gas exchange and excess air formation in natural porous media

Gas exchange between seepage water and soil air within the unsaturated and quasi-saturated zones is fundamentally different from gas exchange between water and gas across a free boundary layer, e.g., in lakes or rivers. In addition to the atmospheric equilibrium fraction, most groundwater samples contain an excess of dissolved atmospheric gases which is called “excess air”. Excess air in groundwater is not only of crucial importance for the interpretation of gaseous environmental tracer data, but also for other aspects of groundwater hydrology, e.g., for oxygen availability in bio-remediation and in connection with changes in transport dynamics caused by the presence of entrapped air bubbles. Whereas atmospheric solubility equilibrium is controlled mainly by local soil temperature, the excess air component is characterized by the (hydrostatic) pressure acting on entrapped air bubbles within the quasi-saturated zone. Here we present the results of preliminary field experiments in which we investigated gas exchange and excess air formation in natural porous media. The experimental data suggest that the formation of excess air depends significantly on soil properties and on infiltration mechanisms. Excess air was produced by the partial dissolution of entrapped air bubbles during a sprinkling experiment in fine-grained sediments, whereas similar experiments conducted in coarse sand and gravel did not lead to the formation of excess air in the infiltrating water. Furthermore, the experiments revealed that the noble gas temperatures determined from noble gases dissolved in seepage water at different depths are identical to the corresponding in situ soil temperatures. This finding is important for all applications of noble gases as a paleotemperature indicator in groundwater since these applications are always based on the assumption that the noble gas temperature is identical to the (past) soil temperature.     

The near-solidus transition from garnet lherzolite to spinel lherzolite

The position of the transition from spinel lherzolite to garnet lherzolite in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS) has been determined experimentally at near-solidus temperatures. In reversed experiments, the transition occurs between 18 and 20 kbar at 1200 °C and between 26 and 27 kbar at 1500 °C, corresponding to higher pressures than previously envisaged. A position for the transition deeper within the Earth further complicates the explanation of the so-called garnet signatures in the trace element and isotope patterns of mid-ocean ridge basalts. If melting during adiabatic upwelling beneath a mid-ocean ridge begins at the depth required for the stability of garnet in peridotitic compositions, simple melting models predict that the amount of melt produced should be much greater than the observed thickness of the oceanic crust. A partial solution to the apparent conflict might be that (1) the rather simplistic melting models are in error, (2) that melting begins in garnet pyroxenite veins that are believed to be stable at lower pressures than garnet lherzolite or (3) that melting does not involve garnet at all, but it is clinopyroxene causing the trace element patterns observed in basalts erupted at mid-ocean ridges. A second set of reversal experiments were conducted to investigate the solubility of alumina in both orthopyroxenes and clinopyroxenes at the high temperatures near the solidus in the system CMAS. The results are compatible with most previous studies, and may be used as a starting point to calibrate thermodynamic models for pyroxenes in chemical systems, approximating upper mantle chemistry. Received: 9 August 1999 / Accepted: 29 October 1999