A computer simulation study of OH defects in Mg2SiO4 and Mg2GeO4 spinels

Classical atomistic simulation techniques have been used to investigate the energies of hydrogen defects in Mg₂SiO₄ and Mg₂GeO₄ spinels. Ringwoodite (γ-Mg₂SiO₄) is considered to be the most abundant mineral in the lower part of the transition zone and can incorporate large amounts of water in the form of hydroxyls, whereas the germanate spinel (γ-Mg₂GeO₄) corresponds to a low-pressure structural analogue for ringwoodite. The calculated defect energies indicate that the most favourable mechanisms for hydrogen incorporation are coupled either with the reduction of ferric iron or with the creation of tetrahedral vacancies. Hydrogen will go preferentially into tetrahedral vacancies, eventually leading to the formation of the hydrogarnet defect, before associating with other negatively charged point defects. The presence of isolated hydroxyls is not expected. The same trend is observed for germanate, and thus γ-Mg₂GeO₄ could be used as a low-pressure analogue for ringwoodite in studies of water-related defects and their effect on physical properties.     

Hydrogen from coal: Production and utilisation technologies

Although coal may be viewed as a dirty fuel due to its high greenhouse emissions when combusted, a strong case can be made for coal to be a major world source of clean H₂ energy. Apart from the fact that resources of coal will outlast oil and natural gas by centuries, there is a shift towards developing environmentally benign coal technologies, which can lead to high energy conversion efficiencies and low air pollution emissions as compared to conventional coal fired power generation plant. There are currently several world research and industrial development projects in the areas of Integrated Gasification Combined Cycles (IGCC) and Integrated Gasification Fuel Cell (IGFC) systems. In such systems, there is a need to integrate complex unit operations including gasifiers, gas separation and cleaning units, water gas shift reactors, turbines, heat exchangers, steam generators and fuel cells. IGFC systems tested in the USA, Europe and Japan employing gasifiers (Texaco, Lurgi and Eagle) and fuel cells have resulted in energy conversions at efficiency of 47.5% (HHV) which is much higher than the 30–35% efficiency of conventional coal fired power generation. Solid oxide fuel cells (SOFC) and molten carbonate fuel cells (MCFC) are the front runners in energy production from coal gases. These fuel cells can operate at high temperatures and are robust to gas poisoning impurities. IGCC and IGFC technologies are expensive and currently economically uncompetitive as compared to established and mature power generation technology. However, further efficiency and technology improvements coupled with world pressures on limitation of greenhouse gases and other gaseous pollutants could make IGCC/IGFC technically and economically viable for hydrogen production and utilisation in clean and environmentally benign energy systems.     

Computer modelling of hydrogen defects in the clinopyroxenes diopside and jadeite

Atomistic computer simulation techniques have been employed to model mechanisms of hydrogen incorporation in the clinopyroxenes diopside and jadeite. Calculation of solution reaction energies for the pure phases indicates that hydrogen is most easily incorporated via the formation of [V_Si(OH)₄] ^x hydrogarnet type defects. When components of the two phases are mixed, then solution energies can become exothermic. The substitution of Al for Si in diopside and of Mg or Ca for Al in jadeite, provides favourable routes for hydrogen incorporation, with exothermic values of solution energy. Thus the amount of water present in these minerals in the Earth’s upper mantle will vary with composition. Simulation of IR frequencies associated with O–H stretching at specific defect clusters has also been carried out. An analysis of hydrogen–oxygen bond lengths gives good agreement, although comparison of experimental and calculated IR frequencies are problematic. This is partly due to the complexity of experimental spectra, but may also be due in part to deficiencies in the ability of the model to accurately describe the O–H stretching frequency.     

Implications of ozone depletion for surface-water photochemistry: Sensitivity of clear lakes

Increased ultraviolet-B radiation (UV-B) in aquatic ecosystems brought about by stratospheric ozone depletion may result in increased formation rates of photochemical reaction products in the surface waters of aquatic ecosystems. In this study, the potential impact of increases in lower wave-length radiation on the formation of hydrogen peroxide (H₂O₂) and singlet oxygen (¹O₂) was modelled for lakes over a range of dissolved organic carbon (DOC) concentrations. The impact of increased UV-B radiation on the production of carbon monoxide (CO) was also calculated for two humic stained systems. The relative increases of H₂O₂ and¹O₂ production were greater in the clear lakes (70% increase in photochemical reaction rates near the surface) than the coloured systems (25%). Production of CO in the study sites also increased under depleted ozone conditions implying increased DOC losses to the overlying atmosphere.     

Discharge of H2 from the Atotsugawa and Ushikubi Faults,Japan, and its relation to earthquakes

The concentration of H₂ in soil gases has been measured weekly at five stations on the Atotsugawa and Ushikubi faults in northern central Main Island, Japan, since 1981 in search of possible relationship with earthquakes. The observed H₂ concentration varies from lower than 1 ppm to 7.8% in time and place. When a large earthquake (M: 7.7, epicenter distance: 486 km) occurred on 26 May 1983, an outstanding discharge of H₂ was observed at all five stations, preseismically at three of them, and coseismically at the other two. Simultaneous H₂ emission was also observed at some stations in seven other occasions. These periods of unusual H₂ discharge nearly coincided with occurrences of major earthquakes in Japan, but not of local minor earthquakes along the Atotsugawa fault. This fault, being a deep fracture zone, may be sensitive to large-scale crustal stress changes which incidentally cause the major earthquakes. Increased H₂ may be produced by rock fracture caused by the increased stresses on the fault and by the earthquakes themselves. Local minor earthquakes along Atotsugawa fault with magnitude lower than 3 may be unable to cause sufficient rock fracture to produce significant H₂.     

Water organisation at the solid–aqueous solution interfaceOrganisation de l'eau à l'interface solide–solution aqueuse

The aim of this review is to examine the present knowledge about water structure close to an interface or confined in porous spaces. First, the structure of liquid water is briefly described. Though its understanding remains incomplete, it appears that it is largely dominated by the hydrogen bond network and its dynamical evolution. The presence of any ‘foreign’ substance in water perturbs such a structure by changing at least locally the hydrogen bond network. For this reason, the presence of a solid interface significantly modifies the structure of the first adsorbed layers. Whatever the support, it is now clearly evidenced that structural perturbations are limited to distances lower than 10–15 Å from the interface. The nature, energetic heterogeneity and hydrophilicility/hydrophobicity of the solid surface influence the arrangement of water molecules. This surface organisation must definitely be considered when studying adsorption phenomena at the solid–aqueous solution interface. The relevance of such problems to geosciences is illustrated by a few situations in which water structure plays a prominent role. To cite this article: L.J. Michot et al., C. R. Geoscience 334 (2002) 611–631.     

The Impact of Human Activities on Freshwater Aquatic Systems

The roles of oxygen and its activated species (superoxide radicals, hydrogen peroxide, hydroxyl radicals), as well as that of sulfur compounds, are considered in relation to biological quality and the self-cleaning capacity of freshwater aquatic systems. The effects on the aquatic redox-processes are discussed in terms of atmospheric fallout of sulfur compounds, bottom sediment composition, and input of wastewaters containing reducing substances. It is shown that the totality of anthropogenic influences, and/or unfavourable natural geochemical conditions, as well as climatic effects in a region can increase the significance of one-electron transfer processes in bio-geochemical cycles of oxygen, sulfur and manganese, compared with the significance of two-electron transfer processes. The resulting, reactive intermediate products of one-electron transfer processes are very important with respect to the composition and properties of aquatic systems. Examples are given of practical applications of wastewater treatment, using hydrogen peroxide and UV-irradiation, and of regulation of consumers’ activities which affect natural waters.     

鞍山-海城地区地震地下水地球化学研究

通过测量辽宁省鞍山-海城地区地震重点监测区地下水离子浓度和氢、氧同位素组成,讨论了该区地下水化学类型的时空变化及其成因。测量结果表明,取样点水温变化范围为11.0～97.0℃,水样的总固溶物（TDS）在197.89～829.99mg/L之间,水样分为8种化学类型。大部分水样的δD、δ¹⁸O值均沿中国东北地区大气降水线分布,少数有所偏离,表明该区的地下水主要接受大气降水的补给,并可能有深部水的供给。研究区Ca-HCO₃和Ca·Mg-HCO₃型水主要是岩石风化溶解和阳离子交换作用的结果;Ca-HCO₃·Cl和Ca·Na-Cl·SO₄型水主要受岩石风化溶解、阳离子交换作用、深部卤水混入或人类活动影响;Ca-HCO₃·SO₄和Ca-SO₄·HCO₃型水与岩石风化溶解以及深部流体混入有关;Na-SO₄·HCO₃和Na-HCO₃·SO₄型水主要是深部来源水体的混入造成的。采样期间研究区发生2次M_L≥3.0地震,采样点在地震发生月份出现了明显的离子浓度异常变化;Na⁺、Mg²⁺、Ca²⁺、Cl^-和SO₄^2-浓度变化明显,对地震活动响应较灵敏。     

Geochemistry of the Martian Meteorite GRV 99027

GRV 90027 is a Martian lherzolitic shergottites (L-S) containing poikilitic, non-poikilitic, and melted pocket components. GRV 99027 is mainly composed of olive (55 vol%) and pyroxene (37.5 vol%), with minor maskelynite (6 vol%) and chromite (1.5 vol%), and trace whitelockite and troilite, ect. In this paper, the mineralogy and petrology of GRV 99027 are reported; in addition, the geochemical characteristics of the REEs and H isotopes in the GRV 99027 are also further investigated. The ΣREE in GRV 99027 is relatively low; HREEs are enriched in olivine and pyroxene grains; LREEs are enriched in plagioclase with a high positive Eu anomaly. High ΣREE value is found in rare mineral whitlockite (less than 0.2 vol%), LREE≈HREE, and whitlockite has a negative Eu anomaly. The REE distribution patterns of the whole -rock of GRV 99027 is similar to but different from that of other L-S Martian meteorites, indicating that they came from different location of Mars. GRV 99027 has a high δD value. Different water-bearing minerals give different contribution for δD value. The δD of phosphates generally does not correlate with water content, and δD has a weak negative correlation with water content. GRV 99027 can be classified as an L-S Martian meteorite based on mineralogical assemblage patterns, REE distribution patterns, and hydrogen isotope. The isotope data of Sr, Nd, Pb, Os and REE from other L-S Martian meteorites were collected to discuss the formation history of the GRV 99027. Similar to other L-S Martian meteorites, GRV 99027 originated from part of Mar's mantle; during one strong impact event about 4M years ago, the meteorites were ejected from deep mantle into space, and traveled for a different duration in space (indicated by different cosmic exposure time), and captured by the Earth later in different time, ultimately falling on the Antarctica as L-S Martian meteorites.     

Asteroid impact in the Black Sea. Death by drowning or asphyxiation?

Normally the consequences of an impact of an asteroid in a water body are discussed in terms of the beach run up of impact-generated waves. If even a small asteroid would hit the Black Sea, however, the potential emissions of toxic and flammable gases could be more disastrous to the region (comprised of Romania, Ukraine, Russia, Georgia, Turkey and Bulgaria) than the tsunami caused by the impact.