Generation of hydrogen ions and hydrogen gas in quartz–water crushing experiments: an example of chemical processes in active faults

To understand the fundamental chemical processes of fluid–rock interaction during the pulverization of quartz grains in fault zones, quartz grains were crushed within pure water. The crushing experiments were performed batch style using a shaking apparatus. The crushing process induced a decrease in pH and an increase in hydrogen gas with increased shaking duration. The amount of hydrogen ions generated was five times larger than that of the hydrogen gas, which was consistent with the amount of Si radicals estimated from electron spin resonance measurements by Hochstrasser and Antonini (1972). This indicates that hydrogen gas was generated by consuming most of the Si radicals. The generation of hydrogen ions was most likely related to the presence of silanols on the newly formed mineral surface, implying a change of proton activities in the fluid after pulverization of quartz.     

Space group and hydrogen sites of δ-AlOOH and implications for a hypothetical high-pressure form of Mg(OH)<Subscript>2</Subscript>

The space group and hydrogen positions of -(Al_0.84Mg_0.07Si_0.09)OOH are investigated using a single crystal synthesized using a multi-anvil apparatus under conditions of 1000 °C and 21 GPa. The space group determined by single-crystal X-ray diffraction is to Pnn2, with unit-cell parameters of a=4.6975(8) Å, b= 4.2060(6) Å, c=2.8327(4) Å, and V=55.97(1) ų. Partial occupancy of the Al site by Mg and Si suggests the possibility of a limited solid solution between -AlOOH, stishovite, and a hypothetical CaCl₂-type Mg(OH)₂ that is 16% denser than brucite. Difference-Fourier maps reveal two small but significant Fourier peaks attributable to hydrogen atoms. Atomic distances and angles around the first peak indicate a hydrogen bond with O···O distances of 2.511 Å, while those around the second peak are suggestive of a bifurcated hydrogen bond with O···O distances of 2.743 and 2.743 Å.     

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.     

Metallogenic characteristics of the Wushan intrusive massive sulphide deposit, Jiangxi Province

The metallogenic characteristics of the Wushan deposit are discussed based on its regional geology, mine geology, mineralization temperature and stable isotopic compositions. The deposit is closely related to granodiorite both spatially and genetically, thus belonging to intrusive massive sulphidr deposits, which art. different in metallogenic features from that of the volcanogenic massive sulphidr deposits.     

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.     

辉锑锡铅矿的穆斯堡尔谱及其晶体化学研究

辉锑锡铅矿是结构复杂而尚未确定,以及晶体化学尚有争议的一种稀有矿物。X射线衍射结果表明其结构是由假四方亚层(称T层)和假六方亚层(称H层)穿插组成的层状结构。T层的化学成分具有MeS形式,H层则具有MeS_2形式。本文通过广西大厂的辉锑锡铅矿的穆斯堡尔谱研究,确定了矿物中Sn的大部分为Sn~(4+),而Sn~(2+)只占较少的部分;Fe中含有Fe~(3+)和Fe~(3+)。它们在T层和H层中的分布为Sn~(2+)(T)占5.6%,Sn~(4+)(T)占25.9%,Sn~(4+)(H)占68.5%,Fe~(2+)(T)占59.5%,Fe~(3+)(H)占40.5%。从Sn、Fe的穆斯堡尔谱参数还可看出H层的共价性比T层的强。     

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.