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.     

Identification and investigation of sulphur plumes along the Namibian coast using the MERIS sensor

In the upwelling area along the Namibian coast of SW-Africa sulphur discolorations were investigated to study the impact of hydrogen sulphide on the ecosystem using satellite imagery. The formation of colloidal sulphur in the upper water layer results from the oxidation of hydrogen sulphide. The occurrence of sulphur plumes as well as their temporal and spatial development was investigated in relation to the driving meteorological and oceanographic conditions. Because of the sporadic occurrence of sulphur events and the limited number of ship-borne investigations in that area remote sensing of ocean colour is the only method to follow these phenomena continuously and synoptically. In the past the sulphur plumes were studied by true colour images derived from ocean colour satellite data like sea-viewing wide field of view sensor or moderate resolution imaging spectroradiometer and identified by their typical milky turquoise discoloration.     

Hydrogen incorporation in enstatite in the system MgO–SiO2–H2O–NaCl

The incorporation of hydrogen in enstatite in a hydrous system containing various amounts of NaCl was investigated at 25 kbar. The hydrogen content in enstatite shows a clear negative correlation to the NaCl-concentration in the system. The most favourable explanation is the reduction of water fugacity due to dilution. Other reasons for the limited hydrogen incorporation at high NaCl levels, such as a significant influence of Na⁺ on the defect chemistry or an exchange between OH^- and Cl⁻in enstatite, appear much less important. A partition coefficient D _Na ^En/Fluid = 0.0013 could be determined, demonstrating that Na is less incompatible in enstatite than H. The new results support the idea that dissolved components have to be considered when the total hydrogen storage capacity in nominally anhydrous minerals is estimated, especially in geological settings with high levels of halogens, such as subduction zones.     

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.     

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.     

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.     

厦门大气降水的氢氧同位素研究

本文研究了厦门地区大气降水的氢、氧同位素组成,提出了大气降水线方程的δD＝8．16δ^18O＋10．68,并与全国及全球降水线进行比较,揭示了该降水线方程的特征。对全年氚过剩值（d）及降水线特征研究表明,厦门岛全年降不涞源较为单一,主要为海洋性气团。降水中δD与δ^18O的降水量效应明显,且该影响远远掩盖了温度效应。     

盐场卤水成色原因分析及脱色方法研究

以天津汉沽盐场高镁卤水为研究对象,对其杂质形式、成色原因进行了系统分析。研究表明,卤水中的成色物质主要是大量的饱和脂类、羧酸类、醇醚类、胺类及不饱和的芳烃类、醛酮类、烯烃类等有机物质,经过氧化氢氧化-氢氧化锆吸附联合脱色工艺后,卤水色度及CODCr去除率分别可达99%和85%,镁离子的损失率可控制在1%以下,吸附剂氢氧化锆经脱附再生后可循环使用,大大降低了工艺运行成本。     

河道水体中氢氧稳定同位素组成的微分方程模型

介绍了前人提出并被广泛应用的瑞利分馏模型,指出了其优缺点。针对其不足,在作了一定的假定和简化的前提下,基于瑞利分馏原理和水力学基本定律分别推导了:①静止水体的氢氧稳定同位素组成随时间变化的微分方程模型,揭示了静止水体的同位素组成与时间、分馏系数和蒸发率之间的关系;②河道中运动水体的同位素组成随时间和空间变化的微分方程模型,导出了河道运动水体中稳定同位素组成与分馏系数、流速、流量、蒸发率之间的定量关系。最后通过数学推导论述了上述各模型之间的内在联系。上述模型的建立为定量计算和精确模拟运动水体中氢氧稳定同位素组成的变化提供了确定性的数学基础,也为更客观、更充分的解译水的稳定同位素数据提供了帮助。     

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.