Water mineral surfaces

Due to low water contents, high specific surface areas and pore structures (see the previous section), the water-rock interactions within the Tournemire shales must be characterized by strong short range (nanometre-scale) water (or solute) molecules-mineral interactions. Therefore, the physico-chemical characteristics of the water and its solutes will be different from that of free water which is conventionally considered to take part in water-rock interactions (Horseman et al. 1996). The difference arises from factors such as the very low mobility of water in thin films, the high suction potentials developed owing to water-mineral surface electrostatic interactions and the membrane filtration of anions. The 9% porosity given above must be considered as a maximum value since waters bound chemically to mineral surfaces are included in the estimates in reality free waters are of most importance to the present study. 

Volatilization. The susceptibility of a herbicide to loss through volatilization has received much attention, due in part to the realization that herbicides in the vapor phase may be transported large distances from the point of application. Volatilization losses can be as high as 80—90% of the total applied herbicide within several days of application. The processes that control the amount of herbicide volatilized are the evaporation of the herbicide from the solution or soHd phase into the air, and dispersal and dilution of the resulting vapor into the atmosphere (250). These processes are influenced by many factors including herbicide application rate, wind velocity, temperature, soil moisture content, and the compound s sorption to soil organic and mineral surfaces. Properties of the herbicide that influence volatility include vapor pressure, water solubility, and chemical stmcture (251). 

Air pollutants may enter plant systems by either a primary or a secondary pathway. The primary pathway is analogous to human inhalation. Figure 8-2 shows the cross section of a leaf. Both of the outer surfaces are covered by a layer of epidermal cells, which help in moisture retention. Between the epidermal layers are the mesophyll cells—the spongy and palisade parenchyma. The leaf has a vascular bundle which carries water, minerals, and carbohydrates throughout the plant. Two important features shown in Fig. 8-2 are the openings in the epidermal layers called stomates, which are controlled by guard cells which can open and close, and air spaces in the interior of the leaf. 

Inorganic reactions in the soil interstitial waters also influence dissolved P concentrations. These reactions include the dissolution or precipitation of P-containing minerals or the adsorption and desorption of P onto and from mineral surfaces. As discussed above, the inorganic reactivity of phosphate is strongly dependent on pH. In alkaline systems, apatite solubility should limit groundwater phosphate whereas in acidic soils, aluminum phosphates should dominate. Adsorption of phosphate onto mineral surfaces, such as iron or aluminum oxyhydroxides and clays, is favored by low solution pH and may influence soil interstitial water concentrations. Phosphorus will be exchanged between organic materials, soil inter-... 

The thermodynamic properties of U-Th series nuclides in solution are important parameters to take into account when explaining the U-Th-Ra mobility in surface environments. They are, however, not the only ones controlling radionuclide fractionations in surface waters and weathering profiles. These fractionations and the resulting radioactive disequilibria are also influenced by the adsorption of radionuclides onto mineral surfaces and their reactions with organic matter, micro-organisms and colloids. 

Geckeis H, Klenze R, Kim J1 (1999) Solid-water interface reactions of actinides and homologues sorption onto mineral surfaces. Radiochim Acta 87 13-21... 

The practical applications of NaBH4 reductions on mineral surfaces for in situ generated SchifFs bases have been successfully demonstrated. The solid-state reductive amination of carbonyl compounds on various inorganic solid supports such as alumina, clay, silica etc. and especially on K 10 clay surface rapidly afford secondary and tertiary amines [126]. Clay behaves as a Lewis acid and also provides water from its interlayers thus enhancing the reducing ability of NaBH4 [22],... 

KoC is an important parameter which describes the potential for movement or mobility of pesticides in soil, sediment and groundwater. Because of the structural complexity of these agrochemical molecules, the above simple relationship which considers only the chemical s hydrophobicity may fail for polar and ionic compounds. The effects of pH, soil properties, mineral surfaces and other factors influencing sorption become important. Other quantities, KD (sorption partition coefficient to the whole soil on a dry weight basis) and KqM (organic matter-water partition coefficient) are also commonly used to describe the extent of sorption. K0M is often estimated as 0.56 KoC, implying that organic matter is 56% carbon. 

Leoni [366] observed that in the extraction preconcentration of organochlo-rine insecticides and PCB s from surface and coastal waters in the presence of other pollutants such as oil, surface active substances, etc., the results obtained with an absorption column of Tenax-Celite are equivalent to those obtained with the continuous liquid-liquid extraction technique. For non-saline waters that contain solids in suspension that absorb pesticides, it may be necessary to filter the water before extraction with Tenax and then to extract the suspended solids separately. Analyses of river and estuarine sea waters, filtered before extraction, showed the effectiveness of Tenax, and the extracts obtained for pesticide analysis prove to be much less contaminated by interfering substances than corresponding extracts obtained by the liquid-liquid technique. Leoni et al. [365] showed that for the extraction of organic micro pollutants such as pesticides and aromatic polycyclic hydrocarbons from waters, the recoveries of these substances from unpolluted waters (mineral and potable waters) when added at the level of 1 xg/l averaged 90%. 

Rate constants for the dissolution and precipitation of quartz, for example, have been measured in deionized water (Rimstidt and Barnes, 1980). Dove and Crerar (1990), however, found that reaction rates increased by as much as one and a half orders of magnitude when the reaction proceeded in dilute electrolyte solutions. As well, reaction rates determined in the laboratory from hydrothermal experiments on clean systems differ substantially from those that occur in nature, where clay minerals, oxides, and other materials may coat mineral surfaces and hinder reaction. 

Even where it is not occluded, the mineral surface may not be reactive. In the va-dose zone, the surface may not be fully in contact with water or may contact water only intermittently. In the saturated zone, a mineral may touch virtually immobile water within isolated portions of the sediment s pore structure. Fluid chemistry in such microenvironments may bear little relationship to the bulk chemistry of the pore water. Since groundwater flow tends to be channeled through the most permeable portions of the subsurface, furthermore, fluids may bypass many or most of the mineral grains in a sediment or rock. The latter phenomenon is especially pronounced in fractured rocks, where only the mineral surfaces lining the fracture may be reactive. 

The first class, discussed in detail in Chapter 6, was reaction between a fluid and the minerals it contacts. The kinetics of the reactions by which minerals dissolve and precipitate was the subject of the preceding chapter (Chapter 16). The second class of reactions commonly observed to be in disequilibrium in natural waters, as discussed in Chapter 7, is redox reactions. The subject of this chapter is modeling the rates at which redox reactions proceed within the aqueous solution, or when catalyzed on a mineral surface or by the action of an enzyme. In the following chapter (Chapter 18), we consider the related question of how rapidly redox reactions proceed when catalyzed in the geosphere by the action of microbial life. 

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