Mineral surfaces processes

Electrochemical processes at some sulfide mineral surfaces lead to the formation of oxidation products as in the case of the hydrophobization of... 

Other Interaction Processes. The selectivity of flotation reagents in a pulp and their functions depend on their interactions with the mineral phases to be separated, but other physicochemical and hydrodynamic processes also play roles. AH adsorption—desorption phenomena occur at the sohd—hquid interfacial region. Surface processes that influence such adsorptions include activation and depression. Activators and depressants are auxiUary reagents. 

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). 

Under natural conditions the rates of dissolution of most minerals are too slow to depend on mass transfer of the reactants or products in the aqueous phase. This restricts the case to one either of weathering reactions where the rate-controlling mechanism is the mass transfer of reactants and products in the soHd phase, or of reactions controlled by a surface process and the related detachment process of reactants. 

Coupling to a mineral surface requires the presence of active hydroxyls on the substrate. The coupling reaction is a multi-step process that proceeds from a state of physisorption through hydrogen bond formation to actual covalent bond formation through condensation of surface hydroxyls with silanols ... 

Wachtershanser has also suggested that early metabolic processes first occurred on the surface of pyrite and other related mineral materials. The iron-sulfur chemistry that prevailed on these mineral surfaces may have influenced the evolution of the iron-sulfur proteins that control and catalyze many reactions in modern pathways (including the succinate dehydrogenase and aconitase reactions of the TCA cycle). 

Eberl, D. D., Srodon, J., and Northrop, H. R. (1986). Potassium fixation in smectite by wetting and drying. In "Geochemical Processes at Mineral Surfaces," pp. 296-325. American Chemical Society, Washington, DC, ACS Symposium Series 323. 

The wettability of the rock is responsible for the behavior of a reservoir subjected to any oil-recovery process. Because the chemical composition of the mineral surface is mostly responsible for its wetting behavior, the relationship between wettability and chemical composition of the surface is key information. 

Flotation is certainly the major separation method based on the surface chemistry of mineral particles. It is, however, not the only method. Selective flocculation and agglomeration may be mentioned as other methods used commercially to a limited extent. The former is for hematite, while the latter is for coal and finely divided metallic oxide minerals. Both processes use the same principles as described for flotation to obtain selectivity. In selective flocculation, polymeric flocculants are used. The flocculants selectively adsorb on the hematite, and the hematite floes form and settle readily. Thereby separation from the sili-... 

Comminution leads to an increase in surface area and exposes the mineral grains to attack by the solvent. The mineral grains may not, however, be liberated completely from the associated gangue material by this process. As long as a direct contact between some portions of the mineral grain and the leachant is not inhibited or lost, the mineral leaching process proceeds in an uninterrupted manner. 

The geological process of the formation of serpentine from peridotite probably involves the synthesis of carbon compounds under FTT conditions (see Sect. 7.2.3). The hydrogen set free in the serpentinisation process can react with CO2 or CO in various ways. The process must be quite complex, as CO2 and CO flow through the system of clefts and chasms in the oceanic crust and must thus pass by various mineral surfaces, at which catalytic processes as well as adsorption and desorption could occur. 

An increase of the pH in the aqueous medium, and capture of SO42- by the mineral surface, could lead to the liberation of Pi. In addition, there seem to be selfregulation mechanisms for the Pi sorption-desorption process, depending on the S042 concentration at the interface. Processes such as enrichment and liberation... 

Another hypothesis on homochirality involves interaction of biomolecules with minerals, either at rock surfaces or at the sea bottom thus, adsorption processes of biomolecules at chiral mineral surfaces have been studied. Klabunovskii and Thiemann (2000) used a large selection of analytical data, provided by other authors, to study whether natural, optically active quartz could have played a role in the emergence of optical activity on the primeval Earth. Some researchers consider it possible that enantioselective adsorption by one of the quartz species (L or D) could have led to the homochirality of biomolecules. Asymmetric adsorption at enantiomor-phic quartz crystals has been detected L-quartz preferentially adsorbs L-alanine. Asymmetrical hydrogenation using d- or L-quartz as active catalysts is also possible. However, if the information in a large number of publications is averaged out, as Klabunovskii and Thiemann could show, there is no clear preference in nature for one of the two enantiomorphic quartz structures. It is possible that rhomobohedral... 

It should be possible to use the special properties of chiral structures for particular separation problems. According to Belinski and Tencer, one possible way in which nature solved the ribose problem could have involved an enantioselective and diastereoselective purification process acting on a mixture of biomolecules, which left ribose as the only molecule available for further reactions. The authors propose a theoretical mechanism in which a type of chromatographic process occurs at chiral mineral surfaces. This paper is likely to stimulate new experiments as well as the quest for as yet unknown surfaces which can separate racemic carbohydrate mixtures. The question arises, however, as to whether there were minerals present on the young Earth which are now unknown, as they no longer exist on the Earth of today (Belinski and Tencer, 2007). 

The great importance of minerals in prebiotic chemical reactions is undisputed. Interactions between mineral surfaces and organic molecules, and their influence on self-organisation processes, have been the subject of much study. New results from Szostak and co-workers show that the formation of vesicles is not limited to one type of mineral, but can involve various types of surfaces. Different minerals were studied in order to find out how particle size, particle shape, composition and charge can influence vesicle formation. Thus, for example, montmorillonite (Na and K10), kaolinite, talc, aluminium silicates, quartz, perlite, pyrite, hydrotalcite and Teflon particles were studied. Vesicle formation was catalysed best by aluminium solicate, followed by hydrotalcite, kaolinite and talcum (Hanczyc et al., 2007). 

Cr(VI).Other remediation processes for Cr(VI) contaminated soils include H2S injection, aqueous Fe(II) injection, and the use of reduced Fe solids. Aqueous-phase Cr(VI)-Fe(II) redox reactions may be significant if Fe2+ concentrations are in equilibrium with relatively soluble, ferric hydroxide-like phases (Tokunaga et al., 2003). The overall interactions involving microbial activity, organic carbon degradation, Fe2+, and mineral surfaces control the net rates of Cr(VI) reactions in soils. 

Sposito, G. Distinguish adsorption from surface precipitation. In Geochemical Processes at Mineral Surfaces. J.A. Davis, K.F. Hayes, eds. Washington D.C. Americal Chemical Society Symposium Series No. 323,1986. 

Even if the solubility limit of relevant solid phases is not exceeded, a large fraction of trace metals in natural waters often occurs bound to particles of various size ranges (nanometres to millimetres). An important process for binding of metals to particles is adsorption to mineral surfaces (often oxides or hydroxides) [29]. 

Pyrite Oxidation. The oxidation of Fe(ll) minerals by Fe3+ is also of importance in the oxidation of pyrite by 02. This process is mediated by the Fe(II)-Fe(III)system. Pyrite is oxidized by Fe3+ (which forms a surface complex with the pyrite (cf. formula VI in Fig. 9.1) (Luther, 1990). The rate determining step at the relatively low pH values encountered under conditions of pyrite dissolution is the oxygenation of Fe(II) to Fe(III) usually catalyzed by autotrophic bacteria (Singer and Stumm, 1970 Stumm-Zollinger, 1972). Thus, the overall rate of pyrite dissolution is insensitive to the mineral surface area concentration. Microbially catalyzed oxidation of Fe(II) to Fe(III) by oxygen could also be of some significance for oxidative silicate dissolution in certain acid environments. 

Dissolved iron(III) is (i) an intermediate of the oxidative hydrolysis of Fe(II), and (ii) results from the thermal non-reductive dissolution of iron(III)(hydr)oxides, a reaction that is catalyzed by iron(II) as discussed in Chapter 9. Hence, iron(II) formation in the photic zone may occur as an autocatalytic process (see Chapter 10.4). This is also true for the oxidation of iron(II). As has been discussed in Chapter 9.4, the oxidation of iron(II) by oxygen is greatly enhanced if the ferrous iron is adsorbed at a mineral (or biological) surface. Since mineral surfaces are formed via the oxidative hydrolysis of Fe(II), this reaction proceeds as an autocatalytic process (Sung and Morgan, 1980). Both the rate of photochemical iron(II) formation and the rate of oxidation of iron(II) are strongly pH-dependent the latter increases with... 

Honeyman, B. D., and J. O. Leckie (1986), "Macroscopic Partitioning Coefficient for Metal Ion Adsorption Proton Stoichiometry at Variable pH and Adsorption Density", in J. A. Davis and K. F. Hayes, Eds., Geochemical Processes at Mineral Surfaces, ACS Symposium, Washington, DC. 

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