Oxidation primary minerals

There are over 65 known vanadium-bearing minerals, some of the more important are Hsted in Table 1. Patronite, bravoite, sulvanite, davidite, and roscoehte are classified as primary minerals, whereas all of the others are secondary products which form in the oxidizing zone of the upper Hthosphere. 

Copper ore minerals maybe classified as primary, secondary, oxidized, and native copper. Primaryrninerals were concentrated in ore bodies by hydrothermal processes secondary minerals formed when copper sulfide deposits exposed at the surface were leached by weathering and groundwater, and the copper reprecipitated near the water table (see Metallurgy, extractive). The important copper minerals are Hsted in Table 1. Of the sulfide ores, bornite, chalcopyrite, and tetrahedrite—teimantite are primary minerals and coveUite, chalcocite, and digenite are more commonly secondary minerals. The oxide minerals, such as chrysocoUa, malachite, and azurite, were formed by oxidation of surface sulfides. Native copper is usually found in the oxidized zone. However, the principal native copper deposits in Michigan are considered primary (5). 

Secondary minerals. As weathering of primary minerals proceeds, ions are released into solution, and new minerals are formed. These new minerals, called secondary minerals, include layer silicate clay minerals, carbonates, phosphates, sulfates and sulfides, different hydroxides and oxyhydroxides of Al, Fe, Mn, Ti, and Si, and non-crystalline minerals such as allophane and imogolite. Secondary minerals, such as the clay minerals, may have a specific surface area in the range of 20-800 m /g and up to 1000 m /g in the case of imogolite (Wada, 1985). Surface area is very important because most chemical reactions in soil are surface reactions occurring at the interface of solids and the soil solution. Layer-silicate clays, oxides, and carbonates are the most widespread secondary minerals. 

The waste organic acids dissolved carbonate minerals, alumino-silicate minerals, and iron/manganese-oxide coatings on the primary minerals in the injection zone. 

Smectite is the first secondary mineral to form upon rock weathering in the semi-arid to sub-humid tropics. Smectite clay retains most of the ions, notably Ca2+ and Mg2+, released from weathering primary silicates. Iron, present as Fe2+ in primary minerals, is preserved in the smectite crystal lattice as Fe3+. The smectites become unstable as weathering proceeds and basic cations and silica are removed by leaching. Fe3+-compounds however remain in the soil, lending it a reddish color aluminum is retained in kaolinite and A1-oxides. Leached soil components accumulate at poorly drained, lower terrain positions where they precipitate and form new smectitic clays that remain stable as long as the pH is above neutral. Additional circumstances for the dominance of clays are ... 

The processes described and their kinetics is of importance in the accumulation of trace metals by calcite in sediments and lakes (Delaney and Boyle, 1987) but also of relevance in the transport and retention of trace metals in calcareous aquifers. Fuller and Davis (1987) investigated the sorption by calcareous aquifer sand they found that after 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface precipitation. Clean grains of primary minerals, e.g., quartz and alumino silicates, sorbed less Cd2+ than grains which had surface patches of secondary minerals, e.g., carbonates, iron and manganese oxides. Fig. 6.11 gives data (time sequence) on electron spin resonance spectra of Mn2+ on FeC03(s). 

Abiotic organic reactions, such as hydrolysis, elimination, substitution, redox, and polymerization reactions, can be influenced by surfaces of clay and primary minerals, and of metal oxides. This influence is due to adsorption of the reactants to surface Lewis and Br nsted sites. Temperature and moisture content are the most important environmental variables. Under ambient environmental temperatures, some reactions are extremely slow. However, even extremely slow transformation reactions may be important from environmental and geochemical viewpoints. 

Oxidation of Organic Compounds by Oxides and Primary Minerals... 

Similarly to Mn(IV)- and Fe(III)-oxides, some primary minerals were shown to promote polymerization of hydroquinone (19). Olivines, pyroxenes, and amphiboles accelerated the polymerization reaction to a greater extent than micas and feldspars. Microcline and quartz were ineffective- The effect was greatest for tephroite, a manganese-bearing silicate with the ideal chemical formula M SiO. Fayalite, the corresponding Fe(II) analog (Fe2Si0 ), was effective, but to a lesser extent. 

The dissociation of water coordinated to exchangeable cations of clays results in Brtfnsted acidity. At low moisture content, the Brrfnsted sites may produce extreme acidities at the clay surface-As a result, acid-catalyzed reactions, such as hydrolysis, addition, elimination, and hydrogen exchange, are promoted. Base-catalyzed reactions are inhibited and neutral reactions are not influenced. Metal oxides and primary minerals can promote the oxidative polymerization of some substituted phenols to humic acid-like products, probably through OH radicals formed from the reaction between dissolved oxygen and Fe + sites in silicates. In general, clay minerals promote many of the reactions that also occur in homogenous acid or oxidant solutions. However, rates and selectivity may be different and difficult to predict under environmental conditions. This problem merits further study. 

Weathering of snbsurface solid phases occnrs as a result of their direct interaction with liqnid phases, which may also in tnm be affected by the gaseous environment. Examples of weathering processes inclnde reactions that convert primary minerals snch as qnartz and clays into metal oxides and metal hydroxides. 

The degree of transformation can be quantified analytically through the ratio of Fe in the oxides (commonly extracted with the strong reductant sodium dithionite (Fed)) to the total amount of Fe (Fct) and also by the ratio of Fe"/Fe ", because the iron located in the primary minerals of the parent rock is predominantly Fe". With age, the ratio Fea/Fct gradually approaches unity and the total Fe"/Fe " approaches zero (Leigh, 1996). Therefore, both can serve as an indicator of the maturity of a soil as a function of time (chronosequence) (e.g. Italy Arduino et al., 1984 Nepal Baum-ler et al. 1991, Spain Simon et al. 2000 USA Barret, 2001 Egli et al. 2001). The... 

Mineralogical interpretations of Halley dust analyses remain controversial. Lawler et al. (1989) saw no clustering of compositions that might suggest crystalline minerals (Fig. 12.5), whereas Fomenkova et al. (1992) identified compositions that were consistent with a number of minerals, including pyroxene, phyllosilicate, carbonate, FeNi metal, iron sulfide, and iron oxide. The characterization of minerals in returned comet dust (see below) supports the identification of some of these primary minerals but calls into question the identification of those formed by alteration. 

Another major theme is the application of nanocrystalline Ti02 as a photocatalyst for environmental remediation. During the past several decades a broad research community composed of chemists, engineers, and materials scientists has developed technologies that use 2 as the light absorber and primary oxidant to mineralize organic pollutants in water- and air-streams. Three chapters in this... 

Spinel is found as a metamorphic mineral, and also as a primary mineral in basic rocks, because in such magmas the absence of alkalies prevents the. formation of feldspars, and any alnininnin oxide present will form corundum or combine with magnesia to form spinel. This fact accounts for the finding of both ruby and spinel togedier. 111 addmon to the localities mentioned above, which yield beautiful specimens, spinel is found in Italy and Sweden and in Madagascar, Also in the United States in Orange County, New York, and ill Sussex County. New Jersey, are many well-known spinel localities. Spinel is found also in Macon County, North Carolina, and in Canada in Quebec and Ontario. 

FIGURE 21.2 Primary mineral sources of metals. The s-block metals occur as chlorides, silicates, and carbonates. The d- and p-block metals are found as oxides and sulfides, except for the group 3B metals, which occur as phosphates, and the platinum-group metals and gold, which occur in uncombined form. There is no mineral source of technetium (Tc in group 7B), a radioactive element that is made in nuclear reactors. 

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