Silicate primary soil minerals

Primarily, Fe is released from the lithosphere into surface environments including soils by veathering of primary silicate and sulphide minerals (Tab. 16.1). In the presence of O2 and H2O and in the common pH range (>2) of surface environments, the released Fe" is oxidized to Fe " which in turn, is immediately hydrolysed to form Fe " oxides and oxide hydroxides. For Fe" silicates these reactions involve breakage of an Fe"-0-Si bond and the formation of Fe "OH and SiOH groups. For example, goethite may be formed from the oxidation and hydrolysis of olivine (fayalite) through the reaction ... 

The spring waters of the Sierra Nevada result from the attack of high C02 soil waters on typical igneous rocks and hence can be regarded as nearly ideal samples of a major water type. Their compositions are consistent with a model in which the primary rock-forming silicates are altered in a closed system to soil minerals plus a solution in steady-state equilibrium with these minerals. Isolation of Sierra waters from the solid alteration products followed by isothermal evaporation in equilibrium with the eartKs atmosphere should produce a highly alkaline Na-HCO.rCOA water a soda lake with calcium carbonate, magnesium hydroxy-silicate, and amorphous silica as precipitates. 

The total amount of Fe in soils varies widely, ranging from 200 pg g to more than 10%. In soils, Fe is found as oxides, hydroxides, and phosphates, as well as in the lattice structure of primary silicate and clay minerals. 

Secondary silicates form as clay minerals in soils after weathering of the primary silicates in igneous minerals. The secondary silicates include amorphous silica (opal) at high soluble silica concentrations and the very important aluminosilicate clay minerals kaolinite, smectite (montmorillonite), vermiculite, hydrous mica (il-lite), and others. Kaolinite tends to form at the low silicate concentrations of humid soils, whereas smectite forms at the higher silicate and Ca concentrations of arid and semiarid soils. The clay fraction of soils usually contains a mixture of these day minerals, plus considerable amorphous silicate material, such as allophane and imogolite, which may not be identifiable by x-ray diffraction. 

Layer silicates, sheet-like phyllosilicates such as the familiar micas, are in primary rocks and in soils. The soil minerals are often called clay minerals. Since other components can also be in the clay fraction, layer silicates is a mom accurate term. A typical layer silicate is a combination of a layer of Al-, Mg-, or Fe(II)-0 octahedra plus one or two layers of Si-0 tetrahedra. The tetrahedral and octahedral sheets bond together by sharing oxygens at the corners of the tetrahedra and octahedra. Layer silicate minerals are differentiated by (1) the number and sequence of tetrahedral and octahedral sheets, (2) the layer charge per unit cell, (3) the type of interlayer bond... 

Iron and manganese occur in a number of soil minerals. Sodium and chlorine (as chloride) occur naturally in soil and are transported as atmospheric particulate matter from marine sprays (see Chapter 10). Some of the other micronutrients and trace elements are found in primary (unweathered) minerals that occur in soil. Boron is substituted isomorphically for Si in some micas and is present in tourmaline, a mineral with the formula NaMg3AlgB3Sig027(0H,F)4. Copper is isomorphically substituted for other elements in feldspars, amphiboles, olivines, p5Toxenes, and micas it also occurs as trace levels of copper sulfides in silicate minerals. Molybdenum occurs as molybdenite (M0S2). Vanadium is isomorphically substituted for Fe or A1 in oxides, pyroxenes, amphiboles, and micas. Zinc is present as the result of isomorphic substitution for Mg, Fe, and Mn in oxides, amphiboles, olivines, and pyroxenes and as trace zinc sulfide in silicates. Other trace elements that occur as specific minerals, sulfide inclusions, or by isomorphic substitution for other elements in minerals are chromium, cobalt, arsenic, selenium, nickel, lead, and cadmium. 

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. 

Once a layer-silicate clay forms, it does not necessarily remain in the soil forever. As conditions change it too may weather and a new mineral may form that is more in equilibrium with the new conditions. For example, it is common in young soils for the concentrations of cations such as K, Ca, or Mg in the soil solution to be high, but as primary minerals are weathered and disappear, cation concentrations will decrease. With a decrease in solution cations, a layer-silicate such as vermiculite will no longer be stable and can weather. In its place. 

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 ... 

Most primary and secondary minerals found in soil systems are barely soluble in the soil solution. The amount of mass from the bulk phase to hydrated ions in soil solution is negligible compared to the total mass of the solid phase. In arid and semi-arid soils, concentrations of most trace metals in soil solution may be controlled by their carbonates and to some extent by their hydroxides. Other than carbonates, trace elements in arid and semi-arid soils may also occur as sulfate, phosphate or siliceous compounds, or as a minor component adsorbed on the surface of various solid phase components. The solubility of carbonates, sulfates and other common minerals of trace elements in arid and semi-arid soils will be discussed in Chapter 5. Badawy et al. (2002) reported that in near neutral and alkaline soils representative of alluvial, desertic and calcareous soils of Egypt, the measured Pb2+ activities were undersaturated with regard to the solubility of... 

Bloesch, P.M. Bell, L.C. Hughes, J.D. (1987) Adsorption and desorption of boron by goethite. Aust. J. Soil Res. 25 377-390 Blomiley, E.R. Seebauer, E.G. (1999) New approach to manipulating and characterising powdered photo adsorbents. NO on Cl treated Ee20j. Langmuir 15 5970-5976 Bloom, P.R. Nater, E.A. (1991) Kinetics of dissolution of oxide and primary silicate minerals. In Sparks, D.L. Suarez, D.L. (eds.) Rates of soil chemical processes. Soil Sci. 

Aqua regia extraction is a strong partial extraction method that dissolves carbonates, most sulphide minerals, some silicates like olivine and trioctahedral micas, clay minerals and primary and secondary salts and hydroxides (Salminen, 1995). It can be considered a quasi-total extraction method, since actual total concentrations can be higher. On the other hand, this leaching method overestimates the bioavailable amount of toxic elements in a soil since metals trapped in the silicate lattice are released very slowly in the environment and are not easily involved in plant nutrition processes. 

The results show that the sorption of cyanide on soils and sediments is fast it reaches equilibrium within 10 minutes. The sorbed quantity, however, is low. From 10 4-10 3 mol/dm3 cyanide solutions, it is about 10 7 mol/g. This means an approximately 10-3 dm3/g distribution ratio for cyanide ion. This value is typical for the anion sorption of soils, and it is explained by the interfacial properties of soil components. The main mineral components of soils (primary silicates, clay minerals, oxides) have negative surface charges at pH applied (about 8.5), inhibiting the... 

The result of these various processes is that the Earth s cmst, the parent material for soils, is dominated (in mass) by eight elements (oxygen, silicon, aluminum, iron, calcium, sodium, magnesium, and potassium). These elements, with the exception of oxygen, are not the dominant elements of the solar system. Thus, soils on Earth form in a matrix dominated by oxygen and silicon, the elements which form the backbone of the silicate minerals that dominate both the primary and secondary minerals found in soils. 

Figure 12 Surface area parameters (a) surface area of primary silicate minerals contained in soils of the Merced chronosequence (after White et al., 1996). (b) Surface roughness of sihcate minerals as functions of the duration of experimental and natural weathering (source White and Brantley, 2003).

Alexandre et al. (1997) found that the biogenic sihca input into the biogeochemical silica cycle from the dissolution of phytoliths is twice as large as silica input from primary silicate mineral weathering in the tropical Congo rainforest. Biogenic (opaline) silica dissolves faster than sihcate minerals. While most of the phytoliths dissolve rapidly with a mean residence time of 6 months (Alexandre et al., 1994), and the sihca is recycled by the forest, a small part (7.5%) does not dissolve and is preserved in the soil. 

Source After H. Sverdrup and P. Warfvinge. Weathering of primary silicate minerals in the natural soil environment in relation to a chemical weathering model. Water, Air and Soil Pollution 38 387-408. 1988 by Kluwer Academic Publ. Used by permission. 

Layer Silicates. Although the common primary minerals include island, chain, sheet, and framework silicates, the most stable and persistent silicates, which occur as weathering products (secondary minerals) in the clay fraction of soils, are sheet silicates. Figure 2.9a depicts the structure of the tetrahedral sheet in these minerals, which is comparable to the tetrahedral structure of mica. For the layer silicate clays, however, numerous structural combinations of the tetrahedral sheet with octahe-drally coordinated metal cations are possible. 

The solid phase of soils can consist of many Al-bearing materials, including organic matter oxides and hydroxides of Al noncrystalline aluminosilicates layer silicate clays and various primary minerals. Any model of Al solubility that is based on the dissolution reaction of only one of these materials is likely to be too simple. Nevertheless, some of these models will now be considered in turn. 

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