Minerals: Pi mary Nikolaos |. Barbayiannis Vissarion Z. Keramidas Soil Science Lab, Aristotle University of Thessaloniki, Thessaloniki, Greece INTRODUCTION According to the Glossary of Soil Science Terms\" primary minerals are those that have not been altered chemically since their deposition or crystallization from molten lava (magma). Primary minerals identified in soils belong mainly to the classes of silicates, oxides of Fe, Zr, and Ti, and phosphates (apatite). Their study is essential because: a) they serve as sources of plant nutrients; b) they are, in certain cases, the precursors of secondary clay minerals; and e) they provide infor- mation about soil development. SILICATES Of the primary minerals found in soils, silicates are the most abundant, comprising nearly 40% of the common minerals, The building unit of the silicates, is the silicon tetrahedron. Silicate structures. may consist of single tetrahedra (nesosilicates), double tetrahedra (sorosilicates), rings (cyclosilicates), single or double chains (inositicates), sheets (phyllosilicates), ot framework patterns (tectosilicates). Typical silicate minerals most likely to be found in soils are presented in Table 1 Olivines. Olivines are olive-green nesosilicates in which divalent cations mainly Mg™~ and Fe** join the silicon tetra- hedra by forming octahedra of Mg** or Fe”*. The forsterite-fayalite series include the most abundant naturally occurring olivines, with Mg** and Fe** being the respective cation of the series end members. Olivines are the first minerals to crystallize in the initial stages of magma solidification and they are highly unstable minerals because the high ratio of the divalent cations to silicon in its structure renders them vulnerable to chemical attack. Therefore, olivines are very easily weathered in soils and for this reason they are considered relatively rare soil constituents and ean be found only in very young soils and in the coarser sand fractions. 1084 opr 0208 To cs Zircon Zircon is another nesosilicate mineral. Tts structure consists of alternating edge-sharing silicon tetrahedra that are held together with Zc” ions that are located in the center of triangular dodecahedra."! Zircon is found as residual grains in the sand and, silt fractions of soils and because of its stability in pedogenic environments it is frequently related to the degree of soil development and soil age. Pyroxenes and Amphiboles Pyroxenes and amphiboles are “ferro-magnesian"’ minerals with single and double chain structures, respectively (Table 1). Pyroxene chains have silicon tetrahedra sharing two O atoms. In amphiboles the chains are formed by silicon tetrahedra sharing alter- natively two and three O atoms. In both classes of minerals, the chains are held together mainly by divalent cations (Mg**, Fe**, or Ca**) located at the center of an octahedron ‘Augite and hornblende are the most important minerals of the pyroxenes and amphiboles, respec- tively. Pyroxenes and amphiboles are formed at lower temperatures and pressures during magma solidifica- tion compared to olivines and are more stable in the weathering environment. In soils, however, they weather relatively faster and are largely confined in the sand and silt fractions. Some of them may occur in the clay fraction of soils that are young and have not been subjected to intensive weathering! Feldspars Feldspars are tectosilicates, with three-dimensional framework of corner linked silicon and aluminum tetrahedra, The aluminum tetrahedral result from Al substitution for Si and the charge deficit created is compensated by Na, K, and Ca, Feldspars are virtually present in all sediments and soils in quantities that vary with the nature of the parent material and the stage of weathering, The majority of feldspars belong to the ternary system NaAlSisO, (albite) -KAISi:Os Encyclopedia of Sol Science DOL: 10.1081 /E-ESS-120042713 Copyright © 2006 by Taylor & Francs, All rights reserved,Minerals: Primary Table 1 Common primary minerals of the silicate class found in soils 108s Silicon tetrahedra arrangement "Name of mineral oF group Teal formula ‘Nesoallicates (Si0,)™ (single) Olivine (MaFo)SI0, Zircon 18304 Sorosilicates ($i0;)° (double) Epidote CaXALFO)ALO(Si0,)(Si30 OH) Cyclosilicates (SiO) (rings) Inosiicates Tourmaline (Na,Co)(LiMg.AINALFe.Mn)(BO,) (SiO »XOH)s (ingle chains) (Sis)? Pyroxenes Augite (CaNaj(Mg.Fe AINSiAD.0. Hypersthene (Mg.Fe)Si0, (Double chains) ($i0.)* Amphiboles Hornblende (CaNa.s(Mg,Fe ADsSi(Si,AD):O24(0H)2 Phyltsiicates (SisO,o)* (sheets) Micas Muscovite KAI(AISisO,0\OH)> Tectosilicates (S104) (framework) Foldspars Orthoclase KAISi(Os Albite NaAlSiOs Anorthite CaAl,SiOs Quartz SiO: From Ray (K-feldspar) -CaAl,SizOs (anorthite). In K-feldspars one out of every four Si is replaced by Al, with K balancing the charge. Most common K-feldspars are sanidine, orhoclase, microcline, and adularia, Sodium and calcium feldspars form a series called “plagio- clase” with compositions ranging from pure albite (Na-feldspar) to pure anorthite (Ca-feldspar) The presence of feldspars in soils is related to the overall mineralogical composition and the prevailing environmental conditions, including climate, topogra- phy, degree of leaching, presence of chelating agents, redox status, and soil solution composition." Feldspars usually follow the stability sequence: anorthite < albite < K-feldspars! Weathering of plagioclase minerals increases the supply of Ca in soils in a manner similar to that of ‘weathering of K-feldspars in the clay, and silt fractions provides an important source of K in soils Micas Micas are 2:1 phyllosilicate minerals formed by two silicon tetrahedral sheets and an aluminum octahedral sheet in between. One out of four Si in the tetrahedral sheet is replaced by Al and the high negative layer charge developed is balanced by nonhydrated inter- layer cations that hold the layers tightly together. The most abundant and important micas in soils (muscovite and biotite) have K as the interlayer cation, which upon weathering is released in the soil solution and serves as a plant nutrient. opr 0208 To cs Micas are formed in soils from the parent material, and as they tend to weather to other minerals they are expected to prevail in younger, less weathered soils." In young soils they tend to occur as discrete sand and silt particles, while in more weathered soils they are usually found in the clay fraction. Biotite is uncom- mon in most soils because it is transformed very easily to other secondary minerals, even under mild weather- ing conditions. Muscovite is commonly found in soils of advanced weathering. Like the other primary minerals in soils, mica becomes unstable in the weathering conditions at the soil surface, This is demonstrated by the fact that biotite is almost absent from the surface horizons of most, except very young, soils. Micas are considered as the precursors of several secondary 2:1 minerals and clay minerals in soil like illites, vermicutites, and smectites.®°1 Quartz Quartz is one of the seven polymorphs of SiO, found in soils and sediments: quartz, cristobalite, tridymite, coesite, stishovite, Iechatelerite (silica glass), and opal!" Quartz and disordered cristobalite are the typical forms found in soils while tridymite is present mostly in soils developed ftom siliceous voleanic rocks. Quartz. belongs to the tectosilicate class of the silicate minerals (Table 1), which have each O of silicon tetrahedra linked to Si atoms of adjacent tetrahedra, forming a three-dimensional framework structure.1086 Owing to its resistance to weathering, quartz is gener- ally concentrated in the sand and silt fractions, and generally elluvial (surface) horizons are enriched owing to weathering and removal of less resistant minerals. Quartz is considered as inert sceletic material and exhibits very small to nil anion and cation exchange properties. In certain horizons, however, poorly erystal- line quartz and other silica minerals may serve as cementing agents. In normal soils, quartz particles are also considered as important components of the soil structure because they are linked together or to clay domains through organic matter bridges!""! Quartz is also a suitable mineral to assess parent material unifor- mity and degree of weathering because of its abundance, resistance to weathering, and immobility OXIDES Iron OF the several iron oxides and hydroxides found in soils, magnetite (FesO,), is the only one of primary origin, The erystal structure of magnetite, like all iron oxides, consists of Fe ions surrounded by six O in a sixfold coordination Magnetite occurs as black grains in the heavy fraction of the sand and sit fraction of soils and is of lithogenic origin!) As magnetite is found in the coarser soil fractions and is easily transformed to ‘maghemite in the finer fractions, its influence on soil ‘chemistry is minor. Titanium Rutile (Ti2) and ilmenite (FeTiOs) are the main primary titanium minerals found in soils. Rutile is tetragonal and consists of TiOg polyhedra that share their opposite edges and form chains along the c-axis. Titanium oxides are common accessory minerals of igneous and metamorphic rocks and have been identi- fied in the sand and silt fractions of soils originating from such rocks. Rutile develops a negative charge through adsorp- tion of OH” on surface Ti ions. This charge is pH dependent, Charge development plays an important role in sandy acid soils and influences physical and chemical properties such as formation of stable aggre- gates and retention of nutrients such as phosphate Titanium oxides, in the similar way as zircon, are ‘most frequently related to soil genesis studies. Theit occurrence in the nonclay fraction in the different horizons of soils and the parent material provides information about the profile uniformity and soil development. opr 0208 To cs ‘Minerals: Primary PHOSPHATES Phosphate minerals comprise only a small part of the inorganic fraction of soils and their basic structural unit is the orthophosphate ion (PO,* ), which forms tetrahedron where P is surrounded by four O* ‘The high affinity of PO,* for cations, forms structures, that are classified as framework, chain, and layer phosphates, similar to silicates."°) Apatite [CaoPO.)e (CL.F,OH)s] is the most frequently reported phosphate of igneous origin and has been identified with photo- graphic microscopy as discrete grains in the sand and silt fraction of a number of soils. Along with their weathering products, apatites are considered as a natural source of P for plants. CONCLUSIONS Primary minerals identified in soils belong mainly to the classes of silicates, oxides of Fe, Zr, and Ti, and phosphates and are usually found in the sand and silt fractions. In soils they are inherited from the parent material and their presence is predicated by the nature of the mineral and the intensity of weathering which results in the formation of secondary clay minerals in soils and the release of clements, essential for plant growth, in the soil solution, Therefore, primary miner- als play a significant role in soil formation and in the ong run they serve as sources of plant nutrients. ARTICLES OF FURTHER INTEREST Clay Minerals: Weathering and Alteration of, p. 281 Magnesium, p. 1045. Potassium, p. 1354, REFERENCES 1. Soil science society of America. Glossary of Soil Science Terms; Bigham, JM., Bd; SSSA: Madison, WI, 1997; 134 pp. Shultze, D.E. An introduction to soil mineralogy. In Minerals in Soil Environments, 2nd Ed.; Series 1; Dixon, I.B,, Weed, S.B., Fas; SSSA: Madison, WI, 1989; 1-34 3. Deer, W.A.: Howie, RA: Zussman, J. An Introduction to the Rock Forming Minerals, Longman Lid: Essex, England, 1992; 696 pp. 4. Huang, PM. Feldspars, olivines and amphiboles. In Minerals in Soil Environments, 2nd Ed.; Series 1.B., Weed, $.B, Eds; SSSA: Madison, WI. 1050, 5. Churchman, GJ. The alteration and formation of soil ‘minerals by weathering. In Handbook of Soil Science Sumner, ME, Ed; CRC Press: Boca Raton, FL, 2000; F3-F76‘Minerals: Primary 6. Allen, B.L; Hajek, BF. Mineral occurrence in soil cavironments, In Minerals in Soil Environments, 2nd Ed: Series 1; Dixon, J.B, Weed, S.B, Eds: SSSA: Madison, WI, 1989: 199-278. 7. Fanning, D.S; Keramidas, V.Z; ElDesoky, M.A. Micas. In Minerals in Soil Environments, 2nd Ed; Series 1; Dixon, J.B., Weed, $.B., Eds; SSSA: Madison, WI, 1989; 951-634, 8. von Reichenbach, H.G.; Rich, C1. Fine grained micas in soils. In Soil Components. Part 2. Inorganic Compo- nents, Giescking, JE., Ed.; Springer: Berlin, 1975; 59-95, 9. Borchardt, G. Smecttes. In Minerals in Soil Environ- ments, 2nd Ed. Series 1: Dixon, J.B, Weed, S.B. Eds.; SSSA: Madison, WI, 1989; 675-727, opr 0208 To cs 1087 Drees, LR; Wilding, LP Smeck, NIE; Senkeyi, Abu L. Silica in soils: quartz and disordered silica polymorphs. In Minerals in Soil Environments, 2ad Ed; Series 1; Dixon, LB, Weed, SB, ds: SSSA: Madison, WI, 1989; 913-974, Emerson, W.W. The structuze of soil crumbs. J. Soi Sc 1959, 10, 235-244 Schwertman, U.; Taylor, R.M. Iron oxides. In Minerals in Soil Environments, 2nd Ed; Series 1; Dixon, IB, Weed, S.B., Eds; SSSA: Madison, WI, 1989: 379-438, Lindsay, W-L; Viek, LG. Chien, S.H. Phosphate minerals. In Minerals in Soil Environments, 2nd Ed. Series 1; Dixon, J.B., Weed, $.B., Eds; SSSA: Madison, WI, 1989; 1089-1130,