Geological Society, London, Engineering Geology Special Publications 2.

The composition of clay materials
Geological Society, London, Engineering Geology Special Publications 2006; v. 21; p. 13-27 doi:10.1144/GSL.ENG.2006.021.01.02

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80- ~gz . smectite in bentonites. 14). mineral and organic compositional variations reflect the weathered parent rocks and the physical. Some clay materials may be dominated by one mineral phase. occur either as 'bound phases'. phases in clay materials. Detrital mineralogy of sedimentary rocks as a function of ~rain size (after Blatt et al. However. 1972). it needs to be stressed that. The mineralogy can be broadly subdivided into the clay and non-clay minerals. e. chemical and biological factors controlling the soil forming processes (see Chapter 3). 2.g. 2.1.'co t. The majority of clay minerals have sheet silicate structures (see Text Box on p.1. if not predominant.2. so-called 'amorphous' inorganic phases. opal in diatomaceous earths. 2. minerals are crystalline solids with well-ordered crystal structures but clay minerals and other inorganic phases in clay materials are often poorly crystalline compared to minerals such as quartz and feldspar. 1972). Shaw & Weaver (1965) reported the modal mineralogical composition of siliciclastic mudrocks to be: 60% clay minerals 30% quartz and chert 5% feldspar 4% carbonates 1% organic matter 1% iron oxides There is a general increase in the predominance of clay minerals in sedimentary rocks with decreasing grain size 100 - (Fig. adsorbed onto the surfaces of the solid particles.1) (Blatt et al. most clay materials are composed of heterogeneous mineral mixtures.kl r ~ r ~--- Sand I Silt I Clay FIG. The liquid and vapour phases. Based on the bulk mineral analysis of over 400 samples. Clay minerals The clay minerals are a group of hydrous aluminosilicates that are characteristically found in the clay ( < 2 gm) fractions of sediments and soils. In soils. The solid phases are of mineral and organic phases that make up the framework of the clay materials. liquid and vapour phases. By definition. whilst clay minerals are usually significant. of which water is usually the most important. I he composition of clay materials Clay materials are composed of solid. In this chapter the nature of the mineralogical. However. or as 'free phases' within pore spaces. including poorly crystalline. . other mineral phases are usually present in varying amounts and can significantly affect the properties and behaviour of the materials. organic and aqueous phases present in clay materials are described plus the nature of swelling and ionic exchange properties in solid phases.

iiii!!::i FIG. :ii:..2.~il i ~iil.! ~:: ~. 2. Composite layers in clay mineral structures.:i:.: ::i:iii~::i::::i~: i:!. :ii::ii/:i: i iii~:!:i:::i::~: !i. ~.:~:~.i!:%i! :i::~ ~ i~i~::: ! iliii !i::!ii:!!i iiii:!i}:i~:~i::ii: i :i! )i:!i:.!ii:i :i:iii~if: i :i~iiI i i::~iiiii iii iii if i!~ i iiiiiiili.:ii!~.:~i: !i::!ilii:ii:::ii. .!ii!.i: : iir:.14 THE COMPOSITION OF CLAY MATERIALS Th~.:she~i Nr i i!i!::if: ii.: ~: :~: ~.!:ii~ili!ii!!i!i ii!:!?i !if: ~?i ii:: :i?.

2. Removal of the water layer causes the halloysite structure to collapse to a 7A interlayer spacing.6).1). Classification of clay minerals Sheet silicate type 1:1 ~p___~ Kaolin and serpentine 2:1 type Illites Chlorites Smectites (Montmorillonites) Vermiculites Mixed layer clays with smectite/ vermiculite Mixed layer clays without smecfite/vermiculite Palygorskite and sepiolite Property Non-swelling Non-swelling Non-swelling Swelling Swelling Swelling Non-swelling Non-swelling There are two types of composite layer structures in the clay minerals: 9 the two layer or 1 : 1 type represented by the kaolin and serpentine groups. The illlite-mica group The kaolin group of minerals is the most common of the clay minerals with the two layer 1 : 1 type of structure.1.5).2. The term kandite has also been used to describe kaolin group minerals but is not the preferred name. Specific names have also been Illite is the term generally used for all clay grade micas and most commonly has a dioctahedral 2:1 or three-layer composite layer structure (Fig.1. Halloysite is a kaolin group mineral that contains one water layer in the interlayer sites. 2. .4) or water layers. dickite and nacrite of general formula A14Si4Oa0(OH)8. There are three principal polymorphs (or polytypes). Potassium is the principal interlayer cation and lenses of water may also be present in the interlayer sites (FIR. 2. A1)xSi4_xAlx)O10(OH)8)is the most important member of the serpentine group in studies of sedimentary rocks.3. 2. Halloysites usually have a characteristic tubular morphology though other spheroidal habits have been reported (Fig. Chamosite is not a 7A serpentine mineral but a 14A chlorite mineral (see Section 2.2). smectite. no net negative charge on the composite layers and consequently no compensating interlayer cations (Fig.0 per O10 (OH)2 formula unit. 16) Kaolinite can range from well crystallized varieties to poorly crystalline forms that can be differentiated by X-ray powder diffraction analysis (see Section 8. 2. It commonly occurs in oolitic ironstones and in pedogenic environments but has often been misnamed chamosite. General structures of clay minerals. vermiculite and chlorite groups (Fig. producing a 10)~ interlayer spacing rather than the 7A spacing of the kaolinite structure. The collapsed form is referred to as 7A halloysite (or metahalloysite) as opposed to the hydrated 10A halloysite.1. Kaolins have dioctahedral structures with.1.6). kaolinite.7-1. 2.5).THE COMPOSITIONOF CLAYMATERIALS 2 layer (I:I]type Tetrahedral layer Octrehedral layer 3 layer (2:1)type | Interlayer sites X X KAOLINITE ILLITES SMECTITES VERMICULITES CHLORITES FIG.1. 2. 2. 9 the three layer or 2:1 type represented by the illitemica. ideally. 2. TABI~E 2. The kaolin and serpentine groups given to kaolin-rich deposits that occur in different formation environments (see Text Box on p. Berthierine (Fe 2+.3 and Table 2. The serpentine group of minerals is the trioctahedral equivalent of the kaolin group. Its general formula is A14Si4010(OH)8"H20. Mg)6_x (Fe 3+. In the illite structure substitution of [Si4+]iv by [A13+]iv and [R3+]w by [W+] vI produces a net negative charge of about 0. The tubular morphology arises from the distortion and curving of the 1 : 1 layer structure from which the tubular habit develops.

The hydration of the interlayer cations causes the interlayer crystalline swelling that characterizes the smectites.7) that are most commonly dioctahedral but trioctahedral varieties do exist. Crystal structure of kaolinite (A14Sc40l0 (OH)8).55A1045)O. Water is sorbed into the interlayer sites .4. Illite Ko. which is offset by hydrated interlayer cations. usually basaltic. 2.6 per O10(OH)2 unit of structure. Mg > Fe 2+ and Fe 3+ > F e z + However.3.2-0. They have a layer charge of 0.67Alo. principally Ca and Na. celadonites are most commonly formed in association with the alteration of volcanic.65R2+0. Fe 3+)Si40~o(OH)2. Unlike glauconites that are most often found in modern and ancient sediments. Smectites Smectites are three-layer or 2:1 clay minerals (Fig.16 THE COMPOSITIONOF CLAY MATERIALS FIG.33) (Si3. 'glauconite' is also used to describe any green (pelletal) clay material irrespective of composition (see Text Box on p. The term 'glaucony' has been proposed as a general term when the specific mineral composition is not known (Millot 1970). rocks.0(OH)2 Muscovite KA12(Si3A1)Olo(OH)2 Sericite is also used to generally signify fine-grained micacaeous material of an indeterminate nature that may include illite but also other clay and sheet silicate minerals..s(R3+. Glauconite (sensu stricto) is a dioctahedral Fe-rich illite of general formula K(R 2+067R3+. Celadonite is the more Mg-rich equivalent of glauconite of ideal formula K(Mg. 2.35) (Si3. Fe 2+. 18). 2..1.33)Olo(OH)2 with Fe 3+ >> A1.

8)..THE COMPOSITIONOF CLAYMATERIALS 1/ composed predominantly of montmorillonite and/or to indicate genesis of montmorillonites from alteration of volcanic ash.1. In the UK Fullers Earth is used in a similar way to bentonite though in North America Fullers Earth can be composed of palygorskite rather than smectite (montmorillonite). Dioctahedral smectites: Montmorillonites R+y(A12_y R2+y)Si4Olo(OH)z'nH20 Beidellite R+yAlz(Si4_yAly)O10(OH)2"nH20 Nontronite R+yFe3+2(Si4_yAly)Olo(OH)z'nH20 Trioctahedral smectites: Saponite R+x_y(Mg3_y(A1.5.8 per O10(OH)2. Chlorite The chlorites have a 2:1 type structure with a second octahedral layer in the interlayer sites having a net positive charge to offset the net negative charge on the 2:1 layers (Fig. Vermiculite FIG. The principal interlayer cations are hydrated magnesium. As a rock term. it used to signify a commercial clay deposit Vermiculites are similar in structure to the smectites (Fig. Na and Camontmorillonites can absorb up to three layers at 90% relative humidity but in some instances at 100% humidity.1.9) but have a larger net negative charge on the composite layer of 0. . Na-montmorillonites can absorb more and the 2:1 layers disperse.Fe 2+)3_y(A1.6-0.6. 2.Fe 3+)y)(Si4_x Alx) Olo(OH)2"nH20 Hectorite R+x_y(Mg3_yLiy)Si4Olo'(OH)z'nH20 2. Vermiculites are trioctahedral with the general formula: Mg (x-y~/2(Mg. Bentonite is often used synonymously with montmorillonite but is a rock term rather than a mineral name. 2. 2.5. 2. Vermiculites exhibit swelling properties similar to the smectites but to a lesser extent due to the higher layer charge. in monomolecular sheets (Fig.4. FIG. 2.10). 1978. Photomicrograph of tubular habit of halloysite (from Kohyama et al. Crystal structure of muscovite. reproduced by permissionof the authors and publishers). Fe3 +)y (Si4_x Alx)O10(OH)2"nH20 2.

7. 2. . Crystal structure of dioctahedral smecite. 2.18 THE COMPOSITION OF CLAY MATERIALS FI6. FIG.8. One layer and two layer water structures in smectite (from Velde 1992).

THE COMPOSITION OF CLAY MATERIALS 19 FI6. FIG. 2. Generally the 2:1 clay minerals are most commonly involved in forming mixed layer clay minerals.9. Fe 3+)xSi4_x Al~Olo(OH)8 2.10. The general formula of the chlorites is (Mg. Crystal structure of chlorite. The most commonly reported mixed layer . Fe 2+)6_x(A1. 2.1. Mixed layer clay minerals The majority of chlorites are trioctahedral but some dioctahedral and mixed dioctahedral (2:1 layers) trioctahedral (interlayers) forms are known and can be identified by X-ray diffraction analysis (see Chapter 8). Mixed layer clay minerals describe those mineral phases in which different sheet silicate units occur in the stacking sequence. though kaolinite-smectites and serpentine-chlorites have been reported.6. Crystal structure of vermiculite.

The nature of illite-smectite as defined by the interstratified and interparticle models (after Nadeau & Bain 1986).g.1. [AP + ] v . H20. but palygorkite is the preferred mineral name. A 'dry' smectite absorbs water into the interlayer sites in discrete layers with the water forming hydration sheaths around the interlayer cations. clays are the illite-smectites and to a much lesser extent the chlorite-smectites. or ordered.1). Sepiolite and palygorskite Exchange cations.organics I 2OA "lllite" Sm lq Exchangecations. Specific names are also given to certain types of ordered mixed layer clay minerals.H2O. 2. Complete dissociation of the clay layers occurs when the repulsive forces of the negatively charged clay surfaces exceed the forces of attraction between the hydrated interlayer cations and the clay particles.8. Vermiculites. At very high humidities Na-smectites when immersed in water exhibit osmotic swelling and may completely dissociate. i.12).1).e. The interstratification may be random.20 Interstratified Model THE COMPOSITION OF CLAY MATERIALS Interparticle Model 10A "Smectite" m Sm Sm Exchangecations. AABAABAA or AAABAAB.11.organics Although sepiolite and palygorskite are often described as 2:1 sheet silicates. 10A "Smectite" 2. I I I K+ K+ K+ K+ 3OA "lllite" The name attapulgite is often used for commercial deposits of palygorskite. Generally mixed layer illite-smectites with more than 45% smectite are randomly interstratified. show less swelling and will not completely dissociate in water. those with 30-45% smectite can be random or ordered and with less than 30% smectite are ordered (Bethke & Altaner 1986). 2. The sorption of water and organic molecules into the interlayer sites is responsible for the characteristic intraparticle swelling properties of smectites and vermiculites (Table 2. Consequently they have fibrous rather than the typically platy habits of the true sheet silicates. with no discernible pattern in the stacking sequence.7.organics ) Sm Sm ( K+ K+ The mixed layer phases may also show segregations into AB sequences with separate domains of A or B rather than continuously alternating sequences. the sheets are not continuous but form alternate ribbons of 2:1 sheet silicate structures (Fig. Water and organic molecules may be sorbed onto the surface of and into the interlayer sites of clay minerals.1. The clay minerals can be classified into swelling and nonswelling varieties (Table 2. ABABAB. H20. 2. Swelling properties of clay minerals I J / / Tetrahedral layers L Octahedral layers "N Tetrahedral layers Fro. Mg being the principal cation in the octahedral sites but in some palygorskites aluminium can be the more common octahedral cation. e. . having a higher interlayer charge than smectites. > [Mg2 +]vi. Compositionally they are Mg-rich.

Low 1992).13. 2. A13+ for Si4+. Crystal structures of palygorskite and sepiolite. Sepiolite and palygorskite have open channel sites similar to zeolites (see Section 2. Fe3+).1. Illites may have lenses of water in the interlayer sites.13) (van Olphen 1977). 2. .2. In addition to intraparticle swelling. When suspended in water some of the interlayer cations on the surface of the clay particles go into solution producing a negatively charged clay surface surrounded by a diffuse' double layer' of hydrated cations (Fig. Guven & Pallastro 1993. 2.g. Ion exchange properties of clay minerals The 2 : 1 clay minerals have a net negative charge on their composite layers due to cation substitutions (e. surface cations (Guven 1993. Interparticle associations of clays control their flocculation and dispersion in natural waters. It seems probable that 'swelling chlorites' are most likely to be mixed layer chlorite/smectites or chlorite/vermiculites rather than a swelling chlorite s e n s u s t r i c t o .THE COMPOSITION OF CLAY MATERIALS 21 PALYGORSKITE -I-- solution -I- + m + - 0 m +-+ + + + _ -t-I-- + - L SEPIOLITE j m + + 0 m ++ + + + + + + + + + + -I- \ ( \ / \ f I 27~.12. out not complete layers and do not show intraparticle swelling. Moore & Reynolds (1997) commented that swelling chlorites are such a poorly described phase they were unable to calculate their diffraction characteristics. but in reality limited cation substitution may occur producing a very small net negative charge on the composite layer offset by a small number of interlayer cations. Mg 2+ for AP +. all clay minerals can show interparticle swelling which is governed by similar factors that control intraparticle swelling. Halloysites in the hydrated state have a water layer between the 7N kaolin layers producing their characteristic 10/~ interlayer spacing. that is the nature of the clay minerals and the nature of and concentration of cations adsorbed onto the clay surface in the diffuse double layer and hydration of d i s t a n c e from c l a y s u r f a c e FIa.7) into which water and organic compounds can be absorbed or desorbed without significantly affecting the unit cell dimensions and thus are not regarded as swelling clays. ~ Tetrahedrallayer Octahedrallayer Tetrahedral layer I Ion concn n+ Fro. Distribution of ions in the clay-water layer of thickness d and formation water. Kaolins ideally have neutral composite layer structures. 2. In minerals such as illites and smectites the net negative charge is offset by interlayer cations and in the chlorites by the interlayer octahedral sheet. FEZ+. Chlorites are non-swelling clay minerals but there have been reported instances of'swelling chlorites'.9. Kaolinite in contrast to halloysite does not swell in the presence of water though increasingly disordered kaolinites contain lenses of water.

Edge site anion exchange as a function of pH (from Yariv and Cross. A13+ and A1045-....HOH OH Si In alkaline solution negatively charged Ca tion exchanger )o Si \ OH / Si O_AI'I-2 // /OAI034 Si ? AI .. being negatively charged in alkaline solutions and positively charged in acidic solutions (Fig. Oxides and organic matter commonly coat clay particles and also have ion exchange properties.A I +2 \OAIO~ 4 In alkaline solution in the presence of AIO4 s" ions negatively charged Cation exchanger In acid solution in the presence of AI3+ions positively charged Anion exchanger Flc. In acid solution positively charged Anion exchanger O-. 2.HOH Si A(-OH + 2 /\O. This pH dependent charge accounts for only a small percentage of the total charge in illites and smectites.OAIO~ 4 \ /o \ / Si Si O .H Si \o / A I .. The degree to which exchange reactions take place depends on the nature of the clay minerals and the concentrations of the cations/anions involved and of other ionic species.. 2.NON /\o Si \o. The ions principally adsorbed onto the clay surfaces and. OH-.. The nature of the charge is determined by the presence of certain ions.O-. but is more significant for kaolins and chlorites. on the edges of the clay particles. to a lesser extent. In addition to cation exchange it is also possible to have anion exchange but usually to a lesser extent than cation exchange. This gives rise to the phenomenon of cation/anion exchange.A I +2 \ \o A [ . On the edges of the clay particles the disruption of the clay structure produces broken bond edge sites which may be negatively or positively charged..14).14.. whose presence is pH dependent..O . 1979). can be exchanged with other available ions. which are strongly . H /O-. notably H +.22 THE COMPOSITION OF CLAY MA'IERIALS OH Si O.

Cations of higher valence will usually replace those of lower valence and. 2.2. Because the edge sites are also involved in ion exchange and as the nature of the charge on the edge sites is pH dependent the cation exchange capacity of individual clay minerals are also pH dependent. Quartz and chert Quartz is commonly present in clay materials.2. In swelling clay minerals.2). 2. less commonly.THE COMPOSITIONOF CLAYMATERIALS TABLE 2. Calcite (CaCO3) and dolomite (CaMg(CO3)2 are the predominant carbonate minerals in clay materials. relatively hard material composed of finely crystalline quartz crystals or fibrous chalcedonic quartz. According to Shaw & Weaver (1965) there is an average of about 4% by weight of carbonate minerals in siliciclastic mudrocks but this can be highly variable. the greater the concentration of a particular cation in solution. Carbonates 2. Silicification may occur during early diagenesis with the dissolution of biogenic silica. feldspars in clay materials are predominantly detrital in origin. the cations will be hydrated and it is the size of the hydrated cation that needs to be considered. smaller sized cations will replace larger sized cations. It is a dense. biochemical or biogenic origin. the more readily it will replace equivalent cations adsorbed onto the clay surfaces and interlayers. though siderite (FeCO3) may also be locally important. Chert is a general description for fine-grained siliceous sediments of chemical. vaterite (hexagonal) also occur in Recent clay materials. The carbonate may be present as clasts derived from organic skeletal remains and the weathering of pre-existing carbonate rocks or as diagenetic cements and nodules. However. Cation exchange capacities of some clay minerals (meq/lOOg) at p H = 7 (after Drever 1982) 23 Smectite Illite Kaolin Chlorite 80-150 10-40 1-10 < 10 dependent on pH. and can alter the cation/anion exchange capacities of associated clays in natural systems. a possible source for the later inorganic precipitation of quartz (Millot 1970). it is important to note that in the diffuse layer. but some may be biogenic or authigenic in origin.2.2.3). . Non-clay mineralogy 2. Cherts usually occur as either bedded or nodular forms. These processes are considered to be often related to the maturation of organic matter during diagenesis (Curtis 1983). Feldspars As with quartz. usually derived from the diagenetic alteration of volcanogenic or biogenic opaline silica (see Text Box below). The nodular forms hosted in chalks and other carbonates are specifically referred to as flints.2. but there is petrological evidence to suggest they may also form diagenetic cements around existing feldspar grains. Jasper is a red coloured chert that contains hematite impurities. if of the same valence. Berner 1981). predominantly in the silt grade material (Fig. whereas for other clays only the outer surface sites will be involved. aragonite (orthorhombic) and. Metastable polymorphs of CaCO3. It is generally detrital. 2. Ion exchange is a dynamic process governed by the law of mass action. Dolomite and siderite formation are favoured in sulphate-depleted environments (Baker & Kastner 1981.3. The source of carbonate for the formation of diagenetic carbonate cements or nodules may be from the recrystallization of primary (skeletal) carbonate material and/or direct precipitation from alkaline bicarbonate-rich pore waters. The presence of authigenic siderite is indicative of anoxic sulphate-depleted conditions at the time of its formation (Table 2. The bedded forms are commonly associated with volcanic sequences whereas nodular cherts are mainly hosted in chalks or mudrocks. Generally. Diagenefic modification of clay minerals may also cause the mobilization of SiO2 which may reprecipitate as a quartz cement in mudrocks or adjacent sandstone beds.1.2. the interlayer cation sites will also provide exchange sites.1). This explains the higher cation exchange capacities of the smectites compared to the illites (Table 2.

For example. scattered crystals and infilling/replacing/pseudomorphing skeletal fragments.6. with gypsum (CaSO4"2H20). Boehmite is isomorphous with lepidocrosite and diaspore with goethite. As described above.3-2.g.silicon oxyhydroxides. Classification of oxic-anoxic environments using authigenic Fe-mineral indicators (Berner 1981) Environment Oxic Anoxic (sulphidic) Anoxic (non-sulphidic) (a) post-oxic (b) methanic Authigenic Fe-minerals Hematite.0 for allophane (Moore & Reynolds 1997).4. Ion exchange in oxides and hydroxides. that characteristically occur in soils derived from the weathering of volcanic "ocks. followed by anhydrite (CaSO4) being the most common. Weathering of pyrite produces iron hydroxides/oxides and mobilizes sulphate which may be incorporated into sulphate minerals such as gypsum and jarosite.6.2. 0 2 2. Iron oxides and hydroxides are present in various mineral forms in clay materials.1. barite (BaSO4) and the more water-soluble sodium and magnesium sulphates may also occur. Pyrrhotite (Fel_xS) is a stable monosulphide mineral phase that occcasionally has been reported in clay materials but stoichiometric FeS. The SiO2:A1203 ratio varies from 1-1. The ettringite group of minerals. lepidocrosite orange. Oxides and hydroxides 2. Marcasite is an orthorhombic dimorph of pyrite that has occasionally been reported in clay materials. They are commonly associated with aluminous smectites formed by the weathering and alteration of . Sulphates may form nodules or veins in clay materials. the mineral troilite.2. the ZPC for boehmite is 8. Goethite is yellow-brown. when conditions are more acidic than the ZPC the oxide/hydroxide will be positively charged and negatively charged for conditions more alkaline than the ZPC.3. mixed calcium carbonate sulphate silicates. Sulphates 2. In addition there are aluminium . which can cause significant damage to concrete structures (Thaumasite Expert Group 1999). though gypsum and various iron sulphates may also form during weathering of shales containing pyrite. and especially thaumasite (Ca3(SO4)(CO3)(Si(OH)6)'12H20). charge arising from broken bonds is pH dependent (Fig.1.5. 2. Generally allophane forms spherules and appears to be less well ordered than imogolite with its typically cylindrical habit. Ettringite group.2.OH). Jarosite (KFe3(SO4)dOH)6) is a distinctively yellow mineral that characteristically forms as surface coatings and aggregates from the oxidation of pyrite to iron sulphate.14). Aluminium oxides and hydroxides. notably hematite (c~-Fe203). imogolite and allophane. Sedimentary authigenic pyrite forms in anoxic sulphidic environments (Table 2.2 and 6 to 7 for goethite (Eslinger & Pevear 1988). 2.2.3). 2. goethite (~-FeO.4). Limonite is a general term for a mixture of iron oxides and hydroxides of a poorly crystalline nature. nodular aggregates. In the oxides and hydroxides the charge on the surfaces arises largely from broken surface bonds producing unshared surface and edge O and OH rather than the cation substitutions that are largely responsible for imparting charge to the clay mineral structures. boehmite (y-AIO'OH) and diaspore (~A10"OH) are the most common of the aluminium oxides and hydroxides and are typically significant constituents of laterites and bauxites. has attracted attention recently because of the observation of the growth of such minerals at concrete-clay boundaries.7. 2.2. TABLE 2. Metastable monosulphide (e.2. is only found in meteorites. the oxidation of the sulphide being the source of the sulphate. The presence of these iron oxides and hydroxides produces the characteristic red/brown/yellow colours of many clay materials depending on which mineral is present.5. Gibbsite (AI(OH)3).3.2 for imogolite to 1.2. Zeolites Zeolites are hydrous framework silicates and those that occur in clay materials are predominantly alkali varieties (Table 2. Iron sulphides Pyrite (FeS2) is the most common of the sulphides found in clay materials occurring as veins. The pH at which the charge is zero is referred to as the zero point of charge or ZPC. mackinawite and griegite) are found in modem muds as precursors to later formation of pyrite.2. but celestite (SrSO4). 2. maghemite (7Fe203).2. goethite (no organic matter preserved) Pyrite (organic matter preserved) Glauconite. Their occurrence may suggest hypersaline conditions of formation. Fe2+/Fe 3+silicates siderite (no sulphides some organic matter preserved) Siderite after pyrite (organic matter preserved) 2.5.24 THE COMPOSITIONOF CLAYMATERIALS Their nominal formula is SiA1203(OH)4but both have poorly ordered crystal structures and are often described as amorphous. There is some evidence to suggest that marcasite forms under more acidic conditions than pyrite. lepidocrosite (7-FeO'OH).5. followed by further reaction with illite/mica or K-feldspars: 12FeSO4 + 4KAlaSi3Os(OH)2 + 48H20 + = 4KFe3(SO4)2(OU)6 + 8AI(OH)3 + 12Si(OH)4 + 4H2SO4. maghemite brown-black and hematite red. Iron oxides and hydroxides.

less siliceous varieties which with increasing metamorphism are in turn replaced by albite and eventually K-feldspars.24H20 (K.3. Generally the organic materials can be subdivided into labile and refractory organic fractions. Zeolites can be used as indicators of diagenesis and low grade metamorphism of argillaceous sediments. which has a very distinctive blue colour. CO3)3(OH. Phosphates may occur in a cryptocrystalline form referred to sensu lato as 'collophane'. Organic matter volcanics.F. oxic conditions. 2. Some micro-organisms are aerobic.2.9. abundance and distribution of organic matter can influence the physico-chemical behaviour of clay materials. This is one of many thiobacillus bacteria that exist in clay materials which derive energy from oxidizing inorganic sulphur usually under aerobic conditions. accumulations of vertebrate skeletal fragments). may form in lacustrine environments and soils.4.K. In addition to being present in phosphate minerals. acquiring their energy from reactions with oxygen. The leaching process involves the breakdown of cellular material by intracellular enzymes producing soluble compounds. other micro-organisms may also be present such as protozoa and small algae. ooliths. cements or replacements of calcareous skeletal clasts in environments with low clastic sedimentation and high organic productivity enriched in phosphate.Na. Halides Halite (NaC1) and.K) 3A13SisOI6. Analcite is also characteristically found as an authigenic mineral in hypersaline muddy sediments. which is consequently consumed. faecal or diagenetic in origin. 2. carbon dioxide and nitrate as energy sources and produces sulphate. The nature. generally survive burial and can be preserved in ancient sediments as kerogen. Organic matter is present in a variety of forms in clay materials including discrete organic particles. phosphorus is sorbed onto clay and other colloidal particles and this mechanism can be a major factor in controlling phophorus mobility in soil and aqueous environments. 105 to 106 fungi and 104 protozoa (Campbell 1992). The mixed alkali (K.g. to a much less extent. Evaporation of sea water and chloride-rich brines can create a sequence of evaporitic minerals that are often cyclic due to replenishment of the evaporating brines or interbedded with fine-grained siliciclastic or carbonate sediments.K)CaaAIgSi27072. Others are anaerobic. Phosphates may be bioclastic (e. The calcic forms persist to higher temperatures.Na)6 AI6Si30072-20H20 (Na. sugars and reduced nitrogen compounds (Campbell 1992). C1). One variety. absorbed onto clay and other associated colloidal particles (e. The bacteria Thiobacillus denatrificans uses sulphide.2. The nature and abundance of micro-organisms in clay materials and the inorganic compounds available for . The iron-rich phosphate mineral.H20 (Ca.8. Labile organic matter generally does not survive burial whereas refractory organics are non-metabolizable. These micro-organisms show a wide range of sizes and morphologies and can also exist in various dormant states such as spores and cysts that are resistant to dessication and temperature changes. Phosphates The most common phosphate minerals occurring in clay materials are the carbonate apatite group (Cas(PO4. In addition to bacteria.Ca)A12Si10024. pisoliths. leading to oxygen-deficient conditions. Kerogen has been defined as the organic constituents that are insoluble in aqueous alkaline and common organic solvents (Tissot & Welte 1984) which is the equivalent of 'humin' in soil science (Tyson 1995). generating their energy by reducing inorganic chemical species (sulphate.6H20 (Na2K2CaMg)4_sA19Si27072"27H20 (Na. other halides such as sylvite (KC1) and camallite (KMgC13"6H20) are characteristically found in clay materials associated with evaporitic sedimentary and soil environments. nitrate. The labile organic components degrade via leaching and decomposition processes. Authigenic phosphates can precipitate in mudrocks and sandstones as nodules. carbon dioxide) or organic species (fermentation reactions) and/or oxidizing other inorganic species (sulphide.7H20 25 2. ferrous ions) in the absence of oxygen. Kerogen makes up 95% or more of the organic matter preserved in sedimentary rocks. Zeolites have open framework silicate structures with the capability of acting as 'molecular sieves' by absorbing cations.g. Thiobacillus ferrooxidans also oxidizes ferrous ions to ferric in acidic environments and is a key influence in the natural degradation of pyrite (Hawkins & Pinches 1992). Common zeolites occurring in clay materials Natrolite Analcite Phillipsite Erionite Heulandite Clinoptilolite Mordenite Na2A12Si3010"2H20 NaA1Si2Or.THE COMPOSITION OF CLAY MATERIALS TABLE2. vivianite. anions and polar organic molecules into the open channels within their structures. fungi and viruses. In soils there are 107 to 108 bacteria per gram of dry mass. Na and some Ca) zeolites are progressively replaced by more sodic. iron oxides) and micro-organisms. Micro-organisms can flourish even under apparently very adverse conditions such as hydrothermal vents on mid-ocean ridges with temperatures above 200~ hypersaline soda lakes with a pH > 10 or in acid mine drainage waters with a pH of <2. The decomposition process relates to the bacterial colonization and the fermenting activity of the bacteria which is greatest under warm.

In the smectites the water molecules form single. These can affect. In the hydrated state there appears to be no preferential ordering of the water molecules and only weak interactions with the halloysite surfaces. for example. 9 being bonded to the cations by bridging water molecules. other minerals and organic matter. It needs to be emphasized that all mineral surfaces are capable of adsorbing water onto their surface. With increasing ionic strength there is a lesser tendency for cations to diffuse away from the negatively charged clay particles and the absorbed water layer becomes compressed and less diffuse than at lower ionic strengths. The nature and behaviour of the water absorbed into the interlayer sites of clay minerals is a function of: 9 the polar nature of the water molecules. depending on the humidity of the surrounding environment. 1993). 1987). double or triple water layers. There is also evidence that dehydration of the halloysite is accompanied by delamination of the halloysite layers thus inhibiting halloysite rehydration (Newman 1987). The degree to which this surface acidity is produced is an essential factor in creating the conditions for clay minerals to act as effective catalysts of various organic reactions. The resultant net negative charge can be offset by the presence of charge balancing H3O§ corresponding to a proton-donating Bronsted acid site.3. this is most significant for the clay minerals because their fine grain size and platy habit produce very large surface areas and thus give a relatively greater capacity for water adsorption. the exchange cations and cation hydration and the salinity of the aqueous solution. fertilizers. molecules with a strong tendency to form hydrogen bonds and polar organic molecules onto the charged clay surfaces. The catalytic behaviour is related to the large surface areas of clays and other colloids. The absorption of water into sepiolites and palygorskites involves adsorption onto the external surfaces and absorption into the channel sites within the crystal structure. There are significant differences in the interlayer water present in halloysites compared with the smectites and vermiculites that help explain why rewetting of dehydrated halloysites does not cause the structure to rehydrate. The water adsorbed onto the clay mineral surfaces has properties midway between bulk liquid water and ice and forms a structured water layer and a more diffuse less structured water layer. However. 9 capillary condensation of water into micro-pores. In the interlayer sites of expandable clay minerals the water forms coordinated shells around interlayer cations. The density of the water in the interlayer sites of swelling clay minerals is considered to be greater than that of liquid water and to increase with increasing pressure (Skipper et al. 2. In addition. the chemical behaviour of pollutants. pesticides in soils and the physical properties of flocculation and dispersion in aqueous environments (Johnston 1996).26 THE COMPOSITION OF CLAY MATERIALS oxidation and/or reduction will have a major influence in determining their chemical behaviour. 9 the size and charge of the interlayer cations and their hydration state. Clay surfaces also have acidic properties due to the presence of A1 substituting for Si in the tetrahedral sites. The thickness of the adsorbed surface water layer varies depending on the clay surface charge.1. Organic molecules are absorbed onto the charged clay mineral surfaces and interlayer sites by: 9 competing with and replacing the water molecules and forming complexes with interlayer cations. Organic-clay complexes and interactions Organic-clay complexes represent part of the humin or kerogen organic fraction. The packing of the water molecules absorbed onto the outer surfaces of the sepiolites and palygorskites is much less dense than than that of a surface water monolayer on other sheet silicates (Newman 1987). Such complexes and organo-clay reactions can have significant influences on chemical mobility and catalysis of chemical reactions.4. . Most organic compounds of interest as environmental pollutants are small non-ionic molecules and their sorption onto clay minerals involves weak interactions via van der Waal forces and hydrogen bonding (Sawhney 1996). which is analogous to the absoption of water into the channel sites of zeolite structures. Guven (1993) defined three forms of hydration in clay materials: 9 interlamellar hydration involving adsorption of water onto the internal surfaces of clay mineral particles. The vermiculites can exhibit single or double water layers depending on the humidity conditions. crystal size and habit. Moore & Reynolds (1997) argued that with increasing pressure the interlayer water should have a similar density to that of liquid pore waters. AP + ions on the edges of clay particle are capable of being electron pair acceptors and thus can act as Lewis acid sites (Rupert et al. 9 the location and value of the charge on the silicate layers of the clay mineral structures. 9 bonding of organic cations. The presence of adsorbed water layers covering the clay particles produces the characteristic cohesive plastic behaviour of clay materials. which is a function of mineralogy. However. 2. 9 continuous osmotic hydration involving unlimited adsorption of water onto the internal and external surfaces of primary mineral and organic particles. adsorbed onto or absorbed into clay minerals. Water In clay materials water is present in the inter-particle pore spaces.

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The varying properties o f the individual clay minerals and their often c o m p l e x interactions with fluid phases under different physical and c h e m i c a l conditions can play a m a j o r role in controlling the b e h a v i o u r o f clay materials.