Maria Franca Brigatti

Structure and Mineralogy of Clay Minerals

Abstract Phyllosilicates, and among them clay minerals, are of great interest not only for the scientific community but also for their potential applications in many novel and advanced areas. However, the correct application of these minerals requires a thorough knowledge of their crystal chemical properties. This chapter provides crystal chemical and structural details related to phyllosilicates and describes the fundamental features leading to their different behaviour in different natural or technical processes, as also detailed in other chapters of this book. Phyllosilicates, described in this chapter, are minerals of the (i) kaolin-serpentine group (e.g. kaolinite, dickite, nacrite, halloysite, hisingerite, lizardite, antigorite, chrysotile, amesite, carlosturanite, greenalite); (ii) talc and pyrophyllite group (e.g. pyrophyllite, ferripyrophyllite); (iii) mica group, with particular focus to illite; (iv) smectite group (e.g. montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite); (v) vermiculite group; (vi) chlorite group; (vii) some 2:1 layer silicates involving a discontinuous octahedral sheet and a modulated tetrahedral sheet such as kalifersite, palygorskite and sepiolite; (viii) allophane and imogolite and (ix) mixed layer structures with particular focus on illite-smectite.

SUMMARY OF RECOMMENDATIONS OF NOMENCLATURE COMMITTEES RELEVANT TO CLAY MINERALOGY: REPORT OF THE ASSOCIATION INTERNATIONALE POUR L'ETUDE DES ARGILES (AIPEA) NOMENCLATURE COMMITTEE FOR 2006

Brindley et al. (1951) reported the earliest efforts to obtain international collaboration on nomenclature and classification of clay minerals, initiated at the International Soil Congress in Amsterdam in 1950. Since then, national clay groups were formed, and they proposed various changes in nomenclature at group meetings of the International Clay Conferences. Most of the national clay groups have representation on the Nomenclature Committee of the Association Internationale pour l’Etude des Argiles (AIPEA, International Association for the Study of Clays), which was established in 1966. The precursor committee to the AIPEA Nomenclature Committee was the Nomenclature Subcommittee of the Comite International pour l’Etude des Argiles (CIPEA, International Committee for the Study of Clays). The AIPEA Nomenclature Committee has worked closely with other international groups, including the Commission on New Minerals and Mineral Names (CNMMN) of the International Mineralogical Association (IMA), which is responsible for the formal recognition of new minerals and mineral names, and the International Union of Crystallography (IUCr), which considered extensions to the nomenclature of disordered, modulated and polytype structures (Guinier et al. , 1984) published earlier by a joint committee with the IMA (Bailey, 1977). In contrast to the other national clay groups, however, The Clay Minerals Society (CMS) Nomenclature Committee, which was established in 1963 at the same time as the CMS and predates the AIPEA Nomenclature Committee, remains in existence and occasionally produces recommendations. The precursor to this committee was the Nomenclature SubCommittee, which was organized in 1961 by the (US) National Research Council. The Chair of the AIPEA Nomenclature Committee is a standing member of the CMS Nomenclature Committee so that the committees are in close contact. The purpose of the AIPEA Nomenclature Committee has been to make general and specific recommendations concerning: (1) definitions of mineralogical and crystallographic clay-related terms; (2) classification and terminology …

Chapter 2 Structures and Mineralogy of Clay Minerals

Publisher Summary This chapter describes structures and mineralogy of clay minerals. Phyllosilicates considered in this chapter ideally contain a continuous tetrahedral sheet. Each tetrahedron consists of a cation, T, coordinated to four oxygen atoms and linked to adjacent tetrahedra by sharing three corners (the basal oxygen atoms, Ob) to form an infinite two-dimensional hexagonal mesh pattern along the a, b crystallographic directions. The free corners (the tetrahedral apical oxygen atoms, Oa) of all tetrahedra point to the same side of the sheet and connect the tetrahedral and octahedral sheets to form a common plane with octahedral anionic position Ooct. Ooct anions lie near to the center of each tetrahedral 6-fold ring, but are not shared with tetrahedra. The 1:1 layer structure consists of the repetition of one tetrahedral and one octahedral sheet, while in the 2:1 layer structure one octahedral sheet is sandwiched between two tetrahedral sheets. In the 1:1 layer structure, the unit cell includes six octahedral sites (i.e., four cis and two trans-oriented octahedral) and four tetrahedral sites. Six octahedral sites and eight tetrahedral sites characterize the 2:1 layer unit cell. Structures with all the six octahedral sites occupied are known as “trioctahedral.” If only four of the six octahedra are occupied, the structure is referred to as “dioctahedral.” The structural formula is often reported based on the half unit-cell content—that is, it is based on three octahedral sites.

Kinetics of heavy-metal removal and recovery in sepiolite

Fixed beds of Mg-enriched sepiolite were percolated through Co2+, Cu2+, Zn2+, Cd2+ and Pb2+ single- and multicomponent heavy-metal solutions to study both the dynamic interactions between mineral and heavy-metal cations and the ion-sorption kinetics. The metal concentrations in the eluates were determined by atomic adsorption and/or inductively-coupled plasma and kinetics by the classical kinetic approach, using isothermal experiments at room temperature. The experimental results suggest that: (i) the amount of heavy metal sorbed by the mineral increases for smaller cations; ii) the sepiolite sorption efficiency sequence is, for single component solution, Pb2+<Cd2+<Co2+<Zn2+<Cu2+, and, for multicomponent solution, Pb2+=Co2+<Cd2+<Zn2+<Cu2+. Therefore, the ability of sepiolite to remove Cu2+, Zn2+, Cd2+ and Pb2+ is virtually independent of the competitive cation interactions, whereas its affinity for Co2+ is lower when other metals coexist in the solution. The cationic sorption-exchange equilibrium constants (k), obtained by fitting the data with Langmuir equations are: kCo2+=4.798×10−3, kCu2+=3.424×10−3, kZn2+=2.907×10−3, kPb2+=1.009×10−2 [meq min]−1, kCd2+=1.187×10−2 [meq min]−1/2 for monocomponent solution experiment. The desorption study concerning the nature of eluting agents shows that Mg2+ is more effective than Na+ in removing heavy metals. Rapid kinetics and equilibrium of exchange of Mg2+ for heavy metals were observed; this is thought to indicate that the main process occurs at easily accessible sites at the outer and channel surface. Moreover, other processes can be assigned to the exchange of Mg2+ in the octahedral sites at the channel edges.

REPORT OF THE ASSOCIATION INTERNATIONALE POUR L’ÉTUDE DES ARGILES (AIPEA) NOMENCLATURE COMMITTEE FOR 2001: ORDER, DISORDER AND CRYSTALLINITY IN PHYLLOSILICATES AND THE USE OF THE “CRYSTALLINITY INDEX”

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kubler index’, and the ‘Arkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllo-silicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, e.g. ‘Hinckley index’ or ‘Kubler index’, or in honor of a researcher who investigated the importance of the parameter extensively, e.g. ‘Arkai index’. In contrast to a crystalline solid, an ‘amorphous’ solid is one in which the constituent components are arranged randomly. However, many variations occur between the two extremes of crystalline vs. amorphous. For example, one type of amorphous material might consist simply of atoms showing no order and no periodicity. Alternatively, another amorphous material may consist of atoms arranged, for example, as groups of tetrahedra ( i.e. limited order) with each group displaced or rotated ( e.g. without periodicity) relative to another. Thus, this latter material is nearly entirely amorphous, but differs from the first. Likewise, disturbance of order and periodicity may occur in crystalline materials. The terms ‘order’ and ‘disorder’ refer to the collective nature or degree of such disturbances. Although seemingly simple notions, ‘crystalline’ and ‘amorphous’ are complex concepts. Crystalline substances may show a periodic internal structure based on direction. For example, two-dimensional periodicity is common in phyllosilicates where two adjacent sheets or layers must mesh. For example, in serpentine, …

Report of the Association Internationale pour l’Etude des Argiles (AIPEA) Nomenclature Committee for 2001: Order, disorder and crystallinity in phyllosilicates and the use of the ‘Crystallinity Index’

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kubler index’, and the ‘Arkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions, or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllosilicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, as in ‘Hinckley index’ or ‘Kubler index’, or in honour of a researcher who investigated the importance of the parameter extensively, as in ‘Arkai index’. In contrast to a crystalline solid, an ‘amorphous’ solid is one in which the constituent components are arranged randomly. However, many variations occur between the two extremes of crystalline vs. amorphous. For example, one type of amorphous material might consist simply of atoms showing no order and no periodicity. Alternatively, another amorphous material may consist of atoms arranged, for example, as groups of tetrahedra (i.e. limited order) with each group displaced or rotated (e.g. without periodicity) relative to another. Thus, this latter material is nearly entirely amorphous, but differs from the first. Likewise, disturbance of order and periodicity may occur in crystalline materials. The terms ‘order’ and ‘disorder’ refer to the collective nature or degree of such disturbances. Although seemingly simple notions, ‘crystalline’ and ‘amorphous’ are complex concepts. Crystalline substances may show a periodic internal structure based on direction. For example, two-dimensional periodicity is common in phyllosilicates where two adjacent sheets or layers must mesh. For example, …

Crystal chemical variations in Li- and Fe-rich micas from Pikes Peak batholith (central Colorado)

Abstract The crystal structure and M-site populations of a series of micas-1M from miarolitic pegmatites that formed within host granitic rocks of the Precambrian, anorogenic Pikes Peak batholith, central Colorado, were determined by single-crystal X-ray diffraction data. Crystals fall in the polylithionitesiderophyllite- annite field, being 0 ≤ Li ≤ 2.82, 0.90 ≤ Fetotal ≤ 5.00, 0.26 ≤ [6]Al ≤ 2.23 apfu. Ordering of trivalent cations (mainly Al3+) is revealed in a cis-octahedral site (M2 or M3), which leads to a lowering of the layer symmetry from C12/m(1) (siderophyllite and annite crystals) to C12(1) diperiodic group (lithian siderophyllite and ferroan polylithionite crystals). On the basis of mean bond length, the ordering scheme of octahedral cations is mostly meso-octahedral, whereas the mean electron count at each M site suggests both meso- and hetero-octahedral ordering, the calculated mean atomic numbers being M1 = M3 ≠ M2, M2 = M3 ≠ M1 and M1 ≠ M2 ≠ M3. As the siderophyllite content increases, so do the a, b, and c unit-cell parameters, as well as the refractive indices, primarily nβ. The tetrahedral rotation angle, α, is generally small (1.51 ≤ α ≤ 5.04°) and roughly increases with polylithionite content, whereas the basal oxygen out-of-plane tilting, Δz, is sensitive both to octahedral composition and degree of order (0.0 ≤ Δz ≤ 0.009 Å for siderophyllite and annite, 0.058 ≤ Δz ≤ 0.144 Å for lithian siderophyllite and ferroan polylithionite crystals).

Interaction between montmorillonite and pollutants from industrial waste-waters: exchange of Zn2+ and Pb2+ from aqueous solutions

Abstract The interactions between montmorillonite (sample SAz-1 from the Source Clay Repository of the Clay Minerals Society) and Zn2+ and Pb2+ solutions of different ionic strengths (from about 10−5 to 1 M) are studied in order to observe changes in the clay-solution system and mineral crystal chemistry. In both types of solution the stationary state of exchange, attained within 20 min, depends on the solutions ionic strength. The uptake can be interpreted by means of a Langmuir-type equation with Zn2+ somewhat more easily exchanged than Pb2+. The shifting of the d(001) spacing from 15.3 A (natural sample) to 12.8 A (Zn2+-exchanged montmorillonite) and 12.4 A (Pb2+-exchanged montmorillonite) suggests that the kind of interlayer cation affects the c dimension of the layer. Upon heating, the exchanged montmorillonite layer collapses (d(001),Zn = 9.5 A; d(001),Pb = 10.0 A) and the closest packing is attained at T = 200°C for Pb2+ - and at 380°C for Zn2+-exchanged samples. In addition to reactions observed for natural and Pb2+-exchanged samples in the temperature ranges 20–250°C and 500–700°C, the thermal analyses of Zn2+-exchanged montmorillonite show a reaction at about 380°C which can be related either to strongly bonded water molecules or to “brucitic-like” interlayers or to Zn2+-exchanged octahedra.

REDUCTION AND SORPTION OF CHROMIUM BY Fe(II)-BEARING PHYLLOSILICATES: CHEMICAL TREATMENTS AND X-RAY ABSORPTION SPECTROSCOPY (XAS) STUDIES

The reduction of hexavalent chromium species in aqueous solutions by interaction with Fe(II)-bearing solid surfaces was studied using a 0.96 × l0−3 M Cr(VI) solution and iron-rich clays with different Fe(II)/Fe(III) ratios, layer charge, and exchange properties, i.e., chlorite, corrensite, and montmorillonite. Experimental studies demonstrated that Fe(II)-bearing phyllosilicates reduce aqueous Cr(VI) ions at acidic pH. Chlorite and corrensite, owing to the high Fe(II)/Fe(III) ratio, are electrochemically reactive, as rapid Cr(VI) reduction indicated. In contrast, montmorillonite showed minimum to nil reactivity towards Cr(VI). Furthermore, corrensite, which is high in both Fe(II)/Fe(III) ratio and exchange capacity, adsorbs the greatest amount of chromium.X-ray absorption spectroscopy at Al, Mg, Fe, and Cr K-edges was used to investigate the adsorbed chromium species. The montmorillonite sample, unaffected by treatment with Cr(VI) solution, displays no change at any investigated edge. Edge shape and energy also do not change for the Mg and Al spectra in corrensite, and changes are minor in chlorite. By contrast, the Fe K-edge changes both in chlorite and corrensite, and indicates an increase of Fe(III) in treated samples at the expense of pre-existing Fe(II). Cr K-edge spectra show that chlorite and corrensite sorb Cr(III), which implies its reduction from Cr(VI) in the interacting solution.

Crystal chemistry of Mg-, Fe-bearing muscovites-2M 1

Abstract Phengitic muscovite-2M1 crystals [[12](K0.88-0.99Na0.01-0.09Ca0.00-0.06Ba0.00-0.01)[6](Al1.64-1.88Fe2+0.06-0.29Fe3+0.01-0.16Mg0.00-0.16Mn0.00-0.07Ti0.00-0.06)[4](Si2.87-3.30Al0.70-1.13)(OH)1.56-2.07F0.00-0.41O9.91-10.25] from pegmatites and peraluminous granites were refined to investigate the influence of phengitic substitution on the mica structure. Single-crystal X-ray diffraction data were collected for eleven crystals in the C2/c space-group (agreement factor 2.1% ≤ Robs ≤ 3.9%). Tetrahedral Si and Al cation disorder was found for each sample, with the mean tetrahedral cation-oxygen distances ranging from 1.639 Å ≤ ≤ 1.647 Å and 1.640 Å ≤ ≤ 1.646 Å. As phengitic substitution increases, the octahedral sheet expands and requires a less distorted (more hexagonal) tetrahedral ring (7.70° ≤ α ≤ 11.38°) and low corrugation of the basal O plane (0.1796 Å ≤ Δz ≤ 0.2296 Å). The electron density at the M2 site is greater than that required for the ideal muscovite-2M1 structure, and a small excess of electron density is found in the M1 site. The inner sixfold coordination of the interlayer (A) cation is elongated along c*, which is consistent with the high α values and the long A-O11 bond length.