Acta Geodyn. Geomater., Vol.2, No.2 (138), 53-68, 2005

CLAY INCLUDING RELATED PHYLLOSILICATES: INTERDISCIPLINARY RESEARCH AND INWARD INTEGRATION

Jiří KONTA

Professor Emeritus, Faculty of Sciences, Charles University, Albertov 6, 128 43 Prague 2 home address: Korunní 127, 13000 Prague 3, Czech Republic Corresponding author‘s e-mail: [email protected]

(Received September 2004, accepted April 2005)

ABSTRACT More than 110 species of clay minerals and related phyllosilicates were discovered mostly in the 20th and 19th centuries, including 13 regular interstratifications (R1 range) naturally occurring or synthesized and referred to between 1950-2003. This contribution to theoretical and applied clay science, whose evolution is based on mineralogical roots, stresses interdisciplinary research among clay science, basic sciences (physics, chemistry, mathematics, geometry), earth-, biological-, applied- and related sciences and engineering technologies as a basis for substantial past and future discoveries. Not only a novel desirable cooperation with other theoretical and applied disciplines, but also a close inward integration among the six major research regions of clay science is necessary for its further development. Two diagrammatic presentations show: 1) a desirable multidisciplinary cooperation and mutual influence among sciences and technologies affecting the development and progress of clay science; 2) a view of desirable integration among the six major research regions within clay science in the near future.

KEYWORDS: theoretical and applied clay science, history, names of clay species and related phyllosilicates (more than 110), research regions and subregions, interdisciplinary cooperation, desirable inward integration

1. INTRODUCTION different geological formations and ages are closely Clay minerals are essential constituents of connected with the genesis and extraction of earth oil argillaceous sediments and accompanying argillized and gas (from Weaver, 1956; Burst, 1969; Shutov et volcanoclastics, weathering crusts, soils and al., 1969; up to Drits et al., 1997; Sakharov et al., hydrothermal clay accumulations. Most of these 1999a, b; Niu et al., 2000; or Plançon and Drits, 2000; genetically different mineral accumulations contain and others quoted by Konta, 2000). important clay raw materials used by man through No wonder that clay minerals, clay raw millennia. Argillaceous accumulations are typical of materials, many different argillaceous accumulations, the surface region of the Earth. This means that many and soils are intensively studied by mineralogists, clay raw materials are easily accessible and petrologists, geologists, clay- and soil scientists, extractable anywhere in the world. At present, clay chemists, physicists and engineers of engaged raw materials are used in numerous industrial technological branches. The results of their branches, especially in ceramics, paper, rubber, investigation may fall in one or more of the six major p lastics, chemical, agrochemical, dyes, foundry, and research regions of clay science: 1) crystal structures cement industries and as silicate binding materials, in (including chemistry); 2) research methods (including pharmaceutic, cosmetic, food, petroleum industries, modelling); 3) investigation of natural accumulations and in civil engineering and ecological projects (Grim, and genetic conditions of clay and related minerals; 4) 1962; Konta, 1995). Soil science and agriculture have physical and physicochemical properties of clay applied theoretical clay science and its methodology minerals and argillaceous rocks; 5) modified clays (by for a long time (Gjems, 1967; Jackson, 1969; chemical or physical treatments); 6) applied clay Gieseking, 1975; Stucki and Banwart, 1980; Smart science including exploitation and beneficiation of and Tovey, 1981, 1982; Bolt, 1982; Sposito, 1984; clay raw materials and ecological projects. Kodama, 1985; Dixon and Weed, 1989; Mackenzie, Although clay science has mineralogical roots in th th 1990). The knowledge of electrochemical properties the 18 and especially 19 century, it emerged as an of clay minerals occurring in the oil-bearing strata has authentic scientific discipline in the mid-20th-century b een of great utility (Wyllie, 1955). The diagenetic (Konta, 2000). The primary merit lies in the use of X- transformations of clay minerals in sediments of ray diffraction method and wide interdisciplinary 54 J. Konta

cooperation of mineralogy, petrology, chemistry synthesized in the 1:1 ratio, i.e. R1 range, and (inorganic, organic, analytical, physical chemistry and published in the period between 1950-2000 (here until especially colloid chemistry), physics, mathematics, 2003) are referred by Konta (2000). They have been soil science and engineering technologies. Each of named as mineral species: rectorite (di Mi-di Mo, these disciplines has contributed to the development Bradley, 1950), corrensite (Ch-Ve or Ch-Sm, of clay science either by its theory, or research Lippmann, 1954, 1956), (Ta-Sa, Alietti, 1956; methods, experimental materials and research results. Veniale and v.d. Marel, 1968), tosudite (di Ch-di Mo, Sudo and Kodama, 1957; Frank-Kamenetsky et al., 2. MINERALOGICAL ROOTS OF CLAY SCIENCE 1965), Ka-Mo (not named, Altschuler et al., 1963), First mineralogical descriptions and chemical hydrobiotite (Bi-Ve, Veniale and v.d. Marel, 1969), characterization of clay minerals and related kulkeite (Ta-Ch, Schreyer et al., 1982), Bi-Ch (not yet p hyllosilicates, including their macrocrystalline named, Olives and Amouric, 1984), Bd-Mo equivalents denoting mineral species or giving group (synthetic, Yamada and Nakasawa, 1993), dozyite th and series names, go back to the 18 century: chlorite (Sp-Ch, Bailey et al., 1995), trioctahedral rectorite /a group name/, /a series name/, /a (Mi-Sa, synthetic, Yamada et al., 1999), Ch-Sa group name/, , ; terms mica, (synthetic, Yamada et al., 1999), brinrobertsite (Pyph- (or kaolin), talc, similarly as "clay" or fuller's Sm, Dong et al., 2002). Abbreviations used: Bd = earth (Robertson, 1986), being still much older. beidellite, Bi = , Ch = chlorite, di = Mineralogists of the 19th century were much more dioctahedral, Ka = kaolinite, Mi = mica, Mo = successful in the description of new layer hydro- montmorillonite, Pyph = , Sa = , silicates: , , , , Sm = smectite, Sp = serpentine, Ta = talc, Ve = batavite, biotite /a series name/, , , . /a series name/, clinochlore, corundo- Nomenclature of the according to Rieder p hyllite, , delessite, diabantite, , et al. (1998) has been respected. For chlorites, the /a series name/, , kaolinite, nomenclature by Foster (1962) has been adopted. , /a polytype/, , Other names of chlorite species according to several , , penninite /or pennine/, diverse classification schemes (cf. Brindley, 1961) are phengite /a series name/, , polylithionite, not applied here. Polymorphs, but exceptionally p yrophyllite, ripidolite, , saponite, , polytypes, are taken as mineral species. Group names , serpentine, , stevensite, and series names are indicated. tainiolite, thuringite, vermiculite /trioctahedral and More than 110 species together th dioctahedral, distinguished in the 20 century/, with series names and related phyllosilicates including volkonskoite, zinnwaldite /a series name/. Mineralo- their macrocrystalline structural equivalents together gical research during the 20th century discovered with the named regular interstratifications are known further clay mineral species and related up to the year 2003. Numerous varieties and polytypes p hyllosilicates: , , attapulgite, would substantially exceed this number. Random baumite, beidellite, berthierine /“kaolinite-type interstratifications of phyllosilicates are common in chamosite”/, boromuscovite, brammalite /a series nature, occurring in hundreds of possible name/, brindleyite, brunsvigite, cardenite, , combinations (see literature evaluated by Konta, chromophyllite, clinochrysotile, cookeite, /a 2000). polytype/, donbassite, eastonite, ferroalumino- New methods of the 20th century, especially X- celadonite, ferroantigorite, ferroceladonite, ferro- ray diffraction, and later IR spectrometry, TEM, SEM, corundo phyllite, garnierite, , griffithite, HRTEM and EDAX together with other chemical and hectorite, , /a series name, or physical methods (see Konta, 2000) enabled not only hydromica/, , lepidomelane, lizardite /Mg discoveries of new phyllosilicates and their OD and Al species/, loughlinite, masutomilite, medmon- diversities, but to remove many superfluous names of tite, metahalloysite, , montdorite, “mineral species” from the system of phyllosilicates. nanpingite, nepouite, nickelian lizardite /nepouite Names like “picrolite, baltimorite, marmolite, series/, nickel vermiculite, norrishite, orthochrysotile, williamsite, antillite, aphrodite” and others in the pimelite, preiswerkite, sheridanite, sudoite, tetra-ferri- chrysotile-antigorite series of minerals are disregarded annite, tetra-ferriphlogopite, tobelite, willemseite, (Nagy and Faust, 1956). All serpentine minerals, i.e. wonesite. The primary literature regarding some of 1:1 trioctahedral phyllosilicates, belong either to these names and their first locality has been quoted by chrysotile (ortho- and clinochrysotile) or antigorite or Bergaya et al. (2001). The priority authors with the lizardite (Whittaker and Zussman, 1956). “Anauxite” years of the first publications about nearly all having excess silica compared to kaolinite is not more phyllosilicate species known prior to 1954 are referred mineral species of the 1:1 dioctahedral phyllosilicates. to in the Chemical Index of Minerals (Hey, 1955). “Anauxite” and kaolinite structures are identical Many useful data can be found in the book, Mineraly (Bailey and Langston, 1969; Allen et al., 1969). Opal ilaste, by Stoch (1974). The original discoveries of particles associated with the kaolinite plates in the regular phyllosilicate interstratifications occurring or “anauxite” from Bilina were observed first under

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polarizing microscope and determined by index of correspond the definition of clay minerals. Due to refraction (Konta, 1957). Further superfluous names some of their properties resembling clay minerals, the of “mineral species” disappeared in the course of research results on LDH, hydrotalcites, hydrotalcite- modern investigation from the mineralogical system like compounds and zeolites are welcomed in journals of chlorites, micas and other phyllosilicate groups. specialized in clay science or become symposial parts The real clay minerals belong to the following of clay conferences. groups: mica (the dominating mineral having the mica Some alkali hydrated silicates, mentioned by structure in clays is illite /a series name/ and its Bergaya et al. (2001), discovered in the second half of th interstratifications with other clay minerals are the 20 century deserve more attention of mine- common), vermiculite, smectite, serpentine-kaolinite, ralogists, crystallographers and engineers of potential talc-pyrophyllite, chlorite, pseudophyllosilicates or technological branches. These silicates are distingui- hormites (sepiolite-palygorskite) and allophane. shed according to their different Na2O (or Micas as macroscopic equivalents of illite are taken in Li2O):SiO2:H2O ratios (kanemite, kenyaite, magadiite, the system because their investigation helped much in makatite, silinaite; see Eugster, 1967; Lagaly et al., the recognition of 2:1 clay/grade phyllosilicates. 1972). They occur together with layered crystalline Micas without or with extremely small amount of silicic acid (silhydrite) in salina environments or can + molecular water (H2O or H3O ) in the interlayer space be easily synthesized. It seems, however, that they are are typical of mineral assemblages other than clays or not consistent with clay minerals having phyllosilicate they occur in clays as clastic remnants from other non- structure and alternating tetrahedral and octahedral clay assemblages. Similarly, brittle micas (, sheets (Annehed et al., 1981). chernykhite, , , , kinoshitalite) having also the phyllosilicate structure, do not occur 3. RAPID PROGRESS DUE TO in natural assemblages typical of clay minerals. They INTERDISCIPLINARY RESEARCH b elong to the system of phyllosilicates but are usually The investigation of clay minerals, clay raw ignored by experts working with clays. materials or soils lies not only in the recognition of Bergaya et al. (2001) quoted some authors who clay mineral species, their order-disorder states, and introduced new layered materials, namely layered genetic conditions. The understanding of such double hydroxides (LDH). Their general formula can phenomena or properties as exchange, ion 2+ 3+ x+ be written as [M 1-xM x(OH)2] . The layer crystal exchange capacity, swelling and shrinkage, thermal structure of LDH is similar to that of brucite, dehydration and rehydration, adsorption, absorption, Mg(OH) 2. When combined with one of anions, they desorption, sorption selectivity of phyllosilicates, are called “anionic clays”. Hydrotalcites are acidity of clays, catalytic activity, plasticity, particle “hydrotalcite-type anionic compounds” or more size distribution, dispersion in water or other liquids descriptively “layered double hydroxides of divalent and the effect of electrolytes, flocculation and and trivalent metals combined with carbonate anion”. deflocculation of clay particles, differences in surface For example, a common hydrated hydroxycarbonate area, sealing properties, porosity, permeability, 2+ 3+ of M , M has a formula [Mg3Al(OH)8]2CO3.nH2O. hydraulic conductivity, transport of chemicals through Divalent metals M2+ can be e.g. Mg2+, Ni2+, Zn2+, clays, ion diffusion, thixotropy and quasiviscosity of 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ Ca , Sr , Ba , Fe , Co , Cd , Cu , Mn . clay suspensions necessitated cooperation of Trivalent metals M3+ in these compounds are Al3+, mineralogy or sedimentary petrology with other Fe 3+, Cr3+, Ga3+. Hydrotalcite-like compounds have a science disciplines and experts of different production 2+ 3+ n- general formula [M 1-xM x(OH)2]A x/nmH2O, where technologies (Konta, 2001). The research beginnings n------2- A means anion, e.g. F , Cl , ClO4 , OH , NO3 , CO3 , of the majority of these phenomena or properties 2- SO 4 or organic or complex anion, and x is atomic preceded the era of the determination of crystal 3+ 2+ 3+ ratio of M /(M +M ) (Moroz et al., 2001). structure of clay minerals by X-ray diffraction. Some Due to the layered structure, LDH, hydrotalcites of the initial research reports, for example, on the and hydrotalcite-like compounds reveal some absorption and desorption (Thompson, 1850; Way, p roperties related to the behaviour of clay minerals. 1850, 1852, 1854; van Bemmelen, 1878), on thermal They found use in practice, e.g. for their excellent dehydration and rehydration (Le Chatelier, 1887), catalytic, or sorptive capacities and simple, easy plasticity and cohesion (Atterberg, 1910), ion synthesis. LDH, however, are not hydrosilicates with exchange (Wiegner, 1912), particle size distribution alternating tetrahedral and octahedral sheets, which is (see references by Andreasen, 1929), the acidity of p rimary a diagnostic condition for clay minerals. colloidal clay in soils (see references by Bradfield, Similarly, although not layered hydrosilicates, zeolites 1923) or on thixotropy (Freundlich, 1928; Buzagh, with their catalytic, sorptive and ion exchange 1929; Hauser and Reed, 1937) go back even more properties are widely used in practical applications than 100 to 150 years ago. It was quite natural that the close to those of natural or modified clay minerals. recognition of the above-mentioned properties or The above shortly mentioned inorganic behaviour of clay matter attracted attention and compounds cannot be included in the system of clay cooperation of the basic sciences and experts of minerals or phyllosilicates, because they do not various production technologies. Ceramic technology,

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for example, still is in need of more information, corrugated surfaces. “Local balance of forces” in layer namely about green and dry strength, dilatancy of structures may provide a means of structural control dense suspensions, sintering temperature, sintering over polytypism. range, fusion temperature, thermal dilatation of The application of spectroscopic methods and p repared bodies, firing colour and others. The research modernized electron microscopy with the theoretical of these and related phenomena and properties of clay basis in physics or physical chemistry helped a lot in matter above all, needed the support of the basic the investigation of different structural and chemical sciences, namely mathematics, physics and chemistry. inconformities commonly occurring in the crystals of Similar interdisciplinary cooperation took place phyllosilicates. First simple infrared studies of later in the research of the and crystal phyllosilicates fall into the mid-20th-century (Adler, chemistry of phyllosilicates (from 1928 till the 1950; Hunt, 1950; Keller and Pickett, 1950). Later, p resent). Especially the intense entry of chemists and chemists Farmer (1968) specialized in the research of physicists into the mineralogical research and the soils, and Parker (1969) specialized in ceramic clays application of the X-ray diffraction method brought successfully applied infrared spectroscopy to the about the first determination of atomic structure and investigation of the stacking relationships in phyl- crystal chemistry of some common clay minerals losilicates. Other spectroscopic methods (Mössbauer, (Mauguin, 1928; Pauling, 1930a, b; Gruner, 1932a, b, Raman, electron spin resonance, neutron scattering 1933, 1934 a, b, 1935a, b; Hofmann et al., 1933; method, diffuse reflectance spectroscopy, ultraviolet Kazantsev, 1934; and others, see literature by Konta, and visible light spectroscopy) and different magnetic 2000). The discovery of polytypism, first in the resonance methods highly contributed to the kaolinite minerals (Hendricks, 1939) and later in knowledge of phyllosilicates and their modified micas (Heinrich and Levinson, 1955), and the derivatives (Bailey, 1975 and other authors; Fripiat, following refinement of crystal structures in all groups 1981; see literature evaluated by Konta, 2000). of phyllosilicates and their polytypes was a result of a Crystal chemistry of clay minerals encountered cooperation among physicists, crystallographers, new horizons by the discovery of different chemical chemists and mineralogists in later decades (see domains and cationic order-disorder states in literature compiled by Konta, 2000). Physicist individual structural sheets (Gatineau, 1964) and Zvyagin with Pinsker (1949) introduced electron interlayer space (Besson et al., 1974; Stul and diffraction analysis into the investigation of clay grade Mortier, 1974; Lagaly and Weiss, 1976). crystals. Physicist Brindley with Robinson (1946, Geologists and sedimentary petrologists Weaver 1948) are first credited with the discovery of structural (1956), Kossovskaya and Shutov (1955, 1958, 1963), order-disorder states in a whole series of . Burst (1969), Shutov et al. (1969), Dunoyer de Ten years later, Brindley and Nakahira (1958) opened Segonzac (1969), Weaver and Beck (1971) were the a new topic in the structural mineralogy by the first first to recognize the genetic importance and practical explanation of the nature of the interlayer use of mixed-layer clay minerals, namely, their bonds in kaolinite minerals. A strong influence of postsedimentary transformations in the sedimentary physical chemistry and physics upon the research of lithosphere. order-disorder states of phyllosilicates is evident. This Since 1940 electron microscopy, the domain of extensive research topic is connected with the physicists, successfully applied by mineralogists, has investigation and the role of defects in solid state enabled to study the shape variability of clay and p hysical chemistry followed in literature for about 70 related minerals (von Ardenne et al., 1940). Later, it years (Lidiard, 2003). The phenomenon of different has been adopted as transmission (TEM or STEM) disorder states is proper to any crystalline material. and scanning (SEM) electron microscopy, both Radoslovich (1959, 1960, 1962, 1963a, b) and methods simultaneously used e.g. for the investigation his coworkers (Radoslovich and Norrish, 1962; Veitch of morphological changes in a continuous smectite-to- and Radoslovich, 1963) discovered further irregular- illite conversion series (Ahn and Peacor, 1986; Inoue, ities in the atomic structure of muscovite and later in 1986). Page and Wenk (1979) using TEM were the the structure of other phyllosilicates. They measured first to observe fine-scale intergrowths of micas with cell dimensions, composition limits, interatomic other clay minerals including chlorite in fine-grained forces, symmetry and distortion of octahedra and alteration products of plagioclase. Veblen and Buseck tetrahedra in phyllosilicates. They found that actual (1979) used TEM for the study of mixed layering in layer structures depart from the ideal hexagonal serpentine minerals. However, the fine intergrowths, arrangement. Twists and tilts of the tetrahedral TO4 mixed-layering defects and different clay mineral groups in the mica structure have been documented in interstratifications were still more effectively studied detail in their studies. They showed that 1M, 2M and using high resolution transmission electron 3 T polytypes are common in nature. The trigonal form microscope (HRTEM), as shown by McKee and of the tetrahedral network accommodates the Buseck (1978), Buseck and Veblen (1981) or Veblen interlayer K+ more satisfactorily in the observed (1983). HRTEM helped much in the study of mica polytypes than in the unobserved or rare forms. diagenetic transformation of phyllosilicates, e.g. Basal are no longer coplanar but form mixed-layer Il-Sm (Guthrie and Veblen, 1989), or

CLAY MINERALS INCLUDING RELATED PHYLLOSILICATES: INTERDISCIPLINARY RESEARCH … 57

illitisation of smectite (Amouric and Olives, 1991). numerous scientific disciplines and technologies is not Środoń et al. (1990) used the HRTEM for a privilege of the clay science alone, but of any measurement of the expandability of mixed-layer Il- science or technology. Sm. HRTEM has been used for the investigation of some inconformities in the order-disorder states up to 4. EXISTING AND DESIRABLE CLOSE the position of individual atoms (literature quoted by INTEGRATION OF SIX MAJOR RESEARCH Konta, 2000). REGIONS WITHIN CLAY SCIENCE Specialized physicists and crystallographers In clay science, the continuing and strenghtening applying the necessary mathematics developed and influence of basic sciences for over more than seventy later refined the modelling as well as the simulation of years led, first of all, to a strong progress in the crystal structures. This included the defects and the recognition of crystal structures and crystal chemistry dynamics of structural transformations using of individual phyllosilicates (the 1st research region). computer technology (Reynolds, 1967, 1985; Bookin The successful development and application of the et al., 1978; see more literature collected by Konta, research methods is closely connected with the 2000). Towards the end of the 20th century, the great impressive crystal structure research region including contributions of physicists and crystallographers crystal chemistry. Today, we can say that the working in clay science led to the modular analysis of knowledge in these two major research regions, i.e. 1) crystal structures (Zvyagin, 1997, 2001). Modular crystal structures and 2) research methods, has got crystallography involves consideration, description, ahead of the other four major research regions of clay and derivation of modular structures, i.e. to science. The progress in the remaining four research simultaneously detect components, polymorphism, regions of clay science depends now on the polytypism and order-disorder (OD) diversity. transmission of the attained structural discoveries, According to Zvyagin (2001), electron diffraction their effective integration, and the use of the most texture patterns are especially effective for the modern methods. investigation of delicate inconformities in layer The 2nd research region of clay science, structures. They display separately the features of “Research methods”, comprises nearly 100 different structural layers and how the layers are stacked. methods for the investigation of clay minerals and Electron diffraction applications have produced argillaceous rocks (Konta, 2000). Each of these refinements or even a revision of results obtained methods can be an individual research subregion. I from other techniques, which have imported to change don’t know any scientist who has mastered all these ideas and conclusions in areas of polymorphism, methods. I don’t know any laboratory or institution polytypism and OD structures. The modular which uses half or more of these research methods. crystallographic analysis requires an experienced But this is not important. Much more significant for crystallographer indeed. any research project is to know how to establish an The strong influence of chemistry, physics and effective cooperation among the institutions and engaged technologies led to the preparation and individuals mastering the right methods. investigation of modified clays. They comprise The 3rd research region of clay science, i.e. + 2+ hydrophilic monocationic clays (e.g. with Na or Ca “Investigation of natural accumulations and genetic or other inorganic interlayer cation), organoclays, conditions of clay and related minerals”, can be pillared clays (mostly with RIII and RIV oligomeric thematically divided into nine subregions: a) inorganic cations), acid activated clays, specifically weathering processes, the behaviour of parent calcined clays and systematically milled or ground constituents (minerals and volcanic glass) and newly clays. formed clay minerals in the weathering crusts and In summary, chemistry, physics together with soils; b) hydrothermal clay minerals and their applied mathematics, and clay mineralogy influenced transformations; c) clay minerals in muds, clays and all research regions of clay science. The greatest sedimentary rocks deposited in rivers, lakes, seas and progress, however, has been attained in the oceans, and eolian deposits; d) erosion, transport, and investigation of crystal structures and crystal sedimentation of clay particles, basin analysis; e) chemistry of clay minerals. burial diagenesis; f) isotopes (O, H) and temperature The investigation of clay minerals and history of clay minerals, and Rb-Sr, K-Ar or other argillaceous accumulations, and the current state of isotope dating; g) synthesis of clay minerals; h) clay science, have been and will continue to be the kinetic and thermodynamic approach, phase equilibria result of an interdisciplinary and multidisciplinary diagrams; i) medium- and high-temperature crystalline cooperation. It is done by nature, and still more by phases of clay minerals, notably in the SiO2-Al2O3- extensive and multilateral use of clay matter. The H2O system, but also in other chemical systems. The historical, existing, and future interdisciplinary subregion “burial diagenesis” seems to be the most integration of scientific disciplines and technologies deeply and the most widely examined theme. The for a better recognition and use of clay materials can paper on the distribution, methods of identification be illustrated by a simple diagram (Fig. 1) showing and petrological importance of mixed-layer clay their mutual influence. Such a desirable interaction of minerals in sedimentary lithosphere by Weaver (1956)

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Fig. 1 Existing and desirable cooperation of clay science with the most influential theoretical, applied and related sciences, and respective technologies. The mutual influence is illustrated by arrows of varying strength.

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was an initial work based on statistically large the NW European continental shelf and their relations experimental material. His study of more than 6,000 to facies and hydrocarbon accumulation”. Vol. 21 sedimentary rock samples has shown that mixed-layer (No. 4), October 1986, contains 21 papers on clay minerals are abundant in sedimentary basins, “Features of mineral diagenesis in hydrocarbon being present in approximately 70 % of the rocks. The reservoirs”. Vol. 24 (No. 2), June 1989, with 17 investigation was supported by Shell Development papers, is oriented to “Clay diagenesis in hydrocarbon Company, Houston, Texas. Weaver stated that reservoirs and shales”. Vol. 29 (No. 4), October 1994, random interstratifications Il-Mo with ratio ranging contains 21 papers devoted to “Diagenesis, from 9:1 to 1:9, and Il-Ch-Mo are most abundant. Ch- overpressure and reservoir quality”. The last issue Mo and Ch-Ve are common but relatively less Vol. 24 (No. 1), March 2000, contains 25 papers on abundant. Three different regular Ch-Ve inter- 322 pages and is entitled “Mineral diagenesis and stratifications have been found. Similarly important reservoir quality – the way forward” (papers from have been the independently obtained data on the Jeans, 2000, to Macaulay et al., 2000). Similar issue depth mineral zonality with well defined phyl- appeared in Clays and Clay Minerals, 1993, Vol. 41 losilicate, zeolite and other mineral associations in (No. 2), with 12 papers, p. 117-267, on the theme North Siberian sediments of different geological ages “Geothermometry and geochronology using clay published by Kossovskaya and Shutov (1955, 1958, minerals”. It is not known that another genetic process 1963), and Shutov et al. (1969). Burst (1969) studying would be as much financially supported and as deeply the diagenesis of Gulf Coast clayey sediments finally and widely studied as “burial diagenesis” of clay dared to state its possible relation to petroleum minerals or argillaceous rocks. migration. Burst was the first who referred that during Close integration of geology with clay the transformation of smectite to illite, a dehydration mineralogy, crystallography and crystal chemistry process takes place, which is strongly correlated with over the past three decades has enabled some the production of hydrocarbons and primary oil mineralogical generalizations in burial diagenesis. migration. Dunoyer de Segonzac (1969) published From numerous published results, let us quote the further remarkable results on the diagenetic latest views important for geological interpretations. transformations of clay minerals and the parallel Meunier et al. (1998) deduced several possible changes of organic combustible substance from the reactions that may occur during the diagenetic bore holes of the Douala Basin, Cameroon. The transformations of clay minerals: 1) low-charge Cretaceous and Tertiary strata of pelites and lutites of montmorillonite + K+(mica) → high-charge the thickness of about 4 000 m contain, with montmorillonite + illite + ; 2) high-charge increasing depth, gradually transformed phyllo- montmorillonite layers → illite + chlorite + quartz; 3) silicates in two different rows. Montmorillonite low-charge montmorillonite → high-charge beidellite transforms in the following sequences: 1) in the Mg- + saponite + quartz; 4) high-charge beidellite + rich environment Mo → Ch-Mo or Ch-Ve → saponite + K+ → ordered Il-Sm + chlorite + quartz. corrensite → chlorite, while 2) in the K-rich Lanson et al. (1998) also showed that diagenetic environment Mo → Il-Mo or Il-Ve → rectorite → history of the Tet:Oct 2:1 phyllosilicates in different illite. The nonvolatile organic C to total organic C sedimentary basins varied as a function of the ratio increases with depth from 0.1 to about 0.5-0.8. geothermal gradient and its duration. They quoted Later on, other authors of numerous papers measured numerous authors who systematically studied and the reflectance of vitrinite, one form of the solid reported on smectite illitization in argillaceous organic combustible substance, which increases with diagenetic series of different basins during the past the depth and the carbon content (e.g. Barker and thirty years. Their common diagenetic evolution Elders, 1981; Price, 1983; Sweeney and Burnham, scheme depending on the time-temperature conditions 1990; Barker, 1991; Velde and Lanson, 1993; and experienced by the sediments can be expressed by the many others; see also an excellent monograph by following reaction sequence: smectite → randomly Degens, 1967). interstratified Il-Sm → ordered Il-Sm → illite. Well The great progress in the investigation of crystallized illite is the ultimate reaction product for diagenetic transformations of clay minerals in the illitization of both Il-Sm precursors and kaolinite- sedimentary basins of different geological ages, group minerals. Kaolinite can be diagenetically although mostly achieved in laboratories of dozens of transformed into smectite under higher activity of universities, has occurred thanks to wide financial Mg2+ and Ca2+, e.g. from the dolomite source, as support granted by oil production companies, and experimentally proved by Nadeau (1998). geological or exploration surveys or the bureaus of Transformation of kaolinite to dickite in several economic geology of rich countries interested in buried oil-bearing sandstone reservoirs proceeds with hydrocarbon research programs. Good evidence of increasing depth and temperature in the following such concentrated research activities can be found in sequence (Beaufort et al., 1998): disordered kaolinite five specialized issues of the Clay Minerals journal (600 m) → kaolinite ± disordered dickite → published between 1984-2000. Vol. 19 (No. 3), June disordered dickite ± ordered dickite → ordered dickite 1984, is devoted to “Patterns of mineral diagenesis on + disordered dickite → ordered dickite (5,000 m). The

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dissolution of clastic feldspar accelerates the sites. This has been also the cause why clay mineral crystallization of ordered dickite starting from a depth assemblages from weathering crusts and soils formed about 3,000 m. Drits et al. (1998) investigated the from various types of rock under varying conditions in changes in the crystal structure of 2:1 layers in the whole world were distinguished relatively early in diagenetic or hydrothermal and illite-smectites the 20th century (see books by Grim, 1953; Chukhrov, still into greater details. The determined amounts of 1955; Keller, 1957; Loughnan, 1969; Stoch, 1974). cis (wcv) and trans (wtv) vacant 2:1 layers using both Similar knowledge has been attained in the WILDFIRE simulation program and calculations investigation of hydrothermal clay associations. Now, based on some X-ray reflections enable an evaluation can the most promissing discoveries using modern of the mechanism of illitization in various geological methods, and under the influence of all the recognized environments. Significant changes in wcv and wtv order-disorder states of clay minerals, be expected in during illitization are likely due to a dissolution- the investigation of clay pseudomorphs after known precipitation, whereas almost constant values indicate rockforming silicates and volcanic glasses. It has been a solid-state transformation. shown by several authors (see quotations and authors’ The historical monograph by Konta (2000) results by Proust and Velde, 1978; Konta, 1981) that reports upon a number of further papers on the clay pseudomorphs, after rockforming silicates in progressive burial diagenesis and clay mineral weathering crusts, preserve the chemical micromilieu transformations. They include formation of of original primary minerals not only in the root parts crystallites, dissolution/crystallization, precipitation but also in the completely argillized upper parts of the and crystal growing, solid state transformation, profiles. The movement of aqueous solutions is changes in tetrahedral and octahedral sheets and initially controlled by the capillary system of the interlayer space, Ostwald ripening, ion exchange, original and by the crystal structure of + changes in layer charge, NH4 ion in Il-Sm individual primary silicates. But later, the flow is interstratifications, changes in particle morphology, combined with ion diffusion in the very dense TEM, SEM and HRTEM imaging, the role of water in capillary system within the clay mass. The narrow the Sm-to-Il reaction, oxidation/reduction, capillary and interlayer ways, the tortuosity of compaction, dehydration, participation of non-clay pathways and large specific surface area of newly materials, changes in the orientation of the formed clay matter retard any big scale equilibrium. anisometric components (by SEM), clay minerals in The individual chemical and microstructural different microenvironment of the pore space, micromilieu in each clay pseudomorph plays a big determination of Il-Sm and other structures using role during the whole argillization. It influences not multispecimen X-ray diffraction profile fitting, only the resultant chemical composition but also the determination of reliable and detailed structural order-disorder states of newly formed clay minerals. models for mixed-layer minerals (MPFP = multi- Volcanic glass in contact with water is less stable and specimen profile), isotope systematics, its argillization proceeds more rapidly compared with laboratory synthesis of clay mineral inter- the crystalline primary silicates of the corresponding stratifications, and on other themes. chemical composition. The removal of dissolved The activities of major clay-mineral-forming components from glass, however, is retarded due to elements, i.e. Al, Mg, Fe, Si shielded by oxygens limited system of cracks and no cleavage system ±hydroxyls, and Ca, Mg, Na, K, NH4 hydrated with typical for most crystalline minerals. This is the interlayer water, and the thermal gradients with time reason why volcanic glasses still better preserve their control the resulting mineral assemblage in any geochemical milieu than crystalline primary silicates argillaceous accumulation. This is valid not only for (compare the results by Gilg et al., 2003). the burial diagenesis of argillaceous sediments or What still lies before us is the investigation of hydrothermal assemblages but also for weathering clay minerals in the accessible universe. Are the crusts and soils. The argillization of primary astronomers and the seekers of life in outer space rockforming minerals and volcanic glass has been aware that the planets or moons without clay minerals expressed in literature by many stoichiometric or some clay remnants never possessed hydrosphere equations in the mineral(volcanic glass)-water-(acid) and thus life on their surfaces? th systems (Keller, 1957; Loughnan, 1969 and many The 4 research region of clay science focuses others). Thermodynamic or kinetic reaction diagrams on „Physical and physicochemical properties of clay may help a lot in the interpretation of genetic minerals“ related to the structure, crystal chemistry, conditions and solubility of clay minerals (e.g. Zen, layer charge, charge density, adsorbed ions, interlayer 1962; Helgeson et al., 1969; Lippmann, 1981;Tardy bondings, and properties of their aggregates including and Fritz, 1981; Aagaard and Helgeson, 1983; size distribution (Konta, 2000). It comprises the Garrels, 1984). following research subregions: a) clay-water system, Can we expect such great results as in the “burial colloidal properties and surface chemistry; b) diagenesis” in the investigation of clay minerals of dispersion in water and the effect of electrolytes; c) weathering crusts or hydrothermal accumulations? flocculation and deflocculation; d) stability of The suitable samples are at one’s disposal in many suspensions in various liquids; e) swelling and

CLAY MINERALS INCLUDING RELATED PHYLLOSILICATES: INTERDISCIPLINARY RESEARCH … 61

shrinkage; f) adsorption of water and corresponding of 0.5, but for the others after removal of 2 up to 2.5 technological properties; g) sorption selectivity of cations per unit cell containing 4 octahedral cations. phyllosilicates; h) organo-clay systems; i) transport of Suquet et al. (1991) prepared similar porous material chemicals through clays; j) true density of clay by a mild attack of a macrocrystalline vermiculite minerals and argillaceous rocks; k) bulk density; l) using 1 M HCl at 80 oC for 2 hours. By electron porosity, preferred particle orientation and tortuosity microscopy, infrared spectrometry, X-ray powder of pathways; m) stability of clay minerals and other diffraction and thermal analysis, it has been shown rockforming silicates in various environments; n) that the leached vermiculite is composed of more or optical properties; o) magnetic properties. Modern less attacked layers retaining their original platy investigation in any of these subregions requires morphology, and non-crystalline hydrated silica. The knowledge of modern discoveries in the crystal all hitherto published results testify that acid structure and crystal chemistry of phyllosilicates. activation leading to an effective sorbent (bleaching The 5th research region “Modified clays” covers earth) must be a partial dissolution of expanding at least eleven theoretical and simultaneously widely phyllosilicates in inorganic acids. The final product applied subregions: a) homoionic clays with one of must not be solely three-dimensional amorphous common hydrophilic inorganic interlayer cations (Na+ silica. We have to admit, however, that we don’t know or Ca2+ or others); b) clay minerals with one polar yet the structure and morphology of remanent silica organic molecule adsorbed (e.g. pyridine, quinoline, after the optimum acid treatment. ethylene glycol); c) expansible phyllosilicates with A very promissing field in the preparation of organic cation changing the original hydrophilic clay clay sorbents and quick inorganic reactants is the (with Na+, Ca2+ and other cations) to an organophilic investigation of precisely reproducible grinding or clay of desired microporosity (organo-clay molecular milling leading to a product of constant properties. sieve); d) expansible clay minerals with negatively First, it is necessary to study the optimum energetical charged organic polymer (polyanion); e) clay minerals procedure and the optimum time length of the used with non-ionic organic polymer; f) expansible mechanical treatment. There is a fundamental phyllosilicates pillared with various oligomeric difference between dry and wet grinding or milling. inorganic oxycations, mostly /III/- and /IV/-valent The structural phenomena “finite crystal size as a cations, which can be widely used as sorbents and lattice disorder” and “mechanically disordered catalysts; g) pillared inorgano-organo-clays; h) structures” (Brindley, 1980) play a decisive role pillared and delaminated hydroxy-R/III/ interlayered during grinding or milling of clay raw materials. The smectites; i) H+-smectites and acid activated clays; j) mechanically disordered structures and received short- thermally treated (calcined) clays; k) milled or ground range ordering attracted attention of scientists for clays, delaminated but sometimes altered up to short- more than fifty years (Bloch, 1950; Gregg et al., 1953; range structures (‘amorphous state’). These research Mackenzie and Milne, 1953; Robertson, 1953; subregions are under strong influence of chemistry, Takahashi, 1959; Miller and Oulton, 1970; Petkof, physics and the demands of industrial technologies. 1975; Číčel and Kranz, 1981; Papirer and Roland, The preparation and investigation of differently 1981; Cornejo and Hermosin, 1988; Pérez-Rodríguez modified clays required great effort of many experts. et al., 1988; Suquet, 1989; Drief and Nieto, 1999; One good example of the continual research Reynolds and Bish, 2002). We still don’t know the endeavour has been referred by Komadel (2003) in his temperature evolved on the surface of clay minerals critical review of results obtained on: a) H+-saturated during grinding or milling. The point-evolved smectites where exchangeable cations are replaced temperature during dry treatment is probably high. with protons; b) acid activated smectites; c) smectites Can it cause partial dehydroxylation and support local with reduced structural Fe(III) to Fe(II) causing the molecule or ion migration? Can a mere delamination increase of negative charge on the 2:1 layers; d) Li+- during wet grinding in the presence of water or saturated ; e) interaction of smectites another suitable liquid be advantageous for the with methylene blue which is a very sensitive method preparation of novel chemically modified clays? Do to probe layer charge density of natural and the defined mechanical treatments accelerate chemical chemically modified smectites. According to reactions between dry or slightly wet clays and Madejová et al. (1998), IR spectra of a smectite chemicals? These and many other questions pertaining treated in 6 M HCl at 80 oC for 0, 3, 4 and 8 hours to the remaining subregions of the 5th research region show a gradual decrease of the Si-O-Al bending of clay science need, above all, a support from the 1st vibration near 520 cm-1, which is the most sensitive and 2nd research regions. More information about the band to the presence of residual Al in the octahedral research of other modified clays can be found in the sheet. They simultaneously showed an increase of the monograph by Konta (2001). -1 th Si-O vibrations near 1100 cm assigned to amorphous The 6 research region “Applied clay science silica with a three-dimensional framework. Novak and including the exploitation and beneficiation of raw Gregor (1969) found that the maximum surface area materials focusing on the application in various and the highest decolorizing ability is attained for industrial branches, soil science and agriculture, civil some acid treated dioctahedral smectites after removal engineering and ecological projects”, needs still a

62 J. Konta

Fig. 2 A suggested view of the existing as well as desirable interaction among the six major research regions of clay science significant for their further development and practical applications. This view accentuates the expected development of clay mineralogy, petrology of argillaceous accumulations, soil science, and practical applications. Thin arrows: a mutual weak impact; thicker arrows: a mutual more intense impact; the heaviest arrows: the most successful integration and the most developed research between the first two research regions; the bold-hyphenated arrows: a desirable more intense integration.

stronger integration with the remaining five research know the demands of modern industry and regions. The applied research is usually oriented technologies? There is no doubt that great results have according to some immediate demands of the practice. been achieved in theoretical clay science. The Fig. 1 shows the existing and desirable cooperation of effective integration of research regions, 1 to 5 with clay science with the most important theoretical, the 6th region, needs also to organize modern applied and related sciences and respective techno- conferences, e.g. on the theme, “Order-disorder states logies. The special journal Applied Clay Science, in the crystal structures and crystal chemistry of clay edited by Elsevier in Amsterdam is one of the minerals and their application in technologies”. Such commendable initiatives supporting the 6th research and similar topics can bring more support to clay region of clay science. Further development of applied science from industry. clay science needs, however, much stronger support of Fig. 2 is an attempt to summarize partly the interested industrial companies. Also it is necessary to existing, and partly the desirable interaction among ask: Do the present-day clay scientists sufficiently the six major research regions of clay science. Thin

CLAY MINERALS INCLUDING RELATED PHYLLOSILICATES: INTERDISCIPLINARY RESEARCH … 63

arrows indicate a mutually weak impact, which is great. It will bring further progress to clay science perhaps common but insufficient. The thicker arrows itself, as well as to all earth sciences and other indicate a more intense impact of the results radiating cooperating scientific and engineering disciplines. from one to another region. The heaviest arrows More intense integration among the six research express the most successful integration and most regions of clay science opens new horizons in both the developed research between the two first research theory and application. regions. These also are marked by the heaviest points. The strong dashed arrows show a desirable more REFERENCES intense integration between a) the crystal structure Aagaard, P. and Helgeson, H.C.: 1983, Activi- (including chemistry) research and the investigation of ty/composition relations among silicates and natural accumulations and genetic conditions of clay aqueous solutions II. Chemical and thermo- and related minerals; b) the crystal structure dynamic consequences of ideal mixing of atoms (including chemistry) and modified clays research among energetically equivalent sites in mont- regions. The integration sub a) reached some morillonites, illites, and mixed layer clays. Clays remarkable discoveries in the recognition of the and Clay Minerals, 31, 207-217. diagenetic and epigenetic transformations of buried Adler, H.H.: 1950, Infrared investigations of clay and clay minerals, depending on the geothermal gradient related minerals. American Petroleum Institute, and its duration in different geological formations. Project 49, Prelim. Report 8, 1-72, New York, Columbia University. 5. CONCLUSION Ahn, J.H. and Peacor, D.R.: 1986, Transmission and Clay minerals as hydrous phyllosilicates with analytical electron microscopy of the smectite- alternating tetrahedral (Tet) and octahedral (Oct) to-illite transition. Clays and Clay Minerals, 34, structural sheets (where Tet:Oct = 2:1 or Tet:Oct:Oct 165-179. = 2:1:1 or Tet:Oct = 1:1) are the most common Alietti, A.: 1956, Il minerale a strati misti saponite- crystalline reaction products between the surface talco di Monte Chiaro (Val di Taro, Appennino lithosphere and the hydrosphere. They occur Emiliano). Academia Nazionale dei Lincei, ordinarily in soils, different argillaceous rocks, and Rend. Cl. Sci. Fisiche, Math. e Nat. Ser. 8, 21 clay raw materials of continental and marine (fasc. 3-4), 201-207. environments formed through the geological history Allen, V.T., Fahey, J.J. and Ross, M.: 1969, Kaolinite of the Earth. Due to their admirable physical and and anauxite in the Ione Formation, California. chemical properties, clay minerals are used in many American Mineralogist, 54, 206-211. industrial branches and are important in agriculture Altschuler, Z.S., Dwornik, E.J. and Kramer, H.: 1963, and forestry, civil engineering, and ecology. 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