Regional differences in clay mineralogy are found in British Lower Palaeozoic slate belts formed during Caledonian terrane amalgamation. Extensional basins in Wales, the northern Lake District and the Isle of Man are characterized by a greater diversity of species in clay mineral assemblages. Slates that evolved in these basins contain both the K- and Na-rich products of the 2:1 dioctahedral reaction series. Pyrophyllite, rectorite and corrensite are sporadically distributed but kaolinite is rarely recorded even in lowest-grade mudstones. In contrast, clay assemblages that evolved in the convergent basins of the Scottish Southern Uplands and northern England generally contain fewer mineral species, and Na-micas and pyrophyllite are rare or absent. Na-bearing clays may have been generated from low-temperature mixing of hydrothermal fluids and seawater in the extensional basins. Such fluids appear to have been unavailable in the convergent basins through lack of volcanic activity in the early stages of basin development.

The laser Raman microprobe spectrum of gibbsite displays four intense v (OH)- stretching bands at ~3365, 3435, 3525 and 3618 cm-1, bayerite shows three near 3425, 3545 and 3564 cm-1, nordstrandite has three near 3492, 3566 and 3623 cm-1, and doyleite one broad band centred at -3545 cm-1 with sometimes a prominent shoulder near 3615 cm-1. The four polymorphs also possess distinctly different Raman signatures of medium to strong bands in the region 100–1200 cm-1. These differences provide a non-destructive routine determinative procedure by direct microsampling of untreated crystals, fragments, and microcrystalline powders. Sample preparation is minimal. Excessive noise and non-quenchable fluorescence are the principle limitations of the technique.

The apparatus described enables investigations to be carried out in any desired gas or vapour at pressures not far removed from atmospheric. Two different specimen-holder blocks have been developed: a nickel one for use with inert gases (e.g., nitrogen) and high sensitivity of recording, and a ceramic one for use with active gases and vapours (e.g., oxygen or water vapour) and rather lower sensitivities. Evacuation of the system to pressures of less than 0·05 mm Hg is also possible. The temperature control system consists of a commercial anticipatory temperature controller and a motorized autotransformer; the differential thermal curve is recorded photographically. Some results are given to illustrate the high sensitivity of the apparatus, its application to highlyorganic soil-clays and to the study of combustion reactions.

Factors influencing the degree of intercalation (‘reactivity’) of kaolinite group minerals have been investigated using six kaolin minerals, with variable crystallinity and particle size. Tests were performed to measure the degree of intercalation with potassium acetate, formamide, dimethylsulphoxide and hydrazine.

These experiments indicate that intercalation degree depends on a number of factors, including particle size, degree of ordering, type of guest molecules, method of intercalation, and presence and types of impurities. Anew method for determination of the degree of intercalation is proposed, which is not dependent on the intensity of complex reflections. The results indicate that formamide is the most sensitive reagent to distinguish differently ordered kaolin minerals whereas hydrazine appears as the most appropriate reagent to differentiate kaolin minerals from other 7 Å phases.

Interstratified illite-smectites from Carboniferous sediments from the Alston and Askrigg blocks and the intervening Stainmore trough of the northern Pennines, UK, were examined by XRD. Both blocks are underlain by Caledonian granites. During late Carboniferous times sediments overlying the Alston block were intruded by the Whin Sill. The percentage smectite in illite-smectite (%S in I/S) varies from ∼35% to <5% only homogeneous mudstones give consistent results. In the case of the Askrigg block and Stainmore trough, a good inverse correlation was found between %S in I/S and vitrinite reflectance. Both illitization of illite-smectite and vitrinite reflectance increase towards the centre of the block. This is thought to be related to high heat-flow centred about the granite basement. In the case of the Alston block, there is no direct relationship between clay and vitrinite data, vitrinite reflectance being controlled by the position and thickness of the Whin Sill. Except where close to the contact, the Whin Sill had no apparent effect on %S in I/S. As observed for the Askrigg block, %S in I/S is directly related to the position of the underlying granite. The progressive illitization of illite-smectites of low expandability is very slow when compared to vitrinite alteration in response to rapidly increasing temperature. Consequently, %S in I/S is a potential indicator of thermal maturation in situations where vitrinites, by virtue of their rapid response to increasing temperatures, fail to provide a regional view of heat-flow patterns.

Brazil is a significant producer of kaolin with almost 2.5 Mt in 2005 representing 10% of the world's total of 25.0 Mt. Brazil is now the second largest producer in the world, after the USA, having overtaken the United Kingdom in 2005. The kaolin resources are widespread throughout the country and are varied in their origin, physical and chemical properties and morphology. The kaolin industry in Brazil has shown a dramatic rise over the last 15 years with production of beneficiated kaolin increasing from 0.66 Mt in 1990 to 2.5 Mt in 2005. The reason for the growth is solely the development of large kaolin deposits in the Amazon Basin that account for 90% of Brazil's production. In 2005 there are just two companies involved in the production and sales of kaolin from the Amazon Basin, namely Imerys (RCC — Rio Capim Caulim) and Caemi (a subsidiary of CVRD — Companhia Vale do Rio Doce) with kaolin operations of CADAM (Jari River) and PPSA (Capim River operations).

Ion-exchanged montmorillonites behave as solid acid catalysts and are effective and selective catalysts for the hydration of ethylene. The reaction proceeds predominantly in the interlamellar environment of the clay catalyst. Ethylene conversions were found to be markedly dependent on the choice of exchangeable cation, with Al being the best of those examined.

In soils and other weathering environments, hematite and goethite are usually formed in the presence of clay minerals. Two-line ferrihydrite was aged in the presence of six different clay minerals in aqueous suspension at 25°C and pH 4, 5, 6 and 7 for 16 years. The transformation into hematite/goethite mixtures was complete in the systems with gibbsite, kaolinite, illite and smectite, but incomplete in those with soil smectite and allophane. Soil smectite and allophane, as well as increasing pH, favoured hematite over goethite. The grainy and multi-domainic hematite crystals in the allophane system contained Si and Al (EDX) and showed a Si – O vibration at ∼920 cm– 1 (FTIR). The unit-cell contraction due to structural Al was counteracted by structural OH, which was removed at 200°C. Heating also increased the magnetic hyperfine field at RT by 1.2 – 1.6 T. Hematite crystals with irregular shape and grainy interior have also been observed in soils.

The clay mineralogy of the Cretaceous strata of the British Isles is described and discussed within its lithostratigraphical and biostratigraphical framework using published and unpublished sources as well as 1400 new clay mineral analyses. The regional clay mineral variation is described systematically for the following strata:

1. (1) Southern England — Purbeck Limestone Group (Berriasian/Ryazanian; Lulworth and Durlston formations), Wealden Group (Valanginian—Barremian/Aptian; Ashdown, Wadhurst Clay, Tunbridge Wells Sands, Grinstead Clay Member, Wealden Clay, Wessex and Vectis formations), Lower Greensand (Aptian—Lower Albian; Atherfield Clay, Hythe, Sandgate, Folkestone Sands, Ferruginous Sands, Woburn Sands and Faringdon Sponge Gravels formations), Selborne Group (Middle—Upper Albian; Gault Clay and Upper Greensand formations) and the Chalk Group (Cenomanian—Lower Maastrichtian).

2. (2) Eastern England — Cromer Knoll Group (Ryazanian—Upper Albian; Speeton Clay, Spilsby Sandstone, Sandringham Sands, Claxby Ironstone, Tealby, Roach Ironstone, Dersingham, Carstone and Red Chalk (or Hunstanton Red Limestone) formations).

3. (3) Scotland — Inner Hebrides Group (Cenomanian—Campanian; Morvern Greensand, Gribun Chalk, Coire Riabhach Phosphatic Hibernian Greensands formations).

4. (4) Northern Ireland — Hibernian Greensands (Cenomanian—Santonian) and Ulster White Limestone formations (Santonian—Lower Maastrichtian).

The stratigraphical patterns of clay mineral variation divide naturally into two types; firstly, the more complex pattern of the Lower Cretaceous strata and secondly, the simple pattern of the Upper Cretaceous. Clay mineral variations in the non-marine and marine Lower Cretaceous strata of England are best explained by the interplay of two main clay mineral assemblages between which all gradations occur. The assemblage which dominates the main clay formations consists of mica, kaolin and poorly defined mixed-layer smectite-mica-vermiculite minerals, and sometimes includes vermiculite and traces of chlorite. It is dominantly of detrital origin and detailed evidence indicates it is derived largely from the reworking of Mesozoic sediments although ultimately from weathered Palaeozoic sediments and metasediments. Although mainly of detrital origin, this assemblage contains a persistent component that formed coevally with the approximate depositional age of its host sediment. Whether this component is of soil origin or was neoformed in the sediment shortly after deposition is unclear. There is little firm evidence indicating the sources of this clay mineral detritus. However, in the strata of the Wealden Group of southern England, mineral trends suggest three sources; one of these was to the west (Cornubian Massif), another must have been the Anglo- Brabant landmass. In the Selborne Group (Middle—Upper Albian) and in the overlying Lower Chalk (Cenomanian) where this assemblage makes its last appearance in the Cretaceous of England, there is good evidence of easterly and south-easterly sources.

The second main assemblage tends to be largely monominerallic, and usually dominated by smectite with or without small amounts of mica; less frequently, kaolin, berthierine or glauconite sensu lato is the sole or dominant component. It is considered to be of volcanogenic origin, derived from the argillization of volcanic ash under different conditions of deposition and diagenesis. The source of the ash in Berriasian—Aptian times seems to have been an extensive volcanic field in the southern part of the North Sea and in the Netherlands, whereas in the Albian (and extending into the Cenomanian) a westerly source dominated. The current controversy about the role of climate or pattern of volcanic activity controlling the clay mineral stratigraphy of the Lower Cretaceous is reviewed.

In the lower part of the Upper Cretaceous strata of England, Scotland and Ireland, sand-grade glauconite is particularly abundant. Much of it represents the glauconitization of pene- contemporanous volcanic ash, possibly of basaltic origin, associated with continental breakup and the opening up of the Atlantic Ocean and the earliest stages in the development of the Hebridean Tertiary Igneous Province. The Upper Cretaceous Chalk facies of England and Ireland is dominated by a smectite-rich clay assemblage containing mica, and the various hypotheses for its origin (detrital, neoformation, volcanogenic) are reviewed in the light of available mineralogical, chemical and geological data.

Late Triassic sandstones from Quadrant 22 in the North Sea contain two generations of chlorite cement. Grain-coating chlorites consisting of curved, irregular crystal plates formed very early in diagenesis and are largely confined to marginal marine beds. Later diagenetic pore-filling chlorites, consisting of euhedral platy crystals, occur throughout the sequence in fluvial as well as marginal marine beds. Both generations of cement show similar XRD patterns; the 001 basal reflection of 14·0–14·06 Å is broad and of low intensity, whereas the 002 reflection at 7·05 Å is sharp and intense. Slight contraction of the 14 Å basal spacing to 13·6 Å occurs after heating to 600°C. Electron microprobe analyses show the cements to be Fe-rich clinochlores with Fe/(Fe + Mg) ratios varying between 0·41 and 0·50. They are more Mg- and Si-enriched than most other reported North Sea authigenic chlorites. The grain-coating chlorites have an average composition of (Fe3·06Al3·93Mg3·32) [(Si6·76Al1·24)O20] (OH)16. The pore-filling chlorites tend to show more variable compositions. The high Si values probably reflect both minor interstratification with smectite or vermiculite and contamination of the analyses by a closely associated illite/smectite clay. An origin related to alteration of a precursor swelling chlorite or corrensite is attractive on chemical and morphological grounds for the early grain-coating chlorites. However, direct precipitation from porewaters is the favoured origin for the later pore-filling chlorites, with the required ions being supplied by mineral decomposition reactions involving detrital silicate minerals and dolomite cements.

At room temperature both Fe(III)-exchanged montmorillonite and Fe(III)-hectorite gave similar Mössbauer spectra, each consisting of a single doublet with parameters characteristic of ferric iron. At 77 K the Fe(III)-hectorite gave a spectrum similar to that observed at room temperature, but with the montmorillonite an additional distinct doublet, with relatively large values of both isomer shift and quadrupole splitting, was observed. The Fe(II)-exchanged samples behaved very differently at room temperature and 77 K. At 77 K well-defined doublets were produced; these had quadrupole splittings similar to those shown by the ion and appreciably greater than those observed for Fe(II) in the structural sites in layer-silicates. At room temperature, however, there was no absorption corresponding to ferrous ions in either of the specimens, because the recoil-free fraction was low as a result of the loose association between the ion and the mineral lattice.

Dissolution kinetics of sepiolite from Eskisehir (Turkey) have been investigated at various temperatures and particle sizes using dilute hydrochloric and nitric acids. Dissolution reaction rate constants were calculated and apparent activation energies were dependent on acid concentration. For both acids, apparent activation energy values reached a minimum of ∼11 kcal/mol at an acid concentration of 0·75 M. For the second-order reaction which is independent of the acid concentration, the activation energy was 14·5 kcal/mol for both acids. The reaction rate constants were proportional to the acid concentrations, and inversely proportional to the square-root of the initial particle radii of the sepiolite.

Quantitative gas chromatographic analyses supplemented by X-ray diffraction studies of the adsorption of ethanol and acetone (as model polar organic compounds) on homoionic montmorillonite revealed marked variation in the number of molecules associated with each exchange cation. The results show increasing association in the order K+ <Na+<Ba2+<Ca2+. K+ and Na+ associate with two and three molecules, respectively, of either ethanol or acetone, and the resulting complexes expand to form a monolayer (∼13 Å). Ba2+ and Ca2+ form both monolayer complexes as well as double layer complexes. In the single layer complexes Ba2+ associates with either four molecules of ethanol or four molecules of acetone, Ca2+ associates with five molecules of ethanol or four molecules of acetone. In the double-layer complexes the observed cation-molecule ratios are 1 : 8 for both Ba2+-ethanol and Ba2+-acetone, 1 : 10 for Ca2+-ethanol, and 1 : 8 for Ca2+-acetone.

The striking dependence of ethanol and acetone adsorption on the nature of the exchangeable cation suggests that cation-dipole interactions play an important role in the adsorption process. Structural models of the organic complexes are presented.

Water adsorption by interlamellar complexes of poly(ethylene glycols) and montmorillonite has been determined using a silica spiral spring, and supplementary data obtained by X-ray and infrared techniques. The adsorbed water enters the interlamellar region, where it is associated with the exchangeable cation. The lattice swells to accommodate the intercalated water. Only weak hydrogen bonds are formed between the surface of the clay and the adsorbed water or between adsorbed PEG molecules and adsorbed water. The presence of PEG did not prevent extensive swelling of sodium montmorillonite.

SWy-1 and SAz-1 smectites and an Italian bentonite from Sardinia were mechanically deformed via high-energy ball milling for 20 h, in a controlled thermodynamic environment at constant temperature (25°C) under vacuum. The deformed smectites have a lower cation exchange capacity (CEC) and form thicker particles than the original ones, due to agglomeration of smectite crystallites. The 001 diffraction maximum shifted to lower d spacings, the intensity of the 060 reflection decreased and the background at 20-30°2θ increased, suggesting partial amorphization of the smectite. Moreover, the layer charge of the smectites decreased. The intensity of the complex stretching band at 3625 cm-1, and the AlAlOH, and AlFe3+OH bending bands at 916 cm-1 and 886 cm-1, respectively, decreased, while the band at AlMgOH bending at 849 cm-1, disappeared. Deformation mainly disrupted the octahedral sheet and preferentially destroyed those sites occupied by Mg cations, thus explaining the observed decrease in layer charge. Octahedral sites occupied by Fe were least affected. The disruption of the octahedral sheet is substantiated further by the almost total disappearance of the dehydroxylation peak, which is more pronounced in the Mg-rich SAz-1 smectite.

During an extensive survey of brickmaking clays by the differential thermal analysis method (carried out from 1947 onwards) it was observed that the clays of the Keuper Marl gave a series of very similar thermal curves which could not be explained by the presence of known clay minerals. Dr D. M. C. MacEwan of Rothamsted Experimental Station kindly carried out an X-ray examination of one of the samples for us, and he has reported the results of this examination, and the examination of a Keuper Marl sample from another source, to the last meeting of this Group. He postulated the existence of a “hydrated chloritic material”—sometimes exhibiting an expanding lattice stabilised by glycerol.

Since then the Keuper Marls have been further studied at the Building Research Station both by thermal analysis and X-ray methods and this paper is an interim report of this work. MacEwan's findings have been confirmed and some additional information is presented.

Examination of clays from surface and basal horizons of four Scottish soils by differential thermal analysis, before and after heating to 600°C and by infra-red spectroscopy indicates that these contain a proportion of highly hydrated amorphous material, resembling allophane in its properties, and that this component is particularly high in clays from the surface horizons with the greatest organic matter content. This conclusion is consistent with the cation-exchange capacities of the clays and with the amounts of silica and alumina extractable from them by hot sodium carbonate solutions. The ratio of silica to alumina in these extracts indicates that the amorphous material is highly siliceous.

Basal spacing data for neutral amine complexes with montmorillonite and vermiculite are explained on the basis of two layers of fully extended amine molecules inclined at about 65° to (001) with the NH2 groups closely associated with pairs of silicate oxygen atoms. The molecular orientation is shown to be favourable for good intermolecular packing and for possible NH..O bonding, but the results do not constitute proof of such bonding. Packing of the molecules on the silicate surfaces and with respect to each other may explain the formation of double layer complexes. The amine data are correlated with corresponding data for the low-temperature (or below melting point) series of alcohol-montmorillonite complexes and it is suggested that the molecular layers may have some solid-like characteristics.

Nearly pure sepiolite clay crops out in a playa-like depression near El Bur, Central Plateau region of Somalia. The deposit is associated with the Lower to Mid-Eocene Taleh Formation that includes, besides limestone, dolomite and gypsiferous marls, extensive anhydrite and various evaporites, primarily gypsum. The material was examined by XRD, DTA, IR and EM. The XRD and DTA analyses indicated that from 40 cm down to a depth of 300 cm, the material consists of well crystallized sepiolite, accompanied in some layers by minor calcite and traces of quartz and halite. The chemical composition, determined by XRF, indicated a low-Fe mineral, with the formula: (Si11.888Al0.l12)(Mg7.313Al0.154Fe0.084)O30(OH2)4(OH2)4.x8H2O.

The fibres, arranged in the form of interwoven mats, are straight and have lengths varying between 2-6 µm and widths of 20-40 nm. Commonly, they are aggregated into units of two parallel-lying fibres, with a random orientation against each other, creating a dense network of pores. The high viscosity and external surface area (306-346 m2g-1) of the material, compared to those of the Spanish Vallecas sepiolite, suggest the high industrial suitability of this clay. The extent of the deposit is not known. Lithology and geomorphology indicate a lacustrine, closed basin evaporative environment of formation for this deposit. In contrast to the palaeolacustrine environments of formation of Spanish and Turkish sepiolite deposits, the E1 Bur sepiolite apparently is more recent.

Clays from the Ae and C horizons of five Podzol soil series in New Brunswick were examined by X-ray, chemical and infrared absorption methods. All the experimental evidence indicated that the Ae horizons contained predominantly a dioctahedral randomly interstratified mica-vermiculite-smectite clay, whereas the C horizons contained abundant dioctahedral mica (illite) and trioctahedral chlorite. Since no trace of chlorite as a separate phase or as one component of the interstratified structure was found in the Ae horizons, it was concluded that, while the inherited chlorite was decomposed in all of the Ae horizons, mica was differentially hydrated giving an interstratified structure. Fourier transforms of the three-component interstratified clay revealed different ratios of hydrated layers (vermiculite and smectite) to non-hydrated layers and different stacking sequences. The proportion of hydrated layers and randomness of stacking was related to the degree of weathering as measured by the accumulation of TiO2 in the Ae horizon and it was suggested that they may be related to the degree of podzolization.