Smectites in the montmorillonite-beidellite pseudo-binary system were synthesized from glass at the hydrothermal conditions 100 MPa and 250–500°C. Products were analysed by X-ray powder diffraction for randomly oriented and glycolated samples, and also according to the Greene-Kelly test. A new mixed-layer mineral consisting of regularly interstratified montmorillonite-beidellite was found below 400°C for M50B50 composition, where M and B denote the compositions of ideal Na-montmorillonite and Na-beidellite, respectively. Montmorillonite was obtained as a single phase below 375°C in the composition range from M100B0 to M78B22. Above 375°C, montmorillonite decomposed into an assemblage of beidellite, saponite and a silica mineral. Beidellite as a single phase was synthesized below 400°C for M0B100 composition. Above 450°C, Na-rectorite (regularly interstratified paragonite-beidellite), Mg-free dioctahedral smectite and/or Mg-rich trioctahedral smectite appeared together with silica minerals. These smectites showed the same swelling behaviour as that of montmorillonite. Phase relations in the montmorillonite-beidellite pseudo-binary system indicate no complete solid-solution series.

Mössbauer spectra of Fe2+Fe3+ and Fe2+Al hydroxycarbonates taken in the paramagnetic state were fitted using two Fe2+ and Fe3+ doublets each. These spectra can be interpreted in terms of an ordered cation arrangement in the pyroaurite-type structure. The inner Fe2+ doublet seems to be the outcome of excess Fe3+ in the samples studied. The outer Fe2+ doublet (quadrupole splitting ∼2·8 mm s−1, FWHM = 0·26 mm s−1) is relatively well-defined and can, together with the fact that this doublet disappears on oxidation, possibly serve to identify these compounds in natural systems.

Clay minerals are ubiquitous constituents in soils on Earth, are occasionally found in meteorites, and may also occur on planetary surfaces in the presence of water. However, little is known about the fundamental Mössbauer parameters (the intrinsic isomer shift, δI, the characteristic Mössbauer temperature, θM, and the recoil-free fraction, f) that are characteristic of clay minerals and critical to the correct interpretation of the Fe3+/ΣFe ratios as well as the mineral modes. Spectra of well characterized single mineral samples at multiple temperatures may be used for the determinations of f. Hence, measurements of five-layer silicates with a range of layer types are presented here: nontronite, Fe-smectite, glauconite, annite and biotite. The spectra were fitted using three different software packages: WMOSS from Science, Engineering & Education Co. in Minnesota; Recoil, from the University of Ottawa in Canada; and two programs used at the University of Ghent in Belgium. Four different approaches to modelling line shapes were used: (1) Lorentzian; (2) pseudo-Voigt (convolution of Lorentzian and Gaussian curves); (3) quadrupole-splitting distributions (QSD); and (4) a technique that does not assume a particular line shape (subsequently referred to as ‘model-independent’). Values of δI, θM and f were determined using the method of De Grave & Van Alboom (1991).

Results show that multiple doublets are routinely required by all models to represent Fe-site occupancy, even when all the Fe atoms of the same valence are in the same site, as is the case for dioctahedral smectite, nontronite, mica and glauconite. Consistent values of centre shift (δ) and quadrupole splitting (Δ) were obtained for the two distributions of M2Fe3+ in the smectites. In glauconite, a single Fe2+ doublet was clearly resolved and gave systematic values for δ, Δ and area, but the two Fe3+ doublets were less defined. In annite, two Fe2+ and two Fe3+ doublets were modelled, while three Fe2+ and one Fe3+ doublet were used for biotite. Three different programs that use Lorentzian line shapes gave very similar results for δ, Δ and area. The two different implementations of QSD line shapes gave similar but sometimes slightly different results, and the pseudo-Voigt and model-independent fits usually fell between the ranges for Lorentzian and QSD results.

The value of δI is ~0.58 mm/s for Fe3+ and ~1.31 mm/s for Fe2+ across all models and line shapes, which is expected because the Fe3+ has an additional shielding 3d electron. Values for θM data are nearly identical for Fe3+ in nontronite and Fe-smectite (~450 K), somewhat varied for Fe3+ in glauconite and biotite (θM = ~730 K and ~615 K, respectively), and relatively distinct for Fe2+ (~350 K). Some values for θM and f could not be determined due to the non-monotonic behaviour of the fitted values for δ as a function of temperature. Values of f295 were 0.821–0.917 for Fe3+ and 0.662–0.743 for Fe2+, consistent with previous studies of the recoil-free fraction in micas and other silicates. Calculated scatter in δ, Δ, area and f values as a function of different line shapes and computer software was significantly reduced at lower temperatures. Sources of error in each of the calculated parameters are discussed.

Green-blue Fe(II)Fe(III)-and Fe(II)Al(III)-hydroxycarbonates with a pyroaurite structure were prepared by Taylor & McKenzie (1980) and Taylor (1980). They were thought to be related to the unstable mineral phases which occur naturally in the dark green-blue mottles of wet, anaerobic horizons of gleyed soils. These synthetic compounds are unstable to oxidation, suffering structural and colour changes, with the ultimate products depending on the environmental conditions. This instability makes it difficult to identify them and study their characteristics by X-ray diffraction and other methods.

The technique described in this note has been found to stabilize the synthetic green-blue compounds satisfactorily. It involves handling and storage of the compounds in a CO2 atmosphere, such as might occur under natural anaerobic conditions in a soil below the ground-water level. The same principles can be applied to collect field samples and maintain them in a stable state.

Previous work on the structural and thermal properties of various types of kaolinite have led to different conclusions, rendering comparison of analytical results difficult. The objectives of the present study were to investigate the thermal behaviour of kaolinite and to carry out a kinetic analysis of the decomposition of kaolinite at high temperatures. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetry-differential scanning calorimetry (TG-DSC) were used to study the mechanism of the thermal decomposition. The modified Coats–Redfern, Friedman, Flynn–Wall–Ozawa and Kissinger decomposition models were used to determine the decomposition mechanism of the kaolinite sample. The dehydroxylation of kaolinite occurred at ∼600°C with the formation of metakaolin, which then transformed into either γ-alumina or aluminium-silicon spinel together with amorphous silica. The results of the XRD and FTIR analyses indicated that the γ-alumina, or aluminium-silicon spinel and amorphous silica phases, transformed into mullite and α-cristobalite, respectively, after decomposition at 900°C. Good linearity was observed with the modified Coats–Redfern, Flynn–Wall–Ozawa and Kissinger models from room temperature to 1400°C and the range of the activation energy determined was 120–180 kJ/mol.

This study uses transmission electron microscopy (TEM) and analytical electron microscopy (AEM) supported by X-ray diffraction (XRD) and scanning electron microscopy (SEM) to investigate the mineralogical and textural changes produced in carbonated clays by firing. Sample bars were prepared using raw clays composed of quartz, illite and carbonates with minor amounts of smectite, chlorite, feldspars and Fe oxides. The raw samples were then fired at temperatures of between 800 and 1050°C. The XRD data show that increases in firing temperature result in dehydroxylation of clay minerals, carbonate decomposition and the formation of Ca-bearing silicates (e.g. gehlenite, wollastonite, pyroxenes and anorthite). The sizes of the Ca-silicate crystals make the use of the SEM inappropriate since they lie below the resolution threshold. However, TEM/AEM do provide the required textural and compositional characterization, revealing that there is a broad range of pyroxene compositions, some of which resemble fassaite, and that Ca/Mg ratios increase with temperature. The TEM also shows significant dehydroxylation and vitrification of the clay-rich matrix at T of ~800°C. Observed mineralogical and textural changes probably occurred in a system with a local disequilibrium much like small-scale, high-temperature metamorphic reactions (i.e. pyrometamorphism). The importance of these results is that they enable the selection of more appropriate raw clay composition and firing dynamics (temperature, firing duration and cooling rate) for both the brickmaking industry and brick conservation in the field of cultural heritage.

The adsorption of the anionic dye Congo Red (CR) by Na-, Cs-, Mg-, Cu-, Al- and Fe-montmorillonite was investigated by electronic spectroscopy. Spectra of the aqueous suspensions of different clay concentrations and different loadings were recorded. The spectra were curve fitted and were compared to spectra of aqueous solutions of CR at different pH values. Four bands representing anionic varieties and two representing protonated varieties of CR were identified in spectra of CR-treated Na-, Cs-, Mg-, Cu- and Al-montmorillonite. Spectra of CR-treated Femontmorillonite were slightly different, showing three bands representing anionic varieties and four representing protonated CR. The ratio between areas of bands, which represent the protonated varieties, and those representing the anionic varieties were determined showing correlation with the acidity of the metallic cation. The clay in the aqueous suspensions became coloured after the adsorption of CR. The following stainings were obtained, Na- and Mg-clay, red, Cs-clay, violet-red, Cu-clay, reddish-violet, Al-clay, dark violet and Fe-clay, dark blue. It appears that CR can serve as an indicator of the surface acidity of montmorillonite. The effects of aging on the sorption of the dye and on the surface-acidity of the CR-clay complex were investigated.

The Devonian sedimentary rocks of the UK are made up of a continental red bed facies, the Old Red Sandstone (ORS), and sediments of a marine origin. The latter are confined to southwest England whereas the ORS occurs much more extensively, particularly in South Wales, the West Midlands, Northern England, the Midland Valley of Scotland and the Orcadian basin. The ORS also occurs extensively offshore where it contains important hydrocarbon reservoirs. Highly variable suites of clay mineral assemblages are characteristic of the ORS. In the West Midlands and Monmouthshire, the Downton Group is characterized by illitic, smectitic, and mixed-layer illite-smectite minerals. A tuff bed (Townsend Tuff) also contains expansible minerals but when the bed is traced westwards it is found that the clay mineralogy changes progressively to an illite-chlorite assemblage, suggesting the influence of diagenetic or metamorphic change. It is not known, however, whether such a transformation is typical of the Downton Group as a whole. The overlying Ditton Group in its eastern outcrops contains a high-spacing mineral identified as tosudite, together with regularly interstratified illite-smectite and well crystallized kaolinite. Further west this assemblage gives way to illite and chlorite, with the latter being trioctahedral or dioctahedral, while in Dyfed the Ditton Group may contain smectite and poorly crystallized kaolinite in addition to illite and chlorite. The geographical distribution of clay minerals in the Ditton Group may also be accounted for by progressive diagenetic to low-grade metamorphic reactions, although it is necessary to postulate retrogressive diagenesis to account for the smectite and kaolinite that occur in the Dyfed samples. The clay mineralogy of the overlying Brecon Group and the Upper ORS also consists of mixtures of illite and chlorite in the west and central parts of the region. No data are available for the Brecon Group in the eastern parts of the outcrop but the Upper ORS from around Monmouth and Portishead contains assemblages rich in kaolinite and mixed-layer illite-smectite with only minor amounts of chlorite. The distribution of clay minerals in the Upper ORS is again suggestive of a progressive westerly increase in the influence of diagenetic alteration, although the influence of provenance cannot be discounted.

In Scotland the clay mineralogy of the Lower ORS in the Midland valley is characterized by a variety of interstratified minerals, including regularly interstratified trioctahedral chlorite-vermiculite, a tosudite mineral similar to that described from South Wales and illite-smectite, as well as occasional illite, chlorite and smectite. The oldest Stonehaven Group is kaolinitic but in the younger groups kaolinite is either completely absent or present in only minor amounts. It is clear that detrital inputs, particularly from associated volcanic rocks, have contributed to the clay minerals found in these rocks, although the contribution could be indirect with diagenetic clay minerals forming from volcanic detritus after deposition. Diagenetic alteration may also be important, particularly with respect to the origin of the tosudite mineral. The Middle ORS lacustrine sediments of the Orcadian Basin of Scotland are characterized by mixtures of trioctahedral chlorite and dioctahedral illite, with interstratified chlorite-smectite, illite-smectite, kaolinite and occasional reports of minor montmorillonite. The most recent interpretations of the origins of the clay minerals in these rocks emphasize the role of progressive diagenetic and low-grade metamorphic reactions, based on correlations of clay mineral assemblages and parameters such as illite crystallinity with organic maturation data. This interpretation argues that the illite-smectite in the shales is derived largely from a precursor detrital smectite. However, the finding of two populations of morphologically and structurally distinct illite-smectite particles in the Middle and Upper ORS sandstones suggests a more complex picture involving different diagenetic episodes. In addition, the likelihood of a smectitic-rich detrital input to the ORS may also be a point of debate. The clay mineralogy of the North Sea offshore is also described briefly, in addition to the marine Devonian in southwest England. The latter is characterized by chlorite and illite assemblages of low-grade metamorphic origin, although smectite and kaolinite are also found occasionally in these rocks. The offshore ORS, however, contains a variety of clay minerals, including an assemblage similar to that found in the Lower ORS south of the Highland Boundary Fault and notably contains a tosudite-like mineral.

Early Cambrian sediments on the East European platform in North Estonia, represented mostly by clays and silty clays, were deposited under normal marine conditions. The sediments were never affected by significant tectonic or thermal events after sedimentation 530 Ma ago, and the clays still have high water contents. The clay fraction, divided into four sub-fractions, was studied using X-ray methods and Rb/Sr dating. Decomposition of the XRD curves was used to quantify the amounts of illitic minerals in the sub-fractions. Dating by Rb/Sr showed that the finest fraction (<0.06 µm) was formed 50–150 Ma after sedimentation. The coarser fractions also contain considerable amounts of diagenetically formed minerals. This shows that neoformation of illitic minerals in marine sediments with high water/sediment ratios is a very important process even at temperatures <35°C.

Hydrogen-forms of <2 µm fractions of six bentonites of various Fe contents were prepared by H+→OH-→H+ ion exchange using resins. Potentiometric titration curves revealed that the number of strong acid sites varied and accounted for 60-95% of the total acidity in the freshly prepared H-forms. The number of strong acid sites decreased and that of the weak acid sites increased on ageing. The process of autotransformation in aqueous dispersion at 90~ was completed within four days. Layer-charge distributions of all samples were inhomogeneous with layer charges from 0.25-0.39 Eq/unit O10(OH)2. Oxalate pretreatment of the samples resulted in changes in the layer-charge distribution due to the removal of readily soluble phases which may have blocked exchange sites. After autotransformation, the alkylammonium exchange method revealed inhomogeneous charge density distributions; the fraction of layers of the highest charge decreased. Comparison of total CEC obtained from potentiometric curves and interlamellar CEC calculated from the mean layer charge confirmed attack of protons from particle edges. However, for several samples the structural attack may also occur from the interlayer space. Autotransformation of the Hsmectites decreased the mean layer charge. Protons probably attack the Mg(O,OH)6 octahedra preferentially during the autotransformation.

In the past, two factors have impeded the quantitative estimate of Fe-oxides in soils by X-ray diffraction. First, Fe-oxides are still quite often considered X-ray amorphous, although numerous results, e.g. a low ratio of oxalate- to dithionite-soluble Fe, have indicated the opposite. Second, even if crystalline, the cocentration of Fe-oxides in many soils is low, thereby complicating their identification by XRD. Recently, however, more sensitive methods such as Mössbauer spectroscopy and Differential-XRD (Schulze, 1981) have been introduced, which substantially reduce the lower limit of detection. Because these two methods are not generally available and, especially in the case of M&oum;ssbauer spectroscopy, are rather time consuming, ordinary XRD should be adapted for quantitative estimation of Fe-oxides.

Determination can be facilitated by using samples in which the Fe-oxides are concentrated by particle-size separation and a 5 M NaOH boiling treatment (Norrish & Taylor, 1961). The latter treatment is particularly suitable for kaolinitic soils as the Fe-oxides are unaffected―provided certain precautions are taken (Käimpf & Schwertmann, 1982a). This paper gives details of a procedure for the quantitative estimation of goethite (Gt) and hematite (Hm) by XRD.

Understanding the composition of clay-rich sediments and their transportation into proximal marine basins allows us to better decipher hydroclimatic changes before and within the Palaeocene–Eocene Thermal Maximum (PETM). Only a limited number of such studies exists from the North Sea Basin, which was proximal to the volcanic activity and early rifting hypothesized to have triggered the PETM. The present study examines core material from well 22/10a-4, UK North Sea, as it exhibits an exceptionally expanded and almost stratigraphically complete fine-grained sedimentary sequence suitable for high-resolution analysis.

Quantitative Newmod-for-Windows™-modelled clay mineral assemblages, rather than traditional semi-quantitative estimates, are dominated by smectite-rich, interlayered illite-smectite that probably developed from volcanogenic deposits on continental landmasses. Soil development before the PETM is consistent with the existence of a seasonal tropical climate with a prolonged dry season. A striking rise and fall of kaolinite content within the PETM onset, prior to the principal carbon-isotope excursion, is reported here. This variation is interpreted as a signal of an enhanced hydrologic cycle producing an increase in erosionally derived kaolinite, followed by a dampening of this detrital source as sea-levels rose. Global variations in PETM kaolinite concentrations are consistent with a latitudinal shift in patterns of precipitation in models of global warming.

Proteins (catalase, albumin, pepsin and lysozyme with different molecular weights and isoelectric points) were differently adsorbed at pH 7.0 on the clay fraction of three raw Na-saturated smectites (Crook and Uri montmorillonites and one hectorite). The adsorption isotherms of proteins on clay minerals showed typical Langmuir characteristics. Lysozyme was adsorbed under the effect of electrostatic interactions between the opposite charges of clay surfaces and protein molecules, whereas catalase and albumin were adsorbed under the effect of non-electrostatic forces. Pepsin was held in relatively high amounts only on the surfaces of hectorite. Proteins were intercalated in the interlayers spaces of smectites, usually undergoing extensive unfolding. Protein-smectite complexes showed different behaviour to heating treatment. Some complexes remained practically unchanged after heating at 200°C. Presence of ‘wrecks’ of interlayered materials was found after heating at 500°C for two hours. The amounts of proteins adsorbed on the external and interlamellar surfaces of clay minerals, partially coated with OH-Al species, were much lower than those fixed on the clean clays. Only lysozyme was intercalated in chlorite-like complexes.

Combined electron micrographs and electron diffraction diagrams of single crystals of hydrated kaolins from Hongkong, North Carolina and Indiana show that they have tubular crystal form, but a structure different from that of halloy-site, or of kaolinite, being two-layer triclinic, with β=83°, α=91·8°. They differ in degree of crystallinity, and show some inter-layer water.

The Scherrer equation links the measured width of an X-ray diffraction peak (Scherrer width, SW) to the number of stacked cells (N) in the direction normal to the diffracting planes. The formula is only valid for one d-value occurring in the coherently diffracting domain. This equation can be modified for weakly swelling mixed-layer minerals. This assumes that the peak broadening caused by the mixed-layering is proportional to the amount of swelling component (S) and that the effects of size and mixed-layering are additive.

If two SW can be measured on XRD patterns from samples treated in two different ways (such as air dried or glycolated), N and S can be determined. This equation is applicable to illite-smectite mixed-layer minerals with high illitic content. The results are most accurate for N>30. The use of Scherrer's equation is discussed.

Fifteen Swedish and Finnish soil samples from spodic B horizons containing imogolite-type materials were equilibrated with dilute NaCl and HC1 at 8°C. For the NaCl extracts, apparent equilibrium with respect to an AI(OH)3 phase was reached in one to two weeks. Equilibrium with respect to an imogolite-type phase was slower, especially at large soil:solution ratios. The results show that log *Ks (gibbsite), i.e. the logarithm of the solubility constant for reactive AI(OH)3 at 8°C was ~9.40 (8.29 at 25°C) while log *Ks (imogolite) was variable; for the soil studied in most detail it was 7.66 (6.64 at 25°C) As well-ordered gibbsite rarely forms in spodic B horizons, it is suggested that Al(OH)3 and poorly-ordered allophanic materials may be slowly converted to less soluble and less reactive imogolite-type materials.

The structure of Silica Springs allophane from New Zealand has been studied by high-resolution 27A1 and 29Si NMR spectroscopy, IR spectroscopy and electron microscopy. Experimental NMR conditions were chosen to give a quantitative relationship between signal strength and Al content. Aluminium is present in both octahedral (Alvi) and tetrahedral (Aliv) coordination, and the ratio Alvi:Aliv was obtained for three samples with different total Al:Si ratios. In all cases the Aliv:Si ratio was 1 : 3, consistent with the ratio in ideal muscovite. The negative charge arising from Aliv was apparently balanced by positive charge at adjacent Alvi sites. Both NMR and IR spectra indicate that Si exists in a condensed network, probably a sheet, with Si atoms linked (through oxygen) to one, two and, possibly, three other Si atoms, but not four. The spectra are consistent with a mixture of Si-O-Si, Si-O-Al, and Si-OH linkages. A structure based on fragments of single curved 1 : 1 aluminosilicate layers, with the tetrahedral sheet on the outer surfaces, is suggested, the diameter of curvature being 2–3 nm. The tetrahedral sheet is more or less complete and has a Aliv : Si ratio of 1 : 3; the octahedral Alvi sheet is incomplete. Electron micrographs suggest that, at least in some cases, the fragments form more or less complete spherules. This proposal seems to accord with Farmer's concept of “aluminous hydrous feldspathoids”. The minimum pH at which Silica Springs allophane has precipitated corresponds to the initial presence of tetrahedrally coordinated Al species in solution.

Ammonium-rich illite was identified in shales from the meta-anthracite coalfields of Zemplinicum (the Western Carpathians) together with K-illite and Na-illite using X-ray diffraction (XRD), infrared absorption and chemical analyses. The NH4-abundance in illite was quantified by the position of the 005 XRD reflection and by chemical analysis. Ammonium-bearing illite was probably formed in the temperature interval 200-270°C by illitization of a kaolinite precursor in the presence of ammonium.