The crystal structure of amesite-2H1 from the Postmasburg Mn ores of South Africa has been refined to R = 4.7% using Siemens P4 rotating-anode MoKα X-ray data and SHELXL-93 software. Partial ordering of tetrahedral Si,Al and especially of octahedral Mg,Al has reduced the ideal P63cm symmetry to triclinic P1 (refined as C1). Tetrahedral rotation of 15° moves the basal oxygens toward the octahedral cations in the same layer but away from the OH H-donors of the next layers. The ordering pattern of AlIV and AlVI is unique in that the locus of Al-rich sites consists of 2 intersecting sets of zigzag lines parallel to X2 and X3, plus 2 Al-rich octahedra in layer 2 instead of the usual 1 site.

The Mg-vermiculite from Santa Olalla has been treated with aliphatic amides—formamide (FM), acetamide (AM) and propionamide (PM)—in aqueous solution. These treatments produce the transformation towards NH4-vermiculite and interstratified NH4-vermiculite-Mg-vermiculite phases. The NH4-vermiculite, Mg-vermiculite and interstratified (mixed-layer) phases have been identified from basal X-ray diffraction (XRD) interval peaks between 10.3 Å and 14.4 Å, and confirmed by direct Fourier transform method, as well as by atomic absorption spectrometry (AAS), infrared (IR) spectroscopy and thermal analysis.

According to their NH4-vermiculite/Mg-vermiculite probability coefficients ratio (PA/PB), and PAA, these interstratified phases can be divided into 3 categories: 1) If the PA/PB ratio is ≥ 7/3 and PAA ≥ 0.7, there are interstratified phases with a strong tendency toward segregation (case of FM, AM and PM). 2) If the PA/PB ratio is between 5/5 and 6/4, with PAA in the range 0.45–0.6, there are nearly regular alternating and random interstratified phases (case of AM and PM). 3) If the PA/PB ratio is ≤ 5/5 and PAA ≤ 0.45, there are interstratified phases with a strong tendency toward alternation (case of PM).

Experimental evidence reported in the present work indicates that the mechanism of interaction of Mg-vermiculite with FM, AM and PM in an aqueous medium takes place by ion exchange of NH4 between the layers. The hydrolysis of these aliphatic amides leads to the liberation of NH4+ into the medium. It has been found that the NH4+ sorption depends on the physico-chemical characteristics of the particular aliphatic amide, and the transformation of Mg-vermiculite to interstratified and/or NH4-vermiculite phases depends on the amide concentration. These treatments allow one to control the formation of interstratified and NH4-vermiculite phases.

The mineralogy and geochemistry of shales reflect the composition of the initially deposited precursor mud, subsequently modified by diagenetic processes. To see if significant geochemical differences exist between shales that mainly owe their present-day composition to either deposition or diagenesis, we compare the published mineralogical, bulk and clay-fraction geochemical, and clay-fraction O-isotopic compositions of 2 shales. One shale is from the Western Canada Sedimentary Basin (WCSB), and its composition mainly reflects primary (depositional) chemical and mineralogical variations (smectitic to illitic illite/smectite) within this unit. The other shale is from the United States Gulf Coast (USGC), and its composition mainly reflects mixed-layer illite/smectite (I/S) diagenesis of deposited smectitic clay material. The chemical and mineralogical trends of WCSB and USGC shales, including one of increasing illite content in I/S with depth or maturity, are essentially indistinguishable, in both bulk shale and clay fraction, despite the contrasting genetic interpretations for the origin of the contained I/S. Thus, similar mineralogical and chemical trends with depth or temperature can result either from inherited depositional compositional heterogeneity of the sediment, from burial metamorphism of shale or a combination of both. Interestingly, the O-isotopic compositions of the clay fractions from the WCSB and USGC are significantly different, a fact that reflects original clay formation from source material and water of quite different isotopic compositions. The discrimination between depositional and diagenetic contributions to shale composition continues to pose challenges, but a combination of bentonite, illite polytype, clay isotopic and trace and rare earth elemental analyses together with illite age analysis holds promise for future work.

Because of the large surface area and common occurrence of smectites in the clay fractions, they are important in sorption/desorption reactions of organic pollutants entering soils and sediments. Results of sorption and desorption of atrazine by Al- and Ca-saturated smectite reported here showed that Al-saturated smectite sorbed much higher amounts of atrazine than Ca-saturated smectite. Al-saturated smectite sorbed 3820 mg kg−1 as compared to 1902 mg kg−1 by the Ca-saturated smectite during 5 consecutive sorptions from 10 ppm atrazine solution. Sorption isotherms over 2–10 ppm atrazine concentration range were nonlinear in all cases. Freundich coefficients, Kf, obtained from the sorption isotherms were much higher for Al- than Ca-saturated smectite; Kf varied from 405 to 3035 for Al-saturated and 100 to 306 for Ca-saturated. The pH values of Al- and Ca-saturated smectites were 3–4 units higher than the pKa (1.68) of atrazine, which suggests that atrazine was sorbed as neutral molecules. Stronger H-bonding between the more polarized H2O associated with the trivalent Al ion than the divalent Ca ion is likely responsible for the greater sorption by Al-smectite.

The chemical composition of mixed-layer serpentine/chlorite (Sp/Ch) in Tuscaloosa Formation sandstone was analyzed by energy dispersive X-ray spectroscopy (EDX) in the scanning electron miscroscope (SEM) and by X-ray diffraction (XRD). EDX results indicate little depth-controlled variation in composition, whereas XRD results suggest distinct decreases in octahedral Fe and tetrahedral Al. XRD-determined compositions appear to be erroneous and actually reflect progressive changes in Sp/Ch unit-cell dimensions caused by polytype transformations of Ibb layers to Iaa layers in a mixed-layer Ibb/Iaa polytype. The relative lack of variation in Sp/Ch composition, especially when compared to other studies of chlorite minerals over similar temperature ranges, is attributed to a reaction mechanism whereby mineralogic transformations (serpentine layers to chlorite layers and Ibb layers to Iaa layers) occur on a layer-by-layer basis within coherent crystallites, rather than by dissolution-precipitation crystal growth.

The lack of titanium in chlorite minerals is attributed to high levels of octahedral Al3+ that prohibit inclusion of the highly charged Ti4+ in the octahedral sheet. Anatase (TiO2) in the Tuscaloosa Formation apparently formed when Ti was liberated during crystallization of Sp/Ch following the breakdown of a Ti-bearing precursor (detrital ultramafic clasts and/or odinite). Odinite, an Fe-rich 7-Å phyllosilicate that forms in some shallow marine sands, apparently existed as a short-lived, poorly crystallized intermediary between dissolution of the ultramafic clasts and formation of Sp/Ch.

This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays.

The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River. In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspore, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore (“burley” clay).

The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality.

The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite. The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water, nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay.

Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.

Experimental alteration of obsidian was performed in 0.001 to 0.5 N NaOH and KOH solutions at 150 and 200 °C for 1 to 30 d. The products were examined by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray analysis (EDX). Changes in chemical composition and pH value of solutions during the reactions were also measured. As the pH of reacting solutions was increased, smectite, phillipsite and rhodesite crystallized progressively in NaOH solutions, while smectite, merlinoite and sanidine grew successively in KOH solutions. In addition, a small amount of less-soluble, poorly ordered boehmite was present as products of all the experiments. Smectite mainly appeared at slightly high pH, Si/Al and Na/K conditions, whereas rhodesite should be produced in extremely high pH, Na/K and Si/Al conditions. Sanidine was also formed in conditions of very high pH and Si/Al and very low Na/K. In intermediate conditions of pH and Si/Al, crystallization of phillipsite was stimulated in solutions of Na/K > 10, while formation of merlinoite was favored in conditions of Na/K < 1.

In the Tertiary lacustrine sediments of the Jbel Rhassoul (Morocco), stevensite and sepiolite, confined to the dolomitic facies, are commonly mixed at lower parts of the so-called “Formation Intermédiaire”. Transmission electron microscopy (TEM) observations reveal a relation between these 2 magnesian clay minerals. One can observe the different transition steps, from the initial folded layers of stevensite to the fibers emerging from the layers, and finally to the complete replacement of stevensite by sepiolite. That transition can also be observed by scanning electron microscopy (SEM), where the fibers seem to grow at the expense of stevensite. Thermodynamic calculations have been applied to provide geochemical conditions for the formation of sepiolite after stevensite. Early deposition of the “Formation Intermédiaire” occurred under climatic conditions varying between dry and wet. During dry periods, the relative silica enrichment and the pH decrease in the lake water should destabilize stevensite, leading to the formation of sepiolite. Subsequently, a perennial wet climate would lead to the formation of pure stevensite without any trace of sepiolite.

Pennsylvanian underclay from Illinois is characterized by well-developed mineral zonation: towards the coal bed, marly limestone gradually evolves into carbonate-free clay, chlorite becomes undetectable and illite/smectite changes from ordered and illite-dominated into random and smectite-dominated, with both types present in the middle of the profile. Transmission electron microscopy (TEM) observations of the bulk material imply that disappearance of calcite is due to dissolution. Movement of SiO2 in the upper part of the profile is evidenced by quartz cementation of clay aggregates; crystallization of kaolinite, by the presence of vermicular aggregates absent from less-altered samples. Illitic material in unaltered (limestone) samples consists of rare, large, Al-rich crystals of mica, interpreted as detrital, and abundant thin crystals of illite/smectite intimately mixed in approximately equal proportions with even thinner crystals of discrete illite. Both are more Mg- and Fe-rich than the large mica crystals and are interpreted as diagenetic, based on their 1Md polytype and the correlation with coal rank. Illitic material of the upper, carbonate-free section of the profile contains the same 3 types of crystals, but in different proportions: illite/smectite crystals dominate and their composition is more smectitic. Two distinct morphologies of the aggregates of crystals with different proportions of the component layers are observed. It explains why 2 different illite/smectites are detectable by X-ray diffraction (XRD) in these samples. The analysis of chemical data suggests that the underclay is a residue after dissolution of all of the calcite and half of the quartz from the original limestone (paleosol and/or telogenetic process). The TEM observations are not decisive regarding the origin of variation within the illitic material. It may result from burial diagenetic illitization of more-smectitic material, similar to the composition preserved in the center of underclay profile, or it may represent telogenetic alteration of illitic clay by acid waters penetrating down from the coal bed. The aggradation model explains the increase in percent K2O, MgO and illite layers in the uppermost part of the profile. Whichever is the direction of reaction, it proceeds on an aggregate-by-aggregate basis and not fundamental particle-by-particle, and cannot be explained by simple opening or collapse of interlayers.

Altered perthites from a weathered pegmatite in the Spruce Pine District, North Carolina, were characterized by electron microprobe as a K-rich microcline host with lesser Na-rich plagioclase having a lamellar morphology. Light-optical and transmission electron microscopy (TEM) show microtextural elements such as phase boundaries, holes and microfractures that could serve as potential nucleation sites for alteration to clay minerals.

The host microcline contains albite and pericline twinning textures that vary in character; the amount of each twinning type and/or the size of twin individuals changes on a μm scale. Plagioclase ranges from large lamellar vein and film albite (visible in the light microscope) to cryptoperthite whose size ranges from μm to perhaps 100 Å. The smallest-scale albite appears to be a late-stage phase of exsolution in which lamellae have nucleated heterogeneously on albite-twin composition planes in the microcline.

Alteration is concentrated in vein and film albite, especially along grain boundaries with microcline. Powder X-ray diffraction (XRD) patterns of intensely altered pegmatite show halloysite. Holes, microfractures, vein albite/host microcline boundaries and microcline/halloysite boundaries trend parallel to the traces of (010) and {110}, suggesting that these directions are pathways along which fluids migrate. Cleavage and microfractures occur along, and holes are bounded by, these directions. Holes are associated with dislocations and the latter are observed at feldspar/clay boundaries. Twin domains and cryptoperthitic albite are less susceptible to alteration than coarse lamellar albite and regions containing negative crystals and microfractures. However, microtextures in some areas containing halloysite suggest that once fluids penetrate the crystal, alteration may proceed preferentially in more strongly twinned regions.

Fifty-two Bidi-Koum bauxites from Guinea, Africa, of diversified chemical composition were characterized for their mineral composition. First, 14 element oxide concentrations were determined by X-ray fluorescence (XRF) using a fusion sample preparation technique. Loss of Mass (LOM) and organic carbon (OC) concentrations were also determined. The initial X-ray diffraction (XRD) phase quantification was carried out employing XDB software. This software allows for full interpretation of a sample diffractogram and helps generate initial concentrations of identified minerals based on a standardless approach. In the stage that followed, the mass balance procedure on the XDB software helped refine the final phase composition. Then, gibbsitic Al2O3 concentrations obtained by wet chemistry for all samples and kaolinitic SiO2 concentrations obtained for selected samples were compared with the concentrations obtained using the XDB software. Phases that were quantified are: gibbsite, boehmite, kaolinite, wavellite, goethite, hematite, quartz, anatase, rutile and illite. Phase concentrations were obtained for illite from K2O and for wavellite from P2O5 concentrations. The alumina substitution in the goethite lattice was also estimated.

Iron-manganese concretions are common in upper sola of Alfisols in the Inner Bluegrass Region of Kentucky. Their nature and quantities appear to be related to the fluctuation of seasonal perched water tables above clayey argillic horizons. This study was conducted to examine changes in the macro-and micromorphology, chemistry and mineralogy of concretions as a function of size, color and soil depth. Total Mn and Fe contents increased, while SiO2 decreased with concretion size. Black concretions contained higher Mn, while brown concretions were higher in Fe. Crystalline Mn- and Fe-oxides fractionated with a sequential extraction procedure increased, but amorphous Mn and Fe decreased with concretion size. Goethite was the only crystalline Fe oxide mineral identified by X-ray diffraction (XRD) analysis. Manganese oxide minerals were very difficult to detect due to the diffuse nature of their XRD peaks and poor crystallinity. Examination of soil thin sections showed concretions of soil horizons overlying restrictive clayey layers to exhibit differentiated fabrics, sharp external boundaries and generally spherical shapes. Concretions found within clayey restrictive layers or above lithic interfaces usually had less structural organization, softer matrices and diffuse external boundaries due to longer term saturated conditions. Scanning electron microscopy (SEM) examinations suggested that the concretionary matrix, in spite of its density, has numerous cavities and an extensive micropore system within which dissolved plasmic Fe and Mn can diffuse and precipitate.

Formation processes of weathering products of pumice collected from a rhyolitic pyroclastic flow deposit were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX). SEM clearly showed the presence of some weathering products adhering to the surface of pumice. XRD showed that the products were composed mainly of noncrystalline materials with a relatively small amount of halloysite (10 Å). TEM and EDX revealed texture transformation sequences from the earliest weathering product to a final product of halloysite as follows: 1) precipitation of very thin flaky or film-like noncrystalline Al-hydroxide; 2) transformation into irregularly aggregated Al-Fe-Si-rich fibrous material; 3) morphological changes to rounded aggregates; 4) development of halloysite-like curled domains with successive decrease in Fe content; and 5) further development of curled domains in rounded aggregates. These materials must be metastable phases at early reaction stages with kinetics limiting formation of the stable equilibrium phase of kaolinite.

A structural model for the geometry of Fe(III) octahedra near the surface of finely divided ferrihydrite was elaborated based on the bond-valence theory and by considering the interaction of water molecules in the 2 nearest hydration spheres. In contrast to bulk Fe atoms, which are bonded to bridging oxo (O) and hydroxo (OH) ligands, surface Fe atoms are also octahedrally coordinated to H2O ligands forming the 1st hydration shell ((H2O)I). In the wet state, external water molecules of the 2nd hydration shell ((H2O)II) are singly H-bonded to (H2O)I, while they are doubly coordinated in the dry state. Accordingly, wet ferrihydrite contains twice as many sorbed water molecules as dry ferrihydrite, and the structural difference due to the 2nd hydration shell accounts quantatively for the 15% increase of ferrihydrite weight experimentally measured in moist atmosphere. The interaction of surface Fe atoms with their 2 nearest hydration spheres modifies the geometry of surface Fe octahedra as compared to bulk octahedra, and idealized Fe-OH and Fe-H2O bond lengths in the wet and dry state were evaluated by the bond-valence theory. Our structural model provides a sound crystal-chemical basis to describe many apparent incongruities of Fe X-ray absorption near edge structure (K-XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopic data that have led to differing interpretations of the coordination environment of Fe in ferrihydrite by various investigators.

The standard form of the Scherrer equation, which has been used to calculate the mean thickness of the coherent scattering domain (CSD) of illite crystals from X-ray diffraction (XRD) full width data at half maximum (FWHM) intensity, employs a constant, Ksh, of 0.89. Use of this constant is unjustified, even if swelling has no effect on peak broadening, because this constant is valid only if all CSDs have a single thickness. For different thickness distributions, the Scherrer “constant” has very different values.

Analysis of fundamental particle thickness data (transmission electron microscopy, TEM) for samples of authigenic illite and illite/smectite from diagenetically altered pyroclastics and filamentous illites from sandstones reveals a unique family of lognormal thickness distributions for these clays. Experimental relations between the distributions’ lognormal parameters and mean thicknesses are established. These relations then are used to calculate the mean thickness of CSDs for illitic samples from XRD FWHM, or from integral XRD peak widths (integrated intensity/maximum intensity).

For mixed-layer illite/smectite, the measured thickness of the CSD corresponds to the mean thickness of the mixed-layer crystal. Using this measurement, the mean thickness of the fundamental particles that compose the mixed-layer crystals can be calculated after XRD determination of percent smectitic interlayers. The effect of mixed layering (swelling) on XRD peak width for these samples is eliminated by using the 003 reflection for glycolated samples, and the 001, 002 or 003 reflection for dehydrated, K-sa-turated samples. If this technique is applied to the 001 reflection of air-dried samples (Kubler index measurement), mean CSD thicknesses are underestimated due to the mixed-layering effect.

The technique was calibrated using NEWMOD©-simulated XRD profiles of illite, and then tested on well-characterized illite and illite/smectite samples. The XRD measurements are in good agreement with estimates of the mean thickness of fundamental particles obtained both from TEM measurements and from fixed cations content, up to a mean value of 20 layers. Correction for instrumental broadening under the conditions employed here is unnecessary for this range of thicknesses.

It is usual in Mössbauer spectroscopy analysis to take the subspectra areas as a measure of the concentration of the Fe compounds that generate them. In soils, the presence of different-size particles of different nature makes the semiquantitative Mössbauer studies difficult, and some handling of the sample must be carried out in order to get reliable area results (Bowman et al. 1967; Muir 1968; Williamson et al. 1981).

Nonlinear-optical investigations of new materials are important for 2 complementary reasons. first, the requirements for materials to be used in device applications that utilize nonlinear interactions are very demanding. New approaches to materials research can yield materials with favorable properties compared to traditional nonlinear materials, as shown recently in several supramolecular systems (Cox et a1. 1990; Stucky and MacDougall 1990; Clays et a1. 1993; Kelderman et a1. 1993; Kauranen et a1. 1995; Lehn 1995). This is particularly true for 2nd-order nonlinear optics that require noncentrosymmetric materials (Prasad and Williams 1991). On the other hand. nonlinear-optical processes can provide new techniques to study the properties of new materials. The nonlinear techniques have the potential of being more sensitive than the existing techniques or providing information that is not accessible at all using the existing techniques (Shen 1984). Here again, 2nd-order processes are particularly important because they provide an extremely sensitive tool to study symmetry properties of materials.

In order to remove impurities, natural illite is often subjected to chemical pretreatments before analysis, the assumption being that such pretreatments have little or no effect on the composition of illite. Bulk analyses are sometimes reported before and after pretreatment (Aja et al. 1991) but, because the contribution of the impurities to the bulk composition is unknown, the possible effects of chemical pretreatments on the composition of illite cannot be assessed. Recently, Rosenberg and Hooper (1996) have shown that analytical transmission electron microscopy (ATEM) techniques, which exclude impurities, can be used to determine the bulk compositions of relatively pure illite by averaging the analyses of at least 50 crystals per sample. This approach can be applied to impure illite in order to determine the effect of chemical pretreatments on the composition of natural illite.