Dioctahedral tosudite, a regular interstratification of dioctahedral chlorite-dioctahedral smectite, occurs associated with kaolin in the hydrothermal area of Delgado, Neutla, Mexico. Its composition corresponds to the formula:

$$\left( {S{I_{13.77}}A{L_{2.23}}} \right)A{L_8}{O_{40}}{\left( {OH} \right)_8} \cdot C{A_{0.39}}N{A_{0.03}}{K_{1.06}} \cdot \left( {A{L_{3.79}}F{E^{ + 3}}_{0.09}F{E^{ + 2}}_{0.06}M{G_{0.26}}} \right){\left( {OH} \right)_{12}}.$$

A modified version of the Bertaut-Warren-Averbach (BWA) technique (Bertaut 1949, 1950; Warren and Averbach 1950) has been developed to measure coherent scattering domain (CSD) sizes and strains in minerals by analysis of X-ray diffraction (XRD) data. This method is used to measure CSD thickness distributions for calculated and experimental XRD patterns of illites and illite-smectites (I-S). The method almost exactly recovers CSD thickness distributions for calculated illite XRD patterns. Natural I-S samples contain swelling layers that lead to nonperiodic structures in the c* direction and to XRD peaks that are broadened and made asymmetric by mixed layering. Therefore, these peaks cannot be analyzed by the BWA method. These difficulties are overcome by K-saturation and heating prior to X-ray analysis in order to form 10-Å periodic structures. BWA analysis yields the thickness distribution of mixed-layer crystals (coherently diffracting stacks of fundamental illite particles). For most I-S samples, CSD thickness distributions can be approximated by lognormal functions. Mixed-layer crystal mean thickness and expandability then can be used to calculate fundamental illite particle mean thickness. Analyses of the dehydrated, K-saturated samples indicate that basal XRD reflections are broadened by symmetrical strain that may be related to local variations in smectite interlayers caused by dehydration, and that the standard deviation of the strain increases regularly with expandability. The 001 and 002 reflections are affected only slightly by this strain and therefore are suited for CSD thickness analysis. Mean mixed-layer crystal thicknesses for dehydrated I-S measured by the BWA method are very close to those measured by an integral peak width method.

Quantification of mineral assemblages in near-surface Earth materials is a challenge because of the often abundant and highly variable crystalline and chemical nature of discrete clay minerals. Further adding to this challenge is the occurrence of mixed-layer clay minerals, which is complicated because of the numerous possible combinations of clay layer types, as defined by their relative proportions and the ordering schemes. The problem of ensuring accurate quantification is important to understanding landscape evolution because mineral abundances have a large influence on ecosystem function. X-ray diffraction analysis of the variable cation-saturated clay fraction in soil and regolith from the Calhoun Critical Zone observatory near Clinton, South Carolina, USA, was coupled with modeling using NEWMOD2 to show that mixed-layer clays are often dominant components in the mineral assemblages. Deep samples in the profile (>6.5 m) contain mixed-layer kaolinite/smectite, kaolinite/illite-like, kaolinite-vermiculite, illite-like/biotite, and illite-like/vermiculite species (with ‘illite-like’ defined herein as Fe-oxidized 2:1 layer structure with a negative layer charge of ~0.75 per unit formula, i.e. weathered biotite). The 2:1 layers in the mixed-layer structures are proposed to serve as exchange sites for K+, which is known to cycle seasonally between plant biomass and subsurface weathering horizons. Forested landscapes have a greater number of 2:1 layer types than cultivated landscapes. Of two nearby cultivated sites, the one higher in landscape position has fewer 2:1 layer types. Bulk potassium concentrations for the forested and two cultivated sites show the greatest abundances in the surface forested site and lowest abundance in the surface upland cultivated site. These observations suggest that landscape use and landscape position are factors controlling the mixed-layer mineral assemblages in Kanhapludults typical of the S.E. United States Piedmont. These mixed-layer clays are key components of the proposed mechanism for K+ uplift concepts, whereby subsurface cation storage may occur in the interlayer sites (with increased negative 2:1 layer charge) during wetter reduced conditions of the winter season and as biomass decay releases cation nutrients. Cation release from the mixed-layer clays (by decreased 2:1 layer charge) occurs under drier oxidized conditions during the growing seasons as biota utilize cation nutrients. The types and abundances of mixed layers also reflect long-term geologic factors including dissolution/alteration of primary feldspar and biotite and the subsequent transformation and dissolution/precipitation reactions that operate within the soil horizons. Thus, the resulting mixed-layer clay mineral assemblages are often complex and heterogeneous at every depth within a profile and across landscapes. X-ray diffraction (XRD) assessment, using multiple cation saturation state and modeling, is essential for quantifying the clay mineral assemblage and pools for cation nutrients, such as potassium, in the critical zone.

Pedogenic alteration of illite from red earth sediments in Jiujiang in subtropical China was investigated using X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Illite, hydroxy-interlayered vermiculite (HIV), kaolinite and mixed-layer illite-HIV (I-HIV) are present in the soils. The characteristic reflections of the clay phases were 14 Å, 10–14 Å, 10 Å, and 7 Å, respectively. After Mg-glycerol saturations, the 14 Å peak of the samples did not expand, and after heating at 350°C and 550°C it shifted to 13.8 Å and 12 Å respectively, with no residual 14 Å reflection, suggesting the occurrence of hydroxy-interlayered vermiculite. The randomly interstratified I-HIV clays were characterized by a broad peak at 10–14 Å, which did not change its position after Mg-glycerol saturation, but collapsed to 10 Å after heating at 350°C and 550°C. HRTEM analysis showed different lattice fringes of 12 Å, 10 Å and 7 Å . Mixed-layer I-HIV, HIV-K and illite-kaolinite (I-K) were observed in the HRTEM images which represented the intermediate phases during illite alteration. The merging of two 10 Å illite layers into a 12 Å HIV layer, lateral transformation of one HIV layer into one kaolinite layer and alteration of one illite layer into two kaolinite layers illustrated the mechanisms of illite-to-HIV, HIV-to-kaolinite and illite-tokaolinite transformation, respectively. The proposed pedogenic alteration of illite and the weathering sequence of the clay minerals in Jiujiang is illite → I-HIV → HIV → HIV-K → kaolinite. In addition, illite may transform directly to kaolinite.