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Clay mineralogy of the Jiujiang soils, classified as red earth (on summit and slope), were investigated using X–ray diffraction (XRD), cation exchange capacity (CEC) determination, and high-resolution transmission electron microscopy (HRTEM). The XRD results show that the soils included kaolinite, illite, vermiculite, and mixed-layer I/S and K/S as clay minerals. In XRD patterns of clay separates the low-angle shoulder on the kaolinite (001) peak shifted to ~ 8 A on glycolation, indicating the presence of mixed-layer K/S clays in the soils. Kaolinite content in the interstratified kaolinite–smectites was estimated to be ~ 95% for samples of the middle to lower soil profile and ~ 60% for that of the upper portion, respectively. A broad reflection for 10–14 A disappeared and an 18.7 A peak occurred in the XRD patterns after formamide treatment. The 10 A peak became much more intense on heating to 400 °C, indicating that the 10–14 A peak was expandable and easily contractible and thus originated from mixed-layer illite–smectite (I/S) clays. After heating to 550 °C, the 7 A peak disappeared while the 10 A peak became more intense and showed a low-angle tail, indicating the interstratified smectite component was hydroxy interlayered. The higher CEC values of the Jiujiang clay separates (22.2–27.3 cmol/kg) also pointed to the occurrence of smectite in the soils. HRTEM analysis showed different lattice fringes for clay particles in the samples; a great majority of layer spacings were in the range 10–20 A, with a minority of ~ 7 and ~ 25 A. Particles with ~ 7 A fringes showed a lateral transition of two 7 A kaolinite layers merging into one 12 A smectite layer. This can be interpreted as the partial intercalation of one smectite layer in kaolinite. There was no long-range order in the stacking sequence of K/S layers, and the interstratification was of a random nature. In the uniform soil horizon of the upper profile, there was more vermiculite and illite, but less I/S and K/S, while in the net-like soil horizon of the middle-lower profile there was more kaolinite, I/S, and K/S, with only a trace of vermiculite. The occurrence of K/S clays confirmed that the Jiujiang red earth was derived from syndepositional pedogenesis and the climates changed from warm and seasonally dry to warm and more humid conditions during the soil-forming period.

Our results enabled us to differentiate at least two water motions during dehydration of Ca- and Na-SAz-1 (initially equilibrated at RH = 55%) by using a "controlled water loss" time-of-flight procedure. This work confirms that (a) interlayer and cationic water in dioctahedral smectites are characterized by slower motions than interparticle water, (b) interlayer cations influenced the dynamics of water loss, probably through its affect on clay fabric, and (c) interparticle water behaves more like bulk water. At 55% RH the Ca montmorillonite held more interparticle water, but on dehydration under controlled conditions, it retained interlayer and cationic water more strongly than Na montmorillonite. The multiple energy states of water held by surfaces of a clay mineral can be effectively probed with time- of-flight and fixed elastic window neutron scattering. We used these techniques to quantitatively differentiate water types, including rotational and translational diffusions, in Ca- and Na- montmorillonite (SAz-1) and charge-reduced preparations equilibrated at RH = 33% and 55%, whose gravimetric water contents are in proportion with their layer charge. Quasi-elastic neutron scattering results revealed significant differences within interlayer water populations and between interlayer and interparticle waters. Interlayer cationic and H-bonded waters have residence times ranging from a few nanoseconds to tenths of picoseconds, while interparticle water, obtained for the RH = 55% equilibrated samples, showed an average diffusivity faster than interlayer water, yet slower than bulk water. Refereed/Peer-reviewed

Data in the literature for soils that are dominated by each of the main types of clay minerals were examined and compared with those for reference clay minerals of the same types to determine the extent to which the nature and properties of clay-size minerals in soils could be explained by those of clay minerals with the same name from non-soil, ‘geological’ environments. Published information on soils from Australia, New Zealand and Iran was sourced for this study. The clay fractions of each of the soils are dominated by either one of the common phyllosilicates: kaolinite, halloysite, illite/mica, vermiculite, smectite,and palygorskite, or by the nanocrystalline mineral, allophane. Data for samples of kaolinite that hadbeen extracted from soils from several countries (Australia, Thailand, Indonesia and Brazil) and purified before characterization have also been examined. In soils, each dominant clay mineral is generally associated with other materials, including iron oxides, other phyllosilicates and/or nanocrystalline minerals and organic matter. As the most studied example of an extracted phyllosilicate, kaolinite shows a wide range of properties in different soils, but a narrower range of properties within a particular locality. However, almost all of the soil kaolinites studied have larger specific surface areas and higher cation exchange capacities than reference kaolinites. The literature also reveals that, among phyllosilicates in soils, illites have a wide range of potassium contents, expandable minerals (vermiculites and smectites) may be interlayered by hydroxy-Al species particularly, and smectitic layers often occur interstratified with other layers, including those of illite, kaolinite and halloysite. The variability of soil phyllosilicates and their common association with other, often poorly crystallized but highly reactive minerals and compounds can be explained by their formation in the highly heterogeneous and dynamic soil environment. Phyllosilicates from non-soil or geological sources are poor models for the representation of secondary clay-size minerals in soils. In philosophical terms, the reduction of soil mineralogy to mineralogy as it is practiced within geology is misleading because of the differences between the minerals formed in soil and geological environments. In other words, clay minerals as they are defined as mineralogical entities for geology are of a different ‘kind’ to clay minerals in soils and cannot serve as ‘types’ or ‘stereotypes’ to enable explanation of the contribution of secondary clay-size minerals to soil properties or behavior. It is more useful to view clay minerals in soils as secondary inorganic compounds of clay-size than to follow their definition for non-soil purposes as plastic phyllosilicate minerals. Refereed/Peer-reviewed