The fertility of soils with respect to K+ and NH4+ is often difficult to measure, but is essential for achieving effective agronomic practices. This problem is especially important in the Vertisols of Thailand. The purpose of the study reported here was to characterize the composition and layer-charge behavior of Thai Vertisols in order to understand better their K+ and NH4+ fertility. Topsoil and subsoil clay of 12 representative highly smectitic Vertisols from Thailand were studied. Interlayer swelling of smectite with alkylammonium cations, cation exchange capacity (CEC), and chemical composition were determined. These data and the re-expansion on glycerol treatment of Li-saturated, heated smectite demonstrated that high-charge, Fe-rich beidellite is the major clay mineral in these soils. The beidellite has a heterogeneous layer-charge distribution as measured by the alkylammonium method, with mean values ranging from 0.43 to 0.62 charges per half unit cell. The layer charge determined by CEC and structural formula methods for some almost pure smectites is smaller (0.32–0.54) and greater (0.46–0.69), respectively, than determined by the alkylammonium method. The structural formulae of beidellite confirm that the layer charge originates mostly in the tetrahedral sheet.

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