The understanding of the structural formula of smectite minerals is basic to predicting their physicochemical properties, which depend on the location of the cation substitutions within their 2:1 layer. This implies knowing the correct distribution and structural positions of the cations, which allows assigning the source of the layer charge of the tetrahedral or octahedral sheet, determining the total number of octahedral cations and, consequently, knowing the type of smectite. However, sometimes the structural formula obtained is not accurate. A key reason for the complexity of obtaining the correct structural formula is the presence of different exchangeable cations, especially Mg. Most smectites, to some extent, contain Mg²⁺ that can be on both octahedral and interlayer positions. This indeterminacy can lead to errors when constructing the structural formula. To estimate the correct position of the Mg²⁺ ions, that is their distribution over the octahedral and interlayer positions, it is necessary to substitute the interlayer Mg²⁺ and work with samples saturated with a known cation (homoionic samples). Seven smectites of the dioctahedral and trioctahedral types were homoionized with Ca²⁺, substituting the natural exchangeable cations. Several differences were found between the formulae obtained for the natural and Ca²⁺ homoionic samples. Both layer and interlayer charges increased, and the calculated numbers of octahedral cations in the homoionic samples were closer to four and six in the dioctahedral and trioctahedral smectites, respectively, with respect to the values calculated in the non-homoionic samples. This change was not limited to the octahedral sheet and interlayer, because the tetrahedral content also changed. For both dioctahedral and trioctahedral samples, the structural formulae improved considerably after homoionization of the samples, although higher accuracy was obtained the more magnesic and trioctahedral the smectites were. Additionally, the changes in the structural formulae sometimes resulted in changing the classification of the smectite.

A review and a synthesis of the geological, mineralogical, and crystal chemical data available in the literature on active Spanish bentonitic exploitations were done, and at the same time, new data are provided from a set of representative samples from these deposits. They were located in three different areas with different geological origins: (1) Miocene sedimentary deposits from the Tajo Basin (Madrid–Toledo provinces) in the center of the Iberian Peninsula, where bentonites appear in two different units named for their colors (Green Clays and Pink Clays); (2) samples from Tamame de Sayago (Zamora province) originating from the hydrothermal alteration of granitic Variscan rocks; and 3) Miocene deposits originating from the hydrothermal alteration of volcanic or subvolcanic rocks from the Cabo de Gata volcanic area (Almería Province) in the southern part of Spain, where the three main deposits (Cortijo de Archidona, Los Trancos, and Morrón de Mateo) were studied. The bentonites from the Tajo Basin were formed mainly by trioctahedral smectites, and there were significant mineralogical differences between the Green and Pink Clays, both in terms of the contents of impurities and in terms of smectite crystallochemistry and crystallinity. The smectites from Tamame de Sayago were dioctahedral (montmorillonite–beidellite series), and they appeared with kaolinite, quartz, and mica in all possible proportions, from almost pure bentonite to kaolin. Finally, the compositions of the bentonites from the three studied deposits in Cabo de Gata were quite similar, and zeolites and plagioclases were the main impurities. The structural formulae of the smectites from Cortijo de Archidona and Los Trancos showed a continuous compositional variation in beidellite–montmorillonite, while in Morrón de Mateo, the smectites were mainly montmorillonite, although there was continuous compositional variation from Al montmorillonites to Fe–Mg-rich saponites. The variation in the smectite composition is due to the intrusion of a volcanic dome, which brings new fluids that alter the initial composition of the smectites.

A representative group of palygorskites from the six most important Spanish deposits and six other occurrences were studied comparing their mineralogy, textural features, crystal-chemistry, and surface properties. These palygorskites have different geological origin: (1) sedimentary in large Tertiary continental basins, (2) hydrothermally altered volcanic rocks in the southern Spanish Peninsula, also Tertiary in age; and (3) fault-hosted pure palygorskites. The most common impurities are quartz and carbonates, both calcite and dolomite, but also feldspar, illite, smectite, and sepiolite have been identified. The structural formulae obtained show great variability between samples, as well as with respect to the theoretical formula for palygorskite, as they range from magnesian to aluminous palygorskites. The most common fibre length ranges between 1 and 10^m m but the palygorskites of hydrothermal origin are much longer, with lengths over 10μm. The shorter fibres give rise to tightened textures, while longer fibres usually generate more open textures. These properties, along with the degree of compaction, condition the porosity of the sample, which in turn influences its surface properties. The specific surface areas obtained range between 30 m² g^-1 and 263 m² g^-1, depending on the impurities content and on the texture and crystal-chemistry; the highest values correspond to Mg-rich palygorskite.