On the structural formula of smectites: a review and new data on the influence of exchangeable cations

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.

Hydration of Na-saturated synthetic stevensite, a peculiar trioctahedral smectite

Smectite interlayer water plays a key role in the mobility of elements and molecules and affects a variety of geological processes. In trioctahedral smectites, in contrast to saponite and hectorite, the layer charge of which originates from isomorphic substitutions, the stevensite layer charge originates from the presence of octahedral vacancies. Despite its common occurrence in lacustrine environments, stevensite hydration has received little attention compared to saponite and hectorite. Early reports mention a specific hydration behaviour, however, with the systematic presence of a low-angle reflection attributed to the regular interstratification of various hydration states. The present study aims to revisit this specific hydration behaviour in more depth. Within this scope, the hydration behaviour of the three smectite varieties above are compared using synthetic trioctahedral smectites of similar layer charge and various compositions of their octahedral sheets. The chemical composition of the octahedral sheet does not appear to influence significantly smectite hydration for saponite and hectorite. Compared to its saponite and hectorite equivalents, H2O content in stevensite is lower by ~2.0 mmol H2O per g of dry clay. Consistent with this lower H2O content, Zn-stevensite lacks a stable monohydrated state, with dehydrated layers prevailing from 60% to 0% relative humidity. The presence of the regular interstratification of 0W and 1W layers is responsible for the low-angle reflection commonly observed for stevensite under air-dried conditions. Finally, the stevensite identification method based on X-ray diffraction of heated and ethylene glycol-solvated samples is challenged by the possible influence of the octahedral sheet chemical composition (Zn or Mg in the present study) on hectorite swelling behaviour in synthetic Zn-smectites. The origin of this effect remains undetermined and further work is needed to propose a more general identification method.

Spanish Bentonites: A Review and New Data on Their Geology, Mineralogy, and Crystal Chemistry

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.

Effects of Temperature, Alkali Source, and Mg/Al Ratio on Phase Purity and Yield of Hydrothermal Synthesized Smectites

Smectites are a major type of clay minerals. Hydrothermally synthesized smectites have become a major research topic because of the unstable quality or excessive impurity of natural smectites. The high-phase purity and yield of hydrothermally synthesized smectites are vital in advanced industries and materials applications. In this study, a Taguchi orthogonal array was integrated with eight factors to avoid biased experimental results, thus creating relatively robust factor portfolios to investigate the effects of temperature, alkali sources, and the magnesium (Mg)/aluminum (Al) ratio on the phase purity and yield of hydrothermally synthesized smectites. The synthesized environment was mainly established using trioctahedral smectites based on the formula Na2x(Al2(1−x)Mg2x□)Si4O10(OH)2X-ray diffraction and Rietveld refinement were used for the quantitative analysis of the products’ mineral facies and calculating the synthesized smectites’ phase purity and yield. The Taguchi method was employed to calculate each factor’s effect on the product quality. The results indicated that among the numerous factor portfolios, a relatively high temperature, ammonia solution as the alkali source, and a relatively high Mg/Al ratio were conducive to enhanced phase purity and yield of synthesized smectites. The optimized products of the synthesized smectites achieved a phase purity of 92.5% and a yield of 88.3%.

The First X-ray Powder Diffraction Measurements on Mars

The CheMin instrument on the Curiosity rover measures XRD and XRF data using Co radiation in transmission geometry. It has analyzed <150 μm portions of eolian soil (Rocknest) and two drill-hole powders (John Klein and Cumberland) from a mudstone [1, 2, Figure 1]. XRD data for Rocknest soil revealed plagioclase, forsteritic olivine, augite, and pigeonite. John Klein and Cumberland are similar, with much less Fe-forsterite and more magnetite than Rocknest. Data were analyzed via Rietveld methods (Topas), and profiles were modeled using beryl-quartz data measured on Mars. CheMin's broad profiles limited analysis of minor phases (<3 wt. %), although the presence of minor phases was evaluated individually for every sample by including each in the Rietveld model and evaluating their effect on the fit. We found no evidence for any perchlorate, carbonate, or sulfate mineral (apart from anhydrite, and bassanite in the mudstones). No phyllosilicate was detected in the soil, but mudstone samples contained two different phyllosilicates, likely trioctahedral smectites. The John Klein XRD pattern had a broad ~10Å peak, whereas Cumberland showed broad peaks at ~13.2Å and ~10Å. The background in all XRD patterns suggested the presence of amorphous/poorly ordered components, which were analyzed using FULLPAT, giving ~27% amorphous content in Rocknest and ~20% in the mudstones. This mineralogy is very similar to that found in soils on the flanks of Mauna Kea volcano, Hawaii. Mineralogy differences between the Rocknest material and the mudstones may be explained by alteration of Fe-forsterite to smectite + magnetite. Combining these results with compositional estimates from unit-cell parameters and bulk chemistry will allow determinations of individual phase compositions, including that of the amorphous component(s). The exact nature of the amorphous component is unclear, but other data show that it is hydrous.