Spectral Response (VNIR-SWIR) Associated with the Octahedral Sheet of Smectites

A mineralogical characterization of a group of bentonite samples was done by X-ray diffraction (XRD), chemical analysis by inductively coupled plasma mass spectroscopy (ICP-MS), and visible-near infrared and short-wave infrared spectroscopy (VNIR-SWIR). As tested by XRD, all samples are very pure, composed mainly of smectites with very small amounts of impurities, such as quartz and feldspar. The results of the chemical analysis show high contents of Al2O3 in all the samples except for COU(V), which has high contents of Fe2O3 and R4, which is a trioctahedral smectite. Within VNIR-SWIR spectra, absorption feature characteristics of the smectites due to the presence of Fe are observed at lowest wavenumber while, at the SWIR region, the absorptions are related to the M-OH bonds and there are differences among the samples according to their octahedral content.

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.

Theoretical Study of Octahedral Substitution Effect in Delaminated Pyrophyllite: Physicochemical Properties and Applications

We have studied, using DFT calculations, some geometrical and electronic properties of delaminated pyrophyllite (D-P) and the corresponding layers that resulted from three isomorphic substitution on the octahedral sheet (Mg2+,...

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.

Experimental and Theoretical Studies of Methyl Orange Uptake by Mn–Rich Synthetic Mica: Insights into Manganese Role in Adsorption and Selectivity

Manganese–containing mica (Mn–mica) was synthesized at 200 °C/96 h using Mn–carbonate, Al–nitrate, silicic acid, and high KOH concentration under hydrothermal conditions. Mn–mica was characterized and tested as a new adsorbent for the removal of methyl orange (MO) dye from aqueous solutions. Compared to naturally occurring mica, the Mn–mica with manganese in the octahedral sheet resulted in enhanced MO uptake by four times at pH 3.0 and 25 °C. The pseudo–second order equation for kinetics and Freundlich equation for adsorption isotherm fitted well to the experimental data at all adsorption temperatures (i.e., 25, 40 and 55 °C). The decrease of Langmuir uptake capacity from 107.3 to 92.76 mg·g−1 within the temperature range of 25–55 °C suggested that MO adsorption is an exothermic process. The role of manganese in MO selectivity and the adsorption mechanism was analyzed via the physicochemical parameters of a multilayer adsorption model. The aggregated number of MO ions per Mn–mica active site ( n ) was superior to unity at all temperatures signifying a vertical geometry and a mechanism of multi–interactions. The active sites number (DM) of Mn–mica and the total removed MO layers (Nt) slightly changed with temperature. The decrease in the MO adsorption capacities (Qsat = n·DM·Nt) from 190.44 to 140.33 mg·g−1 in the temperature range of 25–55 °C was mainly controlled by the n parameter. The results of adsorption energies revealed that MO uptake was an exothermic (i.e., negative ΔE values) and a physisorption process (ΔE < 40 kJ mol −1). Accordingly, the adsorption of MO onto Mn–mica was governed by the number of active sites and the adsorption energy. This study offers insights into the manganese control of the interactions between MO ions and Mn–mica active sites.

Structural Characterization of Octahedral Sheet in Dioctahedral Smectites by Thermal Analysis

The structures of octahedral sheets of dioctahedral phyllosilicates show cis-vacant (cv) and trans-vacant (tv) configurations due to the different distributions of the octahedral cations over cis- and trans-sites. On the basis of the different dehydroxylation temperatures, a thermal analysis is an effective method used to identify the cv and tv configurations of an octahedral sheet in dioctahedral smectites. The proportions of cv and tv configurations were determined by fitting the derivative thermogravimetry (DTG) curves. A wide range of cv and tv proportions were detected in the samples. The dehydroxylation temperatures of samples consisting of cv configuration are about 150 to 200 °C higher than those consisting of tv configurations. The samples were classified as tv varieties when octahedral Fe3+ > 0.46 mol/FU, and the pure tv dioctahedral smectites were found when Fe3+ > 1.8 mol/FU. A clear linear relationship was found between the content of octahedral Fe3+ and Al3+ and the proportion of cv and tv configurations. The substitution of Al3+ by Fe3+ in the octahedral sheets is the main factor for the formation of tv varieties. There was no relationship detected between the layer charge density, octahedral Mg2+ content, and the proportion of tv and cv. The present results indicate that the iron content has a significant effect on the structure of the octahedral sheet.

Polygenic chamosite from a hydrothermalized oolitic ironstone (Saint-Aubin-des-Châteaux, Armorican Massif, France): crystal chemistry, visible–near-infrared spectroscopy (red variety) and geochemical significance

Several generations of chamosite, including a red variety, occur in the Ordovician hydrothermalized oolitic ironstone from Saint-Aubin-des-Châteaux (Armorican Massif, France). Their chemical re-examination indicates a low Mg content (0.925 < Fe/(Fe + Mg) < 0.954), but a significant variation in IVAl. Minor vanadium is present at up to 1.1 wt.% oxide. Variations in IVAl, the vanadium content and the colour of chamosite are related to the hydrothermal reworking of the ironstone. Taking into account other published data, the ideal composition of chamosite is (Fe5–xAl1+x)(Si3–xAl1+x)O10(OH)8, with 0.2 < x < 0.8 (0.2: equilibrium with quartz; 0.8: SiO2 deficit). The red chamosite (IIb polytype) has a mean composition of (Fe3.87Mg0.23Mn0.01□0.07Al1.74V0.07)(Si2.33Al1.67)O10(OH)8. This chamosite is strongly pleochroic, from pale yellow (E || (001)) to deep orange red (E ⊥ (001)). Visible–near-infrared absorbance spectra show a specific absorption band centred at ~550 nm for E ⊥ (001), due to a proposed new variety of Fe/V intervalence charge-transfer mechanism in the octahedral sheet, possibly Fe2+ – V4+ → Fe3+ – V3+. While the formation of green chamosite varieties is controlled by reducing conditions due to the presence of organic matter as a buffer, that of red chamosite would indicate locally a weak increase of fO2 related to oxidizing hydrothermal solutions.

Microwave-Assisted Acid Activation of Clays Composed of 2:1 Clay Minerals: A Comparative Study

The effect of the microwave-assisted acid treatment (MAT) on the structure and texture of dioctahedral (montmorillonite) and trioctahedral (saponite) smectites, kerolitic clays and sepiolites were studied by scanning electron microscopy, nitrogen adsorption, X-ray fluorescence, X-ray diffraction and Fourier transform infrared spectroscopy. This study shows that in the smectite group of minerals the effectiveness of MAT is notably influenced by the chemical composition of the octahedral sheet, whereas in kerolitic clays it is influenced by the proportion of the expandable phase in the mixed layer sequence. On the other hand, the reactivity of sepiolites depends on the width of the natural fibres. With these treatments, extremely high specific surface area (SSA) increments are achieved in just 16 min. The SSA increments reach values up to 231 m2/g (%ΔSBET = 80) in sepiolites, 198 m2/g (%ΔSBET = 155) in Mg-smectites, and 161 m2/g (%ΔSBET = 61) in kerolitic clays.

Influence of the Structure and Experimental Surfaces Modifications of 2:1 Clay Minerals on the Adsorption Properties of Methylene Blue

In this work the adsorption capacities of methylene blue on Mg-smectite and sepiolite and its derived material obtained after acid treatment and/or the addition of Fe at its surfaces are studied. Natural smectite with high Mg-content in its octahedral sheet (Mg-smectite) displays higher adsorption capacity than the sepiolite due to the ability of Mg-smectite to expand the basal spacing to accommodate methylene blue cations between adjacent layers and the inability of sepiolite to adsorb these cations within the structural channels. The acid-activation of Mg-smectite causes a clear decrease in the adsorption capacity attributed to the partial loss of the interlayer positions by the loss of the octahedral sheet and subsequent formation of amorphous silica. Moreover, the adsorption of the Mg-smectite decreases even more when iron oxohydroxides species are incorporated in its interlayer spacing making inaccessible the interlayer active sites for the adsorption of methylene blue cations. On the contrary, the microwave-assisted acid treatment of sepiolite causes a slight increase in the adsorption capacity related with the dispersion of fibers. Nevertheless, contrary to that observed with Mg-smectite, higher increasing of adsorption capacities are obtained after the formation of new adsorption centers due to the incorporation of iron oxohydroxides species at the external surfaces of sepiolite.