The use of microorganisms to remove Fe (oxyhydr)oxides from kaolins has the potential to be an effective method for upgrading the whiteness and brightness, and therefore the commercial value, of the kaolin. The purpose of the present study was to compare kaolin products obtained by currently used chemical leaching methods with a bioleaching treatment using Aspergillus niger in order to remove Fe from kaolin (from Canakkale, Turkey). The effects of pulp density, temperature, and oxalic acid concentration on the chemical leaching experiments were investigated using the ANOVA-Yates test. The greatest degree of removal of Fe from the kaolin sample (at 15% w/v pulp density, temperature of 80°C, oxalic acid concentration of 0.2 M, and a particle size of <63 µm) was found to be 94.89% in 120 min of leaching. The Fe content decreased from 1.723%) Fe2O3 to 0.088% Fe2O3. In a shake flask, bioleaching of kaolin by Aspergillus niger resulted in removal of 77.13% of the total Fe, suggesting that this strain is effective at removing Fe impurities from kaolin. The removal efficiency generally decreased with increased pulp density. The Fe content of the kaolin decreased from 1.723% Fe2O3 to 0.394% Fe2O3 (at 1% w/v pulp density, temperature of 25°C, Aspergillus niger 3 × 107 spores, and particle size of <63 µm) after 21 days of bioleaching.

The potential use of near-infrared (NIR) spectroscopy as a characterization tool for organo-clays would be a great asset but little work has been done in this regard because the application of NIR to clay mineral studies is a relatively new phenomenon. The purpose of this study was to use NIR spectroscopy to investigate the effect of alkylammonium cations on the acid dissolution of a high-charge montmorillonite (SAz-1). Detailed analysis of the spectra of Li+-, TMA+- (tetramethylammonium), and HDTMA+- (hexadecyltrimethylammonium) saturated SAz-1 montmorillonite in the NIR region was achieved by comparing the first overtone (2ν) and combination (ν+δ) bands of XH groups (X = O, C) with the fundamental stretching (ν) and bending (δ) vibrations observed in the mid-infrared (MIR) region. Comprehensive analysis of the vibrational modes of CH3-N, CH3-C, and -CH2-C groups of TMA+ and HDTMA+ cations detected in the MIR and NIR regions was also performed. Both MIR and NIR spectra demonstrated that exchange of Li+ by TMA+ only slightly improved the resistance of SAz-1 layers to dissolution in 6 M HCl at 80°C, while exchange by the larger HDTMA+ cations almost completely protected the montmorillonite layers from acid attack. Use of NIR spectra in reaching these conclusions was crucial. Only in the NIR region could the creation of SiOH groups be monitored, which is an important indicator of the acidification of the montmorillonite surface. The OH-overtone region in the spectra of Li-SAz-1 and TMA-SAz-1 revealed that the SiOH band near 7315 cm−1 increases in intensity with enhanced acid treatment. In contrast, no SiOH groups were identified in the NIR spectra of HDTMA-SAz-1 treated in HCl, indicating that HDTMA+ completely covers the inner and outer surfaces of the montmorillonite and hinders access ofprotons to the Si-O− bonds created upon acid treatment.

The potential for structural failure of consolidated clay materials, which is of great importance in many applications, typically are assessed by measuring the localized strain bands that develop under anisotropic load stress. Most methods are precluded from providing a full understanding of the strain anisotropy because they only give two-dimensional information about the stressed clay blocks. The purpose of the present study was to investigate three-dimensional strain localization in a kaolinite matrix, caused by strain anisotropy due to a biaxial plane-strain test, using a relatively new method known as Anisotropy of Magnetic Susceptibility (AMS). This method involves induction of magnetism in an oriented sample in different directions and measurement of the induced magnetization in each direction. The AMS analyses were performed on core samples from different parts of the deformed kaolinite matrix. The degree of magnetic anisotropy (P′), which is a measure of the intensity of magnetic fabric and a gauge of strain intensity, was shown to be greater in cores containing shear bands than in those containing none. A threshold value for P′ for the deformed kaolinite matrix was identified, above which shear bands may develop. The comparison of the shape parameter (T), obtained from undeformed and deformed samples, illustrated a superimposition of prolate strain over the original oblate fabric of the kaolinite matrix. The orientation of the principal strain axis revealed that reorientation or rotation of the principal axis occurred along the shear bands.

The nature of component layers of mixed-layer illite-smectite and their possible evolution in the course of illitization have been debated since the 1960s. The present study is a new attempt to solve these problems, using samples collected from diverse geological formations around the world. Twenty three purified illite-smectites from bentonites and hydrothermal rocks, covering the complete range of expandability, were analyzed chemically, including ${\text{NH}}_4^{+}$\$\end{document} determination, and their structural formulae were calculated. The exchangeable cations (EXCH) were plotted vs. the fixed cations (FIX) yielding the following experimental regression:$\text{EXCH}=-0.43\times \text{FIX}+0.41\left({\text{R}}^2=0.98\right)$\$\end{document}

FIX and EXCH depend on the charge of the illite (Qi) and smectite (Qs) interlayers, and the fractions of these interlayers in the bulk clay leading to: $\text{EXCH}=-Q_{\text{s}}\text{/}{Q}_{\text{i}}\times \text{FIX}+Q_{\text{s}}$\$\end{document}

Analysis of these relations and independent measurements of the total specific surface area (TSSA) indicate that the layer charges of both types do not change in the course of illitization. The smectite layer charge is equal to 0.41 and the illite layer charge is equal to 0.95 per O10(OH)2. End-member illite has a well defined composition that is close to intermediate between muscovite and phengite, with fixed cations content greater than that specified in the AIPEA classification of layer silicates:${\text{FIX}}_{0.95}\left({\text{Si}}_{3.25}{\text{Al}}_{0.75}\right)\left({\text{Al}}_{1.81}{\text{Fe}}_{0.01}{\text{Mg}}_{0.19}\right){\text{O}}_{10}{\left(\text{OH}\right)}_2$\$\end{document}

The established relationship allows the calculation of the mean number (N) of 2:1 layers in all fundamental particles and also the fraction of smectitic layers (fs) from FIX:$N=Q_{\text{i}}\text{/}(Q_{\text{i}}-\text{FIX})f_{\text{s}}=(Q_{\text{i}}-\text{FIX})\text{/}{Q}_{\text{i}}$\$\end{document}

N and fs can be used to calculate TSSA, and all three parameters can also be calculated from cation exchange capacity and from X-ray diffraction peak positions, utilizing the regressions established here.

The transformation of clay minerals into organo-clays by surfactant intercalation is of great environmental and industrial importance because it causes the clay to attract hydrophobic contaminants and other non-polar organic compounds, but a better understanding is needed of the mechanisms by which different classes of surfactants are intercalated. The purpose of this study was to synthesize and characterize an organo-clay comprising triethylene glycol monodecyl ether (C10E3) non-ionic surfactant, which has a lamellar phase at room temperature, intercalated into Ca-montmorillonite from Wyoming (SWy-2). The C10E3 non-ionic surfactant differed from previous non-ionic surfactants used in the formation of a lamellar phase in that it consisted of the stacking of molecules by hydrophobic interaction. C10E3-clay composites were characterized by complementary techniques (adsorption isotherms, X-ray diffraction, and infrared spectroscopy) and were compared to benzyldimethyltetradecyl ammonium chloride (BDTAC) cationic surfactant-clay composites for different loadings of the surfactant. For large loadings, the amount of C10E3 adsorbed, which can be described by the Langmuir equation, seemed to reach a steady state close to that of the cationic surfactant. The adsorption processes of the two surfactants were different. For the cationic surfactant, the adsorption, as described in the literature, was due to ion exchange between organic cations and Ca2+ counterions. The adsorption of C10E3 did not depend on electrostatic interaction but rather was due to several interaction mechanisms (H-bonding, ion-dipole, and hydrophobic interaction). For both surfactants, the expansion was limited to two adsorbed monolayers parallel to the clay surface. The expansion of the basal spacing to 17 Å suggested a complete dissociation of the C10E3 lamellar phase when adsorbed on the Ca-smectite. Organo-clays made using the non-ionic surfactant were stable, changing the chemical nature of clay to hydrophobic, and allowing for other cations to be exchanged, which has importance in the manufacture of new nanocomposites or geochemical barriers.

The term ‘montmorillonite’ encompasses a wide range of chemical compositions and structures. Comprehensive and reliable characterization is essential for unambiguous classification. Twenty eight purified, Na-exchanged smectites (<0.2 µm) were characterized by layer-charge measurement using the alkylammonium method, by cation exchange capacity (CEC) measurement with Cu-triethylenetetramine, by determination of the chemical composition using X-ray fluorescence analysis, by calculation of the structural formula following determination of the octahedral structure (trans-vacant vs. cis-vacant) by simultaneous thermal analysis, and by X-ray diffraction analysis. Mössbauer spectroscopy was applied to determine the oxidation state and coordination of Fe and changes thereof during purification of the source materials.

The charge derived from chemical composition was considerably greater (by up to 30%) than the measured layer charge. The independently measured layer charge was used to calculate the structural formula. The measured CEC values, comprising the permanent charges and the pH-dependent edge charges, were consistent with measured layer charge but not with layer charge derived from the chemical composition. Therefore, the structural formula of smectites should be calculated using the measured layer charge.

The dehydroxylation temperature, which conveys information about the structure of the octahedral sheet, was correlated to the amount of Mg and Fe3+ and the location of charges. No relationship was found among the dehydroxylation temperature and the mean layer charge or the Mg content. In contrast, a clear relationship was observed between the Fe content and the dehydroxylation temperature. Montmorillonites with an Fe content <0.3/f.u. are cis-vacant and those containing Fe3+ > 0.3 mol/f.u. are trans-vacant, mostly with additional cis-vacancies. Tetrahedral substitution also appeared to be a function of the number of trans-vacancies.

The parameters analyzed provide the basis for a new descriptive classification system.

The chemistry of Al transformation has been well documented, though little is known about the mechanisms of structural perturbation of Al precipitates by carbonates at a molecular level. The purpose of the present study was to investigate the structural perturbation of Al precipitates formed under the influence of carbonates. Initial carbonate/Al molar ratios (MRs) used were 0, 0.1, and 0.5 after aging for 32 days, then the samples were analyzed by X-ray absorption near edge structure spectroscopy (XANES), X-ray diffraction (XRD), Fourier-transform infrared absorption spectroscopy (FTIR), and chemical analysis. The XRD data were in accord with the FTIR results, which revealed that as the carbonate/Al MR was increased from 0 to 0.1, carbonate preferentially retarded the formation of gibbsite and had relatively little effect on the formation of bayerite. As the carbonate/Al MR was increased to 0.5, however, the crystallization of both gibbsite and bayerite was completely inhibited. The impact of carbonate on the nature of Al precipitates was also evident in the increase of adsorbed water and inorganic C contents with increasing carbonate/Al MR. The Al K- and L- edge XANES data provide the first evidence illustrating the change in the coordination number of Al from 6-fold to mixed 6- and 4-fold coordination in the structural network of short-range ordered (SRO) Al precipitates formed under the increasing perturbation of carbonate. The fluorescence yield spectra of the O K-edge show that the intensity of the peak at 534.5 eV assigned to σ* transitions of Al-O and O-H bonding decreased with increasing carbonate/Al MR. The XANES data, along with the evidence from XRD, FTIR, and chemical analysis showed clearly that carbonate caused the alteration of the coordination nature of the Al-O bonding through perturbation of the atomic bonding and structural configuration of Al hydroxides by complexation with Al in the SRO network of Al precipitates. The surface reactivity of an Al-O bond is related to its covalency and coordination geometry. The present findings were, therefore, of fundamental significance in understanding the low-temperature geochemistry of Al and its impacts on the transformation, transport, and fate of nutrients and pollutants in the ecosystem.

‘Ghassoul’ clay is a Mg-rich clay from Morocco which is of great industrial use and interest, but its characterization is still incomplete. The purpose of this study was to provide further details regarding the structure and characteristics of this important commercial clay mineral. Mineralogical and physicochemical characterizations of the raw form of ‘Ghassoul’ clay from Jbel Ghassoul in Morocco, and of its <2 µm size fraction, purified and Na+-saturated, were carried out using X-ray diffraction (XRD), X-ray fluorescence (XRF), infrared spectroscopy (IR), and differential and thermogravimetric analysis (DTA/TG). The XRD data revealed that the raw Ghassoul clay consists mainly of a Mg-rich trioctahedral smectite, stevensite, together with quartz and dolomite. The IR spectra consisted of vibrations typical of trioctahedral smectites. The DTA/TG curves were also similar to those of trioctahedral smectites. Chemical analysis confirms that this Mg-rich trioctahedral smectite is a stevensite characterized by a limited isomorphic substitution of Si4+ by Al3+. The thermal transformations examined by in situ XRD as a function of the firing temperature from 100 to 1200°C indicated that stevensite was transformed to enstatite (MgSiO3) at temperatures >800°C and that quartz was transformed to cristobalite when the temperature exceeded 1100°C. These transformations were irreversible. The specific surface area and cation exchange capacity (CEC) of the ‘Ghassoul’ clay are 133 m2/g and 75 meq/100 g, respectively. The main exchangeable cation is Mg2+ (53 meq/100 g).

Large transition-metal contents add desirable physical properties, such as redox reactivity, magnetism, and electric or ionic conductivity to micas and make them interesting for a variety of materials-science applications. A Mn- and F-rich tainiolite mica, , was synthesized by a high-temperature melt-synthesis technique. Subsequent annealing for 10 days led to a single-phase and coarsegrained material. Single-crystal X-ray diffraction studies were performed and characteristic geometric parameters were compared to the analogous ferrous compound, synthetic Fe-rich tainiolite, . Both tainiolite structures are outside the compositional stability limits for the 2:1 layer structure, and incorporating the relatively large cation Mn2+ requires significant structural adjustments in both the octahedral and tetrahedral sheets. As expected, increasing the ionic radius of the octahedral cation from 0.78 Å (VIFe2+) to 0.83 Å (VIMn2+) reduces the octahedral flattening angle from <Ψ> = 57.05° to <Ψ> = 56.4°, the smallest value ever observed for a tetrasilicic mica. However, even this small <Ψ> value is insufficient to match the lateral sizes of the tetrahedral and octahedral sheets and, in addition, unusual structural adjustments in the tetrahedral sheet are required. The average tetrahedral bond length <T-O> is much greater (1.643 Å) than the average value observed for tetrasilicic micas (1.607 Å,) and a significant difference between the <T-O>apical (1.605 Å) and the <T-O>basal bond lengths (1.656 Å) and an enlarged basal flattening angle (τbas = 106.29°) are noted. These parameters indicate: (1) that the 2:1 layer might be more flexible than previously thought, to allow matching of the lateral dimensions of the tetrahedral and octahedral sheets; and (2) that many other compositions that appear interesting from a materials-science point of view might be accessible.