The arguments of Vidal et al. (2010) against the incorporation of H3O+ rather than of H2O in the interlayer position of illite are disputable. Stoichiometric arguments do indeed suggest that the excess water in the Silver Hill illite is in the formof H3O+. No reason exists to assume less water content in the IMt-2 sample than in those determined by Hower and Mowatt (1966) and confirmed by the thermogravimetric analyses of Nieto et al. (2010). The comparison between element contents calculated from end-members and those from the structural formula in figure 1 of Vidal et al. (2010) is not an experimental result, but rather a trivial mathematical artifact. The fact that thermodynamic models, based on the incorporation of interlayer H2O in illite, may provide reasonable estimates neither proves nor disproves the presence of H3O+; this is because thermodynamics is a non-atomistic, macroscopic approach.

The Ypresian phosphatic series of the Gafsa-Metlaoui basin, southwestern Tunisia, is represented by an alternation of phosphatic levels and interbedded facies, which are composed of marly clay and silica-rich rocks. The present work aimed to clarify the genesis of palygorskite and sepiolite of the interbedded facies and to understand the depositional environment of the phosphatic series. The interbedded facies of the Stah and Jellabia mines were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Energy Dispersive X-ray microanalysis (EDX) of individual constituents and their aggregates. The data obtained indicate that samples are made up of francolite, calcite, dolomite, quartz, feldspars, and clay minerals; the latter consist of palygorskite-sepiolite minerals associated with smectite. Observations by SEM revealed the occurrence of palygorskite and sepiolite as fine and filamentous fibers with thread-like facies and coating dolomite, calcite, and a marly matrix. Such features can be considered as textural evidence of authigenic palygorskite-sepiolite. At the bottom of the Stah section, SEM observations revealed that the fine fibers are more abundant within silica-rich rocks. Silica is commonly available due to bacterial activity saturating its environment with the silicic acid required for the formation of palygorskite-sepiolite. In the interbedded facies of the Jellabia section, the moderate fibrous clay content and the presence of well crystallized dolomite revealed that the shallow-marine water was characterized by high-Mg and low-Si activities.

Proteins and protein-like molecules are abundant in various geochemical environments; they form complexes with mineral surfaces and with dissolved organic matter. To evaluate the effect of proteins on rates of dissolution of minerals, experiments on the dissolution of amorphous silica in solutions containing various concentrations of bovine serum albumin (BSA) were performed in this study. The dissolution experiments were carried out by a batch method using solutions of 0.1 mM NaCl with 0.00, 0.05, 0.1, 0.2, 0.5, and 1.0 mg/mL of BSA at three different pH conditions, 6, 5, and 4. The results of the experiments demonstrated that BSA exhibited strong rate-enhancement effects on the dissolution of amorphous silica and were dependent on BSA concentration and the solution pH. At pH 6, the dissolution rates of amorphous silica appeared to increase successively by ~1.6, 2.2, 2.4, 2.5, and 2.9 times with increasing BSA concentrations of 0.05, 0.1, 0.2, 0.5, and 1.0 mg/mL, respectively. The rates of dissolution increased by greater degrees, ~3.1–5.8 and 4.9–13.0 times at pH 5 and 4, respectively. According to the calculated charge distributions of amino acid residues of the BSA molecule, the dissolution rates of amorphous silica were likely to be enhanced by attractive electrostatic interactions of the positively charged side chains of lysine, arginine, and histidine residues with the negatively charged >SiO− sites on the amorphous silica surface. The negatively charged side chains such as glutamic acid and aspartic acid residues may inhibit the attractive interaction, depending on the degree of deprotonation.

Methods for predicting the volume change and swelling-pressure behavior of expansive clays require detailed understanding of coupled interactions between clay microstructure and macrostructure under hydraulic, thermal, and mechanical loads. In this study a suite of water-vapor sorption experiments was conducted using compacted bentonites hydrated in controlled relative humidity (RH) environments maintained under free and constrained volume-change boundary conditions. Emphasis was placed on examining the influences of compaction and predominant exchange cation on the water uptake, volume change, and swelling pressure response. Densely compacted specimens exhibited greater volume changes under free swelling conditions and greater swelling pressures under fully confined conditions. Water uptake, volume change, and swelling pressure were all more significant for Colorado (Ca2+/Mg2+) bentonite than forWyoming (Na+) bentonite. Plastic yielding, evident as a peak in the relationship between swelling pressure and RH, was more evident and occurred at lower RH for the Colorado bentonite. This observation was interpreted to reflect the limited capacity for interlayer swelling in Ca2+/Mg2+ bentonites and corresponding structural collapse induced by the onset of water uptake in larger intra-aggregate and inter-aggregate pores. A semi-quantitative model for the evolution of clay microstructure resulting from interlayer hydration was considered to attribute the experimental observations to differences in the efficiency with which transitions in basal spacing translate to bulk volume changes and swelling pressure. Results provide additional insight and experimental evidence to more effectively model the mechanical behavior of compacted bentonites used as buffer or barrier materials in waste repository applications.

The chemical and biological methods employed to date in the removal of free cyanide (CN−) and metal-cyanide complexes from aqueous fluids have proved expensive and problematic. A simpler and more economical approach was attempted in the present study using zeolite and sepiolite. The effectiveness of zeolite from Manisa-Gördes (Turkey) and of sepiolite Eskişehir-Sivrihisar (Turkey) at removing free and Cu-complexed cyanide, [Cu(CN)3]2− was investigated. For removal of CN−, the system performance was examined in terms of concentration, particle size, and retention time. Material with smaller particle sizes (<0.106 mm) performed better, particularly in the case of sepiolite. The maximum CN− removal capacities of zeolite and sepiolite were calculated as 571 and 695 meq/100 g for free CN adsorption, and 455 and 435 meq/100 g for Cu-complexed CN adsorption, respectively. The time to reach equilibrium was calculated as 1050 min. Acid activation, a simple cation adsorption removal method, did not improve the process, instead leading to reduced CN adsorption. Hydroxylated surfaces of metal oxides at the edges of zeolite develop charges and exchange with anions in water. Mg2+ ions located at the edges of the octahedral sheet can create complexes with CN− anions. Moreover, hydrogen bonding with anions (CN− in this case) and H+ of zeolitic water bonded to coordinated water molecules can also create complexes. These two complexes are considered to be effective mechanisms for sepiolite. The effects of both acid activation and CN adsorption were clearly observed in the Fourier-transform infrared spectra. Removal of CN was characterized by the Langmuir isotherm, indicating monolayer coverage with chemical bonding to the surface, which deteriorated during acid activation. The study indicated that zeolite and sepiolite can be used efficiently and easily for removal of free and Cu-complexed CN.

The morphology, dehydroxylation, and dissolution properties of single- and multi-metal (Cr, Zn, Cd, and Pb)-substituted goethites prepared using hydrothermal methods are reported. The crystal morphology varied with the nature and the number of metals present in the system. The presence of Cr produced broader crystals while Zn, Cd, and Pb produced narrower crystals than pure goethite. The presence of multiple metals retards the crystal growth of the mineral. Metal substitution caused changes in the unit-cell parameters and the infrared (IR) spectra of the samples. The IR spectra were also sensitive to the morphology of the crystals. The separation of γO and δOH bending frequencies increased with increase in area and aspect ratio of the (100) crystal face. The dissolution-kinetics studies (1 M HCl, 40ºC) of single-metal-substituted goethite provided the following dissolution rate order: Zn- > Pb(II)- ≥ Pb(IV)- > unsubstituted > Cd- > Cr-goethite. More complex results were obtained for the multi-metal-substituted samples. In the di-metal-substituted goethites, incorporation of Cr suppressed the dissolution rate of Zn-substituted goethite by 85% and Cd suppressed the dissolution rate of Zn-substituted goethite by 53%. Similarly, incorporated Cr and Cd suppressed the dissolution rate of Pb(II)-substituted goethite by 50%. The dissolution rates of multi-metal-substituted goethite were linearly related to the steric strains derived from the lattice parameters of the mineral. Dissolution studies also showed that Cr, Zn, Cd, and Pb(IV) were distributed homogeneously throughout goethite crystals while Pb(II) was enriched in the near-surface regions of the crystals. Incorporation of Cr and Pb(II) increased, while Zn and Pb(IV) decreased the dehydroxylation temperature of single-metal-substituted goethites. Incorporation of Zn suppressed the effect of Cr on the dehydroxylation temperature in multi-metal-substituted goethites.

In the paper ‘Porosity evolution of free and confined bentonites during interlayer hydration” from Clays and Clay Minerals, vol. 58, (2010), 399–414

In deep geological repositories for high-level nuclear wastes, interactions between steel canisters and clay-rich materials may lead to mineralogical transformations with a loss of the confining properties of the clays. Experiments simulating the conversion of smectite to Fe-rich clay phases in contact with Fe metal have been carried out to evaluate such a possibility by taking into account the effects of a series of critical parameters, including temperature, pH, and Fe/clay (Fe/C) and liquid/clay (L/C) ratios. The mineralogical and chemical transformations observed in these experiments have been compared with data from the literature, and subsequently used to propose a conceptual model for the main mineralogical transformations which can be expected in clay formations surrounding high-level nuclear waste repositories. In the presence of Fe metal and under low oxygen fugacity (<-40) the main mineralogical sequences are as follows:

1. (1) up to 150°C, under neutral pH, and L/C > 5: dioctahedral smectite (di-sm) → 7 Å Fe-rich phase (berthierine, odinite-cronstedtite) for large Fe/C ratios (>0.5), or di-sm → Fe-rich di-sm + Fe-rich trioctahedral smectite (tri-sm) for small Fe/C ratios (0.1)

2. (2) up to 150°C, under alkaline pH (10–12), and L/C > 5: di-sm → Fe di-sm (±palygorskite) for a small Fe/C ratio (0.1)

3. (3) at 300°C, Fe/C = 0.1, and L/C > 5: di-sm → Fe-rich saponite → trioctahedral chlorite + feldspar + zeolite (near-neutral pH); di-sm → Fe-rich vermiculite + mordenite (pH 10–12).

Low temperatures (<150°C) and large L/C and Fe/C ratios seem to favor the crystallization of the serpentine group minerals instead of Fe-rich trioctahedral smectites or chlorites, the latter being favored by higher temperatures. The role of L/C and Fe/C ratios and the competition between them at different temperatures is a crucial point in understanding the transformation of smectite in contact with Fe metal.

Widespread alteration in the Upper Cretaceous pyroclastic units of the Tirebolu (Giresun) area, NE Turkey, has resulted in significant occurrences of bentonite with economic potential. No detailed geological, mineralogical, or geochemical characterization of these occurrences has been carried out to date. The aim of this study was to describe the geological background, the mineralogical, chemical, and stable-isotope characteristics of the bentonite, and major aspects of their formation, e.g. type and source of low-temperature alteration, mass balance, chemical evolution of the smectites, and geochemistry of major and trace elements. The bentonite contains abundant smectite with occasional kaolinite and mordenite, volcanogenic feldspar, quartz, biotite, hornblende, glass shards, and pumice fragments, along with the diagenetic minerals, opal-CT, and, in some locations, calcite. X-ray diffraction patterns of the clay fractions exhibit characteristics of pure montmorillonite and beidellite-type smectite. Micromorphologically, the smectite exhibits a honeycomb texture, the kaolinite occurs in both vermiform and irregular platy forms, and the mordenite occurs in fibrous form. All of these minerals are edged with devitrified volcanic glass and resorbed feldspar. Chemically, the smectites are Ca-smectite. Geochemical data indicate that alteration of the pyroclastic units took place under suboxic and anoxic environmental conditions during bentonite formation. Field observations and mineralogical, geochemical, oxygen, and hydrogen isotopic data indicate that the alteration of feldspar and volcanic glass in the pyroclastics by mixed meteoric and sea water in a shallow marine environment under alkaline and acidic conditions, respectively, controlled by environmental Al, Ca, and Na concentrations, resulted in the formation of authigenic smectite, mordenite, and kaolinite. A large Ca content in the smectite originated from surrounding units, which resulted in high alkalinity; Mg originated from seawater.

As advances in technology have led to increased use of bentonites, more high-quality bentonite has been sought. The volume of high-quality bentonites available is shrinking and use of bentonite reserves containing impurities is inevitable. The aim of this study was to apply Box–Behnken experimental design and response surface methodology to model and optimize some operational parameters of a hydrocyclone to produce three groups of bentonite concentrates. The four significant operational parameters of hydrocyclones are feed solid ratio, inlet pressure, vortex diameter, and apex diameter, and these parameters were varied and the results evaluated using the Box–Behnken factorial design. In order to produce bentonite concentrates using a hydrocyclone, mathematical model equations were derived by computer simulation programming applying a least-squares method, using Minitab 15. Second-order response functions were produced for the swelling and to establish the quantity of smectite in the bentonite concentrates. Predicted values were found to be in good agreement with the experimental values (R2 values of between 0.829 and 0.999 for smectite and three different swelling groups for the bentonites). Although in natural states these bentonites are not suitable for industrial use, enhancements were obtained giving up to 81.45% smectite and by increasing swelling by 194% for the three bentonite groups. The swelling properties of the bentonites are improved by increasing the proportion of smectite content. The graphics were designed to relate swelling and smectite content according to the two-dimensional hydrocyclone factors, and each factor was evaluated in itself. The present study revealed that the Box–Behnken and response surface methodology can be applied efficiently to model the hydrocyclone for bentonite; the method is economical and provides the maximum amount of information in a short period of time and with the smallest numberof experiments.