The adsorption of 13C-labeled benzene on imogolite has been studied on samples which had been evacuated and then heated to remove water below their decomposition point. After adsorption of labeled benzene, the samples were studied by nuclear magnetic resonance using non-spinning techniques. The results show that benzene can occupy more than one pore type and that water does not displace benzene from the intra-tube pores at atmospheric pressure. A further finding is that there are at least two types of adsorbed benzene in so called inter-tube pores, one of which is more rigidly held than that in intratube pores. The presence of disordered materials at the edge of pores could also play a role in altering the pore mouth thereby creating new types of pores. Moreover, where two tubes do not pack properly, space might be created where an adsorbed molecule may bind more tightly than expected in a conventional pore.

Several Al-substituted goethites were synthesized by hydrolysis of Fe3+ salt solutions. The kinetics of the reductive dissolution of these goethites in dithionite-ethylenediaminetetra acetic acid (D-EDTA) was studied at pH 5.5, at 303, 323 and 333 K. The initial dissolution rate (R) per unit of surface area decreases with Al substitution. In the sample with greater Al content (G″7), the kinetic profiles of the dissolved Fe fraction vs. time gave a small positive intercept. The kinetic profile of R as a function of EDTA initial concentration shows a significant weakening in the presence of Al. The maximum is flatter and wider in Al-substituted goethite than that of pure goethite. In sample G″7, where the Al content is 11.3 mol.% the maximum is obtained when the [D]:[EDTA] initial ratio is ∼4.5 vs. 2 in un-substituted goethite. These results can be attributed to the lesser density of the more active dimeric sites, the presence of more strongly bonded Al-O-Fe with regard to Fe-O and the small value for the ≡ Al-EDTA surface species constant. Activation energy (Ea) increases with Al substitution. Its value is doubled from GO (pure goethite) to G″7 (11.3 mol.% of Al). The frequency factor (A) acts in the opposite sense to Ea, but it is not sufficient to outweigh the effect of Ea.

The adsorption of metals by clay minerals is a complex process involving different mechanisms, and is controlled by different variables which can interact. The aim of this work was to study the retention mechanisms of Cd on illite. We obtained Cd adsorption isotherms at constant pH, adsorption edges as a function of pH, adsorption isotherms at 5, 25 and 45°C (pH = 7), and response surfaces of the simultaneous effect of pH, initial concentration, ionic strength, and temperature on the retention of Cd on illite. Below pH 6, adsorption of Cd on illite is via ion exchange with H3O+ and Na+ ions which saturate the exchange sites, the exchange with Na+ being the main mechanism between pH 4.5 and 6.0. For pH values >6, the effect of ionic strength on the amount of Cd2+ retained decreased with pH, being negligible at pH 8; the proton stoichiometry was greater than for pH values <6 and an increase in the temperature favored the retention of Cd. These facts are compatible with a more specific process involving hydrolyzed species, in which Cd can associate with illite as an inner sphere complex.

Twelve nontronites and two ferruginous smectites have been characterized with respect to Fe3+ occupancy of tetrahedral sites. The techniques used were near infrared, Fe-K X-ray absorption near-edge and X-ray absorption fine-structure spectroscopies, along with two X-ray diffraction techniques. The results show that calculations of the structural formulae of many nontronites should be adjusted to include Fe3+ in tetrahedral sites. The nontronite from Spokane County, Washington, (∼44% Fe2O3) is essentially an end-member with its non-siliceous tetrahedral sites occupied by Fe3+. Samples with chemical compositions similar to Garfield nontronite (∼36.5% Fe2O3) may have small amounts (<5% of total Fe3+) of tetrahedral Fe3+. Tetrahedral Fe3+ is unlikely to be present in samples containing less than ∼34% Fe2O3.

The coarse, non-clay fraction of many flint-like kaolinitic claystones often contains mineral grains diagnostic of the claystone's origin and, in the case of tonsteins (altered volcanic ashes), may also provide minerals suitable for radiometric dating. Separation of the non-clay mineral fraction is often difficult because flint clays and flint-like clays resist slaking in water and thus are difficult to disaggregate. Chemical disaggregation of resistant kaolinitic claystones may be achieved by immersion in either hydrazine monohydrate or DMSO for periods ranging from one day to several weeks. Generally, hydrazine monohydrate works more quickly and efficiently than DMSO to disaggregate most kaolinitic claystones and flint clays.

The method for prediction of Gibbs free energies of formation, based on the parameter ΔGO=Mz+(clay) characterizing the oxygen affinity of the cation Mz+, on the smectites, considered as hydrated clay minerals, has been used for micas and brittle micas, and yielded underestimated values. This method of prediction can be improved by a new set of parameters ΔGO=Mz+(clay), characterizing the electronegativity of a cation in a specific site (interlayer, octahedral, tetrahedral in the 10 Å minerals), determined by minimizing the difference between experimental Gibbs free energies and calculated Gibbs free energies of formation from constituent oxides. By considering the crystal structure of 10 Å and 14 Å minerals, and assuming the same electronegativity of cations, ΔGO=Mz+(o), in the octahedral sheets, an attempt is made to determine the electronegativity of cations in the brucitic sheet, ΔGO=Mz+(b). The results indicate that this prediction method compared to other determinations, gives values within 0.25% of the experimentally-estim ated values. The relationships between ΔGO=Mz+(clay) corresponding to the electronegativity of a cation in the interlayer, octahedral, tetrahedral or brucitic sites and known ΔGO=Mz+(aq) were thus determined, allowing the determination of the electronegativity of transition metal ions and trivalent ions in each of the four sites and consequently contribute to the prediction of Gibbs free energies of formation of different micas and chlorites. Examples are given for low-Fe clinochlore whose solubility is measured experimentally and the results appear excellent when compared with experimental values.

Polarized micro-Raman spectra of a single large crystal of Keokuk kaolinite were recorded in the OH-stretching region with the laser beam directed along the different crystal axes. The Raman spectra are characterized by five OH-stretching bands at 3694, 3683, 3668, 3650 and 3620 cm−1 labeled A, Z, B, C and D, respectively. The relative intensities of these five bands depend on the orientation of the crystal and the scattering geometry. The spectra agree with the assertion that bands A and Z arise from out-of-plane vibrations, whereas band D corresponds to an in-plane vibration. The area ratios of the various bands were calculated from fitted curves of spectra recorded with the electric vector of the laser beam parallel to different crystallographic planes. The increments in the relative areas of bands B and C were parallel to those of bands A and Z and it appears that out-of-plane vibrations made considerable contributions to these bands also. From the change of area ratios with the change in the direction of the electric vector of the laser beam, bands A and Z were attributed to LO and TO frequencies of one inner-surface hydroxyl vibration. Bands A + Z, B, C and D were attributed to the vibrations of the hydroxyls assigned by Bish (1993) as OH(3), OH(4), OH(2) and OH(1), respectively. These observations were supported by photoacoustic and transmission IR spectra.

This study of magnetic minerals in a weathering profile developed on plateau basalts of the subtropical southern Paraná Basin explores the evolution of titanomagnetite to titanomaghemite. Six samples studied by optical microscopy, X-ray diffraction (XRD), electron microprobe, Mössbauer spectroscopy (MS) and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) support the interpretations.

The profile studied has two major parts: an upper, porous red-clay Latosol, ∼2–8 m deep, separated by a stone line from an underlying alterite which has two different facies — its argillaceous alterite consists of a clayey matrix with a well-developed fissure system whereas the underlying boulder alterite consists of rock cores surrounded by highly-porous cortexes of Al-goethite.

Optical microscopy showed the titanomagnetite-titanomaghem ite changes in color and shape through the profile. The decrease in the lattice parameter a of the magnetic separates from the rock cores to the alterite facies was detected by XRD. Mössbauer spectroscopy identified non-stoichiometric magnetite in the rock cores and Ti-substituted maghemite in the argillaceous alterite. Chemical analysis of the titanomagnetite-titanomaghe mite grains showed that the relative proportions of TiO2 and Fe2O3 vary in the different weathering facies. By SEM and EDS we also detected the presence of minor components as Si, Al, Ca, K, Mg and Mn.

These results led to the interpretation that the titanomagnetites from the fresh Parana basalts, located in the subtropical zone of Brazil, are unstable and gradually change to titanomaghemites. The evolution of these magnetic minerals is registered in the weathering facies related to climatic changes throughout geological time.

Porous silica products obtained by selective leaching of phlogopite using an acid solution were investigated by XRD, MAS NMR, SEM, TEM, DTA/TG, and N2 and Ar gas adsorptions. The phlogopite powder was leached by a nitric acid solution at various concentrations (0.01–10 M) at 5–150°C for 10 min–480 h. Selective leaching of the phlogopite powder became extensive when the concentration of nitric acid was >1 M. Only SiO2 remained after the treatment, the other components (MgO, Al2O3, K2O and Fe2O3) being selectively leached from the product. At higher leaching temperatures, the leaching rate became faster and the resulting maximum specific surface area of the porous silica product became larger at each leaching temperature. The porous silica products were found by SEM and TEM, to maintain their original platy particle shape even after the selective leaching. The 29Si MAS NMR spectra of the products, however, revealed that the linkage structure of SiO4 tetrahedra converted to a framework type from a layered type in the original phlogopite. The porous silica product with the maximum specific surface area (532 m2/g) was obtained by leaching in a nitric acid solution with concentration of 5 M at 90°C for 15 min. The pore-size distribution of the porous silica product was bimodal with micropores of ∼0.7 nm and mesopores of ∼4 nm. The pore size of the products changed from 0.7 nm to 4 nm and further to 6 nm with increased leaching time. The present results are discussed in relation to those reported for phlogopite by other workers.

Kaolin samples from the Jari deposit (Amazon region) were studied using various techniques to characterize its structural and crystallochemical aspects, and to establish its origin and evolution. A profile 60 m thick was selected in a kaolin mine (Morro do Felipe) located at the banks of the Jari river. Despite the great thickness of the deposit and the variety of kaolin types, the mineralogical composition is rather homogeneous and is mainly kaolinite associated with gibbsite and small amounts of quartz, anatase, goethite and hematite. The field observations and the morphological analysis indicate the existence of sedimentary features throughout the whole profile except for the upper aluminous clayey layer (Belterra Clay). This is evidence that the Rio Jari kaolin deposit originated from sedimentary material, the Alter do Chão Formation. The presence of alternating clay and sandy layers is explained by sedimentation processes with great depositional energy variation. Thus, the accumulation of thick clay layers was related to a low-energy phase, and during the high-energy phases, the deposition process led to the accumulation of sandy materials, constituted essentially of quartz and showing strong textural and structural variation. Later on, periods of hydromorphy were responsible for iron removal and consequently for the bleaching of the sedimentary formation. The crystallinity data show an increase of the structural disorder toward the surface associated with an increase in the amount of structural Fe in the kaolinite. The Rio Jari kaolin deposits should be considered as having originated from kaolinitic clay sediments of the Alter do Chão formation (protore) that was submitted to intensive lateritic weathering processes.

Birnessite can be used as a precursor in the preparation of manganese oxides. Synthesis of pure birnessite is difficult because of a side reaction, which yields hausmannite. This study aimed to develop a modified oxidation-deprotonation reaction (ODPR) method to eliminate the formation of hausmannite, and to investigate the influence of alkalinity on the synthetic products. In contrast to the conventional synthesis of birnessite through oxygen or permanganate oxidation, the ODPR method can produce birnessite without any impurities, within 5 h, and in a reproducible fashion. The distinctive feature of the ODPR method is the bubbling of N2 gas into NaOH and Mn2+ solutions before mixing the NaOH with Mn2+, in order to keep oxygen away from each solution. As soon as white pyrochroite was formed, oxygen gas was forced in as an oxidant to initiate the oxidation reaction. A black suspension with a blue tint appeared after 5 h of reaction. These precipitates were collected and examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared (IR) and Raman spectroscopy. The average oxidation state of the Mn oxides was also determined. The results showed that pure birnessite with good crystallinity was formed. Oxidation of 1 M NaOH mixed with Mn2+ solution formed random-stacked birnessite. However, the oxidation of 4 M NaOH mixed with Mn2+ formed birnessite. Random-stacked birnessite can be transformed into birnessite by ageing suspensions at 313 to 373 K.

The clay mineralogy of soil samples from the Morrow Plot Experiment (University of Illinois, Urbana Campus) was investigated. Analysis of soil samples taken at various intervals between 1913 and 1996 indicates that there is a significant influence of cropping method on the clay minerals in the soils. Curve decomposition methods were used to identify and follow the evolution of the different clay minerals: mica, illite and two randomly mixed-layered illite-smectite phases. The most striking difference is seen for continuous corn and corn-oats-hay rotations. Little change in clay mineralogy is seen in the rotation plot while a significant loss of illitic material from different phases was noted for the continuous-corn cultivation plots. Use of NPK fertilizer since 1955 appears to restore the clay mineralogy in continuous-corn cropping compared to that of the 1913 samples. From these data it appears that the I-S minerals play the role of a K buffer, becoming K-poor when the soil cannot furnish enough K from mineral reserves of detrital phases and K-rich when the soil is able to release enough K to enter into the I-S minerals, where it is available during a growing season, for plant growth.

The assignment of the 29Si CP/MAS-NMR spectrum of naturally-occurring sepiolite clay was re-examined using 29Si COSY and 1H-29Si HETCOR pulse sequences. Each of the three main resonances at −92.1, −94.6 and −98.4 ppm has been attributed to one of the three pairs of equivalent Si nuclei in the basal plane, and the resonance at −85 ppm to Q2(Si-OH) Si nuclei. On the basis of the COSY experiment, the resonance at −92.1 ppm is unambiguously assigned to the intermediate, near-edge Si sites. The HETCOR experiment revealed that the resonance at −94.6 ppm cross-polarizes almost entirely from the Mg-OH protons, and therefore is assigned to the central Si position. The remaining resonance at −98.4 ppm correlates strongly to the protons of the structural water molecules and therefore is assigned to the edge Si sites. Nearly complete rehydration was achieved at room temperature by exposing sepiolite samples that had been partially dehydrated at 120°C to water vapor or to D2O vapor. The rehydration results support the 29Si NMR peak assignments that were made on the basis of the COSY and HETCOR experiments.

The 29Si CP/MAS-NMR spectrum corresponding to the folded sepiolite structure in which approximately one half of the structural water has been removed by heating to 350°C is reported for the first time. The chemical shift values and relative intensities are significantly different compared to the resonances that are observed in the corresponding spectrum of the true sepiolite anhydride. These observations support the earlier claim that sepiolite heated to ∼350°C exists as a distinct phase to be differentiated from that of the completely dehydrated state.

Bentonite, biotite, illite, kaolin, vermiculite and zeolite were acidified or alkalized with hydrochloric acid or sodium hydroxide at concentrations of 0.1, 1.0 and 5.0 mole dm−3 at room temperature for two weeks. In acid treatments, dissolution of Al prevailed over Si and the opposite was observed in alkali treatments. The XRD patterns showed severe alteration of the crystal structure after acid treatments, whereas sharpening of the XRD peaks after alkali treatments was observed. Illite and kaolin were most resistant to acid attack. with a few exceptions, the surface areas of the minerals computed from both water and nitrogen adsorption isotherms increased with acid and alkali treatments. with increasing reagent concentration, the nitrogen surface area increased faster than the water surface area. well-defined trends were not noted in either changes of average water or nitrogen adsorption energies or in relative amounts of adsorption sites, indicating that the effects of acid and alkali attack are controlled by the individual character of the minerals.

Sudoites exhibit different crystal-chemical and textural properties which may be related to the structural and valence state of Fe. Mössbauer spectroscopic analysis shows that all Fe previously analyzed using a microprobe (from 1 wt.% to 7.2 wt.% total Fe as Fe2O3) is structural and occurs in both oxidation states (40% Fe2+ and ∼60% Fe3+). Electron microprobe analyses from ∼200 sudoites indicate that Fe occurs in both octahedral sheets according to three main types of substitution: Fe3+ = octahedral Al; Fe2+ = Mg; and Fe3+ + Fe2++ □ = 3Mg. Decreasing tetrahedral substitution balances Fe3+ substitution in the trioctahedral sheet. Increasing octahedral Fe results in a more dioctahedral character of sudoite.

X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, differential thermal analysis (DTA) and scanning electron microscope-transmission electron microscope (SEM-TEM) analyses showed that increasing octahedral Fe is associated with decreased stacking order and thermal stability due to the greater number of defects. In addition, with increasing octahedral Fe in sudoite, particles became smaller and more anhedral and consequently less stable with increasing Fe content. These structural and textural variations are interpreted as a result of the distortion of the sudoite structure by substitutions of Fe3+ with larger ionic radii for Al and Mg octahedral cations and by the formation of octahedral vacancies.

Crystal-size distributions (CSDs) for clay minerals with depth were measured from the Salton Sea Geothermal Field (SSGF) as a test for the presence and meaning of theoretical crystal-size distributions in a natural system. The SSGF is a classic open hydrothermal system, and crystals are forming directly without apparent modification of early-formed crystals, over a wide range of temperature. Thus, the measured CSDs are the actual distributions for a single episode in which all crystals grew at the same time from solution at different temperatures and depths, rather than through modifications of shallower samples.

Some TEM images of ion-milled samples from a range of depths were used to measure the crystal thicknesses of illite, chlorite and biotite. Grain-size histograms flatten, broaden and shift to larger sizes with increasing depth. Values of α and β were calculated and used to verify that the measured distributions are log normal. Reduced grain-size distributions for illite in SSGF samples obey steady-state constraints.

The observations appear to be consistent with evolution of illite with increasing depth in the SSGF system by growth in an open system giving rise to log-normal distributions, followed by supply-controlled growth in an open system. Because crystals at different depths grew simultaneously under different temperature and fluid conditions as a function of depth, they do not represent different stages of a single evolving system. The relations imply that isochemical and isothermal systems which permit an evolving system to be sampled are rare or non-existent. The data for distributions for a given depth in the SSGF are consistent with growth in an open system. The collective relations therefore imply that caution should be used in interpreting conditions of crystal growth in natural systems even where CSDs give results which are necessary for, but not sufficient to prove, a given modeled mechanism.

The impact of alkaline solutions (pH = 13.2) on the clay mineralogy of the Callovo-Oxfordian formation hosting the French underground laboratory for nuclear waste disposal investigation (Meuse-Haute Marne site) has been studied experimentally. Initially, each of the four samples selected as representative of the mineralogical transition in this Callovo-Oxfordian formation consists of a mixture of three main clay phases: discrete illite, discrete smectite and a randomly interstratified mixed-layered mineral (MLM) containing ∼65% of non-expandable layers. Clay separates were altered in batch reactors at 60°C using high solution:solid ratios. The mineralogy of this clay fraction and solution chemistry were monitored as a function of reaction time. In addition, the interactions between organic matter and clay particles were investigated using scanning transmission X-ray microscopy (STXM).

The clay mineralogy is little affected even though the pH is still high after 1 y reaction time. The only significant mineralogical evolution is the partial dissolution of the discrete smectite component leading to the formation of a new randomly interstratified illite-expandable MLM. Additional mineralogical transformations lead, for one sample, to the dissolution of micro-crystalline quartz and, for another sample, to the crystallization of a tobermorite-like phase. The low reactivity of clay minerals may be attributed to the presence of organic matter in the samples. In their initial state, all outer surfaces of clay particles are indeed covered with organic matter. After 1 y reaction time, STXM studies showed the basal surfaces of clay particles to be devoid of organic matter, but their edges, which are the most reactive sites, were still protected.

The ability to remove K rapidly with a solution containing sodium tetraphenylborate (NaTPB) from the interlayers of naturally-occurring phlogopite using a microwave-assisted technique has been examined. Samples were equilibrated with a 1.0 N sodium chloride (NaCl) – 0.2 N NaTPB – 0.01 M disodium ethylenediaminetetraacetic acid (EDTA) solution at 60, 80 and 100°C under both conventional and microwave-assisted heating methods and for periods of time ranging from 1 to 3 h. The samples also underwent treatments of either continuous time periods or for successive treatments of 1 h with a washing step between each treatment.

Following sample treatment, the expansion of the c-axis value (d001) from 10.0 to 12.2 Å indicated the presence of hydrated Na ions in the phlogopite structure. Under most treatment conditions the 10.0 Å peak remained even after treatment due to incomplete K removal. Chemical analysis and X-ray diffraction (XRD) revealed that samples heated using microwave radiation exchanged their interlayer K for Na much more rapidly than under conventional heating for all treatment times and temperatures. The successive treatments also degraded the mica more rapidly than the continuous treatments. The greatest amount of K (95%) was removed when the mica was treated three times for 1 h at 60°C. The results suggest that successive treatments of phlogopite mica heated under microwave radiation will rapidly remove K from the mica. Decreasing the amount of time required to prepare K-depleted phlogopite micas will make these materials more appealing as ion exchangers for separation of Cs from nuclear wastes.

We investigated the sorption of Ni to gibbsite of two different surface areas at pH 7.5, in the presence and absence of citrate, over a time period of 180 days. Extended X-ray absorption fine-structure spectroscopy was employed to elucidate the sorption mechanisms at the molecular level. In agreement with former results, Ni-Al layered double hydroxide (LDH) formed in the presence of gibbsite of low surface area. However, gibbsite of high surface area suppressed the formation of the surface precipitate. Instead, two Al atoms neighboring Ni at distances of 2.95–2.98 Å indicated formation of an inner-sphere sorption complex, where each NiO6-octahedron shares edges with two AlO6-octahedra. Focused multiple scattering arising from Al atoms at a distance of 6 Å suggest that sorbed Ni(OH)2(OH2)4 monomers epitaxially extend the hexagonal arrangement of Al atoms in gibbsite. Only after 30 days or more was a small amount of LDH formed. The presence of citrate prevented the formation of LDH, while maintaining the formation of inner-sphere sorption complexes.

Cronstedtite from Lostwithiel, Cornwall, England, in which two polytypic groups (A and C) are present within the same crystal, has been investigated using various techniques to reveal the distribution of the two groups and the relationship between polytypic structure and chemical composition. X-ray precession photographs from cleaved fragments of pyramidal crystals revealed the variable proportions of the two groups from the top to the base. Near the top, the crystal consists entirely of group C, with 1T as the dominant polytype. Near the base, both groups A and C are present. Back-scattered electron images from cross-sections parallel to the pyramidal axis showed mosaic contrast near the base, suggesting that two compositionally-different domains of several tens of microns in size are present, whereas the contrast was uniform near the top. Electron microprobe chemical analysis indicated the compositions $\left({\text{Fe}}_{2.31}^{2+}{\text{Fe}}_{0.69}^{3+}\right)\left({\text{Si}}_{1.31}{\text{Fe}}_{0.69}^{3+}\right){\text{O}}_5{\left(\text{OH}\right)}_4$ and $\left({\text{Fe}}_{2.16}^{2+}{\text{Fe}}_{0.84}^{3+}\right)\left({\text{Si}}_{1.16}{\text{Fe}}_{0.84}^{3+}\right){\text{O}}_5{\left(\text{OH}\right)}_4$. Electron back-scattered patterns (EBSPs) confirmed that the domain with Si-rich composition belongs to group C and that with Si-poor composition to group A. This is the first evidence that specific chemical compositions are related to the polytypic structures in cronstedtite. Transmission electron microscopy revealed that intergrowth of groups A and C at the monolayer level is also present as stacking disorder in both domains near the base, whereas such intergrowth was not observed in the region near the top.