Experimental cation exchange capacities (CEC) of kaolinites were determined and compared to theoretical calculations of CEC. The comparison reveals that the exchangeable cations occur mostly on the edges and on the basal (OH) surfaces of the mineral. It also shows that permanent negative charge from isomorphous substitution of Al3+ for Si4+ is insignificant. The CEC of kaolinite strongly depends on the particle size (both thickness and diameter in the (00l plane) and pH value. Particle size is more important than crystallinity in affecting kaolinite CEC. This study shows that the hydroxyls on the exposed basal surfaces may be ionizable in aqueous solutions. The amount of negative charge on the edges and the exposed basal hydroxyls depends on pH and other ion concentrations. A higher pH value gives rise to more negative charges, which lead to a higher CEC value. This study indicates that charge from broken edges and exposed OH planes rather than charge from Al/Si substitution determines the kaolinite CEC, even at zero point charge. A high CEC in some kaolinites is found to be due to smectite layers on the surface of the kaolinite crystals.

Structural Fe3+ in kaolinites and dickites covering a broad range of disorder was investigated using electron paramagnetic resonance (EPR) spectroscopy at both the X and Q-band frequencies. A procedure based on a numerical diagonalization of the spin Hamiltonian was used to accurately determine the second and fourth-order fine-structure parameters. A least-squares fitting method was also developed to model the EPR spectra of Fe3+ ions in disordered local environments, including multimodal site-to-site distributions. Satisfactory fits between calculated and observed X and Q-band spectra were obtained regardless of the stacking order of the samples.

In well-ordered kaolinite, Fe3+ ions are equally substituted in sites of axial symmetry (Fe(II)sites, namely Fe(II)a and Fe(II)b) which were determined to be the two non-equivalent Al1 and Al2 sites of the kaolinite structure. In dickite, Fe3+ ions were also found to be equally substituted for Al3+ in the two non-equivalent Al sites of the dickite structure. In poorly ordered kaolinites, the distribution of the fine-structure parameters indicates that Fe3+ ions are distributed between Fe(II) sites and other sites with the symmetry of the dickite sites.

Hence, when stacking disorder prevails over local perturbations of the structure, the near isotropic resonance owing to Fe3+ ions in rhombically distorted sites (Fe(I) sites) is a diagnostic feature for the occurrence of C-layers in the kaolinite structure, where C refers to a specific distribution of vacant octahedral sites in successive layers.

Many soils developed from volcanic rocks in southern Brazil exhibit spontaneous magnetization caused by the presence of fine-grained maghemite (γ-Fe2O3), but few attempts were made to quantify or characterize this important soil component. To that end, clays were separated from freely drained soils derived from acid (≥63% SiO2), intermediate (54–62% SiO2), and basic (≤53% SiO2) igneous rocks produced by the Paraná flood volcanism. The sample set included soils with a wide range of pedogenic development on different landscape positions. The Fe oxide mineralogy of these samples was examined by using a combination of selective dissolution, magnetic susceptibility, and X-ray diffraction (XRD) techniques. Hematite and maghemite were the primary Fe oxides in mature soils (Oxisols, Ultisols, and Alfisols) developed from basic rocks; whereas goethite was dominant in all other soils, especially those formed from acid-intermediate rocks. The association of maghemite with basic rock materials suggests that it was primarily formed by oxidation of lithogenic magnetite. A strong, positive correlation (R2 = 0.89) was obtained between mass specific magnetic susceptibility (χ) of the clay fractions and maghemite contents estimated by XRD. Either method could be used for quantitative analyses, but χ was more sensitive than XRD at low maghemite concentrations (<2 wt. %). The clay-sized maghem-ites were superparamagnetic with an estimated value for the mass specific magnetic susceptibility (χlf) value of 91,000 × 10−8 m3 kg−1 and frequency dependent variations of 10–15%. The maghemites also had low unit cell constants, which, if attributed entirely to replacement of Fe by Al, would correlate with Al substitutions in the range of 5–16 mole %. Selective dissolution of the soil maghemites was achieved by treatment of Fe oxide concentrates with 1.8 M H2SO4 at 75°C for 2 h.

Otay-type waxy bentonites of San Diego County are illite-smectite (I-S) with 85% dioctahedral smectite mixed with dioctahedral illite showing a Reichweite of 0. Primary or secondary waxy bentonite exposures are found in all Eocene and Oligocene formations of southwest San Diego County and western Baja California north of Ensenada. Primary waxy bentonites formed when hot volcanic ash fell into quiet marine or brackish coastal water. The transformation from glass to bentonite occurred within hours or days but consolidation of the bentonite into its waxy consistency took longer. Primary waxy bentonite consists of 95 wt% I-S with the remainder consisting of volcanic glass shards, sanidine fourling twins, hexagonal biotite crystals and amorphous manganese oxides and hydroxides. Secondary waxy bentonite is primary waxy bentonite that was mixed with nonvolcanic detritus either before consolidation or after consolidation and subsequent erosion. The hydrophobic character of primary waxy bentonite allows it to reflect, accurately, the chemistry and petrology of the original volcanic material. Chemical analysis of primary waxy bentonites shows that the original lava was subduction-related and exhibited petrologic variations nearly identical to those of the modern Cascades of the northern Pacific coast of the lower United States. Primary and secondary waxy bentonites as well as smectites derived from the weathering of volcanic ash that fell outside the waxy bentonite-producing environments are the previously unrecognized products of extensive Eocene and Oligocene subduction-related volcanic activity. Baja California exposures of waxy bentonite demonstrate pre-Pliocene subduction tectonics that gave way to rifting tectonics.

High-resolution transmission electron microscopy (HRTEM) examinations have indicated that three types of surface layers may exist in natural kaolinite crystals. Type 1 has the expected 7-Å surface layer as terminations. Type 2 has one 10-Å pyrophyllite-like (or low-charge beidellite-like) layer as the surface layer on one side of a kaolinite particle (i.e., the layer sequence is TOTOTO … TOTOTOT, where T stands for tetrahedral sheet, O for octahedral sheet). Some industrial-grade highly-ordered kaolinites have such a 10-Å 2:1 surface layer on one side of the crystal. The spacing between the 10-Å layer and the adjacent 7-Å layer is not expandable. Type 3 kaolinite has one or several 10-Å collapsed smectite-like layers at one or both sides of a stack, i.e., (TOT)TOTO … TOTOTOT(TOT), forming a special kind of kaolinite-smectite interstratification. This type has only been recognized in some poorly-ordered kaolinites. The surface smectite layer(s) contribute to higher cation exchange capacity (CEC) values. These 10-Å surface layers were not detectable by X-ray diffraction (XRD). HRTEM and electron diffraction examination also revealed the structural features of individual kaolinite crystals. All kaolinites (from various origins and sources) studied show C-face-centering Of non-hydrogen atoms. Defects within the layer structure are common in both well-ordered kaolinite and poorly-ordered kaolinite.

X-ray diffraction (XRD) profile analysis of eight synthetic hematite samples was performed to identify the best parameters for determining the apparent mean crystallite dimension (D) and, consequently, surface area, The samples are comparable to soil hematite with respect to crystallinity. The procedure included: a) deconvolution of the XRD peaks to Gauss and Cauchy components and subtraction of the instrumental profile, b) determination of D from full-width at half-maximum, integral breadth, and integral breadth measurements of the Cauchy component, and c) comparison of deduced surface areas with those obtained by the N2-BET adsorption method. As expected, D values are strongly influenced by the broadening parameters. An appropriate selection of peaks is required to obtain size values along the crystallographic axes a (hkl: 110,300) and c (hkl: 104, 116) and to calculate reliable surface areas. Using the Cauchy component of the above peaks, the calculated surface areas compared well with those measured by the N2-BET adsorption method.

Clinoptilolite and mordenite occur as diagenetic products of medium-grained, moderately welded and poorly sorted pyroclastic flows belonging to the Tertiary calc-alkaline volcanism of Sardinia. Both clinoptilolite and mordenite occur within pyroclastic flows of the same stratigraphic unit. Mordenite frequently occurs in the late volcanic sequences from Anglona area (northern Sardinia). Textural features indicate that zeolites are products of glass alteration. Thin sections show either complete alteration of glassy shards by clinoptilolite and mordenite or unaltered shards with clinoptilolite or mordenite confined to the cineritic matrix. During the zeolitization process, interacting fluids were important in the mobilization and distribution of alkali elements. The compositional variations of clinoptilolite and mordenite within a single sample showed trends that suggest steps in a continuous process probably evolving towards equilibrium conditions.

The sorption of Cd, Cu, Pb, and Zn ions by Na-rich bentonite, Al and Zr-pillared Na-rich bentonite (Al-MX80, Zr-MX80), the uncalcined hydroxy-intercalated precursors (HAl, HZr-MX80), and commercial Al-pillared bentonite EXM 534 was investigated. Experiments were conducted in ultrapure water and artificial leachate with varying pH. The experiments were performed over periods to 30 wk. Sorption characteristics were described with one and two-site Langmuir isotherms. The non-exchangeable quantities of heavy metals were determined by fusion of the sorbents after ion exchange with ammonium acetate.

The sorption of Cd, Cu, Pb, and Zn by bentonite was dominated by cation exchange. In artificial leachate, the sorption was reduced due to competition with alkali and alkaline-earth cations. The sorption of Cu, Zn, and Pb at pH 4.9 and Cd at pH 6.9 by Al and Zr-hydroxy-intercalated and pillared MX80 was governed also by cation exchange. In contrast, the sorbed quantities of Zn at pH 6.9 exceeded the cation exchange capacity (CEC) of HAl, HZr, Al, Zr-MX80, and EXM 534 and were partially non-exchangeable. The increase of the sorption of Zn with pH and its independence of the ionic strength of the solution at neutral pH suggest a complexation of Zn ions to surface hydroxyl groups of the intercalated Al and Zr-polyhydroxo cations and pillars. This complexation is the dominating sorption mechanism. Removal of dissolved Zn from solution with time is attributed to surface precipitation. Al-hydroxy and pillared bentonites are considered potential sorbents of Zn ions from neutral pH aqueous solutions, such as waste waters and leachates.

The oxygen and hydrogen isotope compositions of volcanic ash layers from coastal outcrops of the Miocene Monterey Formation elucidate the progressive burial diagenesis of glass to bentonite and metabentonite. Volcanic glass that texturally appears unaltered is found to have δl8O and δD values that are significantly higher than fresh volcanic glasses. The positive shift in δ18O and δD values is proportional to the amount of hydration and chemical alteration of the glass samples. Initial hydration of the glass results in the exchange of Na for H; later hydration results in the loss of K and Fe in exchange for H and Na. The δ18O values of the most hydrated glass, and clay minerals from bentonite and metabentonite layers are approximately in equilibrium with slightly modified seawater. The δD values of the hydrated glass, and clay minerals from bentonite and metabentonite layers, are significantly depleted in D relative to seawater and suggest meteoric exchange associated with tectonic uplift and erosion in the Pliocene and Pleistocene. Smectite from bentonite layers has δ18O and δD values similar to the most hydrated glass samples, suggesting similar glass-water and smectite-water fractionation factors. Kaolinite and mixed-layered illite-smectite (I-S) altered from smectite have lower δ18O and higher δD values than their precursor. The δ18O and δD of nonvolcanic siliceous mudstones from the Pt. Arguello oil field show an unusual decrease in δD with increasing burial depth that probably reflects the presence of organic hydrogen in the analyzed samples as well as possible D-depleted formation waters from detrital illite-water and hydrocarbon-water exchange.

The objective of this study was to investigate the influence of layer charge on the hydration of Mg-saturated expandable 2:1 phyllosilicates. Water retained by 12 Mg-saturated clays at 54% relative humidity was quantified gravimetrically. X-ray diffraction and total chemical analysis were used to determine the hydratable surface area (447–759 m2 g−1) and layer charge [0.327–0.754 electrons per formula unit (e f.u.−1)] of each sample. Water retained by the clays increased with both hydratable surface area and layer charge of the clays. However, the increase in H2O content with layer charge occurred only on external surfaces of the clays. This result suggests that the H2O on external surfaces is localized around the cation/charge sites rather than forming multi-layers as was suggested previously. A model is proposed for the hydration of expandable 2:1 phyllosilicates. The model assumes that interlayer volume controls interlayer hydration and that the number of cation/charge sites on external surfaces controls hydration of external surfaces.

Mn-substituted goethite was synthesized and the interaction between arsenite (As(III)) and Mn-substituted goethite was investigated by both solution chemistry and X-ray adsorption near edge structure (XANES) spectroscopy. Results indicate that the oxidation of As(III) is favored by Mn-substituted goethite. This reaction was more sensitive to temperature than to pH. Different reaction mechanisms may account for As(III) oxidation. Since As(III) is more mobile and toxic than As(V), the oxidation reaction of As(III) with Mn-substituted goethite may decrease arsenic toxicity under some conditions.

The effects of neodymium (Nd) on the transformation of ferrihydrite to iron oxides was studied. The possible isomorphous substitution of Nd3+ for Fe3+ in iron oxides was examined also. Nd was used as an inactive substitute of trivalent radioactive actinide elements. Hydrolysis of ferric nitrate solution containing 0–30 mole % of Nd formed Nd, Fe-rich ferrihydrite as initial precipitates, which were poorly crystalline. Aging of the Nd-containing ferrihydrite in 0.3 M OH− at 40°C and at pH 9.2 at 70°C formed Nd-free goethite and Nd-substituted hematite. The abundance of these crystalline phases was related to Nd in the parent solutions. Phase abundance, unit-cell parameters, and peak width were estimated by use of the Rietveld method.

Synthetic goethites studied by high-resolution thermogravimetry (HRTGA) show variability in surface characteristics and structural stability as a function of aging conditions. Goethites were synthesized at either pH 6 or 11, at temperatures of 40 or 70°C, and in the presence or absence of sorbed Mn or Pb. Data from HRTGA analysis revealed at least four distinct weight-loss events near goethite dehydroxylation that relate to 1) three events involving the evolution of water associated with surface Fe-O functional groups and 2) bulk dehydroxylation of goethite during transformation to hematite. The relative mass of evolved surface and bulk structural water was related to the predominant particle morphology as determined by transmission electron microscopy (TEM). Differentiation of surface and bulk decomposition reactions allowed the identification of bulk structural dehydroxylation. Goethite crystallin-ity, estimated by the bulk dehydroxylation temperature, appeared to depend on the kinetics of crystallization. This trend was most evident for systems aged at pH 11 and 40°C. Greater concentrations of coprecipitated Mn or Pb dramatically improved goethite crystallinity as indicated by higher dehydroxylation temperatures and smaller widths of the (110) Bragg reflection. Comparison of bulk dehydroxylation temperatures for these samples to other preparations suggests that structural defects predominated over the effects of particle size and Mn/Pb substitution in determining goethite thermal stability. A conceptual model is proposed to account for the disparate dehydroxylation profiles displayed by goethites of varying crystallinity.

Monte Carlo simulations based on tested water-water, cation-water, and water-clay potential functions were applied to calculate radial distribution functions for O-O, O-H and H-H spatial correlations in the interlayer region of the two-layer hydrates of Na- and K-montmorillonite. The simulated radial distribution functions then were used to compute the total radial distribution function for interlayer water, a physical quantity that can be determined experimentally by H/D isotopic-difference neutron diffraction. The simulated total radial distribution functions were compared with that for bulk liquid water, and with a total radial distribution function determined experimentally for the two-layer hydrate of Na-montmorillonite by Powell et al. (1997). This comparison suggested that water molecules in the two-layer hydrate of montmorillonite have nearest-neighbor configurations which differ significantly from the tetrahedral ordering of nearest neighbors that characterizes bulk liquid water.

Two clay fractions of a Cambrian claystone from Estonia, consisting essentially of illite and 20% expandable illite-smectite, (I-S) were treated with C12 and C18 alkylammonium cations for K-exchange. Both the untreated and treated samples were dated by the K-Ar method. The treated clays lost several percent of their original K2O, with greater losses for longer-chain cations and for longer reaction time, in accordance with previously published studies. The dates of the treated clay fractions were 20–30 Ma lower than those of the untreated clays. The decrease in the dates suggests preferential opening of older, detrital clays. The K-Ar dates of the illite layers susceptible to K extraction by the various treatments were calculated by subtracting K2O and radiogenic 40Ar values of the consecutive step products, and they were plotted against the total % K2O removed, used as an indicator of the reaction progress. Extrapolation of the plot revealed a detrital (1550 Ma) and a diagenetic (380 Ma) age for the 2 illitic minerals present in the investigated shale sample. The inferred Devonian age of diagenesis of the Estonian clay corresponds to the period of massive dolomitization in the area. Both alteration processes can be related to a Devonian incursion of hot or alkaline fluids, which helps to explain the occurrence of 20% expandable I-S in claystones that have never been buried more than 1000 m.

Extrapolated K-Ar ages and K2O contents of the illitic minerals, estimated from the X-ray diffraction (XRD) data, were used to model the experimental data. A good agreement was reached when dilution effects (chlorite and expanded illite) were taken into account.

Clay mineralogical studies by X-ray diffraction performed on extracted <2-µm fractions do not always represent all clay mineral constituents present in the soil. In this work, transmission X-ray diffraction (TXRD) was applied to undisturbed microsamples of optically homogeneous mineral soil fabrics and features. These microsamples were isolated by microdrilling their periphery in soil thin sections, then removing them, and transferring them to glass capillaries for TXRD analysis. The usefulness of this technique for supplying in situ mineralogical information on identification, structure, and natural orientation of soil constituents was tested on mineral microfabrics and features of primary and secondary phyllosilicates. The study demonstrated that TXRD allowed detailed, representative interpretations of undisturbed mineral features and fabrics. In particular, this technique allowed us (1) to compare mineralogical compositions at selected microlocalities, (2) to study natural preferred orientations, and (3) to detect small amounts of minor mineral interstratification phases. In addition, complementary information on crystallography and crystal chemistry may be obtained by performing analytical transmission electron microscopy on the same microsample.

Vermiculite crystals from Santa Olalla, Spain, were first Na exchanged and then intercalated with monomethylammonium (= NH3(CH3)+, MMA) and dimethylammonium (= NH2(CH3)2+, DMA) molecules, respectively, by immersion in 1 M ammonium-chloride solutions at 65°C for 2–3 wk. MMA-and DMA-exchange with vermiculite resulted in crystals with near perfect three-dimensional stacking, suitable for single crystal X-ray diffraction analysis. Unit cell parameters are: a = 5.353(2) Å, b = 9.273(3) Å, c = 11.950(6) Å, and ß = 98.45(4)° for MMA-exchanged vermiculite and a = 5.351(2) Å, b = 9.268(4) Å, c = 12.423(8) Å, and ß = 98.33(5)° for DMA-exchanged vermiculite. Refinement results are R = 0.059 and wR = 0.073 (MMA-exchanged vermiculite) and R = 0.059 and wR = 0.064 (DMA-exchanged vermiculite). The results are based on structures which show substitutional disorder, and thus the presented models are derived from average structures.

There are two distinct sites for the MMA molecule in MMA-exchanged vermiculite. One crystallo-graphically unique MMA is oriented such that the N-C axis of the molecule is perpendicular to the basal oxygen plane, with the N ion offset from the center of the interlayer by 1.04 Å. The other MMA is located such that the N ion is at the center of the interlayer between adjacent 2:1 layers, presumably with the N-C axis of the molecule oriented parallel to the basal oxygen plane. This represents the first known occurrence of an organic molecule located exactly between the two adjacent 2:1 layers. Both sites are located between hexagonal cavities of adjacent layers. DMA molecules in DMA-exchanged vermiculite are located such that the N ion is offset from the central plane in the interlayer by 0.95 A. A static model is proposed with two orientations of DMA to produce a DMA “zigzag” orientation of molecules parallel to the (001) plane. The plane defined by the C-N-C atoms in the molecule is perpendicular to the (001) plane. An alternate model is more dynamic, and it involves the rotation of DMA molecules about one C-N axis.

Identical starting material was used in previous studies on tetramethylammonium (TMA)-exchanged vermiculite and tetramethylphosphonium (TMP)-exchanged vermiculite. The effect of onium-ion substitutions on the 2:1 layer shows that the tetrahedral rotation angle, α, is significantly smaller for MMA-and DMA-exchanged vermiculite vs. TMA and TMP-exchanged vermiculite. Tetrahedral and octahedral bond distances of the 2:1 layer of the TMA, TMP, MMA, and DMA-exchanged structures may be explained by the location of the organic cation relative to the basal oxygen atom plane and by the differences in the geometries of the organic molecule. Thus, the 2:1 layer is affected by the interlayer molecule, and the 2:1 layer is not a rigid substrate, but interacts significantly with the onium ions.

The residual kaolin deposits near Lastarria, South-Central Chile, were formed by weathering of subvolcanic quartz porphyry stocks, which intruded the metamorphic basement of the Coastal Cordillera. The clay fractions (<2 µm) consist mainly of poorly-ordered, very fine-grained kaolinite and lath-shaped illite (17–38 wt. %) with minor amounts of quartz, sanidine, and goethite. A sample from the top of the deposit contains major quantities of gibbsite morphologically indistinguishable from kaolinite flakes. The gibbsite-free clays contain 35.5–36.6 wt. % Al2O3, 0.4–2.6 wt. % Fe2O3, 1.3–3.9 wt. % K2O, and have low TiO2 concentrations (<0.02 wt. %). The absence of quartz veining, the abundance of melt inclusions, and the scarcity of secondary fluid inclusions in quartz phenocrysts from altered rocks imply a lack of significant hydrothermal activity in the quartz porphyries. The δ 18O and δD values of the kaolins indicate formation in a weathering environment at significantly higher annual mean air temperatures (∼12°C) than present mean temperatures of ∼9.4°C. Uplift of the region alone probably cannot account for the change in climate. The stable isotope composition of gibbsite is consistent with an origin of desilication of kaolinite at superficial temperatures. Various criteria proposed to distinguish supergene from hypogene kaolins are discussed.

Samples containing illite and illite-smectite, having different crystal shapes (plates, “barrels”, and filaments), were selected for sorption experiments with cesium. There is a positive correlation between total surface area and Cs-sorption capacity, but no correlation between total surface area and the distribution coefficient, Kd. Generally Kd increases with the edge surface area, although “hairy” (filamentous) illite does not fit this pattern, possibly because elongation of crystals along one axis reduces the number of specific sorption sites.

Jordanian natural kaolin and bentonite show good catalytic activity towards debutylating 2-tert-butylphenol, and varying debutylation vs. isomerization selectivity after acid activation. The resulting catalytic activity of these samples is dependent on the acid employed for activation; the samples treated with acetic acid showed relatively low conversions, whereas those treated with hydrochloric or phosphoric acid were found to be very active. Treatments with strong acids such as HCl have various effects on the activity of the samples depending on the concentration of the acid. For example, treatment with 1 M HCl gives the highest activity, whereas a treatment using 12 M HCl produced the lowest activity. The debutylation selectivity of the acid-activated samples is affected by the acid type and/or concentration. This selectivity ranges from 20 to 60%, whereas that of water-treated samples is between 46–82%.