Seven kaolins from Georgia (southeastern U.S.A.), ranging from high to low commercial grade, were characterized by X-ray powder diffraction and chemical techniques to establish that the variation in quality was caused by impurities. The Ca and Cs cation-exchange capacities (CEC) varied from 2.67 to 8.17 and from 3.29 to 8.77 meq/100g, respectively. Selective dissolution and correlation analyses strongly indicated that expandable 2:1 minerals, particularly smectite (1.2-5.9%), were responsible for most of the observed variations in Ca CEC (r = 0.85*). The external surface CEC of kaolinite ranged from 0 to 1 meq/ 100 g. The positive significant correlation (r = 0.90**) between the Ca CEC and the K-mica content (03.9%) suggested that Ca CEC may be related to the degree of mica weathering through an expandable mineral stage.

The Cs-retention capacity (0.19–1.14 meq/100 g) was closely related to Cs-measured vermiculite content (r = 0.80*), and this content plus specific surface (R = 0.93**) or mica content (R = 0.86*). The Cs retention appeared to be primarily related to the presence of interlayer wedges at mica/vermiculite XY interfaces.

The charge density distribution among different classes of a series of reduced charge mont-morillonites is heterogeneous as in the parent Camp Berteau clay. In addition, charge reduction proceeds inhomogeneously. Up to 20% differences in charge density can be accounted for by aikyl chains extending at the edges of the clay particle. A realistic charge density-cation-exchange capacity relationship for hec-torite, Otay montmorillonite, and a series of reduced charge montmorillonites of Camp Berteau is obtained by accounting for the influence of particle radius and for the extent of alkyl chains lying outside the clay layers in the charge density calculations.

Sequential cation-exchange capacity (CEC) measurements were obtained from standard clays using a mechanized, variable-rate leaching device. The device consists of a motorized screwjack and as many as 24 leaching tubes coupled to 60-ml plastic syringes. Controlled withdrawal of the syringe plungers produces a vacuum that permits samples in the leaching tubes to be extracted at a uniform rate. A single, 8-hr leaching of clays with 35 ml of salt solution was found to be comparable to multiple saturations or displacements using a centrifuge. CECs consistent with published values were obtained for reference 2:1 clay minerals using both acetate and chloride salts of Na, Ca, and Mg. Potassium-exchange capacities were also successfully measured following in situ thermal treatment of samples in the leaching tubes. Variations in measured CECs for kaolin-group minerals due to salt intercalation were minimized by using chloride rather than acetate salts and by washing with a dilute aqueous solution of the saturating cation following initial saturation. The mechanical extractor significantly reduced the effort required to perform conventional CEC determinations without sacrificing analytical precision.

A mixed-layer kaolinite/smectite (K/S) containing trace amounts of quartz, discrete kaolinite, goethite-hematite, and calcite was hydrothermally reacted with deionized water at 150°, 200°, and 250°C for 1 to 12 months. The starting K/S contained 50% smectite consisting of 15% low-charge and 35% high-charge layers. The X-ray powder diffraction and chemical analyses of the reacted products indicated a progressive reaction from high-charge to low-charge smectite as a function of time and temperature. The reaction reached completion after 4 months at 250°C, at which point high-charge smectite layers entirely reacted to low-charge smectite layers, the latter maintaining a constant proportion of about 90% for longer run durations. For long reaction times, discrete kaolinite totally reacted, whereas quartz showed only partial dissolution and iron oxides remained stable. Thus, the reaction of high-charge to low-charge smectite layers may be expressed as: high-charge smectite + kaolinite (both interstratified and discrete component) + quartz → low-charge smectite.

A program of simultaneous linear equations has been developed to calculate component proportions and/or component property values for mineral mixtures in soil clays and sediments. The analysis is based on quantitatively measured chemical and physical properties of samples and involves (1) qualitative identification of the mineral components in the mixture by any appropriate means; (2) quantitative measure of the sample property values selected for use in the program; (3) estimation of the proportion of each component in the mixture by a technique such as X-ray powder diffraction; (4) assignment of limits to component property ranges; (5) selection of one of four available calculation options and application of the simultaneous linear-equations program; (6) examination of the residuals of the analysis and, if appropriate, adjustment of the initial estimates for component proportions or property ranges and then repeating step 5; and (7) verification of the final component proportions by comparison with information from step 1. Completeness and/or accuracy of the final results for component proportions may be checked by the closeness of approach to 1.0 for the sum of the component proportions. The method requires that, at minimum, the number of properties measured must equal the number of components in the samples being analyzed and that the minimum number of samples must equal the number of properties measured.

Using the clay fractions of 15 Pennsylvania soils containing kaolinite, illite, smectite, vermiculite, chlorite, interstratified vermiculite/chlorite, quartz, and noncrystalline material, and measuring methylene blue cation-exchange capacity, the amount of Ca displaced by Mg from a Ca-saturated clay, the amount of K displaced by NH4 from a K-saturated clay heated to 110°C, % K2O, % SiO2, % MgO, and weight loss at 110°–300°C and 300°–950°C, the adjustment of property values was found to have the lowest residual value and the most consistent results. The source of analytical errors was also located by examination of residual tables. Samples that were similar in composition gave more reliable component proportions.

The cation-exchange capacity (CEC) of Na-Al- and Ca-Al-montmorillonite after neutralization with NaOH or Ca(OH)2 was studied at three Al levels: 10, 25, and 50% of the CEC. Hydroxy-Al polymers were effective in reducing the CEC of Na-montmorillonite (by more than 46%), the exact effectiveness being dependent on the hydroxy-Al content. The hydroxy-Al polymers were less effective in reducing the CEC of Ca-montmorillonite (less than 26%). The CEC reduction was equal to or larger than the amount of the untitrated Al. The electrostatic charges of the clay which were blocked by the hydroxy-Al polymers were compensated for by both the positive charge of the hydroxy-Al polymers and the trapped cations on the clay surfaces. These cations remained on the clay even after extensive washing with 0.1 M KCl.

The interaction between N-methyl 8-hydroxy quinoline methyl sulfate, a drug that absorbs erymathogenic near-ultraviolet radiation, and smectite was studied by X-ray powder diffraction (XRD) and adsorption and desorption techniques. From the adsorption studies, (1) the amount of the drug adsorbed by Na-smectite increased with the pH of the solution to pH 6.5 and then decreased as the pH was further increased; (2) the maximum amount adsorbed at pH 6.5 was 102 meq/100 g of clay; and (3) the maximum amount of drug adsorbed, according to the adsorption isotherms at pH 4, was close to the cation-exchange capacity of the smectite (80 meq/100 g). The XRD studies showed that the drug molecules were adsorbed in the interlayer space of smectite and that cation exchange was the chief mechanism responsible for these interactions. The results of the adsorption-desorption cycles of the drug by smectite showed that this clay is a good support for this compound. In addition, an alternative method was developed to obtain the intercalation compound to avoid the standard method of exchange by impregnation. The method consisted of grinding a mixture of the drug with the clay. The characteristics of the complex thus formed were similar to those of the complex formed by exchange at pH 4 to 7.

To gain insight into the pharmacological properties of the intercalation compound studied, its capacity for absorption of visible and near-ultraviolet light was investigated. The diffuse reflectance spectrum of the complex showed intense absorption bands, absent or weak in the spectra of the pure drug or the untreated clay, at 250, 290, and ~390 nm.

Published chemical data for suites of mixed-layer minerals from diagenetic sedimentary rocks, hydrothermally altered tufts, and a metasomatic bentonite bed indicate that the layer charge and composition of the different components of illite/smectite (I/S) differ from one geological environment to another. It appears that the composition of the elemental smectite and illite layers in the I/S is more or less constant for samples within each geologic setting. In the examples considered, the smectite layers are predominantly montmorillonitic in character (i.e., the charge is in the octahedral site), whereas the illite layers show different types of charge sites, depending upon the suite studied. Illite layers appear to have about the same charge in all three suites studied, slightly more than 0.7 per O10(OH)2 unit, whereas the smectite layers in the different suites range in charge from about 0.3 to 0.7 per O10(OH)2 unit. Cation-exchange capacities reflect these differences in charge, although not ideally. The differences in the composition of the component layers in each geologic suite of mixed-layer clays are probably due either to differences in the bulk chemistry of the rocks in the different suites or to differences in intensive variables, such as temperature and pressure, of the regime under which they have formed.

Reference smectites were examined to determine relationships between Li uptake, cation-exchange capacity (CEC), and octahedral layer charge after Li saturation and heating at 250°C (Hofmann-Klemen effect). Direct measurements of exchangeable Li after heating led to overestimates of charge reduction due to entrapment of Li in collapsed interlayers. Expansion of interlayers by sequential washings with 1 N MgCl2, 0.01 N MgCl2, and ethanol and subsequent determinations of exchangeable Mg provided accurate measurements of reduced charge. The CEC reductions observed in dioctahedral samples as a result of Li saturation and heating equaled octahedral charge values derived from published mineral formulae, and interlayer charge estimates obtained by alkylammonium exchange confirmed that measured CEC reductions were a consequence of uniform decreases in octahedral layer charge.

Dioctahedral specimens retained 1 to 10 meq/100 g of non-exchangeable Li in excess of CEC reduction and were acidified in direct proportion to their total Fe contents, apparently as a result of the deprotonation of structural hydroxyl groups. Mild acid treatment reprotonated these hydroxyl groups, released excess Li, and resulted in total Li contents comparable to measured CEC reductions. Heating (250°C) Mg-saturated hectorite induced a loss of octahedral Li, acidification, and a reduction of CEC, indicating that Mg had partially replaced octahedral Li. These results suggest that octahedral Li is mobile at low temperatures and that cation movement into or out of the octahedral sheet is favored if the layer charge is reduced.

Infrared (IR) spectra in the fundamental and near-IR regions were obtained for Na-saturated Wyoming montmorillonite and reduced-charge Na/Li-saturated Wyoming montmorillonites hydrated under water vapor at 50% RH and dehydrated under vacuum. For the Na-montmorillonite, changes in the intensities of the structural OH-bending modes, particularly that of the MgAlOH group, were observed as the clay was dehydrated. This result was interpreted as evidence that exchangeable Na ions lose solvation water and settle into the ditrigonal cavities on the clay surface as it becomes desiccated. For the Na/Li-montmorillonites, the structural OH-bending modes also decreased in IR intensity because of Li+ migration into the octahedral sheet. The fundamental IR spectra of D2O adsorbed by the montmorillonites showed characteristic absorptions at 2685, 2510, 2400, and 1205 cm-1 that decreased in intensity proportionally to the cation-exchange capacity. This result, along with corroborating data from X-ray powder diffractograms and from near-IR diffuse reflectance spectra of H2O adsorbed by the clays, suggest that the exchangeable cations on Na-montmorillonite dissociated from the clay surface as it hydrated and played a significant role in organizing the structure of adsorbed water at low water contents.

Dealumination of vermiculite was carried out using (NH4)2SiF6 solutions. The dealuminated products were studied by high-resolution solid state 29Si and 27Al nuclear magnetic resonance. A decrease in the cation-exchange capacity (CEC) resulted from the partial removal of Al from the tetrahedral layer, which decreased the framework negative charge, and from the partial replacement of Mg by Al in the octahedral layer, which increased its positive charge contribution. The lowest CEC was obtained by swelling the structure with butyl-ammonium prior to the reaction with (NH4)2SiF6. Thus, CECs in the range observed for beidellite were measured; however, the lowest (Al/Si)IV ratio was still more than twice as high as in beidellite. In addition, the dealumination reaction yielded noncrystalline silica as a by-product.

In contact with a solution of Al hydroxypolymer (Al13), the dealuminated vermiculite showed no 18-Å reflection characteristic of Al13-intercalated smectite; instead it showed an ill-defined interstratification. For some samples, however, a significant increase in the specific surface area (as much as 230 m2/g) was observed, suggesting that an intercalation of Al moieties did occur. The 27Al resonance spectra of the intercalated structure showed at least two components in octahedral coordination. On thermal activation, a resonance line attributable to pentacoordinated Al was observed.

Na-beidellite, a member of the smectite group, was grown hydrothermally from a gel of composition 0.35Na2O·2.35Al2O3·7.3SiO2 in NaOH solutions at a pH between 7.5 and 13.5, a pressure of 1 kbar, and a temperature of 350°C. The synthetic Na-beidellite was characterized by means of scanning electron microscopy, X-ray powder diffraction, infrared spectroscopy, electron microprobe, inductively coupled plasma-atomic emission spectroscopy, and thermogravimetric analysis. The unit-cell parameters of the orthorhombic cell are: a = 5.18, b = 8.96, and c = 12.54 Å. The cation-exchange capacity was determined to be 70 meq/100 g. A maximum of 40 wt. % water was present and reversibly lost by heating to about 55°C. The loss of water caused a decrease of the basal spacing to 9.98 Å. At temperatures ≥600°C, the Na-beidellite started to dehydroxylate, reaching its maximum in the range 600°–630°C. At 1100°C the remaining solid recrystallized to Al6Si2O13 (mullite) and SiO2 (cristobalite).

Weathering of a copper stratiform deposit (schist) at Salobo, Brazil, has produced two distinct Cu-bearing minerals from a biotite parent: vermiculite and a manganese oxide containing as much as 13% and 25% CuO, respectively. Manganiferous products were formed as the result of an interhorizon transfer of solutions through a fissure system. Thus, the structural orientation of the schists was a major factor in controlling the supergene concentration of Cu. The Cu-vermiculite formed by the weathering of Fe-biotite, although the unweathered biotites in the parent rocks were found to contain no copper, suggesting that Cu was supplied by weathering solutions. X-ray powder diffraction (XRD) and cationexchange capacity data for the Cu-vermiculite differ from those of typical Mg-vermiculite and are similar to those of hydroxy- Al-vermiculite. A comparison of the XRD pattern of the Cu-vermiculite with that of a Cu-free vermiculite indicates that Cu atoms are located in interlayer sites. Cu probably occurs in a brucite-like layer. The position and structure of the Cu K-absorption spectrum suggest that the Cu is divalent and exists in 6-fold coordination.

The instability of palygorskite and sepiolite under soil conditions was investigated to determine if these fibrous minerals transform directly to smectite under laboratory conditions. The treatment of 100 mg (0.12 mmole) of palygorskite with 1 mmole of NaOH solution (17 ml) at 150°C for 24 hr yielded a smectite. Analcime and smectite were formed when ≥ 3 mmole of NaOH was used. The addition of ≤ 6 mmole NaOH to sepiolite destroyed it gradually. On addition of ≥ 8 mmole NaOH, sepiolite altered to an X-ray amorphous material. In the presence of Al and Si, however, it transformed to smectite and analcime. Transmission electron microscopy, cation-exchange capacity, and X-ray powder diffraction studies of the products suggest that alteration wa. (1) via solution, o. (2) by a structural reorganization wherein the basic 2:1 silicate structural units were unchanged.

A cation-exchange capacity (CEC) method based on ion-sieving properties was developed for the quantitative determination of clinoptilolite in soils. In this method, both zeolitic and non-zeolitic exchange sites in the soil sample are saturated with Na+. The CEC of the non-zeolitic exchange sites is determined by replacing the Na− in these sites with tert-butylammonium ions. The tert-butylammonium ion cannot be exchanged into the zeolitic exchange sites because it is too large to pass through the channels in the clinoptilolite structure. The sample is next washed with NH4OAc to replace the Na+ in the zeolitic exchange sites. The amount of soil zeolite is then estimated by comparing the CEC of zeolitic exchange sites to the total zeolite CEC (175 meq/100 g for pure clinoptilolite). Prior to the CEC analyses, carbonates and organic matter must be removed to minimize interference with the exchange process. A high correlation (r2 = .96) was observed between the abundance of clinoptilolite estimated using the CEC method and the abundance estimated by semiquantitative X-ray powder diffraction analysis.

The CEC procedure was used to quantify clinoptilolite in an Aridic Calciustoll soil from south Texas. About 2–5% clinoptilolite occurs in the A and B horizons, and concentrations progressively increase with soil depth to as much as 20% in the CBk2 horizon.

A white calcium bentonite (CaB) from the Kütahya region, Turkey, contains 35 wt. % opal-CT and 65 wt. 9c Ca-rich montmorillonite (CaM). Samples were heated at various temperatures between 100–1300°C for 2 h. Thermal gravimetric (TG), derivative thermal gravimetric (DTG), and differential thermal analysis (DTA) curves were determined. Adsorption and desorption of N2 at liquid N2 temperature for each heat-treated sample was determined. X-ray diffraction (XRD) and cation-exchange capacity (CEC) data were obtained. The change in the <d(001) value and the deformation of the crystal structure of CaM depend on temperature. Deformation is defined here as changes of the clay by dehydration, dehydroxylation, recrystallization, shrinkage, fracture, etc. The activation energies related to the dehydration and dehydroxylation of CaB calculated from the thermogravimetric data are 33 and 59 kJ mol−1, respectively. The average deformation enthalpies, in the respective temperature intervals between 200–700°C and 700–900°C, were estimated to be 25 and 205 kJ mol−1 using CEC data and an approach developed in this study. The specific surface area (S) and the specific micropore-mesopore volume (V) calculated from the adsorption and desorption data, respectively, show a “zig zag” variation with increasing temperature to 700°C, but decrease rapidly above this temperature. The S and V values were 43 m2 g−1 and 0.107 cm3 g−1, respectively, for untreated bentonite. They reach a maximum at 500°C and are 89 m2 g−1 and 0.149 cm3 g−1 respectively. The XRD data clearly show that, at 500°C, where the irreversible dehydration is completed without any change in the crystal structure, the porosity of CaM reaches its maximum.