Mössbauer spectra were obtained for five Ca-exchanged nontronites and one Ca-exchanged vermiculite as the 2-layer hydrates following dehydration at 200°C. Exchange of the samples with Ca2+ and subsequent dehydration resulted in the appearance of a shoulder at about −0.50 mm/s in the Mössbauer spectra of some of the samples. The appearance of these shoulders necessitated the inclusion of doublets with Mössbauer parameters corresponding to tetrahedrally-coordinated Fe3+ (IVFe3+) in the model used to fit the Mössbauer spectra. That the IVFe3+ sites detected in these samples were those in the nontronite structure was confirmed using samples whose IVFe3+ contents have been previously determined from chemical analysis. It appears that this sample preparation method allowed IVFe3+ contents to be determined to within 40%. On this basis, the IVFe3+ content appeared to be unrelated to the total Fe content for the samples studied.

Nineteen drill core samples of lower Dogger opalinum shale from wells drilled in connection with a tunnel project near Brugg, northern Switzerland, were investigated. The shale is a well known swelling rock that has caused problems in underground construction work. Swelling pressures determined under constant volume conditions to obtain maximum values were 0.7 to 2.2 N/mm2. The samples contained 37–59% clay-size material and about 35% quartz, 7–18% carbonate minerals, and about 5% feldspar, pyrite, and organic matter. In addition to kaolinite, illite, and chlorite, the clay-size fraction also contained mixed-layer illite/smectite with about 30% swelling layers. The specific surface area of the clay fraction was 135 m2/g. The specific surface charge of the clay (6.7 × 104 esu/cm2), the ion concentration in the pore fluid of the specimen after the swelling test (10−2 mmole/cm3), the valence of the ions in the double layer of the clay particles (+1), and the half distance between the clay plates in the specimen (8–15 Å) allowed the calculation of the swelling pressure for each sample according to the Gouy double layer theory.

The mean value of the calculated swelling pressures was found to be of the same order of magnitude as the measured values, indicating that the technique can be used where cylindrical or rectangular specimens are not available for direct measurement.

Hollow spherical particles of aluminosilicate having diameters of 80 to 100 Å and high electric charge were synthesized by heating solutions containing Si and Al concentrations of about 2 mM (Si/Al molar ratio = 1.0–1.2; pH = 9.0) at 95°–100°C for 7 days. Electron microscopy, X-ray powder diffraction, and infrared spectroscopy suggested that the walls of the spherical particles consisted of monolayer aluminosilicate, most probably having a 1:1 layer structure. Chemical analysis supported this supposition but indicated modifications as shown in the formula (Si1.85Alo0.62)IV(Al1.38)VI(OH)4.10O4.96Na0.62, compared with (Si2)lv(Al2)VI(OH)4O5 for an ideal 1:1 layer silicate. High-resolution 29Si and 27A1 nuclear magnetic resonance spectroscopy indicated the substitution of Al for Si in the tetrahedral sheet, the presence of A1IV and A1VI, and the presence of Si bonded through oxygen to three Al atoms and one H. A natural counterpart of the synthesized aluminosilicate may be a precursor of halloysites formed by weathering of volcanic ash and pumice and have a close structural relation with allophane and imogolite

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.

The Dolná Ves K-bentonite deposit is one of a few known economic accumulations of illite-smectite in the world. Several studies have been done on the illite-smectitic component isolated from the Dolná Ves K-bentonite, but there is a shortage of analytical data on the K-bentonite itself. The main goal of the present study was to perform mineralogical and physico-chemical characterizations of various technological types of K-bentonites from the Dolná Ves deposit to better understand the relationships between the various qualitative types and their properties. The type I (high-grade) K-bentonite contains 88–91 wt.% of illite-smectite. The type II (low-grade) K-bentonite contained substantially less illite-smectite, ranging from 37 to 63 wt.%. The illite-smectites isolated from the type I K-bentonites displayed greater expandability, contained more octahedral Mg and less octahedral Fe, had greater cation exchange capacity (CEC), smaller thickness of fundamental particles, and thinner illite-smectite crystals in comparison with illite-smectites from the type II K-bentonites. The LOI (loss-on-ignition) and Al2O3 content increased with increasing amount of illite-smectite. The increase in the expandability by 10% corresponded to an increase in CEC by ~10 meq/100 g. The type I K-bentonites had much greater mass loss at <250°C due to greater expandability. The best tilemaking performance was expected for the type I K-bentonite. This raw material could also be potentially valuable for the pharmaceutical, cosmetic and food industries. Overall, the results showed that the studied technological types of K-bentonites from the Dolná Ves deposit differ not only in terms of illite-smectite contents but also in terms of the nature of the illite-smectites.

The mineralogy of partially kaolinized strata interbedded with lignite at the San Miguel mine, Atascosa County, Texas, was investigated by X-ray powder diffraction and optical and scanning electron microscopy. The San Miguel lignite occurs in the lower Jackson Group (late Eocene) of southern Texas. Based on mineralogical and micromorphological data, some of these clay partings are probably volcanic in origin and were exposed to variable degrees of in situ kaolinization in a swamp environment. Coexistence of kaolinite, clinoptilolite, and opal-CT in several of these strata suggests that the partially kaolinized volcanic layers were subjected to a subsequent resilication process following burial. Kaolinite is the dominant mineral in the oldest and most kaolinized volcanic layer (underclay) below the lowest lignite bed (seam D). The kaolinite exhibits a well-developed vermicular morphology. The youngest volcanic layer, which occurs stratigraphically above the uppermost lignite seam, is characterized by pseudomorphs of volcanic glass shards and consists mainly of clinoptilolite. Movement of siliceous ground water from this layer to the underlying strata apparently provided silica-rich solutions from which opal-CT and large (as long as 300 μm) euhedral crystals of clinoptilolite precipitated in the fossilized plant roots, veinlets, and fractures within the underlying strata. Micromorphological relationships between the Sirich (opal-CT and clinoptilolite) and sulfide (marcasite and pyrite) minerals in the fossil roots and fractures suggest that the marcasite formed before and pyrite after the resilication process.

An iron-rich chlorite, ripidolite, was oxidized by air-heating at 480°C, i.e., below the dehydroxylation temperature and subsequently reduced in hydrogen at the same temperature. On the basis of chemical, differential thermal, infrared, Mössbauer, and X-ray powder diffraction analyses, Fe(II) seems to be present only in the 2:1 layer of the original chlorite in a type of site similar to that of Fe(II) in biotite, with OH in cis-positions. These data also suggest that octahedral Al and Fe(III) are located in the hydroxide sheet of the original chlorite. The structural changes of the mineral due to the oxidation and the subsequent reduction appear limited to minor structural rearrangements and, perhaps, to the introduction of OH in both cis- and trans-positions. The results of the investigation are in agreement with a reaction of the form: [Fe(II)OH]+ ⇋ [Fe(III)O]+ + H(H+ + e−).

Synthetic aluminous hematites and goethites have been examined by Fourier-transform infrared spectroscopy. For aluminous hematites prepared at 950°C a linear relationship exists between Al content and the location of the band near 470 cm−1, up to 10 mole % Al substitution which is shown to be the solubility limit. The spectra of aluminous goethites prepared in two different ways are qualitatively similar to each other, but differ as to the relationship between the position of the band near 900 cm−1 and the Al content. The spectra of the two series of hematites produced by calcining the goethites at 590°C also show a strong dependence of band position and intensity on the goethite preparative method.

A standardless method of energy dispersive X-ray fluorescence in conjunction with scanning electron microscopy was used to analyze selected areas of clay-size particles of talc, pyrophyllite, and kaolinite supported by a carbon planchet. Peak intensity ratios of fluorescing elements relative to silicon were converted directly to weight or mole ratios using conversion factors determined theoretically. The conversion factors depend upon particle thickness and mass adsorption coefficients of the sample for the elements analyzed. The effects of particle thickness become significant above ~0.1 μm. Without using particle thickness corrections, the mean molar ratios of metal to Si agreed to within 6.1,0.5, and 9.7% of the theoretical ratios for kaolinite, pyrophyllite, and talc, respectively.

The Nriagu polymer model of 2:1 layer type clay minerals develops from the premise that clay minerals are condensation copolymers of solid hydroxides. In the Mattigod-Sposito formulation of the model, standard state chemical potentials (standard Gibbs energies of formation from the elements) of 2:1 clay minerals are predicted quantitatively with a linear correlation equation relating the standard Gibbs energy of the polymerization reaction (ΔGor) to the half-cell layer charge of the clay mineral and to the valence and ionic radius of the exchangeable cation. It is now shown that this correlation equation can be derived from two basic assumptions: (1) that the standard Gibbs energy change for the transfer of a cation in a pure hydroxide solid to a hydroxide component in the tetrahedral or octahedral sheet of a 2:1 clay mineral is independent of the nature of the cation and (2) that the difference between ΔGor for the polymerization reaction to form a 2:1 clay mineral and ΔGor for the same reaction to form the zero layer-charge analog of the clay mineral is proportional to the number of interlayer exchangeable cations per unit cell of the clay mineral and to the radius of its exchangeable cation. Both of these assumptions can be tested experimentally, independent of the polymer model.

Investigations were conducted to determine the hydrothermal transformations of synthetic birnessite exchanged with different metal ions. Autoclaving in a Teflon-lined stainless steel pressure vessel at 155°C for 24 hr of Mg-, Ca-, La-, and Co-saturated birnessite yielded manganese minerals having 10-Å X-ray powder diffraction (XRD) spacings. The autoclaved Mg-birnessite yielded a mineral identical to natural todorokite in its infrared (IR) spectrum and XRD patterns. High-resolution transmission electron microscopy (HRTEM) provided images having 10-, 12.5-, 15-, and 20-Å wide fringes indicating heterogeneous channel widths in the crystallographic a direction, and IR spectroscopy produced bands at 757, 635, 552, 515, 460, and 435 cm-1, confirming the product obtained by autoclaving Mg-birnessite to be todorokite. Prolonged autoclaving of Mg-birnessite yielded manganite (γ-MnOOH) as a by-product; manganite did not form when the autoclaving time was shortened to 8 hr. Also, when Ca-saturated samples were autoclaved, the product gave d-values of 10 Å, but the XRD lines were broad and heterogeneity of the channel sizes was evident from HRTEM observations. The Ca-derivative had an IR spectrum similar to that of natural todorokite. Images showing 10-Å lattice fringes were observed by HRTEM for the Ni-saturated sample, which also produced an XRD pattern similar to that of the Mg-saturated sample. Co- and Lasaturated samples did not form todorokite, although HRTEM of La-saturated samples indicated some 10-Å lattice fringes that were unstable in the electron beam. Birnessite saturated with Na, K, NH4, Cs, Ba, or Mn(II) gave products having 7-Å spacings upon autoclaving.

Large-pore La-Al-pillared montmorillonite was prepared by reacting montmorillonite with hydrothermally treated mixtures of aluminum chlorohydrate and lanthanum chloride. The large-pore La-Al-pillared montmorillonite is characterized by basal spacings of about 26 Å, surface areas of 300–500 mVg, and pore volumes in the range 0.2–0.3 cm2/g. Large-pore pillared montmorillonite products were obtained from solutions refluxed for >72 hr or treated in autoclaves at 120°–160°C for 12–96 hr. The most favorable pillaring solution for the production of large-pore La-Al-pillared montmorillonite had an OH/Al ratio of 2.5, a La:Al ratio of 1:5, and was 2.5 M with respect to Al. The elemental composition of large pore La-Al-pillared montmorillonite is similar to that of a conventional Al-pillared montmorillonite that has a basal spacing of about 19 Å. The 26-Å spacing is believed to be associated with the formation of large polymeric La-bearing Al-cations upon hydrothermal treatment of the solutions.

The effect of the surface acidity of montmorillonite and kaolinite on the hydrolysis rate constants of different agricultural chemicals was studied at variable moisture contents. Ethyl acetate, cyclohexene oxide, isopropyl bromide, 1-(4-methoxyphenyl)-2,3-epoxypropane, and N-methyl p-tolyl carbamate were chosen as representatives of classes of chemicals that exhibit acid-catalyzed, base-catalyzed, and neutral hydrolysis. In addition to being commercially available in pure forms, these chemicals have well-characterized homogeneous kinetics. The presence of montmorillonite or kaolinite in water suspensions had a small effect on the hydrolysis rate constants (kh), whereas, the addition of moisture to oven-dried clays up to the limits of sorbed water resulted in an increase in the rate of hydrolysis of the epoxide by a factor of 10.

The increase in the hydrolysis rate constant suggests that the surface pH of montmorillonite or kaolinite might be 1–2 pH units lower than the bulk pH. The kh value for the carbamate on Na-montmorillonite surface (bulk pH = 8.5) is 6.4 × 10−8/sec which is equivalent to the rate constant at pH values ≤7. The hydrolysis rate constant of the epoxide was reduced by a factor of 4 when the moisture content exceeded the limit of sorbed water. The addition of humic acid to the clay minerals resulted in about a 40% reduction of the epoxide hydrolysis rate constant.

Mn-substituted iron oxides were synthesized by coprecipitating Fe(NO3)3 and Mn(SO4) solutions with NH4OH, adjusting the suspensions to pH 4 or 6, and then keeping the suspensions at 55°C for 62 days. The Mn mole fraction of the final products ranged from 0 to 0.3. X-ray powder diffraction patterns showed that goethite and hematite formed in each Fe-containing system. Groutite formed in systems having initial Mn mole fractions ≥0.35. Only manganite and hausmannite formed in the pure Mn systems. The oxalate-soluble Fe in the samples increased as the Mn mole fraction increased and was slightly larger for the pH 6 series.

For samples that contained the largest Mn mole fraction, the b and c dimensions of the goethite unit cell were shifted toward those of groutite, and the b and c dimensions of the groutite unit cell were shifted toward those of goethite. Assuming the Vegard rule holds for the unit-cell c dimension, the goethite accommodated a maximum Mn mole fraction of 0.34, and the groutite accommodated a maximum Fe mole fraction of 0.31. The unit-cell dimensions of hematite did not vary systematically with the mole fraction of Mn in solution, probably because little Mn substituted into the hematite structure.

Due to their unique polarity, pore-size distribution, and high surface areas, pillared and delaminated clays are potentially useful materials for the adsorption of environmental toxicants. To determine their properties for adsorption of chlorinated phenols, alumina-pillared montmorillonite (APM), chromia-pillared montmorillonite (CPM), and alumina-delaminated Laponite (ADL) were reacted with aqueous pentachlorophenol (PCP) solutions in batch equilibrium experiments. An hydroxy-Al Laponite (HAL) in which the Na+ exchange ions were replaced by ions of the type Al13O4(OH)(24+x)(H2O)(12-x)(7-x)+ was included in the study. With ADL as the adsorbent, the extent of PCP adsorption increased with decreasing pH, and then became constant at pH ≤ pKa. Thus, the neutral phenol was preferred over the phenolate form. Binding of neutral PCP at pH 4.7 to all adsorbents never reached saturation values, and the loadings achieved were limited by the water solubility of the adsorbate. Among the pillared and delaminated clays investigated, ADL exhibited the largest capacity for physical adsorption of PCP at pH 4.7. Differences in the PCP binding capacities for APM, CPM, and ADL suggested that adsorption was dependent on the pore structure and surface composition of the modified clay adsorbent, not on surface area alone. HAL exhibited quantitative uptake of PCP at the 8 µmole/g level, indicating that a chemi-sorption mechanism may operate for PCP binding to this adsorbent. Adsorption of 3-chlorophenol, 3,5-dichlorophenol, and 3,4,5-trichlorophenol by ADL at pH 7.4 increased as the degree of hydrophobicity and chlorination of the phenol increased; hence, the binding capacity was not limited by the molecular size of the adsorbate. In contrast to the adsorption properties observed for pillared, delaminated, and hydroxy-interlayered clays, Na+-montmorillonite and Na+-Laponite did not adsorb PCP from aqueous solution.

A 14-Å mineral coexisting with kaolin minerals, mica, and gibbsite in a Korean Ultisol and showing X-ray powder diffraction features of “chloritized” vermiculite was studied by a combination of methods. The 14-Å mineral collapsed on saturation with K+ after extraction with hot 1/3 M sodium citrate, but the Si/Al ratio of the extracted material was close to 1.0 and kaolin minerals dissolved, as indicated by difference infrared spectroscopy. The 14-Å mineral was also collapsed by heating at or above 350°C. The difference infrared spectra and the X-ray powder diffraction patterns indicated that two forms of kaolin mineral are present that differ in thermal stability; one decomposed by heating at or below 375°C and the other by heating above 375°C. The former kaolin mineral is probably associated with vermiculite and the latter is present as a discrete form. The 14-Å mineral was inferred to be an intergradient vermiculite-kaolin mineral, in which most vermiculite layers each partially transform into double kaolin layers, and to represent an intermediate phase during the transformation of 2:1 to 1:1 layer silicates in acid soils.

The methylation of the fibrous clays, sepiolite and palygorskite, should be facilitated by their large content of surface silanol groups and the low acidity and inaccessibility of coordinated water molecules. Infrared spectroscopy showed that the reaction of diazomethane with these clays resulted in the methylation of their silanol surface groups. The grafting of CH3 groups on the surfaces of these clays produced a decrease in the surface area due primarily to the lowering of the microporosity.

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.