The adsorption on montmorillonite of two monovalent organic cations, methylene blue (MB) and thioflavin T (TFT), was studied in four different situations: (1) separate adsorption of MB or TFT; (2) competitive adsorption of TFT and Cs; (3) competitive adsorption of the two organic cations from their equimolar solutions; and (4) adsorption of TFT on a clay whose cation-exchange capacity (CEC) had been previously saturated with MB. MB and TFT adsorbed to as much as 120% and 140% of the CEC, respectively. Cs did not appear to compete with TFT for the adsorption sites of the clay. TFT molecules adsorbed more strongly than those of MB and displaced them from the clay surface. A model was developed to evaluate the strength of the clay-organic cation interactions. The specific binding of the cations to the negatively charged surface, determined by solving the electrostatic equations, appears to account for adsorption exceeding the CEC and formation of positively charged complexes, which are due to non-coulombic interactions between the organic ligands.

The charge reversal predicted by the model beyond the CEC of the clay was confirmed by microelec-trophoretic experiments. Particles in a sample of montmorillonite loaded with 50 meq TFT/100 g clay moved to the positive electrode, whereas in samples containing the two dyes, MB and TFT, coadsorbed at a total concentration of 100–120 meq/100 g clay, the particles moved to the negative electrode. Binding coefficients describing the formation of neutral and charged complexes of TFT and the clay were larger than those for MB and the clay, thereby explaining the preferential adsorption of TFT observed experimentally. The binding coefficients for the formation of neutral complexes of either MB and TFT and the clay were more than six orders of magnitude larger than those previously reported for inorganic monovalent cations.

The influence of Al on the products formed by aerial oxidation at pH 5.5-7 and 20°C of Fe(II) chloride, sulfate and carbonate solutions, was examined. In all cases Al at levels Al/Al + Fe = 0.09−0.30 inhibited the formation of y phases (lepidocrocite and maghemite) in favor of goethite under conditions where, in the absence of Al, these y phases formed. The influence of Al in these laboratory studies was supported by field observations.

At higher levels of Al, ferrihydrite formation was favored. This effect of Al was seen to be the result of a slowing down in the hydrolysis/oxidation rate of the Fe(II) system.

The presence of Al not only changed the direction of mineral formation, but also caused the formation of Al substitued goethites which resembled in particle size and morphology the natural aluminiferous goethite extracted from a soil.

Nickel nitrate solution is potentiometrically titrated (a) with montmorillonite, (b) without montmorillonite, in the nitrate solution. X-ray powder diffraction and chemical analyses are made of the products formed by the clay at various stages of titration. The pH values of the titration curve (a) are lower than those of curve (b) until the brucite-like hydroxynickel interlayer is more or less complete. The resulting product then closely resembles a chlorite. The preferential precipitation of hydroxide in the interlayer region is explained in terms of the acidic character of montmorillonite interlayers.

The ordering conformation of surfactant molecules in intercalated montmorillonite prepared at various concentrations was investigated by 13C MAS NMR. The 13C MAS NMR study demonstrates the coexistence of ordered and disordered chain conformations. Two main resonance peaks are associated with the backbone alkyl chains: the resonance at 33 ppm corresponds to the ordered conformation (all-trans), and the resonance at 30 ppm corresponds to the disordered conformation (mixture of trans and gauche). Deconvolution of 13C MAS NMR spectra indicates that the ordering conformation of surfactant molecules within the gallery of montmorillonite depends very much on their orientation and packing density. When amine chains are oriented parallel to the silicate layers, the amount of all-trans conformer decreases with the increase of amine concentration. However, the amount of all-trans conformer increases with the increase of amine concentration when amine chains radiate from the silicate layers. Furthermore, 13C MAS NMR spectra show that the intercalated surfactant molecules in the clay minerals never attained the complete liquidlike or solidlike behavior.

Well-characterized American Petroleum Institute clay standards, source clays from The Clay Minerals Society, and other secondary minerals were used to determine the effects of U concentration, temperature, and solution composition on U-sorption properties. Uranium concentrations ranged from about 1.00 × 10−4 M to 4.00 × 10−7 M, temperatures from 5° to 65°C and solution compositions containing 0.01 M NaCl and 0.01 M NaHCO3. Silica gel efficiently sorbed uranyl carbonate anion complexes. The higher cation-exchange capacity materials most readily sorbed uranyl ions from the 0.01 M NaCl solution. Temperature increases tended to affect uranyl ion sorption adversely except when the U was present as carbonate complexes. Noncrystalline ferric oxyhydroxides sorbed uranyl ions much more efficiently than any of the secondary crystalline minerals studied. A method for accurately extrapolating U-sorption efficiencies between experimental points based on the Freundlich equation is presented.

Feroxyhite (δ′-FeOOH) in association with goethite and lepidocrocite was found as a dominant mineral in some rusty precipitates from Finland. These precipitates formed in the interstices of sand grains from rapidly flowing, Fe(II)-containing water which was very quickly oxidized as it flowed through the sediment. The mineral is distinguished from other FeOOH forms and from ferrihydrite mainly by its X-ray powder diffractogram. Further characteristics are an acicular morphology (possibly thin, rolled plates), an internal magnetic field at 4°K of ∼510 kOe, Fe-OH stretching bands at ∼2900 cm−1 and Fe-OH bending bands at 1110, 920, 790, and 670 cm−1, and an oxalate solubility between ferrihydrite and goethite or lepidocrocite. Feroxyhites with very similar properties were synthesized by oxidation of an Fe(II) solution with H2O2 at a pH between 5 and 8.

Most bulk chemical analyses of sepiolite and palygorskite available in the literature are erroneous because samples analyzed are admixtures of minerals that are difficult to separate or identify by other techniques. Some chemical analyses performed on selected individual particles by energy dispersive X-ray analysis (EDX) are also influenced by the same problem. Chemical analyses are summarized for sepiolite and palygorskite reported in the literature (bulk and EDX analyses). The analyses are evaluated by comparison to three sepiolite and three palygorskite pure samples analyzed by EDX techniques. Results indicate that sepiolite is a true trioctahedral mineral, very pure (near end-member) with negligible structural substitution and with eight octahedral positions filled with magnesium, close to the theoretical formula Mg8Si12O30(OH)4(OH2)4(H2O)8. Palygorskite is intermediate between di- and trioctahedral phyllosilicates. The octahedral sheet contains mainly Mg, Al, and Fe with a R2/R3 ratio close to 1, and with four of the five structural positions occupied. The theoretical formula is close to (Mg2R23+?1)(Si8-xAlx)O20(OH)3(OH2)4·R2+x/2(H2O)4, where x = 0–0.5. Sepiolite and palygorskite are thus more compositionally limited than previously reported.

The substitution of Fe3+ in the kaolinite structure is studied by EPR spectrometry and by FTIR spectrometry on a large set of kaolins from different origins (sedimentary and primary ores, soil kaolins). The IR bands at 3598 and 875 cm−1, observed in the literature only in the case of disordered kaolins or in Fe-rich environments (synthetic, lateritic), are revealed by high-resolution IR analysis, whatever the origin and the total Fe content of the samples. The EPR bands corresponding to Fe3+ substituted in sites II of the octahedral sheet increase when the IR absorbance near 3600 cm−1 increases. Two IR absorption bands near 4465 cm−1 and 7025 cm−1 are observed for the first time, both in transmission and diffuse reflectance on all samples. These bands are assigned to the combination of the 3598 and 875 cm−1 bands and to the first harmonic of the band at 3598 cm−1, respectively. The area of the band at 4465 cm−1 in diffuse reflectance is quantitatively correlated to the abundance of Fe3+ located in centers II as measured by ESR. This directly confirms the assignment of the two IR bands at 3598 and 875 cm−1 to OH stretching and deformation vibration bands in octahedral FE3+ environment in the kaolinite structure, respectively. Effects due to the size of particles and to the main kaolins impurities on the near infrared spectra, are also discussed.

The morphology of illite/smectite (I/S) from deeply buried bentonites and hydrothermally altered Tertiary volcanic rocks from Japan changes in parallel with the proportion of expandable layers in the I/S. As viewed by scanning electron microscopy, the morphologies range from the typical “cornflake,” “maple leaf,” or “honeycomb” habit of smectite to the typical platy or scalloped (with curled points) habit of illite. Although the changes are more subtle near either end member, at a composition of 60-70% illite layers, the morphology changes from sponge-like or cellular to platy or ribbon-like. The change of morphology at this composition correlates with a change in layer stacking from turbostratic to rotational ordering of the 1Md type. Turbostratic stacking can be thought of as randomly distributed translations of successive layers by any magnitude and in any direction. The rotationally ordered structure, which allows nearly precise juxtaposition of quasihexagonal oxygen surfaces from adjacent layers, probably permits more crystalline regularity in the a-b plane, which promotes a more plate-like or sheet-like habit.

Polycations of limited molecular size were prepared from 0.1 M solutions of Fe(III)(NO3)3 and A1(NO3)3 by ultrafiltration. Various amounts of the polycations were added to Na-kaolinite, Na-mont-morillonite, and a Na-soil clay and the effect on the flocculation of the clay and electrophoretic mobility compared. Flocculation occurred just before zero net charge was obtained. Addition of further polycation resulted in the dispersion of clay with a net positive charge. The Al polycations possessed a high positive charge (0.49 per gram atom of Al), and their interaction with the clays indicated a planar shape. Adsorption of Al polycations decreased markedly the cation-exchange capacities of the kaolinite and the soil clay but had little effect on surface areas determined by low-temperature N2 adsorption. The Fe polycations were spheres 10–100 Å in diameter with a positive charge of 0.2 per gram atom. The surface areas of the kaolinite and the soil clay were substantially increased by the addition of the Fe polycations but their cation-exchange capacities were reduced by one fifth. Al polycations increased the surface areas of the montmorillonite (to 300 m2) presumably by propping open the interlamellar spaces and rendering the a-b planes accessible for nitrogen adsorption. The Al polycations in interlamellar spaces prevented collapse to 14 Å on heating to 150°C. There was no evidence of regular interlayer Fe as might be anticipated from the size of the spheres.

Caustic nuclear wastes have leaked from tanks at the US Department of Energy’s Hanford site in Washington State (USA) causing hundreds of thousands of gallons of waste fluids to migrate into the underlying sediments. In this study, four simulant tank waste (STW) solutions, which are high in NaOH (1.4 and 2.8 mol/kg), NaNO3 (3.7 mol/kg) and NaAlO2 (0.125 and 0.25 mol/kg), were prepared and reacted with reference kaolinite KGa-1 and KGa-2 at 50 and 80°C for up to 2 months. The structure and morphology of the resulting products were characterized using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. The products were also examined for cation exchange and Cs+ sorption as a function of ionic strength and types of cations in the background solutions. Cancrinite and sodalite were the only new minerals observed in all of the conditions tested in this experiment. Two major chemical processes were involved in the reactions: dissolution of kaolinite and precipitation of cancrinite and sodalite. Increasing NaOH concentration and temperature, and decreasing NaAlO2 concentration increased the transformation rate. Both cancrinite and sodalite appeared stable thermodynamically under the experimental conditions. The newly formed feldspathoids were vulnerable to acid attack and pronounced dissolution occurred at pH below 5.5. Cancrinite and sodalite can incorporate NaNO3 ion pairs in their cages or channels. Sodium in cancrinite and sodalite was readily exchangeable by K+, but less easily by Cs+ or Ca2+. The feldspathoid products sorb nearly an order of magnitude more Cs+ than the unaltered kaolinite. The Cs adsorption is reduced by competing cations in the background solutions. At low ionic strength (0.01 M NaNO3 or 0.005 M Ca(NO3)2), Ca2+ was more competitive than Na+. When the concentration of the background solution was increased 10 times, Na+ was more competitive than Ca2+.

Hydroxy-interlayered minerals (HIMs) are typical of moderately acidic soils. Barnhisel and Bertsch (1989) defined the hydroxy-interlayered clay minerals as a solid-solution series between smectite, vermiculite and pedogenic or aluminous chlorite end-members. Their experimental data for the relationship between the decrease in cation exchange capacity (CEC) and the amount of Al fixed in the interlayers of smectites and vermiculites is reinterpreted using calculated structural, chemical and X-ray diffraction (XRD) evidence. The adsorbed Al ions are in a 6-fold coordination state: [Al(OH)x(H2O)y](3−x)+ with x+y = 6. The polymerization process occurs before saturation of the exchange sites by Al ions. Some of the adsorbed Al ions form polynuclear cations keeping a constant positive charge.

X-ray diffraction patterns of oriented preparations in the ethylene glycol-solvated state suggest that HIMs consist of randomly interstratified expandable and chlorite-like layers (17 and 14.2 Å). Chlorite-like layers result from the selective adsorption of Al complex ions in specific interlayer zones that behave similarly to Al-chlorite (donbassite-like) with incomplete (60%) ‘gibbsite-like’ sheets (chlorite60). Using this framework, HIM XRD patterns can be interpreted by comparison with calculated chlorite60-dismectite mixed-layer mineral patternss using the NEWMOD software.

The effects of temperature on the swelling properties of smectites are important for a variety of different geological conditions, but studies on this topic have been rather limited. The purpose of this study was to investigate the swelling behavior of Na- and Ca-montmorillonite at various temperatures greater than room temperature, up to 150°C, using in situ X-ray diffraction (XRD) analysis. A sample chamber was designed, the temperature and humidity of which were controlled precisely, for environmental in situ measurements. The XRD measurements were performed at small relative humidity (RH) intervals for precise observation of the swelling behavior.

The swelling behavior of Na-montmorillonite showed distinct zero-, one-, and two-layer hydration states. The basal spacings of Na-montmorillonite changed continuously with RH for various temperatures in the transition region between the zero- and one-layer hydration states, and the swelling curves of the transition region moved to greater degrees of RH with increasing temperature. The basal spacings jumped from the one- to two-layer hydration states for all temperatures at almost the same RH.

The basal spacings of Ca-montmorillonite changed continuously from the zero- to the two-layer hydration states at all temperatures. This behavior is remarkably different from that of Na-montmorillonite. At low-RH conditions, the d001 value of Ca-montmorillonite decreased with increasing temperature. The swelling curves of Ca-montmorillonite did not show a plateau at any temperature for the one-layer hydration state. The swelling curves of Ca-montmorillonite moved to greater RH with temperature, similar to the transformation region between the zero- and one-layer hydration states in Na-montmorillonite. These differences between Na- and Ca-montmorillonite are related to the hydration powers of exchangeable cations.

The limitations of existing methods for the prediction of swelling behavior of compacted soils are examined. Both the purely theoretical approach and the purely empirical approach are found to be inadequate. The present study is based on a semi-empirical approach in which a model of swelling behavior is developed leading to equations relating swelling potential or swelling pressure of a compacted soil to its plasticity index, clay content and initial molding water content. The model is based on the concepts of the diffuse double layer, modified by introducing empirical constants to account for elastic swelling effects and other limitations involved in the direct application of double layer theory to real soils. The empirical constants are evaluated from the results of experimental investigations carried out on a large number of soil samples representing a wide variation of clay content as well as consistency limits.

It is shown that the predicted values of the swelling potential and swelling pressure based on the proposed model agree closely with the experimental results of this study and those reported in the literature. Furthermore, the equations developed in this study are of a more general nature and appear to be applicable to a larger range of soil types than those previously published.

The reduction and reoxidation of three nontronite samples, GAN (API H-33a, Garfield, Washington), SWa-1 (ferruginous Washington smectite), and NG-1 (Hohen Hagen, Federal Republic of Germany) were studied with visible absorption and Mössbauer spectroscopy. The intensity of the intervalence electron transfer (IT) band at 730 nm in these nontronites was monitored during reduction and reoxidation at 277, 294, and 348 K. The results showed that the intensity of the band followed the number of Fe(II)-O-Fe(III) groups in the clay crystal, increasing to a maximum at about Fe(II): total Fe = 0.4; upon complete reduction, the band decreased to about the intensity of the unaltered, oxidized sample. With reoxidation of the sample with O2, the intensity of the band increased sharply, followed by a gradual decay back to the original, oxidized intensity. The ultimate level of Fe reduction achieved was at least 92%. Concomitantly, the color changed from yellow through green, blue-green, dark blue, light blue, and light gray as the Fe(II) content increased. The GAN nontronite was more difficult to reduce than the SWa-1 or NG-1 samples. The rate and level of reduction increased with the amount of reducing agent added.

Clay minerals in the upper 50 cm of sediment that surround the Cu- and Ni-rich manganese nodules in the North Equatorial Pacific form two fractions: terrigenous (mostly eolian) illite, chlorite, and kaolinite, and authigenic smectite. Smectite increases with depth in box cores from 26 to 39% and from 53 to 66% in the easternmost and westernmost areas respectively, and with distance seaward from the Americas from 26 to 53% in surface deposits. The change in the amount of smectite relative to other clay minerals is due to dilution by terrigenous debris; smectite probably forms at a uniform rate over much of the North Pacific deep-sea floor. The δO18 value for the smectite is +29.6‰ which suggests that it formed authigenically at a temperature characteristic of the deep-sea floor. The smectite is an Fe-rich montmorillonite that probably forms by the low-temperature chemical combination of Fe hydroxides and silica. Silica is derived from dissolution of biogenic debris, and the Fe hydroxide is from volcanic activity at the East Pacific Rise, 4000 to 5000 km to the east. Al in the authigenic montmorillonite may be derived from the dissolution of large amounts of biogenic silica or from river-derived Al that is adsorbed on Fe-Mn hydroxides in the oceans. The Fe-montmorillonite contains relatively abundant Cu, Zn, and Mn and is of possible economic importance as a source of these and other metals.

A modified version of the Bertaut-Warren-Averbach (BWA) technique (Bertaut 1949, 1950; Warren and Averbach 1950) has been developed to measure coherent scattering domain (CSD) sizes and strains in minerals by analysis of X-ray diffraction (XRD) data. This method is used to measure CSD thickness distributions for calculated and experimental XRD patterns of illites and illite-smectites (I-S). The method almost exactly recovers CSD thickness distributions for calculated illite XRD patterns. Natural I-S samples contain swelling layers that lead to nonperiodic structures in the c* direction and to XRD peaks that are broadened and made asymmetric by mixed layering. Therefore, these peaks cannot be analyzed by the BWA method. These difficulties are overcome by K-saturation and heating prior to X-ray analysis in order to form 10-Å periodic structures. BWA analysis yields the thickness distribution of mixed-layer crystals (coherently diffracting stacks of fundamental illite particles). For most I-S samples, CSD thickness distributions can be approximated by lognormal functions. Mixed-layer crystal mean thickness and expandability then can be used to calculate fundamental illite particle mean thickness. Analyses of the dehydrated, K-saturated samples indicate that basal XRD reflections are broadened by symmetrical strain that may be related to local variations in smectite interlayers caused by dehydration, and that the standard deviation of the strain increases regularly with expandability. The 001 and 002 reflections are affected only slightly by this strain and therefore are suited for CSD thickness analysis. Mean mixed-layer crystal thicknesses for dehydrated I-S measured by the BWA method are very close to those measured by an integral peak width method.

The electrochemical properties of kaolinite before and after modification with chlorodimethyl-octadecylsilane have been studied by electrophoretic mobility, surface charge titration, and extrapolated yield stress measurements as a function of pH and ionic strength. A heteropolar model of kaolinite, which views the particles as having a pH-independent permanent negative charge on the basal planes and a pH-dependent charge on the edges, has been used to model the data. The zeta potential and surface charge titration experimental data have been used simultaneously to calculate acid and ion complexation equilibrium constants using a surface complex model of the oxide-solution interface. The experimental data were modeled following subtraction of the basal plane constant negative charge, describing only the edge electrical double layer properties. Extrapolated yield stress measurements along with the electrochemical data were used to determine the edge isoelectric points for both the unmodified and modified kaolinite and were found to occur at pH values of 5.25 and 6.75, respectively. Acidity and ion complexation constants were calculated for both sets of data before and after surface modification. The acidity constants, pKa1 = 5.0 and pKa2 = 6.0, calculated for unmodified kaolinite, correlate closely with acidity constants determined by oxide studies for acidic sites on alumina and silica, respectively, and were, therefore, assigned to pH-dependent specific chemical surface hydroxyl groups on the edges of kaolinite. The parameters calculated for the modified kaolinite indicate that the silane has reacted with these pH-dependent hydroxyl groups causing both a change in their acidity and a concomitant decrease in their ionization capacity. Infrared data show that the long chain hydrocarbon silane is held by strong bonding to the kaolinite surface as it remains attached after washing with cyclohexane, heating, and dispersion in an aqueous environment.

Parallel-oriented and exceptionally long (> 10 μm) tubes of halloysite occur in the pallid zone of a deeply-weathered lateritic profile on granite in southwest Australia.

Transmission electron microscopy and selected-area electron diffraction of ultrathin sections showed that kaolinite plates within pseudomorphs of mica crystals had fractured at irregular intervals along the a crystallographic axis to produce laths elongated along the b axis. The laths near the edges of the pseudomorphs were less constrained by the pseudomorph and had rolled to produce halloysite tubes. The tubes varied in diameter and degree of roundness. Some tubes were polyhedral rather than cylindrical in cross section. The length and number of planar faces in a tube and the angle between faces varied, exhibiting no consistent pattern.

Tubes in dispersed clay samples showed two types of twinning. In the first type, tubes and associated laths were joined together side by side. In the second type, single tubes bifurcated into two individual tubes. It is proposed that the first type of twinning occurred by folding of adjacent laths that remained joined together while the second type occurred due to exfoliation of a thick lath followed by folding of the exfoliated lath fragments into tubes.

Analytical electron microscopy showed that the chemical compositions of halloysite tubes, laths, and kaolinite plates were similar with the average cation exchange capacity of single tubes being small (4.5 meq/100 g) but higher than values for laths (2.8 meq/100 g) and plates (1.9 meq/100 g).

Nanomorphological structure of well-crystallized Georgia and poorly crystallized North Queensland kaolinite particles have been compared using field emission scanning electron microscopy (SEM) and atomic force microscopy (AFM). In general, there is good agreement in information from the 2 very different imaging techniques. AFM gives more detailed information on step and ledge dimensions, microvalleys and crystallographic orientation of irregularities on basal planes and edges of the crystallites. There are major differences in nanomorphology and surface structure between the 2 kaolin samples with the Georgia kaolin showing 200–500-nm, relatively flat basal planes with some cascade-like step growth 50–100 nm wide. The edges, apparently flat and right-angled in SEM images, appear beveled in AFM images due to artifacts from the aspect ratio of the AFM tip. The North Queensland kaolinite has much more complex surface structure with anhedral crystallites attached to larger particles, high density of steps and nm-scale irregularities (often crystallographically directed). The additional step edge site contribution from the attached crystallites is estimated as a minimum of 6%, giving a total edge contribution above 30% of the kaolinite total surface area. These structures will generate a substantial pH-dependent charge across the surfaces of the North Queensland kaolinite platelets. An idealized, uniform, pH-independent, negatively charged basal plane cannot be assumed from these structures. There is also some evidence, from both SEM and AFM images, of curvature in the thinner, poorly ordered structures of the North Queensland kaolinite particles.