The Li+ ion is used frequently as an environmentally acceptable surrogate for sorbing radionuclides in field tracer tests, and experiments using Li are an important part of assessing the potential transport of radionuclides in saturated alluvium south of Yucca Mountain, Nevada, the site of a proposed nuclear waste repository. Equilibrium partition constants (Li+ Kds) were measured using batch studies incorporating a wide range of Li+ concentrations and two different grain-size fractions of alluvium samples from multiple depth intervals in two wells. Cation exchange capacity, surface area, bulk mineralogy from quantitative X-ray powder diffraction, and trace Mn- and Fe-oxyhydroxide mineralogy from extractive studies were evaluated as predictors for linearized Li+ Kd values (K1in) in the alluvium. Many of the predictor variables are correlated with each other and this was considered in the analysis. Linearized Kd values were consistently higher for fine particle-size fractions than for coarse fractions. Single and multivariate linear regression analyses indicated that the clinoptilolite + smectite content, taken together as a combined variable, was the best predictor for Li+ sorption in the alluvium, although clinoptilolite content was clearly a better predictor when the two variables were considered separately in simple linear regressions. Even so, Li+ Klin predictions based on clinoptilolite and smectite abundance were accurate only to within about ±100%. This uncertainty suggests that there is either a high inherent variability in Li+ Klin values or that additional alluvium characteristics not measured or evaluated here may play an important role in simple Li+ cation exchange in the alluvium.

A few days after Dr. RudoIf Wegscheider of the University of Vienna celebrated his sixtieth birthday in October, 1919, he began his next class with the following words:

An experimental technique for studying the swelling of clay under constraint and some preliminary results for the swelling of Wyoming bentonite in several media are presented and discussed. Fractionated, powdered clay is mixed with an equal weight of non-swelling microporous porcelain, which serves to distribute the swelling agent rapidly and uniformly. The mix is compacted in a cell at high pressure and permitted to imbibe fluid through a porous porcelain plate under simultaneously applied almost equal pressures from 0 to 10,000 psig on both sides of the fluid-gel interface. The unidirectionally constrained volume change of the sample is measured by displacement of mercury in a steel buret. Degree of swelling is taken as the volume ratio of gel to 105° C dry clay.

In the range of pressure from 0 to 10,000 psig, the colloidal magnesium sodium montmorillonite swells from about 93 to 231 percent (volume ratio 1.93 to 3.31) depending on the composition of imbibed fluid. Aqueous 0.171N sodium chloride and magnesium chloride solutions produce 14 and 11 percent, respectively, more swelling at 1,500 than at 0 psig. Swelling in calcium chloride solution is insensitive to this pressure change. At 10,000 psig these solutions, and hydrochloric acid, produce less swelling than at 1,500 psig and, in fact, produce almost equal swellings of 130± 4 percent. It is inferred that swelling in chloride solutions at this pressure may be essentially cation-independent. Within the concentration range of 0 to 171N there appears to be little practical difference in the degree of swelling of the clay by sodium chloride and calcium chloride solutions; the swelling is a linear function of the logarithm of the salt concentration.

Comparison of d(001) spacings calculated from swelling ratios with those obtained by X-ray diffraction lead to the conclusion that the method measures crystalline swelling in contradistinction to osmotic swelling.

Electron microscope studies show that most of the clay minerals have morphological characteristics which can be effectively used to aid in their identification. In addition, detailed studies at high magnification have provided structural information not obtainable by other means.

In the kaolinite group each of the common minerals has a clear-cut and diagnostic morphology. However, much more work is needed on flint clays and the kaolins in soils before the same can be said of these varieties. Continued study of halloysite reveals significant details pertinent to the form and structure of the tubular crystals.

Illites from different sources show interesting differences in form which reflect variation in the degree of crystallinity. An illite from the Ordovician Oswego formation shows an unusual development of narrow to broad lath-shaped crystals. Except for lower content of iron and magnesium the material has all the characteristics of other illites. The thinnest laths are of the same order of thickness as the flakes of more common illites. Certain mixed-layer minerals are identical in morphology with some varieties of illite.

The minerals of the moutmorillonite group have been the most difficult of the clay minerals to characterize on the basis of morphology. The lath-shaped crystals of certain beidellites, sauconite, nontronite, and hectorite are diagnostic. The metal shadowing technique shows that many of the laths approach one unit cell in thickness.

The morphology of many montmorillonites is dependent upon the mode of sample preparation. The replica method offers a means of studying clay particles in their natural state but this technique is still in the early stages of development as it relates to the clay minerals.

Three techniques have been used to determine what clay mineral surfaces are involved in the selective bonding of Co: (a) polyphosphate ions were used to block edge surfaces of montmorillonite and vermiculite from Co, (b) collapse of the interlamellar spaces with potassium saturation was used to block internal basal surfaces of vermiculite from Co, and (c) autoradiographs were prepared of vermiculite and mica particles that had reacted with Co58. In each case Co in low concentration was allowed to combine with the mineral in the presence of high concentrations of CaCl2.

The preliminary sorption of polyphosphate ions had no appreciable effect on the sorption of Co by the minerals studied, indicating that the edge surfaces were not likely to be involved in the Co reaction. The blocking of internal basal areas had only a very slight effect suggesting that these surfaces were involved in the sorption of Co, but only to a limited extent. Autoradiographs of naturally occurring vermiculite particles revealed a somewhat uneven distribution of Co over the planar surface of the particles. Removal of the outer layers of the crystals, either before or after the material had combined with Co but before autoradiography, resulted in a concentration of the metal along edges and cracks.

Apparently the external basal surfaces are principally involved in the specific sorption of Co by layer silicates. It is suggested that chemical weathering and physical abrasion of the surfaces introduce defect structures which favor the chemical bonding of heavy metals.

A sorption apparatus consisting of (1) a high vacuum system (<10−5 mm Hg), (2) an oil manometer to determine the equilibrium vapor pressure, (3) a quartz helix to determine weight of adsorbate, and (4) a constant temperature control for the adsorption chamber has been used to obtain water vapor sorption isotherms on kaolinite. Equilibrium between water vapor and the clay surface can be obtained in 2 hours with this equipment. The estimated error in relative pressure (P/P0) and amount of water adsorbed (X) are ± 0.001 and ± 0.07 mg H2O/g clay respectively. Reproducibility of sorption isotherms for clay samples similarly prepared are within these limits. When retested those clay samples that had stood in the laboratory for a few weeks gave sorption isotherms slightly different from the initial isotherm. This variation, while not excessive, seriously limited interpretation of the sorption data.

In order to study the variation of sorption characteristics with curing conditions, two samples were stored at an elevated temperature (70°C) under two different conditions of moisture content and pressure; one sample as a water slurry (1 g clay per 10 ml H2O) and the other completely dry in an evacuated (<10−5 mm Hg) container. The effect on the sorption isotherms was in both cases very marked but of a different character.

Compared with the sorption behavior of the initial Li kaolinite, the sample stored as a slurry showed greater water adsorption at all values of P/P0 and a disappearance of the marked hysteresis which persists to very low P/P0 on the initial sample; however, when stored in vacuo, Li kaolinite at all values of P/P0 adsorbed less water than the initial Li kaolinite. Data are presented to show that the sample stored as a slurry has been converted to an Al kaolinite. The reduced water sorption upon storage in vacuo is shown to be a permanent change.

The viscosity of certain kaolin—water systems was correlated with natural montmorillonite content of the kaolin, as determined quantitatively by the Hinckley—Bates (1960) strontium-exchange technique. Transition from low viscosity to high viscosity occurred when montmorillonite content of the Georgia clays studied exceeded 5%.

Pillared clays (PILCs) with magnetic properties have significant potential for application in industry and the environment, but relatively few studies of these types of materials have been carried out. The aim of the present work was to gain insight into the magnetic and structural properties of pillared clays by examining in detail the influence of the calcination temperature and the nature of different pillared clays on these properties.

Magnetic layered systems from different pillared clays were prepared and characterized. Firstly, Ti-, Al-, and Zr-pillared clays (Ti-PILCs, Al-PILCs, and Zr-PILCs, respectively) were produced at different calcination temperatures and then magnetic pillared clays (Ti-M-PILCs, Al-M-PILCs, and Zr-M-PILCs) were prepared at ambient temperature. The synthesis involves a reduction in aqueous solution of the original Fe-exchanged pillared clay using NaBH4. The structural properties of pillared clays and their magnetic forms were investigated using X-ray diffraction, N2 adsorption, cation exchange capacity determination, and X-ray fluorescence (XRF) measurements. The properties of the magnetic pillared clays were investigated by superconducting quantum interference devices and Mössbauer spectroscopy. An evaluation of the data obtained allowed an estimation of the pillared structure in one PILC-model before and after magnetization. The model was determined on the basis of a simple geometric model and experimental data leading to the calculation of a filling factor (FF) which contained information about the number of intercalated pillared layers and the unaffected layers. In the case of Ti precursors, the best calcination temperature was 400°C, which maintained the highest specific surface area and pore volume with magnetic parameters suitable for magnetic application. Similar experiments with Al- and Zr-pillars have been discussed. A correlation between the XRF data, porosity, FF calculation, and magnetic properties led to the conclusion that the sample Al-M-PILC previously calcined at 500°C was the most stable material after the magnetization process. The same examination in the case of Zr materials suggested that the most stable sample had been calcined at 300°C (sample Zr-M-PILC-300).

In recent soil mechanics literature attempts have been made to explain the engineering properties of clays in terms of surface chemical theories, particularly the Gouy—Chapman theory. Experimental confirmation of these theoretical predictions have been restricted almost exclusively to studies performed on fine grain size fractions of montmorillonite. It seemed desirable to determine experimentally the effect of physico-chemical variables on the engineering properties of a more typical engineering material. The < 2 μ fraction of Fithian illite was selected.

A study was made of the effect of variations in the pore water electrolyte concentration on the engineering properties of homoionic Ca- and Mg-illite. Pore water electrolyte concentrations ranged from 1 N down to about 10-4 N. Engineering tests included Atterberg limits, one-dimensional consolidation tests, and effective stress triaxial tests.

The electrolyte concentration was found to have only a small effect on the Atterberg limits, the maximum limits occurring at electrolyte concentrations between 0.01 N and 0.1 N. For virgin consolidation the soil seemed strongest at about the same range in electrolyte concentrations but the effect was not large. Electrolyte concentration had almost no effect on the position of the rebound (swelling) curves. The most important effect of electrolyte concentration seemed to be its effect on the geometric arrangement of the particles for samples that were sedimented from dilute suspension. The geometric arrangement of particles seems to be a more significant variable than the osmotic repulsion between particles.

There still appears to be merit in the old mechanical approach where the compression characteristics are explained by elastic bending (reversible), slippage (partially reversible), and rupture (irreversible) of particles. Double layer phenomena seem to exert a much smaller influence on the engineering properites of nonexpanding lattice clay minerals than is commonly inferred in the literature.

Pyridine N-oxide and montmorillonite form interlamellar complexes with basal spacings of 14·7 and 21 Å. The former corresponds to a monolayer with a tilted orientation of the pyridine ring; the latter comprises a double layer of molecules between the clay sheets. Infrared spectra show that pyridine N-oxide bonds through the NO group; in the 21 Å complexes it is coordinated to the exchangeable cations through water molecules acting as bridges which themselves are directly coordinated to the cations. In the 14·7 Å complexes a splitting of the ν(NO) band occurs with the more polarizing cations Mg and Ca; the two bands correspond to pyridine N-oxide molecules directly coordinated to the cation and to other molecules coordinated through bridging by water molecules. Cs montmorillonite forms complexes with a basal spacing of approximately 14·7 Å which also shows a splitting of the ν(NO) band.

Antibiotic-resistant genes (ARGs) have been regarded as emerging contaminants that threaten public health worldwide. Poultry excreta, often used as a fertilizer in agriculture, are a major route for the proliferation and dissemination of ARGs in the environment. The aim of the present study was to assess the potential of dietary palygorskite (Plg) supplementation as nutritional manipulation for the modulation of microbial community structure and the attenuation of ARGs in the cecal contents of broilers fed with chlortetracycline (CTC). In total, 256 one-day-old, mixed-sex, broiler chicks were allocated randomly into a 2 × 2 factorial design of four treatments, which consisted of two levels of CTC (0 or 50 mg/kg) and Plg (0 or 10 g/kg). By employing in vivo feeding and slaughter experiments, after collecting the cecal contents and extracting the total genomic DNA, 16S rRNA V3-V4 hypervariable amplicon pyrosequencing and quantitative PCR-based approaches were used to address the impact of Plg on microbiota and the abundance of ARGs in broilers. The results showed that broilers given a diet supplemented with Plg had greater α-diversity indices including Chao1, phylogenetic diversity tree, and observed-species index calculations, when compared with those without Plg supplementation. Birds given a diet supplemented with Plg had fewer Firmicutes at the phylum level, but a greater abundance of Alistipes at the bacterial genus level. Dietary Plg counteracted the CTC-induced increased abundance of ARGs, among which tet(K) had a pronounced decrease, along with a similar decreased tendency for other measured ARGs and intI1. Overall, the results indicated that Plg supplementation caused pronounced changes in cecal microbial diversity and microbiota community composition of broilers, and effectively reduced ARGs, indicating that Plg supplementation is a potential alternative measure for the attenuation of ARGs in the cecal contents of broilers.

Sepiolite-based composites have great potential for application as flame-retardant and thermal-insulation material but their application and development are limited by poor mechanical properties. The objective of the present study was to combine polyvinyl alcohol (PVA) and 3-aminopropyltriethoxysilane (KH-550) with sepiolite (Sep) to improve its aerogel strength. A universal testing machine, thermogravimetry, and microcalorimetry were used to investigate the mechanical properties, thermal-stability, and flame-retardant properties, respectively, of aerogels. The results indicated that KH-550 can enhance effectively the mechanical properties and flame retardancy of aerogels. The compressive modulus of PVA/Sep vs KH-550/PVA/Sep aerogel was 209.28 vs. 474.43 kPa, the LOI index changed from 26.4 to 30.4%. The porosity of the aerogels was > 96% and the density was < 0.05 g/cm3. The thermal conductivity remained at between 0.0340 and 0.0390 W/(m·K), and the aerogel could recover to > 85% after a 50% compressive deformation. These data indicated that Sep-based aerogel would act as a flame retardant and a thermal insulating material with excellent mechanical properties.

Ion-exchange modeling is one of the most widely used methods to predict ion adsorption data on clay minerals. The model parameters (e.g. number of adsorption sites and the cation adsorption capacity of each site) are optimized normally by curve fitting experimental data, which does not definitively identify the local environment of the adsorption sites. A new approach for constructing an ion-exchange model was pursued, whereby some of the parameters needed were obtained independently, resulting in fewer parameters being based on data-curve fitting. Specifically, a reversed modeling approach was taken in which the number of types of sites used by the model was based on a previous first-principles Density Functional Theory study, and the relative distribution of these sites was based on the clay’s chemical composition. To simplify the ion-exchange reactions involved, montmorillonite was Na-saturated to produce a well-controlled Na-montmorillonite (NaMnt) adsorbent. Ion adsorption data on NaMnt were collected from batch experiments over a wide range of pH, Cs+ concentrations, and in the presence of coexisting cations. Ion-exchange models were developed and optimized to predict these cation adsorption data on NaMnt. The maximum amount of adsorption of monovalent cations on NaMnt was obtained from the plateau of the adsorption envelope data at high pH. The remaining equilibrium constants (pK) were optimized by curve fitting the edges of the adsorption envelope data. The resultant three-site ion-exchange model was able to predict the retention of Li+, Na+, K+, and Cs+ very well as a function of pH. The model was then tested on adsorption envelopes of various combinations of these cations, and on Cs+ adsorption isotherms at three different pH values. The pK values were constant for all assays. The interlayer spacing of NaMnt was also analyzed to investigate its relation with cation adsorption strength. An X-ray diffraction study of the samples showed that the measured d001 values for these cations were consistent with their adsorption pK values. The Cs+ cation showed a strong ability to collapse the interlayer region of montmorillonite. In the presence of multiple competing cations, the broadening and presence of multiple d001 XRD peaks suggested that the cations in the interlayers may be segregated.

Glauconites occurring within the Ukra Member of Kutch Basin have remained unexplored in terms of their economic significance. The present study aimed to present a detailed physicochemical characterization of glauconite occurring in the siliciclastic rocks of Guneri and Umarsar area of the Kutch district, Gujarat, India to explore their economic potential. The study involved an integrated petrographical, mineralogical, and geochemical investigation of glauconitic rocks to highlight the occurrence, nature, and maturity of glauconite. The characterization was carried out using X-ray diffraction (XRD), X-ray fluorescence (XRF), and electron probe microanalysis (EPMA) combined with energy dispersive X-ray (EDX), Field emission gun scanning electron microscopy (FEG-SEM), Fourier-transform infrared spectroscopy (FTIR), and inductively coupled plasma mass spectroscopy (ICP-MS). Petrographic and bulk XRD analysis revealed that the glauconite occurs as green pellets constituting ~30 and 40% of the glauconitic sandstone and shale, respectively. Whole-rock analysis showed that the value of K2O varies considerably from 3.93 wt.% (sandstone) to 5.63 wt.% (shale). Mineral chemistry indicated the distinctive chemical composition of glauconite pellets containing 7.4–8.4 wt.% of K2O. The parameters, such as the distance between the (001) and (020) peaks and the large K2O content (~8 wt.%) of the glauconite fraction reflect an evolved to highly evolved stage of maturation. The morphological and spectral signatures further support the high degree of maturation in glauconites. Trace-element analysis implied that the glauconitic sandstone and shale contain elements such as Zn, Mn, Cu, Co, Mo, and Ni, which serve as essential micronutrients for plants. These data sets collectively constitute part of a preliminary study which is prerequisite to beneficiation, but further evaluation of its potential as a potash fertilizer also is needed.

The total concentrations of rare-earth elements (REE) in the mined kaolin (0.02–0.06 wt.%), kaolin mine tailings (0.03–1.9 wt.%), and the kaolin-associated Marion Member sand lithology (0.03–4.6 wt.%) opened questions regarding the modes of occurrence of the REE and the role(s) of chemical weathering and secondary processes to explain the presence of REE in these materials. The REE were hosted primarily by phosphate minerals (monazite, xenotime) based on mineralogic analyses (scanning electron microscopy, X-ray diffraction). Enrichments in the light rare-earth elements (LREE: La–Gd) and the high correlation coefficient values were noted between P and the total REE concentrations (r2 = 0.99) for the sands and the mine tailings. Lower correlation coefficient values were noted between total REE concentrations and Zr (r2 = 0.31). The coarse fractions of the mined kaolins were enriched in the heavy rare-earth elements (HREE: Y, Tb–Lu) relative to the kaolin-associated sand lithologies. The REE inventory cannot be explained solely by mineral inheritance within the mined kaolins. Lower correlation coefficient values between P and total REE, positive Eu/Eu* anomalies, and the presence of xenotime overgrowths on zircon showed the importance of the role of chemical weathering of the detrital minerals during post-depositional processes (such as diagenesis) leading to redistributed and fractionated REE within the mined kaolin. The possibility of adsorption of the REE to kaolin mineral surfaces in the fine fraction of the mined kaolins remains open and permits further study to characterize fully the multi-modal fractionation of REE possible in the Georgia kaolin deposits.

In order to obtain nanopatterned surfaces, natural allophane particles originating from Japanese soils were immobilized as single particles on Si wafer substrates.When derived from aqueous suspensions, only a few nanoparticles were deposited and detected on the surface due to the weak adsorption of allophanes on the substrate. The amount of immobilized allophane was increased significantly, however, by using an organic solvent in combination with a micelle-based technique to suspend the allophane particles. The micelles were formed from a tailored, aliphatic diblock copolymer that was dissolved in toluene and contained several allophane particles. A cleaned silica chip was used as a substrate on which a monolayer of micelles was immobilized equidistant from each other by dip coating. To remove the polymer from the substrate and to produce free, single allophane nanoparticles, ultraviolet (UV) irradiation was used. After UV treatment, single allophane particles formed ring-shaped deposition patterns with a high surface density. Transmission electron microscopy (TEM) was used to verify the presence of single allophane nanoparticles in the Japanese samples which came from natural sources. The single allophane particles as well as the allophane-containing di-block copolymer micelles, both immobilized on Si substrates and TEM sample grids, were imaged by atomic force microscopy and TEM. In this way, the diameters of the single allophane particles, as well as the distances between the immobilized micelles and the particles and their topography on the substrates, were determined.

The interaction of telone with acid and base saturated montmorillonite furnished adsorption isotherms which possessed combined features of H (high affinity) and C (linear rising) class isotherms; a fall in pH, an increase in electrical conductivity and formation of chloride ions. The observations were indicative of a process of chemisorption, both at the planar and lateral sites of montmorillonites, followed by penetration and swelling of the substrate micropores with telone. A reaction mechanism for the process of chemisorption has been proposed.

The present study deals with accurate identification of polytypes, twins, and allotwins – oriented crystal associations of more than one polytype. The trioctahedral 1:1 layered silicate cronstedtite was studied using single-crystal X-ray diffraction data collected with a four-circle diffractometer equipped with a CCD detector. The sample from the skarn occurrence, Ouedi Beht, El Hammam, Morocco, was explored. It contains cronstedtite in fibrous massive aggregates in the central part, and euhedral crystals in surrounding veinlets and druses. The reciprocal space (RS) sections created by the diffractometer software and presented here were used to determine the OD (ordered-disordered) subfamilies (Bailey’s group A, B, C, D) and to identify polytypes. The chemical compositions of some crystals were determined thereafter by electron probe microanalysis (EPMA-WDS). Some crystals studied are more or less complicated allotwins. Polytypes were thus separated by cleaving crystals into smaller parts in many cases. All polytypes found belong to subfamilies A or D. The following polytypes of the subfamily A were identified: 2M1 (a = 5.49, b = 9.51, c = 14.40 Å, β = 97.30°, space group Cc), 1M (a = 5.51, b = 9.54, c = 7.33 Å, β = 104.5°, Cm), 3T (a = 5.51, c = 21.32 Å, P31), 6T2 (a = 5.50, c = 42.60 Å, P31). 2M1 and 3T were present as isolated crystals or separated by cleaving, otherwise all these polytypes are parts of allotwins. The 2M1 polytype is sometimes twinned by reticular pseudo merohedry with twin index n = 3 and 120° rotation about the chex axis as the twin operation. Allotwins of 1M + twinned 2M1 polytypes are also present. Another kind of twinning, with rotation by (2n+1)×60° about chex is rare. The subfamily D is represented mostly by 2H1 and 2H2 polytypes, a = 5.50, c = 14.25 Å, space groups P63cm (2H1), P63 (2H2). In addition, several six-layer (a = 5.49, c = 42.80 Å), mostly non-MDO polytypes were separated from allotwins by cleaving. In order to identify them, 24 possible stacking sequences were modeled, diffraction patterns calculated, graphical identification diagrams constructed, and comparisons made with actual RS sections. This simulation revealed that five pairs of sequences provided identical diffraction patterns. Polytypes actually found correspond to the following sequences: 1 (6T1), 5 (proposed Ramsdell’s symbol 6T3), 8+10 (6T5), 11+12 (6T4), 24 (6T6, trigonal polytypes, space group type P3), 22 (6R1), and 23 (6R2, rhombohedral polytypes, space group type R3c and R3, respectively). The RS section corresponding to the hexagonal polytype 6H2 (sequence 14) was also found. However, diffraction patterns geometrically indistinguishable can be produced by the twin with rotation by 180° about chex as a twin operation of the rhombohedral polytype 6R2 (sequence 23). Several aggregates with fiber texture of polytype 2H2 were separated from the central part. Use of EPMA-WDS revealed Fe and Si along with significant amounts of Mn and Mg. Crystals from veins were more Mn- and Mg-rich than these from the central part. Traces of Cl, S, and Al are present also.

Organophilic bentonites prepared by reacting various amounts of n-laurylamine hydrochloride and dimethyldioctadecyl ammonium chloride with bentonite have been studied by the method of Fourier transforms. The transform curves obtained from the x-ray diffraction patterns of these samples show how different numbers of organic layers between clay laminae are produced by different kinds and amounts of organic material added to the clay. It has been found that as the organic material reacts by base exchange with the clay surfaces, the number of organic layers between each two clay platelets increases in a regular and stepwise manner.