Particle concentration, charge, solution chemistry (i.e. ionic strength), and the nature of organic matter (OM) are the major factors controlling particle flocculation in aqueous environments. In the present study, the nature of clay fabric associated with clay—OM interaction at a range of ionic strengths was the focus. In the flocculation experiments, the aqueous suspension of montmorillonite and chitin was mixed with NaCl/MgSO4 electrolyte solution. Advanced sample-preparation techniques and visualization methods using transmission electron microscopy were used to observe directly the micro- and nano-scale clay—OM fabric of the resulting flocs. Such direct observation elucidated the role of OM in clay flocculation; few attempts have been made in the past due to the technical difficulties in preserving the original structure. A comparison of clay fabric at two different ionic strengths of 0 and 0.14 M revealed that the individual hexagonal clay particles settled slowly with little intra-aggregate void space (void ratio: 0.07) at 0 M while rapid flocculation and settling of clay particles at 0.14 M, with or without OM, resulted in a more open fabric with greater void space (void ratio: 0.33). The silver-staining technique demonstrated effectively the location of electron-transparent chitin in montmorillonite aggregates. Chitin appeared to link the face-to-face (FF) contacts of clay domains by bridging between negatively charged face surfaces. However, the resultant void ratio and the average hydrodynamic diameter (dH) values were lower than in the OM-free system after flocculation. The results indicated that the interplay between ionic strength and OM content affected the floc architecture and void ratio.

Calcite crystals exposed to clay volatiles react with some components of these volatiles, giving rise to a variety of surface morphologies. F, Cl, and S in different proportions were detected by electron microprobe analysis of the calcite surfaces. Under identical experimental conditions, volatiles from every clay mineral examined caused a specific morphology and chemical composition of the calcite surfaces, but these varied with temperature of the calcite. Changes in pH values and mass spectra of the volatiles after passage through calcite demonstrate that even on rapid heating some clay volatile-calcite reactions occur at temperatures as low as 150°C. Species other than those detectable by electron microprobe analysis also participate in the reactions in which CO2 is liberated.

The surface charge density of mica (001) cleavages was determined by counting the number of fission particle tracks in a given area of a 6-mm muscovite disc replica with optical and scanning electron microscopy after saturation of the layer charge by washing with 0.5 M UO2(NO3)2 solution, dilution of the excess salt by washing with 0.01 M UO2(NO3)2 in 0.005 M HNO3 (pH 2.4), blotting off the excess liquid, thermal neutron activation in contact with the muscovite disc, etching the muscovite, and counting the 235U fission tracks/cm2. In initial studies, the uranyl cations were found to hydrolyze from the cleavage surface continuously during the washings with water, ethanol or acetone to remove excess salts, but the uranyl cations in the interlayers near broken edges and crystallographical steps were strongly retained even against washings with 0.5 M CaCl2 solution. The hydrolysis of UO22 + from the smooth portions of the flake surfaces was avoided by the use of three 1-hr final washings with the 0.01 M UO2(NO3)2 in 0.005 M HNO3 solution. Each flake was pressed between filter papers three times to remove the excess solution. A negligible amount of excess salt remained on the cover glass controls. The UO22 + cations retained (mean, 3.6 ± 0.2 × 10−7 mequiv./cm2) on the cleavage surfaces of various micas were nearly equivalent to the theoretical surface charge (cation exchange capacity, 3.5 × 10−7 mequiv./cm2), showing that hydrolysis was prevented. The uranium on the unblemished mica planar surfaces increased with increasing uranyl concentrations in the final washing solution, indicating that the excess salt remaining on the surfaces had become significant. With a given UO22 + salt concentration, the uranium on the surface increased on increasing the solution pH from 2.5 to 3.5, attributable to the formation of polymeric ions such as U2O52 + and U3O82 + with higher uranium retention per unit positive charge equivalent to the fixed negative charge of the mineral surface. Uranyl cations replaced much of the interlayer cations from vermiculites even after K, Rb and Cs presaturation and drying from 110°C were employed. Strong adsorption of uranyl cations (in a form not replaced by washings with a neutral salt solution), which occurred in the defects of micaceous minerals, is important in the interpretation of actinide element retention in soils and sediments wherein these minerals are abundant.

In the argillaceous fraction of a sedimentary series of petroliferous sandstones from the Sahara two successive diagenetic changes are considered. The first is kaolinization of the original silicates. This is followed by illitization of the kaolinite by saline waters. The same formation is kaolinitic where it produces petroleum and illitic where it is nonproductive.

The physical properties of clay are of extreme importance in soil science. Plant growth, and hence crop production, within any environmental condition is largely controlled by soil structure which results from reactions involving clay. The active clay material in soil, particularly in combination with small amounts of organic matter, exerts a tremendous effect on soil properties. This effect may be on structure (the arrangement of soil particles), or on consistence (the response of the soil to mechanical manipulation). Where structure is favorable soil grains are clumped together into effectively larger aggregates so that soils have a more open arrangement and water and air can move freely and roots function normally. Where structure is unfavorable, soils tend to be heavy and impervious, and both the physical and chemical properties of the soil become unfavorable for plant growth. Soils which are low in clay, such as sands and silts, exhibit a rather narrow range over which physical properties can change and may be unfavorable for plants, being droughty and lacking in fertility. Structure of soil may change through action of natural forces, management practices, or cropping systems, and it is of great importance that we understand how structure affects plants, and how it is formed and stabilized by reactions involving clay.

Combination of clay with relatively small amounts of certain organic compounds greatly changes the physical properties of the system and the nature of the combination and the mechanics of the soil structure-forming process are but little understood. Such changes greatly affect soil consistence and soil-water relationships as well as soil structure. The problem is made difficult since the results of any particular combination or change in clay characteristics must be interpreted not in terms of the clay system alone but in light of the resultant effect on the complex and dynamic system which constitutes a soil. Solution of such problems, however, may be of great importance to our future ability to produce food and fiber abundantly and efficiently from our limited soil resource.

Ion adsorption-type rare earth deposits (IADs) are developed via prolonged weathering of REE-rich volcanic and metamorphic rocks. Intense magmatic activity which occurred during the Yanshanian (199.6–65.5 Ma) and Caledonian periods (542–359.2 Ma) provided an abundant material basis for the formation of IADs in South China. High concentrations of REE and the high proportion of ion-exchangeable REE were found in the Maofeng Mountain regolith, Guangzhou city. However, the geochemical patterns and mechanisms of REE enrichment in the regolith were still poorly understood. The present study investigated the regolith profile (0–8 m) developed in Maofeng Mountain based on metallogenic and geochemical characteristics, sequential extraction, and physical and chemical parameters of the regolith profile. The bedrock contained abundant REE resources (245–287 mg kg–1) and the chondrite-normalized REE patterns showed the enrichment of light REE (LREE) and negative cerium (Ce) and europium (Eu) anomalies. The distribution patterns of REE in the bedrock were inherited by the regolith. REE enrichment of the regolith occurred mainly in the completely weathered layer (B1, B2, and B3 horizons), particularly in the depth range 2.5–4.5 m (849–2391 mg kg–1). The position of REE enrichment was controlled by the soil pH (5.52–6.02), by the amount of kaolinite and halloysite, and by the permeability of the metamorphic rock. In the REE-enriched horizon (2–8 m), the REE were hosted mainly in ion-exchangeable fractions (75–2158 mg kg–1), representing 79% of the total REE. Given the pH of 4.73–6.02, REE fractionation driven by the adsorption of kaolinite was limited. Fe–Mn (oxyhydr)oxides played an important role in REE enrichment and the reducible fraction holds up to 21% (139 mg kg–1) of the total REE. The enrichment of LREE was observed in the reducible fraction potentially because of the preferential release of LREE from the LREE-bearing minerals (monazite) and then scavenged by Fe–Mn (oxyhydr)oxides. Positive Ce anomalies (Ce/Ce*: 10) were found in the reducible fraction because trivalent Ce was oxidized by Fe–Mn (oxyhydr)oxides to cerianite (CeO2). The present study helps to understand the enrichment and fractionation of REE in the IADs of South China.

An infrared method has been developed for estimating kaolinite in sediments. Hydroxyl stretching bands of kaolinite in sediments can be recorded by using a differential technique which eliminates the overlapping owing to other mineralic constituents present. By adding known amounts of an appropriate standard to the sample and by measuring intensities of the OH bands before and after the addition it is possible to calculate the proportion of kaolinite in the test sample. The choice of the added standard is made from characteristic features of the hydroxyl stretching bands.

An electro-optic birefringence technique was employed to study the orientation mechanism of montmorillonite in an electric field. The instantaneous reversal of the field polarity produced evidence of a low voltage permanent dipole and a high voltage induced dipole. This technique was used to study theeffect ofelectrolyte concentration on the rotational diffusion coefficient, a measure of the rate at which the particles rotate or relax, within the solution, from a preferred orientation. Thus, a measure of the immediate environment of the particles was obtained that is not an average effect for the whole system, yet allows for the full development of the clay-cation-water interactions under the experimental conditions. It was found that particle rotation could be accounted for using the measured particle size and normal water viscosity only when the double layer was fully developed, with no free ions or other perturbations. As soon as perturbations were applied, either by adding salts or applying an electric field, the measured particle size and normal viscosity would not account for the data. Either the rotating moiety has to be larger, that is, be a particle plus a water hull, or the viscosity greater, or in some cases both.

Cation exchange of dimethyldioctadecylammonium (DMDO) ion for dimethylbenzyllauryl-ammonium (DMBL) ion previously reacted with centrifuged homoionic Na+ bentonite has been demonstrated. The amount of DMBL ion removed from the clay was determined by ultraviolet spectroscopy.

In order to shift the exchange equilibrium toward removal of the DMBL cation, a large excess of DMDO cation was required. At the limit of these experiments, it was found that 16 percent of the DMBL cation was exchanged.

Anthropogenic activity releases hazardous contaminants and pollutants that are not removed fully by water treatments. Among such pollutants, bisphenol-A (BPA) and bisphenol-S (BPS) are included in a series of Endocrine Disruptive Compounds, which may cause disruption due to hormone blockage or mimicking. Thus, even though those pollutants are not considered lethal, they are hazardous to health due to their similarity to 17β-estradiol, and they have been shown to cause developmental malformation in Zebrafish and breast and prostate tumors in rodents. Both BPA and BPS have been found in water sources at concentrations >30 μg L–1 and since water treatment plants are ineffective at removing them, their concentration is constantly increasing. The purpose of the present study, using a collection of experiments performed by B.Sc. and M.Sc. students, was to apply clay-based materials to the removal of such health hazards from water. Specifically adapted modified clays as neutral organoclays can optimize the interaction between pollutants and the matrix to achieve efficient adsorption. Such an approach is very effective for relatively insoluble pollutants such as BPA, but less so for the more soluble BPS. On the other hand, BPS can be photodegraded catalytically using raw clay or TiO2-impregnated clay. At low catalyst concentration, the modified clay was as effective as a commercial TiO2 catalyst, whereas combining it with H2O2 yielded considerably better results. In summary, clay minerals offer solutions for the removal of health-hazardous pollutants from water, based on different procedures and mechanisms. The versality of clay minerals allows 'tailoring' specifically adapted materials that might improve their efficiency based on such very specific pollutant-matrix interactions.

As a common mineral phase on Earth and Martian regolith, natural rutile was reported as a potential candidate for use as a Fenton catalyst in this study. The influences of Fe and V in various chemical states on the generation of reactive oxygen species (ROSs) and the catalytic activity of rutile were examined. A series of rutile samples with various surface and bulk states of Fe and V were obtained initially by hydrogen annealing of natural rutile at ~773–1173 K. X-ray diffraction, electron paramagnetic resonance spectra, and X-ray photoelectron spectroscopy demonstrated that the atomic fractions of Fe(III) and V(V) decreased sharply with increasing temperature, along with the accumulation of surface Fe(II) and bulk V(III). All as-prepared materials showed enhanced Fenton degradation efficiency on methylene blue (MB) compared with P25-TiO2, and the treated samples exhibited up to 3.5-fold improvement in efficiency at pH 3 compared to the untreated sample. The improved efficiency was attributed mainly to Fenton catalysis involving Fe(II) and V(III). The dissolved Fe2+ played a crucial role in the homogeneous Fenton reaction, while the bound V(III) favored adsorption primarily and may have facilitated heterogeneous Fenton reaction and the regeneration of Fe2+. The pH regulated the reaction mechanism among homogeneous (pH = 3) and heterogeneous (pH = 3.7) Fenton catalysis and physical adsorption (pH = 5, 6). The aim of the present study was to improve the understanding of the potential role of natural rutile with advanced oxidation functions in Earth systems and even on Mars, which also provide an inspiration for screening natural rutile and any other similar, Earth-abundant, low-cost minerals for environmental application.

Portions of Wyoming bentonite were saturated with a series of short-chain aliphatic amine and quaternary ammonium cations, and the amine content remaining after washing was determined by combustion analysis. For those amine cations containing one or two carbon atoms, the amount of amine found was greatly in excess of the cation-exchange capacity. It is thought that this excess consists of amine cations or uncharged amine molecules which have become partly embedded in the holes associated with the oxygen rings of the silica sheet surfaces. For the larger tertiary amine cations, slightly less than the exchange capacity was found, presumably owing to blocking of some exchange sites by steric interference.

Upon treatment of the amine-saturated clays with glycerol and quantitative determination of the glycerol retained as a monolayer, it was found that these clays retain considerably less glycerol than the original bentonite. The glycerol retention values were employed to provide quantitative estimates of the interlayer clay surface left unoccupied between cation pillars. The percentage of original interlayer surface left unoccupied ranged from about 75 percent for methylamine to essentially zero for the larger tertiary amine cations.

The validity of the areas calculated from the glycerol retention results was indirectly confirmed by deriving estimates of the cross-sectional areas of the several cations from the observed reductions in amount of glycerol retained. These experimentally derived cross-sectional areas were found to be in satisfactory agreement with areas of the cations projected from atom models.

Due to the environmental problems derived from the use of common surfactants as modifiers for clay mineral adsorbents to mitigate mycotoxin contamination of animal feeds, finding non-toxic modifiers to prepare safe and efficient adsorbents is necessary. The objective of the present study was, therefore, to modify acidified palygorskite with polyhexamethylene biguanide (PHMB) to obtain antibacterial polyhexamethylene biguanide/palygorskite (PHMB/Plg) composites for the removal of zearalenone, a common mycotoxin. The PHMB/Plg composites were characterized and analyzed by X-ray diffraction, Fourier-transform infrared spectroscopy, field-emission scanning electron microscopy, and isothermal nitrogen adsorption analysis. The adsorption properties of the composites with respect to zearalenone and their antibacterial activity with respect to Escherichia coli and Staphylococcus aureus were studied. The results indicated that the hydrophobicity of palygorskite was enhanced after modification with PHMB, which could effectively improve the adsorption property of palygorskite toward the nonpolar zearalenone molecules. The adsorption capacity of PHMB/Plg increased with increasing amounts of polyhexamethylene biguanide and increasing pH. The adsorption data were described well by pseudo-second order kinetics and by the Langmuir adsorption model. The maximum adsorption capacity was 2777 μg/g. When the amount of PHMB added increased to 15 wt.%, the composites obtained exhibited good antibacterial performance, and the minimum inhibitory concentrations for Escherichia coli and Staphylococcus aureus were both at 2.5 mg/mL.

Layers of volcanic ash and Andosol soils derived from the ash may play an important role in preserving snow and ice as well as in the development of permafrost conditions in (a) the immediate vicinity of volcanoes at high elevations or at high latitudes and (b) land areas that are often distant from volcanic activity and are either prone to permafrost or covered by snow and ice, but have been affected by subaerial ash deposition. The special properties of volcanic ash are critically reviewed, particularly in relation to recent research in Kamchatka in the Far East of Russia. Of special importance are the thermal properties, the unfrozen water contents of ash layers, and the rate of volcanic glass weathering.Weathering of volcanic glass results in the development of amorphous clay minerals (e.g. allophane, opal, palagonite), but occurs at a much slower rate under cold compared to warm climate conditions. Existing data reveal (1) a strong correlation between the thermal conductivity, the water/ice content, and the mineralogy of the weathered part of the volcanic ash, (2) that an increase in the amounts of amorphous clay minerals (allophane, palagonite) increases the proportion of unfrozen water and decreases the thermal conductivity, and (3) that amorphous silica does not alter to halloysite or other clay minerals, even in the Early Pleistocene age (Kamchatka) volcanic ashes or in the Miocene and Pliocene deposits of Antarctica due to the cold temperatures. The significance of these findings are discussed in relation to past climate reconstruction and the influence of volcanic ash on permafrost aggradation and degradation, snow and ice ablation, and the development of glaciers.

Recent studies indicate that a template method for creating Al-pillared clays, in which surfactant micelles foster the creation of a homogeneous mesoporous network within the pillar, effectively enhance catalyst performance and adsorbent properties. No studies, however, have described the relative effects of the surfactant concentration and Al content on the textural and acidic properties and on the catalytic activity of the Al-pillared clays. The purpose of the present study was to fill this gap, using the isomerization of 1-butene as the test process for catalytic activity. Modified pillared clays (MPC) were prepared from a synthetic clay, TS-1, using different amounts of a non-ionic surfactant (Igepal CO-720) and a fixed concentration of a solution containing the Al polycation [Al13O4-(OH)24]7+. MPC with a fixed amount of surfactant and different amounts of Al were also prepared. The catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), temperature-programmed desorption of ammonia, 27Al magic-angle spinning nuclear magnetic resonance (27Al MAS NMR), and N2 adsorption/desorption isotherms. Isomerization of 1-butene at 250°C was used to test the catalytic activity. Analyses by XRD and XRF showed that the synthesized solids were amorphous and that the amount of pillaring by Al increased with the amount of Al complex used. Interestingly, the surface area and pore volume were directly proportional to the amount of surfactant employed and decreased with increasing amounts of Al pillaring. All solids showed activity for 1-butene isomerization, with a maximum conversion of ∼75%. Only cis- and trans-2-butene were observed. The absence of isobutene suggested that acid sites of moderate strength were formed, in agreement with the results obtained from the desorption of ammonia.

Conversion of tertiary butylacetate to isobutylene and acetic acid and cracking of n-octane were used as model reactions to monitor the catalytic activity of a condensate and aqueous extract derived from a sample of montmorillonite. The condensate was obtained by condensing the vapor phase evolved on heating the clay and the extract was derived from the clay by prolonged water extraction. Both condensate and extract were colloidal systems, which were separated into solid and liquid fractions by distillation. Reactions carried out in a dynamic system established that the solid components acted as true acid catalysts, whereas the liquid fractions were inactive under the experimental conditions adopted. The catalytic activity per weight of the condensate exceeded that of either the parent clay or the extract.

The present results confirm that colloidal size catalysts of high activity can be generated from clays. Such materials, mobilized and transported alone or with formation fluids, may act as catalysts in places removed in space and time from their source. This finding refutes objections previously raised to the operation of bulk clays as catalysts for reactions with particulate organics and supports the concept that acid catalysts derived from clays may participate in organic geochemical reactions in an aqueous medium.