Understanding the behavior of secondary minerals under alkaline conditions is important for predicting the potential alteration of the constituent minerals in radioactive-waste disposal facilities. A previous study reported the formation of uncommon Fe- and Mg-bearing clays under natural alkaline conditions in the Philippines; these were referred to as iron-magnesium-silicate-hydrates (F-M-S-H) and nontronite-like minerals. The current study aimed to investigate the structural and chemical characteristics and to understand the formation pathways of these clays by performing a detailed characterization. F-M-S-H comprised tetrahedral–octahedral–tetrahedral (TOT) layers, imperfect interlayer hydroxide sheets, and interlayer Ca ions. The systematic changes in the characteristics of F-M-S-H at different sampling depths, such as the gradual decrease of the interlayer hydroxide sheets to form smectitic domains, were caused by the differing interaction periods between each sediment at different sampling depths and alkaline seepage. Furthermore, F-M-S-H was ferrous in form prior to oxidation. In contrast, a nontronite-like mineral comprised nontronite and part of an interlayer hydroxide sheet. This mineral was inferred to be formed under chemically different conditions from F-M-S-H, and probably formed in the presence of aqueous Fe3+ and Mg ions.

Addition of HCl, H2SO4, and H3PO4 to montmorillonite clay and a montmorillonitic soil had little effect on the liquid limit of these materials over a wide range of concentrations. The liquid limit of a kaolinitic soil clay was reduced markedly by both HCl and H2SO4, whereas H3PO4 decreased the liquid limit value at lower concentrations and increased it at higher ones. These results are discussed in light of the charge variability and of anion retention by the kaolinitic soil.

Boron and lithium were analyzed in three nanometer-sized (<20, 20-50 and 50-100 nm) separates of two Santonian (85.8-83.5 Ma) bentonite samples collected closely in the Campos Basin along the southeastern Atlantic coast (Brazil). The B and Li data give various trends that suggest varied crystallization conditions for separates that consist of overwhelming smectite with less than 9% illitic layers. The δ11B of the few illitic tetrahedral sites from one of the samples remains quite constant, while its contents are strictly correlated with those of K, which suggests that illitization proceeded by interaction with pore fluids of the host sediments that supplied the K. In the second sample, the δ11B of the illite layers from the two coarser fractions is indicative of an early volcanic origin, while the smaller size fraction also interacted with sedimentary fluids. Favored by octahedral substitutions of the smectite layers, the δ7Li is more strictly regulated by a volcanic link. In turn, the information of the B and Li isotopic compositions and contents from studied mixed-layers suggests a various origin for the few illite layers of the smectite-rich I-S that contain more B than the smectite layers that host more Li. The difference appears to be sample-site and crystal-size dependent, fueled by pore fluids of the hosting turbidites.

The Upper Eocene Jackson Group is the chief host rock of the uranium deposits in the Karnes area of the southeast Texas Coastal Plain. It is highly tuffaceous and the uranium deposits are within approximately 100 ft of the unconformity with the overlying Catahoula Tuff (Miocene?). Glass shards, fragments of sanidine and plagioclase, grains of finegrained volcanic rocks, and biotite and other minerals in these sediments were highly reactive chemically, causing complex diagenetic alteration and the development of alkaline carbonate pore water. Extensive caliche development and silica induration associated with a recent hotter, drier climate favored the concentration of uranium. The origin of these shallow uranium deposits is believed to have been controlled by the complex diagenesis of the highly reactive volcanic detritus, by development of a “builtin” solvent for uranium (the alkaline carbonate pore water), and by climatic, structural, and permeability conditions that allowed concentration and deposition of uranium rather than dilution and dispersal. The tuffaceous rocks are considered to have been the source of the uranium and associated molybdenum, phosphorus, and arsenic.

The particle size distribution, total and exchangeable Mg, and mineralogical compositions were determined on eight well-drained, noncultivated subsoils from Pennsylvania. No correlation was found between the clay content and total Mg (r =.29), or between the clay content and exchangeable Mg (r =.35). Serpentine, talc, and hypersthene were found in the very fine sand and silt fractions of soils having relatively high exchangeable Mg. Mica and 14-Å clay minerals were the only Mg-bearing minerals noted in the same fractions of soils having relatively low exchangeable Mg. Of the Mg-bearing clay minerals found in the clay fractions (smectite, vermiculite, chlorite, illite, and interstratified chlorite/vermiculite), only smectite decreased as the exchangeable Mg in the soils decreased. Two distinctly different distribution patterns of Mg were found for soils having relatively high and low exchangeable Mg. The former soils showed a decreasing Mg content as the particle size decreased, and the latter soils showed the opposite. Exchangeable Mg correlated significantly with the amount of Mg in whole soil, sand, and silt, but not with the amount of Mg in the clay, an indication that sand and silt but not clay were the important sources of exchangeable Mg in these soils.

A hybrid of montmorillonite (Mnt) and rifampicin (RIF) was synthesized and the structure and stability of the drug carrier system clarified. Density functional theory calculations involving dispersion corrections (DFT-D3) were performed to characterize interactions acting in the interlayer space of montmorillonite intercalated with rifampicin. The structure and stability of the RIF-Mnt intercalated complex were determined. Calculations revealed the deformation of the molecular structure of rifampicin after intercalation into the Mnt interlayer space due to the clay environment. The ansa chain of RIF was bent in the interlayer space compared with the structure of the RIF molecule in the monocrystal. RIF was keyed into the Mnt surface by means of numerous hydrogen bonds of weak to moderate strength. The calculated vibrational spectrum from ab initio molecular dynamics (AIMD) was in good agreement with the FTIR measured spectra and helped to analyze the overlapped vibrational bands. Based on analysis of structural stability, theoretical calculations revealed that Mnt is a suitable drug carrier for delayed release of the RIF drug. Batch adsorption experiments showed the large adsorption capacity of montmorillonite for RIF.

Photocatalytic degradation of polluted water by means of minerals, such as clays and oxides, which have surfaces that exhibit catalytic properties, has been suggested to be a useful new strategy to promote both organic and inorganic pollutant degradation. Nevertheless, much still remains to be studied about the capability of mixed metal oxides derived from lanthanum-containing layered double hydroxides to promote pollutant removal by means of photocatalytic degradation with the mineral surfaces. The objective of the present study was to investigate the synthesis of ternary MgAlLa mixed-metal oxides (MgAlLa-M) with various Mg/Al/La molar ratios through a hydrotalcite-like precursor route by co-precipitation of appropriate amounts of metal salts from homogeneous solution, followed by calcination at 600°C. The crystal structure, surface morphology, and optical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and UV-Vis diffuse reflectance spectroscopy (DRS). Analysis by XRD showed that MgO, La2O3, MgAl2O4, and La10Al4O21 phases coexisted in calcined samples as MgAlLa-M. The samples showed a small band gap of 3.11–3.35 eV according to DRS. The photocatalytic activities of the samples were evaluated by degradation of methylene blue (MB) under visible light irradiation. MgAlLa-M had better photocatalytic properties than hydrotalcite precursors, and the MgAlLa-0.5-M possessed the best photocatalytic activity. The photocatalytic degradation efficiency of MB dye with MgAlLa-0.5-M under visible light irradiation for 1 h was 99.89% in the presence of H2O2, which exceeded the binary MgAl-M (84.06%) under the same conditions. The high photocatalytic activity of the sample was attributed to the addition of La(III). In addition, the possible mechanism of photocatalytic degradation of MB by MgAlLa-M was discussed. The results showed that •O2– plays a major role in the MgAlLa-0.5-M/H2O2 system.

Studies of the mineralogy of the northern part of the Atlantic Coastal Plain indicate that the heavy mineral content of the Cretaceous and Cenozoic sediments consists basically of two suites, a restricted mineral suite characterized by very stable minerals, and a full suite consisting of a great variety of igneous and metamorphic minerals. The restricted suite occurs in the nonmarine sediments and the full suite in the marine deposits.

The nonmarine Cretaceous deposits consist of kaolinite, with variable amounts of illite and its alteration products. Transition sediments like those of the Magothy formation contain kaolinite, illite, chloritic material and, occasionally, some montmorillonite. The marine sediments are characterized primarily by illite and montmorillonite. Thus, a limited heavy mineral suite and kaolinite are associated in nonmarine deposits, and a full suite and montmorillonite are found in marine sediments.

On the basis of available data the conclusion is reached that the different heavy mineral and clay mineral suites are a result of different source areas for the marine and non-marine sediments.

The suggestion is made that the formational concept cannot be employed with regard to the nonmarine sediments of the northern Coastal Plain but that, instead, a new concept be adopted based on depositional conditions within the framework of the control of the heavy and clay mineral assemblages.

Bentonite is considered as an ideal buffer/backfill material for preparing an engineering barrier for high-level radioactive waste (HLW) disposal. During initial sample preparation, the tendency of wet bentonite powder to gather into large agglomerates and the water to be spread unevenly in the traditional water content adjustment process decreases the homogeneity of compacted bentonite. The main purpose of this study was to solve this problem by applying a new wetting method, which mixes ice powder with bentonite powder (the ice-bentonite mixing method). This new method was used to adjust the water distribution in Gaomiaozi County, China (GMZ) bentonite powder and was compared to the traditional spray method. The screening method was used to separate macro-agglomerates (≥ 0.25 mm) from the water and bentonite mixture. The properties, the content of the various size agglomerates in loose mixtures, and the heterogeneity defects observed in compacted bentonite were compared. An index (P) was defined to quantitatively evaluate the water distribution in a loose bentonite/water mixture. Macro-agglomerates in loose mixtures produced heterogeneities in water content, density, and shrinkage. By using the ice-bentonite mixing method, fewer macro-agglomerates were formed and a homogeneous distribution of water was produced in the compacted bentonite. A homogeneous water distribution had the tendency to decrease the number of shrinkage cracks after the drying process and to maintain high mechanical strength in the compacted bentonite. Although the production of ice powder was laborious, the ice-bentonite mixing method has workability advantages: (i) a high mixing efficiency, (ii) a low mass loss rate, and (iii) a small deviation between measured water content and target water content. The low thawing efficiency of ice-bentonite mixtures can be solved by using a microwave-assisted thawing method. This research can improve the sample preparation method used to produce compacted buffer/backfill materials for HLW disposal.

Alteration of basalt is a ubiquitous process on the vast oceanic crust surface and results in the formation of secondary-phase minerals that include clay minerals and Fe-(oxyhydr)oxides. Thus, this process is a significant consequence of water/rock interactions that could reveal the (bio)geochemical conditions of formation. Core samples at the basalt/sediment interface from a depth of 74.79 m below sea floor (mbsf) were recovered during the International Ocean Discovery Program (IODP) expedition 329 (2010.10.10–2010.12.13) in the South Pacific Gyre (SPG). Two distinct regions of yellow- and red-colored sediment were observed. The mineralogy, elemental composition, Fe oxidation state, and mineral structure of the altered basalt samples were analyzed using transmission electron microscopy (TEM) with selected area electron diffraction (SAED) patterns, energy dispersive spectroscopy (EDS), electron energy loss spectroscopy (EELS), and micro X-ray fluorescence (μ-XRF). In the yellow sediment, K-nontronite and feroxyhyte (δ’-FeO(OH)) were the dominant mineral phases, while Mg-rich smectite (saponite), chlorite, and hematite were found predominantly in the reddish sediment. The appearance of K-nontronite and feroxyhyte mineral assemblages in altered sediment indicated that oxidative conditions prevailed during basalt alteration. Variation in the Fe-oxidation states in the K-nontronite structure, however, may indicate that local reducing conditions persisted throughout the biogeochemical reactions.

X-ray diffraction, differential thermal, chemical analysis and cation exchange data indicate a progressive genesis upon hydrothermal alteration of rhyolitic materials in an extensive fault zone. Kaolinite, a Ca-Mg beidellite, mixed-layer beidellite-hydrous mica and beidellite-vermiculite clay minerals, quartz, cristobalite and feldspar commonly occur in the deposit.

Detailed studies show that the sequence of the 2:1 clay mineral alteration is beidellite-hydrous mica mixed-layer → beidellite-vermiculite mixed-layer → beidellite. This mineralogical change parallels a progressive decrease in the layer charge and amount of fixed K+ present and an increase in exchangeable Ca+ and Mg+ respectively.

The influence of dissolved species and particle morphology on the electrokinetic behavior and the initial yield stress values of Cuban lateritic aqueous suspensions was studied. The lateritic samples were mixtures of serpentine and goethite in different relative proportions. The addition of silicate and Mg ionic species, which are normally found in natural waters used in industrial processes, affected the electrokinetic and flow behavior of the lateritic suspensions. Specific adsorption of these species on particle surfaces was shown by a shift of the isoelectric point and the maximum of the initial yield stress to more acidic pH (Si ionic species adsorption) and more basic pH (Mg ionic species adsorption), when compared to suspensions containing only non-adsorbing electrolytes. The initial yield-stress values determined in samples consisting entirely of goethite varied from sample to sample. A detailed crystallochemical characterization revealed that these changes were associated with the axial ratio (i.e. ratio of particle length to width) of the mineral particles. Goethite samples with larger particle size (smaller number of particles for a given solid concentration) and greater axial ratios presented initial yield-stress values greater than those goethites with smaller particle size and lower axial ratio.

The aim of the present study was to discriminate between distinct types of clay units by applying multivariate statistical techniques, which have seldom been applied to the exploitation of ceramic clays. At the outcrop scale, texturally similar argillaceous or clayey layers of different ceramic types cannot be effectively distinguished, which can result in the misuse and loss of raw materials. Representative samples of clayey raw materials from central Portugal Cenozoic deposits with potential use in the manufacture of structural clay products were first assessed for granulometric, mineralogical, chemical, and technological properties. Based on those properties and the use of multivariate statistical techniques, i.e., factor analysis (FA) and cluster analysis (CA), a novel statistical approach that combined all these variable properties was produced. This approach made it possible to distinguish the ceramic suitability and perceive which parameters most influence that suitability. The use of R-mode FA made it feasible to differentiate and group samples based on the most influential variables: the contents of Al2O3, Fe, illite, quartz, feldspars, and K2O. The use of R-mode CA substantiated the FA results in the identification of influential variables, such as Al2O3, Fe, and illite. The use of Q-mode CA established two main clusters: clayey-silt samples and sandy and/or feldspathic samples, the clayey-silt samples encompassed three sub-clusters. These three sub-clusters match ceramic types with different suitabilities and relate sample stratigraphic setting to the encompassing stratigraphic units. Diagrams that relate the grain size, the content of different oxides, the content of different minerals, and the plasticity to the ceramic suitability illustrate the CA groupings. An adequate blend of sand and clay for red stoneware (bricks and tiles) manufacture was indicated as a major requirement for most raw materials of the clayey-silt cluster. Raw materials represented by the sandy and/or feldspathic cluster can either be used to blend with materials that lack sand or to blend with excessively plastic samples.

This work describes the separation of alunite from natural alunitic kaolins by applying a selective flocculation procedure. In order to determine the most efficient separating procedure preliminary experiments were performed with artificial mixtures of alunite and kaolin. The same procedure was then applied to natural alunitic kaolin which enabled the preparation of kaolin of considerable purity.

The birefringence of complexes of montmorillonite with aromatic liquids depends on the type of liquid, and this fact was used to determine the proportion of expanding layers in some partly expanding minerals. A simple method of assessing samples for the presence of expanding minerals probably could be devised on the same lines.

A relation was derived which describes negative adsorption (salt exclusion) in systems in which double layer interaction takes place but where the surface potential remains finite, such as in clay pastes and sediments. Exclusion volumes calculated for montmorillonite pastes in equilibrium with 1:1 type electrolytes were found to compare favorably with data obtained by F. A. M. de Haan in an earlier study.