Widespread lateritized ultramafic rocks in the southern part of the Muratdağı region of Turkey constitute a significant source of Ni-Cr-bearing ore with economic potential. However, no mineralogical or geochemical characterizations of these important materials have been performed previously. The aim of the present study was to describe the mineralogy, geochemistry, and genesis of Ni-Cr-bearing smectite in garnierite and ferruginous saprolite associated with the lateritized ophiolite-related ultramafic rocks. The lateritic zones are well developed over serpentinized harzburgitic mantle peridotites. The lateritized units and related bedrocks were examined using polarized-light microscopy, X-ray diffraction, scanning and transmission electron microscopies, and chemical and isotopic methods. The garnierite-containing saprolites are enriched in smectite, Fe-(oxyhydr)oxide phases, and opal-CT. Micromorphological images revealed that flaky smectite and, locally, Fe-rich particles, alunite, gypsum, gibbsite, and sulfur crystals developed along the fractures and dissolution voids. The development of saprolite demonstrates chemical weathering. The presence of silicified and Fe-(oxyhydr)oxide phases associated with gypsum, alunite, and local native sulfur in vertical and/or subvertical fractures and fault infillings are indicative of hydrothermal processes along the extensional, tectonically related fault systems. Chemical weathering and hydrothermal processes, which probably started during the Oligocene and Miocene, led to the formation of nontronite, Fe-bearing montmorillonite, and local Fe-rich kaolinite. Nickel and Cr are concentrated significantly in the saprolite zone and are positively correlated with Fe2O3 content, which is controlled by the formation of nontronite, montmorillonite, and Fe-(oxyhydr)oxide phases. Nickel-Cr-bearing nontronite and montmorillonite precipitated from alkaline water as a result of the increasing (Fe2O3+Al2O3+Cr2O5+Ni+Co)/(MgO+SiO2) ratio under the control of both chemical weathering and hydrothermal processes. The Fe and Mg (associated with Ni and Cr) required for the formation of smectite were supplied by solutions from both chemical weathering and hydrothermal alteration of Ni-Cr-bearing olivine and pyroxene in the harzburgitic bedrock; the Al was supplied by schists, granite, and volcanic units.

The state and dynamics of water and cations in pure and mixed Na-Cs-montmorillonite as a function of the interlayer water content were investigated in the present study, using Monte Carlo and classical, molecular-dynamics methods. While highly idealized, the simulations showed that the swelling behavior of hetero-ionic Na-Cs-montmorillonite is comparable to the swelling of a homo-ionic Na- or Cs-montmorillonite. The mixed Na-Cs-montmorillonite is characterized by intermediate interlayer distances compared to homo-ionic Na- and Cs-montmorillonites. Dry, hetero-ionic Na-Cs-montmorillonite is characterized by a symmetric sheet configuration, as is homo-ionic Cs-montmorillonite.

We found that at low degrees of hydration the absolute diffusion coefficient of Cs+ is less than for Na+, whereas at greater hydration states the diffusion coefficient of Cs+ is greaterthan for Na+. An analysis of the relative diffusion coefficients (the ratio between the diffusion coefficient of an ion in the interlayer and its diffusion coefficient in bulk water) revealed that water and Na+ are always less retarded than Cs+. With large interlayer water contents, tetralayer or more, Na+ ions preferentially form outer-sphere complexes. The mobility perpendicular to the clay surface is limited and the diffusion is equivalent to two-dimensional diffusion in bulk water. In contrast, Cs+ ions preferentially form ‘inner-sphere complexes’ at all hydration states and their two-dimensional diffusion coefficient is less than in bulk water.

The question remains unanswered as to why experimentally derived relative diffusion coefficients of Cs+ in the interlayer of clays are about 20 times less than those we obtained by classical molecular dynamics studies.

Sedimentary and diagenetic processes control the distribution of clay minerals in sedimentary basins, although these processes have seldom been studied continuously in continental sedimentary basins. The Songliao Basin, northeast China, is a large continental, petroleum-bearing basin, and provides a unique study site to understand the sedimentary and diagenetic processes that influence clay assemblages. In this paper, the clay mineralogy of a 2500 m-thick Late Cretaceous (late Turonian to Maastrichtian) terrestrial sedimentary succession (SK-1s and SK-1n cores), retrieved by the International Continental Scientific Drilling Program in the Songliao Basin, was examined. The objective was to determine the diagenetic and paleoenvironmental variations that controlled the formation of clay mineral assemblages, and to determine the thermal and paleoenvironmental evolution of the basin. The results from both cores show that illite is ubiquitous through the succession, smectite is frequently encountered in the upper strata, and ordered mixed-layer illite-smectite (I-S), chlorite, and kaolinite are abundant in the lower strata. Burial diagenesis is the primary control on the observed decrease of smectite and increasing illite, I-S, and chlorite with depth. Observations of clay-mineral diagenesis are used to reconstruct the paleotemperatures and maximum burial depths to which the sediments were subjected. The lowermost sediments could have reached a maximum burial of ~1000 m deeper than today and temperatures ~50°C higher than today in the latest Cretaceous. The transition of smectite to I-S in the SK-1 cores and the inferred paleotemperatures provide new constraints for basin modeling of oil maturation at elevated temperatures in the Songliao Basin. Authigenic kaolinite and smectite are enriched in sandstones with respect to the coeval mudstones from the SK-1n core, as a result of early diagenesis with the participation of primary aluminosilicates and pore fluids. In the upper part of both SK-1 cores, variations in smectite and illite were controlled primarily by paleoenvironmental changes. Increases in smectite and decreases in illite from the late Campanian to Maastrichtian are interpreted as resulting from increasing humidity, a conclusion consistent with previous paleoenvironmental interpretations.

Natural smectites bind aflatoxins from water effectively, but the complex chemical environment in the guts of mammals and other animals can limit binding of aflatoxins. Many efforts have been made to enhance the adsorption capacity and affinity of smectites for aflatoxins in the presence of biological compounds. The main objective of the present study was to modify smectite structures by pillaring and cation exchange to enhance aflatoxin B1 adsorption capacity and selectivity. Smectite was pillared with Al and Al-Fe polycations or saturated with Ca, Mg, Zn, or Li. Structural changes in smectites with or without heat treatment were determined using X-ray diffraction and Fourier-transform infrared spectroscopy. Equilibrium aflatoxin B1 adsorption to the smectites was measured in aqueous solution and in simulated gastric fluid. Pillaring with the polycations expanded smectites in the z-direction to 18.6 Å and the expansion was stable after heating at 500°C. Changes in the Al–OH–Al infrared bands in the stretching region supported the formation of pillared clays. Migration of Mg, Zn, and Li into the octahedral sites of the smectite was observed as Mg and Zn saturation yielded a d spacing of 15 Å at 200°C which collapsed to 9.6 Å at 400°C. The 14.6 Å peak of the Li-saturated smectite collapsed to 9.6 Å at 200°C while the 15 Å Ca-saturated smectite peak was stable up to 400°C. The unheated Al- and AlFe-pillared smectites adsorbed significantly more aflatoxin B1 from an aqueous suspension than did unpillared clay. In both water and simulated gastric fluid, heat treatment decreased aflatoxin B1 adsorption to pillared smectites, but heat treatment increased aflatoxin B1 adsorption to unpillared smectites. Without heat treatment, smectites saturated with divalent cations (Ca, Mg, Zn) adsorbed more aflatoxin B1 from an aqueous suspension than the smectite saturated with a monovalent cation (Li). Ca-saturated smectite showed the greatest aflatoxin B1 adsorption, 114 g kg–1, from aqueous suspension after 400°C heat treatment. The Zn-, Mg-, and Li-saturated smectites showed maximum aflatoxin adsorption of 107, 93, and 90 g kg–1, respectively, after 200°C heat treatment. From simulated gastric fluid with pepsin, the 200°C heated, Zn-saturated smectite had maximum aflatoxin B1 adsorption of 68 g kg–1. Pillared smectites effectively adsorbed aflatoxin B1 from aqueous suspension, but Ca- and Zn-saturated smectites after heat treatment might improve the selectivity of smectites for aflatoxin B1 over pepsin and enhance the efficacy of smectite as a feed additive.

This study was undertaken to investigate the changes in flocculation properties of Fe-rich smectite (nontronite, NAu-1) suspensions, including settling velocity, aggregate size and floc architecture associated with microbial Fe(III)-reduction in the smectite structure. The dissimilatory Fe-reducing bacterium Shewanella oneidensis MR-1 was incubated with lactate as the electron donor and structural Fe(III) as the sole electron acceptor for 3, 12, 24 and 48 h in an anaerobic chamber. Two controls were prepared; the first was identical to the experimental treatments except that heat-killed cells were used (non-reduced control), and the second control was the same as the first except that the incubation was carried out in an aerobic environment. The extent of Fe(III) reduction for the 48 h incubation was observed to reach up to 18%. Neither the non-reduced control nor the aerobically inoculated sample showed Fe(III) reduction. Compared with the non-reduced control, there was a 2.7 μm increase in mean aggregate size and a 30-fold increase in average settling velocity in the bioreduced smectite suspensions as measured using a Micromeritics Sedigraph®. The aerobically inoculated smectite showed a similar aggregate-size distribution to that of the non-reduced control. Significant changes in physical properties of smectite suspensions induced by microbial Fe(III) reduction were measured directly using transmission electron microscopy. The floc architecture of bioreduced smectite revealed less open structures compared to those of a non-reduced control. The aspect ratio (thickness/length) of individual smectite particle increased from 0.11 for the non-reduced control to 0.18 on average for the bioreduced smectite suspensions. The effects of pH on the clay flocculation were minimal in this study because the value of pH remained nearly constant at pH = 7.0–7.3 before and after the experiments. We therefore suggest that the increase in net negative charge caused by microbial Fe(III) reduction significantly promoted clay flocculation by increasing the electrochemical attraction in the smectite suspensions.

Due to the great technological importance of the microstructure of kaolinite, characterizing its evolution during dry milling of kaolin and analyzing the microstructural information obtained from different methods were the main aims of this work. The microstructural alteration of kaolinite is evaluated by X-ray diffraction and electron microscopy methods, comparing the results obtained and analyzing the correlations between them. The Warren-Averbach and Voigt-function methods of X-ray diffraction microstructural analysis have been applied successfully to the study of the effects of two different, vibrating-cup dry-milling configurations in the microstructure of kaolinite from the reflections corresponding to (001) diffracting planes. The crystallite-size estimates obtained from the two methods correlate well. Field emission scanning electron microscopy measurements of kaolinite particle thickness are in good agreement with the crystallite size estimated by the two methods. The Warren-Averbach method also provided estimates of the contribution to line broadening. Vibrating-cup milling has been proved to be a more efficient method of strain comminution of kaolinites than other milling techniques, reaching extensive microstructural degradation within seconds.

Red clay is considered to be of significant value to the economy in Morocco, particularly in the Safi region, because of its abundance. This raw material has long been known for its quality in the manufacture of clay materials, but its use was limited to traditional ceramics. The red clay raw material was the subject of the current study with the objective of opening new industrial applications that will give added value to the Safi red clay. The physicochemical, mineralogical, and thermal properties of the Moroccan red clay were determined by X-ray fluorescence (XRF), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis, X-ray diffraction (XRD), oriented aggregate, and particle-size analyses, powder density by helium pycnometry, carbonate content using the Bernard method, differential thermal analysis (TG–DTA), and the BET surface area. The compacted dry powder particles were calcined at three sintering temperatures: 900, 1000, and 1100°C for 2 h. The effect of sintering temperature on ceramic properties, such as apparent porosity, water adsorption, bulk density, and mechanical strength, was examined. Dense ceramics with lower porosity and greater mechanical resistance (~300%) were produced by increasing the sintering temperature from 900 to 1100°C. The conclusion was that the evolution of physicochemical and thermal properties is related to mineralogical changes, which show that anorthite is the major phase at higher temperatures.

The fungus Aspergillus flavus Link ex Fries can infect grains and oil seeds and develop Aflatoxin B1 (AfB1) in the fieldor in storage. Aflatoxin contamination is a serious health hazard — it is extremely toxic and hepatocarcinogenic for animals and humans. A practical approach to solve this problem is to use smectite clay as an amendment to animal feed. The objective of this research is to investigate smectite clay—AfB1 interactions by employing Fourier transform infrared (FTIR) spectroscopy to determine how clay composition influences AfB1 adsorption by smectites. When AfB1 was present in the clay, the spectral region from 1800 to 1300 cm−1 was altered, and the regions between 4000 and 1800 and 1300 and 400 cm−1 were unchanged except for the intensity in the broad region near 3400 cm−1 related to the abundance of water. The 1300–400 cm−1 region is attributed only to smectite clay properties, and it relates to the relative adsorption potential of the different smectites. Bonding between AfB1 and smectite clay appears to be in the furan rings. Other possible bonding is with the two oxygens in the coumarin ring of AfB1 and interlayer cations or their associated water molecules. The FTIR evidence of octahedral Fe in smectite and amorphous silica in the clays both indicate greater AfB1 adsorption potential. Other smectites with spectral absorption indicating predominantly Al in the octahedral positions adsorbed less AfB1.

Ecologic building materials such as adobe bricks have become of greater economic importance in recent years. In the present work, the addition of selected materials to improve the compressive and bending strengths of adobe bricks was tested. The raw material (loam UD) was analyzed for its mineralogical and chemical composition. The loam studied consisted of quartz, feldspar, and the clay minerals chlorite, vermiculite, illite, and kaolinite. Prerequisites for using this loam for brick making were its grain-size distribution and the absence of expandable clay minerals.

To optimize the compressive and bending strengths of the adobe bricks, seven natural and ‘eco-friendly’ synthetic additives were admixed with the raw material and homogenized.

From this material, small adobe bricks and bars were made. One series of bricks and bars was made without additives but instead was coated with a hydrophobic impregnation cream. The bricks were stored for up to 20 days at 100 and 75% relative humidity (RH). After 1, 5, and 20 days, the compressive and bending strengths were measured to identify the critical humidity level for brick strength. The compressive and bending strengths of loam UD at dryconditions without additives showed values of 9 N/mm2 and 4.8 N/mm2, respectively. With some of the additives, the strength improved by up to 30%. The greatest increases in strength were achieved by mixing the loam with Acronal S650. Finely ground trass and diatomite also increased the dry strength. After storage at high levels of RH, these mixtures lost >50% strength. In contrast, the loam mixed with blast-furnace slag has a small initial strength but showed the smallest decreases in strength after exposure to high levels of RH.

The sedimentary series from Academician Ridge, Lake Baikal, eastern Siberia, was examined using cation exchange capacity (CEC) to estimate the amount of expandable clay minerals (ECM) and high-temperature X-ray diffraction (HT-XRD) to determine their basic classification. The comparison of the magnetic susceptibility (MS) at sub-millennial resolution and the δl8O record of a reference Atlantic core (ODP 980) was used to create an age model. The most closely studied part of the series covered the major part of the last glacial cycle (120–20 ky BP). The HT-XRD analysis is based on monitoring the course of ECM dehydration with 5°C steps between 25 and 250°C and enabled us to improve the discrimination between ECM, chlorite and micas. The CEC obtained at millennial resolution showed that the neoformation of ECM in warmer periods of the last interglacial was either insignificant or fully compensated by their dissolution or dilution. The CEC record was correlated with the main climatic stages in the period studied. Both MS and CEC records reflected the environmental changes at about millennial resolution, including climatic instabilities between 117 and 73 ky BP (late MIS5).

Alkaline solutions have significant effects on the mineral composition and on the microstructure of bentonite; in relevant geoenvironmental engineering applications, therefore, the properties of bentonite buffer materials must be taken into consideration in the presence of alkaline solutions. The objective of the present study was to determine the effect of alkaline conditions on the swelling of bentonite mixed with sand. Bentonite-sand mixtures were soaked in a NaOH solution and allowed to react over prescribed periods of 6, 12, and 24 months. Swelling deformation tests were conducted on the alkali-treated bentonite-sand mixtures; the swelling of the mixtures decreased significantly with increased reaction time. The fractal ec-σ relationship (ec is void ratio of bentonite, σ is vertical stress) was employed to express the swelling characteristics of the alkali-treated mixtures, wherein the swelling coefficient decreased as the bentonite content was reduced. Dissolution traces over the clay surfaces degraded the microstructural phase, thereby slightly increasing the fractal dimension. At higher dosages of bentonite, the swelling of bentonite-sand mixtures always followed a similar ec-σ relationship as that found for bentonite alone. On the contrary, in the mixtures with a small bentonite content that surpassed the designated threshold pressure, the void ratio of clay in the mixtures deviated from the ec-σ curve due to the appearance of the sand skeleton. The bentonite content for a particular bentonite-sand mixture at which deviation from the ec-σ curve began was ~50%. This deviation was almost negligible at 50% initial bentonite content in the bentonite-sand mixtures; after treatment with NaOH solution, however, a pronounced deviation in the ec-σ curve was observed which was caused mainly by the decrease in the bentonite percentage. Finally, the vertical pressure threshold was also estimated using the ec-σ relation for bentonite-sand mixtures with small bentonite contents over a range of various alkaline solution reaction times.

The composition of altered volcanic ash of the Late Ordovician Kinnekulle bed was studied in geological sections of the Baltic Paleobasin. The composition of altered ash varies with paleosea depth from northern Estonia to Lithuania. The ash bed in shallow shelf limestones contains an association of illite-smectite (I-S) and K-feldspar, with the K2O content ranging from 7.5 to 15.3%. The limestone in the transition zone between shallow- and deep-shelf environments contains I-S-dominated ash with K2O content from 6.0 to 7.5%. In the deep-shelf marlstone and shale, the volcanic ash bed consists of I-S and kaolinite with a K2O content ranging from 4.1 to 6.0%. This shows that authigenic silicates from volcanic ash were formed during the early sedimentary-diagenetic processes. The composition of the altered volcanic ash can be used as a paleoenvironmental indicator showing the pH of the seawater or porewater in sediments as well as the sedimentation rate.

Acid-activated bentonites are utilized in many applications, including those that depend on their rheological properties and behavior, but little information is available regarding the rheological characteristics of this important industrial material. The purpose of this study was to investigate the effects of solids concentration, salt concentration, and pH value on the shear rate, shear stress, and other flow parameters of acid-activated bentonite suspensions. Activated Na-bentonite was prepared using sulfuric acid. Flow curves of the suspensions were modeled using the Herschel-Bulkley equation, which performed well for this system. The Herschel-Bulkley yield stress increased with the solids concentration and showed a maximum and minimum at the NaCl concentrations of 0.001 M and 0.01 M, respectively, and increased again slightly with further increases in NaCl concentration. The yield stress was at a maximum and a minimum at pH values of ≈5 and ≈7, respectively, followed by a slight increase with pH under alkaline conditions. The variations in dispersion rheological properties can be attributed to the change in the particle-association modes under different conditions.

Magnetite (Fe3O4) is a key economically valuable component in iron ore and is extracted by dissolution processes, but among the Fe (oxyhydr)oxides its solubility behavior is one of the least understood. The objective of this study was to improve understanding of magnetite dissolution mechanisms leading to thermodynamic equilibrium by comparing the dissolution of two solid samples, one synthetic and one industrial, using oxalic, sulfuric, and nitric acids at varying concentrations and temperatures. Of the three solid-liquid systems investigated, only the system consisting of magnetite and oxalic acid reached an equilibrium state within the duration of an individual experiment (6 h). In this system, increasing the acid concentration resulted in a significant increase in the equilibrium concentration of dissolved Fe. When dissolving synthetic and industrial magnetite, increasing the temperature not only increased the rate of reaction but also affected the concentration of dissolved Fe. Significant effects were observed when increasing the temperature from 15 to 35°C, but only slight differences were seen on further increases in temperature. Observations regarding the equilibrium state of the sulfuric and nitric acid systems could not be made because equilibrium was not reached. The most important individual observation regarding the equilibrium state of the nitric- and sulfuric-acid systems seems to be that in future studies a much longer reaction time is necessary, due to slow kinetics of the dissolution mechanism. A proton-based mechanism has been hypothesized as the one governing the dissolution of magnetite by these two acids, but only the dissolution of the industrial sample yielded results that were similar for these two acids and consistent with that hypothesis.

Using bentonites to adsorb aflatoxin is an effective method of minimizing the toxicity of aflatoxin to animals and humans. Early studies indicated a more than 10-fold difference in aflatoxin adsorption capacity among different bentonites. The determining mineralogical and chemical properties of the clays in aflatoxin adsorption are still poorly understood. The objective of this study was to test the hypothesis that a bentonite’s selectivity and adsorption capacity for aflatoxin is mainly determined by the ‘size matching’ requirement, on a nm scale, between the non-polar interlayer surface domains and the aflatoxin molecules. The non-polar surface domain size of smectites was varied by (1) selecting smectites with different charge densities; and (2) changing the valence and the size of exchange cations to control the amount of water in the hydration shells of the cations. Infrared spectroscopy and X-ray diffraction were also used to characterize the aflatoxin-smectite complexes to investigate if layer-charge density would affect the bonding strength between aflatoxin and the minerals. A large aflatoxin adsorption capacity and high selectivity for aflatoxin were achieved by selecting smectites that had low charge density as represented by their <110 meq/100 g cation exchange capacity. An individual smectite’s selectivity and adsorption capacity for aflatoxin could be enhanced or weakened by replacing the exchange cation. When the smectite was saturated with divalent cations that have smaller hydrated radius (e.g. Ba2+), the smectite’s adsorption capacity and affinity for aflatoxin were enhanced. Aflatoxin entered the interlayer of all six smectites tested. The strength of its bonding to the smectites was not affected by the layer-charge density of the smectites. The results confirmed the importance of nm-scale polarity and size match between aflatoxin molecules and the adsorbing sites on smectite. The high selectivity for aflatoxin can be achieved by selecting a smectite with adequate charge density or by replacing the exchange cations with divalent cations that have low hydration energy.