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Research indicates that smectite, a clay mineral, emerges from an intermediate phase in the formation of kaolinite from silicate gels. Studies were conducted for both dioctahedral and trioctahedral smectite.

We studied mixed-layer illite-smectite (I/S) (< 1 or 0.5 [[micro]meter] size fractions) in 28 diagenetic bentonite samples, Pliocene to Ordovician in age, from different locations in North America and Europe to investigate the smectite-to-illite transformation mechanism. XRD-measured illite contents ranged from 3 to 100%, and layer ordering varied continuously from R = 0 to R [greater than or equal to] 3. XRD polytype analysis showed that with progressive illitization, US changes from a predominantly cis-vacant to a trans-vacant structure, although considerable scatter is present in the data. There is no evolution of illite in the I/S from 1[M.sub.d] to 1M polytypes with progressive illitization. Microprobe chemical analysis and combustion analysis for N showed that [Mathematical Expression Omitted] comprised 9-22% of the total fixed cation content. We calculated an interlayer charge for the illite end-member of 1.5 per [O.sub.20](O[H.sub.4]). Sample morphology was studied by atomic force microscopy, which showed a constant aspect ratio and particle diameter over the whole I/S series. Particle thickness increased with percent illite. Oxygen isotope compositions of the I/S clays did not display any systematic trends. Our results suggest that illitization of bentonite US proceeds via a solid-state mechanism, with local lattice rearrangements that permit structural (octahedral cis/trans occupancy) and chemical changes in 2:1 layers and cause interlayer coalescence.

An experiment using XRD and TG analysis as well as BET surface area measurements is conducted to determine the effects of humidity on a mixed-layer of illite/smectite containing 11% of illite. Results show that exchange cation influences the absorptive capacity of clay by affecting the surface area of the said material. The number of water moles found per half formula unit of the clay is estimated to be 4.5.

A series of bentonite illite/smectite with a range of Fe content (0.08-0.95 atoms per half formula unit) and illite composition (3-97% illite) was analyzed by Fourier transform infrared spectroscopy, 27Al magic-angle spinning NMR spectroscopy and theoretical computations by reverse Monte Carlo simulations. All samples showed a high dispersion of the Mg cations and a tendency for Fe segregation which increased with progressing illitization. The illite-rich samples indicated medium- or long-range ordering of the octahedral cations.

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This study investigated soil clay mineralogy of mangrove forests along the Brazilian coast in eight regions of different environmental characteristics, with a focus on the crystallochemical features and genesis of 2:1 phyllosilicates. Samples from two different depths (0-30 and 60-90 cm) and two clay size fractions (<2 and <0.2 mm) were studied. The analytical tools used were x-ray diffraction, Fourier-transform infrared spectroscopy, and transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS). A complex assemblage was found in both fractions, including high proportions of kaolinite, illite (Fe-illite/glauconite), and smectite (Fe-beidellite, Fe-montmorillonite), minor amounts of gibbsite and quartz, and traces of K-feldspar, halloysite, and amphibole crystals (TEM-EDS data). Evidence of illite-smectite and possibly kaolinite-smectite mixed-layer phases was found in the <0.2-mm fraction. An authigenic transformation process likely taking place, from kaolinite to Fe-illite/glauconite, through transitory kaolinite- smectite and illite-smectite phases. The reaction is triggered by high Fe activity in solution generated by dissolution of Fe oxides and pyrite present in the sediment, at approximately neutral pH and high salt content in the water. Smectite illitization takes place by substitution of Al3+ for Si4+ in the tetrahedral sheet, of Fe and Mg2+ for Al3+ in the octahedral sheet, and progressive Fe reduction, all of which produces an increase in the layer charge and K uptake. The sequential nature of the transformation (kaolinite-smectite-illite) suggests a solid-state transformation process. Two unusual kaolinite-rich mangroves were found, indicating low reactivity or high deposition rate of continental sediments of soils derived from the Barreiras Group, dominated by kaolinite. [ABSTRACT FROM AUTHOR]

Biological activity plays a substantial role in the geochemistry of the Earth's surface. Particularly interesting are effects on clay formation because clays are abundant and have high surface-to-volume ratio, resulting in clays making up a large fraction of the overall mineral-fluid interface and having an effective control of mineral reactions. Thus, biological control on clay composition would affect element budget globally and the mineralogy of subsequent diagenetic processes. Biological acceleration of clay production would result in enhanced clay control of mineral reactions and faster organic C sequestration, by adsorption on clay minerals, with implications for the C and related cycles. We investigated the combined effect of microbial activity and water chemistry on the composition of neoformed clay by reacting volcanic glass with natural waters covering a large composition range (fresh water from a lake and a spring, seawater, and hypersaline water). The microbes (bacteria, fungi, and algae) were totally or partially identified using molecular and microscopy techniques. The solid alteration products were analyzed using cryo-SEM to investigate the mineral-microbe interface and TEM-AEM to study the composition of the neoformed clay. The solution chemistry was also investigated. We found that clay composition was controlled mainly by glass chemistry, rather than biological activity, through a mechanism of in situ transformation. The resulting clay was Al-rich (dioctahedral composition). In one case (inorganic experiment, freshwater lake), the specific inorganic conditions of pH and Mg and Si concentration promoted formation of Mg-rich (trioctahedral clay). Microbes, however, did influence clay composition by confining glass grains in biofilms where water chemistry is significantly different from the bulk solution. Alteration in such conditions generated significant amounts of trioctahedral, Mg-rich clay in the hypersaline water experiment, whereas it favored production of dioctahedral, Al-rich clay in the freshwater lake experiment. It is thus demonstrated that biofilms can exert an effective control on clay mineralogy. [ABSTRACT FROM AUTHOR]

The hydrothermal reactivity of the <1 µm fraction, K-saturated SWy-2 Wyoming low-charge montmorillonite was studied in the 250-400 °C temperature range with reactions lasting between 5 and 120 days, with a solid/solution mass ratio of 1:10, and in 1 mol/L KCl solution. From X-ray diffraction (XRD) profile modeling results on K-saturated and ethylene-glycol solvated samples the illitization process appears to occur as a progressive replacement of expandable layers by layers with illitic behavior, in a single illite-smectite phase. However this treatment overestimates the amount of illite layers because of the presence of smectitic non-expandable layers. This was revealed by calcium exchange of the products, which causes re-expansion of the apparent illite layers. The illitization model then obtained consists of four phases with increasing illite content: discrete smectite, a randomly interstratified mixed-layered mineral (MLM) and two ordered MLMs that progressively replace the phases with less illite content. This polyphase model is consistent with results from transmission electron microscopy and chemical microanalysis, which show several types of particle morphology with different interlayer K content and Al-for-Si substitution that seem to correspond to the several phases detected by XRD. Thus, the actual illitization mechanism of smectite in our experiments is not a progressive reaction but a dissolution-precipitation process following the Ostwald step rule in which metastable smectite transforms into illite through a series of metastable illite-smectite phases. [ABSTRACT FROM AUTHOR]

Abstract: Amino acid–smectite interaction may have catalyzed prebiotic reactions essential for the emergence of life. Lysine solutions (0.05 M) were reacted with Na-smectite in adsorption–desorption experiments. The lysine–smectite complexes were heated at 80 °C for 10 days to investigate (1) possible slow processes taking place at surface temperature that would be accelerated at higher temperature and (2) processes taking place in hydrothermal systems. Three sets of experiments were performed: thermal treatment in closed tubes and water added regularly; thermal treatment in closed tubes without adding water; and thermal treatment in open tubes and no added water. After lysine desorption (displacement with 0.1 M CaCl2), the solutions were investigated using circular dichroism (CD) and the smectite samples using FTIR and CHN elemental analysis. CD spectra were dependent on the solution pH, which was controlled by lysine protonation state. The lysine protonation state was altered by the adsorption–desorption process, with a higher Lys+/Lys± ratio after desorption. The CD and CHN analyses show that the thermal treatment in a moist state causes stronger smectite–lysine binding. FTIR data suggest that the stronger binding is caused by more or stronger H bonds between –NH+ 3 lysine groups and smectite basal O atoms. [Copyright &y& Elsevier]

Phlogopite flakes strewn on the soil of Caldara di Manziana (Italy) display multiple minute perforations. The site is a caldera linked to recent volcanism (90 ka to 0.8 Ma) with present emanations of CO2 (~150 t d−1) and H2S (~2.55 t d−1). Stereomicroscopy and SEM–EDX observation of the phlogopite crystals shows holes and depressions <200 µm to 2 mm across. They are circular, pseudo-hexagonal, or irregular. Within the depressions, there are deposits of phlogopite alteration products consistent with a sulphuric acid attack, showing loss of Mg and K. Some are thin and homogeneous; others are thick, irregular, and chemically heterogeneous, including plates, flakes, tubes of Fe-beidellite or Fe-bearing halloysite, silica, Fe oxides, and gypsum. Areas of phlogopite surface are also altered. Sulphuric acid is produced from the H2S gas by the mediation of sulphur-oxidizing bacteria. Pseudo-hexagonal perforations are interpreted to result from slow acid attack with dissolution controlled by phlogopite crystal symmetry. Some depressions developed surrounding films of pseudo-hexagonal shape, interpreted as jarosite crystallizing radially outwards from the depressions. This style of acid attack is possibly promoted by local high humidity and precipitation that generate long-lived water droplets and films on mineral surfaces where sulphuric acid is active for prolonged times. [ABSTRACT FROM AUTHOR]

The physicochemical and textural characteristics of river sediments and, essentially, their clays, are at the center of a network of biological and geochemical factors that are mutually modifying. Therefore, the contamination, the characteristics of the clays, and the associated microorganisms strongly influence each other. In this work, sediments from two sites of the urban Reconquista River, near Buenos Aires City, Argentina, exposed to different environmental contexts were characterized. The huge differences in the organic matter content in the vertical profile between both sediments strongly evidenced the polluted status of San Francisco (SF) site as opposed to the Dique Roggero (DR) site. Thorough physicochemical and textural characterization of the sediments and their clay fraction performed by pH, Oxidation-reduction potential (ORP), spectrophotometry, XRD, laser diffraction, N2 adsorption–desorption isotherms, EDS, and SEM measurements revealed that organic matter (DR: 41 ± 5 g kg−1; SF: 150 ± 30 g kg−1) intervened in the retention of heavy metals (DR: 5.6 mg kg−1 Zn, 7 mg kg−1 Cu, 3.1 kg−1 Cr; SF: 240 mg kg−1 Zn, 60 mg kg−1 Cu, 270 mg kg−1 Cr) and affected the level of association and the formation of mineral–organic aggregates (DR: 15 ± 3 μm; SF: 23 ± 4 μm). This can be decisive in the surface interaction required for the establishment of bacterial assemblages, which determine the biogeochemical processes occurring in sediments and have a key role in the fate of contaminants in situ and in the remediation processes that need to be applied to restore the anoxic contaminated sediments. [ABSTRACT FROM AUTHOR]