Dehydroxylated sericites were stirred in the various salt solutions, or washed several times with various salt solutions using a centrifuge. By these treatments a seriate of the 2M type was easily transformed into an interstratified mineral of the rectorite type when a sericite was treated with sodium salts, and random mixed-layer mineral was formed from 1M sericite. The formation of a rectorite-type mixed-layer mineral from 2M sericite can be explained by the (OH) bond direction after the extraction of the potassium ions.

In Upper Cretaceous-Tertiary marine shales (Campos Formation) from the Campos basin, Brazil, mixed-layer illite/smectite (I/S) has remained randomly interstratified to depths of 3500 m and to temperatures as high as 100°C, in contrast to the typical pattern of shale diagenesis in, for example, the Gulf Coast area. X-ray powder diffraction analysis of the bulk shale and several size fractions from samples from one well in the Brazilian basin and from one in the Gulf Coast region were carried out to assess the factors that might have controlled the lack of illitization in the Campos Formation shales.

In samples from the Gulf Coast well, the clay minerals are I/S (montmorillonite-type), discrete illite, chlorite, and minor kaolinite. In contrast, the clay minerals in samples from the Campos basin well are kaolinite, clay-size biotite, and I/S (nontronite-type). Kaolinite is abundant in this well, and the variation of its abundance with depth seems to reflect variations in sea-level stands. The original composition of the I/S (nontronite-type) was probably the main factor controlling the lack of illitization in the shales of the Campos Formation.

Chemical analysis by X-ray fluorescence (XRF) and calculated structural formulae of clay-size fractions of smectites from Cretaceous bentonites and illitic clays from Cretaceous, Devonian, and Ordovician bentonites and Jurassic and Permian sandstones indicate the nature and extent of various types of ionic substitution. The determination of tetrahedral (Al, Si) and octahedral (Al, Mg, Fe) composition shows the variable chemistry of these materials. Structural formulae of the illitic clays show that they have tetrahedral charges between 0.4 and 0.8 per half unit cell, and can be divided into phengitic types having octahedral charges of 0.2-0.4 and muscovitic types having octahedral charges <0.2. Evaluation of the formulae in the light of X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) data shows that the occupancy of non-exchangeable interlayer sites (predominantly K) varies from 47% to 90% of that of ideal muscovite. In some minerals as much as 20% of these sites is occupied by ammonium ions (determined independently). The amount of surface silicate charge balanced by non-exchangeable cations versus that balanced by exchangeable cations has been examined in conjunction with TEM data and suggests that in most samples the charges are about equal. The octahedral composition of smectites in Cretaceous bentonites precludes their having served as transformation precursors for most of the Cretaceous illitic bentonites. The results suggest that these illitic clays originated by neoformation.

Infrared spectroscopy is used to distinguish between octahedral and tetrahedral substitutions in an interstratified illite-smectite clay. The Hofmann-Klemen (Li) test suggests that the AlMg□ and FeMg□ octahedral vacancies are preferentially occupied by Li after thermal treatment at 250°C. The ammonium (Chourabi-Fripiat) test reveals the beidellitic character by the formation of two OH stretching modes upon deammonation. The illitic layers are not affected since K is not exchangeable.

A dispersion-centrifugation-decantation procedure was used to isolate various particle size fractions from a sample of clay (<2 µm fraction) separated by sedimentation from the Ap horizon of a Webster soil (fine-loamy, mixed, mesic Typic Haplaquoll). The 0.02–0.06 µm size fraction was found to be enriched in an illitic phase associated with randomly interstratified smectite/illite. X-ray powder diffraction, chemical analysis, and high-resolution transmission electron microscopy confirmed that most of the illitic material in the 0.02–0.06 µm size fraction was composed of two-layer elementary illite particles with a layer charge of −0.47 per formula unit. The results demonstrate that this low-charge illitic phase can be physically separated from soil materials and that the low-charge illitic phase has chemical, morphological, and mineralogical properties that are uniquely different from those of smectite and illite.

Pedogenic smectite from a young (Holocene) tropical soil was reacted in Al-rich solution at 150ºC for a range of reaction times (3 to 120 days) in orderto study mechanisms and rates associated with the transformation of smectite to kaolinite via interstratified kaolinite-smectite (K-S). As has been observed in tropical soils, the overall reaction rate is logarithmic, with rapid initial transformation of smectite to K-S with ~50% smectite layers, followed by progressively slower transformation of intermediate K-S to kaolinite-rich K-S and eventually Fe-kaolinite. Sub-micron hexagonal non-Fe-bearing kaolinite forms in the final stage (after 120 days) as a minor mineral in an assemblage dominated by Fe-kaolinite. The pedogenic smectite used as starting material consisted of two end-members, Fe-beidellite and Al-smectite, enabling comparison of reaction pathways. Fe-beidellite transforms to K-S or Fe-kaolinite within 3 days, whereas Al-smectite transforms much more slowly, appearing to reach a maximum rate in intermediate stages. This difference is probably due to hydrolysis of relatively weak Mg-O and Fe-O bonds (relative to Al-O bonds) in Fe-beidellite octahedral sheets, which drives rapid reaction, whereas the driving force behind transformation of Al-smectite is more likely to be related to stripping of tetrahedral sheets which reaches its maximum rate at intermediate stages. Multiple analytical approaches have indicated that Al is rapidly fixed from solution into smectite interlayers within K-S, and that K-S and Fe-kaolinite inherit octahedral Fe and Mg from precursor smectite; as the reaction progresses, octahedral sheets become progressively more Al-rich and Fe and Mg are lost to solution. These results demonstrate that: (1) early-formed pedogenic smectite in tropical soils is expected to transform to kaolinite via interstratified K-S; (2) K-S has a strong potential to sequester plant-toxic Al in tropical soil; and (3) the presence in tropical soils of Fe-kaolinites with relatively large cation exchange capacities may be related to inheritance of octahedral sheets from precursor smectite and K-S.

Tropical soils range from nutrient-depleted lateritic soils rich in halloysite or kaolinite to Inceptisols rich in interstratified kaolinite-smectite (K-S), smectite, or related 2:1 clays. Given the strong influence of clay minerals on tropical soil quality, better understanding of factors influencing their occurrence is important for modeling and managing tropical environments. This study examines the alteration of smectite to kaolinite by way of intermediate K-S and halloysite in a 120 ka moist tropical chronosequence. Iron-rich smectite (11.6 ± 2.2% Fe2O3) is the dominant mineral in Holocene soils (1–8 ka) originating from sediments rich in plagioclase and clinopyroxene. The cation exchange capacity (CEC) of smectite is 54–84 cmolc/kg and pH is 6.1 to 7.4. Within 50 ka, smectite fixes Al-hydroxy complexes into interlayers, K+ is retained preferentially over Ca2+, and 2:1 layers are stripped of tetrahedral sheets; the resulting K-S inherits flaky smectite crystal habit and the 2:1 layers — which only expand partially — include Al-hydroxy smectite and some illite-like layers. After 50 ka, the dominant mineral is K-S, the CEC is 18–28 cmolc/kg, and the pH is 5.3. Flaky Fe-kaolinite with ~10% residual smectite layers and halloysite (7.4% Fe2O3) also occur in 50 ka soil. The 120 ka soils are dominated by flaky Fe-kaolinite (<10% residual smectite layers) and halloysite (4.9% Fe2O3), and Fe-poor hexagonal kaolinite also occurs (5–10% of soil). The CEC is 11–16 cmolc/kg and the pH is 4.7–5.3.

Changes in crystal chemistry of the soil clays (decreasing Fe, Mg, Ca, and K; increasing Al) over time reflects two reaction mechanisms: (1) cell-preserved transformation of smectite layers to kaolinite layers that accompanies conversion of smectite to K-S and eventually kaolinite; this results in the formation of flaky Fe-rich kaolinites after 50 ka; and (2) dissolution of K-S followed by crystallization of halloysite. Neoformation of hexagonal kaolinite and/or halloysite with low Fe (<3% Fe2O3) follows dissolution of Fe-kaolinite or halloysite after 100 ka. This sequence is probably common in moist tropical soils and these findings may inform modeling of soil composition in tropical landscapes where tectonic, volcanic, or geomorphic activity periodically exposes unweathered parent material, producing a range of soil ages.

Structural transformations between the different hydration states of three vermiculite samples from Sta. Olalla (Huelva, Spain), Paulistana (Piaui, Brasil) and West China, have been observed by X-ray diffraction at atmospheric pressure, P = 1.4 x 10–2 mbar and P = 2.4 x 10–4 mbar. The samples were studied in flake and powder forms. The effect of vacuum has been proven to be the same as that of temperature, i.e. it causes dehydration of vermiculite, but with a different evolution through the different hydration states. In fact, under vacuum, the process seems to be inhibited at a one-water layer hydration state (1-WLHS), without a further dehydration of samples to a zero-water layer hydration state (0-WLHS).

Furthermore, the dehydration process has been shown to occur through different interstratified states in each vermiculite. This result has been related to the interlayer Mg-cation content, due to its affinity to water molecules. The interstratified states have been analysed by the direct Fourier-transform method. The vermiculite from Sta. Olalla exhibits the most complex process, with formation of three different interstratified phases: two phases characterized by an interstratification of interplanar distances, d = 11.5 –13.8 Å and d = 9.6 –11.5 Å , respectively, and a practically segregated phase characterized by d = 13.8 Å . For the vermiculite from China, an interstratified phase not previously reported has been found, with an interplanar distance of 12.10 Å.

The inhibition of dehydration at 1-WLHS, as observed, could be used in applications such as adsorption and separation technology of gases and liquids, or in heterogeneous catalysis processes.