Cambridge University Press (CUP)

Quantification of mineral assemblages in near-surface Earth materials is a challenge because of the often abundant and highly variable crystalline and chemical nature of discrete clay minerals. Further adding to this challenge is the occurrence of mixed-layer clay minerals, which is complicated because of the numerous possible combinations of clay layer types, as defined by their relative proportions and the ordering schemes. The problem of ensuring accurate quantification is important to understanding landscape evolution because mineral abundances have a large influence on ecosystem function. X-ray diffraction analysis of the variable cation-saturated clay fraction in soil and regolith from the Calhoun Critical Zone observatory near Clinton, South Carolina, USA, was coupled with modeling using NEWMOD2 to show that mixed-layer clays are often dominant components in the mineral assemblages. Deep samples in the profile (>6.5 m) contain mixed-layer kaolinite/smectite, kaolinite/illite-like, kaolinite-vermiculite, illite-like/biotite, and illite-like/vermiculite species (with ‘illite-like’ defined herein as Fe-oxidized 2:1 layer structure with a negative layer charge of ~0.75 per unit formula, i.e. weathered biotite). The 2:1 layers in the mixed-layer structures are proposed to serve as exchange sites for K+, which is known to cycle seasonally between plant biomass and subsurface weathering horizons. Forested landscapes have a greater number of 2:1 layer types than cultivated landscapes. Of two nearby cultivated sites, the one higher in landscape position has fewer 2:1 layer types. Bulk potassium concentrations for the forested and two cultivated sites show the greatest abundances in the surface forested site and lowest abundance in the surface upland cultivated site. These observations suggest that landscape use and landscape position are factors controlling the mixed-layer mineral assemblages in Kanhapludults typical of the S.E. United States Piedmont. These mixed-layer clays are key components of the proposed mechanism for K+ uplift concepts, whereby subsurface cation storage may occur in the interlayer sites (with increased negative 2:1 layer charge) during wetter reduced conditions of the winter season and as biomass decay releases cation nutrients. Cation release from the mixed-layer clays (by decreased 2:1 layer charge) occurs under drier oxidized conditions during the growing seasons as biota utilize cation nutrients. The types and abundances of mixed layers also reflect long-term geologic factors including dissolution/alteration of primary feldspar and biotite and the subsequent transformation and dissolution/precipitation reactions that operate within the soil horizons. Thus, the resulting mixed-layer clay mineral assemblages are often complex and heterogeneous at every depth within a profile and across landscapes. X-ray diffraction (XRD) assessment, using multiple cation saturation state and modeling, is essential for quantifying the clay mineral assemblage and pools for cation nutrients, such as potassium, in the critical zone.

In non-aqueous systems, kaolinite can show, in addition to the physical interactions, considerable chemical activity. This study considers the chemical reactions that can occur at the kaolinite surface and explains these reactions in terms of acid-base interactions. In certain applications the chemical activity must be controlled if satisfactory products are to be obtained; for example, when kaolinite is used as a filler in rubber or as a diluent for insecticide powders. The concept of acid-base interactions is used to explain rheological and film properties in kaolinite-organic systems. The strength of the surface acid sites of kaolinite varies with the moisture content. At 1% moisture the surface is equivalent to 48% sulphuric acid whereas at 0% it is equivalent to 90% sulphuric acid. Therefore, the moisture level is extremely important and dry kaolinite will promote or catalyze many chemical reactions and where acid-base interactions are involved the presence of even small amounts of water usually retards or inhibits the reaction. Several examples explaining these interactions are given in the paper.

Hydrotalcite-like compounds, [Mg1-xAlx(OH)2]x+ [xX−·n H2O], where X− = ½CO32− or OH−, were prepared by hydrothermal syntheses at $$P_{H{_2}O}=100\;MPa$$ and T = 100°–350°C. Starting materials were MgO, γ-Al2O3, H2O, and MgC2O4·2H2O. The synthesis depended on temperature, pressure, the Al/(Al + Mg) ratio x, and the CO2 content of the starting material. Previously an Al content of x = 0.33 was thought to be the upper limit in these double-layer compounds, but by using pressure the Al-content was increased to x = 0.44. Up to x = 0.33, a0 decreased linearly to about 3.04 Å, but for x ≥0.33, a0 remained nearly constant at this value. For the synthesized products the layer thickness c’ varied between 7.40 and 7.57 Å in contrast to the natural phases wherein c’ varies from 7.60 to 7.80 Å. At higher temperatures CO2-free syntheses, i.e., those without Mg-oxalate, resulted in a disordered hydrotalcite-like phase. The transition temperature between the ordered and the disordered hydrotalcite-like phase depended on the Al-content, x.

The literature reports that freezing of aqueous aluminosilicate clay suspensions can produce clay aggregates that disperse with agitation. Our experiments indicate that colloidal suspensions extracted from north Idaho loess soils (Boralfs), when frozen, form silt- and sand-sized agglomerates that resist dispersion with agitation. XRD and TEM analyses showed that colloids are dominantly halloysite between 0.10 to 0.30 μm in diameter. The colloidal halloysite has anomalously high mole ratios of Si/Al and a high Fe content. Freeze-produced agglomerates are light yellow to yellowish-brown in color, occur in the form of plates, wedges, cuspates, or laths, and often exhibit uniform optical properties, suggesting a crystalline product. Selected area electron diffraction, however, indicates that the agglomerates are polycrystalline. With proper orientation, agglomerates produce acute bisectrix interference figures that are optically negative with variable 2V, generally μ30°. XRD analyses and IR spectra imply that the agglomerates are halloysite. Measured optical properties, however, are difFerent than those reported for halloysite and may be affected by the high Fe content and polycrystalline nature of the agglomerates. Grains, exhibiting similar optical properties as laboratory-produced agglomerates, are a minor proportion of the very-fine sand fraction in some horizons of the soils studied. Freeze-aided agglomeration of colloidal material may be an important process in temperate climates. It may be overlooked because of particle destruction by soil pretreatments or morphological order and/or optical similarity to some micaceous minerals.

The effects of ultrasound treatment on the mean particle size, crystal structure, crystallite dimensions and specific surface area of natural muscovite and biotite samples have been investigated. Sonication of macroscopic flakes of muscovite and biotite produced a drastic particle-size reduction. The conditions for the preparation of micron and submicron-sized muscovite and biotite particles of narrow particle-size distribution by sonochemistry are described. The effect of sonication on particle-size reduction is more significant for muscovite than for biotite. Thus, for long sonication times (100 h), submicron and micron particles are predominant in muscovite and biotite, respectively. The resulting materials are crystalline, as assayed by X-ray diffraction, only broadening of the diffraction lines due to size-reduction was observed. Nuclear magnetic resonance studies revealed that the coordination of Al and Si was not modified by the treatment. Chemical analysis showed that the composition of the sample was not affected by the sonication except for a small contamination by Ti from the tip cup of the sonication instrument.

The stable carbon isotope composition of CO2 occluded in the gibbsite structure is proposed as a potential atmospheric paleo-PCO2 proxy. Analysis of pedogenic gibbsite from a modern Ultisol in the Piedmont of Georgia, USA, was conducted to test the basis for this concept and to help constrain the parameters used to describe physical and biological processes affecting such factors as the respiration rate of CO2. Co-variation of the δ13C and δ18O values with depth along a gradient parallel to the mixing line between the atmosphere and the soil organic material implies that diffusion is the process that determines the stable isotope composition of soil CO2. In the upper 40 cm, the measured δ13C values are not consistent with the expected diffusive depth profile assumed in paleo-PCO2 models. The isotope signature is reset downward in the depth profile with a concentration of the most atmosphere-like δ13C and δ18O values occurring at the top of the Bt horizon by some as-yet-unknown process. Bioturbation, recrystallization, and physical translocation are potential explanations for this observation. Regardless of the process at work, the net effect is an apparent two-component mixing curve between the top of the Bt horizon and deep within the saprolite. In cases where the A horizon is eroded but the Bt horizon is preserved it is possible that δ13C values of gibbsite-occluded CO2 can serve as a proxy for atmospheric paleo-PCO2. Careful textural study of all paleosols is therefore essential to match stable carbon isotope signatures with the horizons preserved. Understanding of modern dynamics and preservation of these isotopic signatures may also be important for those that employ other carbonate proxies.

The transformation process between palygorskite and smectite was studied by examining the morphological and structural relationships between these two minerals in an assemblage from the Meigs Member of the Hawthorne Formation, southern Georgia. Studied samples were related to an alteration horizon with a tan clay unit above and a blue clay unit below. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to study the mechanism of transformation. From AFM data, both clay units contain euhedral palygorskite fibers. Many fibers are found as parallel intergrowths joined along the [010] direction to form ‘raft-like’ bundles. Degraded fibers, which are common in the tan clay, have a distinctly segmented morphology, suggesting a dissolution texture. Many of the altered palygorskite fibers in the tan clay exhibit an oriented overgrowth of another mineral phase, presumably smectite, displaying a platy morphology. This latter mineral forms along the length of the palygorskite crystals with an interface parallel to {010} of the palygorskite. The resulting grain structures have an elongate ‘wing-like’ morphology. Imaging by TEM of tan clay material shows smectite lattice-fringe lines intergrown with 2:1 layer ribbon modules (polysomes) of the palygorskite. These features indicate an epitaxial overgrowth of smectite on palygorskite and illustrate the structural relationship between platy overgrowths on fibers observed in AFM data. The epitaxial relationship is described as {010} [001] palygorskite ‖ {010} [001] smectite. Energy dispersive spectroscopy indicates that the smectite is ferrian montmorillonite. Polysomes of palygorskite fibers involved in these textures commonly vary and polysome widths are consistent with double tetrahedral chains (10.4 Å), triple tetrahedral chains (14.8 Å), quadruple tetrahedral chains (21.7 Å) and quintuple tetrahedral chains (24.5 Å). The transformation of palygorskite to smectite and the resulting intergrowths will cause variations in bulk physical properties of palygorskite-rich clays. The observation of this transformation in natural samples suggests that this transformation mechanism may be responsible for the lower abundance of palygorskite in Mesozoic and older sediments.