Bulk and size-fractionated kaolinites from seven localities in Australia as well as the Clay Minerals Society Source Clays Georgia KGa-1 and KGa-2 have been studied by X-ray diffraction (XRD), laser scattering, and electron microscopy in order to understand the variation of particle characteristics across a range of environments and to correlate specific particle characteristics with intercalation behavior. All kaolinites have been intercalated with N-methyl (NMF) after pretreatment with hydrazine hydrate, and the relative efficiency of intercalation has been determined using XRD. Intercalate yields of kaolinite: NMF are consistently low for bulk samples that have a high proportion of small-sized particles (i.e., <0.5 µm) and for biphased kaolinites with a high percentage (>60%) of low-defect phase. In general, particle size appears to be a more significant controlling factor than defect distribution in determining the relative yield of kaolinite: NMF intercalate.

The rehydration and rehydroxylation properties of homoionic rectorites (saturated with Ca2+, Mg2+, Na+, or K+) were further investigated. The rehydration properties of the rectorite were characterized as follows: (1) basal spacings of rehydrated materials after heating above 500°C changed to 22.5 Å for H2O-complexes, 26.85 Å for ethylene glycol-complexes, and 27.65 Å for glycerol-complexes; (2) rehydrated Ca- and Mg-materials exhibited single layer hydrates at <50% RH, and rehydrated K-material showed double layer hydrates at 80% RH; (3) IR absorption spectra due to rehydrated H2O and OH exhibited the same or very close absorption intensities and frequencies to each other; (4) DTA-TGA curves of rehydrated materials indicated that the amount of rehydrated H2O approached about 4.2 wt. %, and about one-half of OH was rehydroxylated after heating at 800°C; and (5) interlayer cations of expandable layer components became non-exchangeable after heating above 500°C. These results suggest the following rehydration mechanism of rectorite: the interlayer cations migrate into the hexagonal holes of the SiO4 network by thermal dehydration. The cations migrated below 400°C easily return to the interlayer space and their original hydrated configurations have been recovered completely on rehydration. However, those migrated above 500°C are fixed to the hexagonal holes but water molecules are regained in the interlayer space. Consequently, electrostatic effects of interlayer cations on formation of water molecule layers are considerably reduced.

Hisingerite, first described in 1810, has been variously regarded as noncrystalline, as a septechlorite, as ferric allophane, as ferric halloysite and as poorly crystalline nontronite. Hisingerite from the original localities of Gillinge and Riddarhyttan in Sweden has a composition close to Fe2O3·2SiO22H2O. X-ray diffraction (XRD) analysis of Riddarhyttan hisingerite yields very broad maxima at 7.7, 4.44, 3.57, 2.56, 2.26, 1.69 and 1.54 Å, and that from Gillinge is similar. Cation exchange capacities are 2.2 meq/100 g (Riddarhyttan) and zero (Gillinge). Transmission electron microscopy (TEM) shows a fabric of concentric spheres and part spheres, with diameters of about 140 Å and walls up to six 7-Å layers thick. High-resolution images of the sphere walls reveal a 2-layer structure similar to that of kaolinite. A calculated diffraction pattern based on a model of 4 concentric shells of ferric kaolinite structure matches the observed pattern quite closely. Some other hisingerites, notably that from Bellevue King Mine, Idaho, show 10-Å layers as well as 7-Å layers, and this hisingerite has a CEC of 32 meq/100 g and a weak 15.5-Å X-ray reflection in addition to a pattern similar to Riddarhyttan hisingerite. It is concluded that hisingerite is a curved ferric 7-Å 1:1 layer silicate analogous to halloysite, and that many of the hisingerites reported in the literature contain admixed nontronite.

Extensive hydrothermal alteration is observed around volcanogenic massive sulfide deposits. These deposits are related to Late Cretaceous volcanism in various parts of the Eastern Pontide province. Mineral assemblages resulting from alteration consist of mostly clay minerals and silica polymorphs, some sulfate minerals, and scarce zeolite minerals. The clay minerals are kaolinite, illite, and smectite. These minerals were examined using X-ray diffraction (XRD), scanning electron microscopy (SEM)-energy dispersive spectrometry (EDS), X-ray fluorescence spectroscopy (XRF), and differential thermal analysis (DTA)-thermal gravimetry (TG) techniques. The illite and the toseki deposits are a result of hydrothermal alteration of dacitic-andesitic volcanites. Two groups of bentonite deposits occur; the first mainly formed by hydrothermal solution whereas the second group resulted from halmyrolysis.

The smectite in these alteration zones is generally montmorillonitic in composition and the interlayer cation is mostly Ca and lesser amounts of Na. The SiO2 and Fe2O3 contents of the hydrothermal bentonites are higher than those of the halmyrolysis smectites; however, the MgO content of both groups is similar. The Na2O and K2O contents of both groups are generally <0.5%. The hydrothermal bentonites are not plastic and have open honeycomb microtextures, although the halmyrolitic smectites are plastic with ultrafine and rod-shaped textures. Illite, which contains some smectite layers, is a 1M polymorph, and has an asymmetry to the low-angle side of the XRD peaks. The impure illite deposits contain various combinations of smectite, kaolinite and gypsum, galena, sphalerite, pyrite, goetite, and quartz. The illite has >35 wt. % Al2O3. The toseki raw material, which may be possibly useful as a porcelain raw material, is composed mainly of illite, kaolinite and quartz, or illite and quartz. The crystallinity of the kaolinite is poor.

High resolution transmission electron microscopy (HRTEM) have been performed on dispersed portions of one R > 1 and two R3 illite/smectite (I/S) samples from Silurian K-bentonites. R > 1 sample was studied by HRTEM before and after alkylammonium ion treatment and R3 samples were studied only after alkylammonium ion treatment. The HRTEM images of the chemically untreated R > 1 sample were predominated by lattice fringe contrast with 20–40 Å periods, interpreted to represent various ordered I/S units. HRTEM images of the three alkylammonium-treated samples displayed very small, dispersed particles composed of illite packets separated by alkylammonium expanded interlayers. In the R > 1 sample, illite packets were mostly 20 Å to 40 Å thick whereas in R3 samples they were predominantly over 40 Å. Although a good degree of dispersion of the bulk samples was achieved, dispersed particles recorded on images were thicker than the fundamental particles postulated by Nadeau and coworkers. Alkylammonium ion-expanded interlayer thicknesses point out a trend toward a higher charge in the expandable interlayers (i.e., illite particle surfaces) with increasing illite content from the R > 1 sample to the R3 samples. In the R3 samples, the interlayer charge is sufficiently high to be vermiculitic.

Structural Fe in ferruginous smectite (sample SWa-1, Source Clays Repository of the Clay Minerals Society) was reduced by a mixture of five Pseudomonas species of bacteria in a defined Fe-free medium to determine the effect of microbial reduction on clay swelling. Iron(II), total Fe, and gravimetric water content (mw/mc) were determined in clay gels equilibrated at applied pressures of 0.1, 0.3, and 0.5 MPa. The water content of microbially reduced SWa-1 decreased at all three applied pressures as the Fe(II) content approached about 0.8 mmol Fe(II)/g-clay. As Fe(II) increased from 0.8 mmol/g-clay, however, further change in mw/mc was negligible. Concurrent with microbial reduction of structural Fe was a significant decrease in the swelling pressure (PI) of SWa-1: for example, when mw/mc = 1.2 (g/g), PI changed from 0.47 MPa at Fe(II) = 0.2, to 0.19 MPa at Fe(II) = 0.9 mmol/g-clay. Both biologically and chemically reduced smectites displayed lower values of mw/mc and a concurrent decrease in II as Fe(II) content increased, but the effect of Fe(II) on mw/mc was greater for the microbially reduced smectites at all applied pressures.

The crystal structure of synthetic deuterated kaolinite was refined by Rietveld analysis using time-of-flight (TOF) neutron powder diffraction data. For non-hydrogen atoms, Cl symmetry was assumed. Starting models were tested in which only the direction of O-D vectors was varied. The constraints were introduced to all Al-O, Si-O and O-D bonds. The refinement adopting the former gives Pl(C1), a = 5.169(1) Å, b = 8.960(2) Å, c = 7.410(2) Å, α = 91.26(2)°, ß = 104.99(2)°, γ = 89.93(1)°, Rwp = 3.17%, R1 = 5.78% and S = 1.34 with constraints of l(Al-O)= 1.93 ± 0.05 Å, l(Si-O)= 1.62 ± 0.03 Å and l(D-O) = 0.95 ± 0.15 Å. The inner O-D vector points toward the tetrahedral sheet. All inner-surface O-D groups form H bonding with basal O atoms in the next kaolinite layers. The results agreed with those obtained from natural kaolinite.

An internal standard X-ray diffraction (XRD) analysis technique permits reproducible and accurate calculation of the mineral contents of rocks, including the major clay mineral families: Fe-rich chlorites + berthierine, Mg-rich chlorites, Fe-rich dioctahedral 2:1 clays and micas, Al-rich dioctahedral 2:1 clays and micas, and kaolinites. A single XRD pattern from an air-dried random specimen is used. Clays are quantified from their 060 reflections which are well resolved and insensitive to structural defects. Zincite is used as the internal standard instead of corundum, because its reflections are more conveniently located and stronger, allowing for a smaller amount of spike (10%). The grinding technique used produces powders free of grains coarser than 20 µm and suitable for obtaining random and rigid specimens.

Errors in accuracy are low, <2 wt. % deviation from actual values for individual minerals, as tested on artificial shale mixtures. No normalization is applied and thus, for natural rocks, the analysis is tested by the departure of the sum of the measured components from 100%. Our approach compares favorably with other quantitative analysis techniques, including a Rietveld-based technique.

Sepiolite from Mara (Zaragoza, Spain) and palygorskite from Attapulgus (Georgia, USA) were activated by treatment at different concentrations with solutions of boiling HCl under reflux conditions. The natural and treated solids were characterized by mineralogical, chemical and textural analyses.

Acid attack resulted in a progressive dissolution of the octahedral layer of these silicates. Silica contents increased and octahedral cations (Al, Mg and Fe) decreased with the intensity of the acid attack. In both cases, fibrous free silica was obtained.

The sepiolite was destroyed more rapidly than palygorskite under the conditions used because of its magnesic composition and the larger size of its structural microchannels. The maximum increase in specific surface area was obtained for sepiolite at 3 N and for palygorskite at 9 N. Cleaning and disaggregation of the particles and the increase in the number of micropores were responsible for this increase in specific surface area.

The Clay Minerals Society Source Clay kaolinites, Georgia KGa-1 and KGa-2, have been subjected to particle size determinations by 1) conventional sedimentation methods, 2) electron microscopy and image analysis, and 3) laser scattering using improved algorithms for the interaction of light with small particles. Particle shape, size distribution, and crystallinity vary considerably for each kaolinite. Replicate analyses of separated size fractions showed that in the <2 µm range, the sedimentation/centrifugation method of Tanner and Jackson (1947) is reproducible for different kaolinite types and that the calculated size ranges are in reasonable agreement with the size bins estimated from laser scattering. Particle sizes determined by laser scattering must be calculated using Mie theory when the dominant particle size is less than ∼5 µm. Based on this study of two well-known and structurally different kaolinites, laser scattering, with improved data reduction algorithms that include Mie theory, should be considered an internally consistent and rapid technique for clay particle sizing.

SiO2 sols were made unstable by addition of Ca2+ ions. The resulting states of instability were classified as gelation, flocculation, and precipitation by means of observation, by checking the Tyndall effects on the supernatant or suspending solution, as appropriate, and by measuring the apparent densities of flocculated mass. The concentrations of free Ca2+ ions left in solution were measured by means of a Ca2+ ion selective electrode. The amounts sorbed onto SiO2 particles were then calculated by material balance. It was found that while the amount sorbed dictates the limit of stability, the SiO2 concentration in the mixture is an important factor deciding the state of instability. Depending on the SiO2 concentration, there were two distinct flocs with the apparent floc density of 6 ± 1 and 12 ± 1 mg SiO2/ml.

In general, the N2-BET surface areas of sepiolite samples range from 95 to 400 m2/g depending on deposits.

The surface areas of five sepiolites, all varying in crystallite size, were measured on heating, and were compared with a model calculation. A sharp decrease in the surface area, due to crystal folding, was observed between 200° and 400°C. Both before and after the folding, each sepiolite sample had peculiar values. Our model sufficiently explains this difference in surface areas among the samples. In the model, which is based on the Brauner-Preisinger structural model, surface area is a function of the crystallite size and the ratios of the coverage for nitrogen adsorption on both the internal and external surfaces. These ratios of the coverage can be inversely estimated from the model. The ratios of the coverage on the internal surface are less than 0.19, and that on the external surface between 0.7 and 1.0.

The hydrothermal synthesis of Mg-beidellite in which limited amounts of Ga and Cr are clearly shown to be incorporated into nonexchangeable positions in the clay layer framework is reported for the first time. Elemental analyses indicate that, up to at least 15 mole percent, Ga can replace Al virtually completely; Cr incorporation is more difficult. It appears that the Ga that is incorporated into the beidellite is located primarily in the octahedral sheet. Pillaring of the synthesized beidellite by replacing the Mg2+ with large AlO4Al12(OH)24(H2O)127+ ions showed that approximately 5.5 meq Al3+ was required per g of beidellite to achieve complete pillaring. This amount is very similar to that required for montmorillonite, and suggests that the cation exchange capacity (CEC) of the beidellite is about 98 meq/g.

The layer charge characteristics of expanding phyllosilicates in four salt-affected soils in Alberta, Canada were investigated using X-ray diffraction analysis of alkylammonium saturated samples. The layer charge was found to be lower and more heterogeneous than previously reported for non-saline Alberta soils, with the mean layer charge ranging between 0.261 to 0.339 tool (—)/O10(OH)2. Layer charge characteristics varied inconsistently with location, depth and particle size, likely the result of both different origins and weathering processes. Different degrees of K depletion from the micaceous component after equilibration with alkylammonium compounds may also account for some variability between samples. Extreme broadening and essential disappearance of smectite diffraction maxima was noted for some samples after intercalation with alkylammonium cations of all carbon chain lengths, indicating unusual alteration of the layer charge characteristics in some salt-affected soils.

The stacking order of a bi-ionic K/Mg vermiculite from Malawi (Nyasaland), has been determined from Weissenberg data. The sample corresponds to a K/Mg interstratified vermiculite containing 50% K layers (dK = 1.01 nm) and 50% Mg layers with two layers of water (dMg = 1.44 nm). The observed intensities along (0, 0), (h, 0), (0, k) and (1, k) reciprocal rods were compared to the calculated intensities given by model defect structures. It was found that: 1) The (h, 0), (0, k) and (1, k) rods reveal the interstratification phenomenon which was previously observed on the (0, 0) rod; 2) The exchange of Mg by K does not occur randomly in a single interlayer, but occurs in interlayer domains sufficiently extensive to allow the reorganisation of the layer stacking and development of the ordered K-vermiculite structure from the semi-ordered structure characteristic of magnesium vermiculites; 3) For this sample, the interlayer water of the Mg phase occurs in two coexisting configurations; one configuration has water molecules forming octahedral coordination around the Mg2+, the other has water which is not linked to the Mg2+ cation forming two planes.

Because of the large surface area and common occurrence of smectites in the clay fractions, they are important in sorption/desorption reactions of organic pollutants entering soils and sediments. Results of sorption and desorption of atrazine by Al- and Ca-saturated smectite reported here showed that Al-saturated smectite sorbed much higher amounts of atrazine than Ca-saturated smectite. Al-saturated smectite sorbed 3820 mg kg−1 as compared to 1902 mg kg−1 by the Ca-saturated smectite during 5 consecutive sorptions from 10 ppm atrazine solution. Sorption isotherms over 2–10 ppm atrazine concentration range were nonlinear in all cases. Freundich coefficients, Kf, obtained from the sorption isotherms were much higher for Al- than Ca-saturated smectite; Kf varied from 405 to 3035 for Al-saturated and 100 to 306 for Ca-saturated. The pH values of Al- and Ca-saturated smectites were 3–4 units higher than the pKa (1.68) of atrazine, which suggests that atrazine was sorbed as neutral molecules. Stronger H-bonding between the more polarized H2O associated with the trivalent Al ion than the divalent Ca ion is likely responsible for the greater sorption by Al-smectite.

Thermal maturity of the Lower Cretaceous Sindong and Hayang groups in the Gyeongsang Basin, Korea, was investigated using the Kübler illite “crystallinity” index (KI) which is based on the numerical expression of the 10-Å peak width after calibration to the Crystallinity Index Standard scale. The metamorphic grade of the Sindong and Hayang groups ranges from late diagenetic zone to high anchizone. Depth of burial was not a major factor controlling KI variation in the basin because Hayang mudrocks have higher thermal maturity than the underlying Sindong mudrocks. Short-lived heating by the emplacement of the Upper Cretaceous plutonic rocks is responsible for the higher thermal maturity in the Hayang mudrocks. A linear NNE-SSW trending belt is drawn by connecting the lowest KI values, and it seems to reflect a hidden fault trace beneath the Hayang Group. Emplacement of Upper Cretaceous plutonic rocks and introduction of hydrothermal fluids along the inferred fault may have been the main cause of the lowering of KI values along this belt. This inferred fault is interpreted to represent the buried eastern boundary of the Nagdong Trough, which was the main depositional site for the Sindong Group in the western part of the Gyeongsang Basin. Deposition of the Hayang Group occurred in the enlarged basin when the basin extended eastward. This study provides an example that KI values can be used in the reconstruction of an early history of basin evolution.

Tomato has been cultivated in Greece for more than 200 years, even though is not native to the country. Greece with a favourable environment all-round the year, has become a major competitor in tomato production around Europe. However, there is an increasing demand to improve tomato crop, to withstand harsh environmental conditions (extreme temperatures, salinity, etc.), and to develop high-quality final products. People have devoted a significant effort to crop improvement through phenotypic screening resulting in a large number of tomato landraces. An increasing demand to clarify the relationships among local tomato landraces and hybrids utilizing the most preferred molecular markers the simple sequence repeats (SSR-markers) is the main objective of this study. Twenty-seven tomato landraces and two tomato hybrids cultivated in Crete, Greece, were genotyped utilizing eleven simple sequence repeats (SSR) along with the Structure analysis of the germplasm. A neighbour-joining dendrogram of the 27 landraces and the two hybrids was produced. The Structure analysis indicated that nine ancestral populations are hidden inside the group of all the genotypes tested, using Evanno's method. The final objective was to make these data publicly available through the first Greek relational database (Greek Tomato Database-GTD). GTD was developed allowing the users to update and enrich the database, with new and supplemental information. This work is the first molecular fingerprint of the 27 landraces of Greece which is documented along with the phenotypic information in the GTD.