Sulphur reduction catalysts represent a viable option for S reduction in the fluid catalytic cracking (FCC) process. In this paper, a kaolin in situ crystallization catalyst was modified with vanadium and evaluated in a fixed fluid bed (FFB) reactor. The relation between the acidity of the catalyst, the S reduction rate and the catalyst activity is discussed. The results show that increasing weak Lewis acid acidity favours S reduction in the FCC process. Increasing the V content enhances the weak Lewis acidity, so causing the S reduction rate to increase. The kaolin in situ crystallization catalyst modified with 0.6 wt.% of V leads to a 34.5% reduction in the S content of the liquid product. Comprehensive evaluation of the FFB results and the S reduction ability indicates that the catalyst modified with 0.45 wt.% V provided the best performance.

Vermiculite minerals are locally available in the Mozambique Belt of Tanzania but are not currently commercially exploited. In part this may be due to lack of any precise characterization. This study was carried out as a first step to assess the suitability of these vermiculites for crop production by characterization of their mineralogical and chemical compositions. X-ray diffraction and scanning electron microscopy combined with an energy-dispersive X-ray system were used to establish the mineralogy. Electron microprobe analysis and inductively coupled plasma-mass spectrometry were used to study the chemical compositions and to identify any possible issues related to chemical composition that might affect their use if applied as soil conditioners. The samples were characterized as vermiculites and hydrobiotites with a wide variety of accessory minerals. Accessory minerals that might be of some concern are galena, fibrous amphiboles and sepiolite. The total levels of Ni in all vermiculites, and Cr in some, were also found to be high relative to common European standards and this might limit their potential as soil conditioners. It is clear that a field assessment of the bioavailability of various elements would be necessary before decisions relating to potential agricultural use could be made.

Because of their large potential for agricultural, industrial and medicinal applications, nanomaterials have been the focus of much research during the past few decades. Nanoclays are natural nanomaterials that occur in the clay fraction of soil, among which montmorillonite and allophane are the most important species. Montmorillonite is a crystalline hydrous phyllosilicate (layer silicate). Organically-modified montmorillonites or ‘organoclays’, formed by intercalation of quaternary ammonium cations, have long been used as rheological modifiers and additives in paints, inks, greases and cosmetics and as carriers and delivery systems for the controlled release of drugs. Perhaps the largest single usage of organoclays over recent years has been in the manufacture of polymer-clay nanocomposites. These organic–inorganic hybrid materials show superior mechanical, thermal and gas-barrier properties. Organoclays are also useful in pollution control and water treatment. Allophane is a non-crystalline aluminosilicate derived from the weathering of volcanic ash. A large proportion of the agricultural land in Chile is covered by volcanic soils,the clay fraction of which is dominated by allophane. Consisting of nanosize (3.5–5.0 nm) hollow spherules, allophane is a suitable support material for enzyme immobilization. Allophane is also effective at adsorbing phenolic compounds and colour from kraft mill effluents and phosphate from water and wastewater.

Precise measurement of the content and the layer charge of illite and smectite is an important aspect of the mineralogical calibration of geophysical well logs and of the evaluation of mechanical and chemical properties of sedimentary rocks. Ate chnique for obtaining such measurements was developed during mineralogical studies of the Miocene clastic rocks from the Carpathian Foredeep. X-ray diffraction (XRD), chemical, cation exchange capacity (CEC), H2O sorption, and ethylene glycol monoethyl ether (EGME) sorption data were obtained for 65 samples of sandstones, shales and carbonates. The illite + smectite sum, involving all detected 2:1 minerals (smectite, illite-smectite, illite, glauconite and muscovite) was measured by XRD. The content of the illitic component was evaluated separately using % K2O and accounting for % K2O in K-feldspar. The content of the smectitic component was estimated from EGME retention using the reference data for a smectite standard, and from CEC assuming the smectitic layer charge of 0.41/O10(OH)2 (Środoń et al., in press). All these measurements produced very consistent results.

Separation of nitrogen, the major impurity of natural gas, is necessary for quality improvement of the gas. In this study, purified and some ion-exchanged forms of clinoptilolite were used to separate N2 from natural gas. Competitive adsorption of mixtures of N2, CH4 and C2H6 by Cu2+ (Cu-Cp)-, Zn2+ (Zn-Cp)-, Ni2+ (Ni-Cp)- and Mn2+ (Mn-Cp)-exchanged samples was studied at different pressures and ambient temperature. Among the cations studied, Cu2+ has the lowest selectivity towards N2. Samples were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, BET N2 adsorption and wet chemical analysis techniques.

The mineralogy of the glazed surfaces of Japanese sekishu roof tiles covered by a crustose lichen – Lecidella asema (Nyl.) Knoph & Hertel – was investigated using transmission electron microscopy (TEM). The study sought to identify the Ti-Fe mineral observed as a low concentration of Ti and Fe in a previous study of the glazed surfaces of the same roof tile. The TEM analysis revealed that: (1) a thin layer of the Ti-Fe mineral pseudobrookite exists on the glaze surface; (2) the pseudobrookite consists of well-ordered single crystals, continuously and widely distributed on the glaze surface.

A new structural model for ferrihydrite that challenges the standard ferrihydrite model established by X-ray diffraction and confirmed by neutron diffraction and single-crystal electron nanodiffraction was recently proposed by Michel et al. (2007a) from the simulation of the pair distribution function obtained by Fourier transformation of diffraction data measured at λ = 0.137 Å. The new ferrihydrite model is isostructural to akdalaite (Al10O14(OH)2), a mineral having the Baker-Figgis δ-isomer of the Al13-Keggin structure as its structural motif. The new model is unrealistic because: (1) it is completely periodic (i.e. defect-free); (2), it has 20% tetravalent octahedral iron (VIFe4+), 20% divalent tetrahedral iron (IVFe2+), and some IVFe–O distances equal to or larger than the VIFe3+–O distances, thus violating Pauling's 2nd rule; (3) it does not describe X-ray diffraction and EXAFS spectroscopic data; and, (4) it is inconsistent with electron microscopy results and contradicts previous X-ray scattering studies.

New chemical and structural data on sepiolite-falcondoite in garnierite veins from the Falcondo Ni-laterite deposits, central Dominican Republic, are reported. Samples of Ni-sepiolite-falcondoite vary in colour from whitish green to green depending on the NiO content (wt.%) and the amount of silica present. The texture is normally schistose and friable but samples with considerable quartz and/or amorphous silica are compact and hard. Back-scattered electron images indicate that the samples are composed of at least three generations of Ni-sepiolite-falcondoite. The extreme refined cell parameters for Ni-sepiolite-falcondoite vary from 13.400(2), 27.006(4), 5.273(1) Å to 13.340(3), 27.001(6), 5.267(1) Å (space group Pncn). As the Ni content increases there is a small reduction in the a parameter. Chemical compositions determined by electron probe microanalysis cover a large interval of the Ni-sepiolite-falcondoite solid solution (Fal3 and Fal77). Individual samples show a considerable range in composition with the widest range determined in one sample from 4.63 to 22.40 wt.% NiO.

A series of Cu-substituted goethites, single and co-substituted with Cr, Zn, Cd and/or Pb was prepared, having molar ratios equal to 2.00, 3.33 and 5.00 mol%. All the samples contained only goethite, except Cu-, (Cu,Zn)- and (Cu,Pb)-samples synthesized at 5.00 mol% where hematite was also formed. The presence of Cr/Cd suppressed the hematite-forming effects of Cu. The general sequence of metal entry into the single-metal-substituted goethites was Zn = Cr > Cd > Cu > Pb and in di- (5.00 mol%) and tri- (3.33 mol%) metal-substituted goethites was Cu > Zn > Cd > Cr >> Pb. Cu incorporation increased all the unit-cell parameters in single-metal-substituted goethite, and these parameters increased in combination with other metals as follows: Cd > Zn > Cr > Pb in the multimetal-substituted goethites. The Cu-substituted goethite dissolved faster than pure goethite. Co substitutions of Cr/Pb reduced the dissolution rate (kFe), while substitutions of Cd/Zn increased kFe.

Melt blending using a twin-screw extruder was used to prepare composites of polypropylene (PP)/organic rectorite (PR). The organic rectorite (OREC) was modified with dodecyl benzyl dimethyl ammonium bromide (1227). Wide-angle X-ray diffraction (WAXD) and transmission electron microscopy were used to investigate the dispersion of OREC in the composites. The d spacings of OREC in PR composites was greater than in OREC itself. The dispersion of OREC particles in the PP polymer matrix was fine and uniform when the clay content was small (2 wt.%). The rheology was characterized using a capillary rheometer. The processing behaviour of the PR system improved as the amount of OREC added increased. Non-isothermal crystallization kinetics were analysed using differential scanning calorimetry. It was shown that the addition of OREC had a heterogeneous nucleation effect on PP, and can accelerate the crystallization. However, only when fine dispersion was achieved, and at lower rates of temperature decrease, was the crystallinity greater. Wide-angle X-ray diffraction and polarized light microscopy were used to observe the crystalline form and crystallite size. The PP in the PR composites exhibited an a-monoclinic crystal form, as in pure PP, and in both cases a spherulite structure was observed. However, the smaller spherulite size in the PR systems indicated that addition of OREC can reduce the crystal size significantly, which might improve the ‘toughness’ of the PP. The mechanical properties (tensile and impact strength) improved when the amount of OREC added was appropriate. Dynamic mechanical analysis showed that the storage modulus (E′) and loss modulus (E″) of the nanocomposites were somewhat greater than those of pure PP when an appropriate amount of OREC was added. Finally, thermogravimetric analysis showed that the PR systems exhibited a greater thermal stability than was seen with pure PP.

The spatial distribution of the Atterberg limits can be used to distinguish the consistency and behaviour of a soil and its engineering properties, which strongly depends on the water content of the soil and types of silts and clays in the soil. By spatial modeling, and comparing the results of ordinary kriging with the cokriging approach, this study aims to find correlations between the Atterberg limits and the selected physical soil parameters in order to examine how effective they are in generating an understanding of the dynamics of a physical soil system.

In 156 soil samples, the Atterberg limits and soil moisture conditions were determined, and auxiliary functions were selected by application of cokriging using correlation analysis and regression equations obtained by the residual maximum likelihood (REML). These techniques were evaluated by the results of the mean absolute error (MAE) and the mean squared error (MSE). Cokriging analysis was found to be more effective at estimating the liquid limit (WLL) and the plastic limit (WPL) than kriging analysis and with smaller error values. On the other hand, the kriging approach, which had smaller MAE and MSE values, was more effective at estimating the plasticity index (WPI) values than the cokriging method. Unlike the REML regression equations, the field capacity (FC) value was the more suitable parameter for the cokriging estimates. When the necessary labour and time were considered for determining the Atterberg limits, both kriging and cokriging were found to be applicable for estimation of these limits.

The composition and particle morphology of diagenetic mixed-layer illite-smectite (I-S) in the shallow buried Ordovician Kinnekulle K-bentonite were studied to understand the process of illitization in the Baltic Basin. The same K-bentonite bed from 12 different locations in the Basin was sampled and analysed by means of X-ray diffraction (XRD), atomic-force microscopy (AFM) and K-Ar dating. Illite-smectite in the samples was identified as a highly illitic R1 type illite-smectite vermiculite (high-charge smectite) mixed-layer mineral with 63–78% illitic layers. Illite-smectite was characterized by log-normally distributed thin particles with an area-weighted mean thickness varying from 1.9 to 3.6 nm and 2.1 to 3.8 nm by XRD-PVP and AFM analysis, respectively. The K-Ar diagenetic ages of the mixed-layer minerals suggest an illitization age of 370 to 420 Ma that agrees with the latest phase of the Caledonian orogeny. Illitization of the Kinnekulle bentonite was probably driven by the intrusion of K-rich fluids.

The clay mineralogy and chemical composition of the white veins, red matrix and both Fe- and Mn-bearing nodules occurring in a laterite profile in Hubei, south China were investigated using X-ray diffraction, scanning electron microscopy equipped with an energy-dispersive spectrometer, and high-resolution transmission electron microscopy. The results show that the mineral components of the red matrix are mainly quartz, kaolinite, halloysite, goethite and minor illite, whereas the white net-like veins contain mostly quartz, kaolinite, halloysite, and illite. In the net-like horizon, the chemical index of alteration (CIA, the ratio of Al2O3/(Al2O3+CaO+K2O+Na2O)) and the TiO2/Al2O3 ratio are 89.8% and 0.021 for the white vein and 90.7% and 0.025 for the red matrix, respectively. Both white-vein and red-matrix components have similar TiO2/Al2O3 ratios, and are similar to the ratio 0.027 of the unaltered bedrock. The similarity in TiO2/Al2O3 values indicates that all three portions of the laterite soil share the same origin. Also, although the white-vein and red-matrix components differ in Fe2O3 abundance, the similar CIA values do imply similar degrees of alteration. The Fe-bearing and Mn-bearing nodules were produced by the local accumulation of Fe2O3 and MnO, respectively. Halloysite in the weathering profile occurs in two different morphologies, tubular and platy crystals. Tubular halloysite occurs both in the red matrix and the Fe-bearing nodule whereas platy halloysite occurs only in the white vein and Mn-bearing nodule assemblages. Crystallization of small tubular halloysite from Si and Al concretions in the red matrix is observed, indicating that the morphology of these crystals in the weathering environment is mainly controlled by Fe3+ cations, whereas platy halloysite may be derived from the hydration of kaolinite.

The effects of mechano-chemical treatment on the surface characteristics and sorption properties of hydrotalcite were studied. Non-milled (crushed) and milled samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), particle size analysis and specific area. A milling time of 2 h decreased the particle size of the hydrotalcite samples from 21 to 8.0 nm, the specific area from 97 to 5.7 m2 g–1 and the total pore volume from 0.41 to 0.01 cm3. After the crushed and milled samples had been separately calcined at 500ºC, they were agitated with 10–2 M Na2MoO4 aqueous solutions for 48 h. The molybdate ion content in the regenerated non-milled hydrotalcite samples (HTc-MoO4) was found to be 6.0 meq g–1 while in the milled hydrotalcite (HTm-MoO4) samples this content was 2.5 meq g–1. The lower molybdate content was thought to be a result of compaction and, hence, reduced reactivity of the milled HT samples.

Two types of mineral fillers, talc and mica, were compounded into polypropylene (PP) via a twin-screw extruder. The morphologies and mechanical properties of the resultant composites were investigated. The dispersion of minerals in PP was observed using Focused Ion Beam (FIB) techniques. The particle size distribution (PSD) and aspect ratio (AR) of particles in the polymer phase were obtained from FIB image analysis. It was found that FIB imaging displays directly the micron to mesoscale level dispersion of particles in polymeric composites. The technique has significant potential for characterizing such materials, having some advantages over ‘traditional’ scanning and transmission electron microscopy in terms of generating representative data in a realistic timescale. The PSD and AR distribution and degree of dispersion in the composites give insights into the modification of mechanical properties of the composites studied.

Alteration minerals dickite and kaolinite were detected in two hydrothermal Pb-Zn-Ag sulphide deposits in the northern Kosovo region. Dickite is associated with skarn mineralization in the Trepča (Stari Trg) deposit and kaolinite occurs in vein sulphide parageneses in the Crnac deposit. The mineralogical characteristics of dickite and kaolinite were determined by X-ray powder diffraction, Raman spectroscopy and scanning electron microscopy with EDS detector. Fluid-inclusion microthermometry and ion chromatography of leachates provided information on the P-T-X conditions of the genesis of dickite at Trepča. It was formed at temperatures between 290 and 330ºC and pressures between 12 and 60 MPa from a fluid with salinity in the range 6–8.5 wt.% NaCl eq. and pH <5.5. Kaolinite was deposited from a fluid with minimum temperatures between 210 and 250ºC, minimum pressure of 1.7 to 3.7 MPa, and salinity between 4.6 and 5.1 wt.% NaCl eq. Both dickite and kaolinite are related to the acidic pre-mineralization phase in the deposits.

The percolation of water through waste landfill sites produces leachates with large amounts of pollutants. Clay barriers are often used to limit soil and underground water pollution. A better understanding of the interaction between ammonium smectite and carboxylic acids would contribute significantly to our understanding of such systems. The SWy-2 (Wyoming smectite) was exchanged with NH4+ and then batched with carboxylic acids (acetic, formic, chloroacetic and oxalic) in concentrations between 0.01 M and 1 M. The solid phases obtained were analysed chemically and characterized by infrared absorption spectroscopy (IR) and powder X-ray diffraction (XRD). Ionic chromatography was used for the quantitative measurement of ammonium ions in the solution after the interaction. For the four acids, the interaction was characterized by a cationic exchange of NH4+ to H3O+. A partial exchange to Al3+ due to a partial dissolution of the sample in strong acidic medium was observed with chloroacetic and oxalic acids for which adsorption of molecules on the clay sample occurs, mainly through H-bonding with the cation. Moreover, the intercalation of oxalic acid in the interlayer space was highlighted.

The climatic history of the Dead Sea region during the Pliocene and its global connection are observed from climate-sensitive rocks and clay minerals of the Sedom formation. The Sedom formation consists of evaporative halitic rock salt units and calcareous shale units that were deposited in the Dead Sea Basin during the Pliocene. The precipitation of the rock salts took place in the hypersaline sabkha environment of the Sedom Lagoon. The extensive evaporative conditions are related to an extremely dry and warm arid climate at that time. In the arid climate, the influx of meteoric water by the drainage system of the Sedom Lagoon was limited and permitted a large concentration of lagoonal brine as well as a small rate of detritus transportation to the lagoon. Accessory sepiolite found in the rock salt appears to be neoformed from brine enriched with Mg and poor in Al under the extreme salinity condition. The small amounts of Al are in accordance with the small number of detrital minerals in the rock salts. The replacement in the deposition of the rock salt members with the calcareous shale members demonstrates a decrease in the salinity of the brine in the Sedom Basin and an increase in the deposition of detritus. The change in conditions was related to a period of deposition under a more humid climate where the erosion and the transport of detritus by the drainage system to the Sedom Basin was higher, causing the deposition of calcareous shales. Palygorskite found in the calcareous shales appears to be neoformed from brine enriched with Mg and containing Al in conditions of reduced salinity of the Sedom Basin. The larger amounts of Al are in accordance with the abundance of detrital minerals in the calcareous shales.

The depositional cycles of the Sedom formation, the cyclic fluctuation of the climatic-hydrologic conditions from an arid to a more humid climate and their correlation with sea-level fluctuations and transgression-regression cycles of the Mediterranean Sea seem to be a response to corresponding global interglacial and glacial periods during the Pliocene.

Clay is the main construction material for clay cores of earth-fill dams. Clay minerals swell when they become wet and shrink when they dry out; cracks develop as they lose moisture. If precautions are not taken to prevent seepage through these cracks, dam failures may result. In this study, sand was added to montmorillonite-dominant clay soils to investigate the effect of sand-inclusion rates on the engineering characteristics of clay soils used in the construction of clay cores of earth-fill dams. Changes in the consistency limits, compaction characteristics, permeability, stress-strain relationships and swelling characteristics with increasing sand inclusion rates were evaluated. Based on the results from experimental trials, a 30% sand inclusion rate appears to be the optimum proportion; most of the swelling occurred in the voids of grains and led to permeability levels below the allowable limits for earth-fill dams.