Soil solution chemistry, especially pH and the presence of multivalent ions, affects the surface charge (SC) of Fe oxides and accordingly colloidal stability and sorption properties. The SC of synthetic goethite and hematite was quantified in the presence of different electrolytes (NaCl, CaCl2, Na2SO4 and CaSO4) by combining the streaming potential with polyelectrolyte titration. The point of zero charge (PZC) for goethite was observed at pH 8.2 and the stability field around the PZC, where colloids are flocculated, is more extended (±1 pH unit) than that of hematite with a PZC at pH 7.1 (±0.5 pH unit). The SC decreases with increasing SO4 concentration, indicating adsorption of SO4 on the oxide, whereas the presence of Ca increases the SC. At pH 4, the addition of 0.1 mmol l–1 Na2SO4 induced a decrease in SC from 1.5 to 0.380 μmolc m–2 for goethite and from 0.85 to 0.42 μmolc m–2 for hematite. In a suspension with 0.1 mmol l–1 Na2SO4, the number of colloids is already reduced, and both oxides flocculate rapidly and completely at >0.5 mmol l–1 Na2SO4. While the addition of SO4 did not affect charge titrations with the cationic polyelectrolyte, the anionic polyelectrolyte formed complexes with Ca, resulting in an overestimation of positive SC. The electrolyte CaSO4 is most efficient at keeping goethite and hematite in the pH range 4–10 in the flocculated state. Besides pH, the presence of multivalent ions should also be considered when predicting colloid mediated transport and adsorption properties of anionic substances by Fe oxides in soil systems.

The effects of acid and Al concentration, type of Al salt, treatment temperature and time of removal of Mg from sepiolite have been investigated, as has the use of modified sepiolite as an active fluid catalytic cracking (FCC) matrix. The samples were characterized by N2 adsorption and X-ray diffraction. Mg removal from sepiolite increased with increasing acid and Al ion concentration, treatment time and temperature. The temperature had the greatest impact on Mg removal. After acid and Al modification, 29% of the Mg was removed. When using the modified sepiolites as active matrices in FCC catalysts, the specific surface area, pore volume and mesoporous pore volume of the catalysts increased and they exhibited excellent performance in resisting the effects of heavy-metals as a result of the introduction of Mg oxide from the modified sepiolite.

A new practical and precise method for determining soil aggregate stability is described. Four air-dry aggregate fractions (<0.25, 0.25–0.5, 0.5–1.0 and 1.0–2.0 mm) were added to thoroughly stirred water in a Mastersizer 2000 laser diffractometer. The suspension obtained was passed directly through the measuring system. The dynamics of median (equivalent diameter d50) particle-size distribution decrease (interpolated with a logarithmic function) was assumed to be the measure of soil aggregate stability. In order to show the applicability of the new method, the results obtained (for selected and diverse soils) were compared with those from the wet sieving standard method. The main conclusion is that the proposed method is convenient and can be successfully used for the estimation of soil aggregate stability. Moreover, it has wider application because standard sieving methods are restricted to aggregates >0.25 mm whereas, with the use of the laser diffraction method, smaller aggregates can be measured. The energy delivered to the aggregates in the process of aggregate disintegration is more reproducible in the method described here. The method also provides an opportunity to verify that the soil aggregates are completely destroyed (lack of the changes of the median value shows the end of soil aggregate disintegration).

The clay mineralogy and chemistry of a green lacustrine marl that has been pedogenically modified in the upper part was investigated in order to better understand the formation of low-temperature Fe-rich 10 Å clay. Twelve samples in a vertical sequence have been investigated using X-ray diffraction (XRD), chemical analysis, scanning electron microscopy (SEM) and laser particle size analysis. The clay assemblage has a range of overall illite-smectite (I-S) compositions (64–100%) resulting from several I-S phases that, for the sake of modelling, have been simplified to one to three I-S phases of increasing illitic content. Where the lacustrine marl has been pedogenically modified, the smectite-rich I-S is much reduced in abundance or absent and the 10 Å -rich component is both more abundant and more illitic. These assemblages are a consequence of illitization of detrital I-S in the lake and soil, and dissolution of other clays (kaolinite and chlorite) in the hypersaline lake. Interlayer K, octahedral Fe and octahedral + interlayer Mg increase with intensity of illitization (increase range 0.32–0.63, 0.68–1.67, 0.18–0.24 per O10(OH)2, respectively), first in the increasingly saline lake, and latterly as a result of wetting and drying in a gley soil. In the soil environment, reduction of Fe(III) to Fe(II) resulted in increased layer charge but, as by this stage very few smectite interlayers remained, this did not result in an equivalent increase in illite. Laser particle-size analysis, supported by SEM observation, shows the existence of a bimodal distribution of clay particle size (maxima at 0.2 and 1.5–1.8 μm) in which the finer fraction increases largely in the pedogenically affected samples, probably due to particle break-up caused by seasonal wetting and drying. This ‘dual action’ illitization, first in a hypersaline lake and latterly through wetting and drying, may be responsible for both the intensity of illitization and exceptionally high (for the Solent Group) Fe content of the authigenic illite. The chemical characteristics of the illitic I-S and the illite end-member correspond to glauconite. Hence, this is an example of onshore, non-pelletal glauconite formation.

The Aktoprak Basin, Turkey, provides important clues regarding regional palaeoclimatic changes which have not so far been elucidated. The purpose of the present study is to fill this gap using mineralogical, geochemical and isotopic characterization of cyclic sedimentation within Neogene sedimentary units. Early Miocene alluvial-fan to cyclic shallow-lacustrine sediments of the Aktoprak Basin consist of conglomerate, sandstone, mudstone, marl, limestone and palaeosol. The increasingly fine upward grain size and bed thicknesses suggest that the alluvial fan was fed by an ephemeral braided river. The cyclic sandflat–mudflat–shallow-lake succession is predominantly composed of small-scale sandstone-mudstone beds. Sandstone intervals in the sedimentary cycles are interpreted to be a result of sedimentation from shallow, ephemeral braided-river channels, the deposits having evolved under water-saturated conditions in response to climate changes. The mudstone intervals are interpreted as having been laid down via sedimentation during distal sheet floods which developed either under sub-aerial exposure or in a water-saturated environment. Palaeocurrent measurements indicate that the general transport direction in the Early Miocene was from east to west. The lacustrine sediments of the Aktoprak Basin consist of calcite + quartz + feldspar + serpentine coexisting mainly with smectite ± palygorskite ± illite ± chlorite. Illite and chlorite are either detrital, having originated from basement units, or the illite formed authigenically from smectite. Calcite and clay appear as cement-building conglomerate, sandstone and mudstone. The clay content decreases with increasing calcite and the presence of an inverse relationship between CaO and other oxides may correspond to an inverse relationship between calcite and other minerals. Furthermore, Al2O3, Fe2O3, TiO2, MgO, Ni, Co, Cu, Sr, Ba and Zr values in the smectite-bearing mudstone and sandstone are consistent with the chemical compositions of rocks in the surrounding area, mainly ophiolitic and volcanogenic associations. Micromorphologically, the development of smectite as a cement on leached feldspar, the occurrence of palygorskite fibres as bridges between crystals and rock fragments, as well as the presence of ‘edging’ smectite flakes suggest an authigenic origin. Field observations, mineralogy, geochemistry and the results of δ18O and δ13C isotopic determinations reveal that periodic palaeoclimatic changes were controlled by alternating wet and dry periods that resulted in a relative upward decrease in precipitation of authigenic smectite ± palygorskite within the sections, under the influence of geochemical and pH fluctuations in meteoric water within the shallow-lake environment.

The present paper shows the importance of Inverse Gas Chromatography (IGC) for the determination of the surface properties of bentonites. These properties are dispersive surface energy, acid-base properties, surface heterogeneity, sorption isotherms, BET surface areas and heat of sorption, using different probe molecules. IGC can contribute to the interpretation, prediction and optimization of the studied materials' properties. The paper focuses on two distinctive bentonite samples from Porto Santo Island, Madeira archipelago. In view of their potential value, achieved through their incorporation in products for dermopharmacy and dermocosmetics, particle size and particle surface properties are of fundamental importance.

Corrensite and chlorite-rich chlorite-smectite (Chl-S) mixed-layers occurring in the Macigno Formation of northwestern Tuscany were investigated by XRPD/SEM techniques. The samples from the Macigno outcrops were affected by metamorphism corresponding to the high-diagenesis/low-anchizone transition boundary. The basal spacing of corrensite measured from 00l reflections on EG–Mg2+-saturated samples ranges from 30.97 to 31.18 Å with a coefficient of variation (CV) of 0.46–0.77%, consistent with the rational pattern of a 1:1 Chl-S periodic stacking sequence. X-ray patterns of heated K+-saturated specimens reveal the presence of two types of corrensite, probably with different interlayer charges on their respective smectite-like layers. The chlorite-rich Chl-S mixed layers coexisting with corrensite consist of R2 chlorite (0.70–0.75)/S and chlorite (0.90)/S with long-range ordering R ⩾ 1. SEM observations show that corrensite and chlorite-rich Chl-S mixed-layers are closely mixed on a sub-micron scale. Some grains of corrensite and chlorite-rich Chl-S mixed-layers include zones (2–10 μm) of chlorite composition, as shown by microprobe analyses.

This paper presents the results of acidic leaching of kaolinite from the flotation waste of the RTB Bor copper mine, Serbia. The kaolinitic concentrate from the flotation waste contains 32% Al2O3. Kinetic investigations were conducted on the leaching of kaolinite roasted at 750°C for 60 min under air using H2SO4, HNO3 and HCl. Activation energies for the process were 74, 63 and 63.2 kJ mol–1 for sulphuric, nitric and hydrochloric acids, respectively. The kinetic function D3: [1 – (1 – α)1/3]2 = kt was chosen to describe the fractional conversion dependence on time and temperature. This enabled effective management of the leaching process to be carried out.

The relationship between three parameters, the Tmax given by Rock-Eval pyrolysis, the illite content in illite-smectite mixed layers (I-S) and the Ku¨bler Index (KI) has been investigated in the Cretaceous–Neogene, sedimentary syn-orogenic successions in the Northern Apennines (Italy). A strong relationship was found between maturity stages of kerogen, illite content in I-S and KI. The oil formation zone for continental organic matter (Type III), delimited by Tmax between 434 and 465ºC, corresponded to rocks with short-range ordering R1, I-S with illite content between 60 and 85% and KI values in the range 0.85–0.65 (ºΔ2θ). Over-mature rocks were characterized by Tmax >465ºC, a long-range ordered I-S with an illite content >85% and KI in the range 0.65–0.45 (ºΔ2θ). The relationship permits use of both mineralogical parameters and Tmax to estimate palaeotemperatures in sedimentary successions and it can be exploited in hydrocarbon research to evaluate the petroleum potential.