The size, shape, and continuity of pores in mineral solids greatly influence the behavior of percolating liquids and solids in porous media, which has significant practical environmental implications. In order to expand understanding of these properties in soil minerals, the present study was undertaken to analyze the pore characteristics of bentonite, illite, and kaolinite in the forms of powder and aggregates of different dimensions, combining water-vapor desorption and mercury-intrusion techniques. Different granulometric fractions of milled quartz glass were also studied. With increasing aggregate size of the minerals, larger pore volumes (up to 25%), smaller surface areas (down to 15%), larger average radii (up to 15%), and smaller fractal dimensions (down to 6%) were measured using water-vapor adsorption-desorption data. The differences were smallest for bentonite, possibly due to the smallest particle size of this mineral and/or to its very large water-vapor adsorption capacity. The degree of water-vapor adsorption on quartz was too small to rely on the data obtained.

The pore volumes and average radii, measured by mercury-intrusion porosimetry, were up to few times larger for the mineral powders than for their aggregate counterparts. Similar values were noted for aggregates >1 mm in diameter, for which the input of interaggregate spaces into total porosity of the sample bed was negligible. Two pathways of mercury intrusion were detected in porosimetric curves: filling of interaggregate spaces, and penetration into aggregates. Similar penetration thresholds into aggregates of different sizes were calculated. With increasing size of quartz grains, the pore volume of the quartz bed decreased whereas the average pore radius increased. Mercury intrusion detected pore-fractal behavior of bentonite and kaolinite, but for aggregated minerals the calculated values of fractal dimensions were >3, values which increased with increasing aggregate size. Very similar pore parameters were measured for aggregates prepared from a natural deposit of kaolinite and for artificially prepared aggregates from powder of the same mineral, indicating that artificial aggregation can simulate natural processes.

Both water desorption and mercury intrusion detected fractal behavior in the limited range of pores. A test to find fractal build up of the aggregates in extended scales based on a dependence of surface area of unit volume of aggregate bed on aggregate size showed no fractal-aggregate build-up.

The modification of minerals with metals can promote changes in their surface and, consequently, in their physicochemical properties. Minerals could have played an important role in the origin of life as they can protect molecules against degradation by radiation and hydrolysis, pre-concentrate molecules from dilute solutions and catalyse the formation of polymers. Thus, the current work studied the modification of montmorillonite with Cu2+ and Fe3+ ions. These modified montmorillonites were used to study the interaction with adenine dissolved in distilled water and artificial seawater 4.0 Gy (Gy = billion years ago). The most important result of this work is that the adsorption of adenine onto modified montmorillonites is a complex interaction among adenine, salts in seawater and Cu2+/Fe3+-montmorillonite (Cu2+/Fe3+-Mont) . The adsorption of Cu2+ and Fe3+ onto montmorillonite decreased its surface area and pore volume. The Sips isotherm model showed the best fit of the data and n values indicate that the adenine adsorption process was homogeneous. The highest adenine adsorption was obtained in artificial seawater 4.0 Gy onto Fe3+-Mont at 60°C and the lowest in distilled water or artificial seawater 4.0 Gy onto montmorillonite [montmorillonite washed with distilled water (Mont-STD)] at 60°C. Adenine adsorption onto Mont-STD/montmorillonite modified with 500 ml of 0.1 mol l−1 of CuCl2 and Fe3+-Mont was an exothermic process and an endothermic process, respectively. For all adsorptions ΔG was negative. The adsorption of adenine onto Fe3+-Mont was ruled out by entropy and the other samples by enthalpy and entropy, being a major contribution for Gibbs free energy from enthalpy. The Fourier transform-infrared data indicate that the interaction of adenine with minerals may occur through the NH2 functional group.

The amorphous aluminosilicate allophane was synthesized by rapid mixing of inorganic solutions with high initial concentrations (10 – 100 mmol/l) followed by hydrothermal treatment. X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed homogeneous products having a hollow spherical amorphous structure with a particle diameter of 3 – 5 nm. The amorphous products had a high BET specific surface area (490 – 552 m2/g) in comparison with natural allophane and had a narrow pore-size distribution (2 – 5 nm in diameter). The results of water vapour adsorption isotherm studies showed a gradual increase over the range of relative water vapour pressure of 0.6 – 0.9 and reached a maximum of ∼85 wt.%. The synthetic allophane shows promise as an adsorbent material because of its high adsorption-desorption capacity and its unique structure.

The purpose of this study was to determine whether a bentonite from the Gafsa deposit (western Tunisia) could be used to remove the Foron Blue 291 (FB) azo dye from wastewater. Batch adsorption and desorption experiments were conducted using untreated and purified bentonite and the influence of contact time, pH, adsorbent mass and temperature of the dye solution on the adsorption of FB was evaluated. Kinetic and isotherm data were fitted using two non-linear kinetic and two non-linear isotherm equations. In addition, the fits were evaluated using the coefficient of determination (R2) and the RMSE. The percentage of dye removal increased with increasing amount of adsorbent until total discolouration was achieved. The adsorption isotherms followed the Langmuir model, with the purified bentonite having a higher adsorption capacity than the raw material due to its higher specific surface area. In addition, the FB molecules were removed from the liquid medium by physical adsorption. Batch desorption experiments were conducted to study the desorption kinetics and the characteristics of the desorption isotherms as well as to quantify the portion of the FB (by mass) that was irreversibly fixed on the solid. Overall, the desorption kinetics were similar to the adsorption kinetics, which indicated that the adsorption-desorption process of azo dye is non-singular; irreversibility occurred that was underlined by an observed thermodynamic index of irreversibility (TII) of 0.69–0.94. The desorption isotherms of the FB depended on the mass of the FB that was initially adsorbed on the bentonite sample, suggesting hysteresis. The amount of irreversibly retained FB was between 46 and 68% of the initial adsorbed mass.

In this study, a clinoptilolite modified with apolaccase was used to adsorb Reactive Black 5 (RB5) dye from aqueous solution using the batch procedure. The influences of pH, contact time, temperature and absorbent dosage on the adsorption were investigated. The optimum adsorption was obtained at pH = 6, contact time = 60 min, temperature = 25ºC and adsorbent dosages of 1.62 and 1.59 mg/50 mL per gram of clinoptilolite and of apolaccase-modified clinoptilolite (LMC), respectively). The adsorption experimental data fitted both the Langmuir and Freundlich isotherm models well. In addition, pseudo-first-order and pseudo-second-order kinetics were used to study the kinetics of RB5 dye adsorption onto natural clinoptilolite and LMC. Adsorption appears to follow pseudo-second-order kinetics with a high correlation coefficient. Thermodynamic parameters such as changes in the free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) of adsorption were calculated. The thermodynamic parameters indicate that the adsorption of RB5 dye onto LMC was less spontaneous, feasible and endothermic. The LMC can be used as an alternative low-cost adsorbent for the dye removal from aqueous solutions.

Calcigel bentonite-polyacrylamide (PAA) composites were investigated for their formation characteristics and their macroscopic hydro-mechanical and microscopic structural properties. The composites prepared were different in terms of the polymer charge, i.e. cationic (PAA+), anionic (PAA−), non-ionic (PAA°) and in terms of the polymer-to-clay ratio. The latter varied according to the individual maximum sorption capacity established from adsorption isotherms. Oedometer and waterretention testswere conducted on composites prepared under initial slurry conditions. The microstructure of the composites was investigated using environmental scanning electron microscopy (ESEM). At low stress, distinctly increased void ratios were found for all types of the composites, whereas under highstress conditions only the PAA+-composite prepared at 100% of the maximum sorption capacity showed an increase in void ratio. Analyses by ESEM on this composite indicated structural changes related to the preferential face-to-face aggregation, which help to explain the macroscopic behaviour and also account for the increased hydraulic permeabilities observed.

Polycyclic aromatic hydrocarbons are increasingly widespread pollutants introduced into the environment via oil spillage and incomplete anthropogenic combustion of fossil fuels. In this work, the capacity of stevensite and sepiolite to adsorb phenanthrene (PHE) has been evaluated experimentally by batch testing. Both clay minerals are distributed widely in the Madrid Basin, are of low cost and can be applied with minimal environmental impact. In the context of few previous studies, adsorption isotherms have been developed to understand the adsorption mechanisms and were fitted to the Freundlich and linear models with virtually the same results. Although stevensite showed greater adsorption capacity than sepiolite, the isotherms were constructed for equilibrium concentrations up to 0.8–1.0 mg/L due to the low solubility of PHE in water. When compared to other adsorbents the ability of stevensite to retain PAHs should be examined further in order to add and complement novel functions in reactive barriers.

Hydrolysis and adsorption of the sulfonylurea herbicides rimsulfuron and primisulfuron were investigated under laboratory conditions. Degradation in aqueous solutions was determined between pH 3 and 8 and between 5 and 35 C. Rimsulfuron degraded faster than primisulfuron. Half-lives at different temperatures at pH 4 ranged from 0.16 to 5.8 d for rimsulfuron and from 0.47 to 16.1 d for primisulfuron. Primisulfuron hydrolysis at 30 C decreased with increasing pH, but rimsulfuron decreased up to pH 7, then increased, suggesting rapid degradation in alkaline conditions. Adsorption, measured in six Colorado soils, was complete within 2 h in all soils. Adsorption isotherms were determined by batch equilibration of 75 to 600 μg L−1. Rimsulfuron was adsorbed in amounts 3.7 to 7 times higher than primisulfuron, with adsorption distribution coefficients (Kd) ranging from 0.1 to to 1.18 for primisulfuron and from 0.71 to 5.1 for rimsulfuron. Adsorption of both herbicides was slightly correlated with soil clay content, and primisulfuron adsorption was also correlated with organic matter content.

Adsorption of five phenylurea herbicides, metobromuron [3-(p-bromophenyl)-1-methoxy-1-methylurea], monolinuron [3-(p-chlorophenyl)-1-methoxyl-1-methylurea], linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea], chlorbromuron [3-(4-bromo-3-chlorophenyl)-1-methoxy-1-methylurea], and CGA-15646 [3-(3-chloro-4-methylphenyl)-1,1-dimethylurea] by eight selected soils of Czechoslovakia were studied. Constants from Freundlich and Langmuir equations were calculated and correlated with the major soil properties. Freundlich K values ranged from 1.84 to 128, and the Freundlich equation was better fitted to the adsorption isotherms than was the Langmuir equation. Soil organic-matter content was the most important factor influencing the range of adsorption.