The present paper examines the phosphate adsorption from aqueous solutions onto goethite, bentonite, and bentonite–goethite system. The properties of the materials were studied by X-ray diffraction (XRD), attenuated total reflectance (ATR), and NMR spectra and by the measurement of the specific surface area, the point of zero charge (p.z.c.) and the pore-specific volume. ATR and NMR spectra of bentonite and bentonite–goethite system show peaks which correspond to tetrahedrally and octahedrally coordinated Al. The specific surface area of the system differs according to the appropriate method used, while system’s p.z.c. is higher than bentonite and lower than goethite. The pore-specific volume of bentonite–goethite system is higher than that of bentonite or goethite. According to XRD spectrum of bentonite–goethite system, goethite coats the (001) spacing of bentonite while the coating of (010) plane of bentonite is limited. The crystallinity of the system decreases and the negative permanent charge increases. Phosphate adsorption experiments took place at different pH (3.8–9.0) and concentrations (40.3–443.5 μmol L⁻¹) and constant capacitance model was applied to describe adsorption. A ligand exchange mechanism characterizes the model because the charge is divided among adsorbate and adsorbent. The constant capacitance model describes the adsorption mechanism in all examined pH. This model can be utilized in such systems using the surface protonation-dissociation constant of goethite and showing the exact shape of the adsorption isotherms for different pH values. Τhe produced low-cost bentonite–goethite system presents the highest adsorption of P per kilogram of goethite.

The sorption behaviors of brilliant blue FCF dye by natural clay and modified with iron chloride were determined. The materials were characterized by X-ray diffraction and scanning electron microscopy, and the zero point charges were also determined. The effects of pH, contact time, dye concentration, and temperature were considered. The results showed that clay does not suffer any important change in its structure after the chemical treatments. The pH influences the sorption of the dye in the unmodified clay, but this effect was not observed in the iron-modified clay. The equilibrium time and the sorption capacity for the unmodified clay were 48 h and 6.16 mg/g, while for the iron-modified clay, 24 h and 14.22 mg/g, respectively. The sorption kinetics results were best adjusted to the pseudo-first-order and pseudo-second-order models. Sorption isotherms were best adjusted to the Langmuir model, indicating that both clays have a homogeneous surface. Thermodynamic parameters (E, ΔS, ΔG and ΔH) were calculated for the natural clay from the data of the sorption kinetics at temperatures between 20 and 50 °C, indicating that the sorption process is exothermic. For the case of the iron-modified clay, it was not possible to calculate these thermodynamic parameters because the sorption capacities were similar in the temperature range selected.

Organoclays possess unique adsorption behaviour towards hydrophobic organic contaminants. They can also remediate ionic contaminants such as heavy metals and metalloids. The objective of the present study was to prepare organoclay and organoclay mixtures efficient to adsorb both cationic and anionic contaminants. The adsorbents were characterised by X-ray diffraction and infrared spectroscopy. Trivalent (Cr3+) and hexavalent (Cr2O 7 2-) chromium were selected as the model contaminants representing cationic and anionic properties. Bentonite modified with cationic surfactant hexadecyl trimethylammonium bromide at double the cation exchange capacity of the clay remarkably improved Cr2O7 2- adsorption capacity (as high as 0.49 mmol g-1). Similarly, its modification with anionic surfactant sodium dodecyl sulphate at the same dosage improved Cr3+ adsorption (as high as 0.36 mmol g -1). When these two organoclays were physically mixed in equal proportions (1:1), the resultant organoclay mixture efficiently adsorbed both Cr3+ (as high as 0.21 mmol g-1) and Cr2O 7 2- (as high as 0.32 mmol g-1) implying that the mixture could remediate both anionic and cationic contaminants simultaneously. The adsorption of Cr3+ by the organoclay and organoclay mixture fitted well to the Langmuir isothermal model whereas the adsorption of Cr2O7 2- fitted well to the Freundlich model. © 2013 Springer Science+Business Media Dordrecht.

Acid mine drainage (AMD) has long been a significant environmental problem that impairs water resources in historic or current mining industries throughout the world. One of the methods using passive treatment system at low cost to remove metals from solution involves the use of clays. The ability of three different adsorbents (montmorillonite K-10, bentonite (NT-25), and hydrotalcite (HT)) to remove Fe and Mn from aqueous solutions and acid mine drainage samples has been studied at different optimized conditions such as pH, amount of adsorbent and contact time. Flame atomic absorption spectrometer (FAAS) was used for measuring Fe and Mn concentrations. Langmuir and Freundlich isotherms were applied and isotherm coefficients were computed. A kinectic study was also developed for HT using the first order, second order and intraparticle diffusion models. A great amount of clay (more than 100 mg) and also contact times higher than 60 min had also no influence in the adsorption capacity for all adsorbents. HT was found to be the best among the studied clays removing more than 90 % of Fe and Mn for all AMD samples investigated. Moreover, the maximum adsorption capacity was 63.7 mg Mn g⁻¹ HT and 666.7 mg Fe g⁻¹ HT.

The effect of modified montmorillonites on the biodegradation and adsorption of selected steranes, diasteranes and hopanes was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The unmodified montmorillonite was treated with didecyldimethylammonium bromide, hydrochloric acid and the relevant metallic chloride to produce organomontmorillonite, acid activated montmorillonite and homoionic montmorillonite respectively which were used in this study. The study indicated that organomontmorillonite, acid activated montmorillonite and potassium montmorillonite did not support the biodegradation of the selected steranes, diasteranes and hopanes as alteration of the biomarkers via biodegradation varied from a paltry 2-6 %. The adsorption of the selected biomarkers on acid activated montmorillonite and organomontmorillonite was also poor. However, adsorption of the biomarkers on potassium montmorillonite was relatively high. Sodium montmorillonite and unmodified montmorillonite appear to stimulate the biodegradation of the selected biomarkers moderately (30-35 %) with adsorption occurring at low level. Calcium montmorillonite and ferric montmorillonite effected significant biodegradation (51-60 %) of the selected biomarkers.

Nanocomposite hydrogels based on poly(methacrylamide-co-acrylic acid) and nano-sized montmorillonite were prepared by aqueous dispersion and in situ radical polymerization. Optimum sorption conditions were determined as a function of montmorillonite content, contact time, pH, and temperature. The equilibrium data of Cu(2+) and Ni(2+) conformed to the Freundlich and Langmuir isotherms in terms of relatively high regression values. The maximum monolayer adsorption capacity of the nanocomposite hydrogel (with 3 wt% montmorillonite content), as obtained from the Langmuir adsorption isotherm, was found to be 49.26 and 46.94 mg g(-1) for Cu(2+) and Ni(2+), respectively, at contact time = 60 min, pH = 6.8, adsorbent dose = 100 mg/ml, and temperature = 318 K. Kinetic studies of single system indicated that the pseudo-second order is the best fit with a high correlation coefficient (R (2) = 0.97-0.99). The result of five times sequential adsorption-desorption cycle shows a good degree of desorption and a high adsorption efficiency.

Water in lakes and reservoirs accumulate phosphorous (P) from both internal and external loads. The external P load (EPL) coming from the watershed is considered to be the main cause of eutrophication of water bodies, and control strategies therefore focus on its reduction. However, algae blooms and anoxic conditions often continue even after EPL have been controlled, being the internal P load (IPL) originating from the sediment the main sources of P. To assess the efficiency of the adsorbent Phoslock (a modified bentonite) in controlling P concentrations in water and immobilize releasable P in sediments, mesocosm trials were carried out in a eutrophied reservoir and a model was described and applied that determines the amount of adsorbent and the application frequency necessary to control P concentrations in a eutrophied reservoir. The mesocosm trials confirm that Phoslock reduced P concentrations to or below the limits that define water in mesotrophic state, in approximately 2 weeks. The modeling results suggest that periodic reapplications of the adsorbent are required, unless EPL is reduced by 36 %, which allows the P concentrations in the water column to be constant. Such reduction in EPL would allow future applications of the adsorbent to be required only for control of IPL. The developed model allows planning remediation actions by determining quantities and frequencies for application of adsorbents for P control in eutrophied lakes and reservoirs.

Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu²⁺ and Zn²⁺ from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu²⁺ and Zn²⁺ from a aqueous solution containing a 100 mg/l of Cu²⁺ and Zn²⁺, where 92.9 % Cu²⁺ and 58.3 % Zn²⁺ were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu²⁺ and Zn²⁺. A kinetics study indicated that removing Cu²⁺ and Zn²⁺ with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu²⁺and Zn²⁺ on bentonite and the degradation of Cu²⁺and Zn²⁺ by nZVI on the bentonite. However, Cu²⁺ removal by B-nZVI was reduced rather than adsorption, while Zn²⁺ removal was main adsorption. Finally, Cu²⁺, Zn²⁺, Ni²⁺, Pb²⁺ and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters.