The characteristics and mechanisms of competitive adsorption of trace metals on bacteria-associated clay mineral composites have never been studied, despite their being among the most common organic–mineral complexes in geological systems. Herein, competitive adsorption of Pb and Cd on Pseudomonas putida–montmorillonite composite was investigated through adsorption–desorption experiment, isothermal titration calorimetry (ITC), and synchrotron micro X-ray fluorescence (μ-XRF). From the experiment, stronger competition was observed on clay mineral than on bacteria–clay composite because more non-specific sites accounted for heavy metal adsorption on clay mineral surface at the studied pH 5. Both competing heavy metals tended to react with bacterial fractions in the composite, which was verified by the higher correlation of Cd (and Pb) with Zn (R2 = 0.41) elemental distribution than with Si (R2 = 0.10). ITC results showed that competitive adsorption exhibited a lower entropy change (ΔS) at the metal-sorbent interfaces compared with single-metal adsorption, revealing that Cd and Pb are bound to the same types of adsorption sites on the sorbent. The competitive effect on bacteria–clay composite was found to be helpful for a better understanding on the fixation, remobilization and subsequent migration of heavy metals in multi-metal contaminated environments.

Fe₃O₄-CuO@montmorillonite was prepared using coprecipitation method, and its structure was determined by XRD, IR, and transmission electron micrograph (TEM). Montmorillonite in Fe₃O₄-CuO@montmorillonite nanocomposite allowed the silicate layer of montmorillonite to behave as a barrier, which prevented the agglomeration and natural crystallization of Fe₃O₄ and CuO. Furthermore, the chlorine dioxide (ClO₂) oxidative degradation of anthracene-contaminated soil was studied in detail using Fe₃O₄-CuO@montmorillonite as a magnetic heterogeneous catalyst. The operating parameters such as ClO₂ concentration, catalyst dosage, reaction time, and pH were evaluated. Compared with the conventional ClO₂ oxidation process without the catalyst, the ClO₂ catalytic oxidation system could significantly enhance the degradation efficiency. Under the optimal condition (anthracene concentration 89.8 mg/kg, water soil mass ratio 3:1, initial pH 7, ClO₂ concentration 1 mol/kg, catalyst dosage 1 g/kg, reaction time 30 min, and reaction temperature 25 °C), anthracene degradation efficiency achieved 96.2 %. The catalyst could be easily reused by magnetic separation and used at least 8 cycles without obvious loss of activity. The kinetic studies revealed that the ClO₂ catalytic oxidation degradation of anthracene-contaminated soil with Fe₃O₄-CuO@montmorillonite as catalyst followed pseudo-first-order kinetics with respect to ClO₂ concentration. Thus, this study showed potential application of ClO₂ catalytic oxidation process in remediation of organic pollutant-contaminated soil.

Textile wastewater was treated by adsorption in batch and column systems using electrochemically modified montmorillonite clay and activated carbon. Textile wastewater was obtained from a denim manufacturing process; according to the characterization of wastewater, non-biodegradable organic matter was found and it limits the application of biological treatments, and then an alternative method was evaluated. The adsorption process was performed with natural and modified materials; iron-modified montmorillonite was prepared at pH 7 using iron electrodes and activated carbon was treated with copper electrodes at pH 2, and 10–12 % of iron and copper respectively were found in the modified materials. Adsorption kinetics and isotherms of chemical oxygen demand (COD), color, and total organic carbon (TOC) were evaluated; the adsorption capacities for color were 50, 37, and 44 U PtCo/g for natural clay, activated carbon, and iron-modified clay, respectively. Adsorption kinetics of COD, color, and TOC data were best adjusted to Elovich model and isotherms data to Freundlich model, indicating chemisorption on heterogeneous materials. The regeneration of materials was performed in the presence and absence of hydrogen peroxide. Continuous systems were evaluated for color and TOC. Fe-modified clay was the best adsorbent, and data were best adjusted to Thomas and Yoon-Nelson models.

Chitosan-montmorillonite composite was extensively used for the removal of heavy metals from wastewater. In wastewater, copper (Cu²⁺) usually coexist with the organic ligands, which had unknown effect on Cu²⁺ adsorption by the composite materials. In order to understand further on that, the adsorption of copper by the composite materials must be studied. In the present study, montmorillonite was coated with chitosan, and X-ray diffraction (XRD) patterns of the composite proved the intercalation of chitosan in the montmorillonite. Fourier transform infrared (FTIR) spectra of the composite identified the presence of amino group on the composite, and that of the composite saturated with metals identified the interaction between the amino groups and metals. Langmuir adsorption isotherm indicated that the composite had more capacity to adsorb Cu²⁺ from wastewater than montmorillonite. The adsorption capacity of Cu²⁺ by montmorillonite and chitosan-montmorillonite composite was studied, respectively, as a function of pH and in the presence of acetate. Compared to the montmorillonite at low ligand concentration (0.08 mmol/L) or low pH (<4.0), the coexisting acetate increased more Cu²⁺ adsorption by the composite. The acetate ligand presented less depression on the adsorption by the composite than that by montmorillonite at high ligand concentration (4 mmol/L) or high pH (>4.5). Therefore, the composite is more suitable for removing Cu²⁺ than montmorillonite in acid aqueous medium.

A modified montmorillonite (MMT) was prepared using an acid activation-sodium activation-iron oxide coating method to improve the adsorption capacities of natural MMTs. For MMT, its interlamellar distance increased from 12.29 to 13.36 Å, and goethite (α-FeOOH) was intercalated into its clay layers. Two novel media-injected permeable reactive barrier (MI-PRB) configurations were proposed for removing arsenic from groundwater. Sand tank experiments were conducted to investigate the performance of the two MI-PRBs: Tank A was filled with quartz sand. Tank B was packed with quartz sand and zero-valent iron (ZVI) in series, and the MMT slurry was respectively injected into them to form reactive zones. The results showed that for tank A, total arsenic (TA) removal of 98.57 % was attained within the first 60 mm and subsequently descended slowly to 88.84 % at the outlet. For tank B, a similar spatial variation trend was observed in the quartz sand layer, and subsequently, TA removal increased to ≥99.80 % in the ZVI layer. TA removal by MMT mainly depended on both surface adsorption and electrostatic adhesion. TA removal by ZVI mainly relied on coagulation/precipitation and adsorption during the iron corrosion. The two MI-PRBs are feasible alternatives for in situ remediation of groundwater with elevated As levels.

Transformation of inorganic arsenic species has drawn great concern in recent decades because of worldwide and speciation-dependent pollution and the hazards that they pose to the environment and to human health. As(III) photooxidation in aquatic systems has received much attention, but little is known about photochemical transformation of arsenic species on top soil. As(III) photooxidation on natural montmorillonite under UV-A radiation was investigated by using a moisture- and temperature-controlled photochemical chamber with two black-light lamps. Initial As(III) concentration, pH, layer thickness, humic acid (HA) concentration, the presence of additional iron ions, and the contribution of reactive oxygen species (ROS) were examined. The results show that pH values of the clay layers greatly influenced As(III) photooxidation on montmorillonite. As(III) photooxidation followed the Langmuir–Hinshelwood model. HA and additional iron ions greatly promoted photooxidation, but excess Fe(II) competed with As(III) for oxidation by ROS. Scavenging experiments revealed that natural montmorillonite induced the conversion of As(III) to As(V) by generating ROS (mainly HO• and HO₂ •/O₂ •⁻) and that HO• radical was the predominant oxidant in this system. Our work demonstrates that photooxidation on the surface of natural clay minerals in top soil can be important to As(III) transformation. This allows understanding and predicting the speciation and behavior of arsenic on the soil surface.

This work investigates influence of different aluminosillicate nanoparticles (NPs) which are found in air in selected workplaces on the properties of the phospholipid (DPPC) monolayer at air–saline interface considered as ex vivo model of the lung surfactant (LS). The measurements were done under physiological-like conditions (deformable liquid interface at 37 °C) for NP concentrations matching the calculated lung doses after exposure in the working environment. Measured surface pressure–area (π–A) isotherms and compressibility curves demonstrated NP-induced changes in the structure and mechanical properties of the lipid monolayer. It was shown that hydrophilic nanomaterials (halloysite and bentonite) induced concentration-dependent impairment of DPPC’s ability of attaining high surface pressures on interfacial compression, suggesting a possibility of reduction of physiological function of natural LS. Hydrophobic montmorillonites affected DPPC monolayer in the opposite way; however, they significantly changed the mechanical properties of the air–liquid interface during compression. The results support the hypothesis of possible reduction or even degradation of the natural function of the lung surfactant induced by particle–phospholipid interactions after inhalation of nanoclays. Presented data do not only supplement the earlier results obtained with another LS model (animal-derived surfactant in oscillating bubble experiments) but also offer an explanation of physicochemical mechanisms responsible for detrimental effects which arise after deposition of inhaled nanomaterials on the surface of the respiratory system.