The capacity and mechanism of the adsorption of aqueous barium (Ba), cobalt (Co), strontium (Sr), and zinc (Zn) by Ecuadorian (NatAllo) and synthetic (SynAllo-1 and SynAllo-2) allophanes were studied as a function of contact time, pH, and metal ion concentration using kinetic and equilibrium experiments. The mineralogy, nano-structure, and chemical composition of the allophanes were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and specific surface area analyses. The evolution of adsorption fitted to a pseudo-first-order reaction kinetics, where equilibrium between aqueous metal ions and allophane was reached within <10 min. The metal ion removal efficiencies varied from 0.7 to 99.7% at pH 4.0 to 8.5. At equilibrium, the adsorption behavior is better described by the Langmuir model than by the Dubinin–Radushkevich model, yielding sorption capacities of 10.6, 17.2, and 38.6 mg/g for ${\mathrm{Ba}}^{2+}$ , 12.4, 19.3, and 29.0 mg/g for ${\mathrm{HCoO}}_2^{-}$ ; 7.2, 15.9, and 34.4 mg/g for ${\mathrm{Sr}}^{2+}$ ; and 20.9, 26.9, and 36.9 mg/g for ${\mathrm{Zn}}^{2+}$ , by NatAllo, SynAllo-2, and SynAllo-1, respectively. The uptake mechanism is based on a physical adsorption process rather than chemical ion exchange. Allophane holds great potential to effectively remove aqueous metal ions over a wide pH range and could be used instead of other commercially available sorbent materials such as zeolites, montmorillonite, carbonates, and phosphates for special wastewater treatment applications.

Hydrated aluminosilicates were synthesized with and without aqueous heavy metals (Me), such as cobalt (Co), chromium (Cr), and zinc (Zn), by a sol–gel process at different initial molar ratios of Ca/(Si + Al) (0.6–1.6) and Me/Si (0.0–2.0), and constant Al/Si ratio (0.05) using equilibrium-approaching experiments. The chemical composition of the reactive solutions during aluminosilicate precipitation and maturation was monitored by ICP-OES. The mineralogy, nanostructure, and chemical composition of the precipitates were studied by XRD and high-resolution TEM. At Me/Si ratios ≤ 0.2, calcium–aluminium–silicate–hydrates (C–A–S–H) with a defect 14 Å tobermorite-like structure formed, whereas at a Me/Si ratio of 2.0, either trioctahedral Co- and Zn-smectite or amorphous Cr gels precipitated, independent of the initial Ca/(Si + Al) ratio used for gel synthesis. The immobilization capacities for \( {\text{Co}}^{2 + } \), \( {\text{Cr}}^{3 + } \), and \( {\text{Zn}}^{2 + } \) by C–A–S–H, Cr gel, and trioctahedral smectite are 3–40 mg/g, 30–152 mg/g, and 122–141 mg/g, respectively. The immobilization mechanism of heavy metals is based on a combination of isomorphous substitution, interlayer cation exchange, surface (ad)sorption, and surface precipitation. In engineered systems, such as underground concrete structures and nuclear waste disposal sites, hydrated aluminosilicates should exhibit a high detoxication potential for aqueous heavy metals.

Nanoscale zero-valent iron (nZVI) based (nano)composites supported by clay mineral substrates are a promising technology for the in-situ remediation of groundwater and (sub)soils contaminated with chlorinated hydrocarbons, such as trichloroethene (TCE). However, the physicochemical processes and interaction mechanisms between nZVI particles, clay minerals and TCE are poorly understood, yet. We immobilized nZVI particles on a commercial bentonite substrate to prepare a novel nZVI-B nanocomposite and tested its performance for TCE removal from solution against pure nZVI in batch reactors. The nZVI-B exhibited a higher reactivity (2.2·10^-3 L h^-1·m^-2) and efficiency (94%) for TCE removal than nZVI (2.2·10^-4 L h^-1·m^-2; 45%). Sorption of TCE onto the clay surfaces and reductive de-chlorination in "micro-reactors" developing within the nZVI-B controlled the kinetics and the magnitude of TCE loss from solution. Contrary to pure nZVI, no signs of nZVI particle agglomeration or inactivation due to oxide shell formation were found in nZVI-B. We attribute this to the uptake of dissolved Fe species that are liberated via progressing nZVI particle corrosion by the bentonite substrate to form Fe-smectite (nontronite domains), which prevented from a deterioration of the properties and reactivity of the nZVI-B. The use of nZVI-B in permeable reactive barriers at contaminated field sites could be feasible, where a system-inherent reduction of the soil-bearing capacity has to be minimized.

Silver nanoparticles (AgNPs) are of great interest due to their antimicrobial properties, but their reactivity and toxicity pose a significant risk to aquatic ecosystems. In biological systems, AgNPs tend to aggregate and dissolve, so they are often stabilized by agents that affect their physicochemical properties. In this study, microalga Chlorella vulgaris was used as a model organism to evaluate the effects of AgNPs in aquatic habitats. Algae were exposed to AgNPs stabilized with citrate and cetyltrimethylammonium bromide (CTAB) agents and to AgNO₃ at concentrations that allowed 75% cell survival after 72 h. To investigate algal response, silver accumulation, ROS content, damage to biomolecules (lipids, proteins, and DNA), activity of antioxidant enzymes (APX, PPX, CAT, SOD), content of non-enzymatic antioxidants (proline and GSH), and changes in ultrastructure were analyzed. The results showed that all treatments induced oxidative stress and adversely affected algal cells. AgNO₃ resulted in the fastest death of algae compared to both AgNPs, but the extent of oxidative damage and antioxidant enzymatic defense was similar to AgNP-citrate. Furthermore, AgNP-CTAB showed the least toxic effect and caused the least oxidative damage. These results highlight the importance of surface-stabilizing agents in determining the phytotoxicity of AgNPs and the underlying mechanisms affecting aquatic organisms.

Silver nanoparticles (AgNPs) are used in a wide range of consumer products because of their excellent antimicrobial properties. AgNPs released into the environment are prone to transformations such as aggregation, oxidation, or dissolution so they are often stabilised by coatings that affect their physico-chemical properties and change their effect on living organisms. In this study we investigated the stability of polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB) coated AgNPs in an exposure medium, as well as their effect on tobacco germination and early growth. AgNP-CTAB was found to be more stable in the solid Murashige and Skoog (MS) medium compared to AgNP-PVP. The uptake and accumulation of silver in seedlings was equally efficient after exposure to both types of AgNPs. However, AgNP-PVP induced only mild toxicity on seedlings growth, while AgNP-CTAB caused severe negative effects on all parameters, even compared to AgNO₃. Moreover, CTAB coating itself exerted negative effects on growth. Cysteine addition generally alleviated AgNP-PVP-induced negative effects, while it failed to improve germination and growth parameters after exposure to AgNP-CTAB. These results suggest that the toxic effects of AgNP-PVP are mainly a consequence of release of Ag⁺ ions, while phytotoxicity of AgNP-CTAB can rather be ascribed to surface coating itself.