Effect of Si/Al molar ratio on the immobilization of selenium and arsenic oxyanions in geopolymer.

The effect of Si/Al molar ratio of geopolymer on the immobilization of Se and As oxyanions was studied through leaching test and solid characterizations including XRD, FTIR, TG, NMR, XAFS, and N2 adsorption-desorption isotherm. As a whole, the leaching percentages of Se and As oxyanions increased with the increase of the Si/Al molar ratio of geopolymer. Linear combination fitting confirmed that most of selenite, selenate and arsenate ions existed in geopolymers through electrostatic interaction. Thus, Al tetrahedrons in geopolymer structure control the charge stability for these oxyanions to a large extent. Differently, as for arsenate ions, they were recrystallized into an arsenate compound (Na3.25(OH)0.25(H2O)12)(AsO4) in geopolymers. The additive of these pollutants has an adverse effect on the compactness of geopolymer, then influencing the leaching performance in turn. However, the changes in leaching results did not follow the variation trend of specific surface areas and pore volumes of geopolymers with different Si/Al ratios. The number and distribution of Al tetrahedron and compactness of geopolymer have a synergistic effect on the immobilization of these oxyanions. Besides, the compressive strengths of geopolymer samples are always higher than 20 MPa, which meets the requirement of safe disposal of hazardous waste.

Attachment of cerium oxide nanoparticles of different surface charges to kaolinite: Molecular and atomic mechanisms.

Sustainable applications of nanotechnology in agriculture require insights into the interactions between engineered nanoparticles (ENPs) and clay minerals, a key component in soil that governs the soil properties and functions. This study investigated the charge-dependent interactions of cerium oxide nanoparticles (CeO2NPs) with kaolinite at atomic level with several complementary surface characterization techniques. High resolution transmission electron microscope (HRTEM) and atomic force microscope (AFM) images showed strong attachment of positively charged and neutral CeO2NPs to the surface of kaolinite while the negatively charged CeO2NPs demonstrated low affinity to the surface of kaolinite, indicating strong electrostatic interactions between CeO2NPs and kaolinite surface. Attached CeO2NPs on kaolinite surface displayed charge-dependent aggregation, with neutral CeO2NPs showing the most substantial aggregation on kaolinite surface. The variation in hydrodynamic size and surface charge of kaolinite with the charge on CeO2NPs was observed. The attachment of CeO2NPs also changed the surface charge density distribution on the surface of kaolinite, converting a relatively homogenously charged basal plane into a heterogeneously charged plate. The change on kaolinite surface charge density may markedly affect the interactions of clay minerals with surrounding macro- and micro-nutrients in soil pore water and affect their bioavailability to plants.