Behavior of Ag species in presence of aquatic sediment minerals - In context of aquatic environmental safety

Abstract

In recent years, there has been a growth in the number of products containing Ag nanoparticles (AgNPs) in many areas and their use suggests that the water-soil environment may be exposed to the contaminant with different Ag species. Therefore, the sorption of two Ag forms (i.e. Ag(I) ions and nanoparticles - AgNPs) on clay minerals (montmorillonite and kaolinite) and iron (oxyhydr)oxides (ferrihydrite) as a function of solution:mineral ratio (100:1, 250:1, 500:1), solution pH (3.0, 5.5 and 7.0) and initial Ag concentration (0.1-100 mg/dm³) was studied using batch method. In addition the binding strength/mobility of the bonded Ag species was researched. The results show a great sorption potential of clay minerals for both Ag forms and lower sorption capacity of ferrihydrite, in particular for Ag(I) ions. The maximum sorption capacities of montmorillonite, kaolinite and ferrihydrite estimated from three-parameter isotherm model of Sips were 94.39 mg/g, 117.8 mg/g and 26.48 mg/g for AgNPs and 17.92 mg/g, 21.14 mg/g and 3.072 mg/g for Ag(I) ions, respectively. Aggregation process plays an important role in sorption and mobility of AgNPs. The sequential extraction study indicated different binding mechanisms of the Ag forms onto the clay minerals and ferrihydrite, which depended on the active sites of minerals as well as the Ag species nature in the solution. Ag(I) was weakly bound by clay minerals but presence of iron (oxyhydr)oxides decreased the Ag(I) mobility and bioavailability. On the other hand, AgNPs bound with the active centers of minerals in a very strong way and were not able to release into water. The study of the binding of Ag forms by clay minerals and (oxyhydr)oxides allows to determine the influence of their physicochemical and structural properties, including e.g. pore size on Ag sorption. These results allow these properties to be taken into account in the study of environmental samples, including waters and soils. Moreover, the results showed that in the study of behavior of Ag forms in contact with the minerals, in addition to the sorption capacity, the susceptibility to their release is very important. Studies on sorption/desorption of AgNPs and Ag(I) ions as a form of oxidation of AgNPs is important for understanding the transport and fate of the Ag species in soil, sediments and surface water because of different their behavior in contact with the minerals.

Keywords: Ag nanoparticles; Clay minerals; Iron (oxyhydr)oxides; Sequential extraction; Sorption.