A Raman-Based Imaging Method for Characterizing the Molecular Adsorption and Spatial Distribution of Silver Nanoparticles to Hydrated Mineral Surfaces.

Although minerals are known to affect the environmental fate and transformation of heavy-metal ions, little is known about their interaction with the heavily exploited silver nanoparticles (AgNPs). Proposed here is a combination of hitherto under-utilized micro-Raman-based mapping and chemometric methods for imaging the distribution of AgNPs on various mineral surfaces and their molecular interaction mechanisms. The feasibility of the Raman-based imaging method was tested on two macro- and micronized mineral models, muscovite [KAl2(AlSi3O10)(OH)(2)] and corundum (alpha-Al2O3), under key environmental conditions (ionic strength and pH). Both AgNPs(-) and AgNPs(+) were found to covalently attach to corundum (pH(pzc) = 9.1) through formation of Ag-O-Al- bonds and thereby to potentially experience reduced environmental mobility. Because label-free Raman imaging showed no molecular interactions between AgNPs- and muscovite (pH(pzc) = 7.5), a label-enhanced Raman imaging approach was developed for mapping the scarce spatial distribution of AgNPs(-) on such mineral surfaces. Raman maps comprising of n = 625-961 spectra for each sample/control were rapidly analyzed in Vespucci, a free open-source software, and the results were confirmed via ICP-OES, AFM, and SEM-EDX. The proposed Raman-based imaging requires minimum to no sample preparation; is sensitive, noninvasive, cost-effective; and might be extended to other environmentally relevant systems.