Evaluation of ATR-FTIR Spectroscopy with Multivariate Analysis to Study the Binding Mechanisms of ZnO Nanoparticles or Zn2+ to Chelex-100 or Metsorb

Abstract

Advancements in nanotechnology and the expected increases in production of commercial products with incorporated manufactured nanomaterials will very likely lead to increasing contamination of nanoparticles (NPs) in the environment. Though studying adverse impacts of NPs in the environment and their ecotoxicological fate and behavior is not new, limited information is available. A major challenge in this respect is the lack of a proper sampling technique that could provide data on concentrations of these materials in the environment. Diffusive gradient in thin-films (DGT) is a well-established method that can measure available concentrations of trace metals in soils and waters. Using this approach, different binding resins are employed as a sink to collect targeted chemicals during fixed times. Here, we examine the suitability of two common types of the DGT binding agents, commercially available Chelex-100 and Metsorb, to investigate whether these materials could irreversibly retain a model nanoparticle, ZnO, and if so, what would be the difference between bound ZnO NP and Zn(2+) ion. Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy was used to study the binding materials before and after exposure to ZnO NP and Zn(2+). Based on computational analysis using principal component analysis and linear discriminant analysis (PCA-LDA), it was demonstrated that both Chelex-100 and Metsorb form chemical bonds with ZnO NP and Zn(2+), however the binding mechanisms of these zinc species as inferred from their infrared (IR) spectra are statistically different (95% confidence level). The experimental results suggest that the binding resins hold ZnO NP with fewer and weaker chemical bonds compared to Zn(2+). This research shows the potential of the DGT method to measure available concentrations of nanoparticles in the environment and demonstrate how ATR-FTIR spectroscopy, when used with computational analysis, can differentiate between diverse chemical species that are simultaneously retained by the binding layer in a DGT device.