Reduced Graphene Oxide Aerogels Cartridges for Solid Phase Extraction of Benzotriazoles

Abstract

UV-benzotriazoles have been identified as water micropollutants that cause serious problems for human health and the environment. Their low concentration in water bodies complicates their detection by direct water analysis, slowing the corrective actions to avoid bioaccumulation. In this regard, the use of graphene-based materials with a high affinity for non-polar molecules has been demonstrated to be a potential tool for the optimal separation and concentration of this type of molecules in solid phase extraction (SPE) processes. This work evaluates the potential of novel reduced graphene oxide aerogels (rGO) as extractants of mixtures of three UV-benzotriazoles in water at low concentrations. These rGO aerogels incorporate graphenic domains into a tough structure of polymeric chains by adding graphene oxide during the synthesis of resorcinol-formaldehyde gels. Aerogels with a different content and ordering of graphenic domains were obtained and characterized using Raman, XRD, SEM and nitrogen adsorption isotherms (-196 °C). The rGO aerogels that performed better as solid phase extractants were those containing 60% rGO. Aerogels with lower rGO contents (40%) required a high-temperature (2000 °C) treatment to render competitive results. The SPE methodology using selected rGO aerogels was optimized by varying the elution solvent, elution time and volume. The best performances, i.e., recoveries of 80-100% and enrichment factors of 12.5-50, were accomplished when using 0.8 mL of tetrahydrofuran (THF) as an elution solvent. As a result, a fast (10 min) and simple extraction method of UV-benzotriazoles in water was attained, achieving a detection limit of 1 ng mL-1. Selected aerogels were finally tested for the SPE of spiked samples of river waters, showing a similar performance to that observed with synthetic mixtures.