Rapid Single-Step Detection of Polyfluoroalkyl Substances (PFAS) Using Electropolymerized Phenoxazine Dyes

Per- and polyfluoroalkyl substances (PFAS) are highly stable ubiquitous contaminants that have been recently added to the list of regulated chemicals. While methods for PFAS detection exist, analysis is difficult, involving a tedious protocol and expensive instrumentation. Here, we demonstrate the first implementation of a phenoxazine dye as a sensing probe that facilitates rapid and inexpensive detection of representative PFAS, e.g., perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), at sensitivity levels covering the recently established Environmental Protection Agency (EPA) limits. The method comprises an electrode modified with a stable redox film of Meldola blue (MB) in its electropolymerized form (epMB), which provides amino sites for electrostatic interactions with PFAS. Long-chain PFAS bind specifically to the epMB, inducing a hydrophobic-type cluster formation through ion-pair and F–F interactions. This binding generates concentration-dependent changes in the epMB/epMB+ oxidation, enabling rapid and sensitive quantification in a single step with high sensitivity, reaching a limit of detection of 0.4 ppt for PFOS and 1.65 ppt for PFOA. The sensor demonstrates good selectivity toward common interfering compounds like humic acid, sodium chloride and fluoride, metallic ions (Cu, Hg, As), as well as pesticides. In addition to PFOS and PFOA, the sensors can measure other perfluoroalkyl compounds, demonstrating potential as a tool for rapid quantification of a total PFAS index, with affinity for long-chain PFAS. This work highlights the integration of redox receptors into an electrochemical sensor to solve the grand challenge of PFAS analysis using a rapid and inexpensive procedure, with potential for field deployment.