Uptake and release of perfluoroalkyl carboxylic acids (PFCAs) from macro and microplastics

Microplastics and per- and polyfluoroalkyl substances (PFAS) are two of the most notable emerging contaminants reported in the environment. Micron and nanoscale plastics possess a high surface area-to-volume ratio, which could increase their potential to adsorb pollutants such as PFAS. One of the most concerning sub-classes of PFAS are the perfluoroalkyl carboxylic acids (PFCAs). PFCAs are often studied in the same context as other environmental contaminants, but their amphiphilic properties are often overlooked in determining their fate in the environment. This lack of consideration has resulted in a diminished understanding of the environmental mobility of PFCAs, as well as their interactions with environmental media. Here, we investigate the interaction of PFCAs with polyethylene microplastics, and identify the role of environmental weathering in modifying the nature of interactions. Through a series of adsorption-desorption experiments, we delineate the role of the fluoroalkyl tail in the binding of PFCAs to microplastics. As the number of carbon atoms in the fluoroalkyl chain increases, there is a corresponding increase in the adsorption of PFCAs onto microplastics. This relationship can become modified by environmental weathering, where the PFCAs are released from the macro and microplastic surface after exposure to simulated sunlight. This study identifies the fundamental relationship between PFCAs and plastic pollutants, where they can mutually impact their thermodynamic and transport properties.