Exploring the source, migration and environmental risk of perfluoroalkyl acids and novel alternatives in groundwater beneath fluorochemical industries along the Yangtze river, China

The widely used legacy perfluoroalkyl acids (PFAAs) with serious environmental hazards are gradually restricted and being replaced by novel alternatives. Here, for an efficient control of emerging environmental risks in groundwater, we systematically studied the source apportionment, spatial attenuation, composition change and risk zoning of 12 PFAAs and five novel alternatives within a region of ~200 km2 around a mega fluorochemical industrial park (FIP) along the Yangtze River, and in-depth explored potential association between groundwater and soil pollution as well as influencing factors on contaminant migration and risk distribution in the aquifer. Short-chain PFAAs and novel alternatives together accounted for over 70% in groundwater, revealing their prevalence in replacing legacy perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Novel alternatives for PFOA were mainly hexafluoropropylene oxide dimer acid (GenX) and hexafluoropropylene oxide trimer acid (HFPO-TA), while those for PFOS were 6:2 chlorinated polyfluorinated ether sulfonic acid (6:2 Cl-PFESA) and 6:2 fluorotelomer sulfonic acid (6:2 FTS). PFAAs (maximum total: 1339 ng/L) and novel alternatives (maximum total: 208 ng/L) in groundwater were mostly derived from the FIP, and exhibited an exponentially decreasing trend with increasing distance. Compared with those in groundwater, more diverse sources of PFAAs and novel alternatives in surface soil were identified. The transport of these chemicals may be retarded by clayed surface soils with high organic matter contents. High aquifer permeability could generally promote the dilution and migration of PFAAs and novel alternatives in groundwater, as well as reduce the differences in their spatial distribution. Shorter-chain components with smaller molecules and higher hydrophilicity exhibited greater migration capacities in the aquifer. In addition, different levels of health risk from PFOS and PFOA were zoned based on drinking groundwater, and high risks tended to be distributed in areas with relatively poor aquifer water yield due to higher pollutant accumulation