Transport and transformation of perfluoroalkyl acids, isomer profiles, novel alternatives and unknown precursors from factories to dinner plates in China: New insights into crop bioaccumulation prediction and risk assessment.

Perfluoroalkyl acids (PFAAs) are contaminants of global concern, and the inadvertent consumption of PFAA-contaminated crops may pose a threat to public health. Therefore, systematically studying their source tracing, bioaccumulation prediction and risk assessments in crops is an urgent priority. This study investigated the source apportionment and transport of PFAAs and novel fluorinated alternatives (collectively as per- and polyfluoroalkyl substances, PFASs) from factories to agricultural fields in a fluorochemical industrial region of China. Furthermore, bioaccumulation specificities and prediction of these chemicals in different vegetables were explored, followed by a comprehensive risk assessment from agricultural fields to dinner plates which considered precursor degradation. A positive matrix factorization model revealed that approximately 70 % of PFASs in agricultural soils were derived from fluorochemical manufacturing and metal processing. Alarming levels of ∑PFASs ranged 8.28-84.3 ng/g in soils and 163-7176 ng/g in vegetables. PFAS with short carbon chain or carboxylic acid group as well as branched isomers exhibited higher environmental transport potentials and bioaccumulation factors (BAFs) across a range of vegetables. The BAFs of different isomers of perfluorooctanoic acid (PFOA) decreased as the perfluoromethyl group moved further from the acid functional group. Hexafluoropropylene oxide dimer acid (GenX) showed relatively low BAFs, probably related to its ether bond with a high affinity to soil. Vegetables with fewer Casparian strips (e.g., carrot and radish), or more protein, possessed larger BAFs of PFASs. A bioaccumulation equation integrating critical parameters of PFASs, vegetables and soils, was built and corroborated with a good contamination prediction. After a total oxidizable precursors (TOP) assay, incremental perfluoroalkyl carboxylic acids (PFCAs) were massively found (325-5940 ng/g) in edible vegetable parts. Besides, precursor degradation and volatilization loss of PFASs was firstly confirmed during vegetable cooking. A risk assessment based on the TOP assay was developed to assist the protection of vegetable consumers.