First Discovery of Iodinated Polyfluoroalkyl Acids by Nontarget Mass-Spectrometric Analysis and Iodine-Specific Screening Algorithm

Per- and polyfluoroalkyl acids (PFAAs) including polyfluoroalkyl carboxylic acids and polyfluoroalkyl sulfonic acids are a large category of crucial environmental pollutants of global concern. Besides known PFAAs, numerous unknown species may exist in the environment, urgently needing discovery and characterization. This study implemented nontarget analysis for a group of novel PFAA pollutants, viz., iodinated PFAAs (I-PFAAs) in wastewater from a fluorochemical manufacturing park by liquid chromatography–high-resolution mass spectrometry in combination with an iodine-specific data-processing algorithm. The algorithm took into account the diagnostic fragment iodine ion (I–) together with carbon and sulfur isotopologue distributions. In total, 18 I-PFAA formulas involving 21 congeners were identified. Semiquantification was conducted, and the total concentrations of I-PFAAs were 1.9–274.7 μg/L, indicating severe pollution of I-PFAAs in the wastewater. The determined concentrations along with predicted environmental behaviors and toxicities demonstrate that I-PFAAs merit further in-depth investigation. The analytical method including the instrumental analysis and data-processing algorithm can be extended to screening and identification of I-PFAAs in other matrices. Furthermore, the analysis results for the first time provide recognition on the occurrence, distribution features, and pollution status of I-PFAAs in the environment.