Per- and polyfluoroalkyl substances (PFASs) constitute a large category of synthetic environmental pollutants, many of which remain unknown and warrant comprehensive investigation. This study comprehensively characterized PFASs in fluorinated-industrial wastewater by nontarget, quasi-target and target analyses using liquid chromatography-high-resolution mass spectrometry and data-processing algorithms. The algorithms based on characteristic in-source neutral losses and isotopologue distributions were applied to screening and identifying PFASs, while semiquantitative and quantitative analyses were utilized to determine their concentrations and distributions in the wastewater. In total, 175 formulae of PFASs, including traditional, little-known and unknown species were identified and further ascertained in terms of concentrations and distributions. The total concentrations of PFASs in the wastewater were 5.3–33.4 μg mL⁻¹, indicating serious pollution of PFASs. This study not only provides an efficient approach for screening and identification of unknown PFASs, but also presents a practicable and simple way to comprehensively depict environmental pollution signatures of PFASs.

全氟和多氟烷基物质 (PFAS) 构成了一大类合成环境污染物，其中许多仍然未知，需要进行全面调查。本研究使用液相色谱-高分辨率质谱法和数据处理算法，通过非目标、准目标和目标分析全面表征了含氟工业废水中的 PFAS。基于特征源内中性损失和同位素体分布的算法应用于筛选和识别 PFAS，同时利用半定量和定量分析确定它们在废水中的浓度和分布。总共确定了 175 种 PFAS 的配方，包括传统的、鲜为人知的和未知的物种，并进一步确定了浓度和分布。⁻¹，说明PFASs污染严重。本研究不仅为未知 PFAS 的筛选和鉴定提供了一种有效的方法，而且为全面描述 PFAS 的环境污染特征提供了一种可行且简单的方法。