Major point sources of per- and polyfluoroalkyl substances (PFASs) cause ubiquitous spread of PFASs in the environment. In this study, surface water and aquatic invertebrates at three Swedish sites impacted by PFAS point sources were characterized, using homologue, isomer and extractable organofluorine (EOF) profiling as well as estimation of bioaccumulation factors (BAFs) and mass discharge. Two sites were impacted by fire training (sites A and R) and the third by industrial runoff (site K). Mean Σ25PFASs concentration in water was 1920 ng L-1 at site R (n = 3), which was more than 20- and 10-fold higher than those from sites A and K, respectively. PFOS was the most predominant PFAS in all waters samples, constituting 29-79% of Σ25PFAS concentrations. Several branched isomers were detected and they substantially contributed to concentrations in surface water (e.g. 49-78% of ΣPFOS) and aquatic invertebrates (e.g. 15-28% of ΣPFOS). BAFs in the aquatic invertebrates indicated higher bioaccumulation for long chain PFASs and lower bioaccumulation for branched PFOS isomers compared to linear PFOS. EOF mass balance showed that Σ25target PFASs in water could explain up to 55% of EOF at site R. However, larger proportions of EOF (>92%) remained unknown in water from sites A and K. Mass discharges were for the first time estimated for EOF and revealed that high amounts of EOF (e.g. 8.2 g F day-1 at site A) could be transported by water to recipient water bodies relative to Σ25PFASs (e.g. 0.15 g day-1 at site A). Overall, we showed that composition profiling, BAFs and EOF mass balance can improve the characterization of PFASs around point sources.