Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers

This study presents the first comprehensive assessment of per- and polyfluoroalkyl substances (PFAS) in surface waters of northern Serbia (Middle Danube region), combining targeted analysis of 25 PFAS with high-resolution mass spectrometry suspect screening (SSA) at 12 settlement-adjacent sites on major rivers and part of the Danube–Tisa–Danube (DTD) canal network. The sum of 10 quantified PFAS showed pronounced spatial variability: the Great Bačka Canal (GBC) exhibited the highest mean and maximum values (18.4 ng/L and 52.6 ng/L, respectively); the Danube averaged 9.05 ng/L (2.92–22.2 ng/L); the Tisa averaged 10.5 ng/L (4.53–16.5 ng/L); and the Sava and Tamiš exhibited the lowest means (~5.4 ng/L each). In total, 19 of 24 sites exceeded the proposed EU group Environmental Quality Standard (EQS) of 4.4 ng/L, expressed as PFOA-equivalents, with exceedances of 5.4–20.2 ng/L; PFOS exceeded the 0.65 ng/L inland surface water annual average (AA) EQS in 17 samples. SSA expanded coverage beyond targets, revealing ultra-/short-chain PFAS and replacements, with TFA as the most abundant (337–1165 ng/L; mean 513 ng/L) and notable maxima for PFPrA (51.3 ng/L), ADONA (24.9 ng/L), and TFMS (11.2 ng/L). Compared with European freshwaters, the maximum obtained here lies in the lower-mid part of the reported range, consistent with short-chain perfluoroalkyl carboxylic acids (PFCA) dominance and diffuse-source influences.