While perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) are ubiquitous in aquatic environments, non-targeted methods have recently revealed the presence of numerous unidentified per- and polyfluoroalkyl substances (PFAS). Besides those methods, the total oxidizable precursor (TOP) assay has proved useful to estimate the contribution of unattributed perfluoroalkyl acids precursors (pre-PFAAs). In this study, an optimized extraction method was developed to examine the spatial distribution of 36 targeted PFAS in surface sediments collected at French nationwide scale (n = 43), including neutral, anionic and zwitterionic molecules. In addition, a TOP assay procedure was implemented to estimate the contribution of unattributed pre-PFAAs in these samples. Conversion yields of targeted pre-PFAAs were determined for the first time under realistic conditions and led to differences in oxidation profiles compared to the common spiked ultra-pure water method. PFAS were detected in 86 % of samples and ∑PFAStargeted was in the range < Limit of Detection – 23 ng g−1 dry weight (dw) (median: 1.3 ng g−1 dw), with ∑pre-PFAAstargeted representing on average 29 ± 26 % of ∑PFAS. Among pre-PFAAs, compounds of emerging interest such as the fluorotelomer sulfonamidoalkyl betaines 6:2 FTAB and 8:2 FTAB were respectively detected in 38 % and 24 % of samples, with levels similar to those of L-PFOS (<0.36–2.2, <0.50–6.8 and < 0.08–5.1 ng g−1 dw, respectively). A hierarchical cluster analysis coupled with a geographic information system-based approach revealed similarities between groups of sampling sites. For instance, elevated contribution of FTABs were associated with the proximity to airport activities where betaine-based aqueous film-forming foam (AFFFs) might have been used. In addition, unattributed pre-PFAAs were strongly correlated with ∑PFAStargeted and they accounted for 58 % of ∑PFAS (median value); they were generally found in larger quantity near industrial and urban areas where the highest ∑PFAStargeted were also observed.