Determination of organic fluorinated compounds content in complex samples through combustion ion chromatography methods: a way to define a "Total Per- and Polyfluoroalkyl Substances (PFAS)" parameter?

Emerging contaminants are a growing concern for scientists and public authorities. The group of per-polyfluoroalkyl substances (PFAS), known as 'forever chemicals', in complex environmental liquid and solid matrices was analysed in this study. The development of global analytical methods based on combustion ion chromatography (CIC) is expected to provide accurate picture of the overall PFAS contamination level via the determination of extractable organic fluorine (EOF) and adsorbable organic fluorine (AOF). The obtained results may be put into perspective with other methods such as targeted analyses (LC-MS/MS). The impact of pH, the presence of dissolved organic carbon and suspended particles on AOF measurements were explored. The effectiveness of the washing step to remove adsorbed inorganic fluorine (IF) has been proven for samples containing up to 8 mgF.L-1. CIC-based methods showed good repeatability and reproducibility for the complex matrices studied. Environmental applications of these methods have been tested. AOF and EOF analyses could explain between 1 % and 23 % and 0.1 % to 2 % of total organic fluorine (TOF), respectively. The sum of PFAS compounds expressed as fluorine could explain from 0.2 % to 11 % and from 0.003 % to 5 % for AOF and EOF, respectively. These results also suggest that some fluorinated compounds are not adsorbed or extractable and/or lost by volatilisation during the application of AOF and EOF analytical procedure. These findings highlight that AOF and EOF are not entirely efficient as proxy to assess "total PFAS" for assessing environmental contamination by PFAS. However, these methods could still be applied to gain a better understanding of the sources and fate of PFAS in the environment.

Metal availability in a highly contaminated, dredged-sediment disposal site: field measurements and geochemical modeling.

Two complementary approaches were used to characterize arsenic and metal mobilizations from a dredged-sediment disposal site: a detailed field study combined with hydrogeochemical modeling. Contaminants in sediments were found to be mainly present as sulfides subject to oxidation. Secondary phases (carbonates, sulfates, (hydr)oxides) were also observed. Oxidative processes occurred at different rates depending on physicochemical conditions and contaminant contents in the sediment. Two distinct areas were identified on the site, each corresponding to a specific contaminant mobility behavior. In a reducing area, Fe and As were highly soluble and illustrated anoxic behavior. In well-oxygenated material, groundwater was highly contaminated in Zn, Cd and Pb. A third zone in which sediments and groundwater were less contaminated was also characterized. This study enabled us to prioritize remediation work, which should aim to limit infiltration and long-term environmental impact.