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Measuring log Kow coefficients of neutral species of perfluoroalkyl carboxylic acids using reversed-phase high-performance liquid chromatography

Xiang, Qian, Shan, Guoqiang, Wu, Wei, Jin, Hangbiao, Zhu, Lingyan
Environmental pollution 2018 v.242 pp. 1283-1290
agrochemicals, fatty acids, models, moieties, pH, partition coefficients, perfluorocarbons, polycyclic aromatic hydrocarbons, reversed-phase high performance liquid chromatography
Accurate measuring n-octanol/water partition coefficients (log Kₒw) of perfluoroalkyl carboxylic acids (PFCAs) using experimental approach has been proven to be very difficult due to their special properties. The ionizable carboxyl groups in PFCAs make their log Kₒw dependent on pH. In this study, the log Kₒw values of neutral species of PFCAs (C₄≤ₙ≤₁₄) were measured based on reversed-phase high-performance liquid chromatography (RP-HPLC) with the mobile phase pH varying in the range of 1.09–5.00. The relationship between log Kₒw and retention times was established using some reference compounds (including agrochemicals, polycyclic aromatic hydrocarbons) with known log Kₒw values, and then validated with alkyl fatty acids, which have similar chemical structures as PFCAs. The apparent log Kₒw (i.e., log Dₒw) of the C₄–₁₄ PFCAs were calculated based on their retention times using the established model, and they displayed a negative linear relationship with the mobile phase pH in the range of 1.09–4.00. Consequently, the log Dₒw values were converted to the corresponding log Kₒw values (1.05–7.19) based on the relationship of log Dₒw = log Kₒw + pKₐ – pH. The log Kₒw increased with perfluorinated carbon chain length with a greater rate for C₄ to C₅ PFCAs than for C₅–₁₄ PFCAs.