US EPA

4238293 

Journal Article 

Degradation of perfluorinated compounds by sulfate radicals - New mechanistic aspects and economical considerations 

Lutze, HV; Brekenfeld, J; Naumov, S; von Sonntag, C; Schmidt, TC 

2018 

1 

Water Research
ISSN: 0043-1354
EISSN: 1879-2448 

129 

509-519 

English 

29247911 

10.1016/j.watres.2017.10.067 

WOS:000424716800050 

Perfluorinated organic compounds (PFC) are an important group of pollutants, which are difficult to be degraded in conventional water treatment. Even hydroxyl radical based processes are not capable to degrade these compounds. Sulfate radicals can oxidize a group of PFC, i.e., perfluorinated carboxylic (PFCAs) acids. However, information in literature on kinetics and reaction mechanism is largely based on model simulations which are prone to errors. The present study provides mechanistic insights based on product formation, material balances, competition kinetics experiments and quantum chemical calculations. Furthermore, energy requirements for sulfate radical based degradation of PFCA is evaluated in the present study. PFCAs can be partly mineralized in chain reactions initiated by sulfate radicals (SO4─). The perfluorinated acetic acid (TFA), propionic acid, and butanoic acid are largely degraded in a primary reaction with sulfate radicals. In case of PFCA with a chain length of > 4 carbons low yields of PFCA products were observed. Regarding reaction kinetics sulfate radicals react very slow with PFCAs (≈ 104 M-1 s-1). Thus, the energy demand required for generation of SO4─by photolysis of S2O82─(UV/S2O82-) is very high. A 90% degradation of a PFCA by UV/S2O82-was estimated to be 55 kW h m-3in pure water.