Effect of initial solution pH on photo-induced reductive decomposition of perfluorooctanoic acid.
The effects of initial solution pH on the decomposition of perfluorooctanoic acid (PFOA) with hydrated electrons as reductant were investigated. The reductive decomposition of PFOA depends strongly on the solution pH. In the pH range of 5.0-10.0, the decomposition and defluorination rates of PFOA increased with the increase of the initial solution pH. The rate constant was 0.0295 min(-1) at pH 10.0, which was more than 49.0 times higher than that at pH 5.0. Higher pH also inhibits the generation of toxic intermediates during the PFOA decomposition. For example, the short-chain PFCAs reached a lower maximum concentration in shorter reaction time as pH increasing. The peak areas of accumulated fluorinated and iodinated hydrocarbons detected by GC/MS under acidic conditions were nearly 10-100 times more than those under alkaline conditions. In short, alkaline conditions were more favorable for photo-induced reduction of PFOA as high pH promoted the decomposition of PFOA and inhibited the accumulation of intermediate products. The concentration of hydrated electron, detected by laser flash photolysis, increased with the increase of the initial pH. This was the main reason why the decomposition of PFOA in the UV-KI system depended strongly on the initial pH.
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, PR China.
Yan
Y
Qu
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, PR China. Electronic address: myrazh@tongji.edu.cn.
Chao-Jie
CJ
Zhang
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, PR China.
Pei
P
Chen
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, PR China.
Qi
Q
Zhou
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, PR China.
Wei-Xian
WX
Zhang
D002210:Caprylates / Q000737:chemistry*; D004785:Environmental Pollutants / Q000737:chemistry*; D005466:Fluorocarbons / Q000737:chemistry*; D054879:Halogenation; D006863:Hydrogen-Ion Concentration; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010782:Photolysis; D012996:Solutions
D002210:Caprylates; D004785:Environmental Pollutants; D005466:Fluorocarbons; D012996:Solutions; C023036:perfluorooctanoic acid
Defluorination; Perfluorooctanoic acid; Photo-induced reductive decomposition; pH effect