Activated Persulfate Oxidation of Perfluorooctanoic Acid (PFOA) in Groundwater under Acidic Conditions.
Perfluorooctanoic acid (PFOA) is an emerging contaminant of concern due to its toxicity for human health and ecosystems. However, successful degradation of PFOA in aqueous solutions with a cost-effective method remains a challenge, especially for groundwater. In this study, the degradation of PFOA using activated persulfate under mild conditions was investigated. The impact of different factors on persulfate activity, including pH, temperature (25 °C-50 °C), persulfate dosage and reaction time, was evaluated under different experimental conditions. Contrary to the traditional alkaline-activated persulfate oxidation, it was found that PFOA can be effectively degraded using activated persulfate under acidic conditions, with the degradation kinetics following the pseudo-first-order decay model. Higher temperature, higher persulfate dosage and increased reaction time generally result in higher PFOA degradation efficiency. Experimental results show that a PFOA degradation efficiency of 89.9% can be achieved by activated persulfate at pH of 2.0, with the reaction temperature of 50 °C, molar ratio of PFOA to persulfate as 1:100, and a reaction time of 100 h. The corresponding defluorination ratio under these conditions was 23.9%, indicating that not all PFOA decomposed via fluorine removal. The electron paramagnetic resonance spectrometer analysis results indicate that both SO₄(-)• and •OH contribute to the decomposition of PFOA. It is proposed that PFOA degradation occurs via a decarboxylation reaction triggered by SO₄(-)•, followed by a HF elimination process aided by •OH, which produces one-CF₂-unit-shortened perfluoroalkyl carboxylic acids (PFCAs, Cn-1F2n-1COOH). The decarboxylation and HF elimination processes would repeat and eventually lead to the complete mineralization all PFCAs.
College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, China. phyin@issas.ac.cn.|Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China. phyin@issas.ac.cn.
Penghua
P
Yin
College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, China. melopasserby@126.com.|Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China. melopasserby@126.com.
Zhihao
Z
Hu
Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China. xsong@issas.ac.cn.
Xin
X
Song
College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, China. jgliu2005@163.com.
Jianguo
J
Liu
Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China. nlin@issas.ac.cn.
Na
N
Lin
D002210:Caprylates / Q000737:chemistry*; D005466:Fluorocarbons / Q000737:chemistry*; D060587:Groundwater / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D010084:Oxidation-Reduction; D017670:Sodium Compounds / Q000737:chemistry; D013431:Sulfates / Q000737:chemistry; D013696:Temperature; D014874:Water Pollutants, Chemical / Q000737:chemistry*
D002210:Caprylates; D005466:Fluorocarbons; D017670:Sodium Compounds; D013431:Sulfates; D014874:Water Pollutants, Chemical; C023036:perfluorooctanoic acid; C024625:sodium persulfate
PFOA; activated persulfate; defluorination; free radicals