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Frontiers of Environmental Science & Engineering

Front Envir Sci Eng    2012, Vol. 6 Issue (1) : 17-25
Decomposition of perfluorooctanoic acid by microwave-activated persulfate: Effects of temperature, pH, and chloride ions
Yuchi LEE1, Shanglien LO1(), Jeff KUO2, Chinghong HSIEH1
1. Research Center for Environmental Pollution Prevention and Control Technology, Graduate Institute of Environmental Engineering, Taiwan University, Taipei 10672, China; 2. Department of Civil and Environmental Engineering, California State University, Fullerton, CA 92834-6870, USA
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Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S2O82-) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects of pH (pH= 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01–0.15 mol·L-1), and temperature (60°C, 90°C, and 130°C) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol·L-1 at 90°C and 0.06 mol·L-1 at 60°C, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.

Keywords microwave      perfluorooctanoic acid      pH      persulfate      chloride ions      perfluorocarboxylic acids     
Corresponding Authors: LO Shanglien,   
Issue Date: 01 February 2012
 Cite this article:   
Yuchi LEE,Shanglien LO,Jeff KUO, et al. Decomposition of perfluorooctanoic acid by microwave-activated persulfate: Effects of temperature, pH, and chloride ions[J]. Front Envir Sci Eng, 2012, 6(1): 17-25.
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Yuchi LEE
Shanglien LO
Jeff KUO
Chinghong HSIEH
Fig.1  Comparison of PFOA decomposition (254 μmol·L) at different temperatures with or without persulfate (PS, 10 mmol·L), and with or without MW
Fig.2  Comparison of the formation of during decomposition of PFOA (254 μmol·L) with 10 mmol·L and microwave at 60°C, 90°C, and 130°C
Fig.3  Comparison of PFOA decomposition with 10 mmol·L PS at 90°C under different pHs
Fig.4  Comparison of formation of during decomposition of PFOA with 10 mmol·L PS and MW at different pHs
Fig.5  Comparison of solution pH value on the defluorination ratios of PFOA (254 μmol·L) with 10 mmol·L and microwave at 90°C
Entryinitial pHrate constant/h-1 a)decomposition efficiency / final pH
0.5h b)1h b)2h b)4h b)
1 c)3.76— / 2.72— / 2.38— / 2.31— / 2.30 10.23.91%/ 2.8419.8%/ 2.5224.9%/ 2.41
38.80.5320.5%/ 2.5445.3%/ 2.2764.9%/ 2.2174.2%/ 2.19
43.60.7529.8%/ 2.1751.1%/ 2.1478.5%/ 2.1181.4%/ 2.08
52.30.8238.2%/ 2.0462.1%/ 1.9981.8%/ 1.9485.7%/ 1.88
Tab.1  Calculated pseudo-first-order constants, decompsition ratio of PFOA and solution pH under MW irradiation at 90°C at different initial pH values. Initial pH value in the original 254 μmol·L PFOA solution (without pH adjustment) was around 3.6, pH adjustments were made by NaOH or HSO
Fig.6  Comparison of various ZVI applying on PFOA (240.7 μmol·L) decomposition under MW irradiation at 90°C
Fig.7  Comparison of chloride ions (0-0.15 mol·L) on persulfate oxidation constants of PFOA at 60°C and 90°C
Fig.8  Comparison of the PFOA concentration, defluorination ratio, and mass balance of F element during decomposition of PFOA (254 μmol·L) with 10 mmol·L PS and MW at 90°C under phosphate-buffered pH 2.5
Fig.9  Concentrations of intermediates formed at various reaction times by degradation of PFOA (254 μmol·L) with 10 mmol·L PS at 90°C
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