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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2016, Vol. 10 Issue (3) : 438-446
Degradation of carbon tetrachloride in thermally activated persulfate system in the presence of formic acid
Minhui XU,Xiaogang GU,Shuguang LU(),Zhouwei MIAO,Xueke ZANG,Xiaoliang WU,Zhaofu QIU,Qian SUI
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237, China
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The thermally activated persulfate (PS) degradation of carbon tetrachloride (CT) in the presence of formic acid (FA) was investigated. The results indicated that CT degradation followed a zero order kinetic model, and CO2-· was responsible for the degradation of CT confirmed by radical scavenger tests. CT degradation rate increased with increasing PS or FA dosage, and the initial CT had no effect on CT degradation rate. However, the initial solution pH had effect on the degradation of CT, and the best CT degradation occurred at initial pH 6. Cl- had a negative effect on CT degradation, and high concentration of Cl- displayed much strong inhibition. Ten mmol·L-1HCO3- promoted CT degradation, while 100 mmol·L-1NO3- inhibited the degradation of CT, but SO42- promoted CT degradation in the presence of FA. The measured Cl- concentration released into solution along with CT degradation was 75.8% of the total theoretical dechlorination yield, but no chlorinated intermediates were detected. The split of C-Cl was proposed as the possible reaction pathways in CT degradation. In conclusion, this study strongly demonstrated that the thermally activated PS system in the presence of FA is a promising technique in in situ chemical oxidation (ISCO) remediation for CT contaminated site.

Keywords persulfate      carbon tetrachloride      thermal activation      formic acid      carbon dioxide radical anion     
Corresponding Authors: Shuguang LU   
Online First Date: 18 June 2015    Issue Date: 05 April 2016
 Cite this article:   
Minhui XU,Xiaogang GU,Shuguang LU, et al. Degradation of carbon tetrachloride in thermally activated persulfate system in the presence of formic acid[J]. Front. Environ. Sci. Eng., 2016, 10(3): 438-446.
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Minhui XU
Xiaogang GU
Shuguang LU
Zhouwei MIAO
Xueke ZANG
Xiaoliang WU
Zhaofu QIU
Qian SUI
Fig.1  CT degradation in the thermally activated PS system in the presence of FA (50°C, [CT]0 = 10 μmol·L-1, [PS] = 20 mmol·L-1, [FA] = 30 mmol·L-1)
Fig.2  Effect of scavenger on CT degradation (50°C, [CT]0 = 10 μmol·L-1, [PS] = 20 mmol·L-1, [FA] = 30 mmol·L-1)
Fig.3  Effect of dosages of PS and FA, and initial CT concentration on CT degradation. (a) PS (50°C, [CT]0 = 10 μmol·L-1, [FA] = 30 mmol·L-1); (b) FA (50°C, [CT]0 = 10 μmol·L-1, [PS] = 20 mmol·L-1); (c) CT (50°C, [PS] = 20 mmol·L-1, [FA] = 30 mmol·L-1)
Fig.4  Effect of initial solution pH on CT degradation. (a) Cl-; (b) H C O 3 - ; (c) N O 3 - ; (d) S O 4 2 - . (50°C, [CT]0 = 10 μmol·L-1, [PS] = 20 mmol·L-1, [FA] = 30 mmol·L-1)
pH initial 30 min 90 min final (180 min)
unadjusted pH 2.59 2.52 2.45 2.33
pH= 3 3.02 2.97 2.85 2.61
pH= 6 5.98 4.86 4.44 3.50
pH= 9 8.90 5.16 4.64 3.50
pH= 12 12.00 11.97 11.92 11.86
Tab.1  pH variation along with reaction at different initial solution pH conditions
Fig.5  Effect of solution matrix on CT degradation (50°C, [CT]0 = 10 μmol·L-1, [PS] = 20 mmol·L-1, [FA] = 30 mmol·L-1)
Fig.6  Performance of CT degradation versus PS decomposition and Cl- release. (50°C, [CT]0 = 0.1 mmol·L-1, [PS] = 20 mmol·L-1, [FA] = 30 mmol·L-1)
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