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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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Front Envir Sci Eng    2012, Vol. 6 Issue (4) : 445-454    https://doi.org/10.1007/s11783-012-0419-6
RESEARCH ARTICLE
Identification and ecotoxicity assessment of intermediates generated during the degradation of clofibric acid by advanced oxidation processes
Wenzhen LI1, Yu DING2, Qian SUI1, Shuguang LU1(), Zhaofu QIU1, Kuangfei LIN1
1. State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process; Shanghai Key Laboratory of Functional Materials Chemistry, East China University of Science and Technology, Shanghai 200237, China; 2. Datang Energy Corporation, Hulunbeier 021008, China
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Abstract

The aim of this study was to identify the intermediates in clofibric acid degradation under various advanced oxidation processes, namely ultraviolet (UV), UV/H2O2, vacuum ultraviolet (VUV), VUV/H2O2, and solar/TiO2 processes, as well as to assess the toxicity of these intermediates. Eleven intermediates have been detected by gas chromatography-mass spectrometer, most of which were reported for the first time to our best knowledge. Combining the evolution of the dissolved organic carbon, Cl- and specific ultraviolet absorption at 254 nm, it could be deduced that cleavage of aromatic ring followed by dechlorination was the mechanism in solar/TiO2 process, while dechlorination happened first and accumulation of aromatic intermediates occurred in the other processes. Different transformation pathways were proposed for UV-, VUV-assisted and solar/TiO2 processes, respectively. The acute toxicity was evaluated by means of Photobacterium phosphoreum T3 spp. bioassay. It was believed that aromatic intermediates increased the toxicity and the ring-opening pathway in solar/TiO2 process could relieve the toxicity.
Keywords clofibric acid      advanced oxidation processes      intermediates      toxicity      Photobacterium phosphoreum T3 spp.     
Corresponding Author(s): LU Shuguang,Email:lvshuguang@ecust.edu.cn   
Issue Date: 01 August 2012
 Cite this article:   
Wenzhen LI,Yu DING,Qian SUI, et al. Identification and ecotoxicity assessment of intermediates generated during the degradation of clofibric acid by advanced oxidation processes[J]. Front Envir Sci Eng, 2012, 6(4): 445-454.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-012-0419-6
https://academic.hep.com.cn/fese/EN/Y2012/V6/I4/445
Fig.1  Degradation performance of clofibric acid in (a) UV and VUV, (b) UV/HO and VUV/HO, (c) solar/TiO processes ( = 100 mg·L, [HO]= 100 mg·L, [TiO]= 1000 mg·L, = 25°C)
Fig.2  (a) DOC mineralization, (b) Cl release and (c) SUVA evolution in UV, UV/HO, VUV, VUV/HO and solar/TiO processes (C = 100 mg L, [HO]= 100 mg L, [TiO]= 1000 mg L, = 25°C)
Fig.3  Possible degradation pathways of clofibric acid in (a) UV-, VUV-assisted and (b) solar/TiO processes (C = 100 mg L, [HO]= 100 mg L, [TiO]= 1000 mg L, = 25°C)
No.retention time /mincompoundformulamolecular weight /(g mol-1)structurem/z/(relative intensity,%)similarity/%
14.07methacrylic acidC4H6O28641(100), 86(73), 40(30), 69(18), 68(13), 42(10), 95(9), 45(7)94
24.57ethylbenzeneC8H1010691(100), 106(50), 65(12), 92(12), 51(11), 77(10), 78(9), 105(8)95
35.43p-benzoquinoneC6H4O2108108(100), 54(80), 82(37), 80(36), 52(21), 53(19), 50(8)98
46.28phenolC6H6O9494(100), 66(42), 65(29), 40(12), 95(8), 55(8), 63(7), 50(5)98
59.42acetic acid,4-chlorophenol esterC8H7ClO2170128(100), 130(32), 43(30), 168(26), 65(14), 41(11), 100(9), 170(8)87
69.72parachlorophenolC6H5ClO128128(100), 65(40), 130(35), 64(17), 100(16), 63(13), 129(8), 73(8)97
711.262-methyl-2,3-dihydrob-enzofuranC9H10O134134(100), 119(84), 91(37), 133(21), 65(20), 77(16), 51(12), 94(11)89
811.33hydroquinoneC6H6O2110110(100), 107(20), 82(11), 81(10), 108.95(7), 52.75(7), 110.9(7)78
912.655-chloro-2-methyl-2,3-dihydro-1-benzofuranC9H9ClO168168(100), 153(93), 125(62), 105(40), 170(32), 155(30), 77(25), 89(25)77
1012.892-methyl-5-hydroxybe-nzofuranC9H8O2148147(100), 148(93), 91(21), 65(16), 149(9), 74(7), 51(6), 63(6)90
1114.802,3-2H-benzofuran-5-ol-2-one, 3,3-dimethylC10H10O3178150(100), 135(87), 107(53), 178(51), 77(25), 79(19), 53(11), 51(10)86
1215.40clofibric acidC10H11ClO3214128(100), 130(32), 41(11), 129(10), 65(9), 75(8), 214(7), 100(5)95
Tab.1  Main photodegradation intermediates identified by GC-MS in UV, UV/HO, VUV, VUV/HO and solar/TiO processes
Fig.4  Toxicity assessment by inhibition of (T, spp.) for intermediates of clofibric acid oxidation in (a) UV and VUV, (b) UV/HO and VUV/HO (100 times dilution of samples) and (c) solar/TiO processes ( = 10 mg L, [HO] = 100 mg L, [TiO] = 1000 mg L, = 10°C)
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