UV/Fenton process was employed to remove clopyralid; meanwhile, various UV-based oxidation processes were compared, such as UV irradiation, UV/H2O2, and UV/Fe(II). Results illustrated that UV/Fenton exhibited the highest degradation rate, and UV irradiation alone hardly affected degradation of clopyralid. Rate constants, T1/2 (half-time) and EEO (electrical energy per order) were calculated to evaluate degradation rate and energy consumption among all these approaches. Some influencing factors, such as pH, irradiation time, and molar concentration ratio of hydrogen peroxide to ferrous ions, were studied to obtain an optimal degradation condition for UV/Fenton process. To evaluate the efficiency of UV/Fenton process applied for clopyralid degradation in aqueous solution, change of chemical oxygen demand in solution after UV/Fenton treatment was measured. Ion chromatograph was used to analyze formation of inorganic ions and short-chain carboxylic acids during photodegradation process. It was found that concentrations of chloride and ammonium were increased with irradiation time, and some short-chain carboxylic acids were detected.
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References
1.
AbramovicB.F., AnderluhV.B., SojicD.V., and GaalF.F. (2007). Photocatalytic removal of the herbicide clopyralid from water. J. Serbian Chem. Soc., 72, 1477.
2.
AffamA.C., ChaudhuriM., KuttyS.R.M., and MudaK. (2014). UV Fenton and sequencing batch reactor treatment of chlorpyrifos, cypermethrin and chlorothalonil pesticide wastewater. Int. Biodeterioration Biodegradation., 93, 195.
3.
AleboyehA., MoussaY., and AleboyehH. (2005). The effect of operational parameters on UV/H2O2 decolourisation of Acid Blue 74. Dyes Pigments. 66, 129.
4.
AlfanoO.M., BrandiR.J., and CassanoA.E. (2001). Degradation kinetics of 2,4-D in water employing hydrogen peroxide and UV radiation. Chem. Eng. J., 82, 209.
5.
AndreozziR., Di SommaI., MarottaR., PintoG., PollioA., and SpasianoD. (2011). Oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol by means of Fe(III)-homogeneous photocatalysis and algal toxicity assessment of the treated solutions. Water Res. 45, 2038.
6.
AntoniouM.G., de la CruzA.A., and DionysiouD.D. (2010). Degradation of microcystin-LR using sulfate radicals generated through photolysis, thermolysis and e(-) transfer mechanisms. Appl. Catalysis B Environ., 96, 290.
7.
BauerR., and FallmannH. (1997). The Photo-Fenton oxidation – a cheap and efficient wastewater treatment method. Res. Chem. Intermed., 23, 341.
8.
BoltonJ.R., BircherK.G., TumasW., and TolmanC.A. (2001). Figures-of-merit for the technical development and application of advanced oxidation technologies for both electric- and solar-driven systems - (IUPAC Technical Report). Pure Appl. Chem., 73, 627.
9.
BuxtonG.V., GreenstockC.L., HelmanW.P., and RossA.B. (1988). Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (.OH/.O -) in aqueous solution. J. Phys. Chem. Reference Data., 17, 513.
10.
ÇatalkayaE.Ç., and ŞengülF. (2006). Application of Box–Wilson experimental design method for the photodegradation of bakery's yeast industry with UV/H2O2 and UV/H2O2/Fe(II) process. J. Hazard. Mater., 128, 201.
11.
ChenR.Z., and PignatelloJ.J. (1997). Role of quinone intermediates as electron shuttles in Fenton and photoassisted Fenton oxidations of aromatic compounds. Environ. Sci. Technol., 31, 2399.
12.
ChuW., WangY.R., and LeungH.F. (2011). Synergy of sulfate and hydroxyl radicals in UV/S2O82−/H2O2 oxidation of iodinated X-ray contrast medium iopromide. Chem. Eng. J., 178, 154.
13.
CorredorM.C., MelladoJ.M.R., and MontoyaM.R. (2006). EC(EE) process in the reduction of the herbicide clopyralid on mercury electrodes. Electrochim. Acta., 51, 4302.
14.
De GerónimoE., AparicioV.C., BárbaroS., PortocarreroR., JaimeS., and CostaJ.L. (2014). Presence of pesticides in surface water from four sub-basins in Argentina. Chemosphere, 107, 423.
15.
DonaldD.B., CessnaA.J., SverkoE., and GlozierN.E. (2007). Pesticides in surface drinking-water supplies of the northern Great Plains. Environ. Health Perspect., 115, 1183.
16.
DuY., SuY., LeiL., and ZhangX. (2009). Role of oxygen in the degradation of atrazine by UV/Fe(III) process. J. Photochem. Photobiol. A Chem., 208, 7.
17.
EyheraguibelB., Ter HalleA., and RichardC. (2009). Photodegradation of Bentazon, Clopyralid, and Triclopyr on Model Leaves: Importance of a Systematic Evaluation of Pesticide Photostability on Crops. J. Agric. Food Chem., 57, 1960.
18.
GallardH., de LaatJ., and LegubeB. (1998). Effect of pH on the oxidation rate of organic compounds by Fe-II/H2O2. Mechanisms and simulation. New J. Chem., 22, 263.
19.
GarbinJ.R., MiloriD.M.B.P., SimõesM.L., da SilvaW.T.L., and NetoL.M. (2007). Influence of humic substances on the photolysis of aqueous pesticide residues. Chemosphere. 66, 1692.
20.
GhodbaneH., and HamdaouiO. (2010). Decolorization of antraquinonic dye, C.I. Acid Blue 25, in aqueous solution by direct UV irradiation, UV/H2O2 and UV/Fe(II) processes. Chem. Eng. J., 160, 226.
21.
ISO. (2012). Water Quality-Determination of the Chemical Oxygen Demand-Dichromate Method. Geneva, Switzerland: International Organization for Standardization.
22.
JungY.S., LimW.T., ParkJ.Y., and KimY.H. (2009). Effect of pH on Fenton and Fenton-like oxidation. Environ. Technol., 30, 183.
23.
KarciA., Arslan-AlatonI., and BekboletM. (2013). Advanced oxidation of a commercially important nonionic surfactant: Investigation of degradation products and toxicity. J. Hazard. Mater., 263, 275.
24.
KasiriM.B., and KhataeeA.R. (2011). Photooxidative decolorization of two organic dyes with different chemical structures by UV/H2O2 process: Experimental design. Desalination. 270, 151.
25.
KhanJ.A., HeX.X., KhanH.M., ShahN.S., and DionysiouD.D. (2013). Oxidative degradation of atrazine in aqueous solution by UV/H2O2/Fe2+, UV/S2O82-/Fe2+ and UV/HSO5-/Fe2+ processes: A comparative study. Chem. Eng. J., 218, 376.
26.
KimY.H., KoS.O., ShinW.S., ChoiS.J., JungY.S., OhH.S., and ParkJ.Y. (2008). ENVR 217-Effect of pH on Fenton and Fenton-like reactions. Am. Chem. Soc., 235(abstract).
27.
KiwiJ., PulgarinC., and PeringerP. (1994). Effect of Fenton and photo-Fenton reactions on the degradation and biodegradability of 2 and 4-nitrophenols in water treatment. App. Catalysis B Environ., 3, 335.
28.
LiG., WongK.H., ZhangX., HuC., YuJ.C., ChanR.C.Y., and WongP.K. (2009). Degradation of Acid Orange 7 using magnetic AgBr under visible light: The roles of oxidizing species. Chemosphere. 76, 1185.
29.
LiW.G., WangY., and IriniA. (2014). Effect of pH and H2O2 dosage on catechol oxidation in nano-Fe3O4 catalyzing UV-Fenton and identification of reactive oxygen species. Chem. Eng. J., 244, 1.
30.
LinS.H., and LoC.C. (1997). Fenton process for treatment of desizing wastewater. Water Res. 31, 2050.
31.
LiuN., SijakS., ZhengM., TangL., XuG., and WuM. (2015). Aquatic photolysis of florfenicol and thiamphenicol under direct UV irradiation, UV/H2O2 and UV/Fe(II) processes. Chem. Eng. J., 260, 826.
32.
MalatoS., BlancoJ., VidalA., AlarcónD., MaldonadoM.I., CáceresJ., and GernjakW. (2003). Applied studies in solar photocatalytic detoxification: An overview. Solar Energy. 75, 329.
33.
MasiáA., CampoJ., Vázquez-RoigP., BlascoC., and PicóY. (2013). Screening of currently used pesticides in water, sediments and biota of the Guadalquivir River Basin (Spain). J. Hazard. Mater., 263, Part 1, 95.
34.
Orellana-GarcíaF., ÁlvarezM.A., López-RamónV., Rivera-UtrillaJ., Sánchez-PoloM., and MotaA.J. (2014). Photodegradation of herbicides with different chemical natures in aqueous solution by ultraviolet radiation. Effects of operational variables and solution chemistry. Chem. Eng. J., 255, 307.
35.
OzcanA., OturanN., SahinY., and OturanM.A. (2010). Electro-Fenton treatment of aqueous Clopyralid solutions. Int. J. Environ. Anal. Chem., 90, 478.
36.
PaoliniM., SaponeA., and GonzalezF.J. (2004). Parkinson's disease, pesticides and individual vulnerability. Trends Pharmacol. Sci., 25, 124.
37.
PignatelloJ.J., OliverosE., and MacKayA. (2006). Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry. Crit. Rev. Environ. Sci. Technol., 36, 1.
38.
SojicD., DespotovicV., AbramovicB., TodorovaN., GiannakopoulouT., and TrapalisC. (2010). Photocatalytic Degradation of Mecoprop and Clopyralid in Aqueous Suspensions of Nanostructured N-doped TiO2. Molecules. 15, 2994.
39.
SojicD.V., AnderluhV.B., OrcicD.Z., and AbramovicB.F. (2009). Photodegradation of clopyralid in TiO2 suspensions: Identification of intermediates and reaction pathways. J. Hazard. Mater., 168, 94.
40.
TanC., GaoN., DengY., ZhangY., SuiM., DengJ., and ZhouS. (2013). Degradation of antipyrine by UV, UV/H2O2 and UV/PS. J. Hazard. Mater., 260, 1008.
41.
TangW.Z., and HuangC.P. (1996). 2,4-dichlorophenol oxidation kinetics by Fenton's reagent. Environ. Technol., 17, 1371.
42.
TizaouiC., MezughiK., and BickleyR. (2011). Heterogeneous photocatalytic removal of the herbicide clopyralid and its comparison with UV/H2O2 and ozone oxidation techniques. Desalination. 273, 197.
43.
ToanP.V., SebesvariZ., BläsingM., RosendahlI., and RenaudF.G. (2013). Pesticide management and their residues in sediments and surface and drinking water in the Mekong Delta, Vietnam. Sci. Total Environ., 452, 28.
44.
WestphalK., SaligerR., JagerD., TeevsL., and PrusseU. (2013). Degradation of Clopyralid by the Fenton Reaction. Ind. Eng. Chem. Res., 52, 13924.
45.
XuG., BuT.T., WuM.H., ZhengJ.A., LiuN., and WangL. (2011). Electron beam induced degradation of clopyralid in aqueous solutions. J. Radioanal. Nucl. Chem., 288, 759.
46.
XuG., LiuN., WuM.H., BuT.T., and ZhengM. (2013). The photodegradation of clopyralid in aqueous solutions: Effects of light sources and water constituents. Ind. Eng. Chem. Res., 52, 9770.
47.
XuX.-R., LiX.-Y., LiX.-Z., and LiH.-B. (2009). Degradation of melatonin by UV, UV/H2O2, Fe2+/H2O2 and UV/Fe2+/H2O2 processes. Separation Purif. Technol., 68, 261.
48.
ZimbronJ.A., and ReardonK.F. (2009). Fenton's oxidation of pentachlorophenol. Water Res. 43, 1831.
