AJAC  Vol.5 No.8 , June 2014
Investigations on the Degradation of Triazine Herbicides in Water by Photo-Fenton Process
Abstract: In this work, the degradation of 2-chloro-4,6-diamino-1,3,5-triazine in aqueous solutions by photo-Fenton process has been investigated. The preliminary results have shown that the degradation of 2-chloro-4,6-diamino-1,3,5-triazine by photo-Fenton process is more rapid and more effective than Fenton and UV/H2O2 processes. The effects of certain experimental parameters on kinetics and efficiency of the degradation of 2-chloro-4,6,-diamino-1,3,5-triazine by photo-Fenton process, have been evaluated. Under optimal conditions, photo-Fenton process achieved more than 90% of chloride release and about 30% of nitrate formation. The results of total organic carbon (TOC) and total Kjeldahl nitrogen (TKN) analyses have shown that no carbon dioxide and ammonia are formed during photo-Fenton treatment of aqueous solutions containing 40 mg/L triazine. These results indicate that only substituent groups of triazine ring are released; however, nitrogen atoms of triazine ring remain unaffected. A simple mechanism of degradation of 2-chloro-4,6-diamino-1,3,5-triazine has been proposed. The degradation starts by a rapid release of chlorine atoms as chloride ions to form 2-hydroxy-4,6-diamino-1,3,5-triazine. The amino groups of 2-hydroxy-4,6-diamino-1,3,5-triazine undergo are oxidized into nitro groups by hydroxyl radicals to form 2-hydroxy-4,6-dinitro-1,3,5-triazine which undergoes a slow release of nitro groups and their substitution with hydroxyl groups to form cyanuric acid and nitrate ions. The degradation of cyanuric acid by photo-Fenton process has also been investigated. The results of TOC and TKN analyzes show that no carbon dioxide is formed during the treatment.
Cite this paper: Dbira, S. , Bedoui, A. and Bensalah, N. (2014) Investigations on the Degradation of Triazine Herbicides in Water by Photo-Fenton Process. American Journal of Analytical Chemistry, 5, 500-517. doi: 10.4236/ajac.2014.58059.

[1]   Duguet, J.P. (1994) Occurrence of Pesticides in Natural Waters and Removal Duringdrinking Water Treatment Processes. Water Supply, 12, 111-115.

[2]   Konstantinou, I.K., Hela, D.G. and Albanis, T.A. (2006) The Status of Pesticide Pollution Insurface Waters (Rivers and Lakes) of Greece. Part I: Review on Occurrence and Levels. Environmental Pollution, 141, 555-570.

[3]   Stamatis, N., Konstantinou, I. and Hela, D. (2010) Pesticide Inputs from the Sewage Treatment Plant of Agrinio to River Acheloos, Western Greece: Occurrence and Removal. Water Science and Technology, 62, 1098-1105.

[4]   Sinha, S., Rao, M., Vasudev, K. and Odetokun, M. (2012) A Liquid Chromatography Mass Spectrometry-Based Method to Measure Organophosphorous Insecticide, Herbicide and Non-Organophosphorous Pesticide in Grape and Apple Samples. Food Control, 25, 636-646.

[5]   Griffini, O., Bao, M.L., Barbieri, C., Burrini, D. and Pantani, F. (1997) Occurrence of Pesticides in the Arno River and in Potable Water—A Survey of the Period 1992-1995. Bulletin of Environmental Contamination and Toxicology, 59, 202-209.

[6]   Giudice, B.D., Massoudieh, A., Huang, X. and Young, T.M. (2008) A Stochastic Simulation Procedure for Selecting Herbicides with Minimum Environmental Impact. Environmental Science Technology, 42, 354-360.

[7]   Glæsner, N., Bælum, J., Strobel, B.W. and Jacobsen, C.S. (2010) Atrazine Is Not Readily Mineralized in 24 Temperate Soils Regardless of Pre-Exposure to Triazine Herbicides. Environmental Pollution, 158, 3670-3674.

[8]   Dombek, T., Davis, D., Stine, J. and Klarup, D. (2004) Degradation of Terbutylazine (2-Chloro-4-ethylamino-6-terbutylamino-1,3,5-Triazine), Deisopropyl Atrazine (2-Amino-4-chloro-6-ethylamino-1,3,5-triazine), and Chlorinated Dimethoxy Triazine (2-Chloro-4,6-dimethoxy-1,3,5-triazine) by Zero Valent Iron and Electrochemical Reduction. Environmental Pollution, 129, 267-275.

[9]   Kim, S.Y., Jo, Y.A., Choi, J. and Choi, M.J. (2001) Characterization of s-Triazine Antibodies and Comparison of Enzyme Immunoassay for the Determination of s-Triazine. Microchemical Journal, 68, 163-172.

[10]   Singh, P., Suri, C.R. and Cameotra, S.S. (2004) Isolation of a Member of Acinetobacter Species Involved in Atrazine Degradation. Biochemical and Biophysical Research Communications, 317, 697-702.

[11]   Bensalah, N., Khodary, A. and Abdel-Wahab, A. (2011) Kinetic and Mechanistic Investigations of Mesotrione Degradation in Aqueous Medium by Fenton Process. Journal of Hazardous Materials, 189, 479-485.

[12]   De Laat, J., Le, G.T. and Legube, B. (2004) A Comparative Study of the Effects of Chloride, Sulfate and Nitrate Ions on the Rates of Decomposition of H2O2 and Organic Compounds by Fe(II)/H2O2 and Fe(III)/H2O2. Chemosphere, 55, 715-723.

[13]   Virender, K., Theodoros, M., Maria, G., X.X., He, Miguel, P., Changseok, H., Weihua, S., Kevin, E., Armah, A., Triantafyllos, K., Anastasia, H. and Dionysios, D. (2012) Destruction of Microcystins by Conventional and Advanced Oxidation Processes: A Review. Separation and Purification Technology, 91, 3-17.

[14]   Neamtu, M., Yediler, A., Siminiceanu, I., Macoveanu, M. and Kettrup, A. (2004) Decolourization of Disperse Red 354 Azo Dye in Water by Several Oxidation Processes—A Comparative Study. Dyes and Pigments, 60, 61-68.

[15]   Chan, C.Y., Tao, S., Dawson, R. and Wong, P.K. (2004) Treatment of Atrazine by Integrating Photocatalytic and Biological Processes. Environmental Pollution, 131, 45-54.

[16]   Hua, W., Bennett, E.R. and Letcher, R.J. (2006) Ozone Treatment and the Depletion of Detectable Pharmaceuticals and Atrazine Herbicide in Drinking Water Sourced from the Upper Detroit River, Ontario, Canada. Water Research, 40, 2259-2266.

[17]   Muñoz, I., Peral, J., Ayllon, L.J., Malato, S., Passarinho, P. and Domenech, X. (2006) Life Cycle Assessment of a Coupled Solar Photocatalytic-Biological Process for Waste Water Treatment. Water Research, 40, 3533-3540.

[18]   Bedoui, A., Elsaid, K., Bensalah, N. and Abdel-Wahab, A. (2011) Treatment of Pharmaceutical-Manufacturing Waste-waters by UV Irradiation/Hydrogen Peroxide Process. Journal of Advanced Oxidation Technologies, 14, 226-234.

[19]   Ahmed, B., Mohamed, H., Limem, E. and Nasr, B. (2009) Degradation and Mineralization of Organic Pollutants Contained in Actual Pulp and Paper Mills Wastewaters by a UV/H2O2 Process. Industrial and Engineering Chemistry Research, 48, 3370-3379.

[20]   Konstantinou, K.I. and Albanis, A.T. (2003) Photocatalytic Transformation of Pesticides in Aqueous Titanium Dioxide Suspensions Using Artificial and Solar Light: Intermediates and Degradation Pathways. Applied Catalysis B: Environmental, 42, 319-335.

[21]   Ahmed, B., Limem, E., Abdel-Wahab, A. and Nasr, B. (2011) Photo-Fenton Treatment of Actual Agro-Industrial Wastewaters. Industrial and Engineering Chemistry Research, 50, 6673-6680.

[22]   Martín, B.M.M., Pérez, S.J.A., Fernández, A.F.G., López, J.L., Garcia-Ripoll, A.M., Arques, I.O. and Rodriguez, S.M. (2008) Combined Photo-Fenton and Biological Oxidation for Pesticide Degradation: Effect of Photo-Treated Intermediates on Biodegradation Kinetics. Chemosphere, 70, 1476-1483.

[23]   Elahmadi, M.F., Bensalah, N. and Gadri, A. (2009) Treatment of Aqueous Wastes Contaminated with Congo Red Dye by Electrochemical Oxidation and Ozonation Processes. Journal of Hazardous Materials, 168, 1163-1169.

[24]   Oturan, N., Hamza, M., Ammar, S., Abdelhédi, R. and Oturan, M.A. (2011) Oxidation/Mineralization of 2-Nitrophenol in Aqueous Medium by Electrochemical Ad-vanced Oxidation Processes Using Pt/Carbon-Felt and BDD/Carbon-Felt Cells. Journal of Electroanalytical Chemistry, 661, 66-71.

[25]   Comninellis, C., Kapalka, A., Malato, S., Parsons, S.A., Poulios, I. and Mantzavinos, D. (2008) Advanced Oxidation Processes for Water Treatment: Advances and Trends for R&D. Journal of Chemical Technology and Biotechnology, 83, 769-776.

[26]   Andreozzi, R., Caprio, V., Insola, A. and Marotta, R. (1999) Advanced Oxidation Processes (AOP) for Water Purification and Recovery. Catalysis Today, 53, 51-59.

[27]   Pignatello, J.J., Oliveros, E. and Mackay, A. (2006) Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry. Critical Reviews in Environmental Science and Technology, 36, 1-84.

[28]   Kaichouh, G., Oturan, N., Oturan, M.A., ElHourch, A. and Elkacemi, K. (2008) Mineralization of Herbicides Imazapyr and Imazaquin in Aqueous Medium by Fenton, Photo-Fenton and Electro-Fenton Processes. Environmental Technology, 29, 489-496.

[29]   Hladik, M.L., Bouwer, E.J. and Roberts, A.L. (2008) Neutral Degradates of Chloroacetami Deherbicides: Occurrence in Drinking Water and Removal during Conventional Water Treatment. Water Research, 42, 4905-4914.

[30]   Borras, N., Oliver, R., Arias, C. and Brillas, E. (2010) Degradation of Atrazine by Electrochemical Advanced Oxidation Processes Using a Boron-Doped Diamond Anode. Journal of Physical Chemistry A, 114, 6613-6621.

[31]   Oturan, N., Brillas, E. and Oturan, M.A. (2012) Unprecedented Total Mineralization of Atrazine and Cyanuric Acid by Anodic and Electro-Fenton with a Boron-Doped Diamond Anode. Environmental Chemistry Letters, 10, 165-170.

[32]   Bandala, E.R., Dominguez, Z., Rivas, F. and Gelover, S. (2007) Degradation of Atrazine Using Solar Driven Fenton-Like Advanced Oxidation Processes. Journal of Environmental Science and Health, Part B: Pesticides, Food Contaminants, and Agricultural Wastes, 42, 21-26.

[33]   Watanabe, N., Horikoshi, S., Hidaka, H. and Serpone, N. (2005) On the Recalcitrant Nature of the Triazinic Ring Species, Cyanuric Acid, to Degradation in Fenton Solutions and in UV-Illuminated TiO2 (Naked) and Fluorinated TiO2 Aqueous Dispersions. Journal of Photochemistry and Photobiology A: Chemistry, 174, 229-238.

[34]   Ravichandran, L., Selvam, K. and Swaminathan, M. (2007) Photo-Fenton Defluoridation of Pentafluorobenzoic Acid with UV-C Light. Journal of Photochemistry and Photobiology A: Chemistry, 188, 392-398.

[35]   Cesaro, A., Naddeo, V. and Belgiorno, V. (2013) Wastewater Treatment by Combination of Advanced Oxidation Processes and Conventional Biological Systems. Journal of Bioremediation Biodegradation, 4, 208.

[36]   Rathi, A., Rajor, H.K. and Sharma, R.K. (2003) Photodegradation of Direct Yellow-12 Using UV/H2O2/Fe2+. Journal of Hazardous Materials, 102, 231-241.

[37]   Szumera, J., Wetniak, M., Olejniczak, A. and Lukaszewicz, J.P. (2010) Transfer of Triazine-Iron(II) Chromic Complexes Left by Iron Items on Textile Background and Human Skin. Journal of Forensic Sciences, 55, 944-952.

[38]   Gun, J., Ekeltchik, I., Lev, O., Shelkov, R. and Melman, A. (2005) Bis-(Hydroxyamino) Triazines: Highly Stable Hydroxylamine-Based Ligands for Iron(III) Cations. Chemical Communications, 42, 5319-5321.

[39]   Yu, C., Zhu, L., Xiao, J., Tang, H., Guo, G., Zeng, Q. and Wang, X. (2009) Ultrasonic Extraction and Determination of Cyanuric Acid in Pet Food. Food Control, 20, 205-208.

[40]   Oh, Y.C. and Jenks, W.S. (2004) Photocatalytic Degradation of a Cyanuric Acid, a Recalcitrant Species. Journal of Photochemistry and Photobiology A: Chemistry, 162, 323-328.

[41]   Tetzlaff, T.A. and Jenks, W.S. (1999) Stability of Cyanuric Acid to Photocatalytic Degradation. Organic Letters, 1, 463-465.