Investigations on the Degradation of Triazine Herbicides in Water by Photo-Fenton Process

Sondos Dbira, Ahmed Bedoui, Nasr Bensalah

Department of Chemistry and Earth Sciences, College of Arts and Sciences, Qatar University, Doha, Qatar.
Department of Chemistry, Faculty of Sciences of Gabes, University of Gabes, Gabes, Tunisia.

DOI: 10.4236/ajac.2014.58059                

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.

Keywords

Photo-Fenton Process, Hydroxyl Radicals, s-Triazine Herbicides, Degradation, Cyanuric Acid

Conflicts of Interest

The authors declare no conflicts of interest.

References

[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. http://dx.doi.org/10.1016/j.envpol.2005.07.024
[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. http://dx.doi.org/10.2166/wst.2010.932
[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. http://dx.doi.org/10.1016/j.foodcont.2011.11.031
[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. http://dx.doi.org/10.1016/j.foodcont.2011.11.031
[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. http://dx.doi.org/10.1021/es070959n
[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. http://dx.doi.org/10.1016/j.envpol.2010.07.039
[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. http://dx.doi.org/10.1016/j.envpol.2003.10.008
[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. http://dx.doi.org/10.1016/S0026-265X(00)00143-0
[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. http://dx.doi.org/10.1016/j.bbrc.2004.03.112
[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. http://dx.doi.org/10.1016/j.jhazmat.2011.02.060
[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. http://dx.doi.org/10.1016/j.chemosphere.2003.11.021
[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. http://dx.doi.org/10.1016/j.seppur.2012.02.018
[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. http://dx.doi.org/10.1016/S0143-7208(03)00129-3
[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. http://dx.doi.org/10.1016/j.envpol.2004.02.022
[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. http://dx.doi.org/10.1016/j.watres.2006.04.033
[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. http://dx.doi.org/10.1016/j.watres.2006.08.001
[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. http://dx.doi.org/10.1021/ie801755u
[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. http://dx.doi.org/10.1016/S0926-3373(02)00266-7
[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. http://dx.doi.org/10.1021/ie200266d
[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. http://dx.doi.org/10.1016/j.chemosphere.2007.08.027
[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. http://dx.doi.org/10.1016/j.jhazmat.2009.02.139
[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. http://dx.doi.org/10.1016/j.jelechem.2011.07.017
[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. http://dx.doi.org/10.1002/jctb.1873
[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. http://dx.doi.org/10.1016/S0920-5861(99)00102-9
[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. http://dx.doi.org/10.1080/10643380500326564
[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. http://dx.doi.org/10.1080/09593330801983516
[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. http://dx.doi.org/10.1016/j.watres.2008.09.008
[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. http://dx.doi.org/10.1021/jp1035647
[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. http://dx.doi.org/10.1007/s10311-011-0337-z
[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. http://dx.doi.org/10.1080/03601230601017965
[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. http://dx.doi.org/10.1016/j.jphotochem.2005.03.013
[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. http://dx.doi.org/10.1016/j.jphotochem.2006.12.041
[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. http://dx.doi.org/10.4172/2155-6199.1000208
[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. http://dx.doi.org/10.1016/S0304-3894(03)00213-9
[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. http://dx.doi.org/10.1111/j.1556-4029.2010.01333.x
[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. http://dx.doi.org/10.1039/b508138f
[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. http://dx.doi.org/10.1016/j.foodcont.2008.04.004
[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. http://dx.doi.org/10.1016/S1010-6030(03)00372-1
[41]	Tetzlaff, T.A. and Jenks, W.S. (1999) Stability of Cyanuric Acid to Photocatalytic Degradation. Organic Letters, 1, 463-465. http://dx.doi.org/10.1021/ol9906662