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  1. 1. P.A.Fasnabi, C.S.Remya, G.Madhu/ International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 Vol. 2, Issue 6, November- December 2012, pp.1672-1675 Degradation of Acetamiprid in Wastewater by Ozonation P.A.Fasnabi, C.S.Remya, G.Madhu Department of Chemical Engineering, Govt Engineering College, Thrissur-9, IndiaChemical Engineering Group, School of Engineering, Cochin University of Science and Technology, Kochi-22, IndiaABSTRACT Pesticides belong to the class of persistent studied by Benitez et al. He could obtain similarchemicals in the environment which cause serious degradation at pH 2 and 9 which indicates thehealth hazards. Advanced Oxidation Processes negligible contribution of the reaction with hydroxyl(AOPs) represent the fast developing area in radical generated by the ozone self-decomposition atwater and wastewater treatment by which non pH 9 [12]. K.lafi et al. could obtain 90% removal ofbiodegradable and difficult to biodegradable the pesticide deltamethrin using ozonation in acompounds can be removed. This paper discusses period of 210 min [1]. Amat et al. treated a pair ofthe use of ozonation for the removal of insecticide commercial anionic surfactants with ozonation in anacetamiprid from water. Response surface alkaline medium. After only 10 min of treatment,Methodology was used for the optimisation of the surfactants were almost completely eliminated [14].process parameters: ozone flow rate and pH. The present work focuses on the degradation of acetamiprid by ozonation. The effect of parametersKeywords - Acetamiprid, Advanced Oxidation like ozone flow rate and pH were also studied.Process, Ozonation Response surface methodology was used for optimisation of the process.1. INTRODUCTION Pesticides have become an unavoidable 2. EXPERIMENTALcommodity in our modern life. The introduction of 2.1 PROCEDURESpesticides in the environment cause serious issues of Acetamiprid (97%) was purchased fromwhich water pollution is of primary importance. Rallis India. The properties of acetamiprid is givenRemoval of these compounds from water is a in Table 1. Sulphuric acid and sodium hydroxidechallenge to the environmental engineers because were used for adjusting the pH. The reagents weremost of them are nonbiodegradable [1]. Acetamiprid not subjected to further purification. Distilled waterbelongs to a new class of insecticides, was used for making the solutions throughout.neonicotinoids, The use of neonicotinoids is Ozone generator of capacity 2g/hr was used as theincreasing tremendously because of their ability to source of ozone.replace most of the organophosphates. They are Table1. Properties of Acetamipridcommonly applied to cotton, vegetables, flowers, Common Name Acetamipridfruits etc. Name (IUPAC): (E)-N-[(6-chloro-3- Most of the chemical treatment methods pyridyl)methyl]-N-cyano-N-utilized for pesticides degradation cause the methyl acetamidinformation of secondary pollutants. Advanced Molecular C10H11ClN4oxidation processes employ different methods for Formulageneration of the hydroxyl radicals. Hydroxyl Molecular Weight 222.68radicals are very reactive and not highly selective.They can convert the pollutants to CO2 and water or Pesticide Type Insecticideatleast to degradable compounds [2-5]. Ozonation is Chemical Family Neonicotinoid Insecticidea widely used technique for the removal of Application Sites Control of Sucking-Typepollutants from water and wastewater[6-8]. The Insects on Leafy Vegetables,degradation of compounds occurs through the action Fruiting Vegetables, Coleof ozone itself as well as through the radicals Crops, Citrus Fruits, Pomegenerated in aqueous medium. The major reactions Fruits, Grapes, Cotton, andtaking place are [9-11]: Ornamental Plants andO3 + OH-→ O3.-+ OH. (1) FlowersO3.- → O2 + O.- (2) Carrier WaterO.- + H- → OH. (3) Physical State Solid, PowderOzonation was utilized by Esplugas et al. for the Color White powderremoval of phenol from wastewater [9]. 100% Odour Odorlessdegradation was obtained at a pH of 9.4 in 80 Solubility in 4.25 x 10+3 mg/L at 25°Cminutes. Degradation of carbofuran by ozone was Water 1672 | P a g e
  2. 2. P.A.Fasnabi, C.S.Remya, G.Madhu/ International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 Vol. 2, Issue 6, November- December 2012, pp.1672-1675 The stock solution of acetamiprid p, and the significant level (1-p) are also given in thecontaining 0.5 mg /cm3 was prepared using distilled Tables 3-5. It can be observed from the tables 3 to 5water. 500ml of the solution was taken and pH was that all the terms except the interaction term of pHadjusted using H2SO4/ NaOH. The flow rate of and ozone flow rate are highly influential in theozone was adjusted to the desired level and it was model for the prediction of pesticide removal, CODpassed through diffusers in to the solution for and TOC from the waste water.2hours. After the treatment the solution wasanlaysed for COD, TOC and concentration of the Table 3: Estimated Regression coefficients andinsecticide. TOC was measured using Shimadzu corresponding p values for COD removal (%)TOC-L-CPH analyzer. Concentration of pesticide Factor Coefficient of p value Significancewas analysed by Hitachi Elite Lachrome High the model in Level (%)Performance Liquid Chromatograph equipped with uncodedUV detector. The mobile phase was a mixture of factorswater /acetonitrile (70-30). It was eluted at a rate of1 ml/min. COD was measured by standard methods Constant -266.109 0.003 >47%[12]. A 834.206 0.002 >99% B 313.705 0.006 >98%2.2 RESPONSE SURFACE METHODOLOGY Response surface methodology (RSM) is Aa -2.577 0.000 >99%essentially a particular set of mathematical and bb -156.538 0.002 >99%statistical methods for designing experiments,building models, evaluating the effect of variables, ab 6.268 0.194 >80%and searching optimum conditions of variables topredict target responses [15-17]. Its important Table 4: Estimated Regression coefficients andapplications are in the designs, development, corresponding p values for Pesticide removal (%)formulation of new processes, and in the Factor Coefficient p value Significanceimprovement of existing designs. Its purpose is to of the model Level (%)determine the optimum operating conditions through in uncodedexperimental methods. In this work, central factorscomposite design with two factors at five levels wasapplied using Minitab 15 (Minitab Inc., State Constant -7.4615 0.533 >47%College, PA,trial version). The parameters used are A 8.5787 0.000 >99%ozone flow rate and pH which are denoted by A andB respectively. The levels of independent variables B 44.5947 0.022 >98%are given in Table 2. Aa -0.5431 0.000 >99% bb -23.5968 0.007 >99%Table 2: Independent variables and their levels forthe central composite design ab 1.0447 0.239 >80%Variable Coded Levels Table 4: Estimated Regression coefficients and -α -1 0 +1 +α corresponding p values for TOC removal (%)pH 4.38 5.5 8.25 11 12.1 39 Factor Coefficient p value SignificanceOzone 0.702 0.814 1.086 1.357 1.46 of the Level (%)Flow rate 9 model in(g/hr) uncoded factors3. RESULTS AND DISCUSSION Constant -34.1129 0.001 >47%3.1 RESPONSE SURFACE METHODOLOGY A 4.9307 0.000 >99% A second-order polynomial model, as B 38.4338 0.004 >98%given in Equation 4 was fitted to the experimentaldata Aa -0.3349 0.000 >99%Y= Constant + aA + bB + aaA2 + bbB2+ abAB bb -16.822 0.003 >99%(4) 0.2980 0.555 >45% abwhere Y is the response variable; a and b are theregression coefficients for linear effects; aa, bb are Equation 5 can be represented in terms of uncodedthe quadratic coefficients and ab is the interaction variables ascoefficient. The significance of the regression Y1 = -266.109 + 34.20572A + 313.705B – 2.577A2coefficients was analyzed using p test. The values of –156.538B2 + 6.268AB (5) 1673 | P a g e
  3. 3. P.A.Fasnabi, C.S.Remya, G.Madhu/ International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 Vol. 2, Issue 6, November- December 2012, pp.1672-1675 Y2 = -7.46154 + 8.57873A + 44.5947B – 0.5431A2 Contour Plot of %TOC removal vs Ozone flowrate(g/hour), pH – 23.5968B2 + 1.0447AB (6) 1.4 7.5 Y3 = -34.1129 + 4.9307A + 38.4338B – 0.3349A2 – 1.3 16.8222B2 + 0.2980AB Ozone flowrate(g/hour) 1.2 (7) Where Y1, Y2, Y3 correspond to response of COD, 1.1 pesticide and TOC removal percentages 1.0 respectively. 2.5 0.9 3.2 EFFECT OF VARIABLES 0.8 2.5 5.0 0.0 The results of the Experimental runs are given 5 6 7 8 9 10 11 12 pH Figure 1-3. Contour plots shows that the maximum exists in the domain selected for study. Fig 3: Combined Effect of pH and Ozone flow rate Contour Plot of %COD removal vs Ozone flowrate(g/hour), pH on TOC Removal 40 1.4 The optimum conditions predicted for the 1.3 process were pH 8.2 and ozone flow rate of Ozone flowrate(g/hour) 1.18g/hr. The COD removal(%), pesticide removal 1.2 (%) and TOC removal at this conditions were 53.9, 1.1 56.9 and 8.7% respectively. TOC removal is low 1.0 since the degradation products of acetamiprid exist in the medium and mineralization was not complete. 0.9 0 The optimum conditions were checked 0.8 experimentally and results obtained were close to 20 20 the predicted value. 5 6 7 8 9 10 11 12 pH 4. CONCLUSION The ozonation process for the removal of Fig 1: Combined Effect of pH and Ozone flow rate acetamiprid from aqueous solutions was on COD removal investigated. As ozonation is normally used for disinfection, the removal of pesticide is an addedContour Plot of %Pesticide removal vs Ozone flowrate(g/hour), pH advantage. Eventhough the degradation is not complete, a removal efficiency of 57% was obtained 45 51 1.4 which shows that ozonation can be used as a first 1.3 step in the treatment process. The optimum pH Ozone flowrate(g/hour) obtained was 8.1, which shows that the process is 1.2 more effective in alkaline medium. This can be 1.1 explained by the equations 1-3. Ozonation is a 1.0 viable process for acetamiprid removal and it does 51 not produce sludge as in Fenton process. 0.9 Combination of Ozone with other reagents like 0.8 54 H2O2 and UV can be tried for improving the 45 48 48 removal of pesticide. 5 6 7 8 9 10 11 12 pH 5. ACKNOWLEDGEMENT The authors wish to thank centre for Fig 2: Combined Effect of pH and Ozone flow rate Engineering Research and Development (CERD), on Pesticide Removal Kerala for financial support REFERENCES [1] Walid K. Lafi, Z. Al-Qodah, Combined advanced oxidation and biological treatment processes for the removal of pesticides from aqueous solutions, J.Haz.Mat. B137 ,2006, 489-497 [2] J.M.Poyatos, M.M, munio, M.C.Almecija, J.C. Torres, E. Hontoria, F. Osoria, 1674 | P a g e
  4. 4. P.A.Fasnabi, C.S.Remya, G.Madhu/ International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 Vol. 2, Issue 6, November- December 2012, pp.1672-1675 Advanced oxidation processses for anionic surfactants by means of ozone wastewater treatment-Sate of the Art, and/or UV irradiation, Envir. Engg. Water Air Soil pollut, 205, ,2010, 187-204. Sci.24(6) (2007) 790-794[3] R. Munter, Advanced oxidation processes – [14] Standard Methods for the Examination of current status and prospects, Proc.Estonian Water and Waste Water, 20th edn, AWWA, Acad. Acy. Chem. 50, 2001, 59-80 washington, DC, 1998[4] M.B. Ray, J.Paul Chen, Lawrence K.Wang, [15] R. H. Myers, D. C. Montgomery, Response Simo Olavi Penkonen, Advanced surface methodology; process and product Oxidation Processes : In AL.K. Wang, Y-T optimization using designed Hung, N.K Shammas (eds), Handbook of experiments,2002. Environmental Engineering, Vol [16] Korbahti, B. K. Response Surface 4:Advanced Physicochemical Treatment Optimization of Electrochemical Treatment processes,( The Humana Press Inc.),463- of Textile Dye Wastewater. J. Hazard. 464 Mater. 2007, 145, 277.[5] Serge Chiron, Amadeo Fernandez Alba, [17] Deniz, B.; Ismail, H. Boyaci Modeling and Antonio Rodriguez, Eloy Garcia Calvo, Optimization I: Usability of Response Pesticide Chemical Oxidation: State of art, Surface Methodology. J. Food Eng. 2007, Water.Res. 34,2002, 366-377 78, 836.[6] R.G. Rice, 1997, Application of ozone for industrial wastewater treatment — a review, Ozone Science and Engineering, International Ozone Association, USA, 1997, pp. 477–515.[7] Staehelin, J ., and J . Hoignè, Decomposition of ozone in water in the presence of organic solutes acting as promoters and inhibitors of radical chain reaction. Environmental Science and Technology,1985, 1206-1213 .[8] C. Kruithof and P.C. Kamp, The dilemma of pesticide control and by-product formation in the Heemsterk drinking water treatment plant design, Proceedings EAG Ozone Generation and Application to Water and Wastewater Treatment, Moskwa, 1998, 331–347[9] Santiago Esplugas, Jaime Gimenez, sandra Contrerars, Esther Pascual, Miguel Rodriguez, Comparison of different advanced oxidation processes for phenol degrdation, Water Research, 36 ,2002,1034-1042[10] Serge Chiron, Amadeo Fernandez Alba, Antonio Rodriguez, Eloy Garcia Calvo, Pesticide Chemical Oxidation: State of art, Water.Res. 34,2002,366-377[11] J. Hoigne, Chemistry of aqueous ozone and transformation of pollutants by ozonation and advanced oxidation process, in : J Hurbec (eds) The Handook of Environmental Chemistry Vol 5 , Part C, Quality and treatment of Drinking Water II, Springer, Berlin, Germany 1998[12] F. Javier Benitez, Juan L. Acero, Fracisco J. Real, Degradation of carbofuran by using ozone, UV radiation and advanced oxidation processes. J.Haz.Mat B89 ,2002,51-65[13] Amat A.M, Miranda M.A, Vincente R, Segui S, Degradation of two commercial 1675 | P a g e