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Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design
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Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design

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prepared by M.C. Lu*, R.M. Briones**, and M.D.G. de Luna**, *** *Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan (E-mail: …

prepared by M.C. Lu*, R.M. Briones**, and M.D.G. de Luna**, *** *Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan (E-mail: mmclu@mail.chna.edu.tw) ** Environmental Engineering Graduate Program, University of the Philippines, 1011 Diliman, Quezon City, Philippines (Email: rowenambriones@yahoo.com) *** Department of Chemical Engineering, University for Urban Environments in Asia, 25-28 May 2011, Manila, Philippines. organized by International Water Association (IWA).

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  • 1. Oxidation of Acetaminophen by Fluidized-bed Fenton Process: Optimization using Box-Behnken Design M.C. Lu*, R.M. Briones**, and M.D.G. de Luna**, *** *Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan (E-mail: mmclu@mail.chna.edu.tw) ** Environmental Engineering Graduate Program, University of the Philippines, 1011 Diliman, Quezon City, Philippines (Email: rowenambriones@yahoo.com) *** Department of Chemical Engineering, University of the Philippines, 1011 Diliman, Quezon City, Philippines Abstract One of the most frequently used over-the-counter analgesic and antipyretic is acetaminophen (ACT). This drug finds its way into effluent wastewaters in concentrations that still pose an environmental threat even after conventional treatment. This study demonstrates the effectiveness of a fluidized-bed Fenton process in the degradation of acetaminophen in synthetic wastewater. Box-Behnken experimental design was employed to optimize initial pH, Fe2+ and H2O2 concentrations. The best ACT removal was achieved at pH 3.00 with both initial Fe2+ and H2O2 concentrations at their maximum. At this operating condition, almost 98% degradation was attained within only 20 minutes of reaction time. Optimization of operating conditions gave the best removal efficiency at pH=3.22, [Fe2+] = 0.06mM and [H2O2] = 19.87mM. Verification studies resulted in a 97.83% ACT removal with an initial rate of 0.234 mM/min. COD and TOC removals of 38.18% and 59.62%, respectively, were achieved. Parametric studies showed that a single stage slow degradation occurs at very low FH ratio. At higher FH ratio, a fast initial degradation followed by slow degradation occurs. Keywords: Fluidized-bed Fenton process; Box-Behnken design; acetaminophenINTRODUCTIONPharmaceuticals and personal care products (PPCPs) from pharmaceutical companies and humanuse reach surface waters usually unaltered. PPCPs are persistent and mostly resistant to microbialattack. Most of these substances are found to be endocrine disrupting compounds (EDCs), anemerging class of pollutants. Even at low concentrations, PPCPs have shown severe effects to theenvironment. A recent study attributed the rapid decline of vulture population in Northern India todiclofenac, a non-steroidal anti-inflammatory drug (NSAID) used as analgesic to treat arthritic andrheumatic conditions (Rizzo, et al., 2009). PPCPs were not only detected in effluents fromwastewater treatment plants (WWTPs) but also in surface and ground waters (Larsen, et al., 2004).The discharge of these substances into sewers and WWTPs poses serious problems and challengesin their removal. Existing water and WWTPs are not designed to remove these unregulated micro-pollutants. Many studies have shown that the reduction of pharmaceutical compounds inconventional WWTPs is usually incomplete. Though incomplete, WWTPs with tertiary treatmenthave better removal of PPCPs (Zhou, et al., 2009). To mitigate environmental contamination fromPPCPs, complete removal of these compounds in wastewaters is the best solution.Acetaminophen (ACT) is a non-steroidal anti-inflammatory drug (NSAID) used as an over-the-counter analgesic and antipyretic. It is one of the most frequently used drugs and ranked as the 5thmost used drug in the Philippines in 2006 (IMS, 2007). When ingested, 58-68% of this drug is
  • 2. excreted by the body unchanged (Zhang, et al., 2008). It is present in wastewaters in concentrationsexceeding 1000 ng/L (Wiegel, et al., 2004). Figure 1. Structure of acetaminophenAdvanced oxidation processes (AOPs) can achieve total degradation of target pollutants producingorganic acids, inorganic salts and CO2 as by-products. These processes generate hydroxyl radicals(•OH) in solution. Hydroxyl radicals are very powerful nonselective oxidizing agents which attackorganic matter in wastewater thereby promoting its degradation. Fenton oxidation, one of the mostimportant AOPs known, utilizes Fenton’s reagent, a combination of H2O2 and Fe2+, to producehydroxyl radicals for complete mineralization of organics (Khataee, et al., 2008). (1) (2) (3)Values of rate constants suggest that ferric ions are produced (Equation 1) more rapidly than theyare reduced to Fe2+ (Equation 3) resulting in the formation of excess Fe3+at the end of the process.Neutralization of the final solution leads to the formation and accumulation of Fe(OH)3 sludge -amajor disadvantage of the Fenton process.Fluidized-bed (FB) Fenton minimizes sludge production as the carrier itself acts as a seedingmaterial for crystallization of Fe3+ ions. Aside from the homogenous catalytic reaction betweenH2O2 and Fe2+ in solution, heterogeneous chemical reaction also occurs as the iron oxide-coatedcarrier also acts as a catalyst to produce •OH (Chou, Huang, & Huang, 1999).This study focused on the degradation of synthetic acetaminophen wastewater by chemicaloxidation using FB-Fenton process. It is a preliminary research in advanced wastewater treatmenttechnology particularly in sewage and pharmaceutical industries.MATERIALS AND METHODSChemicals and analytical methodsAll chemicals used, including 35% H2O2, 4-hydroxy acetanilide (ACT), FeSO4•7H2O, HClO4, HCl,H2SO4, NH4C2H3O2, C12H8N2•H2O, K2TiO4, acetonitrile, NaOH, were purchased from Merck. Allsolutions were prepared using Millipore system deionized water with a resistivity of 18.2 M .Residual H2O2 in solution was analyzed using titanium oxalate method. Residual ferrousconcentration was determined by complexation with 1,10-phenanthroline. Both methods wereanalyzed using a Thermo Spectronic Genesys 20 spectrophotometer at 400 nm for H2O2 and 510nm for ferrous ions. ACT concentration was determined with SpectraSYSTEM SN4000 HPLCequipped with Asahipak ODP-50 6D using 20 mM phosphoric acid and acetonitrile at 85:15, flowrate of 1 mL/min and at 220 nm. COD was measured using closed reflux titrimetric method,
  • 3. Standard Methods 5220 C. Total iron concentration was determined by Perkin Elmer AAnalyst 200AAS.Fluidized-bed Fenton and Fenton experimentsThe reactor with a working volume of 1.45 L was made of a cylindrical glass with inlet, outlet andrecirculating sections. It was equipped with a Suntex portable pH meter. All batch experimentswere done at room temperature. Synthetic acetaminophen wastewater at 5 mM was poured into thereactor and the pump was turned on. The initial pH was adjusted by adding concentrated HClO4 or0.1N NaOH. The desired amount of FeSO4•H2O was added into the solution as ferrous source.Glass beads of diameters 4 mm and 2 mm were added as support followed by the addition of SiO2carrier with a diameter of 0.5 mm. The pH of the solution was further adjusted. Samples were takenfor analyses of initial conditions. Samples taken were immediately injected into tubes containingsodium hydroxide solution to quench Fenton reaction and were filtered through a 0.22 µm syringemicrofilters. Hydrogen peroxide was finally added to start the reaction. The pH of the solution wasnot further adjusted as the reaction proceeded. Samples were taken at different time intervals of 0,3, 5, 10, 20, 40, 60, 90 and 120 minutes.Fenton experiments were done following the same procedure as in fluidized-bed Fenton process butwithout the addition of glass bead support and SiO2 carriers.Design of experimentOptimization of operating conditions was done using Box-Behnken design (BBD), a three-leveldesign used to fit second-order models. It can be expanded to estimate the combinations of thirdorder terms, i.e. x12x2, x12x3 and x1x22(Davis & Draper, 1998). This design has the advantage ofhaving very efficient number of required runs to fit the model. Design-Expert 7.0 software (Stat-Ease, Inc., Minneapolis, USA) was used to determine the number of experiments needed tooptimize and analyze the system.Three important parameters namely: pH, Fe2+ and H2O2, were studied and optimized using BBD. Atotal of 17 experimental runs were conducted with five replicates at the center point. All runs wereconducted at room temperature. Based on previous FB-Fenton studies (Muangthai, Ratanatamsakul,& Lu, 2010), the amount of carrier material has little significant impact on removal efficiency.Hence, its amount and size were fixed at 100g and 0.5mm respectively. Table 1 shows the levelsfor each factor used in the BBD.Table 1. Levels of factors used in Box-Behnken Design Levels Factors Symbol Low (-1) Center (0) High (+1) pH A 2 3 4 Fe2+ (mM) B 0.01 0.055 0.1 H2O2 (mM) C 5 15 25RESULTS AND DISCUSSIONBox-Behnken designAside from fitting a model for ACT removal, initial rate was also included as a response to predictthe efficiency of the process at optimum conditions. Using Design-Expert software, a reduced cubicmodel best fits ACT removal. For initial rate, a full quadratic model is sufficient and gives an
  • 4. insignificant lack of fit. Results of ANOVA gives adjusted R2 values of 0.9979 and 0.9764 for ACTremoval and initial rate, respectively.The best ACT removal was achieved at pH 3 and with the highest initial Fe2+ and H2O2concentrations of 0.01 and 25 mM, respectively. Almost 98% degradation was attained within only20 min of reaction time. The worst removal was 20.91% at pH=2, [Fe2+]=0.01mM and[H2O2]=15mM.Correlation of each factor on ACT removal and initial rate. Table 2 shows the correlation of eachparameter studied on ACT removal efficiency and initial rate. All three parameters have significantpositive effects on both responses and must be considered in the analysis of the effect of eachfactor.Table 2. Correlation values of each factor on ACT removal and initial rate Correlation Factor ACT removal Initial rate pH 0.304 0.481 Fe2+ 0.429 0.654 H2O2 0.555 0.211Although all parameters have positive effect on ACT removal, 3D surface plots reveal pH level andFe2+ concentration levels where removal of ACT start to decrease.
  • 5. (a) (a)(b) (b)(c) (c)Figure 2. 3D surface plots of the two parameter Figure 3. 3D surface plots of the two parameter interaction effects of initial pH, [Fe2+] and interaction effects of initial pH, [Fe2+] and [H2O2] on initial rates: (a) [H2O2]=25mM, (b) [H2O2] on ACT removal: (a) [H2O2]=25mM, pH=3, (c) [Fe2+]=0.055mM. (b) pH=3, (c) [Fe2+]=0.055mM.
  • 6. Optimization using BBD. As generated by Design Expert 7.0 software, the equations for ACTremoval and initial rate, respectively, by fluidized-bed Fenton process in terms of coded factors areas follows:% ACT removal= 92.99 + 3.15A + 5.51B + 16.89C – 12.68AB + 3.17AC + 4.25BC – 10.72A2 - 12.71B2 – 7.57C2 + 15.09A2B + 12.21AB2Initial rate, mM/min = 0.22 + 0.21A + 0.29B + 0.094C + 0.28AB – 0.0079AC + 0.099BC + 0.073A2 + 0.12B2 + 0.014C2where A, B and C are initial pH, initial Fe2+ concentration and initial H2O2 concentration,respectively with values of (-1) to (1) indicating the level.For a cost effective operation, the amount of chemicals added were kept at a minimum while ACTremoval was set to a target of 95-100% for best removal efficiency. The software generated onlyone solution with the criteria as shown in Table 3.Table 3. Optimum condition factors and responses as predicted by Design-Expert 7.0 Factor Condition pH 3.22 [Fe2+] 0.06 mM [H2O2] 19.87 mM ACT removal 100% Initial rate 0.3185 mM/minComparison between conventional Fenton and fluidized-bed Fenton process at the optimumcondition. To validate the model generated by the software, FB-Fenton reaction was carried out atoptimum conditions and the resulting efficiency was compared to that of conventional Fentonprocess using the same parameters. As shown in Table 4, the experimental results obtained for themodel at optimum conditions were close to the predicted values indicating a good fit for the rangeof concentrations investigated.Table 4. Comparison between actual and predicted values Response Actual Predicted Difference ACT removal, % 97.83 100 2.17 Initial rate, mM/min 0.2343 0.3185 0.0842Figure 4 shows the comparison between Fenton and fluidized-bed Fenton using optimumconditions of the latter. The trends for both methods were almost the same for residual H2O2,residual ACT and residual COD. The marked difference is evident in total residual iron.Total residual iron from the Fenton process was much higher than that from the FB-Fenton process.FB-Fenton process resulted to 62.92% iron removal compared to only 9.06% using Fenton process.This was expected since FB-Fenton was developed to reduce sludge formation in the form of ironprecipitates. The presence of SiO2 in the reactor provides a site for crystallization of iron oxidesonto the surface of these carriers thereby reducing the amount of iron in solution. SEM/EDSanalysis supports this as results showed an increase in iron from 0.83% to 2.10%.
  • 7. (a) (c) Fenton process (a) Fenton process FB-Fenton process 1.0 FB-Fenton process 1.0 0.8 0.8 Total iron (C/Co) [H2O2] (C/Co) 0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0 0 20 40 60 80 100 120 0 20 40 60 80 100 120 Time (min) Time (min) (b) (d) Fenton process Fenton process FB-Fenton process 1.0 FB-Fenton process 1.0 0.8 0.8 [ACT] (C/Co) COD (C/Co) 0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0 0 20 40 60 80 100 120 0 20 40 60 80 100 120 Time (min) Time (min)Figure 4. Comparison of residual (a) H2O2, (b) ACT (c) total iron and (d) COD between Fentonand Fluidized-bed Fenton processes at optimum condition: [ACT]=5mM, pH=3.22,[Fe2+]=0.06mM, [H2O2]=19.87mMParametric StudiesTo be able to discuss in detail the effect of each factor on the removal efficiency, parametric studieswere done. This involved changing the value of the parameter being studied while keeping othervariables constant.Effect of initial pH. Previous studies have shown that the pH of the contaminated solution is a veryimportant parameter that should be controlled in Fenton processes to achieve effective removal.The concentration of Fe2+ in solution was found to be maximum at pH=2.8 (Brillas, Sires, &Oturan, 2009). However, the operative optimum pH depends on the pollutant/s in solution.As shown in Fig. 5, only a small amount of ACT was removed at pH=2 (20.9%) as compared to theremoval at pH=3 (68.0%) and pH=4 (77.0%). But if pH of the solution was not adjusted (pH=6.5),ACT removal decreased drastically to 8.65%. At a very low pH, the high H+ concentration insolution scavenges •OH as shown in Equation 4 thereby decreasing the degradation rate (Devi, etal., 2010). Also, at low pH conditions, reduction of ferric to ferrous is inhibited (Equation 5). (4) (5)
  • 8. ACT removal 0.3 Initial rate 80 Initial rate (mM/min) ACT removal (%) 60 0.2 40 0.1 20 0 0.0 2 4 6 pH Figure 5. Effect of pH: [ACT]=5 mM, [Fe2+]=0.01 mM, [H2O2]=15 mMAt pH between 3 and 5, the predominant species is Fe2+ and degradation occurs at a faster rate inthis region. However, at a very high pH, Fe2+ is unstable and is easily oxidized to Fe3+ in solution.This precipitates out as Fe(OH)3 and reduces the amount of free Fe2+ in solution to catalyze Fentonreaction. Also, hydrogen peroxide is unstable at higher pH levels as it decomposes to water andoxygen. (6)Effect of initial ACT concentration. To determine the effect of acetaminophen on the degradationrate and removal, different concentrations of 2.5, 5, 7.5 and 10mM ACT were treated while fixingother factors constant at pH=3, [Fe2+]=0.01mM and [H2O2]=5mM. Results showed a 50% decreasein ACT removal after 2 hours of reaction time as the concentration was increased 4 times from 2.5to 10mM. The decrease in the rate of degradation at higher concentrations was observed becausethere is lower hydroxyl radical available in the solution compared to the target organic compounds.A lower oxidant to pollutant ratio resulted to a decrease in removal efficiency.It is also important to note that the degradation rate follows the trend of H2O2 concentration insolution. This implies that the amount of H2O2 available is directly related to the removal rate. Ifthere is no or little observed decline in H2O2 concentration, it is possible that ACT degradation hasstopped and that the process has reached its maximum removal effectiveness. In Fig. 7 (a) and (b),ACT concentration is almost constant at 40 min which coincides with the slow H2O2 disappearance.
  • 9. 0.20 ACT removal Initial rate 60 0.15 Initial rate (mM/min) ACT removal (%) 45 0.10 30 0.05 15 0 0.00 3 6 9 [ACT] (mM) Figure 6. Effect of ACT: pH=3, [Fe2+]=0.01mM, [H2O2]=5mM (a) (b) 1.2 ACT=5mM ACT=5mM ACT=10mM 1.0 ACT=10mM 1.0 0.8 0.8 [H2O2] (C/Co) [ACT] (C/Co) 0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0 0 20 40 60 80 100 120 0 20 40 60 80 100 120 Time (min) Time (min)Figure 7. Effect of ACT on FB-Fenton process: pH=3, [Fe2+]=0.1mM, [H2O2]=25mM, (a) ACTremaining and (b) residual H2O2Effect of initial [Fe2+]:[H2O2] ratio. Removal of ACT increased as initial Fe2+ concentrationincreased from 0.01 to 0.1 mM as depicted in Fig. 8. However, at Fe2+ concentration of 0.1 mM,ACT degradation started to decrease. This suggests that there is a competing reaction whichinvolves Fe2+ aside from its catalytic role shown in Equation 1. Fe2+ does not act merely as acatalyst to speed up Fenton reaction, it also reacts with •OH (Equation 7) (Kang, Lee, & Yoon,2002).There is a certain Fe2+:H2O2 ratio wherein scavenging of •OH in the solution manifests asobserved by a decrease in removal efficiency. (7)
  • 10. ACT removal ACT removal 65 1.0 2.0 Initial rate Initial rate 100 60 0.8 95 1.5 Initial rate (mM/min) Initial rate (mM/min) ACT removal (%) ACT removal (%) 55 0.6 90 1.0 50 0.4 85 0.5 45 0.2 80 40 0.0 75 0.0 0.0 0.3 0.6 0.0 0.3 0.6 2+ 2+ [Fe ] (mM) [Fe ] (mM)Figure 8. Effect of Fe2+: pH=3, [ACT]=5 mM, Figure 9. Effect of Fe2+: pH=3, [ACT]=5mM,[H2O2]=5 mM [H2O2]=25mM ACT removal 0.10 Initial rate 80 0.08 Initial rate (mM/min) ACT removal (%) 0.06 70 0.04 60 0.02 50 0.00 0 10 20 30 [H2O2] (mM) Figure 10. Effect of H2O2: pH=3, [ACT]=5 mM, [Fe2+]=0.01 mMAside from organic compounds, •OH can react with other species present in solution (Ting, Lu, &Huang, 2009) which depletes the amount of available •OH in solution. (8) (9) (10)For the concentration range of H2O2 studied between 5 and 25 mM at [Fe2+]=0.01 mM, there wasno observed decrease in ACT removal. Figure 10 shows that an increase in H2O2 concentrationleads to better removal. However, as the concentration was increased from 20 to 25mM, there wasonly a slight increase in removal. From previous studies made, a very high H2O2 concentrationresulted in a decreased reduction because this H2O2 will scavenge the •OH produced as in Equation8. There is a certain threshold concentration wherein the effect of increasing H2O2 does not result toan increase in removal. Beyond this optimum condition, it was observed that little or no change indegradation occurs.
  • 11. Another observation from this study was the difference in degradation rates at various Fe2+concentrations not only at low H2O2 but also at high H2O2 concentrations. It was observed that forsome runs, degradation occurs in two stages (Fig. 7(a)). There is a fast initial degradation ratefollowed by a slow rate in ACT removal. However, for other runs, degradation of ACT occurs in asingle slow rate all throughout the reaction time. The two-stage degradation was observed to occurat [Fe2+] higher than 0.02mM.This two-stage degradation is due to the very fast reaction of ferrous ions with hydrogen peroxide(Lu, Chen, & Chang, 1999). During the first minutes, there is a large amount or hydroxyl radicalproduced that attacks organic compounds. This results to a rapid decomposition of ACT in solution(Fig. 8 and 9) for the initial 20 minutes. This first stage is the Fe2+/H2O2 stage. However, as thereaction proceeds, ferrous ions are converted to ferric ions as shown in Equation 1. This limits theamount of ferrous that can react with H2O2 to produce •OH. The Fe3+ions produced reacts withH2O2 at a slower rate to produce hydroperoxyl radicals (•OH2) as in Equation 3, which is a weakeroxidant with E°=1.65 as compared to the oxidizing potential of •OH at 2.80. Thus, the degradationrate is much slower. The second stage is known as the Fe3+/H2O2 stage.CONCLUSIONThis study applied Box-Behnken design in the optimization of fluidized-bed Fenton process on thedegradation of the drug, acetaminophen. The optimum condition was found to be at pH=3.22,[Fe2+]=0.06mM and [H2O2]=19.87mM. Actual ACT removal at the optimum was 97.83%.Comparison of conventional Fenton and fluidized-bed Fenton process at optimum conditionshowed that FB-Fenton has reduced sludge formation with total iron removal at 62.92% comparedto 9.06% of Fenton process and higher TOC removal, 59.62% vs. 16.37%.Parametric studies revealed that ACT removal without pH adjustment was almost negligible at only8.65% which proves that initial pH adjustment is crucial and necessary for this system. IncreasingFe2+ concentration to 0.1mM at [H2O2]=5mM decreased ACT removal. Increasing H2O2concentration always lead to an increase in ACT removal for the concentration range studied. Atwo-stage degradation rate was observed at Fe2+ concentrations higher than 0.02mM. FB-Fentonproves to be a promising method, requiring minimal space, complete degradation andmineralization with reduced sludge production.ACKNOWLEDGEMENTThis research was financially supported by the National Science Council, Taiwan (Grant: NSC 99-2221-E-041-012-MY3), the Department of Science and Technology, Philippines and theEngineering Research and Development for Technology (ERDT), Philippines.REFERENCESBrillas, E., Sires, I., & Oturan, M. A. (2009). Electro-Fenton Processes and Related Electrochemical Technologies Based on Fentons Reaction Chemistry. Chemical Reviews .Chou, S., Huang, C., & Huang, Y.-H. (1999). Effect of Fe2+ on catalytic oxidation in a fluidized- bed reactor. Chemosphere 39 (12) , 1997-2006.Davis, T. P., & Draper, N. R. (1998). Fitting 3rd order terms in Box-Behnken Experiments. University of Wisconsin, Department of Statistics.Devi, L. G., Raju, K. S., Kumar, S. G., & Rajashekhar, K. E. (2010). Photo-degradation of di azo dye Bismarck Brown by advanced photo-Fenton process: Influence of inorganic anions and
  • 12. evaluation of recycling efficiency of iron powder. Journal of the Taiwan Institute of Chemical Engineers .Kang, N., Lee, D. S., & Yoon, J. (2002). Kinetic modeling of Fenton oxidation of phenol and monochlorophenols. Chemosphere 47 (9) , 915-924.Khataee, A. R., Vatanpour, V., & Amani Ghadim, A. R. (2008). Decolorization of C.I. Acid Blue 9 solution by UV/Nano-TiO2, Fenton, Fenton-like, electro-Fenton and electrocoagulation processes: A comparatice study. Journal of Hazardous Materials 161 (2-3) , 1225-1233.Larsen, T. A., Lienert, J., Joss, A., & Siegrist, H. (2004). How to avoid pharmaceuticals in the aquatic environment. Journal of Biotechnology 113 (1-3) , 295-304.Lu, M.-C., Chen, J.-N., & Chang, C.-P. (1999). Oxidation of dichlorvos with hydrogen peroxide using ferrous ion as catalyst. Journal of Hazardous Materials 65 (3) , 277-288.Muangthai, I., Ratanatamsakul, C., & Lu, M.-C. (2010). Removal of 2,4 dichlorophenol by fluidized-bed Fenton process. Sustain. Environ. Res. 20 (5) , 325-331.Rizzo, L., Meric, S., Kassinos, D., Guida, M., Russo, F., & Belgiorno, V. (2009). Degradation of diclofenac by TiO2 photocatalysis: UV absorbance kinetics and process evaluation through a set of toxicity bioassays. Water Research 43 (4) , 979-988.Ting, W.-P., Lu, M.-C., & Huang, Y.-H. (2009). Kinetics of 2,6-dimethylaniline degradation by electro-Fenton process. Journal of Hazardous Materials 161 (2-3) , 1484-1490.Wiegel, S., Aulinger, A., Brockmeyer, R., Harms, H., Loffler, J., Reincke, H., et al. (2004). Pharmaceuticals in the river Elbe and its tributaries. Chemosphere 57 (2) , 107-126.Zhang, X., Wu, F., Wu, X., Chen, P., & Deng, N. (2008). Photodegradation of acetaminophen in TiO2 suspended solution. Journal of Hazardous Materials 157 (2-3) , 300-307.Zhou, J. L., Zhang, Z. L., Grover, D., & Jiang, J. Q. (2009). Pharmaceutical residues in wastewater treatment works effluents and their impact on receiving river water. Journal of Hazardous Materials 166 (2-3) , 655-661.

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