Degradation of Paracetamol by Electro-Fenton and Photoelectro-Fenton Processes Using a Double Cathode Electrochemical Cell

M.C. Lu *, M.L.Veciana**, M.D.G. de Luna*** * Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan **Environmental Engineering Graduate Program, University of the Philippines, 1011 Diliman, Quezon City, Philippines *** Department of Chemical Engineering, University of the Philippines, 1011 Diliman, Quezon City, Philippines

Abstract Acetaminophen is a widely used drugs worldwide and is one of the most frequently detected drugs in bodies of water making it a high priority trace pollutant. This study investigated the appliccability of the electro-Fenton and photoelectro-Fenton process using a double cathode electrochemical cell in the treatment of acetaminophen containing wastewater. It used the BoxBehnken design to determine the effects of initial Fe2+ and H2O2 concentrations and applied current density. Results showed that all parameters positively effect the degradation efficieny of acetaminophen with the initial Fe2+ concentration being the most significant parameter for both process. The optimum conditions obtained for maximum removal of acetaminophen were 0.087 mM Fe2+, 16.26 mM H2O2 and 37.67 Amp/m2 for the electro-Fenton process and 0.08 mM Fe2+, 14.81 mM H2O2 and 37.67 Amp/m2 for the photoelectro-Fenton process. The acetaminophen removal efficiences for electro-Fenton was 97.93% and COD removal of 42.72% while a 96.97% acetaminphen removal and 42.26% COD removal was observed for the photoelectroFenton method operated at optimum conditions. Therefore, due to a neglible difference between the treatment efficiencies of the two processes, the electro-Fenton method was proven to be more economically advantageous. Also the models obtanied from the study were applcable to a wide range of acetaminophen concentrations and can be used in scale-ups. Keywords Acetaminophen, electro-Fenton process, photoelectro-Fenton process

INTRODUCTION Acetaminophen (ACT) is one of the most frequently used drugs worldwide. It is one of the most frequently detected pharmaceutical products in sewage treatment plant effluents, surface water and drinking water (Kim et al., 2007). It is considered a high priority trace pollutant owing to its high detection frequency of 22.38% and adverse environmental effects (Murray et al, 2010). Detection of this compound is greater at highly populated areas such as urban centers where drug usage is expected to reach elevated proportions. The proliferation of new synthetic compounds render conventional wastewater treatment ineffective. Advanced oxidation processes (AOPs) are now preferred to biological treatment especially for industrial effluents. AOPs generate powerful non-selective oxidants called hydroxyl radicals. Hydroxyl radicals can degrade and mineralize a wide variety of pollutants (Masomboon et al., 2010). This is often operated at near ambient and air pressure. (Glaze et al.,

1987) These techniques transfer the pollutants from one phase to a less harmful phase making them more practical than other existing technologies. (Elmolla & Chaudhuri, 2010a ) One of the widely used AOP is the Fenton process which uses hydrogen peroxide (H2O2) and ferrous ions (Fe2+) in the generation of hydroxyl radicals which can degrade and mineralize a wide variety of pollutants. (Masomboon et al., 2010) In this process, hydrogen peroxide is catalyzed by the ferrous ion to produce the hydroxyl radicals as shown in equation 1. (Ting et al., 2009) Fe2+ + H2O2 Fe3+ + OH + OH k = 5376M1 s1 (1)

These hydroxyl radicals then react with the pollutants like organic compounds resulting to its degradation and mineralization. (Masomboon et al., 2010) OH + organics products (2)

Ferrous ions are able to regenerate through the reduction of ferric species (Fe3+) by hydrogen peroxide as shown in equation 3. (Ting et al., 2009) This reaction enables the propagation of the Fenton reaction. H2O2 + Fe3+ Fe2+ + HO2 + H+ k = 0.01M1 s1 (3)

One of the major disadvantages of the Fenton process is the large production of ferric hydroxide sludge during the neutralization stage of the process. As can be observed in equations 1 and 3, a large difference between the rate constants can be seen, which results to the consumption of ferrous ions more rapidly rather than its regeneration. Because of this, additional treatment and separation process is needed before the sludge can be disposed. (Ting et al., 2009) The Electro-Fenton (EF) process was developed to address this disadvantage. In this process, electrical current is applied to induce the reduction of ferric hydrogen sludge to form ferrous ions on the cathode. This does not only reduces the amount of sludge formed but also enhances the degradation of target compounds. (Masomboon et al., 2010) Another electrochemical process being studied is the Photoelectro-Fenton (PEF) process. It is a type of Fenton technology which uses the same conditions as that of the Electro-Fenton process. The only difference between these two processes is the simultaneous irradiation of UVA light. This accelerates the degradation rate of organic pollutants in the reaction and also increases the regeneration rate of Fe2+. Additional peroxide OH can also be observed due to the photolysis of [Fe(OH)]2+ and Fe(III) complexes that forms carboxylic acids as shown in equations and . (Brillas et al, 2009) [Fe(OH)]2+ + hV Fe(OOCR)2+ + hV Fe2+ + OH Fe2+ + CO2 + R (4) (5)

Advanced oxidation methods are being applied to treat acetaminophen containing wastewater. Studies have already been made using Solar Photo Fenton but it was unable to remove

acetaminophen efficiently which only obtained an effiecieny of 16.3%. (Klamerth et al., 2010) Photo-fenton , uses UV light to increase the production of hydroxyl radicals thereby increasing the efficiency of the treatment process. (Elmolla & Chaudhuri, 2009a ) For the case of solar photo fenton it uses solar energy as light source. Heterogenous AOP were also applied in the treatment of acetaminophen which includes TiO2 Phtocatalysis which gained 95% removal in 80 minutes. (Yang et al., 2008) Photocatalytic methods includes the illumination of semiconductors such as titanium dioxide (TiO2) with high energy photons. This process produces hydroxyl radicals which then oxidizes the target pollutants. (Elmolla & Chaudhuri, 2010a,b,c)Other methods includes photodegradation of ACT in TiO2 suspended solution which was able to remove 95% ACT in 100 minutes (Zhang et al., 2008). The application of membrane bioreactor was also used and was able to remove 100% ACT in 48 hours. (Shariati et al., 2010) In this study the applicability of electrocehmical Fenton processes in the treatment of acetaminophen containing wastewater was investigated. Unlike the above mentioned processes, electro-fenton and phoelectro-Fenton processes has the ability to treat even high conccentrations of wastewater making its application possible as a pre-treatment process before the actual treatment. The effects of important operating parameters were also studied and the system was optimized to obtain the maximum removal at the most economical conditions.

MATERIALS AND METHODS Chemicals and Analytical Methods All chemicals used in this study were of analytical grade and were purchased from Merck. Reagents were prepared using de-ionized water from a Millipore system with a resistivity of 18.2 M cm. Synthetic wastewater with an initial concentration of 5mM was prepared from an anlytical grade acetaminophen having a 99% purity also supplied by Merck. All experiments were conducted at room temperature and were run for 2 hours. Samples were taken at identified intervals for analyses and were immediately mixed into bottles containing NaOH solution to increase its pH and stop the reaction. These were then filtered using 0.2m filters to ensure the removal of precipitates before analysis. Residual paracetamol concentration was measured using a high performance liquid chromatography (HPLC) with Spectra SYSTEM model SN4000 pump and Asahipak ODP-506D column (150mm6mm5_m) where the mobile phase was 60% acetonitrile with 40% DI water. Optimization of parameters were done for maximum paracetamol removal using Design Expert 7 software (Stat-Ease, Inc.,Minneapolis, USA.). Closed-reflux titration based from standard methods were used for COD measurement. Samples were kept for 12 hours before the analysis to remove the effect of H2O2 on the COD data. The ferrous (Fe2+) ion concentration and remaining hydrogen peroxide (H2O2) in the solutions were measured using spectrophotometric analysis. The Fe2+ concentration was detected at 510 nm after complexation with 1,10 phenanthroline solution while the remaining H2O2 were analyzed at 400 nm after complexing with K2TiO4.

Experimental Apparatus A cylindrical reactor having concentric electrodes were used in this study as shown in figures 1 a and b.Two stainless steel cathodes having and inside diameters of 2 and 13 cm respectively and a titanium coated RuO2/IrO2-coated DSA anode witn an inside diamter of 7 cm comprised the 3.5L electrochemical-cell reactor (diameter: 13 cm and height: 35 cm). This was operated at constant current mode. For the photoelectro-Fenton process 16 UVA lights emiiting 360 nm at 3 W each were used.
DSA Anode UVA Light (360 nm)

Power Supply

Power Supply

+
Cathode Anode 13 7 2 Cathode

Power + -

(a)

(b)

Figure. 1. Schematic diagram of Reaction System.a. Electro-Fenton b. Photoelectro-Fenton Electro-Fenton Process Synthetic wastewater having an initial concentration of 5 mM were treated by both processes. Pre-determined amount of FeSo47H2O was added into the wastewater solution. The pH was then adjusted to 3 before turning on the powersupply at desired current. Samples were taken before the addition of H2O2 to get the initial conditions of the system. The time starts after the addition of the H2O2 to initiaite the reaction. Samples taken at specified time intervals were then mixed with NaOH solution and then filtered using 0.2m filters to remove possible precipitates. Photoelectro-Fenton Process Same experimental conditions were carried out using the photoelectro-Fenton process. As shown in Figure 1.b, 16 UVA lights were used having a maximum frequency of 360 nm. Each lights supplies a photoionization energy of 3 W amounting to a total of 48 W. Box-Behnken Experimental Design The Box-Behnken Design (BBD) was used to investigate the effects of important operating parameters in the degradation of acetaminophen and optimize the system. This is a type of response surface method (RSM) which is based on three-level incomplete factorial designs. It

requires fewer runs when compared to other RSM designs making its application more economical. Lower and upper limits of these parameters were as follows: 0.01 - 0.1 mM, 5 - 25 mM and 37.67 - 113.01 A/m2 for initial [Fe2+], initial [H2O2] and applied current density respectively. The high, middle and low levels were designated with 1,0 and -1 respectively. These range were chosen based from prior experiments. The degradation of ACT was selected as a response factor. RESULTS AND DISCUSSION Three experimental factors which includes the initial concentration of Fe2+ and H2O2 and current density were varied for this study. These factors were chosen because it greatly affects the treatment efficiency of the processes being investigated. Based from the results a minimum of 48.6 % and 54.6% were observed for the electro-Fenton and photoelectro-Fenton processes respectively. These were obtained at an initilal Fe2+ and H2O2 concentrations of 0.01 mM and 15 mM respectively with an applied current density of 37.67 A/m2 and an intial pH of 3. The maximum removal on the other hand for both processes were achieved at an initial concentration of 0.1 mM for Fe2+ and 25 mM for H2O2 and an applied current density of 75.34 A/m2 also at the same initial pH. A 99.8% removal was observed for the electro-Fenton process and a 100% removal was achieved by the photoelectro-Fenton process after two hours of treatment. Based from these results, the difference between the efficiencies of these two processes decreases as the concentrations of the Fenton reagents increases. At higher concentrations of Fentons reagent, an enough supply of hydroxyl radicals are produced which is enough for the treatment of the pollutant.

Effect of Various Parameters in Acetaminophen Degradation Efficiency Table 1 shows the correlation factors obatined from the BBD model for both electro-Fenton and photoelectro-Fenton processes. These values can have a value of +1 to -1 where a positive number indicates that it has a direct effect on the acetaminophen degradation efficiency and a negative value means that it affects the efficiency in reverse. A higher value would also mean that it has a greater effect on the response. Table 1. Correlation factors of different operating parameters Parameter Electro-Fenton Photoelectro-Fenton 2+ Initial Fe Conc. 0.662 0.520 Initial H2O2 Conc. 0.318 0.395 Current Density 0.296 0.320 All of the factors showed a positive effect on the treatment efficiency of both processes. An increase in the initial concentrations of both Fe2+ and H2O2 results in a increase of hydroxyl radicals as shown in equations 1. This radicals then react with the organic pollutant to transform it into less harmful products. More radicals means that more pollutant can be degraded resulting

to a higher treatment efficiency of the process. On the otherhand, increasing the amount of applied current density can result to faster regeneration of the Fe2+ ions as shown in equations 6 and 7, thereby making more Fe2+ ions available for hydroxyl radical production. (Masomboon et al., 2010) On Cathode Side : Fe3+ + eOn Anode Side : Fe2+ Fe2+ Fe3+ + e(6)

(7)

Based from these factors, the initial Fe2+ concentration was the most significant factor among the three for both processes. As what was observed, the initial Fe2+ concentration dictates the behaviour of degradation of acetaminophen. Also, the effect of varying Fe2+ concentration was more pronounced in the electro-Fenton process than the photoelectro-Fenton process having a correlation factor of 0.662 compared to 0.520. In the electro-Fenton process, the Fe3+ ions are continuously regenerated in the cathode side. This increases the regeneration rate of Fe2+ ions thereby increasing the treatment efficiency of the process. However, the photoelectro-Fenton process also has the ability of regenerating Fe2+ ions from ferric complexes such as Fe(OH)2+ and the like aside from its regeneration in the cathode side as shown in equations 4 and 5 as mentioned by Brillas, et al. In this way, the regeneration efficiency of Fe2+ is higher in the photoelectro-fenton process than in the electro-Fenton process. This is the reason why higher degradation efficiencies were obtained for the PEF process even at lower initial Fe2+ concentration than the EF process. Thus, the effects of varying Fe2+ concentration is lower resulting to a lower correlation factor. On the other hand, results also showed that the PEF process has a higher correlation factor for both the initial H2O2 concentration and the applied current density than the EF process. Due to higher regeneration efficiency of the Fe2+ ions, the need for more H2O2 to produce more hydroxyl radicals is more pronounce in the PEF than the EF process. Optimum points and validation of the Model An empirical correlation between the acetaminophen degradation efficiency and the three factors were obtained using the Box-Behnken experimental design for both processes. A reduced cubic model was fitted for both processes having an r-squared value of 0.9999. Electro-Fenton Process % ACT Degradation = 6.21 + 930.07A + 0.22B+ 68.46C + 75.32AB - 858.29AC - 0.74BC - 5452.29A2 - 5.44x10-003B2 - 7.86C2 - 330.63A2B + 4552.33A2C - 0.87AB2

Photoelectro-Fenton Process % ACT Degradation = 19.38 +1287.88A 1.70B+ 76.18C + 72.82AB -1221.21AC - 0.24BC 10315.67A2 + 0.06B2 - 12.24C2 -88.88A2B + 7406.28A2C 1.80AB2

These models can be use to predict the acetaminophen degradation for any values of the parameters with the initial Fe2+ (mM) and H2O2 (mM) concentrations and current (Amp) being represented by A, B and C. These were obtained by correlating the response functions with the variations in the operating parameters using the Design Expert 7 software. Optimum operating conditions for each processes are shown in table 2. These values were obtained using the optimization tool incorporated in the Design Expert 7 software. For this analysis, the response factor which is the acetaminophen degradation was set at maximum while the applied current and initial hydrogen peroxide concentration was set at minimum. This was done to ensure that maximum removal can be obtained at the least possible operating cost. However, the initial Fe2+ concentration being the one most significant factor for the acetaminophen removal was set in range. Table 2. Optimum operating conditions for electro-Fenton and photoelctro-Fenton process Parameter Initial pH Initial Fe2+ Conc. Initial H2O2 Conc. Current Density mM mM A/m2 Unit Electro-Fenton 3 0.087 16.26 37.67 Photoelectro-Fenton 3 0.08 14.81 37.67

The electro-Fenton process has a higher requirement for both intial Fe2+ and H2O2 concentration compared to the photoelectro-Fenton process. This is mainly because the photoelectro-Fenton process has a higher efficiency in the regeneration of Fe2+ ions and hydroxyl radical formation due to the application of UV lights as shown in equations 4 and 5. On the other hand, the same amount of current density at 37.67 A/m2 was needed for both processes to obtain 100% removal. But if the amount of energy consumption for UV lights application is to be considered, the electro-Fenton process proves to be more energy efficient compared to the photoelectro-Fenton process. In order to validate the models used, both processes were run at optimum conditions. Table 3 shows the ACT degradation for each processes. Another run was done at 50 mM ACT using the same ratios of parameters at the optimum condition (using the Electro-Fenton process Optimum

Condition). This was done to investigate the applicability of the model for possible scale-up operations. Table 3. Comparison of predicted and actual acetaminophen degradation for each processes % ACT Degradation Process Predicted Electro-Fenton Photoelectro-Fenton Electro-Fenton (50 mM ACT) 100 Actual 97.93 96.97 95.34 2.07 3.03 4.66 % Difference

As can be observed, the difference between the predicted and actual results for both processes is small. This only proves the reliability of the model used. The usage of the same optimum conditions even at higher concentration yielded a 95.34% ACT removal which differed by 4.66% from the predicted results. The same trend was also obeserved for the COD removal for both low and high initial ACT concentration resulting to a 42.72% and 41.14% respectively. The models obtained from these study are not restricted to the given initial ACT concentration It was proven that the model can be used to a wide range of ACT concentrations and can be applied for scaleup operations. Process Comparison To determine the best process for the removal of acetaminophen containing wastewater, each processses were run at optimum conditions. Two Fenton processes for each set of optimum conditions were also done. The results for ACT, COD and TOC removals are shown in Table 4. Table 4. Comaprison of Acetaminophen, COD and TOC removal efficiencies of each processes at optimum conditions Process %ACT %COD % TOC Removal Removal Removal Electro-Fenton 97.93 42.72 Fenton (EF Optimum) 95.83 27.48 Photoelectro-Fenton 96.97 42.26 Fenton (PEF Optimum) 95.49 29.21 The difference between the degradation efficiencies of each process runs at the optimum conditions are negligible for each processes. As can be observed, the Electro-Fenton process was able to degrade 97.93% while the photoelectro-Fenton process was able to obtain a 96.97% degradation efficiency. Both Fenton processes on the other hand was able to degrade about 95%

of the total pollutant. A fast degradation of the target compound was observed in the first 40 minutes of the treatment time as shown in Figure 2.a.

Figure 2. Acetaminophen removal for different processes operated at optimum conditions. (Electro-fenton: Fe2+ = 0.087 mM, H2O2 = 16.26 mM, Current Density = 37.67 Amp/m2; Photoelectro-Fenton: : Fe2+ = 0.08 mM, H2O2 = 14.81 mM, Current Density = 37.67 Amp/m2) However, the difference between the COD removal efficiencies between the Fenton and electrogenerated Fenton processes are evident as shown in Figure 3. The electro-Fenton process ws able to remove 42.72% COD while the photoelectro-Fenton process ws able to remove 42.26 %. The Fenton processes on the other hand were only able to obtain 27-29% COD even when operated at the same conditions. These results shows that the electrochemically operated Fenton processes are superior to the Fenton process when it comes to chemical oxygen demand removal. Formation of intermediates during the degradation process is one of the reason of low COD removal efficiency in the Fenton process. These intermediates are able to form complexes with the reagents making it harder to remove thereby decreasing the COD removal efficiency. Electro-Fenton and photoelectro-Fenton processes has the ability to regenerate this complexes back to simple organic acids thereby increasing the degradation efficiency.

Figure 3. COD removal for different processes operated at optimum conditions. (Electrofenton(EF): Fe2+ = 0.087 mM, H2O2 = 16.26 mM, Current Density = 37.67 Amp/m2; Photoelectro-Fenton (PEF) : Fe2+ = 0.08 mM, H2O2 = 14.81 mM, Current Density = 37.67 Amp/m2) Since the difference between the treatment efficiencies of electro-Fenton and photoelectroFenton processes are not concrete, the use of energy-related parameters are utilized in these study as presented in Table 5. These are important parameters for comparison to see the viability of each process. Table 5. Comparison of H2O2 efficiency, current efficiency and energy cost for electro-Fenton and photoelectro-Fenton processes Process %H2O2 %Current Energy Cost Efficiency Efficiency (kWh COD-1) Electro-Fenton 134 408 3.53 Photoelectro-Fenton 149 413 3.56 The H2O2 efficiency, current efficiency and energy cost for both processes were calculated using equations 8,9 and 10. (8)

(9)

(10)

The availble oxygen is the theoretical amount of reactive oxygen in the hydrogen peroxide added. Other variables included in the equations are (COD)t which is the experimental COD decay (g O2/L) at time t (s), F is the Faradays constant (96487 C/mol), Vs is the volume of the solution (L), I is the current applied (A) and 8 is the oxygen equivalent mass (g/eq). Ecell on the otherhand is the average cell voltage (V) for the electrolysis time. The H2O2 efficiency can have a value greater than 100 since the COD removal is not only attributed to Fenton reaction alone. This scenario was also observed by Masomboon et al. in their study regarding the degradation of dimethyaniline. The photoelcetro-Fenton process has a slightly higher H2O2 and current efficiencies than the electro-Fenton process. But in terms of energy consumption the electroFenton process requires lower energy since it does not need additional UVA irradaition for degradation making the electro-Fenton process more suitable and economical. CONCLUSION The electro-Fenton process was proven to be more efficient in the treatment of acetaminophen containing wastewater than the photoelectro-Fenton method. Although the difference between the removal efficiencies of both processes are negligible, it is more energy efficient than the photoelectro-Fenton method. All parameters also showed a positive effect on the degradation efficiency with the Fe2+ initial concentration being the most impportant parameter among the three for both processes. Also the Box-Behnken statistical design was proven to be an effective way of optimizing the given process. The optimum conditions obtained for maximum removal of acetaminophen were 0.087 mM Fe2+, 16.26 mM H2O2 and 37.67 Amp/m2 for the electro-Fenton process and 0.08 mM Fe2+, 14.81 mM H2O2 and 37.67 Amp/m2 for the photoelectro-Fenton process. The models obtained were also not limited to the specific set of conditions employed during the study but can be used at a wider range of acetaminophen concentrations.

ACKNOWLEDGMENT This research was finacially supported by the National Science Council, Taiwan (Grant: NSC 962628-E-641-001-MY3) REFERENCES
APHA, AWWA, and WPCF, 2000. Standard Methods for the Examination of Water and Wastewater, 20th ed. Brillas, E., Sires, I. & Oturan, M.A., 2009. Electro-Fenton Process and Related Electrochemical Technologies Based on Fentons Reaction Chemistry, Elmolla, E.S. & Chaudhuri M., 2010a. Comparison of different advanced oxidation processes for treatment of antibiotic aqueous solution, Desalination, vol. 256,pp. 4347 Elmolla, E.S. & Chaudhuri M., 2010b. Degradation of amoxicillin, ampicillin and cloxacillin antibiotics in aqueous solution by the UV/ZnO photocatalytic process, Journal of Hazardous Materials, vol.173, pp. 445449 Elmolla, E.S. & Chaudhuri M., 2010c. Photocatalytic degradation of amoxicillin, ampicillin and cloxacillin antibiotics in aqueous solution using UV/TiO2 and UV/H2O2/TiO2 photocatalysis, Desalination, vol. 252,pp. 46-52

Elmolla, E.S. & Chaudhuri M., 2009a. Degradation of the antibiotics amoxicillin, ampicillin and cloxacillin in aqueous solution by the photo-Fenton process, Journal of Hazardous Materials, vol.172, pp. 14761481 Glaze, W.H., Kang, J.W., & Chapin. D.H., 1987. The Chemistry Of Water Treatment Processes Involving Ozone, Hydrogen Peroxide and Ultraviolet Radiation. Ozone Science Engineering, vol.9, pp. 335-352 Klamerth N., Rizzo K., Malato S., Maldonado M.I, Aguera A. & Fernandez-Alba A.R., 2010. Degradation of Fifteen emerging contaminants at g/L-1 initial concentrations by mild solar photo-Fenton in MWTP effluents. Water Research , vol.44, pp. 545 55 Kim Y., Choi K., Jung J., Park S., Kim P-G. And Park J.,2007. Aquatic Toxicity of Acetaminophen, Carbamazepine,Cimetidine,Diltiazem and Six Major Sulfomides and Their Potential Ecological Risks in Korea, Environment International, vol.33, pp.370-375 Masomboon, N., Ratanatamskul, C. & Lu, M.-C., 2010. Chemical oxidation of 2,6 dimethylaniline by electrochemically generated Fentons reagent, Journal of Hazardous Materials, vol. 176, pp.9298 Murray K.E., Thomas S.M. & Boduor A.A., 2010 Prioritizing Research for Trace pollutants and Emerging Contaminants in the Fresh water Environment, Environmental Pollution, vol. 158 pp.3462-3471 Ting, W-.P., Lu, M.-C. & Huang, Y.-H., 2008. The reactor design and comparison of Fenton, electro-Fenton and phototelectro-Ffenton processes for mineralization of benzene sulfonic acid, Journal of Hazardous Materials, vol. 156, pp.421-427 Ting, W-.P., Lu, M.-C. & Huang, Y.-H., 2009. Kinetics of 2,6-dimethylaniline degradation by electro-Fenton process, Journal of Hazardous Materials, vol. 161, pp.14841490 Yang L., Yu L.E., Ray M.B., 2008. Degradation of Paracetamol in Aqueous solutions by TiO2photocatalysis, Water Research, vol. 42, pp.3480-3488 Zhang X.., Wu F., Wu X.W., Chen P., Deng N.., 2008. Photodegradation of Acetaminophen in TiO2 suspended solution, Journal of Hazardous Materials, vol. 157, pp.300-307