prepared by 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, Phi for Urban Environments in Asia, 25-28 May 2011, Manila, Philippines. organized by International Water Association (IWA).
Suplemen HUD Magz Edisi 5 /2015. Kota BATAM Menyongsong MEA 2015
Degradation of Paracetamol by Electro-Fenton and Photoelectro-Fenton Processes Using a Double Cathode Electrochemical Cell
1. 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 Box-
Behnken 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 photoelectro-
Fenton 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.,
2. 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 = 53–76M−1 s−1 (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 = 0.01M−1 s−1 (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 Fe2+ + •OH (4)
Fe(OOCR)2+ + hV Fe2+ + CO2 + R• (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
3. 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 0.2µm 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 (150mm×6mm×5_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.
4. 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
Power
+ - + -
Cathode
Anode
13 7 2
Cathode
(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 FeSo4·7H2O 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 0.2µm 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
5. 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 Fenton’s 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
6. 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+ + e- → Fe2+ (6)
On Anode Side :
Fe2+ → Fe3+ + e- (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
7. 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 Unit Electro-Fenton Photoelectro-Fenton
Initial pH 3 3
Initial Fe2+ Conc. mM 0.087 0.08
Initial H2O2 Conc. mM 16.26 14.81
Current Density A/m2 37.67 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
8. 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 % Difference
Predicted Actual
Electro-Fenton 97.93 2.07
Photoelectro-Fenton 100 96.97 3.03
Electro-Fenton (50 mM ACT) 95.34 4.66
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 scale-
up 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%
9. 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.
10. Figure 3. COD removal for different processes operated at optimum conditions. (Electro-
fenton(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 photoelectro-
Fenton 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)
11. (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 electro-
Fenton 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 96-
2628-E-641-001-MY3)
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