Clean – Soil, Air, Water 2012, 40 (2), 179–187 179

Fatma Beduk
Mehmet Emin Aydin
Research Article
Senar Ozcan
Degradation of Malathion and Parathion by
Department of Environmental
Engineering, Selcuk University, Konya,
Ozonation, Photolytic Ozonation, and
Turkey Heterogeneous Catalytic Ozonation Processes
The oxidation of organophosphorus pesticides (OPPs), such as malathion and parathion,
in aqueous solution was studied using conventional ozonation (O3), photolytic ozona-
tion (O3/UV, O3/UV/H2O2), and heterogeneous catalytic ozonation (O3/TiO2/UV) pro-
cesses. Experiments were performed in batch mode at laboratory scale and
processes were compared in terms of disappearance kinetics. The best results of
pesticide mineralization were obtained when TiO2 particles in combination with ozone
(O3) and UV photolysis (l ¼ 254 nm) were applied. Decomposition of 99% of parent
compounds were achieved in 10 min and oxon derivatives were completely removed in
30 min. The initial reaction rate increases linearly with increasing catalyst amount.
Toxicity measurements of the treated solutions were carried out in order to evaluate
the efficiency of the treatment methods. No detoxification was achieved for O3 and
O3/UV applications. Heterogeneous photocatalytic ozonation was shown to be feasible
for achieving complete decomposition of OPPs and their oxon intermediates.
Keywords: Catalysis; Malathion; Oxidation; Ozone, Parathion
Received: February 6, 2011; revised: May 3, 2011; accepted: May 7, 2011
DOI: 10.1002/clen.201100063

1 Introduction involving the hydroxyl radical [16]. Radicals are unstable and reac-
tive, because one of their electrons is unpaired. On the other hand,
Organophosphorus pesticides (OPPs) were introduced because
ozone alone is insufficient to achieve a complete mineralization of
of their lower persistency in the environment relative to organo-
OPPs [14]. Besides, disappearance of parent compounds does not
chlorine pesticides. However, they were found in environment with
always indicate the successful treatment, because the degraded
enough frequency to constitute an ecotoxicological risk [1–3].
products may be more toxic than the parent compounds. The
Exposure to them could lead to inhibition of acetylcholinesterase
majority of OPPs give rise to only slight inhibition of AChE by
(AChE) in target tissues which leads to accumulation of acetylcholine
themselves, unless they undergo oxidative activation resulting
[4, 5]. In the environment, the fate of OPPs is associated with both
with oxon formation [17, 18]. Because of that reason, complete
abiotic and biotic processes, including hydrolysis, volatilization,
degradation of oxon derivatives of OPPs is critical for application
photo oxidation, chemical oxidation, and microbial transformation.
of oxidation processes.
Their degradation in natural environment by various processes
Photolytic ozonation is another way of enhancing ozone reactiv-
sometimes results in the formation of oxygen analogues [6]. This
ity. The mechanism of ozone photolysis was studied by Peyton and
process involves the substitution of the sulfur atom in the P —
— S bond Glaze [19] who confirmed the formation of hydrogen peroxide as the
of the organophosphate pesticide with an oxygen atom resulting in
first reaction intermediate of ozone photolysis. It was also proposed
formation of oxon derivatives.
that the secondary reactions lead to the production of hydroxyl
A promising way to perform the mineralization of these substan-
radical (OH
). This process was successfully applied for removal of
ces is the application of advanced oxidation processes (AOP).
nitrobenzene [20], herbicides such as linuron [21], synthetic organic
Photolysis [7, 8], photocatalysis [9–11], the Fenton and photo-
compounds, e.g., oxalic and acetic acids [22]. Photolytic ozonation
Fenton processes [12, 13], and ozone based oxidation [14, 15] for
was also used to oxidize phenols [23] and natural organic matter [24].
OPPs degradation were investigated in recent years. Among the
Ozone was used in combination with hydrogen peroxide to
different AOP technologies, ozone is capable of oxidizing a variety
generate OH radicals. Researchers have demonstrated that the
of organic and inorganic compounds in aqueous solution, either by
addition of hydrogen peroxide can enhance the oxidation of organic
direct reaction of molecular ozone, or through a radical mechanism
compounds [8].
Heterogeneous catalytic ozonation (HeCO) processes with metal
ions or metal oxides are also acting as catalysts in order to enhance
Correspondence: Dr. F. Beduk, Department of Environmental Engineering, the reactivity of ozone [25]. The use of ozone and catalysts dates back
Selcuk University, Campus, 42031 Konya, Turkey to the 1970s. In the initial studies, attention focused on mainly
E-mail: fatmabeduk@selcuk.edu.tr metals salts such as Fe(II), Mn(II), Ni(II), or Co(II) use. Homogenous
Abbreviations: HeCO, heterogeneous catalytic ozonation; OPPs, (HoCO) and HeCO processes depend on the water solubility of the
organophosphorus pesticides catalyst [16]. Photocatalytic oxidation of organic compounds by

ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com

180 F. Beduk et al.
titanium dioxide (TiO2), a semiconductor, has attracted attention for
treating contaminated waters [9, 26, 27]. The photoexcitation of a
semiconductor promotes valence band electrons into the conduc-
tion band leaving free electron holes. The catalytic activity of the
catalysts is mainly based on the catalytic decomposition of ozone
and the enhanced generation of hydroxyl radicals.
The degradation of OPPs using TiO2 photocatalysis [9–11] and
ozonation [14, 15] has been previously investigated. However, in
these investigations the HeCO of OPPs and the factors affecting oxon
decomposition were not particularly investigated. In this study, it
was aimed to evaluate the behavior of malathion, parathion, and
their toxic degradation products such as malaoxon and paraoxon
during HeCO process. The results of conventional, photolytic, and
HeCO were compared. Processes were compared in terms of disap-
pearance kinetics. Toxicity measurements of the treated solutions
were carried out in order to evaluate the efficiency of the treatment
methods. For this purpose, Daphnia magna and Vibrio fischeri, two
different biotests from different trophic levels were chosen.
2 Experimental
2.1 Reagents and solvents
All chemicals used were of analytical grade. Single malathion,
malaoxon, parathion, and paraoxon standards were from
Accustandard Co. (USA). Solvents used dichloromethane, methanol,
and acetone were from Merck Co. (residue grade, Darmstadt,
Germany). Sodium sulfate and hydrogen peroxide (35%) were also
from Merck Co. A commercial TiO2 photocatalyst was used with a
BET surface of 35–65 m2/g and diameter of 45 mm (ACROS). Standard
stock solution of 1000 mg/L of pesticides was prepared in methanol.
Stock solutions were stored in the dark at 48C. Working solutions
were prepared by dilution of standard stock solution with distilled
water before each experiment.
2.2 Oxidation procedure
2.2.1 Ozone (O3)
Ozone experiments were performed in a bench-scale glass reactor
with an effective volume of 2.0 L. Glass reactor was filled with
1000 mL solution containing malathion and parathion at different
concentrations. After constant level of ozone achieved in the reactor
OPPs added in. Shematic diagram of experimental set up is given
in Fig. 1. Shen et al. [28] used a similar method for degradation of
p-chloronitrobenzene in water by ozonation.
Figure 1. Shematic diagram of experimental set-up [(1) O2 tank, (2) flow-
meter, (3) ozone generator, (4) diffuser, (5) reactor, (6) magnetic stirrer, (7)
sampling port, (8) dosage unit, and (9) KI absorption bottles].
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Clean – Soil, Air, Water 2012, 40 (2), 179–187
For the ozonation, a corona discharge type ozone generator OZ-
10G (A to Z Ozone Systems Inc., Louisville) was used. Generator was
fed with predetermined amount of pure O2 by using flow meter.
Dissolved ozone was adjusted to desired concentration by changing
amount of pure O2 flow. Non-consumed gaseous ozone was
trapped in two bottles of 2% KI solution. The concentration of
aqueous ozone was detected using Spectrophotometric Test Kit
Method (00607 Reagent Test). The method depends on ozone reaction
with dipropyl-p-phenyldiamine (DPD) to form a red-violet dye that is
determined photometrically. The accuracy of a measurement value
for 0.05–4.00 mg/L O3 measurement is maximum 0.10 mg/L O3.
The produced ozone is injected into the reactor from the bottom
by glass diffuser system and mass transfer of ozone gas was
accelerated with magnetic stirring. A sampling port was located
at the bottom of the reactor. The experiment was conducted for
90 min. At desired time intervals (2, 10, 20, 30, 60, and 90 min) 50 mL
of samples were withdrawn from the sampling port and the residual
OPPs and OPP–oxon intermediates were immediately analyzed by
GC-MS as described in Section 2.4.
Control experiment was conducted under the same experimental
conditions. This experiment involved 1 L deionized test water spiked
200 mg of OPPs without ozonation to determine the stability of
analytes and OPP–oxon formation in unozonated water within
experiment duration.
2.2.2 O3/UV
The O3/UV experiments were carried out following the same pro-
cedure with O3 experiments but only two UV lamps were placed on
two opposite sides of the reactor. The lamps used in this study were
medium pressure mercury arc UV lamps (Osaka Ltd.) emitting in the
wavelength of 254 nm. For safety purposes, the entire system was
placed inside a box to avoid UV light escaping to the surroundings.
Experiments were performed with and without adding H2O2. An
appropriate volume of the stock solution of H2O2 was added into the
mixture to yield desired concentrations of 20, 40, and 100 mg/L.
Immediately after the addition of the H2O2, the UV light was turned
on. GC-MS was used to analyze the residual OPPs and OPP–oxon
intermediates.
Control experiment was conducted under the same experimental
conditions. Control experiments were also carried out following the
same procedure with UV irradiation and 200 mg/L of OPPs but with-
out addition of any catalyst.
2.2.3 O3/UV/TiO2
The photocatalytic ozonation was carried out following the same
procedure with O3/UV experiments but only difference was the
desired amounts of TiO2 (0.5, 1.0, and 1.5 g/L) were added in the
reactor. A standard experiment involved the addition of 200 mg of
OPPs to 1 L deionized water to yield 200 mg/L concentration. OPPs
solution with the appropriate amount of catalyst was magnetically
stirred before and during the illumination. At specific time intervals,
samples were withdrawn from the reactor for analysis. In order to
remove the TiO2, the solution was centrifuged at 4000 rpm for 10 min.
2.3 Extraction procedure
Traditional liquid–liquid extraction procedure was adopted from
US EPA Method 3510C [29]. Fifty milliliters of water were placed in a
www.clean-journal.com
Clean – Soil, Air, Water 2012, 40 (2), 179–187 Degradation of Malathion and Parathion 181

200-mL capacity of separatory funnel. Extraction was carried out 3.2 Ozonation of OPPs (O3)
with 20 mL dichloromethane. The dichloromethane extract was
dried with anhydrous sodium sulfate. Then, the extract was concen- 3.2.1 Effect of pH
trated to exactly 1 mL using rotary evaporator (Buchi B-160 Vocabox,
Switzerland) and a gentle nitrogen stream. Then, GC-MS analysis was The effect of pH is important in ozonation removal of organic
performed as described in Section 2.4. molecules since it influences the formation of hydroxyl radicals
(OH
). Ozonation at low pH involves mainly the direct ozone reaction
(ozonolysis) with high selectivity while high pH involves non-selec-
2.4 GC-MS analysis tive OH
radical attack on molecules [33]. Three pH values (3.0, 6.5,
and 9.0) were experimented for the degradation of malathion and
The determination of OPPs and OPP–oxon were carried out by gas
parathion. O3 concentration was adjusted to 1.5 mg/L. Degradation
chromatograph (GC, Agilent 6890N, Agilent Technologies, Palo Alto,
of malathion increased in pH 9.0 (Fig. 2a). Malathion with an initial
CA, USA) equipped with mass-selective detector (MS, Agilent 5973,
concentration of 200 mg/L was almost degraded in 20 min at pH 9.0,
Agilent Technologies, Foster City, CA, USA). The features and operat-
while a further 10 min was required for its complete degradation at
ing conditions of GC-MS system were as follows: GC, equipped with
pH 3.0 and 6.5. Initial parathion concentration of 200 mg/L was
programmed temperature vaporizing (PTV) injector, DB-5 MS 5%
completely degraded in 60 min at all investigated pH levels but
phenylmethyl siloxane fused silica capillary column (30 m length,
the reaction rate was higher at pH 9.0 (Fig. 2b). When degradation
0.25 mm i.d., and 0.25 mm film thickness), and helium (purity
of parathion is compared with malathion, it is seen that a longer
99.999%) as carrier gas at constant flow rate of 1.9 mL/min. PTV
oxidation time is required for complete decomposition of parathion.
program was as follow: 808C, 128C/s to 3508C, and hold at 3508C
This can be explained with lower OH
radical reactivity of parathion
for 2 min. Injections were performed by an Agilent 7683 B Series
automatic injector (Agilent Technologies). The oven temperature
program was as follow: Initial temperature 408C for 4.2 min,
758C/min to 1408C for 2 min, 58C/min to 2008C for 2 min, 28C/min
to 2408C for 5 min, and 158C/min to 3008C for 5 min. MS detector was
operated in selected ion monitoring (SIM) mode with three selected
ions for OPPs and their oxon intermediates. Characteristic ions (m/z)
selected for SIM mode were 125, 173, and 93 for malathion, 291, 107,
and 97 for parathion, 127, 99, and 55 for malaoxon, and 109, 149, and
81 for paraoxon. Analytical curves were drawn using seven points in
the concentration range of 0.1–10 ng/mL.

2.5 Toxicity measurements

For toxicity determination of the treated solutions D. magna and
V. fischeri were used. The toxicity tests on D. magna bioassay were
performed following the standard operational procedures of
the respective Daphtoxkit FTM toxkits microbiotest [30] and
Luminescence bacteria test with V. fischeri was carried out according
to DIN/EN/ISO 11348-2 (Luminescent bacteria test LCK 482) [31]
measured with Dr. Lange LUMIStox 300 Luminometer. The variation
of % inhibition of the bioluminescence as a function of time during
the oxidation processes was determined. In order to assess the acute
toxicity, test results were expressed in EC50. EC50 values are the
concentration responsible for the inhibition/mortality in 50% of
the tested population in the different volumes of the sample.

3 Results and discussion

3.1 Analytical results
Disappearance of the parent compounds were monitored by GC-MS.
Formation and disappearance of oxon intermediates were also moni-
tored by GC-MS. The calibration curves gave a high level of linearity
for studied OPPs and OPP–oxon derivatives with correlation coeffi-
cients (r) ranging between 0.992 and 0.998. The limits of detection
(LODs) for all OPPs and OPP–oxon derivatives were determined
according to the signal-to-noise ratio (S/N) of three [32]. LODs
Figure 2. Effect of pH on ozonation removal of malathion (a) and parathion
obtained for OPPs and OPP–oxon derivatives were ranged between (b) and formation of malaoxon (a) and paraoxon (b). (CO3 ¼ 1:5 mg=L and
0.004 and 0.021 ng/mL. COPP: 200 mg/L).

ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com

182 F. Beduk et al.
[14]. Besides, malathion and parathion have specific functional
groups (e.g., CH3 and OCH3) and atoms carrying negative charge
(N, P, O, and S) which make them susceptible to ozonolysis occurring
at lower pH [34].
Among the reactions that take place at the ozonation process,
the reaction between ozone and the malathion and parathion is the
rate determining step, the rate equation can be given according to
the Eq. (1).
dC
 ¼ k0 t
dt
where, C is the concentration of the compound and k0 is the rate
constant.
In order to evaluate the malathion and parathion degradation
kinetics the logarithm of ln(C0/C) against time was plotted. The linear
regression curve was fit well therefore it was concluded that mala-
thion and parathion oxidation followed the first-order kinetic. The
rate constant was determined by calculating the slope of the line
obtained. The degradation rate constants of parathion and mala-
thion by ozonation at different solution pH are given in Tab. 1. The
degradation reaction rate constants of organic compounds by ozo-
nation increased at alkaline condition. Rate constants are higher
at pH 3 when compared with pH 6.5 probably because of better
ozonolysis effect at more acidic conditions. Wu et al. [14] explained
the disappearance kinetic of parathion with the first-order kinetic
law. Reported results showed that rate constants at different pH
values were the same for ozonation of parathion while they
increased at alkaline conditions for other OPPs, such as diazinon
and methyl parathion.
Oxidation attack of ozone on the P — — S bond of malathion and
parathion results in the formation of malaoxon and paraoxon.
Malaoxon and paraoxon were not completely oxidized in the ozona-
tion process at experimented pH cases (Fig. 2). Malaoxon and paraoxon
reached maximum levels of 24 and 25 mg/L (in average 12% of decayed
malathion and parathion), respectively, at pH 9 while these values
were 27 and 29 mg/L at pH 3 (in average 14% of decayed malathion and
parathion). Decomposition of OPPs and their oxon intermediates were
better at alkaline conditions. Oxon accumulation can be explained
with low hydroxyl radical formation. Ozonation of malathion and
parathion with 1.5 mg/L of O3 appeared not to be efficient because of
oxon formation and persistency. Additional free hydroxyl radicals can
be produced in the aqueous media by combining ozone with hydro-
gen peroxide or UV irradiation.
3.2.2 Effect of O3 concentration
Ozone concentration was adjusted to 1, 1.5, and 2 mg/L. Solution pH
was adjusted to 9, which was the optimized value in prior step.
Table 1. The degradation rate constants of OPPs by ozonation at different
solution pH (n ¼ 3) (COPP: 200 mg/L and CO3 ¼ 1:5 mg=L)
Compound pH Rate constant (k0 ) Correlation
(min1) coefficient (R)
Malathion 3 0.09 0.98
6.5 0.08 0.97
9 0.18 0.99
Parathion 3 0.11 0.92
6.5 0.09 0.97
9 0.13 0.93
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Clean – Soil, Air, Water 2012, 40 (2), 179–187
GC/MS chromatogram of malathion, parathion, malaoxon, and para-
oxon is given in Fig. 3 conducted in 2 mg/L of O3 application exper-
iments. Oxidation of malathion and parathion and formation of
malaoxon and paraoxon corresponding to rate of reaction with time
can be seen in the chromatogram. Increasing ozone concentration
increased decomposition rates of diazinon and malathion and their
oxon intermediates. In three different O3 concentration cases, 100%
removal of malathion and parathion was achieved. For 1.5, 2, and
2.5 mg/L ozone concentrations paraoxon reached maximum levels of
20, 12, and 7 mg/L, respectively, and malaoxon reached maximum
(1)
levels of 12, 8, and 7 mg/L, respectively. Results showed that OPPs
removal increased with increasing ozone dosage, however, 2.0 mg/L
of ozone dosage with 30 min oxidation time was more
economical and efficient. Removal efficiency of 2.5 mg/L O3 was
80 mg parathion/mg O3 and it was 100 mg parathion/mg O3 for
2 mg/L O3 application. Li et al. [27] reported similar results for
dissolved organic carbon removal by using combined ozone systems.
Oxidation of dissolved organic carbon increased with ozone dosage,
however, 3 mg/L ozone dosage with 15 min oxidation time was more
economical and efficient.
The degradation rate constants of parathion and malathion by
ozonation at different ozone concentrations are given in Tab. 2.
Malathion and parathion oxidation followed the first-order kinetic
law. The degradation reaction rate constants of OPPs by ozonation
increased with increasing dissolved ozone concentrations.
Malathion has higher reaction rates than parathion for different
dissolved ozone concentrations. According to the frontier orbital
theory, the reactivity of reactants is largely dependent on the ener-
gies of the frontier molecular orbital [35]. Because ozone is a strong
electrophile (13.0 eV) it can be expected that a pesticide with a high
energies of the frontier molecular orbital will have a high rate
Figure 3. GC-MS chromatogram of malathion and parathion and their
ozonation products (malaoxon and paraoxon) acquired 2 min (a) and
60 min (b) after the ozone reaction (CO3 ¼ 2:0 mg=L, COPP: 200 mg/L,
pH 9.0).
www.clean-journal.com
Clean – Soil, Air, Water 2012, 40 (2), 179–187
Table 2. The degradation rate constants of OPPs by ozonation at different
ozone concentrations (n ¼ 3) (COPP: 200 mg/L, pH 9)
Compound O3 Rate constant (k0 ) Correlation
(mg/L) (min1) coefficient (R)
Malathion 1.5 0.18 99
2.0 0.26 99
2.5 0.41 99
Parathion 1.5 0.13 93
2.0 0.17 99
2.5 0.22 98
constant of ozonation. Lower reactivity of parathion can be
explained as due to the electron withdrawing groups on the
benzene ring, which decrease the electron density of the ring and
hence decrease the electrophilic attack by ozone.
As mentioned before, 1.5 mg/L ozone application was not enough
for oxons’ oxidation. Parathion with an initial concentration of
200 mg/L, decayed to 20, 12, and 7 mg/L of paraoxon after 1.5, 2.0,
and 2.5 mg/L ozone applications for 90 min. Malathion with an initial
concentration of 200 mg/L, decayed to 12, 8, and 7 mg/L of malaoxon
after 1.5, 2.0, and 2.5 mg/L ozone application in the same period.
These results show that ozone alone, even in high concentrations, is
not efficient for complete detoxification of OPPs.
3.3 Photolytic ozonation of OPPs (O3/UV)
The photooxidation of two OPPs, malathion and parathion, by
UV, O3/UV, and O3/UV/H2O2 in aqueous solution were studied. No
significant hydrolysis occurred within the time scale of the photoly-
sis experiments. First experiments were carried out employing UV
irradiation of malathion and parathion (200 mg/L concentration
level) to determine direct photolysis without addition of any cata-
lyst. No obvious degradation of the malathion and parathion were
determined in this time period. Malathion (95.6%) and parathion
(92.3%) remained after 90 min of UV irradiation. Oxon analogues
were not determined. Zamy et al. [36] also reported that no degra-
dation products were determined after irradiation of OPPs because
of low concentration of photoproducts. Direct photolysis proceeds by
absorbing light. The rate of direct photolysis depends on the molar
absorption coefficient and on the efficiency of the photochemical
transformation. Direct photolysis of OPPs both by low pressure and
medium pressure lamps was reported to be very slow with low
quantum yields [37].
For O3/UV application, monochromatic irradiation (254 nm)
was combined with 2 mg/L of O3. The disappearance of pesticides
appeared to follow first-order kinetics. The first-order rate constants
of malathion and parathion with O3/UV were determined to be
0.34 and 0.21 min1, respectively. Comparison of processes on the
removal of parathion and malathion and formation of oxon inter-
mediates are given in Fig. 4a–d. Reaction rates increased for both of
the OPPs when O3 was combined with UV irradiation, but complete
decomposition of oxon intermediates were not possible at the end
of 90 min. Within 10 min, malaoxon and paraoxon reached their
optimum levels of 13 and 18 mg/L. Malaoxon (2 mg/L) and paraoxon
(8 mg/L) were left at the end of the 90 min of O3/UV application.
Indirect photolysis proceeds through the reaction between
contaminants and transient oxidizing radicals. OH
is the major
oxidizing radical in the O3/UV process (Eqs. (2) and (3)). The
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Degradation of Malathion and Parathion 183
absorption coefficient for ozone has been reported to be 3600 M/cm
at a wavelength of 254 nm [38].
O3 þ H2 O þ hn ! H2 O2 þ O2 (2)
H2 O2 þ hn ! 2HO
(3)
In O3 and O3/UV applications, complete decomposition of oxon
intermediates were not possible at the end of 90 min. O3/UV/H2O2
process was used so as to complete oxidation of malaoxon and
paraoxon. Addition of H2O2 increased the degradation rates of mala-
thion, parathion, and their oxon intermediates by generating
hydroxyl radicals. Dissociated form of hydrogen peroxide (HO 2)
reacts with ozone. This reaction leads to the production of ozonide
ion (O

3 ) and hydroperoxide radical (HO2 ) [39]. Addition of 20, 40, and
100 mg/L hydrogen peroxide were experimented. Malathion and
parathion oxidation with O3/UV/H2O2 followed the first-order kinetic
law. Calculated reaction rate constant are given in Tab. 3 and the
comparison of O3/UV/H2O2 process with other experimented pro-
cesses on the removal of parathion and malathion and formation
of oxon intermediates are given in Fig. 4a–d. The increased addition of
hydrogen peroxide did not result in a linear increase in the reaction
rate constants of malathion and parathion. At the same initial
malathion and parathion concentrations, the photodegradation rates
initially increased rapidly with increasing addition of hydrogen per-
oxide from 0 to 20 mg/L and from 20 to 40 mg/L. However, an increase
of the hydrogen peroxide concentration from 40 to 100 mg/L resulted
with a sharp decrease in the reaction rates. Excessive amount of H2O2
use causes radical scavenging (Eqs. (4)–(6)) [40] because non-selective
oxidizing effect of OH
radical.
H2 O2 þ OH
! H2 O þ HO2 (4)
HO2 þ OH
! H2 O þ O2 (5)
OH
þ OH
! H2 O2 (6)
Langlais et al. [41] reported similar results for oxidation of atrazine
by using O3 alone and in combination with hydrogen peroxide.
O3/H2O2 combination accelerated atrazine oxidation when com-
pared with O3 alone, but increasing amounts of H2O2 did not result
with increase in reaction rate. Optimum O3/H2O2 ratio was deter-
mined to be 0.35–0.45. Complete decomposition of paraoxon and
malaoxon were achieved by using optimum concentration of H2O2
(40 mg/L) in combination with O3/UV (Fig. 4c and d). Malaoxon
reached its optimum concentration in 10 min and 100% removal
was achieved in 30 min. Similarly, paraoxon reached its optimum
concentration in 10 min and 100% removal was achieved in 60 min.
Paraoxon is a more persistent pesticide toward oxidation process
when compared with malaoxon. Wu et al. [14] reported similar
results about persistency of paraoxon toward ozonation when
compared with diazoxon and methyl-paraoxon.
3.4 Heterogeneous catalytic ozonation of
OPPs (O3/UV/TiO2)
3.4.1 Effect of catalyst concentration
In order to determine effect of catalyst concentration on the photo-
catalytic ozonation process 0.5, 1.0, and 1.5 g/L of TiO2 was added
to neutral deionized water. For the photocatalytic process,
www.clean-journal.com
184 F. Beduk et al. Clean – Soil, Air, Water 2012, 40 (2), 179–187

Figure 4. Comparison on the removal of malathion (a) and parathion (b) and formation of malaoxon (c) and paraoxon (d) with O3, O3/UV, O3/UV/H2O2,
and O3/UV/TiO2 processes. (COPP ¼ 200 mg/L, CO3 ¼ 2 mg=L, CTiO2 ¼ 1 g=L, CH2 O2 ¼ 40 mg=L, 254 nm UV, pH 6.5).

generally pH has a varied effect on the process. It is expected that concluded that the effect of pH is negligible so pH adjustment is not
increase or decrease in the pH should affect the rate of degradation required in the photocatalytic degradation [34].
as adsorption increases at lower pH and the concentration of The comparison of O3/UV/TiO2 process with other experimented
OH
radicals are relatively higher at alkaline pH values. It can be processes on the removal of parathion and malathion and formation
of oxon intermediates are given in Fig. 4a–d. O3/UV/TiO2 process can
compensate for the decrease of the degradation rate of OPPs and
Table 3. The degradation rate constants of OPPs by ozonation at
oxon derivatives by reacting with positive holes and electrons
different H2O2 concentrations (n ¼ 3) (COPP: 200 mg/L, pH 9)
to decrease the recombination rate of holes and electrons.
Compound H2O2 Rate constant (k0 ) Correlation Decomposition of 99% of parent compounds were achieved in
concentration (min1) coefficient (R) 10 min and oxon derivatives were completely removed in 30 min.
(mg/L) For O3/UV/TiO2 process reaction rates increased for malathion and
Malathion 20 0.37 0.98 parathion when compared with O3, O3/UV, and O3/UV/H2O2 pro-
40 0.43 0.98 cesses. Malathion and parathion oxidation with O3/UV/TiO2 followed
100 0.02 0.91 the first-order kinetic law. Calculated reaction rate constants for
Parathion 20 0.25 0.98 different amounts of TiO2 are given in Tab. 4. The increased addition
40 0.44 0.99
of TiO2 did not result in a linear increase in the reaction rate
100 0.05 0.94
constants of OPPs. It was determined that the initial reaction rate

ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com

Clean – Soil, Air, Water 2012, 40 (2), 179–187 Degradation of Malathion and Parathion 185

Table 4. The degradation rate constants of OPPs by O3/TiO2/UV at

different TiO2 concentrations (n ¼ 3) (COPP ¼ 200 mg/L, pH 6.5,
CO3 ¼ 2 mg=L)

Compound TiO2 Rate constant (k0 ) Correlation

concentration (min1) coefficient (R)
(g/L)

Malathion 0.5 0.80 0.97

1 1.06 0.95
1.5 0.44 0.93
Parathion 0.5 0.83 0.99
1 1.05 0.99
1.5 0.39 0.96

increases linearly with an increase amount of catalyst up to a level

corresponding to the optimum of light absorption. Optimum con-
centration of TiO2 is 1 g/L. Doong and Chang [11] studied photo-
catalytic degradation of parathion using UV radiation in
combination with hydrogen peroxide and TiO2. In the study, it
was reported that initial rate constants increased with the increase
of TiO2 loading from 0.1 to 1 g/L, however, the degradation rates of
parathion decreased when the TiO2 dose was increased to 2 g/L.
In catalytic ozonation process the presence of dissolved ozone in
the irradiated TiO2 aqueous suspension increases the OH
radical
production and decreases the electron–hole recombination, increas-
ing the efficiency of the photocatalytic process [42]. In the process,
reactions on the catalyst surface involve several steps such as
adsorption, ozone decomposition reaction, surface oxidation reac-
tion, and desorption process. The adsorption process is influenced by
surface properties of the catalyst such as surface area, pores volume,
and surface active sites. The structure of the organic molecule,
its pKa, polarity, molecular weight, and functional groups determine
its affinity to the catalyst surface. [25]. Farre et al. [42] compared
HeCO with HoCO and O3/UV processes for the degradation of bio-
recalcitrant pesticides such as alachlor, atrazine, etc. No noticeable Figure 5. Effect of initial malathion (a) and parathion (b) concentrations on
degradation of pesticides occurred when O3/UV was applied. The best removal of malathion and parathion and formation of malaoxon and para-
results were obtained by the application of HoCO system for all oxon with O3/UV/TiO2 process. (COPP ¼ 200 mg/L, CO3 ¼ 2 mg=L,
CTiO2 ¼ 1 g=L, pH 6.5).
pesticides solutions investigated.

3.4.2 Effect of analyte concentration

Figure 5a and b shows the time course of the concentrations of the
OPPs and their oxon intermediates when optimized conditions of
O3/UV/TiO2 process were applied. In order to determine effect of
analyte concentration on the photocatalytic ozonation process
100, 200, and 500 of OPPs were used. Ninety-nine percent of
malathion and parathion were oxidized in 10 min. When 500 mg/L
of malathion and parathion were oxidized, 2.6% of malathion decayed
to malaoxon, and 3.6% of parathion was decayed to paraoxon.
Complete decomposition of malaoxon was achieved in 20 min while
90 min was needed for complete paraoxon removal.
3.5 Results of toxicity measurements
In our study, toxicity measurements of the treated solutions were
carried out in order to evaluate the efficiency of the treatment
methods. For toxicity determination of the treated solutions
D. magna and V. fischeri, two different biotests from different
trophic levels were chosen. The microtox test using luminescent
bacteria was employed as representative for the decomposers. As
representatives of the primary consumers the crustacea D. magna
was used. The variation of % inhibition of the bioluminescence as
a function of time during the ozonation, photolytic ozonation,
and heterogeneous catalytic processes were determined. Treated
solutions with O3, O3/UV, O3/UV/H2O2, and O3/UV/TiO2 showed no
inhibition effect on V. fischeri test organism. For V. fischeri toxicity test
EC50 values for parathion and paraoxon were 12 650 and 4140 mg/L,
respectively. EC50 values for malathion and malaoxon were 12 564
and 4290 mg/L. Neither of the treated solutions by using different
oxidation processes showed any inhibition effect on the test
organism.
Treated solutions with O3 and O3/UV showed a severe toxicity
effect on D. magna. From the beginning of the O3 and O3/UV pro-
cesses, treated solutions showed 100% inhibition effect until the end
of oxidation processes, because malaoxon and paraoxon decompo-
sition was not complete at the end of 90 min. However, almost
complete detoxification was achieved only in the presence of hydro-
gen peroxide in photolytic ozonation process and HeCO process. For
D. magna toxicity test EC50 values for parathion and paraoxon were
0.798 and 0.757 mg/L, respectively. EC50 values for malathion and

ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com

186 F. Beduk et al.
malaoxon were 0.948 and >4 mg/L, respectively. Toxicity effect of
OPPs and their oxon derivatives are higher to D. magna test organism
than bioluminescence bacteria.
4 Conclusions
Ozone is known to be a powerful oxidant, but it does not cause the
complete oxidation of OPPs. In order to provide greater ozonation
process efficiency, advanced oxidation methods have been investi-
gated and compared. O3/UV, O3/UV/H2O2, and O3/TiO2/UV involve the
generation of hydroxyl radicals, which are active oxidative species.
In this study, O3/TiO2/UV was shown to be feasible for achieving
complete decomposition of OPPs and their toxic oxon intermediates.
The authors have declared no conflict of interest.
References
[1] I. K. Konstantinou, D. G. Hela, T. A. Albanis, The Status of Pesticide
Pollution in Surface Waters (Rivers and Lakes) of Greece. Part I.
Review on Occurrence and Levels, Environ. Pollut. 2006, 141, 555–570.
[2] L. Hoferkamp, M. H. Hermanson, D. C. G. Muir, Current Use
Pesticides in ARCTIC Media, 2000–2007, Sci. Total Environ. 2010,
408, 2985–2994.
[3] S. O. Pehkonen, Q. Zhang, The Degradation of Organophosphorus
Pesticides in Natural Waters: A Critical Review, Crit. Rev. Environ. Sci.
Technol. 2002, 32, 17–72.
[4] K. E. Banks, P. K. Turner, S. H. Wood, C. Matthews, Increased Toxicity
to Ceriodaphnia dubia in Mixtures of Atrazine and Diazinon at
Environmentally Realistic Concentrations, Ecotoxicol. Environ. Saf.
2005, 60, 28–36.
[5] S. S. Koprucu, K. Koprucu, M. S. Ural, U. Ispir, M. Pala, Acute Toxicity
of Organophosphorous Pesticide Diazinon and Its Effects on
Behavior and Some Hematological Parameters of Fingerling
European Catfish (Silurus glanis L.), Pestic. Biochem. Physiol. 2006, 86,
99–105.
[6] X. Zhao, H. M. Hwang, A Study of the Degradation of
Organophosphorus Pesticides in River Waters and the
Identification of Their Degradation Products by Chromatography
Coupled with Mass Spectrometry, Arch. Environ. Contam. Toxicol. 2009,
56, 646.
[7] Y. Ku, J. L. Chang, S. C. Cheng, Effect of Solution pH on the Hydrolysis
and Photolysis of Diazinon in Aqueous Solution, Water Air Soil Pollut.
1998, 108, 445–456.
[8] H. Shemer, K. G. Linden, Degradation and By-Product Formation of
Diazinon in Water during UV and UV/H2O2 Treatment, J. Hazard.
Mater. 2006, 136, 553–559.
[9] E. Evgenidou, I. Konstantinou, K. Fytianos, I. Poulis, T. Albanis,
Photocatalytic Oxidation of Methyl Parathion over TiO2 and ZnO
Suspensions, Catal. Today 2007, 124, 156–162.
[10] M. B. Kralj, U. Cernigoj, M. Franko, P. Trebse, Comparison of
Photocatalysis and Photolysis of Malathion, Isomalathion,
Malaoxon, and Commercial Malathion-Products and Toxicity
Studies, Water Res. 2007, 41, 4504–4514.
[11] R. Doong, W. Chang, Photodegredation of Parathion in
Aqueous Titanium Dioxide and Zero Valent Iron Solutions in the
Presence of Hydrogen Peroxide, J. Photochem. Photobiol., A 1998, 116,
221–228.
[12] M. I. Badawy, M. Y. Ghaly, T. A. Gad-Allah, Advanced Oxidation
Processes for the Removal of Organophosphorus Pesticides from
Wastewater, Desalination 2006, 194, 166–175.
[13] R. Doong, W. Chang, Photoassisted Iron Compound Catalytic
Degradation of Organophosphorous Pesticides with Hydrogen
Peroxide, Chemosphere 1998, 37, 2563–2572.
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Clean – Soil, Air, Water 2012, 40 (2), 179–187
[14] J. Wu, C. Lan, G. Y. S. Chan, Organophosphorus Pesticide Ozonation
and Formation of Oxon Intermediates, Chemosphere 2009, 76, 1308–
1314.
[15] Y. Ku, J. L. Chang, Y. S. Shen, S. Y. Lin, Decomposition of Diazinon in
Aqueous Solution by Ozonation, Water Res. 1998, 32, 1957–1963.
[16] F. J. Beltran, Ozone Reaction Kinetics for Water and Wastewater Systems,
Lewis Publishers, Boca Raton, FL 2005.
[17] T. S. Kim, J. K. Kim, K. Choi, M. K. Stenstrom, et al., Degradation
Mechanism and the Toxicity Assessment in TiO2 Photocatalysis and
Photolysis of Parathion, Chemosphere 2006, 62, 926–933.
[18] D. Virag, Z. Naar, A. Kiss, Microbial Toxicity of Pesticide Derivatives
Produced with UV-Photodegradation, Bull. Environ. Contam. Toxicol.
2007, 79, 356–359.
[19] G. R. Peyton, W. H. Glaze, Destruction of Pollutants in Water with
Ozone in Combination with Ultraviolet Radiation. 3. Photolysis of
Aqueous Ozone, Environ. Sci. Technol. 1988, 22, 761.
[20] A. Latifoglu, M. D. Gurol, The Effect of Humic Acids on Nitrobenzene
Oxidation by Ozonation and O3/UV Processes, Water Res. 2003, 37,
1879–1889.
[21] Y. F. Rao, W. Chu, A New Approach to Quantify the Degradation
Kinetics of Linuron with UV, Ozonation and UV/O3 Processes,
Chemosphere 2009, 74, 1444–1449.
[22] P. P. Kuo, E. S. K. Chian, B. J. Chang, Identification of End Products
Resulting from Ozonation and Chlorination of Organic Compounds
Commonly Found in Water, Environ. Sci. Technol. 1977, 11 (13), 1177.
[23] S. Dong, D. Zhou, X. Bi, Liquid Phase Heterogeneous Photocatalytic
Ozonation of Phenol in Liquid–Solid Fluidized Bed: Simplified
Kinetic Modeling, Particuology 2010, 8, 60–66.
[24] J. Gong, Y. Liu, X. Sun, O3 and UV/O3 Oxidation of Organic
Constituents of Biotreated Municipal Wastewater, Water Res.
2008, 42, 1238–1244.
[25] B. Kasprzyk-Hordern, M. Ziólek, J. Nawrocki, Catalytic Ozonation
/
and Methods of Enhancing Molecular Ozone Reactions in Water
Treatment, Appl. Catal., B 2003, 46, 639–669.
[26] C. Kormann, D. F. Bahnemann, M. R. Hoffmann, Photolysis of
Chloroform and Other Organic Molecules in Aqueous TiO2
Suspensions, Environ. Sci. Technol. 1991, 25, 494–500.
[27] L. Li, W. Zhu, P. Zhang, Q. Zhang, Z. Zhang, AC/O3-BAC Processes for
Removing Refractory and Hazardous Pollutants in Raw Water, J.
Hazard. Mater. 2006, 135, 129–133.
[28] J. M. Shen, Z. L. Chen, Z. Z. Xu, Y. Y. Li, B. B. Xu, F. Qi, Kinetics and
Mechanism of Degradation of p-Chloronitrobenzene in Water by
Ozonation, J. Hazard. Mater. 2008, 152, 1325–1331.
[29] US EPA, US EPA Method 3510C, Separatory Funnel Liquid–Liquid
Extraction (Revision 3–December, 1996), SW846 CH 4.2.1, US EPA,
Washington, DC 1996.
[30] Creasel, Standard Operational Procedure, Daphtoxkit FTM Magna,
Crustacean Toxicity Screening Test for Freshwater, Creasel, Nazareth,
Belgium 2009.
[31] International Organisation for Standardisation, ISO 11348-2, Water
Quality – Determination of the Inhibitory Effect of Water Samples on
the Light Emission of Vibrio fischeri (Luminescent Bacteria Test), Part 2:
Method Using Liquid-Dried Bacteria, International Organisation for
Standardisation, Geneva, Switzerland 1998.
[32] A. Tor, M. E. Aydin, Application of Liquid-Phase Microextraction to
the Analysis of Trihalomethanes in Water, Anal. Chim. Acta 2006, 575
(1), 138–143.
[33] W. R. Chen, C. Wu, M. S. Elovitz, K. G. Linden, L. H. Suffet, Reactions
of Thiocarbamate, Triazine ad Urea Herbicides, RDX and Benzenes
on EPA Contaminant Candidate List with Ozone and with Hydroxyl
Radicals, Water Res. 2008, 42, 137–144.
[34] T. E. Agustina, H. M. Ang, V. K. Vareek, A Review of Synergistic Effect
of Photocatalysis and Ozonation on Wastewater Treatment, J.
Photochem. Photobiol., C 2005, 6, 264–273.
[35] J. Y. Hu, T. Morita, Y. Magara, T. Aizawa, Evaluation of Reactivity of
Pesticides with Ozone in Water Using the Energies of Frontier
Molecular Orbitals, Water Res. 2000, 34, 2215–2222.
www.clean-journal.com
Clean – Soil, Air, Water 2012, 40 (2), 179–187
[36] C. Zamy, P. Mazellier, B. Legube, Phototransformation of Selected
Organophosphorus Pesticides in Dilute Aqueous Solutions, Water
Res. 2004, 38, 2305–2314.
[37] C. Wu, K. G. Linden, Degradation and Byproduct Formation of
Parathion in Aqueous Solutions by UV and UV/H2O2 Treatment,
Water Res. 2008, 42, 4780–4790.
[38] D. Bahnemann, E. J. Hart, Rate Constants of the Reaction of the
Hydrated Electron and Hydroxyl Radical with Ozone in Aqueous
Solution, J. Phys. Chem. 1984, 88, 5999.
[39] M. D. Gurol, A. Akata, Kinetics of Ozone Photolysis in Aqueous
Solution, AIChE J. 1996, 42, 3283–3292.
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Degradation of Malathion and Parathion 187
[40] M. Pérez, F. Torrades, J. A. Garcı́a-Hortal, X. Doménech, J. Peral,
Removal of Organic Contaminants in Paper Pulp Treatment
Effluents by Fenton and Photo-Fenton Reactions, Appl. Catal. 2002,
36, 63–74.
[41] B. Langlais, D. A. Reckhow, R. B. Deborah, Ozone in Water
Treatment Application and Engineering, 1st Ed., CRC Press, Boca
Raton, FL 1991.
[42] M. J. Farre, M. I. Franch, S. Malato, J. A. Ayllon, J. Peral, X. Domenech,
Degradation of Some Biorecalcitrant Pesticides by Homogeneous
and Heterogeneous Photocatalytic Ozonation, Chemosphere 2005, 58,
1127–1133.
www.clean-journal.com