Available online at www.sciencedirect.

com

ScienceDirect
APCBEE Procedia 8 (2014) 151 155

2013 4th International Conference on Agriculture and Animal Science (CAAS 2013)
2013 3rd International Conference on Asia Agriculture and Animal (ICAAA 2013)

UV/ozone Treatment of the Pyrethroid Insecticide Fenvalerate

in Aqueous Solutions
Nga T. T. Tran a,*, Thanh H. Trinh b, Nam M. Hoang a, Thang M. Ngo a
b

a
HCMC University of Technology, Ho Chi Minh City, Vietnam
Universiti Teknologi PETRONAS, 31750 Seri Iskandar, Perak, Malaysia

Abstract
Fenvalerate is a common Pyrethroid insecticide exits stably in water and soil. This study subjected to enhance the
degradation of fenvalerate (in the form of aqueous emulsion of a commercial formulation) using UV/ozone process.
Experiment results indicated that fenvalerate was decomposed rapidly under UV irradiation (99% within 10 minutes).
Degradation yield also showed an increase when ozone was applied. UV/ozone degradation rates of fenvalerate followed
first-order kinetics. In alkaline medium, there was a slight increase in yield. Sodium nitrate acted as a photo-sensitizer for
UV irradiation process so it helped to increase reaction rate at an optimum concentration of 2.5 mM. Moreover, some
degradation products were identified and tentatively assigned by GC-MS.

Authors. Published
by Elsevier
B.V. This and/or
is an open
access
articleunder
underresponsibility
the CC BY-NC-ND
license
2014
2013The
Published
by Elsevier
B.V. Selection
peer
review
of Asia-Pacific
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Chemical, Biological & Environmental Engineering Society
Selection and peer review under responsibility of Asia-Pacific Chemical, Biological & Environmental Engineering Society
Keywords: Fenvalerate, ozone, UV irradiation, water treatment.

1. Introduction
Pyrethroids comprise a class of synthetic compounds which have structures based on those of the naturally
occurring pyrethrin insecticides [1]. Synthetic pyrethroids have been widely used as pesticide in agriculture,
forestry and public health due to their high insecticidal activity, long-term stability, and good compatibility [1]
and [2]. Fenvalerate is one of the most potent pyrethroid insecticides, controlling a wide range of insect pests
[3]. It has two chiral centers, in the acid and alcohol moieties, and thus contains four stereoisomers with
*

Corresponding author. Tel.: +6-011-185-93681; fax: +6-053-687-649

E-mail address: tonga.tnt@gmail.com

2212-6708 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection and peer review under responsibility of Asia-Pacific Chemical, Biological & Environmental Engineering Society
doi:10.1016/j.apcbee.2014.03.018

152

Nga T.T. Tran et al. / APCBEE Procedia 8 (2014) 151 155

DS,2R-, DR,2S-, DR,2R-, and DS,2S- configurations [3]. Fenvalerate has the potential to accumulate in soil,
while its potential to pollute ground water is expected to be minimal because of its extreme lipophilic.
However, fenvalerate can combine with clay, soil, sediment particulates or organic material which present in
surface water in suspension form, and this raises the potential to pollute surface water [1].
In natural environment, pyrethroids can be degraded through several possible processes, including photodegradation, biodegradation, and hydrolysis [2]. Lutnicka stated that fenvalerates half-time in an aquatic
ecosystem was about 4 days [4]. Liu et al. reported their results on photo-degradation of deltamethrin and
fenvalerate under simulated natural conditions. In their study, photo-degradation of both pyrethroids follow
first-order kinetics under the conditions of different solvents (n-hexane and 50% methanol/water) and under
different light irradiations [2]. Colombo studied on photo-Fenton degradation of the insecticide esfenvalerate
in aqueous medium. Degradation results were significantly greater, and the rate of oxidation more rapid, using
a photo-Fenton (Fe3+) process compared with its Fe2+ counterpart [1].
Therefore, this research studied on UV/ozone degradation of fenvalerate in water. The effects of solvents,
pH and sodium nitrate on the degradation of fenvalerate using UV/ozone were investigated. In addition, the
photo-products were verified using gas chromatography mass spectrometry (GC-MS).
2. Experimental
2.1. Chemicals
Fenvalerate 91% was obtained from VIPESCO (Vietnam Pesticide Joint Stock Company). Acetonitrile
(HPLC grade), methanol (HPLC grade) and acetone (ACS) were obtained from J. T. Baker, while acetic acid
(glacial 99.8%) was from Merck.
2.2. Photodegradation Procedure
Fig. 1 depicts a schematic diagram of UV/ozone
1. Ozone generator
system. A Lino JSC Lin 4.2x model ozone generator
2. Desicator
3. Rotameter (1-10 L/min)
(Vietnam) with ozone production capacity of 2 g/h was
4. Ozone trap
5. Rotameter (1-3 L/min)
applied as ozone source. The output flow from ozone
6. Reactor
7. UV lamp
generator was split to two streams and the active one
8. Ozone sparger
adjusted by a rotameter (0.33 L/min) flowing through
the reactor. UV irradiation used a BT 014 model 14W
UVC-lighting lamp (1.5 cm i.d., 20 cm length; Taiwan).
The reactor was filled with 2 L of test solution and
covered by an aluminum foil to avoid any UV leakage.
Photo-degradations were conducted for two cases:
ozone and non-ozone. In those experiments, initial
Fig. 1. Schematic diagram of the experimental UV/ozone
concentration of fenvalerate was 50 M containing 5%
solvent which was acetone, acetonitrile or methanol. In UV/Ozone process, the effects of pH and sodium
nitrate on fenvalerate degradation were also investigated.

2.3. Analytical Procedures

Fenvalerate and photoproducts were analyzed by Agilent 7890A gas chromatography coupled to an
Agilent 5975C mass spectrometer. Qualitative analysis was carried out on a HP-5MS (30m x 250m i.d.;

153

Nga T.T. Tran et al. / APCBEE Procedia 8 (2014) 151 155

0.25m). For GC method, the GC oven temperature was programmed as follows: 80C, hold for 0 min,
10C/min to a next temperature of 220C, hold for 1 min, 5C/min to a final temperature of 280C, hold for
13 min. Injector and detector temperature were set at 280 and 300C respectively. The 1 L sample was
injected into GC with split (5:1) mode. Helium was used as carrier gas at the rate of 1 mL/min.
Quantitative analysis was carried out by Agilent 1200 HPLC. In this study, a Gemini C18 column (5 m,
4.6 x 250 mm, Phenomenex) was applied. The mobile phase was methanol/acetic acid 0.01% (85:15). The
chromatographic conditions were: oven temperature 40oC; flow rate 1.0 mL/min; injection volume 80 L; and
the Diode Array Detector (DAD) registered signals at wavelengths of 204, 212 and 254 nm.
3. Results and Discussion
3.1. UV/ozone Process
When using ozone, fenvalerate degraded slowly. The degradation yield was only 5% after 90 min of
reaction time (Fig. 2a). Its degradation rate was faster (above 80%) under UV irradiation. In the 5% acetone
solution, UV/ozone combination enhanced and accelerated the degradation of fenvalerate because fenvalerate
was degraded not only by direct photolysis but also by hydroxyl radicals mechanism [5] and [6]. On the other
hand, UV/ozone treatment was more actively than individual agent in 5% ACN solution, and photodegradation of fenvalerate was rapidly.
Fenvalerates degradation yields of UV/ozone process in ACN or MeOH were higher compared in acetone
(Fig. 2b). In 5% ACN or MeOH solution, it took only 5 minutes to degrade 99% fenvalerate, while
approximately 20% removal was achieved in 5% acetone solution. The rate of photo-degradation in MeOH
was lower than in ACN but significantly faster than in acetone. The Neperian Logarithm of percentage
fenvalerate versus reaction time was plotted and found to be linear. Similar to Lius result, UV/ozone
degradation rate of fenvalerate could be described by the kinetic equations of pseudo-first order reactions [2].
100

ln(C/C0) = -0.05 x t
2

R = 0.9992

ln(C/C0) = -0.942 x t
-2

60

ln(C/C0)

Degradation yields, %

80

5% Acetone-UV/Ozone
5% Acetone-UV
5% ACN-UV/Ozone
5% ACN-UV
5% ACN-Ozone
(a)

40
20

R = 0.9941

5% ACN
5% Acetone
5% MeOH

-4

ln(C/C0) = -1.08 x t
2

R = 0.9741

-6

(b)

0
0

20

40

60

80

10

15

20

25

30

Treatment time, min

Treatment time, min

100

100

80

80

Degradation yields, %

Degradation yields, %

Fig. 2. (a) Degradation yield of fenvalerate under UV and/or 1L/min ozone; (b) Effect of solvent onto degradation rate by UV/ozone.

pH 8.5
pH 7.3
pH 5.8

60
40
20

(a)

UV/O3-NaNO3 10mM

60

UV/O3-NaNO3 7.5mM
UV/O3-NaNO3 5mM

40

UV/O3-NaNO3 2.5mM
UV/O3

20

(b)

Treatment time, min

Treatment time, min

Fig. 3. Effect of pH (a) and NaNO3 concentration (b) onto UV/ozone degradation of fenvalerate in 5% ACN solution

154

Nga T.T. Tran et al. / APCBEE Procedia 8 (2014) 151 155

Fig. 3a demonstrates that the degradation efficiency also increased as pH of reaction solution increased. It
can be explained that the hydrolytic stability of fenvalerate in alkaline medium is lower than in acidic
medium [7]. On the other hand, decomposed ozone generates more free radicals in water as pH increases [5].
Higher pH lightly increases the degradation yield, but pH adjustment will increase more costs in the real
treatment systems [8]. Beltran mentioned in his book that nitrites and nitrates, usually found in natural water,
also act as indirect photosensitizers to produce secondary oxidants such as hydroxyl radicals [5]. The presence
of sodium nitrate enhanced degradation yield, and reached a maximum at sodium nitrate concentration of
2.5 mM (Fig. 3b). Liu also reported a similar result within range of suitable concentration around 2 mM [2].
3.2. Photo-degradation Products
Fig. 4 shows HPLC chromatograms of UV/ozone treated fenvalerate samples in different mediums. On
these chromatograms, fenvalerate (peak III) was presented by the split peak due to its stereoisomers. Peaks I
and II, before fenvalerate peak, were products of photo-degradation process because they did not appear at
initial time of the reaction and increased due to the increase of treatment time. After 5 minutes, fenvalerate
was completely degraded except 5% acetone solvent. However, peaks I and II still existed even when
treatment time was extended to 90 minutes. It means that the products from photo-degradation of fenvalerate
were more difficult to degrade comparing with fenvalerate. In contrast to ACN and MeOH, acetone solvent
reduced the photo-degradation of fenvalerate as in Fig. 4a.
To confirm structure of photo-products, 1000 M fenvalerate sample in 100% ACN treated with UV was
analyzed with GC-MS as in Fig. 5a. Some photo-products were detected using NIST 2008 library and some of
them were tentatively assigned based on their mass spectrum and referred Katagi and Lius researches on
photo-degradation of fenvalerate [2] and [9]. The results are shown in Table 1 and the formation pathways of
photoproducts are demonstrated in Fig. 5b.
350

III

250
200

0 min
5 min
90 min

I II

150
100

(a)

50
0
-50
0

10

12

14

16

18

350

III

Fen 50PM-5% ACN-UV/O3

300
250
200

UV signal (204nm), relative

Fen 50PM-5% Acetone-UV/O3

300

UV signal (204nm), relative

UV signal (204nm), relative

350

0 min
5 min
90 min

I II

150
100

(b)

50
0
-50
0

10

12

Retention time, min

Retention time, min

14

16

18

Fen 50PM-5% MeOH-UV/O3

300
250

III

I II

0 min
5 min
90 min

200
150
100

(c)

50
0
-50
0

10

12

14

16

Retention time, min

Fig. 4. HPLC chromatograms of UV/ozone degradation samples in various solvents. (a) 5% acetone; (b) 5% ACN; (c) 5% MeOH

4x10

3x10

90 min

2x10

Total ion - TIC

1x10
5
4x100

45

89

30 min

3x10

2x10

1x10
5
4x100
5

0 min

3x10

2x10

(a)

1x10
0
6

10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40

Retention time, min

Fig. 5. (a) GC-MS chromatograms of UV degradation sample in 100% ACN; (b) Photo-degradation pathways of fenvalerate

18

155

Nga T.T. Tran et al. / APCBEE Procedia 8 (2014) 151 155

Table 1. Photochemical degradation intermediates of fenvalerate

Fig. 4

Fig. 5b

m/z (a Molecular ions )

Peak

RT (min)

Product

6.828

4-chloro-benzaldehyde

139a, 111, 75, 50

9.888

4-Chlorobenzoic acid, 2-methoxyethyl ester

139, 111, 75

13.790

3-phenoxy-benzaldehyde

6, 7

28.5-29.2

3-(4-chlorophenyl)-4-methyl-2-(3-phenoxyphenyl)pentanenitrile

8, 9

31.7-32.3

Fenvalerate

198a, 181, 167, 141

I, II

375a, 209, 167, 125

III

419a, 209, 181, 167, 125

4. Conclusions
UV/ozone process showed an enhancement and acceleration on degradation of fenvalerate compared with
using single process (UV or ozone). UV/ozone degradation rate of fenvalerate could be described by the
kinetic equations of pseudo-first order reactions. Degradation rate in MeOH was lower than in ACN but it was
significantly faster than in acetone. The treatment process in 5% ACN solution obtained 99% removal yield
after 5 minutes of reaction time. When pH was increased, the degradation efficiency was also increased.
Moreover, the presence of sodium nitrate enhanced degradation yield, and the degradation efficiency reached
an optimum sodium nitrate concentration of 2.5 mM. Finally, UV/ozone degradation process had more
efficient than other processes so that it could be applied as a water treatment method for contaminated
fenvalerate in water.
Acknowledgements
This study was financially supported by the VNU-HCM, and the Key Laboratory of Chemical and
Petroleum Technology, VNU-HCM.
References
[1] Colombo R., Ferreira T. C. R., Alves S. A., and Lanza M. R. V. Photo-Fenton degradation of the insecticide esfenvalerate in
aqueous medium using a recirculation flow-through UV photoreactor. Journal of Hazardous Materials 2011; 198: 3705.
[2] Liu P., Liu Y., Liu Q., and Liu J. Photodegradation mechanism of deltamethrin and fenvalerate. Journal of Environmental
Sciences 2010; 22: 11238.
[3] Ma Y., Chen L., Lu X., Chu H., Xu C., and Liu W. Enantioselectivity in aquatic toxicity of synthetic pyrethroid insecticide
fenvalerate. Ecotoxicology and Environmental Safety 2009; 72: 19138.
[4] Lutnicka H., Bogacka T., and Wolska L. Degradation of pyrethroids in an aquatic ecosystem model. Water Research 1999; 33:
34416.
[5] J. Beltran F. Chemical Degradation Methods for Wastes and Pollutants - Chapter 1. Marcel Dekker; 2003.
[6] Catalkaya E. C. and Kargi F. Color, TOC and AOX removals from pulp mill effluent by advanced oxidation processes: A
comparative study. Journal of Hazardous Materials 2007; 139: 24453.
[7] Lee P. W. Fate of fenvalerate (Pydrin insecticide) in the soil environment. J. Agric. Food Chem. 1985; 33: 9938.
[8] Melin G. Treatment Technologies for Removal of Methyl Tertiary Butyl Ether (MTBE) from Drinking Water - Chapter 3 Advanced Oxidation Processes. Center for Groundwater Restoration and Protection -National Water Research Institut; 1999.
[9] Katagi T. Photodegradation of the pyrethroid insecticide esfenvalerate on soil, clay minerals, and humic acid surfaces. J. Agric.
Food Chem. 1991; 39: 13516.