Journal of Industrial and Engineering Chemistry 19 (2013) 305–309

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Journal of Industrial and Engineering Chemistry

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Mechanism and kinetic study for the degradation of lindane by photo-Fenton

process
Ines Nitoi a, Tatiana Oncescu b, Petruta Oancea b,*
a
National Research & Development Institute for Industrial Ecology – ECOIND, Sos. Panduri 90-92, Bucharest 050663, Romania
b
Department of Physical Chemistry, Faculty of Chemistry, University of Bucharest, Bd. Elisabeta 4-12, Bucharest 030016, Romania

A R T I C L E I N F O A B S T R A C T

Article history: Because application of classical treatment methods cannot allow an easily Lindane (gamma
Received 13 June 2012 1a,2a,3b,4a,5a,6b-hexachlorocyclohexane) degradation, development of more powerful water
Accepted 19 August 2012 treatment techniques, like advanced oxidation processes (AOPs), was necessary. The degradation of
Available online 24 August 2012
lindane (g-HCH) has been studied using the photo-Fenton reaction. The degradation kinetics under
irradiation was optimized in respect to H2O2 concentration and Fe2+ concentration at a constant lindane
Keywords: concentration. The degradation rate follows pseudo-first order kinetics with respect to lindane and
Lindane
organic clorine mineralization. Application of photo-Fenton system also assures total organic carbon
Photo-Fenton
removal with 95% efficiency at 2 h irradiation. The possible pathways of lindane photodegradation is also
Kinetic model
Advanced oxidation processes proposed.
ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction element and hydrogen peroxide is easy to handle and environ-

g-HCH, also called lindane, the active component of HCH
technical insecticide, had been widely used in agriculture
throughout the world since the 1940s. The production and
agricultural use of lindane are the primary causes of environmental
contamination [1]. The production of lindane generates large
amounts of waste hexachlorocyclohexane isomers, and it is
estimated that every ton of lindane manufactured produces about
9 tons of toxic waste [2].
The traditional treatment technologies applied for the removal
of pesticide from contaminated ground/wastewater, such as
coagulation, flocculation, membrane separation or adsorption on
activated carbon, only do a phase transfer of the pollutant.
A modern oxidation technology like the photo-Fenton process
has been applied for the degradation of several classes of pesticides
and refractory compounds [3–5]. Generally, Fenton process
involves application of iron salts and hydrogen peroxide to
produce hydroxyl radicals. This reaction is spontaneous and can
occur without the influence of light [4].
Fe2þ þ H2 O2 ! Fe3þ þ HO þ OH
This reagent is an attractive oxidative system for wastewater
treatment due to the fact that iron is very abundant and non-toxic
* Corresponding author.
E-mail address: petrutaoancea73@yahoo.com (P. Oancea).
mentally safe. The rate of pollutants degradation can be consider-
ably increased via photochemical reaction in the UV/Fenton
processes [6–8]. In this case the regeneration of Fe2+, with
production of new OH radicals, follows a photoreduction process:
Fe3þ þ H2 O ! FeðHOÞ2þ þ Hþ (2)
FeðOHÞ2þ þ hn ! Fe2þ þ HO (3)
In photo-Fenton process, in addition to the above reactions, the
formation of hydroxyl radicals occurs also by the following
reactions:
Fe3þ þ H2 O þ hn ! HO þ Fe2þ þ Hþ (4)
H2 O2 þ hn ! 2HO (5)
Prior studies have shown that g-HCH undergoes dehydrochlo-
rination in heterogeneous catalytic reduction system with Pd/C, Pt/
C and Roney-Ni [9] and with Pd/Al2O3 [10] to yield benzene as the
(1)
major final product. In addition, the photochemical transformation
of lindane in the presence of humate-coated a-Fe2O3 has been
reported also [11]. Other studies revealed that lindane is very
resistant to degradation by ozonation [12]. Only a few studies like
Nienow et al. [13] focused on the application of advanced oxidation
processes for lindane degradation in UV/H2O2 system, limited data
being available for photo-Fenton degradation of g-HCH (lindane).

1226-086X/$ – see front matter ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2012.08.016
306 I. Nitoi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 305–309

In the present study, we investigated the lindane degradation 2

and organic chlorine mineralization in synthetic water solution by 2.0 R =0.9983
photo-Fenton process. The influence of working conditions
(Fenton’s reagents doses, irradiation time) on the process
efficiency was investigated. 1.5

lnL0 /L
2. Materials and methods b
1.0
2.1. Materials

The following reagents were used: g-HCH lindane (Merck) of 0.5

99% purity; hydrogen peroxide solution (Merck) reagent-grade
30 wt.% solution; FeSO47H2O (Merck) 98 wt.% purity, Na2SO3
(Merck) 98 wt.% purity used for the removal of unconsumed H2O2 0.0
from irradiated samples; KI (Merck) 99 wt.% purity and Na2S2O3 0 10 20 30 40 50 60
(Fluka) 0.1 N used for iodometric determination of H2O2; n-hexane t, min.
(UniSolv) GC grade was used for lindane extraction from aqueous
Fig. 1. First order reaction kinetic for the degradation of lindane (L) by photo-Fenton
samples.
oxidation: [L]0 = 3.47  106 M, [H2O2] = 2.94  103 M, and [Fe2+] = 0.147 
103M, pH 3.
2.2. Methods

The photodegradation experiments were carried out in a k2

L þ  OH!Lox (7)
laboratory scale UV reactor – Heraeus system using a medium-
pressure mercury lamp which emits in the UV–vis range (l = 240–
k3
500 nm). The lamp equipped with a quartz water cooling jacket is Fe2þ þ  OH!Fe3þ þ HO (8)
immersed in the center of the reactor containing the pollutant
solution. The synthetic solutions with Lindane content were k4
magnetically stirred. The photon’s flow of the emitted radiations Fe3þ þ H2 O þ hn!Fe2þ þ  OH þ Hþ (9)
was determined by ferrioxalate actinometry [14] and a value
I0 = 6  106 einstein s1 was found. Solution with 1010 mg/L H2 O2 þ hn!2 OH
k5
(10)
(3.47 mM) content of lindane was photo-oxidized in the following
working conditions: pH = 3; molar ratio [Fe2+]:[H2O2] = 1:20–1:8; k6
tirr = 1–4 h. H2 O2 þ  OH! OOH þ H2 O (11)
We mention that the selection of working pH was made
considering that Fe3+ ions resulted from the Fe2+ catalytic k7
Fe3þ þ H2 O2 !Fe2þ þ HO 2 þ Hþ (12)
generation of OH radicals (1) are hydrolyzing at pH > 3 forming
photoinactive insoluble hydroxospecies. The rate of lindane oxidation is:
In order to determine the yields for lindane degradation and
organic chlorine mineralization, the initial and irradiated samples d½L
 ¼ k2 ½ OH½L (13)
were analyzed for pollutant and Cl concentrations by gas- dt
chromatography (GC-ECD) and ion chromatography (IC), respec- in which k2 is the rate constant of process (7).
tively. For irradiated samples, the GC and IC analyses were The concentration of OH obtained by applying steady-state
performed after sample pretreatment by dosage of Na2SO3 in order assumption are:
to remove the unconsumed oxidizing agent (concentration
determined by iodometric method). All experiments were d½ OH
¼ k1 ½Fe2þ ½H2 O2  þ k4 ½Fe3þ ½H2 O þ 2k5 ½H2 O2   k2 ½L½ OH
duplicated to assure data quality. dt
 k3 ½Fe2þ ½ OH  k6 ½ OH½H2 O2  ¼ 0 (14)

3. Results and discussions The value of k4 is very low (3.33  106 M1 s1) [15], so that, the
term k4 ½Fe3þ ½H2 O can be neglected.
3.1. Kinetic study Combining Eq. (13) with (14) yields:

In the present study, zero, first and second order reaction d½L k2 ½L½H2 O2 ðk1 ½Fe2þ  þ 2k5 Þ
 ¼ (15)
kinetics were tested to investigate the degradation of lindane by dt k2 ½L þ k3 ½Fe2þ  þ k6 ½H2 O2 
photo-Fenton process, k0, k1, k2 being their apparent kinetic rate
constants. Comparing the regression coefficients (R2) obtained by Therefore Eq. (15) leads to:
graphical representation we concluded that first-order reaction
kinetics fits best (R2 = 0.9983) (Fig. 1). ½L½H2 O2  k2 ½L þ k3 ½Fe2þ  þ k6 ½H2 O2 
¼ (16)
From the slope, a first order rate constant kI = 3.48  104 s1 ðd½L=dtÞ k2 ðk1 ½Fe2þ  þ 2k5 Þ
was calculated.
Indeed Eq. (13) apparently follows first order kinetics due to the
Our experiments carried out at different initial concentrations
excess of OH radical in comparison with the pollutant:
of lindane pointed out the variation of kI with concentration. The
following reactions confirm this affirmation: d½L
 ¼ kapp ½L ¼ kI ½L (17)
dt
k1
Fe2þ þ H2 O2 !Fe3þ þ  OH þ HO (6) kI being the pseudo-first-order rate constant determined before.
 I. Nitoi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 305–309 307

8
22
Cl -2 -1
R2 =0.9916 7
k I= (7.40 +/- 0.039) x 10 min
20 2
R =0.9999
6
18
[H 2 O 2 ]/k app Ms

-ln(1-Cl-t/Cl-)
16
4
14
3
12
2
10
1
8
0.00 7.50x10-7 1.50x10-6 2.25x10-6 3.00x10-6 3.75x10-6 0
0 10 20 30 40 50 60 70
[L] 0 , M
t, min.
Fig. 2. The relationship between [H2O2]/kapp and [L]0; [Fe2+] = 0.368  103 M; Fig. 3. First-order-kinetic for mineralization of Cl for [L]0 = 3.47  106 M;
[H2O2] = 7.35  103 M, pH = 3, 60 min of irradiation. [Fe2+] = 3.676  103 M; [H2O2] = 29.41  103 M; [Fe2+]/[H2O2] = 1/8.

The initial condition of photo-Fenton conjoining Eqs. (16) and Cl -

3.5x10 -6
(17) lead to:
3.0x10 -6 1/8
½H2 O2 0 k3 ½Fe2þ 0 þ k6 ½H2 O2 0 ½L0 1/20
¼ 2þ
þ 2þ
(18) 1/10
kapp k2 ðk1 ½Fe 0 þ 2k5 Þ k1 ½Fe 0 þ 2k5
Concentration, M
-6
2.5x10

From the slope of the graphical representation of Eq. (18) (Fig. 2) 2.0x10 -6
results the rate constant k1 = 272 M1 s1 and from the intercept
results the rate constant k2 = 1.39  105 M1 s1 of process (7). 1.5x10 -6
The value obtained for k2 shows that the oxidation of lindane is
not diffusion controlled. 1.0x10 -6
1/10
H2O2 plays a very important role as a source of OH generation Lindane
1/8
in photo-Fenton’s reaction. The effect of the concentrations of H2O2 5.0x10 -7 1/20
on photodegradation of lindane was put into evidence varying the
initial concentration of H2O2 from 7.35  103 to 29.41  103 M 0.0
but maintaining constant the initial pollutant concentration 0 10 20 30 40 50 60
3.47  106 M at molar ratio [Fe2+]:[H2O2] = 1:20. The results t, min
obtained are presented in the Table 1.
Fig. 4. Kinetic curves of lindane degradation and organic chlorine mineralization to
From Table 1 results a slight increase of rate constant with the
molar ratios 1/20, 1/10 and 1/8.
increase of H2O2 and Fe2+ concentrations which accelerate the
generation of OH taking into account (1), (3) and (5) reactions.
lindane 3.47  106 M and hydrogen peroxide 29.41  103 M
3.2. The influence of Fe 2+
concentration concentration. The results obtained under these conditions are
presented in the Table 2.
The increase of Fe2+ concentration has a similar effect on Within the investigated range of Fe2+ concentration, the rate
pollutant degradation as the increase of H2O2 concentration. We constant kapp value doubles. The increase of the molar ratio [Fe2+]/
studied the influence of Fe2+ concentration in the range of 1.47– [H2O2] at constant H2O2 concentration leads to higher OH
3.67  103 M, on the kinetic photodegradation at constant production in reactions (6) and (9) thus improving kapp.

Table 1
The influence of H2O2 concentration on the lindane photodegradation by UV/Fe2+/H2O2 system.

[L] (M) [H2O2] (M) [Fe2+] (M) [Fe2+]/[H2O2] kapp (s1)

3.47  106 7.35  103 0.36  103 1/20 (3.48  0.002)  104
3.47  106 14.71  103 0.75  103 1/20 (4.48  0.016)  104
3.47  106 22.06  103 1.10  103 1/20 (5.61  0.017)  104
3.47  106 29.41  103 1.47  103 1/20 (6.85  0.064)  104

Table 2
The influence of Fe2+ concentration on the lindane photodegradation by UV/Fe2+/H2O2.

[L] (M) [H2O2] (M) [Fe2+] (M) [Fe2+]/[H2O2] kapp (s1)

3.47  106 29.41  103 1.47  103 1/20 (6.85  0.064)  104
3.47  106 29.41  103 2.94  103 1/10 (12.9  0.041)  104
3.47  106 29.41  103 3.67  103 1/8 (13.25  0.086)  104
308 I. Nitoi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 305–309

Different optimum molar ratio of [Fe2+]/[H2O2] has been pro-
posed for the degradation of other pollutants in aqueous solution in
the range of 1:1 to 1:400 [16]. In the present study, the optimum
molar ratio [Fe2+]/[H2O2] = 1:8 was experimentally established.
In parallel with the study of lindane degradation, the organic
chlorine mineralization was evaluated. Calculated rate constants
for chloride release also follow first order kinetics. We exemplified
the data obtained for 3.67  103 M Fe2+ concentration and molar
ratio [Fe2+]/[H2O2] = 1/8 in Fig. 3.
Kinetic curves of organic chlorine mineralization and lindane
degradation at different molar ratios [Fe2+]/[H2O2] are presented
in Fig. 4.
Lindane concentration decreases faster in the first 30 min of
irradiation simultaneous with Cl release. After 1 h of irradiation,
advanced organic chlorine mineralization and lindane degradation
were registered. The first-order rate constants obtained in various
experimental conditions are summarized in Table 3.
In all cases, organic chlorine rate constants are slightly lower
than the corresponding lindane degradation rate constant in the
limit of experimental errors. This means that the chlorine is not
directly released from lindane molecules, but from its oxidation
intermediates formed during the photooxidation process.
3.3. Reaction mechanism
During the photooxidation experiments we identified by GC,
chlorinated intermediates such as hexachlorobenzene and
trichlorobenzene. Their concentrations decreased after 2 h, 95%

C H Cl
H C
. H . H
Cl
H HO Cl
C Hexachlorocyclohexane
C Cl radical
H -H2 H
C H Cl H
H C H Cl

Hexachlorocyclohexane
HO
. -H2O

Cl
Cl Cl
Hexachlorobenzene
Cl Cl

Cl

HO
. -HCl
Cl Cl

Cl Cl
1,2,3 Trichlorobenzene + 1,2,4 Trichlorobenzene
Cl
Cl

HO
. -HCl
OH OH

OH
OH
1,2,3 Trihydroxybenzene + 1,2,4 Trihydroxybenzene

OH

HO
. OH

O O

OH O
+

O OH

CO2 + H2O

Fig. 5. Reaction mechanism of lindane degradation.

 I. Nitoi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 305–309 309

Table 3
Rate constants kapp obtained for organic chlorine mineralization (kCl) and lindane (kL) for 3.47  106 M initial lindane concentration after 1 h irradiation.

[H2O2] (M) [Fe2+] (M) [Fe2+]/[H2O2] kLapp (s1) kCl

app (s
1
)
3 3 4
7.35  10 0.368  10 1/20 (3.48  0.002)  10 (2.51  0.064)  104
14.71  103 0.753  103 1/20 (4.48  0.016)  104 (4.26  0.041)  104
22.06  103 1.102  103 1/20 (5.61  0.017)  104 (5.01  0.086)  104
29.41  103 1.47  103 1/20 (6.85  0.064)  104 (6.46  0.051)  104
29.41  103 2.94  103 1/10 (12.9  0.041)  104 (10.33  0.076)  104
29.41  103 3.676  103 1/8 (13.25  0.086)  104 (12.33  0.058)  104

of the total organic carbon being removed. After 4 h of irradiation,
the efficiency of organic chlorine mineralization reached 99.91%.
This results shows that lindane is completely destroyed via same
intermediates with less chlorine atoms in the molecules. In the
light of these observations we proposed the following simplified
scheme for the reactions mechanism of the lindane degradation
(Fig. 5).
The mechanism proposed is in agreement with those
proposed by Zaleska [17] and Wang et al. [18] which studied
the reactions which take place in heterogenous photocatalytical
degradation of lindane. New experiments are necessary for the
identification of intermediates like trihydroxibenzene and
different hidroxyquinone isomer in order to complete this
mechanism.
3.4. Oxidation efficiency evaluation
In order to assess the process efficiency with respect to the
electrical energy consumption associated with the lindane
removal through photo-Fenton process we calculated the energy
per order of magnitude, EEO expressed in kWh/m3/order [19]:
P  1000
EEO ¼
60  logðci =c f Þ
where P, ci and cf are the power of UV lamp and the initial and final
lindane concentration, respectively. The calculated value under
our experimental conditions is 31.4 kWh/m3/order, which is a
acceptable value in terms of process costs [20].
4. Conclusions
In this work, we evaluated the oxidation capacity of the UV/
Fe2+/H2O2 system on lindane degradation from which resulted the
following conclusions:
- The kinetics of lindane degradation and organic chlorine
mineralization follow pseudo first-order kinetics.
- Optimal experimental conditions for the advanced degradation
of lindane at initial concentration of 3.47  106 M were:
pH = 3, [H2O2] = 29.41  103 M, [Fe2+] = 3.67  103 M, and
tir = 1 h.
- The value of kLapp higher than kCl
app confirms that chlorine
liberation does not take place simultaneously with the
attack of OH radical on lindane; chlorinated intermediates
formation during the photooxidation process was revealed by
GC–MS.
Acknowledgments
This work was supported by Project PNII 32-131 and the
strategic grant POSDRU/89/1.5/S/58852, Project ‘‘Postdoctoral
programme for training scientific researchers’’ cofinanced by the
European Social Found within the Sectoral Operational Program
Human Resources Development 2007–2013.
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