Applied Catalysis B: Environmental 101 (2011) 515–521

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Applied Catalysis B: Environmental

journal homepage: www.elsevier.com/locate/apcatb

Kinetics of dodecylbenzenesulphonate mineralisation by

TiO2 photocatalysis
Montserrat Sanchez, Maria J. Rivero, Inmaculada Ortiz ∗
Department of Chemical Engineering and Inorganic Chemistry, ETSIIT, University of Cantabria, Avda. de los Castros s/n, 39005 Santander, Spain

a r t i c l e i n f o a b s t r a c t

Article history: In this work, the kinetics of mineralisation of sodium dodecylbenzenesulphonate (DBS) by TiO2 pho-
Received 22 July 2010 tocatalysis has been studied. Although several works have studied the kinetics of photodegradation of
Received in revised form 14 October 2010 the primary pollutant, the formation of organic intermediates brings a worse situation when those com-
Accepted 19 October 2010
pounds are hardly oxidised. Total mineralisation is thus the desired objective in any oxidation process,
Available online 25 October 2010
being the kinetics a good indicator of the process efficacy. Working between 50 mg L−1 and 200 mg L−1 of
DBS and catalyst loadings between 0.5 g L−1 and 5 g L−1 , the mineralisation kinetics of DBS degradation
Keywords:
by TiO2 photocatalysis has been experimentally and theoretically analysed. The mineralisation kinetic
DBS
TiO2
curves presented two different zones with different slopes, the second one attributed to the intermediate
Mineralisation kinetics compounds and with a lower rate. Data in the two zones fitted to second order kinetic models with dif-
ferent values of the kinetic parameters. Additionally, the kinetics of DBS removal has also been analysed
observing that kinetic data corresponding to high surfactant concentration followed a second order trend
similar to the mineralisation results.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction properties in one molecule [2]. Unless removed prior to discharge

Wastewater recycling is emerging as an integral part of water-
demand management. Some of the reasons for its increasing
importance are that it can provide the preservation of high-quality
fresh-water supplies as well as potentially reduce environmental
pollution and overall water costs. Domestic water recycling is an
attractive option due to a relatively high domestic water consump-
tion coupled with high population density. Grey water is any type
of domestic water that comes from kitchen sinks, baths, wash-
ing machines and hand basins, excluding black waters (toilets and
urinals). Grey water characteristics vary according to geographi-
cal location, demographics and level of occupancy. It generally has
relatively low organic strength and does not have high suspended
solids or turbidity, indicating that a great proportion of the con-
taminants are dissolved [1].
Synthetic surfactants are commonly present in grey water due
to their presence in personal care products and detergents. Surfac-
tants are a diverse group of chemicals designed to have cleaning
or solubilisation properties. They generally consist of a polar head
group (either charged or uncharged) that is well solvated in water
and a nonpolar hydrocarbon tail, which is not easily dissolved in
water. Hence, surfactants combine hydrophobic and hydrophilic
∗ Corresponding author.
E-mail address: ortizi@unican.es (I. Ortiz).
or reuse, they will exert a biochemical oxygen demand (BOD) and
contribute to depletion of dissolved O2 . Low concentrations of sur-
factant (e.g., 1 mg L−1 ) are also toxic to certain fishes [3]. Linear
alkylbenzene sulphonates (LAS) are a type of anionic surfactants
that are relatively degraded under aerobic conditions, but only very
slowly or not all under anaerobic conditions [4].
Dodecylbenzenesulphonate (DBS) is an important anionic sur-
factant frequently used in shampoo formulations and in detergents
for washing machines [5] and is therefore commonly found in grey
water. This compound can cause ecological problems because its
biodegradation requires a period of two days, while branched iso-
mers of DBS are not biodegraded even after a week of exposure to
bacteria [6,7].
Several advanced oxidation processes have been applied to
DBS degradation such as Fenton, photo-Fenton, electro-oxidation,
ozonation, catalytic and non-catalytic wet air oxidation [8–10].
Recently, TiO2 photocatalysis has been used for the degrada-
tion of organic compounds. TiO2 is broadly used as a photocatalyst
because of its nontoxicity, photochemical stability and low cost
[11,12]. TiO2 photocatalysis is an advanced oxidation process in
which hydroxyl radicals, superoxide radical anions and hydroper-
oxyl radicals are produced [13,14]. The organic pollutants are
attacked and oxidised by these radicals. In addition to hydroxyl
radicals, superoxide radical anions – and in some cases the positive
holes – have also been suggested as possible oxidising species that
can attack organic compounds present at or near the surface of TiO2
[15].

0926-3373/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2010.10.023
516 M. Sanchez et al. / Applied Catalysis B: Environmental 101 (2011) 515–521

Literature offers several articles related to the degradation of
surfactants. Most of them report valuable fundamental and exper-
imental studies mainly investigating the evolution with time of
some parameters such as the surfactant concentration, CO2 [16–18]
and in some cases TOC [19,20]. Few articles report a theoretical
study of the degradation kinetics and when it is done it is referred
to initial times.
High removal percentages of the primary surfactant and the for-
mation of oxidation intermediates more stable than the surfactant
under the operating conditions have been observed. Thus, this work
aims at the theoretical and experimental analysis of the kinetics
of mineralisation of DBS contained in aqueous solutions through
the evolution of the DOC parameter. Thus, it is reported for the
first time the kinetic modelling of the mentioned photocatalytic
mineralisation offering a very useful tool for process design and
optimisation.
2. Experimental
2.1. Materials and reagents
Dodecylbenzenesulphonate (DBS) was obtained from
Sigma–Aldrich. The catalyst, TiO2 , was Degussa P 25 (Evonik).
HCl 0.1 N from Panreac was used in the experiments carried
out in acidic conditions and NaOH 32% from Panreac was used
in the experiments carried out in basic conditions. Deionised
water was supplied by a Milli-Q water purification unit (Millipore
Waters).
2.2. Experimental apparatus and procedure
from experimental data by Eq. (1):
V (Ci − Ce )
q= (1)
M
where q is the adsorbed amount (mmol g−1 ), V is the volume (L)
of solution, Ci is the initial DBS concentration (mmol L−1 ), Ce is the
equilibrium DBS concentration (mmol L−1 ) and M is the amount of
adsorbent (g).
All experiments were carried out at room temperature, and sam-
ples were filtered through a 0.45 ␮m polypropylene filter prior to
analysis.
The irradiation experiments were carried out in a batch 1.0 L
cylindrical glass photoreactor with a 150 W medium-pressure Hg
lamp with a maximum emission at 370 nm (Heraeus Noblelight
TQ 150 z1) immersed in a quartz sleeve placed in the middle of
the reactor. The reactor was surrounded by a water-cooling jacket
(PolyScience Digital Temperature Controller) to maintain constant
temperature. A magnetic stirrer (Selecta Agimatic-S) was used to
provide proper mixing. The amount of radiation emitted by the UV
lamp was 0.004 ␮Einsteins s−1 as determined by hydrogen perox-
ide actinometry experiments.
First, 0.75 L of DBS solution was mixed with TiO2 between
0.5 g L−1 and 5 g L−1 in the photoreactor. After 30 min of premixing
in the dark, photocatalytic degradation was initiated by switching
on the UV lamp. The suspension was sampled at defined time inter-
vals and passed through a 0.45 ␮m syringe filter prior to analysis.
Dissolved organic carbon (DOC) analysis was performed using a
Shimadzu TOC-V CPH analyser.
Ion chromatography (Dionex 120 IC with IonPac AS9-HC col-
umn) was employed to determine the concentrations of the organic
acids such as acetic acid and formic acid.

Adsorption equilibrium data were obtained by introducing 3. Results and discussion

0.1 g L−1 to 5 g L−1 of TiO2 into 100 mL of 10 mg L−1 or 150 mg L−1
DBS solutions in Falcon tubes. Equilibrium was reached after
30 min. The concentration of individual components was measured
with an UV–vis spectrophotometer (Thermo Genesys 10UV) in the
range of the linear relationship between absorbance and concen-
tration at 223 nm [6,21]. The adsorbed amount (q) was calculated
3.1. Adsorption of DBS onto TiO2
Experimental analysis of dark adsorption of DBS onto TiO2
was performed in order to determine the initial surfactant con-
centration on its photocatalytic degradation. Fig. 1 shows the

0.35 0.045
0.04
0.3 a b
0.035
0.25
0.03
q (mmolg-1)
q (mmolg )

0.2 0.025
0.15 0.02
0.015
0.1
0.01
0.05 0.005
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0 0.1 0.2 0.3 0.4 0.5 0.6
c (mmolL -1) c (mmolL-1)

0.016 0.025
0.014 c 0.02
d
0.012
q (mmolg-1)
q (mmolg )

0.01 0.015
0.008
0.01
0.006

0.004 0.005
0.002
0
0
0 0.1 0.2 0.3 0.4 0.5
0 0.05 0.1 0.15 0.2 0.25 0.3
c (mmolL )-1 c (mmolL-1)

Fig. 1. Adsorption isotherms at different TiO2 concentrations: (a) TiO2 = 0.1 g L−1 ; (b) TiO2 = 0.5 g L−1 ; (c) TiO2 = 2 g L−1 ; (d) TiO2 = 5 g L−1 .
 M. Sanchez et al. / Applied Catalysis B: Environmental 101 (2011) 515–521 517

Table 1
Adsorption isotherm parameters.
a 60
[TiO2 ] (g L−1 ) Kads (mM−1 ) qm (mmol g−1 ) 
50
0.1 26.14 0.32 0.39
0.5 26.14 0.039 1.91

DBS (mg L-1)

40
2 26.14 0.017 0.089
5 26.14 0.021 0.088
30

20
experimental data and the Langmuir-type isotherm obtained after
fitting the experimental data to Eq. (2): 10

qm Kads Ce 0
q= (2)
1 + Kads Ce 0 0 30 60 90 120 150 180 210 240 270 300 330 360 390
Dark
Adsorption Illuminating period (min)
where q is the amount of DBS adsorbed onto the TiO2 at equilibrium,
qm is the theoretical maximum amount of DBS adsorbed onto the
TiO2 surface, Ce is the DBS solution concentration at equilibrium
and Kads is the adsorption constant. b 35
The estimated values of qm and Kads and the weighted standard
30
deviation, calculated by Eq. (3), are listed in Table 1:
 25

DOC (mg L-1)

n 2
i=1
((Cexp − Csim )/Cexp )
= (3) 20
N−1
15
In general, qm decreased as TiO2 concentration increased, while
the Langmuir constant Kads did not vary, indicating that the adsorp- 10
tion density was higher for lower TiO2 concentrations because of 5
the limitation of TiO2 adsorption capacity [22].
0
0 0 30 60 90 120 150 180 210 240 270 300 330 360 390
3.2. Influence of solution pH Dark
Adsorption Illuminating period (min)

The effect of pH on DBS degradation is a complex issue since it

governs (i) the equilibrium of water dissociation which, in turn,
affects the level of hydroxyl radicals generation, (ii) the surface
charge of titania with respect to its point of zero charge (pzc) and,
(iii) the oxidative power of the photogenerated holes [23].
This study was carried out with an initial DBS concentration of
50 mg L−1 and a catalyst concentration of 5 g L−1 in the presence
of UV light. The kinetic evolution of DBS at different pH conditions
between 2.8 and 12.3 is shown in Fig. 2. The experiment performed
under basic conditions, pH 12.3, showed the lowest degradation
rate. The experiments performed at near-neutral solution pH (pH
5.8–6.5), the value depended on the initial DBS concentration due
to the dissociation of DBS in water, or at acidic conditions (pH 2.8)
showed slight differences during the first 120 min whereas in acidic
conditions higher DBS reductions were achieved. But after 120 min
the results at both acidic and natural pH results were similar. The
reason is that as reaction proceeds, solution pH is likely to drop
due to the formation of acidic by-products so both pH values were
similar.
0.16 pH=3
0.14
DBS (mmolL -1)
Fig. 3. Influence of catalyst dosage on the degradation (a) and mineralisation (b) of
50 mg L−1 of DBS. : [TiO2 ] = 0.5 g L−1 ; : [TiO2 ] = 2 g L−1 ; : [TiO2 ] = 5 g L−1 .
The zero-point charge (pzc) value of TiO2 is found at pH 6.25.
Therefore, the TiO2 surface is positively charged in acidic media
(pH < 6.25), whereas it is negatively charged under alkaline condi-
tions (pH > 6.25) [24]. The DBS molecule has a sulphate anion in its
structure, so under acidic conditions in which the TiO2 surface is
positively charged, the degradation of DBS should be higher than
in basic conditions.
3.3. Effect of photocatalyst dosage
The effect of TiO2 dosage on the DBS photodegradation rate was
investigated by varying TiO2 concentrations from 0.5 g L−1 to 5 g L−1
and working at a constant initial DBS concentration of 50 mg L−1 .
DOC analysis was carried out simultaneously to DBS measure-
ments to characterise surfactant mineralisation. Fig. 3 presents the
kinetic data for DBS and DOC photodegradation. The degradation
pH=6.5 pH=12 rate both for DBS and DOC was higher when the TiO2 concentration
was increased. The increase in the removal rate of DBS was likely
due to the increase in the total surface area (or number of active

0.12
0.1
sites) available for the photocatalytic reaction as the dosage of TiO2
increased.
0.08
The influence of the catalyst amount on the rate of DBS degrada-
0.06 tion was significant for times lower than 180 min. At longer times
0.04 the evolution of the DBS concentration was very similar for the
0.02
three amounts of catalyst used. It has been observed that when DBS
concentration is high, strong dependence on TiO2 concentration is
0
0 100 200 300 400
observed. But when DBS concentration is low, smaller quantity of
t (min) catalyst is required. Therefore, for long times of experiment, as DBS
concentration is similar in all the cases, the catalyst concentration
Fig. 2. Influence of pH on the photocatalytic degradation of DBS. is not a determining factor.
518 M. Sanchez et al. / Applied Catalysis B: Environmental 101 (2011) 515–521

Table 2
Parameters obtained from the DBS fitting to a pseudo-first and second order kinetic models.

[TiO2 ] g L−1 C0 (mg L−1 ) Ce (mg L−1 ) Pseudo-first order kinetic model Second order kinetic model
−1
kapp (min ) r 2
k (mg L−1 min−1 ) r2

0.5 50 46.86 1.46 × 10−2 0.98 5.09 × 10−4 0.99a

0.5 100 96.32 5.70 × 10−3 0.95 1.44 × 10−4 0.98
0.5 150 143.50 4.60 × 10−3 0.98 6.52 × 10−5 0.98
0.5 200 188.52 4.46 × 10−3 0.90 3.98 × 10−5 0.99
2 50 41.25 1.24 × 10−2 0.98 5.69 × 10−4 0.99a
2 100 90.65 8.80 × 10−3 0.94 1.98 × 10−4 0.99a
2 150 138.62 4.90 × 10−3 0.87 7.15 × 10−5 0.99
2 200 188.19 4.30 × 10−3 0.77 4.86 × 10−5 0.97
5 50 24.02 1.31 × 10−2 0.98 5.96 × 10−4 0.98a
5 100 67.59 8.40 × 10−3 0.94 2.22 × 10−4 0.98a
5 150 115.02 5.70 × 10−3 0.92 1.09 × 10−4 0.99
5 200 165.29 4.90 × 10−3 0.87 7.15 × 10−5 0.99
a
Fitted until CDBS ≈ 15 mg L−1 .

3.4. Kinetic modelling
3.4.1. DBS removal
Kinetic modelling of DBS photocatalytic degradation together
with the determination of the kinetic parameters is a necessary
step in process design and optimisation [22,24–26]. In the case
of DBS degradation, few attempts have been performed to obtain
suitable models. Hidaka et al. [17] reported the kinetic parameters
of the Langmuir–Hinshelwood model obtained from the fitting of
initial-rate values for one concentration of catalyst; they also com-
pared the degradation rate of DBS with the degradation rate of other
surfactants.
In addition to the Langmuir–Hinshelwood model, a pseudo-first
order kinetic model and a second order kinetic model (Eq. (4)) have
been used to describe the degradation kinetics of different com-
pounds [22,27,28]. In this work, experimental data were fitted to a
pseudo-first order kinetic model, Eq. (4):
−dC
= kapp C
dt
and to a second order kinetic model to describe the photocatalytic
oxidation behaviour of DBS, Eq. (5):
−dC
= kC 2 (5)
dt
where C (mg L−1 ) is the DBS concentration at time t, t (min) is the
reaction time, kapp (min−1 ) is the pseudo-first order kinetic con-
stant and k (mg L−1 min−1 ) is the second order kinetic constant.
The values of k were obtained by applying a least-squares regres-
sion analysis (Table 2).
In general, experimental data fitted well to the second order
kinetic model for the early minutes of irradiation when the DBS con-
centration is high. Some authors have also reported photocatalytic
results that fit to second order kinetics for different solutes [27,29].
A possible explanation for second order photodegradation kinet-
ics is the aggregation or dimer formation with increasing organic
compound concentration [29].
When the initial DBS concentration is higher than 150 mg L−1 ,
the whole kinetic curve can be described by a second order kinetic
model. But when the initial concentration is in the range between
(4)
50 mg L−1 and 100 mg L−1 only the initial part of the curve, that is

100
45
40 a 90 b
80
35
70
DBS (mgL-1)

DBS (mgL-1)

30
60
25 50
20 40
15 30
10 20
5 10
0 0
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
t (min) t (min)
160
c 180
140
160
d
120
140
DBS (mgL-1)

DBS (mgL-1)

100 120

80 100
80
60
60
40
40
20 20
0 0
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
t (min) t (min)

Fig. 4. Pseudo-first order kinetic model ( ) and second order kinetic model ( ) for TiO2 = 2 g L−1 and (a) DBS = 50 mg L−1 ; (b) DBS = 100 mg L−1 ; (c)
DBS = 150 mg L−1 ; (d) DBS = 200 mg L−1 .
 M. Sanchez et al. / Applied Catalysis B: Environmental 101 (2011) 515–521
Fig. 5. Parity plot of DOC calculated theoretically from identified compounds and
DOC measured concentration.
for DBS concentrations higher than 15 mg L−1 is described satisfac-
torily by the second order kinetic model while the second part of
the experimental data is better described by a pseudo-first order
kinetic model. Experiments carried out with low concentrations are
usually described by the pseudo-first order kinetic model [27]. Fig. 4
shows the comparison of the experimental data and the simulated
curves with the pseudo-first and second order kinetic models.
In general, the value of the second order kinetic constant was
lower when the amount of DBS was increased for the same amount
of catalyst.
3.4.2. Mineralisation of DBS
DOC analyses were carried out simultaneously to DBS measure-
ments in order to characterise the surfactant mineralisation.
For a catalyst concentration of 5 g L−1 and a DBS amount of
50 mg L−1 , DBS removal reached 97% and DOC removal 91% after
360 min of photocatalytic degradation. Besides, the worst DOC
removal was about 22% after 360 min of irradiation, while the DBS
removal was about 77% when the catalyst dosage was 0.5 g L−1 and
the DBS concentration 200 mg L−1 . Thus, the mineralisation effi-
ciency was always lower than DBS degradation but this difference
increased when the initial concentration of DBS was relatively high
and TiO2 concentrations were low. The difference between the min-
eralisation and the degradation processes implied that there were
transient organic intermediates present in the photocatalytic sys-
tem that had not been completely mineralised [27,30].
The results showed that complete mineralisation was reached
after 360 min corresponding to a final DOC lower than 10 mg L−1 ,
when the initial DBS concentration was 50 mg L−1 and 100 mg L−1
excluding the experiment operated at a catalyst concentration of
0.5 g L−1 and DBS concentration of 50 mg L−1 .
Several mechanisms of cleavage for degradation of DBS could
be expected: decarboxylation of alkyl-side chain, aromatic ring
cleavage including desulphonation and conversion of short chain
carboxylic acids to CO2 and H2 O [10]. The mineralisation was
Table 3
Parameters obtained from the TOC fitting to a second order kinetic model in two stages.
[TiO2 ] g L−1 C0 (mg L−1 ) Ce (mg L−1 ) TOC parameters
k (First stage) (mg L−1 min−1 )
−4
0.5 50 46.86 2.11 × 10
2 50 41.25 3.80 × 10−4
2 100 90.65 1.99 × 10−4
5 50 24.02 1.93 × 10−4
5 100 67.59 1.71 × 10−4
519
followed through the analysis of some intermediate compounds
formed in the oxidation route of DBS. Organic acids such as acetic
acid and formic acid were detected in all the experiments. The theo-
retical DOC was quantified from the amount of DBS and the organic
acids analysed. Fig. 5 shows the parity plot showing that measured
DOC values matched up with calculated values for the initial data of
every experiment when most of DOC is due to DBS. As intermediate
compounds were not fully detected, the deviation increased with
reaction time.
When the mineralisation was not complete, the discrepancy
between measured DOC and calculated DOC was attributed to
intermediate compounds not fully detected. At short reaction
times (i.e. 40 min), this discrepancy was relatively low because
most of DOC was due to DBS; but after prolonged irradiation (i.e.
360 min), the difference between measured DOC and calculated
DOC increased. At the end of the experiments some short carboxylic
acids were identified, but other end-products were not quantified.
Similar results have been observed by Velegraki and Mantzavinos
[31].
Accumulation of acetic acid during oxidation increased with
time up to 13.5 mg L−1 . However, formic acid was variable and it
was identified at very low concentrations less than 2 mg L−1 . Simi-
lar results have been obtained applying wet air oxidation (WAO) to
DBS degradation [10]. SO4 −2 was also analysed in order to identify
the products of the reaction. The appearance of this anion comes
from the aromatic ring cleavage, one step of DBS degradation [10].
Hidaka et al. [6] also observed SO4 −2 appearance during the pho-
tocatalytic degradation of DBS.
It was also observed that mineralisation took place in two stages
as it is shown in Fig. 6. The first stage was fitted to a second order
kinetic model using Eq. (5). The second stage was also fitted to a sec-
ond order kinetic model that could be justified by considering that
the reaction rate does not depend only on the initial substrate con-
centration but also on intermediate compounds recently formed
but using the following equation:
−dCDOC
= kCDOC C(DOC)i (6)
dt
where CDOC is the dissolved organic carbon concentration at time t
in mg L−1 , t is the time in min, C(DOC)i is the dissolved organic carbon
concentration due to the organic intermediates and k is the second
order kinetic constant. Considering that the formation of organic
intermediates is proportional to time (Eq. (7)):
C(DOC)i = at (7)
The resulted equation is Eq. (8):
−dCDOC
= k CDOC t (8)
dt
where k is the modified kinetic constant in min−2 .
The first stage could mainly correspond to DBS removal due to
the same tendency in the kinetics of DBS disappearance. The second
stage, when most of the DBS has disappeared, is mostly due to DBS
degradation intermediates.
The values of the kinetic constants are shown in Table 3.
r2 k (Second stage) (min−2 ) r2
−5
0.99 1.64 × 10 0.99
0.87 1.87 × 10−5 0.99
0.81 1.81 × 10−5 0.93
0.99 7.64 × 10−6 0.94
0.88 5.54 × 10−6 0.94
520 M. Sanchez et al. / Applied Catalysis B: Environmental 101 (2011) 515–521

35
30
30
a b
25
DOC (mgL-1) 25
20

DOC (mgL-1)
20
15
15

10 10

5 5

0
0
0 100 200 300 400
0 100 200 300 400
t (min) t (min)

16 60

14
c d
50
12
40

DOC (mgL-1)
DOC (mgL-1)

10
30
8

6 20

4 10

2
0
0 0 100 200 300 400
0 100 200 300 400 t (min)
t (min)

45
40
e
35
30
DOC (mgL-1)

25
20
15
10
5
0
0 100 200 300 400
t (min)

Fig. 6. Fitting of DOC in two stages to the second order kinetic models for (a) DBS = 50 mg L−1 and TiO2 = 0.5 g L−1 ; (b) DBS = 50 mg L−1 and TiO2 = 2 g L−1 ; (c) DBS = 50 mg L−1
and TiO2 = 5 g L−1 ; (d) DBS = 100 mg L−1 and TiO2 = 2 g L−1 ; (e) DBS = 100 mg L−1 and TiO2 = 5 g L−1 . : experimental data; : simulated model.

4. Conclusions
In this work, adsorption of DBS onto TiO2 was evaluated in
terms of the Langmuir isotherm, obtaining a Kads value of 26 mM−1 .
The experimental results derived from the photocatalytic treat-
ment demonstrated that the natural pH of the solution (5.8–6.5)
was more suitable for DBS degradation than basic pH (12.3). Fur-
thermore, increasing the TiO2 dosage from 0.5 g L−1 to 5 g L−1
contributed positively to DBS photocatalytic degradation.
The kinetics of mineralisation of DBS by TiO2 photocatalysis has
also been studied. Complete mineralisation was achieved when the
initial concentration of DBS was 50 mg L−1 and 100 mg L−1 . DOC
data were fitted with two different second order kinetic models
in two stages considering that at the beginning of the process DBS
concentration was dominant but as long as photocatalysis occurred,
intermediate compounds increased their proportion. The first stage
was fitted up to 60–90 min and the kinetic constants lay between
1.71 × 10−4 mg L−1 min−1 and 3.80 × 10−4 mg L−1 min−1 . The sec-
ond stage (from 60–90 min to 360 min) kinetic constant values
were between 1.64 × 10−5 min−2 and 5.54 × 10−6 min−2 .
Besides, the measured DOC and the theoretical DOC, calculated
from the analysed organic compounds, were compared. They were
relatively similar for the initial data, but as intermediate com-
pounds were not fully identified, the deviation increased with
reaction time. The kinetics of DBS degradation was fitted to pseudo-
first and second order kinetic models. In general, data fitted well
the second order kinetic model for the early minutes of irradiation
when DBS concentration was high. For low concentrations, experi-
mental data were better described by the pseudo-first order kinetic
model. Experiments carried out with low concentration are usually
described by pseudo-first order kinetic models. The value of the
second order kinetic constant decreased when the amount of DBS
increased for the same amount of catalyst and they lay between
3.98 × 10−5 mg L−1 min−1 and 5.96 × 10−4 mg L−1 min−1 .
Acknowledgements
Financial support from the Spanish Ministry of Education and
Science (CTQ2008-00690) and CONSOLIDER (CSD2006-44) are
gratefully acknowledged.
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