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

or reuse, they will exert a biochemical oxygen demand (BOD) and
Wastewater recycling is emerging as an integral part of water- contribute to depletion of dissolved O2 . Low concentrations of sur-
demand management. Some of the reasons for its increasing factant (e.g., 1 mg L−1 ) are also toxic to certain fishes [3]. Linear
importance are that it can provide the preservation of high-quality alkylbenzene sulphonates (LAS) are a type of anionic surfactants
fresh-water supplies as well as potentially reduce environmental that are relatively degraded under aerobic conditions, but only very
pollution and overall water costs. Domestic water recycling is an slowly or not all under anaerobic conditions [4].
attractive option due to a relatively high domestic water consump- Dodecylbenzenesulphonate (DBS) is an important anionic sur-
tion coupled with high population density. Grey water is any type factant frequently used in shampoo formulations and in detergents
of domestic water that comes from kitchen sinks, baths, wash- for washing machines [5] and is therefore commonly found in grey
ing machines and hand basins, excluding black waters (toilets and water. This compound can cause ecological problems because its
urinals). Grey water characteristics vary according to geographi- biodegradation requires a period of two days, while branched iso-
cal location, demographics and level of occupancy. It generally has mers of DBS are not biodegraded even after a week of exposure to
relatively low organic strength and does not have high suspended bacteria [6,7].
solids or turbidity, indicating that a great proportion of the con- Several advanced oxidation processes have been applied to
taminants are dissolved [1]. DBS degradation such as Fenton, photo-Fenton, electro-oxidation,
Synthetic surfactants are commonly present in grey water due ozonation, catalytic and non-catalytic wet air oxidation [8–10].
to their presence in personal care products and detergents. Surfac- Recently, TiO2 photocatalysis has been used for the degrada-
tants are a diverse group of chemicals designed to have cleaning tion of organic compounds. TiO2 is broadly used as a photocatalyst
or solubilisation properties. They generally consist of a polar head because of its nontoxicity, photochemical stability and low cost
group (either charged or uncharged) that is well solvated in water [11,12]. TiO2 photocatalysis is an advanced oxidation process in
and a nonpolar hydrocarbon tail, which is not easily dissolved in which hydroxyl radicals, superoxide radical anions and hydroper-
water. Hence, surfactants combine hydrophobic and hydrophilic 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
∗ Corresponding author. can attack organic compounds present at or near the surface of TiO2
E-mail address: [email protected] (I. Ortiz). [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 from experimental data by Eq. (1):
surfactants. Most of them report valuable fundamental and exper-
V (Ci − Ce )
imental studies mainly investigating the evolution with time of q= (1)
M
some parameters such as the surfactant concentration, CO2 [16–18]
and in some cases TOC [19,20]. Few articles report a theoretical where q is the adsorbed amount (mmol g−1 ), V is the volume (L)
study of the degradation kinetics and when it is done it is referred of solution, Ci is the initial DBS concentration (mmol L−1 ), Ce is the
to initial times. equilibrium DBS concentration (mmol L−1 ) and M is the amount of
High removal percentages of the primary surfactant and the for- adsorbent (g).
mation of oxidation intermediates more stable than the surfactant All experiments were carried out at room temperature, and sam-
under the operating conditions have been observed. Thus, this work ples were filtered through a 0.45 ␮m polypropylene filter prior to
aims at the theoretical and experimental analysis of the kinetics analysis.
of mineralisation of DBS contained in aqueous solutions through The irradiation experiments were carried out in a batch 1.0 L
the evolution of the DOC parameter. Thus, it is reported for the cylindrical glass photoreactor with a 150 W medium-pressure Hg
first time the kinetic modelling of the mentioned photocatalytic lamp with a maximum emission at 370 nm (Heraeus Noblelight
mineralisation offering a very useful tool for process design and TQ 150 z1) immersed in a quartz sleeve placed in the middle of
optimisation. 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
2. Experimental
provide proper mixing. The amount of radiation emitted by the UV
lamp was 0.004 ␮Einsteins s−1 as determined by hydrogen perox-
2.1. Materials and reagents
ide actinometry experiments.
First, 0.75 L of DBS solution was mixed with TiO2 between
Dodecylbenzenesulphonate (DBS) was obtained from
0.5 g L−1 and 5 g L−1 in the photoreactor. After 30 min of premixing
Sigma–Aldrich. The catalyst, TiO2 , was Degussa P 25 (Evonik).
in the dark, photocatalytic degradation was initiated by switching
HCl 0.1 N from Panreac was used in the experiments carried
on the UV lamp. The suspension was sampled at defined time inter-
out in acidic conditions and NaOH 32% from Panreac was used
vals and passed through a 0.45 ␮m syringe filter prior to analysis.
in the experiments carried out in basic conditions. Deionised
Dissolved organic carbon (DOC) analysis was performed using a
water was supplied by a Milli-Q water purification unit (Millipore
Shimadzu TOC-V CPH analyser.
Waters).
Ion chromatography (Dionex 120 IC with IonPac AS9-HC col-
umn) was employed to determine the concentrations of the organic
2.2. Experimental apparatus and procedure 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 3.1. Adsorption of DBS onto TiO2
30 min. The concentration of individual components was measured
with an UV–vis spectrophotometer (Thermo Genesys 10UV) in the Experimental analysis of dark adsorption of DBS onto TiO2
range of the linear relationship between absorbance and concen- was performed in order to determine the initial surfactant con-
tration at 223 nm [6,21]. The adsorbed amount (q) was calculated 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, 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 .
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 The zero-point charge (pzc) value of TiO2 is found at pH 6.25.
50 mg L−1 and a catalyst concentration of 5 g L−1 in the presence Therefore, the TiO2 surface is positively charged in acidic media
of UV light. The kinetic evolution of DBS at different pH conditions (pH < 6.25), whereas it is negatively charged under alkaline condi-
between 2.8 and 12.3 is shown in Fig. 2. The experiment performed tions (pH > 6.25) [24]. The DBS molecule has a sulphate anion in its
under basic conditions, pH 12.3, showed the lowest degradation structure, so under acidic conditions in which the TiO2 surface is
rate. The experiments performed at near-neutral solution pH (pH positively charged, the degradation of DBS should be higher than
5.8–6.5), the value depended on the initial DBS concentration due in basic conditions.
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 3.3. Effect of photocatalyst dosage
conditions higher DBS reductions were achieved. But after 120 min
the results at both acidic and natural pH results were similar. The The effect of TiO2 dosage on the DBS photodegradation rate was
reason is that as reaction proceeds, solution pH is likely to drop investigated by varying TiO2 concentrations from 0.5 g L−1 to 5 g L−1
due to the formation of acidic by-products so both pH values were and working at a constant initial DBS concentration of 50 mg L−1 .
similar. 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
0.16 pH=3 pH=6.5 pH=12 rate both for DBS and DOC was higher when the TiO2 concentration
0.14 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
DBS (mmolL -1)

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 and to a second order kinetic model to describe the photocatalytic
oxidation behaviour of DBS, Eq. (5):
3.4.1. DBS removal
Kinetic modelling of DBS photocatalytic degradation together −dC
= kC 2 (5)
with the determination of the kinetic parameters is a necessary dt
step in process design and optimisation [22,24–26]. In the case
where C (mg L−1 ) is the DBS concentration at time t, t (min) is the
of DBS degradation, few attempts have been performed to obtain
reaction time, kapp (min−1 ) is the pseudo-first order kinetic con-
suitable models. Hidaka et al. [17] reported the kinetic parameters
stant and k (mg L−1 min−1 ) is the second order kinetic constant.
of the Langmuir–Hinshelwood model obtained from the fitting of
The values of k were obtained by applying a least-squares regres-
initial-rate values for one concentration of catalyst; they also com-
sion analysis (Table 2).
pared the degradation rate of DBS with the degradation rate of other
In general, experimental data fitted well to the second order
surfactants.
kinetic model for the early minutes of irradiation when the DBS con-
In addition to the Langmuir–Hinshelwood model, a pseudo-first
centration is high. Some authors have also reported photocatalytic
order kinetic model and a second order kinetic model (Eq. (4)) have
results that fit to second order kinetics for different solutes [27,29].
been used to describe the degradation kinetics of different com-
A possible explanation for second order photodegradation kinet-
pounds [22,27,28]. In this work, experimental data were fitted to a
ics is the aggregation or dimer formation with increasing organic
pseudo-first order kinetic model, Eq. (4):
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
−dC model. But when the initial concentration is in the range between
= kapp C (4)
dt 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) 515–521 519

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.
Fig. 5. Parity plot of DOC calculated theoretically from identified compounds and Similar results have been observed by Velegraki and Mantzavinos
DOC measured concentration. [31].
Accumulation of acetic acid during oxidation increased with
for DBS concentrations higher than 15 mg L−1 is described satisfac- time up to 13.5 mg L−1 . However, formic acid was variable and it
torily by the second order kinetic model while the second part of was identified at very low concentrations less than 2 mg L−1 . Simi-
the experimental data is better described by a pseudo-first order lar results have been obtained applying wet air oxidation (WAO) to
kinetic model. Experiments carried out with low concentrations are DBS degradation [10]. SO4 −2 was also analysed in order to identify
usually described by the pseudo-first order kinetic model [27]. Fig. 4 the products of the reaction. The appearance of this anion comes
shows the comparison of the experimental data and the simulated from the aromatic ring cleavage, one step of DBS degradation [10].
curves with the pseudo-first and second order kinetic models. Hidaka et al. [6] also observed SO4 −2 appearance during the pho-
In general, the value of the second order kinetic constant was tocatalytic degradation of DBS.
lower when the amount of DBS was increased for the same amount It was also observed that mineralisation took place in two stages
of catalyst. 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
3.4.2. Mineralisation of DBS
the reaction rate does not depend only on the initial substrate con-
DOC analyses were carried out simultaneously to DBS measure-
centration but also on intermediate compounds recently formed
ments in order to characterise the surfactant mineralisation.
but using the following equation:
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 −dCDOC
= kCDOC C(DOC)i (6)
360 min of photocatalytic degradation. Besides, the worst DOC dt
removal was about 22% after 360 min of irradiation, while the DBS
where CDOC is the dissolved organic carbon concentration at time t
removal was about 77% when the catalyst dosage was 0.5 g L−1 and
in mg L−1 , t is the time in min, C(DOC)i is the dissolved organic carbon
the DBS concentration 200 mg L−1 . Thus, the mineralisation effi-
concentration due to the organic intermediates and k is the second
ciency was always lower than DBS degradation but this difference
order kinetic constant. Considering that the formation of organic
increased when the initial concentration of DBS was relatively high
intermediates is proportional to time (Eq. (7)):
and TiO2 concentrations were low. The difference between the min-
eralisation and the degradation processes implied that there were C(DOC)i = at (7)
transient organic intermediates present in the photocatalytic sys-
tem that had not been completely mineralised [27,30]. The resulted equation is Eq. (8):
The results showed that complete mineralisation was reached −dCDOC
after 360 min corresponding to a final DOC lower than 10 mg L−1 , = k CDOC t (8)
dt
when the initial DBS concentration was 50 mg L−1 and 100 mg L−1
excluding the experiment operated at a catalyst concentration of where k is the modified kinetic constant in min−2 .
0.5 g L−1 and DBS concentration of 50 mg L−1 . The first stage could mainly correspond to DBS removal due to
Several mechanisms of cleavage for degradation of DBS could the same tendency in the kinetics of DBS disappearance. The second
be expected: decarboxylation of alkyl-side chain, aromatic ring stage, when most of the DBS has disappeared, is mostly due to DBS
cleavage including desulphonation and conversion of short chain degradation intermediates.
carboxylic acids to CO2 and H2 O [10]. The mineralisation was The values of the kinetic constants are shown in Table 3.

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 ) r2 k (Second stage) (min−2 ) r2

−4 −5
0.5 50 46.86 2.11 × 10 0.99 1.64 × 10 0.99
2 50 41.25 3.80 × 10−4 0.87 1.87 × 10−5 0.99
2 100 90.65 1.99 × 10−4 0.81 1.81 × 10−5 0.93
5 50 24.02 1.93 × 10−4 0.99 7.64 × 10−6 0.94
5 100 67.59 1.71 × 10−4 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 pounds were not fully identified, the deviation increased with
reaction time. The kinetics of DBS degradation was fitted to pseudo-
In this work, adsorption of DBS onto TiO2 was evaluated in first and second order kinetic models. In general, data fitted well
terms of the Langmuir isotherm, obtaining a Kads value of 26 mM−1 . the second order kinetic model for the early minutes of irradiation
The experimental results derived from the photocatalytic treat- when DBS concentration was high. For low concentrations, experi-
ment demonstrated that the natural pH of the solution (5.8–6.5) mental data were better described by the pseudo-first order kinetic
was more suitable for DBS degradation than basic pH (12.3). Fur- model. Experiments carried out with low concentration are usually
thermore, increasing the TiO2 dosage from 0.5 g L−1 to 5 g L−1 described by pseudo-first order kinetic models. The value of the
contributed positively to DBS photocatalytic degradation. second order kinetic constant decreased when the amount of DBS
The kinetics of mineralisation of DBS by TiO2 photocatalysis has increased for the same amount of catalyst and they lay between
also been studied. Complete mineralisation was achieved when the 3.98 × 10−5 mg L−1 min−1 and 5.96 × 10−4 mg L−1 min−1 .
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 Acknowledgements
in two stages considering that at the beginning of the process DBS
concentration was dominant but as long as photocatalysis occurred, Financial support from the Spanish Ministry of Education and
intermediate compounds increased their proportion. The first stage Science (CTQ2008-00690) and CONSOLIDER (CSD2006-44) are
was fitted up to 60–90 min and the kinetic constants lay between gratefully acknowledged.
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 References
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