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WAT E R R E S E A R C H

42 (2008) 585 594

Available at www.sciencedirect.com

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

Photocatalytic degradation of non-steroidal

anti-inflammatory drugs with TiO2 and simulated
solar irradiation
Fabiola Mendez-Arriaga, Santiago Esplugas, Jaime Gimenez
Chemical Engineering Department, University of Barcelona, Mart i Franque`s 1, 08028 Barcelona, Spain

art i cle info

ab st rac t

Article history:

The aim of this work is to evaluate and compare the degradation achieved for three non-

Received 4 January 2007

steroidal anti-inflammatory drugs (NSAIDs) by heterogeneous TiO2 photocatalytic means in

Received in revised form

aqueous solution at laboratory scale. The selected pharmaceutical compounds were

29 June 2007

diclofenac (DCF), naproxen (NPX) and ibuprofen (IBP). These compounds were used in their

Accepted 1 August 2007

sodium salt chemical form.

Available online 6 August 2007

Keywords:
Diclofenac
Ibuprofen
Naproxen
NSAID
Photocatalysis
Solar

Previous experiments (adsorption, photolysis and thermodegradation) were developed

to evaluate non-catalytic degradation for each NSAID. Photocatalytic experiments were
carried out in a Xe-lamp reactor in order to study the influences of different operational
conditions (catalyst load, temperature and dissolved oxygen concentration). These results
showed that the optimum amount of TiO2, to achieve maximum degradation, of IBP was
1 g/L. In contrast, the maximum degradation for DCF or NPX was observed at a TiO2 loading
of 0.1 g/L. Temperature had a significant effect only for NPX degradation, achieving almost
99% phototransformation. No significant differences were observed for DCF and IBP at 20,
30 and 40 1C. Dissolved oxygen concentration was an important parameter to increase the

TiO2

degradation for NPX and IBP. However, it was observed that its rate of mineralization did
not increase. Intermediate metabolites were detected in all cases. Hydroxyl metabolites
were the most important residual compounds after the photocatalytic treatment of IBP. The
inhibition percentage of bioluminescence from Vibro fischerias a toxicity parameter
increased during the irradiation time due to the residual concentration of the hydroxyl
metabolites generated. However, after 120 min, in experiments with 40 mg/L of dissolved
oxygen, a decrease of the % inhibition was observed. Only photocatalytic treatment of IBP
drives to a satisfactory biodegradability index BOD5/COD (between 0.16 and 0.42) and, only
in this case, a post-biological treatment could be suggested.
& 2007 Elsevier Ltd. All rights reserved.

1.

Introduction

Recent studies have demonstrated the presence of pharmaceutical compounds in rivers, lakes and superficial freshwater
(Halling-Sorensen et al., 1998; Ternes, 1998; Daughton and
Ternes, 1999; Carballa et al., 2004). Non-steroidal anti-inflammatory drugs (NSAIDs) are a special group of pharmaceuticals

that are often found as a persistent toxic waste and are one of
the most widely available drugs in the world. In Spain, 55% of
the consumed Top 200 drugs are ingested orally, and approximately 5% of them correspond to NSAIDs (Takagi et al., 2006).
Some important examples of this family of medicines are
ibuprofen, naproxen, diclofenac and ketoprofen, although there
are more than 50 different types available commercially.

Corresponding author. Tel.: +34 93 402 1293; fax: +34 93 402 1291.

E-mail addresses: fmendeza@ub.edu (F. Mendez-Arriaga), gimenez@angel.qui.ub.es (J. Gimenez).

0043-1354/$ - see front matter & 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2007.08.002

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In the environment, NSAIDs have been detected in hospital

wastewaters (Kummerer, 2001), in and out STP (sewage
treatment plant) effluents (Carballa et al., 2004), in surface
water such as rivers and lakes (Boyd et al., 2003), in marine
waters (Weigel et al., 2004) as well as in soil matrices (Scheytt
et al., 2006).
The detection levels rarely exceed the mg/L levels (Stumpf
et al., 1998; Ternes, 1998; Tixier et al., 2003); however, their
presence at low or high concentrations could bring about
harmful toxicological consequences (Fent et al., 2006; Prakash
Reddy et al., 2006).
Frequently, NSAIDs are prescribed for skeletalmuscle pain
and inflammatory rheumatic disorders; however, they also
present analgesic and antipyretic effects. The main common
characteristic in the NSAID group is the carboxylic aryl acid
moiety that provides their acidic properties.
Investigations on physical and chemical remediation technologies had recently reported the removal of some NSAIDs.
Filtration, adsorption, coagulationflocculation and flotation
(Carballa et al., 2005) are some examples. On the other hand,
advanced oxidation processes (AOPs) appear to be an alternative for the degradation of hazardous pollutants (Bauer
et al., 1999) and are usually clean technologies with an
economic advantage when AOPs are used with a natural light
source (Malato et al., 2001). AOPs are a potential alternative
for the degradation of NSAIDs by non-selective hydroxyl
radical attack on organic molecules and, sometimes, complete mineralization is achieved (Ravina et al., 2002). Actually,
AOPs have been employed to remove NSAIDs. Special
development did show the ozonation process (Huber, 2003;
Ternes, 2003; Zweiner, 2000) and recently the photo-Fenton
solar process (Perez-Estrada et al., 2005a, b).
Studies with TiO2 heterogeneous catalysts have also been
reported. Oxidation of organic compounds by means of TiO2
was achieved by hydroxyl radical generation through the
e/h+ pair generated when the semiconductor is exposed to
UV radiation. In a recent study, Calza et al. (2006) present an
exhaustive study on the heterogeneous photocatalytic degradation of DCF over TiO2 aqueous suspension at low DCF
concentrations (0.079.24 ppm).
In our study, relatively high initial concentrations of NSAID
were tested to obtain the most plausible amount of photoproducts and their subsequent characterization in order to
measure the final toxicity and biodegradability achieved. The
aim of this research is to describe the capability of TiO2 to
remove pollutants in aqueous solutions with high NSAID
concentrations, as well as to compare the degradation degree
of three separate NSAIDs, at different operation conditions in
a tubular laboratory reactor with a solar-simulated light
source.

42 (2008) 585 594

nyl]propanoic acid), all of them in their sodium salt form,

were purchased from Sigma-Aldrich and used without pretreatment (Fig. 1).

2.2.

NSAID concentrations were monitored after sample filtration

(Durapore PVDF Millipore 0.22 mm) in a high-performance
liquid chromatograph (HPLC) from Waters using a C18 RP
Trace Extrasil OD52-5 Micromet 25  0.46 Teknockroma column, and a Waters 996 photodiode array detector using the
Empower Pro software 2002 Water Co. Conditions of each
HPLC analysis are shown in Table 1.
Total organic carbon (TOC) was measured in a Shimadzu
TOC-V CNS instrument. Spectrophotometric measurements
to obtain the absorption spectrum were carried out in a
Perkin-Elmer UV/VIS Lambda 20 (220700 nm range) spectrophotometer. BOD5 determinations were carried out according
to the Standard Methods (5120) by a respirometric single
measuring system and OxiTop procedure. COD determination
was carried out according to Norm. France NFT 90101.
Multi-temperature measurements (Crison 621) and pH (Crison
GLP 22) were monitored online. Air and pure oxygen sparged
through the system were purchased at Air Liquide, both were
used to vary the dissolved oxygen concentration. Dissolved
oxygen concentration was measured online by Crison Oxi
330i WTW Oxi Cal-SL sensor. Microtox tests were employed to
obtain the inhibition of bioluminescence of Vibrio fischeri at
15 min of incubation time. Millipore water quality (18 MO) was
used during all experiments. For the identification of byproducts, the final sample mixture was analyzed by electrospray ionization/mass spectrometry using a PerSeptive, TOF
Mariner Jasco AS-2050 plus IS mass spectrometer.

2.3.

Experimental section

2.1.

Materials

Synthetic amorphous titanium dioxide (Degussa P-25) was

used as received. The NSAIDs DCF (2-[2-[(2,6-dichlorophenyl)amino]phenyl]acetic acid), NPX ((S)-6 methoxy-a-methyl 2
naphthaleneacetic acid)) and IBP (2-[3-(2-methylpropyl)phe-

Photoreactor

A stirred tank (1.5 L) was filled with the NSAIDTiO2 solution.

The aqueous suspension was continuously pumped (Heidolph Pumpdrive 5130 120300 rpm) to the Solarbox (Co.fo.me.gra 220 V 50 Hz) and recirculated to the batch tank. In the
Solarbox, the Duran tubular photoreactor (0.078 L) was
irradiated by the Xe-OP lamp (Phillips 1 kW) with a photon
flux equal to 6.9 mEinstein/s (290400 nm). The jacket temperature of the stirred tank was controlled with an ultrathermostat bath (Selecta; Frigiterm-10). All connections and
pipes employed were made of Teflon and/or glass material to
avoid losses by adsorption. The different types of equipment
and instruments employed in our installation are depicted in
Fig. 2.

3.
2.

Analytical procedures

Results and discussion

3.1.
Previous experiments: photolysis, thermodegradation and adsorption
To avoid confusion between photocatalytic and other degradation phenomena, it was necessary to evaluate the nonphotocatalytic influence of photolysis, thermodegradation
and adsorption of each NSAID onto the TiO2 catalyst.

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42 (2008) 585 594

Na+O-

O
O

O-Na+

O-Na+

Cl
NH

Cl

DCF

NPX

IBP

Fig. 1 Non-steroidal anti-inflammatory drugs selected.

Table 1 Parameters of HPLC analysis employed

NSAID

DCF
NPX
IBP
a
b
c
d
e

Mobile phase composition

Flow-rate
(mL/min)a

Injection
volume (mL)

l Detection
(nm)

Temperature
(1C)

Acetonitrileb10 mM ammonium
formiatec (5050)
Acetonitrileb0.05 M ammonium
phosphate dihydrogend (8020)
Acetonitroleb0.25 acetic acide (7525)

1.25

20

280

25

1.00

20

254

25

1.75

20

254

25

All in isocratic mode.

Panreac 99.8%.
Fluka 99% HPLC grade.
Aldrich 98% ACS.
Fluka grade LCMS.

Fig. 2 Experimental equipment and instrument design.

Photolysis experiments were carried out with 1.5 L volume

solutions (200 ppm initial concentration) placed in the stirred
tank and pumped to the Solarbox without the catalyst. The Xe
lamp was switched on and aliquots were taken to evaluate
the NSAID concentrations and TOC at different irradiation
times. The temperature was maintained constant at 30 1C.
Calza et al. (2006) confirmed that no significant influence by
photolysis at short-time experiments on DCF was detected;
however, in our experience, DCF and NPX concentrations
decreased until 75% when the DCF or NPX solution was
continually exposed to the Xe lamp during 2 h (see Fig. 4a).
This degradation by the photolysis phenomenon has an

important influence on DCF and NPX degradation due to

their absorption spectra, which overleap on the Xe-lamp
emission spectrum, specifically above 290 nm (see Fig. 3). The
results of these experiments are in agreement with Packer
et al. (2003). On the other hand, the small absorbance in the
UV region for IBP (see also Fig. 3) helps to explain why any
photolysis degradation was reached.
TOC decrease was only significant for DCF photolysis
(25%) (see Fig. 4b) and it could be possible due to the
photolysis contribution and also because of the sub-products
generated. The initial transparent solution of DCF changed
during photolysis to a light-brown color at the end of the

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2.5
Emission spectrum
of Xe Lamp 1 kW

liquid equilibrium phase

2

3
Abs (AU)

3.0

1.5

NPX
2

1
1

0.5

NSAID mM

DCF

Irradiance (W m2)

42 (2008) 585 594

2.0

1.0
adsorbed phase

IBP
0
0
290 300 310 320 330 340 350 360 370 380 390 400

0.0
0

Wavelength (nm)
Fig. 3 Absorption spectra of DCF, NPX and IBP in Millipore
H2O and emission spectrum of Xe lamp (Allen et al., 2000).

0.2

0.4
0.6
TiO2 g/L

0.8

Fig. 5 DCF (&), NPX (n) and IBP (J) supernatant

concentrations and their respective adsorbed
concentrations on different loadings of TiO2 at an NSAID
concentration of 500 ppm (filled points).

250
NSAID (mg/L)

DCF

NPX

IBP

200
150
100
50
0
0

30

60

90

120

150

Irradiation time (min)

250
DCF

NPX

IBP

TOC (mg/L)

200
150
100

close to the initial concentration. This result was also seen in

measured TOC values.
On the other hand, adsorption isotherms were obtained for
each NSAID. To evaluate the decrease of the pollutant due to
adsorption on the catalyst, different compositions of NSAID
TiO2 solution were prepared in 25 mL hermetic closed flasks
and submerged in a thermostatic bath at constant temperature (30 1C). The equilibrium concentration of each adsorbed
NSAID was determined by the difference after measuring the
supernatant concentration at 24 h darkness. In Fig. 5, the
NSAID adsorption on TiO2 is depicted varying TiO2 loading at
an initial NSAID concentration of 500 ppm.
Low percentages of adsorption were reached in all cases:
4.8470.39, 8.8371.29 and 2.1171.3 for DCF, NPX and IBP,
respectively. From a practical point of view, the adsorption
stage between any NSAID and the catalyst TiO2 does not
represent a significant loss in reduction on the concentration
of the substrate during the main photocatalytic process.

50

3.2.

0
0

30

60

90

120

150

Irradiation time (min)

Fig. 4 (a) Photolysis experiments. [NSAID] vs. irradiation
time for each NSAID. (b) Photolysis experiments. [TOC] vs.
irradiation time for each NSAID.

Conditions, technical parameters, operational process values

and results of NSAID, TOC conversions, biodegradability
index (BOD5/COD) and toxicity for photocatalytic experiments
are shown in Table 2.

3.2.1.
rate
experiments. The pH values during the photolysis experiment
decreased from 6 to 3, but no precipitation was observed. The
acidic decrease allows us to conclude that there is an
important influence of the photolysis effect on the degradation of DCF.
To evaluate the possible degradation due to temperature, 1 L
of NSAID solution (each one separated) with a 200 ppm initial
concentration was placed in the stirred tank and heated at 20,
40, 60 and 80 1C. Once the set point temperature was reached,
an aliquot for HPLC and another one for TOC analysis were
taken. No thermo-degradation and TOC decreases were
observed for any NSAID tested in the 2080 1C range.
Concentration profiles in all cases were always constant and

Photocatalytic experiments

Process conditions: influence of temperature and flow

Any temperature effects on DCF and IBP mineralization were

observed in the tested range (20, 30 and 40 1C). In the case of
NPX, an increase in degradation and a slight rise in TOC
conversion were reached for experiments carried out at 40 1C.
At the end of the experiments, a brown color was observed,
which could be explained by a polymerization reaction.
Flow rates (0.1, 0.2 and 0.4 mL/min) have not influenced the
degradation rate in any NSAID tested in accordance with the
operational configuration of our system, because the ratio
between the irradiated volume and the total volume is 0.052.
The range of flow rates tested does not produce an important
difference in the crossing irradiated volume per minute and
no effect is observed.

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42 (2008) 585 594

Table 2 Experimental photocatalytic setup, XNSAID, XTOC, BOD5/COD and/or % Vibrio fisheri (V.f.) inhibition
NSAID

TiO2
(g/L)

Dissolved O2
(mg/L)

Flow-rate
recirculation
(L/min)

Temperature
(1C)

X
NSAID

X
TOC

BOD5/COD and/or
(% V.f. inhibition)

DCF

D1a
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11

0
0.07
0.1
0.5
1
2
0.1
0.1
0.1
0.1
0.1

82b
82
82
82
82
82
82
82
82
82
40

0.2
0.2
0.2
0.2
0.2
0.2
0.1
0.4
0.2
0.2
0.2

30
30
30
30
30
30
30
30
20
40
30

0.95
0.94
0.90
0.89
0.75
0.69
0.90
0.94
0.87
0.91
0.98

0.25
0.52
0.59
0.50
0.38
0.29
0.68
0.68
0.68
0.69
0.70

0.02
o0.02
o0.02
o0.02
o0.02
o0.02
o0.02
0.02
o0.02
0.02
0.02 (14)

NPX

N1a
N2
N3
N4
N5
N6
N7
N8
N9
I1a
I2
I3
I4
I5
I6
I7

0
0.1
0.5
1
0.1
0.1
0.1
0.1
0.1
0
0.1
0.2
0.5
0.75
1
1

82
82
82
82
82
82
82
82
40
82
82
82
82
82
82
82

0.2
0.2
0.2
0.2
0.1
0.4
0.4
0.4
0.4
0.2
0.2
0.2
0.2
0.2
0.2
0.1

30
30
30
30
30
30
20
40
40
30
30
30
30
30
30
30

0.90
0.44
0.28
0.28
0.48
0.60
0.62
0.99
0.99
0.0
0.14
0.26
0.38
0.55
0.70
0.61

0.07
0.19
0.11
0.12
0.18
0.20
0.20
0.26
0.26
0.0
0.05
0.10
0.14
0.11
0.13
0.13

0.02
o0.02
o0.02
o0.02
o0.02
o0.02
o0.02
0.03
0.05 (97)
0.02
0.02
0.02
0.02
0.02
0.02
0.02

IBP

I8
I9
I10
I11
I11 (0 h)
I11 (0.5 h)
I11 (1.0 h)
I11 (2.0 h)
I11 (3.0 h)
I11 (6.0 h)
I11 (12.0 h)
I12
I12 (0.5 h)
I12 (1.0 h)
I12 (2.0 h)
I12 (3.0 h)
I13 (25 ppm)
I14 (50 ppm)
I15 (100 ppm)

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

82
82
82
40
40
40
40
40
40
40
40
8
8
8
8
8
40
40
40

0.4
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1

30
20
40
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30

0.71
0.65
0.79
0.99
0
0.19
0.21
0.59
0.70
0.99
0.99
0.68
0.20
0.28
0.33
0.49
0.99
0.99
0.99

0.18
0.13
0.15
0.14
0
0.05
0.11
0.14
0.15
0.16
0.17
0.14
0.03
0.06
0.10
0.12
0.80
0.74
0.50

0.02
0.02
0.02
0.16 (87)
0 (77)
(79)
0.03 (82)
0.10 (91)
(88)
0.20
0.29
0.04 (79)
0.04 (89)
0.04 (87)
0.04 (78)
0.04 (84)
0.42
0.30
0.19

Irradiation time: 4 h excluding the experiments indicated.

Initial concentration: 200 ppm excluding the experiments indicated.
a
Photolysis experiment.
b
82 expression indicates a free [O2] consumption, from an initial concentration of 8 mg/L to a final concentration of 2 mg/L.

3.2.2.

Influence of TiO2 loading

In heterogeneous photocatalysis, the rate of degradation is

not always proportional to the catalyst load. An optimal point
exists where TiO2 loaded shows a maximum degradation rate.
Over this value, scattering phenomena can appear and active

sites on the surface of the catalyst do not bring more e/h+

generation and therefore increase in degradation rate does
not occur.
For DCF and NPX, the addition of TiO2 does not improve the
degradation rate in comparison with photolysis experiments;

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however, for TOC rate degradation, an enhancement was

shown when TiO2 was employed. Only for IBP the TiO2 loaded
has an important rise in the IBP conversion (00.75) but a
slight increase in the mineralization rate was achieved
(0.030.21). Within the TiO2 load range tested, 1 g/L was found
to be the optimum value to achieve a maximum conversion of
IBP and TOC. Fig. 6 shows the highest conversion obtained for
each NSAID tested.
An approach to describe the apparent kinetic order of the
photodegradation reaction was achieved through the simple
first-order kinetics model. The kinetics constant (K), shown in
Table 3, highlights the fact that the reaction rate of NSAID
degradation is not so different for each compounds tested.

3.2.3. Ibuprofen caseinitial concentration varying: influence

on biodegradability index
From a practical point of view, biodegradability and toxicity
tests were carried out for the conditions where higher NSAID
and TOC conversions were reached. Even though good
conversions are obtained, the by-products generated can be
less biodegradable or more toxic than the original ones, and
then the photocatalytic process lacks practical application to
a next biological process.
In this sense, pure NSAID solutions (with initial concentrations ranging from 2 to 500 ppm) were tested and the
biodegradability index obtained in all cases was zero.
Biodegradability indexes reached had no significant improvement for DCF or NPX still at saturated O2 concentrations
under any combination of operational conditions at initial
high concentrations (see last column in Table 2). This leads to
the conclusion that the final dissolution at the end of the
photocatalytic treatment would not be able to be biologically
treated, although acceptable conversions were observed.

1
DCF

NPX

IBP

NSAID/NSAIDo

0.8
0.6
0.4
0.2
0
0

50

100
150
200
Irradiation time (min)

250

300

Fig. 6 Maximum degradation ratio for each NSAID tested.

DCF at 0.1 g/L TiO2; NPX at 0.1 g/L TiO2; and IBP at 1 g/L TiO2.
Table 3 Kinetic constant values for each NSAID
At 30 1C and 0.2 mL/min
DCF
NPX
IBP

TiO2 (g/L)

K (min1)

0.1
0.1
1.0

9.6  103
7.0  103
9.1  103

42 (2008) 585 594

Only the case of IBP showed an enhancement in the BOD5/

COD index when the solution had an excess of dissolved
oxygen. Next sections will focus on IBP results due to the
improvement in its biodegradability index.
In Figs. 7a, b and 8 are shown IBP removal, TOC conversion
and biodegradability index, respectively, as a function of the
initial IBP concentration (200, 100, 50 and 25 ppm) at 1 g/L of
TiO2 and 40 mg/L of dissolved oxygen. At the lowest initial
concentration of IBP, it is possible to obtain the maximum
degradation in approximately 60 min, with a mineralization
rate of almost 50%. The biodegradability index reached the
highest BOD5/COD relationship at the lowest initial substrate
concentration (Fig. 8). The photocatalytic process showed a
higher effectiveness in degradation at low initial concentrations of IBP. Its higher biodegradability index can be related to
the high oxidation level reached by the by-products generated.
Removal at the end of reaction and mineralization are lower
at high initial concentrations of IBP; however, in all cases the
photocatalytic treatment shows an enhancement in the
biodegradability index in comparison to IBP (high or low
concentrations) without treatment (from 0 to 0.160.42).

3.2.4. Dissolved O2 concentration varying: influence on

biodegradability index
Dissolved O2 concentration plays an important role on
photocatalytic processes (Blanco and Malato, 2003). In aerobic
photocatalytic heterogeneous systems the absorbed oxygen is
the principal acceptor species. An important enhancement in
the IBP degradation was observed at saturated dissolved O2
concentration (40 mg/L) and a reduction of irradiation time
was also observed. Mineralization shows, however, a slight
enhancement, approximately only 15% (see Fig. 9).
Under free oxygen consumption (28 g/L) or constant (8 g/L)
of dissolved oxygen, the reaction rate is remarkably stopped
and the maximum conversion of IBP obtained is almost 70%,
probably because of the subsequent exhaust or insufficient
concentration of O2 in dissolution. A high recombination of
e/h+ pair is reached and no more hydroxyl radicals are
available to react. Therefore, transfer of the hydroxyl radical
to the solution limits the photocatalytic reaction. Under
excess of oxygen in dissolution, the conversion of IBP is
almost complete possibly being the most efficient production
of hydroxyl radicals due to the less recombination of e/h+
species in the bulk of the catalyst. On the other hand, the
sparge got a major exposition or contact between the TiO2, O2
and the pollutant, raising the probability of collisions among
the IBP and the reactive species. In contrast, the slight
improvement on the TOC removals could be explained due
to the strong ability of IBP to scavenge the hydroxyl radical
generated. If the acceptor specie (O2) is present in excess, the
production of hydroxyl radicals increases. IBP then acts more
efficiently as a scavenger of those hydroxyl radicals and
diminishes almost totally its concentration by the hydroxylation process. Mineralization is not higher because the primary
process present is the generation of hydroxyl metabolites.
The probable generation of acid compounds (propionic,
formic and hydroxypropionic acid) from the loss of the
carboxyl moiety of IBP is not the main reaction.

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1.00

200
25 ppm
50 ppm
100 ppm
200 ppm

25 ppm
50 ppm
100 ppm
200 ppm

0.75
X TOC

150
IBP ppm

591

42 (2008) 585 594

100

0.50

0.25

50

0.00
0

50

100
150
Irradiation Time (min)

200

250

50

100
150
Irradiation Time (min)

200

250

Fig. 7 (a) Initial IBP concentration effect on IBP removal. (b) Initial IBP concentration effect on XTOC.

0.5

0.4

0.4

0.3

BOD5/COD

BOD5/COD

IBP biodegradability ratio

0.3
0.2

0.2
0.1

0.1

0
1 hr

0
25 ppm

50 ppm
100 ppm
IBP initial concentration

200 ppm

Fig. 8 Initial IBP concentration effect on the BOD5/COD after

4 h of photocatalytic treatment.

2 hr

4 hr
6 hr
Irradiation Time

12 hr

Fig. 10 Irradiation time effect on BOD5/COD. [IBP]o

200 ppm, 1 g/L TiO2, 40 mg/L O2, 30 1C.

0.4
0.5

X IBP

0.75

0.3
0.5
0.2
0.25

X TOC

0.4

BOD5/COD

0.3
0.2
0.1
0
8-2 (free
consume)

0.1

8 g/L (O2 eq
AIR)

40 g/L (O2
SAT)

Oxygen concentration
0

0
0

60

120

180

240

Irradiation time (min)

Fig. 9 O2 effect on the XTOC (empty points) and XIBP
(filled points): (B) 82 g/L O2 consumed; (&) 8 g/L O2; and
(n) 40 g/L O2.

Moreover, at long irradiation exposure times, hydroxylation

also appears to be the main reaction because the conversion
of IBP is completed and mineralization did not increase. (see
Section 3.2.5).
The improvement of the biodegradability ratio of IBP due to
high dissolved oxygen concentration is the most important
aspect to remark under an excess of dissolved oxygen in the

Fig. 11 Dissolved oxygen concentration effect on BOD5/

COD. All cases [IBP]o 200 ppm, 1 g/L TiO2, 30 1C, 4 h.

dissolution and it is also observed at long irradiation times. In

Figs. 10 and 11, the irradiation time effect and concentration
of dissolved oxygen on BOD5/COD are shown.

3.2.5.

Intermediates generated and their toxicity

No differences were observed in the type of by-products

identified among experiments carried out at saturated or
free O2 concentrations. However, the intensity obtained in
experiments where O2 was not in excess was two times
higher than those where O2 was maintained at saturated
concentrations.

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42 (2008) 585 594

O
HO
O

O-

OH

O-

H
O-

OH

[205]
I

OH

O
O-

HO
O

[221]

HO II

O-

O[221]

III

OO

HO

OH

[162]
O

H 3C

O-

C 2H 5

OH

[221] HO

[178]

HO

OH

[178]

O-

OH H3C

[133]
O
OH
OH

O
OH
IV

[238] HO

Fig. 12 Intermediates observed at the end of photocatalytic treatment of IBP. [IBP]o 200 ppm, 1 g/L TiO2, 40 mg/L O2, 4 h
irradiation time.

IBP 8-2 free O2 consume

IBP 40 mg/L O 2

20

95

85
80

10

75
5

% inhibition Vib.fisch.

90
15
EC50 (%v/v)

Fig. 12 shows the by-products detected by LCMS from the

photocatalytic treatment (in marked circle) and possible
transformation pathways followed by ibuprofen.
The most probable degradation (or transformation) of
IBP is due to a dominant photochemical scavenger of the
OHdmediated process by the inclusion of the radical in
the methylpropyl phenyl positions I (1-hydroxyIBP) and
II (2-hydroxyIBP)), and in the arylcarboxylic moiety (III
and IV). Direct demethylation or decarboxylation was not
observed. However, complementary results obtained from
the degradation of IBP by means of the photo-Fenton reagent
(not yet published) helped to assure that the hydroxylation
process can be the first step of degradation, followed by
a second step of demethylation or decarboxylation with
other different by-products with smaller m/z (178, 162, 133)
and also propionic, formic or hydroxypropionic acid or
sodium salts. Only at low initial concentrations of IBP did
the biodegradability increase (Fig. 8) due to the photocatalytic
reaction. Then, the highest concentration of hydroxylated
by-products is produced. From these, the formation of acidic
or salt compounds could continue with the degradation
process. In contrast, at high initial concentrations of IBP
(200 ppm), the only step of the hydroxylation reaction is seen
and a slight formation of acidic compounds is observed
(Fig. 12).
During the photocatalytic reaction, the generation of byproducts increases until a maximum concentration is
reached. In our case, it can be related to the toxicity results

70
0

65
0

30

60
120
180
Irradiation Time (min)

240

Fig. 13 Changes of EC50% v/v (in bars) and % inhibition

(linked symbols) of Vibrio fisheri bioluminescence as a
function of irradiation time.

obtained. The toxicity of the solution at different reaction

times was measured by a Microtox assay and can be observed
in Fig. 13. The increase in the inhibition of the bacteria test
goes hand in hand with the increase in toxic by-products,
which corresponds to hydroxyl forms of ibuprofen, generated
during the photocatalytic reaction. The most important
difference (expressed in inhibition percentages), between
the experiments at 40 and 28 mg/L free oxygen consumption,
is the production rate of the toxic by-products at oxygen

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saturation conditions. It is possible to observe a maximum

value of % inhibition at 120 min and, after that, a decrease
appears due to the diminishing concentration of toxic byproducts. In the case of non-saturated conditions, the
production of toxic metabolites is still increasing and it could
be possible for them to rise until a maximum value of
approximately 92% for times longer than 240 min. Analog
results are observed for the EC50 (% v/v) parameter. At 40 mg/L
of O2, EC50 seems to give a minimum value and then it
increases in accordance with the maximum concentration of
hydroxyl metabolites generated.
Moreover, Packer et al. (2003) assured that the half-life time
of IBP in the environment can be function of the OHd
concentration, i.e. [1015], [1016] and [1017] M, corresponding
to 29, 296 and 2960 h, respectively. IBP degradation by OHd
scavenger reaction is a slow process in a normal environment. In contrast, the application of a photocatalytic treatment on the degradation of IBP increases the concentration
rate of the hydroxyl radical, thus promoting the generation of
faster hydroxyl metabolites. The metabolites generated during the photocatalysis process are also reported as a product
of the biochemical pathway (Zweiner et al., 2002) but no more
than 10% of the original amount of IBP. By photocatalytic
means, it is possible to increase the percentage up to 100%
conversion of the initial IBP concentration. Biological treatment seems to be a good post-alternative after a photocatalytic treatment, because reports on biofilms or batch
biological reactors have shown the ability to reduce 90% of the
initial IBP and its metabolites (Zweiner et al., 2002). In this
way, the photocatalytic by-products, generated and promoted
at excess O2 concentration, increased the biodegradability
index at high concentrations of IBP.

4.

Conclusions

Although NSAIDs are a group of pollutants with special

characteristics for specific functions like drugs in human use,
no general pattern is possible to assign in the photochemical
reactions for their degradation by catalytic means. No general
tendencies were found for the photolytic degradation, adsorption or thermodegradation experiments. However, a
strong influence by photolysis is observed in the case of
DCF and NPX.
For all cases, an improvement is reached on the TOC
reduction when increasing the TiO2 loading. For DCF and NPX
cases, the by-products generated were not recommended for
a post-biological treatment due to the low biodegradability
index reached (sometimes equal to the original one).
Only IBP was an important increase in its removal and
biodegradability index reached after a photocatalytic process.
In IBP degradation, the main photocatalytic process is
hydroxylation and it depends strongly on aerated or nonaerated conditions. The photocatalytic degradation of IBP is
only an early transformation process going through hydroxylated by-products, but complete mineralization is not
observed. High oxidation levels can be assured by direct
decarboxylation attack on the hydroxyl radical avoiding the
hydroxylation step. By photocatalytic means, a direct attack
on the carboxylic moiety is not observed. Moreover, the

42 (2008) 585 594

593

hydroxylation rate is directly related to the concentration of

dissolved oxygen due to higher hydroxyl radical concentrations that are able to react.
The hydroxyl metabolites generated are in accordance with
the toxicological results obtained. The inhibition percentage
decreases if concentrations of the toxic metabolites decrease
at long irradiation times, but also if the hydroxyl radical rate
increases with an excess in the dissolved oxygen concentration. IBP, as a pollutant in water at high concentrations, can
be degraded in a biological treatment after pre-oxidation by
photocatalysis treatment with TiO2.

Acknowledgments
The authors would like to thank the financial support from
the Spanish Ministry of Education and Science (Projects
CTQ2005-00446/PPQ and CTQ2004-02311/PPQ), the Barcelona
University for the predoctoral grant, Marc Esplugas for his
help in the management of the research and to Dr. Marta
Vilaseca Casas and Dr. Mara Reixach Riba for their help and
technical support in the HPLC and LCMS analyses.
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