ARTICLE IN PRESS

WAT E R R E S E A R C H 42 (2008) 3480– 3488

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Degradation of paracetamol in aqueous solutions by TiO2

photocatalysis

Liming Yanga,, Liya E. Yua, Madhumita B. Rayb

a
Division of Environmental Science and Engineering, National University of Singapore, Singapore 119260, Singapore
b
Department of Chemical and Biochemical Engineering, University of Western Ontario, London, Ontario, Canada N6A 5B9

ar t ic l e i n f o abs tra ct

Article history: In this study, photo/photocatalytic oxidation of common analgesic and antipyretic drug,
Received 11 January 2008 paracetamol (acetaminophen), was investigated to determine the optimal operating
Received in revised form conditions for degradation in water. UVA (365 nm) radiation alone degraded negligible
15 April 2008 amount of paracetamol, whereas paracetamol concentration decreased substantially
Accepted 23 April 2008 under an irradiation of UVC (254 nm) with marginal changes in total organic carbon
Available online 7 May 2008 (TOC). In the presence of TiO2, much faster photodegradation of paracetamol and effective
mineralization occurred; more than 95% of 2.0 mM paracetamol was degraded within
Keywords:
80 min.
Photocatalytic degradation
The degradation rate constant decreased with an increase in the initial concentration of
Kinetics
paracetamol, while it increased with light intensity and oxygen concentration. The
Paracetamol
degradation rate also increased with TiO2 loading until a concentration of 0.8 g L1. The
Titanium dioxide
degradation rate slowly increased between pH 3.5 and 9.5, but significantly decreased with
Intermediates
increasing pH between 9.5 and 11.0. Based on the experimental data, a kinetic equation
describing paracetamol photocatalytic degradation with various process parameters is
obtained.
& 2008 Elsevier Ltd. All rights reserved.

1. Introduction genic bacteria, genotoxicity, and endocrine disruption (Ar-

Pharmaceutical compounds have recently been detected in
sewage effluents (Carballa et al., 2004; Miao et al., 2004; Rabiet
et al., 2006; Nikolaou et al., 2007), surface and ground water
(Kolpin et al., 2002; Anderson et al., 2004; Rabiet et al., 2006;
Nikolaou et al., 2007), and even drinking water (Stackelberg et
al., 2004; Rabiet et al., 2006). Pharmaceutical compounds
commonly found in aquatic environments include antibio-
tics, anticonvulsants, antipyretics, cytostatic drugs, hormone,
etc. (Ikehata et al., 2006; Nikolaou et al., 2007). Frequent
occurrence of pharmaceuticals in aquatic environments and
drinking water has raised a concern about their potential
effects on environment and human health. Some of the
adverse health effects caused by pharmaceutical pollutants
include aquatic toxicity, resistance development in patho-
cand-Hoy et al., 1998; Kümmerer, 2004). The presence of trace
pharmaceutical and other xenobiotic compounds in drinking
water is also of public concerns since little is known about
potential chronic health effects associated with long-term
ingestion of these compounds through drinking water
(Stackelberg et al., 2004). These compounds make their way
to water bodies through various sources, such as direct
disposal of surplus drugs in households, excretion by humans
and animals, and inadequate treatment of manufacturing
effluents (Ikehata et al., 2006; Nikolaou et al., 2007). To
avoid undesired accumulation of drugs in aquatic environ-
ments, development of powerful oxidation techniques is
underway to remove these compounds from water (Zwiener
and Frimmel, 2000; Balcioğlu and Ötker, 2003; Ikehata et al.,
2006).

Corresponding author. Tel.:+65 6516 8478; fax: +65 6774 4202.

E-mail address: eseyl@nus.edu.sg (L. Yang).
0043-1354/$ - see front matter & 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2008.04.023
 ARTICLE IN PRESS
WAT E R R E S E A R C H
Being a common analgesic and antipyretic drug, paraceta-
mol (acetaminophen) is heavily used all over the world. In a
study conducted in 2000, paracetamol was ranked as one of
the top three drugs prescribed in England, and the mass of
paracetamol through prescription alone totaled more than
400 tons in that year (Sebastine and Wakeman, 2003).
Paracetamol has been found with a concentration of up to
6 mg L1 in European STP effluents (Ternes, 1998), up to
10 mg L1 in natural waters in USA (Kolpin et al., 2002), and
even more than 65 mg L1 in the Tyne river, UK (Roberts and
Thomas, 2006). Recently, removal of aqueous paracetamol by
electrochemical (Brillas et al., 2005; Sirés et al., 2006; Water-
ston et al., 2006), ozonation, and H2O2/UV oxidation methods
(Vogna et al., 2002; Andreozzi et al., 2003; Skoumal et al., 2006)
has been reported. However, semiconductor photocatalysis,
one of the most promising advanced oxidation processes for
the destruction of aquatic pollutants, has not been reported
for the degradation of paracetamol. Among various semi-
conductor photocatalysts, TiO2 has received a great deal of
attention due to its chemical stability, non-toxicity, and low
cost (Carp et al., 2004; Kabra et al., 2004; Konstantinou and
Albanis, 2004).
Reaction mechanisms of photocatalytic processes have
been discussed extensively in the literature (Hoffmann
et al., 1995; Mills and Le Hunte, 1997; Bhatkhande et al.,
2002; Konstantinou and Albanis, 2004; Kabra et al., 2004; Carp
et al., 2004). In brief, illumination of aqueous TiO2 suspension
with irradiation energy greater than the band gap energy (Ebg)
of the semiconductor (hn 4Ebg ¼ 3.2 eV in the case of anatase
TiO2) generates valence band holes (h+vb) and conduction band
electrons (e cb):
lo385 nm þ
TiO2 þ hv ! e
cb þ hvb
The photogenerated valence band holes and conduction
band electrons can recombine to liberate heat or make their
ways to the surface of TiO2, where they can react with species
adsorbed onto the catalyst surface:
hþ d
vb þ H2 O ! OH þ H
þ
hþ  d
vb þ OH ! OH
Organics þ hþ
vb ! products
d
e
cb þ O2 ! O2
Organics þ e
cb ! products
Produced hydroxyl radicals (dOH) along with other oxidants,
e.g., superoxide radical anion (Od
2 ), can further mineralize
organic compounds to end products (water and CO2).
Organics þ ðd OH; O d
2 ; etc:Þ ! products
In this work, photodegradation of paracetamol in aqueous
TiO2 suspension using both UVA and UVC irradiation was
studied to determine optimal removal conditions with respect
to initial concentrations of paracetamol, catalyst loading,
light intensity, oxygen concentration, and pH. A kinetic
equation for paracetamol photocatalytic degradation is also
reported.
42 (2008) 3480 – 3488 3481
2. Materials and methods
2.1. Photocatalytic reaction system
Photooxidation of paracetamol was conducted in an annular
cylindrical reactor with a quartz sleeve at the center of the
reactor to house a UV light source. Experiments were
conducted in a semi-batch fashion; 150 mL suspension of
TiO2 and paracetamol (Sigma-Aldrich, USA) in Millipore
Direct-Q water was recirculated between a reservoir and the
photoreactor at a flow rate of 0.15 L min1 using a pump
(Micropump, Cole-Parmer, USA), with a residence time of the
solution outside of the reactor less than 30 s. A magnetic
stirrer was used to induce satisfactory mixing of the solution
in the reservoir. The suspension was tangentially introduced
into the photoreactor through a sintered stainless-steel
distributor positioned at the bottom of the photoreactor,
providing well-mixed suspension. The temperature of the
system was maintained at 26 1C by a cooling water jacket
surrounding the reservoir. Depending on the degradation
rates under individual reaction conditions, aliquots were
sampled every 20–45 min and filtered through a 0.2 mm PTFE
syringe filter to remove the catalyst particles before analyses.
Total volume of the withdrawn sample was less than 5% (by
volume) of the circulated solution. To investigate pH effects,
pH of the reaction media was adjusted using H2SO4 and NaOH
to a desired value throughout the experiments. Oxygen was
bubbled into the reaction system to enhance oxygen con-
centration in the reaction medium, for example up to
36.3 mg L1, much higher than the saturated value (8.2 mg L1
at 26 1C). Under anoxic conditions, the reactor was continu-
(1) ously purged with argon gas. Temperature (2672 1C), pH
(using Thermo Orion 720A+pH meter, USA), and oxygen
concentration (using SCHOTT Handylab OX12 coupled with
9009/61 sensor, Germany) of reaction media were measured
online throughout each experiment.
Non-porous titanium dioxide (TiO2, P25, Degussa AG,
(2) Germany) with primary particle diameter of 21 nm, specific
surface area of 50715 m2 g1, and a crystal distribution of 80%
anatase and 20% rutile was used as the photocatalyst. Two
(3)
types of UV light sources were used, one was black light blue
UVA lamp (8 W, FL8BLB, Sanyo Denki, Japan) providing a
(4)
principal output at 365 nm UV radiation; the other (15 W, UVC,
Ster-L-RayTM, Atlantic Ultraviolet Corp., USA) with a principal
(5)
output at 254 nm to enhance photocatalytic degradation via
direct photolysis accompanied with a small amount of
(6)
radiation at 185 nm, which can induce the formation of ozone
from dissolved oxygen followed by generation of H2O2. The
radiation of 185 nm can also be absorbed by water to directly
produce dOH. To adjust the intensity of a light source, various
types of mesh screens made of stainless steel were adopted;
(7) actual light intensity was measured at the external quartz
sheath surface using a digital radiometer with a 254-nm
sensor (Series 9811, Cole-Parmer, USA).
2.2. Chemical analysis
Paracetamol was analyzed using a Shimadzu 10A Series high-
performance liquid chromatography system (Shimadzu,
 ARTICLE IN PRESS
3482 WAT E R R E S E A R C H
Japan) coupled with a SPD-M10A VP photodiode array detector
selected at l ¼ 210 nm and a ZORBAX Eclipse Plus C18
analytical column (4.6  250 mm, 5 mm) (Agilent, USA) with a
constant temperature of 30 1C. The eluent consists of 50:50 (v/
v) water:acetonitrile (Fluka, Germany) with a flow rate of
1.0 mL min1. To monitor the extent of mineralization during
paracetamol degradation, changes in total organic carbon
(TOC) were measured using a TOC analyzer (Shimadzu 5000A,
Japan).
To identify potential intermediates during photocatalytic
oxidation of paracetamol, 50 mL of the reactant solution was
withdrawn and concentrated to complete dryness under a
mild nitrogen stream through a Pierce ReactiVap microcon-
centrator (Pierce Inc., Illinois, USA). Then, 50 mL of tetrahydro-
furan (GC grade, Merck, Germany) was added to re-dissolve the
compounds. A volume of 20 mL of a derivatization reagent, N, O-
bis(trimethylsilyl)-trifluoroacetamide (Sigma, USA) was added
to replace acidic hydrogen with non-polar trimethylsilyl
groups. After 20–30 min, the derivatized sample was injected
into GC–MS equipped with an HP-5 MS capillary column (5%
phenyl methyl siloxane, 30.0 m  250 mm  0.25 mm, Agilent,
USA); the GC–MS separation followed a profile of maintaining
column temperature at 60 1C for the initial 3 min followed by
an incremental increase of 8 1C min1 up to 280 1C, and the
oven temperature was held at 280 1C for 3 min. For each GC–MS
injection, 1-phenyldodecane (Aldrich, USA) was co-injected to
monitor the instrument performance.
3. Results and discussion
3.1. Effects of UV light and TiO2 loading
Fig. 1 shows the degradation of paracetamol with an initial
concentration of 4.0 mM under five reaction conditions. The
degradation of paracetamol in water can be approximately
modeled following pseudo-first-order kinetics. It should be
noted that, UVA (365 nm) radiation alone degraded a negli-
gible amount of paracetamol (in hollow up-triangle, Fig. 1),
whereas UVC (254 nm) radiation successfully removed para-
cetamol (in hollow reversed triangle, Fig. 1). This was
expected; our laboratory tests using UV–visible spectra
(Shimadzu Mini UV–VIS spectrometer) showed that parace-
tamol exhibited minimal absorbance to light at a wavelength
4350 nm, while significantly absorbed light at 254 nm (the
molar extinction coefficient e (254 nm)E750 M1 cm1).
O presence of both TiO2 and UVC successfully mineralized
HO NH
⎯⎯→
hv
products
In addition to photolysis under UVC, paracetamol could
also be oxidized by dOH, which were generated from the
reaction between a small fraction of 185 nm UV and water
molecules. However, in the presence of TiO2, the direct
photolysis can be suppressed because of turbidity and
utilization of photons to activate TiO2.
With TiO2 alone (without UV radiation), loss of paracetamol
was not evident (solid square, Fig. 1), indicating insignificant
adsorption of paracetamol onto TiO2. This also suggests that
42 (2008) 3480– 3488
5.0
4.0
Concentration (mM)
3.0
2.0
With TiO2 , without UV
Without TiO2, with UVA
1.0 With TiO2 , with UVA
Without TiO2 , with UVC
With TiO2 , with UVC
0.0
0 100 200 300
Reaction Time (min)
Fig. 1 – Photocatalytic degradation of paracetamol (4.0 mM)
using five reaction conditions: (’) with TiO2 (0.4 g L1),
without UV (initial pH, 5.4); (n) without TiO2, with UVA
(initial pH, 5.5); (E) with TiO2 (0.4 g L1), with UVA (initial pH,
5.8); (,) without TiO2, with UVC (initial pH, 5.3); (K) with
TiO2 (0.4 g L1), with UVC (initial pH, 5.6). Curves are fitted
with first-order kinetics.
stereochemical configuration of paracetamol is unsuitable to
chelate with Ti, leading to negligible chemical adsorption of
paracetamol onto TiO2 surface. However, in the presence of
TiO2 with UVA and/or UVC radiation (solid diamond and solid
dot, Fig. 1), much faster degradation of paracetamol occurred
compared to reactions without TiO2 and radiation only. For
example, under the same light source (UVC, 254 nm), the first-
order rate constant in the presence of TiO2 is more than four
times higher than that in the absence of TiO2 (last column,
Tests 1.3 and 1.5 in Table 1).
To monitor the extent of mineralization during photolysis
and photocatalytic oxidation of paracetamol, TOC was
monitored as shown in Fig. 2. In the absence of TiO2, although
half of paracetamol was consumed by 300 min under UVC
irradiation (hollow reversed triangle, Fig. 1), corresponding
TOC exhibited negligible change by 300 min (hollow reversed
triangle, Fig. 2), indicating low mineralization of paracetamol
intermediates by UVC irradiation alone. Similarly, with TiO2,
half of paracetamol was degraded within 300 min via UVA
(solid diamond, Fig. 1), but TOC showed slight change in
300 min (in solid diamond, Fig. 2). On the other hand, the
about 60% of TOC in 300 min (up to 85% by 450 min) (in solid
(8)
dot, Fig. 2). Hence, following discussions focus on photo-
catalytic studies using UVC (254 nm) irradiation only.
In general, photocatalytic oxidation rate constants empiri-
cally correlate to UV intensity as k1pIb (where I is the light
intensity). Under various light intensities at 254 nm, the
pseudo-first-order rate constant vs. light intensity (Fig. S1,
Supplementary appendix) shows a satisfactory correlation
with bE2.07 (41), indicating that electron–hole pairs formed
via UV in this study were consumed rapidly by chemical
reactions, instead of through the recombination of electron–
hole pairs (Daneshvar et al., 2004).
 ARTICLE IN PRESS
WAT E R R E S E A R C H 42 (2008) 3480 – 3488 3483

Table 1 – Degradation of paracetamol under various conditions

Test C0a(mM) TiO2 Oxygen pHb UV lightc Rate

loading concentration (mW cm2) constant
(g L1) (mg L1) (103 min1)

1. Photocatalytic degradation of paracetamol

1.1 4.0 0.4 36.3d 5.4–5.3 NAd,e NRf
1.2 4.0 0 43.0d 5.5-5.3 UVA NRf
1.3 4.0 0 36.6d 5.3–3.3 UVCg 2.370.2
1.4 4.0 0.4 42.8d 5.8–3.6 UVA 1.970.2
1.5 4.0 0.4 36.3d 5.6–3.3 UVCg 10.571.6
1.6 2.0 0.4 0.2h 5.9–5.5 UVCg 2.870.3
2. Effect of light intensity
2.1 4.0 0.4 36.3d 5.6–3.3 UVC (12.6) 10.571.6
2.2 4.0 0.4 33.2d 5.1–3.5 UVC (5.4) 2.070.1
2.3 4.0 0.4 32.9d 5.1–3.5 UVC (4.1) 0.870.07
2.4 4.0 0.4 34.2d 5.1–3.4 UVC (1.2) 0.370.01
3. Effects of TiO2 loadings
3.1 4.0 0 37.5d 5.3–4.1 UVCg 2.370.2
3.2 4.0 0.04 NAd,e 5.1–4.0 UVCg 4.970.5
3.3 4.0 0.1 NAd,e 5.2–3.9 UVCg 6.470.7
3.4 4.0 0.25 NAd,e 5.5–3.9 UVCg 8.670.8
3.5 4.0 0.4 36.3d 5.6–3.3 UVCg 10.571.6
3.6 4.0 0.8 NAd,e 5.4–3.3 UVCg 13.771.2
3.7 4.0 2.0 NAd,e 5.6–3.2 UVCg 14.371.6
3.8 4.0 5.0 NAd,e 5.5–3.5 UVCg 14.771.7
4. Effects of initial concentrations
4.1 2.0 0.4 34.0d 5.1–3.5 UVCg 19.573.1
4.2 4.0 0.4 36.3d 5.6–3.5 UVCg 10.571.6
4.3 6.0 0.4 33.2d 5.0–3.3 UVCg 4.970.4
4.4 10.0 0.4 NAd,e 5.0–3.3 UVCg 3.770.2
5. Effects of oxygen
5.1 4.0 0.4 1.3h 5.8–4.8 UVCg 1.670.1
5.2 4.0 0.4 5.5i 5.2–3.8 UVCg 3.470.1
5.3 4.0 0.4 13.8j 4.8–3.4 UVCg 6.270.7
5.4 4.0 0.4 36.3d 5.2–3.2 UVCg 10.571.6
6. Effects of pHs
6.1 4.0 0.4 36.1d 3.5 UVCg 11.070.9
6.2 4.0 0.4 34.0d 5.5 UVCg 11.871.8
6.3 4.0 0.4 35.7d 7.0 UVCg 12.271.4
6.4 4.0 0.4 36.5d 9.5 UVCg 16.571.6
6.5 4.0 0.4 35.0d 11.0 UVCg 9.370.8

a
c0: initial concentration of paracetamol.
b
To examine effects of pH, pH is adjusted as a constant throughout the individual experiment.
c
UVC (254 nm with a small portion of 185 nm UV light) or UVA (365 nm UV light) is applied in this study.
d
Purging oxygen to super-saturation (saturated O2 solubility, 8.2 mg L1 at 26 1C) in the reaction system.
e
NA: not applied.
f
NR: no obvious reaction.
g
The light intensity is around 12.6 mW cm2.
h
Purging argon in the reaction system.
i
Air saturation in the reaction system.
j
Purging argon and oxygen mixture in the reaction system.

Effects of TiO2 loading (up to 7 g L1) on photocatalytic
degradation of paracetamol are examined in Fig. 3, which
shows that the degradation rate constant of paracetamol
increased with TiO2 loading and reached a plateau at a TiO2
loading of 0.8 g L1, and decreased slightly beyond 5.0 g L1. As
expected, while higher catalyst loadings increase available
active sites, light penetration in the reaction system de-
creases, activating a smaller amount of TiO2 in the suspen-
sion. In addition, at a larger catalyst loading, more of the
originally activated TiO2 may be deactivated through collision
with ground-state catalysts according to the following
equation:
TiO2 þ TiO2 ! TiO#2 þ TiO2 (9)
where TiO2 has active species adsorbed on its surface and
TiO#2 is the deactivated form of TiO2 (Neppolian et al., 2002).
Since agglomeration and sedimentation of TiO2 under large
catalyst loadings would also take place (So et al., 2002; San
 ARTICLE IN PRESS
3484 WAT E R R E S E A R C H 42 (2008) 3480– 3488

1.2 0.025 300

Normalized TOC (TOCt / TOC0)

Rate Constant k (min-1)

250
1.0 0.020
1
k1 = 27.54× c 0 + 1.97 200

1/k1 (min)
0.8 0.015 r 2 =0.93
150
0.6 0.010
100

0.005 50
0.4 UVC
UVA + TiO 2
0.000 0
0.2 UVC + TiO 2
0.0 2.0 4.0 6.0 8.0 10.0 12.0
Initial Concentration (mM)
0.0
0 100 200 300 Fig. 4 – Effects of initial concentrations of paracetamol on
Reaction Time (min) photocatalytic degradation rate constants (k1) with a TiO2
loading of 0.4 g L1 (solid line). The dashed line
Fig. 2 – Normalized organic carbon (TOC) during photo/ corresponding to the secondary y-axis represents the
photocatalytic oxidation of paracetamol with an initial correlation between 1/k1 and initial concentration. Errors
concentration of 4.0 mM using (,): UVC photooxidation were analyzed using linear regression with a 95%
without TiO2 (initial pH, 5.3); (E): UVA photooxidation with confidence level.
TiO2 (TiO2 loading, 0.4 g L1; initial pH, 5.8); (K): UVC
photocatalytic oxidation with TiO2 (TiO2 loading, 0.4 g L1;
initial pH, 5.6).
2 mM was degraded, whereas at an initial concentration of
0.018 10 mM, less than 20% of paracetamol was removed (data not
shown). At a higher initial concentration, two factors could
0.015
hinder the degradation of paracetamol; firstly, increased
Rate Constant k1 (min-1)

0.012 amount of paracetamol may occupy a greater number of

TiO2 active sites, which subsequently suppresses generation
0.009 of the oxidants (Eqs. (2), (3), and (5)) and results in lower
degradation rates. Secondly, a higher paracetamol concentra-
0.006 tion absorbs more photons, consequently decreasing avail-
able photons to activate TiO2. Thus, a shortage of photons to
0.003
activate TiO2 surface essentially retarded the degradation of
0.000 paracetamol at a high initial concentration. Hence, the overall
reaction rates were lowered with the higher initial paraceta-
mol concentration. This has been observed in many photo-
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
-1
chemical reactions where activation by photon absorption is
TiO2 Loading (g L )
typically the first step for reaction.
Photocatalytic oxidation kinetics of organic compounds can
Fig. 3 – Effects of TiO2 loading on the photocatalytic
be successfully modeled using the Langmuir–Hinshelwood
degradation of paracetamol with an initial concentration of
(L–H) equation to describe a correlation between degradation
4.0 mM (initial pH, 5.1–5.6).
rate constants and initial concentrations (Daneshvar et al.,
2004; Behnajady et al., 2006):
et al., 2007), available catalyst surface for photon absorption
kini Kparacetamol
would actually decrease, causing insignificant increase in the k1 ¼
1 þ Kparacetamol ½paracetamol0
degradation rate beyond an optimal TiO2 dosage, 0.8 g L1 in
this study. Although the optimal TiO2 loading was 0.8 g L1, with a linearized expression of
the following experiments were conducted at a lower catalyst
1 1 1
loading of 0.4 g L1. ¼  ½paracetamol0 þ
k1 kini kini Kparacetamol

where k1 is the pseudo-first-order rate constant (min1), kini is

3.2. Effects of initial concentrations and oxygen the intrinsic reaction rate constant (mM min1), and Kparace-
concentration tamol is the L–H adsorption constant of paracetamol over TiO2 surface
(mM1) in aqueous environments. A satisfactory linear
Fig. 4 shows that the pseudo-first-order degradation rate correlation (r2 ¼ 0.93) between 1/k1 and [paracetamol]0 given
constant of paracetamol (solid line) decreased when the in Fig. 4 (dashed line corresponding to the secondary y-axis)
initial concentrations of paracetamol increased from 2 to indicates that despite poor adsorption of paracetamol on
10 mM (Tests 4.1–4.4 in Table 1). Within 80 min of reactions, TiO2, surface reactions of paracetamol, such as oxidation by
more than 95% of paracetamol at an initial concentration of surface dOH, remain important (Chen and Ray, 1998). kini and
 ARTICLE IN PRESS
WAT E R R E S E A R C H 42 (2008) 3480 – 3488 3485

Kparacetamol were obtained as 3.63  102 mM min1 and reactions and produce H2O2 (Eqs. (10)–(11)), one of the
13.98 mM1, respectively. important precursors of generating dOH (Eqs. (12)–(13)).
Since degradation of paracetamol mainly occurred on the Hence, through enhancing dOH–paracetamol oxidation,
TiO2 surface, minimizing the electron–hole pair recombina- superoxide can indirectly degrade paracetamol:
tion would accelerate photocatalysis of paracetamol. An
O
2
d þ Hþ ! HOd
2 (10)
efficient trapping of electrons enables reactions of valence
band holes (h+vb) with species adsorbed over the TiO2 surface HOd þ 
2 þ H þ ecb ! H2 O2 (11)
(Eqs. (2)–(4)). Using oxygen as a most economical electron

acceptor (Eq. (5)), photocatalytic degradation efficiencies can H2 O2 þ e d
cb ! OH þ OH (12)
be enhanced in a photocatalytic reaction system (Sánchez et
al., 1998; Shibata et al., 1998; Bamwenda et al., 2001). H2 O2 þ hv ! 2d OH (13)
Compared to the addition of Ar (5.1, Table 1), Fig. 5 shows It should also be noted that, under a high concentration of
that an addition of oxygen of 36.3 mg L1 significantly oxygen, a small amount of UV radiation at 185 nm can induce
increased the photocatalytic degradation rate of paracetamol formation of ozone followed by generation of H2O2 to produce
up to more than six times, corresponding to the reaction rate more dOH. This is an additional pathway contributing to
constant changing from 1.6  103 to 10.5  103 min1 (Tests paracetamol degradation when more oxygen is introduced
5.1 and 5.4 in Table 1). Effects of oxygen concentration on the into the reaction system.
degradation of paracetamol could be described using non- Since an expression of degradation kinetics is useful to
competitive Langmuir kinetic equation as k1 ¼ kO2 KO2 ½O2 =ð1 þ design a large-scale photoreactor, a series of experiments
KO2 ½O2 Þ (Chen and Ray, 1998; Daneshvar et al., 2004), where k1 were carried out with a constant TiO2 concentration of
is the pseudo-first-order rate constant, kO2 is the intrinsic rate 0.4 g L1 (Tests 2, 4, and 5 in Table 1) under various initial
constant (mg L1 min1) of paracetamol reaction, and KO2 is concentrations of paracetamol, light intensity, and oxygen
Langmuir adsorption constant of oxygen over TiO2 surface concentration. Applying a constant temperature (around
(mg1 L). The noncompetitive Langmuir kinetic equation can 26 1C) employed for all our tests to the kinetic expression
be linearized as 1=k1 ¼ 1=kO2 KO2  1=½O2  þ 1=kO2 . A plot of the reported by others (Chen and Ray, 1998; Daneshvar et al.,
1/k1 against 1/[O2] results in a satisfactory linear correlation 2004)
(r2 ¼ 0.97) (inset of Fig. 5), indicating that introducing oxygen  
Ea KO2  ½O2 
into the reaction system effectively inhibits electron–hole rparacetamol ¼ k0paracetamol  Ib  exp 
RT 1 þ KO2  ½O2 
recombination as oxygen consumes conduction band elec-
Kparacetamol  ½paracetamol
trons, allowing valence band holes to directly (Eq. (4)) and  ,
1 þ Kparacetamol  ½paracetamol0
indirectly oxidize paracetamol (Eqs. (2)–(3), and (7)). Based on
the intercept and slope of the fitted curve, kO2 and KO2 were we combined the two terms (k0 paracetamol and exp(Ea/RT))
obtained as 8.58  103 mg L1 min1 and 0.17 mg1 L, respec- into one (kparacetamol) in the equation, resulting in
tively. It is worth noting that oxygen reacting with conduction KO2  ½O2 
rparacetamol ¼ kparacetamol  Ib 
band electrons forms superoxide radical anion (O d
2 ) (Eq. (5)), 1 þ KO2  ½O2 
which could also directly degrade paracetamol (Eq. (7)). In Kparacetamol  ½paracetamol
 .
addition, superoxide radical anion can undergo further 1 þ Kparacetamol  ½paracetamol0

Thus, employing experimentally obtained kinetic constants

Kparacetamol, b, and KO2 and known experimental parameters
0.015 (initial concentration, light intensity, and oxygen concentra-
× +
tion) as well as resultant pseudo-first-order rate constants
(Tests 2, 4, and 5), a kinetic equation for paracetamol
Rate Constrant k1 (min-1)

0.012
photocatalytic degradation in this study is given as
0:17  ½O2 
0.009 rparacetamol ¼ 2:2  104  I2:07 
1 þ 0:17  ½O2 
13:98  ½paracetamol
0.006  (14)
1 þ 13:98  ½paracetamol0
Fig. 6 shows the theoretically calculated vs. experimentally
0.003 obtained pseudo-first-order rate constants (Tests 2, 4, and 5,
Table 1). Most of the calculated data show good agreement
0.000 with the experimental data (r2 ¼ 0.87 excluding the right-top
0 10 20 30 40 point), except the point corresponding to Test 4.1 (Table 1)
-1
[O2] (mg L ) with an initial paracetamol concentration of 2.0 mM (r2 ¼ 0.73
including the right-top point). Under this initial concentration
Fig. 5 – Effects of oxygen concentration on photocatalytic (lower than 4.0 mM), the deviation between calculated and
degradation rate constants (k1) of paracetamol with a TiO2 experimental values is probably due to stronger effects of
loading of 0.4 g L1. Errors were analyzed based on linear photolysis, unlike other tests where photolysis was some-
regression with 95% confidence level. The inset represents what lower due to high initial concentration (e.g. 4.0 mM) of
the relationship between 1/k1 and 1/[O2]. paracetamol. This was supported by an enhanced correlation
 ARTICLE IN PRESS
3486 WAT E R R E S E A R C H 42 (2008) 3480– 3488

25 Table 2 – Identified intermediates during photocatalytic

degradation of paracetamol

20
Experimental k1 (min-1)

Intermediates Structures

15
Formic acida,b

10
Acetamidea,c

a,c
Oxamic acid
0
0 5 10 15 20 25
-1
Calculated k1 (min )
a,d
Hydroxy-acetic acid
Fig. 6 – Comparison between experimental and calculated
first-order rate constants for the photocatalytic oxidation of
a,d
paracetamol. Malonic acid

a,d
Butenedioic acid
(r2) between the calculated and experimentally tested values;
the r2 increases from 0.73 to 0.92 (hollow square point, Fig. 6)
when we subtract the degradation rate constant of direct
photolysis (Test 1.6, Table 1) from the overall rate constant
Succinic acida,d
(Test 4.1, Table 1).
In addition to the paracetamol degradation kinetics, poten-
tial photocatalytic intermediates and products were identified.
Table 2 summarizes 11 identified intermediates along with Malic acida,d
their molecular structure during Test 1.5 (Table 1), including
three aromatic compounds, six saturated, and one unsatu-
rated carboxylic acids and acetamide. Data of IC analyses Hydroquinonea,d
(Waters 2690, USA) showed that the nitrogen in paracetamol
molecule was eventually mineralized to ammonium and
nitrate ions (data not shown). These intermediates indicate Acetamide, N-(2,4-
ihydroxyphenyl)-d,e
that degradation of paracetamol involves a cleavage of the
benzene ring followed by subsequent reactions to form water
and carbon dioxide. Full information of concentrations of the
Acetamide, N-(3,4-
identified intermediates and corresponding reaction mechan-
ihydroxyphenyl)-d,e
isms in detail are provided elsewhere (Yang et al., 2008).

3.3. Effect of pH a
Identified based on authentic standards.
b
Identified through IC based on authentic standard’s elution time.
In the photocatalytic process, pH can also influence the c
Identified through HPLC based on authentic standard’s elution
degradation rates. Fig. 7 shows that the rate constant increases time.
d
slightly with increasing pH up to 9.5. This can be attributed to Identified through GC–MS based on spectrum library.
e
Identified based on principal mass fragments (m/z) of trimethyl-
enhanced formation of dOH, because at high pH (e.g., 9.5) more
silyl (TMS) derivatives (Vogna et al., 2002).
hydroxide ions available on TiO2 surface can be easily oxidized
and form more dOH (Eq. (3)) (Zheng et al., 1997; Galindo et al.,
2000), which consequently increases the efficiency of para-
Thus, increasing pH (e.g., to 11.0) gradually increases the
cetamol degradation. On the other hand, the reaction rate
electrostatic repulsion between TiO2 surface and paracetamol
constant significantly decreased at pH 11.0 (9.3 min1, Fig. 7),
(pKa ¼ 9.5) (Brunner et al., 1998), which is negatively charged
mainly due to surface ionization of TiO2. As the point of zero
at pH above 9.5
charge of the TiO2 is 6.3, TiO2 surface is positively charged in
acidic media (pH o6.3, Eq. (15)), whereas it is negatively
O O
charged at alkaline conditions (pH 46.3, Eq. (16)):

TiOH þ Hþ 2TiOH2þ (15) HO NH O NH + H

TiOH þ OH 2TiO þ H2 O (16) (17)


WAT E R R E S E A R C H
0.020
0.016
Rate Constant k1 (min-1)
0.012
0.008
0.004
0.000
2.0 4.0 6.0 8.0
pH Value
Fig. 7 – Effects of pH on the photocatalytic degradation rate
constants of paracetamol with an initial concentration of
4.0 mM and TiO2 loading of 0.4 g L1.
and further reduced already poor adsorption of paracetamol.
Hence, it is not surprising that the degradation rate of
paracetamol is decreased at a pH higher than 9.5. In addition,
at a higher pH, the formation of superoxide radical anion
(O d
2 ) through oxygen reduction by electrons can be sup-
pressed (Eq. (10)), which will result in less formation of H2O2
and dOH (Eqs. (11)–(13)), and consequently lower the degrada-
tion of paracetamol. Taken together, while the role of pH at
3.5–9.5 may be insignificant, under a stronger alkaline
condition (pH49.5), effects of pH on the degradation of
paracetamol should be taken into account to assess changes
in degradation of paracetamol.
4. Conclusions
Photocatalytic degradation of paracetamol in water was
studied using TiO2 as the catalyst with light sources of UVA
or UVC. With UVA radiation, no obvious degradation of
paracetamol was found in the absence of TiO2, although
significant reduction in paracetamol concentration was ob-
served during the irradiation with UVC radiation only,
demonstrating the effects of photolysis. A minimal change
in TOC in 300 min of irradiation indicates ineffective miner-
alization of paracetamol in the absence of TiO2. A much faster
degradation and effective mineralization of paracetamol took
place under UVC irradiation in the presence of TiO2. Experi-
mental results showed that the rate constants decrease with
an increase in the initial concentration of paracetamol, but
increase with increase in light intensity and additional
oxygen. The reaction rate constants also increased with
larger TiO2 loading and reached a plateau at TiO2 concentra-
tion of 0.8 g L1 and decreased slightly at a very high
concentration of 7.0 g L1. The rate constant increases slightly
with increase in pH up to 9.5, after which a significant
decrease is observed. This can be attributed to enhanced
formation of dOH because at high pH (e.g., 9.5); however, at pH
11.0, electrostatic repulsion between TiO2 surface and para-
cetamol can actually retard the degradation of paracetamol.
Based on light intensity of 254 nm radiation, oxygen concen-
ARTICLE IN PRESS
42 (2008) 3480 – 3488 3487
trations, and initial concentrations of paracetamol, a kinetic
model for paracetamol photocatalytic degradation rate was
developed. Eleven intermediates of paracetamol photodegra-
dation were identified, including three aromatic compounds,
seven carboxylic acids and acetamide.
Acknowledgments
We thank Mr. Nyi Nyi Naing for his assistance on chemical
analyses. This work was financially supported by the National
University of Singapore (R-288-000-015-112).
10.0 12.0
Appendix A. Supplementary materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.watres.2008.04.023.
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