You are on page 1of 39

Cent. Eur. J. Chem.

• 10(4) • 2012 • 989-1027


DOI: 10.2478/s11532-012-0049-7

Central European Journal of Chemistry

TiO2-assisted photodegradation
of pharmaceuticals – a review
Review Article

Alfred Y.C. Tong1,2*, Rhiannon Braund2 ,


David S. Warren1, Barrie M. Peake1
1
Chemistry Department, University of Otago,
Dunedin 9054, New Zealand

2
New Zealand National School of Pharmacy,
University of Otago, Dunedin 9054, New Zealand

Received 21 December 2011; Accepted 13 April 2012

Abstract: Pharmaceutical compounds have been detected in the environment and potentially arise from the discharge of excreted and improperly
disposed medication from sewage treatment facilities. In order to minimize environmental exposure of pharmaceutical residues,
a potential technique to remove pharmaceuticals from water is the use of an advanced oxidation process (AOP) involving titanium
dioxide (TiO2) photocatalysis. To evaluate the extent UV/TiO2 processes have been studied for pharmaceutical degradation, a literature
search using the keywords ‘titanium dioxide’, ‘photocatalysis’, ‘advanced oxidation processes’, ‘pharmaceuticals’ and ‘degradation’
were used in the ISI Web of Knowledge TM, Scopus TM and ScienceDirect TM databases up to and including articles published
on 23 November 2011. The degradation rates of pharmaceuticals under UV/TiO2 treatment were dependent on type and amount
of TiO2 loading, pharmaceutical concentration, the presence of electron acceptors and pH. Complete mineralization under particular
experimental conditions were reported for some pharmaceuticals; however, some experiments reported evolution of toxic intermediates
during the photocatalytic process. It is concluded that the UV/TiO2 system is potentially a feasible wastewater treatment process,
but careful consideration of the treatment time, the loading and the type of TiO2 (doped vs. undoped) used for a particular pharmaceutical
is necessary for a successful application (198 words).
Keywords: Pharmaceuticals • Titanium dioxide • Photocatalysis • Advanced oxidation process • UV
© Versita Sp. z o.o.

1. Introduction systems must have arisen from their medicinal usage prior
to their appearance in urine or faeces. More worrying,
Pharmaceuticals have been detected in trace their appearance may also be due to unused medications
concentrations in the natural aquatic environment at which have been disposed of improperly down the toilet,
concentrations of ng L-1 to µg L-1 [1-6]; and this has via the sewage system [36] or dumped into rubbish as
been a global phenomenon [7-10]. The presence of landfill waste, leading to excessive discharge of leachate
these compounds occur in sites as diverse as surface into environmental waters [37].
water [11-14], drinking water [15-18] and sewage The observed discharge of pharmaceuticals into the
influent and effluent from water treatment plants [19-34]. environment from sewage treatment plants suggests
Pharmaceuticals persist in the environment due to their many conventional treatment processes are often not
inability to be degraded by natural physical processes effective in reducing their levels in the wastewater stream.
such as sunlight photolysis or microbial processes [35]. For instance, it has been reported that carbamazepine
Many compounds that have been detected, such as is poorly removed in the wastewater stream by primary
paracetamol, carbamazepine, diclofenac, and ibuprofen, sedimentation and secondary microbial degradation
are entirely synthetic and classed as xenobiotics [34]. treatment processes [38]. Furthermore, the removal
As a result, pharmaceuticals detected in natural waters efficiencies of a pharmaceutical at a particular

* E-mail: alfred.tong@otago.ac.nz
989
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

sewage treatment facility may vary depending on wastewater treatment of pharmaceuticals will also be
the sedimentation tank retention time, and the use of evaluated.
activated sludge treatment or membrane biofilters
[39-42].
To improve the removal efficiencies, novel methods 2. Results and discussion
of treating pharmaceutically-rich sewage influent have
been developed. Such treatment methods include 2.1. Influence of pharmaceutical and
advanced oxidation processes (AOPs) [43] involving TiO2 concentration on photocatalytic
ultraviolet (UV) irradiation alone [44,45], combining UV degradation
irradiation with hydrogen peroxide to generate hydroxyl Many of the studies reported an inverse relationship
(HO.) radicals as an effective oxidising agent [46-49] between the rate of TiO2-assisted photodegradation
and incorporating hydrogen peroxide with Fe2+ ions and the concentration of the substrate pharmaceutical
(photo-Fenton) which increases the efficiency of HO. due to the saturation of active sites on the TiO2
radical generation [50-54]. More recently, heterogenous surface [70-75]. Furthermore, since pharmaceuticals
photocatalysts such as suspended titanium dioxide or photoproducts produced from TiO2 photocatalysis
(TiO2) have been used to generate HO. radicals [55]. may themselves absorb UV radiation, their presence
The success of TiO2 as a photocatalyst is dependent on decreases the amount of incident radiation available
its physicochemical properties as a semiconductor [56]. to create valence hole-conduction band electron pairs
Although the two most common forms of crystalline in the TiO2 material which mediates photocatalysis
TiO2, anatase and rutile, show similar band gap energies, [70,76]. For example, the apparent UV-A assisted TiO2-
it has been reported that the photocatalytic activity of photocatalytic degradation rate constant for a 5 mg L-1
anatase is greater than that of rutile due to differences aqueous solution of diclofenac in deionized water was
in the band gap position in these two polymorphs 0.1 min-1 but was decreased to an initial rate of 0.03 min-1
[57,58]; and thus TiO2 photocatalysts generally have a for a 20 mg L-1 diclofenac solution [70]. Moreover, 85%
high proportion of anatase. Many studies on the TiO2 of a 5 mg L-1 aqueous atenolol solution in Milli-Q water
photocatalysed conversion of pesticides, dyes and was photoconverted during 240 minutes irradiation with
synthetic compounds [59-68] have used photocatalysts Aeroxide P25 TiO2 and UV-A; however only 54% of
with a high anatase content (such as Aeroxide P25, a 20 mg L-1 solution was degraded under the same
which is also known as Aeroxide P25 and typically conditions [71]. Similar decreases in photocatalytic
consists of a 80:20 or 75:25 ratio of anatase:rutile, or degradation rates (from 0.0195 min-1 to 0.0037 min-1)
pure anatase photocatalysts such as Hombikat UV100). were observed with 2 – 10 mmol L-1 aqueous paracetamol
Most of these studies have shown that the use of TiO2 solutions with UV-C irradiation and oxygen saturation in
photocatalysts for the production of hydroxyl radicals from Milli-Q water at 26°C [77]. In addition, a decrease in the
UV irradiation significantly increased degradation rate pseudo-first order degradation constant (from 0.229 min-1 to
constants relative to homogenous direct UV photolysis. 0.078 min-1) for the UV-A/TiO2 photocatalytic treatment
And compared with other homogenous AOPs, such as of propanolol in Milli-Q water (pH = 7.0) was observed
UV/H2O2/Fe2+ (photo-Fenton), the photocatalyst can be when a 200 µM solution of propanolol was irradiated as
easily separated from the reaction solution and recycled opposed to a 50 µM solution.
without the addition of extra reagents such as H2O2 or The amount of TiO2 used may also significantly
iron salts [69]. Thus from the current literature, the use affect the degradation rate. The apparent first-order
of TiO2 as a photocatalyst may be an industrially-feasible rate constant for amoxicillin degradation (10 mg L-1)
tertiary sewage treatment process for the degradation of increased from 0.0172 min-1 to 0.0237 min-1 when the
pharmaceuticals in wastewater. suspended TiO2 catalyst concentration was increased
Therefore, the aim of this review is to survey the from 0.2 g L-1 to 0.8 g L-1 [78], and this was accompanied
extent of the use of TiO2 mediated photocatalysis for by an increase in mineralization kinetics measured
the photodegradation of pharmaceuticals in aqueous by total organic carbon experiments (0.0182 min-1 to
solution. The removal efficiency obtained from various 0.0235 min-1 for 0.2 g L-1 and 0.8 g L-1 TiO2 loadings
experimental parameters and the safety of TiO2 respectively). This phenomenon is predicted, because
photocatalysis as observed from current ecotoxicity an increase in TiO2 loading provides more binding
data on different classes of pharmaceuticals and their sites for substrate molecules to adsorb to the TiO2
photoproducts will be reported. In addition, the feasibility surface [79]. However, an increase in TiO2 loading from
of using TiO2-assisted photodegradation processes in 0.2 to 0.8 g L-1 did not significantly increase the apparent

990
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

degradation rate contant (kapp) of carbamazepine properties of a pharmaceutical only partially account for
(kapp = 0.0311 min-1 and 0.037 min-1 respectively) [78]. the observed degradation rates. It has been proposed by
Furthermore, no increase in the paracetamol degradation Yang et al. 2010 [74] that the increased degradation rate
rate was observed with experiments using TiO2 observed with propanolol when treated with the UV-A/
loadings > 0.8 g L-1 and the same initial pharmaceutical TiO2 system at pH = 5 relative to photodegradation at
concentration [77]. With excessive TiO2 loadings, It has pH = 7 is because of the favourable adsorption of the
been suggested that the TiO2 particles in the centre of electron-dense rings in propanolol onto the positively-
an irradiating vessel may be shielded from the incident charged surface of the photocatalyst at this pH. This
UV by other TiO2 particles, and thus particles in the phenomenon, however, was not observed with other
centre do not contribute significantly to the production beta-blocker pharmaceuticals which lack the electron-
of (h+, e -) pairs [80]. As observed with the data collected rich naphthyl rings, such as metoprolol and atenolol.
in these previous studies, it is often not possible to Given that the pH of wastewater is variable, it is
predict the optimal loading of TiO2 for the removal of again virtually impossible to evaluate the degradation
a certain concentration of a particular pharmaceutical of a particular pharmaceutical based solely on
without the use of computer-aided modelling to experiments carried out at one particular pH. Even if
determine optimal conditions for the photocatalytic sewage water from one particular sewage facility is
reaction which one study has used and addressed [106]. used as the matrix, it may not be representative of
Such modelling is necessary to determine the optimal sewage water from another facility. Most sewage water
quantity of TiO2 needed for efficient photocatalysis in is near neutral pH [84], however, a pH = 8.2 has been
any particular sewage treatment facility, given that the reported for tertiary treated wastewater [96]. Therefore,
expected concentration of a certain pharmaceutical in to characterize more fully the degradation behaviour
the wastewater is known. of a particular pharmaceutical by TiO2 photocatalytic
mechanisms, a detailed analysis of how pH changes
2.2. Influence of pH on photocatalytic affect photocatalysis is necessary.
degradation
The pH of the solution can affect TiO2-assisted 2.3. Influence of experimental apparatus and
photodegradation rates. The surface of the photocatalyst matrix conditions on degradation rate
may become positively or negatively charged depending Photocatalytic rates for the degradation of
on the ambient pH. TiO2 has a point of zero charge at pharmaceuticals may be dependent on the type of
around pH = 6 [72]; thus, the surface of the photocatalyst matrix and experimental apparatus used. For instance,
will be positively charged in solutions below this pH the apparent degradation rate of carbamazepine was
and negatively charged above. Therefore, the pH will reduced from 0.28 min-1 to 0.16 min-1 in distilled water
impact the adsorption of pharmaceuticals onto the compared to bog lake water with 0.5 mg L-1 natural
TiO2 surface depending on their chemical structure. organic matter (NOM) [84]. The NOM not only acted
An et al. (2010) [81] investigated the pH dependence as an inner filter which absorbed an estimated ~3.5%
of TiO2-assisted photodegradation of ciprofloxacin and of the incident radiation, but effectively scavenged
found the photocatalytic process to be most efficient valence holes, and therefore, reduced the production
at pH = 9 (k = 0.38 min-1), whereas more extreme of HO.radicals. Furthermore, the NOM used in this study
pH conditions significantly affected the degradation had an overall negative charge and thus was attracted
rates (k = 0.06 min-1 and 0.07 min-1 at pH = 3 and 11 to the positively-charged surface of TiO2 under the
respectively). This is due to the chemical structure of experimental pH range (5.0 – 6.5). Similar results were
ciprofloxacin: at high pH, both the basic nitrogen on the reported in a recent study concerning the degradation of
piperazinyl moiety (pKa = 8.6) and the carboxyl group ranitidine in effluent water [85]. The pseudo-first order
(pKa = 6.1) are deprotonated with the overall charge degradation constant of ranitidine in distilled water was
being negative. Therefore, the molecule is repelled by over ten times greater than degradation in effluent water.
the negative surface charge of the TiO2 and minimal In addition, only 8% of the degraded ranitidine achieved
adsorption occurs. Similarly, at low pH, both these complete mineralization in an effluent water matrix
functional groups are protonated, and hence, the overall after 55 min irradiation compared with 37% in distilled
positive charge of ciprofloxacin repels the postively- water after 73 min irradiation. Many studies have also
charged surface of the photocatalyst. Similar variations involved photodegradation experiments in oxygen-
in degradation rates have also been reported for other saturated or anoxic conditions [86-89]. The TiO2-assisted
pharmaceuticals [82,83]. However the acid-base photodegradation of statin drugs undertaken in the

991
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Immobilized
TiO2 on UV-A Philips 126W Complete loss of
17α- ethinylestradiol 57–63–6 [111] 0.01 - titanium High pressure Hg kapp = 0.086 min-1 estrogenic activity
alloy lamp. after 1 h.
surface.
UV-A lamp max 355
Aeroxide ~3% remaining
[114] 0.89 400 nm, 8W, Io = 116.6 -
P25 180 min
W m-2.
UV-C lamp max 254 ~14%
Aeroxide
0.90 400 nm 8W, Io = 114.5 remaining 50 -
P25
W m-2 min
8W low pressure
Intermediates
Aeroxide Hg lamp, 365-370 <10% remaining
[115] 5.00 500 predominantly
P25 nm. Io =7.38×10-8 121 min.
present 40 min.
einstein s-1
Immobilized
UV-A Philips 126W Complete loss of
TiO2 on
17β-estradiol 50–28–2 [111] 0.01 - High pressure Hg kapp = 0.106 min-1 estrogenic activity
titanium
lamp. after 1 h
alloy surface
Complex
intermediates
including. 2-
hydroxyestradiol,
Low pressure Hg Complete 10e-17b-dihydroxy-
Aeroxide
[116] 10.00 500 UV-A lamp, Io = degradation 50 1,4-estradien-3-one
P25
7.38×10-8 einstein s-1. min. 10e-hydroperoxide-
17b-hydroxy-1,4-
estradien-3-one and
17b-hydroxy-1,4-
estradien-3-one.
10e-17b-dihydroxy-
Xenon lamp with 365
1,4-estradien-3-one,
Aeroxide nm band pass filter, 99% degradation
[117] 0.27 1000 androsta-
P25 200W. Io = 6 mW 30 min.
4,16-dien-3-one,
cm-2.
testosterone
UV-A lamp max 355
Aeroxide ~5% remaining
[114] 0.66 400 nm, 8W, Io = 116.6 -
P25 180 min
W m-2.
UV-C lamp max 254
Aeroxide ~8% remaining
0.69 400 nm 8W, Io = 114.5 -
P25 50 min
W m-2
Aeroxide TQ-150 reactor, 238-
[118] 0.10 1000 kapp = 0.84 h-1 -
P25 579 nm, 150 W

Aeroxide TQ-150 reactor, 238-


0.25 1000 kapp = 0.82 h-1 -
P25 579 nm, 150 W

Aeroxide TQ-150 reactor, 238-


0.50 1000 kapp = 0.79 h-1 -
P25 579 nm, 150 W

Aeroxide TQ-150 reactor, 238-


1.00 1000 kapp = 0.83 h-1 -
P25 579 nm, 150 W

Aeroxide TQ-15-32 15W 254


0.10 1000 kapp = 2.31 h-1 -
P25 nm lamp.

Aeroxide TQ-15-32 15W 254


0.25 1000 kapp = 2.28 h-1 -
P25 nm lamp.

Aeroxide TQ-15-32 15W 254


0.50 1000 kapp = 2.30 h-1 -
P25 nm lamp.

Aeroxide TQ-15-32 15W 254


1.00 1000 kapp = 2.29 h-1 -
P25 nm lamp.
Guanidine.
Xenon solar lamp> Increased toxicity
15.00 Aeroxide kapp = 0.231
Amiloride 2609-46-3 [112] 200 340 nm, up to maximum 40%
P25 min-1
Io = 30 W cm-2 inhibition (Vibrio
fischeri 4 h).

992
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Blacklight 126W 300- TOC removal >


10.00 Aeroxide 420 nm. kapp = 0.0237 80%. Incomplete
Amoxicillin 26787-78-0 [78] 800
P25 Io = 4.7×10-7 einstein min-1 toxicity reduction
s-1. (121 min).
42% degradation
Fluka 100% 6W UV-A lamp 365
[80] 104.00 500 300 min (pH -
Anatase nm.
= 5.0)
55% degradation
Fluka 100% 6W UV-A lamp 365
104.00 1000 300 min (pH -
Anatase nm.
= 5.0)
56% degradation
Fluka 100% 6W UV-A lamp 365
104.00 1500 300 min (pH -
Anatase nm.
= 5.0)

55% degradation
Fluka 100% 6W UV-A lamp 365
104.00 2000 300 min (pH -
Anatase nm.
= 5.0)

61% degradation
Fluka 100% 6W UV-A lamp 365
104.00 1000 300 min (pH -
Anatase nm.
= 3.0)

55% degradation
Fluka 100% 6W UV-A lamp 365
104.00 1000 300 min (pH -
Anatase nm.
= 5.0)

59% degradation
Fluka 100% 6W UV-A lamp 365
104.00 1000 300 min (pH -
Anatase nm.
= 8.0)
71% degradation
Fluka 100% 6W UV-A lamp 365
104.00 1000 300 min (pH = -
Anatase nm.
11.0)
> 80%
Natural solar First intermediate
Aeroxide conversion 2 h
[91] 25.00 1000 irradiation; 16 mW p-hydroxybenzoic
P25 irradiation (pH
cm-2 acid.
= 6.0)
Natural solar 80% conversion First intermediate
Aeroxide
50.00 1000 irradiation; 16 mW 2 h irradiation p-hydroxybenzoic
P25
cm-2 (pH = 6.0) acid.
< 60%
Natural solar First intermediate
Aeroxide conversion 2 h
100.00 1000 irradiation; 16 mW p-hydroxybenzoic
P25 irradiation (pH
cm-2 acid.
= 6.0)
~70%
Natural solar First intermediate
Iron (0.42%) conversion 2 h
25.00 1000 irradiation; 16 mW p-hydroxybenzoic
doped TiO2 irradiation (pH
cm-2 acid.
= 6.0)
~65%
Natural solar First intermediate
Iron (0.89%) conversion 2 h
25.00 1000 irradiation; 16 mW p-hydroxybenzoic
doped TiO2 irradiation (pH
cm-2 acid.
= 6.0)
~62%
Natural solar First intermediate
Iron (1.33%) conversion 2 h
25.00 1000 irradiation; 16 mW p-hydroxybenzoic
doped TiO2 irradiation (pH
cm-2 acid.
= 6.0)
~75%
Natural solar First intermediate
Iron (2.2%) conversion 2 h
25.00 1000 irradiation; 16 mW p-hydroxybenzoic
doped TiO2 irradiation (pH
cm-2 acid.
= 6.0)
Natural solar 70% conversion First intermediate
Iron (3.0%)
25.00 1000 irradiation; 16 mW 2 h irradiation p-hydroxybenzoic
doped TiO2
cm-2 (pH = 6.0) acid.
>60%
Artificial UV 15W low First intermediate
Aeroxide conversion 6 h
10.00 1000 pressure 365 nm p-hydroxybenzoic
P25 irradiation (pH
lamp, 0.5 mW cm-2. acid.
= 3.0)

993
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Artificial UV 15W low 90% conversion First intermediate


Aeroxide
10.00 1000 pressure 365 nm 6 h irradiation p-hydroxybenzoic
P25
lamp, 0.5 mW cm-2. (pH = 6.0) acid.
>80%
Artificial UV 15W low First intermediate
Aeroxide conversion 6 h
10.00 1000 pressure 365 nm p-hydroxybenzoic
P25 irradiation (pH
lamp, 0.5 mW cm-2. acid.
= 9.0)
33% degradation
Fluka 100% 6W UV-A lamp 365
Ampicillin 69–53–4 [80] 105.00 500 300 min (pH -
Anatase nm.
= 5.0)
52% degradation
Fluka 100% 6W UV-A lamp 365
105.00 1000 300 min (pH -
Anatase nm.
= 5.0)
54% degradation
Fluka 100% 6W UV-A lamp 365
105.00 1500 300 min (pH -
Anatase nm.
= 5.0)
52% degradation
Fluka 100% 6W UV-A lamp 365
105.00 2000 300 min (pH -
Anatase nm.
= 5.0)
78% degradation
Fluka 100% 6W UV-A lamp 365
105.00 1000 300 min (pH -
Anatase nm.
= 3.0)
52% degradation
Fluka 100% 6W UV-A lamp 365
105.00 1000 300 min (pH -
Anatase nm.
= 5.0)
74% degradation
Fluka 100% 6W UV-A lamp 365
105.00 1000 300 min (pH -
Anatase nm.
= 8.0)
91% degradation
Fluka 100% 6W UV-A lamp 365
105.00 1000 300 min (pH -
Anatase nm.
= 8.0)
Less toxic
9W UV-A lamp
29123– 20.00 Aeroxide Conversion > photoproducts
Atenolol [71] 250 (350 – 400 nm). Io =
68–7 P25 60% 15-30 min irradiation
3.37×10-6 einstein s-1.
(Daphnia magna)
TOC < 10%
(250 min).
26.63 Aeroxide High pressure Hg kapp (pH = 7)
[74] 2000 Aromatic
P25 lamp 365 nm (126 W) 0.075 min-1
Hydroxylated
Intermediates.
21 degradation
1500 W Xenon lamp products.
41859– 1.00 Aeroxide kapp = 2.81×10-2
Bezafibrate [119] 100 > 290 nm. Io = 750 4 chlorobenzoic
67–0 P25 min-1
W m-2 acid and 4-
chlorobenzamide.
Modified
Natural Sunlight 10 kapp =0.416 s-1
Caffeine 58–08–2 [120] 0.10 - SiO2 TiO2 -
am – 5 pm (distilled water)
mix
Solar pilot plant,
Aeroxide Undetectable
[121] 0.10 5 average Io = 30 -
P25 114 min.
W m-2.
Immobilized
TiO2 Solar light simulator
Undetectable
[122] 0.10 - synthesized 290 – 800 nm. Io = -
25 min
by sol-gel 765 W m-2.
process
Compound Parabolic
Aeroxide Collector, natural kapp = 0.054
0.10 5 -
P25 sunlight. Io = 30 min-1
W m-2.
Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp = 0.053
0.10 - -
synthesized sunlight. Io = 30 min-1
by sol-gel W m-2
process

994
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Used
Immobilized Compound Parabolic
TiO2 Collector, natural kapp = 0.079
0.10 - -
synthesized sunlight. Io = 30 min-1
by sol-gel W m-2
process

9 W UV-A lamp,
40% DOC
10.00 Aeroxide (350-400 nm). Conversion =
Carbamazepine 298–46–4 [96] 100 removal
P25 Io = 3.37×10-6 74% (121 min)
(121 min)
einsteins s-1.

4.20 Aeroxide Xenon Solar simulator kapp (pH = 6.5)


[84] 100 -
P25 > 290 nm. 0.28 min-1

kapp
4.20 Aeroxide Xenon Solar simulator
100 (0.5 mg L-1 DOM) -
P25 >290 nm.
= 0.16 min-1

10,11-dihydro-
carbamazepine-
1000W 10,11-epoxide,
Xenon Solar lamp. Acridine.
4.30 Aeroxide kapp =
100 Io> 400 nm = Potentially
P25 4.7×10-3 s-1.
1.35×10-4 ecotoxic
einstein m-2 s-1. mutagenic and
carcinogenic
photoproducts.
TiO2 fibre
catalyst
on fixed Low pressure 10W
[123] 1.00 - kapp = 0.13 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
kapp = 0.15 h-1
Titanate 8W UV-A lamp (membrane
[89] 10.00 0.1 -
nanofibres i.. 360 nm. bioreactor
matrix)
kapp = 0.8 h-1
Titanate 8W UV-A lamp (membrane
10.00 0.5 -
nanofibres 360 nm. bioreactor
matrix)
kapp = 1.00 h-1
Titanate 8W UV-A lamp (membrane
10.00 1.0 -
nanofibres 360 nm. bioreactor
matrix)

Aeroxide 8W UV-A lamp kapp = 0.5 h-1


10.00 0.1 -
P25 360 nm. (saline matrix)

Titanate 8W UV-A lamp kapp = 5.0 h-1


10.00 0.1 -
nanofibres. 360 nm. (saline matrix)

Aeroxide 8W UV-A lamp kapp = 4.7 h-1


10.00 0.1 -
P25. 360 nm. (saline matrix)

126 W medium
5.00
Aeroxide pressure mercury kapp (pH= 3)
[82] 1000 -
P25 UV lamp (Helios 1.52×10-1 min-1
Italquartz Milan)

Immobilized
TiO2 Solar light simulator
30% remaining
[122] 0.10 - synthesized 290 – 800 nm. -
50 min
by sol-gel Io = 765 W m-2.
process
Compound Parabolic
Aeroxide Collector, kapp =
0.10 5 -
P25 natural sunlight. 0.029 min-1
Io = 30 W m-2.

995
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
0.10 5 -
synthesized sunlight. Io = 30 0.083 min-1
by sol-gel W m-2.
process
Used
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
0.10 5 -
synthesized sunlight. Io = 30 0.085 min-1
by sol-gel W m-2.
process
Incomplete
126 W Blacklight reduction in
5.00 Aeroxide 300-420 nm kapp = toxicity
[78] 200
P25 Io = 4.7×10-7 0.0317 min-1 121 min
einstein s-1 TOC
removal > 80%
126 W Blacklight
5.00 Aeroxide 300-420 nm kapp =
400 As above
P25 Io = 4.7×10-7 0.0311 min-1
einstein s-1

126 W Blacklight
5.00 Aeroxide 300-420 nm kapp =
800 As above
P25 Io = 4.7×10-7 0.037 min-1
einstein s-1

Medium Pressure
5.00 Aeroxide Hg lamp > 300 nm. kapp (pH = 7.5)
[124] 100 -
P25 Io = 5.1×10-6 0.022 min-1
einsteins s-1.

UV-A lamp 365 nm, Io


Aeroxide Complete <10% DOC
Chloramphenicol 56–75–7 [125] 50.00 1000 = 1.12×10-4 einstein
P25 removal 90 min 240 min
min-1.

UV-A lamp 365 nm,


Tronox 100% 50% removal 50% DOC
50.00 1000 Io = 1.12×10-4
Anatase 90 min 240 min
einstein min-1.

~55%
Nano-TiO2 300W medium-
degradation
[126] 15.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 3)
~75%
Nano-TiO2 300W medium-
degradation
15.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
~65%
Nano-TiO2 300W medium-
degradation
15.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 7)
~60%
Nano-TiO2 300W medium-
degradation
15.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 9)
~40%
Nano-TiO2 300W medium-
degradation
15.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 11)
~60%
Nano-TiO2 300W medium-
degradation
15.00 500 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
~60%
Nano-TiO2 300W medium-
degradation
15.00 750 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)

996
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

~65%
Nano-TiO2 300W medium-
degradation
15.00 1260 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
~50%
Nano-TiO2 300W medium-
degradation
15.00 1500 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
~75%
Nano-TiO2 300W medium-
degradation
5.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
~70%
Nano-TiO2 300W medium-
degradation
10.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
~65%
Nano-TiO2 300W medium-
degradation
15.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
~60%
Nano-TiO2 300W medium-
degradation
20.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
~55%
Nano-TiO2 300W medium-
degradation
25.00 1000 (100% pressure Hg lamp, > -
30 min
anatase) 365 nm.
(pH = 5)
Hydroxylation,
365 nm High- decarboxylation,
85721– Aeroxide kapp (pH = 3)
Ciprofloxacin [81] 33.18 1500 pressure Hg lamp. and piperazine
33–1 P25 0.06±0.01 min-1
Io= 0.38 mW cm-2 ring cleavage

365 nm High-
Aeroxide kapp (pH = 5)
33.18 1500 pressure Hg lamp. As above
P25 0.14±0.01 min-1
Io= 0.38 mW cm-1
365 nm High-
33.18 Aeroxide kapp (pH = 7)
1500 pressure Hg lamp. As above
P25 0.25±0.02 min-1
Io= 0.38 mW cm-1
365 nm High-
33.18 Aeroxide kapp(pH = 9)
1500 pressure Hg lamp. As above
P25 0.38±0.01 min-1
Io= 0.38 mW cm-1
365 nm High- kapp (pH = 11)
33.18 Aeroxide
1500 pressure Hg lamp. 0.07 ± 0.01 As above
P25
Io= 0.38 mW cm- min-1
450 W Xenon arc Cleavage of
33.18 Aeroxide lamp.> 324 nm kapp = 1.53×10-1 piperazine ring.
[95] 500
P25 Io = 9×10-5 einstein min-1 No decrease in
min-1 TOC >3 h
Hombikat 450 W Xenon arc
33.18; UV 100 lamp > 400 nm Io= kapp (pH = 3)
500 As above
(100% 1.6×10-4 einstein 3.72×10-2 min-1
anatase) min-1
Cleavage of the
piperazine ring.
450 W Xenon arc
Ciprofloxacin Loss of
33.18 Hombikat lamp > 324 nm. Io
[127] 500 undetectable at antibacterial
UV100 = 1.83×10-7 einstein
20 min activity
cm-2 s-1
proportional to
irradiation time.
UV-A lamp 365 nm,
Aeroxide kapp (pH = 3)
[128] 15.00 500 Io= 485 µW cm-2, -
P25 0.097 min-1
300-440 nm
UV-A lamp 365 nm,
Aeroxide kapp (pH = 7)
15.00 500 Io= 485 µW cm-2, -
P25 0.137 min-1
300-440 nm

997
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

UV-A lamp 365 nm,


Aeroxide kapp (pH = 10)
15.00 500 Io= 485 µW cm-2, -
P25 0.068 min-1
300-440 nm
Aeroxide UV-C lamp 254 nm , kapp (pH = 3)
15.00 500 -
P25 Io = 389 µW cm-2. 0.129 min-1
Aeroxide UV-C lamp 254 nm , kapp (pH = 7)
15.00 500 -
P25 Io = 389 µW cm-2. 0.163 min-1
Aeroxide UV-C lamp 254 nm , kapp (pH = 10)
15.00 500 -
P25 Io = 389 µW cm-2. 0.089 min-1
60% Chemical
Complete
126W medium Oxygen
Aeroxide degradation
[129] 0.20 571 pressure Hg lamp demand
P25 (pH = 3 effluent)
(Philips Brazil). remaining 60
60 min
min
TiO2 fibre
catalyst
81113– on fixed Low pressure 10W
Clarithromycin [123] 1.00 - kapp = 0.32 h-1 -
11–9 support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
4-chlorophenol,
isobutyric acid,
Xenon short-arc lamp
hydroquinone.
Aeroxide solar simulator. Io< kapp =
Clofibric acid 882-09-7 [93] 0.53 500 Presence of
P25 400 nm = 1.35×10-4 17×10-3 s-1
unidentified
einsteins m-2 s-1.
intermediates
45 min.

Xenon short-arc lamp


0.53 Hombikat solar simulator. Io< kapp =
500 As above
UV100 400 nm = 1.35×10-4 22×10-3 s-1
einsteins m-2 s-1.

TiO2 fibre
catalyst
on fixed Low pressure 10W
[123] 1.00 - kapp = 4.98 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
126 W medium
10.00 Aeroxide pressure mercury kapp(pH = 3)
[82] 1000 -
P25 UV lamp; Helios 3.28×10-2 min-1.
Italquartz, Milan.
126 W medium
10.00 Aeroxide pressure mercury kapp(pH = 11)
1000 -
P25 UV lamp; Helios 5.93×10-2 min-1
Italquartz, Milan.
4-chlorophenol,
Medium pressure isobutyric acid,
18.00 Aeroxide Hg lamp 366-578 kapp = 9.45×10 -2
hydroquinone,
[94] 1000
P25 nm. Io = 2.38×10-6 min-1 benzoquinone,
einstein s-1 4-
chlorocatechol.
Medium pressure
18.00 Hg lamp 366-578 kapp =1.11×10-1
1000 Anatase As above
nm. Io = 2.38×10-6 min-1
einstein s-1
Medium pressure
18.00 Hg lamp 366-578 kapp =1.02×10-2
1000 Rutile As above
nm. Io = 2.38×10-6 min-1
einstein s-1
Medium Pressure Hg kapp = 0.025
5.00 Aeroxide
[124] 100 lamp > 300 nm. Io = min-1. -
P25
5.1×10-6 einsteins s-1
47% degradation
Fluka 100% 6W UV-A lamp 365
Cloxacillin 61–72–3 [80] 105.00 500 300 min (pH -
Anatase nm.
= 5.0)

998
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

58% degradation
Fluka 100% 6W UV-A lamp
105.00 1000 300 min -
Anatase 365 nm.
(pH = 5.0)
59% degradation
Fluka 100% 6W UV-A lamp
105.00 1500 300 min -
Anatase 365 nm.
(pH = 5.0)
60% degradation
Fluka 100% 6W UV-A lamp
105.00 2000 300 min -
Anatase 365 nm.
(pH = 5.0)
95% degradation
Fluka 100% 6W UV-A lamp
105.00 1000 300 min -
Anatase 365 nm.
(pH = 3.0)
58% degradation
Fluka 100% 6W UV-A lamp
105.00 1000 300 min -
Anatase 365 nm.
(pH = 5.0)
82% degradation
Fluka 100% 6W UV-A lamp
105.00 1000 300 min -
Anatase 365 nm.
(pH = 8.0)
100%
Fluka 100% 6W UV-A lamp degradation
105.00 1000 -
Anatase 365 nm. 300 min
(pH = 11.0)
121 min,
crude photoproduct
9W UV-A lamp mixture
15307– 5.00 Aeroxide kapp =
Diclofenac [70] 250 (350 – 400 nm). Io = more toxic than
86–5 P25 0.1 min-1
3.37×10-6 einstein s-1. diclofenac
(Daphnia
magna).
9W UV-A lamp
10.00 Aeroxide (350 – 400 nm).
500 kapp = 0.03 min-1 As above
P25 Io = 3.37×10-6
einstein s-1
Modified
Natural Sunlight kapp = 0.4057 s-1
[120] 0.10 - SiO2 TiO2 -
10 am – 5 pm. (distilled water)
mix
Modified
Natural Sunlight kapp = 0.3238 s-1
0.10 - SiO2 TiO2 -
10 am – 5 pm (wastewater)
mix
Complete
1500 W Xenon arc mineralization
15.00 Aeroxide kapp= 0.058 min-1
[106] 200 lamp > 290 nm. 2h. Maximal
P25
Io = 750 W m-2. toxicity 72 min
(Vibrio fischeri)
100% ~20% TOC
Aeroxide Hg vapour lamp
[130] 20.00 200 degradation remaining
P25 126W
10 min. 80 min.
High-pressure
30% TOC
29.62 Aeroxide Hg lamp, > 297 nm.
[105] 1500 t1/2 =~ 3 min remaining
P25 Io(313 nm) = 3×10-5
(1 h)
einstein s-1.
TiO2 fibre
catalyst
on fixed Low pressure 10W
[123] 1.00 - kapp = 16.00 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
Solar pilot plant,
Aeroxide Undetectable
[121] 0.10 5 average -
P25 60 min.
Io = 30 W m-2.
38% TOC
Xenon lamp, Removal.
200.00 Aeroxide kapp =
[73] 1000 290 – 400 nm. Io = Minimal toxicity
P25 9.6×10-3 min-1.
6.9×10-6 einstein s-1. Vibrio fischeri
4h

999
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Immobilized
TiO2 Solar light simulator
Undetectable
[122] 0.10 - synthesized 290 – 800 nm. -
<5 min
by sol-gel Io = 765 W m-2.
process
Compound Parabolic
Aeroxide Collector, natural kapp =
[122] 0.10 5 -
P25 sunlight. 0.029 min-1
Io = 30 W m-2.
Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 - -
synthesized sunlight. 0.128 min-1
by sol-gel Io = 30 W m-2
process
Used
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 - -
synthesized sunlight. 0.085 min-1
by sol-gel Io = 30 W m-2
process
Compound Parabolic
Complete
Aeroxide Collector, natural ~12% remaining
[51] 50.00 200 degradation
P25 sunlight. DOC 200 min
200 min
Io = 30 W m-2
126 W Blacklight Less toxic
2.50 Aeroxide kapp =
[78] 800 300-420 nm Io = intermediates with
P25 0.1244 min-1
4.7×10-7 einstein s-1 higher TiO2 loadings
450 W Xenon arc Cleavage of
35.94 Hombikat lamp > 400 nm kapp(pH 3.0). piperazine ring.
Enrofloxacin 93106-60-6 [95] 500
UV100 Io= 1.6×10-4 19×10-1 min-1 No decrease in
einstein min-1 TOC > 3 h
9W UV-A lamp, 90%
Aeroxide
Erythromycin 115-07-8 [131] 10.00 250 350-400 nm, Io= - mineralization
P25
4.69×10-6 einstein s-1 (TOC) 121 min.
9W UV-A lamp, ~80%
Hombikat
[131] 10.00 250 350-400 nm, Io= - mineralization
UV (anatase)
4.69×10-6 einstein s-1 (TOC) 121 min.

9W UV-A lamp, ~80%


Aeroxide
[131] 10.00 100 350-400 nm, Io= - mineralization
P25
4.69×10-6 einstein s-1 (TOC) 121 min.
Complete
9W UV-A lamp,
Aeroxide mineralization
[131] 10.00 500 350-400 nm, Io= -
P25 (TOC) 90 min
4.69×10-6 einstein s-1
(pH = 5-5.4).
60%
9W UV-A lamp,
Aeroxide mineralization
[131] 10.00 500 350-400 nm, Io= -
P25 (TOC) 90 min
4.69×10-6 einstein s-1
(pH = 7-7.4).
90%
9W UV-A lamp,
Aeroxide mineralization
[131] 2.50 500 350-400 nm, Io= -
P25 (TOC) 30 min
4.69×10-6 einstein s-1

90%
9W UV-A lamp,
Aeroxide mineralization
[131] 5.00 500 350-400 nm, Io= -
P25 (TOC) 40 min
4.69×10-6 einstein s-1

Immobilized
TiO2 on UV-A Philips 126W Complete loss of
Estrone 53–16–7 [111] 0.01 - titanium High pressure Hg kapp = 0.086 min-1 estrogenic activity
alloy lamp. after 1 h.
surface.
UV-A lamp
Aeroxide ~5% remainng
[114] 1.00 400 max 355 nm, 8W, -
P25 180 min
Io = 116.6 W m-2.

1000
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

UV-C lamp
Aeroxide ~8% remaining
[114] 0.78 400 max 254 nm 8W, -
P25 180 min
Io = 114.5 W m-2

Aeroxide TQ-150 reactor,


[118] 0.10 1000 kapp = 0.86 h-1 -
P25 238-579 nm, 150 W

Aeroxide TQ-150 reactor,


[118] 0.25 1000 kapp = 0.82 h-1 -
P25 238-579 nm, 150 W

Aeroxide TQ-150 reactor,


[118] 0.50 1000 kapp = 0.84 h-1 -
P25 238-579 nm, 150 W

Aeroxide TQ-150 reactor,


[118] 1.00 1000 kapp = 0.86 h-1 -
P25 238-579 nm, 150 W

Aeroxide TQ-15-32 15W


[118] 0.10 1000 kapp = 2.34 h-1 -
P25 254 nm lamp.

Aeroxide TQ-15-32 15W


[118] 0.25 1000 kapp = 2.40 h-1 -
P25 254 nm lamp.

Aeroxide TQ-15-32 15W


[118] 0.50 1000 kapp = 2.45 h-1 -
P25 254 nm lamp.

Aeroxide TQ-15-32 15W


[118] 1.00 1000 kapp = 2.50 h-1 -
P25 254 nm lamp.

UV-A lamp
Aeroxide ~8% remaining
Estriol 50-27-1 [114] 1.00 400 max 355 nm, 8W, -
P25 180 min
Io = 116.6 W m-2

UV-C lamp
Aeroxide ~5% remainng
[114] 1.10 400 max 254 nm 8W, -
P25 180 min
Io = 114.5 W m-2

TiO2
integrated
with
126W medium
activated
76824– pressure lamp 248- kapp =
Famotidine [132] 33.00 - charcoal, -
35–6 579 nm, 0.0045 min-1
stationary
λmax = 366 nm.
support
(0.5% w/w
TiO2)
TiO2
integrated
with 126W medium
activated pressure lamp 248- kapp =
[132] 32.00 - -
charcoal, 579 nm, 0.0881min-1
stationary λmax = 366 nm.
support (1%
w/w TiO2)
TiO2
integrated
with
126W medium
activated
pressure lamp 248- kapp =
[132] 29.00 - charcoal, -
579 nm, 0.0965 min-1
stationary
λmax = 366 nm.
support
(2.5% w/w
TiO2)
TiO2
integrated
with 126W medium
activated pressure lamp kapp = 0.1324
[132] 27.00 - -
charcoal, 248-579 nm, λmax = min-1
stationary 366 nm.
support (5%
w/w TiO2)

1001
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

TiO2
integrated
with
126W medium
activated
pressure lamp 248- kapp =
[132] 25.00 - charcoal, -
579 nm, 0.1445 min-1
stationary
λmax = 366 nm.
support
(7.5% w/w
TiO2)
TiO2
integrated
with
126W medium
activated
pressure lamp 248- kapp =
[132] 25.00 - charcoal, -
579 nm, 0.1739 min-1
stationary
λmax = 366 nm.
support
(10% w/w
TiO2)
TiO2 fibre
catalyst
31879– on fixed Low pressure 10W
Fenoprofen [123] 1.00 - kapp = 4.85 h-1 -
05–7 support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
Immobilized
TiO2 Solar light simulator
Undetectable
Flumequine 42835-25-6 [122] 0.10 - synthesized 290 – 800 nm. -
10 min
by sol-gel Io = 765 W m-2.
process
Compound Parabolic
Aeroxide Collector, natural kapp =
[122] 0.10 5 -
P25 sunlight. 0.141 min-1
Io = 30 W m-2.
Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 5 -
synthesized sunlight. 0.460 min-1
by sol-gel Io = 30 W m-2.
process
TiO2
Suntest Solar XLS+
prepared kapp =
[133] 20.00 1.6 Reactor, -
by sol-gel 0.03 min-1
Io = 500 W m-2.
technique
TiO2
prepared
Suntest Solar
by sol-gel
[133] 20.00 1.6 XLS+ Reactor, kapp = 0.07 min-1 -
technique
Io = 500 W m-2.
doped with
thiourea
TiO2
prepared
Suntest Solar
by sol-gel
[133] 20.00 1.6 XLS+ Reactor, kapp = 0.08 min-1 -
technique
Io = 500 W m-2.
doped with
thiourea
Suntest Solar Complete
Aeroxide 80% degradation
[134] 20.00 0.5 XLS+ Reactor, mineralization
P25 1h
Io = 500 W m-2. 60 min.

450 W Xenon arc Cleavage of


26.13 Hombikat lamp > 400 nm kapp = piperazine ring.
[95] 500
UV100 Io= 1.6×10-4 1.37×10-2 min-1 No decrease in
einstein min-1 TOC > 3 h
75W high pressure
kapp (pH = 5)
Aeroxide Hg lamp,
Fluoxetine 54910-89-3 [158] 34.00 100 = 0.075 ± 0.002 -
P25 Io= 2-4 mW cm-2,
min-1
360 nm

1002
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

75W high pressure


kapp (pH = 11)
Aeroxide Hg lamp,
[158] 34.00 100 = 0.77 ± 0.09 -
P25 Io= 2-4 mW cm-2,
min-1
360 nm
75W high pressure
kapp (pH = 11) 50%
Aeroxide Hg lamp,
[158] 34.00 50 = 0.55 ± 0.04 mineralization 60
P25 Io= 2-4 mW cm-2,
min-1 min irradiation
360 nm
75W high pressure
kapp (pH = 11)
Aeroxide Hg lamp,
[158] 34.00 10 = 0.38 ± 0.05 -
P25 Io= 2-4 mW cm-2,
min-1
360 nm
126 W medium
5.00 Aeroxide pressure mercury kapp (pH = 3)
Furosemide 54–31–9 [82] 1000 -
P25 UV lamp; Helios 3.21×10-2 min-1.
Italquartz, Milan.
126 W medium
5.00 Aeroxide pressure mercury
[82] 1000 kapp =1.13×10-1 -
P25 UV lamp; Helios
Italquartz, Milan.
TiO2 fibre
catalyst
on fixed Low pressure 10W
Gemfibrozil 25812-30-0 [123] 1.00 - kapp = 0.64 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
126 W Medium
Complete Complete
Aeroxide pressure Hg lamp
[86] 47.00 400 degradation mineralization
P25 360 nm,
0.5 h 3.2 h
Io = 10 mW cm-2
126 W Medium
Complete
47.00 Hombikat pressure Hg lamp Complete
[86] 400 mineralization
UV 100 360 nm, degradation 3 h
15 h
Io = 10 mW cm-2
Modified
93479– Natural Sunlight kapp =0.2771 s-1
Glimepiride [120] 0.10 - SiO2 TiO2 -
97–1 10 am – 5 pm. (distilled water)
mix
Modified
Natural Sunlight kapp =0.2203 s-1
[120] 0.10 - SiO2 TiO2 -
10 am – 5 pm. (wastewater)
mix
9W UV-A lamp, 350-
15687– 10.00 Aeroxide 400 nm. 62% removal by
Ibuprofen [96] 250 -
27–1 P25 Io = 3.37×10-6 121 min
einsteins s-1.
9W UV-A lamp,
10.00 Aeroxide 350-400 nm. 65% removal by 46% DOC
[96] 500
P25 Io = 3.37×10-6 121 min removal
einsteins s-1.
9W UV-A lamp,
5.00 Aeroxide 350-400 nm. 80% removal by
[96] 250 -
P25 Io = 3.37×10-6 121 min
einsteins s-1.
9W UV-A lamp,
10.00 Aeroxide 350-400 nm. 70% removal by
[96] 250 -
P25 Io= 3.37×10-6 121 min
einsteins s-1.
9W UV-A lamp,
20.00 Aeroxide 350-400 nm. 65% removal by
[96] 250 -
P25 Io = 3.37×10-6 121 min
einsteins s-1.
Modified
Natural sunlight kapp = 0.2411 s-1
[120] 0.10 - SiO2 TiO2 -
10 am – 5 pm. (distilled water)
mix
Modified
Natural sunlight kapp = 0.2802 s-1
[120] 0.10 - SiO2 TiO2 -
10 am – 5 pm. (wastewater)
mix

1003
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

TiO2 fibre
catalyst
on fixed Low pressure 10W
[123] 1.00 - kapp = 1.33 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
Xenon lamp,
200.00 Aeroxide 290 – 400 nm. kapp =
[73] 1000 -
P25 Io = 6.9×10-6 9.1× 10-3 min-1
einstein s-1.
UV-vis Xenon Arc
6.60 Aeroxide lamp with Ultrasound kapp = DOC removal =
[135] 10
P25 Sonolysis at 1.84×10-3 min-1 55%
300 Hz, 80W
Complete 80% TOC
Aeroxide Solar pilot plant removal with remaining after
[136] 200.00 100
P25 photoreactor, solar energy solar energy
70 kJ L-1 80 kJ L-1

Complete
Aeroxide Solar pilot plant removal with
[136] 100.00 100 -
P25 photoreactor, solar energy
30 kJ L-1

Complete
Aeroxide Solar pilot plant removal with
[136] 50.00 100 -
P25 photoreactor, solar energy
10 kJ L-1
Complete
Aeroxide Solar pilot plant removal with
[136] 20.00 100 -
P25 photoreactor, solar energy
5 kJ L-1
Immobilized
TiO2 Solar light simulator
Undetectable
[122] 0.10 - synthesized 290 – 800 nm. -
30 min
by sol-gel Io = 765 W m-2.
process
Compound Parabolic
Aeroxide Collector, natural kapp =
[122] 0.10 5 -
P25 sunlight. 0.013 min-1
Io = 30 W m-2.
Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 - -
synthesized sunlight. 0.048 min-1
by sol-gel Io = 30 W m-2
process
Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 - -
synthesized sunlight. 0.128 min-1
by sol-gel Io = 30 W m-2
process

Xenon arc lamp > Complete Complete


Aeroxide
Imipramine 50–49–7 [137] 15.00 200 290 nm, degradation ~ mineralization
P25
Io = 750 W m-2. 1.5 h. 24 h.

TiO2 fibre
catalyst
on fixed Low pressure 10W
Indomethacin 53–86–1 [123] 1.00 - kapp = 5.11 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
Medium Pressure
5.00 Aeroxide Hg lamp > 300 nm. Io kapp (pH = 7.5)
Iomeprol 78649-41-9 [124] 100 -
P25 = 5.1×10-6 0.032 min-1
einstein s-1.

1004
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

1000W Xenon solar


Deiodination of
short-arc lamp
5.20 Aeroxide kapp = iopromol
Iopromol 73334-07-3 [93] 500 Io< 400 nm =
P25 5.25×10-3 s-1 occurs.
1.35×10-4
.
einstein m-2 s-1.
1000W Xenon solar
short-arc lamp Deiodination of
5.20 Hombikat kapp =
[93] 500 Io< 400 nm = iopromol
UV100 9.24×10-3 s-1
1.35×10-4 occurs
einstein m-2 s-1.
TiO2 fibre
catalyst
on fixed Low pressure 10W
Isopropylantipyrine 479–92–5 [123] 1.00 - kapp = 4.37 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.

TiO2 fibre
catalyst
22071– on fixed Low pressure 10W
Ketoprofen [123] 1.00 - kapp = 31.09 h-1 -
15–4 support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.

Immobilized
TiO2 Solar light simulator
Undetectable
Ketorolac 74103-06-3 [122] 0.10 - synthesized 290 – 800 nm. -
20 min
by sol-gel Io = 765 W m-2.
process
Compound Parabolic
Aeroxide Collector, natural kapp =
[122] 0.10 5 -
P25 sunlight. 0.035 min-1
Io = 30 W m-2.
Immobilized
Compound Parabolic
TiO2
Collector, natural kapp =
[122] 0.10 5 synthesized -
sunlight. 0.086 min-1
by sol-gel
Io = 30 W m-2.
process
Elimination of
piperazinylic
365 nm High- ring, loss of
100986– 36.14 Aeroxide kapp (pH = 7.0) =
Levofloxacin [138] 2000 pressure Hg lamp, fluorine atom,
85–4 P25 0.18 min-1
Io = 0.38 mW cm-2 multiple
hydroxylations.
.
365 nm High- 6 hr irradiation:
134678- Aeroxide kapp (pH = 7.0) =
Lamivudine [156] 0.10 250 pressure Hg lamp. 83%
17-4 P25 0.0395 min-1
Io = 0.38 mW cm-2 mineralization.

365 nm High- 6 hr irradiation:


Aeroxide kapp (pH = 7.0) =
[156] 0.10 1000 pressure Hg lamp. 83%
P25 0.0542 min-1
Io = 0.38 mW cm-2 mineralization

365 nm High- 6 hr irradiation:


Aeroxide kapp (pH = 7.0) =
[156] 0.10 3000 pressure Hg lamp. 83%
P25 0.0412 min-1
Io = 0.38 mW cm-2 mineralization

365 nm High- 6 hr irradiation:


Aeroxide kapp (pH = 3.0) =
[156] 0.10 1000 pressure Hg lamp. 83%
P25 0.0571 min-1
Io = 0.38 mW cm-2 mineralization
365 nm High- 6 hr irradiation:
Aeroxide kapp (pH = 5.0) =
[156] 0.10 1000 pressure Hg lamp. 83%
P25 0.0472 min-1
Io = 0.38 mW cm-2 mineralization
365 nm High- 6 hr irradiation:
Aeroxide kapp (pH = 9.0) =
[156] 0.10 1000 pressure Hg lamp. 83%
P25 0.0597 min-1
Io = 0.38 mW cm-2 mineralization
365 nm High- 6 hr irradiation:
Aeroxide kapp (pH = 11.0)
[156] 0.10 1000 pressure Hg lamp. 83%
P25 = 0.0322 min-1
Io = 0.38 mW cm-2 mineralization

1005
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

~ 50%
126W Medium
50 .00 Aeroxide Complete mineralization
Lincomycin 154–21–2 [75] 400 pressure Hg lamp.
P25 degradation 3 h after 5 h.
Io = 8.5 mW cm-2

No significant
mineralization
126W Medium
50.00 Merck 100% Complete 5 h. Thiomethyl
[75] 400 pressure Hg lamp.
Anatase degradation 3 h group to sulfone
Io= 8.5 mW cm-2
and sulfoxide
derivatives.

kapp =
Aeroxide
[139] 11.50 200 Solar Photoreactor 6.23×10-3 M -
P25
einstein-1

Elimination of
piperazynilic
365 nm High-
35.13 Aeroxide kapp (pH = 7.0) ring, loss of
Lomefloxacin 98019-51-7 [138] 2000 pressure Hg lamp,
P25 =0.13 min-1 fluorine atom,
Io= 0.38 mW cm-2
multiple
hydroxylations

Anatase
Hydroxylated
films on kapp (closed
3×20 W UV-A lamps derivatives.
75330– glass lactone form) =
Lovastatin [87] 10.00 - at 365 nm (Phillips Intermediates
75–5 slides 175 0.046 ± 0.006
CLEO model). less toxic than
×12.5×2 min-1.
parent statins
mm

Anatase
kapp (open Hydroxylated
films on
3×20 W UV-A lamps hydroxy acid derivatives.
glass
[87] 10.00 - at 365 nm (Phillips form with O2) = Intermediates
slides 175
CLEO model) 0.105 ± 0.004 less toxic than
×12.5×2
min-1. parent statins
mm

Anatase
kapp (open Hydroxylated
films on
3×20 W UV-A lamps hydroxy acid derivatives.
glass
[87] 10.00 at 365 nm (Phillips form purged with Intermediates
slides 175
CLEO model) N2) = 0.089 less toxic than
×12.5×2
0.003 min-1 parent statins
mm

Complete
Compound Parabolic degradation
75%
Aeroxide Collector, natural of major
Metamizole 68-89-3 [140] 50.00 200 mineralization 30
P25 sunlight. intermediate
min
Io = 30 W m-2. 4-methylantipy-
rine 65 min

Modified
Natural Sunlight kapp = 3.1407
Methotrexate 59–05–2 [120] 0.025 - SiO2 TiO2 -
10 am – 5 pm. (distilled water)
mix

Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A
37350– Aeroxide Complete
Metoprolol [157] 2.68 1000 (366 nm), kapp= 0.2 min-1
58–6 P25 mineralization
Io = 8.8×10-9 einstein
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation
Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A
[157] Aeroxide kapp= Complete
18.88 1000 (366 nm),
P25 0.0625 min-1 mineralization
Io = 8.8×10-9 einstein
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation

1006
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A kapp=
Aeroxide Complete
[157] 37.76 1000 (366 nm), 0.03
P25 mineralization
Io = 8.8×10-9 einstein min-1
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation

Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A kapp=
Wackherr Complete
[157] 2.68 1000 (366 nm), 0.35
TiO2 mineralization
Io = 8.8×10-9 einstein min-1
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation

Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A kapp=
Wackherr Complete
[157] 18.88 1000 (366 nm), 0.14
TiO2 mineralization
Io = 8.8×10-9 einstein min-1
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation

Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A
Wackherr kapp= Complete
[157] 37.76 1000 (366 nm),
TiO2 0.11 min-1 mineralization
Io = 8.8×10-9 einstein
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation

Hydroxyl radical
125W high pressure attack aromatic
Hg lamp, UV-A benzene ring.
[157] Aeroxide kapp=
13.40 1000 (366 nm), Complete
P25 0.075
Io = 8.8×10-9 einstein mineralization
min-1
min-1 mL-1. Aeroxide >
Wackherr 4h
irradiation
Hydroxyl radical
attack aromatic
125W high pressure benzene ring.
Hg lamp, UV-A Complete
[157] Aeroxide kapp=
13.40 2000 (366 nm), mineralization
P25 0.07 min-1
Io = 8.8×10-9 einstein Aeroxide >
min-1 mL-1. Wackherr 4h
irradiation

Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A
Aeroxide kapp= Complete
[157] 13.40 5000 (366 nm),
P25 0.06 min-1 mineralization
Io = 8.8×10-9 einstein
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation

Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A
Wackherr kapp= Complete
[157] 13.40 1000 (366 nm),
TiO2 0.18 min-1 mineralization
Io = 8.8×10-9 einstein
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation

1007
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A
[157] Wackherr kapp= Complete
13.40 2000 (366 nm),
TiO2 0.16 min-1 mineralization
Io = 8.8×10-9 einstein
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation
Hydroxyl radical
attack aromatic
125W high pressure
benzene ring.
Hg lamp, UV-A kapp= 0
[157] Wackherr Complete
13.40 5000 (366 nm), .15
TiO2 mineralization
Io = 8.8×10-9 einstein min-1
Aeroxide >
min-1 mL-1.
Wackherr 4h
irradiation
15W low pressure Hg
30%
Aeroxide lamp, UV-C 2 ~40% remaining
[141] 133.70 1000 mineralization
P25 54 nm, Io = 3.3×10-6 180 min
180 min (TOC)
einstein s-1.
1000W xenon lamp
~55%
Aeroxide 290-400 nm, 94% removal
[142] 50.00 400 mineralization
P25 Io = 3.34×10-5 240 min
360 min
einstein s-1;

Less toxic
High-pressure photoproducts
26.74 Aeroxide kapp (pH = 7.0)
[74] 2000 mercury lamp, 15-30 min
P25 0.072 min-1
365 nm. 126W. (Daphnia
magna)

UV-A lamp 365 nm,


354812- Aeroxide kapp (pH = 3)
Moxifloxacin [128] 15.00 500 Io= 485 µW cm-2, -
41-2 P25 0.069 min-1
300-440nm

UV-A lamp 365 nm,


Aeroxide kapp (pH = 7)
[128] 15.00 500 Io= 485 µW cm-2, -
P25 0.227 min-1
300-440nm

UV-A lamp 365 nm,


Aeroxide kapp (pH = 10)
[128] 15.00 500 Io= 485 µW cm-2, -
P25 0.081 min-1
300-440nm

Aeroxide UV-C lamp 254 nm , kapp (pH = 3)


[128] 15.00 500 -
P25 Io = 389 µW cm-2. 0.146 min-1

Aeroxide UV-C lamp 254 nm , kapp (pH = 7)


[128] 15.00 500 -
P25 Io = 389 µW cm-2. 0.236 min-1

Aeroxide UV-C lamp 254 nm , kapp (pH = 10)


[128] 15.00 500 -
P25 Io = 389 µW cm-2. 0.144 min-1

TiO2 fibre
catalyst
22204– on fixed Low pressure 10W
Naproxen [123] 1.00 - kapp = 3.73 h-1 -
53–1 support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
Xenon lamp,
Aeroxide 290 – 400 nm. kapp =
[73] 200.00 1000 -
P25 Io = 6.9×10-6 7.0× 10-3 min-1
einstein s-1.
126 W medium
5.00 Aeroxide pressure Hg lamp; kapp (pH = 3)
[82] 1000 -
P25 Helios Italquartz, 7.86×10-2 min-1
Milan.
126 W medium
Aeroxide pressure Hg lamp; kapp(pH = 11)
[82] 5.00 1000 -
P25 Helios Italquartz, 4.91×10-1 min-1
Milan

1008
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Elimination of
piperazynilic
365 nm High-
Aeroxide kapp (pH = 7.0) = ring, loss of
Norfloxacin 70458-96-7 [138] 32.00 2000 pressure Hg lamp,
P25 0.14 min-1 fluorine atom,
Io = 0.38 mW cm-2
multiple
hydroxylations
Complete
126W medium 20% TOC
Aeroxide degradation
[143] 80.00 1000 pressure mercury remaining.80
P25 of norfloxacin
lamp min
80 min
450 W Xenon arc Cleavage of
Hombikat lamp > 400 nm kapp (pH = 3)= piperazine ring.
[95] 32.00 500
UV100 Io= 1.6×10-4 7.19×10-2 min-1 No decrease in
einstein min-1 TOC > 3 h
Irradiation for
15-30 minutes
9W UV-A lamp
induces higher
83380– Aeroxide (350 – 400 nm). Conversion>
Ofloxacin [71] 10.00 250 toxicity to
47–6 P25 Io = 3.37×10-6 80% 250 min
Daphnia magna
einstein s-1.
than 1 h
irradiation.

< 10% Incomplete


1kW Solar simulator
Aeroxide conversion in pH mineralization.
[144] 10.00 250 xenon lamp,
P25 = 8 wastewater, 2% DOC
Io = 272.3 W m-2.
121 min removal

~25%
1kW Solar simulator
Aeroxide conversion in pH 6% DOC
[144] 10.00 500 xenon lamp,
P25 = 8 wastewater, removal
Io = 272.3 W m-2.
121 min

~45%
1kW Solar simulator
Aeroxide conversion in pH 8% DOC
[144] 10.00 1000 xenon lamp,
P25 = 8 wastewater, removal
Io = 272.3 W m-2.
121 min

~45%
1kW Solar simulator
Aeroxide conversion in pH 10% DOC
[144] 10.00 2000 xenon lamp,
P25 = 8 wastewater, removal
Io = 272.3 W m-2.
121 min

~60%
1kW Solar simulator
Aeroxide conversion in pH 12% DOC
[144] 10.00 3000 xenon lamp,
P25 = 8 wastewater, removal
Io = 272.3 W m-2.
121 min
~45%
1kW Solar simulator
Aeroxide conversion in pH
[144] 10.00 4000 xenon lamp, -
P25 = 8 wastewater,
Io = 272.3 W m-2.
121 min
1kW Solar simulator kapp (pH = 2
Aeroxide
[144] 10.00 3000 xenon lamp, wastewater) = -
P25
Io = 272.3 W m-2. 0.019 min-1
1kW Solar simulator kapp (pH = 8
Aeroxide
[144] 10.00 3000 xenon lamp, wastewater) = -
P25
Io = 272.3 W m-2. 0.009 min-1
1kW Solar simulator kapp (pH = 10
Aeroxide
[144] 10.00 3000 xenon lamp, wastewater) = -
P25
Io = 272.3 W m-2. 0.008 min-1
Immobilized
TiO2 Solar light simulator
Undetectable
[122] 0.10 - synthesized 290 – 800 nm. -
<5 min
by sol-gel Io = 765 W m-2.
process
Immobilized
Compound Parabolic
TiO2
Collector, natural Undetectable
[122] 0.10 - synthesized -
sunlight. 10 min
by sol-gel
Io = 30 W m-2
process

1009
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 5 -
synthesized sunlight. 1.577 min-1
by sol-gel Io = 30 W m-2.
process

Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 5 -
synthesized sunlight. 0.228 min-1
by sol-gel Io = 30 W m-2.
process

126 W medium
10.00 Aeroxide pressure mercury kapp(pH = 3)
[82] 1000 -
P25 UV lamp; Helios 2.94×10-1 min-1.
Italquartz, Milan.
126 W medium
10.00 Aeroxide pressure mercury kapp(pH = 11)
[82] 1000 -
P25 UV lamp; Helios 7.27×10-2 min-1.
Italquartz, Milan.
100%
Aeroxide Blacklight 365 nm degradation 50% removal
Oxolinic Acid 14698-29-4 [145] 20.00 1000
P25 UV-A, Io = 14 W m-2. 30 min DOC 60 min
(pH = 7.5)
80% degradation
Aeroxide Blacklight 365 nm 50% removal
[145] 20.00 1000 10 min
P25 UV-A, Io = 14 W m-2. DOC 60 min
(pH = 7.5)
66% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 200 15 min -
P25 UV-A, Io = 14 W m-2.
(pH = 7.5).

42% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 200 15 min -
P25 UV-A, Io = 14 W m-2.
(pH = 11).

66% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 1500 15 min -
P25 UV-A, Io = 14 W m-2.
(pH =7.5).

50% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 1500 15 min -
P25 UV-A, Io = 14 W m-2.
(pH =11).

79% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 850 15 min -
P25 UV-A, Io = 14 W m-2.
(pH =7.5).

60% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 850 15 min -
P25 UV-A, Io = 14 W m-2.
(pH =11).
49% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 200 15 min -
P25 UV-A, Io = 14 W m-2.
(pH =9.25).
63% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 1500 15 min -
P25 UV-A, Io = 14 W m-2.
(pH =9.25).
76% degradation
Aeroxide Blacklight 365 nm
[145] 20.00 850 15 min -
P25 UV-A, Io = 14 W m-2.
(pH =9.25).
Aeroxide
Chemical
P25 TiO2
Complete oxygen
immobilized Blacklight UV-A
[146] 18.00 - degradation demand < 5%
on sintered 360 nm lamp, 36W
121 min 160 min, TOC <
glass
40% 180 min
cylinders
Complete
Aeroxide Blacklight UV-A 360
[146] 18.00 1000 degradation -
P25 nm lamp, 36W
40 min

1010
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Inhibition
Aeroxide
(Vibrio
P25
50.00 2×254nm UV lamps, >90% removal Qinghaiensis)
Oxytetracycline 79–57–2 [147] 100 dispersed
Io = 845×10-6 W cm-2 (pH =7) 210 min decreased to
on zeolite
30% after 270
5A
min
Inhibition
Aeroxide
(Vibrio
P25 >80% removal
50.00 2×254nm UV lamps, Qinghaiensis)
[147] 100 dispersed (pH = 7)
Io = 845×10-6 W cm-2 decreased to
on zeolite 210 min.
13% after 270
13X
min

Solar pilot plant,


Aeroxide Undetectable
Paracetamol 103–90–2 [121] 0.10 5 average -
P25 145 min.
Io = 30 W m-2.

Immobilized
TiO2 Solar light simulator
Undetectable
[122] 0.10 - synthesized 290 – 800 nm. -
25 min
by sol-gel Io = 765 W m-2.
process

Compound Parabolic
Aeroxide Collector, natural kapp =
[122] 0.10 5 -
P25 sunlight. 0.027 min-1
Io = 30 W m-2.
Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 - -
synthesized sunlight. 0.080 min-1
by sol-gel Io = 30 W m-2
process

Used
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 - -
synthesized sunlight. 0.045 min-1
by sol-gel Io = 30 W m-2
process
60%
mineralization 300
UV-C source 254 nm,
604.80 Aeroxide kapp = 10.5 ± min.
[99] 400 with minor distribution
P25 1.6×10-3 min-1. Carboxylic acids,
185 nm
hydroquinone,
acetamide

604.80 Aeroxide 8 W UV-A source: kapp = 1.9 ± Slight change in


[99] 400
P25 blacklight 365 nm. 0.2×10-3 min-1 TOC

Nano
TiO2: High
7.56 250W metal halide pH = 9:~100%
[72] 2000 Technology Hydroquinone
lamp, > 365 nm removal
Nano Co.,
China
Nano
TiO2: High pH = 9 and
7.56 250W metal halide
[72] 2000 Technology pH = 6.5: ~95% Hydroquinone
lamp, > 365 nm
Nano Co., removal
China
Nano
TiO2: High pH = 3:~92%
7.56 250W metal halide
[72] 2000 Technology removal Hydroquinone
lamp, >365 nm
Nano Co., (pH = 3)
China
Nano
TiO2: High
7.56 250W metal halide pH = 11:~70%
[72] 2000 Technology Hydroquinone
lamp, > 365 nm removal .
Nano Co.,
China

1011
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

TiO2 fibre
catalyst
on fixed Low pressure 10W
Phenacetin 62–44–2 [123] 1.00 - kapp = 0.15 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
Solar pilot plant, >196 min
Aeroxide
Phenazone 60–80–0 [121] 0.10 5 average Io = 30 to complete -
P25
W m-2. degradation
Immobilized
TiO2 Solar light simulator
50% remaining
[122] 0.10 - synthesized 290 – 800 nm. -
50 min
by sol-gel Io = 765 W m-2.
process

Compound Parabolic
Aeroxide Collector, natural kapp =
[122] 0.10 5 -
P25 sunlight. 0.019 min-1
Io = 30 W m-2.

Immobilized
Compound Parabolic
TiO2
Collector, natural ~25% remaining
[122] 0.10 5 synthesized -
sunlight. 50 min
by sol-gel
Io = 30 W m-2.
process
Used
Immobilized Compound Parabolic
TiO2 Collector, natural kapp = 0.022
[122] 0.10 5 -
synthesized sunlight. min-1
by sol-gel Io = 30 W m-2.
process

126 W medium
10.00 Aeroxide pressure mercury kapp (pH = 3)
[82] 1000 -
P25 UV lamp; Helios 1.74×10-1 min-1.
Italquartz, Milan.

126 W medium
10.00 Aeroxide pressure mercury kapp(pH = 11)
[82] 1000 -
P25 UV lamp; Helios 1.60×10-1 min-1
Italquartz, Milan.

TiO2 fibre
catalyst
on fixed Low pressure 10W
Phenobarbital 50–06–6 [123] 1.00 - kapp = 0.62 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
TiO2 fibre
catalyst
on fixed Low pressure 10W
Phenytoin 57–41–0 [123] 1.00 - kapp = 2.65 h-1 -
support, UV-C 254 nm lamp.
Ube Ltd.,
Japan.
Anatase
kapp Hydroxylated
films on
3×20 W UV-A lamps (open hydroxy derivatives.
81103– glass
Pravastatin [87] 10.00 - at 365 nm (Phillips acid form, O2) = Intermediates
37–0 slides 175
CLEO model). 0.107 ± 0.006 less toxic than
×12.5×2
min-1 parent statins
mm
Anatase kapp
Hydroxylated
films on (open hydroxy
3×20 W UV-A lamps derivatives.
glass acid form,
[87] 10.00 - at 365 nm (Phillips Intermediates
slides 175 purged with N2)
CLEO model). less toxic than
×12.5×2 = 0.083 ± 0.004
parent statins
mm min-1
Solar pilot plant,
Aeroxide Undetectable
Progesterone 57-83-0 [121] 0.10 5 average Io = 30 -
P25 145 min
W m-2.

1012
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Immobilized
TiO2 Solar light simulator
Undetectable
[122] 0.10 - synthesized 290 – 800 nm. -
<5 min
by sol-gel Io = 765 W m-2.
process
Compound Parabolic
Aeroxide Collector, natural ~20% remaining
[122] 0.10 5 -
P25 sunlight. 90 min
Io = 30 W m-2.

Fresh
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 - -
synthesized sunlight. 0.071 min-1
by sol-gel Io = 30 W m-2
process

1000W xenon lamp


~55%
Aeroxide 290-400 nm, 94% removal
Propanolol 525–66–6 [142] 50.00 400 mineralization
P25 Io = 3.34×10-5 240 min
360 min
einstein s-1;

TOC < 10%


(250 min).
25.93 Aeroxide High-pressure Hg kapp (pH = 7)=
[74] 2000 Aromatic
P25 lamp, 365 nm. 126W. 0.182 min-1
Hydroxylated
Intermediates

~ 60%
126W Medium Complete
66357– 50 .00 Aeroxide mineralization
Ranitidine [75] 400 pressure Hg lamp. degradation
35–5 P25 5h
Io = 8.5 mW cm-2 0.5 h

Merck 126W Medium No significant


Complete
[75] 50.00 400 (100% pressure Hg lamp. mineralization
degradation 1 h
anatase) Io = 8.5 mW cm-2 5h

126 W medium
10.00 Aeroxide pressure mercury kapp (pH = 3)
[82] 1000 -
P25 UV lamp; Helios 9.74×10-2 min-1.
Italquartz, Milan.

126 W medium
10.00 Aeroxide pressure Hg UV kapp (pH = 11)
[82] 1000 -
P25 lamp; Helios 5.35×10-2 min-1
Italquartz, Milan.

37%
Sunlight, pilot plant mineralization
kapp
10.00 Aeroxide (latitude 37°N, 73 min;.
[85] 200 (distilled water)
P25 longitude propionic, oxalic
= 0.146 min-1.
2.4°W). and formic
acids
Intermediates:
Sunlight, pilot plant
kapp Hydroxylated
10.00 Aeroxide (latitude 37°N,
[85] 200 (effluent water) = ranitidine ;
P25 longitude
0.00997 min-1 desmethylated
2.4°W).
ranitidine.
Complete
mineralization 3
h.
Xenon arc lamp Complete
18559– 15.00 Aeroxide Intermediates
Salbutamol [107] 200 1500 W > 290 nm. degradation
94–9 P25 more toxic than
Io = 750 W m-2 30 min.
salbutamol
(Vibrio fischeri ,
15 min).
Less than
TiO2 fibres kapp =
High pressure 40%
100.00 distributed 0.0016 min-1
Salicylic acid 69–72–7 [89] 2500 Hg lamp at 365 nm. mineralization.
on a glass (with oxygen
500 W. Refractory
film. bubbled).
carboxylic acids

1013
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

TiO2 fibres 2,3


High pressure Hg ~25% removal
100.00 distributed dihydroxybenzoic
[89] 2500 lamp at 365 nm. (without bubbled
on a glass acids, muconic
500 W oxygen).
film. acid.
Wackherr 40 W UV-B lamp,
50.00 Standard Spectrum kapp (pH = 3.6)
[83] 500 -
(100% 290 nm – 320 nm. 2.9×10-5 s-1
anatase). Io = 2.6×10-4 W cm-2.
Wackherr 40 W UV-B lamp,
50.00 Standard Spectrum kapp(pH = 5.2)
[83] 500 -
(100% 290 nm – 320 nm. 3.26×10-5 s-1
anatase). Io = 2.6×10-4 W cm-2

Wackherr 40 W UV-B lamp,


50.00 Standard Spectrum kapp (pH = 7.4)
[83] 500 -
(100% 290 nm – 320 nm. 3.57×10-5 s-1
anatase). Io = 2.6×10-4 W cm-2

Aldrich
13.80 (70:30 400W high pressure kapp = 3.33×10-8
[148] 1000 -
anatase: Hg lamp mol L-1 s-1.
rutile).
450 W Hanovia High-
TiO2
21.00 pressure Hg lamp, > 75% removal of
prepared
[149] 1000 280 nm. salicylic acid -
by a sol-gel
Io = 193 µeinsteins (45 min, pH= 4).
process
L-1 min-1.
Immobilized
anatase TiO2
prepared UV –C low pressure
by an Hg lamp, ~ 80% removal
[150] 10.00 - -
atomic layer 250-260 nm. (pH = 3) 1 hr
deposition Io = 0.2 mW cm-2
process on
glass plates.
Immobilized
anatase TiO2
prepared UV –C low pressure
by an Hg lamp, ~65% removal
[150] 10.00 - -
atomic layer 250-260 nm. (pH = 4.2) 1 hr
deposition Io = 0.2 mW cm-2
process on
glass plates.
Immobilized
anatase TiO2
prepared UV –C low pressure
by an Hg lamp, ~70% removal
[150] 10.00 - -
atomic layer 250-260 nm. (pH = 6) 1 hr
deposition Io = 0.2 mW cm-2
process on
glass plates.
Immobilized
anatase TiO2
prepared UV –C low pressure
by an Hg lamp, ~50% removal
[150] 10.00 - -
atomic layer 250-260 nm. (pH = 8) 1 hr
deposition Io = 0.2 mW cm-2
process on
glass plates.
Immobilized
anatase TiO2
prepared UV –C low pressure
by an Hg lamp, ~65% removal
[150] 10.00 - -
atomic layer 250-260 nm. (pH = 10) 1 hr
deposition Io = 0.2 mW cm-2
process on
glass plates.

1014
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

TiO2 films
Hydroxylated
of anatase kapp
3×20 W UV-A lamps derivatives
79902– on glass (closed lactone
Simvastatin [87] 10.00 - 365 nm (Phillips far less toxic
63–9 slides 175 form) = 0.052 ±
CLEO model). than parent
×12.5×2 0.008 min-1.
(Vibrio fischeri)
mm

TiO2 films kapp


Hydroxylated
of anatase (open hydroxy
3×20 W UV-A lamps derivatives
on glass acid form in the
[87] 10.00 - 365 nm (Phillips far less toxic
slides 175 presence of O2)
CLEO model). than parent
×12.5×2 = 0.114 ± 0.007
(Vibrio fischeri)
mm min-1.

TiO2 films
kapp Hydroxylated
of anatase
3×20 W UV-A lamps (open hydroxy derivatives
on glass
[87] 10.00 - 365 nm (Phillips acid form purged far less toxic
slides 175
CLEO model). with N2) = 0.095 than parent
×12.5×2
± 0.006 min-1. (Vibrio fischeri)
mm
30-70% TOC
(300 min).
kapp =
UV-A lamp λmax = Toxicity of
Riedel de- 0.0132 min-1.
[108] 366 nm. photoproducts
Sulfacetamide 144–80–9 21.42 2500 Haen TiO2 Complete
Io = 8.76×10-9 (Chlorella
standard. degradation
einstein s-1 cm-2. vulgaris) lower
300 min
than parent.

Removal 240 min TOC


High-pressure Efficiency: 85.2% levels < 20%.
28.47 Aeroxide
Sulfachlorpyridazine 80–32–0 [76] 2000 mercury lamp, (60 min). kapp Clevage of S-N
P25
365 nm. 126W (pH = 7.0) bond and
0.031 min-1. hydroxylation.

kapp =
UV-A lamp with
Riedel de- 0.0131 min-1. 30-70% TOC
λmax = 366 nm.
Sulfadiazine 68–35–9 [108] 25.03 2.5 Haen TiO2 Complete (300 min)
Io= 8.76×10-9
standard. degradation
einstein s-1 cm-2.
300 min.

9W UV-A
20% DOC
350-400 nm lamp,
Aeroxide 65% degradation 360 min. Sulfate,
Sulfamethazine 57-68-1 [97] 50.00 1000 λmax = 366 nm.
P25 60 min. ammonium,
Io= 2.02×10-4
nitrate ions.
einstein min-1

9W UV-A 70% DOC


350-400 nm lamp, 360 min. Sulfate,
Tronox 100% 39% degradation
[97] 50.00 1000 λmax = 366 nm. ammonium,
anatase 60 min.
Io= 2.02×10-4 nitrate ions.
einstein min-1

UV-A Xenon Arc lamp kapp =


Aeroxide
Sulfamethiazole 144–82–1 [90] 27.00 100 Io = 9 x10-5 0.033 min-1 -
P25
einstein min-1 (pH = 3)

[151] Aeroxide Xenon lamp > 80% 25% TOC


Sulfamethoxazole 723–46–6 100.00 500
[152] P25 290 nm, 1000W degradation, 6 h. removal, 6h.

[151] Aeroxide Xenon lamp > 88% 88% TOC


100.00 1000
[152] P25 290 nm, 1000W degradation, 6 h. removal, 6 h.

[151] Aeroxide Xenon lamp > 91% 40% TOC


100.00 2000
[152] P25 290 nm, 1000W degradation, 6 h removal, 6 h.
kapp =
UV-A lamp with λmax
Riedel de- 0.0301 min-1. 30-70% TOC
25.33 = 366 nm.
[108] 2500 Haen TiO2 Complete (300 min)
Io= 8.76×10-9
standard degradation
einstein s-1 cm-2.
200 min

1015
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

Oxalic acid.
Minimal
High-pressure Hg toxicity
25.33 Aeroxide
[109] 1500 lamp, > 290 nm, t1/2= 5 min reduction
P25
Io = 0.112 einstein h-1 (Daphnia
magna)
121 min.
100% ~20% TOC
Aeroxide Hg vapour lamp
[130] 20.00 200 degradation remaining 80
P25 126W
10 min. min.
80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 25.33 100 Io = 9 x10-5 0.054 min-1
P25 Ammonium,
einstein min-1 (pH = 3)
nitrate ions
detected.

80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 25.33 100 Io = 9 x10-5 0.076 min-1
P25 ammonium,
einstein min-1 (pH = 3, O2)
nitrate ions
detected.

80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 1.27 100 Io = 9 x10-5 0.36 min-1
P25 ammonium,
einstein min-1 (pH = 3)
nitrate ions
detected.
80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 2.28 100 Io = 9 x10-5 0.30 min-1
P25 ammonium,
einstein min-1 (pH = 3)
nitrate ions
detected.
80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 12.00 100 Io = 9 x10-5 0.11 min-1
P25 ammonium,
einstein min-1 (pH = 3)
nitrate ions
detected.

80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 58.00 100 Io = 9 x10-5 0.025 min-1
P25 ammonium,
einstein min-1 (pH = 3)
nitrate ions
detected.

80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 122.00 100 Io = 9 x10-5 0.015 min-1
P25 ammonium,
einstein min-1 (pH = 3)
nitrate ions
detected.

80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 25.33 100 Io = 9 x10-5 0.042 min-1
P25 ammonium,
einstein min-1 (pH = 5)
nitrate ions
detected.

80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 25.33 100 Io = 9 x10-5 0.064 min-1
P25 ammonium,
einstein min-1 (pH = 9)
nitrate ions
detected.

1016
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Aeroxide Sulfate,
[90] 25.33 100 Io = 9 x10-5 0.063 min-1
P25 ammonium,
einstein min-1 (pH = 11)
nitrate ions
detected.
80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
Hombikat Sulfate,
[90] 25.33 100 Io = 9 x10-5 0.0054 min-1
UV Anatase ammonium,
einstein min-1 (pH = 3)
nitrate ions
detected.
80% reduction
DOC 6 h.
UV-A Xenon Arc lamp kapp =
TiOxide Sulfate,
[90] 25.33 100 Io = 9 x10-5 0.0028 min-1
Rutile ammonium,
einstein min-1 (pH = 3)
nitrate ions
detected.

Solar pilot plant,


Aeroxide Undetectable
[121] 0.10 5 average -
P25 145 min.
Io = 30 W m-2.

Immobilized
TiO2 Solar light simulator
Undetectable
[122] 0.10 - synthesized 290 – 800 nm. -
20 min
by sol-gel Io = 765 W m-2.
process
Compound Parabolic
Aeroxide Collector, natural kapp =
[122] 0.10 5 -
P25 sunlight. 0.035 min-1
Io = 30 W m-2.

Immobilized
Compound Parabolic
TiO2
Collector, natural ~25% remaining
[122] 0.10 5 synthesized -
sunlight. 50 min
by sol-gel
Io = 30 W m-2.
process

Used
Immobilized Compound Parabolic
TiO2 Collector, natural kapp =
[122] 0.10 5 -
synthesized sunlight. 0.085 min-1
by sol-gel Io = 30 W m-2.
process

Toxic
photoproducts 13
UV-C 254 nm lamps, h (Daphnia
Aeroxide Complete
[153] 60.00 500 Io = 1.3×10-3 magna 48 h).
P25 removal 60 min
einstein min-1 L-1 Sulfanilic acid, 3-
amino-5-
methylisoxazole
9W UV-A lamp,
Complete
Aeroxide 350 – 400 nm. >90% reduction
[79] 10.00 500 degradation
P25 Io = 2.81×10-4 TOC 121 min
30 min
einstein min-1.
9W UV-A lamp,
Complete
Aeroxide 350 – 400 nm. >80% reduction
[79] 10.00 250 degradation ~
P25 Io = 2.81×10-4 TOC 121 min
45 min
einstein min-1.
9W UV-A lamp,
~80%
Hombikat 350 – 400 nm. ~60% reduction
[79] 10.00 250 degradation
UV anatase Io = 2.81×10-4 TOC 121 min
121 min
einstein min-1.
9W UV-A lamp,
Complete
Aeroxide 350 – 400 nm. ~75% reduction
[79] 30.00 500 degradation
P25 Io = 2.81×10-4 TOC 121 min
90 min
einstein min-1.

1017
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

9W UV-A lamp,
Complete
Aeroxide 350 – 400 nm. ~80% reduction
[79] 20.00 500 degradation
P25 Io = 2.81×10-4 TOC 121 min
45 min
einstein min-1.
9W UV-A lamp,
Complete
Aeroxide 350 – 400 nm. ~80% reduction
[79] 10.00 100 degradation
P25 Io = 2.81×10-4 TOC 121 min
45 min
einstein min-1.
9W UV-A lamp,
Complete
Aeroxide 350 – 400 nm. ~85% reduction
[79] 10.00 250 degradation
P25 Io = 2.81×10-4 TOC 121 min
45 min
einstein min-1.

9W UV-A lamp,
Complete
Aeroxide 350 – 400 nm. ~90% reduction
[79] 10.00 750 degradation
P25 Io = 2.81×10-4 TOC 121 min
30 min
einstein min-1.

9W UV-A lamp, >90% reduction


Aeroxide 350 – 400 nm. (Ultrapure water,
[79] 10.00 500 -
P25 Io = 2.81×10-4 pH = 3.9-4.1)
einstein min-1. 20 min

9W UV-A lamp, >80% reduction


Aeroxide 350 – 400 nm. (Ultrapure water,
[79] 10.00 500 -
P25 Io = 2.81×10-4 pH = 7.2-7.8).20
einstein min-1. min

9W UV-A lamp, >80% reduction


Aeroxide 350 – 400 nm. (Groundwater,
[79] 10.00 500 -
P25 Io = 2.81×10-4 pH = 4.8-5.6)
einstein min-1. 20 min.

9W UV-A lamp, >70% reduction


Aeroxide 350 – 400 nm. (Groundwater,
[79] 10.00 500 -
P25 Io = 2.81×10-4 pH = 7.8-8.3)
einstein min-1. 20 min.

9W UV-A lamp, >90% reduction


Aeroxide 350 – 400 nm. (Wastewater,
[79] 10.00 500 -
P25 Io = 2.81×10-4 pH = 4.8-5.6)
einstein min-1. 20 min.

9W UV-A lamp, ~80% reduction


Aeroxide 350 – 400 nm. (Wastewater,
[79] 10.00 500 -
P25 Io = 2.81×10-4 pH = 7.5-8.2)
einstein min-1. 20 min.

kapp
(pH = 7.0)
High-pressure 240 min TOC
24.93 Aeroxide 0.043 min-1.
Sulfapyridine 144–83–2 [76] 2000 mercury lamp, levels < 20%.
P25 Removal
365 nm. 126W
Efficiency:
92.5%(60 min).
kapp =
UV-A lamp
Riedel de- 0.0175 min-1.
λmax = 366 nm. 30-70% TOC
Sulfathiazole 72–14–0 [108] 25.53 2500 Haen TiO2 Complete
Io = 8.76×10-9 (300 min).
standard degradation
einstein s-1cm-2.
200 min
UV-A Xenon Arc lamp kapp =
Aeroxide
[90] 25.53 100 Io = 9 x10-5 0.053 min-1 -
P25
einstein min-1 (pH = 3)
UV-A Xenon Arc lamp kapp =
Aeroxide
Sulfisoxazole 128-69-5 [90] 26.73 100 Io = 9 x10-5 0.055 min-1 ( -
P25
einstein min-1 pH = 3)
kapp
(pH = 7.0)
240 min TOC
26.73 Aeroxide High-pressure Hg 0.031 min-1
[76] 2000 levels < 20%.
P25 lamp, 365 nm. 126W Removal
efficiency: 85.0%
(60 min)

1018
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Continued
Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.
Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts
Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

126 W Medium
Complete Complete
20.00 Aeroxide pressure mercury
Tamoxifen 10540-29-1 [86] 400 degradation mineralization
P25 lamp at 360 nm,
60 min 22 h
Io = 10 mW cm-2.
126 W Medium
Merck Complete Complete
20.00 pressure mercury
[86] 400 (100% degradation mineralization
lamp at 360 nm,
anatase). 83 min 28 h
Io = 10 mW cm-2
126W Medium
>98% decrease Mineralization
50.00 Aeroxide pressure mercury
Tetracycline 60–54–8 [75] 400 in concentration near completion
P25 lamp.
2h 5h
Io = 8.5 mW cm-2
50%
126W Medium mineralization;
Merck
pressure mercury Complete loss of
[75] 50.00 1000 (100%
lamp. degradation 2 h dimethylamine
anatase)
Io = 8.5 mW cm-2 group;
dealkylation.
~90%
Aeroxide Solarium UV-A lamp,
[103] 0.50 20 degradation -
P25 15W
60 min
~90%
Aeroxide Solarium UV-A lamp,
[103] 0.50 20 degradation -
P25 30W
60 min
~90%
Aeroxide Solarium UV-A lamp,
[103] 0.50 20 degradation -
P25 60W
60 min
~75%
Aeroxide Solarium UV-A lamp,
[103] 1.00 20 degradation -
P25 15W
60 min
~90%
Aeroxide Solarium UV-A lamp,
[103] 1.00 20 degradation -
P25 60W
60 min
~50%
Aeroxide Solarium UV-A lamp,
[103] 2.00 20 degradation -
P25 15W
60 min
~70%
Aeroxide Solarium UV-A lamp,
[103] 2.00 20 degradation -
P25 60W
60 min
~90%
Aeroxide Solarium UV-A lamp,
[103] 0.50 20 degradation -
P25 30W
60 min
~67%
Aeroxide Blacklight 365 nm,
[103] 0.50 20 degradation -
P25 32W
60 min

~90%
Aeroxide Solarium UV-A lamp,
[103] 0.50 20 degradation -
P25 60W
60 min

~53%
N-doped Solarium UV-A lamp,
[103] 0.50 20 degradation -
TiO2 60W
60 min

~52%
Fe-doped Solarium UV-A lamp,
[103] 0.50 20 degradation -
TiO2 60W
60 min
~69%
Zr-doped Solarium UV-A lamp,
[103] 0.50 20 degradation -
TiO2 60W
60 min
90%
Mineralization
UV (>254 nm) Philips
( 2 h) CO2, NH3
40.00 Aeroxide HPLN 126W; kapp =
[101] 500 and H2O. No
P25 Io (360 nm) = 71.6×10-3 s-1
antibacterial
1220 µW cm-2
effects
1h

1019
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Table 1. Pharmaceuticals reported to degrade via TiO2 assisted photocatalytic processes.


Continued

Pharmaceutical CAS Ref. [Pharmaceutical] [TiO2] TiO2 Apparatus Degradation Photoproducts


Number (mg L-1) (mg L-1) catalyst conditions kinetics and
mineralization

75%
6×20W Solarium Mineralization
lamps (2 h) CO2, NH3
40.00 Aeroxide kapp =
[101] 500 (300-400 nm) Philips H2O. No
P25 39.3×10-3 s-1.
HB31; Io (360nm) = antibacterial
1980 µW cm-2 effects
1h

160 W Philips
40.00 Aeroxide Blacklight (365 nm). Io kapp = Neglibible
[101] 500
P25 (360 nm) = 5.53×10-3s-1. mineralization.
59 µW cm-2

30% TOC
remaining 60 min.
Complete
Aeroxide Suntest XLS+ Solar Complete
[154] 20.00 1500 degradation
P25 lamp, Io = 250 W m-2. removal
15 min, pH = 8.7
antibacterial
activity

Aeroxide Xenon lamp > 100% ~50% TOC


Trimethoprim 738–70–5 [152] 100.00 500
P25 290 nm, 1000W degradation 6 h. removal, 6h.

Aeroxide Xenon lamp > 100% ~50% TOC


[152] 100.00 1000
P25 290 nm, 1000W degradation 6 h. removal, 6h.

Aeroxide Xenon lamp > 100% ~50% TOC


[152] 100.00 2000
P25 290 nm, 1000W degradation 6 h. removal, 6h.

97.5% ~20% TOC


Aeroxide Hg vapour lamp
[130] 20.00 200 degradation remaining
P25 126W
30 min. 90 min.

Compound Parabolic kapp (Distilled ~30% DOC


Aeroxide
[155] 20.00 200 Collector, natural water) = remaining
P25
sunlight, 30 W m-2. 0.22 min-1 100 min

Compound Parabolic kapp (Sewage ~30% DOC


Aeroxide
[155] 20.00 200 Collector, natural water) = remaining
P25
sunlight, 30 W m-2. 0.081 min-1 360 min

presence of bubbled oxygen progressed at faster rates predominant photocatalysts [71,96]. For example, Silva
compared with nitrogen-purged solutions [87]. Providing and Faria (2008) [94] compared the photodegradation
the dissolved oxygen content in solutions is not limiting, rates of clofibric acid using either commercial Aeroxide
any increases in oxygen concentration should increase P25, anatase or rutile. The anatase photocatalyst
the O2∙- production, which in turn, favors H2O2 and HO. degraded clofibric acid faster than the rutile potocatalyst
radical formation [90]. but slower than Aeroxide P25 which has a mixed
anatase:rutile composition. Another study confirmed
2.4. Effect of TiO2 type on photocatalytic that Aeroxide P25 is more photocatalytically efficient
degradation than pure form anatase or rutile photocatalysts probably
The form of the TiO2 used in experiments, such as as a result of reduced recombination of valence hole-
whether the TiO2 is in a suspension or immobilized form, conduction band electron events on the surface or the
or whether the TiO2 has been doped, has a significant bulk of the photocatalyst [97].
influence on photodegradation rates [91,92], and The use of various doped TiO2 photocatalysts has
degradation efficiencies of these TiO2 materials vary been reported to remove potential organic contaminants
from one pharmaceutical to another. The photocatalytic such as phenol and azo dyes [98]. Little research has
activity of various forms of TiO2 (pure anatase, pure been done on the removal of pharmaceuticals with
rutile or an anatase-rutile mixture) have been compared these doped TiO2 photocatalysts, and while commerical
in many studies [71,75,86,93-96]. As predicted by the preparations of doped materials are available in some
band gap differences between anatase and rutile, higher countries for research (i.e., Japan) [100], much of
conversion rates have been observed for anatase- the present literature focuses on the synthesis and

1020
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

characterisation of these doped materials [102]. However, alone, thus the observed degradation kinetics from the
a previous report has observed the degradation of salicylic UV-A/TiO2 process was solely derived from the TiO2
acid by a samarium-nitrogen doped TiO2 under visible photocatalysis of the pharmaceutical.
light [104] having a photocatalytic efficiency greater
than that of extemporaneously-prepared undoped TiO2. 2.6. Effect of electron acceptors on
While doping may be an effective strategy to decrease the photocatalytic degradation of
the band gap energy of TiO2, and thus allow visible-light pharmaceuticals
photocatalysis of organic contaminants, the decrease The addition of electron acceptors to the
in the band gap energy may increase the ability for photodegradation mixture significantly enhances
recombination [102] resulting in unpredictability of photodegradation rates of substrates. As noted
the photocatalytic efficiency of doped TiO2 materials. previously, oxygen saturation increases degradation
Klauson et al. [91] observed that a 0.42% iron-doped rates. Paul et al. (2007) [95] observed a marked
TiO2 material increased pharmaceutical photocatalysis improvement in degradation of ciprofloxacin and other
by 10% compared to undoped TiO2; however, when the fluoroquinolones when bromate ion (BrO3-) was added as
dopant concentration in the TiO2 was increased, the an electron acceptor. BrO3- - promoted degradation when
resultant material was less efficient in photocatalysis. used in conjunction with visible light irradiation, whereas
Indeed, Choina et al. [103] observed that N, Fe or Zr the absence of BrO3- or molecular oxygen (anoxic
doping of TiO2 did not enhance the photodegradation conditions) prevented any significant photodegradation.
of tetracyclines after 60 min degradation, compared Since the band gap energy of TiO2 [57] does not permit
to undoped Aeroxide P25 alone. While there is some the formation of electron-hole pairs using visible light,
evidence to suggest that doping of TiO2 increases the authors suggest that the photocatalytic oxidation of
photocatalytic efficiency, many of these materials are fluoroquinolones is mediated by the transfer of electron(s)
not tandardized. Therefore, it is difficult to conclude to the electron acceptor resulting in the formation of
whether they are truly more efficient than Aeroxide P25 unstable radical fluoroquinolone species which are
or other standardized undoped materials. In addition, further oxidized. Furthermore, the addition of hydroxyl
it would be useful to understand the photocatalytic radical scavengers (such as methanol) and superoxide
abilities of one standardized doped TiO2 material on a scavengers (such as superoxide dismutase) decreased
range of pharmaceutical compounds and compare its the degradation rate of ciprofloxacin under UV but not
photocatalytic efficiency with undoped TiO2. visible light irradiation. Such results suggested that
the visible light-induced photocatalysis of ciprofloxacin
2.5. UV-C vs UV-A photodegradation of is not mediated by electron-hole pairs as there are no
pharmaceuticals significant changes to the photodegradation rate as a
The radiation source used to generate the (h+-e-) result of HO. or O2∙- quenching.
pairs in the TiO2 photocatalysts may also affect Other systems utilized to increase photodegradation
photodegradation. Yang et al. (2009) [99] reported that and mineralization rates have included the addition of
TiO2-assisted paracetamol degradation rates using ozone or hydrogen peroxide to the TiO2 system [105]
UV-C were significantly faster than UV-A. Furthermore, which may lead to the formation of additional hydroperoxyl
the photodegradation of tetracycline [101] was or hydroxyl radicals, respectively, when irradiated by
reportedly faster using UV-B (>254 nm) and Solarium UV [89]. However, these experimental variations have
lamps, in contrast to blacklight (365 nm) assisted led to variable results. Diclofenac mineralization (i.e.,
photodegradation. In addition, the power of the lamps the conversion of the pharmaceutical completely to
used for irradiation processes may significantly affect inorganic compounds such as CO2, H2O and NH3) was
removal of pharmaceutical compounds as observed improved with the addition of ozone to the UV/TiO2
with the photocatalytic degradation of the antibacterial system [105] and only 10% of the total organic carbon
tetracycline [103]. While the ability to generate (h+-e-) content (TOC) remained in the irradiated suspension
pairs is independent of the wavelength of radiation used compared with 30% TOC remaining in the absence of
if the radiation is higher-energy than the TiO2 band gap, ozone. As TOC measures the concentration of parent
other processes, such as direct photolysis, may further pharmaceuticals and any intermediate photoproducts,
increase the apparent degradation rates observed as the parameter is a good indicator of mineralization
with the UV-C induced TiO2-assisted degradation of achieved by the photocatalytic process. Since the
paracetamol [99] In contrast, no significant degradation intermediate photoproducts formed via diclofenac
was found for the drug when irradiated with UV-A photodegradation and photocatalysis are more

1021
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

toxic than the parent pharmaceutical, adding ozone identified in the study, along with the toxic compound
improves the efficiency and acceptability of the UV/TiO2 hydroquinone. Rizzo et al. (2009) [78] reported that a
system as a feasible wastewater treatment process. 121-minute irradiation of diclofenac in aqueous solution
However, the addition of a high concentration of H2O2 lead to insignificant reductions in toxicity to Daphnia
(> 20 mmol L-1) to a UV/TiO2 photocatalytic fibre system magna with a TiO2 loading of 0.2 g L-1. However,
inhibited the degradation of salicylic acid [89] while lower irradiated suspensions were less toxic than the
H2O2 concentrations promoted salicylic acid degradation. unirradiated suspension when the TiO2 concentration
It was suggested in the study that H2O2 may also act as was increased to 0.4 g L-1 and 0.8 g L-1. These results
an electron acceptor for conduction band electrons and suggest that chloroderivative intermediates formed in
may compete with molecular oxygen for adsorption sites the photodegradation pathway for diclofenac are clearly
on the surface of the TiO2 photocatalyst. more toxic than diclofenac and an extended irradiation
time (> 2 h) or an increase in TiO2 concentration must be
2.7. Degradation pathways for pharmaceuticals employed to ensure an efficient removal of diclofenac
and ecotoxicity of photoproducts to form non-toxic and presumably mineralized products.
The photodegradation pathways and extent of Similar toxic intermediates were identified from the TiO2-
mineralization for TiO2 - photocatalysed pharmaceuticals assisted photodegradation of ibuprofen [73]. However,
have been reported widely with some reports observing again it is important to note that sewage effluent and
complete mineralization of pharmaceuticals [86,103,108]. environmental concentrations of ibuprofen are likely to
Significant decreases in toxicity to the test organism has be much lower than those used in these experiments,
been observed for many studies after treatment with and thus, the behaviour of the UV/TiO2 photocatalytic
UV/TiO2 [71,87,104]. Piecha et al. (2010) [87] observed system to such lowered concentrations may vary from
that the photoproducts derived from UV/TiO2 treatment these experimental results.
of statin drugs were of significantly lower toxicity to Vibrio The production of intermediates which are more toxic
fischeri compared to the parent statins. In addition, the than the parent pharmaceutical have also been reported
degradation of sulfa drugs was observed to produce for the TiO2 – assisted degradation of amiloride [112],
a mixture of photoproducts with reduced toxicity [108] the selective beta-2-adrenergic agonist salbutamol
after 300 minutes irradiation.This is consistent with [107], the antiepileptic agent carbamazepine [78,93]
another study [109] which reported some toxicity even and the antibacterial agent ofloxacin [71]. Unirradiated
after treatment of sulfamethoxazole with UV/TiO2 for amiloride solutions were not shown to be toxic to Vibrio
121 minutes. In contrast, UV/TiO2 treatment of atenolol fischeri, but there was a 40% increase in toxicity to this
(TiO2 loading = 150 mg L-1) in aqueous suspension organism after 4 h treatment with UV/TiO2. Identified
for 15-30 minutes resulted in a significant reduction in photoproducts after prolonged photocatalysis included
toxicity to Daphnia magna [71], and no antibacterial small molecules such as guanidine which was resistant
effects were observed after a 1 hr UV/TiO2 treatment of to UV/TiO2 treatment and not fully mineralized to
an aqueous tetracycline suspension [101]. nitrogenous by-products until > 45 h photocatalysis
Many studies have evaluated the ecotoxicity from [112]. It is possible that the toxicity of the irradiated
the photoproducts of non-steroidal anti-inflammatory amiloride was attributed to the formation of smaller,
drug (NSAIDs) during the photocatalytic process, unknown molecules. Similarly a solution of salbutamol
particularly diclofenac and ibuprofen [70,73,78,102]. [107] that had been irradiated in the presence of TiO2
Previous experiments on the direct UV photolysis and for 15 minute was observed to be more toxic than the
the UV/H2O2 and photoFenton mediated degradation unirradiated suspension, and a decrease in toxicity to
of diclofenac has shown that identified photoirradiation Vibrio fischeri was only observed after irradiating the
intermediates, including 8-chlorocarbazoleacetic acid, salbutamol suspension for 60 minutes. A potentially
were more toxic than diclofenac [110], and indeed, some mutagenic and carcinogenic compound, acridine, was
of these intermediates may also be formed by UV/TiO2 elucidated in the UV/TiO2 treatment of carbamazepine
systems. Calza et al. (2006) [106] observed that the [93].
toxicity of a 20-minute irradiated solution of diclofenac These findings clearly suggest that UV/TiO2 processes
had a 72% growth inhibition of the luminescent successfully remove pharmaceuticals in aqueous
bacterium Vibrio fischeri, whereas only 24% growth suspension if an appropriate treatment timeframe is
inhibition was observed with unirradiated suspensions. applied, and this parameter is especially important to
Several hydroxylated and chlorophenol derivatives, consider when treating wastewater suspected of being
including 2,6-dichlorophenol and 4-chlorocatechol were rich in pharmaceuticals. The treatment timeframe should

1022
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

ideally be derived from bioassays which can provide In addition, much of the current literature concerning
information on whether certain timeframes are adequate the photocatalytic degradation of pharmaceuticals use
to prevent the production of toxic intermediates and undoped TiO2 materials such as Aeroxide P25. While it
ensure the complete removal of toxic intermediates has been observed that the use of doped TiO2 materials
[113]. has enhanced the photodegradation of various organic
contaminants such as dyes and pesticides, little is known
about the photocatalytic behaviour of these materials
3. Conclusions and future in the degradation of pharmaceutical compounds.
developments Patents concerning the characterisation and synthesis
of doped materials are abundantly available;
The literature suggests that TiO2 - assisted however, the photoactivity of these novel materials
degradation systems may be potentially feasible on pharmaceutical compounds is poorly defined.
wastewater treatment processes for the degradation Also, while there are standardized methods
of pharamceuticals, given that some studies have on the preparation of doped TiO2 photocatalytic
reported on the complete mineralization of particular materials, commercially-prepared doped materials
pharmaceuticals. However, several questions need are less available as research reagents. Furthermore,
to be answered before such technique can be while theoretically feasible, there are limitations
employed successfully in any wastewater treatment to undoped TiO2 which may render it impractical
facility: for sewage treatment after treatment times
- What pharmaceuticals are expected to appear and loadings for the optimal removal of a particular
in the influent of a wastewater treatment facility? pharmaceutical is considered. As the band gap of
This question can be answered at least in part undoped TiO2 requires UV to create valence hole-electron
from a knowledge of the particular medications pairs, the cost of installing UV lamps and the energy
used and disposed by a population served required to run these lamps in some sewage treatment
by the particular wastwater treatment plant. Such facilities may render the technique economically
information can be obtained from studies which unfeasible. The use of TiO2 at concentrations of 1-2 g L-1
identify and quantify the type and amount of particular to achieve optimal effects in the removal of a
pharmaceuticals, or modelled from prescription data particular pharmaceutical may also be cost-inhibitive.
relating to the population served by a wastewater Therefore, in order to establish effective strategies
treatment facility. in the removal of pharmaceuticals from sewage
-What pharmaceutical concentrations are expected? water, further research comparing the photocatalytic
The removal of pharmaceuticals at higher concentrations abilities of both doped and undoped materials
may benefit from increased TiO2 loadings (for example, on the photodegradation of pharmaceutical compounds
in the range of 1-2 g L-1). should be carried out. Because of the unpredictable
-What potential effects does the wastewater matrix efficiency of doped TiO2 materials, such research
have on photocatalysis? As noted in this review, natural is neccessary to determine whether these doped
organic matter may act as inner filters or adsorb / materials are truly more viable as photocatalysts
trap radical species and inhibit TiO2 photocatalysis than undoped TiO2 for the photocatalytic degradation
mechanisms, thereby leading to decreased degradation of pharmaceuticals. The use of inexpensive materials
of pharmaceuticals in the wastewater compared to for the synthesis of doped TiO2 photocatalysts
solutions involving pure water which are the most likely would increase the sewage treatment feasibility
situation in the laboratory. of these materials. Once studies are completed
-What are the operating conditions of the plant on the ability of these doped TiO2 photocatalysts
(pH, type and intensity of UV-irradiation available)? to remove pharmaceutical compounds from water,
Such operating conditions may drastically affect it would be of benefit to commercialize
the photocatalytic rates or types of photoproducts an effective doped photocatalyst for sewage treatment
produced. use.

1023
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

References

[1] S.A. Snyder, P. Westerhoff, Y. Yoon, D. L. Sedlak, [23] S.D. Kim, J. Cho, I.S. Kim, B.J. Vanderford,
Environmental Engineering Science 20, 449 S.A. Snyder, Water Research 41, 1013 (2007)
(2003) [24] S. Managaki, A. Murata, H. Takada, B.C. Tuyen,
[2] D.W. Kolpin, E.T. Furlong, M.T. Meyer, N.H. Chiem, Environ. Sci. Technol. 41, 8004
E.M. Thurman, S.D. Zuagg, L.B. Barber, (2007)
H.T. Buxton, Environmental Science & Technology [25] W. Xu, G. Zhang, S. Zou, Z. Ling, G. Wang, W. Yan,
36, 1212 (2002) Water Environment Research 81, 248 (2009)
[3] O.V. Enick, M.M. Moore, Environmental Impact [26] P.M. Palmer, L.R. Wilson, P. O’Keefe, R. Sheridan,
Assessment Review 27, 707 (2007) T. King, C.Y. Chen, Science of the Total Environment
[4] J. Siemens, G. Huschek, C. Siebe, M. Kaupenjohann, 394, 90 (2008)
Water Research 42, 2125 (2008) [27] M. Leclercq, O. Mathieu, E. Gomez, C. Casellas,
[5] J.P. Bound, N. Voulvoulis, Water Research 40, H. Fenet, D. Hillaire-Buys, Archives of
2885 (2006) Environmental Contamination and Toxicology 56,
[6] D. Fatta-Kassinos, S. Meric, A. Nikolaou, Anal. 408 (2008)
Bioanal. Chem. 399, 251 (2011) [28] J. Radjenovic, M. Petrovic, D. Barcelo, Water
[7] B.E. Haggard, J.M. Galloway, W.R. Green, Research 43, 831 (2009)
M.T. Meyer, J. Environ. Qual. 35, 1078 (2006) [29] D. Camacho-Muñoz, J. Martín, J.L. Santos,
[8] S.G. Alonso, M. Catala, R.R. Maroto, J.L.R. Gil, I. Aparicio, E. Alonso, Journal of Hazardous
A.G. de Miguel, Y. Valcarcel, Environment Materials 183, 602 (2010)
International 36, 195 (2010) [30] S. Zorita, L. Martensson, L. Mathiasson, Science of
[9] F. Comeau, C. Surette, G.L. Brun, R. Losier, Science the Total Environment 407, 2760 (2009)
of the Total Environment 396, 132 (2008) [31] J.L. Packer, J.J. Werner, D.E. Latch, K. McNeill,
[10] G.G. Ying, R.S. Kookana, D.W. Kolpin, Journal of W.A. Arnold, Aquatic Sciences 65, 342 (2003)
Environmental Monitoring 11, 1498 (2009) [32] O.A.H. Jones, N. Voulvoulis, J.N. Lester,
[11] H.R. Buser, T. Poiger, M.D. Muller, Journal of the Environmental Pollution 145, 738 (2007)
American Chemical Society 32, 3449 (1998) [33] D. Stulten, S. Zuhlke, M. Lamshoft, M. Spiteller,
[12] C. Tixier, H.P. Singer, S. Oellers, S.R. Muller, Science of the Total Environment 405, 310 (2008)
Environmental Science & Technology 37, 1061 [34] Y.J. Zhang, S.U. Geissen, C. Gal, Chemosphere
(2003) 73, 1161 (2008)
[13] M.L. Sacca, C. Accinelli, J. Fick, R. Lindberg, [35] A.L. Boreen, W.A. Arnold, K. McNeill, Aquatic
B. Olsen, Chemosphere 75, 28 (2009) Sciences 65, 320 (2003)
[14] B. Kasprzyk-Hordern, R.M. Dinsdale, A.J. Guwy, [36] J.P. Bound, N. Voulvoulis, Environ. Health Perspect.
Water Research 3498 (2008) 114, 1705 (2005)
[15] M.J. Benotti, R.A. Trenholm, B.J. Vanderford, [37] A.Y.C. Tong, B.M. Peake, R. Braund, Environment
J.C. Holady, B.D. Stanford, S.A. Snyder, Environ. International 37, 292 (2011)
Sci. Technol. 43, 597 (2009) [38] N. Vieno, T. Tuhkanen, L. Kronberg, Water Research
[16] Y.C. Guo, S.W. Krasner, Journal of the American 41, 1001 (2007)
Water Resources Association 45, 58 (2009) [39] R. Rosal, A. Rodriguez, J.A. Perdigon-Melon,
[17] M.J. Focazio, D.W. Kolpin, K.K. Barnes, A. Petre, E. Garcia-Calvo, M.J. Gomez, A. Aguera,
E.T. Furlong, M.T. Meyer, S.D. Zaugg, L.B. Barber, A.R. Fernandez-Alba, Water Res. 44, 578 (2009)
E.M. Thurman, Science of the Total Environment [40] N. Paxeus, Water Science and Technology 50, 253
402, 201 (2008) (2004)
[18] G.M. Bruce, R.C. Pleus, S.A. Snyder, Environmental [41] S. Suarez, J.M. Lerna, F. Omil, Bioresource
Science & Technology 44, 5619 (2010) Technology 100, 2138 (2009)
[19] T.A. Ternes, Water Research 32, 3245 (1998) [42] R. Reif, S. Suarez, F. Omil, J.M. Lema, Desalination
[20] R. Kanda, P. Griffin, H.A. James, J. Fothergill, 221, 511 (2008)
Journal of Environmental Monitoring 5, 823 (2003) [43] M. Klavarioti, D. Mantzavinos, D. Kassinos, Environ.
[21] N. Nakada, T. Tanishima, H. Shinohara, K. Kiri, Int. 35, 402 (2009)
H. Takada, Water Research 40, 3297 (2006) [44] Q.T. Liu, H.E. Williams, Environmental Science &
[22] H. Chang, H. Hu, B. Shao, Environ. Sci. Technol. Technology 41, 803 (2007)
41, 3462 (2007) [45] Y.N.B. Li, D.E. Moore, B. Tattam, International

1024
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

Journal of Pharmaceutics 183, 110 (1999) [69] S.A. Santos Melo, A.G. Trovo, I.R. Bautitz,
[46] W.Z. Li, S.G. Lu, Z.F. Qiu, K.F. Lin, Journal of R.F. Pupo Nogueira, Revista Brasileira de Zootecnia
Hazardous Materials 176, 1051 (2010) 38, 188 (2009) (In Portuguese)
[47] R. Andreozzi, V. Caprio, R. Marotta, D. Vogna, [70] A. Achilleos, E. Hapeshi, N.P. Xekoukoulotakis,
Water Research 37, 993 (2003) D. Mantzavinos, D. Fatta-Kassinos, Chemical
[48] F.L. Rosario-Ortiz, E.C. Wert, S.A. Snyder, Water Engineering Journal 161, 53 (2010)
Research 44, 1440 (2010) [71] E. Hapeshi, A. Achilleos, M.I. Vasquez, C. Michael,
[49] D. Vogna, R. Marotta, A. Napolitano, R. Andreozzi, N.P. Xekoukoulotakis, D. Mantzavinos, D. Kassinos,
M. d’Ischia, Water Research 38, 414 (2004) Water Research 44, 1737 (2010)
[50] M. Ravina, L. Campanella, J. Kiwi, Water Research [72] X. Zhang, F. Wu, X. Wu, P. Chen, N. Deng, Journal
36, 3553 (2002) of Hazardous Materials 157, 300 (2008)
[51] L.A. Pérez-Estrada, M.I. Maldonado, W. Gernjak, [73] F. Mendez-Arriaga, S. Esplugas, J. Gimenez, Water
A. Agüera, A.R. Fernández-Alba, M.M. Ballesteros, Research 42, 585 (2008)
S. Malato, Catalysis Today 101, 219 (2005) [74] H. Yang, G.Y. Li, T.C. An, Y.P. Gao, J.M. Fu, Catalysis
[52] A. Goi, Y. Veressinina, M. Trapido, Chemical Today 153, 200 (2010)
Engineering Journal 143, 1 (2008) [75] M. Addamo, V. Augugliaro, A. Di Paola,
[53] A.G. Trovo, S.A.S. Melo, R.F.P. Nogueira, E. Garcia-Lopez, V. Loddo, G. Marci, L. Palmisano,
J. Photochem. Photobiol. A-Chem. 198, 215 Journal of Applied Electrochemistry 35, 765 (2005)
(2008) [76] H. Yang, T.C. An, G.Y. Li, W.H. Song, W.J. Cooper,
[54] S.A.S. Melo, A.G. Trovo, I.R. Bautitz, .F.P. Nogueira, H.Y. Luo, X.D. Guo, Journal of Hazardous Materials
Quim. Nova 32, 188 (2009) 179, 834 (2010)
[55] D.A. Panayotov, J.T. Yates, Chemical Physics [77] L. Yang, L.E. Yu, M.B. Ray, Water Research 42,
Letters 410, 11 (2005) 3480 (2008)
[56] T.L. Thompson, J.T. Yates, Journal of Physical [78] L. Rizzo, S. Meric, M. Guida, D. Kassinos,
Chemistry B 110, 18230 (2005) V. Belgiorno, Water Research 43, 4070 (2009)
[57] T.L. Thompson, J.T. Yates, Topics in Catalysis 35, [79] N.P. Xekoukoulotakis, C. Drosou, C. Brebou,
197 (2005) E. Chatzisymeon, E. Hapeshi, D. Fatta-Kassinos,
[58] T.L. Thompson, J.T. Yates, Chemical Reviews 106, D. Mantzavinos, Catalysis Today 161, 163 (2011)
4428 (2006) [80] E.S. Elmolla, M. Chaudhuri, Desalination 256, 43
[59] L.G. Devi, N. Kottam, S.G. Kumar, K.E. Rajashekhar, (2010)
Central European Journal of Chemistry 8, 142 [81] T.C. An, H. Yang, G.Y. Li, W.H. Song, W.J. Cooper,
(2010) X.P. Nie, Applied Catalysis B-Environmental 94,
[60] L.G. Devi, B.N. Murthy, Central European Journal 288 (2010)
of Chemistry 7, 119 (2009) [82] R. Molinari, F. Pirillo, V. Loddo, L. Palmisano,
[61] N.N. Binitha, Z. Yaakob, R. Resmi, Central European Catalysis Today 119, 205 (2006)
Journal of Chemistry 8, 182 (2010) [83] M.E. Carlotti, S. Sapino, D. Vione, C. Minero,
[62] C. Karunakaran, R. Dhanalakshmi, Central E. Peira, M. Trotta, Journal of Dispersion Science
European Journal of Chemistry 7, 134 (2009) and Technology 28, 805 (2007)
[63] K.J. Zhang, W. Xu, X.J. Li, S.J. Zheng, G. Xu, [84] T.E. Doll, F.H. Frimmel, Water Research 39, 403
Central European Journal of Chemistry 4, 234 (2005)
(2006) [85] J. Radjenovic, C. Sirtori, M. Petrovic, D. Barcelo,
[64] Q.O. Sun, Y.M. Xu, Journal of Physical Chemistry C S. Malato, Chemosphere 79, 368 (2010)
115, 18911 (2010) [86] S. Yurdakal, V. Loddo, V. Augugliaro, H. Berber,
[65] M. Faisal, M. Abu Tariq, M. Muneer, Adv. Sci. Lett. G. Palmisano, L. Palmisano, Catalysis Today 130,
3, 512 (2010) 9 (2007)
[66] J. Senthilnathan, L. Philip, J. Environ. Sci. Health [87] M. Piecha, M. Sarakha, P. Trebse, Journal of
Part B-Pestic. Contam. Agric. Wastes 44, 262 Photochemistry and Photobiology a-Chemistry
(2009) 213, 61 (2010)
[67] D.V. Sojic, V.B. Anderluh, D.Z. Orcic, B.F. Abramovic, [88] F. Mendez-Arriaga, S. Esplugas, J. Gimenez, Water
J. Hazard. Mater. 168, 94 (2009) Research 42, 585 (2008)
[68] K. Sahel, N. Perol, F. Dappozze, M. Bouhent, [89] G. Laera, B. Jin, H. Zhu, A. Lopez, Catalysis Today
Z. Derriche, C. Guillard, J. Photochem. Photobiol. 161, 147 (2011)
A-Chem. 212, 107 (2010) [90] L.H. Hu, P.M. Flanders, P.L. Miller, T.J. Strathmann,

1025
Unauthenticated
Download Date | 11/6/15 8:40 AM
TiO2-assisted photodegradation
of pharmaceuticals – a review

Water Research 41, 2612 (2007) (2007)


[91] D. Klauson, J. Babkina, K. Stepanova, [111] H.M. Coleman, E.J. Routledge, J.P. Sumpter,
M. Krichevskaya, S. Preis, Catalysis Today 151, B.R. Eggins, J.A. Byrne, Water Research 38,
39 (2010) 3233 (2004)
[92] N. Miranda-García, M.I. Maldonado, [112] P. Calza, C. Massolino, G. Monaco, C. Medana,
J.M. Coronado, S. Malato, Catalysis Today 151, C. Baiocchi, Journal of Pharmaceutical and
107 (2010) Biomedical Analysis 48, 315 (2008)
[93] T.E. Doll, F.H. Frimmel, Catalysis Today 101, 195 [113] L. Rizzo, Water Research 45, 4311 (2011)
(2005) [114] G.L. Puma, V. Puddu, H.K. Tsang, A. Gora,
[94] C.G. Silva, J.L. Faria, Photochemical & B. Toepfer, Applied Catalysis B-Environmental 99,
Photobiological Sciences 8, 705 (2009) 388 (2010)
[95] T. Paul, P.L. Miller, T.J. Strathmann, Environmental [115] W.L. Sun, S. Li, J.X. Mai, J.R. Ni, Chemosphere
Science & Technology 41, 4720 (2007) 81, 92 (2010)
[96] A. Achilleos, E. Hapeshi, N.P. Xekoukoulotakis, [116] J. Mai, W. Sun, L. Xiong, Y. Liu, J. Ni, Chemosphere
D. Mantzavinos, D. Fatta-Kassinos, Separation 73, 600 (2008)
Science and Technology 45, 1564 (2010) [117] Y. Ohko, K.I. Iuchi, C. Niwa, T. Tatsuma,
[97] S. Kaniou, K. Pitarakis, I. Barlagianni, I. Poulios, T. Nakashima, T. Iguchi, Y. Kubota, A. Fujishima,
Chemosphere 60, 372 (2005) Environmental Science & Technology 36, 4175
[98] B. Kosowska, S. Mozia, A.W. Morawski, B. Grzmil, (2002)
M. Janus, K. Kaucki, Solar Energy Materials and [118] Y. Zhang, J.L. Zhou, B. Ning, Water Research 41,
Solar Cells 88, 269 (2005) 19 (2007)
[99] L.M. Yang, L.E. Yu, M.B. Ray, Environmental [119] D.A. Lambropoulou, M.D. Hemando,
Science & Technology 43, 460 (2009) I.K. Konstantinou, E.M. Thurman, I. Ferrer,
[100] A. Zaleska, Recent Patents on Engineering 2, T.A. Albanis, A.R. Fernandez-Alba, Journal of
157 (2008) Chromatography A 1193, 38 (2008)
[101] C. Reyes, J. Fernandez, J. Freer, M.A. Mondaca, [120] W. Alahmad, M.A. Alawi, Jordan Journal of
C. Zaror, S. Malato, H.D. Mansilla, Journal of Pharmaceutical Sciences 3, 127 (2010)
Photochemistry and Photobiology a-Chemistry [121] N. Klamerth, N. Miranda, S. Malato, A. Agüera,
184, 141 (2006) A.R. Fernández-Alba, M.I. Maldonado,
[102] F. Han, V.S.R. Kambala, M. Srinivasan, J.M. Coronado, Catalysis Today 144, 125 (2009)
D. Rajarathnam, R. Naidu, Applied Catalysis A: [122] N. Miranda-García, M.I. Maldonado,
General 359, 25 (2009) J.M. Coronado, S. Malato, Catalysis Today 151,
[103] J. Choina, H. Duwensee, G.-U. Flechsig, 107 (2010)
H. Kosslick, A.W. Morawski, V.A. Tuan, A. Schulz, [123] R.R. Giri, H. Ozaki, S. Ota, R. Takanami,
Central European Journal of Chemistry 8, 1298 S. Taniguchi, International Journal of
(2010) Environmental Science and Technology 7, 251
[104] Y. Ma, J. Zhang, B. Tian, F. Chen, L. Wang, (2010)
J. Hazard. Mater. 182, 386 (2010) [124] M. Ziegmann, F.H. Frimmel, Water Science and
[105] J.F. Garcia-Araya, F.J. Beltran, A. Aguinaco, Technology 61, 273 (2010)
Journal of Chemical Technology and Biotechnology [125] A. Chatzitakis, C. Berberidou, I. Paspaltsis,
85, 798 (2010) G. Kyriakou, T. Sklaviadis, I. Poulios, Water
[106] P. Calza, V.A. Sakkas, C. Medana, C. Baiocchi, Research 42, 386 (2008)
A. Dimou, E. Pelizzetti, T. Albanis, Applied [126] J. Zhang, D. Fu, Y. Xu, C. Liu, Journal of
Catalysis B-Environmental 67, 197 (2006) Environmental Sciences 22, 1291 (2010)
[107] V.A. Sakkas, P. Calza, C. Medana, A.E. Villioti, [127] T. Paul, M.C. Dodd, T.J. Strathmann, Water
C. Baiocchi, E. Pelizzetti, T. Albanis, Applied Research 44, 3122 (2010)
Catalysis B-Environmental 77, 135 (2007) [128] X. Van Doorslaer, K. Demeestere,
[108] W. Baran, J. Sochacka, W. Wardas, Chemosphere P.M. Heynderickx, H. Van Langenhove, J. Dewulf,
65, 1305 (2006) Applied Catalysis B: Environmental 3, 540 (2011)
[109] F.J. Beltran, A. Aguinaco, J.F. Garcia-Araya, [129] T.G. Vasconcelos, K. Kümmerer, D.M. Henriques,
A. Oropesa, Water Research 42, 3799 (2008) A.F. Martins, Journal of Hazardous Materials 169,
[110] M. Schmitt-Jansen, P. Bartels, N. Adler, 1164 (2009)
R. Altenburger, Anal. Bioanal. Chem. 387, 1389 [130] L.H. da Cruz, F.G. Henning, A.B. dos Santos,

1026
Unauthenticated
Download Date | 11/6/15 8:40 AM
A. Y.C. Tong et al.

P. Peralta-Zamora, Quimica Nova 33, 1280 [144] I. Michael, E. Hapeshi, C. Michael,


(2010) D. Fatta-Kassinos, Water Research 44, 5450
[131] N.P. Xekoukoulotakis, N. Xinidis, M. Chroni, (2010)
D. Mantzavinos, D. Venieri, E. Hapeshi, [145] A.L. Giraldo, G.A. Peñuela, R.A. Torres-Palma,
D. Fatta-Kassinos, Catalysis Today 151, 29 N.J. Pino, R.A. Palominos, H.D. Mansilla, Water
(2010) Research 44, 5158 (2010)
[132] D. Keane, S. Basha, K. Nolan, A. Morrissey, [146] R.A. Palominos, A. Mora, M.A. Mondaca,
M. Oelgemoeller, J.M. Tobin, Catalysis Letters M. Pérez-Moya, H.D. Mansilla, Journal of
141, 300 (2010) Hazardous Materials 158, 460 (2008)
[133] J. Nieto, J. Freer, D. Contreras, R.J. Candal, [147] C. Zhao, H.P. Deng, Y. Li, Z. Z. Liu, Journal of
E.E. Sileo, H.D. Mansilla, Journal of Hazardous Hazardous Materials 176, 884 (2010)
Materials 155, 45 (2008) [148] T. Mohammadi, A. Z. Isfahani, Acta Chimica
[134] R. Palominos, J. Freer, M.A. Mondaca, Slovenica 55, 172 (2008)
H.D. Mansilla, Journal of Photochemistry and [149] R.P.S. Suri, J. Liu, D.W. Hand, J.C. Crittenden,
Photobiology A: Chemistry 193, 139 (2008) D.L. Perram, M.E. Mullins, Water Environment
[135] F. Mendez-Arriaga, R.A. Torres-Palma, C. Petrier, Research 65, 665 (1993)
S. Esplugas, J. Gimenez, C. Pulgarin, Water [150] S. Vilhunen, M. Bosund, M.-L. Käriäinen,
Research 43, 3984 (2009) D. Cameron, M. Sillanpä, Separation and
[136] F. Méndez-Arriaga, M.I. Maldonado, J. Gimenez, Purification Technology 66, 131 (2009)
S. Esplugas, S. Malato, Catalysis Today 144, 113 [151] M.N. Abellán, B. Bayarri, J. Giménez, J. Costa,
(2009) Applied Catalysis B: Environmental 74, 233
[137] P. Calza, V.A. Sakkas, A. Villioti, C. Massolino, (2007)
V. Boti, E. Pelizzetti, T. Albanis, Applied Catalysis [152] M.N. Abellan, J. Gimenez, S. Esplugas, Catalysis
B: Environmental 84, 379 (2008) Today 144, 132 (2009)
[138] T.C. An, H. Yang, W.H. Song, G.Y. Li, H.Y. Luo, [153] D. Nasuhoglu, V. Yargeau, D. Berk, Journal of
W.J. Cooper, Journal of Physical Chemistry A Hazardous Materials 186, 67 (2011)
115, 2569 (2010) [154] R.A. Palominos, M.A. Mondaca, A. Giraldo,
[139] V. Augugliaro, E. García-López, V. Loddo, G. Peñuela, M. Pérez-Moya H.D. Mansilla,
S. Malato-Rodríguez, I. Maldonado, G. Marcì, Catalysis Today 144, 100 (2009)
R. Molinari, L. Palmisano, Solar Energy 79, 402 [155] C. Sirtori, A. Aguera, W. Gernjak, S. Malato, Water
(2005) Research 44, 2735 (2010)
[140] L.A. Pérez-Estrada, S. Malato, A. Agüera, [156] T. An, J. An, H. Yang, G. Li, H. Feng, X. Nie,
A.R. Fernández-Alba, Catalysis Today 130, 207 J. Hazard. Mater. 197, 229 (2011)
(2007) [157] B. Abramovic, S. Kler, D. Sojic, M. Lausevic,
[141] F.J. Rivas, O. Gimeno, T. Borralho, M. Carbajo, T. Radovic, D. Vione, J. Hazard. Mater. 198, 123
Journal of Hazardous Materials 179, 357 (2010) (2011)
[142] V. Romero, N. De la Cruz, R.F. Dantas, P. Marco, [158] F. Mendez-Arriaga, T. Otsu, T. Oyama,
J. Giménez, S. Esplugas, Catalysis Today 161, J. Gimenez, S. Esplugas, H. Hidaka, N. Serpone,
115 (2011) Water Research 45, 2782 (2011)
[143] M.M. Haque, M. Muneer, Journal of Hazardous
Materials 145, 51 (2007)

1027
Unauthenticated
Download Date | 11/6/15 8:40 AM

You might also like