Desalination 276 (2011) 379–385

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Degradation of the emerging contaminant ibuprofen in aqueous solution

by gamma irradiation
B.G. Zheng a,b, Z. Zheng c,⁎, J.B. Zhang c, X.Z. Luo c, J.Q. Wang a, Q. Liu a, L.H. Wang a
a
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093, China
b
Institute of Resources and Environment, Zhengzhou Institute of Aeronautical Industry Management, Zhengzhou 450015, China
c
Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, China

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

Article history: This study focused on the degradation of the worldwide Non-steroidal Anti-Inflammatory Drug (NSAID)
Received 19 October 2010 ibuprofen (IBP) by gamma irradiation. Factors affecting IBP degradation efficiency were examined. The results
Received in revised form 6 March 2011 showed that IBP concentration decreased with an increasing absorbed dose. When IBP concentration of
Accepted 30 March 2011
28.3 mg/L and an absorbed dose of 1.1 kGy were chosen, IBP degradation value was 100%. The degradation
Available online 6 May 2011
process of IBP could be depicted by first order reaction kinetics when the absorbed dose was less than 0.9 kGy.
Keywords:
0.1% H2O2 and humic acid additives enhanced IBP degradation process, while 0.5% H2O2 additive restrained
−
Non-Steroidal Anti-inflammatory Drug the degradation of IBP. The additions of CO2−
3 , NO3 , CH3OH and thiourea restrained the degradation process.

Ibuprofen The pH value affected the IBP degradation. The degradation efficiency was more efficient under acidic
Gamma irradiation condition than in neutral or alkaline media. The solution pH value became lower with increasing absorbed
Degradation dose after gamma irradiation. High performance liquid chromatography (HPLC) and electrospray ionisation
mass spectrometry (ESMS) techniques were employed to identify the IBP derivatives. The mono- and quadric-
hydroxylated of IBP and the products due to the oxidation of propanoic acid, and isobutyl substituents of IBP
were identified.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction effluents of wastewater treatment plants (WTPs) [8,9]. Concentra-

Recently, the presence of various pharmaceutical pollutants in the
environment has received much attention due to the unknown
environmental impact and possible damages to the botany and fauna
present in aquatic systems [1,2]. The major sources of pharmaceutical
pollutants are the continuous disposal of wastewaters released from
the pharmaceutical industries, excretory products of medically
treated humans and animals [3]. Pollutant found with more than 70
million annual prescriptions in the world is the Non-Steroidal Anti-
Inflammatory Drug (NSAID), one of the most consumed medications
corresponds to the classification [4,5].
The compound 2-[3-(2-methylpropyl)phenyl]propanoic acid,
commercially available as ibuprofen (IBP), is widely used as an
NSAID especially prescribed for the treatment of fever, migraine,
muscle aches, arthritis and tooth aches [3]. According to literature [6],
several kilotons of IBP are produced worldwide each year, part of
which is rejected to the effluents, excreted by patients in its original
form or as metabolites from human biodegradation. Despite possible
environmental problems caused by the use of IBP, its consumption is
unlikely to be restricted since it is beneficial to humankind [7]. Some
reports have confirmed the presence of the IBP and the metabolites, in
tions of IBP in the environment are reported between 10 ng/L and
169 μg/L [10]. Although the concentrations of IBP are very low in
aquatic systems, and they may present a potential hazard for human
health, the metabolites are more harmful than the parent organic
compounds [11–13].
NSAID IBP is not easily degraded under the typical biological
treatments in the municipal wastewater treatment plants. Therefore,
a lot of enhanced technologies that can reduce IBP presence in the
environment have been carried out, such as photodegradation, solar
photodegradation methods [4,14–17], biological treatments [18–26],
advanced oxidation processes [3,27–30], unidirectional downward
freezing method [31].
The first gamma irradiation study for IBP oxidation was conducted
in yellow water under specific conditions [32]. When the initial
concentration of IBP was 3.5 μg/L, the complete removal of IBP in
yellow water would be obtained under higher gamma irradiation dose
(10 kGy). However, the byproducts of IBP degradation and the
influence of important operational parameter were not discussed in
this study. Therefore, the further studies would be carried out.
The major goals of the study were to investigate the derivatives of
IBP during gamma irradiation and illustrate the effect of operational
parameters, such as solution pH and various additives (CO2- -
3 , NO3,

⁎ Corresponding author. Tel./fax: + 86 21 65643342. CH3OH, H2O2, thiourea and humic acid) on gamma irradiation.
E-mail address: zzhenghj@fudan.edu.cn (Z. Zheng). Additionally, the degradation kinetics of IBP was also investigated.

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.03.078
380 B.G. Zheng et al. / Desalination 276 (2011) 379–385

2. Experimental details
2.1. Chemicals and reagents
IBP, CH3CN, and CH3OOH were purchased from Sigma-Aldrich and
HPLC grade. Humic acid was high purity product and purchased from
Sigma-Aldrich. H2O2, NaNO3 (NO-3), (NH2)2CS, HCl, and NaOH were
analytical-grade and obtained from Shanghai Chemicals Factory,
China. The ultrapure water was obtained from milli-Q system (Elix5
milliQ A10, USA).
2.2. Experimental procedures
2.2.1. Sample preparation
According to the study of Madhavan [3], IBP solution at initial
concentration of 28.3 mg/L was prepared by solid IBP with ultrapure
water. It was employed to test the effect of absorbed dose on
degradation efficiency and to examine the change of solution pH and
total organic carbon (TOC) after gamma irradiation. The different
additives (H2O2, CH3OH, NO-3, CO2-3 , thiourea, humic acid) of different
concentrations were added into IBP aqueous solution (28.3 mg/L) to
examine their effects on the degradation efficiency of IBP. HCl
(0.01 mol/L) and NaOH (0.01 mol/L) were put into 28.3 mg/L IBP
solution to test the effect of pH value on degradation efficiency. IBP
solutions at different concentration were prepared to test the effect of
initial concentration on degradation in the same absorbed dose.
2.2.2. Irradiation process
Gamma irradiation was performed using high-level 60Co source
(1.85 × 1016 Bq) at the Institute of Atomic Energy, Jiangsu Academy of
Agriculture Sciences, P.R. China. IBP solutions (25 mL each) were
placed into 50 mL airtight glass vessels and all aqueous solutions were
allowed to reach equilibrium with atmospheric pressure and room
temperature (22 °C ± 2) before irradiation. Then they were placed in a
radiation field with a specific distance from the source to achieve the
desired series of absorbed dose. 0.2, 0.5, 0.7, 0.9 and 1.1 kGy were
selected as the absorbed doses. The doses that samples absorbed were
determined with silver dichromate dosimeter.
2.3. Analysis
Analysis of IBP was performed using a HPLC system (Agilent, USA,
1200 Series high-performance liquid chromatography). The column
temperature was 30 °C and a sample volume of 20 μL was injected
from an autosampler. Chromatographic separation was achieved on a
Hypersil ODS HPLC column (250 mm × 4.6 mm i.d., 5 μm, Agilent,
USA), the mobile phase consisted of 75% acetonitrile and 25% acetic
acid (0.25 mol/L), the flow rate was 1 mL/min. The determination
wavelength was set at 254 nm [4]. Five or six point linear standard
calibration curves were constructed and periodically throughout the
analyses period to verify the stability of the system.
The degradation efficiency for each sample was calculated from
the following Eq. (1).
C −Ct
η= 0 × 100% ð1Þ
C0
(150 mm × 2.1 mm i.d., 5 μm, Finnigan, Thermo, USA). 20 μL IBP
solutions after gamma irradiation were injected automatically into
the HPLC-MSES system. The eluent consisted of 30% of 1.0 mmol/L
acetic acid in water and 70% of acetonitrile. The flow rate was 0.2 mL/
min, the other LC conditions were the same as the conditions used in
determining IBP concentration. The spray voltage was 3.5 kV and the
sheath gas flow rate was 18 arb. The spectra were acquired in the
negative ion scan mode, over the m/z range from 50 to 1000 [3].
Total organic carbon (TOC) was determined by TOC analyzer
(Shimadzu, TOC-5000A). The pH value was measured by pH monitor
(Shanghai Kangyi Instrument Co., Ltd. China, PHS-2C).
2.4. IBP radiation chemical yield (G-value)
Radiation chemical yield of IBP (defined by the number of
molecules formed or destroyed in solutions absorbing 100 eV of
radiation energy) can be calculated using Eq. (2) [33–35].
ðΔRÞðNA Þ
G=
ð2Þ
ðDÞ 6:24 × 1016
ΔR The amount of reduced IBP (mol/L);
NA Avogadro constant, 6.023 × 1023 (molecules/mol);
D The absorbed dose (Gy);
6.24 × 1016 Conversion constant from Gy to 100 eV/L.
3. Results and discussion
3.1. Radiolytic degradation of IBP
Degradation of water pollutants by gamma irradiation is initiated
by the primary products of water radiolysis, such as hydrogen atoms
H; hydrated electrons e− aq; hydroxyl radicals ·OH, and the less reactive
species H3O+, which are given in Eq. (3) (The values in brackets are
the radiation chemical yields of these species (G values) per 100 eV of
absorbed energy) [34]. Under certain conditions, the reactions
between these radicals occur in aqueous solution during gamma
irradiation. As follows: (i) In the presence of dissolved oxygen, the
radicals H· and e− . .−
aq are converted into HO2 and O2 , as in Eqs. (4) and
(5); (ii) At higher radiation dose, the reaction between the ·OH and
the e−
aq can be represented by Eq. (6); (iii) under acidic conditions, the
H+ readily reacts with e− ·
aq to generate H·, as in Eq. (7); (iv) HO2 and its
.−
conjugate base O2 exist in a pH-dependent equilibrium, as in Eq. (8);
(v) Any other reactions could occur during gamma irradiation, as in
Eqs. (9)–(11) [36].
−
H2 O→eaq ð2:6Þ + H·ð0:55Þ + ·OHð2:7Þ + H2 ð0:45Þ ð3Þ
þ
+ H2 O2 ð0:71Þ + H3 O ð2:6Þ
· 10
H· + O2 = HO2 k = 2:1 × 10 L = mol·s ð4Þ
− ·− 10
eaq + O2 = O2 k = 1:9 × 10 L = mol·s ð5Þ

− − 10
eaq + ·OH = OH k = 3:0 × 10 L = mol·s ð6Þ
η The degradation efficiency of IBP (%);
Ct The residual concentration of IBP after gamma irradiation − þ
eaq + H = H·
10
k = 2:3 × 10 L = mol·s ð7Þ
(mg/L);
C0 The initial concentration of IBP (mg/L). · ·− þ 5 −1
HO2 = O2 + H k = 8 × 10 s ð8Þ
HPLC-ESMS analysis was performed in order to identify IBP
· ·− 7
derivatives. HPLC-ESMS system with Beta Basic-C18 HPLC column HO2 + O2 = H2 O2 + O2 ðpHb7Þ k = 9:7 × 10 L = mol·s ð9Þ
 B.G. Zheng et al. / Desalination 276 (2011) 379–385 381

Fig. 1. Degradation of IBP under different absorbed dose.

Fig. 2. Effects of IBP concentrations on its degradation kinetics.

· · 5
HO2 + HO2 = H2 O2 + O2 k = 8:3 × 10 L = mol·s
− − 7
H· + OH = eaq + H2 O k = 2:2 × 10 L = mol·s
Gamma irradiation of IBP in aqueous solution was conducted at
absorbed doses of 0.2, 0.5, 0.7, 0.9 and 1.1 kGy. The concentration
variations of IBP with absorbed doses are compared in Fig. 1. It could
be observed that the concentration of IBP decreased with the
increasing of absorbed does. These results are similar to the reported
for radiolytic degradation of IBP in yellow water by Lazarova [32].
When 1.1 kGy was selected as the absorbed dose, IBP degradation
efficiency was 100%.
According to Eq. (2), the G values of IBP (28.3 mg/L) at different
absorbed doses are shown in Table 1. The results showed that the G
values decreased with the increasing of absorbed dose. The reasons
may include the competitive reactions for radicals between the parent
compound and the degradation products, or the recombination
reactions of radical–radical (·OH, e−aq and H·), as shown by Eqs.
ð10Þ increased with lower initial IBP concentrations. These results are similar
to the previously reported results by Lee and Bruce [39,40].
ð11Þ
3.2. Influence of operational parameters on the IBP gamma irradiation
process
3.2.1. Effect of solution pH
Fig. 3 shows the effect of pH on IBP degradation efficiency. It
indicated that pH value was an important factor that affected the IBP
degradation. The degradation efficiency increased in acid conditions.
With an absorbed dose of 0.7 kGy, IBP degradation efficiency was
92.01% at pH 1.45, whereas the degradation efficiency was only
80.25% at pH 11.05 with the same absorbed dose. A change in H+ and
OH− concentration in solution modifies the radical composition
generated during gamma irradiation (Eqs. (4–15)). Thus, under acidic
conditions and in accordance with Eq. (7), the relative concentration
of H· was higher. However, in alkaline solution, H· readily reacts with
OH− to generate e− aq (Eq. (11)), thereby increasing the concentration

(12–15) [36,37], so, the radical concentrations for reaction with IBP of e−
aq, enhancing the probability of recombination between ·OH and

reduced. The radiation chemical yield trend reported here is e−

aq (Eq. (14)) and reducing the effective radical concentrations (e.g.

consistent with published findings for radiolytic degradation of ·OH radical) and the degradation efficiency of IBP decreased at high
malathion and lindane [38]. pH levels [41].

9
·OH + ·OH = H2 O2 k = 5:5 × 10 L=mol·s ð12Þ 3.2.2. Effects of CO2- -
3 and NO3 additives on IBP degradation
Generally, it was impossible that there was only one pollutant in
·OH + H· = H2 O k = 7:0 × 10 L=mol·s
9
ð13Þ wastewater. Therefore, it was necessary to study the effect of other
compounds existing in IBP solution. Here, CO2- -
3 and NO3 were chosen

− − 10
as the model radical scavengers to study their effect on IBP
·OH + eaq = OH k = 3:0 × 10 L=mol·s ð14Þ degradation behavior.

− − 10
H2 O + H· + eaq = H2 + OH k = 2:5 × 10 L=mol·s ð15Þ

The degradation kinetics of IBP followed first order kinetics when the
absorbed dose was less than 0.9 kGy. The changes in ln(C0/Ct) as the
absorbed dose are described in Fig. 2. Fig. 2 shows a trend and the slope of
this plot yielded the first order dose constant. When the initial
concentration of IBP was 28.3 mg/L, the dose constant was 3.24 kGy− 1.
However, when the initial concentrations were 38.1, 47.2 and 58.6 mg/L,
the dose constants were 2.28, 1.91 and 1.58 kGy− 1. The dose constant

Table 1
The G value of IBP removals under different absorbed dose (× 10− 5 molecules/
(100 eV)).

Absorbed dose (kGy) 0.2 0.5 0.7 0.9 1.1

G (molecules/(100 eV)) 2.62 2.07 1.70 1.40 1.20
Fig. 3. Effect of pH on degradation of IBP by gamma irradiation.
382 B.G. Zheng et al. / Desalination 276 (2011) 379–385

Fig. 4. Effects of CO2- -

3 and NO3 on IBP degradation by gamma irradiation. Fig. 6. Effects of CH3OH and thiourea on IBP degradation by gamma irradiation.

Fig. 4 shows the effects of CO2- -

3 and NO3 additives on IBP H2O2 was added, it would not supply more ·OH in aqueous solution.
degradation by gamma irradiation. The results showed that the However, it could compete with IBP for ·OH (Eq. (19)) and reduced
degradation efficiency in the presence or absence of these additives IBP degradation efficiency. These results are similar with the
was improved with an increasing absorbed dose. As shown in Fig. 4, at previously reported results by Sánchez-Polo [41].
the same absorbed dose the degradation efficiency was lower in the
presence of CO2- -
3 and NO3 than that in the absence of them, and the −
H2 O2 + eaq = ·OH + HO
− 10
k = 1:1 × 10 L=mol·s ð18Þ
increase of these additives would result in the decrease of the
degradation efficiency. It indicated that CO2- -
3 and NO3 additives · 7
restrained IBP degradation process. The reason was that·OH and e− aq
H2 O2 + ·OH = H2 O + HO2 k = 2:7 × 10 L = mol·s ð19Þ
could be scavenged by CO2- -
3 , as shown by Eqs. (16,17) [42]. NO3 was
the scavenger of e−
aq and it inhibited the degradation process of IBP According to Fig. 5, when humic acid was added, IBP degradation
[43]. efficiency was higher than that in the absence of humic acid with the
same absorbed dose. The reason was that humic acid could absorb
2
·OH + CO3 = OH
−  8
+ CO3 · k = 3:9 × 10 L=mol·s ð16Þ irradiation and generate excited triplet states (3HA*) and various
reactive oxygen species, including hydroxyl radicals (·OH), singlet
− 2 3 5 oxygen (1O2) and hydrogen peroxide (H2O2) [44], so the radical
eaq + CO3 = CO3 k = 3:9 × 10 L=mol·s ð17Þ
concentrations for reaction with IBP increased.

3.2.4. Effects of CH3OH and thiourea additives on the IBP degradation

3.2.3. Effects of H2O2 and humic acid additives on the IBP degradation
It is well-known that H2O2 is ·OH radical promoter, it could
accelerate the degradation of pollutions in aqueous solution [36].
Fig. 5 shows the effect of H2O2 on IBP degradation by gamma
irradiation. The results showed that 0.1% H2O2 accelerated the
degradation of IBP, supplying ·OH in the medium (Eq. (18)).
However, when the H2O2 dose was 0.5%, it inhibited the IBP
degradation process. It indicated that when a massive dosage of
Fig. 6 shows the effects of CH3OH and thiourea on IBP degradation
by gamma irradiation. In the presence or absence of these additives,
IBP degradation efficiency increased with an increasing absorbed
dose. When CH3OH was added, the degradation efficiency of IBP was
much lower than in the absence of CH3OH with the same absorbed
dose. The reason was CH3OH reacted more rapidly than IBP with ·OH
and e− aq in aqueous solution (Eqs. (20) and (21)) [45]. The results also
showed that ·OH radicals play an important role in IBP degradation by

Fig. 5. Effects of H2O2 and humic acid on IBP degradation by gamma irradiation. Fig. 7. Change of pH value after gamma irradiation.
 B.G. Zheng et al. / Desalination 276 (2011) 379–385 383

dose. Thiourea inhibited the degradation process. The experimental

results obtained using thiourea as radical scavenger indicated that
primary active species, such as e−
aq, and H·, also participate in the
degradation reaction of IBP, since thiourea was a very strong
scavenger of all three radicals (·OH, e− aq, H·) [36], the reaction
patterns are shown by Eqs. (22)–(24) [41].

9
·OH + H2 NCSNH2 →unknown products k = 3:9 × 10 L=mol·s
ð22Þ

9
H· + H2 NCSNH2 →unknown products k = 6 × 10 L=mol·s ð23Þ

− 9
Fig. 8. Change of TOC after gamma irradiation. eaq + H2 NCSNH2 →unknown products k = 2:9 × 10 L=mol·s
ð24Þ

gamma irradiation, it was closely associated with the radiolytic

degradation of IBP, since an increase in CH3OH concentration
produced a remarkable decrease in degradation efficiency. 3.3. Variation of solution pH

·OH + CH3 OH→H2 O + ·CH2 OH + CH3 O·
− −
eaq þ CH3 OH→H· + CH3 O
8
k = 4:7 × 10 L = mol·s The effect of gamma irradiation on pH value is shown in Fig. 7. It
ð20Þ was noteworthy that the pH value decreased with the increasing of
absorbed dose, pH values decreased from 6.29 to 6.15, 5.76, 5.12, 4.46
4 and 3.81 at the absorbed doses of 0.2, 0.5, 0.7, 0.9, 1.1 kGy. The
k = 1:0 × 10 L=mol·s
decrease of pH value is possibly due to a large amount of H3O+
ð21Þ produced in the irradiation process (Eq. (3)).

When thiourea was added, the degradation efficiency of IBP was 3.4. Variation TOC during the radiation
lower than that in the absence of additive with the same absorbed
It has been reported that some of the intermediate products of IBP
were more toxic than the parent organic compounds [11–13]. Hence,
Table 2 the complete degradation of the pollutants should be ensured before
Ibuprofen and its derivatives during gamma irradiation.
discharging them into the ecosystem. The total organic carbon (TOC)
O CH3 O value was made from the experiments carried out, and the change of
H3C TOC is shown in Fig. 8 during gamma radiation. The obtained results
H3C
OH OH
indicated that gamma radiation could lead to both degradation and
partial mineralization of IBP in aqueous solution, but complete
mineralization was not achieved with the 1.1 kGy absorbed dose.

3.5. IBP derivatives from gamma irradiation process

HO CH3
In order to identify the IBP derivatives, sample collected at the
CH3 CH3 HO CH3 absorbed dose of 1.1 kGy was analyzed by means of HPLC-ESMS. The
CH3
derivatives and their mass spectrums are shown in Table 2 and Fig. 9.
CH3 It was observed that an attack of hydroxyl radicals on both the
Ibuprofen I II propanoic acid and isobutyl substituents of IBP structure results in the
m/z. 205 m/z. 177 m/z. 221 formation of products such as 2-[4-(1-hydroxyisobutyl)phenyl]
propionic acid (II), 2-hydroxy-2-[2-hydroxy-4-(2,3-dihydroxy-2-
CH3 O
methylpropyl)phenyl]propanoic acid (IV), 1-ethyl-4-(1-hydroxy)iso-
CH3
butylbenzene (I), 4-ethylbenzaldehyde (III) and 4-ethylphenol (V).
H3C
According to Fig. 9(a) and (b), the peaks that appear at m/z 221
OH
HO and 269 show the formation of mono- and quadric-hydroxylated
HO products of IBP, such as products (II) and (IV). Fig. 9(a) and (c) show
the peaks of m/z 177 and 133, it indicate the formation of product (I)
and (III). The peak of m/z 121 appears in Fig. 9(d), this shows the
formation of product (V). Méndez-Arriaga et al. studied the photo-
O OH
Fenton and photocatalytic degradation of IBP and reported the
HO CH3 formation of products (II) and (I) and argued that the hydroxylation
HO process can be the first step of the degradation, followed by a second
CH3 step of demethylation or decarboxylation with other different
byproducts with smaller m/z values [4,17]. Madhavan et al. [3]
III IV V reported the formation of products (III) and (V) by the sonolysis
m/z. 133 m/z. 269 m/z. 121 degradation of IBP. Skoumal et al. [46] also reported the formation of
product (III) by the photoelectron-Fenton degradation of IBP.
384 B.G. Zheng et al. / Desalination 276 (2011) 379–385
a b
c d
Fig. 9. The mass spectrums of IBP derivatives.
4. Conclusion
Gamma irradiation could effectively degrade IBP in aqueous
solution. At the absorbed dose of 1.1 kGy, IBP degradation efficiency
was 100%. The degradation reaction of IBP could be depicted by first
order reaction kinetics when the absorbed dose was less than
0.9 kGy.
The pH value affect the IBP degradation efficiency, the degradation
yield was higher under acidic conditions than in neutral and alkaline
media. The CO2- -
3 and NO3 additives inhibited IBP degradation process.
0.1% H2O2 and humic acid additives enhanced the degradation
process, but 0.5% H2O2 restrained the IBP degradation process. The
addition of CH3OH and thiourea also inhibited the IBP degradation
process. The pH value and TOC of solution decreased with an
increasing absorbed dose. HPLC-ESMS was employed for the identi-
fication of the derivatives. Gamma irradiation IBP leads to the
formation of its mono- and quadric-hydroxylated intermediates,
and the products due to the oxidation of propanoic acid and isobutyl
substituents of the IBP were also identified.
Acknowledgements
The authors would like to specially thank the support from the
major project on control and rectification of water body pollution, P.R.
China (Foundation item No. 2008ZX07101-004) and the National
Natural Science Foundation of China 11075039.
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