ABATEMENT OF METOPROLOL BY PHOTO-FENTON:

S. Esplugas, V. Romero, O. Gonzalez, B. Bayarri, P. Marco, J. Gimenez. Department of Chemical Engineering.

Faculty of Chemistry. University of Barcelona. C/ Mart I Franqus, 1. 08028 Barcelona. Spain. Tel.
+34934021293. FAX +34934021291. E-mail: Santiago.esplugas@ub.edu

, Fe

The aim of this work is to study the removal of the emerging

contaminant Metoprolol tartrate salt (MET) by photo-Fenton process.
Optimal conditions for MET degradation were found varying the
temperature of the process (14 and 25C) and the initial
pharmaceutical (25, 50 and 100 mg/L), Fe (II) (2.5 and 10 mg/L), and
H2O2 (25 and 150 mg/L) concentrations. In addition, the evolution of
important parameters such as H2O2 concentration and TOC were
assessed during the reaction. Results showed complete MET removal
and only 24% of mineralization after 5 minutes of irradiation by photoFenton, at 25 C, using 10 mg Fe/L and 150 mg H2O2/L. 77.5% of
mineralization was obtained at the end of the reaction (90 min), when
H2O2 was totally consumed.
Pseudo-firstorder rate constants (k) were calculated from the
experimental data for all the experiments. Working with the highest Fe
(II) and H2O2 concentrations, the maximum k value obtained was 1.11
min-1 and 0.14 min-1 for the lowest concentrations at 25 C.

Introduction
Lately, pharmaceutical emerging pollutants have
received substantial attention due to their persistent
toxic character and high biological activity [1].
Among them, the -blockers are widely used as
androgenic receptors [2,3,4]. -blockers have been
found, at low concentration, in surface waters and
they cannot be totally eliminated in sewage
treatment plants [1,5,6-9]. The -Blocker drug
Metoprolol Tartrate Salt (MET) has been chosen as
target compound. Photo-Fenton experiments using
black-light blue (BLB) lamps were performed in
order to degrade and mineralize MET solutions.
Besides, optimal degradation conditions were
found.
Material and Methods
Chemicals
All the MET solutions were prepared in Milli-Q
water. MET was purchased from Sigma-Aldrich
Chemical Co. (Spain).
Hydrogen peroxide (30% w/w, from Merck) and
ferrous sulfate heptahydrate (FeSO47H2O, >98%,
from SigmaAldrich) were also used. All reagents
were of analytical grade.
Techniques and analytical instruments
All samples were previously filtered with a
polyethersulfone membrane filter (0.45 m,Chmlab
group) in order to remove the catalyst before
analytical procedures. MET concentrations were
monitored by a HPLC supplied by Waters
Corporation using a SEA18 column (5m 25x0.46
cm), from Teknokroma-Spain, and a Waters 996
photodiode array detector. The mobile phase was
composed by water (pH 3 adjusted by
orthophosporic acid) and acetonitrile (80:20), and
injected at a flow-rate of 0.85 mL/min. MET was

quantified at 221.9 nm. Total organic carbon (TOC)

was measured in a Shimadzu TOC-V CNS
instrument.
During the experiments the H2O2 consumption was
followed
using
the
metavanadate
spectrophotometric
procedure
[12]
(spectrophotomer Hach Lange DR 3900 at 450
nm). Fe (II) was measured by 1-10 Fenontraleine
method and absorbance by spectrometer Perkin
Elmer UV/VIS Lambda 20 at 254 nm.
Experimental set-up
All experiments were performed in a batch reactor.
The photochemical reactor was a Pyrex-jacket
thermostatic 2 L vessel (inner diameter 11 cm;
height 23 cm), equipped with three 8W BLB lamps
(Philips TL 8W-08 FAM) placed in its center, which
emitted radiation between 350 and 400 nm, with a
maximum at 365 nm. The radiation entering the
photoreactor (6.0 Einstein/s) was measured by oNitrobenzaldehyde (o-NB) actinometry in the 290400 nm range. Good mixing was provided using a
magnetic stirrer. The reaction temperature was kept
constant at 14 or 25 C, depending on the
experiments carried out. The system was let to
react until all the H2O2 was consumed.
Results and Discussion
Influence of Fe (II)
When Fe (II) concentration increases, MET removal
does it. Fe (II) acts as catalyst promoting the
generation of radicals OH from decomposition of
the hydrogen peroxide. Therefore, a higher Fe(II)
concentration leads to higher OH generation which
increases the MET degradation.

MET was completely degraded after 5 minutes of

irradiation using 10 mg Fe(II)/L and 150 mg H2O2/L.
These conditions led to the fastest MET
degradation. The lowest degradation was obtained
using 2.5 mg Fe (II)/L and 25 mg H2O2/L, which
provided 98% of MET conversion after 130 minutes
of irradiation. . In figure 1, it can be appreciated
MET removal as function of consumed H2O2
changing temperature and catalyst concentration.

a)
1
0.8

H2O2/(H2O2)0

MET degradation

optimal conditions correspond to 150 mg H2O2/L, 10

mg Fe/L and 25 C. The worst condition (see Figure
2 b) was obtained using the minimum concentration
and temperature.

a)

0.6

0.4
0.2

1
0

0.8

50

100

150

200

250

300

350

400

MET/MET0

Time (min)
25C, 10 mg Fe/L, 150 mg H2O2/L
14C, 10 mg Fe/L, 150 mg H2O2/L

0.6

25C, 2.5 mg Fe/L, 150 mg H2O2/L

14C, 2.5 mg Fe/L, 150 mg H2O2/L

0.4

b)

0.2

0
0

10

15

20

25

0.8

25C, 2.5 mg Fe/L, 25 mg H2O2/L

14C, 10 mg Fe/L, 25 mg H2O2/L

25C, 10 mg Fe/Le, 25 mg H2O2/L

14C, 2.5 mg Fe/L, 25 mg H2O2/L

H2O2 /(H2O2)0

H2O2 consumed
0.6
0.4
0.2

b)
0

MET/MET0

50

100

150

200

Time (min)

0.8
25C, 10 mg Fe/L, 25 mgH2O2/L
14C, 10 mg Fe/L, 25 mg H2O2/L

0.6

25C, 2.5 mg Fe/L, 25 mg H2O2/L

14C, 2.5 mg Fe/L, 25 mg H2O2/L

Figure 2. H2O2 consumption along photo-Fenton reaction

time using several Fe (II) concentrations at 14 and 25C.

0.4
0.2
0
0

20

40

60

80

100

120

H2O2 consumed

25C, 10 mg Fe/L, 150 mg H2O2/L

25C, 2.5 mg Fe/L, 150 mg H2O2/L

14C, 10 mg Fe/L, 150 mg H2O2/L

14C, 2.5 mg Fe/L, 150 mg H2O2/L

Figure 1. Removal of MET by photo-Fenton reaction using

several Fe (II) concentrations: a) H2O2 concentration 25
mg/L and b) H2O2 concentration 150 mg/ L.

Kinetics
Photodegradation in optically dilute solution usually
follows the first order reaction kinetics [10,11]. In
this study, the results have been fitted to pseudofirst order and kinetic constants (k) are summarized
in table 1. For a certain H2O2 concentration (150
mg/L), higher temperature (25 C) and Fe (II) (10
mg/L) concentrations led to higher kinetic constants
(1.11 min -1).

Influence of H2O2 concentration

The addition of oxidizing species increases the
efficiency of the photocatalytic process due to H2O2
acts as electron acceptor and reacts with electrons
from the photoactivated surface of the catalyst,
being thus an extra source of HO:
H2O2 + e- HO+ OHWhen solution was irradiated in presence of 150
H2O2 mg/L, the best result was obtained compared
with the lowest H2O2 concentration because its
oxidant power.
Figure 2 shows the H2O2 consumption along the
reaction time and it can be seen, in a), that the

Influence of temperature
Temperature has played an important role in photoFenton processes and in this effect could also be
observed in our experiments with just a moderate T
variation of 11 C. Kinetic constants obtained at
both temperatures shows perceptible differences.
At consumed H2O2 (22.87 mg /L) and working with
10 mg Fe (II)/L and 25 mg /L H2O2, MET conversion
was 98.4% at 25C and 93.1% at 14C. At
consumed H2O2 (24.06 mg /L) and working with 2.5
mg Fe (II)/L and 25 mg /L H2O2, MET conversion
was 98.5% at 25C and 96.6% at 14C

Table 1. Pseudo-first order kinetic constants for MET degradation for the different experimental conditions assayed.
Temperature
C

[Fe (II)]
mg/L

[H2O2]
mg/L

k
-1
(min )

25

10

150

1.11

14

10

150

0.60

25

2.5

150

0.19

14

2.5

150

0.13

25

10

25

0.37

14

10

25

0.21

25

2.5

25

0.14

14

2.5

25

0.08

Conclusions
In our study a complete MET degradation was obtained at the highest concentrations of Fe (II) and H2O2.
Nevertheless, at 14C the total time of reaction was 10 minutes to obtain 100% of MET degradation that
means the double of time that working at 25 C. It is possible to conclude that under the same operational
conditions, the higher is the temperature, the faster MET degradation and the lower time of H2O2
consumption are achieved.

Acknowledgments

Authors are grateful to CICYT (Project CTQ2011-26258) and Consolider-Ingenio NOVEDAR 2010
CSD2007-00055 for funds received to carry out this work and Programa dajuts per a la contractaci de
Personal Investigador Novell (FI-DGR) 2012FI_B 01060 from Generalitat de Catalunya.

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