Photonic Efficiency of the Photodegradation of Paracetamol in Water

by the Photo-Fenton Process

P70

E. Yamal-Turbay1, E. Ortega1, L.O. Conte3, M. Graells1, H.D. Mansilla2, O.M. Alfano3, M. Prez-Moya1.
(1) Escola Universitria dEnginyeria Tcnica Industrial de Barcelona, C/Comte dUrgell 187, 08036 Barcelona
(2) Facultad de Ciencias Qumicas, Universidad de Concepcin, Chile (3) INTEC, Universidad Nacional del
Litoral and CONICET, Santa Fe, Argentina

This work is aimed at determining the photonic efficiency of the

photodegradation of paracetamol (PCT) by the photo-Fenton
treatment as a means to assess its degradation and mineralization
performance. Photonic efficiency is determined under different
experimental conditions, identifying the influence of the hydrogen
peroxide to iron(II) ratio on both contaminant degradation and
sample mineralization.
The Photo-Fenton process demonstrated to be effective in
degrading PCT and a convenient combination of reagent loads
showed to yield 80% mineralization.
Accordingly, photonic efficiencies of PCT degradation were
determined to be higher than the ones of mineralization. In both
cases, photonic efficiencies decrease with reaction time and
higher efficiencies are possible when suitable reagent doses are
supplied.
Introduction
The presence of pharmaceuticals in sewage
effluents, surface and ground water and even in
drinking water is a matter of increasing concern
because of their potential harmful effects on the
environment and human health. They can act as
endocrine disruptors or promote resistance in
bacteria, among other environmental effects [1].
Particularly, paracetamol (PCT) is a widely used
analgesic, anti-inflammatory and antipyretic,
reported as the most popular non-opioid analgesic
sold in Spain in the last years [2]. It has been found
in European sewage treatment plants in
concentrations around 6 g L-1 [3].
A lot of efforts have been devoted to remediate
this kind of contaminants from effluents before their
final disposal, as conventional wastewater
treatment plants fail to remove them. Advanced
oxidation process (AOPs) have been studied as
alternatives to whether eliminate recalcitrant
contaminants before or after the waste water
treatment plant. Among these AOPs, the photoFenton process has proven to be effective in
degrading pharmaceuticals and its effectiveness in
treating PCT from different matrices has been
already demonstrated [4,5].
In this work, PCT degradation and mineralization
by photo-Fenton is addressed in order to assess
the efficiency of the process by means of apparent
quantum efficiency for different experimental
conditions.
Apparent quantum efficiency is defined by
Benzaqun et al. [6] as the ratio of the number of
reactant molecules degraded during a given time, to
the total number of photons arriving at the reactor
wall, during the same period of time.
Mathematically, it can be expressed for a generic
reagent A as follows:

A,app

[reaction rate of A]
photons arriving at the reactor wall]

[rate of

(1)
Applying the previous concept to PCT
degradation, photonic efficiency can be calculated
as:

app,PCT

PCT
t0

CtPCT VT
f

(2)

qw Aw (t f t0 )

where app,PCT is the photonic efficiency of PCT

PCT
degradation (mol/Einstein), C tPCT and Ct are PCT
0

concentrations at initial and final time (t0 and tf),

respectively (mol/L), VT the total irradiated volume
(L), qw the spectral net radiation flux at the reactor
wall (Einstein/cm2s) and Aw the irradiated area
(cm2).
In a similar way, in order to evaluate the photonic
efficiency of mineralization, the photonic efficiency
of TOC (app,TOC) can be expressed as:

app,TOC

TOC
t0

CtTOC VT
f

qw Aw (t f t0 )

(3)

Materials and Methods

Materials
98% purity PCT by Aldrich was purchased to
prepare 40 mg L-1 samples in distilled water. Fenton
reagents: H2O2 33% w/v (Panreac) and
Fe2SO47H2O (Merck) were used as received. Initial
pH was set at 3.00.1 by adding HCl 37% (J.T.
Baker).
HPLC gradient grade methanol (J.T. Baker) and
filtered milli Q grade water were used as HPLC
mobile phases.

Pilot plat
The photochemical pilot plant consists in a 15 L
system: glass reservoir, cylindrical photoreactor and
a pumping system set to keep a constant
recirculation flow of 12 L min-1 which guarantees a
perfect mixing. In all of the experiments
temperature was kept at 282C.
The annular photochemical reactor consists of
two concentrically arranged cylinders (an outer one
made of Pyrex and an inner one made of quartz
with an Actinic BL TL-DK 36W/10 1SL lamp inside
of it) and it is linked to the Pyrex reservoir and to a
monitoring system. The incident photon flux (I =
qw.Aw) was determined by a potassium ferrioxalate
actinometry [7] and it was 3.356x10-4 Einstein min-1.

supplied, increasing mineralization in almost 10

percentage points. In all of the studied cases, total
PCT remediation is achieved within the first 10
minutes treatment.

Analytical methods
Total organic carbon (TOC) concentration was
measured at regular time intervals of 15 minutes by
means of a Shimadzu VCHS/CSN TOC analyzer.
PCT concentration was determined via HPLC,
using an Agilent 1200 series with UV-DAD array
detector. Stationary phase was an Akady 5 m C18 150x4.6 mm column, maintained at 25C and
the diode array detector was set at 243 nm. Mobile
phase was a mixture of methanol:water (25:75)
flowing at 0.4 mL min-1 and 20 L samples were
injected by a manual injector. Under these
conditions, retention time was 8.6 minutes. A ninelevel calibration curve (range 0-50 mg L-1) was used
for contaminant quantification. Before injection,
samples were treated with 0.1M sodium sulfite and
methanol (in proportion 50:10:40) to stop reaction
and prevent further degradation of PCT and its
intermediates. This concentration was measured at
1.5, 2.5, 5, 7.5 and 10 minutes treatment.

Figure 1. PCT degradation and mineralization

performance for different reagent doses. PCT initial
-1
concentration = 40 mg L

PCT degradation and mineralization performance

Results are presented in Figure 1, where the
legend indicates the concentrations of Fe(II) (first
value) and H2O2 (second value). Fe(II) initial
concentrations were set at 5 and 10 mg L-1 (the
latter is the legal limit permitted in Spain for
disposal [8]). On the other hand, H2O2
concentrations were set at 94.5 and 378 mgL-1 (half
and twice the stoichiometric value, respectively).
When half the stoichiometric H2O2 load is used
(94.5 mg L-1), the influence of the initial
concentration of Fe(II) is not observed, but when
H2O2 stoichiometric load is doubled (378 mg L-1),
better results are obtained when maximum Fe(II) is

0.9
0.8
0.7
C/C0

0.6
0.5
0.4
0.3
0.2
0.1
0.0
0

10

20

30

40
50
t(min)

60

70

80

90

Photonic efficiency of PCT degradation (app,PCT)

Photonic efficiency was calculated for different
ratios H2O2:Fe(II) (RH/Fe) and Figure 2 presents the
results for 10 mg L-1 Fe(II) initial concentration at
different reaction times. A better ratio is observed at
RH/Fe = 37.8 during the first 2.5 minutes treatment,
but photonic efficiency seems to be independent of
the ratio after 5 minutes, as expected due to the
maximum residual PCT in whatever experimental
condition after 5 minutes reaction time is 3.24 mg L1
(more than 90% degradation).

Figure 2. Photonic efficiency of PCT degradation for

Fe(II) = 10 mg L-1 and different ratios H2O2:Fe(II)
8

7.608

tf=1,5min

6.867

7
6.181

6
5.219
5
app,PCT

Results and Discussion

First, process performance is evaluated at
different experimental conditions regarding two
objectives: PCT degradation and mineralization.
Later, associated photonic efficiencies are
presented.
The calculation of the absolute quantum
efficiencies, a more accurate parameter, will be part
of a further work. This determination requires the
calculation of the local volumetric rate of photon
absorption (LVRPA) to evaluate the number of
photons absorbed by the activated species.

5_94.5
10_94.5
5_378
10_378

1.0

4.143

4
2.819

2.947

3.269

2
1
0
9.45

18.90

37.80
RH/Fe

75.60

151.20

Figure 3. Photonic efficiency for PCT degradation at

1.5 min treatment as a function of H2O2:Fe(II) ratio for two
Fe(II) initial concentration (Blue: 10 mg L-1. Red: 5 mg L-1)

Regarding the influence of the Fe(II), Figure 3

shows the results obtained for 1.5 minutes
treatment and efficiencies are a 50% lower when 5
mg L-1 Fe(II) are supplied instead of 10 mg L-1. No

optimum is observed for 5 mg L-1 Fe(II) within the

experimental conditions tested and it might be at
higher RH/Fe as the increasing trend shows.

are lower and do not exhibit a clear trend.

3.00

3.5
3

tf=15
tf=45
tf=75

tf=30
tf=60

2.50
2.141
2.00

app,TOC

Photonic efficiency of mineralization (app,TOC)

Photonic efficiencies of mineralization are lower
than PCT degradation, as Figure 4 demonstrates
and they exhibit an increasing trend for higher RH/Fe.
As in the case of PCT degradation, app,TOC
decreases with time. In the most favorable case (10
mg L-1 Fe(II) and RH/Fe = 75.6), a 44% mineralization
is achieved during the first 15 min treatment and
92% is possible at 75 min.

3.048

tf=15min

1.858

1.50

1.891

1.246
0.933

1.00
0.50

1.036

0.309

0.00
9.45

18.9

37.8
RH/Fe

75.6

151.2

Figure 5. Photonic efficiency for mineralization at 15 min

treatment as a function of H2O2:Fe(II) ratio for two Fe(II)
initial concentration (Blue: 10 mg L-1. Red: 5 mg L-1)

Fe=10

app,TOC

2.5
2
1.5
1
0.5
0
9.45

18.9

R H/Fe

37.8

75.6

Figure 4. Photonic efficiency of mineralization for Fe(II) =

10 mg L-1 and different ratios H2O2:Fe(II)

Figure 5 shows app,TOC for the two Fe(II)

concentrations studied at 15 minutes treatment and
it presents an increasing trend when 10 mg L-1
Fe(II) is supplied. At 5 mg L-1 Fe(II) the efficiencies

Within the tested experimental conditions, higher

efficiencies of mineralization are obtained with 10
mg L-1 Fe(II) and higher RH/Fe = 75.6. As PCT
degradation is achieved during the first 10 min
treatment, this parameter combination seems to
satisfactorily achieve both objectives: PCT
degradation and mineralization. Even though the
photonic efficiency for PCT degradation is even
higher at RH/Fe = 37.8, which means less Fenton
reagent cost.

Conclusions
Within the experimental loads studied, increasing Fe(II) load does not provide any improvement when substoichiometric H2O2 is used (94.5 mg L-1), but when twice the stoichiometric H2O2 is supplied (378 mg L-1), a
10 percentage point improvement in mineralization is possible using 10 mg L -1 Fe(II) instead of 5 mg L-1. In
all of the cases, PCT is completely removed during the first 10 minutes treatment.
Photonic efficiency of mineralization decreases with time and results suggest that higher Fe(II) initial
concentrations and higher H2O2:Fe(II) rates lead to higher efficiencies.
Photonic efficiency of PCT degradation does not depend on H2O2 load after 5 min operation and, as in the
case of mineralization, are higher when higher Fe(II) initial concentration is used. For the first 1.5 minutes
treatment, a local optimum of H2O2:Fe(II) ratio equal to 37.8 is observed.
Acknowledgements
Financial support received from the Spanish "Ministerio de Economa y Competitividad" and the European Regional
Development Fund (both funding the research Projects EHMAN, DPI2009-09386 and SIGERA, DPI2012-37154-C02-01) are
fully appreciated. Evelyn Yamal-Turbay appreciates financial support from Universidad de Carabobo through professional
grant CD-4352. O.M. Alfano and L.O. Conte acknowledge financial support from UNL, CONICET and ANPCyT of Argentina.
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