Journal of Pharmaceutical and Biomedical Analysis 106 (2015) 4651

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Journal of Pharmaceutical and Biomedical Analysis

journal homepage: www.elsevier.com/locate/jpba

Studies on the kinetics of carbamazepine degradation in aqueous

matrix in the course of modied Fentons reactions
Agnieszka Karpinska, Aneta Sok, Joanna Karpinska
Institute of Chemistry, University of Bialystok, Poland

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

Article history: The present article describes a study into the kinetics of carbamazepine degradation under inuence of
Received 15 March 2014 the standard Fentons reagent, light-enhanced Fentons reagent, as well as modied Fentons systems
Received in revised form 23 June 2014 in which iron(II) ion is replaced by Cu(I), Cu(II), Ni(II), Mn(II), Cr(III) and V(V) ions. In the course of the
Accepted 24 June 2014
study it was established that V(V) ion modied Fentons reagent was equally effective in relation to
Available online 2 July 2014
carbamazepine as the standard reagent. Parameters of both standard and modied Fentons reagents
were optimized. It was observed that an increased concentration of inorganic ions and acidic pH levels
Keywords:
precipitated the decomposition of carbamazepine.
Carbamazepine
Fenton reagent 2014 Elsevier B.V. All rights reserved.
Modied Fenton reagent
Photodegradation
Kinetics of reaction

1. Introduction can be non-immediate, cumulating slowly and imperceptibly over

Dynamic expansion of pharmaceutical markets along with
elevated drug consumption are principal reasons behind the
increasing pollution of water environments with pharmaceutics
and products of their partial decomposition. These substances pen-
etrate into water environments mostly by way of municipal waste,
and as biological agents, they pose serious harm to water organisms
and to humans [1]. For this reason, one of the overriding goals of
environmental chemistry has become to analyze the life cycle of
biologically active pharmaceutical substances existent in untreated
and treated sewage, as well as in surface water (e.g. rivers, streams,
lakes), groundwater, and drinking water [2].
Presence of drugs in surface water is a result of various fac-
tors, the most inuential among them being: amounts in which the
drugs are taken, frequentness and periodicity of their use, forms
of their excretion (i.e. as metabolites or in an unchanged form),
and effectiveness of their neutralization during sewage treatment.
Small as the individual quantities of drugs that enter water envi-
ronments may be, the sheer constancy of the process leads to their
considerable accumulation, followed by increased concentration
in water milieus. Pharmaceutical substances prevalent in water
ecosystems may be harmful to indigenous water organisms, and
in an indirect way to humans. Worse still, the negative effects
Corresponding author.
E-mail address: joasia@uwb.edu.pl (J. Karpinska).
a time span of many years to a moment when they become severe
threat to human health, especially considering the fact that life-
times of many drugs in the natural environment reach up to ca.
one year, and there are substances which sustain much longer
[3]. One of the compounds frequently found in various sections
of water ecosystems is carbamazepine (5H-dibenzo[b,f]azepine-5-
carboxamide), a drug belonging to the derivatives of dibenzazepine
(Fig. 1) which, apart from its common application in the treatment
of epilepsy, is administered in neuropathic pains and multiple scle-
rosis. Carbamazepine exhibits mood-stabilizing properties, and is
often used in the therapy of manic episodes and bipolar affec-
tive disorders [4,5]. It is characterized by strong lipophilicity;
also, ca. 7080% of the drug bonds with proteins. In the liver,
carbamazepine is oxidized, deaminated, hydroxylated and partly
estericated with glucuronic acid. Its main route of excretion
is urine, and the metabolites include pharmacologically inert
trans-10,11-dihydro-10,11-dihydroxy carbamazepine and phar-
macologically active carbamazepine-10,11 epoxide. The biological
half-life of the drug is relatively long, and it depends on the duration
of the treatment period. In particular, the elimination half-life from
the human organism corresponds to the treatment time, amount-
ing to 2445 h when a single dose is administered, and 1524 h
in long-term therapies [6]. Due to the fact that carbamazepine
is so widely used, it belongs to drugs which are most frequently
detected in environmental samples, considering the whole gamut
of pharmaceutical substances present in the environment. Its mean
concentration in municipal waste reaches 2.1 g L1 [7]; more-
over, it can be found in surface or even drinking water [7,8].

http://dx.doi.org/10.1016/j.jpba.2014.06.033
0731-7085/ 2014 Elsevier B.V. All rights reserved.
 A. Karpinska et al. / Journal of Pharmaceutical and Biomedical Analysis 106 (2015) 4651
N with double distilled water.
Fig. 1. Carbamazepine structure.
Numerous experiments have conrmed that the compound
is highly resistant to photodegradation and biodegradation in
conventional sewage treatment plants. Specically, its photode-
composition lasts between 50 and 100 days [9,10], and the ensuing
photoproducts impinge on the natural environment event to a
greater extent than the original compound. For that matter, one
of the most frequently encountered products of this photodecom-
position is acridine, often present in municipal waste [9,11].
In recent years, much attention has been devoted to research on
advanced oxidation processes (AOPs). These processes are charac-
terized by great efciency in the cases of contaminants with high
degree of chemical stability and low susceptibility to biological
degradation [12,13]. Many organic compounds present in water
and sewage in the course of AOP undergo complete mineraliza-
tion to carbon dioxide and water, or, alternatively, in the course
of incomplete oxidation processes, are subjected to decomposition
into much simpler molecules such as e.g. alcohols, aldehydes, or
biodegradable carboxylic acids.
All methods of advanced oxidation are reliant on genera-
tion of highly reactive free radicals, especially hydroxyl radicals
( HO) [14]. It happens that in AOPs the ( HO) radicals are often-
times provided by the Fentons reaction. Fentons reagent exhibits
strong oxidative properties in relation to some compounds pre-
cisely due to the triggered formation of ( HO) radicals [15,16].
However, in order to boost the performance, efciency and cost-
effectiveness of the reaction, further improvements of Fentons
reagent are sought after. The classic Fentons reaction, despite its
already high efciency, has certain limitations related to the sta-
bility of the solutions pH. Essentially, the acidic character of the
solution has to be maintained to ensure that iron(III) hydroxide
does not precipitate. Many researchers have been introducing var-
ious improvements to the Fentons reaction, mostly using various
sources of iron ions, or other transition metals ions [1720] along-
side additional sources of energy. Accordingly, one can distinguish
UV radiation enhanced Fentons reaction (photo-Fenton), ultra-
sound aided Fentons reaction (sono-Fenton), both UV radiation
and ultrasound supported Fentons reaction (sono-photo-Fenton),
Fentons reaction improved by the presence of photocatalyst
(UV/TiO2 + Fentons reaction), the sono-photocatalytic Fentons
reaction (US + UV/TiO2 + Fentons reaction), as well as the electro-
Fentons reactions. All of these have been used for the purpose of
efcient removal of harmful substances [2124].
The experiments described within the scope of the present
article aimed at investigating the kinetics of carbamazepine decom-
position under the inuence of transition metal hydrogen
peroxide type Fentons reagent, and comparing the results to those
obtained by means of the classic and photocatalytic Fentons reac-
tions.
2. Experimental part
2.1. Reagents
Carbamazepine used in the research was produced by
SigmaAldrich, USA. Its stock solution with the concentration of
102 mol L1 was prepared in a 50 mL laboratory ask by dissolv-
ing an appropriate weighted amount of the compound in 10 mL of
47
ethanol, and lling up the ask to the full measure with double
distilled water. Working solutions of desired concentrations were
obtained individually by appropriately diluting the model solution
Inorganic salts: hydrated iron(II) sulfate, hydrated cop-
per(II) sulfate, copper(I) chloride, hydrated manganese(II) sulfate,
hydrated chromium(III) sulfate, hydrated nickel(II) nitrate, ammo-
nium metavanadate were purchased from POCh (Poland). Model
solutions of Fe(II), Cu(I), Cu(II), Mn(II), Cr(III) and Ni(II) ions with
concentrations of 102 mol L1 each were obtained by dissolving
in double distilled water appropriate weighted amounts of the
reagents with the addition of 2 mL 3 mol L1 of sulfuric acid. Indi-
vidual working solutions were prepared by appropriately diluting
the stock solutions. In the case of ammonium metavanadate, the
model solution with the concentration of 102 mol L1 was pre-
pared by dissolving its appropriate weighted amount in 0.1 mol L1
solution of sulfuric acid.
Hydrogen peroxide (CHEMPUR, Poland) in the concentration of
101 mol L1 was prepared on a daily basis by suitably diluting its
30% solution in MilliQ water.
Samples of raw and treated sewage were taken from the local
wastewater treatment plant on 16th March 2013. The samples were
adjusted to pH 2 with hydrochloric acid and stored in refrigerator
at 0 C.
2.2. Equipment
Evaluation of the kinetics was carried out observing the changes
in absorbance of the carbamazepine solutions by Hitachi U-2800A
spectrophotometer.
In the irradiation experiments 16 AU standard UV lamp (Cobra-
bid, Poland) was used; it was tted with radiators emitting 256 nm
and 366 nm radiation. Considering that the goal of the research was
to analyze the course of photodegradation of carbamazepine in the
natural environment, the experimental solutions were irradiated
with  = 366 nm UVA radiation.
To determine qualitative compositions of the post-reaction
mixtures, a chromatographic system consisting of: a 3D detector
Spectra System UV 3000, a low-gradient pump P2000 (Therma Sep-
aration, USA), 15 cm long ODS-2 column (SUPELCO INC), and 20 L
Rheodyne injection valve was put into use. ChromQuest Chro-
matography Data System software version for Windows NT was
used for the acquisition and storage of data.
2.3. Experimental procedure
2.3.1. Analysis of the standard and photocatalytic reactions
between Fentons reagent and carbamazepine
A 10 mL volumetric ask was lled in turn with proper mea-
sured volumes of Fe(II) and H2 O2 solution with the concentration
of 5 105 mol L1 , 1 mL of carbamazepine solution (CBZ) with the
concentration of 5 104 mol L1 , and MilliQ water to the full mea-
sure. The reaction was observed over a time span of 120 min, during
which the absorbance of the solution was periodically recorded,
with the rst measurement taken after 5 min. Solutions of reagents
with identical composition to the scrutinized sample but not con-
taining carbamazepine were used as blanks.
In assessment of the photocatalytic Fentons reaction, the reac-
tion solution was set up in the same manner as above. Next, the
mixture was placed in a crystallizing dish and exposed to 366 nm
wavelength radiation. Absorbance was measured every 10 min, the
rst measurement taken 5 min after the reagents were blended.
2.3.2. Effectiveness of modied Fentons reagents
The following modied Fentons systems were taken into
consideration: V(V)-H2 O2 , Cu(I)-H2 O2 , Cu(II)-H2 O2 , Ni(II)-H2 O2 ,
48 A. Karpinska et al. / Journal of Pharmaceutical and Biomedical Analysis 106 (2015) 4651
Mn(II)-H2 O2 , Cr(III)-H2 O2 . The experimental procedure in this
case was as described below: into a 10 mL volumetric ask 1 mL
of CBZ solution with the concentration of 5 104 mol L1 was
introduced, later adding proper volume of the analyzed metal ion
solution and H2 O2 so as to obtain the Me:H2 O2 molar ratio equal 1:1
(CMe = CH2 O2 = 1 102 mol L1 ); subsequently, MilliQ water was
added to the full measure. Changes in the concentration of CBZ were
observed in the course of 120 min, during which the spectra of the
examined solutions at the analytical wavelength of 282 nm were
recorded in the xed time intervals. The rst measurement was
taken 5 min after all the reagents were mixed. Solutions of reagents
with identical composition and concentration to the scrutinized
sample but not containing carbamazepine were used as blanks. In
the examination of inuence of UV radiation on the decomposition
of carbamazepine in the modied Fentons reactions, all the cor-
responding solutions were irradiated with  = 366 nm wavelength
radiation.
2.3.3. Kinetics of carbamazepine decomposition in the presence of
natural matrix raw and treated sewage
To assess the impact of natural matrix, i.e. raw and treated
wastewater on the kinetics of decomposition of the analyzed
compound under inuence of the standard Fentons reagent, two
Fenton systems at various compositions were checked. The fol-
lowing procedure was applied: into two 10 mL volumetric asks
proper amounts of Fe(II) and H2 O2 solution with the concentra-
tion of 5 103 mol L1 were added, so as to obtain Fe(II):H2 O2
molar ratios equal respectively 1:1, 4:1. The nal concentration
of Fe(II) ions were equal to 5 104 and 2 103 mol L1 , respec-
tively. Later, 1 mL of 5 104 mol L1 CBZ solution was added to
each of them, and the asks were lled up with raw wastewater
solution to the full measures. Identical procedure was carried out
for the samples with treated wastewater. In the next step, portions
of the test solution were extracted in the xed time intervals and
each time the spectrum was registered using the mixture of the
reagents not containing carbamazepine as blank. All the measure-
ments were taken at the analytical wavelength of 282 nm in 10 min
intervals, with the rst measurement carried out 5 min from the
beginning of the experiment. Effectiveness of the modied Fentons
reagent with regard to carbamazepine in natural matrix conditions
was evaluated in the same way as above, the only difference being
that instead of Fe(II) ions, 1 mL of V(V) solution and 2 mL of H2 O2
solution with the concentrations of 5 102 mol L1 were used.
2.3.4. Chromatographic analysis of the products of decomposition
and photo-decomposition of carbamazepine
During the experiments, the following chromatographic setup
was used: mobile phase water, methanol, acetonitrile (64/30/6,
v/v/v); ODS-2 column; mobile phase ow rate 1 mL/min,
 = 282 nm. In the above conditions, CBZ retention time equaled
26 min.
3. Results and the discussion
3.1. Kinetics of carbamazepine degradation in the model solutions
under the inuence of the standard and modied Fentons reagent
All the kinetic analyses were conducted by means of spec-
trophotometry. For this reason, the experiments were initiated by
registering the absorption spectrum of carbamazepine within the
range of 190400 nm (Fig. 2) with the purpose of establishing the
analytical wavelength. Essentially, the spectrum of carbamazepine
has two characteristic peaks: an intensive one at 200 nm and a
less intensive one at 282 nm. Changes in the concentration of
carbamazepine under the inuence of the used reagents were
monitored measuring absorbance of the experimental solutions
Fig. 2. The UV-spectra of carbamazepine: 5 106 mol L1 , -----
5 105 mol L1 , 1 104 mol L1 .
at the wavelength of 282 nm. It was observed that at  = 282 nm
LambertBeer law was preserved within the concentration range
of 107 104 mol L1 (the determined model curve equation was
y = 1.3 104 x + 2.3 103 , where x carbamazepine concentra-
tion).
In all the described experiments, the used concentration of car-
bamazepine was 5 105 mol L1 . First of all, the effectiveness of
the classic and photocatalytic Fentons reactions was evaluated.
To this end, the importance of: the order in which the reagents
were mixed, the concentrations of Fe(II) and H2 O2 solutions and
their molar ratios, and pH level on the rate of CBZ degradation was
evaluated. The second-order kinetics model was assumed for the
observed processes. As a result, it was concluded Fentons reagent
was the most potent when the constituents were mixed in the
following order: Fe(II) solution, H2 O2 solution, and the drug solu-
tion. Next, concentrations of the used Fe(II) and H2 O2 solutions
were optimized, taking into account solutions with the concen-
trations between 5 106 and 5 103 mol L1 and keeping 1:1
molar ratio of the components of Fentons reagent. It was concluded
that when high concentrations of Fe(II) and H2 O2 (i.e. higher than
103 mol L1 ) were employed, the reaction proceeded too quickly,
whereas with the concentrations below 105 mol L1 the progress
was too slow. That is why the concentration of 5 104 mol L1 was
chosen as optimal; the rate of CBZ decomposition for this particular
concentration allowed for accurate measurements of the changes
in the drug content in the test solution.
In addition, pace of the Fentons reaction is heavily reliant on
the pH of the solution. The optimum pH range for the process is
35. This is because of the fact that too low pH levels encourage the
formation of Fe(II) ions which are of low reactivity, e.g. Fe(OH)2+ ,
whereas in the opposite case (pH > 5) complex bonds tent to occur,
causing hydroxides to precipitate. Within the framework of the
described experiments, effectiveness of Fentons reagent with the
composition of Fe(II):H2 O2 = 1:1 (c = 5 104 mol L1 ) at pH lev-
els between 2 and 5 was assessed. During the analysis, pH of the
solutions was controlled by the addition of either H2 SO4 or NaOH.
Ultimately, it was established that decomposition of CBZ proceeded
the most slowly at pH 5, whereas its rate was the fastest at pH 3.
Therefore, the latter value was adopted for further tests.
Furthermore, the importance of molar ratio of the reagents
for the efciency of carbamazepine degradation was subject to
scrutiny. Accordingly, several test solutions were set up for which
the Fe(II): H2 O2 molar ratio equaled 1:1, 1:2, 1:4, 1:5, 1:10, 2:1, 4:1,
5:1, 10:1. The nal concentration of carbamazepine in each one
of the mixtures was 5 105 mol L1 . It was resolved that excess
of hydrogen peroxide in relation to iron ions was disadvantageous
from the perspective of carbamazepine degradation. Specically,
the more marked the presence of hydrogen peroxide, the slower
 A. Karpinska et al. / Journal of Pharmaceutical and Biomedical Analysis 106 (2015) 4651
Fig. 3. The spectra of CBZ registered after 120 min of reaction in the system
CBZ-modied Fentons reagent (cCBZ = 5 105 mol L1 , ---- cV(V) = 1 103 mol L1 ,
1 1
cH2 O2 = 5 104 mol L , cV(V) = 2.5 103 mol L1 , cH2 O2 = 5 104 mol L ,
cV(V) = 5 103 mol L1 , cH2 O2 = 5 104 mol L
1
).
was the observed process. In fact, only minimal decrease in
carbamazepine concentration was registered in such cases. On the
other hand, the increase in the concentration of iron in relation
to hydrogen peroxide facilitated CBZ degradation. For example,
Fentons reagent with the composition of Fe(II):H2 O2 = 10:1 caused
20% decrease in carbamazepine concentration over 120 min. The
molar ratios of Fe(II):H2 O2 equaled 1:1 and 1:4 were applied for
the verication of the practical usefulness of the classic Fentons
system at the presence of natural matrix.
Next, the course of carbamazepine photodegradation process
under the inuence of the photocatalytic Fentons reagent was
investigated. Due to the fact that the discussed experiments
assumed natural environment setting for the analyzed Fentons
reactions, in the photocatalytic tests 366 nm wavelength radia-
tion was used. This radiation belongs to the mid-UVA spectral
region. The experiment was carried out using Fentons reagent with
Fe(II):H2 O2 molar ratio equal 10:1 (pH 3, cCBZ = 5 105 mol L1 ).
No signicant improvement in effectiveness of Fentons reagent
was noticed under UVA radiation.
In the subsequent stage, the performance of modied Fen-
tons reagents was studied. The modications in question involved
replacement of Fe(II) ions with Cr(III), Cu(I), Cu(II), Ni(II), Mn(II) and
V(V) ions. For this purpose, a series of CBZ solutions was prepared,
and to each of the solutions the selected ion and hydrogen perox-
ide were introduced, preserving the molar ratio Me:H2 O2 = 1:1. The
nal concentration of CBZ amounted to 5 105 mol L1 , and as far
as the modied Fentons reagents were concerned, their concen-
trations were 103 mol L1 . It should be mentioned here that the
solutions were shielded against light. Every 10 min the progress of
the reaction was monitored, measuring the absorbance of each of
the solutions at 282 nm. As in the case of classical Fenton reaction,
the second-order kinetics model was established for the studied
reactions. In particular, it was noticed that the decrease in the
concentration of carbamazepine in the period of 120 min. varied
between the used ions: it was contained between 11% (Ni2+ ) and
16% (Cu2+ ), having been lower than in the case of the standard Fen-
tons reaction. The only exception to this rule was the V(V)-H2 O2
conguration: it was observed that in the presence vanadium (V)
ions the 21% of carbamazepine lost was detected after 120 min. The
further experiments showed that in the presence of a hundred-
fold excess of vanadium (V) ions carbamazepine underwent rapid
degradation. To be precise, after 120 min from the mixing of the
solution, the drug almost completely decomposed (Fig. 3).
That is why all further studies concerning the efciency of the
modied Fentons reagent were conducted preferring the solu-
tion of ammonium metavanadate over iron(II) salts. Similarly to
49
the case of the standard Fentons reaction, degradation of CBZ
under the modied Fentons reagent is dependent on the con-
centrations of the individual components of the reagent, pH of
the solution and V(V):H2 O2 molar ratio. In the rst place, the
importance of the concentration of reagents was surveyed. The
following concentrations of the substances composing the modi-
ed Fentons reagent were taken into account: 5 104 , 103 and
5 103 mol L1 , preserving the molar ratio 1:1. It was observed
that degradation of carbamazepine in the presence of the modi-
ed Fentons reagent with the concentration of 5 103 mol L1
occurred very quickly. Essentially, already after 5 min 60% of the
analyzed drug decomposed. Hence, for further experiments the
concentration of 5 103 mol L1 was chosen as optimum. In a
similar vein to the standard Fentons reaction, pH has no small
impact on the effectiveness of the modied reaction. In this case, it
was discovered that low ambient pH (2) was the most advanta-
geous with the V(V)-H2 O2 reagent. In the following step, the molar
ratio V(V):H2 O2 was optimized. This involved analyzing degrada-
tion of carbamazepine under the inuence of the modied Fentons
reagent with various molar compositions (V(V):H2 O2 = 1:2, 1:4,
1:10, 2:1, 5:1, 10:1). The conclusions drawn this time were similar
to those for the standard Fentons reaction, i.e. excess of vanadium
(V) ions in relation to H2 O2 hastens the process, whereas overabun-
dance of hydrogen peroxide in relation to vanadium (V) ions is an
inhibiting factor as far as the degradation of carbamazepine is con-
cerned. This observation can be explained by its action as hydrogen
radical scavenger according to the equation [25]:
H2 O2 + OH OH2 + H2 O
Having noticed that with the growing concentration of V(V) in
relation to H2 O2 the degradation proceeded much quicker, it has
to be added that with a tenfold excess of the metal ions, already
after 5 min after the mixing of reagents, CBZ in the test solution
underwent total decomposition. It was observed that at the higher
concentrations of components (equal 102 mol L1 ) of modied
Fentons reagent even solutions contained an overabundance of
hydrogen peroxide were so efcient as those with an excess of
metavanadium ion. As at the presence of an excess of vanadium
ions the decomposition of CBZ proceeded very quickly, the fur-
ther experiments were done using modied Fentons reagent with
the composition V(V):H2 O2 = 1:2 (cV(v) = 5 103 mol L1 , cH2 O2 =
102 mol L1 ).
Also, the effect of UV radiation on the kinetics of CBZ degradation
in the modied Fentons reagent setting was investigated. Just as
in the former case of the standard photocatalytic Fentons reaction,
 = 366 nm wavelength radiation was applied. The experimental
trial showed that there were no signicant differences between
the photocatalytic and the dark reactions as far as the analyzed
process was concerned.
The data gathered in Table 1 presents dependency between the
constant rate of carbamazepine decomposition and the molar ratio
of the components, for both the standard and the modied Fentons
reagent. In particular, the discussed experiments indicate that the
standard reagent surpasses the modied reagent in efciency for
low molar ratios inorganic ion: H2 O2 as well as for low concentra-
tions of the reagent. In the case of the modied reagent, the excess
of V(V) caused the degradation of carbamazepine to proceed more
rapidly. When the excess of V(V) was tenfold in relation to H2 O2 ,
CBZ decomposed very quickly.
The efciency of the modied Fenton reagent can be attributed
to the presence of VO2 + ion [26]. In acidic aqueous environment in
the presence of hydrogen peroxide the following equilibriums are
determined [26]:
VO2 + + H2 O2 VO(O2 )+ + H2 O
50 A. Karpinska et al. / Journal of Pharmaceutical and Biomedical Analysis 106 (2015) 4651

Table 1
Kinetic characteristics of carbamazepine degradation under inuence of studied processes.

Studied process pH Final concentration of Final concentration of k (L mol1 min1 ) t1/2 (h)
metal ion (mol L1 ) H2 O2 (mol L1 )

Classical Fenton 5 5 104 5 104 10.08 33.09

reaction 4 5 104 5 104 32.13 10.38
3 5 104 5 104 80.87 4.12
3 1 103 5 104 53.34 6.25
3 2 103 5 104 45.55 7.32
3 2.5 103 5 104 65.74 5.07
3 5 103 5 104 177.35 1.88

Vanadium ion modied 2 5 104 5 104 18.71 17.82

Fenton process 2 1 103 5 104 28.82 11.57
2 2 103 5 104 518.26 8.63
2 5 103 5 104 Total degrdation after 5 min
2 5 103 5 103 124.95 2.67
2 5 103 1 102 242.74 1.37
2 5 103 2 5 102 236.63 1.41
2 1 102 5 103 Total degradation after 5 min.

Table 2
+ + The rates of carbamazepine degradation under inuence of studied processes at the
VO(O2 ) + H2 O2 VO(O2 )2 + 2H presence of natural matrix.

Raw sewage Treated sewage

+
VO(O2 )2 + H HVO(O2 )2 Classic Fentons reaction
Fe(II):H2 O2 = 1:1 k = 14.73/L min1 mol1 23.57/L min1 mol1
cFe(II) = 5 104 mol L1
It is assumed that the generated in the presence of hydro- 1
cH2 O2 = 5 104 mol L
gen peroxide the monoperoxo and diperoxo vanadium species are
responsible for degradation of carbamazepine. Fe(II):H2 O2 = 4:1 24.50/L min1 mol1 54.46/L min1 mol1
cFe(II) = 2 103 mol L1
Finally, a qualitative chromatographic analysis of carba- 1
cH2 O2 = 5 104 mol L
mazepine solutions subjected to the inuence of the standard and
the modied Fentons reagent was carried out. The rst chro- Modied Fentons reaction
matograms were recorded 5 min after the mixing of the reagents, V(V):H2 O2 = 2:1 560 min 560 min
and all subsequent records were taken every 20 min. Carba- cV(V) = 5 103 mol L1 1098.80/L min1 mol1 k = 331.16/L min1 mol1
1
mazepine retention time in the discussed chromatographic setting cH2 O2 = 1 102 mol L 70120 min 70120 min
k = 420.49/L min1 mol1 k = 11.81/L min1 mol1
was 26.56 0.21 min. Some gradual decrease of the peak of the
analyzed drug was noted; however, no new peaks related to the
potential products of decomposition were observed. The HPLC 4. Conclusion
technique results conrmed the conclusions concerning the out-
come of the spectrophotometric measurements. The presented study describes research on the kinetics of car-
bamazepine degradation under the inuence of the standard and
3.2. Standard and modied Fentons reaction in the presence of the modied Fentons reagent. In the course of the conducted
natural matrix experiments it was concluded that the V(V)-H2 O2 reagent system
when applied to carbamazepine is just as effective as the standard
The process of carbamazepine degradation under the inuence Fentons reagent. Analogically to the classic Fentons reaction, effec-
of the standard and the modied Fentons reagent was also stud- tiveness of the modied reagent is increased when there is an
ied when raw and treated municipal waste was introduced into the excess of metal ions in relation to hydrogen peroxide. The presence
reaction environment. The wastewater samples had been retrieved of the excess of hydrogen peroxide worked as radicals scavenger.
from a local municipal waste treatment plant. In the experi- The action of modied by metavanadate Fenton-reagent could be
ments, the following reagents were used: the standard Fentons explained by presence of VO2 + ion which undergoes reactions
reagent with the components in 1:1 molar ratio (cFe(II) = cH2 O2 = with compounds present in reaction environment with generation
of monoperoxo and diperoxo vanadium species. The presence of
5 104 mol L1 ) and 4:1 molar ratio (cFe(II) = 2 103 mol L1 ,
organic carbon rich matrix promote the reaction of CBZ decompo-
cH2 O2 = 5 104 mol L1 , as well as the modied Fentons reagent sition under the modied Fentons reagent.
V(V):H2 O2 = 1:2 (cV(v) = 5 103 mol L1 , cH2 O2 = 102 mol L1 ).
The achieved results are compiled in Table 2. Basically, it was estab- References
lished that in the standard Fentons reaction the presence of natural
matrix had inhibitive effects on the investigated process, while in [1] A. Kumar, I. Xagoraraki, Pharmaceuticals, personal care products and
the case of the modied Fentons quite the inverse phenomenon endocrine-distrupting chemicals in U.S. surface and nished drinking waters:
a proposed ranking system, Sci. Tot. Environ. 408 (2010) 59725989.
was observed. To be precise, a rapid decline in the concentration of [2] S.D. Richardson, T.A. Ternes, Water analysis: emerging contaminants and cur-
CBZ was being observed over the period of initial 60 min from the rent issues, Anal. Chem. 83 (2011) 46144648.
mixing of the reagents, but later the process slowed down. Iden- [3] S. Mompelat, B.L. Bot, O. Thomas, Occurrence and fate of pharmaceutical prod-
ucts and by-products, from resource to drinking water, Environ. Int. 35 (2009)
tical situation occurred when the natural matrix was constituted 803814.
by treated wastethe reaction proceeded intensively over the rst [4] W. Janiec, Compendium of pharmacology, in: W. Janiec, U. Cega, M. Pytlik
hour. Taking into account these observations it could be assumed (Eds.), Psychotropic Drugs, Medical Publishing House PZWL, Warsaw, 2010.
[5] T. Saji, S.M. Chandra, A. Ashutosh, P. Saroy Kumar, Identication and structural
that the presence of organic matrix promote the regeneration of
elucidation of an known impurity in carbamazepine active pharmaceuti-
VO2 + ion which complete the catalytic cycle [26]. cal ingredient by liquid chromatographytandem mass spectrometry and
 A. Karpinska et al. / Journal of Pharmaceutical and Biomedical Analysis 106 (2015) 4651
semi-preparative chromatographic isolation, J. Pharm. Biomed. Anal. 56 (2011)
423428.
[6] J. Pacha, Introduction to clinical toxicology, in: B. Groszek, J. Wilamowska
(Eds.), Carbamazepine, Publishing House of Jagiellonian University, Krakw,
2009.
[7] T.E. Doll, F.H. Frimmel, Fate of pharmaceutical photodegradation by simulated
solar UV-light, Chemosphere 52 (2003) 17571769.
[8] S.K. Khetan, T.J. Collins, Human pharmaceuticals in the aquatic environment: a
challenge to green chemistry, Chem. Rev. 107 (2007) 23192364.
[9] Y. Zhang, S.-U. Geissen, C. Gal, Carbamazepine and diclofenac: removal in
waste water treatment plants and occurrence in water bodies, Chemosphere
73 (2008) 11511161.
[10] F.I. Hai, X. Li, W.E. Price, L.D. Nghiema, Removal of carbamazepine and
sulfamethoxazole by MBR under anoxic and aerobic conditions, Bioresour.
Technol. 102 (2011) 1038610390.
[11] V. Calisto, M.R.M. Domingues, G.L. Erny, W.I. Esteves, Direct photodegrada-
tion of carbamazepine followed by micellar electrokinetic chromatography and
mass spectrometry, Water Res. 45 (2011) 10951104.
[12] J.M. Poyatos, M.M. Munio, M.C. Almecija, J.C. Torres, E. Hontoria, F. Osorio,
Advanced oxidation processes for wastewater treatment: state of the art, Water
Air Soil Pollut. 205 (2010) 187204.
[13] R. Lamsal, M.E. Walsh, G.A. Gagnon, Comparison of advanced oxidation pro-
cesses for the removal of natural organic matter, Water Res. 45 (2011)
32633269.
[14] B. Modrzejewska, A.J. Guwy, R. Dinsdale, D.L. Hawkes, Measurement of hydro-
gen peroxide in an advanced oxidation process using an automated biosensor,
Water Res. 41 (2007) 260268.
[15] K. Barbusinski, Henry John Horstman Fenton short biography and brief history
of Fenton Reagent Discovery, Metrologia 14 (2009) 12.
[16] H. Zhang, H.J. Choi, Ch.-P. Huang, Optimization of Fenton process
for the treatment of landll leachate, J. Hazard. Mater. 125 (2005)
166174.
51
[17] K. Choi, W. Lee, Enhanced degradation of trichloroethylene in nano-scale
zero-valent iron Fenton system with Cu(II), J. Hazard. Mater. 211212 (2012)
146150.
[18] E.R. Bandala, M.A. Pelaez, D.D. Dionysiou, S. Gelover, J. Garciaa, D.
Macias, Degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) using cobalt-
peroxymonosulfate in Fenton-like process, J. Photochem. Photobiol. A: Chem.
186 (2007) 357363.
[19] X. Li, Z. Xiong, X. Ruan, D. Xia, Q. Zeng, A. Xu, Kinetics and mechanism of organic
pollutants degradation with cobaltbicarbonatehydrogen peroxide system:
investigation of the role of substrates, Appl. Catal. A: Gen. 411412 (2012)
2430.
[20] T. Rhada, J.-Y. Piquemala, L. Sicarda, F. Herbsta, E. Briotc, M. Benedettid, A.
Atlamsani, Polyol-made Mn3 O4 nanocrystals as efcient Fenton-like catalysts,
Appl. Catal. A: Gen. 386 (2010) 132139.
[21] K. Ninomiya, H. Takamatsu, A. Onishi, K. Takahashi, N. Shimizu,
SonocatalyticFenton reaction for enhanced OH radical generation and its
application to lignin degradation, Ultrason. Sonochem. 20 (2013) 10921097.
[22] I. Sires, C. Arias, P.L. Cabot, F. Centellas, J.A. Garrido, R.M. Rodriguez, E. Brillas,
Degradation of clobric acid in acidic aqueous medium by electro-Fenton and
photoelectro-Fenton, Chemosphere 66 (2007) 16001669.
[23] H. Shemer, Y.K. Kunukcu, K.G. Linden, Degradation of the pharmaceutical
metronidazole via UV, Fenton and photo-Fenton processes, Chemosphere 63
(2006) 269276.
[24] R. Salazar, S. Garcia-Segura, M.S. Ureta-zanartu, E. Brillas, Degradation of dis-
perse azo dyes from waters by solar photoelectro-fenton, Electrochim. Acta 56
(2011) 63716379.
[25] R.F. Pupo Nogueira, M.C. Oliveira, W.C. Paterlini, Simple and fast spec-
trophotometric determination of H2 O2 in photo-Fenton reactions using
metavanadate, Talanta 66 (2005) 8691.
[26] M. Jian, L. Zhu, J. Wang, J. Zhang, G. Li, Ch. Hu, Sodium metavanadate cat-
alyzed direct hydroxylation of benzene to phenol with hydrogen peroxide in
acetonitrile medium, J. Mol. Catal. A: Chem. 235 (2006) 17.