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
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 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
N with double distilled water.
Inorganic salts: hydrated iron(II) sulfate, hydrated cop-
per(II) sulfate, copper(I) chloride, hydrated manganese(II) sulfate,
Fig. 1. Carbamazepine structure. 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
Numerous experiments have conrmed that the compound concentrations of 102 mol L1 each were obtained by dissolving
is highly resistant to photodegradation and biodegradation in in double distilled water appropriate weighted amounts of the
conventional sewage treatment plants. Specically, its photode- reagents with the addition of 2 mL 3 mol L1 of sulfuric acid. Indi-
composition lasts between 50 and 100 days [9,10], and the ensuing vidual working solutions were prepared by appropriately diluting
photoproducts impinge on the natural environment event to a the stock solutions. In the case of ammonium metavanadate, the
greater extent than the original compound. For that matter, one model solution with the concentration of 102 mol L1 was pre-
of the most frequently encountered products of this photodecom- pared by dissolving its appropriate weighted amount in 0.1 mol L1
position is acridine, often present in municipal waste [9,11]. solution of sulfuric acid.
In recent years, much attention has been devoted to research on Hydrogen peroxide (CHEMPUR, Poland) in the concentration of
advanced oxidation processes (AOPs). These processes are charac- 101 mol L1 was prepared on a daily basis by suitably diluting its
terized by great efciency in the cases of contaminants with high 30% solution in MilliQ water.
degree of chemical stability and low susceptibility to biological Samples of raw and treated sewage were taken from the local
degradation [12,13]. Many organic compounds present in water wastewater treatment plant on 16th March 2013. The samples were
and sewage in the course of AOP undergo complete mineraliza- adjusted to pH 2 with hydrochloric acid and stored in refrigerator
tion to carbon dioxide and water, or, alternatively, in the course at 0 C.
of incomplete oxidation processes, are subjected to decomposition
into much simpler molecules such as e.g. alcohols, aldehydes, or 2.2. Equipment
biodegradable carboxylic acids.
All methods of advanced oxidation are reliant on genera- Evaluation of the kinetics was carried out observing the changes
tion of highly reactive free radicals, especially hydroxyl radicals in absorbance of the carbamazepine solutions by Hitachi U-2800A
( HO) [14]. It happens that in AOPs the ( HO) radicals are often- spectrophotometer.
times provided by the Fentons reaction. Fentons reagent exhibits In the irradiation experiments 16 AU standard UV lamp (Cobra-
strong oxidative properties in relation to some compounds pre- bid, Poland) was used; it was tted with radiators emitting 256 nm
cisely due to the triggered formation of ( HO) radicals [15,16]. and 366 nm radiation. Considering that the goal of the research was
However, in order to boost the performance, efciency and cost- to analyze the course of photodegradation of carbamazepine in the
effectiveness of the reaction, further improvements of Fentons natural environment, the experimental solutions were irradiated
reagent are sought after. The classic Fentons reaction, despite its with = 366 nm UVA radiation.
already high efciency, has certain limitations related to the sta- To determine qualitative compositions of the post-reaction
bility of the solutions pH. Essentially, the acidic character of the mixtures, a chromatographic system consisting of: a 3D detector
solution has to be maintained to ensure that iron(III) hydroxide Spectra System UV 3000, a low-gradient pump P2000 (Therma Sep-
does not precipitate. Many researchers have been introducing var- aration, USA), 15 cm long ODS-2 column (SUPELCO INC), and 20 L
ious improvements to the Fentons reaction, mostly using various Rheodyne injection valve was put into use. ChromQuest Chro-
sources of iron ions, or other transition metals ions [1720] along- matography Data System software version for Windows NT was
side additional sources of energy. Accordingly, one can distinguish used for the acquisition and storage of data.
UV radiation enhanced Fentons reaction (photo-Fenton), ultra-
sound aided Fentons reaction (sono-Fenton), both UV radiation 2.3. Experimental procedure
and ultrasound supported Fentons reaction (sono-photo-Fenton),
Fentons reaction improved by the presence of photocatalyst 2.3.1. Analysis of the standard and photocatalytic reactions
(UV/TiO2 + Fentons reaction), the sono-photocatalytic Fentons between Fentons reagent and carbamazepine
reaction (US + UV/TiO2 + Fentons reaction), as well as the electro- A 10 mL volumetric ask was lled in turn with proper mea-
Fentons reactions. All of these have been used for the purpose of sured volumes of Fe(II) and H2 O2 solution with the concentration
efcient removal of harmful substances [2124]. of 5 105 mol L1 , 1 mL of carbamazepine solution (CBZ) with the
The experiments described within the scope of the present concentration of 5 104 mol L1 , and MilliQ water to the full mea-
article aimed at investigating the kinetics of carbamazepine decom- sure. The reaction was observed over a time span of 120 min, during
position under the inuence of transition metal hydrogen which the absorbance of the solution was periodically recorded,
peroxide type Fentons reagent, and comparing the results to those with the rst measurement taken after 5 min. Solutions of reagents
obtained by means of the classic and photocatalytic Fentons reac- with identical composition to the scrutinized sample but not con-
tions. taining carbamazepine were used as blanks.
In assessment of the photocatalytic Fentons reaction, the reac-
2. Experimental part 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
2.1. Reagents wavelength radiation. Absorbance was measured every 10 min, the
rst measurement taken 5 min after the reagents were blended.
Carbamazepine used in the research was produced by
SigmaAldrich, USA. Its stock solution with the concentration of 2.3.2. Effectiveness of modied Fentons reagents
102 mol L1 was prepared in a 50 mL laboratory ask by dissolv- The following modied Fentons systems were taken into
ing an appropriate weighted amount of the compound in 10 mL of 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
2.3.3. Kinetics of carbamazepine decomposition in the presence of at the wavelength of 282 nm. It was observed that at = 282 nm
natural matrix raw and treated sewage LambertBeer law was preserved within the concentration range
To assess the impact of natural matrix, i.e. raw and treated of 107 104 mol L1 (the determined model curve equation was
wastewater on the kinetics of decomposition of the analyzed y = 1.3 104 x + 2.3 103 , where x carbamazepine concentra-
compound under inuence of the standard Fentons reagent, two tion).
Fenton systems at various compositions were checked. The fol- In all the described experiments, the used concentration of car-
lowing procedure was applied: into two 10 mL volumetric asks bamazepine was 5 105 mol L1 . First of all, the effectiveness of
proper amounts of Fe(II) and H2 O2 solution with the concentra- the classic and photocatalytic Fentons reactions was evaluated.
tion of 5 103 mol L1 were added, so as to obtain Fe(II):H2 O2 To this end, the importance of: the order in which the reagents
molar ratios equal respectively 1:1, 4:1. The nal concentration were mixed, the concentrations of Fe(II) and H2 O2 solutions and
of Fe(II) ions were equal to 5 104 and 2 103 mol L1 , respec- their molar ratios, and pH level on the rate of CBZ degradation was
tively. Later, 1 mL of 5 104 mol L1 CBZ solution was added to evaluated. The second-order kinetics model was assumed for the
each of them, and the asks were lled up with raw wastewater observed processes. As a result, it was concluded Fentons reagent
solution to the full measures. Identical procedure was carried out was the most potent when the constituents were mixed in the
for the samples with treated wastewater. In the next step, portions following order: Fe(II) solution, H2 O2 solution, and the drug solu-
of the test solution were extracted in the xed time intervals and tion. Next, concentrations of the used Fe(II) and H2 O2 solutions
each time the spectrum was registered using the mixture of the were optimized, taking into account solutions with the concen-
reagents not containing carbamazepine as blank. All the measure- trations between 5 106 and 5 103 mol L1 and keeping 1:1
ments were taken at the analytical wavelength of 282 nm in 10 min molar ratio of the components of Fentons reagent. It was concluded
intervals, with the rst measurement carried out 5 min from the that when high concentrations of Fe(II) and H2 O2 (i.e. higher than
beginning of the experiment. Effectiveness of the modied Fentons 103 mol L1 ) were employed, the reaction proceeded too quickly,
reagent with regard to carbamazepine in natural matrix conditions whereas with the concentrations below 105 mol L1 the progress
was evaluated in the same way as above, the only difference being was too slow. That is why the concentration of 5 104 mol L1 was
that instead of Fe(II) ions, 1 mL of V(V) solution and 2 mL of H2 O2 chosen as optimal; the rate of CBZ decomposition for this particular
solution with the concentrations of 5 102 mol L1 were used. concentration allowed for accurate measurements of the changes
in the drug content in the test solution.
2.3.4. Chromatographic analysis of the products of decomposition In addition, pace of the Fentons reaction is heavily reliant on
and photo-decomposition of carbamazepine the pH of the solution. The optimum pH range for the process is
During the experiments, the following chromatographic setup 35. This is because of the fact that too low pH levels encourage the
was used: mobile phase water, methanol, acetonitrile (64/30/6, formation of Fe(II) ions which are of low reactivity, e.g. Fe(OH)2+ ,
v/v/v); ODS-2 column; mobile phase ow rate 1 mL/min, whereas in the opposite case (pH > 5) complex bonds tent to occur,
= 282 nm. In the above conditions, CBZ retention time equaled causing hydroxides to precipitate. Within the framework of the
26 min. described experiments, effectiveness of Fentons reagent with the
composition of Fe(II):H2 O2 = 1:1 (c = 5 104 mol L1 ) at pH lev-
3. Results and the discussion 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.
3.1. Kinetics of carbamazepine degradation in the model solutions Ultimately, it was established that decomposition of CBZ proceeded
under the inuence of the standard and modied Fentons reagent the most slowly at pH 5, whereas its rate was the fastest at pH 3.
Therefore, the latter value was adopted for further tests.
All the kinetic analyses were conducted by means of spec- Furthermore, the importance of molar ratio of the reagents
trophotometry. For this reason, the experiments were initiated by for the efciency of carbamazepine degradation was subject to
registering the absorption spectrum of carbamazepine within the scrutiny. Accordingly, several test solutions were set up for which
range of 190400 nm (Fig. 2) with the purpose of establishing the the Fe(II): H2 O2 molar ratio equaled 1:1, 1:2, 1:4, 1:5, 1:10, 2:1, 4:1,
analytical wavelength. Essentially, the spectrum of carbamazepine 5:1, 10:1. The nal concentration of carbamazepine in each one
has two characteristic peaks: an intensive one at 200 nm and a of the mixtures was 5 105 mol L1 . It was resolved that excess
less intensive one at 282 nm. Changes in the concentration of of hydrogen peroxide in relation to iron ions was disadvantageous
carbamazepine under the inuence of the used reagents were from the perspective of carbamazepine degradation. Specically,
monitored measuring absorbance of the experimental solutions the more marked the presence of hydrogen peroxide, the slower
A. Karpinska et al. / Journal of Pharmaceutical and Biomedical Analysis 106 (2015) 4651 49
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 )
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.
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