Chemical Engineering Journal 220 (2013) 6–14

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Chemical Engineering Journal

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Degradation of bisphenol A by ozonation and determination of

degradation intermediates by gas chromatography–mass spectrometry
and liquid chromatography–mass spectrometry
Erdal Kusvuran ⇑, Deniz Yildirim
University of Cukurova, Faculty of Sciences and Letters, Department of Chemistry, 01330 Balcali, Adana, Turkey

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" The stoichiometric ratio between

ozone and BPA was calculated to be
10.30 at pH 3.0.
" Mineralization of the BPA solution is
not as successful as the oxidative
degradation.
" Ten oxidation products are identified
during BPA ozonation.
" Henry’s constant, kH, increased 5.5%
depending on growth of ionic
strength of BPA solution.

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

Article history: In this study, bisphenol A (BPA), an endocrine disrupter, was removed by ozonation process. During ozon-
Received 4 August 2012 olysis, degradation kinetics and degradation intermediates of BPA were determined and degradation stoi-
Received in revised form 12 December 2012 chiometry was also calculated. The degradation of BPA was found to be optimal at pH 3.0 and BPA
Accepted 19 January 2013
solution with 0.509 mM concentration was completely degraded after 25 min ozonation time. The stoi-
Available online 29 January 2013
chiometric ratio between ozone and BPA were calculated to be 10.30. The pseudo-first order degradation
rate constant, kObs, decreased in the range of 19.3–13.3 s1 when the initial concentration of BPA was
Keywords:
raised from 0.051 to 0.509 mM. In addition, the second order rate constant, kapp(BPA), was also calculated
Bisphenol A
Ozonation
in the range of 2.18  104–3.56  104 M1 s1. Henry’s constant, kH, increased as 5.5% depending on
LC–MS/MS growth of ionic strength of BPA solution during ozonation. As a result of the increase of kH, dissolved
GC–MS ozone reduced throughout the ozonation. Ten different intermediates occurred during the ozonation of
BPA and were identified via GC–MS and LC–MS/MS. Malonic and oxalic acids were observed among
0
the intermediates in the first 5 min of ozonation and taken as markers of mineralization. kTOC value
1 1
was calculated as 2.11 M min for BPA mineralization and the mineralization of ozonation was
achieved about 30% at the end of 25 min ozonation.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction since the polymerization of the para-hydroxyphenyl rings of BPA

2,2-Bis(4-hydroxyphenyl)propane (bisphenol A, BPA) is a dimer
of two para-hydroxyphenyls bonded through a methylene bridge
and indispensable monomer for the production of various poly-
meric materials such as polycarbonate, epoxy resins, polyacrylates
⇑ Corresponding author. Tel.: +90 322 551 20 57; fax: +90 322 551 22 55.
E-mail address: erdalkusvuran@yahoo.com (E. Kusvuran).
can be easily controlled. Hence, the production of BPA has been
found increasing market demand. For example, 7.6  108 and
5.6  107 kg of BPA are produced in the United States and China,
respectively per year [1]. Notwithstanding its high commercial va-
lue, it has been shown that BPA is an endocrine disruptor even at a
low concentration (1.0–10.0 mg L1) and can cause to detrimental
health problems on people such as carcinogenesis [2–5]. Therefore,
governments limited legally total BPA intake around 50 lg per

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.01.064
 E. Kusvuran, D. Yildirim / Chemical Engineering Journal 220 (2013) 6–14
kilogram of body weight per day [6]. It was reported that BPA was
detected in municipal wastewater on account of untreated indus-
trial wastewater and demonstrated that a low amount of BPA
was also very harmful for aquatic ecosystem [7].
A number of methodologies based on physical and chemical
treatment processes are currently continued to apply the removal
of BPA [8–14]. Advanced oxidation processes (AOPs) have been re-
garded as a new technology for the decomposition of several or-
ganic matters. These processes include ozonolysis [15–19],
Fenton [20], photocatalysis [21–23] and wet-air oxidation methods
[24]. Ozonation process is a faster and cheaper process than photo-
catalysis and wet-air oxidation, respectively and besides, no extra
chemicals are required like Fenton process. When considering
the overall factors, ozonation has provided the highly affirmative
results among the AOPs [25].
Recently, the degradation of BPA using ozonation has been de-
scribed by several researchers [26–30]. These studies presented
significant information about BPA-ozone stoichiometry and degra-
dation kinetic of BPA, however, none of them took into account of
Henry’s constant which is an important parameter affecting onto
solubility of ozone. Furthermore, a few studies were conducted
for analyzing the degradation intermediates of BPA using liquid
chromatography–mass spectrometry [31,32]. However, complete
chromatographic identification of degradation intermediates is of-
ten difficult and requires more chromatographic techniques to
identify degradation intermediates completely due to the probable
existence of overlapping or embedded peaks [33]. The combination
of gas chromatography–mass spectrometry and liquid chromatog-
raphy–mass spectrometry is a powerful technique for evidence of
degradation intermediates and provides an effective way for the
quantification and identification of intermediates. Therefore, this
study aimed to scrutinize degradation and mineralization pro-
cesses of BPA by ozone and its degradation intermediates by gas
chromatography–electrospray ionization mass spectrometry (GC–
EI–MS) and liquid chromatography–electrospray ionization tan-
dem mass spectrometry (LC–ESI–MS/MS).
2. Materials and methods
2.1. Materials
Bisphenol A (99%, BPA) was supplied from Riedel-de Haen AG
(Germany). Potassium iodide (KI), sodium thiosulfate (Na2S2O3)
and 1-(Trimethylsilyl) imidazole were purchased from Merck KgaA
(Darmstadt, Germany). Ozonation experiments were carried out by
using an Ozo-1VTT model ozone generator (Ozomax, Canada) com-
bined with pure oxygen gas (99.9%). The flow rate of oxygen gas
was adjusted with a flow meter settled on the tube. The ozone
gas flow rates and concentration of ozone gas used during all
experiment were 720 mL min1 and 0.239 mmol min1.
2.2. Ozonation experiments
The BPA solutions were prepared in the range of 0.051–0.509 mM
concentration using distilled water. The most concentrated BPA
solution was obtained by placing excess BPA into distilled water
(5.0 L) at pH 10.0 and the solution was stirred with a magnetic stirrer
for 1 h. Using this method, 2.0 g of BPA was successfully dissolved in
the water. The BPA solution was stirred on a magnetic stirrer for an
additional hour again after 1.0 M H3PO4 solution (0.5 L) was added.
The desired pHs of BPA solutions were adjusted by using concen-
trated NaOH and H2SO4 solution. These solutions were then filtered
through 0.1 lm filter paper and stored in a dark bottle at ambient
temperature (20 °C) until used for ozonation reactions. The amount
of BPA in this solution was detected by using a liquid chromatogra-
phy instrument equipped with UV detector (HPLC- UV, Thermo
7
Separation Products, Spectra System UV 2000) and a C18 intersil
ODS-3 column (4.6  150 mm) at 278 nm. The mobile phase was
methanol/water mixture (60/40, v/v) at a flow rate of 1.0 mL min1.
HPLC detection limit of BPA was calculated as 5.93 (Signal/Noise) for
0.5  102 mM BPA concentration. These experiments were repli-
cated three times.
Ozonation experiments were carried out with 0.5 L BPA solution
in a 1.0 L cylindrical glass reactor. BPA solutions were fed with
ozone gas by diffusing from the bottom of the reactor. Ozone traps
containing 0.5 L of KI solution (20 g L1) were connected at the out-
let of this reactor to capture the unreacted ozone. Excess ozone in
this traps were detected using an iodimetric method according to a
previously reported procedure [34,35]. In order to detect amount
of ozone produced during ozonation at a constant O2 gas velocity,
0.5 L of KI solution (pH 3.0) was measured into the reactor. The
content of trap and reactor was titrated with Na2S2O3
(0.010 mol L1). The consumed ozone by BPA was determined by
using the equation below:
O3Consumed ¼ O3Total  ðO3Trap þ O3Residual þ O3Headspace Þ ð1Þ
where Consumed O3 is the amount of ozone interacted with BPA
molecules, Total O3 is the ozone generated during an experiment
and Trap O3 is the ozone captured by the trap. The Residual O3
and Headspace O3 is the residual dissolved ozone and the amount
of ozone collected above the reaction mixture.
O3Residual and O3Headspace are very small when compared with O3-
Trap. Therefore, they can be neglected and the final equation can be
written as shown below:
O3Consumed ¼ O3Total  O3Trap ð2Þ
One milliliter samples were taken at 0, 1, 2, 3, 5, 7, 10, 15, 20
and 25 min for cumulative ozonation times and analyzed by HPLC
during ozonation of BPA. To determine the total organic carbon
content (TOC) of the BPA solutions, 10 mL of samples withdrawn
from the reaction mixture were analyzed by Tekmar Dohrmann
Apollo 9000 instrument for all BPA initial concentrations after
25 min ozonation time.
2.3. Gas chromatography–mass spectrometry (GC–EI–MS), liquid
chromatography (LC–UV) and liquid chromatography–mass
spectrometry (LC–ESI–MS/MS) analyses for the degradation products
of BPA
The intermediates occurred during ozonolysis of BPA were
determined by GC–EI–MS (Shimadzu, 2010) combined with a RES-
TEK Rtx-5MS (0.25 lm, 60 m  0.25 mm, 5% diphenyl-95% di-
methyl polysiloxane) column and an electron impact (EI)
detector (70 eV). The temperature program was an initial temper-
ature of 50 °C, held for 9 min, then increased at 5 °C min1 to
240 °C and held for 12 min. The temperatures of the ion source,
injection port and interface were 230, 260 and 250 °C, respectively.
To determine the degradation products of BPA, the ozone was
fed into the reaction mixture by diffusion after 0.5 L of BPA solu-
tion (0.509 mM in pH 3.0 phosphate buffer) was measured into
the reactor. After the BPA solution was ozonized for 5 min,
250 mL of this solution was withdrawn into a separation funnel.
Subsequently, 2 mL saturated NaCl solution was pipetted and
75 mL diethyl ether was measured into the funnel before the solu-
tion was vigorously shaken. Addition of diethyl ether was repeated
two more times and organic phases were combined in Erlenmeyer
flask. The contents of Erlenmeyer flask were concentrated to 5 mL
after drying with solid anhydrous Na2SO4. Fifty microliters of n-
trimethylsilylimidazole (Supelco) was used for silylation of the
product of BPA ozonized and analyzed by GC–EI–MS. The same
procedure was applied for characterizing the intermediates of the
ozonation reaction at the other times (10, 15, 20 and 25 min).
8 E. Kusvuran, D. Yildirim / Chemical Engineering Journal 220 (2013) 6–14

The degradation products of BPA were also analyzed using LC–
UV and LC–ESI–MS/MS. LC–UV analyses performed on an ODS-3
C18 column (4.6  150 mm) at 278 nm. The mobile phase was
methanol/water mixture (60/40, v/v) at a flow rate of
1.0 mL min1. LC–MS analyses achieved with a triple quadrupole
instrument using electro spray ionization mode (Thermo Scientific,
TSQ Quantum Access Hyper Quads Model). The column was a
Hypersil gold C18 column (2.1  50 mm) packed with 1 lm spher-
ical particles. The mobile phase was methanol/water mixture (60/
40, v/v) at a flow rate of 0.250 mL min1.
During this process, the small amount of ozone bubbles dissolves
in solution while the big ones leave from reaction mixture. As a re-
sult, in basic pH, dissolved ozone produces no much more OH rad-
icals compare with in molecular ozone in acidic pH. It was reported
that ozone molecules consumed by decomposition reactions in ba-
sic solution [38,39]. Moreover, because OH radicals are non-selec-
tive, they can be consumed with other OH radical to yield
hydrogen peroxide and further self decomposition reactions may
be occurred. The degradation pH of BPA was therefore determined
to be 3.0 and all further experiments were conducted at this pH.

3. Results and discussion 3.2. Ozone-BPA stoichiometry

3.1. The effect of pH on ozonolytic degradation
The ozonation experiments were carried out with 0.509 mM
BPA solution in phosphate buffer at pH values of 3.0, 7.0, and
10.0 for 25 min ozonation time. Degradation of BPA at the neutral
and alkali pH conditions was determined as 87.0% and 94.0%,
respectively, but 99.5% decomposition was obtained at pH 3.0
(Fig. 1).
The effect of pH on the reaction between ozone and substrate is
well known. The reaction of organics with ozone is directed in two
ways by pH. One of them is direct attack or electrophilic attack (at
acidic pH) and the other is mainly free radical attack (at basic pH)
[36]. Moreover, the amount of ozone reacted with organics is lim-
ited by dissolved ozone in the reaction mixture. If the reaction be-
tween dissolved ozone and organics carried out in an instant of
time zone is assumed a cycle, the number of cycle will increase
depending on initial organic concentration. In a cycle, dissolving
ozone in reaction mixture and reaching equilibrium will need time
[37]. The gas form of ozone firstly inputs bottom in reaction med-
ium, then it bubbles from bottom to up in the reaction mixture.
In this section, the stoichiometric relationship between ozone
and BPA was examined for degradation of each initial BPA concen-
tration and the obtained results were demonstrated in Table 1 and
Fig. 2. When the decomposition percentage was achieved over 99,
the ozone consumption was calculated via Eq. (1). The longest
ozonation time was detected as 25 min from Fig. 1. After this time,
ozone consumed by 0.509 mM initial BPA concentration was calcu-
lated as 54% of total ozone (5.982 mmol) produced. The shortest
ozonation time was observed as 10 min for 0.051 mM BPA initial
concentration. The ozone consumed by BPA at this concentration
was calculated as 14.9% of the total ozone (2.393 mmol). The stoi-
chiometric ratio between ozone-BPA was, therefore, calculated to
be 10.30 from Fig. 2. Garoma and Matsumoto [30] reported that
the stoichiometric ratio of ozone to BPA varied in the range of
7.0–9.5 in the ozonation time range of 20–30 min. Therefore, the
ozone-BPA reaction can be written as:
BPA þ 10:3O3 ! OP
where OP is the oxidation products.
3.3. The degradation products of BPA during ozonation process

The formed intermediates during ozonation of BPA were silylat-

0.6 ed to derivatize the non-volatile organics and then identified via
GC–MS. The results are demonstrated in Fig. 3 and Table 2. Fig. 3
0.5 shows the total ion chromatogram (TIC) belonging to BPA
(0.509 mM) treated with ozone for 5 min. In this chromatogram,
pH=3.0 nine peaks were identified.
0.4
pH=7.0 The decrease of BPA concentration in solution was followed by
[BPA] (mM)

pH=10.0 LC–UV at 278 nm (Fig. 4). Seven peaks belonging to intermediates

0.3
of the degradation of BPA were detected in the HPLC chromato-
gram after 5 min ozonation time for 0.509 mM initial concentra-
0.2 tion. However, in the ozonation time of 25 min, the three peaks
with retention times (tR) 6.32, 4.49 and 3.92 min disappeared
0.1 and a new peak was observed at tR 2.66 min. In addition, the peak
for BPA (tR 13.05 min) was disappeared completely after this time
(Fig. 5).
0.0
0 5 10 15 20 25 The identification of two more degradation products (PN10 and
PN11) which was not observed by GC–EI–MS was achieved with
t (min) LC–ESI–MS/MS (Table 2). The possible higher compounds, such as
primary oxidation products (PN10 and PN11) mentioned in
Fig. 1. Ozonolytic degradation of BPA at various pH values ([BPA]0 = 0.509 mM).
Fig. 6, were not observed by GC–EI–MS analysis since they were

Table 1
The amount of consumed ozone by BPA molecules during ozonolysis experiments for different initial BPA concentrations, titrated volume of KI trap contents and titrant volume.

Initial [BPA] (mmol) Ozonation time (min) Volume (mL) (trap content) Titranta vol. 0.010 M Na2S2O3 Excess O3 in trap (mmol) Consumed O3 by BPA (mmol)
0.509 25 25 551.40 2.757 3.225
0.381 25 32 726.56 3.633 2.349
0.254 20 37 635.14 3.176 1.610
0.127 15 42 547.62 2.738 0.851
0.051 10 43 406.98 2.035 0.358
a
The trap contents titrated by 0.010 M Na2S2O3 were normalized to a reaction volume of 0.5 L.
 E. Kusvuran, D. Yildirim / Chemical Engineering Journal 220 (2013) 6–14 9

5 degradation times of BPA were inversely proportional to the initial

concentration of BPA. During the oxidative degradation of BPA for
the 0.051 mM initial concentration, the peak of BPA in the HPLC
4 nO =10.30n[BPA]
3 chromatogram disappeared at the end of the 7 min ozonation
2
r =0.999 whereas the degradations of BPA for 0.127, 0.254, 0.381 and
nO (mmol)

3
0.509 mM initial concentrations were >99.9%, 90.2%, 84.5%, 77.4%
and 71.9%, respectively.
As mentioned before, the ozone first attacks BPA for addition
3

2 and cleavage of the double bonds to produce various intermediates

then also began to react with these degradation intermediates con-
taining double bonds in their chemical structures (Table 2). There-
1 fore, the reaction kinetic between BPA and ozone can be written as
given in the following equation:
0 d½BPAT
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35  ¼ ½O3 ðk1 ½BPA þ k2 ½BPA  þ k3 ½BPA2  ð3Þ
dt
n[BPA] (mmol)
where [BPA]T is the total BPA concentration including neutral and
anionic species of BPA and [BPA]T can be written as:
Fig. 2. Stoichiometric relationship between ozone and BPA.

½BPAT ¼ ½BPA þ ½BPA  þ ½BPA2  ð4Þ

either non-volatile or thermally unstable. As a result of combining
the evaluation of GC–EI–MS and LC–ESI–MS/MS results, a degrada-
tion mechanism was proposed for ozone-BPA reaction and pre-
sented in Fig. 7.
The reaction of molecular ozone with carbon–carbon double
bonds yields the ozonides formed via addition of ozone in double
bond. Ozonides are well known unstable intermediates and de-
graded rapidly to carbonyl groups [40]. During the ozonation of
BPA, malonic acid and oxalic acid was observed in the first 5 min.
The presence of these acids showed that the mineralization of
the intermediates began simultaneously with the start of ozona-
tion of BPA. Unlike oxalic acid, malonic acid then disappeared on
TIC after 5 min ozonation. The malonic acid was assumed to have
been consumed by other intermediates since its degradation by
ozone is not favored over degradation of BPA or intermediates con-
taining carbon–carbon double bonds. Additionally, PN4 disap-
peared after 5 min of ozonation treatment, the same as for
malonic acid. The areas of PN3, 6, 7, and 9 were observed to de-
crease with increases in ozonation time, although the area of
PN5 remained at the same level. The area of PN8 increased until
up to 15 min, then decreased between 15 min and 20 min and in-
creased again at 25 min.
3.4. Kinetics of BPA ozonation
The effect of initial BPA concentrations on the ozonolytic degra-
dation of BPA was investigated in the BPA concentration range
from 0.051 to 0.509 mM at pH 3.0. Fig. 8 shows the degradation
of BPA at various initial concentrations. According to Fig. 8, the
 2
At pH 3.0, the concentrations of [BPA ] and [BPA ] species can
be omitted (Ka1 2.5  1010 and Ka2 6.3  1011 for BPA) and
[BPA]T = [BPA], hence, Eq. (3) can be simply written as:
d½BPA
 ¼ k½BPA½O3  ð5Þ
dt
where k is the rate constant of BPA-ozone reaction and [O3] is the
ozone concentration.
On the other hand, the O3 concentration consumed in the liquid
phase is determined using Eq. (2).
½O3Consumed  ¼ ½O3Total   ½O3Trap 
Since only dissolved ozone in reaction mixture reacted with
BPA, the effective ozone concentration in a liquid phase depended
on partial pressure and the Henry constant. Accordingly, dissolved
ozone could be calculated as shown in the following equation:
P
½O3 L ¼ ð6Þ
kH
where [O3]L is concentration of ozone in liquid phase, P is the partial
pressure of ozone and kH is the Henry constant of ozone. For ozone,
the Henry’s constant varies depending on temperature, ionic
strength and pH in a solution [41–43]. When the temperature and
pH held constant for a reaction media, its ionic strength becomes
a dominant factor which affects on ozone solubility. During ozona-
tion of diluted solution, ionic strength occurred with degradation of
substrate may be ignored if substrate concentration is prepared le-
vel of milimolar [44]. Finally, Eq. (7) is obtained when Eq. (6) is
written into a second order kinetic equation.

Fig. 3. The GC–EI–MS total ion chromatogram for 0.509 mM BPA concentration treated with ozone for 5 min.
10 E. Kusvuran, D. Yildirim / Chemical Engineering Journal 220 (2013) 6–14

Table 2
Organic intermediates identified by GC–EI–MS and LC–EIS–MS/MS.

Peak no. Name Open structure

1 Oxalic acid O
OH
HO
O
2 Malonic acid HO OH

O O
3 1,2-Dihydroxy benzene OH
OH

4 2-(p-Hydroxyphenyl)-2-propanol OH

HO
5 4-Hydroxy-benzoic acid O

OH

HO
6 1,4-Dihydroxy benzene OH

HO
7 Trihydroxybenzene OH
HO

OH
8 4-(p-Hydroxy phenyl),4,4-dimethyl,1-buten-3-on O
HO

9 BPA
HO OH

10 4-(2-(4-Hydroxy phenyl)propan-2yl)cyclohexa-3,5-diene-1,2-dione

11 (2E,4Z)-3-(2-(4-Hydroxyphenyl)propan-2-yl)hexa-2,4-dienedioic acid

 
d½BPA P where kObs is the observed pseudo-first order rate constant, and can
 ¼ k½BPA ð7Þ
dt kH be calculated from the slope of the plot of ln([BPA]/[BPA]0) versus
time. Plots of the linear form of the pseudo-first order kinetic model
When P and kH are assumed as constant under the experimental are given in Fig. 8. For initial BPA concentrations of 0.051–
conditions, the final kinetic equation can then be arranged as 0.509 mM, the first order rate constants were in the range from
shown in Eq. (7). 13.3 to 19.3 s1. These results revealed that the first-order model
gave a good fit and the coefficient of determination was determined
d½BPA
 ¼ kObs ½BPA ð8Þ to be between 0.991 and 0.999. As confirmation, Garoma et al. [30]
dt also reported that they observed linearism between ln([BPA]/
[BPA]0) and time. In addition, it was noted that kobs was inversely
P
kObs ¼ k ð9Þ proportion to the initial concentrations of BPA. Furthermore, when
kH
the initial concentration of BPA increased from 0.051 to 0.509 mM,
 E. Kusvuran, D. Yildirim / Chemical Engineering Journal 220 (2013) 6–14 11

Fig. 4. HPLC chromatogram of the solution of BPA for first 8 min ozonation ([BPA]0 = 0.509 mM).

PN7 PN8 kobs decreased from 19.3 to 13.3 s1. Partial pressure of ozone in
PN6 PN1
reaction media may be assumed as a constant because ozone is
PN2 PN5
0.5 PN3 PN9 fed continuously and k is already a constant. In this case, kH may
PN4 decrease depending on increase of ionic strength. Therefore, an in-
Concentration (mM)

versely proportional relationship was observed between first-order

0.4
rate constant and BPA concentration in this study.
On the other hand, BPA-ozone degradation rate can be calcu-
0.3
lated using the following equation:
½BPAT;0 kappðBPAÞ ½PhenolT;0
0.2 ln ¼ ln ð10Þ
½BPA kappðPhenolÞ ½Phenol
0.1 As simply indicated in Eq. (4) ([BPA]T = [BPA]), kapp(BPA) value in
Eq. (10) can be rewritten as:
0.0
k ¼ kappðBPAÞ
0 5 10 15 20 25

Time (min) Finally, when k value is replaced in Eq. (9) and the equation is
rearranged, Eq. (11) is obtained,
Fig. 5. The concentration variation of BPA and intermediates during ozonation.

Fig. 6. The LC–ESI–MS/MS total ion chromatogram for 0.509 mM BPA concentration at the end of 5 min ozonation to identify PN10 and PN11.
12 E. Kusvuran, D. Yildirim / Chemical Engineering Journal 220 (2013) 6–14

Fig. 7. Proposed degradation mechanism for BPA.

kObs P value of 5.46  104 M represented the P/kH ratio when the con-
¼ ð11Þ
kappðBPAÞ kH
kapp(BPA) represents the rate constant of the reaction between molec-
ular ozone and molecular BPA. kapp(BPA) value was calculated in the
range of 2.18  104–3.56  104 M1 s1 via Fig. 9. Lee and Gunten
[16] reported that the second order rate constant of BPA was
2.4  104 M1 s1 by using quantitative structure-activity relation-
ship model.
The kObs/kapp(BPA) ratios for each BPA concentration were ob-
served as 5.42  104, 5.39  104, 5.33  104, 5.26  104 and
5.18  104 M, respectively. When P/kH ratios were plotted versus
BPA concentrations (Fig. 10), a straight line with a slope value of
0.05 and an intercept value of 5.46  104 M was observed. The
centration of [BPA] = 0 mM. This value also belonged to ionic
strength of the buffer solution in the absence of BPA and indicated
that there was no ionic strength to be derived from BPA. When
[BPA] = 0 and [BPA] = 0.509 mM, the corresponding kH (atm M1)
values were calculated as 1.83  103 P and 1.93  103 P indicating
that kH value increased 5.5% with concentration increase. This find-
ing can be explained due to increasing of the ionic strength of solu-
tion during BPA ozonation. Andreozzi et al. [41] investigated the
relationship between Henry’s constant and ionic strength and they
reported that Henry’s constant was a proportional to ionic
strength. Depending on the increment of Henry constant, the solu-
bility of ozone reduced and this caused the change of first order
and second order rate constants.
 E. Kusvuran, D. Yildirim / Chemical Engineering Journal 220 (2013) 6–14 13

-ln ([BPA] / [BPA]0)

4 -0.30
0,5
0.5 Y = 2.11X-0.63
3

ln (CTOC25/CTOC0)
2
2 r =0.998
0,4
0.4 1
-0.35
[BPA]0 (mM)

0
0 5 10 15 20 25
0.3
0,3 t (min)

[BPA]0=0.509 mM
0,2
0.2 [BPA]0=0.381 mM -0.40
[BPA]0=0.254 mM
[BPA]0=0.127 mM
0,1
0.1
[BPA]0=0.051 mM
-0.45
0.10 0.12 0.14 0.16
0 5 10 15 20 25
25.CO3 (M.min)
t (min)
0
Fig. 11. Plot of lnðC TOC 25 =C TOC0 Þ versus tCo3 to determine kTOC value (t = 25 min).
Fig. 8. Degradation of BPA in solutions of various initial concentrations by
ozonation (pH 3.0) and the linear transform ln([BPA]/[BPA]0) versus time.

3.5. Mineralization of BPA

The mineralization of BPA was measured using TOC analyzer.

8 kapp(BPA) = 1.67.kapp(Phenol) After 25 min ozonation time, TOC value reduced about 30% while
kapp(BPA) = 1.93.kapp(Phenol) initial BPA concentration was completely depleted at the end of
7 kapp(BPA) = 2.23.kapp(Phenol) 25 min. This finding shows that the reaction medium contains sat-
kapp(BPA) = 2.59.kapp(Phenol) urated organic compounds such as carboxylic acids. The minerali-
6
ln ( [BPA]T,0/ [BPA] )

kapp(BPA) = 2.74.kapp(Phenol) zation of BPA was also estimated from the equation according to
Rivas et al. [29].
5
dCTOC COH
 ¼ kTOC 1 CTOC aCO3 ; a¼ ð12Þ
4 dt CO3

3
dCTOC 0
 ¼ kTOC CO3 dt ð13Þ
2 CTOC
When this equation was integrated, Eq. (14) was obtained.
1
Z CTOC t Z t
0 CTOC t 0
0  lnðCTOC Þ ¼ kTOC CO3 dt ¼  ln ¼ kTOC CO3 t ð14Þ
CTOC 0 CTOC 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0

When the ozonation time was taken a constant for 25 min and
ln ( [Phenol]T,0/ [Phenol] )
lnðC TOC25 =C TOC 0 Þ values were plotted versus tCo3, Fig. 11 was ob-
0
tained. kTOC value was calculated as 2.11 M1 min1 from slope of
Fig. 9. Linear transform of ln([BPA]T,0/[BPA]) versus ln([Phenol]T,0/[Phenol]) to
determine kapp(BPA)/kapp(Phenol) ratio at different initial [BPA] concentration levels. plot. Table 3 also shows the experimental and calculated TOC re-
moval values for different initial BPA concentrations after 25 min
ozonation. As shown in Table 3, the calculated and experimental
TOC values were almost similar for 0.509 mM BPA concentration.
However, % relative error increased when the initial BPA concen-
6
tration was decreased.

5
4. Conclusion

4 p/kH=-0.05 [BPA)]+5.46
In this study, the optimum decomposition pH was determined
as 3.0 for BPA ozonation and the stoichiometric ratio between
4

2
P/kHx10

3 r =0.99 ozone and BPA was calculated to be 10.30 at this pH. Ten different
intermediates formed during ozonation of BPA were identified by
GC–MS and LC–MS/MS. The presence of malonic and oxalic acids
2
after an ozonation time of 5 min demonstrated that the minerali-
zation of intermediates began simultaneously with the ozonation
1 of BPA. The first-order rate constants were calculated in the range
of 19.3–13.3 s1. Similarly, the value of the second order rate con-
0 stant determined in a range of 2.18  104–3.56  104 M1 s1.
0 1 2 3 4 5 When BPA concentration was raised from 0 to 0.509 mM, Henry’s
4 constant, kH, increased 5.5% depending on growth of ionic strength
[BPA]x10
of BPA solution during ozonation. In this study, mineralization of
Fig. 10. The change of P/kH ratios towards initial BPA concentrations. BPA solution was not as successful as degradation of BPA for
14 E. Kusvuran, D. Yildirim / Chemical Engineering Journal 220 (2013) 6–14
Table 3
The experimental and calculated TOC25/TOC0 values of BPA for different initial BPA concentrations.
Initial BPA Consumed O3 by BPA TOC0 TOC25
(mmol L1) (mmol L1) (mg L1) (mg L1)
0.509 0.161 91.4 68.8
0.381 0.117 68.6 47.7
0.254 0.110 45.0 30.3
0.127 0.103 22.9 15.1
0.051 0.095 9.2 6.0
0
ozonation times up to 25 min. kTOC value was estimated as
2.11 M1 min1. At the end of 25 min ozonation time, all BPA mol-
ecules were completely degraded, while BPA were mineralized
only about 30%.
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