Chlorination of bisphenol A in aqueous media: Formation of chlorinated bisphenol A congeners and degradation to chlorinated phenolic compounds

Article abstract of DOI:10.1016/S0045-6535(01)00198-9

Bisphenol A (BPA) chlorination in aqueous media was studied to describe the degradation profile of this compound and the formation of chlorinated products. Chlorinated compounds were extracted with dichloromethane and determined by GC/MS. BPA still remain

Full text of DOI:10.1016/S0045-6535(01)00198-9

Chemosphere 46 (2002) 1215–1223
www.elsevier.com/locate/chemosphere
Chlorination of bisphenol A in aqueous media: formation
of chlorinated bisphenol A congeners and degradation
to chlorinated phenolic compounds
*
Takashi Yamamoto , Akio Yasuhara
Regional Environment Division, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-0053, Japan
Received 11 December 2000; received in revised form 31 August 2001; accepted 18 September 2001
Abstract
The chlorination of bisphenol A (BPA) in aqueous media was investigated in order to describe the degradation
profile of this compound and the formation of chlorinated products. Aqueous solutions of BPA (approx. 1 mg/l) were
chlorinated by sodium hypochlorite solution at room temperature and under weakly alkaline conditions. Chlorinated
compounds were extracted with dichloromethane and determined by gas chromatography/mass spectrometry (GC/
MS). BPA was consumed completely within 5 min of chlorination, when the initial chlorine concentration was 10.24
mg/l (molar ratio to BPA, 58.7). On the other hand, when the initial chlorine concentration was 1.03 mg/l (molar ratio,
6.56), 9.3% of BPA still remained after 60 min chlorination. Five chlorinated BPA congeners, 2-chlorobisphenol A
(MCBPA), 2; 6-dichlorobisphenol A (2; 6-D2CBPA), 2; 20-dichlorobisphenol A (2; 20-D2CBPA), 2; 20,6-trichlorobis-
phenol A (T3CBPA) and 2; 20; 6; 60-tetrachlorobisphenol A (T4CBPA) were formed in the earlier stages of chlorination.
Several chlorinated phenolic compounds, 2; 4; 6-trichlorophenol (T3CP), 2; 6-dichloro-1; 4-benzoquinone (D2CBQ),
2; 6-dichloro-1; 4-hydroquinone (D2CHQ), C9H10Cl2O2, C9H8Cl2O and C10H12Cl2O2, were also formed by further
chlorination. Ó 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Bisphenol A; Chlorination; Chlorinated bisphenol A congeners
1. Introduction
estimate human exposure and environmental concen-
trations of the compound. BPA migrates at ppb levels
from polycarbonate products (Krishnan et al., 1993) or
the epoxy coating on cans (Brotons et al., 1995) to water
during thermal processes. BPA also migrates from PVC
hoses to water at room temperature and at neutral pH
(Yamamoto and Yasuhara, 2000). Concentrations of
BPA of 4.0–1730 lg=l were found in water after exposure
to PVC hoses for 24 h. Moreover, water that had only
passed through a PVC hose was contaminated with BPA
at ppb levels. These plastic-to-water migrations are
thought to be a significant source of human exposure.
BPA that has migrated from plastics to tap water may
react with residual chlorine in the tap water that had been
added as a disinfectant. As far as the environmental oc-
currence of BPA is concerned, hazardous waste landfill
Bisphenol A (BPA) is used in the manufacture of
polycarbonate and epoxy resins. It is also used as stabi-
lizer or antioxidant for many types of plastics such as
polyvinyl chloride (PVC) (Ash and Ash, 1995). Annual
production of this compound in Japan was about
250,000 tons in 1996 (Ministry of International Trade
and Industry of Japan, 1997). Since the recent recogni-
tion that BPA possesses weak estrogenic properties
(Krishnan et al., 1993), many studies have been done to
* Corresponding author. Tel.: +81-298-50-2547; fax: +81-
298-50-2570.
E-mail address: tyama@nies.go.jp (T. Yamamoto).
0045-6535/02/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S0045-6535(01)00198-9

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T. Yamamoto, A. Yasuhara / Chemosphere 46 (2002) 1215–1223
site leachates (Yasuhara et al., 1997, 1999; Yamada et al.,
1999; Yamamoto et al., 2000) or sewage treatment plant
effluents (Lee and Peart, 2000) are thought to be signifi-
cant sources. Several landfill leachates were found to be
contaminated by BPA at ppm levels and effluents from
these landfills were still contaminated at ppb levels. Some
of these landfill sites and sewage treatment plants have
chlorinating disinfection facilities and landfill leachates
or sewage effluents are chlorinated before being dis-
charged. Although human exposure to, and environ-
mental contamination with, BPA are closely related to
chlorination processes, the chlorination reactions of BPA
in aqueous media are not well described. Therefore, we
carried out experiments on the chlorination of BPA in
aqueous media to investigate the products of BPA
chlorination and their degradation profiles.
and from Tokyo Chemicals (Japan). BPA-d16 was of
environmental analytical grade (Wako). Dichlorome-
thane, acetone, sodium chloride, and anhydrous sodium
sulfate were of pesticide analysis grade (Wako). Hydro-
chloric acid and sodium thiosulfate were of reagent
grade (Wako). Sodium hypochlorite solution (5% avail-
able chlorine) was purchased from Kanto Chemicals
(Japan). Purified water used in experiments was made by
a MilliQ water purification system (Waters, US). The
BPA spike solution was prepared by dissolving 50 mg of
BPA in 50 ml of acetone. The surrogate compound solu-
tion was prepared by dissolution of BPA-d16 in acetone.
For preparing stock solutions for calibration, 50 mg each
of BPA, T4CBPA and T3CP were dissolved in 50 ml of
acetone. A series of calibration solutions (0.001–10 ng=ll
for each compound) was prepared by dilution of the
stock solution with acetone followed by spiking of the
surrogate solution. Sodium hypochlorite solution was
diluted with purified water before being used and avail-
able chlorine was determined by iodometric titration.
2. Experimental
2.1. Materials and reagents
2.2. Chlorination procedure of BPA
BPA was purchased from Wako Pure Chemicals
(Japan). 2; 4; 6-Trichlorophenol (T3CP), 2; 20; 6; 60-tetra-
chlorobisphenol A (T4CBPA) were of technical grade
The acetone solution of BPA (500 ll) was placed in a
glass bottle which was then heated to evaporate the
Table 1
Levels of BPA and chlorination products from various chlorination conditions
Initial Cla Reaction time
BPA
T4CBPA T3CP
2-Mb
(lmol/l) (lmol/l) (lmol/l)
2; 6-D2
2; 20-D2
2; 20; 6-T3
(lmol/l)
b
b
b
Residual Cl
(mg/l)
(min)
(mg/l)
(lmol/l) (lmol/l) (lmol/l)
(lmol/l)
1.03 (29.2)
0
5
–
4.45
2.97
1.26
1.28
0.41
N.D.c
0.01
0.11
0.20
0.31
N.D.
0.005
0.008
0.014
0.021
N.D.
0.94
0.98
1.02
0.56
N.D.
0.19
0.39
0.44
0.27
N.D.
0.22
0.31
0.33
0.18
N.D.
0.10
0.36
0.70
0.62
0.61
0.43
0.31
0.13
17.2
12.1
15
30
60
8.74
3.77
2.07 (58.3)
5.12(144)
0
5
–
4.45
05.620.2 0.008
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
1.18
0.80
0.58
0.22
33.3
0.83
0.41
0.65
0.53
15
30
60
22.6
16.4
0.070
0.009
N.D.
1.38
1.70
0.74
0.015
0.024
0.062
0.16
0.03
N.D.
0.12
0.02
N.D.
1.02
0.61
0.08
1.16
0.82
0.07
6.21
0
–
4.91
N.D.
0.98
1.67
1.04
0.60
N.D.
0.014
0.039
0.11
N.D.
0.17
0.06
0.03
N.D.
0.11
0.07
0.04
N.D.
0.39
0.05
0.06
N.D.
0.54
0.13
0.10
5
2.93
2.60
2.04
1.61
82.7
73.3
57.5
45.5
0.064
0.005
N.D.
N.D.
15
30
60
0.093
0.020.02 0.02 0.04
10.24
(289)
0
5
–
4.91
N.D.
0.73
0.70
0.47
0.25
N.D.
0.022
0.029
0.037
0.040
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
0.04
N.D.
0.13
0.02
7.90
7.38
7.23
5.99
223
N.D.
N.D.
N.D.
N.D.
15
30
60
208
204
169
N.D.
N.D.
N.D.
N.D.
N.D.
BPA ¼ bisphenol A; T4CBPA ¼ 2; 20; 6; 60-tetrachlorobisphenol A; T3CP ¼ 2; 4; 6-trichlorophenol; 2-M ¼ 2-chlorobisphenol A;
2; 6-D2 ¼ 2; 6-dichlorobisphenol A; 2; 20-D2 ¼ 2; 20-dichlorobisphenol A; 2; 20; 6-T3 ¼ 2; 20; 6-trichlorobisphenol A.
a Molar concentrations (lmol/l) are shown in parentheses.
b These congeners are tentatively determined using calibration curves for BPA and T4CBPA.
c N.D.: non detectable; detection limits were 0.002 lmol/l for BPA, 0.005 lmol/l for T4CBPA, 0.002 lmol/l for T3CP.

T. Yamamoto, A. Yasuhara / Chemosphere 46 (2002) 1215–1223
1217
solvent. The bottle was then charged with 500 ml of
purified water and allowed to stand for some time to
dissolve the BPA (1 lg of BPA per ml water). A pre-
determined amount of sodium hypochlorite solution
was then added to the aqueous BPA solution. Initial
concentrations of available chlorine and BPA and the
reaction times are listed in Table 1. The reaction tem-
peratures and pHs of the solutions were not especially
adjusted, but they ranged from 20 to 25 °C and from 8
to 9, respectively. For the duration of the reaction, the
bottle was placed in the dark. After predetermined re-
action time, a portion of the chlorinated sample was
taken for residual chlorine determination (iodometric
titration which was quenched by addition of 0.1 mol/l
sodium thiosulfate solution).
different reaction times. The levels of BPA, T4CBPA and
T3CP are listed in Table 1. Other chlorination products
were not determined because of the lack of standard
samples. BPA reacted rapidly in highly chlorinated
water. When the initial chlorine concentration was 10.24
mg/l (289 lmol=l, molar ratio to BPA 58.7), BPA dis-
appeared completely within 5 min. When the initial
chlorine concentration was 5.12mg/l (144 lmol=l, molar
ratio 29.3), only 1.3% of BPA remained after 5 min and
it was not detected after more than 30 min chlorination.
In the case of an initial chlorine concentration of 1.03
mg/l (29:2 lmol=l, molar ratio to BPA 6.56), 9.3% of
BPA still remained after a reaction time of 60 min. As
for the concentrations of the typical chlorination prod-
uct T4CBPA that was formed; the dependence on reac-
tion time was quite different at low and high chlorine
levels. When the initial chlorine concentration was 10.24
mg/l, the amount T4CBPA formed decreased with re-
action time. On the other hand, when the initial chlorine
concentration was 1.03 mg/l, T4CBPA steadily increased
with reaction time. When the initial chlorine concen-
tration was 2.07 and 5.12 mg/l, the T4CBPA concen-
tration was maximized at 30 and 15 min, respectively.
These results suggest that when the initial chlorine
concentration is not enough for the amount of BPA,
chlorine will be consumed by the formation of chlori-
nated BPA congeners and chlorination will stop there.
When the initial chlorine concentration was 1.03 mg/l,
consumption of chlorine in a reaction time of 5 min was
0.42mg/l (11 :9 lmol=l, molar ratio 2.67). Since the
molar ratio of consumed chlorine to the initial amount
of BPA was below 4, only a small quantity of T4CBPA
was formed. On the other hand, chlorine consumption in
a reaction time of 5 min was 2.34 mg/l (66:0 lmol=l,
molar ratio 13.5), when the initial chlorine concentration
was 10.24 mg/l. In this case, when the molar ratio was
larger than 4, further chlorination occurred with decom-
position of T4CBPA. The yields of T3CP were very small
(less than 1% of the initial BPA) through the all experi-
mental conditions. There are two possible reason to ex-
plain these results; (i) the reaction path for formation of
T3CP is minor compared with the other degradation
2.3. Analysis of BPA and chlorination products
Chlorinated samples (400 ml) were transferred to a
separatory funnel. 8 g of sodium chloride were added
and completely dissolved. They were then fortified with
the surrogate compound solution (1 lg of BPA-d16), and
acidified with 1 mol/l of hydrochloric acid. The sample
was extracted twice with 50 ml of dichloromethane by
shaking for 5 min. The combined extracts were dried
over with anhydrous sodium sulfate, evaporated to ap-
prox. 5 ml with a rotary evaporator, transferred to a test
tube and concentrated to 1 ml under a flow of nitrogen.
Each concentrated extract was analyzed by gas chro-
matography/mass spectrometry (GC/MS) {model 5890II
plus (Hewlett Packard, US) GC equipped with a splitless
injector (260 °C) and a PTE-5 capillary column (30 m Â
0:25 mm i.d., 0:25 lm film thickness, Supelco, US)}.
Injection volume was 1 ll. Helium was used as the
carrier gas with a flow rate of 1 ml/min. The initial
column temperature was 60 °C and was raised to 280 °C
at a rate of 10 °C/min and then held for 2min. For
quantitative analysis, a model 5972MSD mass spectro-
meter (Hewlett Packard, US) was operated in selected
ion monitoring (SIM) mode. Ionization was by electron
ionization (70 eV). The ionization chamber temperature
was maintained at 180 °C. Mass numbers of monitored
ions were m/z 213 for BPA, 351 for T4CBPA, 196 for
T3CP and 224 for BPA-d16. Dwell time was 50 ms for
each channel. For qualitative analysis, the mass spec-
trometer was operated in scan mode and the scan range
was from m/z 25 to 500. Scan rate was 1.4 scan/s.
3. Results and discussion
3.1. Degradation of BPA under several different chlori-
nation conditions
Chlorination experiments were carried out with var-
ious initial concentrations of available chlorine and for
Fig. 1. Total ion chromatogram of chlorinated BPA congeners
(initial chlorine concentration 5.12mg/l, reaction time 5 min).

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T. Yamamoto, A. Yasuhara / Chemosphere 46 (2002) 1215–1223
pathways for T4CBPA, or (ii) the degradation rate of
T3CP is faster than that of its formation. We cannot on
these data decide between these explanations.
numbers of the molecular ions ðMþÞ of peaks #2to #5
are 262, 296, 296, 330, respectively. Considering these
stepwise increases in mass number and the isomer pat-
tern of Mþ, these peaks may be interpreted as chlori-
nated BPA congeners. Since the chlorination of phenol
in aqueous media usually starts at the ortho- or para-
position (Burttschell et al., 1959; Onodera et al., 1984),
peak #2may be interpreted as ortho-chlorinated isomer,
2-chlorobisphenol A (MCBPA). In the case of dichlo-
robisphenol A (D2CBPA), two isomers, 2; 20-D2CBPA
and 2; 6-D2CBPA may be present. These two isomers
can be distinguished by specific fragment ions that de-
pend on their structure. The mass spectrum of BPA has
a fragment ion at m/z 119. This fragment ion is assigned
to C8H7Oþ (4-hydroxystyrene radical) formed by
3.2. Formation of chlorinated BPA congeners
Several compounds were formed in the earlier stages
of the chlorination reaction. The total ion chromato-
gram of an extract of the chlorinated sample is presented
in Fig. 1. Mass spectra of these peaks are shown in Fig.
2. Peak #1 in Fig. 1 may be interpreted as BPA by
comparing of its mass spectrum with one of authentic
material; peak #6 may be interpreted as T4CBPA by its
chromatographic retention time. Mass spectra of peaks
#2to #5 are very similar to that of BPA The mass
Fig. 2. Mass spectra of chlorinated BPA congeners. (a) BPA (peak #1 in Fig. 1), (b) 2-MCBPA (peak #2), (c) 2; 20-D2CBPA (peak #3),
(d) 2; 6-D2CBPA (peak #4), (e) 2; 20; 6-T3CBPA (peak #5), (f) 2; 20; 6; 60-T4CBPA (peak #6).

T. Yamamoto, A. Yasuhara / Chemosphere 46 (2002) 1215–1223
1219
Fig. 2( continued)
cleavage of the isopropylidene chain. The mass spectrum
of MCBPA has significant fragment ions at m/z 119 and
153. The fragment ion m/z 153 is assigned to C8H6ClOþ
(3-chloro-4-hydroxystyrene radical). The mass spectrum
of T4CBPA does not have these fragment ions but has
another fragment ion at m/z 187 which can be assigned
to C8H5Cl2Oþ (3,5-dichloro-4-hydroxystyrene radical).
So, the mass spectrum of 2; 20-D2CBPA should have a
fragment ion at m/z 153 and lack those at m/z 119 and
187, since each aromatic ring bears one chlorine atom.
On the other hand, the mass spectrum of 2; 6-D2CBPA
should have fragment ions at m/z 119 and 187 and lack
that at m/z 153, since one only of its aromatic rings has
two chlorine atoms. Therefore, peak #3 may be inter-
preted as 2; 20-D2CBPA, since the mass spectrum of
peak #3 has a fragment ion at m/z 153 and no fragment
ions at m/z 119 or 187. Peak #4 also may be interpreted
as 2; 6-D2CBPA because of the lack of a fragment ion at
m/z 153 in its mass spectrum. Peak #5 may be inter-
preted as 2; 20; 6-trichlorobisphenol A (T3CBPA) by a
similar interpretation.
The levels of chlorinated BPA congeners which are
tentatively determined using calibration curves of BPA
and T4CBPA, are listed in Table 1. When initial chlorine
concentration was 1.03 or 2.07 mg/l and reaction time
was within 30 min, the sums of the yields of BPA and
chlorinated BPA congeners were over 70% of initial
BPA. Therefore, if initial chlorine concentration is

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T. Yamamoto, A. Yasuhara / Chemosphere 46 (2002) 1215–1223
relatively low to BPA concentration, chlorine will be
nearly consumed by formation chlorinated BPA cong-
eners and further chlorination will be stopped.
What environmental impact are these chlorinated
BPA congeners likely to give? One of the most inter-
esting and significant properties of these compounds is
estrogenicity. Does the estrogenicity of chlorinated BPA
congeners increase when compared with the original
BPA? Unfortunately, there are no reports about the
estrogenicity of chlorinated BPA. Only brominated
BPA, 2; 20; 6; 60-Tetrabromobisphenol A (T4BBPA), has
Fig. 3. Total ion chromatogram of cleavage products (initial
chlorine concentration 10.24 mg/l, reaction time 5 min).
€
been examined for its estrogenic properties. Korner et al.
Fig. 4. Mass spectra of cleavage compounds. (a) D2CBQ (peak #1 in Fig. 3), (b) T3CP (peak #2), (c) C9H8Cl2O (peak #3), (d) D2CHQ
(peak #4), (e) C10H12Cl2O2 (peak #5), (f) C9H10Cl2O2 (peak #6).

T. Yamamoto, A. Yasuhara / Chemosphere 46 (2002) 1215–1223
1221
Fig. 4 (continued)
(1998) estimated that the estrogenicity of T4BBPA was
5 Â 10ꢀ6 times that of 17b-estradiol and about one tenth
the estrogenicity of BPA ð5 Â 10ꢀ5Þ by E-screen assay.
From this result, it can be assumed that halogenation of
BPA somewhat weakens its estrogenic properties. As for
the acute toxicity of chlorinated BPA, the oral LD50
values for T4CBPA for rats and mice are 7432and 5050
mg/kg, respectively (National Institute for Occupational
Safety and Health, 1987). Although these values are
lower than those for BPA (3250 and 2500 mg/kg), there
is no reason to disregard these chlorinated BPA cong-
eners since their degree of chlorination may increase
with environmental and biological accumulation, as has
been observed for other organochlorine compounds.
3.3. Cleavage products of chlorinated BPA congeners
Chlorinated phenolic compounds were formed dur-
ing the chlorination through the degradation of chlori-
nated BPA congeners. A typical total ion chromatogram
of an extract of a chlorinated sample is shown in
Fig. 3. 2; 6-Dichloro-1,4-benzoquinone (D2CBQ, peak
#1), T3CP (peak #2), 2; 6-dichloro-1; 4-hydroquinone
(D2CHQ, peak #4) are identified by comparing their

1222
T. Yamamoto, A. Yasuhara / Chemosphere 46 (2002) 1215–1223
mass spectra (Fig. 4(a),(b) and (d)) and retention times
with those of authentic standards. Peak intensities of
T3CP, D2CBQ and D2CHQ were lower than one of the
other products. The mass spectrum of peak #3 is shown
in Fig. 4(c). The ion recorded at m/z 202 may be taken to
be Mþ. The isomeric pattern of this molecular ion sug-
gest that the molecule from which it is derived has two
chlorine atoms. A fragment ion at m/z 187 is generated
by loss of CH3 and a fragment ion at m/z 162may be
formed by loss of C3H4 from Mþ. Since this fragmen-
tation pattern resembles the fragmentation pattern of a-
methylstyrene (The National Institute of Standards and
Technology, 2000a), the formula of this compound is
taken to be C9H8Cl2O (2-(3,5-dichloro-4-hydroxyphe-
nyl)-prop-1-ene). The mass spectrum of peak #5 is
presented in Fig. 4(e). The molecular ion is at m/z 234. A
fragment ion appearing at m/z 219 may be generated by
loss of CH3. The isomeric pattern of this fragment ion
indicates that this compound has two chlorine atoms.
Since the fragment ion at m/z 203 is likely to have
been formed by loss of CH3O, this compound may be
assumed to possess a methoxy group. The presumed
formula of this compound is C10H12Cl2O2 (2-(3,5-di-
chloro-4-hydroxyphenyl)-2-methoxypropane). The mass
spectrum of peak #6 is shown in Fig. 4(f). The molecular
ion appears at m/z 220. The fragment ion at m/z 205 may
be generated by loss of CH3. The fragment ion at m/z
202 is assumed to have been generated by dehydration,
and the fragment ion m/z 162may be formed by release
of C2H3O from ðM–CH3Þþ. This fragment pattern re-
sembles that of 2-phenylpropan-2-ol (National Institute
of Standards and Technology, 2000b). Therefore, the
presumed formula of this compound is C9H10Cl2O2 (2-
(3,5-dichloro-4-hydroxyphenyl)-propan-2-ol). Non- or
mono-chlorinated phenolic compounds were not found
among the all experimental conditions. This result may
suggest that T4CBPA is the only congener cleaved to
form chlorinated phenolic products since cleavage of
lower chlorinated BPA congeners give non- or mono-
chlorinated phenolic compounds. We also could not find
cleavage products when the initial chlorine concentra-
tion was 1.03 mg/l. This result also suggests that the rate
of cleavage of the isopropylidene chain may be much
slower than the rate of chlorination of the aromatic
ring. Therefore, formation reaction of chlorinated BPA
congeners (Cl ¼ 1–4) preceded the cleavage reaction of
the isopropylidene chain.
Fig. 5. Presumed chlorination reaction scheme of BPA.
oxidation of T3CP. D2CHQ may be present as a result of
the redox equilibrium with D2CBQ. The sums of the
yields of these chlorinated phenolic compounds, which
were estimated from their peak areas recorded by GC/
MS measurements (in scan mode and not quantitative),
were not exceeded 10% of initial BPA. Therefore, this
scheme may be not stoichiometric and other compounds
may exist, which are not detectable by our analytical
procedure (solvent extraction – GC/MS determination).
For one thing, highly polar compounds and volatile
compounds formed from these chlorinated phenolic
compounds by further chlorination.
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