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Department of Environmental Engineering, Peking University, The Key Laboratory of Water and
Sediment Sciences, MOE, Beijing 100871, China; 2 Engineering Directorate, Lawrence Livermore
National Laboratory, 7000 East Ave., Livermore, CA 94550-9234, USA
( author for correspondence, e-mail: sunweiling@iee.pku.edu.cn, Tel.: +86-10-6276 7014;
Fax: +86-10-6275 1184)
Abstract. Bisphenol A is widely used for the production of epoxy resins and polycarbonate plastics,
and it has been found in many wastewaters or surface waters. Adsorption of bisphenol A on sediments
sampled from several representative hydrologic stations of the Yellow River was studied, and some
factors that may affect the sorption of bisphenol A were analyzed using the LC-MS/MS following
solid-phase extraction. The results show that neither linear nor Freundlich isotherms is fit to the
experimental data due to the high carbonate content in sediments. Bisphenol A has greater adsorption
after the elimination of the carbonate in the sediment, and the adsorption of bisphenol A on the treated
sediment can be described by both the linear and the Freundlich isotherms. The adsorption amount
of bisphenol A is related to both the total organic carbon and dissolved organic carbon of sediments.
The effects of Ca2+ and K+ on the adsorption of bisphenol A were also studied. It is found that Ca2+
and K+ showed different effects on the adsorption of bisphenol A because of their different valences.
Keywords: adsorption, bisphenol A, LC-MS/MS, sediment, SPE
1. Introduction
Bisphenol A (BPA) is mostly manufactured for the plastics industry. It is an intermediate in the production of epoxy resins and polycarbonate plastics. The plastics
are utilized in many food and drink packaging productions to line metal food cans,
bottle tops and water supply pipes. Some polymers containing BPA are even used
in dental treatment. In recent years, negative effects have been reported on the endocrine systems in humans and animals (Watts et al., 2001; Belfroid et al., 2002;
Kashiwada et al., 2002; Matsumoto et al., 2003). BPA is mainly discharged in the
manufacturing process (washing residue and wastewater), and it may also be inadvertently released as fugitive dust emission from closed systems during processing,
handling, and transportation (Staples et al., 1998). As BPA is widely used in both
households and industry, it may present in raw sewage, waste water effluents and
concentrated in sewage sludge. Some researchers have reported detection of BPA
in some rivers and landfill leachates (Staples et al., 1998; Furhacker et al., 2000;
Yamamoto et al., 2001).
Water, Air, and Soil Pollution (2005) 167: 353364
C
Springer 2005
354
W. L. SUN ET AL.
Besides mixing within the water column, BPA is subject to biodegradation, adsorption to soils and suspended solids and sediments, and possibly photodegradation. Adsorption reaction may influence the rate of other processes such as biodegradation and photolysis (Bekbolet et al., 1999). The adsorption reaction is governed
by the chemical and physical properties of the solids or sediments and chemicals
involved, and the mineral or organic components of sediments, dissolved organic
matter and the major cations in solution may be involved in the adsorption reaction
(Spark and Swift, 2002).
The Yellow River, as the second longest river of China, is noted for its high sediment concentration and thus sediments effect on water quality must be considered.
In recent years, increasing wastewaters, derived from point sources (industries and
living) and non-point sources (insecticides, fertilizers, waste residues, and landfills),
are discharged into the Yellow River. There are numerous hazardous pollutants in
these wastewaters, which may pose a severe threat on the river ecosystem. This paper focuses on the adsorption behavior of BPA on the sediment of the Yellow River
and relevant factors that may affect the adsorption. The results are of significance
to analyze and assess the transportation and transformation of BPA in water and
sediment systems.
2. Materials and Methods
2.1. REAGENTS
AND MATERIALS
All standards and chemicals used were of the highest purity commercially available.
Purified water used in experiments was made by Milli-Q Gradient System (Millipore, USA). HPLC-grade methanol (Scharlau, Belgium), BPA (purity 97%, ACROS
ORGANICS, Geel Belgium) and standard of BPA (purity 98.5%, D-86199 Augsburg Germany) were all purchased from J&K Chemical (Belgium). All the reagents
and solutions were stored in the dark at 4 C to prevent photochemical degradation.
The solid samples used in this study were collected at Tong Guan, San Menxia,
and Hua Yuankou sites of the Yellow River in August 2001. The samples were
air dried, grieved and screened into 0.063 mm. The characteristics and the mineral
components of sediments are shown in Tables I and II respectively. Total organic
carbon (TOC), chemical composition and grain size of the sediments were analyzed
using Muti 3000 TOC/TN analyzer (Analytic Jena, Germany), ICP (Jarvell-Ash,
ICAP-9000, America), and FRITSCH A22 laser particle size analyzer (FRITSCH,
Germany) respectively.
2.2. SAMPLE
PREPARATION
Proper amount of sediment was added into a 250 mL triangular flask, and 150 mL
pure water and 1050 L BPA solution (33.6 g mL1 ) were added and mixed.
The concentration range of BPA (C0 ) is 2 to 12 ng mL1 ; All the equilibrium
355
ADSORPTION OF BISPHENOL A
TABLE I
Characteristics of sediments at different sites in the Yellow River
Chemical components (%)
Sample d50 (mm) CaO
MgO K2 O
Na2 O SiO2
Al2 O3 MnO P2 O5
Fe2 O3 TOC
TS
SS
HB
TB
SB
2.077
1.762
1.494
1.562
1.639
1.214
1.685
2.014
1.920
1.917
8.750
7.633
7.115
7.214
7.145
4.680
3.712
3.814
3.288
4.434
0.048
0.048
0.058
0.050
0.104
7.456
6.604
5.518
5.905
6.091
2.263
2.023
1.999
2.065
2.063
60.775
66.970
70.580
70.570
68.540
0.115
0.119
0.164
0.122
0.162
0.098
0.194
0.103
0.280
0.137
0.667
0.316
0.123
0.125
0.109
TS = Tong Guan suspended solid, SS = San Menxia suspended solid, TB = Tong Guan bottom
sediment, SB = San Menxia bottom sediment, HB = Huan Yuankou bottom sediment.
ANALYSIS
A HP 1100 LC/MSn Trap SL System consisting of a series 1100 HPLC and trap mass
spectrometer equipped with electrospray interface (ESI) was used to separation and
quantification of BPA. Chromatography was performed using a Zorbax Eclipse
XDB-C18 (150 2.1 mm) reversed-phase HPLC column. The BPA was eluted
with 45% solvent A (100% water) and 55% solvent B (100% methanol) in 10 min,
and the flow rate was 0.4 mL min1 .
The MSD was tuned automatically using built-in calibrating delivery system.
Operating parameters of ESI source were optimized in MRM mode using flow
injection analysis of BPA. Optimum conditions for the BPA analysis were as follows: Capillary 3500 V, Nebulizer 35.0 psi, Dry Gas 8.0 L min1 , Dry Temperature
330 C.
3. Results and Discussion
3.1. ANALYTICAL
METHOD OF
LC-MS/MS
The analytical determination of BPA from surface and wastewater commonly uses
of GC-MS or GC-MS/MS (Yamamtoto and Yasuhara, 1999, 2002; Belfroid et al.,
356
W. L. SUN ET AL.
2002), HPLC (Fromme et al., 2002; Kubo et al., 2003; Yoon et al., 2003), and
each analytical technique has issues regarding pretreatment requirements, compound recoveries, detection limits, and compound specificities. However, LC-MS
or LC-MS/MS is a selective and sensitive method for determination of BPA in
drinking water, surface water, wastewater, and in liver and muscle tissue from a
relevant aquatic fish species (Pedersen and Lindholst, 1999).
When MSn detector for n > 2 is used to analyze organic chemicals, quantitative
analysis is often conducted with the mass spectrum of fragment ions (n = or > 2)
to decrease background noises and develop a sensitive method. The extractive ion
chromatography (EIC) of fragment ion m/z 212 and the fragment mass spectrum
of BPA with a scan range of m/z 100350 are shown in Figure 1. In addition to
the precursor ion, [M-H] m/z 227, three fragment ions (m/z 212, 153, 133) can
be detected. The m/z 212 fragment probably resulted from a cleavage of one of the
CH3 groups is the main fragment ion of BPA, so quantitative analysis was carried
out using MS/MS mode for the ion m/z 212. The retention time of the m/z 212
fragment is 5.8 min. The calibration curve of BPA consisted of five points at the
concentrations of 27.8, 101.8, 305.5, 672.0, 1680.0 ng mL1 . Calibration curve was
generated using linear regression analysis with all values weighted equally, and the
R 2 of the calibration curve was >0.999. The limit of detection was determined at
a signal-to-noise ratio (S/N) >3. The limit of quantification for BPA in water was
approximately 0.16 ng mL1 , and the recovery of the samples is within the range
of 80 to 120%.
x104
1.2
EIC 212 m /z
1.0
0.8
0.6
0.4
Intensity
0.2
0.0
0
250
275
8 Time (min)
x104
212
1.25
1.00
0.75
0.50
0.25
133
227
153
0.00
100
125
150
175
200
225
300
325 m/z
ADSORPTION OF BISPHENOL A
3.2. ADSORPTION
ISOTHERMS OF
357
BPA
50
40
30
T reated SB
SB
20
10
0
0
3
6
9
12
Equilibrium concentration (ng/mL)
358
W. L. SUN ET AL.
is alkaline (pH 7.58.5) due to its high carbonate content, and BPA has greater
water solubility at alkaline pH values due to its disassociation constants, pKa 9.6
to 10.2 (Staples et al., 1998). BPA dissolved predominantly in the water at lower
concentrations, and is adsorbed by sediments at higher concentrations. Therefore,
the adsorption isotherms of the solid samples in the Yellow River are of an approximate S type. The adsorption data suggest a modest adsorption of BPA on
sediment, which is comparable to the reported values (Ying et al., 2003).
To analyze the effect of the carbonate on the BPA adsorption, carbonate in the
bottom sediment of San Menxia was eliminated with acetic acid (Loeppert et al.,
1984). Compared with the SB (Figure 2), the adsorption amount of BPA on treated
SB increases about 9 ng g1 on average and the adsorption data can be described by
both the linear isotherm (R 2 = 0.9402, K d = 4.116) and the nonlinear Freundlich
isotherm (R 2 = 0.9345, K f = 6.248, n = 1.278). As shown in Table II, the carbonate
(calcite) content of the solid samples in the Yellow River is from 6% to 17.5%, which
is of importance to the adsorption of BPA. The elimination of carbonate decreases
the pH of the water-sediment system (pH 5.56.0), consequently increases the
adsorption owing to the decreasing solubility of BPA at lower pH.
3.3. ADSORPTION
OF
BPA
The adsorption amount of BPA measured on different solid samples are in the
following order TS>SS>SB>HBTB (Figure 3). The Total organic carbon (TOC)
of different samples are in the order of TS>SS>TBHB>SB according to the
characteristics of the solid samples (Table I), and the TOC of the suspended solids
are higher than those of bottom sediments evidently. For the suspended solids, the
adsorption amount of BPA correlates with TOC, and it is contrary for the bottom
sediments. The same results were reached at two different water-sediment ratios.
The adsorption of BPA on sediments may be affected by many factors. Concentrations of target contaminants (nonylphenol (NP), octylphenol (OP), BPA, and
Montmorillonite
5.0
1.5
1.0
1.0
1.0
Sample
TS
SS
HB
TB
SB
2.0
2.5
2.5
1.5
2.5
Chlorite
7.0
4.0
4.0
3.5
3.5
Kaolinite
20.5
13.5
11.0
14.0
11.5
Illite
25.5
25.0
31.5
25.5
26.5
Quartz
5.0
17.0
11.0
17.5
17.0
Feldspar
15.5
25.5
27.5
23.5
23.5
Plagioclase
17.5
7.0
6.0
6.0
6.0
Calcite
TABLE II
Mineral components of sediments at different sites in the Yellow River
1.5
2.5
2.0
4.5
3.5
Dolomite
0.5
1.5
3.5
3.0
5.0
Amphibole
ADSORPTION OF BISPHENOL A
359
360
W. L. SUN ET AL.
polychlorinated biphenyls (PCBs)) are not related to TOC (Khim et al., 1999). For
soils that have higher organic matter levels (>5%), the mobility of the pesticides has
been related to TOC, and with the nature of the organic matter <5% TOC has little
influence on sorption processes (Spark and Swift, 2002). However, the adsorption
of chemicals may be related to both TOC and minerals, and the interactions of
mineral-mineral and mineral-organics can decrease the number of adsorption sites
of the sediment or soil (Bekbolet et al., 1999; Spark and Swift, 2002). Barriuso
et al. (1992) showed that the adsorption of chemicals is related not only to the total
organic matter of soils but also to the dissolved organic matter (DOM) in the water
and soil system.
The adsorption amount of BPA on the suspended solids with higher TOC content
in the Yellow River is positively correlated with the TOC and grain size (Table I).
The adsorption amount of BPA on the bottom sediments is negatively correlated
with the TOC and grain size, which may be resulted from: (1) The adsorption
of BPA on the bottom sediments may be related to the Ferric minerals due to
the complexation among the dissolved Fe3+ ion, organic matter, and BPA; (2)
The adsorption of BPA may be related to DOM. The proportions of dissolved
organic carbon (DOC/TOC) for the solid samples are shown in Figure 4. The DOC
proportion of TS is lower than that of SS, and the DOC proportions of the bottom
sediments are in the following order: HBTB>SB. This order is corresponding to
that for BPA adsorption that shows a negative correlation with the DOC proportion
for either the suspended solids or bottom sediments at different sampling locations.
The DOM is endogenous (water soluble and humic compounds directly extracted
from sediment) (Barruiso et al., 1992). BPA, which interacts with organic matter,
will react with both the soluble and solid phase fractions, therefore, competitive
effects, the reversibility of these two types of interaction, will govern the distribution
of the BPA between the solid and soluble phases of the organic matter. Thus, the
adsorption amount of BPA on SB with lower DOC proportion is higher than those
of HB and TB evidently.
ADSORPTION OF BISPHENOL A
361
Figure 5. Effect of metal ions on the BPA adsorption (SS, water/sediment = 50/1, C0 =
6.72 ng mL1 ).
3.4. EFFECTS
OF IONS ON
BPA
ADSORPTION
Different ions have different effects on the adsorption of BPA on solid samples
(Figure 5). The adsorption amount of BPA increases with increasing Ca2+ and
decreases with increasing K+ within the ion concentration range of 04 mmol L1 .
Furthermore, Ca2+ and K+ have greater effects on the adsorption of BPA for higher
ion concentrations (>2 mmol L1 ). In the previous study, increasing the ionic
strength caused the adsorption of 2,4-dichlorophenoxy (2,4-D) to increase on soils,
and had no significant effect on the adsorption of atrazine and isoproturon (Spark
and Swift, 2002).
The adsorption isotherms of BPA also change after adding the metal ions
(Figure 6). The experimental data were subjected to regression analysis using a nonlinear Freundlich isotherm and linear isotherm, and the parameters and correlation
90
Ca2+
Pure water
K+
75
60
45
30
15
0
0
2
4
6
8
10
Equilibrium concentration (ng/mL)
Figure 6. Effect of metal ions on the adsorption isotherms of BPA (SS, water/sediment = 25/1, ion
concentration = 4 mmol L1 ).
362
W. L. SUN ET AL.
TABLE III
Adsorption parameters of BPA
Freundlich isotherm
(S = K f Ce1/n )
Linear isotherm
(S = K d Ce )
Metal ions
Kf
R2
Kd
R2
Pure water
Ca2+
K+
8.869
18.41
8.367
1.245
1.740
1.448
0.6032
0.7579
0.4323
6.963
9.122
5.936
0.8009
0.8389
0.6402
coefficients (R 2 ) of the adsorption isotherms are given in Table III. Adding Ca2+
and K+ can increase and decrease the BPA adsorption respectively, which is consistent with the above results (Figure 5). Furthermore, the correlation coefficients
increase after adding the Ca2+ , which is contrary to those of adding K+ .
The interactions between moleculars involved in adsorption are Van der Waals
interactions, hydrogen bonding, charge transfer, ion-bonding, direct and induced
ion-dipole, dipole-dipole interactions and chemisorption (Bekbolet et al., 1999).
BPA exists as charged species at alkaline pH values, so could engage in ion-bonding
as well as the other bonding mechanisms referred to above. In addition, soil or sediment organic matter tends to exhibit predominantly negatively charged adsorption
surfaces.
There may be two respects for the positive effect of Ca2+ on BPA adsorption. On
one hand, the charge interaction of the BPA ionic species with the negatively charged
sediment mineral and organic matter surfaces is more likely involve interaction with
cationic species such as Ca2+ in salt bridge arrangements (Spark and Swift, 2002).
On the other hand, increasing Ca2+ concentration may decrease the solubility of
carbonate in the sediment, which results in the decrease of the pH in reaction
systems. So the solubility of the BPA decreases and adsorption increases.
Different from Ca2+ , K+ is monovalent. It cannot act as salt bridge between
organic matter and BPA, but can bond with BPA in the solution, which will decrease
the adsorption amount of BPA.
3.5. E FFECT
BPA
ADSORPTION
363
ADSORPTION OF BISPHENOL A
30
SS
24
SB
18
12
6
0
0
20
40
60
80
Water-sediment ratio
improvement of water quality in the Yellow River, which is characterized with high
sediment concentration.
4. Conclusions
(1) The extent of adsorption of BPA depends on the nature and properties of the
sediment and the BPA. The adsorption isotherms of BPA are different from those
in other studies due to the high carbonate content of the sediments in the Yellow
River. BPA adsorption on treated sediment increases and the experimental data
are fit to both the linear and the nonlinear Freundlich isotherms due to the
elimination of the carbonate.
(2) The adsorption of BPA is related to the total organic matter and dissolved organic matter, and negative correlation is observed between adsorption amounts
and dissolved organic carbon proportions for the suspended solids and sediments respectively.
(3) Divalent and monovalent ions have different effects on the adsorption of
BPA.
Acknowledgement
Financial support is from the major state basic research program of the Peoples
Republic of China under the Grant No. G1999043603.
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