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Simultaneous Determination and Assessment of 4-Nonylphenol, Bisphenol A and
Simultaneous Determination and Assessment of 4-Nonylphenol, Bisphenol A and
Environment International
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e n v i n t
a r t i c l e
i n f o
Article history:
Received 9 June 2009
Accepted 14 April 2010
Available online 7 May 2010
Keywords:
Contaminants
Drinking water
Baby bottle
Endocrine disrupting chemicals
Risk
a b s t r a c t
This study investigated the levels of 4-nonylphenol (4-NP), bisphenol A (BPA) and triclosan (TCS) in bottled
water and tap water in Guangzhou and release of these chemicals from baby bottles using gas
chromatographymass spectrometry with negative chemical ionization. Results show that 4-NP was present
in all the bottled water while 17 out of 21 contained BPA and 18 out of 21 contained TCS. Their
concentrations in bottled water ranged from 108 to 298 ng/L, 17.6 to 324 ng/L and 0.6 to 9.7 ng/L,
respectively. Five of the tap water samples from six drinking water plants were found to contain 4-NP and
BPA both in June and December, while TCS was detected in the same ve plants only in June. The highest
concentrations in tap water for 4-NP, BPA and TCS were 1987, 317 and 14.5 ng/L, respectively. Daily intakes
of 4-NP, BPA and TCS of adults by drinking 2 L of tap water were estimated to be 1410, 148 and 10 ng/day,
respectively. BPA was found to be released within 24 h from four brands of baby bottles at room temperature
(24 C), 40 C and 100 C. Increased temperature led to higher release of BPA from the baby bottles.
Estimated daily intakes of 4-NP, BPA and TCS for infants were 705, 1340 and 5 ng/day, respectively, by
drinking 1 L of tap water from a baby bottle at 40 C. This study showed that the exposure to the three
compounds from drinking water is unlikely to pose a health risk.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
In the last decades, 4-nonylphenol (4-NP), bisphenol A (BPA) and
triclosan (TCS) attracted a lot of attention due to their potential
endocrine disrupting effects on, or toxicity to wildlife as well as their
human health concerns (Alexander et al., 1988; Yokota et al., 2001;
Orvos et al., 2002; Rule et al., 2005; Ying, 2006; Fiss et al., 2007; Soares
et al., 2008; Uchiyama et al., 2008; Yang et al., 2008). These three
chemicals have been widely used in domestic products such as
surfactants and food packaging lms for 4-NP (White et al., 1994;
Khim et al., 1999; Guenther et al., 2002; Ying et al., 2002; Gatidou et al.,
2007; Uchiyama et al., 2008), polycarbonates (PC) and epoxy resins
products (such as baby bottles and food containers) for BPA (Olea et al.,
1996; Biles et al., 1997; Vandenberg et al., 2007), and personal care
products (such as toothpaste, cosmetics, skin care creams and lotions,
soaps and dental products) for TCS (Jones et al., 2000; McAvoy et al.,
2002; Tsai et al., 2008). It is therefore necessary to understand human
exposure to these chemicals through consumer products.
There are various routes of human exposure to the three
chemicals, especially through consumption of food and water.
Previous studies reported presence of 4-NP, BPA and TCS in human
milk and food (Ademollo et al., 2008; Allmyr et al., 2006, 2008;
558
Table 1
Parameters of the target compounds and selected ions in GC-NCI-MS.
Compoundsa
c
4-n-NP (I.S.)
4-NP
BPA-d16 (I.S.)
BPA
13
C12-TCS (I.S.)
TCS
a
b
c
Supplier
M.W.c
R.T. (min)c
Ionsb
Dr. Ehrenstorfer
Dr. Ehrenstorfer
Supelco
Supelco
Cambridge
Dr. Ehrenstorfer
220
220
244
228
301.5
289.5
19.04
17.63
25.51
25.62
20.41
20.42
414.1
414.1
630.0
616.0
494.0
484.8
415.0
415.0
630.9
617.0
495.8
483.8
416.0
416.0
420.1
405.9
298.9
286.8
300.8
288.8
2.5. Analysis
GC-MS analysis of the derivatized samples was carried out using
an Agilent 6890 N gas chromatograph connected to an Agilent 5975B
MSD mass spectrometer with a chemical ionization (CI) source
(Agilent, USA). The target compounds were separated on a capillary
column DB5-MS (30 m 0.25 mm, 0.25 m lm thickness). Helium
was used as the carrier gas and maintained at a constant ow rate of
1.0 mL/min, and the reaction gas was high-purity methane
(N99.999%) with a constant ow of 2.0 mL/min. The temperatures of
both ion source and quadrupole were set at 150 C. A sample volume
of 1 L was injected in splitless mode at an inlet temperature of 300 C.
The GC oven temperature program applied was as follows: from 80 C
(1 min) to 220 C at 10 C/min, from 220 C to 260 C at 4 C/min, and
from 260 C to 300 C (8 min) at 5 C /min, then to the temperature of
310 C (15 min) at 20 C /min. The MS interface temperature was
maintained at 310 C. The characteristic ion fragments of the
derivatized 4-NP, BPA and TCS were selected for quantication and
conrmation under selected ion monitoring mode (Table 1).
559
Table 3
Concentrations of 4-NP, BPA and TCS in bottled water.
Samples
Compounds (ng/L)c
4-NP
S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21
Min
Max
Median
a
b
c
129 3
127 30
145 8
126 16
127 7
111 14
108 6
122 12
130 2
111 24
148 43
236 29
219 6
298 53
217 16
210 47
186 35
163 21
271 63
181 3
204 5
108
298
170
BPA
TCS
55.4 4.9
55.3 6.5
44.7 4.5
ND b
ND
ND
ND
22.8 1.7
129 97
78.5 7.1
155 40
324 47
56.2 17.6
285 18
52.0 18.3
17.6 0.7
45.2 47
18.0 2.0
23.4 4.6
19.3 0.2
19.0 0.4
17.6
285
82.4
9.7 2.6
8.7 2.0
7.8 0.5
ND
ND
ND
0.6 0.1
1.6 0.1
2.1 0.8
2.1 0.2
2.6 0.1
3.6 0.4
3.4 0.2
3.2 0.0
3.6 0.1
1.9 0.0
2.9 1.3
2.2 0.2
2.2 0.1
2.5 0.2
2.5 0.2
0.6
9.7
3.5
Mean (ng/mL) standard deviation (n = 3, replicate samples taken at the same time).
ND: not detected.
4-NP: 4-nonylphenol; BPA: bisphenol-A; TCS: triclosan.
Table 2
Recoveries (%) and limits of detection of the target compounds.
Compoundsa
4-NP
BPA
TCS
a
b
c
Spiked concentrationsb
5 ng/L
100 ng/L
200 ng/L
92 4
118 8
105 7
115 13
103 1
98 2
74 5
105 3
97 3
LOD
(ng/L)c
LOQ
(ng/L)c
2.0
0.7
0.2
7.0
2.0
0.5
The concentrations of 4-NP, BPA and TCS in tap water from the six drinking water
plants were listed in Table 4. In the June sampling, the three target compounds were all
detected in the six drinking water plants except for Plant 6 without TCS being detected,
and the highest concentrations of all the three target compounds were 1070 ng/L for 4NP, 317 ng/L for BPA and 14.5 ng/L for TCS, which was found in Plant 5. The
concentrations of 4-NP in tap-water samples were the highest among the three target
compounds, ranging from 196 to 1070 ng/L. As for BPA, the concentration varies a lot
from 2.3 to 317 ng/L. The concentrations of TCS ranged from below the LOQ to 14.5 ng/
L. In the December sampling, 4-NP and BPA were detected with concentrations up to
1990 ng/L for 4-NP and 123 ng/L for BPA, but no TCS was detected in all six plants.
3.3. Baby bottles
This study showed that BPA was released from the baby bottles at RT (24 C), 40 C
and 100 C (Table 5). Temperature affected the migration of BPA from baby bottles to a
certain degree, with BPA released signicantly at 100 C. The highest migration of BPA
was found in Brand 3, and the amount released into the water were 267, 987 and
4500 ng at 24 C, 40 C and 100 C within the rst 24 h. The lowest migration of BPA
was found in Brand 1 and Brand 4. No signicant 4-NP and TCS were found released
from the baby bottles at the three temperatures.
Table 6 shows that BPA migrated out continuously into water from the baby bottles
under normal use conditions at 24 C and 40 C. The amount of BPA released from the
baby bottles in the following days was lower than that of the rst day.
4. Discussion
Drinking water is an important route of human exposure to
contaminants including 4-NP, BPA and TCS. Trace levels of these
chemicals were detected in bottled water from a local supermarket in
Guangzhou. The concentration of 4-NP in the bottled water of this
560
Table 4
Concentrations of 4-NP, BPA and TCS in tap water from six water supply plants.
Phenolic compounds (ng/L)d
Plants
4-NP
BPA
June
a
P1
P2
P3
P4
P5
P6
Min
Max
Median
a
b
c
d
December
406 25
199 66
1160 62
1150 89
566 38
186 13
186
199
909
327 29
286 29
886 13
196 13
1070 106
241 25
196
1073
502
42.5 0.6
54.3 1.8
171 2
7.0 0.8
317 5
2.3 1.6
2.3
317
99.0
Brand
B1
B2
B3
B4
b
December
June
December
14.7 1.2
123 8.4
61.8 5.9
23.8 1.5
19.8 15.6
ND b
19.8
123
48.6
14.1 1.2
4.1 0.4
11.9 0.1
4.1 0.1
14.5 1.2
bLOQ c
bLOQ
14.5
9.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
Mean (ng/mL) standard deviation (n = 3, replicate samples taken at the same time).
ND: not detected.
bLOQ: below the limit of quantitation.
4-NP: 4-nonylphenol; BPA: bisphenol-A; TCS: triclosan.
Table 5
Migration of bisphenol A from baby bottles at different temperatures within 24 h.
TCS
June
40 C
100 C
ND
117 30 a
267 100
ND b
13 7
206 51
987 181
92
309 107
311 185
4500 1940
34 4
study was similar to the results of Shao et al. (2005). BPA was detected
in 17 out of 21 bottled water samples in this study, while no BPA was
detected in the previous study (Shao et al., 2005). Toyo'oka and
Oshige (2000) reported the presence of 4-NP in mineral water from
poly(ethylene terephthalate) (PET) bottles in concentrations ranging
from 19 to 78 ng/L. Bottled water is usually sold in plastic containers,
normally PET and high-density polyethylene (HDPE) as well as poly
(vinyl chloride) (PVC). 4-NP could leach out from HDPE and PVC
containers (Loyo-Rosales et al., 2004). BPA could be released into the
water from polycarbonate (PC) drinking bottles at room temperature
(Le et al., 2008). However, it is not clear whether the BPA detected in
this study came from the drinking bottles or the water itself, or both.
Estrogenicity in bottled mineral water has been reported in Germany,
ranging from 2 to 40 ng/L EEQ (estradiol equivalent) (Wagner and
Oehlmann, 2009), suggesting the presence of estrogenic compounds
in the bottled water.
Compared to the U.S.A. drinking water survey data by Benotti et al.
(2009), the concentrations of BPA and TCS in tap water were similar
while the levels of 4-NP were 10 times higher than that in their study.
BPA was also detected at 160 ng/L in Brazilian drinking water, which
was attributed to a large input of raw sewage into surface water (Sodr
Table 6
Migration of bisphenol A from baby bottles at different times under normal use conditions.
Brand
B1
B2
B3
B4
a
b
Day 1
Day 3
Day 5
Day 7
24 C
40 C
24 C
40 C
24 C
40 C
24 C
40 C
ND b
117 30 a
267 100
ND
13 7
206 51
987 181
92
1.9 3.2
44 40
84 16
24 31
27 3
52 14
237 17
24 1
ND
11 8
33 22
ND
38 6
79 17
254 42
51 5
ND
27 17
51 29
ND
35 18
74 26
161 48
12
4-NP
BPA
TCS
Adults (ng/day)b
Infants (ng/day)b
Bottled water
Tap water
340
165
7
1410
148
10
705
1340
5
NP, 1340 ng/day of BPA and 5 ng/day of TCS. From the results, it can be
concluded that different types of water showed large variations of 4NP consumption for adults.
Daily intakes of 4-NP, BPA and TCS through consuming only tap
water and mineral water varied between adults and infants. And the
most concern according to this study is that the daily BPA intake for
infants was 3 times that for adults while infants were more vulnerable
to these toxic substances. However, the daily intake values of 4-NP,
BPA and TCS are much lower than their tolerable daily intake (TDI)
values, which are 5 g/kg body weight for NP (Nielsen et al., 2000),
50 g/kg body weight for BPA (Tsai, 2006) and 50 mg/kg body weight
for TCS (Dayan, 2007). The exposure anticipated from drinking water
is just one of the many sources of EDC contamination; other sources
such as food should be included in order to have a proper risk
assessment for the three compounds. We also need to bear in mind
that health risk assessment with a single compound may not fully
reect the effects of exposures to EDC mixture in the real
environment.
5. Conclusion
This study demonstrated that 4-NP, BPA and TCS were ubiquitous
in drinking water including tap water, mineral water and pure
drinking water. BPA can be released into the water from PC baby
bottles at room temperature, 40 C and 100 C. Daily intake of 4-NP,
BPA and TCS through drinking tap water is 1410 ng/day, 148 ng/day
and 10 ng/day, respectively for adults, and 705 ng/day, 1340 ng/day,
and 5 ng/day, respectively for infants. Most disturbingly, the daily
intake of BPA for infants is nearly 10 times that for adults. However,
based on this study, exposure to these three compounds from
drinking water poses little risk to human health. But further research
is needed to consider mixture effects and combined ingestion routes
including food and water in order to make a more realistic human
health risk assessment of daily intake of 4-NP, BPA and TCS.
Acknowledgments
The authors would like to acknowledge the nancial support from the
National Natural Science Foundation of China (NSFC40688001, 40771180
and 40821003) and from the Guangdong Provincial Natural Science
Foundation (8251064004000001). This is the contribution No. 1187 from
GIGCAS.
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