Supplementary Data for
Occurrence and human exposure of parabens and their chlorinated
derivatives in swimming pools
Wenhui Li a, Yali Shi b, Lihong Gao a, Jiemin Liu a,*, Yaqi Cai b,*
a
School of Chemistry and Biological Engineering, University of Science and Technology
Beijing, University of Science and Technology Beijing, Beijing 100083, China;
b
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center
for Eco-Environmental Science, Chinese Academy of Sciences, Beijing 100085, China
*Corresponding author
Tel: +86 10 62849182; fax: +86 10 62849182;E-mail: caiyaqi@rcees.ac.cn
Tel.: +86 010 62333751; E-mail: liujm@ustb.edu.cn
1
Parameters are calculated according Exposure Factors Handbook (US EPA, 2011)
The permeability coefficient of parabens (Kp, cm h-1) was calculated using the
equation:
log K p = −2.80 + 0.66 log K ow − 0.0056 MW
(1)
where Kp is the dermal permeability coefficient of parabens in water (cm h-1)
; Kow is
the Octanol/water partition coefficient of the parabens (dimensionless)
; MW is the
molecular weight (g mol-1)
The dimensionless ratio of the permeability coefficient of a compound through the
stratum corneum relative to its permeability coefficient across the viable epidermis (B,
dimensionless) was calculated using the equation:
B = Kp
√𝑀𝑊
2.6
(as an approximation)
(2)
The effective diffusion coefficient (DSC, cm2 h-1) of the chemical in the stratum corneum
was calculated using the equation:
log( Dsc ⁄lsc ) = −2.80 − 0.0056 MW
(3)
where lsc is the Apparent thickness of stratum corneum (cm), and lsc = 0.001 cm.
The lag time (τ, h) was calculated using the equation:
τ = l2sc ∖ (6Dsc )=0.105×10(0.0056 MW)
2
(4)
Captions:
Table S1 Physicochemical characteristics of the target compounds
Table S2 Details of pool design and operating parameter values
Table S3 Experimental conditions of electrospray tandem mass spectrometry
Table S4 Correlation coefficients (r), linear range, recoveries (%) and method detection
limits (MDLs, S/N=3) of target compounds
Table S5 Spearman's coefficients of the concentrations of target compounds and with
operating parameters of 39 pools.
Fig.S1. Box-and-whisker plots of concentrations of parabens and chlorinated derivatives
in indoor and outdoor swimming pools
Fig.S2. Box-and-whisker plots of concentrations of parabens and chlorinated derivatives
on the weekend and weekdays.
3
Table S1 Physicochemical characteristics of the target parabens
Analytes
Structure
SW
(g mo1-1)
(mg L-1)
p-Hydroxybenzoic
acid (PHBA)
138.12
14,500
2.7; 8.4
1.39[1]
1.13×10-11 [2]
Methyl paraben
(MeP)
152.15
5981
8.17[3]
1.66[3]
3.61×10-9
Ethyl paraben
(EtP)
166.17
960[4]
8.22
2.19
4.79×10-9
Propyl paraben
(PrP)
180.20
390[4]
8.35
2.71
6.37×10-9
Butyl paraben
(BuP)
194.23
207[5]
8.37
3.24[4]
8.45×10-9
Pentyl Paraben
(PeP)
208.25
n.a.
n.a.
3.48
n.a.
Heptyl paraben
(HeP)
236.31
n.a.
n.a.
4.41
1.98×10-8
Benzyl paraben
(BzP)
228.24
160[5]
8.18[6]
3.56 [3]
2.92×10-10
Octyl paraben
(OcP)
250.34
n.a.
n.a.
4.88
n.a.
Methyl
3-chloro-4-hydroxyb
enzoate (3-Cl-MeP)
186.59
2.64[7]
n.a.
2.27
n.a.
4
pKa
logKow
Hc
MW
(atm m3 mol-1)
Methyl
3,5-dichloro-4-hydro
xybenzoate
(3,5-2Cl-MeP)
Ethyl
3-chloro-4-hydroxyb
enzoate (3-Cl-EtP)
221.04
3.29[7]
n.a.
2.88
n.a.
200.62
2.31[8]
n.a.
n.a.
n.a.
Ethyl
3,5-dichloro-4-hydro
xybenzoate
(3,5-2Cl-EtP)
235.06
2.34[8]
n.a.
3.32
n.a.
The table includes information on the hydrophobicity (log Kow); aqueous solubility (Sw) at
neutral pH; acid-base reactivity (pKa); Henry’s Law constant (Hc) at 25 °C. n.a.: not available
5
Table S2 Details of pool design and operating parameter values
NO.
Type
Functional areas
Disinfection type
Size (m3)
Date
Opening Hours (h)
Price (RMB)
Visitors
TOC (mg L-1)
S01
Indoor
Community
Chlorine
500
Weekday
11
40
25
15.4
S02
Indoor
Community
Chlorine
600
Weekend
10
35
25
10.2
S03
Indoor
School
Chlorine
1200
Weekday
13
30
80
3.13
S04
Indoor
School
Chlorine
1700
Weekend
11
30
112
5.88
S05
Indoor
School
Chlorine
1200
Weekday
13.5
30
45
12.5
S06
Indoor
School
Chlorine
1200
Weekend
10
20
37
4.37
S07
Indoor
School
Ozone/ Chlorine
2000
Weekday
9.5
20
62
1.55
S08
Indoor
Municipal
Chlorine
1600
Weekend
10
50
192
9.50
S09
Indoor
School
Chlorine
400
Weekday
11
30
13
1.63
S10
Indoor
School
Chlorine
1600
Weekend
10
30
30
7.92
S11
Indoor
Municipal
Ozone/ Chlorine
600
Weekend
11
35
213
7.16
S12
Indoor
Community
Chlorine
480
Weekend
12
50
73
8.92
S13
Indoor
Community
Chlorine
400
Weekday
11
38
35
10.4
S14
Indoor
Community
Chlorine
300
Weekend
12
30
57
13.8
S15
Indoor
Community
Chlorine
400
Weekday
14
40
12
5.67
S16
Indoor
Municipal
Chlorine
600
Weekend
12
30
43
8.79
S17
Outdoor
Municipal
Chlorine
12000
Weekend
7
30
472
3.48
S18
Outdoor
Municipal
Chlorine
18000
Weekday
10
30
150
4.48
S19
Outdoor
Municipal
Chlorine
2400
Weekday
7.5
30
134
2.66
S20
Indoor
Health club
Chlorine
450
Weekend
13
35
28
11.9
S21
Indoor
School
Chlorine
400
Weekend
16
20
55
7.72
S22
Indoor
School
Chlorine
2000
Weekend
12
25
156
4.12
6
S23
Indoor
School
Chlorine
2250
Weekend
11.5
30
104
3.27
S24
Indoor
Community
Chlorine
1200
Weekend
14
40
17
6.88
S25
Indoor
School
Chlorine
2000
Weekday
12.5
50
76
7.94
S26
Indoor
School
Chlorine
2000
Weekday
12
50
46
7.66
S27
Indoor
School
Chlorine
2000
Weekend
12
50
74
6.69
S28
Indoor
Municipal
Chlorine
1600
Weekend
11
50
205
4.67
S29
Indoor
Hotel
Chlorine
3200
Weekday
12
100
1000
12.5
S30
Indoor
Hotel
Chlorine
240
Weekday
12
100
102
2.15
S31
Indoor
Hotel
Chlorine
160
Weekend
13
100
23
8.06
S32
Indoor
Hotel
Chlorine
500
Weekend
13
90
44
10.1
S33
Indoor
Community
Chlorine
600
Weekend
13
60
13
8.80
S34
Indoor
Health club
Chlorine
400
Weekday
12
40
12
9.83
S35
Indoor
Health club
Chlorine
1200
Weekend
12.5
50
121
10.6
S36
Indoor
Community
Chlorine
500
Weekend
12
40
23
10.0
S37
Indoor
Municipal
Chlorine
2000
Weekend
12
50
243
13.7
S38
Outdoor
Municipal
Chlorine
1600
Weekend
8
20
1131
12.9
S39
Indoor
Health club
Chlorine
600
Weekend
12
50
13
21.7
7
Table S3 Experimental conditions of electrospray tandem mass spectrometry
Analytes
Parent
Daughter
Declustering
Entrance
Collision
Collision
Collision cell
ion
ion
Potential/
Potential/
cellent
Energy/
exit potential/
(m/z)
(m/z)
MeP
151.0
EtP
165.0
PrP
179.0
BuP
193.0
PeP
207.1
HeP
235.1
BzP
227.0
OcP
249.1
PHBA
137.0
3-Cl-MeP
185.0
3,5-2Cl-MeP
218.9
3-Cl-EtP
199.0
3,5-2Cl-EtP
232.9
PHBA-d4
141.0
MeP-d4
EtP-d5
155.0
170.0
V
V
potential/V
eV
V
a
91.9
136.0
93.0 a
137.0
93.0
136.0 a
91.9 a
136.0
91.9 a
93.0
92.0 a
135.9
91.9
136.0 a
93.0 a
136.0
93.0 a
65.1
126.0 a
142.0
160.0 a
176.0
127.0
170.9 a
161.1 a
205.0
-27
-27
-25
-25
-30
-30
-30
-30
-35
-35
-40
-40
-25
-25
-45
-45
-23
-23
-30
-30
-40
-35
-32
-32
-36
-36
-5
-5
-5
-5
-5
-5
-5
-5
-10
-10
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-7
-6
-14
-7
-8
-6
-8
-8
-9
-9
-12
-8
-8
-8
-10
-10
-8
-8
-7
-7
-8
-8
-8
-7
-8
-8
-26
-27
-30
-17
-28
-20
-35
-21
-34
-30
-38
-25
-34
-18
-35
-27
-20
-43
-26
-24
-28
-28
-26
-20
-30
-22
-10
-14
-10
-13
-10
-14
-10
-13
-10
-10
-10
-14
-10
-14
-13
-10
-10
-8
-13
-14
-15
-15
-13
-15
-16
-18
97.1 a
-23
-5
-8
-18
-10
69.1
-23
-7
-15
-40
-10
96.1 a
-25
-10
-10
-28
-10
112.1
-25
-10
-10
-28
-10
91.9
-26
-5
-8
-30
-10
-26
-5
-8
-30
-10
94.0
PrP-d7
BuP-d9
BzP-d7
a
186.1
202.1
233.9
a
91.9
-30
-5
-8
-33
-10
94.0
a
-30
-5
-8
-33
-10
91.9
a
-30
-5
-8
-34
-10
136.0
-30
-5
-8
-35
-10
91.9
-40
-9
-10
-40
-11
136.0 a
-40
-9
-26
-22
-13
quantitative ion
8
Table S4 Correlation coefficients (r2), linear range, recoveries (%) and method detection limits
(MDLs, S/N=3) of target compounds
Analytes
Surrogates
r2
Linear range (μg L-1)
Recovery (%)
MDLs (ng L-1)
MeP
MeP-d4
0.9997
0.1-500
97.5±7.4
0.07
EtP
EtP-d5
0.9987
0.1-500
92.7±5.1
0.03
PrP
PrP-d7
0.9993
0.1-500
94.3±5.7
0.08
BuP
BuP-d9
0.9998
0.05-200
94.4±6.9
0.03
Pep
BuP-d9
0.9984
0.05-500
97.6±3.8
0.03
Bzp
BzP-d7
0.9923
0.05-200
104±1.9
0.02
Hep
BuP-d9
0.9992
0.05-500
92.4±3.3
0.02
Ocp
BuP-d9
0.9995
0.1-200
94.2±5.9
0.06
PHBA
PHBA-d4
0.9907
1.0-500
85.9±11
0.40
3-Cl-MeP
MeP-d4
0.9998
0.1-500
101±4.3
0.07
3,5-2Cl-MeP
MeP-d4
0.9995
0.1-500
98.3±2.7
0.05
3-Cl-EtP
EtP-d5
0.9996
0.1-500
95.0±5.3
0.10
3,5-2Cl-EtP
EtP-d5
0.9996
0.1-500
101±5.6
0.16
9
Table S5 Pearson's coefficients of the concentrations of target compounds and with parameters of 39 pools
Parameters
∑PBs
Pearson
∑Cl-PBs
Sig. (2-tailed) Pearson
Correlation
∑PBs+∑Cl-PBs
PHBA
Sig. (2-tailed)
Correlation
Pearson
Sig. (2-tailed)
Correlation
Pearson
Sig. (2-tailed)
Correlation
Price (RMB)
0.336*
0.036
0.037
0.825
-0.229
0.160
0.326*
0.042
Vistors
-0.083
0.617
-0.301
0.062
0.067
0.683
-0.093
0.573
Size (m3)
-0.116
0.480
-0.350*
0.029
-0.091
0.583
-0.128
0.436
Opening Hours (h)
0.210
0.200
0.327*
0.042
0.077
0.642
0.220
0.178
TOC (mg L-1)
0.217
0.185
0.471**
0.002
0.118
0.475
0.237
0.147
**. Correlation is significant at the 0.01 level (2-tailed); *. Correlation is significant at the 0.05 level (2-tailed)
10
Fig.S1. Box-and-whisker plots of concentrations of parabens and chlorinated derivatives in indoor
and outdoor swimming pools.
11
Fig.S2. Box-and-whisker plots of concentrations of parabens and chlorinated derivatives on the
weekend and weekdays.
12
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