Supporting Information
Benzotriazole, Benzothiazole, and Benzophenone Compounds in Indoor Dust from the United States and East Asian Countries
Lei Wang†,‡, Alexandros G. Asimakopoulos†, Hyo-Bang Moon§, Haruhiko Nakata¶, Kurunthachalam Kannan†,e* †
Wadsworth Center, New York State Department of Health, and Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Empire State Plaza, P.O. Box 509, Albany, New York 12210-0509, United States
‡
Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria / Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Tianjin 300071, China
§
Department of Marine Sciences and Convergence Technology, College of Science and Technology, Hanyang University, Ansan 426-791, South Korea
¶
Graduate School of Science & Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555, Japan
*Corresponding author: K. Kannan Wadsworth Center Empire State Plaza, P.O. Box 509 Albany, NY 12201-0509 Tel: 1-518-474-0015 Fax: 1-518-473-2895 E-mail:
[email protected]
For submission to: Environmental Science and Technology
Pages: 9 Figures: 2
S1
Figure S1. LC-MS/MS chromatograms of BTH and 2-OH-BTH in extracts of rubber particles with or without heating at 200 oC for 60 min. Figure S2. Component distribution of BTRs, BTHs, BPs in indoor dust of rural residential rooms, urban residential rooms, and urban offices from China.
Tables: 5 Table S1. Target analytes and some physicochemical property parameters. Table S2. Gradient elution processes used in LC for BTRs/BTHs and BPs. Table S3. Coefficients of MS/MS analysis for target analytes. Table S4. Recoveries (%) of BTRs, BTHs, and BPs from spiked procedure blank and spiked matrices (n=6) of indoor dust. Table S5. Concentrations and Detection Rates of BTRs, BTHs, and BPs in Indoor Dusts of rural residential rooms, urban residential rooms, and urban offices from China (ng/g).
S2
Figure S1
BTH
2-OH-BTH
Figure S1. LC-MS/MS chromatograms of BTH and 2-OH-BTH in extracts of rubber particles with or without heating at 200 oC for 60 min. Experimental process: Rubber particles were heated in Muffle furnace at 200 oC for 60 min, and then 50 mg of heated rubber, as well as 50 mg of non-heated rubber, was extracted respectively by 2 mL of ethyl acetate for 1 h. The extracts were dried under nitrogen, re-dissolved in 1 mL of methanol, and analyzed by LC-MS/MS.
S3
Figure S2. (BTRs) 1H-BTR 1-OH-BTR TTR XTR 5-Cl-BTR
Rural houses (n=5)
Urban houses (n=38)
Offices (n=12)
(BTHs)
BTH 2-OH-BTH 2-Me-S-BTH 2-Amino-BTH 2-SCNMeS-BTH
Rural houses (n=5)
Urban houses (n=38)
Offices (n=12)
(BPs)
2OH-4MeO-BP 4OH-BP 2,4-OH-BP 22'-OH-4-MeO-BP 22'44'-OH-BP
Rural houses (n=5)
Urban houses (n=38)
Offices (n=12)
Figure S2. Component distribution of BTRs, BTHs, BPs in indoor dust of rural residential rooms, urban residential rooms, and urban offices from China.
S4
Table S1 Target analytes and some physicochemical property parameters Analyte
Full Name
Molecular Formula
CAS
Molecular Weight
Log Kowa
Henry's Law Constant b
1-H-BTR
1-hydrogen-benzotriazole
C6H5N3
95-14-7
119.12
1.17
1.47E-7
1-OH-BTR
1- hydroxybenzotriazole
C6H5N3O
2592-95-2
135.12
0.11
NA
4-Me-1-H-BTR
c
4-methyl-1-hydrogenbenzotriazole
C7H7N
29878-31-7
133.16
1.71
1.62E-7
5-Me-1-H-BTR
c
5-methyl-1-hydrogenbenzotriazole
C7H7N3
136-85-6
133.16
1.71
1.62E-7
5-Cl-BTR
5-Chloro-1-hydrogenbenzotriazole
C6H4ClN3
94-97-3
153.57
1.81
1.09E-7
5,6-2Me-1-HBTR
5,6-dimethyl-1-hydrogenbenzotriazole
C8H9N3
4184-79-6
147.18
NA
NA
BTH
benzothiazole
C7H5NS
128366-289
135.19
2.17
3.74E-7
2-OH-BTH
2-hydroxybenzothiazole
C7H5NOS
934-34-9
151.19
2.35
3.87E-7
2-NH2-BTH
2-aminobenzothiazole
C7H6N2S
136-95-8
150.20
2.00
1.32E-10
C8H7NS2
615-22-5
181.28
3.22
1.09E-8
2-(Thiocyanomethylthio) benzothiazole
C9H6N2S3
64441-45-8
238.35
3.12
6.49E-12
2-hydroxy-4methoxybenzophenone
C14H12O3
131-57-7
228.24
3.52
1.50E-8
2-OH-4-MeO-BP 4-OH-BP
4-hydroxybenzophenone
C13H10O2
1137-42-4
198.22
2.67
2.02E-10
2,4-2OH-BP
2,4-dihydroxybenzophenone
C13H10O3
131-56-6
214.22
2.96
2.65E-11
22'-2OH-4-MeOBP
2,2′-dihydroxy-4methoxybenzophenone
C14H12O4
131-53-3
244.24
3.82
1.97E-9
2,2′,4,4′tetrahydroxybenzophenone
C13H10O5
131-55-5
246.22
2.78
3.61E-16
2-Me-S-BTH 2-SCNMeS-BTH
22'44'-4OH-BP a
predicted data cited from chemspider.com, which is generated using the US Environmental Protection Agency’s EPISuite™, (KOWWIN v1.67 estimate); b
predicted data cited from chemspider.com, which is generated using the US Environmental Protection Agency’s EPISuite™, [HENRYWIN v3.10] (25 °C), with a unit of atm-m3/mole; c
The mixture of isomers 4-Me-1-H-BTR and 5- Me-1-H-BTR, i.e. tolyltriazole (TTR), was considered as a target BTR compound in this study; NA: not available.
S5
Table S2. Gradient elution processes used in LC for BTRs/BTHs and BPs BTRs/BTHs Time
BPs
Mobile B (%)
Time
Mobile B (%)
0.00
95
0.00
95
2.00
95
5.50
95
4.00
50
8.50
60
8.00
0
11.00
0
14.00
0
20.00
0
15.00
95
20.50
95
20.00
95
25.00
95
Note: The mobile phases were composed of methanol (A) and 10% methanol in Milli-Q water containing 2 mM of ammonium acetate (B); Flow rate = 200 µL/min.
S6
Table S3. Coefficients of MS/MS analysis for target analytes Q1
Q3
DP (volts)
EP (volts)
CE (volts)
CXP (volts)
120
65.2
60
5
35
1.5
1-OH-BTR
136.0
64.1
40
8
45
1.5
TTR
134.2
79.2
50
8
25
1.5
5,6-2Me-1-H-BTR
148.0
93.3
40
5
25
1.5
5-Cl-1-H-BTR
154.0
99.3
35
8
35
1.5
1-D6-BTR
124.2
69.1
60
5
35
1.5
BTH
136.0
109.2
60
8
40
1.5
2-OH-BTH
152.0
80.3
60
8
40
1.5
2-Me-S-BTH
182.0
167.3
50
10
30
1.5
2-NH2-BTH
151.0
124.1
60
6
35
1.5
2-SCNMeS-BTH
180.0
136.3
45
4
25
1.5
235
151
25
10
30
7
2-OH-4-MeO-BP
227
211
-30
-10
-27
-10
4-OH-BP
197
92
-30
-10
-40
-4
2,4-2OH-BP
213
91
-30
-10
-40
-4
22'-2OH-4-MeO-BP
243
93
-25
-10
-40
-5
22'44'-4OH-BP
245
91
-25
-10
-40
-5
233
217
-25
-10
-30
-7
Positive a 1-H-BTR
13
C12-2-OH-4-MeO-BP
Negative
13
b
C12-2-OH-4-MeO-BP
Note: DP=Declustering potential; EP=Entrance potential; CE= Collision energy; CXP: Collision cell exit potential. a
: Curtain gas (CUR): 10; Collision gas (CAD): 4; Ionspray voltage (IS): -4700; Temperature (TEM): 615; Ion source gas 1 (GS1): 68; Ion source gas 2 (GS2): 69; b
: CUR: 20; CAD: 7; IS: 4500; TEM: 500; GS1: 65; GS2: 70.
S7
Table S4. Recoveries (%) of BTRs, BTHs, and BPs from spiked procedure blank and spiked matrices (n=6) of indoor dust Analytes
spiked procedure blank (%)
spiked matrix corrected by internal standard (%)
1-H-BTR
75.9
93.8
1-OH-BTR
69.4
70.6
TTR
93.2
113.1
5,6-2Me-1-H-BTR
92.7
106.4
5-Cl-1-H-BTR
91.3
107.6
BTH
47.2
43.7
2-OH-BTH
94.1
96.6
2-Me-S-BTH
76.2
66.9
2-NH2-BTH
95.4
96.3
2-SCNMeS-BTH
94.8
97.4
2-OH-4-MeO-BP
94.6
98.5
4-OH-BP
93.3
88.4
2,4-2OH-BP
90.7
90.1
22'-2OH-4-MeO-BP
92.1
87.6
22'44'-4OH-BP
87.9
78.5
S8
Table S5. Concentrations and Detection Rates of BTRs, BTHs, and BPs in Indoor Dusts of rural residential rooms, urban residential rooms, and urban offices from China (ng/g) BTRs 1H-
1-OH-
BTR
BTR
TTR
_ 5,6-
5-Cl-
2Me-
BTR
ΣBTRs
BTHs BTH
1-H-
_
2-
2-
2-NH2-
2-
OH-
MeS-
BTH
BTH
BTH
BPs
_
2-
4-
2,4-
22'-
22'44'-
SCNMeS
OH-
OH-
2OH-
2OH-
4OH-
-BTH
4-
BP
BP
4-
BP
ΣBTHs
BTR
MeO-
MeO-
BP
BP
ΣBPs
Rural residential rooms (n=5) Median
1.148
1.306
0.4586
3.158
