Chinese Journal of Chromatography ›› 2020, Vol. 38 ›› Issue (12): 1456-1464.DOI: 10.3724/SP.J.1123.2020.07021
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LIN Xiao, QIU Tian, ZHANG Xu, HU Xiaojian, YANG Yanwei, ZHU Ying*()
Received:
2020-07-22
Online:
2020-12-08
Published:
2020-12-01
Contact:
ZHU Ying
CLC Number:
LIN Xiao, QIU Tian, ZHANG Xu, HU Xiaojian, YANG Yanwei, ZHU Ying. Determination of eight environmental phenols in human urine samples by high-throughput solid-phase extraction-ultra-performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(12): 1456-1464.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2020.07021
Time/min | Flow rate/(mL/min) | φ(A)/% | φ(B)/% | Curve |
---|---|---|---|---|
Initial | 0.3 | 80 | 20 | initial |
2.00 | 0.3 | 80 | 20 | 6 |
15.00 | 0.3 | 20 | 80 | 6 |
15.30 | 0.3 | 20 | 80 | 6 |
16.00 | 0.3 | 80 | 20 | 6 |
18.00 | 0.3 | 80 | 20 | 6 |
Table 1 Mobile phase gradient of UPLC
Time/min | Flow rate/(mL/min) | φ(A)/% | φ(B)/% | Curve |
---|---|---|---|---|
Initial | 0.3 | 80 | 20 | initial |
2.00 | 0.3 | 80 | 20 | 6 |
15.00 | 0.3 | 20 | 80 | 6 |
15.30 | 0.3 | 20 | 80 | 6 |
16.00 | 0.3 | 80 | 20 | 6 |
18.00 | 0.3 | 80 | 20 | 6 |
Compound | Retention time/min | Parent ion (m/z) | Daughter ion (m/z) | Cone voltage/V | Collision energy/eV |
---|---|---|---|---|---|
Bisphenol A (BPA) | 8.09 | 227.0 | 212.0* | 10 | 25 |
133.0 | 10 | 18 | |||
Bisphenol F (BPF) | 6.31 | 199.0 | 93.0* | 10 | 21 |
105.0 | 10 | 20 | |||
Tetrachlorobisphenol A | 12.69 | 364.7 | 285.9 | 60 | 34 |
(TCBPA) | 313.9* | 60 | 22 | ||
Tetrabromobisphenol A | 13.76 | 543.0 | 418.0* | 10 | 40 |
(TBBPA) | 420.0 | 10 | 42 | ||
Bisphenol S (BPS) | 3.78 | 248.9 | 107.8* | 8 | 26 |
91.8 | 8 | 32 | |||
Bisphenol AF (BPAF) | 10.12 | 334.9 | 264.9* | 8 | 38 |
196.9 | 8 | 22 | |||
Bisphenol B (BPB) | 9.15 | 241.8 | 146.9 | 10 | 28 |
212.0* | 10 | 18 | |||
Triclosan (TCS) | 13.43 | 286.8 | 35.0* | 20 | 10 |
289.0 | 35.0 | 20 | 12 | ||
Compound | Retention time/min | Parent ion (m/z) | Daughter ion (m/z) | Cone voltage/V | Collision energy/eV |
BPA-d16 | 7.98 | 241.2 | 223.2 | 10 | 18 |
BPF-d10 | 6.19 | 209.0 | 97.0 | 30 | 23 |
TCBPA-13C12 | 12.70 | 376.9 | 326.0 | 6 | 32 |
TBBPA-13C12 | 13.75 | 554.9 | 431.0 | 10 | 41 |
BPS-13C12 | 3.77 | 260.9 | 113.8 | 44 | 30 |
BPAF-13C12 | 10.12 | 346.9 | 277.0 | 10 | 40 |
BPB-13C12 | 9.15 | 253.0 | 224.0 | 8 | 16 |
TCS-13C12 | 13.42 | 299.0 | 35.0 | 20 | 12 |
Table 2 MS parameters of the eight target compounds and isotope internal standards
Compound | Retention time/min | Parent ion (m/z) | Daughter ion (m/z) | Cone voltage/V | Collision energy/eV |
---|---|---|---|---|---|
Bisphenol A (BPA) | 8.09 | 227.0 | 212.0* | 10 | 25 |
133.0 | 10 | 18 | |||
Bisphenol F (BPF) | 6.31 | 199.0 | 93.0* | 10 | 21 |
105.0 | 10 | 20 | |||
Tetrachlorobisphenol A | 12.69 | 364.7 | 285.9 | 60 | 34 |
(TCBPA) | 313.9* | 60 | 22 | ||
Tetrabromobisphenol A | 13.76 | 543.0 | 418.0* | 10 | 40 |
(TBBPA) | 420.0 | 10 | 42 | ||
Bisphenol S (BPS) | 3.78 | 248.9 | 107.8* | 8 | 26 |
91.8 | 8 | 32 | |||
Bisphenol AF (BPAF) | 10.12 | 334.9 | 264.9* | 8 | 38 |
196.9 | 8 | 22 | |||
Bisphenol B (BPB) | 9.15 | 241.8 | 146.9 | 10 | 28 |
212.0* | 10 | 18 | |||
Triclosan (TCS) | 13.43 | 286.8 | 35.0* | 20 | 10 |
289.0 | 35.0 | 20 | 12 | ||
Compound | Retention time/min | Parent ion (m/z) | Daughter ion (m/z) | Cone voltage/V | Collision energy/eV |
BPA-d16 | 7.98 | 241.2 | 223.2 | 10 | 18 |
BPF-d10 | 6.19 | 209.0 | 97.0 | 30 | 23 |
TCBPA-13C12 | 12.70 | 376.9 | 326.0 | 6 | 32 |
TBBPA-13C12 | 13.75 | 554.9 | 431.0 | 10 | 41 |
BPS-13C12 | 3.77 | 260.9 | 113.8 | 44 | 30 |
BPAF-13C12 | 10.12 | 346.9 | 277.0 | 10 | 40 |
BPB-13C12 | 9.15 | 253.0 | 224.0 | 8 | 16 |
TCS-13C12 | 13.42 | 299.0 | 35.0 | 20 | 12 |
96-well SPE plate | BPF/% | TCS/% |
---|---|---|
Oasis HLB (60 mg) | 79.6-83.3 | 83.6-106.0 |
Oasis HLB (30 mg) | 100.3-128.1 | 88.7-139.8 |
Prime HLB (30 mg) | 59.4-62.2 | 46.4-130.0 |
Table 3 Recoveries of BPF and TCS with three types of SPE columns
96-well SPE plate | BPF/% | TCS/% |
---|---|---|
Oasis HLB (60 mg) | 79.6-83.3 | 83.6-106.0 |
Oasis HLB (30 mg) | 100.3-128.1 | 88.7-139.8 |
Prime HLB (30 mg) | 59.4-62.2 | 46.4-130.0 |
Compound | Internal standard | Regression equation | Linear range/(μg/L) | r | LOD/(μg/L) | LOQ/(μg/L) |
---|---|---|---|---|---|---|
BPA | BPA-d16 | Y=0.00473X+1.74×10-4 | 0.5-50 | 0.9995 | 0.07 | 0.23 |
BPF | BPF-d10 | Y=0.00267X-3.62×10-4 | 0.01-50 | 0.9997 | 0.002 | 0.007 |
TCBPA | TCBPA-13C12 | Y=0.0149X-3.49×10-5 | 0.05-50 | 0.9998 | 0.009 | 0.03 |
TBBPA | TBBPA-13C12 | Y=0.0189X+3.5×10-5 | 0.01-50 | 0.9995 | 0.004 | 0.01 |
BPB | BPB-13C12 | Y=0.00097X+4.8×10-5 | 1.00-50 | 0.9997 | 0.24 | 0.79 |
BPS | BPS-13C12 | Y=0.0243X+3.75×10-4 | 0.05-50 | 0.9994 | 0.007 | 0.02 |
BPAF | BPAF-13C12 | Y=0.0213X+4.60×10-4 | 0.50-50 | 0.9995 | 0.09 | 0.30 |
TCS | TCS-13C12 | Y=0.0162X+1.77×10-3 | 5.00-200 | 0.9994 | 1.09 | 3.63 |
Table 4 Regression equations, linear ranges, correlation coefficients (r), LODs and LOQs of the eight environmental phenols
Compound | Internal standard | Regression equation | Linear range/(μg/L) | r | LOD/(μg/L) | LOQ/(μg/L) |
---|---|---|---|---|---|---|
BPA | BPA-d16 | Y=0.00473X+1.74×10-4 | 0.5-50 | 0.9995 | 0.07 | 0.23 |
BPF | BPF-d10 | Y=0.00267X-3.62×10-4 | 0.01-50 | 0.9997 | 0.002 | 0.007 |
TCBPA | TCBPA-13C12 | Y=0.0149X-3.49×10-5 | 0.05-50 | 0.9998 | 0.009 | 0.03 |
TBBPA | TBBPA-13C12 | Y=0.0189X+3.5×10-5 | 0.01-50 | 0.9995 | 0.004 | 0.01 |
BPB | BPB-13C12 | Y=0.00097X+4.8×10-5 | 1.00-50 | 0.9997 | 0.24 | 0.79 |
BPS | BPS-13C12 | Y=0.0243X+3.75×10-4 | 0.05-50 | 0.9994 | 0.007 | 0.02 |
BPAF | BPAF-13C12 | Y=0.0213X+4.60×10-4 | 0.50-50 | 0.9995 | 0.09 | 0.30 |
TCS | TCS-13C12 | Y=0.0162X+1.77×10-3 | 5.00-200 | 0.9994 | 1.09 | 3.63 |
Compound | Spiked/ (μg/L) | Recovery/ % | Inter-day RSD/% | Intra-day RSD/% | Compound | Spiked/ (μg/L) | Recovery/ % | Inter-day RSD/% | Intra-day RSD/% |
---|---|---|---|---|---|---|---|---|---|
BPA | 2.5 | 98.7 | 9.6 | 12. 3 | BPB | 2.5 | 101.9 | 3.3 | 4.2 |
5 | 100.0 | 5.8 | 9.4 | 5 | 100.7 | 4.8 | 6.6 | ||
25 | 88.7 | 12.0 | 7.2 | 25 | 93.9 | 0.8 | 6.9 | ||
BPF | 2.5 | 89.2 | 10.6 | 11.9 | BPS | 2.5 | 98.2 | 2.0 | 4.5 |
5 | 83.5 | 9.3 | 15.2 | 5 | 96.4 | 2.3 | 3.4 | ||
25 | 81.0 | 8.1 | 14.0 | 25 | 94.6 | 0.5 | 3.2 | ||
TCBPA | 2.5 | 93.5 | 1.2 | 6.8 | BPAF | 2.5 | 95.4 | 2.3 | 3.4 |
5 | 95.7 | 2.4 | 4.5 | 5 | 96.6 | 2.1 | 3.0 | ||
25 | 93.6 | 0.4 | 4.9 | 25 | 92.6 | 0.7 | 3.2 | ||
TBBPA | 2.5 | 96.0 | 1.7 | 3.9 | TCS | 2.5 | 94.4 | 17.2 | 17.8 |
5 | 97.4 | 3.6 | 5.7 | 5 | 97.6 | 19.4 | 11.8 | ||
25 | 93.9 | 1.2 | 2.5 | 25 | 94.7 | 6.2 | 8.4 |
Table 5 Recoveries and RSDs of the eight environmental phenols at three spiked levels (n=5)
Compound | Spiked/ (μg/L) | Recovery/ % | Inter-day RSD/% | Intra-day RSD/% | Compound | Spiked/ (μg/L) | Recovery/ % | Inter-day RSD/% | Intra-day RSD/% |
---|---|---|---|---|---|---|---|---|---|
BPA | 2.5 | 98.7 | 9.6 | 12. 3 | BPB | 2.5 | 101.9 | 3.3 | 4.2 |
5 | 100.0 | 5.8 | 9.4 | 5 | 100.7 | 4.8 | 6.6 | ||
25 | 88.7 | 12.0 | 7.2 | 25 | 93.9 | 0.8 | 6.9 | ||
BPF | 2.5 | 89.2 | 10.6 | 11.9 | BPS | 2.5 | 98.2 | 2.0 | 4.5 |
5 | 83.5 | 9.3 | 15.2 | 5 | 96.4 | 2.3 | 3.4 | ||
25 | 81.0 | 8.1 | 14.0 | 25 | 94.6 | 0.5 | 3.2 | ||
TCBPA | 2.5 | 93.5 | 1.2 | 6.8 | BPAF | 2.5 | 95.4 | 2.3 | 3.4 |
5 | 95.7 | 2.4 | 4.5 | 5 | 96.6 | 2.1 | 3.0 | ||
25 | 93.6 | 0.4 | 4.9 | 25 | 92.6 | 0.7 | 3.2 | ||
TBBPA | 2.5 | 96.0 | 1.7 | 3.9 | TCS | 2.5 | 94.4 | 17.2 | 17.8 |
5 | 97.4 | 3.6 | 5.7 | 5 | 97.6 | 19.4 | 11.8 | ||
25 | 93.9 | 1.2 | 2.5 | 25 | 94.7 | 6.2 | 8.4 |
Compound | Contents/(μg/L) | |
---|---|---|
This method | NIST certified | |
BPA | 2.75 | 3.11 |
TCS | 17.8 | 18.0 |
Table 6 Average measured contents and certified contents of SRM 3672 (n=6)
Compound | Contents/(μg/L) | |
---|---|---|
This method | NIST certified | |
BPA | 2.75 | 3.11 |
TCS | 17.8 | 18.0 |
Compound | DF/% | Range/ (μg/L) | Mean/ (μg/L) | GM/ (μg/L) | 1st quartile/ (μg/L) | Median/ (μg/L) | 3rd quartile/ (μg/L) |
---|---|---|---|---|---|---|---|
BPA | 100 | 0.09-7.58 | 1.00 | 0.63 | 0.31 | 0.69 | 1.33 |
BPF | 21.9 | ND-2.34 | 0.122 | 0.0017 | 0.00 | 0.00 | 0.00 |
TCBPA | 23.4 | ND-0.12 | 0.0084 | 0.0069 | 0.00 | 0.00050 | 0.0041 |
TBBPA | 46.9 | ND-1.26 | 0.029 | 0.0054 | 0.00 | 0.0032 | 0.014 |
BPB | 0.00 | ND | 0.00 | 0.00 | 0.00 | 0.00 | |
BPS | 96.9 | ND-32.5 | 0.766 | 0.088 | 0.032 | 0.086 | 0.21 |
BPAF | 0.00 | ND | 0.00 | 0.00 | 0.00 | 0.00 | |
TCS | 57.8 | ND-161 | 8.35 | 1.81 | 0.33 | 1.44 | 3.73 |
Table 7 Determination values of the eight environmental phenols in human urine
Compound | DF/% | Range/ (μg/L) | Mean/ (μg/L) | GM/ (μg/L) | 1st quartile/ (μg/L) | Median/ (μg/L) | 3rd quartile/ (μg/L) |
---|---|---|---|---|---|---|---|
BPA | 100 | 0.09-7.58 | 1.00 | 0.63 | 0.31 | 0.69 | 1.33 |
BPF | 21.9 | ND-2.34 | 0.122 | 0.0017 | 0.00 | 0.00 | 0.00 |
TCBPA | 23.4 | ND-0.12 | 0.0084 | 0.0069 | 0.00 | 0.00050 | 0.0041 |
TBBPA | 46.9 | ND-1.26 | 0.029 | 0.0054 | 0.00 | 0.0032 | 0.014 |
BPB | 0.00 | ND | 0.00 | 0.00 | 0.00 | 0.00 | |
BPS | 96.9 | ND-32.5 | 0.766 | 0.088 | 0.032 | 0.086 | 0.21 |
BPAF | 0.00 | ND | 0.00 | 0.00 | 0.00 | 0.00 | |
TCS | 57.8 | ND-161 | 8.35 | 1.81 | 0.33 | 1.44 | 3.73 |
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