Chinese Journal of Chromatography ›› 2022, Vol. 40 ›› Issue (4): 354-363.DOI: 10.3724/SP.J.1123.2021.10017
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WANG Mengmeng, XIE Linna, ZHU Ying*(), LU Yifu*()
Received:
2021-10-22
Online:
2022-04-08
Published:
2022-04-01
Contact:
ZHU Ying, LU Yifu
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CLC Number:
WANG Mengmeng, XIE Linna, ZHU Ying, LU Yifu. Determination of polybrominated diphenyl ethers in serum using isotope internal standard-gas chromatography-high resolution dual-focus magnetic mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(4): 354-363.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2021.10017
Compound | Abbreviation | Retention time/min | Monitoring ion [M+] (m/z) | Internal standard |
---|---|---|---|---|
2,2',4-Tribromodiphenyl ether | BDE-17 | 7.82 | 405.8027/407.8002 | 13C12-BDE-28 |
2,4,4'-Tribromodiphenyl ether | BDE-28 | 8.02 | 405.8027/407.8002 | 13C12-BDE-28 |
2,2',4,4'-Tetrabromodiphenyl ether | BDE-47 | 9.51 | 483.7132/485.7111 | 13C12-BDE-47 |
2,3',4,4'-Tetrabromodiphenyl ether | BDE-66 | 9.75 | 483.7132/485.7111 | 13C12-BDE-77 |
2,3',4',6-Tetrabromodiphenyl ether | BDE-71 | 9.31 | 483.7132/485.7111 | 13C12-BDE-47 |
2,2',3,4,4'-Pentabromodiphenyl ether | BDE-85 | 11.52 | 563.6216/565.6196 | 13C12-BDE-100 |
2,2',4,4',5-Pentabromodiphenyl ether | BDE-99 | 11.00 | 563.6216/565.6196 | 13C12-BDE-99 |
2,2',4,4',6-Pentabromodiphenyl ether | BDE-100 | 10.71 | 563.6216/565.6196 | 13C12-BDE-100 |
2,2',3,4,4',5'-Hexabromodiphenyl ether | BDE-138 | 12.86 | 641.5322/643.5302 | 13C12-BDE-138 |
2,2',4,4',5,5'-Hexabromodiphenyl ether | BDE-153 | 12.20 | 641.5322/643.5302 | 13C12-BDE-153 |
2,2',4,4',5,6'-Hexabromodiphenyl ether | BDE-154 | 11.78 | 641.5322/643.5302 | 13C12-BDE-154 |
2,2',3,4,4',5',6-Heptabromodiphenyl ether | BDE-183 | 13.78 | 721.4406/723.4386 | 13C12-BDE-183 |
2,3,3',4,4',5,6-Heptabromodiphenyl ether | BDE-190 | 14.95 | 721.4406/723.4386 | 13C12-BDE-183 |
Decabromodiphenyl ether | BDE-209 | 22.42 | 797.3355/799.3329 | 13C12-BDE-209 |
2,4,4'-Tribromodiphenyl ether-13C12 | 13C12-BDE-28 | 8.00 | 417.8429/419.8409 | |
2,2',4,4'-Tetrabromodiphenyl ether-13C12 | 13C12-BDE-47 | 9.50 | 497.7514/499.7493 | |
3,3',4,4'-Tetrabromodiphenyl ether-13C12 | 13C12-BDE-77 | 10.11 | 497.7514/499.7493 | |
2,2',4,4',5-Pentabromodiphenyl ether-13C12 | 13C12-BDE-99 | 11.00 | 575.6619/577.6598 | |
2,2',4,4',6-Pentabromodiphenyl ether-13C12 | 13C12-BDE-100 | 10.70 | 575.6619/577.6598 | |
2,2',3,4,4',5'-Hexabromodiphenyl ether-13C12 | 13C12-BDE-138 | 12.85 | 655.5704/657.5683 | |
2,2',4,4',5,5'-Hexabromodiphenyl ether-13C12 | 13C12-BDE-153 | 12.19 | 655.5704/657.5683 | |
2,2',4,4',5,6'-Hexabromodiphenyl ether-13C12 | 13C12-BDE-154 | 11.77 | 655.5704/657.5683 | |
2,2',3,4,4',5',6-Heptabromodiphenyl ether-13C12 | 13C12-BDE-183 | 13.77 | 733.4809/735.4788 | |
Decabromodiphenyl ether-13C12 | 13C12-BDE-209 | 22.41 | 809.3757/811.3731 |
Table 1 Retention times and MS parameters of the 14 polybrominated diphenyl ethers (PBDEs) and their corresponding isotope internal standards
Compound | Abbreviation | Retention time/min | Monitoring ion [M+] (m/z) | Internal standard |
---|---|---|---|---|
2,2',4-Tribromodiphenyl ether | BDE-17 | 7.82 | 405.8027/407.8002 | 13C12-BDE-28 |
2,4,4'-Tribromodiphenyl ether | BDE-28 | 8.02 | 405.8027/407.8002 | 13C12-BDE-28 |
2,2',4,4'-Tetrabromodiphenyl ether | BDE-47 | 9.51 | 483.7132/485.7111 | 13C12-BDE-47 |
2,3',4,4'-Tetrabromodiphenyl ether | BDE-66 | 9.75 | 483.7132/485.7111 | 13C12-BDE-77 |
2,3',4',6-Tetrabromodiphenyl ether | BDE-71 | 9.31 | 483.7132/485.7111 | 13C12-BDE-47 |
2,2',3,4,4'-Pentabromodiphenyl ether | BDE-85 | 11.52 | 563.6216/565.6196 | 13C12-BDE-100 |
2,2',4,4',5-Pentabromodiphenyl ether | BDE-99 | 11.00 | 563.6216/565.6196 | 13C12-BDE-99 |
2,2',4,4',6-Pentabromodiphenyl ether | BDE-100 | 10.71 | 563.6216/565.6196 | 13C12-BDE-100 |
2,2',3,4,4',5'-Hexabromodiphenyl ether | BDE-138 | 12.86 | 641.5322/643.5302 | 13C12-BDE-138 |
2,2',4,4',5,5'-Hexabromodiphenyl ether | BDE-153 | 12.20 | 641.5322/643.5302 | 13C12-BDE-153 |
2,2',4,4',5,6'-Hexabromodiphenyl ether | BDE-154 | 11.78 | 641.5322/643.5302 | 13C12-BDE-154 |
2,2',3,4,4',5',6-Heptabromodiphenyl ether | BDE-183 | 13.78 | 721.4406/723.4386 | 13C12-BDE-183 |
2,3,3',4,4',5,6-Heptabromodiphenyl ether | BDE-190 | 14.95 | 721.4406/723.4386 | 13C12-BDE-183 |
Decabromodiphenyl ether | BDE-209 | 22.42 | 797.3355/799.3329 | 13C12-BDE-209 |
2,4,4'-Tribromodiphenyl ether-13C12 | 13C12-BDE-28 | 8.00 | 417.8429/419.8409 | |
2,2',4,4'-Tetrabromodiphenyl ether-13C12 | 13C12-BDE-47 | 9.50 | 497.7514/499.7493 | |
3,3',4,4'-Tetrabromodiphenyl ether-13C12 | 13C12-BDE-77 | 10.11 | 497.7514/499.7493 | |
2,2',4,4',5-Pentabromodiphenyl ether-13C12 | 13C12-BDE-99 | 11.00 | 575.6619/577.6598 | |
2,2',4,4',6-Pentabromodiphenyl ether-13C12 | 13C12-BDE-100 | 10.70 | 575.6619/577.6598 | |
2,2',3,4,4',5'-Hexabromodiphenyl ether-13C12 | 13C12-BDE-138 | 12.85 | 655.5704/657.5683 | |
2,2',4,4',5,5'-Hexabromodiphenyl ether-13C12 | 13C12-BDE-153 | 12.19 | 655.5704/657.5683 | |
2,2',4,4',5,6'-Hexabromodiphenyl ether-13C12 | 13C12-BDE-154 | 11.77 | 655.5704/657.5683 | |
2,2',3,4,4',5',6-Heptabromodiphenyl ether-13C12 | 13C12-BDE-183 | 13.77 | 733.4809/735.4788 | |
Decabromodiphenyl ether-13C12 | 13C12-BDE-209 | 22.41 | 809.3757/811.3731 |
Fig. 2 Chromatograms of (a) the 14 PBDEs and (b) their isotope internal standards a. The mass concentrations of 13 PBDEs were 50 μg/L and that of BDE-209 was 250 μg/L; b. The mass concentrations of the isotope internal standards of 13 PBDEs were 50 μg/L and that of 13C12-BDE-209 was 250 μg/L.
Compound | Linear range/(μg/L) | Linear equation | r | MDL/(μg/L) | LOQ/(μg/L) |
---|---|---|---|---|---|
BDE-17 | 0.08-5 | y=0.7414x+0.0435 | 0.999 | 0.02 | 0.07 |
BDE-28 | 0.08-5 | y=0.7717x+0.0006 | 0.999 | 0.02 | 0.06 |
BDE-47 | 0.08-5 | y=1.0190x+0.009 | 0.999 | 0.01 | 0.04 |
BDE-66 | 0.08-5 | y=0.6454x-0.0144 | 0.999 | 0.03 | 0.09 |
BDE-71 | 0.08-5 | y=0.7503x+0.0230 | 0.999 | 0.02 | 0.08 |
BDE-85 | 0.08-5 | y=0.5084x-0.0226 | 0.998 | 0.03 | 0.09 |
BDE-99 | 0.08-5 | y=0.8007x+0.0084 | 0.999 | 0.03 | 0.10 |
BDE-100 | 0.08-5 | y=0.9413x-0.0028 | 0.999 | 0.02 | 0.06 |
BDE-138 | 0.08-5 | y=1.0211x-0.0127 | 0.999 | 0.04 | 0.13 |
BDE-153 | 0.08-5 | y=0.9191x+0.0155 | 0.999 | 0.03 | 0.10 |
BDE-154 | 0.08-5 | y=0.9278x+0.0002 | 0.999 | 0.03 | 0.09 |
BDE-183 | 0.08-5 | y=0.8414x-0.0075 | 0.999 | 0.04 | 0.12 |
BDE-190 | 0.08-5 | y=0.2424x-0.0073 | 0.999 | 0.08 | 0.27 |
BDE-209 | 0.40-25 | y=0.5393x+0.0363 | 0.999 | 0.51 | 1.70 |
Table 2 Linear ranges, linear equations, correlation coefficients (r), method detection limits (MDLs), and limits of quantification (LOQs) of the 14 PBDEs
Compound | Linear range/(μg/L) | Linear equation | r | MDL/(μg/L) | LOQ/(μg/L) |
---|---|---|---|---|---|
BDE-17 | 0.08-5 | y=0.7414x+0.0435 | 0.999 | 0.02 | 0.07 |
BDE-28 | 0.08-5 | y=0.7717x+0.0006 | 0.999 | 0.02 | 0.06 |
BDE-47 | 0.08-5 | y=1.0190x+0.009 | 0.999 | 0.01 | 0.04 |
BDE-66 | 0.08-5 | y=0.6454x-0.0144 | 0.999 | 0.03 | 0.09 |
BDE-71 | 0.08-5 | y=0.7503x+0.0230 | 0.999 | 0.02 | 0.08 |
BDE-85 | 0.08-5 | y=0.5084x-0.0226 | 0.998 | 0.03 | 0.09 |
BDE-99 | 0.08-5 | y=0.8007x+0.0084 | 0.999 | 0.03 | 0.10 |
BDE-100 | 0.08-5 | y=0.9413x-0.0028 | 0.999 | 0.02 | 0.06 |
BDE-138 | 0.08-5 | y=1.0211x-0.0127 | 0.999 | 0.04 | 0.13 |
BDE-153 | 0.08-5 | y=0.9191x+0.0155 | 0.999 | 0.03 | 0.10 |
BDE-154 | 0.08-5 | y=0.9278x+0.0002 | 0.999 | 0.03 | 0.09 |
BDE-183 | 0.08-5 | y=0.8414x-0.0075 | 0.999 | 0.04 | 0.12 |
BDE-190 | 0.08-5 | y=0.2424x-0.0073 | 0.999 | 0.08 | 0.27 |
BDE-209 | 0.40-25 | y=0.5393x+0.0363 | 0.999 | 0.51 | 1.70 |
Compound | 0.2 (1.0) μg/L* | 0.4 (2.0) μg/L* | 0.8 (4.0) μg/L* | Intra-day RSD/% | Inter-day RSD/% | |||
---|---|---|---|---|---|---|---|---|
Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | |||
BDE-17 | 92.5 | 4.0 | 82.9 | 4.0 | 100.2 | 6.2 | 4.8 | 8.4 |
BDE-28 | 118.6 | 2.5 | 119.3 | 4.1 | 120.7 | 6.6 | 4.4 | 8.4 |
BDE-47 | 105.2 | 2.8 | 113.2 | 2.5 | 97.2 | 6.3 | 3.8 | 4.8 |
BDE-66 | 118.9 | 3.8 | 116.5 | 1.9 | 115.4 | 6.6 | 4.1 | 8.0 |
BDE-71 | 75.5 | 5.6 | 81.6 | 4.1 | 99.7 | 6.4 | 5.3 | 12.4 |
BDE-85 | 119.7 | 3.7 | 116.8 | 3.7 | 108.2 | 4.7 | 4.0 | 9.5 |
BDE-99 | 102.3 | 11.9 | 109.3 | 2.2 | 115.0 | 3.4 | 5.8 | 10.9 |
BDE-100 | 100.1 | 7.5 | 106.6 | 1.4 | 119.4 | 6.7 | 5.2 | 5.7 |
BDE-138 | 98.7 | 6.4 | 99.9 | 4.6 | 109.8 | 6.1 | 5.7 | 9.1 |
BDE-153 | 88.8 | 5.7 | 98.7 | 2.6 | 107.1 | 7.3 | 5.2 | 8.6 |
BDE-154 | 94.7 | 11.4 | 104.3 | 2.2 | 110.0 | 8.9 | 7.5 | 5.2 |
BDE-183 | 88.8 | 10.4 | 97.8 | 3.1 | 103.8 | 7.3 | 6.9 | 9.6 |
BDE-190 | 88.1 | 15.4 | 97.1 | 5.5 | 93.9 | 11.9 | 10.9 | 7.6 |
BDE-209 | 89.1 | 13.9 | 89.8 | 5.2 | 97.3 | 3.8 | 7.6 | 4.2 |
Table 3 Spiked recoveries and intra-day and inter-day relative standard deviations (RSDs) of the 14 PBDEs in serum samples (n=6)
Compound | 0.2 (1.0) μg/L* | 0.4 (2.0) μg/L* | 0.8 (4.0) μg/L* | Intra-day RSD/% | Inter-day RSD/% | |||
---|---|---|---|---|---|---|---|---|
Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | |||
BDE-17 | 92.5 | 4.0 | 82.9 | 4.0 | 100.2 | 6.2 | 4.8 | 8.4 |
BDE-28 | 118.6 | 2.5 | 119.3 | 4.1 | 120.7 | 6.6 | 4.4 | 8.4 |
BDE-47 | 105.2 | 2.8 | 113.2 | 2.5 | 97.2 | 6.3 | 3.8 | 4.8 |
BDE-66 | 118.9 | 3.8 | 116.5 | 1.9 | 115.4 | 6.6 | 4.1 | 8.0 |
BDE-71 | 75.5 | 5.6 | 81.6 | 4.1 | 99.7 | 6.4 | 5.3 | 12.4 |
BDE-85 | 119.7 | 3.7 | 116.8 | 3.7 | 108.2 | 4.7 | 4.0 | 9.5 |
BDE-99 | 102.3 | 11.9 | 109.3 | 2.2 | 115.0 | 3.4 | 5.8 | 10.9 |
BDE-100 | 100.1 | 7.5 | 106.6 | 1.4 | 119.4 | 6.7 | 5.2 | 5.7 |
BDE-138 | 98.7 | 6.4 | 99.9 | 4.6 | 109.8 | 6.1 | 5.7 | 9.1 |
BDE-153 | 88.8 | 5.7 | 98.7 | 2.6 | 107.1 | 7.3 | 5.2 | 8.6 |
BDE-154 | 94.7 | 11.4 | 104.3 | 2.2 | 110.0 | 8.9 | 7.5 | 5.2 |
BDE-183 | 88.8 | 10.4 | 97.8 | 3.1 | 103.8 | 7.3 | 6.9 | 9.6 |
BDE-190 | 88.1 | 15.4 | 97.1 | 5.5 | 93.9 | 11.9 | 10.9 | 7.6 |
BDE-209 | 89.1 | 13.9 | 89.8 | 5.2 | 97.3 | 3.8 | 7.6 | 4.2 |
Compound | Experimental result/ (ng/g) | Certified value/ (ng/g) |
---|---|---|
BDE-17 | 0.453 | 0.458±0.032 |
BDE-28 | 0.466 | 0.462±0.019 |
BDE-47 | 0.656 | 0.651±0.029 |
BDE-66 | 0.471 | 0.440±0.041 |
BDE-99 | 0.484 | 0.492±0.015 |
BDE-100 | 0.489 | 0.475±0.027 |
BDE-153 | 0.412 | 0.455±0.054 |
BDE-154 | 0.418 | 0.441±0.039 |
BDE-183 | 0.425 | 0.453±0.042 |
Table 4 Comparison of experimental results and certified values of SRM1958 (n=6)
Compound | Experimental result/ (ng/g) | Certified value/ (ng/g) |
---|---|---|
BDE-17 | 0.453 | 0.458±0.032 |
BDE-28 | 0.466 | 0.462±0.019 |
BDE-47 | 0.656 | 0.651±0.029 |
BDE-66 | 0.471 | 0.440±0.041 |
BDE-99 | 0.484 | 0.492±0.015 |
BDE-100 | 0.489 | 0.475±0.027 |
BDE-153 | 0.412 | 0.455±0.054 |
BDE-154 | 0.418 | 0.441±0.039 |
BDE-183 | 0.425 | 0.453±0.042 |
Method | Sample volume/ mL | MDLs/(μg/L) | |||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
BDE- 17 | BDE- 28 | BDE- 71 | BDE- 47 | BDE- 66 | BDE- 100 | BDE- 99 | BDE- 85 | BDE- 154 | BDE- 153 | BDE- 138 | BDE- 183 | BDE- 190 | BDE- 209 | ||
GC-MS/MS[ | 1 | 0.03 | 0.03 | / | 0.06 | 0.03 | 0.04 | 0.05 | / | 0.03 | 0.04 | / | 0.05 | 0.2 | / |
GC/ITD-MS/MS[ | 1 | 0.4 | 0.3 | / | 0.2 | 0.07 | 0.5 | 0.1 | 0.3 | 0.2 | 0.1 | / | 1.3 | / | / |
GC-HRMS[ | 2~5 | / | 0.01 | / | 0.02 | / | 0.02 | 0.03 | 0.04 | 0.02 | 0.02 | 0.03 | 0.04 | / | / |
This method | 0.5 | 0.02 | 0.02 | 0.02 | 0.01 | 0.03 | 0.02 | 0.03 | 0.03 | 0.03 | 0.03 | 0.04 | 0.04 | 0.08 | 0.51 |
Table 5 Comparison of the developed method with other reported methods for the determination of PBDEs in serum samples
Method | Sample volume/ mL | MDLs/(μg/L) | |||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
BDE- 17 | BDE- 28 | BDE- 71 | BDE- 47 | BDE- 66 | BDE- 100 | BDE- 99 | BDE- 85 | BDE- 154 | BDE- 153 | BDE- 138 | BDE- 183 | BDE- 190 | BDE- 209 | ||
GC-MS/MS[ | 1 | 0.03 | 0.03 | / | 0.06 | 0.03 | 0.04 | 0.05 | / | 0.03 | 0.04 | / | 0.05 | 0.2 | / |
GC/ITD-MS/MS[ | 1 | 0.4 | 0.3 | / | 0.2 | 0.07 | 0.5 | 0.1 | 0.3 | 0.2 | 0.1 | / | 1.3 | / | / |
GC-HRMS[ | 2~5 | / | 0.01 | / | 0.02 | / | 0.02 | 0.03 | 0.04 | 0.02 | 0.02 | 0.03 | 0.04 | / | / |
This method | 0.5 | 0.02 | 0.02 | 0.02 | 0.01 | 0.03 | 0.02 | 0.03 | 0.03 | 0.03 | 0.03 | 0.04 | 0.04 | 0.08 | 0.51 |
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