Abstract
A pulsed large-volume injection gas chromatography coupled with electron-capture negative ionization quadrupole mass spectrometry (pLVI-GC/ECNI-qMS) was developed for the simultaneous determination of typical halogenated persistent organic pollutants (H-POPs). By monitoring the characteristic ions of large mass-to-charge ratio (m/z) for each of the H-POPs rather than the chlorine and/or bromine ions, this method avoided the possible interferences arising from the H-POPs themselves and from complex matrices encountered frequently in current GC/qMS methods; and allowed, on the other hand, the use of 13C-labeled and perdeuterated analogues as internal standards for reliable quantification. pLVI up to 120 µL improved the instrumental detection limits down to pg-fg mL−1, comparable to or lower than those obtained by the recognized GC/high-resolution MS methods reported so far. The H-POPs including 12 polybrominated diphenyl ethers, 1 polybrominated biphenyl, 10 polychlorinated biphenyls (PCBs), 4 hexachlorocyclohexane isomers, and hexachlorobenzene were involved in this study. The method developed demonstrated good linearity (r 2=0.9904−0.9999) within 0.5 to 50,000 pg mL−1 for PCBs and 0.05 to 5000 pg mL−1 for other H-POPs, and was satisfactory in terms of both repeatability (0.07%–2.2%) and reproducibility (2.1%–8.4%). It was validated by analyzing a NIST standard reference material SRM-1946 of Lake Superior fish tissue with low 0.01 to 63 pg g−1 method detection limits, and successfully applied to the determination of the H-POPs in five reference materials of different matrices.
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Eljarrat, E.; Barcelo, D. Priority Lists for Persistent Organic Pollutants and Emerging Contaminants Based on Their Relative Toxic Potency in Environmental Samples. Trends Anal. Chem. 2003, 22, 655–665.
Koester, C. J.; Simonich, S. L.; Esser, B. K. Environmental Analysis. Anal. Chem. 2003, 75, 2813–2829.
Liu, H. X.; Zhang, Q. H.; Cai, Z. W.; Li, A.; Wang, Y. W.; Jiang, G. B. Separation of Polybrominated Diphenyl Ethers, Polychlorinated Biphenyls, Polychlorinated Dibenzo-p-Dioxins, and Dibenzo-Furans in Environmental Samples Using Silica Gel and Florisil Fractionation Chromatography. Anal. Chim. Acta. 2006, 557, 314–320.
Pirard, C.; De Pauw, E.; Focant, J.-F. New Strategy for Comprehensive Analysis of Polybrominated Diphenyl Ethers, Polychlorinated Dibenzo-p-Dioxins, Polychlorinated Dibenzofurans, and Polychlorinated Biphenyls by Gas Chromatography Coupled with Mass Spectrometry. J. Chromatogr. A. 2003, 998, 169–181.
Hites, R. A. Polybrominated Diphenyl Ethers in the Environment and in People: A Meta-Analysis of Concentrations. Environ. Sci. Technol. 2004, 38, 945–956.
Santos, F. J.; Galceran, M. T. The Application of Gas Chromatography to Environmental Analysis. Trends Anal. Chem. 2002, 21, 672–685.
de Boer, J. Capillary Gas Chromatography for the Determination of Halogenated Microcontaminants. J. Chromatogr. A. 1999, 843, 179–198.
Chu, S. G.; Hong, C.-S.; Rattner, B. A.; McGowan, P. C. Methodological Refinements in the Determination of 146 Polychlorinated Biphenyls, Including Nonortho-and Monoortho-Substituted PCBs, and 26 organochlorine pesticides as Demonstrated in Heron Eggs. Anal. Chem. 2003, 75, 1058–1066.
Alaee, M.; Backus, S.; Cannon, C. Potential Interference of PBDEs in the Determination of PCBs and Other Organochlorine Contaminants Using Electron Capture Detection. J. Sep. Sci. 2001, 24, 465–469.
Korytar, P.; Haglund, P.; de Boer, J.; Brinkman, U. A. T. Comprehensive Two-Dimensional Gas Chromatography for the Analysis of Organohalogenated Microcontaminants. Trends Anal. Chem. 2006, 25, 373–396.
Liu, H. X.; Zhang, Q. H.; Song, M. Y.; Jiang, G. B.; Cai, Z. W. Method of Development for the Analysis of Polybrominated Diphenyl Ethers, Polychlorinated Biphenyls, Polychlorinated Dibenzo-p-Dioxins, and Dibenzo-Furans in Single Extract of Sediment Samples. Talanta. 2006, 70, 20–25.
Zeng, E. Y.; Chou, C. C.; Yu, C. Potential Application of Gas Chromatography/Tandem Mass Spectrometry in the Measurement of Coeluting Isomers. Anal. Chem. 2002, 74, 4513–4518.
Clarkson, P. J.; Larrazabal-Moya, D.; Staton, I.; McLeod, C. W.; Ward, D. B.; Sharifi, V. N.; Swithenbank, J. The Use of Tree Bark as a Passive Sampler for Polychlorinated Dibenzo-p-Dioxins and Furans. Int. J. Environ. Anal. Chem. 2002, 82, 843–850.
Cai, Z. W.; Jiang, G. B. Determination of Polybrominated Diphenyl Ethers in Soil from e-Waste Recycling Site. Talanta 2006, 70, 88–90.
Hernandez, F.; Portoles, T.; Pitarch, E.; Lopez, F. J.; Beltran, J.; Vazquez, C. Potential of Gas Chromatography Coupled to Triple Quadrupole Mass Spectrometry for Quantification and Confirmation of Organohalogen Xenoestrogen Compounds in Human Breast Tissues. Anal. Chem. 2005, 77, 7662–7672.
Focant, J.-F.; Sjodin, A.; Turner, W. E.; Patterson, D. G., Jr. Measurement of Selected Polybrominated Diphenyl Ethers, Polybrominated and Polychlorinated Biphenyls, and Organochlorine Pesticides in Human Serum and Milk Using Comprehensive Two-Dimensional Gas Chromatography Isotope Dilution Time-of-Flight Mass Spectrometry. Anal. Chem. 2004, 76, 6313–6320.
Korytar, P.; Parera, J.; Leonards, P. E. G.; de Boer, J.; Brinkman, U. A. T. Quadrupole Mass Spectrometer Operating in the Electron-Capture Negative Ion Mode as Detector for Comprehensive Two-Dimensional Gas Chromatography. J. Chromatogr. A. 2005, 1067, 255–264.
Santos, F. J.; Galceran, M. T. Modern Developments in Gas Chromatography-Mass Spectrometry-Based Environmental Analysis. J. Chromatogr. A. 2003, 1000, 125–151.
Rothweiler, B.; Berset, J.-D. High Sensitivity of Ortho-Substituted Polychlorobiphenyls in Negative Ion Mass Spectrometry (NCI-MS): A Comparison with EI-MS and ECD for the Determination of Regulatory PCBs in Soils. Chemosphere. 1999, 38, 1517–1532.
Hyotylainen, T.; Hartonen, K. Determination of Brominated Flame Retardants in Environmental Samples. Trends Anal. Chem. 2002, 21, 13–29.
Stapleton, H. M. Instrumental Methods and Challenges in Quantifying Polybrominated Diphenyl Ethers in Environmental Extracts: A review. Anal. Bioanal. Chem. 2006, 386, 807–817.
Eljarrat, E.; Lacorte, S.; Barcelo, D. Optimization of Congener-Specific Analysis of 40 Polybrominated Diphenyl Ethers by gas Chromatography/Mass Spectrometry. J. Mass Spectrom. 2002, 37, 76–84.
Covaci, A.; de Boer, J.; Ryan, J. J.; Voorspoels, S.; Schepens, P. Determination of Polybrominated Diphenyl Ethers and Polychlorinated Biphenyls in Human Adipose Tissue by Large-Volume Injection Narrow-Bore Capillary Gas Chromatography/Electron Impact Low-Resolution Mass Spectrometry. Anal. Chem. 2002, 74, 790–798.
Ackerman, L. K.; Wilson, G. R.; Simonich, S. L. Quantitative Analysis of 39 Polybrominated Diphenyl Ethers by Isotope Dilution GC/Low-Resolution MS. Anal. Chem. 2005, 77, 1979–1987.
Bjorklund, J.; Tollback, P.; Hiarne, C.; Dyremark, E.; Ostman, C. Influence of the Injection Technique and the Column System on Gas Chromatographic Determination of Polybrominated Diphenyl Ethers. J. Chromatogr. A. 2004, 1041, 201–210.
Bjorklund, J.; Tollback, P.; Ostman, C. Mass Spectrometric Characteristics of Decabromodiphenyl Ether and the Application of Isotopic Dilution in the Electron Capture Negative Ionization Mode for the Analysis of Polybrominated Diphenyl ethers. J. Mass Spectrom. 2003, 38, 394–400.
Ong, V. S.; Hites, R. A. Electron Capture Mass Spectrometry of Organic Environmental Contaminants. Mass Spectrom. Rev. 1994, 13, 259–283.
Zeng, X.; Freeman, P. K.; Vasil’ev, Y. V.; Voinov, V. G.; Simonich, S. L.; Barofsky, D. F. Theoretical Calculation of Thermodynamic Properties of Polybrominated Diphenyl Ethers. J. Chem. Eng. Data. 2005, 50, 1548–1556.
Vetter, W. A GC/ECNI-MS Method for the Identification of Lipophilic Anthropogenic and Natural Brominated Compounds in Marine Samples. Anal. Chem. 2001, 73, 4951–4957.
Teuten, E. L.; Xu, L.; Reddy, C. M. Two Abundant Bioaccumulated Halogenated Compounds are Natural Products. Science. 2005, 307, 917–920.
Eljarrat, E.; de la Cal, A.; Barcelo, D. Potential Chlorinated and Brominated Interferences on the Polybrominated Diphenyl Ether Determinations by Gas Chromatography-Mass Spectrometry. J. Chromatogr. A. 2003, 1008, 181–192.
Tollback, P.; Bjorklund, J.; Ostman, C. Large-Volume Programmed-Temperature Vaporizer Injection for Fast Gas Chromatography with Electron Capture and Mass Spectrometric Detection of Polybrominated Diphenyl Ethers. J. Chromatogr. A. 2003, 991, 241–253.
Stapleton, H.; Schantz, M.; Wise, S. Measurement of Polybrominated Diphenyl Ethers in Environmental Matrix Standard Reference Materials. Organohalogen Comp. 2004, 66, 3745–3748.
Zhu, L. Y.; Hites, R. A. Determination of Polybrominated Diphenyl Ethers in Eenvironmental Standard Reference Materials. Anal. Chem. 2003, 75, 6696–6700.
US EPA Method 1668 Revision A, Chlorinated Biphenyl Congeners in Water, Soil, Sediment, and Tissue by HRGC/HRMS.
US EPA Draft Method 1614, Brominated Diphenyl Ethers in Water, Soil, Sediment, and Tissue by HRGC/HRMS.
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Published online April 29, 2007
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Zhao, Y., Yang, L. & Wang, Q. Pulsed large volume injection gas chromatography coupled with electron-capture negative ionization quadrupole mass spectrometry for simultaneous determination of typical halogenated persistent organic pollutants. J Am Soc Mass Spectrom 18, 1375–1386 (2007). https://doi.org/10.1016/j.jasms.2007.04.019
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DOI: https://doi.org/10.1016/j.jasms.2007.04.019