Abstract
Due to the high lipophilicity of dioxins are related compounds, more than 90% of the human exposure to dioxins is due to consumption of lipid-rich food such as meat; milk and dairies, as well as fish and derived products. The measurement of these trace level analytes requires a complex and tedious procedure including sample extraction, sample clean-up, and physico-chemical analysis after Chromatographic separation. The determination of dioxins and related compounds requires a method that provides extremely high sensitivity and selectivity. High-resolution gas chromatography (HRGC) in combination with high-resolution mass spectrometry (HRMS) is the ‘gold’ standard method. In selected ion monitoring (SIM) mode, HRGC-HRMS (10,000 resolution) can achieve detection limit at the femtogram (10-15 g) level for most of the dioxin congeners. This paper explains the specificities and the pitfalls that could be met by analysts during the analytical development of this particular technique. Sample preparation, cleanup, selection of GC columns, specific aspects of double focusing sector instruments in SIM mode, high-resolution in mass, quantification by isotope dilution technique, quality assurance and quality control requirements and future perspectives are discussed and illustrated. A brief discussion of the bio-analytical approach is also provided to complete the analytical picture. Levels and trends for dioxins in food are discussed in the final part of the manuscript in the context of European regulation.
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References
Aarts, J.M., Denison, M.S., Cox, M.A., Schalk, A.C., Garrison, P.A., Tullis, K., Haan, L.H.J., Brouwer, A., 1995, Species-Specific Antagonism of Ah Receptor Action by 2,2χ,5,5χ-Tetrachloro- and 2,2χ,3,3χ,4,4χ-Hexachlorobiphenyl, Eur. J. Pharmacol. Environ. Toxicol., 293: 463-474.
Abraham, K., Knoll, A., Ende, M., Päpke, O., Helge, H., 1996, Intake, Fecal Excretion, and Body Burden of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans in Breast-Fed and Formula-Fed Infants, Pediatr. Res., 40: 671-679.
Baughman, R., Meselson, M., 1973, An Analytical method for detecting TCDD (dioxin): levels of TCDD in samples from Vietnam, Environ. Health Perspect., 5: 27-35.
Beck, H., Dross, A., Mathar, W., 1994, PCDD and PCDF exposure and levels in humans in Germany, Environ. Health Perspect., 102(Suppl. 1): 173-185.
Behnisch, P.A., Hosoe, K., Sakai, S.-I., 2001, Bioanalytical Screening Methods for Dioxin and Dioxin- Like Compounds - A Review of Bioassay/Biomarker Technology, Environ. Int., 27: 413-439.
Camel, V., 2001, Recent extraction techniques for solid matrices - supercritical fluid extraction, pressurized fluid extraction and microwave-assisted extraction: their potential and pitfall, Analyst, 126: 1182-1193.
EN1948, 1996, European Standard, Stationary source emission - determination of the mass concentration of PCDDs/PCDFs - Part 3: Identification et Quantification, December 1-51.
EPA method 1613 revision B, Tetra-through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS, October 1994, 1-86.
Eppe, G., Cofino, W.P., De Pauw, E., 2004, Performances and limitations of the HRMS method for dioxins, furans and dioxin-like PCBs analysis in animal feedingstuffs: I. results of an inter-laboratory study, Anal. Chim. Acta, 519(issue 2): 231-242.
Erickson, M.D., 1997, Analytical Chemistry of PCBs. CRC, Boca Raton, FL.
Eurachem, 1998, The fitness for purpose of analytical methods, a laboratory guide to method validation and related topics, December 1998. Available at http://www.eurachem.org/guides/valid.pdf
European Commission, 2000a, Compilation of EU Dioxin Exposure and Health Data, Task 4 - Human Exposure, DG environment, United Kingdom Department of the Environment, Transport and the Regions (DETR). Available at http://europa.eu.int/comm/environment/dioxin
European Commission, 2000b, Opinion of the SCF on the Risk Assessment of Dioxins and Dioxin-Like PCBs in Food, Health and Consumer Protection Directorate-General, Directorate C - Scientific Health Opinions, Unit C3 - Management of Scientific Committees II, Scientific Co-operation and Network.
FAO/WHO (Food and Agriculture Organization of the United Nations/World Health Organization), 2001, Joint Expert Committee on Food Additives and Contaminants Meeting, Rome, Italy.
Focant, J.-F., Pirard, C., De Pauw, E. 2004a, Automated sample preparation-fractionation for the measurement of dioxins and related compounds in biological matrices: a review, Talanta, 63: 1101- 1113.
Focant, J.-F., Sjödin, A., Patterson, D.G., 2004b, Improved separation of the 209 polychlorinated biphenyl congeners using comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry, J. Chromatogr. A, 1040: 227-238.
Focant, J.F., Cochran, J.W., Dimandja, J.M.D., De Pauw, E., Sjödin, A., Turner, W.E., Patterson, D.G., 2004c, High-throughput analysis of human serum for selected polychlorinated biphenyls (PCBs) by gas chromatography-isotope dilution time-of-flight mass spectrometry (GC-IDTOFMS), The Analyst, 129: 331-336.
Focant, J.-F., Pirard, C., Eppe, G., De Pauw, E., 2005a, Recent advances in mass spectrometric measurement of dioxins, J. Chromatogr. A, 1067: 265-275.
Focant, J.-F., Eppe, G., Scippo, M.-L., Massart, A.-C., Pirard, C., Maghuin-Rogister, G., De Pauw, E., 2005b, Comprehensive two-dimensionnal gas chromatography with isotope dilution time-of-flight mass spectrometry for the measurement of dioxins and polychlorinated biphenyls in foodstuffs. Comparison with other techniques, J. Chromatogr. A, 1086: 45-60.
ISO17025, 2005, The International Organization for Standardization, General Requirements for the Competence of Calibration and Testing Laboratories, September 2005.
Kumagai, S., Koda, T., Miyakita, H., Yamaguchi, K., Katagi, P., Yasuda, N., 2000, Polychlorinated dibenzo- p-dioxin and dibenzofuran concentrations in the serum samples of workers at continuously burning municipal waste incinerators in Japan, Occupational and Environmental Medicine, 57: 204-210.
LaKind, J.S., Berlin, C.M., Park, C.N., Naiman, D.Q., Gudka, N.J., 2000, Methodology for characterizing distributions of incremental body burdens of 2,3,7,8-TCDD and DDE from breast milk in North American nursing infants, J. Toxicol. Environ. Health A, 59: 605-639.
LaKind, J.S., Berlin, C.M., Naiman, D.Q., 2001, Infant exposure to chemicals in breast milk in the United States: What we need to learn from a breast milk monitoring program, Environ. Health Perspect., 109: 75-88.
Larsen, B., Cont, M., Montanarella, L., Platzner, N., 1995, Enhanced selectivity in the analysis of Chlorobiphenyls on a carborane phenylmethylsiloxane copolymer gas-chromatography phase (HT-8), J. Chromatogr. A, 708: 115-129.
Liem, A.K.D., 1999, Basic Aspects of Methods for the determination of dioxins and PCBs in foodstuffs and human tissues, Trends Anal. Chem., 18: 429-439.
Liem, A.K.D., Atuma, S., Becker, W., Darnerud, P.O., Hoogebrugge, R., Schreiber, G.A., 2000, Dietary Intake of dioxins and dioxin-like pcbs by the general population of ten European countries. Results of EU-SCOOP Task 3.2.5 (Dioxins), Organohalogen Compd., 48: 13-16.
Lorber, M., 2002, A Pharmacokinetic model for estimating exposure of Americans to dioxin-like compounds in the past, present, and future, Sci. Tot. Environ., 288: 81-95.
OJEC (Official Journal of the European Communities), 2001, Communication from the Commission to the Council, the European Parliement and the Economic and Social Committee, Community Strategy for Dioxins, Furans and Polychlorinated Biphenyls, 2001/C 322/02.
OJEC (Official Journal of the European Communities), 2002, EU Commission Recommendation (EC) No 2002/201/EC of March 4 2002 on the reduction of the presence of dioxins, furans, and PCBs in feedingstuffs and foodstuffs, 9.3.2002, L67/69-73.
OJEC (Official Journal of the European Communities), 2006a, EU Commission Regulation (EC) No 1883/2006 of December 19 2006 laying down methods of sampling and analysis for the official control of levels of dioxins and dioxin-like PCBs in certain foodstuffs, 20.12.2006, L364/32-43.
OJEC (Official Journal of the European Communities), 2006b, EU Commission Regulation (EC) No 1881/2006 of December 19 2006 setting maximum levels for certain contaminants in foodstuffs, 20.12.2006, L364/5-23.
OJEC (Official Journal of the European Communities), 2006c, EU Commission Directive 2006/13/EC of February 3 2006 amending annexes I and II to Directive 2002/32/EC of the European Parliament and of the Council on undesirable substances in animal feed as regards dioxins abd dioxin-like PCBs, 4.2.2006, L32/44-53.
Patterson, D.G., Holler, J.S., Lapeza, C.R., Alexander, L.R., Groce, D.F., O’Connor, R.C., Smith, S.J., Liddle, J.A., Needham, L.L., 1986, High-Resolution gas chromatography/high-resolution mass spectrometry analysis of human adipose tissue for 2,3,7,8-tetrachlorodibenzo-p-dioxin, Anal. Chem., 58: 705-713.
Patterson Jr., D.G., Needham, L.L., Pirkle, J.L., Roberts, D.W., Bagby, J., Garrett, W.A., 1988. Correlation between serum and adipose tissue levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin in 50 persons from Missouri, Arch. Environ. Contam. Toxicol., 17, 139-143.
Patterson, D.G., Turner, W.E., Alexander, L.R., Isaacs, S., Needham, L.L., 1989, The analytical methodology and method performance of 2,3,7,8-TCDD in serum for the Vietnam veteran agent orange validation study, the ranch hand validation and half-life studies, and selected NIOSH worker studies, Chemosphere, 18: 875-882.
Plombey, J.B., Lausevic, M., March, R.E., 2000, Determination of dioxins/furans and PCBs by quadrupole ion-trap gas chromatography-mass spectrometry, Mass Spectrom. Rev., 19: 305-365.
SCAN (Scientific Committee on Animal Nutrition), 2000, Dioxin Contamination of Feedinstuffs and Their Contribution to the Contamination of Food of Animal Origin. Available at http://europa.eu.int/ comm/food/fs/sc/scan/out55_en.pdf
SCF (Scientific Committee on Food), 2000, Risk Assessment of Dioxins and Dioxin-Like PCBs in Food. Available at http://europa.eu.int/comm/food/fs/sc/scan/out78_en.pdf
Schecter, A., Fürst, P., Fürst, C., Päpke, O., Ball, M., Ryan, J.J., Cau, H.D., Dai, L.C., Quynh, H.T., Cuong, H.Q., Phuong, N.T.N., Phiet, P.H., Beim, A., Constable, J., Startin, J., Samedy, M., Seng, Y.K., 1994, Chlorinated dioxins and dibenzofurans in human tissue from general populations: a selective review, Environ. Health Perspect., 102: 159-171.
UNEP (United Nations Environment Programme), 2001, Available at http://www.chem.unep.ch/pops/
Van den Berg, M., Birnbaum, L.S., Denison, M., De Vito, M., Farland, W., Feeley, M., Fiedler, H., Hakansson, H., Hanberg, A., Haws, L., Rose, M., Safe, S., Schrenk, D., Tohyama, C., Tritscher, A., Tuomisto, J., Tysklind, M., Walker, N., Peterson, R.E., 2006, The 2005 World Health Organization reevaluation of human and Mammalian toxic equivalency factors for dioxins and dioxin-like compounds, Toxicol. Sci., 93: 223-241.
Van Leeuwen, F.X.R., Feeley, M., Schrenk, D., Larsen, J.C., Farland, W., Younes, M., 2000, Dioxins: WHO’s tolerable daily intake revisited, Chemosphere, 40: 1095-1101.
WHO (World Health Organization), 1999, Joint FAO/WHO Food Standards Programme Codex Committee on Food Additives and Contaminants, Codex Alimentarius Commission, Food and Agriculture Organization of the United Nations.
WHO (World Health Organization), 2000, Consultation on Assessment of the Health Risk of Dioxins, Re-Evaluation of the Tolerable Daily Intake (TDI): Executive Summary, Food Addit. Contam., 17: 223-240.
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Focant, JF., Eppe, G., De Pauw, E. (2008). Analytical Measurement and Levels of Dioxins and PCBs in Biological Samples. In: Faye, B., Sinyavskiy, Y. (eds) Impact of Pollution on Animal Products. NATO Science for Peace and Security Series Series C: Environmental Security. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8359-4_3
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