Supercritical fluid extraction of pesticides from meat: a systematic approach for optimisation

Abstract

A method for quantification of pesticide residues in meat and fatty matrices was developed using supercritical fluid extraction (SFE). The SFE method allows selective extraction of residues and subsequent gas chromatography analysis without further clean-up. Quantification was done by GC using nitrogen–phosphorus detection and electron capture detection. Initial method development was made using organophosphorus pesticides (OPPs). The dependence of fat and OPP residue recovery on supercritical fluid density, temperature, flow rate and extraction time was investigated through a reduced factorial design. Since temperature and density were found to have pronounced effect on the recovery of OPPs these extraction parameters were studied using a new arbitrary measure for co-extractivity. An optimisation score was established as relative pesticide recovery subtracted by relative fat recovery. Using this algorithm a response plane was modelled varying the primary factors temperature and density. The applicability of this approach and the algorithm was verified. The polarity range covered by the SFE method was demonstrated using OPPs: chlorpyrifos, chlorpyrifos-methyl, malathion, pirimifos-methyl and prothiofos. Additionaly the final method was evaluated using four pesticides that are not OPPs: carbofuran, phorate, procymidone and vinclozolin. All pesticides showed good recovery (78–95%), and limits of detection (0.01–0.03 mg kg^–1) and limits of determination (0.01–0.05 mg kg^–1) meet the requirements set by the European Council (Directive 96/33/EEC). Compared to traditional methods based on organic solvent extraction, the SFE method is fast, less labour intensive, uses smaller amounts of potentially harmful solvents and has the potential to be fully automated.

References

1. S. Bøwadt and S. B. Hawthorne, J. Chromatogr. A., 1995, 703, 549.
2. T. L. Chester, J. D. Pinkston and D. E. Raynie, Anal. Chem., 1996, 68, 487R.
3. S. Mitra and N. K. Wilson, J. Chromatogr. Sci., 1991, 29, 305.
4. T. Veress, J. Chromatogr. A, 1994, 668, 285.
5. X. Lou, H.-G. Janssen and C. A. Cramers, J. High Resolut. Chromatogr., 1995, 18, 483.
6. J. W. King, J. Chromatogr. Sci., 1989, 27, 355.
7. K. D. Bartle, A. A. Clifford, S. B. Hawthorne, J. J. Langenfeld, D. J. Miller and R. Robinson, J. Supercrit. Fluids, 1990, 3, 143.
8. M. T. G. Hierro and G. Santa-Maria, Food Chem., 1992, 45, 189.
9. J. M. Levy, L. Dolata, R. M. Ravey, E. Storozynsky and K. A. Holowczak, J. High Resolut. Chromatogr., 1993, 16, 368.
10. J. J. Langenfeld, S. B. Hawthorne, D. J. Miller and J. Pawliszyn, Anal. Chem., 1994, 66, 909.
11. T. M. Fahmy, M. E. Paulaitis, D. M. Johnson and M. E. P. McNally, Anal. Chem., 1993, 56, 1462.
12. C. A. Eckert, B. L. Knutson and P. G. Debenedetti, Nature (London), 1996, 383, 313.
13. P. Battersby, J. R. Dean, S. M. Hitchen, W. R. Tomlinson and P. Myers, Anal. Proc., 1993, 30, 473.
14. J. Arul, A. Boudreau, J. Makhlouf, R. Tardif and M. R. Sahasrabudhe, J. Food Sci., 1987, 52, 1231.
15. P. Lembke and H. Engelhardt, Chromatographia, 1993, 35, 509.
16. M. L. Hopper, J. W. King, J. H. Johnson, A. A. Serino and R. J. Butler, J. AOAC Int., 1995, 78, 1072.
17. M. V. Palmer and S. S. T. Ting, Food Chem., 1995, 52, 345.
18. M. Valcárcel and M. T. Tena, Fresenius' J. Anal. Chem., 1997, 358, 561.
19. J. S. Ho and P. H. Tang, J. Chromatogr. Sci., 1992, 30, 344.
20. D. H. Gere, C. R. Knipe, P. Castelli, J. Hedrick, L. G. Randal Frank, H. Schulenberg-Schell, R. Schuster, L. Doherty, J. Orolin and H. B. Lee, J. Chromatogr. Sci., 1993, 31, 246.
21. M. Hopper, J. AOAC Int., 1997, 80, 639.
22. S. M. Walters, Anal. Chim. Acta, 1990, 236, 77.
23. O. W. Parks and R. J. Maxwell, J. Chromatogr. Sci., 1994, 32, 290.
24. J. E. Frances, J. W. King and J. M. Snyder, J. Agric. Food Chem., 1991, 39, 1871.
25. K.-S. Nam and J. W. King, J. High Resolut. Chromatogr., 1994, 17, 577.
26. B. Murugaverl, A. Gharaibeh and K. J. Voorhees, J. Chromatogr. A, 1993, 657, 223.
27. J. E. France and J. W. King, J. AOAC Int., 1991, 74, 1013.
28. K.-S. Nam and J. W. King, J. Agric. Food Chem., 1994, 42, 1469.
29. S. M. Lee and S. Richmann, J. Assoc. Off. Anal. Chem., 1991, 74, 893.
30. B. M. Kaufmann and M. Clower Jr., J. AOAC Int., 1994, 78, 1079.
31. Official Methods of Analysis, ed. Helrich K, Association of Official Analytical Chemists Inc, Virginia, 15th edn., 1990, vol. 2, section 950.46.
32. K. Coulibaly and J. S. Smith, Agric. Food Chem., 1993, 41, 1719.
33. T. Stijve and E. Cardinale, Mitt. Geb. Lebensmittelunters. Hyg., 1974, 65, 131.
34. J. W. King and J. E. France, in Analysis with Supercritical Fluids: Extraction and Chromatography, ed. Wenclawiak B., Springer, Berlin, 1992, ch. 3.6.
35. A. A. Clifford, in Supercritical Fluid Extraction and its Use in Chromatographic Sample Preparation, ed. Westwood S. A., Blackie, Glasgow, 1993, ch. 1.
36. M. Kane, J. R. Dean, S. M. Hitchen, C. J. Dowle and R. L. Tranter, Anal. Chim. Acta, 1993, 271, 83.
37. T. M. Young and W. J. Weber Jr., Anal. Chem., 1997, 69, 1612.
38. N. Husers and W. Kleibohmer, J. Chromatogr. A., 1995, 697, 107.
39. K. G. Furton, E. Jolly and J. Rein, J. Chromatogr., 1993, 629, 3.
40. V. Janda, K. D. Bartle and A. A. Clifford, J. Chromatogr., 1993, 642, 283.
41. S. D. House, P. A. Larson, R. R. Johnson, J. DeWries and D. L. Martin, J. AOAC Int., 1994, 77, 960.
42. L. H. Ali, G. Angyal, C. M. Weaver and J. I. Rader, Food Chem., 1997, 58, 149.
43. U. G. Ahlborg, A. L. Black, J. F. Borzelleca, D. J. Clegg, M. J. Hamilton, F. Ives, J. R. Lundehn, K. Voldum-Clausen and W. J. Zhuang, Pesticides in Food—Plant Production and Protection Paper, FAO, Rome, 1991, 111, 15.
44. A. Noble, J. Chromatogr., 1993, 642, 3.
45. F. M. Lanças, M. E. C. Queiroz and I. C. E. Silva, Chromatographia, 1995, 40, 421.
46. K. Li, C. P. Ong and S. F. Y. Li, J. Chromatog. Sci., 1994, 32, 5653.
47. European Committee for Standardization (CEN), Fatty Food—Determination of Pesticides and Polychlorinated Biphenyls (PCBs), EN 1528, part 1–4, Brussels, 1996.
48. K. Hartonen, S. Bøwadt, S. B. Hawthorne and M. L. Riekkola, J. Chromatogr. A, 1997, 774, 229.
49. J. W. King, M. L. Hopper, R. G. Luchtefeld, S. L. Taylor and W. L. Orton, J. AOAC Int., 1993, 76, 857.
50. V. Leoni, A. M. Caricchia and S. Chiavarini, J. AOAC Int., 1992, 75, 511.
51. A. M. Gillespie, S. L. Daly, D. M. Gilvydis, F. Schneider and S. M. Walters, J. AOAC Int., 1995, 70, 109.
52. M. L. Hopper and J. W. King, J. Assoc. Off. Anal. Chem., 1991, 74, 661.
53. Council Directive 96/33/EEC, Off. J. Eur. Commun., 1996, L144, 35.
54. M. D. Burford, S. B. Hawthorne and D. J. Miller, Anal. Chem., 1993, 65, 1497.
55. J. W. King, J. M. Snyder, S. L. Taylor, J. H. Johnson and L. D. Rowe, J. Chromatogr. Sci., 1993, 31, 1.
56. D. L. Stalling, R. C. Tindle and J. L. Johnson, J. AOAC Int., 1972, 55, 32.
57. W. Specht and R. C. Tindle, Fresenius' Z. Anal. Chem., 1985, 322, 443.
58. P. Armishaw and R. G. Millar, J. AOAC Int., 1993, 76, 1917.
59. F. Hernández, R. Serrano, J. Beltran and F. J. López, J. AOAC Int., 1996, 79, 123.
60. Pesticide Analytical Manual, ed. McMahon, B. M., and Hardin, N. F., US Food and Drug Administration, Washington, DC, 3rd edn., 1994, vol. 1, section 2, p. 5.
61. R. K. Juhler, J. Chromatogr., 1997, 789, 145.
62. H. Obana, K. Kikuchi, M. Okihashi and S. Hori, Analyst, 1997, 122, 217.