Application of Microwave-Assisted Extraction for the Analysis of Dithiocarbamates in Food Matrices

  • Euphemia Papadopoulou-Mourkidou
  • Emmanuil Nikolaos Papadakis
  • Zisis Vryzas
Protocol
Part of the Methods in Biotechnology book series (MIBT, volume 19)

Abstract

Microwave-assisted extraction (MAE) is a simple, fast, and accurate method developed for the analysis of N,N-dimethyldithiocarbamate (DMDTC) and ethylenebis(dithiobamate) (EBDTC) fungicides in fruits and vegetables. Residues are extracted from the plant matrices and hydrolyzed to CS2 in a single step in the presence of 1.5% SnCl2 in 5N hydrochloric acid using a laboratory microwave oven operated in the closed-vessel mode. The evolved CS2, trapped in a layer of isooctane overlaying the reaction mixture, is analyzed by gas chromatography/flame photometric detection (GC/FPD). Sets of 12 samples are processed simultaneously. Quantification is based on external standard calibration curves made with either standard solutions of individual DMDTCs (thiram, ziram) or EBDTCs (maneb, zineb, mancozeb), which are processed as the field samples, or using standard solutions of CS2 made in isooctane. Calibration curves are better fitted with quadratic equations with correlation coefficients >0.999; however, good linear correlation coefficients can also be obtained in narrower calibration ranges. Limits of detection (LODs) and limits of quantitation (LOQs) are in the range 0.005–0.1 mg/kg. Recoveries are >80%, with respective relative standard deviation values <20%.

Key Words

CS2 Dithiocarbamates fruits and vegetables fungicides gas chromatographic analysis microwave-assisted extraction (MAE) residues 

References

  1. 1.
    Keppel, G. E. (1969) Modification of the carbon disulfide evolution method for dithiocarbamate residues. J. AOAC 52, 162–167.Google Scholar
  2. 2.
    Keppel, G. E. (1971) Collaborative study of the determination of dithiocarbamate residues by a modified carbon disulfide evolution method. J. AOAC 54, 528–532.Google Scholar
  3. 3.
    Kesari, R. and Gupta, V. K. (1998) A sensitive spectrophotometric method for the determination of dithiocarbamate fungicide and its application in environmental samples. Talanta 45, 1097–1102.CrossRefPubMedGoogle Scholar
  4. 4.
    Ahmad, N., Guo, L., Mandarakas, P., and Appleby, S. (1995) Determination of dithiocarbamate and its breakdown product ethylenethiourea in fruits and vegetables. J. AOAC Int. 78, 1238–1243.Google Scholar
  5. 5.
    Woodrow, J. E. and Seiber, J. N. (1995) Analytical method for the dithiocarbamate fungicides ziram and mancozeb in air: Preliminary field results. J. Agric. Food Chem. 43, 1524–1529.CrossRefGoogle Scholar
  6. 6.
    Ahmad, N., Guo, L., Mandarakas, P., Farah, V., Appleby, S., and Gibson, T. (1996) Headspace gas-liquid chromatographic determination of dithiocarbamate residues in fruits and vegetables with confirmation by conversion to ethylenethiourea. J. AOAC Int. 79, 1417–1422.PubMedGoogle Scholar
  7. 7.
    Royer, A., Ménand, M., Grimault, A., and Communal, P. Y. (2001) Development of automated headspace gas chromatography determination of dithiocarbamates in plant matrixes. J. Agric. Food Chem. 49, 2152–2158.CrossRefPubMedGoogle Scholar
  8. 8.
    Vryzas, Z., Papadakis, E. N., and Papadopoulou-Mourkidou, E. (2002) Microwave-Assisted Extraction (MAE)-acid hydrolysis of dithiocarbamates for trace analysis in tobacco and peaches. J. Agric. Food Chem. 50, 2220–2226.CrossRefPubMedGoogle Scholar
  9. 9.
    Gustafsson, K. H. and Fahlgren, C. (1983) Determination of dithiocarbamate fungicides in vegetable foodstuffs by high-performance liquid chromatography. J. Agric. Food Chem. 31, 461–463.CrossRefPubMedGoogle Scholar
  10. 10.
    Ekroth, S. B., Ohlin, B., and Österdahl, B.-G. (1998) Rapid and simple method for determination of thiram in fruits and vegetables with high-performance liquid chromatography with ultraviolet detection. J. Agric. Food Chem. 46, 5302–5304.CrossRefGoogle Scholar
  11. 11.
    Lo, C.-C., Ho, M.-H., and Hung, M.-D. (1996) Use of high-performance liquid chromatography and atomic absorption methods to distinguish propineb, zineb, maneb, and mancozeb fungicides. J. Agric. Food Chem. 44, 2720–2723.CrossRefGoogle Scholar
  12. 12.
    Weissmahr, K. W., Houghton, C. L., and Sediak, D. L. (1998) Analysis of the dithiocarbamate fungicides ziram, maneb, and zineb and the flotation agent ethylxanthogenate by ion-pair reversed-phase HPLC. Anal. Chem. 70, 4800–4804.CrossRefGoogle Scholar
  13. 13.
    Steinheimer, T. R. (1993) HPLC determination of atrazine and principal degradates in agricultural soils and associated surface and ground water. J. Agric. Food Chem. 41, 588–595.CrossRefGoogle Scholar
  14. 14.
    Molins, C., Hogendoorn, E.A., Heusinkveld, H. A. G., van Harten, D. C., van Zoonen, P., and Baumann, R.A. (1996) Microwave assisted solvent extraction for the efficient determination of triazines in soil samples with aged residues. Chromatographia 43, 527–532.CrossRefGoogle Scholar
  15. 15.
    Hoogerbrugge, R., Molins, C., and Baumann, R. A. (1997) Effects of parameters on microwave assisted extraction of triazines from soil: evaluation of an optimization trajectory. Anal. Chim. Acta 348, 247–253.CrossRefGoogle Scholar
  16. 16.
    Xiong, G., Liang, J., Zou, S., and Zhang, Z. (1998) Microwave-assisted extraction of atrazine from soil followed by rapid detection using commercial ELISA kit. Anal. Chim. Acta 371, 97–103.CrossRefGoogle Scholar
  17. 17.
    Papadakis, E. N. and Papadopoulou-Mourkidou, E. (2002) Determination of metribuzin and major conversion products in soils by microwave-assisted water extraction followed by liquid chromatographic analysis of extracts. J. Chromatogr. A 962, 9–20.CrossRefPubMedGoogle Scholar
  18. 18.
    Vryzas, Z. and Papadopoulou-Mourkidou, E. (2002) Determination of triazine and chloroacetanilide herbicides in soils by microwave-assisted extraction (MAE) coupled to gas chromatographic analysis with either GC-NPD or GC-MS. J. Agric. Food Chem. 50, 5026–5033.CrossRefPubMedGoogle Scholar
  19. 19.
    Molins, C., Hogendoorn, E. A., Dijkman, E., Heusinkveld, H. A. G., and Baumann, R. A. (2000) Determination of linuron and related compounds in soil by microwave-assisted solvent extraction and reversed-phase liquid chromatography with UV detection. J. Chtromatogr. A 869, 487–496.CrossRefGoogle Scholar
  20. 20.
    Hogendoorn, E. A., Huls, R., Dijkman, E., and Hoogerbrugge, R. (2001) Microwave assisted solvent extraction and coupled-column reversed-phase liquid chromatography with UV detection-Use of an analytical restricted-access-medium column for the efficient multi-residue analysis of acidic pesticides in soils. J. Chromatogr. A 938, 23–33.CrossRefGoogle Scholar
  21. 21.
    Patsias, J., Papadakis, E. N., and Papadopoulou-Mourkidou, E. (2002) Analysis of phenoxyalkanoic acid herbicides and their phenolic conversion products in soil by microwave assisted solvent extraction and subsequent analysis of extracts by on-line solid-phase extraction-liquid chromatography. J. Chromatogr. A 959, 153–161.CrossRefPubMedGoogle Scholar
  22. 22.
    Eskilsson, C. S. and Björklund, E. (2000) Analytical-scale microwave-assisted extraction. J. Chromatogr. A 902, 227–250.CrossRefPubMedGoogle Scholar
  23. 23.
    Buldini, P. L., Ricci, L., and Sharma, J. L. (2002) Recent applications of sample preparation techniques in food analysis. J. Chromatogr. A 975, 47–70.CrossRefPubMedGoogle Scholar
  24. 24.
    Camel, V. (2000) Microwave-assisted solvent extraction of environmental samples. Trends Anal. Chem. 19, 229–248.CrossRefGoogle Scholar

Copyright information

© Humana Press Inc. 2006

Authors and Affiliations

  • Euphemia Papadopoulou-Mourkidou
    • 1
  • Emmanuil Nikolaos Papadakis
    • 1
  • Zisis Vryzas
    • 1
  1. 1.Pesticide Science LaboratoryAristotle University of ThessalonikiThessalonikiGreece

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