Skip to main content
SpringerLink
Log in

Determination of carbofuran, carbaryl and their main metabolites in plasma samples of agricultural populations using gas chromatography–tandem mass spectrometry

  • Original Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

A gas chromatography–tandem mass spectrometric (GC-MS/MS) method has been developed for the determination of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate), carbaryl (1-naphthyl-N-methylcarbamate) and their main metabolites in human blood plasma. Optimization of the isolation of the compounds from plasma matrix included the precipitation, denaturation and digestion of plasma proteins. Derivatization was achieved by the use of trifluoroacetic acid anhydride and was optimized for temperature, time and volume of derivatization agent. In the proposed method, a mild precipitation technique was applied using β-mercaptoethanol and ascorbic acid in combination with solid-phase extraction technique using Oasis HLB (Hydrophobic Lipophilic Balance) cartridges for further clean up of samples. Carbamate linkage was not hydrolyzed to its phenol product, but both carbamate phenol and ketones were transformed into trifluoroacetyl derivatives in order to become volatile compounds and were determined using tandem mass spectrometry. The linearity of the method was shown for nine concentrations in the range of 0.50–250 ng mL−1 in fortified plasma aliquots. Limits of detection (LODs) for all compounds ranged from 0.015–0.151 ng mL−1. Inter-day and intra-day assays (RSD) for all compounds, at three concentration levels of 2.5, 25 and 100 ng mL−1 (n=3) in fortified plasma samples were less than 18%. Accuracy (%E r) was calculated at three concentration levels, 8, 80 and 160 ng mL−1 (n=3), and ranged from −12.0 to 15.0%. Matrix effect was evaluated so mean recoveries were calculated for all compounds and ranged from 81–107%. Specificity for the use of this method to biological monitoring studies was achieved including four main metabolites of CF, 1-naphthol and 2-naphthol from the naphthalene metabolism pathways, and both the parent compound of carbofuran and carbaryl. The proposed method was applied to plasma samples of pesticide users.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Needham LL, Barr DB, Caudill SP, Pirkle JL, Turner WE, Osterloh J, Jones RL, Sampson JEJ (2005) Neurotoxicology 26:531–545

    Article  CAS  Google Scholar 

  2. Colosio C, Birindelli S, Corsini E, Galli CL, Maroni M (2005) Toxicol Appl Pharmacol 207:S320–S328

    Article  CAS  Google Scholar 

  3. Department of Health and Human Services, Centers for Disease Control and Prevention (2005) Third national report on human exposure to environmental chemicals

  4. Needham LL, Patterson DG Jr, Barr DB, Grainger J, Calafat AM (2005) Anal Bioanal Chem 381:397–404

    Article  CAS  Google Scholar 

  5. Hernandez F, Sancho JV, Pozo OJ (2005) Anal Bioanal Chem 382:934–946

    Article  CAS  Google Scholar 

  6. Maroni M, Colosio C, Ferioli A, Fait A (2000) Toxicology 143:1–118

    Article  CAS  Google Scholar 

  7. Ferslew KE, Hagardorn AN, McCormick WF (1992) J Forensic Sci 37:337–344

    CAS  Google Scholar 

  8. Jokanovic M, Maksimovic M (1997) Eur J Clin Chem Clin Biochem 35:11–16

    CAS  Google Scholar 

  9. Ameno K, Lee S-K, In S-W, Yang J-Y, Yoo Y-C, Ameno S, Kubota T, Kinoshita H, Ijiri I (2001) Forensic Sci Int 116:59–61

    Article  CAS  Google Scholar 

  10. Usmani KA, Hodgson E, Rose RL (2004) Chem-Biol Interact 150:221–232

    Article  CAS  Google Scholar 

  11. Krieger RI, Lee PW, Fahmy AH, Chen M, Fukuto TR (1976) Pestic Biochem Physiol 6:1–9

    Article  CAS  Google Scholar 

  12. Knaak JB, Munger DM, McCarthy JF, Satter LD (1970) J Agric Food Chem 18:832–837

    Article  CAS  Google Scholar 

  13. Cook RF, Jackson JE, Shuttleworth JM, Fullmer OH, Fujie GH (1977) J Agric Food Chem 25:1013–1017

    Article  CAS  Google Scholar 

  14. Office of Environmental Health Hazard Assessment, California Environmental Protection Agency, Pesticide and Environmental Toxicology Section (1999) Public health goal for carbofuran in drinking water, draft for review

  15. Liu KH, Byon JY, Sung HJ, Lee HK, Kim K, Lee HS, Kim JH (2001) Chromatographia 53:687–690

    Article  CAS  Google Scholar 

  16. Liu KH, Sung HJ, Lee HK, Song BH, Ihm YB, Kim K, Lee HS, Kim JH (2002) Pestic Manage Sci 58:57–62

    Article  CAS  Google Scholar 

  17. Hill RH Jr, Shealy DB, Head SL, Williams CC, Bailey SL, Gregg M, Baker SE, Needham LL (1995) Anal Toxicol 19:323–329

    CAS  Google Scholar 

  18. Shealy DB, Bonin MA, Wooten JV, Ashley DL, Needham LL (1996) Environ Int 22:661–675

    Article  CAS  Google Scholar 

  19. Shealy DB, Barr JR, Ashley DL, Patterson DG Jr, Camann DE, Bond AE (1997) Environ Health Perspect 105:510–513

    Article  CAS  Google Scholar 

  20. Hill RH Jr, Head SL, Baker SE, Gregg M, Shealy DB, Bailey SL, Williams CC, Sampson EJ, Needham LL (1995) Environ Res 71:99–108

    Article  CAS  Google Scholar 

  21. Meeker JD, Ryan L, Barr DB, Herrick RF, Bennett DH, Bravo R, Hauser R (2004) Environ Health Perspect 112:1665–1670

    Article  CAS  Google Scholar 

  22. Preuss R, Koch HM, Wilhelm M, Pischetsrieder M, Angerer J (2004) Int J Hyg Environ Health 207:441–445

    Article  CAS  Google Scholar 

  23. Martinez Fernandez J, Parrilla Vazquez P, Martinez Vidal JL (2000) Anal Chim Acta 412:131–139

    Article  Google Scholar 

  24. Parrilla Vazquez P, Martinez Vidal JL, Martinez Fernandez J (2000) J Chromatogr B 738:387–394

    Article  CAS  Google Scholar 

  25. Barr DB, Barr JR, Maggio VL, Whitehead RD Jr, Sadowski MA, Whyatt RM, Needham LL (2002) J Chromatogr B 778:99–111

    Article  CAS  Google Scholar 

  26. Kumasawa T, Suzuki O (2000) J Chromatogr B 747:241–254

    Article  Google Scholar 

  27. Lacassie E, Marquet P, Gaulier J-M, Dreyfuss M-F, Lachatre G (2001) Forensic Sci Int 121:116–125

    Article  CAS  Google Scholar 

  28. Aprea C, Colosio C, Mammone T, Minoia C, Maroni M (2002) J Chromatogr B 769:191–219

    Article  CAS  Google Scholar 

  29. U.S. Department of Health and Human Services, Food and Drug Administration, Centers for Biologic Evaluation and Researh (CBER) (1999) Guidance for industry: for the submission of chemistry, manufacturing and controls and establishment description information for human plasma-derived biological products, animal plasma or serum derived products

  30. Thompson M, Ellison SLR, Wood R (2002) Pure Appl Chem 74:835–855

    CAS  Google Scholar 

  31. Fura A, Harper TW, Zhang H, Fung L, Shyu WC (2003) J Pharm Biomed Anal 32:513–522

    Article  CAS  Google Scholar 

  32. Buechler J, Schwab M, Mikus G, Fischer B, Hermle L, Marx C, Gron G, Spitzer M, Kovar K-A (2003) J Chromatogr B 793:207–222

    Article  CAS  Google Scholar 

  33. Poon K-F, Lam PKS, Lam MHW (1999) Chemosphere 39:905–912

    Article  CAS  Google Scholar 

  34. Vandenabeele-Trambouze O, Garrelly L, Mion L, Boiteau L, Commeyras A (2001) Adv Environ Res 6:67–80

    Article  CAS  Google Scholar 

  35. Molina M, Perez-Bendito D, Silva M (1999) Electrophoresis 20:3439–3449

    Article  CAS  Google Scholar 

  36. Lopez-Blanco MC, Cancho-Grande B, Simal-Gandara J (2002) J Chromatogr A 963:117–123

    Article  CAS  Google Scholar 

  37. Johnson KA, Harper FD, Weisskopf CP (1997) J Environ Qual 26:1435–1438

    Article  CAS  Google Scholar 

  38. Won JW, Webster MG, Bezabeh DZ, Henkel MJ, Ngim KK, Krynitsky AJ, Ebeler SE (2004) J Agric Food Chem 52:6361–6372

    Article  CAS  Google Scholar 

  39. Bogialli S, Curini R, Di Corcia A, Nazzari M, Tamburro D (2004) J Agric Food Chem 52:665–671

    Article  CAS  Google Scholar 

  40. Takino M, Yamaguchi K, Nakahara T (2004) J Agric Food Chem 52:727–735

    Article  CAS  Google Scholar 

  41. Blasco C, Fernandez M, Pena A, Lino C, Silveira I, Font G, Pico Y (2003) J Agric Food Chem 51:8132–8138

    Article  CAS  Google Scholar 

  42. Miller-Stein C, Boppana VK, Rhodes GR (1994) J Chromatogr B 661:291–297

    Article  CAS  Google Scholar 

  43. Honing M, Riu J, Barcelo J, van Baar BLM, Brinkman UATh (1996) J Chromatogr A 733:283–294

    Article  CAS  Google Scholar 

  44. Tsumura Y, Ujita K, Nakamura Y, Tonogai Y, Ito Y (1995) J Food Prot 58:217–222

    CAS  Google Scholar 

  45. Nunes GC, Ribeiro ML, Polese L, Barcelo D (1998) J Chromatogr A 795:43–51

    Article  CAS  Google Scholar 

  46. Soriano JM, Jimenez BJ, Font G, Molto JC (2001) Crit Rev Anal Chem 31:19–52

    Article  CAS  Google Scholar 

  47. Vassilakis I, Tsipi D, Scoullos M (1998) J Chromatogr A 823:49–58

    Article  CAS  Google Scholar 

  48. Liska I, Bilikova K (1998) J Chromatogr A 795:61–69

    Article  CAS  Google Scholar 

  49. Zrostlikova J, Hajslova J, Kovalczuk T, Stepan R, Poustka J (2003) J AOAC Int 86:612–622

    CAS  Google Scholar 

  50. Aburuz S, Milleship J, Heaney L, McElnay J (2003) J Chromatogr B 798:193–201

    Article  CAS  Google Scholar 

  51. Knapp DR (1979) Handbook of analytical derivatisation reactions. Wiley-Interscience, Charleston, SC

    Google Scholar 

  52. Petropoulou S-SE, Gikas E, Tsarbopoulos A, Siskos PA (2006) J Chrom A 1108:99–110

    Article  CAS  Google Scholar 

Download references

Acknowledgements

S.-S.E.P. is grateful to the Public Benefit Foundation of Alexandros S. Onassis for providing her research scholarship in order to carry out this research in the field of environmental analytical chemistry. Thanks is also given to Dr. Spiros Garbis, Academy of Science, Foundation for Biomedical Research, Division of Biotechnology, Athens, Greece, for helpful discussions and Paraskevi Magnisali for supplying the control plasma matrix for developing the presented method.

Author information

Authors and Affiliations

  1. Bioanalytical Laboratory, GAIA Research Center, The Goulandris Natural History Museum, 100 Othonos str., 145 62, Kifissia, Greece

    Syrago-Styliani E. Petropoulou & Anthony Tsarbopoulos

  2. Analytical Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 15771 Zographos, Athens, Greece

    Syrago-Styliani E. Petropoulou & Panayotis A. Siskos

  3. Laboratory of Instrumental Analysis, Department of Pharmacy, University of Patras, 265 04, Rio, Greece

    Anthony Tsarbopoulos

Authors
  1. Syrago-Styliani E. Petropoulou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Anthony Tsarbopoulos
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Panayotis A. Siskos
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Panayotis A. Siskos.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Petropoulou, SS.E., Tsarbopoulos, A. & Siskos, P.A. Determination of carbofuran, carbaryl and their main metabolites in plasma samples of agricultural populations using gas chromatography–tandem mass spectrometry. Anal Bioanal Chem 385, 1444–1456 (2006). https://doi.org/10.1007/s00216-006-0569-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-006-0569-0

Keywords

Search

Navigation