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Determination of the Phenoxyacid Herbicides MCPA, Mecoprop and 2,4-D in Kidney Tissue Using Liquid Chromatography with Electrospray Tandem Mass Spectrometry

Abstract

An analytical method was developed to determine the phenoxyacid herbicides 2,4-D, MCPA and mecoprop in kidney tissue from animals where poisoning is suspected. Samples were Soxhlet extracted using diethyl ether and the extracts cleaned-up using anion exchange solid phase extraction cartridges. Analysis was performed using liquid chromatography with negative-ion electrospray tandem mass spectrometry (LC-MS/MS). The method was evaluated by analysing control kidney samples fortified at 1 and 5 mg/kg. Mean recoveries ranged from 82 to 93% with relative standard deviations from 3.2 to 19%. The limit of detection was estimated to be 0.02 mg/kg.

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References

  1. Arnold EK, Beasley VR, Parker AJ, Stedelin JR (1991) 2,4-D Toxicosis II—a pilot study of clinical pathological and electroencephalographic effects and residues of 2,4-D in orally dosed dogs. Vet Hum Toxicol 33:446–449

    CAS  Google Scholar 

  2. Aydin H, Özdemir N, Uzunoren N (2005) Investigation of the accumulation of 2,4-dichlorophenoxyacetic acid (2,4-D) in rat kidneys. Forensic Sci Int 153:53–57. doi:10.1016/j.forsciint.2005.04.018

    Article  CAS  Google Scholar 

  3. Barnekow DE, Hamburg AW, Puvanesarajah V, Guo M (2001) Metabolism of 2,4-dichlorophenoxyacetic acid in laying hens and lactating goats. J Agric Food Chem 49:156–163. doi:10.1021/jf000119r

    Article  CAS  Google Scholar 

  4. Brown PM, Turnbull G, Charman S, Charlton AJA, Jones AJ (2005) Analytical methods used in the United Kingdom wildlife incident investigation scheme for the detection of animal poisoning by pesticides. Assoc Off Anal Chem Int 88:204–220

    CAS  Google Scholar 

  5. Dickow LM, Gerken DF, Sams RA, Ashcraft SM (2001) Simultaneous determination of 2,4-D and MCPA in canine plasma and urine by HPLC with fluorescence detection using 9-anthryldiazomethane (ADAM). J Anal Toxicol 25:35–39

    CAS  Google Scholar 

  6. Drill VA, Hiratzka T (1953) Toxicity of 2,4-dichlorophenoxyacetic acid and 2,4,5-trichlorophenoxyacetic acid: a report on their acute and chronic toxicity in dogs. Arch Ind Hyg Occup Med 7:61–67

    CAS  Google Scholar 

  7. Fletcher MR, Grave RC (1992) Post-registration surveillance to detect wildlife problems arising from approved pesticides. Brighton Crop Prot Conf: Pest Dis 1–3:793–798

    Google Scholar 

  8. Frantz SW, Kropscott BE (1993) Pharmacokinetic evaluation of a single oral-administration of the 2-ethylhexyl (isooctyl) ester of 2,4-d to Fischer 344 rats. J Clean Technol Env 3:115–125

    Google Scholar 

  9. Garthwaite DG, Thomas MR, Anderson HM, Stoddart H (2005) Pesticide usage survey report 202: arable crops in Great Britain 2004. Pesticide Usage Survey Group, Central Science Laboratory, Sand Hutton

    Google Scholar 

  10. Garthwaite DG, Thomas MR, Anderson HM, Battersby A (2006) Pesticide usage survey report 210: grassland & fodder crops in Great Britain 2005. Pesticide Usage Survey Group, Central Science Laboratory, Sand Hutton

    Google Scholar 

  11. Henriksen T, Svensmark B, Lindhardt B, Juhler RK (2001) Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC-MS. Chemosphere 44:1531–1539. doi:10.1016/S0045-6535(00)00532-4

    Article  CAS  Google Scholar 

  12. Kuang H, Chu XG, Hou YX, Xu CL (2006) Simultaneous determination of 13 phenoxy acid herbicide residues in soybean by GC-ECD. Anal Lett 39:2617–2627. doi:10.1080/00032710600824755

    Article  Google Scholar 

  13. Moret S, Hidalgo M, Sanchez JM (2006) Development of an ion-pairing liquid chromatography method for the determination of phenoxyacetic herbicides and their main metabolites: application to the analysis of soil samples. Chromatographia 63:109–115. doi:10.1365/s10337-005-0711-8

    Article  CAS  Google Scholar 

  14. Nilsson T, Baglio D, Galdo-Miguez I, Madsen JO, Facchetti S (1998) Derivatisation/solid-phase microextraction followed by gas chromatography mass spectrometry for the analysis of phenoxy acid herbicides in aqueous samples. J Chromatogr A 826:211–216. doi:10.1016/S0021-9673(98)00740-7

    Article  CAS  Google Scholar 

  15. Rimmer DA, Johnson PD, Brown RH (1996) Determination of phenoxy acid herbicides in vegetation, utilising high-resolution gel permeation chromatographic clean-up and methylation with trimethylsilyldiazomethane prior to gas chromatographic analysis with mass-selective detection. J Chromatogr A 755:245–250. doi:10.1016/S0021-9673(96)00615-2

    Article  Google Scholar 

  16. Schulze GE, Blake JW, Dougherty JA (1985) The metabolic-fate of 2,4-dichlorophenoxyacetic acid-normal-butyl ester in the Wistar rat. Arch Toxicol 57:231–236. doi:10.1007/BF00324783

    Article  CAS  Google Scholar 

  17. Shin HS (2006) Determination of phenoxy acid pesticides in frog and fish tissues by gas chromatography-mass spectrometry. Chromatographia 63:579–583. doi:10.1365/s10337-006-0805-y

    Article  CAS  Google Scholar 

  18. Thompson HM (1996) Interactions between pesticides; a review of reported effects and their implications for wildlife risk assessment. Ecotoxicology 5:59–81. doi:10.1007/BF00119047

    Article  CAS  Google Scholar 

  19. Thorstensen CW, Lode O, Christiansen AL (2000) Development of a solid-phase extraction method for phenoxy acids and bentazone in water and comparison to a liquid-liquid extraction method. J Agric Food Chem 48:5829–5833. doi:10.1021/jf0000124

    Article  CAS  Google Scholar 

  20. Timchalk C (2004) Comparative inter-species pharmacokinetics of phenoxyacetic acid herbicides and related organic acids evidence that the dog is not a relevant species for evaluation of human health risk. Toxicology 200:1–19. doi:10.1016/j.tox.2004.03.005

    Article  CAS  Google Scholar 

  21. Tomlin CDS (2006) The e-Pesticide manual, a world compendium, 14th edn. British Crop Protection Council, Alton

    Google Scholar 

  22. Van Ravenzwaay B, Hardwick TD, Needham D, Pethen S, Lappin GJ (2003) Comparative metabolism of 2,4-dichlorophenoxyacetic acid (2,4-D) in rat and dog. Xenobiotica 33:805–821. doi:10.1080/0049825031000135405

    Article  Google Scholar 

  23. Van Ravenzwaay B, Pigott G, Leibold E (2004) Absorption, distribution, metabolism and excretion of 4-chloro-2-methylphenoxyacetic acid (MCPA) in rats. Food Chem Toxicol 42:115–125. doi:10.1016/j.fct.2003.08.017

    Article  Google Scholar 

  24. Wu JM, Lee HK (2006) Injection port derivatization following ion-pair hollow fiber-protected liquid-phase microextraction for determining acidic herbicides by gas chromatography/mass spectrometry. Anal Chem 78:7292–7301. doi:10.1021/ac060966e

    Article  CAS  Google Scholar 

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Acknowledgments

Funding for this work was provided by the UK Department for Environment Food and Rural Affairs (Defra).

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Correspondence to Andrew J. A. Charlton.

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Charlton, A.J.A., Stuckey, V. & Sykes, M.D. Determination of the Phenoxyacid Herbicides MCPA, Mecoprop and 2,4-D in Kidney Tissue Using Liquid Chromatography with Electrospray Tandem Mass Spectrometry. Bull Environ Contam Toxicol 82, 711–715 (2009). https://doi.org/10.1007/s00128-009-9636-5

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Keywords

  • Acid herbicides
  • Pesticide poisoning
  • Liquid chromatography
  • Mass spectrometry