False-positive liquid chromatography/tandem mass spectrometric confirmation of sebuthylazine residues using the identification points system according to EU directive 2002/657/EC due to a biogenic insecticide in tarragon

Rapid Commun Mass Spectrom. 2009 Apr;23(8):1196-200. doi: 10.1002/rcm.3982.

Abstract

In pesticide residue analysis using liquid chromatography/tandem mass spectrometry (LC/MS/MS) the confirmation of a sebuthylazine finding in a tarragon (Artemisia dranunculus) sample was demonstrated to be false positive. A coeluting interfering matrix compound produced product ions in MS/MS analysis, perfectly corresponding to the multiple reaction monitoring (MRM) of two sebuthylazine transitions. Using the EU directive 2002/657/EC which regulates the confirmation of suspected positive findings would have resulted in a false-positive finding. A third LC/MS/MS transition with a deviant ion ratio and a gas chromatography (GC)/MS/MS analysis revealed the false-positive results. With optimized high resolving ultra-performance liquid chromatography (UPLC) conditions it was possible to separate spiked sebuthylazine from the interfering matrix compound. Using its exact mass and isotope ratios from LC/time-of-flight (TOF) MS measurements, the compound was identified as nepellitorine, a - not surprising - endogenous alkamide in tarragon (Arthemisia dranunculus). False-positive results, especially in heavy matrix samples such as herbs, can be dealt with by further confirmatory analysis, e.g. a third transition, GC analysis if possible or more advantageous by an orthogonal criterion like exact mass.

MeSH terms

  • Artemisia / chemistry*
  • Chromatography, Liquid / methods*
  • European Union
  • False Positive Reactions
  • Gas Chromatography-Mass Spectrometry / methods
  • Guidelines as Topic*
  • Insecticides / analysis*
  • Molecular Structure
  • Pesticide Residues / analysis*
  • Pesticide Residues / chemistry
  • Reference Standards
  • Tandem Mass Spectrometry / methods*

Substances

  • Insecticides
  • Pesticide Residues