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.
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.
Schürmann
Andreas
A
Official Food Control Authority, Fehrenstrasse 15, 8032 Zürich, Switzerland. andreas.schuermann@klzh.ch
Dvorak
Veronika
V
Crüzer
Claudio
C
Butcher
Patrick
P
Kaufmann
Anton
A
D019306:Artemisia / Q000737:chemistry*; D002853:Chromatography, Liquid / Q000379:methods*; D005062:European Union; D005189:False Positive Reactions; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods; D017408:Guidelines as Topic; D007306:Insecticides / Q000032:analysis*; D015394:Molecular Structure; D010573:Pesticide Residues / Q000032:analysis* / Q000737:chemistry; D012015:Reference Standards; D053719:Tandem Mass Spectrometry / Q000379:methods*
D007306:Insecticides; D010573:Pesticide Residues