Desorption Electrospray Ionization Mass Spectrometry for Trace Analysis of Agrochemicals in Food

Juan F. García-Reyes†‡, Ayanna U. Jackson†, Antonio Molina-Díaz‡ and R. Graham Cooks*†
Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, and Analytical Chemistry Research Group, Department of Physical and Analytical Chemistry, University of Jaén, 23071 Jaén, Spain
Anal. Chem., 2009, 81 (2), pp 820–829
DOI: 10.1021/ac802166v
Publication Date (Web): December 17, 2008
Copyright © 2008 American Chemical Society
* To whom correspondence should be addressed. Phone: 765-494-5262. Fax: 765-494-9421. E-mail: cooks@purdue.edu., †

Purdue University.

, ‡

University of Jaén.

Food and Feed Chemistry

Abstract

Desorption electrospray ionization (DESI) is applied to the rapid, in situ, direct qualitative and quantitative (ultra)trace analysis of agrochemicals in foodstuffs. To evaluate the potential of DESI mass spectrometry (MS) in toxic residue testing in food, 16 representative multiclass agricultural chemicals (pesticides, insecticides, herbicides, and fungicides) were selected (namely, ametryn, amitraz, azoxystrobin, bitertanol, buprofezin, imazalil, imazalil metabolite, isofenphos-methyl, malathion, nitenpyram, prochloraz, spinosad, terbuthylazine, thiabendazole, and thiacloprid). The DESI-MS experiments were performed using 3 μL of solution spotted onto conventional smooth poly(tetrafluoroethylene) (PTFE) surfaces, with examination by MS and tandem mass spectrometry (MS/MS) using an ion trap mass spectrometer. Optimization of the spray solvent led to the use of acetonitrile/water (80:20) (v/v), with 1% formic acid. Most of the compounds tested showed remarkable sensitivity in the positive ion mode, approaching that attainable with conventional direct infusion electrospray mass spectrometry. To evaluate the potential of the proposed approach in real samples, different experiments were performed including the direct DESI-MS/MS analysis of fruit peels and also of fruit/vegetable extracts. The results proved that DESI allows the detection and confirmation of traces of agrochemicals in actual market-purchased samples. In addition, MS/MS confirmation of selected pesticides in spiked vegetable extracts was obtained at absolute levels as low as 1 pg for ametryn. Quantitation of imazalil residues was also undertaken using an isotopically labeled standard. The data obtained were in agreement with those from the liquid chromatography mass spectrometry (LC−MS) reference method, with relative standard deviation (RSD) values consistently below 15%. The results obtained demonstrate the sensitivity of DESI as they meet the stringent European Union pesticide regulation requirements (maximum residue levels) for a large percentage of the studied compounds.

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History

  • Published In Issue January 15, 2009
  • Article ASAPDecember 17, 2008
  • Received: October 13, 2008
    Accepted: November 26, 2008

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