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Accurate Mass Fragment Library for Rapid Analysis of Pesticides on Produce Using Ambient Pressure Desorption Ionization with High-Resolution Mass Spectrometry

Abstract

U.S. food imports have been increasing steadily for decades, intensifying the need for a rapid and sensitive screening technique. A method has been developed that uses foam disks to sample the surface of incoming produce. This work provides complimentary information to the extensive amount of published pesticide fragmentation data collected using LCMS systems (Sack et al. Journal of Agricultural and Food Chemistry, 59, 6383–6411, 2011; Mol et al. Analytical and Bioanalytical Chemistry, 403, 2891–2908, 2012). The disks are directly analyzed using transmission-mode direct analysis in real time (DART) ambient pressure desorption ionization coupled to a high resolution accurate mass-mass spectrometer (HRAM-MS). In order to provide more certainty in the identification of the pesticides detected, a library of accurate mass fragments and isotopes of the protonated parent molecular ion (the [M+H]+) has been developed. The HRAM-MS is equipped with a quadrupole mass filter, providing the capability of “data-dependent” fragmentation, as opposed to “all -ion” fragmentation (where all of the ions enter a collision chamber and are fragmented at once). A temperature gradient for the DART helium stream and multiple collision energies were employed to detect and fragment 164 pesticides of varying chemical classes, sizes, and polarities. The accurate mass information of precursor ([M+H]+ ion) and fragment ions is essential in correctly identifying chemical contaminants on the surface of imported produce. Additionally, the inclusion of isotopes of the [M+H]+ in the database adds another metric to the confirmation process. The fragmentation data were collected using a Q-Exactive mass spectrometer and were added to a database used to process data collected with an Exactive mass spectrometer, an instrument that is more readily available for this screening application. The commodities investigated range from smooth-skinned produce such as apples to rougher surfaces like broccoli. The minimal sample preparation and absence of chromatography has shortened the analysis time to about 15 min per sample, and the simplicity and robustness of the technique make it ideal for rapid screening.

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References

  1. Sack, C., Smoker, M., Chamkasem, N., Thompson, R., Satterfield, G., Masse, C., Mercer, G., Neuhaus, B., Cassias, I., Chang, E., Lin, Y., MacMahan, S., Wong, J., Zhang, K., Smith, R.E. Collaborative validation of the QuEChERS procedure for the determination of pesticides in food by LC-MS/MS. J. Agr. Food Chem. 59, 6383–6411 (2011)

  2. Mol, H.G.J., Zomer, P., de Koning, M.: Qualitative aspects and validation of a screening method for pesticides in vegetables and fruits based on liquid chromatography coupled to full scan high resolution (Orbitrap) mass spectrometry. Anal. Bioanal. Chem. 403, 2891–2908 (2012)

  3. Neff, R.A., Hartle, J.C., Laestadius, L.I., Dolan, K., Rosenthal, A.C., Nachman, K.E.: A comparative study of allowable pesticide residue levels on produce in the United States. Glob. Health 8, 2–16 (2012)

    Article  Google Scholar 

  4. Casida, J.E.: Pest toxicology: the primary mechanisms of pesticide action. Chem. Res. Toxicol. 22, 609–619 (2009)

    CAS  Article  Google Scholar 

  5. Godfred, D., Osei, A.: Dietary intake of organophosphorus pesticide residues through vegetables from Kumasi, Ghana. Food Chem. Toxicol 46, 3703–3706 (2008)

    Article  Google Scholar 

  6. Soler, C., Mañes, J., Picó, Y.: The role of liquid chromatography-mass spectrometry in pesticide residue determination in food. Crit. Rev. Anal. Chem. 38, 93–117 (2008)

    CAS  Article  Google Scholar 

  7. Crawford, E., Musselman, B.: Evaluating a direct swabbing method for screening pesticides on fruit and vegetable surfaces using direct analysis in real time (DART) coupled to an Exactive benchtop Orbitrap mass spectrometer. Anal. Bioanal. Chem. 10, 2807–2812 (2012)

    Article  Google Scholar 

  8. Farŕe, M., Picó, Y., Barceló, D.: Direct peel monitoring of xenobiotics in fruit by direct analysis in real time coupled to a linear quadrupole ion trap-orbitrap mass spectrometer. Anal. Chem. 85, 2638–2644 (2013)

    Article  Google Scholar 

  9. Wang, L., Zhao, P., Zhang, F., Li, Y., Pan, C.: Direct analysis in real time mass spectrometry for the rapid identification of four highly hazardous pesticides in agrochemicals. Rapid Commun. Mass Spectrom. 26, 1859–1867 (2012)

    CAS  Article  Google Scholar 

  10. Cody, R.B., Laramѐe, J.A., Durst, H.D.: Versatile new ion source for the analysis of materials in open air under ambient conditions. Anal. Chem. 77, 2297–2302 (2005)

    CAS  Article  Google Scholar 

  11. Jones, C.M., Fernández, F.M.: Transmission mode direct analysis in real time mass spectrometry for fast untargeted metabolic fingerprinting. Rapid Commun. Mass Spectrom. 27, 1311–1318 (2013)

    CAS  Article  Google Scholar 

  12. Cajka, T., Danhelova, H., Zachariasova, M., Riddellova, K., Hajslova, J.: Application of direct analysis in real time ionization-mass spectrometry (DART-MS) in chicken meat metabolomics aiming at the retrospective control of feed fraud. Metabolomics 9, 545–557 (2013)

    CAS  Article  Google Scholar 

  13. Self, R.L.: Direct analysis in real time-mass spectrometry (DART-MS) for rapid qualitative screening of toxic glycols in glycerin-containing products. J. Pharm. Biomed. Anal. 80, 155–158 (2013)

    CAS  Article  Google Scholar 

  14. Lesiak, A.D., Musah, R.A., Cody, R.B., Domin, M.A., Dane, A.J., Shepard, J.R.E.: Direct analysis in real time mass spectrometry (DART-MS) of “bath salt” cathinone drug mixtures. Analyst (Cambridge, U. K.) 138, 3424–3432 (2013)

    CAS  Article  Google Scholar 

  15. Vaclavik, L., Zachariasova, M., Hrbek, V., Hajslova, J.: Analysis of multiple mycotoxins in cereals under ambient conditions using direct analysis in real time (DART) ionization coupled to high resolution mass spectrometry. Talanta 82, 1950–1957 (2010)

    CAS  Article  Google Scholar 

  16. Chernetsova, E.S., Bochkov, P.O., Zatonskii, G.V., Abramovich, R.A.: New approach to detecting counterfeit drugs in tablets by DART mass spectrometry. Pharm. Chem. J. 45, 306–308 (2011)

    CAS  Article  Google Scholar 

  17. Edison, S.E., Lin, L.A., Gamble, B.M., Wong, J., Zhang, K.: Surface swabbing technique for the rapid screening for pesticides using ambient pressure desorption ionization with high-resolution mass spectrometry. Rapid Commun. Mass Spectrom. 25, 127–139 (2011)

  18. Edison, S.E., Lin, L.A., Parrales, L.: Practical considerations for the rapid screening for pesticides using ambient pressure desorption ionisation with high-resolution mass spectrometry. Food Addit. Contam. Part 28, 1393–1404 (2011)

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Acknowledgments

The authors thank to Travis Falconer, Greg Mercer, and Detlef Schumann for helpful discussions and assistance with preparing figures.

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Correspondence to Sara E. Kern.

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Kern, S.E., Lin, L.A. & Fricke, F.L. Accurate Mass Fragment Library for Rapid Analysis of Pesticides on Produce Using Ambient Pressure Desorption Ionization with High-Resolution Mass Spectrometry. J. Am. Soc. Mass Spectrom. 25, 1482–1488 (2014). https://doi.org/10.1007/s13361-014-0912-1

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  • DOI: https://doi.org/10.1007/s13361-014-0912-1

Keywords

  • DART ionization
  • Exactive Orbitrap
  • Q-Exactive Orbitrap
  • Pesticide analysis
  • Surface screening technique
  • Rapid analysis