Abstract
Flow injection combined with tandem mass spectrometry (MS/MS) was investigated for the rapid detection of highly polar pesticides that are not amenable to multi-residue methods because they do not partition into organic solvents and require dedicated chromatographic conditions. The pesticides included in this study were amitrole, chlormequat, cyromazine, daminozide, diquat, ethephon, fosetyl-Al, glufosinate, glyphosate and its metabolite aminomethylphosphonic acid, maleic hydrazide, mepiquat and paraquat. The composition of the flow-injection solvent was optimized to achieve maximum MS/MS sensitivity. Instrumental limits of detection varied between <0.05 and 1 pg. Fruit, vegetable, cereal, milk and kidney samples were extracted with water (1 % formic acid in case of paraquat/diquat) and ten times diluted in either methanol/0.1 % formic acid, methanol/0.1 % ammonia or acetonitrile/0.1 % ammonia, depending on the pesticide. The ion suppression observed depended strongly on both the matrix and the pesticide. This could be largely compensated for by matrix-matched calibration, but more accurate quantification was obtained by using isotopically labelled standards (commercially available for most of the pesticides studied). The method detection limits ranged from 0.02 mg/kg for chlormequat and mepiquat to 2 mg/kg for maleic hydrazide and were 0.05–0.2 mg/kg for most other pesticide/matrix combinations. This was sufficiently low to test compliance with EU maximum residue limits for many relevant pesticide/commodity combinations. The method substantially reduces the liquid chromatography–MS/MS capacity demand which for many laboratories is prohibitive for inclusion of these pesticides in their monitoring and surveillance programmes.
Similar content being viewed by others
References
Regulation (EC) no 396/2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin. Off J Eur Union L 70:1–16. http://ec.europa.eu/sanco_pesticides/public/index.cfm. Accessed 15 Nov 2013
Lambropoulou DA, Albanis TA (2007) Anal Bioanal Chem 389:1663–1683
Botitsi HV, Garbis SD, Economou A, Tsipi DF (2011) Mass Spectrom Rev 30:907–939
Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fud W, Mastovska K, Hoh E, Leepipatpiboon N (2010) J Chromatogr A 1217:2548–2560
Mol HGJ, Van Dam RCJ, Vreeken RJ, Steijger OM (1999) J Chromatogr A 833:53–60
Mol HGJ, Van Dam RCJ, Vreeken RJ, Steijger OM (2000) J AOAC Int 83:742–747
Esparza X, Moyano E, Galceran MT (2009) J Chromatogr A 1216:4402–4406
Granby K, Johannesen S, Vahl M (2003) Food Addit Contam 20:692–698
Martins-Júnior HA, Lebre DT, Wang AY, Pires MAF, Bustillos OV (2009) Rapid Commun Mass Spectrom 23:1029–1034
Goscinny S, Unterluggauer H, Aldrian J, Hanot V, Masselter S (2012) Food Anal Methods 5:1177–1185
Botero-Coy AM, Ibáñez M, Sancho JV, Hernández F (2013) J Chromatogr A 1292:132–141
Li X, Xu J, Jiang Y, Chen L, Xu Y, Pan C (2009) Acta Chromatogr 21:559–576
Marín JM, Pozo ÓJ, Beltrán J, Hernández F (2006) Rapid Commun Mass Spectrom 20:419–426
Kolberg DIS, Mack D, Anastassiades M, Hetmanski MT, Fussell RJ, Meijer T, Mol HGJ (2012) Anal Bioanal Chem 404:2465–2474
Hernández F, Sancho JV, Pozo ÓJ, Villaplana C, Ibáñez M, Grimalt S (2003) J AOAC Int 86:832–838
Kubilius DT, Bushway RJ (1999) J Liq Chromatogr Relat Technol 22:593–601
Mamani Moreno C, Stadler T, Da Silva AA, Barbosa LCA, De Queiroz MELR (2012) Talanta 89:369–376
Anastassiades M, Kolberg DI, Mack D, Wildgrube C, Sigalova I, Roux D, Fügel D (2013) Quick methods for the analysis of residues of numerous highly polar pesticides in foods of plant origin involving simultaneous extraction with methanol and LC–MS/MS determination (QuPPe-Method), version 7.1. http://www.crl-pesticides.eu/library/docs/srm/meth_QuPPe.pdf. Accessed 15 Nov 2013
Nanita SC, Pentz AM, Bramble FQ (2009) Anal Chem 81:3134–3142
Nanita SC, Stry JJ, Pentz AM, McClory JP, May JH (2011) J Agric Food Chem 59:7557–7568
Nanita SC, Padivitage NLT (2013) Anal Chim Acta 768:1–11
Stahnke H, Reemtsma T, Alder L (2009) Anal Chem 81:2185–2192
Stahnke H, Kittlaus S, Kempe G, Alder L (2012) Anal Chem 84:1474–1482
SANCO/12571/2013, “Method validation and quality control procedures for pesticides residues analysis in food and feed”, http://www.eurl-pesticides.eu/library/docs/allcrl/AqcGuidance_Sanco_2013_12571.pdf. Accessed 9 Jan 2014
Acknowledgement
The Dutch Ministry of Economic Affairs is acknowledged for financially supporting this work (WOT-02-001-017).
Author information
Authors and Affiliations
Corresponding author
Additional information
Published in the topical collection Advanced Food Analysis with guest editors Michel W.F. Nielen, Jana Hajslova, and Rudolf Krska.
Rights and permissions
About this article
Cite this article
Mol, H.G.J., van Dam, R.C.J. Rapid detection of pesticides not amenable to multi-residue methods by flow injection–tandem mass spectrometry. Anal Bioanal Chem 406, 6817–6825 (2014). https://doi.org/10.1007/s00216-014-7644-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-014-7644-8