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Rapid Determination of Ethephon in Grapes by Hydrophilic Interaction Chromatography Tandem Mass Spectrometry

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Abstract

Ethephon analysis usually requires indirect and laborious method including a derivatization step before gas chromatography tandem mass spectrometry (GC-MS/MS) determination. In this paper, the described method is quick and based on simple procedure without any clean-up. After addition of ethephon D4 as surrogate, a methanolic extraction was performed. The determination is done by high-performance liquid chromatography (LC) coupled to MS/MS in electrospray-negative mode. The chromatographic separation was achieved on a hydrophilic interaction liquid chromatography (HILIC) column. This methodology significantly reduces the time of analysis to around 10 min for sample extraction and 10 min for determination. The analytical performance was evaluated with grape samples spiked at the limit of quantification, 50 μg kg−1, and at 200 μg kg−1. The results obtained met the SANCO/12571/2013 criteria with recoveries around 96 %, typical of an isotopic dilution method (extraction efficiency was ≈ 60 %). Relative standard deviations in within-day repeatability and day-to-day reproducibility conditions were lower than 5 and 11 %, respectively. Furthermore, the described method is environmental friendly and allows a significant reduction of solvent and reagent consumption.

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References

  • Alpert AJ (1990) Hydrophilic-interaction chromatography for the separation of peptides, nucleic acids and other polar compounds. J Chromatogr A 499:177–196

    Article  CAS  Google Scholar 

  • Anastassiades M, Kolberg D, Mack D, Wildgrube C, Sigalov I, Dörk D (2013) Quick method 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). http://www.crl-pesticides.eu/library/docs/srm/meth_QuPPe.pdf

  • Bonnechère A, Hanot V, Van Loco J (2011) A rapid and environmental friendly determination of the dithiocarbamate metabolites ethylenethiourea and propylenethiourea in fruit and vegetables by ultra high performance liquid chromatography tandem mass spectrometry. J Chromatogr A 1218:4627–4631

    Article  Google Scholar 

  • Bruns S, Lach G, Parlar H (2009) Analysis of ethephon residues in tomato purée method performance assessment. Fresenius Environ Bull 18:2219–2223

    CAS  Google Scholar 

  • Chirita RI, West C, Zubrzycki S, Finaru AL, Elfakir C (2011) Investigations on the chromatographic behaviour of zwitterionic stationary phases used in hydrophilic interaction chromatography. J Chromatogr A 1218:5939–5963

    Article  CAS  Google Scholar 

  • Dinh NP, Jonsson T, Irgum K (2011) Probing the interaction mode in hydrophilic interaction chromatography. J Chromatogr A 1218:5880–5891

    Article  CAS  Google Scholar 

  • European Commission RASFF (2014) Rapid alert system for food and feed. http://ec.europa.eu/food/food/rapidalert/index_en.htm

  • Federal Agency for the Safety of the Food Chain (2013) Controls of pesticide residues in food and feed—Belgium 2012. http://www.afsca.be/thematischepublicaties/_documents/2012_Final_Belgium_controlsofpesticideresidues.pdf

  • Federal Public Service Health Food Chain Safety and Environment (2014). Int Commun

  • Guo Y, Gaiki S (2011) Retention and selectivity of stationary phases for hydrophilic interaction chromatography. J Chromatogr A 1218:5920–5938

    Article  CAS  Google Scholar 

  • Guo Z-X, Cai Q, Yang Z (2007) Ion chromatography/inductively coupled plasma mass spectrometry for simultaneous determination of glyphosate, fosamine, ethephon at nanogram levels in water. Rapid Commun Mass Spectrom 21:1606–1612

    Article  CAS  Google Scholar 

  • Hemström P, Irgum K (2006) Hydrophilic interaction chromatography. J Sep Sci 29:1784–1821

    Article  Google Scholar 

  • Hooijschuur EWJ, Kientz C, Dijksman J, Brinkman UAT (2001) Potential of microcolumn liquid chromatography and capillary electrophoresis with flame photometric detection for determination of polar phosphorus-containing pesticides. Chromatographia 54:295–301

    Article  CAS  Google Scholar 

  • Kawachi Y, Ikegami T, Takubo H, Ikegami Y, Miyamoto M, Tanaka N (2011) Chromatographic characterization of hydrophilic interaction liquid chromatography stationary phases: hydrophilicity, charge effects, structural selectivity, and separation efficiency. J Chromatogr A 1218:5903–5919

    Article  CAS  Google Scholar 

  • Krautz S, Hanika G (2004) Eine einfache und schnelle gaschromatographische Bestimmung von Ethephon in Obste, Gemüse and Getreide mittels Head-space-Analyse. J Mol Nutr Food Res 34:569–570

    Google Scholar 

  • Kumar A, Heaton JC, McCalley DV (2013) Practical investigation of the factors that affect the selectivity in hydrophilic interaction chromatography. J Chromatogr A 1276:33–46

    Article  CAS  Google Scholar 

  • Marin JM, Pozo OJ, Beltran J, Hernandez F (2006) An ion-pairing liquid chromatography/tandem mass spectrometric method for determination of ethephon residues in vegetables. Rapid Commun Mass Spectrom 20:419–426

    Article  CAS  Google Scholar 

  • Noga S, Bocian S, Buszewski B (2013) Hydrophilic interaction liquid chromatography columns classification by effect of solvation and chemometric methods. J Chromatogr A 1278:89–97

    Article  CAS  Google Scholar 

  • Pierik R, Tholen D, Poorter H, Visser EJW, Voesenek LACJ (2006) The Janus face of ethylene: growth inhibition and stimulation. Trends Plant Sci 11:176–183

    Article  CAS  Google Scholar 

  • Royer A, Laporte F, Bouchonnet S, Communal P-Y (2006) Determination of ethephon residues in water by gas chromatography with cubic mass spectrometry after ion exchange purification and derivatisation with N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide. J Chromatogr A 1108:129–135

    Article  CAS  Google Scholar 

  • SANCO/12571/2013 (2013) Guidance document on analytical quality control and validation procedures for pesticide residues analysis in food and feed. http://www.eurl-pesticides.eu/library/docs/allcrl/AqcGuidance_Sanco_2013_12571.pdf

  • Takenaka S (2002) New method for ethephon (2-chloroethylphosphonic acid) residue analysis, and detection of residual levels in the fruit and vegetables of Western Japan. J Agric Food Chem 50:7515–7519

    Article  CAS  Google Scholar 

  • The Commission of the European Communities (2005) Regulation (EC) no 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC. Off J Eur Union L70:1–16

    Google Scholar 

  • The Commission of the European Communities (2007) Commission Regulation (EC) no 333/2007 of 28 March 2007 laying down the methods of sampling and analysis for the official control of the levels of lead, cadmium, mercury, inorganic tin, 3-MCPD and benzo(a)pyrene in foodstuffs. Off J Eur Union L88:29–38

    Google Scholar 

  • The Commission of the European Communities (2012) Commission Implementing Regulation (EU) No 788/2012 of 31 August 2012 concerning a coordinated multiannual control programme of the Union for 2013, 2014 and 2015 to ensure compliance with maximum residue levels of pesticides and to assess the consumer exposure to pesticide residues in and on food of plant and animal origin. Off J Eur Union 235:8–27

    Google Scholar 

  • The Pesticide Manual (2009) A world compendium. The pesticide manual, 15th edn. British Crop Production Council, Alton

    Google Scholar 

  • Tseng S-H, Chang P-C, Chou S-S (2000) A rapid and simple method for the determination of ethephon residue in agricultural products by GC with headspace sampling. J Food Drug Anal 8:213–217

    CAS  Google Scholar 

  • Xue J, Wang S, You X, Dong J, Han L, Liu F (2011) Multi-residues determination of plant growth regulators in apples and tomatoes by liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom 25:3289–3297

    Article  CAS  Google Scholar 

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Acknowledgments

The authors are grateful for the financial support provided by the Belgian Federal Agency for the Safety of the Food Chain (AFSCA-FAVV).

Conflict of Interest

Vincent Hanot declares that he has no conflict of interest. Laure Joly declares that she has no conflict of interest. Aurore Bonnechère declares that she has no conflict of interest. Joris Van Loco declares that he has no conflict of interest. This article does not contain any studies with human or animal subjects.

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  1. Food, Medicines and Consumer Safety Department, Scientific Institute of Public Health, Rue Juliette Wytsman 14, 1050, Ixelles, Belgium

    Vincent Hanot, Laure Joly, Aurore Bonnechère & Joris Van Loco

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  1. Vincent Hanot
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  2. Laure Joly
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  3. Aurore Bonnechère
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  4. Joris Van Loco
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Correspondence to Laure Joly.

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Hanot, V., Joly, L., Bonnechère, A. et al. Rapid Determination of Ethephon in Grapes by Hydrophilic Interaction Chromatography Tandem Mass Spectrometry. Food Anal. Methods 8, 524–530 (2015). https://doi.org/10.1007/s12161-014-9921-8

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  • DOI: https://doi.org/10.1007/s12161-014-9921-8

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