Determination of pesticide residues in olives by liquid extraction surface analysis followed by liquid chromatography/tandem mass spectrometry

Authors

  • M. C. Gómez-Almenar IFAPA Centro Venta del Llano
  • J. A. García-Mesa IFAPA Centro Venta del Llano

DOI:

https://doi.org/10.3989/gya.0828142

Keywords:

Food analysis, Liquid extraction, Olives, Pesticide residues, UPLC-MS/MS

Abstract


Nowadays, pesticides are essential in modern agriculture for crop protection, however, this use supposes a potential risk for human health and the environment. Traditional techniques of pesticide determination require the use of laborious and complex extraction methods to separate pesticides from the matrix, above all in fatty matrices like olives. For this reason, a new simple, rapid, cheap and selective method for the extraction and quantification of the most frequently used pesticides in olive growing has been developed. Pesticide determination was carried out by ultra-performance liquid chromatography (UPLC) coupled with triple-quadrupole tandem mass spectrometry (MS/MS). Mean recoveries were found in a range between 73 and 114% with relative standard deviations lower than 20% in most pesticides evaluated and the limits of detection (LODs) and quantification (LOQs) were lower than 4 μg· kg-1 and 8 μg· kg-1, respectively. Finally, this method was applied to the analysis of 25 olive samples where Dimethoate and Terbuthylazine were detected in some cases, but their results were lower than 15 μg· kg-1.

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References

Amvrazi EG, Albanis TA. 2006. Multiresidue method for determination of 35 pesticides in virgin olive oil by using liquid- liquid extraction techniques coupled with solid-phase extraction clean up and gas chromatography with nitrogen phosphorus detection and electron capture detection. J. Agric. Food Chem. 54, 9642–51. http://dx.doi.org/10.1021/jf061375s PMid:17177482

Anastassiades M, Lehotay SJ, Štajnbaher D, Schenck FJ. 2003. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce. J. AOAC Int. 86, 412–31. PMid:12723926

Angioni A, Porcu L, Pirisi F. 2011. LC/DAD/ESI/MS method for the determination of imidacloprid, thiacloprid, and spinosad in olives and olive oil after field treatment. J. Agric. Food Chem. 59, 11359-66. http://dx.doi.org/10.1021/jf2028363 PMid:21942716

Aramendía MA, Borau V, Lafont F, Marinas A, Marinas JM, Moreno JM, Urbano FJ. 2007. Determination of herbicide residues in olive oil by gas chromatography–tandem mass spectrometry. Food Chem. 105, 855–61. http://dx.doi.org/10.1016/j.foodchem.2007.01.063

Ballesteros E, García Sánchez A, Ramos Martos N. 2006. Simultaneous multidetermination of residues of pesticides and polycyclic aromatic hydrocarbons in olive and olivepomace oils by gas chromatography/tandem mass spectrometry. J. Chromatogr. A, 1111, 89–96. http://dx.doi.org/10.1016/j.chroma.2006.01.101 PMid:16480730

Cervera M, Portolés T, Pitarch E, Beltrán J, Hernández F. 2012. Application of gas chromatography time-of-flight mass spectrometry for target and non-target analysis of pesticide residues in fruits and vegetables. J. Chromatogr. A, 1244, 168–177. http://dx.doi.org/10.1016/j.chroma.2012.04.063 PMid:22608778

Covas, M. 2007. Olive oil and the cardiovascular system. Pharmacol. Res. 55, 175–186. http://dx.doi.org/10.1016/j.phrs.2007.01.010 PMid:17321749

Cunha SC, Lehotay SJ, Mastovska K, Fernandes JO, Beatriz M, Oliveira P. 2007a. Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives. J. Sep. Sci. 30, 620–632. http://dx.doi.org/10.1002/jssc.200600410 PMid:17444232

Cunha SC, Fernandes JO, Beatriz M, Oliveira PP. 2007b. Comparison of matrix solid-phase dispersion and liquidliquid extraction for the chromatographic determination of fenthion and its metabolites in olives and olive oils. Food Addit. Contam. 24, 156–164. http://dx.doi.org/10.1080/02652030600970374 PMid:17364916

Cunha SC, Fernandes JO, Beatriz M, Oliveira PP. 2007c. Determination of phosmet and its metabolites in olives by matrix solid-phase dispersion and gas chromatography– mass spectrometry. Talanta, 73, 514–522. http://dx.doi.org/10.1016/j.talanta.2007.04.014 PMid:19073064

DG SANCO. 2013. EU pesticides database. pesticide UE-MRLs: Regulation (EC) no 396/2005. Active substances: Regulation (EC) no 1017/2009. Retrieved from http://ec.europa.eu/sanco_pesticides/public/?event=homepage&CFID=681651&CFTOKEN=66471355&jsessionid=08a0a5b8c1773dd56e8f27333345207652c2TR.

Eikel D, Henion J. 2011. Liquid extraction surface analysis (LESA) of food surfaces employing chip-based nano-electrospray mass spectrometry. Rapid Commun. Mass Spectrom. 25, 2345–2354. http://dx.doi.org/10.1002/rcm.5107 PMid:21766377

European Committee for Standardization. 2013. CEN standard method EN 15662: Food of plant origin—determination of pesticide residues using GC–MS and/or LC-MS/ MS following acetonitrile extraction/partitioning and clean up by dispersive SPE—QuEChERS method. Retrieved from https://www.google.es/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&cad=rja&ved=0CDcQFjAA&url=http%3A%2F%2Fwww.cen.eu%2Fcen%2Fproducts%2Fen%2Fpages%2Fdefault.aspx&ei=WLRyUrjVKceR7AaI7YDoAw&usg=AFQjCNGQvfsZyiJUoTaNOxlai5qKShrEXg.

Ferrer C, Gómez MJ, García-Reyes JF, Ferrer I, Thurman EM, Fernández-Alba AR. 2005. Determination of pesticide residues in olives and olive oil by matrix solid-phase dispersion followed by gas chromatography/mass spectrometry and liquid chromatography/tandem mass spectrometry. J. Chromatogr. A, 1069, 183–194. http://dx.doi.org/10.1016/j.chroma.2005.02.015 PMid:15830944

García-Reyes JF, Ferrer C, Gómez-Ramos MJ, Fernández-Alba AR, García-Reyes JF, Molina-Díaz A. 2007a. Determination of pesticide residues in olive oil and olives. Trac-Trends Anal. Chem. 26, 239–251. http://dx.doi.org/10.1016/j.trac.2007.01.004

García-Reyes JF, Hernando MD, Molina-Díaz A, Fernández-Alba AR 2007b. Comprehensive screening of target, nontarget and unknown pesticides in food by LC-TOF-MS. Trac-Trends Anal. Chem. 26, 828–841. http://dx.doi.org/10.1016/j.trac.2007.06.006

Gilbert-López B, García-Reyes JF, Fernández-Alba AR, Molina- Díaz A. 2010a. Evaluation of two sample treatment methodologies for large-scale pesticide residue analysis in olive oil by fast liquid chromatography–electrospray mass spectrometry. J. Chromatogr. A, 1217, 3736–3747. http://dx.doi.org/10.1016/j.chroma.2010.04.025 PMid:20447638

Gilbert-López B, García-Reyes JF, Lozano A, Fernández-Alba AR, Molina-Díaz A. 2010b. Large-scale pesticide testing in olives by liquid chromatography–electrospray tandem mass spectrometry using two sample preparation methods based on matrix solid-phase dispersion and QuEChERS. J. Chromatogr. A, 1217, 6022–6035. http://dx.doi.org/10.1016/j.chroma.2010.07.062 PMid:20728894

Gilbert-López B, García-Reyes JF, Mezcua M, Ramos-Martos N, Fernández-Alba AR, Molina-Díaz A. 2010c. Multiresidue determination of pesticides in fruit-based soft drinks by fast liquid chromatography time-of-flight mass spectrometry. Talanta, 81, 1310–1321. http://dx.doi.org/10.1016/j.talanta.2010.02.026 PMid:20441900

Guardia Rubio M, Ruiz Medina A, Molina Díaz A, Fernández de Córdova ML. 2006. Determination of pesticides in washing waters of olive processing by gas chromatography-tandem mass spectrometry. J. Sep. Sci. 29, 1578–1586. http://dx.doi.org/10.1002/jssc.200500269 PMid:16922273

Guardia Rubio M, Ayora-Ca-ada MJ, Ruiz-Medina A. 2007a. Effect of washing on pesticide residues in olives. J. Food Sci. 72, 139–143. http://dx.doi.org/10.1111/j.1750-3841.2006.00252.x PMid:17995829

Guardia Rubio M, Ruiz Medina A, Pascual Reguera M, Fernández de Córdova M. 2007b. Multiresidue analysis of three groups of pesticides in washing waters from olive processing by solid-phase extraction-gas chromatography with electrón capture and thermionic specific detection. Microchem. J. 85, 257–264. http://dx.doi.org/10.1016/j.microc.2006.06.005

Guardia Rubio M, Marchal-López RM, Ayora-Ca-ada MJ, Ruiz-Medina A. 2007c. Determination of pesticides in olives by gas chromatography using different detection systems. J. Chromatogr. A, 1145, 195–203. http://dx.doi.org/10.1016/j.chroma.2007.01.068 PMid:17289055

Kmellár B, Fodor P, Pareja L, Ferrer C, Martínez-Uroz MA, Valverde A, Fernandez-Alba AR. 2008. Validation and uncertainty study of a comprehensive list of 160 pesticide residues in multi-class vegetables by liquid chromatographytandem mass spectrometry. J. Chromatogr. A, 1215, 37–50. http://dx.doi.org/10.1016/j.chroma.2008.10.121 PMid:19036377

Koesukwiwat U, Lehotay SJ, Miao S, Leepipatpiboon N. 2010. High throughput analysis of 150 pesticides in fruits and vegetables using QuEChERS and low-pressure gas chromatography– time-of-flight mass spectrometry. J. Chromatogr. A, 1217, 6692–6703. http://dx.doi.org/10.1016/j.chroma.2010.05.012 PMid:20627307

Lehotay SJ, Maštovská K, Lightfield AR. 2005. Use of buffering and other means to improve results of problematic pesticides in a fast and easy method for residue analysis of fruits and vegetables. J. AOAC Int. 88, 615–629. PMid:15859090

Lehotay SJ, O'Neil M, Tully J, García AV, Contreras M, Mol H, Parker A. 2007. Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: Collaborative study. J. AOAC Int. 90, 485–520. PMid:17474521

Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fu W, Mastovska, K, Leepipatpiboon N. 2010. Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J. Chromatogr. A, 1217, 2548–2560. http://dx.doi.org/10.1016/j.chroma.2010.01.044 PMid:20144460

Long R, Gan J, Nett M. 2005. Pesticide choice: Best management practice (BMP) for protecting surface water quality in agriculture. University of California. Division of Agriculture and Natural Resources. Publication Number: 8161, 8161 doi:ISBN-13: 978-1-60107-330-3.

Ruiz-Canela M, Martínez-González MA. 2011. Olive oil in the primary prevention of cardiovascular disease. Maturitas, 68, 245–250. http://dx.doi.org/10.1016/j.maturitas.2010.12.002 PMid:21216542

Sánchez AG, Martos NR, Ballesteros E. 2006. Multiresidue analysis of pesticides in olive oil by gel permeation chromatography followed by gas chromatography–tandem mass-spectrometric determination. Anal. Chim. Acta, 558, 53–61. http://dx.doi.org/10.1016/j.aca.2005.11.019

Wilkowska A, Biziuk M. 2011. Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chem. 125, 803–812. http://dx.doi.org/10.1016/j.foodchem.2010.09.094

Yuzhou L, Xin D. 2012. Methodology for evaluating pesticides for surface water protection I: Initial screening. Department of Pesticide Regulation. Environmental Monitoring Branch.

Published

2015-06-30

How to Cite

1.
Gómez-Almenar MC, García-Mesa JA. Determination of pesticide residues in olives by liquid extraction surface analysis followed by liquid chromatography/tandem mass spectrometry. Grasas aceites [Internet]. 2015Jun.30 [cited 2024Mar.28];66(2):e078. Available from: https://grasasyaceites.revistas.csic.es/index.php/grasasyaceites/article/view/1543

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Research