Analysis of Pesticides in Olive Oil Using a Modified QuEChERS Method with LC-MS/MS and GC-MS/MS

Narong Chamkasem, Tiffany Harmon

Abstract


A simple and high-throughput screening method for the analysis of pesticides in olive oil is presented. A modified QuEChERS sample preparation method was developed to improve the extraction recovery of highly lipophilic pesticides. The acetonitrile extract of the olive oil was directly injected to LC-MS/MS, while other GC-amenable compounds were treated with the modified QuEChERS procedure for GC-MS/MS analysis. The method is an extension of the LIB 4517 to include olive oil. The average recoveries for 80 pesticides quantified by LC-MS/MS at 200, 500, and 1000 ng/g fortifying levels were 91% or better (RSD < 5.5%), while GC-MS/MS analysis demonstrated 81% or better (RSD < 7.2%) for average recovery from 59 compounds at the same spike levels. This method showed an improved recovery of several challenging lipophilic
pesticides in olive oils.


Keywords


QuEChERS, Pesticides Analysis, LC-MS/MS, GC-MS/MS, Olive oil

Full Text:

PDF

References


M. R. Guardia-Rubio, M. F.-D. Cordova, M.J.Ayora-Canada, A. Ruiz-Medina, Determination of pesticide residues in olive oil and olives, Trends in Analytical Chemistry 26 (2007) 239–251.

E. Amvrazi, T. Albanis, 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 (2006) 9642–9651.

P. Cabras, A. Angioni, V.L.Garau, F. Pirisi, M. Pala, Acephate burpofezin residues in olives and olive oil., Food Addit Contam 17 (2000) 855–858.

A. Gillespie, S. Daly, D. Gilvydis, F. Schneider, S. Walter, Multicolumn solid-phase extraction cleanup of organophosphorus and organochlorine pesticide residues in vegetable oils and butterfat, J.AOAC Int. 78 (1995) 431–437.

M. L. Hopper, Automated one-step supercritical fluid extraction and clean-up system for the analysis of pesticide residues in fatty matrices, . J. Chromatogr. A 840 (1999) 93–105.

S. Barrek, O. Paisse, M. F. Grenier-Loustalot, Determination of residual pesticides in olive oil by gcms and hplcms after extraction by sizeexclusion chromatography, J. Agric, Food Chem. 2006, 54, 9642-9651. 376 (2003) 355–359.

M. R. Guardia-Rubio, M. F.-D. Cordova, M.J.Ayora-Canada, A. Ruiz-Medina, Simplified pesticide multiresidue analysis in virgin olive oil by gas chromatography with thermoionic specific, electron-capture and mass spectrometric detection, J. Chromatogr. A 1108 (2006) 231–239.

M. Anastassiades, S. J. Lehotay, D. Stajnbaher, F. J. Schenck, 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 (2003) 412431.

M. Anastassiades, B. Tasdelen, E. Scherbaum, (eprw 2006), crete, greece, new developments in quechers methodology. paper, european pesticide residue workshop, 2006.

S. Lehotay, K. Mastovska, S. Yun, Evaluation of two fast and easy methods for pesticide residue analysis in fatty food matrixes., J. AOAC Int. 88 (2005) 630–638629.

S. Cunha, S. Lehotay, K. Mastovska, J. O. Fernandes, M. Beatriz, P. P. Oliveira, Evaluation of the quechers sample preparation approach for the analysis of pesticide residues in olives, J. Sep. Sci. 30 (2007) 620–632.

Chamkasem, N.; Ollis, L.W.; Harmon, T.; Mercer, G (2012) Laboratory Information Bulletin 4517. Analysis of 136 pesticide in olive oil using a modified QuEChERS method with LC-MS/MS and GC-MS/MS, U.S. Food and Drug Administration, Division of Field Science, HCC-140, Rockville MD.

N. Chamkasem, L. W. Ollis, T. H. S. Lee, G. Mercer, Analysis of 136 pesticides in olive oil using a modified quechers method with lc-ms/ms and gc-ms/ms, J. Agric. Food Chem. 61 (2013) 2315–2329.

EC Council Directive 2002/657/EC of 12 August, 1990 on implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results. O. J. Eur. Communities 2002, L221, 8.

U. Koesukwiwat, S. J. Lehotay, K. MaÅtovsk, K. J. Dorweiler, N. N. Leepipatpiboon, Extension of the quechers method for pesticide residues in cereals to flaxseeds, peanuts, and doughs, J. Agric. Food Chem. 58 (2010) 5950–5958.

Y. Lin; N. Chamkasem;K. Zhang; J. Wong. (2012) Laboratory Information Bulletin 4509. Inter-laboratory validation of the analysis of 250 Pesticide resdidues in food products using a modified QuEChERS and LCMS/MS, U.S. Food and Drug Administration, Division of Field Science, HCC-140, Rockville MD.

A. Veneziano, G. Vacca, S. Arana, F. D. Simone, L. Rastrelli, Determination of carbendazim thiabendazole and thiophanate-methyl in banana (musa acuminata) samples imported to italy, Food Chemistry 87 (2003) 383–386.

M. Okihashi, S. Takatori, Y. Kitagawa, Y. Tanaka, Simultaneous analysis of 260 pesticide residues in agricultural products by gas chromatography/triple quadrupole mass spectrometry, J. AOAC Int. 90 (2007) 1165–1179.

J. Wong, K. Zhang, K. Tech, D. G. Hayward, C. M. Makovi, A. J. Krynistky, F. Schenck, K. K. Banerjee, S. Dasgupta, D. Brown, Multiresidue pesticide analysis in fresh produce by capillary gas chromatography-mass spectrometry/selective ion monitoring (gc-ms/sim) and -tandem mass spectrometry (gc-ms/ms), J. Agric. Food Chem. 58 (2010) 5868–5883.

E. Korta, Bakkali, L. A. Berrueta, G. Gallo, F. F. Vicente, V. Kilchenmann, S. Bogdanov, Study of acaricide stability in honey. characterization of amitraz degradation products in honey and beeswax, J. Agric. Food Chem. 49 (2001) 5835–5842.

Pesticide residues in foods by MeCN extraction and partitioning with magnesium sulfate. Ocial Methods of Analysis of AOAC International; AOAC International: Gaithersburg, MD, 2007; Method 2007.1.

J. HajÅlov, M. Godula, K. MaÅtovsk, Performance of programmed temperature vaporizer, pulsed splitless and on-column injection techniques in analysis of pesticide residues in plant matrices, J. Chromatogr. A 937 (2001) 73–86.

U.S. Food and Drug Administration (1994) Pesticide Analytical Manual Vol. I, Multiresidue Methods, 3rd Ed., U.S. Department of Health and Human Service.