Development and Validation of a Method for the Simultaneous Determination of 20 Organophosphorus Pesticide Residues in Corn by Accelerated Solvent Extraction and Gas Chromatography with Nitrogen Phosphorus Detection
American Journal of Applied Chemistry
Volume 2, Issue 4, August 2014, Pages: 46-54
Received: Jul. 17, 2014;
Accepted: Aug. 5, 2014;
Published: Aug. 10, 2014
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Vesna Kostik, Medical Faculty, Department of Pharmacy, University “Goce Delchev”, Shtip, Republic of Macedonia
Biljana Gjorgeska, Medical Faculty, Department of Pharmacy, University “Goce Delchev”, Shtip, Republic of Macedonia
Bistra Angelovska, Medical Faculty, Department of Pharmacy, University “Goce Delchev”, Shtip, Republic of Macedonia
The method for simultaneous determination of 20 organophosphorus pesticide residues in corn samples has been developed and validated. For the extraction of organophosporus pesticide residues from the samples, the accelerated solvent technique with the mixture of dichloromethane: acetone (1:1, V/V) was used. Clean up was done using liquid – liquid extraction with n – hexane, followed by solid phase extraction on primary secondary amine adsorbent, and elution with the mixture of acetone: toluene (65:35). The determination of the pesticides was carried out by gas chromatography with nitrogen phosphorus detection. Separation and quantitative determination of the analytes were performed on a fused silica capillary ZB-35 column (30 m x 0.25 mm i.d. x 0.25 µm, Phenomenex). The recovery was investigated in blank corn samples fortified with mevinphos, diazinon, dimethoate, bromofos-methyl, chlorfenvinphos, fenamiphos, ethion and phosalone at 5 ng/g, 10 ng/g, 15 ng/g , 20 ng/g and 25 ng/g, respectively and with methacrifos, phorate, etrimfos, parathion-methyl, pirimiphos - methyl, fenitrothion, chlorpyrifos, malathion, parathion, bromofos-ethyl, phosmet and azinphos-methyl at 10 ng/g, 20 ng/g, 30 ng/g, 40 ng/g and 50 ng/g, respectively. The recovery ranged from 76.0% to 112.0%. Repeatability expressed as relative standard deviation (RSD) was less than 8.2%. Linearity expressed as correlation coefficient (R2) ranged from 0.9935 to 0.9996. Measurement uncertainty (Ux) was lower than 14.2% for all tested pesticides. The limits of quantification (LOQ) were bellow 5 ng/g for all tested pesticides. The satisfactory Z-score results of international proficiency tests confirm good analytical performances of the developed method.
Development and Validation of a Method for the Simultaneous Determination of 20 Organophosphorus Pesticide Residues in Corn by Accelerated Solvent Extraction and Gas Chromatography with Nitrogen Phosphorus Detection, American Journal of Applied Chemistry.
Vol. 2, No. 4,
2014, pp. 46-54.
R.J.Cremlyn, “Agrochemicals – preparation and mode of action”. John Wiley & Sons, Ltd. Baffins Lane, Chichester, West Sussex, England, pp.105 -145, 1991.
D. J. Ecobichon, “Pesticide use in developing countries”, Toxicology, vol. 160 (1-3), pp.27 – 33, 2001.
T. Cserháti and M. Szőgyi, “Chromatographic determination of pesticides in food and food products”, Eur.Chem. Bull., vol. 1(3-4), pp. 58-68, 2012.
P. Cabras and A. Angioni, “Pesticides residues in grapes, wine and their processing products,” Journal of Agricultural and Food Chemistry, vol. 48 (4), pp. 967-973, 2000.
S. Navarro, J. Oliva, G. Navarro and A. Barba, ”Dissipation of chlorpyrifos, fenarimol, mancozeb, metalaxyl, penconazole, and vinclozol in in grapes,” American Journal of Enology and Viticulture,” vol. 52 (1), pp.35-40, 2001.
T. Kostov and Z. Pacanoski, ”Weeds with major economic impact on agriculture in the Republic of Macedonia ”, Pak. J. Weed Sci. Res., vol.13 (3-4), pp.227-239, 2007.
T. Đorđević, S. Šiler- Marinković, R. Đurović- Pejčev, S. Dimitrijević-Branković , J.Gajić and U. Miljendić, ” Efficiencies in different methods for determination of organophosphate pesticide residues in fermented wheat substrate”, Pestic. Phytomed. vol. 28 (2), pp.133-140, 2013.
U. Uygun, R. Uzkara, A. Uzbey and H. Koksel, “Residue levels of malathion and fenitrothion and their metabolites in postharvest treated barley during storage and malting”, Food Chemistry, vol. 100 (3), pp. 1165-1169, 2007.
J.Sonchieua, M.Benoit-Ngassoum, J. Bosco-Tchatchueng, A. Kumar-Srivastava and L.P.Srivastava, “Survey of pesticide residues in maize, cowpea and millet from northern Cameroon part I”, Food Additives and Contaminants: Part B. vol.1 (3), pp.178-184 , 2010.
D .R.Sharma, R.B.Thapa, H.K.Manandhar, S.M. Shrestha and S.B.Pradhan, “Use of pesticides in Nepal and impacts on human’s health and environment”, The Journal of Agriculture and Environment vol. 13, pp. 67-74 , 2012.
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/EECText.
S. Zilić, M. Milasinović, D. Terzić, M. Barac and D. Ignjatović-Mičić, “Grain characteristics and composition of maize specialty hybrids”, Spanish Journal of Agricultural Research, vol. 9 (1), pp. 230-241, 2011.
B. Tang, J.E. Zhang, L.G. Zang, Y. Z. Zhang, X.Y. Li and L. Zhou, “Determination of nine organophosphorus pesticides in cereals and kidney beans by capillary gas chromatography with flame photometric detection”, Journal of Chromatographic Science, 43 (7), pp. 337-341, 2005.
M. B. Mariani, V. D'Aiuto and V. Giannetti, “Multiresidue method for the determination of organophosphorus pesticides in cereal matrixes”,J. AOAC Int., vol.93 (3), pp. 999 – 1006, 2010.
D.H. Kim, G.S. Heo and D.W. Lee, “Determination of organophosphorus pesticides in wheat flour by supercritical fluid extraction and gas chromatography with nitrogen–phosphorus detection”, Journal of Chromatography A, vol. 824 (1), pp. 63-70, 1998.
P. Liu and Y. Ma, “Determination of 36 pesticide residues in corn using gas chromatography mass spectrometry”, Journal of Hunan Agricultural University, vol. 7, pp. 1-13, 2005.
Y. Hirara, M. Kimura, T. Inoue, Sh. Uchikawa, S. Otani, A. Haganuma, N. Matsumoto, A. Hirata, Sh. Maruyama, T. Ilizuka, M. Ukyo, M. Ota, H. Hirose, S. Suzuki and Y. Uchida, “Validation of multiresidue screening methods for the determination of 186 pesticides in 11 agricultural products using gas chromatography”, Journal of Health Science, vol. 51(5), pp. 617-627, 2005.
J. Zhao, “Gas Chromatography Simultaneous Determination of Fourteen Organic Phosphorus Residues in food”, Analysis and Testing Technology and Instruments, vol. 18 (2), pp. 106 – 110, 2012.
S. Hanwen, G. Xusheng , L. Yunkai and W. Anbang, “Application of accelerated solvent extraction in the analysis of organic contaminants, bioactive and nutritional compounds in food and feed”, Journal of Chromatography A, vol. 1237, pp. 1-23 , 2012.
J. L Ezzell, B.E. Richter, W.D Felix., S. R. Black and J. E. Meikle, “A comparison of Accelerated Solvent Extraction with conventional solvent extraction for organophosphorus pesticides and herbicides”, LC-GC, vol. 13, pp. 390 – 398 , 1995.
B. Albero, C. Sánchez-Brunete and J. L. Tadeo, “Determination of organophosphorus pesticides in fruit juices by matrix solid – phase dispertion gas chromatography”, Journal of Agricultural and Food Chemistry, vol. 51 (24), pp. 6915 – 6921, 2003.
M. Anastassiades, S.J. Lehotay, D. Stajhbaher and F.J. Schenck, “Fast and easy multi-residue method employing acetonitrile extraction/partitioning and dispersive solid- phase extraction for the determination of pesticide residues in produce”, J. AOAC Int., vol. 86 (2), pp. 412 – 431, 2003.
S. Lehotay, A. de Kok, M. Hiemstra and P. van Bodegraven, “Validation of a Fast and Easy Method for the Determination of Residues from 229 Pesticides in Fruits and Vegetables Using Gas and Liquid Chromatography and Mass Spectrometric Detection”, J. AOAC Int., vol.88 (2), pp. 595 – 614, 2005.
S. Lehotay, “Determination of Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with Magnesium Sulfate: Collaborative Study”, J. AOAC Int., vol. 90 (2), pp. 485-520, 2007.
M.H. EL- Saeid and M.T.Selim, “Multiresidue analysis of 86 pesticides using gas chromatography mass spectrometry: II – no leafy vegetables”, Journal of Chemistry, vol. 2013, pp. 1 – 10, 2013.
F.J. Schenck, S.J. Lehotay and V. Vega, “Comparison of solid-phase extraction sorbents for cleanup in pesticide residue analysis of fresh fruits and vegetables”, J. Sep. Sci. vol. 25 (14), pp. 883 – 890, 2002.
Guidance document on analytical quality control and validation procedures for pesticide residues analysis in food and feed, European Commission, Directorate General Health and Consumer Protection, SANCO/12571 rev.0.0 , 2013.
J.C. Miller and J. N. Miller, “Statistic for analytical chemistry”, 3rd Ed., Ellis Horwood Ptr. Prentice Hall, pp. 104 – 141, 1993.
Quantifying Uncertainty in Analytical Measurement, Eurachem/CITAC Guide CG 4, 3rd Ed., S. L. R. Ellison (LGC, UK), A. Williams (UK), pp. 4-31, 2012.