[en] n effective analysis method was developed based on a chemometric tool for the simultaneous quantification of five different post-harvest pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), carbendazim, thiabendazole, iprodione, and prochloraz) in fruits and vegetables. In the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method, the factors and responses for optimization of the extraction and cleanup analyses were compared using the Plackett–Burman (P–B) screening design. Furthermore, the significant factors (toluene percentage, hydrochloric acid (HCl) percentage, and graphitized carbon black (GCB) amount) were optimized using a central composite design (CCD) combined with Derringer’s desirability function (DF). The limits of quantification (LOQs) were estimated to be 1.0 μg/kg for 2,4-D, carbendazim, thiabendazole, and prochloraz, and 1.5 μg/kg for iprodione in food matrices. The mean recoveries were in the range of 70.4–113.9% with relative standard deviations (RSDs) of less than 16.9% at three spiking levels. The measurement uncertainty of the analytical method was determined using the bottom-up approach, which yielded an average value of 7.6%. Carbendazim was most frequently found in real samples analyzed using the developed method. Consequently, the analytical method can serve as an advantageous and rapid tool for the determination of five preservative pesticides in fruits and vegetables.
Christia, C., Bizani, E., Christophoridis, C. & Fytianos, K. Pesticide residues in fruit samples: comparison of different QuEChERS methods using liquid chromatography-tandem mass spectrometry. Environ. Sci. Pollut. Res. 22, 13167-13178 (2015).
Chen, W., Jiao, B., Su, X., Zhao, Q. & Sun, D. Dissipation and residue of 2,4-D in citrus under field condition. Environ. Monit. Assess. 187, 1-8 (2015).
Wang, S., Xu, Y., Pan, C., Jiang, S. & Liu, F. Application of matrix solid-phase dispersion and liquid chromatography-mass spectrometry to fungicide residue analysis in fruits and vegetables. Anal. Bioanal. Chem. 387, 673-685 (2007).
National Food Safety Standard-Maximum Residue Limits for Pesticides in Food, National Health and Family Planning Commission of the Peoples Republic of China, Ministry of Agriculture of the Peoples Republic of China, Beijing, 2014, GB 2763-2014.
European Commission EU pesticides database, http://ec.europa.eu/sanco-pesticides/public/index.cfm (Accessed: 10 August 2009).
EFSA. The 2013 European Union report on pesticide residues in food. EFSA J. 13, 4038 (2015).
EFSA. The 2011 European Union report on pesticide residues in food. EFSA J. 12, 3694 (2014).
Williams, K. J., James, C. R., Thorpe, S. A. & Reynolds, S. L. Two Analytical Methods for the Measurement of 2,4-D in Oranges: an ELISA Screening Procedure and a GC-MS Confirmatory Procedure. Pestic. Sci. 50, 135-140 (1997).
Ramrez Restrepo, A., Gallo Ortiz, A. F., Hoyos Ossa, D. E. & Penuela Mesa, G. A. QuEChERS GC-MS validation and monitoring of pesticide residues in different foods in the tomato classification group. Food Chem. 158, 153-161 (2014).
Lin, L. et al. Determination of imidacloprid, carbendazim and thiabendazole residues in vegetables and fruits by HPLC. Adv. Mater. Res. 781, 1392-1396 (2013).
Subhani, Q., Huang, Z., Zhu, Z. & Zhu, Y. Simultaneous determination of imidacloprid and carbendazim in water samples by ion chromatography with fluorescence detector and post-column photochemical reactor. Talanta 116, 127-132 (2013).
Sack, C., Vonderbrink, J., Smoker, M. & Smith, R. E. Determination of Acid Herbicides Using Modified QuEChERS with Fast Switching ESI+/ESI-LC-MS/MS. J. Agric. Food Chem. 63, 9657-9665 (2015).
Walters, J. Environmental fate of 2,4-dichlorophenoxyacetic acid. Environmental monitoring and pest management. Department of Pesticide Regulation, Sacramento, CA 95814-3510 (1999).
Ucls, A. et al. Application of zirconium dioxide nanoparticle sorbent for the clean-up step in post-harvest pesticide residue analysis. Talanta 144, 51-61 (2015).
Ferrer, C., Martnez-Buene, M. J., Lozano, A. & Fernandez-Alba, A. R. Pesticide residue analysis of fruit juices by LC-MS/MS direct injection. One year pilot survey. Talanta 83, 1552-1561 (2011).
Bogialli, S. et al. Simple and rapid assay for analyzing residues of carbamate insecticides in bovine milk: hot water extraction followed by liquid chromatography-mass spectrometry. J. Chromatogr. A 1054, 351-357 (2004).
Kmellar, B., Pareja, L., Ferrer, C., Fodor, P. & Alba, A. R. F. Study of the effects of operational parameters on multiresidue pesticide analysis by LC-MS/MS. Talanta 84, 262-273 (2011).
Chung, S. W. & Chan, B. T. Validation and use of a fast sample preparation method and liquid chromatography-tandem mass spectrometry in analysis of ultra-trace levels of 98 organophosphorus pesticide and carbamate residues in a total diet study involving diversified food types. J. Chromatogr. A 1217, 4815-4824 (2010).
Stahnke, H., Kittlaus, S., Kempe, G. & Alder, L. Reduction of matrix effects in liquid chromatography-electrospray ionization-mass spectrometry by dilution of sample extracts: How much dilution is needed? Anal. Chem. 84, 1474-1482 (2012).
Anastassiades, M., Lehotay, S. J., Tajnbaher, D. & Schenck, F. J. 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, 412-431 (2003).
Brown, S. D., Sum, S. T., Despagne, F. & Lavine, B. K. Chemometrics. Anal. Chem. 68, 21-62 (1996).
Li, S. et al. Chemometric-assisted QuEChERS extraction method for the residual analysis of thiacloprid, spirotetramat and spirotetramats four metabolites in pepper: application of their dissipation patterns. Food Chem. 192, 893-899 (2016).
Manbohi, A. & Ahmadi, S. H. In-tube magnetic solid phase microextraction of some fluoroquinolones based on the use of sodium dodecyl sulfate coated Fe3O4 nanoparticles packed tube, Anal. Chim. Acta 885, 114-121 (2015).
Plackett, R. L. & Burman, J. P. The design of optimum multifactorial experiments. Biometrica 33, 305-325 (1944).
Candiotia, L. V., De Zanb, M. M., Camara, M. S. & Goicoechea, H. C. Experimental design and multiple response optimization. Using the desirability function in analytical methods development. Talanta 124, 123-138 (2014).
Khodadoust, S., Ghaedi, M. & Hadjmohammadi, M. R. Dispersive nano solid material-ultrasound assisted microextraction as a novel method for extraction and determination of bendiocarb and promecarb: Response surface methodology. Talanta 116, 637-646 (2013).
Hibbert, D. B. Experimental design in chromatography: a tutorial review. J. Chromatogr. B 910, 2-13 (2012).
Montgomery D. C. Design and analysis of experiment. 3rd ed. New York: John Wiley and Sons; 1991.
Monzn, C. M., Teglia, C. M., Del, M. R. & Goicoechea, H. C. Chemometric optimization and validation of a novel dispersive liquid-liquid microextraction-HPLC method for gliclazide, glibenclamide and glimepiride quantitation in serum samples. Microchem. J. 127, 113-119 (2016).
Derringer, G. & Suich, R. Simultaneous optimization of several response variables. J. Qual.Technol. 12, 214-219 (1980).
Almeida Bezerra, M., Erthal Santelli, R., Padua Oliveira, E., Silveira Villar, L. & Escaleira, L. A. Response surface methodology (RSM) as a tool for optimization in analytical chemistry. Talanta 76, 965-977 (2008).
Gritti, F. & Guiochon, G. Repeatability of the efficiency of columns packed with sub-3 μ m core-shell particles: Part III. 2.7 μ m Poroshell 120 EC-C18 particles in 4.6 mm and 2.1 mm×100 mm column formats. J. Chromatogr. A 1252, 56-66 (2012).
Hayes, R., Ahmed, A., Edge, T. & Zhang, H. Core-shell particles: Preparation, fundamentals and applications in high performance liquid chromatography. J. Chromatogr. A 1357, 36-52 (2014).
Nguyen, T. D., Lee, B. S., Lee, B. R., Lee, D. M. & Lee, G. H. A multiresidue method for the determination of 109 pesticides in rice using Quick Easy Cheap Effective Rugged and Safe (QuEChERS) sample preparation method and gas chromatography/mass spectrometry with temperature control and vacuum concentration. Rapid Commun. Mass Spectrom. 21, 3115-3122 (2007).
Garabrant, D. H. & Philbert, M. A. Review of 2,4-Dichlorophenoxyacetic Acid (2,4-D) Epidemiology and Toxicology. Crit. Rev. Toxicol. 32, 233-257 (2002).
Xiong, W. et al. Separation and Quantitation of Three Acidic Herbicide Residues in Tobacco and Soil by Dispersive Solid-Phase Extraction and UPLC-MS/MS. J. Chromatogr. Sci. 52, 1326-1331 (2014).
Vander Heyden, Y. et al. Ruggedness tests on the high-performance liquid chromatography assay of the United States Pharmacopeia XXII for tetracycline hydrochloride. A comparison of experimental designs and statistical interpretations. Anal. Chim. Acta 312, 245-262 (1995).
Method validation and control procedures for pesticide residues analysis in food and feed. European Commission, Directorate of General Health and Consumer Protection. Document no. SANCO/12571/2013.
Dams, R., Huestis, M. A., Lambert, W. E. & Murphy, C. M. Matrix effect in bioanalysis of illicit drugs with LC-MS/MS: influence of ionization type, sample prepara-tion, and biofluid. J. Am. Soc. Mass Spectrom. 14, 1290-1294 (2003).
Abreu, S. D., Caboni, P., Cabras, P., Alves, A. & Garau, V. L. A comparison of a gas chromatographic with electron-capture detection and a gas chromatographic with mass spectrometric detection screening methods for the analysis of famoxadone in grapes and wines. J. Chromatogr. A 1103, 362-367 (2006).
Eurachem/CITAC guide: Quantifying Uncertainty in Analytical Measurement, Ellison, S.L.R.; Williams, A. (eds), 3th ed., 2012.
Jang, J. et al. A matrix sensitive gas chromatography method for the analysis of pymetrozine in red pepper: Application to dissipation pattern and PHRL. Food Chem. 146, 448-454 (2014).
Khodadoust, S. & Hadjmohammadi, M. Determination of N-methylcarbamate insecticides in water samples using dispersive liquidliquid microextraction and HPLC with the aid of experimental design and desirability function. Anal. Chim. Acta 699, 113-119 (2011).
Stalikas, C., Fiamegos, Y., Sakkas, V. & Albanis, T. Developments on chemometric approaches to optimize and evaluate microextraction. J. Chromatogr. A 1216, 175-189 (2009).
Box, G. E. P. & Wilson, K. B. On the experimental attainment of optimum conditions. J. R. Stat. Soc. Ser. B 13, 1-45 (1951).
Khodadoust, S. & Ghaedi, M. Optimization of dispersive liquid-liquidmicroextraction with central composite design for preconcentration ofchlordiazepoxide drug and its determination by HPLC-UV. J. Sep. Sci. 36, 1734-1742 (2013).
Chen, Z. et al. Response surface methodology for the enantioseparation ofdinotefuran and its chiral metabolite in bee products andenvironmental samples by supercritical fluidchromatography/tandem mass spectrometry. J. Chromatogr. A 1410, 181-189 (2015).