Rapid Multi-Residue Determination of Pesticides in Animal-Derived Food via Modified QuEChERS Sample Preparation and GC/MS
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A group of methods were developed for the determination of etofenprox, kresoxim-methyl, cyprodinil, azoxystrobin, and pyrimethanil residues in animal-derived food (milk, egg, pig liver, pig fat, pork, and chicken) by using QuEChERS (quick, easy, cheap, effective, rugged, and safe)-gas chromatography/mass spectrometry (GC/MS). With acetonitrile as the extraction solvent, the samples were pretreated with the improved QuEChERS method including extraction, salting-out, and purification processes. Then, all the sample extracts were analyzed with GC/MS in selected-ion monitoring (SIM) mode and quantified by the external standard method using the matrix-matched standard method. Under electron ionization conditions, the analysis was carried out with a DB-5 MS capillary column (30 m × 0.25 mm, 0.25 μm) at a flow rate of 2.0 mL min−1. 163, 116, 224, 344, and 198 were selected as quantitative ion of etofenprox, kresoxim-methyl, cyprodinil, azoxystrobin, and pyrimethanil, respectively. Under the optimal conditions, the calibration curves showed good linearity in the range of 0.0002–5.0 mg L−1 for the five pesticides mentioned above, with correlation coefficients (R2) were more than 0.99. The average recoveries of the five pesticides spiked at three levels were 72.46–104.88%, with the RSDs (n = 5) of 0.70–11.26%. The LODs (S/N > 3) of five pesticides were 0.0002–0.02 mg L−1; the LOQs were 0.0002–0.01 mg kg−1 in milk, egg, pig liver, pig fat, pork, and chicken samples. Such methods showed the advantages of simplicity, rapidness, and sensitivity, and could meet the requirements for the determination of five pesticides residues in various animal derived foods.
KeywordsPesticide residue GC/MS QuEChERS Animal-derived food
The authors sincerely thank Institute for the Control of Agroehemicals, Ministry of Agriculture of P. R. China.
This study was funded by the Transformation and Popularization Project of Agricultural Scientific and Technological Achievements of Tianjin (Project Number 201502290).
Compliance with Ethical Standards
Conflict of Interest
Xu Qin declares that he has no conflict of interest. Lijie Zhao declares that he has no conflict of interest. Qingqing Huang declares that she has no conflict of interest. Yiyun Liu declares that she has no conflict of interest. Yingming Xu declares that he has no conflict of interest. Dongmei Qin declares that she has no conflict of interest. Yetong Liu declares that she has no conflict of interest.
This article does not contain any studies with human participants or animals performed by any of the authors.
- Abdulra'uf LB, Ibrahim HB, Lawal AR, Tan GH (2016) Pesticide use: properties and environmental fate. Al-Hikmah J Pure Appl Sci 3:22–29Google Scholar
- Anastassiades M, Lehotay SJ, Stajnbaher 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(2):412–431Google Scholar
- Codex Alimentarius Commission (2016) Codex pesticides residues in food online database. [Internet]. [Cited 2017 Sep 12]. Available from: http://www.fao.org/fao-who-codexalimentarius/standards/pesticide-mrls/en/
- Guardia-Rubio M, Córdova MLFD, Ayora-Canada MJ, Ruiz-Medina A (2006) Simplified pesticide multiresidue analysis in virgin olive oil by gas chromatography with thermoionic specific, electron-capture and mass spectrometric detection. J Chromatogr A 1008(2):231–239. https://doi.org/10.1016/j.chroma.2006.01.006 CrossRefGoogle Scholar
- Hamscher G, Prieβ B, Nau H (2007) Determination of phoxim residues in eggs by using high-performance liquid chromatography diode array detection after treatment of stocked housing facilities for the poultry red mite (Dermanyssus gallinae). Anal Chim Acta 586(1-2):330–335. https://doi.org/10.1016/j.aca.2006.09.041 CrossRefGoogle Scholar
- Hernik A, Góralczyk K, Strucinski P, Czaja K, Korcz W, Minorczyk M, Lyczewska M, Ludwicki JK (2014) Characterising the individual health risk in infants exposed to organochlorine pesticides via breast milk by applying appropriate margins of safety derived from estimated daily intakes. Chemosphere 94:158–163. https://doi.org/10.1016/j.chemosphere.2013.09.067 CrossRefGoogle Scholar
- Martini E, Merola G, Tomassetti M, Campanella L (2015) Agent orange herbicides, organophosphate and triazinic pesticides analysis in olive oil and industrial oil mill waste effluents using new organic phase immunosensors. Food Chem 169:358–365. https://doi.org/10.1016/j.foodchem.2014.07.137 CrossRefGoogle Scholar
- Moreno-González D, Huertas-Perez JF, Garcia-Campana AM, Gamiz-Gracia L (2014) Determination of carbamates in edible vegetable oils by ultra-high performance liquid chromatography–tandem mass spectrometry using a new clean-up based on zirconia for QuEChERS methodology. Talanta 128:299–304. https://doi.org/10.1016/j.talanta.2014.04.045 CrossRefGoogle Scholar
- National Health and Family Planning Commission of the PRC, Ministry of Agriculture of the PRC, China Food and Drug Administration (2016) GB 2763–2016 (national food safety standard-maximum residue limits for pesticides in food). Standards Press of China, BeijingGoogle Scholar
- Nortes-Mendez R, Robles-Molina J, Lopez-Blanco R, Vass A, Molina-Diaz A, Garcia-Reyes JF (2016) Determination of polar pesticides in olive oil and olives by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry and high resolution mass spectrometry. Talanta 158:222–228. https://doi.org/10.1016/j.talanta.2016.05.058 CrossRefGoogle Scholar
- Pang GF, Cao YZ, Zhang JJ, Fan CL, Liu YM, Li XM, Jia GQ, Li ZY, Shi YQ, Wu YP, Guo TT (2006) Validation study on 660 pesticide residues in animal tissues by gel permeation chromatography cleanup/gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry. J Chromatogr A 1125(1):1–30. https://doi.org/10.1016/j.chroma.2006.05.023 CrossRefGoogle Scholar
- Rahman M, El-Aty A, Na T, Park J, Kabir H, Chung HS, Lee HS, Shin H, Shim J (2017) Simultaneous quantification of methiocarb and its metabolites, methiocarb sulfoxide and methiocarb sulfone, in five food products of animal origin using tandem mass spectrometry. J Chromatogr B 1060:387–394. https://doi.org/10.1016/j.jchromb.2017.06.025 CrossRefGoogle Scholar
- Rajski L, Lozano A, Ucles A, Ferrer C, Fernandez-Alba AR (2013) Determination of pesticide residues in high oil vegetal commodities by using various multi-residue methods and clean-ups followed by liquid chromatography tandem mass spectrometry. J Chromatogr A 1304:109–120. https://doi.org/10.1016/j.chroma.2013.06.070 CrossRefGoogle Scholar
- Walorczyk S (2014) Validation and use of a QuEChERS-based gas chromatographic-tandem mass spectrometric method for multiresidue pesticide analysis in blackcurrants including studies of matrix effects and estimation of measurement uncertainty. Talanta 120:106–113. https://doi.org/10.1016/j.talanta.2013.11.087 CrossRefGoogle Scholar
- Wang PC, Lee RJ, Chen CY, Chou CC, Lee MR (2012) Determination of cyromazine and melamine in chicken eggs using quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction coupled with liquid chromatographyetandem mass spectrometry. Anal Chim Acta 752:78–86. https://doi.org/10.1016/j.aca.2012.09.029 CrossRefGoogle Scholar