Food Analytical Methods

, Volume 10, Issue 6, pp 1826–1843 | Cite as

Determination of 103 Pesticides and Their Main Metabolites in Animal Origin Food by QuEChERS and Liquid Chromatography–Tandem Mass Spectrometry

Article

Abstract

A rapid and sensitive analytical multiresidue method has been developed for the simultaneous determination of 103 pesticides (herbicides, insecticides, and fungicides) and 18 metabolites in foods of animal origin using liquid chromatography-tandem with triple quadrupole in dynamic multiple reaction monitoring (DMRM) mode. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation technique was established, and the efficiency of the dispersive solid-phase extraction (d-SPE) cleanup step was evaluated by comparing the effects of different d-SPE sorbent combinations (primary secondary amine (PSA) + graphitized carbon black (GCB), PSA + C18, C18, and C18 + GCB). The limits of quantification (LOQs) ranged from 1 to 10 μg/kg, and the coefficient of determination (R 2) was ≥0.995 within the calibration linearity range of 0–250 μg/L for all pesticides. The combination of C18 + GCB was validated at two spiking levels (10 and 50 μg/kg) in chicken, fish, pork, and rabbit. Satisfactory recoveries (70–119%) and RSDs ≤17% were achieved for all analytes, except for naptalam (60–69%), pyrimethanil (40–49%), and thiabendazole (62–66%) at 10 μg/kg spiking level. The validated method was successfully applied to the analysis of real samples of food of animal origin.

Keywords

Animal origin foods Pesticide residues Metabolites QuEChERS LC-MS/MS 

Notes

Compliance with Ethical Standards

Funding

This work has been carried out with support from the Public Welfare Fund of Inspection and Quarantine of China (201410177), the National Key Research and Development Program of China (2016YFD0401105), and the Shrimp and Crab Innovation Team of Shandong Agriculture Research System of China (SDAIT-13-07).

Conflict of Interest

Huili Zhang declares that she has no conflict of interest. Jianhua Wang declares that he has no conflict of interest. Li Li declares that she has no conflict of interest. Ying wang declares that she has no conflict of interest.

Ethical Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed Consent

Not applicable.

References

  1. Akoto O, Oppong-Otoo J, Osei-Fosu P (2015) Carcinogenic and non-carcinogenic risk of organochlorine pesticide residues in processed cereal-based complementary foods for infants and young children in Ghana. Chemosphere 132:193–199. doi: 10.1016/j.chemosphere.2015.02.056 CrossRefGoogle Scholar
  2. Amendola G, Pelosi P, Barbini DA (2015) Determination of pesticide residues in animal origin baby foods by gas chromatography coupled with triple quadrupole mass spectrometry. Journal of Environ Sci Heal B 50(2):109–120. doi: 10.1080/03601234.2015.975607 CrossRefGoogle Scholar
  3. Anagnostopoulos C, Miliadis GE (2013) Development and validation of an easy multiresidue method for the determination of multiclass pesticide residues using GC–MS/MS and LC–MS/MS in olive oil and olives. Talanta 112:1–10. doi: 10.1016/j.talanta.2013.03.051 CrossRefGoogle Scholar
  4. Anagnostopoulos C, Bourmpopoulou A, Miliadis G (2013) Development and validation of a dispersive solid phase extraction liquid chromatography mass spectrometry method with electrospray ionization for the determination of multiclass pesticides and metabolites in meat and milk. Anal Lett 46(16):2526–2541. doi: 10.1080/00032719.2013.803251 CrossRefGoogle Scholar
  5. 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(2):412–431Google Scholar
  6. Carneiro RP, Oliveira FAS, Madureira FD, Silva G, de Souza WR, Lopes RP (2013) Development and method validation for determination of 128 pesticides in bananas by modified QuEChERS and UHPLC–MS/MS analysis. Food Control 33(2):413–423. doi: 10.1016/j.chroma.2015.01.040 CrossRefGoogle Scholar
  7. Chatterjee NS, Utture S, Banerjee K, Shabeer TPA, Kamble N, Mathew S, Kumar KA (2016) Multiresidue analysis of multiclass pesticides and polyaromatic hydrocarbons in fatty fish by gas chromatography tandem mass spectrometry and evaluation of matrix effect. Food Chem 196:1–8. doi: 10.1016/j.foodchem.2015.09.014 CrossRefGoogle Scholar
  8. Chen SB, Yu XJ, He XY, Xie DH, Fan YM, Peng JF (2009) Simplified pesticide multiresidues analysis in fish by low-temperature cleanup and solid-phase extraction coupled with gas chromatography/mass spectrometry. Food Chem 113(4):1297–1300. doi: 10.1016/j.foodchem.2008.08.045 CrossRefGoogle Scholar
  9. Chen LN, Song FR, Liu ZQ, Zheng Z, Xing JP, Liu SY (2012) Multi-residue method for fast determination of pesticide residues in plants used in traditional Chinese medicine by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. J Chromatogr A 1225:132–140. doi: 10.1016/j.chroma.2011.12.071 CrossRefGoogle Scholar
  10. China National food safety standard (2014) Maximum residue limits for pesticides in food. Vol GB:2763–2014Google Scholar
  11. Christia C, Bizani E, Christophoridis C, Fytianos K (2015) Pesticide residues in fruit samples: comparison of different QuEChERS methods using liquid chromatography–tandem mass spectrometry. Environ Sci Pollut Res 22(17):13167–13178. doi: 10.1007/s11356-015-4456-0 CrossRefGoogle Scholar
  12. Chung SWC, Chan BTP (2010) 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(29):4815–4824. doi: 10.1016/j.chroma.2010.05.043 CrossRefGoogle Scholar
  13. EU Pesticides Database (n.d.) available at: http://ec.europa.eu/sanco_pesticides
  14. European Commission DG-SANTE (2015) Guidance document on analytical quality control and method validation procedures for pesticide residues analysis in food and feed, No. SANTE/11945/2015Google Scholar
  15. González-Curbelo MÁ, Herrera-Herrera AV, Hernández-Borges J (2013) Analysis of pesticides residues in environmental water samples using multiwalled carbon nanotubes dispersive solid-phase extraction. J Sep Sci 36(3):556–563. doi: 10.1002/jssc.201200782 CrossRefGoogle Scholar
  16. Han LJ, Sapozhnikova Y, Lehotay SJ (2016) Method validation for 243 pesticides and environmental contaminants in meats and poultry by tandem mass spectrometry coupled to low-pressure gas chromatography and ultrahigh-performance liquid chromatography. Food Control 66:270–282. doi: 10.1016/j.foodcont.2016.02.019 CrossRefGoogle Scholar
  17. Hanot V, Goscinny S, Deridder M (2015) A simple multi-residue method for the determination of pesticides in fruits and vegetables using a methanolic extraction and ultra-high-performance liquid chromatography-tandem mass spectrometry: optimization and extension of scope. J Chromatogr A 1384:53–66. doi: 10.1016/j.foodcont.2013.02.027 CrossRefGoogle Scholar
  18. He ZY, Wang L, Peng Y, Luo M, Wang WW, Liu XW (2015) Multiresidue analysis of over 200 pesticides in cereals using a QuEChERS and gas chromatography–tandem mass spectrometry-based method. Food Chem 169:372–380. doi: 10.1016/j.foodchem.2014.07.102 CrossRefGoogle Scholar
  19. Hingmire S, Oulkar DP, Utture SC, Shabeer TPA, Banerjee K (2015) Residue analysis of fipronil and difenoconazole in okra by liquid chromatography tandem mass spectrometry and their food safety evaluation. Food Chem 176:145–151. doi: 10.1016/j.foodchem.2014.12.049 CrossRefGoogle Scholar
  20. Holmes B, Dunkin A, Schoen R, Wiseman C (2015) Single-laboratory ruggedness testing and validation of a modified QuEChERS approach to quantify 185 pesticide residues in salmon by liquid chromatography−and gas chromatography−tandem mass spectrometry. J Agric Food Chem 63:5100–5106. doi: 10.1021/jf5055276 CrossRefGoogle Scholar
  21. Hong Kong pesticide MRL database (2014). http://www.cfs.gov.hk/english/mrl/mrl_preinput.php.
  22. Jones KC, de Voogt (1999) Persistent organic pollutants (POPs): state of the science. Environ Pollut 100(1):209–221. doi: 10.1016/S0269-7491(99)00098-6 CrossRefGoogle Scholar
  23. Layne J, Farcas T, Rustamov I, Ahmed F (2001) Volume-load capacity in fast-gradient liquid chromatography: effect of sample solvent composition and injection volume on chromatographic performance. J Chromatogr A 913(1):233–242. doi: 10.1016/S0021-9673(00)01199-7 CrossRefGoogle Scholar
  24. LeDoux M (2011) Analytical methods applied to the determination of pesticide residues in foods of animal origin. A review of the past two decades. J Chromatogr A 1218(8):1021–1036. doi: 10.1016/j.chroma.2010.12.097 CrossRefGoogle Scholar
  25. Lehotay SJ(2007) Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. J AOAC Int 90:485–520Google Scholar
  26. Liu M, Hashi Y, Song YY, Lin JM (2005) Simultaneous determination of carbamate and organophosphorus pesticides in fruits and vegetables by liquid chromatography–mass spectrometry. J Chromatogr A 1097(1):183–187. doi: 10.1016/j.chroma.2005.10.022 CrossRefGoogle Scholar
  27. Lozano A, Rajski Ł, Belmonte-Valles N et al (2012) Pesticide analysis in teas and chamomile by liquid chromatography and gas chromatography tandem mass spectrometry using a modified QuEChERS method: validation and pilot survey in real samples. J Chromatogr A 1268:109–122. doi: 10.1016/j.chroma.2012.10.013 CrossRefGoogle Scholar
  28. Masiá A, Vásquez K, Campo J, Picó Y (2015) Assessment of two extraction methods to determine pesticides in soils, sediments and sludges. Application to the Túria River Basin J Chromatogr A 1378:19–31. doi: 10.1016/j.chroma.2014.11.079 Google Scholar
  29. Mayer-Helm B (2009) Method development for the determination of 52 pesticides in tobacco by liquid chromatography–tandem mass spectrometry. J Chromatogr A 1216(51):8953–8959. doi: 10.1016/j.chroma.2009.10.077 CrossRefGoogle Scholar
  30. Molina-Ruiz JM, Cieslik E, Walkowska I (2015) Optimization of the quechers method for determination of pesticide residues in chicken liver samples by gas chromatography-mass spectrometry. Food Anal Methods 8(4):898–906. doi: 10.1007/s12161-014-9966-8 CrossRefGoogle Scholar
  31. Muñoz E, Muñoz G, Pineda L, Serrahima E, Centrich F (2012) Multiresidue method for pesticide residue analysis in food of animal and plant origin based on GC or LC and MS or MS/MS. J AOAC Int 95(6):1777–1795. doi: 10.5740/jaoacint.11-036 CrossRefGoogle Scholar
  32. Muralidharan S, Dhananjayan V, Jayanthi P (2009) Organochlorine pesticides in commercial marine fishes of Coimbatore, India and their suitability for human consumption. Environ Res 109(1):15–21. doi: 10.1016/j.envres.2008.08.006 CrossRefGoogle Scholar
  33. Positive List System (2005) Positive List System for Agricultural Chemical Residues in Foods (2005) MRLs Databases http://www.m5.ws001.squarestart.ne.jp/foundation/search.html
  34. Sapozhnikova Y (2014) Evaluation of low-pressure gas chromatography–tandem mass spectrometry method for the analysis of >140 pesticides in fish. J Agric Food Chem 62(17):3684–3689. doi: 10.1021/jf404389e CrossRefGoogle Scholar
  35. Souza R, Pareja L, Cesio MV, Heinzen H (2016) Development of a straightforward and cheap ethyl acetate based method for the simultaneous determination of pesticides and veterinary drugs residues in bovine liver and muscle. Chromatographia 1–12. doi: 10.1007/s10337-016-3026-z
  36. Tran SC, Le HT, Thai-Nguyen TH (2015) Determination of pesticide multi-residues in green tea using a modified QuEChERS extraction and liquid chromatography tandem mass spectrometry technique. Acta Aliment 44(3):409–419. doi: 10.1556/066.2015.44.0012 CrossRefGoogle Scholar
  37. Walorczyk S (2008) Application of gas chromatography/tandem quadrupole mass spectrometry to the multi-residue analysis of pesticides in green leafy vegetables. Rapid Commun Mass Spectrom 22(23):3791–3801. doi: 10.1002/rcm.3800 CrossRefGoogle Scholar
  38. Wang J, Chow W, Leung D, Chang J (2012) Application of ultrahigh-performance liquid chromatography and electrospray ionization quadrupole orbitrap high-resolution mass spectrometry for determination of 166 pesticides in fruits and vegetables. J Agric Food Chem 60(49):12088–12104. doi: 10.1021/jf303939s CrossRefGoogle Scholar
  39. Wu G, Bao XX, Zhao SH, Wu JJ, Han AL, Ye QF (2011) Analysis of multi-pesticide residues in the foods of animal origin by GC–MS coupled with accelerated solvent extraction and gel permeation chromatography cleanup. Food Chem 126(2):646–654. doi: 10.1016/j.foodchem.2010.10.105 CrossRefGoogle Scholar
  40. Zhang JM, Wu YL, Lu YB (2013) Simultaneous determination of carbamate insecticides and mycotoxins in cereals by reversed phase liquid chromatography tandem mass spectrometry using a quick, easy, cheap, effective, rugged and safe extraction procedure. J Chromatogr B 915:13–20. doi: 10.1016/j.jchromb.2012.12.016 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  1. 1.Ocean University of ChinaQingdaoChina
  2. 2.Technical Center of Inspection and QuarantineShandong Entry-Exit Inspection and Quarantine BureauQingdaoChina
  3. 3.Chinese Academy of Inspection and Quarantine BureauBeijingChina
  4. 4.Marine Biology Institute of Shandong ProvinceQingdaoChina

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