Determination of 103 Pesticides and Their Main Metabolites in Animal Origin Food by QuEChERS and Liquid Chromatography–Tandem Mass Spectrometry
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.
KeywordsAnimal origin foods Pesticide residues Metabolites QuEChERS LC-MS/MS
Compliance with Ethical Standards
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.
This article does not contain any studies with human participants or animals performed by any of the authors.
- 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
- 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
- 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
- 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
- China National food safety standard (2014) Maximum residue limits for pesticides in food. Vol GB:2763–2014Google Scholar
- 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
- EU Pesticides Database (n.d.) available at: http://ec.europa.eu/sanco_pesticides
- 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
- 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
- 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
- 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
- Hong Kong pesticide MRL database (2014). http://www.cfs.gov.hk/english/mrl/mrl_preinput.php.
- 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
- 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
- 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
- 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
- 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
- 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