Skip to main content
Log in

A Modified QuEChERS Sample Preparation Method for the Analysis of 70 Pesticide Residues in Tea Using Gas Chromatography-Tandem Mass Spectrometry

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

A modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the simultaneous determination of 70 pesticides in tea was developed using gas chromatography-tandem mass spectrometry. Prior to acetonitrile extraction of the target compounds from tea matrix, samples were soaked in distilled water to improve the extraction efficiency. A mixture of adsorbents containing primary–secondary amine, octadecylsilane, graphite carbon black, and multiwalled carbon nanotubes was applied for the cleanup. Additional steps of concentration and solvent exchange were performed to reduce the amount of co-extracts and to decrease the limit of detection of the method. For all pesticides, good linear calibrations with coefficients (R 2) ≥0.99 were obtained at the concentration levels of 10, or 50 to 1,000 μg ml−1. The limits of quantifications (LOQs) were 5–25 μg ml−1, respectively. The recovery rates of samples spiked with 20, 100, and 200 μg kg−1 of analytes ranged from 71 % to 105 %. In addition, the relative standard deviations were lower than 20 %. A total of 331 tea samples were analyzed using this method, and the levels of five pesticide residues in nine tea samples exceeded the strictest maximum residual limits (MRLs).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  • Anastassiades M, Lehotay S, Stajnbaher SF (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):421–431

    Google Scholar 

  • Cajka T, Sandy C, Bachanova V, Drabova L, Kalachova K, Pulkrabova J, Hajslova J (2012) Streamlining sample preparation and gas chromatography-tandem mass spectrometry analysis of multiple pesticide residues in tea. Anal Chim Acta 743:51–60

    Article  CAS  Google Scholar 

  • Chen GQ, Cao PY, Liu RJ (2011) A multi-residue method for fast determination of pesticides in tea by ultra performance liquid chromatography-electrospray tandem mass spectrometry combined with modified QuEChERS sample preparation procedure. Food Chem 125:1406–1411

    Article  CAS  Google Scholar 

  • Chen Y, Al-Taher F, Juskelis R, Wong JW, Zhang K, Hayward DG, Zweigenbaum J, Stevens J, Cappozzo J (2012) Multiresidue pesticide analysis of dried botanical dietary supplements using an automated dispersive SPE cleanup for QuEChERS and high performance liquid chromatography-tandem mass spectrometry. J Agric Food Chem 60(40):9991–9999

    Article  CAS  Google Scholar 

  • Fan CL, Chang QY, Pang GF, Li ZY, Kang J, Pan GQ, Zheng SZ, Wang WW, Yao CC, Ji XX (2013) High-throughout analytical techniques for determination of residues of 653 multiclass pesticides and chemical pollutants in tea: Part II. Comparative study of extraction efficiencies of three sample preparation techniques. J AOAC Int 96(2):432–440

    Article  CAS  Google Scholar 

  • Frenich AG, Romero-González R, Gómez-Pérez ML, Vidal JLM (2011) Multi-mycotoxin analysis in eggs using a QuEChERS-based extraction procedure and ultra-high-pressure liquid chromatography coupled to triple quadrupole mass spectrometry. J Chromatogr A 1218(28):4349–4356

    Article  CAS  Google Scholar 

  • Gómez-Ramos MM, Ferrer C, Malato O, Agüera A, Fernández-Alba AR (2013) Liquid chromatography-high-resolution mass spectrometry for pesticide residue analysis in fruit and vegetables: screening and quantitative studies. J Chromatogr A 1287:24–37

    Article  Google Scholar 

  • González-Curbelo MÁ, Hernández-Borges J, Borges-Miquel TM, Rodríguez-Delgado MÁ (2011) Determination of pesticides and their metabolites in processed cereal samples. Food Addit Contam A 29(1):104–116

    Article  Google Scholar 

  • Guan YQ (2013) Modified QuEChERS method for the analysis of 11 pesticide residues in tea by liquid chromatography-tandem mass spectrometry. Anal Methods. doi:10.1039/C3AY40441B

    Google Scholar 

  • Guillarme D, Casetta C, Bicchi C, Veuthey JL (2010) High throughput qualitative analysis of polyphenols in tea samples by ultra-high pressure liquid chromatography coupled to UV and mass spectrometry detectors. J Chromatogr A 1217:6882–6890

    Article  CAS  Google Scholar 

  • Hu YY, Zheng P, He YZ, Sheng GP (2005) Response surface optimization for determination of pesticide multiresidues by matrix solid-phase dispersion and gas chromgatography. J Chromatogr A 1098(1–2):188–193

    Article  CAS  Google Scholar 

  • Huang ZQ, Li YJ, Chen B, Yao SZ (2007) Simultaneous determination of 102 pesticide residues in Chinese teas by gas chromatography–mass spectrometry. J Chromatogr, B 853:154–162

    Article  CAS  Google Scholar 

  • Kanrar B, Mandal S, Bhattacharyya A (2010) Validation and uncertainty analysis of a multiresidue method for 42 pesticides in made tea, tea infusion and spent leaves using ethyl acetate extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1926–1933

  • Kolberg DI, Prestes OD, Adaime MB, Zanella R (2011) Development of a fast multiresidue method for the determination of pesticides in dry samples (wheat grains, flour and bran) using QuEChERS based method and GC–MS. Food Chem 125:1436–1442

    Article  CAS  Google Scholar 

  • Kuang H, Miao H, Hou XL, Zhao YF, Shen JZ, Wu YN (2010) Determination of enantiometric fractions of cypermethrin and cis-bifenthrin in Chinese teas by GC/ECD. J Sci Food Agric 90:1374–1379

    Article  CAS  Google Scholar 

  • Lacina O, Zachariasova M, Urbanova J, Vaclavikova M, Cajka T, Hajslova J (2012) Critical assessment of extraction methods for the simultaneous determination of pesticide residues and mycotoxins in fruits, cereals, spices and oil seeds employing ultra-high performance liquid chromatography–tandem mass spectrometry. J Chromatogr A 1262:8–18

    Article  CAS  Google Scholar 

  • 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 1218:1021–1036

    Article  CAS  Google Scholar 

  • Lee JM, Park JW, Jang GC, Hwang KJ (2008) Comparative study of pesticide multi-residue extraction in tobacco for gas chromatography–triple quadrupole mass spectrometry. J Chromatogr A 1187:25–33

    Article  CAS  Google Scholar 

  • Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fu WS, Mastovska K, Hoh E, Leepipatpiboon N (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and Vegetables. J Chromatogr A 1217(16):2548–2560

    Article  CAS  Google Scholar 

  • Li N, Lei L, Nian L, Zhang R, Wu ST, Ren RB, Wang YQ, Zhang HQ, Yu AM (2013) A modified QuEChERS method for the determination of some herbicides in yogurt and milk by high performance liquid chromatography. Talanta 105:219–228

    Article  CAS  Google Scholar 

  • Li Y, Chen X, Fan CL, Pang GF (2012) Compensation for matrix effects in the gas chromatography-mass spectrometry analysis of 186 pesticides in tea matrices using analyte protectants. J Chromatogr A 1266:131–142

    Article  CAS  Google Scholar 

  • Lombardo-Agüí M, García-Campaña M, Gámiz-Gracia L, Cruces-Blanco C (2012) Determination of quinolones of veterinary use in bee products by ultra-high performance liquid chromatography–tandem mass spectrometry using a QuEChERS extraction procedure. Talanta 93:193–199

    Article  Google Scholar 

  • Lu CH, Liu XG, Dong FS, Xu J, Song WC, Zhang CP, Li YB, Zheng YQ (2010) Simultaneous determination of pyrethrins residues in teas by ultra-performance liquid chromatography/tandem mass spectrometry. Anal Chim Acta 678:56–62

    Article  CAS  Google Scholar 

  • Lu DS, Qiu XL, Feng C, Jin YE, Lin YJ, Xiong LB, Wen YM, Wang DL, Wang GQ (2012) Simultaneous determination of 45 pesticides in fruit and vegetable using an improved QuEChERS method and on-line gel permeation chromatography–gas chromatography/mass spectrometer. J Chromatogr, B 2012(895–896):17–24

    Article  Google Scholar 

  • Moeder M, Bauer C, Popp P, Pinxteren MV, Reemtsma T (2012) Determination of pesticide residues in wine by membrane-assisted solvent extraction and high-performance liquid chromatography-tandem mass spectrometry Anal Bioanal Chem 403(6):1731–1741

    CAS  Google Scholar 

  • Nie SP, Xie MY (2011) A review on the isolation and structure of tea polysaccharides and their bioactivities. Food Hydrocolloid 25:144–149

    Article  CAS  Google Scholar 

  • Niell S, Pareja L, González G, González J, Vryzas Z, Cesio V, Papadopoulou-Mourkidou E, Heinzen H (2011) Simple determination of 40 organophosphate pesticides in raw wool using microwave-assisted extraction and GC-FPD anaylysis. J Agric Food Chem 59(14):7601–7608

    Article  CAS  Google Scholar 

  • Pang GF, Fan CL, Zhang F, Yan L, Chang QY, Cao YZ, Liu YM, Li ZY, Wang QJ, Hu XY, Ping L (2011) High-throughput GC/MS and HPLC/MS/MS techniques for the multiclass, multiresidue determination of 653 pesticides and chemical pollutants in tea. J AOAC Int 94:1253–1296

    CAS  Google Scholar 

  • Pyzunska K (2011) Carbon nanotubes as sorbents in the analysis of pesticides. Chemosphere 83:1407–1413

    Article  Google Scholar 

  • Rajski L, Lozano A, Belmonte-Valles N, Uclés A, Uclés S, Mezcua M, Fernandez-Alba AR (2013) Comparison of three multiresidue methods to analyse pesticides in green tea with liquid and gas chromatography/tandem mass spectrometry. Analyst (Cambridge, U K) 138:921–931

    Article  CAS  Google Scholar 

  • Ravelo-Pérez LM, Hernandez-Borges J, Rodriguez-Delgado MA (2008) Multiwalled carbon nanotubes as efficient solid-phase extraction materials of organophosporous pesticides from apple, grape, orange and pineapple fruit juices. J Chromatogr A 1211:33–42

    Article  Google Scholar 

  • Ravelo-Pérez LM, Herrera-Herrera AV, González-Curbelo MA, Hernández-Borges J, Rodríguez-Delgado MA (2010) Carbon nanotubes: solid-phase extraction. J Chromatogr A 1217:2618–2641

    Article  Google Scholar 

  • 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/EEC, Off. J. Eur. Union L 70(2005), 1–16

  • Santilio A, Stefanelli P, Girolimetti S, Dommarco R (2011) Determination of acidic herbicides in cereals by QuEChERS extraction and LC/MS/MS. J Environ Sci Heal B 46(6):535–543

    CAS  Google Scholar 

  • Sharangi AB (2009) Medicinal and thereapeutic potentialities of tea (Camellia sinensis L.) – a review. Food Res Int 42:529–535

    Article  CAS  Google Scholar 

  • Springer VH, Lista AG (2010) A simple and fast method for chlorsulfuron and mersulfuron methyl determination in water samples using multiwalled carbon nanotubes (MWCNTs) and capillary electrophoresis. Talanta 83:126–129

    Article  CAS  Google Scholar 

  • Steiniger D, Lu GP, Butler J, Phillips E, Fintschenko Y (2010) Determination of multiresidue pesticides in green tea by using a modified QuEChERS extraction and ion-trap gas chromatography/mass spectrometry. J AOAC Int 93:1169–1179

    CAS  Google Scholar 

  • Surma M, Sadowska-ROciek AB, Cieślik EJ (2013) Evaluation of the QuEChERS method with GC-MS detection for the determination of organochlorine pesticides in food of animal origin. Food Anal Methods. doi:10.1007/s12161-013-9635-3

    Google Scholar 

  • Walorczyk S, Gnusowski B (2009) Development and validation of a multi-residue method for the determination of pesticides in honeybees using acetonitrile-based extraction and gas chromatography–tandem quadrupole mass spectrometry. J Chromatogr A 1216:6522–6531

    Article  CAS  Google Scholar 

  • Wang J, Chow W, Leung D (2011) Applications of LC/ESI-MS/MS and UHPLC/Qq-TOF-MS for the determination of 141 pesticides in tea. J AOAC Int 94(6):1685–1714

    Article  CAS  Google Scholar 

  • Xu XM, Yu C, Han JL, Li JP, El-Sepai F, Zhu Y, Huang BF, Cai ZX, Wu HW, Ren YP (2011) Multi-residue analysis of pesticides in tea by online SEC-GC/MS. J Sep Sci 34:210–216

    Article  CAS  Google Scholar 

  • Yang X, Xu DC, Qiu JW, Zhang H, Zhang YC, Dong AJ, Ma Y, Wang J (2009) Simultaneous determination of 118 pesticide residues in Chinese teas by gas chromatography-mass spectrometry. Chem Pap 63(1):39–46

    Article  CAS  Google 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 915–916:13–20

    Article  Google Scholar 

  • Zhang X, Mobley N, Zhang JG, Zheng XM, Lu L, Ragin O, Smith CJ (2010) Analysis of agricultural residues on tea using d-SPE sample preparation with GC-NCI-MS and UHPLC-MS/MS. J Agric Food Chem 58:11553–11560

    Article  CAS  Google Scholar 

  • Zhang X, Xu H (2013) Determination of triazoles in tea samples using dispersive solid phase extraction combined with dispersive liquid–liquid microextraction followed by liquid chromatography-tandem mass spectrometry. Food Anal Methods. doi:10.1007/s12161-013-9617-5

    Google Scholar 

  • Zhao HX, Zhao SC, Deng LG, Mao JS, Guo CY, Yang GS, Lu X, Aboul-Enein HY (2013) Rapid determination of organonitrogen, organophosphorus and carbamate pesticides in tea by ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Food Anal Methods 6(2):497–505

    Article  Google Scholar 

  • Zhao PY, Wang L, Jiang YP, Zhang FZ, Pan CP (2012a) Dispersive cleanup of acetonitrile extracts of tea samples by mixed multiwalled carbon nanotubes, primary secondary amine, and graphitized carbon black sorbents. J Agric Food Chem 60:4026–4033

    Article  CAS  Google Scholar 

  • Zhao PY, Wang L, Luo JH, Pan CP (2012b) Determination of pesticide residues in complex matrices using multi-walled carbon nanotubes as reversed-dispersive solid phase extraction sorbent. J Sep Sci 35:153–158

    Article  CAS  Google Scholar 

  • Zheng HB, Zhao Q, Mo JZ, Huang YQ, Luo YB, Yu QW, Feng YQ (2013) Quick, easy, cheap, effective, rugged and safe method with magnetic graphitized carbon black and primary secondary amine as adsorbent and its application in pesticide residue analysis. J. Chromatogr A. doi:10.1016/j.chroma.2013.04.040

Download references

Acknowledgments

This work was supported by the earmarked fund for Modern Agro-Industry Technology Research System (NYCYTX-26) and the Zhejiang Province Natural Science Foundation (LY12B07004).

Conflict of Interest

Hongping Chen has no conflict of interest. Peng Yin has no conflict of interest. Qinghua Wang has no conflict of interest. Ying Jiang has no conflict of interest. Xin Liu has no conflict of interest. This article does not contain any studies with human or animal subjects.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Xin Liu.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 120 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chen, H., Yin, P., Wang, Q. et al. A Modified QuEChERS Sample Preparation Method for the Analysis of 70 Pesticide Residues in Tea Using Gas Chromatography-Tandem Mass Spectrometry. Food Anal. Methods 7, 1577–1587 (2014). https://doi.org/10.1007/s12161-014-9791-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-014-9791-0

Keywords

Navigation