Skip to main content
SpringerLink
Log in

Determination of 72 Chemical Pesticides and Estimation of Measurement of Uncertainty in Rice Using LC-MS/MS and GC-MS/MS

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

A multi-residue method was developed and validated for the simultaneous determination of 39 and 33 chemical pesticides in rice using LC-MS/MS and GC-MS/MS, respectively. The coefficient of determination was 0.994 to 0.999 over the linear concentration range of 0.01 to 0.1 μg mL-1. The LOD and LOQ were in the range of 0.31 to 3.35 and 1.04 to 10.06 μgkg-1, repsectively. The mean recoveries at 0.01, 0.05, and 0.1 mgkg-1 were found within the range 70 to 120% with satisfactory precision (RSD < 15%). Measurement uncertainty (Uexp) values estimated at 0.05 mgkg-1 spiking level were found lower than 20 μgkg-1 for all tested pesticides. A rice and wheat powder check samples under the proficiency test were analyzed using a standardized method, and the Z score recorded within the acceptable range of −2 to +2. The proposed method was applied to analyze the pesticides in real samples collected from the market and quantified the residues. The developed method could be useful for monitoring 72 chemical pesticides in rice matrices and can be adopted for the pesticide monitoring program.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Aguilera A, Rodríguez M, Brotons M, Boulaid M, Valverde A (2005) Evaluation of supercritical fluid extraction/aminopropyl solid-phase “in-line” clean-up for analysis of pesticide residues in rice. J Agric Food chem 53(24):9374–9382

    Article  CAS  Google Scholar 

  • Anastassiades M, Lehotay SJ, Stajnbaher SFJ (2003) A fast and easy multi-residue method employing acetonitrile extraction/partitioning and dispersive solid-phase extraction for the determination of pesticide residues in produce. J AOAC Int 86:412–431

    Article  CAS  Google Scholar 

  • Aparecida de Sousa F, Costa AIG, Ribeiro de Queiroz MEL, Teófilo RF, Neves AA, Paulino de Pinho G (2012) Evaluation of matrix effect on the GC response of eleven pesticides by PCA. Food Chem 135(1):179–185

    Article  Google Scholar 

  • Banerjee K, Oulkar DP, Dasgupta S, Patil SB, Patil SH, Savant R, Adsule PG (2007) Validation and uncertainty analysis of a multi-residue method for pesticides in grapes using ethyl acetate extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1173:98–109

    Article  CAS  Google Scholar 

  • Banerjee K, Utture S, Dasgupta S, Kandaswamy C, Pradhan S, Kulkarni S, Adsule P (2012) Multiresidue determination of 375 organic contaminants including pesticides, polychlorinated biphenyls and polyaromatic hydrocarbons in fruits and vegetables by gas chromatography–triple quadrupole mass spectrometry with introduction of semi-quantification approach. J Chromatogr A 1270:283–295

    Article  CAS  Google Scholar 

  • CIBRC (2018) Major Uses of Pesticides; Registered under the Insecticides Act 1968,. Government of India, Ministry of Agriculture & Farmers Welfare, Department of Agriculture, Cooperation & Farmers Welfare, Directorate of Plant Protection, Quarantine and Storage, Central Insecticide Board & Registration Committee N.H.-IV, Faridabad-121 001 (Haryana). UP TO- 31.05

  • DWR Vision 2050 (2015) Directorate of Weed Research. Indian Council of Agricultural Research New Delhi, pp 1–2

    Google Scholar 

  • Ellison SLR, Williams A (eds) (2012) EURACHEM/CITAC guide: quantifying uncertainty in analytical measurement, 3rd edn ISBN 978-0-948926-30-3. http://www.eurchem.org. Accessed 09 Jan 2020

    Google Scholar 

  • European Commission (2008) Regulation (EC) No. 299/2008 of the European Parliament and of the Council of 11 March 2008 on maximum residue levels of pesticides in or on food and feed of plant and animal origin. Off J Eur Commun L 9:67

    Google Scholar 

  • European Commission (2019) SANTE/11813/2017 of 1st January 2020. Guidance document on analytical quality control and method validation procedures for pesticide residues and analysis in food and feed, pp 1–53

    Google Scholar 

  • FSSAI (2018) Notification-pesticide/stds-FSSAI/2017. Food Safety and Standards Authority of India. Ministry of Health and Family Welfare, 2018. Available from: file:///C:/Users/HP/Downloads/Gazette_Notification_MRL_Pesticides_03_01_2019.pdf. Accessed 15 Dec 2019

    Google Scholar 

  • Grande-Martínez Á, Arrebola-Liébanas FJ, Martínez-Vidal JL, HernándezTorres ME, Garrido-Frenich A (2016) Optimization and validation of a multi-residue pesticide method in rice and wheat flour by modified QuEChERS and GC–MS/MS. Food Anal Methods. 9:548–563. https://doi.org/10.1007/s12161-015-0214-7

    Article  Google Scholar 

  • Gu LL (2017) General situation of pesticide registration and analysis of pesticide import and export of China. Pesticides Letters 11:3–49

    Google Scholar 

  • He Z, Wang L, Peng Y, Wang MLW, Liu X (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

    Article  CAS  Google Scholar 

  • Hercegová A, Dömötörová M, Matisová E (2007) Sample preparation methods in the analysis of pesticides residues in baby food with subsequent chromatographic determination. J Chromatogr A 1153:54–73

    Article  Google Scholar 

  • Hernandez F, Cervera M, Portoles T, Beltran J, Pitarch E (2013) The role of GC–MS/MS with triple quadrupole in pesticide residue analysis in food and the environment. Anal Methods 5(21):5875–5894

    Article  CAS  Google Scholar 

  • IRRI (2006) Bringing hope, improving lives: Strategic Plan 2007-2015 Manila, p 61

    Google Scholar 

  • Kanrar B, Mandal S, Bhattacharyya A (2010) Validation and Uncertainty Analysis of a Multiresidue Method for 67 Pesticides in Made Tea, Tea Infusion, and Spent Leaves Using Ethyl Acetate Extraction and Gas Chromatography/Mass Spectrometry. J AOAC Int 93(2):411–424

    Article  CAS  Google Scholar 

  • Koesukwiwat U, Sanguankaew K, Leepipatpiboon N (2008) Rapid determination of phenoxy acid residues in rice by modified QuEChERS extraction and liquid chromatography-tandem mass spectrometry. Anal Chim Acta 626:10–20

    Article  CAS  Google Scholar 

  • Kolberg DI, Prestes OD, Adaime MB, Zanella R (2011) Development of a fast multi-residue method for the determination of pesticides in dry samples (wheat grains, flour and bran) using QuEChERS based method and GC–MS. Food Chem 125(4):1436–1442

    Article  CAS  Google Scholar 

  • Lee J, Shin Y, Lee J, Lee J, Kim BJ, Kim JH (2018) Simultaneous analysis of 310 pesticide multi-residues using UHPLC-MS/MS in brown rice, orange, and spinach. Chemosphere. 207:519–526. https://doi.org/10.1016/j.chemosphere.2018.05.116

    Article  CAS  PubMed  Google Scholar 

  • Lee SJ, Park HJ, Kim W, Jin JS, Abd El-Aty A, Shim JH (2009) Multiresidue analysis of 47 pesticides in cooked wheat flour and polished rice by liquid chromatography with tandem mass spectrometry. Biomed Chromatogr 23(4):434–442

    Article  CAS  Google Scholar 

  • Lehotay SJ, Kok A, Hiemstra M, Van Bodegraven P (2005) Validation of a fast and easy method for the determination of residues from 229 pesticides in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection. J AOAC 88:595–613

    Article  CAS  Google Scholar 

  • Libin L, Hashi Y, Yaping Q, Haixia Z, Jinming L (2006) Rapid analysis of multiresidual pesticides in agricultural products by gas chromatography-mass spectrometry. Chinese J Anal Chem 34(6):783–786

  • Liu LB, Hashi Y, Qin YP, Zhou HX, Lin JM (2007) Development of automated online gel permeation chromatography–gas chromatograph mass spectrometry for measuring multiresidual pesticides in agricultural products. J Chromatogra B 845(1):61–68

    Article  CAS  Google Scholar 

  • Magnusson B & Örnemark U. (2014). Eurachem guide: the fitness for purpose of analytical methods—a laboratory guide to method validation and related topics. ISBN 978-91-87461-59-0. Available from www.eurachem.org.

    Google Scholar 

  • Mastovska K, Dorweiler KJ, Lehotay SJ, Wegscheid JS, Szpylka KA (2009) Pesticide multi-residue analysis in cereal grains using modified QuEChERS method combined with automated direct sample introduction GC–TOFMS and UPLC–MS/MS techniques. J Agric Food Chem 58(10):5959–5972

    Article  Google Scholar 

  • Mastovska K, Hajslova J, Lehotay SJ (2004) Ruggedness and other performance characteristics of low-pressure gas chromatography–mass spectrometry for the fast analysis of multiple pesticide residues in food crops. J Chromatogr A 1054:335–349

    CAS  PubMed  Google Scholar 

  • Mol HG, Plaza-Bolaños P, Zomer P, de Rijk TC, Stolker AA, Mulder PP (2008) Toward a generic extraction method for simultaneous determination of pesticides, mycotoxins, plant toxins, and veterinary drugs in feed and food matrixes. Anal Chem 80(24):9450–9459

    Article  CAS  Google Scholar 

  • NABL document 141 (2016) National Accreditation Board for Testing and Calibration Laboratories, Guidelines for Estimation and Expression of Uncertainty in Measurement, p 48

    Google Scholar 

  • NABL document 162 (2008) National Accreditation Board for Testing and Calibration Laboratories, Guidelines for Proficiency Testing Program for Testing and Calibration Laboratories, p 31

    Google Scholar 

  • Naik HR, Pallavi MS, Bheemanna M, PavanKumar K, Chandra Sekhara Reddy V, Udaykumar Nidoni R, Paramasivam M, Yadav S (2020) Simultaneous determination of 79 pesticides in pigeonpea grains using GC-MS/MS and LC-MS/MS. Food Chem 347:128986. https://doi.org/10.1016/j.foodchem.2020.128986

    Article  CAS  Google Scholar 

  • Nguyen TD, Han EM, Seo MS, Kim SR, Yun MY, Lee DM, Lee GH (2008) A multi-residue method for the determination of 203 pesticides in rice paddies using gas chromatography/mass spectrometry. Anal Chim Acta 619:67–74

    Article  CAS  Google Scholar 

  • Ni Y, Yang H, Zhang H, He Q, Huang S, Qin M, Chai S, Gao H, Ma Y (2018) Analysis of four sulfonylurea herbicides in cereals using modified Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method coupled with liquid chromatography– tandem mass spectrometry. J Chromatograph A. 1537:27–34. https://doi.org/10.1016/j.chroma.2018.01.017

    Article  CAS  Google Scholar 

  • Pareja L, Fernández-Alba AR, Cesio V, Heinzen H (2011) Analytical methods for pesticide residues in rice, Trends Anal Chem 30(2):270–291

  • Pengyan L, Qingxue L, Yusong M, Xuan J (2006) Analysis of Pesticide Multiresidues in Rice by Gas Chromatography-Mass Spectrometry Coupled with Solid Phase Extraction. Chin J Chromatogr 24:228–234

    Article  Google Scholar 

  • Savary S, Horgan F, Willocquet L, Heong KL (2012) A review of principles for sustainable pest management in rice. Crop Prot 32:54–63

    Article  Google Scholar 

  • Silva CM, da Habermann S, Gustavo M, Mary RR, Zocolo GJ (2012) The role of matrix effects on the quantification of abscisic acid and its metabolites in the leaves of Bauhinia variegata L. using liquid chromatography combined with tandem mass spectrometry. Braz J Plant Physiol 24(3):223–232. https://doi.org/10.1590/S1677-04202012000300009

    Article  Google Scholar 

  • Stahnke H, Alder L (2015) Matrix Effects in Liquid Chrom ato graphy–Electros pray Ionization–Mass Spectrometry. In: Tsipi D, Botitsi H, Economou A (eds) Mass Spectrometry for the Analysis of Pesticide Residues and Their Metabolites, 1st edn. Wiley, pp 161–186

  • Takatori S, Okihashi M, Okamoto Y, Kitagawa Y, Kakimoto S, Murata H (2008) A rapid and easy multiresidue method for the determination of pesticide residues in vegetables, fruits, and cereals using liquid chromatography/tandem mass spectrometry. J AOAC Int 91(4):871–883

    Article  CAS  Google Scholar 

  • Tomer N (2013) Determination of Chlorinated Pesticide in Vegetables, Cereals and Pulses by Gas Chromatography in East National Capital Region, Delhi. India Res J Agric Forestry Sci 1:27–28

    Google Scholar 

  • Tsipi D, Botitsi H, Economou A (2015) Mass Spectrometry for the Analysis of Pesticide Residues and Their Metabolites. John Wiley & Sons, Inc. https://doi.org/10.1002/9781119070771

  • Tsochatzis ED, Menkissoglu-Spiroudi U, Karpouzas DG, Tzimou-Tsitouridou R (2010) A multi-residue method for pesticide residue analysis in rice grains using matrix solid-phase dispersion extraction and high-performance liquid chromatography–diode array detection. Anal Bioanal Chem 397:2181–2190. https://doi.org/10.1007/s00216-010-3645-4

  • Uddin R, Iqbal S, Khan MF, Parveen Z, Ahmed M (2011) Muhammad Abbas, Determination of Pesticide Residues in Rice Grain by Solvent Extraction, Column Cleanup, and Gas Chromatography-Electron Capture Detection. Bull Environ Contam Toxicol 86:83–89. https://doi.org/10.1007/s00128-010-0178-7

    Article  CAS  PubMed  Google Scholar 

  • Walorczyk S (2007) Development of a multi-residue screening method for the determination of pesticides in cereals and dry animal feed using gas chromatography–triple quadrupole tandem mass spectrometry. J Chromatogr A 1165(1):200–212

    Article  CAS  Google Scholar 

  • Wang PX, Yang J, Wang J, Cui AJ, Dong HT, Zhao LW, Zhang ZY, Wang RB, Xu WJ, Li YC, Zhang H, Zhang JJ (2012) Multi-residue method for determination of seven neonicotinoid insecticides in grains using dispersive solid-phase extraction and dispersive liquid–liquid micro-extraction by high performance liquid chromatography. Food Chem 134:1691–1698

    Article  CAS  Google Scholar 

  • Wenzl T, Haedrich J, Schaechtele A, Robouch P, Stroka J (2016) Guidance Document on the Estimation of LOD and LOQ for Measurements in the Field of Contaminants in Feed and Food; EUR 28099, Publications Office of the European Union, Luxembourg, 2016, ISBN 978-92-79-61768-3. https://doi.org/10.2787/8931

    Book  Google Scholar 

  • Zhang WJ, van der Werf W, Pang Y (2011) A simulation model for vegetable-insect pest-insect nucleo polyhedro virus epidemic system. J Environ Entomol 33(3):283–301

    Google Scholar 

  • Zhang X, Shen Y, Yu X, Liu X (2012) Dissipation of chlorpyrifos and residue analysis in rice, soil and water under paddy field conditions. Ecotoxicol Environ Saf 78:276–280

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors gratefully acknowledge the University of Agricultural Sciences, Raichur, India, for laboratory facility and financial support. This project was undertaken with the financial support of Rashtriya Krishi Vikasa Yojana, Government of Karnataka, and University Faculty Research Programme for sustainable grain production and quality supply of food grains. The authors also acknowledge the Directorate of Research, UAS, Raichur, India, for technical support to conduct this project.

Funding

This research was supported by the Rashtriya Krishi Vikas Yojana, Government of Karnataka, and the University of Agricultural Sciences, Raichur, India. [Research grants number: COM/UAS/6270/2019-20].

Author information

Authors and Affiliations

  1. Pesticide Residues and Food Quality Analysis Laboratory, University of Agricultural Sciences, Raichur, Karnataka, 584104, India

    R Harischandra Naik, M S Pallavi, K Pavan Kumar, B.K Vanitha, V Chandra Sekhara Reddy, A Shwetha, Nandini S, Naveenkumar P, R Udaykumar Nidoni & M Bheemanna

Authors
  1. R Harischandra Naik
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M S Pallavi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. K Pavan Kumar
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. B.K Vanitha
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. V Chandra Sekhara Reddy
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A Shwetha
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Nandini S
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Naveenkumar P
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. R Udaykumar Nidoni
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. M Bheemanna
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to R Harischandra Naik.

Ethics declarations

Ethics Approval

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

Consent to Participate

Informed consent does not apply to this study.

Conflict of Interest

Harischandra Naik R declares that there is no conflict of interest. Pallavi M S declares that there is no conflict of interest. Pavan Kumar K declares that there is no conflict of interest. Vanitha B.K declares that there is no conflict of interest. Chandra Sekhara Reddy V declares that there is no conflict of interest. Shwetha A declares that there is no conflict of interest. Nandini Nandini declares that there is no conflict of interest. Naveen Kumar declares that there is no conflict of interest. Udaykumar Nidoni R declares that there is no conflict of interest. Bheemanna M declares that there is no conflict of interest.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

ESM 1

(DOCX 25 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Harischandra Naik, R., Pallavi, M.S., Pavan Kumar, K. et al. Determination of 72 Chemical Pesticides and Estimation of Measurement of Uncertainty in Rice Using LC-MS/MS and GC-MS/MS. Food Anal. Methods 14, 1788–1805 (2021). https://doi.org/10.1007/s12161-021-02000-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-021-02000-9

Keywords

Search

Navigation