Skip to main content
Log in

Clean-up Procedure Development and Method Validation for Pesticide Residues Analysis in Carrots

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

    We’re sorry, something doesn't seem to be working properly.

    Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.

Abstract

In this work, a method was developed, validated, and applied to determination of ten pesticide residues (trifluralin, carbofuran, chlorothalonil, pendimethalin, captan, tebuconazole, pyraclostrobin, difenoconazole, deltamethrin, and azoxystrobin), from seven distinct classes, in carrot samples, employing a QuEChERS procedure for the analyte extraction and gas chromatography coupled to mass spectrometry (GC-MS) for quantification. The dispersive clean-up step was optimized using different sorbents at different concentrations and mixings. The method proved to be efficient and robust, showing recoveries in the range 72–117%, and RSD ranging from 4.9 to 16.6% (except for chlorothalonil and captan) at fortification levels of 45, 90, 180, and 450 μg kg−1 with seven replicates analyzed for each level (n = 28). Chlorothalonil and captan could not be validated due to analyte stability problems. Detection limits were between 15 and 45 μg kg−1, and the quantification limits were between 45 and 90 μg kg−1. The method was successfully applied to real samples.

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

  • Abad FC, Winck PR, da Silva JM, Caramão EB, Zini CA (2010) Multiresidue determination of pesticides in carrots using pressurized liquid extraction and gas chromatography with mass spectrometry detector. J Braz Chem Soc 21:461–468

    Article  CAS  Google Scholar 

  • ANVISA. Agência Nacional de Vigilância Sanitária (2003) Resolução RE n° 899, de 29 de maio de 2003, Guia para validação de métodos analíticos e bioanalíticos. Diário Oficial da União de 02 de junho de 2003. Brasília (Brazil)

  • ANVISA (2016) Relatório das analises de amostras monitoradas no período de 2013 a 2015. Available from: http://portal.anvisa.gov.br/documents/111215/0/Relat%C3%B3rio+PARA+2013-2015_VERS%C3%83O-FINAL.pdf/494cd7c5-5408-4e6a-b0e5-5098cbf759f8. Accessed 27 March 2018

  • ANVISA (2018a) Monografias de agrotóxicos. Available from: http://portal.anvisa.gov.br/registros-e-autorizacoes/agrotoxicos/produtos/monografia-de-agrotoxicos. Accessed 27 March 2018

  • ANVISA (2018b) Programa de Análise de Resíduos de Agrotóxicos em Alimentos, http://portal.anvisa.gov.br/programa-de-analise-de-registro-de-agrotoxicos-para. Accessed 27 March 2018

  • Avramides EJ (2005) Long-term stability of pure standards and stock standard solutions for the determination of pesticide residues using gas chromatography. J Chromatogr A 1080:166–176

    Article  CAS  PubMed  Google Scholar 

  • CEASA Campinas (2018) Cenoura: Informações Nutricionais. Available from: http://www.ceasacampinas.com.br/novo/Serv_Hortifrutis_Cenoura.asp. Accessed 27 March 2018

  • Cervera MI, Portolés T, Pitarch E, Beltran J, Hernández F (2012) Application of gas chromatography time-of-flight mass spectrometry for target and non-target analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1244:168–177

    Article  CAS  PubMed  Google Scholar 

  • Chasin AADM, Nascimento EDS, Ribeironeto LM, Siqueira MEPBD, Andraus MH, Salvadori MC, Fernícola NAGD, Gorni R, Salcedo S (1998) Validação de métodos em análises toxicológicas: uma abordagem geral. Rev Bras Toxicol 11:1–6

    Google Scholar 

  • Cherta L, Portolés T, Beltran J, Pitarch E, Mol JGJ, Hernández F (2013a) Application of gas chromatography-(triple quadrupole) mass spectrometry with atmospheric pressure chemical ionization for the determination of multiclass pesticides in fruits and vegetables. J Chromatogr A 1314:224–240

    Article  CAS  PubMed  Google Scholar 

  • Cherta L, Beltran J, López F, Hernández F (2013b) Application of fast gas chromatography–mass spectrometry in combination with the QuEChERS method for the determination of pesticide residues in fruits and vegetables. Food Anal Methods 6:1170–1187

    Article  Google Scholar 

  • Chowdhury MAZ, Fakhruddin ANM, Islam MN, Oniruzzaman M, Gan SH, Alam MK (2013) Detection of the residues of nineteen pesticides in fresh vegetable samples using gas chromatography-mass spectrometry. Food Control 34:457–465

    Article  CAS  Google Scholar 

  • Chui QSH, Barros CB, Silva TD (2009) Parametros r e R obtidos de programa interlaboratorial – como usá-los. Quim Nova 32:2209–2213

    Article  Google Scholar 

  • Cunha SC, Lehotay SJ, Mastovska K, Fernandes JO, Oliveira BMPP (2007) Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives. J Sep Sci 30:620–632

    Article  CAS  PubMed  Google Scholar 

  • Dorweiler KJ, Gurav JN, Walbridge JS, Ghatge VS, Savant RH (2016) Determination of stability from multicomponent pesticide mixes. J Agric Food Chem 64:6108–6124

    Article  CAS  PubMed  Google Scholar 

  • EURL – SRM – Analytical Observations Report (2017) Quantification of residues of folpet and captan in QuEChERS extracts, version 3.1, CVUA Stuttgart, Germany, Available from: http://www.eurl-pesticides.eu/userfiles/file/EurlSRM/meth_CaptanFolpet_EurlSRM.pdf. Accessed 20 June 2018

  • Farajzadeh MA, Yadeghari A, Khoshmaram L (2017) Combination of dispersive solid phase extraction and dispersive liquid–liquid microextraction for extraction of some aryloxy pesticides prior to their determination by gas chromatography. Microchem J 131:182–191

    Article  CAS  Google Scholar 

  • Fariña LSC, Rodrigues IMMA, Henriques MHF, araiva RJL (2007) Otimização do rendimento do sumo da cenoura durante o processo produtivo. R Bras Tecnol Agroindustr 1:64–81

    Article  Google Scholar 

  • Gallagher ML (2005) Vitaminas. In: Mahan LK, Escott-stump S (eds) Krause, alimentos, nutrição & dietoterapia, 11th edn. Roca, São Paulo, pp 72–114

    Google Scholar 

  • García-Olmo J, De Pedro E, Garrido A, Paredes A, Sanabria C, Santolalla M, Salas J, García-Hierro JR, González I, García-Cachan MD, Guirao J (2002) Determination of the precision of the fatty acid analysis of Iberian pig fat by gas chromatography. Results of a mini collaborative study. Meat Sci 60:103–109

    Article  PubMed  Google Scholar 

  • González-Curbelo MÁ, Socas-Rodríguez B, Herrera-Herrera AV, González-Sálamo J, Hernández-Borges J, Rodríguez-Delgado MÁ (2015) Evolution and applications of the QuEChERS method. Trends Anal Chem 71:169–185

    Article  CAS  Google Scholar 

  • Guimarães JA, Filho, MM, Moura, AP, Carvalho, ADF (2012) Technical Release 82 – ISSN 1414.9850. Available from: http://www.cnph.embrapa.br/paginas/serie_documentos/publicacoes2012/cot_82.pdf. Accessed 27 March 2018

  • Hennion M-C (2000) Graphitized carbons for solid-phase extraction. J Chromatogr A 885:73–95

    Article  CAS  PubMed  Google Scholar 

  • INMETRO, Instituto Nacional de Metrologia, Normalizacão e Qualidade Industrial (2017) Orientacões sobre validação de métodos de ensaios químicos, DOQ-CGCRE-008, Rev 6, Nov 2017

  • Kirchner M, Matisová E, Otrekal R, Hercegová A, de Zeeuw J (2005) Search on ruggedness of fast gas chromatography-mass spectrometry in pesticide residues analysis. J Chromatogr A 1084:63–70

    Article  CAS  PubMed  Google Scholar 

  • Kruve A, Kunnapas A, Herodes K, Leito I (2008) Matrix effects in pesticide multi-residue analysis by liquid chromatography-mass spectrometry. J Chromatogr A 1187:58–66

    Article  CAS  PubMed  Google Scholar 

  • Kuhn ER (2002) Water injections in GC – how wet can you get? LCGC N Am 20:474–478

    CAS  Google Scholar 

  • Lehotay SJ, de 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 Int 88:595–614

    CAS  PubMed  Google Scholar 

  • Li L, Quinlivan PA, Knappe DRU (2002) Effects of activated carbon surface chemistry and pore structure on the adsorption of organic contaminants from aqueous solution. Carbon 40:2085–2100

    Article  CAS  Google Scholar 

  • Mac Loughlin TM, Peluso MAL, Etchegoyen MAA, Alonso LL, de Castro MAC, Percudani MAC, Marino DJG (2018) Pesticide residues in fruits and vegetables of the argentine domestic market: occurrence and quality. Food Control 93:129–138

    Article  CAS  Google Scholar 

  • Mamum MIR, Park JH, Choi JH, Kim HK, Choi WJ, Han S-S, Hwang K, Jang N-IK, Assayed ME, El-Dib MA, Shin H-C, Abd El-Aty AM, Shim J-H (2009) Development and validation of a multiresidue method for determination of 82 pesticides in water using GC. J Sep Sci 32:559–574

    Article  CAS  Google Scholar 

  • Mastovská M, Lehotay S (2004) Evaluation of common organic solvents for gas chromatographic analysis and stability of multiclass pesticide residues. J Chromatogr A 1040:259–272

    Article  CAS  PubMed  Google Scholar 

  • Munaretto JR, Ferranato G, Ribeiro LC, Martins ML, Adaime MB, Zanella R (2013) Development of a multiresidue method for the determination of endocrine disruptors in fish fillet using gas chromatography–triple quadrupole tandem mass spectrometry. Talanta 116:827–834

    Article  CAS  PubMed  Google Scholar 

  • Orso D, Martins ML, Donato FF, Rizzetti TM, Kemmerich M, Adaime MB, Zanella R (2014) Multiresidue determination of pesticide residues in honey by modified QuEChERS method and gas chromatography with electron capture detection. J Braz Chem Soc 25:1355–1364

    CAS  Google Scholar 

  • Peruga A, Barreda M, Beltrán J, Hernandez F (2013) A robust GC-MS/MS method for the determination of chlorothalonil in fruits and vegetables. Food Addit Contam Part A 30:98–307

    Article  CAS  Google Scholar 

  • Rahman MM, Abd El-Aty AM, Shim J-H (2013) Matrix enhancement effect: a blessing or a curse for gas chromatography? – a review. Anal Chim Acta 801:14–21

    Article  CAS  PubMed  Google Scholar 

  • SANTE 11813/2017, European Comission (2017) Guidance document on analytical quality control and method validation procedures for pesticide residues and analysis in food and feed

  • Viera MS, Rizzetti TM, de Souza MP, Martins ML, Prestes OD, Adaime MB, Zanella R (2017) Multiresidue determination of pesticides in crop plants by the quick, easy, cheap, effective, rugged, and safe method and ultra-high-performance liquid chromatography tandem mass spectrometry using a calibration based on a single level standard addition in the sample. J Chromatogr A 1526:119–127

    Article  CAS  PubMed  Google Scholar 

  • Wu X, Zhang R, Liu X, Guan W, Liu X, Wang Z, Ma Y, Pan C (2015) Evaluation of graphene for effective cleanup of fruit and vegetable extracts in pesticide residue analysis. Food Anal Methods 8:243–253

    Article  Google Scholar 

Download references

Acknowledgments

The authors would like to thank to the Federal University of Rio Grande and to the Post Graduate Program in Technological and Environmental Chemistry for free and high quality education, as well as to the National Council for Scientific and Technological Development for the fellowship provided to Juliana L. da S. Batista.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Márcia H. S. Kurz.

Ethics declarations

Conflict of Interest

Márcia H. S. Kurz declares that she has no conflict of interest. Juliana L. da S. Batista declares that she has no conflict of interest. Lenise G. de Oliveira declares that she has no conflict of interest. Rodrigo Hoff declares that he has no conflict of interest. Manoel L. Martins declares that he has no conflict of interest. Fábio F. Gonçalves declares that he 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

Additional informed consent was obtained from all individual participants for whom identifying information is included in this article.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kurz, M.H.S., da S. Batista, J.L., de Oliveira, L.G. et al. Clean-up Procedure Development and Method Validation for Pesticide Residues Analysis in Carrots. Food Anal. Methods 12, 282–292 (2019). https://doi.org/10.1007/s12161-018-1359-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-018-1359-y

Keywords

Navigation