Skip to main content
SpringerLink
Log in

Development of a Methodology for the Simultaneous Analysis of Multiclass Contaminants in Milk

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

A simple methodology for the simultaneous determination of 67 pesticides, 25 veterinary drugs, and aflatoxin M1 in raw milk was developed and validated. After evaluating different combinations of sample preparation protocols, an extraction with acetonitrile:water (2:1) with QuEChERS citrate buffer salts and a combination of RP-C18 and anhydrous magnesium sulfate for the dispersive clean-up, using gas and liquid chromatography couples to mass spectrometry for determination, was selected. Recovery percentages were between 70 and 120%, with relative standard deviations below 20% at 5, 20, and 50 μg kg−1. Aflatoxin M1 was recovered in the range 66 to 88% at 0.05, 0.1, and 0.5 μg kg−1 with relative standard deviation between 8 and 11%. The quantification limits for all the analytes with the exception of diclofenac were below their respective maximum residue limits. The method was applied for the analysis of 20 commercial samples, some of which showed at least one contaminant below their maximum residue limits.

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

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • Acosta Y (2008) Utilización de ensilaje de grano húmedo: Alternativas de corrección proteica. Jornada de Actualización Técnica en Lechería. INIA La Estanzuela. Florida, Uruguay, 43–49. http://www.ainfo.inia.uy/digital/bitstream/item/574/1/14445240610133839.pdf/. Accessed 18.02.2019

  • Ahn YG, Shin JH, Kim H, Khim J, Lee M, Hong J (2007) Application of solid-phase extraction coupled with freezing-lipid filtration clean-up for the determination of endocrine-disrupting phenols in fish. Anal Chim Acta 603:67–75. https://doi.org/10.1007/s00216-014-8386-3

    Article  CAS  PubMed  Google Scholar 

  • Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck F (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. J Assoc Anal Commun Int 86:412–431

    CAS  Google Scholar 

  • Anderson CR, Rupp HS, Wu WH (2005) Complexities in tetracycline analysis-chemistry, matrix extraction, cleanup, and liquid chromatography. J Chromatogr A 1075:23–32. https://doi.org/10.1016/j.chroma.2005.04.013

    Article  CAS  PubMed  Google Scholar 

  • Burgueño A, Peréz-Parada A, Heinzen A (2015) Determinación de 64 residuos de pesticidas en leche materna por GC-MS y LC-MS/MS y aplicación piloto en muestras reales. Cuarto Encuentro Nacional de Química. Montevideo, Uruguay

    Google Scholar 

  • Cajarville C, Mendoza A, Santana A, Repetto JL (2012) En tiempos de intensificación productiva, ¿Cuánto avanzamos en el conocimiento de los nuevos sistemas de alimentación de la vaca lechera? Veterinaria 48:35–39 http://www.ainfo.inia.uy/digital/bitstream/item/11770/1/AUPA-2012-35-39-Cajarville.pdf/ Accessed 18.02.2019

    Google Scholar 

  • Ciscato C, Barbosa C, Gebara A (2016) Multiresidue analysis of pesticides in bovine milk by GC/MS/MS with BondElut QuEChERS EN Kits. Agilent Application Note. https://www.agilent.com/cs/library/applications/5991-6916EN.pdf, Accessed 18.02.2019

  • Codex Alimentarius Commission, (2015) Codex Veterinary Drug Residue in Food, 38th Session. http://www.codexalimentarius.org/standards/vetdrugs/veterinary-drugs/en/ Accessed 19.02.2019

  • Codex Alimentarius Commission, (2018) Codex Pesticides Residues in Food Online Database, http://www.fao.org/fao-who-codexalimentarius/codex-texts/dbs/pestres/en/ Accessed 18.02.2019

  • Danezis GP, Anagnostopoulos CJ, Liapis K, Koupparis MA (2016) Multi-residue analysis of pesticides, plant hormones, veterinary drugs and mycotoxins using HILIC chromatography – MS/MS in various food matrices. Anal Chim Acta 942:121–138. https://doi.org/10.1016/j.aca.2016.09.011

    Article  CAS  PubMed  Google Scholar 

  • Dasenaki ME, Thomaidis NS (2015) Multi-residue determination of 115 veterinary drugs and pharmaceutical residues in milk powder, butter, fish tissue and eggs using liquid chromatography tandem mass spectrometry. Anal Chim Acta 880:103–121. https://doi.org/10.1016/j.aca.2015.04.013

    Article  CAS  PubMed  Google Scholar 

  • Dasenaki ME, Bletsou AA, Koulis GA, Thomaidis NS (2015) Qualitative Multiresidue screening method for 143 veterinary drugs and pharmaceuticals in milk and fish tissue using liquid chromatography quadrupole-time-of-flight mass spectrometry. J Agric Food Chem 63(18):4493–4508. https://doi.org/10.1021/acs.jafc.5b00962

    Article  CAS  PubMed  Google Scholar 

  • European Commission, (2008) Regulation (EC) No.299/2008 of the European Parliament and of the Council of 11 March 2008 amending Regulation (EC) No. 396/2005 on maximum residue levels of pesticides in or on food and feed of Plant and animal origin, Off J Eur Commun L9

  • European Commission (2010) Regulation (EU) No 37/2010 of the Commission of 22 December 2009 on pharmacologically active substances and their classification as regards the maximum residue limits in foodstuffs of animal origin. L 15 1:1–72

    Google Scholar 

  • European Commission DG-SANTE (2017) Method validation and quality control procedures for pesticide residue analysis in food and feed. Document No. SANTE/11813/2017.http://ec.europa.eu/food/plant/pesticides/guidance_documents/docs/qualcontrol_en.pdf/ Accessed 20.11.2018

  • Frenich AG, Romero-González R, Del Mar Aguilera-Luiz M (2014) Comprehensive analysis of toxics (pesticides, veterinary drugs and mycotoxins) in food by UHPLC–MS. Trends Anal Chem 63:158–169. https://doi.org/10.1016/j.trac.2014.06.020

    Article  CAS  Google Scholar 

  • Imamoglu H, Olgun EVO (2016) Analysis of veterinary drug and pesticide residues using the ethyl acetate multiclass/multiresidue method in milk by Liquid Chromatography-Tandem Mass Spectrometry. J Anal Methods Chem 2:1–17. https://doi.org/10.1155/2016/2170165

    Article  CAS  Google Scholar 

  • Iqbal S, Jinap S, Peroz A, Razis AFA (2015) Aflatoxin M1 in milk and dairy products, occurrence and recent challenges: a review. Trends Food Sci Technol 46(1):110–119. https://doi.org/10.1016/j.tifs.2015.08.005

    Article  CAS  Google Scholar 

  • Jadhava MR, Pudale A, Raut P, Utture S, TPA, Shabeer Banerjee K (2019) A unified approach for high-throughput quantitative analysis of the residues of multi-class veterinary drugs and pesticides in bovine milk using LC-MS/MS and GC-MS/MS. Food Chem 272:292–305. https://doi.org/10.1016/j.foodchem.2018.08.033

    Article  CAS  Google Scholar 

  • Kellnerová E, Navrátilová P, Borkovcová I (2014) Effect of pasteurization on the residues of tetracyclines in milk. Acta Vet Brno 83:21–26. https://doi.org/10.2754/avb201483S10S21

    Article  Google Scholar 

  • Khaniki JGR (2007) Chemical Contaminants in Milk and Public Health Concerns: a Review. J Dairy Sci 2(2):104–1115. https://doi.org/10.3923/ijds.2007.104.115

    Article  CAS  Google Scholar 

  • Kmellar B, Fodor P, Pareja L, Ferrer C, Martínez-Uroz MA, Valverde A, Fernández-Alba AR (2008) Validation and uncertainty study of a comprehensive list of 160 pesticide residues in multi-class vegetables by liquid chromatography-tandem mass spectrometry. J Chromatogr A 1215:37–50. https://doi.org/10.1016/j.chroma.2008.10.121

    Article  CAS  PubMed  Google Scholar 

  • Le Doux 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. https://doi.org/10.1016/j.chroma.2010.12.097

    Article  CAS  Google Scholar 

  • Lehotay SJ, Sapozhnikova Y (2017) Fast, automatic, and accurate determination and identification of targeted analytes in high-throughput analysis by chromatography–tandem mass spectrometry. Pittcon Conference & Expo, Chicago, Illinois. https://www.itspsolutions.com/sites/default/files/Pittcon%202017%20Lehotay_0.pdf/ Accessed 18.03.2019

  • Mac Lachlan DJ (2011) Estimating the transfer of contaminants in animal feedstuffs to livestock tissues, milk and eggs: a review. Anim Prod Sci 51:1067–1078. https://doi.org/10.1071/AN11112

    Article  CAS  Google Scholar 

  • Marilyn JS, Lehotay SJ, Lightfield AR (2015) Validation of a streamlined multiclass, multiresidue method for determination of veterinary drug residues in bovine muscle by liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 407(15):4423–4435

    Article  Google Scholar 

  • Mc Glinchey TA, Rafter PA, Regan F, Mc Mahon PA (2008) A review of analytical methods for the determination of aminoglycoside and macrolide residues in food matrices. Anal Chim Acta 624:1–15. https://doi.org/10.1016/j.aca.2008.05.054

    Article  CAS  Google Scholar 

  • Ministerio de Ganadería Agricultura y Pesca MGAP (2015) Manual del Programa Nacional de Residuos Biológicos, https://www.gub.uy/ministerioganaderia-agricultura-pesca/sites/ministerio-ganaderia-agricultura-pesca/files/documentos/publicaciones/manualv-6pnrbcapitulocarne-ultimaversion.pdf. Accessed 20 Feb 2019

  • Mol HGJ, Rooseboom A, Van Dam R, Roding M, Arondeus K, Sunarto S (2007) Modification and re-validation of the ethyl acetate-based multi-residue method for pesticides in produce. Anal Bioanal Chem 389:1715–1754. https://doi.org/10.1007/s00216-007-1357-1

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Mol HGJ, Plaza-Bolaños P, Zomer P, De Rijk TC, Stolker AAM, Mulder PPJ (2008) Toward a generic extraction method for simultaneous determination of pesticides, mycotoxins, plant toxins, and veterinary drugs in feed and food matrices. Anal Chem 80:9450–9459. https://doi.org/10.1021/ac801557f

    Article  CAS  PubMed  Google Scholar 

  • Ortelli D, Cognard E, Jan P, Edder P (2009) Comprehensive fast multiresidue screening of 150 veterinary drugs in milk by ultra-performance liquid chromatography coupled to time of flight mass spectrometry. J Chromatogr B 877:2363–2374. https://doi.org/10.1016/j.jchromb.2009.03.006

    Article  CAS  Google Scholar 

  • Shimadzu Automatic Adjustment of Retention Time Function (AART), (2019) https://www.shimadzu.eu/automatic-adjustment-retention-time-function-aart/. Accessed 18.02.2019

  • Sobhanzadeh E, Abu Bakar NK, Bin Abas MR, Nemati K (2011) A simple and efficient multi-residue method based on QuEChERS for pesticides determination in palm oil by liquid chromatography time-of-flight mass spectrometry. Environ Monit Assess 184:5821–5828. https://doi.org/10.1007/s10661-011-2384-0

    Article  CAS  PubMed  Google Scholar 

  • 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 79(17–18):1101–1112. https://doi.org/10.1007/s10337-016-3026-z

    Article  CAS  Google Scholar 

  • The Food and Agriculture Organization of the United Nations (FAO) (2015) World Agriculture: Towards 2015/2030 - An FAO perspective. (2015) http://www.fao.org/3/y4252e/y4252e05b.htm. Accessed 01 Mar 2019

  • Wittenberg JB, Simon KA, Wong JB (2017) Targeted multiresidue analysis of veterinary drugs in milk-based powders using liquid chromatography-tandem mass spectrometry (LC-MS/MS). J Agric Food Chem 65(34):7288–7293. https://doi.org/10.1021/acs.jafc.6b05263

    Article  CAS  PubMed  Google Scholar 

  • Xie J, Peng T, Zhu A, He J, Cheng Q, Hu X, Chen H, Fan C, Jiang W, Chen M, Li J, Ding S, Jiang H (2015) Multi-residue analysis of veterinary drugs, pesticides and mycotoxins in dairy products by liquid chromatography-tandem mass spectrometry using low-temperature cleanup and solid phase extraction. J Chromatogr B 1002:19–29. https://doi.org/10.1016/j.jchromb.2015.08.005

    Article  CAS  Google Scholar 

  • Zheng G, Han C, Liu Y, Wang J, Zhu M, Wang C, Shen Y (2014) Multiresidue analysis of 30 organochlorine pesticides in milk and milk powder by gel permeation chromatography-solid phase extraction-gas chromatography-tandem mass spectrometry. J Dairy Sci 97:6016–6026. https://doi.org/10.3168/jds.2014-8192

    Article  CAS  PubMed  Google Scholar 

  • Zorraquino MA, Roca M, Fernández N, Molina MP, Althaus R (2008) Heat Inactivation of B-lactams antibiotics in milk. J Food Prot 71(6):1193–1196. https://doi.org/10.4315/0362-028X-71.6.1193

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

The authors acknowledge Dra. Florencia Puigvert for language help.

Funding

This study was funded by PEDECIBA Química (Programa de Desarrollo de las Ciencias Básicas, Uruguay), CSIC-INI (Programa de Iniciación a la Investigación, Comisión Sectorial de Investigación Científica, Universidad de la República), and RALACA/FAO/International Atomic Energy Agency.

Author information

Authors and Affiliations

  1. Programa de Posgrados de la Facultad de Química, Universidad de la República, General Flores 2124, Montevideo, 11800, Uruguay

    Rodrigo Souza

  2. Departamento de Química del Litoral, Cenur Litoral Norte, Universidad de la República, Ruta 3 Km 363, Paysandú, 60000, Uruguay

    Paula Fernández, Agustina Muela & Lucia Pareja

  3. Cátedra de Farmacognosia y Productos Naturales, Departamento de Química Orgánica, Facultad de Química, Universidad de la República, General Flores 2124, Montevideo, 11800, Uruguay

    María Verónica Cesio & Horacio Heinzen

Authors
  1. Rodrigo Souza
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Paula Fernández
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Agustina Muela
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. María Verónica Cesio
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Horacio Heinzen
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Lucia Pareja
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Lucia Pareja.

Ethics declarations

Conflict of Interest

Rodrigo Souza declares that he has no conflict of interest. Paula Fernández declares that she has no conflict of interest. Agustina Muela declares that she has no conflict of interest. Lucia Pareja declares that she has no conflict of interest. Veronica Cesio declares that she has no conflict of interest. Horacio Heinzen 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

Not Applicable.

Code Availability

Not applicable

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 26 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Souza, R., Fernández, P., Muela, A. et al. Development of a Methodology for the Simultaneous Analysis of Multiclass Contaminants in Milk. Food Anal. Methods 14, 1075–1086 (2021). https://doi.org/10.1007/s12161-020-01953-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-020-01953-7

Keywords

Search

Navigation