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Analytical and Bioanalytical Chemistry

, Volume 411, Issue 7, pp 1433–1442 | Cite as

Critical assessment of two sample treatment methods for multiresidue determination of veterinary drugs in milk by UHPLC-MS/MS

  • Delia Castilla-Fernández
  • David Moreno-González
  • Miriam Beneito-Cambra
  • Antonio Molina-DíazEmail author
Research Paper

Abstract

In this work, two sample treatment procedures have been evaluated for the determination of veterinary drug residues in milk. In order to cover a wide range of polarities, a total of 66 veterinary drugs with log Kow ranging from − 1 to 5 were selected. Two sample cleanup steps, (i) dispersive solid-phase extraction (dSPE) using enhanced matrix removal lipid as sorbent and (ii) solid-phase extraction (in pass-through mode) using Oasis HLB PRiME cartridges, were critically assessed in terms of sample throughput, recovery, matrix effect, cleanliness of extracts, limit of quantification, and repeatability. The veterinary drugs tested (viz. benzimidazoles, cephalosporins, imidazothiazoles, macrolides, NSAIDs, penicillins, quinolones, steroids, sulfonamides, and β-agonists) were analyzed by ultra-high-performance liquid chromatography tandem mass spectrometry. According to the results, both methods exhibited similar recovery rates between 70 and 120% for most of compounds tested. Matrix effects were satisfactory for both methodologies, although the tolerance to matrix effects was slightly higher with HLB PRiME with nearly negligible matrix effects in most cases. Limits of quantitation were also well below the current maximum residue levels established by the European Union. Notably, sample throughput was higher in the case of HLB PRiME, since this pass-through SPE cleanup approach involved fewer steps than the EMR-Lipid dSPE approach. The results in terms of analysis time, sensitivity, precision, cleanliness of extracts, and matrix effect showed the suitability of both procedures for the monitoring of veterinary drugs residues in milk samples in a single run.

Graphical abstract

Keywords

Sample treatment Veterinary drugs Milk HLB PRiME EMR-Lipid UHPLC-MS/MS 

Notes

Acknowledgments

D.C.F. thanks the Andalusian government and European Union for Youth Guarantee research contract (SNGJ-JINV-P-010). D.M.G. thanks the Spanish Ministerio de Economía y Competitividad (MINECO) for a Juan de la Cierva Formación postdoctoral fellowship (Ref. FJCI-2014-19573).

Funding information

This study received funding from Ministerio de Economía y Competitividad (MINECO) (Ref. CTQ-2015-71321-P).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

216_2019_1582_MOESM1_ESM.pdf (202 kb)
ESM 1 (PDF 201 kb)

References

  1. 1.
    Pereira PC. Milk nutritional composition and its role in human health. Nutrition. 2014;30:619–27.CrossRefPubMedGoogle Scholar
  2. 2.
    Milk and Dairy Products in Human Nutrition, in: Muehlhoff E. Bennett A. MacMahon D. (Eds.), Food and Agriculture Organization of the United Nations, Rome, 2013 http://www.fao.org/docrep/018/i3396e/i3396e.pdf. Accessed 30 Oct 2018.
  3. 3.
    Oliver SP, Murinda SE, Jayarao BM. Impact of antibiotic use in adult dairy cows on antimicrobial resistance of veterinary and human pathogens: a comprehensive review. Foodborne Pathog Dis. 2011;8.Google Scholar
  4. 4.
    Jacoby GA. Mechanisms of resistance to quinolones. Clin Infect Dis. 2005;41:120–6.CrossRefGoogle Scholar
  5. 5.
    World Health Organization (WHO). Antibiotic resistence, 2018, http://www.who.int/news-room/fact-sheets/detail/antibiotic-resistance. accessed 30 October 2018.
  6. 6.
    European Commission Regulation (EU) No 37/2010 of 22 December 2009 on pharmacologically active substances and their classification regarding maximum residue limits in foodstuffs of animal origin Off. J. Eur Communities 2010; L15:1–72.Google Scholar
  7. 7.
    Li J, Ren X, Diao Y, Chen Y, Wang Q, Jin W, et al. Multiclass analysis of 25 veterinary drugs in milk by ultra-high performance liquid chromatography-tandem mass spectrometry. Food Chem. 2018;257:259–64.CrossRefPubMedGoogle Scholar
  8. 8.
    Dasenaki ME, Thomaidis NS. 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. 2015;880:103–21.CrossRefPubMedGoogle Scholar
  9. 9.
    Wang J, Leung D, Chow W, Chang J, Wong JW. Development and validation of a multiclass method for analysis of veterinary drug residues in milk using ultrahigh performance liquid chromatography electrospray ionization quadrupole orbitrap mass spectrometry. J Agric Food Chem. 2015;63:9175–87.CrossRefPubMedGoogle Scholar
  10. 10.
    Kaufmann A, Butcher P, Maden K, Walker S, Widmer M. Multi-residue quantification of veterinary drugs in milk with a novel extraction and cleanup technique: salting out supported liquid extraction (SOSLE). Anal Chim Acta. 2014;820:56–68.CrossRefPubMedGoogle Scholar
  11. 11.
    Masiá A, Morales Suarez-Varela M, Agustin Llopis-Gonzalez A, Picó Y. Determination of pesticides and veterinary drug residues in food by liquid chromatography-mass spectrometry: a review. Anal Chim Acta. 2016;936:40–61.CrossRefPubMedGoogle Scholar
  12. 12.
    Rossi R, Saluti G, Moretti S, Diamanti I, Giusepponi D, Galarini R. Multiclass methods for the analysis of antibiotic residues in milk by liquid chromatography coupled to mass spectrometry: a review. Food Addit Contam A. 2018;35:241–57.CrossRefGoogle Scholar
  13. 13.
    Junza A, Amatya R, Barron D, Barbosa J. Comparative study of the LC- MS/MS and UPLC-MS/MS for the multi-residue analysis of quinolones, penicillinsand cephalosporins in cow milk, and validation according to the regulation 2002/657/EC. J Chromatogr B. 2011;879:2601–10.CrossRefGoogle Scholar
  14. 14.
    Schwaiger B, König J, Lesueur C. Development and validation of a multi-class UHPLC-MS/MS method for determination of antibiotic residues in dairy products. Food Anal Methods. 2018;11:1417–34.CrossRefGoogle Scholar
  15. 15.
    Bohm DA, Stachel CS, Gowik P. Multi-method for the determination of antibiotics of different substance groups in milk and validation in accordance with Commission Decision 2002/657/EC. J Chromatogr A. 2009;1216:8217–23.CrossRefPubMedGoogle Scholar
  16. 16.
    Chico J, Rúbies A, Centrich F, Companyó R, Prat MD, Granados M. High-throughput multiclass method for antibiotic residue analysis by liquid chromatography–tandem mass spectrometry. J Chromatogr A. 2008;1213:189–99.CrossRefPubMedGoogle Scholar
  17. 17.
    Zhang Y, Li X, Liu X, Zhang J, Cao Y, Shi Z, et al. Multi-class, multi-residue analysis of trace veterinary drugs in milk by rapid screening and quantification using ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. J Dairy Sci. 2015;98:8433–44.CrossRefPubMedGoogle Scholar
  18. 18.
    Zhou J, Xua JJ, Cong JM, Cai ZX, Zhang JS, Wang JL, et al. Optimization for quick, easy, cheap, effective, rugged and safe extraction of mycotoxins and veterinary drugs by response surface methodology for application to egg and milk. J Chromatogr A. 2018;1532:20–9.CrossRefPubMedGoogle Scholar
  19. 19.
    López-Blanco R, Nortes-Méndez R, Robles-Molina J, Moreno-González D, Gilbert-López B, García-Reyes JF, et al. Evaluation of different cleanup sorbents for multiresidue pesticide analysis in fatty vegetable matrices by liquid chromatography tandem mass spectrometry. J Chromatogr A. 2016;1456:89–104.CrossRefPubMedGoogle Scholar
  20. 20.
    Parrilla Vázquez Hakme PE, Uclés S, Cutillas V, Martínez Galera M, Mughari AR, Fernández-Alba AR. Large multiresidue analysis of pesticides in edible vegetable oils by using efficient solid-phase extraction sorbents based on quick, easy, cheap, effective, rugged and safe methodology followed by gas chromatography–tandem mass spectrometry. J Chromatogr A. 2016;1463:20–31.CrossRefPubMedGoogle Scholar
  21. 21.
    Moreno-González D, Hamed AM, Gilbert-López B, Gámiz-Gracia L, García-Campaña AM. Evaluation of a multiresidue capillary electrophoresis-quadrupole-time-of-flight mass spectrometry method for the determination of antibiotics in milk sample. J Chromatogr A. 2017;1510:100–7.CrossRefPubMedGoogle Scholar
  22. 22.
    Wang J, Fan X, Liu YDZ, Feng Y, Jia L, Zhang J. Extraction optimization of sixteen cephalosporins in milk by filtered solid phase extraction and ultra high pressure liquid chromatography coupled to tandem mass spectrometry. Anal Methods. 2017;91:282–1289.Google Scholar
  23. 23.
    Huang D. Tran KV. Young MS. A simple cleanup protocol using a novel SPE device for UPLC-MS/MS analysis of multi-residue veterinary drugs in milk. Waters Application Note. 2015.Google Scholar
  24. 24.
    Zhao L. Lukas D. Multiresidue analysis of veterinary drugs in bovine liver by LC/MS/MS Agilent Bond Elut Enhanced Matrix Removal—Lipid, Agilent Technologies Application Note. 2015.Google Scholar
  25. 25.
    Wittenberg JB, Simon KA, Wong JW. Targeted multiresidue analysis of veterinary drugs in milk-based powders using liquid chromatography−tandem mass spectrometry (LC-MS/MS). J Agric Food Chem. 2017;65:7288–93.CrossRefPubMedGoogle Scholar
  26. 26.
    U.S. Department of Agriculture Agricultural Research Service. USDA National Nutrient Database for Standard Reference, Release 26, http://ndb.nal.usda.gov 2011. Accessed 30 Oct 2018.
  27. 27.
    Jensen RG. The composition of bovine milk lipids: January 1995 to December 2000. J Dairy Sci. 2002;85:295–350.CrossRefPubMedGoogle Scholar
  28. 28.
    European Commission decision of 12 August 2002 implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results, Commission Decision 2002/657/EEC. Off. J. Eur. Communities 2002; L221: 1–36.Google Scholar
  29. 29.
    Matuszewski BK, Constanzer ML, Chavez-Eng CM. Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS. Anal Chem. 2003;75:3019–30.CrossRefPubMedGoogle Scholar
  30. 30.
    Ferrer-Amate C, Unterluggauer H, Fischer RJ, Fernández-Alba AR, Masselter S. Development and validation of a LC–MS/MS method for the simultaneous determination of aflatoxins, dyes and pesticides in spices. Anal Bional Chem. 2010;397:93–107.CrossRefGoogle Scholar
  31. 31.
    Young MS, Shia J, Shah D, Tran K, Huang D. Oasis PRiME HLB Food Applications Notebook. Agilent Technologies 2017.Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Delia Castilla-Fernández
    • 1
  • David Moreno-González
    • 1
  • Miriam Beneito-Cambra
    • 1
  • Antonio Molina-Díaz
    • 1
    • 2
    Email author
  1. 1.Analytical Chemistry Research Group, Department of Physical and Analytical Chemistry, Campus Las LagunillasUniversity of JaénJaénSpain
  2. 2.Center for Advanced Studies in Olives Grove and Olive Oils (CEAOAO), Science and Technology Park GEOLITMengíbarSpain

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