Critical assessment of two sample treatment methods for multiresidue determination of veterinary drugs in milk by UHPLC-MS/MS
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.
KeywordsSample treatment Veterinary drugs Milk HLB PRiME EMR-Lipid UHPLC-MS/MS
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).
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.
- 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.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
- 5.World Health Organization (WHO). Antibiotic resistence, 2018, http://www.who.int/news-room/fact-sheets/detail/antibiotic-resistance. accessed 30 October 2018.
- 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
- 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.CrossRefGoogle Scholar
- 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.CrossRefGoogle Scholar
- 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.CrossRefGoogle Scholar
- 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.CrossRefGoogle Scholar
- 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.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.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
- 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.
- 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
- 31.Young MS, Shia J, Shah D, Tran K, Huang D. Oasis PRiME HLB Food Applications Notebook. Agilent Technologies 2017.Google Scholar