Rapid determination of antibiotic residues in cereals by liquid chromatography triple mass spectrometry

  • Beatriz Albero
  • José Luis Tadeo
  • Esther Miguel
  • Rosa Ana PérezEmail author
Research Paper


Antibiotics may be present in agricultural soils through the application of organic amendments as fertilizers or by irrigation of fields with recycled water. As a result of these agricultural practices, antibiotics in soil can lead to their uptake by plants, entering in this way the food chain. Studies on the levels of antibiotics in cereal samples are scarce in the available literature. In this work, an analytical method was developed for the determination of 19 antibiotics (fluoroquinolones, sulfonamides, tetracyclines, and lincosamides) in four types of cereal grains (wheat, barley, rice, and oat). Ultrasound-assisted matrix solid-phase dispersion was selected as extraction technique with recoveries of target analytes ranging from 73 to 127% for the four cereals analyzed. Limits of quantification obtained ranged from 0.8 to 5.8 ng g−1. Compared with methods described for the analysis of antibiotics in cereals, the developed method uses a lower volume of extraction solvent and very good recoveries were obtained for all compounds. The validated method was applied to the analysis of different types of cereals samples, harvested from agricultural fields or purchased from local supermarkets. The analysis of the five cereal samples grown in fields with 3 years of consecutive organic amendments revealed that none of the nineteen antibiotics selected were found in any sample. Eleven commercial samples of cereals of different types and presentations were analyzed and enrofloxacin was detected in one rice sample; the presence of enrofloxacin in cereals or its incorporation into crops from soil or water not previously reported.

Graphical abstract 


Grains Uptake Antibiotics LC-MS/MS Analysis 



The authors wish to thank the Spanish Ministry of Economy, Industry and Competitiveness for financial support, project (RTA2014-00012C03). The authors would like to thank Dr. Mª Carmen Lobo Bedmar (IMIDRA) and Dr. Jose Luis Tenorio (INIA) for the cereal samples grown in the agricultural fields and the wheat grown in the experimental farm “La Canaleja” (Madrid), respectively.

Compliance with ethical standards

Conflict of interest

The authors declare that they have 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.

Supplementary material

216_2019_2003_MOESM1_ESM.pdf (873 kb)
ESM 1 (PDF 873 kb)


  1. 1.
    Carvalho IT, Santos L. Antibiotics in the aquatic environments: a review of the European scenario. Environ Int. 2016;94:736–57.CrossRefGoogle Scholar
  2. 2.
    Klein EY, Van Boeckel TP, Martinez EM, Pant S, Gandra S, Levin SA, et al. Global increase and geographic convergence in antibiotic consumption between 2000 and 2015. Proc Natl Acad Sci U S A. 2018;115:E3463–70.CrossRefGoogle Scholar
  3. 3.
    Christou A, Agüera A, Bayona JM, Cytryn E, Fotopoulos V, Lambropoulou D, et al. The potential implications of reclaimed wastewater reuse for irrigation on the agricultural environment: the knowns and unknowns of the fate of antibiotics and antibiotic resistant bacteria and resistance genes – a review. Water Res. 2017;123:448–67.CrossRefGoogle Scholar
  4. 4.
    Tasho RP, Cho JY. Veterinary antibiotics in animal waste, its distribution in soil and uptake by plants: a review. Sci Total Environ. 2016;563–564:366–76.CrossRefGoogle Scholar
  5. 5.
    Madikizela LM, Ncube S, Chimuka L. Uptake of pharmaceuticals by plants grown under hydroponic conditions and natural occurring plant species: a review. Sci Total Environ. 2018;636:477–86.CrossRefGoogle Scholar
  6. 6.
    Pan M, Wong CKC, Chu LM. Distribution of antibiotics in wastewater-irrigated soils and their accumulation in vegetable crops in the Pearl River Delta, southern China. J Agric Food Chem. 2014;62:11062–9.CrossRefGoogle Scholar
  7. 7.
    Chung HS, Lee YJ, Rahman MM, Abd El-Aty AM, Lee HS, Kabir MH, et al. Uptake of the veterinary antibiotics chlortetracycline, enrofloxacin, and sulphathiazole from soil by radish. Sci Total Environ. 2017;605–606:322–31.CrossRefGoogle Scholar
  8. 8.
    Albero B, Tadeo JL, Escario M, Miguel E, Pérez RA. Persistence and availability of veterinary antibiotics in soil and soil-manure systems. Sci Total Environ. 2018;643:1562–70.CrossRefGoogle Scholar
  9. 9.
    Pan M, Chu LM. Fate of antibiotics in soil and their uptake by edible crops. Sci Total Environ. 2017;599–600:500–12.CrossRefGoogle Scholar
  10. 10.
    OECD/FAO. “Cereals”, in OECD-FAO agricultural outlook 2016-2025. OECD Publ Paris. 2016;7:98–123.Google Scholar
  11. 11.
    FAO Cereal Supply and Demand Brief | World Food Situation | Food and Agriculture Organization of the United Nations. Accessed 10 May 2019.
  12. 12.
    Boonsaner M, Hawker DW. Investigation of the mechanism of uptake and accumulation of zwitterionic tetracyclines by rice (Oryza sativa L.). Ecotoxicol Environ Saf. 2012;78:142–7.CrossRefGoogle Scholar
  13. 13.
    Franklin AM, Williams CF, Andrews DM, Woodward EE, Watson JE. Uptake of three antibiotics and an antiepileptic drug by wheat crops spray irrigated with wastewater treatment plant effluent. J Environ Qual. 2015;45:546–54.CrossRefGoogle Scholar
  14. 14.
    Gottschall N, Topp E, Metcalfe C, Edwards M, Payne M, Kleywegt S, et al. Pharmaceutical and personal care products in groundwater, subsurface drainage, soil, and wheat grain, following a high single application of municipal biosolids to a field. Chemosphere. 2012;87:194–203.CrossRefGoogle Scholar
  15. 15.
    Grote M, Schwake-Anduschus C, Michel R, Stevens H, Heyser W, Langenkamper G, et al. Incorporation of veterinary antibiotics into crops from manured soil. Landbauforsch Volkenrode. 2007;57:25–32.Google Scholar
  16. 16.
    Haiba E, Lillenberg M, Kipper K, Astover A, Herodes K, Ivask M, et al. Fluoroquinolones and sulfonamides in sewage sludge compost and their uptake from soil into food plants. Afr J Agric Res. 2013;8:3000–6.Google Scholar
  17. 17.
    Hussain S, Naeem M, Chaudhry MN, Iqbal MA. Accumulation of residual antibiotics in the vegetables irrigated by pharmaceutical wastewater. Expo Heal. 2016;8:107–15.CrossRefGoogle Scholar
  18. 18.
    Schwake-Anduschus C, Langenkämper G. Chlortetracycline and related tetracyclines: detection in wheat and rye grain. J Sci Food Agric. 2018;98:4542–9.CrossRefGoogle Scholar
  19. 19.
    Freitag M, Yolcu DH, Hayen H, Betsche T, Grote M. Screening zum antibiotika-transfer aus dem boden in getreide in regionen Nordrhein-Westfalens mit großen viehbeständen. J fur Verbraucherschutz und Leb. 2008;3:174–84.CrossRefGoogle Scholar
  20. 20.
    Hawker DW, Cropp R, Boonsaner M. Uptake of zwitterionic antibiotics by rice (Oryza sativa L.) in contaminated soil. J Hazard Mater. 2013;263:458–66.CrossRefGoogle Scholar
  21. 21.
    Jacobsen AM, Halling-Sørensen B, Ingerslev F, Hansen SH. Simultaneous extraction of tetracycline, macrolide and sulfonamide antibiotics from agricultural soils using pressurised liquid extraction, followed by solid-phase extraction and liquid chromatography-tandem mass spectrometry. J Chromatogr A. 2004;1038:157–70.CrossRefGoogle Scholar
  22. 22.
    Abuin S, Codony R, Compañó R, Granados M, Prat MD. Analysis of macrolide antibiotics in river water by solid-phase extraction and liquid chromatography–mass spectrometry. J Chromatogr A. 2006;1114:73–81.CrossRefGoogle Scholar
  23. 23.
    Pérez RA, Albero B, Miguel E, Sánchez-Brunete C. Determination of parabens and endocrine-disrupting alkylphenols in soil by gas chromatography-mass spectrometry following matrix solid-phase dispersion or in-column microwave-assisted extraction: a comparative study. Anal Bioanal Chem. 2012;402:2347–57.CrossRefGoogle Scholar
  24. 24.
    Dorival-García N, Labajo-Recio C, Zafra-Gómez A, Juárez-Jiménez B, Vílchez JL. Improved sample treatment for the determination of 17 strong sorbed quinolone antibiotics from compost by ultra high performance liquid chromatography tandem mass spectrometry. Talanta. 2015;138:247–57.CrossRefGoogle Scholar
  25. 25.
    Chuang YH, Zhang Y, Zhang W, Boyd SA, Li H. Comparison of accelerated solvent extraction and quick, easy, cheap, effective, rugged and safe method for extraction and determination of pharmaceuticals in vegetables. J Chromatogr A. 2015;1404:1–9.CrossRefGoogle Scholar
  26. 26.
    Albero B, Sánchez-Brunete C, Miguel E, Tadeo JL. Application of matrix solid-phase dispersion followed by GC–MS/MS to the analysis of emerging contaminants in vegetables. Food Chem. 2017;217:660–7.CrossRefGoogle Scholar
  27. 27.
    Chitescu CL, Oosterink E, De Jong J, Stolker AAM. Ultrasonic or accelerated solvent extraction followed by U-HPLC-high mass accuracy MS for screening of pharmaceuticals and fungicides in soil and plant samples. Talanta. 2012;88:653–62.CrossRefGoogle Scholar
  28. 28.
    De Alwis H, Heller DN. Multiclass, multiresidue method for the detection of antibiotic residues in distillers grains by liquid chromatography and ion trap tandem mass spectrometry. J Chromatogr A. 2010;1217:3076–84.CrossRefGoogle Scholar
  29. 29.
    Bernal E (2014) Limit of detection and limit of quantification determinationin gas chromatography. In: Guo X, editor. Advances in gas chromatography. Intech, 2014.Google Scholar

Copyright information

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

Authors and Affiliations

  • Beatriz Albero
    • 1
  • José Luis Tadeo
    • 1
  • Esther Miguel
    • 1
  • Rosa Ana Pérez
    • 1
    Email author
  1. 1.Departamento de Medio Ambiente y AgronomíaInstituto Nacional de Investigación y Tecnología Agraria y Alimentaria (INIA)MadridSpain

Personalised recommendations