Detection of Antibiotic Residues in Honeys from Different Regions in Türkiye by Liquid Chromatography-Tandem Mass Spectrometry Method

Abstract

This study aimed to investigate 29 antibiotics and their metabolites in 27 honey samples obtained from different provinces of Turkey by Liquid Chromatography-Tandem Mass Spectrometry Method (LS-MS/MS). This study showed that the correlation coefficients of the calibration graphs were 0.999, the limit of detection (LOD) was 0.94–3.40 ng/g, and the limit of quantification (LOQ) was 3.11–11.22 ng/g. To express the accuracy of the method, intra- and inter-day recoveries were tested using three different concentrations from 0.25 to 1 μg/kg. Intra-day recoveries for antibiotics and metabolites were found to be 95.56–115.56% with relative standard deviation values between 0.43 and 6.58; inter-day recoveries were found to be 90.00–108.89% with relative standard deviation values between 0.54 and 5.31. The analysis results showed that no antibiotic residues were found in any of the honey samples. The honey did not pose any danger to food safety or public health.

Keywords

• Antibiotic residue
• honey
• LS-MS/MS

References

1. Ağaoğlu, S., Alemdar, S., Ercan, N. (2020). Antibiotic residues in filtered honeys. Turkish Journal of Agriculture-Food Science and Technology, 8(11), 2408-2415. https://doi.org/10.24925/turjaf.v8i11.2408-2415.3687
2. Ahmed, M.B., Rajapaksha, A.U., Lim, J.E., Vu, N.T., Kim, I.S., Kang, H.M., Lee, S.S., Ok, Y.S. (2015). Distribution and accumulative pattern of tetracyclines and sulfonamides in edible vegetables of cucumber, tomato, and lettuce. Journal of Agricultural and Food Chemistry, 63, 398–405. https://doi.org/10.1021/jf5034637. Epub 2015 Jan 9.
3. Ahmed, M.B.M., Taha, A.A., Mehaya, F.M.S. (2023). Method validation and risk assessment for sulfonamides and tetracyclines in bees’ honey from Egypt, Libya and Saudi Arabia. Environ Geochem Health, 45, 997-1011. https://doi.org/10.1007/s10653-022-01258-0
4. Aksoy, A. (2019). Simultaneous screening of antibiotic residues in honey by biochip multi-array technology. Medycyna Weterynaryjna, 75(9), 567-571. https://doi.org/dx.doi.org/10.21521/mw.6240
5. Anon (2023). Leading producers of natural honey worldwide in 2021*(in 1,000 metric tons). https://www.statista.com/statistics/report-content/statistic/812172
6. Aydemir Atasever, M., Yüksel, A.T. (2022). Determination of some antibiotic residues in honey produced in Erzurum region. Veterinary Sciences and Practices, 17(3), 76-80. https://doi.org/10.5152/VetSciPract.2022.220105
7. Bayram, N.E. (2023). Nectar honey from Turkey: crystallization and physicochemical profile. European Food Research and Technology, 249,1049-1057. https://doi.org/10.1007/s00217-022-04194-6
8. Bonerba, E., Panseri, S., Arioli, F., Nobile, M., Terio, V., Di Cesare, F., Tantillo, G., Maria Chiesa, L. (2021). Determination of antibiotic residues in honey in relation to different potential sources and relevance for food inspection. Food Chemistry, 334, 127575. https://doi.org/10.1016/j.foodchem.2020.127575

9. Brar, D.S., Pant, K., Krishnan, R., Kaur, S., Rasane, P., Nanda, V., Saxena, S., Gautam, S. (2023). A comprehensive review on unethical honey: Validation by emerging techniques. Food Control, 145, 109482. https://doi.org/10.1016/j.foodcont.2022.109482
10. Chiesa, L.M., Panseri, S., Nobile, M., Ceriani, F., Arioli, F. (2018). Distribution of POPs, pesticides and antibiotic residues in organic honeys from different production areas. Food Addit Contam A 35:1340-55.
11. Cunningham, M.M., Tran, L., McKee, C.G., Polo, R.O., Newman, T., Lansing, L., Griffiths, J.S., Bilodeau, G.J., Rott, M., Guarna, M.M. (2022). Honey bees as biomonitors of environmental contaminants, pathogens, and climate change. Ecological Indicators, 134, 108457. https://doi.org/10.1016/j.ecolind.2021.108457
12. Derebaşı, E., Bulut, G., Col, M., Güney, F., Yaşar, N., Ertürk, Ö. (2014). Physicochemical and residue analysis of honey from Black Sea region of Turkey. Fresenius Environmental Bulletin, 23(1), 10-17.
13. Er Demirhan, B., Demirhan, B. (2022). Detection of antibiotic residues in blossom honeys from different regions in Turkey by LC-MS/MS Method. Antibiotics, 11, 357. https://doi.org/10.3390/ antibiotics11030357
14. Erdoğdu, A.T., Coşkun, Y., Güven, S.İ. (2011). Determination of sulphonamide antibiotics residues in honey presented for consumption. The Journal of Bornova Veterinary Science, 33, 37-44.
15. EU (2010). 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 EU 2009, L15, 72.
16. FDA-Food and Drugs Administration (2023). Code of Federal Regulations - Title 21 - Food and Drugs, Chapter I--Food and Drug Administration Department of Health and Human Services Subchapter E - Animal Drugs, Feeds, and Related Products Part 556 Tolerances for Residues of New Animal Drugs in Food., https://www.accessdata.fda.gov/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm, (Accessed May 10, 2023)
17. FSANZ-Food Standards Australia and New Zealand (2016). Australia New Zealand food standards code - Standard 1.4.2. schedule 20 - Maximum residue limits (2016), https://www.foodstandards.gov.au/code/Pages/default.aspx., (Accessed April 10, 2023)
18. Gunes, N., Cibik, R., Gunes, M.E., Aydin, L. (2008). Erythromycin residue in honey from the Southern Marmara region of Turkey. Food Additives and Contaminants, 25(11), 1313-1317. https://doi.org/10.1080/02652030802233472
19. Gunes, M.E., Gunes, E., Cibik, R. (2009). Oxytetracycline and sulphonamide residues analysis of honey samples from Southern Marmara Region in Turkey. Bulgarian Journal of Agricultural Science, 15, 163-167.
20. Gürel Yücel, M., Seçilmiş, H., Tasci, F. (2023). Investigation of tylosin and tilmicosin residues in meat by high-performance liquid chromatography method. Polish Journal of Veterinary Sciences 26(1), 39-46. https://doi.org/10.24425/pjvs.2023.145005
21. Health Canada (2022). List of Maximum Residue Limits (MRLs) for Veterinary Drugs in Foods, https://www.canada.ca/en/health-canada/services/drugs-health-products/veterinary-drugs/maximum-residue-limits-mrls/list-maximum-residue-limits-mrls-veterinary-drugs-foods.html, (Accessed April 11, 2023)
22. Hitabatuma, A., Wang, P., Su, X., Ma, M. (2022). Metal-organic frameworks-based sensors for food safety. Foods, 11, 382. https://doi.org/10.3390/foods11030382
23. ICH-International Council for Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (2005). Validation of analytical procedures: text and methogology Q2 (R1). In: International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use. IFPMA, Geneva, Switzerland, pp 1-13.
24. Kırkan, E., Tahir, A.O., Bengu, A.Ş., Aslan, H., Ciftci, M., Aydoğan, C. (2020). Rapid determination of sulfonamide residues in honey samples using non-targeted liquid chromatographyhigh resolution mass spectrometry. Separation Science Plus, 1–9. https://doi.org/10.1002/sscp.202000051
25. Kıvrak, İ., Kıvrak, Ş., Harmandar, M. (2017). Development of a rapid method for the determination of antibiotic residues in honey using UPLC-ESI-MS/MS. Food Science and Technology (Campinas), 36(1), 90-96. https://doi.org/10.1590/1678-457X.0037
26. Kumar, A., Gill, J.P.S., Bedi, J.S., Chhuneja, P.K. (2020a). Residues of antibıotics in raw honeys from different apiaries of Northern India and evaluation of human health risks. Acta Alimentaria, 49(3), 314-320.
27. Kumar, A., Gill, J.P.S., Bedi, J.S., Chhuneja, P.K., Kumar, A. (2020b). Determination of antibiotic residues in Indian honeys and assessment of potential risks to consumers. Journal of Apicultural Research, 59(1), 25-34. https://doi.org/10.1080/00218839.2019.1677000
28. Kutlu, M.A., Gül, A., Özdemir, F.A., Kılıç, Ö. (2017). Determination of antibiotic residues from honey produced in Hizan District, Bitlis Province. Turkish Journal of Agricultural and Natural Sciences, 4(4), 523-527.
29. Marazuela, M.D., Bogialli, S. (2009). A review of novel strategies of sample preparation for the determination of antibacterial residues in foodstuffs using liquid chromatography-based analytical methods. Analytica Chimica Acta, 645, 5-17.
30. Mehrabi, A., Mahmoudi, R., Khoshmaram, N.B., Norian, R., Mosavi, S., Ebrahimi, H., Alizadeh, A., Kazemi, M. (2022). ELISA evaluation of erythromycin residues in honey samples collected from different areas of Qazvin, Iran. Journal of Chemical Health Risks, 12. https://doi.org/10.22034/jchr.2022.1905023.1158
31. Paoletti, F., Sdogati, S., Barola, C., Giusepponi, D., Moretti, S., Galarini, R. (2022). Two-procedure approach for multiclass determination of 64 antibiotics in honey using liquid chromatography coupled to time-of-flight mass spectrometry. Food Control, 136, 108893. https://doi.org/10.1016/j.foodcont.2022.108893
32. Ranneh, Y., Akim, A. M., Hamid, H. A., Khazaai, H., Fadel, A., Zakaria, Z. A., Albujja, M., Bakar, M. F. A. (2021). Honey and its nutritional and anti-inflammatory value. BMC Complementary Medicine and Therapies, 21(1), 30. https://doi.org/10.1186/s12906-020-03170-5
33. Sarkar, S., Souza, M.J., Martin-Jimenez, T., Abouelkhair, M.A., Kania, S.A., Okafor, C.C. (2023). Tetracycline, sulfonamide, and erythromycin residues in beef, eggs, and honey sold as “antibiotic-free” products in East Tennessee (USA) farmers’ markets. Veterinary Sciences,10, 243. https://doi.org/10.3390/vetsci10040243
34. Savarino, A.E., Terio, V., Barrasso, R., Ceci, E., Panseri, S., Chiesa, L.M., Bonerba, E. (2020). Occurrence of antibiotic residues in apulian honey: potential risk of environmental pollution by antibiotics. Italian Journal of Food Safety, 9(1), 8678. https://doi.org/10.4081/ijfs.2020. 8678
35. Shoaei, F., Talebi-Ghane, E., Ranjbar, A., Mehri, F. (2023). Evaluation of antibiotic residues in honey: a systematic review and meta-analysis. International Journal of Environmental Health Research, 1-12. https://doi.org/10.1080/09603123.2023.2197285
36. Tasci, F., Secilmis Canbay, H., Doganturk, M. (2021). Determination of antibiotics and their metabolites in milk by liquid chromatography-tandem mass spectrometry method. Food Control, 127, 108147. https://doi.org/10.1016/j.foodcont.2021.108147
37. TFC-Turkish Food Codex (2017). Turkish food codex regulation on classification of pharmacological active substances that can be found in animal foods and maximum residue limits. Official gazette, 7 Mar 2017 Tuesday, No: 30000. http://www.resmigazete.gov.tr/ default.aspx.
38. Tutun, H., Kahraman, H.A., Aluc, Y., Avci, T., Ekici, H. (2019). Investigation of some metals in honey samples from West Mediterranean region of Turkey. Veterinary Research Forum, 10(3), 181-186. https://doi.org/10.30466/vrf.2019.96726.2312
39. Valverde, S., Ares, A.M., Stephen Elmore, J., Bernal, J. (2022). Recent trends in the analysis of honey constituents. Food Chemistry, 387, 132920. https://doi.org/10.1016/j.foodchem.2022.132920
40. Wang, Y., Dong, X., Han, M., Yang, Z., Wang, Y., Qian, L., Huang, M., Luo, B., Wang H., Chen, Y., Jiang, Q. (2022). Antibiotic residues in honey in the Chinese market and human health risk assessment. Journal of Hazardous Materials, 440, 129815. https://doi.org/10.1016/j.jhazmat.2022.129815
41. Yang, Y., Lin, G., Liu, L., Lin, T. (2022). Rapid determination of multi-antibiotic residues in honey based on modified QuEChERS method coupled with UPLC–MS/MS. Food Chemistry, 374, 131733. https://doi.org/10.1016/j.foodchem.2021.131733
42. Zergui, A., Boudalia, S., Joseph, M.L. (2023). Heavy metals in honey and poultry eggs as indicators of environmental pollution and potential risks to human health. Journal of Food Composition and Analysis, 119, 105255. https://doi.org/10.1016/j.jfca.2023.105255