Investigation of some neonicotinoids in honey by LC-MS/MS

Halil Ergün; Levent Altıntaş

doi:10.33988/auvfd.1563914

Research Article

Year 2025, Volume: 72 Issue: 3, 267 - 276, 01.07.2025

Halil Ergün , Levent Altıntaş

https://doi.org/10.33988/auvfd.1563914

Abstract

References

References 1. Arslan MB, Küçükaydin S, Şahin B, et al (2021): Determination of phenolic compounds of Turkish red pine (Pinus brutia Ten.) infested by Marchalina hellenica Genn. Turk J For, 1, 35-43.
2. Campillo N, Vinas P, Ferez-Melgarejo, et al (2013): Liquid chromatography with diode array detection and tandem mass spectrometry for the determination of neonicotinoid insecticides in honey samples using dispersive liquid-liquid microextraction. J Agric Food Chem, 61, 4799-4805.
3. Can Z, Yıldız O, Sahın H, et al (2015): An investigation of Turkish honey: their physicochemical properties, antioxidant capacities, and phenolic profiles. Food Chem, 180, 133-141.
4. Carbonell-Rozas L, Lara FJ, Del Olmo Iruela, et al (2020): Capillary liquid chromatography is an effective method for the determination of seven neonicotinoid residues in honey samples. J Sep Sci, 43, 3847-3855.
5. European Commission (2013): Commission Implementing Regulation (EU) No 485/2013 of 24 May 2013 amending Implementing Regulation (EU) No 540/2011. Available at https://eur-lex.europa.eu/eli/reg_impl/2013/485/oj. (Accessed 10 Jan, 2022).
6. European Commission (2018): European Commission. Commission Implementing Regulation (EU) 2018/113 of 24 January 2018 renewing the approval of the active substance acetamiprid in accordance with Regulation (EC) No 1107/2009 of the European Parliament and of the Council concerning the placing of plant protection products on the market, and amending the Annex to Commission Implementing Regulation (EU) No 540/2011. Off J Euro Union 2018; L 20, pp: 7–10. Available at https://eur-lex.europa.eu/legal-content/EN/TXT/?uri=CELEX%3A32018R0113. (Accessed 10 Jan, 2022).
7. European Commission (2024): EU pesticides database. Available at https://ec.europa.eu/food/plant/pesticides/. (Acecessed 5 Jan, 2024).
8. European Commission (2002): Commission Decision (2002/657/EC) of 12 August 2002 implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results. Off J Eur Commun, 50, 8-36.
9. FAO (2019): Honey. Available at http://www.fao.org/publications/card/en/c/CA4657EN/. (Accessed 10 Jan, 2022).
10. Gawel M, Kiljanek T, Niewiadowska A, et al (2019): Determination of neonicotinoids and 199 other pesticide residues in honey by liquid and gas chromatography coupled with tandem mass spectrometry. Food Chem, 282, 36-47.
11. Gbylik-Sikorska M, Sniegocki T, Posyniak A (2015): Determination of neonicotinoid insecticides and their metabolites in honey bee and honey by liquid chromatography tandem mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci, 990, 132-140.
12. Hou J, Xie W, Hong D, et al (2019): Simultaneous determination of ten neonicotinoid insecticides and two metabolites in honey and Royal-jelly by solid-phase extraction and liquid chromatography-tandem mass spectrometry. Food Chem, 270, 204-213.
13. ICH (2006): ICH Harmonised Tripartite Guideline Validation of Analytical Procedures: Text and Methodology Q2 (R1). Current Step.
14. İçli N (2022): Evaluation of HMF levels in unbranded flower honeys in terms of food safety. Ank Univ Vet Fak Derg, 69, 431-436.
15. İplikçioğlu ÇG, Korkmaz SD, Cengiz G, et al (2020): Türkiye’deki bal örneklerinde neonikotinoid varlığının LC-MS/Q-TOF yöntemi ile tespiti. MAKÜ Sag Bil Enst Derg, 8, 11-17.
16. Jovanov P, Guzsvány V, Lazić S, et al (2015): Development of HPLC-DAD method for determination of neonicotinoids in honey. J Food Compos Anal, 40, 106-113.
17. Kaygısız F (2023): Factors affecting the choice of marketing channel by beekeepers in Türkiye. Ank Univ Vet Fak Derg, 70, 165-173.
18. Kumar A, Gill JPS, Bedi JS (2018): Multiresidue determination of pesticides in market honey from northern India using QuEChERS approach and assessment of potential risks to consumers. Curr Sci, 115, 283-291.
19. Ligor M, Bukowska M, Ratiu IA, et al (2020): Determination of Neonicotinoids in Honey Samples Originated from Poland and Other World Countries. Molecules, 25, 5817.
20. Mahamat AT, Altıntaş L, Aluç Y (2023): Investigation of the presence of some antibiotics in raw goat milk collected from Ankara, Kırıkkale and Çankırı provinces. Ankara Univ Vet Fak Derg, 70, 285-291.
21. Ministry of Agriculture and Forestry (2019): Gıda Kontrol Genel Müdürlüğü. Available at https://aydin.tarimorman.gov.tr/Duyuru/263/Neonicotinoid-Grubu-Aktif-Maddelerinin-Yasaklanmasi-Ve-Kisitlanmasi-Hk. (Accessed 10 Jan, 2022).
22. Mitchell EAD, Mulhauser B, Mulot M, et al (2017): A worldwide survey of neonicotinoids in honey. Science, 358, 109-111.
23. Mrzlikar M, Heath D, Heath E, et al (2019): Investigation of neonicotinoid pesticides in Slovenian honey by LC-MS/MS. Lwt 104, 45-52.
24. Paya P, Anastassiades M, Mack D, et al (2007). Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection. Anal Bioanal Chem, 389, 1697-1714.
25. Song S, Zhang C, Chen Z, et al (2018): Simultaneous determination of neonicotinoid insecticides and insect growth regulators residues in honey using LC-MS/MS with anion exchanger-disposable pipette extraction. J Chromatogr A, 1557, 51-61.
26. Tananaki C, Thrasyvoulou A, Giraudel, J, et al (2007): Determination of volatile characteristics of Greek and Turkish pine honey samples and their classification by using Kohonen self organising maps. Food Chem, 101, 1687-1693.
27. Tanner G, Czerwenka C (2011): LC-MS/MS analysis of neonicotinoid insecticides in honey: methodology and residue findings in Austrian honeys. J Agric Food Chem, 59, 12271-12277.
28. TÜİK (2021): Türkiye İstatistik Kurumu, Hayvansal Üretim İstatikleri, Aralık 2020 Available at https://data. tuik. gov.tr > Bulten > DownloadFilePDF. (Accessed 09 Feb, 2021).
29. UKİP (2018): Ulusal Kalıntı İzleme Planı, Gıda ve Kontrol Genel Müdürlüğü, Gıda Kontrol ve Laboratuvarlar Daire Başkanlığı. Available at https://avys.omu.edu.tr/storage/app/public/zpekmezci/124021/Numune%20alma.pdf. (Accessed 26 Feb, 2021).
30. Yücel Y, Sultanoglu P (2013): Characterization of honeys from Hatay Region by their physicochemical properties combined with chemometrics. Food Bioscience, 1, 16-25.

Investigation of some neonicotinoids in honey by LC-MS/MS

Year 2025, Volume: 72 Issue: 3, 267 - 276, 01.07.2025

Halil Ergün , Levent Altıntaş

https://doi.org/10.33988/auvfd.1563914

Abstract

Honey is a natural substance that is susceptible to contamination by environmental pollutants. The presence of contaminants in honey is an indicator of environmental pollution. Furthermore, it may pose risks to consumer health. This research aimed to optimise a method for the detection of residual quantities of the pesticides acetamiprid (ACE), clothianidin (CLO), imidacloprid (IMI), thiamethoxam (TMX) and thiacloprid (THI) in honey, and subsequently to apply this optimised method to an investigation into the prevalence of neonicotinoidal contamination. The QuEChERS (quick, easy, cheap, effective, robust and safe) method, in conjunction with liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS), was employed for the determination of five neonicotinoid in honey. The method was optimized and validated in accordance with European Commission guidelines (2002/657/EC). The method demonstrated a linear correlation with R² values exceeding 0.99 for all investigated compounds. Mean recoveries ranged between 70% and 110% (99% on average), and relative standard deviations (RSDs) were generally below 20%. The method's CCα (decision limit) and CCβ (detection capability) both ranged from 5 to 20 ng/g and 5-21 ng/g, respectively. Following method validation, the concentrations of IMI, ACE, TMX, CLO, and THI in all honey samples (flower, pine, and chestnut honey) available for retail in Ankara, Türkiye were determined to be ˂LOD based on the analytical results. It was concluded that the proposed method is usable and advantageous because it is effective, reliable, sensitive, and reproducible and can be used for the simultaneous analysis of more than one analyte in a short time using a few reagents.

Keywords

Honey , LC-MS/MS , neonicotinoid , residue , validation

Ethical Statement

This study does not present any ethical concerns. The study was submitted to the General Directorate of Food Control of the Ministry of Agriculture and Forestry of the Republic of Türkiye, and necessary permissions were obtained (27.12.2023/E-71037622-903.03.02.02-12602914).

References

References 1. Arslan MB, Küçükaydin S, Şahin B, et al (2021): Determination of phenolic compounds of Turkish red pine (Pinus brutia Ten.) infested by Marchalina hellenica Genn. Turk J For, 1, 35-43.
2. Campillo N, Vinas P, Ferez-Melgarejo, et al (2013): Liquid chromatography with diode array detection and tandem mass spectrometry for the determination of neonicotinoid insecticides in honey samples using dispersive liquid-liquid microextraction. J Agric Food Chem, 61, 4799-4805.
3. Can Z, Yıldız O, Sahın H, et al (2015): An investigation of Turkish honey: their physicochemical properties, antioxidant capacities, and phenolic profiles. Food Chem, 180, 133-141.
4. Carbonell-Rozas L, Lara FJ, Del Olmo Iruela, et al (2020): Capillary liquid chromatography is an effective method for the determination of seven neonicotinoid residues in honey samples. J Sep Sci, 43, 3847-3855.
5. European Commission (2013): Commission Implementing Regulation (EU) No 485/2013 of 24 May 2013 amending Implementing Regulation (EU) No 540/2011. Available at https://eur-lex.europa.eu/eli/reg_impl/2013/485/oj. (Accessed 10 Jan, 2022).
6. European Commission (2018): European Commission. Commission Implementing Regulation (EU) 2018/113 of 24 January 2018 renewing the approval of the active substance acetamiprid in accordance with Regulation (EC) No 1107/2009 of the European Parliament and of the Council concerning the placing of plant protection products on the market, and amending the Annex to Commission Implementing Regulation (EU) No 540/2011. Off J Euro Union 2018; L 20, pp: 7–10. Available at https://eur-lex.europa.eu/legal-content/EN/TXT/?uri=CELEX%3A32018R0113. (Accessed 10 Jan, 2022).
7. European Commission (2024): EU pesticides database. Available at https://ec.europa.eu/food/plant/pesticides/. (Acecessed 5 Jan, 2024).
8. European Commission (2002): Commission Decision (2002/657/EC) of 12 August 2002 implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results. Off J Eur Commun, 50, 8-36.
9. FAO (2019): Honey. Available at http://www.fao.org/publications/card/en/c/CA4657EN/. (Accessed 10 Jan, 2022).
10. Gawel M, Kiljanek T, Niewiadowska A, et al (2019): Determination of neonicotinoids and 199 other pesticide residues in honey by liquid and gas chromatography coupled with tandem mass spectrometry. Food Chem, 282, 36-47.
11. Gbylik-Sikorska M, Sniegocki T, Posyniak A (2015): Determination of neonicotinoid insecticides and their metabolites in honey bee and honey by liquid chromatography tandem mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci, 990, 132-140.
12. Hou J, Xie W, Hong D, et al (2019): Simultaneous determination of ten neonicotinoid insecticides and two metabolites in honey and Royal-jelly by solid-phase extraction and liquid chromatography-tandem mass spectrometry. Food Chem, 270, 204-213.
13. ICH (2006): ICH Harmonised Tripartite Guideline Validation of Analytical Procedures: Text and Methodology Q2 (R1). Current Step.
14. İçli N (2022): Evaluation of HMF levels in unbranded flower honeys in terms of food safety. Ank Univ Vet Fak Derg, 69, 431-436.
15. İplikçioğlu ÇG, Korkmaz SD, Cengiz G, et al (2020): Türkiye’deki bal örneklerinde neonikotinoid varlığının LC-MS/Q-TOF yöntemi ile tespiti. MAKÜ Sag Bil Enst Derg, 8, 11-17.
16. Jovanov P, Guzsvány V, Lazić S, et al (2015): Development of HPLC-DAD method for determination of neonicotinoids in honey. J Food Compos Anal, 40, 106-113.
17. Kaygısız F (2023): Factors affecting the choice of marketing channel by beekeepers in Türkiye. Ank Univ Vet Fak Derg, 70, 165-173.
18. Kumar A, Gill JPS, Bedi JS (2018): Multiresidue determination of pesticides in market honey from northern India using QuEChERS approach and assessment of potential risks to consumers. Curr Sci, 115, 283-291.
19. Ligor M, Bukowska M, Ratiu IA, et al (2020): Determination of Neonicotinoids in Honey Samples Originated from Poland and Other World Countries. Molecules, 25, 5817.
20. Mahamat AT, Altıntaş L, Aluç Y (2023): Investigation of the presence of some antibiotics in raw goat milk collected from Ankara, Kırıkkale and Çankırı provinces. Ankara Univ Vet Fak Derg, 70, 285-291.
21. Ministry of Agriculture and Forestry (2019): Gıda Kontrol Genel Müdürlüğü. Available at https://aydin.tarimorman.gov.tr/Duyuru/263/Neonicotinoid-Grubu-Aktif-Maddelerinin-Yasaklanmasi-Ve-Kisitlanmasi-Hk. (Accessed 10 Jan, 2022).
22. Mitchell EAD, Mulhauser B, Mulot M, et al (2017): A worldwide survey of neonicotinoids in honey. Science, 358, 109-111.
23. Mrzlikar M, Heath D, Heath E, et al (2019): Investigation of neonicotinoid pesticides in Slovenian honey by LC-MS/MS. Lwt 104, 45-52.
24. Paya P, Anastassiades M, Mack D, et al (2007). Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection. Anal Bioanal Chem, 389, 1697-1714.
25. Song S, Zhang C, Chen Z, et al (2018): Simultaneous determination of neonicotinoid insecticides and insect growth regulators residues in honey using LC-MS/MS with anion exchanger-disposable pipette extraction. J Chromatogr A, 1557, 51-61.
26. Tananaki C, Thrasyvoulou A, Giraudel, J, et al (2007): Determination of volatile characteristics of Greek and Turkish pine honey samples and their classification by using Kohonen self organising maps. Food Chem, 101, 1687-1693.
27. Tanner G, Czerwenka C (2011): LC-MS/MS analysis of neonicotinoid insecticides in honey: methodology and residue findings in Austrian honeys. J Agric Food Chem, 59, 12271-12277.
28. TÜİK (2021): Türkiye İstatistik Kurumu, Hayvansal Üretim İstatikleri, Aralık 2020 Available at https://data. tuik. gov.tr > Bulten > DownloadFilePDF. (Accessed 09 Feb, 2021).
29. UKİP (2018): Ulusal Kalıntı İzleme Planı, Gıda ve Kontrol Genel Müdürlüğü, Gıda Kontrol ve Laboratuvarlar Daire Başkanlığı. Available at https://avys.omu.edu.tr/storage/app/public/zpekmezci/124021/Numune%20alma.pdf. (Accessed 26 Feb, 2021).
30. Yücel Y, Sultanoglu P (2013): Characterization of honeys from Hatay Region by their physicochemical properties combined with chemometrics. Food Bioscience, 1, 16-25.

There are 30 citations in total.

Details

Primary Language	English
Subjects	Veterinary Pharmacology
Journal Section	Research Article
Authors	Halil Ergün 0000-0001-6460-3255 Levent Altıntaş 0000-0002-5148-723X
Early Pub Date	February 28, 2025
Publication Date	July 1, 2025
Submission Date	October 9, 2024
Acceptance Date	February 17, 2025
Published in Issue	Year 2025 Volume: 72 Issue: 3

Cite

APA	Ergün, H., & Altıntaş, L. (2025). Investigation of some neonicotinoids in honey by LC-MS/MS. Ankara Üniversitesi Veteriner Fakültesi Dergisi, 72(3), 267-276. https://doi.org/10.33988/auvfd.1563914
AMA	Ergün H, Altıntaş L. Investigation of some neonicotinoids in honey by LC-MS/MS. Ankara Univ Vet Fak Derg. July 2025;72(3):267-276. doi:10.33988/auvfd.1563914
Chicago	Ergün, Halil, and Levent Altıntaş. “Investigation of Some Neonicotinoids in Honey by LC-MS MS”. Ankara Üniversitesi Veteriner Fakültesi Dergisi 72, no. 3 (July 2025): 267-76. https://doi.org/10.33988/auvfd.1563914.
EndNote	Ergün H, Altıntaş L (July 1, 2025) Investigation of some neonicotinoids in honey by LC-MS/MS. Ankara Üniversitesi Veteriner Fakültesi Dergisi 72 3 267–276.
IEEE	H. Ergün and L. Altıntaş, “Investigation of some neonicotinoids in honey by LC-MS/MS”, Ankara Univ Vet Fak Derg, vol. 72, no. 3, pp. 267–276, 2025, doi: 10.33988/auvfd.1563914.
ISNAD	Ergün, Halil - Altıntaş, Levent. “Investigation of Some Neonicotinoids in Honey by LC-MS MS”. Ankara Üniversitesi Veteriner Fakültesi Dergisi 72/3 (July2025), 267-276. https://doi.org/10.33988/auvfd.1563914.
JAMA	Ergün H, Altıntaş L. Investigation of some neonicotinoids in honey by LC-MS/MS. Ankara Univ Vet Fak Derg. 2025;72:267–276.
MLA	Ergün, Halil and Levent Altıntaş. “Investigation of Some Neonicotinoids in Honey by LC-MS MS”. Ankara Üniversitesi Veteriner Fakültesi Dergisi, vol. 72, no. 3, 2025, pp. 267-76, doi:10.33988/auvfd.1563914.
Vancouver	Ergün H, Altıntaş L. Investigation of some neonicotinoids in honey by LC-MS/MS. Ankara Univ Vet Fak Derg. 2025;72(3):267-76.

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