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Determination of insecticides in honey samples collected from Gümüşhane-Turkiye; Box-Behnken design evaluation of experimental parameters

Year 2025, Volume: 5 Issue: 1, 176 - 186, 31.01.2025
https://doi.org/10.61112/jiens.1567692

Abstract

This study deals with the investigation of cyfluthrin, cypermethrin, deltamethrin, and malathion residues in local honey samples from Gümüşhane, Turkey. The determination was performed with GC/MS-MS method with HP-5MS column under certain conditions: 120 ℃ oven temperature, 250 ℃ injection temperature, 121.9 kPa pressure and 1.2-1.8 mL/min flow rates. The samples were picked from eighteen stations of Gümüşhane. Standard addition method was employed in chromatographic determination. No pesticide detected in samples of fifteen stations, nevertheless, subjected pesticides were determined in samples collected from other three stations. The residue levels varied from 0.18 mg/kg to 9.50 mg/kg at 1.5 mL/min flow rate. The results were also evaluated with Box-Behnken Design (BBD) optimization. Multivariate experimental design (flow rate and station, pesticide type) was employed for constructing quadratic models. Regression analysis showed that the experimental results and the predictive values yielded by model are quite close to each other with determination coefficient (R2) of 0.985.

Ethical Statement

The authors declare that there is no financial or personal conflicting interest that could influence the work reported in this paper.

Thanks

The authors thank Sevim Razak from Ekoteks Laboratuvar ve Gözetim Hizmetleri A.Ş. for their supporting this study and allowing their laboratory opportunities.

References

  • Saleh MA (1980) Mutagenic and carcinogenic effects of pesticides. Journal of Environmental Science and Health Part B 15(6):907–927. https://doi.org/10.1080/03601238009372222
  • Mukherjee I (2009). Determination of Pesticide Residues in Honey Samples. Bulletin of Environmental Contamination and Toxicology, 83 (6): 818–821. https://doi.org/10.1007/s00128-009-9772-y
  • Zhang L, Zhao M, Xiao M, Im M-H, Abd El-Aty AM et al (2022) Recent Advances in the Recognition Elements of Sensors to Detect Pyrethroids in Food: A Review. Biosensors, 12:402. https://doi.org/10.3390/bios12060402
  • El-Osmani R, Net S, Dumoulin D, Bigan M, Ouddane B et al (2014) An experimental design approach to the optimisation of pesticide extraction from water. Anal Methods 6(16):6514-6521. https://doi.org/10.1039/c4ay00610k
  • Ndungu NN, Kegode TM, Kurgat JK, Baleba SBS, Cheseto X et al (2024) Bio-functional properties and phytochemical composition of selected Apis mellifera honey from Africa. Heliyon 10:e30839. https://doi.org/10.1016/j.heliyon.2024.e30839
  • Jakkielska D, Frankowski M, Zioła-Frankowska A (2024) Speciation analysis of arsenic in honey using HPLC-ICP-MS and health risk assessment of water-soluble arsenic. Journal of Hazardous Materials 471:134364. https://doi.org/10.1016/j.jhazmat.2024.134364
  • Sabater C, Calvete I, Vázquez X, Ruiz L, Margolles A (2024) Tracing the origin and authenticity of Spanish PDO honey using metagenomics and machine learning. International Journal of Food Microbiology 421:110789. https://doi.org/10.1016/j.ijfoodmicro.2024.110789
  • Ek-Huchim JP, Rodríguez-Cab EM, López-Torres E, Dzul-Caamal R, Canepa-Pérez IM et al (2024) Pesticides and polycyclic aromatic hydrocarbons in honey and Apis mellifera from the Yucatán Peninsula, Mexico. Journal of Food Composition and Analysis 132:106293. https://doi.org/10.1016/j.jfca.2024.106293
  • Wang X, Dong Y, Luan Y, Tian S, Li C et al (2024) Integrated assessment of the spatial distribution, sources, degradation, and human risk of tetracyclines in honey in China. Journal of Hazardous Materials 473:134681. https://doi.org/10.1016/j.jhazmat.2024.134681
  • Demir E, Recai I (2018) Voltammetric determination of phenmedipham herbicide using a multiwalled carbon nanotube paste electrode. Turkish Journal of Chemistry 42:4. https://doi.org/10.3906/kim-1709-41
  • Saqaf JM, Soylak M (2021) Supramolecular solvents: a review of a modern innovation in liquid-phase microextraction technique. Turkish Journal of Chemistry 45:6. https://doi.org/10.3906/kim-2110-15
  • Ostiguy N, Drummond FA, Aronstein K, Eitzer B, Ellis JD et al (2019) Honey Bee Exposure to Pesticides: A Four-Year Nationwide Study. Insects 10:13. https://doi.org/10.3390/insects10010013
  • Jovanov P, Guzsvány V, Franko M, Lazić S, Sakač M et al (2013) Multi-residue method for determination of selected neonicotinoid insecticides in honey using optimized dispersive liquid–liquid microextraction combined with liquid chromatography-tandem mass spectrometry. Talanta 111:125-133. https://doi.org/10.1016/j.talanta.2013.02.059
  • Tolcha T, Gemechu T, Al-Hamimi S, Megersa N, Turner C (2020) High density supercritical carbon dioxide for the extraction of pesticide residues in onion with multivariate response surface methodology. Molecules 25(4):1012. https://doi.org/10.3390/molecules25041012
  • Amvrazi EG, Martini MA, Tsiropoulos NG. (2012). Headspace single-drop microextraction of common pesticide contaminants in honey–method development and comparison with other extraction methods. International Journal of Environmental Analytical Chemistry 92(4):450-465. https://doi.org/10.1080/03067319.2011.585716
  • Nemati M, Altunay N, Tuzen M, Farajzadeh MA, Afshar Mogaddam MR (2022) In‐situ sorbent formation for the extraction of pesticides from honey. Journal of Separation Science 45(14):2652-2662. https://doi.org/10.1002/jssc.202100963
  • Tette PAS, Guidi LR, Abreu Glória MB, Fernandes C (2016) Pesticides in honey: A review on chromatographic analytical methods. Talanta 149:124-141. https://doi.org/10.1016/j.talanta.2015.11.045
  • Briggs GG, Elliott M, Farnham AW, Janes NF, Needham PH et al (1976) Insecticidal activity of the pyrethrins and related compounds VIII. Relation of polarity with activity in pyrethroids. Pesticide Science 7(3):236–240. https://doi.org/10.1002/ps.2780070305
  • Hamadamin AY, Hassan KI (2020) Gas chromatography-mass spectrometry based sensitive analytical approach to detect and quantify non-polar pesticides accumulated in the fat tissues of domestic animals. Saudi J Biol Sci 27(3):887-893. https://doi.org/10.1016/j.sjbs.2019.12.029
  • Lu, FC (1995) A Review of the Acceptable Daily Intakes of Pesticides Assessed by WHO. Regulatory Toxicology and Pharmacology 21(3):352-364. https://doi.org/10.1006/rtph.1995.1049
  • U.S. Environmental Protection Agency. Pesticide Fact Sheet Number 199:Cypermethrin. Office of Pesticides and Toxic Substances, Washington, DC, 1989.2-9.
  • Pesticide Residues in Food 2000 - Deltamethrin; International Programme on Chemical Safety, Food and Agriculture Organization of the United Nations and World Health Organization: Geneva, Switzerland, 2001; pp 79-110.
  • Revised Reregistration Eligibility Decision (RED) for Malathion; EPA 738-R-06-030; U.S Environmental Protection Agency, Office of Prevention, Pesticides and Toxic Substances, Office of Pesticide Programs, U.S. Government Printing Office: Washington, DC, 2009.
  • El-Nahhal Y (2020) Pesticide residues in honey and their potential reproductive toxicity. Science of The Total Environment 741:139953. https://doi.org/10.1016/j.scitotenv.2020.139953
  • Tolcha T, Gemechu T, Al‐Hamimi S, Megersa N, Turner C (2021) Multivariate optimization of a combined static and dynamic supercritical fluid extraction method for trace analysis of pesticides pollutants in organic honey. Journal of Separation Science 44(8):1716-1726. https://doi.org/10.1002/jssc.202100047

Determination of insecticides in honey samples collected from Gümüşhane-Turkiye; Box-Behnken design evaluation of experimental parameters

Year 2025, Volume: 5 Issue: 1, 176 - 186, 31.01.2025
https://doi.org/10.61112/jiens.1567692

Abstract

This study deals with the investigation of cyfluthrin, cypermethrin, deltamethrin, and malathion residues in local honey samples from Gümüşhane, Turkey. The determination was performed with GC/MS-MS method with HP-5MS column under certain conditions: 120 ℃ oven temperature, 250 ℃ injection temperature, 121.9 kPa pressure and 1.2-1.8 mL/min flow rates. The samples were picked from eighteen stations of Gümüşhane. Standard addition method was employed in chromatographic determination. No pesticide detected in samples of fifteen stations, nevertheless, subjected pesticides were determined in samples collected from other three stations. The residue levels varied from 0.18 mg/kg to 9.50 mg/kg at 1.5 mL/min flow rate. The results were also evaluated with Box-Behnken Design (BBD) optimization. Multivariate experimental design (flow rate and station, pesticide type) was employed for constructing quadratic models. Regression analysis showed that the experimental results and the predictive values yielded by model are quite close to each other with determination coefficient (R2) of 0.985.

References

  • Saleh MA (1980) Mutagenic and carcinogenic effects of pesticides. Journal of Environmental Science and Health Part B 15(6):907–927. https://doi.org/10.1080/03601238009372222
  • Mukherjee I (2009). Determination of Pesticide Residues in Honey Samples. Bulletin of Environmental Contamination and Toxicology, 83 (6): 818–821. https://doi.org/10.1007/s00128-009-9772-y
  • Zhang L, Zhao M, Xiao M, Im M-H, Abd El-Aty AM et al (2022) Recent Advances in the Recognition Elements of Sensors to Detect Pyrethroids in Food: A Review. Biosensors, 12:402. https://doi.org/10.3390/bios12060402
  • El-Osmani R, Net S, Dumoulin D, Bigan M, Ouddane B et al (2014) An experimental design approach to the optimisation of pesticide extraction from water. Anal Methods 6(16):6514-6521. https://doi.org/10.1039/c4ay00610k
  • Ndungu NN, Kegode TM, Kurgat JK, Baleba SBS, Cheseto X et al (2024) Bio-functional properties and phytochemical composition of selected Apis mellifera honey from Africa. Heliyon 10:e30839. https://doi.org/10.1016/j.heliyon.2024.e30839
  • Jakkielska D, Frankowski M, Zioła-Frankowska A (2024) Speciation analysis of arsenic in honey using HPLC-ICP-MS and health risk assessment of water-soluble arsenic. Journal of Hazardous Materials 471:134364. https://doi.org/10.1016/j.jhazmat.2024.134364
  • Sabater C, Calvete I, Vázquez X, Ruiz L, Margolles A (2024) Tracing the origin and authenticity of Spanish PDO honey using metagenomics and machine learning. International Journal of Food Microbiology 421:110789. https://doi.org/10.1016/j.ijfoodmicro.2024.110789
  • Ek-Huchim JP, Rodríguez-Cab EM, López-Torres E, Dzul-Caamal R, Canepa-Pérez IM et al (2024) Pesticides and polycyclic aromatic hydrocarbons in honey and Apis mellifera from the Yucatán Peninsula, Mexico. Journal of Food Composition and Analysis 132:106293. https://doi.org/10.1016/j.jfca.2024.106293
  • Wang X, Dong Y, Luan Y, Tian S, Li C et al (2024) Integrated assessment of the spatial distribution, sources, degradation, and human risk of tetracyclines in honey in China. Journal of Hazardous Materials 473:134681. https://doi.org/10.1016/j.jhazmat.2024.134681
  • Demir E, Recai I (2018) Voltammetric determination of phenmedipham herbicide using a multiwalled carbon nanotube paste electrode. Turkish Journal of Chemistry 42:4. https://doi.org/10.3906/kim-1709-41
  • Saqaf JM, Soylak M (2021) Supramolecular solvents: a review of a modern innovation in liquid-phase microextraction technique. Turkish Journal of Chemistry 45:6. https://doi.org/10.3906/kim-2110-15
  • Ostiguy N, Drummond FA, Aronstein K, Eitzer B, Ellis JD et al (2019) Honey Bee Exposure to Pesticides: A Four-Year Nationwide Study. Insects 10:13. https://doi.org/10.3390/insects10010013
  • Jovanov P, Guzsvány V, Franko M, Lazić S, Sakač M et al (2013) Multi-residue method for determination of selected neonicotinoid insecticides in honey using optimized dispersive liquid–liquid microextraction combined with liquid chromatography-tandem mass spectrometry. Talanta 111:125-133. https://doi.org/10.1016/j.talanta.2013.02.059
  • Tolcha T, Gemechu T, Al-Hamimi S, Megersa N, Turner C (2020) High density supercritical carbon dioxide for the extraction of pesticide residues in onion with multivariate response surface methodology. Molecules 25(4):1012. https://doi.org/10.3390/molecules25041012
  • Amvrazi EG, Martini MA, Tsiropoulos NG. (2012). Headspace single-drop microextraction of common pesticide contaminants in honey–method development and comparison with other extraction methods. International Journal of Environmental Analytical Chemistry 92(4):450-465. https://doi.org/10.1080/03067319.2011.585716
  • Nemati M, Altunay N, Tuzen M, Farajzadeh MA, Afshar Mogaddam MR (2022) In‐situ sorbent formation for the extraction of pesticides from honey. Journal of Separation Science 45(14):2652-2662. https://doi.org/10.1002/jssc.202100963
  • Tette PAS, Guidi LR, Abreu Glória MB, Fernandes C (2016) Pesticides in honey: A review on chromatographic analytical methods. Talanta 149:124-141. https://doi.org/10.1016/j.talanta.2015.11.045
  • Briggs GG, Elliott M, Farnham AW, Janes NF, Needham PH et al (1976) Insecticidal activity of the pyrethrins and related compounds VIII. Relation of polarity with activity in pyrethroids. Pesticide Science 7(3):236–240. https://doi.org/10.1002/ps.2780070305
  • Hamadamin AY, Hassan KI (2020) Gas chromatography-mass spectrometry based sensitive analytical approach to detect and quantify non-polar pesticides accumulated in the fat tissues of domestic animals. Saudi J Biol Sci 27(3):887-893. https://doi.org/10.1016/j.sjbs.2019.12.029
  • Lu, FC (1995) A Review of the Acceptable Daily Intakes of Pesticides Assessed by WHO. Regulatory Toxicology and Pharmacology 21(3):352-364. https://doi.org/10.1006/rtph.1995.1049
  • U.S. Environmental Protection Agency. Pesticide Fact Sheet Number 199:Cypermethrin. Office of Pesticides and Toxic Substances, Washington, DC, 1989.2-9.
  • Pesticide Residues in Food 2000 - Deltamethrin; International Programme on Chemical Safety, Food and Agriculture Organization of the United Nations and World Health Organization: Geneva, Switzerland, 2001; pp 79-110.
  • Revised Reregistration Eligibility Decision (RED) for Malathion; EPA 738-R-06-030; U.S Environmental Protection Agency, Office of Prevention, Pesticides and Toxic Substances, Office of Pesticide Programs, U.S. Government Printing Office: Washington, DC, 2009.
  • El-Nahhal Y (2020) Pesticide residues in honey and their potential reproductive toxicity. Science of The Total Environment 741:139953. https://doi.org/10.1016/j.scitotenv.2020.139953
  • Tolcha T, Gemechu T, Al‐Hamimi S, Megersa N, Turner C (2021) Multivariate optimization of a combined static and dynamic supercritical fluid extraction method for trace analysis of pesticides pollutants in organic honey. Journal of Separation Science 44(8):1716-1726. https://doi.org/10.1002/jssc.202100047
There are 25 citations in total.

Details

Primary Language English
Subjects Environmental and Sustainable Processes, Food Engineering
Journal Section Research Articles
Authors

Erol Erçağ 0000-0003-4927-2405

Berrin Saygı Yalçın 0000-0001-6579-3345

Murat Şahin 0000-0003-2471-1555

Fehime Jülide Hızal Yücesoy 0000-0002-5921-0155

Publication Date January 31, 2025
Submission Date October 16, 2024
Acceptance Date January 2, 2025
Published in Issue Year 2025 Volume: 5 Issue: 1

Cite

APA Erçağ, E., Saygı Yalçın, B., Şahin, M., Hızal Yücesoy, F. J. (2025). Determination of insecticides in honey samples collected from Gümüşhane-Turkiye; Box-Behnken design evaluation of experimental parameters. Journal of Innovative Engineering and Natural Science, 5(1), 176-186. https://doi.org/10.61112/jiens.1567692


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