Abstract
Fungicide residues of soil samples taken from Batak Plain of Çanakkale province of Türkiye were assessed. Fungicide residue analyses were performed with the use of QuEChERS method and LC-MS/MS device. Blank samples were spiked at two different limit of quantification (LOQ) levels for method verification. Overall recovery was identified as 85.69% with an RSD of 12.36% (n=360; SD=10.59). A total of 110 soil samples were taken in November 2020. Present analyses revealed that 59.09% of samples contained fungicide residues at different concentrations. Propiconazole had the highest concentration (1736.06 μg/kg) in one sample, taken from the edge of the field where pesticide wastes were found and 26 fungicides were found at different concentrations in the same sample. Azoxystrobin was encountered in majority of the samples (29 samples). The most frequent fungicides were ordered as; boscalid and tebuconazole (22 samples) > metalaxyl (17 samples) > fluopyram (15 samples). Thirteen triazole fungicides were found in soil samples, mostly at moderately hazardous level (Class II). Risk assessments revealed that hazard levels of fungicides for adults and children were low with a hazard quotient (HQ) and hazard index (HI) of <1. Despite the safe nature of fungicides in soil samples, the greatest HQ values were identified for propiconazole (326.52E-08 for adults and 2449.00E-08 for children). The sum of hazard quotients for all fungicides was 86.31E-08 8 for adult and 647.35E-08 for children. In terms of soil pollution, it is important for farmers to apply fungicides with low HQ levels.
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References
Abdel Ghani, S. B., & Hanafi, A. H. (2016). QuEChERS method combined with GC–MS for pesticide residues determination in water. Journal of Analytical Chemistry, 71, 508–512. https://doi.org/10.1134/S1061934816050117
Adeyinka, G. C., Moodley, B., Birungi, G., & Ndungu, P. (2019). Evaluation of organochlorinated pesticide (OCP) residues in soil, sediment and water from the Msunduzi River in South Africa. Environmental Earth Sciences, 78, 1–13. https://doi.org/10.1007/s12665-019-8227-y
Anastassiades, M., Lehotay, S. J., Štajnbaher, D., & Schenck, F. J. (2003). Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. Journal of AOAC international, 86(2), 412–431. https://doi.org/10.1093/jaoac/86.2.412
Anonymous, (2014). Technical guidelines for risk assessment of contaminated sites. FAO FAOLEX Database. https://www.fao.org/faolex/results/details/en/c/LEX-FAOC193194/. Accessed Jan 2023.
Anonymous, (2021). Fungicide data, Çanakkale Directorate of Provincial Agriculture and Forestry. pp 1 (in Turkish).
Aysal, P., Ambrus, A., Lehotay, S. J., & Cannavan, A. (2007). Validation of an efficient method for the determination of pesticide residues in fruits and vegetables using ethyl acetate for extraction. Journal of Environmental Science and Health, Part B, 42(5), 481–490. https://doi.org/10.1080/19312450701392490
Balkan, T., & Kara, K. (2023). Dissipation kinetics of some pesticides applied singly or in mixtures in/on grape leaf. Pest Management Science, 79, 1234–1242. https://doi.org/10.1002/ps.7299
Cessna, A. J., & Allan, J. (2009). Pesticides in the environment: Real or Imagined. In Agriculture and Agri-food Canada. Research Centre.
Chen, C., Qian, Y., Chen, Q., Tao, C., Li, C., & Li, Y. (2011). Evaluation of pesticide residues in fruits and vegetables from Xiamen, China. Food Control, 22(7), 1114–1120. https://doi.org/10.1016/j.foodcont.2011.01.007
Cui, K., Wu, X., Zhang, Y., Cao, J., Wei, D., Xu, J., et al. (2021). Cumulative risk assessment of dietary exposure to triazole fungicides from 13 daily consumed foods in China. Environmental Pollution, 286, 117550. https://doi.org/10.1016/j.envpol.2021.117550
EFSA. (2007). Cumulative risk assessment of pesticides to human health: The way forward. In EFSA Scientific colloquium summary report 7. Parma: European Food Safety Authority. https://efsa.onlinelibrary.wiley.com/doi/epdf/10.2903/sp.efsa.2007.EN-117.
EU, (2022) European Union Pesticides database. https://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/mrls/?event=search.pr. Accessed Oct 2022.
Fu, G. P., Li, G. Y., Ji, Y., & Wu, Z. F. (2012). WHO Recommendations for public health pest control methods and pesticide dosage ranges. Pest Science Administration, 33(11), 4–9. https://doi.org/10.3969/j.issn.1002-5480.2012.11.003
Gikas, G. D., Parlakidis, P., Mavropoulos, T., & Vryzas, Z. (2022). Particularities of fungicides and factors affecting their fate and removal efficacy: A review. Sustainability, 14(7), 4056. https://doi.org/10.3390/su14074056
Hasnaki, R., Ziaee, M., & Mahdavi, V. (2023). Pesticide residues in corn and soil of corn fields of Khuzestan, Iran, and potential health risk assessment. Journal of Food Composition and Analysis, 115, 104972. https://doi.org/10.1016/j.jfca.2022.104972
Hathout, A., Amer, M., Hussain, O., Yassen, A. A., Mossa, A. T. H., & Elgohary, M. R. (2022). Estimation of the most widespread pesticides in agricultural soils collected from some Egyptian governorates. Egyptian Journal of Chemistry, 65(1), 35–44. https://doi.org/10.21608/ejchem.2021.72087.3591
Jing, X., Zhang, W., Xie, J., Wang, W., Lu, T., Dong, Q., & Yang, H. (2021). Monitoring and risk assessment of pesticide residue in plant-soil-groundwater systxem about medlar planting in Golmud. Environmental Science and Pollution Research, 28, 26413–26426. https://doi.org/10.1007/s11356-021-12403-0
Kazar Soydan, D., Turgut, N., Yalçın, M., Turgut, C., & Karakuş, P. B. K. (2021). Evaluation of pesticide residues in fruits and vegetables from the Aegean region of Turkey and assessment of risk to consumers. Environmental Science and Pollution Research, 28, 27511–27519. https://doi.org/10.1007/s11356-021-12580-y
Medić Pap, S., Popović, B., Stojić, N., Danojević, D., Pucarević, M., Červenski, J., & Šperanda, M. (2022). The environmental issue of pesticide residues in agricultural soils in Serbia. International Journal of Environmental Science and Technology, 1-14. https://doi.org/10.1007/s13762-022-04424-0
Omeroglu, P. Y., Boyacioglu, D., Ambrus, A., Karaali, A., & Saner, S. (2012). An overview on steps of pesticide residue analysis and contribution of the individual steps to the measurement uncertainty. Food Analytical Methods, 5(5), 1469–1480. https://doi.org/10.1007/s12161-012-9396-4
Polat, B., & Tiryaki, O. (2019). Determination of some pesticide residues in conventional-grown and IPM-grown tomato by using QuEChERS method. Journal of Environmental Science and Health, Part B, 54(2), 112–117. https://doi.org/10.1080/03601234.2018.1531663
Polat, B. (2021). Reduction of some insecticide residues from grapes with washing treatments. Turkish Journal of Entomology, 45(1), 125–137. https://doi.org/10.16970/entoted.843754
Polat, B., & Tiryaki, O. (2022). Determination of insecticide residues in soils from Troia agricultural fields by the QuEChERS method. Turkish Journal of Entomology, 46(3), 251–261. https://doi.org/10.16970/entoted.1101713
PubChem, (2022). PubChem database National Library National Center of Biotechnology Information. https://pubchem.ncbi.nlm.nih.gov/#query. Accessed Sept 2022.
Sadeghi-Yarandi, M., Karimi, A., Ahmadi, V., Sajedian, A. A., Soltanzadeh, A., & Golbabaei, F. (2020). Cancer and non-cancer health risk assessment of occupational exposure to 1, 3-butadiene in a petrochemical plant in Iran. Toxicology and Industrial Health, 36(12), 960–970. https://doi.org/10.1177/074823372096
SANTE, (2021) Guidance SANTE 11312/2021.Analytical quality control and method validation procedures for pesticide residues analysis in food and feed. SANTE.11312/2021. https://www.accredia.it/documento/guidance-sante-11312-2021-analytical-quality-control-and-method-validation-procedures-for-pesticide-residues-analysis-in-food-and-feed/
Singh, R. P., Mahajan, M., Gandhi, K., Gupta, P. K., Singh, A., Singh, P., et al. (2023). A holistic review on trend, occurrence, factors affecting pesticide concentration, and ecological risk assessment. Environmental Monitoring and Assessment, 195(4), 1–18. https://doi.org/10.1007/s10661-023-11005-2
Tadesse, A. W. (2021). Occurrences, Potential Sources and Health Impacts of Organochlorine Pesticides in Soil from Wuhan, Central China. Bulletin of Environmental Contamination and Toxicology, 107(2), 296–311. https://doi.org/10.1007/s00128-021-03245-0
Temur, C., Tiryaki, O., Uzun, O., & Basaran, M. (2012). Adaptation and validation of QuEChERS method for the analysis of trifluralin in wind-eroded soil. Journal of Environmental Science and Health, Part B, 47(9), 842–850. https://doi.org/10.1080/03601234.2012.693878
Tiryaki, O., Baysoyu, D., Seçer, E., & Aydın, G. (2008). Testing the stability of pesticides during sample processing for the chlorpyrifos and malathion residue analysis in cucumber, including matrix effects. Bulletin of Environmental Contamination and Toxicology, 80, 38–43. https://doi.org/10.1007/s00128-007-9308-2
Tiryaki, O., & Temur, C. (2010). The fate of pesticide in the environment. Journal of Biological and Environmental Sciences, 4(10), 29–38.
Top, Z. N., Tiryaki, O., & Polat, B. (2023). Monitoring and environmental risk assessment of agricultural fungicide and insecticides in water, sediment from Kumkale Plain, Çanakkale-Turkey. Journal of Environmental Science and Health, Part B, 1-12. https://doi.org/10.1080/03601234.2023.2187598
TSI, (2021) Turkish Statistical Institute. Data Portal for Statistics. Pesticide Usage. https://data.TSI.gov.tr/Kategori/GetKategori?p=tarim-111&dil=1. Accessed: February 2021.
USEPA, (1998). Human health risk assessmet protocol: Chapter 7 risk and hazard characterization. http://www.columbia.edu/itc/sipa/envp/louchouarn/courses/envchem/RiskCharacterizationRegion6.pdf. Accessed May 2022
USEPA, (2007). Method1699: Pesticides in water, soil, sediment, biosolids, and tissue by HRGC/HRMS: Environmental Protection Agency, Washington, USAEPA-821-R-08-001, pp 96. https://www.nemi.gov/methods/method_summary/9690. Accessed Mar 2022.
USEPA, (2013). Environmental Protection Agency. Tebuconazole, pesticide tolerances, EPA-HQ-OPP-2012-0427, FRL-9392-1, Federal Register Volume, 78, 68741-68748, Document Number: 2013-27147. 68741-68748. https://www.federalregister.gov/documents/2013/11/15/2013-27147/tebuconazole-pesticide-tolerances. Accessed May 2023
USEPA, (2020). Regional screening level (RSL) resident soil to GW table (TR = 1E−06, HQ = 1). https://www.epa.gov/risk/regional-screeninglevels-rsls-generic-tables. Accessed May 2023.
USEPA, (2021). Tebuconazole 3.6 FL, Label Amendment - Addition of crop uses & label corrections. United States Environmental Protection Agency Washington, 20460. https://www3.epa.gov/pesticides/chem_search/ppls/042750-00099-20210301.pdf. Accessed May 2023.
Vickneswaran, M., Carolan, J. C., & White, B. (2021). Simultaneous determination of pesticides from soils: a comparison between QuEChERS extraction and Dutch mini-Luke extraction methods. Analytical Methods, 13(46), 5638–5650. https://doi.org/10.1039/D1AY01248G
WHO, (2019). The WHO Recommended Classification of Pesticides by Hazard and Guidelines to Classication. https://apps.who.int/iris/rest/bitstreams/1278712/retrieve. Accessed Dec 2022.
Yıldırım, I., & Özcan, H. (2007). Determination of pesticide residues in water and soil resources of Troia (Troy). Fresenius Environmental Bulletin, 16(1), 63–70.
Zaidon, S. Z., Ho, Y. B., Hamsan, H., Hashim, Z., Saari, N., & Praveena, S. M. (2019). Improved QuEChERS and solid phase extraction for multi-residue analysis of pesticides in paddy soil and water using ultra-high performance liquid chromatography tandem mass spectrometry. Microchemical Journal, 145, 614–621. https://doi.org/10.1016/j.microc.2018.11.025
Acknowledgements
This study was supported by Scientific Research Projects Department of Çanakkale Onsekiz Mart University (Project number: FBA-2020-3228). Thanks are extended to Prof. Dr. Zeki Gökalp for help with preparation of the manuscript and technical staff of Çanakkale Food Control Directorate (Pesticide Residue Laboratory) for LC-MS/MS analyses.
Funding
This study was partially funded by Scientific Research Projects Department of Çanakkale Onsekiz Mart University-Turkey (FBA-2020-3228)
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Burak Polat designed the research, performed soil sampling, involved chemical analysis and risk assessment. Osman Tiryaki was responsible for chemical analysis and risk assessment and QA/QC procedure. Both authors discussed the results and wrote the manuscript.
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Polat, B., Tiryaki, O. Determination of fungicide residues in soil using QuEChERS coupled with LC-MS/MS, and environmental risk assessment. Environ Monit Assess 195, 986 (2023). https://doi.org/10.1007/s10661-023-11550-w
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DOI: https://doi.org/10.1007/s10661-023-11550-w