Verification of QuEChERS Method for the Analysis of Pesticide Residues and Their Risk Assessment in Some Fruits Grown in Tokat, Turkey

Abstract

This study sought to determine pesticide residues in some fruits in Tokat province, Turkey and to assess the health risks associated with the determined residues. QuEChERS analytical method was verified to determine 260 pesticides by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Pesticide solutions corresponded 10 and 50 µg kg­-1 were applied to the pesticide-free apple matrix for the method verification. The linearities (R2), limit of detections, limit of quantifications and mean recovery values of the pesticides ranged between 0.990-0.999, 0.83-3 μg kg­-1, 2.76-9.99 μg kg­-1 and 70.3-119% (with relative standard deviation ≤20%), respectively. The results were evaluated according to the European Union maximum residue limits (EU-MRL). The residues were lower and higher than the EU-MRL with a ratio of 37.7% and 32.1% of the tested samples, respectively. The residue levels of diflubenzuron in apples, permethrin in cherries, and dimethoate in pears, apples, and peaches were higher than the EU-MRL. The results of health risk assessments indicated that omethoate and dimethoate have acute and chronic toxicity potential for consumers. Hence, the pesticide use in the study area must be reduced to avoid health risks. Furthermore, alternative management methods should be developed to lower the use of pesticides.

Keywords

• LC-MS/MS
• Fresh fruit
• Method verification
• Health risk
• QuEChERS

References

1. Aberoumand A & Deokule S S (2010). Elements evaluation of some edible vegetables and fruits of Iran and India. Asian Journal of Agricultural Sciences, 2(1): 35–37
2. Akhtar S, Naz S, Tuseef S M, Mahmood S, Nasir M & Ahmad A (2010). Physico-chemical attributes and heavy metalcontent of mangoes (Mangifera indica) cultivated in different regions of Pakistan. Pakistan Journal of Botany, 42(4): 2691–2702
3. Arias-Estévez M, López-Periago E, Martínez-Carballo E, Simal-Gándara J, Mejuto J C & García-Río L (2008). The mobility and degradation of pesticides in soils and the pollution of groundwater resources. Agriculture, Ecosystems & Environment, 123:247–260
4. Ay R, Karaca İ & Seçilmiş H (2003). Determination of the residue levels of some insecticide, commonly used in apple orchards in Isparta province, by HPLC. Turkish Journal of Entomology, 27 (4): 293-304
5. Ay R, Yaşar B, Demirözer O, Aslan B, Yorulmaz S, Kaya M & Karaca İ (2007). The determination of the residue levels of some commonly used pesticides in Isparta apple orchards. Turkish Journal of Entomology, 31 (4): 297-306
6. Baldi I, Filleul L, Mohammed-Brahim B, Fabrigoule C, Dartigues J F, Schwall S, Drevet J P, Salamon R & Brochard P (2001). Neuropsychologic effects of long-term exposure to pesticides: results from the French Phytoner study. Environmental Health Perspective, 109: 839–844. DOI: 10.1289/ehp.01109839
7. Balkan, T, & Yılmaz Ö (2022). Method validation, residue and risk assessment of 260 pesticides in some leafy vegetables using liquid chromatography coupled to tandem mass spectrometry. Food Chemistry, 384, 132516, DOI: 10.1016/j.foodchem.2022.132516
8. BfR (2013). Federal institute for risk assessment. Retrieved in August, 14, 2021 http://mobile.foodqualitynews.com/Public-Concerns/Pesticide-residue-assessment-must-be-simpleand-transparent-says-BfR.

9. Cantor K P, Blair A, Everett G, Gibson R, Burmeister L F, Brown L M, Shuman L & Dick F R (1992). Pesticides and other agricultural risk factors for non-Hodgkin's lymphoma among men in Iowa and Minnesota. Cancer Research, 52: 2447–2455
10. Claeys W L, Schmit J F, Bragard C, Maghuin-Rogister G, Pussemier L & Schiffers B (2011). Exposure of several belgian consumer groups to pesticide residues through fresh fruit and vegetable consumption. Food Control, 22 (3), 508–516
11. Cristina H M G, Gabriel H M, Petru N, Radu S, Adina N & Ducu S (2014). The monitoring of mineral elements content in fruit purchased in supermarkets and food markets in Timisoara, Romania. Annals of Agricultural and Environmental Medicine, 21 (1):98–105
12. El Hawari K, Mokh S, Al Iskandarani M, Halloum W & Jaber F (2019). Pesticide residues in Lebanese apples and health risk assessment. Food Additives & Contaminants: Part B, 12:2, 81-89, DOI: 10.1080/19393210.2018.1564370
13. Ersoy N, Tatlı Ö, Özcan S, Evcil E, Çoşkun Ş L & Erdoğan E (2011a). Determination of Pesticide Residues in Some Vegetable Species by LC-MS/MS and GC-MS. Selçuk Tarım ve Gıda Bilimleri Dergisi 25 (3): 79-85
14. Ersoy N, Tatlı Ö, Özcan, S, Evcil E, Coşkun L Ş, Erdoğan E & Keskin G (2011b). Determination of Pesticide Residues in Grape and Strawberry Using LC-MS/MS and GC-MS. Selçuk Tarım ve Gıda Bilimleri Dergisi 25 (2): 70-80
15. Ersoy N, Tatlı Ö, Özcan S, Evcil E, Çoşkun Ş L & Erdoğan E (2011c). Some Pesticide Residues of Stone and Nuts Fruit Species. Selçuk Tarım ve Gıda Bilimleri Dergisi 25 (1): 75-83
16. Ersoy N, Tatlı Ö, Özcan S, Evcil E, Çoşkun Ş L & Erdoğan E (2011d). Pesticide Residue Levels in Some Pome Fruits Consumed to Public in Konya Province. Selçuk Tarım ve Gıda Bilimleri Dergisi 25 (1): 84-89
17. European Commission, 2002. Commission Directive 2002/63/EC of 11 July 2002 establishing community methods of sampling for the official control of pesticide residues in and on products of plant and animal origin and repealing Directive 79/700/EEC. Official Journal of the European Communities, 2: 30–43
18. European Commission, 2019. SANTE/12682/2019 Guidance document on analytical quality control and method validation procedures for pesticide residues and analysis in food and feed. 1–49
19. European Commission, 2022. European Union Pesticide MRLs Database (v.2.2). Retrieved in January, 22, 2022 from https://ec.europa.eu/food/plant/pesticides/eu-pesticides database/mrls/?event=se arch.pr
20. Fan X, Zhao S & Hu J (2019). Dissipation behavior and dietary risk assessment of lambda-cyhalothrin, thiamethoxam and its metabolite clothianidin in apple after open field application. Regulatory Toxicology and Pharmacology, 101, 135-141, DOI: 10.1016/j.yrtph.2018.11.003
21. Fernandez-Alba A R & García-Reyes J F (2008). Large-scale multi-residue methods for pesticides and their degradation products in food by advanced LC-MS. Trends in Analytical Chemistry, 27(11), 973–990, DOI: 10.1016/j.trac.2008.09.009
22. Gondo T F, Kamakama M, Oatametse B, Samu T, Bogopa J & Keikotlhaile B M (2021). Pesticide residues in fruits and vegetables from the southern part of Botswana, Food Additives & Contaminants: Part B, 14:4, 271-280, DOI: 10.1080/19393210.2021.1950845
23. Hamilton D & Crossley S (eds.) (2004). Introduction, in Pesticide Residues in Food and Drinking Water: Human Exposure and Risks, John Wiley & Sons, Ltd, Chichester, pp. 1–25
24. Hamzawy A H (2022). Residual pesticides in grape leaves (Vitis vinifera L.) on the Egyptian market and human health risk. Food Additives & Contaminants: Part B, 15:1, 62-70, DOI: 10.1080/19393210.2021.2022005
25. Kaya T & Tuna A L (2019). Investigation of Pesticide Residue Levels in Fruit and Vegetables Collected from Three Farmers Market in İzmir Province. Turkish Journal of Agricultural Engineering Research, 6 (1), 32-38
26. Lehotay S J (2007). Determination of Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with Magnesium Sulfate: Collaborative Study. Journal AOAC International, 90, 485–520
27. Li Z, Nie J, Yan Z, Cheng Y, Lan F, Huang Y, Chen Q, Zhao X & Li A (2019). A monitoring survey and dietary risk assessment for pesticide residues on peaches in China, Regulatory Toxicology and Pharmacology, 97, 152-162, DOI: 10.1016/j.yrtph.2018.06.007
28. Li Z X, Nie J Y, Yan Z, Xu G F, Li H F, Kuang L X, Pan L G, Xie H Z, Wang C, Liu C, Zhao X B & Guo Y Z. (2015). Risk assessment and ranking of pesticide residues in Chinese pears. Journal of Integrative Agriculture, 14, 2328–2339, DOI: 10.1016/S2095-3119(15)61124-8
29. Liu Y, Shen D, Li S, Ni Z, Ding M, Ye C & Tang F (2016). Residue levels and risk assessment of pesticides in nuts of China. Chemosphere, 144: 645-651. DOI: 10.1016/j.chemosphere.2015.09.008
30. Lozowicka B (2015). Health risk for children and adults consuming apples with pesticide residue. Science of the total environment, 502: 184-198, DOI: 10.1016/j.scitotenv.2014.09.026
31. Mutengwe M T, Chidamba L & Korsten L (2016). Monitoring pesticide residues in fruits and vegetables at two of the biggest fresh produce markets in Africa. Journal of Food Protection, 79(11):1938–1945, DOI:10.4315/0362-028X. JFP-16-190
32. Nalcı T, Dardeniz, A, Polat B & Tiryaki O (2018). Determination of pesticide residue amounts of early and middle/late turfan grape cultivars by QuEChERS analysis method. COMU Journal of Agriculture Faculty, 6: 39 – 44
33. Skrovankova S, Sumczynski D, Mlcek J, Jurikova T, & Sochor J (2015). Bioactive Compounds and Antioxidant Activity in Different Types of Berries. International journal of molecular sciences, 16(10), 24673–24706, DOI:10.3390/ijms161024673
34. Słowik-Borowiec M, Szpyrka E, Rupar J, Matyaszek A & Podbielska M (2015). Pesticide residues in stone fruits from the south-eastern region of Poland in 2012-2104. Roczniki Panstwowego Zakladu Higieny, 66(3), 211–216
35. Stachniuk A, Szmagara A, Czeczko R & Fornal E (2017). LC-MS/MS determination of pesticide residues in fruits and vegetables, Journal of Environmental Science and Health, Part B, 52:7, 446-457, DOI: 10.1080/03601234.2017.1301755
36. Syrku R, Țurcanu G, Opopol N, Pynzaru I, Manceva T & Scurtu R (2019). Pesticides residue determination in vegetables and fruits commonly used in Republic of Moldova and estimation of human intake. In: Chemistry Journal of Moldova. 2(14), 62-71. DOI: 10.19261/cjm.2019.584
37. Yakar Y (2018). Determination of Pesticide Residues in Seedless Table Grapes. Yuzuncu Yil University Journal of Agricultural Sciences, 28 (4), 444-447, DOI: 10.29133/yyutbd.453960
38. WHO (2017). Inventory of Evaluations Performed by the Joint Meeting on Pesticide Residues (JMPR). Retrieved in September,15, 2017 from http://apps.who.int/pesticide-residues-jmpr-database/Home/ Range/All