Investigation of insecticide residues in potato grown in Türkiye by LC-MS/MS and GC-MS and health risk assessment

Year 2022, Volume: 46 Issue: 4, 481 - 500, 07.01.2023

Tarık Balkan Özlem Yılmaz

https://doi.org/10.16970/entoted.1201475

Cited By: 3

Abstract

Insecticide, acaricide, nematicide and metabolite residues were assayed in 104 potato samples collected from local markets in Tokat, Türkiye in 2022 and the potential health risk for consumers assessed. Analytical method verification was performed for 135 pesticide active substances in potato matrices by liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry. Matrix-matched calibration curves were constructed and good linearity was obtained with a coefficient of determination between 0.990 and 0.999. Average recoveries varied from 73.2 to 119.6%. Repeatability and intra-laboratory reproducibility conditions of the method expressed as %RSD were less than 20%. These figures were within the SANTE/11312/2021 recovery limits (70-120%) and the values specified for the repeatability (RSD ≤ 20%). The limits of quantification were lower than the maximum residue limits set by the European Union for the potato. No pesticide residues were found at detectable limits in 93 samples. Two samples contained residues below the maximum residue limit (MRL), while nine samples contained residues above the MRLs. Clothianidin and thiamethoxam residues detected in one sample, while acetamiprid were detected in nine samples. The health risk assessment study indicated that potato consumption was safe for consumers.

Keywords

Acute risk, chronic risk, matrix effect, method verification, pesticide residue

LC-MS/MS ve GC-MS ile Türkiye menşeli patateslerde insektisit kalıntılarının araştırılması ve sağlık risk değerlendirmesi

Abstract

Bu çalışmada, 2022 yılında Tokat'ta yerel pazarlarda satılan patateslerde insektisit, akarisit, nematisit ve metabolit kalıntıları taranmış ve bu kalıntıların tüketiciler açısından potansiyel sağlık riskleri değerlendirilmiştir. Sıvı kromatografi-tandem kütle spektrometrisi ve gaz kromatografi-kütle spektrometrisi ile 135 pestisit etken madde kalıntısını belirlemek için metot doğrulaması yapılmıştır. Matris uyumlu kalibrasyon eğrileri oluşturulmuş ve 0.990 ile 0.999 arasında değişen korelasyon katsayısı ile uygun bir doğrusallık elde edilmiştir. Ortalama geri kazanımlar %73.2 ile %119.6 arasında, %RSD olarak ifade edilen yöntemin tekrarlanabilirlik koşulları ve laboratuvar içi tekrar üretilebilirlik koşulları %20'den daha düşük bulunmuştur. Bu rakamlar, SANTE/11312/2021 dokümanındaki geri kazanım limitleri (%70-120) ve tekrarlanabilirlik için belirtilen değerlere (RSD ≤ %20) uygundur. Miktar tayin limitleri, Avrupa Birliği tarafından patates için belirlenen maksimum kalıntı limitlerinden daha düşük seviyelerde bulunmuştur. 93 örnekte tespit edilebilir limitlerde pestisit kalıntısına rastlanmamıştır. İki numunede MRL değerleri altında, 9 numunede ise MRL değerleri üzerinde pestisit kalıntısı tespit edilmiştir. Bu örneklerden birinde hem clothianidin hem de thiamethoxam, dokuzunda ise acetamiprid tespit edilmiştir. Sağlık risk değerlendirmesi ise patates tüketiminin tüketiciler için güvenli olduğunu göstermiştir.

Keywords

Akut risk, kronik risk, matriks etkisi, metot doğrulaması, pestisit kalıntısı

References

• Akoto, O., S. Gavor, M. K. Appah & J. Apau, 2015. Estimation of human health risk associated with the consumption of pesticide-contaminated vegetables from Kumasi Ghana. Environmental Monitoring and Assessment, 187 (5): 1-9.
• Anonymous, 2022. Türk gıda kodeksi pestisitlerin maksimum kalıntı limitleri yönetmeliği. (Web page: https://www.resmigazete.gov.tr/eskiler/2021/09/20210927M1-1.htm) (Date accessed: November 2022) (in Turkish).
• AOAC, 2007. AOAC Official Method: Pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate gas chromatography/mass spectrometry and liquid chromatography/tandem mass spectrometry. First Action 2007. (Web page: https://nucleus.iaea.org/fcris/methods/AOAC_2007_01.pdf) (Date accessed: November 2022).
• Bakırcı, G. T., D. B. Y. Acay, F. Bakırcı & S. Ötleş, 2014. Pesticide residues in fruits and vegetables from the Aegean region, Turkey. Food Chemistry, 160: 379-392.
• Balkan, T., 2021. Determination of chlorsulfuron and pendimethalin residues in soil using modified quechers method by liquid chromatography-tandem mass spectrometry. European Journal of Science & Technology, 31 (Supp. 1): 539-544.
• Balkan, T. & K. Kara, 2022. Determination of pesticide residues and risk assessment in some vegetables grown in Tokat province. Plant Protection Bulletin, 62 (2): 26-35.
• Balkan T. & Ö. Yılmaz, 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.
• Çatak, H. & O. Tiryaki, 2020. Insecticide residue analyses in cucumbers sampled from Çanakkale open markets. Turkish Journal of Entomology, 44 (4): 449-460.
• Česnik, H. B., A. Gregorčič, Š. B. Bolta & V. Kmecl, 2006. Monitoring of pesticide residues in apples, lettuce and potato of the Slovene origin, 2001-04. Food Additives and Contaminants, 23 (2): 164-173.
• Česnik, H. B., S. Velikonja-Bolta & A. Gregorčič, 2010. Pesticide residues in cauliflower, eggplant, endive, lettuce, pepper, potato and wheat of the Slovene origin found in 2009. Acta Chimica Slovenica, 57 (4): 972-979.
• Danek, M., X. Fang, J. Tang, J. Plonka & H. Barchanska, 2021. Simultaneous determination of pesticides and their degradation products in potatoes by MSPD-LC-MS/MS. Journal of Food Composition & Analysis, 104: 104129.
• EC, 2002. European Commission: 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, L 187 (45): 30-43.
• EC, 2005. European Commission: Regulation (EC) No 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC. Official Journal of the European Union, L 70 (48): 1-16.
• EFSA, 2015. European Food Safety Authority: Revisiting the International Estimate of Short-Term Intake (IESTI equations) used to estimate the acute exposure to pesticide residues via food. EFSA Supporting Publication, 12 (12): 1-81.
• EURACHEM, 2014. Eurachem Guide: The Fitness for Purpose of Analytical Methods – A Laboratory Guide to Method Validation and Related Topics, (2nd ed. 2014). ISBN 978-91-87461-59-0. (Web page: https://www.eurachem.org/ images/stories/Guides/pdf/MV_guide_2nd_ed_EN.pdf) (Date accessed: December 2022).
• EU-MRL, 2022. European Union (EU-MRL) Pesticides Database: Pesticide Residues MRLs. Directorate General for Health & Consumers. (Web page: https://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/mrls/?event= search.pr.) (Date accessed: November 2022).
• FAO, 2008. International year of the potato, new light on a hidden treasure. (Web page: https://www.fao.org/3/i0500e/ i0500e01.pdf) (Date accessed: November 2022).
• FAO, 2022. Crops and livestock products, crops primary, potatoes. (Web page: https://www.fao.org/faostat/en/#data/QCL) (Date accessed: October 2022).
• IUPAC, 2022. The PPDB-Pesticide properties database, international union of pure and applied chemistry. (Web page: http://sitem.herts.ac.uk/aeru/iupac/index.htm) (Date accessed: November 2022).
• Lee, J., L. Kim, Y. Shin, J. Lee, J. Lee, E. Kim, J.-K. Moon & J.-H. Kim, 2017. Rapid and simultaneous analysis of 360 pesticides in brown rice, spinach, orange, and potato using microbore GC-MS/MS. Journal of Agricultural and Food Chemistry, 65: 3387-3395.
• Liu, Y., D. Shen, S. Li, Z. Ni, M. Ding, C. Ye, & F. Tang, 2016. Residue levels and risk assessment of pesticides in nuts of China. Chemosphere, 144: 645-651.
• Narenderan, S. T. & S. N. Meyyanathan, 2019. Sample treatment and determination of pesticide residues in potato matrices: a review. Potato Research, 62 (1): 47-67.
• Polat, B. & O. Tiryaki, 2022. Determination of insecticide residues in soils from Troia agricultural fields by the QuEChERS method. Turkish Journal of Entomology, 46 (3): 251-261.
• Poulsen, M. E., J. H. Andersen, A. Petersen & B. H. Jensen, 2017. Results from the Danish monitoring programme for pesticide residues from the period 2004-2011. Food Control, 74: 25-33.
• PPPDA, 2022. Plant Protection Product Database Application. (Web page: https://bku.tarim.gov.tr) (Date accessed: December 2022) (in Turkish).
• Reis, D., P. Silva, R. Perestrelo & J. S. Câmara, 2020. Residue Analysis of Insecticides in Potatoes by QuEChERS-dSPE/UHPLC-PDA. Foods, 9 (8): 1000 (1-17).
• Saha, A., T. P. A. Shabeer, K. Banerjee, S. Hingmire, D. Bhaduri, N. K. Jain & S. Utture, 2015. Simultaneous analysis of herbicides pendimethalin, oxyfluorfen, imazethapyr and quizalofop-p-ethyl by LC-MS/MS and safety evaluation of their harvest time residues in peanut (Arachis hypogaea L.). Journal of Food Science and Technology, 52 (7): 4001-4014.
• SANTE, 2021. SANTE/11312/2021, Analytical quality control and method validation procedures for pesticide residues analysis in food and feed, 1-55. (Web page: https://food.ec.europa.eu/system/files/2022-02/pesticides_mrl_ guidelines_wrkdoc_ 202 1- 11312.pdf) (Date accessed: September 2022).
• Sivaperumal, P., R. Thasale, D. Kumar, T. G. Mehta & R. Limbachiya, 2022. Human health risk assessment of pesticide residues in vegetable and fruit samples in Gujarat State, India. Heliyon, 8 (10): e10876.
• Soydan, K. D., N. Turgut, M. Yalçın, C. Turgut & P. B. K. Karakuş, 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 (22): 27511-27519.
• Srivastava, A. K., P. Trivedi, M. K. Srivastava, M. Lohani & P. L. Srivastava, 2011. Monitoring of pesticide residues in market basket samples of vegetable from Lucknow City, India: QuEChERS method. Environmental Monitoring and Assessment, 176 (1-4): 465-472.
• Sun, H., F. Luo, X. Zhang, L. Zhou, Z. Lou & Z. Chen, 2021. Residue analysis and dietary exposure risk assessment of acibenzolar-S-methyl and its metabolite acibenzolar acid in potato, garlic, cabbage, grape and tomato. Ecotoxicology and Environmental Safety, 207: 111178.
• Szarka, A., N. Kurucová & S. Hrouzková, 2022. Evaluation of the matrix effects in herbal-based potions in pesticide residues analysis by dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry. Analytical and Bioanalytical Chemistry Research, 9 (3): 269-280.
• Szpyrka, E., A. Kurdziel, A. Matyaszek, M. Podbielska, J. Rupar & M. Słowik-Borowiec, 2015. Evaluation of pesticide residues in fruits and vegetables from the region of south-eastern Poland. Food Control, 48 (2015): 137-142.
• TAGEM, 2017. Patates Entegre Mücadele Teknik Talimatı. (Web page: https://www.tarimorman.gov.tr/TAGEM/Belgeler/ yayin/Patates%20Entegre-11.10.2017.pdf) (Date accessed: November 2022).
• TGK-MRL, 2022. Republic of Turkey, ministry of food, agriculture and livestock, general directorate of food and control, department of plant protection products, MRL rates. (Web page: https://bku.tarimorman.gov.tr/MRLOrani/ Index?csrt=2789820862056200932) (Date accessed: November 2022).
• Thompson, T. S., R. Dimock, R. W. Bradbury, R. Rieve & M. Fehr, 2011. Pesticides in fresh potatoes sold in farmers’ markets in Alberta, Canada. Bulletin of Environmental Contamination & Toxicology, 87 (5): 580.
• TUIK, 2019. Turkey Health Interview Survey. (Web page: https://data.tuik.gov.tr/Bulten/DownloadIstatistikselTablo?p= WEBW229PP/91tMV2m71fU6pRWq2F1ZD/lzOFFk0bNDi2rjAC8QDCRN62nr2M3n1K) (Date accessed: November 2022).
• TUIK, 2022. Turkish Statistical Institute. Poultry production statistics. (Web page: https://biruni.tuik.gov.tr/medas/ ?kn=80&locale=en) (Date accessed: November 2022).
• Wang, S., Z. Hou, S. Liang & S. Lu, 2020. Residue behavior and risk assessment of rimsulfuron and quizalofop-p-ethyl in potato under field conditions. Bulletin of Environmental Contamination and Toxicology, 105 (4): 602-606.
• Weber, D. C., 2013. "Biological Control of Potato Insect Pests, 399-437". In: Insect Pests of Potato (Eds. A. Alyokhin, V. Vincent & P. Giordanengo) Academic Press, Oxford, UK. 598 pp.
• Yang, L., Q. Zheng, S. Lin, Y. Wang, Q. Zhu, D. Cheng, J. Chen & Z. Zhang, 2020. Dissipation and residue of dimethomorph in potato plants produced and dietary intake risk assessment. International Journal of Environmental Analytical Chemistry, 102 (6): 1332-1344.