Investigation of Neonicotinoids Insecticides with LC-MS/MS in Honey Produced in Giresun

Yıl 2023, Cilt: 8 Sayı: 3, 326 - 332, 30.09.2023

Seda Dicle Korkmaz , Özlem Küplülü

https://doi.org/10.35229/jaes.1323223

Öz

Neonicotinoids are a significant threat to the environment and the food chain given their wide commercial distribution, mode of action, systemic properties, persistence, toxicity profiles of insecticides and metabolites, and their effects on living organisms.These substances, developed as an alternative to organophosphate and carbamate insecticides, pass to all parts of plants, including pollen and nectar, and can be transferred to products produced from these plants, especially bee products. With these systemic effects, neonicotinoids lead to negative effects on living things such as honey bees and wild bees, as well as other vertebrates. Currently, studies on neonicotinoid derivatives and their effects are increasing rapidly, and according to the results of the study, bans and restrictions are imposed on their use in different countries.The aim of the study was to determine the presence and amount of neonicotinoids in honey produced in Giresun province and to measure the level of pollution in the environment and possible public health risks it is revealed. Giresun province, known as the capital of hazelnuts in Turkey, where beekeeping is widespread and many agricultural activities are carried out, has the characteristics and importance to reveal the purpose of the study. For this purpose, 50 honey samples taken during the new harvest period from growers engaged in stationary beekeeping in areas close to Giresun's nut-growing regions were used as materials. Neonicotinoid in samples the presence of (acetamiprid, clothianidin, thiacloprid, imidacloprid,nitenpyram, thiamethoxam and dinotephran) was detected by LC-MS/MS. According to the analysis results; imidacloprid was detected in 9 of 50 honey samples, thiomethoxam in 2, and both imidacloprid and thiomethoxam in 1 were above 10 ppb, which is the limit value, and neonicotinoids were determined in a total of 12 samples. As a result, the presence of possible neonicotinoids in honey, which is recommended for therapeutic consumption, a sine qua non of healthy diets with high nutritional value, is a potential danger to public health. Neonicotinoid contamination in honey and other bee products, which are often consumed, especially by children and decrepit people, is extremely important in terms of the health risks it may pose. Within the framework of good agricultural practice, the selection of beekeeping areas and the introduction of restrictions on the use of neonicotinoids in this direction in parallel with the EU are important for preventing possible risks.

Anahtar Kelimeler

Contaminant, honey, public health, LC-MS/MS, neonicotinoid

Proje Numarası

SAĞ-BAP-A-250221-57

Giresun’da Üretilen Ballarda Neonikotinoid Kalıntı Varlığının LC-MS/MS ile Araştırılması

Öz

Neonikotinoidler; geniş ticari yayılımları, etki biçimleri, sistemik özellikleri, kalıcılıkları ile insektisit ve metabolitlerinin toksisite profilleri, canlı organizmalar üzerindeki etkileri göz önüne alındığında çevreye ve besin zincirine önemli bir tehdittir. Organofosfatlı ve karbamatlı insektisitlere alternatif olarak geliştirilen bu maddeler, polen ve nektar dâhil bitkilerin tüm kısımlarına geçmekte, başta arı ürünleri olmak üzere bu bitkilerden üretilen ürünlere aktarılabilmektedir. Neonikotinoidler, sistemik etkileriyle bal arıları ve yabani arılar gibi canlıların yanı sıra, diğer omurgalılar üzerinde de olumsuz etkilere yol açmaktadır. Günümüzde neonikotinoid türevleri ve oluşturdukları etkilere ilişkin çalışmalar hızla artmakta, çalışma sonuçlarına göre farklı ülkelerde kullanımlarına yasak ve kısıtlamalar getirilmektedir. Çalışmanın amacı, Giresun ilinde üretilen ballarda neonikotinoid varlığı ve miktarının tespit edilerek çevredeki kirlilik seviyesinin ölçülmesi ile olası halk sağlığı risklerinin ortaya konulmasıdır. Türkiye'de fındığın başkenti olarak bilinen, arıcılığın yaygın olduğu ve bir çok tarımsal faaliyetin yapıldığı Giresun ili, çalışmanın amacını ortaya koyacak özellikte ve önemdedir. Bu amaçla Giresun'un özellikle fındık tarımı yapılan bölgelerine yakın alanlarda sabit arıcılık yapan yetiştiricilerden yeni hasat döneminde alınan 50 adet bal örneği materyal olarak kullanıldı. Örneklerde neonikotinoid (acetamiprid, clothianidin, thiacloprid, imidacloprid, nitenpyram, thiamethoxam ve dinotefran) varlığı, Sıvı kromatografi-kütle spektrometresi/kütle spektrometresi (LC-MS/MS) ile tespit edildi. Analiz sonuçlarına göre; 50 bal örneğinin 9’unda imidacloprid, 2’sinde thiomethoxam, 1’inde ise hem imidacloprid hem thiomethoxam 10 ppb’nin üzerinde saptanmış olup toplam 12 örnekte neonikotinoid belirlenmiştir.
Sonuç olarak; besleyici değeri yüksek, sağlıklı diyetlerin olmazsa olmazı, tedavi amaçlı tüketimi önerilen ballardaki olası neonikotinoid varlığı halk sağlığı açısından potansiyel bir tehlikedir. Özellikle çocuklar ve yaşlılar tarafından sıklıkla tüketilen bal ve diğer arı ürünlerindeki neonikotinoid kontaminasyonu, oluşturabileceği sağlık riskleri açısından son derece önemlidir. İyi tarım uygulaması çerçevesinde arıcılık yapılan alanların seçimi ve AB’ye paralel olarak bu yönde neonikotinoid kullanımına sınır getirilmesi oluşabilecek risklerin önlenmesi açısından önem taşımaktadır. Ayrıca bölgedeki arı yetiştiricilerinin konu ile ilgili bilgilendirme ve bilinçlendirilmesi açısından da önemlidir.

Anahtar Kelimeler

Bal, halk Sağlığı, kontaminant, L-MS/MS, neonikotinoid

Destekleyen Kurum

Giresun Üniversitesi BAP Koordinasyon Birimi

Proje Numarası

SAĞ-BAP-A-250221-57

Teşekkür

Bu çalışmada desteklerini esirgemeyen tüm yazarlara ve Giresun Üniversitesi BAP Koordinasyon Birimine teşekkür ederim.

Kaynakça

• Anastassiades, M., Lehotay, S.J., Stangbaher, D. & Schenck, F.J. (2003). Quick,easy,cheap, effective (QueChERS) method for determining pesticide residue. Journal of AOAC International, 86(2), 412-431. DOI: 10.1093/jaoac/86.2.412
• Bonmatin, J.M., Giorio, C., Girolami, V., Goulson, D., Bonmatin L., Kreutzweiser, D. P., Krupke, C., Liess, M., Long, E., Marzaro M., Mitchell E.A.D., Noome, D.A., Simon-Delso, N. & Tapparo, A. (2015). Environmental fate and exposure; neonicotinoids and fipronil. Environmental Science and Pollution Research, 22(1), 35-67. DOI: 10.1007/s11356-014-3332-7
• Chen, M., Tao, L., Mclean, J. & Lu, C. (2014). Quantitative Analysis of Neonicotinoid Insecticide Residues in Foods: Implication for Dietary Exposures. Journal of Agricural Food Chemical, 62, 6082-6090. DOI: 10.1021/jf501397m
• Cicero, N., Naccari, C., Cammilleri, G., Giangrosso, G., Cicero, A., Gervasi, T. & Ferrantelli, V. (2017). Monitoring of neonicotinoid pesticides in beekeeping. Natural product research, 31(11), 1258-1262. DOI: 10.1080/14786419.2016.1236101
• Cimino, A.M., Boyles, A.L., Thayer, K.A. & Perry, M.J. (2017). Effects of Neonicotinoid Pesticide Exposure on Human Health: Systematic Review. Environmental Health Perspective, 125(2): 155- 162. DOI: 10.1289/EHP515
• Çil, G.İ., Korkmaz, S.D., Ozansoy, G. & Küplülü, Ö. (2020). Türkiye ’deki bal örneklerinde neonikotinoid varlığının LC-MS/Q-TOF Yöntemi ile tespiti. MAKU J. Health Sci. Ins., 8(1):11-17. DOI: 10.24998/maeusabed.695570
• Decourtye, A. & James, D. (2010). Insect nicotinic acetylcholine receptors. In: Thany, S. H. (eds) Ecotoxicity of neonicotinoid insecticides to bees. 85-95p, Springer, New York.
• Démares, F.J., Pirk, C.W., Nicolson, S.W. & Human, H. (2018). Neonicotinoids decrease sucrose responsiveness of honeybees at first contact. Journal of Insect Physiology, 108, 25-30. DOI: 10.1016/jinsphys.2018.05.004
• Eurochem Guide. (2014). The Fitness for Purpose of Analytical Methods–A Laboratory Guide to Method Validation and Related Topics. B. Magnusson and U. Ornemark (eds.) (2nd ed.) ISBN978-91-87461-590 https://www.eurachem.org/images/stories/Guides /pdf/MV_guide_2nd_ed_EN.pdf (5.6.2021)
• European Commission. (2002/657/EC). Commission Decision of 12 August 2002 implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results (Text with EEA relevance) (notified under document number C (2002) 3044) https://op.europa.eu/en/publication- detail/-/publication/ed928116-a955-4a84-b10a- cf7a82bad858/language-en (22.6.2021)
• European Commission. (2014). Safety of the food chain Chemicals, contaminants, pesticides. Guidance document on analytical quality control and validation procedures for pesticide residues analysis in food and feed.SANCO/12571/2013. https://www.eurlpesticides.eu/library/docs/allcrl/ AqcGuidance_Sanco_2013_12571.pdf (8.6.2022) European Commission. (2020). Neonicotinoids. https://ec.europa.eu/food/plant/pesticides/approv al_active_substances/approval_renewal/neonicoti noids_en (27.02.2020).
• Gbylik-Sikorska, M., Sniegocki, T. & Posyniak, A. (2015). Determination of neonicotinoid insecticides and their metabolites in honey bee and honey by liquid chromatography tandem massspectrometry. Journal of Chromatography B, 990, 132-140. DOI: 10.1016/j.jchromb.2015.03016
• Gibbons, D., Morrissey C. & Mineau, P. (2015). A review of the direct and indirect effects of neonicotinoids and fibronil on vertebrate wildlife. Enviromental Science Pollution Research International, 22(1): 103-108. DOI: 10.1007/s11356-014-3180-5
• Jovanov, P., Guzsvány, V., Lazić, S., Franko, M., Sakač, M., Šarić, L. & Kos, J. (2015). Development of HPLC-DAD method for determination of neonicotinoids in honey. Journal of Food Composition and Analysis, 40, 106-113. DOI: 10.1016/j.jfca.2014.12.021
• Kartal, M.N. (2019). Neonicotinoid pesticide applications outcomes; contaminate honey and honey bees. Turkish Journal of Public Health, 17(1):88-91. DOI: 10.20518/tjph.405719
• Koc, F., Yigit, Y., Das, Y.K., Gurel, Y., & Yarali, C. (2008). Determination of Aldicarb Propoxur Carbofuran Carbaryl and Methiocarb Residues in Honey by HPLC with Post-column Derivatization and Fluorescence. Journal of Food and Drug Analysis, 16(3), 39-45. DOI: 10.38212/2224- 6614.2356
• Lehotay, S.J., Mastovska, K. & Lightfield A.R. (2005). Use of Buffering and other means to improve results of problematic pesticides in a fast and easy method for residue analysis of fruits and vegetables. Journal of AOAC International, 88 (2), 615-629.
• Lu, C.A., Chang, C.H., Tao, L. & Chen, M. (2016). Distributions of neonicotinoid insecticides in the Common wealth of Massachusetts: a temporal and spatial variation analysis for polen and honey samples. Environmental Chemistry, 13(1), 4-1. DOI: 10.1071/EN15064
• Main, A.R., Headley, J.V., Peru, K.M., Michel, N.L., Cessna, A.J. & Morrissey, C.A. (2014). Wide spread use and frequent detection of neonicotinoid insecticides in wetlands of Canada's Prairie Pothole Region. PloSone, 9(3).
• Mitchell, E.A., Mulhauser, B., Mulot, M., Mutabazi, A., Glauser, G. & Aebi, A. (2017). A world wide survey of neonicotinoids in honey. Science, 358(6359), 109-111.
• PMRA. (2015). Pesticide Incident Reporting Database. Health Canada Pest Management Regulatory Agency. http://pr‐rp.hc‐sc.gc.ca/pi‐ip/disclaimer‐ avertissement‐eng.php (Erişim 27.02.2020)
• Proietto Galeano, M., Scordino, M., Sabatino, L., Pantò, V., Morabito, G., Chiappara, E. & Gagliano, G. (2013). UHPLC/MS-MS analysis of six neonicotinoids in honey by modified QuEChERS: method development, validation, and uncertainty measurement. International Journal of Food Science, 2013. DOI: 10.1155/2013/863904
• Sánchez-Hernández, L., Hernández-Domínguez, D., Bernal, J., Neusüß, C., Martín, M.T. & Bernal, J.L. (2014). Capillary electrophoresis-mass spectrometry as a new approach analyze neonicotinoid insecticides. Journal of Chromatography A, 1359, 317-324. DOI: 10.1016/j.chroma.2014.07.028
• Sánchez-Hernández, L., Hernández-Domínguez, D., Martín, M.T., Nozal, M.J., Higes, M. & Yagüe, J.L.B. (2016). Residues of neonicotinoids and their metabolites in honey and polen from sunflower and maize seed dressing crops. Journal of Chromatography A, 1428, 220-227. DOI: 10.1016/j.chroma.2015.10.066
• Simon-Delso, N., Amaral-Rogers, V., Belzunces, L.P., Bonmatin, J.M., Chagnon, M., Downs,C. & Goulson, D. (2015). Systemic insecticides (neonicotinoids and fibronil): trends, uses, mode of action and metabolites. Environmental Science and Pollution Research, 22(1), 5-24. DOI: 10.1007/s11356-014-3470-y
• Tanner, G. & Czerwenka, C. (2011). LC-MS/MS analysis of neonicotinoid insecticides in honey: methodology and residue findings in Austrian honeys. Journal of Agricultural and Food Chemistry, 59(23), 12271-12277. DOI: 10.1021/jf202775m
• Tarım ve Orman Bakanlığı Gıda ve Kontrol Genel Müdürlüğü. (TOB). (2022). Imidacloprid, Thiomethoxam ve Thiram Aktif Maddeli Bitki Koruma Ürünleri Hk. (6950658 sayı). https://bku.tarimorman.gov.tr/Duyuru/DuyuruDe tay/85?csrt=3598786223508364038 (13.2.2023)
• Tomizawa, M. & Casida, J.E. (2005). Neonicotinoid insecticide toxicology: mechanisms of selective action. Annual Reviews in Pharmacology and Toxicology, 45, 247-268.
• Zhang, Q., Li, Z., Chang, C.H., Lou, J.L., Zhao, M.R. & Lu, C. (2018). Potential human exposures to neonicotinoid insecticides: a review. Environmental Pollution, 236, 71-81. DOI: 10.1016/j.envpol.2017.12.101
• Zhang, Q., Lu, Z., Chang, C., Yu, C. & Wang, X. (2019). Dietary risk of neonicotinoid insecticides through fruit and vegetable consumption in school-age children. Environment International, 126, 672- 681. DOI: 10.1016/j.envint.2019.02.051