Method Validation of QuEChERS -LC MS/MS Method for Some Pesticide Residues in Honey

sayi25-5.pdf ()

Method Validation of QuEChERS -LC MS/MS Method for Some Pesticide Residues in Honey

Objective:Honey, made by honey bee, is one of the oldest known food in human history. The problem of pesticide residue in honey not only threatens human health, but also causes economic losses by decreasing the export potential of honey and causing losses in bee colonies. Pesticide residues can be found in honey either directly arising from applications inside the hive or indirectly as a result of spraying the plants used by bees to make nectar and honey. In this study, it was aimed to analyze and validate some pesticides using LC MS/MS technique based on SANTE / 11813/2019 document.

Materials and Methods: Determination of 70 pesticide residue levels in honey samples using the AOAC 2007.01 version of the QuEChERS method was performed by the LC-MS / MS multiple residue method. Calibration curves for each target pesticide residue were constructed in the range of 2,5 to 100,0 μg/kg (r2 ≥ 0,995).

Results: LOQ values of all pesticides were determined as 10,0 μg/kg, below the MRL determined by the European Commission (EC). The average recoveries for the selected 70 pesticides were between 70-120% and the calculated standard deviations (RSD) were determined as 20%. Expanded measurement uncertainties were also calculated below 50%.

Conclusion: As a result, the validation studies for all pesticides studied have met the conditions specified in the document SANTE/11813/2019. The widespread use of pesticide residue analysis in honey is very important to ensure consumers’ access to safe food.

 

References

  • Ali, H., Khan, E. and Ilahi, I. 2019. Environmental Chemistry and Ecotoxicology of Hazardous Heavy Metals: Environmental Persistence, Toxicity, and Bioaccumulation. Journal of Chemistry, 1-14.
  • Anonymous, 2007. AOAC Official Method, Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with Magnesium Sulfate, 2007.01.
  • Anonim, 2012, Tük Gıda Kodeksi, Bal Tebliği (2012/58). Başbakanlık Basımevi, Ankara.
  • Anonymous, 2017 FAOSTAT. Tonnes Tonnes. FAO, 2019 CA4657EN/1/05.19 .http://www. fao.org/3/ca4657en/ca4657en.pdf (Erişim Tarihi: 28.01.2021)
  • Anonim, 2019. Avrupa Komisyonu Sağlık ve Gıda Güvenliği Genel Müdürlüğü, Gıda ve Yemde Pestisit Kalıntıları ve Analizleri İçin Analitik Kalite Kontrol ve Metot Validasyonu Prosedürleri Rehber Dokümanı (SANTE/ 11813/2019), 2019.
  • Anonim, 2021. Pestisit validasyon prosedürleri rehber dokumanı gıda ve yemde pestisit kalıntıları analizi için analitik kalite kontrol ve metot validasyonu prosedürleri. (Web page: https://www.tarimorman.gov.tr/GKGM/Belgeler/DB_Gida_Kont/Pestisit_El_Kitabi.pdf) (Erişim Tarihi: 28.01.2021).
  • Barganska, Z., Konieczka, P. and, Namiesnik, J., 2018. Comparision of two Methods for the Determination of Selected Pesticides in Honey and Honeybee Samples. Molecules, 23:2582.
  • Çobanoğlu, S. and Tüze, Ş. 2008. Determination of Amitraz (Varroaset) Residue in Honey by High Performance Liquid Chromatography (HPLC). Tarım Bilimleri Dergisi, 14, 169-174.
  • Erdoğrul, Ö. 2007. Levels of Selected Pesticides in Honey Samples from Kahramanmaraş, Turkey. Food Control, 18, 866–871.
  • Flores, C., Rsales, V., Ramirez, O., Loza, L. and Ugalde, J., 2017. Agricultural Pesticide Residues in Honey and Wax Combs from Southeastern, Central and Northeastern Mexico. Journal of Apicultural Research, 56:667-679.
  • Harizanis, P.C., Alissandrakis, E., Tarantilis, P.A. and Polissiou, M., 2008. Solid-Phase Microextraction/Gas-Chromatographic/Mass Spectrometric Analysis of p –dichlorobenzene and Naphthalene in Honey. Food Additives and Contaminants 25:1272-1277.
  • Koç F., Yigit, Y., Das, Y.K., Gürel, Y. and Yaralı, C., 2008. Determination of Aldicarb, Propoxur, Carbofuran, Carbaryl and Methiocarb Residues in Honey by HPLC with Post-column Derivatization and Fluorescence Detection after Elution from a Florisil Column. Journal of Food and Drug Analysis, 16, 39-45.
  • Kolankaya, D., Sorkun, K., Özkrım, A. ve Erkmen, B. 2002. Adapazarı-Karasu’da Fındık Zararlısına Karşı Kullanılan İnsektisitlerin Bal Arılarına Etkisi. Mellifera 2, 30-31.
  • Kumova, U., 2001. Varroa jacobsoni Kontrolünde Ülkemizde Kullanılan Bazı İlaçların Etkinliğinin Araştırılması. Turkish Journal of Veterinary and Animal Sciences, 25, 597–602.
  • Lehotay, S. J., Maśtovská, K. and 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 Inter. 88(2):615-629.
  • Lopez, M.I., Pettis, J.S., Smith, I.B. and Chu, P.S., 2008. Multiclass Determination and Confirmation of Antibiotic Residues in Honey using LC-MS/MS. J. Agric. Food Chem. 56:1553-1559.
  • Moosbeckhofer, R., Wallner, K., Pechhacker, H., Luh, M. and Womastek, R., 1995. Residue Level in Honey, Wax and Propolis After Ten Years of Varroa Treatment in Austria. The XXXIVth International Apicultural Congress. 15-19 August 1995. Lausanne, Switzerland.
  • Muku, C., Güçlü, G. ve Selli S., 2019. Doğu Akdeniz Bölgesi Ballarının Pestisit ve Naftalin Kalıntılarının LC/MS/MS ve HS-SPME GC/MS Teknikleriyle Belirlenmesi. Çukurova Tarım ve Gıda Bilimleri Dergisi, 142-148.
  • Oliviera, R., Queiroz, S., Luz, C., Prto, R. and Rath, S., 2016. Bee Polen as a Bioindicator of Environmental Pesticide Contamination. Chemosphere, 163:525-53.
  • Pinho, P.P, Neves, A.A., de Queiroz, R.M.E.L. and Silvério, F.O. 2010. Optimization of the Liquid–Liquid Extraction Method and Low Temperature Purification (LLE–LTP) for Pesticide Residue Analysis in Honey Samples by Gas Chromatography. Food Control, 21, 1307–1311.
  • Polat, B. and 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.
  • Polat, B. and Tiryaki, O., 2020. Assessing Washing Methods for Reduction of Pesticide Residues in Capia Pepper with LC-MS/MS. Journal of Environmental Science and Health, Part B, 55(1), 1-10.
  • Rissato, S.R., Galhianea, M.S, Knollb, F.R.N. and Aponc, B.M., 2004. Supercritical Fluid Extraction for Pesticide Multiresidue Analysis in Honey: Determination by Gas Chromatography with Electron-Capture and mass Spectrometry Detection. Journal of Chromatography A, 1048, 153–159.
  • Shendy, A., Ghobashy, M., Mhammed, M., Alla, S. and Ltfy, H., 2016. Simultaneous Determination of 200 Pesticide Residues in Honey using Gas Chromatgraphy Tandem Mass Spectrometry in Conjuction with Stream Lined Quantification Approach. Journal of Chromatography A, 1427:143-160.
  • Sorkun, K., Yılmaz, B., Özkırım, A., Özkök, A., Gençay, Ö. ve Bölükbaşı, D.N., 2008 Yaşam için Arılar. Türkiye Arı Yetiştiricileri Merkez Birliği, Ankara, p. 135 Tiryaki, O. and Temur, C., 2010. The fate of pesticide in the environment. J. Biol. Environ. Sci, 4(10), 29-38.
  • Toptancı, İ. ve Bayrak, A., 2012. Turunçgil Ballarında Pestisit Kalıntı Düzeylerinin Belirlenmesi Akademik Gıda, 10 (3), 22-25. https://dergipark.org.tr/tr/pub/akademik-gida/issue/55821/764684. (Erişim Tarihi: 28.01.2021)