Development of QuEChERS method Combined with dispersive liquid-liquid microextraction for determination of some pesticides in cucumber samples using High-performance liquid chromatography

Subject Areas : Food Hygiene

Fatemeh Nasiri ¹ , Azar Haghighat ² , Mohammad Reza Afshar Mogaddam ³ , Jalil Khandaghi ⁴

1 - M.Sc Graduate of Food Science and Technology, Sarab Branch, Islamic Azad University, Sarab, Iran
2 - Department of Food Science and Technology, Sarab Branch, Islamic Azad University, Sarab, Iran
3 - Food and Drug Safety Research Center, Tabriz University of Medical Sciences, Tabriz, Iran and Pharmaceutical Analysis Research Center, Tabriz University of Medical Sciences, Tabriz, Iran
4 - Department of Food Science and Technology, Sarab Branch, Islamic Azad University, Sarab, Iran and Department of food Biotechnology, Biotechnology Research Center, Tabriz Branch, Islamic Azad University, Tabriz, Iran

Received: 2023-06-11 Accepted : 2023-08-06 Published : 2023-06-22

Keywords: cucumber, insecticide, High-performance liquid chromatography, microextraction, QuEChERS,

Abstract :

Due to the widespread use of pesticides to protect agricultural products around the world and the accumulation of residues of these substances in plant tissue, most of the products that have been exposed to pesticides contain amounts of pesticide residues. The most popular and sensitive method for determining low amounts of pesticide residues in order to find out their maximum residue levels (MRLs) in food products is the chromatographic assay. In the present study, the diazinon, chlorpyrifos, imidacloprid, acetamiprid, thiacloprid and fenvalerate insecticides were extracted from cucumber samples by using QuEChERS method in combination with liquid-liquid microextraction and were determined by HPLC-DAD. For this purpose, the effective factors in the developed extraction method were optimized and the mentioned method was validated. Based on the results, the target analytes were successfully extracted simultaneously using 2 ml of a mixture of acetonitrile, methanol, and acetone (in the QuEChERS step). Further, the highest efficiency in the second extraction step was obtained using 65 µl of hexanol and 15% NaCl. The LOD between 0.36 and 0.57 ng/g, high repeatability in the range of 3.6 to 6.8 (based on the RSD%), and extraction recovery of analytes in the range of 76 to 84% of the developed method's merit figures indicate the method's high capability in extracting particular pesticides. Overall, the procedure described in this study is a simple and cheap method and has a good ability to extract the desired pesticides from cucumber samples.

References:

• Abdel-Ghany, M.F., Hussein, L.A., El Azab, N.F., El-Khatib, A.H., and Linscheid, M.W. (2016). Simultaneous determination of eight neonicotinoid insecticide residues and two primary metabolites in cucumbers and soil by liquid chromatography–tandem mass spectrometry coupled with QuEChERS. Journal of Chromatography B, 1031: 15-28.


• Afshar Mogaddam, M., Khandaghi, J., and Vajdi HokmAbad, S. (2023). Use of Temperature-controlled Ionic Liquid-assisted Dispersive Liquid-Liquid Microextraction Method for the Detection of Amoxicillin, Cloxacillin and Erythromycin Residues in Cow Milk using High Performance Liquid Chromatography. Iranian Journal of Nutrition Sciences & Food Technology, 18(1): 119-126. [In Persian]


• Afshar Mogaddam, M.R., Khandaghi, J., Farajzadeh, M.A., and Najafzadeh, D. (2020). Development of in-situ synthesis of lighter than water deep eutectic solvents under ultrasonic energy in a narrow tube and application in liquid–phase microextraction. International Journal of Environmental Analytical Chemistry, 1-14.


• Baig, S.A., Akhtera, N.A., Ashfaq, M., and Asi, M.R. (2009). Determination of the organophosphorus pesticide in vegetables by high-performance liquid chromatography. American-Eurasian Journal of Agriculture and Environmental Science, 6(5): 513-519.


• Cheng, H. (1990). Pesticides in the soil environment—an overview. Pesticides in the Soil Environment: Processes, Impacts and Modeling, 2: 1-5.


• Darvishnejad, F., Raoof, J.B., and Ghani, M. (2020). MIL-101 (Cr)@ graphene oxide-reinforced hollow fiber solid-phase microextraction coupled with high-performance liquid chromatography to determine diazinon and chlorpyrifos in tomato, cucumber and agricultural water. Analytica Chimica Acta, 1140: 99-110.


• Dashtbozorgi, Z., Ramezani, M.K., and Waqif-Husain, S. (2013). Optimization and validation of a new pesticide residue method for cucumber and tomato using acetonitrile-based extraction-dispersive liquid–liquid microextraction followed by liquid chromatography-tandem mass spectrometry. analytical methods, 5(5): 1192-1198.


• EU Pesticides database. (2005). Pesticide EU-MRLs. Regulation EC No. 396, Available at: http://ec.europa.eu/sanco-pesticides.


• Fakhim Rasoolzadeh, R., Afshar Moghaddam, M., and Khandaghi, (2020). Application of a novel microextraction method for determination of organophosphorous pesticides from fruit juice using high performance liquid chromatography. Food Hygiene, 38 (2): 31-43. [In Persian]


• Farajzadeh, M.A., Afshar Mogaddam, M. R., and Alizadeh Nabil, A.A. (2015). Polyol‐enhanced dispersive liquid–liquid microextraction coupled with gas chromatography and nitrogen phosphorous detection for the determination of organophosphorus pesticides from aqueous samples, fruit juices, and vegetables. Journal of Separation Science, 38(23): 4086-4094.


• Ghasemi, R., Mirzaei, H., Afshar Mogaddam, M.R., Khandaghi, J., and Javadi, A. (2022). Application of magnetic ionic liquid-based air–assisted liquid–liquid microextraction followed by back-extraction optimized with centroid composite design for the extraction of antibiotics from milk samples prior to their determination by HPLC–DAD. Microchemical Journal, 181: 107764.


• Gholizadeh, S., Mirzaei, H., Khandaghi, J., Afshar Mogaddam, M.R., and Javadi, A. (2022). Ultrasound–assisted solvent extraction combined with magnetic ionic liquid based-dispersive liquid–liquid microextraction for the extraction of mycotoxins from tea samples. Journal of Food Composition and Analysis, 114, 104831.


• Lehotay, S., Stajnbaher, D., Schenck, F., and Anastassiades, M. (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: 412-431.


• Mitra, S., and Brukh, R. (2003). Sample preparation techniques in analytical chemistry, John Wiley pub. New Jersey, pp. 12-35., 1-36.


• Mostafalou, S., and Abdollahi, M. (2013). Pesticides and human chronic diseases: evidences, mechanisms, and perspectives. Toxicology and applied pharmacology, 268(2), 157-177.


• Rasi, H., AfsharMogaddam, M., & Khandaghi, J. (2021). Application of a new extraction method coupled to high performance liquid chromatography for tetracyclines monitoring in cow milk. Journal of food science and technology (Iran), 18(113): 339-349. [In Persian]


• Rastpour, N., Khandaghi, J., Farajzadeh, M.A., and Afshar Mogaddam, M.R. (2022). Deep eutectic solvent-based QuEChERS method combined with dispersive liquid–liquid microextraction for extraction of benzoylurea insecticides in cabbage leaves samples. International Journal of Environmental Analytical Chemistry, 102(12): 2778-2791.


• Rezaee, M., Assadi, Y., Hosseini, M.R.M., Aghaee, E., Ahmadi, F., and Berijani, S. (2006). Determination of organic compounds in water using dispersive liquid–liquid microextraction. Journal of Chromatography a, 1116(1-2): 1-9.


• Sheikhzadeh, F., Afshar Mogaddam, M.R., Farajzadeh, M.A., and Khandaghi, J. (2020). Development of microwave radiations-induced homogeneous liquid-liquid microextraction method for extraction of pyrethroid pesticides in fruit and vegetable samples. International Journal of Environmental Analytical Chemistry, 1-12.


• Van der Hoff, G. R., and Van Zoonen, P. (1999). Trace analysis of pesticides by gas chromatography. Journal of Chromatography a, 843(1-2): 301-322.


• Vázquez, P.P., Mughari, A.R., and Galera, M.M. (2008). Solid-phase microextraction (SPME) for the determination of pyrethroids in cucumber and watermelon using liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection. Analytica Chimica Acta, 607(1): 74-82.


• Zahiri, E., Khandaghi, J., Farajzadeh, M.A., & Afshar Mogaddam, M.R. (2020). Combination of dispersive solid phase extraction with solidification organic drop–dispersive liquid–liquid microextraction based on deep eutectic solvent for extraction of organophosphorous pesticides from edible oil samples. Journal of Chromatography a, 1627: 461390.


• Zare Sani, M., Afshar Mogaddam, M.R., and Khandaghi, J. (2021). Combination of cold induced HLLME with an effervescence-assisted DLLME based on deep eutectic solvent decomposition; application in extraction of some pyrethroid and carbamate pesticides from edible oils. International Journal of Environmental Analytical Chemistry, 1-16.


• Zeiadi, S., Afshar Mogaddam, M.R., Farajzadeh, M.A., and Khandaghi, J. (2020). Combination of dispersive solid phase extraction with lighter than water dispersive liquid–liquid microextraction for the extraction of organophosphorous pesticides from milk. International Journal of Environmental Analytical Chemistry, 1-14.


• Zhang, D., and Lu, S. (2022). Human exposure to neonicotinoids and the associated health risks: A review. Environment International, 163: 107201.