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Eurasian Journal of Analytical Chemistry
Volume 12, Issue 2 (March 2017), pp. 17-30

DOI: 10.12973/ejac.2017.00151a

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Research Article

Published online on Dec 07, 2016

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Determination of Carbendazim and Chlorpyrifos in Selected Fruits and Vegetables Samples Using QuEChERS-HPLC-FD

Orhan Hazer, Mohammed Akkbik, Dilara Demir, & Yasemin Turhan


A new method was developed to determine pesticide residues in fruit and vegetable extracts with short time analysis. An optimum results were achieved using binary mobile phase consisting of (methanol: water; 95:5, v/v) and fluorescence detection (λEx and  λEm set at 280 and 340 nm, respectively) was used. The dynamic range was between 0.100 to 10 mg L-1 with relative standard deviation less than 0.45%, (n=4). Limits of detection and recoveries for carbendazim and chlorpyrifos were 0.073 mg L-1 (84.2-106.5%) and 0.062 mg L-1  (85.7-90.3%), respectively.  The results revealed that the concentrations of carbendazim and chlorpyrifos residue in all collected samples were below than the EU legal limit.

Keywords: carbendazim, chlorpyrifos, fruit & vegetable extracts, QuEChERS -HPLC-FD

  1. Obare, S. O., De, C., Guo, W., Haywood, T. L., Samuels, T. A., Adams, C. P., Masika, N. O., Murray,   D. H., Anderson, G. A., Campbell, K., & Fletcher, K. (2010). Fluorescent Chemosensors for Toxic Organophosphorus Pesticides. Sensors, 10, 7018.
  2. Islam, S., Afrin, N., Hossain, M. S., Nahar, N., Mosihuzzaman, M., & Mamun, M. I. R. (2009). Analysis of some pesticide residues in cauliflower by high performance liquid chromatography. American Journal of Environmental Sciences, 5(3), 325.
  3. Bedendo, G. C., Jardim, I. C. S. F., & Carasek, E. (2012). Multiresidue determination of pesticides in industrial and fresh orange juice by hollow fiber microporous membrane liquid–liquid extraction and detection by liquid chromatography electrospray tandem mass spectrometry. Talanta, 88, 573.
  4. Sungur, Ş., & Tunur, Ç. (2012). Investigation of pesticide residues in vegetables and fruits grown in various regions of Hatay, Turkey. Food Additives Contaminants, 5(4), 265.
  5. Hossain, M. S., Fakhruddin, A. N. M., Chowdhury, M. A. Z., Alam, M. K. (2013). Degradation of chlorpyrifos an organophosphorus insecticide in aqueous solution with gamma irradiation and natural sunlight. J Chem Eng, 1, 270–274.
  6. Topuz, S., Özhan, G. & Alpertunga, B. (2005). Simultaneous determination of various pesticides in fruit juices by HPLC-DAD. Food Control, 16, 87. 
  7. Venkateswarlua, P., Rama Mohan, K., Ravi Kumar, C.H., & Seshaiah, K. (2007). Monitoring of multi-class pesticide residues in fresh grape samples using liquid chromatography with electrospray tandem mass spectrometry. Food Chemistry, 105, 1760.
  8. Chen, Y. P., Ning, B., Liu, N., Feng, Y., Liu, Z., Liu, X., & Gao, Z. X. (2010). A rapid and sensitive fluoroimmunoassay based on quantum dot for the detection of chlorpyrifos residue in drinking water. Journal of Environmental Science and Health B, 45, 508.
  9. Chen, L., Song, F., Liu, Z., Zheng, Z., Xing, J., & Liu, S. (2012). Multi residue method for fast determination of pesticide residues in plants used in traditional chinese medicine by ultra high performance liquid chromatography coupled to tandem mass spectrometry. Journal of Chromatography A, 1225, 132.
  10. Michael, C. R. A., Jane, A. H., & Freya, K. (2004). Health effect of chronic pesticide exposure, Cancer and Neurotoxicity. Annual Review of Public Health, 25, 155.
  11. Beard, J. (2006). DDT and human health. Science of the total Environment, 355, 78.
  12. Leandroa, C. C., Hancock, P., Fussell, R. J., & Keely, B. J. (2006). Comparison of ultra-performance liquid chromatography and high-performance liquid chromatography for the determination of priority pesticides in baby foods by tandem quadrupole mass spectrometry. Journal of Chromatography A, 1103, 94.
  13. Isin, S., & Yildirim, I. (2007). Fruit growers perceptions on the harmful effects of pesticides and their reflection on practices, The case of Kemalpasa, Turkey. Crop Protection, 26, 917.
  14. Esturk, O., Yakar, Y., & Ayhan, Z. (2014). Pesticide residue analysis in parsley, lettuce and spinach by LC-MS/MS. Food Science Technology, 51(3), 458.
  15. Whitney, K. D., Seidler, F. J., & Slotkin, T. A. (1995). Developmental neurotoxicity of chlorpyrifos, cellular Mechanisms. Toxicology and Applied Pharmacology, 134, 53.
  16. Salm, P., Taylor, P., Roberts, D., & Silva, J. D. (2009), Liquid chromatography–tandem mass spectrometry method for the simultaneous quantitative determination of the organophosphorus pesticides dimethoate, fenthion, diazinon and chlorpyrifos in human blood. Journal of Chromatography B, 877, 568.
  17. Han, X. L., Tian, F. F., Ge, Y. S., Jiang, F. L., Lai, L., Li, D. W., Yu, Q. L., Wang, J., Lin, C., & Liu, Y. (2012). Spectroscopic structural and thermodynamic properties of chlorpyrifos bound to serum albumin, A comparative study between BSA and HSAPhotochem. Photochemistry Photobiology B, 109, 1-11.
  18. Cochran, R. C., Kishiyama, J., Aldous, C., Carr, W. C., & Pfeifer, K. F. (1995), Chlorpyrifos, Hazard assessment based on a review of the effects of short term and long term exposure in animals and humans. Food and Chemical Toxicology, 33(2), 165.
  19. Lu, S. Y., Liao, J. W., Kuo, M. L., Wang, S. C., Hwang, J. S., & Ueng, T. H. (2004). Endocrine disrupting activity in carbendazim induced reproductive and developmental toxicity in rats. Journal of Toxicology and Environmental Health, 67, 1501.
  20. Aire, T. A. (2005). Short term effects of carbendazim on the gross and microscopic features of the testes of Japanese quails (Coturnix coturnix japonica). Anatomy and Embryology, 210, 43.
  21. Alavanja, M. C. R., Dosemeci, M., Samanic, C., Lubin, J., Lynch, C. F., Knott, C., Barker, J., Hoppin, J. A., Sandler, D. P., Coble, J., Thomas, K., & Blair, A. (2004) .Pesticides and Lung  Cancer Risk in the Agricultural Health Study Cohort. American Journal of Epidemiology, 160, 876.
  22. Saad, B., Haniffa, N. H., Saleha, M. I., Hashimb, N. H., Abub, A., & Ali, N. (2004). Determination of ortho-phenylphenol, diphenyl and diphenylamine in apples and oranges using HPLC with fluorescence detection. Food Chemistry, 84, 313.
  23. Jacobsen, H., Qstergaard, G., Lam, H. R., Poulsen, M. E., Frandsen, H., Ladefoge, O., & Meyer, O. (2004). Repeated dose 28-day oral toxicity study in Wistar rats with a mixture of five pesticides often found as residues in food, alphacypermethrin, bromopropylate, carbendazim, chlorpyrifos and mancozeb. Food and Chemical Toxicology, 42, 1269.
  24. Asensio-Ramos, M., Hernandez-Borges, J., Borges-Miquel, T. M., & Rodriguez-Delgado, M. A. (2011). Ionic liquid-dispersive liquid–liquid microextraction for the simultaneous determination of pesticides and metabolites in soils using high-performance liquid chromatography and fluorescence detection. Journal of Chromatography A, 1218, 4808.
  25. Daam, M. A., & Van den Brink, P. J. (2007). Effects of Chlorpyrifos, Carbendazim, and Linuron on the Ecology of a Small Indoor Aquatic Microcosm. Archives of Environmental Contamination and Toxicology, 53, 22.
  26. A. O. A. C. Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with Magnesium Sulfate. (AOAC Official Method 2007.01.)
  27. Song, D., & Wang, J. (2003). Modified resolution factor for asymmetrical peaks in chromatographic separation. Journal of Pharmaceutical and Biomedical Analysis, 32, 1105.
  28. Wang, M., Qu, F., Shan, X. Q., & Lin, J. M. (2003). Development and optimization of a method for the analysis of low-molecular-mass organic acids in plants by capillary electrophoresis with indirect UV detection. Journal of Chromatography A, 989, 285.
  29. Sankalia, J. M., Sankalia, M. G., Sutariya, V. B., & Mashru, R. C. J. (2007). Nateglinide quantification in rabbit plasma by HPLC, Optimization and application to pharmacokinetic study. Journal of Pharmaceutical and Biomedical Analysis, 44, 196.
  30. Parveen, Z., Khuhro, M. I., Rafiq, N., & Kausar, N. (2004). Evaluation of Multiple Pesticide Residues in Apple and Citrus Fruits. Bulletin of Environmental Contamination and Toxicology, 73, 312.
  31. Liu, Z., Liu, W., Wu, Q., Zang, X., Zhou, X., Zeng, X., & Wang, Z. (2012). Determination of carbendazim and thiabendazole in apple juice by hollow fibre-based liquid phase microextraction-high performance liquid chromatography with fluorescence detection. International Journal of Environmental Analytical Chemistry, 92(5), 582.
  32. Martindale, R. W. (1988). Determination of residues of a range of fungicides, antisprouting agents and (organochlorine and organophosphorus) insecticides in potatoes by gas liquid and high performance liquid chromatography. Analyst, 113, 1229.
  33. González-Curbelo, M. A., Socas-Rodríguez, B., Herrera-Herrera, A. V., González-Sálamo, J., Hernández-Borges, J., & Rodríguez-Delgado, M. Á. (2015). Evolution and applications of the QuEChERS method. Trends in Analytical Chemistry, 71, 169.
  34. Zhu, J., Dai, X. J., Fang, J. J., & Zhu, H. M. (2013). Simultaneous detection and degradation patterns of kresoxim-methyl and trifloxystrobin residues in citrus fruits by HPLC combined with QuEChERS. Journal of Environmental Science and Health Part B, 48, 470.
  35. Sack, C., Smoker, M., Chamkasem, N., Thompson, R., Satterfield, G., Masse, C., Mercer, G., Neuhaus, B., Cassias, I., Chang, E., Lin, Y., MacMahon, S., Wong, J., Zhang, K., & Smith, R. E. (2011). Collaborative Validation of the QuEChERS Procedure for the Determination of Pesticides in Food by LC-MS/MS. Journal of Agricultural and Food Chemistry, 59, 6383.
  36. Hill, A. S., Skerritt, J. H., Bushway, R. J., Pask, W., Larkin, K. A., Thomas, M., Korth, W., & Bowmer, K. (1994). Development and application of laboratory and field immunoassays for chlorpyrifos in water and soil matrixes. Journal of Agricultural and Food Chemistry, 42(9), 2051.
  37. Crum, S. J. H., van Kammen-Polman, A. M. M., & Leistra, M. (1999).  Sorption of Nine Pesticides to Three Aquatic Macrophytes. Archives of Environmental Contamination and Toxicology, 37, 310.
  38. El-Shahawi, M. S. (1997). Retention profiles of some commercial pesticides, pyrethroid and aca-ricide residues and their application to tomato and parsley plants. Journal of Chromatography A, 760, 179.