Evaluation of Factors Inf luencing Recovery of Herbicide 2,4-D from Drinking Water

Document Type : Research Article


1 Department of Occupational Health, School of Public Health, Tehran University of Medical Sciences, P.O. Box 14155-6446, Tehran, I.R. IRAN

2 Department of Pharmacology, School of Medicine, Kashan University of Medical Sciences, Kashan, I.R. IRAN

3 School of Biomedical and Life Sciences, University of Surrey, GU2 7XH, UK



Many modern analytical methods deal with the trace-level determination of compounds of interest in highly complex environmental samples by means of chromatographic techniques. The introduction of a “clean” sample into an analytical instrument can make analyses easier and prolongs the equipment life. The use of solid-phase extraction (SPE) has grown and is a fertile technique of sample preparation as it provides better results than those produced by liquid-liquid extraction (LLE). The application of SPE can give selectivity of extraction providing a purified and concentrated extract. Through this study, optimization of trace enrichment and sample clean-up method via the use of bonded silica cartridges is discussed. SPE using bonded silica has been optimized with respect of sample pH, sample concentration, elution solvent strength, sample volume, and elution volume. In this investigation a variety of non-polar sorbent cartridges were also screened. During this study, the octadecyl bonded silica cartridge (C18) has proven successful in simplifying sample preparation. The present approach proved that 2,4-D could be retained on C18 based on specific interaction. Further study employed methanol to extract the analyte from spiked water and gave a clean sample for high pressure liquid chromatography equipped with ultra violet detection system. The optimized method was validated with three different pools of spiked samples and showed good reproducibility over six consecutive days as well as six within-day experiments.


Main Subjects

[1] Moretto, A., and Lotti, M., “Toxicology of Pesticides. In Occupational Toxicology”, Stacey, N. H., Taylor and Francis Ltd., London, UK, pp. 177-204, (1993).
[2] Winder, C., “Toxicology of Metals. In Occupational Toxicology”, Stacy, N. H.,  Taylor and Francis Ltd., London, UK, pp. 156-204, (1993).
[3] Oliveria, G.H., and Neto, J.P., Toxicology of 2,4-Diclorophenoxyacetic Acid (2,4-D) and Its Determination in Serum and Brain Tissue Using Gas Chromatography-Electron Capture Detection, J. Anal. Toxicol., 16, pp. 251 (1995).
[4] Aprea, C., Sciarra, G. and Boozi, N., Analytical Methods For the Determination of Urinary 2,4-D and MCPA in Occupationally Exposed Subjects and in the general Population, J.Anal.Toxicol., 21, p. 262 (1997).
[5] Polcaro, C. M., Marra, C., Desiderio, C. and Fanali, S., Stereoselective Aanalysis of Acid Herbicides
in Natural Watersby Capillary Electrophoresis, Electrophoresis, 20, p. 2420 (1999).
[6] Hennion, M. C.,  and  Scribe,   P.,   Sample   Handling Strategies For the Analysis of Organic Compounds From EnvironmentalWater Samples. In Environ-mental Analysis: Techniques, Applications and Quality Assurance, Barcelo, D., Elsevier, Amsterdam, 13, pp. 23 (1993).
[7] Pool, S. K., Dean, T. A., Oudsema, J. W., and Poole, C. F., Sample preparation for Chromatographic Separation: An Overview, Analytica Chimica Acta, 236, p. 3 (1990).
[8] McDowall, R. D., Sample Preparation For Biomedical Analysis, J. Chromatogr., 492, p. 3 (1989).
[9] McDowall, R. D., Sample Preparation For HPLC Analysis of Drugs in Biological Fluids, J. Phrm, Biomed. Anal., 7, p. 1087 (1989).
[10] Henriksen, T., Svensmark, B., Lindhardt, B., and Juhler R. K., Analysis of acidic pesticides in situ derivatization with alkylchloroformate and solid-phase microextractio (SPME) for GC-MS. Chemosphare, 44, p. 1531 (2001).
[11] Ding, W., Liu, C., and Yeh, S. Analysis of chlorophenoxy acid herbicides in water by large-volume on-line derivatization and gas chromato-graphy- mass spectrometry, Journal of Chromato-graphy A, 896, p. 111 (2000).
[12] Wells, M. J. M., and Yu l. Z., Solid-phase extraction of acidic herbicides, Journal of Chromatography A, 885, p. 237 (2000).
[13] Barcelo, D., Occurrence, Handling and Chromato-graphic Determination of Pesticides in Aquatic Environment, Analyst, 116, p. 681 (1991).
[14] Lagana, A., Bacaloni, A., Leva, I. D., Faberi, A., Fago, G., and Marino, A., Occurrence and determination of herbicides and their major transformation products in environmental waters, Analytica Chimica Acta, 462, p. 187 (2002).
[15] Barrett, D. A., Brown,V. A., Shaw, P. N., and Davies, M. C., Characterization of a Range of Alkyl-Bonded Silica HPLC Stationary Phases: Chromato-graphic Behaviour of Neutral Acidic, and Basic Test Solutes, J. Chromatogr. Sci., 34, p. 146 (1996).
[16] Trocewicz, J., Determination of Herbicides in Surface Water by Means of a Supported Liquid Membrane Technique and High-Performance Liquid Chromatography, J. Chromatogr. A, 752, p. 121 (1996).
[17] Wells, M. J. M., “Off-line Multistage Extraction Chromatography For Ultraselective Herbicide Residue Isolation”, In: Proceedings of the Third Annual International Symposium on Sample Preparation and Isolation Using Bonded Silicas, Analytichem International, Harbor City, CA, USA, (1986).
[18] Worthing, C. R., and Hance, J. R., “The Pesticide Manua”,. 9th Ed., The British Crop Protection Council, London, UK, (1991).
[19] Prapamontol, T., The Development, Validation and Application of Chromatographic Methods to Study Organochlorine Pesticides in Milk and Water, A PhD Thesis, University of Surrey, Surrey, UK, (1991).