JEAS  Vol.6 No.3 , September 2016
Development of Ecologically Acceptable Chlorpyrifos Formulation for Effective and Safe Application
Abstract: Application of the commercial formulation of chlorpyrifos has resulted in considerable environmental contamination. This study was designed to develop environmentally acceptable chlorpyrifos formulation for safe and effective application. This involved the modification of clay surfaces from hydrophilic to hydrophobic via ion-exchange reaction with organic cations. The resulting organo-clay complexes were tested for adsorption and release of chlorpyrifos. HPLC and FTIR measurements showed considerable adsorption and strong interaction between chlorpyrifos molecules and the organo-clay complexes. Basal spacing results emphasized the formation of suitable micro-pores for chlorpyrifos molecules. HPLC and bioassay techniques confirmed the slow release of chlorpyrifos. Leaching potential showed retention of chlorpyrifos in the top soil. Therefore application of organoclay formulation of chlorpyrifos may reduce their potential environmental contamination and produce safe applications.
Cite this paper: El-Nahhal, Y. , Wheidi, B. and El-Kurdi, S. (2016) Development of Ecologically Acceptable Chlorpyrifos Formulation for Effective and Safe Application. Journal of Encapsulation and Adsorption Sciences, 6, 91-108. doi: 10.4236/jeas.2016.63008.

[1]   Tomlin, C.D.S. (2006) The Pesticide Manual, A World Compendium, 14th Edition British Crop Protection Council. Alton, Hampshire, 186-187.

[2]   El-Nahhal, Y. (2004) Contamination and Safety Status of Plant Food in Arab Countries. Journal of Applied Science, 4, 411-417.

[3]   Phillips, P.J. and Bode, R.W. (2004) Pesticides in Surface Water Runoff in South-East New York State, USA: Seasonal and Storm Flow Effects on Concentrations. Pest Management Science, 60, 531-543.

[4]   Becker, K., Seiwert, M., Angerer, J., Kolossa-Gehring, M., Hoppe, H.W., Ball, M., Schulz, C., Thumulla, J. and Seifert, B. (2006) GerES IV Pilot Study: Assessment of the Exposure of German Children to Organophosphorus and Pyrethroid Pesticides. International Journal of Hygiene and Environmental Health, 209, 221-233.

[5]   Rahmanikhah, Z., Abbas, E.S., Bahramifar, N. and Bousjien, Z.Sh. (2010) Organophosphorous Pesticide Residues in the Surface and Ground Water in the Southern Coast Watershed of Caspian Sea Iran. World Applied Sciences Journal, 9, 160-166.

[6]   Angioni, A., Dedola, F., Garau, A., Sarais, G., Cabras, P. and Caboni, P. (2011) Chlorpyrifos Residues Levels in Fruits and Vegetables after Field Treatment. Journal of Environmental Science and Health. Part B, 46, 544-549.

[7]   Schecter, A., Papke, O., Isaac, J., Hrimat, N., Neiroukh, F., Safi, J. and El-Nahhal, Y. (1997) 2,3,7,8 Chlorine Substituted Dioxins and Dibenzofuran Congeners in 2,4-D, 2,4,5-T and Pentachlorophenol. Organohalogen Compounds, 32, 51-55.

[8]   Harnly, M., McLaughlin, R., Bradman, A., Anderson, M. and Gunier, R. (2005) Correlating Agricultural Use of Organophosphates with Outdoor Air Concentrations: A Particular Concern for Children. Environmental Health Perspectives, 113, 1184-1189.

[9]   Zhong, G., Xie, Z., Cai, M., Moller, A., Sturm, R., Tang, J., Zhang, G., He, J. and Ebinghaus, R. (2012) Distribution and Air-Sea Exchange of Current-Use Pesticides (CUPs) from East Asia to the High Arctic Ocean. Environmental Science & Technology, 46, 259-267.

[10]   Garbarino, J.R., Snyder-Conn, E., Lieker, T.J. and Hoffman, G.L. (2002) Contaminants in Arctic Snow Collected over Northwest Alaskan Sea Ice. Water, Air, & Soil Pollution, 139, 183-214.

[11]   Hore, P., Robson, M., Freeman, N., Zhang, J., Wartenberg, D., Ozkayna, H., Tulve, N., Sheldon, L., Needham, L., Barr, D. and Lioy, P.J. (2005) Chlorpyrifos Accumulation Patterns for Child-Accessible Surfaces and Objects and Urinary Metabolite by Children for 2 Weeks after Crack-and-Crevice Application. Environmental Health Perspectives, 113, 211-219.

[12]   Morgan, M.K., Sheldon, L.S., Croghan, C.W., Jones, P.A., Robertson, G.L., Chuang, J.C., Wilson, N.K. and Lyu, C.W. (2005) Exposures of Preschool Children to Chlorpyrifos and Its Degradation Product 3,5,6-Trichloro-2-Pyridinol in Their Everyday Environments. Journal of Exposure Analysis and Environmental Epidemiology, 15, 297-309.

[13]   Safi, J., Abu Foul, N., El-Nahhal, Y. and El-Sebae, A. (2002) Monitoring of Pesticide Residues on Cucumber, Tomatoes and Strawberries in Gaza Governorates, Palestine. Nahrung/ Food, 46, 34-49.<34::AID-FOOD34>3.0.CO;2-W

[14]   Safi, J., Awad, Y. and El-Nahhal, Y. (2014) Bioremediation of Diuron in Soil and by Cyanobacterial Mat. American Journal of Plant Sciences, 5, 1081-1089.

[15]   Schecter, A., Papke, O., Ryan, J., Furst, P., Isaac, J., Hrimat, N., Neiroukh, F., Safi, J., El-Nahhal, Y., Abu El-Haj, S., Avni, A., Richter, E., Chuwers, P. and Fischbein, A. (1997) Dioxins, Dibenzofurans and PCBs in Human Blood, Human Milk and Food from Israel, The West Bank and Gaza. Organohalogen Compounds, 33, 457-461.

[16]   Anderson, T.D. and Lydy, M.J. (2002) Increased Toxicity to Invertebrates Associated with a Mixture of Atrazine and Organophosphate Insecticides. Environmental Toxicology and Chemistry, 21, 1507-1515.

[17]   USEPA (US Environmental Protection Agency) (2011) Chlorpyrifos Facts.

[18]   Belden J.B., Gilliom, J.R. and Lydy, J.M. (2007) How Well Can We Predict the Toxicity of Pesticide Mixtures to Aquatic Life. Integrated Environmental Assessment and Management, 3, 364-372.

[19]   Jin, Y., Liu, Z., Peng, T. and Fu, Z. (2015) The Toxicity of Chlorpyrifos on the Early Life Stage of Zebrafish: A Survey on Endpoints at Development, Locomotor Behavior, Oxidative Stress and Immunotoxicity. Fish & Shellfish Immunology, 43, 405-414.

[20]   Kais, B., Stenel, D., Batel, A. and Braunbech, T. (2015) Acetylcholinesterase in Zebrafish Embryos as a Tool to Identify Neurotoxic Effects in Sediments. Environmental Science and Pollution Research International, 22, 16329-16339.

[21]   EL-Nahhal, Y., EL-Najjar, Sh. and Afifi, S. (2015) Impact of Organic Contamination on Some Aquatic Organisms. Toxicology International, 22, 45-53.

[22]   El-Nahhal, Y. (2016) Biochemical Changes Associated with Long Term Exposure to Pesticide among Farmers in the Gaza Strip. Occupational Diseases and Environmental Medicine, 4, 72-82.

[23]   Sindi, R.A., Harris, W., Arnott, G., Flaskos, J., Lloyd Mills, C. and Hargreaves, A.J. (2016) Chlorpyrifos- and Chlorpyrifos Oxon-Induced Neurite Retraction in Pre-Differentiated N2a Cells Is Associated with Transient Hyperphosphorylation of Neurofilament Heavy Chain and ERK 1/2. Toxicology and Applied Pharmacology, 308, 20-31.

[24]   Zeljezic, D., Mladinic, M., Zunec, S., LucicVrdoljak, A., Kasuba, V., Tariba, B., Zivkovic, T., Marjanovic, A.M., Pavicic, I., Milic, M., Rozgaj, R. and Kopjar, N. (2016) Cytotoxic, Genotoxic and Biochemical Markers of Insecticide Toxicity Evaluated in Human Peripheral Blood Lymphocytes and an HepG2 Cell Line. Food and Chemical Toxicology, 96, 90-106.

[25]   Chen, S., Chen, M., Wang, Z., Qiu, W., Wang, J., Shen, Y., Wang, Y. and Ge, S. (2016) Toxicological Effects of Chlorpyrifos on Growth, Enzyme Activity and Chlorophyll a Synthesis of Freshwater Microalgae. Environmental Toxicology and Pharmacology, 45, 179-186.

[26]   MoA (Ministry of Agriculture) (2013) Department of Plant Protection. Annual Report, Gaza.

[27]   El-Nahhal, Y. and Lagaly, G. (2005) Salt Effects on the Adsorption of a Pesticide on Modified Bentonite. Colloid and Polymer Science, 283, 968-974.

[28]   El-Nahhal, Y., Nir, S., Polubesova, T., Margulies, L. and Rubin, B. (1997) Organo-Clay Formulations of Alachlor: Reduced Leaching and Improved Efficacy. Proceedings of Brighton Crop Protection Conference, Brighton, November 1997, 21-26.

[29]   El-Nahhal, Y. (2003) Adsorptive Behavior of Acetochlor on Organoclay Complexes. Bulletin of Environmental Contamination and Toxicology, 70, 1104-1111.

[30]   El-Nahhal, Y. (2002) Adsorptive of Chlorpyrifos on Organoclay Complexes: Influence of Salt Concentration. In: Ottner, F. and Gier, S., Eds., Berichte der Deutschen Ton-und To nmineralgruppe e. V, Band 9, Beitrage zur Jahrestagung, Wien, 17-30.

[31]   El-Nahhal, Y. (2003) Adsorption Mechanism of Chloroacetanilide Herbicides to Modified Montmorillonite. Journal of Environmental Science and Health Part B, 38, 591-604.

[32]   El-Nahhal, Y., Nir, S., Polubesova, T., Margulies, L. and Rubin, B. (1998) Leaching, Phototoxicity and Weed Control of New Formulation of Alachlor. Journal of Agricultural and Food Chemistry, 46, 3305-3313.

[33]   El-Nahhal, Y., Lagaly, G. and Rabinovitz, O. (2005) Organo-Clay Formulations of Acetochlor: Effect of High Salt. Journal of Agricultural and Food Chemistry, 53, 1620-1624.

[34]   El-Nahhal, Y. (2003) Persistence, Mobility, Efficacy and Safety of Chloroacetanilide Herbicide Formulation under Field Conditions. Environmental Pollution, 124, 33-38.

[35]   El-Nahhal, Y. (2004) Leaching Behavior of Metolachlor in Soil. Journal of Environmental Engineering & Science, 3, 187-194.

[36]   El-Nahhal, Y., Abadsa, M. and Affifi, S. (2014) Leaching Potential of Diuron and Linuron in Gaza Soils. American Journal of Plant Sciences, 5, 4040-4049.

[37]   El-Nahhal, Y., EL-dahdouh, N., Hamdona, N. and Alshanti, A. (2016) Toxicological Data of Some Antibiotics and Pesticides to Fish, Mosquitoes, Cyanobacterial Mats and to Plants. Data in Brief, 6, 871-880.

[38]   EL-Nahhal, Y., Kerkez, M.F.S. and Abu Heen, Z. (2015) Toxicity of Diuron, Diquat and Terbutryn Cyanobacterial Mats. Ecotoxicology and Environmental Contamination, 10, 71-82.

[39]   Nir, S., El-Nahhal, Y., Undabeytia, T., Rytwo, G., Polubesova, T., Mishael, Y., Rabinovitz, O. and Rubin, B. (2006) Clays and Pesticides. In: Bergaya, F., Theng, B.K.G. and Lagaly, G., Eds., Handbook of Clay Science, Elsevier, Amsterdam, 677-691.

[40]   El-Nahhal, Y. and Safi, J. (2004) Adsorption Behavior of Phenanthrene on Organoclays under Different Salinity Levels. Journal of Colloid and Interface Science, 269, 265-273.

[41]   Suciu, N.A. and Capri, E. (2009) Adsorption of Chlorpyrifos, Penconazole and Metalaxyl from Aqueous Solution by Modified Clays. Journal of Environmental Science and Health Part B, 44, 525-532.

[42]   Nir, S., Undabeytia, T., Yaron, D., El-Nahhal, Y., Polubesova, T., Serban, S., Rytwo, G., Lagaly, G. and Rubin B. (2000) Optimization of Adsorption of Hydrophobic Herbicides on Montmorillonite Preadsorbed by Monovalent Organic Cations: Interaction between Phenyl rings. Environmental Science and Technology, 34, 1269-1274.

[43]   Baglieri, A., Nègre, M., Trotta, F., Bracco, P. and Gennari, M. (2013) Organo-Clays and Nanosponges for Acquifer Bioremediation: Adsorption and Degradation of Triclopyr. Journal of Environmental Science and Health Part B, 48, 784-792.

[44]   Rubin, B., El-Nahhal, Y., Nir, S. and Margulies, L. (2000) Slow Release Formulations of Pesticides. US Patent No. 6,261,997.

[45]   MacEwan, C. and Wilson, J. (1980) Interlayer and Intercalation Complexes of Clay Minerals. In: Brindley, G.W. and Brown, G., Eds., Crystal Structures of Clay Minerals and Their X-Ray Identification, Mineralogical Society, London, 197-248.

[46]   Stevens, J.J. and Anderson, S.J. (1996) Orientation of Trimethylphenylammonium (TMPA) on Wyoming Montmorillonite: Implications for Arene Sorption. Clays and Clay Minerals, 44, 132-141.

[47]   Olivella, M.A., Bassicaupi, C., Bianchi, A., Fiol, N. and Villaescusa, I. (2015) New Insights into the Interactions between Cork Chemical Components and Pesticides. The Contribution of π-π Interactions, Hydrogen Bonding and Hydrophobic Effects. Chemosphere, 119, 863-870.

[48]   Jaynes, W.F. and Boyd, S.A. (1991) Clay Mineral Type and Organic Compound Sorption by hexadecyltrimethylammoium-Exchanged Clays. Soil Science Society of America Journal, 55, 43-48.

[49]   El-Nahhal, Y. and Safi, J. (2005) Adsorption of Benzene and Naphthalene to Modified Montmorillonite. Journal of Food, Agriculture and Environment, 3, 295-298.

[50]   El-Nahhal, Y., Nir, S., Serban, C., Rabinovitch, O. and Rubin, B. (2000) Montmorillonite-Phenyltrimethylammonium Yields Environmentally Improved Formulations of Hydrophobic Herbicides. Journal of Agricultural and Food Chemistry, 48, 4791-4801.

[51]   Armenta, S., Quintas, G., Grrigues, S. and de la Guadia, M. (2005) A Validated and Fast Procedure for FTIR Determination of Cypermetherin and Chlorpyrifos. Talanta, 67, 634-639.

[52]   Schmidt, P., Dybal, J. and Trchova, M. (2006) Investigations of the Hydrophobic and Hydrophilic Interactions in Polymer-Water Systems by ATR FTIR and Raman Spectroscopy. Vibrational Spectroscopy, 42, 278-283.

[53]   Shah, R.M., Alam, M., Ahmad, D., Waqas, M., Ali, Q., Binyamin, M. and Shad S.A. (2016) Toxicity of 25 Synthetic Insecticides to the Field Population of Culex quinquefasciatus Say. Parasitology Research, 1-7.