Stability and neurotoxic impact of organophosphate pesticides in aqueous environments

Keywords: organophosphate, pesticide, pH stability, toxicity

Abstract


Introduction/purpose: Organophosphates are widely used nowadays. They have applications as pesticides, drugs, plasticizers, flame retardants, or chemical warfare agents. Their acute toxicity is ascribed to inhibiting acetylcholinesterase (AChE), a key enzyme in the transmission of nerve impulses in animals. Their toxic effects manifest by acetylcholine accumulation in the nerve synapses and can lead to paralysis or death. Organo-thiophosphate pesticides (OPs) are used in large quantities. Their oxo-analogs can also be found in the environment due to oxidation. Once accumulated in the environment, they exhibit toxic effects on non-target organisms.

Methods: The hydrolysis of OPs in different pH was systematically analyzed, and their neurotoxic effects were evaluated. The concentration of the investigated pesticides during decomposition was monitored by ultra-performance liquid chromatography (UPLC). At the same time, a decrease in the toxicity of the treated samples was observed by measuring the activity of the enzyme AChE.

Results: OPs decompose rapidly in alkaline aqueous solutions but are highly stable in acidic solutions. Chlorpyrifos hydrolyzes the fastest and dimethoate the slowest. The toxicity of these OP solutions decreases over time, indicating that more toxic products were not formed. 

Conclusion: The presented results can provide a sound basis for further efforts to find simple and efficient decomposition methods of OPs.

References

Aćimović, D.D. & Vasić Anićijević, D.D. 2022. Electrooxidative Removal of Organophosphates - A Combined Experimental and Theoretical Approach. In: Organophosphates: Detection, Exposure and Occurrence. Volume 1: Impact on Health and the Natural Environment, pp.215-250 [online]. Available at: https://vinar.vin.bg.ac.rs/handle/123456789/10726?locale-attribute=en [Accessed: 03 October 2024]. ISBN: 1-68507-724-2.

Anićijević, V.J. & Karkalić, R.M. 2022. Organophosphates as Chemical Warfare Agents. In: Lazarević-Pašti, T. (Ed.) Organophosphates: Detection, Exposure and Occurrence. Volume 2: Acute Exposure and Treatments. Hauppauge, NY: Nova Science Publishers, Inc. ISBN: 978-1-68507-734-1.

Anićijević, V.J. & Lazarević-Pašti, T.D. 2020. Chapter 1. Organophosphates: Application, Effects on Human Health and Removal. In: Marquis, F. (Ed.) Organophosphate Pesticides. Hauppauge, NY: Nova Science Publishers, Inc. ISBN: 978-1-53618-307-8.

Anićijević, V.J., Petković, M., Pašti, I.A. & Lazarević-Pašti, T.D. 2022. Decomposition of Dimethoate and Omethoate in Aqueous Solutions — Half-Life, Eco-Neurotoxicity Benchmarking, and Mechanism of Hydrolysis. Water, Air, & Soil Pollution, 233, art.number:390. Available at: https://doi.org/10.1007/s11270-022-05861-w.

Baker, B.P., Benbrook, C.M., Groth III, E. & Lutz Benbrook, K. 2002. Pesticide residues in conventional, integrated pest management (IPM)-grown and organic foods: insights from three US data sets. Food Additives & Contaminants, 19(5), pp.427-446. Available at: https://doi.org/10.1080/02652030110113799.

Bootharaju, M.S. & Pradeep, T. 2012. Understanding the Degradation Pathway of the Pesticide, Chlorpyrifos by Noble Metal Nanoparticles. Langmuir, 28(5), pp.2671-2679. Available at: https://doi.org/10.1021/la2050515.

Ellman, G.L., Courtney, K.D., Andres, V., Jr. & Featherstone, R.M. 1961. A new and rapid colorimetric determination of acetylcholinesterase activity. Biochemical Pharmacology, 7(2), pp.88-95. Available at: https://doi.org/10.1016/0006-2952(61)90145-9.

Elmorsy, E., Al-Ghafari, A., Al Doghaither, H., Salama, M. & Carter, W.G. 2022. An Investigation of the Neurotoxic Effects of Malathion, Chlorpyrifos, and Paraquat to Different Brain Regions. Brain Sciences, 12(8), art.number:975. Available at: https://doi.org/10.3390/brainsci12080975.

Greaves, A.K. & Letcher, R.J. 2017. A Review of Organophosphate Esters in the Environment from Biological Effects to Distribution and Fate. Bulletin of Environmental Contamination and Toxicology, 98, pp.2-7. Available at: https://doi.org/10.1007/s00128-016-1898-0.

Grue, C.E., Hart, A.D.M. & Mineau, P. 1991. Biological consequences of depressed brain cholinesterase activity in wildlife. In: Mineau, P. (Ed.) Cholinesterase-inhibiting insecticides. Their impact on wildlife and the environment., pp.151-209. Elsevier Science Publishers B.V. ISBN: 0-444-88707-5.

He, J., Song, L., Chen, S., Li, Y., Wei, H., Zhao, D., Gu, K. & Zhang, S. 2015. Novel restricted access materials combined to molecularly imprinted polymers for selective solid-phase extraction of organophosphorus pesticides from honey. Food Chemistry, 187, pp.331-7. Available at: https://doi.org/10.1016/j.foodchem.2015.04.069.

Kunstadter, P., Prapamontol, T., Sirirojn, B.-O., Sontirat, A., Tansuhaj, A. & Khamboonruang, C. 2001. Pesticide Exposures among Hmong Farmers in Thailand. International Journal of Occupational and Environmental Health, 7(4), pp.313-325. Available at: https://doi.org/10.1179/107735201800339227

Lazarević-Pašti, T.D., Pašti, I.A., Jokić, B., Babić, B.M. & Vasić, V.M. 2016. Heteroatom-doped mesoporous carbons as efficient adsorbents for removal of dimethoate and omethoate from water. RSC Advances, 6, pp.62128-62139. Available at: https://doi.org/10.1039/C6RA06736K.

Legradi, J.B., Di Paolo, C., Kraak, M.H.S., van Der Geest, H.G., Schymanski, E.L., Williams, A.J., Dingemans, M.M.L., Massei, R., Brack, W., Cousin, X., Begout, M.-L., van der Oost, R., Carion, A., Suarez-Ulloa, V., Silvestre, F., Escher, B. I., Engwall, M., Nilén, G., Keiter, S.H., Pollet, D., Waldmann, P., Kienle, C., Werner, I., Haigis, A.-C., Knapen, D., Vergauwen, L., Spehr, M., Schulz, W., Busch, W., Leuthold, D., Scholz, S., vom Berg, C.M., Basu, N., Murphy, C.A., Lampert, A., Kuckelkorn, J., Grummt, T. & Hollert, H. 2018. An ecotoxicological view on neurotoxicity assessment. Environmental Sciences Europe, 30, art.number:46. Available at: https://doi.org/10.1186/s12302-018-0173-x.

Lockridge, O., Verdier, L. & Schopfer, L.M. 2019. Half-life of chlorpyrifos oxon and other organophosphorus esters in aqueous solution. Chemico-Biological Interactions, 311, art.number:108788. Available at: https://doi.org/10.1016/j.cbi.2019.108788.

London, L., De Grosbois, S., Wesseling, C., Kisting, S., Rother, H.A. & Mergler, D. 2002. Pesticide Usage and Health Consequences for Women in Developing Countries: Out of Sight Out of Mind? International Journal of Occupational and Environmental Health, 8(1), pp.46-59. Available at: https://doi.org/10.1179/oeh.2002.8.1.46.

Peshin, R., Hansra, B.S., Nanda, R., Singh, K., Sharma, R., Garg, L., Bajiya, M.R., Showkat, A., Kumar, R. & Yangsdon, S. 2020. Pesticides Hazardous Hotspots: Empirical Evidences from North India. Environmental Management, 66, pp.899-915. Available at: https://doi.org/10.1007/s00267-020-01317-1.

Rasmussen, J.J., Wiberg-Larsen, P., Baattrup-Pedersen, A., Cedergreen, N., Mcknight, U.S., Kreuger, J., Jacobsen, D., Kristensen, E.A. & Friberg, N. 2015. The legacy of pesticide pollution: An overlooked factor in current risk assessments of freshwater systems. Water Research, 84, pp.25-32. Available at: https://doi.org/10.1016/j.watres.2015.07.021.

Richendrfer, H. & Creton, R. 2015. Chlorpyrifos and malathion have opposite effects on behaviors and brain size that are not correlated to changes in AChE activity. Neurotoxicology, 49, pp.50-58. Available at: https://doi.org/10.1016/j.neuro.2015.05.002.

Silva, V., Mol, H.G.J., Zomer, P., Tienstra, M., Ritsema, C.J. & Geissen, V. 2019. Pesticide residues in European agricultural soils–A hidden reality unfolded. Science of The Total Environment, 653, pp.1532-1545. Available at: https://doi.org/10.1016/j.scitotenv.2018.10.441.

Sparling, D.W. & Fellers, G. 2007. Comparative toxicity of chlorpyrifos, diazinon, malathion and their oxon derivatives to larval Rana boylii. Environmental Pollution, 147(3), pp.535-539. Available at: https://doi.org/10.1016/j.envpol.2006.10.036.

Ubaid Ur Rahman, H., Asghar, W., Nazir, W., Sandhu, M. A., Ahmed, A. & Khalid, N. 2021. A comprehensive review on chlorpyrifos toxicity with special reference to endocrine disruption: Evidence of mechanisms, exposures and mitigation strategies. Science of The Total Environment, 755(2), art.number:142649. Available at: https://doi.org/10.1016/j.scitotenv.2020.142649.

Van Scoy, A., Pennell, A. & Zhang, X. 2016. Environmental Fate and Toxicology of Dimethoate. In: de Voogt, W. (Ed.) Reviews of Environmental Contamination and Toxicology Volume 237, pp.53-70. Cham: Springer. Available at: https://doi.org/10.1007/978-3-319-23573-8_3.

Vasić Anićijević, D.D. 2020. Chapter 3. Computational modelling of organophosphorous pesticides–density functional theory calculations. In: Marquis, F. (Ed.) Organophosphate Pesticides. Hauppauge, NY: Nova Science Publishers, Inc. ISBN: 978-1-53618-307-8.

Wang, X., Xing, H., Jiang, Y., Wu, H., Sun, G., Xu, Q. & Xu, S. 2013. Accumulation, histopathological effects and response of biochemical markers in the spleens and head kidneys of common carp exposed to atrazine and chlorpyrifos. Food and Chemical Toxicology, 62, pp.148-58. Available at: https://doi.org/10.1016/j.fct.2013.08.044.

Wolfe, N.L., Zepp, R.G., Gordon, J.A., Baughman, G.L. & Cline, D.M. 1977. Kinetics of chemical degradation of malathion in water. Environmental Science & Technology, 11(1), pp.88-93. Available at: https://doi.org/10.1021/es60124a001.

Published
2025/02/01
Section
Original Scientific Papers