Abstract
Purpose
DDT and its metabolites continues to be detected in agricultural soils despite its restriction for indoor use only. As Persistent Organic Pollutants (POPs), DDT and its metabolites have been shown to be carcinogens, endocrine disruptors and skin irritants thus studies devoted to determine their transformation kinetics are crucial. The transformation kinetics of DDE in soils has been interpreted in terms of first order kinetics which cannot resolve between adsorption and biodegradation and hence is of limited scope in terms of kinetic and thermodynamic description of the transformation process. The aim of the present work was to interpret the kinetics in terms of the multi-phase pseudo-zero order rate law which is capable of resolving between adsorption and biodegradation.
Methods
The study is based on persistence data reported in literature that was carried out using 14 C as radio tracer. The residual 14 C DDE radioactive amounts were plotted as a function of time to give persistence curves.
Results
Presented data shows that, the transformation kinetics of DDE in Philippine soil indeed conform to the tri-phasic linear rate law, indicative of the existence of three speciation forms attributed to free DDE molecules in solution in the soil pore water, and DDE adsorbed to soil colloidal particles types 1 and 2. On the basis of the multi-phase pseudo-zero order rate law adopted in this study, 13 kinetic parameters and 10 thermodynamic parameters can be adequately specified. The kinetic parameters are; the zero order and first order rate constants for; the abiotic and biotic transformation of free DDE molecules in solution in the sediment pore water, the biotic transformation of DDE adsorbed to soil colloidal particles types 1 and 2, the abiotic and microbial factors, the adsorption factors for the two adsorbed speciation forms and the persistence lifetimes of each speciation form. The 10 thermodynamic parameters include the initial adsorption speciation equilibrium concentration and the speciation partition coefficient for each speciation form, the adsorption equilibrium constant and the adsorption free energy for each adsorbed speciation form.
Conclusion
Applying the multi-phase pseudo-zero order rate law to interpret transformation kinetics of persistent organic pollutants like DDE, enables one to adequately compute the different kinetic and thermodynamic parameters thereby giving the full picture of how all the speciation forms are transformed in the environment.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data Availability
All data analyzed during this study are included in this article.
References
PPDB (AERU) (2022) Pesticide properties data base, research unit. University of Hertfordshire, UK
Kelce WR, Stone CR, Laws SC, Gray LE, Kemppainen JA, Wilson EM (1995) Persistent DDT metabolite p, p’–DDE is a potent androgen receptor antagonist. Nature 375:581–585. https://doi.org/10.1038/375581a0
Paranjape K, Gowariker V, Krishnamurthy VN, Gowariker S (2015) The Pesticide Encyclopedia. CABI, Wallingford, UK. https://doi.org/10.1108/RR-03-2015-0055
International Agency for Research on Cancer (IARC) (1991) Occupational exposure in insecticides application, and some pesticides. IARC Monographs on the evaluation of carcinogenic risks to humans, 53. IARC, Lyon
Wolff MS, Collman GW, Barrett JC, Huff J (1996) Breast cancer and environmental risk factors: epidemiological and experimental findings. Ann Rev Pharmacol Toxicol 36:573–596
Dunlap TR (1981) DDT: scientists, citizens and public policy. Princeton University Press, Princeton, New Jersey, USA
Beard J (2006) Australian rural health research collaboration, DDT and human health. Sci Total Environ 355(1–3):78–89
Ecobichon DJ (2001) Pesticide use in developing countries. Toxicology 160(1–3):27–33
UNEP Secretariat of the Stockholm Convention (2010) stockholm convention on persistent organic pollutants (POPs) text and annexes as amended in 2009. United Nations Environment Programme, Geneva
Colopy J (1995) Poisoning the developing world: the exportation of unregistered and severely restricted pesticides from the United States. UCLA J Environ Law Policy. https://doi.org/10.5070/L5132018871
Bottrell DG (1984) Government influence on pesticide use in developing countries. Int J Insect Sci 5:151–55
Wesseling C, McConnell R, Partanen T, Hogstedt C (1997) Agricultural pesticides use in developing countries: Health effects and research needs. Int J Health Serv 27(2):273–308
Atreya K, Sitaula BK, Johnsen FH, Bajra-Charya RM (2011) Continuing issues in the limitation of pesticide use in developing countries. J Agric Environ Ethics 24(1):49–62
Soulas G, Lagacherie B (2001) Modelling of microbial degradation of pesticides in soils, Biol Fertil. Soils 33:551–557. https://doi.org/10.1007/s003740100363
Zaranyika MF, Dzomba P (2019) Dissipation of chlortetracycline in the aquatic environment: characterization in terms of a generalized multi-phase pseudo-zero order rate law. Int J Chem Kinet 51:1–14
Zaranyika MF, Matimati E, Mushonga P (2020) Degradation kinetics of DDT in tropical soils: a proposed multi-phase zero order kinetic model that takes into account evaporation, hydrolysis, photolysis, microbial degradation and adsorption by soil particulates. Sci Afr 9:e00467
Zaranyika MF, Dzomba P (2022) Aquatic bioaccessibility of tetracycline antibiotics to higher Fauna: prediction based on the water-column/sediment partition coefficient. Sci Afr. https://doi.org/10.1016/j.sciaf.2022.e01113
Varca LM, Magallova ED (1994) Dissipation and degradation of DDT and DDE in philippine soil under field conditions. J Environ Sci Health Part B 29(1):25–36
FAO/IAEA Joint Division (1994) Agrochemicals and food section, international atomic energy agency, appraisal of overall programme accomplishments. J Environ Sci Health Part B 29(1):205–226
Dzomba P, Zaranyika MF (2022) Degradation of tetracycline in tropical river ecosystems: generation and dissipation of metabolites; kinetic and thermodynamic parameters. React Kinet Mech Catal. https://doi.org/10.1007/s11144-022-02249-z
Atkins PW, de Paula J (2006) Physical Chemistry, 8th edn. Oxford University Press, Great Britain
Acknowledgements
The authors continue to appreciate ANCAP and IPCs support to attend conferences where this paper was initially discussed. The comments were so helpful in writing the paper.
Funding
The authors do not receive any direct funding for the present study.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of Interest
The author declare that there are no conflicts of interest to declare.
Additional information
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zaranyika, M.F., Dzomba, P. Towards Complete Kinetic and Thermodynamic Description of the Degradation of Persistent Organic Pollutants in Soil Ecosystems on the Basis of the Multi-phase Pseudo-zero Order Rate Law: A case Study of DDE in Philippine Soil. Chemistry Africa 7, 421–427 (2024). https://doi.org/10.1007/s42250-023-00728-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s42250-023-00728-x