Degradation kinetics of chlorpyrifos and diazinon in volcanic and non-volcanic soils: influence of cyclodextrins

The intensive use of insecticides such as chlorpyrifos (CPF) and diazinon (DZN) in the agricultural activities worldwide has produced contamination of soils and/or transport to non-target areas including their distribution to surface and groundwaters. Cyclodextrins (CDs) have been proposed as an alternative in remediation technologies based on the separation of contaminants from soils because they could allow a higher bioavailability for their degradation with a low environmental impact. In this work, the degradation pattern of CPF and DZN and the formation and dissipation of the major degradation products 3,5,6-trichloro-2-pyridinol (TCP) and 2-isopropyl-6-methyl-4-pyrimidinol (IMPH) was established in four agricultural volcanic and non-volcanic soils belonging to Andisol, Ultisol, and Mollisol orders. Both pesticides were highly adsorbed in these soils, consequently, with a greater probability of contaminating them. In contrast, the adsorption of their two main metabolites was low or null; therefore, they are potential groundwater contaminants. The degradation processes were studied in the natural and amended soils with beta-cyclodextrin (beta-CD) and methyl-beta-cyclodextrin (M beta-CD) for CPF and DZN, respectively. A slow degradation of CPF and DZN was obtained for volcanic soils with observable residues until the end of the incubation time (150-180 days). In Mollisols, the higher degradation rate of CPF was favored by the neutral to basic pH, and for DZN it was related to the lower adsorption and higher bioavailability. The amendment of soils with CDs produced slower degradation rates which led to a greater concentration of the compounds at the end of the incubation time. This effect was more pronounced for DZN. The exception was the Andisol, with no significant changes for both compounds regarding the unamended soil. No residues of TCP were observed for this soil in both conditions during the whole incubation time; nevertheless, the accumulation of TCP was significant in the Ultisol and Mollisols, but the concentrations were lower for the amended soils. The accumulation of IMPH was important in Mollisol amended soils; however, their residues were observed in the volcanic soils during the whole incubation period in the natural and amended soils. An important enhancement of the microbial activity occurred in the system beta-CD/CPF in Mollisols, without a more effective degradation of the insecticide. The opposite effect was observed in the system M beta-CD/DZN mainly in the oxidative activity in all soils. The higher degradation of DZN and IMPH in natural Mollisols was related to the higher hydrolytic and oxidative activities. The stability of the inclusion complexes formed could play an important role for explaining the results obtained with the amendments.