Adsorption and desorption characteristics of arsenic in calcareous soils as a function of time; equilibrium and thermodynamic study.

Irrigation of carbonate-rich agricultural soils with arsenic (As)-contaminated water leads to the accumulation of As in these soils. In this regard, there is an opportunity to adsorb and fix the As in soil and decrease the As transportation to the plants and subsequently the human food chain. So, the present study aimed to investigate the adsorption-desorption characteristics of As in calcareous soils and the potential of As fixation over time. First, to achieve this purpose, 53 soil samples were gathered from the study site and after the laboratory analysis, the soils were categorized into four groups based on their physicochemical properties. Then, four representative samples of these groups were selected, namely soil 1, soil 2, soil 3, and soil 4. Afterward, the As adsorption-desorption was investigated in a lab-scale batch experiment. Next, the effect of age was assessed by incubating the As-adsorbed soils for 60 days, and to study the impact of temperature, the adsorption was performed at four temperature levels (10, 20, 30, and 40 °C). Finally, the isotherm models were fitted to experimental data, and the amount of loosely and tightly held As was quantified. Results revealed that the As adsorption isotherms were L-type, in which As adsorption increased with the increase of As loading. The double-site Langmuir (DSL) estimated that a limited amount of As was adsorbed on high-energy surfaces and a large amount of As was adsorbed on low-energy surfaces. Desorption results showed that a significant amount of As desorbed immediately; however, the desorption significantly decreased with the increase of age, especially at low equilibrium concentrations. By aging the loosely held As transformed into non-labile forms so that in soils 1, 2, 3, and 4, the fraction of As adsorbed on high-energy surfaces increased from 72.5, 93.2, 63.2, and 123 mg/kg to 167, 141, 70.6, and 196 mg/kg, respectively, and the fraction of As adsorbed on low-energy surfaces decreased from 397, 256, 202, and 317 mg/kg to 182, 238, 173, and 172 mg/kg, respectively (after aging for 60 days). Aging proved to be a promising solution for decreasing As transport into the human food chain and could be employed for crops with longer irrigation cycles. ΔH values were positive and varied from 9.26 to 13.0 kJ/mol, confirming the endothermic nature of adsorption. ΔG values were negative and varied from - 18.8 to - 22.8 kJ/mol at all temperatures, demonstrating the spontaneous nature of adsorption.