A predictive model of the effects of aging on cobalt fate and behavior in soil

Metal toxicity to terrestrial organisms is influenced by a number of factors including the organisms affected and ecotoxicological end points, soil properties, aging processes, and metal speciation. The toxicity of metals added to soils can change over time through aging processes, which may reduce availability of metals via diffusion into micropores, incorporation into crystal lattices, or Ostwald ripening of precipitates. Metals which have been in contact with soil for longer periods are less able to exchange with the soil solution, rendering them less available to soil biota. The objective of this work was to investigate and model the effects of long- term aging on cobalt(ll) (Co2+) (isotopic) exchangeability and potential bioavailability in a wide range of soils, as this is the form of Co commonly used in ecotoxicological investigations. After addition to soil, added soluble Co(ll) rapidly partitioned to the soil solid phase, and in alkaline soils a large percentage of this surface-bound Co was fixed through aging reactions in forms that were no longer in equilibrium with the soil solution Co. Analyses indicated that soil pH and incubation time were the most important factors affecting Co(II) aging. The rate and extent of aging of added Co(ll) could be accurately predicted across all soils using a semi-mechanistic model that suggested Co was fixed through reactions that we postulate were related to surface oxidation/precipitation/ nucleation as driven by hydrolysis reactions at the surface of soil minerals.