Formation and Stability of Ni−Al Hydroxide Phases in Soils

The formation of mixed metal−aluminum hydroxide surface precipitates is a potentially significant uptake route for trace metals (including Co, Ni, and Zn) in environmental systems. This paper investigates the effect of mixed Ni−Al hydroxide precipitate formation and aging on Ni solubility and bioavailability in laboratory contaminated soils. Two Delaware agricultural soils were reacted with a 3 mM Ni solution for 12 months at pH’s above and below the threshold for mixed Ni−Al hydroxide formation. Ni speciation was determined at 1, 6, and 12 months using X-ray absorption spectroscopy (XAS). Precipitate solubility was examined through desorption experiments using HNO3 and EDTA as desorbing agents, whereas metal bioavailability was assessed using a Ni-specific bacterial biosensor. For both soils, the formation of Ni−Al hydroxide surface precipitates resulted in a reduction in the fraction of desorbed and bioavailable Ni. However, precipitate dissolution was greater, particularly with EDTA, than in published studies on isolated soil clay fractions, and less affected by aging processes. These results suggest that mixed Ni−Al hydroxide phases forming in real world environments may be both longer-lasting and more susceptible to ligand-promoted dissolution than previously expected.