Acid mine drainage (AMD) typically involves waters with low pH (pH 2-4) and high concentrations of Fe, SO4 and potentially toxic trace metals. Adsorption onto iron oxyhydroxides is the dominant mechanism controlling the transport and toxicity of trace metals in water bodies impacted by AMD. The purpose of this study was to apply the Diffuse Layer Model (DLM) to describe the adsorption of trace metals by iron oxyhydroxides from these systems, using synthetic iron oxyhydroxide minerals, ferrihydrite, pure acicular goethite, SO4-rich goethite prepared from FeSO4 oxidation and a synthetic schwertmannite.
The ferrihydrite adsorption of the trace metals Cu, Zn, Cd and Co from single sorbate systems was accurately described using the DLM with two surface site types (type-1 and type-2) having site densities of 0.005 and 0.2 mol (mol Fe)−1 respectively. The ferrihydrite adsorption of SO4 from single sorbate systems was accurately described using the DLM with adsorption on the type-2 sites. However, the enhanced adsorption of Cu, Zn, Cd and Co in the presence of SO4 was not predicted using adsorption constants derived from single sorbate systems. By including a neutral ternary complex with stoichiometry ≡Fe(2)OHMeSO4 (where ≡Fe(2)OH is a type-2 surface site and Me is the trace metal) the effect of SO4 on metal adsorption was accurately described for the range of Me, Fe and SO4 concentrations studied. The adsorption of Cu and Zn onto schwertmannite at total metal to iron ratios (MeT:Fe) up to 8 x 10−3 was almost identical to that predicted for ferrihydrite in the presence of 0.01 mol kg−1 SO4. To model the ferrihydrite adsorption of Pb from single sorbate systems a third higher affinity site (type-0) with a site density of 0.00035 mol (mol Fe)−1 was required. The effect of SO4 on Pb adsorption could only be modelled by including a neutral ternary complex on both the type 1 and type 2 sites in the case of Pb.
Metal adsorption onto a pure acicular goethite could be accurately described by the DLM with two surface site types. The type 2 site density that provided the best fit to the goethite adsorption data was 0.027 mol (mol Fe)−1 corresponding to 2.3 nm−2. The type-1 site density that provided the best fit to goethite adsorption of Cu, Pb and Cd was 0.00028 mol (mol Fe)−1 corresponding to 0.024 nm−1. For Zn adsorption on goethite the type-1 site density was significantly larger at 0.0015 mol (mol Fe)−1 corresponding to 0.13 nm−2. In all cases studied the presence of SO4 caused an increase in the extent of metal adsorption by goethite. This increased adsorption of metals in the presence of SO4 was accurately predicted by including ternary complex formation at both the high and low affinity adsorption sites.
For both ferrihydrite and goethite the values of adsorption constants for ternary complex formation (logKxMeTC) were related to the adsorption constant for metal adsorption in the absence of SO4 (logKxMeINT). This was evident from a plot of logKxMeTC as a function of logKxMeINT for all metals, which showed a linear relationship with slope of 0.69 and intercept of 8.03. This relationship suggests that the enhancement of metal adsorption on both oxyhydroxides due to SO4 occurs by the same process.
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