Modelling Cu, Zn, Cd and Pb Adsorption by Iron Oxyhydroxides in SO4-rich Systems Simulating Acid Mine Drainage

Abstract

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-2. 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.

When comparing Cu, Zn and Cd adsorption onto ferrihydrite and acicular goethite the effect of the larger goethite adsorption constants are approximately compensated for by the lower goethite site densities. Therefore the Cu, Cd and Zn adsorption isotherms on ferrihydrite and acicular goethite are fairly similar at low adsorption densities. In the case of Pb, the site densities and adsorption constants are both larger on ferrihydrite and there is a large difference between the ferrihydrite and acicular goethite adsorption isotherms.

Sulfate-rich goethite had considerably higher site densities, per mol of oxide, than the pure acicular goethite. Adsorption onto the sulfate-rich goethite could be modelled reasonably accurately using the parameters developed to model adsorption onto the pure acicular goethite but with a higher surface area and a higher ratio of type-1 to type 2 sites. In general, therefore, the parameters developed for pure goethite are apparently similar to those for the sulfate-rich goethite, but are not directly transferable. The difficulty in measuring the surface area of the highly aggregated sulfate-rich goethite makes comparisons between the two goethites more difficult.

The adsorption of Cu, Zn and Cd onto the SO4-rich goethite exceeds that of ferrihydrite because the higher adsorption constants of goethite are combined with the considerably higher site densities of the SO4-rich goethite compared to the acicular goethite. In contrast the higher site densities of the SO4-rich goethite does not completely compensate for the low logKINT values of Pb adsorption on goethite. Therefore SO4-rich goethite adsorption of Pb is lower than that of ferrihydrite.

When applied to literature data from AMD oxides the parameters derived in this thesis have significantly improved the ability of the DLM to predict trace metal adsorption in AMD systems, compared to using ferrihydrite as a proxy for all iron oxyhydroxides and adsorption data derived only from single sorbate systems.