Sulfate enhances the adsorption and retention of Cu(II) and Zn(II) to dispersed and aggregated iron oxyhydroxide nanoparticles

The adsorption and retention of metal ions to nanoscale iron (hydr)oxides in aqueous systems is significantly influenced by prevailing environmental conditions. We examined the influence of sulfate, the second most common anion in seawater that is present in many other natural aquatic systems, on the adsorption and retention of Cu(II) and Zn(II) to synthetic iron oxyhydroxide nanoparticles (NPs) and their aggregates. Batch uptake experiments with monodisperse NPs and NPs aggregated by changes in pH, ionic strength, and temperature were conducted over sulfate concentrations ranging from 0 to 0.30 M. The introduction of 0.03 M sulfate significantly increased the initial adsorption and retention of Zn(II) and Cu(II) compared to sulfate -free conditions; with increasing sulfate >0.03 M, Zn(II) retention continuously increased, while Cu(II) retention was considerably more variable but increased slightly. NP aggregation, when induced by pH and ionic strength, was positively correlated with metal ion retention, while aggregation temperature was negatively correlated with both adsorption and retention. Aqueous geochemical modeling indicated that Zn(II) readily complexes with sulfate to form ZnSO4 (aq), but that stable aqueous CuSO(4 )species are uncommon. EXAFS spectroscopic analysis suggests structural incorporation of Zn(II) and Zn(II)-sulfate ternary surface complexation, while Cu(II) primarily forms inner-sphere bidentate surface complexes. Collectively, the effects of sulfate in both reducing surface charge repulsion, initiating ternary surface complexation, and enabling structural incorporation aid to enhance both metal adsorption and retention to iron oxyhydroxide NPs and their aggregates.