Long-term interaction of metals and phosphate with ferrihydrite in artificial seawater and implications for past and present environments

The FeIII hydroxide ferrihydrite (Fh) is highly reactive towards dissolved metals and other aqueous compounds. This reactivity suggests a possible role for Fh in environmental remediation and in controlling ambient concentrations of metals and nutrients in both modern and ancient aqueous environments. Though the reactivity of Fh towards a variety of aqueous compounds has been determined in previous studies, its reactivity under seawater-like conditions has not been systematically explored. Since solution chemistry can have a profound effect on the uptake of metals and oxyions through its effects on the surface chemistry of Fh and the speciation of metals in solution, the dearth of experiments under seawater-like conditions translates into a knowledge gap of metal-Fh interactions in natural marine systems. Furthermore, metal- and nutrient-Fh interactions have been investigated under dissimilar conditions, making a quantitative comparison of these interactions difficult. Lastly, the fate of the aqueous metals and nutrients taken up by Fh upon its aging has been examined in only a few studies and mostly for a duration up to ∼8 months. We bridged these gaps in a series of adsorption and co-precipitation experiments of various metals and phosphate with Fh, in seawater-analog solutions, at circumneutral pH (pH 7.5 and 8.0) and 25 °C. We quantified the effect of interaction with Fh on the aqueous concentrations of CdII, CoII, CrVI, CuII, MnII, MoVI, NiII, VV, UVI, ZnII, and phosphate (PO43−). The experimental results are provided as uptake percentages (quantified as the metal:Fe ratio in the solid phase relative to the metal:Fe ratio added) at different metal:Fe ratios and as a series of partition coefficients of the studied metals and PO43− between aqueous solution and Fh. Additionally, aging experiments of up to ∼4 years in duration were used to determine the potential effects of grain coarsening, surface modification and mineral transformation on the uptake of the metals and PO43−. Uptake of CrVI, MoVI and UVI was negligible in both the adsorption and co-precipitation experiments. Uptake of VV and PO43− by co-precipitation was as much as twice their uptake by adsorption, and we suggest that stabilization of colloidal Fh with a large surface area explains these findings. For CuII, NiII, CoII, MnII, and CdII differences in uptake between the co-precipitation and adsorption experiments were less pronounced, and we ascribe these differences to relatively minor inc