Colloidal and solid phase partitioning between ferrihydrite, humic acid and copper coprecipitates

Our understanding of the interactions between Fe oxides, humic acids (C), and Cu precipitation products in the environment are limited by our ability to measure specific forms and chemical interactions. Here, we examine the effect of solution pH, Fe:C molar ratio from 1:0 to 1:3, and Cu concentration on dissolved and colloidal Cu concentrations after sorption (SOR) or coprecipitation (CPT) reactions. This included specifically measuring the colloidal phases formed using asymmetrical flow field flow fractionation coupled to a total organic carbon analyzer and an inductively coupled plasma mass spectrometer. In the case of 1:0 Fe:C reactions, more Cu was associated with bulk solids and colloidal solids in CPT reaction products, particularly at pH 5 and 6. As C content increased, precipitation reactions led to more Cu retained in the bulk solid phase at lower pH, but more in the dissolved and colloidal phase at higher pH. Of the colloids formed at pH 7, about 10% of the dissolved Cu is present as Fe–C–Cu ternary phases, with the remainder as Cu–C or inorganic Cu phases, yet at pH 6, only Fe–Cu colloids were observed. Applying an additivity approach while using a NICA-Donnan C complexation model combined with a ferrihydrite surface complexation model, the model often predicts higher than observed dissolved Cu in CPT reactions with no C present, but lower than observed dissolved Cu with C present. In applying the model specifically to colloidal phases, much lower concentrations of colloid bound Cu is predicted than observed in the 1:0 Fe:C scenario, but as C content increases, more colloidal Cu is predicted than observed. Given the availability and lability of Cu in environmental systems is assumed to correspond to dissolved Cu, this work notes some differences in the dissolved and colloidal phases formed in different contexts.