Arsenate co-precipitation with Fe(II) oxidation products and retention or release during precipitate aging.

Abstract

The co-precipitation of arsenate (As(V)) with Fe(III)-precipitates is of great importance in water treatment and critically affects the fate of As in environmental systems. We studied the effects of dissolved phosphate (P; 0-1 mM), silicate (Si; 0 or 0.5 mM) and Ca (0, 0.5 and 4 mM) on the sequestration of 7 μM As(V) by Fe(III)-precipitates formed by the oxidation of 0.5 mM Fe(II) in aerated bicarbonate-buffered solutions with an initial pH of 7.0 as well as the retention or release of As(V) after precipitate aging for 30 d at 40 °C. Dissolved As(V) concentrations in fresh precipitate suspensions greatly varied as a function of the initial dissolved P/Fe ratio ((P/Fe)init) and the concentrations of Ca and Si. Limited As(V) removal was observed at (P/Fe)init that exceeded the critical ratio (P/Fe)crit above which exclusively (Ca-)Fe(III)-phosphate forms. Effective As(V) removal was observed at (P/Fe)init < (P/Fe)crit, where initial formation of (Ca-)Fe(III)-phosphate is followed by the formation of Si-ferrihydrite in Si-containing electrolytes and of poorly-crystalline lepidocrocite and hydrous ferric oxide in the Si-free electrolytes. The retention of As(V) and P by fresh Fe(III)-precipitates was most effective in systems containing both Ca and Si. In the Si- and Ca-free electrolytes at (P/Fe)init of ∼0.2-0.6, the rapid onset of precipitate aging with conversion of Fe(III)-phosphate to ferrihydrite resulted in a substantial remobilization of As(V) (up to 55% of initially precipitated As(V)). Ca reduced As remobilization during aging by stabilizing Ca-Fe(III)-phosphate and promoting Ca-phosphate formation, and Si by stabilizing Si-ferrihydrite against transformation. Consequently, also after aging, the lowest dissolved As(V) and P fractions were observed in precipitate suspensions containing both Ca and Si.