Oxidation of Pharmaceuticals by Ferrate(VI) in Hydrolyzed Urine: Effects of Major Inorganic Constituents

Destruction of pharmaceuticals excreted in urine can be an efficient approach to eliminate these environmental pollutants. However, urine contains high concentrations of chloride, ammonium, and bicarbonate, which may hinder treatment processes. This study evaluated the application of ferrate(VI) (Fe^VIO₄^2-, Fe(VI)) to oxidize pharmaceuticals (carbamazepine (CBZ), naproxen (NAP), trimethoprim (TMP), and sulfonamide antibiotics (SAs)) in synthetic hydrolyzed human urine and uncovered new effects from urine's major inorganic constituents. Chloride slightly decreased pharmaceuticals' removal rate by Fe(VI) due to the ionic strength effect. Ammonium (0.5 M) in undiluted hydrolyzed urine posed a strong scavenging effect, but lower concentrations (≤0.25 M) of ammonium enhanced the pharmaceuticals' degradation by 300 μM Fe(VI), likely due to the reactive ammonium complex form of Fe(V)/Fe(IV). For the first time, bicarbonate was found to significantly promote the oxidation of aniline-containing SAs by Fe(VI) and alter the reaction stoichiometry of Fe(VI) and SA from 4:1 to 3:1. In depth investigation indicated that bicarbonate not only changed the Fe(VI)/SA complexation ratio from 1:2 to 1:1 but provided a stabilizing effect for Fe(V) intermediate formed in situ, enabling its degradation of SAs. Overall, the results of this study suggested that Fe(VI) is a promising oxidant for the removal of pharmaceuticals in hydrolyzed urine.