Selective oxidation of pharmaceuticals and suppression of perchlorate formation during electrolysis of fresh human urine.

Urine comprises only a small (~1%) volumetric fraction of municipal wastewater, but represents a dominant source of pharmaceuticals, many of which may pass through conventional wastewater treatment and pose risks to aquatic ecosystems. Point-source treatment of source-separated urine presents a unique opportunity to degrade pharmaceuticals before dilution with wastewater, and electrochemical advanced oxidation processes are one increasingly investigated option. However, they often lead to the formation of oxidation byproducts including chlorate, perchlorate at very high concentrations. Here, we show that the high urea content of fresh human urine suppresses the formation of oxychlorides by inhibiting formation of HOCl/OCl during electrolysis, while still enabling pharmaceutical degradation due to the slow rate of urea oxidation by OH. This results in improved performance compared to equivalent treatment of hydrolyzed aged urine. This electrochemical oxidation scheme is shown to degrade the model contaminants cyclophosphamide and sulfamethoxazole with surface-area-to-volume-normalized pseudo-first-order rate constants greater than 0.08 cm/min in authentic fresh human urine. It results in ~100 × decrease in pharmaceutical concentrations in 2 h while generating ~1000 × lower oxychloride byproduct concentrations in synthetic fresh urine than synthetic hydrolyzed aged urine matrixes. Importantly, this proof-of-principle shows that simple and safe electrochemical methods can be used for point-source-remediation of pharmaceuticals in fresh human urine (before storage and hydrolysis), without formation of significant oxychloride byproducts.