Selective degradation of endogenous organic metabolites in acidified fresh human urine using sulphate radical-based advanced oxidation

The metabolome of real human urine is highly complex. Many of the organic compounds in urine significantly influence treatment parameters such as energy demand and product purity when urine is treated in resource-oriented sanitation systems. In a study  published in Water Research, Ali Mehaidli and Prithvi Simha from our research group developed a method using heat-activated peroxydisulphate for the selective degradation of organic compounds in human urine.

Key Findings

• Optimal Conditions: The best conditions for peroxydisulphate activation in real urine were a dose of 60 mM, a temperature of 90°C, and a reaction time of 1 hour at a pH of 3.0. Under these conditions, over 90% of the peroxydisulphate was activated.
• Selective Degradation: More than 150 organic metabolites were degraded in real urine, with a significant reduction in chemical oxygen demand and total organic carbon, indicating effective degradation of complex organic molecules.
• Minimal Urea Loss: The process resulted in less than 10% loss of total nitrogen, with most of the urea remaining intact. This is crucial for maintaining the nutrient value of urine for recycling purposes.
• Chloride Oxidation: The treatment did not oxidise chloride, suggesting minimal risk of forming harmful chlorinated byproducts

Abstract: The human urine metabolome is complex, containing a wide range of organic metabolites that affect treatment of urine collected in resource-oriented sanitation systems. In this study, an advanced oxidation process involving heat-activated peroxydisulphate was used to selectively oxidise organic metabolites in urine over urea and chloride. Initial experiments evaluated optimal conditions (peroxydisulphate dose, temperature, time, pH) for activation of peroxydisulphate in unconcentrated, non-hydrolysed synthetic urine and real urine acidified to pH 3.0. Subsequent experiments determined the fate of 268 endogenous organic metabolites (OMs) and removal of COD from unconcentrated and concentrated real urine (80–90% mass reduced by evaporation). The results revealed >90% activation of 60 mM peroxydisulphate in real unconcentrated urine heated to 90 °C for 1 h, resulting in 43% ΣOMs degradation, 22% COD removal and 56% total organic carbon removal, while >94% of total nitrogen and >97% of urea in real unconcentrated urine were recovered. The mechanism of urea degradation was identified to be chemical hydrolysis to ammonia, with the rate constant for this reaction determined to be 1.9 × 10⁻⁶ s⁻¹ at pH 3.0 and 90 °C. Treating concentrated real urine resulted in similar removal of COD, ΣOMs degradation and total nitrogen loss as observed for unconcentrated urine, but with significantly higher chloride oxidation and chemical hydrolysis of urea. Targeted metabolomic analysis revealed that peroxydisulphate treatment degraded 157 organic metabolites in urine, of which 67 metabolites were degraded by >80%. The rate constant for the reaction of sulphate radicals with oxidisable endogenous organic metabolites in urine was estimated to exceed 10⁸ M⁻¹ s⁻¹. These metabolites were preferentially oxidised over chloride and urea in acidified, non-hydrolysed urine treated with peroxydisulphate. Overall, the findings support the development of emerging urine recycling technologies, including alkaline/acid dehydration and reverse osmosis, where the presence of endogenous organic urine metabolites significantly influences treatment parameters such as energy demand and product purity.

Mehaidli, A. P., Mandal, R., & Simha, P. (2024). Selective degradation of endogenous organic metabolites in acidified fresh human urine using sulphate radical-based advanced oxidation. Water Research, 121751.