title: Direct electrochemical oxidation of ammonia on graphite as a treatment option for stored source-separated urine.
abstract: Electrolysis can be a viable technology for ammonia removal from source-separated urine. Compared to biological nitrogen removal, electrolysis is more robust and is highly amenable to automation, which makes it especially attractive for on-site reactors. In electrolytic wastewater treatment, ammonia is usually removed by indirect oxidation through active chlorine which is produced in-situ at elevated anode potentials. However, the evolution of chlorine can lead to the formation of chlorate, perchlorate, chlorinated organic by-products and chloramines that are toxic. This study focuses on using direct ammonia oxidation on graphite at low anode potentials in order to overcome the formation of toxic by-products. With the aid of cyclic voltammetry, we demonstrated that graphite is active for direct ammonia oxidation without concomitant chlorine formation if the anode potential is between 1.1 and 1.6 V vs. SHE (standard hydrogen electrode). A comparison of potentiostatic bulk electrolysis experiments in synthetic stored urine with and without chloride confirmed that ammonia was removed exclusively by continuous direct oxidation. Direct oxidation required high pH values (pH > 9) because free ammonia was the actual reactant. In real stored urine (pH = 9.0), an ammonia removal rate of 2.9 ± 0.3 gN·m(-2)·d(-1) was achieved and the specific energy demand was 42 Wh·gN(-1) at an anode potential of 1.31 V vs. SHE. The measurements of chlorate and perchlorate as well as selected chlorinated organic by-products confirmed that no chlorinated by-products were formed in real urine. Electrode corrosion through graphite exfoliation was prevented and the surface was not poisoned by intermediate oxidation products. We conclude that direct ammonia oxidation on graphite electrodes is a treatment option for source-separated urine with three major advantages: The formation of chlorinated by-products is prevented, less energy is consumed than in indirect ammonia oxidation and readily available and cheap graphite can be used as the electrode material.
authors.affiliation: Eawag, Swiss Federal Institute of Aquatic Science and Technology, Überlandstrasse 133, 8600 Dübendorf, Switzerland.
authors.forename: Hanspeter
authors.initials: H
authors.lastname: Zöllig
authors.affiliation: Eawag, Swiss Federal Institute of Aquatic Science and Technology, Überlandstrasse 133, 8600 Dübendorf, Switzerland.
authors.forename: Cristina
authors.initials: C
authors.lastname: Fritzsche
authors.affiliation: Eawag, Swiss Federal Institute of Aquatic Science and Technology, Überlandstrasse 133, 8600 Dübendorf, Switzerland.
authors.forename: Eberhard
authors.initials: E
authors.lastname: Morgenroth
authors.affiliation: Eawag, Swiss Federal Institute of Aquatic Science and Technology, Überlandstrasse 133, 8600 Dübendorf, Switzerland. Electronic address: kai.udert@eawag.ch.
authors.forename: Kai M
authors.initials: KM
authors.lastname: Udert
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D004560:Electricity; D055664:Electrochemical Techniques / Q000379:methods*; D004566:Electrodes; D004572:Electrolysis; D004573:Electrolytes / Q000737:chemistry; D005260:Female; D006108:Graphite / Q000737:chemistry*; D006801:Humans; D010084:Oxidation-Reduction; D014556:Urine / Q000737:chemistry*
chemical_list: D004573:Electrolytes; D000641:Ammonia; D006108:Graphite
keywords: Chlorinated by-products; Decentralized; Nitrogen removal; NoMix technology; On-site; Potential controlled electrolysis