Chlorination byproducts (CBPs) are harmful to human health and the environment. Their formation in chlorine mediated electro-oxidation is a concern for electrochemical urine treatment. We investigated the formation of chlorate, perchlorate, and organic chlorination byproducts (OCBPs) during galvanostatic (10, 15, 20 mA · cm(-2)) electro-oxidation of urine on boron-doped diamond (BDD) and thermally decomposed iridium oxide film (TDIROF) anodes. In the beginning of the batch experiments, the production of perchlorate was prevented by competing active chlorine and chlorate formation as well as by direct oxidation of organic substances. Perchlorate was only formed at higher specific charges (>17 Ah · L(-1) on BDD and >29 Ah · L(-1) on TDIROF) resulting in chlorate and perchlorate being the dominant CBPs (>90% of initial chloride). BDD produced mainly short chained OCBPs (dichloromethane, trichloromethane, and tetrachloromethane), whereas longer chained OCBPs (1,2-dichloropropane and 1,2-dichloroethane) were more frequently found on TDIROF. The OCBPs were primarily eliminated by electrochemical stripping: On BDD, this pathway accounted for 40% (dichloromethane) to 100% (tetrachloromethane) and on TDIROF for 90% (1,2-dichloroethane) to 100% (trichloromethane) of what was produced. A post-treatment of the liquid as well as the gas phase should be foreseen if CBP formation cannot be prevented by eliminating chloride or organic substances in a pretreatment.

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.

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aThe separate collection and treatment of urine allows for an environmentally friendly and cost-efficient management of the nutrients contained in urine. The primary goal should be to recover all these nutrients. However, in some cases it will be economically or ecologically more sensitive to recover only the phosphorus, while nitrogen is removed together with organic substances (measured as chemical oxygen demand, COD) and pathogens. In this study, we investigated the use of galvanostatic electrolysis for the removal of nitrogen and COD from real stored urine. Non-active type boron-doped diamond (BDD) and active type thermally decomposed iridium oxide film (TDIROF) anodes were evaluated using batch experiments. On both anodes, ammonia was exclusively removed by indirect oxidation with active chlorine (AC: Cl 2 , HClO, and ClO ). It can be concluded that BDD and TDIROF anodes could be combined in series for a fast, complete, and more energy efficient electrochemical urine treatment: COD could be removed on BDD before the residual ammonia would be removed on TDIROF.

In recent years, a large number of urine-diverting dehydration toilets (UDDTs) have been installed in eThekwini to ensure access to adequate sanitation. The initial purpose of these toilets was to facilitate faeces drying, while the urine was diverted into a soak pit. This practice can lead to environmental pollution, since urine contains high amounts of nutrients. Instead of polluting the environment, these nutrients should be recovered and used as fertiliser. In 2010 the international and transdisciplinary research project VUNA was initiated in order to explore technologies and management methods for better urine management in eThekwini. Three treatment technologies have been chosen for the VUNA project. The first is struvite precipitation, a technology which has already been tested in multiple projects on urine treatment. Struvite precipitation is a simple and fast process for phosphorus recovery. Other nutrients, such as nitrogen and potassium, remain in the effluent and pathogens are not completely inactivated. Therefore, struvite precipitation has to be combined with other treatment processes to prevent environmental pollution and hygiene risks. The second process is a combination of nitrification and distillation. This process combination is more complex than struvite precipitation, but it recovers all nutrients in one concentrated solution, ensures safe sanitisation and produces only distilled water and a small amount of sludge as by-products. The third process is electrolysis. This process could be used for very small on-site reactors, because conversion rates are high and the operation is simple, as long as appropriate electrodes and voltages are used. However, nitrogen is removed and not recovered and chlorinated by-products are formed, which can be hazardous for human health. While urine electrolysis requires further research in the laboratory, struvite precipitation and nitrification/distillation have already been operated at pilot scale.