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This study aimed to investigate whether separating organics depletion from nitrification increases the overall performance of urine nitrification. Separate organics depletion was facilitated with membrane aerated biofilm reactors (MABRs). The high pH and ammonia concentration in stored urine inhibited nitrification in the first stage and therewith allowed the separation of organics depletion from nitrification. An organics removal of 70 % was achieved at organic loading rates in the influent of 3.7 g COD d -1 m -2 . Organics depletion in a continuous flow stirred tank reactor (CSTR) for organics depletion led to ammonia stripping through diffused aeration of up to 13 %. Using an MABR, diffusion into the lumen amounted for 4 % ammonia loss only. In the MABR, headspace volume and therefore ammonia loss through the headspace was negligible. By aerating the downstream MABR for nitrification with the off-gas of the MABR for organics depletion, 96 % of the ammonia stripped in the first stage could be recovered in the second stage, so that the overall ammonia loss was negligibly low. Nitrification of the organics-depleted urine was studied in MABRs, CSTRs, and sequencing batch reactors in fed batch mode (FBRs), the latter two operated with suspended biomass. The experiments demonstrated that upstream organics depletion can double the nitrification rate. In a laboratory-scale MABR, nitrification rates were recorded of up to 830 mg N L -1 d -1 (3.1 g N m -2 d -1 ) with ambient air and over 1500 mg N L -1 d -1 (6.7 g N m -2 d -1 ) with oxygen-enriched air. Experiments with a laboratory-scale MABR showed that increasing operational parameters such as pH, recirculation flow, scouring frequency, and oxygen content increased the nitrification rate. The nitrification in the MABR was robust even at high pH setpoints of 6.9 and was robust against process failures arising from operational mistakes. The hydraulic retention time (HRT) required for nitrification was only 1 to 2 days. With the preceding organics depletion, the HRT for our system requires 2 to 3 days in total, whereas a combined activated sludge system requires 4 to 8 days. The N 2 O concentration in the off-gas increases with increasing nitrification rates; however, the N 2 O emission factor was 2.8 % on average and independent of nitrification rates. These results indicate that the MABR technology has a high potential for efficient and robust production of ammonium nitrate from source-separated urine., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Kai M. Udert reports a relationship with VunaNexus that includes: board membership and travel reimbursement. VunaNexus uses biological and physical processes for nutrient recovery from urine. The study was not influenced by the relationship of Kai M. Udert with VunaNexus. Aurea Heusser and Kai M. Udert have a patent pending to Eawag. The patent includes the separate removal of organics from source-separated urine, intermediate pharmaceutical removal by adsorption and subsequent nitrification. The other authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Separate collection and treatment of urine optimizes nutrient recovery and enhances micropollutant removal from municipal wastewater. One typical urine treatment train includes nutrient recovery in three biological processes: anaerobic storage, followed by aerobic organics degradation concurrently with nitrification. These are usually followed by activated carbon adsorption to remove micropollutants. However, removing micropollutants prior to nitrification would protect nitrifiers from potential inhibition by pharmaceuticals. In addition, combining simplified biological treatment with activated carbon adsorption could offer a cheap and robust process for removing micropollutants where nutrient recovery is not the first priority, as a partial loss of ammonia occurs without nitrification. In this study, we investigated whether activated carbon adsorption could also take place between the three biological treatment steps. We tested the effectiveness of micropollutant removal with activated carbon after each biological treatment step by conducting experiments with anaerobically stored urine, organics-depleted urine, and nitrified urine. The urine solutions were spiked with 19 pharmaceuticals: amisulpride, atenolol, atenolol acid, candesartan, carbamazepine, citalopram, clarithromycin, darunavir, diclofenac, emtricitabine, fexofenadine, hydrochlorothiazide, irbesartan, lidocaine, metoprolol, N 4 -acetylsulfamethoxazole, sulfamethoxazole, trimethoprim, venlafaxine, and two artificial sweeteners, acesulfame and sucralose. Batch experiments were conducted with powdered activated carbon (PAC) to determine how much activated carbon achieve which degree of micropollutant removal and how organics, pH, and speciation change from ammonium to nitrate influence adsorption. Micropollutant removal was also tested in granular activated carbon (GAC) columns, which is the preferred technology for micropollutant removal from urine. The carbon usage rates (CUR) per person were lower for all urine solutions than for municipal wastewater. The results showed that organics depletion would be needed when micropollutant removal was the sole aim of urine treatment, as the degradation of easily biodegradable organics prevented clogging of GAC columns. However, CUR did hardly improve with organics-depleted urine compared to stored urine. The lowest CUR was achieved with nitrified urine. This resulted from the additional organics removal during nitrification and not the lower pH or the partial conversion of ammonium to nitrate. In addition, we showed that the relative pharmaceutical removal in all solutions was independent of the initial pharmaceutical concentration unless the background organics matrix changed considerably. We conclude that removal of micropollutants in GAC columns from organics-depleted urine can be performed without clogging, but with the drawback of a higher carbon usage compared to removal from nitrified urine., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Kai M. Udert reports a relationship with VunaNexus that includes: board membership and travel reimbursement. Aurea Heusser and Kai M. Udert have a patent pending to Eawag. The patent includes the separate removal of organics from source-separated urine but is only marginally relevant for the publication. The other authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Sensor drift is commonly observed across engineering disciplines, particularly in harsh media such as wastewater. In this study, a novel stabilizing controller for nitrification of high strength ammonia solutions is designed based on online signal derivatives. The controller uses the derivative of a drifting nitrite signal to determine if nitrite-oxidizing bacteria (NOB) are substrate limited or substrate inhibited. To ensure a meaningful interpretation of the derivative signal, the process is excited in a cyclic manner by repeatedly exposing the NOB to substrate-limited and substrate-inhibited conditions. The resulting control system successfully prevented nitrite accumulations for a period of 72 days in a laboratory-scale reactor. Slow disturbances in the form of feed composition changes and temperature changes were successfully handled by the controller while short-term temperature disturbances are shown to pose a challenge to the current version of this controller. Most importantly, we demonstrate that drift-tolerant control for the purpose of process stabilization can be achieved without sensor redundancy by combining deliberate input excitation, qualitative trend analysis, and coarse process knowledge., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Ammonia recovery from urine avoids the need for nitrogen removal through nitrification/denitrification and re-synthesis of ammonia (NH 3 ) via the Haber-Bosch process. Previously, we coupled an alkalifying electrochemical cell to a stripping column, and achieved competitive nitrogen removal and energy efficiencies using only electricity as input, compared to other technologies such as conventional column stripping with air. Direct liquid-liquid extraction with a hydrophobic gas membrane could be an alternative to increase nitrogen recovery from urine into the absorbent while minimizing energy requirements, as well as ensuring microbial and micropollutant retention. Here we compared a column with a membrane stripping reactor, each coupled to an electrochemical cell, fed with source-separated urine and operated at 20 A m -2 . Both systems achieved similar nitrogen removal rates, 0.34 ± 0.21 and 0.35 ± 0.08 mol N L -1 d -1 , and removal efficiencies, 45.1 ± 18.4 and 49.0 ± 9.3%, for the column and membrane reactor, respectively. The membrane reactor improved nitrogen recovery to 0.27 ± 0.09 mol N L -1 d -1 (38.7 ± 13.5%) while lowering the operational (electrochemical and pumping) energy to 6.5 kWh e kg N -1 recovered, compared to the column reactor, which reached 0.15 ± 0.06 mol N L -1 d -1 (17.2 ± 8.1%) at 13.8 kWh e kg N -1 . Increased cell concentrations of an autofluorescent E. coli MG1655 + prpsM spiked in the urine influent were observed in the absorbent of the column stripping reactor after 24 h, but not for the membrane stripping reactor. None of six selected micropollutants spiked in the urine were found in the absorbent of both technologies. Overall, the membrane stripping reactor is preferred as it improved nitrogen recovery with less energy input and generated an E. coli- and micropollutant-free product for potential safe reuse. Nitrogen removal rate and efficiency can be further optimized by increasing the NH 3 vapor pressure gradient and/or membrane surface area., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this study, we investigated the prevention of enzymatic urea hydrolysis in fresh urine by increasing the pH with calcium hydroxide (Ca(OH)2) powder. The amount of Ca(OH)2 dissolving in fresh urine depends significantly on the composition of the urine. The different urine compositions used in our simulations showed that between 4.3 and 5.8 g Ca(OH)2 dissolved in 1 L of urine at 25 °C. At this temperature, the pH at saturation is 12.5 and is far above the pH of 11, which we identified as the upper limit for enzymatic urea hydrolysis. However, temperature has a strong effect on the saturation pH, with higher values being achieved at lower temperatures. Based on our results, we recommend a dosage of 10 g Ca(OH)2 L(-1) of fresh urine to ensure solid Ca(OH)2 always remains in the urine reactor which ensures sufficiently high pH values. Besides providing sufficient Ca(OH)2, the temperature has to be kept in a certain range to prevent chemical urea hydrolysis. At temperatures below 14 °C, the saturation pH is higher than 13, which favors chemical urea hydrolysis. We chose a precautionary upper temperature of 40 °C because the rate of chemical urea hydrolysis increases at higher temperatures but this should be confirmed with kinetic studies. By considering the boundaries for pH and temperature developed in this study, urine can be stabilized effectively with Ca(OH)2 thereby simplifying later treatment processes or making direct use easier., (Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Monitoring of nitrite is essential for an immediate response and prevention of irreversible failure of decentralized biological urine nitrification reactors. Although a few sensors are available for nitrite measurement, none of them are suitable for applications in which both nitrite and nitrate are present in very high concentrations. Such is the case in collected source-separated urine, stabilized by nitrification for long-term storage. Ultraviolet (UV) spectrophotometry in combination with chemometrics is a promising option for monitoring of nitrite. In this study, an immersible in situ UV sensor is investigated for the first time so to establish a relationship between UV absorbance spectra and nitrite concentrations in nitrified urine. The study focuses on the effects of suspended particles and saturation on the absorbance spectra and the chemometric model performance. Detailed analysis indicates that suspended particles in nitrified urine have a negligible effect on nitrite estimation, concluding that sample filtration is not necessary as pretreatment. In contrast, saturation due to very high concentrations affects the model performance severely, suggesting dilution as an essential sample preparation step. However, this can also be mitigated by simple removal of the saturated, lower end of the UV absorbance spectra, and extraction of information from the secondary, weaker nitrite absorbance peak. This approach allows for estimation of nitrite with a simple chemometric model and without sample dilution. These results are promising for a practical application of the UV sensor as an in situ nitrite measurement in a urine nitrification reactor given the exceptional quality of the nitrite estimates in comparison to previous studies., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In eThekwini, South Africa, the production of agricultural fertilizers from human urine collected from urine-diverting dry toilets is being evaluated at a municipality scale as a way to help finance a decentralized, dry sanitation system. The present study aimed to assess a range of human and environmental health hazards in source-separated urine, which was presumed to be contaminated with feces, by evaluating the presence of human pathogens, pharmaceuticals, and an antibiotic resistance gene. Composite urine samples from households enrolled in a urine collection trial were obtained from urine storage tanks installed in three regions of eThekwini. Polymerase chain reaction (PCR) assays targeted 9 viral and 10 bacterial human pathogens transmitted by the fecal-oral route. The most frequently detected viral pathogens were JC polyomavirus, rotavirus, and human adenovirus in 100%, 34% and 31% of samples, respectively. Aeromonas spp. and Shigella spp. were frequently detected gram negative bacteria, in 94% and 61% of samples, respectively. The gram positive bacterium, Clostridium perfringens, which is known to survive for extended times in urine, was found in 72% of samples. A screening of 41 trace organic compounds in the urine facilitated selection of 12 priority pharmaceuticals for further evaluation. The antibiotics sulfamethoxazole and trimethoprim, which are frequently prescribed as prophylaxis for HIV-positive patients, were detected in 95% and 85% of samples, reaching maximum concentrations of 6800 μg/L and 1280 μg/L, respectively. The antiretroviral drug emtricitabine was also detected in 40% of urine samples. A sulfonamide antibiotic resistance gene (sul1) was detected in 100% of urine samples. By coupling analysis of pathogens and pharmaceuticals in geographically dispersed samples in eThekwini, this study reveals a range of human and environmental health hazards in urine intended for fertilizer production. Collection of urine offers the benefit of sequestering contaminants from environmental release and allows for targeted treatment of potential health hazards prior to agricultural application. The efficacy of pathogen and pharmaceutical inactivation, transformation or removal during urine nutrient recovery processes is thus briefly reviewed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In wastewater treatment, the rate of ammonia oxidation decreases with pH and stops very often slightly below a pH of 6. Free ammonia (NH3) limitation, inhibition by nitrous acid (HNO2), limitation by inorganic carbon or direct effect of high proton concentrations have been proposed to cause the rate decrease with pH as well as the cessation of ammonia oxidation. In this study, we compare an exponential pH term common for food microbiology with conventionally applied rate laws based on Monod-type kinetics for NH3 limitation and non-competitive HNO2 inhibition as well as sigmoidal pH functions to model the low pH limit of ammonia oxidizing bacteria (AOB). For this purpose we conducted well controlled batch experiments which were then simulated with a computer model. The results showed that kinetics based on NH3 limitation and HNO2 inhibition can explain the rate decrease of ammonia oxidation between pH 7 and 6, but fail in predicting the pH limit of Nitrosomonas eutropha at pH 5.4 and rates close to that limit. This is where the exponential pH term becomes important: this term decreases the rate of ammonia oxidation to zero, as the pH limit approaches. Previously proposed sigmoidal pH functions that affect large pH regions, however, led to an overestimation of the pH effect and could therefore not be applied successfully. We show that the proposed exponential pH term can be explained quantitatively with thermodynamic principles: at low pH values, the energy available from the proton motive force is too small for the NADH production in Nitrosomonas eutropha and related AOB causing an energy limited state of the bacterial cell. Hence, energy limitation and not inhibition or limitation of enzymes is responsible for the cessation of the AOB activity at low pH values., (Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The nitritation/anammox process has been mainly applied to high-strength nitrogenous wastewaters with very low biodegradable organic carbon content (<0.5 g COD∙g N(-1)). However, several wastewaters have biodegradable organic carbon to nitrogen (COD/N) ratios between 0.5 and 1.7 g COD∙g N(-1) and thus, contain elevated amounts of organic carbon but not enough for heterotrophic denitrification. In this study, the influence of elevated COD/N ratios was studied on a nitritation/anammox process with suspended sludge. In a step-wise manner, the influent COD/N ratio was increased to 1.4 g COD∙g N(-1) by supplementing digester supernatant with acetate. The increasing availability of COD led to an increase of the nitrogen removal efficiency from around 85% with pure digester supernatant to >95% with added acetate while the nitrogen elimination rate stayed constant (275 ± 40 mg N∙L(-1)∙d(-1)). Anammox activity and abundance of anammox bacteria (AMX) were strongly correlated, and with increasing influent COD/N ratio both decreased steadily. At the same time, heterotrophic denitrification with nitrite and the activity of ammonia oxidising bacteria (AOB) gradually increased. Simultaneously, the sludge retention time (SRT) decreased significantly with increasing COD loading to about 15 d and reached critical values for the slowly growing AMX. When the SRT was increased by reducing biomass loss with the effluent, AMX activity and abundance started to rise again, while the AOB activity remained unaltered. Fluorescent in-situ hybridisation (FISH) showed that the initial AMX community shifted within only 40 d from a mixed AMX community to "Candidatus Brocadia fulgida" as the dominant AMX type with an influent COD/N ratio of 0.8 g COD∙g N(-1) and higher. "Ca. Brocadia fulgida" is known to oxidise acetate, and its ability to outcompete other types of AMX indicates that AMX participated in acetate oxidation. In a later phase, glucose was added to the influent instead of acetate. The new substrate composition did not significantly influence the nitrogen removal nor the AMX activity, and "Ca. Brocadia fulgida" remained the dominant type of AMX. Overall, this study showed that AMX can coexist with heterotrophic bacteria at elevated influent COD/N ratios if a sufficiently high SRT is maintained., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

When magnesium is added to source-separated urine, struvite (MgNH(4)PO(4)·6H(2)O) precipitates and phosphorus can be recovered. Up to now, magnesium salts have been used as the main source of magnesium. Struvite precipitation with these salts works well but is challenging in decentralized reactors, where high automation of the dosage and small reactor sizes are required. In this study, we investigated a novel approach for magnesium dosage: magnesium was electrochemically dissolved from a sacrificial magnesium electrode. We demonstrated that this process is technically simple and economically feasible and thus interesting for decentralized reactors. Linear voltammetry and batch experiments at different anode potentials revealed that the anode potential must be higher than -0.9 V vs. NHE (normal hydrogen electrode) to overcome the strong passivation of the anode. An anode potential of -0.6 V vs. NHE seemed to be suitable for active magnesium dissolution. For 13 subsequent cycles at this potential, we achieved an average phosphate removal rate of 3.7 mg P cm(-2) h(-1), a current density of 5.5 mA cm(-2) and a current efficiency of 118%. Some magnesium carbonate (nesquehonite) accumulated on the anode surface; as a consequence, the current density decreased slightly, but the current efficiency was not affected. The energy consumption for these experiments was 1.7 W h g P(-1). A cost comparison showed that sacrificial magnesium electrodes are competitive with easily soluble magnesium salts such as MgCl(2) and MgSO(4), but are more expensive than dosing with MgO. Energy costs for the electrochemical process were insignificant. Dosing magnesium electrochemically could thus be a worthwhile alternative to dosing magnesium salts. Due to the simple reactor and handling of magnesium, this may well be a particularly interesting approach for decentralized urine treatment., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Human urine has the potential to be a sustainable, locally and continuously available source of nutrients for agriculture. Phosphate can be efficiently recovered from human urine in the form of the mineral struvite (MgNH4PO4·6H2O). However, struvite formation may be coupled with the precipitation of other constituents present in urine including pathogens, pharmaceuticals, and heavy metals. To determine if struvite fertilizer presents a microbiological health risk to producers and end users, we characterized the fate of a human virus surrogate (phage ΦX174) and the eggs of the helminth Ascaris suum during a low-cost struvite recovery process. While the concentration of phages was similar in both the struvite and the urine, Ascaris eggs accumulated within the solid during the precipitation and filtration process. Subsequent air-drying of the struvite filter cake partially inactivated both microorganisms; however, viable Ascaris eggs and infective phages were still detected after several days of drying. The infectivity of both viruses and eggs was affected by the specific struvite drying conditions: higher inactivation generally occurred with increased air temperature and decreased relative humidity. On a log-log scale, phage inactivation increased linearly with decreasing moisture content of the struvite, while Ascaris inactivation occurred only after achieving a minimum moisture threshold. Sunlight exposure did not directly affect the infectivity of phages or Ascaris eggs in struvite cakes, though the resultant rise in temperature accelerated the drying of the struvite cake, which contributed to inactivation., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Blockages caused by inorganic precipitates are a major problem of urine-collecting systems. The trigger of precipitation is the hydrolysis of urea by bacterial urease. While the maximum amount of precipitates, i.e. the precipitation potential, can be estimated with equilibrium calculations, little is known about the dynamics of ureolysis and precipitation. To gain insight in these processes, we performed batch experiments with precipitated solids and stored urine from a urine-collecting system and later simulated the results with a computer model. We found that urease-active bacteria mainly grow in the pipes and are flushed into the collection tank. Both, bacteria and free urease, hydrolyse urea. Only few days are necessary for complete urea depletion in the collection tank. Two experiments with precipitated solids from the pipes showed that precipitation sets in soon after ureolysis has started. At the end of the experiments, 11% and 24% of urea was hydrolysed while the mass concentration of newly formed precipitates already corresponded to 87% and 97% of the precipitation potential, respectively. We could simulate ureolysis and precipitation with a computer model based on the surface dislocation approach. The simulations showed that struvite and octacalcium phosphate (OCP) are the precipitating minerals. While struvite precipitates already at low supersaturation, OCP precipitation starts not until a high level of supersaturation is reached. Since measurements and computer simulations show that hydroxyapatite (HAP) is the final calcium phosphate mineral in urine solutions, OCP is only a precursor phase which slowly transforms into HAP.

Precipitation in urine-separating toilets (NoMix toilets) and waterless urinals causes severe maintenance problems and can strongly reduce the content of soluble phosphate. In this study, we present a computer model for estimating the precipitation potential (PP) in urine-collecting systems. Calculating the PP enables to predict the composition and mass concentration of precipitates. We used our computer model for investigating how urea hydrolysis and dilution with flushing water affect precipitation. In a previous study, we found that microbial urea hydrolysis (ureolysis) triggers precipitation and that the amount of precipitates is limited by calcium and magnesium. With the present simulations, we could confirm these findings. We determined that only a small fraction of urea has to be hydrolysed for reaching 95% of the maximum PP. Since urease-positive bacteria are abundant in urine-collecting systems, strong precipitation is very likely. In further simulations, we determined that struvite (MgNH(4)PO(4).6H(2)O) and hydroxyapatite (HAP, Ca(10)(PO(4))(6)(OH)(2)) are the main precipitate compounds. If urine is highly diluted with tapwater, calcite (CaCO(3)) occurs as well. HAP is the only calcium phosphate mineral, although several others were supersaturated. Additionally, the simulations indicated that urine dilution diminishes the risk of blockages, since the mass concentration of precipitates decreases with the volume of flushing water. Rainwater flushing is more effective than flushing with tapwater. Moreover, flushing with tapwater leads to high phosphate fixation, because the total amount of calcium and magnesium ions increases, while the total amount of phosphate keeps constant. Finally, we compared simulation results with field measurements and found good agreement at low and very high urine dilution.