En récupérant les nutriments contenus dans les urines, nous développons un système sanitaire, qui produit des engrais
In Autarky entwickeln wir kleine Anlagen für die getrennte Behandlung von Urin, Abwasser und Fäkalien direkt in der Toilette.
La gestion durable d'eaux potable et usées appliquée et mise en pratique dans le bâtiment modulaire NEST.
Le programme de recherche stratégique inter- et transdisciplinaire vise à développer des systèmes d'approvisionnement en eau et d'assainissement innovants, non raccordés au réseau.
Stickstoffentfernung aus Urin mit Nitritation/Anammox
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Modeling the low pH limit of Nitrosomonas eutropha in high-strength nitrogen wastewaters
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.
Formation of chlorination byproducts and their emission pathways in chlorine mediated electro-oxidation of urine on active and nonactive type anodes
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.
Zöllig, H.; Remmele, A.; Fritzsche, C.; Morgenroth, E.; Udert, K. M. (2015) Formation of chlorination byproducts and their emission pathways in chlorine mediated electro-oxidation of urine on active and nonactive type anodes, Environmental Science and Technology, 49(18), 11062-11069, doi:10.1021/acs.est.5b01675, Institutional Repository
Direct electrochemical oxidation of ammonia on graphite as a treatment option for stored source-separated urine
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.
Observability of anammox activity in single-stage nitritation/anammox reactors using mass balances
In nitritationammox reactors, several bacterial groups contribute to the overall nitrogen conversion. Knowing the activity of the main bacterial groups, especially of anaerobic ammonium-oxidising bacteria (AMX), is extremely helpful to understand the process and optimise its operation. Mass balances of dissolved compounds such as ammonium, nitrite and nitrate commonly allow the determination of bacterial activities in a nitritationammox process, but the activity of heterotrophic bacteria (HET) is usually neglected. However, even in wastewater with a low organic substrate content, heterotrophic denitrification can contribute substantially to nitrogen removal. The goal of this study was to critically evaluate the applicability of mass balances for the determination of the relevant bacterial activities in a nitritationammox process with high HET activity. We set up and solved mass balances of different degrees of complexity. Both linear equation systems, with catabolic reactions alone and with balances according to the activated sludge model stoichiometry, do not allow estimation of any of the considered bacterial activities. When kinetic rate expressions are included, it is possible to compute the concentrations of all considered bacterial groups, but the estimation uncertainty is far too high for practical purposes: the relative standard deviation for AMX is 5280%. In a completely autotrophic system, the relative standard deviation for AMX is only 5%, which proves that the high standard deviations are due to the complexity of the nitration–anammox process with HET activity. The high standard deviations of the calculated bacterial concentrations can be significantly reduced by adding an additional mass balance for the total biomass (standard deviation for AMX activity 1210%). The required number of measurements to achieve an acceptable precision, in our example about 600 conversion rate measurements to reach a 50% standard deviation for the AMX concentration, is still far too high though for practical purposes. To conclude, mass balances including kinetics theoretically allow the observation of the bacterial activities in nitritationammox reactors with high HET activity. However, the required precision of the calculated conversion rates, the uncertainty of stoichiometric and kinetic parameters and the reactor dynamics (unsteady conditions) make mass balances unsuitable for practical estimation of AMX activity. Due to high frequency and new online instruments, mass balances might become a suitable tool in the future.
Schielke-Jenni, S.; Villez, K.; Morgenroth, E.; Udert, K. M. (2015) Observability of anammox activity in single-stage nitritation/anammox reactors using mass balances, Environmental Science: Water Research and Technology, 1(4), 523-534, doi:10.1039/c5ew00045a, Institutional Repository
Successful application of nitritation/anammox towastewater with elevated organic carbon to ammonia ratios
The nitritation/anammox process has been mainly applied to high-strength nitrogenous wastewaters with very low biodegradable organic carbon content (<0.5g COD·g N–1). However, several wastewaters have biodegradable organic carbon to nitrogen (COD/N) ratios between 0.5 and 1.7g 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 1.4g 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 ± 40mg 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.
Source separation and decentralization for wastewater management
Is sewer-based wastewater treatment really the optimal technical solution in urban water management? This paradigm is increasingly being questioned. Growing water scarcity and the insight that water will be an important limiting factor for the quality of urban life are main drivers for new approaches in wastewater management. Source Separation and Decentralization for Wastewater Management sets up a comprehensive view of the resources involved in urban water management. It explores the potential of source separation and decentralization to provide viable alternatives to sewerbased urban water management. During the 1990s, several research groups started working on sourceseparating technologies for wastewater treatment. Source separation was not new, but had only been propagated as a cheap and environmentally friendly technology for the poor. The novelty was the discussion whether source separation could be a sustainable alternative to existing end-of-pipe systems, even in urban areas and industrialized countries. Since then, sustainable resource management and many different sourceseparating technologies have been investigated. The theoretical framework and also possible technologies have now developed to a more mature state. At the same time, many interesting technologies to process combined or concentrated wastewaters have evolved, which are equally suited for the treatment of source-separated domestic wastewater. The book presents a comprehensive view of the state of the art of source separation and decentralization. It discusses the technical possibilities and practical experience with source separation in different countries around the world. The area is in rapid development, but many of the fundamental insights presented in this book will stay valid. Source Separation and Decentralization for Wastewater Management is intended for all professionals and researchers interested in wastewater mamagement, wheter or not they are familiar with source separation.
Struvite precipitation from urine with electrochemical magnesium dosage
When magnesium is added to source-separated urine, struvite (MgNH4PO4·6H2O) 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 MgCl2 and MgSO4, 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.
Complete nutrient recovery from source-separated urine by nitrification and distillation
In this study we present a method to recover all nutrients from source-separated urine in a dry solid by combining biological nitrification with distillation. In a first process step, a membrane-aerated biofilm reactor was operated stably for more than 12 months, producing a nutrient solution with a pH between 6.2 and 7.0 (depending on the pH set-point), and an ammonium to nitrate ratio between 0.87 and 1.15 gN gN−1. The maximum nitrification rate was 1.8 ± 0.3 gN m−2 d−1. Process stability was achieved by controlling the pH via the influent. In the second process step, real nitrified urine and synthetic solutions were concentrated in lab-scale distillation reactors. All nutrients were recovered in a dry powder except for some ammonia (less than 3% of total nitrogen). We estimate that the primary energy demand for a simple nitrification/distillation process is four to five times higher than removing nitrogen and phosphorus in a conventional wastewater treatment plant and producing the equivalent amount of phosphorus and nitrogen fertilizers. However, the primary energy demand can be reduced to values very close to conventional treatment, if 80% of the water is removed with reverse osmosis and distillation is operated with vapor compression. The ammonium nitrate content of the solid residue is below the limit at which stringent EU safety regulations for fertilizers come into effect; nevertheless, we propose some additional process steps that will increase the thermal stability of the solid product.
Low-cost struvite production using source-separated urine in Nepal
This research investigated the possibility of transferring phosphorus from human urine into a concentrated form that can be used as fertilizer in agriculture. The community of Siddhipur in Nepal was chosen as a research site, because there is a strong presence and acceptance of the urine-diverting dry toilets needed to collect urine separately at the source. Furthermore, because the mainly agricultural country is landlocked and depends on expensive, imported fertilizers, the need for nutrient security is high. We found that struvite (MgNH4PO4·6H2O) precipitation from urine is an efficient and simple approach to produce a granulated phosphorus fertilizer. Bittern, a waste stream from salt production, is a practical magnesium source for struvite production, but it has to be imported from India. Calculations show that magnesium oxide produced from locally available magnesite would be a cheaper magnesium source. A reactor with an external filtration system was capable of removing over 90% of phosphorus with a low magnesium dosage (1.1 mol Mg mol P), with coarse nylon filters (pore width up to 160 ± 50 μm) and with only one hour total treatment time. A second reactor setup based on sedimentation only achieved 50% phosphate removal, even when flocculants were added. Given the current fertilizer prices, high volumes of urine must be processed, if struvite recovery should be financially sustainable. Therefore, it is important to optimize the process. Our calculations showed that collecting the struvite and calcium phosphate precipitated spontaneously due to urea hydrolysis could increase the overall phosphate recovery by at least 40%. The magnesium dosage can be optimized by estimating the phosphate concentration by measuring electrical conductivity. An important source of additional revenue could be the effluent of the struvite reactor. Further research should be aimed at finding methods and technologies to recover the nutrients from the effluent.
Direct and mediated electrochemical oxidation of ammonia on boron-doped diamond electrode
Direct (non-mediated) electrochemical oxidation of ammonia on boron-doped diamond (BDD) electrode proceeds mainly at high pH (>8) via free ammonia (NH3) oxidation. To enhance ammonia oxidation on BDD at low pH (<8), where mainly ammonium (NH4+) is present, oxidation of ammonia was mediated by active free chlorine. In this process, electro-generated in situ active chlorine rapidly reacts with ammonia instead of being further electro-oxidized to chlorate at the electrode surface. Thus, active chlorine effectively removes ammonia from an acidic solution, while the formation of by-products such as chlorate and possibly perchlorate is minimized.
Estimating the precipitation potential in urine-collecting systems
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 (MgNH4PO4·6H2O) and hydroxyapatite (HAP, Ca10(PO4)6(OH)2) are the main precipitate compounds. If urine is highly diluted with tapwater, calcite (CaCO3) 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.
Urea hydrolysis and precipitation dynamics in a urine-collecting system
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.