The application of struvite (magnesium ammonium phosphate,!MgNH&PO& ∙ 6H+O) precipitation and its recycling use for the purpose of ammonia removal from both synthetic solutions and landfill leachate were investigated in this study. The results demonstrated that chemical precipitation by struvite formation is efficient for ammonia removal from aqueous solutions. In addition, by recycling the thermal residue of struvite, continuously removing ammonia can technically be achieved. In the struvite precipitation, ammonia removal significantly depended on the pH and chemical molar ratios of NH& ,:!Mg+,:!PO& ./. For synthetic solution (TAN=1,000 mg/L), remarkable TAN removal efficiency of over 98% has been reported when the molar ratio of NH& ,:!Mg+,:!PO& ./ equals 1.0:1.2:1.2, 1.0:1.3:1.3, 1.0:1.3:1.4 and 1.0:1.5:1.5 at optimum pH 9. The optimum combinations of reagents applied in landfill leachate (TAN=1,878 mg/L) were!NH& ,:!Mg+,:!PO& ./ =1.0:1.3:1.3, 1.0:1.4:1.3, 1.0:1.5:1.4 and 1.0:1.5:1.5 at optimum pH 9.5, all of which displayed excellent TAN removal efficiencies of over 99%. Response surface method (RSM) helped to analyze the data and optimize the results. The struvite pyrolysate provided best performance of removing ammonia in both simulated wastewater and landfill leachate at a dosage of 60 g/L, when struvite was previously heated at 105 􀀁 by oven for 2.5 h. In the recycling phase, the struvite pyrolysate resulting from NaOH-mediated pyrolysis was more effective at continuously treating ammonia synthetic solution than was direct heating, with an initial mode of 87.4% at the beginning to 75.1% in the fifth round and direct heating of struvite from 80.9% in the first cycle and 60.6% in the final cycle. The struvite pyrolysate formed by NaOH-mediated pyrolysis performed with greater ability to continuously eliminate ammonia from landfill leachate (97.2% removal at the beginning and 72.3% in the fifth round), than did directly heated struvite (98.4% in the first cycle and 81.3% in the final cycle). Additionally, microwave irradiation could also dissociate struvite, which subsequently demonstrated moderate TAN removal in recycling phases.

Source-separating urine for nutrient recovery may provide multiple benefits with regards to wastewater management, water conservation, and an impending phosphorus fertilizer shortage. Municipal wastewater systems are designed to treat the combination of urine, feces and graywater produced in household applications. Urine accounts for 1% of wastewater by volume, but provides 70-90% of nitrogen, 35-70% of phosphorus and 50% of the contaminants of emerging concern entering municipal wastewater treatment (Larsen and Gujer 1996). Research has shown managing source-separated urine for nutrient recovery is a more cost effective and less treatment intensive method than using traditional systems found in municipal wastewater plants. Phosphorus fertilizer shortages are projected as current sources diminish and become increasingly difficult to extract and refine. Phosphorus based-fertilizer recovery, in the form of 99.9% pure struvite (MgNH4PO4•6H2O), has been demonstrated successfully in full-scale sidestream treatment using dewatering liquor from anaerobically digested solids (centrate) processed through upflow fluidized bed reactor technologies (Britton et al. 2005). Prior research determined the influence of pH, magnesium to phosphorus (Mg:P) molar ratio, and age of urine on purity, pharmaceutical content and pathogen inclusion in struvite precipitated from source-separated urine. This is the first known example of an attempt to produce a commercially viable struvite product from source-separated urine in a fluidized bed reactor of a design that has been used successfully for struvite recovery in conventional wastewater applications. In order to assess the feasibility of nutrient recovery of phosphorus-based fertilizer recovery from source-separated urine, the first office-based urine separation and collection building was implemented in the U.S. Urine was collected, in a 400 gallon capacity underground sealed manhole, from HRSD's Main office building beginning in March 2015 from 5 men's waterless urinals and one women's separating toilet. Urine was collected from the manhole on a monthly basis in 275 and 330 gallon plastic totes stored at the HRSD Nansemond WWTP in Suffolk, VA. Collected urine was allowed to age while in storage to encourage the precipitation of excess multivalent cations that may interfere with struvite precipitation and inactivation of pathogens that may be present. An upflow fluidized bed reactor (UFBR) was used to recover struvite as a slow-release phosphorus based fertilizer (prill), the reactor was loaned to HRSD by the University of British Columbia. A magnesium solution was injected at the bottom of the reactor to facilitate precipitation along with the recycle urine stream and feed urine as shown. Prill production design for the reactor was 0.5 kilograms per day, but while using centrate to determine best operations practices, under loading the reactor to 0.25 kilograms per day maximized struvite recovery while minimizing particulate phosphorus loss. Urine was fed into the reactor for struvite removal based on phosphorus loading with recovery determined through removal of orthophosphate and harvesting of the struvite product. Consistency, size and quality of product including compactness, crystal structure, purity and presence of pharmaceuticals and pathogens were assessed. The UFBR was run for 50 days total; 10 days for a short term run to compare to operation of the reactor under the same conditions with centrate from anaerobically digested solids as a feed source, 30 days to assess consistency of operations over long term with respect to struvite recovery, and a 10 day test with urine spiked with pharmaceuticals and bacteriophage to evaluate inclusion of trace organics and viruses in recovered struvite. In total 2,040 gallons of urine were fed to the reactor targeting 12.45 kilograms of struvite recovery, a mass of 7.54 kilograms of prills were harvested from the reactor with 1.90 kilograms of phosphorus lost as particulate struvite (representing an recovery efficiency of 60.5%). Overall reactor operation using urine as a feed solution behaved similar to centrate, with slightly less removal of phosphorus. Urine-derived prills were lower in quality due to the lack of compact density seen in struvite recovered during full scale operation but had a visible orthombic pattern seen in precipitated struvite. Pharmaceuticals that were present in urine feed solution were found in struvite but at less than 1% of the feed mass. Some of this inclusion may have occurred due to porous characteristics of the small-scale UFBR recovered struvite rather than through actual inclusion in the mineral crystal itself. Spiking of caffeine and ibuprofen to high concentrations in the urine yielded no statistical difference from the non-spiked tote. Urine was non-detect for bacteriophage pathogen indicators leading to the assumption that no pathogens were present in urine-derived struvite. Spiking the urine with double-stranded DNA (T3) and single-stranded RNA (MS2) bacteriophage capable of infecting bacterial cells such as Escherichia coli yielded 10^6 plaque forming units per milliliter in source separated urine. Creating urine-derived struvite prills with minimal inclusion of pharmaceuticals using upflow fluidized bed technology is feasible on a small scale. Large-scale application, recovering 500 kilograms per day of struvite or more, will most likely create a higher quality prill with regards to compactness and diminished presence of pharmaceuticals and virus inclusion. Pretreatment of urine and post-treatment of prills with heat will aid in inactivation of virus that may be present. ' / Master of Science

Phosphorus (P) recovery and re-use is very important today for sustainable nutrient cycling and water quality protection due to the declining global P reserves and increasingly stringent wastewater treatment regulations. P recovery as struvite (MgNH4PO4·6H2O) is a promising technology because it can be used as a slow-release fertilizer. The objective of this study was to investigate different pretreatment methods to enhance struvite precipitation in dairy manure. Generally there are two challenges that need to be overcome to precipitate struvite in liquid dairy manure. The first is the relatively high calcium (Ca) concentration. The present study investigated the effectiveness of two calcium binding reagents to reduce the calcium inhibitory effects to enhance the struvite precipitation. A chemical equilibrium model (Visual MINTEQ 2.60) was used to determine the pH to acidify manure and to precipitate struvite. Then, bench-scale experiments were conducted to validate the model results using synthetic and untreated manure. First, the manure was acidified (pH 4.5) to liberate the particulate-bounded Mg2+, Ca2+ and inorganic P. Second, EDTA and/or oxalate compounds were added to the manure. Third, pH was increased to 7.5 for struvite precipitation from the liquid filtrate. Results showed that struvite-containing crystals were obtained from the samples treated with calcium removal compounds, with a total suspended solids (TSS) concentration less than 4,000 mg/L. The second challenge is the low dissolved reactive P (DRP, i.e. PO4-P) to total P (TP) ratio. This study investigated different pretreatment methods for P release to enhance struvite precipitation in liquid dairy manure: enhanced biological phosphorus removal (EBPR), microwave heating (MW) and anaerobic digestion (AD). All of the pretreatment methods resulted in P release but struvite crystals were observed only in precipitates obtained in manure pretreated with MW+H2SO4 acidification. Without oxalic acid to reduce the Ca2+ effects, all the other pretreatment methods were not effective in enhancing struvite precipitation in liquid dairy manure. Hardly any struvite or crystalline-like solids were found in the non-centrifuged samples, regardless of any pretreatment, indicating the effects of suspended solids and organic matter on struvite precipitation. A partial economic analysis was conducted to assess the chemical costs of P recovery from liquid dairy manure with different pretreatment methods; P recovery amounts as struvite were modeled by Visual Minteq 2.61.Three pretreatment conditions (untreated manure + oxalic acid, MW + H2SO4 acidification, and AD) were selected based on the precipitation results. MW + H2SO4 acidification produced the highest struvite quantities among the pretreatment methods to enhance struvite recovery, also with the lowest chemical addition costs. / Master of Science

Struvite is a salt that is formed out of  Mg2+,NH4+ and PO43- and it crystallizes in form of MgNH4PO4.6H2O. Struvite‟s (magnesium ammonium phosphate or MAP) precipitation has recently been regarded as an interesting technique to remove phosphate and ammonium from waste water. The high elimination rates and the possibility of recycling the struvite as a direct slow release fertilizer make this process feasible and appealing. However, the costs due to the raw chemicals needed are drawbacks that leave aside the application of the process in some facilities. The MAP biological dissolution makes possible a recycling of magnesium and phosphate, a fact that reduces the process‟s costs and will help making it even more feasible and environmentally friend. This thesis goes also through the parameters, reactions and different techniques that optimize the struvite precipitation process.

A recuperação de nitrogênio e fósforo presente no esgoto tem se tornado uma alternativa bastante promissora para fornecer uma fonte renovável e ecologicamente sustentável de nutrientes para a agricultura e, consequentemente, melhorar a qualidade do efluente final do sistema de tratamento. Os compostos de fósforo, durante o tratamento de esgoto, numa primeira etapa são removidos por processos biológicos, sendo incorporados no lodo pelos organismos heterotróficos ordinários e organismos acumuladores de fósforo (PAOs). Seguidamente, em condições anaeróbias, o fósforo armazenado no lodo pode ser liberado para a fase líquida e em seguida recuperado como estruvita (MgNH4PO4 .6H2O) num processo de cristalização sob condições controladas. No Brasil, ainda não existem documentados estudos em escala piloto, que simulem condições reais, utilizando sistemas EBPR e reatores de precipitação. Por tal motivo, esta pesquisa foi desenvolvida com o intuito de contribuir com uma melhor compreensão do fenômeno de recuperação de fósforo como cristais de estruvita. A pesquisa foi dividia em três etapas: 1) Operação da configuração UCT modificado e digestor anaeróbio de lodo misto e testes preliminares no reator de precipitação de estruvita; 2) Delineamento e realização de experimentos de precipitação e 3) caracterização dos sólidos obtidos nos experimentos de precipitação. A primeira etapa consistiu em dar partida ao sistema biológico de remoção de fósforo (UCT modificado) e digestor anaeróbio de lodo, e consequentemente a produção do sobrenadante. Paralelamente, foram realizados testes no reator de precipitação. A partir do filtrado e o planejamento fatorial 33, foram definidos o pH, dosagem de magnésio e tempo de detenção hidráulico como fatores que exercem influência na precipitação de estruvita. Definiram-se as remoções de nitrogênio e fósforo como as variáveis respostas ao delineamento experimental. Os resultados mostraram remoções de nitrogênio entre 30 e 40% para pH 8,50 e 9,50, enquanto que remoções de fósforo acima de 80% foram obtidas para uma dosagem de magnésio de 80 mg Mg2+/L e pH 8,50 e 9,50. A influência do tempo de detenção hidráulico não foi significativa tanto na remoção de nitrogênio quanto de fósforo. As imagens obtidas pelas análises de MEV constataram a presença de um sistema ortorrômbico, típica dos cristais de estruvita. No entanto, observou-se que os tamanhos dos cristais mudaram consideravelmente em função dos tempos A caracterização dos sólidos por difração de raios X mostrou que na maioria dos experimentos foi obtida estruvita (23 das 27 condições experimentais), seguida de bobbierrita e newberita, em alguns casos, phosphamita, biphosphamita e brucita. Para as condições de pH 8,50 e 9,50 foi obtida pureza da estruvita entre 80 e 97%. / The recovery of nitrogen and phosphorus present in sewage has become a very promising alternative to provide a renewable and ecologically sustainable source of nutrients for agriculture and a consequently improve of the final effluent quality of the treatment system. The phosphorus compounds are initially removed by biological processes, being incorporated in the sludge through phosphorus-accumulating organisms (PAOs). Later, the phosphorus stored under anaerobic conditions in the sludge, is released to the liquid phase and finally recovered as struvite (MgNH4PO4 .6H2O) following its crystallization process under a controlled setting. No pilot-scale studies, which simulate the real conditions using EBPR and precipitation reactors, have been documented in Brazil so far. Therefore, this research aimed to contribute to improve the understanding of the phosphorus recovering phenomenon as struvite crystals. This project was divided in three main stages: 1) Operation of the UCT-modified setting and the anaerobic digester of mixed sludge; 2) Design and performance of precipitation experiments and. 3) Characterization of the obtained solids during the precipitation experiments. At the first stage, the biological system for phosphorus removal (UCT-modified), and the anaerobic sludge digester were initiated, followed by the production of supernatant. Simultaneously, precipitation tests were carried out at the reactor. Following the factorial design, and using the recovered supernatant, the pH, addition of magnesium and hydraulic retention time, were identified as factors influencing the struvite precipitation. The phosphorus and nitrogen removal were defined as the dependent variables for the experimental design. The results showed a nitrogen removal between 30% and 40% for pH values of 8.50 and 9.50, independently of the used magnesium dose. On the otherhand, over 80% of phosphorus removal was attained with addition of magnesium of 80 mg Mg2+/L and pH values of 8.50 and 9.50. The hydraulic retention time have not influenced the total nitrogen and phosphorus removal, but the grain-size of the struvite crystals precipitated. The characterization of the recovered solids by X-ray diffraction showed that struvite was precipitated in most of the performed experiments (23 of 27 settings), although bobierrite, newberyite, phosphamite, biphosphamite and brucite, were formed as well. The maximum values for struvite pureness, between 80% and 97%, were obtained with pH values of 8.50 and 9.50. The MEV analyses supported the presence of a orthorhombic crystallographic system, which is a typical feature of struvite.

A recuperação de nitrogênio e fósforo presente no esgoto tem se tornado uma alternativa bastante promissora para fornecer uma fonte renovável e ecologicamente sustentável de nutrientes para a agricultura e, consequentemente, melhorar a qualidade do efluente final do sistema de tratamento. Os compostos de fósforo, durante o tratamento de esgoto, numa primeira etapa são removidos por processos biológicos, sendo incorporados no lodo pelos organismos heterotróficos ordinários e organismos acumuladores de fósforo (PAOs). Seguidamente, em condições anaeróbias, o fósforo armazenado no lodo pode ser liberado para a fase líquida e em seguida recuperado como estruvita (MgNH4PO4 .6H2O) num processo de cristalização sob condições controladas. No Brasil, ainda não existem documentados estudos em escala piloto, que simulem condições reais, utilizando sistemas EBPR e reatores de precipitação. Por tal motivo, esta pesquisa foi desenvolvida com o intuito de contribuir com uma melhor compreensão do fenômeno de recuperação de fósforo como cristais de estruvita. A pesquisa foi dividia em três etapas: 1) Operação da configuração UCT modificado e digestor anaeróbio de lodo misto e testes preliminares no reator de precipitação de estruvita; 2) Delineamento e realização de experimentos de precipitação e 3) caracterização dos sólidos obtidos nos experimentos de precipitação. A primeira etapa consistiu em dar partida ao sistema biológico de remoção de fósforo (UCT modificado) e digestor anaeróbio de lodo, e consequentemente a produção do sobrenadante. Paralelamente, foram realizados testes no reator de precipitação. A partir do filtrado e o planejamento fatorial 33, foram definidos o pH, dosagem de magnésio e tempo de detenção hidráulico como fatores que exercem influência na precipitação de estruvita. Definiram-se as remoções de nitrogênio e fósforo como as variáveis respostas ao delineamento experimental. Os resultados mostraram remoções de nitrogênio entre 30 e 40% para pH 8,50 e 9,50, enquanto que remoções de fósforo acima de 80% foram obtidas para uma dosagem de magnésio de 80 mg Mg2+/L e pH 8,50 e 9,50. A influência do tempo de detenção hidráulico não foi significativa tanto na remoção de nitrogênio quanto de fósforo. As imagens obtidas pelas análises de MEV constataram a presença de um sistema ortorrômbico, típica dos cristais de estruvita. No entanto, observou-se que os tamanhos dos cristais mudaram consideravelmente em função dos tempos A caracterização dos sólidos por difração de raios X mostrou que na maioria dos experimentos foi obtida estruvita (23 das 27 condições experimentais), seguida de bobbierrita e newberita, em alguns casos, phosphamita, biphosphamita e brucita. Para as condições de pH 8,50 e 9,50 foi obtida pureza da estruvita entre 80 e 97%. / The recovery of nitrogen and phosphorus present in sewage has become a very promising alternative to provide a renewable and ecologically sustainable source of nutrients for agriculture and a consequently improve of the final effluent quality of the treatment system. The phosphorus compounds are initially removed by biological processes, being incorporated in the sludge through phosphorus-accumulating organisms (PAOs). Later, the phosphorus stored under anaerobic conditions in the sludge, is released to the liquid phase and finally recovered as struvite (MgNH4PO4 .6H2O) following its crystallization process under a controlled setting. No pilot-scale studies, which simulate the real conditions using EBPR and precipitation reactors, have been documented in Brazil so far. Therefore, this research aimed to contribute to improve the understanding of the phosphorus recovering phenomenon as struvite crystals. This project was divided in three main stages: 1) Operation of the UCT-modified setting and the anaerobic digester of mixed sludge; 2) Design and performance of precipitation experiments and. 3) Characterization of the obtained solids during the precipitation experiments. At the first stage, the biological system for phosphorus removal (UCT-modified), and the anaerobic sludge digester were initiated, followed by the production of supernatant. Simultaneously, precipitation tests were carried out at the reactor. Following the factorial design, and using the recovered supernatant, the pH, addition of magnesium and hydraulic retention time, were identified as factors influencing the struvite precipitation. The phosphorus and nitrogen removal were defined as the dependent variables for the experimental design. The results showed a nitrogen removal between 30% and 40% for pH values of 8.50 and 9.50, independently of the used magnesium dose. On the otherhand, over 80% of phosphorus removal was attained with addition of magnesium of 80 mg Mg2+/L and pH values of 8.50 and 9.50. The hydraulic retention time have not influenced the total nitrogen and phosphorus removal, but the grain-size of the struvite crystals precipitated. The characterization of the recovered solids by X-ray diffraction showed that struvite was precipitated in most of the performed experiments (23 of 27 settings), although bobierrite, newberyite, phosphamite, biphosphamite and brucite, were formed as well. The maximum values for struvite pureness, between 80% and 97%, were obtained with pH values of 8.50 and 9.50. The MEV analyses supported the presence of a orthorhombic crystallographic system, which is a typical feature of struvite.

The focus of this thesis is the posibility of obtaining phosphorus from liquid digestate. The theoretical part of the thesis is focused on summarizing the current situation regarding phosphorus recovery. The research summarizes the essential information about the method of struvite precipitation, by which phoshphorus is obtained in the form of struvite, which can be further used as a fertilizer. Based on the process information, an experimental device was designed to obtain phosphorus in the form of struvite, corresponding to industry standards. It is a cylindrical vessel with a conical bottom, in which the liquid digestate with the chemicals is mixed with a stirrer. The functionality of the device was tested experimentally on the created device. The results of the experiment were analyzed by XPS method, which confirmed the formation of struvite. For future operation, modifications of the device and pre-treatment of the liquid digestate were proposed, which could improve the whole process and its results.

Efforts to remove and recover nutrients from wastewater are motivated by the United Nations Sustainable Development Goals and the National Academy of Engineering Grand Challenges of Engineering. Of the seventeen Sustainable Development Goals (SDGs), multiple SDGs relate to managing nutrients in wastewater. SDG 6, which is to “ensure availability and sustainable management of water and sanitation for all,” contains targets that aim to improve water quality by reducing pollution, halve the amount of untreated wastewater released to the environment, and increase recycling and safe reuse of wastewater (UN, 2017). SDG 2 seeks to improve food security and SDG 12 seeks to sustainably manage natural resources. Similarly, the National Academy of Engineering Grand Challenges of Engineering highlight managing the nitrogen cycle and providing access to clean water (NAE, 2019). Centralized wastewater treatment plants (WWTPs) have historically been designed to remove nutrients (such as nitrogen and phosphorus) and other contaminants prior to discharge. Modern wastewater treatment practices integrate recovery of resources including nutrients, energy, and water. The many available technologies, coupled with competing priorities, can complicate community decision-making on the choice of technology and the scale at which to implement the technology (i.e. building, community, or city), as well as determining how new upstream treatment may affect existing downstream treatment. Technologies that recover energy or manage nutrients such as anaerobic digestion, struvite precipitation, and microbial fuel cells can be implemented at a variety of scales in urban settings and may also be viable for influent types such as agricultural waste. Therefore, the overall goal of this dissertation is to contribute to the achievement of multiple sustainable development goals through the removal and recovery of nitrogen and phosphorus from a variety of influents at a variety of scales. One type of decision-making tool that assists in the choice of nutrient management technologies is a House of Quality. I developed a tool based on the House of Quality that integrated multiple priorities at three scales in a sewershed and produced rankings that generally align with current wastewater treatment practice. Accordingly, top-ranked city-scale technologies are those commonly employed (e.g. A2O, oxidation ditch) that use the dissolved organic carbon present in the wastewater to drive denitrification. Similarly, conventional treatment (e.g. flush toilet connected to a sewer) is ranked highest at the building scale because of its easy maintenance, small footprint, and inoffensive aesthetics. However, future trends such as technology development will likely affect the technologies, weightings, and scores and therefore improve the ranking of novel and emerging technologies. This trend may be amplified by the implementation of test beds, which can provide opportunities to improve the technical characteristics of developing technologies while minimizing risk for municipalities. The House of Quality planning tool was utilized in an in silico case study to analyze nutrient management technologies at three scales across the Northwest Regional Water Reclamation Facility sewershed in Hillsborough County, FL. The study demonstrated that employing treatment technologies upstream from the centralized wastewater treatment (i.e. building-scale source separation and community-scale technologies) could reduce nitrogen loading to the mainstream treatment train by over 50%. Sidestream treatment (i.e. the liquid effluent of anaerobic digestion that typically recycles back to the beginning of the mainstream treatment process) has minimal impact in nitrogen reduction, but is effective in reducing phosphorus loading to the mainstream due to high quantities of phosphorus recycling back to the head of the plant. These results can inform decision-makers about which context-specific nutrient management technologies to consider at a variety of scales, and illustrate that sidestream technologies can be the most effective in reducing phosphorus loading while building- and community-scale technologies can be most effective in reducing nitrogen loading to the centralized treatment plant. Struvite precipitation and microbial fuel cells (MFCs) can be used in combination to manage nutrients and recover energy in sidestreams of centralized WWTPs. Because the liquid effluent from engineered struvite precipitation often contains high concentrations of total nitrogen, I constructed and demonstrated a fixed-film nitrification reactor and a two-chambered MFC to further reduce total nitrogen and recover energy. The primary benefit of the MFC in the technology demonstrated here is not its ability to produce energy, but rather its ability to remove additional nitrogen through nitritation and denitritation. The sidestream nutrient removal prevents nutrients from returning to mainstream treatment, reducing operational costs. Such improvements to wastewater treatment processes can facilitate the transition to the resource recovery facility of the future by becoming a net-energy producer while also achieving the simultaneous benefits of nutrient recovery/removal and reduced costs associated with mainstream treatment. Nutrients and energy can also be recovered in agricultural settings. In this dissertation I studied an agricultural waste treatment system comprising a small-scale tubular anaerobic digester integrated with a low-cost, locally produced struvite precipitation reactor. This study investigated two digesters that treated swine waste in rural Costa Rica. I also facilitated construction of a pilot-scale struvite precipitation reactor that was built on site using local labor and local materials for approximately $920. Local products such as bittern (magnesium source) and soda ash (base) allowed for the production of struvite, a fertilizer that can replace synthetic fertilizer for rural farmers. Liquid-phase concentrations of PO43–-P and NH4+-N in agricultural wastewater increased by averages of 131% and 116%, respectively, due to release from the swine waste during anaerobic digestion. Despite this increase in liquid-phase concentrations, an average of 25% of total phosphorus and 4% of total nitrogen was removed from the influent swine manure through sedimentation in the digesters. During struvite precipitation, an average of 79% of PO43–-P and 12% of NH4+-N was removed from the waste stream and produced a solid with percentages (mass basis) of Mg, N, P of 9.9%, 2.4%, and 12.8%, respectively, indicating that struvite (MgNH4PO4) was likely formed. The treatment system offers multiple benefits to the local community: improved sanitation, removal of nutrients to prevent eutrophication, recovery of struvite as a fertilizer, and production of a final effluent stream that is suitable quality to be used in aquaculture. These are examples of how, more generally, quantifying nutrient recovery from agricultural waste and understanding recovery mechanisms can facilitate progress toward multiple sustainable development goals by improving sanitation, promoting sustainable management of wastes and natural resources, improving food security, and supporting local ecosystems. Managing nutrients from a variety of influent types at different scales can contribute to the achievement of multiple sustainable development goals. Worldwide trends of population growth and resource depletion highlight the need for models to easily allow decision-makers the ability to understand the fate of nutrients and implement infrastructure accordingly.

Η δέσμευση του P με την μορφή του στρουβίτη θεωρείται από τις εναλλακτικές μεθόδους ανάκτησης του P από τα υγρά απόβλητα. Ο στρουβίτης χρησιμοποιείται ως αργά αποδεσμευόμενο λίπασμα, ως υλικό για την σταθεροποίηση αμμωδών εδαφών και συμβάλλει στην αειφόρο ανάπτυξη. Η καταβύθιση του στρουβίτη σε υπέρκορα διαλύματά του υπό σταθερή θερμοκρασία εξαρτάται από τον υπερκορεσμό και από την παρουσία ξένων ιόντων ή ουσιών. Στόχος της παρούσας διατριβής, ήταν η μελέτη της κινητικής της καταβύθισης του στρουβίτη σε συνθήκες σύστασης αντίστοιχες των αστικών αποβλήτων. Η θερμοδυναμική ανάλυση γίνεται με μοντελοποίηση του ειδομορφισμού της υδατικής φάσης ενώ η μελέτη της κινητικής με την μέθοδο του σταθερού υπερκορεσμού η οποία επιτρέπει την διερεύνηση του ρόλου των ιόντων Ca, των βαρέων μετάλλων και οργανικών υδατοδιαλυτών ενώσεων με μεγάλη ακρίβεια και επαναληψιμότητα. Επίσης, διερευνήθηκε ο ετερογενής σχηματισμός του στρουβίτη με την χρήση κρυσταλλικών φύτρων στρουβίτη, SiO2, CaCO3 και πυριτικής άμμου για την μελέτη της πρόσφυσης του καταβυθιζόμενου στερεού στα υποστρώματα αυτά. Προσδιορίστηκε επίσης το γινόμενο διαλυτότητας του στρουβίτη προσεγγίζοντας την ισορροπία από υπέρκορα και ακόρεστα διαλύματα σε διαφορετικές τιμές ιονικής ισχύος. Με την ενζυμική υδρόλυση πολυφωσφορικών οξέων από ειδικά ένζυμα, τις φωσφατάσες, και την σταδιακή απελευθέρωση φωσφορικών ιόντων επετεύχθη ελεγχόμενη καταβύθιση του στρουβίτη σε υψηλούς υπερκορεσμούς. Τέλος, μελετήθηκε η κινητική της διάλυσης του στρουβίτη σε ακόρεστα διαλύματα συνθετικού αποβλήτου και σε διαφορετικές τιμές pH. Από τα κινητικά αποτελέσματα, με βάση την κλασσική θεωρία τη πυρηνογένεσης, προέκυψαν στενά όρια μεταστάθειας του συστήματος και η επιφανειακή διάχυση των δομικών μονάδων ότι είναι το βραδύ στάδιο, το οποίο ελέγχει την καταβύθιση. Το ποσοστό απομάκρυνσης φωσφόρου ήταν 60-65% και από τις δοκιμές συσσωμάτωσης, προέκυψαν ελαφρά σταθεροποιημένα δοκίμια κατάλληλα για εφαρμογές σε καλλιεργήσιμα εδάφη. / Phosphorus precipitated in the form of struvite is a new prospective alternative in phosphorus recovery from wastewaters. Struvite may be used as a slow-released fertilizer, as fitment for stabilization of sandy soil areas and contributing towards sustainable development. Struvite precipitation in supersaturate solution at constant temperature depends on the supersaturation and the presence of foreign ions or substrates. The aim of this thesis was the investigation of struvite precipitation kinetics at conditions similar to municipal wastewaters. The thermodynamic analysis had been done by suitable speciation of aqueous medium while the kinetics of precipitation was investigated with constant solution supersaturation method. This method provides reliable and highly reproducible kinetics results of the effect of calcium ions, heavy metals and organic soluble compounds on the spontaneous precipitation of struvite. The heterogeneous formation of struvite was also investigated in order to examine struvite precipitated adhesion at different substrates. Struvite crystals, SiO2, CaCO3, and silicate sand were used to inoculate the supersaturated solutions. The thermodynamic solubility product of struvite was determined once equilibrium had been attained, when undersaturated and supersaturated solutions were allowed to reach equilibrium, at different ionic strengths values. Controlled struvite precipitation in solutions highly supersaturated was also achieved by the slow evolution of the supersaturation when sufficient phosphate was released from the enzymic action through the phosphatase mediated decomposition of polyphosphates. Finally, the kinetics of struvite dissolution was examined in undersaturate synthetic wastewater solutions at different pH values. The kinetics results, according to the classical nucleation theory, showed that the system stability range was very narrow and a surface diffusion controlled mechanism. A phosphorus recovery corresponding to 60-65% of the initially present phosphorus is feasible. Laboratory experiments using loose sand packs showed mildly consolidated agglomerates that can be used properly for cultivable land.

The majority of the nutrients in household wastewater are found in the urine and in order to facilitate the use the nutrients in the urine as fertilizer, the urine can be can be concentrated. To extract the nutrients from the urine, various technologies for urine concentration are being developed today. As the technologies are relatively new, urine concentration systems have not been installed on a larger scale. In this study, sustainability of three different urine concentration technologies was evaluated through a fictional case study for 2100 people that took inspiration from a planned residential area in Malmö, Sweden, where technology for urine concentration will be implemented in at least one of the buildings. The technologies were evaluated through a multi-criteria assessment (MCA), where different criteria within sustainability categories environment, technical, economic and health were determined based on the Sustainable Development Goals (SDGs). The technologies examined were alkaline dehydration, nitrification-distillation and ion-exchange using a pre-step of struvite precipitation. For the alkaline dehydration technology, fresh urine is added to an alkaline medium, in order to prevent nitrogen losses, and then dried. In the nitrification-distillation technology, stored urine is treated by first being stabilized by a partial nitrification and then distilled in order to reduce the volume. For the ion-exchange and struvite precipitation system, phosphorus is first precipitated from stored urine and nitrogen is then extracted through ion-exchange. The urine concentration technologies were assumed to be installed in semi-centralized treatment plants in basements in the residential area. The other household wastewater was assumed to be treated in the local wastewater treatment plant (WWTP). The results showed that all three urine concentration technologies may contribute to a significant increase in nitrogen recovery from the household sewer. However, this may come at the expense of increased annual costs for the population. Before it is possible to determine whether urine concentration can be an alternative as a complement to the existing wastewater treatment, further studies of the urine concentration technologies and their sustainability are required. However, this study indicated that urine concentration technologies perform well in many of the sustainability criteria examined and therefore have potential to contribute to the SDGs, especially regarding nitrogen recovery. This study can therefore be an incentive for further studies, where the sustainability of an implementation of urine concentration in Sweden is addressed. / Majoriteten av näringen i hushållsavloppsvattnet finns i urinen och för att underlätta användningen av växtnäringsämnena i urinen som gödningsmedel kan den koncentreras. För att utvinna näringen ur urinen utvecklas idag olika tekniker för urinkoncentrering. Då teknikerna är relativt nya har system för urinkoncentrering inte installerats i en större skala. Därför utvärderades hållbarheten för tre olika urinkoncentreringsmetoder genom en fiktiv fallstudie som innefattade 2100 personer. Fallstudien fick inspiration från ett planerat bostadsområde i Malmö, Sverige, där teknik för urinkoncentrering ska implementeras i minst en av byggnaderna. Teknikerna utvärderades genom en multikriterieanalys (MKA), där kriterier inom hållbarhetskategorierna miljö, teknik, ekonomi och hälsa valdes utifrån de Globala målen. De tekniker som utvärderades var alkalisk urintorkning, nitrifikations-destillering och jonbyte där struvitutfällning tillämpades som förbehandling. För den alkaliska urintorkningen tillförs färsk urin till ett alkaliskt medium, för att förhindra kväveförluster, och torkas sedan. I nitrifikations-destillerings tekniken behandlas lagrat urin genom att det först stabiliseras genom en partiell nitrifikation för att sedan destilleras för att reducera volymen. För systemet med jonbyte och struvitfällning, fälls först fosfor från lagrat urin ut och sedan utvinns kvävet genom jonbyte. Urinkoncentreringsteknikerna antogs anläggas i semi-centraliserade reningsverk i källare i bostadsområdet. Övrigt hushållsvatten antogs renas i det lokala avloppsreningsverket. Resultatet visade att samtliga av de tre teknikerna för urinkoncentrering kan bidra till en betydande ökning kväveåtervinning från hushållsavloppet. Dock kan detta komma på bekostnad av ökade årliga kostnader för de boende i området. Innan det är möjligt att avgöra om urinkoncentrering kan vara ett alternativ som ett komplement till den befintliga avloppsreningen i Sege Park krävs vidare studier av urinkoncentreringsteknikerna och deras hållbarhet. Däremot visade denna studie att urinkoncentreringsteknikerna presterar bra i många av de undersökta hållbarhetskriterierna och har därför potential att bidra till de Globala målen, främst när det gäller kväveåtervinning. Denna studie kan därför vara ett incitament för vidare studier som behandlar hållbarheten av en implementering av urinkoncentrering i Sverige.