This thesis presents research work on microbial electrochemistry applications for phosphorus recovery from real wastewater and bioanode sensor development. Phosphorus is a valuable but limited resource which is essential for land fertilizers. Recovering phosphorus using microbial electrolysis cells has been emphasized in wastewater treatment research. Stainless steel mesh (SSM) cathode MECs used in this study showed insufficient phosphorus recovery (68%) because struvite crystals were smaller than the open space between mesh wires (80 µm). Besides, lack of readily biodegradable substrates in the dewatering centrate resulted in limited electric current generation (< 0.2 A/m2) and local pH condition near the cathode. Thus, the following experiments were conducted with stainless steel foil (SSF) cathodes and acetate addition to improve recovery efficiency. Under high electric current density (> 2 A/m2), a thick layer of struvite crystals was formed on the SSF cathode and the phosphorus recovery was increased to 96%. These findings prove that MECs can applied as efficient tools to recover nutrients from real wastewater. Bioanode sensors can be used for real-time and in-situ assessment of water quality. However, the sensor performances are often limited by the narrow detection range, long analysis time, and hysteresis. In order to overcome the challenges for practical applications, a new operation method consisting of three sequences (Normal Operation, Reset Step, and Test Step) was proposed and examined using MEC-based bioanode sensors. Reset Step can eliminate hysteresis effects and produce accurate linear correlations between the soluble COD (chemical oxygen demand) and electric current. The total analysis time was found to be 3 min or even less. The increased detection range (from 75 to 130 mg-COD/L) was achieved by applying a high applied voltage during Test Step. The demonstrated results indicate that MECs can be used for accurate estimation of biodegradable organics in natural or engineered water systems. / Thesis / Master of Applied Science (MASc)

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

Livestock wastewater contains a large amount of nutrients that are available for recovery. In this study, a proof of concept process based on forward osmosis (FO) was proposed and investigated for in-situ formation of struvite from digested swine wastewater. This FO system took advantage of a drawback reverse solute flux (RSF) and used the reversed-fluxed Mg^{2+} for struvite precipitation, thereby accomplishing recovery of both water and nutrient. With 0.5 M MgCl2 as a draw solution, high purity struvite formed spontaneously in the feed solution and the water flux through the FO membrane reached 3.12 LMH. The precipitated struvite was characterized and exhibited a similar composition to that of commercial struvite. The FO system achieve >50% water recovery, >99% phosphate recovery (given sufficient magnesium supply), and >93% ammonium nitrogen removal from the digested swine wastewater. The recovered products (both struvite and water) could potentially generate a value of 1.35 $ m^{-3}. The results of this study have demonstrated the feasibility of nutrient recovery from livestock wastewater facilitated by FO treatment. / Master of Science

Le phosphore est un élément crucial pour la vie sur Terre, de par son implication dans les processus bioénergétiques, le stockage et le traitement de l'information génétique. C'est également l'un des nutriments limitants en agriculture, aux côtés de l'azote et du potassium. Depuis la révolution verte au milieu du 20ième siècle, le monde agricole est dépendant des engrais phosphorés à bas coûts, fabriqués à partir d'une ressource fossile et nécessaires à l'amélioration des rendements des cultures à même de répondre aux besoins en nourriture d'une population en forte croissance. Cependant cette ressource, la roche phosphatée, s'épuise progressivement. De plus, son utilisation est très peu efficiente : moins de 20% du phosphore extrait se retrouve effectivement dans la nourriture consommée. L'une des raisons de cette faible efficience est la spécialisation de régions entières dans des productions agricoles spécifiques. Ainsi, les régions spécialisées dans les cultures à hauts rendements ont besoin de grandes quantités d'engrais minéraux alors que les régions d'élevage intensif ont des excédents de lisier sans terres agricoles suffisamment grandes et proches pour servir de zones d'épandage. L'épandage excessif de lisier en Bretagne est la cause première d'eutrophisation des cours d'eau. Le phosphore contenu dans le lisier porcin pourrait être recyclé sous forme de struvite (MgNH4PO4,6H2O), un engrais phosphaté à dissolution lente, très concentré et facilement transportable vers les régions de cultures végétales nécessitant une fertilisation phosphatée importante. Le phosphore du lisier porcin étant initialement présent sous une forme minérale solide, il est nécessaire de le dissoudre avant de le précipiter en struvite. Parce-que la dissolution par acidification chimique est trop chère et implique un mauvais bilan environnemental, le procédé développé lors de cette thèse utilise l'acidogénèse, un procédé biologique au cours duquel la matière organique est convertie en acides organiques en absence d'oxygène, acidifiant naturellement le lisier porcin. Différents déchets organiques ont été testés en tant que co-substrats dans du lisier porcin brut ou digéré, provoquant une fermentation de type lactique lorsque le co-substrat possédait une forte teneur en glucides facilement biodégradables, et une fermentation avec de nombreux acides organiques produits lorsque la teneur en glucides facilement biodégradables était faible. Il a pu être démontré que la fermentation lactique était le fait de bactéries appartenant au genre Lactobacillus, alors que divers Clostridiales dominaient lors des autres fermentations avec la production d'acétate, propionate, butyrate et valérate. Un réacteur en semi continu alimenté d'un mélange de lisier brut de petit pois et de carottes a permis la dissolution de 50% du phosphore total soit 750 mg-P/L. Après centrifugation, 3.4 g d'hydroxyde de magnésium par litre de surnageant a été ajouté afin d'élever le pH à 8 et ainsi précipiter la struvite. 99% du phosphore dissous a alors été abattu. Le solide obtenu contenait 70% de struvite, un léger excès de phosphore et de magnésium, ainsi que de la matière organique. L'acidogénèse permet l'hydrolyse de la matière organique complexe et la formation d'acides organiques. De ce fait, ce procédé de recyclage du phosphore contenu dans le lisier porcin pourrait être implémenté dans les nombreuses unités de méthanisation présentes en Bretagne et qui traitent des effluents animaux ainsi que des déchets organiques d'origine agricole, industrielle et municipale. La struvite obtenue pourrait être vendue dans les régions ayant besoin de fertilisation phosphatée alors que la matière organique du digestat pourrait être maintenue en Bretagne. Un tel procédé réduirait significativement l'eutrophisation due à l'épandage excessif du lisier tout en diminuant les besoins en fertilisants minéraux fossiles grâce à une source alternative aux performances fertilisantes équivalentes. / Phosphorus is a crucial nutrient for life, implicated in cellular bioenergetics as well as storage and processing of genetic information. It is also one of the limiting nutrients in agriculture with nitrogen and potassium. Since the green revolution in the middle of the 20th century, agriculture has relied on increasing amounts of cheap mineral P-fertilizers produced from a fossil resource to improve crop yields and sustain population growth. However, the resource is depleting and its use efficiency is poor: less than 20% of extracted P is actually consumed in food. One of the reasons for this is the specialization of entire regions into on type of agricultural production or another. Thus, regions focusing on high yield crops require large applications of fossil mineral fertilizers while intensive livestock breeding areas cannot find an output for their P-rich manure due to the distance with crop fields in need of P fertilization. Over application of animal manure in Brittany is the main cause of eutrophication in the region. Phosphorus could be recovered from pig manure as struvite, a concentrated, slow-release mineral fertilizer easily transported to crop-oriented regions in need of P fertilization. P in pig slurry is mostly under a solid inorganic form, requiring dissolution prior to precipitation as struvite. Because chemical acidification is too expensive and harmful to the environment, the process developed in this PhD relied on acidogenesis, a biological process in which organic matter is converted to organic acids under anaerobic conditions, thus naturally acidifying the swine slurry. Various organic wastes were tested as organic co-substrates on raw and digested pig slurry, leading to lactic acid fermentation when the co-substrate had a high content in easily biodegradable carbohydrates and a fermentation with diverse organic acids produced at low content in easily biodegradable carbohydrates. Lactobacillus was the genus responsible for lactic acid fermentation and various Clostridiales dominated otherwise, producing acetate, propionate, butyrate and valerate. A reactor was operated with semi-continuous feeding of raw swine slurry and carrot/pea, leading to the dissolution of 50% total-phosphorus or 750 mg-P/L. After centrifugation, struvite was precipitated in the supernatant by adding magnesium hydroxide to increase the pH to 8. 99% of dissolved P precipitated. The solid recovered contained 70% of struvite, a slight excess of P and Mg as well as organic matter. Because hydrolysis of organic matter and production of organic acids occurs during acidogenesis, the process could be implemented in the many anaerobic digestion units installed in Brittany treating animal manure and agricultural, industrial and municipal organic waste. The struvite recovered could be sold to regions in need while the digestate impoverished in P and rich in organic matter could be kept locally. Such process would reduce eutrophication due to over application of pig manure and also reduce the reliance on fossil P fertilizer by offering an alternative source with equivalent fertilizing performances.

La réduction des apports phosphorés des eaux usées régie par la Directive Européenne de 1991 (91/271/EEC) est considérée comme le facteur clé de la lutte contre la pollution des rivières et des lacs. Ces travaux concernent exclusivement l'étude de la formation maîtrisée de struvite (MgNH4PO4.6H2O) par précipitation comme alternative originale de récupération du phosphore et, par voie de conséquence, de l'ammonium à partir d'eaux usées. Un atout de ce procédé concerne la valorisation du précipité en tant que fertilisant. Dans ce contexte général, l'objectif consiste à développer une démarche combinant des aspects expérimentaux et de modélisation de la précipitation de la struvite. Un effluent synthétique contenant du phosphore, du magnésium et de l'ammonium a servi de solution modèle pour étudier le rôle de la température, de la concentration en réactifs, et du pH sur l'efficacité de la précipitation de la struvite ainsi que sur la distribution de la taille des cristaux obtenus. Les essais expérimentaux ont été réalisés par précipitation en cuve agitée. Diverses méthodes d'analyse des phases solide et liquide (spectrophotométrie, absorption atomique, granulométrie laser, MEB et Morphométrie) ont été utilisées. Le dosage du magnésium, ainsi que celui d'ammonium et du phosphore permet de déterminer le taux de conversion de ces composés et d'étudier une éventuelle formation d'un sous-produit. L'approche développée dans ce mémoire permet de déterminer les conditions de pH et de température favorisant l'efficacité maximale pour la récupération de la struvite. Deux voies complémentaires ont été proposées. La première étape concerne la modélisation des équilibres chimiques, d'une part, pour calculer le taux de conversion du phosphate final en fonction du pH à l'équilibre pour plusieurs températures et, d'autre part, pour évaluer l'impact de la température sur la constante de solubilité de la struvite. La stratégie numérique implique un algorithme génétique (NSGA II) pour initialiser efficacement un algorithme de résolution classique (Newton Raphson) et garantir la robustesse de la procédure. Dans la seconde étape, un modèle numérique basé sur un bilan de population couplé avec le modèle thermodynamique prédit la distribution de taille des particules,. Cette approche s'est avérée particulièrement stable d'un point de vue numérique lors du calcul des paramètres des vitesses de nucléation et de croissance, utilisés ensuite pour prédire la distribution de taille à l'aide d'une méthode de reconstruction. La forme de la distribution de taille des cristaux obtenue est typique d'un modèle nucléation – croissance. La méthodologie proposée trouve tout son intérêt pour traiter des effluents de qualité variable et prédire l'efficacité du procédé dans lequel le contrôle du pH et de la sursaturation constituent des paramètres clés. / The reduction of phosphorus contribution in wastewater, governed by the European directive of 1991 (91/271/EEC) is regarded as the key factor of the fight against pollution of rivers and lakes. This work concerns exclusively the study of the controlled struvite formation (MgNH4PO4.6H2O) by precipitation as an alternative removal of phosphorus and, consequently, of ammonium from waste-water discharges. The valorization of the precipitate as a fertilizer constitutes an asset of the process. In this general context, the objective consists in developing a methodology combining an experimental approach with struvite precipitation modelling. A synthetic effluent containing phosphorus, magnesium and ammonium was used as a model solution to study the role of temperature, concentration in reagents and pH on struvite precipitation efficiency as well as on particle size distribution in a stirred tank reactor. Various analysis methods of both solid and liquid phases (spectrophotometry, atomic absorption, laser granulometry, MEB and Morphology) were used. The residual concentration of magnesium, ammonium and phosphorus allows to determine the conversion rate of these compounds and to study a likely formation of a co-product. The proposed framework is based on a two-level modelling approach. The former level, based on an equilibrium prediction of the study system Mg-PO4-NH4, involves, on the one hand, the computation of the final conversion rate of phosphate as a function of equilibrium pH at different temperatures and, on the other hand, the temperature impact assessment on struvite solubility product. The numerical strategy implies a genetic algorithm (NSGA II) to initialize a traditional algorithm of resolution (Raphson Newton) and to guarantee the robustness of the process. In the second stage, a population balance-based model coupled with the thermodynamic one predicts the particle size distribution. This approach turns out to be particularly numerically stable for the identification of nucleation and particle growth kinetics parameters that are then used to predict the size distribution, typical of a nucleation - growth model, using a method of reconstruction. The proposed methodology is particularly interesting for the treatment of industrial waste-water discharges that may be of variable quality as well as for the prediction of the process efficiency for which pH control and supersaturation constitute key parameters.

<p>In connection with Henriksdals wastewater treatment plant (WWTP) a smaller plant is situated called Sjöstadsverket where new methods for wastewater treatment are tested and evaluated in different process lines. On one of the lines experiments with enhanced biological phosphorous removal (EBPR), have been carried out to evaluate if it is a good alternative to traditional chemical phosphorus removal. This thesis evaluates the results from the experiments conducted during fall 2005.</p><p>The incoming water from Hammarby Sjöstad consists of only household wastewater, which gives a wastewater with high concentrations of nutrients and organic carbon. This is partly positive, because one of the limiting factors for effective biological phosphorus removal is the lack of easily biodegradable organic carbon. The high concentrations of ammonium and phosphorus demand a high reduction to achieve the requirements of outgoing concentration.</p><p>To optimize the process experiments with different recirculations and different aeration techniques have been made. The experiments have shown that it is possible to obtain good results, with periods of very low outgoing phosphorus concentrations below 0,15 mg/L. It was, however, hard to obtain a stable process and to keep a good sludge quality during the period.</p><p>Primary sludge was hydrolysed to increase the amount of easily degradable organic material into the biological step of the process. The hydrolyse had a high efficiency during the test period, but with big variations. The most desirable fraction of organic material, VFA, increased to approximately 1500 mg/L during the best periods. This is only 9 % of the amount VFA in the primary sedimentation, but could be increased with a higher flux.</p><p>When the bioP sludge is fermented as a part of sludge treatment, a supernatant from digester sludge with high concentrations of phosphorus is received. To avoid to return phosphor into the activated sludge process and to recycle phosphorus, experiments with phosphorus precipitation were made. By using struvite precipitation up to 92 % of the phosphorus in the supernatant was reduced and precipitated. This was 12 % of the total amount of incoming phosphourus and was achieved at a pH just over 9 in the experiment tank and a Mg:P quote of 1:1.</p> / <p>I anslutning till Henriksdal’s reningsverk ligger Sjöstadsverket som är ett mindre reningsverk där nya reningsmetoder testas och utvärderas i på ett antal olika försökslinjer. På en av linjerna har försök med biologisk fosforrening, även kallat BioP, utförts för att undersöka om det är ett alternativ till konventionell kemisk rening av fosfor. Detta arbete sammanfattar resultaten från de experiment som utförts under hösten 2005.</p><p>I Hammarby Sjöstad, som förser Sjöstadsverket med avloppsvatten, separeras dag och spillvatten, vilket bidrar till ett näringsrikt vatten med en hög halt organiskt material. Detta är delvis positivt, då en av de begränsande faktorerna för en effektiv biologisk fosforrening är bristen på lättillgängligt organiskt material. De höga halterna inkommande fosfor och kväve kräver dock en högre reningsgrad för att de stränga utsläppsmålen ska nås. För att optimera processen har försök med olika inställningar på recirkulationsgrader genomförts och försök med olika luftningsstrategier. Försöksperioden har visat att det går att få mycket bra resultat, med periodvis utgående fosfathalter under 0,15 mg/L. Det har dock varit svårt att få en stabil process och behålla en bra slamkvalitet under hela försöksperioden.</p><p>Primärslam från försedimenteringen har hydrolyserats för att öka mängden lättillgängligt organiskt material in till det biologiska reningssteget. Hydrolysen fungerade bra under hela försöksperioden, dock med stora variationer. Den mest önskvärda fraktionen lättillgängligt organiskt material, VFA, hade under de bästa perioderna ökat till ca 1500 mg/L i hydrolysen. Detta utgör approximativt 9 % av mängden VFA i försedimenteringen, men skulle kunna ökas vid ett större flöde.</p><p>Då BioP-slammet rötas som en del av slambehandlingen fås ett fosforrikt rejektvatten. För att undvika att få in fosfor till aktivslamprocessen och för att ta till vara på fosfor som näringsämne har försök med fosforåtervinning från rejektvatten gjorts. Genom att använda sig av struvitfällning kunde upp till 92 % av fosforn i rejektvattnet reduceras och fällas ut. Detta motsvarar 12 % av den totala inkommande fosforhalten och uppnåddes vid pH strax över 9 i struvitfällningstanken och med en Mg:P kvot på 1:1.</p>

O ciclo aberto que o fósforo percorre na sociedade contemporânea pode ser visto como uma das maiores falhas da sua sustentabilidade. Sendo este um elemento básico para qualquer ser vivo, é realmente incômodo pensar que todo o fósforo que percorre as diversas instâncias da sociedade (como agricultura, alimentos ou consumo humano) provém direta ou indiretamente da mineração, portanto, de uma fonte esgotável. Se algumas estimativas da duração de toda a reserva de rochas fosfatadas do planeta não estivessem beirando a casa de um século, esse tema, acerca da geração de uma fonte renovável e sustentável de P, não teria o mesmo peso. A presente pesquisa, realizada com uma visão multidisciplinar levando em conta estudos mineralógicos; agrícolas; de crescimento de cristais; formação de carapaça de crustáceos marinhos; tratamento de esgoto; termodinâmica e cinética de precipitações químicas traz à luz da realidade nacional uma discussão acerca dos parâmetros que possibilitam a recuperação do fósforo (e do nitrogênio) diretamente do esgoto. Nos últimos anos, diversas tentativas de precipitação de estruvita no Brasil não foram bem sucedidas. Por esse motivo, essa dissertação foi desenvolvida com o intuito de contribuir com uma melhor compreensão a respeito dos fenômenos envolvidos na formação e crescimento desses cristais. Para isso, foram realizados ensaios com amostras de água ultrapura; efluente do reator anaeróbio de fluxo ascendente com manto de lodo da estação de tratamento de esgoto (ETE) Anhumas; urina pura e efluente dos processos de desaguamento do lodo da ETE Franca (um sistema de lodos ativados convencionais). Este último apresentou altas concentrações de cálcio, o maior interveniente na formação de estruvita, devido ao recebimento de lodo de estação de tratamento de água. A investigação experimental foi dividida em três etapas: (1) Primeiramente, as principais variáveis da reação de cristalização foram avaliadas e percebeu-se que, o que a rege é o quanto o meio se encontra supersaturado com relação aos sais de estruvita. Portanto, as variáveis que influenciam na supersaturação (como pH e concentração de reagentes) podem ser manipuladas para que a reação ocorra da maneira que for desejável. (2) Quando a água residuária contém cálcio, forma-se uma fase amorfa de carbonato de cálcio, que é muito reativa e bastante metaestável (que nesse caso acaba sendo estabilizada), na qual o fósforo e o magnésio adsorvem, podendo inclusive causar uma falsa impressão de que se formou estruvita, devido ao consumo dos reagentes. Deste entendimento, foi possível uma proposta bastante simples de solução para o problema: semeadura com cristais de estruvita. (3) A última etapa da dissertação explica o porquê da dificuldade de encontrar os picos de estruvita nos difratogramas de raios-x, tanto em algumas pesquisas nacionais quanto no começo do presente estudo. Esta dificuldade está relacionada às mudanças de fases do cristal quando exposto a altas temperaturas, isto é, durante o processo de secagem em estufa. / The opened cycle in which the phosphorus flows within the contemporary society is one of the biggest lack on its sustainability. Being this element so primary for the life of any being, it is really uncomfortable to think that all phosphorus that runs through all instances of our society (as agriculture, foods or human consumption) comes directly or indirectly from mining, thus a non-renewable source. By means of a multidisciplinary vision taking into account mineralogical, agriculture, crystal growth, marine crustaceous, wastewater treatment, chemical kinetics and thermodynamic studies the parameters which govern this crystallization reaction were brought to light, in order to make possible the recovery of phosphorus directly from sewage. For this reason, the development of this research was to create a better comprehension around the phenomena of formation and growth of struvite crystals. The crystallization media used were ultrapure water, effluent from an upflow anaerobic sludge bed reactor also treating domestic sewage in real scale, urine, and effluent of the dewatering processes of the sludge from a conventional activated sludge system (anaerobically digested) treating domestic sewage in real scale (because this WWTP receives WTP sludge with a high content of calcium, the major interfering ion on struvite formation). This study was made in three steps: (1) At first, the main parameters (usually controlled) of this crystallization reaction were evaluated. It was concluded that what controls the reaction is how much the crystallization media is supersaturated of the struvite salts. Thus, all parameters which have an influence on that (as pH and reagents concentration) can be manipulated for the reaction to occur in the desirable way. (2) The ion which interfere the most on the formation of struvite (calcium) was also studied, and the conclusion was that an amorphous calcium carbonate phase, was formed, which is a very metastable morphology of this salt, and thus it is not found in other conditions which are not as specific as those. With this theory, a proposal of a simple solution for this problem was formulated: struvite seeding. (3) The last step of this research explains why the characteristic peaks of struvite crystals were so difficult to be found on the x-ray diffractograms on the beginning of this study and by other Brazilian researchers. This difficult is related to the phase transitions due to the exposition of the crystals to higher temperatures.

O ciclo aberto que o fósforo percorre na sociedade contemporânea pode ser visto como uma das maiores falhas da sua sustentabilidade. Sendo este um elemento básico para qualquer ser vivo, é realmente incômodo pensar que todo o fósforo que percorre as diversas instâncias da sociedade (como agricultura, alimentos ou consumo humano) provém direta ou indiretamente da mineração, portanto, de uma fonte esgotável. Se algumas estimativas da duração de toda a reserva de rochas fosfatadas do planeta não estivessem beirando a casa de um século, esse tema, acerca da geração de uma fonte renovável e sustentável de P, não teria o mesmo peso. A presente pesquisa, realizada com uma visão multidisciplinar levando em conta estudos mineralógicos; agrícolas; de crescimento de cristais; formação de carapaça de crustáceos marinhos; tratamento de esgoto; termodinâmica e cinética de precipitações químicas traz à luz da realidade nacional uma discussão acerca dos parâmetros que possibilitam a recuperação do fósforo (e do nitrogênio) diretamente do esgoto. Nos últimos anos, diversas tentativas de precipitação de estruvita no Brasil não foram bem sucedidas. Por esse motivo, essa dissertação foi desenvolvida com o intuito de contribuir com uma melhor compreensão a respeito dos fenômenos envolvidos na formação e crescimento desses cristais. Para isso, foram realizados ensaios com amostras de água ultrapura; efluente do reator anaeróbio de fluxo ascendente com manto de lodo da estação de tratamento de esgoto (ETE) Anhumas; urina pura e efluente dos processos de desaguamento do lodo da ETE Franca (um sistema de lodos ativados convencionais). Este último apresentou altas concentrações de cálcio, o maior interveniente na formação de estruvita, devido ao recebimento de lodo de estação de tratamento de água. A investigação experimental foi dividida em três etapas: (1) Primeiramente, as principais variáveis da reação de cristalização foram avaliadas e percebeu-se que, o que a rege é o quanto o meio se encontra supersaturado com relação aos sais de estruvita. Portanto, as variáveis que influenciam na supersaturação (como pH e concentração de reagentes) podem ser manipuladas para que a reação ocorra da maneira que for desejável. (2) Quando a água residuária contém cálcio, forma-se uma fase amorfa de carbonato de cálcio, que é muito reativa e bastante metaestável (que nesse caso acaba sendo estabilizada), na qual o fósforo e o magnésio adsorvem, podendo inclusive causar uma falsa impressão de que se formou estruvita, devido ao consumo dos reagentes. Deste entendimento, foi possível uma proposta bastante simples de solução para o problema: semeadura com cristais de estruvita. (3) A última etapa da dissertação explica o porquê da dificuldade de encontrar os picos de estruvita nos difratogramas de raios-x, tanto em algumas pesquisas nacionais quanto no começo do presente estudo. Esta dificuldade está relacionada às mudanças de fases do cristal quando exposto a altas temperaturas, isto é, durante o processo de secagem em estufa. / The opened cycle in which the phosphorus flows within the contemporary society is one of the biggest lack on its sustainability. Being this element so primary for the life of any being, it is really uncomfortable to think that all phosphorus that runs through all instances of our society (as agriculture, foods or human consumption) comes directly or indirectly from mining, thus a non-renewable source. By means of a multidisciplinary vision taking into account mineralogical, agriculture, crystal growth, marine crustaceous, wastewater treatment, chemical kinetics and thermodynamic studies the parameters which govern this crystallization reaction were brought to light, in order to make possible the recovery of phosphorus directly from sewage. For this reason, the development of this research was to create a better comprehension around the phenomena of formation and growth of struvite crystals. The crystallization media used were ultrapure water, effluent from an upflow anaerobic sludge bed reactor also treating domestic sewage in real scale, urine, and effluent of the dewatering processes of the sludge from a conventional activated sludge system (anaerobically digested) treating domestic sewage in real scale (because this WWTP receives WTP sludge with a high content of calcium, the major interfering ion on struvite formation). This study was made in three steps: (1) At first, the main parameters (usually controlled) of this crystallization reaction were evaluated. It was concluded that what controls the reaction is how much the crystallization media is supersaturated of the struvite salts. Thus, all parameters which have an influence on that (as pH and reagents concentration) can be manipulated for the reaction to occur in the desirable way. (2) The ion which interfere the most on the formation of struvite (calcium) was also studied, and the conclusion was that an amorphous calcium carbonate phase, was formed, which is a very metastable morphology of this salt, and thus it is not found in other conditions which are not as specific as those. With this theory, a proposal of a simple solution for this problem was formulated: struvite seeding. (3) The last step of this research explains why the characteristic peaks of struvite crystals were so difficult to be found on the x-ray diffractograms on the beginning of this study and by other Brazilian researchers. This difficult is related to the phase transitions due to the exposition of the crystals to higher temperatures.

The wastewater treatment process has developed with the primary goals of protecting receiving water ecosystems and human health. Over time, there have been continuous innovations in process efficiencies, energy recovery, and nutrient removal. Wastewater offers opportunity for recovery of resources of various economic values, and recent research aims at process innovation to optimize resource recovery while still achieving the primary goals of the treatment process. The objective of this study is to assess the logistical and economic feasibility of recovery of nitrogen and phosphorus at two municipal treatment plants in the Tampa Bay area, one employing aerobic digestion and the other anaerobic digestion. The study is conducted using literature review of applicable processes, mass balance on the fate of nutrients (N and P) through the treatment plants and special attention to sludge handling. Based on the whole-plant mass balance conducted at the facilities, it is estimated that over 80% of the nutrient influent is routed to the solids handling side of the plant, warranting special attention to this area for nutrient recovery. Sludge digested through anaerobic and anaerobic processes have distinctly different characteristics and opportunities for resource recovery are specific to each process. Mass balances for nitrogen in the anaerobic digestion process show a high concentration of dissolved ammonia. The feasibility of struvite precipitation by addition of phosphate and magnesium compounds is evaluated through batch reaction using anaerobic sludge filtrate. Aerobic sludge contains most of the nutrient resources in the solid phase, ready for recovery if handled properly. Phosphorus release is a potential concern and specific phosphorus release rates are evaluated for a municipal scale aerobic digester.

A cement material has been developed that has a controllable set time, compressive strength of about 50 MPa and shrinkage of under 2% when heated to 960 degrees centigrade. The main compound of this material has been shown to be the potassium analogue of struvite, in which potassium ion is substituted for the ammonium ion. The cement is formed by reacting a slurry made with potassium carbonate and monoammonium phosphate with magnesium oxide. Ihe amount and rate of addition of water to the mixture is controlled to determine the set time. It has been demonstrated that this cement may be used as a matrix in conjunction with cenospheres or cellulose fibres to form a low density composite material, and with silica powder to form a high strength composite. As well as optimising the cement mix for maximum strength and minimum shrinkage, a variety of properties of the K-cement were investigated. It was found that long term exposure of the cement to the atmosphere does not result in the formation of magnesium carbonate, but long term exposure to saline solutions can result in the formation of dypingite on the surface. No effect on strength was observed as a consequence of the age of the slurry or the cement, within 1-2 weeks / Doctor of Philosophy (PhD)