High energy consumption in conventional wastewater treatment contributes to a large amount of greenhouse emissions and causes environmental problems such as acid rain and climate change. Many technologies, microbial electrolysis cells (MECs), electrodialysis (ED), and anaerobic digestion (AD), were developed to make wastewater treatment more efficient and economical. This thesis investigated novel MECs and ED to decrease energy consumption in wastewater treatment and recover resources from wastewater. In addition, inhibition of ammonia and acetic acid on high-solid AD was examined in this research. The multi-electrode stack design was applied in MECs to treat municipal wastewater. Rapid organic removal and minimized biosolids production were observed in the stacked MECs. In addition to municipal wastewater treatment, MECs can also recover/remove heavy metals from industrial wastewater. Various removal/recovery mechanisms of toxic heavy metals were discussed in this thesis. ED with bipolar membranes (BPMs) was examined to produce high-purity ammonium sulfate from real wastewater steams. This examination indicates valuable nutrients resources (e.g., ammonium sulfate) can be recovered from wastewater and used as land fertilizers for food production. Membrane scaling problems were also evaluated in ED systems since the formation of inorganic scalants can affect the efficiency of nutrients recovery significantly. In addition, the inhibition of ammonia and acetic acid on AD performance was incorporated in a modified anaerobic digestion model (ADM) for reliable simulation of individual biological reactions in high-solid AD. This research contributes to the body of knowledge by developing wastewater treatment technologies with less energy consumption and biosolids production. The reduction of energy consumption and biosolids production can reduce fossil fuel combustion and waste disposal. Resources, such as ammonia and heavy metals, can be recovered and reused by using the investigatory technologies. Therefore, with these developed technologies, wastewater treatment meets the goal of sustainable development and helps to establish a new green circular economy. / Thesis / Doctor of Philosophy (PhD) / High energy consumption is a main challenge in wastewater treatment. However, a large amount of energy in wastewater can be recovered and reused. The recovery of energy from wastewater can reduce energy costs, save resources, and protect the environment. This research aims to develop novel wastewater treatment technologies to save energy by recovering nutrients and producing biogas from wastewater. Bioelectrochemical systems are used to produce hydrogen gas and recover heavy metals from municipal or industrial wastewater. Electrodialysis systems are applied in ammonia recovery and fertilizer production. Anaerobic digestion systems are employed to produce methane gas as a renewable energy source from wasted sludge. These technologies reduce energy consumption in wastewater treatment and help to establish a new green circular economy for resource recovery.

Submitted by Jean Medeiros (jeanletras@uepb.edu.br) on 2018-05-10T14:20:27Z No. of bitstreams: 1 PDF - Nathália Nunes de Melo.pdf: 18947535 bytes, checksum: 4cfce3961def8f699d9241cbcdbd3859 (MD5) / Made available in DSpace on 2018-05-10T14:20:27Z (GMT). No. of bitstreams: 1 PDF - Nathália Nunes de Melo.pdf: 18947535 bytes, checksum: 4cfce3961def8f699d9241cbcdbd3859 (MD5) Previous issue date: 2018-02-27 / Conselho Nacional de Desenvolvimento Científico e Tecnológico - CNPq / The treatment of sewage sludge is a challenge for environmental sanitation due to its difficulty to stabilize and large number of undesirable elements. On the other hand, it is found in its composition a high concentration of nutrients that can be reused in the nature in a beneficial way, but that end up being wasted in the conventional treatments. In the present work the treatment of sewage sludge in an anaerobic dynamic membrane bioreactor (AnDMBR) was carried out, in which it was possible to verify that the use of the dynamic membrane provided an excellent performance for the sludge filtration, producing turbidity permeate below 1 NTU after the formation of the separation layer. In addition, 53.2% of the phosphorus concentration and 35.6% of the nitrogen concentration were found in its composition, demonstrating that the use of this technology is a very interesting alternative for the recovery of these nutrients. As long as produced a less pollutant and nutrient-recovering permeate, there was also a marked stabilization of the concentrate, which showed a reduction of the organic fraction from 0.76 to 0.54 and the F/M ratio of 0.07 kgCOD/KgVSS to 0.02 KgCOD/KgVSS, furthermore a considerable methane production was observed. / O tratamento do lodo de esgoto consiste em um desafio na área de saneamento ambiental por se tratar de um resíduo de difícil estabilização e com grande quantidade de elementos indesejáveis. Por outro lado, é encontrada na sua composição uma elevada concentração de nutrientes que podem ser reutilizados na natureza de maneira benéfica, mas que acabam sendo desperdiçados nos tratamentos convencionais. No presente trabalho foi realizado o tratamento do lodo de esgoto em um biorreator anaeróbio de membrana dinâmica (BRAnMD), no qual foi possível verificar que a utilização da membrana dinâmica proporcionou um ótimo desempenho para a filtração do lodo, produzindo um permeado com turbidez abaixo de 1 NTU após o período de formação da camada de separação. Além disso, na sua composição foi encontrada 53,2% da concentração do fósforo afluente e 35,6% da concentração de nitrogênio, demonstrando, dessa forma, que a utilização dessa tecnologia consiste em uma alternativa bastante interessante para a recuperação desses nutrientes. À medida que produzia um permeado menos poluente e recuperava de nutrientes, verificou-se também uma estabilização acentuada do concentrado, que apresentou uma redução da fração orgânica de 0,76 para 0,54 e da relação A/M de 0,07 KgDQO/KgSSV para 0,02 KgDQO/KgSSV além de possibilitar uma considerável produção de metano.

L'utilisation des microalgues dans le traitement des eaux usées est de plus en plus étudiée pour intégrer/remplacer les systèmes de traitement actuels permettant d'éliminer les nutriments et autres polluants. Cependant, l’utilisation des microalgues dans le traitement des eaux usées en est principalement au stade de la recherche, par exemple faible élimination des nutriments et croissance de la biomasse des microalgues. Le but de cette thèse était de permettre une élimination efficace des éléments nutritifs et de la matière organique des eaux usées par les microalgues tout en favorisant la production de biomasse de microalgues. C. vulgaris et S. acuminatus ont été cultivés dans des photobioréacteurs discontinus avec des digestats issus de la digestion anaérobie (AD) de boues biologiques de boue de vidange provenant d’une station d’épuration municipale (ADMW) et d’une usine de traitement des eaux usées d’une usine de pâtes et papiers (ADPP). Les rendements d’élimination de l’ammonium étaient supérieurs à 97% lorsque les deux microalgues étaient cultivées séparément dans de l’ADPP. Toutefois, 24 et 44% de l’ammonium ont été retirés de l’ADMW par C. vulgaris et S. acuminatus, respectivement. Les deux microalgues ont efficacement éliminé le phosphate (> 96%), tandis que la couleur (74–80%) et la DCO soluble (27–39%) ont été partiellement éliminées de ADMW et d'ADPP. La plus forte concentration de biomasse de S. acuminatus (7,8 à 10,8 g L-1 VSS) dans l'ADPP figure parmi les rendements les plus élevés signalés pour les microalgues dans les eaux usées réelles. Des rendements de biomasse supérieurs de S. acuminatus ont été obtenus dans de l'ADPP thermophile (10,2 ± 2,2 et 10,8 ± 1,2 g L-1) par rapport à de l'ADPP mésophile prétraité (7,8 ± 0,3 g L-1). En outre, les concentrations les plus élevées en biomasse et en méthane de microalgues ont été obtenues dans le même système intégré de culture de AD et de microalgues. Les concentrations de fer (0,1, 1,0 et 1,9 mg L-1) et de sulfure de soufre (3,7, 20 et 35,8 mg L-1) affectaient davantage l'efficacité de l'élimination de l'azote et la concentration de la biomasse de microalgues davantage dans les ammonium probablement dû à différents mécanismes d'assimilation de microalgues. Dans cette étude, le milieu contenant du nitrate comme source d'azote avec 1,0 mg de L-1 de fer et 35,8 mg de L-1 de sulfate et de soufre a permis d'obtenir la plus forte concentration de biomasse de microalgues. L'effet de la concentration en fer sur l'efficacité d'élimination des nitrates et la croissance des microalgues était plus significatif que la concentration en sulfate, alors que l'effet d'interaction entre le sulfate et le fer n'était pas observé. L'efficacité moyenne d'élimination de l'ammonium (14 à 30%) et la concentration en biomasse de microalgues (0,55 à 1,17 g de POC L-1) dans un photobioréacteur à membrane à flux continu ont été améliorées par addition de zéolite (0,5 g L-1). La zéolite fournissait probablement un habitat pour la croissance attachée de microalgues et une grande disponibilité d'ammonium pour la croissance à la surface de la zéolite en raison de l'adsorption d'ammonium par la zéolite. Une augmentation supplémentaire de la concentration en zéolite (de 0,5 à 1 et 5 g L-1) n’a pas amélioré l’efficacité de l’élimination de l’ammonium ni la concentration de la biomasse, probablement en raison de la turbidité accrue de la solution provoquée par la fragmentation de la zéolite ajoutée en particules plus fines, ce qui a réduit la disponibilité de lumière. Ces travaux ont montré la possibilité d'utiliser des microalgues dans le traitement des eaux usées pour éliminer efficacement les nutriments et les matières organiques, tout en favorisant la croissance des microalgues. La sélection d'espèces de microalgues adaptées aux eaux usées spécifiques pour éliminer les nutriments et les matières organiques est essentielle pour promouvoir les applications de traitement des eaux usées à base d'algues / Use of microalgae in wastewater treatment has been increasingly studied to integrate with or replace the present treatment systems for removal of nutrients and other pollu-tants. The potential advantages of this integration (wastewater treatment and microalgal cultivation) could be simultaneous recovery of nitrogen and phosphorus and the use of produced microalgal biomass as feedstock for e.g. biofuel, fertilizer and/or energy. However, the use of microalgae in wastewater treatment is mainly in research stage due to e.g. low nutrient removal and microalgal biomass growth. The aim of this thesis was to enable efficient nutrient and organic matter removal from wastewaters by mi-croalgae while promoting microalgal biomass production. Chlorella vulgaris and Scenedesmus acuminatus were successfully grown in batch photobioreactors with liquid digestates from anaerobic digestion (AD) of biosludge from a municipal wastewater treatment plant (ADMW) and a pulp and paper mill wastewater treatment plant (ADPP). The final ammonium removal efficiencies were above 97% when cultivating both microalgae separately in ADPP, however, only 24% and 44% of ammonium were removed from ADMW by C. vulgaris and S. acuminatus, respectively. Both microalgae efficiently removed phosphate (>96%), while color (74–80%) and sol-uble COD (27–39%) were partially removed from ADMW and ADPP. The obtained highest S. acuminatus biomass concentration (7.8–10.8 g L-1 VSS) in ADPP is among the highest yields reported for microalgae in real wastewaters. Higher S. acuminatus biomass yields were obtained in thermophilic ADPP (without and with pretreatment prior to AD: 10.2±2.2 and 10.8±1.2 g L-1, respectively) than in pretreated mesophilic ADPP (7.8±0.3 g L-1). In addition, the highest microalgal biomass concentration and methane yields were obtained in the same integrated AD and microalgal culti-vation system (thermophilic AD with pretreatment).The iron (0.1, 1.0, and 1.9 mg L-1) and sulfate-sulfur (3.7, 20, and 35.8 mg L-1) concen-trations were found to affect nitrogen removal efficiency and microalgal biomass con-centration more in the media with nitrate than with ammonium, probably due to different microalgal assimilation mechanisms for nitrate and ammonium. In this study, synthetic medium with nitrate as nitrogen source with 1.0 mg L-1 iron and 35.8 mg L-1 sulfate-sulfur enabled the highest microalgal biomass concentration. The effect of iron concentration on nitrate removal efficiency and microalgal growth was more significant than that of sulfate concentration, while the interaction effect between sulfate and iron was not observed. The average ammonium removal efficiency (14 to 30%) and microalgal biomass con-centration (0.55 to 1.17 g particulate organic carbon per L) in continuous-flow mem-brane photobioreactor were promoted by adding a low concentration of zeolite (0.5 g L-1). The zeolite likely provided a habitat for attached growth of microalgae and high availability of ammonium for growth on the surface of the zeolite due to ammonium adsorption to zeolite. Further increase in zeolite concentration (from 0.5 to 1 and 5 g L-1) did not improve ammonium removal efficiency or biomass concentration. This was likely due to the increased solution turbidity caused by breaking apart of added zeolite particles into finer particles, which reduced light availability.In summary, this work showed the possibility of utilizing microalgae in wastewater treatment to efficiently remove nutrients and organic matter, and simultaneously pro-mote microalgal growth. Selecting suitable microalgal species for the specific wastewater to remove nutrients and organic matter is essential to promote algae-based wastewater treatment applications

Bioelectrochemical systems (BES) is a platform technology that is able to realize versatile engineering functions and recover valuable resources in an energy-efficient manner. One of the potential applications of BES is to remove and recover nutrients simultaneously from nutrient-rich wastewater, such as digested manure from livestock. A four-chamber BES was developed and used in this study to explore the potential to remove and recover hexavalent Chromium from synthetic wastewater, and ammonia and phosphate from digested manure. The BES was able to achieve 99.6% removal of Chromium by membrane adsorption in 5 days but failed to recover in the concentration chamber. Nutrients were removed from the waste stream and recovered in the recirculated catholyte by the electrical field generated from the waste. The BES was demonstrated to achieve substantial COD removal, nutrients removal and recovery. On average, the removal efficiencies were about 50% for COD, 85% for NH4-N and 40% for PO4-P, and the concentration of NH4-N recovered in the catholyte was 670 mg/L after 5 cycles under an applied voltage of 0.8 V. PO4-P was not recovered in solution, probably because it has precipitated under the alkaline condition together with Mg2+ and Ca2+ concentrated in the catholyte. It was also demonstrated that nutrients removal and recovery depended on the current generation and were mostly completed at high current. To sum up, the BES was proven to be an effective and sustainable approach to remove and recover nutrients from digested manure. / Master of Science

A vinhaça é um dos resíduos provenientes da indústria sucroalcooleira, sendo gerados em média 12 litros do efluente para cada litro de álcool produzido. Uma elevada carga orgânica torna a vinhaça potencial agente poluidor, podendo a disposição direta no solo representar solução ambientalmente desvantajosa para este resíduo. Diante do crescimento do setor sucroalcooleiro no Brasil e da necessidade de gestão do volumoso resíduo, este estudo avaliou duas formas de tratamentos físico-químicos da vinhaça, a precipitação química e a flotação por ar dissolvido (FAD), além de um tratamento biológico através do cultivo de microalgas no efluente do sistema FAD. Avaliou-se, adicionalmente, o potencial nutritivo do sólido separado pela FAD para aplicação como suprimento em alimentação animal. A precipitação química foi estudada variando-se pH (via adição NaOH) e tempo de reação, tendo atingido eficiências de remoção de fósforo, amônia e potássio de 31,3 ± 3,4%, 7,8 ± 4,1% e 9,7 ± 0,7%, respectivamente na faixa de pH de 8,5 a 9,5. Na FAD apenas o parâmetro dosagem apresentou significância estatística na separação dos sólidos suspensos da vinhaça. A dosagem e o percentual de recirculação foram avaliados em ensaios de clarificação e de espessamento de lodo de vinhaça. Desses ensaios obteve-se que todas as faixas de dosagens e recirculações geraram eficiências de remoção de sólidos extremamente elevadas, sendo a dosagem de 20 mg/L de polímero e 13% de recirculação adotadas como vantajosas, apresentando remoção de 98,5% da turbidez. Tal configuração gerou parâmetros de projeto de flotadores de alta eficiência, com elevadas taxas de aplicação superficial. O sólido separado na FAD apresentou interessante potencial nutritivo quando comparado bromatologicamente a produtos já utilizados como alimento para bovinos. O cultivo no efluente do sistema FAD não apresentou resultados positivos mesmo na mínima concentração testada (10% v/v de vinhaça) com relação a crescimento de Chlorella vulgaris Beijerink (1890), provavelmente pela vantagem competitiva das bactérias e possível toxicidade da vinhaça em concentrações elevadas. / The stillage is a waste from the sugar and alcohol industry, which generated on average 12 liters of effluent per liter of alcohol produced. A high organic load makes the vinasse a potential pollutant agent and a direct placement in soil represent environmentally disadvantageous solution to this residue. Given the growth of this sector in Brazil and the need for this bulky waste management, this study evaluated two forms of physicochemical treatments of vinasse: chemical precipitation and dissolved air flotation (DAF), and biological treatment through microalgae cultivation in the effluent of the FAD system. Additionally, it was assessed the nutritional potential of solid separated by FAD for application as animal food supply. Chemical precipitation was studied at varying pH (by adding NaOH) and reaction time, reaching efficiencies of phosphorus, ammonia and potassium removal of 31.3 ± 3.4%, 7.8 ± 4.1% and 9.7 ± 0.7% respectively in the pH range of 8.5 to 9.5. In FAD, only the dosage parameter showed statistical significance in the separation of suspended solids of the stillage. The dosage and the percentage of recirculation were analysed in tests of clarification and thickening sludge stillage. From these tests it was found that all dosages and recirculations ranges generated extremely high solids removal efficiencies, in wich the dosage of 20 mg/ L of polymer and 13% recirculation was adopted as advantageous, with turbidity removal about of 98.5%. Such configuration generated design parameters of high efficiency floaters, with high flow rates. The separated solid in FAD showed interesting nutritional potential when bromatologically compared to products already used as food for cattle. The cultivation in the effluent of FAD system did not show positive results even at the minimum concentration tested (10% v/v vinasse with respect to growth of Chlorella vulgaris Beijerink (1890), probably due the competitive advantage of bacterias and possible toxicity of vinasse in high concentrations.

A vinhaça é um dos resíduos provenientes da indústria sucroalcooleira, sendo gerados em média 12 litros do efluente para cada litro de álcool produzido. Uma elevada carga orgânica torna a vinhaça potencial agente poluidor, podendo a disposição direta no solo representar solução ambientalmente desvantajosa para este resíduo. Diante do crescimento do setor sucroalcooleiro no Brasil e da necessidade de gestão do volumoso resíduo, este estudo avaliou duas formas de tratamentos físico-químicos da vinhaça, a precipitação química e a flotação por ar dissolvido (FAD), além de um tratamento biológico através do cultivo de microalgas no efluente do sistema FAD. Avaliou-se, adicionalmente, o potencial nutritivo do sólido separado pela FAD para aplicação como suprimento em alimentação animal. A precipitação química foi estudada variando-se pH (via adição NaOH) e tempo de reação, tendo atingido eficiências de remoção de fósforo, amônia e potássio de 31,3 ± 3,4%, 7,8 ± 4,1% e 9,7 ± 0,7%, respectivamente na faixa de pH de 8,5 a 9,5. Na FAD apenas o parâmetro dosagem apresentou significância estatística na separação dos sólidos suspensos da vinhaça. A dosagem e o percentual de recirculação foram avaliados em ensaios de clarificação e de espessamento de lodo de vinhaça. Desses ensaios obteve-se que todas as faixas de dosagens e recirculações geraram eficiências de remoção de sólidos extremamente elevadas, sendo a dosagem de 20 mg/L de polímero e 13% de recirculação adotadas como vantajosas, apresentando remoção de 98,5% da turbidez. Tal configuração gerou parâmetros de projeto de flotadores de alta eficiência, com elevadas taxas de aplicação superficial. O sólido separado na FAD apresentou interessante potencial nutritivo quando comparado bromatologicamente a produtos já utilizados como alimento para bovinos. O cultivo no efluente do sistema FAD não apresentou resultados positivos mesmo na mínima concentração testada (10% v/v de vinhaça) com relação a crescimento de Chlorella vulgaris Beijerink (1890), provavelmente pela vantagem competitiva das bactérias e possível toxicidade da vinhaça em concentrações elevadas. / The stillage is a waste from the sugar and alcohol industry, which generated on average 12 liters of effluent per liter of alcohol produced. A high organic load makes the vinasse a potential pollutant agent and a direct placement in soil represent environmentally disadvantageous solution to this residue. Given the growth of this sector in Brazil and the need for this bulky waste management, this study evaluated two forms of physicochemical treatments of vinasse: chemical precipitation and dissolved air flotation (DAF), and biological treatment through microalgae cultivation in the effluent of the FAD system. Additionally, it was assessed the nutritional potential of solid separated by FAD for application as animal food supply. Chemical precipitation was studied at varying pH (by adding NaOH) and reaction time, reaching efficiencies of phosphorus, ammonia and potassium removal of 31.3 ± 3.4%, 7.8 ± 4.1% and 9.7 ± 0.7% respectively in the pH range of 8.5 to 9.5. In FAD, only the dosage parameter showed statistical significance in the separation of suspended solids of the stillage. The dosage and the percentage of recirculation were analysed in tests of clarification and thickening sludge stillage. From these tests it was found that all dosages and recirculations ranges generated extremely high solids removal efficiencies, in wich the dosage of 20 mg/ L of polymer and 13% recirculation was adopted as advantageous, with turbidity removal about of 98.5%. Such configuration generated design parameters of high efficiency floaters, with high flow rates. The separated solid in FAD showed interesting nutritional potential when bromatologically compared to products already used as food for cattle. The cultivation in the effluent of FAD system did not show positive results even at the minimum concentration tested (10% v/v vinasse with respect to growth of Chlorella vulgaris Beijerink (1890), probably due the competitive advantage of bacterias and possible toxicity of vinasse in high concentrations.

A escassez das fontes de fósforo e o alto consumo de energia associado à produção de fertilizantes nitrogenados serão problemas que deverão ser enfrentados no futuro. A recuperação de nutrientes das águas residuárias na forma de estruvita tem sido considerada como uma alternativa para atenuar estes problemas. Na América Latina, a produção de estruvita a partir de esgoto ainda não é uma tecnologia bem conhecida e, portanto, a finalidade deste trabalho é contribuir com uma melhor compreensão dos fenômenos envolvidos. Para isso, a pesquisa foi dividida em três etapas: 1) produção de estruvita a partir de efluente de reator anaeróbio de fluxo ascendente com manto de lodo (RAFA); 2) produção de estruvita a partir de sobrenadante de digestor anaeróbio de lodo de um processo com remoção biológica de fósforo (DALRBF) e 3) influência do cálcio na estruvita produzida na etapa 2. Nas três etapas, ajustaram-se as concentrações de magnésio, a fim de obter razões fósforo:magnésio (P:Mg) pré-estabelecidas, e o pH entre 8,00 e 10,50. Os resultados da primeira etapa mostraram que não foi possível produzir estruvita no efluente do RAFA nas condições testadas. No entanto, foram observadas remoções de fósforo e de nitrogênio, devido à formação de fosfatos de cálcio e de magnésio amorfos. Os resultados da segunda etapa comprovaram a viabilidade de produção de estruvita de sobrenadante de DALRBF e mostraram que os consumos molares dos íons fosfato (PO43-), amônio (NH4+) e magnésio (Mg2+) ou as remoções destes (%) não devem ser os únicos parâmetros para avaliar a formação de estruvita, pois outros compostos cristalizam ou precipitam e reduzem a qualidade do mineral. Para um meio com condições semelhantes às testadas nesta etapa, uma razão P:Mg 1:2 e um pH igual a 9,50 asseguram a máxima recuperação de nutrientes como estruvita com concentração mínima de impurezas, facilitando seu posterior uso como fertilizante. Os resultados da terceira etapa mostraram que uma fase amorfa de fosfato de cálcio ou de magnésio se forma na superfície da estruvita. / The shortage of the phosphorus sources and high-energy consumption associated to the nitrogen fertilizers production will be problems in the future. The nutrient recovery from wastewater as struvite has been considered as an alternative to alleviate these problems. In Latin America, production of struvite from wastewater is not yet a wellknown technology and therefore the purpose of this work is to contribute to a better understanding of the phenomena involved. This research work was performed in three phases: 1) production of struvite from upflow anaerobic sludge blanket reactor effluent; 2) production of struvite from anaerobic digester supernatant of enhanced biological phosphorus removal process (ADS-EBPR) and 3) influence of calcium in the struvite produced in the phase 2. In three phases, the magnesium concentrations were adjusted to obtain the preset phosphorus:magnesium (P:Mg) ratios and the pH was adjusted between 8,00 and 10,50. The results of the first phase showed that it is not possible to produce struvite in the upflow anaerobic sludge blanket reactor effluent in the tested conditions. However, removal of nitrogen and phosphorus was observed because amorphous calcium and magnesium phosphates were produced. The results of the second phase showed that it is possible to produce struvite in the ADS-EBPR and the molar consumptions of phosphate (PO43-), ammonia (NH4+) and magnesium (Mg2+) or removals (%) should not be the only parameters to evaluate the struvite formation, because other compounds crystallize or precipitate and reduce the quality of the mineral. In the similar conditions tested in this phase, a P:Mg ratio 1:2 and pH 9,50 assure maximum nutrients recovery as struvite with minimum impurities concentration, facilitating its subsequent use as fertilizer. The results of the third phase showed that amorphous calcium or magnesium phosphates were produced on the struvite surface.

A escassez das fontes de fósforo e o alto consumo de energia associado à produção de fertilizantes nitrogenados serão problemas que deverão ser enfrentados no futuro. A recuperação de nutrientes das águas residuárias na forma de estruvita tem sido considerada como uma alternativa para atenuar estes problemas. Na América Latina, a produção de estruvita a partir de esgoto ainda não é uma tecnologia bem conhecida e, portanto, a finalidade deste trabalho é contribuir com uma melhor compreensão dos fenômenos envolvidos. Para isso, a pesquisa foi dividida em três etapas: 1) produção de estruvita a partir de efluente de reator anaeróbio de fluxo ascendente com manto de lodo (RAFA); 2) produção de estruvita a partir de sobrenadante de digestor anaeróbio de lodo de um processo com remoção biológica de fósforo (DALRBF) e 3) influência do cálcio na estruvita produzida na etapa 2. Nas três etapas, ajustaram-se as concentrações de magnésio, a fim de obter razões fósforo:magnésio (P:Mg) pré-estabelecidas, e o pH entre 8,00 e 10,50. Os resultados da primeira etapa mostraram que não foi possível produzir estruvita no efluente do RAFA nas condições testadas. No entanto, foram observadas remoções de fósforo e de nitrogênio, devido à formação de fosfatos de cálcio e de magnésio amorfos. Os resultados da segunda etapa comprovaram a viabilidade de produção de estruvita de sobrenadante de DALRBF e mostraram que os consumos molares dos íons fosfato (PO43-), amônio (NH4+) e magnésio (Mg2+) ou as remoções destes (%) não devem ser os únicos parâmetros para avaliar a formação de estruvita, pois outros compostos cristalizam ou precipitam e reduzem a qualidade do mineral. Para um meio com condições semelhantes às testadas nesta etapa, uma razão P:Mg 1:2 e um pH igual a 9,50 asseguram a máxima recuperação de nutrientes como estruvita com concentração mínima de impurezas, facilitando seu posterior uso como fertilizante. Os resultados da terceira etapa mostraram que uma fase amorfa de fosfato de cálcio ou de magnésio se forma na superfície da estruvita. / The shortage of the phosphorus sources and high-energy consumption associated to the nitrogen fertilizers production will be problems in the future. The nutrient recovery from wastewater as struvite has been considered as an alternative to alleviate these problems. In Latin America, production of struvite from wastewater is not yet a wellknown technology and therefore the purpose of this work is to contribute to a better understanding of the phenomena involved. This research work was performed in three phases: 1) production of struvite from upflow anaerobic sludge blanket reactor effluent; 2) production of struvite from anaerobic digester supernatant of enhanced biological phosphorus removal process (ADS-EBPR) and 3) influence of calcium in the struvite produced in the phase 2. In three phases, the magnesium concentrations were adjusted to obtain the preset phosphorus:magnesium (P:Mg) ratios and the pH was adjusted between 8,00 and 10,50. The results of the first phase showed that it is not possible to produce struvite in the upflow anaerobic sludge blanket reactor effluent in the tested conditions. However, removal of nitrogen and phosphorus was observed because amorphous calcium and magnesium phosphates were produced. The results of the second phase showed that it is possible to produce struvite in the ADS-EBPR and the molar consumptions of phosphate (PO43-), ammonia (NH4+) and magnesium (Mg2+) or removals (%) should not be the only parameters to evaluate the struvite formation, because other compounds crystallize or precipitate and reduce the quality of the mineral. In the similar conditions tested in this phase, a P:Mg ratio 1:2 and pH 9,50 assure maximum nutrients recovery as struvite with minimum impurities concentration, facilitating its subsequent use as fertilizer. The results of the third phase showed that amorphous calcium or magnesium phosphates were produced on the struvite surface.

Many environmental crises are threatening to collapse human societies, but also life on the Earth as we may know. Climate change due to anthropogenic global emissions is one of the main issues, but also soil degradation, and the management of the enormous amount of organic wastes that are harmfully released into the environment by human activities. On the one hand, direct spreading of biowastes onto the land is often limited due to eutrophication or pollution by toxic compounds. On the other hands, these biomasses may contain nutrients, such as phosphorus (listed as a critical raw material) and nitrogen, which could be recovered to sustain the high demand in expensive soil amendments and fertilizers. Thus, finding new solution to close the loop towards circular economy and sustainable processes is crucial, nowadays, to convert the global trends and restore the delicate equilibrium in the water-food-energy nexus, with soil ‘under special surveillance’. In this framework, many researchers are focusing their attention on hydrothermal carbonization (HTC) as a possible candidate, in particular to treat moist biowastes and obtain useful solid (hydrochar) and liquid (HTC liquor) products. Nutrients contained in biowastes are sensitive to HTC process parameters and initial feedstock properties, thus it is crucial to analyze their distribution and (im)mobilization among the HTC products for their reuse in soil. On the other hand, since some organic compounds are generated during the thermochemical process, which may be responsible for toxicity to plants and other organisms, analysis of their possible toxicity towards the biosphere becomes crucial before implementation at a large scale. This thesis collects our efforts to explore new processes and deepen the knowledge about the possibility to produce amendments suitable for soil application from hydrochar. The core is from a process engineering perspective, focusing on the production phase and the characterization of the products, never forgetting any possible limits or the implications on ecotoxicological issues. In the first part of the thesis, ‘How to make hydrochar a soil amendment?’ is the main question. Based on few pioneer studies about composting of hydrochar, we assessed a complete analysis of hydrochar co-compost, produced from the 25-day aerobic stabilization of digestate of organic fraction of municipal solid waste, together with a fraction of its hydrochar, and green waste. Under the umbrella of C2Land project (funded by The European Institute of Innovation & Technology -EIT), we produced this new amendment in specifically designed bioreactors, then we characterized the products from the point of view of physico-chemical properties, nutrients distribution, toxicity to plants and mammalian cells. We are confident that the crucial result of toxicity removal from hydrochar through composting will attract the interest of many stakeholders, since implementing HTC in anaerobic/aerobic plants is almost ready to be applied at a large scale. Moreover, an experimental campaign performed at the University of Leeds further explored the effect of some other post-treatments on hydrochar composition and phytotoxicity, depending on the initial feedstocks (manure, sewage digestate, water hyacinth, and grass). The second part of the thesis was dedicated to nutrients recovery, necessary when some harmful matrixes - such as the municipal sewage sludge digestate - are not allowed to be reused for agricultural purposes, due to law limitations or pollution issues. In this case, nutrients recovery (N, P) could be achieved chemically, via HTC and struvite precipitation, being struvite recognized as a good fertilizer. Firstly, we performed a techno-economic assessment of the implementation at a district level of HTC-centered sewage sludge management. The mass reduction of waste streams may have some important effects on transportation costs, while the recirculation of HTC liquor back to the anaerobic digestors can imply more biomethane production with increased revenues. A mass balance for the potential of N and P recovery through struvite precipitation in the centralized facility was also assessed. Secondly, a near-zero waste treatment process for municipal sewage sludge via HTC was designed according to the available literature and preliminarily analyzed at lab level. The fractionation of the different types of phosphorus was analyzed through the STM-P protocol before and after HTC, confirming the mineralization of organic phosphorus during the process. Citric acid was validated as a good green solvent for phosphorus extraction and high-quality struvite precipitation, even if the process was not still optimized in terms of yields. Future works may identify the best process parameters for final metal recovery from liquid byproducts in order to internally recirculate them back to water line, and to characterize the leached hydrochar as purified renewable fuel or soil amendment. Thus, the proof-of-concept chain would be confirmed and could be applied to the sustainable HTC-centered biorefineries of the future.