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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.

Um fertilizante que pode ser obtido a partir de dejetos de animais é o mineral estruvita (NH4PO4Mg.6H2O). O objetivo deste estudo foi sintetizar estruvita a partir da recuperação de P em excretas de aves de postura, por meio de um processo termo-químico e precipitação alcalina. A recuperação de P das excretas foi realizada através de incineração a 550°C, e extração ácida. A solução obtida foi caracterizada quimicamente sendo, em seguida, submetida a uma modelagem no software Visual MINTEQ 3.1, onde se definiu a concentração ideal de Mg para a síntese da estruvita (EP), considerando um valor de pH de 8,5. A EP foi caracterizada quanto a composição química e mineralógica, seguindo mesmo procedimento para uma estruvita formada naturalmente (EN) e uma estruvita comercial - Crystal Green® (CG). Foram realizados ensaios de solubilização das estruvitas EP, EN e CG, com sistema de fluxo intermintente de soluções com uma bomba peristáltica durante 8 horas. Foram preparadas 5 soluções com diferentes valores de pH (4, 5, 6, 7, 8) e 4 soluções com pH ajustado a 6, compostas por diferentes ácidos orgânicos: citrato tri-potássico, ácido oxálico, ácido ácetico, ácido málico, e ácido cítrico em pH natural de 3,9. A avaliação agronômica foi realizada em casa de vegetação, sob o cultivo de trigo e soja por 38 dias, em vasos contendo amostras de um Cambissolo Eutrófico. Neste estudo foi avaliado a solubilização das estruvitas de EP, EN e CG, comparadas com Superfosfato triplo (TSP), aplicadas a uma dose de 25 mg de P por vaso. A avaliação da solubilização foi feita por meio da coleta da solução do solo com o auxílio dos dispositivos Rhizons®. Ao final, foi avaliada a produção de massa seca, teor acumulado de P nos tecidos das plantas, além da eficiência relativa das estruvitas em relação ao TSP. Com o objetivo de avaliar a difusão de P no solo foi realizada marcação isotópica com 33P na estruvita (33ST) e no TSP (33TSP). A 33ST e o 33TSP foram aplicados em uma massa equivalente de 0,25 g em micropotes preenchidos com solo acondicionados em uma câmara com umidade relativa de 100% durante 21 dias. As coletas de solo dos micropotes foram realizadas aos 1º, 7º, 14º e 21º dias após a adubação, sendo coletadas amostras a cada 1 mm até a profundidade de 10 mm e, a partir desta, a cada 5 mm até a profundidade de 30 mm. O P foi extraído do solo e determinada a intensidade de 33P. A recuperação de P das excretas de aves de postura por meio do tratamento termo-químico foi de 75% do P total. As estruvitas EP, EN e CG apresentaram maior solubilidade em soluções com valores de pH ácido. Os ácidos orgânicos não apresentaram influência na solubilização das estruvitas. O TSP apresentou os maiores teores de P na planta e maior massa seca em comparação às estruvitas. A estruvita precipitada apresentou 80% de eficiencia em relação ao TSP. O TSP apresentou maior movimentação de P no solo em comparação a estruvita. / A fertilizer that can be obtained from animal wastes is the mineral struvite (NH4PO4Mg.6H2O).The objective of this study was to synthesize struvite from P recovery in chicken manure through the thermochemical process and alkaline precipitation. The recovery of P from chicken manure was carried out with the incineration at 550°C, and acid extraction. The solution obtained was chemically characterized and then subjected to a modelling in Visual MINTEQ 3.1 software, where the ideal concentration of Mg for the synthesis of struvite (PS) was defined, considering a pH value of 8.5. The PS was characterized in terms of the concentration of elements and mineralogical composition following procedure for a natural struvite (NS) and a commercial struvite - Crystal Green® (CG). Were carried out solubilization assays using a intermittent solutions flow system on the samples PS, NS and CG with a peristaltic pump during 8 hours. Was prepared 5 solutions with different pH (4, 5, 6, 7, 8) and 4 solutions with pH adjusted to 6 composed of different organic acids: tri-potassium citrate, oxalic acid, acetic acid, malic acid, besides citric acid at natural pH equivalent to 3.9. The agonomic evaluation was carried out in a greenhouse under wheat and soybean cultivation for 38 days, in pots containing samples of an Eutrophic Cambisol. In this study the solubilization of struvites PS, NS and CG was compared to a Triple Superphosphate (TSP) applied at 25 mg of P per pot. The solubilization evaluation was done by means of the soil solution sampling with the devices Rhizons®. At the end, dry matter production, accumulated P content in the plant tissues and the relative efficiency of the struvite were evaluated in relation to TSP. With the objective of evaluating P diffusion has done the labeleing with a 33P in the struvite(33ST) and in the TSP (33TSP). The 33ST and 33TSP were applied an equivalent mass of 0.25 g in micro-pots containing soil and then packed in a chamber at 100% relative humidity for 21 days. Soil samples were collected at 1st, 7th, 14th and 21st days after fertilization sampling every 1 mm to a depth of 10 mm and from this, every 5 mm to a depth of 30 mm. The P was extracted and being analyzed the 33P intensity. The recovery of P from chicken manure by the thermochemical treatment was 75% of total P. The struvites PS, NS and CG showed higher solubility in solutions with acidic pH. Organic acids had no influence on struvite solubilization. The TSP fertilizer showed the highest tissue P levels and higher dry mass in comparison to struvites. The synthesized struvite showed 80% efficiency in relation to TSP. The TSP presented greater movement of P in the soil in comparison to struvite.

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.

This thesis assessed the technical and economic premises for installing systems that process manure in order to recover nutrients and inherent energy. The main purpose of recovering nutrients was to extract phosphorus from the manure, so as to be able to distribute more of the manure on the farm without exceeding the phosphorus regulation. Three other scenarios were included as reference; conventional manure handling, solid-liquid separation only and solid-liquid separation including energy recovery. Since most important parameters for modeling scenarios in agriculture are site-specific (e.g. soil type, crop rotation and manure composition), the thesis results were based on a case farm. The case farm is a 675 ha dairy farm with approx. 1400 milking cows, located in Östergötland, Sweden. As for the results, it was first concluded that the central characteristics of manure were the content of dry matter (DM), nitrogen (N), phosphorus (P) and potassium (K). The higher the DM content, the more fuel for energy recovery, and the higher the N:P-ratio, the more on-farm N can be utilized before having to consider the P regulation. The technical premises for farm-scale nutrient recovery were limited to commercial techniques from companies operating in Sweden, and included various possible processing methods, such as; pH modification, anaerobic digestion, coagulation-flocculation, precipitation, filtration and reverse osmosis. However, most methods were either too costly or simply not realistic to install on stand-alone farms, resulting in only two feasible options; struvite precipitation and secondary solid-liquid separation with a decanter centrifuge. The comparison in economic performance for all scenarios resulted as follows: nutrient recovery by struvite precipitation was the most profitable scenario of all, if struvite was allowed to replace mineral P fertilizer (i.e. end-product on-farm utilization). If not, it was more profitable to invest in only energy recovery, as nutrient recovery by secondary solid-liquid separation or struvite precipitation with end-product sales were not as profitable. However, the absolutely largest increase in profitability lies within investing in a primary solid-liquid separation. As for the case farm, this investment reduced costs by more than 2 MSEK, while any of the latter scenarios reduce costs by 0,1-0,2 MSEK. Furthermore, the possible utilization of the waste heat from energy recovery increased profitability by a factor of ten.

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.

<p dir="ltr">The chemical constituents of terrestrial and atmospheric waters originate from biomass burning, fertilizer runoff, and anthropogenic activity, among other sources, and their multi-phase chemistry is complex. Sunlight plays an essential role in aquatic chemistry. Photosensitizers in terrestrial and atmospheric waters absorb light to form highly reactive species such as triplet excited carbon (³C*), hydroxyl radical (•OH), and singlet oxygen (¹O₂), driving the photochemical transformations of dissolved organic matter (DOM) in the aqueous phase. Of note, these reactive species transform DOM compounds that do not undergo direct photolysis. DOM frequently undergoes a change in optical properties following photochemical processing, with implications for air quality, water quality, and human and animal health. The presence of inorganic minerals, such as the fertilizer compound struvite, in terrestrial or atmospheric waters introduces further complexity and impacts the photochemical processes that occur. Simplified proxy systems are created in the laboratory to simulate aquatic photochemical processes and evaluate the formation and/or photodegradation of photoproducts. These mixtures typically consist of a representative organic carbon (OC) compound and a photosensitizer, along with struvite or another inorganic mineral.</p>

In dieser Dissertation wird der Einfluss von Transaktionen zur Wiederverwendung von Nährstoffen und gereinigtem kommunalen Abwasser auf die Wertschöpfungsketten der Abwasserbehandlung und Pflanzenproduktion untersucht. Ziel ist es, Kosten und Nutzen sowie die Wertschöpfung von Transaktionen in verknüpften Wertschöpfungsketten der Abwasserbehandlung und Pflanzenproduktion zu analysieren. Darüber hinaus wird untersucht, wie Transaktionen und Interdependenzen zwischen Akteuren in verknüpften Wertschöpfungsketten die lokalen Governance-Strukturen für die Wiederverwendung von Abwasser beeinflussen. Die Analyse wird hauptsächlich durch das Wertschöpfungskettenkonzept, das Konzept der Kreislaufwirtschaft und die Theorie der Transaktionskostenökonomie geleitet. Mit verschiedenen Methoden, wie der Kosten-Nutzen-Analyse, der Wertschöpfungskettenanalyse und der Transaktionskostenanalyse, werden zwei Fallstudien in Deutschland untersucht: (1) die Fällung von Struvit (Magnesium-Ammonium-Phosphat) und dessen Verwendung als Dünger in Berlin-Brandenburg und (2) das Modell der landwirtschaftlichen Abwasserwiederverwendung in Braunschweig. Die Ergebnisse zeigen, dass die Wiederverwendung von Nährstoffen und Abwasser zu geringeren Kosten für die Abwasserbehandlung, höherer Rentabilität und Wertschöpfung in der Pflanzenproduktion und zu einem hohen Anteil an regionaler Wertschöpfung führen. Die Ergebnisse verdeutlichen aber auch, dass die Wiederverwendung von Abwasser zu Einschränkungen, Verdrängungseffekten und Veränderungen in der Verteilung der Wertschöpfung führen kann. Des Weiteren zeigen die Ergebnisse, dass differenzierte Governance-Strukturen erforderlich sind, um den unterschiedlichen Eigenschaften der Transaktionen zwischen Abwasserbehandlung und der Pflanzenproduktion gerecht zu werden. Interdependenzen zwischen Abwasseranbietern und Landwirten erhöhen den Bedarf an hybriden und hierarchischen Elementen in den Governance-Strukuren für die Wiederverwendung von Abwasser. / This dissertation explores the impact of transactions for reusing nutrients and treated municipal wastewater on the value chains of wastewater treatment and crop production. It aims to analyze what costs and benefits and what added-value can result from transactions in linked value chains of wastewater treatment and crop production. Furthermore, it aims to analyze how transactions and interdependences between actors in linked value chains shape the governance structures for reusing wastewater at the local level. The analysis is mainly guided by the value chain concept, the concept of the circular economy and the theory of transaction costs economics. Different methods including cost-benefit analysis, value chain analysis and transaction cost analysis are used to investigate two case studies located in Germany: (1) the precipitation of struvite (magnesium ammonium phosphate) in the wastewater treatment plant in Waßmannsdorf and its application as fertilizer in Berlin-Brandenburg, and (2) the agricultural wastewater reuse scheme of the Wastewater Association Braunschweig. The results show that transactions for reusing nutrients and wastewater result in the development of linked regional value chains with lower costs of wastewater treatment, higher profitability and added-value in crop production, and a high share of regional added-value. However, the results also highlight that the reuse of wastewater can lead to restrictions (e.g., cultivation bans on certain crops), crowding out effects and changes in the distribution of the added-value. Furthermore, the findings suggest that different governance structures are needed to match the different properties of the transactions between wastewater treatment and crop production. Interdependences resulting from transactions between wastewater providers and farmers increase the need for hybrid and hierarchical elements in the governance structures for reusing wastewater.