Throughout Central Florida surface water and ground water are decreasing in quantity and quality in part because of excess Nitrate and Phosphorus nutrients. Stormwater runoff serves as a medium for transport of Nitrate and Phosphorus to surface water and ground water. The goal of this experiment is assess the Nitrate and Phosphorus removal in stormwater using select media. The results of a literature search, batch test experimentation and column test experimentation are used to determine an optimal media blend that may be implemented in detention ponds to reduce Nitrate and Phosphorus. The extensive literature search revealed 32 different media that may be used to remove Nitrate and Phosphorus. Each potential media was qualitatively and quantitatively evaluated based on 5 criteria: 1) relevance, 2) permeability, 3) cost, 4) availability in Florida, and 5) additional environmental benefit. The top 7 performing media: Florida peat, sandy loam, woodchips, crushed oyster shell; crushed limestone, tire crumb and sawdust were selected for batch test experimentation. The aerobic conditions in batch test experimentation prohibited the growth of denitrifying bacteria, therefore media mixes were selected for column test experimentation based on Ammonia and Orthophosphate concentrations. Batch test experimentation showed the most effective media to be 50% sand, 30% tire crumb, 20% sawdust by weight (media mix 1) and 50% sand, 25% sawdust, 15% tire crumb, 10% limestone by weight (media mix 2). Media mix 1, media mix 2 and a control are tested in column test experimentation, where the control is site soil from Hunters Trace development in Ocala, Florida. Column test experimentation models a dry detention pond where water passes through a 48 inch unsaturated zone then a 48 inch saturated zone. To test Nitrate and Orthophosphate removal potential, pond water augmented with Nitrate (0.38, 1.26, 2.5 mg/L NO3-N) and Orthophosphate (0.125, 0.361, 0.785 mg/L PO4-P) was pumped into the columns. Media mix 1 and media mix 2 outperformed the control in both Nitrate and Orthophosphate removal. Media mix 1 and media mix 2 had Nitrate removal efficiencies ranging from 60% to 99% and the control had Nitrate removal efficiencies ranging from 38%-80%. Media mix 1 and media mix 2 averaged Orthophosphate removal efficiencies ranging from approximately 42% to 67%. For every run in every influent Orthophosphate concentration the saturated control added Orthophosphate to the water. The Nitrate and Orthophosphate removal performances for media mix 1 and media mix 2 could not be directly compared because of different influent saturated nutrient concentrations.

This master thesis is based on own studies. A four-month study was performed at Hammarby Sjostad Research Station, which is located in Stockholm. One-stage deammonification process was evaluated in two different system configurations in pilot plant scale. The theoretical background for this thesis works is presented in the first part and where is presented negative impacts of nitrogen compounds in environment and requirements for purified wastewater in European Union (Sweden and Poland). In the next part of the thesis the nitrogen cycle is described and with focus on biological reactions for nitrogen removal. Especially, nitrification/denitrification and anammox processes are described with special focus on parameters affecting the anammox process performance and its advantages and disadvantages of using this process. Experimental results from the four-month study and evaluation of the microbial activity are described in the last part.

Os materiais reativos orgânicos, como turfas e compostos, apresentam um considerável potencial efetivo de utilização na remediação de áreas contaminadas por metais potencialmente tóxicos, haja vista sua elevada capacidade de adsorção, comumente associada a altos teores de matéria orgânica. O emprego do composto orgânico se torna vantajoso por ser uma possibilidade de destinação final correta dos resíduos sólidos urbanos compostáveis, conforme as políticas públicas, podendo agregar valor econômico e ambiental ao resíduo. Nessa perspectiva, na seleção dos materiais reativos mais viáveis para serem empregados na retenção de metais é imprescindível sua caracterização (geológica e geotécnica) e o estudo de sua real capacidade adsortiva, através de ensaios de adsorção. Assim, o objetivo desta pesquisa foi a caracterização geológica e geotécnica de uma turfa (proveniente da bacia hidrográfica do rio Mogi Guaçu, município de Cravinhos) e de quatro compostos (compostos total, indiano, estático e alambrado, advindos de composteiras localizadas na Universidade de São Paulo - São Carlos), bem como ensaios de adsorção (equilíbrio em lote) com chumbo (Pb), zinco (Zn) e cádmio (Cd). Para tanto foram realizados os seguintes ensaios de caracterização: granulometria, massa específica dos sólidos, densidade, teor de umidade, parâmetros físico-químicos (potencial hidrogeniônico (pH), &Delta;pH, potencial de oxi-redução (Eh) e condutividade elétrica (CE), ponto de efeito salino nulo (PESN), matéria orgânica (MO), teor de cinzas (Cz), capacidade de troca catiônica (CTC), capacidade de retenção de água (CRA), composição elementar (C, H e N), carbono orgânico, Difratometria de Raios-X (DRX), Fluorescência de Raios-X (FRX), Microscopia Eletrônica de Varredura/Espectroscopia de Energia Dispersiva por Raios-X (MEV/EDS) e Análise Térmica Diferencial (ATD). A partir do conhecimento minucioso dos parâmetros físicos e químicos dos materiais foi possível proceder o ensaio de equilíbrio em lote com soluções monoelementares de Pb, Zn e Cd com oito concentrações distintas e inferiores a 220 mg L-1 e razão material reativo/solução de 1/50 (conforme definido em etapa preliminar). Quanto aos resultados de caracterização, turfa e compostos apresentaram características promissoras para a adsorção. A turfa revelou um pH moderadamente ácido (5,1), um &Delta;pH negativo (-1,0) atestando para a presença majoritária de cargas negativas na superfície das partículas, o que foi confirmado pelo PESN (3,6) < pH (5,1), um considerável teor de MO (520,43 mg kg-1) e uma CTC elevada (91,00 cmolc kg-1). Já os compostos exibiram valores de pH ligeiramente ácidos a ligeiramente básicos (6,4 a 7,7), &Delta;pH negativo (-0,4 a -1,0), MO promissora (193,92 a 418,70 mg kg-1) e CTC variável (29,00 a 75,00 cmolc kg-1). Em termos gerais, os compostos total e indiano apresentaram características mais favoráveis para a retenção metálica o que foi confirmado por etapa preliminar do ensaio de adsorção. Como o composto indiano sobressaiu levemente na imobilização de Cd e Zn e por ele apresentar maior controle no processo de compostagem ele foi o escolhido para a realização do ensaio de equilíbrio em lote com variadas concentrações de Pb, Zn e Cd, assim como a turfa. Os resultados finais de adsorção atestaram que a turfa e o composto indiano apresentaram a mesma ordem de afinidade metálica: Pb > Cd > Zn, sendo que o composto revelou uma tendência superior de adsorção. A turfa revelou uma porcentagem de remoção metálica (A%) superior a 90% para concentrações de Pb de até 137 mg L-1, enquanto o composto adsorveu mais de 98% do Pb em todas as concentrações estudadas (26 a 214 mg L-1), não atingindo o estado de saturação. Dessa forma, turfa e compostos, caracterizados por um baixo custo e uma significativa disponibilidade, podem ser enquadrados como potenciais materiais reativos orgânicos para a imobilização de cátions metálicos, principalmente Pb2+ e Cd2+. / Organic reactive materials, such as peat and compounds, have a considerable potential for use in the remediation of contaminated areas by potentially toxic metals, due to their high adsorption capacity, commonly associated with high organic matter content. The use of organic compound becomes advantageous because it is a possibility of final destination for the compostable municipal solid waste, according to the public policies, being able to add economic and environmental value to the waste. In this perspective, the selection of the most viable reactive materials to be used in the retention of metals is needful, its characterization (geological and geotechnical) and the study of its real adsorptive capacity through adsorption tests are essential. Thus, the objective of this research was to characterize the geological and geotechnical characteristics of a peat (from Mogi Guaçu\'s basin in the city Cravinhos) and four compounds (total, indian, static and wired, from composters located at the University of São Paulo), besides batch tests with lead (Pb), zinc (Zn) and cadmium (Cd). To achieve the objectives, the following tests were done: particle size analysis, solids specific mass\' determination, density, moisture content, physico-chemical parameters (potential hydrogenion - pH, &Delta;pH, oxy-reduction potential - Eh and electrical conductivity - EC), point of zero salt effect (PZSE), organic matter (OM), ash content, cation exchange capacity (CEC), water retention capacity (WRC), elemental composition (C, H and N), organic carbon, X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), Scanning Electron Microscopy/X-Ray Dispersive Energy Spectroscopy (SEM/DES) and Differential Thermal Analysis (DTA). From the detailed knowledge of the physical and chemical parameters of the materials was possible to perform the batch equilibrium test with monoelemental solutions of Pb, Zn and Cd with different concentrations below 220 mg L-1 and reactive material/solution ratio of 1/50 (as defined in the preliminary stage). Regarding the characterization results, peat and compounds presented promising characteristics for adsorption. The peat showed moderately acidic pH (5.1), negative &Delta;pH (-1.0) attesting to a majority presence of negative charges on the surface of the particles, which was confirmed by the PZSE (3.6) < pH (5.1), a considerably high OM content (520.43 mg kg-1) and a high CEC (91.00 cmolc kg-1). The compounds exhibited from slightly acidic to slightly basic pH values (6.4 to 7.7), negative &Delta;pH (-0.4 to -1.0), promising OM (193.92 to 418.70 mg kg-1) and variable CEC (29.00 to 75.00 cmolc kg-1). In general, terms, the total and indian compounds presented more favorable characteristics for metal retention, what was confirmed by the preliminary step of the adsorption test. As the Indian compound had a small enhancement on the immobilization of Cd and Zn and due, it showed greater control in the composition process, it was chosen for a batch equilibrium test with varying concentrations of Pb, Zn and Cd, as well as a peat. The final adsorption results showed that the peat and the indian compound had the same order of metal affinity: Pb > Cd > Zn, whereby the compound showed a higher adsorption tendency. The peat showed a metal removal percentage (A%) higher than 90% for Pb concentrations up to 137 mg L-1, while the compound adsorbed more than 98% at all concentrations studied (26 to 214 mg L-1) not reaching the saturation state. Thus, peat and organic compounds, characterized by a low cost and a significant availability, can be classified as potential organic low-cost reactive materials for metal cations immobilization, mainly Pb2+ and Cd2+.

In den Pflanzenzellwänden befindliche Polysaccharide stehen dem Prozess nur bedingt als Energiequelle zur Verfügung, da diese in einem Komplex mit Lignin verknüpft sind. Um diese Substanzen für den Biogasprozess verfügbar zu machen und demnach den Substratumsatz bzw. die Prozesseffizienz zu erhöhen, sind geeignete Stoffe oder Techniken einzusetzen bzw. zu entwickeln. In dieser Arbeit wurde zielführend der Einsatz von unterschiedlichen Enzympräparaten in drei verschiedenen Prozessstufen bei ausgewählten Energiepflanzen mit variierender Häcksellänge untersucht. Anhand von Enzymaktivitätsbestimmungen konnten Enzympräparate für die einzelnen Stufen selektiert werden. Die ausgewählten Enzyme wurden einzeln oder in Mischung während der Silierung, direkt vor dem Biogasprozess sowie während des Biogasprozesses zum Substrat dotiert und dieses nach der jeweiligen Vorbehandlung in Batch-Gärtests vergoren. Neben der Biogas- und Methanausbeute wurde zur Bewertung der Enzymleistung der Abbau an Lignocellulose sowie die Freisetzung an niedermolekularen Kohlenhydraten ermittelt. Zusätzlich wurde das Quellen der Lignocellulose mit Hilfe eines Wasserzusatzes in Form einer Vorhydrolyse als Vorbehandlungsmethode mit allgemein positivem Ergebnis geprüft. Das Ziel der verbesserten Substratumsetzung bei Mais und Roggen und folglich einer Erhöhung der Biogasproduktion wurde durch den Zusatz ausgewählter Enzympräparate erreicht. Es konnten Grundlagen bezüglich der Wirkung von Enzymen in Biogasprozessen geschaffen werden, anhand derer deutlich wurde, dass besonders die enzymatische Behandlung in den der Methanisierung vorgelagerten Prozessstufen weiterzuentwickeln ist. / Polysaccharides of plant cell walls are of limited digestibility due to their cross-linking to lignin. In order to make the molecules available for the biogas process and thus increase the substrate utilization and process efficiency appropriate substances or techniques are needed. It was therefore the aim of this work to investigate the effects of different enzyme preparations in three digestion process stages. Selected energy plants with varying degrees of particle sizes (chopping lengths) were used as digester feedstock. Enzyme preparations for the different process stages were chosen by enzyme assays. The selected enzymes were added to the feedstock during the ensiling, directly before the biogas process or during the biogas process separate or in mixtures. Pre-treated substrates were subsequently digested in batch fermentation tests. Beside the biogas and methane yield the degradation degree of lignocellulose and the release of low molecular carbohydrates were investigated for evaluating the enzyme performance. Additionally, the swelling of lignocellulose caused by addition of water in a pre-hydrolysis process was examined as a method of pre-treatment, with generally positive results. The aim of an improved substrate conversion of maize and rye and thus an enhanced biogas production by enzymatic pretreatments was achieved. Scientific fundamentals regarding the impact of enzymes on biogas processes were established. Enzymatic pretreatments in process steps before methanation showed potential for further developments.

L'épandage des boues d'épuration est un mode de valorisation à la fois écologique et économique pour autant que l'on maitrise leur qualité et notamment la concentration des métaux lourds mobilisables. Le cuivre est une molécule très répandue, naturelle dans l'environnement, largement utilisée dans l'industrie et l'agriculture. En conséquence, les quantités de cuivre dans l'environnement ont augmenté, de sorte que ce dernier a été choisi dans cette étude comme représentant de la pollution anthropique pour évaluer sa mobilité en fonction de la qualité des boues épandues et des sols. 9 boues classiques et 2 sols (Sol d’herbe (de France) et sol de riz (du Vietnam)) ont été étudiés ainsi que des boues granulaires. Une méthodologie est proposée pour évaluer l'effet de la boue et de l'origine du sol sur la capacité de lessivage du cuivre lors de l'épandage des boues pour les activités agricoles. Les essais de désorption dans les colonnes de sol amendé par des boues ont montré que: a) quelle que soit l'origine du sol amendé, les boues de lit de roseaux (LR), séchées (BCD), centrifugées (BC) ont présenté une libération de Cu inférieure à 2% tandis que les boues de filtre-presse (BFP), digérées (BD), épaissies (BE) et calcaires (BCh) ont amélioré la disponibilité de Cu dans le sol; b) La lixiviation du cuivre dans le sol d’herbe (du France) amendé par des boues granulaires était supérieure à celle mesurée pour les échantillons classiquesde boues; c) Dans le sol de riz (de Vietnam), l'épandage des boues granulaires a limité la désorption de cuivre par rapport aux échantillons de boue (BCh), de filtre-presse (BFP), digérée (BD) ou centrifugée (BC). Quatre mécanismes sont proposés pour expliquer le devenir du Cu dans les sols: 1) le contrôle; 2) le groupe de Cp1, Cp2, BC, LR and BCD; 3) le groupe de BCh, BD, BE, BFP et 4) le groupe de boue granulaire. Il est constaté que pour le sol de riz contenant une faible teneur en matière organique, l'application de boues granulaires ou d'autres types de boue tels que les boues compostées ou séchées peut non seulement augmenter la teneur en éléments nutritifs, mais aussi réduire la capacité de lixiviation du cuivre. / The spreading of sewage sludge is both ecological and economical in sofar as their quality is controlled and in particular the low level of the heavy metals available. Copper is a very common substance, naturally occurring in the environment, widely used in industry and agriculture. As a result, quantities of copper in the environment have increased, so it has been selected in this study as representing human-induced pollution to assess its mobility in relation to the quality of sludge and soil. 9 different sludges and 2 soils (grass soil from France and paddy soil from Vietnam) were studied as well as granular sludge. A methodology was developed to evaluate the effect of sludge and soil origin on copper leaching ability during sludge application for agricultural activities. Desorption tests in soil-amended sludge columns showed that: a) Whateverthe origin of soil, the centri-dried (BCD), centrifuged (BC), reed-bed (LR) sludges presented a Cu release lower than 2% while filter-pressed (BFP), digested (BD), thickened (BE) and limed (BCh) sludge amended soils increased Cu availability in soil; b) the copper leaching of granular sludge amended grass soil was higher than those measured for conventional sludge samples; c) in paddy soil, landspreading of granular sludge limited the Cu desorption compared to limed (BCh), filter-press (BFP), digested (BD) and centrifuged (BC) sludge samples. Four mechanisms groups are proposed to explain the fate of Cu in soils: 1) the control; 2) the group of Cp1, Cp2, BC, LR and BCD; 3) the group of BCh BD BE and BFP, and 4) the group of granular sludge. It is found that paddy soil containing low organic matter, application of granular sludge orother types such as composted or dried sludge can not only increase the nutrient content but also reduce the leaching capacity of copper.

Os materiais reativos orgânicos, como turfas e compostos, apresentam um considerável potencial efetivo de utilização na remediação de áreas contaminadas por metais potencialmente tóxicos, haja vista sua elevada capacidade de adsorção, comumente associada a altos teores de matéria orgânica. O emprego do composto orgânico se torna vantajoso por ser uma possibilidade de destinação final correta dos resíduos sólidos urbanos compostáveis, conforme as políticas públicas, podendo agregar valor econômico e ambiental ao resíduo. Nessa perspectiva, na seleção dos materiais reativos mais viáveis para serem empregados na retenção de metais é imprescindível sua caracterização (geológica e geotécnica) e o estudo de sua real capacidade adsortiva, através de ensaios de adsorção. Assim, o objetivo desta pesquisa foi a caracterização geológica e geotécnica de uma turfa (proveniente da bacia hidrográfica do rio Mogi Guaçu, município de Cravinhos) e de quatro compostos (compostos total, indiano, estático e alambrado, advindos de composteiras localizadas na Universidade de São Paulo - São Carlos), bem como ensaios de adsorção (equilíbrio em lote) com chumbo (Pb), zinco (Zn) e cádmio (Cd). Para tanto foram realizados os seguintes ensaios de caracterização: granulometria, massa específica dos sólidos, densidade, teor de umidade, parâmetros físico-químicos (potencial hidrogeniônico (pH), &Delta;pH, potencial de oxi-redução (Eh) e condutividade elétrica (CE), ponto de efeito salino nulo (PESN), matéria orgânica (MO), teor de cinzas (Cz), capacidade de troca catiônica (CTC), capacidade de retenção de água (CRA), composição elementar (C, H e N), carbono orgânico, Difratometria de Raios-X (DRX), Fluorescência de Raios-X (FRX), Microscopia Eletrônica de Varredura/Espectroscopia de Energia Dispersiva por Raios-X (MEV/EDS) e Análise Térmica Diferencial (ATD). A partir do conhecimento minucioso dos parâmetros físicos e químicos dos materiais foi possível proceder o ensaio de equilíbrio em lote com soluções monoelementares de Pb, Zn e Cd com oito concentrações distintas e inferiores a 220 mg L-1 e razão material reativo/solução de 1/50 (conforme definido em etapa preliminar). Quanto aos resultados de caracterização, turfa e compostos apresentaram características promissoras para a adsorção. A turfa revelou um pH moderadamente ácido (5,1), um &Delta;pH negativo (-1,0) atestando para a presença majoritária de cargas negativas na superfície das partículas, o que foi confirmado pelo PESN (3,6) < pH (5,1), um considerável teor de MO (520,43 mg kg-1) e uma CTC elevada (91,00 cmolc kg-1). Já os compostos exibiram valores de pH ligeiramente ácidos a ligeiramente básicos (6,4 a 7,7), &Delta;pH negativo (-0,4 a -1,0), MO promissora (193,92 a 418,70 mg kg-1) e CTC variável (29,00 a 75,00 cmolc kg-1). Em termos gerais, os compostos total e indiano apresentaram características mais favoráveis para a retenção metálica o que foi confirmado por etapa preliminar do ensaio de adsorção. Como o composto indiano sobressaiu levemente na imobilização de Cd e Zn e por ele apresentar maior controle no processo de compostagem ele foi o escolhido para a realização do ensaio de equilíbrio em lote com variadas concentrações de Pb, Zn e Cd, assim como a turfa. Os resultados finais de adsorção atestaram que a turfa e o composto indiano apresentaram a mesma ordem de afinidade metálica: Pb > Cd > Zn, sendo que o composto revelou uma tendência superior de adsorção. A turfa revelou uma porcentagem de remoção metálica (A%) superior a 90% para concentrações de Pb de até 137 mg L-1, enquanto o composto adsorveu mais de 98% do Pb em todas as concentrações estudadas (26 a 214 mg L-1), não atingindo o estado de saturação. Dessa forma, turfa e compostos, caracterizados por um baixo custo e uma significativa disponibilidade, podem ser enquadrados como potenciais materiais reativos orgânicos para a imobilização de cátions metálicos, principalmente Pb2+ e Cd2+. / Organic reactive materials, such as peat and compounds, have a considerable potential for use in the remediation of contaminated areas by potentially toxic metals, due to their high adsorption capacity, commonly associated with high organic matter content. The use of organic compound becomes advantageous because it is a possibility of final destination for the compostable municipal solid waste, according to the public policies, being able to add economic and environmental value to the waste. In this perspective, the selection of the most viable reactive materials to be used in the retention of metals is needful, its characterization (geological and geotechnical) and the study of its real adsorptive capacity through adsorption tests are essential. Thus, the objective of this research was to characterize the geological and geotechnical characteristics of a peat (from Mogi Guaçu\'s basin in the city Cravinhos) and four compounds (total, indian, static and wired, from composters located at the University of São Paulo), besides batch tests with lead (Pb), zinc (Zn) and cadmium (Cd). To achieve the objectives, the following tests were done: particle size analysis, solids specific mass\' determination, density, moisture content, physico-chemical parameters (potential hydrogenion - pH, &Delta;pH, oxy-reduction potential - Eh and electrical conductivity - EC), point of zero salt effect (PZSE), organic matter (OM), ash content, cation exchange capacity (CEC), water retention capacity (WRC), elemental composition (C, H and N), organic carbon, X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), Scanning Electron Microscopy/X-Ray Dispersive Energy Spectroscopy (SEM/DES) and Differential Thermal Analysis (DTA). From the detailed knowledge of the physical and chemical parameters of the materials was possible to perform the batch equilibrium test with monoelemental solutions of Pb, Zn and Cd with different concentrations below 220 mg L-1 and reactive material/solution ratio of 1/50 (as defined in the preliminary stage). Regarding the characterization results, peat and compounds presented promising characteristics for adsorption. The peat showed moderately acidic pH (5.1), negative &Delta;pH (-1.0) attesting to a majority presence of negative charges on the surface of the particles, which was confirmed by the PZSE (3.6) < pH (5.1), a considerably high OM content (520.43 mg kg-1) and a high CEC (91.00 cmolc kg-1). The compounds exhibited from slightly acidic to slightly basic pH values (6.4 to 7.7), negative &Delta;pH (-0.4 to -1.0), promising OM (193.92 to 418.70 mg kg-1) and variable CEC (29.00 to 75.00 cmolc kg-1). In general, terms, the total and indian compounds presented more favorable characteristics for metal retention, what was confirmed by the preliminary step of the adsorption test. As the Indian compound had a small enhancement on the immobilization of Cd and Zn and due, it showed greater control in the composition process, it was chosen for a batch equilibrium test with varying concentrations of Pb, Zn and Cd, as well as a peat. The final adsorption results showed that the peat and the indian compound had the same order of metal affinity: Pb > Cd > Zn, whereby the compound showed a higher adsorption tendency. The peat showed a metal removal percentage (A%) higher than 90% for Pb concentrations up to 137 mg L-1, while the compound adsorbed more than 98% at all concentrations studied (26 to 214 mg L-1) not reaching the saturation state. Thus, peat and organic compounds, characterized by a low cost and a significant availability, can be classified as potential organic low-cost reactive materials for metal cations immobilization, mainly Pb2+ and Cd2+.