Moving bed biofilm reactors (MBBRs) have been used effectively to reach low nutrient levels in northern Europe for nearly 20 years at cold temperatures. A relatively new technology to the US, the MBBR has most typically been used in a post-denitrification configuration with methanol for additional nitrate removal. Methanol has clearly been the most commonly used external carbon source for post-denitrification processes due to low cost and effectiveness. However, with the requirement for more US wastewater treatment plants to reach effluent total nitrogen levels approaching 3 mg/L, alternative electron donors could promote more rapid MBBR startup/acclimation times and increased cold weather denitrification rates. Bench-scale MBBRs evaluating four different electron donor sources, specifically methanol, ethanol, glycerol, and sulfide (added as Na2S), were operated continuously at 12 °C, and performance was monitored by weekly sampling and insitu batch substrate limiting profile testing. Ethanol and glycerol, though visually exhibited much higher biofilm carrier biomass content, performed better than methanol in terms of removal rate (0.9 and 1.0 versus 0.6 g N/m²/day.) Maximum denitrification rate measurements from profile testing suggested that ethanol and glycerol (2.2 and 1.9 g N/m²/day, respectively) exhibited rates that were four times that of methanol (0.49 g N/m²/day.) Sulfide also performed much better than any of the other three electron donors with maximum rates at 3.6 g N/m²/day and with yield (COD/NO₃-N) that was similar to or slightly less than that of methanol. Overall, the yield and carbon utilization rates were much lower than expected for all four electron donors and much lower than previously reported; indicating that there could be advantages for attached growth versus suspended growth processes in terms of carbon utilization rates. The batch limiting NO₃-N and COD profiles were also used to find effective K_s values. These kinetic parameters describe NO₃-N and COD limitations into the biofilm, which affect the overall denitrification rates. Compared to the other electron donors, the maximum rate for methanol was quite low, but the estimated K_s value was also low (0.4 mg/L N). This suggests high NO₃-N affinity and low mass transfer resistance. The other three electron donors estimated higher K_s values, indicating that these biofilms have high diffusion resistance. Biofilm process modeling is more complex than for mechanistic suspended growth, since mass transfer affects substrate to and into the biofilm. Simulating the bench-scale MBBR performance using BioWin 3.0, verified that μ_max and boundary layer thickness play key roles in determining rates of substrate utilization. Adjustments in these parameters made it possible to mimic the MBBRs, but it is difficult to determine whether the differences are due to the MBBR process or the model. / Master of Science

The goal of this research was to characterize the effects of temperature changes on the denitrification process in a biological nutrient removal (BNR) system. Specifically, there were three objectives. First, the effects of temperature changes on denitrification rates by a bacterial population from a BNR system were investigated. Next, the role which PHAs (poly-beta-hydroxyalkanoates) played in the denitrification process were examined. Finally, the effect of temperature changes on the production and consumption rates of PHAs was determined. Sacrificial batch experiments were performed to assess the kinetic and chemical trends present in the denitrification process. Mixed liquor from the last anaerobic zone of a pilot scale BNR system was injected into vials. These vials were pre-purged with nitrogen gas in order to prevent dimolecular oxygen (02) from being entrained in the mixed liquor. Next, the vials were placed on a shaker table for 30 minutes in order to allow all external COD to be consumed. Following this, each vial was injected with nitrates and various macronutrients. This process was repeated for three different sets of batch tests; each set was identical except for the added substrate. One set received no added substrate while the other two received either acetate or glucose. Vials were sacrificed over a period of three hours and analyzed for nitrate, phosphate, PHB (polybeta-hydroxybutyrate), PHV (poly-beta-hydroxyvalerate), glucose and acetate. / Master of Science

The purpose of this research was to characterize a flushed dairy manure wastewater and to develop the kinetic and stoichiometric parameters associated with nitrogen removal from the wastewater, as well as to demonstrate experimental and simulated nitrogen removal from the wastewater. The characterization showed that all the wastewaters had carbon to nitrogen ratios large enough for biological nitrogen removal. Analysis of carbon to phosphorus ratios showed that enough carbon is available for phosphorus removal but enough may not be available for both nitrogen and phosphorous removal in anaerobically pretreated wastewater. In addition, kinetic and stoichiometric parameters were determined for the biological nitrogen removal in sequencing batch reactors for the dairy manure wastewater. Results showed that many parameters are similar to those of municipal wastewater treatment systems. This characterization and the derived kinetic and stoichiometric parameters provided some of the information necessary for development of a nitrogen removal process in a sequencing batch reactor. Lab scale treatment of a 1:2 dilution of the anaerobically pretreated wastewater was demonstrated. Treatment was able to achieve between 89 and 93% removal of soluble inorganic nitrogen as well as up to 98% removal of biodegradable soluble and colloidal COD. In addition, a solids removal efficiency of between 79 and 94% was achieved. The lab scale treatment study demonstrated that sequencing batch reactors are capable of achieving high nitrogen removal on wastewaters with the carbon to nitrogen ratios of the dairy manure wastewater. Model simulations of the treatment process were used to develop a sensitivity analysis of the reactor feed configuration as well as the kinetic and stoichiometric parameters. The analysis of the feed configuration demonstrated the advantage of decreasing the amount of feed that is fed in the last feed period so that the effluent nitrate will be minimized. The analysis indicated that the autotrophic growth rate is one of the most important parameters to measure while error in the heterotrophic decay or yield values can lead to miscalculations of oxygen required for treatment. / Master of Science

by Tong Suk Wah. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 196-206). / Abstract --- p.i / Acknowledgments --- p.iv / Table of Contents --- p.v / List of Abbreviations --- p.ix / List of Tables --- p.xi / List of Figures --- p.xv / Chapter 1 --- Introduction / Chapter 1.1 --- Landfilling in Hong Kong --- p.1 / Chapter 1.2 --- Generation of Landfill Leachate --- p.3 / Chapter 1.3 --- Composition of Landfill Leachate --- p.6 / Chapter 1.4 --- Toxicity of Landfill Leachate --- p.12 / Chapter 1.5 --- Treatment of Landfill Leachate --- p.15 / Chapter 1.5.1 --- Physico-chemical treatment --- p.16 / Chapter 1.5.1.1 --- Coagulation/Flocculation/Precipitation --- p.16 / Chapter 1.5.1.2 --- Oxidation --- p.18 / Chapter 1.5.1.3 --- Activated carbon adsorption --- p.19 / Chapter 1.5.1.4 --- Ammonia stripping --- p.20 / Chapter 1.5.1.5 --- Reverse osmosis --- p.21 / Chapter 1.5.2 --- Biological treatment --- p.22 / Chapter 1.5.2.1 --- Aerobic treatment --- p.22 / Chapter 1.5.2.1.1 --- Activated sludge system --- p.23 / Chapter 1.5.2.1.2 --- Aeration lagoon --- p.25 / Chapter 1.5.2.1.3 --- Sequencing batch reactor --- p.26 / Chapter 1.5.2.1.4 --- Trickling filter --- p.27 / Chapter 1.5.2.1.5 --- Rotating biological contactor --- p.27 / Chapter 1.5.2.2 --- Anaerobic treatment --- p.29 / Chapter 1.5.3 --- Co-treatment with municipal wastewater --- p.32 / Chapter 1.5.4 --- Recirculation --- p.33 / Chapter 1.5.5 --- Irrigation --- p.34 / Chapter 1.6 --- Aims of the Thesis --- p.35 / Chapter 2 --- Characterization of Landfill Leachate / Chapter 2.1 --- Introduction --- p.37 / Chapter 2.2 --- Materials and Methods / Chapter 2.2.1 --- Description of landfill sites --- p.39 / Chapter 2.2.2 --- Leachate collection --- p.40 / Chapter 2.2.3 --- Chemical analysis --- p.40 / Chapter 2.2.4 --- Biological analysis --- p.41 / Chapter 2.2.5 --- Statistical analysis --- p.42 / Chapter 2.3 --- Results and Discussion / Chapter 2.3.1 --- Chemical properties of leachate --- p.43 / Chapter 2.3.2 --- Temporal variation of leachate quality --- p.61 / Chapter 2.3.3 --- Correlation of leachate quality and rainfall --- p.65 / Chapter 2.3.4 --- Biological composition of leachate --- p.86 / Chapter 2.4 --- Conclusions --- p.88 / Chapter 3 --- Toxicological Analysis of Landfill Leachate / Chapter 3.1 --- Introduction --- p.92 / Chapter 3.2 --- Materials and Methods / Chapter 3.2.1 --- Leachate collection --- p.93 / Chapter 3.2.2 --- Chemical analysis --- p.94 / Chapter 3.2.3 --- Biological toxicity testing --- p.94 / Chapter 3.2.3.1 --- Microtox test --- p.95 / Chapter 3.2.3.2 --- Algal bioassay、 --- p.95 / Chapter 3.2.3.3 --- Crustacean bioassay --- p.96 / Chapter 3.2.3.4 --- Fish bioassay --- p.98 / Chapter 3.3 --- Results and Discussion / Chapter 3.3.1 --- Chemical properties of leachate --- p.99 / Chapter 3.3.2 --- Microtox test --- p.105 / Chapter 3.3.3 --- Algal bioassay --- p.108 / Chapter 3.3.4 --- Crustacean bioassay --- p.115 / Chapter 3.3.5 --- Fish bioassay --- p.115 / Chapter 3.4 --- Conclusions --- p.120 / Chapter 4 --- Nitrification of Landfill Leachate / Chapter 4.1 --- Introduction --- p.124 / Chapter 4.2 --- Materials and Methods / Chapter 4.2.1 --- Collection and analysis of leachate --- p.127 / Chapter 4.2.2 --- Set-up of nitrification system --- p.128 / Chapter 4.2.3 --- Experiment 1: Effect of additional phosphate on the rate of nitrification --- p.130 / Chapter 4.2.4 --- Experiment 2: Effect of HRT on the rate of nitrification --- p.130 / Chapter 4.2.5 --- Experiment 3: Effect of additional organic carbon on the rate of nitrification --- p.131 / Chapter 4.2.6 --- Statistical analysis --- p.131 / Chapter 4.3 --- Results and Discussion / Chapter 4.3.1 --- Chemical properties of landfill leachate --- p.132 / Chapter 4.3.2 --- Experiment 1: Effect of additional phosphate on the rate of nitrification --- p.132 / Chapter 4.3.3 --- Experiment 2: Effect of HRT on the rate of nitrification --- p.144 / Chapter 4.3.4 --- Experiment 3: Effect of additional organic carbon on the rate of nitrification --- p.154 / Chapter 4.3.5 --- Inhibition of free ammonia and nitrous acid --- p.162 / Chapter 4.3.6 --- Fate of ammonia --- p.166 / Chapter 4.4 --- Conclusions --- p.170 / Chapter 5 --- Denitrification of Nitrified Leachate / Chapter 5.1 --- Introduction --- p.172 / Chapter 5.2 --- Materials and Methods / Chapter 5.2.1 --- Collection and analysis of landfill leachate --- p.175 / Chapter 5.2.2 --- Set-up of treatment system --- p.176 / Chapter 5.2.3 --- Statistical analysis --- p.178 / Chapter 5.3 --- Results and Discussion / Chapter 5.3.1 --- Performance of nitrification system --- p.178 / Chapter 5.3.2 --- Performance of denitrification system --- p.181 / Chapter 5.3.3 --- Improvement of treatment efficiency --- p.187 / Chapter 5.4 --- Conclusions --- p.190 / Chapter 6 --- General Conclusions --- p.192 / References --- p.196 / Appendices / "Appendix 1 Medium for enumeration of heterotrophic bacteria, fungi, carbohydrate-utilizing bacteria, protein-utilizing bacteria and lipid-utilizing bacteria" --- p.207 / Appendix 2 Preparation of Bristol's medium --- p.210 / Appendix 3 Enumeration of ammonia oxidizers by Most Probable Number Method --- p.211 / Appendix 4 Enumeration of nitrite oxidizers by Most Probable Number Method --- p.214

Marine nitrogen (N) is an essential nutrient for all oceanic organisms. The cycling of N between biologically available and unavailable forms occurs through numerous reactions. Because of the vast number of reactions and chemical species involved, the N cycle is still not well understood. This dissertation focuses on understanding some of the reactions involved in the cycling of marine N, as well as improving techniques used to measure dissolved N2 gas. The largest loss term for global marine N is a reaction called denitrification. In this work, denitrification was measured in the sandy sediments of the Georgia continental shelf, an area where this reaction was thought to be unlikely because of the physical properties of the sediments. Nitrogen fixation, which is a reaction that produces biologically available N, was detected in Georgia estuarine sediments. N fixation was measured concurrently with denitrification in these sediments, resulting in a much smaller net loss of marine N than previously thought. Lastly, membrane inlet mass spectrometry (MIMS) is a technique that measures dissolved N2, the end product of denitrification and a reactant in N fixation reactions. This study suggests that N2 measurements by MIMS are influenced by O2 concentrations due to pressure differences inside of the ion source of the mass spectrometer. These findings seek to improve denitrification measurements using MIMS on samples with varying O2 concentrations. In conclusion, this dissertation suggests that the marine N cycle is more dynamic than has been suggested, due to the recognition of input and loss reactions in a wider range of marine and estuarine environments. However, improvements in the understanding of MIMS will help with direct measurements with reactions involved in the global marine N cycle.

This thesis includes both experimental and modelling studies on the treatment of drinking water. Three aspects were studied: (i) removal of fluoride (F– ) by adsorption, (ii) removal of fluoride and other contaminants by solar distillation, (iii) denitrification by a microbial fuel cell. The availability of potable water on earth is about 0.2% of the total available water. This very small quantity is polluted by anthropogenic and natural contaminants. Fluoride is a classic example of a natural contaminant, wherein the dissolution of F– bearing minerals causes the release of F– into the groundwater. Exposure to concentrations > 1 mg/L over ex-tended periods of time results in dental and skeletal fluorosis. Worldwide, about 220 million people are at risk. Nitrate is an example of anthropogenic contaminant, occurring because of addition of high quantities of fertilizers to the soil for better crop yields. The excess fertilizers penetrate the soil and mix with the groundwater, resulting in nitrate contamination. The major effect of nitrate contamination is met haemoglobin , which is caused because of the oxidation of ferrous ion in haemoglobin to ferric ion by the nitrite to form haemoglobin. The effects can be noticed by the change in colour of skin to bluish grey or brownish grey in infants. To counter the drastic effects of these anions, the World Health Organization (WHO) has prescribed permissible limits of 1.5 mg/L and 45 mg/L for F– and NO3 – , respectively. For obtaining contaminant-free water, many methods have been used. Reverse osmosis (RO) is one of the widely-used methods. Even though this process removes most of the contaminants, about 50 - 70% of the inlet water is wasted as a reject stream with higher concentrations of the contaminants. This is a very unsustainable way of using water, particularly in drought-prone areas. So, in the thesis a conceptual strategy with three different methods is developed to treat reject water. In the first part of the thesis, the removal of F– using adsorption was studied. Activated alumina (AA) and a hybrid anion exchange resin embedded with hydrous zirconium oxide nanoparticles (HAIX-Zr) (sample sent by Prof. Arup K SenGupta) were used as the adsorbents. The adsorbents were tested with synthetic water samples and reverse osmosis (RO) reject water. HAIX-Zr had a better adsorption capacity compared to AA when water containing only F– was used. The presence of high concentrations of co-ions affects the uptake of F– drastically, with a decrease of up to 34% and 79% for AA and HAIX-Zr, respectively. With AA, for a synthetic water sample with a small concentration of HCO3 – , there was a two-fold increase in the uptake of F– compared to a water sample containing only F– . There was no removal of NO3 – by AA. HAIX-Zr removes NO3 – , but to a lesser extent than F– . With AA, the pH of the inlet solution affected the adsorption capacity, because of the change in the surface charge of AA. Based on the type of water sample used, the cost of treated water varied from Re. 0.1 - 1.0/L ($ 0.0015 - 0.015/L) for AA and 0.2 - 11.5/L ($ 0.003 - 0.17/L) for HAIX-Zr. A community-level plant was set up to treat the RO reject water using AA. Due to challenges at the field level, the pilot plant had to be stopped after 80 bed volumes of water were treated. From our observations and as also reported by many authors, the adsorption of F– is affected by the presence of many ions. When modelling the adsorption of F– , it is usually taken as a single entity getting adsorbed on the adsorbent. As this is not a proper assumption, a model was developed which takes into account all the speciation reactions that take place during adsorption, and all the species like H+, OH– , Na+, Cl– , and NO3 – present in the solution along with F– . Using the model, the equilibrium constants and rate constants for the reactions were obtained. For one initial concentration of F– , a good fit was obtained to the batch adsorption data, except at short times. Due to uncertainty about the amount of impurity present in the adsorbent, at higher initial concentrations of F– , there was a significant discrepancy between predictions and data. Considering column experiments, the breakthrough curve for F– was simulated using the developed model. For the special case of negligible mass transfer resistances, the predicted break-through volume was within 3% of the observed value. In the second part of the thesis, nitrate removal was investigated using microbial fuel cell (MFC). In a MFC, power is generated by the activity of the microorganisms present in the cell. The organisms present in the anode side release electrons (e– ) by the use of substances that can be oxidized, namely, glucose, acetate, etc. On the cathode side, the organisms have the potential to take in e– and reducible substances, and release reduced products like nitrogen, hydrogen, etc. In the present case, nitrates added to the cathode side were reduced to nitrogen gas by the use of a consortium of micro-organisms taken from seawater. A similar consortium was used in the anode chamber Here, the study was focused on improving the efficiency of MFC for removal of NO3 – , by changing the buffering medium used in the cells. Commonly, phosphate buffer is used, but when using a MFC for treatment, the presence of PO43 – causes water contamination and is not suitable for drinking. There-fore, PO43 – was replaced with HCO3 – on the cathode side of the cell. This resulted in a higher removal of NO3 – and power production compared to the PO43 – buffered solution In the third part of the thesis, contaminant removal using solar distillation was investigated. For this as inclined basin still was used. Investigations were based on the evaporation rate of contaminated water, and the odour and concentrations of ions in the distillate. In order to improve the evaporation rates, different radiation absorbing materials like sand, activated charcoal, and carbon nanoparticles encapsulated in polymer sheets (PCNP) were investigated. It was observed that the evaporation rates were higher with activated carbon than the other materials. Using this technique there was about 99% removal of NO3 – , F– , SO42 – and the concentrations of ions in the distillate were well below the acceptable limits. When sand or PCNP was used as an absorbing/wicking medium, the distillate had an objectionable odour. With the use of AC, the odour could be eliminated because of the adsorption of odour-causing compounds.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-02-09T16:06:33Z No. of bitstreams: 1 TESEDOUTORADO_ANA PAULA DA SILVA_2016.pdf: 3643578 bytes, checksum: aee17ef8cffb8a82bfd826eb5c41ddac (MD5) / Made available in DSpace on 2017-02-09T16:06:33Z (GMT). No. of bitstreams: 1 TESEDOUTORADO_ANA PAULA DA SILVA_2016.pdf: 3643578 bytes, checksum: aee17ef8cffb8a82bfd826eb5c41ddac (MD5) / Coordenação de Aperfeiçoamento de Pessoal Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica, Niterói, RJ. / O Óxido nitroso (N2O) é um importante gás do efeito estufa que contribui para as mudanças climáticas globais através do aquecimento radiativo e depleção do ozônio estratosférico. Segundo o IPCC a concentração atmosférica de N2O aumenta a taxas de 0,2 a 0,3% anualmente, e aumentou do período pré-industrial de 270 ppb para 329 ppb em 2016. A emissão deste gás por solos resulta principalmente dos processos de nitrificação e desnitrificação. O melhor conhecimento da contribuição de cada processo poderá ajudar a prever e mitigar as emissões de N2O por solos. Os métodos atuais para a investigação das taxas brutas de nitrificação e desnitrificação envolvem aplicação de inibidores químicos e/ou marcadores isotópicos 15N, os quais alteram a composição da atmosfera do solo. Neste trabalho a teoria do método da separação barométrica de processos (BaPS) foi utilizada para quantificar as taxas brutas de nitrificação e desnitrificação através de medidas de variações da pressão do ar num sistema hermético e isotérmico sem aplicação de inibidores ou marcadores químicos. Câmaras para incubação do solo equipadas com sensores de pressão, temperatura, O2 e CO2 foram construídas e amostras de solo de uma região que emite altos fluxos de óxido nitroso localizada em Jardim Catarina em São Gonçalo (RJ) foram selecionadas para o estudo dos processos de produção do gás. O fluxo in situ foi medido e o resultado médio foi de 25 ngN2O-Ncm-2h-1. A alta emissão de N2O in situ foi observada após período de alagamento da área de amostragem pelas águas poluídas do Rio Alcântara. O método BaPS foi utilizado para determinar as taxas de respiração do solo, nitrificação bruta e desnitrificação em experimentos no laboratório. Os resultados mostraram que as taxas brutas de desnitrificação foram sempre maiores que as taxas brutas de nitrificação e que os maiores fluxos de N2O gerados estão associados ao processo de desnitrificação. / climate change through radiative warming and the depletion of stratospheric ozone. According to the IPCC, the concentration of N2O atmospheric increases at rates of 0.2 to 0.3% annually, and increased had risen from the pre-industrial period from 270 ppb to 324 ppb by 2011. Its emission from soils results mainly from denitrification and nitrification process. A better knowledge of the contribution of each process should help to predict and mitigate N2O emissions by soils. Current methods for investigation of gross nitrification and denitrification rates involve N tracers and acetylene inhibition techniques These methods have the disadvantage of introducing labeled material into soil or changing the composition of soil atmosphere. In this work, the barometric process separation technique (BaPS) was applied to quantify gross nitrification and denitrification rates by measuring air pressure variations in a hermetic and isothermal system without the application of chemical inhibitors or markers. Soil incubation chambers equipped with pressure, temperature, O2 and CO2 sensors were constructed and soil samples from a region known to emit high nitrous oxide flows located in Jardim Catarina, São Gonçalo (RJ) were selected for this study. In situ flow was measured and the mean result resulted in 25 ngN2O-Ncm-2h-1. The high N2O emission in situ was observed after a period of flooding in the polluted waters of the Alcântara River. The BaPS method was used to determine the rates of soil respiration, gross nitrification and denitrification. The results showed that the gross denitrification rate was always greater than nitrification and that the higher N2O fluxes generated are associated with the denitrification process

O objetivo do presente trabalho foi avaliar o desempenho de um reator de leito fixo e fluxo ascendente (RLFFA) em escala de bancada submetido à baixa aeração e recirculação. O reator foi utilizado como um sistema de pós-tratamento do efluente de indústria de fabricação de ração animal (INCOFAP) a partir de resíduos de abatedouro de aves, caracterizado por elevada carga de nitrogênio amoniacal. Para tanto, o RLFFA foi avaliado quanto à remoção da fração remanescente de matéria orgânica e de nitrogênio do efluente do reator UASB instalado na indústria. O RLFFA foi operado em condições mesofílicas (30°C) e tinha volume total de 11,5 L e volume útil de 6,1 L, com leito estruturado composto por 13 estruturas cilíndricas (3 cm de diâmetro) de espuma de poliuretano, dispostas verticalmente no interior do reator. O reator apresentou sistema de recirculação interna, com razão de recirculação igual a 3, suficiente para garantir a mistura completa. O sistema foi operado em três condições distintas, que foram denominadas de fases, todas com tempo de detenção hidráulica (TDH) de 24 horas e concentração de oxigênio dissolvido próxima a 1,0 mg.L-1. Nas fases 1 e 2, o RLFFA foi alimentado com 20% de efluente do UASB diluídos em água, e a alimentação da Fase 3 foi com 10% de efluente. As relações DQO/N para as Fases de 1 a 3 foram de, respectivamente, 0,28, 0,41 e 0,26. Na Fase 1, a alcalinidade foi mantida em concentração estequiométrica para a ocorrência da nitrificação total, enquanto nas fases 2 e 3 a alcalinidade foi adicionada em excesso. As melhores eficiências de remoção de N-total e DQO foram obtidas na Fase 1, com respectivamente, 48 ± 24% e 63 ± 20%, atingindo remoção máxima de N-total de 79% e 92% para DQO. As análises estatísticas demonstraram independência entre a remoção de DQO e a remoção de N-total, e com demanda de doador de elétrons para desnitrificação heterotrófica via nitrato superior à DQO removida, indicando a ocorrência de vias complementares. A desnitrificação via nitrito e a desnitrificação autotrófica foram observadas nos ensaios cinéticos de desnitrificação via nitrito e teste de atividade para desnitrificação autotrófica utilizando sulfeto como doador de elétrons. A modelagem para qualidade da água do rio Chibarro( local de lançamento do efluente da empresa INCOFAP) utilizando uma modificação do modelo de Streeter-Phelps, indicou que o cenário com a adoção do reator estudado no presente trabalho para tratamento do efluente da INCOFAP permitiu reduzir o impacto para a qualidade da água do rio Chibarro ao se comparar ao sistema atual de tratamento do efluente da empresa INCOFAP. Entretando, ainda faz-se necessária a elevação da eficiência de remoção de N-total no sistema, para atingir a concentração máxima de N-amoniacal permitida de 20 mg.L-1 para o efluente para compatibilização com a capacidade de autodepuração do rio Chibarro. / The objective of this study was to evaluate the performance of a bench scale up-flow fixedbed reactor (UFBR) subjected to low aeration and effluent recirculation.The reactor was used as a post-treatment system of effluent from animal food plant (INCOFAP) using poultry slaughterhouse wastes, characterized by high ammoniacal nitrogen load rate.Therefore, the UFBR was evaluated in respect to residual organic matter and nitrogen removal of industrys UASB reactor effluent. The UFBR was operated in mesophilic conditions (30°C) and it had a total volume of 11.5 L and a working volume of 6.1 L, with a structured bed composed by 13 polyurethane foam vertical cylindrical structures (3 cm of diameter) inside the reactor. The reactor was provided with internal recirculation system with recirculation ratio of 3, suficiente to guarantee a complete mixture. The system was operated in three different phases, with hydraulic retention time (HRT)of 24 hours and dissolved oxygen concentration close to 1.0 mg.L-1.On Phases 1 and 2, the UFBR was fed with 20% of UASB effluent diluted in water,and the Phase 3 was fed with 10% of effluent. On phases 1 to 3 COD/N ratios were, respectively, 0.28, 0.41 and 0.26. The alkalinity on Phase 1 was maintained on stoichiometric concentration to total nitrification, while in phases 2 and 3 excess alkalinity was added. The best total nitrogen and COD removal efficiencies were obtained in Phase 1, with respectively, 48 ± 24% and 63 ± 20% , reaching maximum total nitrogen removal of 79% and 92% for COD. Statistical analysis demonstrated independency between COD and total nitrogen removal, and with higher electron donor demand for nitrate denitrification than COD removal, indicating the occurrence of complementary paths. The nitrite denitrification and autotrophic denitrification were noted in kinetics experiments and activity tests for autotrophic denitrification using sulfide as source of electron donors. The modeling for Chibarro river water quality (site of INCOFAPs effluent release) , using a modified Streeter-Phelps model, indicated the scenario with the adoption of the studied reactor on this work for INCOFAP's effluent treatment provided the reduction of the impact on Chibarros water quality in comparison with the current effluent treatment of INCOFAP. However, it is still necessary an increase on system denitrification efficiency to reach the maximum ammoniacal nitrogen concentration allowed of 20 mg.L-1 for the effluent to make compatible with de selfpurification of Chibarro river.

The feedbacks between hydrology and biogeochemical cycling of nitrogen (N) are of critical importance to global bioavailable N budgets. Human activities are dramatically increasing the amount of bioavailable N in the biosphere, which is causing increasingly frequent and severe impacts on ecosystems and human welfare. Streams are important features in the landscape for N cycling, because they integrate many sources of terrestrially derived N and control export to downgradient systems via internal source and sink processes. N transformations in stream ecosystems are typically very complex due to spatiotemporal variability in the factors controlling N biogeochemistry. Thus, it is difficult to predict if a particular stream system will function as a net source or sink of bioavailable N. A key location for N transformations in stream ecosystems is the hyporheic zone, where stream and ground waters mix. The hyporheic zone can be a source of bioavailable N via nitrification or a sink via denitrification. These N transformations are regulated by the physical and biogeochemical conditions of hyporheic zones. Natural heterogeneity in streams leads to unique combinations of both the physical and biogeochemical conditions which in turn result in unique N source and sink conditions. This dissertation investigates the relationships between physical and biogeochemical controls and the resulting fate of bioavailable N in hyporheic zones. The key physical factor investigated is the supply rate of solutes which is a function of transport processes - advection and dispersion, and transport conditions - hydraulic conductivity and flowpath length. Different physical conditions result in different characteristic residence times of water and solutes in hyporheic zones. The key biogeochemical factors investigated are the dynamics of oxygen (O₂), labile dissolved organic carbon (DOC), and inorganic bioavailable N (NH₄⁺ and NO₃⁻). This dissertation uses ¹⁵N isotope experiments, numerical modeling of coupled transport of the bioavailable N species, O₂ and DOC, and a suite of geophysical measurements to identify the key linkages between hydrological and biogeochemical controls on N transformations in hyporheic zones. Specifically, it was determined that the conditions governing the fate of hyporheic N are both the physical transport and reaction kinetics – the residence time of water and the O2 uptake rate. An important scaling relationship is developed by relating the characteristic timescales of residence time and O₂ uptake. The resulting dimensionless relationship, the Damköhler number for O₂, is useful for scaling different streams hyporheic zones and their role on stream N source – sink dynamics. More generally, these investigations demonstrate that careful consideration and quantification of hydrological processes can greatly inform the investigation of aquatic biogeochemical dynamics and lead to the development of process-based knowledge. In turn, this process-based knowledge will facilitate more robust approaches to quantifying and predicting biogeochemical cycles and budgets. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Sept. 21, 2011 - March 21, 2012

Im Einzugsgebiet der Fassung A des Wasserwerks Thülsfelde wurden in langjährigen Beobachtungen Nitratgehalte an einzelnen Lokationen von bis zu 300 mg/L im oberflächennahen Grundwasser gemessen. Dennoch ist die betrachtete Fassung A des 27 km2 großen Einzugsgebietes weitgehend nitratfrei. In der vorliegenden Arbeit wurde untersucht, welche Prozesse im Untersuchungsgebiet wirken, wie die hierfür in Frage kommenden Abbauprozesse und das für die Prozesse notwendige reaktive Material verteilt sind. Es ist bekannt, dass mikrobielle Reduktionsprozesse die effektivsten Nitratsenken sind. Diese Prozesse benötigen geeignete Reaktionspartner, die im Untergrund auch vorhanden sind, z.B. organischer Kohlenstoff oder Disulfidschwefel. In der vorliegenden Arbeit wurden folgende Teilaufgaben bearbeitet: • Identifikation reaktiver Zonen • Identifikation der Umsetzungsprozesse • Identifikation ihrer räumlichen Lage • Identifikation der Verteilung reaktiven Materials • Aufbau eines Prognosewerkzeuges. Mit den Ergebnissen der Untersuchungen (Gesamtschwefelgehalt, Gesamtkohlenstoffgehalt) an Gesteinsmaterial aus 13 Rammkernsondierungen bis in eine Tiefe von 19 m uGOK sowie einer Bohrung bis in eine Tiefe von 40 m uGOK, konnte im Grundwasserleiter eine vertikale Zonierung des reaktiven Materials abgebildet werden. Bis in eine Tiefe von 20 m uGOK sind nur geringe Gehalte reaktiven Materials gefunden worden (gemessen als Schwefelgesamtgehalte: kleiner 100 [mg/kg]). Erst darunter wurden bis 26 m uGOK Schwefelgesamtgehalte zwischen 100 und 1000 [mg/kg] und in Tiefen bis zu 36 m uGOK bis zu 6400 [mg/kg] Gesamtschwefel gefunden. Die Auswertung der Beschaffenheitsdaten an Vorfeldmessstellen und an der für diese Arbeit projektierten Mehrstufenmessstelle SGM (7 Beprobungshorizonte, bis in 35,6 m uGOK) zeigten, dass genau in den Tiefenbereichen mit ansteigenden Gehalten reaktiven Materials die Redoxgrenze verläuft. Unterhalb von 25 m uGOK ist das Grundwasser praktisch nitratfrei. Untersuchungen zum Grundwasseralter ergaben für den Bereich der Redoxgrenze ein Alter zwischen 15 und 25 Jahren. Dies konnte als Hinweis darauf gedeutet werden, zusammen mit den beschriebenen Erkenntnissen zur Zonierung des reaktiven Materials und der Nitratkonzentrationen in diesem Bereich, dass der Grund für die praktische Nitratfreiheit unterhalb von 20 bis 25 m uGOK Umsatzprozesse im Grundwasserleiter sind. Die durchgeführten Batch-und Säulenversuche zum Abbau von Nitrat an Material aus dem Grundwasserleiter zeigten in ihren Ergebnissen ebenfalls eine vertikale Zonierung über die Tiefe. Mit zunehmender Tiefe wurde eine höhere Abbauleistung (bezogen auf die Ausgangsmassenkonzentrationen von Nitrat in den Versuchsgefäßen) erreicht. Im oberen Grundwasserleiter wurden bis zu 50 % Abbauleistung erreicht, nur in den tiefen Zonen wurden mehr als 50 bis zu 100 % Abbauleistung erreicht. In den Versuchen mit Material aus dem oberen Grundwasserleiter konnten keine vollständigen ablaufenden Reaktionen beobachtet werden. Für die Berechnung des Nitrattransportes wurde ein Grundwasserströmungs- und Transportmodell aufgebaut. Verwendet wurde die Software Modflow und MT3d99. In das Transportmodul MT3d99 wurden für den Abbau von Nitrat aus Feldversuchen ermittelte Geschwindigkeitskonstanten eingebaut. Mit dem Prognosewerkzeug wurden Szenarien unterschiedlicher Nitrateinträge abgebildet. Es konnte gezeigt werden, dass steigende Nitratkonzentrationen im Grundwasserleiter abhängig vom Eintrag und von der reaktiven Kapazität eines Grundwasserleiters sind. Dabei wurde anhand von 3 unterschiedlichen Szenarien deutlich, dass das Vorhandensein z.B. von Disulfidschwefel im Untergrund nur eine Scheinsicherheit darstellt. Der Reaktionspartner wird bei dem mikrobiellen Umsatz aufgebraucht. Es kann innerhalb weniger Jahre zum Ansteigen der Nitratkonzentrationen und zum Nitratdurchbruch kommen. Das aufgebaute Modell ist in der Lage unterschiedliche Szenarien für den Nitrateintrag, z.B. bei Landnutzungsänderungen, unter der Berücksichtigung der Verteilung reaktiven Materials, zu simulieren. Das Ergebnis des Rechenmodells sind Spannweiten von Nitratkonzentrationen für das System Grundwasserleiter. Für die Fassung A bleiben noch Fragen offen: • Wie ist die Verteilung reaktiven Materials im tiefen Grundwasserleiter? • Welche Massen reaktiven Materials sind verfügbar, nicht nur stöchiometrisch? • Wie sind die Reaktionen im tiefen Grundwasserleiter verteilt? • Welche Abbausequenzen existieren im tiefen Grundwasserleiter? (Anlage Rohdaten auf CD-Rom in Printversion 226 MB)