>Magister Scientiae - MSc / In South Africa, water pollution problems have continued to increase due to increasing anthropogenic activities. The increasing number of organic contaminants in various water sources can be attributed to industrial development, population growth and agricultural run- off. These activities have impacted negatively on the availability and accessibility to sustainable clean water resources, exposing citizens to water borne diseases such as cholera, diarrhoea and typhoid fever; commonly reported among children. Advanced oxidation technologies such as dielectric barrier electrohydraulic discharge (EHD), also referred to as dielectric barrier discharge (DBD), have the ability to decompose persistent organics and eliminate microbes. DBD offers advantages such as efficiency, energy saving, rapid processing, use of few or no chemicals, and non-destructive impact on the ecosystem. The system is also capable of generating ozone, hydrogen peroxide, singlet oxygen, superoxide radicals, hydroxyl radicals and other active species. The combination of these reactive species has been reported to degrade biological and chemical pollutants rapidly and efficiently. In this study, the DBD system was optimized by investigating the effect of physico-chemical, electrical parameters and reactor configurations on Methylene Blue (MB) decolouration efficiency. The physico-chemical parameters included MB concentration, solution pH and conductivity, solution volume, NaCl electrolyte concentration in the electrode compartment and air flow rate. As for electrical parameters, the effects of voltage, electrode type and size on MB decolouration efficiency were studied. The effect of the aforementioned parameters on MB decolouration efficiency was assessed by varying one parameter at a time. The following physico-chemical parameters: time (from 0 - 60 minutes), pH (2.5 - 10.5), solution conductivity (5 - 20 mS/cm), MB concentration (0.5 – 10 mg/L), solution volume (500 – 2000 mL), NaCl electrode electrolyte concentration (10 – 50 g/L) and air flow rate (2– 4 L/min) were varied in their respective ranges under the applied experimental conditions: reactor air gap 2 mm, solution volume 1500 mL, NaCl electrolyte concentration of 50 g/L in the electrode compartment, voltage 25 V (7.8 kV), airflow rate 3 L/min, 0.5 mm silver electrode and a running time of 60 minutes. As for electrical parameters, voltage (from 20 - 25 V), electrode type (copper, silver and stainless steel) and electrode diameter (0.5 – 1.5 mm) were also altered individually at the applied experimental conditions. The reactor air gap was varied from 2 to 6 mm. At the same experimental conditions, the free reactive species generated mainly H2O2 and O3, were detected and quantified using the Eisenberg and indigo methods, respectively. The optimum physico-chemical parameters were found to be MB concentration 5 mg/L, concentration of NaCl electrolyte used in the central compartment of the DBD reactor 50 g/L, solution pH 2.5, solution conductivity 10 mS/cm, air flow rate 3 L/min, solution volume 1500 mL and an optimum contact time of 30 minutes. The optimum electrical parameters were found to be: applied voltage 25 and 1.5 mm silver electrode. The following parameters MB concentration, solution conductivity and pH, applied voltage and reactor configuration significantly affected MB decolouration efficiency compared to parameters such as solution volume, the inlet air flow rate, electrode type and size and NaCl electrolyte concentration in the electrode compartment, which were less effective in enhancing MB decolouration. Moreover, for all DBD experiments performed at the applied experimental conditions, complete decolouration of MB was achieved in the first 30 minutes. However, trends between the optimized parameters and MB decolouration efficiency were mostly observed after 10 minutes. The optimized DBD system reduced the treatment time from 30 to 20 minutes without any chemical additives. Moreover, at 5 mg/L MB under the applied optimum conditions, it was proved that besides 99% of MB decolouration reached after 60 minutes, 53% of total organic carbon (TOC) removal was also achieved. The chemical oxygen demand (COD) characterizing MB toxicity was less than 5 mg/L before as well as after the DBD experiment. After 10 minutes of experiment under the following conditions: Applied voltage 25 V, MB concentration 5 mg/L, solution pH (in between 6.04 and 6.64), solution volume 1500 mL, air flow rate 3 L/min, 0.5 mm silver electrode and a contact time of 60 minutes, about 3.73 x 10-5 mol/L H2O2 was produced which decreased to 2.93 x 10-5 mol/L 10 minutes later, while O3 concentration was initially very low and could not be detected. However, 0.5 mol/L of O3 was detected after 20 minutes of operating time, thereafter, H2O2 concentration decreased continuously with time while that of O3 fluctuated as the treatment time increased. Likewise, the energy density for the production of free reactive species reached 0.87 g/ kWh in the first 10 minutes due to the presence of chromophoric functional groups such as =N+(CH3)2 in MB structure that had to be destroyed. Thereafter, the energy consumption decreased progressively to zero with an increase in treatment time due to the destruction of =N+(CH3)2 groups in MB structure with time. The correlation between the rise in the of H2O2 concentration and energy density after 10 minutes was probably due to dissociation of OH- OH bonds in H2O2 by UV light to yield OH radicals which unselectively may have attacked MB dye. Thus, MB decomposition in the current DBD reactor was mostly initiated by H2O2 and O3. The irradiation of H2O2 by UV light generated in the DBD system was found to accelerate dye decomposition in the first 30 minutes of the experiment. The UV-vis analysis of treated MB samples confirmed that the complete decolouration of MB achieved in the first 30 minutes was due to the destruction of the chromophoric [=N+(CH3)2] group in Methylene blue structure, while the FT-IR confirmed the presence of traces of various functional groups such as C=C, C=O, C=N, NH, NH3, NO2, etc. characteristics of carboxylic acids, amines, amides, nitrogen based compounds (salts), aliphatic and unsaturated by-products remaining in the bulk solution after treatment. The salts analysis after treatment showed that 16 mg/L of nitrates and nitrites and 1.1mg/L of sulphates mainly originating from air and MB decomposition were present in the treated samples. The EHD/DBD system used in this study offers an approach to partially treat water/wastewaters and its optimization was able to significantly enhance the decomposition of the target MB dye as indicated by the reduction of total organic carbon (TOC) from 8.3 mg/L to 3.9 mg/L. Compared to previous research, this study successfully optimised a complete double cylindrical dielectric barrier discharge (DBD) reactor at ambient condition without any chemical additives.

Orientador: Ariovaldo José da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agrícola / Made available in DSpace on 2018-08-29T00:00:15Z (GMT). No. of bitstreams: 1 Bicalho_CamillaSantos_M.pdf: 1184147 bytes, checksum: 38517c9f0a392311762a5198cd1a3a1b (MD5) Previous issue date: 2015 / Resumo: Altas concentrações de nitrogênio em corpos d¿água acarretam impactos ambientais negativos como a eutrofização e danos às comunidades aquáticas. Um dos efluentes com maiores concentrações desse nutriente é o de suinocultura, atividade agrícola amplamente desenvolvida no país. Por isso é importante que sejam desenvolvidas e aperfeiçoadas tecnologias de tratamento que removam significativamente esse nutriente antes do lançamento. Nesta pesquisa foi avaliado um sistema de tratamento biológico combinado para remover nitrogênio de efluente sintético simulando água residuária de suinocultura. O sistema de tratamento foi composto por um decanto-digestor, o reator Sharon de nitrificação parcial e um reator Anammox de oxidação anaeróbia da amônia que são tecnologias promissoras de remoção de nitrogênio, que demanda menos energia, produz menos lodo e não há necessidade de adição de DQO ¿ demanda química de oxigênio. Para início do tratamento foi preparado e caracterizado o efluente sintético de suinocultura bruto e microrganismos foram enriquecidos para inocular os reatores Sharon e Anammox. O sistema combinado foi operado em duas fases, 90 dias sem ajuste de pH e segunda fase de 51 dias com ajuste de pH. O enriquecimento dos microrganismos obteve resultado satisfatório para os inóculos, porém seu desempenho foi comprometido por alguns parâmetros monitorados como pH, TDH ¿ tempo de detenção hidráuçica e oxigênio dissolvido que não estavam na faixa ideal de funcionamento, bem como a fase de digestão anaeróbia que se manteve acidificada. Em termos globais não houve remoção de nitrogênio amoniacal, mas houve 12% de remoção de NTK ¿ nitrogênio total Kjeldhal, devido sua composição ter uma parte orgânica. Não houve diferença significativa de remoção de nitrogênio entre as fases sem ajuste e com ajuste de pH. Para a DQO a remoção foi de 36% para o sistema Sharon-Anammox. O sistema tem potencial para altas remoções de nitrogênio, porém para o melhor desempenho sugere-se que seja aumentada a concentração de nitrogênio afluente no sistema, que o ajuste de pH seja em tempo integral e que o experimento seja desenvolvido em batelada para melhor controle do sistema como um todo / Abstract: High nitrogen concentrations in water bodies lead to negative environmental impacts such as eutrophication and damage to aquatic communities. One of the effluents with higher concentrations of this nutrient is the swine wastewater, widespread agricultural activity developed in the country. Due to this it is important to develop and improve treatment technologies which significantly remove this nutrient before discharge. This research aimed to evaluate a combined biological treatment system to remove nitrogen from synthetic effluent simulating swine wastewater. The treatment systems was composed by a decant-digester, Sharon reactor of partial nitrification and Anammox reactor of ammonia anaerobic oxidation which are promising technologies for the removal of nitrogen, requiring less energy and without addition of COD - Chemical demand oxygen. To start the treatment was prepared and characterized synthetic swine wastewater and microorganisms were enriched for inoculum reactor Sharon and Anammox. The combined system operated in two phases, 90 days without pH control and 51 days with pH control. The enrichment of microorganisms obtained a satisfactory result to the inoculums, although its performance was compromised by some monitored parameters like pH, HDT ¿hydraulic detention time and dissolved oxygen, which were not in the ideal range to operate, as well as the anaerobic digestion phase which remained acidified. In global terms there was no ammonia nitrogen removal, but had 12% removal to TKN ¿ total Kjeldhal nitrogen, due to its composition has an organic part. There was no significant difference for nitrogen removal between the phases with pH adjustment and without pH adjustment. To COD the removal was 36% in Sharon-Anammox process. The system has potential to high nitrogen removal, although to a better performance it is suggested that the affluent nitrogen concentration is increased in the system, full-time adjustment of pH and that the experiment is carried out in batch reactor for better control of the system as a whole / Mestrado / Agua e Solo / Mestra em Engenharia

A degradação da qualidade de água no Brasil é um problema sério que afeta grande parte dos rios e lagos. O objetivo desse trabalho é discutir quais mecanismos podem ser usados para a melhora da qualidade das águas tendo em vista a garantia dos seus usos. A legislação brasileira prevê que o sistema de gestão de recursos hídricos deve definir os usos pretendidos para as águas das bacias hidrográficas. Nos casos em que a qualidade das águas precisa ser melhorada para garantir os usos pretendidos, o sistema de gestão de recursos hídricos deve estabelecer etapas progressivas, em que, para cada etapa, são definidas metas de qualidade de água específicas. Utilizando como exemplo o sistema de gestão de qualidade de água de diferentes países, essa dissertação analisa o sistema brasileiro, a definição de metas e a sua relação com o sistema de gestão de recursos hídricos, conforme as definições previstas na Resolução CONAMA 357/05, e identifica os desafios e estratégias para superá-los. Também demonstra que, para que haja mudanças efetivas no cenário de qualidade das águas, será necessário para o país um planejamento estratégico, com prioridades definidas de acordo com as especificidades locais, os investimentos necessários e os aspectos econômicos, enfatizando-se o planejamento e o controle dos serviços de saneamento. / Water quality degradation is a serious problem that affects large extensions of rivers and lakes. The purpose of this thesis is to discuss which mechanism can be used to improve water quality in order to guarantee designated uses. The Brazilian water law establishes that the water resource management system must define the designated uses for the watershed. In cases where water quality must be improved to guarantee such uses, the water resource management system establishes a step-by-step system in which, for each step, specific water quality targets are defined. Using as an example the water quality management system of different countries, this thesis analyses the Brazilian system, the target definitions and its relations with the water resource management system, as defined by CONAMA Resolution 357/05, and identifies the challenges and the strategic seams to surpass them. It also demonstrates that, in order to get an effective change in the water quality scenario, it will be necessary for the country to work on strategic planning, with priorities based not only on specific local characteristics, but also on financial needs and economical aspects, with special emphasis on regulation and control of wastewater systems.

Contaminants of emerging concern (CECs) are an unregulated suite of constituents frequently detected in environmental waters, which possess the potential to cause a host of reproductive and developmental problems in humans and wildlife. Degradation pathways of several CECs are well-characterized in idealized laboratory settings, but CEC fate and transport in complex field settings is poorly understood. In the present study I use a multi-tracer solute injection to study and quantify physical transport and photodegradation in a wastewater effluent-impacted stream in Ankeny, Iowa. Conservative tracers are used to quantify physical transport processes in the stream. Use of reactive fluorescent tracers allows for isolation of the relative contribution of photodegradation within the system. Field data were used to calibrate a one-dimensional transport model, and forward modeling was then used to predict the transport of sulfamethoxazole, an antibiotic in the effluent which is susceptible to photolysis. Results show that accurate predictions of reactive CECs at the scale of stream reaches can be made using the fate and transport model based on field tracer studies. Results of this study demonstrate a framework that can be used to couple field tracer and laboratory CEC studies to accurately predict the transport and fate of CECs in streams.

Philosophiae Doctor - PhD / The popularization and health benefits associated with the "Mediterranean diet" saw a world wide increase in the production and consumption of processed olives and olive oil. During the brining of table olives large quantities of processed olive waste water is seasonally generated. This blackish-brown, malodours liquid is rich in organic and phenolic compounds, which cause environmental problems upon discarding. Currently, processed wastewater is discarded into large evaporation ponds where it poses serious environmental risks. The biodegradation of organic substrates present in the olive wastewater is inhibited by the high concentrations of phenolic compounds.

This thesis examines the effect of solids recycling on nitrification, organic carbon removal, and algal-bacterial productivity in bench-scale photobioreactors (PBRs) simulating winter pond conditions in San Luis Obispo, California and a 6-acre raceway system in Delhi, California. Two sets of duplicate photobioreactors operated with or without solids recycling were fed primary clarifier effluent (1oEff) for the first experiment, and facultative pond effluent (FAC) for the second experiment. In both experiments mean productivity was lower in solids recycled PBRs (3.67 and 2.3 g/m2-day), than in controls without solids recycling (4.15 and 3.9 g/m2-day). When fed 1oEff which contained a high amount of readily biodegradable COD, solids recycled PBRs had 30% less VSS in supernatant than controls after 1 hour of settling in Imhoff cones. However, when fed facultative pond water with no readily biodegradable COD there was little difference in supernatant VSS after settling. The type of wastewater influenced COD removal. PBRs had 40-50% soluble COD removal when fed 1oEff, and 10-20% removal when fed FAC. Mean PBR effluent COD was the same in both treatments and controls in when fed 1oEff (42 mg/L). When fed FAC mean effluent COD was marginally lower in solids recycled PBRs (61 mg/L) then in controls (68 mg/L). Most of the COD in 1oEff was readily biodegradable, while most of the COD in FAC was degraded while in facultative ponds leaving mostly recalcitrant and slowly biodegradable COD in FAC. Nitrification occurred more quickly and more reliably in solids recycled PBRs. The difference in nitrification was seen most notably when using FAC as PBR influent, where solids recycled PBRs had complete nitrification, but controls did not. When fed 1oEff all PBRs had complete nitrification, but solids recycled did so sooner. Overall, PBRs with solids recycling were also more resilient to changes in influent wastewater characteristics and had more consistent effluent water quality when fed wastewater that had occasional spikes in nitrogen and organic carbon. The difference between the two wastewaters indicates a possible inhibitory effect of FAC on nitrification. Microscopy data from both studies, though mostly qualitative, seems to indicate that solids recycling promotes biodiversity in algal-bacterial cultures, which may be part of the reason why solids recycling promoted more resilient and reliable treatment.

Heavy metals in wastewater can cause serious environmental problems and could beharmful to the human body. Therefore, heavy metals need to be removed from thewastewater. Coagulation based methods are popularly used nowadays with provedeffects. New methods such as the application of nanomaterials have brought morepossibilities to increase the removal effects for certain heavy metals. Among thesenanomaterials, graphene oxide has gained a lot of interest because of its large surfacearea and unique structure. Moreover, graphene oxide is an environmentally friendlymaterial. However, most of the reported studies did not use real wastewater samplesbut simulated ones prepared in labs. Therefore, the removal effects need to beexperimentally evidenced by using real wastewater samples. In this project, I studiedthe removal effects of pristine and modified graphene oxide using wastewatercollected at the wastewater treatment plant in Sundsvall (Fillan wastewater treatmentplant). Moreover, I have also studied the heavy metal removal effects of combinedcoagulation method and graphene oxide. Results have shown that graphene oxide hassimilar removal effects to the coagulation method, indicating the enormous potentialof graphene oxide in wastewater treatment. / <p>2021-09-19</p>

Thesis (M.Sc. (Zoology)) -- University of Limpopo, 2020 / The pressing state of South Africa’s freshwater resources due to pollution from the release of raw sewage or poorly treated domestic wastewater, has resulted in the urgent need for the implementation of innovative ways to mitigate this problem. A proposed solution by the Council of Science and Industrial Research (CSIR) is to introduce different cultures of algae in wastewater treatment ponds where facilities have aged and become dilapidated. In turn fish are introduced into sewage maturation pond treated with algae to reduce algal biomass. The assumption being that if fish can survive under these conditions, the nutrients assimilated will be converted into fish biomass when ingested, in an attempt to decrease aquas nutrient loads. The aim of the study was to assess the health and survival of Oreochromis mossambicus exposed to wastewater from the Motetema wastewater treatment plant (WWTP) and to establish the extent to which this species consumes micro-algae within the water column. The aim was accomplished by assessing the consumption of algae by O. mossambicus based on algal cell density counts in fish aquaria and to establish the feeding ratio of fish based on stomach content fullness as well as to monitor the survival rate of O. mossambicus exposed to various concentrations of sewage water over a 96-hour period. To establish fish survival under wastewater conditions, a 96-hour experiment was conducted in glass tanks (60 L), whereby the health and mortality of O. mossambicus exposed to different concentrations of domestic wastewater from Motetema WWTP was investigated. One set of aquariums supplied with compressed air via the use of diffusers while the other set of aquariums were void of aeration so as to simulate conditions at the treatment plant. Treatments comprising of four concentrations of 25, 50, 75 and 100% wastewater and a control of 0% were used. Water quality parameters were monitored every four hours and mortalities were recorded. Water samples were collected twice a day and sent to Capricorn Veterinary laboratory for nutrient analysis. Gill samples were also collected and sent to Onderstepoort Veterinary Institute for histological sections analysis. To assess the consumption of algae, 18 tanks (60 L) were set up in the laboratory, whereby three aquariums served as a control void of algae with the remaining tanks dosed with two algal species (Chlorella vulgaris and Chlorella protothecoides) of concentrations of 33%, 66% and 100%, over a period of ten days. Counts of algal density before and during the course of the experiments were done using a handheld flourometer. Upon mortalities and on the fifth day, fish were randomly selected from fish tanks, euthanised and stomach contents analysed. The stomach of fish was rated based on the percentage fullness and categorised as being empty, ¼ full, ½ full, ¾ full, full or gorged. When mortalities occurred, fish were dissected and their stomach contents analysed for fullness. Upon completion of the trial, two fish per treatment were euthanised and their stomach contents evaluated for algal consumption. Fish remaining at the end of the fish trial were counted and weighed to calculate the weight gain and specific growth rate. Survival rates were also determined. Water quality parameters were monitored three times a day over the duration of the trial. Water samples were collected every second day and send to Capricorn Veterinary laboratory for nutrient analysis. All mortalities were recorded over the duration of the trial period. In exposure and survival trials, physico-chemical parameters of water from the experimental tanks were within the acceptable limit for the growth and survival of O. mossambicus, except for dissolved oxygen and ammonia concentrations. Ammonia levels and mortality rates were significantly higher (p< 0.05) in treatments with wastewater, with ammonia levels exceeding those considered toxic for O. mossambicus. High ammonia concentrations resulted in definite histopathological changes in the gills as well as fish mortalities. After exposure to wastewater moderate signs of aneurism of the gill lamella, mild epithelial lifting, focal hyperplasia and clubbing of the terminal end of the secondary lamellae were recorded. Lesions are explained as a defence mechanism where gills increase the distance between the external environment and the blood, thus serving as a barrier to the entrance of the contaminants. Furthermore, results indicated that effluent levels >25% were detrimental to the fish. Fish survival decreased when exposed to effluent water, with higher number of mortalities recorded in tanks with no aeration. A 100% survival was observed in tanks with 25% treated wastewater in both aerated and non-aerated aquariums. The presence of fish mortalities in treatments >25 domestic wastewater shows that conditions at Motetema WWTP will be unfavourable for fish. Thus, results from the study indicate that domestic wastewater would need to be diluted to less concentrated levels to ensure the survival of fish and mechanical aerators needs to be deployed to increase oxygen levels in treatment ponds. Water quality parameters for the second set of experiments fell within the recommended range for the growth and survival of fish. However, low oxygen levels were recorded from the control group with minimum values of 1.8 mg/l and maximum concentrations of 3.6 mg/l. Furthermore, temperature and pH ranges recorded during this study fell within the desired range for growth and reproduction of Chlorella vulgaris and Chlorella protothecoides. Nutrient concentration (phosphates, sulphates and nitrate) for this study were low, however ammonia and nitrite were above the acceptable level for fish growth and survival. The presence of fish resulted in increased levels of ammonia. High ammonia levels were not mitigated by algae in the tanks. However, the high ammonia levels decreased with the increasing number of fish mortalities. There were slight decreases in chlorophyll-a concentrations over the study period, from tanks comprising of algae and, tanks comprising of algae and fish. Decreases in chlorophyll-a concentrations in tanks with fish were linked to consumption of algae by the fish. This was verified by the presence of algae in the stomach of fish euthanised during and at the end of the experiment. In tanks without fish, decreases in chlorophyll-a concentrations could be attributed to plankton die offs, as aquariums had algae that had settled at the bottom of the tanks. Although, consumption of algae by fish was observed in this study, no full stomachs were recorded over the experiment period. Tanks with 66% algal concentrations had low survival rates. Better survival was observed from treatments with 33% algal concentrations. Toxic secretions could have attributed to the high mortality rate or low survival rates during the study period in tanks with 66% and 100% algal concentrations. In addition to this, ammonia and nitrite values that were above tolerable limits for fish could have also contributed to the high mortality rates (>80%). The use of fish in the tanks as a means to assimilate the algae, seemed to have an opposite effect than the desired one. As the presence of fish in tanks increased ammonia levels, therefore, the effluent would need to be further treated before it can be re-used or released into the environment. Further experiments would need to be conducted to establish whether negative influences could be neutralised, when other species such as Scenedesmus spp. are used together with Chlorella spp. for the treatment of wastewater, in order to make the environment suitable for fish survival. / DSI-NRF SARChI Chair (Ecosystem Health), Flemish Interuniversity Council (VLIR-OUS)

Water and energy are very necessary resources for operating any chemical plant and contribute to total costs. Economic reasons notwithstanding, the processing industry has been incentivised to practise sustainable production in which the consumption of energy and water are more efficient, in response to stringent environmental legislation and public perception. Published literature exists for the independent investigation of water and energy optimisation in batch plants. It has been established for the individual problems that, a true optimum can only be obtained if batch production scheduling and water use or energy optimisation are performed simultaneously. However, the simultaneous optimisation of both water and energy within the same production scheduling framework has been largely ignored, due to the potential complexities of such a problem. Additionally, literature addressing the minimisation of water in fixed load problems has usually assumed that the water using operations (washing) are sequence independent. This is unlikely, as equipment units usually perform more than one task in multipurpose batch plants. Since the sequence of tasks in a unit influences both the occurrence and extent of washing in the unit, appropriate consideration of task sequences during production can contribute to wastewater minimisation. This thesis presents a mathematical formulation for the production scheduling of multipurpose batch plants, in which sequence dependent changeover costs are addressed. When compared to an existing formulation, the proposed formulation leads to a smaller sized model with fewer binary variables, continuous variables and constraints for a given case study, although the same objective was obtained. Expanding upon this, a mathematical formulation for simultaneous batch production scheduling and wastewater minimisation, for which the water requirement in a unit is dependent on tasks and their successors, is presented. The effectiveness of the formulation was demonstrated using two case studies. The results show improvements in profit and reduced wastewater generation when the sequence of tasks is taken into consideration. One case study saw water savings of 48% achieved with this method. The formulation was extended to incorporate process integration in the form of direct water reuse, which resulted in a further improvement in profit and water use. The third contribution in this thesis is a simultaneous method for the optimisation of energy and water embedded within a scheduling framework. In addition, opportunities for direct and indirect heat integration as well as direct and indirect water reuse were explored with the objective of improving the profitability of the plant while minimising water and external utility usage. The applicability of the method was demonstrated with three case studies. The developed formulation proved superior to a method that solved the same problem sequentially. / Thesis (PhD)--University of Pretoria, 2017. / Chemical Engineering / PhD / Unrestricted

La fermentation sombre et les piles à combustible microbiennes (MFC) sont deux technologies émergentes respectivement pour la conversion biologique de l'énergie chimique des composés organiques en hydrogène (H2) et en électricité. En raison des avantages cinétiques et thermodynamiques, la température élevée peut être la clé pour augmenter à la fois la production d'H2 de fermentation sombre et la production d'électricité dans les MFC. Par conséquent, cette thèse se concentre sur la manière dont la température influence la production biologique de H2 et d'électricité à partir d'eaux usées contenant du carbone organique. Deux inocula traités thermiquement (à boues activées fraîches et digérées) ont été comparés pour la production de H2 à partir de xylose à 37, 55 et 70 °C. A la fois à 37 et 55 °C, on obtient un meilleur rendement en H2 par les boues activées fraîches comparé aux boues digérées tandis qu'un très faible rendement en H2 est obtenu par les deux inocula à 70 °C. Ensuite, quatre prétraitements d'inoculum différents (chocs acides, alcalins, thermiques et de congélation) ont été évalués pour créer une efficace communauté productrice de H2 mésophile (37 °C) ou thermophile (55 °C). Les chocs acides et alcalins ont sélectionné des micro-organismes producteurs de H2, appartenant aux Clostridiaceae, au détriment des bactéries produisant du lactate, ce qui a donné respectivement le rendement en H2 le plus élevé à 37 et 55 °C. Bien que le choc thermique ait abouti à un faible rendement en H2 dans un seul lot, il a été montré que la production de H2 par les boues activées fraîches traitées thermiquement augmentait dans l'expérience avec quatre cycles consécutifs. Des boues activées fraîches et traitées thermiquement ont été sélectionnées comme inoculum pour la production continue de H2 à partir d'une eau usée synthétique contenant du xylose dans un réacteur à lit fluidisé (FBR) mésophile (37 °C) et thermophile (55-70 °C, augmenté par étapes). Un rendement en H2 plus élevé a été obtenu dans le FBR thermophile que dans le FBR mésophile. En outre, la production de H2 à 70 °C, qui a échoué dans l'étude précédente, a été couronnée de succès dans le FBR, avec un rendement stable de 1.2 mol H2 mol-1 xylose. La température de fonctionnement de 70 °C s'est également révélée optimale pour la production de H2 à partir d'eaux usées thermomécaniques (TMP) dans un incubateur à gradient de température, car la culture en batch à 70 ° C. Une approche de l'ARN a été utilisée pour étudier la structure et le rôle des communautés microbiennes attachées à l'anode, attachées à la membrane et planctoniques dans un MFC mésophile (37 °C) et thermophile (55 °C) alimenté au xylose. Une communauté anodine dominée par Geobacteraceae a soutenu la production d'électricité à 37 °C, alors que l'établissement de micro-organismes méthanogènes et H2 oxydants a entraîné une faible production d'électricité à 55 °C. Cependant, le développement d'une communauté exoélectrogène thermophile peut être favorisé en appliquant une stratégie de démarrage qui comprend l'imposition d'un potentiel négatif à l'anode et l'inhibition chimique des méthanogènes. Une communauté exoélectrogénique mésophile a également été montré pour produire de l'électricité à partir d'eaux usées de TMP dans un MFC à flux ascendant exploité à 37 °C. En conclusion, une production de H2 plus élevé et plus stable peut être obtenu dans une fermentation sombre thermophile plutôt que mésophile. La fermentation sombre à 70 °C est particulièrement appropriée pour le traitement des eaux usées de TMP car elle est libérée à haute température (50-80 °C) et pourrait être traitée sur site. Les eaux usées de TMP peuvent également être utilisées comme substrat pour la production d'électricité dans les MFC mésophiles. La production d'électricité dans les MFC thermophiles est faisable, mais l'enrichissement des micro-organismes exoélectrogènes thermophiles peut nécessiter une longue période de démarrage / Dark fermentation and microbial fuel cells (MFCs) are two emerging technologies for biological conversion of the chemical energy of organic compounds into hydrogen (H2) and electricity, respectively. Due to kinetic and thermodynamic advantages, high temperature can be the key for increasing both dark fermentative H2 production and electricity production in MFCs. Therefore, this thesis focuses on delineating how temperature influences biological production of H2 and electricity from organic carbon-containing wastewaters. Two heat-treated inocula (fresh and digested activated sludge) were compared, for H2 production from xylose at 37, 55 and 70 °C. At both 37 and 55 °C, a higher H2 yield was achieved by the fresh than digested activated sludge, whereas a very low H2 yield was obtained by both inocula at 70 °C. Then, four different inoculum pretreatments (acidic, alkaline, heat and freezing shocks) were evaluated for creating an efficient mesophilic (37 °C) or thermophilic (55 °C) H2 producing community. Acidic and alkaline shocks selected known H2 producing microorganisms belonging to Clostridiaceae at the expenses of lactate producing bacteria, resulting in the highest H2 yield at 37 and 55 °C, respectively. Although a heat shock resulted in a low H2 yield in a single batch, H2 production by the heat-treated fresh activated sludge was shown to increase in the experiment with four consecutive batch cycles.Heat-treated fresh activated sludge was selected as inoculum for continuous H2 production from a xylose-containing synthetic wastewater in a mesophilic (37 °C) and a thermophilic (55-70 °C, increased stepwise) fluidized bed reactor (FBR). A higher H2 yield was obtained in the thermophilic than in the mesophilic FBR. Furthermore, H2 production at 70 °C, which failed in the earlier batch study, was successful in the FBR, with a stable yield of 1.2 mol H2 mol-1 xyloseadded. Operation temperature of 70 °C was also found optimal for H2 production from thermomechanical pulping (TMP) wastewater in a temperature gradient incubator assay.A RNA approach was used to study the structure and role of the anode-attached, membrane-attached and planktonic microbial communities in a mesophilic (37 °C) and a thermophilic (55 °C) two-chamber, xylose-fed MFC. An anode attached community dominated by Geobacteraceae sustained electricity production at 37 °C, whereas the establishment of methanogenic and H2 oxidizing microorganisms resulted in a low electricity production at 55 °C. However, the development of a thermophilic exoelectrogenic community can be promoted by applying a start-up strategy which includes imposing a negative potential to the anode and chemical inhibition of methanogens. A mesophilic exoelectrogenic community was also shown to produce electricity from TMP wastewater in an upflow MFC operated at 37 °C. In conclusion, a higher and more stable H2 yield can be achieved in thermophilic rather than mesophilic dark fermentation. Dark fermentation at 70 °C is particularly suitable for treatment of TMP wastewater as it is released at high temperature (50-80 °C) and could be treated on site. TMP wastewater can be also used as substrate for electricity production in mesophilic MFCs. Electricity production in thermophilic MFCs is feasible, but enrichment of thermophilic exoelectrogenic microorganisms may require a long start-up period