With ever increasing regulation of the quality of drinking water and wastewater treatment, there is a need to develop methods to remove nitrogenous compounds from water. These processes are mediated by a variety of micro-organisms that can oxidise ammonia to nitrate, and then reduced to gaseous nitrogen by another set of organisms. This two stage process involves the relatively slow oxidation of ammonia to nitrate followed a relatively fast reduction of nitrate to nitrogen. Nitrate reduction normally requires anaerobic environments and the addition of organic matter to provide reducing power (electrons) for nitrate reduction. In practical situations the nitrate reduction can be problematic in those precise quantities of organic matter to ensure that the process occurs while not leaving residual organic matter. The aim of this study was to investigate microbial denitrification using electrochemical sources to replace organic matter as a redactant. The work also involved developing a system that could be optimised for nitrate removal in applied situations such as water processing in fish farming or drinking water, where high nitrate levels represent a potential health problem. Consequently, the study examined a range of developments for the removal of nitrate from water based on the development of electrochemical biotransformation systems for nitrate removal. This also offers considerable scope for the potential application of these systems in broader bio-nanotechnology based processes (particularly in bioremediation). The first stage of the study was to investigate the complex interactions between medium parameters and their effects on the bacterial growth rates. The results proved that acetate is a good carbon source for bacterial growth, and therefore it was used as an organic substrate for the biological process. High nitrate removal rate of almost 87% was successfully achieved by using a microbial fuel cell (MFC) enriched with soil inocula with the cathodes cells fed with nitrate and the anode fed with acetate. The maximum power density obtained was 1.26 mW/m2 at a current density of 10.23 mA/m2. The effects of acetate, nitrate and external resistance on current generation and denitrification activity were investigated, and the results demonstrated that nitrate removal was greatly dependent on the magnitude of current production within the MFC. Increase of acetate (anode) and nitrate (cathode) concentrations improved the process, while increasing external resistance reduced the activity. Furthermore, for a clear understanding of the nitrate reduction process, the analysis of the associated bacteria was performed through biochemical tests and examination of morphological characteristics. A diversity of nitrate reducing bacteria was observed; however a few were able to deliver complete denitrification. Pure cultures in MFC were examined and the voltage output achieved was about 36% of that obtained by mixed cultures. The nitrate removal gained was 56.2%, and this is almost 31% lower than that obtained by the mixed bacterial experiment. In an attempt to improve the MFC, modifications to the electrochemical properties of the electrode were investigated through the use of a cyclic voltammetry using carbon nanomaterials to coat the graphite felts electrodes. Among all the nanomaterials used in this study, graphitised carbon nanofibres (GCNFs) was selected for further investigation as it offered the best electrochemical performance and was thought to provide the largest active surface area. The performance of the MFC system coupled with the GCNFs modified electrodes was evaluated and significant improvements were observed. The highest voltage output achieved was about 41 mV with over 95% nitrate removal. The work is discussed in the context of improved MFC performance, potential analytic applications and further innovations using a bio-nanotechnology approach to analyse cell-electrode interactions.

An activated unsaturated sand filter (AUSF) is one of only a few of the filtration technologies utilized to treat waters and wastewaters that use unsaturated filter media. AUSF employs sand coated with potassium permanganate and operates with an open chamber allowing free air flow into the column of sand. The AUSF also benefits from operation without the need for a sedimentation unit. Previous studies have demonstrated the efficient removal of iron and manganese using an AUSF, however, to date there are still very limited studies available that use AUSF technology for the removal of metals from waters and wastewaters. Thus, there is an urgent need and opportunity to exploit this technology further. This research was conducted in order to develop and study the characteristics and subsequent operational performance of a novel AUSF media. The study focuses on the removal of copper, manganese, zinc and nickel from a synthetic wastewater and extends current knowledge to a passive aeration process rather than the active aeration used in the previous study by Lee et. al. (2004). The characterisation involved the use of sieving, Brunauer- Fmmett-Teller (BET) analysis, water evaporation studies and scanning electron microscopy (SEM) for structural analysis such as particle size, surface area, porosity and topography. Energy dispersive X-ray analysis (EDX), acid/alkali resistance, isoelectric point determination and acid digestion analysis were used to determine the chemical constituency, chemical stability, electrical charge properties and the binding efficiency of the media. Finally, tracer studies were employed to determine the flow characteristics through the particle media. The manganese coated sand was proven effective for the removal of copper in both agitated tank batch studies and continuous column studies. The batch studies showed that the equilibrium sorption of copper followed a Langmuir isotherm and the sorption rate was best modelled using the pseudo-second-order kinetic model. This suggests that adsorption is taking place as a single homogeneous layer on the surface of the sand particle via the chemisorption method. The Weber-Morris and Bangham models were used to determine the rate-controlling mechanism and this was found to be predominantly intra-particle diffusion. This was confirmed for column studies using the Bohart-Adams model that demonstrated that liquid-film mass transfer was not significant. Several mechanisms of metal removal are proposed and these include precipitation, electrostatic attraction, adsorption, ion exchange and complex ion formation. The column studies demonstrated that dispersion was low under the operating conditions and plug flow performance could be inferred, thus justifying the use of the AUSF model employed. Copper was best removed when operating as an unsaturated particle bed and the removal capacity was increased by approximately 100% when compared to a saturated particle bed. Moreover, the pH increase that occurs on exposure of the process water to the unsaturated column further improves removal capacity. Thus, there is no requirement for an expensive pH adjustment as a pre-treatment process prior to this unit operation. In addition, the removal capacity of the AUSF was demonstrated to increase with lower metal concentrations, lower water flow rates, smaller sand particles, an increase in manganese to sand ratio and an increase in particle bed height. The AUSF performance in removing metals followed the order Cu > Mn > Zn > Ni for individual and mixed component solutions and Cu > Ni > Zn > Mn for a synthetic wastewater typical of the electroplating industries. In conclusion, the novel manganese coated AUSF developed is effective in the removal of metals from solution and offers the potential of a sustainable low cost treatment method for the purification of waters and wastewaters.

abstract: Contamination of drinking water supplies from oxo-anion pollutants necessitates treatment prior to potable use. This dissertation aims to inform and improve light delivery (emission spectra, radiant intensity, reactor configuration) in order to enhance the photocatalytic reduction of hexavalent chromium (Cr(VI)) and nitrate, two common oxo-anions in drinking water, and photocatalytic oxidation of two model organic pollutants (methylene blue, (MB) and para-chlorobenzoic acid (pCBA)). By varying the photon fluence dose, two metrics (contaminant quantum yield (Φ), and electrical energy per order (EEO)) were used to assess photocatalytic reactor performance. A detailed literature review and experimental results demonstrated how different irradiance sources with variable intensity and emission spectra synergistically enhanced contaminant removal by a coupled photolytic/photocatalytic reaction mechanism. Cr(VI) was photocatalytically reduced on TiO2 and formed Cr(OH)3(s) in a large-scale slurry reactor, but Cr(III) was then photolyzed and reformed Cr(VI). UV light also led to photo-aggregation of TiO2 which improved its recovery by the ceramic membrane within the reactor. For nitrate reduction, light source emission spectra and fluence dose delineate the preferred pathways as intermediates were reduced via wavelength-dependent mechanisms. HONO was identified as a key nitrate reduction intermediate, which was reduced photocatalytically (UV wavelengths) and/or readily photolyzed at 365nm, to yield nitrogen gases. Photocatalytic nitrate reduction efficiency was higher for discrete wavelength irradiation than polychromatic irradiation. Light delivery through aqueous media to the catalyst surface limits efficiency of slurry-based photocatalysts because absorption and scattering of light in nanomaterial slurries decreases effective photon transmittance and minimizes photolytic reactions. The use of optical fibers coupled to light emitting diodes (OF-LED) with immobilized catalyst demonstrated higher performance compared to slurry systems. OF-LED increased Φ for MB degradation by increasing direct photon delivery to the photocatalyst. Design of OF-LED reactors using bundled optical fibers demonstrated photocatalytic pCBA removal with high Φ and reduced EEO due to increased surface area and catalytic sites compared to single OF/LED couples. This work advances light delivery as well as the suspension and attachment of nanoparticles in photocatalytic water treatment for selective transformation of oxo-anions and organic compounds to innocuous species. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2017

Made available in DSpace on 2014-10-09T12:27:35Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:31Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:34:22Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:10:40Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Thesis (MTech (Engineering))--Cape Peninsula University of Technology, 2007 / The removal of the colour-eausing natural organic matter (NOM) from natural brown water (NSW) to be used for drinking purposes is of paramount importance. One of the methods available to remove NOM from NSW is the use of pressure-driven membrane separation systems. One of the limitations in efficiently applying membrane filtration in the treatment of NOM-eontaining water is membrane fouling that is caused by foulants, such as NOM, that accumulate on the membrane surface and in the membrane pores. Microfiltration (MF), as a membrane separation system, is susceptible to severe membrane fouling during membrane filtration of NSW. Fouling is characterized by a rapid decline in permeate flux and loss of productivity. Progress in developing more effective control and prevention of fouling is impeded by the absence of suitable fouling measurement and characterization techniques. An in situ method for measuring membrane fouling is necessary for detection of membrane fouling during MF of NSW at the eartiest stages so that the corrective actions can be taken before fouling is permanently adsorbed onto the membrane surface. In this study, an ultrasonic-based method was effectively used to detect and measure the growth of membrane fouling dUring MF of NSW, in situ. Fouling exp~riments results showed the formation of a new peak on the ultrasonic response echo signal due to the presence of a fouling layer on the surface of the membrane. The ultrasonic signals acquired during the in-situ detection of membrane fouling were analysed using wavelet transforms (WTs). Wavelet analysis was applied to differential signals to obtain additional information about fouling. Differential signals were calculated by subtracting the baseline measurement signals from the test signals. The presence of the fouling layer on membranes was verified by atomic force microscopy (AFM) and scanning electron microscopy (SEM) analyses of the fouled membranes.

abstract: Hexavalant chromium (Cr(VI)) poses an emerging concern in drinking water treatment with stricter regulations on the horizon. Photocatalytic reduction of Cr(VI) was investigated as an engineering scale option to remove hexavalent chromium from drinking or industrial waters via a UV/titanium dioxide (TiO2) process. Using an integrated UV lamp/ceramic membrane system to recirculate TiO2, both hexavalent and total chromium levels were reduced through photocatalytic processes without additional chemicals. Cr(VI) removal increased as a function of higher energy input and TiO2 dosage, achieving above 90% removal for a 1g/L dose of TiO2. Surface analysis of effluent TiO2 confirmed the presence of chromium species. / Dissertation/Thesis / M.S. Engineering 2013

Neste trabalho desenvolveu-se uma metodologia analítica para determinação do teor de trialometanos THMs em amostras de águas potáveis, utilizando a técnica de purga e armadilha acoplada à cromatografia a gás (GCPT). Os THMs são subprodutos da cloração da água que devem possuir um limite máximo de 100 μg.L-1 segundo a legislação brasileira, estes compostos são suspeitos carcinogênicos humanos com base em estudos em animais de laboratório. A técnica de purga e armadilha extrai eficientemente estes compostos da água e a separação no cromatógrafo a gás ocorre utilizando coluna de leve polaridade e detector por captura de elétrons. Este detector é seletivo e o mais sensível para estes compostos halogenados. A metodologia desenvolvida foi validada nos itens de: linearidade, seletividade, exatidão, precisão, limite de quantificação, limite de detecção e robustez. O limite de detecção para os THMs foi menor do que 0,5 μg.L-1. A exatidão e precisão foram adequadas para ensaios de compostos traços. As amostras de água potável foram coletadas na cidade de Suzano-SP, que pertence à região do Alto do Tietê, nesta região nas margens do rio a vegetação é predominante. Entre todos os THMs, o composto encontrado na água potável em maiores concentrações foi o clorofórmio onde os resultados quantitativos, utilizando esta metodologia apresentaram teores entre 15,9 à 111,0 μg.L-1 em águas potáveis. / This work shows an analytical methodology developed and optimized to determine trihalomethanes level THMs, in drinking water samples, using purge and trap coupled to gas chromatography (GC-PT). THMs are byproducts water chlorination, these compounds must have a maximum of 100 μg.L-1 under Brazilian law, due these compounds be suspected human carcinogens base on studies in laboratory animals. The technique of purge and trap efficiently extracts these compounds from water, and the gas chromatograph separates the THMs. The GC uses a light polarity column and electron capture detector. This detector is selective and more sensitive in the detection of these compounds. The methodology was validated in terms of: linearity, selectivity, accuracy, precision, quantification limit, detection limit and robustness. The detection limit was less than 0,5 μg.L-1. The accuracy and precision were adequate for testing the trace compounds. The drinking water samples were collected in the city of Suzano-SP, which belongs to Alto do Tietê, in this region lay Tietê river with predominant vegetation. The THMs compound found in drinking water at higher concentrations was chloroform where the spread of values found between 15,9 to 111,0 μg.L-1 in drinking water.

Made available in DSpace on 2014-10-09T12:27:35Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:31Z (GMT). No. of bitstreams: 0 / Neste trabalho desenvolveu-se uma metodologia analítica para determinação do teor de trialometanos THMs em amostras de águas potáveis, utilizando a técnica de purga e armadilha acoplada à cromatografia a gás (GCPT). Os THMs são subprodutos da cloração da água que devem possuir um limite máximo de 100 μg.L-1 segundo a legislação brasileira, estes compostos são suspeitos carcinogênicos humanos com base em estudos em animais de laboratório. A técnica de purga e armadilha extrai eficientemente estes compostos da água e a separação no cromatógrafo a gás ocorre utilizando coluna de leve polaridade e detector por captura de elétrons. Este detector é seletivo e o mais sensível para estes compostos halogenados. A metodologia desenvolvida foi validada nos itens de: linearidade, seletividade, exatidão, precisão, limite de quantificação, limite de detecção e robustez. O limite de detecção para os THMs foi menor do que 0,5 μg.L-1. A exatidão e precisão foram adequadas para ensaios de compostos traços. As amostras de água potável foram coletadas na cidade de Suzano-SP, que pertence à região do Alto do Tietê, nesta região nas margens do rio a vegetação é predominante. Entre todos os THMs, o composto encontrado na água potável em maiores concentrações foi o clorofórmio onde os resultados quantitativos, utilizando esta metodologia apresentaram teores entre 15,9 à 111,0 μg.L-1 em águas potáveis. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:34:22Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:10:40Z (GMT). No. of bitstreams: 0 / O Brasil possui a sétima maior reserva geológica de urânio do mundo, com aproximadamente 310 mil toneladas. A Província Uranífera de Lagoa Real, na região de Caetité e Lagoa Real, situado no centro sul da Bahia, é considerada a mais importante província monominerálica do Brasil. A população urbana que vive no distrito uranífero nas cidades de Caetité, Lagoa Real e Livramento de Nossa Senhora usa água potável oriunda do abastecimento público. Na área rural, caracterizada por freqüentes secas, os moradores recebem água de poços escavados e perfurados como também, de pequenas barragens e reservatórios abastecidos pelas chuvas. Este trabalho determinou os níveis de radioatividade alfa e beta total e as concentrações de urânio em diversos tipos de água consumidas pela população urbana e rural da Província Uranífera de Lagoa Real. As atividades α e β total foram determinadas com detector proporcional de fluxo gasoso e baixa radiação de fundo. As concentrações de urânio foram determinadas com o Espectrômetro de Massa com Fonte de Plasma Indutivo (ICP-MS). Os resultados obtidos foram comparados com as recomendações recentes de 2011 da Organização Mundial da Saúde, a portaria nº 2914 de 12/12/2011 do Ministério da Saúde e as resoluções do CONAMA. Os níveis de radiação natural variaram de 0,0041 ± 0,0004 Bq.L-1 a 0,80 ± 0,04 Bq.L-1 para a atividade alfa total e de 0,045 ± 0,003 a 3,0 ± 0,2 Bq.L-1 para a atividade beta total. Tendo como parâmetro a OMS e o MS, apenas duas amostras de água subterrânea, uma localizada na cidade de Lagoa Real e outra na cidade de Caetité apresentaram concentrações alfa total acima do valor de 0,5 Bq.L-1 descrito em suas recomendações, 0,80 ± 0,04 Bq.L-1 e 0,57 ± 0,03 Bq.L-1respectivamente. Para beta total, três amostras apresentaram níveis de radioatividade acima do limite de 1 Bq.L-1 recomendado pela Organização Mundial de Saúde e estabelecido pelo Ministério da Saúde; 3,0 ± 0,2 Bq.L-1; 1,63 ± 0,13 Bq.L-1 e 1,19 ± 0,07 Bq.L-1 todos situados no município de Lagoa Real. Duas amostras de água subterrânea no município de Caetité apresentaram concentrações de urânio acima do valor de 15 μg.L-1 determinado pelo CONAMA, 20,3 ± 0,3 μg.L-1 e 17,1± 0,3 μg.L-1. Em Lagoa Real, uma amostra apresentou níveis de urânio seis vezes superior ao limite estabelecido pelo Conselho Nacional de Meio Ambiente, 89,5 ± 1,5 μg.L-1. A Organização Mundial da Saúde em 2004 estabeleceu em suas recomendações o limite de 15 μg.L-1 como a concentração máxima de urânio na água potável. Em 2011 a OMS aumentou este limite para 30 μg.L-1. Levando-se em consideração as atuais recomendações da OMS, apenas a concentração de uma amostra de água apresentou níveis de urânio acima do recomendado, 89,5 ± 1,5 μg.L-1 no município de Lagoa Real. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP