Orientador: Sarah Arana / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-23T12:36:44Z (GMT). No. of bitstreams: 1 Peterlini_MarianaFrem_M.pdf: 4643636 bytes, checksum: cd0d6e62df40edebf5ce8326f7c80cd0 (MD5) Previous issue date: 2012 / Resumo: A agricultura intensiva no Brasil tem aumentado o risco de contaminação dos recursos hídricos e dos organismos aquáticos por agroquímicos. Esse é o caso da atrazina, detectada em alta frequência em rios e córregos da região. Assim, neste trabalho, o pacu (Piaractus mesopotamicus) foi escolhido como bioindicador por sua importância econômica e ecológica em Bacias do Pantanal. As brânquias e o tegumento foram aqui avaliados como biomarcadores da toxicidade induzida por atrazina, uma vez que estes órgãos se encontram em contato direto com o ambiente aquático. Para avaliar a sensibilidade de alevinos de pacu e determinar a Concentração Letal Média (CL50) à atrazina foram conduzidos experimentos, em duplicata, em sistema estático por 96 horas, com as seguintes concentrações: 0,0; 13,2; 17,6; 22,0; 26,4; 30,8; 35,2; 39,6 mgL-1. A CL50 obtida para a atrazina foi de 28,58 mgL-1 (96h). Foram realizadas análises anatomopatológica, histopatológica qualitativa e semi-quantitativa para brânquias e análises anatomopatológica e histopatológica qualitativa para o epitélio tegumentar. Amostras de brânquia e de pele dorsal e ventral foram fixadas em Bouin e incluídas em parafina. Para o grupo controle não foi registrada qualquer alteração com os métodos empregados. Os alevinos expostos à atrazina apresentaram alterações comportamentais como: escurecimento da pele, boquejamento intenso e distúrbios motores, além disso, nesses aquários houve constante presença de muco na água; e, alterações anatomopatológicas, como: hiperemia na pele, dilatação da região ventral, presença de líquido no estômago e ascite sanguinolenta. Nas brânquias dos grupos tratados foram observadas as seguintes alterações morfológicas: edema e afastamento na região interlamelar, hipertrofia e hiperplasia na região interlamelar, destacamento do epitélio respiratório, hipertrofia de células do epitélio respiratório, congestão, telangiectasia e fusão de lamelas secundárias. Na pele dorsal e ventral dos grupos tratados não se observou alteração histopatológica. As alterações motoras observadas são provavelmente decorrentes do efeito neurotóxico da atrazina. As análises branquiais confirmam o comprometimento respiratório e de osmoregulação nesse órgão, sendo que a análise semi-quantitativa indicou a hipertrofia de células do epitélio respiratório como a lesão mais severa. Finalmente, as brânquias mostraram-se biomarcadores adequados na avaliação dos efeitos tóxicos da atrazina em pacu e o valor da CL50 sugere que a atrazina é levemente tóxica para o pacu, porém pelos demais resultados observados, se infere que só analisar a mortalidade não é o suficiente para determinar o dano causado por agrotóxicos em peixes, assim, recomenda-se o emprego de vários biomarcadores, como por exemplo, análise de vários outros órgãos. Os resultados obtidos reforçam a importância de estudos desta natureza, para embasar medidas ambientais preventivas e reguladoras quanto ao uso desse herbicida / Abstract: The intensive agriculture in Brazil has caused growing increase of pollution risks of hydric resources and the aquatic organisms by agrochemicals. This is the case of atrazine, detected in high frequency in the rivers and streams. Therefore, in this research, the pacu (Piaractus mesopotamicus) was chosen by bioindicator because of its great economic and ecological importance to the water ecosystem of the Pantanal region. The gills and skin were assessed here as biomarkers of induced toxicity by atrazine, considering that these organs are in direct contact with the aquatic environment. To evaluate the sensitivity of pacu fingerlings and determine the Median Lethal Concentration (LC50) by atrazine, experiments were conducted, performed in duplicate, in static system for 96 hours, with the following concentrations: 0.0; 13.2; 17.6; 22.0; 26.4; 30.8; 35.2; 39.6 mgL-1. The LC50 for pacu was 28.58 mgL-1 (96h). Anatomopathological, qualitative histopathological and semiquantitative histopathological analyses were performed for the gills, and anatomopathological and qualitative histopathological analysis were performed for the skin epithelium. Gills and dorsal and ventral skin samples were fixed in Bouin and processed for the inclusion in paraffin. The control group did not register any other alterations with the methods used. The fingerlings exposed to atrazine presented behavioral changes, such as: darkening of the skin, an increase in the frequency of gasping and motor disturbances. Furthermore, these aquariums presented the constant presence of mucus in the water; and, anatomopathological alterations, such as: skin hyperemia, dilation of the ventral region, the presence of liquid in the stomach and bloody ascites. In the gills of treated groups were found the following morphological alterations: edema and spacing in the interlamellar region, hypertrophy and hyperplasia in the interlamellar region, epithelial lifting, hypertrophy of respiratory epithelium cells, congestion, telangiectasis and fusion of the secondary lamellae. For dorsal and ventral skin of treated groups no histological alterations were observed. The motor alterations observed are probably due to the neurotoxic effects of atrazine. The gills analysis confirm respiratory and osmoregulatory compromise in this organ, noting that semi-quantitative analysis indicated the hypertrophy of respiratory epithelium cells as the most severe lesion. Finally, the gills showed adequate biomarkers in the assessment of toxic atrazine effects in pacu and the LC50 value suggests that atrazine is lightly toxic to pacu. However, by other results observed, it is concluded that analyzing the mortality index alone is not enough to determine the damages caused by agrotoxics in fishes, so the use of other biomarkers is recommended, like for instance, analysis some other organs. The results obtained reinforce the importance of research of this nature, in order to establish preventive and regulatory environmental measures regarding the use of this herbicide / Mestrado / Histologia / Mestra em Biologia Celular e Estrutural

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-03-20T17:33:01Z No. of bitstreams: 1 Tese - Renata Barbosa Alvim.pdf: 4406371 bytes, checksum: 35fad183d96f066fe9832adc22b3f739 (MD5) / Made available in DSpace on 2017-03-20T17:33:01Z (GMT). No. of bitstreams: 1 Tese - Renata Barbosa Alvim.pdf: 4406371 bytes, checksum: 35fad183d96f066fe9832adc22b3f739 (MD5) / Coordenação de Aperfeiçoamento de Pessoal Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica, Niterói, RJ / As atividades humanas estão provocando alterações substanciais no ciclo do nitrogênio (N) e fósforo (P), que resultam em aumento das concentrações e alteração na distribuição das formas desses elementos nos sistemas aquáticos. O presente estudo teve como objetivo avaliar os impactos provocados na distribuição das formas de N e P na bacia hidrográfica do rio Piabanha (Região Serrana do estado do Rio de Janeiro), em áreas com cobertura de vegetação natural, agrícola e urbana. Foram inseridos dois pontos fora do limite da bacia do rio Piabanha, no rio Paraibuna (afluente do rio Paraíba do Sul) e no rio Paraíba do Sul, à montante da foz dos rios Paraibuna e Piabanha. A bacia do Piabanha, possui área de drenagem de 2059 km2 e uma população estimada em 500.000 habitantes. Os rios Piabanha e Paquequer nascem em trechos preservados de mata Atlântica, e atravessam o perímetro urbano dos municípios de Petrópolis e Teresópolis, respectivamente. O rio Preto, seu maior afluente, está inserido em uma região com atividades agrícolas, o que aumenta a poluição das águas fluviais devido ao uso de fertilizantes. Foram coletadas amostras de águas fluviais em duas campanhas de amostragem (verão e inverno) em 2013. Foram efetuadas medidas in situ de pH, condutividade, temperatura e concentrações de oxigênio dissolvido e a determinação das formas dissolvidas e particuladas de N e P. As medidas de vazão foram efetuadas in situ e estimadas por cálculos em todos os pontos de amostragem. A sazonalidade foi mais marcante nas cabeceiras e nas áreas agrícolas, possivelmente em razão das chuvas, que arrastam os nutrientes que passam pela vegetação e pelas áreas cultivadas e chegam aos rios. Os maiores valores de condutividade e concentrações de N e P foram verificados nos pontos das áreas urbanas e os menores valores nos pontos localizados nas cabeceiras dos rios. As elevadas concentrações de NH4+ e PO43-, em relação às demais formas, logo a jusante dos maiores centros urbanos, são um forte indicativo da descarga de esgotos, além disso, é a principal causa da poluição das águas dos rios Piabanha e Paquequer. O aumento gradual da abundância relativa do nitrogênio particulado (NP) em relação ao N ao longo do curso do rio Piabanha a partir do setor mais poluído, sugere que este aumento esteja relacionado à hidrodinâmica fluvial, que favorece a aeração e, em decorrência disso, o crescimento aeróbio de biomassa heterotrófica e autotrófica (nitrificação), processos através dos quais, parte do NH4+ assimilado é convertido em biomassa, processo semelhante ao verificado em um sistema de tratamento de esgotos por lodos ativados, onde parte do N é removido da fase aquosa e incorporado ao lodo ativado. A carga de N no rio Paraíba do Sul, a jusante da confluência dos três rios, e próximo à sua foz sugerem que existem processos efetivos em causar perda líquida de N ou retenção ao longo do rio Paraíba do Sul, a principal hipótese seria a sedimentação de NP, especialmente em áreas de represamento de água localizadas entre estes dois pontos de estudo. No trecho final do rio Piabanha, os resultados mostraram a diminuição da carga de P, a principal hipótese é que o P pode estar adsorvido às formas inorgânicas e devido à maior densidade dessas formas, foi removido da água e depositado no sedimento de fundo. O lançamento de esgotos domésticos nas águas fluviais da bacia do rio Piabanha contribui com pelo menos 43% da carga de N lançada no rio Paraíba do Sul. A contribuição atmosférica seria de 31% e a atividade agrícola contribui com pelo menos 15% do N lançado no Paraíba do Sul. Restando um total de 11% de erro associado à incerteza na estimativa das 3 principais fontes de N aqui consideradas. Os valores estimados de fluxo de P para a população e a deposição atmosférica foram maiores que os fluxos encontrados na foz do rio Piabanha. Estima-se que mais de 44% do P que entra na bacia esteja sendo removido das águas superficiais e depositado no sedimento de fundo. / Human activities are causing substantial changes in the nitrogen cycle (N) and phosphorus (P), which results in increased concentrations and changes in the distribution of forms of these elements in aquatic systems. This study focused on evaluating the impacts done during the distribution of forms of N and P in the watershed of the Piabanha River (Mountain region of the state of Rio de Janeiro), in areas with natural vegetation cover, agricultural and urban. Two points outside the boundary of the basin of the Piabanha River basin were inserted in Paraibuna river (tributary of the River Paraiba do Sul) and the Paraíba do Sul River, upstream from the mouth of Paraibuna and Piabanha rivers. The basin Piabanha has a 2059 km2 drainage area and an estimated population of 500,000 inhabitants. The Piabanha and Paquequer rivers rise in the preserved Atlantic Forest stretches, and pass through the urban area of the cities of Petropolis and Teresopolis, respectively. The Preto River, its largest affluent, is inserted in a region with agricultural activities which increases the pollution of fluvial waters due to the use of fertilizers. Samples of fluvial waters were collected in two sampling campaigns (summer and winter) in 2013. In Situ measurements of pH were made as well as conductivity, temperature and dissolved oxygen concentrations and the determination of dissolved and particulate forms of N and P. The flow measurements were carried out in situ and estimated by calculations in all the sampling points. Seasonality was most outstanding in the headwaters and agricultural areas, possibly because of the rains, dragging the nutrients that pass through vegetation and the cultivated areas and reach the rivers. The highest conductivity and concentration values of N and P were found in sections of urban areas and the lowest values in the points located in the headwaters of rivers. High concentrations of NH4 + and PO4-3, in relation to other forms, just downstream of the largest urban centers, are a strong indicator of sewage discharge, moreover, is the leading cause of water pollution of rivers Piabanha and Paquequer. The gradual increase in the relative abundance of particulate nitrogen (PN) to N over the course of Piabanha river from the most polluted sector suggests that this increase is related to the hydrodynamic fluvial, which favors aeration and, as a result, aerobic growth of heterotrophic biomass and autotrophic (nitrification), the processes by which part of the NH4+ absorbed is converted into biomass similar to what was found in a sewage treatment system by activated sludge, in which part of the N is removed from the aqueous phase and incorporated into the activated sludge. The N load in the Paraiba do Sul river, downstream of the confluence of three rivers, and near its mouth suggest that there are effective processes in causing net loss of N or retention along the Paraiba do Sul river, the main hypothesis sedimentation of NP, especially in areas of dammed water located between these two study points. In the final stretch of river Piabanha, the results showed a decreasing load of P, the main assumption is that P can be adsorbed to inorganic forms and due to the greater density of these forms, it was removed from the water and deposited in the bottom sediments. The launch of domestic sewage in the fluvial waters of the basin of the Piabanha river contributes with at least 43% of N load thrown into the Paraiba do Sul River. The atmospheric contribution would be 31% and agriculture contributes with at least 15% of N released in Paraiba do Sul. Leaving a total of 11% of associated error to the uncertainty in the estimation of three main sources of N considered here. The estimated values of P flow to the population and atmospheric deposition were higher than the flows found in the mouth of the Piabanha river. It is estimated that more than 44% of P entering the bowl is being removed from the surface and deposited in the bottom sediment.

M.Sc. / A comparative study was undertaken in the Olifants River catchment, to determine the water quality at two dam sites, namely, Bronkhorstspruit Dam (control) and Loskop Dam (polluted) in the upper Olifants River system and two river point, namely, at Mamba and Balule in the Kruger National Park, in the lower Olifants River system. Data was obtained during the physical and chemical analysis of water and sediment samples, and during bioaccumulation studies using Atomic Absorption spectrometry, testing for aluminium, chromium, copper, iron, lead, manganese, nickel, strontium and zinc. These tests were conducted on the liver, skin, muscle and gills of Clarias gariepinus. The information collected from Mamba and Balule, was compared with a previous study carried out primarily in the Kruger National Park by Marx, (1996). The study undertaken by Marx (1996) was carried out during a drought period, which allowed for the comparison with results recorded after flooding during the present study. This current research project therefore allowed for the comparison between two different water sources, namely, that of dams and rivers, and under varying environmental conditions. The Aquatic Toxicity index (ATI) developed by Wepener et al. (1992) was employed to facilitate the comparison between the water physical and chemical parameters that were measured, at each sample site, with a single variable being calculated for each sample site per survey. The water quality (ATI values) at the two control sites namely, Bronkhorstspruit Dam and Balule deteriorated substantially after the floods. High water levels due to the floods had a dilution effect on the concentration of pollutants however, toxicants were washed in from upstream and due to surface runoff. The removal of the purifying reed beds upstream of Balule and at the inflow to Bronkhorstspruit Dam, resulted in the release of latent sludge containing metals and organic pollutants into the water column. The ATI value's obtained for the two control points were similar or even higher than those obtained for the two polluted sites namely at, Loskop Dam and Mamba for the autumn and winter sampling periods. During following surveys the water quality at all four sample sites improved, returning to pre flood values by the last survey in summer, namely reflecting similar values as those recorded by Marx (1996) at Balule, Mamba and Loskop Dam for the same period. Sediment concentrations recorded a similar trend to that for water at all four sample sites throughout the study. The bioaccumulation study indicated that the gill concentrations recorded were generally the highest, followed by the liver concentrations. From this one may deduce that gills were the dominant site for metal absorption by the fish, with the excretion of metals also taking place via this route. Liver concentrations are an indication of the activation of protective _mechanisms in the fish sampled, the high concentrations recorded indicate the high physiological response the fish have had to the various levels of exposure. The low concentrations recorded in the muscle indicates the effectiveness of the liver in the detoxification of the fish, indicating that only limited storage of the various metals tested for took place at this site. Skin concentrations were quite high, these concentrations represent the products of an excretory process, which takes place via the skin. The order of concentrations recorded during the present study, were similar to the orders recorded by Marx, (1996) and other authors, however, the order of the skin and muscle concentrations were often reversed. This may be due to the increased excretion of these metals via the skin, resulting from increased exposure to these metals after the floods. Thus the increased exposure

D.Phil. / South African water resource management policies as well as the country's water law have been under review over the past three to four years. The Water Law Principles, which were established as part of this review process, indicate a commitment to sustainable development of water resources and the protection of an ecological "Reserve". Such policy goals highlight the limitations of conventional water quality management strategies which rely on stressor monitoring and associated regulation of pollution. The concept of an assimilative capacity is central to the conventional water quality management approach. Weaknesses inherent in basing water management on the concept of assimilative capacity are discussed. Response monitoring is proposed as a way of addressing some of the weaknesses. In fact, the inadequate use of biological indicators and techniques in monitoring and evaluating the quality of resources has been identified as a major factor responsible for the continuing decline in the health of natural resource systems. With advances in environmental monitoring over the last decade, it has become clear that biological techniques and protocols need to become part of monitoring in order to allow effective assessment and protection of aquatic resources. One way of incorporating response measures into resource assessment is through the use of toxicological assays. As an example, a toxicological assessment of the environmental risk associated with an organic pesticide (fenthion) is presented. Acute and chronic assays were conducted with a spectrum of test organisms. These toxicological response results provided an ability to predict the ecosystem response that can be expected from certain concentrations of fenthion in the environment. Theoretically, it would be possible to design a risk assessment experiment for every new anthropogenic substance. However, in terms of cost and time, it would not be practically feasible to execute such experiments. To overcome this problem, a method has been developed to derive water quality criteria for toxic substances using existing toxicological data. This provides water resource managers with a readily available set of values to guide them in decision-making. It is demonstrated how available acute and chronic toxicity data can be synthesised into acute and chronic water quality criteria for the protection of aquatic life. As these criteria are intended to extend protection to ecosystems country-wide, they are very conservative by design. Although a set of numeric water quality criteria provides an important tool to water quality managers, the limitations associated with the use of these criteria must be recognised. x Limitations relate either to the design of toxicity experiments or to the use of a chemical-specific approach alone in water resource management. In order to overcome these limitations, three broad supporting technologies are proposed, namely whole effluent toxicity (WET) testing, sitespecific adjustment of water quality criteria, and in-stream biological assessments. Whole effluent testing aims at evaluating the toxic effects of an effluent on organisms. In doing so, acute and chronic toxicity testing (and thus biological responses) becomes part of effluent regulation. An effluent control programme that incorporates toxicity-based standards and compliance criteria is proposed. One of several approaches that can be used for deriving site-specific water quality criteria is the calculation of a water-effect ratio. It is demonstrated that the water-effect ratio method could result in significant adjustments to the national water quality criteria. Although more development and local testing would be required, such site-specific criteria could be in the interest of both ecosystem protection and economic development. In-stream biological assessments introduces a type of response monitoring which provides insight into the overall integrity of aquatic ecosystems. A comprehensive biomonitoring programme is designed. To adhere to the objectives of this programme, specifications have been developed for the selection of sampling sites, the selection of biological and habitat indicators, and the management of the resulting data. This programme is referred to as the River Health Programme (RHP). The ultimate aim of any monitoring programme is to provide useful data. Such data must contribute to effective decision-making. To ensure that the RHP becomes truly operational as a management information system, a step-wise procedure is proposed for linking the collected data with management actions. It is demonstrated how following of this systematic and iterative procedure would facilitate ongoing learning and improvement of the individual steps (e.g. data collection and assessment, goal setting, selection and implementation of management actions) as well as the overall procedure. As a final step, the dynamics that influence the transition of any new technology from scientific development to operational application are explored. The RHP is used as a case study and theoretical models from the field of the management of technology are used to provide valuable insights. Four key components of the RHP design are analysed, namely the (a) guiding team, (b) concepts, tools and methods, (c) infra-structural innovations and (d) communication. These key components evolved over three broad life stages of the programme, which are called the design, growth and anchoring stages.

D.Phil. (Zoology) / South Africa is a major gold-producing country with the 43 larger mines processing approximately 120 x 106 ton of milled and processed ore and about 30 x I06 ton of mined waste rock. Pollution of both surface and ground water, which can be attributed to the influences of gold-mining, are well known. Acid mine drainage, characterized by a low pH and high concentrations of dissolved metals, and seepage, from active and disused mine-tailings, are two of the main environmental problems associated with gold mining operations in South Africa. A growing concern for the environment and a stricter approach to water pollution by government agencies have made it necessary to investigate the type of effects which the gold mining industry is responsible for, and to develop action to reduce these impacts. The present study focused on procedures to access the effect of gold-mining effluent on the natural surface environment. The study is divided into three separate identities. The mine represented as Ccse study Mine One is considered to be a major contributor of salt loads to the natural stream on the property of the mine. This stream confluences with the Klip River outside the mined area. This mine has only one discharge point of underground mine service water, and is considered to be the main point source of pollution for the mine. As the mine makes use of an open water circuit, the quality and quantity of effluent have a direct effect on the downstream users. It appears that one of the main water quality problems of this open water circuit is the creation of surface water with a very low pH. Part of the problem is the geology of the area which consists of shales, which has a natural low buffering capacity. Because of the low pH the wetlands are not very effective. Metal concentration changes are possibly the direct result of the low pH of the both the water column and sediment. Improving the pH of the surface water can leads to reduced metal concentrations in the water, with possible increased concentrations in the sediment and wetland vegetation. Case Study Mine Two was conducted at a gold mine in the Far West Rand Mine region. The mine can be classified as having a closed water circuit, in that only excess water is discharged. The volume of water discharged is dependent on a number of factors, such as rainfall, wash-down service water and changing demands in sewage treatment systems. The advantage in this type of circuit is that water which has accidentally been spilled can be retained in one of the boundary dams, without the possibility of endangering the downstream users. From the assessment it appears that although the mining activities have influenced the water within the mining area this impact is only confirmed to certain areas. Biotic environmental conditions at certain sites resemble the conditions of the two control sites while other, notably those in contact with processing plants (e.g. metallurgical plant), are far more deteriorated. pH does not seem to be a problem at this specific mine. The main reasons are that the underlying geology of the mine is dolomitic in nature, while the sulphate concentration in the ore appears to be lower than those' found at the Witwatersrand mines. Case study Mine Three is situated in the Klerksdorp gold-mining region. The mine has a complex water circuit as a percentage of the service water is being reused or/and discharged via effluent streams into the Vaal River. Metal concentrations in the sediment core samples indicate a large variability between seasons, sites and depth. Sites in close proximity of slimes dams have high iron and manganese concentrations, whilst those in contact with effluent water from metallurgical plants have relatively high nickel, copper and in concentrations. This can be related to the type of processing material used in the gold-mining process.

M.Sc. / The contamination of water by toxic compounds is one of the most serious environmental problems today. These toxic compounds mostly originate from industrial effluents, agriculture runoff, natural sources (e.g. heavy metals in water from rocks and soil erosion) and human waste. The contamination, which is both “organic” and “inorganic” has an impact on the environment and human health. The demand for water and the pressure to re-use this valuable resource has increased the need for improved techniques and materials to remove pollutants from water. The Nanomaterials Science research group at the University of Johannesburg has focused on developing synthetic polymers that can be employed in water treatment and pollutant monitoring. Recently, cyclodextrins (CD) and carbon nanotubes (CNTs) have been included in polymers for this application. For example, CD-co-hexamethylene-/toluene-diisocyanate polyurethanes and CNT-modified equivalents have been developed and have been successfully applied in removing organic contaminants from water to very low levels.1 Calixarenes are synthetic analogues of cyclodextrins that can be exploited via chemical modification to express a range of properties. In the present study, calixarenes, thiacalixarenes and carbon nanotube-based polymeric materials incorporating these molecules have been synthesised, characterised and tested for removing both organic pollutants (such as p-nitrophenol) and inorganic pollutants (Cd2+, Pb2+) from water. Lead(II) and Cadmium(II) are a threat in South Africa because of their toxicity, and while p-nitrophenol is much less of a problem it represents a useful model organic pollutant. The absorption capacity of the polymers towards heavy metals and organic contaminants was tested by mixing the polymer with synthetic water containing known concentration of the contaminants at about 10 mg/L. Atomic absorption spectrometry (AAS) and ultraviolet-visible spectrometry (UV-vis) were used to determine the levels of heavy metals and organic contaminants, respectively. The target pollutants (Cd2+, 1 see KL Salipira MTech dissertation, University of Johannesburg 2008 Pb2+ and p-nitrophenol) were all successfully removed from water by the various polymers, however the degree of removal and loading capacities of the polymers differed. This information gives some insight into what functional components are needed for making successful adsorbents. It was observed, for example, that ptert- butylcalix[8]arene/hexamethylene diisocyanate (C8A/HMDI) had a higher adsorption capacity towards p-nitrophenol and Pb2+ than towards Cd2+, and also a higher capacity than the corresponding calix[4]arene polymers with smaller calixarene cavities.

[pt] Estudos prévios relacionam a ocorrência de episódios de mortandade de peixes em corpos hídricos como a Lagoa Rodrigo de Freitas (LRF) com a rápida disponibilização de espécies poluentes e nutrientes naturais na coluna d água especialmente durante altas precipitações de chuva, quando ocorre transbordo dos rios poluídos da bacia sobre a água da Lagoa, ocasionando uma demanda de oxigênio dissolvido maior do que o normal para depuração de tais espécies. Nesse contexto existe interesse em evitar episódios críticos de insuficiência de OD na água dos corpos hídricos que possam advir de tais eventos. Estudos realizados no presente trabalho tiveram como objetivo caracterizar as águas de rios da Sub-bacia hidrográfica da LRF através de DBO, COT, SST, Ptotal no canal a montante de deságue para a Lagoa em períodos de chuva e de tempo seco; e avaliar um possível tratamento que proporcione a depuração acelerada dos poluentes utilizando peróxido de hidrogênio, fornecendo oxigênio para as águas poluídas através do processo de decomposição do oxidante. Avaliaram-se diferentes dosagens de H2O2 em tempo reacional de 24h de acordo com limites de ecotoxicidade conhecidos. Testes realizados em amostras de rio coletadas em dias de baixa precipitação contendo concentrações de DBO de até 2,2 mg/L mostraram uma velocidade de decaimento de H2O2 inferior ao para amostras tanto coletadas também em dia de baixa precipitação porém com elevada DBO (24,0 mg/L), quanto para dia de alta precipitação (13,2 mm em 24 h) com relevante concentração de material orgânico. Observou-se uma dosagem suficiente de 15,0 mg/L para as amostras coletadas em baixa precipitação e alta DBO, e dosagem suficiente de 3,0 mg/L para amostras coletas em maior evento de precipitação (13,2 mm em 24 h), acima das quais, não ocorre mais aumento significativo da velocidade de decaimento da [H2O2] e também de velocidade de contribuição de OD para a água. Concluiu-se que a adição de H2O2 nas águas de rios durante eventos de poluição causados por chuvas intensas ou lançamento de esgoto pode contribuir para evitar episódios críticos de insuficiência de OD em rios poluídos por material orgânico e na pluma de poluentes que pode ser formada por transbordo dos rios para a LRF. / [en] Previous studies have associated the occurrence of episodes of death of fish in water bodies such as the Lagoa Rodrigo de Freitas (LRF) to to the rapid availability of pollutants and natural nutrients in the water column species especially during high rain precipitation events, which occur when the rivers overflow and pollute the water of the lagoon, causing a biochemical oxygen demand higher than usual for the rate of natural depuration of the contaminating species. In this context there is interest in avoiding critical episodes DO deficiency in the water bodies that may arise from such events. Studies conducted in the present work aimed at characterizing the rivers of sub-basin of LRF through BOD, TOC, TSS, Ptotal on the canal that overflows into the lagoon in periods of rain and dry weather; and evaluate a possible treatment offering the accelerated depuration of pollutants using hydrogen peroxide, providing oxygen to the polluted water through the self-decomposition process. The study evaluated the effect of different doses H2O2 in 24 hours of reaction time according to known ecotoxicity limits. In tests on samples collected from rivers in days of little rain containing BOD concentrations up to 2.2 mg / L, H2O2 showed a decay rate lower than those of other samples also collected on days of low precipitation, but with high BOD (24, 0 mg / L), and days of high rainfall (24 hours 13.2 mm), with a significant concentration of dissolved organic contaminants. A maximum sufficient dose of 15.0 mg / L was found for the low and high samples precipitation BOD, and a maximum sufficient dose of 3.0 mg / L for most of the samples collected during the precipitation event (13.2 mm 24 hours), above which there is no significant increase over the rate of decomposition of [H2O2], and the rate of generation of DO in the water. It was concluded that the addition of H2O2 into the waters of rivers during pollution events caused by heavy rains or sewage release can help to avoid critical episodes of DO deficiency in polluted rivers by organic matter and pollutant plume that can be formed by overflow of those rivers to the LRF lagoon.

La pollution des ressources en eau est un des défis importants auquel les Hommes doivent faire face. En particulier, de nouvelles solutions doivent émerger, puisque les techniques conventionnelles de traitement utilisées actuellement ne permettent pas une élimination efficace des divers polluants. Parmi les polluants émergents, les composés pharmaceutiques ont récemment été détectés dans différentes sources d'eau à travers le monde. Leurs effets indésirables sur l'environnement naturel et sur l'Homme ont déjà été reconnus mais doivent encore être éclaircis. De nombreux nouveaux procédés de traitement de l'eau apparaissent. En particulier, le procédé électro-Fenton a démontré sa capacité à éliminer les pharmaceutiques et autres contaminants persistants. Ce procédé est basé sur la génération in-situ d'une espèce oxydante très puissante, les radicaux hydroxyles (OH), qui permettent la dégradation non-sélective des polluants. Cependant, cela nécessite l'utilisation d'une quantité d'énergie importante, relativement coûteuse. Une solution viable est de coupler le procédé électro-Fenton avec un procédé biologique. En effet, l'utilisation de ce dernier est beaucoup plus économique, mais il possède une efficacité limitée envers les polluants persistants tels que les pharmaceutiques. Ainsi, le procédé hybride bio-électro-Fenton apparaît comme un bon compromis entre le coût et l'efficacité. Le but de cette thèse de doctorat a donc été d'optimiser le procédé électro-Fenton dans l'optique de le coupler avec un procédé biologique, afin d'éliminer les pharmaceutiques. Les principaux objectifs de cette étude reposent sur l'étude de l'influence des paramètres opératoires utilisés au cours du procédé électro-Fenton sur (a) la dégradation des pharmaceutiques ; (b) la minéralisation de la matière organique ; (c) l'évolution de la biodégradabilité; (d) la consommation énergétique. Cette thèse est composée de trois parties, au cours desquelles la complexité des solutions traitées a progressivement augmentée. Premièrement, une étude a été menée sur des solutions de produits pharmaceutiques seuls afin de mieux comprendre les mécanismes impliqués au cours de leur dégradation. La seconde partie porte sur l'étude expérimentale d'une solution synthétique composée d'un mélange de 13 pharmaceutiques. La dernière étape a consisté à mettre en place un procédé bio-électro-Fenton pour le traitement d'un effluent pharmaceutique réel. Cette démarche progressive a permis de mieux comprendre l'influence des paramètres opératoires utilisés au cours du procédé électro-Fenton. Les principaux résultats obtenus sont notamment l'optimisation de deux paramètres opératoires important : la concentration du catalyseur (Fe2+) et l'intensité du courant. L'influence de ces paramètres s'est révélée similaires au cours du traitement de tous les types de solution testée. Il a donc été possible de conclure que les valeurs optimales sont une concentration en Fe2+ de 0,2 mM et une intensité entre 100 et 500 mA. L'efficacité d'élimination des pharmaceutiques a été plus importante en utilisant des intensités plus faibles (100-300 mA). Cependant, la biodégradabilité de l'effluent, un paramètre important dans l'optique du post-traitement biologique, a été d'avantage augmentée en utilisant des intensités élevées (500-1000 mA). Par ailleurs, l'utilisation d'intensités élevées a aussi mené à augmenter la consommation énergétique, en particulier dans le cas de temps de traitement longs. Il apparaît donc évident qu'un compromis entre efficacité et consommation énergétique doit être trouvé pour chaque cas particulier et effluent à traiter. Pour conclure, les avancées de cette recherche sont principalement attribuées à la nouveauté de la combinaison bio-électro-Fenton. L'étude de l'influence des paramètres opératoires du procédé électro-Fenton a aussi permis d'améliorer la compréhension de cette nouvelle technique et contribue à son développement vers une application industrielle / Water pollution is one of the biggest challenges that humanity faces and combating it requires the development of treatment processes, as conventional methods used nowadays are no longer effective for the removal of various complex pollutants. Recently pharmaceuticals have been recognized to be contaminants of emerging environmental concern as their traces were detected in a spectrum of water bodies around the globe. The long term effects of their presence in a natural environment are not yet fully studied, but the potential outcomes can be detrimental to a sustainable future. Among the variety of currently rising treatment technologies, the electro-Fenton method, an electrochemical advanced oxidation process, has demonstrated an ability to eliminate pharmaceuticals as well as other types of persistent contaminants. This electrocatalytical process generates in situ strong oxidants species - hydroxyl radical (OH) - which non-selectively degrade organic pollutants. Due to the extensive cost in the application of electrical energy, its operation might be cost-prohibitive. A solution would be to combine it with biological processes which are more economically viable, but also less effective in the removal of pharmaceuticals. The combined process is expected to have a synergetic effect between cost and effectiveness. The goal of this PhD thesis is to optimize operating conditions of the electro-Fenton process for a feasible combination with a biological process as a means of treating pharmaceutical pollution. The main objectives addressed by this work are related to the influence of operating parameters of the electro-Fenton process on (a) removal of pharmaceuticals; (b) mineralization of organic matter; (c) enhancement of biodegradability; (d) energy consumption. The thesis has three distinct parts related to the type of treated aqueous solution. First, a mechanistic study was conducted on aqueous solutions of individual pharmaceuticals in order to understand general trends of their removal. Next, a series of experiments was carried out on a synthetic mixture of thirteen pharmaceuticals from different therapeutic classes. Lastly, laboratory bench-scale reactors of a combined bio-electro-Fenton process were operated for the treatment of real wastewater. The advance in the complexity of the treated solution allowed a comprehensive comparison and analysis of the influence of the operating parameters. The main results include the optimal values of two operating parameters: the catalyst (Fe2+) concentration and the applied current intensity for a given electro-Fenton setup. The effects of the operating parameters on the removal of pharmaceuticals and other organic matter were similar regardless of the treated solution. The optimal value for the Fe2+ concentration was concluded to be around 0.2 mM. The optimal current intensity was in the range 100-500 mA. The efficiency of the current in terms of the pharmaceuticals' removal was the highest with the lowest intensity (100-300 mA). At the same time the biodegradability, which was an important factor in the biological post-treatment process, improved with higher intensities of electric current (500-1000 mA). However, high current intensities resulted in an elevated energy consumption, particularly with a prolonged treatment time. A tradeoff would have to be consequently made between energy saving and the removal rates that should be found in any single case. The novelty of the research presented in this PhD thesis is firstly attributed to the novelty of the combination of electro-Fenton to a biological process. A detailed study of the influence of operating parameters of the electro-Fenton process on removal rates and biodegradability enhancement contributed not only to the general knowledge on the electro-Fenton process, but also to the advancement towards its upscaling and then further towards the industrial application of this technique

Diffuse water pollution in urban areas is growing due to polluted runoffs. Therefore, there is a need to treat this kind of pollution. Different structural treatment practices can be used for these purposes. However, little is known about their environmental, economic and social impacts. Therefore, the aim of this study has been to develop an integrated methodology for sustainability evaluation of structural treatment practices, considering environmental, economic and social aspects. Both environmental and economic evaluations have been carried out on a life cycle basis, using life cycle assessment and life cycle costing, respectively. For social evaluation, a number of social indicators, identified and developed in this research, have been used. The methodology has been applied to the case of the Magdalena river catchment in Mexico City. Three structural treatment practices have been analysed: bio-retention unit, infiltration trench and porous pavement. Based on the assumptions and the results from this work, the bio-retention unit appears to be environmentally the most sustainable option for treatment of diffuse water pollution. It is also the second-best option for social sustainability, slightly behind the porous pavement. However, if the costs of treatment are the priority, then the porous pavement would be the cheapest option. If all the sustainability aspects evaluated here are considered of equal importance, then the bio-retention unit is the most sustainable option. Therefore, trade-offs between the different sustainability aspects are important and should be considered carefully before any decisions are made on diffuse water pollution treatment. This also includes the trade-offs with the additional life cycle impacts generated by the treatment options compared to the impacts from the untreated runoff. The decisions can only be made by the appropriate stakeholders; however, some recommendations are given, based on the outcomes of this research.

Abstract available in file 07summary.pdf / Thesis (PhD (Microbiology))--University of Pretoria, 2007. / Microbiology and Plant Pathology / unrestricted