D.Phil. (Chemistry) / Elimination of toxic organic compounds from wastewater is currently one of the most important subjects in water-pollution control. Among the many organic pollutants are dyes and emerging pollutants such as natural organic matter (NOM). Dyes such as Eosin Yellow (EY), an anionic xanthene fluorescent dye, can originate from many sources such as textile industrial processes, paper pulp industries and agricultural processes. Most dyes are problematic because they are resistant to conventional chemical or biological water-treatment methods and therefore persist in the environment. NOM consists of a highly variable mixture of products found in water and soils. NOM is formed as a result of the decomposition of plant and animal material and is a precursor to the formation of disinfection by-products (DBP) during water disinfection. These organic compounds cause undesirable colour, taste and odour in water. NOM affects the capacity of other treatment processes to effectively remove organic micro-pollutants or inorganic species that may be present in the water. Its removal also uses up chemicals and energy and so it is expensive to treat. Titanium dioxide (TiO2) has emerged as one of the most fascinating materials in the modern era due to its semiconducting and catalytic properties. TiO2 is a large band-gap semiconductor that exists mainly in the anatase (band gap 3.2 eV) and rutile (band gap 3.0 eV) phases. Its response to UV light has led to increased interest in its application in the photocatalysis research field. It has been investigated extensively for its super hydrophilicity and use in environmental remediation and solar fuel production. In spite of extensive efforts to apply TiO2 for environmental remediation, photocatalytic activity in the visible region has remained quite low hence the ultimate goal of this research was to fabricate highly photoactive catalysts composed of non-metal, platinum-group metal (PGM) co-doped TiO2 and carbon nanotubes (CNTs) and to apply them for water purification using solar radiation...

Ph.D. / This study explored the possible application of a relatively new electrode called exfoliated graphite electrode (EG electrode) in the electroanalysis of organic and inorganic water pollutants. This study also explored the applicability of this electrode in the removal of heavy metal pollutants in water. The EG material was successfully prepared by intercalating bisulphate ions into graphite flakes (>300 μm) followed by thermal shock at 800°C to obtain an exfoliated graphite. After compressing the EG at high pressure, the obtained circular sheets were used to fabricate electrodes. The electrochemical profiles of EG electrode and glassy carbon electrodes (GCE) were recorded and compared using cyclic voltammetryand square wave voltammetry in the presence of various supporting electrolytes and [Fe(CN)6]3-/4-, [Ru(NH3)6]2+/3+, ferrocene redox probes. In the supporting electrolytes (KCl, H2SO4, NaOH, tetrabutylammoniumtetraflouroborate, phosphate buffers), the potential windows of EG were found, in some cases, to be about 300 mV larger than that of GCE. The diffusion coefficients (cm2s-1) of the redox probes were calculated to be 3.638 x 10-6, 1.213 x 10-6 and 4.411 x 10-6 for [Fe(CN)6]3-/4-, [Ru(NH3)6]2+/3+ and ferrocene, respectively. These values are comparable to those obtained from GCE. Furthermore, EG was modified with various nanomaterials such as poly (propylene imine) dendrimer (PPI), gold nanoparticles, silver nanoparticles, dendrimer–gold nanoparticles composite, cobalt oxide and bismuth. The morphologies of the modified electrodes were studied using scanning electron microscopy and their electrochemical reactivities in the three redox probes were investigated. The current and the reversibility of redox probes were enhanced in the presence of modifiers in different degrees with dendrimer and gold nanoparticles having a favourable edge. The electrochemical determination of o-nitrophenol by square wave voltammetry using a nanocomposite of generation 2 poly(propyleneimine) dendrimer and gold nanoparticles modified GCEand EG electrode were compared. A characteristic reduction peak between -600 mV and -700 mV for o-nitrophenol was observed with enhanced current on both GCE and EG modified electrodes.

D.Phil. (Chemistry) / This thesis describes the improvement of sorption capacity and efficiency of synthetic and biological adsorbents towards selected pollutants by introducing functional groups on the sorbents. Functionalization was achieved by chemically modifying the binding sites of the studied adsorbents. The sorbent materials considered were chemical resins (Amberlite XAD 1180) and biomass (maize tassels and seaweed). The adsorbents were modified with ethylenediamine in order to improve their capacity for extraction of heavy metals, namely lead, copper and cadmium from water. For the removal of phenols from water, maize tassels was modified with polydiallyldimethylammonium chloride (polyDADMAC). The main focus of the proposed study was to formulate cheap and sustainable ways of purifying contaminated water by exploiting the pollutants’ affinity towards the adsorbents. Parameters such as contact time, sorbent quantities, analyte concentrations, desorption solution (for stripping adsorbed metals for sorbent reuse) and pH were optimized. Different isotherms were applied on the experimental data to establish sorption mechanisms and energies involved during the sorption process. The Langmuir isotherm was used to test for monolayer sorption while the Freundlich model tested multilayer adsorption on heterogeneous surfaces...

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[pt] As bifenilas policloradas (PCBs) foram durante muitos anos usadas, principalmente, como fluidos refrigerantes e lubrificantes, em transformadores, capacitores e outros equipamentos elétricos. Os éteres difenílicos polibromados (PBDEs) ainda são amplamente utilizados como retardadores de chamas. Ambos são considerados poluentes orgânicos de extrema toxicidade e reportados como potentes interferentes endócrinos. Existem trabalhos anteriores que já detectaram PCBs na baía de Guanabara, porém, a pesquisa sobre PBDEs é pioneira. Foi desenvolvida e validada uma metodologia para extração, simultânea dos PCBs e PBDEs. Todas as amostras foram coletadas, extraídas, limpas e analisadas por GC-MS. Os PCBs foram os poluentes predominantes; entre eles o PCB-153 (bifenila-2, 2’, 4, 4’, 5, 5’-hexaclorada) provou ser o poluente mais disseminado, apresentando teor máximo de 261 ng.g-1 de peso seco no fígado de tainha. A ocorrência dos PBDEs foi significativamente menor; o PBDE-47 (éter difenílico- 2, 2’, 4, 4’-tetrabromado) foi o mais freqüente, apresentando um teor máximo de 46 ng.g-1 de peso seco no músculo de corvina. Comparando-se com outros ecossistemas, as concentrações de PCBs são maiores e as de PBDEs menores. / [en] Polychlorinated biphenyls (PCBs) have been used mainly as coolants and lubricants in transformers, capacitors, and other electrical equipments. Polybrominated diphenyl ethers (PBDEs) are still widely used as additive flame retardants. Both are among the most toxic environmental pollutants and reported as powerful endocrine disruptor. In Guanabara Bay previous studies have already detected PCBs, but the PBDE investigation is pioneer. A procedure for extracting simultaneously PCBs and PBDEs was developed and validated. Samples were collected, extracted, cleaned and analyzed by GC-MS. PCBs were the predominant pollutants, among them PCB-153 (2, 2’, 4, 4’, 5, 5’- hexachlorobiphenyl) proved to be the most disseminated one, with the highest content of 261 ng.g-1 dry weight (dw) in fish liver. PBDE occurrences were significantly lower, being the PBDE-47 (2, 2’, 4, 4’-tetrabromodiphenyl ether the most frequent, with the highest content of 46 ng.g-1 dry weight (dw) in fish tissue. In comparison to other ecosystems PCBs showed higher contents and PBDEs the lower ones.

This work presents the syntheses, photophysical and photochemical characterization of arylthio zinc phthalocyanines and their gold nanoparticle conjugates. Spectroscopic and microscopic studies confirmed the formation of the phthalocyanine-gold nanoparticle conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines. The studies showed that the presence of gold nanoparticles significantly lowered fluorescence quantum yields and lifetimes. However, this interaction did not restrict the formation of excited singlet and triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and therefore enhanced photocatalytic activity compared to the phthalocyanines. The zinc phthalocyanines and their gold nanoparticle conjugates were successfully incorporated into electrospun polymer fibers. Spectral characteristics of the functionalized electrospun fibers indicated that the phthalocyanines and phthalocyanine-gold nanoparticle conjugates were bound and their integrity was maintained within the polymeric fiber matrices. The photophysical and photochemical properties of the complexes were equally maintained within the electrospun fibers. The functionalized fibers were applied for the photoconversion of 4-chlorophenol and Orange G as model organic pollutants. / Microsoft� Word 2010 / Adobe Acrobat 9.53 Paper Capture Plug-in

La croissance démographique mondiale induit une pression accrue sur les ressources en eau potable. Une des solutions pour répondre à cette problématique environnementale est de réutiliser les eaux en sortie de station d’épuration (STEP). Cependant, la présence de microorganismes pathogènes et de micropolluants bio-récalcitrants et potentiellement toxiques ne permet pas une réutilisation directe des effluents urbains. Les procédés membranaires peuvent alors être envisagés afin d’éliminer efficacement ces polluants à l’état de trace. Cependant, la mise en œuvre des procédés membranaires implique la production de retentâts concentrés en micropolluants dont le traitement n’est, à ce jour, pas envisagé. Cette thèse propose alors d’étudier l’ozonation pour le traitement de retentâts de nanofiltration (NF) dans le cadre de la réutilisation des eaux usées, l’ozone étant un puissant oxydant et précurseur de radicaux hydroxyles. Pour cela, quatre micropolluants pharmaceutiques ont été sélectionnés comme molécules cibles. Par la suite, l’étude de la NF a mis en évidence qu’elle peut constituer une alternative viable au standard industriel qu’est l’osmose inverse en assurant des rétentions élevées pour des coûts opératoires moindres. L’ozonation s’avère efficace comme prétraitement des concentrâts en éliminant totalement les polluants les plus réactifs à l’ozone moléculaire. Toutefois, ce procédé reste limité quant à l’abattement des polluants réfractaire à l’ozone du fait de l’inhibition de la voie radicalaire par la forte teneur en matière organique des retentâts. Finalement, bien que cette association de procédés soit prometteuse, un traitement supplémentaire en aval de l’ozonation serait nécessaire afin de permettre la réutilisation des retentâts traités et aboutir à l’avènement d’une filière épuratoire à zéro rejet liquide / Global population growth induces increased threat on drinking water resources. One way to address this environmental issue is to reuse water from wastewater treatment plant (WWTP). However, the presence of pathogenic microorganisms and potentially toxic organic micropollutants does not allow a direct reuse of urban effluents. Membrane processes such RO or NF can be considered to effectively eliminate these pollutants. However, the integration of membrane processes involves the production of concentrated retentates which require to be disposed. To date, no treatment is set up to manage safely this pollution. This thesis project focuses on the application of ozonation for the treatment of NF retentates in the framework of the wastewater reuse. Ozonation is a powerful oxidation process able to react and degrade a wide range of organic pollutants. Four pharmaceutical micropollutants frequently detected in wastewater, were selected as target molecules. This study highlighted that NF can represent a viable alternative to the commonly used reverse osmosis process ensuring high retention at much lower operating costs. Ozonation appear to be effective to degrade the most reactive pollutants toward molecular ozone. However, this method is limited for the reduction of refractory ozone pollutants due to the inhibition of the radical chain by the high content of organic matter in the retentates. Finally, the ozonation processe appear to be a promising NF retentate treatment and further processing downstream of ozonation should allow reuse of treated retentates and lead to the emergence of a zero liquid discharge treatment scheme.