Les sites actifs de l’époxydation des alcènes dans les catalyseurs au titane supporté sur silice sont des ions Ti(IV) isolés. La stratégie d’isolation de site adoptée ici consiste à greffer l’isopropoxyde de titane par réaction avec les groupements silanol de surface dont la densité est diminuée par « capping » chimique remplaçant le traitement thermique usuel, très énergivore. La technique du pochoir moléculaire à motifs périodiques (PMP) a été appliquée pour forcer l’isolation de site. Dans les silices poreuses mesostructurées par un tensio-actif, c’est ce dernier, partiellement extrait, qui génère l’effet PMP lors du capping. Son élimination à l’étape suivante libère des îlots de groupements silanol sur lesquels sont greffés les ions Ti(IV). Une étude spectroscopique quantitative menée en parallèle par FT-IR et par RMN du solide du 29Si démontre que le pochoir organique inverse formé de groupement organosilyls greffés est conservé à toutes les étapes de synthèse. La spectroscopie UV en corrélation avec l’activité catalytique en époxydation du cyclohexene montent que ces surfaces originales favorisent un nombre beaucoup plus grand de sites mononucléaires isolés que les surfaces de silice non modifiées. La démonstration est faite avec une fonction de capping dipodale, 1-2-ethanebis(dimethylsilyl) (EBDMS), beaucoup plus stable que le monopodal classique, trimethylsilyl (TMS). Par ailleurs, le pochoir organique inverse issu du TMS ou de EBDMS voit sa stabilité augmentée par traitement thermique tout en préservant son effet dispersant pour le titane. Pour ce faire, un suivi quantitatif de la décomposition des organosilanes greffés a été réalisé par RMN du solide du 29Si. Finalement, une description affinée et quantitative du mode de greffage du titane a été réalisée par simulation des spectres UV sur une série de catalyseurs supposant 5 types d’espèces comprenant les sites isolés et les clusters, les derniers se différenciant par leur gamme de taille. / The active sites for epoxydation of alkenes in silica supported titanium catalysts are isolated Ti(IV) ions. The strategy for site isolation consists here to graft titanium isopropoxyde by reaction with surface silanol groups, the density of which is decreased by chemical capping instead of the energy consuming thermal treatment. The molecular stencil patterning technique (MSP) is applied to enforce site isolation. In mesostructured porous silicas, the partly extracted templating surfactant plays the role of a MSP mask during capping. Then, the elimination of the remaining surfactant liberates silanol islands for the grafting of Ti(IV) ions. Quantitative FT-IR and 29Si MAS-NMR studies reveal that the inverse organic stencil made of grafted organosilyls groups is maintained at each synthesis steps. Diffuse reflectance UV spectroscopy in correlation with the catalytic activity in epoxidation of cyclohexene show that these original surfaces favor the formation of a much larger number of isolated mononuclear sites than the unmodified silica surfaces. The demonstration is obtained using a dipodal organosilyl function, 1-2-ethanebis (dimethylsilyl) (EBDMS) that is much more stable than the classic and monopodal, trimethylsilyl (TMS). Besides, it is shown that the inverse organic stencil (from EBDMS or TMS) is stabilized further by thermal treatment while its dispersive effect on titanium can be preserved. The proof relies on a quantitative 29Si solid State NMR study. Finally, a refined description of the grafting mode of titanium was realized by simulation of the UV spectra of a large series of catalysts assuming only 5 different types of species including isolated species and clusters differentiated by the range of sizes.

Submitted by Jean Medeiros (jeanletras@uepb.edu.br) on 2016-04-13T13:00:25Z No. of bitstreams: 1 PDF - Rayanne Sales de Araújo Batista.pdf: 2799391 bytes, checksum: bfd7e21254a6a5383f8798d74f80923d (MD5) / Approved for entry into archive by Secta BC (secta.csu.bc@uepb.edu.br) on 2016-06-13T20:27:28Z (GMT) No. of bitstreams: 1 PDF - Rayanne Sales de Araújo Batista.pdf: 2799391 bytes, checksum: bfd7e21254a6a5383f8798d74f80923d (MD5) / Made available in DSpace on 2016-06-13T20:28:54Z (GMT). No. of bitstreams: 1 PDF - Rayanne Sales de Araújo Batista.pdf: 2799391 bytes, checksum: bfd7e21254a6a5383f8798d74f80923d (MD5) Previous issue date: 2015-03-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Retinoic acid (RA), widely used in dermatological and cosmetic products, has low stability in the presence of air and light, with sensitivity to heat and oxidation, so it is particularly important to implement the quality control of its finished products performing tests indicators of stability. Therefore, the objective was to develop an analytical method to evaluate the thermal stability of an RA cream formulation through the correlation of analytical techniques, high performance liquid chromatography with ultraviolet detection efficiency (HPLC-UV), differential scanning calorimetry (DSC) and vibrational absorption spectroscopy in the infrared Fourier transform spectroscopy (FTIR). Previously been established chromatographic conditions for development of the analytical method using HPLC-UV system, which was subjected to analytical tests specified in RE ANVISA Nº 899/2003 for validation. For evaluation of the thermal stability the cream samples were subjected to thermal stress in an oven at temperatures of 60, 70 and 80 °C and subsequently analyzed by HPLC-UV over the period of 0, 24, 48 and 72 h. DSC analyzes and FTIR spectra were carried out from the binary mixture (BM) of the RA and excipients of the cream formulation to investigate possible physical and/or chemical interactions. According to the data obtained it was possible to develop an analytical method by validated HPLC-UV, and based thereon, for analyzing and quantifying the RA content cream formulation, it has been found that from 70 ° C caused a decrease in the content of RA, and 0-order kinetics; and 80 ° C, followed a kinetic order 2 by setting up a reaction of bimolecular type. The analytical techniques DSC and FTIR showed the absence of chemical and physical interaction in most MB among the components of the formulation, except only for the carrier sodium metabisulfite. Thus, we can infer that it has a well-defined thermal behavior and compatibility of its components. / O ácido retinoico (AR), largamente utilizado em produtos dermatológicos e cosméticos, apresenta baixa estabilidade na presença de ar e luz, com sensibilidade ao calor e à oxidação, assim, é particularmente importante implementar o controle de qualidade de seus produtos acabados realizando ensaios indicadores de estabilidade. Logo, objetivou-se desenvolver um método analítico para avaliar a estabilidade térmica de uma formulação creme de AR através da correlação de técnicas analíticas, cromatografia líquida de alta eficiência com detecção ultravioleta (CLAE-UV), calorimetria exploratória diferencial (DSC) e espectroscopia vibracional de absorção na região do infravermelho com transformada de Fourier (FTIR). Previamente foram estabelecidas as condições cromatográficas para desenvolvimento do método analítico utilizando um sistema de CLAE-UV, o qual foi submetido aos testes analíticos especificados na RE ANVISA nº 899/2003 para validação do mesmo. Para avaliação da estabilidade térmica, as amostras do creme foram submetidas a estresse térmico em estufa nas temperaturas de 60, 70 e 80 º C, e posteriormente analisadas por CLAE-UV no período de 0, 24, 48 e 72 h. As análises de DSC e dos espectros de FTIR foram realizadas a partir das misturas binárias (MB) do AR e excipientes da formulação creme a fim de investigar possíveis interações físicas e/ou químicas. De acordo com os dados obtidos foi possível desenvolver um método analítico por CLAE-UV validado, e com base no mesmo, para análise e quantificação do teor de AR em formulação creme, constatou-se que a partir de 70 ° C ocorreu redução no teor de AR, e cinética de ordem 0; a 80 ° C, obedeceu uma cinética de ordem 2, configurando uma reação do tipo bimolecular. As técnicas analíticas DSC e FTIR mostraram a ausência de interação física e química na maioria das MB entre os componentes da formulação, com exceção apenas para o excipiente metabissulfito de sódio. Desta forma, podemos inferir que a mesma apresenta um comportamento térmico bem definido e compatibilidade entre seus componentes.

A radiação ultravioleta pode tanto ser um benefício, como um malefício para o olho humano. Os benefícios são quando é utilizada em procedimentos oftalmológicos para a correção da visão, como nas cirurgias foto-refrativas - UVC - 193 nm; ou para, entre outros tratamentos, impedir a progressão de patologias, como é o caso do crosslinking do colágeno corneano, para ceratocones em estágios inicias que utiliza UVA - 370 nm. Os malefícios são os já amplamente conhecidos pela comunidade científica e populacional, sobre a incidência excessiva de radiação UV nos olhos, causando danos severos ao olho humano. Entretanto, a córnea tem uma proteção natural contra os raios UVA e UVB. Neste trabalho, estudou-se os dois procedimentos oftalmológicos citados a fim de investigar possíveis danos ao olho humano, como a perda da proteção natural da córnea pós cirurgia foto-refrativa, que retira lamelas da córnea; e a quantidade de radiação que adentra o olho humano, durante o crosslinking do colágeno corneano, que utiliza Riboflavina como sintetizador e bloqueador da radiação UVA. Um sistema portátil foi desenvolvido para avaliação da proteção UV e seus danos para o primeiro caso. O protótipo consiste de um sistema de duplo feixe e analisa a transmitância do tecido corneano na faixa de 300-400 nm, e apresenta um fator de correlação r2>0,98. As medidas com remoção de tecido indicaram a importância das camadas da córnea, e a remoção do estroma apresentou uma perda significativa da proteção natural UV, com aumento de 8,2-10,1 pontos percentuais. Já para o crosslinking, que utiliza a combinação riboflavina e UVA, com irradiância de 3 mw/\'CM POT.2\' por 30 minutos foi feito o monitoramento da transmitância UVA durante o tratamento. Foi realizado o protocolo do procedimento atual, ou seja, uma gota de Riboflavina 0,1%, 400mOsm, foi instilada na córnea desepitelizada, a cada 5 minutos (total de 12 gotas). A irradiação UV (365 ± 5 nm, 3 mW/\'CM POT.2\') foi realizada após 30 min de instalação por uma adicional de mais 30 min. A transmitância média da córnea desepitelizada sem Riboflavina foi de 61,6%; após a 1ª instilação de Riboflavina a transmitância foi de 44,9%; após a 6ª gota 22,4%; após a 7ª gota (início da irradiação), 19,5%; após a 8ª gota, 17,3%; após a 9ª, 15,8%; após a 10ª; 14,5%; após a 11ª; 13,5%; e após a 12ª instilação, 12,6%. A transmitância média em termos de energia durante os 30 min de irradiação apresentou uma variação de 0,590 até 0,380 mW/\'CM POT.2\', valores além do limite atualmente aceito para endotélio de córneas de coelhos, que apresenta um nível de segurança citotóxico de 0,36 mW/\'CM POT.2\'. / Ultraviolet radiation can either be a benefit as an harm to the human eye. The benefits are when used in ophthalmic procedures for vision correction, as in the photorefractive surgery - UVC - 193 nm; or to, among other treatments, preventing the progression of diseases, such as the corneal collagen crosslinking, for keratoconus in the early stages - that uses UVA - 370 nm. The harm effects are already widely known by the scientific community and general population, about excessive incidence of UV radiation in the eye, that can cause severe damage to the human eye. However, the cornea has a natural UVA and UVB protection. In this work, we studied the two ophthalmic procedures cited in order to investigate possible damage to the human eye, as the loss of cornea UV natural protection after photorefractive surgery, which removes corneal lamella; and the amount of radiation that penetrates the human eye during the corneal collagen crosslinking, that uses Riboflavin as a synthesizer and UVA radiation blocking. A portable system was developed to evaluate the UV protection and the UV damage for the first case. The prototype consists of a double beam system that analyzes the corneal tissue transmittance in the 300-400 nm range, and presents a correlation factor r2>0.98. Measurements with tissue removal showed the importance of each corneal layer, specially the stroma removal that shows a significant loss of natural UV protection, with an increase of 8.2 to 10.1 percentage points. As for the crosslinking, using riboflavin and UVA irradiance combination, with 3 mw/\'CM POT.2\' for 30 minutes, was performed a monitoring of UVA transmittance during treatment. Current procedure protocol was performed, i.e., one drop of riboflavin 0.1%, 400mOsm, was applied on the naked cornea, every 5 minutes (total of 12 drops). The UV irradiation (365 ± 5 nm, 3 mW/\'CM POT.2\') was performed after 30 min of instillation for an additional 30 min. The average transmittance of the desepithelized cornea without Riboflavin is 61.6%; after the 1st drop of Riboflavin, transmittance is 44.9%; after 6th drop 22.4%; after 7th drop (irradiation starts), 19.5%; after 8th drop; 17.3%; after 9th drop, 15.8%; after 10h drop, 14.5%; after 11th drop, 13.6%; after 12th drop, 12.6%. The average transmittance in terms of energy during the 30 min irradiation procedure fluctuated from 0.590 to 0.380 mW/\'CM POT.2\', beyond the currently accepted rabbit corneal endothelium safety limit for cytotoxic level of 0.360 mW/\'CM POT.2\'.

O gênero Passifloraceae possui mais de 400 espécies, sendo uma delas Passiflora incarnata L., detentora de diversas aplicações , principalmente no âmbito farmacêutico como uma planta capaz de atuar no sistema nervoso central para o tratamento de distúrbios da ansiedade. As substâncias mais abundantes existentes nas folhas dessa espécie pertencem à classe dos flavonóides, principalmente os C-glicosilados, que podem estar diretamente relacionados à atividade farmacológica da planta. Assim, o objetivo do presente trabalho , foi avaliar a influência (ou não ) de fatores externos na concentração dos flavonóides, em um cultivo experimental realizado na região de Botucatu .Os flavonóides analisados foram a luteolina, homoorientina, vitexina, isovitexina e orientina , com sua quantificação realizada por HPLC-UV/DAD e expressos em flavonóides totais calculados com base no padrão de rutina, através do método descrito por Pereira (2002). Realizou-se a correlação quimiométrica destes resultados pela análise multivariada , através de PCA (análise de componentes principais ) e HCA (análise hierárquica de agrupamentos), para avaliar se ocorreu a influência direta de determinados elementos do solo (pH, macronutrientes e micronutrientes) e do ambiente (temperatura e umidade) no teor de flavonóides encontrados nas folhas. Concluiu-se que as amostras se apresentaram de forma heterogênea no decorrer do cultivo (quanto à classificação ) , porém que alguns minerais presentes no solo (por exemplo, ferro, boro e cobre ), possuem relação inversa à concentração dos flavonóides totais encontrados nas folhas de P. incarnata. / Passifloraceae genus has more than 400 species and one of them is Passiflora incarnata L., which holds different application, mainly on the pharmaceutical scope as an herb capable to act on the central nervous system to the treatment of anxiety disturbs. The more copious compounds that exist on the leaves of this specie belong to flavonoid category, mainly C-glicosilates that could have direct relationship with pharmacologic properties of the herb. So, the objective of this task was to evaluate concentration in experimental growth made on Botucatu?s place. Analysed flavonoids were luteolin, homoorientin, vitexin, isovitexin and orientin, which were quantified by HPLC-UV/DAD and expressed as total flavonoids as rutin, through described method from Pereira (2002). Results were analysed through chemometric´s correlation, with PCA (principal components analysis) and HCA (hierarchic clusters analysis), to evaluate if some soil members (pH, macro and micronutrients) and ambient members (temperature and humidity) affected or not the flavonoids content on the leaves. It was conclude that all samples appeared heterogeneous in the course of growth, but some members present on the soil (as example iron, cupper and bore), have opposite relationship with total flavonoids content on the leaves of P. incarnata.

As projeções mostram que o Brasil poderá consumir aproximadamente 50 bilhões de litros de biodiesel num futuro próximo. Frente a este cenário, surge a preocupação com tratamento de tamanha quantidade de efluente que pode ser gerado na produção do biodiesel. Os Processos Oxidativos Avançados (POAs) têm sido estudados como uma alternativa promissora para o tratamento de uma série de efluentes. O presente trabalho tem como objetivo tratar águas ácidas de lavagem geradas na produção de biodiesel com a fotocatálise heterogênea (TiO2/UV). Para tanto, elaborou-se um planejamento experimental, com a finalidade de se determinar os efeitos das variáveis independentes pH, temperatura e teor de TiO2. Em seguida, ajustou-se um modelo linear aos dados obtidos (R2 = 0,985). A condição ótima de tratamento foi: pH = 3,3; 20°C; e 0,1 g TiO2 L-1. Foram observadas a remoção de DQO, DBO e COD, a redução do espectro de absorção no ultravioleta, a biodegradabilidade e ecotoxicidade. Tanto o processo fotocatalítico quanto a fotólise foram eficazes na degradação dos compostos presentes no efluente. Alcançou-se aproximadamente 80, 78 e 61% de remoção de DQO, DBO e COD, respectivamente, após 240 min de irradiação. O efluente fotocatalisado apresentou uma melhora marginal na biodegradabilidade. A fotólise não é indicada para o tratamento desse efluente por ter gerado ecotoxicidade a sementes de Lactuca sativa. / Projections show that Brazil may consume approximately 50 billion liters of biodiesel in the near future. In face of this scenario, the treatment of the huge amount of wastewaters that can be generated in the production of biodiesel is a worry. Advanced Oxidation Processes (AOPs) have been studied as a promising alternative for treating several wastewaters. The present work is aimed at treating biodiesel washing acid waters with heterogeneous photocatalysis (TiO2/UV). For that purpose, an experimental design was performed to assess the effects of the independent variables pH, temperature, and TiO2 content. Next, a linear model was fit to the obtained data (R2 = 0,985). The optimum treatment condition was: pH = 3,3; 20°C, and 0.1 g TiO2 L-1. The removal of COD, BOD, and DOC, the reduction of the ultraviolet absorption spectrum, biodegradability and ecotoxicity. Both photocatalysis and photolysis were effective in degrading the compounds present in the wastewater. Removals of approximately 80, 78, and 61% of COD, BOD, and DOC, respectively, were achieved after 240 min of irradiation. The photocatalyzed wastewater showed a marginal improvement in biodegradability. Photolysis is not indicated for treating this wastewater as ecotoxicity towards seeds of Lactuca sativa was generated.

O presente trabalho teve como ênfase avaliar a atividade herbicida de aleloquímicos em extratos aquosos de sementes da Canavalia ensiformis (feijão-de-porco) através de ensaios de alelopatia e determinação de compostos fenólicos com atividade alelopática, utilizando a técnica de cromatografia líquida de alta eficiência (HPLC). Com este objetivo realizaram-se bioensaios de germinação, medida do crescimento da radícula e produção de biomassa em placas de Petri, usando como substrato solo e papel e como planta alvo as ervas daninhas corda-de-viola (Ipomoea sp.) e trapoeraba (Commelinna sp). Para os ensaios de alelopatia foram preparados extratos aquosos de sementes de Canavalia ensiformis em diferentes concentrações. Os bioensaios mostraram que os aleloquímicos presentes no extrato de feijão-de-porco quando aplicado em solo, têm um efeito fitotóxico menor do que aqueles bioensaios realizados em papel. Os resultados apontam que a espécie estudada apresenta potencial alelopático. Dentre os metabólitos secundários responsáveis pela atividade alelopática observada nos extratos desta espécie, estão os compostos fenólicos: ácido clorogênico, ácido ferúlico, ácido p-anísico e genisteína. As concentrações determinadas para os compostos fenólicos foram de 13,78 mg L-1 para o ácido clorogênico, 3,75 mg L-1 para o ácido ferúlico, 35,34 mg L-1 para o ácido p-anísico e 7,83 mg L-1 para a genisteína. Esses compostos apresentaram-se como fortes inibidores de germinação. Esta investigação mostra que na presença de solo os aleloquímicos presentes nesta leguminosa possivelmente diminuem sua atividade fitotóxica. / The objective of the present work was to study the herbicide activity of the allelochemicals in aqueous extracts from Canavalia ensiformis seeds through the allelopathy assays and phenolic compounds determination with allelopathi c activity, by High Performance Liquid Chromatography (HPLC). With this goal, germination bioassays, radicle length and biomass production in Petri plates were done, using paper and soil as substrate and the weeds species Ipomoea grandifolia and Commelinna benghalensis as target plants. For the allelopathy assays aqueous extracts from Canavalia ensiformis seeds were prepared in different concentrations. The bioassays showed that the allelochemicals present in the Canavalia ensiformis seeds, has a less phytotoxic effect compared to the bioassays done in paper. The results show that the studied specie has allelopathi c potential. Among the secondary metabolites responsibles for that allelopathic activity in this specie, are founded the phenolic compounds: chlorogenic acid, ferulic acid, p-anisic acid and genistein. The concentrations for the phenoli c compounds were determined: 13,78 mg L-1 for chlorogenic acid, 3,75 mg L-1 for ferulic acid, 35,34 mg L-1 for p-anisic acid and 7,83 mg L-1 for genistein. These compounds present themselves as strong germination inhibitors. This study shows that the allelochemicals present in the Canavalia ensiformis seeds have a lesser phytotoxic activity in soil.

Persistent organic pollutants (POPs) are organic compounds of anthropogenic origin that have been linked to the development of cancer, neurobehavioural impairment, and immune system biochemical alterations. These chemicals have various industrial applications as well as acting as pesticides. Dioxins and furans are some of these compounds that are unintentionally produced in combustion and industrial processes. By definition these compounds have 4 common qualities: they are highly toxic, they are resistant to environmental degradation, they are introduced into the air and water where they travel long distances, and they accumulate in fatty tissues. Photochemical degradation is a method that has been extensively researched in the last few decades. In the aqueous phase it has already been shown to be able to degrade a number of refractory organics, such as dioxins and furans. The ultimate products of this process tend to be carbon dioxide, water, and mineral anions. Air phase work has been also gaining attention in recent decades as a possible alternative to incineration methods in air pollution control. The advantages of photochemical degradation processes are that they can be initiated at low temperatures, are relatively low cost compared to incineration processes, environmentally benign, and have the potential for quick and complete degradation of organic compounds. The main aim of the research is to investigate the photochemical degradation potential of PCDD/ PCDFs in gaseous air streams as a potential air pollution control technology. In order to do this, the photodegradation reaction kinetics were determined for chlorobenzene as a suitable surrogate for PCDD/PCDFs. Three different photodegradation schemes were employed: direct photolysis, UV/O3, and UV/H2O2. In addition, ozonolysis reaction rates were also determined to evaluate the effects of on the overall photodegradation rates for the UV/O3 process. Factors such as humidity levels and temperature were investigated to determine their effects on degradation rates. Temperature and humidity were not greatly influential on the degradation rates of direct photolysis. The degradation rate of chlorobenzene at a temperature of 100°C and high humidity was noticeably reduced, but unchanged at the 10% RH and 60% RH levels for all temperatures. Ozonolysis of chlorobenzene was negligible at 30°C for all humidity levels. Ozonolysis reactions at the 60°C and 100°C levels were higher than direct photolysis rates and in the 100°C case exceeded the UV/O3 degradation rates. Ozone coupled with UV experiments proved to be the most destructive at the low temperature of 30°C and molar ratio of 10:1 ozone to chlorobenzene. There was a clear and positive relationship between the amount of ozone present in the reactor and the degradation rate. At lower ozone to chlorobenzene molar ratios the degradation rates were not much higher than those for direct photolysis of ozone. The 5:1 molar ratio saw a significant increase in degradation rates over the photolysis rates. The fastest degradation rate was achieved for the 10:1 molar ratio and high humidity, which was over 10 times the rate of direct photolysis. In addition, humidity had a noticeably significant positive effect in these reactions. The effect of temperature on the UV/ozone reaction scheme was determined for the 5:1 ozone to chlorobenzene ratio. Temperature had an interesting effect on the degradation rates at higher temperatures. As the reactor temperature increased, the degradation rates from ozonolysis and UV/O3 began to converge at 60°C, ultimately leading to the ozonolysis reaction being faster than the UV/O3. Exploratory experiments for the H2O2 scheme were performed. H2O2 had a positive influence on the degradation rate of chlorobenzene and was about 26% higher than the direct photolysis rates. However for similar conditions, the UV/O3 process had higher degradation rates as was expected from the difference in absorption values between ozone and hydrogen peroxide.

No description available.

The effects of UV pretreatment on alkaline bleaching (EOP) wastewater from a kraft pulp and paper mill were investigated prior to anaerobic digestion (AD) in an upflow anaerobic sludge blanket (UASB) reactor. The aim was to enhance the methane production, increase the reduction of total organic carbon (TOC) and determine the best UV exposure time. The exposure time of 2.6 minutes partially degraded the organic material in the EOP wastewater since it generated higher biogas and methane production than the reference period, while it also increased the reductions of solved chemical oxygen demand (CODsol) and TOCsol. The exposure time of 16 minutes, on the other hand, did not show any significant improvement regarding increased biogas and methane production nor did it increase the reduction of CODsol. However, it did increase the reduction of TOCsol, but not to the same extent as the exposure time of 2.6 minutes. The presence of unwanted microbial growth in the system during the experiment might have affected the effectiveness of the UV pretreatment more during the exposure time of 16 minutes as the amount of growth was more substantial during this period of time. Furthermore, no optimal exposure time could be determined due to lack of time.

Persistent organic pollutants (POPs) are organic compounds of anthropogenic origin that have been linked to the development of cancer, neurobehavioural impairment, and immune system biochemical alterations. These chemicals have various industrial applications as well as acting as pesticides. Dioxins and furans are some of these compounds that are unintentionally produced in combustion and industrial processes. By definition these compounds have 4 common qualities: they are highly toxic, they are resistant to environmental degradation, they are introduced into the air and water where they travel long distances, and they accumulate in fatty tissues. Photochemical degradation is a method that has been extensively researched in the last few decades. In the aqueous phase it has already been shown to be able to degrade a number of refractory organics, such as dioxins and furans. The ultimate products of this process tend to be carbon dioxide, water, and mineral anions. Air phase work has been also gaining attention in recent decades as a possible alternative to incineration methods in air pollution control. The advantages of photochemical degradation processes are that they can be initiated at low temperatures, are relatively low cost compared to incineration processes, environmentally benign, and have the potential for quick and complete degradation of organic compounds. The main aim of the research is to investigate the photochemical degradation potential of PCDD/ PCDFs in gaseous air streams as a potential air pollution control technology. In order to do this, the photodegradation reaction kinetics were determined for chlorobenzene as a suitable surrogate for PCDD/PCDFs. Three different photodegradation schemes were employed: direct photolysis, UV/O3, and UV/H2O2. In addition, ozonolysis reaction rates were also determined to evaluate the effects of on the overall photodegradation rates for the UV/O3 process. Factors such as humidity levels and temperature were investigated to determine their effects on degradation rates. Temperature and humidity were not greatly influential on the degradation rates of direct photolysis. The degradation rate of chlorobenzene at a temperature of 100°C and high humidity was noticeably reduced, but unchanged at the 10% RH and 60% RH levels for all temperatures. Ozonolysis of chlorobenzene was negligible at 30°C for all humidity levels. Ozonolysis reactions at the 60°C and 100°C levels were higher than direct photolysis rates and in the 100°C case exceeded the UV/O3 degradation rates. Ozone coupled with UV experiments proved to be the most destructive at the low temperature of 30°C and molar ratio of 10:1 ozone to chlorobenzene. There was a clear and positive relationship between the amount of ozone present in the reactor and the degradation rate. At lower ozone to chlorobenzene molar ratios the degradation rates were not much higher than those for direct photolysis of ozone. The 5:1 molar ratio saw a significant increase in degradation rates over the photolysis rates. The fastest degradation rate was achieved for the 10:1 molar ratio and high humidity, which was over 10 times the rate of direct photolysis. In addition, humidity had a noticeably significant positive effect in these reactions. The effect of temperature on the UV/ozone reaction scheme was determined for the 5:1 ozone to chlorobenzene ratio. Temperature had an interesting effect on the degradation rates at higher temperatures. As the reactor temperature increased, the degradation rates from ozonolysis and UV/O3 began to converge at 60°C, ultimately leading to the ozonolysis reaction being faster than the UV/O3. Exploratory experiments for the H2O2 scheme were performed. H2O2 had a positive influence on the degradation rate of chlorobenzene and was about 26% higher than the direct photolysis rates. However for similar conditions, the UV/O3 process had higher degradation rates as was expected from the difference in absorption values between ozone and hydrogen peroxide.