Residues of 2,4,6-trinitrotoluene (TNT) in soil and groundwater near former production and processing plants generate large environmental concerns. A cyclodextrin (CD) mediated Fenton remediation of TNT contaminated water and sand (soil analogy) is presented. Kinetic studies were performed to elucidate the role of cyclodextrin in Fenton remediation of TNT contaminated water. The rate and extent of TNT degraded by Fe2+- CD-H2O2 systems were significantly enhanced as compared to the classic Fenton method. Further, in water system with interfering substance - humic acid, which tends to associate with TNT, the addition of cyclodextrin helped to improve the efficiency of Fenton degradation. This technique has also been successfully applied to remediate TNT contaminated soil systems (sand). Four systems were investigated: clean sand, sand and humic acid, sand and fulvic acid, sand and natural organic matter. This technique has shown superior performance than classic Fenton method in all of the four above systems.

No description available.

No description available.

Cyclolinopeptides (CLs) are hydrophobic cyclic peptides found in flaxseed. They show immunosuppressive activity, but the biological function of these compounds is largely unknown. This thesis presents the results of studies that were conducted to determine whether CLs could act as antioxidants. In the first study, flaxseed oil was passed over a silica adsorbent column to remove polar compounds. The polar compounds were then eluted from the silica absorbant using a series of increasingly polar solvents. Individual polar fractions were then added back to the silica-treated flaxseed oil and the oxidative stability index of these samples was determined at 100 °C. A polar fraction containing mainly CLA, β/γ- and δ-tocopherol increased the induction time of silica-treated flaxseed oil from 2.3 ± 0.28 h to 3.2 ± 0.41 h. A positive effect of the polar fraction containing a mixture of CLA and CLD-CLG on the oxidative stability of oil was also observed. The antioxidant mechanism of CLs was investigated in several model systems using electron spin resonance spectroscopy. The concentration of radicals in a DMPO (5,5-dimethyl-1-pyrroline-N-oxide) radical-CLs reaction mixture was monitored. All CLs exhibited dose dependent scavenging activities. CLA–CLC reactions with DMPO-OH at a concentration of 5 mM resulted in a 24–30% decrease in electron paramagnetic resonance (EPR) signal intensity. The reaction of CLs and the stable radical 2,2-diphenyl-1-picrylhydrazyl (DPPH•) revealed a more complex interaction than simple radical scavenging. Peptides (CLG and CLG") that contained both tryptophan and methionine showed stronger radical scavenging activity than did CLs containing methionine or methionine sulfoxide but not tryptophan (CLB and CLC). Irradiation of the reaction mixture of DPPH• and peptide with UV light also affected the radical scavenging behaviour. Scavenging activities of DPPH• by CLB, CLC and CLA were enhanced by light, whereas scavenging of DPPH• by the tryptophan containing peptides CLG and CLG″ was not affected. High-performance liquid chromatography with mass spectrometry (HPLC-MS) analysis of the reaction mixtures after a radical scavenging reaction was used to determine the impact of radical scavenging on the peptides. These reactions revealed new masses that were identified and characterized. It was established that DPPH• reacted with the methionine of CLB and with tryptophan in CLG and CLG, by formation of a new covalently-bonded species. Covalent linkages between these amino acids (alone or in peptides) and DPPH• have not been reported previously.

Neste trabalho foi investigado o mecanismo de fotodegradação de polímeros e também a ação de agentes estabilizantes. Foi investigada a degradação oxidativa de polímeros solúveis em água como poli(vinilpirrolidona), PVP; poli(acrilamida), PAM e poli(etilenoglicol), PEG na presença de peróxido de hidrogênio, reagente de Fenton e sal de ferro. O PVP apresentou a menor fotoestabilidade enquanto a PAM apresentou a maior fotoestabilidade. O sal de ferro não promoveu a degradação. As soluções de PEG foram fotooxidadas com os sistemas UV/H2O2, Fenton e foto-Fenton e as amostras foram analisadas por GPC e HPLC. A análise por GPC das soluções de PEG mostrou que em todas as condições oxidativas usadas, a fotooxidação leva a uma queda acentuada da Mw, caracterizando um mecanismo de quebra de cadeia aleatório. Para os três sistemas usados, a polidispersidade aumenta após a degradação, confirmando o mecanismo de quebra aleatória de cadeia. As medidas de GPC também mostraram que a velocidade de degradação é muito maior com o sistema foto-Fenton (kd = 1,010-4 mol.g-1.min-1), seguida pelo sistema UV/H2O2 (kd = 3,610-5 mol.g-1.min-1). O uso do reagente de Fenton apresentou a menor velocidade de degradação (kd = 1,110-6 mol.g-1.min-1). Os produtos de degradação do PEG, nos três sistemas analisados, foram analisados por HPLC, sendo identificados produtos de menor peso molecular, entre eles, EG, 2EG, 3EG, 4EG, e os ácidos glicólico e fórmico. O mecanismo envolve um processo consecutivo em que os etilenoglicóis de maior peso molecular dão origem aos de menor peso molecular. Etilenoglicóis de cadeia curta foram usados com sucesso como moléculas modelo para prever o mecanismo de fotodegradação do PEG. Fenóis primários combinados com antioxidantes secundários contendo fósforo são os sistemas estabilizantes mais efetivos, amplamente usados na estabilização do processamento e na aplicação de olefinas a longo prazo. O mecanismo de reação de hidrólise dos antioxidantes fosfito, escolhidos para diferenciar na estrutura química e no conteúdo de fósforo, é investigado através da espectrometria de massas. Substituintes diferentes em torno do átomo de fósforo mostram um efeito significativo na estabilidade dos fosfitos com substituintes fenol, produzindo estruturas hidroliticamente estáveis. / The aim of this work was to investigate polymer photodegradation mechanisms and stabilizing agents. The course of photooxidative degradation of some water soluble polymers (poly(vinylpyrrolidone), PVP; poly(acrylamide), PAM and poly(ethylene glycol), PEG) in the presence of hydrogen peroxide, Fenton reagent and iron salt has been investigated. PVP showed the lowest photostability while PAM had the greatest photostability. Iron salt was not efficient promoting degradation. PEG has been photooxidized in Fenton, photo-Fenton and UV/H2O2 systems. Samples were analysed using GPC and HPLC. GPC analysis of PEG solutions showed that in all oxidizing conditions used, the photooxidation of PEG aqueous solutions leads to an abrupt decrease of Mw, which means that the degradation of PEG implies a random chain scission mechanism. Polydispersity increases after degradation in all the systems used, confirming a random chain scission mechanism. GPC analysis also showed that the rate of degradation is much higher for the photo-Fenton system (kd = 1,010-4 mol.g-1.min-1), followed by UV/H2O2 system (kd = 3,610-5 mol.g-1.min-1 ). Fenton reagent has the lowest degradation rate (kd = 1,110-6 mol.g-1.min-1). The degradation products of PEG in all oxidizing systems, were analyzed by HPLC and lower molecular weight products were detected, i.e., EG, 2EG, 3EG, 4EG, glycolic and formic acids. The mechanism involved a consecutive process, were the larger ethyleneglycols gave rise, successively, to smaller ones. This suggested that the mechanism involved successive scissions of the polymer chain. Ethyleneglycols were successfully used as model molecules to predict PEGs photodegradation mechanism. Primary hindered phenols in combination with phosphorous-based secondary antioxidants are one of the most effective stabilizing systems, widely used in the processing stabilization and long-term application of polyolefins. The hydrolysis reaction mechanism of phosphite antioxidants, chosen to differ in chemical structure and phosphorus content, is investigated by mass spectrometric means. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites with phenol substituent producing very hydrolytically stable structures.

Na região sul do Brasil, muito aterros sanitários encontram-se próximos a áreas de mineração de carvão, cujos rejeitos são ricos no mineral pirita (FeS2). Este trabalho teve como objetivo estudar o tratamento de lixiviado de aterro sanitário com coagulantes férricos e ferrosos produzidos a partir da oxidação da pirita em meio aquoso. O lixiviado de aterro sanitário foi coletado no Aterro do Município de Campo Bom no Vale do Rio dos Sinos – RS. Pesquisou-se o efeito da dosagem do coagulante e avaliou-se comparativamente o desempenho com coagulantes comerciais produzidos a partir da dissolução de sucata ferrosa em ácido sulfúrico. Os resultados obtidos demostraram que os coagulantes férricos são eficiente no tratamento por coagulação dos lixiviados em dosagens superiores a 1 g/L. Verificou-se também que os coagulantes ferrosos podem ser aplicados no tratamento do chorume pelo processo Fenton (H2O2/Fe). Foram realizados ensaios considerando diferentes misturas de chorume e DAM, com e sem a adição de H2O2. O efeito de coagulação, em ambos os casos, melhorou as características do efluente em termos de carga orgânica, metais pesados e nutrientes. Porém, quando foi adicionado o H2O2 (Reação de Fenton), o efluente final apresentou melhores resultados em relação a cor, COT (Carbono Orgânico Total), nutrientes e, principalmente, em termos de bactérias do grupo coliforme. Os resultados demonstraram que a drenagem ácida de minas, especialmente as mais concentradas e ricas em Fe+2, podem ser empregadas a baixo custo como fonte de ferro para a Reação de Fenton. Desta maneira, surgem novas tecnologias para o tratamento primário de chorume com o uso de coagulante férricos e ferrosos produzidos a partir da oxidação da pirita presente em rejeitos de carvão. / In southern Brazil, most landfills are close to coal mining areas, whose tailings are rich in the mineral pyrite (FeS2). This work aimed at studying the treatment of landfill leachate with ferrous and ferric coagulants produced from the oxidation of pyrite in aqueous media. The landfill leachate was collected in the landfill of the city of Campo Bom in the region of Vale do Rio dos Sinos – RS, Brazil. The effect of the dosage of coagulant was evaluated and compared performance with commercial coagulants produced from the dissolution of ferrous scrap in sulfuric acid was researched for this paper. The results showed that ferric coagulants are effective in the treatment of leachate by coagulation at dosages greater than 1g / L. It was also found that the ferrous coagulants can be applied in the treatment of leachate by Fenton process (H2O2/Fe). Researches have been performed considering different mixtures of manure and AMD (Acid Mine Drainages), with and without the addition of H2O2. The coagulation effect in both cases, improved the characteristics of the effluent in terms of organic load, heavy metals and nutrients. However, when H2O2 (Fenton reaction) was added, the wastewater showed better results for color, TOC (Total Organic Carbon), nutrients, and especially in terms of coliform bacteria. The results showed that acid mine drainage, especially the most concentrated and rich in Fe +2, can be employed at low cost as a source of iron for the Fenton reaction. Thus, there are new technologies for the primary treatment of manure with the use of ferrous and ferric coagulant produced from the oxidation of pyrite present in coal tailings.

Na região sul do Brasil, muito aterros sanitários encontram-se próximos a áreas de mineração de carvão, cujos rejeitos são ricos no mineral pirita (FeS2). Este trabalho teve como objetivo estudar o tratamento de lixiviado de aterro sanitário com coagulantes férricos e ferrosos produzidos a partir da oxidação da pirita em meio aquoso. O lixiviado de aterro sanitário foi coletado no Aterro do Município de Campo Bom no Vale do Rio dos Sinos – RS. Pesquisou-se o efeito da dosagem do coagulante e avaliou-se comparativamente o desempenho com coagulantes comerciais produzidos a partir da dissolução de sucata ferrosa em ácido sulfúrico. Os resultados obtidos demostraram que os coagulantes férricos são eficiente no tratamento por coagulação dos lixiviados em dosagens superiores a 1 g/L. Verificou-se também que os coagulantes ferrosos podem ser aplicados no tratamento do chorume pelo processo Fenton (H2O2/Fe). Foram realizados ensaios considerando diferentes misturas de chorume e DAM, com e sem a adição de H2O2. O efeito de coagulação, em ambos os casos, melhorou as características do efluente em termos de carga orgânica, metais pesados e nutrientes. Porém, quando foi adicionado o H2O2 (Reação de Fenton), o efluente final apresentou melhores resultados em relação a cor, COT (Carbono Orgânico Total), nutrientes e, principalmente, em termos de bactérias do grupo coliforme. Os resultados demonstraram que a drenagem ácida de minas, especialmente as mais concentradas e ricas em Fe+2, podem ser empregadas a baixo custo como fonte de ferro para a Reação de Fenton. Desta maneira, surgem novas tecnologias para o tratamento primário de chorume com o uso de coagulante férricos e ferrosos produzidos a partir da oxidação da pirita presente em rejeitos de carvão. / In southern Brazil, most landfills are close to coal mining areas, whose tailings are rich in the mineral pyrite (FeS2). This work aimed at studying the treatment of landfill leachate with ferrous and ferric coagulants produced from the oxidation of pyrite in aqueous media. The landfill leachate was collected in the landfill of the city of Campo Bom in the region of Vale do Rio dos Sinos – RS, Brazil. The effect of the dosage of coagulant was evaluated and compared performance with commercial coagulants produced from the dissolution of ferrous scrap in sulfuric acid was researched for this paper. The results showed that ferric coagulants are effective in the treatment of leachate by coagulation at dosages greater than 1g / L. It was also found that the ferrous coagulants can be applied in the treatment of leachate by Fenton process (H2O2/Fe). Researches have been performed considering different mixtures of manure and AMD (Acid Mine Drainages), with and without the addition of H2O2. The coagulation effect in both cases, improved the characteristics of the effluent in terms of organic load, heavy metals and nutrients. However, when H2O2 (Fenton reaction) was added, the wastewater showed better results for color, TOC (Total Organic Carbon), nutrients, and especially in terms of coliform bacteria. The results showed that acid mine drainage, especially the most concentrated and rich in Fe +2, can be employed at low cost as a source of iron for the Fenton reaction. Thus, there are new technologies for the primary treatment of manure with the use of ferrous and ferric coagulant produced from the oxidation of pyrite present in coal tailings.

Na região sul do Brasil, muito aterros sanitários encontram-se próximos a áreas de mineração de carvão, cujos rejeitos são ricos no mineral pirita (FeS2). Este trabalho teve como objetivo estudar o tratamento de lixiviado de aterro sanitário com coagulantes férricos e ferrosos produzidos a partir da oxidação da pirita em meio aquoso. O lixiviado de aterro sanitário foi coletado no Aterro do Município de Campo Bom no Vale do Rio dos Sinos – RS. Pesquisou-se o efeito da dosagem do coagulante e avaliou-se comparativamente o desempenho com coagulantes comerciais produzidos a partir da dissolução de sucata ferrosa em ácido sulfúrico. Os resultados obtidos demostraram que os coagulantes férricos são eficiente no tratamento por coagulação dos lixiviados em dosagens superiores a 1 g/L. Verificou-se também que os coagulantes ferrosos podem ser aplicados no tratamento do chorume pelo processo Fenton (H2O2/Fe). Foram realizados ensaios considerando diferentes misturas de chorume e DAM, com e sem a adição de H2O2. O efeito de coagulação, em ambos os casos, melhorou as características do efluente em termos de carga orgânica, metais pesados e nutrientes. Porém, quando foi adicionado o H2O2 (Reação de Fenton), o efluente final apresentou melhores resultados em relação a cor, COT (Carbono Orgânico Total), nutrientes e, principalmente, em termos de bactérias do grupo coliforme. Os resultados demonstraram que a drenagem ácida de minas, especialmente as mais concentradas e ricas em Fe+2, podem ser empregadas a baixo custo como fonte de ferro para a Reação de Fenton. Desta maneira, surgem novas tecnologias para o tratamento primário de chorume com o uso de coagulante férricos e ferrosos produzidos a partir da oxidação da pirita presente em rejeitos de carvão. / In southern Brazil, most landfills are close to coal mining areas, whose tailings are rich in the mineral pyrite (FeS2). This work aimed at studying the treatment of landfill leachate with ferrous and ferric coagulants produced from the oxidation of pyrite in aqueous media. The landfill leachate was collected in the landfill of the city of Campo Bom in the region of Vale do Rio dos Sinos – RS, Brazil. The effect of the dosage of coagulant was evaluated and compared performance with commercial coagulants produced from the dissolution of ferrous scrap in sulfuric acid was researched for this paper. The results showed that ferric coagulants are effective in the treatment of leachate by coagulation at dosages greater than 1g / L. It was also found that the ferrous coagulants can be applied in the treatment of leachate by Fenton process (H2O2/Fe). Researches have been performed considering different mixtures of manure and AMD (Acid Mine Drainages), with and without the addition of H2O2. The coagulation effect in both cases, improved the characteristics of the effluent in terms of organic load, heavy metals and nutrients. However, when H2O2 (Fenton reaction) was added, the wastewater showed better results for color, TOC (Total Organic Carbon), nutrients, and especially in terms of coliform bacteria. The results showed that acid mine drainage, especially the most concentrated and rich in Fe +2, can be employed at low cost as a source of iron for the Fenton reaction. Thus, there are new technologies for the primary treatment of manure with the use of ferrous and ferric coagulant produced from the oxidation of pyrite present in coal tailings.

Neste trabalho foi investigado o mecanismo de fotodegradação de polímeros e também a ação de agentes estabilizantes. Foi investigada a degradação oxidativa de polímeros solúveis em água como poli(vinilpirrolidona), PVP; poli(acrilamida), PAM e poli(etilenoglicol), PEG na presença de peróxido de hidrogênio, reagente de Fenton e sal de ferro. O PVP apresentou a menor fotoestabilidade enquanto a PAM apresentou a maior fotoestabilidade. O sal de ferro não promoveu a degradação. As soluções de PEG foram fotooxidadas com os sistemas UV/H2O2, Fenton e foto-Fenton e as amostras foram analisadas por GPC e HPLC. A análise por GPC das soluções de PEG mostrou que em todas as condições oxidativas usadas, a fotooxidação leva a uma queda acentuada da Mw, caracterizando um mecanismo de quebra de cadeia aleatório. Para os três sistemas usados, a polidispersidade aumenta após a degradação, confirmando o mecanismo de quebra aleatória de cadeia. As medidas de GPC também mostraram que a velocidade de degradação é muito maior com o sistema foto-Fenton (kd = 1,010-4 mol.g-1.min-1), seguida pelo sistema UV/H2O2 (kd = 3,610-5 mol.g-1.min-1). O uso do reagente de Fenton apresentou a menor velocidade de degradação (kd = 1,110-6 mol.g-1.min-1). Os produtos de degradação do PEG, nos três sistemas analisados, foram analisados por HPLC, sendo identificados produtos de menor peso molecular, entre eles, EG, 2EG, 3EG, 4EG, e os ácidos glicólico e fórmico. O mecanismo envolve um processo consecutivo em que os etilenoglicóis de maior peso molecular dão origem aos de menor peso molecular. Etilenoglicóis de cadeia curta foram usados com sucesso como moléculas modelo para prever o mecanismo de fotodegradação do PEG. Fenóis primários combinados com antioxidantes secundários contendo fósforo são os sistemas estabilizantes mais efetivos, amplamente usados na estabilização do processamento e na aplicação de olefinas a longo prazo. O mecanismo de reação de hidrólise dos antioxidantes fosfito, escolhidos para diferenciar na estrutura química e no conteúdo de fósforo, é investigado através da espectrometria de massas. Substituintes diferentes em torno do átomo de fósforo mostram um efeito significativo na estabilidade dos fosfitos com substituintes fenol, produzindo estruturas hidroliticamente estáveis. / The aim of this work was to investigate polymer photodegradation mechanisms and stabilizing agents. The course of photooxidative degradation of some water soluble polymers (poly(vinylpyrrolidone), PVP; poly(acrylamide), PAM and poly(ethylene glycol), PEG) in the presence of hydrogen peroxide, Fenton reagent and iron salt has been investigated. PVP showed the lowest photostability while PAM had the greatest photostability. Iron salt was not efficient promoting degradation. PEG has been photooxidized in Fenton, photo-Fenton and UV/H2O2 systems. Samples were analysed using GPC and HPLC. GPC analysis of PEG solutions showed that in all oxidizing conditions used, the photooxidation of PEG aqueous solutions leads to an abrupt decrease of Mw, which means that the degradation of PEG implies a random chain scission mechanism. Polydispersity increases after degradation in all the systems used, confirming a random chain scission mechanism. GPC analysis also showed that the rate of degradation is much higher for the photo-Fenton system (kd = 1,010-4 mol.g-1.min-1), followed by UV/H2O2 system (kd = 3,610-5 mol.g-1.min-1 ). Fenton reagent has the lowest degradation rate (kd = 1,110-6 mol.g-1.min-1). The degradation products of PEG in all oxidizing systems, were analyzed by HPLC and lower molecular weight products were detected, i.e., EG, 2EG, 3EG, 4EG, glycolic and formic acids. The mechanism involved a consecutive process, were the larger ethyleneglycols gave rise, successively, to smaller ones. This suggested that the mechanism involved successive scissions of the polymer chain. Ethyleneglycols were successfully used as model molecules to predict PEGs photodegradation mechanism. Primary hindered phenols in combination with phosphorous-based secondary antioxidants are one of the most effective stabilizing systems, widely used in the processing stabilization and long-term application of polyolefins. The hydrolysis reaction mechanism of phosphite antioxidants, chosen to differ in chemical structure and phosphorus content, is investigated by mass spectrometric means. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites with phenol substituent producing very hydrolytically stable structures.

An ancient technology of solar-driven water evaporation and distillation has recently been revived due to the concept of interfacial solar evaporation and the development of photothermal materials. There have been many research interests in improving solar light harvesting and solar-to-water evaporation efficiency within these systems, including new photothermal materials search, structural engineering, and thermal management. The application horizon of both solar-driven water evaporation and distillation has been broadly expanded beyond their conventional domain, including now wastewater treatment, seawater desalination, steam sterilization, electric generation, and chemicals/fuels productions. This dissertation focused on designing of photothermal materials and their applications to clean water production. More specifically: (1) a bi-layered porous rGO membrane with a polystyrene (PS) foam as the heat insulator was designed and proved to be effective for reducing heat conduction to the bulk water and to improve the solar-to-water evaporation efficiency, (2) a tandem-structured SiC-C ceramic monolith was prepared and demonstrated to be mechanically and chemically stable to withstand physical or chemical cleaning during long-term use in real seawater and wastewater, (3) in order to simultaneously treat the contaminated water and get clean distillate water, multi-functional SiC foam modified with mesoporous Au/TiO2 nanocomposites has been prepared, which was demonstrated to possess both photocatalytic reduction and oxidation abilities for complex wastewater treatment, and (4) when the water source was contaminated by VOCs, another efficient multi-functional photothermal material was designed with a honeycomb ceramic plate as the matrix material, and a CuFeMnO4 nanocomposite coating layer acting as both photothermal material and Fenton agent for VOCs removal. Therefore, the light absorption property of photothermal material could be improved by using a porous structure, tandem-structure, porous foam or 3D structure. The solar-to-water evaporation efficiency was improved by including a heat insulator and the reduction of the water channels’ dimension. The ceramic-based material showed potential for long-term use with high mechanical strength to endure physical cleaning. Multi-functional photothermal materials were successfully developed for complex wastewater treatment and clean water generation.