No description available.

A adaptação dos cimentos endodônticos, Ketac-Endo, AH Plus e Endomethásone, à dentina radicular submetida à ação prévia dos agentes de limpeza final laser de Er:YAG, EDTA a 17% e Solução Salina Fisiológica a 0,9% foi estudada pelas microscopias óptica e eletrônica de varredura. Foram empregados 90 caninos humanos extraídos, que após instrumentação pela técnica escalonada de memória e irrigação com hipoclorito de sódio a 1%, foram divididos em três grupos de 30, de acordo com o agente de limpeza final empregado. No grupo A, empregou-se o laser de Er:YAG intracanal, com parâmetros de 100mJ (energia real de 44mJ), 10pps, durante dez segundos, sob refrigeração a ar, com movimentos circulares no sentido apicocoronário, seguido de irrigação com 20ml de solução salina fisiológica a 0,9%. No grupo B, empregaram-se 5ml de EDTA a 17% durante cinco minutos, seguido de irrigação com solução salina fisiolólgica a 0,9%. No grupo C, empregaram-se 20ml de Solução Salina Fisiológica a 0,9%. Após secagem, os canais radiculares foram armazenados em solução salina fisiológica a 0,9% durante 48 horas. Cada grupo foi então dividido em três subgrupos de dez,de acordo com o cimento endodôntico. Os 90 canais radiculares foram obturados pela técnica clássica, seguida da condensação lateral ativa da guta-percha. Após comprovação radiográfica da obturação os canais foram vedados com Cimpat no terço cervical e forame apical, e as raízes armazenadas em solução salina fisiológica a 0,9% em umidade de 100% a 37oC, durante 30 dias. Em seguida, foram seccionadas transversalmente a 5mm do ápice radicular, fotografadas com aumento de quatro vezes e submetidas à análise em microscopia óptica. Para a análise em microscopia eletrônica de varredura, as secções apicais foram moldadas em silicona Aquasil e os moldes obtidos foram metalizados e fotografados em aumentos que variaram de 50 a 200 vezes. As fotos obtidas pelas microscopias foram escaneadas e transferidas para um programa de medida de área (SigmaScan) para mensuração das áreas preenchidas pelos materiais obturadores e das possíveis fendas entre material obturador e parede do canal radicular. Diante dos resultados obtidos com a metodologia empregada e da discussão apresentada pudemos concluir que: 1- Os agentes de limpeza final empregados exerceram efeito diferenciado na adaptação dos cimentos testados. O laser de Er:YAG interferiu na adaptação de todos os cimentos, o EDTA melhorou a adaptação do Endomethásone e do AH Plus em relação ao laser de Er:YAG e à solução salina fisiológica a 0,9% e a solução salina fisiológica melhorou a adaptação do Ketac-Endo, em ambas microscopias empregadas. 2- O Endomethásone apresentou a pior adaptação entre os cimentos e o AH Plus apresentou a melhor adaptação com EDTA na microscopia eletrônica de varredura. 3- A associação das microscopias óptica e eletrônica de varredura mostrou ser um método confiável na detecção das fendas, sendo que a microscopia eletrônica de varredura propiciou melhor visualização. 4- Todos os cimentos testados apresentaram alteração dimensional, verificando-se contração para o Ketac-Endo, expansão para o Endomethásone e AH-Plus, sendo que o AH Plus mostrou-se mais próximo da estabilidade dimensional. / The adaptation of endodontic sealers, Ketac-Endo, AH Plus and Endomethásone to dentinal root submitted to the previous action of final Er:YAG laser cleaning agents, EDTA at 17% and a saline solution at 0.9% was studied by Optical and Scanning Electron Microscopy. Ninety extracted human canines were employed, and following the step back technique preparation and irrigation with sodium hypochlorite solution they were divided into three groups with thirty teeth each, according to the final cleaning agent used. In group A, Er:YAG laser was used intracanal, with the following parameters: 100mJ (real energy 44mJ), 10pps, for 10 seconds under air cooling with circular movements in apicocervical direction and the canals were irrigated with 20ml saline solution at 0.9%. In group B, 5ml of EDTA at 17% irrigated the root canals for 5 minutes, followed by a saline solution at 0.9%. In group C, a saline solution at 0.9% was employed to irrigate the root canals. After drying, the roots were stored in a saline solution at 0.9% for 48 hours. Each group was divided into three subgroups of ten, according to the selected endodontic sealer. The ninety root canals were filled through standard technique, followed by gutta-percha lateral condensation. Following radiographic filling proof, the root canals were sealed with Cimpat in the cervical third and at the apical foramen, and the roots stored in a 0.9% saline solution at 37oC and 100% humidity for 30 days. Afterwards, they were transversally secctioned at 5mm to the root apex, and photographed with a 4x magnification, and submitted to optical microscopic analysis. Before the Scanning Electron Microscopic analysis, the apical root sections were molded with Aquasil and the obtained replicas metallized and photographed with 50x and 200x magnifications. The resulting images, in both microscopies, were scanned and transferred to the area measurement software program (SigmaScan) to measure the areas filled by endodontic materials and the failed areas between the endodontic material and the root canal walls. Through the results with the selected methodology and by means of the presented discussion, we could conclude that: 1- The final cleaning agents employed in the root canals presented different effects in the adaptation of the endodontic sealers. The Er:YAG laser was harmful to the adaptation of all the endodontic sealers; the EDTA improved the adaptation of Endomethásone and AH Plus and the 0.9% saline solution improved the adaptation of Ketac-Endo in both microscopies. 2- Endomethásone presented the worst adaptation compared to the other sealers and AH Plus presented the best adaptation with EDTA by Scanning Electron Microscopic analysis. 3- The Optical Microscopy associated with the Scanning Electron Microscopy proved to be a safe method in detecting filling failures, being, the Scanning Electron Microscopy the best. 4- All endodontic sealers presented dimensional alterations, Ketac-Endo presented contraction, Endomethásone and AH Plus presented expansion, being, AH Plus closer to dimensional stability.

La gesse commune (Lathyrus sativus L.) est une légumineuse cultivée principalement en Inde, au Bangladesh et en Ethiopie qui présente des niveaux de résistance élevés pour de nombreuses contraintes abiotiques, telles que la sécheresse et l'inondation. Dans ce travail, les capacités de tolérance du Lathyrus (lignées locales "Raipur" et "Bangladesh") à une autre contrainte abiotique, la présence de plomb, ont été déterminées des points de vue physiologique et moléculaire. Un système expérimental de culture hydroponique a été mis au point pour ces plantes. Le plomb y est introduit sous forme de nitrate de plomb (Pb(NO3)2). Les teneurs en plomb des différents organes des plantes (racines, tiges, feuilles) ont été déterminées par ICP-OES. Les réponses cellulaires dans ces organes ont été étudiées par RTPCR quantitative (PCR en temps réel). Des amorces spécifiques du Lathyrus ont été dessinées à partir des 11 séquences d'ADN complémentaires (ADNc) isolées pour la première fois et séquencées. L'un des ADNc isolé est complet et code une cystéine protéase (LsCP, 427 aa). Les autres sont des ADNc partiels et correspondent à une aspartique protéase (LsAP, 270 aa), deux ascorbate peroxidases cytosolique (LsAPXc, 195 aa) et peroxisomale (LsAPXp, 226 aa), une protéine de choc thermique ("Heat Shock Protein 70" ; LsHSP70, 287), une homoglutathion synthétase (LshGSHS, 329 aa), une glutathion S-transférase (LsGST, 66 aa), une glutathion réductase (LsGR, 336 aa), une phytochélatine synthétase (LsPCS, 64 aa), une phospholipase D a (LsPLDa, 288 aa), un transporteur membranaire spécifique du Pb (LsCNGC, 136) et une protéine soluble (LsABCt, 331 aa). Les plantes exposées au nitrate de plomb accumulent de grandes quantités de métal dans leurs racines sous forme de plomb fortement lié aux tissus. L'accumulation d'ARN messagers de la LsPLDa suggère que les racines subissent une contrainte cellulaire et s'y adaptent. La stimulation de l'expression des gènes LsGST, LsGR et LsAPX correspondrait à la formation de complexes Pb-glutathion et à une activation du cycle ascorbate-glutathion pour la neutralisation des espaces activées de l'oxygène (ROS) délétères. Dans les feuilles exemptes de plomb, l'augmentation de l'expression des gènes LsCP, LsAP, LsAPXc, LsAPXp, LsHSP70, LsGR et LsPCS semble indiquer l'émission d'un signal racinaire transmis de manière systémique vers le reste de la plante où il déclenche la sur-expression de ces gènes. Ceci pourrait permettre aux tissus épargnés par le polluant de se préparer à son éventuelle arrivée. La chélation du Pb avec de l'EDTA dans le milieu de culture conduit à son transport vers les parties aériennes et à son accumulation dans les feuilles. L'expression du gène LsCNGC chez ces plantes est activée dans les feuilles, suggérant une participation de ce transporteur à l'entrée des complexes Pb-EDTA dans le symplasme. Comme observé chez d'autres espèces végétales, le plomb affecte le métabolisme du glutathion chez la gesse commune. Cependant, la mise en évidence d'une réaction systémique en réponse au plomb à partir des racines ainsi que la surexpression de gènes d'autolyse sont réalisées pour la première fois et pourraient être des éléments contribuant fortement à la tolérance au plomb chez cette espace végétale sous-utilisée. / Grass pea (Lathyrus sativus L.) is a legume plant cultivated mostly in India, Bangladesh and Ethiopia. It possesses high tolerance levels to abiotic stresses like drought and flooding. In the present work, the tolerance of Lathyrus sativus L. (local lines "Raipur" and "Bangladesh") to another abiotic stress: lead, has been determined, using a physiological and a molecular approach. A hydroponic culture system has been set up. Lead was introduced as lead nitrate (Pb(NO3)2). Lead contents in various plant organs (roots, stems, leaves) were determined using ICP-OES. Cell responses in these organs were studied using real-time RT-PCR. Grass pea-specific primers were designed from the 11 complementary DNA sequences that were isolated and sequenced here for the first time. One of the cDNA is full-length and codes a cystein protease (LsCP). The others are partial cDNA and code an aspartic protease (LsAP, 270 aa), two ascorbate peroxidases, a cytosolic (LsAPXc, 195 aa) and a peroxisomal (LsAPXp, 226 aa), a heat shock protein 70 (LsHSP70, 287), a homoglutathione synthetase (LshGSHS, 329 aa), a glutathione-S-transferase (LsGST, 66 aa), a glutathione reductase (LsGR, 336 aa), a phytochelatin synthetase (LsPCS, 64 aa), a phospholipase D a (LsPLDa, 288 aa), a membrane transporter specific of lead (LsCNGC, 136) and a soluble protein (LsABCt, 331 aa). The plants exposed to lead accumulate large amounts of the metal in their roots only and the metal is tightly bound to the tissues. mRNA accumulation for LsPLDa suggest that root tissues are under stress and coping. The increases in LsGST, LsGR and LsAPX transcripts suggest that Pb-glutathione complexes are formed and that the ascorbate-glutathione cycle is stimulated to scavenge deleterious activated oxygen species, in the root tissues. In lead-free leaves, LsCP, LsAP, LsAPXc, LsAPXp, LsHSP70, LsGR et LsPCS genes are overexpressed. This indicates that a root signal is emitted by these leaded tissues and transported systemically to the rest of the plant where it stimulates the expression of the genes mentioned above. This could be a prevention mechanism to prepare leaf tissues for the possibility of lead spreading. Chelation of lead with EDTA in the growth medium facilitates the transport of the pollutant to the leaves where it accumulates. In these tissues, the LsCNGC is over-expressed suggesting that this transporter is involved in the translocation of the Pb-EDTA complexes into the leaf symplasm. As was observed previously in other plant species, lead affects glutathione metabolism in grass pea. However, the observation of a systemic signal originating from the leaves in response to lead and the over-expression of autolytic genes are reported here for the first time and could be contributing elements to lead tolerance in this under-utilized plant species.

O objetivo deste trabalho foi avaliar o efeito do tratamento químico com ácido cítrico, tetraciclina, EDTA e ácido fosfórico em discos de titânio de superfícies lisas e rugosas, após serem contaminados por biofilme bacteriano humano, e inseridos no tecido conjuntivo subcutâneo de ratos. Utilizou-se 180 discos de titânio, sendo 90 lisos e 90 rugosos, que foram colocados em 19 placas de acrílico utilizadas por voluntários durante 7 dias. Estes discos foram divididos em 12 grupos contendo 15 discos cada um: Grupo 1L: 15 discos lisos tratados com ácido cítrico; Grupo 1R: 15 discos rugosos tratados com ácido cítrico; Grupo 2L: 15 discos lisos tratados com tetraciclina ácida; Grupo 2R: 15 discos rugosos tratados com tetraciclina ácida; Grupo 3L: 15 discos lisos tratados com EDTA; Grupo 3R: 15 discos rugosos tratados com EDTA; Grupo 4L: 15 discos lisos tratados com ácido fosfórico; Grupo 4R: 15 discos rugosos tratados com ácido fosfórico; Grupo CL: 15 discos lisos que não receberam descontaminação (controle positivo liso); Grupo CR: 15 discos rugosos que não receberam descontaminação (controle positivo rugoso); Grupo EL: 15 discos lisos que não foram contaminados (controle negativo liso) e Grupo ER: 15 discos rugosos que não foram contaminados (controle negativo rugoso). Estes discos foram implantados no subcutâneo de ratos, os quais foram sacrificados após 7, 28 ou 84 dias. Foi realizada a avaliação microscópica descritiva e quantitativa do tecido conjuntivo formado nestes ratos. Foram avaliadas as médias das espessuras das cápsulas, a densidade de fibroblastos e de neutrófilos nos 3 períodos de tempo. Os resultados mostraram diferença na densidade de neutrófilos principalmente aos 7 dias e o ácido fosfórico mostrou os melhores resultados neste período, e ao final de 84 dias todos os tratamentos apresentaram resultados similares inclusive com relação ao grupo controle contaminado. Com relação à rugosidade os discos de superfícies lisas, apresentaram menor média na espessura da cápsula comparandose com os discos de superfícies rugosas, talvez demonstrando um aspecto de maior biocompatibilidade da superfície lisa após receber o tratamento de descontaminação, o que sugeriria maior efetividade na descontaminação dos protótipos lisos. / The purpose of this investigation was to evaluate the effects of treatment with citric acid, tetracycline, EDTA and phosphoric acid in titanium disks in smooth and roughened surfaces contaminated by bacterial biofilms in the connective tissue of rats. One hundred eighty titanium disks were used; 90 smooth surfaces and 90 roughened titanium surfaces, which were placed in 19 acrylic plates that were used by volunteers for 7 days. These disks were divided into 12 groups containing 15 disks each; Group 1L: 15 smooth disks were treated with citric acid; Group 1R: 15 roughened disks were treated with citric acid; Group 2L: 15 smooth disks were treated with tetracycline acid; Group 2R: 15 roughened disks were treated with tetracycline rough acid; Group 3L: 15 smooth disks were treated with EDTA; Group 3R: 15 roughened disks were treated with EDTA; Group 4L: 15 smooth disks were treated with phosphoric acid; Group 4R: 15 roughened disks were treated with phosphoric acid; Group CL: 15 smooth disks received no econtamination (smooth positive control); CR: 15 roughened disks did not receive decontamination (roughened positive control); EL: 15 smooth disks were not infected (smooth negative control) and ER: 15 roughened disks were not infected (roughened negative control). These disks were implanted subcutaneously in rats that were sacrificed after 7, 28 or 84 days. A descriptive and quantitative microscopic evaluation was performed. The average thickness of the capsules and the density of fibroblasts and neutrophils in three time periods were evaluated. The results showed differences in the density of neutrophilis mainly at 7 days and phosphoric acid showed the best results in this period, and at the end of 84 days, all treatments showed similar results even with the control group infected. In relation to the roughness, the smooth disks had a lower average capsule thickness compared with roughened disks, perhaps demonstrating an aspect of greater biocompatibility smooth surface, which would suggest greater effectiveness in decontamination of smooth disks.

This thesis describes a study of the remobilisation of heavy metals from sediments by three aminopolycarboxylic acids (APCAs). They are nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid. The investigation is introduced by examining the sources, uses and chemistry of these acids. The introduction also includes a discussion of what is known about the inclusion of heavy metals into sediments and their remobilisation from sediments. Typical concentrations of APCAs in natural waters and sediments have been catalogued from the literature. The advantages and disadvantages of various laboratory techniques employed for the remobilisation of heavy metals by APCAs from sediments are assessed, as is the use of such experiments in quantifying the role of APCAs in the remobilisation of heavy metals from sediments. Sediments from three areas were sampled for this study; they were the Alexandra Canal, Captains Flat and Jenolan Caves in New South Wales, Australia. In each area several sites were sampled. For each site there is a brief description of the catchment geology and hydrology. Selected sediment-associated waters in the areas were analysed for their metal concentrations as well as for ultratrace levels of APCAs employing a method developed in the present study. The waters were analysed for the major ions Ca2+, Mg2+, K+, Na+, Cl-, NO3- and SO42-. The sediments from selected sites in each of the areas were dried and fractionated. The dry total and fine sediments were analysed for their metal content and the latter was found to adequately represent the former in this respect. Water samples from the three areas showed different chemistries and exhibited more subtle differences between sites. In general, the Alexandra Canal waters are saline and alkaline and are a mixture of urban runoff and seawater; the Captains Flat waters are acidic and contain high sulfate from acid mine and tailings drainage; the Jenolan Caves waters are neutral and have the features characteristic of waters draining through limestone. The APCA contamination in all water samples when ranked against other global sites is very low. Although the current APCA levels in the waters appear low, it was concluded that they should be closely monitored so that efforts can be made to minimise the risk of APCAs being hazardous environmental contaminants and also that any remobilisation of heavy metals from sediments by APCAs can be controlled. Agitation and column laboratory-scale experiments were carried out in order to obtain an understanding of the remobilisation of metals by contamination levels of APCAs in water, both as the individual APCAs and as a mixture of APCAs. Complimentary experiments were carried out using a molar excess of APCAs calculated from the metal concentrations obtained by acid digestion (assuming 1:1 metal complex formation). Both types of remobilisation experiments were designed to investigate the role that redox potential (Eh) and concentration of APCAs in natural waters have on the remobilisation of heavy metals from the sediments. The agitation experiments were employed to assess metal remobilisation for the situation where the sediments are disturbed while the column experiments explored metal remobilisation for the case where the sediments are left undisturbed in situ. The major conclusions from the agitation experiments that used fine sediment from the Alexandra Canal were that 100 ppm APCA solutions will remobilise metals from the sediments under oxic conditions but only remobilise infinitesimally small amounts of metal under anoxic conditions. The use of fine sediments for the duplicate agitation experiments was found to give adequate duplication of results. A mixture of APCAs in solution acts similarly to the average of the three individual APCA solutions, showing that there are no antagonistic or synergistic effects likely to occur when they are found together in the environment. It was found that the mmoles of the metals remobilised exceeded the mmoles of the APCAs added when 500.0 mL of 100 ppm APCA solution was used on 50.00 g of sediment. This might be due to APCAs remobilising metals from the sediments in ways other than by complexation. Even though an excess of APCAs was available, metal remobilisation was not complete when the experiments were forced to terminate. During the 14 days of the experiment, only one quarter of the metals liberated from the sediment by HNO3 and 30 % H2O2 digestion were remobilised by the APCAs. Therefore an excess of free APCAs remains in solution. Fine sediments from Alexandra Canal, Captains Flat and Jenolan Caves were employed in the oxic agitation experiments using excess APCAs in solution. These experiments resulted in the following major conclusion: when producing an APCA remobilisation signature for trace and ultratrace metals, the geochemistry of the site is of secondary importance to the source of the contaminating metals. This is a feature of the trace and ultratrace metal speciation in the source rather than their concentration in it. From the different levels of calcium present in the three areas it was found that calcium is unlikely to form stable 1:1 APCA complexes at the pH values employed and is unlikely to compete with the heavy metal remobilisation by APCAs. Total sediments from Alexandra Canal and 100 ppm APCA solutions were employed for the column leaching experiments. From mass, pore water volumes and flow measurements it was shown that the ten mini cores taken from the same site were not true replicates. Despite this, when the sediments have settled and the pore waters removed from the cores, the levels of metal being leached stabilise and may represent a clearer picture of the in situ metal leaching from sediment with time. The levels of metal leached from the cores in 14 days suggest that during this period the cores are essentially anoxic, with the oxygen supplied from the oxic leaching solutions used for inorganic and microbial processes in the sediments. Agitation experiments appeared to yield an adequate picture of what would happen if free APCA solution came in contact with fine sediments suspended in the water column. Column leaching experiments employing total sediment were found to be only of limited value in assessing heavy metal remobilisation from undisturbed sediment. These experiments do not give a reliable assessment of the bioavailability of heavy metals and further testing of the acute and chronic toxicity of the sediments is recommended. APCA solutions that have been used in sediment and soil washing under conditions related to those used in the present study may contain an excess of the free APCAs as well as APCA heavy metal complexes and hence may be toxic to biota.

Le nickel est un cofacteur essentiel à l'activité de certaines protéines bactériennes, mais il est également toxique à forte concentration. De ce fait, il est indispensable aux bactéries de posséder un système d'import du Ni2+ spécifique et hautement régulé. Dans le cas d'Escherichia coli, il s'agit d'un système ABC composé des cinq protéines de l'opéron nikabcde : NikA, une protéine périplasmique, NikB et NikC, deux protéines formant un pore à travers la membrane interne, et les protéines NikD et NikE, deux protéines cytoplasmiques hydrolysant l'ATP. La régulation de l'expression de cet opéron est assurée par FNR, l'activateur, et de NikR, le répresseur. Dans un premier temps, nous avons travaillé sur une structure de la protéine NikA, résolue à partir de cristaux appartenant au système orthorhombique. Elle nous a permis de montrer que NikA ne fixait pas le nickel sous une forme pentahydratée comme cela était décrit dans la littérature, mais sous la forme d'un complexe FeEDTA(H2O)-, ce qui suggère que le nickel ne se fixe pas directement à la protéine, mais par l'intermédiaire d'un métallophore de structure proche de celle de l'EDTA. En remplaçant l'étape d'extraction périplasmique à l'EDTA par une étape utilisant le chloroforme, nous avons résolu, une seconde structure de NikA à partir de cristaux appartenant au système cristallin hexagonal. Dans ce cas, on observe, dans le site de fixation de la protéine, un nickel en complexe avec une molécule similaire à l'EDTA, laquelle a de fortes chances d'être le métallophore physiologique, que nous avons tenté de caractériser. Nous abordons aussi des études cristallographiques préliminaires concernant NikR.

This work increased the value of ferrite process (FP) in three directions: firstly, changed the inferiority of FP on cost by transforming the FP sludge into a catalyst; secondly, used ERFP and elutriation to promote the performance of FP; thirdly, developed Fenton oxidation as a pretreatment step for avoiding the interference from chelating agents. Six ferrite catalysts (MxFe(3-x)O4, M = Cu, Zn, Mn, Ni, Cr or Fe) formed from FP were tested. Experimental results indicate that the Cu-ferrite catalyst with a Cu/Fe ratio of 1/2.5 can completely convert CO to CO2 at an inlet CO concentration of 4000 ppm and a space velocity of 6000 hr-1 were held at 140¢J. The catalytic performance of Cu-ferrite did not reduce even when the concentration of O2 was just 1%. This work proves that the ferrite catalysts have good potential for catalyzing oxidation. For developing FP for effectively treating almost all heavy metal waste liquid, hence an extremely difficult treating target- simulated waste liquid was designed. It contains ten heavy metals - Cd, Pb, Cu, Cr, Zn, Ag, Hg, Ni, Sn and Mn, each at a concentration of 0.002 M. Although conventional FP could not be used to treat the simulated waste liquid completely, the enhanced FP, i.e. ERFP, could be used to satisfy regulatory limits. FeSO4 can be added in the extended stage of ERFP intermittently rather than continuously. The optimum operating parameters in the initial stage are pH = 9 , FeSO4 dosage = 0.2 mol/L, temperature = 90 oC, air supply rate = 3 L/min/L and reaction time = 40 min; in the extended stage, they are intermittent dosing, adding 10 mL 1M-FeSO4 solution per liter waste liquid every 5 min, pH = 9, temperature = 90 oC, air supply rate = 3 L/min/L and reaction time = 80min. Elutriation was conducted to reduce the cost of ERFP and ensure that the sludge met Toxicity Characteristic Leaching Procedure (TCLP) standards. An operating pH from 2.88 to 4 and an elutriation time of 6 h were recommended. Used Fenton oxidation to decompose chelating agent in waste liquid and then treated heavy metal by FP, this research showed that under proper operational conditions Fenton/ ERFP could completely solve the chelating agent interference problem. The best condition for decreasing EDTA using the Fenton method was: pH = 2, ferrous ion initial concentration [Fe2+]0 = 1¡Ñ10-2M, hydrogen peroxide addition rate = 5¡Ñ10-4 mol/min/L and reaction time = 10 min. Lastly, a lot of real waste liquids were treated satisfactorily by applying the results of this study.

No description available.

This thesis describes a study of the remobilisation of heavy metals from sediments by three aminopolycarboxylic acids (APCAs). They are nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid. The investigation is introduced by examining the sources, uses and chemistry of these acids. The introduction also includes a discussion of what is known about the inclusion of heavy metals into sediments and their remobilisation from sediments. Typical concentrations of APCAs in natural waters and sediments have been catalogued from the literature. The advantages and disadvantages of various laboratory techniques employed for the remobilisation of heavy metals by APCAs from sediments are assessed, as is the use of such experiments in quantifying the role of APCAs in the remobilisation of heavy metals from sediments. Sediments from three areas were sampled for this study; they were the Alexandra Canal, Captains Flat and Jenolan Caves in New South Wales, Australia. In each area several sites were sampled. For each site there is a brief description of the catchment geology and hydrology. Selected sediment-associated waters in the areas were analysed for their metal concentrations as well as for ultratrace levels of APCAs employing a method developed in the present study. The waters were analysed for the major ions Ca2+, Mg2+, K+, Na+, Cl-, NO3- and SO42-. The sediments from selected sites in each of the areas were dried and fractionated. The dry total and fine sediments were analysed for their metal content and the latter was found to adequately represent the former in this respect. Water samples from the three areas showed different chemistries and exhibited more subtle differences between sites. In general, the Alexandra Canal waters are saline and alkaline and are a mixture of urban runoff and seawater; the Captains Flat waters are acidic and contain high sulfate from acid mine and tailings drainage; the Jenolan Caves waters are neutral and have the features characteristic of waters draining through limestone. The APCA contamination in all water samples when ranked against other global sites is very low. Although the current APCA levels in the waters appear low, it was concluded that they should be closely monitored so that efforts can be made to minimise the risk of APCAs being hazardous environmental contaminants and also that any remobilisation of heavy metals from sediments by APCAs can be controlled. Agitation and column laboratory-scale experiments were carried out in order to obtain an understanding of the remobilisation of metals by contamination levels of APCAs in water, both as the individual APCAs and as a mixture of APCAs. Complimentary experiments were carried out using a molar excess of APCAs calculated from the metal concentrations obtained by acid digestion (assuming 1:1 metal complex formation). Both types of remobilisation experiments were designed to investigate the role that redox potential (Eh) and concentration of APCAs in natural waters have on the remobilisation of heavy metals from the sediments. The agitation experiments were employed to assess metal remobilisation for the situation where the sediments are disturbed while the column experiments explored metal remobilisation for the case where the sediments are left undisturbed in situ. The major conclusions from the agitation experiments that used fine sediment from the Alexandra Canal were that 100 ppm APCA solutions will remobilise metals from the sediments under oxic conditions but only remobilise infinitesimally small amounts of metal under anoxic conditions. The use of fine sediments for the duplicate agitation experiments was found to give adequate duplication of results. A mixture of APCAs in solution acts similarly to the average of the three individual APCA solutions, showing that there are no antagonistic or synergistic effects likely to occur when they are found together in the environment. It was found that the mmoles of the metals remobilised exceeded the mmoles of the APCAs added when 500.0 mL of 100 ppm APCA solution was used on 50.00 g of sediment. This might be due to APCAs remobilising metals from the sediments in ways other than by complexation. Even though an excess of APCAs was available, metal remobilisation was not complete when the experiments were forced to terminate. During the 14 days of the experiment, only one quarter of the metals liberated from the sediment by HNO3 and 30 % H2O2 digestion were remobilised by the APCAs. Therefore an excess of free APCAs remains in solution. Fine sediments from Alexandra Canal, Captains Flat and Jenolan Caves were employed in the oxic agitation experiments using excess APCAs in solution. These experiments resulted in the following major conclusion: when producing an APCA remobilisation signature for trace and ultratrace metals, the geochemistry of the site is of secondary importance to the source of the contaminating metals. This is a feature of the trace and ultratrace metal speciation in the source rather than their concentration in it. From the different levels of calcium present in the three areas it was found that calcium is unlikely to form stable 1:1 APCA complexes at the pH values employed and is unlikely to compete with the heavy metal remobilisation by APCAs. Total sediments from Alexandra Canal and 100 ppm APCA solutions were employed for the column leaching experiments. From mass, pore water volumes and flow measurements it was shown that the ten mini cores taken from the same site were not true replicates. Despite this, when the sediments have settled and the pore waters removed from the cores, the levels of metal being leached stabilise and may represent a clearer picture of the in situ metal leaching from sediment with time. The levels of metal leached from the cores in 14 days suggest that during this period the cores are essentially anoxic, with the oxygen supplied from the oxic leaching solutions used for inorganic and microbial processes in the sediments. Agitation experiments appeared to yield an adequate picture of what would happen if free APCA solution came in contact with fine sediments suspended in the water column. Column leaching experiments employing total sediment were found to be only of limited value in assessing heavy metal remobilisation from undisturbed sediment. These experiments do not give a reliable assessment of the bioavailability of heavy metals and further testing of the acute and chronic toxicity of the sediments is recommended. APCA solutions that have been used in sediment and soil washing under conditions related to those used in the present study may contain an excess of the free APCAs as well as APCA heavy metal complexes and hence may be toxic to biota.

Submitted by Automação e Estatística (sst@bczm.ufrn.br) on 2018-07-02T20:02:09Z No. of bitstreams: 1 JoaoOctavioMedeirosPires_DISSERT.pdf: 1876528 bytes, checksum: c9a8d7b700e3935fa0560f3a05e33f45 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2018-07-04T14:48:35Z (GMT) No. of bitstreams: 1 JoaoOctavioMedeirosPires_DISSERT.pdf: 1876528 bytes, checksum: c9a8d7b700e3935fa0560f3a05e33f45 (MD5) / Made available in DSpace on 2018-07-04T14:48:35Z (GMT). No. of bitstreams: 1 JoaoOctavioMedeirosPires_DISSERT.pdf: 1876528 bytes, checksum: c9a8d7b700e3935fa0560f3a05e33f45 (MD5) Previous issue date: 2018-04-17 / Compostos de Ce2(MoO4)3/TiO2 (molibdato de cério e dióxido de titânio) com diferentes composições foram preparados pelo método de complexação combinado EDTACitrato e pelo método de dopagem por via úmida. Os materiais obtidos foram caracterizados por difração de raios-X (DRX), microscopia eletrônica de varredura com fonte de emissão de campo (MEV-FEG), espectroscopia de energia dispersiva (EDS) e espectroscopia de reflectância difusa (ERD). O potencial catalítico do material foi avaliado por espectrofotometria, onde foi avaliado a variação da concentração de corantes (Azul Maxilon e Amarelo Erionyl a 10ppm) em um reator com bateladas de 30, 60, 90 e 120 minutos de reação, a 45ºC, pH = 6, com incidência de luz visível e 200mg/L de catalisador. De acordo com os resultados do DRX, foi constatado que os compostos obtidos apresentaram as fases esperadas. Através das imagens do MEV foi possivel observar que houve alteração nos tamanhos e formatos do material base (TiO2) devido a incorporação do molibdato de cério, além da verificação da eficiencia dos métodos ao conferir a homogeneidade da dopagem, constatando ineficiencia no método de dopagem via úmida quando feita a 10%. Os resultados do EDS confirmaram a presença dos elementos que foram utilizados para formação do composto final e apresentaram um desvio de 2,2-3,6% entre a composição teórica e a experimental, justificado pelo método de síntese e de dopagem. Por meio da análise de ERD foi constatado que não houve alteração significativa no bandgap do material base (TiO2) ao introduzir o Ce2(MoO4)3. O TiO2 comercial foi utilizado como base de comparação para os testes de fotocatálise. Para o corante ácido amarelo (Amarelo Erionyl) a fotólise não foi significativa, o material obteve valores de até 51,15% de adsorção e obteve como melhor fotocatalisador o 10 wt% Ce2(MoO4)3/TiO2 obtido por impregnação, alcançando 49% de remoção. Para o corante básico azul (Azul Maxilon) houve fotólise de até 9% em 120 minutos, o mesmo obteve os melhores resultados de adsorção com o material base e degradação quando utilizado com o TiO2 puro tratado no método EDTA-Citrato, atingindo 63,27% e 92,195% respectivamente ao fim de 120 minutos. / Ce2(MoO4)3/TiO2 composites (cerium molybdate and titanium dioxide) with different compositions were prepared by combined complexation method EDTA-Citrate and by the wet doping method. The obtained materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and diffuse reflectance spectroscopy (DRS). The material catalytic potential was evaluated by spectrophotometry, in which the dye concentration variation (Maxilon Blue and Erionyl Yellow at 10ppm) was evaluated in a reactor with 30, 60, 90 and 120 minute batch reaction at 45ºC, pH = 6, with visible light incidence and 200mg / L of catalyst. According to the results of the XRD, it was verified that the obtained compounds presented the expected phases. Through the images of the SEM it was possible to observe that there was a change in sizes and formats of the base material (TiO2) due to the incorporation of the cerium molybdate. It was also verified through SEM that the material was not homogeneous for the wet doping method done with 10%. The EDS results confirmed the presence of elements that were used to form the final compound and presented a deviation of 2.2-3.6% between the theoretical and the experimental composition, justified by the synthesis and doping method. By the ERD analysis, it was certified that there was no significant change in the bandgap of the base material (TiO2) when introducing Ce2(MoO4)3. Commercial TiO2 was used as comparison basis for the photocatalysis tests. For the yellow acid dye (Yellow Erionyl) the photolysis was not significant, the material obtained values of up to 25% of adsorption and obtained as best photocatalyst the 10 wt% Ce2(MoO4)3/TiO2 obtained by impregnation, which caused 49% remotion. For the basic blue dye (Maxilon Blue) there was photolysis of up to 9% in 120 minutes, it obtained the best results of adsorption when the base material was tested and degradation when the pure TiO2 treated by EDTA-Citrate was tested, reaching 63.27% and 92.195% respectively at the end of 120 minutes.