O presente estudo teve como objetivo avaliar a ação das soluções de quitosana, EDTA e ácido cítrico sobre a microdureza da dentina radicular. Utilizaram-se 10 incisivos centrais superiores humanos, os quais tiveram suas coroas seccionadas transversalmente e desprezadas. As raízes foram incluídas em resina acrílica de rápida polimerização e o bloco formado raiz/resina adaptado a máquina de corte. Desprezou-se o primeiro corte transversal da porção cervical e dividiu-se o segundo, em quatro quadrantes. Cada quarto foi destinado à confecção do corpo de prova obtendo-se 4 espécimes para cada raiz, um para cada solução (n=10): G1- EDTA 15%; G2- ácido cítrico; G3- quitosana 0,2% e G4- controle. Os espécimes receberam 50 &mu;L da solução por 5 minutos, sendo em seguida, lavados com água deionizada. Utilizou-se um microdurômetro (dureza Knoop) com carga de 10 g durante 15 segundos. Os resultados mostraram que todas as soluções avaliadas apresentaram capacidade de reduzir a microdureza da dentina radicular de forma semelhante entre si e estatisticamente diferente a do grupo controle (p<0,01). Concluiu-se as soluções de quitosana 0,2%, EDTA 15% e ácido cítrico 10% apresentam efeito semelhante na redução da microdureza dentinária. / The aim of this study was to evaluate the action of solutions: chitosan, EDTA and citric acid on the microhardness of the root dentin. There were used 10 human maxillary central incisors which ones had their crown cross-sectioned and discarded. The roots were embedded in acrylic resin of rapid polymerization and the block formed root/resin suitable by cutting machine. Neglecting the first cross-section of the cervical portion and the second was divided in four quadrants. Each quarter was destined to the confection of the specimen and it was got 4 specimen to each root, one for each solution (n=10): G1- EDTA 15%; G2- citric acid;G3- chitosan 0,2 % and G4- control. The specimen received 50 &mu;L of the solution for 5 minutes, and following up they were washed by deionized water. It was used a microhardness (Knoop hardness) with a load of 10g during 15 seconds. The results showed that all the solutions evaluated presented a capacity to reduce the microhardness of the root dentin in a similar way between them, and statically differ from the control group (p<0,01). It was concluded that chitosan 0,2% EDTA 15% and the citric acid 10% presented a similar effect in the reduction of the dentin microhardness.

Níquel laterítico compõe 70% das reservas disponíveis do metal. A produção de níquel a partir dessas reservas representa 40%, dos quais é possível extrair também cobre e cobalto. Isso ocorre devido ao alto teor de impurezas, principalmente ferro. Com a crescente demanda desses metais, o uso das reservas de lateritas de níquel passou a ser mais profundamente investigado, assim como o desenvolvimento de processos hidrometalúrgicos. Nesse caso, o íon férrico prejudica a recuperação do níquel e do cobalto, uma vez que em trocas iônicas esse metal compete na ocupação dos sítios catiônicos. Em processos de extração por solvente um efeito semelhante é observado. Além disso, durante a eventual precipitação do ferro ocorre a coprecipitação. Assim, para a troca iônica, o íon ferroso pode ser menos prejudicial do que o férrico. O presente trabalho teve por objetivo o estudo do processo de redução do íon férrico em solução aquosa, e também a posterior obtenção de cobalto e níquel por meio de resinas quelantes. Estudou-se o processo de redução do íon férrico e o efeito na adsorção de metais por troca iônica. Os ensaios de redução química do íon férrico em solução foram estudados utilizando ditionito de sódio, metabissulfito de sódio e sulfito de sódio. Os ensaios com os agentes redutores ditionito e metabissulfito de sódio foram feitos em São Paulo, e os ensaios com o sulfito de sódio foram feitos na The University of British Columbia. Os agentes redutores foram adicionados na solução monoelementar de ferro para redução do potencial redox. As variáveis potencial redox, entre 860mV e 240mV; pH, entre 0,5 e 3,5; temperatura, entre 25°C e 60°C; e tempo, entre 30min e 96 horas, foram estudadas em frascos erlenmeyer sob agitação constante. Analisou-se, então, a redução do íon férrico em solução multielementar de níquel laterítico. Nos ensaios de troca iônica, realizados em batelada e em coluna, utilizou-se a resina quelante Lewatit TP 207, de grupo funcional iminodiacetato, e a resina Lewatit TP220, de grupo funcional bis-picolilamina. Três soluções foram estudadas: uma preparada com Fe(III), outra com Fe(II) e a terceira com Fe(III) após o processo de pré-redução. Os ensaios em batelada foram realizados com a utilização de frascos erlenmeyer, sob agitação constante, com 100mL de solução para 1mL de resina. Estudou-se o efeito do pH, entre 0,5 e 3,5; tempo, entre 30min e 480min; e temperatura, entre 25°C e 60°C. Nos ensaios em sistema contínuo, as três soluções foram alimentadas em colunas de vidro preenchidas com resina. A solução foi alimentada com bombas peristálticas a vazão constante. Para eluição das colunas, ácido sulfúrico 1mol.L-1 foi alimentado na coluna com utilização de bomba peristáltica. A segunda parte do trabalho, realizado na The University of British Columbia, foi o estudo do uso de sulfito de sódio no processo de pré-redução. Foram estudadas duas resinas: a Lewatit TP 207, seletiva para cobre; e a Lewatit TP 220, seletiva para níquel e cobalto. O sulfito de sódio foi adicionado na solução para redução do potencial, em frascos, e colocado sob agitação constante. Após reação, as soluções foram colocadas em contato com a resina quelante, e ficaram em agitação. Os ensaios em batelada foram realizados e o efeito do pH estudado entre 0,5 e 3,5. No processo em coluna, a Coluna 1, preenchida com a resina Lewatit TP 207, foi utilizada para remoção do cobre; e a solução de saída foi alimentada na Coluna 2, preenchida com a resina Lewatit TP 220. Para a eluição, foram estudados os ácidos clorídricos e sulfúricos em duas diferentes concentrações, 1mol.L-1 e 2mol.L-1. Hidróxido de sódio foi utilizado para remover o ferro na solução obtida na saída da Coluna 2. A separação do cobalto da solução foi feita utilizando a técnica de extração por solventes (Cyanex 272 20%), estudando o efeito do pH, 4,0 e 5,0, e da temperatura, 25°C e 65°C. Os resultados mostraram que a redução do íon férrico utilizando ditionito de sódio foi de 100% na solução monoelementar e de 70% na multielementar contendo os outros metais. Nos ensaios de troca iônica em batelada, utilizando a resina TP 207, 62% do cobre foi adsorvido na solução após processo de pré-redução. Para solução com Fe(II), a adsorção de cobre foi de 61%; e para solução com Fe(III), 49%. Nos ensaios de troca iônica após pré-redução do ferro com sulfito de sódio, a adsorção do cobre foi de 69% em pH 2,0 pela resina TP 207. A resina TP 220 foi mais seletiva para níquel e cobalto em pH 2,0, em que as adsorções destes metais foram 32,5% e 69%, respectivamente. Nos ensaios em coluna, a Coluna 1 foi utilizada para remoção de cobre, porém houve perda de 17% de níquel e 7% de cobalto. Na alimentação da Coluna 2, verificou-se que 98% do níquel e 84% do cobalto foram adsorvidos. A solução obtida da Coluna 2 teve concentração de 618mg.L-1 de ferro, 13231mg.L-1 de níquel e 179mg.L-1 de cobalto. A remoção de 100% do ferro foi possível em pH 4,0. Para separação do cobalto da solução rica em níquel, utilizou-se a extração por solventes com o Cyanex 272 20% em querosene, no qual 99% do cobalto foi separado da solução a 65°C e pH 5,0, sem perda de níquel. Para estudos futuros, a remoção do cobre no início do processo pode ser explorada com a utilização de outras técnicas, a fim de se evitarem perdas de níquel e cobalto. Outro ponto que pode vir a ser explorado é a máxima utilização das colunas de troca iônica nas mesmas condições deste trabalho - solução com Fe(III), com Fe(II) e após processo de pré-redução - sobretudo em escala piloto, para estudar o efeito do estado de oxidação do ferro em um possível envenenamento da resina. / Nickel laterite ores represent 70% of the available metal reserves. The nickel production from these reserves represents 40%, where it is also possible extract copper and cobalt. It occurs due to the high impurities content, mainly iron. With the growing demand of these metals, the use of nickel laterite reserves became more deeply investigated, as well as hydrometallurgical process development. In this case, the ferric iron difficult the nickel and cobalt recovery, once in ion exchange processes this metal competes in the occupation of the cationic sites. In solvent extraction processes the same effect is observed. Besides that, during the eventual iron precipitation there is a co-precipitation. Therefore, for ion exchange, ferrous iron may be less damaging than ferric iron. The aim of this work was to study the reducing process of ferric iron in aqueous solution, and also the subsequent obtaining of cobalt and nickel through chelating resins. It was studied the reducing process of ferric iron and the effect of it in metals adsorption by ion exchange. Experiments of chemical reduction of ferric iron in solution were studied using sodium dithionite, sodium metabisulfite and sodium sulfite. Experiments with reducing agents sodium dithionite and metabisulfite were performed in São Paulo, and experiments with sodium sulfite were performed in The University of British Columbia. Reducing agents were added in ferric iron mono-elementary solution to decrease the redox potential. The variables potential redox, between 860mV and 240mV; pH, between 0,5 and 3,5; temperature, between 25°C e 60°C; and time, between 30min and 96 hours were studied in erlenmeyer flasks under constant stirring. Then, analyzed ferric iron reduction in multielementary solution of nickel laterite. In ion exchange experiments, performed in batch and column, it was used chelating resin Lewatit TP 207, with iminodiacetate functional group, and resin Lewatit TP 220, with bis-picolylamine functional group. Three solutions were studied: prepared with Fe(III), other with Fe(III) and the third with Fe(III) after pre-reducing process. Experiments in batch system were performed using erlenmeyer flasks, under constant stirring, with 100mL of solution to 1mL of resin. It was studied the effect of pH, between 0,5 and 3,5, time, between 30min and 480min, and temperature, between 25°C e 60°C. In experiments in continuous system, the three solutions were fed in glass columns filled with resin. The solution was fed using peristaltic pumps at constant flow rate. For column elution, sulfuric acid 1mol.L-1 was fed to the column using peristaltic pumps. The second part of this work, performed at The University of British Columbia, was the study of sodium sulfite application at prereducing process. It was studied two resins: Lewatit TP 207, selective for copper, and Lewatit TP 220, selective for nickel and cobalt. Sodium sulfite was added to the solution to decrease the potential, in flasks and it was placed under constant stirring. After reaction, the solution was placed in contact to the chelating resin, which was placed under stirring. Batch experiments were performed, and the effect of pH was studied between 0,5 and 3,5. In column process, the Column 1, filled with Lewatit TP 207, was used for copper removal, and output solution was feed in Column 2, filled with Lewatit TP 220. For the elution, it was studied sulfuric and hydrochloric acids in two different concentrations, 1mol.L-1 e 2mol.L-1. Sodium hydroxide was used for iron removal from solution obtained in Column 2 output. Cobalt separation was performed using solvent extraction technique (Cyanex 272 20%), studying the effect of pH, 4,0 and 5,0, and temperature, 25°C e 65°C. Results shows that ferric iron reduction using sodium dithionite was 100% in mono-elementary solution and 70% in multi-elementary solution with other metals. In ion exchange experiments performed in batch using resin TP 207, 62% of copper was adsorbed by the resin after pre-reducing process. For solution with Fe(II), the copper adsorption was 61%, and for solution with Fe(III), 49%. In ion exchange experiments after pre-reducing process using sodium sulfite, the copper adsorption was 69% at pH 2,0 by the resin TP 207. The resin TP 220 was more selective for nickel and cobalt at pH 2,0, where these metals adsorptions were 32,5% and 69%, respectively. In experiments performed in column, the Column 1 was used for copper removal, however there were losses of nickel (17%) and cobalt (7%). In the feeding of Column 2, it was found that 98% of nickel and 84% of cobalt were adsorbed. Solution obtained in Column 2 had concentration of iron 618mg.L-1, nickel was 13231mg.L-1 and cobalt 179mg.L-1. The iron removal was 100% at pH 4,0. For cobalt separation in nickel-rich solution, it was used the solvent extraction with Cyanex 272 20% with kerosene, where 99% of cobalt was separated from solution at 65°C and pH 5,0, without nickel loss. For future studies, the copper removal in the beginning of the process can be explored using other techniques, in order to avoid nickel and cobalt losses. Another point that can be explored is the maximum use of ion exchange columns in the same conditions of this work - solution with Fe(III), with Fe(II) and after the pre-reducing process - mostly on a pilot scale, to study the effect of iron oxidation state on possible resin poisoning.

Le développement de nouvelles réactions de ligation sélectives, capables de former des liens covalents dans des milieux complexes, est en plein essor depuis une dizaine d’années. Malgré de nombreux efforts, peu de réactions chimiques répondent aux critères de bioorthogonalité et la cycloaddition alcyne-azoture est devenue une réaction bioorthogonale essentielle à la fois pour les chimistes mais aussi pour les biochimistes.Le but de ce travail a été d’améliorer la cinétique de la réaction de cycloaddition alcyne-azoture catalysée par le cuivre, de façon à pouvoir réduire au maximum la quantité de cuivre nécessaire à la réaction et donc son éventuelle toxicité, notamment sur les cellules. Les efforts de recherche menés par de nombreux groupes dans le monde ont porté sur l’augmentation des capacités catalytiques du cuivre (I) par complexation avec des ligands appropriés. Dans un premier temps, à partir de ces résultats, une nouvelle série des ligands du cuivre a été développée au laboratoire et testée dans des milieux aqueux et biologiques. Dans un second temps, nous nous sommes intéressés à une nouvelle stratégie qui consiste à concevoir et synthétiser des azotures chélatants du cuivre. Ces azotures servent à la fois de ligands et de réactifs, et permettent d’accélérer considérablement les vitesses de réaction de la cycloaddition alcyne-azoture en milieu aqueux et en milieu complexe. Ces azotures ont été évalués pour des applications de « fishing » dans lysats cellulaires et sur cellules vivantes. / To improve the kinetic of the CuAAC (Copper Catalyzed Azide-Alkyne Cycloaddition) reaction and to overcome the problems of cytotoxicity of copper which preclude many applications in bioconjugation, recent research efforts have focused on the use of appropriate ligands in combination with copper. Indeed, certain ligands can be added to the reaction solution to bind copper, accelerate reaction, prevent the disproportion and slow down the oxygen reaction. During the first part of my PhD, we have synthesized a new library of ligands bearing amines as specific complexing sites for copper. These libraries of ligands were tested on the CuAAC reaction in diluted aqueous media and in complex media through the use of a fluorogenic assays. Ligands developed in the laboratory were compared with known ligands for the CuAAC, described in the literature. In a second part, we envisioned another strategy to accelerate the kinetics of the CuAAC. For that purpose, we synthesized new azides bearing copper complexation sites by introducing in their structure a copper chelating moiety. Those different azides have been tested in the CuAAC reaction with the help of fluorogenic assays, in diluted aqueous media and in cell lysate. Best chelating azides were tested also in “fishing” experiments of proteins in cell lysate and in cells.

Nesta dissertação, duas resinas reticuladas comerciais (denominadas, AmberliteGT73 e AmberliteIRC748) foram empregadas para suportar partículas de prata. Os grupos tiol da GT73 e ácido iminodiacético da IRC748 presentes nessas resinas foram empregados para a fixação de íons Ag+ a partir de solução aquosa. Posteriormente, os íons Ag+ foram reduzidos pelo emprego de três redutores diferentes em pH alcalino, denominados hidrazina, hidroxilamina e formaldeído (pH &#61504; 12). A morfologia e a impregnação de prata dos materiais binários assim obtidos foram avaliadas por meio de microscópio eletrônico de varredura equipado com detector de elétrons retro-espalhados (SEM-BSE). O detector de espectrometria de energia dispersiva de raios-X (EDAX) acoplado ao SEM permitiu a observação de partículas de prata. Os espectros de raios-X revelaram a presença do metal nas superfícies interna e externa das microesferas dos compósitos. A quantidade de prata incorporada foi determinada pelo método titulométrico, empregando solução padrão de tiocianato de potássio. As características antibactericidas dos compósitos foram avaliadas em colunas contendo pérolas de resina por onde foram percoladas suspensões da bactéria Escherichia coli auxotrópica AB1157 (tipo selvagem) nas concentrações de 103 a 107 células/mL. A avaliação biocida mostrou que estes materiais foram completamente bactericidas, sendo efetivos na eliminação da bactéria em poucos minutos. Esta ação biocida foi atribuída à combinação da atuação da prata e dos grupos funcionais das resinas / In this work, two different commercial cross-linked resins (namely, Amberlite&#61666; GT73 and Amberlite&#61666;IRC748) were employed for anchoring silver. The SH and the N(CH2COOH)2 groups, respectively present on these resins, were used for the Ag+ chelation from aqueous solution. The Ag+ ions were reduced by employing three different reductants, namely hydrazine, hydroxylamine and formaldehyde (under alkaline pH). The produced composites were characterized by thermogravimetry (TG-DTG) and scanning electron microscopy equipped with backscattered scanning electron detector (SEM-BSE). Energy dispersive X-ray spectroscopy (EDS) coupled to SEM allowed the observation of submicron particles of silver and chemical microanalysis of emitted X-rays revealed the presence of metal on the internal and external surfaces of the composite microspheres. The amount of incorporated silver was determined by titration. The antibacterial activity of the silver/resin composites were determined towards 103 to 107 cells/mL dilutions of the auxotrophic AB1157 Escherichia coli strain, showing that the networks containing anchored submicron silver particles were completely bactericidal within a few minutes due to the combined action of silver and functional groups of the resins

<p>Skoghalls Bruk fick i juni 2005 tillstånd av miljödomstolen att öka kartongproduktionen från 665 000 till 800 000 ton kartong per år. Villkoren för tillståndet var att under en prövotidsperiod bl.a. utreda möjligheten att minska utsläpp till omkringliggande vatten.</p><p>Syftet med examensarbetet var att kartlägga Skoghalls Bruks avloppssystem med avseende på komplexbildarna EDTA (etylendiamintetraättiksyra) och DTPA (dietylentriaminpentaättiksyra), kväve samt fosfor.</p><p>Dessutom genomfördes nedbrytningsförsök i luftade dammar i laboratorieskala.</p><p>För att få en klarare bild av nedbrytningen i Skoghalls Bruks luftade damm gjordes även en molekylviktsfraktionering på inkommande och utgående avloppsvatten.</p><p>Komplexbildare används inom pappers- och massaindustrin för sin förmåga att binda till sig metalljoner som kan vara skadliga i processen. Metalljoner katalyserar nedbrytningen av väteperoxid i blekningen och påskyndar bildandet av aldehyder i kartongen vilket kan leda till lukt- och smakpåverkan.</p><p>EDTA och DTPA anses vara stabila ämnen, vilket innebär att de är biologiskt svårnedbrytbara. Under den litteraturstudie som genomfördes fanns motsägande uppgifter angående nedbrytningen av komplexbildare, där vissa menade att de genomgår biologisk nedbrytning, men att det sker mycket långsamt. Andra påstod att komplexbildare inte bryts ner överhuvudtaget.</p><p>Komplexbildare kan elimineras genom fotokemisk oxidativ nedbrytning. Då EDTA och DTPA bildar komplex med Fe3+ blir de fotokemiskt labila och oxideras till mindre föreningar vid belysning med ultraviolett ljus. Sammanfattningsvis gav litteraturstudien att det mest effektiva sättet att minska komplexbildare i avloppsvatten innan det släpps till recipienten är att UV-bestråla vid optimala förhållanden, dvs. rätt pH och eventuellt tillsats av Fe3+ om det behövs.</p><p>Provtagning av avloppsvatten i Skoghalls Bruks reningsanläggning gjordes under 6 veckor för att kartlägga utsläppen och de olika delströmmarnas bidrag.</p><p>Nedbrytningsförsök genomfördes i två luftade dammar i laboratorieskala. För att studera temperaturens inverkan konstruerades en sommar- och en vinterdamm med temperaturerna 27 respektive 16°C. Efter referensförsöket, som gjordes för att se eventuella skillnader mellan försöken, undersöktes inverkan av ultraviolett ljus på nedbrytningen av komplexbildare. Sedan tillsattes Fe3+ i form av järnklorid i ett försök att öka den fotokemiska nedbrytningen. Alla försök pågick under två veckor vardera.</p><p>I syfte att undersöka partikelstorleksfördelningen före och efter nedbrytning i Skoghalls Bruks luftade damm gjordes en molekylviktsfraktionering. Inkommande och utgående avloppsvatten från dammen ultrafiltrerades och analyserades med avseende på COD (Chemical Oxygen Demand), komplexbildare, kväve och fosfor.</p><p>Kartläggningen visade att EDTA bröts ner effektivt i reningsanläggningen medan nedbrytningen av DTPA var obetydlig. EDTA reducerades med 88 % över den luftade dammen.</p><p>Avlopp från kartongmaskinerna samt CTMP-fabriken var de avlopp som innehöll mest EDTA. Största mängden DTPA återfanns i blekerifiltratet och i KM 8:s avlopp.</p><p>Skoghalls Bruk släppte ut komplexbildare motsvarande 0,188 kg/ton kartong, i form av 100 % syra i obunden form, under karteringsperioden vilket var klart lägre än gränsvärdet som är 1,6 kg 100 % syra/ton kartong.</p><p>Kväve reducerades med 67 % över den luftade dammen. Det nuvarande gränsvärdet för kväveutsläpp till recipient är 500 kg/dygn, men ett av målen med prövotidsutredningen är att minska utsläppen till 300 kg/dygn. Enligt resultaten från karteringsperioden var kväveutsläppet 204 kg/dygn vilket uppfyller målet för prövotidsutredningen. Av det totala kväveutsläppet kom 39 kg/dygn från komplexbildare. Utsläppet av kväve från mixeriavloppet var 56 kg/dygn till recipient vilket var klart högre än förväntat.</p><p>Den totala fosforreduceringen över reningsanläggningen var 78 %. Utsläppet av fosfor till recipient var 19 kg/dygn vilket är klart lägre än gränsvärdet som är 50 kg/dygn.</p><p>På grund av komplexbildaranalysens mätosäkerhet var det svårt att få entydiga resultat från laboratorieförsöken. Det fastställdes dock att DTPA var svårare att bryta ner än EDTA och att järntillsats i kombination med ultraviolett ljus gav en positiv effekt på nedbrytningen av båda komplexbildarna. Även nedbrytningen av COD, kväve och fosfor ökade vid järntillsats.</p><p>Att DTPA är svårare att bryta ner än EDTA framkom även av resultaten från molekylviktsfraktioneringen. Det visade sig också att EDTA och DTPA inte är helt vattenlösliga utan kan binda till fast material. Största delen av komplexbildarna fanns dock i fraktionen med partiklar med molekylvikt mindre än 1 kDa. Kväve och fosfor fanns i de låg- och högmolekylära fraktionerna.</p> / <p>In June of 2005 Skoghall Mill got permission from the Environmental Court to increase their production of board from 665 000 tons to 800 000 tons per year. The condition for the permission was to, during a trial period, investigate the possibility to decrease the emissions to the surrounding water. The purpose of this master thesis is to do a mapping of Skoghall Mill’s waste water treatment system regarding the chelating agents EDTA (ethylenediaminetetraacetic acid) and DTPA (diethylenetriaminepentaacetic acid), nitrogen and phosphor.</p><p>Also degradation-trials were made with aerated lagoons in laboratory-scale.</p><p>To get a more complete view of the degradation in Skoghalls Mills aerated lagoon a molecular weight fractionation of the incoming and the outgoing water was made.</p><p>Chelating agents are used in the pulp- and paper industry due to its ability to bind metal-ions which are hazardous for the process. The metal-ions catalyze the decomposition of hydrogen peroxide in the bleaching process and the forming of aldehydes in the board which can lead to problems with taste and odour.</p><p>EDTA and DTPA are regarded to be very stable, which means that they are hard to degrade biologically. There was contradictory information about the degradation of chelating agents during the literature survey. Some say that chelating agents are degraded biologically but very slowly. Others say that they don’t degrade at all.</p><p>Chelating agents can be eliminated through photochemical oxidative degradation. When EDTA and DTPA form complexes with Fe3+ they become photolabile and oxidize to smaller compounds at illumination with ultraviolet light. To sum up the literature survey, the most efficient way to reduce chelating agents in sewage water before discharge to receiving waters, is UV treatment at optimal conditions i.e., at the right pH and with addition of Fe3+ if necessary.</p><p>The sampling of the waste water in Skoghalls waste water treatment plant was made during 6 weeks to map the emissions and the contribution of the different sub-streams.</p><p>The degradation-trials were made in two aerated lagoons in laboratory-scale. To study the influence of temperature a summer- and a winter-lagoon were made and the temperatures were sat to, respectively, 27 and 16°C. After the reference-trial, which was made to determine possible differences between the trials, the influence of ultraviolet light on degradation of chelating agents were investigated. In an attempt to enhance the photochemical degradation, Fe3+ in the form of ferric chloride was then added. All trials went on for two weeks each.</p><p>In order to investigate the particle size distribution, before and after degradation in Skoghall Mill’s aerated lagoon, a molecule weight fractionation was made. Incoming and outgoing sewage water from the lagoon was ultra-filtrated and analyzed regarding COD (Chemical Oxygen Demand), chelating agents, nitrogen and phosphor.</p><p>The mapping showed that EDTA was efficiently degraded in the waste water treatment plant, while degradation of DTPA was insignificant. EDTA was reduced by 88 % trough the aerated lagoon.</p><p>Waste water from the board machines and the CTMP-plant contained the largest amount EDTA. DTPA was recovered mostly in the bleaching filtrate and KM 8’s waste water.</p><p>The emission of chelating agents, counted as acid, from Skoghall Mill during the period of the mapping was 0,188 kg/ton board which is well below the emission limit value of 1,6 kg/ton board.</p><p>Nitrogen was reduced by 67 % through the aerated lagoon. The present emission limit value for nitrogen is 500 kg/day. According to the results from the period of the mapping the emission of nitrogen was 204 kg/day which is well below the emission limit value. The contribution of chelating agents to the nitrogen emission was 39 kg/day. 56 kg nitrogen /day were recovered in the waste water from the causticizing area, which is remarkably higher than expected.</p><p>The total reduction of phosphor through the waste water treatment plant was 78 %. The emission of phosphor to receiving waters was 19 kg/day which is well below the emission limit value of 50 kg/day.</p><p>Due to the insecurity in measurement of chelating agents, it was difficult to retain unambiguous results from the laboratory-trials. However it was determined that DTPA was more difficult to degrade than EDTA and that a combination of ultraviolet light and addition of ferric iron had a favourable effect on the degradation of both chelating agents. Also the degradation of COD, nitrogen and phosphor increased when ferric iron was added.</p><p>The fact that DTPA are more difficult to degrade than EDTA was also stated in molecular weight fractionation. It was also shown that EDTA and DTPA weren’t totally water-soluble but can bind to solid material. The largest amount of chelating agents was recovered in the fraction with particles whose molecular weight is less than 1 kDa. Nitrogen and phosphor were recovered in the low- and high-molecular fractions.</p>

Skoghalls Bruk fick i juni 2005 tillstånd av miljödomstolen att öka kartongproduktionen från 665 000 till 800 000 ton kartong per år. Villkoren för tillståndet var att under en prövotidsperiod bl.a. utreda möjligheten att minska utsläpp till omkringliggande vatten. Syftet med examensarbetet var att kartlägga Skoghalls Bruks avloppssystem med avseende på komplexbildarna EDTA (etylendiamintetraättiksyra) och DTPA (dietylentriaminpentaättiksyra), kväve samt fosfor. Dessutom genomfördes nedbrytningsförsök i luftade dammar i laboratorieskala. För att få en klarare bild av nedbrytningen i Skoghalls Bruks luftade damm gjordes även en molekylviktsfraktionering på inkommande och utgående avloppsvatten. Komplexbildare används inom pappers- och massaindustrin för sin förmåga att binda till sig metalljoner som kan vara skadliga i processen. Metalljoner katalyserar nedbrytningen av väteperoxid i blekningen och påskyndar bildandet av aldehyder i kartongen vilket kan leda till lukt- och smakpåverkan. EDTA och DTPA anses vara stabila ämnen, vilket innebär att de är biologiskt svårnedbrytbara. Under den litteraturstudie som genomfördes fanns motsägande uppgifter angående nedbrytningen av komplexbildare, där vissa menade att de genomgår biologisk nedbrytning, men att det sker mycket långsamt. Andra påstod att komplexbildare inte bryts ner överhuvudtaget. Komplexbildare kan elimineras genom fotokemisk oxidativ nedbrytning. Då EDTA och DTPA bildar komplex med Fe3+ blir de fotokemiskt labila och oxideras till mindre föreningar vid belysning med ultraviolett ljus. Sammanfattningsvis gav litteraturstudien att det mest effektiva sättet att minska komplexbildare i avloppsvatten innan det släpps till recipienten är att UV-bestråla vid optimala förhållanden, dvs. rätt pH och eventuellt tillsats av Fe3+ om det behövs. Provtagning av avloppsvatten i Skoghalls Bruks reningsanläggning gjordes under 6 veckor för att kartlägga utsläppen och de olika delströmmarnas bidrag. Nedbrytningsförsök genomfördes i två luftade dammar i laboratorieskala. För att studera temperaturens inverkan konstruerades en sommar- och en vinterdamm med temperaturerna 27 respektive 16°C. Efter referensförsöket, som gjordes för att se eventuella skillnader mellan försöken, undersöktes inverkan av ultraviolett ljus på nedbrytningen av komplexbildare. Sedan tillsattes Fe3+ i form av järnklorid i ett försök att öka den fotokemiska nedbrytningen. Alla försök pågick under två veckor vardera. I syfte att undersöka partikelstorleksfördelningen före och efter nedbrytning i Skoghalls Bruks luftade damm gjordes en molekylviktsfraktionering. Inkommande och utgående avloppsvatten från dammen ultrafiltrerades och analyserades med avseende på COD (Chemical Oxygen Demand), komplexbildare, kväve och fosfor. Kartläggningen visade att EDTA bröts ner effektivt i reningsanläggningen medan nedbrytningen av DTPA var obetydlig. EDTA reducerades med 88 % över den luftade dammen. Avlopp från kartongmaskinerna samt CTMP-fabriken var de avlopp som innehöll mest EDTA. Största mängden DTPA återfanns i blekerifiltratet och i KM 8:s avlopp. Skoghalls Bruk släppte ut komplexbildare motsvarande 0,188 kg/ton kartong, i form av 100 % syra i obunden form, under karteringsperioden vilket var klart lägre än gränsvärdet som är 1,6 kg 100 % syra/ton kartong. Kväve reducerades med 67 % över den luftade dammen. Det nuvarande gränsvärdet för kväveutsläpp till recipient är 500 kg/dygn, men ett av målen med prövotidsutredningen är att minska utsläppen till 300 kg/dygn. Enligt resultaten från karteringsperioden var kväveutsläppet 204 kg/dygn vilket uppfyller målet för prövotidsutredningen. Av det totala kväveutsläppet kom 39 kg/dygn från komplexbildare. Utsläppet av kväve från mixeriavloppet var 56 kg/dygn till recipient vilket var klart högre än förväntat. Den totala fosforreduceringen över reningsanläggningen var 78 %. Utsläppet av fosfor till recipient var 19 kg/dygn vilket är klart lägre än gränsvärdet som är 50 kg/dygn. På grund av komplexbildaranalysens mätosäkerhet var det svårt att få entydiga resultat från laboratorieförsöken. Det fastställdes dock att DTPA var svårare att bryta ner än EDTA och att järntillsats i kombination med ultraviolett ljus gav en positiv effekt på nedbrytningen av båda komplexbildarna. Även nedbrytningen av COD, kväve och fosfor ökade vid järntillsats. Att DTPA är svårare att bryta ner än EDTA framkom även av resultaten från molekylviktsfraktioneringen. Det visade sig också att EDTA och DTPA inte är helt vattenlösliga utan kan binda till fast material. Största delen av komplexbildarna fanns dock i fraktionen med partiklar med molekylvikt mindre än 1 kDa. Kväve och fosfor fanns i de låg- och högmolekylära fraktionerna. / In June of 2005 Skoghall Mill got permission from the Environmental Court to increase their production of board from 665 000 tons to 800 000 tons per year. The condition for the permission was to, during a trial period, investigate the possibility to decrease the emissions to the surrounding water. The purpose of this master thesis is to do a mapping of Skoghall Mill’s waste water treatment system regarding the chelating agents EDTA (ethylenediaminetetraacetic acid) and DTPA (diethylenetriaminepentaacetic acid), nitrogen and phosphor. Also degradation-trials were made with aerated lagoons in laboratory-scale. To get a more complete view of the degradation in Skoghalls Mills aerated lagoon a molecular weight fractionation of the incoming and the outgoing water was made. Chelating agents are used in the pulp- and paper industry due to its ability to bind metal-ions which are hazardous for the process. The metal-ions catalyze the decomposition of hydrogen peroxide in the bleaching process and the forming of aldehydes in the board which can lead to problems with taste and odour. EDTA and DTPA are regarded to be very stable, which means that they are hard to degrade biologically. There was contradictory information about the degradation of chelating agents during the literature survey. Some say that chelating agents are degraded biologically but very slowly. Others say that they don’t degrade at all. Chelating agents can be eliminated through photochemical oxidative degradation. When EDTA and DTPA form complexes with Fe3+ they become photolabile and oxidize to smaller compounds at illumination with ultraviolet light. To sum up the literature survey, the most efficient way to reduce chelating agents in sewage water before discharge to receiving waters, is UV treatment at optimal conditions i.e., at the right pH and with addition of Fe3+ if necessary. The sampling of the waste water in Skoghalls waste water treatment plant was made during 6 weeks to map the emissions and the contribution of the different sub-streams. The degradation-trials were made in two aerated lagoons in laboratory-scale. To study the influence of temperature a summer- and a winter-lagoon were made and the temperatures were sat to, respectively, 27 and 16°C. After the reference-trial, which was made to determine possible differences between the trials, the influence of ultraviolet light on degradation of chelating agents were investigated. In an attempt to enhance the photochemical degradation, Fe3+ in the form of ferric chloride was then added. All trials went on for two weeks each. In order to investigate the particle size distribution, before and after degradation in Skoghall Mill’s aerated lagoon, a molecule weight fractionation was made. Incoming and outgoing sewage water from the lagoon was ultra-filtrated and analyzed regarding COD (Chemical Oxygen Demand), chelating agents, nitrogen and phosphor. The mapping showed that EDTA was efficiently degraded in the waste water treatment plant, while degradation of DTPA was insignificant. EDTA was reduced by 88 % trough the aerated lagoon. Waste water from the board machines and the CTMP-plant contained the largest amount EDTA. DTPA was recovered mostly in the bleaching filtrate and KM 8’s waste water. The emission of chelating agents, counted as acid, from Skoghall Mill during the period of the mapping was 0,188 kg/ton board which is well below the emission limit value of 1,6 kg/ton board. Nitrogen was reduced by 67 % through the aerated lagoon. The present emission limit value for nitrogen is 500 kg/day. According to the results from the period of the mapping the emission of nitrogen was 204 kg/day which is well below the emission limit value. The contribution of chelating agents to the nitrogen emission was 39 kg/day. 56 kg nitrogen /day were recovered in the waste water from the causticizing area, which is remarkably higher than expected. The total reduction of phosphor through the waste water treatment plant was 78 %. The emission of phosphor to receiving waters was 19 kg/day which is well below the emission limit value of 50 kg/day. Due to the insecurity in measurement of chelating agents, it was difficult to retain unambiguous results from the laboratory-trials. However it was determined that DTPA was more difficult to degrade than EDTA and that a combination of ultraviolet light and addition of ferric iron had a favourable effect on the degradation of both chelating agents. Also the degradation of COD, nitrogen and phosphor increased when ferric iron was added. The fact that DTPA are more difficult to degrade than EDTA was also stated in molecular weight fractionation. It was also shown that EDTA and DTPA weren’t totally water-soluble but can bind to solid material. The largest amount of chelating agents was recovered in the fraction with particles whose molecular weight is less than 1 kDa. Nitrogen and phosphor were recovered in the low- and high-molecular fractions.

The novel chelating ligand, Me[NOON]H2 (N,N'-((ethane-1,2-diylbis(oxy))-bis(ethane-2,1-diyl))- bis(2,6-dimethylaniline)), have been synthesized successfully and characterized by NMR. The lithium complexes of the aryl diamide ligand have also been synthesized by n-BuLi react with neutral ligand, Me[NOON]H2. And the lithium complexes is a ether adduct according to the 1H NMR. The lithium complex, Me[NOON]Li2(OEt2) react with Ti(OiPr)4 and TiCl4(THF)2 to form the NOON titanium alkoxide and dichloride complexes respectively, and they have been characterized by 1H NMR and X-ray diffraction. These NOON titanium complexes are expected to be a catalyst for the ring opening polymerization of lactide or caprolactone in the future. The tantalum complexes of diphenolate phosphine ligands have been synthesized and characterized successfully by NMR, X-ray diffraction, and elemental analysis. The tantalum complexes, [tBuOPO]2TaX (X=Me, Et, H) is produced by the reaction of [tBuOPO]2TaCl with Grignard reagent (MeMgBr and EtMgCl) and superhydride(LiHBEt3). These tantalum complexes will be applied in dinitrogen activation in the future work.

Amine bis(phenolate) ligands synthesis can be easily prepared by the reaction of a substituted 2-(bromomethyl)phenol, a substituted phenol, potassium carbonate, triethylamine and the appropriate amine to form the desired compounds in high yields and purities. A series of amine bis(phenolate) ligand precursors with group 4 metals and aluminum complexes have been prepared, characterized by single-crystal X-ray diffraction, and tested for ring opening polymerisation of £`-caprolactone. Group 4 metals complexes which are shown to be active catalysts for the ROP of £`-caprolactone with excellent conversions and polydispersities. All aluminum compounds as four-coordinate aluminum methyl complexes show excellent catalytic activity toward the ring opening polymerization of £`-caprolactone in the presence of benzyl alcohol. And amine bis(phenolate)s ligand ([tert-ButylONO]2-) bond cleavage with zirconium and hafnium complexes that have been prepared, characterized by single-crystal X-ray diffraction. Another zirconium complexes of dianionic amine bis(phenolate) ligands have been synthesized, their X-ray structures solved, and their activity as 1-hexene polymerization catalysts study. Upon treatment with B(C6F5)3, a series of pentacoordinate [ONO]Zr(CH2Ph)2 complex, having no extra donor group, shows only poor activity as a polymerization catalyst. Final reaction of diamine-bis(phenol) ligands containing a mixture of [i-PropylONO]Ti(OiPr)2 in dry THF under RT without exclusion of air and moisture gives {[i-PropylONO]TiO}3 (characterised by X-ray crystallography) is hydrolysed with H2O.

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.

The constitutive studies of this thesis were achieved and presented in three parts. In the first part, the effects of solid state synthesis process parameters and the impurity content of primary calcium precursor on the cement-type hydration efficiency for the conversion of &alpha / -tricalcium phosphate (Ca3(PO4)2 or &alpha / -TCP) into hydroxyapatite (Ca10-xHPO4(PO4)6-x(OH)2-x x = 0&ndash / 1, or HAp) have been investigated (at 37&deg / C). &alpha / -TCP was synthesized by thermal processing of stoichiometric amounts of calcium carbonate (CaCO3) and monetite (CaHPO4) at 1150&ndash / 1350&deg / C for 2 h. Three commercial grade CaCO3 powders of different purity were used as starting materials for the synthesis process and the resultant &alpha / -TCP products for all synthesis routes were compared in terms of the material properties and their reactivities. In the second part of the studies, &alpha / -TCP and chitosan fiber (CF) composites were prepared as injectable bone cement systems which have a potential to degrade in time to be replaced by the natural bone tissue. &alpha / -TCP/CF composites were prepared in different compositions and the effect of CF addition on cement properties were examined by mechanical and injectability tests as well as microstructural and phase analysis studies. In the third part of the studies, metal chelating property of CFs was used on development of controlled zinc release systems that can be applied in local zinc deficiency therapies of bone tissue. For this purpose, CF scaffolds were prepared by wet-spinning technique and appropriate amount of zinc was loaded to these scaffolds in regard to the zinc content of a healthy human bone tissue. Zinc release studies were performed on calcium phosphate (CaP) covered and non-covered CF scaffolds and zinc ion concentrations of the release solutions were determined by ICP-MS.