Made available in DSpace on 2014-12-17T15:42:28Z (GMT). No. of bitstreams: 1 MonicaRO_TESE.pdf: 4155777 bytes, checksum: 6bff63b5cb0f37e64dfe6fcb144dae79 (MD5) Previous issue date: 2014-01-23 / The environmental impact due to the improper disposal of metal-bearing industrial effluents imposes the need of wastewater treatment, since heavy metals are nonbiodegradable and hazardous substances that may cause undesirable effects to humans and the environment. The use of microemulsion systems for the extraction of metal ions from wastewaters is effective when it occurs in a Winsor II (WII) domain, where a microemulsion phase is in equilibrium with an aqueous phase in excess. However, the microemulsion phase formed in this system has a higher amount of active matter when compared to a WIII system (microemulsion in equilibrium with aqueous and oil phases both in excess). This was the reason to develop a comparative study to evaluate the efficiency of two-phases and three-phases microemulsion systems (WII and WIII) in the extraction of Cu+2 and Ni+2 from aqueous solutions. The systems were composed by: saponified coconut oil (SCO) as surfactant, n-Butanol as cosurfactant, kerosene as oil phase, and synthetic solutions of CuSO4.5H2O and NiSO4.6H2O, with 2 wt.% NaCl, as aqueous phase. Pseudoternary phase diagrams were obtained and the systems were characterized by using surface tension measurements, particle size determination and scanning electron microscopy (SEM). The concentrations of metal ions before and after extraction were determined by atomic absorption spectrometry. The extraction study of Cu+2 and Ni+2 in the WIII domain contributed to a better understanding of microemulsion extraction, elucidating the various behaviors presented in the literature for these systems. Furthermore, since WIII systems presented high extraction efficiencies, similar to the ones presented by Winsor II systems, they represented an economic and technological advantage in heavy metal extraction due to a small amount of surfactant and cosurfactant used in the process and also due to the formation of a reduced volume of aqueous phase, with high concentration of metal. Considering the reextraction process, it was observed that WIII system is more effective because it is performed in the oil phase, unlike reextraction in WII, which is performed in the aqueous phase. The presence of the metalsurfactant complex in the oil phase makes possible to regenerate only the surfactant present in the organic phase, and not all the surfactant in the process, as in WII system. This fact allows the reuse of the microemulsion phase in a new extraction process, reducing the costs with surfactant regeneration / O impacto ambiental gerado pelo descarte de efluentes industriais carregados de metais pesados imp?e a necessidade do tratamento desses rejeitos, uma vez que s?o t?xicos e n?o biodegrad?veis, podendo causar s?rios danos ? popula??o e ao meio ambiente. O processo de extra??o de c?tions met?licos utilizando microemuls?es ? eficaz quando acontece em WII, onde a fase microemulsionada encontra-se em equil?brio com uma fase aquosa em excesso. No entanto, a microemuls?o formada nesse sistema possui uma maior quantidade de mat?ria ativa quando comparada ao equil?brio de WIII (microemuls?o em equil?brio com fases aquosa e oleosa, ambas em excesso), ainda pouco estudado, motivando, assim, o desenvolvimento de um estudo comparativo da efici?ncia de extra??o dos ?ons Cu2+ e Ni2+ por sistemas microemulsionados bif?sicos e trif?sicos (WII e WIII). Os constituintes utilizados nos sistemas de extra??o foram: ?leo de coco saponificado - OCS (Tensoativo), n- Butanol (Cotensoativo), querosene (Fase Oleosa) e solu??es sint?ticas de CuSO4.5H2O e NiSO4.6H2O com NaCl 2% (fases aquosas). Foram obtidos os diagramas de fases pseudotern?rios e os sistemas microemulsionados foram caracterizados atrav?s das t?cnicas de tens?o superficial, tamanho de part?culas e microscopia eletr?nica de varredura (MEV). A concentra??o dos ?ons foi determinada por espectrometria de absor??o at?mica. O estudo da extra??o dos c?tions met?licos Cu2+ e Ni2+ na regi?o de WIII contribuiu para um melhor entendimento dos processos de extra??o por microemuls?o, elucidando os v?rios comportamentos apresentados na literatura para esses sistemas. Al?m disso, uma vez que houve uma alta efici?ncia de extra??o, similar aos sistemas de Winsor II, o sistema trif?sico (WIII), por apresentar uma menor quantidade de tensoativo e cotensoativo, e um menor volume de fase aquosa ap?s a extra??o, levou a uma maior concentra??o do metal, representando uma vantagem econ?mica e tecnol?gica do processo. Assim, a extra??o em sistema trif?sico ? vi?vel e, apesar dos percentuais de extra??o em WII e WIII serem semelhantes, o sistema de WIII leva a uma maior concentra??o do metal na fase extrato. O presente trabalho mostrou, ainda, que a etapa de reextra??o para os sistemas em WIII ? mais eficaz pois, diferentemente da extra??o em Winsor II, ela ? realizada na fase oleosa, onde est? depositado o complexo metal/tensoativo, regenerando somente o tensoativo que complexa com o metal na fase org?nica, e n?o todo o tensoativo utilizado, como ? o caso do equil?brio em Winsor II. Este fato viabiliza a reutiliza??o da fase microemuls?o no processo de extra??o, diminuindo os custos de regenera??o do tensoativo

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-02-01T21:27:07Z No. of bitstreams: 1 EmilyCintiaTossiDeAraujoCosta_TESE.pdf: 2216846 bytes, checksum: 5f38e382d8ae3c1bfe9f3db58b62a672 (MD5) / Approved for entry into archive by Elisangela Moura (lilaalves@gmail.com) on 2016-02-02T21:24:40Z (GMT) No. of bitstreams: 1 EmilyCintiaTossiDeAraujoCosta_TESE.pdf: 2216846 bytes, checksum: 5f38e382d8ae3c1bfe9f3db58b62a672 (MD5) / Made available in DSpace on 2016-02-02T21:24:40Z (GMT). No. of bitstreams: 1 EmilyCintiaTossiDeAraujoCosta_TESE.pdf: 2216846 bytes, checksum: 5f38e382d8ae3c1bfe9f3db58b62a672 (MD5) Previous issue date: 2013-09-23 / A contamina??o de ?guas naturais por metais tornou-se assunto de interesse p?blico mundial por serem considerados biocumulativos. A determina??o e o monitoramento de contaminantes met?licos em ?guas ? uma tarefa que deve ser cont?nua e por isto a import?ncia do desenvolvimento, modifica??o e otimiza??o de metodologias anal?ticas capazes de realizar a determina??o dos v?rios contaminantes met?licos em ambientes naturais, pois em muitos casos, a instrumenta??o dispon?vel n?o apresenta sensibilidade anal?tica suficiente para a determina??o de tra?os. Neste estudo, um m?todo de extra??o e pr?-concentra??o utilizando um sistema microemulsionado, no equil?brio de Winsor II foi testado e otimizado para a determina??o dos metais Co, Cd, Pb, Tl, Cu e Ni por Espectrometria de absor??o at?mica de alta resolu??o com fonte cont?nua e atomiza??o em forno de grafite e chama (HR-CS AAS). A otimiza??o do programa de temperatura para o forno de grafite foi realizada atrav?s de curvas de pir?lise e atomiza??o para cada analito sem e com o uso de diferentes modificadores qu?micos. Cd e Pb tiveram condi??es ?timas com modificador permanente Ru, pir?lise em 700?C e atomiza??o em 1700?C, para Tl solu??o Pd/Mg foi o melhor modificador, temperaturas 600?C e 1700?C de pir?lise e atomiza??o, respectivamente e para o Co pir?lise em 800?C e atomiza??o ? 2400?C sem uso de modificador qu?mico, por?m W foi empregado como modificador permanente a fim de se prolongar o tempo de vida ?til do forno. Cu e Ni foram analisados na chama ap?s pr?-concentra??o. Avaliou-se tamb?m fatores que influenciam a efici?ncia de extra??o, atrav?s do efeito salting out. Como compromisso, 6 g L-1 de Na e 1% de HNO3 (v/v) foi definido. Para determina??o do ponto ?timo de extra??o, um planejamento centroide-simplex foi aplicado, sendo escolhido como compromisso as seguintes propor??es: 70% fase aquosa, 10% fase ?leo e 20% Cotensoativo/Tensoativo (C/T = 4). Ap?s extra??o, os metais foram determinados e as Figuras de m?rito obtidas para o m?todo proposto foi: 0,1 a 10 ?g L-1 de faixa linear, LOD 0,094, 0,011, 0,057 e 0,050 ?g L-1 para Pb, Cd, Tl e Co, respectivamente. Testes de adi??o e recupera??o na amostra certificada apresentaram valores de recupera??o ap?s extra??o de 105 e 101% para Pb e Cd, respectivamente, e nas amostras fortificadas a recupera??o para os analitos ficou entre 107 e 108% comprovando que o m?todo proposto pode ser utilizado na extra??o, possibilitou a separa??o dos metais de matrizes complexas, e ainda com bom fator de pr?-concentra??o. / The determination and monitoring of metallic contaminants in water is a task that must be continuous, leading to the importance of the development, modification and optimization of analytical methodologies capab le of determining the various metal contaminants in natural environments, because, in many cases, the ava ilable instrumentation does not provide enough sensibility for the determination of trace values . In this study, a method of extraction and pre- concentration using a microemulsion system with in the Winsor II equilibrium was tested and optimized for the determination of Co, Cd, P b, Tl, Cu and Ni through the technique of high- resolution atomic absorption spectrometry using a continuum source (HR-CS AAS). The optimization of the temperature program for the graphite furnace (HR-CS AAS GF) was performed through the pyrolysis and atomization curves for the analytes Cd, Pb, Co and Tl with and without the use of different chemical modifiers. Cu and Ni we re analyzed by flame atomization (HR-CS F AAS) after pre-concentr ation, having the sample introduction system optimized for the realization of discrete sampling. Salinity and pH levels were also analyzed as influencing factors in the efficiency of the extraction. As final numbers, 6 g L -1 of Na (as NaCl) and 1% of HNO 3 (v/v) were defined. For the determination of the optimum extraction point, a centroid-simplex statistical plan was a pplied, having chosen as the optimum points of extraction for all of the analytes, the follo wing proportions: 70% aqueous phase, 10% oil phase and 20% co-surfactant/surfactant (C/S = 4). After extraction, the metals were determined and the merit figures obtained for the proposed method were: LOD 0,09, 0,01, 0,06, 0,05, 0,6 and 1,5 ?g L -1 for Pb, Cd, Tl, Co, Cu and Ni, re spectively. Line ar ranges of ,1- 2,0 ?g L -1 for Pb, 0,01-2,0 ?g L -1 for Cd, 1,0 - 20 ?g L -1 for Tl, 0,1-5,0 ?g L -1 for Co, 2-200 ?g L -1 and for Cu e Ni 5-200 ?g L -1 were obtained. The enrichment factors obtained ranged between 6 and 19. Recovery testing with the certified sample show ed recovery values (n = 3, certified values) after extraction of 105 and 101, 100 and 104% for Pb, Cd, Cu and Ni respectively. Samples of sweet waters of lake Jiqui, saline water from Potengi river and water produced from the oil industry (PETROBRAS) were spiked and the recovery (n = 3) for the analytes were between 80 and 112% confirming th at the proposed method can be used in the extraction. The proposed method enabled the sepa ration of metals from complex matrices, and with good pre-concentration factor, consistent with the MPV (allowed limits) compared to CONAMA Resolution No. 357/2005 which regulat es the quality of fresh surface water, brackish and saline water in Brazil.