Zeólita modificada com b-ciclodextrina : síntese, caracterização e utilização como adsorvente para a remediação de contaminantes e disruptores endócrinos

Orientador: Profª Drª Ana Lucia Ramalho MercêTese (doutorado) - Universidade Federal do Paraná, Setor de Tecnologia, Programa de Pós-Graduação em Engenharia e Ciência dos Materiais - PIPE. Defesa: Curitiba, 21/08/2015Inclui referências : f. 126-141Área de concentração: Engenharia e ciência de materiaisResumo: Vários contaminantes inorgânicos e orgânicos foram estudados ao longo dos anos. Autores comprovaram o efeito cumulativo nos organismos e na natureza de alguns deles, exemplos tanto inorgânicos, cádmio, chumbo, zinco, quanto orgânicos, Fenotiazina e Bisfenol A. Neste trabalho foi utilizado um novo compósito, de baixo custo como material adsorvente, capaz de adsorver tanto contaminantes inorgânicos (Cd, Pb e Zn) como orgânicos (Bisfenol A - BPA e Fenotiazina). Os compósitos preparados foram comparados com os materiais de partida e caracterizados, avaliando-se inclusive a estrutura e porosidade dos mesmos. Os estudos dos comportamentos desses materiais na adsorção e remediação foram feitos a diferentes condições inclusive de pH, diferentes concentrações, e em matrizes de água bidestilada e em amostra de água de rio natural. Foram estudados os íons metálicos, cádmio (II), chumbo (II) e zinco (II) em concentrações diferentes, em água bidestilada, e água natural de rio. As soluções, em água bidestilada, foram contaminadas com Cd (8, 20, 50 ppm e 220 g/L), Pb (8. 20 e 50 ppm) e Zn (50, 100 e 200 ppm), e em água natural de rio foram contaminadas com Cd (50 ppm), Pb (50 ppm) e Zn (50 ppm). Os resultados das remediações após análise de concentração por Espectroscopia de Absorção Atômica mostraram que a redução de cádmio remediado, por batelada, por um dos compósitos de zeólita alcançou, em água destilada, até 99,9%; a redução de chumbo e de zinco alcançou até 99,8%; com os íons Cd2+, Pb2+ e Zn2+, de forma conjunta presentes em água bidestilada, os resultados mostraram redução de até 99,5%, 98,6%, e 98,2%, respectivamente, e em amostra artificialmente contaminada de água do rio Iguaçu, alcançou até 98,7%, 89,4%, e 91,2%, respectivamente, para os mesmos metais. Resultados de ensaios por MEV e EDS/EDS-MAPA comprovaram a complexação dos íons metálicos com a zeólita ZFA. Foram avaliados também, os contaminantes orgânicos Bisfenol A, Fenotiazina, e o comportamento de adsorção dos materiais zeolíticos, em água bidestilada e água do rio Iguaçu. As soluções, em água bidestilada e água natural de rio, foram contaminadas com 60 ppm de Bisfenol A e 60 ppm de Fenotiazina. A redução para o Bisfenol A e Fenotiazina somente ocorreu quando a remediação se deu com o compósito, alcançando 12,8% e 98,1%, respectivamente, em amostra contaminada artificialmente de água do rio Iguaçu. O estudo das extrações, mostrou que não houve uma variação significativa quanto ao pH. A única influência físicoquímica de influência na extração foi a concentração. Mesmo assim houve variação de análise de concentração apenas para os metais, em água bidestilada. Nos demais ensaios, em água natural de rio, e nos contaminantes orgânicos, não houveum estudo de variação de concentração (foram feitos na mesma concentração). Os resultados desta tese comprovaram a viabilidade da síntese de formação do novo compósito, CDZFA-1. Os resultados comprovaram a eficácia do novo compósito (CDZFA-1) tanto na remediação de contaminantes inorgânicos (metais Cd2+, Pb2+ e Zn2+) quanto de contaminantes orgânicos (Bisfenol A e Fenotiazina) em amostras aquosas, tanto de laboratório quanto em água natural de rio. Palavras-chave: zeólitas, cinzas de carvão, ciclodextrina, filmes poliméricos, cádmio, chumbo, zinco, Fenotiazina, Bisfenol A.Abstract: Various inorganic and organic contaminants were studied over the years. Authors proved the cumulative effect on the organisms and the chemical nature of some of them, both inorganic examples, cadmium, lead, zinc, and organic, such as Phenothiazine and Bisphenol A. In this work it was used a low cost new composite material capable of adsorbing both inorganic (Cd, Pb and Zn) and organic (Bisphenol A - BPA and phenothiazine) contaminants. The previously synthesized composites were compared with the starting materials and characterized, including the evaluation on their structure and porosity. Studies on the behavior of such materials included the adsorption and remediation at different conditions including pH, different concentrations, and medium, bidistilled water matrix and natural river water samples with cadmium (II) lead (II) and zinc (II). The solutions in ultrapure water water, were contaminated with Cd (8, 20, 50 ppm and 220 g / L), Pb (8. 20 and 50 ppm) and Zn (50, 100 and 200 ppm), and natural water river were contaminated with Cd (50 ppm), Pb (50 ppm) and Zn (50 ppm). The results of the remediation tests were quantified by Atomic Absorption Spectroscopy and showed cadmium reduction in the presence of the zeolite composites, in distilled water, up to 99.9%. The reduction of lead and zinc reached up to 99.8%. Solutions containing all metal ions together, Cd2+, Pb2+ and Zn2+ ions, in ultrapure water reached up to reductions of 99.5%, 98.6% and 98.2%, respectively, and in artificially contaminated samples of the Iguaçu river water reached up to 98.7%, 89.4% and 91.2%, respectively, for the same metals. The samples assayed by SEM and EDS / EDS-MAP showed results that confirmed the complexation of metal ions with the ZFA zeolite. The remediation of organic contaminants, Bisphenol A and phenothiazine were also studied, using the zeolite materials in both double-distilled water and natural water from the Iguaçu River. The solutions in ultrapure water and natural water river were contaminated with 60 ppm of BPA and 60 ppm of phenothiazine. The reduction of bisphenol A and Phenothiazineonly occurred when the remediation was performed with the synthesized composite, reaching up to 12.8% and 98.1%, respectively, in an artificially contaminated sample of the Iguaçu River water. The study of the extraction showed that there was no significant variation in the pH. The only physical and chemical influence of influence in the extraction was concentration. Nevertheless, there was variation in the concentration analysis only to metals in bidistilled water. In the other trials in natural river water, and organic contaminants, there was a concentration ranging study (were made at the same concentration). The results of this work confirmed the formation of a new zeolite composite (CDZFA-1) proving the effectiveness of the new composite (CDZFA-1) in the remediation of inorganic contaminants (metals Cd2+, Pb2+ and Zn2+) and organic contaminants (Bisphenol A and Phenothiazine) in both laboratory and natural river water samples. Keywords: Zeolites, coal fly ash, cyclodextrin, polymer films, cadmium, lead, zinc, phenothiazine, Bisphenol A

Implantaçao de um sistema integrado de gestao estratégica da qualidade e meio ambiente em laboratório de pesquisa e desenvolvimento

Orientador: Haroldo de A. PonteDissertaçao (mestrado) - Universidade Federal do Paraná, Setor de Tecnologia, Programa de Pós-Graduaçao em Engenharia - PIPE. Defesa: Curitiba, 2004Inclui bibliografia e anexosÁrea de concentraçao: Engenharia e ciencias de materiai

Zeólita modificada com b-ciclodextrina : síntese, caracterização e utilização como adsorvente para a remediação de contaminantes e disruptores endócrinos

Orientador: Profª Drª Ana Lucia Ramalho MercêTese (doutorado) - Universidade Federal do Paraná, Setor de Tecnologia, Programa de Pós-Graduação em Engenharia e Ciência dos Materiais - PIPE. Defesa: Curitiba, 21/08/2015Inclui referências : f. 126-141Área de concentração: Engenharia e ciência de materiaisResumo: Vários contaminantes inorgânicos e orgânicos foram estudados ao longo dos anos. Autores comprovaram o efeito cumulativo nos organismos e na natureza de alguns deles, exemplos tanto inorgânicos, cádmio, chumbo, zinco, quanto orgânicos, Fenotiazina e Bisfenol A. Neste trabalho foi utilizado um novo compósito, de baixo custo como material adsorvente, capaz de adsorver tanto contaminantes inorgânicos (Cd, Pb e Zn) como orgânicos (Bisfenol A - BPA e Fenotiazina). Os compósitos preparados foram comparados com os materiais de partida e caracterizados, avaliando-se inclusive a estrutura e porosidade dos mesmos. Os estudos dos comportamentos desses materiais na adsorção e remediação foram feitos a diferentes condições inclusive de pH, diferentes concentrações, e em matrizes de água bidestilada e em amostra de água de rio natural. Foram estudados os íons metálicos, cádmio (II), chumbo (II) e zinco (II) em concentrações diferentes, em água bidestilada, e água natural de rio. As soluções, em água bidestilada, foram contaminadas com Cd (8, 20, 50 ppm e 220 g/L), Pb (8. 20 e 50 ppm) e Zn (50, 100 e 200 ppm), e em água natural de rio foram contaminadas com Cd (50 ppm), Pb (50 ppm) e Zn (50 ppm). Os resultados das remediações após análise de concentração por Espectroscopia de Absorção Atômica mostraram que a redução de cádmio remediado, por batelada, por um dos compósitos de zeólita alcançou, em água destilada, até 99,9%; a redução de chumbo e de zinco alcançou até 99,8%; com os íons Cd2+, Pb2+ e Zn2+, de forma conjunta presentes em água bidestilada, os resultados mostraram redução de até 99,5%, 98,6%, e 98,2%, respectivamente, e em amostra artificialmente contaminada de água do rio Iguaçu, alcançou até 98,7%, 89,4%, e 91,2%, respectivamente, para os mesmos metais. Resultados de ensaios por MEV e EDS/EDS-MAPA comprovaram a complexação dos íons metálicos com a zeólita ZFA. Foram avaliados também, os contaminantes orgânicos Bisfenol A, Fenotiazina, e o comportamento de adsorção dos materiais zeolíticos, em água bidestilada e água do rio Iguaçu. As soluções, em água bidestilada e água natural de rio, foram contaminadas com 60 ppm de Bisfenol A e 60 ppm de Fenotiazina. A redução para o Bisfenol A e Fenotiazina somente ocorreu quando a remediação se deu com o compósito, alcançando 12,8% e 98,1%, respectivamente, em amostra contaminada artificialmente de água do rio Iguaçu. O estudo das extrações, mostrou que não houve uma variação significativa quanto ao pH. A única influência físicoquímica de influência na extração foi a concentração. Mesmo assim houve variação de análise de concentração apenas para os metais, em água bidestilada. Nos demais ensaios, em água natural de rio, e nos contaminantes orgânicos, não houveum estudo de variação de concentração (foram feitos na mesma concentração). Os resultados desta tese comprovaram a viabilidade da síntese de formação do novo compósito, CDZFA-1. Os resultados comprovaram a eficácia do novo compósito (CDZFA-1) tanto na remediação de contaminantes inorgânicos (metais Cd2+, Pb2+ e Zn2+) quanto de contaminantes orgânicos (Bisfenol A e Fenotiazina) em amostras aquosas, tanto de laboratório quanto em água natural de rio. Palavras-chave: zeólitas, cinzas de carvão, ciclodextrina, filmes poliméricos, cádmio, chumbo, zinco, Fenotiazina, Bisfenol A.Abstract: Various inorganic and organic contaminants were studied over the years. Authors proved the cumulative effect on the organisms and the chemical nature of some of them, both inorganic examples, cadmium, lead, zinc, and organic, such as Phenothiazine and Bisphenol A. In this work it was used a low cost new composite material capable of adsorbing both inorganic (Cd, Pb and Zn) and organic (Bisphenol A - BPA and phenothiazine) contaminants. The previously synthesized composites were compared with the starting materials and characterized, including the evaluation on their structure and porosity. Studies on the behavior of such materials included the adsorption and remediation at different conditions including pH, different concentrations, and medium, bidistilled water matrix and natural river water samples with cadmium (II) lead (II) and zinc (II). The solutions in ultrapure water water, were contaminated with Cd (8, 20, 50 ppm and 220 g / L), Pb (8. 20 and 50 ppm) and Zn (50, 100 and 200 ppm), and natural water river were contaminated with Cd (50 ppm), Pb (50 ppm) and Zn (50 ppm). The results of the remediation tests were quantified by Atomic Absorption Spectroscopy and showed cadmium reduction in the presence of the zeolite composites, in distilled water, up to 99.9%. The reduction of lead and zinc reached up to 99.8%. Solutions containing all metal ions together, Cd2+, Pb2+ and Zn2+ ions, in ultrapure water reached up to reductions of 99.5%, 98.6% and 98.2%, respectively, and in artificially contaminated samples of the Iguaçu river water reached up to 98.7%, 89.4% and 91.2%, respectively, for the same metals. The samples assayed by SEM and EDS / EDS-MAP showed results that confirmed the complexation of metal ions with the ZFA zeolite. The remediation of organic contaminants, Bisphenol A and phenothiazine were also studied, using the zeolite materials in both double-distilled water and natural water from the Iguaçu River. The solutions in ultrapure water and natural water river were contaminated with 60 ppm of BPA and 60 ppm of phenothiazine. The reduction of bisphenol A and Phenothiazineonly occurred when the remediation was performed with the synthesized composite, reaching up to 12.8% and 98.1%, respectively, in an artificially contaminated sample of the Iguaçu River water. The study of the extraction showed that there was no significant variation in the pH. The only physical and chemical influence of influence in the extraction was concentration. Nevertheless, there was variation in the concentration analysis only to metals in bidistilled water. In the other trials in natural river water, and organic contaminants, there was a concentration ranging study (were made at the same concentration). The results of this work confirmed the formation of a new zeolite composite (CDZFA-1) proving the effectiveness of the new composite (CDZFA-1) in the remediation of inorganic contaminants (metals Cd2+, Pb2+ and Zn2+) and organic contaminants (Bisphenol A and Phenothiazine) in both laboratory and natural river water samples. Keywords: Zeolites, coal fly ash, cyclodextrin, polymer films, cadmium, lead, zinc, phenothiazine, Bisphenol A

Implantaçao de um sistema integrado de gestao estratégica da qualidade e meio ambiente em laboratório de pesquisa e desenvolvimento

Orientador: Haroldo de A. PonteDissertaçao (mestrado) - Universidade Federal do Paraná, Setor de Tecnologia, Programa de Pós-Graduaçao em Engenharia - PIPE. Defesa: Curitiba, 2004Inclui bibliografia e anexosÁrea de concentraçao: Engenharia e ciencias de materiai

β-Cyclodextrin-modified zeolite from fly ash: Synthesis, characterization, and use as cadmium, lead and zinc adsorbent

The ISWA - Solid Waste World Congress 2014. Sao Paulo, Br. PósterCoal Combustion Products (CCPs) are the solid inorganic materials that remain after coal is burned to generated electricity in power plants. The major solid residues included in CCPs are fly ash, bottom ash, boiler slag and FGD materials. With nearly 70% of the total amount fly ash is the most important CCP. Every year a crude estimation of 600 million tons of fly ash generated worldwide and about 4 million tons in Brazil. In this work, zeolite from coal fly ash (ZFA) was prepared by conventional alkaline hydrothermal treatment and modified with β-Cyclodextrin (CD). CD is a cyclic oligosaccharide composed of seven α-D-glucose units connected through α-(1,4) linkages with an internal hydrophobic cavity. CD is the most accessible environmental friendly “safe agent” for material modification due to its low-price and harmless properties. Modified zeolites with CD (CDZFA) were prepared at different modification conditions, such as contact time, ratio of zeolite from coal fly ash mass/volume of CD and different CD concentration . Preliminary adsorption experiments using the crystal violet dye as a model compound indicated that CDZFA-1 was the most effective adsorbent. Zeolitic materials, ZFA and CDZFA-1, were examined for the adsorption of toxic metals Pb+2, Cd+2 and Zn+2 from water in a batch technique. The effects of metal ion concentration and pH on the adsorption were investigated. The zeolitic materials before and after adsorption of metal ions were characterized using thermo analysis (TG/DTG; DSC), FTIR spectroscopy and zeta potential. The metal ion adsorption efficiencies for zeolite from coal fly ash and modified zeolite were compared and both adsorbents exhibited strong affinity for the ions. The reduction of metal ions from water by modified zeolite reached up to 99.49% for Cd2+, 99.88% for Pb2+ and 99.93 % for Zn2+. According to the obtained results, β-Cyclodextrin-modified zeolite from fly ash developed in this study has the potential to be a promising low-cost adsorbent for the removal of toxic metal ions from industrial wastewater.N

Cyclodextrin-modified Zeolite from fly ash: synthesis, characterization and adsorption properties.

Twenty-Eighth International Conference on Solid Waste Technology and Management. Filadelfia, PA, USAThe global annual production of coal fly ash (CFA) is around 800 Mton and it is predicted to increase by the higher demand of electricity due to growing population and economic development. The recycling rate of CFA is only 15% posing important challenges in waste management. Recently, the synthesis of zeolites has produced an environmentally friendly and economically viable way of recycling CFA. Initial findings indicate that zeolite synthesized from fly ash (ZFA) has high adsorptive capacity for dyes, so far. Modified zeolite is being used to remove anions and organic pollutants. In this paper, a modified ZFA was prepared using β-cyclodextrin (β-CD), a cyclic polysaccharide consisting of D-glucose units connected via α(1→4) glycosidic bonds with an hydrophobic cavity. CDs are very accessible environmental friendly agents for remediation due to its biocompatibility and low-prices. Cd(II) is considered as an endocrine disruptor, and its removal from water resources is a UN priority. Thus, the modified ZFA was tested for adsorption of Cd at different pH values. Results showed that, at pH 7-8, modified ZFA yielded a higher adsorption of Cd than initial ZFA.N

NEOTROPICAL ALIEN MAMMALS: a data set of occurrence and abundance of alien mammals in the Neotropics

Biological invasion is one of the main threats to native biodiversity. For a species to become invasive, it must be voluntarily or involuntarily introduced by humans into a nonnative habitat. Mammals were among first taxa to be introduced worldwide for game, meat, and labor, yet the number of species introduced in the Neotropics remains unknown. In this data set, we make available occurrence and abundance data on mammal species that (1) transposed a geographical barrier and (2) were voluntarily or involuntarily introduced by humans into the Neotropics. Our data set is composed of 73,738 historical and current georeferenced records on alien mammal species of which around 96% correspond to occurrence data on 77 species belonging to eight orders and 26 families. Data cover 26 continental countries in the Neotropics, ranging from Mexico and its frontier regions (southern Florida and coastal-central Florida in the southeast United States) to Argentina, Paraguay, Chile, and Uruguay, and the 13 countries of Caribbean islands. Our data set also includes neotropical species (e.g., Callithrix sp., Myocastor coypus, Nasua nasua) considered alien in particular areas of Neotropics. The most numerous species in terms of records are from Bos sp. (n = 37,782), Sus scrofa (n = 6,730), and Canis familiaris (n = 10,084); 17 species were represented by only one record (e.g., Syncerus caffer, Cervus timorensis, Cervus unicolor, Canis latrans). Primates have the highest number of species in the data set (n = 20 species), partly because of uncertainties regarding taxonomic identification of the genera Callithrix, which includes the species Callithrix aurita, Callithrix flaviceps, Callithrix geoffroyi, Callithrix jacchus, Callithrix kuhlii, Callithrix penicillata, and their hybrids. This unique data set will be a valuable source of information on invasion risk assessments, biodiversity redistribution and conservation-related research. There are no copyright restrictions. Please cite this data paper when using the data in publications. We also request that researchers and teachers inform us on how they are using the data