Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos

Detalhes bibliográficos
Ano de defesa: 2011
Autor(a) principal: Wilde, Marcelo Luís lattes
Orientador(a): Martins, Ayrton Figueiredo lattes
Banca de defesa: Sirtori, Carla lattes, Machado, ênio Leandro lattes, Schwaab, Marcio lattes, Dallago, Rogério Marcos lattes
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Federal de Santa Maria
Programa de Pós-Graduação: Programa de Pós-Graduação em Química
Departamento: Química
País: BR
Palavras-chave em Português:
Palavras-chave em Inglês:
Área do conhecimento CNPq:
Link de acesso: http://repositorio.ufsm.br/handle/1/4215
Resumo: β-Blockers are an important group of prescription drugs; as a consequence of the large and continuous use, they are commonly found in the environment. This study assessed, preliminary, the inherent risk of the β-blockers Atenolol, Metoprolol and Propranolol, mostly used in the University Hospital of Santa Maria (HUSM), and showed that Propranolol has high Risk Quotient (RQ) of 0.56. HPLC-FLD and SPE methodologies were developed and optimized with the aid of experimental design in order to analyze the occurrence of β-blockers in the HUSM sewage system. The average concentration for Atenolol, Metoprolol and Propranolol found for a week sampling were 2.45, 4.67 and 0.70 μg L-1 in the sewage of the Emergence; 0.95, 0.70 and 0.315 μg L-1 in the HUSM main sewage, and 1.26, 1.27 and 0.56 μg L-1 in the water course receptor, respectively, As possible remediation methodologies for the Hospital Wastewater (HWW) were investigated Advanced Oxidation Process (AOPs) such as photo-Fenton, K2FeO4, Ozonation and O3/Fe2+. The operational parameters were optimized by Response Surface Methodology (RSM). Using optimized conditions for photo-Fenton, Atenolol, Metoprolol and Propranolol were totally degraded in 5 min in aqueous solution, and the mineralization achieved 80% after 120 min of treatment. In HWW, the β-blockers were also totally degraded, however, only 26.5% of the organic matter and 38.6% of the aromaticity were removed. The ready biodegradability and toxicity of the photo-Fenton s samples were estimated by official methods, which indicated an increase in the biodegradability and toxicity. This behavior may be correlated to the formation of degradation products (DPs), relatively, more toxic. The DPs were identified with aid of Liquid Chromatography tandem Mass Spectrometry (LC-MSn). Other proposed degradation process was oxidation-coagulation using Fe(VI), which achieved above 90% degradation for Atenolol, Metoprolol and Propranolol in HWW, while only 17% COD and 60% aromaticity removal. In aqueous solution this process led to 71.7%, 24.7% and 96.5% degradation of Atenolol, Metoprolol and Propranolol, respectively. No mineralization was found, indicating the formation of DPs, identified by LC-MSn. The ready biodegradability of the post-process samples was tested and the results showed that the oxidation-coagulation with Fe(VI) increased the biodegradability. The applicability of ozonation was evaluated varying the pH (3-11) for HWW and aqueous solution. More than 95% of the β-blockers were degraded independently of the initial pH, while above 50% of the aromaticity was removed. In aqueous solution the β-blockers were degraded in 10 min treatment and the identification of the DPs were carried out for process pH 5, 7 and 9. Catalytic ozonation (O3/Fe2+) was applied to HWW and a mineralization of 49% was achieved, with 77.9% aromaticity removal. The β-blockers were totally degraded. Therefore, the present study represents a high qualified analytical information contribution concerning the occurrence of β-blockers in HWW. The studied AOPs/Fe(VI) processes demonstrated to be suitable to degrade Atenolol, Metoprolol and Propranolol. Moreover, high removal of organic matter and aromaticity were achieved by appling O3/Fe2+ process. In many aspects, this work can be considered original, in especial, by regarding the application of Ferrate(VI) and Catalytic Ozonation to the degradation of β-blockers in HWW.
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spelling 2017-05-182017-05-182011-12-15WILDE, Marcelo Luís. Βeta-blockers in hospital wastewater; occurence, degradation by advanced oxidation process and byproducts identification. 2011. 280 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2011.http://repositorio.ufsm.br/handle/1/4215β-Blockers are an important group of prescription drugs; as a consequence of the large and continuous use, they are commonly found in the environment. This study assessed, preliminary, the inherent risk of the β-blockers Atenolol, Metoprolol and Propranolol, mostly used in the University Hospital of Santa Maria (HUSM), and showed that Propranolol has high Risk Quotient (RQ) of 0.56. HPLC-FLD and SPE methodologies were developed and optimized with the aid of experimental design in order to analyze the occurrence of β-blockers in the HUSM sewage system. The average concentration for Atenolol, Metoprolol and Propranolol found for a week sampling were 2.45, 4.67 and 0.70 μg L-1 in the sewage of the Emergence; 0.95, 0.70 and 0.315 μg L-1 in the HUSM main sewage, and 1.26, 1.27 and 0.56 μg L-1 in the water course receptor, respectively, As possible remediation methodologies for the Hospital Wastewater (HWW) were investigated Advanced Oxidation Process (AOPs) such as photo-Fenton, K2FeO4, Ozonation and O3/Fe2+. The operational parameters were optimized by Response Surface Methodology (RSM). Using optimized conditions for photo-Fenton, Atenolol, Metoprolol and Propranolol were totally degraded in 5 min in aqueous solution, and the mineralization achieved 80% after 120 min of treatment. In HWW, the β-blockers were also totally degraded, however, only 26.5% of the organic matter and 38.6% of the aromaticity were removed. The ready biodegradability and toxicity of the photo-Fenton s samples were estimated by official methods, which indicated an increase in the biodegradability and toxicity. This behavior may be correlated to the formation of degradation products (DPs), relatively, more toxic. The DPs were identified with aid of Liquid Chromatography tandem Mass Spectrometry (LC-MSn). Other proposed degradation process was oxidation-coagulation using Fe(VI), which achieved above 90% degradation for Atenolol, Metoprolol and Propranolol in HWW, while only 17% COD and 60% aromaticity removal. In aqueous solution this process led to 71.7%, 24.7% and 96.5% degradation of Atenolol, Metoprolol and Propranolol, respectively. No mineralization was found, indicating the formation of DPs, identified by LC-MSn. The ready biodegradability of the post-process samples was tested and the results showed that the oxidation-coagulation with Fe(VI) increased the biodegradability. The applicability of ozonation was evaluated varying the pH (3-11) for HWW and aqueous solution. More than 95% of the β-blockers were degraded independently of the initial pH, while above 50% of the aromaticity was removed. In aqueous solution the β-blockers were degraded in 10 min treatment and the identification of the DPs were carried out for process pH 5, 7 and 9. Catalytic ozonation (O3/Fe2+) was applied to HWW and a mineralization of 49% was achieved, with 77.9% aromaticity removal. The β-blockers were totally degraded. Therefore, the present study represents a high qualified analytical information contribution concerning the occurrence of β-blockers in HWW. The studied AOPs/Fe(VI) processes demonstrated to be suitable to degrade Atenolol, Metoprolol and Propranolol. Moreover, high removal of organic matter and aromaticity were achieved by appling O3/Fe2+ process. In many aspects, this work can be considered original, in especial, by regarding the application of Ferrate(VI) and Catalytic Ozonation to the degradation of β-blockers in HWW.Os β-bloqueadores são uma importante classe de fármacos prescritos na terapia de doenças cardiovasculares e como consequência de seu grande e contínuo uso são comumente encontrados no meio ambiente. O presente estudo avaliou preliminarmente o risco inerente dos β-bloqueadores mais usados no Hospital Universitário de Santa Maria (HUSM), Atenolol, Metoprolol e Propranolol, evidenciando que Propranolol apresentou maior risco inerente com Quociente de Risco teórico de 0,56 (risco médio). Métodos HPLC-FLD e de clean-up/pré-concentração por SPE foram desenvolvidos e otimizados com auxílio de Metodologia de Superfície de Resposta (RSM) para avaliar a ocorrência de β-bloqueadores no sistema de esgotos do HUSM. A concentração ambiental mensurada para Atenolol, Metoprolol e Propranolol durante um ciclo semanal no ponto de lançamento Efluente PA foi 2,45; 4,67 e 0,70 μg L-1, no ponto HUSM principal 0,95; 0,70 e 0,32 μg L-1 e para o Córrego onde os efluentes são lançados de 1,26; 1,27 e 0,56 μg L-1, respectivamente. Como metodologia de remediação da contaminação de β-bloqueadores em Efluente Hospitalar (EH) foram investigados os Processos Avançados de Oxidação (PAOs) Foto-Fenton, K2FeO4, Ozonização e O3/Fe2+. Os parâmetros operacionais foram otimizados por RSM. Usando as condições otimizadas para o processo Foto-Fenton, Atenolol, Metoprolol e Propranolol foram totalmente degradados em 120 min de tratamento, contudo somente 26,5 e 38,6% da carga orgânica e aromaticidade, respectivamente, foram removidos em EH. A pronta biodegradabilidade e toxicidade para amostras aquosas do processo Foto-Fenton foram analisadas por métodos oficiais e indicaram aumento na biodegradabilidade e toxicidade. Este comportamento esta relacionado à formação de Produtos de Degradação (PD) relativamente mais tóxicos. Os PDs foram identificados por Cromatografia Líquida acoplada a Espectrometria de Massas (LC-MSn). Outro processo proposto foi oxidação-coagulação com Fe(VI) que alcançou degradação de Atenolol, Metoprolol e Propranolol acima de 90% em EH, enquanto apenas 17 e 60% da matéria orgânica e aromaticidade foram removidos, respectivamente. Em solução aquosa este processo conduziu a degradação de 71,7; 24,7 e 96,5% de Atenolol, Metoprolol e Propranolol, respectivamente. Nenhuma mineralização foi encontrada indicando a formação de PDs, identificados por LC-MSn. A pronta biodegradabilidade para as amostras aquosas pós-processo foram avaliadas e os resultados encontrados mostraram que houve aumento na biodegradabilidade. A aplicabilidade de ozonização foi avaliada variando o pH de 3-11 em EH e solução aquosa. Mais de 95% dos β-bloqueadores foram degradados independente do pH inicial, enquanto mais de 50% da aromaticidade e 30% da matéria orgânica foram. Em solução aquosa todos os β-bloqueadores foram degradados em menos de 10 min e para os processos em pH 5, 7 e 9 foram identificados os PDs. O processo de O3/Fe2+ alcançou 49% de remoção de matéria orgânica, 77,9% de redução da aromaticidade e completa degradação de Atenolol, Metoprolol e Propranolol em EH. Portanto, o presente estudo contribui com informação analítica qualificada sobre a ocorrência de β-bloqueadores em EH. Os processos de degradação estudados mostraram-se adequados para a degradação de Atenolol, Metoprolol e Propranolol. Ademais, a maior remoção de matéria orgânica e aromaticidade foram observadas para o processo de O3/Fe2+. Em muitos aspectos, este trabalho pode ser considerado original, em especial sobre a aplicação de ferrato(VI) e ozonização catalítica para a degradação de β-bloqueadores em EH.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaProcessos avançados de oxidaçãoβ-bloqueadoresEfluente hospitalarFerrato de potássioFoto-FentonOzonizaçãoProdutos de degradaçãoAdvanced oxidation processesβ-blockersHospital wastewaterPotassium ferratePhoto-FentonOzonationDegradation productsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAΒeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutosΒeta-blockers in hospital wastewater; occurence, degradation by advanced oxidation process and byproducts identificationinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisMartins, Ayrton Figueiredohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4787438A0Sirtori, Carlahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4704983Z8Machado, ênio Leandrohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784684U8Schwaab, Marciohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4706157Z4Dallago, Rogério Marcoshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4708861U6http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4705790Z7Wilde, Marcelo Luís100600000000400300300300300300300ade6000d-a348-4d49-a531-6500a65a153af3e9968e-966b-4413-b5ac-e74193b29a82e97ba5e1-bd70-4946-b35e-162e90baaf7b16bb7285-3cf9-4f72-bec0-d2ae192958f1d164c2a4-708c-4052-9b68-c99a08a7a2dafe138a12-6190-4b55-ab58-8975c6abc2a6info:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALWILDE, MARCELO LUIS.pdfapplication/pdf14229714http://repositorio.ufsm.br/bitstream/1/4215/1/WILDE%2c%20MARCELO%20LUIS.pdf0cc1e6749dfed2254f5c5dc22c4f477cMD51TEXTWILDE, MARCELO LUIS.pdf.txtWILDE, MARCELO LUIS.pdf.txtExtracted texttext/plain578462http://repositorio.ufsm.br/bitstream/1/4215/2/WILDE%2c%20MARCELO%20LUIS.pdf.txt3b8722230c94cd838b2d26c2e86036d9MD52THUMBNAILWILDE, MARCELO LUIS.pdf.jpgWILDE, MARCELO LUIS.pdf.jpgIM Thumbnailimage/jpeg6422http://repositorio.ufsm.br/bitstream/1/4215/3/WILDE%2c%20MARCELO%20LUIS.pdf.jpgebc8cf1bf212615097c4a9a40900f580MD531/42152017-07-27 18:14:50.692oai:repositorio.ufsm.br:1/4215Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-27T21:14:50Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.por.fl_str_mv Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos
dc.title.alternative.eng.fl_str_mv Βeta-blockers in hospital wastewater; occurence, degradation by advanced oxidation process and byproducts identification
title Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos
spellingShingle Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos
Wilde, Marcelo Luís
Processos avançados de oxidação
β-bloqueadores
Efluente hospitalar
Ferrato de potássio
Foto-Fenton
Ozonização
Produtos de degradação
Advanced oxidation processes
β-blockers
Hospital wastewater
Potassium ferrate
Photo-Fenton
Ozonation
Degradation products
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos
title_full Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos
title_fullStr Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos
title_full_unstemmed Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos
title_sort Βeta-bloqueadores em efluente hospitalar: ocorrência, degradação por processos avançados de oxidação e identificação de subprodutos
author Wilde, Marcelo Luís
author_facet Wilde, Marcelo Luís
author_role author
dc.contributor.advisor1.fl_str_mv Martins, Ayrton Figueiredo
dc.contributor.advisor1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4787438A0
dc.contributor.referee1.fl_str_mv Sirtori, Carla
dc.contributor.referee1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4704983Z8
dc.contributor.referee2.fl_str_mv Machado, ênio Leandro
dc.contributor.referee2Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784684U8
dc.contributor.referee3.fl_str_mv Schwaab, Marcio
dc.contributor.referee3Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4706157Z4
dc.contributor.referee4.fl_str_mv Dallago, Rogério Marcos
dc.contributor.referee4Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4708861U6
dc.contributor.authorLattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4705790Z7
dc.contributor.author.fl_str_mv Wilde, Marcelo Luís
contributor_str_mv Martins, Ayrton Figueiredo
Sirtori, Carla
Machado, ênio Leandro
Schwaab, Marcio
Dallago, Rogério Marcos
dc.subject.por.fl_str_mv Processos avançados de oxidação
β-bloqueadores
Efluente hospitalar
Ferrato de potássio
Foto-Fenton
Ozonização
Produtos de degradação
topic Processos avançados de oxidação
β-bloqueadores
Efluente hospitalar
Ferrato de potássio
Foto-Fenton
Ozonização
Produtos de degradação
Advanced oxidation processes
β-blockers
Hospital wastewater
Potassium ferrate
Photo-Fenton
Ozonation
Degradation products
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.eng.fl_str_mv Advanced oxidation processes
β-blockers
Hospital wastewater
Potassium ferrate
Photo-Fenton
Ozonation
Degradation products
dc.subject.cnpq.fl_str_mv CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description β-Blockers are an important group of prescription drugs; as a consequence of the large and continuous use, they are commonly found in the environment. This study assessed, preliminary, the inherent risk of the β-blockers Atenolol, Metoprolol and Propranolol, mostly used in the University Hospital of Santa Maria (HUSM), and showed that Propranolol has high Risk Quotient (RQ) of 0.56. HPLC-FLD and SPE methodologies were developed and optimized with the aid of experimental design in order to analyze the occurrence of β-blockers in the HUSM sewage system. The average concentration for Atenolol, Metoprolol and Propranolol found for a week sampling were 2.45, 4.67 and 0.70 μg L-1 in the sewage of the Emergence; 0.95, 0.70 and 0.315 μg L-1 in the HUSM main sewage, and 1.26, 1.27 and 0.56 μg L-1 in the water course receptor, respectively, As possible remediation methodologies for the Hospital Wastewater (HWW) were investigated Advanced Oxidation Process (AOPs) such as photo-Fenton, K2FeO4, Ozonation and O3/Fe2+. The operational parameters were optimized by Response Surface Methodology (RSM). Using optimized conditions for photo-Fenton, Atenolol, Metoprolol and Propranolol were totally degraded in 5 min in aqueous solution, and the mineralization achieved 80% after 120 min of treatment. In HWW, the β-blockers were also totally degraded, however, only 26.5% of the organic matter and 38.6% of the aromaticity were removed. The ready biodegradability and toxicity of the photo-Fenton s samples were estimated by official methods, which indicated an increase in the biodegradability and toxicity. This behavior may be correlated to the formation of degradation products (DPs), relatively, more toxic. The DPs were identified with aid of Liquid Chromatography tandem Mass Spectrometry (LC-MSn). Other proposed degradation process was oxidation-coagulation using Fe(VI), which achieved above 90% degradation for Atenolol, Metoprolol and Propranolol in HWW, while only 17% COD and 60% aromaticity removal. In aqueous solution this process led to 71.7%, 24.7% and 96.5% degradation of Atenolol, Metoprolol and Propranolol, respectively. No mineralization was found, indicating the formation of DPs, identified by LC-MSn. The ready biodegradability of the post-process samples was tested and the results showed that the oxidation-coagulation with Fe(VI) increased the biodegradability. The applicability of ozonation was evaluated varying the pH (3-11) for HWW and aqueous solution. More than 95% of the β-blockers were degraded independently of the initial pH, while above 50% of the aromaticity was removed. In aqueous solution the β-blockers were degraded in 10 min treatment and the identification of the DPs were carried out for process pH 5, 7 and 9. Catalytic ozonation (O3/Fe2+) was applied to HWW and a mineralization of 49% was achieved, with 77.9% aromaticity removal. The β-blockers were totally degraded. Therefore, the present study represents a high qualified analytical information contribution concerning the occurrence of β-blockers in HWW. The studied AOPs/Fe(VI) processes demonstrated to be suitable to degrade Atenolol, Metoprolol and Propranolol. Moreover, high removal of organic matter and aromaticity were achieved by appling O3/Fe2+ process. In many aspects, this work can be considered original, in especial, by regarding the application of Ferrate(VI) and Catalytic Ozonation to the degradation of β-blockers in HWW.
publishDate 2011
dc.date.issued.fl_str_mv 2011-12-15
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identifier_str_mv WILDE, Marcelo Luís. Βeta-blockers in hospital wastewater; occurence, degradation by advanced oxidation process and byproducts identification. 2011. 280 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2011.
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