Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação
Autor(a) principal: | |
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Data de Publicação: | 2006 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4303 |
Resumo: | In the present study, the presence of the antimicrobial ciprofloxacin (CIP) in effluent from the first-aid clinic of the University Hospital of Santa Maria (PA-HUSM) and its degradation by advanced oxidation processes (AOPs) - photo-induced process (medium pressure Hg-lamp 125 W, batch recirculation reactor, pH 3), heterogeneous catalysis (medium pressure Hg-lamp 125 W, helicoidal tubular reactor, pH 3, 400 mg TiO2), ozonation and peroxone (450 mg O3 h-1, pH 9, semi-batch system, 500 mg H2O2 L-1 for peroxone) were investigated. Determination of the CIP concentration developed by high pressure liquid chromatography with fluorescence detection (HPLC-FLD) was measured before (P1) and after (P2) treatment system (cesspit and anaerobic filter), during 7 days. Measured environmental concentrations (MECs) were 19-155 μg L-1 (average: 65±45 μg L-1) and 32-99 μg L-1 (average: 54±21 μg L-1) in P1 and P2, respectively. In addition, risk assessment based on the MECs and ecotoxicity data from the literature was proposed. Using three different values of predicted no-effect concentration (PNEC), MECs/PNEC ratios between 4-1,980 were calculated. These risk quotients imply a high risk for a negative impact of CIP to aquatic environment and suggest that risk management is necessary. These quotients are 48-3,300-fold higher than those found in developed countries and mean a worse-case than the discussed wide world until now. Regarding the treatment of the effluent by AOPs, photo-induced degradation was slowest than the other processes: half-life (t1/2) during photo-induced of CIP was 2.5 h, while heterogeneous photocatalysis, peroxone and ozonation presented 20, 15 and 9 min, respectively. The best results obtained through ozonation were consequence of the higher reactivity of CIP with ozone than with radicalar species formed during the processes. However, about chemical oxygen demand (COD) and integrated absorbance, peroxone and heterogeneous photocatalysis (higher capacity for hydroxyl radical generation) were more effective than the photo-induced and ozonation processes (lower hydroxyl radical generation capacity). The metabolites formed during the processes demonstrated to be very similar. In addition, photo-induced degradation of CIP (medium pressure Hg-lamp 150 W, batch reactor) in environmental concentration of 0.1 mg L-1 (0.3 x 10-6 mol L-1) and pH 9 (NH4Cl/KOH) was studied. The first order rate constant and half-life were 1.56 ±0.11 x 10-2 s-1 (R2 > 0.999) and 44±7 s, respectively. The first formed metabolites were identified by HPLC-FLD and high pressure liquid chromatography with mass detection (LC-MS). Five compounds were qualitatively identified as probable metabolites and were not ready biodegradable by closed bottle test (CBT). They would be products from reactions of defluorination, decarboxilation and break of the piperazine ring. They have been already reported in the literature but under other conditions. |
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Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidaçãoAntimicrobial ciprofloxacin in hospital effluent: environmental exposure, risk assessment and degradation by advanced oxidation processesQuímicaQuímica analíticaEfluente hospitalarCiprofloxacinDegradaçãoCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAIn the present study, the presence of the antimicrobial ciprofloxacin (CIP) in effluent from the first-aid clinic of the University Hospital of Santa Maria (PA-HUSM) and its degradation by advanced oxidation processes (AOPs) - photo-induced process (medium pressure Hg-lamp 125 W, batch recirculation reactor, pH 3), heterogeneous catalysis (medium pressure Hg-lamp 125 W, helicoidal tubular reactor, pH 3, 400 mg TiO2), ozonation and peroxone (450 mg O3 h-1, pH 9, semi-batch system, 500 mg H2O2 L-1 for peroxone) were investigated. Determination of the CIP concentration developed by high pressure liquid chromatography with fluorescence detection (HPLC-FLD) was measured before (P1) and after (P2) treatment system (cesspit and anaerobic filter), during 7 days. Measured environmental concentrations (MECs) were 19-155 μg L-1 (average: 65±45 μg L-1) and 32-99 μg L-1 (average: 54±21 μg L-1) in P1 and P2, respectively. In addition, risk assessment based on the MECs and ecotoxicity data from the literature was proposed. Using three different values of predicted no-effect concentration (PNEC), MECs/PNEC ratios between 4-1,980 were calculated. These risk quotients imply a high risk for a negative impact of CIP to aquatic environment and suggest that risk management is necessary. These quotients are 48-3,300-fold higher than those found in developed countries and mean a worse-case than the discussed wide world until now. Regarding the treatment of the effluent by AOPs, photo-induced degradation was slowest than the other processes: half-life (t1/2) during photo-induced of CIP was 2.5 h, while heterogeneous photocatalysis, peroxone and ozonation presented 20, 15 and 9 min, respectively. The best results obtained through ozonation were consequence of the higher reactivity of CIP with ozone than with radicalar species formed during the processes. However, about chemical oxygen demand (COD) and integrated absorbance, peroxone and heterogeneous photocatalysis (higher capacity for hydroxyl radical generation) were more effective than the photo-induced and ozonation processes (lower hydroxyl radical generation capacity). The metabolites formed during the processes demonstrated to be very similar. In addition, photo-induced degradation of CIP (medium pressure Hg-lamp 150 W, batch reactor) in environmental concentration of 0.1 mg L-1 (0.3 x 10-6 mol L-1) and pH 9 (NH4Cl/KOH) was studied. The first order rate constant and half-life were 1.56 ±0.11 x 10-2 s-1 (R2 > 0.999) and 44±7 s, respectively. The first formed metabolites were identified by HPLC-FLD and high pressure liquid chromatography with mass detection (LC-MS). Five compounds were qualitatively identified as probable metabolites and were not ready biodegradable by closed bottle test (CBT). They would be products from reactions of defluorination, decarboxilation and break of the piperazine ring. They have been already reported in the literature but under other conditions.Conselho Nacional de Desenvolvimento Científico e TecnológicoNeste trabalho, investigou-se a presença do antimicrobial ciprofloxacina (CIP) em efluente do Pronto Atendimento do Hospital Universitário de Santa Maria (PAHUSM) e a sua destruição através de processos avançados de oxidação (PAOs) - processo fotoinduzido (lâmpada de Hg de média pressão de 125 W, reator em batelada com recirculação, pH 3), fotocatálise heterogênea (lâmpada de Hg de média pressão de 125 W, reator tubular helicoidal, pH 3, 400 mg TiO2), ozonização e peroxônio (450 mg h-1 de O3, pH 9, sistema de semi-batelada e 500 mg H2O2 L-1 no caso do peroxônio). A determinação de CIP, realizada através de cromatografia líquida com detector de fluorescência (HPLC-FLD), envolveu dois pontos de amostragem: antes (P1) e depois (P2) do sistema de tratamento (fossa séptica e filtro anaeróbio) durante 7 dias. As concentrações ambientais medidas (CAMs) foram 19-155 μg L-1 (média: 65±45 μg L-1) e 32-99 μg L-1 (média: 54±21 μg L-1) em P1 e P2, respectivamente. Realizou-se avaliação de risco baseado nas CAMs e em dados ecotoxicológicos retirados da literatura. Usando-se três diferentes valores de concentrações preditas de efeito não observado (CPENO), foram calculadas razões CAM/CPENO entre 4-1.980. Estes quocientes indicam alto risco ao meio ambiente e a necessidade de um projeto de gerenciamento de risco. Além disso, estes valores são 48-3.300 vezes maiores que aqueles encontrados em países desenvolvidos, o que significa uma situação bem mais crítica do que as que vinham sendo reportadas e mundialmente discutidas. Na aplicação de PAOs ao efluente do PA-HUSM a oxidação fotoinduzida demonstrou ser muito mais lenta quando comparada aos outros processos: tempo de meia-vida (t1/2) da CIP durante degradação fotoinduzida foi de 2,5 h, enquanto durante os processos de fotocatálise heterogênea, peroxônio e ozonização, t1/2 foi 20, 15 e 9 min, respectivamente. Os melhores resultados obtidos para a ozonização na degradação de CIP foram conseqüência da maior reatividade do fármaco com ozônio do que com espécies radicalares formadas durante os processos. Porém, no que diz respeito à redução da demanda química de oxigênio (DQO) e absorbância integrada, os processos peroxônio e de fotocatálise heterogênea, (maior capacidade de geração de HO ) foram mais efetivos que os processos fotoinduzido e de ozonização (menor capacidade de geração de HO ). Os produtos formados durante os diferentes processos demonstraram ser bastante semelhantes. Avaliou-se também a degradação fotoinduzida de CIP em solução sintética (lâmpada de Hg de média pressão de 150 W, reator em batelada), em concentração ambiental de 0,1 mg L-1 (0,3 x 10-3 mol L-1) e pH 9 (NH4Cl/KOH) por meio de HPLCFLD. A taxa de reação de primeira ordem e t1/2 foram 1,56 ±0,11 x 10-2 s-1 e 44±7 s, respectivamente. As estruturas dos fotometabólitos foram investigadas através de cromatografia líquida com detecção de massas (LC-MS). Cinco prováveis fotometabólitos primários foram identificados e demonstraram não ser prontamente biodegradáveis frente a closed bottle test (CBT). Estes compostos são produtos de defluoração, descarboxilação e abertura do anel piperazínico e já foram identificados em estudos anteriores, porém, nunca nas condições testadas na presente investigação.Universidade Federal de Santa MariaBRQuímicaUFSMPrograma de Pós-Graduação em QuímicaMartins, Ayrton Figueiredohttp://lattes.cnpq.br/2113532494494821Adaime, Martha Bohrerhttp://lattes.cnpq.br/4385786922516848Costa, Adilson Ben dahttp://lattes.cnpq.br/2604778196819181Kunz, Airtonhttp://lattes.cnpq.br/0003350901000829Costa, Rejane Helena Ribeiro dahttp://lattes.cnpq.br/6762004196316452Vasconcelos, Tibiriçá Gonçalves2017-05-252017-05-252006-09-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfapplication/pdfVASCONCELOS, Tibiriçá Gonçalves. Antimicrobial ciprofloxacin in hospital effluent: environmental exposure, risk assessment and degradation by advanced oxidation processes. 2006. 85 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2006.http://repositorio.ufsm.br/handle/1/4303porinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2023-03-07T11:31:44Zoai:repositorio.ufsm.br:1/4303Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2023-03-07T11:31:44Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação Antimicrobial ciprofloxacin in hospital effluent: environmental exposure, risk assessment and degradation by advanced oxidation processes |
title |
Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação |
spellingShingle |
Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação Vasconcelos, Tibiriçá Gonçalves Química Química analítica Efluente hospitalar Ciprofloxacin Degradação CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação |
title_full |
Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação |
title_fullStr |
Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação |
title_full_unstemmed |
Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação |
title_sort |
Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação |
author |
Vasconcelos, Tibiriçá Gonçalves |
author_facet |
Vasconcelos, Tibiriçá Gonçalves |
author_role |
author |
dc.contributor.none.fl_str_mv |
Martins, Ayrton Figueiredo http://lattes.cnpq.br/2113532494494821 Adaime, Martha Bohrer http://lattes.cnpq.br/4385786922516848 Costa, Adilson Ben da http://lattes.cnpq.br/2604778196819181 Kunz, Airton http://lattes.cnpq.br/0003350901000829 Costa, Rejane Helena Ribeiro da http://lattes.cnpq.br/6762004196316452 |
dc.contributor.author.fl_str_mv |
Vasconcelos, Tibiriçá Gonçalves |
dc.subject.por.fl_str_mv |
Química Química analítica Efluente hospitalar Ciprofloxacin Degradação CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Química Química analítica Efluente hospitalar Ciprofloxacin Degradação CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In the present study, the presence of the antimicrobial ciprofloxacin (CIP) in effluent from the first-aid clinic of the University Hospital of Santa Maria (PA-HUSM) and its degradation by advanced oxidation processes (AOPs) - photo-induced process (medium pressure Hg-lamp 125 W, batch recirculation reactor, pH 3), heterogeneous catalysis (medium pressure Hg-lamp 125 W, helicoidal tubular reactor, pH 3, 400 mg TiO2), ozonation and peroxone (450 mg O3 h-1, pH 9, semi-batch system, 500 mg H2O2 L-1 for peroxone) were investigated. Determination of the CIP concentration developed by high pressure liquid chromatography with fluorescence detection (HPLC-FLD) was measured before (P1) and after (P2) treatment system (cesspit and anaerobic filter), during 7 days. Measured environmental concentrations (MECs) were 19-155 μg L-1 (average: 65±45 μg L-1) and 32-99 μg L-1 (average: 54±21 μg L-1) in P1 and P2, respectively. In addition, risk assessment based on the MECs and ecotoxicity data from the literature was proposed. Using three different values of predicted no-effect concentration (PNEC), MECs/PNEC ratios between 4-1,980 were calculated. These risk quotients imply a high risk for a negative impact of CIP to aquatic environment and suggest that risk management is necessary. These quotients are 48-3,300-fold higher than those found in developed countries and mean a worse-case than the discussed wide world until now. Regarding the treatment of the effluent by AOPs, photo-induced degradation was slowest than the other processes: half-life (t1/2) during photo-induced of CIP was 2.5 h, while heterogeneous photocatalysis, peroxone and ozonation presented 20, 15 and 9 min, respectively. The best results obtained through ozonation were consequence of the higher reactivity of CIP with ozone than with radicalar species formed during the processes. However, about chemical oxygen demand (COD) and integrated absorbance, peroxone and heterogeneous photocatalysis (higher capacity for hydroxyl radical generation) were more effective than the photo-induced and ozonation processes (lower hydroxyl radical generation capacity). The metabolites formed during the processes demonstrated to be very similar. In addition, photo-induced degradation of CIP (medium pressure Hg-lamp 150 W, batch reactor) in environmental concentration of 0.1 mg L-1 (0.3 x 10-6 mol L-1) and pH 9 (NH4Cl/KOH) was studied. The first order rate constant and half-life were 1.56 ±0.11 x 10-2 s-1 (R2 > 0.999) and 44±7 s, respectively. The first formed metabolites were identified by HPLC-FLD and high pressure liquid chromatography with mass detection (LC-MS). Five compounds were qualitatively identified as probable metabolites and were not ready biodegradable by closed bottle test (CBT). They would be products from reactions of defluorination, decarboxilation and break of the piperazine ring. They have been already reported in the literature but under other conditions. |
publishDate |
2006 |
dc.date.none.fl_str_mv |
2006-09-01 2017-05-25 2017-05-25 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
VASCONCELOS, Tibiriçá Gonçalves. Antimicrobial ciprofloxacin in hospital effluent: environmental exposure, risk assessment and degradation by advanced oxidation processes. 2006. 85 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2006. http://repositorio.ufsm.br/handle/1/4303 |
identifier_str_mv |
VASCONCELOS, Tibiriçá Gonçalves. Antimicrobial ciprofloxacin in hospital effluent: environmental exposure, risk assessment and degradation by advanced oxidation processes. 2006. 85 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2006. |
url |
http://repositorio.ufsm.br/handle/1/4303 |
dc.language.iso.fl_str_mv |
por |
language |
por |
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info:eu-repo/semantics/openAccess |
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openAccess |
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application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria BR Química UFSM Programa de Pós-Graduação em Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria BR Química UFSM Programa de Pós-Graduação em Química |
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reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
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Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
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UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
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Manancial - Repositório Digital da UFSM |
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Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
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1805922091405410304 |