Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação

Detalhes bibliográficos
Ano de defesa: 2006
Autor(a) principal: Vasconcelos, Tibiriçá Gonçalves lattes
Orientador(a): Martins, Ayrton Figueiredo lattes
Banca de defesa: Adaime, Martha Bohrer lattes, Costa, Adilson Ben da lattes, Kunz, Airton lattes, Costa, Rejane Helena Ribeiro da 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:
Área do conhecimento CNPq:
Link de acesso: 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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spelling 2017-05-252017-05-252006-09-01VASCONCELOS, 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/1/4303In 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.Neste 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.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaQuímicaQuímica analíticaEfluente hospitalarCiprofloxacinDegradaçãoCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAAntimicrobial 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 processesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisMartins, 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/6762004196316452http://lattes.cnpq.br/6407925163803842Vasconcelos, Tibiriçá Gonçalves100600000000400300300500300300300ade6000d-a348-4d49-a531-6500a65a153aea3151e3-7ad5-45a2-8b60-32e1e404f8cbd17a2970-0025-4f55-941c-4c018124a302a453756f-c5f8-44d3-b2a5-b722712058a151bf9c0b-fea1-484c-81ef-df9d24ede7f1b8a318eb-9c30-4d1e-a09e-529dfa2068aainfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTIBIRICA VASCONCELOS.pdfapplication/pdf745788http://repositorio.ufsm.br/bitstream/1/4303/1/TIBIRICA%20VASCONCELOS.pdfadfa12e9e0e889709afadc4131204531MD511/43032023-03-07 08:31:44.302oai:repositorio.ufsm.br:1/4303Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132023-03-07T11:31:44Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.por.fl_str_mv Antimicrobial ciprofloxacina em efluente hospitalar: exposição ambiental, avaliação de risco e degradação através de processos avançados de oxidação
dc.title.alternative.eng.fl_str_mv 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.advisor1.fl_str_mv Martins, Ayrton Figueiredo
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/2113532494494821
dc.contributor.referee1.fl_str_mv Adaime, Martha Bohrer
dc.contributor.referee1Lattes.fl_str_mv http://lattes.cnpq.br/4385786922516848
dc.contributor.referee2.fl_str_mv Costa, Adilson Ben da
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/2604778196819181
dc.contributor.referee3.fl_str_mv Kunz, Airton
dc.contributor.referee3Lattes.fl_str_mv http://lattes.cnpq.br/0003350901000829
dc.contributor.referee4.fl_str_mv Costa, Rejane Helena Ribeiro da
dc.contributor.referee4Lattes.fl_str_mv http://lattes.cnpq.br/6762004196316452
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/6407925163803842
dc.contributor.author.fl_str_mv Vasconcelos, Tibiriçá Gonçalves
contributor_str_mv Martins, Ayrton Figueiredo
Adaime, Martha Bohrer
Costa, Adilson Ben da
Kunz, Airton
Costa, Rejane Helena Ribeiro da
dc.subject.por.fl_str_mv Química
Química analítica
Efluente hospitalar
Ciprofloxacin
Degradação
topic Química
Química analítica
Efluente hospitalar
Ciprofloxacin
Degradação
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.cnpq.fl_str_mv 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.issued.fl_str_mv 2006-09-01
dc.date.accessioned.fl_str_mv 2017-05-25
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dc.identifier.citation.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.
dc.identifier.uri.fl_str_mv 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.
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