Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados

Detalhes bibliográficos
Ano de defesa: 2018
Autor(a) principal: Bisognin, Ramiro Pereira
Orientador(a): Não Informado pela instituição
Banca de defesa: Não Informado pela instituição
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
dARK ID: ark:/26339/001300000g49r
Idioma: por
Instituição de defesa: Universidade Federal de Santa Maria
Brasil
Engenharia Civil
UFSM
Programa de Pós-Graduação em Engenharia Civil
Centro de Tecnologia
Programa de Pós-Graduação: Não Informado pela instituição
Departamento: Não Informado pela instituição
País: Não Informado pela instituição
Palavras-chave em Português:
Link de acesso: http://repositorio.ufsm.br/handle/1/18994
Resumo: The high worldwide consumption of remedies, coupled with the incomplete assimilation by animals and humans and the deficient removal by conventional effluent treatment systems, made the pharmaceuticals a persistent group of micropollutants. For this reason, the main goal of this thesis was to study the degradation and/or simultaneous removal of pharmaceuticals in a wastewater treatment plant (WWTP) by biological processes and by advanced oxidation using ozone, ultraviolet radiation and combinations with peroxide hydrogen. The study was carried out in three stages, the first one consisted in the investigation of the occurrence, fate and removal of 43 pharmaceuticals and hormones in effluent and sludge of the largest WWTP in Rio Grande do Sul (Southem Brazil), in the months of November 2017, March and April 2018. The determination of the pharmaceuticals was performed by a ultra high-performance liquid chromatography coupled to mass-mass spectrometry (UHPLC-MS/MS). Thus, 13 pharmaceuticals were detected in the crude effluent and 11 in the treated one. Although the highest concentrations in the raw effluent were paracetamol (137.98 μg L-1) and caffeine (35.29 μg L- 1), the highest diversity was of antibiotics at concentrations ranging from 0.023 to 1.374 μg L-1, for metronidazole and sulfamethoxazole, respectively. The pharmaceuticals doxycycline, fembendazole, norfloxacin and tetracycline were detected only in the sludge, but the highest concentration was ciprofloxacin (5.034 mg kg-1). During the treatment, increases in the concentration of some pharmaceuticals were recorded, as well as removals above 97%. However, high pharmaceutical loads (511.466 g d-1) were observed in the recipient water body. The second step consisted of the degradation of the 11 pharmaceuticals detected in the WWTP, using O3 in two dosages (0.5 and 0.9 mgO3 mgCOD-1), UV photolysis (254 nm), and the O3/UV, H2O2/UV and O3/H2O2/UV with 0.5 mgO3 mgCOD-1 and 25 mgH2O2 L-1. For degradation assays, the active ingredients ciprofloxacin, oxytetracycline, paracetamol, sulfamethoxazole and trimethoprim had increased concentrations above the predicted no effect concentration (PNEC). The study were performed at a ambient temperature of 20.60 ± 0.30 ºC and pH 6.94 ± 0.02, with aliquots being sampled at 7.5 and 15 min. The O3/H2O2/UV process was more efficient for the degradation of all detected pharmaceuticals, allowing a reduction of 89.32% of oxytetracycline, 96.79% of caffeine, 97.40% of trimethoprim, 97.75% of ciprofloxacin, 99.79% sulfamethoxazole, 99.96% paracetamol and 100% of clindamycin, ofloxacin, sulfadiazine, sulfathiazole and tylosin. The same process was responsible for the highest percentage of mineralization (60.52%), proving the synergetic effect between the combined oxidizing agents. Finally, the third step consisted in evaluating the (eco)toxicity of the three groups of effluents: (a) treated by biological processes, (b) with increased concentration of pharmaceuticals, and (c) posttreated by O3/H2O2/UV. The levels of thiobarbituric acid reactive substances (TBARS) and the activity of the enzymes acetylcholinesterase (AChE), catalase (CAT) and glutathione-S-transferase (GST) were evaluated in different organs of fish of the species Astyanax bimaculatus exposed to effluents for 14 days. Thus, it was evidenced that residuals of pharmaceuticals can cause oxidative stress, affecting biochemical and enzymatic parameters in Astyanax sp., as well the O3/H2O2/UV process can reduce damages to fish even with the possible formation of metabolites, which have been shown be less toxic than the original compounds.
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spelling Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançadosDegradation of pharmaceuticals in effluent of a sewage treatment plant using advanced processesEsgoto sanitárioMicropoluentesTratamento biológicoProcessos oxidativos avançadosBiomarcadores de estresse oxidativoSewageMicropollutantsBiological treatmentAdvanced oxidative processesBiomarkers of oxidative stressCNPQ::ENGENHARIAS::ENGENHARIA CIVILThe high worldwide consumption of remedies, coupled with the incomplete assimilation by animals and humans and the deficient removal by conventional effluent treatment systems, made the pharmaceuticals a persistent group of micropollutants. For this reason, the main goal of this thesis was to study the degradation and/or simultaneous removal of pharmaceuticals in a wastewater treatment plant (WWTP) by biological processes and by advanced oxidation using ozone, ultraviolet radiation and combinations with peroxide hydrogen. The study was carried out in three stages, the first one consisted in the investigation of the occurrence, fate and removal of 43 pharmaceuticals and hormones in effluent and sludge of the largest WWTP in Rio Grande do Sul (Southem Brazil), in the months of November 2017, March and April 2018. The determination of the pharmaceuticals was performed by a ultra high-performance liquid chromatography coupled to mass-mass spectrometry (UHPLC-MS/MS). Thus, 13 pharmaceuticals were detected in the crude effluent and 11 in the treated one. Although the highest concentrations in the raw effluent were paracetamol (137.98 μg L-1) and caffeine (35.29 μg L- 1), the highest diversity was of antibiotics at concentrations ranging from 0.023 to 1.374 μg L-1, for metronidazole and sulfamethoxazole, respectively. The pharmaceuticals doxycycline, fembendazole, norfloxacin and tetracycline were detected only in the sludge, but the highest concentration was ciprofloxacin (5.034 mg kg-1). During the treatment, increases in the concentration of some pharmaceuticals were recorded, as well as removals above 97%. However, high pharmaceutical loads (511.466 g d-1) were observed in the recipient water body. The second step consisted of the degradation of the 11 pharmaceuticals detected in the WWTP, using O3 in two dosages (0.5 and 0.9 mgO3 mgCOD-1), UV photolysis (254 nm), and the O3/UV, H2O2/UV and O3/H2O2/UV with 0.5 mgO3 mgCOD-1 and 25 mgH2O2 L-1. For degradation assays, the active ingredients ciprofloxacin, oxytetracycline, paracetamol, sulfamethoxazole and trimethoprim had increased concentrations above the predicted no effect concentration (PNEC). The study were performed at a ambient temperature of 20.60 ± 0.30 ºC and pH 6.94 ± 0.02, with aliquots being sampled at 7.5 and 15 min. The O3/H2O2/UV process was more efficient for the degradation of all detected pharmaceuticals, allowing a reduction of 89.32% of oxytetracycline, 96.79% of caffeine, 97.40% of trimethoprim, 97.75% of ciprofloxacin, 99.79% sulfamethoxazole, 99.96% paracetamol and 100% of clindamycin, ofloxacin, sulfadiazine, sulfathiazole and tylosin. The same process was responsible for the highest percentage of mineralization (60.52%), proving the synergetic effect between the combined oxidizing agents. Finally, the third step consisted in evaluating the (eco)toxicity of the three groups of effluents: (a) treated by biological processes, (b) with increased concentration of pharmaceuticals, and (c) posttreated by O3/H2O2/UV. The levels of thiobarbituric acid reactive substances (TBARS) and the activity of the enzymes acetylcholinesterase (AChE), catalase (CAT) and glutathione-S-transferase (GST) were evaluated in different organs of fish of the species Astyanax bimaculatus exposed to effluents for 14 days. Thus, it was evidenced that residuals of pharmaceuticals can cause oxidative stress, affecting biochemical and enzymatic parameters in Astyanax sp., as well the O3/H2O2/UV process can reduce damages to fish even with the possible formation of metabolites, which have been shown be less toxic than the original compounds.O elevado consumo mundial de medicamentos, associado à incompleta assimilação por animais e seres humanos e a remoção deficitária por sistemas convencionais de tratamento de efluentes, tornaram os fármacos um grupo de micropoluentes persistentes. Por este motivo, na presente tese objetivou-se estudar a degradação e/ou remoção simultânea de fármacos em efluente de uma estação de tratamento de esgoto sanitário (ETE) por processos biológicos e por oxidação avançada utilizando ozônio, radiação ultravioleta e combinações com peróxido de hidrogênio. O estudo foi desenvolvido em três etapas, a primeira consistiu na investigação da ocorrência, destino e remoção de 43 fármacos e hormônios no efluente e no lodo da maior ETE do Rio Grande do Sul, nos meses de novembro de 2017, março e abril de 2018. A determinação dos fármacos foi realizada por cromatografia líquida de ultra-alta eficiência acoplada à espectrometria de massas em tandem (UHPLC-MS/MS). Assim, foram detectados 13 fármacos no efluente bruto e 11 no tratado. Apesar das maiores concentrações no efluente bruto terem sido de paracetamol (137,980 μg L-1) e cafeína (35,290 μg L-1), a maior diversidade foi de antibióticos, em concentrações que variaram de 0,023 a 1,374 μg L-1 de metronidazol e sulfametoxazol, respectivamente. Os fármacos doxiciclina, fembendazol, norfloxacina e tetraciclina foram detectados somente no lodo, porém a maior concentração foi de ciprofloxacina (5,034 mg kg-1). Durante o tratamento, foram registrados incrementos na concentração de alguns fármacos, como também remoções superiores a 97%. Contudo, constatou-se elevada carga de medicamentos (511,466 g d-1) despejados no corpo hídrico receptor. A segunda etapa consistiu na degradação dos 11 fármacos detectados no efluente da ETE mencionada, utilizando O3 em duas dosagens (0,5 e 0,9 mgO3 mgCOD-1), fotólise UV (254 nm), e as combinações O3/UV, H2O2/UV e O3/H2O2/UV com 0,5 mgO3 mgCOD-1 e 25 mgH2O2 L-1. Para os ensaios de degradação, os princípios ativos ciprofloxacina, oxitetraciclina, paracetamol, sulfametoxazol e trimetoprima tiveram as concentrações aumentadas, acima da concentração prevista sem efeito (CPSE). Os estudos foram realizados a temperatura de 20,60 ± 0,30 ºC e pH 6,94 ± 0,02, com recolhimento de alíquotas a 7,5 e 15 min. O processo O3/H2O2/UV foi o mais eficiente na degradação de todos os fármacos detectados, possibilitando a redução de 89,32% de oxitetraciclina, 96,79% de cafeína, 97,40% de trimetoprima, 97,75% de ciprofloxacina, 99,79% de sulfametoxazol, 99,96% de paracetamol e 100% de clindamicina, ofloxacina, sulfadiazina, sulfatiazol e tilosina. O mesmo processo foi responsável pelo maior percentual de mineralização (60,52%), comprovando o efeito sinérgico entre os agentes oxidantes combinados. Por fim, a terceira etapa consistiu na avaliação da (eco)toxicidade dos três grupos de efluentes: (a) tratado pelos processos biológicos, (b) com concentração aumentada de fármacos, e (c) pós-tratado por O3/H2O2/UV. Foram avaliados os níveis de substâncias reativas ao ácido tiobarbitúrico (TBARS) e a atividade das enzimas acetilcolinesterase (AChE), catalase (CAT) e glutationa S-transferase (GST), em diferentes órgãos de peixes da espécie Astyanax bimaculatus expostos aos efluentes durante 14 dias. Desta forma, evidenciou-se que os resíduos de fármacos podem causar estresse oxidativo, afetando parâmetros bioquímicos e enzimáticos em Astyanax sp., assim como o processo O3/H2O2/UV pode reduzir os danos aos peixes mesmo com a possível formação de metabólitos, os quais se mostraram ser menos tóxicos que os compostos originais.Universidade Federal de Santa MariaBrasilEngenharia CivilUFSMPrograma de Pós-Graduação em Engenharia CivilCentro de TecnologiaWolff, Delmira Beatrizhttp://lattes.cnpq.br/2590812446293555Silveira, Djalma Dias dahttp://lattes.cnpq.br/1988016337388120Prestes, Osmar Damianhttp://lattes.cnpq.br/9632234955509028López, Diosnel Antonio Rodriguezhttp://lattes.cnpq.br/9189275068912186Vasconcellos, Noeli Júlia Schussler dehttp://lattes.cnpq.br/3726530263510005Bisognin, Ramiro Pereira2019-11-20T19:37:19Z2019-11-20T19:37:19Z2018-10-18info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/18994ark:/26339/001300000g49rporAttribution-NonCommercial-NoDerivatives 4.0 Internationalinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2019-11-21T06:02:38Zoai:repositorio.ufsm.br:1/18994Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/PUBhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.com||manancial@ufsm.bropendoar:2019-11-21T06:02:38Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.none.fl_str_mv Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados
Degradation of pharmaceuticals in effluent of a sewage treatment plant using advanced processes
title Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados
spellingShingle Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados
Bisognin, Ramiro Pereira
Esgoto sanitário
Micropoluentes
Tratamento biológico
Processos oxidativos avançados
Biomarcadores de estresse oxidativo
Sewage
Micropollutants
Biological treatment
Advanced oxidative processes
Biomarkers of oxidative stress
CNPQ::ENGENHARIAS::ENGENHARIA CIVIL
title_short Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados
title_full Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados
title_fullStr Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados
title_full_unstemmed Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados
title_sort Degradação de fármacos em efluente de uma estação de tratamento de esgoto sanitário utilizando processos avançados
author Bisognin, Ramiro Pereira
author_facet Bisognin, Ramiro Pereira
author_role author
dc.contributor.none.fl_str_mv Wolff, Delmira Beatriz
http://lattes.cnpq.br/2590812446293555
Silveira, Djalma Dias da
http://lattes.cnpq.br/1988016337388120
Prestes, Osmar Damian
http://lattes.cnpq.br/9632234955509028
López, Diosnel Antonio Rodriguez
http://lattes.cnpq.br/9189275068912186
Vasconcellos, Noeli Júlia Schussler de
http://lattes.cnpq.br/3726530263510005
dc.contributor.author.fl_str_mv Bisognin, Ramiro Pereira
dc.subject.por.fl_str_mv Esgoto sanitário
Micropoluentes
Tratamento biológico
Processos oxidativos avançados
Biomarcadores de estresse oxidativo
Sewage
Micropollutants
Biological treatment
Advanced oxidative processes
Biomarkers of oxidative stress
CNPQ::ENGENHARIAS::ENGENHARIA CIVIL
topic Esgoto sanitário
Micropoluentes
Tratamento biológico
Processos oxidativos avançados
Biomarcadores de estresse oxidativo
Sewage
Micropollutants
Biological treatment
Advanced oxidative processes
Biomarkers of oxidative stress
CNPQ::ENGENHARIAS::ENGENHARIA CIVIL
description The high worldwide consumption of remedies, coupled with the incomplete assimilation by animals and humans and the deficient removal by conventional effluent treatment systems, made the pharmaceuticals a persistent group of micropollutants. For this reason, the main goal of this thesis was to study the degradation and/or simultaneous removal of pharmaceuticals in a wastewater treatment plant (WWTP) by biological processes and by advanced oxidation using ozone, ultraviolet radiation and combinations with peroxide hydrogen. The study was carried out in three stages, the first one consisted in the investigation of the occurrence, fate and removal of 43 pharmaceuticals and hormones in effluent and sludge of the largest WWTP in Rio Grande do Sul (Southem Brazil), in the months of November 2017, March and April 2018. The determination of the pharmaceuticals was performed by a ultra high-performance liquid chromatography coupled to mass-mass spectrometry (UHPLC-MS/MS). Thus, 13 pharmaceuticals were detected in the crude effluent and 11 in the treated one. Although the highest concentrations in the raw effluent were paracetamol (137.98 μg L-1) and caffeine (35.29 μg L- 1), the highest diversity was of antibiotics at concentrations ranging from 0.023 to 1.374 μg L-1, for metronidazole and sulfamethoxazole, respectively. The pharmaceuticals doxycycline, fembendazole, norfloxacin and tetracycline were detected only in the sludge, but the highest concentration was ciprofloxacin (5.034 mg kg-1). During the treatment, increases in the concentration of some pharmaceuticals were recorded, as well as removals above 97%. However, high pharmaceutical loads (511.466 g d-1) were observed in the recipient water body. The second step consisted of the degradation of the 11 pharmaceuticals detected in the WWTP, using O3 in two dosages (0.5 and 0.9 mgO3 mgCOD-1), UV photolysis (254 nm), and the O3/UV, H2O2/UV and O3/H2O2/UV with 0.5 mgO3 mgCOD-1 and 25 mgH2O2 L-1. For degradation assays, the active ingredients ciprofloxacin, oxytetracycline, paracetamol, sulfamethoxazole and trimethoprim had increased concentrations above the predicted no effect concentration (PNEC). The study were performed at a ambient temperature of 20.60 ± 0.30 ºC and pH 6.94 ± 0.02, with aliquots being sampled at 7.5 and 15 min. The O3/H2O2/UV process was more efficient for the degradation of all detected pharmaceuticals, allowing a reduction of 89.32% of oxytetracycline, 96.79% of caffeine, 97.40% of trimethoprim, 97.75% of ciprofloxacin, 99.79% sulfamethoxazole, 99.96% paracetamol and 100% of clindamycin, ofloxacin, sulfadiazine, sulfathiazole and tylosin. The same process was responsible for the highest percentage of mineralization (60.52%), proving the synergetic effect between the combined oxidizing agents. Finally, the third step consisted in evaluating the (eco)toxicity of the three groups of effluents: (a) treated by biological processes, (b) with increased concentration of pharmaceuticals, and (c) posttreated by O3/H2O2/UV. The levels of thiobarbituric acid reactive substances (TBARS) and the activity of the enzymes acetylcholinesterase (AChE), catalase (CAT) and glutathione-S-transferase (GST) were evaluated in different organs of fish of the species Astyanax bimaculatus exposed to effluents for 14 days. Thus, it was evidenced that residuals of pharmaceuticals can cause oxidative stress, affecting biochemical and enzymatic parameters in Astyanax sp., as well the O3/H2O2/UV process can reduce damages to fish even with the possible formation of metabolites, which have been shown be less toxic than the original compounds.
publishDate 2018
dc.date.none.fl_str_mv 2018-10-18
2019-11-20T19:37:19Z
2019-11-20T19:37:19Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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format doctoralThesis
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://repositorio.ufsm.br/handle/1/18994
dc.identifier.dark.fl_str_mv ark:/26339/001300000g49r
url http://repositorio.ufsm.br/handle/1/18994
identifier_str_mv ark:/26339/001300000g49r
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Universidade Federal de Santa Maria
Brasil
Engenharia Civil
UFSM
Programa de Pós-Graduação em Engenharia Civil
Centro de Tecnologia
publisher.none.fl_str_mv Universidade Federal de Santa Maria
Brasil
Engenharia Civil
UFSM
Programa de Pós-Graduação em Engenharia Civil
Centro de Tecnologia
dc.source.none.fl_str_mv reponame:Manancial - Repositório Digital da UFSM
instname:Universidade Federal de Santa Maria (UFSM)
instacron:UFSM
instname_str Universidade Federal de Santa Maria (UFSM)
instacron_str UFSM
institution UFSM
reponame_str Manancial - Repositório Digital da UFSM
collection Manancial - Repositório Digital da UFSM
repository.name.fl_str_mv Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)
repository.mail.fl_str_mv atendimento.sib@ufsm.br||tedebc@gmail.com||manancial@ufsm.br
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