Degradação de pesticidas por processos oxidativos avançados

Detalhes bibliográficos
Autor(a) principal: Gonçalves, Bárbara Rezende
Data de Publicação: 2022
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFU
Texto Completo: https://repositorio.ufu.br/handle/123456789/35618
http://doi.org/10.14393/ufu.te.2022.449
Resumo: Due to the low efficiency in the degradation of emerging contaminants by conventional treatments, Advanced Oxidative Processes (AOPs) have been used to efficiently degrade them in environmental matrices. In this work, different processes were evaluated for the degradation of pesticides in sewage treatment plants (STP) and in distilled water (DW) at a pH close to neutral (pH 6-7). In the first step, the photo-Fenton process modified with ethylenediamine-N,N′-disuccinic acid (EDDS) was evaluated for degradation of a mixture of pesticides (5 µmol L–1 of each) ametrine (AMT), atrazine (ATZ), imidacloprid (IMD) and tebuthiuron (TBH). Initially, the operational parameters (concentration of Fe3+-EDDS, molar ratio Fe:EDDS, mode of addition of EDDS and radiation source) were evaluated, and removals of 80–98% of target pesticides were obtained using 300 µmol L–1 of H2O2 and 30 µmol L–1 of Fe3+-EDDS in a molar ratio of 1:2 in DW, being more efficient than the classic photo-Fenton process (30–84% removal). However, due to the influence of inorganic ions and natural organic matter from the STP effluent, it was necessary to increase the reagent concentration six times (180 µmol L–1 of Fe3+-EDDS and 1800 µmol L–1 of H2O2) to reach the same proportion as in DW. Acute toxicity for Vibrio fischeri was evaluated during treatment in DW, and, despite the formation of more toxic intermediates, these products were degraded throughout the treatment, since there was no bacteria inhibition at the end of the process. In STP it was observed a reduction in toxicity to Drosophila melanogaster flies and antibacterial activity for Escherichia coli. Subsequently, the degradation of TBH alone (100 µg L–1 in DW and 500 µg L–1 in STP) was evaluated, due to its higher recalcitrance. In this step, UV-C radiation was evaluated with different peroxides (H2O2, S2O82– and HSO5–), reaching limit of quantification (12 µg L–1) in both matrices (88% degradation). Fourteen transformation products (TP) were identified, one of them reported for the first time in the literature, and, considering the radical species involved (HO• and SO4•–), two degradation mechanisms were proposed: one by abstraction and the other by electron transfer. Using Eisenia andrei earthworms, it was observed that at the end of the UV-C/peroxides processes there was no formation of more toxic by-products. Therefore, the proposed treatments are interesting alternatives for the degradation of contaminants of emerging concern and effective for the reduction of toxicity in DW and STP effluents.
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spelling Degradação de pesticidas por processos oxidativos avançadosDegradation of pesticides by advanced oxidative processesContaminantes de preocupação emergenteContaminants of emerging concernComplexos de ferroIron complexesEfluente sanitárioSanitary effluentPeróxidosPeroxidesProdutos de TransformaçãoTransformation productsToxicidadeToxicityCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAQuimicaQuímica ambientalÁguas residuais - Aspectos ambientaisDue to the low efficiency in the degradation of emerging contaminants by conventional treatments, Advanced Oxidative Processes (AOPs) have been used to efficiently degrade them in environmental matrices. In this work, different processes were evaluated for the degradation of pesticides in sewage treatment plants (STP) and in distilled water (DW) at a pH close to neutral (pH 6-7). In the first step, the photo-Fenton process modified with ethylenediamine-N,N′-disuccinic acid (EDDS) was evaluated for degradation of a mixture of pesticides (5 µmol L–1 of each) ametrine (AMT), atrazine (ATZ), imidacloprid (IMD) and tebuthiuron (TBH). Initially, the operational parameters (concentration of Fe3+-EDDS, molar ratio Fe:EDDS, mode of addition of EDDS and radiation source) were evaluated, and removals of 80–98% of target pesticides were obtained using 300 µmol L–1 of H2O2 and 30 µmol L–1 of Fe3+-EDDS in a molar ratio of 1:2 in DW, being more efficient than the classic photo-Fenton process (30–84% removal). However, due to the influence of inorganic ions and natural organic matter from the STP effluent, it was necessary to increase the reagent concentration six times (180 µmol L–1 of Fe3+-EDDS and 1800 µmol L–1 of H2O2) to reach the same proportion as in DW. Acute toxicity for Vibrio fischeri was evaluated during treatment in DW, and, despite the formation of more toxic intermediates, these products were degraded throughout the treatment, since there was no bacteria inhibition at the end of the process. In STP it was observed a reduction in toxicity to Drosophila melanogaster flies and antibacterial activity for Escherichia coli. Subsequently, the degradation of TBH alone (100 µg L–1 in DW and 500 µg L–1 in STP) was evaluated, due to its higher recalcitrance. In this step, UV-C radiation was evaluated with different peroxides (H2O2, S2O82– and HSO5–), reaching limit of quantification (12 µg L–1) in both matrices (88% degradation). Fourteen transformation products (TP) were identified, one of them reported for the first time in the literature, and, considering the radical species involved (HO• and SO4•–), two degradation mechanisms were proposed: one by abstraction and the other by electron transfer. Using Eisenia andrei earthworms, it was observed that at the end of the UV-C/peroxides processes there was no formation of more toxic by-products. Therefore, the proposed treatments are interesting alternatives for the degradation of contaminants of emerging concern and effective for the reduction of toxicity in DW and STP effluents.CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorTese (Doutorado)Devido à baixa eficiência na degradação de contaminantes de preocupação emergente pelos tratamentos convencionais, os Processos Oxidativos Avançados (POAs) têm sido utilizados para degradá-los eficientemente em matrizes aquosas ambientais. Neste trabalho diferentes processos foram avaliados para a degradação de pesticidas em efluente tratado gerado na estação de tratamento de esgoto (ETE) e em água destilada (AD) em pH próximo ao neutro (pH 6-7). Na primeira etapa, foi avaliado o processo foto-Fenton modificado com o ácido etilenodiamina-N, N′-disuccínico (EDDS) para a degradação de uma mistura (5 µmol L–1 de cada) dos pesticidas ametrina (AMT), atrazina (ATZ), imidacloprid (IMD) e tebuthiuron (TBH). Inicialmente, avaliou-se os parâmetros operacionais (concentração de Fe3+-EDDS, razão molar Fe:EDDS, modo de adição de EDDS e fonte de radiação), e, foram obtidas remoções de 80–98% dos pesticidas alvo usando 300 μmol L–1 de H2O2 e 30 μmol L–1 de Fe3+-EDDS em uma razão molar de 1:2 em AD, sendo mais eficiente que o processo foto-Fenton clássico (30–84% de remoção). Contudo, devido à influência dos íons inorgânicos e da matéria orgânica natural do efluente de ETE, foi necessário aumentar seis vezes a concentração dos reagentes (180 μmol L−1 de Fe3+-EDDS e 1800 μmol L−1 de H2O2) para atingir a mesma proporção que em AD. A toxicidade aguda para Vibrio fischeri foi avaliada durante o tratamento em AD, e, apesar da formação de intermediários mais tóxicos, estes produtos foram degradados ao longo do tratamento, uma vez que não houve inibição para a bactéria ao final do processo. Em ETE observou-se a redução da toxicidade para as moscas Drosophila melanogaster e da atividade antibacteriana para Escherichia coli. Posteriormente, foi avaliada a degradação somente de TBH (100 μg L–1 em AD e 500 μg L–1 em ETE), devido à sua maior recalcitrância. Nesta etapa, a radiação UV-C foi avaliada com diferentes peróxidos (H2O2, S2O82– e HSO5–), alcançando o limite de quantificação (12 μg L–1) em ambas as matrizes (88% de degradação). Foram identificados quatorze produtos de transformação (PT) sendo um PT inédito na literatura, e, considerando-se as espécies radicalares envolvidas (HO• e SO4•–) foram propostos dois mecanismos de degradação: um por abstração e outro por transferência eletrônica. Utilizando minhocas Eisenia andrei observou-se que ao final dos processos UV-C/peróxidos não houve formação de subprodutos mais tóxicos. Portanto, os tratamentos propostos são alternativas interessante para a degradação de contaminantes de preocupação emergente e eficazes para a redução da toxicidade em AD e efluentes de ETE.Universidade Federal de UberlândiaBrasilPrograma de Pós-graduação em QuímicaTrovó, Alam Gustavohttp://lattes.cnpq.br/7274761440886112Munoz, Rodrigo Alejandro Abarzahttp://lattes.cnpq.br/0884149595277368Teixeira, Antonio Carlos Silva Costahttp://lattes.cnpq.br/0487846437293173Brito, Núbia Natália dehttp://lattes.cnpq.br/9075769086344855Moreira, Renata Pereira Lopeshttp://lattes.cnpq.br/2773378870906771Gonçalves, Bárbara Rezende2022-08-22T17:36:59Z2022-08-22T17:36:59Z2022-06-24info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfGONÇALVES, Bárbara Rezende. Degradação de pesticidas pro processos oxidativos avançados. 2022. 153 f. Tese (Doutorado em Química) - Universidade Federal de Uberlândia, Uberlândia, 2022. DOI http://doi.org/10.14393/ufu.te.2022.449https://repositorio.ufu.br/handle/123456789/35618http://doi.org/10.14393/ufu.te.2022.449porhttp://creativecommons.org/licenses/by-nc-nd/3.0/us/info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFUinstname:Universidade Federal de Uberlândia (UFU)instacron:UFU2022-08-23T06:27:29Zoai:repositorio.ufu.br:123456789/35618Repositório InstitucionalONGhttp://repositorio.ufu.br/oai/requestdiinf@dirbi.ufu.bropendoar:2022-08-23T06:27:29Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU)false
dc.title.none.fl_str_mv Degradação de pesticidas por processos oxidativos avançados
Degradation of pesticides by advanced oxidative processes
title Degradação de pesticidas por processos oxidativos avançados
spellingShingle Degradação de pesticidas por processos oxidativos avançados
Gonçalves, Bárbara Rezende
Contaminantes de preocupação emergente
Contaminants of emerging concern
Complexos de ferro
Iron complexes
Efluente sanitário
Sanitary effluent
Peróxidos
Peroxides
Produtos de Transformação
Transformation products
Toxicidade
Toxicity
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
Quimica
Química ambiental
Águas residuais - Aspectos ambientais
title_short Degradação de pesticidas por processos oxidativos avançados
title_full Degradação de pesticidas por processos oxidativos avançados
title_fullStr Degradação de pesticidas por processos oxidativos avançados
title_full_unstemmed Degradação de pesticidas por processos oxidativos avançados
title_sort Degradação de pesticidas por processos oxidativos avançados
author Gonçalves, Bárbara Rezende
author_facet Gonçalves, Bárbara Rezende
author_role author
dc.contributor.none.fl_str_mv Trovó, Alam Gustavo
http://lattes.cnpq.br/7274761440886112
Munoz, Rodrigo Alejandro Abarza
http://lattes.cnpq.br/0884149595277368
Teixeira, Antonio Carlos Silva Costa
http://lattes.cnpq.br/0487846437293173
Brito, Núbia Natália de
http://lattes.cnpq.br/9075769086344855
Moreira, Renata Pereira Lopes
http://lattes.cnpq.br/2773378870906771
dc.contributor.author.fl_str_mv Gonçalves, Bárbara Rezende
dc.subject.por.fl_str_mv Contaminantes de preocupação emergente
Contaminants of emerging concern
Complexos de ferro
Iron complexes
Efluente sanitário
Sanitary effluent
Peróxidos
Peroxides
Produtos de Transformação
Transformation products
Toxicidade
Toxicity
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
Quimica
Química ambiental
Águas residuais - Aspectos ambientais
topic Contaminantes de preocupação emergente
Contaminants of emerging concern
Complexos de ferro
Iron complexes
Efluente sanitário
Sanitary effluent
Peróxidos
Peroxides
Produtos de Transformação
Transformation products
Toxicidade
Toxicity
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
Quimica
Química ambiental
Águas residuais - Aspectos ambientais
description Due to the low efficiency in the degradation of emerging contaminants by conventional treatments, Advanced Oxidative Processes (AOPs) have been used to efficiently degrade them in environmental matrices. In this work, different processes were evaluated for the degradation of pesticides in sewage treatment plants (STP) and in distilled water (DW) at a pH close to neutral (pH 6-7). In the first step, the photo-Fenton process modified with ethylenediamine-N,N′-disuccinic acid (EDDS) was evaluated for degradation of a mixture of pesticides (5 µmol L–1 of each) ametrine (AMT), atrazine (ATZ), imidacloprid (IMD) and tebuthiuron (TBH). Initially, the operational parameters (concentration of Fe3+-EDDS, molar ratio Fe:EDDS, mode of addition of EDDS and radiation source) were evaluated, and removals of 80–98% of target pesticides were obtained using 300 µmol L–1 of H2O2 and 30 µmol L–1 of Fe3+-EDDS in a molar ratio of 1:2 in DW, being more efficient than the classic photo-Fenton process (30–84% removal). However, due to the influence of inorganic ions and natural organic matter from the STP effluent, it was necessary to increase the reagent concentration six times (180 µmol L–1 of Fe3+-EDDS and 1800 µmol L–1 of H2O2) to reach the same proportion as in DW. Acute toxicity for Vibrio fischeri was evaluated during treatment in DW, and, despite the formation of more toxic intermediates, these products were degraded throughout the treatment, since there was no bacteria inhibition at the end of the process. In STP it was observed a reduction in toxicity to Drosophila melanogaster flies and antibacterial activity for Escherichia coli. Subsequently, the degradation of TBH alone (100 µg L–1 in DW and 500 µg L–1 in STP) was evaluated, due to its higher recalcitrance. In this step, UV-C radiation was evaluated with different peroxides (H2O2, S2O82– and HSO5–), reaching limit of quantification (12 µg L–1) in both matrices (88% degradation). Fourteen transformation products (TP) were identified, one of them reported for the first time in the literature, and, considering the radical species involved (HO• and SO4•–), two degradation mechanisms were proposed: one by abstraction and the other by electron transfer. Using Eisenia andrei earthworms, it was observed that at the end of the UV-C/peroxides processes there was no formation of more toxic by-products. Therefore, the proposed treatments are interesting alternatives for the degradation of contaminants of emerging concern and effective for the reduction of toxicity in DW and STP effluents.
publishDate 2022
dc.date.none.fl_str_mv 2022-08-22T17:36:59Z
2022-08-22T17:36:59Z
2022-06-24
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 GONÇALVES, Bárbara Rezende. Degradação de pesticidas pro processos oxidativos avançados. 2022. 153 f. Tese (Doutorado em Química) - Universidade Federal de Uberlândia, Uberlândia, 2022. DOI http://doi.org/10.14393/ufu.te.2022.449
https://repositorio.ufu.br/handle/123456789/35618
http://doi.org/10.14393/ufu.te.2022.449
identifier_str_mv GONÇALVES, Bárbara Rezende. Degradação de pesticidas pro processos oxidativos avançados. 2022. 153 f. Tese (Doutorado em Química) - Universidade Federal de Uberlândia, Uberlândia, 2022. DOI http://doi.org/10.14393/ufu.te.2022.449
url https://repositorio.ufu.br/handle/123456789/35618
http://doi.org/10.14393/ufu.te.2022.449
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language por
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dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Universidade Federal de Uberlândia
Brasil
Programa de Pós-graduação em Química
publisher.none.fl_str_mv Universidade Federal de Uberlândia
Brasil
Programa de Pós-graduação em Química
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