Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada.
Autor(a) principal: | |
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Data de Publicação: | 2015 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da Universidade Federal do Ceará (UFC) |
Texto Completo: | http://www.repositorio.ufc.br/handle/riufc/14602 |
Resumo: | The substances called endocrine disruptors (ED) are a new category of environmental pollutants that interfere in the functions of the endocrine system, being found in the environment at concentrations in the order ug L-1 and L-1 ng. The WWTP effluent release are important sources of such compounds in the aquatic environment since the conventional methods of water treatment and sewage not completely remove these micropollutants. In this study we assessed the efficiency of pillared clay using tin dioxide as an agent for removing pilarizante DE (of different classes) in environmental matrices. Experimental design was used to evaluate the factors affecting the adsorptive process. For optimization step of the previously validated analytical method it was studied the effectiveness of three commercial SPE cartridges. Tributaries concentrations were obtained, effluents and removal efficiencies of two sewage treatment plants operating in full scale (UASB + chlorination). Finally, DE adsorption experiments were performed in single and multicomponent systems as well as regenerating the adsorbent. The Oasis and Strata-X cartridge efficiency showed high and selective ability, however, only Strata-X cartridge was selected in this study, since it showed higher recovery values (%) 50 (Sulfamethoxazol); 83 (Trimethoprim); 171 (diclofenac); 183 (estrone); 14 (17β-estradiol) and 82 (Bisphenol A). The chromatographic method was selective for all compounds studied, except for the hormone estriol. The quantification limit values (1.28 to 29.97 ng L-1) and detection limit (from 0.42 to 9.89 ng L-1) obtained in this study were low. Most of the recovery values was less than 100%. It was observed that the esgosto tributary of the studied WWTPs still present in their waste considerable amounts of DE, with average values of effluents from 21.94 to 311.79 ng L-1 for ETE Aracapé and 4.41 to 123.47 ng L 1 to ETE Mondubim, which highlights the need for a step of post-treatment in the studied WWTPs. They have found greater efficiencies treatment for compounds bisphenol A (90.8%) and 17α-ethinylestradiol (76.6%) ETE Mondubim. As for the compounds sulfamethoxazole and estrone it was observed an increase in effluent values of 18.9 and 28.6% respectively for the ETE Aracapé. The pillared clay showed higher adsorption capacity compared to the natural clay, due to enlargement of the interlayer space of the clay and increased volume of mesopores as evidenced by the characterization techniques. After analyzing the results of the factorial design was set optimum values of the variables found in the process to make the studies of kinetics and adsorption isotherm, which was temperature - 25 ° C; Agitation - 300 rpm; Mass of adsorbent: 300 mg and pH - 3. The kinetic study indicated 1 hour equilibration time, with the model of pseudo-second order which best fit to the data. The intraparticle diffusion mechanism was not the determining step of the speed and mass transfer process. The majority of the DE compounds obtained greater removal in multicomponent system when compared to single-component studies. The experimental data better adsorption isotherm set the model Freundlich except to refer to the TMP and BPA compounds. The sorbent regeneration tests indicated a significant reduction in the adsorption capacity of pillared clay in the 2nd adsorption cycle for TMP and compounds BPA, with a reduction of 99.5 and 79.2%, respectively. For E2 and E1 compounds, adsorption was affected after the 3rd cycle. |
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Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada.EDs present in environmental matrices: analysis by SPE-HPLC and removal with pillared clay.SaneamentoMicropoluentesAdsorçãoEstação de tratamento de esgotoThe substances called endocrine disruptors (ED) are a new category of environmental pollutants that interfere in the functions of the endocrine system, being found in the environment at concentrations in the order ug L-1 and L-1 ng. The WWTP effluent release are important sources of such compounds in the aquatic environment since the conventional methods of water treatment and sewage not completely remove these micropollutants. In this study we assessed the efficiency of pillared clay using tin dioxide as an agent for removing pilarizante DE (of different classes) in environmental matrices. Experimental design was used to evaluate the factors affecting the adsorptive process. For optimization step of the previously validated analytical method it was studied the effectiveness of three commercial SPE cartridges. Tributaries concentrations were obtained, effluents and removal efficiencies of two sewage treatment plants operating in full scale (UASB + chlorination). Finally, DE adsorption experiments were performed in single and multicomponent systems as well as regenerating the adsorbent. The Oasis and Strata-X cartridge efficiency showed high and selective ability, however, only Strata-X cartridge was selected in this study, since it showed higher recovery values (%) 50 (Sulfamethoxazol); 83 (Trimethoprim); 171 (diclofenac); 183 (estrone); 14 (17β-estradiol) and 82 (Bisphenol A). The chromatographic method was selective for all compounds studied, except for the hormone estriol. The quantification limit values (1.28 to 29.97 ng L-1) and detection limit (from 0.42 to 9.89 ng L-1) obtained in this study were low. Most of the recovery values was less than 100%. It was observed that the esgosto tributary of the studied WWTPs still present in their waste considerable amounts of DE, with average values of effluents from 21.94 to 311.79 ng L-1 for ETE Aracapé and 4.41 to 123.47 ng L 1 to ETE Mondubim, which highlights the need for a step of post-treatment in the studied WWTPs. They have found greater efficiencies treatment for compounds bisphenol A (90.8%) and 17α-ethinylestradiol (76.6%) ETE Mondubim. As for the compounds sulfamethoxazole and estrone it was observed an increase in effluent values of 18.9 and 28.6% respectively for the ETE Aracapé. The pillared clay showed higher adsorption capacity compared to the natural clay, due to enlargement of the interlayer space of the clay and increased volume of mesopores as evidenced by the characterization techniques. After analyzing the results of the factorial design was set optimum values of the variables found in the process to make the studies of kinetics and adsorption isotherm, which was temperature - 25 ° C; Agitation - 300 rpm; Mass of adsorbent: 300 mg and pH - 3. The kinetic study indicated 1 hour equilibration time, with the model of pseudo-second order which best fit to the data. The intraparticle diffusion mechanism was not the determining step of the speed and mass transfer process. The majority of the DE compounds obtained greater removal in multicomponent system when compared to single-component studies. The experimental data better adsorption isotherm set the model Freundlich except to refer to the TMP and BPA compounds. The sorbent regeneration tests indicated a significant reduction in the adsorption capacity of pillared clay in the 2nd adsorption cycle for TMP and compounds BPA, with a reduction of 99.5 and 79.2%, respectively. For E2 and E1 compounds, adsorption was affected after the 3rd cycle.As substâncias denominadas desreguladores endócrinos (DE) são uma categoria recente de poluentes ambientais que interferem nas funções do sistema endócrino, sendo encontradas no meio ambiente em concentrações na ordem de μg L-1 e ng L-1. Os efluentes de ETEs são importantes fontes de lançamento desses compostos no ambiente aquático uma vez que os processos convencionais de tratamento de água e esgoto não removem totalmente esses micropoluentes. Neste trabalho avaliou-se a eficiência da argila pilarizada utilizando o dióxido de estanho como agente pilarizante para remoção de DE (de diferentes classes) em matrizes ambientais. Foi utilizado o planejamento experimental para avaliação dos fatores que afetaram o processo adsortivo. Para etapa de otimização do método analítico anteriormente validado foi estudada a eficiência de três cartuchos SPE comerciais. Foram obtidas concentrações afluentes, efluentes e eficiências de remoção em duas estações de tratamento de esgotos que operavam em escala real (UASB + cloração). Por fim, foram realizados experimentos de adsorção de DE em sistemas mono e multicomponentes, assim como de regeneração do adsorvente. Os cartuchos Oasis e Strata-X mostraram elevada eficiência e capacidade seletiva, entretanto apenas o cartucho Strata-X foi o selecionado neste trabalho, uma vez que o mesmo mostrou maiores valores de recuperação (%) de 50 (Sulfamethoxazol); 83 (Trimetoprima); 171 (Diclofenaco); 183 (Estrona); 14 (17β-estradiol) e 82 (Bisfenol-A). O método cromatográfico mostrou-se seletivo para todos os compostos estudados, exceto para o hormônio estriol. Os valores de limite de quantificação (1,28-29,97 ng L-1) e limite de detecção (0,42-9,89 ng L-1) obtidos neste trabalho foram considerados baixos. A maioria dos valores de recuperação encontrados foi menor que 100%. Foi possível observar que o esgosto afluente às ETEs estudadas ainda apresentam em seus efluentes quantidades consideráveis de DE, com valores médios efluentes entre 21,94-311,79 ng L-1 para ETE Aracapé e 4,41-123,47 ng L-1 para ETE Mondubim, o que evidencia a necessidade de uma etapa de pós-tratamento nas ETEs estudadas. Foram encontradas maiores eficiências de tratamento para os compostos bisfenol A (90,8%) e 17α-etinilestradiol (76,6%) na ETE Mondubim. Já para os compostos sulfametoxazol e estrona foi observado um incremento nos valores efluentes de 18,9 e 28,6%, respectivamente para a ETE Aracapé. A argila pilarizada mostrou maior capacidade de adsorção quando comparada à argila natural, devido ao alargamento do espaço interlamelar da argila e aumento no volume de mesoporos como comprovado pelas técnicas de caracterização. Após análise dos resultados do planejamento fatorial foi fixado os valores ótimos encontrados das variáveis no processo para compor os estudos de cinética e isoterma de adsorção, os quais foram Temperatura – 25 °C; Agitação – 300 rpm; Massa do adsorvente: 300 mg e pH – 3. O estudo cinético indicou tempo de equilíbrio de 1 hora, sendo o modelo de pseudo-segunda ordem o que melhor se ajustou aos dados. O mecanismo de difusão intrapartícula não foi a etapa determinante da velocidade e no processo de transferência de massa. A maioria dos compostos DE estudados obteve maior remoção em sistema multicomponente quando comparados aos estudos monocomponentes. Os dados experimentais de isoterma de adsorção melhor se ajustaram ao modelo de Freundlich com exceção aos referentes aos compostos TMP e BPA. Os testes de regeneração do adsorvente indicaram significante redução da capacidade de adsorção da argila pilarizada no 2º ciclo de adsorção para os compostos TMP e BPA, com redução de 99,5 e 79,2 %, respectivamente. Para os compostos E2 e E1, a adsorção foi afetada após o 3º ciclo.Nascimento, Ronaldo Ferreira doSantos, André Bezerra dosVidal, Carla Bastos2015-12-18T19:04:41Z2015-12-18T19:04:41Z2015info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfVIDAL, C. B. Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. 2015. 159 f. Tese (Doutorado em Engenharia Civil: Saneamento Ambiental)-Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2015.http://www.repositorio.ufc.br/handle/riufc/14602porreponame:Repositório Institucional da Universidade Federal do Ceará (UFC)instname:Universidade Federal do Ceará (UFC)instacron:UFCinfo:eu-repo/semantics/openAccess2022-08-09T18:20:03Zoai:repositorio.ufc.br:riufc/14602Repositório InstitucionalPUBhttp://www.repositorio.ufc.br/ri-oai/requestbu@ufc.br || repositorio@ufc.bropendoar:2024-09-11T18:46:50.537627Repositório Institucional da Universidade Federal do Ceará (UFC) - Universidade Federal do Ceará (UFC)false |
dc.title.none.fl_str_mv |
Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. EDs present in environmental matrices: analysis by SPE-HPLC and removal with pillared clay. |
title |
Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. |
spellingShingle |
Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. Vidal, Carla Bastos Saneamento Micropoluentes Adsorção Estação de tratamento de esgoto |
title_short |
Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. |
title_full |
Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. |
title_fullStr |
Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. |
title_full_unstemmed |
Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. |
title_sort |
Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. |
author |
Vidal, Carla Bastos |
author_facet |
Vidal, Carla Bastos |
author_role |
author |
dc.contributor.none.fl_str_mv |
Nascimento, Ronaldo Ferreira do Santos, André Bezerra dos |
dc.contributor.author.fl_str_mv |
Vidal, Carla Bastos |
dc.subject.por.fl_str_mv |
Saneamento Micropoluentes Adsorção Estação de tratamento de esgoto |
topic |
Saneamento Micropoluentes Adsorção Estação de tratamento de esgoto |
description |
The substances called endocrine disruptors (ED) are a new category of environmental pollutants that interfere in the functions of the endocrine system, being found in the environment at concentrations in the order ug L-1 and L-1 ng. The WWTP effluent release are important sources of such compounds in the aquatic environment since the conventional methods of water treatment and sewage not completely remove these micropollutants. In this study we assessed the efficiency of pillared clay using tin dioxide as an agent for removing pilarizante DE (of different classes) in environmental matrices. Experimental design was used to evaluate the factors affecting the adsorptive process. For optimization step of the previously validated analytical method it was studied the effectiveness of three commercial SPE cartridges. Tributaries concentrations were obtained, effluents and removal efficiencies of two sewage treatment plants operating in full scale (UASB + chlorination). Finally, DE adsorption experiments were performed in single and multicomponent systems as well as regenerating the adsorbent. The Oasis and Strata-X cartridge efficiency showed high and selective ability, however, only Strata-X cartridge was selected in this study, since it showed higher recovery values (%) 50 (Sulfamethoxazol); 83 (Trimethoprim); 171 (diclofenac); 183 (estrone); 14 (17β-estradiol) and 82 (Bisphenol A). The chromatographic method was selective for all compounds studied, except for the hormone estriol. The quantification limit values (1.28 to 29.97 ng L-1) and detection limit (from 0.42 to 9.89 ng L-1) obtained in this study were low. Most of the recovery values was less than 100%. It was observed that the esgosto tributary of the studied WWTPs still present in their waste considerable amounts of DE, with average values of effluents from 21.94 to 311.79 ng L-1 for ETE Aracapé and 4.41 to 123.47 ng L 1 to ETE Mondubim, which highlights the need for a step of post-treatment in the studied WWTPs. They have found greater efficiencies treatment for compounds bisphenol A (90.8%) and 17α-ethinylestradiol (76.6%) ETE Mondubim. As for the compounds sulfamethoxazole and estrone it was observed an increase in effluent values of 18.9 and 28.6% respectively for the ETE Aracapé. The pillared clay showed higher adsorption capacity compared to the natural clay, due to enlargement of the interlayer space of the clay and increased volume of mesopores as evidenced by the characterization techniques. After analyzing the results of the factorial design was set optimum values of the variables found in the process to make the studies of kinetics and adsorption isotherm, which was temperature - 25 ° C; Agitation - 300 rpm; Mass of adsorbent: 300 mg and pH - 3. The kinetic study indicated 1 hour equilibration time, with the model of pseudo-second order which best fit to the data. The intraparticle diffusion mechanism was not the determining step of the speed and mass transfer process. The majority of the DE compounds obtained greater removal in multicomponent system when compared to single-component studies. The experimental data better adsorption isotherm set the model Freundlich except to refer to the TMP and BPA compounds. The sorbent regeneration tests indicated a significant reduction in the adsorption capacity of pillared clay in the 2nd adsorption cycle for TMP and compounds BPA, with a reduction of 99.5 and 79.2%, respectively. For E2 and E1 compounds, adsorption was affected after the 3rd cycle. |
publishDate |
2015 |
dc.date.none.fl_str_mv |
2015-12-18T19:04:41Z 2015-12-18T19:04:41Z 2015 |
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 |
VIDAL, C. B. Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. 2015. 159 f. Tese (Doutorado em Engenharia Civil: Saneamento Ambiental)-Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2015. http://www.repositorio.ufc.br/handle/riufc/14602 |
identifier_str_mv |
VIDAL, C. B. Desreguladores endócrinos presentes em matrizes ambientais: análise por SPE-HPLC e remoção com argila pilarizada. 2015. 159 f. Tese (Doutorado em Engenharia Civil: Saneamento Ambiental)-Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2015. |
url |
http://www.repositorio.ufc.br/handle/riufc/14602 |
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openAccess |
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Universidade Federal do Ceará (UFC) |
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Repositório Institucional da Universidade Federal do Ceará (UFC) |
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Repositório Institucional da Universidade Federal do Ceará (UFC) - Universidade Federal do Ceará (UFC) |
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