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Treatment of Aqueous Effluents Contaminated with Active Pharmaceutical Ingredients Treatment of aqueous effluents contaminated with active pharmaceutical ingredients Hugo Ferrão Dias de Almeida Dissertation presented to obtain the Ph.D degree in Sustainable Chemistry Instituto de Tecnologia Química e Biológica António Xavier | Universidade Nova de Lisboa Oeiras, September, 2017 Title Treatment of aqueous effluents contaminated with active pharmaceutical ingredients. Dissertation presented to obtain the Ph.D degree in Sustainable Chemistry. Cover Image Design adapted from https://wordart.com/create by Hugo F. D. Almeida. Author Hugo Ferrão Dias de Almeida Separation and Extraction Technology Laboratory Instituto de Tecnologia Química e Biológica António Xavier Universidade Nova de Lisboa Av. da República Estação Agronómica Nacional 2780-157 Oeiras Portugal First Edition, September 2017 Copyright © 2017 by Hugo F. D. Almeida All rights reserved Printed in Portugal II I declare that the work presented in this thesis, except where otherwise stated, is based on my own research. The work was mainly performed in the Separation and Extraction Technologies Laboratory of the Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa and CICECO – Instituto de Materiais de Aveiro, Universidade de Aveiro, between March 2013 and March 2017, and supervised by Doctor Isabel M. Marrucho (ITQB-UNL) and Doctor Mara G. Freire (CICECO-UA). Financial support was provided by Fundação para a Ciência e a Tecnologia through the doctoral fellowship SFRH/BD/88369/2012. III IV À minha grande família, juntos alcançamos os nossos sonhos! “The true sign of intelligence is not knowledge but imagination.” ― Albert Einstein V VI Acknowledgments Às minhas orientadoras, Dra. Isabel Marrucho e Dra. Mara Freire, por me proporcionarem a opotunidade de realizar este trabalho, pela orientação científica e pelos conhecimentos transmitidos. Em especial à Mara, pela total confiança no meu trabalho e a motivação que me deu sempre que dela precisei, pelo apoio e paciência ao longo destes anos, pela sua orientação a todos os níveis, mas sobretudo por me ter ajudado a crescer como profissional. Obrigado por tudo! Obrigada por permitirem que chegássemos aqui. Ao Professor Dr. João Coutinho por ter despertado a minha curiosidade pelos líquidos iónicos com uma pergunta tão simples, ―Sabes o que são líquidos iónicos?‖, e por assim me ter dado a oportunidade de iniciar toda esta viagem científica no seu laboratório. A todas as pessoas no ITQB que me ajudaram a alcançar este objectivo. Em especial, à Liliana, ao Filipe e ao David pelas longas horas de conversas, em que dissolvíamos mistérios científicos e nos riamos que nem uns desalmados. As minhas estadias por terras da capital foram bem mais suaves na vossa presença. A todas as pessoas do PATh que me ajudaram a ser o Profissional e a Pessoa que sou hoje. Aos inesquecíveis Catarina, Martinha, Mónia, Filipita, Tânia, Helena, Sónia, Vanessa, Liliana, Francisca, Márcia, Ana Maria, Mafalda, Diana, Mary Jane, Sandra, Teresa, Ana Paula, Rita, Pedro, Jorge, André, Carlos, João, Kiki, Ricardo e Matheus! Partilhar o lab com vocês foi mesmo awesome! Levo e guardo estas amizades comigo. Foi muito bom sentir-me em família no local de trabalho! Arre, as sessões de bolos vão deixar saudades! Aos alunos de mestrado, Sara, Pedro e Milene, por terem confiado em mim para vos ajudar no vosso percurso ao longo do trabalho laboratorial. Espero que tenha sido capaz de vos passar todos os ―truques‖ de laboratório que eu conhecia. Aos meus bros da banda, Shaq e Speeds, pelas músicas que criámos, pelas enormes risadas e viagens infinitas que permitiram descomprimir nas VII alturas de maior tensão. Obrigado bros, é mesmo um prazer partilhar o palco com vocês! Time is smooth! Aos meus compinchas de Gouveia, pelas longas conversas de ―gear‖, música, festivais, bandas e concertos, acompanhados por uma bela cerveja no Manel, e pelas grandes risadas! E como o final é sempre a melhor parte… À família Fidalgo, D. Rosa e Sr. Fidalgo, por me terem recebido de braços abertos e me encherem de energia com a vossa alegria. E à Sófia por estar sempre sorridente e por ser uma ―forte‖, pois eu vou-me abaixo mais depressa nas caminhadas! À Ana Fidalgo, por ser um sonho, por ter estado sempre a meu lado, por me ter apoiado e incentivado quando eu mais precisava, pelas longas conversas noite fora, por discutir comigo os resultados menos bons que iam surgindo e, por no meio de um suspiro, lançar uma piada e tudo ficar mais calmo e sereno.... Agradeço-te por tudo Princesa! Adoro tu! Ao meu Pai e à minha Mãe, pois sem eles não teria conquistado tantas etapas! Obrigado por todos os ensinamentos que tenho na vida, por todos os incentivos para ser melhor! Por todas as alegrias que partilhamos quando estamos juntos e por juntos conseguirmos ultrapassar os obstáculos! Nenhum filho alguma vez poderia ter ou receber melhor! Adoro-vos! E ao meu Irmão Edgar, agradeço as horas infinitas de conversas sobre tudo e sobre nada que me dão tão preciosa lufada de ar fresco, pelo forte abraço à chegada a casa e os risos e gargalhadas que nos levam ao choro! És uma forte influência na minha vida! Adoro-te bro! Evolutions of a birth, a rhyme to tell this crimson tale Evoke the faithful creed, the sacred secrets of society Matt Pike VIII Members of the Jury President Dr. Maria Arménia Abreu Fonseca de Carvalho Teixeira Carrondo, Full Professor at Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Portugal Thesis Supervisors Dr. Isabel Maria Delgado Jana Marrucho Ferreira, Research Coordinator at Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Portugal (supervisor). Dr. Mara Guadalupe Freire Martins, Research Coordinator at Aveiro Institute of Materials (CICECO), Chemistry Department, Universidade de Aveiro, Portugal (co- supervisor). Thesis Examiners Dr. Luís Alexandre Almeida Fernandes Cobra Branco, Principal Investigator at Universidade Nova de Lisboa, Portugal. Dr. Ana Catarina Almeida Sousa, Postdoctoral Researcher at Aveiro Institute of Materials (CICECO), Chemistry Department, Universidade de Aveiro, Portugal. Dr. Ana Paula Mora Tavares, Assistant Researcher at at Aveiro Institute of Materials (CICECO), Chemistry Department, Universidade de Aveiro, Portugal. Dr. Óscar Rodriguez Figueiras, Postdoctoral Researcher at Departamento de Engenharia Química, Universidade de Santiago de Compostela, Espanha. IX X Contents Treatment of aqueous effluents contaminated with active pharmaceutical ingredients Abstract XIII Resumo XV Publications XVII Thesis Layout XXI Chapter 1 1 Chapter 2 67 Chapter 3 111 Chapter 4 157 Chapter 5 197 Chapter 6 239 Chapter 7 275 XI XII Abstract The need to significantly improve human living conditions led to a large increase in the worldwide consumption of pharmaceutical drugs. Over the past few years, the development of advanced analytical tools and investigations on wastewater samples confirmed the presence of residual amounts of active pharmaceutical ingredients (APIs) in wastewater treatment plants (WWTPs), sewage treatment plants (STPs), groundwater and drinking water. Even at low concentrations (ng.L-1 – μg.L-1), the regular contact and ingeston of APIs can lead to deleterious effects towards living organisms. Numerous studies demonstrated that APIs present in WWTPs are a matter of concern towards wildlife and public health. Given the widespread occurance of these drugs in aquatic ecossystems and their deleterious effects, the development of strategies able to mitigate their introduction in the aquatic environment is of great importance. This thesis addresses the development and study of two water cleaning processes to be included in WWTPs, namely liquid-liquid extraction (LLE) and solid-phase extraction (SPE), making use of a novel class of compounds – ionic liquids (ILs). Ionic liquids present excellent solvating qualities, which can be additionally tailored to guarantee the success of specific extractions. In particular, aqueous biphasic systems (ABS) composed of ILs and supported ionic liquid phases (SILPs) were investigated for the removal of non-steroidal anti- inflammatory drugs (NSAIDs) and antibiotics (fluoroquinolones – FQs), two classes of APIs frequently found in aquatic environments. The work presented herein starts with the use of IL-based ABS, formed by the addition of a citrate- based salt (C6H5K3O7), for the extraction and concentration of FQs and NSAIDs from aqueous media (Chapter 2). Afterwards, the extraction capacity of ABS composed of ILs and Al2(SO4)3 was evaluated for four NSAIDs and six FQs. Al2(SO4)3 was used as a salting-out species, as it is already used as a flocculating agent in the purification of drinking water processes (Chapters 3 and 4). In these works, the recyclability of the IL-based ABS was always attempted. In addition to XIII IL-.based ABS strategies, SILPs were synthetized by crafting 1-methyl-3- propylimidazolium chloride into the surface of silica, ensuing the preparation of six materials with different counter ions. Adsorption kinetics and isotherms were performed with diclofenac solutions (Chapter 5). Further, the most promising materials was evaluated to remove three NSAIDs, by carrying out adsorption kinetics and isotherms. In order to develop a continuous removal method, a packed column with SILP was also prepared. Finally, the recovery of NSAIDs and the SILP reusability were evaluated (Chapter 6). The obtained results demostrate that it is possible to design chemical structures of ILs
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