O aumento crescente da população brasileira em combinação com o uso abusivo de medicamentos no mercado nacional, aliados à falta de saneamento básico e de políticas públicas para o correto gerenciamento de alguns tipos de resíduos têm resultado na presença de compostos farmacêuticos em ambientes aquáticos. Estudos indicam que várias dessas substâncias parecem ser persistentes no ambiente e algumas vezes, resistem até mesmo às estações de tratamento de água, fazendo-se presentes na água tratada, que chega à população. O presente trabalho visou analisar quantitativamente a presença dos anti-inflamatórios e do analgésico mais comumente consumido no Brasil: diclofenaco, cetoprofeno, naproxeno, indometacina, ibuprofeno e o paracetamol em águas superficiais, por LC-MS/MS com extração em fase sólida, antes e depois do tratamento convencional, em escala laboratorial pelo ensaio de Jar-Test, bem como caracterizar o risco humano pela presença destes compostos na água após o tratamento. Os métodos utilizados na quantificação destes fármacos apresentaram bons resultados: a análise cromatográfica obteve coeficientes de correlação entre 0,9952-0,9991, com limites de quantificação de 0,5ng/mL- 50ng/mL e desvios padrões entre (0,08-2,08); na recuperação do método de extração em fase sólida o diclofenaco, o cetoprofeno, o naproxeno e a indometacina apresentaram cerca de 100% de recuperação, o ibuprofeno apresentou apenas 48%(±9,37) de recuperação e o paracetamol aproximadamente 19,84% (±2,52); no ensaio de jar-test, observou-se que apenas o cetoprofeno e o ibuprofeno não foram removidos completamente no tratamento utilizado (remoção de 0-15% do cetoprofeno e de 0-35% do ibuprofeno). Amostras ambientais foram coletadas e tratadas pelo ensaio de Jar-Test, e os valores obtidos para o cetoprofeno e ibuprofeno após o tratamento foram de 18,67-19,65ng/L e 147ng/L, respectivamente. Através de cálculos, com a dose de referência de cada um dos compostos e considerando as características desta exposição, foi possível concluir que nestas concentrações o cetoprofeno e o ibuprofeno não causam risco à saúde humana. / The increasing population growth in combination with the misuse of drugs in the domestic market, coupled with the lack of sanitation and public policies for proper management of some types of waste have resulted in the presence of pharmaceutical compounds in aquatic environments. Studies indicate that several of these substances appear to be persistent in the environment and sometimes even resistant to water treatment plants, being present in the treated water which reaches the population. This study aimed to analyze quantitatively the presence of anti-inflammatory and analgesic most commonly consumed in Brazil: diclofenac, ketoprofen, naproxen, indomethacin, ibuprofen and paracetamol in surface waters by LC-MS/MS with solid phase extraction prior and after conventional treatment in a laboratory scale by using Jar-test assay, and to determine the human risk posed by the presence of these compounds in the water after treatment. The methods used to quantify these drugs showed good results: a chromatographic analysis obtained correlation coefficients between 0.9952 to 0.9991, with limits of quantification of 0.5 ng/mL- 50ng/mL and standard deviations between (0.08 - 2.08); recovery method of solid phase extraction to diclofenac, ketoprofen, naproxen and indomethacin showed about 100% recovery, ibuprofen showed only 48% (± 9.37) and paracetamol approximately 19 84% (± 2.52) recovery; in the jar-test, it was observed that only ketoprofen and ibuprofen were not completely removed (removal: 0-15% of ketoprofen and 0-35% of ibuprofen). Environmental samples were collected and handled by jar-test test, and the values obtained for ketoprofen and ibuprofen after treatment were 18.67 to 19.65 ng / L and 147ng / L, respectively. By calculation with a reference dose of each compound and considering the characteristics of this display, it was concluded that these concentrations of ketoprofen and ibuprofen do not cause risk to human health.

Submitted by Franciele Moreira (francielemoreyra@gmail.com) on 2018-04-04T11:53:17Z No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-04-04T13:25:36Z (GMT) No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-04-04T13:25:36Z (GMT). No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-02-28 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Water is an essential natural resource for life that is compromised by the release of emerging contaminants, including synthetic hormones. These compounds can be released directly through industrial effluents and indirectly through domestic sewage. Monitoring emergent contaminants (ECs) in the aquatic environment has become a priority as they pose risks to human health and the environment because of their ability to deregulate the endocrine system. Thus, verification analyzes of the emerging contaminants produced by the pharmaceutical industries are required. The most common analytical methods for analysis of this class of compounds involve the use of liquid or gas chromatography coupled to tandem mass spectrometry (MS / MS) with procedures for the preparation of long samples and long chromatographic runs. In this study, a methodology was developed for the analysis of emerging contaminants in raw and treated industrial wastewater from a local industry's hormone production line by an environmental ionization technique known as Paper Spray Ionization (PSI). Here, we have proposed an analytical approach based on the use of waxed papers. Analyzes of the synthetic hormones levonorgestrel and algestone acetophenide occurred by adding the sample to a triangular paper that was moistened with methanol solution (0.1% formic acid). The paper was fixed at the input of the mass spectrometer through a metal clip which provided a voltage to the paper. The analytical curves presented a linear correlation coefficient above 0.99. For the hormone levonorgestrel the intra-day and inter-day precision ranged from 0.5 to 5.3%, accuracy ranged from -7.0 to 4.2% while recovery ranged from 82.2 to 101.3%. For the hormone algestone acetophenide the intra-day and inter-day precision ranged from 0.9 to 10.7%, accuracy ranged from -7.7 to 8.9% while recovery ranged from 88.4 to 101.6%. The levonorgestrel hormone was also analyzed with the classic LC-MS method, showing consistent results between the two approaches, thus confirming the reliability of the proposed method. / A água é um recurso natural essencial para vida que ultimamente está comprometido pela descarga de contaminantes emergentes, dentre os quais, hormônios sintéticos. Esses compostos podem ser lançados diretamente através de efluentes industriais e indiretamente através de esgoto doméstico. O monitoramento de contaminantes emergentes (ECs) no ambiente aquático tem se tornado uma prioridade, visto que eles apresentam riscos para a saúde humana e para meio ambiente devido a sua capacidade de desregular o sistema endócrino. Dessa forma, é necessário análises de verificação dos contaminantes emergentes produzidos pelas indústrias farmacêuticas. Os métodos analíticos mais comuns para análises dessa classe de compostos envolvem o uso de cromatografia líquida ou gasosa, acoplado a espectrometria de massas tandem (MS/MS) com procedimentos de preparos de amostras demorados e longas corridas cromatográficas. Neste trabalho desenvolveu-se uma metodologia para análise de contaminantes emergentes em água residual industrial bruta e tratada de uma linha de produção de hormônios de uma indústria local, por uma técnica de ionização ambiente conhecida como Paper Spray Ionization (PSI), cuja principal vantagem é o preparo mínimo de amostra. Neste trabalho, a técnica de PSI com papel contendo barreiras de parafinas foi empregada para análise de hormônios em águas residuárias. As análises dos hormônios sintéticos levonorgestrel e algestona acetofenida ocorreram através da adição da amostra sobre um papel triangular que foi umedecido com solução de metanol (0,1% de ácido fórmico). O papel foi fixado na entrada do espectrômetro de massas através de um clipe metálico que forneceu uma voltagem ao papel. As curvas analíticas apresentaram coeficiente de correlação linear acima de 0,99. Para o hormônio levonorgestrel a precisão intra-dias e inter-dias variou de 0,5 a 5,3%, a exatidão variou de -7,0 a 4,2% enquanto a recuperação variou de 82,2 a 101,3%. Para o hormônio algestona acetofenida a precisão intra-dias e inter-dias variou de 0,9 a 10,7%, a exatidão variou de -7,7 a 8,9% enquanto a recuperação variou de 88,4 a 101,6%. O hormônio levonorgestrel também foi analisado com o método clássico LC-MS, mostrando resultados consistentes entre as duas abordagens, confirmando assim a confiabilidade do método proposto.

Emerging contaminants are defined as synthetic or naturally occurring chemicals or microorganisms that are not currently regulated but have the potential to enter the environment and cause adverse ecological and/or human health effects. With recent development in analytical techniques, emerging contaminants have been detected in wastewater, source water, and finished drinking water. These environmental occurrence data have raised public concern about the fate and ecological impacts of such compounds. Concerns regarding emerging contaminants and the many chemicals that are in use or production necessitate a task to assess their potential health effects and removal efficiency during water treatment. Advanced oxidation processes (AOPs) are attractive and promising technologies for emerging contaminant control due to its capability of mineralizing organic compound via reactions with highly active hydroxyl radicals. However, the nonselective reactivity of hydroxyl radicals and the radical chain reactions make AOPs mechanistically complex processes. In addition, the diversity and complexity of the structure of a large number of emerging contaminants make it difficult and expensive to study the degradation pathways of each contaminant and the fate of the intermediates and byproducts. The intermediates and byproducts that are produced may pose potential effects to human and aquatic ecosystems. Consequently, there is a need to develop first-principle based mechanistic models that can enumerate reaction pathway, calculate concentrations of the byproducts, and estimate their human effects for both water treatment and reuse practices. This dissertation develops methods to predict reaction rate constants for elementary reactions that are identified by a previously developed computer-based reaction pathway generator. Many intermediates and byproducts that are experimentally identified for HO* induced reactions with emerging contaminants include common lower molecular weight organic compounds on the basis of several carbons. These lower carbon intermediates and byproducts also react with HO* at relatively smaller reaction rate constants (i.e., k < 109 M-1s-1) and may significantly affect overall performance of AOPs. In addition, the structures of emerging contaminants with various functional groups are too complicated to model. As a consequence, the rate constant predictors are established based on the conventional organic compounds as an initial approch. A group contribution method (GCM) predicts the aqueous phase hydroxyl radical reaction rate constants for compounds with a wide range of functional groups. The GCM is a first comprehensive tool to predict aqueous phase hydroxyl radical reaction rate constants for reactions that include hydrogen-atom abstraction from a C-H bond and/or a O-H bond by hydroxyl radical, hydroxyl radical addition to a C=C unsaturated bond in alkenes and aromatic compounds, and hydroxyl radical interaction with sulfur-, nitrogen-, or phosphorus-atom-containing compounds. The GCM shows predictability; factor of difference of 2 from literature-reported experimental values. The GCM successfully predicts the hydroxyl radical reaction rate constants for a limited number of emerging contaminants. Linear free energy relationships (LFERs) bridge a kinetic property with a thermochemical property. The LFERs is a new proof-of-concept approach for Ab initio reaction rate constants predictors. The kinetic property represents literature-reported and our experimentally obtained hydroxyl radical reaction rate constants for neutral and ionized compounds. The thermochemical property represents quantum mechanically calculated aqueous phase free energy of activation. Various Ab initio quantum mechanical methods and solvation models are explored to calculate the aqueous phase free energy of activation of reactantas and transition states. The quantum mechanically calculcated aqueous phase free energies of activation are within the acceptable range when compared to those that are obtained from the experiments. These approaches may be applied to other reaction mechanisms to establish a library of rate constant predictions for the mechanistic modeling of AOPs. The predicted kinetic information enables one to identify important pathways of AOP mechanisms that are initiated by hydroxyl radical, and can be used to calculate concentration profiles of parent compounds, intermediates and byproducts. The mechanistic model guides the design of experiments that are used to examine the reaction mechanisms of important intermediates and byproducts and the application of AOPs to real fields.

Atualmente no cenário mundial a qualidade da água tem gerado muitas preocupações, pois milhares de produtos sintéticos são produzidos para facilitar muitas práticas industriais, domésticas e pessoais e com isso diversas substâncias químicas utilizadas para esses fins são introduzidas no meio ambiente. Os parabenos são substâncias químicas utilizadas pelas indústrias farmacêuticas, de alimentos e cosméticos e que cuja função é a conservação, sendo que há muitos questionamentos em relação a sua segurança, pois alguns relatórios têm mostrado que a exposição a esses parabenos pode modular ou perturbar o sistema endócrino e com isso gerar consequências prejudiciais à saúde humana e aos ambientes aquáticos. Esse estudo teve como objetivo avaliar a presença dos Parabenos Metilparabeno e Propilparabeno no ambiente aquático e os seus potenciais estrogênicos e a toxicidade aguda. A metodologia se desenvolveu a partir do ensaio in vitro YES para a determinação da atividade estrogênica, ensaios de toxicidade aguda em Daphnia similis e em Aliivibrio fischeri e a quantificação dos parabenos na água do Rio Maracanã-RJ através da cromatografia líquida acoplada ao espectrômetro de massa. Os resultados obtidos para a CE50 dos MP e PP, a partir do ensaio in vitro YES, foi de 18,91 mgL-1 e 7 mgL-1 e a magnitude da resposta foi de 10-5 e 10-4 menos potente que 17ß-estradiol para o MP e o PP, respectivamente. A partir do ensaio de toxicidade aguda, os valores de CE50 obtidos em Daphnia similis, foi de 29,42 mgL-1 e 9,94 mgL-1e em Aliivibrio fischeri foi de 3,047 mgL-1 e 1,946 mgL-1, respectivamente, com isso observou-se que o PP é mais tóxicos em todos os organismos testados, sendo mais tóxicos para um e menos para outros. A água do Rio Maracanã não foi tóxica para a Daphnia similis em nenhum dos dois pontos, já para o Aliivibrio fischeri foi tóxica em apenas um ponto. As concentrações encontradas de MP e PP foram maiores no ponto onde, de acordo com os parâmetros físico-químicos, a qualidade da água não está dentro dos padrões exigidos pela legislação, sendo quantificados na ordem de ngL-1, contudo é válido ressaltar que os DEs não são encontrados no meio ambiente separados, eles interagem entre si e provocam efeitos aditivos ou sinérgicos, sendo muito difícil de prever qual o efeito, por isso é importante o conhecimento do potencial estrogênico das substâncias simples, pois em um estudo com uma matriz ambiental, pode-se observar se houve algum efeito aditivo ou sinérgico de outras substâncias. / Currently on the world stage water quality has generated many concerns, because thousands of synthetic products are produced to facilitate many industrial, domestic and personal practices and thereby various chemicals used for these purposes are introduced into the environment. Parabens are chemicals used by the pharmaceutical, food and cosmetic and whose function is to conserve, and there are many questions regarding its safety , as some reports have shown that exposure to these parabens can modulate or disrupt endocrine system and thereby generate harmful consequences for human health and aquatic environments . The aim of this study was to evaluate the presence of Methylparaben and Propylparaben in the aquatic environment and their potential estrogenic and acute toxicity. The methodology developed from the in vitro YES assay for the determination of estrogenic activity, acute toxicity tests with Daphnia similis and Aliivibrio fischeri and quantification of parabens in water of Maracanã River RJ by liquid chromatography coupled with mass spectrometry. The EC50 results for the PP and MP, from the in vitro YES, was 18,91 mgL -1 and 7 mgL-1 and the magnitude of response was less potent 10-5 and 10-4 that 17ß - estradiol for MP and PP , respectively. From the acute toxicity test, the EC50 values obtained in Daphnia similis was 29,42 mgL-1 and 9,94 mgL-1, and Aliivibrio fischeri was 3,047 mgL-1 and 1,946 mgL-1, respectively, with it was observed that PP is more toxic in all organisms tested, and more toxic to one and less to others . The water of the Maracanã River was not toxic to Daphnia similis in either points, since for Aliivibrio fischeri was toxic at only one point. Found concentrations of MP and PP were higher at the point where, according to the physico-chemical parameters, water quality is not within the standards required by legislation and quantified in order ngL-1, however its worth to note that the DEs are not found in the middle separate environment, they interact with each other and cause additive or synergistic effects , its very difficult to predict what effect , so its important to know the estrogenic potential of simple substances , since in a study with an environmental matrix, one can observe if there were any additive or synergistic effect of other substances .

Emerging organic contaminants (EOCs) have been the focus of global environmental research for over three decades. EOCs have caused widespread concern due to their extensive use. As EOCs were designed to correct, enhance or protect a specific physiological, their target effects in humans and/or farm stocks are relatively well known and documented. However, there is limited knowledge about their unintended effects in the environment. To address the occurrence, distribution and fate of EOCs in the environment, efficient and reliable analytical methods are needed. The relatively low concentration, high polarity, and thermal lability of some EOCs, together with their interaction with complex environmental matrices, make their analysis challenging. Sample preparation followed by GC or HPLC separation and mass spectrometry (MS) detection has become the standard approach for evaluating EOCs in environmental samples. Physicochemical properties of EOCs range from highly water-soluble (hydrophylic) to highly water-insoluble (hydrophobic). Two groups of these EOCs were considered for study in this work. Pharmaceutical and personal care products (PPCPs) were comprehensively studied in five wastewater treatment plants and their receiving watersheds in Amathole districts in Eastern C ape, South Africa. PPCPs have been widely reported in wastewater influents, effluents, receiving rivers and biosolids, but reports of their occurrence in all these matrixes have been limited by the difficulty of analysis. Therefore, a comprehensive validation of methods was carried out on the influents, effluents, sludge and soil from the irrigated golf course where the effluent of one of the study sites was being used for over three decades now for irrigation. In all, thirteen PPCPs from five therapeutic groups were selected for study in this work because of their administering rate and availability of analytical instrument. Good limit of detection (LOD) and limit of quantification (LOQ) were achieved for the method used. The LOD for the aqueous Three different technologies were employed for the treatment of wastewater in the five selected wastewater treatment plants (WWTPs) and study was carried out to evaluate their ability to eliminate the selected compounds from the influents to the effluents using statistical analysis (ANOVA) at p<0.05 on the percentage removal rate across the three plants. The results had shown eight of the compounds having no significant difference among the treatment operations, whereas the remaining five compounds varied significantly among the treatment technologies under investigation. Principal component analysis was performed on the concentration of PPCPs, their removal rate and also on the physicochemical and treatment operation parameters. Hydraulic retention time (HRT) had correlation coefficient, r = 0.90 with the concentration of PPCPs and removal rates. Furthermore, occurrences, seasonal variation, mean concentration distribution pattern of the compounds, and temporal evaluation of the mean concentration of the pharmaceutical compounds in the five WWTPs during one year of sampling were considered. The results revealed that five products which were diclofenac, ibuprofen, paracetamol, triclosan and diethyl toluamide (DDET) were predominant among the PPCPs in all the WWTPs. The removal efficiency was highest in caffeine with 96 percent, and the lowest was obtained with carbamazepine (4 percent). Risk quotient of the concentration of PPCPs in the effluents and receiving waters was determined to assess their chronic toxicity at three trophic levels: fish, algae and matrixes studied ranged from 0.01 μg/L to 0.25 μg/L, and the LOQ from 0.02 μg/L to 0.78 μg/L. In the solid matrixes, LOD varied from 0.01 ng/g to 0.65 ng/g, and the LOQ between 0.08 ng/g and 5.17 ng/g. Better recovery efficiency was obtained with this mixture of solvents, acetone: dichloromethane (1:1), for the recovery of the five therapeutic groups in the solid matrixes using ultrasonication- assisted techniques. The results show percentage recovery values ranging from 68.8 percent to 107.5 percent diaphian. According to the environmental risk assessment results, ibuprofen and triclosan were found to be the most critical compounds due to their high risk quotient values. These findings will, therefore, help in the future evaluation of the efficiency of different treatment technologies in the removal of various PPCPs from the wastewater and their sustainable management in the aquatic resources in Eastern Cape, South Africa. For the lipophilic organochlorine pesticides (OCPs), the limits of detection (LODs) of the tested congeners varied from 0.04 ng/g (α-BHC) to 0.49 ng/g (endosulfan sulfate) and the limits of quantification ranging from 0.22 ng/g (aldrin) to 2.17 ng/g (δ-BHC).

Atualmente no cenário mundial a qualidade da água tem gerado muitas preocupações, pois milhares de produtos sintéticos são produzidos para facilitar muitas práticas industriais, domésticas e pessoais e com isso diversas substâncias químicas utilizadas para esses fins são introduzidas no meio ambiente. Os parabenos são substâncias químicas utilizadas pelas indústrias farmacêuticas, de alimentos e cosméticos e que cuja função é a conservação, sendo que há muitos questionamentos em relação a sua segurança, pois alguns relatórios têm mostrado que a exposição a esses parabenos pode modular ou perturbar o sistema endócrino e com isso gerar consequências prejudiciais à saúde humana e aos ambientes aquáticos. Esse estudo teve como objetivo avaliar a presença dos Parabenos Metilparabeno e Propilparabeno no ambiente aquático e os seus potenciais estrogênicos e a toxicidade aguda. A metodologia se desenvolveu a partir do ensaio in vitro YES para a determinação da atividade estrogênica, ensaios de toxicidade aguda em Daphnia similis e em Aliivibrio fischeri e a quantificação dos parabenos na água do Rio Maracanã-RJ através da cromatografia líquida acoplada ao espectrômetro de massa. Os resultados obtidos para a CE50 dos MP e PP, a partir do ensaio in vitro YES, foi de 18,91 mgL-1 e 7 mgL-1 e a magnitude da resposta foi de 10-5 e 10-4 menos potente que 17ß-estradiol para o MP e o PP, respectivamente. A partir do ensaio de toxicidade aguda, os valores de CE50 obtidos em Daphnia similis, foi de 29,42 mgL-1 e 9,94 mgL-1e em Aliivibrio fischeri foi de 3,047 mgL-1 e 1,946 mgL-1, respectivamente, com isso observou-se que o PP é mais tóxicos em todos os organismos testados, sendo mais tóxicos para um e menos para outros. A água do Rio Maracanã não foi tóxica para a Daphnia similis em nenhum dos dois pontos, já para o Aliivibrio fischeri foi tóxica em apenas um ponto. As concentrações encontradas de MP e PP foram maiores no ponto onde, de acordo com os parâmetros físico-químicos, a qualidade da água não está dentro dos padrões exigidos pela legislação, sendo quantificados na ordem de ngL-1, contudo é válido ressaltar que os DEs não são encontrados no meio ambiente separados, eles interagem entre si e provocam efeitos aditivos ou sinérgicos, sendo muito difícil de prever qual o efeito, por isso é importante o conhecimento do potencial estrogênico das substâncias simples, pois em um estudo com uma matriz ambiental, pode-se observar se houve algum efeito aditivo ou sinérgico de outras substâncias. / Currently on the world stage water quality has generated many concerns, because thousands of synthetic products are produced to facilitate many industrial, domestic and personal practices and thereby various chemicals used for these purposes are introduced into the environment. Parabens are chemicals used by the pharmaceutical, food and cosmetic and whose function is to conserve, and there are many questions regarding its safety , as some reports have shown that exposure to these parabens can modulate or disrupt endocrine system and thereby generate harmful consequences for human health and aquatic environments . The aim of this study was to evaluate the presence of Methylparaben and Propylparaben in the aquatic environment and their potential estrogenic and acute toxicity. The methodology developed from the in vitro YES assay for the determination of estrogenic activity, acute toxicity tests with Daphnia similis and Aliivibrio fischeri and quantification of parabens in water of Maracanã River RJ by liquid chromatography coupled with mass spectrometry. The EC50 results for the PP and MP, from the in vitro YES, was 18,91 mgL -1 and 7 mgL-1 and the magnitude of response was less potent 10-5 and 10-4 that 17ß - estradiol for MP and PP , respectively. From the acute toxicity test, the EC50 values obtained in Daphnia similis was 29,42 mgL-1 and 9,94 mgL-1, and Aliivibrio fischeri was 3,047 mgL-1 and 1,946 mgL-1, respectively, with it was observed that PP is more toxic in all organisms tested, and more toxic to one and less to others . The water of the Maracanã River was not toxic to Daphnia similis in either points, since for Aliivibrio fischeri was toxic at only one point. Found concentrations of MP and PP were higher at the point where, according to the physico-chemical parameters, water quality is not within the standards required by legislation and quantified in order ngL-1, however its worth to note that the DEs are not found in the middle separate environment, they interact with each other and cause additive or synergistic effects , its very difficult to predict what effect , so its important to know the estrogenic potential of simple substances , since in a study with an environmental matrix, one can observe if there were any additive or synergistic effect of other substances .

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No. of bitstreams: 1 TeseGMG.pdf: 4914831 bytes, checksum: 1d048739debba70d1c2f92d0a969f785 (MD5) Previous issue date: 2016-11-21 / Outra / The wastewater treatment plant (WWTPs) play an important role to ensuring the health and preservation of aquatic ecosystems through biological removal (mainly) of pollutants and microorganisms in the sanitary and industrial sewage, avoiding the disposal "in natura" of sewage on water and soil. Among these organic contaminants stand out Emerging Contaminants (EC), like pharmaceuticals, personal care products and endocrine disruptors, drug abuse, etc.In this study, it was investigated the occurrence and evaluated the removal of 12 EC: naproxen (NPX), diclofenac (DCF), ibuprofen (IBU), caffeine (CAF), carbamazepine (CBZ), propranolol (PRP), atenolol (ATL ), 1-hydroxyibuprofen (IBU-1OH), 2-hydroxy-ibuprofen (IBU-2OH), 10,11-dihydro-10,11-dihydroxy-carbamazepine (CBZ-DIOH), 2-hydroxy-carbamazepine (CBZ-2OH) at two wastewater treatment plants operating with biologic system, one aerobic and another one anaerobic. The first one is located in Jundiaí / SP city and the second one in São Carlos / SP. The target compounds were extracted from the aqueous phase by solid phase extraction (SPE). The analytical determinations were done through liquid chromatography coupled to mass spectrometry with triple quadrupole analyzer (UPLC-MS / MS).Pharmaceuticals, metabolites and personal care product triclosan were detected in all samples. The WWTP CSJJundiaí, which operates in aerobic system showed high removal values (R>70%), in all samples, for the CAF, NPX, ATL, IBU-1OH and TCS, moderate removal (70%>R> 20%) for the IBU and IBU-2 OH, low removal (R <20%) and production (R <0%) for CBZ and PRP.On the other hand ETE-Monjolinho, which operates in an anaerobic system presented a less removal of contaminants, where only caffeine had R> 70%.Thecompounds TCS IBU-2OH, IBU-1OH and ATL was moderate removal, CBZ-DIOH, CBZ and IBU was poorly removal, while it was observed production of DCF, PRP and CBZ-2OH (R < 0%). The metabolite CBZ-DIOH was recalcitrant to degradation in both WWTP. Moreover, it was noticed that WWTP can not only promote the degradation of some contaminants but also the production of the same, as is the case of DCF, CBZ, CBZ-2OH, CBZ-DIOH and PRP in both WWTP, and Moreover, it is possible to observe that STPs can promote not only the degradation of some contaminants but also the production of the same, as is the case of DCF, CBZ, CBZ-2 OH, CBZ-DIOH and PRP in both STPs, and ATL, IBU, and IBU-1OH only in ETE-Monjolinho. Despite both WWTP not completely remove the organic contaminants, it was found that WWTP with aerobic biodegradation has proved more effective in removing the EC than anaerobic biodegradation.The currently WWTP technologies are not able to eliminated most of EC, providing this contaminants into water bodies. This work aim to contributes to the understanding the EC in WWTP, in order to support better operating parameters of WWTP or the requirement of new technologies which allowed the removal of these contaminants providing treated wastewater that could helping for the global water scarcity problem. / As Estações de Tratamento de Esgoto (ETEs) desempenham papel importante na garantia da saúde pública e preservação dos ecossistemas aquáticos por meio da remoção biológica (majoritariamente) de poluentes e microorganismos presentes no esgoto sanitário e industrial, evitando o aporte“in natura”do esgoto nos corpos hídricos e solos. Dentre estes contaminantes orgânicos destacam-se os Contaminantes Emergentes (CE), uma categoria composta por fármacos, produtos de higiene pessoal e desreguladores endócrinos, drogas de abuso, entre outros. Neste trabalho foi investigada a ocorrência e avaliada a remoção de 12 CE, sendo eles: naproxeno (NPX), diclofenaco (DCF), ibuprofeno (IBU), cafeína (CAF), carbamazepina (CBZ), propranolol (PRP), atenolol (ATL), 1- hidroxi-ibuprofeno (IBU-1OH), 2-hidroxi-ibuprofeno (IBU-2OH), 10,11-dihidro-10,11-dihidroxi-carbamazepina (CBZ-DIOH), 2-hidroxi-carbamazepina (CBZ-2OH) em duas estações de tratamento de esgoto que operam sistemas biológicos, sendo uma aeróbia e outra anaeróbia. A primeira fica na cidade de Jundiaí/SP e a segunda opera na cidade de São Carlos/SP. Os compostos alvos foram extraídos da fase aquosa por extração em fase sólida (SPE). As determinações analíticas foram feitas por cromatografia líquida de ultra eficiência acoplada àespectrometria de massas com analisador triplo quadrupolo (UPLC-MS/MS). Os fármacos, metabólitos e o produto de higiene pessoal triclosan foram detectados em todas as amostras analisadas. A CSJ-Jundiaí, que opera em regime aeróbio, apresentou ao longo das campanhas amostrais, altos valores de remoção (R>70%) para a CAF, NPX, ATL, IBU-1OH e TCS, remoção moderada (70%> R > 20%) para o IBU e IBU-2OH, baixa remoção (R<20%) e formação/produção (R<0%) para a CBZ e PRP. Já a ETEMonjolinho, que opera em regime anaeróbio, apresentou um panorama menos favorável na remoção dos contaminantes alvos obtendo R>70% apenas para a cafeína. Os compostos TCS, IBU-2OH, IBU-1OH e ATL tiveram remoção moderada, ao passo que CBZ-DiOH, CBZ e IBU apresentaram baixa remoção e formação/produção do DCF, PRP e CBZ-2OH. O metabólito CBZ-DiOH mostrou-se recalcitrante a degradação em ambas ETEs. Além do mais, é possível observar que as ETE podem promover não somente a degradação de alguns contaminantes mas também a formação/produção dos mesmos, como é o caso do DCF, CBZ, CBZ-2OH, CBZ-DiOH e PRP em ambas ETEs, havendo ainda na ETE-Monjolinho a formação de ATL, IBU, e IBU-1OH. Apesar de ambas ETEs não removerem completamente os compostos avaliados, observouse que o tratamento de esgoto empregando a biodegradação aeróbia tem se mostrado mais eficaz na remoção dos CEs frente à biodegradação anaeróbia. Os sistemas atualmente empregados na maioria das ETEs, não livram os corpos aquáticos da presença de CE. Este trabalho contribui para o conhecimento do comportamento de alguns CE em modelos de ETE comumente empregadose pode amparar estratégias de ajustes de condições operacionais ou o uso de tecnologias que possibilitem a remoção destes contaminantes, contribuindo para que os efluentes das ETEspossam ser transformados em água de reuso de boa qualidade, atualmente uma das alternativas para o gerenciamento do problema global da escassez hídrica.

O aumento crescente da população brasileira em combinação com o uso abusivo de medicamentos no mercado nacional, aliados à falta de saneamento básico e de políticas públicas para o correto gerenciamento de alguns tipos de resíduos têm resultado na presença de compostos farmacêuticos em ambientes aquáticos. Estudos indicam que várias dessas substâncias parecem ser persistentes no ambiente e algumas vezes, resistem até mesmo às estações de tratamento de água, fazendo-se presentes na água tratada, que chega à população. O presente trabalho visou analisar quantitativamente a presença dos anti-inflamatórios e do analgésico mais comumente consumido no Brasil: diclofenaco, cetoprofeno, naproxeno, indometacina, ibuprofeno e o paracetamol em águas superficiais, por LC-MS/MS com extração em fase sólida, antes e depois do tratamento convencional, em escala laboratorial pelo ensaio de Jar-Test, bem como caracterizar o risco humano pela presença destes compostos na água após o tratamento. Os métodos utilizados na quantificação destes fármacos apresentaram bons resultados: a análise cromatográfica obteve coeficientes de correlação entre 0,9952-0,9991, com limites de quantificação de 0,5ng/mL- 50ng/mL e desvios padrões entre (0,08-2,08); na recuperação do método de extração em fase sólida o diclofenaco, o cetoprofeno, o naproxeno e a indometacina apresentaram cerca de 100% de recuperação, o ibuprofeno apresentou apenas 48%(±9,37) de recuperação e o paracetamol aproximadamente 19,84% (±2,52); no ensaio de jar-test, observou-se que apenas o cetoprofeno e o ibuprofeno não foram removidos completamente no tratamento utilizado (remoção de 0-15% do cetoprofeno e de 0-35% do ibuprofeno). Amostras ambientais foram coletadas e tratadas pelo ensaio de Jar-Test, e os valores obtidos para o cetoprofeno e ibuprofeno após o tratamento foram de 18,67-19,65ng/L e 147ng/L, respectivamente. Através de cálculos, com a dose de referência de cada um dos compostos e considerando as características desta exposição, foi possível concluir que nestas concentrações o cetoprofeno e o ibuprofeno não causam risco à saúde humana. / The increasing population growth in combination with the misuse of drugs in the domestic market, coupled with the lack of sanitation and public policies for proper management of some types of waste have resulted in the presence of pharmaceutical compounds in aquatic environments. Studies indicate that several of these substances appear to be persistent in the environment and sometimes even resistant to water treatment plants, being present in the treated water which reaches the population. This study aimed to analyze quantitatively the presence of anti-inflammatory and analgesic most commonly consumed in Brazil: diclofenac, ketoprofen, naproxen, indomethacin, ibuprofen and paracetamol in surface waters by LC-MS/MS with solid phase extraction prior and after conventional treatment in a laboratory scale by using Jar-test assay, and to determine the human risk posed by the presence of these compounds in the water after treatment. The methods used to quantify these drugs showed good results: a chromatographic analysis obtained correlation coefficients between 0.9952 to 0.9991, with limits of quantification of 0.5 ng/mL- 50ng/mL and standard deviations between (0.08 - 2.08); recovery method of solid phase extraction to diclofenac, ketoprofen, naproxen and indomethacin showed about 100% recovery, ibuprofen showed only 48% (± 9.37) and paracetamol approximately 19 84% (± 2.52) recovery; in the jar-test, it was observed that only ketoprofen and ibuprofen were not completely removed (removal: 0-15% of ketoprofen and 0-35% of ibuprofen). Environmental samples were collected and handled by jar-test test, and the values obtained for ketoprofen and ibuprofen after treatment were 18.67 to 19.65 ng / L and 147ng / L, respectively. By calculation with a reference dose of each compound and considering the characteristics of this display, it was concluded that these concentrations of ketoprofen and ibuprofen do not cause risk to human health.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The emerging pollutants are substances that enter continuously in the environment and are being more recognize due to the advancement of instrumental and sample preparation techniques. These contaminants include several chemical classes, such as pharmaceuticals, hormones, personal care products, flame retardants and others. Water is one of the most susceptible matrix since the sewage discharge is one of the main routes of environmental pollution. Bar adsorptive microextration (BAμE) has shown great analytical capacity for the analysis of organic compounds in residual level and has become a well-established analytical tool in sample preparation. In this work, a simple and low cost method was validated for the analysis of 13 emerging contaminants in water using BAμE with polymeric sorbent followed by ultra high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). The preparation, stability tests and development of BAμE devices are also discussed. Eleven different coating phases were evaluated. In order to select the best combination of experimental conditions for extraction and back extraction, central composite design (CCD) with four variables was applied. Validation results were satisfactory, since the method presented recoveries between 74% and 118% with relative standard deviations (RSD) < 19%. The analytical performance presented detection and quantification limits of 0.012 to 0.6 and 0.04 to 2 μg L-1, respectively. The proposed method combines a simple and effective sample preparation for the determination of emerging contaminants in water using a microextraction technique (BAμE) followed by UHPLC-MS/MS analysis. The method applicability was evaluated using real samples of surface, drinking and tap water and 6 positive samples were found indicating the presence of bisphenol A (0.08-0.665 μg L-1) and paracetamol (0.104-4.2 μg L-1). / Os contaminantes emergentes são substâncias que entram continuamente no meio ambiente e que estão sendo reconhecidas com maior profundidade devido ao avanço de técnicas instrumentais e de preparo de amostra. Estes compostos englobam diversas classes químicas, como por exemplo, fármacos, hormônios, produtos de higiene e cuidado pessoal, retardantes de chama, dentre outros. Uma das matrizes mais suscetíveis à contaminação é a água tendo em vista que a descarga de esgoto é uma das principais vias de poluição ambiental. A microextração adsortiva em barra (BAμE) tem demonstrado grande capacidade analítica para a análise de compostos orgânicos em nível residual e vem se tornando uma ferramenta analítica bem estabelecida no âmbito de preparo de amostras. Neste estudo foi desenvolvido e validado um método simples e de baixo custo para a determinação de 13 contaminantes emergentes em água utilizando BAμE e empregando sorvente polimérico com posterior análise por cromatografia liquida de ultra eficiência acoplada à espectrometria de massas em série (UHPLC-MS/MS). O preparo das barras bem como os testes de estabilidade foram avaliados. Onze sorventes foram testados para revestir os dispositivos. A fim de avaliar a melhor combinação de parâmetros para a extração e dessorção dos analitos, utilizou-se um planejamento do composto central (CCD) com 4 variáveis. Os resultados da validação foram satisfatórios uma vez que as recuperações obtidas ficaram entre 74% e 118% com desvio padrão relativo RSD < 19%. Os limites de detecção e quantificação foram de 0,012 a 0,6 e 0,04 a 2,0 μg L-1, respectivamente. O método proposto combina uma etapa de preparo de amostra simples e eficaz para a determinação de contaminantes emergentes em água. A aplicabilidade do método foi avaliada utilizando amostras reais de água de superfície, de torneira e mineral e destas, 6 amostras apresentaram bisfenol A (0,08-0,665 μg L-1) e paracetamol (0,104-4,2 μg L-1).

Orientador: Wilson de Figueiredo Jardim / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T13:39:08Z (GMT). No. of bitstreams: 1 Pescara_IgorCardoso_D.pdf: 5286232 bytes, checksum: 74793adc4ea590e2eb8fdeb51a796399 (MD5) Previous issue date: 2014 / Resumo: Este trabalho teve como objetivo avaliar a eficiência dos tratamentos empregados em cinco estações de tratamento de esgoto (ETE) e duas estações de tratamento de água (ETA) na remoção dos hormônios endógenos estrona (E1), 17?-estradiol (E2), estriol (E3), testosterona (TTN) e progesterona (PROG), hormônios sintéticos 17a-etinilestradiol (EE2), dietilestilbestrol (DES), norgestrel (NGT) e mestranol (MEE), produtos de uso industrial bisfenol A (BPA), fenolftaleína (PhPh), n-nonilfenol (nNP), n-octilfenol (nOP) e triclosan (TCS), o fármaco cafeína (CAF) e o pesticida atrazina (ATZ). Foi possível quantificar BPA, E1, E3, CAF e ATZ em esgoto bruto e BPA, E1, CAF e ATZ em água bruta. Para cada composto, tanto os tratamentos realizados pelas ETE quanto os realizados pelas ETA apresentaram eficiências de remoção variáveis. A cafeína foi o composto-alvo mais frequentemente encontrado nas amostras, sendo escolhida como indicador químico para avaliar a eficiência dos tratamentos. Foi encontrada uma taxa média de 99% para a remoção de CAF pelas ETE, sendo as etapas com tratamentos biológicos as mais eficientes. Os tratamentos anaeróbios apresentaram remoções médias superiores a 80% na remoção de CAF, e os tratamentos aeróbios foram capazes de remover cerca de 20% da carga do composto. Nas ETE, os tratamentos de coagulação e desinfecção foram pouco eficientes nas remoções dos compostos-alvo. Já para as ETA, foram observadas remoções de até 80% de CAF pelos tratamentos empregados, sendo a etapa de coagulação a responsável pela maior remoção de CAF da água bruta. A etapa de filtração em carvão ativado apresentou eficiências de remoção menores que 10%, enquanto a desinfecção demonstrou baixa eficiência na remoção de CAF. Na cidade de São José do Rio Preto ¿ SP foi possível quantificar, ao menos uma vez, BPA, E1, E3, PhPh, CAF, TCS e ATZ em água superficial, BPA, TCS e CAF em água subterrânea e BPA, CAF e ATZ em água de abastecimento. / Abstract: Water and wastewater conventional treatments are often considered inefficient to remove micropollutants. The aim of this work was to evaluate the removal efficiency of the endogenous hormones estrone (E1), 17? estradiol (E2), estriol (E3), testosterone (TTN), and progesterone (PROG), the synthetic hormones 17a-ethinylestradiol (EE2), diethylstilbestrol (DES), norgestrel (NGT), and mestranol (MEE), the industrial chemicals bisphenol A (BPA), phenolphthalein (PhPh), n nonylphenol (nNP), n octylphenol (nOP), and triclosan (TCS), the pharmaceutical caffeine (CAF), and the pesticide atrazine (ATZ) by five wastewater treatment plants (WWTP) and two drinking water treatment plants (DWTP). The target compounds BPA, E1, E3, CAF, and ATZ were found in raw sewage, while BPA, E1, CAF, and ATZ in raw water. Both WWTP and DWTP treatments presented variable removal efficiency. Caffeine was the target compound more often detected in samples, thus it was chosen as a chemical indicator to evaluate treatment efficiencies. The average removal of CAF by WWTP was 99%, in which the biological treatment was more efficient. The anaerobic treatment presented an average removal of CAF above 80%, and around 20% for the aerobic treatments. Coagulation and disinfection treatments of WWTP showed low efficiency to remove the target compounds. DWTP treatment efficiency reached up to 80% removal, with coagulation step presenting highest removals of CAF. The activated carbon filtration showed removal efficiency under 10%, whereas the disinfection step presented low efficiency to remove CAF. At São José do Rio Preto city were found, at least once, BPA, E1, E3, PhPh, CAF, TCS, and ATZ in surface water; BPA, TCS, and CAF in groundwater, and BPA, CAF, and ATZ in drinking water / Doutorado / Quimica Analitica / Doutor em Ciências