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Submitted by GLÁUCIA TINOCO CORRÊA null (glauciacorrea_15@hotmail.com) on 2017-09-07T02:49:22Z No. of bitstreams: 1 tese versão online.pdf: 5660272 bytes, checksum: c8ac61b6a73153496fecaf76e1315c4d (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-09-11T20:12:56Z (GMT) No. of bitstreams: 1 correa_gt_dr_araiq.pdf: 5660272 bytes, checksum: c8ac61b6a73153496fecaf76e1315c4d (MD5) / Made available in DSpace on 2017-09-11T20:12:56Z (GMT). No. of bitstreams: 1 correa_gt_dr_araiq.pdf: 5660272 bytes, checksum: c8ac61b6a73153496fecaf76e1315c4d (MD5) Previous issue date: 2017-08-17 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Corantes de cabelo, provenientes principalmente da tintura comercial de cabelo em salões de beleza, quando não convenientemente descartados, podem gerar efluentes de difícil tratamento. Além disso, a análise de corante de cabelo em fios de cabelo tingidos, poderia favorecer informações úteis para análise forense. Em virtude de alto consumo de corantes de cabelo, que podem ser encontrados na forma de tinturas permanente, semipermantes e temporárias, com diferentes estruturas e comportamento físico-químico, a demanda por métodos analíticos sensíveis e robustos para sua quantificação é altamente pertinente. Diante disso, o presente trabalho descreve a construção de sensores eletroquímicos para quantificação de corantes de cabelo do tipo temporário, pois são classe de corantes facilmente removidos do cabelo e, consequentemente, podem ser liberados para o meio ambiente. O sensor eletroquímico consiste no desenvolvimento de um eletrodo compósito com partículas magnéticas modificadas como grupos carboxílicos (CFMP) para determinação dos corantes basic brown 16 (BB16), basic red 51 (BR51) e basic yellow 57 (BY57) em amostras de extratos de fios de cabelos, amostras comercias de tintura temporária, água de lavagem, amostras de água de rio e de torneira. Os três corantes apresentam grupos azos como cromóforos. No presente trabalho, investigou-se a oxidação de aminas e hidroxilas presentes como grupos auxocromos nos corantes. Os resultados mostraram que a oxidação do grupo funcional nos corantes sobre o eletrodo compósito modificados por grupos carboxílicos pode ocorrer em potenciais de 0,44 V, 0,86 V e 0,65, respectivamente para os corantes BB16, BR51 e BY57 e a corrente de pico aumenta significativamente em relação ao eletrodo sem modificação. A interação entre corante + CFMP foi comprovada por espectroscopia de UV/Vis e FTIR. Foram construídas curvas analíticas para os corantes BB16, BR51 e BY57, usando as condições otimizadas na técnica de voltametria de onda quadrada (VOQ): frequência de aplicação dos pulsos (f) = 30 s-1, amplitude de pulsos (a) = 50 mV e incremento de varredura (ΔEs) = 2 mV para os corantes. Relações lineares foram obtidas nos intervalos de 2,0 x 10-7 mol L-1 a 9,0 x 10-7 mol L-1, 1,5 x 10-6 mol L-1 a 5,5 x 10-5 mol L-1, 2,0 x 10-7 mol L-1 a 1,2 x 10-7 mol L-1 para os corantes BB16, BR51 e BY57, respectivamente. Foram obtidos limites de detecção de 1,01 x 10-8 mol L-1, 1,19 x 10-7 mol L-1 e 2,89 x 10-7 mol L-1 para os corantes BB16, BR51 e BY57, respectivamente. O método foi aplicado em amostras de extratos de fios de cabelo, água de lavagem, água de torneira e formulações comerciais. A determinação simultânea dos corantes BB16, BR51 e BY57 foi também proposto usando o método descrito e otimizado. O método foi aplicado em amostras de água de torneira e água de rio com recuperações de aproximadamente 100% e em amostra da tintura de cabelo comercial (COLOR EXPRESS (Vermelho intenso). O método eletroquímico foi comparado com o método de referência usando cromatografia líquida de alta eficiência com detector de arranjo de diodo (HPLC/DAD). / Hair dyes, mainly coming from commercial hair colorants in beauty salons, when not properly discarded, can generate effluents that are difficult to treat. In addition, hair dye analysis in dyed hair strands could be used as useful information for forensic analysis. Due to the high consumption of hair dyes, which can be found in the form of permanent, semipermanent and temporary dye, with different structures and physicochemical behavior, the demand for sensitive and robust analytical methods for their quantification is highly relevant. Therefore, the present work describes the construction of electrochemical sensors for the quantification of hair dyes of the temporary type, because they are class of dyes easily removed from the hair and, consequently, are released in great quantity for the environment. The electrochemical sensor consists of the development of a composite electrode using modified magnetic particles with carboxylic groups (CFMP) to determine the dyes basic brown 16 (BB16), basic red 51 (BR51), and basic yellow 57 (BY57) in samples of yarn extracts Hair samples, commercial samples of temporary tincture, wash water, samples of river water and tap water. The three dyes analyzed have azide groups as chromophores. In the present work, the oxidation of amines and hydroxyls present as auxochromic groups in the dyes was investigated. The results showed that the oxidation of the functional group in the dyes on the composite electrode modified by carboxylic groups can occur in Ea = 0.44 V, Ea = 0.86 V and Ea = 0.65, respectively for the dyes BB16, BR51, and BY57 and the peak current increases significantly with respect to the electrode without modification. The interaction between dye + CFMP was confirmed by UV/Vis and FTIR spectroscopy. Analytical curves for the BB16, BR51, and BY57 dyes were constructed using the optimized conditions in the square wave voltammetry (SWV) technique: pulse frequency (f) = 30 s-1, pulse amplitude (a) = 50 mV and scanning increment (ΔEs) = 2 mV for the dyes. Linear relationships were obtained at intervals of 2.0 x 10-7 mol L-1 to 9.0 x 10-7 mol L-1, 1.5 x 10-6 mol L-1 at 5.5 x 10-5 mol L-1, 2.0 x 10-7 mol L-1 to 1.2 x 10-7 mol L-1 for the dyes BB16, BR51, and BY57, in this order, using the SWV technique. Detection limits of 1.01 x 10-8 mol L-1, 1.19 x 10-7 mol L-1, 2.89 x 10-7 mol L-1 were obtained for the dyes BB16, BR51, and BY57, respectively. The method was applied to hair strands, wash water, tap water, and commercial formulation samples. The simultaneous determination of the dyes BB16, BR51, and BY57 was also proposed using the method described and optimized. The simultaneous determination of the dyes BB16, BR51 and, BY57 was also proposed using the method described and optimized. The method was applied to tap water and river water samples with approximately 100% recoveries and commercial hair dye sample (COLOR EXPRESS®). The electrochemical method was compared with the reference method using high performance liquid chromatography with diode arrangement detector (HPLC/DAD). / FAPESP: 2013/21542-6

The provision of adequate sanitation is an essential service. In terms of schedule 4B of the Constitution of the Republic of South Africa, 108 of 1996 (the Constitution), such provision is a function of local government. It falls within the developmental mandate of local government in that it is a basic service that contributes to the quality of people’s lives. However, the lack of access to adequate sanitation is a problem in South Africa, as roughly 17 million people are still without access to improved sanitation. This lack has a detrimental impact on people’s lives and merits an enquiry into the role of local government in providing such services. In this study, the legal mandate of local government in relation to sanitation is explored from an environmental justice perspective, as access to sanitation is an environmental issue. Although there is no explicit constitutional right to sanitation, it is argued that such a right is implicitly recognised by means of the provision of other rights in the Constitution, legislation and policy documents. The study further unpacks the mechanisms and instruments available to municipalities to enable them to achieve the objectives of environmental justice when providing sanitation services. The urban and rural landscape in South Africa have different features, and the people who live in them have different needs. For this reason the features and challenges of urban and rural municipalities are discussed separately, thus establishing the different approaches that urban and rural municipalities might have to follow in the provision of sanitation services. The study concludes with recommendations and the identification of the various governance tools that municipalities may use in order to realise the right to sanitation whilst achieving the objectives of environmental justice. / LLM, North-West University, Potchefstroom Campus, 2015

The provision of adequate sanitation is an essential service. In terms of schedule 4B of the Constitution of the Republic of South Africa, 108 of 1996 (the Constitution), such provision is a function of local government. It falls within the developmental mandate of local government in that it is a basic service that contributes to the quality of people’s lives. However, the lack of access to adequate sanitation is a problem in South Africa, as roughly 17 million people are still without access to improved sanitation. This lack has a detrimental impact on people’s lives and merits an enquiry into the role of local government in providing such services. In this study, the legal mandate of local government in relation to sanitation is explored from an environmental justice perspective, as access to sanitation is an environmental issue. Although there is no explicit constitutional right to sanitation, it is argued that such a right is implicitly recognised by means of the provision of other rights in the Constitution, legislation and policy documents. The study further unpacks the mechanisms and instruments available to municipalities to enable them to achieve the objectives of environmental justice when providing sanitation services. The urban and rural landscape in South Africa have different features, and the people who live in them have different needs. For this reason the features and challenges of urban and rural municipalities are discussed separately, thus establishing the different approaches that urban and rural municipalities might have to follow in the provision of sanitation services. The study concludes with recommendations and the identification of the various governance tools that municipalities may use in order to realise the right to sanitation whilst achieving the objectives of environmental justice. / LLM, North-West University, Potchefstroom Campus, 2015