Foram estudadas as propriedades ácido-base de alguns polieletrólitos de interesse ambiental; no sentido de se avaliar a adequabilidade do modelo de sítios discretos na determinação e caracterização dos grupos ionizáveis presentes nestas macromoléculas. Estudou-se os seguintes sistemas de polieletrólitos: ácido húmico comercial (Aldrich) e extraído de vermicomposto (Humus de minhoca); microalga Spirulina (cianobactéria), ácido algínico e ácido poliacrílico de massas molares 2000 e 250000g/mol. Foram realizadas titulações potenciométricas alcalimétricas em diferentes meios iônicos à 25°C com os compostos acima citados. Os dados obtidos foram tratados por linearização (Funções de Gran Modificadas) e regressão não-linear. Os resultados obtidos pelo ácido húmico extraído de vermicomposto (humus de minhoca) e da microalga Spirulina mostraram-se indepentes da força iônica; indicando que o modelo de sítios discretos representa adequadamente os dados experimentais. Para as demais amostras, a estequiometria dos grupos determinados mostrou-se independente do meio iônico, porém os valores de pKa foram bastante afetados, devido à forte influência das interações eletrostáticas decorrentes da acumulação de cargas sobre as macromoléculas durante as titulações. Comparativamente os resultados obtidos tanto por regressão não linear como pelas Funções de Gran modificadas foram similares. / Acid base properties of some polyeletrolytes and colloidal suspensions were studied to evaluate the suitability of discrete site distribution model to fit potentiometric data for determination and characterization of ionizable groups presents in these materials. The polyelectrolytes studied were: commercial humic acid from Aldrich, humic acid isolated from vermicompost, mixed species of microalgae Spirulina, alginic acid and polyacrylic acid of molar masses 2000 and 250000 g/mol. Potentiometric titrations were performed in different ionic media to evaluate the effect of eletrostatic interactions on the titration data. Titrations were perfomed at 25°C, and the data were treated bya linear method based on Modified Gran Functions, as well as by a multiparametric Non-Linear Regression method. The results obtained for the vermicompost humic acid and Spirulina were independent of the ionic strength, suggesting that the chemical heterogeneity plays the major role in the acid base properties of these materials. Thus, the discrete site distribution model is well suited to characterize these materials. For the other polyelectrolytes studied, the influence of eletrostatic interactions was noticed. The discrete site distribution model was able to determine the total stoichiometry of the ionizable groups, but the ionization constants and the distribution of site concentration were dependent on the ionic strength and molar mass of these polyelectrolyte.

Nesta pesquisa foram realizados levantamentos geofísicos utilizando os métodos eletromagnético indutivo - EMI (equipamento EM38) e GPR - Ground Penetrating Radar, visando localizar redes de interferências, tais como, tubulações metálicas, cabos elétricos e conduítes de plástico instalados nas linhas 6 e 7 do Sítio Controlado de Geofísica Rasa do IAG/USP. Os dados EMI foram afetados pelo drift instrumental devido à variação de temperatura. A sua correção foi efetiva por meio do uso de uma função quadrática, realçando os alvos mais profundos. A aquisição em distância permitiu detectar alvos metálicos no subsolo com boa precisão e a aquisição em tempo permitiu fazer um mapeamento regional de alvos metálicos no subsolo. Os melhores resultados foram obtidos com a aquisição em distância, com os sensores posicionados a 10 cm de altura, devido às anomalias ficarem mais nítidas, onde a influência da condutividade do background foi reduzida. Os perfis GPR 2D obtidos com a antena de 400 MHz permitiram detectar os alvos até 1 m de profundidade e com a antena de 200 MHz foi possível detectar quase todos os alvos metálicos e não-metálicos instalados nas linhas estudas do SCGR. Para o GPR quase-3D, na forma de depth slices, foram importantes para estimar as dimensões dos alvos e melhorar a visualização dos resultados. Os resultados obtidos com os métodos EMI e GPR são complementares, sendo ambos recomendados no mapeamento de interferências no subsolo, tendo aplicações diretas nas áreas de planejamento urbano e infra-estrutura nos grandes centros urbanos. / This research was conducted geophysical surveys using inductive electromagnetic - IEM (EM38 equipment) and GPR - Ground Penetrating Radar methods, to locate network interference, such as metal pipes, electric cables and plastic conduit installed in lines 6 and 7 of test site of the IAG/USP (SCGR). IEM data were affected by instrumental drift due to temperature variation. The correction was effective through the use of a quadratic function, highlighting the deeper targets. The acquisition targets identified in the distance underground metal with good accuracy and acquisition time allowed to make a survey of regional targets metal underground. The best results were obtained with the acquisition in distance with the sensors placed at 10 cm in height, due to deficiencies become more clear, where the influence of the background conductivity was reduced. The 2D GPR profiles obtained with the antenna of 400 MHz to detect the target by 1 m depth and the antenna of 200 MHz was possible to detect almost all metal targets and non-metallic lines installed in the study SCGR. GPR to the quasi-3D in the form of depth slices, were important for estimating the size of the targets and improve the visualization of results. The results obtained with the IEM and GPR methods are complementary, and both are recommended in mapping interference underground, with direct applications in the areas of urban planning and infrastructure in urban centers.

Foram estudadas as propriedades ácido-base de alguns polieletrólitos de interesse ambiental; no sentido de se avaliar a adequabilidade do modelo de sítios discretos na determinação e caracterização dos grupos ionizáveis presentes nestas macromoléculas. Estudou-se os seguintes sistemas de polieletrólitos: ácido húmico comercial (Aldrich) e extraído de vermicomposto (Humus de minhoca); microalga Spirulina (cianobactéria), ácido algínico e ácido poliacrílico de massas molares 2000 e 250000g/mol. Foram realizadas titulações potenciométricas alcalimétricas em diferentes meios iônicos à 25°C com os compostos acima citados. Os dados obtidos foram tratados por linearização (Funções de Gran Modificadas) e regressão não-linear. Os resultados obtidos pelo ácido húmico extraído de vermicomposto (humus de minhoca) e da microalga Spirulina mostraram-se indepentes da força iônica; indicando que o modelo de sítios discretos representa adequadamente os dados experimentais. Para as demais amostras, a estequiometria dos grupos determinados mostrou-se independente do meio iônico, porém os valores de pKa foram bastante afetados, devido à forte influência das interações eletrostáticas decorrentes da acumulação de cargas sobre as macromoléculas durante as titulações. Comparativamente os resultados obtidos tanto por regressão não linear como pelas Funções de Gran modificadas foram similares. / Acid base properties of some polyeletrolytes and colloidal suspensions were studied to evaluate the suitability of discrete site distribution model to fit potentiometric data for determination and characterization of ionizable groups presents in these materials. The polyelectrolytes studied were: commercial humic acid from Aldrich, humic acid isolated from vermicompost, mixed species of microalgae Spirulina, alginic acid and polyacrylic acid of molar masses 2000 and 250000 g/mol. Potentiometric titrations were performed in different ionic media to evaluate the effect of eletrostatic interactions on the titration data. Titrations were perfomed at 25°C, and the data were treated bya linear method based on Modified Gran Functions, as well as by a multiparametric Non-Linear Regression method. The results obtained for the vermicompost humic acid and Spirulina were independent of the ionic strength, suggesting that the chemical heterogeneity plays the major role in the acid base properties of these materials. Thus, the discrete site distribution model is well suited to characterize these materials. For the other polyelectrolytes studied, the influence of eletrostatic interactions was noticed. The discrete site distribution model was able to determine the total stoichiometry of the ionizable groups, but the ionization constants and the distribution of site concentration were dependent on the ionic strength and molar mass of these polyelectrolyte.

O presente trabalho apresenta estudos espectrofotométricos relacionados à autoxidação dos complexos de Cu(II), Ni(II) e Co(II)/tetraglicina induzida por sulfito. Nossos estudos verificaram que a autoxidação de Cu(II)/tetraglicina (1,0x10-3 mol L-1) em pH = 9,0 (tampão borato) é afetada pela presença de traços de Ni(II) ou Co(II). Na ausência de Ni(II) ou Co(II), a reação é muito ineficiente e lenta com períodos de indução longos (aproximadamente 4 h). Ni(II) ou Co( II) em concentrações baixas ( 10-5 - 10-6 mol L-1) afetam significativamente a cinética: o período de indução diminui drasticamente (a menos de 2 s) e a formação de Cu(III) é fortemente acelerada com simultâneo aumento da eficiência da reação. A atividade catalítica e o sinergismo positivo de Co(II) e Ni(II) podem ser explicados pela oxidação mais rápida de Co(II) ou Ni(II)/tetraglicina pelo oxigênio dissolvido. O processo eletroquímico relacionado aos sistemas Cu(II)/Cu(III)/tetraglicina e Ni(II)/Ni(III)/tetraglicina são reversíveis, possibilitando monitorá-los adequadamente mediante o uso da técnica de eletrodo rotativo disco-anel. Entretanto, o sistema Co(II)/Co(III)/tetraglicina é irreversível. Esses estudos mostraram que as espécies de Cu(III) e Ni(III) geradas no eletrodo disco são instáveis nas condições experimentais empregadas. O efeito sinérgico positivo na presença de Ni(II) (que permitiu aumentar a sensibilidade) foi aproveitado para desenvolvimento de método espectrofotométrico e amperométrico simples e sensível para a determinação indireta de sulfito em meio aquoso. O método espectrofotométrico está baseado na medida de absorbância do complexo de Cu(III)/tetraglicina (gerado na presença de sulfito e traços de Ni(II)) em 365 nm. O método amperométrico em análise por injeção em fluxo baseia-se na medida de corrente (0,1 V vs Ag/AgCl) em função da concentração de Cu(III)/tetraglicina gerado quimicamente, na presença de sulfito e traços de Ni(II). Os métodos desenvolvidos foram empregados para a determinação de S(IV), em vinhos e sucos, após a sua extração da amostra acidificada, os resultados obtidos concordaram com aqueles obtidos pelo método iodométrico. / The present work presents spectrophotometric studies related to the sulfite induced autoxidation of Cu(II), Ni(II) and Co(II)/tetraglycine complexes. The sulfite induced autoxidação of Cu(II)/tetraglycine (1.0x10-3 mol L-1) at pH = 9.0 (borate buffer) is affected by the presence of small quantities of the Ni(II) or Co(II). In the absence of added nickel (II) or cobalt (II), the reaction is very inefficient and slow with one large induction period (about 4 h). Trace amounts of Ni(II) or Co(II) (10-5 - 10-6 M) affect the kinetic significantly: the induction period drastically decreases (less than 2 s) and the formation of Cu(III) is strongly accelerated. The effectiveness of Cu(III) formation becomes much higher. The catalytic activity and the positive synergism of Co(II) and Ni(II) may be explained by the faster oxidation of Co(II) or Ni(II)/tetraglycine complexes by dissolved oxygen. The electrochemistry of Cu(II)/Cu(III)/tetraglycine and Ni(II)/Ni(III)/tetraglycine systems are reversible, such as it was possible to monitor them by using the rotating ring-disk electrode technique. However, the Co(II)/Co(III)/tetraglycine system is irreversible. Those studies showed that the Cu(III) and Ni(III) species generated on the disk electrode are unstable in the employed experimental conditions. The positive sinergistic effect in the presence of Ni(II) (which allowed to increase the sensibility) was taken in advantage for development of one simple and sensitive spectrophotometric and amperometric method for indirect determination of sulfite in aqueous medium. The spectrophotometric method is based on the absorbance measurement of the Cu(III)/tetraglicyne complex (generated in the presence of sulfite and small quantities of Ni(II)) at 365 nm. The amperometric method by flow injection analysis is based on the current measurement (0.1 V vs Ag/AgCl) as function of Cu(III)/tetraglycine concentration chemically generated, in the presence of sulfite and Ni(II). The methods were employed for the determination of S(IV), in wines and juices, after its extraction from acidified samples and the results were in agreement with those obtained by the iodometric procedure.

The objective of our studies is the combination of electromagnetic and direct current (DC) resistivity methods in a joint inversion approach to improve the reconstruction of a given conductivity distribution. We utilize the distinct sensitivity patterns of different methods to enhance the overall resolution power and ensure a more reliable imaging result. In order to simplify the work with more than one electromagnetic method and establish a flexible and state-of-the-art software basis, we developed new DC resistivity and electromagnetic forward modeling and inversion codes based on finite elements of second order on unstructured grids. The forward operators are verified using analytical solutions and convergence studies before we apply a regularized Gauss-Newton scheme and successfully invert synthetic data sets. Finally, we link both codes with each other in a joint inversion. In contrast to most widely used joint inversion strategies, where different data sets are combined in a single least-squares problem resulting in a large system of equations, we introduce a sequential approach that cycles through the different methods iteratively. This way, we avoid several difficulties such as the determination of the full set of regularization parameters or a weighting of the distinct data sets. The sequential approach makes use of a smoothness regularization operator which penalizes the deviation of the model parameters from a given reference model. In our sequential strategy, we use the result of the preceding individual inversion scheme as reference model for the following one. We successfully apply this approach to synthetic data sets and show that the combination of at least two methods yields a significantly improved parameter model compared to the individual inversion results. / Ziel der vorliegenden Arbeit ist die gemeinsame Inversion (\"joint inversion\") elektromagnetischer und geoelektrischer Daten zur Verbesserung des rekonstruierten Leitfähigkeitsmodells. Dabei nutzen wir die verschiedenartigen Sensitivitäten der Methoden aus, um die Auflösung zu erhöhen und ein zuverlässigeres Ergebnis zu erhalten. Um die Arbeit mit mehr als einer Methode zu vereinfachen und eine flexible Softwarebasis auf dem neuesten Stand der Forschung zu etablieren, wurden zwei Codes zur Modellierung und Inversion geoelektrischer als auch elektromagnetischer Daten neu entwickelt, die mit finiten Elementen zweiter Ordnung auf unstrukturierten Gittern arbeiten. Die Vorwärtsoperatoren werden mithilfe analytischer Lösungen und Konvergenzstudien verifiziert, bevor wir ein regularisiertes Gauß-Newton-Verfahren zur Inversion synthetischer Datensätze anwenden. Im Gegensatz zur meistgenutzten \"joint inversion\"-Strategie, bei der verschiedene Daten in einem einzigen Minimierungsproblem kombiniert werden, was in einem großen Gleichungssystem resultiert, stellen wir schließlich einen sequentiellen Ansatz vor, der zyklisch durch die einzelnen Methoden iteriert. So vermeiden wir u.a. eine komplizierte Wichtung der verschiedenen Daten und die Bestimmung aller Regularisierungsparameter in einem Schritt. Der sequentielle Ansatz wird über die Anwendung einer Glättungsregularisierung umgesetzt, bei der die Abweichung der Modellparameter zu einem gegebenen Referenzmodell bestraft wird. Wir nutzen das Ergebnis der vorangegangenen Einzelinversion als Referenzmodell für die folgende Inversion. Der Ansatz wird erfolgreich auf synthetische Datensätze angewendet und wir zeigen, dass die Kombination von mehreren Methoden eine erhebliche Verbesserung des Inversionsergebnisses im Vergleich zu den Einzelinversionen liefert.

The objective of our studies is the combination of electromagnetic and direct current (DC) resistivity methods in a joint inversion approach to improve the reconstruction of a given conductivity distribution. We utilize the distinct sensitivity patterns of different methods to enhance the overall resolution power and ensure a more reliable imaging result. In order to simplify the work with more than one electromagnetic method and establish a flexible and state-of-the-art software basis, we developed new DC resistivity and electromagnetic forward modeling and inversion codes based on finite elements of second order on unstructured grids. The forward operators are verified using analytical solutions and convergence studies before we apply a regularized Gauss-Newton scheme and successfully invert synthetic data sets. Finally, we link both codes with each other in a joint inversion. In contrast to most widely used joint inversion strategies, where different data sets are combined in a single least-squares problem resulting in a large system of equations, we introduce a sequential approach that cycles through the different methods iteratively. This way, we avoid several difficulties such as the determination of the full set of regularization parameters or a weighting of the distinct data sets. The sequential approach makes use of a smoothness regularization operator which penalizes the deviation of the model parameters from a given reference model. In our sequential strategy, we use the result of the preceding individual inversion scheme as reference model for the following one. We successfully apply this approach to synthetic data sets and show that the combination of at least two methods yields a significantly improved parameter model compared to the individual inversion results. / Ziel der vorliegenden Arbeit ist die gemeinsame Inversion (\"joint inversion\") elektromagnetischer und geoelektrischer Daten zur Verbesserung des rekonstruierten Leitfähigkeitsmodells. Dabei nutzen wir die verschiedenartigen Sensitivitäten der Methoden aus, um die Auflösung zu erhöhen und ein zuverlässigeres Ergebnis zu erhalten. Um die Arbeit mit mehr als einer Methode zu vereinfachen und eine flexible Softwarebasis auf dem neuesten Stand der Forschung zu etablieren, wurden zwei Codes zur Modellierung und Inversion geoelektrischer als auch elektromagnetischer Daten neu entwickelt, die mit finiten Elementen zweiter Ordnung auf unstrukturierten Gittern arbeiten. Die Vorwärtsoperatoren werden mithilfe analytischer Lösungen und Konvergenzstudien verifiziert, bevor wir ein regularisiertes Gauß-Newton-Verfahren zur Inversion synthetischer Datensätze anwenden. Im Gegensatz zur meistgenutzten \"joint inversion\"-Strategie, bei der verschiedene Daten in einem einzigen Minimierungsproblem kombiniert werden, was in einem großen Gleichungssystem resultiert, stellen wir schließlich einen sequentiellen Ansatz vor, der zyklisch durch die einzelnen Methoden iteriert. So vermeiden wir u.a. eine komplizierte Wichtung der verschiedenen Daten und die Bestimmung aller Regularisierungsparameter in einem Schritt. Der sequentielle Ansatz wird über die Anwendung einer Glättungsregularisierung umgesetzt, bei der die Abweichung der Modellparameter zu einem gegebenen Referenzmodell bestraft wird. Wir nutzen das Ergebnis der vorangegangenen Einzelinversion als Referenzmodell für die folgende Inversion. Der Ansatz wird erfolgreich auf synthetische Datensätze angewendet und wir zeigen, dass die Kombination von mehreren Methoden eine erhebliche Verbesserung des Inversionsergebnisses im Vergleich zu den Einzelinversionen liefert.