Fatores químicos e físicos que afetam a contaminação por chumbo e cobre em água potável: uma abordagem para o estudo de caso em química analítica

Lead and copper concentrations in drinking water increase considerably on going from municipality reservoirs to the households sampled in Ribeirão Preto (SP-Brazil). Flushing of only 3 liters of water reduced metal concentrations by more than 50%. Relatively small changes in water pH rapidly affected corrosion processes in lead pipes, while water hardness appeared to have a long-term effect. This approach aims to encourage University teachers to use its content as a case study in disciplines of Instrumental Analytical Chemistry and consequently increase knowledge about drinking water contamination in locations where no public monitoring of trace metals is in place.

Propriedades relacionadas à acidez e basicidade a partir da abordagem em química computacional

Analytical Chemistry books lack a clear link between thermodynamic and equilibrium approaches involving acids and bases. In this work, theoretical calculations were performed to search for these relations. An excellent relationship was found between difference in Gibbs free energy, ∆G of acid dissociation reaction and ∆G of hydrolysis reaction of the corresponding conjugate base. A relationship between ∆G of hydrolysis reaction of conjugate acids and their corresponding atomic radius was also identified, showing that stability plays an important role in hydrolysis reactions. Finally, the importance of solvation in acid/base behavior was demonstrated when comparing the corresponding theoretical and experimental ∆G´s.

Experimento utilizando grãos para explorar a calibração em análises químicas

The conventional curriculum of Analytical Chemistry undergraduate courses emphasizes the introduction of techniques, methods and procedures used for instrumental analysis. All these concepts must be integrated into a sound conceptual framework to allow students to make appropriate decisions. Method calibration is one of the most critical parameters that has to be grasped since most analytical techniques depend on it for quantitative analysis. The conceptual understanding of calibration is not trivial for undergraduate students. External calibration is widely discussed during instrumental analysis courses. However, the understanding of the limitations of external calibration to correct some systematic errors is not directly derived from laboratory examples. The conceptual understanding of other calibration methods (standard addition, matrix matching, and internal standard) is imperative. The aim of this work is to present a simple experiment using grains (beans, corn and chickpeas) to explore different types of calibration methods.

CONSTRUÇÃO DE UM DISPOSITIVO DE PRESSURIZAÇÃO A VÁCUO PARA A PREPARAÇÃO DE FASES ESTACIONÁRIAS MONOLÍTICAS VIA PROCESSO SOL-GEL

The filling of capillaries via the sol-gel process is growing. Therefore, this technical note focuses on disseminating knowledge acquired in the Group of Analytical Chemistry and Chemometrics over seven years working with monolithic stationary phase preparation in fused silica capillaries. We believe that the detailed information presented in this technical note concerning the construction of an alternative high pressurization device, used to fill capillary columns via the sol-gel process, which has promising potential for applications involving capillary electrochromatography and liquid chromatography in nano scale, may be enlightening and motivating for groups interested in developing research activities within this theme.

TREATMENT OF WASTE FROM ATOMIC EMISSION SPECTROMETRIC TECHNIQUES AND REUSE IN UNDERGRADUATE LAB CLASSES FOR QUALITATIVE ANALYSIS

Flame atomic absorption spectrometry (FAAS) and inductively coupled plasma optical emission spectrometry (ICP OES) are widely used in academic institutions and laboratories for quality control to analyze inorganic elements in samples. However, these techniques have been observed to underperform in sample nebulization processes. Most of the samples processed through nebulization system are discarded, producing large volumes of waste. This study reports the treatment and reuse of the waste produced from ICP OES technique in a laboratory of analytical research at the Universidade Federal do Ceará, Brazil. The treatment of the waste was performed by the precipitation of elements using (NH4)2CO3. Subsequently, the supernatant solution can be discarded in accordance with CONAMA 430/2011. The precipitate produced from the treatment of residues can be reused as a potential sample in undergraduate qualitative analytical chemistry lab classes, providing students the opportunity to test a real sample.

AVALIAÇÃO DO USO DE PLANILHAS COMPUTACIONAIS COMO UMA FERRAMENTA DIDÁTICA EM QUÍMICA ANALÍTICA QUALITATIVA

The use of spreadsheet softwares is not widespread in Chemical Education in Brazil as a computational education tool. By its turn the Qualitative Analytical Chemistry is considered a discipline with classical and non-flexible content. Thus in this work the spreadsheet software Excel® was evaluated as a teaching tool in a Qualitative Analytical Chemistry course for calculations of concentrations of the species in equilibrium in solutions of acids. After presenting the theory involved in such calculations the students were invited to elaborate the representation of the distribution of these species in a graphical form, using the spreadsheet software. Then the teaching team evaluated the resulting graphics regarding form and contents. The graphics with conceptual and/or formal errors were returned for correction, revealing significant improvement in the second presentation in all cases. The software showed to be motivating for the content of the discipline, improving the learning interest, while it was possible to prove that even in classical disciplines it is possible to introduce new technologies to help the teaching process.

Puun kemiallinen koostumus ja sen uuteaineiden analysointi

Tämä kandidaatintyö jakaantuu teoriaosuuteen ja kokeelliseen osaan. Teoriaosuudessa käsitellään puun kemiallista koostumusta, jossa keskitytään erityisesti puun uuteaineisiin. Puun uuteaineista käsitellään erityisesti hartsihappoja, koska ne ovat taloudellisesti arvokkaita yhdisteitä. Teoriaosuudessa esitellään puun uuteaineille eri analyysimenetelmiä kaasu- ja nestekromatografialla sekä kapillaarielektroforeesilla. Analyysimenetelmät ovat koottu tieteisartikkeleista, joissa on tutkittu ja analysoitu puun uuteaineita. Työn kokeellisessa osuudessa analyysilaitteeksi valittiin kapillaarielektroforeesi (CE). Tavoitteena oli löytää menetelmä, jolla voisi analysoida puun uuteaineista hartsi- ja rasvahappoja. Kapillaarielektroforeesille testattiin viittä erilaista menetelmää. Referenssinäytteinä työssä käytettiin oleiinihappoa ja abietiinihappoa. Yhdellä testatuista menetelmistä saatiin analysoitua oleiinihappoa referenssinäytteistä, mutta mahdollisesti myös abietiinihappoa. Tässä menetelmässä CE:n puskuriliuoksena käytettiin 50 mM boraattia + 100 mM natriumlauryylisulfaattia. Menetelmässä näytteen injektioaika oli 10 sekuntia ja CE:n sähköjännite oli 25 kV. Menetelmä oli toimiva 1000 mg/L liuoksilla, joiden pH oli nostettu 9-10 natriumhydroksidilla. Menetelmän haittapuolena on se, että alle 200 mg/L:n kantaliuoksilla CE:llä ei voitu analysoida oleiini- ja abietiinihappoa. Menetelmä ei siis sovellu esimerkiksi sellaisten näytteiden analysointiin, jossa oleiini- ja abietiinihappo pitoisuudet ovat hyvin pienet (alle 200 mg/L).

Investigating the role of retinoic acid in the vertebrate and invertebrate nervous system

Please consult the paper edition of this thesis to read. It is available on the 5th Floor of the Library at Call Number: Z 9999.5 B56 D64 2007

Analyse par spectrométrie de masse des antibiotiques vétérinaires liés à l’élevage porcin

L’élevage des porcs représente une source importante de déversement d’antibiotiques dans l’environnement par l’intermédiaire de l’épandage du lisier qui contient une grande quantité de ces molécules sur les champs agricoles. Il a été prouvé que ces molécules biologiquement actives peuvent avoir un impact toxique sur l’écosystème. Par ailleurs, elles sont aussi suspectées d’engendrer des problèmes sanitaires et de contribuer à la résistance bactérienne pouvant mener à des infections difficilement traitables chez les humains. Le contrôle de ces substances dans l’environnement est donc nécessaire. De nombreuses méthodes analytiques sont proposées dans la littérature scientifique pour recenser ces composés dans plusieurs types de matrice. Cependant, peu de ces méthodes permettent l’analyse de ces contaminants dans des matrices issues de l’élevage agricole intensif. Par ailleurs, les méthodes analytiques disponibles sont souvent sujettes à des faux positifs compte tenu de la complexité des matrices étudiées et du matériel utilisé et ne prennent souvent pas en compte les métabolites et produits de dégradation. Enfin, les niveaux d’analyse atteints avec ces méthodes ne sont parfois plus à jour étant donné l’évolution de la chimie analytique et de la spectrométrie de masse. Dans cette optique, de nouvelles méthodes d’analyses ont été développées pour rechercher et quantifier les antibiotiques dans des matrices dérivées de l’élevage intensif des porcs en essayant de proposer des approches alternatives sensibles, sélectives et robustes pour quantifier ces molécules. Une première méthode d’analyse basée sur une technique d’introduction d’échantillon alternative à l’aide d’une interface fonctionnant à l’aide d’une désorption thermique par diode laser munie d’une source à ionisation à pression atmosphérique, couplée à la spectrométrie de masse en tandem a été développée. L’objectif est de proposer une analyse plus rapide tout en atteignant des niveaux de concentration adaptés à la matrice étudiée. Cette technique d’analyse couplée à un traitement d’échantillon efficace a permis l’analyse de plusieurs antibiotiques vétérinaires de différentes classes dans des échantillons de lisier avec des temps d’analyse courts. Les limites de détection atteintes sont comprises entre 2,5 et 8,3 µg kg-1 et sont comparables avec celles pouvant être obtenues avec la chromatographie liquide dans une matrice similaire. En vue d’analyser simultanément une série de tétracyclines, une deuxième méthode d’analyse utilisant la chromatographie liquide couplée à la spectrométrie de masse à haute résolution (HRMS) a été proposée. L’utilisation de la HRMS a été motivée par le fait que cette technique d’analyse est moins sensible aux faux positifs que le triple quadripôle traditionnel. Des limites de détection comprises entre 1,5 et 3,6 µg kg-1 ont été atteintes dans des échantillons de lisier en utilisant un mode d’analyse par fragmentation. L’utilisation de méthodes de quantifications ciblées est une démarche intéressante lorsque la présence de contaminants est suspectée dans un échantillon. Toutefois, les contaminants non intégrés à cette méthode d’analyse ciblée ne peuvent être détectés même à de fortes concentrations. Dans ce contexte, une méthode d’analyse non ciblée a été développée pour la recherche de pharmaceutiques vétérinaires dans des effluents agricoles en utilisant la spectrométrie de masse à haute résolution et une cartouche SPE polymérique polyvalente. Cette méthode a permis l’identification d’antibiotiques et de pharmaceutiques couramment utilisés dans l’élevage porcin. La plupart des méthodes d’analyse disponibles dans la littérature se concentrent sur l’analyse des composés parents, mais pas sur les sous-produits de dégradation. L’approche utilisée dans la deuxième méthode d’analyse a donc été étendue et appliquée à d’autres classes d’antibiotiques pour mesurer les concentrations de plusieurs résidus d’antibiotiques dans les sols et les eaux de drainage d’un champ agricole expérimental. Les sols du champ renfermaient un mélange d’antibiotiques ainsi que leurs produits de dégradation relatifs à des concentrations mesurées jusqu’à 1020 µg kg-1. Une partie de ces composés ont voyagé par l’intermédiaire des eaux de drainage du champ ou des concentrations pouvant atteindre 3200 ng L-1 ont pu être relevées.

Fabrication of Potentiometric Sensors for the Determination of Lanthanide Ions

In many fields such as earth science biology, environment and electronics, the knowledge about elemental distributions and chemical speciation is important. The determination of metal levels especially the toxic ones both in the environment and in biological materials are increasingly demanded by the society.Ion selective sensors have become one of the most effective ad powerful means for analytical scientists for the trace level monitoring of metal ions. The wide range of applications ,low material requirements and simplicity of analytical procedure have not only brought ion-selective electrodes in to the lime light of analytical chemistry,but have promoted their use as tools for physiologists,medical researchers,biologists,geologists,environmental protection specialists etc.Potentiometric ion-selective sensors have been developed for the determination of lanthanide ions such as La3+,Nd3+,Pr3+,Sm3+, and Gd3+.The sensors fabricated include both PVC membrane sensor and chemically modified carbon paste sensor. A set of 10 sensors have been developed. The response parameters of all the sensors have been studied and the sensors were applied as an indicator electrode in the potentiometric titration and for the determination of metal ions in real samples.

Development of Electrochemical Sensors for Various Pharmaceuticals

The development of electrochemical sensors is currently one of the active areas of research in analytical chemistry.Voltammetric sensors as an important class of electrochemical sensors are extensively used in pharmaceutical applications.In voltammetric analysis,many active compounds in dosage forms,in contrast to excipients,can be readily oxidised or reduced at the electrode surface by applying a potential.Chemically modified electrodes have great significance in the electrochemical determination of pharmaceuticals.The modification of electrode results in efficient determination of electroactive species at very lower potential without any major interferences.The present study involves the fabrication of 8 voltammetric sensors for the drugs Metronidazole Benzoate, Sulfamethoxazole, Acyclovir, Pam Chloride , Trimethoprim , Tamsulosin Hydrochloride and Ceftriaxone Sodium.Two sensors were developed for the drug tamsulosin hydrochloride while one sensor each was developed for the other drugs.

Studies On Chelating Ion-Exchange Resins

Ion-exchange chromatography has emerged as a practical and rapid method of separation and analysis. A review of literature on chelating resins reveals that eventhough investigations on highly selective resins are intensively pursued from early 1940s, such resins are still insufficiently used in analytical chemistry and process technology. This is mainly due to the complexity of their synthesis and high cost. In this context, it is worthwhile to develop novel chelating resins which are specific or at least selective towards a group of metal ions. Synthesis, characterization and analytical applications of two such resins are presented in this thesis.

Development of Electrochemical and Fluorescent Sensors

Chemical sensors have growing interest in the determination of food additives, which are creating toxicity and may cause serious health concern, drugs and metal ions. A chemical sensor can be defined as a device that transforms chemical information, ranging from the concentration of a specific sample component to total composition analysis, into an analytically useful signal. The chemical information may be generated from a chemical reaction of the analyte or from a physical property of the system investigated. Two main steps involved in the functioning of a chemical sensor are recognition and transduction. Chemical sensors employ specific transduction techniques to yield analyte information. The most widely used techniques employed in chemical sensors are optical absorption, luminescence, redox potential etc. According to the operating principle of the transducer, chemical sensors may be classified as electrochemical sensors, optical sensors, mass sensitive sensors, heat sensitive sensors etc. Electrochemical sensors are devices that transform the effect of the electrochemical interaction between analyte and electrode into a useful signal. They are very widespread as they use simple instrumentation, very good sensitivity with wide linear concentration ranges, rapid analysis time and simultaneous determination of several analytes. These include voltammetric, potentiometric and amperometric sensors. Fluorescence sensing of chemical and biochemical analytes is an active area of research. Any phenomenon that results in a change of fluorescence intensity, anisotropy or lifetime can be used for sensing. The fluorophores are mixed with the analyte solution and excited at its corresponding wavelength. The change in fluorescence intensity (enhancement or quenching) is directly related to the concentration of the analyte. Fluorescence quenching refers to any process that decreases the fluorescence intensity of a sample. A variety of molecular rearrangements, energy transfer, ground-state complex formation and collisional quenching. Generally, fluorescence quenching can occur by two different mechanisms, dynamic quenching and static quenching. The thesis presents the development of voltammetric and fluorescent sensors for the analysis of pharmaceuticals, food additives metal ions. The developed sensors were successfully applied for the determination of analytes in real samples. Chemical sensors have multidisciplinary applications. The development and application of voltammetric and optical sensors continue to be an exciting and expanding area of research in analytical chemistry. The synthesis of biocompatible fluorophores and their use in clinical analysis, and the development of disposable sensors for clinical analysis is still a challenging task. The ability to make sensitive and selective measurements and the requirement of less expensive equipment make electrochemical and fluorescence based sensors attractive.

Desenvolupament de mètodes de determinació de compostos fenòlics en aigües i sòls. Caracterització dels processos d'adsorció en diferents tipus de sòls.

El desenvolupament de mètodes d'anàlisi de compostos fenòlics és una pràctica habitual en molts laboratoris des de l'establiment de mesures legislatives de control de les concentracions d'aquestes substàncies en el medi ambient. Les tècniques cromatogràfiques representen la primera opció per a la determinació de la major part de compostos orgànics, en els que s'inclouen els fenols. Aquests, per les seves propietats de volatilitat i polaritat, poden analitzar-se emprant tant la cromatografia líquida com la cromatografia de gasos i aquesta dualitat s'ha aplicat en aquest treball.

On the development of horizontal CEN standards supporting the implementation of EU directives on sludge, soil and biowaste - Project HORIZONTAL

We give an overview on the development of "horizontal" European Committee for Standardisation (CEN) standards for characterising soils, sludges and biowaste in the context of environmental legislation in the European Union (EU). We discuss the various steps in the development of a horizontal standard (i.e. assessment of the possibility of such a standard, review of existing normative documents, pre-normative testing and validation) and related problems. We also provide a synopsis of European and international standards covered by the so-called Project HORIZONTAL. (C) 2004 Elsevier Ltd. All rights reserved.