The coupling of liquid chromatography (LC) to infrared (IR) spectrometry is an interesting analytical tool, because high resolution provided by LC is combined with the non-destructive and molecular specific information of IR spectrometry. However, the potential of on-line LC-IR employing a flow cell interface, characterized by its technical simplicity, cannot yet be fully exploited due to the limited sensitivity of IR detection and difficulties in on-line measurements arising from the dominating absorption of most of the commonly used mobile phase components. Accordingly, the objective of this Thesis was to promote the use of the on-line hyphenation of LC and IR spectroscopy through the development of instrumental and chemometric tools to overcome existing limitations, thus increasing the applicability of this technique. Chapter 2 describes innovations in the field of isocratic separation. A method for the determination of lecithin and soybean oil in dietary supplements using on-line Gel Permeation Chromatography – Attenuated Total Reflectance – Infrared (GPC-ATR-IR) was developed including a simple procedure to select the optimum wavenumber used for the extraction of characteristic elution profiles. For the monitoring of polymerized triglycerides in deep-frying oil, an approach employing on-line GPC-IR spectrometry and the Science Based Calibration (SBC) multivariate approach for chromatogram-extraction were reported. An on-line LC-IR procedure for the determination of glycolic acid in cosmetics employing the rapid scan data acquisition mode was proposed. Chapter 3 deals with different methods for background correction in on-line LC-IR using reference spectra matrices (RSM). The determination of the critical eluent composition for polyethylene glycols using methanol as organic modifier was discussed employing the absorbance ratio as identification parameter for background correction. For the determination of fructose, glucose, sucrose and maltose in beverages employing acetonitrile as organic modifier, again the absorbance ratio was used as identification parameter. A Partial Least Squares (PLS) procedure as well as the application of point-to-point matching algorithms for automated background correction were discussed for background correction in acetonitrile:water gradients using different examples of applications. Chapter 4 deals with the compensation of the background contribution employing column-wise techniques. Polynomial regressions modelling the background absorbance at each wavenumber throughout the gradient run were applied for acetonitrile:water mobile phase gradients. The use of cubic smoothing splines could be demonstrated for background correction under reversed phase gradient conditions employing different alcohols as organic modifiers. In Chapter 5, background correction based on factor analysis and reference spectra matrices was discussed. The contribution of the background absorption to overall LC-IR signals could be compensated using two approaches based on Principal Component Analysis (PCA) and simple-to-use interactive self modeling analysis (SIMPLISMA), obtaining good results in acetonitrile:water systems. Subsequently, multivariate curve resolution-alternating least squares (MCR-ALS) was applied improving peak and spectral resolution and eliminating remaining signal variation due to background absorption and detector drift. The chemometric extraction of ‘analyte-specific’ chromatograms in on-line LC-IR was discussed in Chapter 6. Obtained results confirm that the SBC method is particularly well suited for recovering ‘analyte-specific’ signals from on-line LC-IR chromatograms. The last chapter describes instrumental developments in on-line LC-IR. On-line IR detection in gradient capillary LC using micromachined nanoliter-flow cells was discussed. Four model compounds were separated and identified using an acetonitrile:H2O gradient with limits of detection in the concentration range of 35-94 ng μL-1, representing an increase in mass sensitivity by a factor of approximately 30 as compared to standard LC systems. The last chapter also focuses on the development of LC with on-line dual Quantum Cascade Laser (QC-laser) detection. Compared to state-of-the-art FTIR spectrometers, the use of the developed QC-laser based system provided a significant improvement in both, sensitivity and data acquisition frequency. / The coupling of liquid chromatography (LC) to infrared (IR) spectrometry is an interesting analytical tool, because high resolution provided by LC is combined with the non-destructive and molecular specific information of IR spectrometry. However, the potential of on-line LC-IR employing a flow cell interface, characterized by its technical simplicity, cannot yet be fully exploited due to the limited sensitivity of IR detection and difficulties in on-line measurements arising from the dominating absorption of most of the commonly used mobile phase components. Accordingly, the objective of this Thesis was to promote the use of the on-line hyphenation of LC and IR spectroscopy through the development of instrumental and chemometric tools to overcome existing limitations, thus increasing the applicability of this technique. Chapter 2 describes innovations in the field of isocratic separation. A method for the determination of lecithin and soybean oil in dietary supplements using on-line Gel Permeation Chromatography – Attenuated Total Reflectance – Infrared (GPC-ATR-IR) was developed including a simple procedure to select the optimum wavenumber used for the extraction of characteristic elution profiles. For the monitoring of polymerized triglycerides in deep-frying oil, an approach employing on-line GPC-IR spectrometry and the Science Based Calibration (SBC) multivariate approach for chromatogram-extraction were reported. An on-line LC-IR procedure for the determination of glycolic acid in cosmetics employing the rapid scan data acquisition mode was proposed. Chapter 3 deals with different methods for background correction in on-line LC-IR using reference spectra matrices (RSM). The determination of the critical eluent composition for polyethylene glycols using methanol as organic modifier was discussed employing the absorbance ratio as identification parameter for background correction. For the determination of fructose, glucose, sucrose and maltose in beverages employing acetonitrile as organic modifier, again the absorbance ratio was used as identification parameter. A Partial Least Squares (PLS) procedure as well as the application of point-to-point matching algorithms for automated background correction were discussed for background correction in acetonitrile:water gradients using different examples of applications. Chapter 4 deals with the compensation of the background contribution employing column-wise techniques. Polynomial regressions modelling the background absorbance at each wavenumber throughout the gradient run were applied for acetonitrile:water mobile phase J. Kuligowski | NEW INSTRUMENTAL AND CHEMOMETRIC DEVELOPMENTS FOR THE ON-LINE HYPHENATION OF LIQUID CHROMATOGRAPHY AND INFRARED SPECTROSCOPY II gradients. The use of cubic smoothing splines could be demonstrated for background correction under reversed phase gradient conditions employing different alcohols as organic modifiers. In Chapter 5, background correction based on factor analysis and reference spectra matrices was discussed. The contribution of the background absorption to overall LC-IR signals could be compensated using two approaches based on Principal Component Analysis (PCA) and simple-to-use interactive self modeling analysis (SIMPLISMA), obtaining good results in acetonitrile:water systems. Subsequently, multivariate curve resolution-alternating least squares (MCR-ALS) was applied improving peak and spectral resolution and eliminating remaining signal variation due to background absorption and detector drift. The chemometric extraction of ‘analyte-specific’ chromatograms in on-line LC-IR was discussed in Chapter 6. Obtained results confirm that the SBC method is particularly well suited for recovering ‘analyte-specific’ signals from on-line LC-IR chromatograms. The last chapter describes instrumental developments in on-line LC-IR. On-line IR detection in gradient capillary LC using micromachined nanoliter-flow cells was discussed. Four model compounds were separated and identified using an acetonitrile:H2O gradient with limits of detection in the concentration range of 35-94 ng μL-1, representing an increase in mass sensitivity by a factor of approximately 30 as compared to standard LC systems. The last chapter also focuses on the development of LC with on-line dual Quantum Cascade Laser (QC-laser) detection. Compared to state-of-the-art FTIR spectrometers, the use of the developed QC-laser based system provided a significant improvement in both, sensitivity and data acquisition frequency.

A la present tesi s'han desenvolupat i aplicat metodologies per reforçar les bases de la qualitat en els laboratoris d'anàlisi, és a dir, orientades a proporcionar dades fiables i vàlides per a l'ús previst. Aquestes activitats s'han dut a terme considerant els requeriments dels sistemes de qualitat ISO 9001, ISO 17025, BPL i GMP. En el primer bloc, s'han desenvolupat eines útils en la qualificació d'equips: - El test OQ (Qualificació Operacional) permet assegurar des d'un punt de vista modular el bon funcionament d'un cromatògraf de líquids. S'han utilitzat els resultats històrics de confirmació metrològica de l'equip per establir els criteris d'acceptació corresponents. - El test PQ (Qualificació d'Execució de Procés) es basa en l'anàlisi d'una barreja de quatre substàncies. L'avaluació dels paràmetres establerts permet comprovar el correcte funcionament del cromatògraf de líquids des d'un punt de vista global o de "caixa negra" i, fins i tot, identificar quin mòdul de l'equip no està funcionant correctament. En el segon bloc, s'ha estudiat la validació de procediments d'anàlisi i la seva aplicació en el càlcul de la incertesa associada a les mesures. - S'ha optimitzat i revalidat el procediment d'anàlisi de nitrogen Kjeldahl en mostres de taurina. Les condicions de treball s'han modificat, tenint en compte els resultats disponibles de la confirmació metrològica de l'equip. - S'ha desenvolupat una metodologia per al càlcul de la incertesa aprofitant els resultats que s'obtenen durant la validació dels procediments d'anàlisi. Aquesta metodologia s'ha aplicat en la determinació de clorurs en lixiviats per HPLC i en la determinació de la distribució d'àcids grassos en mostres de estearat de magnesi per GC. / En la presente tesis se han desarrollado y aplicado metodologías para reforzar las bases de la calidad en los laboratorios de análisis, es decir, orientadas a proporcionar datos fiables y válidos para el uso previsto. Estas actividades se han llevado a cabo considerando los requerimientos de los sistemas de calidad ISO 9001, ISO17025, BPL y GMP. En el primer bloque, se han desarrollado herramientas útiles en la cualificación de equipos: - El test OQ (Cualificación Operacional) permite asegurar desde un punto de vista modular el buen funcionamiento de un cromatógrafo de líquidos. Se han utilizado los resultados históricos de confirmación metrológica del equipo para establecer los criterios de aceptación correspondientes. - El test PQ (Cualificación de Ejecución de Proceso) se basa en el análisis de una mezcla de cuatro sustancias. La evaluación de los parámetros establecidos permite comprobar el correcto funcionamiento del cromatógrafo de líquidos desde un punto de vista global o de “caja negra” e, incluso, identificar qué módulo del equipo no está funcionando correctamente. En el segundo bloque, se ha estudiado la validación de procedimientos de análisis y su aplicación en el cálculo de la incertidumbre asociada a las medidas. - Se ha optimizado y revalidado el procedimiento de análisis de nitrógeno Kjeldahl en muestras de taurina. Las condiciones de trabajo se han modificado, teniendo en cuenta los resultados disponibles de la confirmación metrológica del equipo. - Se ha desarrollado una metodología para el cálculo de la incertidumbre aprovechando los resultados que se obtienen durante la validación de los procedimientos de análisis. Esta metodología se ha aplicado en la determinación de cloruros en lixiviados por HPLC y en la determinación de la distribución de ácidos grasos en muestras de estearato de magnesio por GC. / In this thesis, there have developed and applied methodologies to strengthen the foundations of quality in laboratories, that is, aimed at providing reliable and valid for the intended use. These activities have been carried out considering the requirements of the following quality systems: ISO 9001, ISO 17025, GLP and GMP. In the first block, there have developed useful tools in the qualification of equipment: - OQ test (Operational Qualification) ensures from a modular point of view the proper functioning of a liquid chromatograph. There have used historical results of metrological confirmation of the equipment to set appropriate acceptance criteria. - PQ test (Qualification Process Execution) is based on the analysis of a mixture of four substances. Evaluation of established parameters allows to check proper operation of the liquid chromatograph from a global or "black box" perspective, and even, identify which equipment module is not working properly. In the second block, there have studied the validation of analytical procedures and their application in the calculation of the uncertainty associated with the measures. - It was optimized and revalidated the procedure for Kjeldahl nitrogen analysis in taurine samples. Working conditions have changed, taking into account the available results of the metrological confirmation of equipment. - It has developed a methodology to calculate the uncertainty using the results obtained during validation of analytical procedures. This methodology has been applied in the determination of chloride in the leaching by HPLC and in the determination of fatty acids in samples of magnesium stearate by GC.

Arsenic (As) is one of the common cancers causing contaminant in groundwater of West Bengal, India along with other regions of the world. Scientists believe that As contamination in groundwater of these region are because of the reductive dissolution of iron oxyhydroxide and the oxidation of organic matter. However, our research shows that a combination of carbonate mineral dissolution and the reduction of iron oxyhydroxides accounts for the high As concentration in groundwater. Thus the people of this region are exposed daily to high levels of As through various pathways. Our study on saliva shows that this biofluid is a good biomarker of As exposure. Moreover, by measuring the various forms of As in saliva, individual susceptibility to arsenic related diseases can be understood. Lastly, we propose nano Zero Valent iron doped onto montmorillonite as an effective material to reduce high levels of As in water quickly and efficiently / L'arsènic (As) és un dels contaminants cancerígens més comuns en les aigües subterrànies de Bengala Occidental, Índia, així com d’altres regions. Els científics creuen que la contaminació en arsènic en l'aigua subterrània d'aquesta regió és deguda a la dissolució reductiva dels oxihidròxids de ferro i a l'oxidació de la matèria orgànica. No obstant, la nostra investigació mostra que una combinació de la dissolució mineral de carbonat i la reducció dels oxihidròxids de ferro en són la causa. Com a conseqüència la població d'aquesta regió estan exposats a nivells alts d'As. El nostre estudi mostra que la saliva és un bon biomarcador d'exposició a l’arsènic. A més, mitjançant la determinació de l’especiació d’As en saliva es pot comprendre la susceptibilitat individual a malalties relacionades amb aquest element. Finalment, proposem la utilització de montmorillonita dopada amb nanopartícules de ferro metàl·lic com un material eficaç per reduir els alts nivells d'As en l'aigua

En esta Memoria se abordan distintas metodologías de microextracción acopladas a Espectrometría de Absorción Atómica con Calentamiento Electrotérmico (ETAAS) para la determinación y especiación de algunos elementos metálicos en bebidas y alimentos. Primeramente se estudia el empleo de líquidos iónicos (ILs). Con el fin de conseguir una máxima eficiencia y la inmediata extracción del analito, se recurre al empleo de una reacción de intercambio iónico entre los iones constituyentes del IL. Para la extracción de especies metálicas se forman primero complejos neutros con ligandos orgánicos. Mediante esta línea de trabajo se desarrolla un procedimiento de especiación no cromatográfica para la determinación de Cr(III) y Cr(VI) en aguas y lixiviados obtenidos de las pinturas que recubren algunos juguetes. Sobre estas mismas matrices se proponen asimismo procedimientos para la determinación de plomo y cadmio con excelentes niveles de sensibilidad. La metodología de empleo de ILs también se ha aplicado a la especiación no cromatográfica de As(III), As(V), ácido monometil arsénico, ácido dimetil arsénico y arsenobetaína. En este caso, los procedimientos desarrollados son aplicados a determinación de estas especies en té. Por otra parte, se estudia el empleo de la microextracción líquido líquido para la determinación de algunas especies inorgánicas, solubles en fase acuosa, que están presentes en aceites comestibles. Se pone a punto un procedimiento de microextracción dispersiva (DLLME) rápido y sencillo que permite alcanzar elevados factores de enriquecimiento y por tanto unos límites de detección extremadamente bajos. De esta forma y, en ocasiones, con el empleo combinado de cartuchos de extracción en fase sólida, se optimiza un procedimiento no cromatográfico para la especiación de las especies de arsénico mencionadas anteriormente en muestras de aceite comestible, sobrenadante de conservas de pescado y perlas dietéticas. Esta metodología también se amplía a la determinación de Se(IV), Se(VI), selenocistina, selenometionina y selenocistamina , así como a otros elementos potencialmente tóxicos como plomo y cadmio en aceites comestibles. Finalmente se estudia la microextracción en punto de nube (CPE) para la determinación y preconcentración de Ag(I) y nanopartículas de plata (AgNPs) en aguas y lixiviados de materiales tratados con AgNPs como agente bactericida. Aprovechando la interacción entre Cr(III) y las AgNPs se optimiza un procedimiento que permite la especiación no cromatográfica de Cr(III) y Cr(VI) utilizando las AgNPs como reactivo y CPE como procedimiento de preconcentración. Por otra parte, el ión Cd(II) forma un complejo neutro con pirrolidín ditiocarbamato amónico (APDC) y puede preconcentrarse, aunque de forma incompleta, utilizando CPE. Sin embargo, en presencia de AgNPs la extracción de Cd(II) es prácticamente total. Esta circunstancia permite aplicar el procedimiento desarrollado a la determinación de este ión en aguas, vino y cerveza. Con el fin de ampliar el campo de aplicación de las AgNPs como fase sólida para la retención de analitos se ha recurrido a su funcionalización superficial con 2-mercaptoetano sulfonato sódico (MESNa). Esta idea ha servido para desarrollar procedimientos de determinación de cobre y níquel, muy sensibles, en aguas, vino y cerveza. La preconcentración se realiza mediante CPE con Triton X-114 y la determinación por ETAAS. Si, a su vez, las AgNPs funcionalizadas recubren una partícula magnética de ferrita, pueden separarse mediante la aplicación de un campo magnético. Con esta metodología se ha estudiado la determinación de diversas formas de mercurio (Hg(II), metilmercurio, dimetilmercurio, etilmercurio, fenilmercurio y difenilmercurio) con nanopartículas magnéticas funcionalizadas con MESNa y cisteína (Cys). El comportamiento diferencial de estas formas químicas de mercurio respecto de Fe3O4@Ag@MESNA y Fe3O4@Ag@Cys permite medir concentraciones muy bajas en muestras de aceite. / In this work, different microextraction methodologies coupled to Electrothermal Atomic Absorption Spectrometry (ETAAS) for the determination and speciation of some metals in food and beverages are addressed. Firstly, the use of ionic liquids (ILs) is studied. To obtain maximum and rapid extraction of the analyte, an ion-exchange reaction between the ions of the IL, which is generated in situ, is proposed. For the extraction of metal species, several organic ligands forming neutral complexes are used. Following this methodology, a procedure for the non chromatographic speciation and determination of Cr(III) and Cr(VI) in water and in the lixiviates obtained from some painted toys is developed. The same approach is used for the development of new, sensitive procedures for the determination of lead and cadmium at ultratrace levels. A chapter is devoted to the non- chromatographic speciation of As(III), As(V) , monomethyl arsenic acid, dimethyl arsenic acid and arsenobetaine following a similar actuation way. The usefulness of the analytical procedures is proven by the determination of these species in tea samples. On the other hand, the use of liquid-liquid microextraction methodology is proven suitable for the separation and preconcentration of some metallic species which are present in edible oils and can be extracted into an aqueous phase. Thus, a quick and simple reverse dispersive microextraction (DLLME) approach that achieves high enrichment factors, and consequently, low detection limits, is developed. In this way, and sometimes using conventional solid phase extraction cartridges, a non-chromatographic procedure for the speciation of the above mentioned arsenic-containing species in edible oils, canned fish supernatant and dietary pearls is optimized. This methodology has also been extended to the determination of Se(IV), Se(VI), selenocistine, selenomethionine and selenocystamine, as well as to the measurement of toxic metals (lead and cadmium) in edible oil samples. Finally, cloud point microextraction (CPE) is studied for the preconcentration and determination of Ag (I) and silver nanoparticles (AgNPs) in water and lixiviates obtained from materials to which AgNPs are incorporated for bactericidal purposes. Taking advantage of the interaction between Cr (III) and AgNPs, a procedure that uses AgNPs as a reagent and CPE for preconcentration and allows the non-chromatographic speciation of Cr(III) and Cr(VI) is optimized. On the other hand, it was found that the neutral complex formed between Cd(II) and ammonium pyrrolidine dithiocarbamate (APDC) is partially extracted by CPE but extraction is practically total when AgNPs are present. This fact is used to develop a sensitive procedure for cadmium determination in water, wine and beer samples. The applications of AgNPs are extended when these nanoparticles are functionalized with 2-mercaptoethane sulfonate (MESNa). This simple treatment allows sensitive analytical procedures to be developed for the determination of copper and nickel in water, wine and beer samples. Preconcentration is carried out using CPE with Triton X -114 and the final measurement, as in the rest of the procedures, is carried out by ETAAS . Provided ferrite magnetic nanoparticles are coated with AgNPs, separation of the phases can be accomplished by applying a magnetic field. To take benefit of it, once the magnetic particles are coated, the resulting nanoparticles are functionalized with MESNa and cysteine. This nanomaterial interacts with several forms of mercury (Hg(II), methylmercury, dimethyl ethyl mercury, phenyl mercury and diphenylmercury). The differential behavior of these chemical forms of mercury in respect of Fe3O4@Ag@MESNa and Fe3O4@Ag@Cys allows extremely low concentrations to be determined in edible oil samples.

Con el fin de solucionar los problemas derivados de la falta de sensibilidad o la alta complejidad de los sensores ópticos integrados basados en medidas de absorbancia, a lo largo de la tesis se diseñó y construyó una plataforma versátil, viable para el desarrollo de dispositivos sensores basados en óptica integrada, para la determinación selectiva de diferentes analitos. Éste se basa en un dispositivo construido mediante guías de onda planas, integradas en una matriz de silicio. Además, para simplificar su diseño instrumental, el acoplamiento del dispositivo a la fuente de luz y al detector se realiza mediante fibras ópticas.El diseño planteado para cumplir los requisitos citados consiste en un circuito microfabricado de guías de onda ARROW y en una membrana químicamente activa, de un determinado grosor, depositada en una zona definida del circuito de guías, que actúa simultáneamente como parte de la estructura plana de guiado y como elemento de reconocimiento. El mecanismo de transducción se basa en el fenómeno de absorción, que es modulado por la membrana selectiva al interaccionar con el analito presente en la disolución.Se formularon diversas membranas poliméricas que incorporaban cromoionóforos NIR sensibles a protón de la familia de las cetocianinas y se formuló y caracterizó una membrana modelo selectiva de ión cadmio compuesta por la combinación de una de las cetocianinas (5ee) evaluadas previamente en un sensor integrado, con un ionóforo comercial (ETH 5435) selectivo de cadmio. Su caracterización espectroscópica (estabilidad química y fotoquímica, posición de bandas, respuesta a pH, pKa, tiempo de respuesta) demostró su excelente comportamiento analítico. Se obtuvieron membranas completamente reversibles, de alta sensibilidad y respuesta rápida y reproducible.Para aprovechar las características de respuesta óptimas de las membranas poliméricas desarrolladas, que incorporaban cetocianinas como cromoionóforos de protón, éstas se incorporaron como elemento de reconocimiento de sensores ópticos integrados. Se diseñó un sistema de análisis por inyección en flujo como metodología simple, automática y reproducible para la caracterización de las membranas desarrolladas, y se integró el sensor como detector. Los resultados obtenidos probaron que una de las ventajas que ofrece el uso de la nueva configuración es el incremento de la sensibilidad sin necesidad de aumentar la concentración de cromoionóforo de la membrana, posibilidad que vendría limitada por su solubilidad, y sin aumentar el grosor de ésta, lo que provocaría un incremento del tiempo de respuesta. Para ambas configuraciones y en idénticas condiciones experimentales, se determinó el tiempo de respuesta de las membranas. Los resultados mostraron como la variación total en unidades de absorbancia conseguido para cada salto de concentración se multiplicaba al utilizar el sensor, mientras que el tiempo de respuesta permanecía equivalente en ambas configuraciones, señal inequívoca de que el grosor de las membranas utilizadas era similar. / The present work pretends to address some of the weak points of the absorbance techniques. Besides increasing the dye concentration in the membrane, which is limited by its solubility in the plasticizer, there are two effective alternatives to improve sensitivity: on the one hand, increasing the optical path length and on the other hand, changing the optically active reagent to another one with higher molar absortivity. With that in mind, we first designed and built a new integrated waveguide absorbance optode (IWAO) for chemical sensing based on radiation transmission through the core of a waveguide. The device consisted of a microfabricated planar waveguide circuit, based on antiresonant reflecting optical waveguide structures (ARROW), and on a chemically active membrane, of a suitable thickness, deposited in a defined region of the former and yielding one part of the light guiding planar structure. Concerning the transduction mechanism, it is established by absorbance/transmittance phenomena of the recognition optode membrane as it interacts with a given concentration of the analyte in the sample.We proceed evaluating the optical and analytical characteristics of a series of novel neutral pH indicators, a class of ketocyanine dyes in PVC membranes. Optical membranes were characterized initially with a conventional absorbance/transmittance flow cell in a continuous-flow system to perform a comparative study of the analytical response. All the parameters determining the membrane response were optimized in order to guarantee the same operational conditions, using the conventional technique as well as the IWAO. The absorbance change achieved with the conventional configuration was multiplied using the sensor almost for every step change, while the response times for both devices were comparable. As a result of the excellent elicited results, the developed IWAO became a very promising device, with large applicability that adapted existing absorbance schemes to the design and construction of novel specific optochemical sensors.Ketocyanine dyes appear to be completely soluble in the organic solvent used as the plasticizer, and no aggregation was observed during any of the experiments. The absorbance maxima of ketocyanine dyes in ethanol were slightly red-shifted (longer wavelength) in this less polar solvent, approaching the working wavelength of the IWAO optical system.Membranes showed good performance during calibrations and basicities were calculated from the equilibrium constant, KaMEM, of each ketocyanine in the membrane. Concerning their stability, photostability was studied in dry and humid conditions under the exposure of different light sources. None of the ketocyanine dyes suffered decomposition in the acid form, but all of them slowly decomposed at their basic form and it was possible to conclude that the tested dyes did not leach to the solution.Finally, analytical response characteristics as sensitivity, response time and reproducibility were checked. In conclusion, all of the prepared and tested membranes can be considered very sensitive, fast, and reversible optical transducers, suitable for pH determinations. The composition of a cadmium-selective membrane was optimized using one of the ketocyanine dyes characterized as a pH indicator in a PVC-polymeric membrane, in combination with a commercial cadmium ionophore. We performed a screen-printing like deposition technique to activate the planar sensor platform with this bulk optode. The sensor integration as a detector in a flow injection system (FIA) was proposed to obtain an automated, simple, and sufficiently reproducible analytical methodology with a high sample throughput.In conclusion, the proposed technologically improved IWAO made evident its appropriateness as a versatile platform for the development of ion-selective optical sensors, depending on the membrane composition, which also permitted to obtain disposable transducers. Actually, investigations are focused on improving ion-selective membranes as well as giving ruggedness and portability to the optical system for the future transference of technology and even though, taking profit of the employed technology to develop optical sensors based on other optical phenomena as fluorescence.

Tese (doutorado)—Universidade de Brasília, Instituto de Ciências Biológicas, Departamento de Ecologia, Programa de Pós-Graduação em Ecologia, 2008. / Submitted by Priscilla Brito Oliveira (priscilla.b.oliveira@gmail.com) on 2009-09-22T20:41:40Z No. of bitstreams: 1 Tese - Jose Salomao O. Silva.pdf: 10639671 bytes, checksum: 6acee5ed2d26fee5876be08687546570 (MD5) / Approved for entry into archive by Guimaraes Jacqueline(jacqueline.guimaraes@bce.unb.br) on 2010-06-01T15:35:01Z (GMT) No. of bitstreams: 1 Tese - Jose Salomao O. Silva.pdf: 10639671 bytes, checksum: 6acee5ed2d26fee5876be08687546570 (MD5) / Made available in DSpace on 2010-06-01T15:35:01Z (GMT). No. of bitstreams: 1 Tese - Jose Salomao O. Silva.pdf: 10639671 bytes, checksum: 6acee5ed2d26fee5876be08687546570 (MD5) Previous issue date: 2008 / O Cerrado é uma das principais formações vegetais do Brasil, sendo o segundo maior bioma nacional. A partir da construção de Brasília, esse importante bioma começou a ser mais intensamente fragmentado devido à substituição da cobertura vegetal original por núcleos urbanos, cultivos agrícolas e pastagens, o que perfaz atualmente cerca de 39% do bioma. Com o objetivo de avaliar os efeitos dessas alterações, foram selecionados córregos em bacias que drenam áreas com cobertura natural, rural e urbana nas adjacências da cidade de Brasília-DF. Durante o período estudado (setembro de 2004 a dezembro de 2006) foram coletadas amostras de água dos córregos. Amostras de deposição atmosférica, soluções de escoamento superficial, do solo a 50 cm de profundidade e freáticas foram coletadas apenas nas áreas naturais e rurais. Foram feitas determinações de pH, alcalinidade, condutividade elétrica, NH4 +, NO2 -, NO3 -, Ca+2, Mg+2, K+, Na+, Cl-, SO4 - e PO4 -. Para os córregos foram feitas medições adicionais de carbono orgânico dissolvido (COD), nitrogênio total dissolvido (NTD), oxigênio dissolvido (OD) e turbidez, enquanto que para deposição atmosférica determinou-se COD e NTD. Os córregos das áreas urbanas apresentaram os maiores valores medianos de pH (6), alcalinidade (111 µM), condutividade elétrica (22 µS/cm), OD (8 mg/L), turbidez (12 NTU), COD (139 µM), NTD (33 µM), NH4 + (5 µM), NO2 - (3 µM), NO3 - (11 µM), Ca+2 (20 µM), Mg+2 (10 µM), K+ (10 µM), Na+ (48 µM), Cl- (26 µM) e SO4 - (2 µM). Os córregos das áreas naturais apresentaram os menores valores, enquanto que os rurais exibiram valores intermediários. As comparações entre os componentes do fluxo das áreas naturais e rurais mostraram que as maiores alterações ocorreram nas concentrações das formas nitrogenadas, que apresentaram aumento das concentrações nas áreas com cobertura rural. Mudanças na cobertura vegetal estão causando uma clara diferenciação na química da água dos córregos, assim como nas componentes do fluxo, em especial o nitrogênio. ____________________________________________________________________________________ ABSTRACT / The Cerrado is the second largest Brazilian biome and location of the headwaters of three important hydrological basins in Brazil. In spite of the biological and ecological relevance of this biome, there is little information about how land use changes affect the chemistry of surface water, groundwater and streams. In order to evaluate the effects of these changes we selected streams that drain natural, rural and urban areas near Brasília (Federal District), Brazil and collected samples of streamwater during two years. In natural and rural areas we also collected samples of atmospheric deposition (AD), runoff (R), subsurface water (SW) and groundwater (GW). Urban streams presented the highest median values of pH (6), alkalinity (111 µM), electrical conductivity (22 mS/cm), DO (8 mg/L), turbidity (12 NTU), dissolved organic carbon (DOC) (139 µM), dissolved total nitrogen (DTN) (33 µM), NH4 + (5 µM), NO2 - (3 µM), NO3 - (11 µM), Ca+2 (20 µM), Mg+2 (10 µM), K+ (10 µM), Na+ (48 µM), Cl- (26 µM), SO4 - (2 µM). Natural streams showed the lowest values, while the rural showed intermediate values. Regarding the comparison of flow components between natural and rural areas, major changes were observed for the nitrogen forms with increasing concentrations in rural areas. The results indicated that differences in land cover are related to changes in streamwater chemistry and to changes in flow components, particularly in the case of nitrogen.

Submitted by Marco Antônio de Ramos Chagas (mchagas@ufv.br) on 2018-04-02T17:14:06Z No. of bitstreams: 1 texto completo.pdf: 1090044 bytes, checksum: 6560b87b6a8c4dee0acf6c600e718a6d (MD5) / Made available in DSpace on 2018-04-02T17:14:06Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1090044 bytes, checksum: 6560b87b6a8c4dee0acf6c600e718a6d (MD5) Previous issue date: 2017-07-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esse trabalho, que está apresentado em dois capítulos, teve como objetivos extrair as hemiceluloses das fibras de milho por processo alcalino (cold caustic extraction = CCE) e funcionalizar as mesmas para produção de carboximetilxilanas de alto valor agregado. No Capítulo 1 foi avaliada a extração alcalina a frio de xilanas de fibras de milho, utilizando-se diferentes concentrações de NaOH a temperatura ambiente por 5 horas. As fibras de milho foram caracterizadas quantitativamente quanto aos seus conteúdos de celulose, hemiceluloses (xilanas), ligninas, extrativos, ácidos urônicos totais, grupos acetilas e cinzas. As xilanas extraídas em álcali foram caracterizadas por FT-IR, viscosidade, teor de xilanas e pureza. Os resultados indicam que foi possível extrair xilanas de fibras de milho com alta pureza e com baixa degradação, embora os rendimentos de extração tenham sido relativamente baixos (4,0- 23,9%). A estrutura mais provável das xilanas de fibra de milho é de um acetato de 4-O-metil-glicuronoarabino-xilana. Elas apresentam grande potencial como fonte para aplicações comerciais de alto valor agregado e de larga escala, dando uma destinação nobre a um resíduo de baixo valor. No Capítulo 2, foi avaliada a utilização das xilanas de fibras de milho para a obtenção de derivados hemicelulósicos através de reações de modificação química. Neste estudo, as xilanas foram derivatizadas pela técnica de carboximetilação por ser a mais versátil para se obter éteres de hemiceluloses solúveis e com funções aniônicas, tendo potenciais aplicações. Foi investigada a carboximetilação de xilanas de fibra de milho com monocloroacetato de sódio em meio alcalino alcoólico de 2- propanol em diferentes proporções. As amostras de carboximetilxilanas obtidas foram caracterizadas quanto ao grau médio de substituição, por FT-IR, DSC e rendimento. Os resultados indicam que foi possível obter carboximetilxilanas a partir de xilanas extraídas de fibra de milho, com altos grau de substituição, rendimento e entalpia de fusão. Conclui-se que é possível se obter derivados hemicelulósicos que excluem a utilização de condições extremas de solventes e temperatura, sendo a fibra de milho uma excelente fonte de matéria-prima. / This work, which is presented in two chapters, aimed to extract the hemicelluloses of the fibers of corn by alkaline process (cold caustic extraction = CCE) and the functionalization of the same for production of carboximetilxilanas of high added value. In chapter 1, the cold alkaline extraction of xylans from corn fibers was evaluated using different concentrations of NaOH at room temperature for 5 hours. The corn fibers were characterized quantitatively as cellulose contents, hemicelluloses (xylans), lignins, extractives, total uronic acids, acetyl groups and ashes. The xylans extracted in alkali were characterized by FT-IR, viscosity, xylan content and purity. The results indicate that it was possible to extract xylans from high purity corn fibers with low degradation, although extraction yields were relatively low (4.0-23.9%). The most likely structure of the corn fiber xylans is a 4-O-methyl-glucuronoarabino-xylan acetate. They have great potential as a source for high value-added and large-scale commercial applications, giving a noble destination to a low value waste. In Chapter 2, the use of corn fiber xylans to obtain hemicellulosic derivatives through chemical modification reactions was evaluated. In this study, xylans were derivatized by the carboxymethylation technique because it is the most versatile to obtain ethers of soluble hemicelluloses and with anionic functions, having potential applications. Carboxymethylation of corn fiber xylans with sodium monochloroacetate in alcoholic alkaline medium of 2-propanol in different proportions was investigated. The carboxymethylxylan samples obtained were characterized for the average degree of substitution, FT-IR, DSC and yield. The results indicate that it was possible to obtain carboxymethylxylans from xylans extracted from corn fiber, with high degree of substitution, yield and enthalpy of fusion. It is concluded that it is possible to obtain hemicellulosic derivatives which exclude the use of extreme conditions of solvents and temperature, the corn fibers being an excellent source feedstock.

Submitted by Marco Antônio de Ramos Chagas (mchagas@ufv.br) on 2018-04-04T18:21:22Z No. of bitstreams: 1 texto completo.pdf: 1304813 bytes, checksum: 16cc030a377821634d38cbe0fc3fcd39 (MD5) / Made available in DSpace on 2018-04-04T18:21:22Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1304813 bytes, checksum: 16cc030a377821634d38cbe0fc3fcd39 (MD5) Previous issue date: 2017-07-06 / A fosfina é um gás inflamável, instável e altamente tóxico que é produzido pela hidrólise de fosfetos metálicos como alumínio, manganês ou zinco. Quando o gás é produzido no laboratório é utilizado a metodologia proposta pela FAO, no entanto na última década tem sido introduzidos os princípios da química verde o que suscita um interesse no uso de metodologias com toxicidade reduzida além de propôs um método analítico prático para a padronização de solução gasosa de fosfina. No presente trabalho foi proposto um sistema para produção de fosfina em escala laboratorial mais simples e controlado comparado com o sistema tradicional. Além disso foram desenvolvidos três métodos analíticos para a sua determinação. O primeiro método desenvolvido foi o iodométrico. As condições experimentais em que o método apresentou melhor resposta foi em um tempo de reação de 35 min. Foram obtidas figuras de mérito mostrando um valor de 0,99 como coeficiente de determinação, limite de detecção (LoD) de 0,062 mL e de quantificação (LoQ) de 0,208 mL, em uma faixa analítica de trabalho no intervalo de 0,208 mL até 1,5 mL de fosfina. O segundo foi um método espectrofotométrico baseado na descoloração do azul de metileno. Foram estabelecidas condições experimentais de azul de metileno (40 μmol L -1 ), na presença de Cu(ll) que atua no meio como catalisador, em pH 9,0, para obter a curva analítica com coeficiente de determinação 0,90, LoD 0,79 mmol L -1 e LoQ 2,62 mmol L -1 , em uma faixa analítica de trabalho no intervalo de 2,62 mmol L -1 até 9,0 mmol L -1 . O terceiro método foi o método de análise de imagem baseado na avaliação do sinal analítico obtido de uma imagem digital e foi otimizado para a quantificação de fosfina, pela obtenção de uma curva analítica com coeficiente de determinação de 0,99, LoD de 0,714 mmol L -1 e LoQ de 2,377 mmol L -1 , em uma faixa analítica de trabalho no intervalo de 2,3 mmol L -1 até 9,0 mmol L -1 . Uma curva analítica foi construída para propor outra alternativa de desenvolvimento de método em trabalhos futuros obtendo um coeficiente de determinação de 0,99, valores de LoD de 5,64 μL e LoQ de 18,77 μL, com uma faixa de trabalho de 5,64 μL até 100 μL. / Phosphine is a flammable, unstable and highly toxic gas that is produced by the hydrolysis of metal phosphides such as aluminum, manganese or zinc. When the gas is produced in the laboratory, the methodology proposed by the FAO is used, however in the last one the principles of green chemistry have been introduced, which provokes an interest in the use of methodologies with reduced toxicity, besides proposing a practical analytical method for the standardization of Gaseous phosphine solution. In the present work, a simpler and more controlled system of phosphine production was proposed in laboratory scale compared to the traditional system. In addition, three analytical methods have been developed for their determination. The first method developed was the iodometric. The experimental conditions in which the method presented the best response was at a reaction time of 35 min. We obtained figures of merit showing a value of 0.99 as determination coefficient, detection limit (LoD) of 0.062 mL and quantification (LoQ) of 0.208 mL, in an analytical range of work in the range of 0.208 mL to 1.5 mL of phosphine. The second was a spectrophotometric method based on methylene blue discoloration. Experimental conditions of methylene blue (40 μmol L -1 ) were established in the presence of Cu (II), which acts in the medium as a catalyst at pH 9.0, to obtain the analytical curve with determination coefficient of 0.90, LoD 0.79 mmol L -1 and LoQ 2.62 mmol L -1 , in an analytical working range in the range of 2.62 mmol L -1 to 9.0 mmol L -1 . The third method was the method of image analysis based on the evaluation of the analytical signal obtained from a digital image and was optimized for the quantification of phosphine by obtaining an analytical curve with determination coefficient of 0.99, LoD of 0.714 mmol L -1 and LoQ of 2.377 mmol L -1 , in an analytical working range in the range of 2.3 mmol L -1 to 9.0 mmol L -1 . An analytical curve was constructed to propose another alternative of method development in future works, obtaining a coefficient of determination of 0.99, LoD values of 5.64 μL and LoQ of 18.77 μL, with a working range of 5.64 μL to 100 μL. / Lattes não encontrado

GUEDES, J. A. C. Validação de método analítico empregando QuEChERS e CG-EM para determinação multirresíduo de agrotóxico em goiaba. 2014. 118 f. Dissertação (Mestrado em Química) - Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2014. / Submitted by Daniel Eduardo Alencar da Silva (dealencar.silva@gmail.com) on 2014-11-12T23:12:57Z No. of bitstreams: 1 2014_dis_jacguedes.pdf: 2908960 bytes, checksum: e337bd1f320e54c5990f6af274a22944 (MD5) / Approved for entry into archive by José Jairo Viana de Sousa(jairo@ufc.br) on 2016-03-18T22:41:50Z (GMT) No. of bitstreams: 1 2014_dis_jacguedes.pdf: 2908960 bytes, checksum: e337bd1f320e54c5990f6af274a22944 (MD5) / Made available in DSpace on 2016-03-18T22:41:50Z (GMT). No. of bitstreams: 1 2014_dis_jacguedes.pdf: 2908960 bytes, checksum: e337bd1f320e54c5990f6af274a22944 (MD5) Previous issue date: 2014 / Guava is one of the most popular and widely accepted in Brazil and worldwide tropical fruits. The fruit can be targeted by various pests, reducing considerably the yield thus causing a slowdown or even a shortage of fruit on the market. Aiming the increase in productivity and ultimately the population's demand high amounts of pesticides are used in order to counter potential pests that may lead to a deterioration of the fruit. Thus, the development of analytical methods for multiresidue determination of pesticides in food is essential for the efficient monitoring of these compounds in the products consumed by the population, enabling regulators to obtain faster and more reliable results. In this work a method for the determination of pesticides in guava was developed and validated, running the sample preparation by modified QuEChERS method, replacing the acetonitrile solvent after cleaning step by cyclohexane / ethyl acetate solvent acetate 1:1 and addition of activated charcoal to extract greater cleanliness. The limits of detection (LOD) ranged between 0.002 and 0.010 mg kg -1 and the limits of quantification (LOQ) ranged from 0.005 to 0.030 mg kg-1 . All calibration curves constructed in solvent and in matrix showed statistical significance when compared to the analytical curves and a strong matrix effect for chlorobenzilate, unlike hexachlorobenzene and ametrina where the matrix effect was negligible. In the analyzes of samples of guava sold in the city of Fortaleza, pesticides were found in 7 samples. Pesticides detected, trifloxystrobin is only allowed for the cultivation of guava, however the concentration of this compound is below the maximum residue limit allowed for guava (MRL = 0.050 mg kg-1 ) according to ANVISA / A goiaba é uma das frutas tropicais mais populares e de grande aceitação no Brasil e no mundo. A fruta goiaba pode ser alvejada por diversas pragas, reduzindo consideravelmente o rendimento da produção ocasionando a escassez da fruta no mercado. Visando o aumento da produtividade e consequentemente atender a demanda da população são empregadas elevadas quantidades de agrotóxicos com o intuito de combater as possíveis pragas que venham acarretar a deterioração da fruta. Dessa maneira, o desenvolvimento de métodos analíticos para a determinação multirresíduos de agrotóxicos em alimentos é fundamental para o monitoramento da qualidade dos produtos consumidos pela população, além de possibilitar aos órgãos reguladores a obtenção de resultados mais rápidos e confiáveis. Neste trabalho, foi adaptado e validado um método para a determinação de agrotóxicos na fruta goiaba, executando-se o preparo da amostra através do método QuEChERS modificado, substituindo-se o solvente acetonitrila após a etapa de limpeza (clean up) por solvente ciclohexano / acetato de etila 1:1 e adição de carvão ativo para maior limpeza do extrato. Os limites de detecção (LD) variaram entre 0,002 e 0,010 mg kg-1 e os limites de quantificação (LQ) variaram entre 0,005 e 0,030 mg kg-1. Todas as curvas analíticas construídas usando o solvente e a matriz apresentaram significância estatística. Quando comparadas às curvas analíticas, verificou-se forte efeito matriz para o clorobenzilato, diferentemente do hexaclorobenzeno e da ametrina onde o efeito de matriz foi pouco significativo. Nas análises de amostras de goiaba comercializada na cidade de Fortaleza, foi detectado a presença de agrotóxicos em 7 amostras. Dos agrotóxicos detectados, apenas a trifloxistrobina é permitida para a cultura da goiaba, entretanto a concentração deste composto é inferior ao limite máximo de resíduo permitido para a goiaba (LMR = 0,050 mg kg-1) segundo a ANVISA.

SOUSA, R. F. R. P. Componentes das aguardentes de cana-de-açúcar de Cabo Verde e do Nordeste Brasileiro: uma análise comparativa. 2011. 83 f. Dissertação (Mestrado em Química) - Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2011. / Submitted by Daniel Eduardo Alencar da Silva (dealencar.silva@gmail.com) on 2014-11-28T18:25:22Z No. of bitstreams: 1 2011_dis_rfrpereira.pdf: 734805 bytes, checksum: 7d0d60e680deac8ea9550018ba555356 (MD5) / Approved for entry into archive by José Jairo Viana de Sousa(jairo@ufc.br) on 2016-01-27T20:43:03Z (GMT) No. of bitstreams: 1 2011_dis_rfrpereira.pdf: 734805 bytes, checksum: 7d0d60e680deac8ea9550018ba555356 (MD5) / Made available in DSpace on 2016-01-27T20:43:03Z (GMT). No. of bitstreams: 1 2011_dis_rfrpereira.pdf: 734805 bytes, checksum: 7d0d60e680deac8ea9550018ba555356 (MD5) Previous issue date: 2011 / The aim of this work was to develop/adapt and validate analytical methods to both identify and quantify constituents of greater concern regarding the quality of homemade and industrial sugar cane spirits produced in some islands from Cape-Vert (CV) and in some states – especially Ceará and Piauí – from Brazil (BRA), so that different products can be compared to one another. After optimization of chromatographic conditions, simultaneous analysis was feasible for six volatile compounds, namely: acetaldehyde and ethyl acetate, as well as n-propyl, isobutyl, nbutyl, and isoamyl alcohols. The inorganic composition of the samples was also investigated. Anions (Cl-, CH3COO-, SO4 2- , CO3 = e HCO3 -) were analysed by Ion Chromatography, while cations (Na+, K+, Cu2+, Ca2+, Mg2+,Mn2+,Pb2+, Zn2+,Cd2+, Se2+ e Fe3+) were analysed by Inductively Coupled Plasma-Optical Emission Spectrometry. The methodologies were validated considering the parameters repeatability, recovery, linearity of analytical curve, limit of detection, and limit of quantitation. For alcohols, aldehyde, and ester analysed, precision was respectively in the ranges 0,2 % - 7,0 %, 0,9% -3,2%, 0,3%-0,7%, while recovery varied in the ranges 97,0% - 103,0%, 99,3 - 104,0%, 98,2% - 102,7%, respectively. The limits of detection (mg/100 mL A.A) were 4.2 for acetaldehyde, 2.8 for ethyl acetate, 9.2 for npropyl alcohol, 7.8 for isobutyl alcohol, 3.1 for n-butyl alcohol, and 44.6 for isoamyl alcohol. The results showed that in only five samples from Cape-Vert (four homemade; one industrial) and in three home-made samples from Brazil, the levels of acetaldehyde were found to be higher than the upper limits allowed by Brazilian legislation; the concentrations of n-butyl alcohol were higher than the allowed limits in two samples from Cape-Vert (one home-made; one industrial) and three home-made samples from Brazil. The levels of higher alcohols were higher than the limit concentrations in three samples from Cape-Vert (one home-made; two industrial) and in two home-made samples from Brazil. However, average concentrations (mg/100 mL A.A) of both acetaldehyde (17,2 BRA; 17,6 C-V) and higher alcohols (247,4 BRA; 240,6 C-V) are in accordance with the requirements of Brazilian legislation (30 mg/100 mL A.A for aldehydes; 360 mg/100 mL A.A for higher alcohols). Ethyl acetate concentration (mg/100 mL A.A) was found to be lower in samples from Brazil (24.8 BRA; 70.0 C-V). The concentrations (mg/100 mL AA) of both cations and anions were found to be: Ni2+ 0,7 (BRA) - 0,6(C-V); Se 1,6(BRA)- 0,62(C-V); Cd2+0,03 (BRA)- 0,04(C-V); Cu2+.5,6 (BRA) - 9,2 (C-V); CH3COO- 055 (BRA) - 1,3 (C-V); SO4 2- 0,07 (BRA) - 4,9 (C-V); HCO3 - 0,04 (BRA) - 9,2(C-V); e Cl- 0,56 (BRA) - 2,0(CV). Average concentrations of inorganic compounds in the samples from Brazil and from Cape-Vert differ from each other, but are in accordance with the literature, except for copper, which is in higher concentrations than allowed in both countries. By PCA analysis, groups were identified in bi-dimensional graphs, in which both artisanal and industrial samples were clearly separated / Este trabalho teve como objetivo desenvolver/adaptar e validar metodologias analíticas para identificação e quantificação dos congêneres mais relevantes para a qualidade das aguardentes de cana de açúcar artesanais e industriais produzidas em algumas Ilhas de Cabo Verde (C-V) e no Brasil (BRA), em especial no estado do Ceará visando uma comparação desses produtos. Após o estudo das melhores condições cromatográficas foi possível uma análise simultânea de seis compostos orgânicos voláteis: acetaldeído, acetato de etila, e os álcoois, n-propílico, isobutílico, n-butílico e isoamílico. Também foram estudados os compostos inorgânicos, cátions (Na+, K+, Cu2+, Ca2+, Mg2+,Mn2+,Pb2+, Zn2+,Cd2+, Se2+ e Fe3+) e ânions (Cl-, CH3COO-, SO42- , CO3= e HCO3- ). Os ânions foram determinados por cromatografia de íons (CI) e cátions por espectrometria de emissão ótica com Plasma indutivamente acoplado (ICP- OES). A validação dos métodos foi estudada em função dos parâmetros, precisão intermediária (repetibilidade), recuperação, linearidade da curva analítica, limite de deteção e de quantificação. A precisão e a recuperação obtidas para os álcoois, aldeído e éster presentes nas aguardentes apresentaram uma variação na faixa de 0,2 % - 7,0 %, 0,9% -3,2%, 0,3%-0,7%; e 97,0% -103,0%, 99,3 - 104,0%, 98,2% - 102,7% respectivamente.Os limites de detecção do equipamento obtidos em mg/100 mL de Álcool Anidro (A.A), foram 4,2, para acetaldeído; 2,8 para o acetato de etila; 9,2 para o álcool n-propílico ; 7,8 para o álcool isobutílico; 3,1 para o álcool n-butílico e 44,6 para o álcool isoamílico. Os resultados quantitativos dos compostos orgânicos mostraram, que de acordo com limites máximos permitidos pela legislação brasileira, dos compostos voláteis estudados, apenas cinco das aguardentes de Cabo Verde (quatro artesanais, uma industrial) e três artesanais das aguardentes do Brasil ultrapassaram o limite permitido pela legislação em teores de acetaldeído;relativamente a n-butanol, 60% e 50% das aguardentes industrial e artesanal de Cabo-Verde e Brasil respectivamente apresentam teores superiores ao limite máximo estipulado (3,0 mg/100 mL A.A). Das dez aguardentes brasileiras, que ultrapassaram o limite, três são industriaise sete artesanais enquanto que das doze aguardentes de Cabo-Verde que ultrapassaram em teores esse limite, seis são artesanais e seis industriais. Dentre álcoois superiores, duas industriais e uma artesanal de Cabo-Verde e duasartesanais do Brasil ultrapassaram o limite máximo referido. Os resultados médios, em mg/100 mL A.A, para os compostos orgânicos presentes nas aguardentes de Cabo Verde e do Brasil, indicam que oacetaldeído e álcoois superiores se encontram dentro dos padrões de qualidade exigidos pela legislação brasileira (30 mg/100 mL A.A para aldeídos; 360 mg/100 mL A.A para álcoois superiores) e tem a mesma magnitude para as aguardentes de ambos países 17,2 (BRA) -17,6 (CV) mg/100 mL A.A em acetaldeído, e 247,4 (BRA) -240,6 (CV) mg/100 mL A.A em álcoois superiores. Em contraste o acetato de etila se encontra em menor concentração nas aguardentes do Brasil estudadas (24,8 mg/100 mL A.A) em relação aos aguardentes de Cabo Verde (70,0mg/100 mL A.A). A comparação dos resultados obtidos, em mg/100 mL A.A, para os cátions e ânions estudados mostrou a seguinte relação: Ni2+ 0,7(BRA) - 0,6(C-V); Se2+ 1,6(BRA) - 0,62(C-V); Cd2+0,03 (BRA) - 0,04(C-V); Cu2+.5,6(BRA)-9,2(C-V); CH3COO- 055 (BRA) -1,3(C-V); SO42- 0,07(BRA) - 4,9(C-V); HCO3-0,04 (BRA) - 9,2(C-V); e Cl- 0,56 (BRA) - 2,0(CV). Os valores médios das concentrações dos compostos inorgânicos nas aguardentes estudadas do Brasil e de Cabo Verde diferem entre si, mas são concordantes com os dados da literatura exceto para o cobre, que ultrapassa o limite permitido em ambos os países. Na análise para reconhecimento de padrões utilizou-se a ferramenta quimiométrica “Análise de Componentes Principais”, PCA, que mostrou uma evidente separação das amostras das aguardentes artesanais e industriais dos dois países estudadas.