Dissertations / Theses on the topic 'ICP-MS'

Knowledge about selenium content of foods containing selenium species is very important in terms of both nutrition and toxicity. Bioavailability of selenium species for human body is different from each other. Hence, speciation of selenium is more important than total selenium determination. In the selenium speciation study, chicken breast samples, selenium supplement tablets and egg samples were analyzed for their selenium contents. In chicken breast study, chickens were randomly categorized into three groups including the control group (25 chickens), inorganic selenium fed group (25 chickens) and organic selenium fed group (25 chickens). After the optimization of all the analytical parameters used throughout the study, selenomethionine, selenocystine, Se(IV) and Se(VI) were determined using Cation Exchange-HPLC-ICP-MS system. In selenium supplement tablet study, anion and cation exchange chromatographies were used to determine selenium species. Arsenic is known as toxic element, and toxicity of inorganic arsenic species, As(III) and As(V), is much higher than organic arsenic species like arsenobetaine and arsenosugars. Hence, speciation of arsenic species in any matrix related with human health is very important. In the arsenic speciation study, Cation Exchange-HPLC-ICP-MS and Cation Exchange-HPLC-ES-MS systems were used to determine arsenobetaine content of DORM-2, DORM-3 and DOLT-4 as CRMs. All of the parameters in extraction, separation and detection steps were optimized. Standard addition method was applied to samples to eliminate or minimize the matrix interference. Thiols play an important role in metabolism and cellular homeostasis. Hence, determination of thiol compounds in biological matrices has been of interest by scientists. In the thiol study, Reverse Phase-HPLC-ICP-MS and Reverse Phase-HPLC-ES-MS systems were used for the separation and detection of thiols. For the thiol determination, thiols containing &ndash
S-S- bond were reduced using dithiothreitol (DTT). Reduction efficiencies for species of interest were found to be around 100%. Reduced and free thiols were derivatized before introduction on the column by p-hydroxymercuribenzoate (PHMB) and then separated from each other by using a C8 column. In the real sample measurement, yeast samples were analyzed using HPLC-ES-MS system.

Fundamental and applied aspects of ICP-MS have been investigated to gain an increased understanding of the technique and improve on its analytical capabilities. Dissociation temperatures of polyatomic ions were calculated using a double-focusing sector instrument, to obtain more reliable mass spectral data with controlled vapour introduction via a Dreschel bottle to allow accurate calculation of the ingredients in the plasma. The equilibrium temperature for the plasma, operated at 1280 W calculated using CO*, and as the thermometric probes, was c.a. 5800 - 7400 K, while using ArO* and ArC* as the thermometric probes the temperature calculated was c.a 2000 - 7000 K. Calculated dissociation temperatures were used to elucidate the site of formation of these ions. Results confirmed that strongly bound ions such as CO* and C2* were formed in the plasma whereas weakly bound ions such as ArO* and ArC* were formed in the interface region due to gross deviation of the calculated temperatures from those expected for a system in thermal equilibrium. The use of helium gas in a hexapole collision cell Attenuated the signals of ArH* Ar* ArO*, Arc*, ArCl* and Ara* allowing improved determination of ^^K*, *'Ca*, ^^e* ^^Cr*, ''As* and ^°Se*in standard solutions. The use of the hexapole collision cell also resulted in an enhancement of analyte signals due to the thermalisation of the ion beam. The ion kinetic energy of ions sampled from the plasma and those sampled from the skimmer cone were determined using a modified lens stack to assess the significance for memory effects of material deposited on the skimmer cone. The most probable kinetic energy of Be* ions sampled from the skimmer cone was found to be 2A eV, which was considerably lower than the most probable kinetic energy of Be* ions sampled from the plasma, which was found to be 9.5 eV. The low kinetic energy of the ions deposited on the skimmer cone means they will only contribute to the analytical signal under certain instrumental operating conditions. The feasibility of liquid sample introduction into a LP-ICP-MS system designed for gaseous sample introduction was investigated using a particle beam separator. The low signal was attributed to the low gas kinetic temperature of the plasma which was confirmed by the fact that the signal increased rapidly with increasing temperature of the transfer line between the particle beam separator and the LP-ICP torch. This was also supported by the fact that more volatile compounds gave mass spectra whereas less volatile compounds did not. A limit of detection of 30 mg 1'^ for chlorobenzene was achieved. Finally, silicon and phosphorus speciation was performed by HPLC coupled to sectorfield ICP-MS. Silicones ranging in molecular weight from 162 g mol'^ - 16500 g mol"^ were extracted from spiked human plasma and separated by size exclusion chromatography. Limits of detection ranged from 12 ng ml"' Si* for the 162 gmol'^ silicone to 30 ng ml'' Si* for the 16500 g mol' silicone. Organophosphate pesticides were extracted from spiked plasma and separated by reversed phase chromatography. Recoveries were between 55 - 81 %. Limits of detection were 0.9 ng ml'' P* 1.8 ng ml'' P* 1.6 ng ml"' P* and 3.0 ng ml'' P* for dichlorvos, methyl parathion, malathion and quinolphos respectively. Phosphates were extracted from various food products and separated by ion-exchange chromatography. Limits of detection were 1.0 ng ml"' P* 2.3 ng ml"' P*, and 39 ng ml"' P* for P04^", PaOy"^ and PsOio^" respectively.

Methods of temperature measurement by mass spectrometry have been critically reviewed. It was concluded that the most appropriate method depended critically on the availability of fundamental data, hence a database of fundamental spectroscopic constants, for diatomic ions which cause interferences in ICP-MS, was compiled. The equilibration temperature, calculated using the different methods and using various diatomic ions as the thermometric probes, was between c.a. 400 - 10,000 K in the central channel, and between c.a. 600 - 16,000 K when the plasma was moved 1.8 mm off-centre. The wide range in temperature reflected the range of temperature measurement methods and uncertainty in the fundamental data. Optical studies using a fibre optic connected to a monochromator were performed in order to investigate the presence of interferences both in the plasma and the interface region of the ICP-MS, and the influence of a shielded torch on these interferences. It was possible to determine the presence of some species in the plasma, such as the strongly bound metal oxides, however, no species other than OH were detected in the interface region of the ICP-MS. The OH rotational temperature within the interface region of the ICP-MS was calculated to be between 2,000 - 4,000 K. The effect of sampling depth, operating power, radial position and solvent loading, with and without the shielded torch, on the dissociation temperature of a variety of polyatomic interferences was investigated. These calculated temperatures were then used to elucidate the site of formation for different polyatomic interferences. Results confirmed that strongly bound ions such as MO+ were formed in the plasma, whereas weakly bound ions such as ArO+ were formed in the interface region due to gross deviation of the calculated temperatures from those expected for a system in thermal equilibrium.

The performance of an inductively coupled plasma mass spectrometer, ICP-MS, depends on the instrument's ability to transport sample ions through the vacuum interface and focus the ions into a well-defined beam that will eventually reach the mass analyzer. In this study two main experiments were performed on the Perkin Elmer NexION 300S, a commercial ICP-MS. First, planar laser-induced fluorescence images were taken of the ion beam in a working instrument downstream from a unique quadrupole ion deflector. The images showed the ability of the instrument design to focus the ions in the ion beam. Second, laser-induced fluorescence was used to characterize ion flow through the vacuum interface. The interface is unique to the NexION ICP-MS in that there are three extraction cones. The effect of a three-cone interface on ideal skimming is discussed.

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Universidade Federal de Minas Gerais
Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) are widely multi-element techniques used to analysis complex samples. Otherwise some aspects, such as spectral interferences and low transport efficiency due to pneumatic nebulization limit their applications. In this work the use of the collision-reaction interface (CRI) of ICP-MS in sequential extraction of the As, Cd, Cr, Cu, Pb, V and Zn in sample of soil treated with vinasse for removal of polyatomic interferences and online hydride generation using a Flow Blurring® multinebulizer for the elimination of matrix interferences and improvement of transport efficiency in determining the As, Sb, Se and Sn by ICP OES have been evaluated. In the evaluation of the CRI, it was found that the flow rates of 60 mL min-1 of H2 and 80 mL min-1 of He introduced into the skimmer cone were the flow rates that showed better efficiency in the correction of interferences and was necessary to perform the inorganic matrix matching (majoritarian elements) of the calibration curve and blanks. The sequential extraction of soil samples treated with vinasse showed that the addition this residue contributes to the increase in the concentration of Cu in exchangeable fraction. The proposed method for hydride generation uses an integrated system, in which the formation of volatile species occurs by interaction of aerosols generated by the different multinebulizer orifices in the ICP-OES spray chamber, without the need of any special system. To this end, two of the three multinebulizer orifices are used to continuously nebulize acid and reducing agent, respectively, while the third one is used to sample introduction. The system was optimized to obtain the highest sensitivity using factorial designs. Interference effects of transition metals were corrected by addition of thiourea. The accuracy of the method was verified by determination of antimony, arsenic, selenium and tin in standard reference materials.
Espectrometria de massa com plasma acoplado indutivamente (ICP-MS) e espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES) são técnicas multielementares muito usadas na análise de amostras complexas, porém aspectos como interferências espectrais e baixa eficiência de transporte devido à nebulização pneumática limitam suas aplicações. Neste trabalho foram avaliadas a utilização da interface de reação e colisão (CRI) de ICP-MS na extração sequencial de As, Cd, Cr, Cu, Pb, V e Zn em amostras de solos tratados com vinhaça para remoção das interferências poliatômicas, e geração de hidretos on line usando um multinebulizador Flow Blurring® para a eliminação de interferências de matriz e melhora da eficiência de transporte na determinação de As, Sb, Se e Sn por ICP OES. Na avaliação da CRI, verificou-se que as vazões de 60 mL min-1 de H2 e 80 mL min-1 de He introduzidos no cone skimmer foram as vazões que apresentaram melhor eficiência na correção de interferentes, e que é necessário realizar a compatibilização inorgânica (elementos majoritários) da curva de calibração e dos brancos. A extração sequencial das amostras de solo tratados com vinhaça mostrou que a adição desse resíduo contribui somente para o aumento no teor de Cu na fração trocável. O método proposto para a geração de hidretos utiliza um sistema integrado no qual a formação das espécies voláteis ocorre pela interação dos aerossóis gerados por diferentes orifícios do multinebulizador na câmara de nebulização de ICP OES, sem a necessidade de sistemas especiais. Para isso, dois dos três orifícios do multinebulizador são usados para a nebulização contínua de ácido e agente redutor, respectivamente, enquanto o terceiro é usado para a introdução da amostra. O sistema foi otimizado para obter a maior sensibilidade utilizando experimentos fatoriais. Efeitos de interferência de metais de transição foram corrigidos pela adição de tiouréia. A precisão do método foi comprovada por determinação de antimônio, arsênio, selênio e estanho em materiais de referência certificados.

Les travaux de thèse portent sur le développement de méthodes pour la caractérisation des nanoparticules (NPs) de dioxyde de titane (TiO2) dans les aliments. L’étude a été séparée distinctement en deux axes. Le développement de la méthode AF4-ICP-MS (I) au sein de la Plateforme Nano-Sécurité du CEA de Grenoble et le développement de la méthode Sp-ICP-MS (II) au sein du Laboratoire de la Sécurité Aliments de l’Anses à Maisons-Alfort.Pour le premier axe, les interactions électrostatiques entre les particules et la membrane de l’AF4 ont été étudiées. La charge de surface (potentiel zêta) a été mesuré pour différentes type de particule et membrane en fonction de plusieurs paramètres du solvant tel que le pH, la force ionique ainsi que la présence de tensio-actifs. Suite aux nombreuses analyses effectuées plusieurs conditions de solvant ont été identifiées comme favorable à la répulsion électrostatique entre les particules et la membrane ce qui permettrai de diminuer les pertes de particules au niveau de la membrane. Plusieurs conditions ont donc été testées directement pour l’analyse de NPs de TiO2 en AF4-ICP-MS. Il a ainsi été montré que les conditions favorisant les répulsions électrostatiques permettaient d’améliorer le taux dé récupération des particules au niveau du système AF4. Cependant les analyses ont aussi montré que les NPs de TiO2 n’étaient pas suffisamment dispersées pour pouvoir obtenir une distribution en taille fiable.Le second volet de la thèse, a eu pour but, dans un premier temps, d’optimiser le traitement de données de la méthode Sp-ICP-MS. Plusieurs améliorations ont été réalisées comme le calcul automatique du seuil bruit de fond-particule, le calcul de l'efficacité de transport où encore l'ajout de paramètres de contrôle qualité. Ce traitement de données a ensuite été comparée à un logiciel dédié aux analyses par Sp-ICP-MS et a permis de mettre en avant que la feuille de calcul interne donne des résultats avec une meilleure justesse, tout en fournissant des paramètres supplémentaires.Dans un second temps une optimisation de la méthode Sp-ICP-MS a été réalisée. Plusieurs paramètres ont donc été évalués comme le choix de l’isotope de titane, le temps d’acquisition, le type de solvant pour disperser les particules, ainsi que le mode de prélèvement de l’échantillon et son débit.Enfin, plusieurs aliments ont été analysés après avoir mis en place un protocole d’extraction des NPs. Les résultats obtenus ont permis de déterminer une distribution en taille des NPs de TiO2 présentes dans les échantillons
The thesis focuses on the development of methods for the titanium dioxide (TiO2) nanoparticles (NPs) characterization in food products. The study was separated distinctly into two axes. The development of the AF4-ICP-MS (I) method within the CEA Nano-Safety Platform in Grenoble and the development of the Sp-ICP-MS (II) method within the Food Safety Laboratory of the Anses in Maisons-Alfort.For the first axis, the electrostatic interactions between the particles and the AF4 membrane were studied. The surface charge (zeta potential) was measured for particles and membranes depending on several solvent parameters such as pH, ionic strength and the presence of surfactants. Following the several analyzes carried out, several solvent conditions have been identified as promoting the electrostatic repulsion between the particles and the membrane, which will make it possible to reduce the losses of particles at the level of the membrane. Several conditions were therefore directly tested for NPs analysis of TiO2 in AF4-ICP-MS. It has thus been shown that the conditions favoring electrostatic repulsions make it possible to improve the efficiency of the particles at the level of the AF4 system. However, the analyzes also showed that the TiO2 NPs were not sufficiently dispersed to obtain a reliable size distribution.The second part of the thesis aimed at first optimizing the data treatment of the Sp-ICP-MS method. Several improvements have been made such as the automatic calculation of the background-particle threshold, the calculation of the transport efficiency or the addition of quality control parameters. This data treatment was then compared to a software dedicated to analyzes by Sp-ICP-MS and made it possible to highlight that the internal spreadsheet gives results with a better accuracy, while providing additional parameters.In a second time an optimization of the Sp-ICP-MS method was carried out. Several parameters were therefore evaluated such as the choice of the titanium isotope, the acquisition time, the type of solvent to disperse the particles, as well as the sample collection mode and its flow rate.Finally, several foods were analyzed after setting up an extraction protocol for NPs. The results obtained made it possible to determine a size distribution of the NPs of TiO2 present in the samples

ABSTRACT ARSENIC SPECIATION IN FISH BY HPLC-ICP-MS Ö
ZCAN, Sefika Eroglu M.S., Department of Chemistry Supervisor: Prof. Dr. O. Yavuz ATAMAN September 2010, 103 pages Arsenic speciation in fish samples on the market was performed using isocratic elution with cation exchange column high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS) detection. Total As concentrations were found by ICP-MS using samples digested by nitric acid-hydrogen peroxide solution using microwave oven digestion
the results were in the range of 1.15-12.6 µ
g/g. Separation of organic arsenicals, namely arsenobetaine (AB), dimethylarsinic acid (DMA) and monomethylarsonic acid (MA), have been achieved in 12 minutes. Freeze-dried samples were extracted by deionized water with a shaker system
the concentrations of AB and DMA in the extract was then determined using HPLC-ICP-MS. The accuracy of the method for determining AB concentration was confirmed using certified reference material (CRM), DOLT 4 (dog fish liver)
for this CRM only preliminary data are available for AB. The arsenic compounds in 6 fish muscle samples were investigated. The predominant arsenic compound found in extracts was AB
the concentrations were in the range of 0.86-12.0 µ
g/g. DMA concentration was 0.40±
0.03 µ
g/g in one of the samples
in the others it was below the limit of quantation (0.21 µ
g/g).

Fingerprinting techniques based on elemental composition and multivariate statistical analysis of compositional data can be used for identification and classification of a specific agricultural product according to their geographical provenance. The analytical approach assumes that the elemental composition of an agricultural product such as for example, wine, coffee, tea, olive oil, and fruit juice will reflect the composition of the soil on which they are cultivated thanks to biogeochemical cycling. The geographically/geologically sensitive parameters like element traces composition are of significant relevance in order to identify the origin of some food products. In recent years, many serious diseases appear related to foodstuffs, so providing the motivation for the scientific community to work more intensively in this area. The aim of this PhD thesis has been to characterize the trace and ultra-trace elements content in cow milk samples and evaluate the chemometric techniques in order to investigate the potentiality of multi-element composition as a marker of geographical origin of milk samples coming from different region of production based on ultra-trace triple quadrupole ICP-MS. In this thesis, a brand new ICP-MS facility for ultra-trace elemental analysis was tested and set into operational conditions, including the optimization of several analytical methods for the determination of trace and ultra-trace elements such as Rare Earth elements in raw cow milk. 50 samples from different geographical origin were analyzed and the results evaluated with chemometric method, for the classification of cow milk samples from different origin. The approach elaborated has been proved to be an effective way to characterize food products from different geographical origin, providing a fingerprint of the element patterns in the samples.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
In this work, the aim of this study is to evaluate sample preparation procedures and liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) and LC coupled to chemical vapor generation (CVG) and ICP-MS (LC-CVG-ICP-MS) for identification and quantification of As species in mollusks collected in BTS. Conditions related to As species extraction were assessed with the use of microwave assisted extraction (MAE) and ultrasound-assisted extraction (UAE). The influence of the main parameters involved in extraction of As species such as the type and concentration of extraction solution, sample mass, temperature and extraction time were evaluated. The extraction was possible by using water at 80 °C (0.2 g sample and 6 mL of w ater) for 6 min using MAE. For the chromatographic separation the type of mobile phase [(NH4)2CO3 and (NH4)2HPO4] concentration (1 to 20 mmol L-1), pH (5.0 to 9.0), flow rate (1.05 to 1.45 mL min-1) and elution mode (isocratic and gradient) were evaluated. The volume of sample injected into the chromatograph was fixed to 200 μL. For the separation of As species an anion exchange column (Hamilton PRP-X100, 250 x 4.1 mm) was used. Six As species were detected in the mollusks being identified arsenobetaine (AsB), As(III), dimethylarsenic acid (DMA) and ρ- arsanilic acid (ρ-ASA). The best separation of the As species was obtained by gradient elution mode and using the following program: 0 to 1.4 min using 6 mmol L-1 (NH4)2HPO4 to 1.4 to 2.7 min using 20 mmol L-1 (NH4)2CO3 and 2.7 to 15 min using 6 mmol L-1 (NH4)2HPO4). The mobile phase flow rate was set at 1.25 mL min-1. CVG parameters were evaluated and the concentrations of NaBH4 and HCl, and carrier gas flow rate were set to 1.0% (m/v) 1.0 mol L-1 and 1.15 L min-1, respectively. The extraction procedures and determination of total As were evaluated using certified reference materials BCR 627 (Tuna Fish Tissue), DORM-2 (Dogfish Muscle) and NIST 1566b (Oyster tissue). The agreement of the results obtained was 95 ± 3 to 101 ± 5%, respectively. The sum of the concentrations of As species determined by LC-ICP-MS and the total As concentration in digested samples and extracts measured, determined by ICP OES were also in good agreement on a confidence level of 95% (Student t-Test). The developed methods by employing the LC-ICP-MS and LC-CVGICP- MS for As speciation analyses in bivalves mollusks are considered suitable.
Neste trabalho foi avaliado o preparo da amostra e o uso da cromatografia a líquido acoplada à espectrometria de massa com plasma indutivamente acoplado (LC-ICP-MS) e LC acoplado ao sistema de geração química de vapor (CVG) e ICP-MS para a identificação e quantificação das espécies de As presentes em tecidos de moluscos bivalves. Condições relacionadas à extração das espécies de As foram avaliadas com o emprego de extração assistida por micro-ondas (MAE) e ultrassom (UAE). A influência dos principais parâmetros envolvidos na extração das espécies de As, como o tipo e concentração da solução extratora, massa de amostra, temperatura e o tempo de extração por MAE e o tempo de sonicação por US foram avaliados. Extração de As foi possível usando água a 80 °C (0,2 g de amostra e 6 mL de água) durante 6 min com MAE. Para a separação cromatográfica foram avaliados o tipo de fase móvel [(NH4)2CO3 e (NH4)2HPO4], a concentração (1 a 20 mmol L-1), o pH (5,0 a 9,0), a vazão (1,05 a 1,45 mL min-1) e o modo de eluição (isocrático e gradiente). O volume de amostra injetada no cromatógrafo foi fixado em 200 μL. Para a separação das espécies de As foi utilizada uma coluna de troca aniônica (Hamilton PRPX100, 250 x 4,1 mm). Foram detectadas seis espécies de As nos moluscos, sendo identificadas somente a arsenobetaína (AsB), o As(III), o dimetilarsênio (DMA) e o ácido ρ- arsanílico (ρ-ASA). A melhor separação das espécies de As foi obtida por eluição gradiente utilizando as seguintes condições: 0 a 1,4 min empregando 6 mmol L-1 de (NH4)2HPO4, 1,4 a 2,7 min empregando 20 mmol L-1 de (NH4)2CO3 e 2,7 a 15 min utilizando 6 mmol L-1 de (NH4)2HPO4. A vazão da fase móvel foi fixada em 1,25 mL min-1. Os parâmetros de CVG avaliados foram a concentração de NaBH4 e HCl e a vazão do gás de arraste, as quais foram fixadas em 1,0 % (m/v), 1,0 mol L-1 e 1,15 L min-1, respectivamente. Os procedimentos de extração e determinação de As total foram avaliados utilizando os materiais de referência certificados BCR 627 (Tuna Fish Tissue), DORM-2 (Dogfish Muscle) e NIST 1566b (Oyster tissue). A concordância entre os resultados obtidos foi de 95 ± 3 a 101 ± 5%, respectivamente. Os valores entre a soma das concentrações das espécies de As obtidos por LC-ICP-MS e As total nos digeridos e extratos obtidos, determinado por ICP OES também foram concordantes em um nível de confiança de 95% (Teste t-Student). Desta forma, o método desenvolvido empregando LC-ICP-MS e LC-CVG-ICP-MS foi considerado adequado para determinação de espécies de As em moluscos bivalves.

Com o aumento das exigências regulatórias e estabelecimento de limites mais restritos para impurezas elementares em fármacos e excipientes usados em formulações farmacêuticas, ocorreu uma busca por técnicas analíticas capazes de quantificar elementos em níveis traço e assegurar a qualidade e a segurança dos medicamentos. A espectrometria de massas com plasma acoplado indutivamente (ICP-MS) é uma técnica multielementar, que apresenta alta sensibilidade e é empregada com eficiência na análise de elementos traço em diferentes matrizes. O ICP-MS, acoplado a um sistema separador como o cromatógrafo líquido de alta eficiência (HPLC), possibilita a especiação de elementos químicos, o que é importante, pois a toxicidade pode estar diretamente ligada à forma química do elemento, como ocorre para o Hg e As. Neste sentido, os objetivos deste trabalho foram desenvolver e validar um método de análise simples, rápido e com alta sensibilidade, para determinação de 15 impurezas elementares: As, Cd, Cr, Cu, Ni, Pb, V, Ir, Pd, Pt, Rh, Ru, Hg, Os e Mo, em diferentes fármacos e excipientes, em níveis que atendam aos novos critérios estabelecidos pelos órgãos regulatórios, avaliar a utilização da cela de reação dinâmica (DRC) para eliminação de interferências espectrais na determinação de As, Cr e V, realizar a especiação de As e Hg, e aplicar esta metodologia para análise de diversas amostras comprovando sua robustez, versatilidade e vantagens para utilização em rotina. Foram avaliadas cinco estratégias de preparo de amostra: digestão em micro-ondas sistema fechado e digestão em micro-ondas - sistema aberto, digestão em banho-maria, diluição direta em meio ácido e extração utilizando ponteira de ultrassom. Através de ensaios de recuperação e materiais de referência certificados, os melhores resultados (84 a 101%) foram obtidos com a digestão das amostras em sistema fechado de micro-ondas e extração por ponteira de ultrassom. Os limites de detecção variaram entre 0,001 ng g-1 (103Rh) e 0,083 ng g-1 (75As). Em seguida, a metodologia analítica foi empregada para determinação dos elementos em estudo em 74 amostras de fármacos e excipientes. O elemento mais frequentemente encontrado foi o Cu, seguido por Cr, Mo, Ni, Pd e V. Já os elementos químicos Ir, Pt, Os e Ru não foram detectados. Cabe destacar que as concentrações de Pd, Rh, As, Cd, Cr, Cu, Ni, V e Mo encontraram-se acima do limite preconizado pela farmacopeia americana em algumas amostras. A análise por especiação química de As mostrou que as amostras possuíam apenas as formas inorgânicas e mais tóxicas. Em relação ao Hg, apenas uma amostra apresentou níveis detectáveis deste elemento, mas a concentração estava abaixo do limite estabelecido pela farmacopeia americana.
Due to quality and safety reasons, regulatory requirements and establishment of more restricted limits for elemental impurities in drugs and excipients are increasing. These regulations promoted a search for simple and robust analytical techniques for quantification of trace elements. Inductively coupled plasma mass spectrometry (ICP-MS) is an attractive technique for this purpose, presenting multielement and high sensitivity capabilities. ICP-MS can be hyphenated to separation techniques such as high-performance liquid chromatography (HPLC), enabling chemical speciation analysis. Speciation analysis may reveal the chemical form of the element that may be more directly related to the toxicity. In this sense, the objectives of this work were to develop and validate a simple, fast and highly sensitive method for the determination of 15 elemental impurities: As, Cd, Cr, Cu, Ni, Pb, V, Ir, Pd, Rh, Ru, Hg, Os and Mo, in different drugs and excipients, at levels that meet the new criteria established by the regulatory agencies. We also evaluated the use of the dynamic reaction cell (DRC) to eliminate spectral interferences for As, Cr And V. Finally, for As and Hg, speciation methods were applied. All analysis were performed focusing on robustness, versatility and sample high-throughput. We tested five sample preparation strategies: closed microwave system digestion, microwave digestion - open system, water bath digestion, direct acid dilution and ultrasound probe extraction. Recovery studies in ordinary samples and reference certified materials were observed with the closed microwave digestion system and ultrasound probe extraction (84 and 101%). Detection limits ranged from 0.001 ng g-1 for 103Rh to 0.083 ng g-1 for 75As. The analytical methodology was then applied for the determination of the elements in study in 74 samples of drugs and excipients. The most frequently found element was Cu, followed by Cr, Mo, Ni, Pd and V. The chemical elements Ir, Pt, Os and Ru were not detected. It should be mention that the concentrations of Pd, Rh, As, Cd, Cr, Cu, Ni, V and Mo were above the limit recommended by the American pharmacopeia in some samples. Only inorganic arsenic (most toxic forms) was found in samples by applying speciation analysis. Regarding Hg, only one sample had detectable levels of this element, but the concentration was below the limit established by the American pharmacopeia

O Mercúrio (Hg) é um dos mais tóxicos poluentes do meio ambiente. Ele existe basicamente em três formas: Mercúrio elementar (Hg0), ou Hg metálico, mercúrio inorgânico (Hg-i), principalmente o cloreto mercúrico e o mercúrio orgânico (Hg-o), representado principalmente pelo metilmercúrio (MeHg) e etilmercúrio (EtHg), sendo que as formas orgânicas do Hg são mais tóxicas. Sendo assim, é de suma importância que se tenha métodos de fracionamento (Hg t, Hg-i e Hg-o pela diferença) e de especiação de mercúrio (Hg-i, MeHg, EtHg) para diferenciação das espécies de mercúrio em matrizes biológicas. Neste sentido, o presente trabalho teve como objetivos o desenvolvimento de três métodos analíticos rápidos, simples e sensíveis para: i) fracionamento entre Hg-t e Hg-i em sangue/plasma (Hg-o pela diferença) utilizando sistema de geração de vapor frio em linha com ICP-MS (CV ICP-MS); ii) especiação de Hg em amostras de sangue e plasma utilizando o acoplamento HPLC-ICP-MS; iii) especiação de Hg em amostras de sangue utilizando o acoplamento GC-ICP-MS. No método de fracionamento de mercúrio foi feito o preparo de amostras utilizando hidróxido de tetrametilamônio (TMAH) à temperatura ambiente. No método de especiação por HPLC-ICP-MS foi feita a extração das espécies utilizando banho ultrassônico, ao passo que no método GC-ICP-MS foi feita a extração das espécies assistida por microondas. O método CV ICP-MS foi comparado com a geração de vapor utilizando absorção atômica (CV AAS) não tendo diferença estatística entre os dois métodos. Para validação dos métodos foi utilizado Material de Referência Certificado (NIST 966) e outros Materiais de Referência. Os métodos foram aplicados para análise de amostras de sangue de populações Ribeirinhas da Amazônia brasileira expostas ao mercúrio. Os métodos demonstraram ser simples e rápidos, podendo facilmente serem implantados em rotina de laboratórios clínicos.
Mercury (Hg) is one of the most toxic environmental pollutants. It exists primarily in three forms: elemental mercury (Hg0), or metallic mercury, inorganic mercury (Hg-i), particularly mercuric chloride and organic mercury (Hg-o), mainly represented by methylmercury (MeHg) and ethylmercury (EtHg), and the organic forms of mercury are more toxic than the inorganic ones. Then, it is very important the development of simple and fast methods for mercury fractionation (T-Hg, Hg-i and Hg-o by the difference) or speciation (Hg-i, MeHg, EtHg) in biological samples. Then, the aims of this work were to evaluate three analytical methods for: i) mercury fractionation in blood/plasma samples (Hg-t, Hg-i and Hg-o by difference) by using a ICP-MS on line coupled to a cold-vapor generation system (CV ICP-MS), ii) Hg speciation in blood and plasma by using LC coupled to ICP-MS; iii) Hg speciation in blood samples with the use of GC coupled to ICP-MS. For the fractionation method, samples were previously incubated with tetramethylammonium hydroxide (TMAH) at room temperature. On the other hand, for the speciation of Hg in blood/plasma by using HPLC-ICP-MS the extraction of Hg species was carried out with the use of ultrasonic energy. For the speciation methodology with GC-ICP-MS the extraction of Hg species was carried out with the use of microwave-assisted extraction. Validation of the proposed methods were evaluated based on the analysis of the SRM NIST 966 and ordinary blood samples collected from riparians living in the Brazilian Amazon exposed to mercury. In general the proposed methodologies proved to be simple, fast and easily applied in routine analysis by clinical laboratories.

Les éléments traces et en particulier les métalloïdes tels que l'arsenic, le sélénium, l'antimoine et le tellure peuvent se présenter dans l'environnement sous différentes formes chimiques, qui conditionnent leur toxicité, leur biodisponibilité et leur capacité à migrer. Ce travail présente le développement de deux techniques analytiques de spéciation multiélémentaire, associant une technique séparative (chromatographie liquide, électrophorèse capillaire) et un détecteur spécifique et très sensible, l'ICP-MS. La chromatographie d'échange d'anions couplée à l'ICP-MS a permis la séparation simultanée de onze espèces organiques et inorganiques de l'arsenic (As III, As V, MMa, DMa), du sélénium (Se IV, Se VI, SeCyst, SeMet), de l'antimoine (Sb V) et du tellure (Te IV et Te VI). Les limites de détection, comprises entre 0,02 et 3 g/l, ont permis l'analyse d'extraits de sols et de tissus biologiques (poisson, levures). Plusieurs protocoles ont été testés pour l'extraction du sélénium contenu dans une levure. Différentes classes de composés séléniés (protéines, acides aminés, composés inorganiques) ont été mises en évidence par chromatographie d'exclusion stérique. L'adénosyl-séléhomocystéine a été identifiée par spectrométrie de masse electrospray. Un couplage entre l'électrophorèse capillaire (EC) et l'ICP-MS a été développé. Trois nébuliseurs ont été testés pour l'interface : le Babington, le MCN-100 et le Micromist. Ce dernier a permis des séparations reproductibles et une amélioration de la sensibilité par rapport à l'UV. Les limites de détection sont comprises entre 6 et 58 g/l pour les espèces étudiées de As, Se, Sb et Te. L'analyse d'extraits de sols a montré les possibilités de cette technique pour l'analyse d'échantillons réels.

CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
Neste trabalho, são propostas duas metodologias para análise elementar em óleo lubrificante, óleo combustível e biodiesel, através das técnicas de espectrometria de emissão óptica com plasma indutivamente acoplado e espectrometria de massa com plasma indutivamente acoplado com célula de reação dinâmica. Foram combinadas a facilidade e a rapidez na preparação de amostras através da diluição direta em solventes orgânicos, sem tratamento prévio, com a capacidade multielementar das técnicas espectrométricas em estudo. Em ICP OES, foram avaliados os resultados analáticos para os micronebulizadores PFA-100 e Miramist através da análise de dois materiais de referência certificados, a saber, NIST 1634c (óleo combustível) e NIST 1085b (óleo lubrificante). Um planejamento experimental de alta resolução foi realizado para otimização das vazões de Ar e O2 no fluxo de nebulização, com experimentos em duplicata e triplicata no ponto central. Aumentos na razão sinal-ruído foram observados para Ag, Al, B, Ba, Ca, Cr, Cu, Fe, Mn, Si, Ti e V e as maiores razões foram observadas para o micronebulizador PFA-100. As vazões de Ar e O2 foram escolhidas de forma a maximizar essas razões. Para o Miramist, 0,50 L min(-1) (Ar) e 0,020 L min(-1) (O2) foram usados, enquanto para o PFA-100, 0,45 L min(-1) (Ar) e 0,025 L min(-1) (O2). Os materiais de referência NIST 1634c e NIST 1085b foram empregados para validação do método e as melhores recuperações foram obtidas para o micronebulizador PFA-100, com resultados entre 93% e 110%. Os limites de detecção para os dois micronebulizadores não variaram significativamente entre si, estando entre 0,48 ng g(-1) (Mn) e 15,8 ng g(-1) (Al). Em DRC-ICP-MS, foi realizado um planejamento composto central para otimização das condições operacionais do plasma. As vazõoes de argônio de nebulização e auxiliar apresentaram uma influência relevante sobre o teor de Ba++, LaO+ e sobre a intensidade do elemento índio. Uma condição de compromisso foi empregada, sendo 0,42 L min(-1) (Ar de nebulização) e 1,2 L min(-1) (Ar auxiliar). Para redução das interferências espectrais, o metano foi adotado como gás de reação. Os parâmetros operacionais, como a vazão do gás de reação e o parâmetro de rejeição q (Rpq), foram otimizados, visando a menor incidência de interferências sobre isótopos como 52Cr e 56Fe. Os materiais de referência NIST 1634c e NIST 1085b foram empregados para validação do método e as recuperações estiveram entre 90% e 110% para a maioria dos elementos, enquanto os limites de detecção estiveram entre 0,02 ng g(-1) (52Cr) e 7,4 ng g(-1) (40Ca). Os resultados obtidos para o material de referência NIST 1085b foram comparados entre os dois métodos propostos e os mesmos foram considerados concordantes, não diferindo entre eles em mais de 10% para a maioria dos elementos. Os resultados obtidos na análise elementar das amostras de óleo lubrificante mostram que realmente é possível avaliar o desgaste de equipamentos através da metodologia proposta, pois o aumento significativo de alguns elementos, como Fe, foi detectado nas amostras de lubrificante usado, enquanto a análise de amostras de biodiesel mostrou através da técnica de espectrometria de massa, que há nesse biocombustível a presença de elementos que não são contemplados na legislação brasileira.
Two methodologies for elemental analysis of lubrificant oil, fuel oil and biodiesel are proposed, employing inductively coupled plasma optical emission spectrometry and inductively coupled plasma mass spectrometry with dynamic reaction cell. The methodologies combine the facility and fastness of sample preparation through direct dilution in organic solvents, without any pretreatment, with the multielemental capability of these spectrometric techniques. In ICP OES, the analytical results for the micronebulizers PFA-100 and Miramist were evaluated using two certified reference materials, NIST 1634c (residual fuel oil) and NIST 1085b (wear metals in lubrificant oil). Ar and O2 flow rates were optimized employing a high resolution experimental design was realized, with replicate experiments and triplicate at the central point. Improvement in the signal-to-noise ratio were observed for Ag, Al, B, Ba, Ca, Cr, Cu, Fe, Mn, Si, Ti and V and the highest ratios were obtained with the PFA-100 micronebulizer. The Ar and O2 flow rates were optimized in order to improve these ratios. For Miramist, 0.50 L min(-1) (Ar) e 0.020 L min(-1) (O2) were used and, for PFA-100, 0.45 L min(-1) (Ar) e 0.025 L min(-1) (O2). The reference materials (NIST 1634c and NIST 1085b) were analyzed for validation of the method and the highest recoveries were obtained for the PFA-100 micronebulizer, with results between 93% and 110%. The limits of detection for both micronebulizers were very similar, between a range of 0.48 kg(-1) (Mn) and 15.8 ug kg-1 (Al). In DRC-ICP- MS, a central composite design was realized for the optimization of the plasma operational conditions. The nebulizer and auxiliary flow rates showed a relevant influence on Ba++ and LaO+ content and In intensity. A compromising condition was employed, being 0.42 L min(-1)(Ar nebulizer flow rate), 0.1 L min(-1) (O2 flow rate) and 1.2 L min(-1) (auxiliary flow rate). In order to minimize spectral interference, methane was adopted in this work as reaction gas. The operational conditions of the reaction gas flow rate and rejection parameter q (Rpq), were optimized to minimize the interferences on isotopes, such as 52Cr and 56Fe. Two reference materials (NIST 1634c and NIST 1085b) were employed for method validation and the recoveries were between 90% and 110% for most elements, being the limits of detection between 0.02 ng g(-1) (52Cr) and 7.4 ng g(-1) (40Ca). The results obtained for the reference material NIST 1085b by the two proposed methods were in agreement at a 95% confidence level and did not show difference higher than 10% for most elements. The results obtained by elemental analysis of lubricant oils using the ICP OES methodology showed that it is possible to evaluate equipment wear through the analysis of its oil by the proposed methodology, since a significant increase of some elements concentrations, such as Fe, was detected in used lubricant oil samples. The analysis of biodiesel samples by ICP-MS indicated the presence of elements that are not controlled by the Brazilian legislation.

This thesis is concerned with the application offlow injection techniques for on-line sample preparation for inductively coupled plasma mass spectrometry (ICP-MS). A comprehensive introduction to ICP-MS and the various sample introduction methods which have been applied for the technique is presented in Chapter 1. The advantages and disdvantages of the different sample introduction procedures are also considered and discussed. Since ICP-MS is a highly sensitive technique for multi-element analysis at trace levels, there are few methods which can compete with it. The methods which are available are compared with ICP-MS and the advantages and disadvantages of each are discussed in the context of the available literature. The second chapter contains a detailed review of the various reagents which have been used for the selective retention of trace element ions from solutions containing high concentrations of so called 'matrix species' (e.g. Na, Ca, K and Mg). The use of ion-exchange and chelating reagents for trace analyte retention is discussed together with an appraisal of the properties and applications of activated alumina as either a cation or anion exchanger. Most ion-exchange and chelating reagents consist of an organic functional group covalently immobilised onto a support material. The properties of polymer and controlled pore glass support materials are discussed with respect to their behaviour in on-line systems. In Chapter 3, the use of the chelating reagent 8-hydroxyquinoline, covalently immobilised onto controlled pore glass, for on-line preconcentration and matrix separation with ICP-MS detection, is described. A manually operated manifold, directly coupled to the ICP-MS, was developed for this work. The optimisation and analytical performance ofthis manifold is evaluated for Ti4+, V (as VO2+), Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Ag+, Cd2+, Ce3+ and Pb2+ in saline matrix samples and reference materials. Following the development of the manual manifold described in Chapter 3, the construction of an automated preconcentration I matrix separation manifold, using a commercially available liquid handling system is described in Chapter 4. For this work, a novel iminodiacetate chelating reagent, immobilised onto a controlled pore glass support, was used for analyte retention. An initial manifold design is considered, followed by a refined version of the system, which is optimised for the retention of Mn2+, V (as VO2+), Co2+, Ni2+, Cu2+,Zn2+, Ag +, Cd2+, Ce3+, Pb2+ and U (as UO2+). The performance of the novel iminodiacetate chelating material is evaluated for the analysis of two saline reference waters and some saline industrial effluent samples. In Chapter 5, the effects of humic material in the sample on the on-line retention of Ti4+, V (as VO2+ ), Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Ag+, Cd2+, Ce3+, Pb2+ and U (as UO2+) by the iminodiacetate reagent is explored. Humic material, which arises from soil and decaying vegetable matter, exists in fresh and saline waters at concentrations of typically 1 - 50 ppm. This complex material is composed of a number of different organic molecules which contain a variety of functional groups capable of forming chelates with the analytes of interest in the sample. For this reason, interference effects are expected to occur with increasing levels of humic material in the sample. The effect of increasing levels of elements which have an affinity for the iminodiacetate reagent is examined in terms of the retention efficiency of the analytes of interest. In Chapter 6, the subject of microwave digestion for sample preparation is studied. This work initially involves assessing the efficiency of a simple nitric acid digestion for the digestion of selected reference materials in a batch system. The study continues with an evaluation of on-line microwave digestion with off-line analysis using ICP-MS and concludes with an investigation into the feasibility of directly coupling the on-line microwave digestion system to the ICP-MS instrument. Finally, in Chapter 7, the general conclusions to the thesis and suggestions for future research are presented.

Conselho Nacional de Desenvolvimento Científico e Tecnológico
The development of a method for As speciation in aqueous by-product of pyrolysis process of foliate bituminous is described in the present work. Arsenic species are separated by liquid chromatography (LC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). An anion exchange column was used to separated the As species. The analyzed liquid samples were centrifuged at 10000 rpm for 10 min, the supernatant filtered through a 0.45 mm pore size filter and then kept at 4 ºC until analysis. Before being inject in the chromatograph, the supernatant was filtered once more through a 0.2 mm pore size filter coupled to the syringe. In order to avoid memory effects, the supernatant was ten-fold diluted before filtration in the syringe. The separation column was of anion exchange type Dionex IonPac® AS14 (250mm x 4mm i.d., 9 mm particle size). A Dionex IonPac® AG14 (50mm x 4mm i.d., 9 mm particle size) was used as guard column. Ammonium carbonate ((NH4)2CO3) solution was used as mobile phase, according to the following program: 10 min, 0.0015 mol l-1 (NH4)2CO3; 10 min, 0.012 mol l-1 (NH4)2CO3 and 10 min, 0.02 mol l-1 (NH4)2CO3. Calibration curves of arsenobetaine (AsB), arsenite (As(III)), dimethylarsinic acid (DMA), p-arsanilic acid (p-ASA) and arsenate (As(V)) were obtained from serial dilution of standards and subsequent mixing. The retention time increased from AsB, As(III), DMA, p-ASA to As(V). Although 13 As species were separated and detected, quantification of only 3 species (As(III), DMA and As(V)) was possible. The concentrations found were 4.5, 6.9 and 808 mg l-1 of As(III), DMA and As(V), respectively. The method was validated by recovery tests, being the recoveries within 93 and 107%. The limits of detection (LODs) of AsB, As(III), DMA, p-ASA and As(V) were, 5, 4, 19, 11, 57 ng l-1, respectively, while the relative standard deviation (RSD) was typically bellow 6%.
Neste trabalho foi proposto o desenvolvimento de um método para a análise de especiação de As solúvel em subproduto aquoso do processo de pirólise do folhelho betuminoso, envolvendo a separação e determinação das espécies de As por cromatografia a líquido acoplada à espectrometria de massa com plasma indutivamente acoplado (LC-ICPMS). A separação das espécies de As foi feita em uma coluna de troca aniônica. A amostra foi centrifugada a 10000 rpm por 10 min para separação do material particulado. O sobrenadante foi filtrado a 0,45 mm e armazenado sob refrigeração a 4 ºC até a análise. No momento da injeção no cromatógrafo, a amostra foi filtrada a 0,2 mm por um filtro acoplado na seringa. Foi verificado que a melhor condição de análise é quando a amostra é diluída 10 vezes (com a amostra concentrada foi verificado efeito de memória no sistema). Para a separação das espécies de As foi utilizada uma coluna de troca aniônica Dionex IonPacÒ AS14 (250 mm x 4 mm d.i., 9 mm de tamanho de partícula) e uma colunaguarda Dionex IonPacÒ AG14 (50 mm x 4 mm d.i., 9 mm de tamanho de partícula). Para a separação adequada das espécies de arsênio foi utilizado carbonato de amônio [(NH4)2CO3] como fase móvel, com o seguinte programa de eluição no modo isocrático: 10 min a 0,0015 mol l-1 de (NH4)2CO3; 10 min a 0,012 mol l-1 de (NH4)2CO3; 10 min a 0,02 mol l-1 de (NH4)2CO3. Para a obtenção das curvas de calibração, foram empregadas soluções mistas contendo as espécies arsenobetaína (AsB), arsenito (As(III)), ácido dimetilarsônico (DMA), ácido p-arsanílico (p-ASA) e arsenato (As(V)), as quais são eluídas nesta ordem. Utilizando essas condições, foi possível separar 13 espécies de arsênio na amostra, porém, apenas 3 espécies (As(III), DMA e As(V)) foram quantificadas. A concentração de As(III), DMA e As(V) determinada em uma amostra do efluente investigado foi de 4,5; 6,9 e 808 mg l-1, respectivamente. Tendo-se em vista que não havia material de referência certificado (CRM) disponível, o método foi validado através da recuperação dos analitos adicionados na amostra, sendo que as recuperações ficaram entre 93 e 107%. A precisão do método também é boa, sendo o desvio padrão relativo (RSD) geralmente inferior a 6%. Os limites de detecção (LD) do método para AsB, As(III), DMA, p-ASA e As(V) foram de 5, 4, 19, 11 e 57 ng l-1, respectivamente. Portanto, o método proposto é adequado para a análise de especiação de As, para as espécies investigadas, em subproduto aquoso do processo de pirólise do folhelho betuminoso, apresentando boa exatidão e robustez, apesar da complexidade da matriz da amostra.

Inductively coupled plasma - mass spectrometry is widely accepted as the leading technique for trace element analysis. It suffers however, from a range of interferences both spectral and non - spectral which limit the range of analytes and substrates which may be successfully analyzed. This study has investigated the use of mixed gas plasmas as a means of reducing or removing these interference effects. In addition the use of mixed gas plasmas for sensitivity enhancement has been assessed using both wet and dry sample introduction systems. Simplex optimization procedures have been used throughout. The addition of nitrogen to all three argon gas flows of the ICP was evaluated, and the instrumental operating conditions were optimized to allow for the maximum removal of the ArCl+ interference on As and Se. The addition of nitrogen to the nebulizer gas was particularly effective in the removal of the ArCl+. The use of nitrogen addition also facilitated the determination of arsenic in samples where it was previously found to be impossible. The addition of methane was also applied to all three gas flows of the ICP, however, in this case only the addition to the nebulizer gas was successful in removing interferences. These included ArO+, ClO+ and CeO+ in addition to ArCl+ . Detection limits, recoveries and CRM analysis were all improved by the use of methane addition when compared to nitrogen addition or standard argon plasmas. Hydrogen addition was applied solely to the nebulizer gas and found to significantly increase the magnitude of the interferences from argon based polyatomic ions, whilst reducing those from metal oxides. The addition of hydrogen was useful in reducing MO+ interferences, but the removal of other interferences proved unsuccessful. The addition of ethene to the nebulizer gas has been used to remove many of the polyatomic interferences encountered in ICP-MS, including those based on Na, S and P. Ethene addition was as effective as, and usually better than, the addition of both methane and nitrogen. Detection limits, recoveries, calibrations and CRM analysis were all improved by its use. The use of ethene addition has lead to improvement in the determination of As, Cu, Fe, Gd, Ni, Se, and V in the presence of the relevant interference precursors. Most importantly it has been shown that a whole range of interferences can be reduced simultaneously with the addition of ethene. The plasma operating parameters and ion optics settings of a commercial ICP-MS instrument were optimized to yield maximum SBRs for elements across the mass range. It was shown that simple manual tuning of the instrument did not effect the SBRs, when compared to the simplex optimized conditions. Finally it was shown that the addition of molecular gases to the ICP, did not result in any significant improvements in sensitivity, when compared to the all argon system. Finally it has been shown that the addition of a relatively small amount of hydrogen to the nebulizer gas can lead to an enhancement in the signal obtained using laser ablation sampling. This enhancement was greatest for low mass elements and had no effect on the heavy mass element signal.

Tiivistelmä. ICP-MS eli induktiivisesti kytketty plasma massaspektrometria on erityisesti epäorgaanisessa analytiikassa käytetty mittalaite, jonka avulla voidaan määrittää näytteiden isotooppipitoisuuksia. Alkuaineiden, ja niiden eri isotooppien avulla, on mahdollista saada hyvä kokonaiskuva näytteen alkuainekoostumuksesta. ICP-MS-tekniikka mahdollistaa pienten pitoisuuksien havaitsemisen, joten tekniikka soveltuu erinomaisesti esimerkiksi raskasmetallipitoisuuksien määrittämiseen ympäristönäytteistä. Tekniikan käyttöä puoltaa myös sen nopeus ja laajalle levinnyt käyttäjäkunta, jolloin mittaustulosten vertaaminen eri tutkimusten välillä on mahdollista. ICP-MS perustuu plasman korkean lämpötilan kykyyn hajottaa sinne saapuvat molekyylit atomeiksi ja edelleen ionisoida atomit ioneiksi, jotka voidaan tämän jälkeen havaita massaspektrometrin avulla. Isotooppisuhteiden määritystä ICP-MS-tekniikalla hankaloittaa spektraaliset häiriöt, joita voidaan minimoida näytematriisin käsittelyllä, mittausolosuhteita muuttamalla, laiteparametrien optimoinnilla ja matemaattisilla korjauskeinoilla. Spektraalisista häiriöistä yleisimpiä ovat isobaariset häiriöt, mutta joillekin isotoopeille voi myös kahdesti varautuneet ionit aiheuttaa häiriöitä, kuten ⁶⁹Ga⁺-isotoopin määritystä häiritsee bariumin kahdesti varautunut ¹³⁸Ba²⁺-isotooppi. Plasmakaasuna käytetyn argonin ionisoitumisaste kasvaa lämpötilan kohotessa ja molekyyli-ionihäiriöt lisääntyvät, jotka aiheuttavat massaspektreissä päällekkäisyyksiä. Molekyyli-ionihäiriöt voivat esimerkiksi häiritä raudan isotoopin ⁵⁶Fe⁺ määritystä ⁴⁰Ar¹⁶O⁺-molekyylinä. Tässä tutkielmassa käsitellään alkuaineiden isotooppisuhteiden määritykseen ICP-MS-tekniikan avulla, ICP-MS-tekniikan teoriaan ja laiteratkaisuihin, spektraalisten häiriöiden muodostumiseen sekä niiden minimointiin ja isotooppisuhteiden määrityksen eri sovellutuskohteisiin.

Sample introduction by laser ablation has many desirable features: reduction of the time involved in sample pre-analysis processing, avoiding the use of hazardous reagents and reducing the risk of contamination by reagent impurities. It is also possible to produce spatial analytical profiles across small sections of samples. Laser spots of < 10 μm diameter are possible With the latest commercial instrumentation. Additionally, for plasma spectrometry, the presence of molecular species derived from the plasma gases and the solvent vapour results in interferences, particularly for elements with an atomic mass of less than 80. Sampling with a laser removes the need for a solvent. The type of laser used for sampling is an important consideration. Ultraviolet lasers give better coupling between the laser and sample with ablation being mainly photochemical in nature. With infrared lasers, coupling with some samples is inefficient and is generally thermal m nature leading to poor crater definition. Calibration is one of the main difficulties associated with quantitative analysis by laser ablation. The majority of papers associated with the use of lasers for solid sampling give reference to the difficulty of reproducible calibration and in particular the lack of matrix matched standards The most commonly used calibration method to date involves the use of the National Institute of Standards and Technology (NIST) standard reference materials, particularly the 600 series glass standards. The disadvantages associated with these standards are: the analyst has no control over the elemental make up of the standard, they are relatively expensive and most importantly the matrix is fixed and cannot be matched to the sample. This thesis describes a calibration technique based on the ablation of aqueous standards. Water is transparent to the commonly used UV laser wavelengths, 193,248 and 266 nm resulting in poor energy coupling between the laser and the aqueous standard. The addition of a photo-stable chromophore results in modification of the standards absorption coefficient and enables them to mimic the behaviour of solid samples. the benefit of such standards is that they are easy to produce in any analytical laboratory. The elemental and matrix composition can be controlled by the analyst. The standards also offer the advantage of a constantly renewable surface. Initial work involved design and set-up of an optical system and laser to couple the laser with an ICP-MS. Poly( sodium 4-styrene-sulphonate) was identified as a suitable chromophore. The main criteria for the additive being that it absorbed at the excimer laser wavelengths and had an acceptable lifetime to allow adequate analytical data to be generated Investigation into the characteristics of the chromophore including effect of concentration, laser energy and laser frequency were investigated. Calibration and validation of the aqueous calibration technique was demonstrated by comparison with NIST standard reference materials. The absorption coefficient of the aqueous standard was matched with that of the NIST reference material. Both samples were then analysed by ICP-MS. The count rates observed were initially found to be similar for both samples, however the signal for the aqueous standard remained stable but the signal for the NIST glass decreased. This was thought to be due to the laser channelling into the solid sample causing loss of focus. The aqueous standard in effect provides a constantly renewable surface and no loss of focus. An internal standard was used to correct for the differing sensitivities obtained. The final part of the work involved application of the calibration method to two biological matrices: Bone samples from patients with osteoporosis and porcine liver samples. Elemental profiles across the samples are presented which are in general agreement with the expected and certified concentrations.

Atualmente a metodologia de Lu-Hf é um dos métodos mais utilizados na geocronologia, principalmente nas análises in situ em zircão por LA-ICP-MS. O interesse na aplicação desta metodologia, quando se dispõe de um sistema como o LA-ICP-MS, deve ser consignado à relativa simplicidade, sensibilidade e rapidez da análise. A alta concentração e a baixa mobilidade do Hf no zircão propiciam razões isotópicas e idades modelos bastante precisas, que podem subsidiar importantes inferências não só quanto à idade de extração mantélica, mas também quanto à sua possível história evolutiva, proveniência e estudos afins. Assim, o projeto de tese foi elaborado com base nos principais objetivos, o aprendizado, a implementação e a aplicação da metodologia de Lu-Hf em zircão por ICP-MS. Zircões de três diferentes áreas, previamente datados pela metodologia U-Pb, foram analisados: Anortosito de Capivarita (Brasil), Ofiolito de Aburrá (Colômbia) e a Bacia de Camamu (Brasil). As análises foram feitas utilizando equipamentos como o ICP-MS Neptune (ThermoFinnigan), e os lasers Excimer 193 nm (ArF, GeoLas) e o 213 UP (Nd:YAG, New Wave). O ofiolito estudado consiste de rochas máficas e ultramáficas. Análises de 12 grãos revelaram Hf(t) entre +2,01 e +5,35, enquanto as idades modelo TDM resultaram valores em um intervalo entre 1,15 e 1,44 Ga, sugerindo a presença de um magma juvenil com possível contaminação crustal e forte afinidade com as rochas da Província Rondoniana - San Ignacio. Zircões magmáticos e metamórficos do Anortosito de Capivarita, localizado na porção NE do Escudo Sul-Rio-Grandense, fizeram parte de um estudo de comparação para verificar a reprodutibilidade dos dados obtidos pela metodologia de Lu-Hf desenvolvida no LGI. As análises foram feitas primeiramente no LGI-UFGRS (Brasil) e depois no MAFIIC-MUN (Canadá). Os resultados dos dois laboratórios mostraram boa reprodutibilidade, as idades TDM e os valores de Hf obtidos foram concordantes dentro dos erros experimentais. Estes resultados forneceram informações sobre a proveniência do anortosito e sugeriram uma fonte juvenil para a fusão com algum grau de contaminação crustal Paleoproterozóica. A Bacia de Camamu está relacionada ao rompimento do Gondwana e pertence ao grupo de bacias sedimentares da margem leste brasileira. Zircões detríticos dos Grupos Brotas e Almada, relacionados às fases pré-rifte e rifte da bacia, foram analisados por U-Pb e Lu-Hf. No Grupo Brotas, 70% dos zircões analisados são de idade Cambriana-Vendiana, provenientes do Orógeno Araçuaí- Congo Ocidental levando em conta as medidas de paleocorrente de S-SW para NNE. No Grupo Almada, as principais fontes dos zircões são Paleoproterozóica e Arqueana, de proveniência direta do embasamento adjacente a Oeste da Bacia de Camamu, consistente com as medidas de paleocorrente de oeste para leste das unidades estudadas. Os zircões paleoproterozóicos e arqueanos analisados, mesmo os Neoproterozóicos e os Eopaleozóicos mostram um forte componente crustal retrababalhado com menor contribuição de crosta juvenil. Contudo, a metodologia de Lu-Hf por LA-ICP-MS aplicada em zircões de diferentes áreas mostrou o potencial em fornecer dados precisos e confiáveis para estudos de proveniência e de crescimento crustal, de modo a redimensionar cada vez mais a geocronologia.
Currently the methodology of Lu-Hf is one of the most widely used in geochronology, especially in in situ analysis in zircon by LA-ICP-MS. The interest in the application of this methodology, when it has a system like LA-ICP-MS, should be consigned to relative simplicity, sensitivity and speed of analysis. The high concentration and low mobility of Hf in zircon, provide isotopic ratios and model ages highly accurate that can support not only important inferences about the age of mantle extraction, but also as to its possible evolutionary history, provenance and related studies. Thus, the thesis project was elaborated based on main objectives, learning, implementation and application of Lu-Hf methodology in zircon by ICP-MS. Zircons from three different areas, previously dated by U-Pb method, were analyzed: Capivarita Anorthosite (Brazil), Aburrá Ophiolite (Colombia) and Camamu Basin (Brazil). The Lu-Hf in situ analyses were performed using equipments such as Neptune ICP-MS (ThermoFinnigan), and lasers Excimer 193 nm (ArF, GeoLas) and UP 213 (Nd: YAG, New Wave). The studied ophiolite consists of ultramafic and mafic rocks. Analyses of 12 grains revealed Hf(t) between +2.01 and +5.35, while the TDM model ages values resulted in a range between 1.15 and 1.44 Ga, suggesting the presence of a juvenile magma with possible crustal contamination and strong affinity with the rocks of the Rondonian-San Ignacio Province. Magmatic and metamorphic zircons from Capivarita Anorthosite, located in the NE portion of the Sul-Rio-Grandense Shield, were part of a comparison study to verify the reproducibility of obtained data by Lu-Hf methodology developed in the LGI. Analyses were performed first in the LGI-UFGRS (Brazil) and then at MAFIIC-MUN (Canada). Results from both laboratories show good reproducibility, TDM ages and Hf(t) values obtained are in agreement within experimental errors. These results provide information on the origin of anorthosite and suggested a juvenile source for the melt with some degree of Paleoproterozoic crustal contamination. Camamu Basin is related to the breakup of Gondwana and belongs to the group of sedimentary basins on the eastern Brazilian margin. Detrital zircons of Brotas and Almada Groups, related to the pre-rift and rift phases of the basin, were analyzed by U-Pb and Lu-Hf. In Brotas Group, 70% of analyzed zircons are Vendian-Cambrian age, from the Araçuaí-West Congo Belt taking into account the paleocurrent measurements from S-SW to N-NE. In Almada Group, the main sources of the zircons are Paleoproterozoic and Archean, with direct provenance from the basement adjacent to West Camamu Basin which is consistent with the paleocurrent measurements from west to east of the studied units. The analyzed Paleoproterozoic and Archean zircons, even the Neoproterozoic and Eopaleozoic show a strong reworked crustal component with small contribution of juvenile crust. However, the Lu-Hf methodology by LA-ICP-MS applied to zircons from different areas showed the potential to provide accurate and reliable data for provenance and crustal growth studies in order to resize increasingly the geochronology.

Le germanium est un métalloïde « stratégique » dans l’industrie high-tech, notamment pour la transition énergétique et le secteur des communications. Étant distinctement sidérophile, lithophile, chalcophile et organophile, le Ge possède un fort potentiel comme traceur géochimique. Ces travaux de thèse visent à améliorer la compréhension de la géochimie du cycle du Ge et des facteurs qui contrôlent son incorporation dans les minéraux et les gisements métalliques. Les cibles de cette étude concernent le gisement filonien à Zn de Saint-Salvy (Massif Central, France), le gisement filonien à Cu de Barrigão (Ceinture pyriteuse ibérique, Portugal), et le gisement à Zn–Cu de Kipushi (R.D. Congo). Les porteurs de Ge les plus importants sont respectivement la sphalérite (jusqu’à 2580 ppm), la chalcopyrite (jusqu’à 5750 ppm) et la réniérite (5,0–9,1 %). Les résultats montrent qu’il existe une relation de premier ordre entre la concentration en Ge dans la sphalérite et le type de gisement. La spectroscopie XANES par rayonnement synchrotron met en évidence la présence de Ge4+ en site tétraédrique dans les sulfures analysés. Les corrélations élémentaires observées dans la sphalérite et la chalcopyrite suggèrent une incorporation du Ge par co-substitutions, e.g., 3Zn2+ ↔ Ge4+ + 2(Cu,Ag)+ et 3Fe3+ ↔ 2Ge4+ + Cu+, ou via la création de lacunes cristallographiques, e.g., 2Zn2+ ↔ Ge4+ + ?. La corrélation positive δ74Ge–[Ge]ZnS des sphalérites de Saint-Salvy indiquerait que coefficient de partage (KdGe) augmenterai avec T. Les compositions isotopiques δ74Ge des sulfures étudiés varient de –5,72‰ à +3,67‰. Les compositions légères mesurées dans les gisements de Saint-Salvy et Barrigão semblent liées à des variations de température des fluides (basse à moyennes T) lors de l’incorporation de Ge en système ouvert, alors que la tendance marquée vers les compositions isotopiques lourdes à Kipushi indiquerait un fractionnement de Rayleigh
Germanium is a critical metalloid in many high-tech industries, especially for the energy transition and the communication sector. Being distinctly siderophile, lithophile, chalcophile and organophile, Ge can be a particularly useful geochemical tracer. This thesis aims at understanding the Ge geochemistry and the factors controlling its concentration in Ge-bearing minerals and ore deposits. Three contrasted Ge-bearing deposits were studied, the Saint-Salvy Zn vein-type deposit, French Massif Central, the Barrigão Cu vein-type deposit, Iberian pyrite belt, Portugal, and the Kipushi Zn–Cu carbonate-hosted deposit, Central African copper-belt, D.R. Congo. The most important Ge-bearing minerals are sphalerite (up to 2580 ppm Ge), chalcopyrite (up to 5750 ppm Ge), and renierite (5.0–9.1 wt.% Ge). The results show a first order relation between the Ge content and the deposition temperature. Synchrotron-based XANES spectroscopy showed that Ge4+ occur in tetrahedral sites in the studied sulphides. Element correlations suggest that Ge is chiefly incorporated in sphalerite and chalcopyrite through coupled substitutions, e.g., 3Zn2+ ↔ Ge4+ + 2(Cu,Ag)+ and 3Fe3+ ↔ 2Ge4+ + Cu+, respectively, or via the creation of lattice vacancies, e.g., 2Zn2+ ↔ Ge4+ + ?. The positive δ74Ge–Ge content correlation observed in sphalerite from Saint-Salvy could indicate that Ge partition coefficient (KdGe) increases with temperature. Ge isotopes in sulphides yield δ74Ge values spanning from –5.72‰ to +3.67‰. The light δ74Ge compositions of Saint-Salvy and Barrigão ores appear to be related to variations in low to moderate fluid temperatures during Ge uptake in open system (e.g., fluid cooling), while the trend towards heavy δ74Ge compositions observed at Kipushi likely translates a Rayleigh fractionation effect during ore formation in closed system, associated with significant fluid modification

The work described within this thesis explores the use of HPLC coupled with ICPMS and ESI-MS in order to develop novel methods which overcome specific analytical challenges in the pharmaceutical industry. A membrane desolvation interface has been evaluated for coupling high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS). Desolvation of the sample prior to reaching the plasma was shown to facilitate a versatile coupling of the two instrumental techniques, enabling chromatographic eluents containing up to 100 % organic to be used. This interface also allowed gradient elution to be used with ICP-MS. Tris(2,4,6-trimethoxyphenyl)phosphonium propylamine bromide (TMPP) was used for the derivatisation of maleic, fumaric, sorbic and salicylic acids to facilitate determination by HPLC-electrospray ionisation tandem mass spectrometry (ESIMS/ MS) in positive ion mode. Improvements in detection limits post-derivatisation were achieved, and this method was successfully used for the determination of sorbic acid in a sample of Panadol™. HPLC coupled with sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) has been used for the determination of maleic, sorbic and fumaric acids after derivatisation with TMPP. This allowed 31P+ selective detection to be performed for these compounds, which are normally undetectable by ICP-MS. Optimal reagent conditions for the derivatisation of 0.1 mM maleic acid were: 1 mM TMPP; 10 mM 2-chloro-1-methylpyridinium iodide (CMPI); 11 mM triethylamine. The efficiency of the derivatisation reaction was estimated to be between 10-20%. Detection limits, estimated as 3 times baseline noise, were 0.046 nmol for TMPP and 0.25 nmol for derivatised maleic acid, for a 5 f.JL injection. Following on from this, a novel derivatising reagent, tris(3,5-dibromo-2,4,6- trimethoxyphenyl) phosphonium propylamine bromide (BrTMPP), was synthesised and subsequently characterised by proton NMR spectroscopy and ESI-MS. This was utilised to derivatise maleic acid, with a 9-fold increase in sensitivity gained when analysed by bromine selective detection as apposed to phosphorus selective ICP-MS. This derivatising reagent (BrTMPP) was also utilised to determine the degree of phosphorylation on phosphorylated peptides. A phosphorus containing carboxylic acid was successfully derivatised and the correct Br:P ratio was determined for this compound by ICP-MS. However, phosphorylated peptides were not successfully derivatised by BrTMPP. A combination of UV and phosphorus selective ICP-MS was also used to distinguish between phosphorylated and un-phosphorylated peptides after HPLC separation.

Ce mémoire présente les travaux effectués pour la mesure rapide des éléments des terres rares (ETR), comprenant Sc et Y, dans des matériaux géologiques. La digestion acide sur plaque chauffante, la digestion micro-onde et la digestion par fusion boratée ont été étudiées en tant que méthodes de digestion possibles pour les minéraux porteurs d’ETR. Une nouvelle procédure de digestion a été développée en utilisant un appareil de fusion. La température élevée de la digestion (1050 °C) et l'utilisation de LiBO2 comme fondant se sont montrées efficaces pour la digestion de chaque ETR. L'analyse par activation neutronique (NAA), la spectroscopie d’émission atomique par plasma micro-onde (MP-AES), la spectroscopie d’émission optique couplée à un plasma induit (ICP-OES) et la spectrométrie de masse en tandem couplée à un plasma induit (ICP-MS/MS) ont été explorées à titre des techniques d'analyse possibles pour la mesure des ETR dans divers échantillons de minerais. L'étude comparative a montré que les résultats obtenus par ICP-MS/MS sont en accord avec les résultats de matériaux de références certifiés, alors que les autres techniques d'analyse révèlent plusieurs interférences spectrales pour certains ETR. En outre, la spectrométrie de masse en tandem permet de nouvelles configurations de filtrage de masse, ce qui réduit les interférences polyatomiques lors de la détermination du Sc dans des matrices minérales. La conversion des ions Sc+ en ions ScO+ a fourni des conditions analytiques sans interférence et des limites de détections suffisamment basses, en bas de 3 ng/L, pour quantifier avec précision le Sc. La précision de la méthode proposée a été évaluée par l'analyse de cinq matériaux de référence certifiés différents (BX-N, 2-OKA, NIM-L, SY-3 et GH).
In this work, an innovative analytical protocol is introduced for rapid measurement of rare-earth elements (REE), including Sc and Y, in geological materials. Open-vessel acid digestion, microwave digestion and alkali digestion were investigated as possible digestion methods for minerals bearing REE. A new digestion procedure was developed using a fusion apparatus. The high digestion temperature (1050 ºC) and the use of LiBO2 as a flux were found to be effective for the digestion of every REE. Instrumental neutron activation analysis (NAA), microwave induced plasma atomic emission spectroscopy (MP-AES), inductively coupled plasma optical emission spectroscopy (ICP-OES), and inductively coupled plasma mass spectrometry (ICP-MS) were explored as possible analytical techniques for the measurement of REE in various mineral samples. The comparative study showed that the results obtained by ICP-MS are in good agreement with the certified reference materials (CRM) data, whereas the other analytical techniques reveal several spectral interferences for some REE. Furthermore, the tandem quadrupole instrument enables new mass filtering configurations, which can reduce polyatomic interferences during the determination of Sc in mineral matrices. Conversion of Sc+ ions into ScO+ ions provided interference-free conditions and sufficiently low limits of detection, down to 3 ng/L, to accurately quantify Sc. The accuracy of the proposed methodology was assessed by analyzing five different CRM (BX-N, OKA-2, NIM-L, SY-3 and GH).

Ce manuscrit de thèse intègre l'application de plusieurs méthodologies analytiques à l'analyse de spéciation des matières premières renouvelables et des fractions de pétrole lourd. Des techniques de séparation telles que la chromatographie par perméation de gel (GPC) et la chromatographie en phase liquide supercritique (SFC) ont été combinées avec la détection élémentaire fournie par la spectrométrie de masse haute résolution à plasma à couplage inductif (ICP-MS), afin d'obtenir une empreinte digitale de ces espèces d’intérêt, basé sur leur volume hydrodynamique, présent dans les échantillons à matrices complexes.La combinaison de ces techniques de séparation avec l’ICP-MS n'a pas été une tâche facile. Cependant, afin de fournir à la plate-forme de chimie analytique de nouvelles solutions pour l'analyse de spéciation d'échantillons complexes (1), une alternative bon marché aux nébuliseurs à consommation totale actuelle, produite via l'impression 3D et dont le capillaire a été construit en PEEK, a été développé et validé pour l'analyse des éléments trace dans les matrices organiques via GPC-ICP-MS et (2) une nouvelle interface a été conçue et optimisée pour l'analyse des éléments trace via SFC-ICP-MS. Bien que des résultats très prometteurs aient été obtenus, de nouvelles expérimentations doivent être menées avec ces deux méthodologies afin de mieux comprendre les espèces inorganiques présentes dans les matières premières renouvelables et les bio-huiles.La distribution en taille des espèces de soufre, de nickel et de vanadium dans les fractions de résidus atmosphériques a été obtenue via des analyses GPC-ICP-HRMS afin de suivre et de comprendre leur évolution au cours de deux processus industriels importants destinés à convertir ces fractions de pétrole lourd en carburants de transport: l'hydrodémétallisation et l'hydrodésulfuration. En outre, les distributions de tailles des espèces contenant du phosphore, du sodium, du fer, du magnésium et du soufre dans les huiles de pyrolyse lignocellulosique et les charges d'acide gras ont également été obtenues, démontrant que des agrégats de haut poids moléculaire se forment dans ces échantillons complexes lorsqu'ils sont stockés.Des méthodologies alternatives pour l'analyse des matières premières renouvelables ont été testées. L'utilisation de la vaporisation électrothermique couplée à la spectroscopie d'émission optique à plasma à couplage inductif (ETV-ICP-MS) a fourni des résultats très prometteurs. Une méthodologie qui ne nécessite pas l'utilisation de gaz fréon-R12 a été optimisée et validée pour l'analyse totale de huit éléments trace dans des échantillons complexes. De plus, la répartition des espèces contenant des éléments trace tels que P, Na, Mg et Al entre autres, en fonction de leurs températures de vaporisation, a été obtenue
This thesis incorporates the application of several analytical methodologies to the speciation analysis of renewable feedstocks and petroleum heavy oil fractions. Separation techniques such as gel permeation chromatography (GPC) and supercritical fluid chromatography (SFC) have been combinedwith the elemental detection that inductively coupled plasma mass spectrometry (ICP-MS) provides to obtain a fingerprint of those species of interest, based on their hydrodynamic volume, present in samples with complex matrices. However, the combination of these separation techniques with ICP-MS was not an easy task.With the purpose of providing to the analytical chemistry platform with novel approaches for the speciation analysis of complex samples, two novel tools have been devised during this three-year’s project: (1) a cheap alternative to the current total consumption nebulisers, produced via 3D-printing and whose capillary has been built in PEEK, has been developed and validated for the analysis of trace elements in organic matrices via GPC-ICP-MS and (2) a novel interface has been designed and optimised for the trace element analysis via SFC-ICP-MS. Although very promising results have been obtained, further experiments must be carried out with these two methodologies to obtain a better understanding of the inorganic species present in renewable feedstocks and bio-oils.The size distribution of sulfur, nickel and vanadium species in atmospheric residue fractions has been obtained via GPC-ICP-HRMS analyses to track and understand their evolution during two important industrial processes that are destined to convert these heavy oils into transportation fuels: hydrodemetallization and hydrodesulfurization. Furthermore, the phosphorus-, sodium-, iron-, magnesium- and sulfur-containing species’ size distributions in lignocellulosic fast pyrolysis oils and fatty acid feedstocks have been also obtained, demonstrating that high-molecular aggregates are formed within these complex samples when they are stored.Alternative methodologies for the analysis of renewable feedstocks have been tested. The use of electrothermal vaporisation coupled to inductively coupled plasma optical emission spectroscopy (ETV-ICP-OES) has provided with highly promising results. A methodology that does not require the use of freon-R12 gas has been optimised and validated for the total analysis of eight trace elements in complex samples. Besides, the distribution of the species containing trace elements such as P, Na, Mg and Al among others, based on their vaporisation temperatures, has been obtained
Denne PhD afhandling anvender forskellige analytiske metoder til specieringsanalyse af vedvarende råmaterialer og petroleumstunge oliefraktioner. I afhandlingen anvendes separationsteknikker som gel permeations kromatografi (GPC) og superkritisk væskekromatografi (SFC) i kombination med detektion af elementer somved induktiv koblet plasma-højopløsningsmassespektrometri (ICP-MS). Metoderne anvendes til at måle det kemiske fingeraftryk af specier i komplekse matricer , baseret på speciernes hydrodynamiske volumen. Kombinationen af kromatografiske separationsteknikker med ICP-MS var ikke en let opgave.For at opnå en forbedre analyse af komplekse matricer blev der udviklet en række nye forbedrede metoder til specifikationsanalysen af komplekse prøver: (1) en billig alternativ til den nuværende ”total consumption nebuliser” blev udviklet og valideret til sporstof anlayse i organiske matricer via GPC-ICP-MS. Den nye nebuliser blev produceret ved 3D print af PEEK materiale; (2) et nyt interface blev designet og optimeret til sporelementanalyse ved SFC-ICP-MS. Selvom der er opnået meget lovende resultater, skal yderligere eksperimenter udføres med disse to metoder for at opnå en bedre forståelse af specierne som er tilstede i vedvarende råmaterialer og bioolier.Størrelsesfordelingen af svovl-, nikkel- og vanadiumspecier i atmosfæriske restfraktioner er opnået via GPC-ICP-HRMS-analyser for at spore og forstå deres udvikling under to vigtigeindustrielle processer, der er designet til at omdanne ukonventionelle olier til transportbrændstof: hydrodemetallization og afsvovling.Endvidere er størrelsesfordelingen af forfor-, natrium-, jern-, magnesium- og svovlholdige specier målt i lignocellulosiske pyrolyseolier og fedtsyreholdige-råmaterialer. Disse resultater viser, at der dannes højmolekylære aggregater i disse komplekse prøver, når de opbevares ved normale forhold.Alternative metoder til analyse af vedvarende råmaterialer er blevet testet. Der blev opnået lovende resultater ved anvendelsen af elektrotermisk fordampning koblet til induktivt koblet plasmaoptisk emissionsspektroskopi (ETV-ICP-OES). En ETV-ICP-OES metode som ikke kræver anvendelse af freon-12-gas, er blevet optimeret og valideret til analyse af summen af otte sporstoffer i komplekse prøver. Metoden blev anvendt til analyse af sammensætningen af P, Na, Mg og Al specier baseret bl.a. på deres fordampningstemperaturer

La determinación de arsénico en el agua de consumo humano es importante, ya que es un elemento que en algunas zonas es usual encontrarlo naturalmente y suele alcanzar valores que son tóxicos para la salud. Conociendo los valores de arsénicos presentes en el agua, permite tomar una decisión respecto al tratamiento de remediación a realizar para que se cumplan los límites permitidos por el Código Alimentario Argentino. Se pueden utilizar varios métodos de análisis, pero en este trabajo se propuso como objetivo, comparar dos métodos de ensayo: ICP-OES (Espectrometría de Emisión Óptica por Plasma de Acoplamiento Inductivo) e ICP-MS (Espectrometría de Masas por Plasma de Acoplamiento Inductivo), para determinar si difieren significativamente entre sí. Las muestras fueron tomadas en el departamento de Lavalle, provincia de Mendoza, ya que existen antecedentes de la existencia de altas concentraciones de arsénico en esta zona. Se analizaron 30 muestras de agua en el laboratorio Alex Stewart International Argentina S.A. por ambos métodos. Se pudo concluir que en todas las muestras de agua analizadas se hallaron niveles superiores al límite máximo de arsénico permitido en agua potable. Luego del análisis estadístico de los datos obtenidos, se determinó que ambos métodos no son significativamente comparables, debido a los diferentes límites de detección y rangos de trabajo de cada equipo. Con el ICP-MS se pueden analizar muestras de agua con menores concentraciones del analito y para concentraciones mayores el ICP-OES tiene mejor respuesta. Esto hace que el empleo de ambos métodos pueda aplicarse a rangos de concentración diferentes. Finalmente, se concluye que, en los intentos de ofrecer una propuesta superadora frente a los análisis clásicos existentes, para la determinación de arsénico en agua, las dos metodologías propuestas no pueden ser utilizadas indistintamente, sino solo dentro de sus rangos de concentración, de manera complementaria.
Fil: Llanos, Lorena Vanina. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias.

Il presente lavoro di tesi ha l’obiettivo di studiare dal punto di vista chimico, il tabacco “kentucky” coltivato e lavorato in alcune zone della Regione Veneto. Questo tipo di produzione agricola è considerata di nicchia e la caratterizzazione e quantificazione dei suoi principali costituenti chimici non è mai stata approfondita. Nel presente lavoro di tesi si sono individuati alcuni componenti chimici sviluppando e/o perfezionando metodi analitici utili all’individuazione di una "impronta digitale" chimica del tabacco Kentucky veneto. Il Kentucky è un tabacco scuro appartenente alla classe dei cosiddetti fire cured (cura a fuoco), cioè i tabacchi seccati attraverso il fumo di legni speciali che, penetrando lentamente nelle foglie, ne conferiscono un particolare aroma e il colore scuro. I metodi analitici sviluppati hanno reso possibile l’individuazione e la quantificazione di una serie di composti inorganici ed organici in foglie di tabacco kentucky dopo la cura a fuoco coltivato nel Veronese e in campioni di tabacco lavorato. Il lavoro svolto in laboratorio prevede due fasi lavorative. La prima, consiste nella quantificazione di analiti di tipo inorganico attraverso la digestione acida in microonde delle foglie di sigaro per poter analizzare in ICP-MS la quantità di metalli pesati presenti in essi (TE e REE), tenendo presente dei possibili effetti di frazionamento isotopico che incidono sui risultati finali di concentrazione. La seconda fase invece include la quantificazione di analiti di tipo organico, nello specifico dell’alcaloide Nicotina e delle nitrosammine specifiche del tabacco NNN e NNK (noti anche come, rispettivamente, N-nitrosornicotina e 4-(metilnitrosamino)-1-(3-piridil)-1-butanone) tramite estrazione con MeOH dei campioni già polverizzati e successive analisi. La quantificazione è avvenuta via GC-MS per la nicotina e via HPLC-MS/MS per quanto riguarda le nistrosammine. L'utilizzo di un materiale certificato di riferimento ha permesso di validare i metodi per la quantificazione degli analiti. I risultati ottenuti sono stati sottoposti ad una analisi statistica preliminare per valutare correlazioni utili a individuare una possibile indicazione di tracciabilità.

Orientadores: Marco Aurélio Zezzi Arruda, Ljubica Tasic
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo: Este trabalho consistiu em estudos de metalômica comparativa de sementes de soja transgênica (T) e não-transgênica (NT). Para tanto, as sementes de soja T e NT foram comparadas, em um primeiro, momento levando-se em conta: concentração total dos elementos, comportamento dos elementos durante extração utilizando-se fracionamento sequencial, e bioacessibilidade dos elementos após procedimento de digestão gastrointestinal simulada (in vitro). As análises preliminares foram feitas utilizando-se ICP-MS com analisador de massas quadrupolar, e as análises posteriores utilizando espectrometria de massas de alta resolução com plasma acoplado indutivamente (HR-ICP-MS). Foram determinados 25 elementos em concentrações variando de ng g até %. Foi observado que as sementes de soja T e NT exibem diferenças estatisticamente significantes nas concentrações de Cu, Fe e Sr, sendo os dois primeiros apresentando maiores concentrações na semente T, e, o último, com maior concentração nas sementes de soja NT. Estes resultados também se refletiram nos conteúdos desses elementos em extratos aquosos e resíduos obtidos por meio de fracionamento sequencial. Ainda, os experimentos de bioacessibilidade realizados mostraram que as frações bioacessíveis de Cu, Fe, e outros elementos (Mn, S, Zn) contribuíram em maior porcentagem para a concentração total dos elementos nas sementes de soja T do que para as sementes de soja NT. Posteriormente, foi dada continuidade aos estudos utilizando cromatografia líquida bidimensional off line para as amostras de sementes de soja, sendo a primeira dimensão constituída de cromatografia de exclusão por tamanho (SEC,) e a segunda dimensão constituída de cromatografia de troca aniônica (AEX). Na primeira dimensão cromatográfica foram identificadas três frações contendo metais por meio da hifenação SEC-ICP-MS: a primeira correspondendo a massas molares entre 38,1 e 181,1 kDa, a segunda correspondendo a massas molares entre 8,2 e 17,2 kDa, e a terceira fração correspondendo a massas molares entre 0,4 e 3,8 kDa. As três frações identificadas foram separadas, liofilizadas, e separadas novamente utilizando a cromatografia de troca aniônica. Foram detectados metais em todas as frações separadas por SEC: três sub-frações da primeira fração, uma sub-fração na segunda fração e três sub-frações na terceira fração. Os eluatos foram coletados, liofilizados, digeridos e levados ao espectrômetro de massas com fonte de ionização por electrospray (ESI-MS) para identificação de proteínas. Foram identificadas 33 e, entre elas, duas proteinas previamente relacionadas a metais foram encontradas: seed lipoxygenase 1 e b-conglycinin. Após a separação na segunda dimensão cromatográfica, as sub-frações resultantes foram liofilizadas e submetidas a uma terceira dimensao de separacao, utilizando a eletroforese em gel de poliacrilamida unidimensional (SDS-PAGE). As bandas obtidas por SDS-PAGE foram recortadas e digeridas a fim de analisar os metais presentes nas mesmas, destacando os resultados obtidos para Fe, onde o mesmo foi quantificado nas bandas da sub-fração onde o pico deste elemento foi encontrado nas análises por AEX-ICP-MS. Ainda, as bandas foram digeridas tripticamente a fim de identificar as proteínas presentes, e, novamente, proteínas associadas a metais foram identificadas: chain A lipoxygenase-3 (Soybean) complex with 13(S)-hydroperoxy- 9(Z),11(E)-octadecadienoic acid; beta-amylase [Glycine max]; seed lipoxygenase-1, lipoxygenase [Glycine max], seed lipoxygenase-2 (PISUM SATIVUM) e beta-conglycinin
Abstract: This work consisted of comparative metallomics studies of transgenic (T) and nontransgenic (NT) soybean seeds. To that end, T and NT seeds were compared at first taking into account: the total concentration of the elements, the elements behavior during extraction using sequential fractionation, and bioacessibility of the elements after simulated gastrointestinal digestion procedure (in vitro). Preliminary analyzes were done using ICP-MS with quadrupole mass analyzer, and the subsequent analysis using high-resolution inductively coupled plasma mass spectrometry, (HR-ICP-MS). 25 elements were determined at concentrations ranging from 1 ng g up to %. It was observed that T and NT soybean seeds exhibit statistically significant differences in the concentrations of Cu, Fe and Sr, the first two having higher concentrations in the T seeds, and the last with the highest concentration in soybeans NT. These results were also reflected in the contents of these elements in aqueous extracts and residues obtained through sequential fractionation. Also, the contributions of bioaccessible fractions of Cu, Fe and other elements (Mn, S, Zn) to the total content of the elements in T soybean seeds were higher than those found in NT soybean seeds. Subsequently, studies were continued using bidimensional liquid chromatography, the first dimension consisting of size exclusion chromatography (SEC) and the second dimension of anion exchange chromatography (AEX). In the first chromatographic dimension three fractions containing metals were identified using hyphenation SEC-ICP-MS, the first corresponding to molar masses between 38.1 and 181.1 kDa, the second corresponding to molar masses between 8.2 and 17.2 kDa and the third fraction corresponding to molar masses between 0.4 and 3.8 kDa. The three identified fractions were separated and lyophilized, and again separated using anion exchange chromatography (AEX). Metals were found in all the separated fractions by SEC: three sub-fractions of the first fraction, a subfraction in the second fraction and three sub-fractions in the third fraction. These peaks were collected, lyophilized, digested and taken to the mass spectrometer for protein identification. 33 proteins were identified, and, among them, two proteins previously related to metals were found: seed lipoxygenase 1 and b-conglycinin. After chromatographic separation in the second dimension, the resultant subfractions were lyophilized and subjected to a third separation dimension using onedimensional polyacrylamide gel electrophoresis (SDS-PAGE). After the separation, the bands were cut out and digested to examine the metals contained therein, highlighting the results obtained for Fe, which was quantified in the bands of the sub-fraction where the peak of the element is found in the analysis by ICP-AEX - MS. Also, the bands were digested triptically to identify the proteins, and once again proteins associated to metals were identified: 3-lipoxygenase A chain (Soybean) complex with 13 (S)-Hydroperoxy-9 (Z), 11 ( E)-octadecadienoic acid, beta-amylase [Glycine max]; seed lipoxygenase-1, lipoxygenase [Glycine max] seed lipoxygenase-2 (Pisum sativum) and beta-conglycinin
Doutorado
Quimica Analitica
Doutora em Ciências

Orientadores: Marco Aurélio Zezzi Arruda, Fábio Cesar Gozzo
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo: ANÁLISE DE ESPECIAÇÃO DE METAIS E METALÓIDES LIGADOS A ANIDRASE CARBÔNICA EMPREGANDO MOBILIDADE IÔNICA E ICP-MS. No Capítulo 1, é proposta a técnica de mobilidade iônica na modalidade TWIMS, acoplada a um espectrômetro de massas do tipo ESI-Q-ToF MS/MS para análise de especiação da anidrase carbônica ligada a metais divalentes e em diferentes estados de oxidação, bem como ligada a espécies de selênio em diferentes estados de oxidação. O método é aplicado com sucesso na separação de espécies com diferentes estados de oxidação, mesmo quando as espécies de Se4+ e Se6+são adicionadas em uma mistura com a anidrase carbônica. O método também é aplicado para avaliação do estado de enovelamento da anidrase carbônica, em condições nativas e desnaturadas, sendo considerado satisfatório na elucidação das diferentes conformações da proteína. No Capítulo 2, a técnica de ICP-MS é usada na análise de especiação isotópica de Zn ligado à anidrase. A exatidão das medidas aproximou-se das condições naturais observadas para a razão isotópica de Zn ao final das otimizações. A precisão obtida situa-se dentro da margem observada para analisadores de m/z do tipo quadrupolo. Os principais desafios enfrentados neste capítulo foram minimizar os efeitos de discriminação de massas e a remoção de interferências poliatômicas. A enzima foi enriquecida com os isótopos 67Zn e 68Zn, sendo observada maior razão isotópica para anidrase ligada 67Zn. A atividade da anidrase enriquecida com isótopos de Zn apresentou resultados estatisticamente semelhantes
Abstract: SPECIATION ANALYSIS OF METALS AND METALLOIDS BOUND TO CARBONIC ANHYDRASE USING ION MOBILITY AND ICP - MS . In Chapter 1, ion mobility in TWIMS mode was proposed, coupled to a ESI-Q-ToF MS/MS mass spectrometer for speciation analysis of carbonic anhydrase bound to Ba2+, Zn2+, Cu+, Cu2+, Pb2+, Pb4+, Se4+ and Se6+. The method was successfully applied to separation of selenium species with different oxidation states, even when the species Se4+ and Se6+ were incubated in a mixture with carbonic anhydrase. The method was also applied to evaluation of carbonic anhydrase folding state in native and denatured conditions, and it was considered as satisfactory in the elucidation of different conformations of the protein. In Chapter 2, an ICP-MS was used for the isotopic speciation analysis of Zn bound to anhydrase. The accuracy measurements were closer to natural conditions for Zn isotope ratio, in the end of the optimization. The precision was within the range observed for m/z analyzer such as quadrupole. The main challenges in this chapter were to minimize the effects of mass discrimination and the removal of polyatomic interferences. The enzyme was enriched with 67Zn and 68Zn isotopes, and the highest isotope ratio was observed for 67Zn bound to anhydrase. Anhydrase activity of Zn enriched isotopes yielded similar statistical results
Doutorado
Quimica Analitica
Doutor em Ciências

La levure enrichie en sélénium (Saccharomyces cerevisiae) est l’une des formes de supplémentation alimentaire les plus appréciée chez l’homme et l’animal, notamment pour ses propriétés anti-cancérigènes potentielles. Les travaux de cette thèse ont contribué principalement à la caractérisation globale du selenométabolome (l’ensemble des métabolites de faibles poids moléculaires contenant du sélénium). C’est grâce aux développements et à l’utilisation de chromatographies liquides multidimensionnelles orthogonales couplées à l’ICP MS et à l’ESI MSn à haute résolution que ce travail de recherche a été rendu possible. L’approche méthodologique ainsi mise au point a permis de réaliser des empreintes moléculaires du sélénométabolome et de compléter la liste des composés identifiés (plus de 50, représentant la liste la plus complète à ce jour). Ces résultats ont également permis d’améliorer la compréhension des voies métaboliques utilisées lors de l’utilisation du sélénium par la levure. De plus, l’utilisation de la signature isotopique du sélénium déterminée par ICP MS multicollecteur en association avec les empreintes moléculaires du sélénométabolome représente ici un outil original et de choix permettant la discrimination des levures enrichies en fonction de leurs origines
Selenium-rich yeast (Saccharomyces cerevisiae) is the most popular form of supplemented selenium because of its putative anticancer properties. This thesis offers a contribution to the characterization of selenometabolome (the entirety of the low molecular weight selenium-containing metabolites) owing to the development of multidimensional liquid chromatography with parallel detection by ICP MS and electrospray high-resolution MSn. The developed methods permitted to obtain a selenometabolome’s fingerprint including the identity of over 50 selenium metabolites, the most exhaustive list so far, and to obtain a deeper insight into the Se metabolic pathways in yeast. Besides, isotopic signatures obtained by multicollector ICP MS associated with the selenometabolome fingerprint allowed the discrimination of Se-rich yeast samples according to their origin

Methods for the determination of the actinide elements in water, biological, soil and sediment samples have been developed using on-line solid phase extraction and high performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS). Initial applications utilised a commercially available resin, namely TRU-Spec resin, for efficient removal of the matrix prior to elution of uranium and thorium analytes. Comparative analyses of reference materials and natural water samples from Plymouth and Dartmoor demonstrated significant improvement in precision and speed of analysis by using TRU-Spec coupled to ICP-MS compared with alpha spectrometry. Further applications of the TRU-Spec resin for the determination of the transuranic actinide elements neptunium, plutonium and americium, resulted in the successful determination of 239Pu and 237Np in biological reference materials. Detection limits were 700, 850, and 600 attograms (ag) for 237Np, 233Pu, and 241Am, respectively, for a 0.5 ml sample injection, and better than 200 ag/g with 50 ml pre-concentration when sector field (SF) ICP-MS was used. A method for the selective sequential elution of uranium and plutonium was also developed to facilitate the determination of 239Pu without interference due to the 238U1H+ polyatomic ion, caused by high concentrations of 238U in sediment samples. Investigations were performed into the use of a polymeric substrate, which was dynamically coated with chelating dyes such as xylenol orange and 4-(2-pyridylazo) resorcinol, and a silica substrate coated with permanently bonded iminodiacetic acid. The latter was used for the successful determination of uranium and thorium in certified reference material waters. However, the column was found to have a high affinity for iron, making it unsuitable for the determination of the actinides in soil and sediment samples. Subsequently, a polystyrene substrate which was dynamically coated with dipicolinic acid was used for HPLC coupled with SF-ICP-MS. Using this column it was possible to separate the various actinides from each other and from the matrix. In particular, it was possible to separate plutonium and uranium to facilitate interference-free determination of the former. The column also exhibited some selectivity for different oxidation states of Np, Pu and U. Two oxidation states each for plutonium and neptunium were found, tentatively identified as Np(V) and Pu(III) eluting at the solvent front, and Np(IV) and Pu(IV) eluting much later. Detection limits were 12, 8, and 4 fg for 237Np, 239Pu, and 241Am, respectively, for a 0.5 ml injection, and the system was successfully used for the determination of 239Pu in water, biological and soil reference materials.

New methodologies have been developed for the determination of organotin and organolead compounds in environmental samples. Several high performance liquid chromatographic separations of organotin compounds have been tested and the best system (cation-exchange chromatography with methanol and a citrate buffer) employed for the determination of tributyltin (TBT), triphenyltin (TPhT), dibutyltin (DBT) and monobutyltin (MBT) in environmental samples. The coupling between high performance liquid chromatography (HPLQ and the inductively coupled plasma-mass spectrometer (ICP-MS) for this application has been modified to yield limits of detection of 0.44,0.26,1.4 and 0.23 ng. g-' as Sri for TBT, TPhT, DBT and MBT respectively. Different extraction procedures have been tested for the determination of organotin species in samples of environmental interest, such as sediments and biological materials. The values obtained for TBT, TPhT and DBT in the analysis of a mussel candidate reference material, CRM 477, have been incorporated in the certification campaign of this material. A liquid chromatographic separation for trimethyllead (TML) and triethyllead (TEL) has also been developed. Artificial rain water has been analysed for TML. The system proved to be valid for the determination of TML in this sample, even in the presence of high amounts of inorganic lead. Finally, isotope dilution analysis (IDA) was incorporated in the method. Tributyltin iodide (TBTI) and trimethyllead chloride (TMLCI), isotopically enriched in "Sn and "Pb, respectively, were synthesised. The mussel tissue CRM 477 was analysed with IDA-HPLC-ICPMS for TBT. As for the analysis without isotope dilution, the result obtained was incorporated in the certification campaign. The analysis with this methodology gave a better precision in the overall determination than external calibration analysis. Artificial rain water, at two different concentration levels, was analysed for TML with IDA-HPLC-ICP-MS. Better precision and accuracy was obtained for the analysis of this material with this method than when external calibration procedures were employed. IDA-HPLC-ICP-MS has proved to be a valid technique for the analysis of environmental samples. The technique simplifies the procedure, compensates for different sources of variability and, thus, the overall precision obtained in the analysis is improved compared to other calibration techniques.

Tese (doutorado) - Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas, Programa de Pós-Graduação em Química, Florianópolis, 2016.
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This work presents new approaches for halogen determination in a variety of samples using inductively coupled plasma - mass spectrometry (ICP-MS) and for isotope ratio measurements by multicollector - inductively coupled plasma - mass spectrometry (MC-ICP-MS) and application of the methods developed to real environmental cases. Four methods for solid sampling (SS) analysis by ICP-MS, three using electrothermal vaporization - inductively coupled plasma - mass spectrometry (ETV-ICP-MS) and one using laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS), and two methods for isotopic analysis by MC-ICP-MS, one for Br and another for Cl in sea water, were developed. The methods were applied for studying samples from real study cases, providing significant results with respect to environmental processes. For all three methods using SS-ETV-ICP-MS, the solid samples were directly weighed into graphite "cups" that were subsequently inserted into the graphite furnace, and the instrumental parameters were optimized for high sensitivity and efficient matrix removal. Chlorine determination in biological samples could be carried out using aqueous standard solutions, when using pre-dried modifiers (Pd + Nd or Pd + Ca) or using solid certified reference material (CRM), accompanied with or without the same pre-dried, achieving a limit of quantification (LOQ) of 5 ?g g-1. For Br and Cl determination in coal samples, Cl was accurately determined using calibration against solid standards, whereas Br could also be quantified adequately by using calibration against aqueous standard solutions, both using pre-dried modifiers (Pd + Ca), LOQs of 0.03 ?g g-1 for Br and 7 ?g g-1 for Cl were achieved. F, Cl, Br and I were determined in particulate matter, F was determined via high resolution - continuum source molecular absorption spectrometry (HR-CS MAS) for monitoring the CaF molecule, while Cl, Br and I were determined via SS-ETV-ICP-MS. This method allowed the quantification of the halogens in 14 PM10 samples collected in a Northeastern coastal city in Brazil. The results demonstrated variations of the halogen contents according to meteorological conditions, particularly related to rainfall, humidity and sunlight irradiation. Bromine determination in polymer samples was accomplished via LA-ICP-MS after the optimization of the operational parameters for high sensitivity. Under optimized conditions, it was possible to accurately determine Br in 5 different certified polymer reference materials and 5 real polymer samples by external calibration using different certified materials containing different concentrations of Br and by external calibration against a single certified material monitoring 12C+ as internal standard. The LOQ obtained was 110 ?g g-1 of Br. Bromine and Cl isotopic analysis in seawater via MC-ICP-MS was proven feasible, operated in high mass resolution and by decreasing the memory effect using 5 mmol L-1 of NH4OH in sample, standard and wash solutions. Optimal analyte concentrations were = 3 mg L-1 for Br and = 70 mg L-1 for Cl. The major cation load of seawater was removed via cation exchange chromatography (Dowex 50WX8 resin). In the case of Br, evaporation of the samples at 90°C permitted analyte preconcentration without Br loss or isotope fractionation. Mass discrimination was corrected for by external correction in a sample-standard bracketing approach for both elements. Sr, Ge and Se were also tested as potential internal standards for Br isotopic analysis but provided no advantage. Both methods demonstrated high precision and accuracy based on the comparison of experimental values with certified and literature values. The methods were applied within the context of an environmental study of Br and Cl in sea ice collected during the Sea Ice Physics and Ecosystem eXperiment 2012 voyage at different depths and locations. The concentration of these elements in the samples ranged from 700 to 31000 ?g L-1 for Br and from 200 mg L-1 to 8000 mg L-1 for Cl, and a relation between the concentrations and the corresponding ?81Br and ?37Cl values was found. Lower concentrations and ???values were observed for sea ice collected at greater depths and are probably related to desalinization processes.

Resumo : Os halogênios são um grupo de elementos que apresentam diversas particularidades, tornando-os muito importantes para diversos propósitos. No entanto, esses elementos apresentam elevado grau de toxicidade quando ingeridos ou inalados, e são considerados perigosos quando presentes no meio ambiente, devido principalmente ao fato de poderem reagir com moléculas de O3, promovendo a destruição da camada de ozônio. Considerando a alta aplicabilidade dos halogênios e seus efeitos adversos ao ambiente e em sistemas biológicos, faz-se necessário o estabelecimento de métodos sensíveis, com exatidão e precisão, para a sua determinação. Técnicas como eletrodos de íon seletivos, cromatografia de íons, análise por ativação de nêutrons instrumental, espectroscopia de fluorescência por raios-X, entre outros, foram propostos e aplicados com sucesso para analise de halogêneos em diversas matrizes, no entanto, em alguns casos, morosas etapas de preparo de amostras são necessárias, além de algumas das técnicas apresentarem limitações para analise multielementar, baixa sensibilidade, baixa frequência analítica, incidência de interferências e curta faixa linear para quantificação. Além de problemas para sua quantificação, a medida de razão isotópica de halogênios ainda é um desafio. Algumas técnicas têm sido aplicadas para este propósito como a espectrometria de massas de razão isotópica e espectrometria de massas por ionização química, entretanto, normalmente apresentam baixa precisão além de apresentarem muitos dos problemas apresentados para quantificação. Desta forma, o objetivo geral deste trabalho é apresentar propostas a fim de solucionar os problemas enfrentados para análise de halogênios por espectrometria de massas por plasma indutivamente acoplado (ICP-MS) e analise de razões isotópicas por multicoletor (MC)-ICP-MS, aplicando os métodos desenvolvidos para o estudo de casos ambientais reais. Uma breve introdução abordando os conceitos básicos sobre a importância dos halogênios, uma visão geral sobre funcionamento de equipamentos ICP-MS, determinação e análise isotópica de halogênios por ICP-MS é apresentada no Capítulo 1 o qual é seguindo pelos Capítulos 2, 3 e 4 onde se apresentam novas propostas para determinação de halogênios por meio da analise direta de sólidos utilizando vaporização eletrotérmica (SS-ETV)-ICP-MS e aplicação dos métodos propostos a analise de amostras biológicas, minerais e ambientais em diferentes estudos. O Capítulo 5 apresenta o desenvolvimento de um método simples para determinação direta de Br em amostras de polímeros por ablação a laser (LA)-ICP-MS, enquanto que os Capítulos 6, 7 e 8 abordam o desenvolvimento de métodos para medida da razão isotópica de halogênios em água do mar e amostras de gelo marinho por MC-ICP-MS. No Capítulo 2, uma nova metodologia para a determinação de Cl em amostras biológicas e botânicas usando SS-ETV-ICP-MS é apresentada. As amostras sólidas foram pesadas diretamente em plataformas de grafite (copos de grafite da técnica cup-in-tube) e inseridas no forno de grafite. Os parâmetros de potencial de rádio frequência (RF) e a vazão de gás carreador foram otimizados em 1300 W e 0,7 L min-1, respectivamente. Padrões aquosos foram utilizados para a obtenção da curva de calibração com o auxílio de modificadores pré-secos (Pd + Nd ou Pd + Ca) ou utilizando um material de referencia certificado (CRM) sólido com os mesmos modificadores pré-secos ou sem a utilização de modificadores. O limite de quantificação (LOQ) obtido foi 5 ?g g-1 sob condições otimizadas. A concentração de Cl foi determinada em cinco amostras de referência certificadas, com concentrações certificados para Cl, além de três amostras de referência certificados com concentrações certificadas para Cl indisponíveis, neste último caso, os resultados foram comparados àqueles obtidos utilizando espectrometria de absorção molecular de alta resolução com fonte contínua (HR-CS MAS). As concentrações obtidas demonstraram-se em acordo, a um nível de confiança estatística de 95%, com os valores certificados ou de referência.O Capítulo 3 apresenta um novo método para a determinação direta e simultânea Br e Cl em amostras de carvão utilizando SS-ETV-ICP-MS. O processo não requer pré-tratamento de amostras e necessita de pequenas alíquotas de massa de amostra (cerca de 0,5 mg). Todos os parâmetros operacionais, incluindo vazão de gás carreador e potencial de RF, foram otimizados para o máximo de sensibilidade. O uso de modificadores/ carreadores de aerossóis (Pd, Pd + Al e Pd + Ca) foi avaliado e a combinação de Pd e Ca foi escolhida, permitindo a adoção das temperaturas de pirólise e vaporização de 700 oC e 1900 oC, respectivamente. Cloro foi determinado com o auxilio de calibração utilizando padrões sólidos, enquanto Br foi determinado tanto por calibração aquosa quanto utilizando CRM sólidos. Os LOQs obtidos foram de 0,03 ?g g-1 para Br e 7 ?g g-1 para Cl, interferências espectrais não foram observadas.No Capítulo 4 foi avaliada a viabilidade da análise direta de sólidos por HR-CS MAS para a determinação de F e ETV-ICP-MS para determinação simultânea de Cl, Br e I em material particulado inalável no ar (PM10), coletados na região metropolitana de Aracaju, Sergipe, Brasil. As análises de F por HR-CS MAS foram realizadas monitorando a molécula de CaF que foi gerada a altas temperaturas na câmara de grafite após a adição de cálcio em uma relação Ca/ F de 35. As análises por ETV-ICP-MS foram realizadas utilizando Ca como modificador químico/ carreador de aerossol com a utilização concomitante de Pd como modificador permanente, a fim de evitar perdas de Cl, Br e I durante a etapa de pirólise. A abordagem de analise direta de sólidos resultou em LOQs adequados para a determinação de halogêneos em PM10, usando a calibração por adição de analito ou calibração utilizando um CRM solido. O método permitiu a quantificação dos halogênios em 14 PM10 coletadas em uma cidade costeira do nordeste do Brasil. Os resultados demonstraram variações de teor de halogênios de acordo com as condições meteorológicas, principalmente relacionados a chuvas, umidade e irradiação solar. O Capítulo 5 foi destinado à avaliação da utilização da LA-ICP-MS para análise de Br em amostras de polímeros. Os parâmetros operacionais do LA-ICP-MS, incluindo a vazão de gás carreador, potencial de RF, tamanho da cratera de ablação e frequência do laser foram otimizados para o máximo de sensibilidade. Os valores otimizados foram 0,6 L min-1 para vazão de gás carreador (He), 950 W de potencial de RF, 120 ?m de tamanho da cratera de ablação e 15 Hz de frequência do laser. Sob condições otimizadas foi possível determinar, com exatidão, Br em 5 amostras certificadas de polímeros e 5 amostras reais de polímeros obtidas em estabelecimentos locais em Ghent, Bélgica por calibração externa utilizando CRMs contendo diferentes concentrações de Br e por calibração externa utilizando apenas um CRM monitorando 12C+ como padrão interno. O LOQ obtido foi de 110 ?g g-1 para Br.O Capítulo 6 apresenta um método simples para medida da razão isotópica de Br em água do mar por MC-ICP-MS, utilizando nebulização pneumática para introdução da amostra. Os sinais dos isótopos de Br+ foram medidos livre de interferências utilizando alta resolução. O efeitos de memória para Br foi diminuído utilizando 5 mmol L-1 NH4OH como solução de limpeza entre as medidas. O conteúdo catiônico da água do mar foi removido por cromatografia catiônica utilizando uma resina Dowex 50WX8. Pré-concentração das amostras foi obtida por evaporação a 90°C, sem perda ou fraccionamento isotópico de Br. Discriminação de massas foi corrigida por correção externa utilizando bracketing, embora Sr, Ge e Se foram testados como potenciais padrões internos. Os valores 81Br/ 79Br obtidos para os materiais de referência isotópicos (NaBr) NIST (material de referencia padrão) SRM 977 e (água do mar) IRMM BCR-403 demonstraram estar de acordo com os valores da literatura.No Capítulo 7, a medida da razão isotópica de Cl em água do mar por MC-ICP-MS através de nebulização pneumática tradicional foi realizada utilizando, i) alta resolução de massa (potencial de resolução de 10.000) para resolver interferências espectrais, ii) 5 mmol L-1 NH4OH como solução de limpeza a fim de diminuir o efeito de memória e iii) uma concentração de Cl de = 70 mg L-1. A carga catiônica da água do mar e de sais de cloreto (NaCl, KCl) foi eficientemente removida sem afetar a composição isotópica original da Cl através de cromatografia catiônica utilizando resina de troca iônica Dowex 50WX8. O método desenvolvido demonstrou alta exatidão e precisão, atestadas pela medição da razão isotópica 37Cl/ 35Cl na amostra CRM NIST 975a (valor obtido de 0,319765 ± 0,000022, em comparação com um valor de referência de 0,319768 ± 0,000187 a uma precisão de ~ 0,007%, desvio padrão relativo, n = 3). Além disso, o valor???37Cl (baseado no padrão de cloro em água do mar, SMOC) foi determinado para cinco padrões diferentes que variaram de -0,54 a + 0,89 ?. O Capítulo 8 apresenta um estudo ambiental de Br e Cl em gelo marinho coletados durante a expedição Sea Ice Physics and Ecosystem eXperiment 2012, em diferentes profundidades e locais. Todas as medições de razão isotópicas de Br e Cl foram realizadas de acordo com os métodos apresentados no Capítulo 6 e 7. A concentração destes elementos variou de 700 para 31000 ?g L -1 para Br e de 200 para 8000 mg L-1 para Cl, sendo que as menores concentrações foram relacionados com o gelo coletado em maiores profundidades, estando a diminuição da concentração de Br e Cl provavelmente relacionadas a processos de dessalinização. Os valores de ?81Br e ??37Cl apresentaram relação linear com a suas concentrações, sugerindo que o processo de dessalinização desempenha um papel no fraccionamento isotópico no gelo do mar.

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CAPES
Os organoestânicos, principalmente o tributilestanho (TBT), são contaminantes ambientais, utilizados principalmente em tintas anti-incrustantes para navios. Eles sofrem bioacumulação e podem ser encontrados em mamíferos, inclusive em seres humanos. A principal fonte de exposição é a ingestão de alimentos contaminados. Esse estudo possuiu como objetivo a determinação de estanho em tecidos de ratas expostas cronicamente a TBT utilizando espectrometria de massas com plasma acoplado indutivamente (ICP-MS). Ratas Wistar adultas foram usadas na experimentação, sendo divididas dois grupos: o grupo exposto a 100 ng kg-1 dia-1 de TBT por 15 dias e o grupo de referência que recebeu somente o veículo durante o mesmo período de exposição. Ao final da exposição, os animais foram sacrificados e coletados plasma, coração, rim, pulmão, fígado e ovário para análise. As amostras foram secas em estufa por 72 horas e pulverizadas. A determinação de estanho foi realizada por ICP-MS após a digestão ácida assistida por micro-ondas de uma amostra com aproximadamente 100 mg. O limite de detecção (LD) calculado foi 4,3 ng L-1, o que permite a determinação de estanho em amostras de tecidos de animais usados para experimentação. A exatidão foi verificada pela análise do material de referência certificado de urina, Seronorm Urine (54,6 ± 2,7 μg L-1), tendo como resultado 50,1 ± 3,8 μg L-1. A concentração de estanho foi determinada em amostras de plasma, coração, rim, pulmão, fígado e ovário do grupo exposto a TBT e do grupo controle. Houve diferença estatisticamente significativa entre os dois grupos para todas as amostras analisadas. As diferenças entre os grupos foram mais pronunciadas nas amostras de fígado e rim. Além disso, este estudo mostrou que a presença de estanho no organismo de ratas distribui-se pelos tecidos acarretando em alterações morfofisiológicas já descritas em ovários, coração e fígado
The organotin compounds, especially tributyltin (TBT), are environmental contaminants are mainly used in antifouling paints for ships. The organotin compounds, especially tributyl (TBT), environmental contaminants are mainly used in antifouling paints for ships. They may bioaccumulate and can be found in mammals, including humans. The main source of exposure is ingestion of contaminated food. This study aimed possessed the determination of tin in rats exposed tissue chronically TBT using mass spectrometry with inductively coupled plasma (ICP-MS). Adult Wistar rats were on trial, and divided in two groups: the group exposed to 100 ng TBT kg-1 day-1 for 15 days and the reference group receiving only the vehicle during the same period of exposure. At the end of exposure, the animals were sacrificed and plasma, heart, kidney, lung, liver and ovarian were collected for analysis. The samples were dried for 72 hours and about 100 mg of each sample were subjected to acid digestion microwave. The determination of tin was carried out by ICP-MS after acid digestion microwave assisted by a sample with approximately 100 mg. The limit of detection (LOD) was calculated 4.3 ng L-1, which allows the determination of tin in tissue samples from animals used for experimentation. Accuracy was assessed by analyzing the certificate urine reference material Seronorm Urine (54.6 ± 2.7 ug L-1), resulting in 50.1 ± 3.8 ug L-1. After validation, the tin concentration was determined in plasma, heart, kidney, lung, liver and ovarian samples in the TBT group and in the control group. There was a statistically significant difference between the two groups for all samples. Differences between groups were most prominent in samples of liver and kidney. Furthermore, this study showed that the presence of tin in rat’s body is distributed in the tissues, resulting in morphological and physiological changes already founded in ovary, heart and liver