Introduction 61Cu (T1/2 = 3.33 hr, Eβ= 1.22 MeV, 61.4 %) is an attractive isotope for positron emission tomography (PET) radiopharmaceutical agents such as ATSM and PTSM. Various separation processes have been reported for the production of 61Cu on a medium cyclotron using 13–22 MeV protons on natural and enriched 64Zn target materials [1,2]. This work, investigates production of 61Cu using both natural and enriched 64Zn targets and its separation. Three types of resins were used to assess for their efficiency and speed to separate the desired 61Cu from the 66,67,68Ga and 64Zn and for the recycling of 64Zn target material. The effective specific activity of purified 61Cu, was determined by ICP-MS and its titration with various polyaza and polycarboxylate complexing ligands. Material and Methods 1. Production and Separation Targets were irradiated by proton beam of IBA cyclotron 18/18MeV via the 64Zn(p,α) 61Cu and natZn(p,x) 61Cu reactions using an enriched 64Zn foil(15×15×0.05mm, ~50 mg) and natural foil (diameter 25 mm, 0.05 mm,~ 60 mg). Thirty minute irradiations were conducted with incident proton energies between 11.7–12.0 MeV and beam currents of 20 and 40 µA. Irradiated Zn targets were dissolved in 8M HCl at 150 oC then evaporated to dryness. Trace water to the resultant residue (twice) and resultant solutions evaporated to dryness. The residue was re-dissolved in 2ml of 0.01M HCl before loading onto a Cu-resin column (FIG. 1) Zn and Ga isotopes were collectively eluted using 30 ml of 0.01M HCl. The Cu was then removed using 1.5 ml of 8M HCl and passed directly onto a cation exchange followed by an anion exchange column. An additional 3 ml of 8M HCl was used to rinse the cation exchange column and ensure quantitatively removal of Cu (II) ions. The Cu was finally eluted from the anion exchange column using 3 ml of 2M HCl. The Cu solution was heated up at 150 oC until evaporated to dryness and 61Cu final product dissolved in 400–800 μL of 0.01M HCl. 2. Specific activity of 61Cu The specific activity (GBq/µmol) of the purified 61Cu was determined by ICP-MS and compared with that determined using dota, nota and di-amsar complexing ligands. For each 61Cu production run aliquot of final solution (100 µL) was left to decay before dilut-ing to 10 mL with 10% HNO3. Decayed samples were sent to ChemCentre (Curtin University) for ICP-MS analysis. Each sample was analysed for Cu, Al, Ca, Co, Fe, Ga, Ni, Si, and Zn, which are known to compete with Cu2+ for ligand complexation. Effective specific activity of the 61Cu was deter-mined by titrating various known concentration of ligands with 61Cu solution. The method is detailed in the literature [3]. Briefly, varying concentrations of each ligand was prepared in 0.1M sodium acetate buffer pH 6.5 to a total volume 20 µL. Fixed concentration of diluted 61Cu (0.01M HCl) in 10 µL was added to each ligand solution. The mixtures were vortexed then left to incubate at the room temperature for 30 mins. Two uL aliquots were withdrawn (in triplicate) from each reaction mixture and spot-ted on ITLC –SA. [Mobile phase: 0.1M NaCl: 0.1M EDTA (9:1) for Cu2+ and diamsar mixtures: Rf <0.2 Cu-diamsar; Rf > 0.8 free Cu2+ and 0.1M sodium acetate pH 4.5: H2O: MeOH: ammonium hydroxide (20:18:2:1 v/v) for Cu2+ dota and nota mixtures: Rf >0.8 Cu-dota and Cu-nota Rf < 0.2 free Cu2+]. Complexation of the 61Cu with each ligand was complete within 30 mins at room temperature. Concentration of Cu2+ was deter-mined from the 50% labelling efficiency. Results and Conclusion 1. Production and Separation The radioisotopes production from natZn target must be minimized by the optimum proton energy to reduce a radiation dose in the final product. The excitation functions of 66,67,68Ga ,65Zn and 61Cu are shown in FIG. 2. Proton beam energy of 11.7 MeV was used for both Zn targets to minimise the production of Ga isotopes and prevent formation of 65Zn. For the enriched 64Zn target (99.30%) higher proton energy could be used for the production of 61Cu allowing for increased yields and reduce radio contaminants. Previously, we used anion and cation exchange resin as described in the literature to separate the 61Cu [1]. Unfortunately the literature method was too long (up to 3 hours) and requiring high concentration of HCl and long evaporation times compromising achievable yields [4]. Thieme S. et al., 2013 [2] reported the successful use of Cu-resin for the separation of Cu radioisotopes and it was of interest to the current work to test this material for the separation of 61Cu in our hands. A cation, anion exchange and Cu-resin were combined into closed system to separate the 61Cu within 30 mins (FIG. 1). The system is designed to contain the transfer of solutions be-tween each column using simple plunger to force solution through and between each column. This system afforded an easy, reliable and fast separation of 61Cu that could be completed within 30 min. 2. Specific activity The specific activity of 61Cu was determined using ICP-MS and by titration with three ligands is summarized in TABLE 1. The ICP-MS data show values ranging from 9.2 to 32.4 GBq/μmol for 8 production runs. Specific activity determine using nota and dota were in all cases lower than the ICP MS data indicating some interference from the other metal ion contaminates such as Fe(ii/Iii), Ni (II), Ca (II), Zn (II), Ga (III). The specific activity determine using diamsar, which is known to be highly selective for Cu(II) (and Zn(II) and Fe(III)) in the presence of alkali and alkaline earth ions gave values significantly higher effective specific activity than that obtained using ICP MS. Variations in values can be explained by presence of contaminating metal ions.

En la presente Tesis Doctoral la técnica de ablación laser acoplada a ICP-OES/MS ha sido empleada para analizar muestras sólidas, como catalizadores usados en el refinado del petróleo y polímeros. Se han llevado a cabo dos tipos de análisis, un análisis global de las muestras que proporciona información general y un análisis localizado que permite obtener información acerca de la distribución espacial de los elementos de interés en las muestras. Las diferentes variables de la técnica ablación láser son estudiadas con el fin de seleccionar aquellas que conducen una señal alta y estable, así como a un menor grado de fraccionamiento. Este estudio se realiza para cada tipo de muestra, ya que los resultados dependen de la matriz estudiada. Además, en esta Tesis doctoral se desarrolla un método de calibración para llevar a cabo un análisis cuantitativo de las muestras sólidas, basado en la deposición de patrones líquidos sobre la muestra sólida. Este método es conocido como “dried droplet calibration approach” (DDCA), y permite cuantificar elementos presentes en muestras sólidas sin necesidad de usar materiales de referencia sólidos. Este nuevo método de calibración compensa el fraccionamiento elemental y los efectos de matriz, proporcionando resultados exactos y preciosos para muestras complejas tales como vidrios, catalizadores y polímeros.

[pt] O exame de mineralograma capilar fornece as concentrações de elementos tóxicos e essenciais no cabelo. O uso de produtos capilares, além de poderem representar uma fonte de exposição, é possível que causem alterações na composição mineral do cabelo. Neste trabalho, amostras de cabelo natural foram submetidas a tratamentos com diferentes tinturas e, posteriormente, analisadas seguindo a metodologia pré-estabelecida para determinação multielementar por espectrometria de massas com plasma indutivamente acoplado (ICP-MS). A composição elementar do cabelo humano natural foi comparada com as determinadas nas mesmas amostras de cabelo submetidas a tratamentos com diferentes tintas. Utilizando o teste estatístico Kruskal-Wallis, foi possível identificar diferenças significativas (p < 0,05) para os elementos Na, K e Mg, cujas concentrações aumentaram (de 100 a 5000x) após o uso das tinturas permanentes e semipermantes, enquanto para os cabelos que foram submetidos a tratamentos com corantes naturais isso não foi observado. Alguns elementos como Al, Fe, P tiveram decréscimo em suas concentrações (de 20 a 40%) após o uso desses tratamentos. Diante disso, foi possível determinar que alguns elementos são transferidos ou removidos do cabelo após o uso de determinados produtos, confirmando que tratamentos estéticos podem interferir nos resultados do exame do mineralograma capilar, devendo ser avaliada a necessidade da realização do mesmo em pacientes com cabelo tingido ou a possibilidade de aguardar por, pelo menos, 3 meses sem o uso de tratamentos permanentes antes da coleta da amostra para realização do exame. / [en] The hair mineral analysis test reports the concentrations of toxics and essential elements inside the hair structure. The utilization of hair care products, in addition to being able to represent an exposure source, also can be responsible for certain changes in the mineral composition of the hair. In present work, natural hair samples were treated with different dyes and, posteriorly, studied following the pre-established protocol for multi-element analysis by means of inductively coupled plasma mass spectrometry (ICP-MS). Hence, the element compositions of natural human hair after different treatments were compared. With the help of the Kruskal-Wallis statistical test, it was possible to identify significant differences (p < 0.05) for the elements, such as Na, K and Mg. Their concentrations increased from 100 to 5000x after the use of permanent and semipermanent dyes, while in the case of the hair samples treated with the natural dye no significant difference was observed. The concentrations of some elements, such as Al, Fe, P decreased (from 20 to 40%) after the respective treatments. Therefore, it was established that some elements are transferred or removed from the hair after the use of certain products, confirming that aesthetic treatments can interfere the results of the hair mineral analysis test. It reasons testing in patients with dyed hair or the possibility of waiting for about 3 months without the use of permanent treatments before sample collection for the analysis.

No description available.

[pt] A introdução de solventes orgânicos em espectrômetros com plasma indutivamente acoplado (ICP) representa uma limitação à confiabilidade dos resultados pela incidência de efeitos de matriz. Estratégias de calibração como Standard Dilution Analysis (SDA) e Multi-energy Calibration (MEC) propõem contornar as interferências de matriz, reduzindo o tempo de análise, o consumo de reagentes e a geração de resíduos. Na SDA com dois padrões internos (IS), a aquisição do sinal é feita ao longo do tempo durante a mistura de duas soluções analíticas: uma formada por 50 % de amostra + 50 por cento de solução-padrão contendo os analitos e um IS (S1) e outra formada por 50 por cento de amostra + 50 por cento do branco e um segundo IS (S2). Já na calibração por MEC, que também utiliza duas soluções similares à SDA, porém, sem IS, mede-se simultaneamente sinais dos elementos em diferentes comprimentos de onda. Estes métodos foram aplicados para a determinação de Ca, K, Mg, Na, P, Si e S em amostras de biodiesel diluídas em xileno, por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) e comparados com as calibrações por adição de analito (SA) e padronização interna (IS). Os limites de quantificação não apresentaram diferença significativa em relação aos métodos tradicionais, variando de 0,05 mg kg-1 (Ca) a 1,4 mg kg-1 (Na) para SDA e de 0,01 mg kg-1 (Mg) a 0,98 mg kg-1 (P) para MEC. A veracidade foi verificada através de testes de recuperação em amostras de biodiesel e no material padrão de referência NIST 1084a (Wear metals in lubricating oil), com recuperações de 101 ± 6 por cento para SDA e de 108 ± 8 por cento para MEC. A estabilidade do sinal analítico a longo prazo e os menores impactos econômicos e ambientais fazem a SDA e a MEC interessantes para a determinação elementar em amostras de biodiesel e óleo diluídas em xileno. / [en] Direct introduction of organic solvents into inductively coupled plasma (ICP) spectrometers represents a limitation to reliability of the results due to matrix effects. Different calibration methods, such as Standard Dilution Analysis (SDA) and Multi-energy Calibration (MEC) have been proposed to overcome this kind of interference, reducing analysis time, reagent consumption and waste generation. In SDA with two internal standards (IS), the signal is acquired over time during the mixing process of two analytical solutions: one consisting of 50 percent of sample + 50 percent of analytical standards and IS1 (S1) and the other consisting of 50 percent of sample + 50 percent of blank solution and IS2 (S2). In MEC calibration, which also uses two solutions similarly to SDA, but without IS, signals from the elements are measured simultaneously at different wavelengths. These methods were applied to the determination of Ca, K, Mg, Na, P, Si and S in biodiesel samples diluted in xylene by inductively coupled plasma optical emission spectrometry (ICP OES) and compared to calibrations by standard addition (SA) and internal standardization (IS). Limits of quantification showed no statistically significant difference compared to the traditional methods, whereas the limits found by SDA ranged from 0.05 mg kg-1 (Ca) to 1.4 mg kg-1 (Na) for SDA, and from 0.01 mg kg-1 (Mg) to 0.98 mg kg-1 (P) for MEC. The trueness was verified through recovery tests on biodiesel samples and the standard reference material NIST 1084a (Wear metals in lubricating oil), with recoveries of 101 ± 6 percent for SDA and 108 ± 8 percent for MEC. Long-term signal stability and lower economic and environmental impacts places SDA and MEC as an interesting strategy for elemental determination in biodiesel and oil samples diluted in xylene.

[pt] A Cannabis é um insumo medicinal histórico e em atual expansão para as mais diversas aplicações medicinais, cosméticas, recreativas e têxteis. O mercado medicinal de Cannabis se encontra em destaque no cenário global, principalmente na forma de apresentação de extratos oleosos. Os extratos herbais de Cannabis (CHE) são um dos produtos de maior interesse e mais procurados para abordagens terapêuticas de uma diversidade de condições clínicas. Parâmetros de controle de qualidade regulados e métodos padronizados de avaliação de risco são atualmente demandados para produtos à base de Cannabis. O potencial medicinal da Cannabis é atribuído principalmente à biossíntese de uma classe especial de metabólitos: os fitocannabinoides. O canabidiol (CBD), o tetrahidrocanabinol (THC) e o canabinol (CBN) são destacados como os principais fitocanabinoides alvos de preocupação farmacêutica. Além disso, o monitoramento de impurezas e adjuvantes, como o teor de metais e metaloides, também é fundamental para garantir a segurança e a integridade destes produtos. Técnicas analíticas avançadas retratam alternativas poderosas para o monitoramento de produtos à base de Cannabis. No entanto, etapas analíticas adicionais precisam ser otimizadas criticamente para acompanhar o desempenho instrumental e o Design de Experimentos (DoE) fornece uma abordagem rápida, simples, confiável e eficaz para alcançar otimizações multivariadas bem-sucedidas. Neste trabalho apresentamos o desenvolvimento de dois métodos otimizados por DoE para análise de CHE: um método de quantificação de CBD, THC e CBN por UHPLC-HRMS/MS e três métodos de determinação multielementar por ICP-MS. Para a quantificação de fitocannabinoides, as condições instrumentais foram otimizadas frente a um planejamento do tipo Plackett-Burman para 7 variáveis, buscando-se otimizar a reprodutibilidade do fenômeno de ionização. Valores de desvio-padrão relativo de 2 por cento, 2 por cento e 5 por cento foram alcançados para CBD, THC e CBN, respectivamente. Além disso, planejamentos do tipo Fatorial Completo e Box-Behnken foram utilizadas para propor um protocolo otimizado de extração líquido-líquido assistida por ultrassom com 6,9 mL de metanol:hexano 9:1 v/v, 18 min de tempo de agitação e 25 min de tempo de sonicação. O modelo preditivo construído foi validado, apresentando valores de acurácia entre 86 e 120 por cento. O desempenho analítico foi validado por diretrizes farmacêuticas brasileiras de referência (ANVISA RDC 166/2017) frente a três diferentes abordagens de calibração: calibração externa, adição-padrão e Matrix Matching. Valores satisfatórios de exatidão, precisão, sensibilidade, linearidade e efeito de matriz foram alcançados com a utilização deste último, sendo representativo de uma alternativa eficiente, de maior custobenefício e de maior frequência analítica. A aplicação desta metodologia em um lote de 4 amostras reais revelou uma preocupação significativa em relação à avaliação de risco desses produtos, sendo observada uma discrepância significativa entre a descrição do rótulo e o conteúdo quantificado de CBD (mais de 10.000 vezes menor). THC e CBN não foram encontrados acima do Limite de Quantificação para nenhuma das amostras. Fenômeno que compromete não só seu potencial terapêutico, mas também revelando um ponto cego da segurança do consumidor. Para a determinação multielementar, parâmetros instrumentais atrelados ao plasma e à introdução de amostra foram otimizados por planejamentos do tipo Composto Central para maximização de sensibilidade e minimização de interferências, alcançando-se condições de compromisso com taxas de otimização globais superiores a 80 por cento. Quanto ao preparo de amostra, três métodos foram explorados: digestão ácida aberta em chapa de aquecimento, digestão ácida em vaso fechado e diluição direta com solvente orgânico, assim como três diferentes abordagens de calibração: calibração externa, Matrix Matching e adição-padrão. O desempenho de todos os métodos foi criticamente avaliado em relação à exatidão, precisão, sensibilidade, efeito de matriz e impacto ecológico. O método empregando decomposição em chapa de aquecimento com 6,9 mL de HNO3 diluído 10 por cento v/v com aquecimento por 60 min àa 100 graus C e uma abordagem de calibração por Matrix Matching forneceu o melhor desempenho geral e foi aplicado para analisar um lote de 6 amostras de Cannabis em comparação com óleo de gergelim, um óleo vegetal de consumo comum e muito utilizado como veículo farmacotécnico nos extratos de Cannabis. Em geral, foram determinados baixos teores de metais e metaloides e, comparando os extratos de Cannabis com o óleo vegetal, diferenças estatisticamente significativas foram identificadas apenas para Au, Cu, K, Li, Mg, Mn, Ni, Pb, Ti e Zn. O Pb foi encontrado em níveis mais altos em todas as amostras de Cannabis, variando de 11,7 a 12,4 (micro)g.g-1, em desacordo (teor quase 3 vezes maior) com as diretrizes da FDA para elementos potencialmente tóxicos. Por sua vez, Li, Mg, Mn, Ni, Ti e Zn foram encontrados em níveis discordantes entre as amostras, sugerindo uma heterogeneidade relevante na produção dos óleos e um controle de qualidade não padronizado para esses produtos. / [en] Cannabis herbal extracts (CHE) are one of the most interesting and sought products for therapeutic approaches of a diverse number of clinical conditions. Regulated quality control parameters and risk assessment methods are needed for Cannabis-based products. Advanced analytical techniques portray powerful alternatives to Cannabis-based products monitoring. However, further analytical steps need to be critically optimized to keep up with instrumental performance. In this work, analytical methods for phytocannabinoids quantification by UHPLCHRMS/MS and multielement determination by ICP-MS, both in CHE, were developed and optimized by Design of Experiments. For UHPLC-HRMS/MS, an ultrasound-assisted liquid-liquid extraction with methanol:hexane 9:1 v/v was proposed, analytical performance was successfully validated by gold-standard brazilian pharmaceutical guidelines, proving its efficiency in question. For multielement determination, three sample preparation methods were explored (acid decomposition in open-vessel, acid decomposition in closed-vessel, and organic solvent direct dilution). Their performances were critically evaluated regarding analytical metrics, ecological impact and user-friendliness. The open-vessel method with diluted HNO3 provided the overall best performance and was applied to analyze 6 CHEs and one sesame oil sample. The phytocannabinoids quantification suggested a major discrepancy between CHE label description and quantified content, as CBD was over 10,000-times lower and both THC and CBN could not be determined. Also, in general, low metal and metalloid contents were determined, but significant potentially toxic metals content was found. By comparing with sesame oil, statistically significant differences were identified only for Au, Cu, K, Li, Mg, Mn, Ni, Pb, Ti, and Zn. Lead were found at higher levels for all Cannabis samples in a range 11.7 to 12.4 (micro)g g-1 , in disagreement with FDA guidelines for potentially toxic elements (10 (micro)g g-1 ). Li, Mg, Mn, Ni, Ti and Zn were found at discordant levels between samples, suggesting a relevant heterogeneity and non- standardized quality control for these products.

[pt] Os metais e metaloides representam um problema global pela possibilidade de bioacumulação e biomagnificação ao longo de teias tróficas aquáticas. Os elasmobrânquios, grupo taxonômico que inclui as raias e tubarões, são vulneráveis à pesca e poluentes químicos. Poucos estudos avaliaram a presença e os efeitos de metais e metaloides nestes animais e estudos com amostragem não-letal são ainda escassos. Este estudo avaliou o potencial da bílis como biomarcador de contaminação recente em três espécies de elasmobrânquios ameaçados capturados artesanalmente na cidade do Rio de Janeiro, Gymnura altavela, Dasyatis hypostigma e Pseudobatos horkelii. As concentrações de metais e metaloides biliares foram determinadas por espectrometria de massa com plasma indutivamente acoplado (ICP-MS), as metalotioneínas por espectrometria UV-Vis e as associações entre metais intracelulares e metalotioneínas por cromatografia líquida de alta eficiência com separação por exclusão de tamanho acoplada a ICP-MS (SEC-HPLC-ICP-MS). No geral, Fe apresentou as maiores concentrações (máx. 194,8 mg L-1) e Sn as menores (máx. 0,004 mg L-1), quantificado em apenas cinco indivíduos do total estudado (107). Arsênio e cobre apresentaram maiores médias (10,9 e 5,2 mg L-1, respectivamente) nas amostras de bílis de raia viola, a única espécie capturada em Copacabana. Correlações estatísticas entre as concentrações de metalotioneínas, índices biomorfométricos e concentrações elementares nas frações das amostras de bílis indicam contaminação ambiental e potenciais efeitos sub letais no desenvolvimento e reprodução desses animais. Os resultados obtidos por SECHPLC-ICP-MS indicam diferenças metabólicas nas rotas de destoxificação das diferentes espécies. Conclui-se que o uso de bílis de elasmobrânquios é uma alternativa eficaz e que permite a amostragem não-letal para monitorar a contaminação ambiental recente por metais e metaloides. / [en] Metals and metalloids can represent a significant global issue, due to the potential for high bioaccumulation and biomagnification along aquatic food webs. Elasmobranchs, a taxonomic group that includes rays and sharks, are highly vulnerable to fishing activities and chemical pollutants. Few studies have investigated the presence and impacts of metals and metalloids in these animals, and studies with non-lethal sampling methods are still scarce. This study evaluated the potential of bile as a biomarker of recent contamination in three threatened species of elasmobranchs artisanally captured in the city of Rio de Janeiro, Gymnura altavela, Dasyatis hypostigma, and Pseudobatos horkelii. Biliary metal and metalloid concentrations were determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), metallothioneins by UV-Vis spectrometry, and associations between intracellular metals and metallothioneins were investigated by Size Exclusion-High-Performance Liquid Chromatography coupled to ICP-MS (SEC-HPLC-ICP-MS). Overall, Fe presented the highest concentrations (0.7 more or less 0.1 mg L-1) and Sn the lowest (max. 0.004 mg L-1), quantified in only five individuals of the total studied (107). Arsenic and copper showed higher averages (10.9 and 5.2 mg L-1, respectively) in bile samples from Brazilian guitarfish, the only species caught in Copacabana. Statistical correlations among metallothionein concentrations, biometric indices, and elemental concentrations in bile fractions suggest environmental contamination and potential sublethal effects on the development and reproduction of these animals. Results obtained from SEC-HPLC-ICP-MS indicate metabolic differences in detoxification pathways among the various species. In conclusion, the utilization of elasmobranch bile is an effective alternative that allows non-lethal sampling for monitoring recent environmental contamination by metals and metalloids.

Bei der Schwefelquantifizierung in Kupfer und anderen reinen Metallen zeigte sich in der Vergangenheit eine mangelnde SI-Rückführung und zusätzlich inkonsistente Ergebnisse, wenn verschiedene Methoden verglichen wurden. Um diesen Mangel zu beheben ist ein Referenzverfahren erforderlich, welches SI-rückführbare Werte mit einem zuverlässigen Unsicherheitsbudget ermöglicht. In dieser Studie wurde ein entsprechendes Referenzverfahren zur Quantifizierung von Gesamtschwefel in Kupfer basierend auf der induktiv gekoppelten Plasma-Massenspektrometrie und der Isotopenverdünnungsanalyse (ICP-IDMS) entwickelt. Um diese Probleme zu lösen wurde mit Hilfe der Ionenaustauschchromatographie ein Schwefel-Matrix-Trennverfahren entwickelt. Dieses Trennverfahren wurde mit ICP-IDMS kombiniert, um Schwierigkeiten mit der Kalibrierung zu lösen und fehlende metrologische Konzepte einzuführen. So wurden die in diesem Projekt erzielten IDMS-Messwerte für die Kalibrierung von GDMS und LA-ICP-MS verwendet, beides Verfahren die im industriellen Einsatz üblich sind. Dadurch konnten mit beiden Routineverfahren zuverlässige Ergebnisse erzeilt warden, die zudem auf SI rückführbar sind. Darüber hinaus wurde ein auf der LA-ICP-IDMS basierendes Verfahren entwickelt, um den Probenvorbereitungsschritt von ICP-IDMS mit Schwefel-Matrix-Trennung zu reduzieren. Die Vorteile dieser Methode sind ein geringerer Arbeits- und Zeitaufwand, die SI- Rückführung der Messergebnisse und eine für LA-ICP-MS vergleichsweise hohe Genauigkeit. Die Schlüsselrolle hierbei spielte der innovative Einsatz von Polyethylenfritten als Trägermaterial der aufgelösten Probe. Dadurch war die Quantifizierung von Schwefel in Kupferproben mittels LA-ICP-IDMS möglich. Die wesentlichen Parameter wie Absorptionseffizienz der Fritten und Matrixeffekt wurden untersucht. Das entwickelte Verfahren konnte mit Hilfe der ICP-IDMS vollständig validiert werden. / Sulphur quantification in copper and other pure metals in the past revealed a lack of SI-traceability and also showed inconsistent results, when different methods are compared. Therefore, a reference procedure is required to enable SI-traceable measurement results accompanied by a sound uncertainty budget. In this study, such a procedure was developed for the quantification of total sulphur in copper using inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS). For solving these problems ion exchange chromatography was applied, and a sulphur-matrix separation procedure was developed. This procedure was combined with ICP-IDMS to solve difficulties with the calibration and to realize metrological concepts. An application of the IDMS procedure was realized by using the measurement results of specific copper samples values for calibrating glow discharge mass spectrometry (GDMS) and laser ablation ICP-MS (LA-ICP-MS). Both techniques are considered routine techniques. Thus, they could provide reliable results which are traceable to the SI. Additionally, a procedure based on LA-ICP-IDMS was developed to significantly reduce the sample preparation step of ICP-IDMS with sulphur-matrix separation. This procedure is less laborious and the measurement results are still SI traceable and offer a comparatively high accuracy for LA-ICP-MS. Key for this development was the innovative application of polyethylene frits as support material for the dissolved sample. Thus, the quantification of sulphur in copper samples by LA-ICP-IDMS could be realized. The essential parameters are investigated such as the absorption efficiency of the frit and matrix effects. The developed procedure was fully validated by means of the ICP-IDMS results.

A espectrometria de massas com plasma acoplado indutivamente com simples quadrupolo (q-ICP-MS) e cela de reação dinâmica (DRC-ICP-MS) foi avaliada para determinação seqüencial de Al, As, Cd, Co, Cu, Cr, Mn, Mo, Pb, Pt, Sb, Se, Sn, Te, Tl, V e Zn em sangue. Para as análises, amostras de sangue (200 µL) foram diluídas 1:50 em uma solução contendo 0,01% v/v Triton® X-100 e 0,5% v/v de ácido nítrico. As calibrações foram realizadas com ajuste de matriz, utilizando sangue ovino. Como gás de reação utilizou-se a NH3. O uso do DRC foi fundamental para a determinação de Cr e V. A escolha da melhor vazão do gás e a otimização do parâmetro de rejeição (RPq) foram estudadas utilizando sangue base ovino ou uma solução de matriz sintética (SMS), de acordo com a concentração do analito no sangue base. Os limites de detecção (3s/coeficiente angular) para determinação de 27Al, 75As, 111Cd, 59Co, 63Cu, 55Mn, 98Mo, 208Pb, 195Pt, 123Sb, 82Se, 120Sn, 130Te, 205Tl e 66Zn em sangue por q-ICP-MS foram 0,223; 0,014; 0,003; 0,011; 0,304; 0,009; 0,009; 0,003; 0,001; 0,005; 0,264; 0,006; 0,010; 0,001; 0,834 µg L-1, respectivamente, e para determinação de 52Cr e 51V em sangue por DRC-ICP-MS utilizando o gás de reação amônia os limites de detecção foram de 0,007 e 0,006 µg L-1. Para a determinação de 27Al, 63Cu, 65Cu, 64Zn e 66Zn em sangue por q-ICP-MS através da calibração com ajuste de matriz com SMS os limites de detecção foram 0,083; 0,090; 0,055; 0,281; 0,306 µg L-1, respectivamente. A validação do método foi realizada por meio da análise de materiais de referência do INSP-Canadá, NYSDOH-EUA e Seronorm-Noruega. / The use of inductively coupled plasma mass spectrometry with quadrupole (q-ICP-MS) and dynamic reaction cell (DRC-ICP-MS) was evaluated for sequential determination of Al, As, Cd, Co, Cu, Cr, Mn, Mo, Pb, Pt, Sb, Se, Sn, Te, Tl, V and Zn in whole blood by q-ICP-MS or DRC-ICP-MS methods. Prior to analysis, sample (200 µL) were diluted 1:50 v/v in a solution containing 0.01% v/v Triton® X-100 and 0.5% v/v nitric acid. For all elements, except Cr and V, the instrument was operated in q-ICP-MS mode. The use of DRC was only mandatory for Cr and V. NH3 was evaluated as the reaction gas. Selection of best flow rate of reaction gas and optimization of the quadrupole dynamic bandpass rejection parameter (RPq) were carried out, using base whole blood or synthetic matrix solution (SMS), in according with element base blood concentration. Method detection limits (3s/slope) for 27Al, 75As, 111Cd, 59Co, 63Cu, 55Mn, 98Mo, 208Pb, 195Pt, 123Sb, 82Se, 120Sn, 130Te, 205Tl and 66Zn determination in whole blood by q-ICP-MS against matrix matching calibration (base blood) were 0.223; 0.014; 0.003; 0.011; 0.304; 0.009; 0.009; 0.003; 0.001; 0.005; 0.264; 0.006; 0.010; 0.001; 0.834 µg L-1, respectively, and for 52Cr and 51V determination in whole blood by DRC-ICP-MS the detection limits were 0.007 e 0.006 µg L-1. For 27Al, 63Cu, 65Cu, 64Zn and 66Zn determination by q-ICP-MS through matrix matching calibration with SMS the detection limits were 0.083; 0.090; 0.055; 0.281; 0.306 µg L-1, respectively. Method validation was accomplished by the analysis of reference materials from INSP-Canada, NYSDOH-USA, Seronorm-Norway.

<p>The performance of different types of nebulisers: Vulkan direct injection nebuliser (Vulkan DIN), direct injection high efficiency nebuliser (DIHEN), microconcentric nebuliser coupled to cyclonic or double pass spray chamber (MCN-C or MCN-DP, respectively) was investigated and compared when used for sample introduction to ICP-MS or ICP-OES. With ICP-OES, in axial viewing mode, intensity distributions across the radius of the plasma (radial intensity profiles) were determined for different spectral lines with Esum 1.85-15.41 eV to determine fundamental plasma properties for various matrices using Vulkan DIN and MCN-C. The results showed that with the MCN-C the ionisation temperature (Tion) was about the same across the measured region of the plasma (±3.0 mm) whereas with the Vulkan DIN the Tion was significantly lower in the centre of the plasma. A large deviation from local thermodynamic equilibrium, as well as deteriorated stability, was observed for the plasma when using the Vulkan DIN.</p><p>With ICP-MS noise power spectra (NPS) were generated to identify sources of noise. NPS showed that the magnitude of white noise for the tested sample introduction systems decreased in the following order: Vulkan DIN > DIHEN > MCN-C > MCN-DP. This order follows the decrease of mean droplet size and span of the size distribution, indicating that the white noise is caused by spatial and temporal non-uniform desolvation and ionisation. Another source of noise arose from the peristaltic pump and the magnitude of pump interference noise decreased in the following order: DIHEN > MCN-C/DP > Vulkan DIN. Mains power interference noise and 1/f noise were lower for the direct injection nebulisers compared to the spray chamber systems. The contribution or effects of these noise components on relative standard deviations of steady-state ion-count rate and isotope ratio measurements is discussed in this thesis.</p><p>Aerosols generated by the Vulkan DIN and the DIHEN were also directly characterised using Particle Dynamic Analysis. The Vulkan DIN produced particles with a mean diameter of ~30 µm and a size distribution between 2-80 µm. With the DIHEN the corresponding values were ~11 µm and 1-40 µm, respectively, with a few particles at 55-78 µm. The mean velocity of particles from the Vulkan DIN was ~10 m s-1 and from the DIHEN ~18 m s-1. The lower velocity allows longer residence time counteracting the effects of the larger droplet size.</p>