No description available.

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.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / In this study different methods for speciation of Sb(III) and Sb(V) in meglumine antimoniate (NMG) were evaluated. Liquid chromatography (LC) combined or not with hydride generation (HG) was investigated for separation of Sb(III) and Sb(V). Inductively coupled plasma mass spectrometry (ICP-MS) was used as detector. A flow injection system together with hydride generation (FI-HG) coupled with atomic absorption spectrometry (AAS) was also employed for the selective determination of Sb(III) in presence of Sb(V). Two anion-exchange columns (Dionex, IonPacAS14 and Hamilton, PRP-X100) were evaluated for Sb(III) and Sb(V) separation by LC. Parameters related to the mobile phase, such as type (EDTA, potassium phthalate, and potassium phthalate + EDTA), concentration (0.5 to 10 mmol L-1), pH (3.5 to 7.0), flow rate (0.25 to 1.75 mL min-1) and elution mode (isocratic and gradient) were studied. The volume of sample injected into the chromatograph was set at 200 μL. For the chromatographic separation, the mobile phase which led to improved separations of Sb(III) and Sb(V) was the EDTA in concentrations of 0.5 mmol L-1 and 1.0 mmol L-1 for the IonPac and PRP-X100 columns, respectively. The most appropriate parameters related to the FI-HG system were also evaluated and set, such as reductant of Sb(III) (NaBH4 0.1%, m/v), complexant of Sb(V) (10% m/v citric acid,), water as the sample carrier, analytical path (300 cm), volume of sample (100 μL), total flow rate of solutions (8.5 mL min-1) and flow rate of carrier gas (0.4 mL min-1). In order to identify and/or quantify the species of Sb present in the NMG, the samples were diluted in water only. Through the use of LC-ICP-MS it was only possible to quantify the Sb(V), whereas the presence of Sb(III) was not detected. The determination of Sb(III) was only possible through FI-HG AAS, FI-HG-ICP-MS and LC-HG-ICP-MS (by combination of conditions set for LC and FI-HG individually). Similar results for Sb(III) were obtained through the techniques FI-HG AAS and HGICP- MS. Thus, it was possible to quantify free Sb(III) and Sb(V), while probable compounds of Sb(III) and/or Sb(V) bound to NMG were observed but could not be identified and quantified, mainly because of lack of reference solutions and difficulty in separating the observed Sb species. The precision of methods for determination of Sb(III) and Sb(V) (expressed as relative standard deviation for 5 consecutive measurements) was about 9% and 3% respectively. As there were no certified reference materials to evaluate the accuracy of the developed methods, recovery tests of Sb(III) and Sb(V) were made, where they were in the range 96 to 101% for Sb(V) and 85 to 104% for Sb(III). Moreover, the results were compared with those obtained by official methods to quantify Sb(III), Sb(V) and Sb total in meglumine antimoniate. / Neste trabalho foram avaliados diferentes métodos para a análise de especiação de Sb(III) e Sb(V) em antimoniato de meglumina (NMG). Cromatografia a líquido (LC) combinada, ou não, com a técnica de geração de hidretos (HG) foi investigada para a separação de espécies de Sb. A espectrometria de massa com plasma indutivamente acoplado (ICP-MS) foi empregada como detector. Um sistema de injeção em fluxo (FI) em conjunto com HG (FI-HG) e acoplado à espectrometria de absorção atômica (AAS) foi também empregado para a determinação seletiva de Sb(III) na presença de Sb(V). Duas colunas de troca aniônica (Dionex, IonPacAS14 e Hamilton, PRP-X100) foram avaliadas para separar as espécies de Sb por LC. Parâmetros relacionados com a fase móvel, tais como tipo (EDTA, ftalato de potássio e EDTA + ftalato de potássio), concentração (0,5 a 10 mmol L-1), pH (3,5 a 7,0), vazão (0,25 a 1,75 mL min-1) e o modo de eluição (isocrático e gradiente) foram estudados. O volume de amostra injetada no cromatógrafo foi fixado em 200 μL. Para a separação cromatográfica, a fase móvel que levou a melhores separações de Sb(III) e Sb(V) foi o EDTA nas concentrações de 0,5 mmol L-1 e 1,0 mmol L-1, para as colunas IonPac e PRP-X100, respectivamente. Os parâmetros relacionados com o sistema FI-HG mais adequados foram também avaliados e escolhidos, tais como o redutor do Sb(III) (NaBH4 0,1%, m/v), complexante do Sb(V) (ácido cítrico 10%, m/v), a água como carregador da amostra, o percurso analítico (300 cm), volume de amostra (100 μL), a vazão total das soluções (8,5 mL min-1) e a vazão do gás de arraste (0,4 mL min-1). Para a identificação e/ou quantificação das espécies de Sb presentes no NMG, as amostras foram somente diluídas em água. Com o emprego de LC-ICP-MS foi possível quantificar somente o Sb(V), não sendo detectada a presença da espécie Sb(III). A determinação de Sb(III) foi somente possível mediante as técnicas FI-HG AAS, FI-HG-ICP-MS e LC-HG-ICP-MS (esta mediante combinação das condições ajustadas para LC e FI-HG individualmente). Resultados concordantes para Sb(III) foram obtidos mediante as técnicas FI-HG AAS e FI-HGICP- MS. Desta forma, foi possível quantificar Sb(III) e Sb(V) livres, enquanto que possíveis compostos de Sb(III) e/ou Sb(V) ligados ao NMG foram observados mas não puderam ser identificados e quantificados, principalmente por causa da falta de soluções de referência e dificuldade de separação das possíveis espécies de Sb observadas. A precisão dos métodos de determinação de Sb(III) e Sb(V) (expressa como desvio padrão relativo para 5 medições consecutivas) foi cerca de 9% e 3%, respectivamente. Como não havia materiais de referência certificados para avaliar a exatidão dos métodos desenvolvidos, foram feitos testes de recuperação de Sb(III) e Sb(V), sendo que as mesmas ficaram na faixa de 96 a 101% para o Sb(V) e de 85 a 104% para o Sb(III). Além disso, os resultados obtidos foram comparados com aqueles obtidos por métodos oficiais para a quantificação Sb(III), Sb(V) e Sb total no antimoniato de meglumina.

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.

The advantage of one-bead-one-compound combinatorial libraries is that hundreds of thousands to millions of compounds can be rapidly synthesized and screened simultaneously. The beads supporting the compounds of interest are then isolated and analyzed to decipher the structure of the desired compound. Many methods are currently used to allow deconvolution of the compound on the individual beads. Herein is described a novel method to encode TentaGel beads using absorption of different ratios of lanthanide ions. The encoding process is completed in parallel with the synthesis of the library of compounds. Once the desired beads are identified, the lanthanide ions can be released from the bead and analyzed using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS).

No description available.

Thesis advisor: J. Christopher Hepburn / The Nashoba terrane of SE New England is one of three peri-Gondwanan tectonic blocks caught between Laurentia and Gondwana during the closure of the Iapetus Ocean in the early to mid- Paleozoic. U-Pb analyses (LA-ICP-MS) were carried out on zircon suites from the meta-sedimentary rocks of the Nashoba terrane. The youngest detrital zircons in the meta-sedimentary rocks of the Nashoba terrane are Ordovician in age. There is no significant difference in age between meta-sedimentary units of the Nashoba terrane across the Assabet River Fault Zone, a major fault zone that bisects the NT in a SE and a NW par. Zircon in meta-sedimentary rocks in the Marlboro Fm., the oldest unit of the Nashoba terrane, is rare, which may reflect the basaltic nature of the source material, and is commonly metamict. The Marlboro Fm. contained the oldest detrital grain of all the analyzed samples, with a core of ~3.3 Ga and rim of ~2.6 Ga indicating that it was sourced from Archaen crustal material. Detrital zircons from the Nashoba terrane show a complete age record between the Paleoproterozoic and Paleozoic that strongly supports a provenance from the Oaxiqua margin of Amazonia. The detrital zircon suite of the Nashoba terrane is distinct from both Avalonia and the Merrimack belt; however, they resemble zircon suites from Ganderia. This study proposes that the Nashoba terrane of Massachusetts correlates with the passive trailing edge of Ganderia. Finally, metamorphic zircon analyses of the terrane show that the Nashoba terrane experienced a peak in hydrothermal fluid infiltration during the Neoacadian orogeny. / Thesis (MS) — Boston College, 2011. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

Im Rahmen dieser Arbeit wurden vier verschiedene Methoden zur Separation, Identifikation sowie Quantifizierung von Silber-Nanopartikeln (Ag-NP) entwickelt. Mittels asymmetrischer Fluss-Feldflussfraktionierung (AF4) in Kombination mit einem induktiv gekoppelten Plasma-Massenspektrometer (ICP-MS) konnten eine gute Trennung und hohe Wiederfindungsraten gefunden werden. Eine systematische Studie möglicher Probenverluste während der Methodenoptimierung zeigte, dass der größte Verlust durch die Ag+-Ionen verursacht wurde, während Verluste durch Ablagerungen auf der Membran vernachlässigbar waren. Für Citrat-stabilisierte Ag-NP konnten mittels Hohlfaser-Fluss-Feldflussfraktionierung (HF5) gute Trennergebnisse erreicht und der hydrodynamische Durchmesser bestimmt werden. Zur Bestimmung der Partikelanzahlgrößenverteilung und des geometrischen Durchmessers von Partikeln in unbekannter Matrix wurde die Isotopenverdünnungsanalyse (IVA) erfolgreich mit der Einzelpartikel ICP-MS kombiniert. Weiterhin wurde eine Hochdruckflüssigkeitschromatographie(HPLC)-IVA-ICP-MS-Methode entwickelt, mit welcher NP und ihre korrespondierenden Ionen getrennt und quantifiziert werden konnten. Ein Vergleich der Ansätze zeigt, dass eine Kombination mehrerer Methoden nötig ist, um alle relevanten Informationen über die NP zu erhalten. Zum Abschluss wurde mit den entwickelten Methoden das Umweltverhalten der Ag-NP in einer Huminsäure(HS)-Suspension untersucht. Hierbei wurden erste Stabilisierungseffekte in Bezug auf die Ag-Konzentration und Partikelanzahl festgestellt. Zudem konnte mittels HF5 und HPLC für kleine NP in HA eine Modifikation in Form der Ausbildung eines zweiten, kleineren NP-Signals beobachtet werden. / In this work, four different methods for the separation, identification, and quantification of silver nanoparticles (Ag-NP) were developed. Using asymmetric flow field-flow fractionation (AF4) in combination with inductively coupled plasma mass spectrometry (ICP-MS), a good separation and high recovery rates were found. A systematic investigation of possible sample losses during the method optimization showed that Ag+ ions caused the highest loss and only negligible amounts of Ag residues on the membrane were found. For citrate-stabilized Ag-NP, hollow fiber flow-field flow fractionation (HF5) analyses achieved good results for the separation and calculation of the hydrodynamic diameters. In order to determine the particle number size distribution and the geometric diameter for samples in unknown matrices, isotope dilution analysis (IVA) was successfully combined with single particle ICP-MS. Additionally, a high-performance liquid chromatography (HPLC)-IVA-ICP-MS approach was developed, which was able to separate and quantify NP and their corresponding ions. A comparison of the methods showed that a combination of different approaches is necessary to obtain all relevant information. Finally, the methods were applied to analyze the environmental behavior of Ag-NP in a humic acid (HS) suspension. Here, first stabilization effects in terms of the Ag concentration and particle number concentration were detected. Using HF5 and HPLC for the analysis of small NPs in HS, a modification in the form of a second, smaller NP signal was observed.

Développement de méthodes analytiques pour l’évaluation de l'impact de l'industrie de fertilisants chimiques sur le milieu marin / Development of Analytical methods for the evaluation of the impact of phosphate fertilizer industry on marine environment

Chumbo (Pb) é um elemento tóxico ao qual estão associadas diversas doenças que afligem o ser humano. Dessa forma, o desenvolvimento de novas metodologias para a determinação de Pb no sangue traz uma importante contribuição na monitoração humana exposta a este metal. No presente estudo, é apresentado uma metodologia nova para determinação de Pb utilizando-se a técnica fingerstick com filtro de papel em conjunto com a espectrometria de massas de alta resolução em fonte de plasma indutivo (HR/ICP/MS). Os resultados encontrados mostraram-se robustos para uma digestão total de cerca de 0,1 g de sangue, em valores de referência, e níveis de chumbo inferiores a 5 μgdL-1. O presente método é pouco intrusivo permitindo a coleta e transporte das amostras à longa distância sem perda de integridade e/ou estabilidade. Dessa forma traz uma importante contribuição para o monitoramento da exposição do metal principalmente no atendimento às comunidades distantes. / Lead (Pb) is a toxic element to which several diseases affecting human beings are associated. Therefore, the development of new methodologies for the Pb determination in blood represents an important contribution to monitor human exposition to this metal. In the present study, a new methodology for Pb determination is presented using fingerstick techniques for sample collection and lead detection by using a high resolution inductively coupled plasma mass spectrometry technique. The results are robust for total digestion of 0.1 g of deposited blood and lead levels below to 5 μgdL-1. This method is less intrusive in comparison with the traditional ones. It allows the collection and transport of samples over long distances without loss of integrity and / or stability. Therefore, it brings an important contribution for monitoring the exposure of this metal mainly in the attendance to remote communities.