Thesis (M.S.)--University of Wisconsin--Madison, 1982. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 112-116).

This thesis deals with instrumental and methodological developments for speciation analysis of gaseous mercury (Hg(g)), based on isotope dilution analysis (IDA). The studied species include Hg0, (CH3)2Hg, CH3HgX and HgX2 (where X symbolises a negatively charged counter ion in the form of a halide or hydroxyl ion). Gas chromatography hyphenated with inductively coupled plasma mass spectrometry (GC-ICPMS) was used for separation and detection of Hg(g) species. Permeation tubes were used for the generation of gaseous isotopically enriched Hg standards (tracers). These tracers were continuously added to the sample gas stream during sampling of Hg(g). A mobile prototype apparatus incorporating both the permeation source and a sampling unit for collection of Hg(g) was developed and used for this purpose. Hg(g) species were pre-concentrated on Tenax TA and / or Carbotrap solid adsorbents. Au-Pt was used for pre-concentration of total Hg(g), either as the primary medium, or as backup. Collected species were eluted from these media and introduced to the instrument by thermal desorption. Various degrees of species transformations, as well as losses of analyte during pre-concentration and elution, were found to occur for both Tenax TA and Carbotrap. The performance characteristics of these media were shown to be species specific, as well as matrix dependent. The development of an on-line derivatisation procedure allowed for minimised species transformations, as well as reduced adsorption and memory effects of ionic Hg(g) species within the analytical system. In conclusion, IDA provides an important tool for identification, minimisation and correction of the above mentioned analytical problems. Furthermore, it offers significant advantages with respect to quality assurance, compared to conventional techniques, both when it comes to rational development of new methodology, as well as for continuous validation of existing procedures. The developed methodology for speciation analysis of Hg(g) has been tested in various applications, including the determination of Hg(g) species concentrations in ambient air (both in and outdoor) and in the head space of sediment microcosms. Hg(g) species were formed in the sediments as a result of naturally occurring redox and methylation processes, after addition of an isotope enriched aqueous Hg(II) precursor. The methodology has also been used for assessing the risk of occupational exposure to Hg(g) species during remediation of a Hg contaminated soil and for studying Hg0(g) transport and Au-Pt pre-concentration characteristics in natural gases. Hg0 was used as the model species in the latter experiments, since it is believed to be the dominating form of Hg(g) in natural gas. The results indicate that the occurrence of H2S can cause temperature dependent adsorption and memory effects of Hg0(g) in the presence of stainless steel, thereby providing a plausible explanation to the variability of results for sour gases occasionally observed in the field. Hg0(g) has demonstrated overall high recovery during collection on Au-Pt tubes for all gases tested in this thesis. Recent (unpublished) results however indicate that there are potential species specific and matrix dependent effects associated with the Au-Pt based pre-concentration of Hg(g) in natural gases.

Thesis (M.S. )--Duquesne University, 2007. / Title from document title page. Abstract included in electronic submission form. Includes bibliographical references (p. 59-61) and index.

Thesis (M.S.)--Baylor University, 2009. / Includes bibliographical references (p. 83-88).

Thesis (Ph. D.)--Carleton University, 2004. / Includes bibliographical references (p. 152-160). Also available in electronic format on the Internet.

Orientador: Jacinta Enzweiler / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-17T09:52:02Z (GMT). No. of bitstreams: 1 Cotta_AloisioJoseBueno_D.pdf: 12674950 bytes, checksum: 5c83c715500dcc83803f8d9b7d8712f1 (MD5) Previous issue date: 2010 / Resumo: A espectrometria de massas com plasma indutivamente acoplado (ICP-MS) possibilita determinações multielementares rápidas e com baixos limites de detecção numa variedade de matrizes, dentre elas as geológicas. Neste estudo, métodos comparativos utilizando um ICP-MS quadrupolar equipado com cela de colisão (CC) foram estabelecidos para determinar amplos conjuntos de elementos-traços em águas e em rochas. A aplicabilidade e as limitações da CC para atenuar interferências poliatômicas sobre os isótopos empregados foram amplamente investigadas. Em condições ótimas, muitas interferências puderam ser eliminadas ou significativamente atenuadas, o que tornou os métodos menos dependentes de correções matemáticas. Para a análise de rochas, técnicas clássicas de dissolução envolvendo misturas ácidas, como HF/HNO3, foram utilizadas e um novo procedimento com equipamento que possibilita efetuar a digestão sob pressão de até 13 MPa é proposto. Nesse caso, a precipitação de AlF3, o qual retém alguns elementos-traço, principalmente Co, Sr, Ba e Pb, foi o maior obstáculo à recuperação quantitativa dos analitos. A formação de AlF3 foi evitada com a adição de Mg à porção teste e com o controle da temperatura de digestão. A decomposição por sinterização com peróxido de sódio foi também investigada e verificou-se que a inclusão de uma etapa de aquecimento da dispersão resultante da dissolução do sinterizado em água, antes da separação do precipitado de hidróxidos de Fe e Ti, o qual retém os elementos-traço, auxilia na coprecipitação de Ni, Zr, Nb, Cd, Sn, Sb, Hf, Pb e Th e permite acrescentá-los à lista de elementos determináveis. Os métodos foram validados pela análise de um conjunto de materiais de referência (MR), alguns deles certificados. Os resultados obtidos demonstraram que os métodos desenvolvidos para águas e rochas apresentaram tendência e coeficientes de variação menores que 5% para a maior parte dos mensurandos. Os resultados obtidos para os MR certificados de rochas, BRP-1 e OU-6, foram utilizados para calcular a incerteza do método ao nível aproximado de confiança de 95%. A técnica de diluição isotópica foi aplicada para determinar Cr, Ni, Cu, Zn, Sr e Sn em alguns MR de rochas em uso e em candidatos a MR, com o objetivo de estabelecer o método e contribuir com novos valores para esses MR. As incertezas de todas as etapas do procedimento foram estimadas. Os resultados obtidos evidenciam que o valor certificado de Cr em BRP-1 deveria ser revisto e confirmam a necessidade do estabelecimento da rastreabilidade metrológica durante a certificação de MR. / Abstract: Inductively coupled plasma mass spectrometry (ICP-MS) is suited for fast multi-trace element determinations with low detection limits in a variety of matrices, including geological samples. In this study we established comparative analytical methods for the determination of an expressive number of trace elements in water and rock samples using an ICP-MS equipped with collision cell (CC). The applicability and limitations of CC for polyatomic interference attenuation over the isotopes used were widely investigated. Under optimized conditions, many interferences were eliminated or significantly attenuated, so these methods depend less on mathematical corrections. For rock analyses, classical multi-acid decomposition techniques, with mixtures like HF/HNO3, were used, and a new procedure with equipment that allows digestion at 13 MPa is proposed. In this case, the precipitation of AlF3, which retains some trace elements like Co, Sr, Ba and Pb preferentially, was the major drawback in achieving quantitative recoveries. The formation of AlF3 was inhibited by adding Mg to the test portion and controlling the temperature of digestion. Sample decomposition by sintering with sodium peroxide was also tested and was demonstrated that including a heating step of the sinter dispersion obtained after dissolution in water and before the separation of the precipitated Fe and Ti hydroxides, which retain many trace elements, helps to achieve a quantitative co-precipiation of Ni, Zr, Nb, Cd, Sn, Sb, Hf, Pb and Th and allows to include them to the list of determinable elements. The methods were validated by analysis of a set of reference materials (RM) some of them certified. Relative standard deviations and bias of the results were less than 5% for most of the measurands. The results obtained for the certified RM BRP-1 and OU-6 were used to calculate the measurement uncertainty at the approximate 95% confidence interval. The isotope dilution technique was applied to determine Cr, Ni, Cu, Zn, Sr and Sn in some geochemical RM in use and in candidate RM, with the objective of establishing the method to contribute with new values for the analysed RM. The uncertainties of the whole analytical procedure were estimated. The results obtained show that the certified value of Cr in BRP-1 should be reviewed and confirm the need of establishing the metrological traceability during the certification of RM. / Doutorado / Geologia e Recursos Naturais / Doutor em Ciências

The work presented in this dissertation explores the nature of agro-pastoral strategies developed by Neolithic farmers as a way to understand how early food production was inter-twined with environmental and socio-economic opportunities and constraints. Towards this end, a multi-isotope approach is used to address questions of scale and intensity of crop cultivation and animal management at the archaeological sites of Kouphovouno, southern Greece, Makriyalos, northern Greece, and Çatalhöyük, south-central Turkey. Measurements of stable carbon, nitrogen, oxygen and strontium isotope values of carbonized plant remains, human and animal bone collagen and animal tooth enamel are used to examine the similarities and differences in the types of treatments that individual species of plants and animals received during the agricultural cycle at the distinct locations. The results show that farmers at the three sites developed variable methods for exploiting the arable and pastoral landscape and catering to their economic and culinary needs. The discussion considers the implications of these findings to our understanding of the complexity and adaptability of early farming systems.

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.