The aim of thesis was to establish a methodology for 210Pb measurements by Accelerator Mass Spectrometry (AMS). The potential application is to measure 210Pb in people who have been exposed to radon. This will better our understanding of radon toxicity, which is not possible now with current radiometric and mass spectrometry techniques. The determination of 210Pb by AMS was done in two major studies 1) Studying Pb chemistry in a Cs+ sputter source used in AMS and 2) Evaluating 204,205 & 208Pb spikes for the quantification of 210Pb by isotope dilution. Pb chemistry was investigated using an 834 SIMS-type and a SO-110 Cs+ sputter source at the IsoTrace Laboratory and A.E Lalonde AMS facility, respectively. Different molecular anions of Pb were studied with the 834 SIMS-type Cs+ sputter source and the strongest molecular anion current of Pb and thus greatest ionization efficiency was achieved form the superhalogen PbF3-. The average 208PbF3- current was unaffected by varying the ratio of the fluorinating compounds (AgF2 and CsF) packed into a target. The average current of 208PbF3- was reproducibly increased by chemically mixing the targets of AgF2, CsF and PbF2 in concentrated HF rather than mechanically mixing them the powders with a stir rod. The count rate of 210Pb reproducibly increased by a factor of 20 when μg quantities of PbF2 were present in mg AMS targets compared to AMS targets that had pg quantities of PbF2. The average current of 208PbF3- for pure PbF2 targets in an SO-100 Cs+ sputter source was reproducibly increased when the Cs+ flux was decreased by a factor of 10. This phase of my work maximized the overall efficiency of PbF3-, to a value of 1.8x10-10 ±8x10-11s-, which was a key first step in the measurement by AMS. Then isotope dilution was tested to quantify 210Pb and the next stage of my work evaluated the use of 204,205 & 208Pb spikes. 210Pb was measured in the +3 charge state by isotope dilution assays using 204,205 & 208Pb spikes. 204Pb+3 reproducibly suffered from the molecular interference from 68Zn3+3, which could not be easily removed without negatively impacting the detection limit for 210Pb. 205Pb+3 continually suffered from 205Tl+3 interference which could be readily be removed but not without negatively affecting the II detection limit for 210Pb. 208Pb+3 suffers from no molecular interferences but if a large amount of 208Pb is needed to swamp the Pb in a sample, this could limit the detection limit for 210Pb as the abundance sensitivity is 210Pb/208Pb=1.3×10-12. A calibration curve is required when 208Pb is used as a spike due to a difference in collection efficiency of a Faraday cup, where 208Pb+3 is detected and the gas ionization chamber, where 210Pb+3 is detected. The quantification of 210Pb with 208Pb as a spike yielded a detection limit of 4.4mBq at the IsoTrace facility. A theoretical detection limit of ≤0.11mBq is expected at the A.E Lalonde AMS facility. The expected detection limit at the A.E Lalonde AMS facility is on par with α-spectroscopy but AMS samples can be counted in less than 1 hour whereas alpha spectrometry samples must be counted for about 1 day.

O fósforo (P) é um elemento altamente demandado pela agricultura mundial para produção de alimentos. Os solos de regiões tropicais apresentam baixo teor de P disponível às plantas, devido à escassez natural herdada do material de origem e predominância de processos de fixação, sendo necessário o suprimento deste nutriente via adubação. Os fertilizantes fosfatados solúveis utilizados apresentam baixo aproveitamento devido a reações que se iniciam desde a interface solo-grânulo até o trajeto difusivo do P no solo. Pesquisas têm abordado sobre o potencial do silício (Si) em competir por sítios de adsorção de P no solo, tornando este nutriente mais disponível às plantas e aumentando o aproveitamento dos adubos fosfatados. Visando desenvolver estratégias para melhorar a eficiência agronômica do fosfato monoamônio (MAP) os objetivos deste trabalho foram: a) construir um dispositivo para granular fertilizante em pequenas quantidades, b) avaliar a difusão e disponibilidade do P a partir dos fertilizantes produzidos, em dois solos de característica textural e capacidade máxima de adsorção de P contrastantes e c) avaliar a eficiência agronômica e o aproveitamento do P dos fertilizantes propostos neste estudo em conjunto com o superfosfato orgânico-complexado (SOC) e o MAP, por meio da técnica isotópica com 32P. Foram conduzidos quatro experimentos no Laboratório de Fertilidade do Solo do Centro de Energia Nuclear na Agricultura (CENA-USP), Piracicaba - SP. Os solos utilizados nos ensaios foram classificados como Latossolo Vermelho-Amarelo distrófico (LVAd) e Latossolo Vermelho distrófico (LVd). Conduzidos simultaneamente, o primeiro e segundo experimentos constituíram de estudo da difusão do P por meio da incubação dos fertilizantes em placa de petri preenchidas com cada um dos solos, montados em delineamento inteiramente casualizado, compostos por 11 tratamentos (9 fertilizantes com diferentes proporções P-Si (1-9 a 9-1) no grânulo mais o MAP e o tratamento controle) e cinco repetições. O terceiro e quarto experimentos foram instalados em casa de vegetação com a cultura do milho cultivada nos dois tipos de solo, num delineamento inteiramente casualizado, em esquema fatorial 5x4, sendo cinco fertilizantes fosfatados dentre os quais três foram selecionados no estudo de incubação (proporções P-Si no grânulo: 2-8, 6-4 e 8-2) o SOC e o MAP, aplicados em quatro doses de P (0, 30, 60, 90 mg kg-1). Foi possível construir o granulador projetado, e com uso deste produzir os fertilizantes propostos. No estudo de incubação, observou-se que a presença de Si no grânulo do fertilizante fosfatado alterou o pH do solo ao redor dos grânulo e a difusão e disponibilidade do P em ambos os solos estudados. O P difundiu-se poucos centímetros no solo, ficando restrito às primeiras secções em torno do ponto de aplicação do fertilizante. No experimento em casa de vegetação, observou-se que o fertilizante contendo a maior quantidade de Si no grânulo proporcionou maiores valores de P acumulado, P na planta proveniente do fertilizante e aproveitamento do P do fertilizante, bem como melhores índices de eficiência agronômica relativa em relação ao MAP. O SOC proporcionou os menores resultados em todos os parâmetros avaliados / Phosphorus (P) is a highly demanded element for world agriculture for food production. Tropical soils present low level of this nutrient in phyto-available form due to natural inherited shortage of source material and predominance of fixation processes, requiring the supply of this nutrient via fertilization. The soluble phosphate fertilizers used have low utilization by plants due to reactions that start from the soil-granule interface to the P diffusive path in the soil. Research has addressed on the silicon (Si) potential to compete for P adsorption sites in the soil, making this nutrient more available to plants and increasing the use of fertilizer P. In order to develop strategies to increase the agronomic efficiency of monoammonium phosphate (MAP) the objectives of this study were: a) to build a device for the production of granulated fertilizer in small quantities b) assess the diffusion and availability of P from the fertilizer produced in two contrasting textural characteristics and maximum P adsorption capacity and c) evaluate the agronomic efficiency and utilization of P from fertilizers proposed in this study compared with the organic-complexed superphosphate (OCS) and MAP by 32P isotope technique. Four experiments were conducted at the Soil Fertility Laboratory of Center for Nuclear Energy in Agriculture (CENA-USP), Piracicaba SP, Brazil. The soils used in the experiments were classified as Oxisol and Haplortox collected from the surface layers. The first and second experiments, conducted simultaneously, constituted the fertilizer incubation study in petri dishes in a completely randomized design with 11 treatments (9 fertilizer with different P- Si proportions (1-9 to 9-1) in the granule, plus the MAP and the control) and five replicates. The third and fourth experiments were conducted in a greenhouse with corn grown in the two types of soil in a completely randomized 5x4 factorial design, with five phosphate fertilizer among which three were selected in the study of incubation (proportions P-Si in the granule: 2-8, 6-4 and 8-2), OCS and MAP applied in four rates of P (0, 30, 60, 90 mg kg-1). It was possible to build the projected granulator, and use this to produce the proposed fertilizer. In the study of incubation, it was observed that the presence of Si in phosphate fertilizer granule changed the pH of the soil around the granules and the diffusion of P in both soils. The P diffused few centimeters in both soils, being restricted to the first sections around the applied granule. It was observed that, in the greenhouse experiment, in both soils, the fertilizer containing the highest amount of Si in the granule provided the highest plant accumulated P values, P in the plant derived from fertilizer and of fertilizer P utilization and best relative agronomic efficiency rate in relation to MAP and the OCS. The OCS gave the lowest results in all parameters

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.

Previous work by our research group demonstrated that quantitative chemical analysis of analytes, such as mercury and chromium species, in environmental matrices could be successfully carried out without using calibration curves and with correction for species interconversion by using EPA Method 6800A. This method encompasses isotope dilution mass spectrometry (IDMS) and speciated isotope dilution mass spectrometry (SIDMS), both of which are described in detail in chapter 1. Research described in this dissertation expands upon our earlier work by applying the method to the speciation of mercury in biological matrices, the speciation of glutathione in red blood cells and whole blood, and the analysis of enzyme activity in mammalian tissue. / Bayer School of Natural and Environmental Sciences; / Chemistry and Biochemistry; / PhD; / Dissertation;

none

none

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).

Made available in DSpace on 2014-10-09T12:36:06Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:23Z (GMT). No. of bitstreams: 1 11278.pdf: 1430649 bytes, checksum: a436d2f134f4223026499c63265f2730 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:32:26Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:10:14Z (GMT). No. of bitstreams: 1 03136.pdf: 2220571 bytes, checksum: c01c220ea857b701d3f8df64b71f071a (MD5) / Dissertacao(Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP