A concentric pneumatic nebulizer (CPN) and a custom designed flow focusing nebulizer (FFN) are characterized. As will be shown, the classical Nukiyama-Tanasawa and Rizk-Lefebvre models lead to erroneous size prediction for the concentric nebulizer under typical operating conditions due to its specific design, geometry, dimension and different flow regimes. The models are then modified to improve the agreement with the experimental results. The size prediction of the modified models together with the spray velocity characterization are used to determine the overall nebulizer efficiency and also employed as input to a new Maximum Entropy Principle (MEP) based model to predict joint size-velocity distribution analytically. The new MEP model is exploited to study the local variation of size-velocity distribution in contrast to the classical models where MEP is applied globally to the entire spray cross section. As will be demonstrated, the velocity distribution of the classical MEP models shows poor agreement with experiments for the cases under study. Modifications to the original MEP modeling are proposed to overcome this deficiency. In addition, the new joint size-velocity distribution agrees better with our general understanding of the drag law and yields realistic results.

A concentric pneumatic nebulizer (CPN) and a custom designed flow focusing nebulizer (FFN) are characterized. As will be shown, the classical Nukiyama-Tanasawa and Rizk-Lefebvre models lead to erroneous size prediction for the concentric nebulizer under typical operating conditions due to its specific design, geometry, dimension and different flow regimes. The models are then modified to improve the agreement with the experimental results. The size prediction of the modified models together with the spray velocity characterization are used to determine the overall nebulizer efficiency and also employed as input to a new Maximum Entropy Principle (MEP) based model to predict joint size-velocity distribution analytically. The new MEP model is exploited to study the local variation of size-velocity distribution in contrast to the classical models where MEP is applied globally to the entire spray cross section. As will be demonstrated, the velocity distribution of the classical MEP models shows poor agreement with experiments for the cases under study. Modifications to the original MEP modeling are proposed to overcome this deficiency. In addition, the new joint size-velocity distribution agrees better with our general understanding of the drag law and yields realistic results.

Mass spectrometry is an analytical technique commonly used for determining elemental composition in a substance sample. For this purpose, the sample is placed into some liquid solution called liquid matrix. Unfortunately, the spectrum of the sample is not observable separate from that of the solution. Thus, it is desired to distinguish the sample spectrum. The analysis is usually based on the comparison of the mixed spectrum with the one of the sole solution. Introducing the missing information about the origin of observed spectrum peaks, the author obtains a classic set up for the Expectation-Maximization (EM) algorithm. The author proposed a mixture modeling the spectrum of the liquid solution as well as that of the sample. A bell-shaped probability mass function obtained by discretization of the univariate Gaussian probability density function was proposed or serving as a mixture component. The E- and M- steps were derived under the proposed model. The corresponding R program is written and tested on a small but challenging simulation example. Varying the number of mixture components for the liquid matrix and sample, the author found the correct model according to Bayesian Information Criterion. The initialization of the EM algorithm is a difficult standalone problem that was successfully resolved for this case. The author presents the findings and provides results from the simulation example as well as corresponding illustrations supporting the conclusions.

<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>

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. 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 &gt; DIHEN &gt; MCN-C &gt; 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 &gt; MCN-C/DP &gt; 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. 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.