<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.