Inductively-Coupled Plasma Optical Emission Spectrometry (ICP-OES) is evaluated as a method for the selective determination of several non-metals which emit light in the Vacuum Ultraviolet (VUV) region of the spectrum. In this study, emphasis is placed on those elements which are totally unobservable with standard techniques or have very weak lines in the UV-VIS region of the spectrum. The sensitivity and accuracy of the apparatus and methods devised allows the determination of empirical formulas of gas chromatographic effluents. The results of this study indicate that the background emission of the ICP in the VUV is low level and nearly constant over the entire spectral region investigated (125 - 185 nm.). Promising analytical lines for oxygen, nitrogen, chlorine, bromine, and carbon are also observed in this region. A progression of four experimental configurations were constructed, employing a purged optical path and a unique coolant tube design. The last of these configurations has the capability of spatial resolution of individual portions of the discharge so that emission maps and profiles could be constructed. The results of the maps generated indicate that the region of highest emission intensity is always centered in the discharge. However, the vertical position of this region is found to be dependent upon r.f. power and argon flow rates. Detection limits in the low nanogram region are observed for each non-metal. The dynamic range for each element is in excess of 10⁴ and the selectivity ratio versus carbon is above 100 in each case. A method was developed for determining the elemental composition of the effluents of a GC. Using internal standards, the method is independent of the weight of each component eluted thus sampling errors are eliminated. The average relative errors in multielement analysis are 0.89%, 0.75%, 2.1%, 0.55%, and 0.64% for the percent carbon, oxygen, nitrogen, chlorine, and bromine, respectively.

Supercritical fluid chromatography has recently been coupled to an ICPMS detector. The method has been shown to be suitable for the speciation and analysis of organometallic compounds at trace levels. This study has attempted to further the research initiated by other groups in this field by developing a new interface for coupling these two instruments. The new interface makes use of a modified join between the nebuliser and the torch in the ICP unit. The effect of the mobile phase on the plasma with time has been investigated and little spectral background interference has been observed. The chromatographic conditions were optimised using a flame ionisation detector and a series of tin, arsenic, iron, and mercury compounds were analysed using SFC-ICPMS. Mter focusing the ICP-MS on the element of interest, each compound was evaluated in terms of the change in peak intensity with change in concentration and the theoretical detection limits were compared to the practical detection limit. The restrictor temperature was determined using a rough calibration procedure with bench top experiments. The effect of the restrictor temperature on the peak intensity of each compound was then studied. All results were plotted and a theory for the observed trends and observations is proposed. The results obtained and the interface used have been compared to the results and interfaces of other groups and differences have been explained. Attempts to extract relevant compounds from topsoil using supercritical fluid extraction were made. Finally, sediment samples were collected from relevant points in Durban Bay and an attempt was made to extract these samples using supercritical fluid extraction. The extracted samples were analysed using SFC-ICPMS although little success was obtained. Reasons for the failure of this method on the real samples have been proposed. In the concluding section of this study SFC~ICPMS has been evaluated in terms of its future applicability and use as a viable analytical method. / Thesis (M.Sc.-)-University of Natal, Durban, 1994.

I believe that my research work on the plasmonic spectroscopy of metallic nanostructures has provided an in-depth fundamental understanding of the localized surface plasmon resonance and will have a number of implications for the applications of metallic nanostructures in optics, optoelectronics, and biotechnology. / I will first describe my studies on the plasmonic properties of metallic nanostructures. Specific approaches of modifying the sizes and shapes of Au nanorods have been developed for tailoring their plasmonic properties, including surface plasmon wavelength, absorption, scattering, and extinction cross sections. Single-particle dark-field imaging and spectroscopy have proved that the scattering intensity of overgrown nanorods is larger than that of shortened nanorods from the same starting nanorods. Finite-difference time-domain (FDTD) calculations further show that the scattering-to-extinction ratio increases linearly as a function of the diameter of Au nanorods with a fixed aspect ratio. To obtain a deep understanding on the shape dependence of the localized surface plasmon resonance, I have emplyed FDTD on both Au nanorods and Au nanobipyramids. The results show that, when excited at their LSP wavelengths, Au nanobipyramids exhibit a maximal electric field intensity enhancement that is 3--6 times that of Au nanorods. Au nanorods have been further assembled into chains (end-to-end) and stacks (side-by-side). FDTD calculations have been performed on both Au nanorod chains and stacks with varying gap distances to obtain the dependence of the plasmon shift on the gap distance, which is then used as a plasmonic ruler to estimate the gap distance between assembled nanorods. Moreover, dye--Au nanorod hybrid nanostructures have also been successfully fabricated for the study of the coupling between the transition dipole resonance and the plasmonic resonance. The coupling-induced plasmon shift is found to be strongly dependent on molecular properties, the dye concentration in solutions, and the spacer thickness between dye molecules and the surface of Au nanorods. The coupling can be switched off by means of laser-induced photodecomposition of dye molecules. / Next, I will present my studies on the applications of metallic nanostructures. A SERS substrate has been constructed by assembling silver nanoparticles along silica nanofibers. The enhancement factors are found to be 2 x 10 5 for 4-mercaptobenzoic acid and 4-mercaptophenol, and 7 x 10 7 for rhodamine B isothiocyanate. A novel plasmonic optical fiber device has further been fabricated to detect small changes in the local dielectric environment. For individual Au nanorods, the index sensitivity and figure of merit (FOM) are found to be linearly dependent on the longitudinal plasmon resonance wavelength and reach 200 nm/RIU and 3.8, respectively. For nanorod ensembles, the index sensitivity and FOM of the longitudinal plasmon resonance are found to be 138 nm/RIU and 1.2, respectively. / The study of the plasmonic spectroscopy of metallic nanostructures is of great interest in nanoscale optics and photonics. Metallic nanostructures exhibit rich optical and electrical properties due to their localized surface plasmons (LSPs, collective charge density oscillations that are confined to metallic nanostructures). They can be widely used in a variety of application areas, such as surface-enhanced Raman scattering (SERS), plasmonic sensing, and metal enhanced fluorescence (MEF). In this thesis, a systematic study on the plasmonic spectroscopy of metallic nanostructures has been presented, both theoretically and experimentally. / Ni, Wei hai = 金屬納米結構的等離子體光譜 / 倪衛海. / Adviser: Jianfang Wang. / Source: Dissertation Abstracts International, Volume: 70-06, Section: B, page: 3580. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 135-154). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307. / Ni, Wei hai = Jin shu na mi jie gou de deng li zi ti guang pu / Ni Weihai.

A Charge-Exchange Recombination Spectroscopy (CXRS) diagnostic has been installed on Alcator C-Mod to study the transport of light impurities in plasma. The system provides spatially (1 cm) and temporally (12.5 msec) resolved measurements of the impurity density, temperature and flow velocities of the particular impurity. Two optical arrays: poloidal (19 channels) and toroidal (10 channels), collect the light emitted from excited impurity ion populated by charge exchange process from the Diagnostic Neutral Beam (DNB) particle. The attention of this dissertation is focused on the B⁴⁺ (n = 7 [-->] 6) spectral line emitted by B⁴⁺ ion formed in the following charge exchange reaction (H⁰ + B⁵⁺ [-->] H+ + B⁴⁺*). A complex spectral model was developed to simulate emission. The high magnetic fields of C-Mod result in broad Zeeman patterns which must be taken into account for the interpretation of the line shift and broadening in terms of impurity ion velocity and temperature. After the spectral line fitting and careful identification of the charge exchange component, the calculated Doppler broadening and shifts of the spectral line profile yield information on the ion temperature and rotation. Together with the calculation of the beam density, the absolute calibration of the CXRS optical system provides us with B⁵⁺ density measurement capabilities. One of the main objectives of this work was to use the acquired impurity density, temperature and flow velocity profiles to investigate plasma transport behavior and infer the radial electric field E[subscript R] from plasma force balance equation. The focus here was placed on the region of the Internal Transport Barrier (ITB) formation 0.35 < p < 0.8. Radial electric field E[subscript R] is readily calculated in the region of the ITB foot using measured B⁵⁺ profiles. ExB velocity shearing turbulence stabilization are believed to play an important role in the physics of the ITB formation. The computed E[subscript R] profiles demonstrated the large difference between the H-mode and ITB discharges. Linear gyrokinetic stability analysis (GS2) demonstrated that shearing rate w[subscript ExB] prevails over the linear Ion Temperature Gradient (ITG) growth rates [gamma subscript max] in the region where ITB forms. / text

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Investigations of new applications of the inductively coupled plasma (ICP) for analytical atomic emission spectroscopy are performed. Research efforts are focused in three major areas: emissions below 185 nm, analysis of wear metals in lubricating oils and use of the ICP as a selective detector for high performance liquid chromatography (HPLC). A unique plasma coolant tube containing a side arm which allows direct observation of the discharge is used to investigate emissions in the vacuum ultraviolet (VUV) spectral region between 120 and 185 nm. Emissions from elements which do not emit radiation in the visible region are observed. Oxygen emissions at 130 nm, nitrogen at 149 and 174 nm and carbon at 155 and 165 nm make up the background spectrum. These elements are present as impurities in the argon gas used to sustain the ICP discharge. Fifteen emission lines from bromine are observed. Those at 153 and 163 nm are the most intense. Sulfur also has fifteen emission lines and chlorine has nine in this region of the spectrum. The VUV region is found useful for observation and potential analysis of many elements. A heated sample introduction system attached to a Babington nebulizer is investigated as a means to aerosolize lubricating oils for introduction into the ICP. This allows direct analysis of wear metals in oil samples without requiring the usual sample dilutions. Several commercial brands and weights of motor oil are spiked with iron in order to evaluate this system. Heating the oil as it enters the nebulizer is found to increase the nebulization efficiency as much as sixtyfold in some cases. Differences in nebulization efficiency due to viscosity are almost entirely eliminated through the application of heat. A linear calibration curve extending three orders of magnitude from a detection limit of one ppm iron is determined. The ICP is used as a selective detector for HPLC. Nucleotides separated by anion exchange chromatography are determined in the ICP by observing phosphorus emissions. Methanol and acetonitrile used for reverse phase HPLC are successfully run in the IPC. The method is evaluated by using the ICP to determine phosphorus in compounds separated by using reverse phase conditions. The HPLC is used to separate organic interferences from several silicone samples using reverse phase conditions allowing the ICP to accurately analyze silicon content.

No description available.

A direct injection nebulizer was constructed in our laboratory and was evaluated as an interface between a liquid chromatography column and an inductively coupled plasma-atomic emission spectrometer (ICP-AES). Optimum operating conditions, detection limits, and reproducibility in water and in organic solvents were studied. The detection limits in water were similar to a commercially available device. The detection limits of elements in organic solvents were about ten times higher than those in water. The DIN-ICP system stave more uniform response towards different species of Phosphorus and osmium than did a Meinhard nebulizer-ICP system, even when great differences in volatilitN existed between the species. A Potential application to the speciation of cisplatin and its analogs was also investigated. / Department of Chemistry

Thesis (Master)--İzmir Institute of Technology, İzmir, 2005 / Keywords: ICP-OES, Chemometrics methods, internal standardization, matrix effects. Includes bibliographical references (leaves. 111-120).

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.