The presented thesis deals with optimization of parameters speciation analysis based on a selective hydride generation in a direct transfer mode of hydrides and on-line atomization in an atomic absorption spectrometer. In the first part of the thesis processes during generation were investigated. Important indicator of a reactions taking place in a generator is volume of hydrogen (created by decomposition of NaBH4) which is subsequently introduced to the atomizer. In this part of the thesis a new approach to determine a flow rate of hydrogen delivered to the atomizator was developed. An influence of relevant paremeters of the atomizers and atomic absorption spectrometers on basic analytical characteristics of arsenic determination based on hydride generation was performed in the second part. Three atomic absorption spectrometers were used and three sources of radiation were compared. The most important analytic characteristic was the limit of detection which is influenced by standard deviation of measurement values of blank samples and by sensitivity. The best values of the limit of detection were achieved with electrodeless discharge lamps. Key words: hydride generation, arsenic, speciation analysis, atomic absorption spectrometry

This master's thesis deals with optimization of conditions of chemical hydride generation of tellurium and conditions of its atomization, specifically in three types of atomizers - in a diffusion flame (DF), in a heated multiple microflame quartz tube atomizer (MMQTA) and in a dielectric barrier discharge (DBD) atomizer. Tellurium hydride was generated in a flow injection arrangement and a high-resolution continuum source atomic absorption spectrometer was used for detection. As hydride generation can be only done from tetravalent species of tellurium, at first a simple procedure of pre-reduction of hexavalent species of tellurium by heating a standard in hydrochloric acid at 6 mol dm-3 was verified. Further, conditions of chemical generation were optimized with a goal to achieve as high generation efficiency as possible, namely, concentration of hydrochloric acid and sodium tetrahydroborate, volume of the reaction coil and a flow rate of carrier gas. Subsequently, conditions of atomization of tellurium hydride were examined with chosen optimal generation conditions. In the case of DF, it was an amount of hydrogen in the flame, a total flow rate of gases and observation height. In the case of MMQTA, temperature of the atomizer, a flow rate of carrier gas and a flow rate of air or oxygen needed for...

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The goal of this study is to determine whether or not there is an appreciable difference between concentrations of various metal ions present in conventionally grown and processed and organically grown and processed baby foods. Two prominent, commercially available brands were chosen to undergo comparative studies between both their own conventional and organic varieties of second stage green beans and carrots. Samples were tested for cadmium, calcium, iron, lead, nickel, and zinc. Two containers of each variety of baby food were sampled in triplicate, with purchases of foods being made in separate areas to ensure that each set came from different batches. Samples were digested with nitric acid, appropriately diluted, and analyzed for metal content by flame atomic absorption spectroscopy with the regular standard calibration curve and standard addition method. There was little overall difference in metal content between the conventional and organic foods tested.

The concentrations of heavy metals (Cd, Cu, Fe, Ni, Pb, Zn) were measured in water, and fish samples caught from the pond at Fishery Park in Unicoi County, TN. The water samples were collected once a week for 8 weeks. The amounts of metals in the muscle tissues, gill, and liver of the two fish species were measured. This was to determine if any correlation exists between the metal contents in water and those in the fish samples. The concentration ranges for the heavy metals found in the water samples are as follows: Zn 0.04-0.13; Cu, 0.00-0.00; Pb, 0.00-0.59; Cd, 0.0067-0.0071; Fe, 0.208-0.512; and Ni, 0.044-0.270 ppm. The concentration range for the heavy metals found in the fish tissues are as follows: Zn 0.0-0.48; Cu, 0.00-0.00; Pb, 0.00-0.43; Cd, 0.00-99.7; Fe, 25.7-1245.5; and Ni, 0.00-268.5 ppm. There was a strong correlation found between the water and fish tissue samples.

This study aims to determine the distribution of particulates carrying heavy metals at selected sites on a college campus using dandelion leaves as collectors. As a comparison, sites far away from the campus surrounding Bristol Motor Speedway Car Racing Stadium were also monitored. To reduce the probability of memory effects from the long-term atmospheric deposition or absorption of metals from soil a seasonal plant, dandelion, was used to monitor the metal contents. The metals monitored are cadmium, calcium, copper, chromium, iron, lead, and zinc. Fourteen sites were monitored and samples were collected once a week initially (growing time of the plant), and later at 4-week interval from 28th March to 31st August of 2007. The metal contents of the nitric acid digested and appropriately diluted samples were determined by flame atomic absorption spectrometry using the regular standard calibration curve and also the standard addition method. From the results obtained, and the careful log of the weather and human activities at the different sites, it is concluded that human activities played a major role in the distribution of metal-laden particulates. Also dandelion leaves were proven to be viable collectors of these particulates without memory effects and as indicators of current particulates generated rather than a long-term cumulative one.

This thesis presents the integration of atomic vapor cells with anti-resonant reflecting optical waveguides (ARROWs) fabricated on silicon chips. These potentially provide a compact platform for a number of optical applications, including the study of quantum coherence effects such as electromagnetically induced transparency and single-photon nonlinearities, as well as frequency stabilization standards. The use of hollow waveguides allows for light propagation in low index (vapor) media with compact mode areas. ARROWs make particularly attractive waveguides for this purpose because they can be interfaced with solid core waveguides, microfabricated on a planar substrate, and are effectively single mode. ARROW fabrication utilizes an acid-removed sacrificial core surrounded by alternating plasma deposited dielectric layers, which act as Fabry-Perot reflectors. To demonstrate the effectiveness of the ARROW as a vapor cell, a platform consisting of solid and hollow core waveguides integrated with rubidium vapor cells was developed. A variety of sealing techniques were tested for vapor cell integration with the ARROW chip and for compatibility with rubidium. Rubidium was used because it is of particular interest for studying quantum coherence effects. Liquefied rubidium was transferred from a bulk supply into an on-chip vapor cell in an anaerobic atmosphere glovebox. Optical absorption measurements confirmed the presence of rubidium vapor within the hollow waveguide platform. Further analysis of the measurements revealed high optical density of rubidium atoms in the hollow core. Saturated absorption spectroscopy measurements verified that the on-chip integrated vapor cell was suitable for common precision spectroscopy applications.

Part 1 The coupled shock-tube/mass spectrometer apparatus is characterized in terms of its capabilities for chemical kinetic studies. Criteria for doing kinetic measurements by this experimental technique are discussed. The characterization experiments showed that our apparatus was capable of giving plausible signal shapes for non-reactive dynamic shots at P₁ = 5 torr. Measurements of ion current under static conditions showed that response of the quadrupole mass spectrometer was linear over a range of P₁ = 0-5 torr. Schlieren measurements indicated that the shock wave velocity was erratic and non-reproducible over the last 5 feet of the test section and that the velocity at the endwall could not be predicted from the schlieren data. The electron beam width was found to be ~.1" and the implications of this measurement for further studies on the free jet are outlined. The present beam width is suitable for jet studies in which bulk ionization of gas from a cross-section of the jet is performed. Design improvements needed for future reactive studies on our system are reviewed. In addition, experimental studies of jet risetime with a pulsed molecular beam apparatus showed poor agreement between the experimental and theoretical jet risetimes. The apparent discrepancy is discussed and possible explanations for it are given. Part 2 The rate constant k₁ for the reaction C₅H₁₂ → C₄H₉ + CH₃ was determined from reflected shock experiments (1100-1300°K) in which the progress of reaction was monitored by the appearance of H atoms. Atomic resonance absorption spectrophotometry at the Lyman-α line was performed on three mixtures (20 ppm, 10 ppm, 5 ppm) of neopentane in argon to give k₁ = .17 x 10¹⁸ exp (-84800±6200/RT) sec⁻¹. This result is in very good agreement with earlier single pulse shock tube experiments. In addition, calibration experiments for H atom were performed by shock-heating two mixtures (10 ppm and 5 ppm) of neopentane in argon. The results obtained were in good agreement with previous calibration data. / Doctor of Philosophy