Ph.D. (Chemistry) / Please refer to full text to view abstract

Thesis (M. S.)--Civil and Environmental Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Michael Saunders; Committee Member: Ching-Hua Huang; Committee Member: Marc Frischer.

Chemical speciation has become increasingly important in environmental and industrial systems, because of the difference in properties of the different physico-chemical forms of an element. In modern environmental and industrial analysis the determination of these individual species are required over and above total elemental analysis. In particular, oxidation state speciation has become a focus area of modern analytical chemistry. Hyphenated techniques where two or more analytical techniques are coupled, have been widely used in chemical speciation analysis. In particular, chromatographic techniques coupled with suitable detection systems have been proved to be very useful in trace element speciation. In this study, modified hyphenated techniques have been proposed for vanadium and thallium speciation. Two main species of vanadium, V(IV) and V(V) as a redox couple are widely used in petrochemical industries for the removal of sulphur. The effectiveness of vanadium as a catalyst is dependent on the ratio of the two species. Ion chromatography with an anion exchange column as the separation system, followed by ICP-OES detection at the wavelength of 309.311 nm has been proposed for the determination of the two species. In this method, EDTA was used for the stabilization of V(IV) and for the formation of V(IV) and V(V) EDTA complexes, which can be separated readily by means of a Dionex anion exchange column (AG5 guard column). The detection limits were 0.02 mg/L for V(IV), and 0.05 mg/L for V(V). The use of an ultrasonic nebulizer can enhance the sensitivity and therefore improve detection limits to as low as 2 ƒÝg/L for both species. The method is fast, cost-effective and interference free and was successfully used in the analysis of complex industrial samples. Thallium speciation is important because thallium species have accumulative toxicity to humans. No methods for the simultaneous separation and determination of thallium species could be found in the chemical literature. In this research, a new hyphenated method, namely HPLC coupled with ICP-OES was developed for the simultaneous separation and determination of the two thallium species, Tl(I) and Tl(III). DTPA was used in this method for stabilizing Tl(III) by formation of an anionic Tl(III)-DTPA complex. After stabilization, the two species were separated by using a Dionex cation exchange column, CG12A guard column, followed by ICP-OES detection at the wavelength of 351.924 nm. The detection limits were 0.8 mg/L and 0.1 mg/L for both species when using a V-groove nebulizer and ultrasonic nebulizer, respectively. No spectral interferences were observed. Only iodide can cause a chemical interference by forming a precipitate with Tl(I). / Prof. P.P. Coetzee

Thesis (M.S.)--University of North Carolina at Wilmington, 2003. / Includes bibliographical references (leaves : 43-45).

Thesis (Ph. D.)--West Virginia University, 2004. / Title from document title page. Document formatted into pages; contains xvi, 193 p. : ill. Vita. Includes abstract. Includes bibliographical references.

Mercury occurs naturally in the environment and is released by human activities. Mercury exists in gaseous, liquid, and solid phases, and all phases are of importance when fate s effects of mercury in terrestrial, fresh and marine water, and atmospheric environments. Mercury can be transformed to a highly toxic form of methylmercury. Humans are exposed to the toxicity of methylmercury by eating fish. Methylmercury is bioaccumulated up the food chain by transfer of residues of methylmercury in smaller organisms that are food for larger organisms in the chain. This sequence of process results in higher concentrations in organisms at higher levels in the food chain with human at the top of the food chain. This study is an evaluation of chemical speciation and biological processes that govern mercury distribution and transformation among three environmental media: atmosphere, water, and sediments. Understanding speciation of mercury and biological processes of methylmercury transformation plays an important part in toxicity and exposure of mercury to living organisms. Speciation also influences transport of mercury within and between environmental media while biological processes of methylmercury transformation influence methylmercury production and its transport to the biological communities. Study also covers the demethylation process that can convert methylmercury to inorganic mercury species. Demethylation and methylation processes therefore may occur in parallel further complicating the assessment of mercury fate in the environment. The study will provide integrated fundamental pathways of mercury species transformation through chemical and biological pathways and will contribute to an understanding of fate and transport of mercury species in environmental media. It will also provide a foundation for a state- and region-wide examination of mercury monitoring and control strategies.

Thesis (M.S.)--West Virginia University, 2004. / Title from document title page. Document formatted into pages; contains xiii, 152 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 82-86).

Thesis (Ph. D.)--University of California, Santa Cruz, 1996. / Typescript. Includes bibliographical references (leaves 149-150).

A lack of methods for the separation and determination of air-sensitive Cr(II) and stable Cr(III) complexes in aqueous and organic phase motivated this study. The formation of kinetically stable Cr(III) complexes with common anions was studied using ion chromatography coupled to inductively-coupled plasma emission spectrometry (ICP-OES). Distribution diagrams for the complex species were determined from the results. Estimations of the stability constants were made from these diagrams and compared with stability constants published in the literature. Separation and determination of Cr(II) and Cr(III) and their complexes with PDCA and EDTA in aqueous phase was investigated using ion chromatography. ICP-OES was used for detection purposes. The separation and determination of Cr(II) and Cr(III) complexes with a ligand, bis-(2-decylsulphanyl-ethyl)amine, developed by Sasol Technology (Pty) Ltd., was attempted. The study was undertaken as the Cr(III) complex is used as a catalyst in the trimerisation of ethylene to 1-hexene. The mechanism is still unknown and determining which species are present in the catalytic cycle could clarify which oxidation-reduction couple is involved during the cycle. Reversed phase HPLC was investigated as a possible method for the separation of these complexes. No separation of the species was, however, achieved. / Prof. P.P. Coetzee

Graduation date: 1991