This thesis deals with instrumental and methodological developments for speciation analysis of gaseous mercury (Hg(g)), based on isotope dilution analysis (IDA). The studied species include Hg0, (CH3)2Hg, CH3HgX and HgX2 (where X symbolises a negatively charged counter ion in the form of a halide or hydroxyl ion). Gas chromatography hyphenated with inductively coupled plasma mass spectrometry (GC-ICPMS) was used for separation and detection of Hg(g) species. Permeation tubes were used for the generation of gaseous isotopically enriched Hg standards (tracers). These tracers were continuously added to the sample gas stream during sampling of Hg(g). A mobile prototype apparatus incorporating both the permeation source and a sampling unit for collection of Hg(g) was developed and used for this purpose. Hg(g) species were pre-concentrated on Tenax TA and / or Carbotrap solid adsorbents. Au-Pt was used for pre-concentration of total Hg(g), either as the primary medium, or as backup. Collected species were eluted from these media and introduced to the instrument by thermal desorption. Various degrees of species transformations, as well as losses of analyte during pre-concentration and elution, were found to occur for both Tenax TA and Carbotrap. The performance characteristics of these media were shown to be species specific, as well as matrix dependent. The development of an on-line derivatisation procedure allowed for minimised species transformations, as well as reduced adsorption and memory effects of ionic Hg(g) species within the analytical system. In conclusion, IDA provides an important tool for identification, minimisation and correction of the above mentioned analytical problems. Furthermore, it offers significant advantages with respect to quality assurance, compared to conventional techniques, both when it comes to rational development of new methodology, as well as for continuous validation of existing procedures. The developed methodology for speciation analysis of Hg(g) has been tested in various applications, including the determination of Hg(g) species concentrations in ambient air (both in and outdoor) and in the head space of sediment microcosms. Hg(g) species were formed in the sediments as a result of naturally occurring redox and methylation processes, after addition of an isotope enriched aqueous Hg(II) precursor. The methodology has also been used for assessing the risk of occupational exposure to Hg(g) species during remediation of a Hg contaminated soil and for studying Hg0(g) transport and Au-Pt pre-concentration characteristics in natural gases. Hg0 was used as the model species in the latter experiments, since it is believed to be the dominating form of Hg(g) in natural gas. The results indicate that the occurrence of H2S can cause temperature dependent adsorption and memory effects of Hg0(g) in the presence of stainless steel, thereby providing a plausible explanation to the variability of results for sour gases occasionally observed in the field. Hg0(g) has demonstrated overall high recovery during collection on Au-Pt tubes for all gases tested in this thesis. Recent (unpublished) results however indicate that there are potential species specific and matrix dependent effects associated with the Au-Pt based pre-concentration of Hg(g) in natural gases.

Size exclusion chromatography (SEC) was applied for purification of psychoactive biomolecules from plants. These molecules are in the same molecular weight range, but do not necessarily share other chemical properties, that makes the SEC technique efficient. By applying SEC as a first purification step much of the co-extractives from the plants can easily be removed. Large amounts of target substance can be obtained with little effort if the system is automated. Combining SEC with a second purification step, consisting of normal phase chromatography, provides high purity of the target substance. Both known and unknown psychoactive biomolecules can easily be purified using the purification method developed in this Master's Thesis. Purifications that previously required long time and much "hands-on" can be completed much faster and with less manual work. The method developed was tested on cannabis, coffee and 'Spice' with good results.

Characterization of semi-permeable films promotes the systematic selection of membranes and process design. When acquiring the diffusive and sorption properties of gas transport in non-porous membranes, the time lag method is considered the conventional method of characterization. The time lag method involves monitoring the transient accumulation of species due to permeation on a fixed volume present in a downstream reservoir. In the thesis at hand, an alternative approach to the time lag technique is proposed, termed as the short cut method. The short cut method appoints the use of a two reservoir system, where the species decay in the upstream face of the membrane is monitored, in combination with the accumulation on the downstream end. The early and short time determination of membrane properties is done by monitoring the inflow and outflow flux profiles, including their respective analytical formulas. The newly proposed method was revealed to have estimated the properties at 1/10 the required time it takes for the classical time lag method, which also includes a better abidance to the required boundary conditions. A novel design of the upstream reservoir, consisting of a reference and working volume, is revealed, which includes instructional use, and the mechanics involved with its operation. Transient pressure decay profiles are successfully obtained when the reference and working volumes consisted of only tubing. However when tanks were included in the volumes, large errors in the decay were observed, in particular due to a non-instantaneous equilibration of the pressure during the start up. This hypothesis was further re-enforced by examining different upstream tank-based configurations. iii In the end, a validated numerical model was constructed for the purpose of simulating the two reservoir gas permeation system. A modified form of the finite differences scheme is utilized, in order to account for a concentration-dependent diffusivity of penetrants within the membrane. Permeation behavior in a composite membrane system was disclosed, which provided a new perspective in analyzing the errors associated with the practical aspect of the system.

Characterization of semi-permeable films promotes the systematic selection of membranes and process design. When acquiring the diffusive and sorption properties of gas transport in non-porous membranes, the time lag method is considered the conventional method of characterization. The time lag method involves monitoring the transient accumulation of species due to permeation on a fixed volume present in a downstream reservoir. In the thesis at hand, an alternative approach to the time lag technique is proposed, termed as the short cut method. The short cut method appoints the use of a two reservoir system, where the species decay in the upstream face of the membrane is monitored, in combination with the accumulation on the downstream end. The early and short time determination of membrane properties is done by monitoring the inflow and outflow flux profiles, including their respective analytical formulas. The newly proposed method was revealed to have estimated the properties at 1/10 the required time it takes for the classical time lag method, which also includes a better abidance to the required boundary conditions. A novel design of the upstream reservoir, consisting of a reference and working volume, is revealed, which includes instructional use, and the mechanics involved with its operation. Transient pressure decay profiles are successfully obtained when the reference and working volumes consisted of only tubing. However when tanks were included in the volumes, large errors in the decay were observed, in particular due to a non-instantaneous equilibration of the pressure during the start up. This hypothesis was further re-enforced by examining different upstream tank-based configurations. iii In the end, a validated numerical model was constructed for the purpose of simulating the two reservoir gas permeation system. A modified form of the finite differences scheme is utilized, in order to account for a concentration-dependent diffusivity of penetrants within the membrane. Permeation behavior in a composite membrane system was disclosed, which provided a new perspective in analyzing the errors associated with the practical aspect of the system.

Transport of amorphous and semi-crystalline, oriented, annealed and non-annealed PET films has been studied using pure and mixed gas/vapor feeds to understand the influence of flavor molecules on the efficacy of the barrier material. Methanol has been used as the flavor molecule simulant, and pure methanol vapor sorption studies show swelling and relaxation effects in the polymer. Multi-component transport of O2/methanol and O2/CO¬2/methanol mixtures, performed at different activities of methanol, shows that vapor induced plasticization leads to increases in O2 and CO2 permeability. Annealed, semi-crystalline PET is shown to be most resistant to plasticization effects. It has been shown that the non-annealed film is less stable despite similar crystallinity as the annealed film due to the presence of orientation related stress in the material. Presence of crystals also restricts the chain motion, and helps suppress the plasticization effects. The results have been compared with the predictions of the dual mode model for multi-component mixtures. Plasticization effects at the high activities have been analyzed within the framework of the free volume theory. It has been proposed that only the densified domains of a glassy polymer be considered when evaluating fractional free volume change due to swelling in the polymer-penetrant system. The free volume parameter- BA has been evaluated for O2 and CO2 in PET and is found to be different from that for other high permeability polymers.

Water resource is one of the most important natural resources on earth. In recent years, due to the discharges of large industrial and domestic waste-water into the nature, water pollution problem is getting more and more serious and how to monitor the quality of water in real time has become a very important research issue. The dissolved oxygen is one of the critical indexes for evaluating the quality of water. Although the conventional dissolved oxygen detectors presented a high sensitivity and high accuracy, the high cost, large dimension, low capability of batch fabrication and real-time monitoring will limit their applications. In this thesis, an extended-gate field-effect transistor (EGFET) based dissolved oxygen microsensor is developed utilizing micro-electromechanical system (MEMS) technology. The gate voltages of EGFET under different concentrations of dissolved oxygen can be detected by the Cr/Au sensing electrode. To further enhance the sensitivity of the proposed microsensor, a polystyrene layer with very high permeation rate of the dissolved oxygen gas is adopted and coated on the surface of Cr/Au layer. The main processing steps of the presented microsensor involve four photolithographic and four thin-film deposition processes. The influence of the channel¡¦s width/length ratio, source/drain geometry and polystyrene additional layer on the sensitivity of the EGFET based dissolved oxygen microsensor are investigated in this study. The chip size of the implemented dissolved oxygen microsensor is 11 mm¡Ñ13 mm¡Ñ 0.5 mm and the sensing area is 1 mm¡Ñ1 mm. As the dissolved oxygen concentration varies from 2 ppm to 6 ppm, a very high sensitivity (35.36 mV/ppm) and sensing linearity (98.83%) of the proposed EGFET microsensor can be demonstrated. In addition, the response time of the presented dissolved oxygen microsensor is only about III 180~200 seconds, hence it is very suitable for developing a real-time monitoring microsystem.

During a rod extrusion process, the oxidation layer and the segregation layer at the billet surface are possibly drawn inside the billet and become one part of the product, which portion with surface-permeation has to be cut off and results in a low productivity of the extrusion process. In this paper, the mechanism of permeation of the oxidation and segregation layers at the billet surface is explored using a finite element analysis. The effects of various extrusion conditions, such as extrusion ratio, inclination angle, billet length, the thickness of oxidation layer, etc., on the length of the portion with surface permeation are discussed systematically. Optimal inclination angles for a free surface-permeation product under different extrusion ratios are found out. An empirical equation for the optimal inclination angles is also proposed. Finally, experiments of extrusion of aluminum rods are conducted to validate the analytical model proposed.

Thesis (M.S.)--Mississippi State University. Department of Chemistry. / Title from title screen. Includes bibliographical references.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1969. / Bibliography: leaves 89-91.

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