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Pesticide residue analysis is very important both in agriculture and environmental protection. The effectiveness of the analytical method depends very much on the extraction and preconcentration of the analytes prior to the actual analysis, as these analytes occur in trace concentrations that may be lower than the detection limit of the instrument. Various methods of extraction and pre-concentration have been introduced in an effort to decrease costs and other negative environmental impacts without compromising efficiency. One such method is single-drop micro-extraction (SDME), whose benefits cannot be overemphasised. This method has been recently introduced in the pool of pre-concentration methods for pesticide and other organic residues. In this study, the SDME method has been developed using chloroform as a solvent for preconcentration of a ten-component mixture of triazine (TP619) herbicides, followed by analysis by gas chromatography and flame ionisation detector (ppm level detection) and mass spectrometry for detection at sub-ppb level. The developed method uses the simple introduction of an air bubble to the micro-litre droplet of the organic solvent used for extraction of the triazines. This air-bubble showed the increase in the extraction efficiency of the method by about 30% relative to the optimised extraction without the air bubble. The air bubble works very well with addition of the salt (10% NaCl) to the solution being extracted, with further extraction enhancements being observed. Traditionally, the solution being extracted is stirred to achieve good mass transfer. However, the present method does not require stirring as stirring makes the system unstable resulting in reduced precision. The optimum conditions for the newly developed method, named bubble-in-drop single-drop micro-extraction (BID-SDME) were found to be as follows: 1 μL chloroform, 0.5 μL air bubble, 10% NaCl and static equilibration for 20 minutes, while the sample volume is 1 mL. This method showed linearity in the region of 1 ppm to 0.05 ppb (about six orders of magnitude) as long as the instrumental settings were optimised for increased sensitivity. The RSD values observed in this method were better than those recorded in literature, being <10%. Some instrumental manipulations are necessary to realise the full potential of the instrument. Various settings were explored on the GC-MS to optimise its performance below the ppb level. It was observed that the configuration that gave the best sensitivity and the lowest limits of detection was the high-pressure and split-less injection mode. This improved the detection limits of the instrument by 2 orders of magnitude (from 1 ppb to below 0.05 ppb). The GC-MS performance was further improved by the use of selected ion monitoring (SIM) mode of analysis. This technique reduced the interferences from the co-extracted compounds that can compromise the precision and accuracy of the analytical method especially at low concentration applicable in trace analysis. The new BID-SDME method was applied to various samples (dam water, synthetic hard water, dam sediment, humic and sandy soil samples) giving unsurpassed efficiencies with very low RSD values. In these systems, NaCl addition (10% w/v) not only increased extraction efficiency but also had a matrix-normalising effect as the RSD values were reduced and the matrix effects somewhat diminished. The application of this method to orange juice required the addition of only 5% NaCl (not 10% like the other samples). The results obtained with the extraction of orange juice were better than those recorded in literature. The normalising effect was further observed as the RSD values with addition of the NaCl were reduced the RSD from 11.7 (salt-free solution) to 5.56 (5% NaCl). These application experiments were carried out at the 0.2 ppb level using spiked samples. The method was compared against the other extraction techniques used in trace analysis (especially SPME) and it performed better overall giving lower RSD values and much improved detection limits. The calculated detection limits for the ten triazines used in the mixture were in the region of parts per trillion (0.9-14 ppt) with RSD values of < 10% with the use of internal standard. / Prof. D.B.G. Williams Mr. R. Meyer

Call number: LD2668 .T4 1950 S663 / Master of Science

The three factors of the resolution (Rs)equation(see Equation 1.1)were explored in this thesis. During the course of the research project, an important aim was to explore separation processes that would lead to an increase in productivity without sacrificing Rs. To that end, an increase in the retention factor (k)to enhance Rs was deemed detrimental to the cycle time, hence the production rate, particularly when preparative separations are involved. Consequently the primary objectives were to (i)prepare more efficient columns and (ii)investigate new strategies in manipulating selectivity. The significance of the work contained in this thesis is highlighted in 27th International Symposium on High Performance Liquid Phase Separations and Related Techniques (HPLC 2003)held in Nice, France between 15-19 June, 2003. Many of the papers presented significantly compared to chapters contained in this research / Doctor of Philosophy (PhD)

This thesis describes a developmental process required for the construction and optimisation of two-dimensional liquid chromatographic systems. The text encompasses much of the difficulties and provides a frame work for achieving positive results. The hardware requirements and the concepts for successful completion of heart-cutting and comprehensive modes of separation are addressed. Low molecular weight polystyrenes play an essential role in providing a model framework or theme for the development of two-dimensional liquid chromatographic systems. Low-molecular weight oligostyrenes were initially used to provide a theoretical assessment of combinations of liquid chromatographic systems. Interpretation of theoretical results then allowed for the development of a heart-cutting two-dimensional liquid chromatographic system for the separation of oligostyrene complex samples. This allowed for practice to be compared with the theoretical results, which are presented and provided direction as to what attributes of a two-dimensional liquid chromatographic system are beneficial. Petroleum oils are one of the most complex mixtures found in the natural environment and are included to provide a real-world application that demonstrates the potential power of comprehensive two-dimensional liquid chromatographic systems. Orthogonality is a central theme throughout the whole thesis. Separation correlation is shown to be advantageous in certain instances in the evaluation of hybrid stationary phases, as shown in the analysis of a low molecular weight polystyrene sample. The thesis finishes by the incorporation of monolithic separation media as an alternative second dimension stationary phase support. A method is discussed that allows for a substantial increase in the volume and concentration loading of two-dimensional liquid chromatographic systems that employ monolithic chromatography columns in the second dimension. This is important since volume overloading and concentration overloading in the second dimension can reduce separation performance and hence the final chapter provides a new direction for research. / Doctor of Philosophy (PhD)

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Abraham M. Lenhoff, Dept. of Chemical Engineering. Includes bibliographical references.

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