Pan, Lin2006-07-282006-07-2819971997http://hdl.handle.net/10012/104In this thesis, new SPME and derivation/SPME techniques were developed for the determination of two challenging groups of analytes, fatty acids (C2-C22 acids) and amines (C1-C6 amines), in gaseous and aqueous matrices. The studies illustrated that derivatization coupled with SPME is a versatile technique that can be used for the selective and sensitive determination of fatty acids and amines in aqueous and gaseous matrices. Derivatization/SPME techniques were performed in three ways: derivatization in the sample matrix, derivatization in the SPME fiber coating, and derivatization in the GC injector port. Derivatization in sample matrices increased coating/gas and coating/water partition coefficients of analytes, hence increased the SPME extraction efficiency and method sensitivity. Derivatization in the SPME fiber coating showed potential to quantitatively derivatize and extract polar analytes from sample; therefore could be used as an integrating sampler. In-fiber derivatization and in-injector port derivatization decreased the polarity of target analytes, thus improving their GC separation, detection and quantitation. Direct SPME was applied for the analysis of C2-C10 fatty acids and amines in aqueous solutions. Polar fiber coatings, carbowax divinylbenzene [CAX(DVB)] and poly(acrylate) (PA), extracted polar analytes, C2-C10 fatty acids and C1-C6 amines, in larger amounts than the non-polar poly(dimethylsiloxane) (PDMS) coating. For the analysis of C2-C10 fatty acids, the addition of salt and a strong mineral acid to the matrix greatly enhanced the amounts of these fatty acids extracted into the fiber coatings. Under saturated salt at pH 1.5 conditions, direct SPME had limits of detection (LODs) of pg/mL for the analysis of less polar C6-C10 fatty acids, and LODs in low ng/mL to the high ng/mL levels for more polar C2-C5 fatty acids, when GC/FID was used. For the analysis of amines in water, saturated salt at pH 10 conditions were used and the method had an LOD of ug/mL, while GC/FID was employed. Headspace SPME was also applied for the analysis of C2-C10 fatty acids in water and the results were similar to those with direct SPME. Direct SPME was employed for the analysis of long-chain (C12-C22) fatty acids in aqueous solutions. The PDMS fiber coating was shown to extract these acids in higher amounts than the polar PA coating. The optimum extraction efficiency was obtained when neutral matrix conditions were used. Direct SPME was also used to extract volatile C2-C5 fatty acids and C1-C6 amines from air. The methods had LODs in the mid- to the high pg/mL levels using GC/FID. Trace analysis of fatty acids and amines with high polarity or low volatility, in aqueous and gaseous matrices, was significantly improved when derivatization coupled with SPME was applied. For the analysis of volatile analytes in aqueous solutions, SPME/derivatization provided LODs ranging from low ng/mL levels to high pg/mL levels for C2-C5 fatty acids when GC/ECD was utilized, and low ng/mL to pg/mL range for C1-C6 primary amines when GC/GID was employed. For air analysis, quantitative derivatization and extraction of C2-C5 fatty acids in the SPME fiber coating were achieved with LODs in fg/mL range using GC/ITMS. In-matrix derivatization of volatile amines in air was successful with LODs in low pg/mL level using GC/FID. The kinetics of in-fiber derivatization for the analysis of C2-C5 fatty acids in air was theoretically modelled and the results from the experimental data were consistent with the theoretical estimates. Derivatization of long-chain fatty acids in the SPME fiber coating as well as in the GC injector was found to considerably improve GC separation, detection and quantitation of these acids. These techniques presented a convenient way to improve the GC behaviour of long-chain fatty acids. Potential applications of the derivatization/SPME techniques were demonstrated by analyzing a number of real samples.application/pdf11527656 bytesapplication/pdfenCopyright: 1997, Pan, Lin. All rights reserved.Harvested from Collections CanadaDoctoral Thesis