Handbook Of Polycyclic Aromatic Hydrocarbons Emission Sources And Recent Progress In Analytical Chemistry

Author : Wang Huiyong
Publisher :
ISBN 13 :
Total Pages : 232 pages
Book Rating : 4.:/5 (696 download)

DOWNLOAD NOW!

Download or read book Novel Improvements on the Analytical Chemistry of Polycyclic Aromatic Hydrocarbons and Their Metabolites written by Wang Huiyong and published by . This book was released on 2010 with total page 232 pages. Available in PDF, EPUB and Kindle. Book excerpt: Polycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation pre-concentrates PAH, simplifies matrix composition, and facilitates analytical resolution in the chromatographic column. Among the several approaches that exist to pre-concentrate PAH from water samples, the Environmental Protection Agency (EPA) recommends the use of solid-phase extraction (SPE). High-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) are the basis for standard PAH identification and determination. Ultraviolet (UV) absorption and room temperature fluorescence detection are both widely used in HPLC, but the specificity of these detectors is modest. Since PAH identification is solely based on retention times, unambiguous PAH identification requires complete chromatographic resolution of sample components. When HPLC is applied to "unfamiliar" samples, the EPA recommends that a supporting analytical technique such as GC-MS be applied to verify compound identification and to check peak-purity HPLC fractions. Independent of the volume of extracted water, the approximate time required to separate and determine the sixteen "priority pollutants" (EPA-PAH) via HPLC is approximately 60min. If additional GC-MS analysis is required for unambiguous PAH determination, the total analysis time will reach 2-3 hours per sample. If the concentrations of target species are found to lie outside the detector's response range, the sample must be diluted and the process repeated. These are important considerations when routine analysis of numerous samples is contemplated. Parent PAH are relatively inert and need metabolic activation to express their carcinogenicity. By virtue of the rich heterogeneous distribution of metabolic products they produce, PAH provide a full spectrum of the complexity associated with understanding the initial phase of carcinogenesis. PAH metabolites include a variety of products such as expoxides, hydroxyl aromatics, quinines, dihydrodiols, dioepoxides, tetrols and water soluble conjugates. During the past decades tremendous efforts have been made to develop bio-analytical techniques that possess the selectivity and sensitivity for the problem at hand. Depending on the complexity of the sample and the relative concentrations of the targeted metabolites, a combination of sample preparation techniques is often necessary to reach the limits of detection of the instrumental method of analysis. The numerous preparation steps open ample opportunity to metabolite loss and collection of inaccurate data. Separation of metabolites has been accomplished via HPLC, capillary electrophoresis (CE) and GC-MS. Unfortunately, the existence of chemically related metabolic products with virtually identical fragmentation patterns often challenges the specificity of these techniques. This dissertation presents significant improvements in various fronts. Its first original component--which we have named solid-phase nano-extraction (SPNE)--deals with the use of gold nanoparticles (Au NPs) as extracting material for PAH. The advantages of SPNE are demonstrated for the analysis of PAH in water samples via both HPLC and Laser-Excited Time-Resolved Shpol'skii Spectroscopy (LETRSS). The same concept is then extended to the analysis of monohydroxy-PAH in urine samples via SPE- HPLC and In-Capillary SPNE-CE. The second original component of this dissertation describes the application of Shpol'skii Spectroscopy to the analysis of polar PAH metabolites. The outstanding selectivity and sensitivity for the direct analysis of PAH at trace concentration levels has made Shpol'skii spectroscopy a leading technique in environmental analysis. Unfortunately, the requirement of a specific guest-host combination--typically a non-polar PAH dissolved in an n-alkane-- has hindered its widespread application to the field of analytical chemistry. This dissertation takes the first steps in removing this limitation demonstrating its feasibility for the analysis of polar benzopyrene metabolites in alcohol matrixes.