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Analysis of Benzopyrenes and Benzopyrene Metabolites by Fluorescence Spectroscopy Techniques

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Date Issued:
2016
Abstract/Description:
Polycyclic aromatic hydrocarbons (PAHs) are some of the most common and toxic pollutants encountered worldwide. Presently, monitoring is restricted to sixteen PAHs, but it is well understood that this list omits many toxic PAHs. Among the (")forgotten(") PAHs, isomers with molecular weight 302 are of particular concern due to their high toxicological properties. The chromatographic analysis of PAHs with MW 302 is challenged by similar retention times and virtually identical mass fragmentation patterns.The first original component of this dissertation evolves from a high-resolution spectroscopic approach specifically developed to fulfil this gap. Herein, 4.2 K Laser-Excited Time-Resolved Shpol'skii Spectroscopy (4.2K LETRSS) is applied to the analysis of HMW-PAHs in a complex coal tar standard reference material (SRM 1597a). The spectral and lifetime information obtained with LETRSS provide the required selectivity for the unambiguous determination of PAH isomers in the high-performance liquid chromatography (HPLC) fractions. Complete LETRSS analysis is possible with microliters of HPLC fractions and organic solvent. The excellent analytical figures of merit associated to its non-destructive nature, which provides ample opportunity for further analysis with other instrumental methods, makes this approach a unique alternative for the analysis of isomers of HMW-PAHs in complex environmental samples.The second original component of this dissertation focuses on the development of screening methodology for the routine analysis of PAH metabolites in urine samples. It explores the room-temperature fluorescence (RTF) properties of 3-hydroxy-benzo[a]pyrene, benzo[a]pyrene-trans-9,10-dihydrodiol, benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol and benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol previously extracted with octadecyl-silica membranes. RTF measurements from extraction membranes are carried out with the aid of fiber optic probe that eliminates the need for manual optimization of signal intensities. Relative standard deviations varying from 2.07% (benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol) to 8.55% (3-hydroxy-benzo[a]pyrene) were obtained with a straightforward procedure. Analytical recoveries from human urine samples varied from 87.54 (&)#177; 3.11% (3-hydroxy-benzo[a]pyrene) to 99.77 (&)#177; 2.48% (benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol). The excellent analytical figures of merit and the simplicity of the experimental procedure demonstrate the potential of Solid phase extraction-RTF for screening biomarkers of PAH exposure in numerous urine samples.
Title: Analysis of Benzopyrenes and Benzopyrene Metabolites by Fluorescence Spectroscopy Techniques.
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Name(s): Al-Farhani, Bassam, Author
Campiglia, Andres, Committee Chair
Harper, James, Committee Member
Zou, Shengli, Committee Member
Frazer, Andrew, Committee Member
Lee, Woo Hyoung, Committee Member
University of Central Florida, Degree Grantor
Type of Resource: text
Date Issued: 2016
Publisher: University of Central Florida
Language(s): English
Abstract/Description: Polycyclic aromatic hydrocarbons (PAHs) are some of the most common and toxic pollutants encountered worldwide. Presently, monitoring is restricted to sixteen PAHs, but it is well understood that this list omits many toxic PAHs. Among the (")forgotten(") PAHs, isomers with molecular weight 302 are of particular concern due to their high toxicological properties. The chromatographic analysis of PAHs with MW 302 is challenged by similar retention times and virtually identical mass fragmentation patterns.The first original component of this dissertation evolves from a high-resolution spectroscopic approach specifically developed to fulfil this gap. Herein, 4.2 K Laser-Excited Time-Resolved Shpol'skii Spectroscopy (4.2K LETRSS) is applied to the analysis of HMW-PAHs in a complex coal tar standard reference material (SRM 1597a). The spectral and lifetime information obtained with LETRSS provide the required selectivity for the unambiguous determination of PAH isomers in the high-performance liquid chromatography (HPLC) fractions. Complete LETRSS analysis is possible with microliters of HPLC fractions and organic solvent. The excellent analytical figures of merit associated to its non-destructive nature, which provides ample opportunity for further analysis with other instrumental methods, makes this approach a unique alternative for the analysis of isomers of HMW-PAHs in complex environmental samples.The second original component of this dissertation focuses on the development of screening methodology for the routine analysis of PAH metabolites in urine samples. It explores the room-temperature fluorescence (RTF) properties of 3-hydroxy-benzo[a]pyrene, benzo[a]pyrene-trans-9,10-dihydrodiol, benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol and benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol previously extracted with octadecyl-silica membranes. RTF measurements from extraction membranes are carried out with the aid of fiber optic probe that eliminates the need for manual optimization of signal intensities. Relative standard deviations varying from 2.07% (benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol) to 8.55% (3-hydroxy-benzo[a]pyrene) were obtained with a straightforward procedure. Analytical recoveries from human urine samples varied from 87.54 (&)#177; 3.11% (3-hydroxy-benzo[a]pyrene) to 99.77 (&)#177; 2.48% (benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol). The excellent analytical figures of merit and the simplicity of the experimental procedure demonstrate the potential of Solid phase extraction-RTF for screening biomarkers of PAH exposure in numerous urine samples.
Identifier: CFE0006520 (IID), ucf:51363 (fedora)
Note(s): 2016-05-01
Ph.D.
Sciences, Chemistry
Doctoral
This record was generated from author submitted information.
Subject(s): Laser-Excited time-resolved Shpol'skii spectroscopy
benzo[a]pyrene
High-molecular weight polycyclic aromatic hydrocarbons
SRM 1597a
Solid-phase extraction
benzo[a]pyrene metabolites
Persistent Link to This Record: http://purl.flvc.org/ucf/fd/CFE0006520
Restrictions on Access: campus 2017-11-15
Host Institution: UCF

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