You are here

Time-Resolved Phosphorescence Spectroscopy at Cryogenic Temperatures for the Environmental Analysis of Polycyclic Aromatic Sulfur Heterocycles in Oil Contaminated Sites.

Download pdf | Full Screen View

Date Issued:
2017
Abstract/Description:
The large volume of crude oil released into the Gulf of Mexico by the Deepwater Horizon (DWH) accident has raised considerable concerns over potential ecosystem impacts. The dispersion of harmful oil components into the ocean waters could pose long term risks to flora and fauna. Due to the complexity of oil contaminated sites, the unambiguous identification and quantitation of environmental pollutants often requires the sequence of high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). A classic example is the analysis of the sixteen polycyclic aromatic hydrocarbons included in the priority pollutants list of the U.S. Environmental Protection Agency (EPA-PAHs).This dissertation tackles a different aspect of environmental analysis as is focuses on the photoluminescence spectroscopy of polycyclic aromatic sulfur heterocycles (PASHs). Since considering the EPA-PAHs alone can lead to drastic underestimations of potential toxic effects of oil spills, a strong case can be made for including hetero-aromatic compounds in risk assessments of contaminated sites. PASHs exist in an even greater variety of chemical structures than PAHs and, because of the asymmetry imposed by the heteroatom, the number of PASHs isomers is usually large. The existence of numerous isomers of the same molecular weight increases the difficulty of separation and identification by chromatographic methods.This dissertation demonstrates the capability to differentiate individual PASHs isomers of MW 234 g mol-1 via vibrational spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2K) temperatures. Fluorescence and phosphorescence spectra are presented for isomer determination at the parts-per-billion (ng. mL-1) concentration levels. It is demonstrated that the relatively long phosphorescence decays of PASHs facilitate the time discrimination of strong fluorescence.interference from PAHs and methylated-PAHs often present in Normal-Phase HPLC fractions. The spectral and lifetime databases compiled in this dissertation have paved the road to explore the full dimensionality of photoluminescence spectroscopy.
Title: Time-Resolved Phosphorescence Spectroscopy at Cryogenic Temperatures for the Environmental Analysis of Polycyclic Aromatic Sulfur Heterocycles in Oil Contaminated Sites.
10 views
4 downloads
Name(s): Al Tameemi, Maha, Author
Campiglia, Andres, Committee Chair
Zou, Shengli, Committee Member
Harper, James, Committee Member
Heider, Emily, Committee Member
Coffey, Kevin, Committee Member
University of Central Florida, Degree Grantor
Type of Resource: text
Date Issued: 2017
Publisher: University of Central Florida
Language(s): English
Abstract/Description: The large volume of crude oil released into the Gulf of Mexico by the Deepwater Horizon (DWH) accident has raised considerable concerns over potential ecosystem impacts. The dispersion of harmful oil components into the ocean waters could pose long term risks to flora and fauna. Due to the complexity of oil contaminated sites, the unambiguous identification and quantitation of environmental pollutants often requires the sequence of high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). A classic example is the analysis of the sixteen polycyclic aromatic hydrocarbons included in the priority pollutants list of the U.S. Environmental Protection Agency (EPA-PAHs).This dissertation tackles a different aspect of environmental analysis as is focuses on the photoluminescence spectroscopy of polycyclic aromatic sulfur heterocycles (PASHs). Since considering the EPA-PAHs alone can lead to drastic underestimations of potential toxic effects of oil spills, a strong case can be made for including hetero-aromatic compounds in risk assessments of contaminated sites. PASHs exist in an even greater variety of chemical structures than PAHs and, because of the asymmetry imposed by the heteroatom, the number of PASHs isomers is usually large. The existence of numerous isomers of the same molecular weight increases the difficulty of separation and identification by chromatographic methods.This dissertation demonstrates the capability to differentiate individual PASHs isomers of MW 234 g mol-1 via vibrational spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2K) temperatures. Fluorescence and phosphorescence spectra are presented for isomer determination at the parts-per-billion (ng. mL-1) concentration levels. It is demonstrated that the relatively long phosphorescence decays of PASHs facilitate the time discrimination of strong fluorescence.interference from PAHs and methylated-PAHs often present in Normal-Phase HPLC fractions. The spectral and lifetime databases compiled in this dissertation have paved the road to explore the full dimensionality of photoluminescence spectroscopy.
Identifier: CFE0007275 (IID), ucf:52183 (fedora)
Note(s): 2017-12-01
Ph.D.
Sciences, Chemistry
Doctoral
This record was generated from author submitted information.
Subject(s): Time-Resolved Phosphorescence Spectroscopy -- polycyclic aromatic sulfur heterocycles -- environmental analysis.
Persistent Link to This Record: http://purl.flvc.org/ucf/fd/CFE0007275
Restrictions on Access: campus 2019-06-15
Host Institution: UCF

In Collections