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Evaluation of Exposure to Combustion Products Using Multidimensional Chromatography and Ultra High Resolution Mass Spectrometry

This thesis investigates the exposure of humans to organic combustion products. Combustion of natural and anthropogenic materials can lead to highly complex mixtures of gas-phase and particle-bound chemical compounds, whose composition and health effects have been studied extensively. Nevertheless, the analysis of other potentially toxic products remains a challenge due to lack of analytical standards and methodologies. The research that encompasses this thesis is a progression from the analysis of known combustion products to the identification of previously unknown products.
Targeted analytical techniques, such as gas chromatography tandem mass spectrometry (GC-MS/MS), were utilized to evaluate firefighter exposure to wood smoke chemicals during training exercises. The results suggest that a subset of the firefighters were at higher risk of exposure which could be related to specific operational roles and the use of personal protective gear. Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCGC-TOF) was used for the identification of novel wood smoke markers and the results indicate that firefighters are equally exposed to gas-phase and particle phase compounds..
Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry is a non-targeted technique that is complementary to GCGC. Together, these tools enabled the identification of a suite of halogenated PAHs (haloPAHs) in samples obtained from the Plastimet Inc. fire, one the largest industrial fires in North America. HaloPAHs are similar in structure to toxic polychlorinated dibenzo-p-dioxins (PCDDs), a notorious class
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of toxic chemicals, and they were detected at much higher concentrations. In addition, highly substituted and high molecular weight haloPAHs were detected for the first time in an environmental sample. Finally, negative ion atmospheric pressure chemical ionization (NI-APCI) was explored as an alternative ionization technique for the analysis of mixed bromo/chloro dioxins (PXDDs) in the ash sample. PXDDs, with 1550 possible congeners, are potentially more toxic than their chlorinated counterparts (PCDDs). NI-APCI derived structure diagnostic fragments enabled the differentiation of co-eluting PXDD isomers in the ash sample which has not been possible using traditional ionization techniques (EI/CI) associated with GC-MS. / Thesis / Doctor of Philosophy (PhD)

Identiferoai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/18746
Date January 2016
CreatorsFernando, Sujan
ContributorsMcCarry, Brian E., Jobst, Karl J., Chemistry and Chemical Biology
Source SetsMcMaster University
LanguageEnglish
Detected LanguageEnglish
TypeThesis

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