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Investigation of Reagent Gases for the Positive Chemical Ionization of Select Polybrominated Diphenyl Ethers
Citation:
PAWLECKI-VONDERHEIDE, A. M., K. Thaxton, P. KAUFFMAN, AND J. N. MORGAN. Investigation of Reagent Gases for the Positive Chemical Ionization of Select Polybrominated Diphenyl Ethers. Microchemical Journal. Elsevier BV, AMSTERDAM, Netherlands, 95(2):279-284, (2010).
Impact/Purpose:
The overall goal of this research program is to identify those chemicals, pathways, and activities that represent the highest potential exposures to children and to determine the factors that influence these exposures. The following objectives will address this goal: Revise and refine the existing research plan for children's exposure measurements research. Collect measurement data on children's exposures. Provide analytical support to children's pesticide exposure research. Develop analytical methods for pesticides in duplicate diet food samples. Develop and apply analytical methods for other chemicals including but not limited to brominated diphenyl ethers, phthalates, perfluorinated chemicals. Evaluate the impact of chiral chemistry on the risk to children and exposure assessment. Provide support to the National Children's Study. Perform data analyses to fill critical data gaps. Conduct analyses of dietary samples and refine the dietary model for the dietary exposure algorithm.
Description:
Polybrominated diphenyl ethers (PBDEs) fall into the class of compounds known as brominated flame retardants and their incorporation in a multitude of products is responsible for saving numerous lives. However, toxicology studies have alerted researchers to the potential adverse health effects that may develop as a result of prolonged or extreme exposure to these compounds. Frequent disposal and subsequent leaching has focused concern on environmental concentrations and current reports cite increasing levels. Method development continues in support of this research and the present work examines the feasibility of utilizing gas chromatography ion trap mass spectrometry operating in positive ion chemical ionization mode. In the evaluation of reagents for chemical ionization (methane, methanol and acetonitrile), comparative results of all three reagents demonstrated more difficult protonation as the number of bromine atoms increased. Methane, possessing the lowest proton affinity, provided the highest response for the analytes. Further, when methane chemical ionization was compared to electron impact ionization, the tetra-congener showed approximately 8x greater sensitivity and the penta- and hexa-congeners demonstrated approximately 2x greater. CI parameters, such as ionization and reaction times, were optimized to provide the highest analyte response and this was followed by the investigation of the employment of MSn. In the this mode, optimal excitation amplitude delivered sufficient fragmentation while maintaining maximum signal, yielding final instrument detection limits in the sub µg L-1 range.