Trace-level measurement of complex combustion effluents and residues using multidimensional gas chromatography–mass spectrometry (MDGC–MS)

Abstract

The identification and quantitation of non-method-specific target analytes have greater importance with respect to EPA's current combustion strategy. The risk associated with combustion process emissions must now be characterized. EPA has recently released draft guidance on procedures for the collection of emissions data to support and augment site-specific risk assessments (SSRAs) as part of the hazardous waste incineration permitting process. This guidance includes methodology for quantifying total organic (TO) emissions as a function of compound volatility. The ultimate intent is to compare the amount of organic material identified and quantified by target analyte-specific methodologies to organic emissions quantified by the TO methodology. The greater the amount accounted for by the target analyte-specific methodologies, the less uncertainty may be associated with the SSRAs. A limitation of this approach is that the target analyte-specific methodologies do not routinely quantify compounds of low toxicological interest; nor do they target products of incomplete combustion (PICs). Thus, the analysis can miss both toxic and non-toxic compounds. As a result, it is unknown whether the uncharacterized fraction of the TO emission possesses toxic properties. The hypothesis that we propose to test is that organic emissions and organics extracted from particulate matter (PM) are more complex than standard GC-MS-based instrumentation can currently measure. This complexity can affect quantitation for toxic compounds, thereby potentially affecting risk assessments. There is a pressing need to better characterize these organic emissions from hazardous waste incinerators and PM extracts from various other combustion sources. We will demonstrate that multidimensional gas chromatography–mass spectrometry (MDGC–MS) procedures significantly improve chromatographic separation for complex environmental samples. Sequential repetitive heart-cutting MDGC, with coupled mass spectrometry will be shown to be a complete analysis technique. The ability of this technique to disengage components from complex mixtures taken from hazardous and municipal waste incinerators will be shown.