Analysis of Organic Molecular Markers in Atmospheric Fine Particulate Matter: Understanding the Impact of "Unknown" Point Sources on Chemical Mass Balance Models

Particle-phase organic tracers (molecular markers) have been shown to be an effective method to assess and quantify the impact of sources of carbonaceous aerosols. These molecular markers have been used in chemical mass balance (CMB) models to apportion primary sources of organic aerosols in regions where the major organic aerosol source categories have been identified. As in the case of all CMB models, all important sources of the tracer compounds must be included in a Molecular Marker CMB (MM-CMB) model or the MMCMB model can be subject to biases. To this end, the application of the MM-CMB models to locations where reasonably accurate emissions inventory of organic aerosols are not available, should be performed with extreme caution. Of great concern is the potential presence of industrial point sources that emit carbonaceous aerosols and have not been well characterized or inventoried. The current study demonstrates that emissions from industrial point sources in the St. Louis, Missouri area can greatly bias molecular marker CMB models if their emissions are not correctly addressed. At a sampling site in the greater St. Louis Area, carbonaceous aerosols from industrial point sources were found to be important source of carbonaceous aerosols during specific time periods in addition to common urban sources (i.e. mobile sources, wood burning, and road dust). Since source profiles for these industrial sources have not been properly characterized, method to identify time periods when point sources are impacting a sampling site, needs to avoid obtaining biases source apportionment results. The use of real time air pollution measurements, along with molecular marker measurements, as a screening tool to identify when point sources are impacting a receptor site is presented.