Solid Phase Excitation-Emission Matrix Spectroscopy for In-Situ Chemical Analysis of Combustion Aerosols

Exposure to combustion generated aerosols such as PM from residential woodburning, forest fires, cigarette smoke, and traffic emission have been linked to adverse health outcomes. It is important to assess the chemical composition of PM to examine personal exposure. Excitation-emission matrix (EEM) spectroscopy has been shown as a sensitive and cost-effective technique for evaluation of combustion PM composition and as a source apportionment tool. However, EEM measurements are hindered by a solvent extraction step and a need for benchtop instrumentation. Here, we present a methodology that eliminates this labor-intensive sample preparation and allows to automate and miniaturize the detection platform. A miniature electrostatic collector deposits PM sample onto transparent polydimethylsiloxane (PDMS) coated substrate, where PAH components are extracted into solid-phase (SP) solvent and analyzed using EEM spectroscopy in-situ. We evaluated external and internal excitation schemes to optimized signal to noise ratio. Analysis of woodsmoke and cigarette smoke samples showed good agreement with liquid extraction EEM spectra. Internal excitation is hindered by fluorescent interference from PDMS at λ<250nm. The external excitation EEM spectra are dependent on the incident angle; ranges of 30-40⁰ and 55-65⁰ showed the best results. The proposed SP-EEM technique can be used for development of miniaturized sensors for chemical analysis of combustion generated PM.