Feasibility of coupling a thermal/optical carbon analyzer to a quadrupole mass spectrometer for enhanced PM2.5 speciation

ABSTRACT A thermal/optical carbon analyzer (TOA), normally used for quantification of organic carbon (OC) and elemental carbon (EC) in PM2.5 (fine particulate matter) speciation networks, was adapted to direct thermally evolved gases to an electron impact quadrupole mass spectrometer (QMS), creating a TOA-QMS. This approach produces spectra similar to those obtained by the Aerodyne aerosol mass spectrometer (AMS), but the ratios of the mass to charge (m/z) signals differ and must be remeasured using laboratory-generated standards. Linear relationships are found between TOA-QMS signals and ammonium (NH4+), nitrate (NO3−), and sulfate (SO42-) standards. For ambient samples, however, positive deviations are found for SO42-, compensated by negative deviations for NO3−, at higher concentrations. This indicates the utility of mixed-compound standards for calibration or separate calibration curves for low and high ion concentrations. The sum of the QMS signals across all m/z after removal of the NH4+, NO3−, and SO42- signals was highly correlated with the carbon content of oxalic acid (C₂H₂O₄) standards. For ambient samples, the OC derived from the TOA-QMS method was the same as the OC derived from the standard IMPROVE_A TOA method. This method has the potential to reduce complexity and costs for speciation networks, especially for highly polluted urban areas such as those in Asia and Africa. Implications: Ammonium, nitrate, and sulfate can be quantified by the same thermal evolution analysis applied to organic and elemental carbon. This holds the potential to replace multiple parallel filter samples and separate laboratory analyses with a single filter and a single analysis to account for a large portion of the PM2.5 mass concentration.