Intercomparison and evaluation of four semi-continuous PM_2.5 sulfate instruments

The development and evaluation of time-resolved (minutes) measurement technologies to characterize the physical and chemical make up of ambient aerosols/particulate matter in the atmosphere are essential to our improved understanding of aerosol process science, source attribution, and population exposure. During the PMTACS-NY summer 2001 campaign in Queens/New York, a wide variety of on-line aerosol analysis instruments were deployed together with gas-phase and filter sampling techniques. Here, we report on the intercomparison of four semi-continuous PM_2.5 sulfate instruments and evaluation of these instruments with one set of 6h and three sets of 24-h filter measurements, collected at the same site. The semi-continuous instruments were an aerosol mass spectrometer, a particle-into-liquid sampler coupled with ion chromatograph, a Rupprecht & Patashnick Sulfate Monitor (R&P 8400S), and a continuous sulfate monitor developed by George Allen at Harvard School of Public Health and built in the field by one of us (J.J.S.). We found an excellent almost one-to-one correlation between the four semi-continuous instruments with typical multiple R-squared values >0.9. In addition, the correlations of the semi-continuous data with the filter measurements are also highly linear (R² 0.86-0.98) but the semi-continuous instruments recover only about 85% of the sulfate mass collected by the filter techniques. The most likely explanation for this deviation is a combination of positive sampling artifacts on the filters (collection of particles with diameter greater then 2.5μm, oxidation/condensation processes on the filters) with negative biases of the semi-continuous measurements (inlet line losses, limited collection efficiency for small particles below ca. 0.1μm).