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Chemical activation experiments and computational methods have been used to study the unimolecular reactions of C2H5CH2Br and C2D5CHFBr with 90 and 93 kcal mol–1 of vibrational energy, respectively...

Measurements of the mass concentration and chemical speciation of aerosols are important to investigate their chemical and physical processing from near emission sources to the most remote regions of the atmosphere. A common method to analyze aerosols is to collect them onto filters and to analyze filters off-line; however, biases in some chemical components are possible due to changes in the accumulated particles during the handling of the samples. Any biases would impact the measured chemical composition, which in turn affects our understanding of numerous physico-chemical processes and aerosol radiative properties. We show, using filters collected onboard the NASA DC-8 and NSF C-130 during six different aircraft campaigns, a consistent, substantial difference in ammonium mass concentration and ammonium-to-anion ratios, when comparing the aerosols collected on filters versus the Aerodyne Aerosol Mass Spectrometer (AMS). Another on-line measurement is consistent with the AMS in showing that the aerosol has lower ammonium-to-anion ratios than obtained by the filters. Using a gas uptake model with literature values for accommodation coefficients, we show that for ambient ammonia mixing ratios greater than 10 ppbv, the time scale for ammonia reacting with acidic aerosol on filter substrates is less than 30 s (typical filter handling time in the aircraft) for typical aerosol volume distributions. Measurements of gas-phase ammonia inside the cabin of the DC-8 show ammonia mixing ratios of 45 ± 20 ppbv, consistent with mixing ratios observed in other indoor environments. This analysis enables guidelines for filter handling to reduce ammonia uptake. Finally, a more meaningful limit-of-detection for filters that either do not have an ammonia scrubber and/or are handled in the presence of human emissions is ∼0.2 μg m−3 ammonium, which is substantially higher than the limit-of-detection of the ion chromatography.

Chemical activation experiments and computational methods have been used to study the unimolecular reactions of C