Carbonaceous aerosol (soot) measured in the lower stratosphere during POLARIS and its role in stratospheric photochemistry

This paper describes recent measurements of carbonaceous aerosol made by wire impactors during the Photochemistry Ozone Loss in the Arctic Region in Summer (POLARIS) campaign and assesses their role in stratospheric photochemistry. Ninety-five percent of the carbonaceous aerosol collected during this campaign was in the form of black carbon aerosol (BCA), or soot. A new method of analyzing impactor samples is described that accounts for particle bounce and models the BCA as fractal aggregates to modify the aerodynamic collection efficiency and determine particle surface area. Results are compared to previously used methods. The new method results in an increase in the measured BCA number density of 4 times, surface area density of ∼15 times, and an increase in mass loading of 6.15 times over one previously used approach. Average values of number, surface area, and mass densities are 0.06 no./cm3,0.03 μm2/ cm3, and 0.64 ng/m3, respectively. BCA number densities are ∼1% of total aerosol number density, and BCA surface area density is ∼10% of the measured sulfuric acid aerosol surface area. Including heterogeneous reactions on BCA in a photochemical model can affect photochemistry leading to renoxification and increased ozone depletion. However, these predicted effects are not supported by the POLARIS observations, in particular, the NOx/NOy ratios. The laboratory data is not conclusive enough to determine to what extent the heterogeneous reaction is catalytic or carbon consuming. Including catalytic reactions on BCA does not statistically improve the agreement between model and measurement in any of the several scenarios considered. Furthermore, if the reactions cause even partial carbon oxidation, the BCA would be consumed at a rate inconsistent with POLARIS observations. These inconsistencies lead us to conclude that the presence of BCA in the stratosphere did not affect stratospheric photochemistry during POLARIS.