Uptake of Small Oxygenated Organic Molecules onto Ammonium Nitrate under Upper Tropospheric Conditions

Abstract

The uptake of formic (C1), propanoic (C3), butanoic (C4), and pentanoic (C5) acids onto ammonium nitrate (AN) has been investigated as a function of temperature and relative humidity using a Knudsen cell flow reactor coupled with FTIR-reflection absorption spectroscopy (FTIR-RAS). The uptake of acetone and methanol onto AN was also briefly studied. Initial uptake coefficients (gamma) were determined over the temperature range 200-240 K. Formic, propanoic, and butanoic acids exhibited efficient but temperature-dependent uptake on AN, with larger uptake coefficients observed at lower temperatures. Pentanoic acid was not taken up by AN under any of the conditions studied. Uptake of acetone and methanol onto AN was observed, but in insignificant amounts under atmospherically relevant conditions. Infrared spectra revealed that propanoic and butanoic acids ionized on the surface, despite the fact that the AN films were effloresced. Formic acid reacted with the AN film to produce ammonium formate and ionized nitric acid. Adding small amounts of water vapor (4% RH) to the chamber resulted in dramatically increased gamma values for all of the acids. Furthermore, the IR spectra showed the formation of a liquid layer when propanoic and butanoic acids adsorbed on the surface at RH = 20% and greater. Liquid water features were not observed at a similar relative humidity in the absence of the acids. These results show that small organic acids can be efficiently scavenged by AN and lead to enhanced water uptake under upper tropospheric conditions.