Measurements of acetone, acetic acid, and formic acid in the northern midlatitude upper troposphere and lower stratosphere

Abstract

We have measured acetone, acetic acid, and formic acid concentrations in the upper troposphere and lower stratosphere over Germany. The measurements were performed by ion molecule reaction mass spectrometry using new kinetic data on ion molecule reactions of formic and acetic acids with negative ions obtained at our laboratory. Mean volume mixing ratios between 384 and 832 parts per trillion (pptv) for acetone, 110 and 357 pptv for acetic acid, and 59 and 215 pptv for formic acid were obtained. The correlation between formic acid and acetic acid was very poor (r2 = 0.14). A better correlation could be observed for acetone and acetic acid, with a correlation coefficient r2 = 0.46 and a slope (acetic acid/acetone) of 0.31. For acetic acid a maximum around 9 km was observed. A significant fraction of the acetic acid observed in the lower stratosphere may be due to in situ photochemical production by reactions of HO2 and CH3O2 with peroxy acetyl radicals produced by the photolysis of acetone. In the upper troposphere, vertical transport is much more efficient, and significant acetic acid production is only possible if HOx concentrations are elevated, making the production of acetic acid fast enough to compete with vertical transport.