Shouldn't snowpacks be sources of monocarboxylic acids?

We report the first measurements of the mixing ratios of acetic (CH3COOH) and formic (HCOOH) acids in the air filling the pore spaces of the snowpacks (firn air) at Summit, Greenland and South Pole. Both monocarboxylic acids were present at levels well above 1 ppbv throughout the upper 35 cm of the snowpack at Summit. Maximum mixing ratios in Summit firn air reached nearly 8 ppbv CH3COOH and 6 ppbv HCOOH. At South Pole the mixing ratios of these acids in the top 35 cm of firn air were also generally > 1 ppbv, though their maximums barely exceeded 2.5 ppbv of CH3COOH and 2.0 ppbv of HCOOH. Mixing ratios of the monocarboxylic acids in firn air did not consistently respond to diel and experimental (fast) variations in light intensity, unlike the case for N oxides in the same experiments. Air-to-snow fluxes of CH3COOH and HCOOH apparently support high mixing ratios (means of (CH3COOH/HCOOH) 445/460 and 310/159 pptv at Summit and South Pole, respectively) in air just above the snow during the summer sampling seasons at these sites. We hypothesize that oxidation of carbonyls and alkenes (that are produced by photo- and OH-oxidation of ubiquitous organic compounds) within the snowpack is the source of the monocarboxylic acids. (C) 2002 Elsevier Science Ltd. All rights reserved.