Atmospheric year-round records of dicarboxylic acids and sulfate at three French sites located between 630 and 4360 m elevation

Abstract

An atmospheric year-round study of C2-C5 dicarboxylic acids (oxalic, malonic, succinic, malic, and glutaric) and sulfate was conducted in 2002 and 2003 at three remote western Europe continental sites located at different elevations (from 630 to 4360 m asl). Whatever the site and the season, oxalic acid is always the dominant diacid (average 64% of total dicarboxylic acids) followed by malonic acid (15% of total dicarboxylic acids). High correlation coefficients are observed between C3 (malonic), C4 (malic and succinic), and C5 (glutaric) acids and oxalic acid. These strong relationships between C2-C5 diacids support the hypothesis of a common production of these diacids through the aqueous phase chemistry of glutaric acid. Data gained at different elevations are here useful to compare the mass formation rates of sulfate and dicarboxylic acids. It is shown that in summer the decrease of the sum of dicarboxylic acids with height is far less pronounced than the decrease of sulfate (a factor of 2 instead of 6.8 from 630 to 4360 m asl). That demonstrates that the production of dicarboxylic acids occurs at up to 4300 m elevation while the production of sulfate from SO 2 mainly takes place between the boundary layer and 3000 m elevation. With respect to summer 2002 the sum of dicarboxylic acids was enhanced in summer 2003 (from 136 to 331 ng m -3 STP at 2870 m asl, for instance) whereas a weaker increase is observed for sulfate (from 1700 to 2500 ng m -3 STP at 2870 m asl). These changes are attributed to the particular summer 2003 conditions which led to enhanced level of oxidants (strengthened secondary productions) and warmer temperatures (enhanced emissions of biogenic precursors of diacids). Copyright 2005 by the American Geophysical Union.