A variety of C1-C12 carbonyl compounds were measured in the air of
a boreal coniferous forest located in Hyytiälä, Southern Finland.
24-hour samples were collected during March and April in 2003 using DNPH
(2,4-dinitrophenyl hydrazine) coated C18-cartridges and analyzed by
liquid chromatography-mass spectrometry (LC-MS).
Altogether 22 carbonyl compounds were quantified. The most abundant
carbonyls were acetone (24-hour average 1340ng/m3), formaldehyde
(480ng/m3) and acetaldehyde (360ng/m3). Concentrations of monoterpene
reaction products nopinone (9ng/m3) and limona ketone (5ng/m3)
were low compared to the most abundant low molecular weight carbonyls.
Trajectory analysis showed that highest concentrations of carbonyls were
measured in the air masses coming from the East and the lowest in the air
masses cycled long time over Scandinavia. The total concentration of
carbonyl compounds in Hyytiälä in March/April 2003 was much higher
than the concentration of aromatic hydrocarbons and monoterpenes in April
2002.
Scaling the concentrations against reactivity with the OH-radical showed,
that in spite of relatively low ambient concentrations higher molecular
weight aldehydes contribute significantly to the total OH-reactive mass of
carbonyls. The impact of carbonyl compounds on OH-radical chemistry is
important. Contribution of carbonyls as an OH sink is comparable to that of
NO2 and higher than monoterpenes and aromatic hydrocarbons.
Lifetimes of the measured carbonyls with respect to reactions with OH
radicals, ozone (O3), and nitrate (NO3) radicals as well as
photolysis were estimated. The main sink reactions for most of the carbonyl
compounds in Hyytiälä in springtime are expected to be reactions
with the OH radical and photolysis. For 6-methyl-5-hepten-2-one and limona
ketone also reactions with ozone are important. The sources of carbonyl
compounds are presently highly uncertain. Based on the comparisons with
urban concentrations the direct anthropogenic emissions are not as important
as secondary biogenic and anthropogenic sources or primary biogenic sources
in Hyytiälä. |