1Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA
2Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, Colorado, USA
3Arizona State University, Department of Chemistry and Biochemistry, Arizona, USA
4Air Quality Research Division, Atmospheric Science and Technology Directorate, Science and Technology Branch, Environment Canada, Downsview, Canada
5Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA, USA
Abstract. Cloud and fog droplets efficiently scavenge and process water-soluble compounds and thus modify the chemical composition of the gas and particle phases. The concentrations of dissolved organic carbon (DOC) in the aqueous phase reach concentrations on the order of ~10 mg C L−1 which is typically on the same order of magnitude as the sum of inorganic anions. Aldehydes and carboxylic acids typically comprise a large fraction of DOC because of their high solubility. The dissolution of species in the aqueous phase can lead to (i) the removal of species from the gas phase preventing their processing by gas phase reactions (e.g. photolysis of aldehydes) and (ii) the formation of unique products that do not have any efficient gas phase sources (e.g. dicarboxylic acids).
We present measurements of DOC and select aldehydes in fog water at high elevation and intercepted clouds in a biogenically-impacted location (Whistler, Canada) and in fog water in a more polluted area (Davis, CA). Concentrations of formaldehyde, glyoxal and methylglyoxal were in the micromolar range and comprised ≤2% each individually of the DOC. Comparison of the DOC and aldehyde concentrations to those at other locations shows good agreement and reveals highest levels for both in anthropogenically impacted regions. Based on this overview, we conclude that the fraction of organic carbon (dissolved and insoluble inclusions) in the aqueous phase comprises 1–~40% of total organic carbon. Higher values are observed to be associated with aged air masses where organics are expected to be more highly oxidized and thus more soluble. Accordingly, the aqueous/gas partitioning ratio expressed here as an effective Henry's law constant for DOC (KH*DOC) increases by an order of magnitude from 7×103 M atm−1 to 7×104 M atm−1 during the ageing of air masses.
The measurements are accompanied by photochemical box model simulations. They suggest that the scavenging of aldehydes by the aqueous phase can reduce HO2 gas phase levels by two orders of magnitude due to a weaker net source of HO2 production from aldehyde photolysis in the gas phase. Despite the high solubility of dialdehydes (glyoxal, methylglyoxal), their impact on the HO2 budget by scavenging is <10% of that of formaldehyde. The overview of DOC and aldehyde measurements presented here reveals that clouds and fogs can be efficient sinks for organics, with increasing importance in aged air masses. Even though aldehydes, specifically formaldehyde, only comprise ~1% of DOC, their scavenging and processing in the aqueous phase might translate into significant effects on the oxidation capacity of the atmosphere.