No abstract

[1] Oxalic acid is often the leading contributor to the total dicarboxylic acid mass in ambient organic aerosol particles. During the 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) field campaign, nine inorganic ions (including SO 4 2À) and five organic acid ions (including oxalate) were measured on board the Center for Interdisciplinary Remotely Piloted Aircraft Studies (CIRPAS) Twin Otter research aircraft by a particle-into-liquid sampler (PILS) during flights over Ohio and surrounding areas. Five local atmospheric conditions were studied: (1) cloud-free air, (2) power plant plume in cloud-free air with precipitation from scattered clouds overhead, (3) power plant plume in cloud-free air, (4) power plant plume in cloud, and (5) clouds uninfluenced by local pollution sources. The aircraft sampled from two inlets: a counterflow virtual impactor (CVI) to isolate droplet residuals in clouds and a second inlet for sampling total aerosol. A strong correlation was observed between oxalate and SO 4 2À when sampling through both inlets in clouds. Predictions from a chemical cloud parcel model considering the aqueous-phase production of dicarboxylic acids and SO 4 2À show good agreement for the relative magnitude of SO 4 2À and oxalate growth for two scenarios: power plant plume in clouds and clouds uninfluenced by local pollution sources. The relative contributions of the two aqueous-phase routes responsible for oxalic acid formation were examined; the oxidation of glyoxylic acid was predicted to dominate over the decay of longer-chain dicarboxylic acids. Clear evidence is presented for aqueous-phase oxalic acid production as the primary mechanism for oxalic acid formation in ambient aerosols.

Aerosol nucleation events occurring in the continental boundary layer over the boreal forest region in Finland, during the BIOFOR experiment, have been examined to elucidate the rô le of micrometeorology in promoting such events. Invariably, during the spring campaign of 1999, nucleation events occurred in Arctic and polar air masses during cold air outbreaks. Under clear-sky conditions, typical of these synoptic meteorological patterns, the boundary layer evolution was characterized by the rapid growth of a mixed layer, convection and strong entrainment, first from the residual later and later from the free troposphere. It was found that the freshly nucleated particles were detected within two hours from the onset of strong turbulent kinetic energy, independent of how fast the boundary layer evolved. When considering the growth time from cluster size of #1 nm to detectable sizes of 3 nm, the nucleation and onset of strong turbulence coincided almost exactly. The most likely site for nucleation to take place was the mixed layer or the entrainment zone, while the forest canopy and the free troposphere could be excluded as the nucleation region. There are several possible explanations for the correlation between the onset of turbulence and nucleation: (1) new aerosols or clusters may have been entrained from the residual layer into the mixed layer where they then (in the case of clusters) underwent growth to detectable sizes; (2) two or more precursor gases may have been mixed with each other over the entrainment zone; (3) the adiabatic cooling in the rising convective plumes and the turbulent fluctuation in temperature and vapors by the entrainment flux may have enhanced aerosol formation; (4) a sudden decrease in preexisting aerosol due to dilution of the mixed layer aerosol by entrained air may have reduced the vapor sink enough to initiate nucleation. However, the lack of vertical profile measurements of nucleation mode aerosols, precursor vapors and turbulent fluctuations throughout and above the mixed-layer results in it remaining an open question as to which one of these processes dominates.

Particle concentrations and size distributions have been measured from different heights inside and above a boreal forest during three BIOFOR campaigns