The heterogeneous replacement of chloride by nitrate in individual sea-salt particles was monitored continuously over time in the troposphere with the use of aerosol time-of-flight mass spectrometry. Modeling calculations show that the observed chloride displacement process is consistent with a heterogeneous chemical reaction between sea-salt particles and gas-phase nitric acid, leading to sodium nitrate production in the particle phase accompanied by liberation of gaseous HCl from the particles. Such single-particle measurements, combined with a single-particle model, make it possible to monitor and explain heterogeneous gas/particle chemistry as it occurs in the atmosphere.

Size-segregated atmospheric aerosols were collected from urban and rural locations in Massachusetts using a micro-orifice impactor. The samples were analyzed for polycyclic aromatic hydrocarbons (PAH) with molecular weights between 178 and 302, using gas chromatography/mass spectrometry. Fifteen PAH were quantified in the urban samples and nine in the rural samples. The quantification results are in good agreement with available ambient monitoring data. In the urban samples, PAH were distributed among aerosol size fractions based on molecular weight. PAH with molecular weights between 178 and 202 were approximately evenly distributed between the fine (aerodynamic diameter <2 μm) and coarse (aerodymanic diameter >2 μm) aerosols. PAH with molecular weights greater than 228 were associated primarily with the fine aerosol fraction. In the rural samples, low and high molecular weight PAH were associated with both the fine and coarse aerosols. Slow mass transfer by vaporization and condensation is proposed to explain the observed PAH partitioning among aerosol size fractions.

[1] Submicrometer sea salt aerosol (SSA) particles are routinely observed in the remote marine boundary layer (MBL); these aerosols include cloud condensation nuclei and so affect the earth's radiative balance. Here foams designed to mimic oceanic whitecaps were generated in the laboratory using a range of bubbling flow rates and aqueous media: unfiltered seawater, filtered seawater, artificial seawater, and mixtures of filtered and artificial seawater. The number and sizes of dried foam droplets in the particle diameter, D p , range 15-673 nm were measured. Particle size distributions for natural and artificial seawaters were unimodal with a dN/d logD p mode at D p % 100 nm (%200 nm at 80% RH). The foam droplet mode falls within the range of reported mode diameters (D p = 40-200 nm) for submicrometer SSA particles observed in the remote MBL. The present laboratory results were scaled up to estimate submicrometer SSA particle fluxes; this extrapolation supports the hypothesis that foam droplets are the most important source of SSA particles by number. The foam droplet flux from the oceans was estimated to be 980 cm À2 s À1 for a fractional white cap coverage, W, of 0.2%. These results compared well with foam droplet fluxes reported elsewhere. The origins of variability in foam droplet fluxes were also evaluated. Natural organic matter affected foam droplet flux by a factor of 1.5; this was less than (1) the effect of bubbling flow rate on foam droplet flux (factor of 5) and (2) the uncertainty in W (factor of 3-7).

Size-segregated atmospheric particles were collected in Boston, MA, using a micro-orifice impactor. The samples were analyzed for oxygenated polycyclic aromatic hydrocarbons (OPAH) using gas chromatography/mass spectrometry. Seven PAH ketones (1-acenaphthenone, 9-fluorenone, 11H-benzo[a]fluoren-11-one, 7H-benzo[c]fluoren-7-one, 11H-benzo[b]fluoren-11-one, benzanthrone, and 6H-benzo[cd]pyrene-6-one), four PAH diones (1,4-naphthoquinone, phenanthrenequinone, 5,12-naphthacenequinone, and benzo[a]pyrene-6,12-dione), and one PAH dicarboxylic acid anhydride (naphthalic anhydride) were identified. Seven additional compounds with mass spectra typical of OPAH were tentatively identified. OPAH were generally distributed among aerosol size fractions based on molecular weight. Compounds with molecular weights between 168 and 208 were ap proximately evenly distributed between the fine (aerodynamic diameter, D p, < 2 μm) and coarse (D p > 2 μm) particles. OPAH with molecular weights of 248 and greater were associated primarily with the fine aerosol fraction. Most OPAH were distributed with particle size in a broad, unimodal hump similar to the the distributions observed for PAH in the same samples. These results suggest that OPAH are initially associated with fine particles after formation by either combustion or gas phase photooxidation and then partition to larger particles by vaporization and sorption. Two OPAH were distributed in bimodal distributions with peaks at D p ≈ 2 μm and D p ≈ 2 μm. These bimodal distributions may be indicative of sorption behavior different from PAH and other OPAH.