Iodic acid (HIO3) is known to form aerosol particles in coastal marine regions, but predicted nucleation and growth rates are lacking. Using the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber, we find that the nucleation rates of HIO3 particles are rapid, even exceeding sulfuric acid–ammonia rates under similar conditions. We also find that ion-induced nucleation involves IO3− and the sequential addition of HIO3 and that it proceeds at the kinetic limit below +10°C. In contrast, neutral nucleation involves the repeated sequential addition of iodous acid (HIO2) followed by HIO3, showing that HIO2 plays a key stabilizing role. Freshly formed particles are composed almost entirely of HIO3, which drives rapid particle growth at the kinetic limit. Our measurements indicate that iodine oxoacid particle formation can compete with sulfuric acid in pristine regions of the atmosphere.
SignificanceAerosol particles can form and grow by gas-to-particle conversion and eventually act as seeds for cloud droplets, influencing global climate. Volatile organic compounds emitted from plants are oxidized in the atmosphere, and the resulting products drive particle growth. We measure particle growth by oxidized biogenic vapors with a well-controlled laboratory setup over a wide range of tropospheric temperatures. While higher temperatures lead to increased reaction rates and concentrations of highly oxidized molecules, lower temperatures allow additional, but less oxidized, species to condense. We measure rapid growth over the full temperature range of our study, indicating that organics play an important role in aerosol growth throughout the troposphere. Our finding will help to sharpen the predictions of global aerosol models.
Atmospheric aerosol formation from biogenic vapors is strongly affected by air pollutants, like NOx, SO2, and NH3.
A list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog1,2, but how it occurs in cities is often puzzling3. If the growth rates of urban particles are similar to those found in cleaner environments (1–10 nanometres per hour), then existing understanding suggests that new urban particles should be rapidly scavenged by the high concentration of pre-existing particles. Here we show, through experiments performed under atmospheric conditions in the CLOUD chamber at CERN, that below about +5 degrees Celsius, nitric acid and ammonia vapours can condense onto freshly nucleated particles as small as a few nanometres in diameter. Moreover, when it is cold enough (below −15 degrees Celsius), nitric acid and ammonia can nucleate directly through an acid–base stabilization mechanism to form ammonium nitrate particles. Given that these vapours are often one thousand times more abundant than sulfuric acid, the resulting particle growth rates can be extremely high, reaching well above 100 nanometres per hour. However, these high growth rates require the gas-particle ammonium nitrate system to be out of equilibrium in order to sustain gas-phase supersaturations. In view of the strong temperature dependence that we measure for the gas-phase supersaturations, we expect such transient conditions to occur in inhomogeneous urban settings, especially in wintertime, driven by vertical mixing and by strong local sources such as traffic. Even though rapid growth from nitric acid and ammonia condensation may last for only a few minutes, it is nonetheless fast enough to shepherd freshly nucleated particles through the smallest size range where they are most vulnerable to scavenging loss, thus greatly increasing their survival probability. We also expect nitric acid and ammonia nucleation and rapid growth to be important in the relatively clean and cold upper free troposphere, where ammonia can be convected from the continental boundary layer and nitric acid is abundant from electrical storms4,5.
We have investigated the vapor wall loss of semi-volatile organic compounds (SVOCs) in a Teflon smog chamber. We studied the vapor wall loss of seven SVOCs with known saturation concentrations, including alkanes (hexacosane, pentacosane, docosane, eicosane, and d 62 -squalane), an organic acid (oleic acid), and a polyol (levoglucosan) in single-component and binary-component (organic) systems, using ammonium sulfate (AS) seeds to constrain the particle wall loss. We coated inorganic particles with SVOCs and measured the loss of organics from those particles to constrain the wall losses, observing loss rates proportional to the saturation concentrations of the SVOCs. The loss rate of oleic acid mixed with d 62 -squalane was proportional to its mole fraction in the mixture. Our results show that the vapor wallloss rates of SVOCs are significant, quasi-irreversible, and proportional to the SVOC vapor concentrations. The vapor wall-loss rate constant of the SVOCs that we studied in the CMU chamber is 3.8 § 0.3 h ¡1 ; this is comparable to values in other chambers with similar surface area to volume ratios. Our results are also consistent with a relatively high mass accommodation coefficient for SVOCs, a org > 0.1.
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