Effects of heterogeneous reaction with NO2 on ice nucleation activities of feldspar and Arizona Test Dust.

Mineral dust is an important type of ice nucleating particles in the troposphere; however, the effects of heterogeneous reactions on ice nucleation (IN) activities of mineral dust remain to be elucidated. A droplet-freezing apparatus (Guangzhou Institute of Geochemistry Ice Nucleation Apparatus, GIGINA) was developed in this work to measure IN activities of atmospheric particles in the immersion freezing mode, and its performance was validated by a series of experimental characterizations. This apparatus was then employed to measure IN activities of feldspar and Arizona Test Dust (ATD) particles before and after heterogeneous reaction with NO2 (10±0.5 ppmv) at 40% relative humidity. The surface coverage of nitrate, θ(NO3-), increased to 3.1±0.2 for feldspar after reaction with NO2 for 6 hr, and meanwhile the active site density per unit surface area (ns) at -20°C was reduced from 92±5 to <1.0 cm-2 by about two orders of magnitude; however, no changes in nitrate content or IN activities were observed for further increase in reaction time (up to 24 hr). Both nitrate content and IN activities changed continuously with reaction time (up to 24 hr) for ATD particles; after reaction with NO2 for 24 hr, θ(NO3-) increased to 1.4±0.1 and ns at -20°C was reduced from 20±4 to 9.7±1.9 cm-2 by a factor of ∼2. Our work suggests that heterogeneous reaction with NO2, an abundant reactive nitrogen species in the troposphere, may significantly reduce IN activities of mineral dust in the immersion freezing mode.

Heterogeneous reaction of NO2 with feldspar, three clay minerals and Arizona Test Dust.

Heterogeneous reaction of NO2 with mineral dust aerosol may play important roles in troposphere chemistry, and has been investigated by a number of laboratory studies. However, the influence of mineralogy on this reaction has not been well understood, and its impact on aerosol hygroscopicity is not yet clear. This work investigated heterogeneous reactions of NO2 (∼10 ppmv) with K-feldspar, illite, kaolinite, montmorillonite and Arizona Test Dust (ATD) at room temperature as a function of relative humidity (<1% to 80%) and reaction time (up to 24 hr). Heterogeneous reactivity towards NO2 was low for illite, kaolinite, montmorillonite and ATD, and uptake coefficients of NO2, γ(NO2), were determined to be around or smaller than 1×10-8; K-feldspar exhibited higher reactivity towards NO2, and CaCO3 is most reactive among the nine mineral dust samples considered in this and previous work. After heterogeneous reaction with NO2 for 24 hr, increase in hygroscopicity was nearly insignificant for illite, kaolinite and montmorillonite, and small but significant for K-feldspar; in addition, large increase in hygroscopicity was observed for ATD, although the increase in hygroscopicity was still smaller than CaCO3.

A database for deliquescence and efflorescence relative humidities of compounds with atmospheric relevance.

Deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH), the two parameters that regulate phase state and hygroscopicity of substances, play important roles in atmospheric science and many other fields. A large number of experimental studies have measured the DRH and ERH values of compounds with atmospheric relevance, but these values have not yet been summarized in a comprehensive manner. In this work, we develop for the first-of-its-kind a comprehensive database which compiles the DRH and ERH values of 110 compounds (68 inorganics and 42 organics) measured in previous studies, provide the preferred DRH and ERH values at 298 K for these compounds, and discuss the effects of a few key factors (e.g., temperature and particle size) on the measured DRH and ERH values. In addition, we outline future work that will broaden the scope of this database and enhance its accessibility.