Acidity of Aerosols during Winter Heavy Haze Events in Beijing and Gucheng, China

We investigated the acidity and concentrations of water-soluble ions in PM2.5 aerosol samples collected from an urban site in Beijing and a rural site in Gucheng, Hebei Province from November 2016 to January 2017 to gain an insight into the formation of secondary inorganic species. The average SO4^2–, NO3^–, and NH4^＋ concentrations were 8.3,12.5, and 14.1 μg m^–3, respectively, at the urban site and 14.0, 14.2, and 24.2 μg m^（–3）, respectively, at the rural site.The nitrogen and sulfur oxidation ratios in urban Beijing were correlated with relative humidity（with correlation coefficient r = 0.79 and 0.67, respectively） and the aerosol loadings. Based on a parameterization model, we found that the rate constant of the heterogeneous reactions for SO2 on polluted days was about 10 times higher than that on clear days, suggesting that the heterogeneous reactions in the aerosol water played an essential role in haze events.The ISORROPIA II model was used to predict the aerosol pH, which had a mean（range） of 5.0（4.9–5.2） and 5.3（4.6–6.3） at the urban and rural site, respectively. Under the conditions with this predicted pH value, oxidation by dissolved NO2 and the hydrolysis of N2O5 may be the major heterogeneous reactions forming SO4^2– and NO3^– in haze.We also analyzed the sensitivity of the aerosol p H to changes in the concentrations of SO4^2–, NO3^–, and NH4^＋ under haze conditions. The aerosol p H was more sensitive to the SO4^2– and NH4^＋ concentrations with opposing trends, than to the NO3^– concentrations. The sensitivity of the p H was relatively weak overall, which was attributed to the buffering effect of NH3 partitioning.

Chemical characteristics of haze particles in Xi＇an during Chinese Spring Festival： Impact of fireworks burning

Fireworks burning releases massive fine particles and gaseous pollutants, significantly deteriorating air quality during Chinese Lunar New Year （LNY） period. To investigate the impact of the fireworks burning on the atmospheric aerosol chemistry, 1-hr time resolution of PM2.5 samples in Xi＇an during the winter of 2016 including the LNY were collected and detected for inorganic ions, acidity and liquid water content （LWC） of the fine aerosols. PM2.5 during the LNY was 167 ± 87 μg/m^3, two times higher than the China National Ambient Air Quality Standard （75 μg/m^3）. K^＋ （28 wt.% of the total ion mass） was the most abundant ion in the LNY period, followed by SO^2-4 （25 wt.%） and C1^- （18 wt.%）. In contrast, NO^-3 （34 wt.%） was the most abundant species in the haze periods （hourly PM2.5 〉 75 μg/m^3）, followed by SO^2-4 （29.2 wt.%） and NH^＋4 （16.3 wt.%）, while SC94 （35 wt.%） was the most abundant species in the clean periods （hourly PM2.5 〈 75 μg/m^3）, followed by NO^-3 （23.1 wt.%） and NH^＋4 （11 wt.%）. Being different from the acidic nature in the non-LNY periods, aerosol in the LNY period presented an alkaline nature with a pH value of 7.8 ± 1.3. LWC during the LNY period showed a robust linear correlation with K2SO4 and KC1, suggesting that aerosol hygroscopicity was dominated by inorganic salts derived from fireworks burning. Analysis of correlations between the ratios of NO^-3/SO^2-4 and NH^＋4/SO^2-4 indicated that heterogeneous reaction of HNO3 with NH3 was an important formation pathway of particulate nitrate and ammonium during the LNY period.

Organic aerosol molecular composition and gas–particle partitioning coefficients at a Mediterranean site(Corsica)

Molecular speciation of atmospheric organic matter was investigated during a short summer field campaign performed in a citrus fruit field in northern Corsica（June 2011）. Aimedat assessing the performance on the field of newly developed analytical protocols, this work focuses on the molecular composition of both gas and particulate phases and provides an insight into partitioning behavior of the semi-volatile oxygenated fraction. Limonene ozonolysis tracers were specifically searched for, according to gas chromatography–mass spectrometry（GC–MS） data previously recorded for smog chamber experiments. A screening of other oxygenated species present in the field atmosphere was also performed. About sixty polar molecules were positively or tentatively identified in gas and/or particle phases. These molecules comprise a wide range of branched and linear, mono and di-carbonyls（C_3–C7）,mono and di-carboxylic acids（C_3–C_18）, and compounds bearing up to three functionalities.Among these compounds, some can be specifically attributed to limonene oxidation and others can be related to α- or β-pinene oxidation. This provides an original snapshot of the organic matter composition at a Mediterranean site in summer. Furthermore, for compounds identified and quantified in both gaseous and particulate phases, an experimental gas/particle partitioning coefficient was determined. Several volatile products, which are not expected in the particulate phase assuming thermodynamic equilibrium, were nonetheless present in significant concentrations. Hypotheses are proposed to explain these observations, such as the possible aerosol viscosity that could hinder the theoretical equilibrium to be rapidly reached.