• Energy Research

AbstractA 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.

Organic aerosols (OA) have gained attention as a substantial component of atmospheric aerosols owing to their impact on atmospheric visibility, climate, and human health. Although oxygenated organic molecules (OOMs) are essential contributors to OA formation, the sources, transformations, and fates of the OOMs are not fully understood. Herein, anthropogenic OOMs (AOOMs), anthropogenic volatile organic compounds (AVOCs), and OA were concurrently measured in Xiamen, a coastal city in southeastern China. Our results show that the AOOMs exhibited a high nitrogen content (76%) and a low oxidation degree. Strong photochemical processes of aromatic VOCs were the predominant sources of AOOMs. Also, NOx concentrations and the occurrence of multigeneration OH radical oxidations were the critical factors that might influence the formation of AOOMs. Finally, the newly developed aerosol dynamic model's results show that more than 35% of the OA mass growth rate is attributed to the gas-particle partitioning of AOOMs. Further sensitivity testing demonstrates that the contribution of AOOMs to OA growth is significantly enhanced during high-particulate-concentration periods, especially under low-temperature conditions. This study emphasizes the vital role of photochemically produced AOOMs derived from AVOCs in OA growth in a coastal urban atmosphere.

Abstract. Secondary aerosol is a major component of PM2.5, yet its formation mechanism in the ambient atmosphere is still an open question. Based on field measurements in downtown Beijing, we show that the photolysis of nitrous acid (HONO) could promote the formation of organic and nitrate aerosol in wintertime Beijing as evidenced by the growth of the mass concentration of organic and nitrate aerosols linearly increasing as a function of consumed HONO from early morning to noon. The increased nitrate also lead to the formation of particulate matter ammonium by enhancing the neutralization of nitric acid by ammonia. We further illustrate that over 50 % of the ambient HONO during pollution events in wintertime Beijing might be related to traffic-related emission including direct emission and formation via the reaction between OH and vehicle-emitted NO. Overall, our results highlight that the traffic-related HONO plays an important role in the oxidative capacity and in turn, contribute to the haze formation in winter Beijing. Mitigation of HONO and NOx emission from the vehicles might be an effective way to reduce secondary aerosol mass formation and severe haze events in wintertime Beijing.

Secondary organic aerosol (SOA) formation originating from the emission of anthropogenic volatile organic compounds (VOCs) makes a significant contribution to fine particulate matter (PM2.5) pollution in urban areas. Investigation on the SOA formation potential (SOAFP) can help us understand the contribution of different sources to SOA formation. To characterize the SOAFP of ambient air from anthropogenic VOCs in the urban area of Beijing, field observation was implemented using a twin oxidation flow reactor (Twin-OFRs) system in the winters of 2016 and 2017. Compared to the winter of 2016, the seasonal-average SOAFP in the winter of 2017 was found to decrease by about 74% (18.6 to 4.9 μg/m3), which is more than that of PM1 (59%, 48.7 to 20.2 μg/m3), PM2.5 (61%, 114.4 to 44.8 μg/m3) and CO (57%, 2.1 to 0.9 mg/m3) that mainly comes from the combustion of fossil fuels, suggesting complex affecting factors on SOAFP. The results of wind decomposition mathematical modeling showed that anthropogenic factors and favorable meteorological conditions both contributed significantly to the decrease in SOAFP. The reduction of emissions from scatter coal combustion, which is the key VOCs source for SOAFP, is probably the most important anthropogenic factor affecting SOAFP. In the winter of 2016, the ratio of benzene to toluene is 1.45 that was close to 1.54 representing coal combustion emission; however, it decreased dramatically to 1.05 in the winter of 2017, suggesting considerable reduction of VOC emissions from scatter coal combustion in the latter year due to the coal-to-gas transition in Beijing and surrounding regions. The SOAFP measured in this study considers all ambient VOCs that can react with OH radical, providing another representative method for estimating it. These results could be beneficial to understanding the factors driving SOAFP and its contribution to PM2.5, especially in regions with high-intensity anthropogenic emissions. Synopsis: This study reported the sharp decline of secondary organic aerosol formation potential (SOAFP) between two consecutive winters in Beijing and analyzed the reasons.