To investigate the cloud water chemistry and the effects of cloud processing on aerosol properties, comprehensive field observations of cloud water, aerosols, and gas-phase species were conducted at a mountaintop site in Hong Kong SAR in October and November 2016. The chemical composition of cloud water including water-soluble ions, dissolved organic matter (DOM), carbonyl compounds (refer to aldehydes and acetone), carboxylic acids, and trace metals was quantified. The measured cloud water was very acidic with a mean pH of 3.63, as the ammonium (174 µeq L−1) was insufficient for neutralizing the dominant sulfate (231 µeq L−1) and nitrate (160 µeq L−1). Substantial DOM (9.3 mgC L−1) was found in cloud water, with carbonyl compounds and carboxylic acids accounting for 18 % and 6 % in carbon molar concentrations, respectively. Different from previous observations, concentrations of methylglyoxal (19.1 µM; µM is equal to µmol L−1) and glyoxal (6.72 µM) were higher than that of formaldehyde (1.59 µM). The partitioning of carbonyls between cloud water and the gas phase was also investigated. The measured aqueous fractions of dicarbonyls were comparable to the theoretical estimations, while significant aqueous-phase supersaturation was found for less soluble monocarbonyls. Both organics and sulfate were significantly produced in cloud water, and the aqueous formation of organics was more enhanced by photochemistry and under less acidic conditions. Moreover, elevated sulfate and organics were measured in the cloud-processed aerosols, and they were expected to contribute largely to the increase in droplet-mode aerosol mass fraction. This study demonstrates the significant role of clouds in altering the chemical compositions and physical properties of aerosols via scavenging and aqueous chemical processing, providing valuable information about gas–cloud–aerosol interactions in subtropical and coastal regions.

The Chinese government launched the Air Pollution Prevention and Control Action Plan in 2013, and various stringent measures have since been implemented, which have resulted in significant decreases in emissions and ambient concentrations of primary pollutants such as SO2, NOx, and particulate matter (PM). However, surface ozone (O3) concentrations have still been increasing in urban areas across the country. In a previous analysis, we examined in detail the roles of meteorological variation during 2013–2017 in the summertime surface O3 trend in various regions of China. In this study, we evaluated the effect of changes in multi-pollutant emissions from anthropogenic activities on O3 levels during the same period by using an up-to-date regional chemical transport model (WRF-CMAQ) driven by an interannual anthropogenic emission inventory. The Community Multiscale Air Quality (CMAQ) model was improved with regard to heterogeneous reactions of reactive gases on aerosol surfaces, which led to better model performance in reproducing the ambient concentrations of those gases. The model simulations showed that the maximum daily 8 h average (MDA8) O3 mixing ratio in urban areas increased by 0.46 ppbv per year (ppbv a−1) (p=0.001) from 2013 to 2017. In contrast, a slight decrease in MDA8 O3 by 0.17 ppbv a−1 (p=0.005) in rural areas was predicted, mainly attributable to the NOx emission reduction. The effects of changes in individual pollutant emissions on O3 were also simulated. The reduction of NOx emission increased the O3 levels in urban areas due to the nonlinear NOx and volatile organic compound (VOC) chemistry and decreasing aerosol effects; the slight increase in VOC emissions enhanced the O3 levels; the reduction of PM emissions increased the O3 levels by enhancing the photolysis rates and reducing the loss of reactive gases on aerosol surfaces; and the reduction of SO2 emissions resulted in a drastic decrease in sulfate concentrations, which increased O3 through aerosol effects. In contrast to the unfavorable effect of the above changes in pollutant emissions on efforts to reduce surface O3, the reduction of CO emissions did help to decrease the O3 level in recent years. The dominant cause of increasing O3 due to changes in anthropogenic emissions varied geographically. In Beijing, NOx and PM emission reductions were the two largest causes of the O3 increase; in Shanghai, the reduction of NOx and increase in VOC emissions were the two major causes; in Guangzhou, NOx reduction was the primary cause; in Chengdu, the PM and SO2 emission decreases contributed most to the O3 increase. Regarding the effects of decreasing concentrations of aerosols, the drop in heterogeneous uptake of reactive gases – mainly HO2 and O3 – was found to be more important than the increase in photolysis rates. The adverse effect of the reductions of NOx, SO2, and PM emissions on O3 abatement in Beijing, Shanghai, Guangzhou, and Chengdu would have been avoided if the anthropogenic VOCs emission had been reduced by 24 %, 23 %, 20 %, and 16 %, respectively, from 2013 to 2017. Our analysis revealed that the NOx reduction in recent years has helped to contain the total O3 production in China. However, to reduce O3 levels in major urban and industrial areas, VOC emission controls should be added to the current NOx-SO2-PM policy.

China has suffered from increasing levels of ozone pollution in urban areas despite the implementation of various stringent emission reduction measures since 2013. In this study, we conducted numerical experiments with an up-to-date regional chemical transport model to assess the contribution of the changes in meteorological conditions and anthropogenic emissions to the summer ozone level from 2013 to 2017 in various regions of China. The model can faithfully reproduce the observed meteorological parameters and air pollutant concentrations and capture the increasing trend in the surface maximum daily 8 h average (MDA8) ozone (O3) from 2013 to 2017. The emission-control measures implemented by the government induced a decrease in MDA8 O3 levels in rural areas but an increase in urban areas. The meteorological influence on the ozone trend varied by region and by year and could be comparable to or even more significant than the impact of changes in anthropogenic emissions. Meteorological conditions can modulate the ozone concentration via direct (e.g., increasing reaction rates at higher temperatures) and indirect (e.g., increasing biogenic emissions at higher temperatures) effects. As an essential source of volatile organic compounds that contributes to ozone formation, the variation in biogenic emissions during summer varied across regions and was mainly affected by temperature. China's midlatitude areas (25 to 40∘ N) experienced a significant decrease in MDA8 O3 due to a decline in biogenic emissions, especially for the Yangtze River Delta and Sichuan Basin regions in 2014 and 2015. In contrast, in northern (north of 40∘ N) and southern (south of 25∘ N) China, higher temperatures after 2013 led to an increase in MDA8 O3 via an increase in biogenic emissions. We also assessed the individual effects of changes in temperature, specific humidity, wind field, planetary boundary layer height, clouds, and precipitation on ozone levels from 2013 to 2017. The results show that the wind field change made a significant contribution to the increase in surface ozone over many parts of China. The long-range transport of ozone and its precursors from outside the modeling domain also contributed to the increase in MDA8 O3 in China, especially on the Qinghai–Tibetan Plateau (an increase of 1 to 4 ppbv). Our study represents the most comprehensive and up-to-date analysis of the impact of changes in meteorology on ozone across China and highlights the importance of considering meteorological variations when assessing the effectiveness of emission control on changes in the ozone levels in recent years.

Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase partitioning of semivolatile gases such as HNO3, NH3, HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine-particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicate acidity may be relatively constant due to the semivolatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale.

The dicarbonyls glyoxal (Gly) and methylglyoxal (Mgly) have been recognized as important precursors of secondary organic aerosols (SOAs) through the atmospheric heterogeneous process. In this study, field measurement was conducted at a receptor site in the Pearl River Delta (PRD) region in southern China, and an observation-based photochemical box model was subsequently applied to investigate the production and evolution of Gly and Mgly as well as their contributions to SOA formation. The model was coupled with a detailed gas-phase oxidation mechanism of volatile organic compounds (VOCs) (i.e., Master Chemical Mechanism, MCM, v3.2), heterogeneous processes of Gly and Mgly (i.e., reversible partitioning in aqueous phase, irreversible volume reactions and irreversible surface uptake processes), and the gas–particle partitioning of oxidation products. The results suggested that without considering the heterogeneous processes of Gly and Mgly on aerosol surfaces, the model would overpredict the mixing ratios of Gly and Mgly by factors of 3.3 and 3.5 compared to the observed levels. The agreement between observation and simulation improved significantly when the irreversible uptake and the reversible partitioning were incorporated into the model, which in total both contributed ∼ 62 % to the destruction of Gly and Mgly during daytime. Further analysis of the photochemical budget of Gly and Mgly showed that the oxidation of aromatics by the OH radical was the major pathway producing Gly and Mgly, followed by degradation of alkynes and alkenes. Furthermore, based on the improved model mechanism, the contributions of VOC oxidation to SOA formed from gas–particle partitioning (SOAgp) and from heterogeneous processes of Gly and Mgly (SOAhet) were also quantified. It was found that o-xylene was the most significant contributor to SOAgp formation (∼ 29 %), while m,p-xylene and toluene made dominant contributions to SOAhet formation. Overall, the heterogeneous processes of Gly and Mgly can explain ∼ 21 % of SOA mass in the PRD region. The results of this study demonstrated the important roles of heterogeneous processes of Gly and Mgly in SOA formation and highlighted the need for a better understanding of the evolution of intermediate oxidation products.