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We present the continuously measurements of volatile organic compounds (VOCs) at a receptor site (Wan Qing Sha, WQS) in the Pearl River Delta (PRD) region from September to November of 2017. The average mixing ratios of total VOCs (TVOCs) was 36.3 ± 27.9 ppbv with the dominant contribution from alkanes (55.5%), followed by aromatics (33.3%). The diurnal variation of TVOCs showed a strong photochemical consumption during daytime, resulting in the formation of ozone (O3). Five VOC sources were resolved by the positive matrix factorization (PMF) model, including solvent usage (28.6%), liquid petroleum gas (LPG) usage (24.4%), vehicle exhaust (21.0%), industrial emissions (13.2%) and gasoline evaporation (12.9%). The regional transport air masses from the upwind cities of south China can result in the elevated concentrations of TVOCs. Low ratios of TVOCs/NOx (1.53 ± 0.88) suggested that the O3 formation regime at WQS site was VOC-limited, which also confirmed by a photochemical box model with the master chemical mechanism (PBM-MCM). Furthermore, the observation on high-O3 episode days revealed that frequent O3 outbreaks at WQS were mainly caused by the regional transport of anthropogenic VOCs especially for aromatics and the subsequent photochemical reactions. This study provides valuable information for policymakers to propose the effective control strategies on photochemical pollution in a regional perspective.

Volatile organic compounds (VOCs) play a crucial role in modulating air pollution by ozone and fine particles, particularly in urban areas. While in recent years short-term intervention actions for better air quality during big events in China did present good opportunities to examine the effectiveness of control measures in reducing anthropogenic VOCs emission, it is highly challenging to interpret the real effect of a specific control measure based on field monitoring data when a cocktail of control measures were adopted. Here we took the air quality intervention actions during the 16th Asian Games (AG) in Guangzhou as a case study to explore the impact of short-term multiple measures on VOCs reduction. The average mass concentrations of VOCs decreased by 52-68% during the AG. These percentages could not reflect emission reduction rates as the concentration might be also heavily impacted by dispersion conditions. Diagnostic ratios, such as methyl tert-butyl ether to carbon monoxide (MTBE/CO) and i-pentane/CO, decreased by over 60% during the AG, suggesting a substantial reduction in gasoline related emissions. A method linking emission reduction rates of two sources with their contribution percentages before and during the AG by using a receptor model was further formulated. With the available reduction rate of 34% for vehicular exhaust obtained during the traffic restriction drill in our previous study, VOCs emissions from gasoline evaporation and solvent use reduced by 45.7% and 13.6% during the AG, respectively. Total VOCs emissions decreased by 25.3% on average during the AG, and the emission control of vehicular exhaust, oil evaporation, and solvent use accounted for 17.0%, 6.3% and 2.0% of total VOCs emission reduction, respectively. This study presented an observed-based method with diagnostic/quantitative approaches to single out the effectiveness of each control measures in reducing VOCs emissions.

The heterogeneous reactivity of dinitrogen pentoxide ( N2O5 ) on ambient aerosols plays a key role in the atmospheric fate of NOx and formation of secondary pollutants. To better understand the reactive uptake of N2O5 on complex ambient aerosols, an in situ experimental approach to direct measurement of N2O5 uptake coefficient ( γ N2O5 ) was developed for application in environments with high, variable ambient precursors. The method utilizes an aerosol flow tube reactor coupled with an iterative chemical box model to derive γ N2O5 from the depletion of synthetically generated N2O5 when mixed with ambient aerosols. Laboratory tests and model simulations were performed to characterize the system and the factors affecting γ N2O5 , including mean residence time, wall loss variability with relative humidity (RH), and N2O5 formation and titration with high levels of NO, NOx , and O3 . The overall uncertainty was estimated to be 37 %–40 % at γ N2O5 of 0.03 for RH varying from 20 % to 70 %. The results indicate that this flow tube coupled with the iterative model method could be buffered to NO concentrations below 8 ppbv and against air mass fluctuations switching between aerosol and non-aerosol modes. The system was then deployed in the field to test its applicability under conditions of high ambient NO2 and O3 and fresh NO emission. The results demonstrate that the iterative model improved the accuracy of γ N2O5 calculations in polluted environments and thus support the further field deployment of the system to study the impacts of heterogeneous N2O5 reactivity on photochemistry and aerosol formation.

The relation of acute fluctuations of air pollution to hospital admission for bronchiectasis remained uncertain, and large-scale studies were needed. We collected daily concentrations of particulate matter (PM), sulfur dioxide (SO2), nitrogen dioxide (NO2), carbon monoxide (CO), ozone (O3), and daily hospitalizations for bronchiectasis for 21 cities across Guangdong Province from 2013 through 2017. We examined their association using two-stage time-series analysis. Our analysis was stratified by specific sub-diagnosis, sex and age group to assess potential effect modifications. Relative risks of hospitalization for bronchiectasis were 1.060 (95%CI 1.014-1.108) for PM10 at lag0-6, 1.067 (95%CI 1.020-1.116) for PM2.5 at lag0-6, 1.038 (95%CI 1.005-1.073) for PMcoarse at lag0-6, 1.058 (95%CI 1.015-1.103) for SO2 at lag0-4, 1.057 (95%CI 1.030-1.084) for NO2 at lag0 and 1.055 (95%CI 1.025-1.085) for CO at lag0-6 per interquartile range increase of air pollution. Specifically, acute fluctuations of air pollution might be a risk factor for bronchiectasis patients with lower respiratory infection but not with hemoptysis. Patients aged ≥65 years, and female patients appeared to be particularly susceptible to air pollution. Acute fluctuations of air pollution, particularly PM may increase the risk of hospital admission for bronchiectasis exacerbations, especially for the patients complicated with lower respiratory infection. This study strengthens the importance of reducing adverse impact on respiratory health of air pollution to protect vulnerable populations.

Cross-regional transport potentially contributes to PM2.5 nitrate (pNO3), and this can occur as indirect transport, through which pNO3 precursors are transported to targeted regions, wherein they subsequently react with locally emitted ones to produce pNO3. However, the process has been rarely studied, which limits its comprehensive understanding. We applied the CMAQ model to study the contributions and mechanisms of pNO3 transport during autumn in the Pearl River Delta (PRD), a metropolitan region under the growing influence of cross-regional transport on PM2.5 pollution. Results showed that cross-regional transport contributed to 58% pNO3 monthly in the PRD, and this mostly occurred as indirect transport contributions (accounting for 43% among all contributions). For the first time, we identified the mechanism of indirect pNO3 transport in the PRD, which mainly involves transported O3 and locally emitted NOx reacting to produce pNO3 through N2O5 heterogeneous hydrolysis. pNO3 contributions in different periods and regions indicated differences in the indirect transport contributions to N2O5 heterogeneous hydrolysis under varying O3 availability conditions, which are determined by wind fields and the intensity of NOx emissions. On the regional scale, the pNO3 level is controlled by both transported O3 and local NOx emissions, but pNO3 sensitivity to these two precursors varies among cities. This study demonstrates the notable effect and complex process of cross-regional pNO3 transport in the PRD. Considering the important role of transported O3 for pNO3, O3 reduction within a larger scale is required to achieve PM2.5 pollution control target.

Based on the observation by a Regional Air Quality Monitoring Network including 16 monitoring stations, temporal and spatial variations of ozone (O3), NO2 and total oxidant (Ox) were analyzed by both linear regression and cluster analysis. A fast increase of regional O3 concentrations of 0.86 ppbV/yr was found for the annual averaged values from 2006 to 2011 in Guangdong, China. Such fast O3 increase is accompanied by a correspondingly fast NOx reduction as indicated by a fast NO2 reduction rate of 0.61 ppbV/yr. Based on a cluster analysis, the monitoring stations were classified into two major categories – rural stations (non-urban) and suburban/urban stations. The O3 concentrations at rural stations were relatively conserved while those at suburban/urban stations showed a fast increase rate of 2.0 ppbV/yr accompanied by a NO2 reduction rate of 1.2 ppbV/yr. Moreover, a rapid increase of the averaged O3 concentrations in springtime (13%/yr referred to 2006 level) was observed, which may result from the increase of solar duration, reduction of precipitation in Guangdong and transport from Eastern Central China. Application of smog production algorithm showed that the photochemical O3 production is mainly volatile organic compounds (VOC)-controlled. However, the photochemical O3 production is sensitive to both NOx and VOC for O3 pollution episode. Accordingly, it is expected that a combined NOx and VOC reduction will be helpful for the reduction of the O3 pollution episodes in Pearl River Delta while stringent VOC emission control is in general required for the regional O3 pollution control.