Trends and Challenges Regarding the Source-Specific Health Risk of PM2.5-Bound Metals in a Chinese Megacity from 2014 to 2020.

Identifying the health risk of PM2.5 is essential for urban air pollution control. In 2013, China announced the ever-strict national Air Pollution Prevention and Control Action Plan, and its health benefit should be evaluated to provide reference for future policymaking. In this study, we conducted a seven-year (2014-2020) continuous observation of PM2.5 in Shenzhen, the third largest city in China, which has relatively good air quality. The results showed that the annual mean PM2.5 and total concentration of 21 associated metals dropped from 37.7 to 18.5 µg/m3 and from 2.4 to 1.1 µg/m3, respectively. Combining methods for source apportionment and health risk assessment, we found that the total carcinogenic risk (CR) of five hazardous metals (Cd, Cr, Ni, Co, and Pb) showed a clear decreasing trend. However, the total CR (1.8 × 10-6) in 2020 still exceeded the widely acceptable risk level (i.e., 1 × 10-6), with the primary contributor changing from industrial emissions (61%) to vehicle emissions (63%). Further analysis indicated that the CR of vehicles mainly came from Cr and Ni released by braking and tire wearing and has fluctuated in recent years, highlighting a great challenge of controlling nonexhaust emissions of vehicles (including electric cars) in the future.

Coarse particles compensate for missing daytime sources of nitrous acid and enhance atmospheric oxidation capacity in a coastal atmosphere.

Large missing sources of daytime atmospheric nitrous acid (HONO), a vital source of hydroxyl radicals (OH) through its photolysis, frequently exist in global coastal regions. In this study, ambient HONO and relevant species were measured at a coastal site in the Pearl River Delta (PRD), China, during October 2019. Relatively high concentrations (0.32 ± 0.19 ppbv) and daytime peaks at approximately 13:00 of HONO were observed, and HONO photolysis was found to be the dominant (55.5 %) source of the primary OH production. A budget analysis of HONO based on traditional sources suggested large unknown sources during the daytime (66.4 %), which had a significant correlation with the mass of coarse particles (PM2.5-10) and photolysis frequency (J(NO2)). When incorporating photolysis of the abundant nitrate measured in coarse particles with a reasonable enhancement factor relative to fine particles due to favorable aerosol conditions, the missing daytime sources of HONO could be fully compensated by coarse particles serving as the largest source at this coastal site. Our study revealed great potential of coarse particles as a strong daytime HONO source, which has been ignored before but can efficiently promote NOx recycling and thus significantly enhance atmospheric oxidation capacity.

Characterizing formation mechanisms of secondary aerosols on black carbon in a megacity in South China.

Refractory black carbon (rBC) aerosols emitted from incomplete combustion are important climate forcers. Understanding the chemical characteristics and evolution of rBC-related components is particularly crucial to assess rBC environmental impacts. Here, we explored the chemical components of rBC in Shenzhen, China, using a soot-particle aerosol mass spectrometer (SP-AMS). The observations showed that the rBC coating was mainly composed of secondary aerosols with an average mass contribution of 84.7 %. Among them, secondary organic coating occupied ∼57.7 % of the total coating mass. Exploration of the relationship between secondary organic aerosol (SOA) coating and Ox (=NO2 + O3, an indicator of the extent of photochemical processing) showed that SOA coating was generated mainly through photochemical oxidation during the day. Similarly, sulfate coating, with a small mass fraction of 0.9 %, was also dominated by photochemical oxidation. In contrast, nitrate coating responded positively to ambient relative humidity, especially at night, indicating that it was driven by heterogeneous reactions. In addition, the increased ratio of nitrate on rBC to bulk nitrate at night suggested that black carbon surface could facilitate nocturnal nitrate formation.

A novel machine learning method for evaluating the impact of emission sources on ozone formation.

Ambient ozone air pollution is one of the most important environmental challenges in China today, and it is particularly significant to identify pollution sources and formulate control strategies. In present study, we proposed a novel method of positive matrix factorization-SHapley Additive explanation (PMF-SHAP) for evaluating the impact of emission sources on ozone formation, which can quantify the main emission sources of ozone pollution. In this method, we first used the PMF model to identify the source of volatile organic compounds (VOCs), and then quantified various emission sources using a combination of machine learning (ML) models and the SHAP algorithm. The R2 of the optimal ML model in this method was as high as 0.96, indicating that the prediction performance was excellent. Furthermore, we explored the impact of different emission sources on ozone formation, and found that ozone formation in Shenzhen was more affected by VOCs, of which vehicle emission sources may have the greatest impact. Our results suggest that the appropriate combination of traditional models with ML models can well address environmental pollution problems. Moreover, the conclusions obtained based on the PMF-SHAP method were different from the traditional ozone formation potential (OFP) results, providing valuable clues for related mechanism studies.

Decisive role of ozone formation control in winter PM2.5 mitigation in Shenzhen, China.

During the COVID-19 lockdown, atmospheric PM2.5 in the Pearl River Delta (PRD) showed the highest reduction in China, but the reasons, being a critical question for future air quality policy design, are not yet clear. In this study, we analyzed the relationships among gaseous precursors, secondary aerosols and atmospheric oxidation capacity in Shenzhen, a megacity in the PRD, during the lockdown period in 2020 and the same period in 2021. The comprehensive observational datasets showed large lockdown declines in all primary and secondary pollutants (including O3). We found that, however, the daytime concentrations of secondary aerosols during the lockdown period and normal period were rather similar when the corresponding odd oxygen (Ox≡O3+NO2, an indicator of photochemical processing avoiding the titration effect of O3 by freshly emitted NO) were at similar levels. Therefore, reduced Ox, rather than the large reduction in precursors, was a direct driver to achieve the decline in secondary aerosols. Moreover, Ox was also found to determine the spatial distribution of intercity PM2.5 levels in winter PRD. Thus, an effective strategy for winter PM2.5 mitigation should emphasize on control of winter O3 formation in the PRD and other regions with similar conditions.