Does Ozone Pollution Share the Same Formation Mechanisms in the Bay Areas of China?

As important regions of transition between land and sea, the three bay areas of Bohai Bay (BHB), Hangzhou Bay (HZB), and Pearl River Estuary (PRE) in China often suffer from severe photochemical pollution despite scarce anthropogenic emissions. To understand the causes of high ozone (O3) concentrations, the high O3 episode days associated with special synoptic systems in the three bays were identified via observations and simulated by the weather research and forecasting coupled with community multiscale air quality (WRF-CMAQ) model. It was revealed that the interaction between synoptic winds and mesoscale breezes resulted in slow wind speeds over the HZB and PRE, where air pollutants transported from upwind cities gained a long residence time and subsequently participated in intensive photochemical reactions. The net O3 production rates within the bay areas were even comparable to those in surrounding cities. This finding was also applicable to BHB but with lower net O3 production rates, while high levels of background O3 and the regional transport from farther upwind BHB partially elevated the O3 concentrations. Hence, these three bay areas served as O3 "pools" which caused the accumulation of air pollutants via atmospheric dynamics and subsequent intense photochemical reactions under certain meteorological conditions. The results may be applicable to other similar ecotones around the world.

Remarkable spring increase overwhelmed hard-earned autumn decrease in ozone pollution from 2005 to 2017 at a suburban site in Hong Kong, South China.

Ozone (O3) pollution has been a persistent problem in Hong Kong, particularly in autumn when severe O3 pollution events are often observed. In this study, linear regression analyses of long-term O3 data in suburban Hong Kong revealed that the variation of autumn O3 obviously leveled off during 2005-2017, mainly due to the significant decrease of autumn O3 in 2013-2017 (period II), despite the increase in 2005-2012 (period I). In addition, the rise of O3 in summer and winter also ceased since 2013. In contrary, O3 continuously increased throughout the spring of 2005-2017, especially in period II. Consequently, an incessant increase of overall O3 was observed during 2005-2017. A statistical model combining Kolmogorov-Zurbenko filter with multiple linear regressions, and a photochemical box model incorporating CB05 mechanism were applied to probe the causes of the above trends. In general, O3 production was controlled by VOC-limited regime throughout 13 years. The meteorological variability and regional transport facilitated the O3 growth in period Ι. In contrast, the unchanged O3 level in period II was attributable to the negative impact of meteorological variability and reduction of regional transport effect on O3 formation and accumulation, as well as the negligible change in locally-produced O3. In autumn of period II, the inhibitory meteorological variability, reduced regional transport, and alleviated local production were the driving force for the hard-earned decrease of O3. However, the remarkable rise of spring O3 was caused by the reduction of NOx, especially in the spring of period II. The findings of the long-term and seasonal variations of O3 pollution in Hong Kong are helpful for future O3 mitigation.

Photochemical ozone pollution in five Chinese megacities in 2018.

To investigate photochemical ozone (O3) pollution in urban areas in China, O3 and its precursors and meteorological parameters were simultaneously measured in five megacities in China in summer 2018. Moderate wind speeds, strong solar radiation and high temperature were observed in all cities, indicating favorable meteorological conditions for local O3 formation. However, the unusually frequent precipitation caused by typhoons reaching the eastern coastline resulted in the least severe air pollution in Shanghai. The highest O3 level was found in Beijing, followed by Lanzhou and Wuhan, while relatively lower O3 value was recorded in Chengdu and Shanghai. Photochemical box model simulations revealed that net O3 production rate in Lanzhou was the largest, followed by Beijing, Wuhan and Chengdu, while it was the lowest in Shanghai. Besides, the O3 formation was mainly controlled by volatile organic compounds (VOCs) in most cities, but co-limited by VOCs and nitrogen oxides in Lanzhou. Moreover, the dominant VOC groups contributing to O3 formation were oxygenated VOCs (OVOCs) in Beijing and Wuhan, alkenes in Lanzhou, and aromatics and OVOCs in Shanghai and Chengdu. Source apportionment analysis identified six sources of O3 precursors in these cities, including liquefied petroleum gas usage, diesel exhaust, gasoline exhaust, industrial emissions, solvent usage, and biogenic emissions. Gasoline exhaust dominated the O3 formation in Beijing, and LPG usage and industrial emissions made comparable contributions in Lanzhou, while LPG usage and solvent usage played a leading role in Wuhan and Chengdu, respectively. The findings are helpful to mitigate O3 pollution in China.

Real-time molecular characterization of air pollutants in a Hong Kong residence: Implication of indoor source emissions and heterogeneous chemistry.

Due to the high health risks associated with indoor air pollutants and long-term exposure, indoor air quality has received increasing attention. In this study, we put emphasis on the molecular composition, source emissions, and chemical aging of air pollutants in a residence with designed activities mimicking ordinary Hong Kong homes. More than 150 air pollutants were detected at molecular level, 87 of which were quantified at a time resolution of not less than 1 hour. The indoor-to-outdoor ratios were higher than 1 for most of the primary air pollutants, due to emissions of indoor activities and indoor backgrounds (especially for aldehydes). In contrast, many secondary air pollutants exhibited higher concentrations in outdoor air. Painting ranked first in aldehyde emissions, which also caused great enhancement of aromatics. Incense burning had the highest emissions of particle-phase organics, with vanillic acid and syringic acid as markers. The other noteworthy fingerprints enabled by online measurements included linoleic acid, cholesterol, and oleic acid for cooking, 2,5-dimethylfuran, stigmasterol, iso-/anteiso-alkanes, and fructose isomers for smoking, C28 -C34 even n-alkanes for candle burning, and monoterpenes for the use of air freshener, cleaning agents, and camphor oil. We showed clear evidence of chemical aging of cooking emissions, giving a hint of indoor heterogeneous chemistry. This study highlights the value of organic molecules measured at high time resolutions in enhancing our knowledge on indoor air quality.

Photochemistry of ozone pollution in autumn in Pearl River Estuary, South China.

To explore the photochemical O3 pollution over the Pearl River Estuary (PRE), intensive measurements of O3 and its precursors, including trace gases and volatile organic compounds (VOCs), were simultaneously conducted at a suburban site on the east bank of PRE (Tung Chung, TC) in Hong Kong and a rural site on the west bank (Qi'ao, QA) in Zhuhai, Guangdong in autumn 2016. Throughout the sampling period, 3 days with high O3 levels (maximum hourly O3 > 100 ppbv) were captured at both sites (pattern 1) and 13 days with O3 episodes occurred only at QA (pattern 2). It was found that O3 formation at TC was VOC-limited in both patterns because of the large local NOx emissions. However, the O3 formation at QA was co-limited by VOCs and NOx in pattern 1, but VOC-limited in pattern 2. In both patterns, isoprene, formaldehyde, xylenes and trimethylbenzenes were the top 4 VOCs that modulated local O3 formation at QA, while they were isoprene, formaldehyde, xylenes and toluene at TC. In pattern 1, the net O3 production rate at QA (13.1 ± 1.6 ppbv h-1) was high, and comparable (p = 0.40) to that at TC (12.1 ± 1.5 ppbv h-1), so was the hydroxyl radical (i.e., OH), implying high atmospheric oxidative capacity over PRE. In contrast, the net O3 production rate was significantly higher (p < 0.05) at QA (16.3 ± 0.4 ppbv h-1) than that at TC (4.7 ± 0.2 ppbv h-1) in pattern 2, and the OH concentration and cycling rate were also higher, indicating much stronger photochemical reactions at QA. These findings enhanced our understanding of O3 photochemistry in the Pearl River estuary, which could be extended to other estuaries.

Hazardous volatile organic compounds in ambient air of China.

Volatile organic compounds (VOCs) are ubiquitous in the atmosphere and the majority of them have been proved to be detrimental to human health. The hazardous VOCs were studied very insufficiently in China, despite the enormous emissions of VOCs. In this study, the concentrations and sources of 17 hazardous VOCs reported in literature were reviewed, based on which the health effects were assessed. In-depth survey indicated that benzene and toluene had the highest concentrations in eastern China (confined to the study regions reviewed, same for the other geographic generalization), which however showed significant declines. The southern China featured high levels of trichloroethylene. Dichloromethane and chloroform were observed to be concentrated in northern China. The distributions of 1,2-dichloropropane and tetrachloroethylene were homogeneous across the country. Basically consistent with the spatial patterns of ozone, the summertime formaldehyde exhibited higher levels in eastern and northern China, and increased continuously. While transportation served as the largest source of benzene and toluene, industrial emissions and secondary formation were the predominant contributors of halogenated hydrocarbons and aldehydes (formaldehyde and acetaldehyde), respectively. The chronic non-cancer effects of inhalation exposure to the hazardous VOCs were insignificant, however the probabilities of developing cancers by inhaling the hazardous VOCs in ambient air of China were quite high. Formaldehyde was identified as the primary carcinogenic VOC in the atmosphere of most regions. The striking results, especially the high inhalation cancer risks, alerted us that the emission controls of hazardous VOCs were urgent in China, which must be grounded upon full understanding of their occurrence, presence and health effects.

Photochemical evolution of continental air masses and their influence on ozone formation over the South China Sea.

To investigate photochemical ozone (O3) pollution over the South China Sea (SCS), an intensive sampling campaign was conducted from August to November simultaneously at a continental site (Tung Chung, TC) and a marine site (Wan Shan Island, WSI). It was found that when continental air masses intruded the SCS, O3 episodes often occurred subsequently. To discover the causes, a photochemical trajectory model (PTM) coupled with the near-explicit Master Chemical Mechanism (MCM) was adopted, and the photochemical processes of air masses during the transport from TC to WSI were investigated. The simulated O3 and its precursors (i.e. NOx and VOCs) showed a reasonably good agreement with the observations at both TC and WSI, indicating that the PTM was capable of simulating O3 formation for air masses traveling from TC to WSI. The modeling results revealed that during the transport of air masses from TC to WSI, both VOC and NOx decreased in the morning while O3 increased significantly, mainly due to rapid chemical reactions with elevated radicals over the SCS. The elevated radicals over the SCS were attributable to the fact that higher NOx at TC consumed more radicals, whereas the concentration of radicals increased from TC to WSI because of NOx dilution and destruction. Subsequently, the photochemical cycling of radicals accelerated, leading to high O3 mixing ratios over the SCS. Furthermore, based on the source profiles of the emission inventory used, the contributions of six sources, i.e. gasoline vehicle exhaust, diesel vehicle exhaust, gasoline evaporation and LPG usage, solvent usage, biomass and coal burning, and biogenic emissions, to maritime O3 formation were evaluated. The results suggested that gasoline vehicles exhaust and solvent usage largely contributed the O3 formation over the SCS (about 5.2 and 3.8 ppbv, respectively). This is the first time that the contribution of continental VOC sources to the maritime O3 formation was quantified.

Surface O3 photochemistry over the South China Sea: Application of a near-explicit chemical mechanism box model.

A systematic field measurement was conducted at an island site (Wanshan Island, WSI) over the South China Sea (SCS) in autumn 2013. It was observed that mixing ratios of O3 and its precursors (such as volatile organic compounds (VOCs), nitrogen oxides (NOx = NO + NO2) and carbon monoxide (CO)) showed significant differences on non-episode days and episode days. Additional knowledge was gained when a photochemical box model incorporating the Master Chemical Mechanism (PBM-MCM) was applied to further investigate the differences/similarities of O3 photochemistry between non-episode and episode days, in terms of O3-precursor relationship, atmospheric photochemical reactivity and O3 production. The simulation results revealed that, from non-O3 episode days to episode days, 1) O3 production changed from both VOC and NOx-limited (transition regime) to VOC-limited; 2) OH radicals increased and photochemical reaction cycling processes accelerated; and 3) both O3 production and destruction rates increased significantly, resulting in an elevated net O3 production over the SCS. The findings indicate the complexity of O3 pollution over the SCS.