Vertical Evolution of Ozone Formation Sensitivity Based on Synchronous Vertical Observations of Ozone and Proxies for Its Precursors: Implications for Ozone Pollution Prevention Strategies.

Photochemical ozone (O3) formation in the atmospheric boundary layer occurs at both the surface and elevated altitudes. Therefore, the O3 formation sensitivity is needed to be evaluated at different altitudes before formulating an effective O3 pollution prevention and control strategy. Herein, we explore the vertical evolution of O3 formation sensitivity via synchronous observations of the vertical profiles of O3 and proxies for its precursors, formaldehyde (HCHO) and nitrogen dioxide (NO2), using multi-axis differential optical absorption spectroscopy (MAX-DOAS) in urban areas of the Beijing-Tianjin-Hebei (BTH), Yangtze River Delta (YRD), and Pearl River Delta (PRD) regions in China. The sensitivity thresholds indicated by the HCHO/NO2 ratio (FNR) varied with altitude. The VOC-limited regime dominated at the ground level, whereas the contribution of the NOx-limited regime increased with altitude, particularly on heavily polluted days. The NOx-limited and transition regimes played more important roles throughout the entire boundary layer than at the surface. The feasibility of extreme NOx reduction to mitigate the extent of the O3 pollution was evaluated using the FNR-O3 curve. Based on the surface sensitivity, the critical NOx reduction percentage for the transition from a VOC-limited to a NOx-limited regime is 45-72%, which will decrease to 27-61% when vertical evolution is considered. With the combined effects of clean air action and carbon neutrality, O3 pollution in the YRD and PRD regions will transition to the NOx-limited regime before 2030 and be mitigated with further NOx reduction.

Vertical profiles of the transport fluxes of aerosol and its precursors between Beijing and its southwest cities.

The influence of regional transport on aerosol pollution has been explored in previous studies based on numerical simulation or surface observation. Nevertheless, owing to inhomogeneous vertical distribution of air pollutants, vertical observations should be conducted for a comprehensive understanding of regional transport. Here we obtained the vertical profiles of aerosol and its precursors using ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) at the Nancheng site in suburban Beijing on the southwest transport pathway of the Beijing-Tianjin-Hebei (BTH) region, China, and then estimated the vertical profiles of transport fluxes in the southwest-northeast direction. The maximum net transport fluxes per unit cross-sectional area, calculated as pollutant concentration multiply by wind speed, of aerosol extinction coefficient (AEC), NO2, SO2 and HCHO were 0.98 km-1 m s-1, 24, 14 and 8.0 µg m-2 s-1 from southwest to northeast, which occurred in the 200-300 m, 100-200 m, 500-600 m and 500-600 m layers, respectively, due to much higher pollutant concentrations during southwest transport than during northeast transport in these layers. The average net column transport fluxes were 1200 km-1 m2 s-1, 38, 26 and 15 mg m-1 s-1 from southwest to northeast for AEC, NO2, SO2 and HCHO, respectively, in which the fluxes in the surface layer (0-100 m) accounted for only 2.3%-4.2%. Evaluation only based on surface observation would underestimate the influence of the transport from southwest cities to Beijing. Northeast or weak southwest transports dominated in clean conditions with PM2.5 <75 µg m-3 and intense southwest transport dominated in polluted conditions with PM2.5 >75 µg m-3. Southwest transport through the middle boundary layer was a trigger factor for aerosol pollution events in urban Beijing, because it not only directly bringing air pollutants, but also induced an inverse structure of aerosols, which resulted in stronger atmospheric stability and aggravated air pollution in urban Beijing.

Exploring the impact of new particle formation events on PM2.5 pollution during winter in the Yangtze River Delta, China.

New particle formation (NPF) events are an increasingly interesting topic in air quality and climate science. In this study, the particle number size distributions, and the frequency of NPF events over Hefei were investigated from November 2018 to February 2019. The proportions of the nucleation mode, Aitken mode, and accumulation mode were 24.59%, 53.10%, and 22.30%, respectively, which indicates the presence of abundant ultrafine particles in Hefei. Forty-six NPF events occurred during the observation days, accounting for 41.82% of the entire observation period. Moreover, the favorable meteorological conditions, potential precursor gases, and PM2.5 range of the NPF events were analyzed. Compared to non-NPF days, the NPF events preferentially occurred on days with lower relative humidity, higher wind speeds, and higher temperatures. When the PM2.5 was 15-20, 70-80, and 105-115 µg/m3, the frequency of the NPF events was higher. Nucleation mode particles were positively related to atmospheric oxidation indicated by ozone when PM2.5 ranged from 15 to 20 µg/m3, and related to gaseous precursors like SO2 and NO2 when PM2.5 was located at 70-80 and 105-115 µg/m3. On pollution days, NPF events did not directly contribute to the increase in the PM2.5 in the daytime, however, NPF events would occur during the night and the growth of particulate matter contributes to the nighttime PM2.5 contents. This could lead to pollution that lasted into the next day. These findings are significant to the improvement of our understanding of the effects of aerosols on air quality.

Improved Anthropogenic SO2 Retrieval from High-Spatial-Resolution Satellite and its Application during the COVID-19 Pandemic.

Sulfur dioxide (SO2) measured by satellites is widely used to estimate anthropogenic emissions. The Sentinel-5 Precursor (S-5P) operational SO2 product is overestimated compared to the ground-based multiaxis differential optical absorption spectroscopy (MAX-DOAS) measurements in China and shows an opposite variation to the surface measurements, which limits the application of TROPOspheric monitoring instrument (TROPOMI) products in emissions research. Radiometric calibration, a priori profiles, and fitting windows might cause the overestimation of S-5P operational SO2 product. Here, we improve the optimal-estimation-based algorithm through several calibration methods. The improved retrieval agrees reasonably well with the ground-based measurements (R > 0.70, bias <13.7%) and has smaller biases (-28.9%) with surface measurements over China and India. It revealed that the SO2 column in March 2020 decreased by 51.6% compared to March 2019 due to the lockdown for curbing the spread of the COVID-19 pandemic, and there was a decrease of 50% during the lockdown than those after the lockdown, similar to the surface measurement trend, while S-5P operational SO2 product showed an unrealistic increase of 19%. In India, the improved retrieval identified obvious "hot spots" and observed a 30% decrease of SO2 columns during the lockdown.

Vertical distributions of wintertime atmospheric nitrogenous compounds and the corresponding OH radicals production in Leshan, southwest China.

Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations were operated from 02 to 21 December 2018 in Leshan, southwest China, to measure HONO, NO2 and aerosol extinction vertical distributions, and these were the first MAX-DOAS measurement results in Sichuan Basin. During the measurement period, characteristic ranges for surface concentration were found to be 0.26-4.58 km-1 and averaged at 0.93 km-1 for aerosol extinction, 0.49 to 35.2 ppb and averaged at 4.57 ppb for NO2 and 0.03 to 7.38 ppb and averaged at 1.05 ppb for HONO. Moreover, vertical profiles of aerosol, NO2 and HONO were retrieved from MAX-DOAS measurements using the Heidelberg Profile (HEIPRO) algorithm. By analysing the vertical gradients of pollutants and meteorological information, we found that aerosol and HONO are strongly localised, while NO2 is mainly transmitted from the north direction (city center direction). Nitrogen oxides such as HONO and NO2 are important for the production of hydroxyl radical (OH) and oxidative capacity in the troposphere. In this study, the averaged value of OH production rate from HONO is about 0.63 ppb/hr and maximum value of ratio between OH production from HONO and from (HONO+O3) is > 93% before12:00 in Leshan. In addition, combustion emission contributes to 26% for the source of HONO in Leshan, and we found that more NO2 being converted to HONO under the conditions with high aerosol extinction coefficient and high relative humidity is also a dominant factor for the secondary produce of HONO.

Revealing the modulation of boundary conditions and governing processes on ozone formation over northern China in June 2017.

In this study, ozonesonde data were used to evaluate the impact of different boundary conditions on the vertical distribution of ozone over urban Beijing. The comparison shows that the clean and static boundary conditions, referred to as PROFILE, apparently underestimate the ozone concentration over the upper troposphere and stratosphere, whereas the global chemical transport model (CTM) provides much more reasonable performance. Further investigation reveals that the boundary conditions exert larger impacts over areas with high altitudes and close distances to boundaries, such as the Tibetan Plateau, while they yield weak impacts on regions relatively far from the boundary, such as the North China Plain (NCP). Process analysis was conducted to investigate the modulation of physical and chemical processes on ozone formation in June 2017, illustrating that during the daytime of the high-O3 period, the photochemical reactions within the planetary boundary layer (PBL) almost become the only source favorable to ozone accumulation. Motivated by this phenomenon, we constructed a linear regression and found that the maximum daily 8-hr ozone (MDA8) ozone concentration was highly correlated with the surface ozone change rate and chemical reactions in the PBL during the pollution period, with MDA8 ozone exceeding 70 ppbv over NCP. Based on this relationship as well as the design of numerical experiments, we propose a strategy of dynamic emission control. Firstly, the emission reduction during the peak ozone formation period may weaken the fast chemical reactions in the PBL and subsequent surface ozone concentration. Secondly, emission reduction one or two days prior to an episode might achieve larger ozone reduction through the accumulation effect. Lastly, emission control outside of the NCP may surpass the local impact under favorable meteorological conditions. Therefore, the efficacy of dynamic emission control was striking when both the accumulation and transport effect were taken into consideration.

Comparison of mixing layer height inversion algorithms using lidar and a pollution case study in Baoding, China.

Beijing-Tianjin-Hebei area is suffering from atmospheric pollution from a long time. The understanding of the air pollution mechanism is of great importance for officials to design strategies for the environmental governance. Mixing layer height (MLH) is a key factor influencing the diffusion of air pollutants. It plays an important role on the evolution of heavy pollution events. Light detection and ranging (lidar), is an effective remote-sensing tool, which can retrieve high spatial and temporal evolution process within mixing layer (ML), especially the variation of MLH. There are many methods to retrieve MLH, but each method has its own applicable limitations. The Mie-lidar data in Beijing was firstly used to compare three different algorithms which are widely used under different pollution levels. We find that the multi-layer structure near surface may cause errors in the detection of mixing layer. The MLH retrieved based on image edge detection was better than another two methods especially under heavy polluted episode. Then we applied this method to investigate the evolution of the mixing layer height during a pollution episode in December 2016. MLH at Gucheng county showed the positive correlation with the concentration of particulate matters during the start of this pollution episode. The elevated pollution level in Gucheng was not associated with MLH's decrease, and the significantly increased particulate matters raised the boundary layer, which trapped the pollutants near the surface.

Characterization of ozone in the lower troposphere during the 2016 G20 conference in Hangzhou.

Recently, atmospheric ozone pollution has demonstrated an aggravating tendency in China. To date, most research about atmospheric ozone has been confined near the surface, and an understanding of the vertical ozone structure is limited. During the 2016 G20 conference, strict emission control measures were implemented in Hangzhou, a megacity in the Yangtze River Delta, and its surrounding regions. Here, we monitored the vertical profiles of ozone concentration and aerosol extinction coefficients in the lower troposphere using an ozone lidar, in addition to the vertical column densities (VCDs) of ozone and its precursors in the troposphere through satellite-based remote sensing. The ozone concentrations reached a peak near the top of the boundary layer. During the control period, the aerosol extinction coefficients in the lower lidar layer decreased significantly; however, the ozone concentration fluctuated frequently with two pollution episodes and one clean episode. The sensitivity of ozone production was mostly within VOC-limited or transition regimes, but entered a NOx-limited regime due to a substantial decline of NOx during the clean episode. Temporary measures took no immediate effect on ozone pollution in the boundary layer; instead, meteorological conditions like air mass sources and solar radiation intensities dominated the variations in the ozone concentration.