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 distributions and potential sources of wintertime atmospheric pollutants and the corresponding ozone production on the coast of Bohai Sea.

This study investigated the wintertime vertical distributions and source areas of aerosols, NO2, and HCHO in a coastal city of Dongying from December 2020 to March 2021, using ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) and a potential source contribution function (PSCF) model, respectively. Moreover, the chemical production sensitivity of O3 at different height layers was analyzed using HCHO/NO2 ratios. The results revealed that the wintertime averaged highest concentrations of aerosol (1.25 km-1), NO2 (14.81 ppb), and HCHO (2.32 ppb) were mainly distributed at the surface layer, 100-200 m layer, and 200-300 m layer, respectively. Regarding the diurnal cycles, high concentrations of aerosol (>1.4 km-1) and NO2 (>16.0 ppb) usually appeared in the early morning and late afternoon, while high concentrations of HCHO (>2.5 ppb) usually occurred during 12:00-15:00. The PSCF model revealed that the wintertime aerosol mainly originated from Shandong, northern Jiangsu, Korea, and the northwestern Mongolian Plateau. Below 200 m, NO2 was mainly from western Shandong, whereas above 600 m, it was mainly from northern Shandong and the Beijing-Tianjin-Hebei (BTH) region. The corresponding sources for HCHO were central and southern Shandong (below 200 m) and northern Shandong, northern Jiangsu, and southeastern BTH (above 600 m). In addition, the chemical production sensitivity of O3 below 100 m was observed only in the VOC-limited regime. The percentages of O3 production under the NOx-limited, NOx-VOC-limited, and VOC-limited regimes were 10.75% (31.18%), 4.30% (19.35%), and 84.95% (49.47%) at the 500-600 m (900-1000 m) layer. This study has guiding significance for the coordinated control of PM2.5 and O3, and can assist in the implementation of regional joint prevention and control strategies for air pollutants.

Vertical distribution and temporal evolution of formaldehyde and glyoxal derived from MAX-DOAS observations: The indicative role of VOC sources.

Formaldehyde (HCHO) and glyoxal (CHOCHO) are important oxidization intermediates of most volatile organic compounds (VOCs), but their vertical evolution in urban areas is not well understood. Vertical profiles of HCHO, CHOCHO, and nitrogen dioxide (NO2) were retrieved from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations in Hefei, China. HCHO and CHOCHO vertical profiles prefer to occur at higher altitudes compared to NO2, which might be caused by the photochemistry-oxidation of longer-lived VOCs at higher altitudes. Monthly means of HCHO concentrations were higher in summer, while enhanced amounts of NO2 were mainly observed in winter. CHOCHO exhibited a hump-like seasonal variation, with higher monthly-averaged values not only occurred in warm months (July-August) but also in cold months (November-December). Peak values mainly occurred during noon for HCHO but emerged in the morning for CHOCHO and NO2, suggesting that HCHO is stronger link to photochemistry than CHOCHO. We further use the glyoxal to formaldehyde ratio (GFR) to investigate the VOC sources at different altitudes. The lowest GFR value is almost found in the altitude from 0.2 to 0.4 km, and then rises rapidly as the altitude increases. The GFR results indicate that the largest contributor of the precursor VOC is biogenic VOCs at lower altitudes, while at higher altitudes is anthropogenic VOCs. Our findings provide a lot more insight into VOC sources at vertical direction, but more verification is recommended to be done in the future.

Particle-Phase Photoreactions of HULIS and TMIs Establish a Strong Source of H2O2 and Particulate Sulfate in the Winter North China Plain.

During haze periods in the North China Plain, extremely high NO concentrations have been observed, commonly exceeding 1 ppbv, preventing the classical gas-phase H2O2 formation through HO2 recombination. Surprisingly, H2O2 mixing ratios of about 1 ppbv were observed repeatedly in winter 2017. Combined field observations and chamber experiments reveal a photochemical in-particle formation of H2O2, driven by transition metal ions (TMIs) and humic-like substances (HULIS). In chamber experiments, steady-state H2O2 mixing ratios of 116 ± 83 pptv were observed upon the irradiation of TMI- and HULIS-containing particles. Correspondingly, H2O2 formation rates of about 0.2 ppbv h-1 during the initial irradiation periods are consistent with the H2O2 rates observed in the field. A novel chemical mechanism was developed explaining the in-particle H2O2 formation through a sequence of elementary photochemical reactions involving HULIS and TMIs. Dedicated box model studies of measurement periods with relative humidity >50% and PM2.5 ≥ 75 µg m-3 agree with the observed H2O2 concentrations and time courses. The modeling results suggest about 90% of the particulate sulfate to be produced from the SO2 reaction with OH and HSO3- oxidation by H2O2. Overall, under high pollution, the H2O2-caused sulfate formation rate is above 250 ng m-3 h-1, contributing to the sulfate formation by more than 70%.

Vertical distributions of tropospheric SO2 based on MAX-DOAS observations: Investigating the impacts of regional transport at different heights in the boundary layer.

Information on the vertical distribution of air pollutants is essential for understanding their spatiotemporal evolution underlying urban atmospheric environment. This paper presents the SO2 profiles based on ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements from March 2018 to February 2019 in Hefei, East China. SO2 decrease rapidly with increasing heights in the warm season, while lifted layers were observed in the cold season, indicating accumulation or long-range transport of SO2 in different seasons might occur at different heights. The diurnal variations of SO2 were roughly consistent for all four seasons, exhibiting the minimum at noon and higher values in the morning and late afternoon. Lifted layers of SO2 were observed in the morning for fall and winter, implying the accumulation or transport of SO2 in the morning mainly occurred at the top of the boundary layer. The bivariate polar plots showed that weighted SO2 concentrations in the lower altitude were weakly dependent on wind, but in the middle and upper altitudes, higher weighted SO2 concentrations were observed under conditions of middle-high wind speed. Concentration weighted trajectory (CWT) analysis suggested that potential sources of SO2 in spring and summer were local and transported mainly occurred in the lower altitude from southern and eastern areas; while in fall and winter, SO2 concentrations were deeply affected by long-range transport from northwestern and northern polluted regions in the middle and upper altitudes. Our findings provide new insight into the impacts of regional transport at different heights in the boundary layer on SO2 pollution.

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.

Investigating the impact of Glyoxal retrieval from MAX-DOAS observations during haze and non-haze conditions in Beijing.

This study presents the Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements for Glyoxal (CHOCHO) in Beijing, China (39.95°N, 116.32°E). CHOCHO is the smallest compound of di-carbonyl group. As a primary sink of CHOCHO, its photolysis with NOx (oxides of nitrogen) results in the production of tropospheric ozone. Therefore, the focus of CHOCHO DOAS measurements is increasing in trend. We did the measurements from 09 May 2017 to 09 September 2017. The study was conducted to compare different retrieval settings in order to reveal best DOAS fit settings for CHOCHO; furthermore, effect of haze and non-haze days on CHOCHO concentration was examined. The root mean square of residual and Differential Slant Column density (dSCD) error was reduced when measurements were done with lower wavelength limit around 432-438 nm and upper intervals around 455-460 nm. Thus, lower wavelength intervals around 432-438 nm and upper intervals around 457-460 nm were best for the retrieval of dSCDs for CHOCHO. Meteorological conditions like haze or non-haze days did not have significant effect on DOAS fit parameters. The CHOCHO vertical column densities range from 1.33E+14 to 9.77E+14 molecules/cm2 during the study period with average of 6.16E+14 molecules/cm2. The results indicated that during haze days CHOCHO concentration was higher because of lower rate of photolysis and atmospheric oxidation potential. Our results did not show any significant weekend effect on CHOCHO atmospheric concentration.

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.

Observations of HONO and its precursors between urban and its surrounding agricultural fields: The vertical transports, sources and contribution to OH.

The insufficient study on vertical observations of main atmospheric reactive nitrogen oxides (NO2 and HONO) posed a great challenge to evaluate their intertransport between urban and agricultural areas, and to further learn the atmospheric nitrogen chemistry and the atmospheric oxidation capacity at high altitudes. A stereoscopic measurement campaign (satellite remote sensing, hyperspectral unmanned aerial vehicle (UAV) remote sensing and MAX-DOAS observation) was performed in a typical inland city Hefei and its surrounding agricultural fields from June to October 2022. Average aerosol vertical profiles exhibited a Gaussian shape above 100 m with maximum values of 0.67 km-1 and 0.55 km-1 at 300-400 m layer at Anhui University (AHU) and Changfeng (CF), respectively. The distinct layered structure was mainly attributed to regional transport. Average H2O and NO2 vertical profiles all showed a Gaussian shape and an exponential shape at AHU and CF, respectively. Moreover, the diurnal evolution of H2O profiles performed one peak and bi-peak patterns at AHU and CF, respectively, whereas the diurnal evolution of NO2 at two stations all exhibited bi-peak patterns attributed to vehicle emissions. Average HONO vertical profiles showed an exponential shape and a Gaussian shape at AHU and CF, respectively. Higher HONO (> 0.05 ppb) above 1.0 km at 14:00-16:00 was observed at CF. The transport flux analysis showed that the northern transport flux always larger than southern transport flux for aerosol and H2O. The maximum northern transport fluxes appeared at 300 m and surface for aerosol and H2O, respectively. It indicated that surrounding agricultural fields was an important source of atmospheric H2O of city. The southern transport flux was larger than northern transport flux for NO2, with a maximum net transport flux of 9.20 ppb m s-1 at 100 m. It demonstrated that NO2 transported from urban areas was an important source of NO2 in agricultural fields. For HONO, the southern transport flux was larger than northern transport flux under 100 m, whereas it was opposite above 100 m. It indicated that the HONO distributed at high altitudes at agricultural fields had potential to enhance the atmospheric oxidation capacity of urban area. The net horizontal transport fluxes of HONO of our defined cropland were 5.25 µg m-2 s-1 and -3.65 µg m-2 s-1 during non-fertilization and fertilization periods, respectively. It indicated that the cropland could obviously export HONO to surrounding atmosphere during the fertilization period. Deducing the contribution of direct emission, heterogeneous process was a major source of HONO at urban and agricultural areas. The average surface conversion rate of NO2-to-HONO (CHONO) was 0.01467 h-1, and this value decreased with the increase of height at urban station. While average surface CHONO was 0.0322 h-1 at agricultural fields, which was ~1.2-2.8 times higher than that at urban area. The CHONO at agricultural fields significantly increased with the increase of height. The average CHONO at 1.0 km was ~2.0-3.6 times higher than that at surface. That suggested that the heterogeneous process was the main HONO source at high altitudes at CF, and this process obviously correlated with aerosol and H2O. The higher OH production from HONO (P(OH)HONO) occurred at 0-200 m and 100-400 m with averaged values of 0.31 ppb h-1 and 0.39 ppb h-1 at AHU and CF, respectively. The high P(OH)HONO above 1.0 km at CF from September to October was strongly correlated with high O3 (> 80 ppb). This study emphasized the importance of the stereoscopic of HONO on the analysis of its distribution, evolution, source and atmospheric oxidizing contribution.

Efficient dynamic channel assignment through laser chaos: a multiuser parallel processing learning algorithm.

As laser chaos has been proven to be a robust tool to solve the multi-armed bandit (MAB) problem, this study investigates the problem of multiuser dynamic channel assignment using laser chaos in cognitive radio networks with K-orthogonal channels and M secondary users. A novel dynamic channel assignment algorithm with laser chaos series for multiple users, named parallel processing learning with laser chaos (PPL-LC) algorithm, is proposed to efficiently address two main objectives: stable channel assignment and fuzzy stable channel assignment. The latter objective accounts for the realistic scenario where users have fuzzy preferences and do not necessarily pursue the best preference. The PPL-LC algorithm uses the randomness properties of laser chaos to learn the assignment of channels to multiple users without any limitations on the number of channels, which has not been considered in existing laser chaos algorithms. Moreover, the PPL-LC is equipped with parallel processing channel selections, resulting in higher throughput and stronger adaptability with environmental changes over time than comparison algorithms, such as distributed stable strategy learning and coordinated stable marriage MAB algorithms. Finally, numerical examples are presented to demonstrate the performance of the PPL-LC algorithm.

Satellite spectroscopy reveals the atmospheric consequences of the 2022 Russia-Ukraine war.

With increasing geopolitical conflicts and climate change, the effects of war on the atmosphere remain unclear, especially the recent large-scale war between Russia and Ukraine. Here, we assess how war affects human emission activities by observing atmospheric nitrogen dioxide (NO2) using high-resolution satellite spectroscopy. Spatial and temporal responses of atmospheric composition to armed conflict are characterized. Significant decreases in NO2 concentrations of 10.7-27.3 % occurred in most Ukrainian cities at the beginning of the war, in contrast to dramatic increases in NO2 concentrations in Russian cities outside the northern border. Anomalous changes in NO2 were also found in transportation hubs. By excluding the effect of meteorology, the machine learning model indicates that war-induced changes in anthropogenic emissions may account for ∼40 % of the reduction in NO2 pollution for major cities such as Kyiv. Our study demonstrates that satellites can provide a unique perspective on the atmospheric consequences of humanitarian disasters.

Assessing the impact of urban form and urbanization process on tropospheric nitrogen dioxide pollution in the Yangtze River Delta, China.

Optimizing urban form through urban planning and management policies can improve air quality and transition to demand-side control. Nitrogen dioxide (NO2) in the urban atmosphere, mainly emitted by anthropogenic sources such as industry and vehicles, is a key precursor of fine particles and ozone pollution. Both NO2 and its secondary pollutants pose health risks for humans. Here we assess the interactions between urban forms and airborne NO2 pollution in different cities with various stages of urbanization in the Yangtze River Delta (YRD) in China, by using the machine learning and geographical regression model. The results reveal a strong correlation between urban fragmentation and tropospheric NO2 vertical column density (TVCD) in YRD cities in 2020, particularly those with lower or higher levels of urbanization. The correlation coefficients (R2) between NO2 TVCD and the largest patch index (a metric of urban fragmentation) in different cities are greater than 0.8. For cities at other urbanization stages, population and road density are strongly correlated with NO2 TVCD, with an R2 larger than 0.61. This study highlights the interdependence among urbanization, urban forms, and air pollution, emphasizing the importance of customized urban landscape management strategies for mitigating urban air pollution.

Long-term observations of NO2 using GEMS in China: Validations and regional transport.

In 2019, South Korea launched the Geostationary Environment Monitoring Spectrometer (GEMS) to observe trace gases with an hourly temporal resolution. Compared to previous payloads on polar-orbiting satellites, the GEMS payload has significant advantages in detecting the diurnal variation characteristics of NO2. However, there is still a lack of ground-based validations regarding the overall accuracy of GEMS in the Chinese region. In this study, we conducted a systematic ground validation of GEMS NO2 data in China for the first time. We validated the accuracy of GEMS NO2 data in four typical pollution regions in China, namely the Beijing-Tianjin-Hebei region (JJJ), the Yangtze River Delta region (YRD), the Pearl River Delta region (PRD), and the Sichuan Basin region (SCB), based on MAX-DOAS and CNEMC data. The averaged correlations using the two datasets for validation were 0.81 and 0.57, respectively, indicating a high level of accuracy for the data in China. Using the GEMS seasonal averaged NO2 data, we studied the distribution of NO2 levels in the four regions. We found that the highest NO2 in all four regions occurred during winter with concentrations of 1.84 × 1016 molecules cm-2, 1.59 × 1016 molecules cm-2, 1.58 × 1016 molecules cm-2 and 9.47 × 1015 molecules cm-2, respectively. The distribution of NO2 was closely related to the terrain. Additionally, we observed a significant underestimation issue with TROPOMI, exceeding 30 % in many regions. Based on MAX-DOAS, we investigated the vertical distribution of NO2 in the four regions and found that NO2 was mainly concentrated below 0.5 km. with the HNU station having the lowest concentration, averaging only 2.12 ppb, which was approximately 41 % of the highest concentration recorded at the CQ station. Furthermore, we conducted a study on regional and cross-regional transport using a combination of MAX-DOAS and GEMS data. We found that the transport flux of NO2 could increase by over 500 % within 1 h, making a significant contribution to local NO2 concentrations. The joint observations of GEMS and MAX-DOAS will provide reliable data support for NO2 research and control in China, making a substantial contribution to environmental protection and sustainable development.

Source analysis of the tropospheric NO2 based on MAX-DOAS measurements in northeastern China.

Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (Max-DOAS) measurements of nitrogen dioxide (NO2) were continuously obtained from January to November 2019 in northeastern China (NEC). Seasonal variations in the mean NO2 vertical column densities (VCDs) were apparent, with a maximum of 2.9 × 1016 molecules cm-2 in the winter due to enhanced NO2 emissions from coal-fired winter heating, a longer photochemical lifetime and atmospheric transport. Daily maximum and minimum NO2 VCDs were observed, independent of the season, at around 11:00 and 13:00 local time, respectively, and the most obvious increases and decreases occurred in the winter and autumn, respectively. The mean diurnal NO2 VCDs at 11:00 increased to at 08:00 by 1.6, 5.8, and 6.7 × 1015 molecules cm-2 in the summer, autumn and winter, respectively, due to increased NO2 emissions, and then decreased by 2.8, 4.2, and 5.1 × 1015 molecules cm-2 at 13:00 in the spring, summer, and autumn, respectively. This was due to strong solar radiation and increased planetary boundary layer height. There was no obvious weekend effect, and the NO2 VCDs only decreased by about 10% on the weekends. We evaluated the contributions of emissions and transport in the different seasons to the NO2 VCDs using a generalized additive model, where the contributions of local emissions to the total in the spring, summer, autumn, and winter were 89 ± 12%, 92 ± 11%, 86 ± 12%, and 72 ± 16%, respectively. The contribution of regional transport reached 26% in the winter, and this high contribution value was mainly correlated with the northeast wind, which was due to the transport channel of air pollutants along the Changbai Mountains in NEC. The NO2/SO2 ratio was used to identify NO2 from industrial sources and vehicle exhaust. The contribution of industrial NO2 VCD sources was >66.3 ± 16% in Shenyang due to the large amount of coal combustion from heavy industrial activity, which emitted large amounts of NO2. Our results suggest that air quality management in Shenyang should consider reductions in local NO2 emissions from industrial sources along with regional cooperative control.

Inferring vertical variability and diurnal evolution of O3 formation sensitivity based on the vertical distribution of summertime HCHO and NO2 in Guangzhou, China.

The vertical distributions of formaldehyde (HCHO) and nitrogen dioxide (NO2) and their indicative roles in ozone (O3) sensitivity are important for designing O3 mitigation strategies. Using hyperspectral remote sensing observations, tropospheric vertical profiles of HCHO, NO2, and aerosol extinction were investigated in Guangzhou, China from July to September 2019. On both O3 non-exceedance and polluted days, the HCHO and aerosol vertical profiles exhibited similar Gaussian shapes, but the NO2 profile exhibited an exponential decreasing shape. HCHO and aerosol were especially sensitive to O3 pollution, with higher values generally occurring at approximately noon and late afternoon at higher altitudes. We attempted to study the diurnal evolution of O3 sensitivity at different altitudes based on the HCHO to NO2 ratio (FNR) vertical profile. The FNR thresholds marking the transition regime (2.5 < FNR < 4.0) were derived from the relationship between the increase in O3 (∆O3) and FNR. Our results showed that O3 sensitivity tends to be VOC-limited both at lower (below approximately 0.4 km) and higher (above approximately 1.8 km) altitudes throughout the daytime. In the middle altitudes, the photochemical formation of O3 was mainly in the transition/NOx-limited regime in the morning and afternoon but in the VOC-limited regime at noontime. The relationship between TROPOMI column FNR and near-surface O3 sensitivity was further investigated. Compared with the MAX-DOAS near-surface FNR, slightly higher values of column FNR would increase the number of days classified as transition regimes, which was mainly caused by the inhomogeneous vertical distribution of HCHO and NO2 in the lower troposphere. This study provides an improved understanding of vertical variability and diurnal evolution of O3 formation sensitivity.

Identification of ozone sensitivity for NO2 and secondary HCHO based on MAX-DOAS measurements in northeast China.

In this study, tropospheric formaldehyde (HCHO) vertical column densities (VCDs) were measured using multi-axis differential optical absorption spectroscopy (MAX-DOAS) from January to November 2019 in Shenyang, Northeast China. The maximum HCHO VCD value appeared in the summer (1.74 × 1016 molec/cm2), due to increased photo-oxidation of volatile organic compounds (VOCs). HCHO concentrations increased from 08:00 and peaked near 13:00, which was mainly attributed to the increased release of isoprene from plants and enhanced photolysis at noon. The HCHO VCDs observed by MAX-DOAS and OMI have a good correlation coefficient (R) of 0.78, and the contributions from primary and secondary HCHO sources were distinguished by the multi-linear regression model. The anthropogenic emissions showed unobvious seasonal variations, and the primary HCHO was relatively stable in Shenyang. Secondary HCHO contributed 82.62%, 83.90%, 78.90%, and 41.53% to the total measured ambient HCHO during the winter, spring, summer, and autumn, respectively. We also found a good correlation (R = 0.78) between enhanced vegetation index (EVI) and HCHO VCDs, indicating that the oxidation of biogenic volatile organic compounds (BVOCs) was the main source of HCHO. The ratio of secondary HCHO to nitrogen dioxide (NO2) was used as the tracer to analyze O3-NOx-VOC sensitivities. We found that the VOC-limited, VOC-NOx-limited, and NOx-limited regimes made up 93.67%, 6.23%, 0.11% of the overall measurements, respectively. In addition, summertime ozone (O3) sensitivity changed from VOC-limited in the morning to VOC-NOx-limited in the afternoon. Therefore, this study offers information on HCHO sources and corresponding O3 production sensitivities to support strategic management decisions.

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.

Vertical characterization and potential sources of aerosols in different seasons over the Yangtze River Delta using ground-based MAX-DOAS.

Assessing the vertical distribution of aerosols in the atmosphere can elucidate the regional sources of accumulated pollutants at different altitudes. Although studies in Hefei have mainly focused on aerosols in the near-surface atmosphere, few studies have assessed the vertical variability in aerosol concentrations. In this study, the vertical aerosol distribution in Hefei was analyzed continuously for one year (from March 2018 to February 2019) using multi-axis differential optical absorption spectroscopy. The aerosol extinction coefficient was the highest in winter (0.94 km-1), followed by autumn (0.63 km-1), spring (0.57 km-1), and summer (0.47 km-1). Local pollution caused the accumulation of aerosols near the surface. The rate of decrease of the aerosol extinction coefficient was higher in autumn and winter than in spring and summer. The diurnal variations of aerosol extinction coefficient in the different seasons were affected by the planetary boundary layer height, and we observed notable high-altitude transport of aerosols in autumn. We assessed the vertical distribution of the aerosol extinction coefficient under different pollution concentrations and identified peak values mainly below a height of 0.5 km. With increasing height, the extinction coefficient decreased linearly and slowly under low PM2.5 concentrations, whereas decreased more rapidly under high PM2.5 concentrations. Clustering analysis, the weight potential source concentration function, and the concentration weighted trajectory model inferred different seasonal characteristics in the potential source areas of aerosols at different heights. In addition to local pollution sources, Jiangsu Province was found to be the main source of pollution in Hefei at a height of 0.4 km, whereas Hubei Province was the main source of pollution at a height of 2 km.

Identifying the wintertime sources of volatile organic compounds (VOCs) from MAX-DOAS measured formaldehyde and glyoxal in Chongqing, southwest China.

Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations were performed from 27 December 2018 to 16 January 2019 in Changshou, one of subdistricts of Chongqing, China. Primary atmospheric pollutant in Changshou during wintertime was PM2.5, whose contribution averaged about 70.15% ± 9.5% of PM10. The ratio of PM2.5/PM10 decreased when PM2.5 pollution became worse, and it should attribute to biomass burning and the contribution of hygroscopic growth and enhanced heterogeneous chemistry under high relative humidity condition. Moreover, nitrogen dioxide (NO2), formaldehyde (HCHO) and glyoxal (CHOCHO) vertical profiles during the campaign period were retrieved separately. TROPOMI HCHO vertical column densities (VCDs) and MAX-DOAS HCHO VCDs were correlated well (R = 0.93). In order to identify the sources of volatile organic compound (VOC) in Changshou, the ratio of CHOCHO to HCHO (RGF) in five different layers were estimated. The estimated daily averaged RGF were 0.0205 ± 0.0077, 0.0727 ± 0.0286, 0.0864 ± 0.0296, 0.0770 ± 0.0275 and 0.0746 ± 0.0263 in 0-100 m, 100-200 m, 300-400 m, 500-600 m and 700-800 m layers, respectively. The estimated RGF will increase when biomass burnings were dominated. Using NO2 as a tracer of anthropogenic emissions, we found the RGF values gradually decrease with the increase of NO2 levels. RGF values in 0-100 m layer and all the other upper layers are 0.015-0.025 and 0.06-0.14, and that means the dominant sources of VOCs in 0-100 m layer and all the other upper layers are biogenic emission and anthropogenic emission (especially biomass burning), respectively. In addition, we found that RGF has site dependence which is in compliance with several previous studies.

First observation of tropospheric nitrogen dioxide from the Environmental Trace Gases Monitoring Instrument onboard the GaoFen-5 satellite.

The Environmental Trace Gases Monitoring Instrument (EMI) is the first Chinese satellite-borne UV-Vis spectrometer aiming to measure the distribution of atmospheric trace gases on a global scale. The EMI instrument onboard the GaoFen-5 satellite was launched on 9 May 2018. In this paper, we present the tropospheric nitrogen dioxide (NO2) vertical column density (VCD) retrieval algorithm dedicated to EMI measurement. We report the first successful retrieval of tropospheric NO2 VCD from the EMI instrument. Our retrieval improved the original EMI NO2 prototype algorithm by modifying the settings of the spectral fit and air mass factor calculations to account for the on-orbit instrumental performance changes. The retrieved EMI NO2 VCDs generally show good spatiotemporal agreement with the satellite-borne Ozone Monitoring Instrument and TROPOspheric Monitoring Instrument (correlation coefficient R of ~0.9, bias < 50%). A comparison with ground-based MAX-DOAS (Multi-Axis Differential Optical Absorption Spectroscopy) observations also shows good correlation with an R of 0.82. The results indicate that the EMI NO2 retrieval algorithm derives reliable and precise results, and this algorithm can feasibly produce stable operational products that can contribute to global air pollution monitoring.