Atmospheric Oxidation Capacity Research Articles

Shifts of Formation Regimes and Increases of Atmospheric Oxidation Led to Ozone Increase in North China Plain and Yangtze River Delta From 2016 to 2019

AbstractChina is confronting severe ozone (O3) pollution although particulate matter reduced significantly, causing damages to public health and ecological systems. Here we utilized the comprehensive methods of ground‐level observations, satellite data, and source‐oriented chemical transport model to interpret O3 variations throughout China from 2016 to 2019. A remarkably worsened trend of O3 levels has been found both by observation and simulation in these years. Our results showed that the remarkable O3 elevation was found in the North China Plain (NCP) and Yangtze River Delta (YRD) (maximum daily 8 hr average O3 ∼60 ppb) with an annual increasing rate of 10%. In addition, O3 formation regimes also changed in the NCP, where 4.9% grids shifted from VOC‐limited to transition regimes and 9.6% grids shifted from transition to NOx‐limited regimes. The elevation of MDA8 O3 was mainly attributed to the enhanced atmospheric oxidation capacity (AOC) in above regions. Particularly, the increasing rates of OH and HO2 radicals (major oxidants) in NCP and YRD reached ∼15% and ∼5%, respectively. The comprehensive study of long‐term O3 changes, formation regimes, and AOC based on a multimethod approach should be considered when designing O3 control policies.

Hindered visibility improvement despite marked reduction in anthropogenic emissions in a megacity of southwestern China: An interplay between enhanced secondary inorganics formation and hygroscopic growth at prevailing high RH conditions

The PM2.5-bound visibility improvement remains challenging in China despite vigorous control on anthropogenic emissions in recent years. One critical issue could exist in the distinct physicochemical properties especially of secondary aerosol components. Taken the COVID-19 lockdown as an extreme case, we focus on the relationship between visibility, emission cuts, and secondary formation of inorganics with changing optical and hygroscopic behaviors in Chongqing, a representative city characterized with humid weather and poor diffusion conditions in Sichuan Basin, southwest of China.It is found that the increased secondary aerosol abundance (e.g., PM2.5/CO and PM2.5/PM10 as a proxy) with enhanced atmospheric oxidative capacity (e.g., O3/Ox, Ox = O3 + NO2), combined with insignificant meteorological dilution effect, might partly offset the benefit on the improved visibility from substantial reduction in anthropogenic emissions during the COVID-19 lockdown. This is in line with the efficient oxidation rates of sulfur and nitrogen (i.e., SOR, NOR), increasing more significantly with PM2.5 and relative humidity (RH) in comparison to O3/Ox. The resulted larger fraction of nitrate and sulfate (i.e., fSNA) would promote the optical enhancement (i.e., f(RH)) and mass extinction efficiency (MEE) of PM2.5, especially under highly humid conditions (e.g., RH > 80 %, with approximately half of the occurrence frequency). This could further facilitate secondary aerosol formation via aqueous-phase reaction and heterogeneous oxidation, likely due to enhanced water uptake and enlarged size/surface area upon hydration. In combination of gradually increased atmospheric oxidative capacity, this positive feedback would in turn inhibit the visibility improvement particularly at high RH environment.Considering the current air pollution complex status over China, further work on the formation mechanisms of major secondary species (e.g., sulfate, nitrate, and secondary organics), size-resolved chemical and hygroscopic properties, together with their interactions are highly recommended. Our results are hoping to assist in the atmospheric pollution complex mitigation and prevention in China.

Proteinaceous Matter in PM2.5 in Suburban Guiyang, Southwestern China: Decreased Importance in Long‐Range Transport and Atmospheric Degradation

AbstractProteinaceous matter (PrM) is a substantial constituent in bioaerosols. However, the sources and atmospheric processes of PrM remain large uncertainties. The characterizations, sources, and potential atmospheric processes of free amino acids (FAAs) and combined amino acids (CAAs) were investigated via a set of 1‐year fine particle (PM2.5) samples collected in suburban Guiyang (a hilly basin area in Southwest China). The annual average concentrations of FAAs and CAAs were 156.31 ± 41.52 and 315.36 ± 147.66 ng m−3, respectively. The dominant FAA and CAA species were proline, which was different from previous observations with glycine as a major species. The results indicated that the sources or atmospheric processes of aerosol PrM at this study site were different from previous observations in the urban and suburban areas. The analysis of AA‐nitrogen isotope compositions and air mass back trajectories suggested that the abundances of aerosol FAAs and CAAs were highly controlled by primary sources (particularly plants) with less impact from long‐range transport. Furthermore, the contributions of PrM degradation by ozone‐ and hydroxyl radical‐related processes to total FAAs were found to be minor. The overall results suggested that the long‐range transport and atmospheric degradation of PrM were insignificant factors affecting aerosol PrM abundance in this suburban area with the weak atmospheric oxidation capacity, high cloud cover rate, and frequent precipitation. Thus, the findings improve our understanding of the sources and atmospheric processes of aerosol PrM.

Significant contribution of carbonyls to atmospheric oxidation capacity (AOC) during the winter haze pollution over North China Plain

Atmospheric carbonyl compounds play significant roles in the cycling of radicals and have exhibited surprisingly high levels in winter that were well correlated to particulate matter, for which the reason have not been clearly elucidated. Here we measured carbonyl compounds and other trace gasses together with PM2.5 over urban Jinan in North China Plain during the winter. Markedly higher carbonyl concentrations (average: 14.63 ± 4.21 ppbv) were found during wintertime haze pollution, about one to three-times relative to those on non-haze days, with slight difference in chemical composition except formaldehyde (HCHO). HCHO (3.68 ppbv), acetone (3.17 ppbv), and acetaldehyde (CH3CHO) (2.83 ppbv) were the three most abundant species, accounting for ∼75% of the total carbonylson both haze and non-haze days. Results from observational-based model (OBM) with atmospheric oxidation capacity (AOC) indicated that AOC significantly increased with the increasing carbonyls during the winter haze events. Carbonyl photolysis have supplied key oxidants such as RO2 and HO2, and thereby enhancing the formation of fine particles and secondary organic aerosols, elucidating the observed haze-carbonyls inter-correlation. Diurnal variation with carbonyls exhibiting peak values at early-noon and night highlighted the combined contribution of both secondary formation and primary diesel-fuel sources. 1-butene was further confirmed to be the major precursor for HCHO. This study confirms the great contribution of carbonyls to AOC, and also suggests that reducing the emissions of carbonyls would be an effective way to mitigate haze pollution in urban area of the NCP region.

Technical note: Constraining the hydroxyl (OH) radical in the tropics with satellite observations of its drivers – first steps toward assessing the feasibility of a global observation strategy

Abstract. Despite its importance in controlling the abundance of methane (CH4) and a myriad of other tropospheric species, the hydroxyl radical (OH) is poorly constrained due to its large spatial heterogeneity and the inability to measure tropospheric OH with satellites. Here, we present a methodology to infer tropospheric column OH (TCOH) in the tropics over the open oceans using a combination of a machine learning model, output from a simulation of the GEOS model, and satellite observations. Our overall goals are to assess the feasibility of our methodology, to identify potential limitations, and to suggest areas of improvement in the current observational network. The methodology reproduces the variability of TCOH from independent 3D model output and of observations from the Atmospheric Tomography mission (ATom). While the methodology also reproduces the magnitude of the 3D model validation set, the accuracy of the magnitude when applied to observations is uncertain because current observations are insufficient to fully evaluate the machine learning model. Despite large uncertainties in some of the satellite retrievals necessary to infer OH, particularly for NO2 and formaldehyde (HCHO), current satellite observations are of sufficient quality to apply the machine learning methodology, resulting in an error comparable to that of in situ OH observations. Finally, the methodology is not limited to a specific suite of satellite retrievals. Comparison of TCOH determined from two sets of retrievals does show, however, that systematic biases in NO2, resulting both from retrieval algorithm and instrumental differences, lead to relative biases in the calculated TCOH. Further evaluation of NO2 retrievals in the remote atmosphere is needed to determine their accuracy. With slight modifications, a similar methodology could likely be expanded to the extratropics and over land, with the benefits of increasing our understanding of the atmospheric oxidation capacity and, for instance, informing understanding of recent CH4 trends.

Seasonal variation characteristics of atmospheric peroxyacetyl nitrate (PAN) and its source apportionment in a megacity in southern China

Owing to its biotoxicity and inductive effect on photochemical pollution, atmospheric peroxyacetyl nitrate (PAN), which is a typical product of atmospheric photochemical reactions, has attracted much research attention. However, to the best of our knowledge, few comprehensive studies have been conducted on the seasonal variation and key influencing factors of PAN concentrations in southern China. In this study, PAN, ozone (O3), precursor volatile organic compound (VOC), and other pollutant concentrations were measured online for 1 year (from October 2021 to September 2022) in Shenzhen, a megacity in the Greater Bay Area of China. The average concentrations of PAN and peroxypropionyl nitrate (PPN) were 0.54 and 0.08 parts per billion (ppb), and the maximum hourly concentrations reached 10.32 and 1.01 ppb, respectively. The results of the generalized additive model (GAM) showed that the atmospheric oxidation capacity and precursor concentration were the most important factors affecting the PAN concentration. According to the steady-state model, the average cumulative contribution to the peroxyacetyl (PA) radical formation rate by six major carbonyl compounds was calculated at 4.2 × 106 molecules cm−3 s−1, and acetaldehyde (63.0 %) and acetone (13.9 %) contributed the most. Furthermore, the photochemical-age-based parameterization method was used to analyze the source contributions of carbonyl compounds and PA radicals. The results showed that although the primary anthropogenic (40.2 %), biogenic (27.8 %), and secondary anthropogenic (16.4 %) sources were the most important contributors of PA radicals, the biogenic and secondary anthropogenic source contributions both increased considerably in summer, and the cumulative proportion of both sources reached ~70 % in July. In addition, a comparison of PAN pollution processes in different seasons revealed that in summer and winter, the PAN concentration was predominantly limited by precursors and meteorological parameters, such as light intensity, respectively.

Formation pathways of organic aerosols over a tropical coastal atmosphere

The characteristics of non-refractory submicron aerosols (NR-PM1), focusing on organic aerosols, are examined over a tropical coastal location, Thumba, in southern peninsular India. The measurements were carried out using an aerosol chemical speciation monitor during 2017–2021. The results indicated organic aerosols as the major component (67–85%) in the NR-PM1 mass loading during all seasons. Positive matrix factorization (PMF) analysis on the OA mass spectra yielded two factors resolving Hydrocarbon-like organic aerosols (HOA) and Oxygenated organic aerosols (OOA), with the major contribution to OA coming from OOA (mass fraction >50%) during all the seasons. Examination of the diurnal variations revealed the daytime enhancement in OOA and sulfate mass fractions, indicating photochemical production overwhelming the dilution at the surface due to local atmospheric boundary layer expansion. The OOA mass concentration showed a good correlation (R > 0.5) with odd oxygen (O3+NO2) and with an increase in oxygen-to-carbon ratio (ΔO:C = 0.11 to 0.35 with Δodd oxygen = 60 μg m−3 for different seasons) (i.e., increased oxidation degree of OA) signifying the dominance of photochemistry and subsequent enhanced atmospheric oxidative capacity in OOA formation. Interestingly, the aerosol liquid water content (ALWC) doubled during the nighttime (>40 μg m−3) compared to the daytime (<20 μg m−3) in different seasons, indicating the combined impact of varying submicron aerosol composition and ambient relative humidity. Since highly humid (relative humidity >85%) conditions prevail over this tropical coastal station, especially during the nighttime, the role of aqueous-phase formation of OA is also examined. It was found that less oxidized/less-hygroscopic OA were prevalent during the nighttime, resulting in lower aqueous-phase OA processing. During all the seasons, the hygroscopicity of organics (кorganics) reached as high as > 0.22 and was mainly driven by photochemical processing rather than aqueous-phase chemistry. These results highlight the importance of the OA formation pathways in affecting their hygroscopic properties over the tropical atmosphere.

Impact of aerosol in-situ peroxide formations induced by metal complexes on atmospheric H2O2 budgets

Hydrogen peroxide (H2O2), hydroxyl radicals (OH), hydroperoxyl (HO2), and superoxide (O2−) radicals interacting with aerosol particles significantly affect the atmospheric pollutant budgets. A multiphase chemical kinetic box model (PKU-MARK), including the multiphase processes of transition metal ions (TMI) and their organic complexes (TMI-OrC), was built to numerically drive H2O2 chemical behaviors in the aerosol particle liquid phase using observational data obtained from a field campaign in rural China. Instead of relying on fixed uptake coefficient values, a thorough simulation of multiphase H2O2 chemistry was performed. In the aerosol liquid phase, light-driven TMI-OrC reactions promote OH, HO2/O2−, and H2O2 recycling and spontaneous regenerations. The in-situ generated aerosol H2O2 would offset gas-phase H2O2 molecular transfer into the aerosol bulk phase and promote the gas-phase level. When combined with the multiphase loss and in-situ aerosol generation involving TMI-OrC mechanism, the HULIS-Mode significantly improves the consistency between modeled and measured gas-phase H2O2 levels. Aerosol liquid phase could be a pivotal potential source of aqueous H2O2 and influence the multiphase budgets. Our work highlights the intricate and significant effects of aerosol TMI and TMI-OrC interactions on the multiphase partitioning of H2O2 when assessing atmospheric oxidant capacity.

Separating Daily 1 km PM2.5 Inorganic Chemical Composition in China since 2000 via Deep Learning Integrating Ground, Satellite, and Model Data.

Fine particulate matter (PM2.5) chemical composition has strong and diverse impacts on the planetary environment, climate, and health. These effects are still not well understood due to limited surface observations and uncertainties in chemical model simulations. We developed a four-dimensional spatiotemporal deep forest (4D-STDF) model to estimate daily PM2.5 chemical composition at a spatial resolution of 1 km in China since 2000 by integrating measurements of PM2.5 species from a high-density observation network, satellite PM2.5 retrievals, atmospheric reanalyses, and model simulations. Cross-validation results illustrate the reliability of sulfate (SO42-), nitrate (NO3-), ammonium (NH4+), and chloride (Cl-) estimates, with high coefficients of determination (CV-R2) with ground-based observations of 0.74, 0.75, 0.71, and 0.66, and average root-mean-square errors (RMSE) of 6.0, 6.6, 4.3, and 2.3 μg/m3, respectively. The three components of secondary inorganic aerosols (SIAs) account for 21% (SO42-), 20% (NO3-), and 14% (NH4+) of the total PM2.5 mass in eastern China; we observed significant reductions in the mass of inorganic components by 40-43% between 2013 and 2020, slowing down since 2018. Comparatively, the ratio of SIA to PM2.5 increased by 7% across eastern China except in Beijing and nearby areas, accelerating in recent years. SO42- has been the dominant SIA component in eastern China, although it was surpassed by NO3- in some areas, e.g., Beijing-Tianjin-Hebei region since 2016. SIA, accounting for nearly half (∼46%) of the PM2.5 mass, drove the explosive formation of winter haze episodes in the North China Plain. A sharp decline in SIA concentrations and an increase in SIA-to-PM2.5 ratios during the COVID-19 lockdown were also revealed, reflecting the enhanced atmospheric oxidation capacity and formation of secondary particles.

Response of cross-correlations between high PM2.5 and O3 with increasing time scales to the COVID-19: different trends in BTH and PRD.

The air pollution in China currently is characterized by high fine particulate matter (PM2.5) and ozone (O3) concentrations. Compared with single high pollution events, such double high pollution (DHP) events (both PM2.5 and O3 are above the National Ambient Air Quality Standards (NAAQS)) pose a greater threat to public health and environment. In 2020, the outbreak of COVID-19 provided a special time window to further understand the cross-correlation between PM2.5 and O3. Based on this background, a novel detrended cross-correlation analysis (DCCA) based on maximum time series of variable time scales (VM-DCCA) method is established in this paper to compare the cross-correlation between high PM2.5 and O3 in Beijing-Tianjin-Heibei (BTH) and Pearl River Delta (PRD). At first, the results show that PM2.5 decreased while O3 increased in most cities due to the effect of COVID-19, and the increase in O3 is more significant in PRD than in BTH. Secondly, through DCCA, the results show that the PM2.5-O3 DCCA exponents α decrease by an average of 4.40% and 2.35% in BTH and PRD respectively during COVID-19 period compared with non-COVID-19 period. Further, through VM-DCCA, the results show that the PM2.5-O3 VM-DCCA exponents [Formula: see text] in PRD weaken rapidly with the increase of time scales, with decline range of about 23.53% and 22.90% during the non-COVID-19 period and COVID-19 period respectively at 28-h time scale. BTH is completely different. Without significant tendency, its [Formula: see text] is always higher than that in PRD at different time scales. Finally, we explain the above results with the self-organized criticality (SOC) theory. The impact of meteorological conditions and atmospheric oxidation capacity (AOC) variation during the COVID-19 period on SOC state are further discussed. The results show that the characteristics of cross-correlation between high PM2.5 and O3 are the manifestation of the SOC theory of atmospheric system. Relevant conclusions are important for the establishment of regionally targeted PM2.5-O3 DHP coordinated control strategies.

Biogenic volatile organic compounds dominated the near-surface ozone generation in Sichuan Basin, China, during fall and wintertime

The complex air pollution driven by both Ozone (O3) and fine particulate matter (PM2.5) significantly influences the air quality in the Sichuan Basin (SCB). Understanding the O3 formation during autumn and winter is necessary to understand the atmospheric oxidative capacity. Therefore, continuous in-site field observations were carried out during the late summer, early autumn and winter of 2020 in a rural area of Chongqing. The total volatile organic compounds (VOCs) concentration reported by a Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) were 13.66 ± 9.75 ppb, 5.50 ± 2.64 ppb, and 9.41 ± 5.11 ppb in late summer, early autumn and winter, respectively. The anthropogenic VOCs (AVOCs) and biogenic VOCs (BVOCs) were 8.48 ± 7.92 ppb and 5.18 ± 2.99 ppb in late summer, 3.31 ± 1.89 ppb and 2.19 ± 0.93 ppb in autumn, and 6.22 ± 3.99 ppb and 3.20 ± 1.27 ppb in winter. A zero-dimensional atmospheric box model was employed to investigate the sensitivity of O3-precursors by relative incremental reactivity (RIR). The RIR values of AVOCs, BVOCs, carbon monoxide (CO), and nitrogen oxides (NOx) were 0.31, 0.71, 0.09, and -0.36 for late summer, 0.24, 0.59, 0.22, and -0.38 for early autumn, and 0.30, 0.64, 0.33 and -0.70 for winter, and the results showed that the O3 formation of sampling area was in the VOC-limited region, and O3 was most sensitive to BVOCs (with highest RIR values, > 0.6). This study can be helpful in understanding O3 formation and interpreting the secondary formation of aerosols in the winter.

Validating HONO as an Intermediate Tracer of the External Cycling of Reactive Nitrogen in the Background Atmosphere.

In the urban atmosphere, nitrogen oxide (NOx═NO + NO2)-related reactions dominate the formation of nitrous acid (HONO). Here, we validated an external cycling route of HONO and NOx, i.e., formation of HONO resulting from precursors other than NOx, in the background atmosphere. A chemical budget closure experiment of HONO and NOx was conducted at a background site on the Tibetan Plateau and provided direct evidence of the external cycling. An external daytime HONO source of 100 pptv h-1 was determined. Both soil emissions and photolysis of nitrate on ambient surfaces constituted likely candidate mechanisms characterizing this external source. The external source dominated the chemical production of NOx with HONO as an intermediate tracer. The OH production was doubled as a result of the external cycling. A high HONO/NOx ratio (0.31 ± 0.06) during the daytime was deduced as a sufficient condition for the external cycling. Literature review suggested the prevalence of high HONO/NOx ratios in various background environments, e.g., polar regions, pristine mountains, and forests. Our analysis validates the prevalence of external cycling in general background atmosphere and highlights the promotional role of external cycling regarding the atmospheric oxidative capacity.

Insight into the Mechanism and Kinetics of the Heterogeneous Reaction between SO2 and NO2 on Diesel Black Carbon under Light Irradiation.

The heterogeneous oxidation of SO2 by NO2 has been extensively proposed as an important pathway of sulfate production during haze events in China. However, the kinetics and mechanism of oxidation of SO2 by NO2 on the surface of complex particles remain poorly understood. Here, we systematically explore the mechanism and kinetics of the reaction between SO2 and NO2 on diesel black carbon (DBC) under light irradiation. The experimental results prove that DBC photochemistry can not only significantly promote the heterogeneous reduction of NO2 to produce HONO via transferring photoinduced electrons but also indirectly promote OH radical formation. These reduction products of NO2 as well as NO2 itself greatly promote the heterogeneous oxidation of SO2 on DBC. NO2 oxidation, HONO oxidation, and the surface photo-oxidation process are proven to be three major surface oxidation pathways of SO2. The kinetics results indicate that the surface photooxidation pathway accounts for the majority of the total SO2 uptake (∼63%), followed by the HONO oxidation pathway (∼27%) and direct oxidation by NO2 (∼10%). This work highlights the significant synergistic roles of DBC, NO2, and light irradiation in enhancing the atmospheric oxidation capacity and promoting the heterogeneous formation of sulfate.

Secondary aerosol formation drives atmospheric particulate matter pollution over megacities (Beijing and Seoul) in East Asia

Atmospheric particulate matter (PM) pollution in Beijing and Seoul is an urgent concern because of the dense population and the role of the capital city. This study aimed to understand haze formation over East Asia during winter by simultaneously measuring the in situ aerosol chemical composition in the two megacities. During the sampling period, a similar pollution situation characterized by extremely low SO2 (approximately 1 ppbv) and high NOx (approximately 20 ppbv) concentrations and secondary inorganic aerosol (SIA)-dominated PM was found in both cities. Nitrate dominated the inorganic components in the submicron particles in both cities and was more pronounced in Seoul than in Beijing. The enhanced SIA mass concentrations during pollution episodes were observed to be associated with an increased local atmospheric oxidation capacity (indicated by O3+NO2=Ox concentration) and ambient relative humidity under similar stagnant weather conditions. Regarding the thermodynamic equilibrium, abundant aerosol liquid water promoted the partitioning of gaseous HNO3 into its particle phase when pollution events occurred. This result emphasized the importance of local secondary aerosol formation for atmospheric PM pollution in East Asian megacities. The box model simulation of nitrate formation indicated that the homogeneous oxidation of NO2 by OH radicals was the major nitrate formation pathway in both megacities. The downward transport of nitrate from the residual layer also significantly contributed to nitrate concentrations. NOx and volatile organic compounds (VOCs) exhibited a non-linear relationship with nitrate formation. Reducing VOCs concentrations was an efficient approach to mitigate nitrate in both megacities. A reduction of more than 50% in NOx concentrations was required for the effective reduction of nitrate. This study highlighted that Beijing and Seoul were experiencing similar PM pollution situations, and nitrate reduction should be considered to improve their air quality.

Age effects of Moso bamboo on leaf isoprene emission characteristics.

Isoprene is a highly reactive volatile organic compound that significantly affects atmospheric oxidant capacity, regional air quality, and climate change. Moso bamboo (Phyllostachys edulis), a species widely distributed in tropical and subtropical regions, particularly in China, is a strong isoprene emitter with great potential for carbon sequestration. Carbon sequestration is negatively correlated with culm age; however, the effect of this correlation on isoprene emissions remains unknown. In this study, we investigated the photosynthetic and isoprene emission characteristics of Moso bamboo at different culm ages. The results showed that the age effect on isoprene emission was different from that on photosynthesis; the net photosynthesis rate (Pn) was the highest in young, followed by mature, and then old bamboo, whereas the isoprene emission rate (Iso) was the highest in young, followed by old, and then mature bamboo. Moreover, the percentage of carbon loss as isoprene emission (C-loss) during photosynthesis of old bamboo was 35% higher than that of mature bamboo under standard conditions (leaf temperature: 30°C; light intensity: 1000 µmol m-2 s-1). Therefore, we strongly recommend considering the culm age when establishing an isoprene emission model of Moso bamboo. Additionally, because the Iso and C-loss of old bamboo were higher than those of mature bamboo, we suggest that attention should be paid to the management of bamboo age structure and timely felling of aged bamboo to reduce environmental risk.

Measurement report: Spatiotemporal variability of peroxy acyl nitrates (PANs) over Mexico City from TES and CrIS satellite measurements

Abstract. Peroxy acyl nitrates (PANs) are photochemical pollutants with implications for health and atmospheric oxidation capacity. PANs are formed via the oxidation of non-methane volatile organic compounds (NMVOCs) in the presence of nitrogen oxide radicals (NOx = NO + NO2). While urban environments are large sources of PANs, in situ observations in urban areas are limited. Here we use satellite measurements of PANs from the Tropospheric Emission Spectrometer (TES) and the Suomi National Polar-orbiting Partnership (S-NPP) Cross-track Infrared Sounder (CrIS) to evaluate the spatiotemporal variability of PANs over and around Mexico City. Monthly mean maxima in PANs over the Mexico City Metropolitan Area (MCMA) occur during spring months (March–May). This time of year coincides with a peak in local photochemistry and more frequent air stagnation. Local fire activity also typically peaks between February and May, which leads to strong interannual variability of PANs over the MCMA. We use S-NPP CrIS data to probe the spatial outflow pattern of PANs produced within urban Mexico City during the month with the largest mixing ratios of PANs (April). Peak outflow in April occurs to the northeast of the city and over the mountains south of the city. Outflow to the northwest appears infrequently. Using observations during 2018 versus 2019, we also show that PANs were not significantly reduced during a year, with a significant decrease in NOx over Mexico City. Our analysis demonstrates that the space-based observations provided by CrIS and TES can increase understanding of the spatiotemporal variability of PANs over and surrounding Mexico City.

Elucidate the formation mechanism of particulate nitrate based on direct radical observations in the Yangtze River Delta summer 2019

Abstract. Particulate nitrate (NO3-) is one of the dominant components of fine particles in China, especially during pollution episodes, and has a significant impact on human health, air quality, and climate. Here a comprehensive field campaign that focuses on the atmospheric oxidation capacity and aerosol formation and their effects in the Yangtze River Delta (YRD) was conducted from May to June 2019 at a regional site in Changzhou, Jiangsu Province in China. The concentrations of NO3-, OH radicals, N2O5, NO2, O3, and relevant parameters were measured simultaneously. We showed a high NO3- mass concentration with 10.6 ± 8.9 µg m−3 on average, which accounted for 38.3 % of total water-soluble particulate components and 32.0 % of total PM2.5, followed by the proportion of sulfate, ammonium, and chloride by 26.0 %, 18.0 %, and 2.0 %, respectively. This result confirmed that the heavy nitrate pollution in eastern China happened not only in winter, but also in summer. This study's high nitrate oxidation ratio (NOR) emphasized the solid atmospheric oxidation and fast nitrate formation capacity in the YRD. It was found that OH + NO2 during daytime dominated nitrate formation on clean days, while N2O5 hydrolysis vastly enhanced and became comparable with that of OH + NO2 during polluted days (67.2 % and 30.2 %, respectively). The updated observed-constraint Empirical Kinetic Modeling Approach (EKMA) was used to assess the kinetic controlling factors of both local O3 and NO3- productions, which indicated that the O3-targeted scheme (VOCs : NOx = 2:1) is adequate for mitigating the O3 and nitrate pollution coordinately during summertime in this region. Our results promote the understanding of nitrate pollution mechanisms and mitigation based on field observation and model simulation and call for more attention to nitrate pollution in the summertime.

Large Contribution of Nitrous Acid to Soil-Emitted Reactive Oxidized Nitrogen and Its Effect on Air Quality.

Soil emissions have long been recognized as an important source of nitric oxide (NO), which regulates atmospheric oxidative capacity and the production of air pollutants. Recent research has also indicated that nitrous acid (HONO) can be emitted in significant quantities from soil microbial activities. However, only a few studies have quantified emissions of HONO along with NO from a wide range of soil types. In this study, we measured emissions of HONO and NO from soil samples collected from 48 sites across China and found much higher emissions of HONO than of NO, especially for samples from northern China. We performed a meta-analysis of 52 field studies in China, which revealed that long-term fertilization increased the abundance of nitrite-producing genes much more than the abundance of NO-producing genes. This promotion effect was greater in northern China than in southern China. In simulations using a chemistry transport model with laboratory-derived parametrization, we found that HONO emissions had a greater effect than NO emissions on air quality. Moreover, we determined that with projected continuous reductions in anthropogenic emissions, the contribution from soils to maximum 1 h concentrations of hydroxyl radicals and ozone and daily average concentrations of particulate nitrate in the Northeast Plain will increase to 17%, 4.6%, and 14%, respectively. Our findings highlight the need to consider HONO in the assessment of the loss of reactive oxidized nitrogen from soils to the atmosphere and its effect on air quality.

Sensitivity analysis of atmospheric oxidation capacity in Beijing based on the GRAPES-CUACE adjoint model

In this study, based on the evaluation index of atmospheric oxidation capacity (AOIe), the GRAPES-CUACE atmospheric chemistry model was used to simulate and analyze the variation characteristics of atmospheric oxidation capacity (AOC) in Beijing during typical pollution processes in each season in 2017. The sensitivity analysis of the AOIe in Beijing was further conducted using the GRAPES-CUACE adjoint model, and the contribution of precursor emissions in Beijing and surrounding areas to the AOIe in Beijing was quantitatively evaluated. The findings revealed that, on average, Beijing's AOC was strongest in summer, followed by spring and autumn, and weakest in winter. The contribution of oxidation capacity of gaseous-phase oxidation products (AOIe_G) to AOIe was dominant in all seasons, and the oxidation capacity of particle-phase oxidation products (AOIe_P) contributed a relatively larger proportion during PM2.5 pollution periods in winter. Adjoint sensitivity analysis showed that the Beijing peak AOIe value was controlled by both NOx and VOCs in summer, VOCs in winter, and somewhere in between in spring and autumn. Overall, Beijing and Hebei emissions contributed the most to the Beijing peak AOIe value, with a combined contribution of 63–83.6%, while Tianjin, Shanxi, and Shandong emissions also made a non-negligible contribution. In terms of emission source types, VOCs emissions contributed the most to the Beijing peak AOIe value (42.9–79.4%); NOx emissions contributed the most in summer (43.1%) and the least in winter (16.5%); CO emissions contributed a proportion of 4–17.4%. These results further demonstrate that the AOIe index is an appropriate indicator to quantify AOC, laying the foundation for subsequent research based on AOIe. Besides, this study provides more refined results on the sensitivity of AOIe in Beijing to precursor emissions and detects the critical emission sources and their contributions to AOIe in Beijing, which is conducive to a more comprehensive understanding of AOC and improving air quality in Beijing.

Ground-level gaseous pollutants (NO2, SO2, and CO) in China: daily seamless mapping and spatiotemporal variations

Abstract. Gaseous pollutants at the ground level seriously threaten the urban air quality environment and public health. There are few estimates of gaseous pollutants that are spatially and temporally resolved and continuous across China. This study takes advantage of big data and artificial-intelligence technologies to generate seamless daily maps of three major ambient pollutant gases, i.e., NO2, SO2, and CO, across China from 2013 to 2020 at a uniform spatial resolution of 10 km. Cross-validation between our estimates and ground observations illustrated a high data quality on a daily basis for surface NO2, SO2, and CO concentrations, with mean coefficients of determination (root-mean-square errors) of 0.84 (7.99 µg m−3), 0.84 (10.7 µg m−3), and 0.80 (0.29 mg m−3), respectively. We found that the COVID-19 lockdown had sustained impacts on gaseous pollutants, where surface CO recovered to its normal level in China on around the 34th day after the Lunar New Year, while surface SO2 and NO2 rebounded more than 2 times slower due to more CO emissions from residents' increased indoor cooking and atmospheric oxidation capacity. Surface NO2, SO2, and CO reached their peak annual concentrations of 21.3 ± 8.8 µg m−3, 23.1 ± 13.3 µg m−3, and 1.01 ± 0.29 mg m−3 in 2013, then continuously declined over time by 12 %, 55 %, and 17 %, respectively, until 2020. The declining rates were more prominent from 2013 to 2017 due to the sharper reductions in anthropogenic emissions but have slowed down in recent years. Nevertheless, people still suffer from high-frequency risk exposure to surface NO2 in eastern China, while surface SO2 and CO have almost reached the World Health Organization (WHO) recommended short-term air quality guidelines (AQG) level since 2018, benefiting from the implemented stricter “ultra-low” emission standards. This reconstructed dataset of surface gaseous pollutants will benefit future (especially short-term) air pollution and environmental health-related studies.