Investigation of spatiotemporal distribution and formation mechanisms of ozone pollution in eastern Chinese cities applying convolutional neural network.

Severe ground-level ozone (O3) pollution over major Chinese cities has become one of the most challenging problems, which have deleterious effects on human health and the sustainability of society. This study explored the spatiotemporal distribution characteristics of ground-level O3 and its precursors based on conventional pollutant and meteorological monitoring data in Zhejiang Province from 2016 to 2021. Then, a high-performance convolutional neural network (CNN) model was established by expanding the moment and the concentration variations to general factors. Finally, the response mechanism of O3 to the variation with crucial influencing factors is explored by controlling variables and interpolating target variables. The results indicated that the annual average MDA8-90th concentrations in Zhejiang Province are higher in the northern and lower in the southern. When the wind direction (WD) ranges from east to southwest and the wind speed (WS) ranges between 2 and 3 m/sec, higher O3 concentration prone to occur. At different temperatures (T), the O3 concentration showed a trend of first increasing and subsequently decreasing with increasing NO2 concentration, peaks at the NO2 concentration around 0.02 mg/m3. The sensitivity of NO2 to O3 formation is not easily affected by temperature, barometric pressure and dew point temperature. Additionally, there is a minimum [Formula: see text] at each temperature when the NO2 concentration is 0.03 mg/m3, and this minimum [Formula: see text] decreases with increasing temperature. The study explores the response mechanism of O3 with the change of driving variables, which can provide a scientific foundation and methodological support for the targeted management of O3 pollution.

Characteristics and Source Apportionment of Volatile Organic Compounds in a Coastal Industrial Area: A Case Study in the Yangtze River Delta of China.

In recent years, the coastal area in East China has experienced elevated volatile organic compounds (VOCs) levels during specific periods. VOCs have become one of the major atmospheric pollutants in these areas. In this study, 64 compounds including alkanes, alkenes, halohydrocarbons, aromatics, and oxygenated VOCs (OVOCs) were obtained by the TO-15 method through a 12-month campaign in industrial, urban and suburban areas in the Yangtze River Delta of China. The overall trends of total VOC (TVOC) concentrations at eight sampling sites were as follows: winter > autumn > spring > summer. The proportion of VOC categories was various at industrial sites, while OVOCs and halohydrocarbons had high proportions at urban sites and suburban sites, respectively. Coating, vehicle emission, petrochemical source, industrial source, and gasoline volatilization were identified as the major VOC emission sources by the positive matrix factorization model. Petrochemical and coating sources were the prime VOC sources at industrial sites. Aromatics contributed the most ozone formation potential at industrial sites, while OVOCs provided the main contributions at both urban and suburban sites during four seasons. According to the health risk assessment, a high probability of non-carcinogenic risk existed at three industrial sites. Special attention should be given to certain VOCs, such as acrolein and 1,2-dibromoethane in industrial areas.

Radical chemistry and VOCs-NOx-O3-nitrate sensitivity in the polluted atmosphere of a suburban site in the North China Plain.

In this study, the chemical mechanisms of O3 and nitrate formation as well as the control strategy were investigated based on extensive observations in Tai'an city in the NCP and an observation-constrained box model. The results showed that O3 pollution was severe with the maximum hourly O3 concentration reaching 150 ppb. Higher O3 concentration was typically accompanied by higher PM2.5 concentrations, which could be ascribed to the common precursors of VOCs and NOx. The modeled averaged peak concentrations of OH, HO2, and RO2 were relatively higher compared to previous observations, indicating strong atmospheric oxidation capacity in the study area. The ROx production rate increased from 2.8 ppb h-1 to 5 ppb h-1 from the clean case to the heavily polluted case and was dominated by HONO photolysis, followed by HCHO photolysis. The contribution of radical-self combination to radical termination gradually exceeded NO2 + OH from clean to polluted cases, indicating that O3 formation shifted to a more NOx-limited regime. The O3 production rate increased from 14 ppb h-1 to 22 ppb h-1 from clean to heavily polluted cases. The relative incremental reactivity (RIR) results showed that VOCs and NOx had comparable RIR values during most days, which suggested that decreasing VOCs or NOx was both effective in alleviating O3 pollution. In addition, HCHO, with the largest RIR value, made important contribution to O3 production. The Empirical Kinetic Modeling Approach (EKMA) revealed that synergistic control of O3 and nitrate can be achieved by decreasing both NOx and VOCs emissions (e.g., alkenes) with the ratio of 3:1. This study emphasized the importance of NOx abatement for the synergistic control of O3 and nitrate pollution in the Tai'an area as the sustained emissions control has shifted the O3 and nitrate formation to a more NOx-limited regime.

Seasonal and height dynamics of volatile organic compounds in rubber plantation: Impacts on ozone and secondary organic aerosol formation.

Rubber trees emit a range of volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes, as part of their natural metabolism. These VOCs can significantly influence air quality through photochemical reactions that produce ozone and secondary organic aerosols (SOAs). This study examines the impact of VOCs detected in a rubber tree plantation in Northeastern Thailand on air quality, highlighting their role in atmospheric reactions that lead to the formation of ozone and SOAs. VOCs were collected at varying heights and seasons using Tenax-TA tubes paired with an atmospheric sampler pump and identified by gas chromatography-mass spectrometry. In total, 100 VOCs were identified, including alkanes, alkenes, terpenes, aromatics, and oxygenated VOCs. Principal Coordinate Analysis (PCoA) revealed distinct seasonal VOC profiles, with hydrocarbons, peaking in summer and terpenes in the rainy season. The Linear Mixed-Effects (LME) model indicates that VOC concentrations are more influenced by seasonal changes than by sampling heights. Secondary organic aerosol potential (SOAP) and ozone formation potential (OFP) of selected VOC species were also determined. The total SOAP ranged from 67.24 µg/m3 in summer to 17.87 µg/m3 in winter, while the total OFP ranged from 377.87 µg/m3 in summer to 139.39 µg/m3 in winter. Additionally, positive matrix factorization (PMF) analysis identified four main VOC sources: gasoline combustion (18.3 %), microbial activity (38.6 %), monoterpene emissions during latex production (15.0 %), and industrial sources (28.1 %). These findings provide essential information for managing air pollution in rubber tree plantations. By adopting focused air quality management strategies, plantation operators can mitigate the adverse effects of VOCs, promoting a healthier and more sustainable future.

Quantification for photochemical loss of volatile organic compounds upon ozone formation chemistry at an industrial city (Zibo) in North China Plain.

Volatile organic compounds (VOCs) are consumed by photochemical reactions during transport, leading to inaccuracies in estimating the local ozone (O3) formation mechanism and its subsequent strategy for O3 attainment. To comprehensively quantify the deviations in O3 formation mechanism by consumed VOCs (C-VOCs), a 5-month field campaign was conducted in a typical industrial city in Northern China over incorporating a 0-D box model (implemented with MCMv3.3.1). The averaged C-VOCs concentration was 6.8 ppbv during entire period, and Alkenes accounted for 62% dominantly. Without considering C-VOCs, the relative incremental reactivity (RIR) of anthropogenic VOCs (AVOC, overestimated by 68%-75%) and NOx (underestimated by 137%-527%) demonstrated deviations at multiple scenarios, and the RIR deviations for precursors in High-O3-periods (HOP) were lower than Low-O3-periods (LOP). The RIR deviations from individual species involved C-VOCs calculation did not impact the identification for the high-ranking-RIR AVOC species but non-negligible. Monthly comparisons showed that higher C-VOCs concentrations would lead to higher RIR deviations. The daily maximum of net Ox production rate (P(Ox)) and the regional transport Ox (Trans(Ox)) without C-VOCs were underestimated by 56%-194% and 81%-243%, respectively. After considering C-VOCs, the contribution of HO2+NO for Ox gross production (G(Ox)) decreased by 7% (LOP) and 7% (HOP), but OH + NO2 for Ox destruction (D(Ox)) decreased by 16% (LOP) and 23% (HOP), and alkenes + O3 increased for D(Ox) by 12% (LOP) and 22% (HOP). This implies that VOCs-NOx-O3 sensitivity was deviated between with/without C-VOCs, and severe O3 pollution rendered deviations in O3 formation, especially via NOx-driving chemistry. Based on RIR(NOx)/RIR(AVOC) with/without C-VOCs, the sensitivity regime shifted from VOCs-limited (-0.93) to transition (1.38) at LOP, and from VOCs-limited (0.19) to NOx-limited (3.79) at HOP. Our results reflected that the NOx limitation degree was underestimated without constraint C-VOCs, especially HOP, and provided implication to more precise O3 pollution control strategies.

Temporal evolution of speciated volatile organic compound (VOC) emissions from solvent use sources in the Pearl River Delta Region, China (2006-2019).

Volatile organic compounds (VOCs) emitted from solvent use sources constitute an important part of ozone (O3) and secondary organic aerosols (SOA) in the Pearl River Delta (PRD) region, China. While stringent control measures targeting VOCs have been implemented in recent years, an assessment of historical trends is imperative to evaluate their effectiveness. In this study, trends of VOC emissions, compositions, and reactivity from solvent use sources in the PRD region from 2006 to 2019 were estimated using a developed methodology, which considered the improvement of manufacturing equipment and removal efficiency. Results showed that total VOC emissions from solvent use sources displayed an overall increase from 277 kt in 2006 to 400 kt in 2019 despites some fluctuations, with metal products contributing more than 20 % each year. Aromatics and oxygenated VOCs (OVOCs) accounted for over 70 % of total VOC emissions, increasing by 21 kt and 52 kt respectively. OFP and SOAFP increased by 40 % and 23 % respectively from 2006 to 2019. Specific aromatic species, including m/p-xylene, toluene, 1,2,3,5-tetramethylbenzene, o-xylene and ethylbenzene were identified as key species in both VOC emission amount and reactivity. This study aims to facilitate the understanding of VOC emission evolution from solvent use sources in the region and provide insights into the impact of enacted measures, aiding in the future development of more targeted and efficient strategies in the PRD region.

Exhaust and evaporative volatile organic compounds emissions from vehicles fueled with ethanol-blended-gasoline.

By 2020, China has implemented the use of 10% ethanol-blended-gasoline (E10), which is expected to notably impact vehicular volatile organic compounds (VOCs) emissions. The adoption of E10 reduced certain emissions but raised concerns with about more reactive oxygenated volatile organic compounds (OVOCs). This study aimed to evaluate the impact of E10 on the total VOCs emissions from both exhaust and evaporative emissions by conducting tests on the CHINA V (or CHINA VI) light-duty gasoline vehicles (LDGVs) using 0% ethanol blended gasoline (E0) and E10. E10 reduces VOCs emissions in the exhaust, and reduces the ozone and secondary organic aerosol generation potential of VOCs in the exhaust, as evidenced by the lower emission factors (EFs), ozone formation potentials (OFPs) and secondary organic aerosol formation potential (SOAFPs) in the CHINA V LDGVs. Evaporative emissions showed differences in emitted VOCs, with lower EFs, OFPs and SOAFPs for the CHINA V LDGVs fueled with E10. The CHINA VI LDGVs also exhibited reduced EFs, OFPs and SOAFPs. These findings highlight the environmental benefits of E10 in the CHINA VI-compliant LDGVs; however, the effectiveness of the earlier CHINA V standard vehicles requires further evaluation.

Characteristics of Volatile Organic Compounds Emitted from Airport Sources and Their Effects on Ozone Production.

In recent years, commercial air transport has increased considerably. However, the compositions and source profiles of volatile organic compounds (VOCs) emitted from aircraft are still not clear. In this study, the characteristics of VOCs (including oxygenated VOCs (OVOCs)) emitted from airport sources were measured at Shenzhen Bao'an International Airport. The results showed that the compositions and proportions of VOC species showed significant differences as the aircraft operating state changed. OVOCs were the dominant species and accounted for 63.17%, 58.44%, and 51.60% of the total VOC mass concentration during the taxiing, approach, and take-off stages. Propionaldehyde and acetone were the main OVOCs, and dichloromethane and 1,2-dichloroethane were the main halohydrocarbons. Propane had the highest proportion among all alkanes, while toluene and benzene were the predominant aromatic hydrocarbons. Compared with the source profiles of VOCs from construction machinery, the proportions of halogenated hydrocarbons and alkanes emitted from aircraft were significantly higher, as were those of propionaldehyde and acetone. OVOCs were still the dominant VOC species in aircraft emissions, and their calculated ozone formation potential (OFP) was much higher than that of other VOC species at all stages of aircraft operations. Acetone, propionaldehyde, formaldehyde, acetaldehyde, and ethylene were the greatest contributors to ozone production. This study comprehensively measured the distribution characteristics of VOCs, and its results will aid in the construction of a source profile inventory of VOCs emitted from aircraft sources in real atmospheric environments.

Characterization of VOC emissions and health risk assessment in the plastic manufacturing industry.

Volatile organic compounds (VOCs) significantly contribute to ozone pollution formation, and many VOCs are known to be harmful to human health. Plastic has become an indispensable material in various industries and daily use scenarios, yet the VOC emissions and associated health risks in the plastic manufacturing industry have received limited attention. In this study, we conducted sampling in three typical plastic manufacturing factories to analyze the emission characteristics of VOCs, ozone formation potential (OFP), and health risks for workers. Isopropanol was detected at relatively high concentrations in all three factories, with concentrations in organized emissions reaching 322.3 µg/m3, 344.8 µg/m3, and 22.6 µg/m3, respectively. Alkanes are the most emitted category of VOCs in plastic factories. However, alkenes and oxygenated volatile organic compounds (OVOCs) exhibit higher OFP. In organized emissions of different types of VOCs in the three factories, alkenes and OVOCs contributed 22.8%, 67%, and 37.8% to the OFP, respectively, highlighting the necessity of controlling them. The hazard index (HI) for all three factories was less than 1, indicating a low non-carcinogenic toxic risk; however, there is still a possibility of non-cancerous health risks in two of the factories, and a potential lifetime cancer risk in all of the three factories. For workers with job tenures exceeding 5 years, there may be potential health risks, hence wearing masks with protective capabilities is necessary. This study provides evidence for reducing VOC emissions and improving management measures to ensure the health protection of workers in the plastic manufacturing industry.

[Characteristics of VOCs Emissions and Ozone Formation Potential for Typical Chemicals Industry Sources in China].

This study selected five typical types of chemical industry volatile organic compounds (VOCs) emission characteristics in China for analysis. The results from 70 source samples showed that alkanes were the dominant VOCs category from synthetic material industry sources, petrochemical industry sources, and coating industry sources (accounting for 43%, 63%, and 68%, respectively); olefins were the main VOCs category from the daily supplies chemical industry (46%); and halogenated hydrocarbons were the dominate VOCs category from specialty chemicals industry account source emissions (43%). Additionally, the machine learning method was applied in this study to analyze the marker components of the above industries. The results showed that decane and tetrahydrofuran were the source markers of the synthetic material industry; n-butanol and toluene were the markers of the daily supplies industry source; 1,2,3-trimethylbenzene and 1,3,5-trimethylbenzene were the markers of the petrochemical industry source; propylene and 3-methyl pentane were the source markers of the coating industry; and P-Xylene and cumene were the markers of the specialty chemicals industry source. The maximum incremental reactivity method (MIR) was used to estimate the ozone formation potential (OFP) of different VOCs-sources. The calculation results showed that when considering per unit TVOCs concentration emissions, the contribution to the ozone generation potential was in the order of the daily supplies chemical industry, specialty chemical industry, petrochemical industry, synthetic material industry, and coating industry. Therefore, we suggest that more attention should be paid to the key active species emitted by various industry sources rather than only the total amount of VOCs emissions in future ozone prevention and control efforts.

Elucidating the unexpected importance of intermediate-volatility organic compounds (IVOCs) from refueling procedure.

Evaporative emissions release organic compounds comparable to gasoline exhaust in China. However, the measurement of intermediate volatility organic compounds (IVOCs) is lacking in studies focusing on gasoline evaporation. This study sampled organics from a real-world refueling procedure and analyzed the organic compounds using comprehensive two-dimensional gas chromatography coupled with a mass spectrometer (GC×GC-MS). The non-target analysis detected and quantified 279 organics containing 93 volatile organic compounds (VOCs, 64.9 ± 7.4 % in mass concentration), 182 IVOCs (34.9 ± 7.4 %), and 4 semivolatile organic compounds (SVOCs, 0.2 %). The refueling emission profile was distinct from that of gasoline exhaust. The b-alkanes in the B12 volatility bin are the most abundant IVOC species (1.9 ± 1.4 µg m-3) in refueling. A non-negligible contribution of 17.5 % to the ozone formation potential (OFP) from IVOCs was found. Although IVOCs are less in concentration, secondary organic aerosol potential (SOAP) from IVOCs (58.1 %) even exceeds SOAP from VOCs (41.6 %), mainly from b-alkane in the IVOC range. At the molecular level, the proportion of cyclic compounds in SOAP (12.1 %) indeed goes above its mass concentration (3.1 %), mainly contributed by cyclohexanes and cycloheptanes. As a result, the concentrations and SOAP of cyclic compounds (>50 %) could be overestimated in previous studies. Our study found an unexpected contribution of IVOCs from refueling procedures to both ozone and SOA formation, providing new insights into secondary pollution control policy.

Spatiotemporal variations, sources, and atmospheric transformation potential of volatile organic compounds in an industrial zone based on high-resolution measurements in three plants.

Industrial emissions are significant sources of volatile organic compounds (VOCs). This study conducted a field campaign at high temporal and spatial resolution to monitor VOCs within three plants in an industrial park in southern China. VOC concentrations showed significant spatial variability in this industrial zone, with median concentrations of 75.22, 40.53, and 29.41 µg/m3 for the total VOCs in the three plants, respectively, with oxygenated VOCs (OVOCs) or aromatics being the major VOCs. Spatial variability within each plant was also significant but VOC-dependent. Seasonal variations in the VOC levels were governed by their industrial emissions, meteorological conditions, and photochemical losses, and they were different for the four groups of VOCs. The temporal and spatial variations in the VOC compositions suggest similar sources of each class of VOCs during different periods of the year in each plant. The diurnal patterns of VOCs (unimodal or bimodal) clearly differed from those at most industrial/urban locations previously, reflecting a dependence on industrial activities. The secondary transformation potential of VOCs also varied temporally and spatially, and aromatics generally made the predominant contributions in this industrial park. The loss rate of OH radicals and ozone formation potential were highly correlated, but the linear relationship substantially changed in summer and autumn due to the intensive emissions of an OVOC species. The lifetime cancer and non-cancer risks via occupational inhalation of the VOCs in the plants were acceptable but merit attention. Taking the secondary transformation potential and health risks into consideration, styrene, xylene, toluene, trichloroethylene, and benzene were proposed to be the priority VOCs regulated in the plants.

Comparative analysis for the impacts of VOC subgroups and atmospheric oxidation capacity on O3 based on different observation-based methods at a suburban site in the North China Plain.

The persistent O3 pollution in the Beijing-Tianjin-Hebei (BTH) region remains unresolved, largely due to limited comprehension of O3-precursor relationship and photochemistry drivers. In this work, intraday O3 sensitivity evolution from VOC-limited (volatile organic compound) regime in the forenoon to transition regime in the late afternoon was inferred by relative incremental reactivity (RIR) in summer 2019 at Xianghe, a suburban site in BTH region, suggesting that VOC-focused control policy could combine with stringent afternoon NOx control. Then detailed impacts of VOC subgroups on O3 formation were further comprehensively quantified by parametric OH reactivity (KOH), O3 formation potential (OFP), as well as RIR weighted value and O3 formation path tracing (OFPT) approach based on photochemical box model. O3 episode days corresponded to stronger O3 formation, depicted by higher KOH (10.4 s-1), OFP (331.7 µg m-3), RIR weighted value (1.2), and F(O3)-OFPT (15.5 ppbv h-1). High proportions of isoprene and OVOCs (oxygenated VOCs) to the total KOH and the OFPT method were demonstrated whereas results of OFP and RIR-weighted presented extra great impacts of aromatics on O3 formation. The OFPT approach captured the process that has already happened and included final O3 response to the original VOC, thus reliable for replicating VOC impacts. The comparison results of the four methods showed similarities when utilizing KOH and OFPT methods, which reveals that the potential applicability of simple KOH for contingency VOC control and more complex OFPT method for detailed VOC- and source-oriented control during policy-making. To investigate propulsion of VOC-involved O3 photochemistry, atmospheric oxidation capacity (AOC) was quantified by two atmospheric oxidation indexes (AOI). Both AOIp_G (7.0 × 107 molec cm-3 s-1, potential AOC calculated by oxidation reaction rates) and AOIe_G (8.5 µmol m-3, estimated AOC given redox electron transfer for oxidation products) were stronger on O3 episode days, indicating that AOC promoted the radical cycling initiated from VOC oxidation and subsequent O3 production. Result-oriented AOIe_G reasonably characterized actual AOC inferred by good linear correlation between AOIe_G and O3 concentrations compared to process-oriented AOIp_G. Therefore, with continuous NOx abatement, AOIe_G should be considered to represent actual AOC, also O3-inducing ability.

PM2.5 pollution modulates the response of ozone formation to VOC emitted from various sources: Insights from machine learning.

Numerous studies have linked ozone (O3) production to its precursors and fine particulate matter (PM2.5), while the complex interaction effects of PM2.5 and volatile organic compounds (VOCs) on O3 remain poorly understood. A systematic approach based on an interpretable machine learning (ML) model was utilized to evaluate the primary driving factors that impact O3 and to elucidate how changes in PM2.5, VOCs from different sources, NOx, and meteorological conditions either promote or inhibit O3 formation through their individual and synergistic effects in a tropical coastal city, Haikou, from 2019 to 2020. The results suggest that under low PM2.5 levels, alongside the linear O3-PM2.5 relationship observed, O3 formation is suppressed by PM2.5 with higher proportions of traffic-derived aerosol. Vehicle VOC emissions contributed maximally to O3 formation at midday, despite the lowest concentration. VOCs from fossil fuel combustion and industry emissions, which have opposing effects on O3, act as inhibitors and promoters by inducing diverse photochemical regimes. As PM2.5 pollution escalates, the impact of these VOCs reverses, becoming more pronounced in shaping O3 variation. Sensitivity analysis reveals that the O3 formation regime is VOC-limited, and effective regional O3 mitigation requires prioritizing substantial VOC reductions to offset enhanced VOC sensitivity induced by the co-reduction in PM2.5, with a focus on industrial and vehicular emissions, and subsequently, fossil fuel combustion once PM2.5 is effectively controlled. This study underscores the potential of the SHAP-based ML approach to decode the intricate O3-NOx-VOCs-PM2.5 interplay, considering both meteorological and atmospheric compositional variations.

Real-world emission characteristics of carbonyl compounds from on-road vehicles in Beijing and Zhengzhou, China.

Carbonyl compounds have a profound role in atmospheric chemistry, which can cause the formation of ozone and secondary organic aerosols. On-road vehicle emissions are an important source of carbonyl compounds, but systematic knowledge of real-world emission characteristics is still scarce. In this study, a total of 181 on-road vehicles of 16 types in Beijing and Zhengzhou, China, were tested using portable emission measurement system under real-world driving conditions. The total carbonyl compound emission factors of gasoline vehicles, diesel vehicles, motorcycles, and agricultural transport vehicles were 24.9 ± 11.4 mg/km, 42.5 ± 21.5 mg/km, 20.4 ± 6.8 mg/km, and 78.3 ± 34.3 mg/km, respectively. Vehicles fueled with E10 ethanol gasoline had significantly higher carbonyl compound emission factors compared to E0 gasoline vehicles. It was observed that the continuous tightening of emission standards has effectively reduced the emissions of carbonyl compounds from on-road vehicles. The carbonyl compound emission factors on highways were 1.3-1.9 times lower than those on general roads. The total carbonyl compound emissions from on-road vehicles in Beijing and Zhengzhou in 2019 were estimated to be 3.5 kt and 3.1 kt, with corresponding ozone formation potentials of 24.4 kt and 21.4 kt, respectively. Formaldehyde, acetaldehyde, propionaldehyde and acetone were the most significant contributors to total carbonyl compound emissions, and among them, formaldehyde, acetaldehyde and propionaldehyde were the main contributors to total ozone formation potential. Our results provide updated and supplementary information on on-road vehicle emission factors for carbonyl compounds and can facilitate the improvement of emission inventories and help in the development of control strategies to improve air quality.

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.

Evolution of Ozone Formation Sensitivity during a Persistent Regional Ozone Episode in Northeastern China and Its Implication for a Control Strategy.

In recent years, the magnitude and frequency of regional ozone (O3) episodes have increased in China. We combined ground-based measurements, observation-based model (OBM), and the Weather Research and Forecasting and Community Multiscale Air Quality (WRF-CMAQ) model to analyze a typical persistent O3 episode that occurred across 88 cities in northeastern China during June 19-30, 2021. The meteorological conditions, particularly the wind convergence centers, played crucial roles in the evolution of O3 pollution. Daily analysis of the O3 formation sensitivity showed that O3 formation was in the volatile organic compound (VOC)-limited or transitional regime at the onset of the pollution episode in 92% of the cities. Conversely, it tended to be or eventually became a NOx-limited regime as the episode progressed in the most polluted cities. Based on the emission-reduction scenario simulations, mitigation of the regional O3 pollution was found to be most effective through a phased control strategy, namely, reduction of a high ratio of VOCs to NOx at the onset of the pollution and lower ratio during evolution of the O3 episode. This study presents a new possibility for regional O3 pollution abatement in China based on a reasonable combination of OBM and the WRF-CMAQ model.

Research on ozone formation sensitivity based on observational methods: Development history, methodology, and application and prospects in China.

Observation-based method for O3 formation sensitivity research is an important tool to analyze the causes of ground-level O3 pollution, which has broad application potentials in determining the O3 pollution formation mechanism and developing prevention and control strategies. This paper outlined the development history of research on O3 formation sensitivity based on observational methods, described the principle and applicability of the methodology, summarized the relative application results in China and provided recommendations on the prevention and control of O3 pollution in China based on relevant study results, and finally pointed out the shortcomings and future development prospects in this field in China. The overview study showed that the O3 formation sensitivity in some urban areas in China in recent years presented a gradual shifting tendency from the VOC-limited regime to the transition regime or the NOx-limited regime due to the implementation of the O3 precursors emission reduction policies; O3 pollution control strategies and precursor control countermeasures should be formulated based on local conditions and the dynamic control capability of O3 pollution control measures should be improved. There are still some current deficiencies in the study field in China. Therefore, it is recommended that a stereoscopic monitoring network for atmospheric photochemical components should be further constructed and improved; the atmospheric chemical mechanisms should be vigorously developed, and standardized methods for determining the O3 formation sensitivity should be established in China in the near future.

Characteristics and source apportionment of ambient volatile organic compounds and ozone generation sensitivity in urban Jiaozuo, China.

In recent years, many cities have taken measures to reduce volatile organic compounds (VOCs), an important precursor of ozone (O3), to alleviate O3 pollution in China. 116 VOC species were measured by online and offline methods in the urban area of Jiaozuo from May to October in 2021 to analyze the compositional characteristics. VOC sources were analyzed by a positive matrix factorization (PMF) model, and the sensitivity of ozone generation was determined by ozone isopleth plotting research (OZIPR) simulation. The results showed that the average volume concentration of total VOCs was 30.54 ppbv and showed a bimodal feature due to the rush-hour traffic in the morning and at nightfall. The most dominant VOC groups were oxygenated VOCs (OVOCs, 29.3%) and alkanes (26.7%), and the most abundant VOC species were acetone and acetylene. However, based on the maximum incremental reactivity (MIR) method, the major VOC groups in terms of ozone formation potential (OFP) contribution were OVOCs (68.09 µg/m3, 31.5%), aromatics (62.90 µg/m3, 29.1%) and alkene/alkynes (54.90 µg/m3, 25.4%). This indicates that the control of OVOCs, aromatics and alkene/alkynes should take priority. Five sources of VOCs were quantified by PMF, including fixed sources of fossil fuel combustion (27.8%), industrial processes (25.9%), vehicle exhaust (19.7%), natural and secondary formation (13.9%) and solvent usage (12.7%). The empirical kinetic modeling approach (EKMA) curve obtained by OZIPR on O3 exceedance days indicated that the O3 sensitivity varied in different months. The results provide theoretical support for O3 pollution prevention and control in Jiaozuo.

Unveiling the importance of VOCs from pesticides applicated in main crops for elevating ozone concentrations in China.

Volatile organic compounds (VOCs) are considered as important precursors of ozone in the air, while the contribution of VOCs from pesticide application (PVOCs) to ozone production is unknown. Utilizing data from the Ministry of Agriculture and Rural Affairs of the People's Republic of China and ChinaCropPhen1km, this paper developed PVOC emission inventories with a resolution of 1 km for the main crops (rice, maize, and wheat) from 2012 to 2019 in China. The results revealed that pesticide application is an important VOC emission source in China. Specially, the PVOC emissions from the major grain-producing regions in June accounted for approximately 30% of the annual total PVOC emissions in the local regions. The simulation with the Weather Research and Forecasting Community Multiscale Air Quality model (WRF-CMAQ) indicated that the PVOC emissions increased the mean maximum daily 8-hour average (MDA8) ozone concentration across China by 2.5 ppb in June 2019. During the same period, PVOCs in the parts of North China Plain contributed 10% of the ozone formation. Under the comprehensive emission reduction scenario, it is anticipated that by 2025, the joint implementation of measures including reducing pesticide application, improving pesticide utilization efficiency and promoting solvent substitution will decrease PVOC emissions by 60% compared with 2019, thereby mitigating ozone pollution.