Atmospheric Oxidation Capacity Research Articles

Multi-scale analysis of the chemical and physical pollution evolution process from pre-co-pollution day to PM2.5 and O3 co-pollution day

PM2.5 and O3 are two of the main air pollutants that have adverse impacts on climate and human health. The evolution process of PM2.5 and O3 co-pollution are of concern because of the increased frequency of PM2.5 and O3 co-pollution days. Here, we examined the chemical coupling and revealed the driving factors of the PM2.5 and O3 co-pollution evolution process from cleaning day, PM2.5 pollution day, or O3 pollution day, applied by theoretical analysis and model calculation methods. The results demonstrate that PM2.5 and O3 co-pollution day frequently occurred with high concentrations of gaseous precursors and higher sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR), which we attribute to the enhancement of atmospheric oxidation capacity (AOC). The AOC is positively correlated with O3 and weakly correlated with PM2.5. In addition, we found that the correlation coefficients of PM2.5-NO2 (0.62) were higher than that of PM2.5-SO2 (0.32), highlighting the priority of NOx controlling to mitigate PM2.5 pollution. Overall, our discovery can provide scientific evidence to design feasible solutions for the controlling PM2.5 and O3 co-pollution process.

Response of ozone to meteorology and atmospheric oxidation capacity in the Yangtze river Delta from 2017 to 2020

China implemented a stringent clean air initiative to improve air quality in 2013. By 2017, fine particulate matter (PM2.5) levels in the Yangtze River Delta (YRD) region dropped significantly, but ozone (O3) pollution surged, which aroused concerns about its adverse impact on crops, climate and human health. Due to the complex influences of atmospheric processes, the variation of O3 is highly nonlinear, making the control of O3 pollution highly challenging. It is urgent to deepen the understanding of the role of meteorological factors and atmospheric oxidation capacity (AOC) during O3 episodes. To provide references for O3 pollution control, the study used the Weather Research and Forecasting model (WRF) and the Community Multi-scale Air Quality model (CMAQ) simulations in the YRD from 2017 to 2020 to analyze the causes of severe O3 pollution. Observations revealed a slight decline in heavily O3 polluted days in the YRD region and the simulation results showed that O3 pollution was more prevalent at temperatures above 25 °C and relative humidity below 80%. The increase in volatile organic compounds (VOCs), hydroxyl radical (OH) and nitrate radical (NO3) was also more conducive to the formation of O3 pollution. For areas that are primarily VOC-limited areas, such as Shanghai, a stricter policy on VOC control is needed to reduce O3 pollution more effectively.

A light - Driven acidic positive feedback mechanism of sulfate formation

As the main source of atmospheric sulfate aerosol, the aqueous-phase oxidation of SO2 has been of great concern. Traditionally, the aqueous-phase oxidation of SO2 is considered a consumption process of atmospheric oxidation capacity; however, we report here that •OH radicals and other reactive oxygen species (ROS) can be generated in the photochemical reactions of bulk HSO3− solution. This •OH production pathway results in the fast sulfate formation in the photooxidation of dissolved SO2. The photochemical process is determined to be pH-dependent in which sulfate formation is promoted by decreasing pH. Hence, a light - driven acidic positive feedback mechanism is proposed that the oxidation of dissolved SO2 and the formation of •OH radicals have a synergistic promoting effect. These results indicate that the photochemistry of dissolved SO2 could be a missing source of aqueous •OH radicals as well as sulfate at regional to global scales.

Atmospheric Oxidation Capacity Elevated during 2020 Spring Lockdown in Chengdu, China: Lessons for Future Secondary Pollution Control.

This study presents the measurement of photochemical precursors during the lockdown period from January 23, 2020, to March 14, 2020, in Chengdu in response to the coronavirus (COVID-19) pandemic. To derive the lockdown impact on air quality, the observations are compared to the equivalent periods in the last 2 years. An observation-based model is used to investigate the atmospheric oxidation capacity change during lockdown. OH, HO2, and RO2 concentrations are simulated, which are elevated by 42, 220, and 277%, respectively, during the lockdown period, mainly due to the reduction in nitrogen oxides (NOx). However, the radical turnover rates, i.e., OH oxidation rate L(OH) and local ozone production rate P(O3), which determine the secondary intermediates formation and O3 formation, only increase by 24 and 48%, respectively. Therefore, the oxidation capacity increases slightly during lockdown, which is partly attributed to unchanged alkene concentrations. During the lockdown, alkene ozonolysis seems to be a significant radical primary source due to the elevated O3 concentrations. This unique data set during the lockdown period highlights the importance of controlling alkene emission to mitigate secondary pollution formation in Chengdu and may also be applicable in other regions of China given an expected NOx reduction due to the rapid transformation to electrified fleets in the future.

Long-term evolution of carbonaceous aerosols in PM2.5 during over a decade of atmospheric pollution outbreaks and control in polluted central China

Against the backdrop of an uncertain evolution of carbonaceous aerosols in polluted areas over the long term amid air pollution control measures, this 11-year study (2011–2021) investigated fine particulate matter (PM2.5) and carbonaceous components in polluted central China. Organic carbon (OC) and elemental carbon (EC) averaged 16.5 and 3.4 μg/m3, constituting 16 and 3 % of PM2.5 mass. Carbonaceous aerosols dominated PM2.5 (35 and 27 %) during periods of excellent and good air quality, while polluted days witnessed other components as dominants, with a significant decrease in primary organic aerosols and increased secondary pollution. From 2011 to 2021, OC and EC decreased by 53 and 76 %, displaying a high-value oscillation phase (2011–2015) and a low-value fluctuation phase (post-2016). A substantial reduction in high OC and EC concentrations in 2016 marked a milestone in significant air quality improvement attributed to effective control measures, especially targeting OC and EC, evident from their decreased proportion in PM2.5. Primary OC (POC) in winter exhibited the most pronounced reduction (8 % per year), and the seasonal disparities in PM2.5 and carbonaceous components were reduced, showcasing the effectiveness of control measures. Contrary to the more pronounced reduction of EC, which decreased in proportion to PM2.5, secondary OC (SOC) in PM2.5 exhibited an increasing trend. Along with rising OC/EC, SOC/OC, and SOC/EC ratios, this indicates a growing prominence of secondary pollution compared to the decrease in primary pollution. SOC shows an increasing trend with NO2 rise (r = 0.53), without O3 promoting SOC. Positive correlations of SOC with SO2, CO (r = 0.41, 0.59), also highlight their influence on atmospheric conditions, oxidative capacity, and chemical reactions, indirectly impacting SOC formation. The implementation of precise precursor emission reduction measures holds the key to future efforts in mitigating SOC pollution and reducing PM2.5 concentrations, thereby contributing to improved air quality.

Parameterized atmospheric oxidation capacity during summer at an urban site in Taiyuan and implications for O3 pollution control

In recent years, summer ozone pollution shows a significant upward trend in many cities of China, affecting human health and ecosystems. The atmospheric oxidation capacity (AOC) is the core driving force for converting primary pollutants into secondary pollutants. In order to better understand the characteristics of AOC in summer, the comprehensive observation of VOCs (including OVOCs) was conducted at an urban site in Taiyuan from July 20 to August 3, 2020. The parameterized analysis of AOC and ROH was carried out by combining with the simulated photolysis rates (JO1D, JNO2 and JNO3). The results showed that the mean value of MDA8 O3, AOC and ROH were 84.2 ppbv, 2.4 × 107 molecules cm−3 s−1 and 28.3 s−1, respectively. The major reductants of AOC were CO (37.6%), isoprene (21.7%) and formaldehyde (16.8%). Diurnal variations of AOC showed a peak at noon, the major oxidants for AOC were OH (97.7%) and O3 (78.7%) during the daytime and nighttime, respectively. The mean value of MDA8 O3, AOC and VOCs-AOC during the pollution period (MDA8 O3 > 75 ppbv) were 33.0%, 45.0% and 59.3% higher than the non-pollution period, respectively. The OH reactivity ratio of NOx and VOCs indicated that O3 formation occurred under a VOC-limited regime. The backward trajectory analysis showed that VOCs from southwestern airmass had the highest AOC (2.0 × 107 molecules cm−3 s−1), and the domain contributors were isoprene (39.0%), formaldehyde (24.9%), acetaldehyde (9.8%) and ethylene (4.4%). This study could provide some references for regulating AOC to alleviate O3 pollution.

Quantifying the contributions of meteorology, emissions, and transport to ground-level ozone in the Pearl River Delta, China

Ozone pollution presents a growing air quality threat in urban agglomerations in China. It remains challenge to distinguish the roles of emissions of precursors, chemical production and transportations in shaping the ground-level ozone trends, largely due to complicated interactions among these 3 major processes. This study elucidates the formation factors of ozone pollution and categorizes them into local emissions (anthropogenic and biogenic emissions), transport (precursor transport and direct transport from various regions), and meteorology. Particularly, we attribute meteorology, which affects biogenic emissions and chemical formation as well as transportation, to a perturbation term with fluctuating ranges. The Community Multiscale Air Quality (CMAQ) model was utilized to implement this framework, using the Pearl River Delta region as a case study, to simulate a severe ozone pollution episode in autumn 2019 that affected the entire country. Our findings demonstrate that the average impact of meteorological conditions changed consistently with the variation of ozone pollution levels, indicating that meteorological conditions can exert significant control over the degree of ozone pollution. As the maximum daily 8-hour average (MDA8) ozone concentrations increased from 20 % below to 30 % above the National Ambient Air Quality Standard II, contributions from emissions and precursor transport were enhanced. Concurrently, direct transport within Guangdong province rose from 13.8 % to 22.7 %, underscoring the importance of regional joint prevention and control measures under adverse weather conditions. Regarding biogenic emissions and precursor transport that cannot be directly controlled, we found that their contributions were generally greater in urban areas with high nitrogen oxides (NOx) levels, primarily due to the stronger atmospheric oxidation capacity facilitating ozone formation. Our results indicate that not only local anthropogenic emissions can be controlled in urban areas, but also the impacts of local biogenic emissions and precursor transport can be potentially regulated through reducing atmospheric oxidation capacity.

The Impact of Agroecosystems on Nitrous Acid (HONO) Emissions during Spring and Autumn in the North China Plain.

Solar radiation triggers atmospheric nitrous acid (HONO) photolysis, producing OH radicals, thereby accelerating photochemical reactions, leading to severe secondary pollution formation. Missing daytime sources were detected in the extensive HONO budget studies carried out in the past. In the rural North China Plain, some studies attributed those to soil emissions and more recent studies to dew evaporation. To investigate the contributions of these two processes to HONO temporal variations and unknown production rates in rural areas, HONO and related field observations obtained at the Gucheng Agricultural and Ecological Meteorological Station during spring and autumn were thoroughly analyzed. Morning peaks in HONO frequently occurred simultaneously with those of ammonia (NH3) and water vapor both during spring and autumn, which were mostly caused by dew and guttation water evaporation. In spring, the unknown HONO production rate revealed pronounced afternoon peaks exceeding those in the morning. In autumn, however, the afternoon peak was barely detectable compared to the morning peak. The unknown afternoon HONO production rates were attributed to soil emissions due to their good relationship to soil temperatures, while NH3 soil emissions were not as distinctive as dew emissions. Overall, the relative daytime contribution of dew emissions was higher during autumn, while soil emissions dominated during spring. Nevertheless, dew emission remained the most dominant contributor to morning time HONO emissions in both seasons, thus being responsible for the initiation of daytime OH radical formation and activation of photochemical reactions, while soil emissions further maintained HONO and associated OH radial formation rates at a high level, especially during spring. Future studies need to thoroughly investigate the influencing factors of dew and soil emissions and establish their relationship to HONO emission rates, form reasonable parameterizations for regional and global models, and improve current underestimations in modeled atmospheric oxidation capacity.

Molecular characteristics and formation mechanisms of biogenic secondary organic aerosols in the mountainous background atmosphere of southern China

Biogenic secondary organic aerosols (BSOA) play a crucial role in atmospheric chemistry, with significant implications for air quality and human health. However, the mechanisms by which anthropogenic emissions influence the formation of BSOA in the real atmosphere have not been fully understood. In this study, fine aerosol (PM2.5) samples were collected during both the wet and dry seasons at a high-altitude (1690 m) background site in the Nanling Mountains. Eleven typical secondary organic aerosols (SOA) tracers derived from isoprene (SOAI), α/β-pinene (SOAM), β-caryophyllene (SOAS), and toluene (SOAA), as well as water-soluble inorganic ions and the ambient concentrations of isoprene and its two primary oxidation products, were measured. The results showed that the concentrations and composition of SOA tracers exhibited significant seasonal variations. The total concentration of SOA tracers in the wet season (159 ± 100 ng m−3) was almost three times higher than that in the dry season (61 ± 68 ng m−3). SOAI dominated in both seasons, followed by SOAM, SOAS, and SOAA. Compared with other studies, the concentrations of SOAI and SOAA in the wet season were relatively high, which was mainly attributed to the rapid oxidation of their precursors due to the higher atmospheric oxidative capacity. C5-alkene triols had a significantly higher proportion in SOAI species than in other mountaintop sites. Temperature was the main factor causing the seasonal difference in the concentration of SOAI. Anthropogenic pollutants significantly promoted the formation of SOAI in the wet season. The influence of anthropogenic pollutants on the reaction pathway of IEPOX was consistent in both seasons, favoring the formation of C5-alkene triols. Our study provides vital insights into the molecular characteristics and formation mechanisms of BSOA in a high-altitude background region. It also highlights that the complex air pollution not only affects BSOA concentrations but also the reaction pathways of biogenic volatile organic compounds (BVOCs) transforming into BSOA.

Rapid hydrolysis of NO2 at High Ionic Strengths of Deliquesced Aerosol Particles.

Nitrogen dioxide (NO2) hydrolysis in deliquesced aerosol particles forms nitrous acid and nitrate and thus impacts air quality, climate, and the nitrogen cycle. Traditionally, it is considered to proceed far too slowly in the atmosphere. However, the significance of this process is highly uncertain because kinetic studies have only been made in dilute aqueous solutions but not under high ionic strength conditions of the aerosol particles. Here, we use laboratory experiments, air quality models, and field measurements to examine the effect of the ionic strength on the reaction kinetics of NO2 hydrolysis. We find that high ionic strengths (I) enhance the reaction rate constants (kI) by more than an order of magnitude compared to that at infinite dilution (kI=0), yielding log10(kI/kI=0) = 0.04I or rate enhancement factor = 100.04I. A state-of-the-art air quality model shows that the enhanced NO2 hydrolysis reduces the negative bias in the simulated concentrations of nitrous acid by 28% on average when compared to field observations over the North China Plain. Rapid NO2 hydrolysis also enhances the levels of nitrous acid in other polluted regions such as North India and further promotes atmospheric oxidation capacity. This study highlights the need to evaluate various reaction kinetics of atmospheric aerosols with high ionic strengths.

Diurnal emission variation of ozone precursors: Impacts on ozone formation during Sep. 2019

With the issue of ozone (O3) pollution having increasingly gained visibility and prominence in China, the Chinese government explored various policies to mitigate O3 pollution. In some provinces and cities, diurnal regulations of O3 precursor were implemented, such as shifting O3 precursor emission processes to nighttime and offering preferential refueling at night. However, the effectiveness of these policies remains unverified, and their impact on the O3 generation process requires further elucidation. In this study, we utilized a regional climate and air quality model (WRF-Chem, v4.5) to test three scenarios aimed at exploring the impact of diurnal industry emission variation of O3 precursors on O3 formation. Significant O3 variations were observed mainly in urban areas. Shifting volatile organic compounds (VOCs) to nighttime have slight decreased daytime O3 levels while moving nitrogen oxides (NOx) to nighttime elevates O3 levels. Simultaneously moving both to nighttime showed combined effects. Process analysis indicates that the diurnal variation in O3 was mainly attributed to chemical process and vertical mixing in urban areas, while advection becomes more important in non-urban areas, contributing to the changes in O3 and O3 precursors levels through regional transportation. Further photochemical analysis reveals that the O3 photochemical production in urban areas was affected by reduced daytime O3 precursors emissions. Specifically, decreasing VOCs lowered the daytime O3 production by reducing the ROx radicals (ROx = HO + HO˙2 + RO˙2), whereas decreasing NOx promoted the daytime O3 production by weakening ROx radical loss. Our results demonstrate that diurnal regulation of O3 precursors will disrupt the ROx radical and O3 formation in local areas, resulting in a change in O3 concentration and atmospheric oxidation capacity, which should be considered in formulating new relevant policies.

Origins of formaldehyde in a mountainous background atmosphere of southern China

Formaldehyde (HCHO) is one of the key indicators of severe photochemical pollution and strong atmospheric oxidation capacity in southern China. However, current information on the origins of regional HCHO and the impacts of polluted air masses remains scarce and unclear. In this study, an intensive observation of HCHO was conducted at a mountainous background site in southern China during typical photochemical pollution episodes. The concentrations of HCHO reached up to 6.14 ppbv and averaged at 2.68 ± 1.11 ppbv. Source appointment using a photochemical age-based parameterization method revealed significant contributions of secondary formation (50 %) and biomass burning (42 %). Meanwhile, under the influence of the East Asian Winter Monsoon, polluted air masses from central and western China can significantly increase the regional HCHO levels. The simulation results adopting the Rapid Adaptive Optimization Model for Atmospheric Chemistry model further demonstrated that the intrusion of active anthropogenic pollutants (e.g., small-molecule alkenes) can accelerate the net production rate of HCHO, particularly through BVOC-oxidation pathways. This study suggests a potential enhanced mechanism of HCHO production resulting from anthropogenic-biogenic interactions. It highlights that polluted air masses carrying abundant HCHO from upwind areas may facilitate severe photochemical pollution in the Greater Bay Area.

Trends and Interannual Variability of the Hydroxyl Radical in the Remote Tropics During Boreal Autumn Inferred From Satellite Proxy Data

AbstractDespite its importance for the global oxidative capacity, spatially resolved trends and variability of the hydroxyl radical (OH) are poorly constrained. We demonstrate the utility of a tropospheric column OH (TCOH) product, created from machine learning and satellite proxy data, in determining the spatial variability in trends of tropical OH over the oceans during September through November. While OH increases domain‐wide by 2.1%/decade from 2005–2019, we find significant spatial heterogeneity in regional trends, with decreases in some areas of 2.5%/decade. Our analysis of the trends in the proxy data indicate anthropogenic‐driven changes in emissions of OH drivers as well as increasing temperatures cause these trends. This OH product is potentially a significant advance in constraining OH spatial variability and serves as a useful complement to existing tools in understanding the atmospheric oxidative capacity. Comprehensive observations of TCOH are required to assess the fidelity of this method.

Detecting causal relationships between fine particles and ozone based on observations in four typical cities of China

As the concentration of fine particles (PM2.5) is declining, ozone (O3) concentration has been increasing in China in recent years. To collaboratively control PM2.5 and O3, it is critical to understand the relationship between the two and identify major controlling factors. We use a convergent cross-mapping method to detect the causal relationship between daily PM2.5 and maximum daily 8 h average (MDA8) O3 concentrations in Beijing, Taizhou, Shenzhen and Chengdu, China, in the four seasons in 2015–2021. In addition, we also examined causal effects of atmospheric oxidation capacity, precursors and meteorological elements on PM2.5 and MDA8 O3 in the four cities. PM2.5 and MDA8 O3 are strongly positively correlated and show bidirectional causal relationships during the Beijing and Taizhou summer and in the four seasons in Shenzhen, due mainly to the strong photochemical reactions in the daytime. During the Beijing winter, PM2.5 and MDA8 O3 show bidirectional causal relationships, but the two are significantly negatively correlated, driven by NO2 and relative humidity. Weak bidirectional, unidirectional and no causal effects between PM2.5 and MDA8 O3 are detected in other seasons in the four cities. In these seasons and cities, the top three causal factors of PM2.5 differ from those of MDA8 O3. Season-, city- and pollutant-specific control measures of PM2.5 and MDA8 O3 are required.

Size-resolved water-soluble organic carbon and its significant contribution to aerosol liquid water

Size-segregated aerosols collected in Beijing from 2021 to 2022 were used to investigate the contribution of organic aerosols to the aerosol liquid water content (ALWC), the influencing factors of ALWC, and the concentrations and size distribution characteristics of water-soluble organic carbon (WSOC) after clean air actions. The results showed that the concentration of WSOC in particulate matter (PM)1.8 was 3.52 ± 2.43 μg/m3 during the sampling period. Obvious changes were observed in the size distribution of WSOC after clean air actions, which may be attributed to the enhancement of atmospheric oxidation capacity and the decrease in PM concentration. The contribution of organic aerosols to the ALWC in fine PM was 18.1 % during the sampling period, which was more significant at lower particles concentration and smaller particle size ranges. The ambient relative humidity (RH) and the ratio of NO3−/SO42− had an apparent influence on ALWC. The continuous increase in the nitrate proportion significantly reduced the deliquescence point of the aerosols, making them prone to hygroscopic growth at lower RH. Analysis of the relation among nitrogen oxidation ratio (sulfur oxidation ratio), ALWC and PM1.8 mass concentrations suggests that organic matter has a significant effect on the formation of secondary inorganic aerosols in the initial phase of pollution formation and plays a crucial role in aerosol pollution formation in Beijing. These results are conducive to understanding the formation mechanism of aerosols and provide scientific data and theoretical support for the formulation of more effective emission-reduction measures.

Hydrolysis reactivity reveals significant seasonal variation in the composition of organic peroxides in ambient PM2.5

Atmospheric organic peroxides (POs) play a key role in the formation of O3 and secondary organic aerosol (SOA), impacting both air quality and human health. However, there still remain technical challenges in investigating the reactivity of POs in ambient aerosols due to the instability and lack of standards for POs, impeding accurate evaluation of their environmental impacts. In the present study, we conducted the first attempt to categorize and quantify POs in ambient PM2.5 through hydrolysis, which is an important transformation pathway for POs, thus revealing the reactivities of various POs. POs were generally categorized into hydrolyzable POs (HPO) and unhydrolyzable POs (UPO). HPO were further categorized into three groups: short-lifetime HPO (S-HPO), intermediate-lifetime HPO (I-HPO), and long-lifetime HPO (L-HPO). S-HPO and L-HPO are typically formed from Criegee intermediate (CI) and RO2 radical reactions, respectively. Results show that L-HPO are the most abundant HPO, indicating the dominant role of RO2 pathway in HPO formation. Despite their lower concentration compared to L-HPO, S-HPO make a major contribution to the HPO hydrolysis rate due to their faster rate constants. The hydrolysis of PM2.5 POs accounts for 19 % of the nighttime gas-phase H2O2 growth during the summer observation, constituting a noteworthy source of gas-phase H2O2 and contributing to the atmospheric oxidation capacity. Seasonal and weather conditions significantly impact the composition of POs, with HPO concentrations in summer being significantly higher than those in winter and elevated under rainy and nighttime conditions. POs are mainly composed of HPO in summer, while in winter, POs are dominated by UPO.

Analysis of Photochemical Characteristics and Sensitivity of Atmospheric Ozone in Nanjing in Summer

Tropospheric ozone (O3) is mainly produced through a series of photochemical reactions of nitrogen oxides (NOx) and volatile organic compounds (VOCs). The reaction process presents complex non-linear relationships. In this work, datasets of atmospheric ozone and volatile organic compounds (VOCs) observed during the summer of 2018 in Nanjing were used. Combining with the framework for 0-D atmospheric model-master chemical mechanism (F0AM-MCM), the characteristics of photochemical reactions for ozone (O3) formation in Nanjing during the O3 episode days and non-episode days were investigated. The results showed that φ(O3) and φ(TVOCs) in the O3 episode days were 47.8×10-9 and 49.0×10-9, respectively, exceeding those in the non-episode days by factors of 1.8 and 1.6. Furthermore, F0AM, the empirical kinetic modeling approach (EKMA), and relative incremental reactivity (RIR) were utilized for the calculation of ozone chemical sensitivity. It was found that O3 formation in Nanjing was attributed to both VOCs and NOx limitation. In addition, the modeled ·OH and HO2 concentrations in the O3 episode days were 1.3 and 1.8 times higher than those in the non-episode days. The higher formation and loss rates of ·OH and HO2 were also found during O3 episode days. These findings reflected that the enhancements of atmospheric oxidation capacity resulted in increased production rates of O3, providing an explanation for the enhancements of O3 concentrations in Nanjing during the O3 episode days. The findings also improved the understanding of the O3 photochemical characteristics over Nanjing in the summer during the O3 episode days.

Additional HONO and OH Generation from Photoexcited Phenyl Organic Nitrates in the Photoreaction of Aromatics and NOx.

HONO acts as a major OH source, playing a vital role in secondary pollutant formation to deteriorate regional air quality. Strong unknown sources of daytime HONO have been widely reported, which significantly limit our understanding of radical cycling and atmospheric oxidation capacity. Here, we identify a potential daytime HONO and OH source originating from photoexcited phenyl organic nitrates formed during the photoreaction of aromatics and NOx. Significant HONO (1.56-4.52 ppb) and OH production is observed during the photoreaction of different kinds of aromatics with NOx (18.1-242.3 ppb). We propose an additional mechanism involving photoexcited phenyl organic nitrates (RONO2) reacting with water vapor to account for the higher levels of measured HONO and OH than the model prediction. The proposed HONO formation mechanism was evidenced directly by photolysis experiments using typical RONO2 under UV irradiation conditions, during which HONO formation was enhanced by relative humidity. The 0-D box model incorporated in this mechanism accurately reproduced the evolution of HONO and aromatic. The proposed mechanism contributes 5.9-36.6% of HONO formation as the NOx concentration increased in the photoreaction of aromatics and NOx. Our study implies that photoexcited phenyl organic nitrates are an important source of atmospheric HONO and OH that contributes significantly to atmospheric oxidation capacity.

A portable instrument for measurement of atmospheric Ox and NO2 based on cavity ring-down spectroscopy

Atmospheric Ox (nitrogen dioxide (NO2) + ozone (O3)) can better reflect the local and regional change characteristics of oxidants compared to O3 alone, so obtaining Ox accurately and rapidly is the basis for evaluating the O3 production rate. Furthermore, Ox has proved to be a more representative indicator and can serve as a reflection of pollution prevention efficacy. A portable instrument for measuring atmospheric Ox and NO2 based on cavity ring-down spectroscopy (Ox/NO2-CRDS) was developed in this work. The NO2 concentration is accurately measured according to its absorption characteristic at 407.86 nm. Ambient O3 is converted into NO2 by chemical titration of high concentrations of nitrogen oxide (NO), and the O3 conversion efficiencies obtained are nearly 99%. The detection limit of the Ox/NO2-CRDS system for Ox is 0.024 ppbv (0.1 s), and the overall uncertainty of the instrument is ± 6%. Moreover, the Kalman filtering technique was applied to improve the measurement accuracy of Ox/NO2-CRDS. The system was applied in a comprehensive field observation campaign at Hefei Science Island from 26 to 30 September 2022, and the time concentration series and change characteristics of Ox and NO2 were obtained for five days. The measured Ox concentrations were compared with those of two commercial instruments, and the consistency was good (R2 = 0.98), indicating that this system can be deployed to accurately and rapidly obtain the concentrations of atmospheric Ox and NO2. It will be a useful tool for assessing the atmospheric oxidation capacity and controlling O3 pollution.摘要大气Ox (二氧化氮(NO2)+臭氧(O3))相比于O3能够更好的反应区域氧化剂的变化特征, Ox也是反应大气污染防治效果的一个关键指标. 本研究基于腔衰荡光谱技术研发了一套大气Ox和NO2同步测量系统 (Ox/NO2-CRDS). NO2浓度是利用其在407.86 nm处的特征吸收获取, 环境大气的O3通过高浓度的NO被转化为NO2进行间接测量, O3转化效率高于99%, Ox/NO2-CRDS的系统探测限为0.024 ppbv (0.1 s), 系统总不确定度为± 6%. 该Ox/NO2-CRDS系统成功应用于2022年9月26日–30日的合肥市科学岛综合外场观测中, 获取了连续5天的NO2和Ox的时间浓度序列和变化特征, 并将Ox的测量结果与商业化的设备进行了对比验证, 二者具有较好的一致性 (R2 = 0.98), 表明Ox/NO2-CRDS能够被应用于大气Ox和NO2的高灵敏探测. 未来该系统也将会变成评估大气氧化性以及控制臭氧污染的重要工具.

Typhoon- and pollution-driven enhancement of reactive bromine in the mid-latitude marine boundary layer.

Tropospheric reactive bromine is important for atmospheric chemistry, regional air pollution, and global climate. Previous studies have reported measurements of atmospheric reactive bromine species in different environments, and proposed their main sources, e.g. sea-salt aerosol (SSA), oceanic biogenic activity, polar snow/ice, and volcanoes. Typhoons and other strong cyclonic activities (e.g. hurricanes) induce abrupt changes in different earth system processes, causing widespread destructive effects. However, the role of typhoons in regulating reactive bromine abundance and sources remains unexplored. Here, we report field observations of bromine oxide (BrO), a critical indicator of reactive bromine, on the Huaniao Island (HNI) in the East China Sea in July 2018. We observed high levels of BrO below 500m with a daytime average of 9.7±4.2 pptv and a peak value of ∼26 pptv under the influence of a typhoon. Our field measurements, supported by model simulations, suggest that the typhoon-induced drastic increase in wind speed amplifies the emission of SSA, significantly enhancing the activation of reactive bromine from SSA debromination. We also detected enhanced BrO mixing ratios under high NOx conditions (ppbv level) suggesting a potential pollution-induced mechanism of bromine release from SSA. Such elevated levels of atmospheric bromine noticeably increase ozone destruction by as much as ∼40% across the East China Sea. Considering the high frequency of cyclonic activity in the northern hemisphere, reactive bromine chemistry is expected to play a more important role than previously thought in affecting coastal air quality and atmospheric oxidation capacity. We suggest that models need to consider the hitherto overlooked typhoon- and pollution-mediated increase in reactive bromine levels when assessing the synergic effects of cyclonic activities on the earth system.