HONO Photolysis Research Articles

Exploration of radical chemistry, precursor sensitivity and O3 control strategies in a provincial capital city, northwestern China

As the core city in northwestern China, Xi'an has suffered from serious O3 pollution in recent years. An observational model, coupled with the Master Chemical Mechanism (V3.3.1) and comprehensive data, analyzed atmospheric oxidation capacity (AOC), O3 formation mechanism, precursor sensitivity and control strategies in Xi'an. The study examined two periods (period I and II), with notable temperature and humidity differences. Despite lower precursor levels in period I, an O3 episode (peak value: 102.68 ppb) occurred only in period I, highlighting the crucial influence of meteorological conditions. Higher removal rate of primary pollutants occurs in period I, but meteorological conditions may not alter the dominant factor of AOC. Period I exhibited markedly high OH reactivity, with aromatics, alkenes, and NOx being the main contributors. HONO photolysis (50.78%) in the morning and O3 photolysis (34.13%) in the afternoon were the main HOx sources in period I, while HONO photolysis (62.86–80.68%) was significant at daytime for period II. Higher temperatures in period I accelerated all reaction rates involved in radical cycling, especially emphasizing RO2 + NO → RO + NO2. The results of sensitivity analysis showed that O3 sensitivity regime is VOC-limited in Xi'an, but the specific reactive species target VOC reductions emissions exhibited discrepancies for two distinct periods. A 20% decrease in VOCs and a 50% decrease in NOx (VOCs/NOx = 0.4) was proposed to be the optimal solution to achieve the O3 control target in period I. This study enhances our understanding of O3 formation under different meteorological conditions and provides scientific evidence for O3 pollution abatement policies in northwestern China, with potential applicability to other cities in this region and similar countries.

Origins of atmospheric nitrous acid and their contributions to OH radical from ship plumes, marine atmosphere, and continental air masses over South China Sea

Nitrous acid (HONO) is an important source of atmospheric hydroxyl radical (OH). However, HONO abundance in the marine boundary layer remain largely unknown. Here, ship-based measurements were performed to characterize the origins of HONO from ship plumes, marine atmosphere, and continental emissions over South China Sea (SCS) during September 2021. The results showed that the HONO concentrations were measured at substantial levels (1.0 ± 0.8 ppbv) in polluted plumes due to generally high NOx concentrations (52.3 ± 52.5 ppbv). Comparably, much lower HONO concentrations (0.086 ± 0.102 ppbv) were observed for marine atmosphere. During nighttime, the heterogeneous conversion of NO2 was the predominant source of HONO and occurred mainly on the sea surfaces through NO2 deposition. The HONO yield from this deposition (the proportion of NO2 that was converted to HONO) was 0.08 and 0.06 for the marine atmosphere and continental emissions, respectively. In contrast, daytime known HONO formation of marine atmospheric origins was mainly attributed to homogeneous OH + NO reaction, although the contribution of heterogeneous NO2 conversion might not be negligible. Approximately half of HONO sources during daytime are unknown, which were likely from photo-enhanced NO2 conversation on the sea surfaces. Our results showed that for marine atmosphere and ship plumes, the daily contributions of HONO photolysis to OH radical formation were about 20.8 % and 72.2 %, respectively, while the contributions from ozone photolysis were 79.2 % and 27.8 %. An average HONO concentration of 0.17 ppbv was measured in close shore regions when air masses originated from mainland China, with the contributions from HONO and ozone to OH radical of 21.4 % and 78.6 % respectively, similar to those for the marine atmosphere. This study suggests that HONO in the SCS has various sources (e.g., marine atmosphere, ship plumes, and continental emissions) and makes significant contributions to the OH abundance which affects the oxidation capacity in this area.

Relative humidity driven nocturnal HONO formation mechanism in autumn haze events of Beijing

Nitrous acid (HONO), a key precursor of hydroxyl radicals (OH), is one of the factors affecting atmospheric chemistry and air quality. Currently, the proposed sources of HONO are not able to fully explain observed HONO concentrations. In this study, a comprehensive field observation of HONO was conducted in the autumn of 2021 in urban Beijing. The box model using a default Master Chemical Mechanism (MCM) was unable to reproduce the observed HONO concentrations with a normalized mean bias (NMB) of −92.8%. The NMB improved to −46.1% after the inclusion of seven additional HONO formation pathways. Several factors like vehicle emission factor (1.23%) and nocturnal NO2 heterogeneous uptake coefficient on the ground surface (8.25 × 10−6) were calculated based on observational data. The enhancement factor for nocturnal NO2 heterogeneous conversion was established as a function of relative humidity (RH) and incorporated into the model, which compensated for the missing nocturnal HONO sources and well-reproduced the observed HONO concentrations, with an NMB of −5.1%. The major source of HONO at night was found to be the heterogeneous reaction of NO2 on the ground surface, contributing up to 85.6%. During the daytime, it was the homogeneous reaction of NO with OH, accounting for 41.8%. The daytime primary source of OH was mainly the photolysis of HONO, which constituted 73.6% and therefore promoted the formation of secondary pollutants and exacerbated haze events.

Oxidant concentrations and photochemistry in a vehicle cabin.

Indoor air quality (IAQ) in vehicles can be important to people's health, especially for those whose occupations require them to spend extensive time in vehicles. To date, research on vehicle IAQ has primarily focused on direct emissions as opposed to chemistry happening in vehicle cabins. In this work, we conducted time-resolved measurements of the oxidants and oxidant precursors ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), and nitrous acid (HONO) inside the cabin of a 2012 Toyota Rav4 under varying ventilation conditions (i.e., car off, car on with passive ventilation, car on with mechanical ventilation via the recirculating fan, and car on with mechanical ventilation via the direct fan). Ozone levels inside the vehicle were significantly lower than outdoors under most conditions, and were approximately half the outdoor levels when the direct fan was in operation. Nitric oxide and NO2 concentrations were very low both inside the vehicle and outdoors. Nitrous acid levels in the vehicle were lower than reported values in other indoor environments, though much higher than expected outdoor levels. We also investigated the potential for photochemical production of radicals in the vehicle. Time- and wavelength-resolved solar irradiance spectra were collected, and steady state hydroxyl radical (OH) and nitrate radical (NO3) concentrations were calculated. Steady state OH concentrations were predicted to be similar to those in air masses in residences illuminated by sunlight, suggesting the importance of HONO photolysis in vehicles. Conversely, nitrate radicals (NO3) were not considered significant indoor oxidants in our study due to rapid titration by NO. Overall, our findings emphasize the importance of both air exchange and photochemistry in shaping the composition of air inside vehicles.

Impact of soil–atmosphere HONO exchange on concentrations of HONO and O3 in the North China Plain

Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) and plays a vital role in atmospheric photochemistry and nitrogen cycling. Soil emissions have been considered as a potential source of HONO. Lately, the HONO emission via soil-atmosphere exchange (ESA-exchange) from soil nitrite has been validated and quantified through chamber experiments, but has not been assessed in the real atmosphere. We coupled ESA-exchange and the other seven potential sources of HONO (i.e., traffic, indoor and soil bacterial emissions, heterogeneous reactions on ground and aerosol surfaces, nitrate photolysis, and acid displacement) into the Weather Research and Forecasting model with Chemistry (WRF-Chem), and found that diurnal variations of the soil emission flux at the Wangdu site were well simulated. During the non-fertilization period, ESA-exchange contributed ∼28 % and ∼35 % of nighttime and daytime HONO, respectively, and enhanced the net ozone (O3) production rate by ∼8 % across the North China Plain (NCP). During the preintensive/intensive fertilization period, the maximum ESA-Exchange contributions attained ∼70 %/83 % of simulated HONO in the afternoon across the NCP, definitely asserting its dominance in HONO production. ESA-Exchange enhanced the OH production rate via HONO photolysis by ∼3.5/7.0 times, and exhibited an increase rate of ∼13 %/20 % in the net O3 production rate across the NCP. The total enhanced O3 due to the eight potential HONO sources ranged from ∼2 to 20 ppb, and ESA-exchange produced O3 enhancements of ∼1 to 6 ppb over the three periods. Remarkably, the average contribution of ESA-exchange to the total O3 enhancements remained ∼30 %. This study suggests that ESA-exchange should be included in three-dimensional chemical transport models and more field measurements of soil HONO emission fluxes and soil nitrite levels are urgently required.

Enhanced nitrous acid (HONO) formation via NO2 uptake and its potential contribution to heavy haze formation during wintertime

A full understanding of the sources of atmospheric nitrous acid (HONO) in the polluted urban atmosphere remains a challenge. In this study, ambient HONO and relevant species were measured during January 2019 at an urban site in Beijing, China, and a budget analysis of HONO was conducted using a box model combined with field observations. Large nighttime “missing sources” of HONO were identified on heavily polluted days based on traditional sources, which had a significant correlation with the relative humidity, ammonia (NH3), and aerosol surface area, and the promotional effect of NH3 for nitrogen dioxide (NO2) uptake on the wet aerosol surface was discussed. Then, an updated parameterization scheme for quantifying the enhanced heterogeneous reactions of NO2 on aerosol surfaces is proposed, and the missing nighttime sources of HONO could be substantially compensated after the new scheme was incorporated. Further evaluation on the contributions of HONO to hydroxyl radicals was conducted, and the authors found that the photolysis of HONO played a dominant role in the primary OH production on the polluted days (78%–90%). The study reveals great potential of an NH3-enhanced uptake coefficient of NO2 on the aerosol surface in the nocturnal HONO budget, and highlights the significance of HONO in the strong atmospheric oxidation capability during episodes with a heavily polluted atmosphere.摘要本文研究了重污染过程中气态亚硝酸 (HONO) 的关键来源并基于化学箱模型对其源汇过程进行了闭合分析. 结果显示, 现有的HONO 源汇机制并不能解释观测期间出现的高HONO事件, 尤其是重污染过程夜间存在大量的HONO "未知源". 本文提出了一套新的HONO 源汇参数化方案, 可以较好的模拟观测期间HONO日间和夜间来源, 并进一步评估了HONO 对羟基自由基 (OH) 的贡献, 发现 HONO 光解主导了重污染天OH生成 (78%–90%). 研究结果揭示了华北城市富氨大气环境促进 NO2在气溶胶表面的摄取和非均相反应进而主导了夜间HONO生成, 凸显了HONO化学对于重污染过程维持大气氧化能力的重要作用.

Coarse particles compensate for missing daytime sources of nitrous acid and enhance atmospheric oxidation capacity in a coastal atmosphere

Large missing sources of daytime atmospheric nitrous acid (HONO), a vital source of hydroxyl radicals (OH) through its photolysis, frequently exist in global coastal regions. In this study, ambient HONO and relevant species were measured at a coastal site in the Pearl River Delta (PRD), China, during October 2019. Relatively high concentrations (0.32 ± 0.19 ppbv) and daytime peaks at approximately 13:00 of HONO were observed, and HONO photolysis was found to be the dominant (55.5 %) source of the primary OH production. A budget analysis of HONO based on traditional sources suggested large unknown sources during the daytime (66.4 %), which had a significant correlation with the mass of coarse particles (PM2.5–10) and photolysis frequency (J(NO2)). When incorporating photolysis of the abundant nitrate measured in coarse particles with a reasonable enhancement factor relative to fine particles due to favorable aerosol conditions, the missing daytime sources of HONO could be fully compensated by coarse particles serving as the largest source at this coastal site. Our study revealed great potential of coarse particles as a strong daytime HONO source, which has been ignored before but can efficiently promote NOx recycling and thus significantly enhance atmospheric oxidation capacity.

Organic aerosol formation from 222 nm germicidal light: ozone-initiated vs. non-ozone pathways.

Germicidal ultraviolet lamps outputting 222 nm light (GUV222) have the potential to reduce the airborne spread of disease through effective inactivation of pathogens, while remaining safe for direct human exposure. However, recent studies have identified these lamps as a source of ozone and other secondary pollutants such as secondary organic aerosol (SOA), and the health effects of these pollutants must be balanced against the benefits of pathogen inactivation. While ozone reactions are likely to account for much of this secondary indoor air pollution, 222 nm light may initiate additional non-ozone chemical processes, including the formation of other oxidants and direct photolytic reactions, which are not as well understood. This work examines the impacts of GUV222 on SOA formation and composition by comparing limonene oxidation under GUV222 and O3-only control conditions in a laboratory chamber. Differences between these experiments enable us to distinguish patterns in aerosol formation driven by ozone chemistry from those driven by other photolytic processes. These experiments also examine the influence of the addition of NO2 and nitrous acid (HONO), and investigate SOA formation in sampled outdoor air. SOA composition and yield vary only slightly with respect to GUV222vs. ozone-only conditions; NO2 and HONO photolysis do not appreciably affect the observed chemistry. In contrast, we observe consistent new particle formation under high-fluence 222 nm light (45 μW cm-2) that differs substantially from ozone-only experiments. This observed new particle formation represents an additional reason to keep GUV222 fluence rates to the lowest effective levels.

HONO chemistry at a suburban site during the EXPLORE-YRD campaign in 2018: formation mechanisms and impacts on O3 production

Abstract. HONO is an important precursor for OH radicals that impact secondary-pollutant production. However, there are still large uncertainties about different HONO sources which hinder accurate predictions of HONO concentration and hence atmospheric oxidation capacity. Here HONO was measured during the EXPLORE-YRD campaign (EXPeriment on the eLucidation of the atmospheric Oxidation capacity and aerosol foRmation and their Effects in the Yangtze River Delta), along with other important parameters, enabling us to comprehensively investigate HONO variation characteristics and evaluate the relative importance of different HONO sources by using a box model. HONO showed significant variations, ranging from several tens of parts per thousand to 4.4 ppb. The average diurnal pattern of HONO / NOx showed a maximum of 0.17 around noon and resembled that of j(O1D), indicating the existence of photo-induced sources. Modeling simulations with only the default HONO source (OH + NO) largely underestimated HONO concentrations, with the modeled-averaged noontime HONO concentration an order of magnitude lower than the observed concentration. The calculated strength of the unknown HONO source (Punknown) showed a nearly symmetrical diurnal profile with a maximum of 2.5 ppb h−1 around noon. The correlation analysis and sensitivity tests showed that the photo-induced NO2 conversion on the ground was able to explain Punknown. Additional HONO sources incorporated into the box model improved the model's performance in simulating HONO concentrations. The revised box model reproduced the nighttime HONO concentration well but still underestimated the daytime HONO concentration. Further sensitivity tests indicated the underestimation of daytime HONO was not due to uncertainties of photo-induced NO2 uptake coefficients on the ground or aerosol surfaces or the enhancement factor of nitrate photolysis but was more likely due to other sources that were not considered in the model. Among the incorporated HONO sources and the default gas-phase source, photo-induced NO2 conversion on the ground dominated the modeled HONO production during the daytime, accounting for 71 % of the total, followed by NO + OH, NO2 hydrolysis on the ground surface, vehicle emissions, photo-induced NO2 conversion on the aerosol surface, nitrate photolysis and NO2 hydrolysis on the aerosol surface. NO2 hydrolysis on the ground surface was the major source of nighttime HONO, contributing 55 % of total HONO production. HONO photolysis contributed 43 % of ROx production during the daytime, followed by O3 photolysis (17 %), HCHO photolysis (14 %), ozonolysis of alkenes (12 %) and carbonyl photolysis (10 %). With observed HONO as a model constraint, the average peak of net ozone production rate increased by 88 % to 12.6 ppb h−1 compared to that without observed HONO as a model constraint, indicating HONO evidently enhanced O3 production and hence aggravated O3 pollution in summer seasons. Our study emphasized the importance of heterogeneous NO2 conversion on the ground surface in HONO production and accurate parameterization of HONO sources in predicting secondary-pollutant production.

Severe photochemical pollution formation associated with strong HONO emissions from dew and guttation evaporation

The unknown daytime source of HONO has been extensively investigated due to unexplained atmospheric oxidation capacity and current modelling bias, especially during cold seasons. In this study, abrupt morning increases in atmospheric HONO at a rural site in the North China Plain (NCP) were observed almost on daily basis, which were closely linked to simultaneous rises in atmospheric water vapor content and NH3 concentrations. Dew and guttation water formation was frequently observed on wheat leaves, from which water samples were taken and chemically analyzed for the first time. Results confirmed that such natural processes likely governed the daily nighttime deposition and daytime release of HONO and NH3, which have not been considered in the numerous HONO budget studies investigating its large missing daytime source in the NCP. The dissolved HONO and NH3 in leaf surface water droplets reached 1.4 and 23 mg L−1 during the morning on average, resulting in averaged atmospheric HONO and NH3 increases of 0.89 ± 0.61 and 43.7 ± 29.3 ppb during morning hours, with relative increases of 186 ± 212 % and 233 ± 252 %, respectively. The high atmospheric oxidation capacity contained within HONO was stored in near surface liquid water (such as dew, guttation and soil surface water) during nighttime, which prevented its atmospheric dispersion after sunset and protected it from photodissociation during early morning hours. HONO was released in a blast during later hours with stronger solar radiation, which triggered and then accelerated daytime photochemistry through the rapid photolysis of HONO and subsequent OH production, especially under high RH conditions, forming severe secondary gaseous and particulate pollution. Results of this study demonstrate that global ecosystems might play significant roles in atmospheric photochemistry through nighttime dew formation and guttation processes.

The significant contribution of nitrate to a severe haze event in the winter of Guangzhou, China

A severe haze pollution occurred in Guangzhou from January 14 to 16, 2021, during which the mass concentration of PM2.5 ranged from 76 to 243 μg m−3. This level of pollution was rarely observed in recent years considering the improved air quality in Guangzhou. Therefore, it is crucial to comprehensively study the formation mechanisms of this severe haze pollution to prevent its reoccurrence. During the haze period, the concentrations of NO and NO2 sharply increased by 7.4 and 3.8 times, respectively, and total volatile organic compounds (TVOCs) increased 7 times, suggesting enhanced primary emissions from vehicles due to stagnant meteorological conditions. Nitrate concentration (43 ± 20 μg m−3) increased 6.7 times and became the dominant species in PM2.5 during the haze period. Notably, gaseous NH3, HONO and HNO3 also exhibited a sharp increase, suggesting the important role of nitrate chemistry in the evolution of haze pollution. The simulation results from chemical box model revealed that the OH + NO2 reaction was the dominant formation pathway for nitrate production (82 %) during the haze period. The net production rate of ROx radicals (including OH, HO2 and RO2) was 4.4 times higher during the haze period (5.8 ppb h−1) compared to the pre-haze period (1.3 ppb h−1). This was mainly attributed to the enhanced HONO and OVOCs photolysis, which increased from 0.6 ppb h−1 to 3.1 ppb h−1 and 0.4 ppb h−1 to 2.1 ppb h−1, respectively. Furthermore, the sensitivity tests demonstrated the reductions in VOCs and NOx were both beneficial for controlling nitrate production by influencing OH production and N2O5 uptake rate. These findings provide insights into the formation mechanisms of nitrate production during severe haze pollution and suggest that joint mitigation of PM2.5 and O3 can be achieved through the control of VOCs emission.

Insights Into NOx and HONO Chemistry in the Tropical Marine Boundary Layer at Cape Verde During the MarParCloud Campaign

AbstractChemical processing of reactive nitrogen species, especially of NOx (= NO + NO2) and nitrous acid (HONO), determines the photochemical ozone production and oxidation capacity in the troposphere. However, sources of HONO and NOx in the remote marine atmosphere are still poorly understood. In this work, the multiphase chemistry mechanism CAPRAM in the model framework SPACCIM was used to study HONO formation at Cape Verde (CVAO) in October 2017, adopted with the input of current parameterizations for various HONO sources. Three simulations were performed that adequately reproduced ambient HONO levels and its diurnal pattern. The model performance for NOx and O3 improves significantly when considering dust‐surface‐photocatalytic conversions of reactive nitrogen compounds with high correlation coefficients up to 0.93, 0.56, and 0.89 for NO, NO2, and O3, respectively. Photocatalytic conversion of the adsorbed HNO3 on dust is modeled to be the predominant contributor for daytime HONO at CVAO, that is, accounting for about 62% of the chemical formation rate at noontime. In contrast, the ocean‐surface‐mediated conversion of NO2 to HONO and other discussed pathways are less important. The average OH levels at midday (9:00–16:00) modeled for cluster trajectory 1, 2, and 3 are 5.2, 5.1, and 5.2 × 106 molecules cm−3, respectively. Main OH formation is driven by O3 photolysis with a contribution of 74.6% to the total source rate, while HONO photolysis is negligible (∼1.8%). In summary, this study highlights the key role of dust aerosols for HONO formation and NOx cycling at CVAO and possibly in other dust‐affected regions, urgently calling for further investigations using field and model studies.

Pollution characteristics, sources, and photochemical roles of ambient carbonyl compounds in summer of Beijing, China

Ambient carbonyls are important precursors of radicals and ground-level ozone (O3). In this study, sources, precursors, and impacts on radicals and O3 of carbonyls were investigated based on online observations of volatile organic compounds (VOCs) at an urban site in Beijing during June 2021. Carbonyls accounted for 36% and 42% of mixing ratios and OH reactivity for total measured VOCs, respectively. Formaldehyde was the most abundant carbonyl, with the mean level of 4.13 ± 2.28 ppb. Source apportionment results based on the multi linear regression (MLR) method suggested that secondary production contributed 41%, 25%, 36%, and 30% of formaldehyde, acetaldehyde, propanal, and acetone, respectively. Key precursors of carbonyls were then identified based on the calculation of their production rates. It was found that alkenes contributed 59%–80% of aldehydes production. Impacts of carbonyls on HOx radicals (OH and HO2) and O3 production were explored using a box model based on observations (OBM). Photolysis of HONO, formaldehyde, and O3 were the dominant primary sources of HOx radicals during daytime of O3 pollution days, with average relative contributions of 52%, 28%, and 19% to the total primary production rate of HOx, respectively. Aldehydes accounted for 32% (20% from formaldehyde) of average HOx removal rates. The relative incremental reactivity (RIR) values of NOx determined by the OBM were negative, suggesting that the O3–VOCs-NOx sensitivity was in the VOCs-limited regime. Using the observed concentrations of carbonyls as constraints of OBM, the absolute values of RIR for NOx tended to increase but those for anthropogenic VOCs tended to decrease. Formaldehyde showed the largest RIR value for anthropogenic VOCs during O3 pollution days. These findings indicated the important impacts of carbonyls on O3 production and O3–VOCs-NOx sensitivity.

Snowpack nitrate photolysis drives the summertime atmospheric nitrous acid (HONO) budget in coastal Antarctica

Abstract. Measurements of atmospheric nitrous acid (HONO) amount fraction and flux density above snow were carried out using a long-path absorption photometer at Halley station in coastal Antarctica between 22 January and 3 February 2022. The mean ±1σ HONO amount fraction was (2.1 ± 1.5) pmol mol−1 and showed a diurnal cycle (range of 1.0–3.2 pmol mol−1) with a maximum at solar noon. These HONO amount fractions are generally lower than have been observed at other Antarctic locations. The flux density of HONO from the snow, measured between 31 January and 1 February 2022, was between 0.5 and 3.4×1012 m-2s-1 and showed a decrease during the night. The measured flux density is close to the calculated HONO production rate from photolysis of nitrate present in the snow. A simple box model of HONO sources and sinks showed that the flux of HONO from the snow makes a >10 times larger contribution to the HONO budget than its formation through the reaction of OH and NO. Ratios of these HONO amount fractions to NOx measurements made in summer 2005 are low (0.15–0.35), which we take as an indication of our measurements being comparatively free from interferences. Further calculations suggest that HONO photolysis could produce up to 12 pmolmol-1h-1 of OH, approximately half that produced by ozone photolysis, which highlights the importance of HONO snow emissions as an OH source in the atmospheric boundary layer above Antarctic snowpacks.

Measurements of Hydroxyl Radical Concentrations during Indoor Cooking Events: Evidence of an Unmeasured Photolytic Source of Radicals.

The hydroxyl radical (OH) is the dominant oxidant in the outdoor environment, controlling the lifetimes of volatile organic compounds (VOCs) and contributing to the growth of secondary organic aerosols. Despite its importance outdoors, there have been relatively few measurements of the OH radical in indoor environments. During the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign, elevated concentrations of OH were observed near a window during cooking events, in addition to elevated mixing ratios of nitrous acid (HONO), VOCs, and nitrogen oxides (NOX). Particularly high concentrations were measured during the preparation of a traditional American Thanksgiving dinner, which required the use of a gas stove and oven almost continually for 6 h. A zero-dimensional chemical model underpredicted the measured OH concentrations even during periods when direct sunlight illuminated the area near the window, which increases the rate of OH production by photolysis of HONO. Interferences with measurements of nitrogen dioxide (NO2) and ozone (O3) suggest that unmeasured photolytic VOCs were emitted during cooking events. The addition of a VOC that photolyzes to produce peroxy radicals (RO2), similar to pyruvic acid, into the model results in better agreement with the OH measurements. These results highlight our incomplete understanding of the nature of oxidation in indoor environments.

Atmospheric oxidation capacity and O3 formation in a coastal city of southeast China: Results from simulation based on four-season observation

The pollution of atmospheric ozone in China shows an obvious upward trend in the past decade. However, the studies on the atmospheric oxidation capacity and O3 formation in four seasons in the southeastern coastal region of China with the rapid urbanization remain limited. Here, a four-season field observation was carried out in a coastal city of southeast China, using an observation-based model combining with the Master Chemical Mechanism, to explore the atmospheric oxidation capacity (AOC), radical chemistry, O3 formation pathways and sensitivity. The results showed that the average net O3 production rate (14.55 ppbv/hr) in summer was the strongest, but the average O3 concentrations in autumn was higher. The AOC and ROx levels presented an obvious seasonal pattern with the maximum value in summer, while the OH reactivity in winter was the highest with an average value of 22.75 sec−1. The OH reactivity was dominated by oxygenated VOCs (OVOCs) (30.6%-42.8%), CO (23.2%-26.8%), NO2 (13.6%-22.0%), and alkenes (8.4%-12.5%) in different seasons. HONO photolysis dominated OH primary source on daytime in winter, while in other seasons, HONO photolysis in the morning and ozone photolysis in the afternoon contributed mostly. Sensitivity analysis indicated that O3 production was controlled by VOCs in spring, autumn and winter, but a VOC-limited and NOx-limited regime in summer, and alkene and aromatic species were the major controlling factors to O3 formation. Overall, the study characterized the atmospheric oxidation capacity and elucidated the controlling factors for O3 production in the coastal area with the rapid urbanization in China.

Formation of a Resonance-Stabilized Radical Intermediate by Hydroxyl Radical Addition to Cyclopentadiene.

The reaction of the OH radical with cyclopentadiene (C5H6) was investigated at room temperature using multiplexed photoionization mass spectrometry. OH radicals in their ground electronic state were generated in the gas phase by 248 nm photolysis of H2O2 or 351 nm photolysis of HONO. Analysis of photoion spectra and temporal profiles reveal that at room temperature and over the 4-8 Torr pressure range, the resonance-stabilized 5-hydroxycyclopent-2-en-1-yl (C5H6OH) is the main observed reaction product. Abstraction products (C5H5) were not detected. The C5H6OH potential energy surface calculated at the CCSD(T)/cc-pVTZ//M06-2X/6-311++G** level of theory suggests that the resonance-stabilized radical product is formed through barrierless addition of the OH radical onto cyclopentadiene's π system to form a van der Waals complex. This weakly bound adduct isomerizes through a submerged energy barrier to the resonance-stabilized addition adduct. Master Equation calculations, including two OH-addition entrance pathways, predict that 5-hydroxycyclopent-2-en-1-yl remains the sole addition product up to 500 K. The detection of an OH-containing resonance-stabilized radical at room temperature further highlights their importance in carbon- and oxygen-rich environments such as combustion, planetary atmospheres, and the interstellar medium.

Atmospheric chemistry of nitrous acid and its effects on hydroxyl radical and ozone at the urban area of Beijing in early spring 2021

The atmospheric chemistry of nitrous acid (HONO) has received extensive attention because of its significant contribution to hydroxyl (OH) radicals. Heterogeneous reaction of NO2 is an important HONO source, and its reaction mechanism is affected by many factors, such as concentration of gaseous NO2, surface adsorbed water, relative humidity and temperature. Although laboratory studies have confirmed the effect of temperature on heterogeneous reaction of NO2, there are few field observations reporting about it. We have conducted a field observation in the early spring 2021 when the temperature ranges widely (−0.1–24.7 °C). Concentrations of HONO and related pollutants at the urban area of Beijing are obtained. The hourly averaged HONO concentration reaches 4.87 ppb with a mean value of 1.48 ± 1.09 ppb. Combined with box model and RACM2 mechanism, we found an optimal temperature (∼10 °C) existing for heterogeneous reaction of NO2 during this measurement. When considering the promotion effect of optimal temperature, the contribution of heterogeneous reaction of NO2 to HONO can increase by 10%. This result will provide essential information for developing an accurate model of HONO chemistry in the atmosphere especially for certain periods or regions with temperature changing largely. Moreover, heterogeneous reaction of NO2 is the vital source of HONO, contributing 63–76% to simulated HONO during this measurement. Note that HONO photolysis is the most important formation pathway of OH radicals, and ambient HONO concentration is the obbligato constraint for evaluating atmospheric oxidation by model simulations.

Vertical distributions of atmospheric HONO and the corresponding OH radical production by photolysis at the suburb area of Shanghai, China

Nitrous acid (HONO) is considered as one of the main sources of the hydroxyl radical (OH), the most relevant oxidant in the atmosphere. Multi-AXis-Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements were conducted to obtain the vertical profiles of aerosol and HONO from November 1, 2020 to January 31, 2021 at a suburb site of Shanghai, China. HONO was mainly distributed near the surface, but high values HONO occasionally occurred around 0.7 km, indicating an unaccounted source of daytime HONO at high altitudes. The positive correlation between HONO and aerosols suggested that the photo-enhanced heterogeneous reactions on the aerosol surface were an important source of daytime HONO at high altitudes. To obtain the vertical distribution of OH production by HONO photolysis (P(OH)HONO), the vertical profiles of photolysis rate of HONO (JHONO) were calculated by establishing a method of combining observations with empirical relationship based on heterogeneous atmospheric and radiative transfer models. The JHONO increased approximately linearly with increasing altitudes and the noontime averages value of JHONO near the ground were 6.68 × 10−4 s−1, which was strongly negatively affected by aerosols in the morning and afternoon. The P(OH)HONO profile varied in different months (November, December, January) that the changes were mainly affected by HONO and JHONO. P(OH)HONO was more positively affected by JHONO at high altitude and noon but greatly influenced by HONO concentrations in the morning and afternoon.

Formation mechanisms and atmospheric implications of summertime nitrous acid (HONO) during clean, ozone pollution and double high-level PM2.5 and O3 pollution periods in Beijing

Nitrous acid (HONO) is a key precursor of the hydroxyl radicals (OH) and has a significant impact on air quality. Nowadays, the source of HONO is still controversial due to its complex formation mechanisms, which is widely explored in extensive field and laboratory studies. In this study, the pollution characteristics and source contribution of HONO under different air quality conditions in summer in Beijing were analyzed. The observation periods were classified as three typical periods: clean, ozone pollution, and double high pollution (co-occurrence of high PM2.5 and O3 concentrations). The average concentrations of observed HONO were 0.38 ± 0.35 ppb, 0.21 ± 0.18 ppb, 0.26 ± 0.20 ppb and 0.54 ± 0.45 ppb during the whole, clean, ozone and double high periods, respectively. The elevated HONO levels at night were attributed to vehicle emissions and the RH-dependent heterogeneous conversion of NO2 to HONO. The average emission ratio (HONO/NOx) was 0.85 % ± 0.38 %, and the mean value of calculated nocturnal NO2 to HONO conversion frequency was 0.0076 ± 0.0031 h−1. Based on daytime HONO budget analysis, the largest potential source of HONO was the homogeneous reaction of NO and OH (0.33 and 0.34 ppb h−1), followed by the unknown source (0.11 and 0.21 ppb h−1) during clean and ozone periods, while the unknown source (0.49 ppb h−1) played the predominant role during double high period. The unknown sources of HONO could be attributed to the photo-enhanced heterogeneous conversion of NO2 and the photolysis of particulate nitrate. Furthermore, the photolysis of ozone (0.17, 0.34 and 0.44 ppb h−1) was the major contributor to primary OH during three typical periods. HONO photolysis contributed considerable amounts of primary OH (0.32 ppb h−1) during double high period. These results are helpful to further understand the linkage between HONO and air quality variation.