N2O5 Uptake Coefficient Research Articles

Identifying Driving Factors of Atmospheric N2O5 with Machine Learning.

Dinitrogen pentoxide (N2O5) plays an essential role in tropospheric chemistry, serving as a nocturnal reservoir of reactive nitrogen and significantly promoting nitrate formations. However, identifying key environmental drivers of N2O5 formation remains challenging using traditional statistical methods, impeding effective emission control measures to mitigate NOx-induced air pollution. Here, we adopted machine learning assisted by steady-state analysis to elucidate the driving factors of N2O5 before and during the 2022 Winter Olympics (WO) in Beijing. Higher N2O5 concentrations were observed during the WO period compared to the Pre-Winter-Olympics (Pre-WO) period. The machine learning model accurately reproduced ambient N2O5 concentrations and showed that ozone (O3), nitrogen dioxide (NO2), and relative humidity (RH) were the most important driving factors of N2O5. Compared to the Pre-WO period, the variation in trace gases (i.e., NO2 and O3) along with the reduced N2O5 uptake coefficient was the main reason for higher N2O5 levels during the WO period. By predicting N2O5 under various control scenarios of NOx and calculating the nitrate formation potential from N2O5 uptake, we found that the progressive reduction of nitrogen oxides initially increases the nitrate formation potential before further decreasing it. The threshold of NOx was approximately 13 ppbv, below which NOx reduction effectively reduced the level of night-time nitrate formations. These results demonstrate the capacity of machine learning to provide insights into understanding atmospheric nitrogen chemistry and highlight the necessity of more stringent emission control of NOx to mitigate haze pollution.

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.

Airborne Observations Constrain Heterogeneous Nitrogen and Halogen Chemistry on Tropospheric and Stratospheric Biomass Burning Aerosol

AbstractHeterogeneous chemical cycles of pyrogenic nitrogen and halides influence tropospheric ozone and affect the stratosphere during extreme Pyrocumulonimbus (PyroCB) events. We report field‐derived N2O5 uptake coefficients, γ(N2O5), and ClNO2 yields, φ(ClNO2), from two aircraft campaigns observing fresh smoke in the lower and mid troposphere and processed/aged smoke in the upper troposphere and lower stratosphere (UTLS). Derived φ(ClNO2) varied across the full 0–1 range but was typically <0.5 and smallest in a PyroCB (<0.05). Derived γ(N2O5) was low in agricultural smoke (0.2–3.6 × 10−3), extremely low in mid‐tropospheric wildfire smoke (0.1 × 10−3), but larger in PyroCB processed smoke (0.7–5.0 × 10−3). Aged biomass burning aerosol in the UTLS had a higher γ(N2O5) of 17 × 10−3 that increased with sulfate and liquid water, but that was 1–2 orders of magnitude lower than values for aqueous sulfuric aerosol used in stratospheric models.

Nocturnal downward transport of NO3 radical from the residual layer to a surface site by the mountain breeze in Seoul, South Korea

Using the long-path differential optical absorption spectroscopy (LP-DOAS) technique, the nocturnal mixing ratios of NO3 radicals were measured at an urban site in Seoul, South Korea, from May 13 to June 12, 2022. The primary objectives of the study were to estimate the NO3 radical concentration in the nighttime boundary layer and to examine the variations in their generation and loss over time, including an evaluation of their sources and sinks. The observed mean NO3 mixing ratios and lifetimes were 16 pptv and 73 s, respectively. NO3 concentrations and lifetimes were closely associated with their production, involving O3 and NO2, as well as the loss processes regulated by NO, VOCs, and aerosol surface area. Applying the steady-state assumption for NO3 and N2O5, the mean N2O5 uptake coefficient on the aerosol surface for the entire period was 0.031. When foggy nights were excluded from the analysis, the uptake coefficient decreased to 0.025. These values are within the higher range of the results reported in other studies. High relative humidity, which averaged 75% at night throughout the collection period, favored high N2O5 uptake coefficients. NO3 concentrations generally peaked shortly after sunset and gradually declined until sunrise. However, we frequently observed distinct increases in NO3 throughout the early morning hours, especially during clear nights, when local circulation with the westerly mountain breeze prevailed at the research site. The mountain breeze transported residual air downward, resulting in 110% and 38% higher NO3 and O3 levels at the sampling locations, respectively, compared to normal conditions. This additional source of nocturnal radicals and O3 has consequences for increased secondary aerosols and O3 production, particularly at urban surface levels where they are readily depleted in the early morning hours. To this end, a more thorough examination is required to measure N2O5 and a larger spectrum of VOCs species, as these parameters are crucial for nighttime radical budgets, secondary aerosols, and O3 generation in cities like Seoul.

Nitrous acid budgets in the coastal atmosphere: potential daytime marine sources

Abstract. Nitrous acid (HONO), a vital precursor of atmospheric hydroxyl radicals (OH), has been extensively investigated to understand its characteristics and formation mechanisms. However, discerning fundamental mechanisms across diverse environments remains challenging. This study utilizes measurements from Mount Lao, a coastal mountain in eastern China, and an observation-based chemical box model (OBM) to examine HONO budgets and their subsequent impacts on atmospheric oxidizing capacity. The model incorporates additional HONO sources, including direct emissions, heterogeneous conversions of NO2 on aerosol and ground surfaces, and particulate nitrate photolysis. The observed mean HONO concentration was 0.46 ± 0.37 ppbv. The updated model reproduced daytime HONO concentrations well during dust and photochemical pollution events. During dust events, daytime HONO formation was dominated by photo-enhanced heterogeneous reactions of NO2 on aerosol surfaces (> 50 %), whereas particulate nitrate photolysis (34 %) prevailed during photochemical pollution events. Nevertheless, the model uncovers a significant unidentified marine HONO source in a “sea case”, with its HONO production rate reaching up to 0.70 ppbv h−1 at noon. Without considering this unidentified source, an extraordinarily high photolysis coefficient of nitrate and/or a heterogeneous uptake coefficient of NO2 would be required to match observed HONO concentrations. This missing marine HONO source affected the peak O3 production rate and OH radical concentration by 36 % and 28 %, respectively, at the observation site. Given the limited HONO observation data in coastal and marine settings, the unidentified HONO source may cause an underestimation of the atmosphere's oxidizing capacity. This study highlights the necessity for further investigation of the role of HONO in atmospheric chemistry in coastal and marine environments.

Atmospheric ammonia in the rural North China Plain during wintertime: Variations, sources, and implications for HONO heterogeneous formation

Atmospheric ammonia (NH3) plays an important role in secondary inorganic aerosol formation. Understanding the temporal variations, sources, and environmental influences of NH3 is conducive to better formulate PM2.5 pollution control strategies for policy-makers. Here, we performed a comprehensive field campaign with the measurements of NH3 and related parameters at a rural site of the North China Plain (NCP) in winter of 2017. The results showed that residential coal combustion contributed dominantly to NH3 during the entire observation period, resulting in the obviously high average concentration of NH3 (31.2 ± 24.6 ppbv). The sensitivity tests of pH-NHx during the three different pollution periods suggested that the rural site was always in the NHx-rich atmosphere where high levels of NHx increased the particle pH inefficiently. Nevertheless, the particle pH still elevated by 1.5–2.2 units at the excessive NHx levels during the three pollution periods. In addition, the HONO/NO2 ratios were found to correlate linearly with NH3 concentrations, implying the acceleration effect of NH3 on HONO production from NO2 heterogeneous reactions. After considering the NH3-enhanced uptake coefficient of NO2 in the nocturnal HONO budget, the unknown source of HONO could be fully explained. Therefore, more attentions should be given for effective emission control of NH3 to improve air quality throughout the NCP, especially in the rural areas.

Formation and impacts of nitryl chloride in Pearl River Delta

Abstract. Here we present a field measurement of ClNO2 (nitryl chloride) and N2O5 (dinitrogen pentoxide) by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) with the Filter Inlet for Gas and AEROsols (FIGAERO) at a regional site in the Pearl River Delta during a photochemical pollution season from 26 September to 17 November 2019. Three patterns of air masses are sampled during this campaign, including the dominating air masses from the north and northeast urban regions (Type A), the southeast coast (Type B), and the South China Sea (Type C). The concentration of ClNO2 and N2O5 was observed to be much higher in Type A and B than in Type C, indicating that the urban nighttime chemistry is more active than the background marine regions. The N2O5 uptake coefficient and ClNO2 production yield were estimated based on the field measurement, and the performance of the previously derived parameterizations was assessed. The nighttime ClNO2 correlated with particulate chloride and the mass concentration of fine particles (most likely due to aerosol surface area) suggested that the ClNO2 formation was limited by the N2O5 uptake at this site. By examining the relationship between particulate chloride and other species, we implied that anthropogenic emissions (e.g., biomass burning) rather than sea salt particles dominate the origin of particulate chloride, although the site was only about 100 km away from the ocean. A box model with detailed chlorine chemistry is used to investigate the impacts of ClNO2 chemistry on atmospheric oxidation. Model simulations showed that the chlorine radical liberated by ClNO2 photolysis during the next day had a slight increase in concentrations of OH, HO2, and RO2 radicals, as well as minor contributions to RO2 radical and O3 formation (< 5 %, on daytime average), in all the three types of air masses. Relatively high contributions were observed in Type A and B. The overall low contributions of ClNO2 to atmospheric oxidation are consistent with those reported recently from wintertime observations in China (including Shanghai, Beijing, Wangdu, and Mt. Tai). This may be attributed to the following: (1) relatively low particle mass concentration limited ClNO2 formation; (2) other reactions channels, like nitrous acid (HONO), oxygenated volatile organic compounds (OVOCs, including formaldehyde), and ozone photolysis had a more significant radical formation rate during the ozone pollution episodes and weakened the ClNO2 contribution indirectly. The results provided scientific insights into the role of nighttime chemistry in photochemical pollution under various scenarios in coastal areas.

Physical and chemical characterization of urban grime: An impact on the NO2 uptake coefficients and N-containing product compounds.

Urban grime represents an important environmental surface for heterogeneous reactions in urban environment. Here, we assess the physical and chemical properties of urban grime collected during six consecutive months in downtown of Guangzhou, China. There is a significant variation of the uptake coefficients of NO2 on the urban grime as a function of the relative humidity (RH). In absence of water molecules (0% RH), the light-induced uptake coefficients of NO2 on urban grime samples collected during six months are very similar in order of ≈10-6. At 80% RH, depending on the sampling month the light-induced uptake coefficient of NO2 can reach one order of magnitude higher values (1.5 × 10-5, at 80% RH) compared to those uptakes at 0% RH. In presence of 80% RH, there are strong correlations between the measured NO2 uptakes and the concentrations of the water soluble carbon, soluble anions, polycyclic aromatic hydrocarbons and n-alkanes depicted in the urban grime. These correlations, demonstrate that surface adsorbed water on urban grime play an important role for the uptakes of NO2. The heterogeneous conversion of NO2 on two-month old urban grime under sunlight irradiation (68 W m-2, 300 nm < λ < 400 nm) at 60% RH leads to the formation of unprecedented HONO surface flux of 4.7 × 1010 molecules cm-2 s-1 which is higher than all previously observed HONO fluxes, thereby affecting the oxidation capacity of the urban atmosphere. During the heterogeneous chemistry of NO2 with urban grime, the unsaturated and N-containing organic compounds are released in the gas phase which can affect the air quality in the urban environment.

Heterogeneous reaction of NO2 with feldspar, three clay minerals and Arizona Test Dust

Heterogeneous reaction of NO2 with mineral dust aerosol may play important roles in troposphere chemistry, and has been investigated by a number of laboratory studies. However, the influence of mineralogy on this reaction has not been well understood, and its impact on aerosol hygroscopicity is not yet clear. This work investigated heterogeneous reactions of NO2 (∼10 ppmv) with K-feldspar, illite, kaolinite, montmorillonite and Arizona Test Dust (ATD) at room temperature as a function of relative humidity (<1% to 80%) and reaction time (up to 24 hr). Heterogeneous reactivity towards NO2 was low for illite, kaolinite, montmorillonite and ATD, and uptake coefficients of NO2, γ(NO2), were determined to be around or smaller than 1×10−8; K-feldspar exhibited higher reactivity towards NO2, and CaCO3 is most reactive among the nine mineral dust samples considered in this and previous work. After heterogeneous reaction with NO2 for 24 hr, increase in hygroscopicity was nearly insignificant for illite, kaolinite and montmorillonite, and small but significant for K-feldspar; in addition, large increase in hygroscopicity was observed for ATD, although the increase in hygroscopicity was still smaller than CaCO3.

Fast Nocturnal Heterogeneous Chemistry in a Coastal Background Atmosphere and Its Implications for Daytime Photochemistry

AbstractNitryl chloride (ClNO2) is an important chlorine reservoir in the atmosphere that affects the oxidation capacity by producing first‐ and second‐generation radicals, but it has been rarely observed in the world. Here, online measurements of both N2O5 and ClNO2 at a coastal background site in the Pearl River Delta (PRD) in southern China, a region with high atmospheric oxidation capacity in the daytime, are presented. We observed continuous accumulation of elevated ClNO2 at night, while N2O5 was generally low. The maximum concentrations of N2O5 and ClNO2 were 1.4 and 1.7 ppbv, respectively, associated with a transported urban plume with high levels of O3 and NO2. The average product of N2O5 uptake coefficient and ClNO2 yield (γ × f = 0.02, with average γ of 0.027 and f of 0.71) was roughly twice those in urban areas in China, indicating active N2O5 heterogenous chemistry and effective ClNO2 formation in the background atmosphere. The production rate of Cl radicals (pCl) from the photolysis of ClNO2 was estimated to be an order of magnitude higher than those at coastal and rural sites in the literature. Such levels of Cl radical production could have considerable contribution to the atmospheric oxidation capacity after sunrise. In addition, NO2 produced by ClNO2 photolysis in the morning accounted for approximately 10% of the NO2 increase within several hours after sunrise. Thus, high nocturnal ClNO2 production and its following daytime photochemistry should be considered seriously in regional air quality modeling in the PRD and regions with similar conditions.

Inorganic Ions Enhance the Number of Product Compounds through Heterogeneous Processing of Gaseous NO2 on an Aqueous Layer of Acetosyringone.

Methoxyphenols represent important pollutants that can participate in the formation of secondary organic aerosols (SOAs) through chemical reactions with atmospheric oxidants. In this study, we determine the influence of ionic strength, pH, and temperature on the heterogeneous reaction of NO2 with an aqueous film consisting of acetosyringone (ACS), as a proxy for methoxyphenols. The uptake coefficient of NO2 (50 ppb) on ACS (1 × 10-5 mol L-1) is γ = (9.3 ± 0.09) × 10-8 at pH 5, and increases by one order of magnitude to γ = (8.6 ± 0.5) × 10-7 at pH 11. The lifetime of ACS due to its reaction with NO2 is largely affected by the presence of nitrate ions and sulfate ions encountered in aqueous aerosols. The analysis performed by membrane inlet single-photon ionization-time-of-flight mass spectrometry (MI-SPI-TOFMS) reveals an increase in the number of product compounds and a change of their chemical composition upon addition of nitrate ions and sulfate ions to the aqueous thin layer consisting of ACS. These outcomes indicate that inorganic ions can play an important role during the heterogeneous oxidation processes in aqueous aerosol particles.

The impact of chlorine chemistry combined with heterogeneous N&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O&amp;lt;sub&amp;gt;5&amp;lt;/sub&amp;gt; reactions on air quality in China

Abstract. The heterogeneous reaction of N2O5 on Cl-containing aerosols (heterogeneous N2O5 + Cl chemistry) plays a key role in chlorine activation, NOx recycling, and consequently O3 and PM2.5 formation. In this study, we use the GEOS-Chem model with additional anthropogenic and biomass burning chlorine emissions combined with updated parameterizations for the heterogeneous N2O5 + Cl chemistry (i.e., the uptake coefficient of N2O5 (γN2O5) and the ClNO2 yield (φClNO2)) to investigate the impacts of chlorine chemistry on air quality in China, the role of the heterogeneous N2O5 + Cl chemistry, and the sensitivity of air pollution formation to chlorine emissions and parameterizations for γN2O5 and φClNO2. The model simulations are evaluated against multiple observational datasets across China and show significant improvement in reproducing observations of particulate chloride, N2O5, and ClNO2 when including anthropogenic chlorine emissions and updates to the parameterization of the heterogeneous N2O5 + Cl chemistry relative to the default model. The simulations show that total tropospheric chlorine chemistry could increase annual mean maximum daily 8 h average (MDA8) O3 by up to 4.5 ppbv but decrease PM2.5 by up to 7.9 µg m−3 in China, 83 % and 90 % of which could be attributed to the effect of the heterogeneous N2O5 + Cl chemistry. The heterogeneous uptake of N2O5 on chloride-containing aerosol surfaces is an important loss pathway of N2O5 as well as an important source of O3 and hence is particularly useful in elucidating the commonly seen ozone underestimations relative to observations. The importance of chlorine chemistry largely depends on both chlorine emissions and the parameterizations for the heterogeneous N2O5 + Cl chemistry. With the additional chlorine emissions, the simulations show that annual MDA8 O3 in China could be increased by up to 3.5 ppbv. The corresponding effect on PM2.5 concentrations varies largely with regions, with an increase of up to 4.5 µg m−3 in the North China Plain but a decrease of up to 3.7 µg m−3 in the Sichuan Basin. On the other hand, even with the same chlorine emissions, the effects on MDA8 O3 and PM2.5 in China could differ by 48 % and 27 %, respectively, between different parameterizations.

A case study of heavy PM2.5 secondary formation by N2O5 nocturnal chemistry in Seoul, Korea in January 2018: Model performance and error analysis

Heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) plays an important role in nighttime nitrate (NO3−) formation in urban areas, and sometimes influences the occurrence of heavy PM2.5 pollution the next day in the Seoul Metropolitan Area (SMA), Korea. Here, we discuss the heavy PM2.5 wintertime episode of January 13–15, 2018, which was mainly induced by nighttime N2O5 heterogeneous reaction in the SMA. In our case, we confirmed that nighttime N2O5 hydrolysis is the most critical factor in the rapid formation of aerosol nitrate at high levels during the night, which prevailed in the morning of the next day. Our Integrated Process Rate (IPR) analysis showed that nighttime nitrate production in the episode was almost solely attributable to N2O5 chemistry, with hourly mean production rates of 0.8 ± 0.4 μg/m3 per hour in SMA, which is comparable to the daytime nitrate photochemical production rates of 0.9 ± 0.5 μg/m3 per hour. We also carried out a series of assessment of N2O5–driven nitrate formation sensitivity, and relevant errors were quantified by applying different N2O5 uptake coefficients in the WRF-CMAQ model. The potential errors of nighttime-average nitrate concentrations induced by N2O5 uptake process were assessed from a linear perspective for the planetary boundary layer (PBL) variances caused by four different PBL parameterization schemes: YSU, ACM2, MYJ, and QNSE. The potential error ranges by N2O5 uptake process were analyzed to be 2.3 to 3.5 μg/m3 (~10% relative to the nighttime-average), while biases of PBL simulations from 4 parameterization schemes were 2.3 ± 1.0 μg/m3, showing similar ranges in our episode. Although N2O5–driven heavy PM2.5 episodes do not occur often in SMA, our findings suggest the importance of N2O5 chemistry in vigorous wintertime nitrate formation and operational prediction errors of such PM2.5 episodes, under the premise of enhanced PBL simulation capabilities.

Contribution of Vehicle Emission and NO2 Surface Conversion to Nitrous Acid (HONO) in Urban Environments: Implications from Tests in a Tunnel.

Nitrous acid (HONO) is an important photochemical precursor to hydroxyl radicals particularly in an urban atmosphere, yet its primary emission and secondary production are often poorly constrained. Here, we measured HONO and nitrogen oxides (NOx) at both the inlet and the outlet in a busy urban tunnel (>30 000 vehicles per day) in south China. Multiple linear regression revealed that 73.9% of the inlet-outlet incremental HONO concentration was explained by NO2 surface conversion, while the rest was directly emitted from vehicles with an average HONO/NOx ratio of 1.31 ± 0.87%, which was higher than that from previous tunnel studies. The uptake coefficient of NO2, γ(NO2), on the tunnel surfaces was calculated to be (7.01 ± 0.02) × 10-5, much higher than that widely used in models. As tunnel surfaces are typical of urban surfaces in the wall and road materials, the dominance of HONO from surface reactions in the poorly lit urban tunnel demonstrated the importance of NO2 conversion on urban surfaces, instead of NO2 conversion on the aerosol surface, for both daytime and night-time HONO even in polluted ambient air. The higher γ(NO2) on urban surfaces and the elevated HONO/NOx ratio from this study can help explain the missing HONO sources in urban areas.

Effect of Inorganic Salts on N-Containing Organic Compounds Formed by Heterogeneous Reaction of NO2 with Oleic Acid.

Fatty acids are ubiquitous constituents of grime on urban and indoor surfaces and they represent important surfactants on organic aerosol particles in the atmosphere. Here, we assess the heterogeneous processing of NO2 on films consisting of pure oleic acid (OA) or a mixture of OA and representative salts for urban grime and aerosol particles, namely Na2SO4 and NaNO3. The uptake coefficients of NO2 on OA under light irradiation (300 nm < λ < 400 nm) decreased with increasing relative humidity (RH), from (1.4 ± 0.1) × 10-6 at 0% RH to (7.1 ± 1.6) × 10-7 at 90% RH. The uptake process of NO2 on OA gives HONO as a reaction product, and the highest HONO production was observed upon the heterogeneous reaction of NO2 with OA in the presence of nitrate (NO3-) ions. The formation of gaseous nitroaromatic compounds was also enhanced in the presence of NO3- ions upon light-induced heterogeneous processing of NO2 with OA, as revealed by membrane inlet single-photon ionization time-of-flight mass spectrometry (MI-SPI-TOFMS). These results suggest that inorganic salts can affect the heterogeneous conversion of gaseous NO2 on fatty acids and enhance the formation of HONO and other N-containing organic compounds in the atmosphere.

Production of HONO from NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; uptake on illuminated TiO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; aerosol particles and following the illumination of mixed TiO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;∕ammonium nitrate particles

Abstract. The rate of production of HONO from illuminated TiO2 aerosols in the presence of NO2 was measured using an aerosol flow tube system coupled to a photo-fragmentation laser-induced fluorescence detection apparatus. The reactive uptake coefficient of NO2 to form HONO, γNO2→HONO, was determined for NO2 mixing ratios in the range 34–400 ppb, with γNO2→HONO spanning the range (9.97 ± 3.52) × 10−6 to (1.26 ± 0.17) × 10−4 at a relative humidity of 15 ± 1 % and for a lamp photon flux of (1.63 ± 0.09) ×1016 photons cm−2 s−1 (integrated between 290 and 400 nm), which is similar to midday ambient actinic flux values. γNO2→HONO increased as a function of NO2 mixing ratio at low NO2 before peaking at (1.26 ± 0.17) ×10-4 at ∼ 51 ppb NO2 and then sharply decreasing at higher NO2 mixing ratios rather than levelling off, which would be indicative of surface saturation. The dependence of HONO production on relative humidity was also investigated, with a peak in production of HONO from TiO2 aerosol surfaces found at ∼ 25 % RH. Possible mechanisms consistent with the observed trends in both the HONO production and reactive uptake coefficient were investigated using a zero-dimensional kinetic box model. The modelling studies supported a mechanism for HONO production on the aerosol surface involving two molecules of NO2, as well as a surface HONO loss mechanism which is dependent upon NO2. In a separate experiment, significant production of HONO was observed from illumination of mixed nitrate/TiO2 aerosols in the absence of NO2. However, no production of HONO was seen from the illumination of nitrate aerosols alone. The rate of production of HONO observed from mixed nitrate/TiO2 aerosols was scaled to ambient conditions found at the Cape Verde Atmospheric Observatory (CVAO) in the remote tropical marine boundary layer. The rate of HONO production from aerosol particulate nitrate photolysis containing a photocatalyst was found to be similar to the missing HONO production rate necessary to reproduce observed concentrations of HONO at CVAO. These results provide evidence that particulate nitrate photolysis may have a significant impact on the production of HONO and hence NOx in the marine boundary layer where mixed aerosols containing nitrate and a photocatalytic species such as TiO2, as found in dust, are present.

Unexpectedly High Indoor HONO Concentrations Associated with Photochemical NO2 Transformation on Glass Windows.

Nitrous acid (HONO) is an important gaseous pollutant contributing to indoor air pollution because it causes adverse health effects and is the main source of hydroxyl radicals (OH). Here, we present direct measurements of HONO produced through light-induced heterogeneous reactions of NO2 with grime adsorbed on glass window. The uptake coefficients of NO2 [γ(NO2)] on the glass plates from the kitchen increased markedly from (2.3 ± 0.1) × 10-6 at 0% RH to (4.1 ± 0.5) × 10-6 at 90% RH. We report a significant quantity of daytime HONO produced in the kitchen, compared to the living room and bedroom. Kinetic modeling suggests that phase state and bulk diffusivity play important roles in the NO2 uptake; the best fit to the measured uptake coefficients is obtained with fixed diffusion coefficients. Photon scattering may be occurring at the surface of the films, leading to enhanced photon-excitation rates of polycyclic aromatic hydrocarbons. By taking these effects into account, the results from this study indicate that the HONO yields obtained in this study can explain the missing HONO in the photochemical models describing the indoor air chemistry.

Observations of N2O5 and NO3 at a suburban environment in Yangtze river delta in China: Estimating heterogeneous N2O5 uptake coefficients

The nitrate radical (NO3) and dinitrogen pentoxide (N2O5) play an important role in the nocturnal atmosphere chemistry. Observations of NO3 radicals and N2O5 were performed in a semirural ground site at Tai'Zhou in polluted southern China using cavity ring down spectroscopy (CRDS) from 23 May to 15 June 2018. The observed NO3 and N2O5 concentrations were relatively low, with 1 min average value of 4.4 ± 2.2 and 26.0 ± 35.7 pptV, respectively. The N2O5 uptake coefficient was determined to be from 0.027 to 0.107 based on steady state lifetime method. Fast N2O5 hydrolysis was the largest contributor to the loss of NO3 and contributed to substantial nitrate formation, with an average value of 14.83 ± 6.01 µg/m3. Further analysis shows that the N2O5 heterogeneous reactions dominated the nocturnal NOx loss and the nocturnal NOx loss rate is 0.14 ± 0.02 over this region.

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO2) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NOx analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO2, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO2 varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO2 degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.

Wintertime N2O5 uptake coefficients over the North China Plain

The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) plays an important role in regulating NOx. The N2O5 uptake coefficient, γ(N2O5), was determined using an iterative box model that was constrained to observational data obtained in suburban Beijing from February to March 2016. The box model determined 2289 individual γ(N2O5) values that varied from <0.001 to 0.02 with an average value of 0.0046 ± 0.0039 (and a median value of 0.0032). We found the derived winter γ(N2O5) values in Beijing were relatively low as compared to values reported in previous field studies conducted during winter in Hong Kong (average value of 0.014) and the eastern U.S. coast (median value of 0.0143). In our study, field evidence of the suppression of γ(N2O5) values due to pNO3− content, organics and the enhancement by aerosol liquid water content (ALWC) is in line with previous laboratory study results. Low ALWC, high pNO3− content, and particle morphology (inorganic core with an organic shell) accounted for the low γ(N2O5) values in the North China Plain (NCP) during wintertime. The field-derived γ(N2O5) values are well reproduced by a revised parameterization method, which includes the aerosol size distribution, ALWC, nitrate and organic coating, suggesting the feasibility of comprehensive parameterization in the NCP during wintertime.