NO2 Mixing Ratios Research Articles

Impact of particulate nitrate photolysis on air quality over the Northern Hemisphere

We use the Community Multiscale Air Quality (CMAQv5.4) model to examine the potential impact of particulate nitrate (pNO3−) photolysis on air quality over the Northern Hemisphere. We estimate the photolysis frequency of pNO3− by scaling the photolysis frequency of nitric acid (HNO3) with an enhancement factor that varies between 10 and 100 depending on pNO3− and sea-salt aerosol concentrations and then perform CMAQ simulations without and with pNO3− photolysis to quantify the range of impacts on tropospheric composition. The photolysis of pNO3− produces gaseous nitrous acid (HONO) and nitrogen dioxide (NO2) over seawater thereby increasing atmospheric HONO and NO2 mixing ratios. HONO subsequently undergoes photolysis, producing hydroxyl radicals (OH). The increase in NO2 and OH alters atmospheric chemistry and enhances the atmospheric ozone (O3) mixing ratio over seawater, which is subsequently transported to downwind continental regions. Seasonal mean model O3 vertical column densities without pNO3− photolysis are lower than the Ozone Monitoring Instrument (OMI) retrievals, while the column densities with the pNO3− photolysis agree better with the OMI retrievals of tropospheric O3 burden. We compare model O3 mixing ratios with available surface observed data from the U.S., Japan, the Tropospheric Ozone Assessment Report – Phase II, and OpenAQ; and find that the model without pNO3− photolysis underestimates the observed data in winter and spring seasons and the model with pNO3− photolysis improves the comparison in both seasons, largely rectifying the pronounced underestimation in spring. Compared to measurements from the western U.S., model O3 mixing ratios with pNO3− photolysis agree better with observed data in all months due to the persistent underestimation of O3 without pNO3− photolysis. Compared to the ozonesonde measurements, model O3 mixing ratios with pNO3− photolysis also agree better with observed data than the model O3 without pNO3− photolysis.

Measurement report: Atmospheric nitrate radical chemistry in the South China Sea influenced by the urban outflow of the Pearl River Delta

Abstract. The nitrate radical (NO3) is a critical nocturnal atmospheric oxidant in the troposphere, which widely affects the fate of air pollutants and regulates air quality. Many previous works have reported the chemistry of NO3 in inland regions of China, while fewer studies target marine regions. Here, we present a field measurement of the NO3 reservoir, dinitrogen pentoxide (N2O5), and related species at a typical marine site (Da Wan Shan Island) located in the South China Sea in the winter of 2021. Two patterns of air masses were captured during the campaign, including the dominant airmass from inland China (IAM) with a percentage of ∼ 84 %, and the airmass from eastern coastal areas (CAM) with ∼ 16 %. During the IAM period, the NO3 production rate reached 1.6 ± 0.9 ppbv h−1 due to the transportation of the polluted urban plume with high NOx and O3. The average nocturnal N2O5 and the calculated NO3 mixing ratios were 119.5 ± 128.6 and 9.9 ± 12.5 pptv, respectively, and the steady-state lifetime of NO3 was 0.5 ± 0.7 min on average, indicating intensive nighttime chemistry and rapid NO3 loss at this site. By examining the reaction of NO3 with volatile organic compounds (VOCs) and N2O5 heterogeneous hydrolysis, we revealed that these two reaction pathways were not responsible for the NO3 loss (< 20 %) since the NO3 reactivity (k(NO3)) towards VOCs was small (5.2×10-3 s−1) and the aerosol loading was low. Instead, NO was proposed to significantly contribute to nocturnal NO3 loss at this site, despite the nocturnal NO concentration always below the parts per billion by volume level and near the instrument detection limit. This might be from the local soil emission or something else. We infer that the nocturnal chemical NO3 reactions would be largely enhanced once without NO emission in the open ocean after the air mass passes through this site, thus highlighting the strong influences of the urban outflow to the downwind marine areas in terms of nighttime chemistry. During the CAM period, nocturnal ozone was higher, while NOx was much lower. The NO3 production was still very fast, with a rate of 1.2 ppbv h−1. With the absence of N2O5 measurement in this period, the NO3 reactivity towards VOCs and N2O5 uptake were calculated to assess NO3 loss processes. We showed that the average k(NO3) from VOCs (56.5 %, 2.6 ± 0.9 × 10−3 s−1) was higher than that from N2O5 uptake (43.5 %, 2.0 ± 1.5 × 10−3 s−1) during the CAM period, indicating a longer NO3 / N2O5 lifetime than that during IAM period. This study improves the understanding of the nocturnal NO3 budget and environmental impacts with the interaction of anthropogenic and natural activities in marine regions.

Impact of temperature-dependent non-PAN peroxynitrate formation, RO2NO2, on nighttime atmospheric chemistry.

The formation of peroxynitrates (RO2NO2) from the reaction of peroxy radicals (RO2) and nitrogen dioxide (NO2) and their subsequent redissociation are typically not included in chemical mechanisms. This is often done to save computational time as the assumption is that the equilibrium is strongly towards the RO2 + NO2 reaction for most conditions. Exceptions are the reactions of the methyl peroxy radical due to its abundance in the atmosphere and of acyl-RO2 radicals due to the long lifetime of peroxyacyl nitrates RO2NO2 (PANs). In this study, the nighttime oxidation of cis-2-butene and trans-2-hexene in the presence of NO2 is investigated in the atmospheric simulation chamber SAPHIR, Forschungszentrum Jülich, Germany, at atmospherically-relevant conditions at different temperatures (≈276 K, ≈293 K, ≈305 K). Measured concentrations of peroxy and hydroperoxy radicals as well as other trace gases (ozone, NO2, volatile organic compounds) are compared to state-of-the-art zero-dimensional box model calculations. Good model-measurement agreement can only be achieved when reversible RO2 + NO2 reactions are included for all RO2 species using literature values available from the latest SAR by [Jenkin et al., Atmos. Chem. Phys., 2019, 19, 7691]. The good agreement observed gives confidence that the SAR, derived originally for aliphatic RO2, can be applied to a large range of substituted RO2 radicals, simplifying generalised implementation in chemical models. RO2NO2 concentrations from non-acyl RO2 radicals of up to 2 × 10 cm-3 are predicted at 276 K, impacting effectively the kinetics of RO2 radicals. Under these conditions, peroxy radicals are slowly regenerated downwind of the pollution source and may be lost in the atmosphere through deposition of RO2NO2. Based on this study, 60% of RO2 radicals would be stored as RO2NO2 at a temperature of 10 °C and in the presence of a few ppbv of NO2. The fraction increases further at colder temperatures and/or higher NO2 mixing ratios. This does not only affect the expected concentrations of RO2 radicals but, as the peroxynitrates can react with OH radicals or photolyse, they could comprise a net sink for RO2 radicals as well as increase the production of NOx (= NO + NO2) in different locations depending on their lifetime. Omitting this chemistry from the kinetic model can lead to misinterpreted product formation and may prevent reconciling observations and model predictions.

Local exposure misclassification in national models: relationships with urban infrastructure and demographics

BackgroundNational-scale linear regression-based modeling may mischaracterize localized patterns, including hyperlocal peaks and neighborhood- to regional-scale gradients. For studies focused on within-city differences, this mischaracterization poses a risk of exposure misclassification, affecting epidemiological and environmental justice conclusions.ObjectiveCharacterize the difference between intraurban pollution patterns predicted by national-scale land use regression modeling and observation-based estimates within a localized domain and examine the relationship between that difference and urban infrastructure and demographics.MethodsWe compare highly resolved (0.01 km2) observations of NO2 mixing ratio and ultrafine particle (UFP) count obtained via mobile monitoring with national model predictions in thirteen neighborhoods in the San Francisco Bay Area. Grid cell-level divergence between modeled and observed concentrations is termed “localized difference.” We use a flexible machine learning modeling technique, Bayesian Additive Regression Trees, to investigate potentially nonlinear relationships between discrepancy between localized difference and known local emission sources as well as census block group racial/ethnic composition.ResultsWe find that observed local pollution extremes are not represented by land use regression predictions and that observed UFP count significantly exceeds regression predictions. Machine learning models show significant nonlinear relationships among localized differences between predictions and observations and the density of several types of pollution-related infrastructure (roadways, commercial and industrial operations). In addition, localized difference was greater in areas with higher population density and a lower share of white non-Hispanic residents, indicating that exposure misclassification by national models differs among subpopulations.ImpactComparing national-scale pollution predictions with hyperlocal observations in the San Francisco Bay Area, we find greater discrepancies near major roadways and food service locations and systematic underestimation of concentrations in neighborhoods with a lower share of non-Hispanic white residents. These findings carry implications for using national-scale models in intraurban epidemiological and environmental justice applications and establish the potential utility of supplementing large-scale estimates with publicly available urban infrastructure and pollution source information.

Radical chemistry and ozone production at a UK coastal receptor site

Abstract. OH, HO2, total and partially speciated RO2, and OH reactivity (kOH′) were measured during the July 2015 ICOZA (Integrated Chemistry of OZone in the Atmosphere) project that took place at a coastal site in north Norfolk, UK. Maximum measured daily OH, HO2 and total RO2 radical concentrations were in the range 2.6–17 × 106, 0.75–4.2 × 108 and 2.3–8.0 × 108 molec. cm−3, respectively. kOH′ ranged from 1.7 to 17.6 s−1, with a median value of 4.7 s−1. ICOZA data were split by wind direction to assess differences in the radical chemistry between air that had passed over the North Sea (NW–SE sectors) and that over major urban conurbations such as London (SW sector). A box model using the Master Chemical Mechanism (MCMv3.3.1) was in reasonable agreement with the OH measurements, but it overpredicted HO2 observations in NW–SE air in the afternoon by a factor of ∼ 2–3, although slightly better agreement was found for HO2 in SW air (factor of ∼ 1.4–2.0 underprediction). The box model severely underpredicted total RO2 observations in both NW–SE and SW air by factors of ∼ 8–9 on average. Measured radical and kOH′ levels and measurement–model ratios displayed strong dependences on NO mixing ratios, with the results suggesting that peroxy radical chemistry is not well understood under high-NOx conditions. The simultaneous measurement of OH, HO2, total RO2 and kOH′ was used to derive experimental (i.e. observationally determined) budgets for all radical species as well as total ROx (i.e. OH + HO2 + RO2). In NW–SE air, the ROx budget could be closed during the daytime within experimental uncertainty, but the rate of OH destruction exceeded the rate of OH production, and the rate of HO2 production greatly exceeded the rate of HO2 destruction, while the opposite was true for RO2. In SW air, the ROx budget analysis indicated missing daytime ROx sources, but the OH budget was balanced, and the same imbalances were found with the HO2 and RO2 budgets as in NW–SE air. For HO2 and RO2, the budget imbalances were most severe at high-NO mixing ratios, and the best agreement between HO2 and RO2 rates of production and destruction rates was found when the RO2 + NO rate coefficient was reduced by a factor of 5. A photostationary-steady-state (PSS) calculation underpredicted daytime OH in NW–SE air by ∼ 35 %, whereas agreement (∼ 15 %) was found within instrumental uncertainty (∼ 26 % at 2σ) in SW air. The rate of in situ ozone production (P(Ox)) was calculated from observations of ROx, NO and NO2 and compared to that calculated from MCM-modelled radical concentrations. The MCM-calculated P(Ox) significantly underpredicted the measurement-calculated P(Ox) in the morning, and the degree of underprediction was found to scale with NO.

Technical note: Gas-phase nitrate radical generation via irradiation of aerated ceric ammonium nitrate mixtures

Abstract. We present a novel photolytic source of gas-phase NO3 suitable for use in atmospheric chemistry studies that has several advantages over traditional sources that utilize NO2 + O3 reactions and/or thermal dissociation of dinitrogen pentoxide (N2O5). The method generates NO3 via irradiation of aerated aqueous solutions of ceric ammonium nitrate (CAN, (NH4)2Ce(NO3)6) and nitric acid (HNO3) or sodium nitrate (NaNO3). We present experimental and model characterization of the NO3 formation potential of irradiated CAN / HNO3 and CAN / NaNO3 mixtures containing [CAN] = 10−3 to 1.0 M, [HNO3] = 1.0 to 6.0 M, [NaNO3] = 1.0 to 4.8 M, photon fluxes (I) ranging from 6.9 × 1014 to 1.0 × 1016 photons cm−2 s−1, and irradiation wavelengths ranging from 254 to 421 nm. NO3 mixing ratios ranging from parts per billion to parts per million by volume were achieved using this method. At the CAN solubility limit, maximum [NO3] was achieved using [HNO3] ≈ 3.0 to 6.0 M and UVA radiation (λmax⁡ = 369 nm) in CAN / HNO3 mixtures or [NaNO3] ≥ 1.0 M and UVC radiation (λmax⁡ = 254 nm) in CAN / NaNO3 mixtures. Other reactive nitrogen (NO2, N2O4, N2O5, N2O6, HNO2, HNO3, HNO4) and reactive oxygen (HO2, H2O2) species obtained from the irradiation of ceric nitrate mixtures were measured using a NOx analyzer and an iodide-adduct high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS). To assess the applicability of the method for studies of NO3-initiated oxidative aging processes, we generated and measured the chemical composition of oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) from the β-pinene + NO3 reaction using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the HR-ToF-CIMS.

Peroxy radical chemistry during ozone photochemical pollution season at a suburban site in the boundary of Jiangsu–Anhui–Shandong–Henan region, China

Ambient peroxy radical (RO2⁎ = HO2 + RO2) concentrations were measured at a suburban site in a major prefecture-level city (Huaibei) in the boundary of Jiangsu–Anhui–Shandong–Henan region, which is the connecting belt of air pollution in the Beijing–Tianjin–Hebei region and the Yangtze River Delta. Measurements were carried out during the period of September to October 2021 to elucidate the formation mechanism of O3 pollution. The observed maximum concentration of peroxy radicals was 73.8 pptv. A zero-dimensional box model (Framework for 0-Dimensional Atmospheric Modeling, F0AM) based on Master Chemical Mechanism (MCM3.3.1) was used to predict radical concentrations for comparison with observations. The model reproduced the daily variation of peroxy radicals well, but discrepancies still appear in the morning hours. As in previous field campaigns, systematic discrepancies between modelled and measured RO2⁎ concentrations are observed in the morning for NO mixing ratios higher than 1 ppbv. Between 6:00 and 9:00 am, the model significantly underpredicts RO2⁎ by a mean factor of 7.2. This underprediction can be explained by a missing RO2⁎ source of 1.2 ppbv h−1 which originated from the photochemical conversion of an alkene-like chemical species. From the model results it shows that the main sources of ROx (= OH + HO2 + RO2) are the photolysis of oxygenated volatile organic compounds (OVOCs, 33 %), O3 and HONO (25 %), and HCHO (24 %). And the major sinks of ROx transitioned from a predominant reaction of radicals with NOx in the morning to a predominant peroxy self- and cross-reaction in the late afternoon. The introduction of an alkene-like species increased RO2 radical concentration and resulted in 14 % increase in net daily integrated ozone production, indicating the possible significance of the mechanism of alkene-like species oxidation to peroxy radicals. This study provides important information for subsequent ozone pollution control policies in Jiangsu–Anhui–Shandong–Henan region.

Impact of HO2 aerosol uptake on radical levels and O3 production during summertime in Beijing

Abstract. The impact of heterogeneous uptake of HO2 on aerosol surfaces on radical concentrations and the O3 production regime in Beijing in summertime was investigated. The uptake coefficient of HO2 onto aerosol surfaces, γHO2, was calculated for the AIRPRO campaign in Beijing, in summer 2017, as a function of measured aerosol soluble copper concentration, [Cu2+]eff, aerosol liquid water content, [ALWC], and particulate matter concentration, [PM]. An average γHO2 across the entire campaign of 0.070±0.035 was calculated, with values ranging from 0.002 to 0.15, and found to be significantly lower than the value of γHO2=0.2, commonly used in modelling studies. Using the calculated γHO2 values for the summer AIRPRO campaign, OH, HO2 and RO2 radical concentrations were modelled using a box model incorporating the Master Chemical Mechanism (v3.3.1), with and without the addition of γHO2, and compared to the measured radical concentrations. The rate of destruction analysis showed the dominant HO2 loss pathway to be HO2 + NO for all NO concentrations across the summer Beijing campaign, with HO2 uptake contributing <0.3 % to the total loss of HO2 on average. This result for Beijing summertime would suggest that under most conditions encountered, HO2 uptake onto aerosol surfaces is not important to consider when investigating increasing O3 production with decreasing [PM] across the North China Plain. At low [NO], however, i.e. <0.1 ppb, which was often encountered in the afternoons, up to 29 % of modelled HO2 loss was due to HO2 uptake on aerosols when calculated γHO2 was included, even with the much lower γHO2 values compared to γHO2= 0.2, a result which agrees with the aerosol-inhibited O3 regime recently proposed by Ivatt et al. (2022). As such it can be concluded that in cleaner environments, away from polluted urban centres where HO2 loss chemistry is not dominated by NO but where aerosol surface area is high still, changes in PM concentration and hence aerosol surface area could still have a significant effect on both overall HO2 concentration and the O3 production regime. Using modelled radical concentrations, the absolute O3 sensitivity to NOx and volatile organic compounds (VOCs) showed that, on average across the summer AIRPRO campaign, the O3 production regime remained VOC-limited, with the exception of a few days in the afternoon when the NO mixing ratio dropped low enough for the O3 regime to shift towards being NOx-limited. The O3 sensitivity to VOCs, the dominant regime during the summer AIRPRO campaign, was observed to decrease and shift towards a NOx-sensitive regime both when NO mixing ratio decreased and with the addition of aerosol uptake. This suggests that if [NOx] continues to decrease in the future, ozone reduction policies focussing solely on NOx reductions may not be as efficient as expected if [PM] and, hence, HO2 uptake to aerosol surfaces continue to decrease. The addition of aerosol uptake into the model, for both the γHO2 calculated from measured data and when using a fixed value of γHO2=0.2, did not have a significant effect on the overall O3 production regime across the campaign. While not important for this campaign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.

Weekend-weekday variations, sources, and secondary transformation potential of volatile organic compounds in urban Zhengzhou, China

Periodical changes of human activities cause weekend-weekday differences of volatile organic compounds (VOCs) and nitrogen oxides (NO + NO2 = NOx) emissions, which induce urban ozone (O3) pollution and secondary organic aerosol (SOA) in fine particulate (with aerodynamic diameters ≤2.5 μm; PM2.5). However, influences of weekend-weekday differences in primary emissions on the production of secondary pollutants remain unknown. The TROPOspheric Monitoring Instrument and surface observations are carried to simultaneously monitor VOCs, NO2, O3, and PM2.5 concentrations in urban Zhengzhou, China during the weekend and the weekday. Reductions in anthropogenic activities result in atmospheric VOCs and NO2 reductions during the weekend. The ratios of formaldehyde columns to NO2 columns during the weekend afternoon and the weekday afternoon (0.53 and 0.39, respectively) are less than 2.30, indicating the O3 formation under the VOC-limited regime. Lower total VOCs (TVOCs) mixing ratios but higher ratios of TVOCs mixing ratios to NO2 mixing ratios during the weekend afternoon perform faster photochemical O3 production. In contrast, higher TVOCs mixing ratios are responsible for higher SOA formation during the weekday. Based on the positive matrix factorization model and VOCs reactivities, solvent usage, vehicle exhaust, and industrial sources are majorly responsible for SOA (80.1%) and O3 (79.9%) formation potential. To reduce O3 concentrations during the weekend and SOA concentrations during the weekday collaboratively, solvent, vehicle, and industrial activities should be transformed from weekday to weekend.

High urban NOx triggers a substantial chemical downward flux of ozone.

Nitrogen oxides (NOx) play a central role in catalyzing tropospheric ozone formation. Nitrogen dioxide (NO2) has recently reemerged as a key target for air pollution control measures, and observational evidence points toward a limited understanding of ozone in high-NOx environments. A complete understanding of the mechanisms controlling the rapid atmospheric cycling between ozone (O3)-nitric oxide (NO)-NO2 in high-NOx regimes at the surface is therefore paramount but remains challenging because of competing dynamical and chemical effects. Here, we present long-term eddy covariance measurements of O3, NO, and NO2, over an urban area, that allow disentangling important physical and chemical processes. When generalized, our findings suggest that the depositional O3 flux near the surface in urban environments is negligible compared to the flux caused by chemical conversion of O3. This leads to an underestimation of the Leighton ratio and is a key process for modulating urban NO2 mixing ratios. As a consequence, primary NO2 emissions have been significantly overestimated.

Variations of the urban PM2.5 chemical components and corresponding light extinction for three heating seasons in the Guanzhong Plain, China

In order to investigate the variations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 μm) chemical components responding to the pollution control strategy and their effect on light extinction (bext) in the Guanzhong Plain (GZP), the comparisons of urban atmospheric chemical components during the heating seasons were extensively conducted for three years. The average concentration of PM2.5 decreased significantly from 117.9 ± 57.3 μg m−3 in the heating season 1 (HS1) to 53.5 ± 31.3 μg m−3 in the heating season 3 (HS3), which implied that the effective strategies were implemented in recent years. The greatest contribution to PM2.5 (∼30%) was from Organic matter (OM). The heightened contributions of the secondary inorganic ions (SNA, including NO3−, SO42−, and NH4+) to PM2.5 were observed with the values of 34% (HS1), 41% (HS2), and 42% (HS3), respectively. The increased percentages of NO3− contributions indicated that the emission of NOx should be received special attention in the GZP. The comparison of PM2.5 chemical compositions and implications across major regions of China and the globe were investigated. NH4NO3 was the most important contributor to bext in three heating seasons. The average bext was decreased from 694.3 ± 399.1 Mm−1 (HS1) to 359.3 ± 202.3 Mm−1 (HS3). PM2.5 had a threshold concentration of 75 μg m−3, 64 μg m−3, and 57 μg m−3 corresponding to the visual range (VR) < 10 km in HS1, HS2, and HS3, respectively. The enhanced impacts of the oxidant on PM2.5 and O3 were observed based on the long-term variations in PM2.5 and OX (Oxidant, the sum of O3 and NO2 mixing ratios) over the five heating seasons and PM2.5 and O3 over six summers from 2016 to 2021. The importance of coordinated control of PM2.5 and O3 was also investigated in the GZP.

A lightweight broadband cavity-enhanced spectrometer for NO2 measurement on uncrewed aerial vehicles

Abstract. We describe the design and performance of a lightweight broadband cavity-enhanced spectrometer for measurement of NO2 on uncrewed aerial vehicles and light aircraft. The instrument uses a light-emitting diode (LED) centered at 457 nm, high-finesse mirrors (reflectivity =0.999963 at 450 nm), and a grating spectrometer to determine optical extinction coefficients between 430 and 476 nm, which are fit with custom spectral fitting software and published absorption cross sections. The instrument weighs 3.05 kg and has a power consumption of less than 35 W at 25 ∘C. A ground calibration unit provides helium and zero air flows to periodically determine the reflectivity of the cavity mirrors using known Rayleigh scattering cross sections. The precision (1σ) for laboratory measurements is 43 ppt NO2 in 1 s and 7 ppt NO2 in 30 s. Measurement of air with known NO2 mixing ratios in the range of 0–70 ppb agreed with the known values within 0.3 % (slope =0.997±0.007; r2=0.99983). We demonstrate instrument performance using vertical profiles of the NO2 mixing ratio acquired on board an uncrewed aerial vehicle between 0 and 110 m above ground level in Boulder, Colorado.

Origin of CO2, CH4, and N2O trapped in ice wedges in central Yakutia and their relationship

AbstractPermafrost thawing as a result of global warming is expected to foster the biological remineralization of intact organic carbon and nitrogen and release greenhouse gas (GHG) into the atmosphere, which will have positive feedback for future global warming. However, GHG budgets and their controls in permafrost ground ice are not yet fully understood. This study aims to better understand the control mechanisms of GHG in ground ice by using new gas and chemistry data. In this study, we present new data on carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) mixing ratios in three different ice wedges, Churapcha, Syrdakh, and Cyuie, located in central Yakutia, Siberia. The GHG mixing ratios in the studied ice wedges range from 0.0% to 13.8% CO2, 1.3–91.2 ppm CH4, and 0% and 0–1414 N2O. In particular, all three ice wedges demonstrate that ice‐wedge samples enriched in CH4 were depleted in N2O mixing ratios and vice versa. N2–O2–Ar compositions indicate that the studied ice wedges were most likely formed by dry snow or hoarfrost, not by freezing of snow meltwater, and the O2‐consuming biological metabolism was active. Most of the observed GHG mixing ratios cannot be explained without microbial metabolism. The inhibitory impact of denitrification products of nitrate (including N2O) could be an important control of the ice‐wedge CH4 mixing ratio.

Diagnosis of Ozone Formation Sensitivities in Different Height Layers via MAX‐DOAS Observations in Guangzhou

AbstractDiagnosing the vertical distributions of ozone formation sensitivities within the boundary layers is the prerequisite for formulating proper ozone control strategies. From 1 January 2020, to 20 August 2021, a multi‐function MAX‐DOAS instrument was set up in Guangzhou to detect the NO2 and HCHO vertical profiles. The ozone formation sensitivities in different height layers were diagnosed using the FNRsec, which was defined as the ratio of secondary HCHO to NO2 VMRs (HCHOsec/NO2). The secondary sources in ambient HCHO participate in the photochemical reactions directly, and the FNRsec can indicate the ozone formation sensitivities more accurately. Therefore, the secondary source was separated from ambient HCHO via a multi‐linear regression method, and its relative contribution was approximately 66.9 ± 6.3%. The sensitivity thresholds of ozone formation were determined by the slope of the linear regression analysis for O3 versus the normalized secondary HCHO or NO2 mixing ratios for different FNRsec ranges, which were 0.22 and 0.36. For the ground layer, the VOC‐limited, transitional, and NOx‐limited regimes accounted for 40.66%, 32.42%, and 26.92%, respectively. Diurnally, the ground layer was usually in the VOC‐limited regime in morning, but in the transitional regime in noon and afternoon. Vertically, the ozone formation sensitivity changed with altitude from VOC‐limited (0.02–0.22 km) to transitional (0.22–0.42 km) to NOx‐limited (0.42–2.02 km). These findings can help formulate proper ozone control strategies in time according to the varying local conditions.

Fate of the nitrate radical at the summit of a semi-rural mountain site in Germany assessed with direct reactivity measurements

Abstract. The reactivity of NO3 plays an important role in modifying the fate of reactive nitrogen species at nighttime. High reactivity (e.g. towards unsaturated volatile organic compounds – VOCs) can lead to formation of organic nitrates and secondary organic aerosol, whereas low reactivity opens the possibility of heterogeneous NOx losses via the formation and uptake of N2O5 to particles. We present direct NO3 reactivity measurements (kNO3) that quantify the VOC-induced losses of NO3 during the TO2021 campaign at the summit of the Kleiner Feldberg mountain (825 m, Germany) in July 2021. kNO3 was on average ∼0.035 s−1 during the daytime, ∼0.015 s−1 for almost half of the nights and below the detection limit of 0.006 s−1 for the other half, which may be linked to sampling from above the nocturnal surface layer. NO3 reactivities derived from VOC measurements and the corresponding rate coefficient were in good agreement with kNO3, with monoterpenes representing 84 % of the total reactivity. The fractional contribution F of kNO3 to the overall NO3 loss rate (which includes an additional reaction of NO3 with NO and photolysis) were on average ∼16 % during the daytime and ∼50 %–60 % during the nighttime. The relatively low nighttime value of F is related to the presence of several tens of parts per trillion by volume (pptv) of NO on several nights. NO3 mixing ratios were not measured, but steady-state calculations resulted in nighttime values between &lt;1 and 12 pptv. A comparison of results from TO2021 with direct measurements of NO3 during previous campaigns between 2008 and 2015 at this site revealed that NO3 loss rates were remarkably high during TO2021, while NO3 production rates were low. We observed NO mixing ratios of up to 80 pptv at night, which has implications for the cycling of reactive nitrogen at this site. With O3 present at levels of mostly 25 to 60 ppbv (parts per billion by volume), NO is oxidized to NO2 on a timescale of a few minutes. We find that maintaining NO mixing ratios of, e.g., 40 pptv requires a ground-level NO emission rate of 0.33 pptv s−1 (into a shallow surface layer of 10 m depth). This in turn requires a rapid deposition of NO2 to the surface (vdNO2∼0.15 cm s−1) to reduce nocturnal NO2 levels to match the observations.

OH and HO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; radical chemistry at a suburban site during the EXPLORE-YRD campaign in 2018

Abstract. The first OH and HO2 radical observation in Yangtze River Delta, one of the four major urban agglomerations in China, was carried out at a suburban site (Taizhou) in summer 2018 from May to June, aiming to elucidate the atmospheric oxidation capacity in this region. The maximum diurnal averaged OH and HO2 concentrations were 1.0×107 and 1.1×109 cm−3, respectively, which were the second highest HOx (sum of OH and HO2) radical concentrations observed in China. HONO photolysis was the dominant radical primary source, accounting for 42 % of the total radical initiation rate. Other contributions were from carbonyl photolysis (including HCHO, 24 %), O3 photolysis (17 %), alkene ozonolysis (14 %), and NO3 oxidation (3 %). A chemical box model based on the RACM2-LIM1 mechanism could generally reproduce the observed HOx radicals, but systematic discrepancy remained in the afternoon for the OH radical, when the NO mixing ratio was less than 0.3 ppb. An additional recycling mechanism equivalent to 100 ppt NO was capable to fill the gap. The sum of monoterpenes was on average up to 0.4 ppb during daytime, which was all allocated to α-pinene in the base model. A sensitivity test without monoterpene input showed the modeled OH and HO2 concentrations would increase by 7 % and 4 %, respectively, but modeled RO2 concentration would significantly decrease by 23 %, indicating that monoterpene was an important precursor of RO2 radicals in this study. Consequently, the daily integrated net ozone production would reduce by 6.3 ppb without monoterpene input, proving the significant role of monoterpene in the photochemical O3 production in this study. In addition, the generally good agreement between observed and modeled HOx concentrations suggested no significant HO2 heterogeneous uptake process during this campaign. Incorporation of HO2 heterogeneous uptake process would worsen the agreement between HOx radical observation and simulation, and the discrepancy would be beyond the combined measurement–model uncertainties using an effective uptake coefficient of 0.2. Finally, the ozone production efficiency (OPE) was only 1.7 in this study, a few folds lower than other studies in (sub)urban environments. The low OPE indicated a slow radical propagation rate and short chain length. As a consequence, ozone formation was suppressed by the low NO concentration in this study.

Evaluation of WRF-Chem model (v3.9.1.1) real-time air quality forecasts over the Eastern Mediterranean

Abstract. We describe and evaluate a high-resolution real-time air quality forecast system over the Eastern Mediterranean, based on a regional, online coupled atmospheric chemistry and aerosol model. The Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) is used to perform daily, 3 d forecasts of regulated pollutants (NO2, O3, PM2.5) over the Eastern Mediterranean, applying three nested domains with horizontal resolutions of 50, 10 and 2 km, the latter focusing on Cyprus. Natural (dust, sea-salt, biogenic) emissions are calculated online, while anthropogenic emissions are based on the Emissions Database for Global Atmospheric Research – Hemispheric Transport of Air Pollution (EDGAR-HTAP) global emission inventory. A high spatial (1 km) and temporal (hourly) anthropogenic emission inventory is used for the island of Cyprus in the innermost domain. The model skill in forecasting the concentrations of atmospheric pollutants is evaluated using measurements from a network of nine ground stations in Cyprus and compared with the forecasting skill of the EU Copernicus Atmosphere Monitoring Service (CAMS). The forecast of surface temperature, pressure, and wind speed is found to be accurate, with minor discrepancies between the modelled and observed 10 m wind speed at mountainous and coastal sites attributed to the limited representation of the complex topography of Cyprus. Compared to CAMS, the WRF-Chem model predicts with higher accuracy the NO2 mixing ratios at the residential site with a normalized mean bias (NMB) of 7 % during winter and −44 % during summer, whereas the corresponding biases for CAMS are −81 % and −84 %. Due to the high temporal resolution of the anthropogenic emission inventory, the WRF-Chem model captures more accurately the diurnal profiles of NO2 and O3 mixing ratios at the residential site. Background PM2.5 concentrations influenced by long-range transport are overestimated by the WRF-Chem model during winter (NMB = 54 %), whereas the corresponding NMB for CAMS is 11 %. Our results support the adoption of regional, online coupled air quality models over chemical transport models for real-time air quality forecasts.

Tropospheric ozone production and chemical regime analysis during the COVID-19 lockdown over Europe

Abstract. The COVID-19 (coronavirus disease 2019) European lockdowns have led to a significant reduction in the emissions of primary pollutants such as NO (nitric oxide) and NO2 (nitrogen dioxide). As most photochemical processes are related to nitrogen oxide (NOx≡ NO + NO2) chemistry, this event has presented an exceptional opportunity to investigate its effects on air quality and secondary pollutants, such as tropospheric ozone (O3). In this study, we present the effects of the COVID-19 lockdown on atmospheric trace gas concentrations, net ozone production rates (NOPRs) and the dominant chemical regime throughout the troposphere based on three different research aircraft campaigns across Europe. These are the UTOPIHAN (Upper Tropospheric Ozone: Processes Involving HOx and NOx) campaigns in 2003 and 2004, the HOOVER (HOx over Europe) campaigns in 2006 and 2007, and the BLUESKY campaign in 2020, the latter performed during the COVID-19 lockdown. We present in situ observations and simulation results from the ECHAM5 (fifth-generation European Centre Hamburg general circulation model, version 5.3.02)/MESSy2 (second-generation Modular Earth Submodel System, version 2.54.0) Atmospheric Chemistry (EMAC), model which allows for scenario calculations with business-as-usual emissions during the BLUESKY campaign, referred to as the “no-lockdown scenario”. We show that the COVID-19 lockdown reduced NO and NO2 mixing ratios in the upper troposphere by around 55 % compared to the no-lockdown scenario due to reduced air traffic. O3 production and loss terms reflected this reduction with a deceleration in O3 cycling due to reduced mixing ratios of NOx, while NOPRs were largely unaffected. We also study the role of methyl peroxyradicals forming HCHO (αCH3O2) to show that the COVID-19 lockdown shifted the chemistry in the upper-troposphere–tropopause region to a NOx-limited regime during BLUESKY. In comparison, we find a volatile organic compound (VOC)-limited regime to be dominant during UTOPIHAN.

Assessment of Impact of Meteorology and Precursor in Long-term Trends of PM and Ozone in a Tropical City

Long-term trends of atmospheric pollutants, particularly ozone (O3) and particulate matter (PM) provide a direct evaluation of the response of the atmosphere to the environmental policies and the variability of anthropogenic and biogenic emissions. Here, we report the assessment of the temporal evolution of the air quality in a tropical urban city (Butuan) in the southern Philippines by evaluating the trends of meteorological conditions (i.e., temperature, R.H., boundary layer height), air pollutants (i.e., PM2.5, NO2, O3) and their precursors (Benzene, Toluene, and Xylene) from 2014 to 2020. During the seven-year measurement, the mean PM2.5 and PM10 mass concentrations were 8.7 ± 3.9 and 24.3 ± 12.0 µg m–3, with no single day exceeded the daily PM limit. The max concentrations of aerosol occurred during the dry season when the loss of particles through wet deposition was limited. Speciation of PM2.5 indicated that fine aerosol was dominated by sea salt and organic matter (OM). Analysis of the ratio of OM and sulfate indicated that the main source of pollution in the city was wildfire/biomass burning. The average O3 and NO2 mixing ratios during the same period were 22.3 ± 9.5 ppb and 8.1 ± 5.4 ppb while increasing at the rate of 0.409 ppb year–1 and 0.683 ppb year–1. The highest O3 concentration occurred during the summer months when photochemistry enhanced the formation of tropospheric O3. The increasing O3 trend was attributed to the contribution of anthropogenic VOCs (AVOCs), based on their ozone-forming potentials (OFPs). The seven-year measurement also showcased the variability of the atmospheric pollutants during the COVID-19 pandemic of 2020, when O3 substantially increased due to reduced vehicle transport activities. Overall, our results provide insights to better comprehend the sources of the variability of O3 and PM on a long-term temporal scale, as well as implications on relevant environmental policies in controlling air pollutants in a tropical developing region.

Nitrous acid production and uptake by Zea mays plants in growth chambers in the presence of nitrogen dioxide

Nitrous acid (HONO) photolysis is an important atmospheric reaction that leads to the formation of hydroxyl radicals (OH), the main diurnal atmospheric oxidants. The process of HONO formation remains unclear, and comparisons between field measurements and model results have highlighted the presence of unknown HONO sources. HONO production on plant surfaces was recently suggested to contribute to atmospheric HONO formation, but there is limited information on the quantification of HONO production and uptake by plants. To address this gap in the existing knowledge, the current study investigated HONO exchange on living Zea mays plants. Experiments were conducted in growth chambers under controlled experimental conditions (temperature, relative humidity, NO2 mixing ratio, light intensity, CO2 mixing ratio) at temperatures ranging between 283 and 299 K. To investigate the effect of drought on HONO plant-atmosphere exchanges, experiments were carried out on two sets of Zea mays plants exposed to two different water supply conditions during their growth: optimal watering (70% of the field capacity) and water stress (30% of the field capacity). Results indicated that the uptake of HONO by control Zea mays plants increased linearly with ambient temperature, and was correlated with CO2 assimilation for temperatures ranging from 283 to 299 K. At 299 K, HONO production on the leaves offset this uptake and Zea mays plants were a source of HONO, with a net production rate of 27 ± 7 ppt h-1. Deposition velocities were higher for HONO than CO2, suggesting a higher mesophyll resistance for CO2 than HONO. As water stress reduced the stomatal opening, it also decreased plant-atmosphere gas exchange. Thus, climate change, which may limit the availability of water, will have an impact on HONO exchange between plants and the atmosphere.