Radical Budget Research Articles

Using observed urban NOx sinks to constrain VOC reactivity and the ozone and radical budget in the Seoul Metropolitan Area

Abstract. Ozone (O3) is an important secondary pollutant that impacts air quality and human health. Eastern Asia has high regional O3 background due to the numerous sources and increasing and rapid industrial growth, which also impacts the Seoul Metropolitan Area (SMA). However, the SMA has also been experiencing increasing O3 driven by decreasing NOx emissions, highlighting the role of the local in situ O3 production on the SMA. Here, comprehensive gas-phase measurements collected on the NASA DC-8 during the National Institute of Environmental Research (NIER)/NASA Korea–United States Air Quality (KORUS-AQ) study are used to constrain the instantaneous O3 production rate over the SMA. The observed NOx oxidized products support the importance of non-measured peroxy nitrates (PNs) in the O3 chemistry in the SMA, as they accounted for ∼49 % of the total PNs. Using the total measured PNs (ΣPNs) and alkyl and multifunctional nitrates (ΣANs), unmeasured volatile organic compound (VOC) reactivity (R(VOC)) is constrained and found to range from 1.4–2.1 s−1. Combining the observationally constrained R(VOC) with the other measurements on the DC-8, the instantaneous net O3 production rate, which is as high as ∼10 ppbv h−1, along with the important sinks of O3 and radical chemistry, is constrained. This analysis shows that ΣPNs play an important role in both the sinks of O3 and radical chemistry. Since ΣPNs are assumed to be in a steady state, the results here highlight the role that ΣPNs play in urban environments in altering the net O3 production, but ΣPNs can potentially lead to increased net O3 production downwind due to their short lifetime (∼1 h). The results provide guidance for future measurements to identify the missing R(VOCs) and ΣPN production.

Summertime Ozone Production at Carlsbad Caverns National Park, New Mexico: Influence of Oil and Natural Gas Development

AbstractSoutheastern New Mexico's Carlsbad Caverns National Park (CAVE) has increasingly experienced summertime ozone (O3) exceeding an 8‐hr average of 70 parts per billion by volume (ppbv). The park is located in the western part of the Permian oil and natural gas (O&G) basin, where production rates have increased fivefold in the last decade. We investigate O3–precursor relationships by constraining the F0AM box model to observations of nitrogen oxides (NOx = NO + NO2) and a suite of volatile organic compounds (VOCs) collected at CAVE during summer 2019. O&G‐related VOCs dominated the calculated VOC reactivity with hydroxyl radicals (OH) on days when O3 concentrations were primarily controlled by local photochemistry. Radical budget analysis showed that NOx levels were high enough to impose VOC sensitivity on O3 production in the morning hours, while subsequent NOx loss through photochemical consumption led to NOx‐sensitive conditions in the afternoon. Maximum daily O3 was responsive to both NOx and O&G‐related VOC reductions, with NOx reductions proving most effective. The model underestimated observed O3 during a 5‐day high O3 episode that was influenced by photochemically aged O&G emissions, as indicated by back‐trajectory analysis, low i‐/n‐pentane ratios, enhanced secondary VOCs, and low ratios of NOx to total reactive oxidized nitrogen (NOy). Model‐observation agreement was improved by constraining model NOx with observed NOy, which approximates NOx at the time of emission, indicating that a large fraction of O3 during this episode was formed nonlocally.

Effects of VOC emission reduction on atmospheric photochemistry and ozone concentrations during high-ozone episodes

We studied atmospheric volatile organic compounds (VOCs) characteristics and sources during fifteen high ozone (O3) episodes (daily 1-h maximum >100 ppbv and maximum 8-h average > 80 ppbv) in Nanjing, China, and used a photochemical box model to study the O3 formation sensitivity of VOCs, O3 photochemistry, radical budget, and reactivity for different emission reduction scenarios together with the base case ones. Overall, emission reduction from biogenic sources, followed by combustion sources, multiple sources, and solvent usage, had the major impacts on the O3 concentrations. According to photochemical box model simulations, isoprene was the most sensitive or influential VOC in the formation of O3, followed by ethylene, o-xylene, and cis-2-pentene. A 20.6 ± 11.7% concentration reduction of the sixteen most sensitive VOCs (SV16) for the production of O3 could bring the O3 concentration below the national standard level (daily 1-h maximum <100 ppbv). Besides, a 30% emission reduction from all the anthropogenic sources was more than enough to bring the O3 concentration below the national standard level. The total emission reduction of alkenes was always enough to bring the O3 concentration below the national standard level, which was not the case for aromatics under severe pollution conditions. The simulated OH reactivity analysis illustrates the importance of alkenes and aromatics, which account for about half of the total OH reactivity. The highest OH reactivity decreased due to the emission reduction for biogenic sources, followed by combustion and multiple sources. Alkenes played a major role in the OH, HO2, and RO2 radical's formation in the study area. The biggest drop in OH, HO2, and RO2 radical concentrations was noticed for biogenic emission reduction, followed by combustion and multiple sources. Due to the emission reduction from VOC sources, the highest O3 formation rates decreased for biogenic sources, followed by combustion and multiple sources. The acquired information is valuable to the scientific community and policymakers for formulating and implementing O3 pollution control strategies.

Influence of updated isoprene oxidation mechanisms on the formation of intermediate and secondary products in MCM v3.3.1

In this study, we developed an observation based photochemical box model with the measurement data collected at a suburban site (i.e., the Xianghe, XH site) of the Beijing-Tianjin-Hebei (BTH) region and the latest version of the Master Chemical Mechanism (MCM v3.3.1), which newly incorporated 498 reaction for the additional 155 species with the oxidation of isoprene by the OH radical. The influence of updated isoprene degradation on the radical budgets, formation of intermediate and secondary products by comparing the simulation results in the original version (MCM v3.2) was firstly analyzed to estimate whether the updates of precursors could influence the model performance on its evolution pathways and related products. The results demonstrated that though the input of isoprene could significantly decrease or increase the concentrations of OH and HO2 radicals in the model simulation, respectively, the difference in the simulated concentrations of these radicals with isoprene oxidation before and after the updates was not statistically significant. For intermediate products, the simulated concentrations of formaldehyde and methacrolein (MACR) did not significantly alter before and after the updates, while the abundance of methyl vinyl ketone (MVK) reduced obviously (the maximum reduction of 31%) due to lower reaction coefficient between ISOPBO2 and NO and the lower branching ratios caused by the newly added pathways involving CISOPA and TISOPA in the updated scheme. On the other hand, the simulation concentrations of acrolein (ACR), glyoxal (Gly) and methylglyoxal (Mgly) increased significantly after the model updates. The dominant pathway for the increment of ACR was the decomposition of CH2CHCH2O produced by PE4E2CO, while those of Gly and Mgly were associated with radicals of C537O and PACLOOA that were both from the new intermediate radical of CISOPC. In addition, 39 isoprene oxidation products among the 155 new added species were identified to partition in the formation of secondary organic aerosol (SOA), which were coupled in the gas-particle partitioning module to optimize the formation of SOA, contributing 1.15 μg m−3 to the increase of SOA mean concentration. The updates of isoprene degradation further resulted in the significant change for its sensitivity in SOA formation, making it as the secondary important SOA precursor at the XH site. Last but not the least, the influence on photochemical ozone formation related to updates of isoprene degradation was ignorable. Overall, the above results confirmed the insufficient description of the degradation of precursors indeed limited the simulation of the intermediate and secondary products, highlighting the needs of exploring and parameterizing the precursor degradation processes for better understanding of their behaviors and SOA formation in the atmosphere.

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.

High Chlorine Concentrations in an Unconventional Oil and Gas Development Region and Impacts on Atmospheric Chemistry.

Growth in unconventional oil and gas development (UOGD) in the United States has increased airborne emissions, raising environmental and human health concerns. To assess the potential impacts on air quality, we deployed instrumentation in Karnes City, Texas, a rural area in the middle of the Eagle Ford Shale. We measured several episodes of elevated Cl2 levels, reaching maximum hourly averages of 800 ppt, the highest inland Cl2 concentration reported to date. Concentrations peak during the day, suggesting a strong local source (given the short photolysis lifetime of Cl2) and/or a photoinitiated production mechanism. Well preproduction activity near the measurement site is a plausible source of these high Cl2 levels via direct emission and photoactive chemistry. ClNO2 is also observed, but it peaks overnight, consistent with well-known nocturnal formation processes. Observations of organochlorines in the gas and particle phases reflect the contribution of chlorine chemistry to the formation of secondary pollutants in the area. Box modeling results suggest that the formation of ozone at this location is influenced by chlorine chemistry. These results suggest that UOGD can be an important source of reactive chlorine in the atmosphere, impacting radical budgets and the formation of secondary pollutants in these regions.

Seasonal variations of O3 formation mechanism and atmospheric photochemical reactivity during severe high O3 pollution episodes in the Pearl River Delta region

In this study, the seasonal differences of O3 formation and photochemical reactivity were investigated during the high O3 episodes observed in autumn of 2014 and winter of 2017 at a downwind rural site of Pearl River Delta region (Heshan site). The mixing ratios of O3 and NO2 were highest in the Period I of autumn, followed by the Period II of autumn and the winter period. Though the total concentrations of VOCs were comparable in these periods, alkenes made greater fraction of VOCs during Period I of autumn, while those of OVOCs and aromatics were higher in winter period, resulting in the largest contributions of alkenes (ROH(alkenes)) and OVOCs (ROVOCs) to the photochemical reactivity in autumn and winter, respectively. The ozonolysis of alkenes (especially for 1-pentene and isoprene) dominated HOx production during Period I of autumn, while in winter period, photolysis of OVOCs increased before noon, and made the greatest contribution to HOx production in late afternoon. As for the HOx destruction, reaction of OH + NO2 dominated in both seasons, with higher rates in Period I of autumn because of higher levels of radical and NO2. Furthermore, the variations in O3 precursors and radical budget resulted in different O3 formation and destruction rates, with the highest contribution from RO2 and NO to O3 formation, as well as photolysis and ozonolysis of alkenes for O3 destruction in Period I of autumn. The net O3 production from photochemistry and contributions of physical processes indicated that local photochemistry dominated the O3 accumulation at noon and in the early afternoon, while dilution in O3 levels caused by physical process increased before noon and in the late afternoon. O3 formation sensitivity could be changed during the photochemical consumption of precursors, which was more NOx-limited in the late afternoon. Overall, our findings highlighted that control measures of photochemical pollution should consider the seasonal variations in the abundance of O3 and its precursors, and O3 formation sensitivity regime.

Direct evaluation of the ozone production regime in smog chamber experiments

Understanding the atmospheric ozone (O3) production regime is necessary for development of strategies to effectively control the amount of atmospheric O3. We have developed an instrument to directly evaluate the O3 production regime by measuring incremental changes of O3 production rate after injection of nitric oxide and propene into sample air. In this study, we conduct smog-chamber experiments on the oxidation of nitrogen oxides (NOx) and volatile organic compounds (VOC) and use the above instrument to measure O3 production during air mass oxidation. We also perform box model simulations with two chemical mechanisms (one near-explicit and one lumped) to cross validate the measured and simulated O3 production regimes. Oxidation experiments are conducted under VOC-rich and NOx-rich conditions; and the simulation generally reproduced O3 concentrations, OH reactivity (OHR), and contribution of NOx to total OHR. The measured O3 production regime changed from VOC-limited to NOx-limited after 1–3 h of irradiation by xenon arc lamps under the VOC-rich condition, whereas the regime remains VOC-limited throughout our experiment under the NOx-rich condition. The simulated timing of the regime transition under the VOC-rich condition is slower than that of the measured data, which could be attributed to overestimation of the NOx concentration. Both the measured and simulated timing of the regime transition estimated from the sensitivity to injection of O3 precursors NOx and VOC agree well with that estimated from the radical budget. The O3 production regimes estimated by the new instrument and by simulations are consistent with each other, suggesting that both methods are useful for estimating O3 production regime.

Is There a Formaldehyde Deficit in Emissions Inventories for Southeast Michigan?

Formaldehyde is a key Volatile Organic Compound (VOC) and ozone precursor that plays a vital role in the urban atmospheric radical budget on par with water vapor, ozone, and nitrous acid. In addition to modulating radical and ozone production, ambient formaldehyde has both carcinogenic and non-carcinogenic inhalation health effects. This study concludes that ambient formaldehyde in the Southeast Michigan (SEMI) ozone nonattainment area may be underestimated up to a factor of two or more by regional air quality models. The addition of plausible amounts of primary formaldehyde to the U.S. National Emissions Inventory based on estimated formaldehyde-to-CO emission ratios partially alleviates this modeling deficit and indicates the presence of formaldehyde concentrations above 5 ppb at a previously unsuspected location northeast of Detroit. Standard 24-h formaldehyde samples obtained during the Michigan-Ontario Ozone Source Experiment (MOOSE) verified the presence of high ambient formaldehyde concentrations at this location. Moreover, the addition of plausible amounts of primary formaldehyde to VOC emissions inventories may add more than 1 ppb of ozone to ambient air in the SEMI nonattainment area, where ozone design values exceeded the U.S. National Ambient Air Quality Standard (NAAQS) by 1–2 ppb for the 2018–2020 design value period.

Experimental chemical budgets of OH, HO2, and RO2 radicals in rural air in western Germany during the JULIAC campaign 2019

Abstract. Photochemical processes in ambient air were studied using the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich, Germany. Ambient air was continuously drawn into the chamber through a 50 m high inlet line and passed through the chamber for 1 month in each season throughout 2019. The residence time of the air inside the chamber was about 1 h. As the research center is surrounded by a mixed deciduous forest and is located close to the city Jülich, the sampled air was influenced by both anthropogenic and biogenic emissions. Measurements of hydroxyl (OH), hydroperoxyl (HO2), and organic peroxy (RO2) radicals were achieved by a laser-induced fluorescence instrument. The radical measurements together with measurements of OH reactivity (kOH, the inverse of the OH lifetime) and a comprehensive set of trace gas concentrations and aerosol properties allowed for the investigation of the seasonal and diurnal variation of radical production and destruction pathways. In spring and summer periods, median OH concentrations reached 6 × 106 cm−3 at noon, and median concentrations of both HO2 and RO2 radicals were 3 × 108 cm−3. The measured OH reactivity was between 4 and 18 s−1 in both seasons. The total reaction rate of peroxy radicals with NO was found to be consistent with production rates of odd oxygen (Ox= NO2 + O3) determined from NO2 and O3 concentration measurements. The chemical budgets of radicals were analyzed for the spring and summer seasons, when peroxy radical concentrations were above the detection limit. For most conditions, the concentrations of radicals were mainly sustained by the regeneration of OH via reactions of HO2 and RO2 radicals with nitric oxide (NO). The median diurnal profiles of the total radical production and destruction rates showed maxima between 3 and 6 ppbv h−1 for OH, HO2, and RO2. Total ROX (OH, HO2, and RO2) initiation and termination rates were below 3 ppbv h−1. The highest OH radical turnover rate of 13 ppbv h−1 was observed during a high-temperature (max. 40 ∘C) period in August. In this period, the highest HO2, RO2, and ROX turnover rates were around 11, 10, and 4 ppbv h−1, respectively. When NO mixing ratios were between 1 and 3 ppbv, OH and HO2 production and destruction rates were balanced, but unexplained RO2 and ROX production reactions with median rates of 2 and 0.4 ppbv h−1, respectively, were required to balance their destruction. For NO mixing ratios above 3 ppbv, the peroxy radical reaction rates with NO were highly uncertain due to the low peroxy radical concentrations close to the limit of NO interferences in the HO2 and RO2 measurements. For NO mixing ratios below 1 ppbv, a missing source for OH and a missing sink for HO2 were found with maximum rates of 3.0 and 2.0 ppbv h−1, respectively. The missing OH source likely consisted of a combination of a missing inter-radical HO2 to OH conversion reaction (up to 2 ppbv h−1) and a missing primary radical source (0.5–1.4 ppbv h−1). The dataset collected in this campaign allowed analyzing the potential impact of OH regeneration from RO2 isomerization reactions from isoprene, HO2 uptake on aerosol, and RO2 production from chlorine chemistry on radical production and destruction rates. These processes were negligible for the chemical conditions encountered in this study.

Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)

Abstract. The oxidation of limonene by the hydroxyl (OH) radical and ozone (O3) was investigated in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) in experiments performed at different nitric oxide (NO) mixing ratios from nearly 0 up to 10 ppbv. For the experiments dominated by OH oxidation, the formaldehyde (HCHO) yield was experimentally determined and found to be (12 ± 3), (13 ± 3), and (32 ± 5) % for experiments with low (∼ 0.1 ppbv), medium (∼ 0.3 ppbv), and high NO (5 to 10 ppbv), respectively. The yield in an ozonolysis-only experiment was (10 ± 1) %, which agrees with previous laboratory studies. The experimental yield of the first-generation organic nitrates from limonene–OH oxidation is calculated as (34 ± 5) %, about 11 % higher than the value in the Master Chemical Mechanism (MCM), which is derived from structure–activity relationships (SARs). Time series of measured radicals, trace-gas concentrations, and OH reactivity are compared to results from zero-dimensional chemical box model calculations applying MCM v3.3.1. Modeled OH reactivity is 5 to 10 s−1 (25 % to 33 % of the OH reactivity at the start of the experiment) higher than measured values at the end of the experiments under all chemical conditions investigated, suggesting either that there are unaccounted loss processes of limonene oxidation products or that products are less reactive toward OH. In addition, model calculations underestimate measured hydroperoxyl radical (HO2) concentrations by 20 % to 90 % and overestimate organic peroxyl radical (RO2) concentrations by 50 % to 300 %. The largest deviations are found in low-NO experiments and in the ozonolysis experiment. An OH radical budget analysis, which uses only measured quantities, shows that the budget is closed in most of the experiments. A similar budget analysis for RO2 radicals suggests that an additional RO2 loss rate constant of about (1–6) × 10−2 s−1 for first-generation RO2 is required to match the measured RO2 concentrations in all experiments. Sensitivity model runs indicate that additional reactions converting RO2 to HO2 at a rate constant of about (1.7–3.0) × 10−2 s−1 would improve the model–measurement agreement of NOx, HO2, and RO2 concentrations and OH reactivity. Reaction pathways that could lead to the production of additional OH and HO2 are discussed, which include isomerization reactions of RO2 from the oxidation of limonene, different branching ratios for the reaction of RO2 with HO2, and a faster rate constant for RO2 recombination reactions. As the exact chemical mechanisms of the additional HO2 and OH sources could not be identified, further work needs to focus on quantifying organic product species and organic peroxy radicals from limonene oxidation.

Atmospheric photo-oxidation of myrcene: OH reaction rate constant, gas-phase oxidation products and radical budgets

Abstract. The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a Large Reaction Chamber). The chemical structure of myrcene consists of one moiety that is a conjugated π system (similar to isoprene) and another moiety that is a triple-substituted olefinic unit (similar to 2-methyl-2-butene). Hydrogen shift reactions of organic peroxy radicals (RO2) formed in the reaction of isoprene with atmospheric OH radicals are known to be of importance for the regeneration of OH. Structure–activity relationships (SARs) suggest that similar hydrogen shift reactions like in isoprene may apply to the isoprenyl part of RO2 radicals formed during the OH oxidation of myrcene. In addition, SAR predicts further isomerization reactions that would be competitive with bimolecular RO2 reactions for chemical conditions that are typical for forested environments with low concentrations of nitric oxide. Assuming that OH peroxy radicals can rapidly interconvert by addition and elimination of O2 like in isoprene, bulk isomerization rate constants of 0.21 and 0.097 s−1 (T=298 K) for the three isomers resulting from the 3′-OH and 1-OH addition, respectively, can be derived from SAR. Measurements of radicals and trace gases in the experiments allowed us to calculate radical production and destruction rates, which are expected to be balanced. The largest discrepancies between production and destruction rates were found for RO2. Additional loss of organic peroxy radicals due to isomerization reactions could explain the observed discrepancies. The uncertainty of the total radical (ROx=OH+HO2+RO2) production rates was high due to the uncertainty in the yield of radicals from myrcene ozonolysis. However, results indicate that radical production can only be balanced if the reaction rate constant of the reaction between hydroperoxy (HO2) and RO2 radicals derived from myrcene is lower (0.9 to 1.6×10-11 cm3 s−1) than predicted by SAR. Another explanation of the discrepancies would be that a significant fraction of products (yield: 0.3 to 0.6) from these reactions include OH and HO2 radicals instead of radical-terminating organic peroxides. Experiments also allowed us to determine the yields of organic oxidation products acetone (yield: 0.45±0.08) and formaldehyde (yield: 0.35±0.08). Acetone and formaldehyde are produced from different oxidation pathways, so that yields of these compounds reflect the branching ratios of the initial OH addition to myrcene. Yields determined in the experiments are consistent with branching ratios expected from SAR. The yield of organic nitrate was determined from the gas-phase budget analysis of reactive oxidized nitrogen in the chamber, giving a value of 0.13±0.03. In addition, the reaction rate constant for myrcene + OH was determined from the measured myrcene concentration, yielding a value of (2.3±0.3)×10-10 cm3 s−1.

Variability and Time of Day Dependence of Ozone Photochemistry in Western Wildfire Plumes.

Understanding the efficiency and variability of photochemical ozone (O3) production from western wildfire plumes is important to accurately estimate their influence on North American air quality. A set of photochemical measurements were made from the NOAA Twin Otter research aircraft as a part of the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) experiment. We use a zero-dimensional (0-D) box model to investigate the chemistry driving O3 production in modeled plumes. Modeled afternoon plumes reached a maximum O3 mixing ratio of 140 ± 50 ppbv (average ± standard deviation) within 20 ± 10 min of emission compared to 76 ± 12 ppbv in 60 ± 30 min in evening plumes. Afternoon and evening maximum O3 isopleths indicate that plumes were near their peak in NOx efficiency. A radical budget describes the NOx volatile - organic compound (VOC) sensitivities of these plumes. Afternoon plumes displayed a rapid transition from VOC-sensitive to NOx-sensitive chemistry, driven by HOx (=OH + HO2) production from photolysis of nitrous acid (HONO) (48 ± 20% of primary HOx) and formaldehyde (HCHO) (26 ± 9%) emitted directly from the fire. Evening plumes exhibit a slower transition from peak NOx efficiency to VOC-sensitive O3 production caused by a reduction in photolysis rates and fire emissions. HOx production in evening plumes is controlled by HONO photolysis (53 ± 7%), HCHO photolysis (18 ± 9%), and alkene ozonolysis (17 ± 9%).

Characterizing nitrate radical budget trends in Beijing during 2013–2019

Nitrate (NO3) radical is an important oxidant in the atmosphere as it regulates the NOx budget and impacts secondary pollutant formation. Here, a long-term observational dataset of NO3-related species at an urban site in Beijing was used to investigate changes in the NO3 budget and their atmospheric impacts during 2013–2019, in this period the Clean Air Actions Plan was carried out in China. We found that (1) changes in NO3 precursors (NO2 and O3) led to a significant increase in NO3 formation in the surface layer in winter but a decrease in summer; (2) a reduction in NOx promoted thermal equilibrium, favoring the formation of NO3 rather than dinitrogen pentoxide (N2O5). The simultaneous decrease in PM2.5, during these years, further weakened the N2O5 heterogeneous uptake; (3) a box model simulation revealed that both the reactions of NO3 with volatile organic compounds (VOC) and N2O5 uptake were weakened in summer, implying that the policy actions implemented help to moderate secondary aerosol formation caused by NO3 and N2O5 chemistry in summer; and (4) during winter, both NO3 + VOC and N2O5 uptake were enhanced. Specifically, for the N2O5 uptake, the rapid increase in NO3 production, or to some extent, NO3 oxidation capacity, far outweighed the negative shift effect, leading to a net enhancement of N2O5 uptake in winter, which indicates that the action policy implemented led to an adverse effect on particulate nitrate formation via N2O5 uptake in winter. This may explain the persistent winter particulate nitrate pollution in recent years. Our results highlight the systematic changes in the NO3 budget between 2013 and 2019 in Beijing, which subsequently affect secondary aerosol formation in different seasons.

Changes in ozone production and VOC reactivity in the atmosphere of the Mexico City Metropolitan Area

Abstract The introduction of aggressive emission control policies propelled three decades ago has led to significant reductions of ozone (O3) levels in the Mexico City Metropolitan Area (MCMA). However, in recent years the levels have stalled, and there is evidence that the production of secondary pollutants may have started to rebound. Similar responses to changes in O3 precursors observed in other urban areas suggest major changes in atmospheric reactivity and O3 production P(O3), prompting the introduction of new emission control policies. In this study, we evaluate the changes in VOC-OH reactivity and P(O3) using data of O3, volatile organic compounds (VOCs), carbon monoxide (CO), and nitrogen oxides (NOx) collected from the 1990s to 2019 by the local air quality monitoring network and during two dedicated 6-week field measurement campaigns in the MCMA. The results show a reduction of VOC-OH reactivity from 38 s−1 in 2003–2006 to about 19 s−1 in 2018 within the urban core, a slight increase from around 8 s−1 to 9 s−1 for the northern peripheral urban sites in the same period, and a small decrease from about 18 s−1 to 15 s−1 during 2014–2016 in the south of the city. Alkanes are still key contributors to VOC-OH reactivity, whereas the contribution from aromatic and alkene species has decreased, in agreement with reductions of VOC emissions from mobile sources. Changes in P(O3) suggest that increases in the relative contributions from highly oxygenated volatile chemical products from solvents consumption, personal care and other products are responsible for sustained high O3 levels in recent years. We also found that there is a marked spatial dependency of P(O3) in the northern, central, and southern areas of the city, suggesting spatially different VOC and NOx sensitivity regimes. Finally, significant increases in NO2/NO ratios suggest changes in the pathways for the nighttime accumulation of HOx radicals and NOy species that could impact the morning photochemistry and radical budgets for secondary aerosol formation. These results strongly suggest a need for new measurements of radical budgets in the MCMA, the expansion of a continuous measurement network of VOCs with the addition of oxygenated species, and the use of these data to support comprehensive modeling studies for the design of effective emission control strategies.

Nitrous acid (HONO) emissions under real-world driving conditions from vehicles in a UK road tunnel

Abstract. Measurements of atmospheric boundary layer nitrous acid (HONO) and nitrogen oxides (NOx) were performed in summer 2016 inside a city centre road tunnel in Birmingham, United Kingdom. HONO and NOx mixing ratios were strongly correlated with traffic density, with peak levels observed during the early evening rush hour as a result of traffic congestion in the tunnel. A day-time ΔHONO∕ΔNOx ratio of 0.85 % (0.72 % to 1.01 %, 95 % confidence interval) was calculated using reduced major axis regression for the overall fleet average (comprising 59 % diesel-fuelled vehicles). A comparison with previous tunnel studies and analysis on the composition of the fleet suggest that goods vehicles have a large impact on the overall HONO vehicle emissions; however, new technologies aimed at reducing exhaust emissions, particularly for diesel vehicles, may have reduced the overall direct HONO emission in the UK. This result suggests that in order to accurately represent urban atmospheric emissions and the OH radical budget, fleet-weighted HONO∕NOx ratios may better quantify HONO vehicle emissions in models, compared with the use of a single emissions ratio for all vehicles. The contribution of the direct vehicular source of HONO to total ambient HONO concentrations is also investigated and results show that, in areas with high traffic density, vehicle exhaust emissions are likely to be the dominant HONO source to the boundary layer.

No Evidence for a Significant Impact of Heterogeneous Chemistry on Radical Concentrations in the North China Plain in Summer 2014

The oxidation of nitric oxide to nitrogen dioxide by hydroperoxy (HO2) and organic peroxy radicals (RO2) is responsible for the chemical net ozone production in the troposphere and for the regeneration of hydroxyl radicals, the most important oxidant in the atmosphere. In Summer 2014, a field campaign was conducted in the North China Plain, where increasingly severe ozone pollution has been experienced in the last years. Chemical conditions in the campaign were representative for this area. Radical and trace gas concentrations were measured, allowing for calculating the turnover rates of gas-phase radical reactions. Therefore, the importance of heterogeneous HO2 uptake on aerosol could be experimentally determined. HO2 uptake could have suppressed ozone formation at that time because of the competition with gas-phase reactions that produce ozone. The successful reduction of the aerosol load in the North China Plain in the last years could have led to a significant decrease of HO2 loss on particles, so that ozone-forming reactions could have gained importance in the last years. However, the analysis of the measured radical budget in this campaign shows that HO2 aerosol uptake did not impact radical chemistry for chemical conditions in 2014. Therefore, reduced HO2 uptake on aerosol since then is likely not the reason for the increasing number of ozone pollution events in the North China Plain, contradicting conclusions made from model calculations reported in the literature.

Observations of organic and inorganic chlorinated compounds and their contribution to chlorine radical concentrations in an urban environment in northern Europe during the wintertime

Abstract. A number of inorganic (nitryl chloride, ClNO2; chlorine, Cl2; and hypochlorous acid, HOCl) and chlorinated, oxygenated volatile organic compounds (ClOVOCs) have been measured in Manchester, UK during October and November 2014 using time-of-flight chemical ionisation mass spectrometry (ToF-CIMS) with the I− reagent ion. ClOVOCs appear to be mostly photochemical in origin, although direct emission from vehicles is also suggested. Peak concentrations of ClNO2, Cl2 and HOCl reach 506, 16 and 9 ppt respectively. The concentrations of ClNO2 are comparable to measurements made in London, but measurements of ClOVOCs, Cl2 and HOCl by this method are the first reported in the UK. Maximum HOCl and Cl2 concentrations are found during the day and ClNO2 concentrations remain elevated into the afternoon if photolysis rates are low. Cl2 exhibits a strong dependency on shortwave radiation, further adding to the growing body of evidence that it is a product of secondary chemistry. However, night-time emission is also observed. The contribution of ClNO2, Cl2 and ClOVOCs to the chlorine radical budget suggests that Cl2 can be a greater source of Cl than ClNO2, contributing 74 % of the Cl radicals produced on a high radiant-flux day. In contrast, on a low radiant-flux day, this drops to 14 %, as both Cl2 production and loss pathways are inhibited by reduced photolysis rates. This results in ClNO2 making up the dominant fraction (83 %) on low radiant-flux days, as its concentrations are still high. As most ClOVOCs appear to be formed photochemically, they exhibit a similar dependence on photolysis, contributing 3 % of the Cl radical budget observed here.

Low levels of nitryl chloride at ground level: nocturnal nitrogen oxides in the Lower Fraser Valley of British Columbia

Abstract. The nocturnal nitrogen oxides, which include the nitrate radical (NO3), dinitrogen pentoxide (N2O5), and its uptake product on chloride containing aerosol, nitryl chloride (ClNO2), can have profound impacts on the lifetime of NOx (= NO + NO2), radical budgets, and next-day photochemical ozone (O3) production, yet their abundances and chemistry are only sparsely constrained by ambient air measurements. Here, we present a measurement data set collected at a routine monitoring site near the Abbotsford International Airport (YXX) located approximately 30 km from the Pacific Ocean in the Lower Fraser Valley (LFV) on the west coast of British Columbia. Measurements were made from 20 July to 4 August 2012 and included mixing ratios of ClNO2, N2O5, NO, NO2, total odd nitrogen (NOy), O3, photolysis frequencies, and size distribution and composition of non-refractory submicron aerosol (PM1). At night, O3 was rapidly and often completely removed by dry deposition and by titration with NO of anthropogenic origin and unsaturated biogenic hydrocarbons in a shallow nocturnal inversion surface layer. The low nocturnal O3 mixing ratios and presence of strong chemical sinks for NO3 limited the extent of nocturnal nitrogen oxide chemistry at ground level. Consequently, mixing ratios of N2O5 and ClNO2 were low (&lt; 30 and &lt; 100 parts-per-trillion by volume (pptv) and median nocturnal peak values of 7.8 and 7.9 pptv, respectively). Mixing ratios of ClNO2 frequently peaked 1–2 h after sunrise rationalized by more efficient formation of ClNO2 in the nocturnal residual layer aloft than at the surface and the breakup of the nocturnal boundary layer structure in the morning. When quantifiable, production of ClNO2 from N2O5 was efficient and likely occurred predominantly on unquantified supermicron-sized or refractory sea-salt-derived aerosol. After sunrise, production of Cl radicals from photolysis of ClNO2 was negligible compared to production of OH from the reaction of O(1D) + H2O except for a short period after sunrise.

"New" Reactive Nitrogen Chemistry Reshapes the Relationship of Ozone to Its Precursors.

Tropospheric ozone pollution has been a major environmental issue, and mitigation of this persistent problem requires a comprehensive understanding of the sensitivity of ozone to its precursors, i.e., nitrogen oxides (NO x) and volatile organic compounds (VOCs). Recent studies have proposed several "new" reactive nitrogen chemical processes, including additional sources of nitrous acid, heterogeneous uptake of dinitrogen pentoxide, and production of nitryl chloride. These processes significantly affect the budgets of radicals and NO x and hence the formation of ozone. In present study, we aim to investigate to what extent these processes alter the relationships between ozone and its precursors. A revised Weather Research and Forecasting model coupled with Chemistry incorporating the "new" nitrogen chemistry was adopted to simulate the ozone sensitivity regime in China in summer. The results showed that nitrogen chemistry changed the ozone sensitivity regime for approximately 40% of the simulated area with human influence, mostly from VOC-sensitive or NO x-sensitive regimes to mixed-sensitive regime. The nitrogen chemistry changed the isopleth plots of the ozone peak values for major cities, suggesting a different strategy for controlling ozone pollution. This study underscores the need to consider unconventional nitrogen chemistry in air quality models used in the design of ozone control strategies.