Sensitivity Of Ozone Production Research Articles

Insights into the long-term (2005–2021) spatiotemporal evolution of summer ozone production sensitivity in the Northern Hemisphere derived with the Ozone Monitoring Instrument (OMI)

Abstract. Tropospheric ozone (O3) formation depends on the relative abundance of precursor species, nitrogen oxides (NOx), and volatile organic compounds (VOCs). Advancements in satellite retrievals of formaldehyde (HCHO) and nitrogen dioxide (NO2) vertical column densities (VCDs), and the corresponding HCHO/NO2 ratios (FNRs), provide the opportunity to diagnose the spatiotemporal evolution of O3 production sensitivity regimes. This study investigates trends of Ozone Monitoring Instrument (OMI)-derived summertime VCD HCHO, NO2, and FNRs in the Northern Hemisphere from 2005 to 2021. FNR trends were analyzed for polluted regions, specifically for 46 highly populated cities, over the entire 17-year period and in 2020 when global anthropogenic emissions were reduced due to COVID-19 lockdown restrictions. It was determined that OMI-derived FNRs have increased on average by ∼ 65 % across cities in the Northern Hemisphere. Increasing OMI-derived FNRs indicates a general transition from radical-limited to NOx-limited regimes. The increasing trend is driven by reduced NO2 concentrations because of emission-control strategies of NOx. OMI FNR trends were compared to ground-based in situ measurements in US cities, and it was determined that they can capture the trends in increasing FNRs (R=0.91) and decreasing NO2 (R=0.98) occurring at the surface. OMI FNRs in urban areas were higher (∼ 20 %) in 2020 for most cities studied here compared to 2019 and 2021. In addition to studying the longest period of OMI FNRs across the Northern Hemisphere to date, the capabilities and challenges of using satellite VCD FNRs to study surface-level O3 production sensitivity regimes are discussed.

Ozone production sensitivity analysis for the Chengdu Plain Urban Agglomeration based on a multi-site and two-episode observation

Chengdu Plain Urban Agglomeration (CPUA) is one of the most serious areas suffering from ozone pollution in China. A comprehensive field observation focused on the ozone production rate and its sensitivity was conducted at CPUA in the summer of 2019. Six sampling sites were set and two ozone pollution episodes were recognized. The daily maximum 8-h average (MDA8) O3 concentration reached 137.9 ppbv in the urban sites during the ozone pollution episode. Peak concentration of O3 was closely related to intense solar radiation, high temperatures, and precursor emissions. The OH-HO2-RO2 radical chemistry and ozone production rate (P(O3)) were calculated using an observation-based model (OBM). The daily peak OH concentration varied in the range of 3-13 × 106 molecules cm−3, and peak HO2 and RO2 were in the range of 2–14 × 108 molecules cm−3 during ozone pollution episodes. During the ozone pollution episode, the average maximum of P(O3) in suburban sites (about 30 ppbv h-1.) was compared with urban sites, and the maximum of P(O3) was 18 ppbv h-1 in rural sites. The relative incremental reactivity (RIR) results demonstrate that it was a VOCs-limited regime in the central urban area of Chengdu, with NOx suppression effect in some regions. In the southern neighboring suburb of Chengdu, it was VOCs-limited as well. However, the northern suburban area was a transition region. In the remote rural areas of the southern CPUA, it was highly NOx-limited. Local ozone production driven by the photochemical process is crucial to the ozone pollution formation in CPUA. The geographically differentiated recognition of the ozone regime found by this study can help to tailor control strategies for local conditions and avoid the negative effects of a one-size-fits-all approach.

Ozone production sensitivity in the highland city of Lhasa: a comparative analysis with Beijing

Ozone production sensitivity in the highland city of Lhasa: a comparative analysis with Beijing

Exploring ozone production sensitivity to NOx and VOCs in the New York City airshed in the spring and summers of 2017–2019

Reducing ozone in the New York City (NYC) region requires understanding the nonlinearity of ozone production (PO3) and its sensitivity to volatile organic compounds (VOCs) and nitrogen oxides (NOx = NO2 + NO). Using observations from the Long Island Sound Tropospheric Ozone Study (LISTOS) in the late spring and summers of 2017–2019 and a 0-D box model, we test the sensitivity of PO3 to ozone precursors. PO3 is greater in the morning than the afternoon due to increased concentrations of NO2 and VOC. This diurnal variation in PO3 is enhanced in the late summer. Based on the model response of PO3 to changes in initial NO2, 14% of samples are within a VOC-limited regime. The metric LROx/LNOx, which compares the radical loss rates via self-reaction to their reaction with NO2, indicates an additional 17% of samples are in transition between NOx and VOC-limited regimes (0.30 <= LROx/LNOx <= 1). We often find PO3 to be VOC-limited in NYC and along the Connecticut coastline (I-95 corridor). In these samples, PO3 is most sensitive to isoprene, propene, and isopentane, and individual VOCs have strong diurnal and seasonal variations. We further compare PO3 calculations using the near explicit Master Chemical Mechanism (MCMv3.3.1) and Carbon Bond 6 revision 2 (CB6r2) for a more direct link to regulatory air quality models. Modeled PO3 is 20% greater in MCMv3.3.1, due largely to the speciation of VOC and organic peroxy radicals, however the bounds of LROx/LNOx used to determine the transition range between PO3 regimes remain the same.

Understanding ozone episodes during the TRACER-AQ campaign in Houston, Texas: The role of transport and ozone production sensitivity to precursors

This study investigated transport pathways and photochemical formation responsible for ozone exceedances during the September 2021 deployment of the Tracking Aerosol Convection Interactions ExpeRiment/Air Quality (TRACER-AQ) campaign in Houston, Texas. We focused on two ozone episodes, September 6th–September 11th (“Episode 1”) and September 23rd–September 26th (“Episode 2”), when the maximum daily eight-hour average (MDA8) ozone at surface monitors exceeded 70 ppbv. Long-range transport patterns of air masses during these episodes were from the central/northern US. High-resolution (4 km resolution) trajectory analysis with FLEXible PARTicle (FLEXPART) dispersion model revealed local recirculation of air masses and the accumulation of pollutants across Houston contribute to the ozone exceedances. Comprehensive Air Quality Model with extensions (CAMx) driven by 1.33-km resolution meteorology from the Weather Research and Forecast (WRF) tool simulated elevated ozone production rates during ozone episodes across the Houston metropolitan area, with ozone production hotspots mostly over Houston city and industrial districts of the Houston Ship Channel (HSC). The regional increase in ozone production rates was due to the transport of VOC-rich air masses (via northerly flows) that brought ozone precursors to the region, which ultimately caused a transition in the ozone formation tendency from generally VOC-limited to NOx-limited conditions. However, the city of Houston and the HSC remained in a VOC-limited regime because of local NOx emissions that, to some extent, preponderated the impact of transported VOCs. While approximately 37 % of the elevated ozone production was attributed to local photochemistry, the remaining ∼63 % increase in ozone production was due to the transported ozone to the region during episodes, bringing ozone to the Houston region and contributing to ozone exceedances. The outcomes of this study illustrated the synergy between transport and ozone production, both long-range and local scale, which resulted in ozone exceedances in Houston.

Variations, sources, and effects on ozone formation of VOCs during ozone episodes in 13 cities in China

In recent years, ozone (O3) pollution has worsened in China and contributes frequently to air pollution problems. To support the implementation of coordinated control for ozone and fine particulate matter, it is essential to study the chemical compositions and sources of volatile organic compounds (VOCs), which are the crucial precursor of both ozone and fine particulate matter. In this study, 117 volatile organic compounds were monitored in 13 cities in Beijing-Tianjin-Hebei Urban Agglomeration and Fenwei plain. Concentrations of total volatile organic compounds ranged from 42 to 279 μg/m3 during the monitoring episode. In all 13 cities, alkanes, halogenated hydrocarbons, aromatics and oxygenated volatile organic compounds (OVOCs) were the dominant volatile organic compounds. Contributions of alkanes, halogenated hydrocarbons, aromatics and oxygenated volatile organic compounds to total ozone formation potential (OFP) were 21.7%–32.6%, 21.0%–27.9%, 24.3%–50.8% and 28.6%–52.3%, respectively. Furthermore, the results of source apportionment by positive matrix factorization (PMF) model indicated that solvent usage, gasoline evaporation, vehicle emissions, petrochemical industry and combustion were essential volatile organic compounds sources in 13 cities. Moreover, the sensitivity of ozone production was studied using an Empirical Kinetic Modeling Approach (EKMA) model, and it was found that ozone formation was volatile organic compounds limited in all 13 cities.

Meteorological and chemical controls on surface ozone diurnal variability in Beijing: A clustering-based perspective

This study aimed to reveal the dominant, recurring patterns of surface ozone diurnal cycles in Beijing, their quantitative characteristics, namely, occurrence frequency and transition probability, and their potential linkages to meteorological and chemical processes based on multi-source observations (surface ozone, satellite-based ozone precursors, ground-based and sonde-based meteorological measurements) and reanalyses (ERA5 meteorological and TCR2 chemical reanalyses). By applying K-means clustering, four distinct ozone diurnal patterns (Cluster 1: all-day low anomaly; Cluster 2: nighttime high-daytime low anomaly; Cluster 3: nighttime low-daytime high anomaly; Cluster 4: extreme pollution pattern with all-day high anomaly) are objectively identified from 2013 to 2020 warm-season (May–September) surface ozone measurements. Despite a relatively low total occurrence, the extreme pollution pattern tended to persist over an extended period (average persistence of 2.3 days). Composite analyses of multi-source meteorology indicate that the elevated nocturnal ozone in Cluster 2 is associated with the compensating downdraft flow of nocturnal convective storms. By contrast, elevated nocturnal ozone in Cluster 4 was associated with the prevailing low-level jet (LLJ) over the whole North China Plain (NCP) region. The LLJ-related dynamical processes trigger regional transport in the residual layer and downward mixing from the residual layer, elevating the background ozone level in downstream Beijing. Moreover, Cluster 4 is under the control of 500-hPa anomalous high pressure, which leads to daytime hot-dry weather favoring the occurrence of extreme afternoon pollution via photochemical ozone production. From Cluster 1 to Cluster 4, satellite-based formaldehyde (CH2O) increased by 71% accompanied by less change in nitrogen dioxide (NO2), causing a shift in ozone production sensitivity. Because extreme pollution pattern typically occurs in the transition regime, synergetic emission control of volatile organic compounds (VOCs) and nitrogen oxides (NOx) would be effective in alleviating severe ozone pollution in Beijing.

The Lack of HONO Measurement May Affect the Accurate Diagnosis of Ozone Production Sensitivity.

Recently, deteriorating ozone (O3) pollution in China brought the precise diagnosis of O3 sensitive chemistry to the forefront. As a dominant precursor of OH radicals, atmospheric nitrous acid (HONO) plays an important role in O3 production. However, its measurement unavailability in many regions especially for second- and third-tier cities may lead to the misjudgment of the O3 sensitivity regime derived from observation-based models. Here, we systematically assess the potential impact of HONO on diagnosing the sensitivity of O3 production using a 0-dimension box model based on a comprehensive summer urban field campaign. The results indicated that the default mode (only the NO + OH reaction is included) in the model could underestimate ∼87% of observed HONO levels, leading to an obvious decrease (∼19%) of net O3 production in the morning, which was in line with the previous studies. The unconstrained HONO in the model was found to significantly push O3 production toward the VOC-sensitive regime. Additionally, it is unrealistic to change NO x but constrain HONO in the model due to the dependence of HONO formation on NO x . Assuming that HONO varied proportionally with NO x , a stronger NO x -sensitive condition could be achieved. Therefore, effective reduction of NO x should be given more attention together with VOC emission control for O3 mitigation.

Potential Strong Inhibition on Ozone Production Sensitivity by Particle Uptake

The accurate identification of ozone (O3) production sensitivity is central to developing O3 pollution control policies. It is determined by the relative ratio of the radical loss to the total primary radical production. However, such radical losses in the traditional sensitivity analysis typically rely on nitrogen oxide (NOx) sinks while ignoring particle uptake (collisions between compounds in the gas phase and condensed phases that result in irreversible uptake due to chemical reactions). Therefore, we combine NOx and particle uptakes to optimize peroxy radical loss estimates and thus analyze the relative sensitivity. We also assess the absolute responses of precursor reduction to O3 production. Such relative and absolute sensitivity analysis is applied to measurements in Chun’an, a county in China, where volatile organic compounds (VOCs) and NOx are both rich. Consequently, the relative sensitivity analysis presents that the dominant precursor for O3 production sensitivity shifts from volatile organic compounds (VOCs) in the morning and evening to NOx in the afternoon, the main driver of which is related to NO depletion. In contrast, the absolute sensitivity analysis confirms that VOCs persistently determine the diurnal ozone production sensitivity. Moreover, they both show that particle uptake does not change the regime classification of O3 production sensitivity (i.e., VOC- or NOx-sensitive regime) but potentially has a strong inhibition on the sensitivity magnitude (within 16% and 38% for VOC- or NOx-sensitive regimes, respectively). Our results partly explain more insensitive O3 production measurements than those suggested by traditional sensitivity analyses, which has important implications for synergistic controls on O3 and fine particulate matter pollution.

Potential Factors Contributing to Ozone Production in AQUAS-Kyoto Campaign in Summer 2020: Natural Source-Related Missing OH Reactivity and Heterogeneous HO2/RO2 Loss.

This study presents total OH reactivity, ancillary trace species, HO2 reactivity, and complex isoprene-derived RO2 reactivity due to ambient aerosols measured during the air quality study (AQUAS)-Kyoto campaign in September, 2020. Observations were conducted during the coronavirus disease (COVID-19) pandemic (associated with reduced anthropogenic emissions). The spatial distribution of missing OH reactivity highlights that the origin of volatile organic compounds (VOCs) may be from natural-emission areas. For the first time, the real-time loss rates of HO2 and RO2 onto ambient aerosols were measured continuously and alternately. Ozone production sensitivity was investigated considering unknown trace species and heterogeneous loss effects of XO2 (≡HO2 + RO2) radicals. Missing OH reactivity enhanced the ozone production potential by a factor of 2.5 on average. Heterogeneous loss of radicals could markedly suppress ozone production under low NO/NOx conditions with slow gas-phase reactions of radicals and change the ozone regime from VOC- to NOx-sensitive conditions. This study quantifies the relationship of missing OH reactivity and aerosol uptake of radicals with ozone production in Kyoto, a low-emission suburban area. The result has implications for future NOx-reduction policies. Further studies may benefit from the combination of chemical transport models and inverse modeling over a wide spatiotemporal range.

Observation-based analysis of ozone production sensitivity for two persistent ozone episodes in Guangdong, China

Abstract. An observation-based method (OBM) is developed to investigate the sensitivity of ozone formation to precursors during two persistent elevated ozone episodes observed at 77 stations in Guangdong. Average OH concentrations derived at the 77 stations between 08:00 and 13:00 local time stay within a narrow range of 2.5×106 to 5.5×106 cm−3 with a weak dependence on the NOx. These values are in good agreement with OH values observed at a rural station in the Pearl River Delta (PRD). They also agree well with a box model constrained by the ambient conditions observed during the two episodes. The OBM has been used to evaluate the ozone production efficiency, ε(NOx or volatile organic compound, VOC), defined as the number of O3 molecules produced per molecule of NOx (or VOC) oxidized. Average values of ε(NOx) and ε(VOC) determined by the OBM are 3.0 and 2.1 ppb ppb−1, respectively, and both compared well with values in previous studies. Approximately 67 % of the station days exhibit ozone formation sensitivity to NOx, and approximately 20 % of the station days are in the transitional regime sensitive to both NOx and VOC, and only approximately 13 % of the station days are sensitive to VOC. These results are in semi-quantitative agreement with the ozone formation sensitivity calculated by the box model constrained by ambient conditions observed during the two episodes. However, our OBM results differ from those of most previous investigations, which suggested that limiting the emission of VOC rather than NOx would be more effective in reducing ozone reduction in Guangdong.

Reduced Aerosol Uptake of Hydroperoxyl Radical May Increase the Sensitivity of Ozone Production to Volatile Organic Compounds

Reduced Aerosol Uptake of Hydroperoxyl Radical May Increase the Sensitivity of Ozone Production to Volatile Organic Compounds

Progress on the vertical observation methods of volatile organic compounds and their applications within the atmospheric boundary layer

<p indent="0mm">Volatile organic compounds (VOCs) are important trace gases in the troposphere that play vital roles in the formation of secondary air pollutants such as ozone and organic aerosol components. An in-depth characterization of the spatiotemporal variability, particularly in three-dimensions, of VOCs in the atmospheric boundary layer is an essential prerequisite for understanding the formation mechanisms of regional pollution episodes. However, vertically resolved VOCs measurements are seldom made during field campaigns due to the limitation of available observation techniques. This review summarizes the progress in vertical observation of VOCs and their applications to the atmospheric boundary layer, focusing on the introduction of platforms for vertical measurement techniques for VOCs, including high-rise buildings, tethered balloons, aircraft, unmanned aerial vehicles (UAVs), and remote sensing. All of these platforms have been used in previous studies and have their respective advantages and disadvantages. High-rise buildings are generally characterized by low altitudes and fixed locations but could serve as long-term platforms for both online and offline VOCs measurements. Tethered balloons, generally used for offline VOCs measurements, have flexible launch locations and altitude ranges. Aircraft can provide platforms for both offline and online VOCs measurements over large spatial scales, but aircrafts are not suitable for long-term observations because of their high operating cost. Similar to tethered balloons, UAVs are used for offline VOCs measurements, while they are much more flexible in utilization and can be launched in complex environments. However, small payload, short flight duration, and availability of airspace are key factors that limit the wide application of UAVs in the field of environmental monitoring. Remote sensing platforms (including ground-based and space-based techniques) could provide vertical measurements of several VOCs species over large temporal and spatial scales. However, the vertical VOCs profiles provided by remote sensing techniques are frequently characterized by large uncertainty. With the rapid development of VOCs measurement techniques (such as UAVs and proton-transfer-reaction time-of-flight mass spectrometry), future studies are expected to obtain vertical VOCs observations with higher spatiotemporal resolutions as well as lower operating costs. Vertical observations of VOCs concentrations could provide valuable opportunities for a thorough analysis of VOCs emissions and variation of their related chemical processes within the atmospheric boundary layer. Therefore, this review also summarizes the progress in applications of vertical VOCs observations in the atmospheric boundary layer, focusing on introducing the key factors influencing VOCs vertical distribution patterns, determination of VOCs emission fluxes, evaluation and calibration of VOCs emission inventories, investigation of the vertical distribution of photochemical ozone production sensitivity, and the vertical distribution of VOCs degradation mechanisms at night. At present, vertical observations are predominantly used to identify impacts of transport and boundary-layer dynamics on the vertical distributions of different VOCs species and to estimate speciated VOCs emissions. However, the vertical variability of the oxidation and degradation mechanisms for different VOCs species and the environmental effects of this variability have been reported in only a few studies. More effort should be made to elucidate how the interactions between VOCs chemistry and vertical transport affect the formation and concentration of secondary air pollutants at ground level. In summary, there is an urgent need to obtain reliable vertical observations of key VOCs species in the atmospheric boundary layer for better investigating the formation mechanisms of regional atmospheric pollution.

An explicit study of local ozone budget and NOx-VOCs sensitivity in Shenzhen China

In China, a significant reduction in primary pollution has been observed due to the Clean Air Action since 2013, and ozone pollution has become increasingly prominent over the past years. Pearl River Delta (PRD) is one of the most successful regions concerning primary pollution control, while is suffering from severe ozone pollution during autumn. In this study, we present a field campaign in Shenzhen, a megacity in PRD, in October 2018 with measurements of ozone and photochemical precursors. These observational data are helpful to analyze the local ozone budget and its sensitivity to precursors with the help of an observation-based model (RACM2-LIM1). The observed ozone concentration was up to 121 ppbv during a photochemical episode from 1 to 8 October, when intensive ozone formation up to tens of ppbv/h was found. Ozone vertical measurement indicates the fast ozone production is happening throughout the planetary boundary layer (PBL), which is an important source of morning ozone increase resulting in ozone pollution. An explicit case study is performed to reveal the diurnal feature of instantaneous ozone production rate (P(Ox)) and accumulative P(Ox) based on the O3-NOx-VOC sensitivity, ROx radical primary production rate (P (ROx)), and LN/Q for three cases including ozone pollution and attainment periods. Results show that nitrogen oxides (NOx = NO + NO2) reduction have positive and negative impact on local ozone production from one pollution episode to the other, which indicates the complexity of O3-precursors sensitivity and difficulty to control ozone pollution in Shenzhen. Finally, comparison among measurements in other campaigns provides additional evidence on local ozone production sensitivity on NOx and anthropogenic volatile organic compounds (AVOCs) with respect to a temporal and spatial change. The NOx reduction in Shenzhen has led to higher ozone production from 2015 to 2018 given the nearly constant VOC. However, the ozone mitigation would be benefit from further NOx reduction in the conditions of 2018.

Relative and Absolute Sensitivity Analysis on Ozone Production in Tsukuba, a City in Japan.

The change in the ozone production rate on reducing its precursors, namely, ozone production sensitivity, is important information for developing a strategy to reduce ozone. We expanded a conventional sensitivity analysis theory by including peroxy radical loss by uptake onto particle surfaces in the aim of examining their potential impact. We also propose a new concept of absolute sensitivity that enables us to evaluate the quantitative effectiveness of precursor reduction toward mitigating ozone production over a given period and area. This study applies the theory to observations in Tsukuba, a city in Japan. The relative sensitivity analysis shows that ozone production was more sensitive to volatile organic compounds (VOCs) in the morning and evening, and it became more sensitive to NOx in the afternoon. NO depletion was a main trigger in this sensitivity regime transition. The absolute sensitivity analysis indicates that the VOC-sensitive period in the morning determines the total ozone production sensitivity in a day. While particles did not have significant impact on regime classification in Tsukuba, they have a potential to decrease the mitigating effect of VOC reduction on ozone production and to moderate the enhancement effect of NOx reduction depending upon uptake coefficients. A further study will benefit from a combination with an observation-constrained box model simulation or chemical transport modeling system, which may provide sensitivity analysis over a large spatial and temporal range.

Sensitivity of ozone production to increasing temperature and reduction of precursors estimated from observation data

The sensitivity of ozone production to increasing temperature and a decreasing concentration of precursors, namely nitrogen oxides and non-methane hydrocarbon, has been estimated with probability theory using observation data for 2004–2015 for the Kanto region, Japan. The sensitivity of ozone, in terms of the number of high ozone concentration days, to temperature was higher at the beginning of the observation period when precursor concentrations were high but lower in more recent years when the precursor concentrations were lower. Analysis of the high ozone concentration days showed that a 10-percent reduction of both precursor concentrations yields a reduction in the number of high concentration ozone days of approximately 4 days per year, whereas a 0.2 °C temperature increase leads to less than a 1-day increase per year. This indicates that precursor concentration is more important than temperature for determining ozone concentration.

Observations of ozone vertical profiles and corresponding precursors in the low troposphere in Beijing, China

A comprehensive investigation of ozone, its precursors as well as aerosols in the low troposphere was conducted over the University of Chinese Academy of Sciences site (abbreviated as UCAS site, a northern suburban site) in Beijing during the period of October 26 to November 6, 2014, with a focus on the comparison between polluted and clean conditions. The vertical profiles of ozone and aerosol extinction coefficients in the low troposphere were measured by differential absorption lidar, and the tropospheric vertical column densities (VCDs) as well as vertical profiles of HCHO and NO2 were measured by ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS). O3 in the boundary layer (0.3–1.0 km) had a positive gradient with height and presented a stratified structure at night on haze days, in contrast to a uniform distribution during clean episodes. The polluted conditions were characterized by higher levels of atmospheric pollutants (O3, aerosol, HCHO and NO2) and more dynamic variations with respect to clean periods. During lightly to moderately polluted periods, elevated concentrations of O3 within the boundary layer were observed with a maximum exceeding 60 ppbv. In haze days, the air masses from urban Beijing and southern Hebei industrial and urbanized areas could bring large amounts of precursors, enhancing O3 formation over the lidar site. The photochemical production of O3 within the boundary layer was controlled by a VOC-limited regime in haze days and turned into a mixed-VOC-NOx-limited regime on clean days. According to sensitivity analysis, when air masses came from southern polluted regions, the sensitivity of ozone production was dominated by VOC-limited regime. The reduction of VOC emissions from urban Beijing and Hebei industrial and urbanized areas would favor the mitigation of O3 pollution at UCAS site.

Characterization of ozone in the lower troposphere during the 2016 G20 conference in Hangzhou

Recently, atmospheric ozone pollution has demonstrated an aggravating tendency in China. To date, most research about atmospheric ozone has been confined near the surface, and an understanding of the vertical ozone structure is limited. During the 2016 G20 conference, strict emission control measures were implemented in Hangzhou, a megacity in the Yangtze River Delta, and its surrounding regions. Here, we monitored the vertical profiles of ozone concentration and aerosol extinction coefficients in the lower troposphere using an ozone lidar, in addition to the vertical column densities (VCDs) of ozone and its precursors in the troposphere through satellite-based remote sensing. The ozone concentrations reached a peak near the top of the boundary layer. During the control period, the aerosol extinction coefficients in the lower lidar layer decreased significantly; however, the ozone concentration fluctuated frequently with two pollution episodes and one clean episode. The sensitivity of ozone production was mostly within VOC-limited or transition regimes, but entered a NOx-limited regime due to a substantial decline of NOx during the clean episode. Temporary measures took no immediate effect on ozone pollution in the boundary layer; instead, meteorological conditions like air mass sources and solar radiation intensities dominated the variations in the ozone concentration.

Measurements of hydroxyl and hydroperoxy radicals during CalNex‐LA: Model comparisons and radical budgets

AbstractMeasurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex‐LA 2010 campaign using the laser‐induced fluorescence‐fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero‐dimensional model using the Regional Atmospheric Chemical Mechanism‐2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.

On the long-term impact of emissions from central European cities on regional air quality

Abstract. For the purpose of qualifying and quantifying the impact of urban emission from Central European cities on the present-day regional air quality, the regional climate model RegCM4.2 was coupled with the chemistry transport model CAMx, including two-way interactions. A series of simulations was carried out for the 2001–2010 period either with all urban emissions included (base case) or without considering urban emissions. Further, the sensitivity of ozone production to urban emissions was examined by performing reduction experiments with −20 % emission perturbation of NOx and/or non-methane volatile organic compounds (NMVOC). The modeling system's air quality related outputs were evaluated using AirBase, and EMEP surface measurements showed reasonable reproduction of the monthly variation for ozone (O3), but the annual cycle of nitrogen dioxide (NO2) and sulfur dioxide (SO2) is more biased. In terms of hourly correlations, values achieved for ozone and NO2 are 0.5–0.8 and 0.4–0.6, but SO2 is poorly or not correlated at all with measurements (r around 0.2–0.5). The modeled fine particulates (PM2.5) are usually underestimated, especially in winter, mainly due to underestimation of nitrates and carbonaceous aerosols. European air quality measures were chosen as metrics describing the cities emission impact on regional air pollution. Due to urban emissions, significant ozone titration occurs over cities while over rural areas remote from cities, ozone production is modeled, mainly in terms of number of exceedances and accumulated exceedances over the threshold of 40 ppbv. Urban NOx, SO2 and PM2.5 emissions also significantly contribute to concentrations in the cities themselves (up to 50–70 % for NOx and SO2, and up to 60 % for PM2.5), but the contribution is large over rural areas as well (10–20 %). Although air pollution over cities is largely determined by the local urban emissions, considerable (often a few tens of %) fraction of the concentration is attributable to other sources from rural areas and minor cities. For the case of Prague (Czech Republic capital), it is further shown that the inter-urban interference between large cities does not play an important role which means that the impact on a chosen city of emissions from all other large cities is very small. At last, it is shown that to achieve significant ozone reduction over cities in central Europe, the emission control strategies have to focus on the reduction of NMVOC, as reducing NOx (due to suppressed titration) often leads to increased O3. The influence over rural areas is however always in favor of improved air quality, i.e. both NOx and/or NMVOC reduction ends up in decreased ozone pollution, mainly in terms of exceedances.