High O3 Episodes Research Articles

Simulated Sensitivity of Ozone Generation to Precursors in Beijing during a High O3 Episode

Simulated Sensitivity of Ozone Generation to Precursors in Beijing during a High O3 Episode

Explicit modeling of isoprene chemical processing in polluted air masses in suburban areas of the Yangtze River Delta region: radical cycling and formation of ozone and formaldehyde

Abstract. In recent years, ozone pollution has become one of the most severe environmental problems in China. Evidence from observations have showed increased frequency of high O3 levels in suburban areas of the Yangtze River Delta (YRD) region. To better understand the formation mechanism of local O3 pollution and investigate the potential role of isoprene chemistry in the budgets of ROx (OH+HO2+RO2) radicals, synchronous observations of volatile organic compounds (VOCs), formaldehyde (HCHO), and meteorological parameters were conducted at a suburban site of the YRD region in 2018. Five episodes with elevated O3 concentrations under stagnant meteorological conditions were identified; an observation-based model (OBM) with the Master Chemical Mechanism was applied to analyze the photochemical processes during these high O3 episodes. The high levels of O3, nitrogen oxides (NOx), and VOCs facilitated strong production and recycling of ROx radicals with the photolysis of oxygenated VOCs (OVOCs) being the primary source. Our results suggest that local biogenic isoprene is important in suburban photochemical processes. Removing isoprene could drastically slow down the efficiency of ROx recycling and reduce the concentrations of ROx. In addition, the absence of isoprene chemistry could further lead to a decrease in the daily average concentrations of O3 and HCHO by 34 % and 36 %, respectively. Therefore, this study emphasizes the importance of isoprene chemistry in the suburban atmosphere, particularly with the participation of anthropogenic NOx. Moreover, our results provide insights into the radical chemistry that essentially drives the formation of secondary pollutants (e.g., O3 and HCHO) in suburban areas of the YRD region.

Ambient volatile organic compounds at a receptor site in the Pearl River Delta region: Variations, source apportionment and effects on ozone formation

We present the continuously measurements of volatile organic compounds (VOCs) at a receptor site (Wan Qing Sha, WQS) in the Pearl River Delta (PRD) region from September to November of 2017. The average mixing ratios of total VOCs (TVOCs) was 36.3 ± 27.9 ppbv with the dominant contribution from alkanes (55.5%), followed by aromatics (33.3%). The diurnal variation of TVOCs showed a strong photochemical consumption during daytime, resulting in the formation of ozone (O3). Five VOC sources were resolved by the positive matrix factorization (PMF) model, including solvent usage (28.6%), liquid petroleum gas (LPG) usage (24.4%), vehicle exhaust (21.0%), industrial emissions (13.2%) and gasoline evaporation (12.9%). The regional transport air masses from the upwind cities of south China can result in the elevated concentrations of TVOCs. Low ratios of TVOCs/NOx (1.53 ± 0.88) suggested that the O3 formation regime at WQS site was VOC-limited, which also confirmed by a photochemical box model with the master chemical mechanism (PBM-MCM). Furthermore, the observation on high-O3 episode days revealed that frequent O3 outbreaks at WQS were mainly caused by the regional transport of anthropogenic VOCs especially for aromatics and the subsequent photochemical reactions. This study provides valuable information for policymakers to propose the effective control strategies on photochemical pollution in a regional perspective.

Characteristics of HONO and its impact on O3 formation in the Seoul Metropolitan Area during the Korea-US Air Quality study

Photolysis of nitrous acid (HONO) is recognized as an early-morning source of OH radicals in the urban air. During the Korea–US Air Quality (KORUS-AQ) campaign, HONO was measured using quantum cascade - tunable infrared laser differential absorption spectrometer (QC-TILDAS) at Olympic Park in Seoul from 17 May, 2016 to 14 June, 2016. The HONO concentration was in the range of 0.07–3.46 ppbv, with an average of 0.93 ppbv. Moreover, it remained high from 00:00–05:00 LST. During this time, the mean concentration was higher during the high-O3 episodes (1.82 ppbv) than the non-episodes (1.20 ppbv). In the morning, the OH radicals that were produced from HONO photolysis were 50% higher (0.95 pptv) during the high-O3 episodes than the non-episodes. Diurnal variations in HOx and O3 concentrations were simulated by the F0AM model, which revealed a difference of ~20 ppbv in the daily maximum O3 concentrations between the high-O3 episodes and non-episodes. Furthermore, the HONO concentration increased with an increase in relative humidity (RH) up to 80%; the highest HONO was associated with the top 10% NO2 in each RH group, confirming that NO2 is one of the main precursors of HONO. At night, the conversion ratio of NO2 to HONO was estimated to be 0.88×10−2 h−1; this ratio was found to increase with an increase in RH. The Aitken mode particles (30–120 nm), which act as catalyst surfaces, exhibited a similar tendency with a conversion ratio that increased along with RH, indicating the coupling of surfaces with HONO conversion. Using an artificial neural network (ANN) model, HONO concentrations were successfully simulated with measured variables (r2 = 0.66 as an average of five models). Among these variables, NOx, aerosol surface area, and RH were found to be the main factors affecting the ambient HONO concentrations. The results reveal that RH facilitates the conversion of NO2 to HONO by constraining the availability of aerosol surfaces. This study demonstrates the coupling of HONO with the HOx-O3 cycle in the Seoul Metropolitan Area (SMA) and provides practical evidence of the heterogeneous formation of HONO by employing the ANN model.

Modelling air quality during the EXPLORE-YRD campaign – Part II. Regional source apportionment of ozone and PM2.5

A source-oriented Community Multiscale Air Quality model was used to quantify the contributions of different sources to ground-level fine particulate matter (PM2.5) and ozone (O3) over the Yangtze River Delta (YRD) region during the EXPLORE-YRD (EXPeriment on the eLucidation of the atmospheric Oxidation capacity and aerosol foRmation, and their Effects in the Yangtze River Delta) campaign (17 May to June 17, 2018). O3 formation in most urban areas of YRD is attributed to volatile organic compounds (VOCs) (81.1%, 78.5%, 60.2%, and 55.1% in Shanghai, Nanjing, Hefei, and Hangzhou, respectively), but is affected more by nitrogen oxides (NOx) in suburban and rural areas. Industry and transportation are the two major sources of O3 and PM2.5. In addition to the two sources, NOx produced owing to power generation, and VOC emissions from biogenic sources are important source of O3. Industry contributes the most to the total mass of PM2.5 in the YRD during the study period (9–25 μg/m3), followed by transportation (2–7 μg/m3). Industry, residential emissions, and transportation are the major sources of primary organic carbon and elemental carbon, whereas industry, transportation, and power generation account for most of the sulphate (SO2− 4) and nitrate (NO− 3) in the YRD. Agriculture is the most dominant source of ammonium emissions (NH+ 4). In Shanghai, Nanjing, Hefei, and Taizhou, secondary organic aerosol (SOA) are mainly contributed by industrial emissions. However, in Hangzhou, biogenic emissions contribute more than 40% of SOA. During all types of pollution episodes, industry and transportation are generally the two greatest sources of O3 and PM2.5 in YRD. The contribution of industry is higher during high PM2.5 pollution episodes, whereas biogenic and open burning contributions are more important during high O3 episodes. Overall, anthropogenic sources dominate the formation of O3 and PM2.5 pollution in the YRD, whereas biogenic emissions contribute significantly to O3 attributable to VOC emissions (O3_VOCs) accounting for 9–20% in urban areas of the YRD.

Ozone affected by a succession of four landfall typhoons in the Yangtze River Delta, China: major processes and health impacts

Abstract. Landfall typhoons can significantly affect O3 in the Yangtze River Delta (YRD) region. In this study, we investigate a unique case characterized by two multiday regional O3 pollution episodes related to four successive landfall typhoons in the summer of 2018 in the YRD. The results show that O3 pollution episodes mainly occurred during the period from the end of a typhoon to the arrival of the next typhoon. The time when a typhoon reached the 24 h warning line and the time when the typhoon dies away in mainland China can be roughly regarded as time nodes. Meanwhile, the variations of O3 were related to the track, duration and landing intensity of the typhoons. The impact of typhoons on O3 was like a wave superimposed on the background of high O3 concentration in the YRD in summer. When a typhoon was near the 24 h warning line before it landed on the coastline of the YRD, the prevailing wind originally from the ocean changed to be from inland, and it transported lots of precursors from the polluted areas to the YRD. Under influences of the typhoon, the low temperature, strong upward airflows, more precipitation and wild wind hindered occurrences of high O3 episodes. After the passing of the typhoon, the air below the 700 hPa atmospheric layer was warm and dry, and the downward airflows resumed. The low troposphere was filed with high concentration of O3 due to O3-rich air transported from the low stratosphere and strong photochemical reactions. It is noteworthy that O3 was mainly generated in the middle of the boundary layer (∼ 1000 m) instead of at the surface. High O3 levels remained in the residual layer at night, and would be transported to the surface by downward airflows or turbulence by the second day. Moreover, O3 can be accumulated and trapped on the ground due to the poor diffusion conditions because the vertical diffusion and horizontal diffusion were suppressed by downward airflows and light wind, respectively. The premature deaths attributed to O3 exposure in the YRD during the study period were 194.0, more than the casualties caused directly by the typhoons. This work has enhanced our understanding of how landfall typhoons affect O3 in the YRD and thus can be useful in forecasting O3 pollution in regions strongly influenced by typhoon activities.

Volatile organic compounds and ozone air pollution in an oil production region in northern China

Abstract. Oil and natural gas (O&NG) exploration presents a significant source of atmospheric volatile organic compounds (VOCs), which are central players of tropospheric chemistry and contribute to formations of ozone (O3) and secondary organic aerosols. The impacts of O&NG extraction on regional air quality have been investigated in recent years in North America, but have long been overlooked in China. To assess the impacts of O&NG exploration on tropospheric O3 and regional air quality in China, intensive field observations were conducted during February–March and June–July 2017 in the Yellow River delta, an oil extraction region in northern China. Very high concentrations of ambient VOCs were observed at a rural site, with the highest alkane mixing ratios reaching 2498 ppbv. High-O3 episodes were not encountered during wintertime but were frequently observed in summer. The emission profiles of VOCs from the oil fields were directly measured for the first time in China. The chemical budgets of ROx radicals and O3 were dissected with a detailed chemical box model constrained by in situ observations. The highly abundant VOCs facilitated strong atmospheric oxidation capacity and O3 formation in the region. Oxygenated VOCs (OVOCs) played an essential role in the ROx primary production, OH loss, and radical recycling. Photolysis of OVOCs, O3, and HONO as well as ozonolysis reactions of unsaturated VOCs were major primary sources of ROx. NOx was the limiting factor of radical recycling and O3 formation. This study underlines the important impacts of O&NG extraction on atmospheric chemistry and regional air quality in China.

Factors controlling surface ozone in the Seoul Metropolitan Area during the KORUS-AQ campaign.

To understand the characteristics of air quality in the Seoul Metropolitan Area, intensive measurements were conducted under the Korea-United States Air Quality (KORUS-AQ) campaign. Trace gases such as O3, NOx, NOy, SO2, CO, and volatile organic compounds (VOCs), photochemical byproducts such as H2O2 and HCHO, aerosol species, and meteorological variables including planetary boundary layer height were simultaneously measured at Olympic Park in Seoul. During the measurement period, high O3 episodes that exceeded the 90 ppbv hourly maximum occurred on 14 days under four distinct synoptic meteorological conditions. Furthermore, local circulation such as land–sea breeze and diurnal evolution of the boundary layer were crucial in determining the concentrations of precursor gases, including NOx and VOC as well as O3. During such episodes, the nighttime NOx and VOC and daytime UV levels were higher compared to non-episode days. The overall precursor levels and photochemical activity were represented fairly well by variations in the HCHO, which peaked in the morning during the high O3 episodes. This study revealed that toluene was the most abundant VOC in Seoul, and its concentration increased greatly with NOx due to the large local influence under stagnant conditions. When O3 was highly elevated concurrently with PM2.5 under dominant westerlies, NOx and VOCs were relatively lower and CO was noticeably higher than in other episodes. Additionally, the O3 production efficiency was the highest due to a low NOx with the highest NOz/NOy ratio among the four episodes. When westerlies were dominant in transport-south episode, the nighttime concentration of O 3 remained as high as 40~50 ppbv due to the minimum level of NOx titration. Overall, the Seoul Metropolitan Area is at NOx-saturated and VOC-limited conditions, which was diagnosed by indicator species and VOC/NOx ratios.

Relating high ozone, ultrafine particles, and new particle formation episodes using cluster analysis

We studied the simultaneity of tropospheric ozone (O3) episodes, high ultrafine particle (UFP; diameter < 100 nm) concentrations, and the occurrence of new particle formation at a regional background station in the Western Mediterranean (northeast Spain), which is affected considerably by the transport of pollutants emitted in the Barcelona metropolitan area and nearby populated and industrial areas. Using cluster analysis, we categorized summer and spring days between 2014 and 2018 according to their daily cycles of O3 concentrations, and then studied the evolution of the particle number size distribution, meteorological variables, and black carbon and sulfur dioxide concentrations. The analysis revealed that, in spring and summer, the highest UFP concentrations coincided with the highest O3 episodes, but new particle formation was largely inhibited during these episodes, probably due to the high aerosol pollution load transported from the Barcelona metropolitan area to the station. In contrast, new particle formation episodes were concurrent with the lowest concentrations of O3 and UFPs, including the number of particles in the 9–25 nm size range. Measurements carried out in an intensive field study, using an air ion spectrometer and a particle size magnifier, support these results. In addition, measurements obtained onboard tethered balloons revealed that sea and land breezes transported regional pollutants vertically up to about 400 m above ground level. This coincided with episodes of vertical recirculation of air masses that lasted for several days, which resulted in high O3 and high UFP episodes, while new particle formation was inhibited.

Adjoint sensitivity of inland ozone to its precursors and meteorological and chemical influences

Adjoint sensitivity analysis of NOx, VOCs, and O3 around the south-eastern part of the Korean Peninsula was performed to estimate their contribution to the high O3 level in the inland city, Daegu. Weather Research and Forecasting (WRF) and Community Multiscale Air Quality (CMAQ) modeling systems were used to simulate local circulation and a high O3 episode day. The adjoint version of the CMAQ model was applied because it is efficient in making decisions for emission control. Areas affecting day time O3 concentration in the receptors were investigated at various times. The results show that the transport of precursors (NOx and VOCs) was more important than that of O3 itself. The main influence area was extended from a neighboring location to eastern coastal city Pohang, affecting mainly on the same day as the receptor time. Another sensitive area was a remote area south of Daegu, where VOCs emitted on the previous day affected O3 concentration at the receptor time in relation with sea-breeze penetration. Sensitivities differed between the lower and upper parts of the boundary layer because of its development during the transport of O3 precursors. After the adjoint sensitivity analysis, the influences of meteorological and chemical effects was investigated separately without the chemical reaction module; the results were 61.9% and 38.1%, respectively. This adjoint result provides valuable information for decision making regarding emission control for air quality.

Surface ozone scenario and air quality in the north-central part of India

Tropospheric pollutants including surface ozone (O3), nitrogen dioxide (NO2), carbon monoxide (CO) and meteorological parameters were measured at a traffic junction (78°2′ E and 27°11′ N) in Agra, India from January 2012 to December 2012. Temporal analysis of pollutants suggests that annual average mixing ratios of tropospheric pollutants were: O3 — 22.97±23.36ppbV, NO2 — 19.84±16.71ppbV and CO — 0.91±0.86ppmV, with seasonal variations of O3 having maximum mixing ratio during summer season (32.41±19.31ppbV), whereas lowest was found in post-monsoon season (8.74±3.8ppbV). O3 precursors: NO2 and CO, showed inverse relationship with O3. Seasonal variation and high O3 episodes during summer are associated with meteorological parameters such as high solar radiation, atmospheric temperature and transboundary transport. The interdependence of these variables showed a link between the daytime mixing ratios of O3 with the nighttime level of NO2. The mixing ratios of CO and NO2 showed tight correlations, which confirms the influence of vehicular emissions combined with other anthropogenic activities due to office/working hours, shallowing, and widening of boundary layer. FLEXTRA backward trajectories for the O3 episode days clearly indicate the transport from the NW and W to S/SE and SW direction at Agra in different seasons.

Phenomenology of high-ozone episodes in NE Spain

Abstract. Ground-level and vertical measurements (performed using tethered and non-tethered balloons), coupled with modelling, of ozone (O3), other gaseous pollutants (NO, NO2, CO, SO2) and aerosols were carried out in the plains (Vic Plain) and valleys of the northern region of the Barcelona metropolitan area (BMA) in July 2015, an area typically recording the highest O3 episodes in Spain. Our results suggest that these very high O3 episodes were originated by three main contributions: (i) the surface fumigation from high O3 reservoir layers located at 1500–3000 m a.g.l. (according to modelling and non-tethered balloon measurements), and originated during the previous day(s) injections of polluted air masses at high altitude; (ii) local/regional photochemical production and transport (at lower heights) from the BMA and the surrounding coastal settlements, into the inland valleys; and (iii) external (to the study area) contributions of both O3 and precursors. These processes gave rise to maximal O3 levels in the inland plains and valleys northwards from the BMA when compared to the higher mountain sites. Thus, a maximum O3 concentration was observed within the lower tropospheric layer, characterised by an upward increase of O3 and black carbon (BC) up to around 100–200 m a.g.l. (reaching up to 300 µg m−3 of O3 as a 10 s average), followed by a decrease of both pollutants at higher altitudes, where BC and O3 concentrations alternate in layers with parallel variations, probably as a consequence of the atmospheric transport from the BMA and the return flows (to the sea) of strata injected at certain heights the previous day(s). At the highest altitudes reached in this study with the tethered balloons (900–1000 m a.g.l.) during the campaign, BC and O3 were often anti-correlated or unrelated, possibly due to a prevailing regional or even hemispheric contribution of O3 at those altitudes. In the central hours of the days a homogeneous O3 distribution was evidenced for the lowest 1 km of the atmosphere, although probably important variations could be expected at higher levels, where the high O3 return strata are injected according to the modelling results and non-tethered balloon data. Relatively low concentrations of ultrafine particles (UFPs) were found during the study, and nucleation episodes were only detected in the boundary layer. Two types of O3 episodes were identified: type A with major exceedances of the O3 information threshold (180 µg m−3 on an hourly basis) caused by a clear daily concatenation of local/regional production with accumulation (at upper levels), fumigation and direct transport from the BMA (closed circulation); and type B with regional O3 production without major recirculation (or fumigation) of the polluted BMA/regional air masses (open circulation), and relatively lower O3 levels, but still exceeding the 8 h averaged health target. To implement potential O3 control and abatement strategies two major key tasks are proposed: (i) meteorological forecasting, from June to August, to predict recirculation episodes so that NOx and VOC abatement measures can be applied before these episodes start; (ii) sensitivity analysis with high-resolution modelling to evaluate the effectiveness of these potential abatement measures of precursors for O3 reduction.

Impact of high-resolution sea surface temperature, emission spikes and wind on simulated surface ozone in Houston, Texas during a high ozone episode

Model-measurement comparisons for surface ozone often show significant error, which could be attributed to problems in meteorology and emissions fields. A WRF-SMOKE-CMAQ air quality modeling system was used to investigate the contributions of these inputs. In this space, a base WRF run (BASE) and a WRF run initializing with NOAA GOES satellite sea surface temperature (SST) (SENS) were performed to clarify the impact of high-resolution SST on simulated surface ozone (O3) over the Greater Houston area during 25 September 2013, corresponding to the high O3 episode during the NASA DISCOVER-AQ Texas campaign. The SENS case showed reduced land-sea thermal contrast during early morning hours due to 1–2 °C lower SST over water bodies. The lowered SST reduced the model wind speed and slowed the dilution rate. These changes led to a simulated downwind O3 change of ∼5 ppb near the area over land with peak simulated afternoon O3. However, the SENS case still under-predicted surface O3 in urban and industrial areas. Episodic flare emissions, dry sunny postfrontal stagnated conditions, and land-bay/sea breeze transitions could be the potential causes of the high O3.In order to investigate the additional sources of error, three sensitivity simulations were performed for the high ozone time period. These involved adjusted emissions, adjusted wind fields, and both adjusted emissions and winds. These scenarios were superimposed on the updated SST (SENS) case. Adjusting NOx and VOC emissions using simulated/observed ratios improved correlation and index of agreement (IOA) for NOx from 0.48 and 0.55 to 0.81 and 0.88 respectively, but still reported spatial misalignment of afternoon O3 hotspots. Adjusting wind fields to represent morning weak westerly winds and afternoon converging zone significantly mitigated under-estimation of the observed O3 peak. For example, simulations with adjusted wind fields and adjusted (emissions + wind fields) reduced under-estimation of the peak magnitude of 100 ppb from 50 ppb to 7 and 9 ppb. Additionally, these sensitivity cases captured the timing and location of the observed O3 hotspots. The simulation case with both adjusted emissions and wind fields showed the best statistics for NOx (correlation: 0.84; IOA: 0.90) and O3 (correlation: 0.87; IOA: 0.92). These comparisons suggest that emissions and wind fields are important in determining the magnitude of high peaks, and wind direction is more critical in determining their timing and location. Particularly, improving the model capability to reproduce small-scale meteorological conditions favoring O3 production, such as stagnation and wind reversal, is crucial for accurate placement of locations of peak O3 and its precursors.

Why does surface ozone peak before a typhoon landing in southeast China?

Abstract. A high O3 episode with the large increases in surface ozone by 21–42 ppbv and the nocturnal surface O3 levels exceeding 70 ppbv was observed in the region between Xiamen and Quanzhou over the southeastern coast of China during 12–14 June 2014, before the Typhoon Hagibis landing. Variations in the surface O3, NO2, CO and meteorology during the Typhoon Hagibis event clearly suggest a substantial impact of the peripheral downdrafts in the large-scale typhoon circulation on such an O3 episode excluding the contributions of photochemical production and the horizontal transport. The influence of vertical O3 transport from the upper troposphere and lower stratosphere (UTLS) region on high surface O3 levels is further confirmed by a negative correlation between surface O3 and CO concentrations as well as dry surface air observed during the O3 episode. This study provides observational evidence of typhoon-driven intrusion of O3 from the UTLS region to surface air, revealing a significant effect of such a process of stratosphere–troposphere exchange (STE) of O3 on tropospheric O3 and ambient air quality.

Understanding high wintertime ozone pollution events in an oil- and natural gas-producing region of the western US

Abstract. Recent increases in oil and natural gas (NG) production throughout the western US have come with scientific and public interest in emission rates, air quality and climate impacts related to this industry. This study uses a regional-scale air quality model (WRF-Chem) to simulate high ozone (O3) episodes during the winter of 2013 over the Uinta Basin (UB) in northeastern Utah, which is densely populated by thousands of oil and NG wells. The high-resolution meteorological simulations are able qualitatively to reproduce the wintertime cold pool conditions that occurred in 2013, allowing the model to reproduce the observed multi-day buildup of atmospheric pollutants and the accompanying rapid photochemical ozone formation in the UB. Two different emission scenarios for the oil and NG sector were employed in this study. The first emission scenario (bottom-up) was based on the US Environmental Protection Agency (EPA) National Emission Inventory (NEI) (2011, version 1) for the oil and NG sector for the UB. The second emission scenario (top-down) was based on estimates of methane (CH4) emissions derived from in situ aircraft measurements and a regression analysis for multiple species relative to CH4 concentration measurements in the UB. Evaluation of the model results shows greater underestimates of CH4 and other volatile organic compounds (VOCs) in the simulation with the NEI-2011 inventory than in the case when the top-down emission scenario was used. Unlike VOCs, the NEI-2011 inventory significantly overestimates the emissions of nitrogen oxides (NOx), while the top-down emission scenario results in a moderate negative bias. The model simulation using the top-down emission case captures the buildup and afternoon peaks observed during high O3 episodes. In contrast, the simulation using the bottom-up inventory is not able to reproduce any of the observed high O3 concentrations in the UB. Simple emission reduction scenarios show that O3 production is VOC sensitive and NOx insensitive within the UB. The model results show a disproportionate contribution of aromatic VOCs to O3 formation relative to all other VOC emissions. The model analysis reveals that the major factors driving high wintertime O3 in the UB are shallow boundary layers with light winds, high emissions of VOCs from oil and NG operations compared to NOx emissions, enhancement of photolysis fluxes and reduction of O3 loss from deposition due to snow cover.

Simulation of ozone formation at different elevations in mountainous area of Hong Kong using WRF-CMAQ model

Field measurements were simultaneously conducted at a mountain (Mt.) site (Tai Mao Shan, TMS) and an urban site (Tsuen Wan, TW) at the foot of the Mt. TMS in Hong Kong. An interesting event with consecutive high-ozone (O3) days from 08:00 on 28 Oct. to 23:00 on 03 Nov., 2010 was observed at Mt. TMS, while no such polluted event was found at the foot of the mountain. The Weather Research and Forecasting (WRF)-Community Multiscale Air Quality (CMAQ) models were used to understand this event. Model performance evaluation showed that the simulated meteorological parameters and air pollutants were well in agreement with the observations. The index of agreement (IOA) of temperature, relative humidity, wind direction and wind speed were 0.93, 0.83, 0.46 and 0.60, respectively. The multi-day high O3 episode at Mt. TMS was also reasonably reproduced (IOA=0.68). Horizontally, the photochemical processes determined the O3 levels in southwestern Pearl River Delta (PRD) and the Pearl River Estuary (PRE), while in eastern and northern PRD, the O3 destruction was over the production during the event. Vertically, higher O3 values at higher levels were found at both Mt. TMS and TW, indicating a vertical O3 gradient over Hong Kong. With the aid of the process analysis module, we found positive contribution of vertical transport including advection and diffusion to O3 mixing ratios at the two sites, suggesting that O3 values at lower locations could be affected by O3 at higher locations via vertical advection and diffusion over Hong Kong.

A study on high ozone formation mechanism associated with change of NOx/VOCs ratio at a rural area in the Korean Peninsula

We present an analysis of high surface ozone (O3) episodes occurring in the rural area of Chuncheon, which is situated 70 km to the prevailing westerly downwind direction of Seoul Metropolitan Area. During the episode days, the daily maximum O3 concentration exceeded 120 ppb and an O3 warning was issued in Chuncheon. Although Chuncheon has much lower emission levels than Seoul, the daily mean and maximum O3 levels were higher in Chuncheon than those in Seoul during the episode days. In addition, the high O3 concentrations in Chuncheon were not dependent on the meteorological condition being generally favorable for O3 production. The inverse trajectory analysis using HYSPLIT clearly shows the features of pollutant transport from Seoul to Chuncheon. For further investigation, we conducted numerical experiments using the atmospheric dynamic Weather Research and Forecasting (WRF) model and the air quality Community Multi-scale Air Quality (CMAQ) model to examine the detail process of these high O3 episodes with the Decoupled Direct Method (DDM-3D) and Integrated Process Rate (IPR) analyses. The DDM-3D analysis results demonstrate that the O3 concentration in the air mass moving from Seoul to Chuncheon was very sensitive to the concentration of nitrogen oxide (NOx) because of abundant biogenic volatile organic compounds (BVOCs). The IPR results also show that the NOx emitted from Seoul strongly affected the high O3 levels over its downwind area, mainly with local BVOC emissions. The produced O3 was gradually accumulated during its transport downwind, leading to an O3 concentration maximum at Chuncheon.

Modeling study of three consecutive high ozone episodes over Taiwan in spring 2007

A three-dimensional photochemistry model is applied to analyze three unusual high O3 episodes that occurred continuously in Taiwan from May 1 to 11, 2007. During this period, the first high ozone episode was observed in northern and central western Taiwan on May 4. Following this episode, the second episode was observed throughout Taiwan on May 7, and continued for several days until May 10, when the third episode was observed in central western and southwestern Taiwan. This was the worst O3 period in Taiwan over the past two decades. During this period, 70% of the local air quality station reported an O3 concentration of over 120 ppb, and a maximum O3 concentration of 175 ppb was observed in background Taiwan.Based on model analyses, the sources of the three high O3 episodes differ. The high O3 concentration observed during the first episode is mainly attributed to the northeastward transport of O3 precursors and concentrations from northern and central western Taiwan under southwesterlies prior to frontal passage, chemically producing O3 over 30 ppb h−1 in northern Taiwan. During the second episode, horizontal advection of Asian outflow during the passage of an anticyclone and front contributes a maximum of 25 ppb h−1 in both northern and southern tip of Taiwan, respectively, increasing to more than 75 ppb h−1 in southwestern Taiwan because of the combination with the local source. During the third episode when the prevailing easterlies associated with a departing anticyclone to the east of Taiwan is blocked by the high central mountain, local O3 chemical production and horizontal transport contribute a maximum of 25 ppb h−1 and 35 ppb h−1 in central and southwestern Taiwan, respectively, under a calm and high background O3 condition.Source from Taiwan contributes more than half of the high O3 concentration over northwestern Taiwan prior to frontal passage during the first episode, but decreases to mostly below 40% over western Taiwan during the second episode when Asian outflow occurs, and increases to more than 60% over central and southwestern Taiwan due to pollution accumulation under an anticyclonic departure.

Simulating near-road reactive dispersion of gaseous air pollutants using a three-dimensional Eulerian model

In this study, the TAMNROM-3D model, a 3D Eulerian near-road air quality model with vehicle induced turbulence parameterization and a MOVES based emission preprocessor, is tested using near-road gaseous pollutants data collected near a rural freeway with 34% heavy duty vehicle traffic. Exhaust emissions of gasses from the vehicles are estimated using a lumped vehicle classification scheme based on the number of vehicle axles and the default county-level MOVES vehicle fleet database. The predicted dilution of CO and NOx in the downwind direction agrees well with observation, although the total NOx emission has to be scaled to 85% of its original emission rate estimated by the MOVES model. Using the atmospheric turbulent diffusion coefficient parameterization of Degrazia et al. (2000) with variable horizontal turbulent diffusion coefficient (Kxx) leads to slightly better predictions than a traditional non-height-dependent Kxx parameterization. The NO2 concentrations can be better predicted when emission of total NOx is split into NO and NO2 using the NO2 to NOx ratio of 29% measured near the road. Simulations using the SAPRC99 photochemical mechanism do not show significant changes in the predicted NO and NO2 concentrations near the road compared to simulations using a simple three-reaction mechanism that involves only NOx and O3. A regional air quality simulation in Houston, Texas during a high O3 episode in August 2000 shows that using the NO2 to NOx ratio of 29% instead of the traditional 5% leads to as much as 6ppb increase in 8-h O3 predictions.

Assessment of the Contribution of Wildfires to Ozone Concentrations in the Central US-Mexico Border Region

The annual trends and spatiotemporal patterns of monthly 8-hour maximum ozone (8-hr max O3) concentrations in the Paso del Norte region were analyzed, and their associations with fires were examined for the 2001–2010 period. Hourly O3 measurements were retrieved from the Environmental Protection Agency (EPA) Air Quality System, while the times and locations of fires were acquired from the MODIS fire detection module. The absolute 8-hr max O3 concentrations were comparable in urban, rural and background sites. Time series analysis of deseasonalized monthly 8-hr max O3 levels showed statistically significant declining trends for most of the sites located in populated areas, and high correlation coefficients among these. Conversely, a 0.12 ppbv/yr increase of 8-hr max O3 concentration was computed for Chiricahua, a background site located in a Class I protected area. Strong relationships between the monthly 8-hr max O3 concentrations and categorical variables representing the number of fire detections for each month in six buffer zones were computed. Fire incidents near the sites (within 400 km) in central Arizona, central Texas and western Mexico triggered a decrease in the 8-hr max O3 concentration by 1 to 12 ppbv in urban and rural sites, and an increase of 3 ppbv in Chiricahua. Conversely, fire incidents in southeast US, Cuba and central Mexico contributed from 5 up to 19 ppbv. These findings indicated that regional fire incidents may trigger high O3 episodes, which may exceed air quality standards.