The exceedance patterns of air quality criteria: a case study of ozone and nitrogen dioxide in Seoul, Korea between 1990 and 2000

In this study, the environmental behavior of two major airborne pollutants, ozone and nitrogen dioxide, was investigated with respect to their exceedance patterns of air quality criteria. For this purpose, we used data sets collected from a total of 31 air quality monitoring stations dispersed across the Seoul metropolitan city between 1990 and 2000. In the case of NO(2), the frequency of hourly exceedance data sets exhibited little changes in the early 90s. However, it increased dramatically after 1995, probably in compliance with a rapid increase in the total number of automobiles. Likewise, the daily exceedance of O(3) in the early 90s was not significant, approaching 100 cases (except in 1994). However, its total quantity began to surpass 300 cases since around 1996. Comparison of those exceedance data was also made among spatially divided data groups. In the case of NO(2), the occurrence of exceedance data was dominated by the western part of the city in both magnitude and frequency. On the other hand, that for O(3) was characterized by notably strong occurrences in the eastern counterpart. The overall results of our analysis of the NO(2) and O(3) exceedance data sets indicate an inextricable linkage between the two pollutants in association with geographical and meteorological factors.     

Ground-level ozone in the Pearl River Delta region: Analysis of data from a recently established regional air quality monitoring network

The ambient air quality monitoring data of 2006 and 2007 from a recently established Pearl River Delta (PRD) regional air quality monitoring network are analyzed to investigate the characteristics of ground-level ozone in the region. Four sites covering urban, suburban, rural and coastal areas are selected as representatives for detailed analysis in this paper. The results show that there are distinct seasonal and diurnal cycles in ground-level ozone across the PRD region. Low ozone concentrations are generally observed in summer, while high O₃ levels are typically found in autumn. The O₃ diurnal variations in the urban areas are larger than those at the rural sites. The O₃ concentrations showed no statistically significant difference between weekend and weekdays in contrast to the findings in many other urban areas in the world. The average ozone concentrations are lower in urban areas compared to the sites outside urban centers. Back trajectories are used to show the major air-mass transport patterns and to examine the changes in ozone from the respective upwind sites to a site in the center of the PRD (Wanqingsha). The results show higher average ozone concentrations at the upwind sites in the continental and coastal air masses, but higher 1 h-max O₃ concentrations (by 8–16 ppbv) at the center PRD site under each of air-mass category, suggesting that the ozone pollution in the PRD region exhibits both regional and super-regional characteristics.     

Measurements and analyses of nitrogen oxides and ozone in the yard and on the roof of a street-canyon in Suzhou

The concentrations of air pollutants such as nitrogen oxides and ozone characterised by very fast chemical reactions can significantly vary within urban street-canyon due to the short distances between sources and receptor. With the primary objective to analyse this issue, NO, NO₂, NO_x, O₃, BTX, and wind flow field were continuously measured for 1 week at two heights (a street-level yard and a 25-m-high rooftop) in an urban canyon in Suzhou (China). The yard ozone concentrations were found to be up to six times lower than on the roof. Different frequency distributions (FD), dynamical and chemical processes of the pollutant variations from yard to roof are discussed to explain the findings. The predominant factors for the dissimilar pollutant vertical diffusion at the two measurement locations were associated to dissimilar fluid-dynamic and heterogeneous removal effects that likely induced dissimilar ozone chemical processes relative to NO_x and BTX precursors.     

香港港口氮氧化物和臭氧的变化特征和周末效应

为了研究香港港口氮氧化物和臭氧（NO2、NOx和O3）的周末效应,本文收集香港港口15年的污染数据进行统计分析。首先分析污染物的日变化特征,结果发现工作日NO2和NOx浓度高于周六,周六浓度高于周日的情形。与此相反,工作日O3浓度低于周六,周六浓度低于周日。其次分析污染物年变化,结果表明近些年NO2和NOx呈降低趋势,O3呈增加趋势。还发现NO2、NOx和O3的周末效应减弱。然后使用线性回归分析光化学氧化剂（OX,O3+NO2）的局地和区域贡献,结果发现受港口作业周期性变化的影响,OX的局地贡献表现出工作日高于周六,周六高于周日的周末效应现象。最后分析了OX局地贡献的昼夜差异,结果显示白天OX局地贡献的周末效应明显强于晚上。     

Integrated biomonitoring of air quality with plants and lichens: a case study on ambient ozone from central Italy

A biennial integrated survey, based on the use of vascular plants for the bioindication of the effects of tropospheric ozone together with the use of automatic analysers of ozone, as well as the mapping of lichen biodiversity was performed in the area of Castelfiorentino (Tuscany, central Italy). Photochemically produced ozone proved to be a fundamental presence during the warm season, with maximum hourly means reaching 114 ppb, exceeding the information threshold as fixed by EU: the use of supersensitive tobacco Bel-W3 confirmed the opportunity of carrying out detailed cost-effective monitoring surveys. The potential for didactical and educational implications of this methodology are appealing. Critical levels set up for the protection of vegetation have exceeded considerably. The comparison of biomass productivity in sensitive and resistant individuals (NC-S and NC-R white clover clones, in the framework of an European network) provided evidence that ambient ozone levels are associated with relevant reduction (up to 30%) in the performance of sensitive material; effects on flowering were also pronounced. The economic assessment of such an impact deserves attention. Mapping of epiphytic lichen biodiversity – which has been used to monitor air quality worldwide – was not related to ozone geographical distribution as depicted by tobacco response.     

Dynamic evaluation of a regional air quality model: Assessing the emissions-induced weekly ozone cycle

Air quality models are used to predict changes in pollutant concentrations resulting from envisioned emission control policies. Recognizing the need to assess the credibility of air quality models in a policy-relevant context, we perform a dynamic evaluation of the Community Multiscale Air Quality (CMAQ) modeling system for the “weekend ozone effect” to determine if observed changes in ozone due to weekday-to-weekend (WDWE) reductions in precursor emissions can be accurately simulated. The weekend ozone effect offers a unique opportunity for dynamic evaluation, as it is a widely documented phenomenon that has persisted since the 1970s. In many urban areas of the Unites States, higher ozone has been observed on weekends than weekdays, despite dramatically reduced emissions of ozone precursors (nitrogen oxides [NO_x] and volatile organic compounds [VOCs]) on weekends. More recent measurements, however, suggest shifts in the spatial extent or reductions in WDWE ozone differences. Using 18 years (1988–2005) of observed and modeled ozone and temperature data across the northeastern United States, we re-examine the long-term trends in the weekend effect and confounding factors that may be complicating the interpretation of this trend and explore whether CMAQ can replicate the temporal features of the observed weekend effect. The amplitudes of the weekly ozone cycle have decreased during the 18-year period in our study domain, but the year-to-year variability in weekend minus weekday (WEWD) ozone amplitudes is quite large. Inter-annual variability in meteorology appears to influence WEWD differences in ozone, as well as WEWD differences in VOC and NO_x emissions. Because of the large inter-annual variability, modeling strategies using a single episode lasting a few days or a few episodes in a given year may not capture the WEWD signal that exists over longer time periods. The CMAQ model showed skill in predicting the absolute values of ozone concentrations during the daytime. However, early morning NO_x concentrations were underestimated and ozone levels were overestimated. Also, the modeled response of ozone to WEWD differences in emissions was somewhat less than that observed. This study reveals that model performance may be improved by (1) properly estimating mobile source NO_x emissions and their temporal distributions, especially for diesel vehicles; (2) reducing the grid cell size in the lowest layer of CMAQ; and, (3) using time-dependent and more realistic boundary conditions for the CMAQ simulations.     

南京北郊春季地面臭氧与氮氧化物浓度特征

2009年3—5月,采用NO-NO2-NH3分析仪和O3分析仪对南京市北郊大气O3、NO、NO2和NOx浓度进行连续观测,研究南京北郊春季大气臭氧与氮氧化物浓度变化特征。结果表明:O3浓度的日变化呈单峰型结构,白天较高,夜晚较低,在06:00左右出现最低值,14:00左右出现峰值,且工作日的O3浓度值明显高于周末的O3浓度值。NOx的日变化呈现双峰型变化规律,早上07:00左右出现第1个峰值,下午14:00—15:00左右达到最低值,午夜23:00左右出现第2个峰值。从3—5月份,NO浓度明显下降,3月份的变化幅度比较大;NO2浓度则明显上升,5月份变化幅度较大。3—5月NO与O3之间呈显著的负相关关系,4—5月NO2、NOx与O3呈显著的负相关关系。     

Assessment of ozone visible symptoms in the field: perspectives of quality control

The second UN/ECE ICP-Forests Intercalibration Course on the Assessment of Ozone Injury on European Tree Species was carried out in August 2001 at Lattecaldo (Canton Ticino, CH) and Moggio (Lombardy, I). Forty-eight experts from several European countries participated in the exercises and assessed visible symptoms of ozone injury both in open-top chambers (OTC) (Lattecaldo) and under open field (Moggio) conditions. Evaluation of the results indicated a large variability among the teams and call for adequate training of the observers prior to symptom assessment for quality assurance purposes. Highest variability was found for the species developing unclear symptoms which could be confused with senescence processes; such species should not be used in the field. The authors provide suggestions to improve the reliability of the ozone injury assessment on forest plant species.     

Vegetation exposure to ozone over the continental United States: Assessment of exposure indices by the Eta-CMAQ air quality forecast model

The main use of air quality forecast (AQF) models is to predict ozone (O₃) exceedances of the primary O₃ standard for informing the public of potential health concerns. This study presents the first evaluation of the performance of the Eta-CMAQ air quality forecast model to predict a variety of widely used seasonal mean and cumulative O₃ exposure indices associated with vegetation using the U.S. AIRNow O₃ observations. These exposure indices include two concentration-based O₃ indices, M7 and M12 (the seasonal means of daytime 7-h and 12-h O₃ concentrations, respectively), and three cumulative exposure-based indices, SUM06 (the sum of all hourly O₃ concentrations ≥ 0.06 ppm), W126 (hourly concentrations weighed by a sigmoidal weighting function), and AOT40 (O₃ concentrations accumulated over a threshold of 40 ppb during daylight hours). During a three-month simulation (July–September 2005), the model over predicted the M7 and M12 values by 8–9 ppb, or a NMB value of 19% and a NME value of 21%. The model predicts a central belt of high O₃ extending from Southern California to Middle Atlantic where the seasonal means, M7 and M12 (the seasonal means of daytime 7-h and 12-h O₃ concentrations), are higher than 50 ppbv. In contrast, the model is less capable of reproducing the observed cumulative indices. For AOT40, SUM06 and W126, the NMB and NME values are two- to three-fold of that for M7, M12 or peak 8-h O₃ concentrations. The AOT40 values range from 2 to 33 ppm h by the model and from 1 to 40 ppm h by the monitors. There is a significantly higher AOT40 value experienced in the United States in comparison to Europe. The domain-wide mean SUM06 value is 14.4 ppm h, which is about 30% higher than W126, and 40% higher than AOT40 calculated from the same 3-month hourly O₃ data. This suggests that SUM06 and W126 represent a more stringent standard than AOT40 if either the SUM06 or the W126 was used as a secondary O₃ standard. Although CMAQ considerably over predicts SUM06 and W126 values at the low end, the model under predicts the extreme high exposure values (>50 ppm h). Most of these extreme high values are found at inland California sites. Based on our analysis, further improvement of the model is needed to better capture cumulative exposure indices.     

Trends in concentration of ground-level ozone and meteorological conditions during high ozone episodes in the Kao-Ping Airshed, Taiwan

This work analyzes the variations in daily maximum 1-hr ozone (O3) concentrations and the long-term trends in annual means of hourly ambient concentrations of O3, nitrogen oxides (nitrous oxide + nitrogen dioxide), and nonmethane hydrocarbons in the three administrative regions of Kao-Ping airshed in southern Taiwan over a recent 8-yr period. The annual or monthly means of all maxima, most 95th percentiles, and some 90th percentiles of the daily maximum 1-hr O3 concentrations exceed the daily limit of 120 parts per billion by volume in all three regions, namely, Kao-hsiung City, Kso-hsiung County, and P'ing-tung County. The monthly means of daily maximum 1-hr O3 concentrations exhibit distinct seasonal variations, with a bimodal form with the maxima in autumn and late winter to the middle of spring and a minimum in summer. The long-term variations in the annual means of hourly O3 concentrations in the three regions exhibit increasing trends. These increases in O3 are associated with the decline in ambient concentrations of nitrogen oxides and nonmethane hydrocarbons. High O3 episodes occur most often in autumn and most rarely in summer. The seasonal mean mixing heights in descending order follow the order of spring, summer, autumn, and winter. Meteorological parameters in autumn and winter indicate that the ground-level O3 tends to accumulate and trigger a high O3 episode on a warm day with sufficient sunlight and low wind in a high-pressure system, consistent with the low mixing heights in these two seasons.     

Nitrogen oxides and ozone in Portugal: trends and ozone estimation in an urban and a rural site

Environmental Science and Pollution Research - This study provides an analysis of the spatial distribution and trends of NO, NO2 and O3 concentrations in Portugal between 1995 and 2010....     

Sulphur dioxide,oxides of nitrogen and ozone measured continuously for 2 years at a rural site

Continuous specific measurements of sulphur dioxide, nitric oxide, nitrogen dioxide and ozone have been made for over 2y at Bottesford, a rural site in central England, 20 km away from town and industry sources and 1 km from traffic sources. Statistics of hourly, daily, monthly, seasonal and yearly values are given.On an annual basis, there was 50% more oxides of nitrogen (nitric oxide plus nitrogen dioxide) than sulphur dioxide, and more ozone than either. The nitric oxide and nitrogen dioxide were approximately equal. No other published annual values of nitric oxide, nitrogen dioxide and ozone at U.K. rural sites are known. The summer nitric oxide values were greater at this site than at three other rural sites in the British Isles for which summer nitric oxide values have been reported, but so was the sulphur dioxide, and the amounts of both these gases probably reflect the size and distance of combustion sources.Diurnal variations of the four gases during summer months at Bottesford were similar to those published for a site in southern England. The diurnal variations for winter months at Bottesford were somewhat different, especially for nitrogen dioxide. No other published winter patterns are known.Usually nitrogen dioxide and ozone concentrations were in opposition, both short and long term, but on rare occasions, for example in relatively clean winter air, the ozone concentration rose and fell directly with the nitrogen dioxide. Hourly ozone values exceeded 50 ppb (10⁻⁹, by volume) for several hours a month in 22 months out of 24. The World Health Organisation guideline for public health exposure limits is given as 50–100 ppb h⁻¹, not to be exceeded more than once per month.     

Monitoring ambient ozone with a network of passive samplers: a feasibility study

Ambient levels of ozone have been measured at 46 mountain forest, desert, Class I Wilderness areas and other remote locations using a network of passive samplers. Typical values were 40-80 ppb (2 week samples) and exhibited temporal variations (studied for up to 1 year) as well as changes with elevation (studied up to 10 500 ft (3 200 m)). The performance of the passive sampler was evaluated with respect to reproducibility, field controls, data capture (>0.95), precision for co-located samples (av. = 11.9%, n = 103), and the role of other atmospheric oxidants as potential interferents (2 locations). Suggestions for additional sampler performance evaluation and network operation are outlined.     

Ground-based remote sensing measurements of aerosol and ozone in an urban area: A case study of mixing height evolution and its effect on ground-level ozone concentrations

We have estimated the mixing height (MH) and investigated the relationship between vertical mixing and ground-level ozone concentrations in Seoul, Korea, by using three ground-based active remote sensing instruments operating side by side: micro-pulse lidar (MPL), differential absorption lidar (DIAL), and differential optical absorption spectroscopy (DOAS). The MH is estimated from MPL measurements of aerosol extinction profiles by the gradient method under convective conditions. Comparisons of the MHs estimated from MPL and radiosonde measurements show a good agreement (r²=0.99). Continuous MPL measurements with high temporal and vertical resolution reveal the diurnal variations of the MH under convective conditions and the presence of a residual layer during the nighttime. Comprehensive measurements of ozone and aerosol by MPL, DIAL and DOAS during an high ozone episode (24–26 May 2000) in Seoul, Korea, reveal that (1) photochemical ozone production and advection from upwind regions (the western part of Seoul) contribute two peaks of ozone concentrations at the ground around 14:00 and 18:00 local time on 25 May 2000, respectively, and (2) the entrainment and the fumigation processes of ozone aloft in the nighttime residual layer into the ground is a major contributor of high concentrations of ground-level ozone observed on the following day (26 May 2000).     

Assessment of air quality benefits from national air pollution control policies in China. Part II: Evaluation of air quality predictions and air quality benefits assessment

Following the meteorological evaluation in Part I, this Part II paper presents the statistical evaluation of air quality predictions by the U.S. Environmental Protection Agency (U.S. EPA)’s Community Multi-Scale Air Quality (Models-3/CMAQ) model for the four simulated months in the base year 2005. The surface predictions were evaluated using the Air Pollution Index (API) data published by the China Ministry of Environmental Protection (MEP) for 31 capital cities and daily fine particulate matter (PM_2.5, particles with aerodiameter less than or equal to 2.5 μm) observations of an individual site in Tsinghua University (THU). To overcome the shortage in surface observations, satellite data are used to assess the column predictions including tropospheric nitrogen dioxide (NO₂) column abundance and aerosol optical depth (AOD). The result shows that CMAQ gives reasonably good predictions for the air quality.The air quality improvement that would result from the targeted sulfur dioxide (SO₂) and nitrogen oxides (NO_x) emission controls in China were assessed for the objective year 2010. The results show that the emission controls can lead to significant air quality benefits. SO₂ concentrations in highly polluted areas of East China in 2010 are estimated to be decreased by 30–60% compared to the levels in the 2010 Business-As-Usual (BAU) case. The annual PM_2.5 can also decline by 3–15 μg m^?3 (4–25%) due to the lower SO₂ and sulfate concentrations. If similar controls are implemented for NO_x emissions, NO_x concentrations are estimated to decrease by 30–60% as compared with the 2010 BAU scenario. The annual mean PM_2.5 concentrations will also decline by 2–14 μg m^?3 (3–12%). In addition, the number of ozone (O₃) non-attainment areas in the northern China is projected to be much lower, with the maximum 1-h average O₃ concentrations in the summer reduced by 8–30 ppb.     

Long term changes in nitrogen oxides and volatile organic compounds in Toronto and the challenges facing local ozone control

Ground level ozone represents a significant air quality concern in Toronto, Canada, where the national 65 ppb 8-h standard is repeatedly exceeded during the summer. Here we present an analysis of nitrogen dioxide (NO₂), ozone (O₃), and volatile organic compound (VOC) data from federal and provincial governmental monitoring sites from 2000 to 2007. We show that summertime VOC reactivity and ambient concentrations of NO₂ have decreased over this period of time by up to 40% across Toronto and the surrounding region. This has not resulted in significant summertime ozone reductions, and in some urban areas, it appears to be increasing. We discuss the competing effects of decreased ozone titration leading to an increase in O₃, and decreased local ozone production, both caused by significant decreases in NO_x concentrations. In addition, by using local meteorological data, we show that annual variability in summer ozone correlates strongly with maximum daily temperatures, and we explore the effect of atmospheric transport from the southwest which has a significant influence on early morning levels before local production begins. A mathematical model of instantaneous ozone production is presented which suggests that, given the observed decreases in NO_x and VOC reactivity, we would not expect a significant change in local ozone production under photochemically relevant conditions. These results are discussed in the context of Toronto's recent commitment to cutting local smog-causing pollutants by 20% by 2012.     

Environmental fate of chlordecone in coastal habitats: recent studies conducted in Guadeloupe and Martinique (Lesser Antilles)

Environmental Science and Pollution Research - The organochlorine pollution by chlordecone, an insecticide spread in the past in banana plantations, is now recognized as a major ecological,...     

Assessment of ambient air quality in the port of Naples

Two experimental monitoring campaigns were carried out in 2012 to investigate the air quality in the port of Naples, the most important in southern Italy for traffic of passengers and one of the most important for goods. Therefore, it represents an important air pollution source located close to the city of Naples. The concentrations of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and BTEX (benzene, toluene, ethylbenzene, and xylenes) in the air were measured at 15 points inside the Naples port area through the use of passive samplers. In addition, a mobile laboratory was positioned in a fixed point inside the port area to measure continuous concentration of pollutants together with particulate matter, ambient parameters, and wind direction and intensity. The pollution levels monitored were compared with those observed in the urban area of Naples and in other Mediterranean ports. Even though the observation time was limited, measured concentrations were also compared with limit values established by European legislation. All the measured pollutants were below the limits with the exception of nitrogen dioxide: its average concentration during the exposition time exceeded the yearly limit value. A spatial analysis of data, according to the measured wind direction and intensity, provided information about the effects that ship emissions have on ambient air quality in the port area. The main evidence indicates that ship emissions influence sulfur dioxide concentration more than any other pollutants analyzed.

Implications: Two monitoring campaigns were carried out to measure BTEX, SO₂, NO₂, and PM₁₀ (particulate matter with an aerodynamic diameter <10 μm) air concentrations in the port of Naples. NO₂ hourly average and PM₁₀ daily average comply with European legislative standards. Spatial variation of pollutants long the axis corresponding to the prevailing wind direction seems to indicate a certain influence of ship emissions for SO₂. For NO₂ and PM₁₀, a correlation between concentrations in the harbor and those measured by the air quality monitoring stations sited in the urban area of Naples was observed, indicating a possible contribution of the near road traffic to the air pollution in the port of Naples.     

Evaluation of air quality models for the simulation of a high ozone episode in the Houston metropolitan area

A high ozone event in the Houston–Galveston–Brazoria area was utilized to study the shortcomings of the current air quality models. To improve the baseline simulations with the Comprehensive Air quality Model with Extensions (CAMx) for developing the state implementation plan, the Texas Commission on Environmental Quality (TCEQ) imputed emissions of highly reactive volatile organic compounds (HRVOCs) by scaling the amount of fugitive emissions of olefins to co-emitted NO_x from selected point sources, effectively multiplying by 3–12 times over the regular inventory values. In this paper, CAMx and the Community Multiscale Air Quality (CMAQ) model were used to determine if the imputed HRVOC emissions were consistent with the observed atmospheric conditions. With the base emissions, CMAQ and CAMx both with the Carbon-Bond 4 (CB-4) mechanism simulated similar ozone concentrations. But with the imputed HRVOC emissions, CMAQ predicted lower ozone peaks than CAMx in the vicinity and downwind of the Ship Channel and other highly HRVOC-rich areas. Based on analyses of sensitivity simulations of CMAQ with different emission inputs and vertical diffusion algorithms in the model, we found that the modeled atmosphere lacked reactivity to produce the observed high ozone event. Although the imputed HRVOC emissions improved ozone prediction at the surface sites, but the ethylene concentrations were not consistent with the measurements at the super sites (La Porte and Clinton) and by NOAA aircraft. Several sensitivity tests designed to provide additional radicals into the system and other research results suggested that the lack of reactivity may need to be corrected by targeted, and probably of episodic, increase of HRVOC emissions, from the sources in the Houston Ship Channel. Additional investigation of the ozone production efficiency for different chemical mechanisms is necessary to pinpoint the emissions uncertainty issues.