Mediterranean rural ozone characteristics around the urban area of Athens

A systematic analysis of surface ozone observations in rural areas surrounding Athens is presented. The analysis is based on ozone data for the rural station Aliartos about 80 km NW of Athens center and for two stations on the northern periphery of the Athens basin: Demokritos, located 10 km NE of Athens center and Liossia, 12 km to the north. The data for these two stations are screened for cases of strong air flow from rural areas. Average hourly summer afternoon ozone mixing ratios are similar for all three stations about 60 ppb and thus exceed for the hours 12:00–20:00 LST the 55 ppb WHO guideline for human health for 8 h ozone exposure. The corresponding winter afternoon mixing ratios are at 35 ppb. However, due to the large diurnal variation, mean monthly ozone mixing ratios at Aliartos, for the months April–September vary from 32 to 40 ppb, which is comparable to the higher average ozone levels at rural stations in south-central Europe. In cases of southerly air flow in the summer in the Athens basin, afternoon ozone levels at Demokritos and Liossia are generally the highest of any in the monitoring network. Hourly average concentrations, however, are only 40% greater than rural values. A background ozone level of such magnitude will have a significant impact on estimates for the effectiveness of pollution control measures for Athens.     

Peroxyacetylnitrate (PAN) in the atmosphere of Edmonton,Alberta, Canada

Peroxyacetyl nitrate (PAN) concentrations were measured from December 1982 to May 1984 in downtown Edmonton, Alberta, as well as upwind and downwind of the city. The highest PAN concentration recorded in Edmonton was 7.5 ppb, and the mean daily maximum was 0.6 ppb. Maximum PAN and ozone concentrations were often reached in the early afternoon but there were many exceptions, with maxima as early as 0900 MST and as late as 2000 MST. PAN often persisted throughout the night in Edmonton, whereas in Calgary it disappeared rapidly in the evening. Edmonton PAN concentrations showed seasonal variation and were limited in the wintertime by the lack of solar radiation and in the summer by the low concentration of pollutants. PAN episodes were highly correlated with the presence of anticyclonic synoptic disturbances (ridges) in the upper air flow. Surface synoptic conditions varied but weak pressure gradients were common to all episodes. Seasonal and diurnal variations of PAN are discussed in relation to observations from Calgary, Alberta; Los Angeles, CA; and other North American cities.     

Secondary ozone maxima in a very stable nocturnal boundary layer: observations from the Lower Fraser Valley,BC

The relationship between near-surface ozone concentration and the structure of the nocturnal boundary layer was investigated during a field campaign conducted in 1998 in the Lower Fraser Valley (LFV), British Columbia Canada. Despite the spatial and temporal variation in frequency and morphology, secondary nocturnal ozone maxima were shown to be an important feature of the diurnal ozone cycle throughout the LFV, and localised increases in ozone occasionally exceeded more than half the previous day's maximum concentration.Turbulence in the nocturnal boundary layer was shown to be weak and intermittent. Vertical profiles of Richardson number and ozone concentration indicated that the temporary turbulent coupling of the residual layer to the surface layer facilitated the transport of ozone stored aloft to the surface. Despite the overall complexity of the system, results show that seven out of the 19 ozone spikes observed at the Aldergrove site coincided with turbulence associated with the development of the down-valley wind system. A further nine spikes occurred during periods when a low-level jet was identified aloft. Significantly, ozone concentrations were shown to be highly variable in the residual layer and played an important role in determining the morphology of secondary ozone maxima at the surface. Largest increases in surface ozone concentration occurred when turbulence coincided with periods when ozone concentrations in excess of 80 ppb were observed aloft.     

An Empirical Model for Forecasting Maximum Daily Ozone Levels in the Northeastern U.S.

A stepwise multiple regression procedure was employed to develop the best .fit equation relating maximum afternoon ozone concentrations to meteorological and emission factors along a 24h upwind air parcel trajectory. The equation was developed using ozone data from receptor sites in Northern New Jersey and the resulting correlation coefficient was 0.96. The four most significant variables were the upwind ozone maximum on the previous day, today’s maximum temperature, the previous day’s upwind maximum temperature and the mean wind speed from the surface to 1000 m. The model was also successfully tested at 5 other sites in the Northeastern Quadrant of the United States. The results indicate that the model could be a potentially useful tool for air pollution forecasters in predicting maximum ozone concentrations in this quadrant of the country.     

Atmospheric characteristics conducive to high-ozone days in the Atlanta metropolitan area

The purpose of this paper is to identify the atmospheric conditions associated with elevated ground-level ozone concentrations during June–August of 2000–2007 at 11 ozone-monitoring stations in the Atlanta, GA, USA metropolitan statistical area (MSA). Analyses were confined to high-ozone days (HODs), which had a daily maximum 8-h average ozone concentration in the 95th percentile of all June–August values. Therefore, each station had 36 HODs. The southeastern and far northern portions of the MSA had HODs with the highest and lowest ozone concentrations, respectively. HODs at nearly all Atlanta MSA ozone-monitoring stations were enabled by migratory anticyclones. HODs for most stations were hot, dry, and calm with low morning mixing heights and high afternoon mixing heights. All sets of HODs had daily mean relative humidities and afternoon mixing heights that, respectively, were significantly less than and significantly greater than mean values for the remaining days. Urbanized Atlanta typically was upwind of an ozone-monitoring station on its HODs; therefore, wind direction on HODs varied considerably among the stations. HODs may have been caused partially by NO_x emissions from electric-utility power plants: HODs in the southern portion of the MSA were linked to air-parcel trajectories intersecting a power plant slightly northwest of Atlanta and plants in the Ohio River Valley, while HODs in the northern portion of the MSA were linked to air-parcel trajectories intersecting two large power plants slightly southeast of the Atlanta MSA. Results from this study suggest that future research in the Atlanta MSA should focus on power-plant contributions to ground-level ozone concentrations as well as the identification of non-monitored locations with potentially high ozone concentrations.     

Climatology of diurnal trends and vertical distribution of ozone in the atmospheric boundary layer in urban North Carolina

Vertical measurements of ozone were made on a 610-m-tall tower located about 15 km southeast of Raleigh, NC, as part of an effort by the state of North Carolina to develop a state implementation plan (SIP) for ozone control in the Raleigh Metropolitan Statistical Area. During summer 1993, 1994, and 1995, ozone was monitored at ground level, 250 m, and 433 m. Boundary layer wind, temperature, and other meteorological variable profiles were determined from balloon soundings. During summer 1996 and 1997, ozone was monitored at ground level, 76 m, 128 m, and 433 m. This paper presents the analysis and discussion of the five-year data. The evolutions of the convective boundary layer during daytime and the stable nocturnal boundary layer (NBL) were found to have marked impacts on ozone concentrations. A strong diurnal pattern, with an afternoon maximum and an early morning minimum, was dominant at ground level, but it was much weaker at elevated levels and insignificant above the NBL at night. Ozone deposition velocities at night during the measurement periods were estimated to range from 0.09 to 0.64 cm/sec. We found evidence of regional transport of ozone and/or its precursors from northwest and north of the site, which may play a role in high ozone events in the Raleigh-Durham area. Ozone concentrations between the various elevated levels were well correlated, while correlations between the ground and upper levels were much weaker. However, a strong correlation was found between the nighttime and early morning ozone concentrations (CR) in the residual layer above the NBL and the maximum ground level concentration (Co max) the following afternoon. Based on this correlation, the latter may be predicted by an observational model Co max = 27.76e 0.016 CR.     

Background ozone monitoring and phytodetection in the greater rural area of Corinth--Greece

Natural background ozone levels were monitored in three places within the greater rural area of Corinth, namely Bogdani Hill, Astronomical Observatory of Krionerion, and Kiato, and compared with ambient ozone monitored in the metropolitan area of Athens. Measurements were made sequentially, for a few weeks at each place, during the summer of 2000. In addition, ozone phytodetection, using tobacco (Nicotiana tabacum L.) plants of the Bel-W3 and Zichnomirodata varieties, was conducted in 12 places (the above included). Moreover, stomatal conductance was measured in the Bel-W3 plants, as well as in leaves of cultivated grape-vines (Vitis vinifera L.) and in needles of Aleppo pine (Pinus halepensis Mill.) trees and compared with the diurnal pattern of ozone concentrations.The 24 and 12 (08:00-20:00) hourly averages of ozone concentrations were high in Athens (37; 51 ppb), at Bogdani Hill (53; 56 ppb) and at the Astronomical Observatory (56; 55 ppb), but relatively low in Kiato (30; 34 ppb). Furthermore, the average daily AOT40 (accumulated exposure over 40 ppb for the daylight hours) (ppbh) was 193 in Athens, 212 at Bogdani Hill, 192 at the Astronomical Observatory and 47 in Kiato. Ozone concentrations exhibited the usual diurnal pattern in Athens (altitude 50 m), where they were maximum during midday and early afternoon hours, as well as at Bogdani Hill (300 m) and in Kiato (5 m) where, however, they were maximal 1-3 h later. At the Astronomical Observatory (altitude 920 m) ozone remained constant during both daylight and night hours. The differences in diurnal patterns are consistent with those in places of different elevation, reported elsewhere.The Bel-W3 plants were injured at all 12 places; Zichnomirodata plants exhibited lower injury and only in some of the places; probable ozone symptoms were also observed on vine plants and pine trees. The greatest injury was observed at the high altitude places of Astronomical Observatory and Mougostos. Stomatal conductance, in all three species, peaked during morning and early midday hours when ozone levels were higher in the high altitude, and lower in the low altitude, places.     

Variations of surface O3 in August at a rural site near Shanghai: influences from the West Pacific subtropical high and anthropogenic emissions

Large day-to-day variability in O₃ and CO was observed at Chongming, a remote rural site east of Shanghai, in August 2010. High ozone periods (HOPs) that typically lasted for 3?C5?days with daily maximum ozone exceeding 102?ppb were intermittent with low ozone periods (LOPs) with daily maximum ozone less than 20?ppb. The correlation analysis of ozone with meteorological factors suggests that the large variations of surface ozone are driven by meteorological conditions correlated with the changes in the location and intensity of the west Pacific subtropical high (WPSH) associated with the East Asian summer monsoon (EASM). When the center of WPSH with weaker intensity is to the southeast of Chongming site, the mixing ratios and variability of surface ozone are higher. When the center of WPSH with stronger intensity is to the northeast of Chongming site, the mixing ratios and variability of surface ozone are lower. Sensitivity simulations using the GEOS-Chem chemical transport model indicate that meteorological condition associated with WPSH is the primary factor controlling surface ozone at Chongming in August, while local anthropogenic emissions make significant contributions to surface ozone concentrations only during HOP.     

泰山顶与济南市大气臭氧浓度变化规律研究

利用2003年7月至9月在泰山顶和济南市3个月的臭氧（O3）自动连续监测数据,对两地O3浓度的频率分布、日变化和日际变化等特征进行对照分析。实验结果表明,泰山顶O3小时平均浓度频率分布比较集中,济南市O3小时平均浓度频率分布比较分散。泰山顶各月O3小时平均浓度的平均值和日均值均高于济南市;泰山顶O3小时平均浓度的最大值低于济南市,而O3小时平均浓度的最小值要高于济南市。泰山顶O3小时平均浓度日变化规律与济南市O3小时平均浓度日变化规律有很大差别,泰山顶O3小时平均浓度日变化很平缓,最大值与最小值相差不大,济南市O3小时平均浓度一般在中午和午后浓度较高,早晨和夜晚较低。     

Sensitivity of ozone to summertime climate in the eastern USA: A modeling case study

The goal of this modeling study is to determine how concentrations of ozone respond to changes in climate over the eastern USA. The sensitivities of average ozone concentrations to temperature, wind speed, absolute humidity, mixing height, cloud liquid water content and optical depth, cloudy area, precipitation rate, and precipitating area extent are investigated individually. The simulation period consists of July 12–21, 2001, during which an ozone episode occurred over the Southeast. The ozone metrics used include daily maximum 8 h average O₃ concentration and number of grid cells exceeding the US EPA ambient air-quality standard. The meteorological factor that had the largest impact on both ozone metrics was temperature, which increased daily maximum 8 h average O₃ by 0.34 ppb K⁻¹ on average over the simulation domain. Absolute humidity had a smaller but appreciable effect on daily maximum 8 h average O₃ (−0.025 ppb for each percent increase in absolute humidity). While domain-average responses to changes in wind speed, mixing height, cloud liquid water content, and optical depth were rather small, these factors did have appreciable local effects in many areas. Temperature also had the largest effect on air-quality standard exceedances; a 2.5 K temperature increase led to a 30% increase in the area exceeding the EPA standard. Wind speed and mixing height also had appreciable effects on ozone air-quality standard exceedances.     

Characteristics of urban ground-level ozone in Korea

This study considers the characteristics of ground-level ozone (O3) in five Korean cities over a time period of 6-8 years. The focus of this study is daily maximum 1-hr and 8-hr concentrations. For all the study cities in the period examined, the mean and most of the percentiles (5, 10, 25, 50, 75, 90, and 95) for the daily maximum 1-hr and 8-hr concentrations showed increasing trends, although not all trends were statistically significant. The daily maximum 1-hr and 8-hr concentrations slowly increased during late winter, and peaks were attained during the summer season (from May to September). All the selected cities exhibited a high degree of correlation between their daily maximum 8-hr and 1-hr concentrations. The daily maximum 8-hr concentrations, which were climatologically equivalent to the Korean 1 hr/100 parts per billion (ppb) standard, were higher than the current 8 hr/60 ppb by a difference of 8-16 ppb. Compared with other cities in Korea, Seoul recorded a substantially higher frequency of days and hours with concentrations above 1 hr/100 ppb, and a higher frequency of days with concentrations above 8 hr/60 ppb and 8 hr/80 ppb. Seoul also recorded a substantially higher frequency of hours with concentrations above 1 hr/100 ppb than days with concentrations above 1 hr/100 ppb, implying that on some days severe exceedances persisted for more than one hour per day. During multiple-day episodes a North Pacific High dominated Korea, which is quite typical in Korea during the summer season.     

On ground truth in cross-border ozone transport

Cross-border transport of ozone is one of the most contentious issues of air pollution management in the U.S. Yet, both the modeling and observational studies are lacking. Models are normally validated by comparing predicted and observed ozone concentrations. However, proper validation of cross-border transport model requires a comparison of predictions against observation-based benchmarks of cross-border ozone transport. Such benchmarks are unavailable, as published observation-based studies always deal only with a combination of local production and cross-border transport, not a cross-border transport itself. We show how to extract necessary benchmarks from observations of rural monitoring sites near state borders. On example of the western border of New York, we find that in about two-thirds of the most polluted days all the ozone came in a steady cross-border inflow after previously passing over one or more large urban areas to the west. In all the enumerated days with direct cross-border inflow, daily maximum 8-hr concentrations of ozone just upwind of the border were over 60 ppb, with an average value of 68 ppb, just short of the 70 ppb ozone regulatory threshold, information also useful to state air pollution authorities.

Implications: The purpose of the cross-border ozone pollution models is to predict cross-border transport of ozone, so the ability of the model to accurately represent observed ozone concentrations is necessary but not sufficient for model validation. The accuracy of predicted ozone concentrations is not necessarily the same as the accuracy of the predictions of ozone transport. Proper model validation requires comparisons against observation-based benchmarks of cross-border transport. Such observations, so far absent, can be obtained from rural monitoring sites near state borders, as illustrated by the example of western New York.     

An evaluation of the interaction of morning residual layer and afternoon mixed layer ozone in Houston using ozonesonde data

The Tropospheric Ozone Pollution Project (TOPP) launched >220 ozonesondes in Houston (July 2004–June 2008) providing examples of pollution transported into, re-circulated within, and exported from the Houston area. Fifty-one launches occurred during the Texas Air Quality Study (TexAQS) II and the summer portion of IONS-06 (INTEX [Intercontinental Transport Experiment] Ozonesonde Network Study). On 11 days during TexAQS II and on 8 other occasions, ozonesondes were launched both at dawn and in the afternoon. Analysis of these “intensive” launch sequences shows that morning residual layer (RL) ozone concentrations ([O₃]) explained 60–70% of the variability found in the afternoon mixed layer (ML). Furthermore, maximum RL [O₃] is nearly identical to the mean ML [O₃] from the previous afternoon (morning minus afternoon = ?1.6 ± 8.4 ppbv). During TexAQS II, mean [O₃] below 1.3 km (the mean ML height from ozonesonde data) increased from 37 ± 22 ppbv in the morning to 74 ± 18 ppbv in the afternoon, suggesting an average net local daily O₃ production of ～500–900 tons over the metropolitan Houston area.     

Ozone pollution and ozone biomonitoring in European cities. Part I: Ozone concentrations and cumulative exposure indices at urban and suburban sites

In the frame of a European research project on air quality in urban agglomerations, data on ozone concentrations from 23 automated urban and suburban monitoring stations in 11 cities from seven countries were analysed and evaluated. Daily and summer mean and maximum concentrations were computed based on hourly mean values, and cumulative ozone exposure indices (Accumulated exposure Over a Threshold of 40 ppb (AOT40), AOT20) were calculated. The diurnal profiles showed a characteristic pattern in most city centres, with minimum values in the early morning hours, a strong rise during the morning, peak concentrations in the afternoon, and a decline during the night. The widest amplitudes between minimum and maximum values were found in central and southern European cities such as Düsseldorf, Verona, Klagenfurt, Lyon or Barcelona. In the northern European cities of Edinburgh and Copenhagen, by contrast, maximum values were lower and diurnal variation was much smaller. Based on ozone concentrations as well as on cumulative exposure indices, a clear north–south gradient in ozone pollution, with increasing levels from northern and northwestern sites to central and southern European sites, was observed. Only the Spanish cities did not fit this pattern; there, ozone levels were again lower than in central European cities, probably due to the direct influence of strong car traffic emissions. In general, ozone concentrations and cumulative exposure were significantly higher at suburban sites than at urban and traffic-exposed sites. When applying the newly established European Union (EU) Directive on ozone pollution in ambient air, it was demonstrated that the target value for the protection of human health was regularly surpassed at urban as well as suburban sites, particularly in cities in Austria, France, northern Italy and southern Germany. European target values and long-term objectives for the protection of vegetation expressed as AOT40 were also exceeded at many monitoring sites.     

An enhanced ozone forecasting model using air mass trajectory analysis

An enhanced ozone forecasting model using nonlinear regression and an air mass trajectory parameter has been developed and field tested. The model performed significantly better in predicting daily maximum 1-h ozone concentrations during a five-year model calibration period (1993–1997) than did a previously reported regression model. This was particularly true on the 28 “high ozone” days ([O₃]>120 ppb) during the period, for which the mean absolute error (MAE) improved from 21.7 to 12.1 ppb. On the 77 days meteorologically conducive to high ozone, the MAE improved from 12.2 to 9.1 ppb, and for all 580 calibration days the MAE improved from 9.5 to 8.35 ppb. The model was field-tested during the 1998 ozone season, and performed about as expected. Using actual meteorological data as input for the ozone predictions, the MAE for the season was 11.0 ppb. For the daily ozone forecasts, which used meteorological forecast data as input, the MAE was 13.4 ppb. The high ozone days were all anticipated by the ozone forecasters when the model was used for next day forecasts.     

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.     

Seasonal and diel variation of atmospheric mercury concentrations in the Reno (Nevada,USA) airshed

This paper describes total gaseous mercury (TGM) concentrations measured in Reno, Nevada from 2002 to 2005. The 3-year mean and median air Hg concentrations were 2.3 and 2.1 ng m⁻³, respectively. Mercury concentrations exhibited seasonality, with the highest concentrations in winter, and the lowest in summer and fall. A well-defined diel pattern in TGM concentration was observed, with maximum daily concentrations observed in the morning and minimum in the afternoon. A gradual increase of TGM concentration was observed in the evening and over night. The early morning increase in TGM was likely due to activation of local surface emission sources by rising solar irradiance and air temperature. The subsequent decline and afternoon minimum in TGM were likely related to increased vertical mixing and the buildup of atmospheric oxidants during the day resulting in increased conversion to oxidized species that are quickly deposited, coupled with weakening of the surface emissions processes. The described diel pattern was seasonally modulated with the greatest amplitude in variation of TGM concentrations occurring in the summer. It is suggested based on the comparison of diel TGM pattern with other gaseous pollutants that natural source surface emissions are a dominant source of TGM in the study area.     

Prediction of the vertical profile of ozone based on ground-level ozone observations and cloud cover

A number of statistical techniques have been used to develop models to predict high-elevation ozone (O3) concentrations for each discrete hour of day as a function of elevation based on ground-level O3 observations. The analyses evaluated the effect of exclusion/inclusion of cloud cover as a variable. It was found that a simple model, using the current maximum ground-level O3 concentration and no effect of cloud cover provided a reasonable prediction of the vertical profile of O3, based on data analyzed from O3 sites located in North Carolina and Tennessee. The simple model provided an approach that estimates the concentration of O3 as a function of elevation (up to 1800 m) based on the statistical results with a +/- 13.5 ppb prediction error, an R2 of 0.56, and an index of agreement, d1, of 0.66. The inclusion of cloud cover resulted in a slight improvement in the model over the simple regression model. The developed models, which consist of two matrices of 24 equations (one for each hour of day for clear to partly cloudy conditions and one for cloudy conditions), can be used to estimate the vertical O3 profile based on the inputs of the current day's 1-hr maximum ground-level O3 concentration and the level of cloud cover.     

High ozone concentrations at night in Jerusalem and Tel-Aviv

Elevated ozone concentrations, in excess of accepted background levels, were frequently measured at night in Jerusalem and Tel-Aviv. High ozone at night is connected with persisting low level inversions, under which the photochemically generated ozone is trapped during the day. With the gradual descent of the inversion towards evening and cessation of traffic, ozone levels rise, reaching peak values about 4 h after midnight. The onset of early morning traffic with increasing NO and other pollutants then decreases the ozone concentrations, which reach a minimum level at about 7–8 h local time.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.