Estimation of Ozone Trend in Central Greece, Based on Meteorologically Adjusted Time Series

Data referring to an approximately 8-year period (1999–2007) are analyzed in order to estimate the trend of the daily maximum hourly value of ozone concentration at the east coast of central Greece, where the summer background ozone concentration is high. A Kolmogorov–Zurbenko filter is applied to remove the short-term component from the raw time series of ozone and meteorological variables. Regression models are developed in order to produce meteorologically adjusted ozone time series, involving the noise-free temperature, relative humidity, and wind speed as independent variables. The analysis verifies that the meteorological adjustment provides better results on estimating ozone’s trend, which is found to be increasing (α?=?0.001) with an annual rate of 1.34?±?0.07?μg/m³. This trend could mainly be attributed to policy and changes in the emissions of ozone’s precursors. Additionally, the short-term component of ozone concentration is also meteorologically adjusted and its impact on the trend is examined. The analysis shows that its contribution is of minor importance when the ozone trend is adjusted by temperature, relative humidity, and wind speed. Moreover, the sea breeze circulation system that is frequently developed in the area influences the short-term and seasonal ozone variation, and therefore, it should be taken into account when producing meteorologically adjusted time series. The study’s conclusions could be exploited by environmental and agricultural authorities in order to develop their long-term strategies towards the air quality management.     

An observational case study of ozone and precursors inflow to South East England during an anticyclone

Summertime photochemical air pollution episodes within the United Kingdom have been proposed via modelling studies to be strongly influenced by regional scale inflow of air from the continental European boundary layer. We present a vertically resolved case study using measurements made from the NERC/Met Office BAe 146 research aircraft on 18th August 2005 over the South East of England and the North Sea during a weak anticyclone centred over Northern Europe. The vertical distribution of ozone, CO, NO(x), peroxyacetyl nitrate (PAN) and a wide range of both nonmethane hydrocarbons (NMHC) and oxygenated volatile organic compounds (OVOCs) were determined between 500 ft (approximately 152 m) and 7000 ft (approximately 2134 m) over the East Anglia coastline and 50 km inland. In excess of 80 ppbV ozone was observed within inflowing boundary layer air over the North Sea coast in a broad N-S sloping feature around 60 km wide. The inflowing feature of European origin was also observed further inland within the boundary layer albeit with lower, more variable, ozone mixing ratios. The increased variability in ozone over land was a product of titration by fresh surface emissions of NO via rapid upward transport in thermals, a hypothesis supported by the observed vertical wind speed component. Fast boundary layer mixing over land was further illustrated by a uniform distribution in reactive alkenes. A comparison between aircraft and surface O(3) UK AUN (Automatic Urban Network) measurements showed good agreement with the inland site, Sibton, but marked differences with the coastal monitoring site at Weybourne, potentially due to gradients established by ocean deposition in stably stratified marine air.     

Forecasting Daily Maximum Ozone Concentrations in the Athens Basin

In the work ozone data from the Liossion monitoring station of the Athens/PERPA network are analysed. Data cover the months May to September for the period 1987–93. Four statistical models, three multiple regression and one ARIMA (0,1,2), for the prediction of the daily maximum 1-hour ozone concentrations are developed. All models together, with a persistence forecast, are evaluated and compared with the 1993's data, not used in the models development. Validation statistics were used to assess the relative accuracy of models. Analysis, concerning the models' ability to forecast real ozone episodes, was also carried out. Two of the three regression models provide the most accurate forecasts. The ARIMA model had the worst performance, even lower than the persistence one. The forecast skill of a bivariate wind speed and persistence based regression model for ozone episode days was found to be quite satisfactory, with a detection rate of 73% and 60% for O3 >180 g m-3 and O3 >200 g m-3, respectively.     

Characteristics of surface ozone at an urban site of Xi'an in Northwest China

Surface ozone concentrations in Xi'an, China were monitored from March 23, 2008 to January 12, 2009 using the Model ML/EC9810 ozone analyzer. The daily average O(3) ranged from <1 ppb to 64.2 ppbv with an annual average of 16.0 ppbv. The seasonal average of O(3) in summer (32.5 ppbv) was more than 10 times higher than that in winter (3.0 ppbv). A significant positive correlation was found between ozone concentration and ambient temperature, indicating that the intensity of solar radiation was one of the several major factors controlling surface ozone production. Using the NOAA HYSPLIT 4 trajectory model, the three longest O(3) pollution episodes were found to be associated with the high biogenic volatile organic carbon (BVOC) emissions from the vegetation of Qinling Mountains. No significant weekday and weekend difference in O(3) levels was detected due to the non-significant change in NO(x) emissions. O(3) depletion by NO emission directly emitted from vehicles, low oxygenated VOC concentrations, and low-level solar radiation caused by high aerosol loading all contributed to the low levels of O(3) found in Xi'an compared to other cities and rural areas.     

Grey Box and Component Models to Forecast Ozone Episodes: A Comparison Study

For the purpose of short-term forecasting of high ozone concentration episodes stochastic models have been suggested and developed in the literature. The present paper compares the quality of forecasts produced by a grey box and a component time-series model. The summer ozone patterns for three European urban areas (two continental and one mediterranean) are processed. By means of forecast performance indices according to EC and WHO guidelines, the following features of the models could be found: The grey box model is highly adaptive and produces forecasts with low error variance that increases with the time horizon of forecast. The component model is more 'stiff' that results in a higher forecast-error variance and poorer adaption in detail. The forecast horizon, however, could be enlarged with this model. The accuracy of predicting threshold exceedance is similar for both models. This can be understood from the assumption of a cyclical time development of ozone that was made for both models.     

Analysis of tropospheric ozone concentration on a Western Mediterranean site: Castellon (Spain)

Ozone dynamics in our study area (Castellon, Spain) is both strongly bound to the mesoscale circulations that develop under the effect of high insolation (especially in summer) and conditioned by the morphological characteristics of the Western Mediterranean Basin. In this work we present a preliminary analysis of ozone time series on five locations in Castellon for the period 1997–2003. We study their temporal and spatial variations at different scales: daily, weekly, seasonally and interannually. Because both the O₃ concentration and its temporal variation depend on the topographic location of the observing station, they can show large differences within tens of kilometer. We also contrast the variation in the ozone concentration with the variations found for meteorological variables such as radiation, temperature, relative humidity and recirculation of the air mass. The link between elevated ozone concentrations and high values of the recirculation factor (r=0.7–0.9) shown the importance of recirculating flows on the local air pollution episodes.     

Factors influencing Aerosol Characteristics over Urban Environment

Atmospheric aerosols are an important contributing factor to turbidity in urban areas besides having impact on health. Aerosol characteristics show a high degree of variability in space and time as anthropogenic share of total aerosol loading is quite substantial and is essential to monitor the aerosol features over long time scales. In the present study extensive observations of columnar aerosol optical depth (AOD), total columnar ozone (TCO) and precipitable water content (PWC) have been carried over a tropical urban city of Hyderabad, India. Significant variations of AOD have been observed during course of the day with low values of AOD during morning and evening hours and high values during afternoon hours. Spectral variation of AOD exhibits high AOD at smaller wavelengths and vice versa except a slight enhancement in AOD at 500 nm. Anomalies in AOD, particulate matter and black carbon concentrations have been observed during May, 2003. Back trajectory analysis of air mass during these episodes suggested variation in air mass trajectories. Analysis of the results suggests that air trajectories from land region north of study area cause high loading of atmospheric aerosols. The results are discussed in the paper.     

Prediction of daily ground-level ozone concentration maxima over New Delhi

The pollution levels in New Delhi from industrial, residential, and transportation sources are continuously growing. As one of the major pollutants, ground-level ozone is responsible for various adverse effects on both humans and foliage. The present study aims to predict daily ground-level ozone concentration maxima over a site situated in New Delhi through neural networks (NN) and multiple-regression (MR) analysis. Although these methodologies are case and site specific, they are being developed and used widely. Therefore, to test these methodologies for New Delhi where no such study is available for ground-level ozone, six models have been developed based on NNs and MR using the same input data set. The changes in the performance capability of the two methods are sensitive to the selection of input parameters. The results are encouraging, and remarkable improvements in the performance of the models have been observed.     

Insights into ozone deposition patterns from decade-long ozone flux measurements over a mixed temperate forest

Long-term fluxes of ozone (O(3)) were measured over a mixed temperate forest using the aerodynamic gradient method. The long-term average O(3) flux (F) was -366 ng m(-2) s(-1) for the period 2000-2010, corresponding to an average O(3) concentration of 48 μg m(-3) and a deposition velocity v(d) of 9 mm s(-1). Average nocturnal ozone deposition amounted to -190 ng m(-2) s(-1), which was about one third of the daytime flux. Also during the winter period substantial O(3) deposition was measured. In addition, total O(3) fluxes were found to differ significantly among canopy wetness categories. During the day, highest deposition fluxes were generally measured for a dry canopy, whereas a rain-wetted canopy constituted the best sink at night. Flux partitioning calculations revealed that the stomatal flux (F(s)) contributed 20% to the total F but the F(s)/F fraction was subject to seasonal and diurnal changes. The annual concentration-based index AOT40 (accumulated dose over a threshold of 40 ppb) and the Phytotoxic Ozone Dose (POD(1) or accumulated stomatal flux above a threshold of 1 nmol m(-2) s(-1)) were related in a curvilinear way. The O(3) deposition was found to be largely controlled by non-stomatal sinks, whose strength was enhanced by high friction velocities (u(*)), optimizing the mechanical mixing of O(3) into the canopy and the trunk space. The long-term geometrical mean of the non-stomatal resistance (R(ns)) was 136 s m(-1) but lower R(ns) values were encountered during the winter half-year due to higher u(*). The R(ns) was also subject to a marked diurnal variability, with low R(ns) in the morning hours, when turbulence took off. We speculate that non-stomatal deposition was largely driven by scavenging of ozone by biogenic volatile organic compounds (BVOCs) and especially NO emitted from the crown or the forest floor.     

Variation of Surface Ozone in the Ambient Air of Auckland, New Zealand

A study has been performed on the characteristics and behavior of surface ozone concentrations at four monitoring sites in Auckland, New Zealand (37 degrees S, 174.8 degrees E) for a four-year period (October 1997-October 2001). One monitoring site (rural) was located upwind of the Auckland urban complex, a second downwind (rural-coastal), and a third within the urban area, while the fourth was an elevated urban-city site located 250 m up the Sky Tower in the central city. In contrast to the high elevation site, the diurnal behaviour of ozone at the three low elevation sites followed a typical solar radiation cycle with high ozone during the day and low nocturnal values. The effect of NO(x) titration was distinct at the urban sites. There was also a seasonal variability in the measured ozone levels with high concentrations in spring and a significant summer minimum. The observed surface ozone concentrations in Auckland were significantly lower than other cities of the world, although a potential for high oxidant formation existed. Observed ozone episodes appear to have been either generated locally or the precursors transported via the prevailing southwest wind. A unique feature of Auckland's air quality is the dilution of polluted city air due to the mixing of east-coast air into the clean west-coast circulation leading to the overall lower average concentrations in summer. A second feature is the potential interaction between sea salt particles and ozone that may provide an additional ozone loss mechanism.     

Air quality assessment of Estarreja, an urban industrialized area, in a coastal region of Portugal

Despite the increasing concern given to air quality in urban and industrial areas in recent years, particular emphasis on regulation, control, and reduction of air pollutant emissions is still necessary to fully characterize the chain emissions–air quality–exposure–dose–health effects, for specific sources. The Estarreja region was selected as a case study because it has one of the largest chemical industrial complexes in Portugal that has been recently expanded, together with a growing urban area with an interesting location in the Portuguese coastland and crossed by important road traffic and rail national networks. This work presents the first air quality assessment for the region concerning pollutant emissions and meteorological and air quality monitoring data analysis, over the period 2000–2009. This assessment also includes a detailed investigation and characterization of past air pollution episodes for the most problematic pollutants: ozone and PM10. The contribution of different emission sources and meteorological conditions to these episodes is investigated. The stagnant meteorological conditions associated with local emissions, namely industrial activity and road traffic, are the major contributors to the air quality degradation over the study region. A set of measures to improve air quality—regarding ozone and PM10 levels—is proposed as an air quality management strategy for the study region.     

Simulation and Evaluation of Control Strategies for Ozone Reduction in a Complex Terrain in Southwestern Spain

During the central months of the year, southwestern Spain is under strong insolation and weak synoptic forcing, promoting the development of sea breezes and mountain-induced winds and creating recirculations of pollutants. The complex topography of the Southwestern Iberia Peninsula induces the formation of vertical layers, into which the pollutants are injected and subjected to long-distance transport and compensatory subsidence. The characteristics of these highly complex flows have important effects on the pollutant dispersion. Air pollution studies in very complex terrains require high-resolution modelling for resolving the flow dynamics. This paper shows the results obtained from using the MM5-CAMx multiscale-nested air quality model to relate the sensitivity regimes for ozone, nitrogen oxides and volatile organic compounds in an area of high geographical complexity. The article assesses the impact on the hourly and eight-hourly maximum daily ozone concentrations of four reduction strategies during two ozone pollution episodes. This analysis of the ozone response has led to a preliminary evaluation of the effectiveness of the most common control strategies: traffic, industry, mixed traffic and industry, and closure of some of the largest industries (oil and petrochemical refineries). Photochemical indicators show that ozone chemistry in southwestern Spain is strongly sensitive to NO _x . However, volatile organic compound-sensitive points are found in areas with anthropogenic influence (highways, cities and industrial parks). Our results indicate that reductions in road traffic lead to ozone reductions over large areas, whereas reductions in industrial emissions, despite sometimes showing greater decreases in the maximum hourly and eight-hourly ground-level ozone levels, lead to ozone reductions in a local area only. In the control study case, with the oil refinery and the petrochemical plants closed, decreases in ozone hourly concentrations are up to 40% higher than in the other emission control scenarios studied. This analysis provides an assessment of the effectiveness of different policies for controlling precursor emissions by comparing the modelled results for different scenarios.     

The Characteristics of Tropospheric Ozone Seasonality Observed from Ozone Soundings at Pohang, Korea

This paper presents the first analysis of vertical ozone sounding measurements over Pohang, Korea. The main focus is to analyze the seasonal variation of vertical ozone profiles and determine the mechanisms controlling ozone seasonality. The maxima ozone at the surface and in the free troposphere are observed in May and June, respectively. In comparison with the ozone seasonality at Oki (near sea level) and Happo (altitude of 1840 m) in Japan, which are located at the same latitude as of Pohang, we have found that the time of the ozone maximum at the Japanese sites is always a month earlier than at Pohang. Analysis of the wind flow at the surface shows that the wind shifts from westerly to southerly in May over Japan, but in June over Pohang. However, this wind shift above boundary layer occurs a month later. This wind shift results in significantly smaller amounts of ozone because the southerly wind brings clean wet tropical air. It has been suggested that the spring ozone maximum in the lower troposphere is due to polluted air transported from China. However, an enhanced ozone amount over the free troposphere in June appears to have a different origin. A tongue-like structure in the time-height cross-section of ozone concentrations, which starts from the stratosphere and extends to the middle troposphere, suggests that the ozone enhancement occurs due to a gradual migration of ozone from the stratosphere. The high frequency of dry air with elevated ozone concentrations in the upper troposphere in June suggests that the air is transported from the stratosphere. HYSPLIT trajectory analysis supports the hypothesis that enhanced ozone in the free troposphere is not likely due to transport from sources of anthropogenic activity.     

Determination of O3, NO2, SO2, CO and PM10 measured in Belgrade urban area

O(3), NO(2), SO(2), CO and PM(10) concentrations, simultaneously determined for the first time in Belgrade urban area in the autumnal period of 2005, are presented. The obtained results display similar behaviour of SO(2), NO(2), CO, PM(10) opposite from that of O(3). The weekend effect was also investigated showing diminution of average daily concentrations of SO(2), NO(2), PM(10) and CO for 72, 40, 37 and 42% respectively, and increase of the average daily concentration of O(3) for 56%. Influence of meteorological conditions on observed concentration levels was studied, too. The observed influence of wind speed on the O(3) nightly concentration levels was analyzed pointing to the phenomena of O(3) transport during episodic measurements. To make an identification of possible pollution sources and analyse the influence of meteorological parameters on pollution levels, air back trajectories for high level concentrations episodes were calculated and analysed. A multivariate receptor modelling (Principal Component Analysis, Cluster Analysis) has been applied to a set of data in order to determine the contribution of different sources. It was found that the main principal components, extracted from the air pollution data, were related to gasoline combustion, oil combustion and ozone transport.     

A study of ground-level ozone pollution, ozone precursors and subtropical meteorological conditions in central Taiwan

Hourly concentrations of ozone (O(3)), 55 volatile organic compounds (VOCs, ozone precursors) and nitrogen oxides (NOx) were measured at an upwind urban site, a downwind suburban site, and a rural site in central Taiwan, from January 2003 to December 2006. VOC and NOx mean concentrations showed a gradient from high to low across the urban (56 ppb and 34 ppb), suburban (38 ppb and 27 ppb) and rural sites (25 ppb and 21 ppb) but a reverse gradient in ozone across these sites (24, 27, and 29 ppb, respectively). Although there was about twice the difference in VOC concentrations between the urban and rural sites, nearly 65% ozone formation potential was contributed to by the same 9 VOCs. Seasonal patterns showed peak ozone levels in autumn and minima in summer at the urban site, but minima in winter at the downwind suburban and rural sites. Ozone precursor levels, on the other hand, were lowest in summer and highest in winter. The diurnal pattern showed that ozone levels peaked one hour later at the rural site than at the urban site. The ethylbenzene to m,p-xylene ratio, an indicator of the age of the air mass, increased from 0.4 at the urban site to 0.6 at the suburban site and 0.8 at the rural site during daily peak ozone times. This finding suggests the transport of ozone and precursors from upwind to downwind producing elevated ozone levels in the suburban and rural areas. Ozone episodes occurred mostly in days with a mean midday UV index of 6.5 (1 UV index=100 J m(-2)) and wind speed at 1.3 m s(-1) at all three sites.     

Vertical ozone characteristics in urban boundary layer in Beijing

Vertical ozone and meteorological parameters were measured by tethered balloon in the boundary layer in the summer of 2009 in Beijing, China. A total of 77 tethersonde soundings were taken during the 27-day campaign. The surface ozone concentrations measured by ozonesondes and TEI 49C showed good agreement, albeit with temporal difference between the two instruments. Two case studies of nocturnal secondary ozone maxima are discussed in detail. The development of the low-level jet played a critical role leading to the observed ozone peak concentrations in nocturnal boundary layer (NBL). The maximum of surface ozone was 161.7 ppbv during the campaign, which could be attributed to abundant precursors storage near surface layer at nighttime. Vertical distribution of ozone was also measured utilizing conventional continuous analyzers on 325-m meteorological observation tower. The results showed the NBL height was between 47 and 280 m, which were consistent with the balloon data. Southerly air flow could bring ozone-rich air to Beijing, and the ozone concentrations exceeded the China’s hourly ozone standard (approximately 100 ppb) above 600 m for more than 12 h.     

Spatial and temporal variation of surface ozone,NO and NO2 at urban,suburban, rural and industrial sites in the southwest of the Iberian Peninsula

Surface ozone is one of the most important photochemical pollutants in the low atmosphere, causing damage to human health, vegetation, materials and climate. The weather (high temperatures and high solar radiation), orography (presence of the Guadalquivir valley) and anthropogenic (the cities of Cádiz, Córdoba, Huelva and Seville and two important industrial complexes) characteristics of the southwestern Iberian Peninsula make this region ideal for the formation and accumulation of ozone. To increase the knowledge of ozone behaviour in this area, the monthly, daily and weekly variations of ozone and its precursors, nitrogen oxides (NO_x?=?NO?+?NO₂), were analysed over a 4-year period (2003 to 2006). Using the k-means cluster technique, 12 representative stations of five different areas with different ozone behaviour were selected from a total of 29 monitoring sites. This is the first time that the analysis of these atmospheric pollutants has been carried out for the whole area, allowing therefore a complete understanding of the dynamics and the relationships of these compounds in this region. The results showed an opposite behaviour among ozone and NO and NO₂ concentrations in urban and suburban zones, marked by maximums of ozone (minimums NO_x) in spring and summer and minimums (maximums) in autumn and winter. A seasonal behaviour, with lower amplitude, was also observed in rural and industrial areas for ozone concentrations, with the NO and NO₂ concentrations remaining at low and similar values during the year in rural zones due to the absence of emission sources in their surroundings. The daily cycles of ozone in urban, suburban and industrial sites registered a maximum value in the early afternoon (14:00–17:00 UTC) while for NO_x two peaks were observed, at 7:00–10:00 UTC and 20:00–22:00. In the case of rural stations, no hourly peak of ozone or NO_x was registered. The weekend effect was studied by using a statistical contrast tests (Student’s t). The results indicated that only areas influenced by important traffic emissions presented a weekend effect for NO and NO₂, whereas an ozone weekend effect was not detected in any case.     

A simple linear model for estimating ozone AOT40 at forest sites from raw passive sampling data

A rapid, empirical method is described for estimating weekly AOT40 from ozone concentrations measured with passive samplers at forest sites. The method is based on linear regression and was developed after three years of measurements in Trentino (northern Italy). It was tested against an independent set of data from passive sampler sites across Italy. It provides good weekly estimates compared with those measured by conventional monitors (0.85 ≤R(2)≤ 0.970; 97 ≤ RMSE ≤ 302). Estimates obtained using passive sampling at forest sites are comparable to those obtained by another estimation method based on modelling hourly concentrations (R(2) = 0.94; 131 ≤ RMSE ≤ 351). Regression coefficients of passive sampling are similar to those obtained with conventional monitors at forest sites. Testing against an independent dataset generated by passive sampling provided similar results (0.86 ≤R(2)≤ 0.99; 65 ≤ RMSE ≤ 478). Errors tend to accumulate when weekly AOT40 estimates are summed to obtain the total AOT40 over the May-July period, and the median deviation between the two estimation methods based on passive sampling is 11%. The method proposed does not require any assumptions, complex calculation or modelling technique, and can be useful when other estimation methods are not feasible, either in principle or in practice. However, the method is not useful when estimates of hourly concentrations are of interest.     

Airborne measurements of peroxy radicals using the PERCA technique

The Peroxy Radical Chemical Amplifier (PERCA) technique is a proven method for measurement of ambient levels of peroxy radicals at ground level, but there are no published instances of the technique being used on an aerial platform. Here we describe deployment of a PERCA on the former UK Meteorological Office C-130 Hercules research aircraft. The instrument uses the established method of chemical amplification and conversion of peroxy radicals to nitrogen dioxide (NO2) by doping the sample air-flow matrix with CO and NO, subsequently measuring the NO2 yield with an improved 'Luminox' LMA-3 NO2 detector. NO2 from the amplification chemistry is distinguished from other sources of NO2 reaching the detector by periodically injecting CO approximately 1 s downstream of the NO injection point (termination mode). Chain lengths (CL's) for the amplification chemistry were typically approximately 260 (ground level) to approximately 200 (7,000 m). This variation with altitude is less than the variation associated with the 'age' of the PFA inlet material where the amplification chemistry occurs; CL's of approximately 200 with old tubing to approximately 300 with new clean tubing were typical (ground level values). The CL determinations were made in-flight using an onboard calibration unit based on the 254 nm photolysis of 7.5 to 10 parts per billion (by volume, ppbv) of CH3I in air, producing CH3O2 in a quantitative manner. The noise-equivalent detection limit for peroxy radicals (HO2 + RO2) is 2 parts per trillion (by volume, pptv) at 3,650 m when the background ambient ozone levels are stable, based on a 5 min average of five 30 s amplification cycles and five 30 s termination cycles. This detection limit is a function of several factors but is most seriously degraded when there is large variability in the ambient ozone concentration. This paper describes the instrument design, considers its performance and proposes design improvements. It concludes that the performance of an airborne PERCA in the free troposphere can be superior to that of ground-based instruments when similar sampling frequencies are compared.     

Biosphere atmosphere exchanges: Ozone and aerosol dry deposition velocities over a pine forest

Measurements of dry deposition velocities for ozone and aerosol particles has been measured over a pine forest in the south-west of France by the eddy correlation method. Low frequency fluctuations in the variations of scalars can introduce erroneous values of vertical fluxes for ozone and aerosol particles but also, in some cases of low wind, for momentum and heat. The dry deposition velocity variations are similar for ozone and aerosol, although the mechanism of deposition are different. In the case of aerosol particles a parametrization, not far from that of Wesely et al. (1985) can be given.