Photochemical modelling of summer ozone episodes in the Greater Madrid area

The mesoscale meteorological model TVM, coupled to a photochemical/transport module in which different chemical mechanisms (RACM, EMEP) are implemented, has been evaluated. Field measurements and numerical results are used to determine the impact of the mesoscale flows on the photochemical smog episodes observed in the Greater Madrid Area for two selected days, characterised by the presence of a thermal low-pressure system over the Iberian Peninsula. During the 14 July 1992, the synoptic flow from the southeast favoured the transport of the precursors to the Guadarrama mountain range, where high concentrations of ozone were registered, exceeding the population information threshold. On the 15 July 1995, the synoptic wind from the northwest interacted with the local thermally driven flows, pushing the pollutants far away from the metropolitan area with the result that high ozone concentrations were measured to the east-southeast of the city.     

Meteorological effects on the evolution of high ozone episodes in the greater Seoul area

Three high O3 episodes--7 days in 1992 (July 3-July 9), 9 days in 1994 (July 21-July 29), and another 3 days in 1994 (August 22-August 24)--were selected on the basis of morning (7:00 a.m.-10:00 a.m.) average wind direction and speed and daily maximum O3 concentrations in the greater Seoul, Korea, of 1990-1997. To better understand their characteristics and life cycles, surface data from the Seoul Weather Station (SWS) and surface and 850-hPa wind field data covering northeast Asia around the Korean Peninsula were used for the analysis. In the July 1992 episode, westerly winds were most frequent as a result of the influence of a high-pressure system west of the Korean Peninsula behind a trough. In contrast, in the July 1994 episode, easterly winds were most frequent as a result of the effect of a typhoon moving north from the south of Japan. Despite different prevailing wind directions, the peak O3 concentrations for each episode occurred when a sea/land breeze developed in association with weak synoptic forcing. The August 1994 episode, which was selected as being representative of calm conditions, was another typical example in which a well-developed     

Episode selection for ozone modelling and control strategies analysis on the Swiss Plateau

An episode selection procedure was developed and applied to select sets of days representing characteristic meteorological conditions leading to high ozone episodes over the Swiss Plateau. The selection procedure was applied to data extending from January 1991 through December 1998, and is comprised of two steps: First, days were classified according to observed air quality and meteorological characteristics using classification and regression trees analysis (CART). Second, the CART results were used in conjunction with observed air quality data to identify sets of days characteristic of those leading to elevated ozone. These sets of days were selected to optimise how well a limited number of days represented seasonal air quality, and that formed longer episodes for use in the air quality modelling. CART analysis was performed for three zones of the Swiss Plateau that have different air quality and meteorological characteristics. The results for two zones were used together in the episode selection procedure in order to identify days representative for the whole Plateau. Meteorological analysis for a third zone suggested that it would be strongly impacted by pollutants transported in from outside the country. One thousand and eight hundred optimisation runs were performed to minimise the likelihood that the set of days was a local optimum, increasing the robustness for use in air quality modelling analysis. Fifteen days, grouped in four episodes ranging from 3 to 5 days were selected along with their calculated representativeness (or weight) to recreate a seasonal metric. The variety of local as well as regional meteorological characteristics showed that the episode selection procedure chose days representing a diverse set of meteorological situations which are associated with elevated ozone. This set of episodes can now be used to test air quality strategies.     

Frequency analysis of high CO concentrations in Madrid by stochastic process modelling

The series of high CO concentrations in Madrid is analyzed through up and downcrossings series techniques. The failure rate probability of interchange of states 1 (CO concentrations < 7mgm⁻³) and 2 (CO concentration ⩾ 7 mg m⁻³) have been computed for the whole year. A seasonal cycle has been detected. The series have been modelled and the probability of high concentrations and of their duration have been studied by application of seasonal models.     

Development and application of a Lagrangian model to determine the origins of ozone episodes in the UK

This paper describes the further development and application of the Edinburgh–Lancaster Model for Ozone (ELMO). We replace straight-line back-trajectories with trajectories and associated meteorology supplied by the US National Oceanic and Atmospheric Administration Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) service to allow more realistic modelling of specific UK ozone episodes. We call this ELMO-2. Model performance is rigorously tested against observed ozone concentrations for two episodes recorded across 14 rural UK monitoring stations during the spring and summer of 1995. For both episodes, the afternoon concentrations (usually coinciding with the daily maxima) are captured well by the model and the diurnal ozone cycle is reproduced, although the amplitude in concentrations is generally smaller than the observed. The summer episode is investigated further through indicator species analysis and source attribution, and found to be mainly VOC-limited. European emissions account for the majority of ozone production. We demonstrate how improved modelling leads to better understanding of regional and local ozone production across the UK under episodic conditions.     

Summer and autumn ozone fluxes to a forest in the Czech Republic Brdy Mountains

In an effort to examine ozone (O3) deposition over a forest site in the Czech Republic, a low cost eddy flux experiment using slow response ozone and temperature sensors was implemented in July 1993 within the Brdy Mountains. Half-hour 2-Hz ozone and sensible heat measurements made at the Brdy Mountains for 98 days during the period 7 July 1994-20 October 1994 are analyzed and reported. While the Czech Brdy Mountains AOT40 level for the overall 104 day period was 7.6 ppm h (15.1 ppm h for the full 24-h summation), indicating a slight potential for 03 injury, the 1994 summer to autumn'measured forest O3 uptake was 2.4 (+/- 0.9) g m(-2), not unusually high compared to other studies. Average summer midday 03 fluxes and depositidn velocities were -1.0 (+/- 0.6) microg m(-2) s(-1) and 1.1 (+/- 0.7) cm s(-1). and autumn values were -0.36 (+/- 0.4) microg m(-2) s(-1) and 0.7 (+/- 0.5) cm s(-1) respectively. A unique contribution of this study is the first time demonstrated use of slow responding sensors for eddy covariance flux measurements at heights of 20 m above a forest.     

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.     

Modeling eelgrass spatial response to nutrient abatement measures in a changing climate

For many coastal areas including the Baltic Sea, ambitious nutrient abatement goals have been set to curb eutrophication, but benefits of such measures were normally not studied in light of anticipated climate change. To project the likely responses of nutrient abatement on eelgrass (Zostera marina), we coupled a species distribution model with a biogeochemical model, obtaining future water turbidity, and a wave model for predicting the future hydrodynamics in the coastal area. Using this, eelgrass distribution was modeled for different combinations of nutrient scenarios and future wind fields. We are the first to demonstrate that while under a business as usual scenario overall eelgrass area will not recover, nutrient reductions that fulfill the Helsinki Commission’s Baltic Sea Action Plan (BSAP) are likely to lead to a substantial areal expansion of eelgrass coverage, primarily at the current distribution’s lower depth limits, thereby overcompensating losses in shallow areas caused by a stormier climate.     

Spatiotemporal modelling of ozone distribution in the State of California

This paper is concerned with the spatiotemporal mapping of monthly 8-h average ozone (O₃) concentrations over California during a 15-years period. The basic methodology of our analysis is based on the spatiotemporal random field (S/TRF) theory. We use a S/TRF decomposition model with a dominant seasonal O₃ component that may change significantly from site to site. O₃ seasonal patterns are estimated and separated from stochastic fluctuations. By means of Bayesian Maximum Entropy (BME) analysis, physically meaningful and sufficiently detailed space–time maps of the seasonal O₃ patterns are generated across space and time. During the summer and winter months the seasonal O₃ concentration maps exhibit clear and progressively changing geographical patterns over time, suggesting the existence of relationships in accordance with the typical physiographic and climatologic features of California. BME mapping accuracy can be superior to that of other techniques commonly used by EPA; its framework can rigorously assimilate useful data sources that were previously unaccounted for; the generated maps offer valuable assessments of the spatiotemporal O₃ patterns that can be helpful in the identification of physical mechanisms and their interrelations, the design of human exposure and population health models, and in risk assessment. As they focus on the seasonal patterns, the maps are not contingent on short-time and locally prevalent weather conditions, which are of no interest in a global and non-forecasting framework. Moreover, the maps offer valuable insight about the space–time O₃ concentration patterns and are, thus, helpful for disentangling the influence of explanatory factors or even for identifying some influential ones that could have been otherwise overlooked.     

Assessing vegetation exposure to ozone: properties of the AOT40 index and modifications by deposition modelling

A discussion is presented on the application of micrometeorological deposition modelling principles to improve the characterisation of vegetation exposure to ozone and thus the use of critical levels as the basis of targeted emission control. The AOT40 (accumulated exposure over a threshold of 40 ppb or nl l(-1)) ozone exposure index is shown to impose a differential weighting that results in a high sensitivity, by a factor of two to 10 depending on the pollution climate, with respect to concentration. This makes it necessary to correct for systematic effects, such as the concentration profile below the measurement height, in order to justify a comparison with the biological data obtained from well-mixed exposure chambers. Available studies indicate a 50-70% lower AOT40 at the vegetation height. The resistance method for estimating the profile is extended to allow for stomatal effects that potentially bias the plant response predicted with an exposure index. This integrated profile-uptake correction refines the current approach and serves as a transitional step towards a real flux-based approach. For the latter, a new deposition parameterisation is tested against field observations.     

Size-mediated foliar response to ozone in black cherry trees

Local ozone concentration and visible foliar injury were measured over the 1994 growing season on open-grown black cherry (Prunus serotina Ehrh.) trees of varying size (age) within forest stands and adjacent openings at a site in north-central Pennsylvania. Relationships were determined between visible ozone injury and ozone exposure, as well as calculated between injury and ozone uptake expressed as the product of stomatal conductance and ozone concentration. In addition, simultaneous measurements of visible symptoms and leaf gas exchange were also conducted to determine the correlation between visible and physiological injury and ozone exposure. By September, the amount of leaf area affected by visible foliar ozone injury was greatest for seedlings (46%), followed by canopy trees (20%) and saplings (15%). A large amount of variability in foliar ozone symptom expression was observed among trees within a size class. Sum40 and Sum60 (ozone concentration > 40 and > 60 nl liter(-1)) cumulative exposure statistics were the most meaningful indices for interpretation of foliar injury response. Seedlings were apparently more sensitive to ozone injury than larger trees because their higher rates of stomatal conductance resulted in higher rates of ozone uptake. Seedlings also had higher rates of early leaf abscission than larger trees with an average of nearly 30% of the leaves on a shoot abscised by 1 September compared to approximately 5% for larger trees. However, per unit ozone uptake into the leaf, larger trees exhibited larger amounts of foliar injury. The amount of visible foliar injury was negatively correlated (r(2) = 0.82) with net photosynthetic rates, but was not related to stomatal conductance. Net photosynthesis and stomatal conductance thus became uncoupled at high levels of visible foliar injury.     

Heavy metal contamination of roadside soils in the Greater Athens area

The airborne contamination of roadside soils with Pb, Cd, Zn and Ni was evaluated for the Greater Athens Area of Greece. High levels of lead enrichment were found in the upper 0-5 cm soil layer along roads with heavy traffic loads. The central section of the study area appeared to have soils with the highest levels of lead enrichment. The contamination decreased exponentially with the distance from the road edge and dropped to a background level at about 50 m. Most of the lead was concentrated in the upper 5 cm of the soil and was associated with carbonates and crystalline oxides. The main source of contamination was automobile exhausts. Roadside soils were also enriched with airborne Cd and Zn, but to a lesser degree than with Pb. The enrichment of the soil with these two elements fell rapidly and exponentially with distance. No evidence of Ni contamination of roadside soils was obtained.     

Dry deposition of ozone on building materials. Chamber measurements and modelling of the time-dependent deposition

Tests of the dry deposition of ozone to the surfaces of a concrete floor tile and an activated carbon cloth (ACC) sample were performed in a deposition chamber. The time-dependent deposition of ozone to the material surfaces was modelled with an adsorption, desorption, reaction model. This made it possible to find deposition velocities at equilibrium, at t=∞, from shorter time runs of 48 h. The total equilibrium deposition velocity on the concrete floor tile was found to decrease from 0.08(10) to 0.057(10) cm s⁻¹ in three consecutive runs on the same sample, and was found to be 0.137(8) cm s⁻¹ on an ACC. All at a linear airflow velocity of 0.092 cm s⁻¹, RH=50% and T=22°C. Varying the airflow in the deposition chamber, the surface deposition velocity was found to equal to the total deposition velocity for the concrete floor tile. A surface deposition velocity of 0.186(8) cm s⁻¹ was found for the ACC sample. The total real area and the reaction rate constant for the decomposition of ozone was found to be larger, and the adsorption rate constant, the desorption rate constant and the mass of ozone on the surface smaller, on the ACC sample than on the concrete floor tile.     

Measurements and modelling of the ozone deposition velocity to concrete tiles,including the effect of diffusion

A range of models were fitted to the experimental time-dependent curves for the deposition velocity of O₃ to concrete floor tile samples. The models included modified Langmuir isotherms assuming adsorption of O₃ on the material surfaces and models assuming direct reaction on and diffusion of O₃ into the material from the air. The best fit was obtained with a simple two-parameter model assuming direct reaction of O₃ with adsorbed surface water and direct diffusion of O₃ into the material from the air. However, models assuming an additional second-order reaction of O₃ with an adsorbed surface species with a given start mass gave improved curve fit in the first 500 min. Applying the best model to experimental data obtained over the whole air humidity range resulted in markedly lower equilibrium deposition velocities than those measured after 48 h. The modelling gave a deposition velocity minimum in the 50–70% relative air humidity range in agreement with observations. The deposition velocity minimum could be explained with a reduced constant for the reaction of O₃ with water or OH⁻ ions on the surface.     

Simulating the growth response of aspen to elevated ozone: a mechanistic approach to scaling a leaf-level model of ozone effects on photosynthesis to a complex canopy architecture.

Predicting ozone-induced reduction of carbon sequestration of forests under elevated tropospheric ozone concentrations requires robust mechanistic leaf-level models, scaled up to whole tree and stand level. As ozone effects depend on genotype, the ability to predict these effects on forest carbon cycling via competitive response between genotypes will also be required. This study tests a process-based model that predicts the relative effects of ozone on the photosynthetic rate and growth of an ozone-sensitive aspen clone, as a first step in simulating the competitive response of genotypes to atmospheric and climate change. The resulting composite model simulated the relative above ground growth response of ozone-sensitive aspen clone 259 exposed to square wave variation in ozone concentration. This included a greater effect on stem diameter than on stem height, earlier leaf abscission, and reduced stem and leaf dry matter production at the end of the growing season. Further development of the model to reduce predictive uncertainty is discussed.     

Chlorophyll a fluorescence, antioxidant enzymes and lipid peroxidation in tomato in response to ozone and benomyl.

Ozone is a widely distributed phytotoxic air pollutant and is known to reduce the yield of several important agricultural crops in Spain. However, benomyl has been found to lessen the adverse impact of ozone on plants. We studied the effects of ozone and benomyl on chlorophyll a fluorescence, antioxidant enzymes, and lipid peroxidation in tomato (Lycopersicon esculentum Mill. cv. Tiny Tim) grown in open-top chambers in the field. Our results indicate that benomyl prevented the peroxidation of membrane lipids and increased protection of PSII from ozone. There was also a significant reduction in the activity of the antioxidant enzyme superoxide dismutase in ozone-exposed plants that had not been treated with benomyl. Comparing plants treated with benomyl to untreated plants we found that, on exposure to ozone, a greater fraction of light absorption energy was cycled through the photosynthetic system in benomyl-treated plants, as shown by the higher PSII-mediated electron flow and the higher fraction of open PSII reaction centers. The values analyzed in the fluorescence parameters and lipid peroxidation were similar for plants without benomyl grown in a charcoal-filtered environment and benomyl-treated plants exposed to ozone.     

Decomposition of 2-nitrophenol in aqueous solution by ozone and UV/ozone processes.

The decomposition of 2-nitrophenol in aqueous solutions by ozone and UV/ozone processes was found to be technically feasible under adequate experimental conditions. Formation of nitrate ions was observed following the decomposition of 2-nitrophenol by ozone and UV/ ozone processes. Increasing ozone dosage and UV light intensity accelerated the decomposition rate of 2-nitrophenol in an aqueous solution. The species distribution of 2-nitrophenol under various solution conditions plays a significant role in determining decomposition behavior. In most experiments conducted in this study, the decomposition of 2-nitrophenol by ozone and UV/ozone processes was favored to occur in alkaline conditions. The addition of 2-butanol accelerated the rate of gaseous ozone transfer to an aqueous phase by reducing the surface tension of aqueous solution and therefore enhancing the decomposition rate of 2-nitrophenol by ozone and UV/ozone processes.     

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.     

The impact of the 1952 London smog event and its relevance for current wood-smoke abatement strategies in Australia

There is a certain complacency about air pollution in rural towns in Australia. An image of crystal clear skies seems to dominate general perceptions, and few locations actually monitor air pollution levels. Nevertheless, where measurements have been made, particulates have been shown to be the major type of air pollution, and they do reach levels expected to impact on human health. In this article, the contemporary attitudes and behaviour of the government and the population in rural and regional Australia are shown to have a strong resemblance to those that were prevalent prior to the smog events in London in December 1952. Wood smoke poses similar significant health issues in many countries. Insights obtained from the London events, together with more recent research results, are applied to the Australian situation to suggest policy options that are likely to be successful in overcoming the health effects of particulate pollution.

Implications: The contemporary attitudes and behaviour of the government and the population in rural and regional Australia are shown to have a strong resemblance to those that were prevalent prior to the smog events in London in December 1952. Insights obtained from the London event of 1952, together with more recent research results, are applied to the Australian situation to suggest policy options that are likely to be successful in overcoming the health effects of particulate pollution.