Increase of Ozone Concentration in an Inland Basin During the Period of Nocturnal Thermal High

Since ground level ozone concentrations in the basin on one day before the occurrence of unusually high air temperature with nocturnal thermal high showed a typical urban type of a maximum ozone concentration at 1300 LST and a minimum at night. However, a maximum ozone concentration under extremely high air temperature of 39.2 °C was detected at 1700 LST or 1800 LST at two environmental monitoring sites, which was 4 or 5 hr delayed from the typical occurrence time, 1300 LST. Its maximum value showed about 50 or 70% increase of the concentration more than the typical maximum value and its concentration gradually decreased until 2100 LST. After 1200 LST until 1800 LST, air temperature was maintained over 35 °C and the high temperature made a great contribution to the increase of O₃ for several hours. The deviated occurrence time of a maximum ozone concentration is mainly attributed to meteorological and topographic effects – shifted occurrence time of maximum air temperature, shrunken atmospheric boundary layer depth and wind. While daytime O₃ concentration due to photochemical production of O₃ from NO₂ increased, NO₂ concentration decreased, with their reverse respondent patterns each night. A secondary maximum concentration of O₃ at 2300 LST or 2400 LST is due to a much shallower depth of nocturnal surface inversion layer with daytime producing more O₃ than that of the daytime convective boundary layer, resulting in the increase of ozone concentration, though the reduction of ozone occurred under the reversal process of O₃ into NO₂.     

Effects of Nitrogen Supply on the Sensitivity to O3 of Growth and Photosynthesis of Japanese Beech (Fagus crenata) Seedlings

To obtain basic information for evaluating critical levels of O₃ under different nitrogen loads for protecting Japanese beech forests, two-year-old seedlings of Fagus crenata Blume were grown in potted andisol supplied with N as NH₄NO₃ solution at 0, 20 or 50 kg ha⁻¹ year⁻¹ and exposed to charcoal-filtered air or O₃ at 1.0, 1.5 and 2.0 times the ambient concentration from 16 April to 22 September 2004. The O₃ induced significant reductions in the whole-plant dry mass, net photosynthetic rate at 380 μmol mol⁻¹ CO₂ (A ₃₈₀), carboxylation efficiency (CE) and concentrations of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) and total soluble protein (TSP) in the leaves. The concentrations of Rubisco and TSP were negatively correlated with the concentration of leaf acidic amino acid, suggesting that O₃ enhanced the degradation of protein such as Rubisco. The N supply to the soil did not significantly change the whole-plant dry mass and A ₃₈₀, whereas it significantly increased the CE and concentrations of Rubisco and total amino acid. No significant interactive effects of O₃ and N supply to the soil were detected on the growth, photosynthetic parameters and concentrations of protein and amino acid in the leaves. In conclusion, N supply to the soil at ≤50 kg ha⁻¹ year⁻¹ does not significantly change the sensitivity to O₃ of growth and net photosynthesis of Fagus crenata seedlings.     

Effect of mixing on NO removal in the selective noncatalytic reduction reaction process

The effect of mixing of NH₃ and NO on the selective noncatalytic reduction (SNCR) reaction was investigated using a bench-scale reactor. Three different experimental conditions were compared for the removal of NO in the bulk gas with NH₃, a reducing agent, by means of mixing and contacting. The temperature that gave the highest NO removal efficiency was about 800°C when NH₃ was injected with air or NH₃ was premixed and air was injected. It is suggested that control of mixing of the reducing agent and the injection conditions could be a good way to increase NO removal efficiency as well as to lower the reaction temperature. When NH₃ was injected with air, the NO removal efficiency increased with increasing injected air flow if the initial NO concentration was low, whereas for high NO concentrations, the NO removal efficiency slightly increased up to an injected air flow rate of 100 ml/min. A proposed mixed-flow model can be used as a prediction tool for the NO removal efficiency covering various conditions of the real SNCR process.     

Green Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Cellulose/Polyvinyl Alcohol Hybride Aerogel and Its Application for Dye Removal

A novel Fe₃O₄/cellulose–polyvinyl alcohol (PVA) aerogel was successfully synthesized by an eco-friendly and facile method in this work. Cellulose/PVA matrix was prepared through an environmental friendly physical cross-linking process and further in-situ decorated with Fe₃O₄. Series of Fe₃O₄ decorated aerogels were prepared and the effects of Fe₃O₄ nanoparticles (NPs) on the aerogels were systematic investigated. As-prepared aerogels exhibited desirable properties including nanostructure, relatively high porosity, improved mechanical and superparamagnetism. The TEM results showed that Fe₃O₄ NPs were integrated in the three-dimensional matrix of cellulose/PVA with a diameter of 9–12 nm. Furthermore, the mechanical strength of the aerogels was significantly enhanced after the introduction of Fe₃O₄ NPs. Meanwhile, the obtained Fe₃O₄/cellulose/PVA aerogel exhibited excellent adsorption performance toward methyl blue dye, and can be reused through fenton-like catalysts oxidative degradation of organic dye in H₂O₂ solution. Therefore, they will have a great potential application as eco-friendly and economical adsorbents.     

A Sensitivity Analysis of Ozone Formation to Ambient Air Composition by Means of Photochemical Models

The prediction of the atmospheric concentration of ozoneand of other photochemical pollutants represents one of themajor scientific challenges in the study of urban airquality. To this aim, photochemical models are widelyapplied as support tools for regulatory purposes, but theirresults are known to be affected by several uncertainties,in boundary conditions, geographical and meteorologicaldata and the chemical composition of emission and ambientair as well. Also the mechanism selected to describe theurban chemistry may lead to large differences in the modelresults. In this work, the influence of ambient air composition onthe results of photochemical model has been studied using a simple Lagrangian trajectory model coupled with different chemical sub-models (CB-IV and a simplified version of EMEP). To this aim a parametric sensitivity study of ozone with respect to its precursors' concentration was performed withreference to the same meteorological conditions and by simulatingdifferent scenarios characterized by specific emitted pollutantsconcentration. Rather than analyzing sensitivity by changing initial composition, an analytical local sensitivity concept has been applied; this allowed evaluation the influence of initial concentration on the predicted ozone concentration andto discriminate between VOC-sensitive and NOx-sensitive kineticregimes. Finally, these results have been successfully comparedwith those obtained applying the concept of photochemical indicators (i.e. O₃/NOy and H₂O₂/HNO₃ ratios).     

The effect of bed properties on methane removal in an aerated biofilter--model studies

The capacity of laboratory-scale aerated biofilters to oxidize methane was investigated. Four types of organic and mineral-organic materials were flushed with a mixture of CH₄, CO₂ and air (1:1:8 by volume) during a six-month period. The filter bed materials were as follows: (1) municipal waste compost, (2) an organic horticultural substrate, (3) a composite of expanded perlite and compost amended with zeolite, and (4) the same mixture of perlite and compost amended with bentonite. Methanotrophic capacity during the six months of the experiment reached maximum values of between 889 and 1036 g m⁻² d⁻¹. Batch incubation tests were carried out in order to determine the influence of methane and oxygen concentrations, as well as the addition of sewage sludge, on methanotrophic activity. Michaelis constants K_M for CH₄ and O₂ were 4.6-14.9%, and 0.7-12.3%, respectively. Maximum methanotrophic activities V_max were between 1.3 and 11.6 cm³ g⁻¹ d⁻¹. The activity significantly increased when sewage sludge was added. The main conclusion is that the type of filter bed material (differing significantly in organic matter content, water-holding capacity, or gas diffusion coefficient) was not an important factor in determining methanotrophic capacity when oxygen was supplied to the biofilter.     

Production characteristics of N2O during stabilization of municipal solid waste in an intermittent aerated semi-aerobic bioreactor landfill

An intermittent aerated semi-aerobic bioreactor landfill has the advantages such as accelerating stabilization of municipal solid waste (MSW), reducing methane, and in situ nitrogen removal. However, the introduction of air into a nutrient rich environment induces nitrification and denitrification processes, as well as the potential to generate N species at intermediate oxidation states, including nitrous oxide (N₂O). In this study, a simulated intermittent aerated semi-aerobic bioreactor landfill was designed and operated for 262 d in order to establish the production characteristics of N₂O. The N₂O concentration changed significantly with the degree of MSW stabilization, a low concentration level ranged from undetectable to 100 ppm in the initial stabilization period, then one or two orders of magnitude higher in the later stabilization period compared with the initial period. It is clear that N₂O production is relevant to the biodegradable organics in leachate and refuse. Once the biodegradable carbon sources were insufficient, which limited the activity of denitrifying organisms, higher N₂O production began.     

Sources and Variability of Indoor and Outdoor Gaseous Aerosol Precursors (O3, NOx and VOCs)

Measurements of indoor and outdoor aerosol concentrations and their gaseous precursors (O₃, NO and NO₂) as well as volatile organic compounds (VOCs) concentrations were performed at two houses in the Oslo metropolitan area. The variability of the concentration of gaseous compounds was studied in respect to their sources in the indoor and outdoor environments. Domestic heating during the winter and photochemical production during the summer were the main sources for outdoor NOx and O₃. In the indoor environment infiltration of outdoor air, candle burning, smoking and indoor chemical reactions were the main sources affecting their concentrations. The concentrations of VOCs outdoors were enhanced during the summer due to biogenic emissions whereas in the indoor environment their values were affected mostly by emissions from materials used during the recent refurbishing of the houses (>0.4 mg/m³).     

Inter-annual Variations of Ozone and Nitrogen Dioxide Over Europe During 1958–2003 Simulated with a Regional CTM

Inter-annual variability of surface ozone (O₃) and nitrogen dioxide (NO₂) over Europe has been studied over the period 1958–2003 using a three-dimensional Chemistry-Transport Model coupled to meteorological data from the ERA40 data set produced at the European Centre of Medium-range Weather Forecasts (ECMWF). Emissions and boundary conditions were kept at present levels throughout the simulation period. It was found that the annual mean NO₂ concentration varies between ±50% and the summer mean O₃ concentration varies between −10 and +20 percent (%) compared to the 46-year average over the model domain. There is also variation in ozone and NO₂ over longer time scales. The last 22 years display high concentrations of ozone in central and south-western Europe and low concentrations in north-eastern Europe. The first 22 years display very high concentrations of NO₂ over the North Sea. There is indication of trends in ozone and nitrogen dioxide but this has to be investigated further. Such information is one factor that should be taken into account when considering future control strategies.     

Experimental and numerical calculations of waste R-134a thermal decomposition for energy and fluorine material recovery

Considering the global warming potential of R-134a (C₂H₂F₄) with the substantial generation of this refrigerant as waste material in various industrial sectors, the development of proper thermal destruction method of R-134a is of great practical significance. For this, experiment and numerical calculations have initially made for a tubular-type furnace in order to figure out the basic combustion characteristics of R-134a. A series of experimental investigations for the thermal decomposition of R-134a have been made as a function of wall temperature of tubular furnace and important reacting species such as O₂ and H₂O necessary for the decomposition of C₂H₂F₄ into HF, CO₂ and H₂O. In general, the thermal decomposition of R-134a is successfully made for the condition of temperature above 800 °C with the supply of stoichiometric amount of O₂ and these results are well agreed with numerical prediction. And this information is employed for the simulation of a full-scale, practical incinerator used for the CDM project. For this, numerical investigation has been made for a commercial-scale incinerator using CH₄–air flames for the proper destruction C₂H₂F₄ together with the control of pollutants such as CO and NO. In general, the destruction rate of C₂H₂F₄ appears more than 99.99 % and the generation of CO and NO species appears rather sensitive to the operational condition such as amount of water vapor. The numerical method of HFCs (hydrofluorocarbons) thermal treatment shows high possibility as a viable tool for the proper design and optimal determination of the operational condition for a HFCs incinerator.     

Energy from Waste – Clean,efficient, renewable: Transitions in combustion efficiency and NOx control

Traditionally EfW (Energy from Waste) plants apply a reciprocating grate to combust waste fuel. An integrated steam generator recovers the heat of combustion and converts it to steam for use in a steam turbine/generator set. This is followed by an array of flue gas cleaning technologies to meet regulatory limitations.Modern combustion applies a two-step method using primary air to fuel the combustion process on the grate. This generates a complex mixture of pyrolysis gases, combustion gases and unused combustion air. The post-combustion step in the first pass of the boiler above the grate is intended to “clean up” this mixture by oxidizing unburned gases with secondary air.This paper describes modifications to the combustion process to minimize exhaust gas volumes and the generation of noxious gases and thus improving the overall thermal efficiency of the EfW plant. The resulting process can be coupled with an innovative SNCR (Selective Non-Catalytic Reduction) technology to form a clean and efficient solid waste combustion system.Measurements immediately above the grate show that gas compositions along the grate vary from 10% CO, 5% H₂ and 0% O₂ to essentially unused “pure” air, in good agreement with results from a mathematical model. Introducing these diverse gas compositions to the post combustion process will overwhelm its ability to process all these gas fractions in an optimal manner. Inserting an intermediate step aimed at homogenizing the mixture above the grate has shown to significantly improve the quality of combustion, allowing for optimized process parameters. These measures also resulted in reduced formation of NO_x (nitrogenous oxides) due to a lower oxygen level at which the combustion process was run (2.6 vol% O_2, wet instead of 6.0 vol% O_2, wet).This reduction establishes optimal conditions for the DyNOR? (Dynamic NO_x Reduction) NO_x reduction process. This innovative SNCR technology is adapted to situations typically encountered in solid fuel combustion. DyNOR? measures temperature in small furnace segments and delivers the reducing reagent to the exact location where it is most effective. The DyNOR? distributor reacts precisely and dynamically to rapid changes in combustion conditions, resulting in very low NO_x emissions from the stack.     

Self-heating of dried industrial wastewater sludge: Lab-scale investigation of supporting conditions

We studied the reactivity of dried sludge produced by treatment of wastewater, mainly from tanneries. The solids transformations have been first characterized with thermal analysis (TGA and DSC) proving that exothermic transformation takes place at fairly low temperature, before the total organic combustion that occurs in air above 400 °C. The onset of low temperature reactions depends on the heating rate and it can be below 100 °C at very small heating rate.Then, we reproducibly determined the conditions to trigger dried sludge self-heating at the laboratory scale, on samples in the 0.2–0.3 kg size. Thermal insulation, some aeration and addition of water are key factors. Mastering the self-heating at this scale allows more detailed investigations as well as manipulation of conditions, to understand its nature, course and remediation. Here we report proves and discussions on the role of air, water, particle size, porosity and biological activity, as well as proving that also dried sludge from similar sources lead to self-heating.Tests demonstrate that air and water are simultaneously required for significant self-heating to occur. They act in diverging directions, both triggering the onset of the reactions and damping the temperature rise, by supporting heat loss. The higher the O₂ concentration, the higher the solids heating rate. More added water prolongs the exothermic phase. Further additions of water can reactivate the material. Water emphasizes the exothermic processes, but it is not sufficient to start it in an air-free atmosphere. The initial solid moisture concentration (between 8% and 15%) affects the onset of self-heating as intuitive. The sludge particles size strongly determines the strength and extent of the heat release, indicating that surface reactions are taking place. In pelletized particles, limitations to water and air permeability mitigates the reaction course.     

Addition of tracers into the polypropylene in view of automatic sorting of plastic wastes using X-ray fluorescence spectrometry

This study focused on the detection of rare earth oxides, used as tracers for the identification of polymer materials, using XRF (X-ray fluorescence) spectrometry. The tests were carried out in a test system device which allows the collection of static measurements of the samples’ spectrum through the use of energy dispersive X-ray fluorescence technology.A sorting process based on tracers added into the polymer matrix is proposed in order to increase sorting selectivity of polypropylene during end-of-life recycling. Tracers consist of systems formed by one or by several substances dispersed into a material, to add a selective property to it, with the aim of improving the efficiency of sorting and high speed identification.Several samples containing rare earth oxides (Y₂O₃, CeO₂, Nd₂O₃, Gd₂O₃, Dy₂O₃, Er₂O₃ and Yb₂O₃) in different concentrations were prepared in order to analyse some of the parameters which can influence the detection, such as the concentration of tracers, the acquisition time and the possible overlapping among the tracers. This work shows that by using the XRF test system device, it was possible to detect 5 of the 7 tracers tested for 1 min exposure time and at a concentration level of 1000 ppm. These two parameters will play an important role in the development of an industrial device, which indicates the necessity of further works that needs to be conducted in order to reduce them.     

Growth and Nitrogen Availability of Red Pine Seedlings under High Nitrogen Load and Elevated Ozone

To evaluate the effect of increasing nitrogen (N) deposition and tropospheric ozone (O₃) concentrations on N-saturated forest ecosystems, we investigated the response of Japanese red pine (Pinus densiflora), an N-saturation sensitive tree species, to increasing N load under elevated O₃ concentrations. One-year-old seedlings of red pine were treated with three levels of N supply (0, 50 and 100 mg N L^-1 fresh soil volume) under two levels of atmospheric O₃ concentration (< 5 and 60 ppb) for two growing seasons. Nitrogen treatment did not stimulate dry matter production of the seedlings. Growth inhibition was observed in the highest N treatment under low O₃ and in the two higher N treatments under elevated O₃. Irrespective of the O₃ concentration, increasing N supply negatively affected root growth and mycorrhizal development in fine roots, resulting in a reduction in P and Mg uptake from the soil. Net photosynthetic rate was significantly reduced by both the highest N treatment under low O₃ and the two higher N treatments under elevated O₃, together with decreased N-availability to Rubisco. Nitrogen assimilated from NO₃ ^- to amino acid in the needles was not affected by the treatments. However, needle protein concentration was reduced by the highest N-treatment under low O₃ and by the two higher N-treatments under elevated O₃. These results suggest that elevated O₃ potentially disturbs the N-availability in the form of protein including Rubisco, and may advance the negative effects of excessive N-deposition on N-sensitive plant species in N-saturated forests.     

Evidence for biodegradation and volatilisation of dissolved petroleum hydrocarbons during in situ air sparging in large laboratory columns

Laboratory column experiments run for up to 13 days compared air sparging of groundwater contaminated by dissolved petroleum hydrocarbons in sterile and non-sterile aquifer sediments as well as uncontaminated sediments and groundwater. Loss of dissolved BTEX compounds in the contaminated columns was very rapid, occurring through volatilisation. The majority of the dissolved total organic carbon (TOC) persisted for much longer periods however. A direct comparison between losses from sterile and non-sterile columns suggested a negligible contribution of biodegradation to the removal of TOC. This was difficult to confirm through examination of O₂ utilisation because oxidation of a small amount of reduced sulphur in the aquifer materials was the dominant sink for O₂. Despite this, it was possible to conclude that less than 22% of the removal of TOC was through biodegradation during the first three days of air sparging.     

PM10, O3, CO Concentrations and Elemental Analysis of Airborne Particles in a School Building

Measurements of indoor and outdoor PM10, as well as indoor O₃ and CO concentrations were conducted and are presented here. These measurements were carried out at an institute building, located in a suburban industrial area in Greece. Both indoor and outdoor PM10 samples were also collected and their elemental composition was identified by ED-XRF analysis. Twenty seven major, minor and trace elements were identified. The measurements took place generally in different periods of institute operation, from June 2004 to February 2005. The indoor PM10 concentrations which were measured during the normal operation period of the institute were found to be many times higher than the respective outdoor PM10 concentrations of the same periods. On the contrary, the indoor PM10 concentrations which were measured during the holiday period were found to be lower than their corresponding outdoor values. Indoor O₃ and CO concentrations were found to be in low level. Indoor PM10 concentrations were found to be in a relative good correlation with O₃ (r = 0.45) and in high correlation (r = 0.98) with CO concentrations. On average, total elements concentrations were much higher indoors relative to outdoors. Based on above findings we attempted to determine the pollution sources of the indoor environment and to investigate some parameters or chemical processes that affect indoor pollutants’ levels.     

Treatment of municipal landfill leachate by catalytic wet air oxidation: Assessment of the role of operating parameters by factorial design

The wet air oxidation (WAO) of municipal landfill leachate catalyzed by cupric ions and promoted by hydrogen peroxide was investigated. The effect of operating conditions such as WAO treatment time (15-30 min), temperature (160-200 °C), Cu²⁺ concentration (250-750 mg L⁻¹) and H₂O₂ concentration (0-1500 mg L⁻¹) on chemical oxygen demand (COD) removal was investigated by factorial design considering a two-stage, sequential process comprising the heating-up of the reactor and the actual WAO. The leachate, at an initial COD of 4920 mg L⁻¹, was acidified to pH 3 leading to 31% COD decrease presumably due to the coagulation/precipitation of colloidal and other organic matter. During the 45 min long heating-up period of the WAO reactor under an inert atmosphere, COD removal values up to 35% (based on the initial COD value) were recorded as a result of the catalytic decomposition of H₂O₂ to reactive hydroxyl radicals. WAO at 2.5 MPa oxygen partial pressure advanced treatment further; for example, 22 min of oxidation at 200 °C, 250 mg L⁻¹ Cu²⁺ and 0-1500 mg L⁻¹ H₂O₂ resulted in an overall (i.e. including acidification and heating-up) COD reduction of 78%. Amongst the operating variables in question, temperature had the strongest influence on both the heating-up and WAO stages, while H₂O₂ concentration strongly affected the former and reaction time the latter. Nonetheless, the effects of temperature and H₂O₂ concentration were found to depend on the concentration levels of catalyst as suggested by the significance of their 3rd order interaction term.     

Long Term Trends in Concentration of Major Pollutants (SO<Subscript>2</Subscript>, CO,NO, NO<Subscript>2</Subscript>, O<Subscript>3</Subscript> and PM<Subscript>10</Subscript>) in Prague – Czech Republic (Analysis of Data Between 1992 and 2005)

To assess the effect of changes in traffic density and fuels used for heating at the beginning of the 1990s, 1992–2005 monthly averages of PM₁₀, SO₂, NO₂, NO, CO and O₃ from Prague, the Czech capital, were analyzed together with long term trends in emissions of major pollutants, fuel consumption and number of vehicles registered in Prague. The data from all monitoring stations were retrieved from the database of the state automated monitoring system. Correlation coefficients between ambient monthly averaged temperature and all pollutants of concern showed distinct seasonal trends. The results showed that while SO₂ and to some extent also CO concentrations dropped namely in the first half of the analyzed period (1992–1997) as a result decreased fossil fuel consumption for local heating, the behaviour of other pollutant concentrations followed a different pattern. PM₁₀ concentrations decreased during the beginning of the 1990s but showed a sign of increase after 2000. Concentrations of ozone and NO₂ did not reveal any significant change throughout the whole studied period. It can be concluded that during the studied period traditional urban sources of pollution, such as coal and oil combustion, lost their importance but were simultaneously substituted by pollutants from automotive transport (namely PM and NO₂) making the problem of air quality even worse.     

Reductive decomposition of waste gypsum with SiO<Subscript>2</Subscript>, Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> additives

From the point of view of a sustainable and environment-friendly society based on the recycling of material resources, it is preferable to utilize waste gypsum as a substitute for lime, which is currently produced by the calcination of limestone. In the present work, the reductive decomposition of CaSO₄ was investigated under an atmosphere of CO: 2 vol%, CO₂: 30 vol%, with N₂ as a carrier gas without and with the addition of SiO₂, Al₂O₃, or Fe₂O₃. It was found that the decomposition temperature of CaSO₄ was significantly reduced from 1673 K to 1223 K when only 5 wt% Fe₂O₃ was added to CaSO₄. In the case of the addition of SiO₂ or Al₂O₃ to CaSO₄, the decomposition temperature was reduced from 1673 K to 1623 K. This was due to the formation of composite oxides (calcium ferrite, calcium silicate, or calcium aluminate) during the reaction of CaSO₄ with the additives at a lower temperature. In addition, the formation of unfavorable product CaS was inhibited in the presence of 5 wt% Fe₂O₃, and this inhibition effect further increased as the addition of Fe₂O₃ was increased. In contrast, no significant effect on the inhibition of CaS formation was observed on the addition of SiO₂ or Al₂O₃.     

Concentrations,Cumulative Exposure and Critical Levels of Ozone in Ireland

Concentrations of tropospheric ozone(O₃) and exceedance of critical levels to vegetationhave been investigated and mapped for Ireland. Hourlyozone concentration data (1995–1997) at 7 sevenmonitoring stations and the CORINE landcover database,supported by a Geographical Information System, wereused. AOT40 (Accumulated exposure Over a Threshold of 40ppb) was calculated for daylight hours for each station,and mapped using surface interpolation. Average O₃concentrations vary from year to year, and were estimatedto be 28 ppb, 26 ppb and 24 ppb for 1995, 1996 and 1997respectively. Ozone concentrations show a large diurnalvariation, with a maximum in the afternoon and a minimumat night-time. The critical level for crops and (semi-)natural vegetation was exceeded in all years examined.The highest exceedance occurred in 1995, where thecritical level was exceeded for almost 35% of the mappedarea. Approximately 15% and 1% of the mapped area wasexposed to exceedance levels during 1996 and 1997respectively. The maximum cumulative exposures (AOT40)were approximately 5000, 3890 and 3230 ppbh in 1995, 1996and 1997 respectively. The critical level for forests wasnot exceeded during the period of investigation.