Implementing an Operational Ozone Forecasting System Based on WRF/CALMET/CALGRID Models: a 5-Month Case Study over Tuscany, Italy

An ozone forecasting system has been developed based on the CALGRID photochemical dispersion model. The system is implemented as an experimental operational web service at the LaMMA Consortium to forecast ozone pollution over Tuscany region, Italy. It takes advantage of two daily forecasts, one reproducing the meteorology over Tuscany and the other providing chemical boundary conditions. Meteorological forecasts are performed by the Weather Research and Forecasting Nonhydrostatic Mesoscale Model (WRF-NMM) mesoscale model, which is operative at LaMMA for the daily forecasting service. Calculated at a 10-km resolution, WRF-NMM outputs are downscaled to the 4-km system’s final resolution through the CALMET diagnostic model. Daily boundary conditions are forecast by the CHIMERE dispersion model of the PREV'AIR European air quality forecasting system. Since CHIMERE uses the MELCHIOR chemical mechanism, a suitable species conversion was required to the SAPRC-90 mechanism implemented in CALGRID. Emission data are provided by the Regional Inventory of the Sources of Emissions of the Tuscan Regional Authority. Each day, a 96-h simulation is run starting from 00 UTC of the preceding day, used to merely initialize the system, resulting in a 3-day forecast of ozone from today issued to the web in terms of ozone daily mean and maximum concentrations over Tuscany. The system was experimentally run over May to September 2007, resulting in a good accuracy compared to station observations.     

Ozone measurements in Europe

Ozone measurements have been apart of EMEP since its third phase in 1984–1986 and since 1988 data have been collected systematically. By 1992 data for 76 sites were being collected by the Chemical Co-ordinating Centre in NILU. The mean ozone concentration increases from 20–25ppb in the western and northern fringes to 30–35 in central areas of Europe. There is also evidence from the last decade of an upward trend of up to 0.5ppb y^?1 at rural sites in the UK. The data have been analysed to estimate the spatial patterns in AOT 40 for ozone effects on crops and forests. The data show that the critical level for cereal crops of 5300 ppb.h above a threshold of 40 ppb is exceeded over almost all of continental Europe south of 65°N and over most of S.Britain. A similar exercise for the AOT 40 for the forest again shows exceedances of the critical load of 10⁴ ppb.h across all the mapped area of Continental Europe south of 65°N including S.Britian. As land use for forestry and ozone dose both increase with altitude, and these effects have not so far been incorporated in the AOT 40 assessment for forests, the degree of exceedence for forests may have been significantly under-estimated.     

Spatial and Temporal Ozone Pattern Concentrations in a NW Region of Spain

Measurements of ozone were carried out at two different sites in the area surrounding a thermal power plant located in the Northwest of Spain during 1993–1995. The concentration of O₃ in the ambient air varied from 6 to 257 μg m^-3 exhibiting a wide temporal, seasonal and spatial variation. On a few occasions 1-hr ozone concentration was more than 180 μg m^-3, which represents the maximum 1-hr limit of ozone in ambient air as prescribed by the European Commission.     

Analysis of major photochemical pollutants with meteorological factors for high ozone days in Istanbul, Turkey

Hourly ozone, NO _x and VOC concentrations, measured during 2001–2003 summer periods, are analyzed in order to examine the interaction patterns between the major photochemical pollutants in ?stanbul. 34 high ozone days throughout the summer periods of the three years are determined and examined in the study together with the meteorological parameters like temperature, wind and vertical structure of the atmosphere. The results show that high levels of ozone are observed mostly under anticyclonic conditions with relatively low wind speeds. High ozone days generally experienced maximum concentrations at afternoon hours and minimum concentrations are reached at rush hours due to NO _x – titration by traffic emissions. High negative correlations with NO _x up to -0.84 are observed at the Saraçhane station while higher correlations for VOC species, up to ?0.75, are calculated for Kadiköy station. Some individual episodes experiencing high ozone concentrations up to 310 μg m^?3 in the early morning hours are also studied. It is found that decreasing inversion heights in the early hours of the day led to suppression of pollutants close to surface and thus, an increase in ozone concentrations was observed. Low wind speeds played a major role in the increase of pollution levels in the region. HYSPLIT model is applied to some particular episodes and the results show that the northeasterly transport to the region was dominant, especially in the early-morning maximums.     

Urban-Scale Seasonal and Spatial Variability of Ultrafine Particle Number Concentrations

In epidemiological studies, ultrafine particle (UFP) data from a single monitoring site are generally used as a measure of population exposure potentially resulting in exposure misclassification. From August 2009 to October 2010, 1-week campaigns were conducted during each season. The temporal and spatial variations of UFP number size distributions were investigated at 12 monitoring sites distributed across a 9?×?9?km urban area in Rochester, New York using a Fast Mobility Particle Sizer^TM spectrometer. The overall average number concentrations of 5.6- to 560-nm particles in summer, winter, spring, and fall were 9,025, 10,939, 4,955, and 14,485?cm^?3, respectively. Coefficients of divergence and correlation coefficients were calculated between site pairs to assess the spatial heterogeneity in the particle number size distributions. Moderate spatial divergence and uniform temporal variation were found for the chosen sites. Elevated UFP number concentrations were observed near highways, off-road diesel engines, and residential wood combustion sources, indicating significant contributions to the UFP exposure of people living adjacent to these sources. Our results suggest that one stationary monitoring site may not represent the actual human UFP exposure over a whole urban area.     

Modeling of Stomatal Conductance for Estimating Ozone Uptake of Fagus crenata Under Experimentally Enhanced Free-air Ozone Exposure

We examined a performance of the multiplicative stomatal conductance model to estimate the stomatal ozone uptake for Fagus crenata. Parameterization of the model was carried out by in-situ measurements in a free-air ozone exposure experiment. The model performed fairly well under ambient conditions, with low ozone concentration. However, the model overestimated stomatal conductance under enhanced ozone condition due to ozone-induced stomatal closure. A revised model that included a parameter representing ozone-induced stomatal closure showed better estimation of ozone uptake. Neglecting ozone-induced stomatal closure induced a 20?% overestimation of the stomatal uptake of ozone. The ozone-induced stomatal closure was closely related to stomatal ozone uptake rather than accumulated concentrations of ozone exceeding 40?nmol mol^?1. Our results suggest that ozone-induced stomatal closure should be implemented to stomatal conductance model for estimating ozone uptake for F. crenata. The implementation will contribute to adequate risk assessments of ozone impacts on F. crenata forests in Japan.     

A Preliminary Investigation of Ozone Concentrations on the Lizard Peninsula Cornwall,U.K. using Continuous Monitoring and Diffusion Tubes

The Lizard Peninsula is an isolated area of unique and sensitive ecology and the occurrence of damaging ozone concentrations over the peninsula in spring challenges the successful sustainable management of the area. Ozone concentrations over Goonhilly Downs on the Lizard Peninsula in Cornwall were measured in spring 2002 using continuous monitoring and spatial mapping (diffusion tubes). Data obtained using a continuous ozone monitor (1/03/02 to 31/03/02) showed that the AOT40 5-day values were in a range from 2 to 800 μg m^-3 hr (AOT40 is the sum of the differences between the measured hourly ozone concentration (μg m^-3) and 80 μg m^-3 (when the concentration exceeds 80 μg m^-3) for the hours when global radiation exceeds 50 Wm^-2). Contour mapping of ozone concentrations measured with diffusion tubes suggested that over a 2 km² sampling area significant microscale variations were occurring with ozone concentrations ranging between 48–129 μg m^-3 for one two-week period and 62–210 μg m^-3 for the other.Unusually high diurnal variations in ozone concentrations were also observed at Goonhilly. It is thought that temperature inversions caused the entrapment of ozone at the surface level.     

The Determination of Ozone in Ambient Air with Free Hanging Filters as Passive Samplers

This paper describes the use of dry free hanging filters, as passive samplers to determine ozone in the ambient air. The filters, with a diameter of 25?mm, were impregnated with 5,5??-disodium indigo disulphonate (IDS), a reagent for ozone. From the amount of reacted indigo compound, found on the filter, and the ozone concentration in the ambient air, a pseudo rate constant k ₁, of the reaction between ozone (O₃) and IDS on the filter, is calculated. The range of measurement is between 9 and 205???g/m³ ambient ozone. The dry filter method is specific for ozone, while the Dutch standard method NEN2789, based on an aqueous solution of IDS, has to be corrected for the presence of NO _x . From wind tunnel and field experiments, k ₁ proved to vary between 0.7 and 1.5?×?10^?6?m³?s^?1 (??g O₃)^?1 at wind velocities between 1 and 3?m/s and at an exposure time of 60?min. Within these conditions, ozone concentrations have been determined with free hanging filters in four busy streets in Yogyakarta, Indonesia and at two background sites using an average value of k ₁ of 1.2?×?10^?6. Subsequently, the traffic NO emission was estimated from the difference of the O₃ concentrations at both sides of a road. For an arbitrary situation, an NO emission of 255???g/s per metre road length was calculated. The filter method is inexpensive and practical, needs no electricity, is easily assembled and can be used to perform measurements in remote areas. It is shown here that this simple measurement technique may support air quality studies, e.g., in developing countries.     

Impact of Emission Reductions between 1980 and 2020 on Atmospheric Benzo[<Emphasis Type="Italic">a</Emphasis>]pyrene Concentrations over Europe

Benzo[a]pyrene (BaP) has been proven to be toxic and carcinogenic. Since 2010, the European Union officially established target values for BaP concentrations in ambient air. In this study BaP concentrations over Europe have been modelled using a modified version of the chemistry transport model Community Multiscale Air Quality (CMAQ) which includes the relevant reactions of BaP. CMAQ has been run using different emission datasets for the years 1980, 2000, and 2020 as input data. In this study, the changes in BaP concentrations between 1980 and 2020 are evaluated and regions which exceed the European annual target value of 1 ng/m³ are identified, i.e. the Po Valley, the Paris metropolitan area, the Rhine-Ruhr area, Vienna, Madrid, and Moscow. Additionally, the impact of emission reductions on atmospheric concentrations of BaP is investigated. Between 1980 and 2000, half of the BaP emission reductions are due to lower emissions from industrial sources. These emission reductions, however, only contribute to one third of the total ground-level BaP concentration reduction. Further findings are that between 2000 and 2020, a large part (40%) of the BaP concentration reduction is not due to changes in BaP emissions but caused by changes in emissions of criteria pollutants which have an impact on the formation of ozone.     

Spatial distribution of soil heavy metal concentrations as indicator of pollution sources at Mount Križna (Great Fatra,central Slovakia)

The objective of this study was to test the suitability of a simple approach to identify the direction from where airborne heavy metals reach the study area as indication of their sources. We examined the distribution of heavy metals in soil profiles and along differently exposed transects. Samples were taken from 10 soils derived from the same parent material along N-, S-, and SE-exposed transects at 0—10, 10—20, and 20—40 cm depth and analyzed for total Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn concentrations. The heavy metal concentrations at 0—10 cm were larger than background concentrations in German arable soils except for Cr (Cd: 0.6—1.8 mg kg^—1; Cr: 39—67; Cu: 40—77; Ni: 87—156; Pb: 48—94; Zn: 71—129; Fe: 26—34 g kg^—1; Mn: 1.1—2.4). Decreasing Cd, Cu, Mn, and Pb concentrations with increasing soil depth pointed at atmospheric inputs. Aluminum and Ni concentrations increased with soil depth. Those of Fe, Cr, and Zn did not change with depth indicating that inputs at most equalled leaching losses. The Pb accumulation in the surface layer (i.e. the ratio between the Pb concentrations at 0—10 to those at 20—40 cm depth) was most pronounced at N-exposed sites; Pb obviously reached Mount Križna mainly by long-range transport from N where several industrial agglomerations are located. Substantial Cd, Cu, and Mn accumulations at the S- and SE-exposed sites indicated local sources such as mining near to the study area which probably are also the reason for slight Cr and Zn accumulations in the SE-exposed soils. Based on a principal component analysis of the total concentrations in the topsoils four metal groups may be distinguished: 1. Cr, Ni, Zn; 2. Mn, Cd; 3. Pb (positive loading), Cu (negative loading); 4. Al, Fe, indicating common sources and distribution patterns. The results demonstrate that the spatial distribution of soil heavy metal concentrations can be used as indication of the location of pollution sources.     

Ozone Formation Potentials of Volatile Organic Compounds and Ozone Sensitivity to Their Emission in the Megacity of São Paulo, Brazil

In the present study, a three-dimensional Eulerian photochemical model was employed to estimate the impact that organic compounds have on tropospheric ozone formation in the Metropolitan Area of São Paulo (MASP). In the year 2000, base case simulations were conducted in two periods: August 22–24 and March 13–15. Based on the pollutant concentrations calculated by the model, the correlation coefficient relative to observations for ozone ranged from 0.91 to 0.93 in both periods. In the simulations employed to evaluate the ozone potential of individual VOCs, as well as the sensitivity of ozone to the VOC/NO _x emission ratio, the variation in anthropogenic emissions was estimated at 15% (according to tests performed previously variations of 15% were stable). Although there were significant differences between the two periods, ozone concentrations were found to be much more sensitive to VOCs than to NO _x in both periods and throughout the study domain. In addition, considering their individual rates of emission from vehicles, the species/classes that were most important for ozone formation were as follows: aromatics with a kOH?>?2?×?10⁴ ppm^?1 min^?1; olefins with a kOH?<?7?×?10⁴ ppm^?1 min^?1; olefins with a kOH?>?7?×?10⁴ ppm^?1 min^?1; ethene; and formaldehyde, which are the principal species related to the production, transport, storage and combustion of fossil fuels.     

Aliphatic hydrocarbons in surface sediments of the Gulf of Trieste (northern Adriatic)—sources and spatial and temporal distributions

Purpose

A medium-term study of sedimentary aliphatic hydrocarbons in the Gulf of Trieste was performed. The content of the aliphatic hydrocarbons, including their spatial and temporal distributions and origins, was determined. The collected data on the content of these compounds for the period of 2004–2013 were then processed using different evaluation indices and statistical analyses.

Materials and methods

Sediment samples were collected using a gravity core sampler. Hydrocarbons were extracted with hexane and dichloromethane (1:1), and their concentrations were determined by gas chromatography (using an FID detector). Principal component analysis (PCA) was performed to establish the differences between the different sampling sites.

Results and discussion

The study’s results reveal spatial and temporal variabilities in the aliphatic hydrocarbons within the investigated area. The mean concentrations of total aliphatic hydrocarbons were in the range of 17.9–84.6 μg g^?1 d.w., while the concentrations of n-alkanes from C12 to C34 were 934–5232 ng g^?1 d.w. The results of the analyses show higher concentrations of hydrocarbons in the coastal areas, with a decrease toward the central part of the Gulf of Trieste. The interannual differences in hydrocarbon concentrations were generally larger close to river estuaries and pollution sources, where degradation processes are more intensive. Different evaluation indices revealed the hydrocarbons to have different origins. The temporal distribution of aliphatic hydrocarbons shows a decrease in concentrations over the past few years at certain sites. Important changes in the concentration and composition of the aliphatic fraction were observed in and after 2010, characterised by intensive fluvial input and long-lasting decreased salinity.

Conclusions

The content and distribution of aliphatic hydrocarbons are largely dependent on coastal sources of these compounds. Although the investigated area could be considered only slightly to moderately contaminated by hydrocarbons, the recently applied measures for pollution reduction should be continued and intensified.

     

Rural O3 Levels in the Middle Ebro Basin During the Plant Growing Season

Ground-level dynamics of O₃, NO _x and benzene, toluene, ethylbenzene and xylenes were characterised at rural sites in the medium Ebro River Basin (Northern Spain) from April to September (2003–2007) and by means of automated and passive monitoring. The study registered high O₃ levels within the area, which were influenced by traffic emissions, and a monthly evolution of these levels consistent with the occurrence of a broad summer maximum, typical of polluted areas. The mean ozone concentration registered in the studied area by means of passive sampling was 87?±?12 μg m^?3. The 2008/50/EC objective value for the protection of vegetation was widely exceeded during this study (AOT40?=?57,147?±?14,114 μg m^?3 h), suggesting that current ambient levels may pose a risk for crops and vegetation in this important agroindustrial region.     

Evaluation of Premature Mortality Caused by Exposure to PM2.5 and Ozone in East Asia: 2000, 2005, 2020

The aim of this study is to assess the premature mortality risks caused by exposure to particulate matter with aerodynamic diameter less than 2.5???m (PM_2.5) and ozone elevated concentrations for the years?2000, 2005, and 2020 in East Asia. The spatial distributions and temporal variations of PM_2.5 and ozone concentrations are simulated using the Models-3 Community Multiscale Air Quality Modeling System coupled with the Regional Emission Inventory in Asia. The premature mortality risks caused by exposure to PM_2.5 and ozone are calculated based on a relative risk (RR) value of 1.04 (95?% confidence interval (CI): 1.01?C1.08) for PM_2.5 concentrations above the annual mean limit of 10???g?m^?3 taken from the World Health Organization?CAir Quality Guideline and based on a RR value of 1.003 (95?% CI: 1.001?C1.004) for ozone concentration above 35?ppb of the SOMO35 index (the sum of ozone daily maximum 8-h mean concentrations above 35?ppb). We demonstrate one of the implications of the policy making in the area of environmental atmospheric management in East Asia by highlighting the annual premature mortalities associated with exposure to PM_2.5 concentrations that just meet an annual mean concentration of 10???g?m^?3, as well as ozone concentrations that have a daily zero SOMO35 index in vulnerable places. Our results point to a growing health risk that may endanger human life in East Asia. We find that the effect of PM_2.5 on human health is greater than the effect of ozone for the age group of 30?years and above. We estimate the corresponding premature mortality due to the effects of both ozone and PM_2.5 in East Asia for the years?2000 and 2005 to be around 316,000 and 520,000 cases, respectively. For future scenarios of the year?2020, policy succeed case, reference, and policy failed case, the estimated annual premature mortality rates are 451,000, 649,000, and 1,035,000 respectively.     

Elemental concentrations in fresh snowfall across a regional transect in the northeastern U.S.: Apparent sources and contribution to acidity

Fresh snowfall was collected on the surface of 8 lakes across a 350 km west-east transect from northeastern New York state to the coast of Maine after a single storm. In addition, every snowfall event during the winter of 1993 was collected on a single lake near the center of the transect. Across the transect, midwestern sources appear to dominate Pb and Cd concentrations, while Sb appears to be derived from midwestern sources as well as local and/or industrial East Coast sources. In all samples, the highest Na, Cl and Mg concentrations reflect a marine influence, but at some transect sites roadspray aerosol appears to contribute to Na and Cl concentrations. The regional pattern of Ca, K, Mn and Sr concentrations and Mn/Sr ratios indicate that woodsmoke may be an important winter source of these elements at some sites. In all samples, H⁺ is strongly correlated with NO₃ ^? (R² = 0.97) and mean NO₃ ^?/SO₄ ^2? molar ratios of 6.4 for transect samples, and 4.7 for temporal samples, are higher than mean NO₃ ^?/SO₄ ^2? reported for other precipitation studies in the same region. The contribution of NO₃ ^? to the snowpack greatly exceeds that of SO₄ ^2?, and may be a major source of acidity in aquatic ecosystems during snowmelt.     

Spatial and Temporal Heavy Metal Concentration (Cu,Pb, Zn,Hg, Fe,Mn, Hg) in Sediments of the Mar Piccolo in Taranto (Ionian Sea,Italy)

The Mar Piccolo (surface area of 20.72 km²) is located in the Northern area of the Taranto town (Ionian Sea, Italy). It is an inner, semi-enclosed basin with lagoon features connected with the Mar Grande through two channels which are very important for water exchange. Mar Piccolo basin is subjected to urbanization, industry, agriculture, aquaculture and commercial fishing. Hence, it is important to have a temporal picture both of heavy metal content and of organic carbon and their distribution (hydrophobic fraction, hydrophilic fraction, humic compounds) to check the progress of pollution in time. Three sediment cores collected on the basis of the pollution sources have been analyzed. Both heavy metal and organic carbon concentrations underline the fact that the anthropogenic input is different in the three sites, and that in time the amount of pollutants coming into the Mar Piccolo have changed in different ways. The high amount of organic hydrophilic compounds present in sediments, both due to the small water depth and to the high accumulation rate, make the sediment site high in oxygen consumption due to a considerable chemical and biochemical transformations of organic matter.     

Soil geochemistry in relation to water chemistry and sensitivity to acid deposition in Finnish Lapland

Ecosystems in Finnish Lapland are threatened by heavy metal pollution and acid deposition derived from emissions of Cu-Ni smelters in Kola Peninsula and to varying extent to pollution from southern Fennoscandian and Central European sources. Extensive chemical analyses of small lake waters collected in Finnish Lapland have demonstrated that a significant number of lakes are acidified (ANC < 0μcq/l) or their buffering capacity is critical (ANC = 0–50μe/l). The relative abundance of mafic, ultramafic and carbonate rock components in the catchment were the chief factors controlling ANC and the main base cation (Ca²⁺, Mg²⁺) concentrations of lake waters. Both humic and clearwater lakes with low buffering capacity (ANC < 50μeq/l) were mainly located in the catchment areas identified as sensitive to acidification on the basis of low content of base cations (Ca²⁺ +Mg²⁺ +K⁺ < 500 meq/kg) in till. The ratio of the catchment area to the lake area was distinctly smaller for acidic lakes than for the well-buffered lakes, indicating the importance of catchment processes in determining the ANC and main base cations. The high sulphur concentrations (median 60μeq/1) of acidic lakes in northeastern Lapland, near the Finnish-Norwegian border, were strongly correlated with the highest deposition of sulphur derived from smelters of Kola Peninsula. The anomalously high concentrations of sulphur of well-buffered lakes in the western part of Lapland were due to sulphide minerals of soil and bedrock. The acidity of humic lakes in southern Lapland was in large part due to the organic acidity derived from peatlands.     

Bioindication of ozone in Estonia by using the tobacco variety Bel W3

The presence of tropospheric ozone was monitored by estimating necrotic flecks on the leaves of the ozone-sensitive tobacco variety Bel W3 in Estonia in 1990 and 1991. The indicator and control plants (variety Samsun) were planted in four localities (Käsmu, northern Estonia; Tartu, central Estonia, with two sites and Kooraste, southern Estonia). The percentage of the leaf area covered with necrotic flecks (necrotic index of the leaf) was determined individually for each leaf from mid-June until the end of September. The mean daily increment of the necrotic index for the period between two observations (typically 6–14 days) was calculated for each plant (NII_plant) and for the site (NII_site). The latter parameter indicates the variability of ozone episodes during the vegatation period. Ozone damage to leaves displayed an irregular pattern throughout the vegetation period, the values of NII_site ranging from 0 to 0.3 (Kooraste, 1990) and 0.9 to 2.8 (Käsmu, 1991). The average NII_site for the vegetation period was highest in northern Estonia (0.77 in 1990 and 1.47 in 1991) and lowest in southern Estonia (0.07 in 1990). High ozone damage in Käsmu can be explained by the close location (70–80 km) of the experimental site to major thermal power plants of Estonia and cities (Tallinn and Helsinki). Higher ozone damage in all the observed sites in 1991 as compared to 1990 can be accounted for different conditions for ozone formation.The number of sunny hours was 27% higher in 1991. In July the difference in sunny hours was almost twofold. It is concluded that ozone damage to plants is likely to occur in sunny summers in Estonia.     

Quantifying the fine scale (1km × 1km) exposure and effects of ozone. Part 1. Methodology and application for effects on forests

Surface ozone concentrations show very large local variability. This, in rural areas, is largely a consequence of the degree to which the surface air is decoupled from the bulk of the atmosphere by nocturnal and winter stability effects and of the aerodynamic roughness and topography of the countryside. Procedures have been developed to simulate these effects and have been used with O₃ data from a regional monitoring network to quantify exposure of vegetation to mean and peak O₃ concentrations. The index of exposure to potentially phytotoxic O₃ concentrations is the AOT40 (accumulated exposure over a threshold of 40 ppb) expressed in ppb.h. The accumulated exposure of crop and forest surfaces to ozone is shown to increase approximately linearly with altitude and along a gradient from 3000 ppb.h in north west Scotland to 7000 ppb.h in the south of England. The area of UK forest which exceeds the critical level for ozone effects (10⁴ ppb.h above 40 ppb) totals 2.0 × 10⁴ km² and represents 47% of afforested land. The areas affected include most of southern and central England and Wales and large plantation forests of Northumberland and the Scottish borders.