Spatial variations of ground level ozone concentrations in areas of different scales

The spatial variation of ground level ozone concentrations was investigated for areas of three different scales: (1) an air quality management district (a region about 100×70 km²) in northern Taiwan, (2) the neighborhood (about 2 km in radius) of an air quality monitoring station, and (3) an open field (about 400×600 m²) surrounded by 3- and 4-story buildings in an elementary school. Analysis of data on hourly ozone concentration, obtained at 13 m above the ground at 21 monitoring stations in the air quality management district, showed that the stations downwind of the urban center in the district had significantly higher ozone concentrations. Measurements for 8-h average ozone concentrations at 1.5 m above the ground by passive samplers showed that, in a flat area about 2 km in radius, the ratios of the ozone concentration at open areas to that at the monitoring station (0.86–0.93) were significantly higher than those obtained at areas with higher traffic flow and density of buildings (0.60–0.68). For the open field in an elementary school, the 8-h average ozone concentrations at 1.5 m above the ground at sites less than 10 m from the nearest building were considerably lower than those at sites farther away from buildings. The results indicated that, in areas of small scales, the spatial distributions of ozone concentration were highly non-uniform and there were appreciable day-to-day variability in spatial distribution. Such variability should be taken into account in determining the extent to which an individual is exposed to ozone.     

Increasing interannual and altitudinal ozone mixing ratios in the Catalan Pyrenees

Interannual, seasonal, daily and altitudinal patterns of tropospheric ozone mixing ratios, as well as ozone phytotoxicity and the relationship with NO_x precursors and meteorological variables were monitored in the Central Catalan Pyrenees (Meranges valley and Forest of Guils) over a period of 5 years (2004–2008). Biweekly measurements using Radiello passive samplers were taken along two altitudinal transects comprised of thirteen stations ranging from 1040 to 2300 m a.s.l. Visual symptoms of ozone damage in Bel-W3 tobacco cultivars were evaluated biweekly for the first three years (2004–2006). High ozone mixing ratios, always above forest and vegetation protection AOT40 thresholds, were monitored every year. In the last 14 years, the AOT40 (Apr–Sept.) has increased significantly by 1047 μg m^?3 h per year. Annual means of ozone mixing ratios ranged between 38 and 67 ppb_v (38 and 74 ppb_v during the warm period) at the highest site (2300 m) and increased at a rate of 5.1 ppb_v year^?1. The ozone mixing ratios were also on average 35–38% greater during the warm period and had a characteristic daily pattern with minimum values in the early morning, a rise during the morning and a decline overnight, that was less marked the higher the altitude. Whereas ozone mixing ratios increased significantly with altitude from 35 ppb_v at 1040 m–56 ppb_v at 2300 m (on average for 2004–2007 period), NO₂ mixing ratios decreased with altitude from 5.5 ppb_v at 1040 m–1 ppb_v at 2300 m. The analysis of meteorological variables and NO_x values suggests that the ozone mainly originated from urban areas and was transported to high-mountain sites, remaining aloft in absence of NO. Ozone damage rates increased with altitude in response to increasing O₃ mixing ratios and a possible increase in O₃ uptake due to more favorable microclimatic conditions found at higher altitude, which confirms Bel-W3 as a suitable biomonitor for ozone concentrations during summer time. Compared to the valley-bottom site the annual means of ozone mixing ratios are 37% larger in the higher sites. Thus the AOT40 for the forest and vegetation protection threshold is greatly exceeded at higher sites. This could have substantial effects on plant life at high altitudes in the Pyrenees.     

The effect of variability in industrial emissions on ozone formation in Houston, Texas

Ambient observations have indicated that high concentrations of ozone observed in the Houston/Galveston area are associated with plumes of highly reactive hydrocarbons, mixed with NO_x, from industrial facilities. Ambient observations and industrial process data, such as mass flow rates for industrial flares, indicate that the VOCs associated with these industrial emissions can have significant temporal variability. To characterize the effect of this variability in emissions on ozone formation in Houston, data were collected on the temporal variability of industrial emissions or emission surrogates (e.g., mass flow rates to flares). The observed emissions variability was then used to construct regionwide emission inventories with variable industrial emissions, and the impacts of the variability on ozone formation were examined for two types of meteorological conditions, both of which lead to high ozone concentrations in Houston. The air quality simulations indicate that variability in industrial emissions has the potential to cause increases and decreases of 10–52 ppb (13–316%), or more, in ozone concentration. The largest of these differences are restricted to regions of 10–20 km², but the variability also has the potential to increase regionwide maxima in ozone concentrations by up to 12 ppb.     

A passive sampler for ambient gaseous oxidized mercury concentrations

This paper reports on the development of a passive sampler for estimating gaseous oxidized mercury concentrations. Atmospheric gaseous oxidized mercury concentrations calculated from passive sampler data were correlated with those obtained using an automated analyzer (r² = 0.71, p < 0.01, n = 110 for one-week deployments; r² = 0.89, p < 0.01, n = 22 for two-week deployments). Sampler uptake was not significantly affected by changes in temperature, humidity, or ozone concentration, but it was slightly dependent on wind speed. As such, an equation for correcting data due to this factor was developed based on wind tunnel and field data. The detection limit for a two-week sampler deployment was ～5 pg m^?3. Field data collected in Nevada and the southeastern United States showed these samplers are useful for investigating spatial and temporal variability in gaseous oxidized mercury concentrations.     

Mobile passive samplers: concept for a novel mode of exposure

Integrative passive sampling with devices such as semipermeable membrane devices generally relies on rigs for month-long static exposures in water. We evaluate here whether mobile exposures of passive samplers can provide reliable estimates of dissolved contaminant concentrations. Mobile exposures were obtained by towing samplers fastened to the end of a benthic trawl net. Significant and reproducible absorption of polycyclic aromatic hydrocarbons during 5 h-long deployments was made possible by high sampling rates resulting from high water turbulences during towing at 1.2-1.5 knots. Sampling rates (72-215 L d⁻¹) estimated from the dissipation of performance reference compounds were supported by in situ calibration with samplers exposed for a 30 days in the vicinity of the test site. Higher fluoranthene and pyrene absorption in samplers exposed to the trawling-induced sediment plume could be attributed to desorption from re-suspended sediments. This mode of exposure has the potential to be used in monitoring programmes.     

Establishing ozone flux–response relationships for winter wheat: Analysis of uncertainties based on data for UK and Polish genotypes

The work outlined in this paper had three objectives. The first was to explore the effects of ozone pollution on grain yield and quality of commercially-grown winter wheat cultivars. The second was to derive a stomatal ozone flux model for winter wheat and compare with those already developed for spring wheat. The third was to evaluate exposure- versus flux–response approaches from a risk assessment perspective, and explore the implications of genetic variation in modelled ozone flux.Fifteen winter wheat cultivars were grown in open-top chambers where they were exposed to four levels of ozone. During fumigation, stomatal conductance measurements were made over the lifespan of the flag leaf across a range of environmental conditions. Although significant intra-specific variation in ‘ozone sensitivity’ (in terms of impacts on yield) was identified, yield was inversely related (R² = 0.63, P < 0.001) to the accumulated hourly averaged ozone exposure above 40 ppb during daylight hours (AOT40) across the dataset. The adverse effect of ozone on yield was principally due to a decline in seed weight. Algorithms defining the influence of environmental variables on stomatal uptake were subtly different from those currently in use, based on data for spring wheat, to map ozone impacts on pan-European cereal yield. Considerable intra-specific variation in phenological effects was identified. This meant that an ‘average behaviour’ had to be derived which reduced the predictive capability of the derived stomatal flux model (R² = 0.49, P < 0.001, 15 cultivars included). Indeed, given the intra-specific variability encountered, the flux model that was derived from the full dataset was no better in predicting O₃ impacts on wheat yield than was the AOT40 index. The study highlights the need to use ozone risk assessment tools appropriate to specific vegetation types when modelling and mapping ozone impacts at the regional level.     

Estimates of ozone AOT40 from passive sampling in forest sites in South-Western Europe

Weekly-fortnightly ozone (O3) concentrations measured by passive sampling at 81 forest monitoring plots in France, Italy, Spain and Switzerland over the period 2000-2002 were used to estimate the cumulative exposure index AOT40. The estimation method is based on a deterministic model which describes the O3 daily profile as a function of relative altitude (the difference between the altitude of the site and the lowest altitude within a 5 km radius) and the time of the day. Estimated AOT40 values (AOT40(e)) were evaluated against co-located automatic measurement stations and with 14 independent automatic stations located throughout Italy whose weekly mean O3 values were used to simulate passive samplers. AOT40 can be predicted by modelling passive sampling data (R2: 0.90; P<0.0001, SE of estimates: 3271 ppb h), although considerable deviations can occur for individual sites. Estimated AOT40 shows a distinct, significant latitudinal and altitudinal gradient. Taking the 3-year average as a whole, exceedance of critical level of 5000 ppb h occurs at 77-100% of the monitored sites, respectively.     

Estimated tropospheric ozone levels on the southeast Spanish Mediterranean coast

The objective of this study is to estimate the spatial variability of tropospheric ozone in an area using a simple model. The area in this case was applied in the western Mediterranean basin. The study period was from May to September in 2003 and 2004.A multiple linear regression between ozone concentrations, altitude and distance to the precursor sources in a fluvial basin can be used to estimate ozone values at other sites during the warmer seasons. The correlation coefficients obtained with 2-week ozone values measured at five points with a passive sampling technique were high enough to apply the model (0.77<r<0.99).To verify the model, ozone concentrations were measured with passive samplers and continuous analyzers at some selected sites, and the values were compared with the estimated concentration. The results of the validations were satisfactory, in 80% of the measurements the estimated levels differ from measured less than 20%, which is included in the bound error for the type of sampler used in this study.     

Neural modelling of the spatial distribution of air pollutants

In this paper, a new method to calculate the average spatial distribution of air pollutants based on diffusive sampling measurements and artificial neural networks evaluation is presented. Most established methods like interpolation algorithms are inflexible or limited in considering important distribution parameters such as emission sources or land use. Of special interest are air quality measurements since they provide a direct view on the actual pollutant level. With diffusive samplers, the average concentration of many gaseous species over a large area can be determined simultaneously. During a project in Cyprus, NO₂ diffusive samplers were exposed at 270 sites in six month-long campaigns throughout one year providing the database for the model described in this paper. A multilayer perceptron was trained with the NO₂ measurement data and distribution parameters like population density and meteorological parameters using a 1 × 1 km grid covering Cyprus. The best fit could be achieved with an emissions inventory including previously simulated concentration plumes and population density data as input nodes for the neural network, resulting in realistic maps of the annual average distribution of NO₂ in Cyprus.     

Performance evaluation of a tailor-made passive sampler for monitoring of tropospheric ozone

Introduction

This study presents the performance evaluation of a tailor-made passive sampler developed for the monitoring of tropospheric ozone.

Methods

The performance of the passive sampler was tested in the field conditions in terms of accuracy, precision, blank values, detection limit, effects of some parameters such as sampling site characteristics and sampling period on the field blanks, self-consistency, experimental and theoretical uptake rates, shelf life and comparison with commercial passive samplers.

Results

There was an agreement (R ²?=?0.84) between the responses of passive sampler and the continuous automatic analyser. The accuracy of the sampler, expressed as percent relative error, was obtained lower than 15%. Method precision in terms of coefficient of variance for three simultaneously applied passive samplers was 12%. Sampler detection limit was 2.42???g?m^?3 for an exposure period of 1?week, and the sampler can be stored safely for a period of up to 8?weeks before exposure. Satisfactory self-consistency results showed that extended periods gave the same integrated response as a series of short-term samplers run side by side. The uptake rate of ozone was found to be 10.21?mL?min^?1 in a very good agreement with the theoretical uptake rate (10.32?mL?min^?1). The results of the comparison study conducted against a commercially available diffusion tube (Gradko diffusion tube) showed a good linear relationship (R ²?=?0.93) between two passive samplers.

Conclusions

The sampler seems suitable to be used in large-scale measurements of ozone where no data are available or the number of existing automated monitors is not sufficient.     

Improving ozone modeling in complex terrain at a fine grid resolution: Part I – examination of analysis nudging and all PBL schemes associated with LSMs in meteorological model

Meteorological variables such as temperature, wind speed, wind directions, and Planetary Boundary Layer (PBL) heights have critical implications for air quality simulations. Sensitivity simulations with five different PBL schemes associated with three different Land Surface Models (LSMs) were conducted to examine the impact of meteorological variables on the predicted ozone concentrations using the Community Multiscale Air Quality (CMAQ) version 4.5 with local perspective. Additionally, the nudging analysis for winds was adopted with three different coefficients to improve the wind fields in the complex terrain at 4-km grid resolution. The simulations focus on complex terrain having valley and mountain areas at 4-km grid resolution. The ETA M–Y (Mellor–Yamada) and G–S (Gayno–Seaman) PBL schemes are identified as favorite options and promote O₃ formation causing the higher temperature, slower winds, and lower mixing height among sensitivity simulations in the area of study. It is found that PX (Pleim–Xiu) simulation does not always give optimal meteorological model performance. We also note that the PBL scheme plays a more important role in predicting daily maximum 8-h O₃ than land surface models. The results of nudging analysis for winds with three different increased coefficients' values (2.5, 4.5, and 6.0 × 10^?4 s^?1) over seven sensitivity simulations show that the meteorological model performance was enhanced due to improved wind fields, indicating the FDDA nudging analysis can improve model performance considerably at 4-km grid resolution. Specifically, the sensitivity simulations with the coefficient value (6.0 × 10^?4) yielded more substantial improvements than with the other values (2.5 and 4.5 × 10^?4). Hence, choosing the nudging coefficient of 6.0 × 10^?4 s^?1 for winds in MM5 may be the best choice to improve wind fields as an input, as well as, better model performance of CMAQ in the complex terrain area. As a result, a finer grid resolution is necessary to evaluate and access of CMAQ results for giving a detailed representation of meteorological and chemical processes in the regulatory modeling. A recommendation of optimal scheme options for simulating meteorological variables in the complex terrain area is made.     

Evaluation of near surface ozone in air quality simulations forced by a regional climate model over Europe for the period 1991–2000

This study aims to evaluate near surface ozone simulated with the modelling system RegCM3/CAMx against ozone measurements from the EMEP database for the recent decade 1991–2000. The RegCM3/CAMx simulations were performed on a 50 km × 50 km grid over Europe driven either by ERA-40 reanalysis (hereafter referred as ERA simulation) or the global circulation model (GCM) ECHAM5 (hereafter referred as ECHAM simulation). A set of statistical metrics is used for the model evaluation, including temporal correlation coefficient, the ratio of the standard deviations and the bias of simulated versus observed values. Overall, a good agreement is found for both ERA and ECHAM simulations at the majority of the selected EMEP stations in all metrics throughout the year based either on monthly or daily ozone values. Based on these results, it is assessed that the modelling system RegCM3/CAMx is suitable to be used for present and future regional climate-air quality simulations with emphasis on near surface ozone. The ERA simulations reproduce more accurately the observed ozone values in comparison to ECHAM simulations because the meteorology of the ERA experiment is closer to real atmospheric conditions than the GCM based experiment. On a seasonal basis, both ERA and ECHAM simulations exhibit a seasonally dependent bias, with winter and spring ozone values being generally under-estimated by the model and summer and autumn values being slightly overestimated. This seasonally dependent bias is also evident from median and peak midday ozone values. However, the highest observed midday ozone peaks in summer, with values higher than 80 ppbv, could not be captured either by ERA or ECHAM simulations. An analysis of day-time and night-time ERA and ECHAM modelled ozone values shows that CAMx performs better during the day-time.     

Nitrogen mediates above-ground effects of ozone but not below-ground effects in a rhizomatous sedge

Ozone and atmospheric nitrogen are co-occurring pollutants with adverse effects on natural grassland vegetation. Plants of the rhizomatous sedge Carex arenaria were exposed to four ozone regimes representing increasing background concentrations (background-peak): 10-30, 35-55, 60-80 and 85-105 ppb ozone at two nitrogen levels: 12 and 100 kg N ha⁻¹ yr⁻¹. Ozone increased the number and proportion of senesced leaves, but not overall leaf number. There was a clear nitrogen × ozone interaction with high nitrogen reducing proportional senescence in each treatment and increasing the ozone dose (AOT40) at which enhanced senescence occurred. Ozone reduced total biomass due to significant effects on root biomass. There were no interactive effects on shoot:root ratio. Rhizome tissue N content was increased by both nitrogen and ozone. Results suggest that nitrogen mediates above-ground impacts of ozone but not impacts on below-ground resource translocation. This may lead to complex interactive effects between the two pollutants on natural vegetation.     

Nitrogen concentrations in mosses indicate the spatial distribution of atmospheric nitrogen deposition in Europe

In 2005/6, nearly 3000 moss samples from (semi-)natural location across 16 European countries were collected for nitrogen analysis. The lowest total nitrogen concentrations in mosses (<0.8%) were observed in northern Finland and northern UK. The highest concentrations (≥1.6%) were found in parts of Belgium, France, Germany, Slovakia, Slovenia and Bulgaria. The asymptotic relationship between the nitrogen concentrations in mosses and EMEP modelled nitrogen deposition (averaged per 50 km × 50 km grid) across Europe showed less scatter when there were at least five moss sampling sites per grid. Factors potentially contributing to the scatter are discussed. In Switzerland, a strong (r² = 0.91) linear relationship was found between the total nitrogen concentration in mosses and measured site-specific bulk nitrogen deposition rates. The total nitrogen concentrations in mosses complement deposition measurements, helping to identify areas in Europe at risk from high nitrogen deposition at a high spatial resolution.     

Degradation kinetics of anthracene by ozone on mineral oxides

To further understand the role of substrates on the heterogeneous reactions of polycyclic aromatic hydrocarbons, the reactions of ozone with anthracene adsorbed on different mineral oxides (SiO₂, α-Al₂O₃ and α-Fe₂O₃) and on Teflon disc were investigated in dark at 20 °C. No reaction between ozone and anthracene on Teflon disc was observed when the ozone concentration was ～1.18 × 10¹⁴ molecules cm^?3. The reactions on mineral oxides exhibited pseudo-first-order kinetics for anthracene loss, and the pseudo-first-order rate constant (k_1,obs) displayed a Langmuir–Hinshelwood dependence on the gas-phase ozone concentration. The adsorption equilibrium constants for ozone (K_O3) on SiO₂-1, SiO₂-2, α-Al₂O₃ and α-Fe₂O₃ were (0.81 ± 0.26) × 10^?15 cm³, (2.83 ± 1.17) × 10^?15 cm³, (2.48 ± 0.77) × 10^?15 cm³ and (1.66 ± 0.45) × 10^?15 cm³, respectively; and the maximum pseudo-first-order rate constant (k_1,max) on these oxides were (0.385 ± 0.058) s^?1, (0.101 ± 0.0138) s^?1, (0.0676 ± 0.0086) s^?1 and (0.0457 ± 0.004) s^?1, respectively. Anthraquinone was identified as the main surface product of anthracene reacted with ozone. Comparison with previous research and the results obtained in this study suggest that the reactivity of anthracene with ozone and the lifetimes of anthracene adsorbed on mineral dust in the atmosphere are determined by the nature of the substrate.     

Long-term atmospheric bulk deposition of polycyclic aromatic hydrocarbons (PAHs) in rural areas of Southern Germany

A novel passive sampling technique using a funnel–adsorber–cartridge device was adopted and validated in the field during a long-term monitoring program on the atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in three rural regions of southern Germany. Apart from seasonal variations, fairly stable annual deposition rates around 200 μg m⁻² yr⁻¹ for the sum of PAHs were obtained. The time-integrating passive samplers showed that spatial variability due to topography was negligible and differences between open-field and forest deposition were within a factor of 2. Based on correlations with ambient temperature, advection was identified as the most important factor that controls the atmospheric deposition of PAHs. Gas-adsorption contributes significantly to the deposition of the semivolatile compounds in forests, but particle deposition seems to be the major pathway for all PAHs.     

Detecting plant effects is necessary to give biological significance to ambient ozone monitoring data and predictive ozone standards

The use of mechanical monitors and passive samplers has made it possible to assess concentrations of ozone over wide areas and to develop air quality standards, like AOT40 and SUM60. Monitored ozone data and AOT40 and SUM60 are also used to predict ozone injury on local and regional scales. The data and the standards do not include or account for environmental and biological variables that affect ozone uptake and plant injury. Ground proofing via vegetation surveys must be done to verify and validate plant injury predictions. If this is not done, then the standards have no biological significance and are only exercises in air quality assessment.     

Verification of diffusive and pumped samplers for volatile organic compounds using a controlled atmosphere test facility

There is a requirement to verify the performance of sorbent-based passive or active samplers and to extend their use, where possible, to monitor volatile organic compounds (VOCs) that are known to be photochemical ozone pre-cursors or are relevant to the activities of the petrochemical industry. We report measurements of the 14-day diffusive uptake rates for the VOCs: i-butane (2-methyl propane), n-butane, i-pentane (2-methyl butane), n-pentane, n-hexane, benzene, toluene, and m-xylene (at environmental level concentrations) for industry standard axial samplers (Perkin–Elmer-type samplers) containing the sorbents Carbopack-X, -Z, -B or Tenax-TA. We also present data on back-diffusion, blank levels, and storage for the above sorbents, and describe the simultaneous use of the sorbent Carbopack-X for pumped sampling of certain VOCs. The results were obtained by dosing samplers in a controlled atmosphere test facility (CATFAC) operating under well-defined conditions of concentration, nominal temperature of 20 °C, wind speed of 0.5 m s^?1, and relative humidities of 0% and 80%. Field measurements were also obtained to provide supplementary data to support the laboratory study. Results are compared to existing published data, where these are available.     

Agricultural ammonia emissions inventory and spatial distribution in the North China Plain

An agricultural ammonia (NH₃) emission inventory in the North China Plain (NCP) on a prefecture level for the year 2004, and a 5 × 5 km² resolution spatial distribution map, has been calculated for the first time. The census database from China's statistics datasets, and emission factors re-calculated by the RAINS model supported total emissions of 3071 kt NH₃-N yr⁻¹ for the NCP, accounting for 27% of the total emissions in China. NH₃ emission from mineral fertilizer application contributed 1620 kt NH₃-N yr⁻¹, 54% of the total emission, while livestock emissions accounted for the remaining 46% of the total emissions, including 7%, 27%, 7% and 5% from cattle, pigs, sheep and goats, and poultry, respectively. A high-resolution spatial NH₃ emissions map was developed based on 1 × 1 km land use database and aggregated to a 5 × 5 km grid resolution. The highest emission density value was 198 kg N ha⁻¹ yr⁻¹.     

Aerosol number size distributions within the exhaust plume of a diesel and a gasoline passenger car under on-road conditions and determination of emission factors

A new setup has been developed and built to measure number size distributions of exhaust particles and thermodynamic parameters under real traffic conditions. Measurements have been performed using a diesel and a gasoline passenger car driving with different speeds and engine conditions. Significant number of nucleation mode particles was found only during high load conditions, i.e. high car and engine speeds behind the diesel car. The number concentration of soot mode particles varied within a factor of two for different engine conditions while the concentration of nucleation mode particles varied up to two orders of magnitude. The results show that roadside measurements are still quite different from those behind the tailpipe. Beside dilution transformation processes within the first meter behind the tailpipe also play an important role, such as nucleation and growth. Emission factors were calculated and compared with those obtained by other studies. Emission factors for particles larger than 25 nm (primary emissions) varied within 1.1 × 10¹⁴ km^?1 and 2.7 × 10¹⁴ km^?1 for the diesel car and between 0.6 × 10¹² km^?1 and 3.5 × 10¹² km^?1 for the gasoline car. The advantage of these measurements is the exhaust dilution under atmospheric conditions and the size-resolved measurement technique to divide into primary emitted and secondary formed particles.