Factors influencing the ground level distribution of ozone in Europe

Ozone is a widely distributed pollutant in the atmospheric boundary layer over north west Europe. Three main sources have been identified: the stratosphere, the free troposphere and boundary layer photochemical production. The pattern of ground level ozone concentrations resulting from these three sources cannot be accurately specified. Ozone shows significant variations in space and time but because of the high cost of continuous monitoring equipment, spatial variations on a national and international basis have not been studied in detail. Variations in ozone concentrations at individual monitoring sites have been given a great deal of attention and experience gained from United Kingdom monitoring sites is described in some detail. The averaging time statistical model of Larsen is employed to relate the exposure levels measured over different averaging periods. Diurnal variations have a major influence on exposure levels at sites nominally exposed to the same regional ozone distribution. The physical and chemical mechanisms which give rise to diurnal variations are detailed so that sites can be screened for different diurnal behaviour characteristics.     

Diurnal variability of total ozone column over Madrid (Spain)

In recent years, research on ozone variability has mainly focused on the analysis of its trend. Additionally some studies have analyzed the annual, seasonal and day-to-day ozone variations. However, intra-diurnal total ozone variations are notably less explored. Thus, the main objective of this paper is to analyze the diurnal variability of total ozone column (TOC) as recorded by a Brewer spectrophotometer in Madrid (Spain). The results show that about 90% of days present non-negligible diurnal variability, indicating that, in general, it should not be assumed that TOC remains constant throughout a particular day in urban areas. In addition, this variability has a notable seasonal behavior which should be considered (the spring and summer months show higher diurnal TOC variations than autumn and winter months). This pattern is likely caused by the diurnal photochemical processes in the lower troposphere related to the formation of tropospheric ozone near the earth’s surface at populated urban locations. Thus, these diurnal fluctuations in tropospheric ozone could explain part of diurnal TOC variations (between 20% and 70% depending on the mixing layer height).     

Secondary ozone maxima in a very stable nocturnal boundary layer: observations from the Lower Fraser Valley,BC

The relationship between near-surface ozone concentration and the structure of the nocturnal boundary layer was investigated during a field campaign conducted in 1998 in the Lower Fraser Valley (LFV), British Columbia Canada. Despite the spatial and temporal variation in frequency and morphology, secondary nocturnal ozone maxima were shown to be an important feature of the diurnal ozone cycle throughout the LFV, and localised increases in ozone occasionally exceeded more than half the previous day's maximum concentration.Turbulence in the nocturnal boundary layer was shown to be weak and intermittent. Vertical profiles of Richardson number and ozone concentration indicated that the temporary turbulent coupling of the residual layer to the surface layer facilitated the transport of ozone stored aloft to the surface. Despite the overall complexity of the system, results show that seven out of the 19 ozone spikes observed at the Aldergrove site coincided with turbulence associated with the development of the down-valley wind system. A further nine spikes occurred during periods when a low-level jet was identified aloft. Significantly, ozone concentrations were shown to be highly variable in the residual layer and played an important role in determining the morphology of secondary ozone maxima at the surface. Largest increases in surface ozone concentration occurred when turbulence coincided with periods when ozone concentrations in excess of 80 ppb were observed aloft.     

Estimation of the Natural Background of Ozone Present at Surface Rural Locations

The natural background in the ozone concentration at rural locations in the United States and western Europe has been estimated by use of several approaches. The approaches utilized include the following: (1) historical trends in ozone concentration measurements, (2) recent ozone measurements at remote sites, (3) use of tracers of air originating in the stratosphere or upper troposphere and (4) results from applications of tropospheric photochemical models. While each of these approaches has its own limitations it appears that the natural background of ozone during the warmer months of the year is in the range of 10 to 20 ppb. Most of the ozone originating in the lower stratosphere or upper troposphere is lost by chemical or physical removal processes as well as undergoing dilution by air in the lower troposphere before reaching ground level rural locations. Lower tropospheric photochemical processes, those below 5 km, are likely to account for most of the ozone measured at rural locations during the warmer months of the year.

A key aspect to improved quantitation of the contributions from lower tropospheric photochemical processes to ozone concentrations continues to be more extensive atmospheric measurements of the distribution of reactive species of nitrogen. The emission densities of anthropogenic sources of NO_x are known to be highly variable over populated areas of continents as well as between continental areas and the oceans. The emission densities of biogenic sources of NO_x are small, likely to be highly variable, but poorly quantitated. These wide variations indicate the need for use of three dimensional tropospheric photochemical models over large continental regions.

Available results do indicate higher efficiencies for ozone formation at lower NO_x concentrations, especially below 1 ppb.     

The Characterization of Ozone and Sulfur Dioxide Air Quality Data for Assessing Possible Vegetation Effects

Since the 1960s, much effort has been devoted to collecting and formatting air quality data. This paper discusses 1) the availability of air quality data for assessing potential biological impacts associated with ozone and sulfur dioxide ambient exposures, 2) examples of how air quality data can be characterized for assessing vegetation effects, and 3) the limitations associated with some exposure parameters used for developing relevant vegetation doseresponse yield reduction models. Data are presented showing that some ozone monitoring sites not continuously affected by local urban sources experience consecutive hourly ozone exposures ≥0.10 ppm in the late evening and early morning hours. These sites experience their maximum ozone concentrations either in the spring or summer months. Sites influenced by local rural sources experience their maximum ozone concentrations during the summer months. It is suggested that further research be performed to identify whether the sensitivity of a target organism at the time of exposure, as well as the pollutant concentration and chemical form that enters into the target organism, is as important in defining effects as air pollutant exposure alone.     

Assessing the risk of foliar injury from ozone on vegetation in parks in the U.S. National Park Service's Vital Signs Network

The risk of ozone injury to plants was assessed in support of the National Park Service's Vital Signs Monitoring Network program. The assessment examined bioindicator species, evaluated levels of ozone exposure, and investigated soil moisture conditions during periods of exposure for a 5-year period in each park. The assessment assigned each park a risk rating of high, moderate, or low. For the 244 parks for which assessments were conducted, the risk of foliar injury was high in 65 parks, moderate in 46 parks, and low in 131 parks. Among the well-known parks with a high risk of ozone injury are Gettysburg, Valley Forge, Delaware Water Gap, Cape Cod, Fire Island, Antietam, Harpers Ferry, Manassas, Wolf Trap Farm Park, Mammoth Cave, Shiloh, Sleeping Bear Dunes, Great Smoky Mountains, Joshua Tree, Sequoia and Kings Canyon, and Yosemite.     

Dicarboxylic acid concentration trends and sampling artifacts

Dicarboxylic acids associated with airborne particulate matter were measured during a summer period in Philadelphia that included multiple air pollution episodes. Samples were collected for two 10 h periods each day using a high-volume sampler with two quartz fiber filters in series, and analyzed by gas chromatography mass spectrometry (GCMS) with diazomethane derivatization. Among the dicarboxylic acids investigated, phthalic acid and adipic acid exhibited the greatest diurnal variations and the strongest linear relationship with maximum daily ozone concentration. Dicarboxylic acids and ozone concentration exhibited a poor linear relationship with organic to elemental carbon ratio. All species investigated were affected by significant sampling artifact errors at low concentrations, but sampling errors were negligible at high concentrations observed during ozone episodes.     

Equatorial measurements of surface ozone

Results from surface ozone measurements at Penang (5.5°N, 100°E) over several years are presented. The study indicates the ozone concentrations undergoing significant diurnal and seasonal variations. The peak concentrations are observed at around mid-day (up to 35 nb) but the O₃ concentration generally drops to zero level in the early evening and remains unchanged until midorning. Monthly-averaged daily 1-h average concentrations are generally small (4–13 nb) and decrease continually from the early part of the year to the end. Frequently, varying local weather conditions seem to influence the O₃ concentrations.     

泰山顶与济南市大气臭氧浓度变化规律研究

利用2003年7月至9月在泰山顶和济南市3个月的臭氧（O3）自动连续监测数据,对两地O3浓度的频率分布、日变化和日际变化等特征进行对照分析。实验结果表明,泰山顶O3小时平均浓度频率分布比较集中,济南市O3小时平均浓度频率分布比较分散。泰山顶各月O3小时平均浓度的平均值和日均值均高于济南市;泰山顶O3小时平均浓度的最大值低于济南市,而O3小时平均浓度的最小值要高于济南市。泰山顶O3小时平均浓度日变化规律与济南市O3小时平均浓度日变化规律有很大差别,泰山顶O3小时平均浓度日变化很平缓,最大值与最小值相差不大,济南市O3小时平均浓度一般在中午和午后浓度较高,早晨和夜晚较低。     

Empirical Evaluation of Ambient Ozone Interpolation Procedures to Support Exposure Models

ABSTRACT

An intercomparison study has been performed with six empirical ozone interpolation procedures to predict hourly concentrations in ambient air between monitoring stations. The objective of the study is to use monitoring network data to empirically identify an improved procedure to estimate ozone concentrations at subject exposure points. Four of the procedures in the study are currently used in human exposure models (nearest monitors daily mean and maximum, regression estimate used in the U.S. Environmental Protection Agency's (EPA) pNEM, and inverse distance weighting), and two are being evaluated for this purpose (kriging in space and kriging in space and time). The study focused on spatial estimation during June 1-June 5, 1996, with relatively high observed ozone levels over Houston, Texas. The study evaluated these procedures at three types of locations with monitors of varying proximity. Results from the empirical evaluation indicate that kriging in space and time provides excellent estimates of ozone concentrations within a monitoring network, while the more often used techniques failed to capture observed pollutant concentrations. Improved estimation of pollutant concentrations within the region, and thus at subject locations, should result in improved exposure modeling.     

Ambient ozone in forests of the Central and Eastern European mountains

Ambient ozone (O(3)) concentrations in the forested areas of the Central and Eastern European (CEE) mountains measured on passive sampler networks and in several locations equipped with active monitors are reviewed. Some areas of the Carpathian Mountains, especially in Romania and parts of Poland, as well as the Sumava and Brdy Mountains in the Czech Republic are characterized by low European background concentrations of the pollutant (summer season means approximately 30 ppb). Other parts of the Carpathians, especially the western part of the range (Slovakia, the Czech Republic and Poland), some of the Eastern (Ukraine) and Southern (Romania) Carpathians and the Jizerske Mountains have high O(3) levels with peak values >100 ppb and seasonal means approximately 50 ppb. Large portions of the CEE mountain forests experience O(3) exposures that are above levels recommended for protection of forest and natural vegetation. Continuation of monitoring efforts with a combination of active monitors and passive samplers is needed for developing risk assessment scenarios for forests and other natural areas of the CEE Region.     

Some insights into short-term variability of total gaseous mercury in urban air

The concentrations of total gaseous mercury (Hg) were determined at hourly intervals along with relevant environmental parameters that include both meteorological plus criteria pollutant data during two field campaigns (September 1997 and May/June 1998). The mean concentrations of Hg for the two study periods were computed as 3.94 and 3.43 ng m⁻³, respectively. By separating the data into daytime and nighttime periods, we further analyzed diurnal variation patterns for both seasons. Using our Hg data sets, we were able to recognize two contrasting diurnal variation patterns of Hg between two different seasons that can be characterized as: (1) the occurrences of peak Hg concentration during daytime (fall) and (2) slight reductions in daytime Hg concentration relative to nighttime (summer). To study the systematic differences in diurnal patterns between two different seasons, we analyzed Hg data in terms of different statistical approaches such as correlation (and linear regression) and factor analysis. Results of these analyses consistently indicated that different mechanisms were responsible for controlling the daytime distribution patterns of Hg. When the relationship between Hg and concurrently determined O₃ is considered, its reaction with ozone is unlikely to limit Hg levels as the dominant sink mechanism (within the ranges of ozone concentrations found during this study, regardless of season). It is on the other hand suspected that the variation of boundary layer conditions between day/night periods may have been important in introducing the relative reduction in daytime Hg levels during summer. To further provide a general account of short-term variations in Hg distribution data, it is desirable to describe other unknown sink mechanisms.     

Ozone measurements in South Carolina using passive samplers

Passive samplers with two different collection substrates were used to obtain an average ozone concentration for 1 month during the summer of 2002 for each South Carolina county. One sampler contained a filter coated with indigo carmine, whose color fades when exposed to ozone. The fading was measured by reflectance spectroscopy. The other sampler contained filters that were coated with nitrite, which is oxidized to nitrate when exposed to ozone. The nitrate was measured by ion chromatography. Calibration curves were developed for the two methods by comparing color fading from indigo carmine and nitrate ion concentration from the nitrite filter with ambient ozone concentration measured by a co-located reference continuous UV ozone analyzer. These curves were used to calculate integrated ozone concentrations for samplers distributed across South Carolina. Using the indigo carmine method, the average ozone concentrations ranged from 21 to 64 ppb (average = 46 +/- 7.9 ppb, n = 58) across the 46 counties in the state during one summer month of 2002. Concentrations for the same time period from the nitrite-coated filters ranged from 23 to 62 ppb (average = 41 +/- 8.1 ppb, n = 58). Also for the same time period, the 23 continuous UV photometric ozone monitors operated by the South Carolina Department of Health and Environmental Control at sites within 10 miles of some of the passive monitors showed ozone concentrations ranging from 28 to 50 ppb (average = 39 +/- 6.3 ppb, n = 22).     

Climatology of diurnal trends and vertical distribution of ozone in the atmospheric boundary layer in urban North Carolina

Vertical measurements of ozone were made on a 610-m-tall tower located about 15 km southeast of Raleigh, NC, as part of an effort by the state of North Carolina to develop a state implementation plan (SIP) for ozone control in the Raleigh Metropolitan Statistical Area. During summer 1993, 1994, and 1995, ozone was monitored at ground level, 250 m, and 433 m. Boundary layer wind, temperature, and other meteorological variable profiles were determined from balloon soundings. During summer 1996 and 1997, ozone was monitored at ground level, 76 m, 128 m, and 433 m. This paper presents the analysis and discussion of the five-year data. The evolutions of the convective boundary layer during daytime and the stable nocturnal boundary layer (NBL) were found to have marked impacts on ozone concentrations. A strong diurnal pattern, with an afternoon maximum and an early morning minimum, was dominant at ground level, but it was much weaker at elevated levels and insignificant above the NBL at night. Ozone deposition velocities at night during the measurement periods were estimated to range from 0.09 to 0.64 cm/sec. We found evidence of regional transport of ozone and/or its precursors from northwest and north of the site, which may play a role in high ozone events in the Raleigh-Durham area. Ozone concentrations between the various elevated levels were well correlated, while correlations between the ground and upper levels were much weaker. However, a strong correlation was found between the nighttime and early morning ozone concentrations (CR) in the residual layer above the NBL and the maximum ground level concentration (Co max) the following afternoon. Based on this correlation, the latter may be predicted by an observational model Co max = 27.76e 0.016 CR.     

Evaluating the performance of regional-scale photochemical modeling systems: Part II—ozone predictions

In this paper, the concept of scale analysis is applied to evaluate ozone predictions from two regional-scale air quality models. To this end, seasonal time series of observations and predictions from the RAMS3b/UAM-V and MM5/MAQSIP (SMRAQ) modeling systems for ozone were spectrally decomposed into fluctuations operating on the intra-day, diurnal, synoptic and longer-term time scales. Traditional model evaluation statistics are also presented to illustrate how the scale analysis approach can help improve our understanding of the models’ performance. The results indicate that UAM-V underestimates the total variance (energy) of the ozone time series when compared with observations, but shows a higher mean value than the observations. On the other hand, MAQSIP is able to better reproduce the average energy and mean concentration of the observations. However, both modeling systems do not capture the amount of variability present on the intra-day time scale primarily due to the grid resolution used in the models. For both modeling systems, the correlations between the predictions and observations are insignificant for the intra-day component, high for the diurnal component because of the inherent diurnal cycle but low for the amplitude of the diurnal component, and highest for the synoptic and baseline components. This better model performance on longer time scales suggests that current regional-scale models are most skillful in characterizing average patterns over extended periods, rather than in predicting concentrations at specific locations, during 1–2 day episodic events. In addition, we discuss the implications of these results to using the model-predicted daily maximum ozone concentrations in the regulatory framework in light of the uncertainties introduced by the models’ poor performance on the intra-day and diurnal time scales.     

Surface ozone measurements in the southwest of the Iberian Peninsula (Huelva,Spain)

Introduction  

Photochemical ozone pollution of the lower troposphere (LT) is a very complex process involving meteorological, topographic emissions and chemical parameters. Ozone is considered the most important air pollutant in rural, suburban and industrial areas of many sites in the world since it strongly affects human health, vegetation and forest ecosystems, and its increase during the last decades has been significant. In addition, ozone is a greenhouse gas that contributes to climate change. For these reasons, it is necessary to carry out investigations that determine the behaviour of ozone at different locations. The aim of this work is to understand the levels and temporal variations of surface ozone in an industrial-urban region of the Southwest Iberian Peninsula.     

Carbon Monoxide Exposures to Los Angeles Area Commuters

Carbon monoxide exposures to commuters were simulated in a 5-day study in Los Angeles County. Exposures were determined by measuring CO in three vehicles as they traveled typical commuter routes. The data collected during this study include measurements of vehicle speed and CO measurements in the interior and exterior of the three vehicles during the morning and evening peak traffic periods. In addition, hourly averaged CO measurements were taken from eight south coastal Air Quality Management District fixed-site monitoring stations and six California Department of Transportation vans in the proximity of the commuter routes. These data were used to investigate the relationship of CO exposures to meteorological parameters, fixed-site monitors, and traffic conditions.

The average ratio of interior CO concentrations to exterior CO concentrations was 0.92. Concentrations inside and outside the vehicles remained about the same even when the vehicles were driven with vents closed and windows up. Smoking was not permitted in the vehicles during the study. The average ratio of the hour average CO concentrations in the vehicles to fixed-site measurements was 3.9. However, this ratio decreases with increasing ambient CO levels. Although CO levels in the vehicles frequently exceeded 40 ppm and sometimes exceeded 60 ppm, the hour average CO concentrations did not exceed 35 ppm. Slow moving congested traffic is associated with higher CO levels in the vehicles than a high volume of traffic moving at a steady speed.     

Determining temporal and spatial variations in ozone air quality

Unless the change in emissions is substantial, the resulting improvement in ozone air quality can be easily masked by the meteorological variability. Therefore, the meteorological and chemical signals must be separated in examining ozone trends. In this paper, we discuss the use of the Kolmogorov-Zurbenko filter in evaluating the temporal and spatial variations in ozone air quality utilizing ozone concentration data from several monitoring locations in the northeastern United States. The results indicate a downward trend in the ozone concentrations during the period 1983-1992 at most locations in the northeastern United States. The results also reveal that ozone is a regional-scale problem in the Northeast.     

Atmospheric mercury monitoring survey in Beijing,China

With the aid of one industrial, two urban, two suburban, and two rural sampling locations, diurnal patterns of total gaseous mercury (TGM) were monitored in January, February and September of 1998 in Beijing, China. Monitoring was conducted in six (two urban, two suburban, one rural and the industrial sites) of the seven sampling sites during January and February (winter) and in four (two urban, one rural, and the industrial sites) of the sampling locations during September (summer) of 1998. In the three suburban sampling stations, mean TGM concentrations during the winter sampling period were 8.6, 10.7, and 6.2 ng/m3, respectively. In the two urban sampling locations mean TGM concentrations during winter and summer sampling periods were 24.7, 8.3, 10, and 12.7 ng/m3, respectively. In the suburban-industrial and the two rural sampling locations, mean mercury concentrations ranged from 3.1-5.3 ng/m3 in winter to 4.1-7.7 ng/m3 in summer sampling periods. In the Tiananmen Square (urban), and Shijingshan (suburban) sampling locations the mean TGM concentrations during the summer sampling period were higher than winter concentrations, which may have been caused by evaporation of soil-bound mercury in warm periods. Continuous meteorological data were available at one of the suburban sites, which allowed the observation of mercury concentration variations associated with some weather parameters. It was found that there was a moderate negative correlation between the wind speed and the TGM concentration at this suburban sampling location. It was also found that during the sampling period at the same site, the quantity of TGM transported to or from the sampling site was mainly influenced by the duration and frequency of wind occurrence from certain directions.     

Fatty acids and ultrastructure of ozone-exposed Aleppo pine (Pinus halepensis Mill.) needles

Fifteen or 18-month-old Aleppo pine seedlings were fumigated with different concentrations and doses of ozone over a period of 2-16 days in controlled-environmental growth chambers. The total fatty acid content and ultrastructure of the current year needles were subsequently analysed. In acute, high concentration exposures, significant reductions in the levels of linolenic acid were detected. Increases in myristic or palmitic acid were common in needles exposed to lower concentrations of ozone. Ultrastructural studies revealed reductions in chloroplast size and a darkening of stroma at low ozone exposures while at high concentrations disruption of the chloroplast membranes was also identified.