Global tropospheric ozone dynamics

An overview of the tropospheric ozone changes is presented focussing mainly on the tropospheric ozone precursors. The complexity of the problem is shown through the consideration of a great number of relevant substances, like nitrogen compounds, volatile organic compounds, peroxyacetyl nitrate, hydroxyl radical, carbon monoxide, alkyl nitrates. The up-to-date knowledge on the relevant numerical modelling is presented in Part II.     

Global tropospheric ozone dynamics

Various causes of tropospheric changes have been considered in Part I in connection with the analysis of observation data. It is clear however, that the principal instrument for understanding numerous and often interacting causes of ozone changes is numerical modelling. A review of the current status of the numerical modelling has been made for the variability of the ozone concentration in the troposphere. Observation data on tropospheric ozone and relevant numerical modelling results show that a necessity exists to get more adequate global observational data.     

Within season and carry-over effects following exposure of grassland species mixtures to increasing background ozone

Few studies have investigated effects of increased background ozone in the absence of episodic peaks, despite a predicted increase throughout the northern hemisphere over the coming decades. In this study Leontodon hispidus was grown with Anthoxanthum odoratum or Dactylis glomerata and exposed in the UK to one of eight background ozone concentrations for 20 weeks in solardomes. Seasonal mean ozone concentrations ranged from 21.4 to 102.5 ppb. Ozone-induced senescence of L. hispidus was enhanced when grown with the more open canopy of A. odoratum compared to the denser growing D. glomerata. There was increased cover with increasing ozone exposure for both A. odoratum and D. glomerata, which resulted in an increase in the grass:Leontodon cover ratio in both community types. Carry-over effects of the ozone exposure were observed, including delayed winter die-back of L. hispidus and acceleration in the progression from flowers to seed-heads in the year following ozone exposure.     

The health benefits of reduced tropospheric ozone in California

Californians are exposed daily to concentrations of ozone (O3) that are among the highest in the United States. Recently, the state adopted a new 8-hr ambient standard of 0.070 ppm, more stringent than the current federal standard. The new standard is based on controlled human studies and on dozens of epidemiologic studies reporting associations between O3 at current ambient levels and a wide range of adverse health outcomes. Clearly, the new O3 standards will require further reductions in the precursor pollutants and additional expenditures for pollution control. Therefore, it is important to quantify the incremental health benefits of moving from current conditions to the new California standard. In this paper, a standard methodology is applied to quantify the health benefits associated with O3 concentration reductions in California. O3 concentration reductions are estimated using ambient monitoring data and a proportional rollback approach in which changes are specific to each air basin, and control strategies may impact concentrations both below and above the standard. Health impacts are based on published epidemiologic studies, including O3-related mortality and morbidity, and economic values are assigned to these outcomes based on willingness-to-pay and cost-of-illness studies. Central estimates of this research indicate that attaining the California 8-hr standard, relative to current concentrations, would result in annual reductions of 630 cases of premature mortality, 4200 respiratory hospital admissions, 660 pediatric emergency room visits for asthma, 4.7 million days of school loss, and 3.1 million minor restricted activity days, with a median estimated economic value of dollar 4.5 billion. Sensitivity analyses indicate that these findings are robust with respect to exposure assessment methods but are influenced by assumptions about the slope of the concentration-response function in threshold models and the magnitude of the O3-mortality relationship. Although uncertainties exist for several components of the methodology, these results indicate that the benefits of reducing O3 to the California standard may be substantial and that further research on the shape of the O3-mortality concentration-response function and economic value of O3-related mortality would best reduce these uncertainties.     

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.     

Perspectives regarding 50 years of research on effects of tropospheric ozone air pollution on US forests

Tropospheric ozone (O(3)) was first determined to be phytotoxic to grapes in southern California in the 1950s. Investigations followed that showed O(3) to be the cause of foliar symptoms on tobacco and eastern white pine. In the 1960s, "X" disease of ponderosa pines within the San Bernardino Mountains was likewise determined to be due to O(3). Nearly 50 years of research have followed. Foliar O(3) symptoms have been verified under controlled chamber conditions. Studies have demonstrated negative growth effects on forest tree seedlings due to season-long O(3) exposures, but due to complex interactions within forest stands, evidence of similar losses within mature tree canopies remains elusive. Investigations on tree growth, O(3) flux, and stand productivity are being conducted along natural O(3) gradients and in open-air exposure systems to better understand O(3) effects on forest ecosystems. Given projected trends in demographics, economic output and climate, O(3) impacts on US forests will continue and are likely to increase.     

Long-term changes in the tropospheric column ozone from the ozone soundings over Europe

The tropospheric column of ozone is analyzed from the measurements of the vertical profile of ozone by balloon-born ozonesondes. The data base includes ∼16,000 ozone profiles collected above six European stations—three of them have begun the ozonesoundings since 1970. We present a trend analysis (with data up to 2005) focusing on detection of the long-term tropospheric ozone variability over the European network. The ozone time series have been examined separately for each station and season (DJF, MAM, JJA, SON) using a flexible trend model. A trend component of the model is taken as a smooth curve without a priori defined shape. A large increase in the European tropospheric ozone since the beginning of the 1970s (net change of ∼10% in summers and ∼30% in winters) and a kind of stabilization in the early 1990s have been corroborated by the study. This pattern comes from the most extensive data set of ozonesoundings over Hohenpeissenberg and Payern. The decadal differences in the trend pattern between these and other European stations are disclosed. The results of a stepwise regression model using various characteristics of the ozone and temperature profiles as explanatory variables for the tropospheric column ozone (TCO₃) variations show that the ozone changes may be reconstructed using the ozone mixing ratio at 500 hPa, the thermal tropopause (TT) height, and the difference between ozonepause and TT heights. It appears that the last two factors induce 20–30% of the net TCO₃ change over Hohenpeissenberg in the 1970–2004 period.     

Difference in ozone uptake in grassland species between open-top chambers and ambient air

Exposure-response data from open-top chamber (OTC) experiments are often directly applied to ambient air (AA) conditions. Because microclimatic conditions are modified and pollutant uptake by plants may differ (i.e. 'chamber effect'), there is concern about the influence of OTCs on these relationships. In addition, AA concentrations are often measured at a height which differs from canopy height and correction for the concentration gradient (i.e. 'gradient effect') is necessary. To quantify the relative contribution of plant characteristics and microclimatic factors to these effects, ozone uptake by horizontal leaves at the top of the canopy was calculated for plants grown in OTCs or AA by using a resistance analogy model. Data from an OTC experiment in 1996/97 for six species typical of productive grasslands were used. Ozone concentration inside OTCs was set equal to the concentration measured at a height of 3 m above ground (C(z(ref))) or at canopy height (C(0)). The gradient effect resulted in a 16-27% lower average C(0) than C(z(ref)), depending on species. The main determinant of the chamber effect was a systematic difference in leaf-to-air vapour pressure deficit between OTCs and AA which affected stomatal resistance and ozone uptake. In case of monocultures both effects were species-specific. In species mixtures the gradient effect differed between mixing ratios, whereas the chamber effect was species-specific. Because of the inter-specific difference in the chamber effect on ozone uptake, it is concluded that ozone effects on species mixtures differ systematically between OTCs and AA. The data underline that extrapolation of ozone flux-response relationships from OTC experiments must be based on canopy-level ozone concentrations, and that these relationships should be applied only to single species under microclimatic conditions similar to those prevailing in the experiment.     

The influence of tropospheric ozone on the air temperature of the city of Toronto,Ontario, Canada

Weekday/weekend variations in tropospheric ozone concentrations were examined to determine whether ground-level greenhouse gases have a significant impact on local climate. The city of Toronto, Canada, was chosen due to a high volume of commuter traffic and frequent exposure to high ozone episodes. Due to day-of-the-week variations in commuter traffic, ozone concentrations were shown to vary significantly between weekdays and weekends. During high ozone episodes weekend air temperatures were significantly higher than those observed on weekdays. As no meteorological phenomenon is known to occur over a 7 day cycle the observed temperature variations were attributed to anthropogenic activity.     

Spatial distribution of tropospheric ozone in western Washington, USA

We quantified the distribution of tropospheric ozone in topographically complex western Washington state, USA (total area approximately 6000 km(2)), using passive ozone samplers along nine river drainages to measure ozone exposure from near sea level to high-elevation mountain sites. Weekly average ozone concentrations were higher with increasing distance from the urban core and at higher elevations, increasing a mean of 1.3 ppbv per 100 m elevation gain for all mountain transects. Weekly average ozone concentrations were generally highest in Cascade Mountains drainages east and southeast of Seattle (maximum=55-67 pbv) and in the Columbia River Gorge east of Portland (maximum=59 ppbv), and lowest in the western Olympic Peninsula (maximum=34 ppbv). Higher ozone concentrations in the Cascade Mountains and Columbia River locations downwind of large cities indicate that significant quantities of ozone and ozone precursors are being transported eastward toward rural wildland areas by prevailing westerly winds. In addition, temporal (week to week) variation in ozone distribution is synchronous within and between all drainages sampled, which indicates that there is regional coherence in air pollution detectable with weekly averages. These data provide insight on large-scale spatial variation of ozone distribution in western Washington, and will help regulatory agencies optimize future monitoring networks and identify locations where human health and natural resources could be at risk.     

Acid mist and ozone effects on the leaf chemistry of two western conifer species

Seedlings of Jeffrey pine (Pinus jeffreyi) and giant sequoia (Sequoiadendron gigantea) were more susceptible to leaf chemical changes following exposure to acid mist (pH 3.4-2.0) or acid mist/ozone combinations, than to ozone alone (0.1-0.2 microl/litre), when plants were exposed to alternating doses of these pollutants for 6-9 weeks. Under acid mist treatment, leaves exhibited higher levels of nitrogen and sulfur, two elements applied in acid mist. In addition, levels of foliar sodium, and, in the case of giant sequia, potassium, as well, increased under acid mist treatment. Iron and manganese were also mobilized, resulting in significant increases in these elements in pine, and decreases in manganese in giant sequoia foliage. The acid treatment also reduced chlorophyll b concentrations in pine, and, to a less significant extent, in giant sequoia. Calcium, magnesium, barium and strontium were differentially accumulated in giant sequoia compared to Jeffrey pine. Under acid mist treatment, all of these elements (except strontium) declined in concentration in giant sequoia, with calcium showing the most significant trend. The more extensive changes in leaf chemistry induced by acid mist are consistent with earlier observations of significant changes in spectral reflectance of these seedlings after 3 weeks of fumigation. Limited foliage samples collected from these two species in 1985 and 1986 in Sequoia/Kings Canyon National Parks in the southern Sierra Nevada do not in themselves indicate any clearcut or severe effects of ozone alone on leaf chemistry of these species, but a mild influence of nitrate-laden acid deposition, possibly in combination with ozone, is consistent with the rise in nitrogen and lignin levels in Jeffrey pine on sites observed to have moderate visible injury symptoms. No firm conclusions about effects of pollutants on leaf chemistry in these field sites is possible without further study.     

Assessment of tropospheric ozone at an industrial site of Chennai megacity

This paper presents the temporal variation in surface-level ozone (O₃) measured at Gummidipoondi near Chennai, Tamilnadu. The site chosen for the present study has high potential for ozone generation sources, such as vehicular traffic and industrial activities. The site is also located near a hazardous waste management facility. The key sources of nitrogen oxides (NO_x), which are considered to be an important precursor of O₃, include hazardous waste incineration, trucks bringing the hazardous wastes, and vehicles plying on the nearby National Highway 16 (NH 16). The measurements clearly showed diurnal variation, with maximum values observed during the noon hours and minimum values observed when solar radiation was less. The data showed a marked seasonal variation in O₃, with the highest hourly average O₃ concentration (497.2 µg/m³) in the summer season. Consequently, in order to identify the long-range transport sources adding to the increased O₃ levels, backward trajectories were computed using the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model. It was found that the polluted air mass originated from the Southeast Asian region and the Indo-Gangetic Plain. The polluted air mass, which advected large amounts of carbon monoxide (CO) plumes, was analyzed using the Measurement of Pollution in the Troposphere (MOPITT) retrievals. The correlations of O₃ with temperature (r = 0.746; P < 0.01) and solar radiation (r = 0.751; P < 0.01) were strongly positive, and that with NO_x was found to be negative. Stronger correlation of O₃ with NO_x was observed during pre-monsoon months (r = 0.627; P < 0.01) and following hours of photochemical reactions. There were substantial differences in concentrations between weekdays and weekends, with higher nitric oxide (NO) and nitrogen dioxide (NO₂), but lower O₃, concentrations on weekdays. A substantial weekday-weekend difference in O₃, which was higher on weekends, appears to be attributable to lower daytime traffic activity and hence reduced emissions of NO_x to a “NO_x-saturated” atmosphere.

Implications: The assessment of ground-level ozone in an industrial area with hazardous waste management facility is very important, as there is high possibility for more generation of tropospheric ozone. Since the location of the study area is coastal, wind plays a major role in O₃ transportation; hence, the effects of wind speed and wind direction have been studied in different seasons. When compared with the other studies carried out in different places across India, the present study area has recorded much greater O₃ mixing ratio. This study can be useful for setting up control strategies in such industrial areas.     

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.     

Effects of rooting medium and fertilizer rate on response of white clover to tropospheric ozone

Two white clover (Trifolium repens L.) clones with varying sensitivity to O(3) are being developed as a system to indicate effects of ambient concentrations of tropospheric O(3) on plants. One clone (NC-S) is highly sensitive to O(3) and the other (NC-R) is highly resistant. The system relies on periodic measurement of foliar injury, foliar chlorophyll, and forage production of NC-S and NC-R grown in 15-liter pots throughout a summer season. Relative amounts of foliar injury and ratios (NC-S/NC-R) for chlorophyll and forage weight can be used to estimate biologically effective ambient O(3) concentrations. The effect of variation in rooting media formulation and fertilizer rate on response of NC-S and NC-R to ambient O(3) was determined in the present study. In the rooting medium experiment, clover was grown in three mixtures of sandy loam topsoil:course washed sand:Metro Mix 220 (ratios (by volume) of 2:1:1, 2:1:5, and 6:1:1). In the fertilizer experiment, clover was grown in the 2:1:1 medium at four fertilizer rates (soluble 5-11-26 (N-P-K) at 0.0, 0.5, 1.0, or 2.0 g per pot). Ozone caused more foliar injury, more chlorosis, and a greater decrease in forage production of NC-S than of NC-R in all studies. Rooting media treatments affected both clones similarly and occasional clone x media interactions were judged to be random. Forage production by NC-S, relative to that of NC-R, was generally greater in the 0.0 fertilizer treatment, but the forage ratios were similar at all other fertilizer treatments. The relative response of NC-S and NC-R to O(3) is fairly stable under cultural conditions that support normal plant growth.     

Free tropospheric ozone production after deep convection of dispersing tropical urban plumes

Ozone generation is computed in a one-dimensional photochemistry code following convective redistribution of tropical urban effluent into the free troposphere. Simulations are run at several stages of pollutant dilution by surrounding surface air. A threshold boundary layer NO_x concentration of 300 pptv is established for significant production enhancements at upper levels. Areas defined by the 300 pptv level are examined in the Gaussian dispersion framework based on a wet season plume event observed in Amazonia. Pollution travels slowly in the sluggish winds of the equatorial trough. Daily storms are likely to interrupt the effluent while coverages are still on the order of few thousand square kilometers and NO_x concentrations are above the threshold. Dry season plume sizes are difficult to assess because local concentration data are scarce, but it is conceivable that the faster trade winds lead to a several fold extension.     

The influence of ozone exposure dynamics on the growth and yield of kidney bean

A field experiment was conducted in open-top chambers to assess the importance of peak exposure concentration and exposure frequency on the responses of kidney bean plants to O3. There were five treatments in the study: charcoal-filtered air, constant exposure to 0.05 ppm O3 (131 microg m(-3)) daily. fluctuating exposure to 0.08 ppm O3 on three alternate days, cluster exposure to 0.08 ppm O3 on three consecutive days, and peak exposure to 0.12 ppm O3 on two consecutive days. Exposures lasted 4 h and produced an average weekly exposure-period concentration of approximately 0.05 ppm in the O3-addition treatments and 0.025 ppm in the charcoal-filtered treatment. Exposures began on June 23 and terminated on September 8. Plants were harvested weekly and assessed for the number, area, and dry mass of leaves; dry mass of stems; dry mass of roots; the number of pods; and the incidence of foliar O3 injury. Yield was assessed at the end of the study. There were no consistent differences between the plants receiving charcoal-filtered air and those receiving O3 exposure. Significant differences were detected among the treatments for several of the growth variables assessed at the interim harvests, but in the final two harvests these differences had mostly disappeared. There were no significant effects of the O3-addition treatments on yield when compared to the plants receiving charcoal-filtered air. This indicates that there were no cumulative impacts on plants exposed to 0.12 ppm O3 for 4 h on two consecutive days followed by filtered air compared to plants receiving charcoal-filtered air. The seasonal 7-h average concentrations of O3 in the peak and filtered air treatments were approximately 0.040 and 0.025 ppm, respectively.     

Physiological and biochemical stress responses in grassland species are influenced by both early-season ozone exposure and interspecific competition

The effects of two-year early season ozone exposure on physiological and biochemical stress response were investigated in model plant communities. Achillea millefolium and Veronica chamaedrys target plants were grown in monocultures and in mixed cultures with Poa pratensis (phytometer) and exposed in open-top chambers over two years for five weeks to charcoal-filtered (CF) air plus 25 nl l(-1) O3 (control) and non-filtered (NF) air plus 50 nl l(-1) O3. Significant O3 effects were detected in different physiological and biochemical parameters, evidencing interspecific differences in metabolic stress responses and a strong influence of the competition factor. O3 induced strong oxidative effects in Achillea irrespective to the different growth modality. Veronica showed less O3-induced effects in monoculture than when grown in competition with the phytometer. Poa exhibited a different behaviour against O3 depending on the species in competition, showing an overall higher sensitivity to O3 when in mixture with Achillea.     

The effects of meteorology on ozone in urban areas and their use in assessing ozone trends

The United States Environmental Protection Agency issues periodic reports that describe air quality trends in the US. For some pollutants, such as ozone, both observed and meteorologically adjusted trends are displayed. This paper describes an improved statistical methodology for meteorologically adjusting ozone trends as well as characterizes the relationships between individual meteorological parameters and ozone. A generalized linear model that accommodates the nonlinear effects of the meteorological variables was fit to data collected for 39 major eastern US urban areas. Overall, the model performs very well, yielding R² statistics as high as 0.80. The analysis confirms that ozone is generally increasing with increasing temperature and decreasing with increasing relative humidity. Examination of the spatial gradients of these responses show that the effect of temperature on ozone is most pronounced in the north while the opposite is true of relative humidity. By including HYSPLIT-derived transport wind direction and distance in the model, it is shown that the largest incremental impact of wind direction on ozone occurs along the periphery of the study domain, which encompasses major NO_x emission sources.     

Effects of elevated ozone on leaf delta13C and leaf conductance of plant species grown in semi-natural grassland with or without irrigation

Stable carbon isotope ratios (delta(13)C) and leaf conductance (g(s)) were measured (2002, 2003) in Holcus lanatus L., Plantago lanceolata L. Ranunculus friesianus (Jord.), and Trifolium pratense L. at two levels of ozone (O(3)) with or without irrigation. In non-irrigated control plots, R. friesianus showed the least negative delta(13)C, and the smallest response to the treatments. Irrigation caused more negative delta(13)C, especially in H. lanatus. Irrespective of irrigation, O(3) increased delta(13)C in relationship to a decrease in g(s) in P. lanceolata and T. pratense. The strongest effect of O(3) on delta(13)C occurred in the absence of irrigation, suggesting that under field conditions lack of moisture in the top soil does not always lead to protection from O(3) uptake. It is concluded that in species such as T. pratense plants can maintain stomatal O(3) uptake during dry periods when roots can reach deeper soil layers where water is not limiting.     

Exposure to moderate concentrations of tropospheric ozone impairs tree stomatal response to carbon dioxide

With rising concentrations of both atmospheric carbon dioxide (CO₂) and tropospheric ozone (O₃), it is important to better understand the interacting effects of these two trace gases on plant physiology affecting land-atmosphere gas exchange. We investigated the effect of growth under elevated CO₂ and O₃, singly and in combination, on the primary short-term stomatal response to CO₂ concentration in paper birch at the Aspen FACE experiment. Leaves from trees grown in elevated CO₂ and/or O₃ exhibited weaker short-term responses of stomatal conductance to both an increase and a decrease in CO₂ concentration from current ambient level. The impairement of the stomatal CO₂ response by O₃ most likely developed progressively over the growing season as assessed by sap flux measurements. Our results suggest that expectations of plant water-savings and reduced stomatal air pollution uptake under rising atmospheric CO₂ may not hold for northern hardwood forests under concurrently rising tropospheric O₃.