Assessing vegetation exposure to ozone: properties of the AOT40 index and modifications by deposition modelling

A discussion is presented on the application of micrometeorological deposition modelling principles to improve the characterisation of vegetation exposure to ozone and thus the use of critical levels as the basis of targeted emission control. The AOT40 (accumulated exposure over a threshold of 40 ppb or nl l(-1)) ozone exposure index is shown to impose a differential weighting that results in a high sensitivity, by a factor of two to 10 depending on the pollution climate, with respect to concentration. This makes it necessary to correct for systematic effects, such as the concentration profile below the measurement height, in order to justify a comparison with the biological data obtained from well-mixed exposure chambers. Available studies indicate a 50-70% lower AOT40 at the vegetation height. The resistance method for estimating the profile is extended to allow for stomatal effects that potentially bias the plant response predicted with an exposure index. This integrated profile-uptake correction refines the current approach and serves as a transitional step towards a real flux-based approach. For the latter, a new deposition parameterisation is tested against field observations.     

Estimates of AOT ozone indices from time-integrated ozone data and hourly air temperature measurements in southwest Sweden

Surface ozone concentration and surface air temperature was measured hourly at three coastal sites, four low elevation inland sites and two high elevation inland sites in southwestern Sweden. Diurnal ozone concentration range (DOR) and diurnal temperature range (DTR) were strongly correlated, both spatially and temporally, most likely because both depended on atmospheric stability. Accumulated ozone exposure above a threshold concentration of x nmol mol⁻¹ (AOTx) was estimated from time-integrated ozone concentration (as from diffusive sampling) and measures of ozone concentration variability. Two methods both estimated 24-h AOTx with high accuracy (modelling efficiencies >90% for x ≤ 40 nmol mol⁻¹). Daytime (08:00–20:00) AOTx could not be equally well estimated. Estimates were better for lower AOT thresholds. Diffusive ozone concentration sampling, combined with hourly temperature monitoring, could be a valuable complement to ozone concentration monitoring with continuous instruments.     

Responses of two birch (Betula pendula Roth) clones to different ozone profiles with similar AOT40 exposure

Saplings of two clones of European white birch (Betula pendula Roth) were exposed to three different ozone profiles resulting in same AOT40 value of 13–14 ppm h in a chamber experiment. The sensitive clone 5 and the more tolerant clone 2 were growing (1) under filtered air (=control), or (2) were exposed to 70 ppb ozone for 24 h d⁻¹ (=profile 1), (3) to 100 ppb ozone for 12 h d⁻¹ at 8:00–20:00 (=profile 2), or (4) to 200 ppb ozone for 4.5 h d⁻¹ at 9:30–14:00 (=profile 3) for 20 d. The saplings were determined for growth, visible leaf injuries, stomatal conductance, and concentrations of Rubisco, chlorophyll and carotenoids. Growth responses and induction of visible foliar injuries under different ozone profiles were variable, resulting in 4–17% lower dry mass of shoot, 16–46% reduction in stem height increment and 11–43% increase in visible injuries in clone 5, which was accompanied by higher leaf turnover rate under profile 3 indicating compensation growth. In clone 2, ozone-induced responses ranged from slight stimulation in stem height growth to 13% decrease in dry mass of shoot and 2–16% increase in visible injuries. Daytime stomatal conductance rates were lowered by 14–54% in clone 5 and 9–74% in clone 2, depending on profile. The additional power-weighted analyses revealed that high peak concentrations and exposure shape were important for induction of visible injuries in both clones and reduction in stomatal conductance in clone 5, whereas growth reductions were rather related to total cumulative exposure. The results indicate that profile of ozone exposure, night-time stomatal conductance (24 h flux), and recovery time for defence and compensations reactions should not be ignored in plant response and ozone flux modelling.     

Evaluation of ozone exposure indices in exposure-response modeling

In exposure-response modeling, a major concern is the numerical definition of exposure in relating crop loss to O3, yet few indices have been considered. This paper addresses research in which plant growth was regressed for soybean, wheat, cotton, corn, and sorghum against 613 numerical exposure indices using the Box-Tidwell model. When the minimum sum of squared errors criterion was used, optimum performance was not attained for any single index; however, near optimum performances were achieved by two censored cumulative indices and from a class of indices called the generalized, phenologically weighted, cumulative impact indices (GPWCIs). The top-performing GPWCIs accumulated concentrations, used sigmoid weighting schemes emphasizing O3 concentrations of 0.06 ppm (118 microg m(-3)) or higher, and had phenological weighting schemes with greatest weight occurring 20 to 40 days prior to crop maturity. These findings indicate that (1) peak concentrations are important, but lower concentrations should be included in the calculations, (2) increased plant sensitivity occurs between flowering and maturity, and (3) plants respond to cumulative exposure impact.     

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.     

A synthesis of AOT40-based response functions and critical levels of ozone for agricultural and horticultural crops

Crop-response data from over 700 published papers and conference proceedings have been analysed with the aim of establishing ozone dose-response functions for a wide range of European agricultural and horticultural crops. Data that met rigorous selection criteria (e.g. field-based, ozone concentrations within European range, full season exposure period) were used to derive AOT40-yield response functions for 19 crops by first converting the published ozone concentration data into AOT40 (AOT40 is the hourly mean ozone concentration accumulated over a threshold ozone concentration of 40 ppb during daylight hours, units ppm h). For any individual crop, there were no significant differences in the linear response functions derived for experiments conducted in the USA or Europe, or for individual cultivars. Three statistically independent groups were identified: ozone sensitive crops (wheat, water melon, pulses, cotton, turnip, tomato, onion, soybean and lettuce); moderately sensitive crops (sugar beet, potato, oilseed rape, tobacco, rice, maize, grape and broccoli) and ozone resistant (barley and fruit represented by plum and strawberry). Critical levels of a 3 month AOT40 of 3 ppm h and a 3.5 month AOT40 of 6 ppm h were derived from the functions for wheat and tomato, respectively.     

Selecting ozone exposure statistics for determining crop yield loss from air pollutants

Numerous ozone exposure statistics were calculated using hourly ozone data from crop yield loss experiments previously conducted for alfalfa, fresh market and processing tomatoes, cotton, and dry beans in an ambient ozone gradient near Los Angeles, California. Exposure statistics examined included peak (maximum daily hourly) and mean concentrations above specific threshold levels, and concentrations during specific time periods of the day. Peak and mean statistics weighted for ozone concentration and time period statistics weighted for hour of the day were also determined. Polynomial regression analysis was used to relate each of 163 ozone statistics to crop yield. Performance of the various statistics was rated by comparing residual mean square (RMS) values. The analyses demonstrated that no single statistic was best for all crop species. Ozone statistics with a threshold level performed well for most crops, but optimum threshold level was dependent upon crop species and varied with the particular statistics calculated. The data indicated that daily hours of exposure above a critical high-concentration threshold related well to crop yield for alfalfa, market tomatoes, and dry beans. The best statistic for cotton yield was an average of all daily peak ozone concentrations. Several different types of ozone statistics performed similarly for processing tomatoes. These analyses suggest that several ozone summary statistics should be examined in assessing the relationship of ambient ozone exposure to crop yield. Where no clear statistical preference is indicated among several statistics, those most biologically relevant should be selected.     

Vegetation exposure to ozone over the continental United States: Assessment of exposure indices by the Eta-CMAQ air quality forecast model

The main use of air quality forecast (AQF) models is to predict ozone (O₃) exceedances of the primary O₃ standard for informing the public of potential health concerns. This study presents the first evaluation of the performance of the Eta-CMAQ air quality forecast model to predict a variety of widely used seasonal mean and cumulative O₃ exposure indices associated with vegetation using the U.S. AIRNow O₃ observations. These exposure indices include two concentration-based O₃ indices, M7 and M12 (the seasonal means of daytime 7-h and 12-h O₃ concentrations, respectively), and three cumulative exposure-based indices, SUM06 (the sum of all hourly O₃ concentrations ≥ 0.06 ppm), W126 (hourly concentrations weighed by a sigmoidal weighting function), and AOT40 (O₃ concentrations accumulated over a threshold of 40 ppb during daylight hours). During a three-month simulation (July–September 2005), the model over predicted the M7 and M12 values by 8–9 ppb, or a NMB value of 19% and a NME value of 21%. The model predicts a central belt of high O₃ extending from Southern California to Middle Atlantic where the seasonal means, M7 and M12 (the seasonal means of daytime 7-h and 12-h O₃ concentrations), are higher than 50 ppbv. In contrast, the model is less capable of reproducing the observed cumulative indices. For AOT40, SUM06 and W126, the NMB and NME values are two- to three-fold of that for M7, M12 or peak 8-h O₃ concentrations. The AOT40 values range from 2 to 33 ppm h by the model and from 1 to 40 ppm h by the monitors. There is a significantly higher AOT40 value experienced in the United States in comparison to Europe. The domain-wide mean SUM06 value is 14.4 ppm h, which is about 30% higher than W126, and 40% higher than AOT40 calculated from the same 3-month hourly O₃ data. This suggests that SUM06 and W126 represent a more stringent standard than AOT40 if either the SUM06 or the W126 was used as a secondary O₃ standard. Although CMAQ considerably over predicts SUM06 and W126 values at the low end, the model under predicts the extreme high exposure values (>50 ppm h). Most of these extreme high values are found at inland California sites. Based on our analysis, further improvement of the model is needed to better capture cumulative exposure indices.     

High-resolution modelling of AOT40 and stomatal ozone uptake in wheat and grassland: a comparison between 2000 and the hot summer of 2003 in Switzerland

The aim was to compare the ozone risk for agricultural crops in Switzerland during the hot and dry year 2003 with the more 'normal' situation in 2000. An improved version of the Ozone DEposition Model ODEM was used at a 2 x 2 km resolution. The distribution of the index AOT40 was compared with the accumulated stomatal ozone flux, AF(st). Averaged AOT40 at 2 m and at canopy height was much higher in 2003 than in 2000, but inter-annual differences in AF(st) for wheat and grasslands were small due to the limiting effect of low soil water contents in 2003. AOT40 suggested larger potential yield losses in wheat in 2003, while using AF(st) with a threshold of 6 nmol m(-2) s(-1) (AF(st)6) yielded similar estimates for both years. The data show that modelling of AF(st) can be used to differentiate ozone risks between regions and years at a national scale.     

A comparison of indices that describe the relationship between exposure to ozone and reduction in the yield of agricultural crops

The objective of this study is to compare the use of several indices of exposure in describing the relationship between O₃ and reduction in agricultural crop yield. No attempt has been made to determine which exposure-response models best fit the data sets examined. Hourly mean O₃ concentration data, based on two-three measurements per hour, were used to develop indices of exposure from soybean and winter wheat experiments conducted in open-top chambers at the Boyce Thompson Institute, Ithaca, New York NCLAN field site. The comparative efficacy of cumulative indices (i.e. number of occurrences equal to or above specific hourly mean concentrations, sum of all hourly mean concentrations equal to or above a selected level, and the weighted sum of all hourly mean concentrations) and means calculated over an experimental period to describe the relationship between exposure to O₃ and reductions in the yield of agricultural crops was evaluated. None of the exposure indices consistently provided a best fit with the Weibull and linear models tested. The selection of the model appears to be important in determining the indices that best describe the relationship between exposure and response. The focus of selecting a model should be on fitting the data points as well as on adequately describing biological responses. The investigator should be careful to couple the model with data points derived from indices relevant to the length of exposure. While we have used a small number of data sets, our analysis indicates that exposure indices that weight peak concentrations differently than lower concentrations of an exposure regime can be used in the development of exposure-response functions. Because such indices may have merit from a regulatory perspective, we recommend that additional data sets be used in further analyses to explore the biological rationale for various indices of exposure and their use in exposure-response functions.     

Risk assessments for forest trees: the performance of the ozone flux versus the AOT concepts

Published ozone exposure-response relationships from experimental studies with young trees performed at different sites across Europe were re-analysed in order to test the performance of ozone exposure indices based on AOTX (Accumulated exposure Over a Threshold of X nmol mol(-1)) and AF(st)Y (Accumulated Stomatal Flux above a threshold of Y nmol m(-2) s(-1)). AF(st)1.6 was superior, as compared to AOT40, for explaining biomass reductions, when ozone sensitive species with differing leaf morphology were included in the analysis, while this was not the case for less sensitive species. A re-analysis of data with young black cherry trees, subject to different irrigation regimes, indicated that leaf visible injuries were more strongly related to the estimated stomatal ozone uptake, as compared to the ozone concentration in the air. Experimental data with different clones of silver birch indicated that leaf thickness was also an important factor influencing the development of ozone induced leaf visible injury.     

Biochemical changes in needles of Pinus radiata D. Don trees in relationship to long-term ozone exposure indices

Ambient concentrations of ozone in Europe are high enough to cause negative effects on vegetation. Therefore, many efforts have been made to determine exposure indices and critical levels for protection of vegetation. In this context, the choice of a suitable attribute to determine the pollutant effect is of paramount importance. Until now, much of the work has been done with attributes such as biomass or growth. In the present work correlation factors have been established between biochemical parameters (peroxidase activity, ascorbate and sulfhydryl contents) of Pinus radiata trees and exposure indices of ozone. Our results show that peroxidase cannot be used as an indicator of effects of long-term exposure to ozone but still remains as an excellent indicator of short-term ozone fluctuations in the field. Ascorbate may act as an intermediate indicator responding to both short fluctuations and long-term exposures to ozone. Finally, sulfhydryl may be used as a long-term indicator in relation to the AOT (average over threshold) exposure index. Our results also point to the fact that Pinus radiata may be affected by ozone at AOT values lower than 10 ppm.h as already observed with other tree species.     

Response of native plants of northeastern United States and southern Spain to ozone exposures; determining exposure/response relationships

Tropospheric ozone has been identified as the most important regional scale air pollutant across much of eastern United States of America and many areas of Mediterranean climes in southern Europe. Recent field surveys in the northeastern USA and in southeastern Spain have revealed many additional plant species that exhibit symptoms typical of ozone-induced injuries. Objectives of this study were to confirm ozone as the cause of the observed foliar symptoms, determine ozone induced exposure/response relationships, and identify possible bio-indicator species. Thirteen native species of northeastern USA and 27 native species of southeastern Spain were selected for study. Plant species were exposed to ozone within 16 CSTR chambers in a greenhouse during the summer seasons of 2000 and 2001; ozone exposures of 30, 60, 90, and 120 ppb were delivered for 7 h/day, 5 days/week. Results have confirmed that with few exceptions, symptoms observed in the field were induced by exposures to ambient ozone. Species differed significantly in terms of the exposures required for the initiation of visible symptoms and subsequent injury progression.     

Statistical estimation of ozone exposure metrics

Data from recent experiments at North Carolina State University and other locations provide a unique opportunity to study the effect of ambient ozone on the growth of clover. The data consist of hourly ozone measurements over a 140 day growing season at eight sites in the US, coupled with clover growth response data measured every 28 days. The objective is to model an indicator of clover growth as a function of ozone exposure. A common strategy for dealing with the numerous hourly ozone measurements is to reduce these to a single summary measurement, a so-called exposure metric, for the growth period of interest. However, the mean ozone value is not necessarily the best summarization, as it is widely believed that low levels of ozone have a negligible effect on growth, whereas peak ozone values are deleterious to plant growth. There are also suspected interactions with available sunlight, temperature and humidity. A number of exposure metrics have been proposed that reflect these beliefs by assigning different weights to ozone values according to magnitude, time of day, temperature and humidity. These weighting schemes generally depend on parameters that have, to date, been subjectively determined. We propose a statistical approach based on profile likelihoods to estimate the parameters in these exposure metrics.     

Ozone pollution and ozone biomonitoring in European cities. Part I: Ozone concentrations and cumulative exposure indices at urban and suburban sites

In the frame of a European research project on air quality in urban agglomerations, data on ozone concentrations from 23 automated urban and suburban monitoring stations in 11 cities from seven countries were analysed and evaluated. Daily and summer mean and maximum concentrations were computed based on hourly mean values, and cumulative ozone exposure indices (Accumulated exposure Over a Threshold of 40 ppb (AOT40), AOT20) were calculated. The diurnal profiles showed a characteristic pattern in most city centres, with minimum values in the early morning hours, a strong rise during the morning, peak concentrations in the afternoon, and a decline during the night. The widest amplitudes between minimum and maximum values were found in central and southern European cities such as Düsseldorf, Verona, Klagenfurt, Lyon or Barcelona. In the northern European cities of Edinburgh and Copenhagen, by contrast, maximum values were lower and diurnal variation was much smaller. Based on ozone concentrations as well as on cumulative exposure indices, a clear north–south gradient in ozone pollution, with increasing levels from northern and northwestern sites to central and southern European sites, was observed. Only the Spanish cities did not fit this pattern; there, ozone levels were again lower than in central European cities, probably due to the direct influence of strong car traffic emissions. In general, ozone concentrations and cumulative exposure were significantly higher at suburban sites than at urban and traffic-exposed sites. When applying the newly established European Union (EU) Directive on ozone pollution in ambient air, it was demonstrated that the target value for the protection of human health was regularly surpassed at urban as well as suburban sites, particularly in cities in Austria, France, northern Italy and southern Germany. European target values and long-term objectives for the protection of vegetation expressed as AOT40 were also exceeded at many monitoring sites.     

Diurnal variations of ozone and other pollutants in an urban area

A theoretical model is used to describe the diurnal variations of primary and secondary pollutants, with emphasis on ozone. This is done for an urban basin with anthropogenic sources of nitrogen oxides and hydrocarbons. We propose a scheme for the decomposition of aromatic compounds. According to this scheme, each aromatic molecule gives rise to six transfers of NO to NO₂ without consumption of odd oxygen. It is concluded that it is not a good approximation to represent urban hydrocarbon emissions by one single species, neither in short term (a few hours) nor multiday simulations. Species with both high and low reactivity ought to be included. We show that the nocturnal minimum in ozone often observed in urban areas, is mainly induced by gas chemistry. It is not a good approximation to omit the chemical development during the night-time in a theoretical analysis of urban photochemical pollution. Such an omission introduces errors also in the day-time chemistry. Application of constant dissociation rate coefficients over the day gives rise to false morning and evening ozone maxima.     

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.