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.     

Distribution of ozone and other air pollutants in forests of the Carpathian Mountains in central Europe.

Ozone (O3) concentrations were monitored during the 1997-1999 growing seasons in 32 forest sites of the Carpathian Mountains. At all sites (elevation between 450 and 1320 m) concentrations of O3, nitrogen dioxide (NO2), and sulfur dioxide (SO2) were measured with passive samplers. In addition, in two western Carpathian locations, Vychodna and Gubalówka, ozone was continuously monitored with ultraviolet (UV) absorption monitors. Highest average hourly O3 concentrations in the Vychodna and Guba?ówka sites reached 160 and 200 microg/m3 (82 and 102 ppb), respectively (except for the AOT40 values, ozone concentrations are presented as microg/m3; and at 25 degrees C and 760 mm Hg, 1 microg O3/m3 = 0.51 ppb O3). These sites showed drastically different patterns of diurnal 03 distribution, one with clearly defined peaks in the afternoon and lowest values in the morning, the other with flat patterns during the entire 24-h period. On two elevational transects, no effect of elevation on O3 levels was seen on the first one, while on the other a significant increase of O3 levels with elevation occurred. Concentrations of O3 determined with passive samplers were significantly different between individual monitoring years, monitoring periods, and geographic location of the monitoring sites. Results of passive sampler monitoring showed that high O3 concentrations could be expected in many parts of the Carpathian range, especially in its western part, but also in the eastern and southern ranges. More than four-fold denser network of monitoring sites is required for reliable estimates of O3 distribution in forests over the entire Carpathian range (140 points). Potential phytotoxic effects of O3 on forest trees and understory vegetation are expected on almost the entire territory of the Carpathian Mountains. This assumption is based on estimates of the AOT40 indices for forest trees and natural vegetation. Concentrations of NO2 and SO2 in the entire Carpathian range were typical for this part of Europe and below the expected levels of phytotoxicity.     

Ambient ozone (O3) in three Class I wilderness areas in the northeastern USA: measurements with Ogawa passive samplers

Ambient ozone (O(3)) was measured in two Class I wilderness areas, one within the White Mountain National Forest in north central New Hampshire (NH) and one within the Green Mountain National Forest in southwestern Vermont (VT), for six weeks between 5 July and 16 August 1994, using Ogawa passive nitrite-coated filter samplers and a one week exposure period each time. Results for 7-day mean ambient O(3) concentrations from the passive samplers were compared to results from a co-located continuous ultraviolet photometric O(3) analyzer both in NH and VT. Although the size of the data set was small, agreement through simple linear regression between mean 7-day O(3) concentrations determined by the continuous monitors, and those obtained from the passive samplers was generally very good (adjusted R(2) = 0.759; p = 0.0003). Overall, excluding the one outlier value, any observed differences in the results obtained by the two methods when comparing co-located passive samplers to the continuous monitor within a given study location, appeared to be solely due to experimental error.     

Ozone distribution and phytotoxic potential in mixed conifer forests of the San Bernardino Mountains, southern California

In the San Bernardino Mountains of southern California, ozone (O(3)) concentrations have been elevated since the 1950s with peaks reaching 600ppb and summer seasonal averages >100ppb in the 1970s. During that period increased mortality of ponderosa and Jeffrey pines occurred. Between the late 1970s and late1990s, O(3) concentrations decreased with peaks approximately 180ppb and approximately 60ppb seasonal averages. However, since the late 1990s concentrations have not changed. Monitoring during summers of 2002-2006 showed that O(3) concentrations (2-week averages) for individual years were much higher in western sites (58-69ppb) than eastern sites (44-50ppb). Potential O(3) phytotoxicity measured as various exposure indices was very high, reaching SUM00 - 173.5ppmh, SUM60 - 112.7ppmh, W126 - 98.3ppmh, and AOT40 - 75ppmh, representing the highest values reported for mountain areas in North America and Europe.     

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 13-week comparison of passive and continuous ozone monitors at forested sites in north-central Pennsylvania

Ogawa passive O3 samplers were used in a 13-week study (June 1-September 1, 1999) involving 11 forested and mountaintop sites in north-central Pennsylvania. Four of the sites were collocated with TECO model 49 O3 analyzers. A significant correlation (p < 0.0001) was found for 24-hr average weekly O3 concentrations between the two methodologies at the four sites with collocated monitors. As expected, there were positive relationships between increasing elevation of the sites and increasing O3 concentrations. No O3 exposure patterns were found on a west-to-east or south-to-north basis; however, the area known for lower O3 exposures within a smaller subsection of the study area showed consistently lower O3 exposures. Preliminary results regarding relationships of symptom responses within O3-sensitive bioindicators are also presented with black cherry (Prunus serotina, Ehrh.) and common milkweed (Asclepias syriaca, L.) showing clear evidence of increasing injury with increasing O3 exposures. Due to the extremely dry conditions encountered in north-central Pennsylvania during the 1999 growing season, O3-induced symptoms were sporadic and quite delayed until late-season rains during the latter portion of the observation period.     

Volatile organic compounds at two oil and natural gas production well pads in Colorado and Texas using passive samplers

A pilot study was conducted in application of the U.S. Environmental Protection Agency (EPA) Methods 325A/B variant for monitoring volatile organic compounds (VOCs) near two oil and natural gas (ONG) production well pads in the Texas Barnett Shale formation and Colorado Denver–Julesburg Basin (DJB), along with a traffic-dominated site in downtown Denver, CO. As indicated in the EPA method, VOC concentrations were measured for 14-day sampling periods using passive-diffusive tube samplers with Carbopack X sorbent at fenceline perimeter and other locations. VOCs were significantly higher at the DJB well pad versus the Barnett well pad and were likely due to higher production levels at the DJB well pad during the study. Benzene and toluene were significantly higher at the DJB well pad versus downtown Denver. Except for perchloroethylene, VOCs measured at passive sampler locations (PSs) along the perimeter of the Barnett well pad were significantly higher than PSs farther away. At the DJB well pad, most VOC concentrations, except perchloroethylene, were significantly higher prior to operational changes than after these changes were made. Though limited, the results suggest passive samplers are precise (duplicate precision usually ≤10%) and that they can be useful to assess spatial gradients and operational conditions at well pad locations over time-integrated periods.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at multiple fenceline locations at petrochemical refineries. This pilot study presents initial data demonstrating the utility of Methods 325A/B for monitoring at ONG facilities. Measurements revealed elevated concentrations reflective of production levels and spatial gradients of VOCs relative to source proximity at the Barnett well pad, as well as operational changes at the DJB well pad. Though limited, these findings indicate that Methods 325A/B can be useful in application to characterize VOCs at well pad boundaries.     

Monitoring ambient ozone with a network of passive samplers: a feasibility study

Ambient levels of ozone have been measured at 46 mountain forest, desert, Class I Wilderness areas and other remote locations using a network of passive samplers. Typical values were 40-80 ppb (2 week samples) and exhibited temporal variations (studied for up to 1 year) as well as changes with elevation (studied up to 10 500 ft (3 200 m)). The performance of the passive sampler was evaluated with respect to reproducibility, field controls, data capture (>0.95), precision for co-located samples (av. = 11.9%, n = 103), and the role of other atmospheric oxidants as potential interferents (2 locations). Suggestions for additional sampler performance evaluation and network operation are outlined.     

Ozone levels in Chongqing: a potential threat to crop plants commonly grown in the region?

Chongqing, a city with a population of >2.5 million, constitutes the biggest industrial and commercial centre in southwest China. Recent industrialization has led to an increasing air pollutant problem which is exacerbated by the topography and prevailing climate of the region. To date, interest has remained firmly focused on the levels of traditional air pollutants (sulphur dioxide [SO2], oxides of nitrogen [NOx], smoke and suspended particulate matter [SPM]), with little attention paid to photochemical oxidants such as ozone (O3). This paper reports the first assessment of ambient O3 levels in southwest China. Measurements were made in and around Chongqing using a combination of UV-absorption (at a site located in the northern sector of the city) and passive samplers (at 20 sites located in and around the city) between 1993 and 1996. The 7-h daily mean O3 concentrations ranged between 2 and 16 ppb (x10(9)) during the winter months, increasing to 18-41 ppb during the summer (June-August), when peak hourly mean O3 concentrations of 93 ppb were attained. Ozone exposures across the region commonly approached (or exceeded) UN-ECE and WHO short-term guidelines for the protection of crops. In addition, controlled chamber studies, in which 11 cultivars of Chinese crops commonly grown in the Chongqing region were screened for relative O3 sensitivity, indicated the potential for subtle effects on the growth of a number of crop plants, if ambient O3 levels continue to rise in the region. Employing ozone exposures somewhat higher than those experienced in the field, several cultivars of commonly grown Chinese cereal, vegetable and salad crops were found to be sensitive to O3 in terms of growth, but this was not always associated with the appearance of visible symptoms of injury and, in contrast to what was generally expected, only three species showed significant O3-induced reductions in root:shoot partitioning. There is a clear and urgent need for a comprehensive study of ambient air quality and its impact on crops and natural vegetation in this, as in other, rapidly developing regions of China.     

Potential bioindicator plant species for ambient ozone in forested mountain areas of central Europe

From 1993 to 2000, trees, shrubs, forbs and vines were evaluated for symptoms of probable ozone injury in the vicinity of passive ozone samplers or active ozone monitors in forest condition assessment networks in mostly mountainous regions, principally the Carpathian Mountain Range, in the central European countries Czech Republic, Poland, Romania, Slovakia and Ukraine. Each country was visited at least twice during the time period. Over the course of eight seasons, 29 species of native plants were identified as potential bioindicators of ozone. This is the first report of probable ozone injury on native plants in central Europe. Forbs and shrubs made up the bulk of the species (21 of 29). Potential bioindicators that are widely distributed include the forbs Centaurea nigra. and Impatiens parviflora and the shrubs Alnus incana, Corylus avellana, and Sambucus racemosa. Ozone concentrations in forcsted areas of central Europe appear to be high enough and of sufficient duration to cause foliar injury on a wide variety of native plants.     

Ambient ozone (O3) and adverse crop response: a unified view of cause and effect

This paper presents a cohesive view of the dynamics of ambient O(3) exposure and adverse crop response relationships, coupling the properties of photochemical O(3) production, flux of O(3) from the atmosphere into crop canopies and the crop response per se. The results from two independent approaches ((a) statistical and (b) micrometeorological) were analyzed for understanding cause-effect relationships of the foliar injury responses of tobacco cv Bel-W3 to the exposure dynamics of ambient O(3) concentrations. Similarly, other results from two independent approaches were analyzed in: (1) establishing a micrometeorological relationship between hourly ambient O(3) concentrations and their vertical flux from the air into a natural grassland canopy; and (2) establishing a statistical relationship between hourly ambient O(3) concentrations in long-term, chronic exposures and crop yield reductions. Independent of the approach used, atmospheric conditions appeared to be most conducive and the crop response appeared to be best explained statistically by the cumulative frequency of hourly ambient O(3) concentrations between 50 ppb and 90 ppb (100 and 180 microg m(-3)). In general, this concentration range represents intermediate or moderately enhanced hourly O(3) values in a polluted environment. Further, the diurnal occurrence of this concentration range (often approximately between 0900 and 1600 h in a polluted, agricultural environment) coincided with the optimal CO(2) flux from the atmosphere into the crop canopy, thus high uptake. The frequency of occurrence of hourly O(3) concentrations > 90 ppb (180 microg m(-3)) appeared to be of little importance and such concentrations in general appeared to occur during atmospheric conditions which did not facilitate optimal vertical flux into the crop canopy, thus low uptake. Alternatively, when > 90 ppb (180 microg m(-3)) O(3) concentrations occurred during the 0900-1600 h window, their frequency of occurrence was low in comparison to the 50-90 ppb (100-180 microg m(-3)) range. Based on the overall results, we conclude that if the cumulative frequency of hourly ambient O(3) concentrations between 50-62 ppb (100-124 microg m(-3)) occurred during 53% of the growing season and the corresponding cumulative frequency of hourly O(3) concentrations between 50-74 ppb (100-148 microg m(-3)) occurred during 71% of the growing season, then yield reductions in sensitive crops could be expected, if other factors supporting growth, such as adequate soil moisture are not limiting.     

Background ozone monitoring and phytodetection in the greater rural area of Corinth--Greece

Natural background ozone levels were monitored in three places within the greater rural area of Corinth, namely Bogdani Hill, Astronomical Observatory of Krionerion, and Kiato, and compared with ambient ozone monitored in the metropolitan area of Athens. Measurements were made sequentially, for a few weeks at each place, during the summer of 2000. In addition, ozone phytodetection, using tobacco (Nicotiana tabacum L.) plants of the Bel-W3 and Zichnomirodata varieties, was conducted in 12 places (the above included). Moreover, stomatal conductance was measured in the Bel-W3 plants, as well as in leaves of cultivated grape-vines (Vitis vinifera L.) and in needles of Aleppo pine (Pinus halepensis Mill.) trees and compared with the diurnal pattern of ozone concentrations.The 24 and 12 (08:00-20:00) hourly averages of ozone concentrations were high in Athens (37; 51 ppb), at Bogdani Hill (53; 56 ppb) and at the Astronomical Observatory (56; 55 ppb), but relatively low in Kiato (30; 34 ppb). Furthermore, the average daily AOT40 (accumulated exposure over 40 ppb for the daylight hours) (ppbh) was 193 in Athens, 212 at Bogdani Hill, 192 at the Astronomical Observatory and 47 in Kiato. Ozone concentrations exhibited the usual diurnal pattern in Athens (altitude 50 m), where they were maximum during midday and early afternoon hours, as well as at Bogdani Hill (300 m) and in Kiato (5 m) where, however, they were maximal 1-3 h later. At the Astronomical Observatory (altitude 920 m) ozone remained constant during both daylight and night hours. The differences in diurnal patterns are consistent with those in places of different elevation, reported elsewhere.The Bel-W3 plants were injured at all 12 places; Zichnomirodata plants exhibited lower injury and only in some of the places; probable ozone symptoms were also observed on vine plants and pine trees. The greatest injury was observed at the high altitude places of Astronomical Observatory and Mougostos. Stomatal conductance, in all three species, peaked during morning and early midday hours when ozone levels were higher in the high altitude, and lower in the low altitude, places.     

Surface ozone in Yosemite National Park

During the summers of 2003 and 2005, surface ozone concentrations were measured with portable ozone monitors at multiple locations in and around Yosemite National Park. The goal of these measurements was to obtain a comprehensive survey of ozone within Yosemite, which will help modelers predict and interpolate ozone concentrations in remote locations and complex terrain. The data from the portable monitors were combined with concurrent and historical data from two long-term monitoring stations located within the park (Turtleback Dome and Merced River) and previous investigations with passive samplers. The results indicate that most sites in Yosemite experience roughly similar ozone concentrations during well-mixed daytime periods, but dissimilar concentrations at night. Locations that are well exposed to the free troposphere during evening hours tend to experience higher (and more variable) nocturnal ozone concentrations, resulting in smaller diurnal variations and higher overall ozone exposures. Locations that are poorly exposed to the free troposphere during nocturnal periods tend to experience very low evening ozone, yielding larger diurnal variations and smaller overall exposures. Ozone concentrations are typically highest for the western and southern portions of the park and lower for the eastern and northern regions, with substantial spatial and temporal variability. Back-trajectory analyses suggest that air with high ozone concentrations at Yosemite often originates in the San Francisco Bay Area and progresses through the Central California Valley before entering the park.     

A comparative study of the performance of passive samplers

Atmospheric concentrations of benzene, toluene, ethylbenzene, and xylenes (o-xylene and m,p-xylene) were assessed in the Tricity area (Gdańsk-Sopot-Gdynia, Poland) with the use of two types of passive samplers: permeation (homemade passive samplers) and diffusive (Radiello and Orsa 5). Samples were collected during 2008 at selected sites in the Tricity area at monitoring stations belonging to the agency of Regional Air Quality Monitoring Foundation. The field study was conducted to compare the performance of these two different types of passive samplers. A statistical approach was formulated, and the experimental data were evaluated using the paired t test, Wilcoxon signed rank-sum test, and Friedman analysis of variance. All the statistical results confirm the hypothesis that the differences between the performances of the three sampling devices are highly significant. Despite the fact that data obtained with the homemade passive sampler indicated that the results were higher compared with those for the Radiello and Orsa 5 diffusive samplers, the authors note that all differences between the homemade permeation sampler and the Radiello and Orsa 5 diffusive samplers are positive.     

Summer-time distribution of air pollutants in Sequoia National Park, California

Concentrations of air pollutants were monitored during the May November 1999 period on a network of forested sites in Sequoia National Park, California. Measurements were conducted with: (1) active monitors for nitric oxide (NO), nitrogen dioxide (NO2) and ozone (O3); (2) honeycomb denuder/filter pack systems for nitric acid vapor (HNO3), nitrous acid vapor (HNO2), ammonia (NH3), sulfur dioxide (SO2), particulate nitrate (NO3-), ammonium (NH4+), and sulfate (SO4(2-)); and (3) passive samplers for O3, HNO3 and NO2. Elevated concentrations of O3 (seasonal means 41-71 ppb), HNO3 (seasonal means 0.4-2.9 microg/m3), NH3 (seasonal means 1.6-4.5 microg/m3), NO3 (1.1-2.0 microg/m3) and NH4+ (1.0-1.9 microg/m3) were determined. Concentrations of other pollutants were low. With increasing elevation and distance from the pollution source area of O3, NH3 and HNO3 concentrations decreased. Ammonia and NH4+ were dominant N pollutants indicating strong influence of agricultural emissions on forests and other ecosystems of the Sequoia National Park.     

Relationship of Indoor N02 Concentrations to Use of Unvented Gas Appliances

In preparation for a prospective study of the relationship of residential nitrogen dioxide exposure and respiratory infections in infants, we conducted a pilot study to assess NO₂ concentrations in a sample of homes in Albuquerque, New Mexico. The methods used to characterize concentrations are described. Three locations in 144 homes were monitored with passive diffusion samplers for two two-week cycles during November and December 1984. Two-week average NO₂ concentrations in the activity room ranged from 2.0 to 168.7 ppb. NO₂ concentrations in the activity room and the infant’s bedroom were fivefold higher in homes with gas stoves than in homes with electric stoves. Sixty-four percent of homes with gas stoves had activity room concentrations that exceeded the highest outdoor concentration. Multiple regression models Indicated that the outdoor concentration, use of a gas stove, particularly one with pilot lights, presence of a gas dryer in the living area, and use of a floor or wall furnace contributed to NO₂ concentrations. Use of a toaster or microwave oven in a house with a gas stove reduced NO₂ concentrations. The results of this study demonstrate a broad range of NO₂ concentrations in Albuquerque. We conclude with suggestions for an exposure assessment strategy that would be valid and feasible in the context of a large epidemiologic study of the health effects of NO₂.     

Responses of hybrid poplar clones and red maple seedlings to ambient O(3) under differing light within a mixed hardwood forest

The responses of ramets of hybrid poplar (Populus spp.) (HP) clones NE388 and NE359, and seedlings of red maple (Acer rubrum, L.) to ambient ozone (O(3)) were studied during May-September of 2000 and 2001 under natural forest conditions and differing natural sunlight exposures (sun, partial shade and full shade). Ambient O(3) concentrations at the study site reached hourly peaks of 109 and 98 ppb in 2000 and 2001, respectively. Monthly 12-h average O(3) concentrations ranged from 32.3 to 52.9 ppb. Weekly 12-h average photosynthetically active radiation (PAR) within the sun, partial shade and full shade plots ranged from 200 to 750, 50 to 180, and 25 to 75 micromol m(-2) s(-1), respectively. Ambient O(3) exposure induced visible foliar symptoms on HP NE388 and NE359 in both growing seasons, with more severe injury observed on NE388 than on NE359. Slight foliar symptoms were observed on red maple seedlings during the 2001 growing season. Percentage of total leaf area affected (%LAA) was positively correlated with cumulative O(3) exposures. More severe foliar injury was observed on plants grown within the full shade and partial shade plots than those observed on plants grown within the sun plot. Lower light availability within the partial shade and full shade plots significantly decreased net photosynthetic rate (Pn) and stomatal conductance (g(wv)). The reductions in Pn were greater than reductions in g(wv), which resulted in greater O(3) uptake per unit Pn in plants grown within the partial shade and full shade plots. Greater O(3) uptake per unit Pn was consistently associated with more severe visible foliar injury in all species and/or clones regardless of differences in shade tolerance. These studies suggest that plant physiological responses to O(3) exposure are likely complicated due to multiple factors under natural forest conditions.     

Effects of ozone on chlorophyll and quantum yield of tobacco (Nicotiana tabacum L.) varieties

Plants of Bel-W3 and of seven commercial tobacco varieties (Nicotiana tabacum L.) were exposed to two relatively low ozone concentrations (90 or 135 ppb) for 20 consecutive days, for 8 h per day. Ozone caused necrotic and chlorotic spots, acceleration of leaf senescence, depression of photosynthetic mechanism, chlorophyll diminution and greater destruction of chl a than of chl b. The higher sensitivity of chl a was also confirmed by exposure of segments of leaves in test tubes to high ozone concentration (>1000 ppb) as well as by bubbling of ozone in extracts of chlorophyll in vitro. The quantum yield (QY) of photosynthesis was positively correlated with the chlorophyll content and negatively correlated with the visible injury and the chl b/a ratio.     

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).