Stochastic model to forecast ground-level ozone concentration at urban and rural areas

Stochastic models that estimate the ground-level ozone concentrations in air at an urban and rural sampling points in South-eastern Spain have been developed. Studies of temporal series of data, spectral analyses of temporal series and ARIMA models have been used. The ARIMA model (1,0,0) x (1,0,1)24 satisfactorily predicts hourly ozone concentrations in the urban area. The ARIMA (2,1,1) x (0,1,1)24 has been developed for the rural area. In both sampling points, predictions of hourly ozone concentrations agree reasonably well with measured values. However, the prediction of hourly ozone concentrations in the rural point appears to be better than that of the urban point. The performance of ARIMA models suggests that this kind of modelling can be suitable for ozone concentrations forecasting.     

Estimating changes in urban ozone concentrations due to life cycle emissions from hydrogen transportation systems

Hydrogen has been proposed as a low polluting alternative transportation fuel that could help improve urban air quality. This paper examines the potential impact of introducing a hydrogen-based transportation system on urban ambient ozone concentrations. This paper considers two scenarios, where significant numbers of new hydrogen vehicles are added to a constant number of gasoline vehicles. In our scenarios hydrogen fuel cell vehicles (HFCVs) are introduced in Sacramento, California at market penetrations of 9% and 20%. From a life cycle analysis (LCA) perspective, considering all the emissions involved in producing, transporting, and using hydrogen, this research compares three hypothetical natural gas to hydrogen pathways: (1) on-site hydrogen production; (2) central hydrogen production with pipeline delivery; and (3) central hydrogen production with liquid hydrogen truck delivery. Using a regression model, this research shows that the daily maximum temperature correlates well with atmospheric ozone formation. However, increases in initial VOC and NO_x concentrations do not necessarily increase the peak ozone concentration, and may even cause it to decrease. It is found that ozone formation is generally limited by NO_x in the summer and is mostly limited by VOC in the fall in Sacramento. Of the three hydrogen pathways, the truck delivery pathway contributes the most to ozone precursor emissions. Ozone precursor emissions from the truck pathway at 9% market penetration can cause additional 3-h average VOC (or NO_x) concentrations up to approximately 0.05% (or 1%) of current pollution levels, and at 20% market penetration up to approximately 0.1% (or 2%) of current pollution levels. However, all of the hydrogen pathways would result in very small (either negative or positive) changes in ozone air quality. In some cases they will result in worse ozone air quality (mostly in July, August, and September), and in some cases they will result in better ozone air quality (mostly in October). The truck pathway tends to cause a much wider fluctuation in degradation or improvement of ozone air quality: percentage changes in peak ozone concentrations are approximately −0.01% to 0.04% for the assumed 9% market penetration, and approximately −0.03% to 0.1% for the 20% market penetration. Moreover, the 20% on-site pathway occasionally results in a decrease of about −0.1% of baseline ozone pollution. Compared to the current ambient pollution level, all three hydrogen pathways are unlikely to cause a serious ozone problem for market penetration levels of HFCVs in the 9–20% range.     

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.     

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.     

Comparison of ozone temporal scales for large urban, small urban, and rural areas in Georgia

Ground-level ozone (O3) time series are characterized by the sum of several distinct temporal scales: long-term, seasonal, synoptic, diurnal (daily), and intraday variation. In this study, the authors use a Kolmorogov-Zurbenko filter to separate the 1981-2001 O3 time-series from many sites in and around Georgia into these various components. The authors compare the temporal components to examine differences between small and large metropolitan areas and between urban and rural areas. They then focus on the synoptic component to define a predominant transport region or airshed for each site.     

Spatially differentiated and source-specific population exposure to ambient urban air pollution

Models assessing exposure to air pollution often focus on macro-scale estimates of exposure to all types of sources for a particular pollutant across an urban study area. While results based on these models may aid policy makers in identifying larger areas of elevated exposure risk, they often do not differentiate the proportion of population exposure attributable to different polluting sources (e.g. traffic or industrial). In this paper, we introduce a population exposure modeling system that integrates air dispersion modeling, Geographic Information Systems (GIS), and population exposure techniques to spatially characterize a source-specific exposure to ambient air pollution for an entire urban population at a fine geographical scale. By area, total population exposure in Dallas County in 2000 was more attributable to vehicle polluting sources than industrial polluting sources at all levels of exposure. Population exposure was moderately correlated with vehicle sources (r = 0.440, p < 0.001) and weakly with industrial sources (r = 0.069, p = 0.004). Population density was strongly correlated with total exposure (r = 0.896, p < 0.001) but was not significantly correlated with individual or combined sources. The results of this study indicate that air quality assessments must incorporate more than industrial or vehicle polluting sources-based population exposure values alone, but should consider multiple sources. The population exposure modeling system proposed in this study shows promise for use by municipal authorities, policy makers, and epidemiologists in evaluating and controlling the quality of the air in the process of urban planning and mitigation measures.     

Estimating micrometeorological inputs for modeling dispersion in urban areas during stable conditions

We examine the performance of three methods to estimate the surface friction velocity and the Monin–Obukhov (MO) length in stable conditions. Estimates from these methods are compared with measurements made at two urban sites: the Wilmington site located in the middle of an urban area, and the VTMX site located on a sloping, smooth area in Salt Lake City. The first method uses the mean wind at a single height (Single U or SU), the second uses the wind speed at a single level and the temperature difference between two levels (U delta T or UDT), and the third method uses two levels of wind speed and temperature (delta U delta T or DUDT). The performance of the SU and UDT methods in estimating u_* are comparable. The SU method yields better estimates of the MO length than the UDT method does. The DUDT method performs poorly in estimating both u_* and L. The major conclusions of this study are that (1) measurements of mean winds and temperatures at one or two levels at an urban location can provide adequate estimates of micrometeorological variables required in modeling dispersion in the stable boundary layer, and (2) methods based on using differences in temperatures and velocities between two levels can provide unreliable estimates of these variables because these differences can be overwhelmed by inevitable uncertainties in the measurement of mean variables.     

Growth response of bigcone Douglas fir (Pseudotsuga macrocarpa) to long-term ozone exposure in southern California

Long-term radial growth of bigcone Douglas fir (Pseudotsuga macrocarpa) was studied throughout its range in the San Bernardino Mountains of southern California, where ambient ozone has been high for approximately the past 40 years. A gradient of both ozone concentration and precipitation exists from west (high) to east (low). Growth rates of bigcone Douglas fir are considerably lower since 1950 throughout the San Bernardino Mountains, with the largest growth reductions in the western part of the range where ozone exposure is highest. Needle retention is also somewhat lower at high ozone sites. Lower annual precipitation since 1950 may have some impact on long-term growth reductions, and short-term growth reductions induced by drought are an important component of long-term growth reductions at sites with high ozone exposure. An ozone-climate stress complex may be responsible for recent reductions in the growth of bigcone Douglas fir.     

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.     

Changes in pigment concentration and composition in Norway spruce induced by long-term exposure to low levels of ozone

Rametes of Norway spruce were fumigated with 30 ppb (nl litre(-1)) ozone above ambient level for 4 years in open-top chambers. They were grown under different light conditions, because some of the chambers received approximately 10% less light than the others. Samples from three age classes were analyzed for nitrogen and pigments using HPLC. It could be demonstrated that the ozone treatment reduced the concentration of chlorophyll (a) and (b), alpha- and beta-carotene, but increased the concentration of antheraxanthin. A significant decrease was found for the violaxanthin/antheraxanthin ratio following the ozone treatment. The concentration of all the pigments and of nitrogen were significantly related to the age classes, and a similar relationship was found for the light levels, except for antheraxanthin and total carotenoids. The ratio of chlorophyll a/b was only significantly related to the age classes.     

The effects of selected NOx reduction scenarios on long-term nitrogen deposition and episodic ozone levels in Europe

For computational reasons, evaluations of NO(x) emission controls usually concentrate on either episodic or annual impacts on pollution or deposition levels. However, previously published model results indicate that the consequences of NO(x) controls can be quite different on these different time scales. In this paper we analyse the impact of a consistent set of NO(x) control scenarios on both the episodic and annual time-scales. Using similar models, we compute levels of episode peak O(3) and NO(2) and annual NO(y)-N and total N deposition at three locations in Europe due to six emission scenarios derived from OECD estimates. An NO(x) control scenario which reduces European emissions by 63%, only results in total annual N deposition reductions of 19, 36 and 26% at the three locations examined because of the influence of ammonia-nitrogen deposition. The same scenario results in either increases or decreases in episode peak O(3) due to the influence of hydrocarbons. Emission reduction strategies should take into account not only NO(x) emissions, but emissions of other pollutants, such as hydrocarbons and ammonia.     

Neural network-based study for predicting ground-level ozone concentration in large urban areas, applied to the Sao Paulo metropolitan area

Events of high concentration of ground-level ozone constitute a matter of major concern in large urban areas in terms of air quality, and public health. In the Sao Paulo Metropolitan Area (SPMA), air quality data generated by a network of air quality measuring stations have been used in a number of studies correlating ozone formation with different variables. A study was carried out on the application of neural network models in the identification of typical sceneries leading to high ground-level ozone concentrations in the SPMA. The results were then applied in the selection of variables, and in the definition of neural network-based models for estimating ozone levels from meteorological variables. When combined with existing weather prediction tools, the models can be applied in the prediction of ozone levels in the SPMA     

Growth-stage dependent crop yield response to ozone exposure

Data from four crop yield-loss field trials were examined to determine if analysis using an imposed phenological weighting function based on seasonal growth stage would provide a more accurate indication of impact of ozone exposure. Alfalfa (Medicago sativa L. cv. Moapa 69), dry bean (Phaseolus vulgaris L. cv. California Dark Red kidney), fresh market and processing tomato (Lycopersicon esculentum Mill. cv. 6718 VF and VF-145-B7879, respectively) were grown at 9-11 ambient field plots within southern California comprising an ambient gradient of ozone. The growing season for each crop was artificially divided into 'quarters' composed of equal numbers of whole days and roughly corresponding to specific growth stages. Ozone exposure was calculated for each of these 'quarters' and regressed against final crop yield using 163 different exposure statistics. Weighting functions were developed using reciprocal residual mean square (1/RMS) or percentage of the best 100 exposure statistics of the 163 tested (TOP100) for each of the quarters. The third quarter of the alfalfa season was clearly most responsive to ozone as measured by both of the weighting functions. Third quarter ozone was also weighted highest by both weighting functions for dry bean. Fresh market and processing tomato were each influenced the greatest by second quartero zone as demonstrated by both weighting functions. The occurrence of ozone during physiologically important events (flowering and initial fruit set in second quarter for tomato; pod development in third quarter for dry bean) appeared to influence the yield of these crops the greatest. Growth-stage-dependent phenological weighting of pollutant exposure may result in more effective predictions of levels of ozone exposure resulting in yield reductions.     

Sensitivity of urban ozone formation to chlorine emission estimates

Recent evidence has demonstrated that chlorine radical chemistry can enhance tropospheric volatile organic compound oxidation and has the potential to enhance ozone formation in urban areas. In order to investigate the regional impacts of chlorine chemistry in southeastern Texas, preliminary estimates of atmospheric releases of atomic chlorine precursors from industrial point sources, cooling towers, water and wastewater treatment, swimming pools, tap water, reactions of chlorides in sea salt aerosols, and reactions of chlorinated organics were developed. To assess the potential implications of these estimated emissions on urban ozone formation, a series of photochemical modeling studies was conducted to examine the spatial and temporal sensitivity of ozone and a unique marker species for chlorine chemistry, 1-Chloro-3-methyl-3-butene-2-one (CMBO), to molecular chlorine emissions estimates. Based on current estimates of molecular chlorine emissions in southeastern Texas, chlorine chemistry has the potential to enhance ozone mixing ratios by up to 11–16 ppbv. Impacts varied temporally, with emissions from cooling towers primarily responsible for a morning enhancement in ozone mixing ratios and emissions from residential swimming pools for an afternoon enhancement. Maximum enhancement in CMBO mixing ratios ranged from 59 to 69 pptv.     

Simplified model for the prediction of ozone generation in polluted urban areas with continuous precursor species emissions

In this paper we study the transient ozone generation process in polluted urban areas, using a simplified set of chemical reactions for the NO_x and hydrocarbon photolysis. We obtained a reduced kinetic mechanism and it is solved using the boundary layer theory due to the appearance of two time scales in the problem associated with the photo-chemical reactions of the NO₂ and unburned fuel, respectively. Assuming a temporal addition of ozone precursor species, we obtained in closed form, the temporal evolution of the ozone concentration as a function of the physico-chemical parameters.     

A statistical assessment of saturation and mobile sampling strategies to estimate long-term average concentrations across urban areas

The objectives of this study were: (1) to quantify the errors associated with saturation air quality monitoring in estimating the long-term (i.e., annual and 5 yr) mean at a given site from four 2-week measurements, once per season; and (2) to develop a sampling strategy to guide the deployment of mobile air quality facilities for characterizing intraurban gradients of air pollutants, that is, to determine how often a given location should be visited to obtain relatively accurate estimates of the mean air pollutant concentrations. Computer simulations were conducted by randomly sampling ambient monitoring data collected in six Canadian cities at a variety of settings (e.g., population-based sites, near-roadway sites). The 5-yr (1998-2002) dataset consisted of hourly measurements of nitric oxide (NO), nitrogen dioxide (NO2), oxides of nitrogen (NOx), sulfur dioxide (SO2), coarse particulate matter (PM10), fine particulate matter (PM2.5), and CO. The strategy of randomly selecting one 2-week measurement per season to determine the annual or long-term average concentration yields estimates within 30% of the true value 95% of the time for NO2, PM10 and NOx. Larger errors, up to 50%, are expected for NO, SO2, PM2.5, and CO. Combining concentrations from 85 random 1-hr visits per season provides annual and 5-yr average estimates within 30% of the true value with good confidence. Overall, the magnitude of error in the estimates was strongly correlated with the variability of the pollutant. A better estimation can be expected for pollutants known to be less temporally variable and/or over geographic areas where concentrations are less variable. By using multiple sites located in different settings, the relationships determined for estimation error versus number of measurement periods used to determine long-term average are expected to realistically portray the true distribution. Thus, the results should be a good indication of the potential errors one could expect in a variety of different cities, particularly in more northern latitudes.     

Characteristics of urban ground-level ozone in Korea

This study considers the characteristics of ground-level ozone (O3) in five Korean cities over a time period of 6-8 years. The focus of this study is daily maximum 1-hr and 8-hr concentrations. For all the study cities in the period examined, the mean and most of the percentiles (5, 10, 25, 50, 75, 90, and 95) for the daily maximum 1-hr and 8-hr concentrations showed increasing trends, although not all trends were statistically significant. The daily maximum 1-hr and 8-hr concentrations slowly increased during late winter, and peaks were attained during the summer season (from May to September). All the selected cities exhibited a high degree of correlation between their daily maximum 8-hr and 1-hr concentrations. The daily maximum 8-hr concentrations, which were climatologically equivalent to the Korean 1 hr/100 parts per billion (ppb) standard, were higher than the current 8 hr/60 ppb by a difference of 8-16 ppb. Compared with other cities in Korea, Seoul recorded a substantially higher frequency of days and hours with concentrations above 1 hr/100 ppb, and a higher frequency of days with concentrations above 8 hr/60 ppb and 8 hr/80 ppb. Seoul also recorded a substantially higher frequency of hours with concentrations above 1 hr/100 ppb than days with concentrations above 1 hr/100 ppb, implying that on some days severe exceedances persisted for more than one hour per day. During multiple-day episodes a North Pacific High dominated Korea, which is quite typical in Korea during the summer season.