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.     

Impact of vertical transport processes on the tropospheric ozone layering above Europe.: Part II: Climatological analysis of the past 30 years

Using the set of multivariate criteria described in a companion paper, ozone-rich layers detected in tropospheric soundings are clustered according to their stratospheric or boundary layer origin. An additional class for aged tropospheric air masses is also considered. This analysis is exclusively based on the measured physical properties of the layers. The database includes 27,000 ozone profiles collected above 11 European stations—two of which provide measurements since 1970. The seasonal cycle of the tropospheric ozone stratification exhibits a clear summer maximum. This increase is due to aged tropospheric air masses that are more frequently detected, suggesting an enhanced lifetime of layers in summer. In terms of ozone content, the relative impact of stratospheric ozone compared to the other sources is highest in winter while export from the boundary layer presents a uniform seasonal cycle. Altitude and thickness distributions of the layers are consistent with the dynamical processes involved in the layering. Northernmost and southernmost stations are more exposed to stratospheric air intrusions into the free troposphere. Long-term trends show that transport from the tropopause region has increased since the mid 1980s. This trend being concomitant with lower ozone content of such layers, a moderate trend of the transport efficiency from the stratosphere on total tropospheric ozone is observed. The increase of ozone detected in tropospheric layers since the mid 1980s cannot be attributed to any recent export process from either the stratosphere or the boundary layer but rather to enhanced photochemical production in aged air masses or to an increase in the lifetime of the layers.     

Application of genetic algorithms for the design of ozone control strategies

Designing air quality management strategies is complicated by the difficulty in simultaneously considering large amounts of relevant data, sophisticated air quality models, competing design objectives, and unquantifiable issues. For many problems, mathematical optimization can be used to simplify the design process by identifying cost-effective solutions. Optimization applications for controlling nonlinearly reactive pollutants such as tropospheric ozone, however, have been lacking because of the difficulty in representing nonlinear chemistry in mathematical programming models. We discuss the use of genetic algorithms (GAs) as an alternative optimization approach for developing ozone control strategies. A GA formulation is described and demonstrated for an urban-scale ozone control problem in which controls are considered for thousands of pollutant sources simultaneously. A simple air quality model is integrated into the GA to represent ozone transport and chemistry. Variations of the GA formulation for multiobjective and chance-constrained optimization are also presented. The paper concludes with a discussion of the practically of using more sophisticated, regulatory-scale air quality models with the GA. We anticipate that such an approach will be practical in the near term for supporting regulatory decision-making.     

Extreme value modeling for the analysis and prediction of time series of extreme tropospheric ozone levels: a case study

The occurrence of high concentrations of tropospheric ozone is considered as one of the most important issues of air management programs. The prediction of dangerous ozone levels for the public health and the environment, along with the assessment of air quality control programs aimed at reducing their severity, is of considerable interest to the scientific community and to policy makers. The chemical mechanisms of tropospheric ozone formation are complex, and highly variable meteorological conditions contribute additionally to difficulties in accurate study and prediction of high levels of ozone. Statistical methods offer an effective approach to understand the problem and eventually improve the ability to predict maximum levels of ozone. In this paper an extreme value model is developed to study data sets that consist of periodically collected maxima of tropospheric ozone concentrations and meteorological variables. The methods are applied to daily tropospheric ozone maxima in Guadalajara City, Mexico, for the period January 1997 to December 2006. The model adjusts the daily rate of change in ozone for concurrent impacts of seasonality and present and past meteorological conditions, which include surface temperature, wind speed, wind direction, relative humidity, and ozone. The results indicate that trend, annual effects, and key meteorological variables along with some interactions explain the variation in daily ozone maxima. Prediction performance assessments yield reasonably good results.     

Emission of non-methane volatile organic compounds (VOCs) from boreal peatland microcosms—effects of ozone exposure

Non-methane volatile organic compounds (VOCs) emitted from boreal peatland microcosms were semiquantitatively determined using gas chromatography–mass spectrometry techniques in a growth chamber experiment. Furthermore, effects of vegetation composition and different ozone concentrations on these emissions were estimated by multivariate data analyses. The study concentrated on the less-studied VOCs, and isoprene was not analyzed. The analyses suggest that a sedge Eriophorum vaginatum is associated with emissions of the four most-emitted VOC groups (cyclic, aromatic, carbonyl and aliphatic hydrocarbon compounds) and also with VOCs emitted in smaller amounts (terpenoids and N-containing compounds). A woody dwarf shrub Andromeda polifolia was strongly associated with emissions of aromatic, carbonyl and terpenoid compounds. Results suggest that exposure to an ozone concentration of 150 ppb leads to an increased emission of most VOC groups. Emission of aromatic compounds seems to increase linearly with increasing ozone concentration. These observations indicate that peatlands may be a source of a vast range of volatile compounds to the atmosphere. For more accurate assessment of the impact of elevated tropospheric ozone on the terpenoid and non-terpenoid VOC emissions from peatlands, well-replicated open-air ozone-exposure experiments should be conducted.     

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.     

Impact of biogenic terpene emissions from <Emphasis Type="Italic">Brassica napus</Emphasis> on tropospheric ozone over saxony (Germany)

INTRODUCTION: The role of biogenic emissions in tropospheric ozone production is currently under discussion and major aspects are not well understood yet. This study aims towards the estimation of the influence of biogenic emissions on tropospheric ozone concentrations over Saxony in general and of biogenic emissions from brassica napus in special. MODELLING TOOLS: The studies are performed by utilizing a coupled numerical modelling system consisting of the meteorological model METRAS and the chemistry transport model MUSCAT. For the chemical part, the Euro-RADM algorithm is used. EMISSIONS: Anthropogenic and biogenic emissions are taken into account. The anthropogenic emissions are introduced by an emission inventory. Biogenic emissions, VOC and NO, are calculated within the chemical transport model MUSCAT at each time step and in each grid cell depending on land use type and on the temperature. The emissions of hydrocarbons from forest areas as well as biogenic NO especially from agricultural grounds are considered. Also terpene emissions from brassica napus fields are estimated. SIMULATION SETUP AND METEOROLOGICAL CONDITIONS: The simulations were performed over an area with an extension of 160 x 140 km2 which covers the main parts of Saxony and neighboring areas of Brandenburg, Sachsen-Anhalt and Thuringia. Summer smog with high ozone concentrations can be expected during high pressure conditions on hot summer days. Typical meteorological conditions for such cases were introduced in an conceptual way. RESULTS: It is estimated that biogenic emissions change tropospheric ozone concentrations in a noticeable way (up to 15% to 20%) and, therefore, should not be neglected in studies about tropospheric ozone. Emissions from brassica napus do have a moderate potential to enhance tropospheric ozone concentrations, but emissions are still under consideration and, therefore, results vary to a high degree. CONCLUSIONS: Summing up, the effect of brassica napus terpene emissions on ozone concentrations is noticeable, but not too pronounced. The results give a preliminary estimate on what the effect due to brassica napus emissions could be until better parameterizations can be derived from measurements.     

Emission,speciation, and evaluation of impacts of non-methane volatile organic compounds from open dump site

Surface emission from Dhapa, the only garbage disposal ground in Kolkata, is a matter of concern to the local environment and also fuels the issues of occupational and environmental health. Surface emission of the Dhapa landfill site was studied using a flux chamber measurement for nonmethane volatile organic compounds (NMVOCs). Eighteen noncarbonyl volatile organic compounds (VOCs) and 14 carbonyl VOCs, including suspected and known carcinogens, were found in appreciable concentrations. The concentrations of the target species in the flux chamber were found to be significantly higher for most of the species in summer than winter. Surface emission rate of landfill gas was estimated by using two different approaches to assess the applicability for an open landfill site. It was found that the emissions predicted using the model Land GEM version 3.02 is one to two orders less than the emission rate calculated from flux chamber measurement for the target species. Tropospheric ozone formation has a serious impact for NMVOC emission. The total ozone-forming potential (OFP) of the Dhapa dumping ground considering all target NMVOCs was estimated to be 4.9E+04 and 1.2E+05 g/day in winter and summer, respectively. Also, it was found that carbonyl VOCs play a more important role than noncarbonyl VOCs for tropospheric ozone formation. Cumulative cancer risk estimated for all the carcinogenic species was found to be 2792 for 1 million population, while the total noncancer hazard index (HI) was estimated to be 246 for the occupational exposure to different compounds from surface emission to the dump-site workers at Dhapa.

Implications:This paper describes the real-time surface emission of NMVOCs from an open municipal solid waste (MSW) dump site studied using a flux chamber. Our study findings indicate that while planning for new landfill site in tropical meteorology, real-time emission data must be considered, rather than relying on modeled data. The formation of tropospheric ozone from emitted NMVOC has also been studied. Our result shows how an open landfill site acts as a source and adds to the tropospheric ozone for the airshed of a metropolitan city.     

Application of Genetic Algorithms for the Design of Ozone Control Strategies

ABSTRACT

Designing air quality management strategies is complicated by the difficulty in simultaneously considering large amounts of relevant data, sophisticated air quality models, competing design objectives, and unquantifiable issues. For many problems, mathematical optimization can be used to simplify the design process by identifying cost-effective solutions. Optimization applications for controlling nonlinearly reactive pollutants such as tropospheric ozone, however, have been lacking because of the difficulty in representing nonlinear chemistry in mathematical programming models.

We discuss the use of genetic algorithms (GAs) as an alternative optimization approach for developing ozone control strategies. A GA formulation is described and demonstrated for an urban-scale ozone control problem in which controls are considered for thousands of pollutant sources simultaneously. A simple air quality model is integrated into the GA to represent ozone transport and chemistry. Variations of the GA formulation for multiobjective and chance-constrained optimization are also presented. The paper concludes with a discussion of the practicality of using more sophisticated, regulatory-scale air quality models with the GA. We anticipate that such an approach will be practical in the near term for supporting regulatory decision-making.     

Increase in springtime tropospheric ozone at a mountainous site in Japan for the period 1998–2006

The trend of tropospheric ozone from 1998 to 2006 was examined based on continuous measurements made at a site on Mt. Happo, Japan. We focused our study on springtime ozone, to coincide with the East Asian continental outflow that dominates the lower tropospheric ozone over Japan during this season. The observed increase of ～1 ppbv yr^?1 in the mean ozone level was statistically significant. We also found that the probability distribution of the springtime ozone mixing ratios was substantially modified, with the ozone mixing ratios greatly increasing at the upper end of the probability distribution. This increase has been particularly large since 2003, with larger increases occurring at the higher percentiles. The number of high-ozone days doubled during 2003–2006 compared to 1999–2002. One of the very likely explanations is the enhancement of regional ozone pollution due to rapidly increasing anthropogenic emissions from East Asia.     

Sequencing diurnal air flow patterns for ozone exposure assessment around Houston,Texas

Understanding the human health impacts of ground level ozone requires detailed knowledge of its spatial–temporal distribution beyond that provided by surface monitoring networks. Here, a novel methodology based on unsupervised multivariate statistical techniques has been developed and used to identify the transport and dispersion patterns of tropospheric ozone. The hierarchical clustering method is used to visualize air flow patterns at two time scales relevant for ozone buildup. Sequentially executed statistical methods consider hourly 1-h surface wind field measurements. First, clustering is performed at the hourly time scale to identify 1-h surface flow patterns. Then, sequencing is performed at the daily time scale to identify groups of days sharing similar diurnal cycles for the surface flow. Selection of appropriate numbers of air flow patterns allows inference of regional transport and dispersion patterns for understanding population exposure to ozone. The methods are applied to the Houston, Galveston, and Beaumont-Port Arthur, TX study domain. Representative hourly wind field patterns are determined for the entire 2004 ozone season. Then, sequencing is performed for the 32 days in exceedance of the NAAQS for 8-h ozone. Four diurnal flow patterns capturing different ozone exceedance scenarios are isolated; each scenario is associated with a distinct spatial distribution for atmospheric pollutants.     

The variability of free tropospheric ozone over Beltsville,Maryland (39N, 77W) in the summers 2004–2007

Ozone profiles are often used to investigate day-to-day and year-to-year variability in origins of free tropospheric ozone. With this in mind, more than 50 ozonesonde launches were conducted in Beltsville, MD, during the summers of 2004 through 2007. Budgets of free tropospheric ozone were calculated for each ozone profile in the four summers using a laminar identification (LID) method and unusual episodes were analyzed with respect to meteorological variables. The laminar method showed that stratosphere-to-troposphere transport (ST) accounted for greater than 50% of the free tropospheric ozone column on 17% of days sampled, a more pronounced influence than regional convective and lightning (RCL) sources. The ST origins were confirmed with trajectories, and tracers (water vapor and potential vorticity). The amount of free tropospheric ozone from ST and RCL sources varied from year-to-year (up to 13%) and can be explained by differences in mean meteorological patterns. On average, almost 30% of the free tropospheric column was attributed to ST influence, about twice as much as RCL, although the LID method may not capture weeks-old lightning influences as in a chemical model. The prevalence of ST ozone in summertime Beltsville soundings was similar to six sounding sites in the IONS-04 campaign [Thompson, A.M., et al., 2007b. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 1. Summertime upper tropospheric/lower stratosphere ozone over northeastern North America. J. Geophys. Res. 112, D12S12; Thompson, A.M., et al., 2007c. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 2. Tropospheric ozone budgets and variability over northeastern North America. J. Geophys. Res. 112, D12S13.] and to statistics from a 30 year climatology of European soundings [Collette, A., Ancellet, G., 2005. Impact of vertical transport processes on the tropospheric ozone layering above Europe. Part II: Climatological analysis of the past 30 years. Atmos. Environ. 39, 5423–5435]. The Beltsville record also demonstrated the value of soundings for air quality forecasting in an urban area. The 22 nighttime soundings collected over Beltsville in 2004–2007 can be divided into distinct polluted and unpolluted subsets, the former 20 ppbv higher in residual layer ozone (1 km) than the latter. These distinctions propagated to daytime differences of 10 ppbv at the surface in the Washington, DC, area, with the high-ozone residual layers leading to non-attainment of the National Ambient Air Quality Standard for ozone. More frequent ozone observations aloft appear essential for better understanding ozone variability and for enabling air quality modelers to achieve more accurate ozone forecasts.     

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

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

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

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

The Southeastern Aerosol Research and Characterization Study: part 1--Overview

This paper presents an overview of a major, long-term program for tropospheric gas and aerosol research in the southeastern United States. Building on three existing ozone (O3)-focused research sites begun in mid-1992, the Southeastern Aerosol Research and Characterization Study (SEARCH) was initiated in mid-1998 as a 7-year observation and research program with a broader focus including aerosols and an expanded geographical coverage in the Southeast. The monitoring network comprises four urban-rural (or urban-suburban) site pairs at locations along the coast of the Gulf of Mexico and inland, including two moderately sized and two major urban areas (Pensacola, FL; Gulfport, MS; Atlanta, GA; and Birmingham, AL). The sites are equipped with an extensive suite of instruments for measuring particulate matter (PM), gases relevant to secondary O3 and the production of secondary aerosol particles, and surface meteorology. The measurements taken to date have added substantially to the knowledge about the temporal behavior and geographic variability of tropospheric aerosols in the Southeast. Details are presented in four papers to follow.     

Diurnal variability of total ozone column over Madrid (Spain)

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

Closing Remarks

Considerable attention has been paid in recent years to photochemical smog pollution close to the earth's surface and to stratospheric ozone depletion. There is reason to suspect that the next round of scientific concern will be devoted to the perturbations in the “free troposphere.” Tropospheric ozone has been building up in many regions of the northern hemisphere. Ozone changes in the upper troposphere will exert a considerable impact on global warming. This could affect moisture levels, cloud amount and distribution, precipitation, and atmospheric dynamics on different scales.

This paper analyzes: (1) the physical and chemical processes contributing to changes in tropospheric ozone concentration; (2) the observational evidence of previous ozone change; and (3) results drawn from computer modelling of past and future radiative forcing caused by rising ozone concentrations in the upper troposphere.

The solar and longwave radiative model developed by Wang et al. (1991) was used for calculating the change in radiative forcing to the troposphere-surface system that can be ascribed to changing concentrations in ozone and other greenhouse gases. Nitric oxide emission from aircraft are a prime suspect for the observed increases in upper tropospheric ozone. The inference can be drawn that a radiative forcing of 0.2 to 0.35 Wm^-2 will result from a doubling of aircraft emissions over the next two decades. This will amount to 10 to 25 percent of the radiative forcing attributable to CO₂ alone for the same period. The effect of doubling aircraft emissions will increase as stratospheric ozone concentrations recover from the recent buildup of harmful chlorofluorocarbons. A large fraction of the radiative forcing that occurred during the 1970 to 1990 period can be attributed to increases in tropospheric ozone as opposed to increases in other greenhouse gases.     

A chamberless field exposure system for ozone enrichment of short vegetation

Only few studies have been conducted as yet which focus on the effects of rising tropospheric ozone levels on semi-natural vegetation under free-air conditions. A new technical approach was used to examine the response of calcareous grassland to ozone employing a chamberless fumigation system. Four different ozone regimes were applied (1-, 1.33-, 1.66- and 2-fold ambient air levels) with five replicates each. Ozone enrichment was carried out on circular plots of 2 m in diameter by a computer controlled exposure system. Transparent windscreens encircling each plot accelerated the mixing of ambient air and ozone released. Thus, the use of blowers could be avoided. The exposure system presented here is regarded as an appropriate technique for free-air trace gas enrichment on short vegetation avoiding microclimatic alterations known to affect plant growth and pollutant uptake. Furthermore, the chosen technical set-up was rather cost-effective. Hence, it enabled the establishment of a larger number of replications providing the basis for results of higher statistical power.     

The Southeastern Aerosol Research and Characterization Study: Part 1—Overview

Abstract

This paper presents an overview of a major, long-term program for tropospheric gas and aerosol research in the southeastern United States. Building on three existing ozone (O₃)-focused research sites begun in mid-1992, the Southeastern Aerosol Research and Characterization Study (SEARCH) was initiated in mid-1998 as a 7-year observation and research program with a broader focus including aerosols and an expanded geographical coverage in the Southeast. The monitoring network comprises four urban-rural (or urban-suburban) site pairs at locations along the coast of the Gulf of Mexico and inland, including two moderately sized and two major urban areas (Pensacola, FL; Gulfport, MS; Atlanta, GA; and Birmingham, AL). The sites are equipped with an extensive suite of instruments for measuring particulate matter (PM), gases relevant to secondary O₃ and the production of secondary aerosol particles, and surface meteorology. The measurements taken to date have added substantially to the knowledge about the temporal behavior and geographic variability of tropospheric aerosols in the Southeast. Details are presented in four papers to follow.     

Response and potential of agroforestry crops under global change

The use of agroforestry crops is a promising tool for reducing atmospheric carbon dioxide concentration through fossil fuel substitution. In particular, plantations characterised by high yields such as short rotation forestry (SRF) are becoming popular worldwide for biomass production and their role acknowledged in the Kyoto Protocol. While their contribution to climate change mitigation is being investigated, the impact of climate change itself on growth and productivity of these plantations needs particular attention, since their management might need to be modified accordingly. Besides the benefits deriving from the establishment of millions of hectares of these plantations, there is a risk of increased release into the atmosphere of volatile organic compounds (VOC) emitted in large amounts by most of the species commonly used. These hydrocarbons are known to play a crucial role in tropospheric ozone formation. This might represent a negative feedback, especially in regions already characterized by elevated ozone level.