Ozone uptake by citrus trees exposed to a range of ozone concentrations

The Citrus genus includes a large number of species and varieties widely cultivated in the Central Valley of California and in many other countries having similar Mediterranean climates. In the summer, orchards in California experience high levels of tropospheric ozone, formed by reactions of volatile organic compounds (VOC) with oxides of nitrogen (NO_x). Citrus trees may improve air quality in the orchard environment by taking up ozone through stomatal and non-stomatal mechanisms, but they may ultimately be detrimental to regional air quality by emitting biogenic VOC (BVOC) that oxidize to form ozone and secondary organic aerosol downwind of the site of emission. BVOC also play a key role in removing ozone through gas-phase chemical reactions in the intercellular spaces of the leaves and in ambient air outside the plants. Ozone is known to oxidize leaf tissues after entering stomata, resulting in decreased carbon assimilation and crop yield. To characterize ozone deposition and BVOC emissions for lemon (Citrus limon), mandarin (Citrus reticulata), and orange (Citrus sinensis), we designed branch enclosures that allowed direct measurement of fluxes under different physiological conditions in a controlled greenhouse environment. Average ozone uptake was up to 11 nmol s^?1 m^?2 of leaf. At low concentrations of ozone (40 ppb), measured ozone deposition was higher than expected ozone deposition modeled on the basis of stomatal aperture and ozone concentration. Our results were in better agreement with modeled values when we included non-stomatal ozone loss by reaction with gas-phase BVOC emitted from the citrus plants. At high ozone concentrations (160 ppb), the measured ozone deposition was lower than modeled, and we speculate that this indicates ozone accumulation in the leaf mesophyll.     

Rapid measurement of indoor mass-transfer coefficients

Indoor air pollutant concentrations can be influenced by how rapidly species are transported to and from surfaces. Consequently, a greater understanding of indoor transport phenomena to surfaces improves estimates of human exposure to indoor air pollutants. Here, we introduce two methods of rapidly and directly measuring species fluxes at indoor surfaces, allowing us to evaluate the transport-limited deposition velocity, v_t (a mass-transfer coefficient). The deposition velocity sensor (DeVS) method employs a small microbalance coated with a pure hydrocarbon, preferably octadecane. We quantify flux (or evaporation rate) of the hydrocarbon into a room by observing the rate of mass loss on the microbalance. The transport-limited deposition velocity, v_t,octadecane, is then obtained by combining the flux with the vapor pressure of the hydrocarbon. Simultaneously, v_t,ozone is quantified using the deposition velocity of ozone (DeVO) method, which acts as a standard to calibrate and evaluate DeVS. Specifically, DeVO evaluates ozone transport to surfaces by quantifying the conversion by ozone of nitrite to nitrate on a glass fiber filter. Simultaneous laboratory chamber experiments demonstrates that v_t for octadecane and ozone are strongly correlated, with the values for ozone 1.5 times greater than that for octadecane. In an office experiments, the DeVS method responds within minutes to step changes in conditions such as occupancy, activities and ventilation. At present, the results are in order-of-magnitude agreement with predicted indoor mass-transfer coefficients.     

Development of a field test method to evaluate gaseous air cleaner performance in a multizone building

The performance of gaseous air cleaners for commercial and residential buildings has typically been evaluated using test protocols developed for a controlled laboratory chamber or a test duct. It is currently unknown how laboratory measurements relate to the actual performance of an air cleaner installed in a real building. However, to date, there are no air cleaner field test protocols available, thereby limiting the existing field data. The National Institute of Standards and Technology (NIST) has conducted a series of experiments to support test procedure development for evaluating the installed performance of gaseous air cleaning equipment, as well as metrics for characterizing field performance. To date, over 100 experiments have been completed, of which 23 portable air cleaner experiments and 6 in-duct air cleaner experiments are described in this paper. Tests were conducted in a finished three-bedroom/two-bathroom manufactured house equipped with several gas chromatographs to semi-continuously measure air change rates and volatile organic compound concentrations. Experimental variables included air cleaner location, isolation of zones by closing doors, and contaminant source location. For each experiment, air cleaner removal of decane was directly measured using the air cleaner inlet and outlet concentrations, as well as with mass balance analyses using measured room concentrations. With a verified mass balance model, a field performance metric was developed to compare installed whole-building performance to the performance predicted by a laboratory result. The results provide insight into the protocols and metrics that might prove useful for characterizing the field performance of air cleaners as well as the impact of air cleaner removal on zonal concentration levels in a variety of situations.     

Weekday vs. Weekend Ambient Ozone Concentrations: Discussion and Hypotheses with Focus on Northern California

Abstract

Since the early 1970s, researchers and data analysts have reported differences between weekday and weekend ozone concentrations, with higher ozone concentrations occurring on Sundays in some locations. At that time, the phenomenon was referred to as the “Sunday effect.” In the late 1980s, additional papers focused on weekday/weekend differences in air quality in the South Coast (Los Angeles) Air Basin.

Analyses of ozone concentrations measured at a number of locations in northern California reveal that average ozone concentrations are frequently higher on weekends than on weekdays. Violations of the California 0.09 ppm 1-hour air quality standard for ozone also occur in disproportionately greater frequency on weekends. We hypothesize that this phenomenon is based largely on the differences between weekday and weekend emission patterns. We believe that the observed differences may provide information regarding which pollutant reduction strategy, NO_x or ROG control, may be more effective in reducing ambient ozone concentrations. For the northern California region, the presence of higher weekend ozone concentrations suggests the need for ROG control is greater than for NO_x control. If both NO_x and ROG are to be controlled, it is important to understand the interdependence of the two pollutants in forming ozone. With the current uncertainty and debate regarding official vehicular emission inventories, this phenomenon emphasizes the importance of using observation-based data to examine ambient pollution and emission relationships. This natural experiment of varying emissions provides an interesting test case for sophisticated air pollution model performance and evaluation.

Using a Bay Area emission inventory and an estimate of its change from weekday to weekend, combined with a generic Empirical Kinetic Modeling Approach (EKMA) diagram, we demonstrate the weekend effect. In addition, changes in the Bay Area emission inventory from 1980 to 1990, when combined with the EKMA diagram, also show why the weekend effect is more evident in the 1990s.

It is our hypothesis that the presence of the weekend effect, positive or negative, combined with changes in emission changes, provides a simple clue to whether an area is NO_xor ROG limited with respect to ozone formation.     

Initial efficiencies of air cleaners for the removal of nitrogen dioxide and volatile organic compounds

The objective of this research was to measure the initial effective cleaning rates (ECRs) of selected air cleaners for removing nitrogen dioxide (NO₂) and six representative volatile organic compounds (VOC) from air. Four portable air cleaners, representing different principles of particle removal and incorporating activated carbon, were investigated. Experiments were conducted in a closed room-size environmental chamber using analyte concentrations similar to those reported in residences. Effects of relative humidity, temperature, filter particle loading and saturation of the adsorbents on the ECRs were not investigated in this preliminary study. However, the effect of extended usage was investigated for one air cleaner.Two of the air cleaners were found to be reasonably effective initially in removing NO₂ and five of the six VOC. These two devices had relatively high flow rates and the greatest amounts of activated carbon. None of the devices removed dichloromethane, the VOC with the highest vapor pressure. One air cleaner emitted 1,1,1-trichloroethane and formaldehyde. After being used in a residence for 150 h, the ECRs for the air cleaner which had the highest initial values decreased to 50% or less of the initial ECRs. This use was only about 15% of the recommended filter lifetime. Conversion of NO₂ to NO was also observed for this device but only after it had been used in the residence.     

Predicting ozone levels

This paper presents a statistical model that is capable of predicting ozone levels from precursor concentrations and meteorological conditions during daylight hours in the Shuaiba Industrial Area (SIA) of Kuwait. The model has been developed from ambient air quality data that was recorded for one year starting from December 1994 using an air pollution mobile monitoring station. The functional relationship between ozone level and the various independent variables has been determined by using a stepwise multiple regression modelling procedure. The model contains two terms that describe the dependence of ozone on nitrogen oxides (NOx) and nonmethane hydrocarbon precursor concentrations, and other terms that relate to wind direction, wind speed, sulphur dioxide (SO₂) and solar energy. In the model, the levels of the precursors are inversely related to ozone concentration, whereas SO₂ concentration, wind speed and solar radiation are positively correlated. Typically, 63 % of the variation in ozone levels can be explained by the levels of NOx. The model is shown to be statistically significant and model predictions and experimental observations are shown to be consistent. A detailed analysis of the ozone-temperature relationship is also presented; at temperatures less than 27 °C there is a positive correlation between temperature and ozone concentration whereas at temperatures greater than 27 °C a negative correlation is seen. This is the first time a non-monotonic relationship between ozone levels and temperature has been reported and discussed.     

Reactions between ozone and building products: Impact on primary and secondary emissions

Reactions of ozone on common building products were studied in a dedicated emission test chamber system. Fourteen new and unused products were exposed to 100–160 ppb of ozone at 23 °C and 50% RH during 48 h experiments. Ozone deposition velocities calculated at steady state were between 0.003 cm s⁻¹ (alkyd paint on polyester film) and 0.108 cm s⁻¹ (pine wood board). All tested product showed modified emissions when exposed to ozone and secondary emissions of several aldehydes were identified. Carpets and wall coverings emitted mainly C₅–C₁₀ n-aldehydes, typical by-products of surface reactions. Linoleum, polystyrene tiles and pine wood boards also showed increased emissions of formaldehyde, benzaldehyde and hexanal associated with reduced emissions of unsaturated compounds suggesting the occurrence of gas-phase reactions. The ozone removal on the different tested products was primarily associated with surface reactions. The relative contribution of gas-phase reactions to the total ozone removal was estimated to be between 5% and 30% for pine wood boards depending on relative humidity (RH) and on the incoming ozone concentration and 2% for polystyrene tiles. On pine wood board, decreasing ozone deposition velocities were measured with increasing ozone concentrations and with RH increasing in the range 30–50%.     

A simple semi-empirical photochemical model for the simulation of ozone concentration in the Seoul metropolitan area in Korea

O₃ concentrations were simulated over the Seoul metropolitan area in Korea using a simple semi-empirical reaction (SEGRS) model which consists of generic reaction set (GRS), photochemical reaction set, and the diagnostic wind field generation model. The aggregated VOC emission strength was empirically scaled by the comparison of the simulated slope of (O₃–2NO–NO₂) concentration as a function of cumulative actinic light flux against measurements on high surface ozone concentration days with the relatively weak easterly geostrophic winds at the 850 hPa level in summer when the effect of horizontal advection was fairly small. The results indicated that the spatial distribution patterns and temporal variations of spatially averaged ground-level ozone concentrations were quite well simulated compared with those of observations with the modified volatile organic compound (VOC) emission strength. The diurnal trend of the surface ozone concentration and the maximum concentration compared observations were also quite reasonably simulated. However, the maximum ozone concentration occurring time at Seoul lagged about 2 h and the ozone concentration in the suburban area was slightly overestimated in the afternoon due to the influx of high ozone concentration from the urban area. It was found that the SEGRS model could be effectively used to simulate or predict the ground-level ozone concentration reasonably well without heavy computational cost provided the emission of ozone precursors are given.     

Uncertainties in predicted ozone concentrations due to input uncertainties for the UAM-V photochemical grid model applied to the July 1995 OTAG domain

The photochemical grid model, UAM-V, has been used by regulatory agencies to make decisions concerning emissions controls, based on studies of the July 1995 ozone episode in the eastern US. The current research concerns the effect of the uncertainties in UAM-V input variables (emissions, initial and boundary conditions, meteorological variables, and chemical reactions) on the uncertainties in UAM-V ozone predictions. Uncertainties of 128 input variables have been estimated and most range from about 20% to a factor of two. 100 Monte Carlo runs, each with new resampled values of each of the 128 input variables, have been made for given sets of median emissions assumptions. Emphasis is on the maximum hourly-averaged ozone concentration during the 12–14 July 1995 period. The distribution function of the 100 Monte Carlo predicted domain-wide maximum ozone concentrations is consistently close to log-normal with a 95% uncertainty range extending over plus and minus a factor of about 1.6 from the median. Uncertainties in ozone predictions are found to be most strongly correlated with uncertainties in the NO₂ photolysis rate. Also important are wind speed and direction, relative humidity, cloud cover, and biogenic VOC emissions. Differences in median predicted maximum ozone concentrations for three alternate emissions control assumptions were investigated, with the result that (1) the suggested year-2007 emissions changes would likely be effective in reducing concentrations from those for the year-1995 actual emissions, that (2) an additional 50% NO_x emissions reductions would likely be effective in further reducing concentrations, and that (3) an additional 50% VOC emission reductions may not be effective in further reducing concentrations.     

Turbulence effects on chemical reactions in smog chamber flows

Turbulent mixing effects on the reaction rate of a non-premixed flow are presented for a moderately slow second-order irreversible chemical reaction. The turbulent mixing process leads to inhomogeneities in the concentration of the reactants. Chemical reactions are normally highly non-linear and large errors can result from using average concentrations in the computation of mean reaction rates. A brief review of the literature on this problem and its application areas is made with particular emphasis placed on near isothermal flows where the fluctuation in the reaction rate constant can be neglected. The reaction between mixing air jets containing dilute nitric oxide, NO, and ozone, O₃, is studied in a large Turbulent Smog Chamber (TSC) under conditions of high Reynolds number, three-dimensional flow. The measured reactant concentrations, obtained with good time and space resolution, are used to investigate the effects of the reactant species concentration fluctuations on the mean reactant species concentration field through their contribution to the mean reaction rate. Two flow geometries have been studied: two opposed jets issuing into a large chamber and a plume-like source issuing into a turbulent background flow. A three-dimensional finite-difference computation has been carried out for the flow in the chamber using the k-ε-g model of turbulence and mixing. The reacting species concentration field is calculated by considering the transport of a ‘perturbation variable’ equal to the mean of the difference between the species concentration and its corresponding fast chemistry value. A closure for the mean chemical reaction rate based on this quantity is presented and its experimental validation discussed.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.     

The impact of building recirculation rates on secondary organic aerosols generated by indoor chemistry

Numerous investigators have documented increases in the concentrations of airborne particles as a consequence of ozone/terpene reactions in indoor environments. This study examines the effect of building recirculation rates on the concentrations of secondary organic aerosol (SOA) resulting from reactions between indoor limonene and ozone. The experiments were conducted in a large environmental chamber using four recirculation rates (11, 14, 19 and 24 air change per hour (ACH)) and a constant outdoor air exchange rate (1 ACH) as well as constant emission rates for limonene and ozone. As the recirculation rates increased, the deposition velocities of ozone and SOA increased. As a consequence of reduced production rates (due to less ozone) and larger surface removal rates, number and mass concentrations of SOA in different size ranges decreased significantly at higher recirculation rates. Enhanced coagulation at higher recirculation rates also reduced particle number concentrations, while shifting size-distributions towards larger particles. The results have health implications beyond changes in exposures, since particle size is a factor that determines where a particle deposits in the respiratory tract.     

Modeling toxic compounds from nitric oxide emission measurements

Determining the amount and rate of degradation of toxic pollutants in soil and groundwater is difficult and often requires invasive techniques, such as deploying extensive monitoring well networks. Even with these networks, degradation rates across entire systems cannot readily be extrapolated from the samples. When organic compounds are degraded by microbes, especially nitrifying bacteria, oxides or nitrogen (NO_x) are released to the atmosphere. Thus, the flux of nitric oxide (NO) from the soil to the lower troposphere can be used to predict the rate at which organic compounds are degraded. By characterizing and applying biogenic and anthropogenic processes in soils the rates of degradation of organic compounds. Toluene was selected as a representative of toxic aromatic compounds, since it is inherently toxic, it is a substituted benzene compound and is listed as a hazardous air pollutant under Section 12 of the Clean Air Act Amendments of 1990. Measured toluene concentrations in soil, microbial population growth and NO fluxes in chamber studies were used to develop and parameterize a numerical model based on carbon and nitrogen cycling. These measurements, in turn, were used as indicators of bioremediation of air toxic (i.e. toluene) concentrations. The model found that chemical concentration, soil microbial abundance, and NO production can be directly related to the experimental results (significant at P < 0.01) for all toluene concentrations tested. This indicates that the model may prove useful in monitoring and predicting the fate of toxic aromatic contaminants in a complex soil system. It may also be useful in predicting the release of ozone precursors, such as changes in reservoirs of hydrocarbons and oxides of nitrogen. As such, the model may be a tool for decision makers in ozone non-attainment areas.     

Codependencies of Reactive Air Toxic and Criteria Pollutants on Emission Reductions

Abstract

It is important to understand the effects of emission controls on concentrations of ozone, fine particulate matter (PM_2.5), and hazardous air pollutants (HAPs) simultaneously, to evaluate the full range of health, ecosystem, and economic effects. Until recently, the capability to simultaneously evaluate interrelated atmospheric pollutants (“one atmosphere” analysis) was unavailable to air quality managers. In this work, we use an air quality model to examine the potential effect of three emission reductions on concentrations of ozone, PM_2.5, and four important HAPs (formaldehyde, acetaldehyde, acrolein, and benzene) over a domain centered on Philadelphia for 12-day episodes in July and January 2001. Although NO_x controls are predicted to benefit PM_2.5 concentrations and sometimes benefit ozone, they have only a small effect on formaldehyde, slightly increase acetaldehyde and acrolein, and have no effect on benzene in the July episode. Concentrations of all pollutants except benzene increase slightly with NO_x controls in the January simulation. Volatile organic compound controls alone are found to have a small effect on ozone and PM_2.5, a less than linear effect on decreasing aldehydes, and an approximately linear effect on acrolein and benzene in summer, but a slightly larger than linear effect on aldehydes and acrolein in winter. These simulations indicate the difficulty in assessing how toxic air pollutants might respond to emission reductions aimed at decreasing criteria pollutants such as ozone and PM_2.5.     

Modeling the long-term frequency distribution of regional ozone concentrations

Efficient methods are developed for modeling emissions – air quality relationships that govern ozone and NO₂ concentrations over very long periods of time. A baseline model evaluation study is conducted to assess the accuracy and speed with which the relationship between pollutant emissions and the frequency distribution of O₃ concentrations throughout the year can be computed along with annual average NO₂ values using a deterministic photochemical airshed model driven by automated objective analysis of measured meteorological parameters. Methods developed are illustrated by application to the air quality situation that exists in Southern California. Model performance statistics for O₃ are similar to the results obtained in previous short-term episodic model evaluation studies that were based on hand-crafted meteorological inputs that are supplemented by expensive field measurement campaigns. Model predictions at one of the highest NO₂ concentration sites in the US indicate that measured violation of the US annual average NO₂ air quality standard at that site occurs because other species such as HNO₃ and PAN are measured as if they were NO₂ by the chemiluminescent NO_x monitors in current use.     

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.     

Evaluating Sources of Indoor Air Pollution

Evaluation of Indoor air pollution problems requires an understanding of the relationship between sources, air movement, and outdoor air exchange. Research is underway to investigate these relationships. A three-phase program is being implemented: 1) Environmental chambers are used to provide source emission factors for specific indoor pollutants; 2) An IAQ (Indoor Air Quality) model has been developed to calculate indoor pollutant concentrations based on chamber emissions data and the air exchange and air movement within the indoor environment; and 3) An IAQ test house is used to conduct experiments to evaluate the model results. Examples are provided to show how this coordinated approach can be used to evaluate specific sources of indoor air pollution. Two sources are examined: 1) para-dichlorobenzene emissions from solid moth repellant; and 2) particle emissions from unvented kerosene heaters.

The evaluation process for both sources followed the three-phase approach discussed above. Para-dichlorobenzene emission factors were determined by small chamber testing at EPA’s Air and Energy Engineering Research Laboratory. Particle emission factors for the kerosene heaters were developed In large chambers at the J. B. Pierce Foundation Laboratory. Both sources were subsequently evaluated in EPA’s IAQ test house. The IAQ model predictions showed good agreement with the test house measurements when appropriate values were provided for source emissions, outside air exchange, in-house air movement, and deposition on “sink” surfaces.     

Air quality during the 2008 Beijing Olympic Games

China is taking major steps to improve Beijing's air quality for the 2008 Olympic Games. However, concentrations of fine particulate matter and ozone in Beijing often exceed healthful levels in the summertime. Based on the US EPA's Models-3/CMAQ model simulation over the Beijing region, we estimate that about 34% of PM_2.5 on average and 35–60% of ozone during high ozone episodes at the Olympic Stadium site can be attributed to sources outside Beijing. Neighboring Hebei and Shandong Provinces and the Tianjin Municipality all exert significant influence on Beijing's air quality. During sustained wind flow from the south, Hebei Province can contribute 50–70% of Beijing's PM_2.5 concentrations and 20–30% of ozone. Controlling only local sources in Beijing will not be sufficient to attain the air quality goal set for the Beijing Olympics. There is an urgent need for regional air quality management studies and new emission control strategies to ensure that the air quality goals for 2008 are met.     

Evaluating sources of indoor air pollution

Evaluation of indoor air pollution problems requires an understanding of the relationship between sources, air movement, and outdoor air exchange. Research is underway to investigate these relationships. A three-phase program is being implemented: 1) Environmental chambers are used to provide source emission factors for specific indoor pollutants; 2) An IAQ (Indoor Air Quality) model has been developed to calculate indoor pollutant concentrations based on chamber emissions data and the air exchange and air movement within the indoor environment; and 3) An IAQ test house is used to conduct experiments to evaluate the model results. Examples are provided to show how this coordinated approach can be used to evaluate specific sources of indoor air pollution. Two sources are examined: 1) para-dichlorobenzene emissions from solid moth repellant; and 2) particle emissions from unvented kerosene heaters. The evaluation process for both sources followed the three-phase approach discussed above. Para-dichlorobenzene emission factors were determined by small chamber testing at EPA's Air and Energy Engineering Research Laboratory. Particle emission factors for the kerosene heaters were developed in large chambers at the J. B. Pierce Foundation Laboratory. Both sources were subsequently evaluated in EPA's IAQ test house. The IAQ model predictions showed good agreement with the test house measurements when appropriate values were provided for source emissions, outside air exchange, in-house air movement, and deposition on "sink" surfaces.