Observing ozone chemistry in an occupied residence.

Outdoor ozone transported indoors initiates oxidative chemistry, forming volatile organic products. The influence of ozone chemistry on indoor air composition has not been directly quantified in normally occupied residences. Here, we explore indoor ozone chemistry in a house in California with two adult inhabitants. We utilize space- and time-resolved measurements of ozone and volatile organic compounds (VOCs) acquired over an 8-wk summer campaign. Despite overall low indoor ozone concentrations (mean value of 4.3 ppb) and a relatively low indoor ozone decay constant (1.3 h-1), we identified multiple VOCs exhibiting clear contributions from ozone-initiated chemistry indoors. These chemicals include 6-methyl-5-hepten-2-one (6-MHO), 4-oxopentanal (4-OPA), nonenal, and C8-C12 saturated aldehydes, which are among the commonly reported products from laboratory studies of ozone interactions with indoor surfaces and with human skin lipids. These VOCs together accounted for ≥12% molecular yield with respect to house-wide consumed ozone, with the highest net product yield for nonanal (≥3.5%), followed by 6-MHO (2.7%) and 4-OPA (2.6%). Although 6-MHO and 4-OPA are prominent ozonolysis products of skin lipids (specifically squalene), ozone reaction with the body envelopes of the two occupants in this house are insufficient to explain the observed yields. Relatedly, we observed that ozone-driven chemistry continued to produce 6-MHO and 4-OPA even after the occupants had been away from the house for 5 d. These observations provide evidence that skin lipids transferred to indoor surfaces made substantial contributions to ozone reactivity in the studied house.

Co-occurrence of extremes in surface ozone, particulate matter, and temperature over eastern North America.

Heat waves and air pollution episodes pose a serious threat to human health and may worsen under future climate change. In this paper, we use 15 years (1999-2013) of commensurately gridded (1° x 1°) surface observations of extended summer (April-September) surface ozone (O3), fine particulate matter (PM2.5), and maximum temperature (TX) over the eastern United States and Canada to construct a climatology of the coincidence, overlap, and lag in space and time of their extremes. Extremes of each quantity are defined climatologically at each grid cell as the 50 d with the highest values in three 5-y windows (∼95th percentile). Any two extremes occur on the same day in the same grid cell more than 50% of the time in the northeastern United States, but on a domain average, co-occurrence is approximately 30%. Although not exactly co-occurring, many of these extremes show connectedness with consistent offsets in space and in time, which often defy traditional mechanistic explanations. All three extremes occur primarily in large-scale, multiday, spatially connected episodes with scales of >1,000 km and clearly coincide with large-scale meteorological features. The largest, longest-lived episodes have the highest incidence of co-occurrence and contain extreme values well above their local 95th percentile threshold, by +7 ppb for O3, +6 µg m-3 for PM2.5, and +1.7 °C for TX. Our results demonstrate the need to evaluate these extremes as synergistic costressors to accurately quantify their impacts on human health.

Ozone concentration in the ground atmosphere and morbidity during extreme heat in the summer of 2010.

Dependence of the population morbidity on the ground-level ozone concentration in the summer of 2010 was studied in a city with low urbanization (Vyatskie Polyany, Kirov oblast) and in Moscow. At a high air temperature and low ozone concentration, the population morbidity was not associated with these parameters in Vyatskie Polyany. When the average daily ground-level ozone concentration exceeded 60 µg/m3 for 13 successive days, the correlation coefficient between ozone concentration and the number of ambulance calls was statistically significant, r = 0.62. Heavy smoke from forest fires reduced ozone concentration, and the number of emergency calls did not increase. In Moscow, the incidence of respiratory diseases and population mortality were growing up at high ozone concentrations.

Impact of physical properties on ozone removal by several porous materials.

Models of reactive uptake of ozone in indoor environments generally describe materials through aerial (horizontal) projections of surface area, a potentially limiting assumption for porous materials. We investigated the effect of changing porosity/pore size, material thickness, and chamber fluid mechanic conditions on the reactive uptake of ozone to five materials: two cellulose filter papers, two cementitious materials, and an activated carbon cloth. Results include (1) material porosity and pore size distributions, (2) effective diffusion coefficients for ozone in materials, and (3) material-ozone deposition velocities and reaction probabilities. At small length scales (0.02-0.16 cm) increasing thickness caused increases in estimated reaction probabilities from 1 × 10(-6) to 5 × 10(-6) for one type of filter paper and from 1 × 10(-6) to 1 × 10(-5) for a second type of filter paper, an effect not observed for materials tested at larger thicknesses. For high porosity materials, increasing chamber transport-limited deposition velocities resulted in increases in reaction probabilities by factors of 1.4-2.0. The impact of physical properties and transport effects on values of the Thiele modulus, ranging across all materials from 0.03 to 13, is discussed in terms of the challenges in estimating reaction probabilities to porous materials in scenarios relevant to indoor environments.

Gas-phase advanced oxidation for effective, efficient in situ control of pollution.

In this article, gas-phase advanced oxidation, a new method for pollution control building on the photo-oxidation and particle formation chemistry occurring in the atmosphere, is introduced and characterized. The process uses ozone and UV-C light to produce in situ radicals to oxidize pollution, generating particles that are removed by a filter; ozone is removed using a MnO2 honeycomb catalyst. This combination of in situ processes removes a wide range of pollutants with a comparatively low specific energy input. Two proof-of-concept devices were built to test and optimize the process. The laboratory prototype was built of standard ventilation duct and could treat up to 850 m(3)/h. A portable continuous-flow prototype built in an aluminum flight case was able to treat 46 m(3)/h. Removal efficiencies of >95% were observed for propane, cyclohexane, benzene, isoprene, aerosol particle mass, and ozone for concentrations in the range of 0.4-6 ppm and exposure times up to 0.5 min. The laboratory prototype generated a OH(•) concentration derived from propane reaction of (2.5 ± 0.3) × 10(10) cm(-3) at a specific energy input of 3 kJ/m(3), and the portable device generated (4.6 ± 0.4) × 10(9) cm(-3) at 10 kJ/m(3). Based on these results, in situ gas-phase advanced oxidation is a viable control strategy for most volatile organic compounds, specifically those with a OH(•) reaction rate higher than ca. 5 × 10(-13) cm(3)/s. Gas-phase advanced oxidation is able to remove compounds that react with OH and to control ozone and total particulate mass. Secondary pollution including formaldehyde and ultrafine particles might be generated, depending on the composition of the primary pollution.

BioArena system for knowing and understanding the biological world: a review with new experimental results.

A simple observation is the basis of the development of BioArena system: according to the first observations during the biological incubation after inoculation there is formaldehyde (HCHO) emission from the chromatographic spots; in this emission process, the level of HCHO molecules decreases time dependently. In fact, the antibiotic effect of an antibiotic-like compound decreases in parallel with the HCHO emission. The investigations demonstrated clearly a unique function and role of endogenous HCHO and its one main reaction product, ozone (O3), in the antiproliferative (e.g., antimicrobial) effect of different molecules with diverse chemical structures. The results in BioArena can be extended for in vivo conditions (e.g., greenhouse experiments), as well. For the pretreatment with different doses of inducers (immunostimulation-inducing molecules) there are always four bioequivalent immunostimulating response ranges (quadruple bioequivalent immune response system) in plants. The inducers (e.g., N-methylated basic amino acids, salicylic acid, cinnamic acid, and trace elements) do not participate directly in the induction of the immunostimulating effect. These new findings support a statement that HCHO and its reaction products (mainly O3), as bioreactive small molecules, are responsible for the immunostimulating activity (in vivo conditions), as well.

Measurements of tropospheric NO2 in Romania using a zenith-sky mobile DOAS system and comparisons with satellite observations.

In this paper we present a new method for retrieving tropospheric NO2 Vertical Column Density (VCD) from zenith-sky Differential Optical Absorption Spectroscopy (DOAS) measurements using mobile observations. This method was used during three days in the summer of 2011 in Romania, being to our knowledge the first mobile DOAS measurements peformed in this country. The measurements were carried out over large and different areas using a mobile DOAS system installed in a car. We present here a step-by-step retrieval of tropospheric VCD using complementary observations from ground and space which take into account the stratospheric contribution, which is a step forward compared to other similar studies. The detailed error budget indicates that the typical uncertainty on the retrieved NO2tropospheric VCD is less than 25%. The resulting ground-based data set is compared to satellite measurements from the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment-2 (GOME-2). For instance, on 18 July 2011, in an industrial area located at 47.03°N, 22.45°E, GOME-2 observes a tropospheric VCD value of (3.4 ± 1.9) × 1015 molec./cm2, while average mobile measurements in the same area give a value of (3.4 ± 0.7) × 10(15) molec./cm2. On 22 August 2011, around Ploiesti city (44.99°N, 26.1°E), the tropospheric VCD observed by satellites is (3.3 ± 1.9) × 10(15) molec./cm2 (GOME-2) and (3.2 ± 3.2) × 10(15) molec./cm2 (OMI), while average mobile measurements give (3.8 ± 0.8) × 10(15) molec./cm2. Average ground measurements over "clean areas", on 18 July 2011, give (2.5 ± 0.6) × 10(15) molec./cm2 while the satellite observes a value of (1.8 ± 1.3) × 10(15) molec./cm2.

Long-term performance of passive materials for removal of ozone from indoor air.

The health effects associated with exposure to ozone range from respiratory irritation to increased mortality. In this paper, we explore the use of three green building materials and an activated carbon (AC) mat that remove ozone from indoor air. We studied the effects of long-term exposure of these materials to real environments on ozone removal capability and pre- and post-ozonation emissions. A field study was completed over a 6-month period, and laboratory testing was intermittently conducted on material samples retrieved from the field. The results show sustained ozone removal for all materials except recycled carpet, with greatest ozone deposition velocity for AC mat (2.5-3.8 m/h) and perlite-based ceiling tile (2.2-3.2 m/h). Carbonyl emission rates were low for AC across all field sites. Painted gypsum wallboard and perlite-based ceiling tile had similar overall emission rates over the 6-month period, while carpet had large initial emission rates of undesirable by-products that decayed rapidly but remained high compared with other materials. This study confirms that AC mats and perlite-based ceiling tile are viable surfaces for inclusion in buildings to remove ozone without generating undesirable by-products. PRACTICAL IMPLICATIONS The use of passive removal materials for ozone control could decrease the need for, or even render unnecessary, active but energy consuming control solutions. In buildings where ozone should be controlled (high outdoor ozone concentrations, sensitive populations), materials specifically designed or selected for removing ozone could be implemented, as long as ozone removal is not associated with large emissions of harmful by-products. We find that activated carbon mats and perlite-based ceiling tiles can provide substantial, long-lasting, ozone control.

Squalene and cholesterol in dust from danish homes and daycare centers.

Given the rate at which humans shed their skin (desquamation), skin flakes that contain squalene and cholesterol are anticipated to be major constituents of indoor dust. These compounds have been detected in more than 97% of the dust samples collected from 500 bedrooms and 151 daycare centers of young children living in Odense, Denmark. The mass fractions of squalene in dust were approximately log-normally distributed (homes: GM = 32 µg/g, GSD = 4.3; daycare centers: GM = 11.5 µg/g, GSD = 4.3); those of cholesterol displayed a poorer fit to such a distribution (homes: GM = 625 µg/g, GSD = 3.4; daycare centers: GM = 220 µg/g, GSD = 4.0). Correlations between squalene and cholesterol were weak (r = 0.22). Furthermore, the median squalene-to-cholesterol ratio in dust (~0.05) was more than an order of magnitude smaller than that in skin oil. This implies sources in addition to desquamation (e.g., cholesterol from cooking) coupled, perhaps, with a shorter indoor lifetime for squalene. Estimated values of squalene's vapor pressure, while uncertain, suggest meaningful redistribution from dust to other indoor compartments. We estimate that dust containing squalene at 60 µg/g would contribute about 4% to overall ozone removal by indoor surfaces. This is roughly comparable to the fraction of ozone removal that can be ascribed to reactions with indoor terpenes. Squalene containing dust is anticipated to contribute to the scavenging of ozone in all settings occupied by humans.

Photochemical modeling in California with two chemical mechanisms: model intercomparison and response to emission reductions.

An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment. Therefore, additional study is required to evaluate the full regulatory implications of upgrading air quality models to SAPRC07.

RO filtration of biologically treated textile and dyeing effluents using ozonation as a pre-treatment.

Bench-scale experiments were conducted to investigate the application of ozonation pre-treatment for biologically treated textile and dyeing wastewater to improve performance of the RO process. Based on ozonation experiments, four specific ozone consumptions (SOC), 0, 0.3, 0.6, 4.0 mg O3/mg DOC0 were chosen for study of the effects of ozonation on the reverse osmosis (RO) process. Membrane flux was recorded. Also, the permeate water quality parameters such as TOC, conductivity were analyzed. In addition, fouled membrane cleaning was studied. The study further examined the nature and mechanisms of membrane fouling using scanning electron microscopy (SEM) and the energy dispersive X-ray spectrometer (EDS). The effect of ozonation on RO filtration was found to depend on SOC. The study revealed that significant improvement can be achieved in the efficiency of RO filtration by employing ozonation with 0.6 mg O3/mg DOC0 SOC. Although the product water purity slightly decreased, the ozonation pre-treatment showed advantages at 0.6 mg O3/mg DOC0 SOC for the following: (i) mitigation of flux decline due to membrane fouling; (ii) improvement in foulants cleanability. In addition, hypotheses were put forward to explain the reasons from the aspect of organic matter characteristics changed by ozonation, such as changing on functional groups and molecular weight of organic matter.

Evaluation of Ozone Removal by Spent Coffee Grounds.

Activated carbon is the most known material used to adsorb ozone. Activating carbonaceous materials by ozonation is commonly used to produce activated carbon, however, requiring sophisticated skills and professional equipment. This paper presents a reversed idea: to adsorb ozone using an unactivated carbonaceous material, coffee. Three powder adsorbents are presented: fresh coffee (unactivated), spent coffee grounds (unactivated), and activated carbon (commercially available). The test is conducted by measuring and comparing the ozone concentration in an ozone-supplied chamber with or without the ozone adsorbent. The results show that, at the specific conditions, the peak ozone concentration is lowered by 38% to 56% when the chamber has the activated carbon. At the same conditions, the peak ozone concentration is lowered by 25% to 43% when the chamber has the coffee powders (either fresh or spent). The elemental analysis demonstrates that the oxygen content after the ozone adsorption increases by 20%, 14.4%, and 34.5% for the fresh coffee, the spent coffee grounds, and the activated carbon, respectively. The characteristic analysis (the Fourier-transform infrared spectroscopy, the thermogravimetric, and the Brunauer-Emmett-Teller) suggests that the unactivated coffee is not porous, however, contains various organic compounds that could react with and consume ozone.

Elimination of laboratory ozone leads to a dramatic improvement in the reproducibility of microarray gene expression measurements.

BACKGROUND: Environmental ozone can rapidly degrade cyanine 5 (Cy5), a fluorescent dye commonly used in microarray gene expression studies. Cyanine 3 (Cy3) is much less affected by atmospheric ozone. Degradation of the Cy5 signal relative to the Cy3 signal in 2-color microarrays will adversely reduce the Cy5/Cy3 ratio resulting in unreliable microarray data. RESULTS: Ozone in central Arkansas typically ranges between approximately 22 ppb to approximately 46 ppb and can be as high as 60-100 ppb depending upon season, meteorological conditions, and time of day. These levels of ozone are common in many areas of the country during the summer. A carbon filter was installed in the laboratory air handling system to reduce ozone levels in the microarray laboratory. In addition, the airflow was balanced to prevent non-filtered air from entering the laboratory. These modifications reduced the ozone within the microarray laboratory to approximately 2-4 ppb. Data presented here document reductions in Cy5 signal on both in-house produced microarrays and commercial microarrays as a result of exposure to unfiltered air. Comparisons of identically hybridized microarrays exposed to either carbon-filtered or unfiltered air demonstrated the protective effect of carbon-filtration on microarray data as indicated by Cy5 and Cy3 intensities. LOWESS normalization of the data was not able to completely overcome the effect of ozone-induced reduction of Cy5 signal. Experiments were also conducted to examine the effects of high humidity on microarray quality. Modest, but significant, increases in Cy5 and Cy3 signal intensities were observed after 2 or 4 hours at 98-99% humidity compared to 42% humidity. CONCLUSION: Simple installation of carbon filters in the laboratory air handling system resulted in low and consistent ozone levels. This allowed the accurate determination of gene expression by microarray using Cy5 and Cy3 fluorescent dyes.

Inactivation of particle-associated microorganisms in wastewater disinfection: modeling of ozone and chlorine reactive diffusive transport in polydispersed suspensions.

Occlusion of microorganisms in wastewater particles often governs the overall performance of a disinfection system, and the associated health risks of post-disinfected effluents. Little is currently known on the penetration of chemical oxidants into particles developed in wastewater treatment. In this work, a reactive transport model that incorporates intra- and extra-particle chemical decay, radial intra-particle diffusion, mass transfer resistance at particle surfaces, and non-linear reaction kinetics within a competitive multi-particle size aqueous environment, was used to analyze the penetration of ozone and chlorine into wastewater particles. Individual characteristics from two secondary wastewater treatment facilities were used in model calibration. Simulations revealed that significant ozone transport within particles greater than 6 microm required large initial concentrations to exhaust the preferential reaction with aqueous soluble matter. Chlorinated samples exhibited apparently slower reactions and thus deeper penetration (22-40 microm). Chlorine penetration was less sensitive to variations in the extra-particle reaction and disinfectant concentration than ozone. Model simulations that considered elevated initial concentrations of chemical disinfectants revealed that complete inactivation of all particle size domains was not possible with current disinfection practices (e.g., contact times). Reduction in the health risks associated with wastewater particles requires treatment that efficiently balances particle removal (filtration) and particle inactivation (disinfection).

Elimination of volatile organic compounds by biofiltration: a review.

Volatile organic compounds (VOCs) are pollutants that are responsible for the formation of the tropospheric ozone, one of the precursors of smog. VOCs are emitted by various industries including chemical plants, pulp and paper mills, pharmaceuticals, cosmetics, electronics and agri-food industries. Some VOCs cause odor pollution while many of them are harmful to environment and human or animal health. For the removal of VOCs, biofiltration, a biological process, has proved to be reliable when properly operated. This process has therefore been widely applied in Europe and North America. The main advantages associated with the use of biofiltration are related to its set-up, maintenance, and operating costs which are usually lower than those related to other VOCs control technologies and because it is less harmful for the environment than conventional processes like incineration. In the present paper, the main parameters (type, moisture, pH, and temperature of filter bed, microbial population, nutrients concentrations, and VOCs' inlet load) to be controlled during the biofiltration are identified and described in detail. The main phenomena involved in biofiltration are also discussed. For improving the efficiency of VOC control biotechnology, new techniques are now proposed that include the use of membranes, biphasic reactors, UV photolysis, and many others.

Kinetics of the ozonation of muconic acid in water.

The removal of muconic acid (specifically trans-trans-butanedioc acid) with ozone from water has been studied for kinetics purposes. Concentrations of muconic acid of 4.4x10(-4)M are completely removed with ozone in less than 14 and 9 min at pH 3 and 7, respectively, and 3x10(-4)M of ozone in the gas. The positive influence of pH was due to the more reactive muconic acid dissociated form with ozone. The process can be described as a second order irreversible gas-liquid reaction developing in the moderate kinetic regime of absorption. At the experimental conditions investigated no free radical reactions are present and muconic acid is entirely oxidized by molecular ozone. Rate constants of the direct reaction between muconic acid and ozone were found to be 1.6x10(4) and 1.4x10(5)M(-1)s(1) at 20 degrees C, pH 3 and 7, respectively, according to film theory.

Continuous extraction and destruction of chloro-organics in wastewater using ozone-loaded Volasiltrade mark245 solvent.

Extracting waterborne contaminants to ozone-loaded Volasiltrade mark245 (a siloxane solvent in which ozone is ten times more soluble than water) has been studied as a means of enhancing reaction kinetics and thus, providing more rapid wastewater decontamination. Investigation was carried out with respect to 2-chlorophenol and dichloromethane. Using a pilot scale continuous flow liquid-liquid/ozone water treatment system, 2-chlorophenol was extracted to the ozone-loaded solvent phase and considerable extents of destruction were achieved. However, the approach was demonstrated to yield slightly less destruction than direct gas contact for the same utilization of ozone and enhanced reaction kinetics were not shown to occur. This was suggested to be due to increased interfacial mass transfer resistance and/or the promotion of less destructive reaction pathways. Modification of the existing pilot system, by conversion from co- to counter-current solvent-loading, enabled greater dissolved ozone concentrations to be achieved within the solvent. Increasing the counter-current exchange column height to approximately 2.5m was suggested for achieving a near optimum level of performance. The liquid-liquid/ozone approach was demonstrated to be an effective means of indirectly exposing wastewater contaminants to concentrated ozone. As such the technology may be applicable as an alternative to direct gas contact in instances where the avoidance of contaminant sparging is desired (i.e. where contaminants are highly volatile, pungent and/or toxic) or foaming occurs.

Effect of substrate Henry's constant on biofilter performance.

Butanol, ether, toluene, and hexane, which have Henry's constants ranging from 0.0005 to 53, were used to investigate the effects of substrate solubility or availability on the removal of volatile organic compounds (VOCs) in trickle-bed biofilters. Results from this study suggest that, although removal of a VOC generally increases with a decrease in its Henry's constant, an optimal Henry's constant range for biofiltration may exist. For the treatment of VOCs with high Henry's constant values, such as hexane and toluene, the transfer of VOCs between the vapor and liquid phases or between the vapor phase and the biofilm is a rate-determining step. However, oxygen (O2) transfer may become a rate-limiting step in treating VOCs with low Henry's constants, such as butanol, especially at high organic loadings. The results demonstrated that in a gas-phase aerobic biofilter, nitrate can serve both as a growth-controlling nutrient and as an electron acceptor in a biofilm for the respiration of VOCs with low Henry's constants. Microbial communities within the biofilters were examined using denaturing gradient gel electrophoresis to provide a more complete picture of the effect of O2 limitation and denitrification on biofilter performance.

Demonstrating attainment of the air quality standards: integration of observations and model predictions into the probabilistic framework.

This paper introduces an integrated observational-modeling approach to transform the deterministic nature of attainment demonstrations of the National Ambient Air Quality Standard (NAAQS) into the probabilistic framework. While the methods presented here can be used to address any air quality standard that is based on extreme values, this paper focuses on the application to the 1-hr and 8-hr NAAQS for ozone. Extreme value statistics and resampling techniques are applied to estimate the probability of exceeding the NAAQS for both 1-hr and 8-hr ozone concentrations. Within the integrated observation-modeling analysis approach, we show that the model-to-model differences in the predicted responses to emission reductions are smaller than the model-to-model differences in predicted absolute ozone concentrations. We illustrate that the emission reductions stemming from a real-world emission control strategy would substantially reduce the probability of exceeding the NAAQS over a large portion of the eastern United States, especially for the 8-hr average ozone concentrations.