Ozone emission rate testing and ranking method using environmental chamber

Ionization-based air cleaners can emit high concentrations of ozone. With the aim to limit the ozone concentration below the standard value in actual use conditions, we propose a standard procedure for testing and ranking the ozone emission of air cleaners. It is demonstrated by testing 27 samples of air cleaners that ozone emission rate can be measured in an airtight environmental chamber, by applying a generation-decay model to the concentration increase curve. The results indicate that deposition velocities v_d on chamber wall surfaces need to be better characterized so that the ozone emission of a tested product could be characterized by a three-parameter model. The model takes into account actual room sizes and surface material deposition effects to predict ozone concentrations in indoor applications. This procedure accounts for ozone decay effect in an explicit manner and allows using alternative testing chamber sizes other than as specified in the current Underwriters Laboratory standard.     

Rural and Urban Ozone Relationships In New York State

High ozone concentrations, often in excess of the national ambient air quality standard for photochemical oxidants, have been measured simultaneously in urban and rural areas of New York State. Average daily rural ozone concentrations were found to correlate well with daily maximum urban ozone concentrations suggesting a common source. Estimations of the quantity of ozone advectively transported into New York State are more than an order of magnitude greater than estimations of the potential photochemical generation of ozone from hydrocarbon emissions within New York State. It is suggested thai the high rural ozone levels are not primarily due to the transport of ozone and ozone precursors from olher urban areas, but are rather due to natural phenomena such as photochemical generation from naturally occurring precursors or transport of ozone from the stratosphere to the troposphere. The effectiveness of a hydrocarbon control strategy for New York State to meet the ambient air quality standard for photochemical oxidants when background levels themselves may be above the standard is questioned.     

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.     

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.     

Design of Afterburners for Varnish Cookers

Currently, outdoor ozone levels in many U.S. cities exceed the primary health-based national ambient air quality standard. While outdoor ozone levels are an important measure of the severity of those exceedances, people typically spend more than 80 percent of their time Indoors, where ozone levels are lower. Indoor ozone levels range from 10 to 80 percent of outdoor levels, with many people receiving a substantial portion of their ozone exposure while indoors. This paper uses an Indoor air quality model (IAQM) to estimate indoor ozone levels by mlcroenvlronment type (home, office, and vehicle) and configuration (windows open, windows closed, older construction, weatherized, and air conditioned). The formulation of IAQM is discussed, along with specification of model parameters for ozone. The multicompartment version of IAQM is described, with a single-compartment version used for the analyses. IAQM-calculated ozone indoor-outdoor ratios compare well with research-reported values. Results indicate that ozone peak-concentration indoor-outdoor ratios range as follows: home—0.65 (windows open), 0.36 (air conditioned), 0.23 (typical construction, windows closed), and 0.05 (energy-efficient construction, windows closed); office—0.82 (heat-Ing, ventilation and air conditioning systems supplying 100 percent outdoor air), 0.60 (typical HVAC), and 0.32 (energy-efficient HVAC); and vehicle—0.41 (85 mph), 0.33 (55 mph), and 0.21 (10 mph). Analysis results are presented to characterize IAQM’s sensitivity to assumed model parameters.     

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.     

Use of an indoor air quality model (IAQM) to estimate indoor ozone levels

Currently, outdoor ozone levels in many U.S. cities exceed the primary health-based national ambient air quality standard. While outdoor ozone levels are an important measure of the severity of those exceedances, people typically spend more than 80 percent of their time indoors, where ozone levels are lower. Indoor ozone levels range from 10 to 80 percent of outdoor levels, with many people receiving a substantial portion of their ozone exposure while indoors. This paper uses an indoor air quality model (IAQM) to estimate indoor ozone levels by microenvironment type (home, office, and vehicle) and configuration (windows open, windows closed, older construction, weatherized, and air conditioned). The formulation of IAQM is discussed, along with specification of model parameters for ozone. The multicompartment version of IAQM is described, with a single-compartment version used for the analyses. IAQM-calculated ozone indoor-outdoor ratios compare well with research-reported values. Results indicate that ozone peak-concentration indoor-outdoor ratios range as follows: home--0.65 (windows open), 0.36 (air conditioned), 0.23 (typical construction, windows closed), and 0.05 (energy-efficient construction, windows closed); office--0.82 (heating, ventilation and air conditioning systems supplying 100 percent outdoor air), 0.60 (typical HVAC), and 0.32 (energy-efficient HVAC); and vehicle--0.41 (85 mph), 0.33 (55 mph), and 0.21 (10 mph). Analysis results are presented to characterize IAQM's sensitivity to assumed model parameters.     

Long term changes in nitrogen oxides and volatile organic compounds in Toronto and the challenges facing local ozone control

Ground level ozone represents a significant air quality concern in Toronto, Canada, where the national 65 ppb 8-h standard is repeatedly exceeded during the summer. Here we present an analysis of nitrogen dioxide (NO₂), ozone (O₃), and volatile organic compound (VOC) data from federal and provincial governmental monitoring sites from 2000 to 2007. We show that summertime VOC reactivity and ambient concentrations of NO₂ have decreased over this period of time by up to 40% across Toronto and the surrounding region. This has not resulted in significant summertime ozone reductions, and in some urban areas, it appears to be increasing. We discuss the competing effects of decreased ozone titration leading to an increase in O₃, and decreased local ozone production, both caused by significant decreases in NO_x concentrations. In addition, by using local meteorological data, we show that annual variability in summer ozone correlates strongly with maximum daily temperatures, and we explore the effect of atmospheric transport from the southwest which has a significant influence on early morning levels before local production begins. A mathematical model of instantaneous ozone production is presented which suggests that, given the observed decreases in NO_x and VOC reactivity, we would not expect a significant change in local ozone production under photochemically relevant conditions. These results are discussed in the context of Toronto's recent commitment to cutting local smog-causing pollutants by 20% by 2012.     

The potential near-source ozone impacts of upstream oil and gas industry emissions

Increased drilling in urban areas overlying shale formations and its potential impact on human health through decreased air quality make it important to estimate the contribution of oil and gas activities to photochemical smog. Flares and compressor engines used in natural gas operations, for example, are large sources not only of NOx but also offormaldehyde, a hazardous air pollutant and powerful ozone precursor We used a neighborhood scale (200 m horizontal resolution) three-dimensional (3D) air dispersion model with an appropriate chemical mechanism to simulate ozone formation in the vicinity ofa hypothetical natural gas processing facility, based on accepted estimates of both regular and nonroutine emissions. The model predicts that, under average midday conditions in June, regular emissions mostly associated with compressor engines may increase ambient ozone in the Barnett Shale by more than 3 ppb beginning at about 2 km downwind of the facility, assuming there are no other major sources of ozone precursors. Flare volumes of 100,000 cubic meters per hour ofnatural gas over a period of 2 hr can also add over 3 ppb to peak 1-hr ozone somewhatfurther (>8 km) downwind, once dilution overcomes ozone titration and inhibition by large flare emissions of NOx. The additional peak ozone from the hypothetical flare can briefly exceed 10 ppb about 16 km downwind. The enhancements of ambient ozone predicted by the model are significant, given that ozone control strategy widths are of the order of a few parts per billion. Degrading the horizontal resolution of the model to 1 km spuriously enhances the simulated ozone increases by reducing the effectiveness of ozone inhibition and titration due to artificial plume dilution.     

Ozone Transport

Elevated concentrations of ozone, often above the national ambient air quality standard for photochemical oxidants, have been measured in both urban and rural areas of Connecticut. One such episode took place on June 10, 1974. Ozone levels, after stabilizing at values slightly above the standard (i.e., 80 to 110 ppb; Connecticut generated ozone concentrations), rose sharply late in the afternoon reaching concentrations as high as 310 ppb (almost 4 times the standard) in Hartford. The trajectory of the air mass, which arrived in Hartford at the time of maximum O₃ occurence, had its origin in the metropolitan New York area during the early morning rush hour on the episode day. This illustrates that the advective transport of O₃ and O₃ precursors into Connecticut from New York are probably responsible for a significant portion (approximately two-thirds) of the elevated O₃ concentrations measured throughout Connecticut on days when winds are from the south-southwest direction. The fact that peak O₃ levels occur late in the afternoon, several hours after maximum sunlight intensity, reinforces the conclusion that excessive O₃ concentrations developed as O₃ and ozone precursors were generated in the vicinity of New York City and then drifted inland into Connecticut on the afternoon sea breeze.

It appears to be unrealistic to develop a hydrocarbon control strategy for Connecticut in order to meet the photochemical oxidant ambient air quality standard when O₃ and/or ozone precursors ad-vectively transported into the State cause oxidant levels to exceed the standard. The complete cessation of all anthropogenic hydrocarbon emissions in Connecticut would not necessarily assure that the standard would be attained here. The implication is that a regional (i.e., the eastern part of the United States) hydrocarbon control strategy is needed to reduce adequately ozone formation and transport so as to allow Connecticut to meet the current oxidant standard.     

European abatement of surface ozone in a global perspective

EU's programme Clean Air for Europe (CAFE) is presently revising the policy on air quality which will lead to the adoption of a thematic strategy on air pollution under the Sixth Environmental Action Programme by mid-2005. For the abatement of surface ozone it is becoming evident that processes outside European control will be crucial for meeting long-term aims and air quality guidelines in Europe in the future. Measurements and modelling results indicate that there is a strong link between climate change and surface ozone. A warmer and dryer European climate is very likely to lead to increased ozone concentrations. Furthermore, increased anthropogenic emissions in developing economies in Asia are likely to raise the hemispheric background level of ozone. A significant increase in the background concentration of ozone has been observed at several sites in Northern Europe although the underlying causes are not settled. The photochemical formation of tropospheric ozone from increased concentrations of methane and CO may also lead to a higher ozone level on a global scale. Gradually, these effects may outweigh the effect of the reduced European ozone precursor emissions. This calls for a global or hemispheric perspective in the revision of the European air quality policy for ozone.     

Attitudes and Responses Towards Air Pollution in Medieval England

ABSTRACT

The concentrations of contaminants in the supply air of mechanically ventilated buildings may be altered by pollutant emissions from and interactions with duct materials. We measured the emission rate of volatile organic compounds (VOCs) and aldehydes from materials typically found in ventilation ducts. The emission rate of VOCs per exposed surface area of materials was found to be low for some duct liners, but high for duct sealing caulk and a neo-prene gasket. For a typical duct, the contribution to VOC concentrations is predicted to be only a few percent of common indoor levels. We exposed selected materials to ~100-ppb ozone and measured VOC emissions. Exposure to ozone increased the emission rates of aldehydes from a duct liner, duct sealing caulk, and neoprene gasket. The emission of aldehydes from these materials could increase indoor air concentrations by amounts that are as much as 20% of odor thresholds. We also measured the rate of ozone uptake on duct liners and galvanized sheet metal to predict how much ozone might be removed by a typical duct in ventilation systems. For exposure to a constant ozone mol fraction of 37 ppb, a lined duct would initially remove ~9% of the ozone, but over a period of 10 days the ozone removal efficiency would diminish to less than 4%. In an unlined duct, in which only galvanized sheet metal is exposed to the air-stream, the removal efficiency would be much lower, ~0.02%. Therefore, ducts in ventilation systems are unlikely to be a major sink for ozone.     

Rural southeast Texas air quality measurements during the 2006 Texas Air Quality Study

The authors conducted air quality measurements of the criteria pollutants carbon monoxide, nitrogen oxides, and ozone together with meteorological measurements at a park site southeast of College Station, TX, during the 2006 Texas Air Quality Study II (TexAQS). Ozone, a primary focus of the measurements, was above 80 ppb during 3 days and above 75 ppb during additional 8 days in summer 2006, suggestive of possible violations of the ozone National Ambient Air Quality Standard (NAAQS) in this area. In concordance with other air quality measurements during the TexAQS II, elevated ozone mixing ratios coincided with northerly flows during days after cold front passages. Ozone background during these days was as high as 80 ppb, whereas southerly air flows generally provided for an ozone background lower than 40 ppb. Back trajectory analysis shows that local ozone mixing ratios can also be strongly affected by the Houston urban pollution plume, leading to late afternoon ozone increases of as high as 50 ppb above background under favorable transport conditions. The trajectory analysis also shows that ozone background increases steadily the longer a southern air mass resides over Texas after entering from the Gulf of Mexico. In light of these and other TexAQS findings, it appears that ozone air quality is affected throughout east Texas by both long-range and regional ozone transport, and that improvements therefore will require at least a regionally oriented instead of the current locally oriented ozone precursor reduction policies.     

Influence of the atmospheric conductivity on the ozone exposure of plants under ambient conditions: Considerations for establishing ozone standards to protect vegetation

This paper provides results of ozone flux density measurements above a permanent grassland ecosystem as they relate to an establishment of air quality guidelines or standards. Using a resistance analogue, the product of zone concentration measured at a standard measurement height and the conductivity of the atmosphere reflect the maximum possible ozone flux density towards the envelope of the plants. In other words, this product can be regarded as the ozone exposure potential of the atmosphere for plants. It could be shown that ozone concentrations between 100 and 180 microg m(-3) are likely to have a great phytotoxic potential and are more important than concentrations greater than 180 microg m(-3). From the results presented one can deduce that the application of dose-response relationships based on chamber experiments to ambient conditions results in an overestimation of, for example, yield loses. Any guideline or standard has to take into account the influence of the atmospheric conductivity on the absorbed dose of ozone.     

The effects of ozone/limonene reactions on indoor secondary organic aerosols

An indoor air quality model was used to predict dynamic particle mass concentrations based on homogeneous chemical mechanisms and partitioning of semi-volatile products to particles. The ozone–limonene reaction mechanism was combined with gas-phase chemistry of common atmospheric organic and inorganic compounds and incorporated into the indoor air quality model. Experiments were conducted in an environmental chamber to investigate secondary particle formation resulting from ozone/limonene reactions. Experimental results indicate that significant fine particle growth occurs due to the interaction of ozone and limonene and subsequent intermediate by-products. Secondary particle mass concentrations were estimated from the measured particle size distribution. Predicted particle mass concentrations were in good agreement with experimental results—generally within ∼25% at steady-state conditions. Both experimental and predicted results suggest that air exchange rate plays a significant role in determining secondary fine particle levels in indoor environments. Secondary particle mass concentrations are predicted to increase substantially with lower air exchange rates, an interesting result given a continuing trend toward more energy efficient buildings. Lower air exchange rates also shifted the particle size distribution toward larger particle diameters. Secondary particle mass concentrations are also predicted to increase with higher outdoor ozone concentrations, higher outdoor particle concentrations, higher indoor limonene emission rates, and lower indoor temperatures.     

Demonstrating Attainment of the Air Quality Standards: Integration of Observations and Model Predictions into the Probabilistic Framework

ABSTRACT

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.     

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.     

Synoptic-scale transport of ozone into Southern Ontario

This study focuses on synoptic-scale transport of ozone as it affects Southern Ontario. This process has been analyzed for the summer in 2001, as an example period of a frequent event that usually occurs during summer in this region. The work was carried out using the mesoscale modeling system generation 5 (MM5)/sparse matrix operator kernel emission modeling system (SMOKE)/community multiscale air quality (CMAQ) regional air quality modeling system, together with observational data from monitoring stations located throughout the modeling domain. Other different analyses have been carried out to supply more information apart from that obtained by the modeling system. A back-trajectory cluster methodology was used to evaluate the magnitude of the effects studied and an analysis of wind direction and cloud cover revealed a significant correlation with ozone concentration (R²=0.5–0.6). Synoptic sea-surface level pressure (SLP) patterns were also analyzed to examine other meteorological aspects. The contribution of natural background ozone to the total amount within the region was compared with that from synoptic-scale transport. The influence of emission of pollutants from selected areas on ozone concentrations in Southern Ontario was also analyzed. As relevant results of these analyses, the model predicts that background ozone is the largest contribution to the ground-level ozone concentration during days in which low values were recorded. However, when smog episodes occurred, the model predicts that around 60% of the ozone formed by anthropogenic emissions of pollutants is due to releases from nearby US states.     

Increase in summer European ozone amounts due to climate change

The local and regional distribution of pollutants is significantly influenced by weather patterns and variability along with the spatial patterns of emissions. Therefore, climatic changes which affect local meteorological conditions can alter air quality. We use the regional air quality model CHIMERE driven by meteorological fields from regional climate change simulations to investigate changes in summer ozone mixing ratios over Europe under increased greenhouse gas (GHG) forcing. Using three 30-year simulation periods, we find that daily peak ozone amounts as well as average ozone concentrations substantially increase during summer in future climate conditions. This is mostly due to higher temperatures and reduced cloudiness and precipitation over Europe and it leads to a higher number of ozone events exceeding information and warning thresholds. Our results show a pronounced regional variability, with the largest effects of climate change on ozone concentrations occurring over England, Belgium, Germany and France. The temperature-driven increase in biogenic emissions appears to enhance the ozone production and isoprene was identified as the most important chemical factor in the ozone sensitivity. We also find that summer ozone levels in future climate projections are similar to those found during the exceptionally warm and dry European summer of 2003. Our simulations suggest that in future climate conditions summer ozone might pose a much more serious threat to human health, agriculture and natural ecosystems in Europe, so that the effects of climate trends on pollutant amounts should be considered in future emission control measures.     

Chlorophyll a fluorescence, antioxidant enzymes and lipid peroxidation in tomato in response to ozone and benomyl.

Ozone is a widely distributed phytotoxic air pollutant and is known to reduce the yield of several important agricultural crops in Spain. However, benomyl has been found to lessen the adverse impact of ozone on plants. We studied the effects of ozone and benomyl on chlorophyll a fluorescence, antioxidant enzymes, and lipid peroxidation in tomato (Lycopersicon esculentum Mill. cv. Tiny Tim) grown in open-top chambers in the field. Our results indicate that benomyl prevented the peroxidation of membrane lipids and increased protection of PSII from ozone. There was also a significant reduction in the activity of the antioxidant enzyme superoxide dismutase in ozone-exposed plants that had not been treated with benomyl. Comparing plants treated with benomyl to untreated plants we found that, on exposure to ozone, a greater fraction of light absorption energy was cycled through the photosynthetic system in benomyl-treated plants, as shown by the higher PSII-mediated electron flow and the higher fraction of open PSII reaction centers. The values analyzed in the fluorescence parameters and lipid peroxidation were similar for plants without benomyl grown in a charcoal-filtered environment and benomyl-treated plants exposed to ozone.