Assessment of a regulatory model's performance relative to large spatial heterogeneity in observed ozone in Houston,Texas

In Houston, some of the highest measured 8-hr ozone (O₃) peaks are characterized by sudden increases in observed concentrations of at least 40 ppb in 1 hr, or 60 ppb in 2 hr. Measurements show that these large hourly changes appear at only a few monitors and span a narrow geographic area, suggesting a spatially heterogeneous field of O₃ concentrations. This study assessed whether a regulatory air quality model (AQM) can simulate this observed behavior. The AQM did not reproduce the magnitude or location of some of the highest observed hourly O₃ changes, and it also failed to capture the limited spatial extent. On days with measured large hourly changes in O₃ concentrations, the AQM predicted high O₃ over large regions of Houston, resulting in overpredictions at several monitors. This analysis shows that the model can make high O₃, but on these days the predicted spatial field suggests that the model had a different cause. Some observed large hourly changes in O₃ concentrations have been linked to random releases of industrial volatile organic compounds (VOCs). In the AQM emission inventory, there are several emission events when an industrial point source increases VOC emissions in excess of 10,000 mol/hr. One instance increased predicted downwind O₃ concentrations up to 25 ppb. These results show that the modeling system is responsive to a large VOC release, but the timing and location of the release, and meteorological conditions, are critical requirements. Attainment of the O₃ standard requires the use of observational data and AQM predictions. If the large observed hourly changes are indicative of a separate cause of high O₃, then the model may not include that cause, which might result in regulators enacting control strategies that could be ineffective.

Implications To show the attainment of the O₃ standard, the U.S. Environmental Protection Agency (EPA) requires the use of observations and model predictions under the assumption that simulations are capable of reproducing observed phenomena. The regulatory model is unable to reproduce observed behavior measured in the observational database. If the large observed hourly changes were indicative of a separate cause of high O₃, then the model would not include that cause. Inaccurate model predictions may prompt air quality regulators to enact control strategies that are effective in the modeling system, but prove ineffective in the real world.     

Issues with ozone attainment methodology for Houston, TX

To comply with the federal 8-hr ozone standard, the state of Texas is creating a plan for Houston that strictly follows the U.S. Environmental Protection Agency's (EPA) guidance for demonstrating attainment. EPA's attainment guidance methodology has several key assumptions that are demonstrated to not be completely appropriate for the unique observed ozone conditions found in Houston. Houston's ozone violations at monitoring sites are realized as gradual hour-to-hour increases in ozone concentrations, or by large hourly ozone increases that exceed up to 100 parts per billion/hr. Given the time profiles at the violating monitors and those of nearby monitors, these large increases appear to be associated with small parcels of spatially limited plumes of high ozone in a lower background of urban ozone. Some of these high ozone parcels and plumes have been linked to a combination of unique wind conditions and episodic hydrocarbon emission events from the Houston Ship Channel. However, the regulatory air quality model (AQM) does not predict these sharp ozone gradients. Instead, the AQM predicts gradual hourly increases with broad regions of high ozone covering the entire Houston urban core. The AQM model performance can be partly attributed to EPA attainment guidance that prescribes the removal in the baseline model simulation of any episodic hydrocarbon emissions, thereby potentially removing any nontypical causes of ozone exceedances. This paper shows that attainment of all monitors is achieved when days with observed large hourly variability in ozone concentrations are filtered from attainment metrics. Thus, the modeling and observational data support a second unique cause for how ozone is formed in Houston, and the current EPA methodology addresses only one of these two causes.     

Application of artificial neural networks to modeling and prediction of ambient ozone concentrations

The deterministic modeling of ambient O3 concentrations is difficult because of the complexity of the atmospheric system in terms of the number of chemical species; the availability of accurate, time-resolved emissions data; and the required rate constants. However, other complex systems have been successfully approximated using artificial neural networks (ANNs). In this paper, ANNs are used to model and predict ambient O3 concentrations based on a limited number of measured hydrocarbon species, NOx compounds, temperature, and radiant energy. In order to examine the utility of these approaches, data from the Coastal Oxidant Assessment for Southeast Texas (COAST) program in Houston, TX, have been used. In this study, 53 hydrocarbon compounds, along with O3, nitrogen oxides, and meteorological data were continuously measured during summer 1993. Steady-state ANN models were developed to examine the ability of these models to predict current O3 concentrations from measured VOC and NOx concentrations. To predict the future concentrations of O3, dynamic models were also explored and were used for extraction of chemical information such as reactivity estimations for the VOC species. The steady-state model produced an approximation of O3 data and demonstrated the functional relationship between O3 and VOC-NOx concentrations. The dynamic models were able to the adequately predict the O3 concentration and behavior of VOC-NOx-O3 system a number of hourly intervals into the future. For 3 hr into the future, O3 concentration could be predicted with a root-mean squared error (RMSE) of 8.21 ppb. Extending the models further in time led to an RMSE of 11.46 ppb for 5-hr-ahead values. This prediction capability could be useful in determining when control actions are needed to maintain measured concentrations within acceptable value ranges.     

The effect of variability in industrial emissions on ozone formation in Houston, Texas

Ambient observations have indicated that high concentrations of ozone observed in the Houston/Galveston area are associated with plumes of highly reactive hydrocarbons, mixed with NO_x, from industrial facilities. Ambient observations and industrial process data, such as mass flow rates for industrial flares, indicate that the VOCs associated with these industrial emissions can have significant temporal variability. To characterize the effect of this variability in emissions on ozone formation in Houston, data were collected on the temporal variability of industrial emissions or emission surrogates (e.g., mass flow rates to flares). The observed emissions variability was then used to construct regionwide emission inventories with variable industrial emissions, and the impacts of the variability on ozone formation were examined for two types of meteorological conditions, both of which lead to high ozone concentrations in Houston. The air quality simulations indicate that variability in industrial emissions has the potential to cause increases and decreases of 10–52 ppb (13–316%), or more, in ozone concentration. The largest of these differences are restricted to regions of 10–20 km², but the variability also has the potential to increase regionwide maxima in ozone concentrations by up to 12 ppb.     

Modeling the effects of VOC/NOx emissions on ozone synthesis in the cascadia airshed of the Pacific Northwest

A modeling system consisting of MM5, Calmet, and Calgrid was used to investigate the sensitivity of anthropogenic volatile organic compound (VOC) and oxides of nitrogen (NOx) reductions on ozone formation within the Cascadia airshed of the Pacific Northwest. An ozone episode that occurred on July 11-14, 1996, was evaluated. During this event, high ozone levels were recorded at monitors downwind of Seattle, WA, and Portland, OR, with one monitor exceeding the 1 hr/120 ppb National Ambient Air Quality Standard (at 148 ppb), and six monitors above the proposed 8 hr/80 ppb standard (at 82-130 ppb). For this particular case, significant emissions reductions, between 25 and 75%, would be required to decrease peak ozone concentrations to desired levels. Reductions in VOC emissions alone, or a combination of reduced VOC and NOx emissions, were generally found to be most effective; reducing NOx emissions alone resulted in increased ozone in the Seattle area. When only VOC emissions were curtailed, ozone reductions occurred in the immediate vicinity of densely populated areas, while NOx reductions resulted in more widespread ozone reductions.     

Modeling the Effects of VOC/NOx Emissions on Ozone Synthesis in the Cascadia Airshed of the Pacific Northwest

ABSTRACT

A modeling system consisting of MM5, Calmet, and Calgrid was used to investigate the sensitivity of anthropogenic volatile organic compound (VOC) and oxides of nitrogen (NO_x) reductions on ozone formation within the Cascadia airshed of the Pacific Northwest. An ozone episode that occurred on July 11-14, 1996, was evaluated. During this event, high ozone levels were recorded at monitors downwind of Seattle, WA, and Portland, OR, with one monitor exceeding the 1 hr/120 ppb National Ambient Air Quality Standard (at 148 ppb), and six monitors above the proposed 8 hr/80 ppb standard (at 82-130 ppb). For this particular case, significant emissions reductions, between 25 and 75%, would be required to decrease peak ozone concentrations to desired levels. Reductions in VOC emissions alone, or a combination of reduced VOC and NO_x emissions, were generally found to be most effective; reducing NO_x emissions alone resulted in increased ozone in the Seattle area. When only VOC emissions were curtailed, ozone reductions occurred in the immediate vicinity of densely populated areas, while NO_x reductions resulted in more widespread ozone reductions.     

Application of Artificial Neural Networks to Modeling and Prediction of Ambient Ozone Concentrations

ABSTRACT

The deterministic modeling of ambient O₃ concentrations is difficult because of the complexity of the atmospheric system in terms of the number of chemical species; the availability of accurate, time-resolved emissions data; and the required rate constants. However, other complex systems have been successfully approximated using artificial neural networks (ANNs). In this paper, ANNs are used to model and predict ambient O₃ concentrations based on a limited number of measured hydrocarbon species, NO_x compounds, temperature, and radiant energy. In order to examine the utility of these approaches, data from the Coastal Oxidant Assessment for Southeast Texas (COAST) program in Houston, TX, have been used. In this study, 53 hydrocarbon compounds, along with O₃, nitrogen oxides, and meteorological data were continuously measured during summer 1993. Steady-state ANN models were developed to examine the ability of these models to predict current O₃ concentrations from measured VOC and NO concentrations. To predict the future concentrations of O₃, dynamic models were also explored and were used for extraction of chemical information such as reactivity estimations for the VOC species.

The steady-state model produced an approximation of O₃ data and demonstrated the functional relationship between O₃ and VOC-NO_x concentrations. The dynamic models were able to the adequately predict the O₃ concentration and behavior of VOC-NO_x-O₃ system a number of hourly intervals into the future. For 3 hr into the future, O₃ concentration could be predicted with a root-mean squared error (RMSE) of 8.21 ppb. Extending the models further in time led to an RMSE of 11.46 ppb for 5-hr-ahead values. This prediction capability could be useful in determining when control actions are needed to maintain measured concentrations within acceptable value ranges.     

Near-source air quality impacts of large olefin flares

Large petrochemicalflares, common in the Houston Ship Channel (the Ship Channel) and other industrialized areas in the Gulfof Mexico region, emit hundreds to thousands of pounds per hour of highly reactive volatile organic compounds (HRVOCs). We employedfine horizontal resolution (200 mx200 m) in a three-dimensional (3D) Eulerian chemical transport model to simulate two historical Ship Channel flares. The model reasonably reproduced the observed ozone rise at the nearest monitoring stations downwind of the flares. The larger of the two flares had an olefin emission rate exceeding 1400 lb/hr. In this case, the model simulated a rate of increase in peak ozone greater than 40 ppb/hr over a 12 kmx12 km horizontal domain without any unusual meteorological conditions. In this larger flare, formaldehyde emissions typically neglected in official inventories enhanced peak ozone by as much as 16 ppb and contributed over 10 ppb to ambient formaldehyde up to approximately 8 km downwind of the flare. The intense horizontal gradients in large flare plumes cannot be simulated by coarse models typically used to demonstrate ozone attainment. Moreover even the relatively dense monitoring network in the Ship Channel may not be able to detect many transient high ozone events (THOEs) caused by industrial flare emissions in the absence of stagnant air recirculation or stalled sea breeze fronts, even though such conditions are unnecessary for the occurrence of THOEs.     

Rethinking the assessment of photochemical modelin systems in air quality planning applications

The U.S. Environmental Protection Agency provides guidelines for demonstrating that future 8-hr ozone (O3) design values will be at or below the National Ambient Air Quality Standards on the basis of the application of photochemical modeling systems to simulate the effect of emission reductions. These guidelines also require assessment of the model simulation against observations. In this study, we examined the link between the simulated relative responses to emission reductions and model performance as measured by operational evaluation metrics, a part of the model evaluation required by the guidance, which often is the cornerstone of model evaluation in many practical applications. To this end, summertime O3 concentrations were simulated with two modeling systems for both 2002 and 2009 emission conditions. One of these two modeling systems was applied with two different parameterizations for vertical mixing. Comparison of the simulated base-case 8-hr daily maximum O3 concentrations showed marked model-to-model differences of up to 20 ppb, resulting in significant differences in operational model performance measures. In contrast, only relatively minor differences were detected in the relative response of O3 concentrations to emission reductions, resulting in differences of a few ppb or less in estimated future year design values. These findings imply that operational model evaluation metrics provide little insight into the reliability of the actual model application in the regulatory setting (i.e., the estimation of relative changes). In agreement with the guidance, it is argued that more emphasis should be placed on the diagnostic evaluation of O3-precursor relationships and on the development and application of dynamic and retrospective evaluation approaches in which the response of the model to changes in meteorology and emissions is compared with observed changes. As an example, simulated relative O3 changes between 1995 and 2007 are compared against observed changes. It is suggested that such retrospective studies can serve as the starting point for targeted diagnostic studies in which individual aspects of the modeling system are evaluated and refined to improve the characterization of observed changes.     

The New England Air Quality Forecasting Pilot Program: development of an evaluation protocol and performance benchmark

The National Oceanic and Atmospheric Administration recently sponsored the New England Forecasting Pilot Program to serve as a "test bed" for chemical forecasting by providing all of the elements of a National Air Quality Forecasting System, including the development and implementation of an evaluation protocol. This Pilot Program enlisted three regional-scale air quality models, serving as prototypes, to forecast ozone (O3) concentrations across the northeastern United States during the summer of 2002. A suite of statistical metrics was identified as part of the protocol that facilitated evaluation of both discrete forecasts (observed versus modeled concentrations) and categorical forecasts (observed versus modeled exceedances/nonexceedances) for both the maximum 1-hr (125 ppb) and 8-hr (85 ppb) forecasts produced by each of the models. Implementation of the evaluation protocol took place during a 25-day period (August 5-29), utilizing hourly O3 concentration data obtained from over 450 monitors from the U.S. Environment Protection Agency's Air Quality System network.     

Near-source air quality impacts of large olefin flares

Large petrochemical flares, common in the Houston Ship Channel (the Ship Channel) and other industrialized areas in the Gulf of Mexico region, emit hundreds to thousands of pounds per hour of highly reactive volatile organic compounds (HRVOCs). We employed fine horizontal resolution (200 m?×?200 m) in a three-dimensional (3D) Eulerian chemical transport model to simulate two historical Ship Channel flares. The model reasonably reproduced the observed ozone rise at the nearest monitoring stations downwind of the flares. The larger of the two flares had an olefin emission rate exceeding 1400 lb/hr. In this case, the model simulated a rate of increase in peak ozone greater than 40 ppb/hr over a 12 km?×?12 km horizontal domain without any unusual meteorological conditions. In this larger flare, formaldehyde emissions typically neglected in official inventories enhanced peak ozone by as much as 16 ppb and contributed over 10 ppb to ambient formaldehyde up to ～8 km downwind of the flare. The intense horizontal gradients in large flare plumes cannot be simulated by coarse models typically used to demonstrate ozone attainment. Moreover, even the relatively dense monitoring network in the Ship Channel may not be able to detect many transient high ozone events (THOEs) caused by industrial flare emissions in the absence of stagnant air recirculation or stalled sea breeze fronts, even though such conditions are unnecessary for the occurrence of THOEs.

Implications: Flare minimization may be an important strategy to attain the U.S. federal ozone standard in industrialized areas, and to avoid inordinate exposure to formaldehyde in neighborhoods surrounding petrochemical facilities. Moreover, air quality monitoring networks, emission inventories, and chemical transport models with higher spatial and temporal resolution and more refined speciation of HRVOCs are needed to better account for the near-source air quality impacts of large olefin flares.     

Ambient ozone and crop loss: establishing a cause-effect relationship

This paper provides the results of a retrospective mathematical analysis of the US NCLAN (National Crop Loss Assessment Network) open-top chamber data. Some 77% of the 73 crop harvests examined, showed no statistically significant yield differences between NF (non-filtered open-top chamber) and AA (chamberless, ambient air) treatments (no easily discernable chamber effects on yield). However, among these cases only seven acceptable examples showed statistically significant yield reductions in NF compared to the CF (charcoal filtered open-top chamber) treatment. An examination of the combined or cumulative hourly ambient O3 frequency distribution for cases with yield loss in NF compared to a similar match of cases without yield loss showed that the mean, median and the various percentiles were all higher (>/= 3 X) in the former in contrast to the latter scenario. The combined frequency distribution of hourly O3 concentrations for the cases with yield loss in NF were clearly separated from the corresponding distribution with no yield loss, at O3 concentrations > 49 ppb. Univariate linear regressions between various O3 exposure parameters and per cent yield losses in NF showed that the cumulative frequency of occurrence of O3 concentrations between 50 and 87 ppb was the best predictor (adjusted R2 = 0.712 and p = 0.011). This analysis also showed that the frequency distribution of hourly concentrations up to 87 ppb O3 represented a critical point, since the addition of the frequency distributions of > 87 ppb O3 did not improve the R2 values. In fact as the frequency of hourly O3 concentrations included in the regression approached 50-100 ppb, the R2 value decreased substantially and the p value increased inversely. Further, univariate linear regressions between the frequencies of occurrence of various O3 concentrations between 50 and 90 ppb and: (a) cases with no yield difference in NF and (b) cases with yield increase in NF compared to the CF treatment (positive effect) provided no meaningful statistical relationship (adjusted R2 = 0.000) in either category. These results support the basis that additional evaluation of the frequency of occurrence of hourly O3] concentrations between 50 and 87 ppb for cases with the yield reductions could provide a meaningful ambient O3 standard, objective or guideline for vegetation.     

Ambient ozone (O3) and adverse crop response: a unified view of cause and effect

This paper presents a cohesive view of the dynamics of ambient O(3) exposure and adverse crop response relationships, coupling the properties of photochemical O(3) production, flux of O(3) from the atmosphere into crop canopies and the crop response per se. The results from two independent approaches ((a) statistical and (b) micrometeorological) were analyzed for understanding cause-effect relationships of the foliar injury responses of tobacco cv Bel-W3 to the exposure dynamics of ambient O(3) concentrations. Similarly, other results from two independent approaches were analyzed in: (1) establishing a micrometeorological relationship between hourly ambient O(3) concentrations and their vertical flux from the air into a natural grassland canopy; and (2) establishing a statistical relationship between hourly ambient O(3) concentrations in long-term, chronic exposures and crop yield reductions. Independent of the approach used, atmospheric conditions appeared to be most conducive and the crop response appeared to be best explained statistically by the cumulative frequency of hourly ambient O(3) concentrations between 50 ppb and 90 ppb (100 and 180 microg m(-3)). In general, this concentration range represents intermediate or moderately enhanced hourly O(3) values in a polluted environment. Further, the diurnal occurrence of this concentration range (often approximately between 0900 and 1600 h in a polluted, agricultural environment) coincided with the optimal CO(2) flux from the atmosphere into the crop canopy, thus high uptake. The frequency of occurrence of hourly O(3) concentrations > 90 ppb (180 microg m(-3)) appeared to be of little importance and such concentrations in general appeared to occur during atmospheric conditions which did not facilitate optimal vertical flux into the crop canopy, thus low uptake. Alternatively, when > 90 ppb (180 microg m(-3)) O(3) concentrations occurred during the 0900-1600 h window, their frequency of occurrence was low in comparison to the 50-90 ppb (100-180 microg m(-3)) range. Based on the overall results, we conclude that if the cumulative frequency of hourly ambient O(3) concentrations between 50-62 ppb (100-124 microg m(-3)) occurred during 53% of the growing season and the corresponding cumulative frequency of hourly O(3) concentrations between 50-74 ppb (100-148 microg m(-3)) occurred during 71% of the growing season, then yield reductions in sensitive crops could be expected, if other factors supporting growth, such as adequate soil moisture are not limiting.     

Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area

A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.     

Modeling an air pollution episode in northwestern United States: Identifying the effect of nitrogen oxide and volatile organic compound emission changes on air pollutants formation using direct sensitivity analysis

Air quality impacts of volatile organic compound (VOC) and nitrogen oxide (NO_x) emissions from major sources over the northwestern United States are simulated. The comprehensive nested modeling system comprises three models: Community Multiscale Air Quality (CMAQ), Weather Research and Forecasting (WRF), and Sparse Matrix Operator Kernel Emissions (SMOKE). In addition, the decoupled direct method in three dimensions (DDM-3D) is used to determine the sensitivities of pollutant concentrations to changes in precursor emissions during a severe smog episode in July of 2006. The average simulated 8-hr daily maximum O₃ concentration is 48.9 ppb, with 1-hr O₃ maxima up to 106 ppb (40 km southeast of Seattle). The average simulated PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) concentration at the measurement sites is 9.06 μg m^?3, which is in good agreement with the observed concentration (8.06 μg m^?3). In urban areas (i.e., Seattle, Vancouver, etc.), the model predicts that, on average, a reduction of NO_x emissions is simulated to lead to an increase in average 8-hr daily maximum O₃ concentrations, and will be most prominent in Seattle (where the greatest sensitivity is??0.2 ppb per % change of mobile sources). On the other hand, decreasing NO_x emissions is simulated to decrease the 8-hr maximum O₃ concentrations in remote and forested areas. Decreased NO_x emissions are simulated to slightly increase PM_2.5 in major urban areas. In urban areas, a decrease in VOC emissions will result in a decrease of 8-hr maximum O₃ concentrations. The impact of decreased VOC emissions from biogenic, mobile, nonroad, and area sources on average 8-hr daily maximum O₃ concentrations is up to 0.05 ppb decrease per % of emission change, each. Decreased emissions of VOCs decrease average PM_2.5 concentrations in the entire modeling domain. In major cities, PM_2.5 concentrations are more sensitive to emissions of VOCs from biogenic sources than other sources of VOCs. These results can be used to interpret the effectiveness of VOC or NO_x controls over pollutant concentrations, especially for localities that may exceed National Ambient Air Quality Standards (NAAQS).

Implications: The effect of NO_x and VOC controls on ozone and PM_2.5 concentrations in the northwestern United States is examined using the decoupled direct method in three dimensions (DDM-3D) in a state-of-the-art three-dimensional chemical transport model (CMAQ). NO_x controls are predicted to increase PM_2.5 and ozone in major urban areas and decrease ozone in more remote and forested areas. VOC reductions are helpful in reducing ozone and PM_2.5 concentrations in urban areas. Biogenic VOC sources have the largest impact on O₃ and PM_2.5 concentrations.     

A numerical analysis of the combined open-top chamber data from the USA and Europe on ambient ozone and negative crop responses

Statistical analysis was performed using selected sets of combined data from the US National Crop Loss Assessment Network and the European Open-Top Chambers Programme to examine the relationships between the occurrences of hourly ambient ozone (O3) concentrations and adverse crop yield responses. The results suggest that the frequency of occurrences of relatively low hourly O3 concentrations ( approximately <35 ppb) are not as important as moderate to higher concentrations in eliciting negative crop biomass responses. They also suggest that daily peak (highest) hourly O3 values ( approximately >90 ppb) may not be as critical, most likely because they frequently do not occur during time periods when conditions that promote atmospheric conductivity (O3 deposition) and plant uptake (O3 absorption) are in coherence.     

Tetrachloroethylene emissions and exposure in dry cleaning

Tetrachloroethylene (PCE) emissions and the exposure of workers in six commercial and three industrial dry-cleaning establishments that use dry-to-dry machines were determined. The personal samples and area samples [8-hr time-weighted average (TWA) and short-term exposure] were collected with charcoal tubes and passive monitors. The temporal variation of PCE concentration in the workplace air was monitored using a Fourier transform infrared analyzer (FTIR). The PCE emission rates were determined by multiplying the average PCE concentration in the room and the total airflow rate in the room. The PCE emissions were related to the cleaning rate in units of kg/hr. The operators' mean TWA exposure in commercial shops and industrial establishments was 28 (4.1 ppm) and 32 mg/m3 (4.6 ppm), and the pressers' exposure was 3.4 (0.5 ppm) and 7.7 mg/m3 (1.1 ppm), respectively. The customer service personnel had the lowest TWA exposure with a mean value of 0.8 mg/m3 (0.1 ppm). The highest peak concentration (2300 mg/m3; 334 ppm) was observed during cleaning of the lint and button trap, during which operation respirators were used. The PCE emission rates ranged from 4 to 118 g/hr corresponding to emission factors (mass of solvent evaporated per mass of cleaned cloths) of 0.3-3.6 g/kg. The workers' exposure to PCE was below the occupational limit values in the United States [according to the American Conference of Governmental Industrial Hygienists (ACGIH)] and in Finland. The outdoor PCE emissions were clearly below the limit values given in the European Union volatile organic compound (VOC) directive requirements.     

An assessment of the sensitivity and reliability of the relative reduction factor approach in the development of 8-hr ozone attainment plans

The updated regulatory framework for demonstrating that future 8-hr ozone (O3) design values will be at or below the National Ambient Air Quality Standards (NAAQS) provides guidelines for the development of a State Implementation Plan (SIP) that includes methods based on photochemical modeling and analytical techniques. One of the suggested approaches is the relative reduction factor (RRF) for estimating the efficacy of emission reductions. In this study, the sensitivity of model-predicted responses towards emission reductions to the choice of meteorology and chemical mechanisms was examined. While the different modeling simulations generally were found to be in agreement on whether predicted future-year design values would be above or below the NAAQS for 8-hr O3 at a majority of the monitoring locations in the eastern United States, differences existed for a small percentage of monitors (approximately 6.4%). Another issue investigated was the ability of the attainment demonstration procedure to predict changes in monitored O3 design values. A retrospective analysis was performed by comparing predicted O3 design values from model simulations using emission estimates for 1996 and 2001 with monitored O3 design values for 2001. Results indicated that an average gross error of approximately 5 ppb was present between modeled and observed design values and that, at approximately 27% of all sites, model-predicted and observed design values disagreed as to whether the design value was above or below the NAAQS. Retrospective analyses such as the one presented in this study can provide valuable insights into the strengths and limitations of modeling and analysis techniques used to predict future design values over time periods of a decade or more for the purpose of developing SIPs. Furthermore, such analyses could provide avenues for improvement and added confidence in the use of the RRF approach for addressing attainment of the NAAQS.     

An assessment of the emissions inventory processing systems EMS-2001 and SMOKE in grid-based air quality models

In the United States, emission processing models such as Emissions Modeling System-2001 (EMS-2001), Emissions Preprocessor System-Version 2.5 (EPS2.5), and the Sparse Matrix Operator Kernel Emissions (SMOKE) model are currently being used to generate gridded, hourly, speciated emission inputs for urban and regional-scale photochemical models from aggregated pollutant inventories. In this study, two models, EMS-2001 and SMOKE, were applied with their default internal data sets to process a common inventory database for a high ozone (O3) episode over the eastern United States using the Carbon Bond IV (CB4) chemical speciation mechanism. A comparison of the emissions processed by these systems shows differences in all three of the major processing steps performed by the two models (i.e., in temporal allocation, spatial allocation, and chemical speciation). Results from a simulation with a photochemical model using these two sets of emissions indicate differences on the order of +/- 20 ppb in the predicted 1-hr daily maximum O3 concentrations. It is therefore critical to develop and implement more common and synchronized temporal, spatial, and speciation cross-reference systems such that the processes within each emissions model converge toward reasonably similar results. This would also help to increase confidence in the validity of photochemical grid model results by reducing one aspect of modeling uncertainty.     

Weekday/Weekend differences in ambient air pollutant concentrations in atlanta and the southeastern United States

The authors quantified changes between mean weekday and weekend ambient concentrations of ozone (O3) precursors (volatile organic compounds [VOC], carbon monoxide [CO], nitric oxide, and oxides of nitrogen [NOx]) in Atlanta and surrounding areas to observe how weekend precursor emission levels influenced ambient O3 levels. The authors analyzed CO, nitric oxide (NO), and NO, measurements from 1998 to 2002 and speciated VOC from 1996 to 2003. They observed a strong weekend effect in the Atlanta region, with median daytime (6:00 a.m. to 3:00 p.m. Eastern Standard Time) decreases of 62%, 57%, and 31%, respectively, in the ambient levels of NO, NOx, and CO from Wednesdays to Sundays, during the ozone season (March to October). They also observed significant decreases in ambient VOC levels between Wednesdays and Sundays, with decreases of 28% for the sum of aromatic compounds and 19% for the sum of Photochemical Assessment Monitoring Stations target compounds. Despite large reductions in O3 precursor levels on weekends, day-of-week differences in O3 mixing ratios in and near Atlanta were much smaller. Averaging overall O3-season days, the 1-hr and 8-hr mean peak daily O3 maxima on Sundays were 4.5% and 2.3% lower, respectively, than their mean levels on Wednesdays (median of 14 site differences), with no sites showing statistically significant Wednesday-to-Sunday differences. When restricted to high-O3 days (highest 3 peak O3 days per day of week per site per year), the 1-hr and 8-hr Sunday O3 mixing ratios were 11% and 10% lower, respectively, than their mean peak levels on Wednesdays (median of 14 site differences), with 6 of 14 sites showing statistically significant Wednesday-to-Sunday differences. The analyses of weekday/weekend differences in O3 precursor concentrations show that different emission reductions than normally take place each weekend will be required to achieve major reductions in ambient ozone levels in the Atlanta area.