Hydrocarbon emissions from industrial release events in the Houston-Galveston area and their impact on ozone formation

Ambient measurements have shown that ozone formation in the Houston-Galveston area of Texas is frequently much more rapid than in other urban areas. One of the contributing factors is believed to be short-term episodic or “event” emissions from industrial facilities, particularly releases that contain significant mass fractions of highly reactive volatile organic compounds (HRVOCs). In this work, time series analyses are used to compare average annual flow rates for air pollutant emissions with those released during reported emission events. The results indicate that the magnitude and frequency of HRVOC event emissions are an important element in accurately reflecting ozone precursor emission patterns in the Houston-Galveston area, particularly in Harris, Brazoria, Galveston, and Chambers counties. More than 50% of the reported episodic (event) emissions of HRVOCs are ethene and approximately a third are propene; the remainders are isomers of butene and 1,3-butadiene. Most events last less than 24 h. The mass released in an event can vary from a few hundred to more than 100,000 lb, and the dominant type of industrial source is chemical manufacturers (SIC 2869). Daily emissions from a single facility can vary from annual average emissions by multiple orders of magnitude at a frequency of several times a year. Because there are so many facilities in the Houston-Galveston area, HRVOC emission variability of this magnitude can be expected daily, at some time and some location in the Houston-Galveston area. If the emission variability occurs at times and locations where atmospheric conditions are conducive to ozone formation, both ambient data and photochemical modeling indicate that industrial emission events can lead to elevated concentrations of ozone. Specifically, peak, area-wide ozone concentration can be increased by as much as 100 ppb for large HRVOC emission events.     

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.     

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.     

Ozone assessment in the southern part of the Alps

In this paper ozone measurements carried out at six alpine and prealpine sites, located in the Italian region of Central Alps are shown. The stations are placed at altitudes between 800 and 1900 m a.s.l., far away from local sources of pollution. Ozone concentrations appear to be quite uniform, with summer mean values varying from 40 to 47 ppb and winter ones from 19 to 35 ppb. The number of hours exceeding the 75 and 100 ppb WHO thresholds and the AOT40 (Average Over Threshold 40 ppb of ozone) are evaluated for the growing season. The temporal variability of weekly ozone cycle at alpine stations provides useful informations to assess an emission control strategy.     

Modelling local and synoptic scale influences on ozone concentrations in a topographically complex region of Southern Italy

A modelling study with the on-line coupled Eulerian chemical-weather model WRF/Chem for the Southern Italian region around Cosenza (Calabria) was conducted to identify the influences of synoptic scale meteorology, local scale wind systems and local emissions on ozone concentrations in this orographically complex region. Four periods of 5–7 days were chosen, one from each season, which had wind pattern characteristics representative of typical local climatological conditions, in order to study the local versus non-local impacts on ozone transport and formation. To account for the complex terrain, the horizontal resolution of the smallest modelling domain was 3 km. Model results were compared with measurements to demonstrate the capability of the model to reproduce ozone concentrations in the region. The comparison was favourable with a mean bias of ?1.1 ppb. The importance of local emissions on ozone formation and destruction was identified with the use of three different emission scenarios. Generally the influence of regional emissions on the average ozone concentration was small. However during periods when mountain-sea wind systems were well developed and synoptic scale winds were weak, the influence of local emissions from the urban area was at its greatest. The maximum influence of local emissions on ozone concentrations was 18 ppb.     

Revised estimates of construction activity and emissions: Effects on ozone and elemental carbon concentrations in southern California

Emissions from diesel-powered construction equipment are an important source of nitrogen oxides (NO_x) and particulate matter (PM). A new emission inventory for construction equipment emissions is developed based on surveys of diesel fuel use; the revised inventory is compared to current emission inventories. California's OFFROAD model estimates are 4.5 and 3.1 times greater, for NO_x and PM respectively, than the fuel-based estimates developed here. The most relevant uncertainties are the overall amount of construction activity/diesel fuel use, exhaust emission factors for PM and NO_x, and the spatial allocation of emissions to county level and finer spatial scales. Construction permit data were used in this study to estimate spatial distributions of emissions; the resulting distribution is well correlated with population growth. An air quality model was used to assess the impacts of revised emission estimates. Increases of up to 15 ppb in predicted peak ozone concentrations were found in southern California. Elemental carbon and fine particle mass concentrations were in better agreement with observations using revised emission estimates, whereas negative bias in predictions of ambient NO_x concentrations increased.     

Surface ozone background in the United States: Canadian and Mexican pollution influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.     

Impact of biogenic emission uncertainties on the simulated response of ozone and fine particulate matter to anthropogenic emission reductions

The role of emissions of volatile organic compounds and nitric oxide from biogenic sources is becoming increasingly important in regulatory air quality modeling as levels of anthropogenic emissions continue to decrease and stricter health-based air quality standards are being adopted. However, considerable uncertainties still exist in the current estimation methodologies for biogenic emissions. The impact of these uncertainties on ozone and fine particulate matter (PM2.5) levels for the eastern United States was studied, focusing on biogenic emissions estimates from two commonly used biogenic emission models, the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the Biogenic Emissions Inventory System (BEIS). Photochemical grid modeling simulations were performed for two scenarios: one reflecting present day conditions and the other reflecting a hypothetical future year with reductions in emissions of anthropogenic oxides of nitrogen (NOx). For ozone, the use of MEGAN emissions resulted in a higher ozone response to hypothetical anthropogenic NOx emission reductions compared with BEIS. Applying the current U.S. Environmental Protection Agency guidance on regulatory air quality modeling in conjunction with typical maximum ozone concentrations, the differences in estimated future year ozone design values (DVF) stemming from differences in biogenic emissions estimates were on the order of 4 parts per billion (ppb), corresponding to approximately 5% of the daily maximum 8-hr ozone National Ambient Air Quality Standard (NAAQS) of 75 ppb. For PM2.5, the differences were 0.1-0.25 microg/m3 in the summer total organic mass component of DVFs, corresponding to approximately 1-2% of the value of the annual PM2.5 NAAQS of 15 microg/m3. Spatial variations in the ozone and PM2.5 differences also reveal that the impacts of different biogenic emission estimates on ozone and PM2.5 levels are dependent on ambient levels of anthropogenic emissions.     

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

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

Natural emissions for regional modeling of background ozone and particulate matter and impacts on emissions control strategies

Natural emissions adopted in current regional air quality modeling are updated to better describe natural background ozone and PM concentrations for North America. The revised natural emissions include organosulfur from the ocean, NO from lightning, sea salt, biogenic secondary organic aerosol (SOA) precursors, and pre-industrial levels of background methane. The model algorithm for SOA formation was also revised. Natural background ozone concentrations increase by up to 4 ppb in annual average over the southeastern US and Gulf of Mexico due to added NO from lightning while the revised biogenic emissions produced less ozone in the central and western US. Natural PM_2.5 concentrations generally increased with the revised natural emissions. Future year (2018) simulations were conducted for several anthropogenic emission reduction scenarios to assess the impact of the revised natural emissions on anthropogenic emission control strategies. Overall, the revised natural emissions did not significantly alter the ozone responses to the emissions reductions in 2018. With revised natural emissions, ozone concentrations were slightly less sensitive to reducing NOx in the southeastern US than with the current natural emissions due to higher NO from lightning. The revised natural emissions have little impact on modeled PM_2.5 responses to anthropogenic emission reductions. However, there are substantial uncertainties in current representations of natural sources in air quality models and we recommend that further study is needed to refine these representations.     

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.     

VOC concentration profiles in an ozone non-attainment area: A case study in an urban and industrial complex metroplex in southern Taiwan

VOCs are important precursors of the atmospheric ozone formation species. This study investigated the airborne concentrations of 52 VOCs at two air quality monitoring stations, Daliao and Tzouying, during wintertime in southern Taiwan. Airborne VOCs samples were taken in stainless steel canisters four times per day and analyzed via gas chromatography/mass spectrometry. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential in this ozone non-attainment region. Toluene, propane, isopentane, propene, n-butane, n-pentane and isoprene contributed 78–79% of the 52 VOCs in Daliao. Toluene, 1-butene, isopentane, propene, propane, n-undecane, and n-butane contributed 71–77% of the 52 VOCs in Tzouying. The VOCs concentrations were higher in Daliao due to the high toluene emissions from a paint plant and a solvent plant in the nearby industrial district. The 24-h VOC concentrations averaged 25 ppb higher in Tzouying than in Daliao. The ozone formation potential of airborne VOCs was 1687–2730 and 1717–2261 μg-O₃/g-VOCs in Daliao and Tzouying, respectively. Ozone concentrations in Tzouying were 44 ppb higher than in Daliao during the 1200–1600 sampling period.     

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.     

Overview of surface measurements and spatial characterization of submicrometer particulate matter during the DISCOVER-AQ 2013 campaign in Houston,TX

The sources of submicrometer particulate matter (PM₁) remain poorly characterized in the industrialized city of Houston, TX. A mobile sampling approach was used to characterize PM₁ composition and concentration across Houston based on high-time-resolution measurements of nonrefractory PM₁ and trace gases during the DISCOVER-AQ Texas 2013 campaign. Two pollution zones with marked differences in PM₁ levels, character, and dynamics were established based on cluster analysis of organic aerosol mass loadings sampled at 16 sites. The highest PM₁ mass concentrations (average 11.6 ± 5.7 µg/m³) were observed to the northwest of Houston (zone 1), dominated by secondary organic aerosol (SOA) mass likely driven by nighttime biogenic organonitrate formation. Zone 2, an industrial/urban area south/east of Houston, exhibited lower concentrations of PM₁ (average 4.4 ± 3.3 µg/m³), significant organic aerosol (OA) aging, and evidence of primary sulfate emissions. Diurnal patterns and backward-trajectory analyses enable the classification of airmass clusters characterized by distinct PM sources: biogenic SOA, photochemical aged SOA, and primary sulfate emissions from the Houston Ship Channel. Principal component analysis (PCA) indicates that secondary biogenic organonitrates primarily related with monoterpenes are predominant in zone 1 (accounting for 34% of the variability in the data set). The relevance of photochemical processes and industrial and traffic emission sources in zone 2 also is highlighted by PCA, which identifies three factors related with these processes/sources (~50% of the aerosol/trace gas concentration variability). PCA reveals a relatively minor contribution of isoprene to SOA formation in zone 1 and the absence of isoprene-derived aerosol in zone 2. The relevance of industrial amine emissions and the likely contribution of chloride-displaced sea salt aerosol to the observed variability in pollution levels in zone 2 also are captured by PCA.

Implications: This article describes an urban-scale mobile study to characterize spatial variations in submicrometer particulate matter (PM₁) in greater Houston. The data set indicates substantial spatial variations in PM₁ sources/chemistry and elucidates the importance of photochemistry and nighttime oxidant chemistry in producing secondary PM₁. These results emphasize the potential benefits of effective control strategies throughout the region, not only to reduce primary emissions of PM₁ from automobiles and industry but also to reduce the emissions of important secondary PM₁ precursors, including sulfur oxides, nitrogen oxides, ammonia, and volatile organic compounds. Such efforts also could aid in efforts to reduce mixing ratios of ozone.     

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.     

Changes in seasonal and diurnal cycles of ozone and temperature in the eastern U.S.

The pollutant tropospheric ozone causes human health problems, and environmental degradation and acts as a potent greenhouse gas. Using long-term hourly observations at five US air quality monitoring surface stations we studied the seasonal and diel cycles of ozone concentrations and surface air temperature to examine the temporal evolution over the past two decades. Such an approach allows visualizing the impact of natural and anthropogenic processes on ozone; nocturnal inversion development, photochemistry, and stratospheric intrusion. Analysis of the result provides an option for determining the duration for a regulatory ozone season. The application of the method provides independent confirmation of observed changes and trends in the ozone and temperature data records as reported elsewhere. The results provide further evidence supporting the assertion that ozone reductions can be attributed to emission reductions as opposed to weather variation. Despite a (～0.5 °C decade^?1) daytime warming trend, ozone decreased by up to 6 ppb decade^?1 during times of maximum temperature in the most polluted locations. Ozone also decreased across the emission reduction threshold of 2002 by 6–10 ppb indicating that emission reductions have been effective where and when it is most needed. Longer time series, and coupling with other data sources, may allow for the direct investigation of climate change influence on regional ozone air pollution formation and destruction over annual and daily time scales.     

Modeling the influence of biogenic volatile organic compound emissions on ozone concentration during summer season in the Kinki region of Japan

Tropospheric ozone adversely affects human health and vegetation, and biogenic volatile organic compound (BVOC) emission has potential to influence ozone concentration in summer season. In this research, the standard emissions of isoprene and monoterpene from the vegetation of the Kinki region of Japan, estimated from growth chamber experiments, were converted into hourly emissions for July 2002 using the temperature and light intensity data obtained from results of MM5 meteorological model. To investigate the effect of BVOC emissions on ozone production, two ozone simulations for one-month period of July 2002 were carried out. In one simulation, hourly BVOC emissions were included (BIO), while in the other one, BVOC emissions were not considered (NOBIO). The quantitative analyses of the ozone results clearly indicate that the use of spatio-temporally varying BVOC emission improves the prediction of ozone concentration. The hourly differences of monthly-averaged ozone concentrations between BIO and NOBIO had the maximum value of 6 ppb at 1400 JST. The explicit difference appeared in urban area, though the place where the maximum difference occurred changed with time. Overall, BVOC emissions from the forest vegetation strongly affected the ozone generation in the urban area.     

Long-range transport and re-circulation of pollutants in the western Mediterranean during the project Regional Cycles of Air Pollution in the West-Central Mediterranean Area

During the warm season (March–September), high ozone concentrations have been reported at the coastal and mountain monitoring stations of the eastern Iberia coast (Millán et al., J. Geophys. Res. 102 (D7) 8811, J. Appl. Meteorol. 4 (2000) 487). The vegetation protection threshold of current Directive 92/72/EEC and the World Health Organisation guideline for the protection of crops and semi-natural vegetation are systematically exceeded during the whole period. The main objective of the present study is to search for the origin of these chronic pollution levels: to search for the reason(s) for such high O₃ concentrations during such a long period. A mesoscale model is used to reproduce the diurnal cycle of winds and stability/layering over the Western Mediterranean Basin (WMB), at a sufficient space/temporal resolution, under a typical recursive synoptic condition during the warm season: data from the flight tracks of the European Project—Regional Cycles of Air Pollution in the West-Central Mediterranean Area—are used to substantiate the model results. Times of residence and the final distribution of pollutants entering the WMB are estimated using single-particle Lagrangian trajectories and a multiple-particle dispersion model. Our results show that the marine boundary layer and the lower troposphere in the region between the Balearic Islands and eastern Iberia are subject to a flow regime that tends to accumulate pollutants within large circulations, covering the entire western basin. We have also shown a diurnal pulsation of the Tramontana/Mistral wind regime, which can transport new pollutants into the area (background concentrations of 50–65 ppb of O₃ of continental European origin) that are added to local emissions and re-circulated within the coastal breezes at eastern Iberia for periods of more than five days. Local emissions and wind configuration contribute to increase the O₃ concentrations up to 100 ppb and even more.     

The sensitivity of modeled ozone to the temporal distribution of point, area, and mobile source emissions in the eastern United States

Ozone remains one of the most recalcitrant air pollution problems in the US. Hourly emissions fields used in air quality models (AQMs) generally show less temporal variability than corresponding measurements from continuous emissions monitors (CEM) and field campaigns would imply. If emissions control scenarios to reduce emissions at peak ozone forming hours are to be assessed with AQMs, the effect of emissions' daily variability on modeled ozone must be understood. We analyzed the effects of altering all anthropogenic emissions' temporal distributions by source group on 2002 summer-long simulations of ozone using the Community Multiscale Air Quality Model (CMAQ) v4.5 and the Carbon Bond IV (CBIV) chemical mechanism with 12 km resolution. We find that when mobile source emissions were made constant over the course of a day, 8-h maximum ozone predictions changed by ±7 parts per billion by volume (ppbv) in many urban areas on days when ozone concentrations greater than 80 ppbv were simulated in the base case. Increasing the temporal variation of point sources resulted in ozone changes of +6 and −6 ppbv, but only for small areas near sources. Changing the daily cycle of mobile source emissions produces substantial changes in simulated ozone, especially in urban areas at night; results suggest that shifting the emissions of NO_x from day to night, for example in electric powered vehicles recharged at night, could have beneficial impacts on air quality.     

Long-term meteorologically independent trend analysis of ozone air quality at an urban site in the greater Houston area

The Houston-Galveston-Brazoria (HGB) area of Texas has a history of ozone exceedances and is currently classified under moderate nonattainment status for the 2008 8-hr ozone standard of 75 ppb. The HGB area is characterized by intense solar radiation, high temperature, and high humidity, which influence day-to-day variations in ozone concentrations. Long-term air quality trends independent of meteorological influence need to be constructed for ascertaining the effectiveness of air quality management in this area. The Kolmogorov-Zurbenko (KZ) filter technique, used to separate different scales of motion in a time series, is applied in the current study for maximum daily 8-hr (MDA8) ozone concentrations at an urban site (U.S. Environmental Protection Agency [EPA] Air Quality System [AQS] Site ID: 48-201-0024, Aldine) in the HGB area. This site, located within 10 miles of downtown Houston and the George Bush Intercontinental Airport, was selected for developing long-term meteorologically independent MDA8 ozone trends for the years 1990–2016. Results from this study indicate a consistent decrease in meteorologically independent MDA8 ozone between 2000 and 2016. This pattern could be partially attributed to a reduction in underlying nitrogen oxide (NO_x) emissions, particularly lowering nitrogen dioxide (NO₂) levels, and a decrease in the release of highly reactive volatile organic compounds (HRVOCs). Results also suggest solar radiation to be most strongly correlated to ozone, with temperature being the secondary meteorological control variable. Relative humidity and wind speed have tertiary influence at this site. This study observed that meteorological variability accounts for a high of 61% variability in baseline ozone (low-frequency component, sum of long-term and seasonal components), whereas 64% of the change in long-term MDA8 ozone post 2000 could be attributed to NO_x emission reduction. Long-term MDA8 ozone trend component was estimated to be decreasing at a linear rate of 0.412 ± 0.007 ppb/yr for the years 2000–2016 and 0.155 ± 0.005 ppb/yr for the overall period of 1990–2016.

Implications: The effectiveness of air emission controls can be evaluated by developing long-term air quality trends independent of meteorological influences. The KZ filter technique is a well-established method to separate an air quality time series into short-term, seasonal, and long-term components. This paper applies the KZ filter technique to MDA8 ozone data between 1990 and 2016 at an urban site in the greater Houston area and estimates the variance accounted for by the primary meteorological control variables. Estimates for linear trends of MDA8 ozone are calculated and underlying causes are investigated to provide a guidance for further investigation into air quality management of the greater Houston area.