A new condensed toluene mechanism for Carbon Bond: CB05-TU

Toluene is ubiquitous in urban atmospheres and is a precursor to tropospheric ozone and aerosol (smog). An important characteristic of toluene chemistry is the tendency of some degradation products (e.g., cresols and methyl-catechols) to form organic nitro and nitrate compounds that sequester NOx (NO and NO₂) from active participation in smog formation. Explaining the NOx sinks in toluene degradation has made mechanism development more difficult for toluene than for many other organic compounds. Another challenge for toluene is explaining sources of radicals early in the degradation process. This paper describes the development of a new condensed toluene mechanism consisting of 26 reactions, and evaluates the performance of CB05 with this new toluene scheme (Toluene Update, TU) against 38 chamber experiments at 7 different environmental chambers, and provides recommendations for future developments. CB05 with the current toluene mechanism (CB05-Base) under-predicted the maximum O₃ and O₃ production rate for many of these toluene–NOx chamber experiments, especially under low-NOx conditions ([NOx]_t=0 < 100 ppb). CB05 with the new toluene mechanism (CB05-TU) includes changes to the yields and reactions of cresols and ring-opening products, and showed better performance than CB05-Base in predicting the maximum O₃, O₃ formation rate, NOx removal rate and cresol concentration. Additional environmental chamber simulations with xylene–NOx experiments showed that the TU mechanism updates tended to improve mechanism performance for xylene.     

Air pollutant concentrations near three Texas roadways,Part I: Ultrafine particles

Vehicular emitted air pollutant concentrations were studied near three types of roadways in Austin, Texas: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway dominated by truck traffic. Air pollutants examined include carbon monoxide (CO), oxides of nitrogen (NO_x), and carbonyl species in the gas-phase. In the particle phase, ultrafine particle (UFP) concentrations (diameter < 100 nm), fine particulate matter (PM_2.5, diameter < 2.5 μm) mass and carbon content and several particle-bound organics were examined. All roadways had an upwind stationary sampling location, one or two fixed downwind sample locations and a mobile monitoring platform that characterized pollutant concentrations fall-off with increased distance from the roadways. Data reported in this paper focus on UFP while other pollutants and near-roadway chemical processes are examined in a companion paper. Traffic volume, especially heavy-duty traffic, wind speed, and proximity to the road were found to be the most important factors determining UFP concentrations near the roadways. Since wind directions were not consistent during the sampling periods, distances along wind trajectories from the roadway to the sampling points were used to study the decay characteristics of UFPs. Under perpendicular wind conditions, for all studied roadway types, particle number concentrations increased dramatically moving from the upwind side to the downwind side. The elevated particle number concentrations decay exponentially with increasing distances from the roadway with sharp concentration gradients observed within 100–150 m, similar to previously reported studies. A single exponential decay curve was found to fit the data collected from all three roadways very well under perpendicular wind conditions. No consistent pattern was observed for UFPs under parallel wind conditions. However, regardless of wind conditions, particle concentrations returned to background levels within a few hundred meters of the roadway. Within measured UFP size ranges, smaller particles (6–25 nm) decayed faster than larger ones (100–300 nm). Similar decay rates were observed among UFP number, surface, and volume.     

Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

Effects of land use data on dry deposition in a regional photochemical model for eastern Texas

Land use data are among the inputs used to determine dry deposition velocities for photochemical grid models such as the Comprehensive Air Quality Model with extensions (CAMx) that is currently used for attainment demonstrations and air quality planning by the state of Texas. The sensitivity of dry deposition and O3 mixing ratios to land use classification was investigated by comparing predictions based on default U.S. Geological Survey (USGS) land use data to predictions based on recently compiled land use data that were collected to improve biogenic emissions estimates. Dry deposition of O3 decreased throughout much of eastern Texas, especially in urban areas, with the new land use data. Predicted 1-hr averaged O3 mixing ratios with the new land use data were as much as 11 ppbv greater and 6 ppbv less than predictions based on USGS land use data during the late afternoon. In addition, the area with peak O3 mixing ratios in excess of 100 ppbv increased significantly in urban areas when deposition velocities were calculated based on the new land use data. Finally, more detailed data on land use within urban areas resulted in peak changes in O3 mixing ratios of approximately 2 ppbv. These results indicate the importance of establishing accurate, internally consistent land use data for photochemical modeling in urban areas in Texas. They also indicate the need for field validation of deposition rates in areas experiencing changing land use patterns, such as during urban reforestation programs or residential and commercial development.     

Air quality modeling of interpollutant trading for ozone precursors in an urban area

Emission trading is a market-based approach designed to improve the efficiency and economic viability of emission control programs; emission trading has typically been confined to trades among single pollutants. Interpollutant trading (IPT), as described in this work, allows for trades among emissions of different compounds that affect the same air quality end point, in this work, ambient ozone (O3) concentrations. Because emissions of different compounds impact air quality end points differently, weighting factors or trading ratios (tons of emissions of nitrogen oxides (NO(x)) equivalent to a ton of emissions of volatile organic compounds [VOCs]) must be developed to allow for IPT. In this work, IPT indices based on reductions in O3 concentrations and based on reductions in population exposures to O3 were developed and evaluated using a three-dimensional gridded photochemical model for Austin, TX, a city currently on the cusp of nonattainment with the National Ambient Air Quality Standards for O3 concentrations averaged over 8 hr. Emissions of VOC and NO(x) from area and mobile sources in Austin are larger than emissions from point sources. The analysis indicated that mobile and area sources exhibited similar impacts. Trading ratios based on maximum O3 concentration or population exposure were similar. In contrast, the trading ratios did exhibit significant (more than a factor of two) day-to-day variability. Analysis of the air quality modeling indicated that the daily variability in trading ratios could be attributed to daily variations in both emissions and meteorology.     

Effects of Land Use Data on Dry Deposition in a Regional Photochemical Model for Eastern Texas

ABSTRACT

Land use data are among the inputs used to determine dry deposition velocities for photochemical grid models such as the Comprehensive Air Quality Model with extensions (CAMx) that is currently used for attainment demonstrations and air quality planning by the state of Texas. The sensitivity of dry deposition and O₃ mixing ratios to land use classification was investigated by comparing predictions based on default U.S. Geological Survey (USGS) land use data to predictions based on recently compiled land use data that were collected to improve biogenic emissions estimates. Dry deposition of O₃ decreased throughout much of eastern Texas, especially in urban areas, with the new land use data. Predicted 1-hr averaged O₃ mixing ratios with the new land use data were as much as 11 ppbv greater and 6 ppbv less than predictions based on USGS land use data during the late afternoon. In addition, the area with peak O₃ mixing ratios in excess of 100 ppbv increased significantly in urban areas when deposition velocities were calculated based on the new land use data. Finally, more detailed data on land use within urban areas resulted in peak changes in O₃ mixing ratios of ~2 ppbv. These results indicate the importance of establishing accurate, internally consistent land use data for photochemical modeling in urban areas in Texas. They also indicate the need for field validation of deposition rates in areas experiencing changing land use patterns, such as during urban reforestation programs or residential and commercial development.     

Modeling alkene chemistry using condensed mechanisms for conditions relevant to southeast Texas,USA

Alkenes are important in photochemical smog formation in southeast Texas due to their high emissions, especially from industrial sources in and around Houston, and their high reactivities. Therefore, properly characterizing the chemistry of alkenes in condensed mechanisms used in regional photochemical models is important in understanding the formation of ozone and other photochemical air pollutants in Houston. The performance of three versions of the SAPRC condensed chemical mechanism family, for predicting ozone and radical formation, was compared. Simulations were compared to environmental chamber data and ambient data. The analyses showed that separately modeling individual alkenes reactions (especially propene for southeast Texas) has the potential to lead to more accurate simulations of alkene chemistry. Caution must be exercised in un-lumping, however. Testing with different formulations of the 1-butene + O₃ reaction demonstrated the complexity and interconnectedness in choices of stoichiometric parameters for un-lumped species and the extent to which lumped mechanisms are un-lumped.     

Applications of satellite remote sensing data for estimating biogenic emissions in southeastern Texas

The sensitivity of biogenic emission estimates and air quality model predictions to the characterization of land use/land cover (LULC) in southeastern Texas was examined using the Global Biosphere Emissions and Interactions System (GloBEIS) and the Comprehensive Air Quality Model with extensions (CAMx). A LULC database was recently developed for the region based on source imagery collected by the Landsat 7 Enhanced Thematic Mapper-Plus sensor between 1999 and 2003, and field data for land cover classification, species identification and quantification of biomass densities.  Biogenic emissions estimated from the new LULC data set showed good general agreement in their spatial distribution, but were approximately 40% lower than emissions from the LULC data set currently used by the State of Texas, primarily because of differences in the biomass estimates of key species such as Quercus. Predicted ozone mixing ratios using the biogenic emissions produced from the new LULC data set were as much as 26 ppb lower in some areas on some days, depending on meteorological conditions. Satellite data and image classification techniques provide useful tools for mapping and monitoring changes in LULC. However, field validation is necessary to link species and biomass densities to the classification system used for accurate biogenic emissions estimates, especially in areas such as riparian corridors that contain dense spatial coverage of key species.