Greg Yarwood

Impact of an Updated Carbon Bond Mechanism on Predictions from the CMAQ Modeling System: Preliminary Assessment

Abstract An updated and expanded version of the Carbon Bond mechanism (CB05) has been incorporated into the Community Multiscale Air Quality (CMAQ) modeling system to more accurately simulate wintertime, pristine, and high-altitude situations. The CB05 mechanism has nearly 2 times the number of reactions relative to the previous version of the Carbon Bond mechanism (CB-IV). While the expansions do provide more detailed treatment of urban areas, most of the new reactions involve biogenics, toxics, and species potentially important to particulate formation and acid deposition. Model simulations were performed using the CB05 and the CB-IV mechanisms for the winter and summer of 2001. For winter with the CB05 mechanism, ozone, aerosol nitrate, and aerosol sulfate concentrations were within 1% of the results obtained with the CB-IV mechanism. Organic carbon concentrations were within 2% of the results obtained with the CB-IV mechanism. However, formaldehyde and hydrogen peroxide concentrations were lower by 25...

Direct evidence for chlorine-enhanced urban ozone formation in Houston, Texas

Urban air pollution is characterized by high ozone levels, formed when volatile organic compounds (VOCs) are oxidized in the presence of nitrogen oxides (NOx). VOC and NOx emissions controls have traditionally been implemented to reduce urban ozone formation, however, a separate chemical species implicated in ozone formation in Houston, TX and possibly other urban areas is the chlorine radical (Cl ). Cl enhances tropospheric VOC oxidation, but is not included in models used to develop air quality attainment plans. We present results of a three-fold approach to elucidate the importance of Cl in urban ozone formation: (1) the first direct evidence of chlorine chemistry in the urban troposphere, (2) enhanced ozone formation (>75 parts per 10 9 (ppb/h) observed when small amounts of chlorine (Cl2) are injected into captive ambient air, and (3) enhanced ozone formation (B16 ppb) predicted by regional photochemical models employing Cl chemistry. These results suggest that reducing chlorine emissions should be considered in urban ozone management strategies. r 2003 Elsevier Science Ltd. All rights reserved.

Ozone impacts of natural gas development in the Haynesville Shale.

The Haynesville Shale is a subsurface rock formation located beneath the Northeast Texas/Northwest Louisiana border near Shreveport. This formation is estimated to contain very large recoverable reserves of natural gas, and during the two years since the drilling of the first highly productive wells in 2008, has been the focus of intensive leasing and exploration activity. The development of natural gas resources within the Haynesville Shale is likely to be economically important but may also generate significant emissions of ozone precursors. Using well production data from state regulatory agencies and a review of the available literature, projections of future year Haynesville Shale natural gas production were derived for 2009-2020 for three scenarios corresponding to limited, moderate, and aggressive development. These production estimates were then used to develop an emission inventory for each of the three scenarios. Photochemical modeling of the year 2012 showed increases in 2012 8-h ozone design values of up to 5 ppb within Northeast Texas and Northwest Louisiana resulting from development in the Haynesville Shale. Ozone increases due to Haynesville Shale emissions can affect regions outside Northeast Texas and Northwest Louisiana due to ozone transport. This study evaluates only near-term ozone impacts, but the emission inventory projections indicate that Haynesville emissions may be expected to increase through 2020.

Establishing Policy Relevant Background (PRB) ozone concentrations in the United States

Policy Relevant Background (PRB) ozone concentrations are defined by the United States (U.S.) Environmental Protection Agency (EPA) as those concentrations that would occur in the U.S. in the absence of anthropogenic emissions in continental North America (i.e., the U.S, Canada, and Mexico). Estimates of PRB ozone have had an important role historically in the EPAs human health and welfare risk analyses used in establishing National Ambient Air Quality Standards (NAAQS). The margin of safety for the protection of public health in the ozone rulemaking process has been established from human health risks calculated based on PRB ozone estimates. Sensitivity analyses conducted by the EPA have illustrated that changing estimates of PRB ozone concentrations have a progressively greater impact on estimates of mortality risk as more stringent standards are considered. As defined by the EPA, PRB ozone is a model construct, but it is informed by measurements at relatively remote monitoring sites (RRMS). This review examines the current understanding of PRB ozone, based on both model predictions and measurements at RRMS, and provides recommendations for improving the definition and determination of PRB ozone.

Sensitivity of urban ozone formation to chlorine emission estimates

Abstract Recent evidence has demonstrated that chlorine radical chemistry can enhance tropospheric volatile organic compound oxidation and has the potential to enhance ozone formation in urban areas. In order to investigate the regional impacts of chlorine chemistry in southeastern Texas, preliminary estimates of atmospheric releases of atomic chlorine precursors from industrial point sources, cooling towers, water and wastewater treatment, swimming pools, tap water, reactions of chlorides in sea salt aerosols, and reactions of chlorinated organics were developed. To assess the potential implications of these estimated emissions on urban ozone formation, a series of photochemical modeling studies was conducted to examine the spatial and temporal sensitivity of ozone and a unique marker species for chlorine chemistry, 1-Chloro-3-methyl-3-butene-2-one (CMBO), to molecular chlorine emissions estimates. Based on current estimates of molecular chlorine emissions in southeastern Texas, chlorine chemistry has the potential to enhance ozone mixing ratios by up to 11–16xa0ppbv. Impacts varied temporally, with emissions from cooling towers primarily responsible for a morning enhancement in ozone mixing ratios and emissions from residential swimming pools for an afternoon enhancement. Maximum enhancement in CMBO mixing ratios ranged from 59 to 69xa0pptv.

A land use database and examples of biogenic isoprene emission estimates for the state of Texas, USA

Using data from a variety of sources, land use and vegetation in Texas were mapped with a spatial resolution of approximately 1 km. Over 600 classifications were used to characterize the land use and land cover throughout the state and field surveys were performed to assign leaf biomass densities, by species, to the land cover classifications. The total leafbiomass densities associated with these land use classifications ranged from 0 to 556 g/m 2 , with the highest assigned total and oak leafbiomass densities located in central and eastern Texas. The land cover data were used as input to a biogenic emissions model, GLOBEIS2. Estimates ofbiogenic emissions ofisoprene based on GLOBEIS2 and the new land cover data showed significant differences when compared to biogenic isoprene emissions estimated using previous land cover data and emission estimation procedures. For example, for one typical domain in eastern Texas, total daily isoprene emissions increased by 38% with the new modeling tools. These results may ultimately affect the way in which ozone and other photochemical pollutants are modeled and evaluated in the state ofTexas. r 2001 Elsevier Science Ltd. All rights reserved.

Modeling weekday/weekend ozone differences in the Los Angeles region for 1997

Abstract Numerous studies of ambient ozone (O3) in the Los Angeles (LA) area have found both increases and decreases in elevated O3 levels on weekends, depending on location and year. Since the mid-1990s, average daily maximum O3 levels have been higher on weekends than on week-days throughout most of the area. We used the Comprehensive Air-Quality Model with extensions to investigate causes of weekday/weekend O3 differences in the LA area for August 3–7, 1997, from the Southern California Ozone Study. Weekday/weekend emission changes were estimated, because explicit weekend inventories are not yet available from regulatory agencies. Changes to on-road motor vehicle (MV) emissions were derived from observed weekday/weekend traffic differences. The estimated changes in MV emissions of nitrogen oxides (NOx) were a 5% increase on Friday, a 27% decrease on Saturday, and a 37% decrease on Sunday, relative to Monday–Thursday levels. The corresponding changes in MV volatile organic carbon (VOC) emissions were an 8% increase on Friday, an 8% decrease on Saturday, and a 15% decrease on Sunday. Modeling these MV emissions changes explained the observed weekend O3 effect very well. Furthermore, changes to the mass of MV NOx emissions were the main contributor to O3 differences rather than changes to the timing of MV emissions. Ozone increases on weekends were caused by NOx emission decreases, because O3 formation is strongly VOC-limited throughout most of the LA area.

Development of a chlorine mechanism for use in the carbon bond IV chemistry model

[1]xa0Chlorine chemistry has been incorporated into the carbon bond IV mechanism and employed in a regional photochemical model (the Comprehensive Air Quality Model with Extensions (CAMx)) for preliminary use in assessing the regional impact of chlorine on ozone formation in Houston, Texas. Mechanisms employed in regional photochemical models do not currently account for chlorine chemistry. However, when chlorine chemistry is accounted for, predicted ozone levels are enhanced by up to 16 ppbv in the Houston area, with the greatest enhancement predicted for morning hours after sunrise. Thirteen reactions have been added to the chemical mechanism used by CAMx to describe chlorine chemistry in the urban atmosphere. The reactions include photolysis of chlorine radical (Cl·) precursors, Cl·+ hydrocarbon reactions, and Cl·+ ozone reactions. The hydrocarbon reactions include the reactions of Cl· with isoprene and 1,3-butadiene that yield unique reaction products, or marker species. The development of this mechanism is presented along with a discussion of the initial set of predictions of chlorine-based ozone enhancement in the Houston area. Of significant interest is that methane may be activated by chlorine to contribute significantly to the predicted ozone enhancement in the Houston area. Such behavior suggests that the impact of chlorine chemistry would be proportional to the availability of Cl· precursor. In urban areas with anthropogenic sources of chlorine radical precursors, chlorine radical chemistry may be important to more accurately predict ozone formation.

Contributions of regional transport and local sources to ozone exceedances in Houston and Dallas: Comparison of results from a photochemical grid model to aircraft and surface measurements

[1]xa0During the 2000 Texas Air Quality Study (TexAQS) and 2006 Texas Air Quality Study (TexAQS II) field experiments, aircraft measured ozone concentrations upwind, across, and downwind of the Houston and Dallas urban areas. Background ozone transported into Houston contributed, on average, approximately 50% and 66% of the total ozone on 8-h ozone exceedance days investigated by aircraft flights during TexAQS and TexAQS II, respectively. Analysis of a flight over Dallas on one exceedance day showed that transported ozone constituted 72% of the total ozone concentration. The aircraft measurements show that these two major metropolitan areas can be brought close to exceeding the 1997 8-h National Ambient Air Quality Standard for ozone of 0.08 ppm solely by the ozone contribution of regional transport before additional contribution from local sources. Large local contributions were also observed, particularly in Houston. Transport contributions to Dallas area ozone were quantified using the Comprehensive Air Quality Model with Extensions (CAMx) photochemical grid model and source apportionment methods. Model-predicted ozone concentrations were compared to ozone measurements from the aircraft and the surface monitoring network, and showed agreement on the importance of regional transport and local ozone formation. These results emphasize the benefits of regional control strategies, and suggest that local controls alone may not be sufficient to ensure attainment of the 8-h ozone standard in Houston and Dallas.

Biogenic hydrocarbon emission estimates for North Central Texas

Abstract Biogenic hydrocarbon emissions were estimated for a 37 county region in North Central Texas. The estimates were based on several sources of land use/land cover data that were combined using geographical information systems. Field studies were performed to collect species and tree diameter distribution data. These data were used to estimate biomass densities and species distributions for each of the land use/land cover classifications. VOC emissions estimates for the domain were produced using the new land use/land cover data and a biogenic emissions model. These emissions were more spatially resolved and a factor of 2 greater in magnitude than those calculated based on the biogenic emissions landuse database (BELD) commonly used in biogenic emissions models.