Comprehensive Air Quality Model With Extensions Research Articles

Source Apportionment of Sulfate and Nitrate over the Pearl River Delta Region in China

In this work, the Weather Research Forecast (WRF)–Sparse Matrix Operator Kernel Emission (SMOKE)–Comprehensive Air Quality Model with Extensions (CAMx) modeling system with particulate source apportionment technology (PSAT) module was used to study and analyze the source apportionment of sulfate and nitrate particulate matter in the Pearl River Delta region (PRD). The results show that superregional transport was an important contributor for both sulfates and nitrates in all 10 cities in this region in both February (winter) and August (summer). Especially in February, the average super-regional contribution of sulfate and nitrate reached up to 80% and 56% respectively. For the local and regional source category, power plant emissions (coal-fired and oil-fired) and industry emissions were important for sulfate formation in this region. Industry emissions and mobile emissions are important for nitrate formation in this region. In August, the sum of these two sources contributed around over 60% of local and regional nitrate. The contributions from power plant emissions and marine emissions became important in August due to the southerly prevailing wind direction. Area sources and biogenic emissions were negligible for sulfate and nitrate formation in this region. Our results reveal that cross-province cooperation is necessary for control of sulfates and nitrates in this region.

Impacts of natural emission sources on particle pollution levels in Europe

The main objective of this work is the study of the impact of windblown dust, sea-salt aerosol and biogenic emissions on particle pollution levels in Europe. The Natural Emissions MOdel (NEMO) and the modelling system consisted of the Weather Research and Forecasting model (WRF) and the Comprehensive Air Quality model with extensions (CAMx) were applied in a 30 km horizontal resolution grid, which covered Europe and the adjacent areas for the year 2009. Air quality simulations were performed for different emission scenarios in order to study the contribution of each natural emission source individually and together to air quality levels in Europe. The simulations reveal that the exclusion of windblown dust emissions decreases the mean seasonal PM10 levels by more than 3.3 μg/m3 (∼20%) in the Eastern Mediterranean during winter while an impact of 3 μg/m3 was also found during summer. The results suggest that sea-salt aerosol has a significant effect on PM levels and composition. Eliminating sea-salt emissions reduces PM10 seasonal concentrations by around 10 μg/m3 in Mediterranean Sea during summer while a decrease of up to 6 μg/m3 is found in Atlantic Ocean during autumn. Sea-salt particles also interact with the anthropogenic component and therefore their absence in the atmosphere decreases significantly the nitrates in aerosols where shipping activities are present. The exclusion of biogenic emissions in the model runs leads to a significant reduction of secondary organic aerosols of more than 90% while an increase in PM2.5 levels in central Europe and Eastern Mediterranean is found due to their interaction with anthropogenic component.

CAMx Ozone Source Attribution in the Eastern United States using Guidance from Observations during DISCOVER-AQ Maryland.

A Comprehensive Air-Quality Model with Extensions (CAMx) version 6.10 simulation was assessed through comparison with data acquired during NASA's 2011 DISCOVER-AQ Maryland field campaign. Comparisons for the baseline simulation (CB05 chemistry, EPA 2011 National Emissions Inventory) show a model overestimate of NOy by +86.2% and an underestimate of HCHO by -28.3%. We present a new model framework (CB6r2 chemistry, MEGAN v2.1 biogenic emissions, 50% reduction in mobile NOx, enhanced representation of isoprene nitrates) that better matches observations. The new model framework attributes 31.4% more surface ozone in Maryland to electric generating units (EGUs) and 34.6% less ozone to on-road mobile sources. Surface ozone becomes more NOx-limited throughout the eastern United States compared to the baseline simulation. The baseline model therefore likely underestimates the effectiveness of anthropogenic NOx reductions as well as the current contribution of EGUs to surface ozone.

Contribution of ship emissions to the concentration and deposition of air pollutants in Europe

Abstract. Emissions from the marine transport sector are one of the least-regulated anthropogenic emission sources and contribute significantly to air pollution. Although strict limits were introduced recently for the maximum sulfur content in marine fuels in the SECAs (sulfur emission control areas) and in EU ports, sulfur emissions outside the SECAs and emissions of other components in all European maritime areas have continued to increase in the last two decades. We have used the air quality model CAMx (Comprehensive Air Quality Model with Extensions) with and without ship emissions for the year 2006 to determine the effects of international shipping on the annual as well as seasonal concentrations of ozone, primary and secondary components of PM2.5, and the dry and wet deposition of nitrogen and sulfur compounds in Europe. The largest changes in pollutant concentrations due to ship emissions were predicted for summer. Concentrations of particulate sulfate increased due to ship emissions in the Mediterranean (up to 60 %), the English Channel and the North Sea (30–35 %), while increases in particulate nitrate levels were found especially in the north, around the Benelux area (20 %), where there were high NH3 land-based emissions. Our model results showed that not only are the atmospheric concentrations of pollutants affected by ship emissions, but also depositions of nitrogen and sulfur compounds increase significantly along the shipping routes. NOx emissions from the ships, especially in the English Channel and the North Sea, cause a decrease in the dry deposition of reduced nitrogen at source regions by moving it from the gas phase to the particle phase which then contributes to an increase in the wet deposition at coastal areas with higher precipitation. In the western Mediterranean region, on the other hand, model results show an increase in the deposition of oxidized nitrogen (mostly HNO3) due to the ship traffic. Dry deposition of SO2 seems to be significant along the shipping routes, whereas sulfate wet deposition occurs mainly along the Scandinavian and Adriatic coasts. The results presented in this paper suggest that evolution of NOx emissions from ships and land-based NH3 emissions will play a significant role in future European air quality.

Evidence for an increase in the ozone photochemical lifetime in the eastern United States using a regional air quality model

AbstractMeasures to control surface ozone rely on quantifying production attributable to local versus regional (upwind) emissions. Here we simulate the relative contribution of local (i.e., within a particular state) and regional sources of surface ozone in the eastern United States (66–94°W longitude) for July 2002, 2011, and 2018 using the Comprehensive Air‐quality Model with Extensions (CAMx). To determine how emissions and chemistry within the domain affect the production, loss, lifetime, and transport of trace gases, we initialize our model with identical boundary conditions in each simulation. We find that the photochemical lifetime of ozone has increased as emissions have decreased. The contribution of ozone from outside the domain (boundary condition ozone, BCO3) to local surface mixing ratios increases in an absolute sense by 1–2 ppbv between 2002 and 2018 due to the longer lifetime of ozone. The photochemical lifetime of ozone lengthens because the two primary gas phase sinks for odd oxygen (Ox ≈ NO2 + O3)—attack by hydroperoxyl radicals (HO2) on ozone and formation of nitrate—weaken with decreasing pollutant emissions. The relative role of BCO3 will also increase. For example, BCO3 represents 34.5%, 38.8%, and 43.6% of surface ozone in the Baltimore, MD, region during July 2002, 2011, and 2018 means, respectively. This unintended consequence of air quality regulation impacts attainment of the National Ambient Air Quality Standard for surface ozone because the spatial and temporal scales of photochemical smog increase; the influence of pollutants transported between states and into the eastern U.S. will likely play a greater role in the future.

A hybrid modeling approach for estimating reactive nitrogen deposition in Rocky Mountain National Park

Abstract Changes in ecosystem function at Rocky Mountain National Park (RMNP) are occurring because of nitrogen deposition associated with emissions of nitrogen from sources in Colorado as well as other areas of the North American continent and beyond. Nitrogen species are in both reduced and oxidized forms. A year-long monitoring program was initiated to better understand their origins as well as the complex chemistry occurring during transport from source to receptor. Specifically, the goals of the study were to characterize the atmospheric concentrations of nitrogen species in gaseous, particulate, and aqueous phases in RMNP and to identify the emission sources of these various species. The apportionment strategy was designed to focus on differentiating between sources within and outside the state of Colorado and then further differentiate between sources along the Front Range of Colorado and the rest of Colorado. It was also desirous to identify the relative contributions to atmospheric nitrogen species from mobile sources, agricultural activities, and large and small point sources within the state of Colorado. The Particle Source Apportionment Technology (PSAT) module available in the chemical transport model, the Comprehensive Air quality Model with extensions (CAMx), is used to develop first-principle estimates of the contributions from different areas of North America. The CAMx_PSAT results are combined with measured species concentrations in a receptor modeling approach to develop final estimates of source apportionment of the various species' concentrations and deposition.

Photochemical grid model estimates of lateral boundary contributions to ozone and particulate matter across the continental United States

Multiple approaches to characterize lateral boundary contributions to photochemical model predicted ozone (O3) and particulate matter less than 2.5 microns in diameter (PM2.5) are available in the Comprehensive Air quality Model with extensions (CAMx). Here, three approaches are used for O3: (1) a comprehensive source apportionment scheme for chemical boundary conditions and emissions (OSAT), (2) chemically reactive tracers (RTRAC), and (3) chemically inert tracers. Two approaches are used for PM2.5: (1) particulate source apportionment (PSAT) and (2) chemically inert tracers. The inert tracer approach resulted in higher O3 lateral boundary contribution estimates because the method does not account for any O3 destruction reactions. OSAT and RTRAC estimate generally similar monthly average contributions during the warmer months although RTRAC estimates higher urban area contribution during the cold months because this RTRAC implementation did not treat O3 titration by NO. Accurate representation of lateral boundary O3 impacts must include appropriate accounting for O3 destruction reactions. OSAT and RTRAC were configured to estimate the contribution to modeled O3 from each of the four lateral faces of the model domain. RTRAC was configured to further stratify the western and northern boundaries by groups of vertical layers. The RTRAC approach showed that the largest O3 contributions to the continental U.S. are from the mid-troposphere, with less contribution from the upper troposphere/lower stratosphere. Inert tracers compared more closely to reactive tracers on average for PM2.5 compared to O3. This close agreement for PM2.5 indicates most of the lateral boundary contribution is from PM2.5 rather than precursor inflow. A strong relationship exists between model predicted PM2.5 boundary contribution and model overestimates of nitrate and organic carbon at IMPROVE monitor locations suggesting global model estimates of these species were overestimated at some places and times.

The natural emissions model (NEMO): Description, application and model evaluation

The aim of this study is the application and evaluation of a new computer model used for the quantification of emissions coming from natural sources. The Natural Emissions Model (NEMO) is driven by the meteorological data of the mesoscale numerical Weather Research and Forecasting (WRF) model and it estimates particulate matter (PM) emissions from windblown dust, sea salt aerosols (SSA) and primary biological aerosol particles (PBAPs). It also includes emissions from Biogenic Volatile Organic Compounds (BVOCs) from vegetation; however, this study focuses only on particle emissions. An application and evaluation of NEMO at European scale are presented. NEMO and the modelling system consisted of WRF model and the Comprehensive Air Quality Model with extensions (CAMx) were applied in a 30 km European domain for the year 2009. The computed domain-wide annual PM10 emissions from windblown dust, sea salt and PBAPs were 0.57 Tg, 20 Tg and 0.12 Tg, respectively. PM2.5 represented 6% and 33% of emitted windblown dust and sea salt, respectively. Natural emissions are characterized by high geographical and seasonal variations; windblown dust emissions were the highest during summer in the southern Europe and SSA production was the highest in Atlantic Ocean during the cold season while in Mediterranean Sea the highest SSA emissions were found over the Aegean Sea during summer. Modelled concentrations were compared with surface station measurements and showed that the model captured fairly well the contribution of the natural sources to PM levels over Europe. Dust concentrations correlated better when dust transport events from Sahara desert were absent while the simulation of sea salt episodes led to an improvement of model performance during the cold season.

Source contributions of urban PM2.5 in the Beijing–Tianjin–Hebei region: Changes between 2006 and 2013 and relative impacts of emissions and meteorology

Anthropogenic emissions in China have been controlled for years to improve ambient air quality. However, severe haze events caused by atmospheric aerosols with aerodynamic diameter less than or equal to 2.5 μm (PM2.5) have continued to occur, especially in the Beijing–Tianjin–Hebei (BTH) region. The Chinese government has set an ambitious goal to reduce urban PM2.5 concentrations by 25% in BTH by 2017 relative to the 2012 levels. Source apportionment (SA) is necessary to the development of the effective emission control strategies. In this work, the Comprehensive Air Quality Model with extensions (CAMx) with the Particulate Source Apportionment Technology (PSAT) is applied to the China domain for the years 2006 and 2013. Ambient surface concentrations of PM2.5 and its components are generally well reproduced. To quantify the contributions of each emission category or region to PM2.5 in BTH, the total emissions are divided into 7 emission categories and 11 source regions. The source contributions determined in this work are generally consistent with results from previous work. In 2013, the industrial (44%) and residential (27%) sectors are the dominant contributors to urban PM2.5 in BTH. The residential sector is the largest contributor in winter; the industry sector dominates in other seasons. A slight increasing trend (+3% for industry and +6% for residential) is found in 2013 relative to 2006, necessitating more attention to these two sectors. Local emissions make the largest contribution (40%–60%) for all receptors. Change of source contribution of PM2.5 in Beijing and northern Hebei are dominate by change of local emission. However, for Tianjin, and central and southern Hebei, change of meteorology condition are as important as change of emission, because regional inflow in these areas is more important than in Beijing and northern Hebei and can increase under unfavorable weather conditions, indicating a strong need for regional joint emission control efforts. The results in this study enhance the quantitative understanding of the source–receptor relationships and provide an important basis for policymaking to advance the control of PM2.5 pollution in China.

Local and distant source contributions to secondary organic aerosol in the Beijing urban area in summer

Quantification of local and distant source contributions to particulate matter is a key issue to improving air quality in large urban areas, but few studies have focused on secondary organic aerosol (SOA) source contributions in a large area, especially in China. In this study, we extended the Comprehensive Air Quality Model with Extensions (CAMX) version 5.4, replacing the two-product approach by the volatility basis-set (VBS) approach, with updated SOA yields based on smog chamber studies. The modules related to the computationally efficient particulate source apportionment technology (PSAT) used in CAMX v5.4 were extended based on the volatility basis set (VBS) approach. The updated version of the CAMX model was then used to calculate the local and distant source contributions to SOA in Beijing for the first time. The results indicated that the VBS approach substantially improved hourly, daily, and monthly SOA simulations, compared with the two-product approach and the observations. In August 2007, the local source contributions to anthropogenic and biogenic SOA in Beijing were 23.8% and 16.6%, respectively; distant sources dominated for both anthropogenic and biogenic SOA in Beijing: Northern Hebei, Middle Hebei, Northeast China, Inner Mongolia, Shandong, and Tianjin (including Xianghe) contributed 5.1% e18.2% to anthropogenic SOA in Beijing; whereas, Inner Mongolia, Northern Hebei, and Northeast China contributed 12.2%, 18.6%, and 10.1%, respectively, to biogenic SOA in Beijing. Additionally, other areas outside China respectively contributed 5.3% and 10.8% to anthropogenic and biogenic SOA in Beijing: this could be related to strong summer monsoon.

Photochemical model simulations of air quality for Houston–Galveston–Brazoria area and analysis of ozone–NO x –hydrocarbon sensitivity

As part of the State Implementation Plan for the Houston–Galveston–Brazoria (HGB) area which has been declared as a non-attainment area, it was required to assess the impacts of pollutant emissions, meteorological conditions, and initial and boundary conditions on air quality. In this study, photochemical model simulations using the Comprehensive Air Quality Model with extensions (CAMx) were conducted for three ozone episodes between May and October of 2006. The CAMx simulations compared fairly well with the hourly average concentrations of ozone measured at the monitoring sites, and the index of agreement (IOA) values for all the three ozone episodes were found greater than 0.65, which proved to be good for CAMx model performance. Both simulated and observed peak ozone concentrations were observed to occur between 12:00 and 15:00 h. The CAMx simulation results showed that there were 68 days where the maximum 8-h mean ozone concentrations exceeded the NAAQS of 75 ppb out of a total of 72 days simulated in the three ozone episodes. For all three episodes, ozone concentrations were highest during the third quarter of the day. The photochemical indicator ratios of hydrogen peroxide (H2O2) to nitric acid (HNO3) ([H2O2]/[HNO3]) showed the HGB area to be a nitrogen oxide (NO x )-sensitive regime for the episodes studied. This indicated that volatile organic compounds (VOCs) are plentiful, and NO x is the limiting precursor for ozone formation in the HGB area. The plentiful VOCs in this region are possibly produced from industries and refineries in the HGB area.

Evaluating NOx emission inventories for regulatory air quality modeling using satellite and air quality model data

The purpose of this study was to assess the accuracy of NOx emissions in the Texas Commission on Environmental Quality's (TCEQ) State Implementation Plan (SIP) modeling inventories of the southeastern U.S. We used retrieved satellite tropospheric NO2 columns from the Ozone Monitoring Instrument (OMI) together with NO2 columns from the Comprehensive Air Quality Model with Extensions (CAMx) to make top–down NOx emissions estimates using the mass balance method. Two different top–down NOx emissions estimates were developed using the KNMI DOMINO v2.0 and NASA SP2 retrievals of OMI NO2 columns. Differences in the top–down NOx emissions estimates made with these two operational products derived from the same OMI radiance data were sufficiently large that they could not be used to constrain the TCEQ NOx emissions in the southeast. The fact that the two available operational NO2 column retrievals give such different top–down NOx emissions results is important because these retrievals are increasingly being used to diagnose air quality problems and to inform efforts to solve them. These results reflect the fact that NO2 column retrievals are a blend of measurements and modeled data and should be used with caution in analyses that will inform policy development. This study illustrates both benefits and challenges of using satellite NO2 data for air quality management applications. Comparison with OMI NO2 columns pointed the way toward improvements in the CAMx simulation of the upper troposphere, but further refinement of both regional air quality models and the NO2 column retrievals is needed before the mass balance and other emission inversion methods can be used to successfully constrain NOx emission inventories used in U.S. regulatory modeling.

Source apportionment of fine particles and its chemical components over the Yangtze River Delta, China during a heavy haze pollution episode

Abstract An extremely high PM 2.5 pollution episode occurred over the eastern China in January 2013. In this paper, the particulate matter source apportionment technology (PSAT) method coupled within the Comprehensive air quality model with extensions (CAMx) is applied to study the source contributions to PM 2.5 and its major components at six receptors (Urban Shanghai, Chongming, Dianshan Lake, Urban Suzhou, Hangzhou and Zhoushan) in the Yangtze River Delta (YRD) region. Contributions from 4 source areas (including Shanghai, South Jiangsu, North Zhejiang and Super-region) and 9 emission sectors (including power plants, industrial boilers and kilns, industrial processing, mobile source, residential, volatile emissions, dust, agriculture and biogenic emissions) to PM 2.5 and its major components (sulfate, nitrate, ammonia, organic carbon and elemental carbon) at the six receptors in the YRD region are quantified. Results show that accumulation of local pollution was the largest contributor during this air pollution episode in urban Shanghai (55%) and Suzhou (46%), followed by long-range transport (37% contribution to Shanghai and 44% to Suzhou). Super-regional emissions play an important role in PM 2.5 formation at Hangzhou (48%) and Zhoushan site (68%). Among the emission sectors contributing to the high pollution episode, the major source categories include industrial processing (with contributions ranging between 12.7 and 38.7% at different receptors), combustion source (21.7–37.3%), mobile source (7.5–17.7%) and fugitive dust (8.4–27.3%). Agricultural contribution is also very significant at Zhoushan site (24.5%). In terms of the PM 2.5 major components, it is found that industrial boilers and kilns are the major source contributor to sulfate and nitrate. Volatile emission source and agriculture are the major contributors to ammonia; transport is the largest contributor to elemental carbon. Industrial processing, volatile emissions and mobile source are the most significant contributors to organic carbon. Results show that the Yangtze River Delta region should focus on the joint pollution control of industrial processing, combustion emissions, mobile source emissions, and fugitive dust. Regional transport of air pollution among the cities are prominent, and the implementation of regional joint prevention and control of air pollution will help to alleviate fine particulate matter concentrations under heavy pollution case significantly.

Path-integral method for the source apportionment of photochemical pollutants

Abstract. A new, path-integral method is presented for apportioning the concentrations of pollutants predicted by a photochemical model to emissions from different sources. A novel feature of the method is that it can apportion the difference in a species concentration between two simulations. For example, the anthropogenic ozone increment, which is the difference between a simulation with all emissions present and another simulation with only the background (e.g., biogenic) emissions included, can be allocated to the anthropogenic emission sources. The method is based on an existing, exact mathematical equation. This equation is applied to relate the concentration difference between simulations to line or path integrals of first-order sensitivity coefficients. The sensitivities describe the effects of changing the emissions and are accurately calculated by the decoupled direct method. The path represents a continuous variation of emissions between the two simulations, and each path can be viewed as a separate emission-control strategy. The method does not require auxiliary assumptions, e.g., whether ozone formation is limited by the availability of volatile organic compounds (VOCs) or nitrogen oxides (NOx), and can be used for all the species predicted by the model. A simplified configuration of the Comprehensive Air Quality Model with Extensions (CAMx) is used to evaluate the accuracy of different numerical integration procedures and the dependence of the source contributions on the path. A Gauss–Legendre formula using three or four points along the path gives good accuracy for apportioning the anthropogenic increments of ozone, nitrogen dioxide, formaldehyde, and nitric acid. Source contributions to these increments were obtained for paths representing proportional control of all anthropogenic emissions together, control of NOx emissions before VOC emissions, and control of VOC emissions before NOx emissions. There are similarities in the source contributions from the three paths but also differences due to the different chemical regimes resulting from the emission-control strategies.

Comparison of regional and global land cover products and the implications for biogenic emission modeling

Accurate estimates of biogenic emissions are required for air quality models that support the development of air quality management plans and attainment demonstrations. Land cover characterization is an essential driving input for most biogenic emissions models. This work contrasted the global Moderate Resolution Imaging Spectroradiometer (MODIS) land cover product against a regional land cover product developed for the Texas Commissions on Environmental Quality (TCEQ) over four climate regions in eastern Texas, where biogenic emissions comprise a large fraction of the total inventory of volatile organic compounds (VOCs) and land cover is highly diverse. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) was utilized to investigate the influences of land cover characterization on modeled isoprene and monoterpene emissions through changes in the standard emission potential and emission activity factor, both separately and simultaneously. In Central Texas, forest coverage was significantly lower in the MODIS land cover product relative to the TCEQ data, which resulted in substantially lower estimates of isoprene and monoterpene emissions by as much as 90%. Differences in predicted isoprene and monoterpene emissions associated with variability in land cover characterization were primarily caused by differences in the standard emission potential, which is dependent on plant functional type. Photochemical modeling was conducted to investigate the effects of differences in estimated biogenic emissions associated with land cover characterization on predicted ozone concentrations using the Comprehensive Air Quality Model with Extensions (CAMx). Mean differences in maximum daily average 8-hour (MDA8) ozone concentrations were 2 to 6 ppb with maximum differences exceeding 20 ppb. Continued focus should be on reducing uncertainties in the representation of land cover through field validation.Implications: Uncertainties in the estimation of biogenic emissions associated with the characterization of land cover in global and regional data products were examined in eastern Texas. Misclassification between trees and low-growing vegetation in central Texas resulted in substantial differences in isoprene and monoterpene emission estimates and predicted ground-level ozone concentrations. Results from this study indicate the importance of land cover validation at regional scales.

Impacts of heterogeneous HONO formation on radical sources and ozone chemistry in Houston, Texas

The chemical mechanisms used in regulatory air quality models typically allow for only homogeneous formation of nitrous acid (HONO), an important radical precursor. This study adds heterogeneous formation on surfaces as a HONO source to the Comprehensive Air quality Model with extensions (CAMx). Modeling was performed for the Houston, Texas, region on April 21, 2009. Comparisons to measurements made at Moody Tower during the Study of Houston Atmospheric Radical Precursors (SHARP) show that adding heterogeneous formation increases HONO concentrations, particularly in the early morning and at night. Heterogeneous HONO formation reduces normalized mean error for morning, daytime, and nighttime HONO concentrations from 77% to 67%, 66%–28%, and 99%–67%. Maximum daily 8-hr O3 concentrations were up to 3.5 ppb greater as a result of heterogeneous HONO formation. Direct HONO emissions equal to 0.8% of NOx emissions were also added to the model, but they were considered separately from heterogeneous HONO formation. Increases over the base case of HONO and O3 were seen, though the magnitudes are not as great as with heterogeneous HONO formation. Maximum daily 8-hr O3 concentrations were up to 0.4 ppb greater than with homogeneous HONO formation alone. Significant early morning and nighttime HONO under predictions were seen compared to SHARP measurements in the direct emissions scenario. Direct HONO emissions led to local increases of HONO and O3 in areas with high NOx emissions, but heterogeneous HONO formation led to regional increases of both. Process analysis was used to determine the effect on O3 chemistry in downtown Houston. Daily total hydroxyl radical (OH) production from HONO photolysis was 3.94 ppb/day with heterogeneous HONO formation, 2.40 ppb/day with direct emissions, and 1.40 ppb/day in the base case. A 10% increase of hydrocarbon and carbon monoxide oxidation by OH was seen with heterogeneous HONO formation, while the increase in the direct emissions scenario was 3%. Nitric oxide (NO) to NO2 conversion increased by 8% with heterogeneous formation, while the increase was only 3% with direct HONO emissions. Radical sources, radical propagation, and oxidant production were enhanced at each step in the chemical cycle – particularly just after sunrise – by the addition of heterogeneous HONO formation and direct HONO emissions, but the effects were greater with heterogeneous formation.

Influence of satellite-derived photolysis rates and NO<sub>x</sub> emissions on Texas ozone modeling

Abstract. Uncertain photolysis rates and emission inventory impair the accuracy of state-level ozone (O3) regulatory modeling. Past studies have separately used satellite-observed clouds to correct the model-predicted photolysis rates, or satellite-constrained top-down NOx emissions to identify and reduce uncertainties in bottom-up NOx emissions. However, the joint application of multiple satellite-derived model inputs to improve O3 state implementation plan (SIP) modeling has rarely been explored. In this study, Geostationary Operational Environmental Satellite (GOES) observations of clouds are applied to derive the photolysis rates, replacing those used in Texas SIP modeling. This changes modeled O3 concentrations by up to 80 ppb and improves O3 simulations by reducing modeled normalized mean bias (NMB) and normalized mean error (NME) by up to 0.1. A sector-based discrete Kalman filter (DKF) inversion approach is incorporated with the Comprehensive Air Quality Model with extensions (CAMx)–decoupled direct method (DDM) model to adjust Texas NOx emissions using a high-resolution Ozone Monitoring Instrument (OMI) NO2 product. The discrepancy between OMI and CAMx NO2 vertical column densities (VCDs) is further reduced by increasing modeled NOx lifetime and adding an artificial amount of NO2 in the upper troposphere. The region-based DKF inversion suggests increasing NOx emissions by 10–50% in most regions, deteriorating the model performance in predicting ground NO2 and O3, while the sector-based DKF inversion tends to scale down area and nonroad NOx emissions by 50%, leading to a 2–5 ppb decrease in ground 8 h O3 predictions. Model performance in simulating ground NO2 and O3 are improved using sector-based inversion-constrained NOx emissions, with 0.25 and 0.04 reductions in NMBs and 0.13 and 0.04 reductions in NMEs, respectively. Using both GOES-derived photolysis rates and OMI-constrained NOx emissions together reduces modeled NMB and NME by 0.05, increases the model correlation with ground measurement in O3 simulations, and makes O3 more sensitive to NOx emissions in the O3 non-attainment areas.

Comprehensive study of emission source contributions for tropospheric ozone formation over East Asia

AbstractEmission source contributions of tropospheric ozone (O3) were comprehensively investigated by using the higher‐order decoupled direct method (HDDM) for sensitivity analysis and the ozone source apportionment technology (OSAT) for mass balance analysis in the comprehensive air‐quality model with extensions (CAMx). The response of O3 to emissions reductions at various levels in mainland China, Korea, and Japan were estimated and compared with results calculated by the brute force method (BFM) where one model parameter is varied at a time. Emissions were assessed at three receptor sites in Japan that experienced severe pollution events in May 2009. For emissions from China, HDDM assessed O3 response with a bias of only up to 3 ppbv (a relative error of 4.5%) even for a 50% reduction but failed to assess a more extreme reduction. OSAT was reasonably accurate at 100% reduction, with a −4 ppbv (−7%) bias, but was less accurate at moderate ranges of reduction (∼50–70%). For emissions from Korea and Japan, HDDM captured the nonlinear response at all receptor sites and at all reduction levels to within 1% in all but one case; however, the bias of OSAT increased with the increasing reduction of emissions. One possible reason for this is that OSAT does not account for NO titration. To address this, a term for potential ozone (PO; O3 and NO2 together) was introduced. Using of PO instead of O3 improved the performance of OSAT, especially for emissions reductions from Korea and Japan. The proposed approach with PO refined the OSAT results and did not degrade HDDM performance.

Comparison of background ozone estimates over the western United States based on two separate model methodologies

Two separate air quality model methodologies for estimating background ozone levels over the western U.S. are compared in this analysis. The first approach is a direct sensitivity modeling approach that considers the ozone levels that would remain after certain emissions are entirely removed (i.e., zero-out modeling). The second approach is based on an instrumented air quality model which tracks the formation of ozone within the simulation and assigns the source of that ozone to pre-identified categories (i.e., source apportionment modeling). This analysis focuses on a definition of background referred to as U.S. background (USB) which is designed to represent the influence of all sources other than U.S. anthropogenic emissions. Two separate modeling simulations were completed for an April–October 2007 period, both focused on isolating the influence of sources other than domestic manmade emissions. The zero-out modeling was conducted with the Community Multiscale Air Quality (CMAQ) model and the source apportionment modeling was completed with the Comprehensive Air Quality Model with Extensions (CAMx). Our analysis shows that the zero-out and source apportionment techniques provide relatively similar estimates of the magnitude of seasonal mean daily 8-h maximum U.S. background ozone at locations in the western U.S. when base case model ozone biases are considered. The largest differences between the two sets of USB estimates occur in urban areas where interactions with local NOx emissions can be important, especially when ozone levels are relatively low. Both methodologies conclude that seasonal mean daily 8-h maximum U.S. background ozone levels can be as high as 40–45 ppb over rural portions of the western U.S. Background fractions tend to decrease as modeled total ozone concentrations increase, with typical fractions of 75–100 percent on the lowest ozone days (<25 ppb) and typical fractions between 30 and 50% on days with ozone above 75 ppb. The finding that estimates of background ozone are not strongly dependent on the technique applied lends credibility to this and earlier modeling work.

Influence of Reactive Volatile Organic Compounds on Ozone Production in Houston-Galveston-Brazoria Area

Secondary pollutant ozone (O3) formation in a particular area is often influenced by various factors. Source of emissions is one of the factors. In south east Texas, Houston-Galveston-Brazoria (HGB) is a marginal non-attainment area for ozone (O3). A summer episode of May 28 to July 2, 2006 is simulated using Comprehensive Air Quality Model with extensions (CAMx). During this period O3 concentration in HGB often exceeds the National Ambient Air Quality Standards (NAAQS) 0.075 ppm of average 8 hour O3 concentration. HGB area has numerous point sources. Various studies found that some specific volatile organic compounds are very reactive in atmosphere. The objective of this study is to analyze the influence of volatile organic compounds present in point source emissions on the air quality of HGB area. For this purpose ozone sensitivity for HGB area is analyzed by the ratio of hydrogen peroxides (H2O2) to nitric acid (HNO3). HGB area is found NOx limited but reactive VOCs are found to be influential too. From (1-4 June, 2006) maximum O3 concentration was found on weekend, June 3. VOCs such as Acetaldehyde (ALD2), Formaldehyde (FORM) and Alkane (ETHA) showed good correlation with O3 concentrations on that day. In addition, Peroxyacetyl nitrate (PAN) formation was found correlated to higher ozone production. Criteria pollutant Sulfur dioxide (SO2) was found to influence the ALD2 and ETHA concentrations, and thus indirectly influenced O3 production.