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The San Joaquin Valley (SJV) of California experiences high concentrations of particulate matter NH4NO3 during episodes of meteorological stagnation in winter. A rich data set of observations related to NH4NO3 formation was acquired during multiple periods of elevated NH4NO3 during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign in SJV in January and February 2013. Here NH4NO3 is simulated during the SJV DISCOVER-AQ study period with the Community Multiscale Air Quality (CMAQ) model, diagnostic model evaluation is performed using the DISCOVER-AQ data set, and integrated reaction rate analysis is used to quantify HNO3 production rates. Simulated NO3- generally agrees well with routine monitoring of 24-hr average NO3-, but comparisons with hourly average NO3- measurements in Fresno revealed differences at higher time resolution. Predictions of gas-particle partitioning of total nitrate (HNO3 + NO3-) and NHx (NH3 + NH4+) generally agree well with measurements in Fresno, although partitioning of total nitrate to HNO3 is sometimes overestimated at low relative humidity in afternoon. Gas-particle partitioning results indicate that NH4NO3 formation is limited by HNO3 availability in both the model and ambient. NH3 mixing ratios are underestimated, particularly in areas with large agricultural activity, and additional work on the spatial allocation of NH3 emissions is warranted. During a period of elevated NH4NO3, the model predicted that the OH + NO2 pathway contributed 46% to total HNO3production in SJV and the N2O5 heterogeneous hydrolysis pathway contributed 54%. The relative importance of the OH + NO2 pathway for HNO3 production is predicted to increase as NOx emissions decrease.

Satellite-based measurements of the column CH2O/NO2 ratio have previously been used to estimate near-surface ozone (O3) sensitivity (i.e., NOx or VOC limited), and the forthcoming launch of air quality-focused geostationary satellites provides a catalyst for reevaluating the ability of satellite-measured CH2O/NO2 to be used in this manner. In this study, we use a 0-D photochemical box model to evaluate O3 sensitivity and find that the relative rate of radical termination from radical-radical interactions to radical-NOx interactions (referred to as LROx/LNOx) provides a good indicator of maximum O3 production along NOx ridgelines. Using airborne measurements from NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relative to Air Quality (DISCOVER-AQ) deployments in Colorado, Maryland, and Houston, we show that in situ measurements of CH2O/NO2 can be used to indicate O3 sensitivity, but there is an important “transition/ambiguous” range whereby CH2O/NO2 fails to categorize O3 sensitivity, and the range and span of this transition/ambiguous range varies regionally. Then, we apply these findings to aircraft-derived column density measurements from DISCOVER-AQ and find that inhomogeneities in vertical mixing in the lower troposphere further degrades the ability of column CH2O/NO2 to indicate near-surface O3 sensitivity (i.e., the transition/ambiguous range is much larger than indicated by in situ data alone), and we hypothesize that the global transition/ambiguous range is sufficiently large to make the column CH2O/NO2 ratio unuseful for classifying near-surface O3 sensitivity. Lastly, we present a case study from DISCOVER-AQ-Houston that suggests that O3 sensitivity on exceedance days may be substantially different than on nonexceedance days (which may be observable from space) and explore the diurnal evolution of O3 sensitivity, O3 production, and the column CH2O/NO2 ratio. The results of these studies suggest that although satellite measurements of CH2O/NO2 alone may not be sufficient for accurately classifying near-surface O3 sensitivity, new techniques offered by geostationary platforms may nonetheless provide methods for using space-based measurements to develop O3 mitigation strategies.

Past work has shown that traffic patterns in the USA and resulting NO x emissions vary by day of week, with NO x emissions typically being higher on weekdays than weekends. This pattern of emissions leads to different levels of ozone on weekends versus weekdays and can be leveraged to understand how local ozone formation changes in response to NO x emission perturbations in different urban areas. Specifically, areas with lower NO x but higher ozone on the weekends (the weekend effect) can be characterized as NO x -saturated and areas with both lower NO x and ozone on weekends (the weekday effect) can be characterized as NO x -limited. In this analysis, we assess maximum daily 8 h average (MDA8) ozone weekend–weekday differences across 51 USA nonattainment areas using 18 years of observed and modeled data from 2002–2019, using the following two metrics: mean MDA8 ozone and percentage of days with MDA8 ozone > 70 ppb (parts per billion). In addition, we quantify the modeled and observed trends in these weekend–weekday differences across this period of substantial NO x emission reductions in the USA. The model assessment is carried out using U.S. Environmental Protection Agency (EPA)'s Air QUAlity TimE Series Project (EQUATES) Community Multiscale Air Quality (CMAQ) model dataset. We identify three types of MDA8 ozone trends occurring across the USA, namely transitioning chemical regime, disappearing weekday effect, and no trend. The transitioning chemical regime trend occurs in a subset of large urban areas that were NO x -saturated (i.e., volatile organic compound (VOC)-limited) at the beginning of the analysis period but transitioned to mixed chemical regimes or NO x -limited conditions by the end of the analysis period. Nine areas have strong transitioning chemical regime trends using both modeled and observed data and with both metrics indicating strong agreement that they are shifting to more NO x -limited conditions: Milwaukee, Houston, Phoenix, Denver, the Northern Wasatch Front, the Southern Wasatch Front, Las Vegas, Los Angeles – San Bernardino County, Los Angeles – South Coast, and San Diego. The disappearing weekday effect was identified for multiple rural and agricultural areas of California which were NO x -limited for the entire analysis period but appear to become less influenced by local day-of-week emission patterns in more recent years. Finally, we discuss a variety of reasons why there are no trends in certain areas including complex impacts of heterogeneous source mixes and stochastic impacts of meteorology. Overall, this assessment finds that the EQUATES modeling simulations indicate more NO x -saturated conditions than the observations but do a good job of capturing year-to-year changes in weekend–weekday MDA8 ozone patterns. [ABSTRACT FROM AUTHOR]

This study reviewed four widely used air quality models and concluded that simple Gaussian dispersion models, ISCST3 and AERMOD, are not suitable for modeling N deposition because they fail to represent chemical and phase transformations of nitrogen oxides (NOX) and ammonia (NH3) emissions. It reviewed two models that do represent chemical speciation and formation of aerosols: CALPUFF and the Community Multiscale Air Quality (CMAQ) model. CALPUFF is a trajectory model that adopts several simplifications that raise important concerns regarding its accuracy. CMAQ is a photochemical grid model and includes state-of-the-art science algorithms. The study performed simulations using each model to assess nitrogen (N) deposition from a power plant. CALPUFF predicted slightly lower deposition rates than did CMAQ, and the spatial features of CALPUFF were poorly resolved. For CMAQ, the study simulated calendar year 2002 to develop baseline N deposition estimates throughout California, and then performed a sensitivity simulation with the new power plant to calculate the change in N deposition. The CMAQ predicted higher deposition rates than the CALPUFF model and provided finer spatial resolution. However, the CMAQ model exhibited numerical noise. The authors recommend exploring other photochemical grid models that might have less numerical noise than CMAQ. Perhaps the most significant outcome of this work is the CMAQ model-simulated baseline annual N deposition for a 4-kilometer resolution grid on a domain that includes much of California. These data have also been converted into an ASCII format that can be readily imported into ArcGIS or other GIS software and used in future ecosystem studies of the effects of N deposition and soil nitrification.

Past work has shown that traffic patterns in the US and resulting NOX emissions vary by day of week, with NOX emissions typically higher on weekdays than weekends. This pattern of emissions leads to different levels of ozone on weekends versus weekdays and can be leveraged to understand how local ozone formation changes in response to NOX emissions perturbations in different urban areas. Specifically, areas with lower NOX but higher ozone on the weekends (the weekend effect) can be characterized as NOX -saturated and areas with both lower NOX and ozone on weekends (the weekday effect) can be characterized as NOX-limited. In this analysis we assess ozone weekend-weekday differences across US nonattainment areas using 18 years of observed and modeled data from 2002–2019 using two metrics: mean ozone and percentage of days > 70 ppb. In addition, we quantify the modeled and observed trends in these weekend-weekday differences across this period of substantial NOX emissions reductions in the US. The model assessment is carried out using EPA's Air QUAlity TimE Series Project (EQUATES) CMAQ dataset. We identify 3 types of ozone trends occuring across the US: disappearing weekend effect, disappearing weekday effect, and no trend. The disappearing weekend effect occurs in a subset of large urban areas that were NOX -saturated (i.e., VOC-limited) at the beginning of the analysis period but transitioned to mixed chemical regimes or NOX-limited conditions by the end of the analysis period. Nine areas have disappearing weekend effect trends in both datasets and with both metrics indicating strong agreement that they are shifting to more NOX-limited conditions: Milwaukee, Houston, Phoenix, Denver, Northern Wasatch Front, Southern Wasatch Front, Las Vegas, Los Angeles – San Bernardino County, Los Angeles – South Coast, and San Diego. The disappearing weekday effect was identified for multiple rural and agricultural areas of California which were NOX -limited for the entire analysis period but appear to become less influenced by local day of week emission patterns in more recent years. Finally, we discuss a variety of reasons why there are no statistically significant trends in certain areas including complex impacts of heterogeneous source mixes and stochastic impacts of meteorology. Overall, this assessment finds that the EQUATES modeling simulations indicate more NOX-saturated conditions than the observations but do a good job of capturing year-to-year changes in weekend-weekday ozone patterns. [ABSTRACT FROM AUTHOR]

Photochemical grid models are being used in technical analyses by the Visibility Improvement State and Tribal Association of the Southeast (VISTAS), a regional air quality planning organization in the southeastern United States, to support state implementation plans for regional haze and related air quality issues. VISTAS has embarked on a multi-phase process of testing and evaluating regional meteorological, emissions and air quality models that will be used to project visibility improvements as required by the regional haze rule. VISTAS has generated 2002 annual emissions and meteorological inputs for two photochemical grid models, the community multi-scale air quality (CMAQ) and the comprehensive air-quality model with extensions (CAMx), at a 36 km resolution for the continental US and at 12 km resolution for the eastern US. The two models were evaluated using speciated PM measurements from various monitoring networks and detailed analysis was performed for organic carbon (OC) mass using the IMPROVE, STN, and SEARCH networks. The differences in model performance between CMAQ and CAMx were used as a diagnostic tool to investigate performance issues for several compounds. CAMx performed substantially better than CMAQ for OC (defined as 1.4×measured organic carbon) which led to investigations into methods for improving the CMAQ OC model performance. The treatment of secondary organic aerosol (SOA) was identified as an area needing improvements in both models. The impact of replacing the CMAQ SOA parameters with those from CAMx was investigated. Further analysis identified several processes that are potentially important for SOA formation that are not treated in either model including, polymerization of the SOA into non-volatile particles and SOA formation from sesquiterpene, isoprene and other biogenic VOCs. A prototype mechanism for several of these missing processes was developed and the CMAQ SOA module was enhanced to include these SOA formation processes. SOA yields, specifically from biogenic emissions, were increased by the modified SOA module and CMAQ model performance for particulate OC at the IMPROVE, SEARCH, and STN sites in the VISTAS region was improved. © 2006 Elsevier Ltd. All rights reserved.

ABSTRACT The Visibility Improvement State and Tribal Association of the Southeast (VISTAS) is one of five Regional Planning Organizations that is charged with the management of haze, visibility, and other [...]

Abstract: The San Joaquin Valley (SJV) of California experiences high concentrations of particulate matter NH4NO3 during episodes of meteorological stagnation in winter. A rich data set of observations related to NH4NO3 formation was acquired during multiple periods of elevated NH4NO3 during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER‐AQ) field campaign in SJV in January and February 2013. Here NH4NO3 is simulated during the SJV DISCOVER‐AQ study period with the Community Multiscale Air Quality (CMAQ) model, diagnostic model evaluation is performed using the DISCOVER‐AQ data set, and integrated reaction rate analysis is used to quantify HNO3 production rates. Simulated NO3− generally agrees well with routine monitoring of 24‐hr average NO3−, but comparisons with hourly average NO3− measurements in Fresno revealed differences at higher time resolution. Predictions of gas‐particle partitioning of total nitrate (HNO3 + NO3−) and NHx (NH3 + NH4+) generally agree well with measurements in Fresno, although partitioning of total nitrate to HNO3 is sometimes overestimated at low relative humidity in afternoon. Gas‐particle partitioning results indicate that NH4NO3 formation is limited by HNO3 availability in both the model and ambient. NH3 mixing ratios are underestimated, particularly in areas with large agricultural activity, and additional work on the spatial allocation of NH3 emissions is warranted. During a period of elevated NH4NO3, the model predicted that the OH + NO2 pathway contributed 46% to total HNO3 production in SJV and the N2O5 heterogeneous hydrolysis pathway contributed 54%. The relative importance of the OH + NO2 pathway for HNO3 production is predicted to increase as NOx emissions decrease. [ABSTRACT FROM AUTHOR]

Determining effective strategies for mitigating surface ozone (O3) pollution requires knowledge of the relative ambient concentrations of its precursors, NO x, and VOCs. The space-based tropospheric column ratio of formaldehyde to NO2 (FNR) has been used as an indicator to identify NO x-limited versus NO x-saturated O3 formation regimes. Quantitative use of this indicator ratio is subject to three major uncertainties: (1) the split between NO x-limited and NO x-saturated conditions may shift in space and time, (2) the ratio of the vertically integrated column may not represent the near-surface environment, and (3) satellite products contain errors. We use the GEOS-Chem global chemical transport model to evaluate the quantitative utility of FNR observed from the Ozone Monitoring Instrument over three northern midlatitude source regions. We find that FNR in the model surface layer is a robust predictor of the simulated near-surface O3 production regime. Extending this surface-based predictor to a column-based FNR requires accounting for differences in the HCHO and NO2 vertical profiles. We compare four combinations of two OMI HCHO and NO2 retrievals with modeled FNR. The spatial and temporal correlations between the modeled and satellite-derived FNR vary with the choice of NO2 product, while the mean offset depends on the choice of HCHO product. Space-based FNR indicates that the spring transition to NO x-limited regimes has shifted at least a month earlier over major cities (e.g., New York, London, and Seoul) between 2005 and 2015. This increase in NO x sensitivity implies that NO x emission controls will improve O3 air quality more now than it would have a decade ago. [ABSTRACT FROM AUTHOR]

Satellite-based measurements of the column CH2O/NO2 ratio have previously been used to estimate near-surface ozone (O3) sensitivity (i.e., NO x or VOC limited), and the forthcoming launch of air quality-focused geostationary satellites provides a catalyst for reevaluating the ability of satellite-measured CH2O/NO2 to be used in this manner. In this study, we use a 0-D photochemical box model to evaluate O3 sensitivity and find that the relative rate of radical termination from radical-radical interactions to radical-NO x interactions (referred to as LRO x/LNO x) provides a good indicator of maximum O3 production along NO x ridgelines. Using airborne measurements from NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relative to Air Quality (DISCOVER-AQ) deployments in Colorado, Maryland, and Houston, we show that in situ measurements of CH2O/NO2 can be used to indicate O3 sensitivity, but there is an important 'transition/ambiguous' range whereby CH2O/NO2 fails to categorize O3 sensitivity, and the range and span of this transition/ambiguous range varies regionally. Then, we apply these findings to aircraft-derived column density measurements from DISCOVER-AQ and find that inhomogeneities in vertical mixing in the lower troposphere further degrades the ability of column CH2O/NO2 to indicate near-surface O3 sensitivity (i.e., the transition/ambiguous range is much larger than indicated by in situ data alone), and we hypothesize that the global transition/ambiguous range is sufficiently large to make the column CH2O/NO2 ratio unuseful for classifying near-surface O3 sensitivity. Lastly, we present a case study from DISCOVER-AQ-Houston that suggests that O3 sensitivity on exceedance days may be substantially different than on nonexceedance days (which may be observable from space) and explore the diurnal evolution of O3 sensitivity, O3 production, and the column CH2O/NO2 ratio. The results of these studies suggest that although satellite measurements of CH2O/NO2 alone may not be sufficient for accurately classifying near-surface O3 sensitivity, new techniques offered by geostationary platforms may nonetheless provide methods for using space-based measurements to develop O3 mitigation strategies. [ABSTRACT FROM AUTHOR]

US surface O3 responds to varying global-toregional precursor emissions, climate, and extreme weather, with implications for designing effective air quality control policies. We examine these conjoined processes with observations and global chemistry-climate model (GFDLAM3) hindcasts over 1980-2014. The model captures the salient features of observed trends in daily maximum 8 h average O3: (1) increases over East Asia (up to 2 ppb yr-1), (2) springtime increases at western US (WUS) rural sites (0.2-0.5 ppb yr-1) with a baseline sampling approach, and (3) summertime decreases, largest at the 95th percentile, and wintertime increases in the 50th to 5th percentiles over the eastern US (EUS). Asian NOx emissions have tripled since 1990, contributing as much as 65% to modeled springtime background O3 increases (0.3-0.5 ppb yr-1) over the WUS, outpacing O3 decreases attained via 50% US NOx emission controls. Methane increases over this period contribute only 15% of the WUS background O3 increase. Springtime O3 observed in Denver has increased at a rate similar to remote rural sites. During summer, increasing Asian emissions approximately offset the benefits of US emission reductions, leading to weak or insignificant observed O3 trends at WUS rural sites. Mean springtime WUS O3 is projected to increase by ∼10 ppb from 2010 to 2030 under the RCP8.5 global change scenario. While historical wildfire emissions can enhance summertime monthly mean O3 at individual sites by 2-8 ppb, high temperatures and the associated buildup of O3 produced from regional anthropogenic emissions contribute most to elevating observed summertime O3 throughout the USA. GFDL-AM3 captures the observed interannual variability of summertime EUS O3. However, O3 deposition sink to vegetation must be reduced by 35% for the model to accurately simulate observed high-O3 anomalies during the severe drought of 1988. Regional NOx reductions alleviated the O3 buildup during the recent heat waves of 2011 and 2012 relative to earlier heat waves (e.g., 1988, 1999). The O3 decreases driven by NOx controls were more pronounced in the southeastern US, where the seasonal onset of biogenic isoprene emissions and NOx-sensitive O3 production occurs earlier than in the northeast. Without emission controls, the 95th percentile summertime O3 in the EUS would have increased by 0.2-0.4 ppb yr-1 over 1988-2014 due to more frequent hot extremes and rising biogenic isoprene emissions. [ABSTRACT FROM AUTHOR]

Surface ozone (O3) responds to varying global-to-regional precursor emissions, climate, and extreme weather, with implications for designing effective air quality control policies. We examine these conjoined processes with observations and global chemistry-climate model (GFDL-AM3) hindcasts over 1980-2014. The model captures the salient features of observed trends in daily maximum 8-hour average O3; (1) increases over East Asia (up to 2 ppb yr-1), (2) springtime increases at western US (WUS) rural sites (0.2-0.5 ppb yr-1) with a 'baseline' sampling approach, (3) summertime decreases, largest at the 95th percentile, and wintertime increases in the 50th to 5th percentiles over the eastern US (EUS). Asian NOx emissions tripled since 1990, contributing as much as 65% to modeled springtime background O3 increases (0.3-0.5 ppb yr-1) over the WUS, outpacing O3 decreases attained via US domestic emission controls. Methane increases over this period raise WUS background O3 by 15%. During summer, increasing Asian emissions approximately offset the effects of US emission reductions, leading to weak or insignificant observed O3 trends at WUS rural sites. While wildfire emissions can enhance summertime monthly mean O3 at individual sites by 2-8 ppb, high temperatures and the associated buildup of O3 produced from regional anthropogenic emissions contribute most to elevating observed summertime O3 throughout the USA. Rising Asian emissions and global methane under the RCP8.5 scenario increase mean springtime O3 above the WUS by ~10 ppb from 2010 to 2030. Historical EUS O3 decreases, driven by regional emission controls, were most pronounced in the Southeast with an earlier onset of biogenic isoprene emissions and NOx-sensitive O3 production. Regional NOx reductions also alleviated the O3 buildup during the recent heat waves of 2011 and 2012 relative to earlier heat waves (e.g., 1988; 1999). Without emission controls, the 95th percentile summertime O3 in the EUS would have increased by 0.2-0.4 ppb yr-1 over 1988-2014 due to more frequent hot extremes and rising biogenic isoprene emissions. [ABSTRACT FROM AUTHOR]

Surface ozone (O3) responds to varying global-to-regional precursor emissions, climate, and extreme weather, with implications for designing effective air quality control policies. We examine these conjoined processes with observations and global chemistry-climate model (GFDL-AM3) hindcasts over 1980-2014. The model captures the salient features of observed trends in daily maximum 8-hour average O3; (1) increases over East Asia (up to 2 ppb yr-1), (2) springtime increases at western US (WUS) rural sites (0.2-0.5 ppb yr-1) with a 'baseline' sampling approach, (3) summertime decreases, largest at the 95th percentile, and wintertime increases in the 50th to 5th percentiles over the eastern US (EUS). Asian NOx emissions tripled since 1990, contributing as much as 65% to modeled springtime background O3 increases (0.3-0.5 ppb yr-1) over the WUS, outpacing O3 decreases attained via US domestic emission controls. Methane increases over this period raise WUS background O3 by 15%. During summer, increasing Asian emissions approximately offset the effects of US emission reductions, leading to weak or insignificant observed O3 trends at WUS rural sites. While wildfire emissions can enhance summertime monthly mean O3 at individual sites by 2-8 ppb, high temperatures and the associated buildup of O3 produced from regional anthropogenic emissions contribute most to elevating observed summertime O3 throughout the USA. Rising Asian emissions and global methane under the RCP8.5 scenario increase mean springtime O3 above the WUS by ~ 10 ppb from 2010 to 2030. Historical EUS O3 decreases, driven by regional emission controls, were most pronounced in the Southeast with an earlier onset of biogenic isoprene emissions and NOx-sensitive O3 production. Regional NOx reductions also alleviated the O3 buildup during the recent heat waves of 2011 and 2012 relative to earlier heat waves (e.g., 1988; 1999). Without emission controls, the 95th percentile summertime O3 in the EUS would have increased by 0.2-0.4 ppb yr-1 over 1988-2014 due to more frequent hot extremes and rising biogenic isoprene emissions. [ABSTRACT FROM AUTHOR]