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The Effect of Entrainment Through Atmospheric Boundary Layer Growth on Observed and Modeled Surface Ozone in the Colorado Front Range

Ozone concentrations at the Earth's surface are controlled by meteorological and chemical processes and are a function of advection, entrainment, deposition, and net chemical production/loss. The relative contributions of these processes vary in time and space. Understanding the relative importance of these processes controlling surface ozone concentrations is an essential component for designing effective regulatory strategies. Here we focus on the diurnal cycle of entrainment through atmospheric boundary layer (ABL) growth in the Colorado Front Range. Aircraft soundings and surface observations collected in July/August 2014 during the DISCOVER-AQ/FRAPPÉ (Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality/Front Range Air Pollution and Photochemistry Éxperiment) campaigns and equivalent data simulated by a regional chemical transport model are analyzed. Entrainment through ABL growth is most important in the early morning, fumigating the surface at a rate of ~5 ppbv/h. The fumigation effect weakens near noon and changes sign to become a small dilution effect in the afternoon on the order of -1 ppbv/h. The chemical transport model WRF-Chem (Weather Research and Forecasting Model with chemistry) underestimates ozone at all altitudes during this study on the order of 10-15 ppbv. The entrainment through ABL growth is overestimated by the model in the order of 0.6-0.8 ppbv/h. This results from differences in boundary layer growth in the morning and ozone concentration jump across the ABL top in the afternoon. This implicates stronger modeled fumigation in the morning and weaker modeled dilution after 11:00 LT.

Entrainment through ABL Growth↗

Surface ozone levels at Table Mountain during STOIC 1989

As a part of the routine operations of the Jet Propulsion Laboratory atmospheric measurements program at the Table Mountain Facility, the surface ozone concentration is continuously monitored using a Dasibi photometer. The influence of the Los Angeles basin to the southwest of the facility and the height of the inversion layer cause large fluctuations in the ozone concentration. Peaks as high as 200 parts per billion by volume (ppbv) were observed during the Stratospheric Ozone Intercomparison Campaign (STOIC) compared to a normal background level near 50 ppbv. These measurements, made during STOIC, were important in assessing the impact of the surface ozone concentration on the various instruments participating in the campaign.

McDermid, I. Stuart↗

Attribution of Trends and Variability in Surface Ozone over the United States

Concentrations of tropospheric ozone, a greenhouse gas and air pollutant, are impacted by changes in precursor emissions as well meteorology and influx from the stratosphere. Observations show a decreasing trend in summertime surface ozone at rural stations in the eastern United States, while some western stations show increasing trends, particularly in springtime. We use the Global Modeling Initiative (GMI) global chemical transport model to investigate the roles of precursor emission changes, meteorological variability, and stratosphere-troposphere exchange (STE) in explaining observed trends in surface ozone from rural sites in the United States from 1991-2010. The model's interannual variability shows significant correlations with observations from many of the surface sites. We also compare the simulated ozone to ozonesonde data for several locations with sufficiently long records. We compare a simulation with time-dependent precursor emissions, including emission reductions over the United States and Europe and increases over Asia, to a simulation with fixed emissions to quantify the impact of changing emissions on the surface trends. The simulation with varying emissions reproduces much of the east-west difference in summertime ozone over the U.S., although it generally underestimates the negative trend in the East. In contrast, the fixed-emission simulation shows increasing ozone at both eastern and western sites. We will discuss possible causes of this behavior, including long-range transport and STE.

ozone↗

Higher Surface Ozone Concentrations Over the Chesapeake Bay than Over the Adjacent Land: Observations and Models from the DISCOVER-AQ and CBODAQ Campaigns

Air quality models, such as the Community Multiscale Air Quality (CMAQ) model, indicate decidedly higher ozone near the surface of large interior water bodies, such as the Great Lakes and Chesapeake Bay. In order to test the validity of the model output, we performed surface measurements of ozone (O3) and total reactive nitrogen (NOy) on the 26-m Delaware II NOAA Small Research Vessel experimental (SRVx), deployed in the Chesapeake Bay for 10 daytime cruises in July 2011 as part of NASA's GEO-CAPE CBODAQ oceanographic field campaign in conjunction with NASA's DISCOVER-AQ air quality field campaign. During this 10-day period, the EPA O3 regulatory standard of 75 ppbv averaged over an 8-h period was exceeded four times over water while ground stations in the area only exceeded the standard at most twice. This suggests that on days when the Baltimore/Washington region is in compliance with the EPA standard, air quality over the Chesapeake Bay might exceed the EPA standard. Ozone observations over the bay during the afternoon were consistently 10-20% higher than the closest upwind ground sites during the 10-day campaign; this pattern persisted during good and poor air quality days. A lower boundary layer, reduced cloud cover, slower dry deposition rates, and other lesser mechanisms, contribute to the local maximum of ozone over the Chesapeake Bay. Observations from this campaign were compared to a CMAQ simulation at 1.33 km resolution. The model is able to predict the regional maximum of ozone over the Chesapeake Bay accurately, but NOy concentrations are significantly overestimated. Explanations for the overestimation of NOy in the model simulations are also explored

boundary layer↗

Influence of Mid-Latitude Cyclones on European Background Surface Ozone Investigated in Observations, MACC and MERRA-2 Reanalyses

The relationship between springtime mid-latitude cyclones and background ozone at two rural monitoring sites on the west coast of Europe -- Mace Head, Ireland and Monte Velho, Portugal -- is explored using a combination of observations and three reanalyses: 1) the European Centre for Medium-Range Weather Forecasts' (ECMWF) ERA-Interim reanalysis, 2) the Monitoring Atmospheric Composition and Climate (MACC) reanalysis and 3) NASA's Modern-Era Retrospective Analysis for Research and Applications Version-2 (MERRA-2) reanalysis. The ERA-Interim cyclone tracks are used here to establish the long-term relationship between cyclones and ozone observations (since 1988). The MACC reanalysis data set, which covers the period 2003-2012, is produced with the ECMWF integrated forecast system (IFS) model two-way coupled to a chemistry transport model (CTM). Since the MACC reanalysis uses a similar atmospheric model to ERA-Interim, MACC is used to explore the mechanisms within the case study cyclones that can influence surface ozone concentrations at Mace Head and Monte Velho. The MERRA-2 reanalysis also provides 3D distributions of ozone, although less ideal for analysis of surface ozone concentrations since MERRA-2 ozone under represents ozone variability outside the stratosphere as it does not have a detailed chemistry scheme or emission sources for the troposphere. The MERRA-2 reanalysis, which has the potential to identify more features within the cyclones as the resolution is higher than the MACC reanalysis, is used in conjunction with the MACC reanalysis to provide a measure of uncertainty to the case study analysis. We found the main source of high ozone to these two sites is from the stratosphere, which is well represented in both the MERRA-2 and the MACC reanalyses, either from direct injection into the cyclone or associated with aged airstreams from decaying downstream cyclones that can become entrained and descend toward the surface within new cyclones over the NA region.

MERRA-2↗

Statistical Analysis of Factors Riving Surface Ozone Variability over Continental South Africa

Statistical relationships between surface ozone (O3) concentration, precursor species and meteorological conditions in continental South Africa were examined from data obtained from measurement stations in north-eastern South Africa. Three multivariate statistical methods were applied in the investigation, i.e. multiple linear regression (MLR), principal component analysis (PCA) and –regression (PCR), and generalised additive model (GAM) analysis. The daily maximum 8-h moving average O3 concentrations were considered in these statistical models (dependent variable). MLR models indicated that meteorology and precursor species concentrations are able to explain ~50% of the variability in daily maximum O3 levels. MLR analysis revealed that atmospheric carbon monoxide (CO), temperature and relative humidity were the strongest factors affecting the daily O3 variability. In summer, daily O3 variances were mostly associated with relative humidity, while winter O3 levels were mostly linked to temperature and CO. PCA indicated that CO, temperature and relative humidity were not strongly collinear. GAM also identified CO, temperature and relative humidity as the strongest factors affecting the daily variation of O3. Partial residual plots found that temperature, radiation and nitrogen oxides most likely have a non-linear relationship with O3,while the relationship with relative humidity and CO is probably linear. An inter-comparison between O3 levels modelled with the three statistical models compared to measured O3 concentrations showed that the GAM model offered a slight improvement over the MLR model. These findings emphasise the critical role of regional-scale O3 precursors coupled with meteorological conditions in daily variances of O3 levels in continental South Africa.

multiple linear regression (MLR)↗

Application of OMI Observations to a Space-Based Indicator of NOx and VOC Controls on Surface Ozone Formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NOx) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the "Ratio") from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios less than 1 and NOx at Ratios greater than 2; both NOx and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria. the OMI data indicate that ozone formation became: 1. more sensitive to NOx over most of the United States from 2005 to 2007 because of the substantial decrease in NOx emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO2. and 2. more sensitive to NOx with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g .. Chicago). the data clearly indicate that ozone formation became more sensitive to NOx from 2005 to 2007. In cities with relatively high isoprene emissions (e.g ., Atlanta), we found that the increase in the Ratio due to decreasing NOx emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.

Duncan, Bryan N.↗

Decadal Changes in Summertime Reactive Oxidized Nitrogen and Surface Ozone over the Southeast United States

Widespread efforts to abate ozone (O3) smog have significantly reduced emissions of nitrogen oxides (NOx) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (International Consortium for Atmospheric Research on Transport and Transformation - July-August 2004), SENEX (Southeast Nexus - June-July 2013), and SEAC4RS (Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys - August-September 2013) and long-term ground measurement networks alongside a global chemistry-climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NO (sub y)) in both 2004 and 2013. Among the major RON species, nitric acid (HNO3) is dominant (approximately 42-45 percent), followed by NOx (31 percent), total peroxy nitrates (Sigma PNs; 14 percent), and total alkyl nitrates (Sigma ANs; 9-12 percent) on a regional scale. We find that most RON species, including NOx, Sigma PNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NO (sub y). This linear response might be in part due to the nearly constant summertime supply of biogenic VOC (Volatile Organic Compounds) emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOx emissions will lead to a continued decline in surface ozone and less frequent high-ozone events.

Li, Jingyi↗

NASA’s High-Resolution GEOS Forecasting and Reanalysis Products: Impact of Stratospheric Intrusions on Surface Ozone Air Quality

A new approach to the study of stratospheric intrusions (SIs)? the introduction of ozone-rich lower stratospheric air into the troposphere ? uses NASA's Goddard Earth Observing System Model (GEOS) model and assimilation products with an objective feature tracking algorithm to investigate the atmospheric dynamics in the UTLS region that generate SIs and the different mechanisms through which SIs may influence tropospheric chemistry and surface air quality. In particular, SIs have been linked with surface ozone air quality exceedances, especially at the high elevations in the western USA in springtime. However, the impact of SIs in the remaining seasons and over the rest of the USA is less clear. Improved understanding of the connections between large-scale climate variability and local-scale dynamically-driven air quality events may support improved seasonal prediction of SI events. While the spring over the western USA does exhibit the largest number of SIs affecting the lower troposphere, we demonstrate that the number of intrusions in the remaining seasons and over the eastern USA is sizable. Using a multitude of observational datasets, including lidar data, ozonesondes and air quality monitoring surface sites, in combination with GEOS forecast and reanalysis products, the transport of ozone from the stratosphere toward the surface is assessed. By focusing on recent reports of high ozone at monitoring station sites likely associated with SIs, we aim to provide the public with tools which are available in near-real time to enhance their capability to identify the impact of stratospheric air on surface ozone concentrations separate from anthropogenic sources.

Knowland, K. Emma↗

Impacts of Climate Change on Surface Ozone and Intercontinental Ozone Pollution: A Multi-Model Study

The impact of climate change between 2000 and 2095 SRES A2 climates on surface ozone (O)3 and on O3 source-receptor (S-R) relationships is quantified using three coupled climate-chemistry models (CCMs). The CCMs exhibit considerable variability in the spatial extent and location of surface O3 increases that occur within parts of high NOx emission source regions (up to 6 ppbv in the annual average and up to 14 ppbv in the season of maximum O3). In these source regions, all three CCMs show a positive relationship between surface O3 change and temperature change. Sensitivity simulations show that a combination of three individual chemical processes-(i) enhanced PAN decomposition, (ii) higher water vapor concentrations, and (iii) enhanced isoprene emission-largely reproduces the global spatial pattern of annual-mean surface O3 response due to climate change (R2 = 0.52). Changes in climate are found to exert a stronger control on the annual-mean surface O3 response through changes in climate-sensitive O3 chemistry than through changes in transport as evaluated from idealized CO-like tracer concentrations. All three CCMs exhibit a similar spatial pattern of annual-mean surface O3 change to 20% regional O3 precursor emission reductions under future climate compared to the same emission reductions applied under present-day climate. The surface O3 response to emission reductions is larger over the source region and smaller downwind in the future than under present-day conditions. All three CCMs show areas within Europe where regional emission reductions larger than 20% are required to compensate climate change impacts on annual-mean surface O3.

Troposphere: constituent transport and chemistry↗

The Effect of Lightning NOx Production on Surface Ozone in the Continental United States

Lightning NO(x) emissions calculated using the US National Lightning Detection Network data were found to account for 30% of the total NO(x) emissions for July August 2004, a period chosen both for having higher lightning NO(x) production and high ozone levels, thus maximizing the likelihood that such emissions could impact peak ozone levels. Including such emissions led to modest, but sometimes significant increases in simulated surface ozone when using the Community Multi-scale Air Quality Model (CMAQ). Three model simulations were performed, two with the addition of lightning NO(x) emissions, and one without. Domain-wide daily maximum 8-h ozone changes due to lightning NO(x) were less than 2 ppbv in 71 % of the cases with a maximum of 10 ppbv; whereas the difference in 1-h ozone was less than 2 ppbv in 77% of the cases with a maximum of 6 ppbv. Daily maximum 1-h and 8-h ozone for grids containing O3 monitoring stations changed slightly, with more than 43% of the cases differing less than 2 ppbv. The greatest differences were 42 ppbv for both 1-h and 8-h O3 , though these tended to be on days of lower ozone. Lightning impacts on the season-wide maximum 1-h and 8-h averaged ozone decreased starting from the 1 st to 4th highest values (an average of 4th highest, 8-h values is used for attainment demonstration in the US). Background ozone values from the y-intercept of O3 versus NO(z) curve were 42.2 and 43.9 ppbv for simulations without and with lightning emissions, respectively. Results from both simulations with lightning NO(x) suggest that while North American lightning production of NO(x) can lead to significant local impacts on a few occasions, they will have a relatively small impact on typical maximum levels and determination of Policy Relevant Background levels.

Kaynak, B.↗

Mapping Yearly Fine Resolution Global Surface Ozone through the Bayesian Maximum Entropy Data Fusion of Observations and Model Output for 1990–2017

Estimates of ground-level ozone concentrations are necessary to determine the human health burden of ozone. To support the Global Burden of Disease Study, we produce yearly fine resolution global surface ozone estimates from 1990 to 2017 through a data fusion of observations and models. As ozone observations are sparse in many populated regions, we use a novel combination of the M3Fusion and Bayesian Maximum Entropy (BME) methods. With M3Fusion, we create a multi-model composite by bias-correcting and weighting nine global atmospheric chemistry models based on their ability to predict observations (8,834 sites globally)in each region and year. BME is then used to integrate observations, such that estimates match observations at each monitoring site with the observational influence decreasing smoothly across space and time until the output matches the multi-model composite. After estimating at 0.5° resolution using BME, we add fine spatial detail from an additional model, yielding estimates at 0.1° resolution. Observed ozone is predicted more accurately (R2=0.81 at test point, 0.63 at 0.1°,0.62 at 0.5°) than the multi-model mean (R2=0.28 at 0.5°). Global ozone exposure is estimated to be increasing, driven by highly populated regions of Asia and Africa, despite decreases in the United States and Russia.

environmental modeling↗

The effect of the sea breeze circulation on surface ozone levels at Wallops Island, Virginia

Surface measurements of windspeed, direction, and ozone concentration collected at Wallops Island, Virginia, during the summers of 1977 and 1978 are analyzed to study the effects of the dominant mesoscale sea breeze circulation on the local photochemical oxidant levels. A bimodality in the atmospheric dynamics is linked to systematic variations in ozone concentration. It is concluded that during certain phases of the two circulation modes, increased wind speed reduces the resistance of the earth's surface to the deposition of ozone, and decreased ozone concentration levels result. For other phases, light winds occur, signifying high resistance to deposition and high ozone levels. This modulation by the local dynamics is a major impediment for pollutant studies in coastal environments, especially those centering on transport, because it tends to mask other processes that may be occurring.

Parsons, C. L.↗

Impact of the 2008 Global Recession on Air Quality over the United States: Implications for Surface Ozone Levels from Changes in NOx Emissions

Satellite and ground observations detected large variability in nitrogen oxides (NOx) during the 2008 economic recession, but the impact of the recession on air quality has not been quantified. This study combines observed NOx trends and a regional chemical transport model to quantify the impact of the recession on surface ozone (O3) levels over the continental United States. The impact is quantified by simulating O3 concentrations under two emission scenarios: business-as-usual (BAU) and recession. In the BAU case, the emission projection from the Cross-State Air Pollution Rule is used to estimate the would-be NOx emission level in 2011. In the recession case, the actual NO2 trends observed from Air Quality System ground monitors and the Ozone Monitoring Instrument on the Aura satellite are used to obtain realistic changes in NOx emissions. The model prediction with the recession effect agrees better with ground O3 observations over time and space than the prediction with the BAU emission. The results show that the recession caused a 12ppbv decrease in surface O3 concentration over the eastern United States, a slight increase (0.51ppbv) over the Rocky Mountain region, and mixed changes in the Pacific West. The gain in air quality benefits during the recession, however, could be quickly offset by the much slower emission reduction rate during the post-recession period.

NOx emissions↗

Interpretation of Probabilistic Surface Ozone Forecasts: A Case Study for Philadelphia

The use of probabilistic forecasting has been growing in a variety of disciplines because of its potential to emphasize the degree of uncertainty inherent in a prediction. Interpretation of probabilistic forecasts, however, is oftentimes difficult, deterring users who may benefit from such forecasts. To encourage broader use of probabilistic forecasts in the field of air quality, a process for interpreting forecasts from a statistical probabilistic air quality surface ozone model [the Regression in Self Organizing Map (REGiS)] is demonstrated. Four procedures to convert probabilistic to deterministic forecasts are explored for the Philadelphia, Pennsylvania, metropolitan area. These procedures calibrate the predicted probability of daily maximum 8-h-average ozone exceeding a standard value by 1) estimating climatological relative frequency, 2) establishing a probability of an exceedance threshold as 50%, 3) maximizing the threat score, and 4) determining the unit bias ratio. REGiS is trained using 2000–11 ozone-season (1 May–30 September) data, calibrated using 2012–14 data, and evaluated using 2015–18 data. Assessment of the calibration data with the Pierce skill score suggests an exceedance threshold based on climatological relative frequency for the conversion from probabilistic to deterministic forecasts. Calibrated REGiS generally compares well to predictions from the U.S. national air quality model and operational “expert” forecasts over the evaluation period. For other probabilistic models and situations, different procedures of converting probabilistic to deterministic forecasts may be more beneficial. The methods presented in this paper represent an approach for operational air quality forecasters seeking to use probabilistic model output to support forecasts designed to protect public health.

Nikolay Balashov↗

The 1977 surface ozone study of eastern Virginia

Data were collected by primarily twelve ground stations positioned throughout the eastern shore - tidewater area of Virginia and North Carolina. From an analysis of the ozone and wind data, certain trends were found such as the existence of a bias in ozone concentrations between stations and a linear correlation between average ozone concentration and latitude. In addition, higher ozone levels were found with surface winds from certain preferred directions at the various sites. The results, however, do not substantiate ozone or ozone precursor transport.

Williams, M. E.↗

Tropospheric Ozonesonde Profiles at Long-Term U.S. Monitoring Sites: 2. Links Between Trinidad Head, CA, Profile Clusters and Inland Surface Ozone Measurements

Much attention has been focused on the transport of ozone (O3) to the western U.S., particularly given the latest revision of the National Ambient Air Quality Standard to 70 parts per billion by volume (ppbv) of O3. This makes quantifying the contributions of stratosphere-to-troposphere exchange, local pollution, and pollution transport to this region essential. To evaluate free-tropospheric and surface O3 in the western U.S., we use self-organizing maps to cluster 18 years of ozonesonde profiles from Trinidad Head, CA. Three of nine O3 mixing ratio profile clusters exhibit thin laminae of high O3 above Trinidad Head. The high O3 layers are located between 1 and 6 km above mean sea level and reside above an inversion associated with a northern location of the Pacific subtropical high. Ancillary data (reanalyses, trajectories, and remotely sensed carbon monoxide) help identify the high O3 sources in one cluster, but distinguishing mixed influences on the elevated O3 in other clusters is difficult. Correlations between the elevated tropospheric O3 and surface O3 at high-altitude monitors at Lassen Volcanic and Yosemite National Parks, and Truckee, CA, are marked and long lasting. The temporal correlations likely result from a combination of transport of baseline O3 and covarying meteorological parameters. Days corresponding to the high O3 clusters exhibit hourly surface O3 anomalies of +5-10 ppbv compared to a climatology; the positive anomalies can last up to 3 days after the ozonesonde profile. The profile and surface O3 links demonstrate the importance of regular ozonesonde profiling at Trinidad Head.

STE↗

Formaldehyde Column Density Measurements as a Suitable Pathway to Estimate Near-Surface Ozone Tendencies from Space

In support of future satellite missions that aim to address the current shortcomings in measuring air quality from space, NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign was designed to enable exploration of relationships between column measurements of trace species relevant to air quality at high spatial and temporal resolution. In the DISCOVER-AQ data set, a modest correlation (r2 = 0.45) between ozone (O3) and formaldehyde (CH2O) column densities was observed. Further analysis revealed regional variability in the O3-CH2O relationship, with Maryland having a strong relationship when data were viewed temporally and Houston having a strong relationship when data were viewed spatially. These differences in regional behavior are attributed to differences in volatile organic compound (VOC) emissions. In Maryland, biogenic VOCs were responsible for approx.28% of CH2O formation within the boundary layer column, causing CH2O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH2O was observed. Box model simulations suggested that ambient CH2O mixing ratios have a weak diurnal trend (+/-20% throughout the day) due to photochemical effects, and that larger diurnal trends are associated with changes in hydrocarbon precursors. Finally, mathematical relationships were developed from first principles and were able to replicate the different behaviors seen in Maryland and Houston. While studies would be necessary to validate these results and determine the regional applicability of the O3-CH2O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near-surface air quality.

Surface Conditions from Column and Vertically Reso↗