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Increasing trends in biomass burning emissions significantly impact air quality in North America. Enhanced mixing ratios of ozone (O3) in urban areas during smoke-impacted periods occur through transport of O3 produced within the smoke or through mixing of pyrogenic volatile organic compounds (PVOCs) with urban nitrogen oxides (NOx = NO + NO2) to enhance local O3 production. Here, we analyze a set of detailed chemical measurements, including carbon monoxide (CO), NOx, and speciated volatile organic compounds (VOCs), to evaluate the effects of smoke transported from relatively local and long-range fires on O3 measured at a site in Boulder, Colorado, during summer 2020. Relative to the smoke-free period, CO, background O3, OH reactivity, and total VOCs increased during both the local and long-range smoke periods, but NOx mixing ratios remained approximately constant. These observations are consistent with transport of PVOCs (comprised primarily of oxygenates) but not NOx with the smoke and with the influence of O3 produced within the smoke upwind of the urban area. Box-model calculations show that local O3 production during all three periods was in the NOx-sensitive regime. Consequently, this locally produced O3 was similar in all three periods and was relatively insensitive to the increase in PVOCs. However, calculated NOx sensitivities show that PVOCs substantially increase O3 production in the transition and NOx-saturated (VOC-sensitive) regimes. These results suggest that (1) O3 produced during smoke transport is the main driver for O3 increases in NOx-sensitive urban areas and (2) smoke may cause an additional increase in local O3 production in NOx-saturated (VOC-sensitive) urban areas. Additional detailed VOC and NOx measurements in smoke impacted urban areas are necessary to broadly quantify the effects of wildfire smoke on urban O3 and develop effective mitigation strategies.

The Fires, Asian, and Stratospheric Transport–Las Vegas Ozone Study (FAST-LVOS) was conducted in May and June of 2017 to study the transport of ozone (O3) to Clark County, Nevada, a marginal non-attainment area in the southwestern United States (SWUS). This 6-week (20 May–30 June 2017) field campaign used lidar, ozonesonde, aircraft, and in situ measurements in conjunction with a variety of models to characterize the distribution of O3 and related species above southern Nevada and neighboring California and to probe the influence of stratospheric intrusions and wildfires as well as local, regional, and Asian pollution on surface O3 concentrations in the Las Vegas Valley (≈ 900 m above sea level, a.s.l.). In this paper, we describe the FAST-LVOS campaign and present case studies illustrating the influence of different transport processes on background O3 in Clark County and southern Nevada. The companion paper by Zhang et al. (2020) describes the use of the AM4 and GEOS-Chem global models to simulate the measurements and estimate the impacts of transported O3 on surface air quality across the greater southwestern US and Intermountain West. The FAST-LVOS measurements found elevated O3 layers above Las Vegas on more than 75 % (35 of 45) of the sample days and show that entrainment of these layers contributed to mean 8 h average regional background O3 concentrations of 50–55 parts per billion by volume (ppbv), or about 85–95 µg m−3. These high background concentrations constitute 70 %–80 % of the current US National Ambient Air Quality Standard (NAAQS) of 70 ppbv (≈ 120 µg m−3 at 900 m a.s.l.) for the daily maximum 8 h average (MDA8) and will make attainment of the more stringent standards of 60 or 65 ppbv currently being considered extremely difficult in the interior SWUS.

The El Niño–Southern Oscillation (ENSO) is known to modulate the strength and frequency of stratosphere-to-troposphere transport (STT) of ozone over the Pacific–North American region during late winter to early summer. Dynamical processes that have been proposed to account for this variability include variations in the amount of ozone in the lowermost stratosphere that is available for STT and tropospheric circulation-related variations in the frequency and geographic distribution of individual STT events. Here we use a large ensemble of Whole Atmosphere Community Climate Model (WACCM) simulations (forced by sea-surface temperature (SST) boundary conditions consistent with each phase of ENSO) to show that variability in lower-stratospheric ozone and shifts in the Pacific tropospheric jet constructively contribute to the amount of STT of ozone in the North American region during both ENSO phases. In terms of stratospheric variability, ENSO drives ozone anomalies resembling the Pacific–North American teleconnection pattern that span much of the lower stratosphere below 50 hPa. These ozone anomalies, which dominate over other ENSO-driven changes in the Brewer–Dobson circulation (including changes due to both the stratospheric residual circulation and quasi-isentropic mixing), strongly modulate the amount of ozone available for STT transport. As a result, during late winter (February–March), the stratospheric ozone response to the teleconnections constructively reinforces anomalous ENSO-jet-driven STT of ozone. However, as ENSO forcing weakens as spring progresses into summer (April–June), the direct effects of the ENSO-jet-driven STT transport weaken. Nevertheless, the residual impacts of the teleconnections on the amount of ozone in the lower stratosphere persist, and these anomalies in turn continue to cause anomalous STT of ozone. These results should prove helpful for interpreting the utility of ENSO as a subseasonal predictor of both free-tropospheric ozone and the probability of stratospheric ozone intrusion events that may cause exceedances in surface air quality standards.

Mass transport is important to many aspects of Pacific-North American climate, including stratosphere-to-troposphere transport of ozone to the planetary boundary layer, which has negative impacts on human health, and water vapor transport, which contributes to precipitation variability. Here, subseasonal forecasts (forecasts 3-6 weeks into the future) of Pacific jet variability are used to predict stratosphere-to-troposphere transport (STT) and tropical-to-extratropical moisture exports (TME) during boreal spring over the Pacific-North American region. To do this, we consider a very simple conditional probability: if 200 hPa zonal winds have a high (positive or negative) loading on a particular 200 hPa Pacific basin zonal wind pattern, then what will the corresponding shift in the probability of STT or TME be during those time periods? We first answer this question in the context of a retrospective analysis, which allows us to understand the regionality of STT and TME for different jet patterns. Then, using the retrospective results as a guide, we utilize zonal wind hindcasts from the European Centre for Medium-Range Weather Forecasts Integrated Forecasting System (taken from the S2S Prediction Project) to test whether STT and TME over specific geographic regions may be predictable for subseasonal forecast leads (weeks 3-6). For both analyses, STT and TME are taken from the ETH-Zürich Feature-based climatology database, which allows us to apply a single, self-consistent measure of transport for both the retrospective (1979-2016) and hindcast (1997-2016) analysis periods.We find that large anomalies in STT to the mid-troposphere over the North Pacific, TME to the west coast of the United States, and TME over Japan are found to have the best potential for subseasonal predictability using upper-level wind forecasts. STT to the planetary boundary layer over the intermountain west of the United States is also potentially predictable for subseasonal leads, but likely only in the context of shifts in the probability of extreme events. While STT and TME forecasts match verifications quite well in terms of spatial structure and anomaly sign, the number of anomalous transport days is underestimated compared to observations. The underestimation of the number of anomalous transport days exhibits a strong seasonal cycle, which becomes progressively worse as spring progresses into summer.

Stratosphere-to-troposphere mass transport to the planetary boundary layer (STT-PBL) peaks over the western United States during boreal spring, when deep stratospheric intrusions are most frequent. The tropopause-level jet structure modulates the frequency and character of intrusions, although the precise relationship between STT-PBL and jet variability has not been extensively investigated. In this study, we demonstrate how the North Pacific jet transition from winter to summer leads to the observed peak in STT-PBL. We show that the transition enhances STT-PBL through an increase in storm track activity which produces highly amplified Rossby waves and more frequent deep stratospheric intrusions over western North America. This dynamic transition coincides with the gradually deepening PBL, further facilitating STT-PBL in spring. We find that La Niña conditions in late winter are associated with an earlier jet transition and enhanced STT-PBL due to deeper and more frequent tropopause folds. An opposite response is found during El Niño conditions. El Niño–Southern Oscillation (ENSO) conditions also influence STT-PBL in late spring or early summer, during which time La Niña conditions are associated with larger and more frequent tropopause folds than both El Niño and ENSO-neutral conditions. These results suggest that knowledge of ENSO state and the North Pacific jet structure in late winter could be leveraged for predicting the strength of STT-PBL in the following months., Atmospheric Chemistry and Physics, 21 (4), ISSN:1680-7375, ISSN:1680-7367

The Fires, Asian, and Stratospheric Transport-Las Vegas Ozone Study (FAST-LVOS) was conducted in May and June of 2017 to study the transport of ozone (O3) to Clark County, Nevada, a marginal non-attainment area in the Southwestern U.S. (SWUS). This 6-week (20 May–30 June 2017) field campaign used lidar, ozonesonde, aircraft, and in-situ measurements in conjunction with a variety of models to characterize the distribution of O3 and related species above southern Nevada and neighbouring California, and to probe the influence of stratospheric intrusions, wildfires, and local, regional, and Asian pollution on surface O3 concentrations in Las Vegas and the surrounding area. In this paper, we describe the FAST-LVOS campaign and present case studies illustrating the influence of different transport processes on background O3 and air quality attainment in the SWUS. The measurements found elevated O3 layers above Las Vegas on more than 75 % (35 of 45) of the sample days, and show that entrainment of these layers contributed to mean 8-h average background O3 concentrations of 50–55 parts-per-billion by volume (ppbv) across southern Nevada. These background concentrations constitute 70–80 % of the current U.S. National Ambient Air Quality Standard (NAAQS) of 70 ppbv, and illustrate some of the challenges facing air quality managers tasked with O3 attainment in the SWUS during late spring and early summer. The companion paper by Zhang et al. (2020) describes the use of the AM4 and GEOS-Chem global models to estimate the impacts of transported O3 on surface air quality in the Southwestern U.S. and Intermountain West during the FAST-LVOS campaign.

International audience; The Soberanes Fire burned 53,470 ha (132,127 acres) along the central California coast between 22 July and 12 October 2016, generating dense smoke and a variety of gaseous compounds that drifted eastward into the San Joaquin Valley Air Basin (SJVAB), an “extreme” nonattainment area for ozone (O3). These gases included nitrogen oxides (NOx) and volatile organic compounds, the photochemical precursors of O3. The fire started during the California Baseline Ozone Transport Study, a field campaign that brought aircraft, surface, and remote sensing measurements of O3 and related species to central California. In this paper, we use the California Baseline Ozone Transport Study measurements to assess the impact of the Soberanes Fire on ozone and particulate air quality in the SJVAB. We focus our analysis on 27 July to 2 August when the smoke haze was heaviest and the highest O3 concentrations in the SJVAB during 2016 were recorded. Our analyses suggest that while 40 to 60 ppbv of fire‐generated O3 was transported to the eastern SJVAB in the 1‐ to 3‐km‐altitude range, relatively little smoke or fire‐generated O3 reached the surface in the Visalia area.

Aerosol retrieval using ozone lidars in the ultraviolet (UV) band is challenging but necessary for correcting aerosol interference in ozone retrieval and for studying the ozone-aerosol correlations. This study describes the aerosol retrieval algorithm for a tropospheric ozone lidar, quantifies the retrieval error budget, and intercompares the aerosol retrieval products at 299 nm with those at 532 nm from a high spectral resolution lidar (HSRL). After the cloud-contaminated data is filtered out, the aerosol backscatter or extinction coefficients at a 30-m and 10-min resolution retrieved by the ozone lidar are highly correlated with the HSRL products, with a coefficient of 0.95 suggesting that the ozone lidar can reliably measure aerosol structures with high spatio-temporal resolution when the signal-to-noise ratio is sufficient. The actual uncertainties of the aerosol retrieval from the ozone lidar generally agree with our theoretical analysis. The backscatter color ratio (backscatter-related exponent of wavelength dependence) linking the coincident data measured by the two instruments at 299 and 532 nm is 1.34 ± 0.11 while the Ångström (extinction-related) exponent is 1.49 ± 0.16 for a mixture of urban and fire smoke aerosols within the troposphere above Huntsville, AL, USA.

Aircraft observations and ozonesonde profiles collected on July 14 and 27, 2011, during the Maryland month-long DISCOVER-AQ campaign, indicate the presence of stratospheric air just above the planetary boundary layer (PBL). This raises the question of whether summer stratospheric intrusions (SIs) elevate surface ozone levels and to what degree they influence background ozone levels and contribute to ozone production. We used idealized stratospheric air tracers, along with observations, to determine the frequency and extent of SIs in Maryland during July 2011. On 4 of 14 flight days, SIs were detected in layers that the aircraft encountered above the PBL from the coincidence of enhanced ozone, moderate CO, and low moisture. Satellite observations of lower tropospheric humidity confirmed the occurrence of synoptic scale influence of SIs as do simulations with the GEOS-5 Atmospheric General Circulation Model. The evolution of GEOS-5 stratospheric air tracers agree with the timing and location of observed stratospheric influence and indicate that more than 50% of air in SI layers above the PBL had resided in the stratosphere within the previous 14 days. Despite having a strong influence in the lower free troposphere, these events did not significantly affect surface ozone, which remained low on intrusion days. The model indicates similar frequencies of stratospheric influence during all summers from 2009–2013. GEOS-5 results suggest that, over Maryland, the strong inversion capping the summer PBL limits downward mixing of stratospheric air during much of the day, helping to preserve low surface ozone associated with frontal passages that precede SIs.

On 2019-02-14, at 1:00 UTC, a large increase of ozone density at 8 km altitude was detected above Hampton, Virginia using the NASA Langley Mobile Ozone Lidar, LMOL. Ozone levels above 70 ppbv were observed down to an altitude of 4.5 km up to 5 h after the start of the event. The NASA GEOS Composition Forecast (GEOS-CF) model was used to investigate the hypothesis of a stratospheric intrusion (SI). The agreement between the model and the observations confirmed the stratospheric origin of the airmass and highlighted the capabilities of GEOS-CF to simulate intrusions. In parallel, MicroPulse Lidar (MPL) observations indicated that depolarizing particulates high in the troposphere showed downward motions linked to the intrusion. Since these particulates are linked to cirrus clouds, it is hypothesised that the SI led to an ice-virga effect. This might suggest that particulate observations can exhibit patterns of stratospheric intrusions and can be used, in certain cases, as a signature of the events. These particulates, likely ice crystals, have opposite distribution gradients compared to O3 at their interface which could be explained by a non-mixing of stratospheric and tropospheric air-masses as well as destruction of O3 by ice crystal-induced processes. Model-data comparison shows that if that latter effect exists, it has small consequences for the observed case. This work shows the capabilities of the LMOL system to detect SI and to validate the vertical and temporal modeling of SI by GEOS-CF, as well as showing that signatures of SI could be detected by MPL.

Tropospheric O3 has been decreasing across much of the eastern U.S. but has remained steady or even increased in some western regions. Recent increases in VOC and NOx emissions associated with the production of oil and natural gas (O&NG) may contribute to this trend in some areas. The Northern Front Range of Colorado has regularly exceeded O3 air quality standards during summertime in recent years. This region has VOC emissions from a rapidly developing O&NG basin and low concentrations of biogenic VOC in close proximity to urban-Denver NOx emissions. Here VOC OH reactivity (OHR), O3 production efficiency (OPE), and an observationally constrained box model are used to quantify the influence of O&NG emissions on regional summertime O3 production. Analyses are based on measurements acquired over two summers at a central location within the Northern Front Range that lies between major regional O&NG and urban emission sectors. Observational analyses suggest that mixing obscures any OPE differences in air primarily influenced by O&NG or urban emission sector. The box model confirms relatively modest OPE differences that are within the uncertainties of the field observations. Box model results also indicate that maximum O3 at the measurement location is sensitive to changes in NOx mixing ratio but also responsive to O&NG VOC reductions. Combined, these analyses show that O&NG alkanes contribute over 80% to the observed carbon mixing ratio, roughly 50% to the regional VOC OHR, and approximately 20% to regional photochemical O3 production.

Aircraft observations and ozonesonde profiles collected on July 14 and 27, 2011, during the Maryland month-long DISCOVER-AQ campaign, indicate the presence of stratospheric air just above the planetary boundary layer (PBL). This raises the question of whether summer stratospheric intrusions (SIs) elevate surface ozone levels and to what degree they influence background ozone levels and contribute to ozone production. We used idealized stratospheric air tracers, along with observations, to determine the frequency and extent of SIs in Maryland during July 2011. On 4 of 14 flight days, SIs were detected in layers that the aircraft encountered above the PBL from the coincidence of enhanced ozone, moderate CO, and low moisture. Satellite observations of lower tropospheric humidity confirmed the occurrence of synoptic scale influence of SIs as do simulations with the GEOS-5 Atmospheric General Circulation Model. The evolution of GEOS-5 stratospheric air tracers agree with the timing and location of observed stratospheric influence and indicate that more than 50% of air in SI layers above the PBL had resided in the stratosphere within the previous 14 days. Despite having a strong influence in the lower free troposphere, these events did not significantly affect surface ozone, which remained low on intrusion days. The model indicates similar frequencies of stratospheric influence during all summers from 2009-2013. GEOS-5 results suggest that, over Maryland, the strong inversion capping the summer PBL limits downward mixing of stratospheric air during much of the day, helping to preserve low surface ozone associated with frontal passages that precede SIs.

The North-America-based Tropospheric Ozone Lidar Network (TOLNet) was recently established to provide high spatio-temporal vertical profiles of ozone, to better understand physical processes driving tropospheric ozone variability, and to validate the tropospheric ozone measurements of upcoming space-borne missions such as Tropospheric Emissions: Monitoring Pollution (TEMPO). The network currently comprises six tropospheric ozone lidars, four of which are mobile instruments deploying to the field a few times per year, based on campaign and science needs. In August 2016, all four mobile TOLNet lidars were brought to the fixed TOLNet site of JPL-Table Mountain Facility for the one-week-long Southern California Ozone Observation Project (SCOOP). This inter-comparison campaign, which included 400 hours of lidar measurements and 18 ozonesondes launches, allowed for the unprecedented simultaneous validation of five of the six TOLNet lidars. For measurements between 3 and 10 km above sea level, a mean difference of 0.7 ppbv (1.7 %), with a root-mean-square deviation of 1.6 ppbv or 2.4 % was found between the lidars and ozonesondes, which is well within the combined uncertainties of the two measurement techniques. The few minor differences identified were typically associated with the known limitations of the lidars at the profiles altitude extremes (i.e., first 1 km above ground and at the instruments highest retrievable altitude). As part of a large homogenization and quality control effort within the network, many aspects of the TOLNet in-house data processing algorithms were also standardized and validated. This thorough validation of both the measurements and retrievals builds confidence in the high quality and reliability of the TOLNet ozone lidar profiles for many years to come, making TOLNet a valuable ground-based reference network for tropospheric ozone profiling.

Recent increases in oil and natural gas (NG) production throughout the western US have come with scientific and public interest in emission rates, air quality and climate impacts related to this industry. This study uses a regional scale air quality model WRF-Chem to simulate high ozone (O3) episodes during the winter of 2013 over the Uinta Basin (UB) in northeastern Utah, which is densely populated by thousands of oil and NG wells. The high resolution meteorological simulations are able to qualitatively reproduce the wintertime cold pool conditions that occurred in 2013, allowing the model to reproduce the observed multi-day buildup of atmospheric pollutants and accompanying rapid photochemical ozone formation in the UB. Two different emission scenarios for the oil and NG sector were employed in this study. The first emission scenario (bottom-up) was based on the US EPA National Emission Inventory (NEI) (2011, version 1) for the oil and NG sector for the UB. The second emission scenario (top-down) was based on the previously derived estimates of methane (CH4) emissions and a regression analysis for multiple species relative to CH4 concentration measurements in the UB. WRF-Chem simulations using the two emission data sets resulted in significant differences for concentrations of most gas-phase species. Evaluation of the model results shows greater underestimates of CH4 and other volatile organic compounds (VOCs) in the simulation with the NEI-2011 inventory than the case when the top-down emission scenario was used. Unlike VOCs, the NEI-2011 inventory significantly overestimates the emissions of nitrogen oxides (NOx), while the top-down emission scenario results in a moderate negative bias. Comparison of simulations using the two emission data sets reveals that the top-down case captures the high O3 episodes. In contrast, the simulation case using the bottom-up inventory is not able to reproduce any of the observed high O3 concentrations in the UB. A sensitivity analysis reveals that the major factors driving high wintertime O3 in the UB are shallow boundary layers with light winds, high emissions of VOCs from oil and NG operations compared to NOx emissions, enhancement of photolysis fluxes and reduction of O3 loss from deposition due to snow cover. Simple emission reduction scenarios show that the UB O3 production is VOC sensitive and NOx insensitive. The model results show a disproportionate contribution of aromatic VOCs to O3 formation relative to all other VOC emissions. We also present modeling results for winter of 2012, when high O3 levels were not observed in the UB. The air quality model together with the top-down emission framework presented here may help to address the emerging science and policy related questions surrounding the environmental impact of oil and NG drilling in western US.

Recently, two air quality campaigns were conducted in the southwestern United States to study the impact of transported ozone, stratospheric intrusions, and fire emissions on ground-level ozone concentrations. The California Baseline Ozone Transport Study (CABOTS) took place in May – August 2016 covering the central California coast and San Joaquin Valley, and the Fires, Asian, and Stratospheric Transport Las Vegas Ozone Study (FAST-LVOS) was conducted in the greater Las Vegas, Nevada area in May – June 2017. During these studies, nearly 1000 hours of ozone and aerosol profile data were collected with the NOAA TOPAZ lidar. A Doppler wind lidar and a radar wind profiler provided continuous observations of atmospheric turbulence, horizontal winds, and mixed layer height. These measurements allowed us to directly observe the degree to which ozone transport layers aloft were entrained into the boundary layer and to quantify the resulting impact on surface ozone levels. Mixed layer heights in the San Joaquin Valley during CABOTS were generally below 1 km above ground level (AGL), while boundary layer heights in Las Vegas during FAST-LVOS routinely exceeded 3 km AGL and occasionally reached up to 4.5 km AGL. Consequently, boundary layer entrainment was more often observed during FAST-LVOS, while most elevated ozone layers passed untapped over the San Joaquin Valley during CABOTS.

The California Research at the Nexus of Air Quality and Climate Change (CalNex) field study was conducted throughout California in May, June, and July of 2010. The study was organized to address issues simultaneously relevant to atmospheric pollution and climate change, including (1) emission inventory assessment, (2) atmospheric transport and dispersion, (3) atmospheric chemical processing, and (4) cloud-aerosol interactions and aerosol radiative effects. Measurements from networks of ground sites, a research ship, tall towers, balloon-borne ozonesondes, multiple aircraft, and satellites provided in situ and remotely sensed data on trace pollutant and greenhouse gas concentrations, aerosol chemical composition and microphysical properties, cloud microphysics, and meteorological parameters. This overview report provides operational information for the variety of sites, platforms, and measurements, their joint deployment strategy, and summarizes findings that have resulted from the collaborative analyses of the CalNex field study. Climate-relevant findings from CalNex include that leakage from natural gas infrastructure may account for the excess of observed methane over emission estimates in Los Angeles. Air-quality relevant findings include the following: mobile fleet VOC significantly declines, and NO_x emissions continue to have an impact on ozone in the Los Angeles basin; the relative contributions of diesel and gasoline emission to secondary organic aerosol are not fully understood; and nighttime NO_3 chemistry contributes significantly to secondary organic aerosol mass in the San Joaquin Valley. Findings simultaneously relevant to climate and air quality include the following: marine vessel emissions changes due to fuel sulfur and speed controls result in a net warming effect but have substantial positive impacts on local air quality.

Substantial uncertainties still exist in the scientific understanding of the possible interactions between urban and natural (biogenic) emissions in the production and transformation of atmospheric aerosol and the resulting impact on climate change. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) program's Carbonaceous Aerosol and Radiative Effects Study (CARES) carried out in June 2010 in Central Valley, California, was a comprehensive effort designed to improve this understanding. The primary objective of the field study was to investigate the evolution of secondary organic and black carbon aerosols and their climate-related properties in the Sacramento urban plume as it was routinely transported into the forested Sierra Nevada foothills area. Urban aerosols and trace gases experienced significant physical and chemical transformations as they mixed with the reactive biogenic hydrocarbons emitted from the forest. Two heavily-instrumented ground sites – one within the Sacramento urban area and another about 40 km to the northeast in the foothills area – were set up to characterize the evolution of meteorological variables, trace gases, aerosol precursors, aerosol size, composition, and climate-related properties in freshly polluted and "aged" urban air. On selected days, the DOE G-1 aircraft was deployed to make similar measurements upwind and across the evolving Sacramento plume in the morning and again in the afternoon. The NASA B-200 aircraft, carrying remote sensing instruments, was also deployed to characterize the vertical and horizontal distribution of aerosols and aerosol optical properties within and around the plume. This overview provides: (a) the scientific background and motivation for the study, (b) the operational and logistical information pertinent to the execution of the study, (c) an overview of key observations and initial findings from the aircraft and ground-based sampling platforms, and (d) a roadmap of planned data analyses and focused modeling efforts that will facilitate the integration of new knowledge into improved representations of key aerosol processes and properties in climate models., United States. Dept. of Energy. Atmospheric System Research Program (Contract DE-AC06-76RLO 1830), United States. National Oceanic and Atmospheric Administration, United States. National Aeronautics and Space Administration. HQ Science Mission Directorate Radiation Sciences Program, United States. National Aeronautics and Space Administration. CALIPSO Program, United States. Dept. of Energy. Atmospheric Radiation Measurement Program (Interagency Agreement No. DE-AI02-05ER63985)

Airborne and surface measurements of ozone (O3) during the Texas Air Quality Study campaigns in 2000 and 2006 (TexAQS 2000 and TexAQS 2006) were used to investigate the relationship between maximum daily O3 and the vector-averaged wind speed , calculated from radar wind profiler data, in the lower atmospheric boundary layer (BL). Both the maximum daily O3 and the peak “add-on” O3 contribution (calculated as the maximum minus the background values) from the Houston area showed a strong correlation (r∼0.7–0.9) with both the reciprocal of this wind speed −1, and the wind speed itself. Data from airborne platforms produced higher correlations in general than surface-measured values. Except for special cases where O3 was measured close to source activity in a location where the BL depth h was suppressed, peak daily ozone concentrations were not strongly correlated with h, and attempts to include 1/h dependence with −1 degraded the correlations—indicating that in general, h was not a strong predictor for maximum daily O3. Inclusion of daily maximum temperature in the regression analysis also failed to improve the correlations significantly. The high correlations for wind speed thus showed that was the meteorological variable most strongly associated with peak daily O3 concentrations. The best-fit regression line of peak daily O3 vs. for the 2000 data lay above the line for 2006 for wind speeds less than 5 m s−1, the difference increasing as the wind speeds weakened. This six-year decrease in O3 concentrations for the weakest-wind, most polluted days suggests that control strategies implemented between 2000 and 2006 may be producing beneficial effects, especially on the most polluted days.

We describe an instrument for simultaneous measurements of glyoxal (CHOCHO) and nitrogen dioxide (NO2) using cavity enhanced absorption spectroscopy with a broadband light source. The output of a Xenon arc lamp is coupled into a 1 m optical cavity, and the spectrum of light exiting the cavity is recorded by a grating spectrometer with a charge-coupled device (CCD) array detector. The mirror reflectivity and effective path lengths are determined from the known Rayleigh scattering of He and dry zero air (N2+O2). Least-squares fitting, using published reference spectra, allow the simultaneous retrieval of CHOCHO, NO2, O4, and H2O in the 441 to 469 nm spectral range. For a 1-min sampling time, the precision (±1σ) on signal for measurements of CHOCHO and NO2 is 29 pptv and 20 pptv, respectively. We directly compare measurements made with the incoherent broadband cavity enhanced absorption spectrometer with those from cavity ringdown instruments detecting CHOCHO and NO2 at 404 and 532 nm, respectively, and find linear agreement over a wide range of concentrations. The instrument has been tested in the laboratory with both synthetic and real air samples, and the demonstrated sensitivity and specificity suggest a strong potential for field measurements of both CHOCHO and NO2.

The "filling-in" (FI) of Fraunhofer lines, often referred to as the Ring effect, was examined using measurements of near ultraviolet sunlight scattered from the zenith sky above Boulder, Colorado during July and August 2005. The FI of the 344.1 nm Fe I line was directly determined by comparing direct sun and cloud-free zenith sky spectra recorded on the same day. The results, obtained over solar zenith angles (SZA) from 20° to 70°, are compared to the predictions of a simple rotational Raman Scattering (RRS) spectral model. The measured FI was found to be up to 70% greater than that predicted by first-order molecular scattering with a much stronger SZA dependence. Simultaneously measured aerosol optical depths and Monte Carlo calculations show that the combination of aerosol scattering and second-order molecular scattering can account for these differences, and potentially explain the contradictory SZA dependences in previously published measurements of FI. These two scattering processes also introduce a wavelength dependence to FI that complicates the fitting of diffuse sunlight observations in differential optical absorption spectroscopy (DOAS). A simple correction to improve DOAS retrievals by removing this wavelength dependence is described.

Evidence suggests deep stratospheric intrusions can elevate western US surface ozone to unhealthy levels during spring. These intrusions can be classified as ‘exceptional events', which are not counted towards non-attainment determinations. Understanding the factors driving the year-to-year variability of these intrusions is thus relevant for effective implementation of the US ozone air quality standard. Here we use observations and model simulations to link these events to modes of climate variability. We show more frequent late spring stratospheric intrusions when the polar jet meanders towards the western United States, such as occurs following strong La Niña winters (Niño3.4, Deep stratospheric ozone intrusions can elevate western US ground-level ozone to unhealthy concentrations, but the factors driving interannual variability are poorly understood. Here, the authors combine observations and numerical simulations showing a link between intrusion events and strong La Niña winters.

A high-ozone (O3) pollution episode was observed on 22 July 2014 during the concurrent “Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality” (DISCOVER-AQ) and “Front Range Air Pollution and Photochemistry Experiment” (FRAPPE) campaigns in northern Colorado. Surface O3 monitors at three regulatory sites exceeded the Environmental Protection Agency (EPA) 2008 National Ambient Air Quality Standard (NAAQS) daily maximum 8-hr average (MDA8) of 75 ppbv. To further characterize the polluted air mass and assess transport throughout the event, measurements are presented from O3 and wind profilers, O3-sondes, aircraft, and surface monitoring sites. Observations indicate thermally-driven upslope flow was established throughout the Colorado Front Range during the pollution episode. As the thermally-driven flow persisted throughout the day, O3 concentrations increased and affected high-elevation Rocky Mountain sites. These observations, coupled with modeling analyses, demonstrate a westerly return flow of polluted air aloft, indicating the mountain-plains solenoid circulation was established and impacted surface conditions within the Front Range.

We describe a two-channel broadband cavity enhanced absorption spectrometer (BBCEAS) for aircraft measurements of glyoxal (CHOCHO), methylglyoxal (CH3COCHO), nitrous acid (HONO), nitrogen dioxide (NO2), and water (H2O). The instrument spans 361–389 and 438–468 nm, using two light-emitting diodes (LEDs) and a single grating spectrometer with a charge-coupled device (CCD) detector. Robust performance is achieved using a custom optical mounting system, high-power LEDs with electronic on/off modulation, high-reflectivity cavity mirrors, and materials that minimize analyte surface losses. We have successfully deployed this instrument during two aircraft and two ground-based field campaigns to date. The demonstrated precision (2σ) for retrievals of CHOCHO, HONO and NO2 are 34, 350, and 80 parts per trillion (pptv) in 5 s. The accuracy is 5.8, 9.0, and 5.0 %, limited mainly by the available absorption cross sections.

Accurate measurements of nitrogen dioxide (NO2), a key trace gas in the formation and destruction of tropospheric ozone, are important in studies of urban pollution. Nitrogen dioxide column abundances were measured during the Texas Air Quality Study 2000 using visible absorption spectroscopy from an aircraft. The method allows for quantification of the integrated total number of nitrogen dioxide molecules in the polluted atmosphere and is hence a useful tool for measuring plumes of this key trace gas. Further, we show how such remote-sensing observations can be used to obtain information on the fluxes of nitrogen dioxide into the atmosphere with unique flexibility in terms of aircraft altitude, and the height and extent of mixing of the boundary layer. Observations of nitrogen dioxide plumes downwind of power plants were used to estimate the flux of nitrogen oxide emitted from several power plants in the Houston and Dallas metropolitan areas and in North Carolina. Measurements taken over the city of Houston were also employed to infer the total flux from the city as a whole.

Data from the oil- and gas-producing basin of northeastern Utah and a box model are used to assess the photochemical reactions of nitrogen oxides and volatile organic compounds that lead to excessive atmospheric ozone pollution in winter. The US experience with air quality degradation from shale gas extraction presents a measurement and modelling framework relevant to similar developments in other regions projected for the near future. High ozone mixing ratios have been observed in oil and gas producing basins in the United States during winter, but the underlying chemistry involved is not fully understood. This study presents a quantitative assessment of the underlying chemistry responsible for the winter ozone pollution events based on data from an oil and gas basin in Utah and a chemical 'box model' simulation. The results show that very high volatile organic carbon concentrations optimize the ozone production efficiency of nitrogen oxides with carbonyl photolysis as a dominant oxidant source. The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality1 to the influence of increased methane leakage on climate2, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides3,4 (NOx = NO + NO2) and volatile organic compounds5,6,7 (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects8. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter9,10,11,12,13. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.

The interannual variability of the springtime maximum in free tropospheric ozone above Colorado is examined using 5-1/2 years (1993-1998) of Differential Absorption Lidar (DIAL) data. Year-to-year differences of up to 20% in the monthly mean mixing ratios are shown to be correlated with changes in the 200 hPa wind speed over the eastern Pacific that are associated with the El Nino/Southern Oscillation (ENSO). This correlation is attributed to variations in the intensity of stratosphere-troposphere exchange (STE) associated with the mean transverse circulation at the subtropical jet exit over the eastern Pacific.

At Earth's surface, ozone is an air pollutant that causes respiratory health effects in humans and impairs plant growth and productivity ( 1 ). The Clean Air Act (CAA) of 1970 mandates that the U.S. Environmental Protection Agency (EPA) assess the ozone standard every 5 years and revise when necessary to protect human health. With a decision expected in October 2015 as to whether the standard will be toughened, we discuss limitations of ozone and precursor observations that hinder the ability of state and local air pollution–control agencies to accurately attribute sources of ozone within their jurisdictions. Attaining a lower standard may be particularly challenging in high elevations of the western United States, which are more likely to be affected by ozone that has been transported long distances or that originated in the stratosphere.

A five-year time series of lidar profiles from a site in Colorado is used to investigate the sources and scales of variability for ozone in the free troposphere. Analysis of 475 daily mean profiles derived from more than 25,000 individual profiles shows that ∼66% of the total variance is due to fluctuations on time scales from 1 day to 1 month, ∼30% on time scales from 1 month to 1 year, and ∼4% on time scales greater than 1 year. The analysis also identifies low-frequency fluctuations correlated with the El Nino/Southern Oscillation (ENSO) (following a ∼6-month lag) that may account for as much as 5% of the total variance in the data. The ENSO-related changes can also lead to apparent ozone trends that range from -0.2 to +0.5 ppbv/yr for different 10-year intervals between 1970 and 1990.

Two independent analyses of the daily maximum 8 h average ozone concentrations measured during the high ozone season (May through October) at Continuous Ambient Monitoring Stations are used to quantify the regional background ozone transported into the Houston-Galveston-Brazoria (HGB) area. The dependence on wind direction is examined, and long-term trends are determined using measurements made between 1998 and 2012. Both analyses show that the regional background ozone has declined during periods of continental outflow: i.e., the conditions associated with most high ozone episodes in HGB. The changes in regional background ozone found for northeasterly and southeasterly flow are -0.50 ± 0.54 and -0.79 ± 0.65 (95% confidence limit) ppbv yr(-1), respectively, which correspond to decreases of ∼7-11 ppbv between 1998 and 2012. This finding is consistent with the summertime downward trend of -0.45 ppbv yr(-1) (range of sites: -0.87 to +0.07 ppbv yr(-1)) for ozone in the eastern U.S. between 1990 and 2010 reported by Cooper et al. and shows that changing background concentrations are at least partially responsible for the decreased surface ozone in the HGB area over the past decade. Baseline ozone concentrations in air flowing into Texas from the Gulf of Mexico have not changed significantly over this period.

The two-dimensional structure of a tropopause fold that formed on the western flank of a cut-off cyclone over the western United States is examined through time series of vertical ozone profiles made using the NOAA Aeronomy Laboratory's Differential Absorption Lidar (DIAL) system at Fritz Peak Observatory (39.9°N, 105.3°W, 2.68 km above sea level). The observations are compared to calculated potential vorticity fields, and the net influx of ozone to the troposphere is estimated to be ∼5.5 × 1032 molecules assuming that the fold is irreversibly mixed into the troposphere below 8.5 km.

[1] The published literature debates the extent to which naturally occurring stratospheric ozone intrusions reach the surface and contribute to exceedances of the U.S. National Ambient Air Quality Standard (NAAQS) for ground-level ozone (75 ppbv implemented in 2008). Analysis of ozonesondes, lidar, and surface measurements over the western U.S. from April to June 2010 show that a global high-resolution (∼50 × 50 km2) chemistry-climate model (GFDL AM3) captures the observed layered features and sharp ozone gradients of deep stratospheric intrusions, representing a major improvement over previous chemical transport models. Thirteen intrusions enhanced total daily maximum 8-h average (MDA8) ozone to ∼70–86 ppbv at surface sites. With a stratospheric ozone tracer defined relative to a dynamically varying tropopause, we find that stratospheric intrusions can episodically increase surface MDA8 ozone by 20–40 ppbv (all model estimates are bias corrected), including on days when observed ozone exceeds the NAAQS threshold. These stratospheric intrusions elevated background ozone concentrations (estimated by turning off North American anthropogenic emissions in the model) to MDA8 values of 60–75 ppbv. At high-elevation western U.S. sites, the 25th–75th percentile of the stratospheric contribution is 15–25 ppbv when observed MDA8 ozone is 60–70 ppbv, and increases to ∼17–40 ppbv for the 70–85 ppbv range. These estimates, up to 2–3 times greater than previously reported, indicate a major role for stratospheric intrusions in contributing to springtime high-O3events over the high-altitude western U.S., posing a challenge for staying below the ozone NAAQS threshold, particularly if a value in the 60–70 ppbv range were to be adopted.

[1] The influence of stratosphere-to-troposphere transport (STT) on surface ozone (O3) concentrations in the greater Los Angeles area during the CalNex and IONS-2010 measurement campaigns has been investigated. Principal component analysis (PCA) of surface O3measurements from 41 sampling stations indicates that ∼13% of the variance in the maximum daily 8-h average (MDA8) O3between May 10 and June 19, 2010 was associated with changes of 2–3 day duration linked to the passage of upper-level troughs. Ozonesondes launched from Joshua Tree National Park and airborne lidar measurements show that these changes coincided with the appearance of stratospheric intrusions in the lower troposphere above southern California. The Lagrangian particle dispersion model FLEXPART reproduces most of these intrusions, and supports the conclusion from the PCA that significant transport of stratospheric air to the surface occurred on May 28–30. This intrusion led to a peak 1-h O3 concentration of 88 ppbv at Joshua Tree National Monument near the ozonesonde launch site on May 28, and widespread entrainment of stratospheric air into the boundary layer increased the local background O3 over the entire area to ∼55 ppbv on May 29–30. This background was 10–15 ppbv higher than the baseline O3 in air transported ashore from the Pacific Ocean, and when combined with locally produced O3 led to several exceedances of the current National Ambient Air Quality Standard (NAAQS) on the following day.

Ozone profiles obtained at Boulder, Colorado and Wallops Island, Virginia indicate that ozone was about 25% below normal during the winter and spring of 1992-93 in the 12-22 km region. This large ozone reduction in the lower stratosphere, though sometimes partially compensated by higher than normal ozone above 24 km, was responsible for the low total column ozone values observed across the United States during this period. Normal temperatures throughout the low ozone region suggest that transport-related effects are probably not the most important cause of the ozone deficits. This region of low ozone at Boulder corresponds closely with the location of the enhanced H2SO4/H2O aerosol from the Pinatubo eruption of 1991 as measured near Boulder and at Laramie, Wyoming. Trajectory analyses suggest that except at low altitudes in spring, air parcels on the days of the ozone measurements generally arrived at Boulder from higher latitude, although seldom higher than 60 deg N, and hence may have been subjected to heterogeneous chemical processing on the surface of Pinatubo aerosol droplets resulting in chlorine-catalyzed ozone destruction, a process which is believed to be more effective under the lower winter temperatures and sunlight levels of higher latitudes.

Observations of the stratospheric NO2 column amount over the Colorado mountains during January, February, and March, 1992 are compared to concurrent lidar measurements. During this period, large aerosol amounts due to the volcanic material injected into the stratosphere by Mt. Pinatubo were observed over Colorado. The observed NO2 column displays a strong anti-correlation with increasing amounts of stratospheric aerosol near 25–30 km for relatively low aerosol loadings. At higher aerosol loadings, the NO2 response appears to saturate, displaying little further reduction. The reasons for the altitude dependence of this relationship are probed with a one-dimensional stratospheric model, and it is shown that such a saturation response is to be expected for conditions where the heterogeneous reaction between N2O5 and H2O dominates the NOx chemistry, as in Prather [1992]. The results therefore provide evidence that heterogeneous reactions influence the chemical composition of the mid-latitude stratosphere, and in the general manner predicted by theory.

Differential absorption lidar (DIAL) is a powerful remote-sensing technique widely used to probe the spatial and temporal distribution of ozone and other gaseous atmospheric trace constituents. Although conceptually simple, the DIAL technique presents many challenging and often subtle technical difficulties that can limit its useful range and accuracy. One potentially serious source of error for many DIAL experiments is nonlinearity in the analog-to-digital converters used to capture lidar return signals. The impact of digitizer nonlinearity on DIAL measurements is examined, and a simple and inexpensive low-frequency dithering technique that significantly reduces the effects of ADC nonlinearity in DIAL and other applications in which the signal is repetitively averaged is described.