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Formaldehyde column density (ΩHCHO) showed a potentially useful correlation with surface ozone during the LISTOS campaign on Long Island Sound and the KORUS‐AQ campaign in Seoul, South Korea. This builds on previous work that identified this relationship from in situ aircraft observations with similar findings for ground‐based and airborne remote sensing of ΩHCHO. In the Long Island Sound region, ΩHCHO and surface ozone exhibited strong temporal (r2 = 0.66) and spatial (r2 = 0.73) correlation. The temporal variability in ΩHCHO (∼1 Dobson units [DU]) was larger than the range in the spatial average (∼0.1 DU). The spatial average is most useful for informing ozone monitoring strategies, demonstrating the challenge in using ΩHCHO satellite data sets for this purpose. In Seoul, high levels of NO2 resulted in Ox better correlating with ΩHCHO than surface ozone due to titration effects. The ΩHCHO–Ox relationship may therefore reflect the sum of surface ozone and related photochemical oxidants, relevant to air quality standards set to regulate this quantity such as the U.S. EPA National Ambient Air Quality Standard (NAAQS). The relationship of ΩHCHO to Ox shifted in Seoul during the campaign demonstrating the need to evaluate this relationship over longer time periods. With sufficient precision in future satellite retrievals, ΩHCHO observations could be useful for evaluating the adequacy of surface air quality monitoring strategies. Plain Language Summary: Surface ozone is hazardous to human health and the environment. Space‐based monitoring techniques provide the opportunity to improve our knowledge of regional surface ozone pollution. Ozone measurements from space have limited ability to detect surface concentrations. Observations of column formaldehyde, a trace gas produced during production of surface ozone, are correlated with surface ozone and related pollutants. This relationship points to a potential use of satellite observations for identifying regions of harmful ozone concentrations to complement sparse surface monitoring networks. Key Points: Column formaldehyde (ΩHCHO) is related spatially and temporally with surface ozone during the LISTOS and KORUS‐AQ field campaignsΩHCHO better correlates with Ox (≡ozone + NO2) which more broadly represents ozone and related photochemical oxidantsSatellite ΩHCHO could be an indicator of ozone and related photochemical oxidants and inform air quality monitoring strategies [ABSTRACT FROM AUTHOR]

Reactive chlorine and bromine species emitted from snow and aerosols can significantly alter the oxidative capacity of the polar boundary layer. However, halogen production mechanisms from snow remain highly uncertain, making it difficult for most models to include descriptions of halogen snow emissions and to understand the impact on atmospheric chemistry. We investigate the influence of Arctic halogen emissions from snow on boundary layer oxidation processes using a one‐dimensional atmospheric chemistry and transport model (PACT‐1D). To understand the combined impact of snow emissions and boundary layer dynamics on atmospheric chemistry, we model Cl2 and Br2 primary emissions from snow and include heterogeneous recycling of halogens on both snow and aerosols. We focus on a 2‐day case study from the 2009 Ocean‐Atmosphere‐Sea Ice‐Snowpack campaign at Utqiaġvik, Alaska. The model reproduces both the diurnal cycle and high quantity of Cl2 observed, along with the measured concentrations of Br2, BrO, and HOBr. Due to the combined effects of emissions, recycling, vertical mixing, and atmospheric chemistry, reactive chlorine is typically confined to the lowest 15 m of the atmosphere, while bromine can impact chemistry up to and above the surface inversion height. Upon including halogen emissions and recycling, the concentration of HOx (HOx = OH + HO2) at the surface increases by as much as a factor of 30 at mid‐day. The change in HOx due to halogen chemistry, as well as chlorine atoms derived from snow emissions, significantly reduce volatile organic compound lifetimes within a shallow layer near the surface. Key Points: A combination of factors including snow emissions, vertical mixing, and atmospheric chemistry explain surface Arctic halogen observationsSnow emissions of halogens impact atmospheric chemistry within a shallow layer near the surfaceSurface HOx concentrations are increased by up to a factor of 30 due to halogen chemistry [ABSTRACT FROM AUTHOR]

Abstract: Strong correlations of O3‐CH2O, O3‐CO and CO‐CH2O were observed during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER‐AQ) aircraft experiment in July 2011 over the Washington‐Baltimore area. The linear regression slopes of observed O3‐CH2O, O3‐CO, and CO‐CH2O do not vary significantly with time (11 a.m. to 4 p.m.) or altitude in the boundary layer. These observed relationships are simulated well by a regional chemical transport model. Using tagged‐tracer simulations, we find that biogenic isoprene oxidation makes the largest contribution to the regression slope of O3‐CH2O across much of the eastern United States, providing a good indicator for O3 enhanced by biogenic isoprene oxidation. In contrast, the regression slope of O3‐CO is controlled by both anthropogenic and biogenic emissions. Therefore, we use the CO‐CH2O relationship to separate biogenic from anthropogenic contributions to CO. By combining these regressions, we can track the contributions to surface O3 by anthropogenic and biogenic factors and build a fast‐response ozone estimator using near‐surface CH2O and CO concentrations as inputs. We examine the quality of O3 estimator by increasing or decreasing anthropogenic emissions by up to 50%. The estimated O3 distribution is in reasonably good agreement with the full‐model simulations (R2 > 0.77 in the range of −30% to +50% of anthropogenic emissions). The analysis provides the basis for using high‐quality geostationary satellites with UV, thermal infrared, or near‐infrared instruments for observing CH2O and CO to improve surface O3 distribution monitoring. The estimation model can also be applied to derive observation‐derived regional metrics to evaluate and improve full‐fledged 3‐D air quality models. [ABSTRACT FROM AUTHOR]

Abstract: Deep convective transport of gaseous precursors to ozone (O3) and aerosols to the upper troposphere is affected by liquid phase and mixed‐phase scavenging, entrainment of free tropospheric air and aqueous chemistry. The contributions of these processes are examined using aircraft measurements obtained in storm inflow and outflow during the 2012 Deep Convective Clouds and Chemistry (DC3) experiment combined with high‐resolution (dx≤3 km) WRF‐Chem simulations of a severe storm, an air mass storm, and a mesoscale convective system (MCS). The simulation results for the MCS suggest that formaldehyde (CH2O) is not retained in ice when cloud water freezes, in agreement with previous studies of the severe storm. By analyzing WRF‐Chem trajectories, the effects of scavenging, entrainment, and aqueous chemistry on outflow mixing ratios of CH2O, methyl hydroperoxide (CH3OOH), and hydrogen peroxide (H2O2) are quantified. Liquid phase microphysical scavenging was the dominant process reducing CH2O and H2O2 outflow mixing ratios in all three storms. Aqueous chemistry did not significantly affect outflow mixing ratios of all three species. In the severe storm and MCS, the higher than expected reductions in CH3OOH mixing ratios in the storm cores were primarily due to entrainment of low‐background CH3OOH. In the air mass storm, lower CH3OOH and H2O2 scavenging efficiencies (SEs) than in the MCS were partly due to entrainment of higher background CH3OOH and H2O2. Overestimated rain and hail production in WRF‐Chem reduces the confidence in ice retention fraction values determined for the peroxides and CH2O. [ABSTRACT FROM AUTHOR]

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]

Abstract: Modeled source attribution information from the Community Multiscale Air Quality model was coupled with ambient data from the 2011 Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality Baltimore field study. We assess source contributions and evaluate the utility of using aircraft measured CO and NOy relationships to constrain emission inventories. We derive ambient and modeled ΔCO:ΔNOy ratios that have previously been interpreted to represent CO:NOy ratios in emissions from local sources. Modeled and measured ΔCO:ΔNOy are similar; however, measured ΔCO:ΔNOy has much more daily variability than modeled values. Sector‐based tagging shows that regional transport, on‐road gasoline vehicles, and nonroad equipment are the major contributors to modeled CO mixing ratios in the Baltimore area. In addition to those sources, on‐road diesel vehicles, soil emissions, and power plants also contribute substantially to modeled NOy in the area. The sector mix is important because emitted CO:NOx ratios vary by several orders of magnitude among the emission sources. The model‐predicted gasoline/diesel split remains constant across all measurement locations in this study. Comparison of ΔCO:ΔNOy to emitted CO:NOy is challenged by ambient and modeled evidence that free tropospheric entrainment, and atmospheric processing elevates ambient ΔCO:ΔNOy above emitted ratios. Specifically, modeled ΔCO:ΔNOy from tagged mobile source emissions is enhanced 5–50% above the emitted ratios at times and locations of aircraft measurements. We also find a correlation between ambient formaldehyde concentrations and measured ΔCO:ΔNOy suggesting that secondary CO formation plays a role in these elevated ratios. This analysis suggests that ambient urban daytime ΔCO:ΔNOy values are not reflective of emitted ratios from individual sources. [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]

Diagnosing carbon dioxide (CO2) and methane (CH4) fluxes at subcontinental scales is complicated by sparse observations, limited knowledge of prior fluxes and their uncertainties, and background and transport errors. Multispecies measurements in flasks sampled during the wintertime ACT‐America campaign were used for background characterization and source apportionment of regional anthropogenic CO2 and CH4 fluxes when ecosystem CO2 exchange is likely to be least active. Continental background trace gas mole fractions for regional enhancements are defined using samples from the upper troposphere and assessed using model products. Trace gas enhancements taken from flask samples in the lower troposphere with background levels subtracted out are then interpreted to inform CO2 and CH4 enhancement variability in the eastern United States. Strong correlations between CO2 and CH4 enhancements in the Midwestern and Mid‐Atlantic United States indicated colocated anthropogenic sources. Oil and natural gas influence was also broadly observed throughout the entire observational domain. In the Midwestern United States, agricultural influence on CO2 and CH4 enhancement variability was evident during above‐average wintertime temperatures. Weaker correlations between CO2 and anthropogenic tracer enhancements in the Southeastern United States indicated potentially nonnegligible wintertime ecosystem CO2 exchange, with biogenic tracers indicating more active surface processing than other regions. These whole‐air flask samples illuminated significant regional CO2 and CH4 sources or sinks during Atmospheric Carbon and Transport‐America (ACT‐America) and can provide additional information for informing regional inverse modeling efforts. Key Points: Multispecies flask samples are used to characterize regional wintertime eastern U.S. CO2 and CH4 enhancement variabilityMid‐Atlantic and Midwestern U.S. CO2 and CH4 enhancements are primarily anthropogenicWinter Southeastern U.S. CO2 and CH4 enhancements indicate influence from biogenic exchange and surface processing [ABSTRACT FROM AUTHOR]