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Nitrous acid (HONO) mixing ratios measured in aged wildfire smoke plumes were higher than expected from known homogeneous chemical reactions. In a representative smoke plume, intercepted hours to days downwind of the source, the missing HONO source was highly correlated to particulate nitrate photolysis and NO2 reactive uptake to particles. Using a multilinear regression involving these two sources, we could explain the missing HONO production in this plume (R2 = 0.77). The resulting fit parameters from this plume had good explanatory power (R2 = 0.64) for missing HONO production in other fire plumes. The mean enhancement factor for particulate nitrate photolysis relative to gas‐phase nitric acid photolysis was 63 and the mean NO2 reactive uptake coefficient to submicron aerosol surface area forming HONO was 4.9 × 10−4. Given the likelihood of other neglected secondary HONO sources, these values are upper‐limits, suggesting a need to revisit HONO formation mechanisms in aged wildfire smoke. Plain Language Summary: A river of smoke from multiple wildfires was sampled far downwind and served as a natural laboratory for evaluating sources of nitrous acid (HONO) in aged wildfire smoke. HONO photolysis is an important source of reactive oxidants that initiate chemical transformations of wildfire emissions. We demonstrate that sources of HONO from chemical processes, known as secondary HONO sources, can largely be explained by two processes – the photolysis of particulate nitrate and the reactive uptake of nitrogen dioxide (NO2) to smoke aerosol particles. High time resolution in situ observations of HONO and auxiliary measurements were used to map out variations in the missing HONO source across a wide span of wildfire characteristics. The results place an upper limit on the magnitude of HONO sources from particulate nitrate photolysis, and suggest that the heterogeneous NO2 reactive uptake to smoke particles could be more important than previous field studies have indicated. These findings demonstrate the existence of additional processes other than direct emissions responsible for HONO formation in fire smoke. This secondary HONO source could increase the oxidizing capacity of wildfire smoke plumes significantly downwind of the emission source and therefore affect the formation and lifetime of other secondary wildfire smoke components. Key Points: Secondary multi‐phase processes dominate daytime HONO levels in aged (>3 hr) fire smokeThe inferred strength of secondary HONO production is most correlated to NO2, aerosol surface area, and particulate nitrateWe find significantly weaker HONO formation from particulate nitrate photolysis than previous reports [ABSTRACT FROM AUTHOR]

We aim to reduce uncertainties in CH2O and other volatile organic carbon (VOC) emissions through assimilation of remote sensing data. We first update a three‐dimensional (3D) chemical transport model, GEOS‐Chem with the KORUSv5 anthropogenic emission inventory and inclusion of chemistry for aromatics and C2H4, leading to modest improvements in simulation of CH2O (normalized mean bias (NMB): −0.57 to −0.51) and O3 (NMB: −0.25 to −0.19) compared against DC‐8 aircraft measurements during KORUS‐AQ; the mixing ratio of most VOC species are still underestimated. We next constrain VOC emissions using CH2O observations from two satellites (OMI and OMPS) and the DC‐8 aircraft during KORUS‐AQ. To utilize data from multiple platforms in a consistent manner, we develop a two‐step Hybrid Iterative Finite Difference Mass Balance and four‐dimensional variational inversion system (Hybrid IFDMB‐4DVar). The total VOC emissions throughout the domain increase by 47%. The a posteriori simulation reduces the low biases of simulated CH2O (NMB: −0.51 to −0.15), O3 (NMB: −0.19 to −0.06), and VOCs. Alterations to the VOC speciation from the 4D‐Var inversion include increases of biogenic isoprene emissions in Korea and anthropogenic emissions in Eastern China. We find that the IFDMB method alone is adequate for reducing the low biases of VOCs in general; however, 4D‐Var provides additional refinement of high‐resolution emissions and their speciation. Defining reasonable emission errors and choosing optimal regularization parameters are crucial parts of the inversion system. Our new hybrid inversion framework can be applied for future air quality campaigns, maximizing the value of integrating measurements from current and upcoming geostationary satellite instruments. Key Points: A two step Hybrid IFDMB‐4DVar inversion systemVOC DC‐8 emissions in Northeast Asia were constrained using CH2O concentrations observed by Ozone Monitoring Instrument, Ozone Mapping and Profiler Suite, and DC‐8 aircraft during KORUS‐AQVOC emissions were increased by 47% leading to improved performance in simulation of O3 and speciated VOCs [ABSTRACT FROM AUTHOR]

Organic aerosols (OA) represent a significant fraction of total submicron particulate matter (PM1) concentrations globally, including densely populated megacities such as Seoul. However, scientific understanding of the atmospheric formation and removal processes of OA, especially for secondary organic aerosols (SOA), is still highly uncertain. In this study, we examine the characteristics of SOA formation in Seoul during spring‐summer 2016 and fall‐winter 2017/2018, using airborne and ground observations along with a 3‐D global chemical transport model, GEOS‐Chem. We use four different SOA schemes in the model, including simplified and complex volatility‐based frameworks, and evaluate them by comparing the simulations with the observations to examine how our scientific understanding embedded in each SOA scheme affects the observed biases. Our analysis of the model performance of each scheme also provides the most suitable approach in simulating SOA in a typical urban environment. Comparisons of the simulated versus observed OA concentrations show that model biases range from −72% to +118%, with considerable variability among different schemes and seasons. We find that the inclusion of semi/intermediate volatile precursors, in addition to the traditional precursors, and chemical aging (functionalization) are important factors to simulate surface SOA concentrations in Seoul. However, a comparison of observed and simulated SOA/∆CO enhancement ratios suggests that most schemes underpredict SOA aging in upper levels in the boundary layer. We also find that the simplified SOA scheme can reproduce observed OA but often shows overestimation in surface air, indicating that uncertainties exist in bottom‐up emissions and precursor parameterization in Seoul. Plain Language Summary: We compare four different modeling approaches for simulating secondary organic aerosol (SOA) formation, accounting for a significant fraction of total fine particulate matter concentrations in Seoul, Korea. Using GEOS‐Chem, a chemical transport model, we find that current SOA schemes show large variabilities. Including an additional precursor species and further oxidation (i.e., chemical aging) of simulated SOA improves model performance. We also find that a simplified scheme with less computational cost can reproduce observed values but generally shows an overestimation in Seoul, indicating uncertainties in parameterization. Key Points: Model evaluation of simulated organic aerosols (OA) using different secondary organic aerosols (SOA) schemes in Seoul shows large variabilityThe inclusion of semi/intermediate volatile precursors and chemical aging are important factors in reducing model biasesThe simplified SOA scheme can reproduce observed OA, but uncertainties exist in precursor parameterization in Seoul [ABSTRACT FROM AUTHOR]

Wildfires are a major source of gas‐phase ammonia (NH3) to the atmosphere. Quantifying the evolution and fate of this NH3 is important to understanding the formation of secondary aerosol in smoke and its accompanying effects on radiative balance and nitrogen deposition. Here, we use data from the Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) to add new empirical constraints on the e‐folding loss timescale of NH3 and its relationship with particulate ammonium (pNH4) within wildfire smoke plumes in the western U.S. during summer 2018. We show that the e‐folding loss timescale of NH3 with respect to particle‐phase partitioning ranges from ∼24 to ∼4000 min (median of 55 min). Within these same plumes, oxidation of nitrogen oxides is observed concurrent with increases in the fraction of pNH4 in each plume sampled, suggesting that formation of ammonium nitrate (NH4NO3) is likely. We find wide variability in how close our in situ measurements of NH4NO3 are to those expected in a dry thermodynamic equilibrium, and find that NH4NO3 is most likely to form in fresh, dense smoke plumes injected at higher altitudes and colder temperatures. In chemically older smoke we observe correlations between both the fraction of pNH4 and the fraction of particulate nitrate (pNO3) in the aerosol with temperature, providing additional evidence of the presence of NH4NO3 and the influence of injection height on gas‐particle partitioning of NH3. Key Points: We estimate e‐folding loss timescales for ammonia in eight western U.S. smoke plumes from 24 to 4000 min old (median = 55 min)Ammonium nitrate formation is favorable in fresh, dense plumes injected higher into the troposphere, nitric acid is normally limitingObserved ammonium and nitrate fractions increase with lower temperatures in medium (1–3 days) and old (>3 days) chemical aged smoke [ABSTRACT FROM AUTHOR]

Reactive nitrogen (Nr) within smoke plumes plays important roles in the production of ozone, the formation of secondary aerosols, and deposition of fixed N to ecosystems. The Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) field campaign sampled smoke from 23 wildfires throughout the western U.S. during summer 2018 using the NSF/NCAR C‐130 research aircraft. We empirically estimate Nr normalized excess mixing ratios and emission factors from fires sampled within 80 min of estimated emission and explore variability in the dominant forms of Nr between these fires. We find that reduced N compounds comprise a majority (39%–80%; median = 66%) of total measured reactive nitrogen (ΣNr) emissions. The smoke plumes sampled during WE‐CAN feature rapid chemical transformations after emission. As a result, within minutes after emission total measured oxidized nitrogen (ΣNOy) and measured total ΣNHx (NH3 + pNH4) are more robustly correlated with modified combustion efficiency (MCE) than NOx and NH3 by themselves. The ratio of ΣNHx/ΣNOy displays a negative relationship with MCE, consistent with previous studies. A positive relationship with total measured ΣNr suggests that both burn conditions and fuel N content/volatilization differences contribute to the observed variability in the distribution of reduced and oxidized Nr. Additionally, we compare our in situ field estimates of Nr EFs to previous lab and field studies. For similar fuel types, we find ΣNHx EFs are of the same magnitude or larger than lab‐based NH3 EF estimates, and ΣNOy EFs are smaller than lab NOx EFs. Plain Language Summary: Smoke from large wildfires in the western U.S. degrades air quality across the whole U.S. Smoke contains a mixture of many different gases and particles, including carbon compounds like carbon dioxide and carbon monoxide, as well as nitrogen compounds such as ammonia and nitrogen oxides. Gases containing nitrogen are important for the production of ozone and the formation of more or larger particles as the smoke moves downwind. During the summer of 2018, we used the National Science Foundation/National Center for Atmospheric Research C130 research aircraft to fly through smoke across the western U.S. and measure many of the most abundant nitrogen compounds. We find that the smoke plumes we sampled emitted more nitrogen in a reduced form than in an oxidized form, and chemical reactions change the form and phase of nitrogen very quickly in the smoke. We compare our field measurements with laboratory measurements with the goal of using them together to improve our forecasts of how and where wildfire smoke will impact air quality. Key Points: Normalized excess mixing ratios of nitrogen species are reported for western U.S. wildfires; median of 66% of emissions are in reduced formWithin minutes after emission, rapid chemistry changes the distribution (species/amount/phase) of reactive nitrogen in fresh smoke plumesFor similar fuel types, NHx emissions factors are similar to or higher than lab‐based estimates; NOy emission factors are smaller [ABSTRACT FROM AUTHOR]

Organic nitrates (RONO2) are an important NOx sink. In warm, rural environments dominated by biogenic emissions, nocturnal NO3‐initiated production of RONO2 is competitive with daytime OH‐initiated RONO2 production. However, in urban areas, OH‐initiated production of RONO2 has been assumed dominant and NO3‐initiated production considered negligible. We show evidence for nighttime RONO2 production similar in magnitude to daytime production during three aircraft campaigns in chemically distinct summertime environments: Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS) in the rural Southeastern United States, Front Range Air Pollution and Photochemistry Experiment (FRAPPÉ) in the Colorado Front Range, and Korea‐United States Air Quality Study (KORUS‐AQ) around the megacity of Seoul. During each campaign, morning observations show RONO2 enhancements at constant, near‐background Ox (≡ O3+NO2) concentrations, indicating that the RONO2 are from a non‐photochemical source, whereas afternoon observations show a strong correlation between RONO2 and Ox resulting from photochemical production. We show that there are sufficient precursors for nighttime RONO2 formation during all three campaigns. This evidence impacts our understanding of nighttime NOx chemistry. Plain Language Summary: Nitrogen oxides are pollutants emitted during combustion which are involved in ozone and secondary aerosol production. One way in which nitrogen oxides are removed from the atmosphere is via chemistry that converts them to organic nitrates. This conversion of nitrogen oxides to organic nitrates has been thought to occur primarily during the day when the chemistry is driven by sunlight. Here we show evidence that nighttime processes generate similar quantities of organic nitrates to those produced by sunlight‐driven processes. Key Points: We show evidence for nocturnal production of organic nitrates similar in magnitude to daytime photochemical productionSignificant nocturnal production of organic nitrates observed from three aircraft campaigns in distinct environmentsNighttime production of organic nitrates impacts our understanding of the nighttime lifetime and fate of NOx [ABSTRACT FROM AUTHOR]

We present a comparison of instruments measuring nitrogen oxide species from an aircraft during the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign over the northeast United States. Instrument techniques compared here include chemiluminescence (CL), thermal dissociation laser‐induced fluorescence (TD‐LIF), cavity ring‐down spectroscopy (CRDS), high‐resolution time of flight, iodide‐adduct chemical ionization mass spectrometry (I‐CIMS), and aerosol mass spectrometry. Species investigated include NO2, NO, total nitrogen oxides (NOy), N2O5, ClNO2, and HNO3. Particulate‐phase nitrate is also included for comparisons of HNO3 and NOy. Instruments generally agreed within reported uncertainties, with individual flights sometimes showing much better agreement than the data set taken as a whole, due to flight‐to‐flight slope changes. NO measured by CRDS and CL showed an average relative slope of 1.16 ± 0.01 across all flights, which is outside of combined uncertainties. The source of the error was not identified. For NO2 measured by CRDS and TD‐LIF the average was 1.02 ± 0.00; for NOy measured by CRDS and CL the average was 1.01 ± 0.00; and for N2O5 measured by CRDS and I‐CIMS the average was 0.89 ± 0.01. NOy budget closure to within 20% is demonstrated. We observe nonlinearity in NO2 and NOy correlations at concentrations above ~30 ppbv that may be related to the NO discrepancy noted above. For ClNO2 there were significant differences between I‐CIMS and TD‐LIF, potentially due in part to the temperature used for thermal dissociation. Although the fraction of particulate nitrate measured by the TD‐LIF is not well characterized, it improves comparisons to include particulate measurements. Key Points: Nitrogen oxides are accurately and precisely measured by a number of independent methodsNew chemical ionization approaches compare well with more established methodsClosure of the NOy budget was observed [ABSTRACT FROM AUTHOR]

Sulfur dioxide (SO2) is emitted in large quantities from coal‐burning power plants and leads to various harmful health and environmental effects. In this study, we use plume intercepts from the Wintertime INvestigation of Transport, Emission and Reactivity (WINTER) campaign to estimate the oxidation rates of SO2 under wintertime conditions and the factors that determine SO2 removal. Observations suggest that OH governs the rate SO2 oxidation in the eastern United States during winter. The range of mean oxidation rates during the day from power plants were 0.22–0.71%/hr, producing SO2 lifetimes of 13–43 days, if SO2 consumption is assumed to occur during 10.5 hr of daylight in cloudless conditions. Though most nighttime rate measurements were zero within uncertainty, there is some evidence of nighttime removal, which suggests alternate oxidation mechanisms. The fastest nighttime observed SO2 oxidation rate was 0.25±0.07%/hr, producing a combined day/night SO2 lifetime of 8.5–21 days. The upper limit of the oxidation rate (the mean+1σ of the fastest day and night observations) is 16.5%/day, corresponding to a lifetime of 6.1 days. The analysis also quantifies the primary emission of sulfate from power plants. The median mole percentage of SO4‐2 from observed plumes was 1.7% and the mean percentage sulfate was 2.8% for intercepts within 1 hr of transit to power plants. The largest value observed from close intercepts was over 7% sulfate, and the largest extrapolated value was 18%, based on intercepts further from their source and fastest observed oxidation rate. Key Points: The daytime conversion rate of SO2 to SO4‐2 was 0.22‐0.71%/hr in winter under clear‐sky conditions, with lifetimes of 140‐450 hrFor 10.5 hr of daylight, the upper limit of the oxidation rate is 16.5%/day, corresponding to a lifetime of 6.1 daysDirect emissions of SO4‐2 relative to total sulfur (SO2 + SO4‐2) had mean and median values of 1.7% and 2.8%, respectively [ABSTRACT FROM AUTHOR]

Abstract: Although urban NOx lifetimes have been examined extensively during summertime conditions, wintertime NOx chemistry has been comparatively less studied. We use measurements of NOx and its oxidation products from the aircraft‐based WINTER (Wintertime INvestigation of Transport, Emissions, and Reactivity) experiment over the northeastern United States during February–March 2015 to describe the NOx lifetime during conditions when days are shorter, actinic flux is reduced, and temperatures are colder. By analyzing regional outflow from the East Coast, we show that NOx is long lived during the winter, with a longer daytime lifetime (29 hr) than nighttime lifetime (6.3 hr). We demonstrate that wintertime NOx emissions have an overall lifetime controlled by the nighttime conversion of NOx to nitric acid (HNO3) via N2O5 heterogeneous chemistry, and we discuss constraints on the rates of NOx conversion to HNO3. Additionally, analysis of the nighttime Ox budget suggests that approximately 15% of O3 is lost overnight through N2O5 production and subsequent reaction with aerosol to form HNO3. [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: 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: Nocturnal dinitrogen pentoxide (N2O5) heterogeneous chemistry impacts regional air quality and the distribution and lifetime of tropospheric oxidants. Formed from the oxidation of nitrogen oxides, N2O5 is heterogeneously lost to aerosol with a highly variable reaction probability, γ(N2O5), dependent on aerosol composition and ambient conditions. Reaction products include soluble nitrate (HNO3 or NO3−) and nitryl chloride (ClNO2). We report the first‐ever derivations of γ(N2O5) from ambient wintertime aircraft measurements in the critically important nocturnal residual boundary layer. Box modeling of the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign over the eastern United States derived 2,876 individual γ(N2O5) values with a median value of 0.0143 and range of 2 × 10−5 to 0.1751. WINTER γ(N2O5) values exhibited the strongest correlation with aerosol water content, but weak correlations with other variables, such as aerosol nitrate and organics, suggesting a complex, nonlinear dependence on multiple factors, or an additional dependence on a nonobserved factor. This factor may be related to aerosol phase, morphology (i.e., core shell), or mixing state, none of which are commonly measured during aircraft field studies. Despite general agreement with previous laboratory observations, comparison of WINTER data with 14 literature parameterizations (used to predict γ(N2O5) in chemical transport models) confirms that none of the current methods reproduce the full range of γ(N2O5) values. Nine reproduce the WINTER median within a factor of 2. Presented here is the first field‐based, empirical parameterization of γ(N2O5), fit to WINTER data, based on the functional form of previous parameterizations. [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]

Abstract: A number of satellite‐based instruments have become an essential part of monitoring emissions. Despite sound theoretical inversion techniques, the insufficient samples and the footprint size of current observations have introduced an obstacle to narrow the inversion window for regional models. These key limitations can be partially resolved by a set of modest high‐quality measurements from airborne remote sensing. This study illustrates the feasibility of nitrogen dioxide (NO2) columns from the Geostationary Coastal and Air Pollution Events Airborne Simulator (GCAS) to constrain anthropogenic NOx emissions in the Houston‐Galveston‐Brazoria area. We convert slant column densities to vertical columns using a radiative transfer model with (i) NO2 profiles from a high‐resolution regional model (1 × 1 km2) constrained by P‐3B aircraft measurements, (ii) the consideration of aerosol optical thickness impacts on radiance at NO2 absorption line, and (iii) high‐resolution surface albedo constrained by ground‐based spectrometers. We characterize errors in the GCAS NO2 columns by comparing them to Pandora measurements and find a striking correlation (r > 0.74) with an uncertainty of 3.5 × 1015 molecules cm−2. On 9 of 10 total days, the constrained anthropogenic emissions by a Kalman filter yield an overall 2–50% reduction in polluted areas, partly counterbalancing the well‐documented positive bias of the model. The inversion, however, boosts emissions by 94% in the same areas on a day when an unprecedented local emissions event potentially occurred, significantly mitigating the bias of the model. The capability of GCAS at detecting such an event ensures the significance of forthcoming geostationary satellites for timely estimates of top‐down emissions. [ABSTRACT FROM AUTHOR]

Abstract: Nitric oxide (NO) is emitted in large quantities from coal‐burning power plants. During the day, the plumes from these sources are efficiently mixed into the boundary layer, while at night, they may remain concentrated due to limited vertical mixing during which they undergo horizontal fanning. At night, the degree to which NO is converted to HNO3 and therefore unable to participate in next‐day ozone (O3) formation depends on the mixing rate of the plume, the composition of power plant emissions, and the composition of the background atmosphere. In this study, we use observed plume intercepts from the Wintertime INvestigation of Transport, Emissions and Reactivity campaign to test sensitivity of overnight NOx removal to the N2O5 loss rate constant, plume mixing rate, background O3, and background levels of volatile organic compounds using a 2‐D box model of power plant plume transport and chemistry. The factor that exerted the greatest control over NOx removal was the loss rate constant of N2O5. At the lowest observed N2O5 loss rate constant, no other combination of conditions converts more than 10% of the initial NOx to HNO3. The other factors did not influence NOx removal to the same degree. [ABSTRACT FROM AUTHOR]

This study quantifies the immediate influences of aerosols from urban anthropogenic and shipping emission sources on carbon and water fluxes in East Asia on a cloudy day in spring 2016 when strong regional pollution transport occurred and intensive field campaign measurements are available. Within National Aeronautics and Space Administration (NASA)'s Land Information System (LIS), a long‐term offline Noah‐multiparameterization (MP) simulation with dynamic vegetation is performed. Modeled soil moisture and leaf area index are evaluated with satellite observations to ensure that land surface conditions are moderately well reproduced. The LIS output is then used to initialize several coupled NASA‐Unified Weather Research and Forecasting model simulations with online chemistry in which urban anthropogenic and shipping emissions are (1) largely based on the Hemispheric Transport of Air Pollution Phase 2 inventory for 2010, (2) reduced by 20% and 50% for all chemical species, and (3) adjusted only for nitrogen oxides (NOx) using satellite observations. Overall, modeled gross primary productivity and evapotranspiration almost linearly increase with the all‐species emission reductions, but their responses to emission‐induced aerosol optical depth (AOD) changes show strong spatial variability resulting from combined radiation and temperature impacts. Using satellite‐observation‐constrained NOx emissions, modeled nitrogen species and AOD better match various measurements at some locations/times. All‐species and NOx‐only emission adjustments lead to different gross primary productivity and evapotranspiration changes with AOD, especially over South Korea. This study demonstrates the importance of accurately quantifying emission impacts on atmosphere‐biosphere interactions. Improving more species' emission inputs for Earth system models, including applying effective chemical data assimilation methods, is strongly encouraged. Key Points: Carbon and water fluxes are calculated by Noah‐MP (with dynamic vegetation) coupled with atmospheric weather and chemistryOverall, GPP and ET almost linearly increase with the all‐species urban/shipping emission reductions on a cloudy day in East AsiaGPP and ET responses to emission‐induced AOD changes differ by region and for all‐species and NOx‐only emission adjustments [ABSTRACT FROM AUTHOR]

Nitryl chloride (ClNO2) plays an important role in the budget and distribution of tropospheric oxidants, halogens, and reactive nitrogen species. ClNO2 is formed from the heterogeneous uptake and reaction of dinitrogen pentoxide (N2O5) on chloride‐containing aerosol, with a production yield, ϕ(ClNO2), defined as the moles of ClNO2 produced relative to N2O5 lost. The ϕ(ClNO2) has been increasingly incorporated into 3‐D chemical models where it is parameterized based on laboratory‐derived kinetics and currently accepted aqueous‐phase formation mechanism. This parameterization models ϕ(ClNO2) as a function of the aerosol chloride to water molar ratio. Box model simulations of night flights during the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) aircraft campaign derived 3,425 individual ϕ(ClNO2) values with a median of 0.138 and range of 0.003 to 1. Comparison of the box model median to those predicted by two other field‐based ϕ(ClNO2) derivation methods agreed within a factor of 1.3, within the uncertainties of each method. In contrast, the box model median was 75–84% lower than predictions from the laboratory‐based parameterization (i.e., [parameterization − box model]/parameterization). An evaluation of factors influencing this difference reveals a positive dependence of ϕ(ClNO2) on aerosol water, opposite to the currently parameterized trend. Additional factors may include aqueous‐phase competition reactions for the nitronium ion intermediate and/or direct ClNO2 loss mechanisms. Further laboratory studies of ClNO2 formation and the impacts of aerosol water, sulfate, organics, and ClNO2 aqueous‐phase reactions are required to elucidate and quantify these processes on ambient aerosol, critical for the development of a robust ϕ(ClNO2) parameterization. Key Points: Box modeling of wintertime measurements over the eastern United States provides the first determinations of ClNO2 yields (ϕ(ClNO2)) from aircraftThe median ϕ(ClNO2) value derived from the box model is overpredicted by 75‐84% by the current laboratory‐based ϕ(ClNO2) parameterizationModeled and parameterized ϕ(ClNO2) values show opposite trends with aerosol water, suggesting an incorrectly parameterized dependence [ABSTRACT FROM AUTHOR]

We present airborne observations of gaseous reactive halogen species (HCl, Cl2, ClNO2, Br2, BrNO2, and BrCl), sulfur dioxide (SO2), and nonrefractory fine particulate chloride (pCl) and sulfate (pSO4) in power plant exhaust. Measurements were conducted during the Wintertime INvestigation of Transport, Emissions, and Reactivity campaign in February–March of 2015 aboard the NCAR‐NSF C‐130 aircraft. Fifty air mass encounters were identified in which SO2 levels were elevated ~5 ppb above ambient background levels and in proximity to operational power plants. Each encounter was attributed to one or more potential emission sources using a simple wind trajectory analysis. In case studies, we compare measured emission ratios to those reported in the 2011 National Emissions Inventory and present evidence of the conversion of HCl emitted from power plants to ClNO2. Taking into account possible chemical conversion downwind, there was general agreement between the observed and reported HCl:SO2 emission ratios. Reactive bromine species (Br2, BrNO2, and/or BrCl) were detected in the exhaust of some coal‐fired power plants, likely related to the absence of wet flue gas desulfurization emission control technology. Levels of bromine species enhanced in some encounters exceeded those expected assuming all of the native bromide in coal was released to the atmosphere, though there was no reported use of bromide salts (as a way to reduce mercury emissions) during Wintertime INvestigation of Transport, Emissions, and Reactivity observations. These measurements represent the first ever in‐flight observations of reactive gaseous chlorine and bromine containing compounds present in coal‐fired power plant exhaust. Key Points: Gaseous inorganic chlorine and bromine species were observed in the exhaust of coal‐fired power plants during the WINTER flight campaignWe present evidence of the conversion of hydrogen chloride (HCl) emitted from power plants to nitryl chloride (ClNO2) downwind of a sourceObserved levels of Br2, BrNO2, and BrCl in some plumes strongly suggest artificial enhancement of bromide in the coal [ABSTRACT FROM AUTHOR]