Impact of Biomass Burning Organic Aerosol Volatility on Smoke Concentrations Downwind of Fires.

Biomass burning particulate matter (BBPM) affects regional air quality and global climate, with impacts expected to continue to grow over the coming years. We show that studies of North American fires have a systematic altitude dependence in measured BBPM normalized excess mixing ratio (NEMR; ΔPM/ΔCO), with airborne and high-altitude studies showing a factor of 2 higher NEMR than ground-based measurements. We report direct airborne measurements of BBPM volatility that partially explain the difference in the BBPM NEMR observed across platforms. We find that when heated to 40-45 °C in an airborne thermal denuder, 19% of lofted smoke PM1 evaporates. Thermal denuder measurements are consistent with evaporation observed when a single smoke plume was sampled across a range of temperatures as the plume descended from 4 to 2 km altitude. We also demonstrate that chemical aging of smoke and differences in PM emission factors can not fully explain the platform-dependent differences. When the measured PM volatility is applied to output from the High Resolution Rapid Refresh Smoke regional model, we predict a lower PM NEMR at the surface compared to the lofted smoke measured by aircraft. These results emphasize the significant role that gas-particle partitioning plays in determining the air quality impacts of wildfire smoke.

An observation-based, reduced-form model for oxidation in the remote marine troposphere.

The hydroxyl radical (OH) fuels atmospheric chemical cycling as the main sink for methane and a driver of the formation and loss of many air pollutants, but direct OH observations are sparse. We develop and evaluate an observation-based proxy for short-term, spatial variations in OH (ProxyOH) in the remote marine troposphere using comprehensive measurements from the NASA Atmospheric Tomography (ATom) airborne campaign. ProxyOH is a reduced form of the OH steady-state equation representing the dominant OH production and loss pathways in the remote marine troposphere, according to box model simulations of OH constrained with ATom observations. ProxyOH comprises only eight variables that are generally observed by routine ground- or satellite-based instruments. ProxyOH scales linearly with in situ [OH] spatial variations along the ATom flight tracks (median r2 = 0.90, interquartile range = 0.80 to 0.94 across 2-km altitude by 20° latitudinal regions). We deconstruct spatial variations in ProxyOH as a first-order approximation of the sensitivity of OH variations to individual terms. Two terms modulate within-region ProxyOH variations-water vapor (H2O) and, to a lesser extent, nitric oxide (NO). This implies that a limited set of observations could offer an avenue for observation-based mapping of OH spatial variations over much of the remote marine troposphere. Both H2O and NO are expected to change with climate, while NO also varies strongly with human activities. We also illustrate the utility of ProxyOH as a process-based approach for evaluating intermodel differences in remote marine tropospheric OH.

Airborne Emission Rate Measurements Validate Remote Sensing Observations and Emission Inventories of Western U.S. Wildfires.

Carbonaceous emissions from wildfires are a dynamic mixture of gases and particles that have important impacts on air quality and climate. Emissions that feed atmospheric models are estimated using burned area and fire radiative power (FRP) methods that rely on satellite products. These approaches show wide variability and have large uncertainties, and their accuracy is challenging to evaluate due to limited aircraft and ground measurements. Here, we present a novel method to estimate fire plume-integrated total carbon and speciated emission rates using a unique combination of lidar remote sensing aerosol extinction profiles and in situ measured carbon constituents. We show strong agreement between these aircraft-derived emission rates of total carbon and a detailed burned area-based inventory that distributes carbon emissions in time using Geostationary Operational Environmental Satellite FRP observations (Fuel2Fire inventory, slope = 1.33 ± 0.04, r2 = 0.93, and RMSE = 0.27). Other more commonly used inventories strongly correlate with aircraft-derived emissions but have wide-ranging over- and under-predictions. A strong correlation is found between carbon monoxide emissions estimated in situ with those derived from the TROPOspheric Monitoring Instrument (TROPOMI) for five wildfires with coincident sampling windows (slope = 0.99 ± 0.18; bias = 28.5%). Smoke emission coefficients (g MJ-1) enable direct estimations of primary gas and aerosol emissions from satellite FRP observations, and we derive these values for many compounds emitted by temperate forest fuels, including several previously unreported species.

Ozone chemistry in western U.S. wildfire plumes.

Wildfires are a substantial but poorly quantified source of tropospheric ozone (O3). Here, to investigate the highly variable O3 chemistry in wildfire plumes, we exploit the in situ chemical characterization of western wildfires during the FIREX-AQ flight campaign and show that O3 production can be predicted as a function of experimentally constrained OH exposure, volatile organic compound (VOC) reactivity, and the fate of peroxy radicals. The O3 chemistry exhibits rapid transition in chemical regimes. Within a few daylight hours, the O3 formation substantially slows and is largely limited by the abundance of nitrogen oxides (NOx). This finding supports previous observations that O3 formation is enhanced when VOC-rich wildfire smoke mixes into NOx-rich urban plumes, thereby deteriorating urban air quality. Last, we relate O3 chemistry to the underlying fire characteristics, enabling a more accurate representation of wildfire chemistry in atmospheric models that are used to study air quality and predict climate.

Large contribution of biomass burning emissions to ozone throughout the global remote troposphere.

Ozone is the third most important anthropogenic greenhouse gas after carbon dioxide and methane but has a larger uncertainty in its radiative forcing, in part because of uncertainty in the source characteristics of ozone precursors, nitrogen oxides, and volatile organic carbon that directly affect ozone formation chemistry. Tropospheric ozone also negatively affects human and ecosystem health. Biomass burning (BB) and urban emissions are significant but uncertain sources of ozone precursors. Here, we report global-scale, in situ airborne measurements of ozone and precursor source tracers from the NASA Atmospheric Tomography mission. Measurements from the remote troposphere showed that tropospheric ozone is regularly enhanced above background in polluted air masses in all regions of the globe. Ozone enhancements in air with high BB and urban emission tracers (2.1 to 23.8 ppbv [parts per billion by volume]) were generally similar to those in BB-influenced air (2.2 to 21.0 ppbv) but larger than those in urban-influenced air (-7.7 to 6.9 ppbv). Ozone attributed to BB was 2 to 10 times higher than that from urban sources in the Southern Hemisphere and the tropical Atlantic and roughly equal to that from urban sources in the Northern Hemisphere and the tropical Pacific. Three independent global chemical transport models systematically underpredict the observed influence of BB on tropospheric ozone. Potential reasons include uncertainties in modeled BB injection heights and emission inventories, export efficiency of BB emissions to the free troposphere, and chemical mechanisms of ozone production in smoke. Accurately accounting for intermittent but large and widespread BB emissions is required to understand the global tropospheric ozone burden.

Novel Analysis to Quantify Plume Crosswind Heterogeneity Applied to Biomass Burning Smoke.

We present a novel method, the Gaussian observational model for edge to center heterogeneity (GOMECH), to quantify the horizontal chemical structure of plumes. GOMECH fits observations of short-lived emissions or products against a long-lived tracer (e.g., CO) to provide relative metrics for the plume width (wi/wCO) and center (bi/wCO). To validate GOMECH, we investigate OH and NO3 oxidation processes in smoke plumes sampled during FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality, a 2019 wildfire smoke study). An analysis of 430 crosswind transects demonstrates that nitrous acid (HONO), a primary source of OH, is narrower than CO (wHONO/wCO = 0.73-0.84 ± 0.01) and maleic anhydride (an OH oxidation product) is enhanced on plume edges (wmaleicanhydride/wCO = 1.06-1.12 ± 0.01). By contrast, NO3 production [P(NO3)] occurs mainly at the plume center (wP(NO3)/wCO = 0.91-1.00 ± 0.01). Phenolic emissions, highly reactive to OH and NO3, are narrower than CO (wphenol/wCO = 0.96 ± 0.03, wcatechol/wCO = 0.91 ± 0.01, and wmethylcatechol/wCO = 0.84 ± 0.01), suggesting that plume edge phenolic losses are the greatest. Yet, nitrophenolic aerosol, their oxidation product, is the greatest at the plume center (wnitrophenolicaerosol/wCO = 0.95 ± 0.02). In a large plume case study, GOMECH suggests that nitrocatechol aerosol is most associated with P(NO3). Last, we corroborate GOMECH with a large eddy simulation model which suggests most (55%) of nitrocatechol is produced through NO3 in our case study.

Rapid cloud removal of dimethyl sulfide oxidation products limits SO2 and cloud condensation nuclei production in the marine atmosphere.

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth's radiation balance and climate. The quantitative assessment of the impact of DMS emissions on CCN concentrations necessitates a detailed description of the oxidation of DMS in the presence of existing aerosol particles and clouds. In the unpolluted marine atmosphere, DMS is efficiently oxidized to hydroperoxymethyl thioformate (HPMTF), a stable intermediate in the chemical trajectory toward sulfur dioxide (SO2) and ultimately sulfate aerosol. Using direct airborne flux measurements, we demonstrate that the irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime (τHPMTF < 2 h) and terminates DMS oxidation to SO2 When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO2 production from DMS is reduced by 35% globally and near-surface (0 to 3 km) SO2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for the conversion of DMS to sulfate while limiting new particle formation in the marine atmosphere and changing the dynamics of aerosol growth. This loss process potentially reduces the spatial scale over which DMS emissions contribute to aerosol production and growth and weakens the link between DMS emission and marine CCN production with subsequent implications for cloud formation, radiative forcing, and climate.

Wildfire-Induced CO Plume Observations From NAST-I During the FIREX-AQ Field Campaign.

The fire influence on regional to global environments and air quality (FIREX-AQ) field campaign was conducted during August 2019 to investigate the impact of wildfire and biomass smoke on air quality and weather in the continental United States. One of the campaign's scientific objectives was to estimate the composition of emissions from wildfires. Ultraspectrally resolved infrared radiance measurements from aircraft and/or satellite observations contain information on tropospheric carbon monoxide (CO) as well as other trace species present in fire emissions. A methodology for retrieving tropospheric CO from such remotely sensed spectral data has been developed for the National Airborne Sounder Testbed-Interferometer (NAST-I) and is applied herein. Retrievals based on NAST-I measurements are used to demonstrate CO retrieval capability and characterize fire emissions. NAST-I remotely sensed CO from ER-2 flights are evaluated with concurrent in situ measurements from the differential absorption carbon monoxide measurements flown on the NASA DC-8 aircraft. Enhanced CO emissions along with plume evolution and transport from the fire ground site locations were captured by moderate vertical and high horizontal resolution observations obtained from the NAST-I IR spectrometer; these were intercompared and verified by the cloud physics lidar and the enhanced MODIS airborne simulator also hosted on the NASA ER-2 aircraft. This study will be beneficial to the science community for studying wildfire-related topics and understanding similar remotely sensed observations from satellites, along with helping to address the broader FIREX-AQ experiment objectives of investigating the impact of fires on air quality and climate.

Wintertime Nitrous Oxide Emissions in the San Joaquin Valley of California Estimated from Aircraft Observations.

Nitrous oxide (N2O) is a long-lived greenhouse gas that also destroys stratospheric ozone. N2O emissions are uncertain and characterized by high spatiotemporal variability, making individual observations difficult to upscale, especially in mixed land use source regions like the San Joaquin Valley (SJV) of California. Here, we calculate spatially integrated N2O emission rates using nocturnal and convective boundary-layer budgeting methods. We utilize vertical profile measurements from the NASA DISCOVER-AQ (Deriving Information on Surface Conditions from COlumn and VERtically Resolved Observations Relevant to Air Quality) campaign, which took place January-February, 2013. For empirical constraints on N2O source identity, we analyze N2O enhancement ratios with methane, ammonia, carbon dioxide, and carbon monoxide separately in the nocturnal boundary layer, nocturnal residual layer, and convective boundary layer. We find that an established inventory (EDGAR v4.3.2) underestimates N2O emissions by at least a factor of 2.5, that wintertime emissions from animal agriculture are important to annual totals, and that there is evidence for higher N2O emissions during the daytime than at night.

Sea spray aerosol concentration modulated by sea surface temperature.

Natural aerosols in pristine regions form the baseline used to evaluate the impact of anthropogenic aerosols on climate. Sea spray aerosol (SSA) is a major component of natural aerosols. Despite its importance, the abundance of SSA is poorly constrained. It is generally accepted that wind-driven wave breaking is the principle governing SSA production. This mechanism alone, however, is insufficient to explain the variability of SSA concentration at given wind speed. The role of other parameters, such as sea surface temperature (SST), remains controversial. Here, we show that higher SST promotes SSA mass generation at a wide range of wind speed levels over the remote Pacific and Atlantic Oceans, in addition to demonstrating the wind-driven SSA production mechanism. The results are from a global scale dataset of airborne SSA measurements at 150 to 200 m above the ocean surface during the NASA Atmospheric Tomography Mission. Statistical analysis suggests that accounting for SST greatly enhances the predictability of the observed SSA concentration compared to using wind speed alone. Our results support implementing SST into SSA source functions in global models to better understand the atmospheric burdens of SSA.

Observing Nitrogen Dioxide Air Pollution Inequality Using High-Spatial-Resolution Remote Sensing Measurements in Houston, Texas.

Houston, Texas is a major U.S. urban and industrial area where poor air quality is unevenly distributed and a disproportionate share is located in low-income, non-white, and Hispanic neighborhoods. We have traditionally lacked city-wide observations to fully describe these spatial heterogeneities in Houston and in cities globally, especially for reactive gases like nitrogen dioxide (NO2). Here, we analyze novel high-spatial-resolution (250 m × 500 m) NO2 vertical columns measured by the NASA GCAS airborne spectrometer as part of the September-2013 NASA DISCOVER-AQ mission and discuss differences in population-weighted NO2 at the census-tract level. Based on the average of 35 repeated flight circuits, we find 37 ± 6% higher NO2 for non-whites and Hispanics living in low-income tracts (LIN) compared to whites living in high-income tracts (HIW) and report NO2 disparities separately by race ethnicity (11-32%) and poverty status (15-28%). We observe substantial time-of-day and day-to-day variability in LIN-HIW NO2 differences (and in other metrics) driven by the greater prevalence of NOx (≡NO + NO2) emission sources in low-income, non-white, and Hispanic neighborhoods. We evaluate measurements from the recently launched satellite sensor TROPOMI (3.5 km × 7 km at nadir), averaged to 0.01° × 0.01° using physics-based oversampling, and demonstrate that TROPOMI resolves similar relative, but not absolute, tract-level differences compared to GCAS. We utilize the high-resolution FIVE and NEI NOx inventories, plus one year of TROPOMI weekday-weekend variability, to attribute tract-level NO2 disparities to industrial sources and heavy-duty diesel trucking. We show that GCAS and TROPOMI spatial patterns correspond to the surface patterns measured using aircraft profiling and surface monitors. We discuss opportunities for satellite remote sensing to inform decision making in cities generally.

Investigation of factors controlling PM2.5 variability across the South Korean Peninsula during KORUS-AQ.

The Korea - United States Air Quality Study (May - June 2016) deployed instrumented aircraft and ground-based measurements to elucidate causes of poor air quality related to high ozone and aerosol concentrations in South Korea. This work synthesizes data pertaining to aerosols (specifically, particulate matter with aerodynamic diameters <2.5 micrometers, PM2.5) and conditions leading to violations of South Korean air quality standards (24-hr mean PM2.5 < 35 µg m-3). PM2.5 variability from AirKorea monitors across South Korea is evaluated. Detailed data from the Seoul vicinity are used to interpret factors that contribute to elevated PM2.5. The interplay between meteorology and surface aerosols, contrasting synoptic-scale behavior vs. local influences, is presented. Transboundary transport from upwind sources, vertical mixing and containment of aerosols, and local production of secondary aerosols are discussed. Two meteorological periods are probed for drivers of elevated PM2.5. Clear, dry conditions, with limited transport (Stagnant period), promoted photochemical production of secondary organic aerosol from locally emitted precursors. Cloudy humid conditions fostered rapid heterogeneous secondary inorganic aerosol production from local and transported emissions (Transport/Haze period), likely driven by a positive feedback mechanism where water uptake by aerosols increased gas-to-particle partitioning that increased water uptake. Further, clouds reduced solar insolation, suppressing mixing, exacerbating PM2.5 accumulation in a shallow boundary layer. The combination of factors contributing to enhanced PM2.5 is challenging to model, complicating quantification of contributions to PM2.5 from local versus upwind precursors and production. We recommend co-locating additional continuous measurements at a few AirKorea sites across South Korea to help resolve this and other outstanding questions: carbon monoxide/carbon dioxide (transboundary transport tracer), boundary layer height (surface PM2.5 mixing depth), and aerosol composition with aerosol liquid water (meteorologically-dependent secondary production). These data would aid future research to refine emissions targets to further improve South Korean PM2.5 air quality.

Constraining remote oxidation capacity with ATom observations.

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July-August 2016 and January-February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NO y concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NO y . The severe model overestimate of NO y during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NO y partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHRmod by 3% to 9% and improves model-measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr-1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Correcting model biases of CO in East Asia: impact on oxidant distributions during KORUS-AQ.

Global coupled chemistry-climate models underestimate carbon monoxide (CO) in the Northern Hemisphere, exhibiting a pervasive negative bias against measurements peaking in late winter and early spring. While this bias has been commonly attributed to underestimation of direct anthropogenic and biomass burning emissions, chemical production and loss via OH reaction from emissions of anthropogenic and biogenic volatile organic compounds (VOCs) play an important role. Here we investigate the reasons for this underestimation using aircraft measurements taken in May and June 2016 from the Korea-United States Air Quality (KORUS-AQ) experiment in South Korea and the Air Chemistry Research in Asia (ARIAs) in the North China Plain (NCP). For reference, multispectral CO retrievals (V8J) from the Measurements of Pollution in the Troposphere (MOPITT) are jointly assimilated with meteorological observations using an ensemble adjustment Kalman filter (EAKF) within the global Community Atmosphere Model with Chemistry (CAM-Chem) and the Data Assimilation Research Testbed (DART). With regard to KORUS-AQ data, CO is underestimated by 42% in the control run and by 12% with the MOPITT assimilation run. The inversion suggests an underestimation of anthropogenic CO sources in many regions, by up to 80% for northern China, with large increments over the Liaoning Province and the North China Plain (NCP). Yet, an often-overlooked aspect of these inversions is that correcting the underestimation in anthropogenic CO emissions also improves the comparison with observational O3 datasets and observationally constrained box model simulations of OH and HO2. Running a CAM-Chem simulation with the updated emissions of anthropogenic CO reduces the bias by 29% for CO, 18% for ozone, 11% for HO2, and 27% for OH. Longer-lived anthropogenic VOCs whose model errors are correlated with CO are also improved, while short-lived VOCs, including formaldehyde, are difficult to constrain solely by assimilating satellite retrievals of CO. During an anticyclonic episode, better simulation of O3, with an average underestimation of 5.5 ppbv, and a reduction in the bias of surface formaldehyde and oxygenated VOCs can be achieved by separately increasing by a factor of 2 the modeled biogenic emissions for the plant functional types found in Korea. Results also suggest that controlling VOC and CO emissions, in addition to widespread NO x controls, can improve ozone pollution over East Asia.

Mapping hydroxyl variability throughout the global remote troposphere via synthesis of airborne and satellite formaldehyde observations.

The hydroxyl radical (OH) fuels tropospheric ozone production and governs the lifetime of methane and many other gases. Existing methods to quantify global OH are limited to annual and global-to-hemispheric averages. Finer resolution is essential for isolating model deficiencies and building process-level understanding. In situ observations from the Atmospheric Tomography (ATom) mission demonstrate that remote tropospheric OH is tightly coupled to the production and loss of formaldehyde (HCHO), a major hydrocarbon oxidation product. Synthesis of this relationship with satellite-based HCHO retrievals and model-derived HCHO loss frequencies yields a map of total-column OH abundance throughout the remote troposphere (up to 70% of tropospheric mass) over the first two ATom missions (August 2016 and February 2017). This dataset offers unique insights on near-global oxidizing capacity. OH exhibits significant seasonality within individual hemispheres, but the domain mean concentration is nearly identical for both seasons (1.03 ± 0.25 × 106 cm-3), and the biseasonal average North/South Hemisphere ratio is 0.89 ± 0.06, consistent with a balance of OH sources and sinks across the remote troposphere. Regional phenomena are also highlighted, such as a 10-fold OH depression in the Tropical West Pacific and enhancements in the East Pacific and South Atlantic. This method is complementary to budget-based global OH constraints and can help elucidate the spatial and temporal variability of OH production and methane loss.

Modeling regional pollution transport events during KORUS-AQ: Progress and challenges in improving representation of land-atmosphere feedbacks.

This study evaluates the impact of assimilating soil moisture data from NASA's Soil Moisture Active Passive (SMAP) on short-term regional weather and air quality modeling in East Asia during the Korea-US Air Quality Study (KORUS-AQ) airborne campaign. SMAP data are assimilated into the Noah land surface model using an ensemble Kalman filter approach in the Land Information System framework, which is semi-coupled with the NASA-Unified Weather Research and Forecasting model with online chemistry (NUWRF-Chem). With SMAP assimilation included, water vapor and carbon monoxide (CO) transport from northern-central China transitional climate zones to South Korea is better represented in NUWRF-Chem during two studied pollution events. Influenced by different synoptic conditions and emission patterns, impact of SMAP assimilation on modeled CO in South Korea is intense (>30 ppbv) during one event and less significant (<8 ppbv) during the other. SMAP assimilation impact on air quality modeling skill is complicated by other error sources such as the chemical initial and boundary conditions (IC/LBC) and emission inputs of NUWRF-Chem. Using a satellite-observation-constrained chemical IC/LBC instead of a free-running, coarser-resolution chemical IC/LBC reduces modeled CO by up to 80 ppbv over South Korea. Consequently, CO performance is improved in the middle-upper troposphere whereas degraded in the lower troposphere. Remaining negative CO biases result largely from the emissions inputs. The advancements in land surface modeling and chemical IC/LBC presented here are expected to benefit future investigations on constraining emissions using observations, which can in turn enable more accurate assessments of SMAP assimilation and chemical IC/LBC impacts.

Characterizing CO and NO y Sources and Relative Ambient Ratios in the Baltimore Area Using Ambient Measurements and Source Attribution Modeling.

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 NO y relationships to constrain emission inventories. We derive ambient and modeled ΔCO:ΔNO y ratios that have previously been interpreted to represent CO:NO y ratios in emissions from local sources. Modeled and measured ΔCO:ΔNO y are similar; however, measured ΔCO:ΔNO y 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 NO y in the area. The sector mix is important because emitted CO:NO x 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:ΔNO y to emitted CO:NO y is challenged by ambient and modeled evidence that free tropospheric entrainment, and atmospheric processing elevates ambient ΔCO:ΔNO y above emitted ratios. Specifically, modeled ΔCO:ΔNO y 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:ΔNO y suggesting that secondary CO formation plays a role in these elevated ratios. This analysis suggests that ambient urban daytime ΔCO:ΔNO y values are not reflective of emitted ratios from individual sources.

Physical Processes Controlling the Vertical and Longitudinal Distributions of Relative Humidity in the Tropical Tropopause Layer Over the Pacific.

The vertical distribution of relative humidity with respect to ice (RHI) in the Boreal wintertime Tropical Tropopause Layer (TTL, ≃14-18 km) over the Pacific is examined with the extensive dataset of measurements from the NASA Airborne Tropical TRopopause EXperiment (ATTREX). Multiple deployments of the Global Hawk during ATTREX provided hundreds of vertical profiles spanning the longitudinal extent of the Pacific with accurate measurements of temperature, pressure, water vapor concentration, ozone concentration, and cloud properties. We also compare the measured RHI distributions with results from a transport and microphysical model driven by meteorological analysis fields. Notable features in the distribution of RHI versus temperature and longitude include (1) the common occurrence of RHI values near ice saturation over the western Pacific in the lower-middle TTL (temperatures greater than 195 K); (2) low RHI values in the lower TTL over the central and eastern Pacific; (3) common occurrence of RHI values following a constant mixing ratio in the middle-to-upper TTL (temperatures between about 190 and 200 K), particularly for samples with ozone greater than about 50-100 ppbv indicating mixtures of tropospheric and stratospheric air; (4) RHI values typically near ice saturation in the coldest airmasses sampled (temperatures less than about 190 K); and (5) common occurrence of RHI values near 100% across the TTL temperature range in air parcels with low ozone mixing ratio (O3 < 50 ppbv) indicative of recent uplift by deep convection. We suggest that the typically saturated air in the lower TTL over the western Pacific is likely driven by a combination of the frequent occurrence of deep convection and the predominance of radiative heating (rising motion) in this region. The low relative humidities in the central/eastern Pacific lower TTL result from the lack of convective influence, the predominance of subsidence, and the relatively warm temperatures in the region. The nearly-constant water vapor mixing ratios in the middle-to-upper TTL likely result from the combination of slow ascent (resulting in long residence times) and wave driven temperature variability on a range of time scales (resulting in most air parcels having experienced low temperature and dehydration). The numerical simulations generally reproduce the observed RHI distribution features and sensitivity tests further emphasize the strong sensitivities of TTL relative humidity to convective input and vertical motions.