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This study evaluates the impact of satellite soil moisture (SM) data assimilation (DA) on regional weather and ozone (O3) modeling over the southeastern US during the summer. Satellite SM data are assimilated into the Noah land surface model using an ensemble Kalman filter approach within National Aeronautics and Space Administration's Land Information System framework, which is semicoupled with the Weather Research and Forecasting model with online Chemistry (WRF-Chem; standard version 3.9.1.1). The DA impacts on the model performance of SM, weather states, and energy fluxes show strong spatiotemporal variability. Dense vegetation and water use from human activities unaccounted for in the modeling system are among the factors impacting the effectiveness of the DA. The daytime surface O3 responses to the DA can largely be explained by the temperature-driven changes in biogenic emissions of volatile organic compounds and soil nitric oxide, chemical reaction rates, and dry deposition velocities. On a near-biweekly timescale, the DA modified the mean daytime and daily maximum 8 h average surface O3 by up to 2–3 ppbv, with the maximum impacts occurring in areas where daytime surface air temperature most strongly (i.e., by ∼2 K) responded to the DA. The DA impacted WRF-Chem upper tropospheric O3 (e.g., for its daytime-mean, by up to 1–1.5 ppbv) partially via altering the transport of O3 and its precursors from other places as well as in situ chemical production of O3 from lightning and other emissions. Case studies during airborne field campaigns suggest that the DA improved the model treatment of convective transport and/or lightning production. In the cases that the DA improved the modeled SM, weather fields, and some O3-related processes, its influences on the model's O3 performance at various altitudes are not always as desirable. This is in part due to the uncertainty in the model's key chemical inputs, such as anthropogenic emissions, and the model representation of stratosphere–troposphere exchanges. This can also be attributable to shortcomings in model parameterizations (e.g., chemical mechanism, natural emission, photolysis and deposition schemes), including those related to representing water availability impacts. This study also shows that the WRF-Chem upper tropospheric O3 response to the DA has comparable magnitudes with its response to the estimated US anthropogenic emission changes within 2 years. As reductions in anthropogenic emissions in North America would benefit the mitigation of O3 pollution in its downwind regions, this analysis highlights the important role of SM in quantifying air pollutants' source–receptor relationships between the US and its downwind areas. It also emphasizes that using up-to-date anthropogenic emissions is necessary for accurately assessing the DA impacts on the model performance of O3 and other pollutants over a broad region. This work will be followed by a Noah-Multiparameterization (with dynamic vegetation)-based study over the southeastern US, in which selected processes including photosynthesis and O3 dry deposition will be the foci.

The Korea-United States Air Quality (KORUS-AQ) field study was conducted during May–June 2016 to understand the factors controlling air quality in South Korea. Extensive aircraft and ground network observations from the campaign offer an opportunity to address issues in current air quality models and reduce model-observation disagreements. This study examines these issues using model evaluation against the KORUS-AQ observations and intercomparisons between models. Six regional and two global chemistry transport models using identical anthropogenic emissions participated in the model intercomparison study and were used to conduct air quality simulations focusing on ozone (O3), aerosols, and their precursors for the campaign. Using the KORUSv5 emissions inventory, which has been updated from KORUSv1, the models successfully reproduced observed nitrogen oxides (NOx) and volatile organic compounds mixing ratios in surface air, especially in the Seoul Metropolitan Area, but showed systematic low biases for carbon monoxide (CO), implying possible missing CO sources in the inventory in East Asia. Although the DC-8 aircraft-observed O3 precursor mixing ratios were well captured by the models, simulated O3 levels were lower than the observations in the free troposphere in part due to too low stratospheric O3 influxes, especially in regional models. During the campaign, the synoptic meteorology played an important role in determining the observed variability of PM2.5 (PM diameter ≤ 2.5 μm) concentrations in South Korea. The models successfully simulated the observed PM2.5 variability with significant inorganic sulfate-nitrate-ammonium aerosols contribution, but failed to reproduce that of organic aerosols, causing a large inter-model variability. From the model evaluation, we find that an ensemble of model results, incorporating individual models with differing strengths and weaknesses, performs better than most individual models at representing observed atmospheric compositions for the campaign. Ongoing model development and evaluation, in close collaboration with emissions inventory development, are needed to improve air quality forecasting.

The U.S. National Aeronautics and Space Administration in partnership with Korea’s National Institute of Environmental Research embarked on the Korea-United States Air Quality (KORUS-AQ) study to address air quality issues over the Korean peninsula. Underestimation of volatile organic compound (VOC) emissions from various large facilities on South Korea’s northwest coast may contribute to this problem, and this study focuses on quantifying top-down emissions of formaldehyde (CH2O) and VOCs from the largest of these facilities, the Daesan petrochemical complex, and comparisons with the latest emission inventories. To accomplish this and additional goals discussed herein, this study employed a number of measurements acquired during KORUS-AQ onboard the NASA DC-8 aircraft during three Daesan overflights on June 2, 3, and 5, 2016, in conjunction with a mass balance approach. The measurements included fast airborne measurements of CH2O and ethane from an infrared spectrometer, additional fast measurements from other instruments, and a suite of 33 VOC measurements acquired by the whole air sampler. The mass balance approach resulted in consistent top-down yearly Daesan VOC emission flux estimates, which averaged (61 ± 14) × 103 MT/year for the 33 VOC compounds, a factor of 2.9 ± 0.6 (±1.0) higher than the bottom-up inventory value. The top-down Daesan emission estimate for CH2O and its four primary precursors averaged a factor of 4.3 ± 1.5 (± 1.9) times higher than the bottom-up inventory value. The uncertainty values in parentheses reflect upper limits for total uncertainty estimates. The resulting averaged top-down Daesan emission estimate for sulfur dioxide (SO2) yielded a ratio of 0.81–1.0 times the bottom-up SO2 inventory, and this provides an important cross-check on the accuracy of our mass balance analysis.

The Korea-United States Air Quality Study (KORUS-AQ) took place in spring 2016 to better understand air pollution in Korea. In support of KORUS-AQ, 2554 whole air samples (WAS) were collected aboard the NASA DC-8 research aircraft and analyzed for 82 C1–C10 volatile organic compounds (VOCs) using multi-column gas chromatography. Together with fast-response measurements from other groups, the air samples were used to characterize the VOC composition in Seoul and surrounding regions, determine which VOCs are major ozone precursors in Seoul, and identify the sources of these reactive VOCs. (1) The WAS VOCs showed distinct signatures depending on their source origins. Air collected over Seoul had abundant ethane, propane, toluene and n-butane while plumes from the Daesan petrochemical complex were rich in ethene, C2–C6 alkanes and benzene. Carbonyl sulfide (COS), CFC-113, CFC-114, carbon tetrachloride (CCl4) and 1,2-dichloroethane were good tracers of air originating from China. CFC-11 was also elevated in air from China but was surprisingly more elevated in air over Seoul. (2) Methanol, isoprene, toluene, xylenes and ethene were strong individual contributors to OH reactivity in Seoul. However methanol contributed less to ozone formation based on photochemical box modeling, which better accounts for radical chemistry. (3) Positive Matrix Factorization (PMF) and other techniques indicated a mix of VOC source influences in Seoul, including solvents, traffic, biogenic, and long-range transport. The solvent and traffic sources were roughly equal using PMF, and the solvents source was stronger in the KORUS-AQ emission inventory. Based on PMF, ethene and propene were primarily associated with traffic, and toluene, ethylbenzene and xylenes with solvents, especially non-paint solvents for toluene and paint solvents for ethylbenzene and xylenes. This suggests that VOC control strategies in Seoul could continue to target vehicle exhaust and paint solvents, with additional regulations to limit the VOC content in a variety of non-paint solvents.

Using a new approach that constrains thermodynamic modeling of aerosol composition with measured gas-to-particle partitioning of inorganic nitrate, we estimate the acidity levels for aerosol sampled in the South Korean planetary boundary layer during the NASA/NIER KORUS-AQ field campaign. The pH (mean ± 1σ = 2.43 ± 0.68) and aerosol liquid water content determined were then used to determine the chemical regime of the inorganic fraction of particulate matter (PM) sensitivity to ammonia and nitrate availability. We found that the aerosol formation is always sensitive to HNO3 levels, especially in highly polluted regions, while it is only exclusively sensitive to NH3 in some rural/remote regions. Nitrate levels are further promoted because dry deposition velocity is low and allows its accumulation in the boundary layer. Because of this, HNO3 reductions achieved by NOx controls prove to be the most effective approach for all conditions examined, and that NH3 emissions can only partially affect PM reduction for the specific season and region. Despite the benefits of controlling PM formation to reduce ammonium-nitrate aerosol and PM mass, changes in the acidity domain can significantly affect other processes and sources of aerosol toxicity (such as e.g., solubilization of Fe, Cu and other metals) as well as the deposition patterns of these trace species and reactive nitrate.

The Seoul Metropolitan Area (SMA) has a population of 24 million and frequently experiences unhealthy levels of ozone (O3). In this work, measurements taken during the Korea-United States Air Quality Study (KORUS-AQ, 2016) are used to explore regional gradients in O3 and its chemical precursors, and an observationally-constrained 0-D photochemical box model is used to quantify key aspects of O3 production including its sensitivity to precursor gases. Box model performance was evaluated by comparing modeled concentrations of select secondary species to airborne measurements. These comparisons indicate that the steady state assumption used in 0-D box models cannot describe select intermediate species, highlighting the importance of having a broad suite of trace gases as model constraints. When fully constrained, aggregated statistics of modeled O3 production rates agreed with observed changes in O3, indicating that the box model was able to represent the majority of O3 chemistry. Comparison of airborne observations between urban Seoul and a downwind receptor site reveal a positive gradient in O3 coinciding with a negative gradient in NOx, no gradient in CH2O, and a slight positive gradient in modeled rates of O3 production. Together, these observations indicate a radical-limited (VOC-limited) O3 production environment in the SMA. Zero-out simulations identified C7+ aromatics as the dominant VOC contributors to O3 production, with isoprene and anthropogenic alkenes making smaller but appreciable contributions. Simulations of model sensitivity to decreases in NOx produced results that were not spatially uniform, with large increases in O3 production predicted for urban Seoul and decreases in O3 production predicted for far-outlying areas. The policy implications of this work are clear: Effective O3 mitigation strategies in the SMA must focus on reducing local emissions of C7+ aromatics, while reductions in NOx emissions may increase O3 in some areas but generally decrease the regional extent of O3 exposure.

South Korea routinely experiences poor air quality with ozone and small particles exceeding air quality standards. To build a better understanding of this problem, in 2016, the KORea-United States cooperative Air Quality (KORUS-AQ) study collected surface and airborne measurements of many chemical species, including the reactive gases hydroxyl (OH) and hydroperpoxyl (HO2). Several different results are reported here. First, OH and HO2 measured on the NASA DC-8 agree to within uncertainties with values calculated by two different box models, both in statistical comparisons and as a function of altitude from the surface to 8 km. These comparisons show substantial scatter, likely due to both variability in instrument performance and the difficulty in interpolating measurements made with frequencies different from those of the model time step. Second, OH and HO2 calculated by a model including HO2 uptake on aerosol particles in the chemical mechanism are inconsistent with observations. Third, in the planetary boundary layer over both ocean and land, measured and model-calculated OH reactivity are sometimes different, and this missing OH reactivity, which is as much as ∼4 s−1, increased from April to June and originated primarily from the Korean peninsula. Fourth, repeated missed approaches at the Seoul Air Base during several days show that the changes in the sum of ozone and nitrogen dioxide are consistent with ozone production rates calculated from HO2 either observed or modeled by the Langley Research Center model.

Land and atmospheric initial conditions of the Weather Research and Forecasting (WRF) model are often interpolated from a different model output. We perform case studies during NASA's SEAC4RS and DISCOVER-AQ Houston airborne campaigns, demonstrating that using land initial conditions directly downscaled from a coarser resolution dataset led to significant positive biases in the coupled NASA-Unified WRF (NUWRF, version 7) surface and near-surface air temperature and planetary boundary layer height (PBLH) around the Missouri Ozarks and Houston, Texas, as well as poorly partitioned latent and sensible heat fluxes. Replacing land initial conditions with the output from a long-term offline Land Information System (LIS) simulation can effectively reduce the positive biases in NUWRF surface air temperature by ∼ 2 °C. We also show that the LIS land initialization can modify surface air temperature errors almost 10 times as effectively as applying a different atmospheric initialization method. The LIS-NUWRF-based isoprene emission calculations by the Model of Emissions of Gases and Aerosols from Nature (MEGAN, version 2.1) are at least 20 % lower than those computed using the coarser resolution data-initialized NUWRF run, and are closer to aircraft-observation-derived emissions. Higher resolution MEGAN calculations are prone to amplified discrepancies with aircraft-observation-derived emissions on small scales. This is possibly a result of some limitations of MEGAN's parameterization and uncertainty in its inputs on small scales, as well as the representation error and the neglect of horizontal transport in deriving emissions from aircraft data. This study emphasizes the importance of proper land initialization to the coupled atmospheric weather modeling and the follow-on emission modeling. We anticipate it to also be critical to accurately representing other processes included in air quality modeling and chemical data assimilation. Having more confidence in the weather inputs is also beneficial for determining and quantifying the other sources of uncertainties (e.g., parameterization, other input data) of the models that they drive.

Satellite-based measurements of the column CH2O/NO2 ratio have previously been used to estimate near-surface ozone (O3) sensitivity (i.e., NOx 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-NOx interactions (referred to as LROx/LNOx) provides a good indicator of maximum O3 production along NOx 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.

Strong correlation between O3 and CO was 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 observed correlation does not vary significantly with time or altitude in the boundary layer. The observations are simulated well by a regional chemical transport model. We analyze the model results to understand the factors contributing to the observed O3-CO regression slope, which has been used in past studies to estimate the anthropogenic O3 production amount. We trace separately four different CO sources: primary anthropogenic emissions, oxidation of anthropogenic volatile organic compounds, oxidation of biogenic isoprene, and transport from the lateral and upper model boundaries. Modeling analysis suggests that the contribution from biogenic isoprene oxidation to the observed O3-CO regression slope is as large as that from primary anthropogenic CO emissions. As a result of decrease of anthropogenic primary CO emissions during the past decades, biogenic CO from oxidation of isoprene is increasingly important. Consequently, observed and simulated O3-CO regression slopes can no longer be used directly with an anthropogenic CO emission inventory to quantify anthropogenic O3 production over the United States. The consistent enhancement of O3 relative to CO observed in the boundary layer, as indicated by the O3-CO regression slope, provides a useful constraint on model photochemistry and emissions.

We examine O3 production and its sensitivity to precursor gases and boundary layer mixing in Korea by using a 3-D global chemistry transport model and extensive observations during the KORea-US cooperative Air Quality field study in Korea, which occurred in May–June 2016. During the campaign, observed aromatic species onboard the NASA DC-8 aircraft, especially toluene, showed high mixing ratios of up to 10 ppbv, emphasizing the importance of aromatic chemistry in O3 production. To examine the role of VOCs and NOx in O3 chemistry, we first implement a detailed aromatic chemistry scheme in the model, which reduces the normalized mean bias of simulated O3 mixing ratios from –26% to –13%. Aromatic chemistry also increases the average net O3 production in Korea by 37%. Corrections of daytime PBL heights, which are overestimated in the model compared to lidar observations, increase the net O3 production rate by ~10%. In addition, increasing NOx emissions by 50% in the model shows best performance in reproducing O3 production characteristics, which implies that NOx emissions are underestimated in the current emissions inventory. Sensitivity tests show that a 30% decrease in anthropogenic NOx emissions in Korea increases the O3 production efficiency throughout the country, making rural regions ~2 times more efficient in producing O3 per NOx consumed. Simulated O3 levels overall decrease in the peninsula except for urban and other industrial areas, with the largest increase (~6 ppbv) in the Seoul Metropolitan Area (SMA). However, with simultaneous reductions in both NOx and VOCs emissions by 30%, O3 decreases in most of the country, including the SMA. This implies the importance of concurrent emission reductions for both NOx and VOCs in order to effectively reduce O3 levels in Korea.

The San Joaquin Valley (SJV) of California experiences high concentrations of particulate matter NH(4)NO(3) during episodes of meteorological stagnation in winter. A rich data set of observations related to NH(4)NO(3) formation was acquired during multiple periods of elevated NH(4)NO(3) 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 NH(4)NO(3) 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 HNO(3) production rates. Simulated NO(3)(−) generally agrees well with routine monitoring of 24-hr average NO(3)(−), but comparisons with hourly average NO(3)(−) measurements in Fresno revealed differences at higher time resolution. Predictions of gas-particle partitioning of total nitrate (HNO(3) + NO(3)(−)) and NHx (NH(3) + NH(4)(+)) generally agree well with measurements in Fresno, although partitioning of total nitrate to HNO(3) is sometimes overestimated at low relative humidity in afternoon. Gas-particle partitioning results indicate that NH(4)NO(3) formation is limited by HNO(3) availability in both the model and ambient. NH(3) mixing ratios are underestimated, particularly in areas with large agricultural activity, and additional work on the spatial allocation of NH(3) emissions is warranted. During a period of elevated NH(4)NO(3), the model predicted that the OH + NO(2) pathway contributed 46% to total HNO(3)production in SJV and the N(2)O(5) heterogeneous hydrolysis pathway contributed 54%. The relative importance of the OH + NO(2) pathway for HNO(3) production is predicted to increase as NOx emissions decrease.

We describe and show results from a series of field campaigns that used balloonborne instruments launched from India and Saudi Arabia during the summers 2014–17 to study the nature, formation, and impacts of the Asian Tropopause Aerosol Layer (ATAL). The campaign goals were to i) characterize the optical, physical, and chemical properties of the ATAL; ii) assess its impacts on water vapor and ozone; and iii) understand the role of convection in its formation. To address these objectives, we launched 68 balloons from four locations, one in Saudi Arabia and three in India, with payload weights ranging from 1.5 to 50 kg. We measured meteorological parameters; ozone; water vapor; and aerosol backscatter, concentration, volatility, and composition in the upper troposphere and lower stratosphere (UTLS) region. We found peaks in aerosol concentrations of up to 25 cm–3 for radii > 94 nm, associated with a scattering ratio at 940 nm of ∼1.9 near the cold-point tropopause. During medium-duration balloon flights near the tropopause, we collected aerosols and found, after offline ion chromatography analysis, the dominant presence of nitrate ions with a concentration of about 100 ng m–3. Deep convection was found to influence aerosol loadings 1 km above the cold-point tropopause. The Balloon Measurements of the Asian Tropopause Aerosol Layer (BATAL) project will continue for the next 3–4 years, and the results gathered will be used to formulate a future National Aeronautics and Space Administration–Indian Space Research Organisation (NASA–ISRO) airborne campaign with NASA high-altitude aircraft.

Ozone (O3) concentrations in the lower troposphere (LT) over Beijing have significantly increased over the past 2 decades as a result of rapid industrialization in China, with important implications for regional air quality and the photochemistry of the background troposphere. We characterize the vertical distribution of lower-tropospheric (0–6 km) O3 over Beijing using observations from 16 ozonesonde soundings during a field campaign in April–May 2005 and MOZAIC (Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft) over 13 days in the same period. We focus on the origin of LT O3 enhancements observed over Beijing, particularly in May. We use a global 3-D chemistry and transport model (GEOS-Chem CTM; GEOS – Goddard Earth Observing System) driven by assimilated meteorological fields to examine the transport pathways for O3 pollution and to quantify the sources contributing to O3 and its enhancements in the springtime LT over Beijing. Output from the Global Modeling Initiative (GMI) CTM is also used. High O3 concentrations (up to 94.7 ppbv) were frequently observed at the altitude of ~ 1.5–2 km. The CTMs captured the timing of the occurrences but significantly underestimated their magnitude. GEOS-Chem simulations and a case study showed that O3 produced in the Asian troposphere (especially from Asian anthropogenic pollution) made major contributions to the observed O3 enhancements. Contributions from anthropogenic pollution in the European and North American troposphere were reduced during these events, in contrast with days without O3 enhancements when contributions from Europe and North America were substantial. The O3 enhancements typically occurred under southerly wind and warmer conditions. It is suggested that an earlier onset of the Asian summer monsoon would cause more O3 enhancement events in the LT over the North China Plain in late spring and early summer.

A significant source of ozone in the troposphere is transport from the stratosphere. The stratospheric contribution has been estimated mainly using global models that attribute the transport process largely to the global scale Brewer-Dobson circulation and synoptic scale dynamics associated with upper tropospheric jet streams. We report observations from research aircraft that reveal additional transport of ozone-rich stratospheric air downward into the upper troposphere by a leading-line-trailing-stratiform (LLTS) mesoscale convective system (MCS) with convection overshooting the tropopause altitude. The fine-scale transport demonstrated by these observations poses a significant challenge to global models that currently do not resolve storm scale dynamics. Thus the upper tropospheric ozone budget simulated by global chemistry-climate models where large-scale dynamics and photochemical production from lightning-produced NO are the controlling factors may require modification.

Herein, we report on the development of a compact proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) for airborne measurements of volatile organic compounds (VOCs). The new instrument resolves isobaric ions with a mass resolving power (m/Δm) of ~1000, provides accurate m/z measurements (Δm < 3 mDa), records full mass spectra at 1 Hz and thus overcomes some of the major analytical deficiencies of quadrupole-MS-based airborne instruments. 1 Hz detection limits for biogenic VOCs (isoprene, α total monoterpenes), aromatic VOCs (benzene, toluene, xylenes) and ketones (acetone, methyl ethyl ketone) range from 0.05 to 0.12 ppbV, making the instrument well-suited for fast measurements of abundant VOCs in the continental boundary layer. The instrument detects and quantifies VOCs in locally confined plumes (< 1 km), which improves our capability of characterizing emission sources and atmospheric processing within plumes. A deployment during the NASA 2013 DISCOVER-AQ mission generated high vertical- and horizontal-resolution in situ data of VOCs and ammonia for the validation of satellite retrievals and chemistry transport models.

During a classic heat wave with record high temperatures and poor air quality from July 18 to 23, 2011, an elevated reservoir of air pollutants was observed over and downwind of Baltimore, MD, with relatively clean conditions near the surface. Aircraft and ozonesonde measurements detected approximately 120 parts per billion by volume ozone at 800 meters altitude, but approximately 80 parts per billion by volume ozone near the surface. High concentrations of other pollutants were also observed around the ozone peak: approximately 300 parts per billion by volume CO at 1200 meters, approximately 2 parts per billion by volume NO2 at 800 meters, approximately 5 parts per billion by volume SO2 at 600 meters, and strong aerosol optical scattering (2 x 10 (sup 4) per meter) at 600 meters. These results suggest that the elevated reservoir is a mixture of automobile exhaust (high concentrations of O3, CO, and NO2) and power plant emissions (high SO2 and aerosols). Back trajectory calculations show a local stagnation event before the formation of this elevated reservoir. Forward trajectories suggest an influence on downwind air quality, supported by surface ozone observations on the next day over the downwind PA, NJ and NY area. Meteorological observations from aircraft and ozonesondes show a dramatic veering of wind direction from south to north within the lowest 5000 meters, implying that the development of the elevated reservoir was caused in part by the Chesapeake Bay breeze. Based on in situ observations, Community Air Quality Multi-scale Model (CMAQ) forecast simulations with 12 kilometers resolution overestimated surface ozone concentrations and failed to predict this elevated reservoir; however, CMAQ research simulations with 4 kilometers and 1.33 kilometers resolution more successfully reproduced this event. These results show that high resolution is essential for resolving coastal effects and predicting air quality for cities near major bodies of water such as Baltimore on the Chesapeake Bay and downwind areas in the Northeast.

Total-column nitrogen dioxide (NO2) data collected by a ground-based sun-tracking spectrometer system (Pandora) and an photolytic-converter-based in-situ instrument collocated at NASA’s Langley Research Center in Hampton, Virginia were analyzed to study the relationship between total-column and surface NO2 measurements. The measurements span more than a year and cover all seasons. Surface mixing ratios are estimated via application of a planetary boundary-layer (PBL) height correction factor. This PBL correction factor effectively corrects for boundary-layer variability throughout the day, and accounts for up to ≈75 % of the variability between the NO2 data sets. Previous studies have made monthly and seasonal comparisons of column/surface data, which has shown generally good agreement over these long average times. In the current analysis comparisons of column densities averaged over 90 s and 1 h are made. Applicability of this technique to sulfur dioxide (SO2) is briefly explored. The SO2 correlation is improved by excluding conditions where surface levels are considered background. The analysis is extended to data from the July 2011 DISCOVER-AQ mission over the greater Baltimore, MD area to examine the method’s performance in more-polluted urban conditions where NO2 concentrations are typically much higher.

Global atmospheric concentrations of methane (CH4), a powerful greenhouse gas, are increasing, but because there are many natural and anthropogenic sources of CH4, it is difficult to assess which sources may be increasing in magnitude. Here we present a dataset of δ2H-CH4 measurements of individual sources and air in the Colorado Front Range, USA. We show that δ2H-CH4, but not δ13C, signatures are consistent in air sampled downwind of landfills, cattle feedlots, and oil and gas wells in the region. Applying these source signatures to air in ground and aircraft samples indicates that at least 50% of CH4 emitted in the region is biogenic, perhaps because regulatory restrictions on leaking oil and natural gas wells are helping to reduce this source of CH4. Source apportionment tracers such as δ2H may help close the gap between CH4 observations and inventories, which may underestimate biogenic as well as thermogenic sources.

The hydroxyl (OH) and hydroperoxyl (HO2) radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF) spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS) for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS) for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by ultraviolet (UV) light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2σ) for the LIF instrument, ±65% (2σ) for the SI-CIMS instrument, and ±50% (2σ) for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 104 cm−3 with a correlation coefficient r2 = 0.72 for OH, and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol−1) with a correlation coefficient r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some similarities for both the CIMS and LIF measurements. First, the observed-to-modeled HO2 ratio increases greatly for higher NO mixing ratios, indicating that the model may not properly account for HOx sources that correlate with NO. Second, the observed-to-modeled OH ratio increases with increasing isoprene mixing ratios, suggesting either incomplete understanding of isoprene chemistry in the model or interferences in the measurements in environments where biogenic emissions dominate ambient volatile organic compounds.

Observations of chemical constituents and meteorological quantities obtained during the two Arctic phases of the airborne campaign ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) are analyzed using an observationally constrained steady state box model. Measurements of OH and HO2 from the Penn State ATHOS instrument are compared to model predictions. Forty percent of OH measurements below 2 km are at the limit of detection during the spring phase (ARCTAS-A). While the median observed-to-calculated ratio is near one, both the scatter of observations and the model uncertainty for OH are at the magnitude of ambient values. During the summer phase (ARCTAS-B), model predictions of OH are biased low relative to observations and demonstrate a high sensitivity to the level of uncertainty in NO observations. Predictions of HO2 using observed CH2O and H2O2 as model constraints are up to a factor of two larger than observed. A temperature-dependent terminal loss rate of HO2 to aerosol recently proposed in the literature is shown to be insufficient to reconcile these differences. A comparison of ARCTAS-A to the high latitude springtime portion of the 2000 TOPSE campaign (Tropospheric Ozone Production about the Spring Equinox) shows similar meteorological and chemical environments with the exception of peroxides; observations of H2O2 during ARCTAS-A were 2.5 to 3 times larger than those during TOPSE. The cause of this difference in peroxides remains unresolved and has important implications for the Arctic HOx budget. Unconstrained model predictions for both phases indicate photochemistry alone is unable to simultaneously sustain observed levels of CH2O and H2O2; however when the model is constrained with observed CH2O, H2O2 predictions from a range of rainout parameterizations bracket its observations. A mechanism suitable to explain observed concentrations of CH2O is uncertain. Free tropospheric observations of acetaldehyde (CH3CHO) are 2–3 times larger than its predictions, though constraint of the model to those observations is sufficient to account for less than half of the deficit in predicted CH2O. The box model calculates gross O3 formation during spring to maximize from 1–4 km at 0.8 ppbv d−1, in agreement with estimates from TOPSE, and a gross production of 2–4 ppbv d−1 in the boundary layer and upper troposphere during summer. Use of the lower observed levels of HO2 in place of model predictions decreases the gross production by 25–50%. Net O3 production is near zero throughout the ARCTAS-A troposphere, and is 1–2 ppbv in the boundary layer and upper altitudes during ARCTAS-B.

A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time high latitude troposphere based on aircraft and satellite measurements of bromine oxide (BrO) and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometer (CIMS) to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br−) was 0.9±0.1, 1.06+0.30/−0.35, 0.4±0.1, and 0.95±0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the space-borne observation of BrO. The good agreement (R2 = 0.76; slope = 0.95; intercept = −3.4 pmol mol−1) between modeled and observed soluble bromide, when BrO was above detection limit (>2 pmol mol−1) under unpolluted conditions (NO−1), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide and that a well characterized MC can be used to derive mixing ratios of some reactive bromine compounds. Tropospheric BrO vertical column densities (BrOVCD) derived from CIMS BrO observations compare well with BrOTROPVCD from OMI on 17 April 2008.

Observations of a comprehensive suite of inorganic and organic trace gases, including non-methane hydrocarbons (NMHCs), halogenated organics and oxygenated volatile organic compounds (OVOCs), obtained from the NASA DC-8 over Canada during the ARCTAS aircraft campaign in July 2008 illustrate that convection is important for redistributing both long- and short-lived species throughout the troposphere. Convective outflow events were identified by the elevated mixing ratios of organic species in the upper troposphere relative to background conditions. Several dramatic events were observed in which isoprene and its oxidation products were detected at hundreds of pptv at altitudes higher than 8 km. Two events are studied in detail using detailed experimental data and the NASA Langley Research Center (LaRC) box model. One event had no lightning NOx (NO + NO2) associated with it and the other had substantial lightning NOx (LNOx > 1 ppbv). When convective storms transport isoprene from the boundary layer to the upper troposphere and no LNOx is present, OH is reduced due to scavenging by isoprene, which serves to slow the chemistry, resulting in longer lifetimes for species that react with OH. Ozone and PAN production is minimal in this case. In the case where isoprene is convected and LNOx is present, there is a large effect on the expected ensuing chemistry: isoprene exerts a dominant impact on HOx and nitrogen-containing species; the relative contribution from other species to HOx, such as peroxides, is insignificant. The isoprene reacts quickly, resulting in primary and secondary products, including formaldehyde and methyl glyoxal. The model predicts enhanced production of alkyl nitrates (ANs) and peroxyacyl nitrate compounds (PANs). PANs persist because of the cold temperatures of the upper troposphere resulting in a large change in the NOx mixing ratios which, in turn, has a large impact on the HOx chemistry. Ozone production is substantial during the first few hours following the convection to the UT, resulting in a net gain of approximately 10 ppbv compared to the modeled scenario in which LNOx is present but no isoprene is present aloft.

New-particle formation in the plumes of coal-fired power plants and other anthropogenic sulfur sources may be an important source of particles in the atmosphere. It remains unclear, however, how best to reproduce this formation in global and regional aerosol models with grid-box lengths that are 10s of kilometers and larger. The predictive power of these models is thus limited by the resultant uncertainties in aerosol size distributions. In this paper, we focus on sub-grid sulfate aerosol processes within coal-fired power plant plumes: the sub-grid oxidation of SO2 with condensation of H2SO4 onto newly-formed and pre-existing particles. We have developed a modeling framework with aerosol microphysics in the System for Atmospheric Modelling (SAM), a Large-Eddy Simulation/Cloud-Resolving Model (LES/CRM). The model is evaluated against aircraft observations of new-particle formation in two different power-plant plumes and reproduces the major features of the observations. We show how the downwind plume aerosols can be greatly modified by both meteorological and background aerosol conditions. In general, new-particle formation and growth is greatly reduced during polluted conditions due to the large pre-existing aerosol surface area for H2SO4 condensation and particle coagulation. The new-particle formation and growth rates are also a strong function of the amount of sunlight and NOx since both control OH concentrations. The results of this study highlight the importance for improved sub-grid particle formation schemes in regional and global aerosol models.

We use aircraft observations obtained during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission to examine the distributions and source attributions of O3 and NOy in the Arctic and sub-Arctic region. Using a number of marker tracers, we distinguish various air masses from the background troposphere and examine their contributions to NOx, O3, and O3 production in the Arctic troposphere. The background Arctic troposphere has a mean O3 of ~60 ppbv and NOx of ~25 pptv throughout spring and summer with CO decreasing from ~145 ppbv in spring to ~100 ppbv in summer. These observed mixing ratios are not notably different from the values measured during the 1988 ABLE-3A and the 2002 TOPSE field campaigns despite the significant changes in emissions and stratospheric ozone layer in the past two decades that influence Arctic tropospheric composition. Air masses associated with stratosphere-troposphere exchange are present throughout the mid and upper troposphere during spring and summer. These air masses, with mean O3 concentrations of 140–160 ppbv, are significant direct sources of O3 in the Arctic troposphere. In addition, air of stratospheric origin displays net O3 formation in the Arctic due to its sustainable, high NOx (75 pptv in spring and 110 pptv in summer) and NOy (~800 pptv in spring and ~1100 pptv in summer). The air masses influenced by the stratosphere sampled during ARCTAS-B also show conversion of HNO3 to PAN. This active production of PAN is the result of increased degradation of ethane in the stratosphere-troposphere mixed air mass to form CH3CHO, followed by subsequent formation of PAN under high NOx conditions. These findings imply that an adequate representation of stratospheric NOy input, in addition to stratospheric O3 influx, is essential to accurately simulate tropospheric Arctic O3, NOx and PAN in chemistry transport models. Plumes influenced by recent anthropogenic and biomass burning emissions observed during ARCTAS show highly elevated levels of hydrocarbons and NOy (mostly in the form of NOx and PAN), but do not contain O3 higher than that in the Arctic tropospheric background except some aged biomass burning plumes sampled during spring. Convection and/or lightning influences are negligible sources of O3 in the Arctic troposphere but can have significant impacts in the upper troposphere in the continental sub-Arctic during summer.

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j (NO 2 ) photolysis frequencies by nominally 17%, while aerosols reduced j (NO 2 ) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h −1 .

A comparison of a model using five widely known mechanisms (RACM, CB05, LaRC, SAPRC-99, SAPRC-07, and MCMv3.1) has been conducted based on the TexAQS II Radical and Aerosol Measurement Project (TRAMP-2006) field data in 2006. The concentrations of hydroxyl (OH) and hydroperoxy (HO2) radicals were calculated by a zero-dimensional box model with each mechanism and then compared with the OH and HO2 measurements. The OH and HO2 calculated by the model with different mechanisms show similarities and differences with each other and with the measurements. First, measured OH and HO2 are generally greater than modeled for all mechanisms, with the median modeled-to-measured ratios ranging from about 0.8 (CB05) to about 0.6 (SAPRC-99). These differences indicate that either measurement errors, the effects of unmeasured species or chemistry errors in the model or the mechanisms, with some errors being independent of the mechanism used. Second, the modeled and measured ratios of HO2/OH agree when NO is about 1 ppbv, but the modeled ratio is too high when NO was less and too low when NO is more, as seen in previous studies. Third, mechanism–mechanism HOx differences are sensitive to the environmental conditions – in more polluted conditions, the mechanism–mechanism differences are less. This result suggests that, in polluted conditions, the mechanistic details are less important than in cleaner conditions, probably because of the dominance of reactive nitrogen chemistry under polluted conditions.

An extensive set of measurements was made in and around Mexico City as part of the MILAGRO (Megacity Initiative: Local and Global Research Observations) experiments in March 2006. Simulations with the Model for Ozone and Related Chemical Tracers, version 4 (MOZART-4), a global chemical transport model, have been used to provide a regional context for these observations and assist in their interpretation. These MOZART-4 simulations reproduce the aircraft observations generally well, but some differences in the modeled volatile organic compounds (VOCs) from the observations result from incorrect VOC speciation assumed for the emission inventories. The different types of CO sources represented in the model have been "tagged" to quantify the contributions of regions outside Mexico, as well as the various emissions sectors within Mexico, to the regional air quality of Mexico. This analysis indicates open fires have some, but not a dominant, impact on the atmospheric composition in the region around Mexico City when averaged over the month. However, considerable variation in the fire contribution (2–15% of total CO) is seen during the month. The transport and photochemical aging of Mexico City emissions were studied using tags of CO emissions for each day, showing that typically the air downwind of Mexico City was a combination of many ages. Ozone production in MOZART-4 is shown to agree well with the net production rates from box model calculations constrained by the MILAGRO aircraft measurements. Ozone production efficiency derived from the ratio of Ox to NOz is higher in MOZART-4 than in the observations for moderately polluted air. OH reactivity determined from the MOZART-4 results shows the same increase in relative importance of oxygenated VOCs downwind of Mexico City as the reactivity inferred from the observations. The amount of ozone produced by emissions from Mexico City and surrounding areas has been quantified in the model by tracking NO emissions, showing little influence beyond Mexico's borders, and also relatively minor influence from fire emissions on the monthly average tropospheric ozone column.

We use observations from the April 2008 NASA ARCTAS aircraft campaign to the North American Arctic, interpreted with a global 3-D chemical transport model (GEOS-Chem), to better understand the sources and cycling of hydrogen oxide radicals (HOx≡H+OH+peroxy radicals) and their reservoirs (HOy≡HOx+peroxides) in the springtime Arctic atmosphere. We find that a standard gas-phase chemical mechanism overestimates the observed HO2 and H2O2 concentrations. Computation of HOx and HOy gas-phase chemical budgets on the basis of the aircraft observations also indicates a large missing sink for both. We hypothesize that this could reflect HO2 uptake by aerosols, favored by low temperatures and relatively high aerosol loadings, through a mechanism that does not produce H2O2. We implemented such an uptake of HO2 by aerosol in the model using a standard reactive uptake coefficient parameterization with γ(HO2) values ranging from 0.02 at 275 K to 0.5 at 220 K. This successfully reproduces the concentrations and vertical distributions of the different HOx species and HOy reservoirs. HO2 uptake by aerosol is then a major HOx and HOy sink, decreasing mean OH and HO2 concentrations in the Arctic troposphere by 32% and 31% respectively. Better rate and product data for HO2 uptake by aerosol are needed to understand this role of aerosols in limiting the oxidizing power of the Arctic atmosphere.

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

The NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was conducted in two 3-week deployments based in Alaska (April 2008) and western Canada (June–July 2008). Its goal was to better understand the factors driving current changes in Arctic atmospheric composition and climate, including (1) influx of mid-latitude pollution, (2) boreal forest fires, (3) aerosol radiative forcing, and (4) chemical processes. The June–July deployment was preceded by one week of flights over California (ARCTAS-CARB) focused on (1) improving state emission inventories for greenhouse gases and aerosols, (2) providing observations to test and improve models of ozone and aerosol pollution. ARCTAS involved three aircraft: a DC-8 with a detailed chemical payload, a P-3 with an extensive aerosol and radiometric payload, and a B-200 with aerosol remote sensing instrumentation. The aircraft data augmented satellite observations of Arctic atmospheric composition, in particular from the NASA A-Train. The spring phase (ARCTAS-A) revealed pervasive Asian pollution throughout the Arctic as well as significant European pollution below 2 km. Unusually large Siberian fires in April 2008 caused high concentrations of carbonaceous aerosols and also affected ozone. Satellite observations of BrO column hotspots were found not to be related to Arctic boundary layer events but instead to tropopause depressions, suggesting the presence of elevated inorganic bromine (5–10 pptv) in the lower stratosphere. Fresh fire plumes from Canada and California sampled during the summer phase (ARCTAS-B) indicated low NOx emission factors from the fires, rapid conversion of NOx to PAN, no significant secondary aerosol production, and no significant ozone enhancements except when mixed with urban pollution.

Measurements of OH, H2SO4, and MSA at South Pole (SP) Antarctica were recorded as a part of the 2003 Antarctic Chemistry Investigation (ANTCI 2003). The time period 22 November, 2003–2 January, 2004 provided a unique opportunity to observe atmospheric chemistry at SP under both natural conditions as well as those uniquely defined by a solar eclipse event. Results under natural solar conditions generally confirmed those reported previously in the year 2000. In both years the major chemical driver leading to large scale fluctuations in OH was shifts in the concentration levels of NO. Like in 2000, however, the 2003 observational data were systematically lower than model predictions. This can be interpreted as indicating that the model mechanism is still missing a significant HOx sink reaction(s); or, alternatively, that the OH calibration source may have problems. Still a final possibility could involve the integrity of the OH sampling scheme which involved a fixed building site. As expected, during the peak in the solar eclipse both NO and OH showed large decreases in their respective concentrations. Interestingly, the observational OH profile could only be approximated by the model mechanism upon adding an additional HOx radical source in the form of snow emissions of CH2O and/or H2O2. This would lead one to think that either CH2O and/or H2O2 snow emissions represent a significant HOx radical source under summertime conditions at SP. Observations of H2SO4 and MSA revealed both species to be present at very low concentrations (e.g., 5 × 105 and 1 × 105 molec cm−3, respectively), but similar to those reported in 2000. The first measurements of SO2 at SP demonstrated a close coupling with the oxidation product H2SO4. The observed low concentrations of MSA appear to be counter to the most recent thinking by glacio-chemists who have suggested that the plateau's lower atmosphere should have elevated levels of MSA. We speculate here that the absence of MSA may reflect efficient atmospheric removal mechanisms for this species involving either dynamical and/or chemical processes.

The measurement of OH reactivity, the inverse of the OH lifetime, provides a powerful tool to investigate atmospheric photochemistry. A new airborne OH reactivity instrument was designed and deployed for the first time on the NASA DC-8 aircraft during the second phase of Intercontinental Chemical Transport Experiment-B (INTEX-B) campaign, which was focused on the Asian pollution outflow over Pacific Ocean and was based in Hawaii and Alaska. The OH reactivity was measured by adding OH, generated by photolyzing water vapor with 185 nm UV light in a moveable wand, to the flow of ambient air in a flow tube and measuring the OH signal with laser induced fluorescence. As the wand was pulled back away from the OH detector, the OH signal decay was recorded; the slope of −Δln(signal)/Δ time was the OH reactivity. The overall absolute uncertainty at the 2σ confidence levels is about 1 s−1 at low altitudes (for decay about 6 s−1), and 0.7 s−1 at high altitudes (for decay about 2 s−1). From the median vertical profile obtained in the second phase of INTEX-B, the measured OH reactivity (4.0±1.0 s−1) is higher than the OH reactivity calculated from assuming that OH was in steady state (3.3&plusmn0.8 s−1), and even higher than the OH reactivity that was calculated from the total measurements of all OH reactants (1.6±0.4 s−1). Model calculations show that the missing OH reactivity is consistent with the over-predicted OH and under-predicted HCHO in the boundary layer and lower troposphere. The over-predicted OH and under-predicted HCHO suggest that the missing OH sinks are most likely related to some highly reactive VOCs that have HCHO as an oxidation product.

The first airborne measurements of nitric oxide (NO) on the Antarctic plateau have demonstrated that the previously reported elevated levels of this species extend well beyond the immediate vicinity of South Pole. Although the current database is still relatively weak and critical laboratory experiments are still needed, the findings here suggest that the chemical uniqueness of the plateau may be substantially greater than first reported. For example, South Pole ground-based findings have provided new evidence showing that the dominant process driving the release of nitrogen from the snowpack during the spring/summer season (post-depositional loss) is photochemical in nature with evaporative processes playing a lesser role. There is also new evidence suggesting that nitrogen, in the form of nitrate, may undergo multiple recycling within a given photochemical season. Speculation here is that this may be a unique property of the plateau and much related to its having persistent cold temperatures even during summer. These conditions promote the efficient adsorption of molecules like HNO3 (and very likely HO2NO2) onto snow-pack surface ice where we have hypothesized enhanced photochemical processing can occur, leading to the efficient release of NOx to the atmosphere. In addition, to these process-oriented tentative conclusions, the findings from the airborne studies, in conjunction with modeling exercises suggest a new paradigm for the plateau atmosphere. The near-surface atmosphere over this massive region can be viewed as serving as much more than a temporary reservoir or holding tank for imported chemical species. It defines an immense atmospheric chemical reactor which is capable of modifying the chemical characteristics of select atmospheric constituents. This reactor has most likely been in place over geological time, and may have led to the chemical modulation of some trace species now found in ice cores. Reactive nitrogen has played a critical role in both establishing and in maintaining this reactor.

An interpretative modeling analysis is conducted to simulate the diurnal variations in OH and HO 2 +RO 2 observed at Summit, Greenland in 2003. The main goal is to assess the HO x budget and to quantify the impact of snow emissions on ambient HO x as well as on CH 2 O and H 2 O 2 . This analysis is based on composite diurnal profiles of HO x precursors recorded during a 3-day period (July 7–9), which were generally compatible with values reported in earlier studies. The model simulations can reproduce the observed diurnal variation in HO 2 +RO 2 when they are constrained by observations of H 2 O 2 and CH 2 O. By contrast, model predictions of OH were about factor of 2 higher than the observed values. Modeling analysis of H 2 O 2 suggests that its distinct diurnal variation is likely controlled by snow emissions and loss by deposition and/or scavenging. Similarly, deposition and/or scavenging sinks are needed to reproduce the observed diel profile in CH 2 O. This study suggests that for the Summit 2003 period snow emissions contribute ∼25% of the total CH 2 O production, while photochemical oxidation of hydrocarbon appears to be the dominant source. A budget assessment of HO x radicals shows that primary production from O( 1 D)+H 2 O and photolysis of snow emitted precursors (i.e., H 2 O 2 and CH 2 O) are the largest primary HO x sources at Summit, contributing 41% and 40%, respectively. The snow contribution to the HO x budget is mostly in the form of emissions of H 2 O 2 . The dominant HO x sink involves the HO 2 +HO 2 reaction forming H 2 O 2 , followed by its deposition to snow. These results differ from those previously reported for the South Pole (SP), in that primary production of HO x was shown to be largely driven by both the photolysis of CH 2 O and H 2 O 2 emissions (46%) with smaller contributions coming from the oxidation of CH 4 and the O( 1 D)+H 2 O reaction (i.e., 27% each). In sharp contrast to the findings at Summit in 2003, due to the much higher levels of NO x , the SP HO x sinks are dominated by HO x –NO x reactions, leading to the formation and deposition of HNO 3 and HO 2 NO 2 . Thus, a comparison between SP and Summit studies suggests that snow emissions appear to play a prominent role in controlling primary HO x production in both environments. However, as regards to maintaining highly elevated levels of OH, the two environments differ substantially. At Summit the elevated rate for primary production of HO x is most important; whereas, at SP it is the rapid recycling of the more prevalent HO 2 radical, through reaction with NO, back to OH that is primarily responsible.

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

As part of the Deep Convective Cloud and Chemistry (DC3) experiment, the National Science Foundation/National Center for Atmospheric Research (NCAR) Gulfstream-V (GV) and NASA DC-8 research aircraft probed the chemical composition of the inflow and outflow of two convective storms (north storm, NS, south storm, SS) originating in the Colorado region on 22 June 2012, a time when the High Park wildfire was active in the area. A wide range of trace species were measured on board both aircraft including biomass burning (BB) tracers hydrogen cyanide (HCN) and acetonitrile (ACN). Acrolein, a much shorter lived tracer for BB, was also quantified on the GV. The data demonstrated that the NS had ingested fresh smoke from the High Park fire and as a consequence had a higher VOC OH reactivity than the SS. The SS lofted aged fire tracers along with other boundary layer ozone precursors and was more impacted by lightning NO_x (LNO_x) than the NS. The NCAR master mechanism box model was initialized with measurements made in the outflow of the two storms. The NS and SS were predicted to produce 11 and 14 ppbv of O_3, respectively, downwind of the storm over 2 days. Sensitivity tests revealed that the ozone production potential of the SS was highly dependent on LNO_x. Normalized excess mixing ratios, ΔX/ΔCO, for HCN and ACN were determined in both the fire plume and the storm outflow and found to be 7.0 ± 0.5 and 2.3 ± 0.5 pptv ppbv^(−1), respectively, and 1.4 ± 0.3 pptv ppbv^(−1) for acrolein in the outflow only.

Several groups have now shown that snow covered polar areas can lead to the release of NO x to the atmosphere as a result of the UV photolysis of nitrate ions. Here we focus on a detailed examination of the NO observations recorded at South Pole (SP). Topics explored include: (1) why SP NO x levels greatly exceed those at other polar sites; (2) what processes are responsible for the observed large day to day NO concentration shifts at SP; and (3) possible explanations for the large variability in NO seen between SP studies in 1998 and 2000. As discussed in the main body of the text, the answer to all three questions lies in the uniqueness of the summertime SP environment. Among these characteristics is the presence of a large plateau region just to the east of SP. This region defines one of the world's largest air drainage fields, being nearly 1000 km across and having elevation of ∼ 3 km . In addition, summertime SP surface temperatures typically do not exceed - 25 ° C , leading to frequent cases where strong near surface temperature inversions occur. It experiences 24 h of continuous sunlight, giving rise to non-stop photochemical reactions both within the snowpack and in the atmosphere. The latter chemistry is unique at SP in that increasing levels of NO x lead to an enhanced lifetime for NO x , thereby producing non-linear increases in NO x . In addition, the rapid atmospheric oxidation of NO x , in conjunction with very rapid dry deposition of the products ( HNO 3 and HO 2 NO 2 ), results in a very efficient recycling of NO x back to the snowpack. Details concerning these unique SP characteristics and the extension of these findings to the greater plateau region are discussed. Finally, the relationship of NO x recycling and total nitrogen deposition to the plateau is explored.

Reported here are modeling results based on ISCAT (Investigation of Sulfur Chemistry of Antarctic Troposphere) 2000 observations recorded at the South Pole (SP) during the Austral Summer of 2000. The observations included a comprehensive set of photochemical parameters, e.g., NO, O3, and CO. It is worthy to note that not only were OH and HO2 observed, but also HOx precursor species CH2O, H2O2, and HONO were measured. Previous studies have suggested that HONO is the major source of OH/HOx in the Arctic; however, observed HONO levels at SP induced dramatic model overprediction of both HOx and NOx when used to constrain the model calculations. In contrast, model predictions constrained by observed values of CH2O and H2O2 are consistent with the observations of OH and HO2 (i.e., within 20%) for more than half of the data. Significant model overpredictions of OH, however, were seen at the NO levels lower than 50 pptv or higher than 150 pptv. An analysis of HOx budget at the median NO level suggests that snow emissions of H2O2 and CH2O are the single most important primary source of SP HOx, contributing 46% to the total source. Major sinks for HOx are found to be dry deposition of HO2NO2 and HNO3 as well as their reactions with OH. Although ISCAT 2000 led to a major progress in our understanding of SP HOx chemistry, critical aspects of this chemistry are still in need of further investigation.

In support of future satellite missions that aim to address the current shortcomings in measuring air quality from space, NASA’s Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign was designed to enable exploration of relationships between column measurements of trace species relevant to air quality at high spatial and temporal resolution. In the DISCOVER-AQ data set, a modest correlation (r(2) = 0.45) between ozone (O(3)) and formaldehyde (CH(2)O) column densities was observed. Further analysis revealed regional variability in the O(3)-CH(2)O relationship, with Maryland having a strong relationship when data were viewed temporally and Houston having a strong relationship when data were viewed spatially. These differences in regional behavior are attributed to differences in volatile organic compound (VOC) emissions. In Maryland, biogenic VOCs were responsible for ~28% of CH(2)O formation within the boundary layer column, causing CH(2)O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH(2)O was observed. Box model simulations suggested that ambient CH(2)O mixing ratios have a weak diurnal trend (±20% throughout the day) due to photochemical effects, and that larger diurnal trends are associated with changes in hydrocarbon precursors. Finally, mathematical relationships were developed from first principles and were able to replicate the different behaviors seen in Maryland and Houston. While studies would be necessary to validate these results and determine the regional applicability of the O(3)-CH(2)O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near-surface air quality.

Methane is an efficient absorber of infrared radiation and a potent greenhouse gas with a warming potential 72 times greater than carbon dioxide on a per molecule basis. Development of methane active remote sensing capability using the differential absorption lidar (DIAL) technique enables scientific assessments of the gas emission and impacts on the climate. A performance evaluation of a pulsed DIAL system for monitoring atmospheric methane is presented. This system leverages a robust injection-seeded pulsed Nd:YAG pumped Optical Parametric Oscillator (OPO) laser technology operating in the 1.645 µm spectral band. The system also leverages an efficient low noise, commercially available, InGaAs avalanche photo-detector (APD). Lidar signals and error budget are analyzed for system operation on ground in the range-resolved DIAL mode and from airborne platforms in the integrated path DIAL (IPDA) mode. Results indicate system capability of measuring methane concentration profiles with

A time-dependent photochemical box model is used to examine the photochemistry of the equatorial and southern subtropical Pacific troposphere with aircraft data obtained during two distinct seasons: the Pacific Exploratory Mission-Tropics A (PEM-Tropics A) field campaign in September and October of 1996 and the Pacific Exploratory Mission-Tropics B (PEM-Tropics B) campaign in March and April of 1999. Model-predicted values were compared to observations for selected species (e.g., NO2, OH, HO2) with generally good agreement. Predicted values of HO2 were larger than those observed in the upper troposphere, in contrast to previous studies which show a general underprediction Of HO2 at upper altitudes. Some characteristics of the budgets Of HOx, NOx, and peroxides are discussed. The integrated net tendency for O3 is negative over the remote Pacific during both seasons, with gross formation equal to no more than half of the gross destruction. This suggests that a continual supply of O3 into the Pacific region throughout the year must exist in order to maintain O3 levels. Integrated net tendencies for equatorial O3 showed a seasonality, with a net loss of 1.06×1011 molecules cm−2 s−1 during PEM-Tropics B (March) increasing by 50% to 1.60×1011 molecules cm−2 s−1 during PEM-Tropics A (September). The seasonality over the southern subtropical Pacific was somewhat lower, with losses of 1.21×1011 molecules cm−2 s−1 during PEM-Tropics B (March) increasing by 25% to 1.51×1011 molecules cm−2 s−1 during PEM-Tropics A (September). While the larger net losses during PEM-Tropics A were primarily driven by higher concentrations of O3, the ability of the subtropical atmosphere to destroy O3 was ∼30% less effective during the PEM-Tropics A (September) campaign due to a drier atmosphere and higher overhead O3 column amounts.

Author(s): Chen, G; Davis, D; Crawford, J; Nowak, JB; Eisele, F; Mauldin, RL; Tanner, D; Buhr, M; Shetter, R; Lefer, B; Arimoto, R; Hogan, A; Blake, D | Abstract: Unexpected high levels of OH and NO were recorded at the South Pole (SP) Atmospheric Research Observatory during the 1998-99 ISCAT field study. Model simulations suggest a major photochemical linkage between observed OH and NO. A detailed comparison of the observations with model predictions revealed good agreement for OH at NO levels between 120 and 380 pptv. However, the model tended to overestimate OH for NO levels l 120 pptv, while it underestimated OH at levels g 380 pptv. The reasons for these deviations appear not to involve NO directly but rather HOx radical scavenging for the low NO conditions and additional HOx sources for the high NO conditions. Because of the elevated levels of NO and highly activated HOx photochemistry, the SP was found to be a strong net source of surface ozone. It is quite likely that the strong oxidizing environment found at the South Pole extends over the entire polar plateau.

Observations of OH, NO, and actinic flux at the South Pole surface during December 1998 suggest a surprisingly active photochemical environment which should result in photochemical production of ozone. Long-term South Pole in situ ozone data as well as sonde data also appear to support this conclusion. Other possible factors contributing to ozone variability such as stratospheric influence and the origin of air transported to the South Pole are also explored. Based on box model calculations it is estimated that photochemistry could add 2.2 to 3.6 ppbv/day of ozone to surface air parcels residing on the Antarctic polar plateau. Although the oxidizing potential of the polar plateau appears to be exceptionally high for a remote site, it is unlikely that it has a significant impact on surrounding regions such as the Southern Ocean and the Antarctic free troposphere. These new findings do suggest, however, that the enhanced oxidizing power of the polar plateau may need to be considered in interpreting the chemical history of climate proxy species in ice cores.

The impact of ship emissions on marine boundary layer (MBL) NOx and SO2 levels over the Pacific Ocean has been explored by comparing predictions (with and without ships) from a global chemical transport model (GCTM) against compiled airborne observations of MBL NOx and SO2. For latitudes >15°N, which define that part of the Pacific having the heaviest shipping, this analysis revealed significant model over prediction for NOx and a modest under prediction for SO2 when ship emissions were considered. Possible reasons for the difference in NOx and SO2 were explored using a full-chemistry box model. These results revealed that for an actual plume setting the NOx lifetime could be greatly shortened by chemical processes promoted by ship plume emissions themselves. Similar chemical behavior was not found for SO2.

Airborne observations of NO during the Subsonics Assessment Ozone and Nitrogen Oxides Experiment (SONEX) reveal episodes of high NOx in the upper troposphere believed to be associated with lightning. Linkage to specific periods of lightning activity is possible through back trajectories and data from the National Lightning Detection Network. Lagrangian model calculations are used to explore the evolution of these high NOx plumes over the 1–2 days between their introduction and subsequent sampling by NASA's DC-8 aircraft. Simulations include expected changes in HNO3, H2O2, CH3OOH, HO2, and OH. Depending on the time of injection and dilution rate, initial NOx concentrations are estimated to range from 1 to 7 ppbv. Similar to many previous studies, simulated HNO3 concentrations tend to be greater than observations. Several possible explanations for this difference are explored. H2O2 observations are shown to be consistent with removal in convective activity. While it is possible that upper tropospheric CH3OOH is enhanced by convection, simulations show such increases in CH3OOH can be short-lived (e.g.

Interactions between atmospheric hydrogen oxides and aircraft nitrogen oxides determine the impact of aircraft exhaust on atmospheric chemistry. To study these interactions, the Subsonic Assessment: Ozone and Nitrogen Oxide Experiment (SONEX) assembled the most complete measurement complement to date for studying HOx (OH and HO2) chemistry in the free troposphere. Observed and modeled HOx agree on average to within experimental uncertainties (±40%). However, significant discrepancies occur as a function of NO and at solar zenith angles >70°. Some discrepancies appear to be removed by model adjustments to HOx-NOx chemistry, particularly by reducing HO2NO2 (PNA) and by including heterogeneous reactions on aerosols and cirrus clouds.

Data for the tropical upper troposphere (8–12 km, 20°N-20°S) collected during NASA's Pacific Exploratory Missions have been used to carry out a detailed examination of the photochemical processes controlling HOx (OH+HO2). Of particular significance is the availability of measurements of nonmethane hydrocarbons, oxygenated hydrocarbons (i.e., acetone, methanol, and ethanol) and peroxides (i.e., H2O2 and CH3OOH). These observations have provided constraints on model calculations permitting an assessment of the potential impact of these species on the levels of HOx, CH3O2, CH2O, as well as ozone budget parameters. Sensitivity calculations using a time-dependent photochemical box model show that when constrained by measured values of the above oxygenated species, model estimated HOx levels are elevated relative to unconstrained calculations. The impact of constraining these species was found to increase with altitude, reflecting the systematic roll-off in water vapor mixing ratios with altitude. At 11–12 km, overall increases in HOx approached a factor of 2 with somewhat larger increases being found for gross and net photochemical production of ozone. While significant, the impact on HOx due to peroxides appears to be less than previously estimated. In particular, observations of elevated H2O2 levels may be more influenced by local photochemistry than by convective transport. Issues related to the uncertainty in high-altitude water vapor levels and the possibility of other contributing sources of HOx are discussed. Finally, it is noted that the uncertainties in gas kinetic rate coefficients at the low temperatures of the upper troposphere and as well as OH sensor calibrations should be areas of continued investigation.