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The Korea-United States Air Quality (KORUS-AQ) field study was conducted during May-June 2016. The effort was jointly sponsored by the National Institute of Environmental Research of South Korea and the National Aeronautics and Space Administration of the United States. KORUS-AQ offered an unprecedented, multi-perspective view of air quality conditions in South Korea by employing observations from three aircraft, an extensive ground-based network, and three ships along with an array of air quality forecast models. Information gathered during the study is contributing to an improved understanding of the factors controlling air quality in South Korea. The study also provided a valuable test bed for future air quality-observing strategies involving geostationary satellite instruments being launched by both countries to examine air quality throughout the day over Asia and North America. This article presents details on the KORUS-AQ observational assets, study execution, data products, and air quality conditions observed during the study. High-level findings from companion papers in this special issue are also summarized and discussed in relation to the factors controlling fine particle and ozone pollution, current emissions and source apportionment, and expectations for the role of satellite observations in the future. Resulting policy recommendations and advice regarding plans going forward are summarized. These results provide an important update to early feedback previously provided in a Rapid Science Synthesis Report produced for South Korean policy makers in 2017 and form the basis for the Final Science Synthesis Report delivered in 2020.

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.

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.

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2x larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R 2 = 0:36) and reactivity (R 2 = 0:54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (~ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL: FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene C oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

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.

Abstract. Organic aerosol (OA) is an important fraction of submicron aerosols. However,it is challenging to predict and attribute the specific organic compounds andsources that lead to observed OA loadings, largely due to contributions fromsecondary production. This is especially true for megacities surrounded bynumerous regional sources that create an OA background. Here, we utilizein situ gas and aerosol observations collected on board the NASA DC-8 duringthe NASA–NIER KORUS-AQ (Korea–United States Air Quality) campaign toinvestigate the sources and hydrocarbon precursors that led to the secondaryOA (SOA) production observed over Seoul. First, we investigate thecontribution of transported OA to total loadings observed over Seoul byusing observations over the Yellow Sea coupled to FLEXPART Lagrangiansimulations. During KORUS-AQ, the average OA loading advected into Seoul was∼1–3 µg sm−3. Second, taking this background intoaccount, the dilution-corrected SOA concentration observed over Seoul was∼140 µgsm-3ppmv-1 at 0.5 equivalent photochemicaldays. This value is at the high end of what has been observed in othermegacities around the world (20–70 µgsm-3ppmv-1 at 0.5equivalent days). For the average OA concentration observed over Seoul(13 µg sm−3), it is clear that production of SOA from locallyemitted precursors is the major source in the region. The importanceof local SOA production was supported by the following observations.(1) FLEXPART source contribution calculations indicate anyhydrocarbons with a lifetime of less than 1 day, which are shown to dominate theobserved SOA production, mainly originate from South Korea. (2) SOAcorrelated strongly with other secondary photochemical species, includingshort-lived species (formaldehyde, peroxy acetyl nitrate, sum of acyl peroxynitrates, dihydroxytoluene, and nitrate aerosol). (3) Results froman airborne oxidation flow reactor (OFR), flown for the first time, show afactor of 4.5 increase in potential SOA concentrations over Seoul versus overthe Yellow Sea, a region where background air masses that are advected intoSeoul can be measured. (4) Box model simulations reproduce SOAobserved over Seoul within 11 % on average and suggest that short-livedhydrocarbons (i.e., xylenes, trimethylbenzenes, and semi-volatile and intermediate-volatility compounds) were the main SOA precursors over Seoul. Toluenealone contributes 9 % of the modeled SOA over Seoul. Finally, along withthese results, we use the metric ΔOA/ΔCO2 toexamine the amount of OA produced per fuel consumed in a megacity, whichshows less variability across the world than ΔOA∕ΔCO.

Abstract. The evolution of organic aerosols (OAs) and their precursors in the boundary layer (BL) of the Colorado Front Range during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ, July–August 2014) was analyzed by in situ measurements and chemical transport modeling. Measurements indicated significant production of secondary OA (SOA), with enhancement ratio of OA with respect to carbon monoxide (CO) reaching 0.085±0.003 µg m−3 ppbv−1. At background mixing ratios of CO, up to  ∼  1.8 µg m−3 background OA was observed, suggesting significant non-combustion contribution to OA in the Front Range. The mean concentration of OA in plumes with a high influence of oil and natural gas (O&G) emissions was  ∼  40 % higher than in urban-influenced plumes. Positive matrix factorization (PMF) confirmed a dominant contribution of secondary, oxygenated OA (OOA) in the boundary layer instead of fresh, hydrocarbon-like OA (HOA). Combinations of primary OA (POA) volatility assumptions, aging of semi-volatile species, and different emission estimates from the O&G sector were used in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) simulation scenarios. The assumption of semi-volatile POA resulted in greater than a factor of 10 lower POA concentrations compared to PMF-resolved HOA. Including top-down modified O&G emissions resulted in substantially better agreements in modeled ethane, toluene, hydroxyl radical, and ozone compared to measurements in the high-O&G-influenced plumes. By including emissions from the O&G sector using the top-down approach, it was estimated that the O&G sector contributed to

The San Joaquin Valley (SJV) of California experiences high concentrations of particulate matter NH4NO3 during episodes of meteorological stagnation in winter. A rich data set of observations related to NH4NO3 formation was acquired during multiple periods of elevated NH4NO3 during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign in SJV in January and February 2013. Here NH4NO3 is simulated during the SJV DISCOVER-AQ study period with the Community Multiscale Air Quality (CMAQ) model, diagnostic model evaluation is performed using the DISCOVER-AQ data set, and integrated reaction rate analysis is used to quantify HNO3 production rates. Simulated NO3- generally agrees well with routine monitoring of 24-hr average NO3-, but comparisons with hourly average NO3- measurements in Fresno revealed differences at higher time resolution. Predictions of gas-particle partitioning of total nitrate (HNO3 + NO3-) and NHx (NH3 + NH4+) generally agree well with measurements in Fresno, although partitioning of total nitrate to HNO3 is sometimes overestimated at low relative humidity in afternoon. Gas-particle partitioning results indicate that NH4NO3 formation is limited by HNO3 availability in both the model and ambient. NH3 mixing ratios are underestimated, particularly in areas with large agricultural activity, and additional work on the spatial allocation of NH3 emissions is warranted. During a period of elevated NH4NO3, the model predicted that the OH + NO2 pathway contributed 46% to total HNO3production in SJV and the N2O5 heterogeneous hydrolysis pathway contributed 54%. The relative importance of the OH + NO2 pathway for HNO3 production is predicted to increase as NOx emissions decrease.

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.

Abstract. Chemical models must correctly calculate the ozone formation rate, P(O3), to accurately predict ozone levels and to test mitigation strategies. However, air quality models can have large uncertainties in P(O3) calculations, which can create uncertainties in ozone forecasts, especially during the summertime when P(O3) is high. One way to test mechanisms is to compare modeled P(O3) to direct measurements. During summer 2014, the Measurement of Ozone Production Sensor (MOPS) directly measured net P(O3) in Golden, CO, approximately 25 km west of Denver along the Colorado Front Range. Net P(O3) was compared to rates calculated by a photochemical box model that was constrained by measurements of other chemical species and that used a lumped chemical mechanism and a more explicit one. Median observed P(O3) was up to a factor of 2 higher than that modeled during early morning hours when nitric oxide (NO) levels were high and was similar to modeled P(O3) for the rest of the day. While all interferences and offsets in this new method are not fully understood, simulations of these possible uncertainties cannot explain the observed P(O3) behavior. Modeled and measured P(O3) and peroxy radical (HO2 and RO2) discrepancies observed here are similar to those presented in prior studies. While a missing atmospheric organic peroxy radical source from volatile organic compounds co-emitted with NO could be one plausible solution to the P(O3) discrepancy, such a source has not been identified and does not fully explain the peroxy radical model–data mismatch. If the MOPS accurately depicts atmospheric P(O3), then these results would imply that P(O3) in Golden, CO, would be NOx-sensitive for more of the day than what is calculated by models, extending the NOx-sensitive P(O3) regime from the afternoon further into the morning. These results could affect ozone reduction strategies for the region surrounding Golden and possibly other areas that do not comply with national ozone regulations. Thus, it is important to continue the development of this direct ozone measurement technique to understand P(O3), especially under high-NOx regimes.

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.

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 (O3) and formaldehyde (CH2O) column densities was observed. Further analysis revealed regional variability in the O3-CH2O 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 CH2O formation within the boundary layer column, causing CH2O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH2O was observed. Box model simulations suggested that ambient CH2O 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 O3-CH2O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near-surface air quality.

We examine wet scavenging of soluble trace gases in storms observed during the Deep Convective Clouds and Chemistry (DC3) field campaign. We conduct high-resolution simulations with the Weather Research and Forecasting model with Chemistry (WRF-Chem) of a severe storm in Oklahoma. The model represents well the storm location, size, and structure as compared with Next Generation Weather Radar reflectivity, and simulated CO transport is consistent with aircraft observations. Scavenging efficiencies (SEs) between inflow and outflow of soluble species are calculated from aircraft measurements and model simulations. Using a simple wet scavenging scheme, we simulate the SE of each soluble species within the error bars of the observations. The simulated SEs of all species except nitric acid (HNO3) are highly sensitive to the values specified for the fractions retained in ice when cloud water freezes. To reproduce the observations, we must assume zero ice retention for formaldehyde (CH2O) and hydrogen peroxide (H2O2) and complete retention for methyl hydrogen peroxide (CH3OOH) and sulfur dioxide (SO2), likely to compensate for the lack of aqueous chemistry in the model. We then compare scavenging efficiencies among storms that formed in Alabama and northeast Colorado and the Oklahoma storm. Significant differences in SEs are seen among storms and species. More scavenging of HNO3 and less removal of CH3OOH are seen in storms with higher maximum flash rates, an indication of more graupel mass. Graupel is associated with mixed-phase scavenging and lightning production of nitrogen oxides (NOx), processes that may explain the observed differences in HNO3 and CH3OOH scavenging.

Measurements of formaldehyde (CH2O) from a tunable diode laser absorption spectrometer (TDLAS) were acquired onboard the NASA DC-8 aircraft during the summer 2004 INTEX-NA campaign to test our understanding of convection and CH2O production mechanisms in the upper troposphere (UT, 6–12 km) over continental North America and the North Atlantic Ocean. The present study utilizes these TDLAS measurements and results from a box model to (1) establish sets of conditions by which to distinguish “background” UT CH2O levels from those perturbed by convection and other causes; (2) quantify the CH2O precursor budgets for both air mass types; (3) quantify the fraction of time that the UT CH2O measurements over North America and North Atlantic are perturbed during the summer of 2004; (4) provide estimates for the fraction of time that such perturbed CH2O levels are caused by direct convection of boundary layer CH2O and/or convection of CH2O precursors; (5) assess the ability of box models to reproduce the CH2O measurements; and (6) examine CH2O and HO2 relationships in the presence of enhanced NO. Multiple tracers were used to arrive at a set of UT CH2O background and perturbed air mass periods, and 46% of the TDLAS measurements fell within the latter category. In general, production of CH2O from CH4 was found to be the dominant source term, even in perturbed air masses. This was followed by production from methyl hydroperoxide, methanol, PAN-type compounds, and ketones, in descending order of their contribution. At least 70% to 73% of the elevated UT observations were caused by enhanced production from CH2O precursors rather than direct transport of CH2O from the boundary layer. In the presence of elevated NO, there was a definite trend in the CH2O measurement–model discrepancy, and this was highly correlated with HO2 measurement–model discrepancies in the UT.

OH and HO2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment-A (INTEX-A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. The HOx results from INTEX-A are compared to those from previous campaigns and to results for other related measurements from. INTEX-A. Throughout the troposphere, observed OH was generally 0.95 of modeled OH; below 8 km, observed HO2 was generally 1.20 of modeled HO2. This observed-to-modeled comparison is similar to that for TRACE-P, another midlatitude study for which the median observed-to-modeled ratio was 1.08 for OH and 1.34 for HO2, and to that for PEM-TB, a tropical study for which the median observed-to-modeled ratio was 1.17 for OH and 0.97 for HO2. HO2 behavior above 8 km was markedly different. The observed-to-modeled HO2 ratio increased from ∼1.2 at 8 km to ∼3 at 11 km with the observed-to-modeled ratio correlating with NO. Above 8 km, the observed-to-modeled HO2 and observed NO were both considerably greater than observations from previous campaigns. In addition, the observed-to-modeled HO2/OH, which is sensitive to cycling reactions between OH and HO2, increased from ∼1.5 at 8 km to almost 3.5 at 11 km. These discrepancies suggest a large unknown HOx source and additional reactants that cycle HOx from OH to HO2. In the continental planetary boundary layer, the observed-to-modeled OH ratio increased from 1 when isoprene was less than 0.1 ppbv to over 4 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HOx sources. Progress in resolving these discrepancies requires a focused research activity devoted to further examination of possible unknown OH sinks and HOx sources. Copyright 2008 by the American Geophysical Union.

High resolution in situ measurements of atmospheric CO2 were made from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment - North America (INTEX-NA) campaign, part of the wider International Consortium for Atmospheric Research on Transport and Transformation (ICARTT). During the summer of 2004, eighteen flights comprising 160h of measurements were conducted within a region bounded by 27 to 53°N and 36 to 139°W over an altitude range of 0.15 to 12 km. These large-scale surveys provided the opportunity to examine the characteristics of the atmospheric CO2 signal over sparsely sampled areas of North America and adjacent ocean basins. The observations showed a high degree of variability (≤ 18%) due to the myriad source and sink processes influencing the air masses intercepted over the INTEX-NA sampling domain. Surface fluxes had strong effects on continental scale concentration gradients. Clear signatures of CO2 uptake were seen east of the Mississippi River, notably a persistent CO2 deficit in the lowest 2-3 km. When combining the airborne CO2 measurements with LANDSAT and MODIS data products, the lowest CO2 mixing ratios observed during the campaign (337 ppm) were tied to mid-continental agricultural fields planted in corn and soybeans. We used simultaneous measurements of CO, O3, C2Cl4, C2H6, C2H2 and other unique chemical tracers to differentiate air mass types. Coupling these distinct air mass chemical signatures with transport history permitted identification of convection, stratosphere-troposphere exchange, long-range transport from Eastern Asia, boreal wildfires, and continental outflow as competing processes at multiple scales influencing the observed concentrations. Our results suggest these are important factors contributing to the large-scale distribution in CO2 Mixing ratios thus these observations offer new constraints in the computation of the North American carbon budget. Copyright 2008 by the American Geophysical Union.

We present a statistical representation of the aggregate effects of deep convection on the chemistry and dynamics of the upper troposphere (UT) based on direct aircraft observations of the chemical composition of the UT over the eastern United States and Canada during summer. These measurements provide unique observational constraints on the chemistry occurring downwind of convection and the rate at which air in the UT is recycled. These results provide quantitative measures that can be used to evaluate global climate and chemistry models.

Formaldehyde (HCHO) columns measured from space provide constraints on emissions of volatile organic compounds (VOCs). Quantitative interpretation requires characterization of errors in HCHO column retrievals and relating these columns to VOC emissions. Retrieval error is mainly in the air mass factor (AMF) which relates fitted backscattered radiances to vertical columns and requires external information on HCHO, aerosols, and clouds. Here we use aircraft data collected over North America and the Atlantic to determine the local relationships between HCHO columns and VOC emissions, calculate AMFs for HCHO retrievals, assess the errors in deriving AMFs with a chemical transport model (GEOS-Chem), and draw conclusions regarding space-based mapping of VOC emissions. We show that isoprene drives observed HCHO column variability over North America; HCHO column data from space can thus be used effectively as a proxy for isoprene emission. From observed HCHO and isoprene profiles we find an HCHO molar yield from isoprene oxidation of 1.6 ± 0.5, consistent with current chemical mechanisms. Clouds are the primary error source in the AMF calculation; errors in the HCHO vertical profile and aerosols have comparatively little effect. The mean bias and 1σ uncertainty in the GEOS-Chem AMF calculation increase from

Local ozone production and loss rates for the arctic free troposphere (58-85° N, 1-6 km, February-May) during the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign were calculated using a constrained photochemical box model. Estimates were made to assess the importance of local photochemical ozone production relative to transport in accounting for the springtime maximum in arctic free tropospheric ozone. Ozone production and loss rates from our diel steady-state box model constrained by median observations were first compared to two point box models, one run to instantaneous steady-state and the other run to diel steady-state. A consistent picture of local ozone photochemistry was derived by all three box models suggesting that differences between the approaches were not critical. Our model-derived ozone production rates increased by a factor of 28 in the 1-3 km layer and a factor of 7 in the 3-6 km layer between February and May. The arctic ozone budget required net import of ozone into the arctic free troposphere throughout the campaign; however, the transport term exceeded the photochemical production only in the lower free troposphere (1-3 km) between February and March. Gross ozone production rates were calculated to increase linearly with NOx mixing ratios up to ∼300 pptv in February and for NOx mixing ratios up to ∼500 pptv in May. These NOx limits are an order of magnitude higher than median NOx levels observed, illustrating the strong dependence of gross ozone production rates on NOx mixing ratios for the majority of the observations. The threshold NOx mixing ratio needed for net positive ozone production was also calculated to increase from NOx ∼ 10 pptv in February to ∼25 pptv in May, suggesting that the NOx levels needed to sustain net ozone production are lower in winter than spring. This lower NOx threshold explains how wintertime photochemical ozone production can impact the build-up of ozone over winter and early spring. There is also an altitude dependence as the threshold NOx needed to produce net ozone shifts to higher values at lower altitudes. This partly explains the calculation of net ozone destruction for the 1-3 km layer and net ozone production for the 3-6 km layer throughout the campaign. © 2004 Kluwer Academic Publishers.

The budget of nitrogen oxides (NOx) in the arctic free troposphere is calculated with a constrained photochemical box model using aircraft observations from the Tropospheric O3 Production about the Spring Equinox (TOPSE) campaign between February and May. Peroxyacetic nitric anhydride (PAN) was observed to be the dominant odd nitrogen species (NOy) in the arctic free troposphere and showed a pronounced seasonal increase in mixing ratio. When constrained to observed acetaldehyde (CH3CHO) mixing ratios, the box model calculates unrealistically large net NOx losses due to PAN formation (62pptv/day for May, 1-3km). Thus, given our current understanding of atmospheric chemistry, these results cast doubt on the robustness of the CH3CHO observations during TOPSE. When CH3CHO was calculated to steady state in the box model, the net NOx loss to PAN was of comparable magnitude to the net NOx loss to HNO3 (NO2 reaction with OH) for spring conditions. During the winter, net NOx loss due to N2O5 hydrolysis dominates other NOx loss processes and is near saturation with respect to further increases in aerosol surface area concentration. NOx loss due to N2O5 hydrolysis is sensitive to latitude and month due to changes in diurnal photolysis (sharp day-night transitions in winter to continuous sun in spring for the arctic). Near NOx sources, HNO4 is a net sink for NOx; however, for more aged air masses HNO4 is a net source for NOx, largely countering the NOx loss to PAN, N2O5 and HNO3. Overall, HNO4 chemistry impacts the timing of NOx decay and O3 production; however, the cumulative impact on O3 and NOx mixing ratios after a 20-day trajectory is minimal. © 2003 Elsevier Science Ltd. All rights reserved.

Physical and chemical properties of the atmosphere at 0-8 km were measured during the Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiments from February to May 2000 at mid (40°-60°N) and high latitudes (60°-80°N). The observations were analyzed using a diet steady state box model to examine HOx and O3 photochemistry during the spring transition period. The radical chemistry is driven primarily by photolysis of O3 and the subsequent reaction of O(1D) and H2O, the rate of which increases rapidly during spring. Unlike in other tropospheric experiments, observed H2O2 concentrations are a factor of 2-10 lower than those simulated by the model. The required scavenging timescale to reconcile the model overestimates shows a rapid seasonal decrease down to 0.5-1 day in May, which cannot be explained by known mechanisms. This loss of H2O2 implies a large loss of HOx resulting in decreases in O3 production (10-20%) and OH concentrations (20-30%). Photolysis of CH2O, either transported into the region or produced by unknown chemical pathways, appears to provide a significant HOx source at 6-8 km at high latitudes. The rapid increase of in situ O3 production in spring is fueled by concurrent increases of the primary HOx production and NO concentrations. Long-lived reactive nitrogen species continue to accumulate at mid and high latitudes in spring. There is a net loss of NOx to HNO3 and PAN throughout the spring, suggesting that these long-term NOx reservoirs do not provide a net source for NOx in the region. In Situ O3 chemical loss is dominated by the reaction of O3 and HO2, and not that of O(1D) and H2O. At midlatitudes, there is net in situ chemical production Of O3 from February to May. The lower free troposphere (1-4 km) is a region of significant net O3 production. The net production peaks in April coinciding with the observed peak of column O3 (0-8 km). The net in situ O3 production at midlatitudes can explain much of the observed column O3 increase, although it alone cannot explain the observed April maximum. In contrast, there is a net in situ O3 loss from February to April at high latitudes. Only in May is the in situ O3 production larger than loss. The observed continuous increase of column O3 at high latitudes throughout the spring is due to transport from other tropospheric regions or the stratosphere not in situ photochemistry.

Airborne measurements of formaldehyde (CH2O) were acquired employing tunable diode laser absorption spectroscopy (TDLAS) during the 2000 Tropospheric Ozone Production About the Spring Equinox (TOPSE) study. This study consisted of seven deployments spanning the time period from 4 February to 23 May 2000 and covered a wide latitudinal band from 40°N to 85°N. The median measured CH2O concentrations, with a few exceptions, did not show any clear temporal trends from February to May in each of five altitude and three latitude bins examined. Detailed measurement-model comparisons were carried out using a variety of approaches employing two different steady state models. Because recent emissions of CH2O and/or its precursors often result in model underpredictions, background conditions were identified using a number of chemical tracers. For background conditions at temperatures warmer than -45°C, the measurement-model agreement on average ranged between -13% and +5% (measurement- model/measurement), which corresponded to mean and median (measurement- model) differences of 3 ± 69 and -6 parts per trillion by volume (pptv), respectively. At very low temperatures starting at around -45°C, significant and persistent (measurement-model) differences were observed from February to early April from southern Canada to the Arctic Ocean in the 6-8 km altitude range. In such cases, measured CH2O was as much as 392 pptv higher than modeled, and the median difference was 132 pptv (83%). Low light conditions as well as cold temperatures may be important in this effect. A number of possible mechanisms involving the reaction of CH3O2 with HO2 to produce CH2O directly were investigated, but in each case the discrepancy was only minimally reduced. Other possibilities were also considered but in each case there was no compelling evidence to support any of the hypotheses. Whatever the cause, the elevated CH2O concentrations significantly impact upper tropospheric HOx levels at high latitudes (>57°N ) in the February-April time frame.