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The fraction of urban volatile organic compounds (VOC) emissions attributable to fossil fuel combustion has been declining in many parts of the world, resulting in a need to better constrain other anthropogenic sources of these emissions. During the National Institute of Environmental Research (NIER) and National Aeronautics and Space Administration (NASA) Korea-United States Air Quality (KORUS-AQ) field study in Seoul, South Korea during May–June 2016, air quality models underestimated ozone, formaldehyde, and peroxyacetyl nitrate (PAN) indicating an underestimate of VOCs in the emissions inventory. Here, we use aircraft observations interpreted with the GEOS-Chem chemical transport model to assess the need for increases in VOC emissions. We find that the largest increases are attributable to compounds associated with volatile chemical products, liquefied petroleum gas (LPG) and natural gas emissions, and long-range transport. Revising model chemistry to better match observed VOC speciation together with increasing model emissions of underestimated VOC species increased calculated OH reactivity by +2 s-1 and ozone production by 2 ppb hr-1. Ozone increased by 6 ppb below 2 km and 9 ppb at the surface, and formaldehyde and acetaldehyde increased by 30 % and 120 % aloft, respectively, all in better agreement with observations. The larger increase in acetaldehyde was attributed to ethanol emissions which we found to be as important for ozone production as isoprene or alkenes. The increased acetaldehyde largely resolved the model PAN bias. The need for additional unmeasured VOCs however was indicated by a remaining model bias of -1 ppb in formaldehyde and 57 % and 52 % underestimate in higher peroxynitrates (PNs) and alkyl nitrates (ANs), respectively. We added additional chemistry to the model to represent an additional six PNs from observed VOCs but were unable to account for the majority of missing PNs. However, four of these PNs were modeled at concentrations similar to other commonly measured PNs (>2 % of PAN) indicating that these should be measured in future campaigns. We hypothesize that emissions of oxygenated VOCs (OVOCs) such as >C5 aldehydes from cooking and/or alkenes associated with volatile chemical products could produce both PNs and ANs and improve remaining model biases. Emerging research on the emissions and chemistry of these species will soon allow for modeling of their impact on local and regional photochemistry. [ABSTRACT FROM AUTHOR]

Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured on board the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2, with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NO y) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO 2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of - 296 ± 51 g kg -1 , consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per parts per million by volume (ppmv) of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO 2 , NO y , and black carbon than with CO. More than half of the NO y in fresh plumes is NO 2 with an R2 of 0.95 and a ratio of NO 2 to NO y of 0.55 ± 0.05 ppbv ppbv -1 , highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NO y to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol. [ABSTRACT FROM AUTHOR]

Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen-species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured onboard the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2 with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NOy) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of -296 ± 51 g kg-1, consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per ppmv of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO2, NOy, and black carbon than with CO. More than half of the NOy in fresh plumes is NO2 with an R2 of 0.95 and a ratio of NO2 to NOy of 0.55 ± 0.05 ppbv ppbv-1, highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NOy to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol. [ABSTRACT FROM AUTHOR]

The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO 2) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO 2 + RO 2 (LROx) to the chemical loss of NO x (LNOx). Subsequently, we challenge the predictive power of HCHO/NO2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LROx/LNOx. FNRs show a strongly linear (R2=0.94) relationship with LROx/LNOx , but only on the logarithmic scale. Following the baseline (i.e., ln(LROx/LNOx) = - 1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NOx -sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the ROx – HOx cycle. We calculate high ozone production rates (PO 3) dominated by large HCHO × NO 2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO 3 and HCHO × NO 2 becomes more pronounced when moving towards NOx -sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO 2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO 2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km 2). A pixel with a grid size of 216 km 2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO 2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO 2 columns, should be above 1.2–1.5 × 10 16 molec. cm -2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric. [ABSTRACT FROM AUTHOR]

Large wildfires influence regional atmospheric composition, but chemical complexity challenges model predictions of downwind impacts. Here, we elucidate key connections within gas-phase photochemistry and assess novel chemical processes via a case study of the 2013 California Rim Fire plume. Airborne in situ observations, acquired during the NASA Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC 4 RS) mission, illustrate the evolution of volatile organic compounds (VOCs), oxidants, and reactive nitrogen over 12 h of atmospheric aging. Measurements show rapid formation of ozone and peroxyacyl nitrates (PNs), sustained peroxide production, and prolonged enhancements in oxygenated VOCs and nitrogen oxides (NO x). Observations and Lagrangian trajectories constrain a 0-D puff model that approximates plume photochemical history and provides a framework for evaluating process interactions. Simulations examine the effects of (1) previously unmeasured reactive VOCs identified in recent laboratory studies and (2) emissions and secondary production of nitrous acid (HONO). Inclusion of estimated unmeasured VOCs leads to a 250 % increase in OH reactivity and a 70 % increase in radical production via oxygenated VOC photolysis. HONO amplifies radical cycling and serves as a downwind NO x source, although impacts depend on how HONO is introduced. The addition of initial HONO (representing primary emissions) or particulate nitrate photolysis amplifies ozone production, while heterogeneous conversion of NO 2 suppresses ozone formation. Analysis of radical initiation rates suggests that oxygenated VOC photolysis is a major radical source, exceeding HONO photolysis when averaged over the first 2 h of aging. Ozone production chemistry transitions from VOC sensitive to NO x sensitive within the first hour of plume aging, with both peroxide and organic nitrate formation contributing significantly to radical termination. To simulate smoke plume chemistry accurately, models should simultaneously account for the full reactive VOC pool and all relevant oxidant sources. [ABSTRACT FROM AUTHOR]

Formaldehyde (HCHO) has been measured from space for more than 2 decades. Owing to its short atmospheric lifetime, satellite HCHO data are used widely as a proxy of volatile organic compounds (VOCs; please refer to Appendix A for abbreviations and acronyms), providing constraints on underlying emissions and chemistry. However, satellite HCHO products from different satellite sensors using different algorithms have received little validation so far. The accuracy and consistency of HCHO retrievals remain largely unclear. Here we develop a validation platform for satellite HCHO retrievals using in situ observations from 12 aircraft campaigns with a chemical transport model (GEOS-Chem) as the intercomparison method. Application to the NASA operational OMI HCHO product indicates negative biases (-44.5 % to -21.7 %) under high-HCHO conditions, while it indicates high biases (+66.1 % to +112.1 %) under low-HCHO conditions. Under both conditions, HCHO a priori vertical profiles are likely not the main driver of the biases. By providing quick assessment of systematic biases in satellite products over large domains, the platform facilitates, in an iterative process, optimization of retrieval settings and the minimization of retrieval biases. It is also complementary to localized validation efforts based on ground observations and aircraft spirals. [ABSTRACT FROM AUTHOR]

Organic aerosol (OA) is one of the main components of the global particulate burden and intimately links natural and anthropogenic emissions with air quality and climate. It is challenging to accurately represent OA in global models. Direct quantification of global OA abundance is not possible with current remote sensing technology; however, it may be possible to exploit correlations of OA with remotely observable quantities to infer OA spatiotemporal distributions. In particular, formaldehyde (HCHO) and OA share common sources via both primary emissions and secondary production from oxidation of volatile organic compounds (VOCs). Here, we examine OA–HCHO correlations using data from summertime airborne campaigns investigating biogenic (NASA SEAC 4 RS and DC3), biomass burning (NASA SEAC 4 RS), and anthropogenic conditions (NOAA CalNex and NASA KORUS-AQ). In situ OA correlates well with HCHO (r=0.59 –0.97), and the slope and intercept of this relationship depend on the chemical regime. For biogenic and anthropogenic regions, the OA–HCHO slopes are higher in low NOx conditions, because HCHO yields are lower and aerosol yields are likely higher. The OA–HCHO slope of wildfires is over 9 times higher than that for biogenic and anthropogenic sources. The OA–HCHO slope is higher for highly polluted anthropogenic sources (e.g., KORUS-AQ) than less polluted (e.g., CalNex) anthropogenic sources. Near-surface OAs over the continental US are estimated by combining the observed in situ relationships with HCHO column retrievals from NASA's Ozone Monitoring Instrument (OMI). HCHO vertical profiles used in OA estimates are from climatology a priori profiles in the OMI HCHO retrieval or output of specific period from a newer version of GEOS-Chem. Our OA estimates compare well with US EPA IMPROVE data obtained over summer months (e.g., slope =0.60 –0.62, r=0.56 for August 2013), with correlation performance comparable to intensively validated GEOS-Chem (e.g., slope =0.57 , r=0.56) with IMPROVE OA and superior to the satellite-derived total aerosol extinction (r=0.41) with IMPROVE OA. This indicates that OA estimates are not very sensitive to these HCHO vertical profiles and that a priori profiles from OMI HCHO retrieval have a similar performance to that of the newer model version in estimating OA. Improving the detection limit of satellite HCHO and expanding in situ airborne HCHO and OA coverage in future missions will improve the quality and spatiotemporal coverage of our OA estimates, potentially enabling constraints on global OA distribution. [ABSTRACT FROM AUTHOR]

The GEOstationary Coastal and Air Pollution Events (GEO-CAPE) Airborne Simulator (GCAS) was developed in support of NASA's decadal survey GEO-CAPE geostationary satellite mission. GCAS is an airborne push-broom remote-sensing instrument, consisting of two channels which make hyperspectral measurements in the ultraviolet/visible (optimized for air quality observations) and the visible–near infrared (optimized for ocean color observations). The GCAS instrument participated in its first intensive field campaign during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign in Texas in September 2013. During this campaign, the instrument flew on a King Air B-200 aircraft during 21 flights on 11 days to make air quality observations over Houston, Texas. We present GCAS trace gas retrievals of nitrogen dioxide (NO2) and formaldehyde (CH2O), and compare these results with trace gas columns derived from coincident in situ profile measurements of NO2 and CH2O made by instruments on a P-3B aircraft, and with NO2 observations from ground-based Pandora spectrometers operating in direct-sun and scattered light modes. GCAS tropospheric column measurements correlate well spatially and temporally with columns estimated from the P-3B measurements for both NO2 (r2=0.89) and CH2O (r2=0.54) and with Pandora direct-sun (r2=0.85) and scattered light (r2=0.94) observed NO2 columns. Coincident GCAS columns agree in magnitude with NO2 and CH2O P-3B-observed columns to within 10 % but are larger than scattered light Pandora tropospheric NO2 columns by 33 % and direct-sun Pandora NO2 columns by 50 %. [ABSTRACT FROM AUTHOR]

An instrumented NASA P-3B aircraft was used for airborne sampling of trace gases in a plume that had emanated from a small forest understory fire in Georgia, USA. The plume was sampled at its origin to derive emission factors and followed ~13.6 km downwind to observe chemical changes during the first hour of atmospheric aging. The P-3B payload included a proton-transfer-reaction timeof- flight mass spectrometer (PTR-ToF-MS), which measured non-methane organic gases (NMOGs) at unprecedented spatiotemporal resolution (10m spatial / 0.1 s temporal). Quantitative emission data are reported for CO2, CO, NO, NO2, HONO, NH3, and 16NMOGs (formaldehyde, methanol, acetonitrile, propene, acetaldehyde, formic acid, acetone plus its isomer propanal, acetic acid plus its isomer glycolaldehyde, furan, isoprene plus isomeric pentadienes and cyclopentene, methyl vinyl ketone plus its isomers crotonaldehyde and methacrolein, methylglyoxal, hydroxy acetone plus its isomers methyl acetate and propionic acid, benzene, 2,3-butanedione, and 2-furfural) with molar emission ratios relative to CO larger than 1 ppbV ppmV-1. Formaldehyde, acetaldehyde, 2-furfural, and methanol dominated NMOG emissions. No NMOGs with more than 10 carbon atoms were observed at mixing ratios larger than 50 pptV ppmV-1 CO. Downwind plume chemistry was investigated using the observations and a 0-D photochemical box model simulation. The model was run on a nearly explicit chemical mechanism (MCM v3.3) and initialized with measured emission data. Ozone formation during the first hour of atmospheric aging was well captured by the model, with carbonyls (formaldehyde, acetaldehyde, 2,3-butanedione, methylglyoxal, 2-furfural) in addition to CO and CH4 being the main drivers of peroxy radical chemistry. The model also accurately reproduced the sequestration of NOx into peroxyacetyl nitrate (PAN) and the OH-initiated degradation of furan and 2-furfural at an average OH concentration of 7.45±1.07 106 cm-3 in the plume. Formaldehyde, acetone/propanal, acetic acid/glycolaldehyde, and maleic acid/maleic anhydride (tentatively identified) were found to be the main NMOGs to increase during 1 h of atmospheric plume processing, with the model being unable to capture the observed increase. A mass balance analysis suggests that about 50% of the aerosol mass formed in the downwind plume is organic in nature. [ABSTRACT FROM AUTHOR]

We quantify both the spatial and temporal variability of column integrated O 3 , NO 2 , CO, SO 2 , and HCHO over the Baltimore/Washington, DC area using output from the Weather Research and Forecasting model with on-line chemistry (WRF/Chem) for the entire month of July 2011, coinciding with the first deployment of the NASA Earth Venture program mission Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ). Using structure function analyses, we find that the model reproduces the spatial variability observed during the campaign reasonably well, especially for O 3 . The Tropospheric Emissions: Monitoring of Pollution (TEMPO) instrument will be the first NASA mission to make atmospheric composition observations from geostationary orbit and partially fulfills the goals of the Geostationary Coastal and Air Pollution Events (GEO-CAPE) mission. We relate the simulated variability to the precision requirements defined by the science traceability matrices of these space-borne missions. Results for O 3 from 0 to 2 km altitude indicate that the TEMPO instrument would be able to observe O 3 air quality events over the Mid-Atlantic area, even on days when the violations of the air quality standard are not widespread. The results further indicated that horizontal gradients in CO from 0 to 2 km would be observable over moderate distances (≥20 km). The spatial and temporal results for tropospheric column NO 2 indicate that TEMPO would be able to observe not only the large urban plumes at times of peak production, but also the weaker gradients between rush hours. This suggests that the proposed spatial and temporal resolutions for these satellites as well as their prospective precision requirements are sufficient to answer the science questions they are tasked to address. [ABSTRACT FROM AUTHOR]