Browsing by Author "Abad, Gonzalo González"

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    Glyoxal yield from isoprene oxidation and relation to formaldehyde: chemical mechanism, constraints from SENEX aircraft observations, and interpretation of OMI satellite data
    (Copernicus Publications, 2017-07-18) Miller, Christopher Chan; Jacob, Daniel J.; Marais, Eloise A.; Yu, Karen; Travis, Katherine R.; Kim, Patrick S.; Fisher, Jenny A.; Zhu, Lei; Wolfe, Glenn M.; Hanisco, Thomas F.; Keutsch, Frank N.; Kaiser, Jennifer; Min, Kyung-Eun; Brown, Steven S.; Washenfelder, Rebecca A.; Abad, Gonzalo González; Chance, Kelly
    Glyoxal (CHOCHO) is produced in the atmosphere by the oxidation of volatile organic compounds (VOCs). Like formaldehyde (HCHO), another VOC oxidation product, it is measurable from space by solar backscatter. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the SENEX campaign over the southeast US in summer 2013 to better understand the CHOCHO time-dependent yield from isoprene oxidation, its dependence on nitrogen oxides (NOx  ≡  NO + NO₂), the behavior of the CHOCHO–HCHO relationship, the quality of OMI CHOCHO satellite observations, and the implications for using CHOCHO observations from space as constraints on isoprene emissions. We simulate the SENEX and OMI observations with the Goddard Earth Observing System chemical transport model (GEOS-Chem) featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NOx conditions following the isomerization of the isoprene peroxy radical (ISOPO₂). The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NOx conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free-tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free-tropospheric background and show southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the southeast US are tightly correlated and provide redundant proxies of isoprene emissions. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NOx conditions apparent in the SENEX data.
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    High-resolution inversion of OMI formaldehyde columns to quantify isoprene emission on ecosystem-relevant scales: application to the southeast US
    (Copernicus Publications, 2018-04-23) Kaiser, Jennifer; Jacob, Daniel J.; Zhu, Lei; Travis, Katherine R.; Fisher, Jenny A.; Abad, Gonzalo González; Zhang, Lin; Zhang, Xuesong; Fried, Alan; Crounse, John D.; St. Clair, Jason; Wisthaler, Armin
    Isoprene emissions from vegetation have a large effect on atmospheric chemistry and air quality. “Bottom-up” isoprene emission inventories used in atmospheric models are based on limited vegetation information and uncertain land cover data, leading to potentially large errors. Satellite observations of atmospheric formaldehyde (HCHO), a high-yield isoprene oxidation product, provide “top-down” information to evaluate isoprene emission inventories through inverse analyses. Past inverse analyses have however been hampered by uncertainty in the HCHO satellite data, uncertainty in the time- and NOₓ-dependent yield of HCHO from isoprene oxidation, and coarse resolution of the atmospheric models used for the inversion. Here we demonstrate the ability to use HCHO satellite data from OMI in a high-resolution inversion to constrain isoprene emissions on ecosystem-relevant scales. The inversion uses the adjoint of the GEOS-Chem chemical transport model at 0.25° × 0.3125° horizontal resolution to interpret observations over the southeast US in August–September 2013. It takes advantage of concurrent NASA SEAC4RS aircraft observations of isoprene and its oxidation products including HCHO to validate the OMI HCHO data over the region, test the GEOS-Chem isoprene oxidation mechanism and NOₓ environment, and independently evaluate the inversion. This evaluation shows in particular that local model errors in NOₓ concentrations propagate to biases in inferring isoprene emissions from HCHO data. It is thus essential to correct model NOₓ biases, which was done here using SEAC4RS observations but can be done more generally using satellite NO₂ data concurrently with HCHO. We find in our inversion that isoprene emissions from the widely used MEGAN v2.1 inventory are biased high over the southeast US by 40 % on average, although the broad-scale distributions are correct including maximum emissions in Arkansas/Louisiana and high base emission factors in the oak-covered Ozarks of southeast Missouri. A particularly large discrepancy is in the Edwards Plateau of central Texas where MEGAN v2.1 is too high by a factor of 3, possibly reflecting errors in land cover. The lower isoprene emissions inferred from our inversion, when implemented into GEOS-Chem, decrease surface ozone over the southeast US by 1–3 ppb and decrease the isoprene contribution to organic aerosol from 40 to 20 %.
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    Mapping hydroxyl variability throughout the global remote troposphere via synthesis of airborne and satellite formaldehyde observations
    (PNAS, 2019-05-20) Wolfe, Glenn M.; Nicely, Julie M.; St. Clair, Jason; Hanisco, Thomas F.; Liao, Jin; Oman, Luke D.; Brune, William B.; Miller, David; Thames, Alexander; Abad, Gonzalo González; Ryerson, Thomas B.; Thompson, Chelsea R.; Peischl, Jeff; McKain, Kathryn; Sweeney, Colm; Wennberg, Paul O.; Kim, Michelle; Crounse, John D.; Hall, Samuel R.; Ullmann, Kirk; Diskin, Glenn; Bui, Paul; Chang, Cecilia; Dean-Day, Jonathan
    The hydroxyl radical (OH) fuels tropospheric ozone production and governs the lifetime of methane and many other gases. Existing methods to quantify global OH are limited to annual and global-to-hemispheric averages. Finer resolution is essential for isolating model deficiencies and building process-level understanding. In situ observations from the Atmospheric Tomography (ATom) mission demonstrate that remote tropospheric OH is tightly coupled to the production and loss of formaldehyde (HCHO), a major hydrocarbon oxidation product. Synthesis of this relationship with satellite-based HCHO retrievals and model-derived HCHO loss frequencies yields a map of total-column OH abundance throughout the remote troposphere (up to 70% of tropospheric mass) over the first two ATom missions (August 2016 and February 2017). This dataset offers unique insights on near-global oxidizing capacity. OH exhibits significant seasonality within individual hemispheres, but the domain mean concentration is nearly identical for both seasons (1.03 ± 0.25 × 10⁶ cm⁻³), and the biseasonal average North/South Hemisphere ratio is 0.89 ± 0.06, consistent with a balance of OH sources and sinks across the remote troposphere. Regional phenomena are also highlighted, such as a 10-fold OH depression in the Tropical West Pacific and enhancements in the East Pacific and South Atlantic. This method is complementary to budget-based global OH constraints and can help elucidate the spatial and temporal variability of OH production and methane loss
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    Nitrogen dioxide and formaldehyde measurements from the GEOstationary Coastal and Air Pollution Events (GEO-CAPE) Airborne Simulator over Houston, Texas
    (EGU, 2018-10-30) Nowlan, Caroline R.; Liu, Xiong; Janz, Scott J.; Kowalewski, Matthew G.; Chance, Kelly; Follette-Cook, Melanie B.; Fried, Alan; Abad, Gonzalo González; Herman, Jay; Judd, Laura M.; Kwon, Hyeong-Ahn; Loughner, Christopher P.; Pickering, Kenneth E.; Richter, Dirk; Spinei, Elena; Walega, James; Weibring, Petter; Weinheimer, Andrew J.
    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 %.
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    Observing atmospheric formaldehyde (HCHO) from space: validation and intercomparison of six retrievals from four satellites (OMI, GOME2A, GOME2B, OMPS) with SEAC4RS aircraft observations over the southeast US
    (EGU Publications, 2016-11-01) Zhu, Lei; Jacob, Daniel J.; Kim, Patrick S.; Fisher, Jenny A.; Yu, Karen; Travis, Katherine R.; Mickley, Loretta J.; Yantosca, Robert M.; Sulprizio, Melissa P.; Smedt, Isabelle De; Abad, Gonzalo González; Chance, Kelly; Li, Can; Ferrare, Richard; Fried, Alan; Hair, Johnathan W.; Hanisco, Thomas F.; Richter, Dirk; Scarino, Amy Jo; Walega, James; Weibring, Petter; Wolfe, Glenn M.
    Formaldehyde (HCHO) column data from satellites are widely used as a proxy for emissions of volatile organic compounds (VOCs), but validation of the data has been extremely limited. Here we use highly accurate HCHO aircraft observations from the NASA SEAC4RS (Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys) campaign over the southeast US in August–September 2013 to validate and intercompare six retrievals of HCHO columns from four different satellite instruments (OMI, GOME2A, GOME2B and OMPS; for clarification of these and other abbreviations used in the paper, please refer to Appendix A) and three different research groups. The GEOS-Chem chemical transport model is used as a common intercomparison platform. All retrievals feature a HCHO maximum over Arkansas and Louisiana, consistent with the aircraft observations and reflecting high emissions of biogenic isoprene. The retrievals are also interconsistent in their spatial variability over the southeast US (r  =  0.4–0.8 on a 0.5°  ×  0.5°  grid) and in their day-to-day variability (r  =  0.5–0.8). However, all retrievals are biased low in the mean by 20–51 %, which would lead to corresponding bias in estimates of isoprene emissions from the satellite data. The smallest bias is for OMI-BIRA, which has high corrected slant columns relative to the other retrievals and low scattering weights in its air mass factor (AMF) calculation. OMI-BIRA has systematic error in its assumed vertical HCHO shape profiles for the AMF calculation, and correcting this would eliminate its bias relative to the SEAC4RS data. Our results support the use of satellite HCHO data as a quantitative proxy for isoprene emission after correction of the low mean bias. There is no evident pattern in the bias, suggesting that a uniform correction factor may be applied to the data until better understanding is achieved.
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    Revisiting the effectiveness of HCHO/NO₂ ratios for inferring ozone sensitivity to its precursors using high resolution airborne remote sensing observations in a high ozone episode during the KORUS-AQ campaign
    (Elsevier, 2020-02-12) Souri, Amir H.; Nowlan, Caroline R.; Wolfe, Glenn; Lamsal, Lok N.; Chan Miller, Christopher E.; Abad, Gonzalo González; Janz, Scott J.; Fried, Alan; Blake, Donald R.; Weinheimer, Andrew J.; Diskin, Glenn S.; Liu, Xiong; Chance, Kelly
    The nonlinear chemical processes involved in ozone production (P(O3₃) have necessitated using proxy indicators to convey information about the primary dependence of P(O₃) on volatile organic compounds (VOCs) or nitrogen oxides (NOₓ). In particular, the ratio of remotely sensed columns of formaldehyde (HCHO) to nitrogen dioxide (NO₂) has been widely used for studying O₃ sensitivity. Previous studies found that the errors in retrievals and the incoherent relationship between the column and the near-surface concentrations are a barrier in applying the ratio in a robust way. In addition to these obstacles, we provide calculational-observational evidence, using an ensemble of 0-D photochemical box models constrained by DC-8 aircraft measurements on an ozone event during the Korea-United States Air Quality (KORUS-AQ) campaign over Seoul, to demonstrate the chemical feedback of NO₂ on the formation of HCHO is a controlling factor for the transition line between NOₓ-sensitive and NOₓ-saturated regimes. A fixed value (~2.7) of the ratio of the chemical loss of NOₓ (LNOₓ) to the chemical loss of HO₂+RO₂ (LROₓ) perceptibly differentiates the regimes. Following this value, data points with a ratio of HCHO/NO₂ less than 1 can be safely classified as NOₓ-saturated regime, whereas points with ratios between 1 and 4 fall into one or the other regime. We attribute this mainly to the HCHO-NO₂ chemical relationship causing the transition line to occur at larger (smaller) HCHO/NO₂ ratios in VOC-rich (VOC-poor) environments. We then redefine the transition line to LNOₓ/LROₓ~2.7 that accounts for the HCHO-NO₂ chemical relationship leading to HCHO = 3.7 × (NO₂ – 1.14 × 10¹⁶ molec.cm⁻²). Although the revised formula is locally calibrated (i.e., requires for readjustment for other regions), its mathematical format removes the need for having a wide range of thresholds used in HCHO/NO₂ ratios that is a result of the chemical feedback. Therefore, to be able to properly take the chemical feedback into consideration, the use of HCHO = a × (NO₂ – b) formula should be preferred to the ratio in future works. We then use the Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument to study O₃ sensitivity in Seoul. The unprecedented spatial (250 × 250 m²) and temporal (~every 2 h) resolutions of HCHO and NO₂ observations form the sensor enhance our understanding of P(O₃) in Seoul; rather than providing a crude label for the entire city, more in-depth variabilities in chemical regimes are observed that should be able to inform mitigation strategies correspondingly.
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    Source and variability of formaldehyde (HCHO) at northern high latitude: an integrated satellite, aircraft, and model study
    (Copernicus Publications, 2022-06-03) Zhao, Tianlang; Mao, Jingqiu; Simpson, William R.; Smedt, Isabelle De; Zhu, Lei; Hanisco, Thomas F.; Wolfe, Glenn; Clair, Jason St.; Abad, Gonzalo González; Nowlan, Caroline R.; Barletta, Barbara; Meinardi, Simone; Blake, Donald R.; Apel, Eric C.; Hornbrook, Rebecca S.
    Here we use satellite observations of HCHO vertical column densities (VCD) from the TROPOspheric Monitoring Instrument (TROPOMI), ground-based and aircraft measurements, combined with a nested regional chemical transport model (GEOS-Chem at 0.5° × 0.625° resolution), to understand the variability and sources of summertime HCHO better in Alaska. We first evaluate GEOS-Chem with in-situ airborne measurements during Atmospheric Tomography Mission 1 (ATom-1) aircraft campaign and ground-based measurements from Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS). We show reasonable agreement between observed and modeled HCHO, isoprene and monoterpenes. In particular, HCHO profiles show spatial homogeneity in Alaska, suggesting a minor contribution of biogenic emissions to HCHO VCD. We further examine the TROPOMI HCHO product in Alaska during boreal summer, which is in good agreement with GEOS-Chem model results. We find that HCHO VCDs are dominated by free-tropospheric background in wildfire-free regions. During the summer of 2018, the model suggests that the background HCHO column, resulting from methane oxidation, contributes to 66–80 % of the HCHO VCD, while wildfires contribute to 14 % and biogenic VOC contributes to 5–9 % respectively. For the summer of 2019, which had intense wildfires, the model suggests that wildfires contribute to 40 to 65 %, and the background column accounts for 30 to 50 % of HCHO VCD in June and July. In particular, the model indicates a major contribution of wildfires from direct emissions of HCHO, instead of secondary production of HCHO from oxidation of larger VOCs. We find that the column contributed by biogenic VOC is often small and below the TROPOMI detection limit. The source and variability of HCHO VCD above Alaska during summer is mainly driven by background methane oxidation and wildfires. This work discusses challenges for quantifying HCHO and its precursors in remote pristine regions.
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    Towards a satellite formaldehyde – in situ hybrid estimate for organic aerosol abundance
    (Copernicus Publications, 2019-03-04) Liao, Jin; Hanisco, Thomas F.; Wolfe, Glenn M.; St. Clair, Jason; Jimenez, Jose L.; Campuzano-Jost, Pedro; Nault, Benjamin A.; Fried, Alan; Marais, Eloise A.; Abad, Gonzalo González; Chance, Kelly; Jethva, Hiren T.; Ryerson, Thomas B.; Warneke, Carsten; Wisthaler, Armin
    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 SEAC4RS and DC3), biomass burning (NASA SEAC4RS), 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.
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    Validation of satellite formaldehyde (HCHO) retrievals using observations from 12 aircraft campaigns
    (Copernicus Publications, 2020-10-29) Zhu, Lei; Abad, Gonzalo González; Nowlan, Caroline R.; Miller, Christopher Chan; Chance, Kelly; Apel, Eric C.; DiGangi, Joshua P.; Fried, Alan; Hanisco, Thomas F.; Hornbrook, Rebecca S.; Hu, Lu; Kaiser, Jennifer; Keutsch, Frank N.; Permar, Wade; St. Clair, Jason; Wolfe, Glenn
    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.