Search

In this study, the WRF-Chem v4.4 model was utilized to evaluate the sensitivity of O 3 simulations with three bottom-up emission inventories (EDGAR-HTAP v2 and v3 and KORUS v5) using surface and aircraft data in East Asia during the Korea-United States Air Quality (KORUS-AQ) campaign period in 2016. All emission inventories were found to reproduce the diurnal variations of O 3 and its main precursor NO 2 as compared to the surface monitor data. However, the spatial distributions of the daily maximum 8 h average (MDA8) O 3 in the model do not completely align with the observations. The model MDA8 O 3 had a negative (positive) bias north (south) of 30° N over China. All simulations underestimated the observed CO by 50 %–60 % over China and South Korea. In the Seoul Metropolitan Area (SMA), EDGAR-HTAP v2 and v3 and KORUS v5 simulated the vertical shapes and diurnal patterns of O 3 and other precursors effectively, but the model underestimated the observed O 3 , CO, and HCHO concentrations. Notably, the model aromatic volatile organic compounds (VOCs) were significantly underestimated with the three bottom-up emission inventories, although the KORUS v5 shows improvements. The model isoprene estimations had a positive bias relative to the observations, suggesting that the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.04 overestimated isoprene emissions. Additional model simulations were conducted by doubling CO and VOC emissions over China and South Korea to investigate the causes of the model O 3 biases and the effects of the long-range transport on the O 3 over South Korea. The doubled CO and VOC emission simulations improved the model O 3 simulations for the local-emission-dominant case but led to the model O 3 overestimations for the transport-dominant case, which emphasizes the need for accurate representations of the local VOC emissions over South Korea. [ABSTRACT FROM AUTHOR]

In this study, the WRF-Chem v4.4 model was utilized to evaluate three bottom-up emission inventories (EDGAR-HTAP v2, v3, and KORUS v5) using surface and aircraft data in East Asia during the Korea-United States Air Quality (KORUS-AQ) campaign period in 2016. All emission inventories were found to reproduce the diurnal variations of O3 and NO2 as compared to the surface monitor data. However, the spatial distributions of the daily maximum 8-hour average (MDA8) O3 in the model do not completely align with the observations. The model MDA8 O3 had a negative (positive) bias north (south) of 30°N over China. All simulations underestimated the observed CO by 50-60% over China and South Korea. In the Seoul Metropolitan Area (SMA), EDGAR-HTAP v2, v3, and KORUS v5 simulated the vertical shapes and diurnal patterns of O3 and other precursors effectively, but the model underestimated the observed O3, CO and HCHO concentrations. Notably, the model aromatic VOCs were significantly underestimated with the three bottom-up emission inventories, although the KORUS v5 shows improvements. The model isoprene estimations had a positive bias relative to the observations, suggesting that the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.04 overestimated isoprene emissions. Additional model simulations were conducted by doubling CO and VOC emissions over China and South Korea to investigate the causes of the model O3 biases and the effects of the long-range transport on the O3 over South Korea. The doubled CO and VOC emission simulations improved the model O3 simulations for the local emission dominant case, but led to the model O3 overestimations for the transport dominant case, which emphasizes the need for accurate representations of the local VOC emissions over South Korea. [ABSTRACT FROM AUTHOR]

Here we use satellite observations of formaldehyde (HCHO) vertical column densities (VCD) from the TROPOspheric Monitoring Instrument (TROPOMI), aircraft measurements, combined with a nested regional chemical transport model (GEOS-Chem at 0.5×0.625∘ resolution), to better understand the variability and sources of summertime HCHO in Alaska. We first evaluate GEOS-Chem with in-situ airborne measurements during the Atmospheric Tomography Mission 1 (ATom-1) aircraft campaign. We show reasonable agreement between observed and modeled HCHO, isoprene, monoterpenes and the sum of methyl vinyl ketone and methacrolein (MVK + MACR) in the continental boundary layer. 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 in summer, reprocessed by GEOS-Chem model output for a priori profiles and shape factors. For years with low wildfire activity (e.g., 2018), we find that HCHO VCDs are largely dominated by background HCHO (58 %–71 %), with minor contributions from wildfires (20 %–32 %) and biogenic VOC emissions (8 %–10 %). For years with intense wildfires (e.g., 2019), summertime HCHO VCD is dominated by wildfire emissions (50 %–72 %), with minor contributions from background (22 %–41 %) and biogenic VOCs (6 %–10 %). 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, in part due to the slow HCHO production from isoprene oxidation under low NO x conditions. This work highlights challenges for quantifying HCHO and its precursors in remote pristine regions. [ABSTRACT FROM AUTHOR]

The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime, influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although the calculated OH reactivity was below the limit of detection for the ATom instrument used to measure OH reactivity throughout much of the free troposphere, the instrument was able to measure the OH reactivity in and just above the marine boundary layer. The mean measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom deployments was 1.9 s -1 , which is 0.5 s -1 larger than the mean calculated OH reactivity. The missing OH reactivity, the difference between the measured and calculated OH reactivity, varied between 0 and 3.5 s -1 , with the highest values over the Northern Hemisphere Pacific Ocean. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions. [ABSTRACT FROM AUTHOR]

Satellite-based measurements of the column CH2O/NO2 ratio have previously been used to estimate near-surface ozone (O3) sensitivity (i.e., NO x 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-NO x interactions (referred to as LRO x/LNO x) provides a good indicator of maximum O3 production along NO x 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. [ABSTRACT FROM AUTHOR]

The nonlinear chemical processes involved in ozone production (P(O 3)) have necessitated using proxy indicators to convey information about the primary dependence of P(O 3) on volatile organic compounds (VOCs) or nitrogen oxides (NO x). In particular, the ratio of remotely sensed columns of formaldehyde (HCHO) to nitrogen dioxide (NO 2) has been widely used for studying O 3 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 NO 2 on the formation of HCHO is a controlling factor for the transition line between NO x -sensitive and NO x -saturated regimes. A fixed value (~2.7) of the ratio of the chemical loss of NO x (LNO x) to the chemical loss of HO 2 +RO 2 (LRO x) perceptibly differentiates the regimes. Following this value, data points with a ratio of HCHO/NO 2 less than 1 can be safely classified as NO x -saturated regime, whereas points with ratios between 1 and 4 fall into one or the other regime. We attribute this mainly to the HCHO-NO 2 chemical relationship causing the transition line to occur at larger (smaller) HCHO/NO 2 ratios in VOC-rich (VOC-poor) environments. We then redefine the transition line to LNO x /LRO x ~2.7 that accounts for the HCHO-NO 2 chemical relationship leading to HCHO = 3.7 × (NO 2 – 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/NO 2 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 × (NO 2 – 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 O 3 sensitivity in Seoul. The unprecedented spatial (250 × 250 m2) and temporal (~every 2 h) resolutions of HCHO and NO 2 observations form the sensor enhance our understanding of P(O 3) 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. • Ozone sensitivity over Seoul on an exceptionally degraded air quality day. • Various thresholds for HCHO/NO 2 should be defined to label chemical regimes. • The inherent dependence of HCHO production on NO x levels complicates the ratio. • We redesign the formula to reflect the chemical feedback of NO x on HCHO. • GeoTASO provides in-depth variabilities in chemical regimes over Seoul. [ABSTRACT FROM AUTHOR]