Search

The NASA Atmospheric Tomography (ATom) mission built a photochemical climatology of air parcels based on in situ measurements with the NASA DC-8 aircraft along objectively planned profiling transects through the middle of the Pacific and Atlantic oceans. In this paper we present and analyze a data set of 10s (2km) merged and gap-filled observations of the key reactive species driving the chemical budgets of O3 and CH4 (O3, CH4, CO, H2O, HCHO, H2O2, CH3OOH, C2H6, higher alkanes, alkenes, aromatics, NOx, HNO3, HNO4, peroxyacetyl nitrate, and other organic nitrates), consisting of 146494 distinct air parcels from ATom deployments 1 through 4. Six models calculated the O3 and CH4 photochemical tendencies from this modeling data stream for ATom 1. We find that 80%-90% of the total reactivity lies in the top 50% of the parcels and 25%-35% in the top 10%, supporting previous model-only studies that tropospheric chemistry is driven by a fraction of all the air. Surprisingly, the probability densities of species and reactivities averaged on a model scale (100 km) differ only slightly from the 2km ATom 10s data, indicating that much of the heterogeneity in tropospheric chemistry can be captured with current global chemistry models. Comparing the ATom reactivities over the tropical oceans with climatological statistics from six global chemistry models, we find generally good agreement with the reactivity rates for O3 and CH4. Models distinctly underestimate O3 production below 2km relative to the mid-troposphere, and this can be traced to lower NOx levels than observed. Attaching photochemical reactivities to measurements of chemical species allows for a richer, yet more constrained-to-what-matters, set of metrics for model evaluation. This paper presents a corrected version of the paper published under the same authors and title (sans "corrected") as 10.5194/acp-21-13729-2021.

The NASA Atmospheric Tomography (ATom) mission built a photochemical climatology of air parcels based on in situ measurements with the NASA DC-8 aircraft along objectively planned profiling transects through the middle of the Pacific and Atlantic oceans. In this paper we present and analyze a data set of 10s (2km) merged and gap-filled observations of the key reactive species driving the chemical budgets of O3 and CH4 (O3, CH4, CO, H2O, HCHO, H2O2, CH3OOH, C2H6, higher alkanes, alkenes, aromatics, NOx, HNO3, HNO4, peroxyacetyl nitrate, other organic nitrates), consisting of 146494 distinct air parcels from ATom deployments 1 through 4. Six models calculated the O3 and CH4 photochemical tendencies from this modeling data stream for ATom 1. We find that 80%-90% of the total reactivity lies in the top 50% of the parcels and 25%-35% in the top 10%, supporting previous model-only studies that tropospheric chemistry is driven by a fraction of all the air. In other words, accurate simulation of the least reactive 50% of the troposphere is unimportant for global budgets. Surprisingly, the probability densities of species and reactivities averaged on a model scale (100km) differ only slightly from the 2km ATom data, indicating that much of the heterogeneity in tropospheric chemistry can be captured with current global chemistry models. Comparing the ATom reactivities over the tropical oceans with climatological statistics from six global chemistry models, we find excellent agreement with the loss of O3 and CH4 but sharp disagreement with production of O3. The models sharply underestimate O3 production below 4km in both Pacific and Atlantic basins, and this can be traced to lower NOx levels than observed. Attaching photochemical reactivities to measurements of chemical species allows for a richer, yet more constrained-to-what-matters, set of metrics for model evaluation.

We report airborne measurements of acetaldehyde (CH3CHO) during the first and second deployments of the National Aeronautics and Space Administration (NASA) Atmospheric Tomography Mission (ATom). The budget of CH3CHO is examined using the Community Atmospheric Model with chemistry (CAM-chem), with a newly-developed online air-sea exchange module. The upper limit of the global ocean net emission of CH3CHO is estimated to be 34 Tg a-1 (42 Tg a-1 if considering bubble-mediated transfer), and the ocean impacts on tropospheric CH3CHO are mostly confined to the marine boundary layer. Our analysis suggests that there is an unaccounted CH3CHO source in the remote troposphere and that organic aerosols can only provide a fraction of this missing source. We propose that peroxyacetic acid (PAA) is an ideal indicator of the rapid CH3CHO production in the remote troposphere. The higher-than-expected CH3CHO measurements represent a missing sink of hydroxyl radicals (and halogen radical) in current chemistry-climate models.

Hydration of the stratosphere by tropopause‐overshooting convection has received increasing interest due to the extreme concentrations of water vapor that can result and, ultimately, the climate warming potential such hydration provides. Previous work has recognized the importance of numerous dynamic and physical processes that control stratospheric water vapor delivery by convection. This study leverages recent comprehensive observations from the NASA Dynamics and Chemistry of the Summer Stratosphere (DCOTSS) field campaign to determine the frequency at which each process operates during real events. Specifically, a well‐established analysis technique known as tracer‐tracer correlation is applied to DCOTSS observations of ozone, water vapor, and potential temperature to identify the occurrence of known processes. It is found that approximately half of convectively‐driven stratospheric hydration samples show no indication of significant air mass transport and mixing, emphasizing the importance of ice sublimation to stratospheric water vapor delivery. Furthermore, the temperature of the upper troposphere and lower stratosphere environment and/or overshoot appears to be a commonly active constraint, since the approximate maximum possible water vapor concentration that can be reached in an air mass is limited to the saturation mixing ratio when ice is present. Finally, little evidence of relationships between dynamic and physical processes and their spatial distribution was found, implying that stratospheric water vapor delivery by convection is likely facilitated by a complex collection of processes in each overshooting event. Plain Language Summary: Thunderstorms are capable of transporting air and water up to the second layer of Earth's atmosphere, the stratosphere. Resulting irreversible modifications to greenhouse gases that regulate climate, such as water vapor and ozone, are important to quantify and poorly understood. This study uses recently‐obtained aircraft observations to improve understanding of irreversible transport in thunderstorms and the environmental and storm factors that control it. By examining how multiple trace gases and other quantities co‐vary, it is found that half of observed stratospheric changes by thunderstorms only exhibit increases in water vapor, which is argued to be driven by transported ice. It is also found that the environmental temperature is an important constraint in any storm because it limits the amount of stratospheric water vapor change that can occur. Key Points: Recent airborne observations reveal key dynamic and physical processes controlling the stratospheric delivery of water vapor by convectionIn situ observations suggest that water vapor is delivered routinely via both air transport and ice sublimationTemperature is an important constraint for water vapor delivery in any stratospheric environment [ABSTRACT FROM AUTHOR]

As part of the Pandonia Global Network (PGN), Pandora spectrometers are widely deployed around the world. These ground-based, remote-sensing instruments are federated such that they employ a common algorithm and data protocol for reporting on trace gas column densities and lower atmospheric profiles using two modes based on direct-sun and sky-scan observations. To aid users in the analysis of Pandora observations, the PGN standard quality assurance procedure assigns flags to the data indicating high, medium, and low quality. This work assesses the suitability of these data quality flags for filtering data in the scientific analysis of nitrogen dioxide (NO2) and formaldehyde (HCHO), two critical precursors controlling tropospheric ozone production. Pandora data flagged as high quality assures scientifically valid data and is often more abundant for direct-sun NO2 columns. For direct-sun HCHO and sky-scan observations of both molecules, large amounts of data flagged as low quality also appear to be valid. Upon closer inspection of the data, independent uncertainty is shown to be a better indicator of data quality than the standard quality flags. After applying an independent uncertainty filter, Pandora data flagged as medium or low quality in both modes can be demonstrated to be scientifically useful. Demonstrating the utility of this filtering method is enabled by correlating contemporaneous but independent direct-sun and sky-scan observations. When evaluated across 15 Pandora sites in North America, this new filtering method increased the availability of scientifically useful data by as much as 90 % above that tagged as high quality. A method is also developed for combining the direct-sun and sky-scan observations into a single dataset by accounting for biases between the two observing modes and differences in measurement integration times. This combined data provides a more continuous record useful for interpreting Pandora observations against other independent variables such as hourly observations of surface ozone. When Pandora HCHO columns are correlated with surface ozone measurements, data filtered by independent uncertainty exhibits similarly strong and more robust relationships than high-quality data alone. These results suggest that Pandora data users should carefully assess data across all quality flags and consider their potential for useful application to scientific analysis. The present study provides a method for maximizing use of Pandora data with expectation of more robust satellite validation and comparisons with ground-based observations in support of air quality studies. [ABSTRACT FROM AUTHOR]

Tropopause-overshooting convection in the midlatitudes provides a rapid transport pathway for air from the lower troposphere to reach the upper troposphere and lower stratosphere (UTLS) and can result in the formation of above-anvil cirrus plumes (AACPs) that significantly hydrate the stratosphere. Such UTLS composition changes alter the radiation budget and impact climate. Novel in situ observations from the NASA Dynamics and Chemistry of the Summer Stratosphere (DCOTSS) field campaign are used in this study to examine UTLS impacts from AACP-generating overshooting convection. Namely, a research flight on 31 May 2022 sampled active convection over the state of Oklahoma for more than 3 h with the NASA ER-2 high-altitude research aircraft. An AACP was bisected during this flight, providing the first such extensive in situ sampling of this phenomenon. The convective observations reveal pronounced changes in air mass composition and stratospheric hydration up to altitudes of 2.3 km above the tropopause and concentrations more than double background levels. Unique dynamic and trace gas signatures were found within the AACP, including enhanced vertical mixing near the AACP edge and a positive correlation between water vapor and ozone. Moreover, the water vapor enhancement within the AACP was found to be limited to the saturation mixing ratio of the low temperature overshoot and AACP air. Comparison with all remaining DCOTSS flights demonstrates that the 31 May 2022 flight had some of the largest tropospheric tracer and water vapor perturbations in the stratosphere and within the AACP. [ABSTRACT FROM AUTHOR]

Deep convective clouds are critically important to the distribution of atmospheric constituents throughout the troposphere but are difficult environments to study. The Deep Convective Clouds and Chemistry (DC3) study in 2012 provided the environment, platforms, and instrumentation to test oxidation chemistry around deep convective clouds and their impacts downwind. Measurements on the NASA DC-8 aircraft included those of the radicals hydroxyl (OH) and hydroperoxyl (HO2), OH reactivity, and more than 100 other chemical species and atmospheric properties. OH, HO2, and OH reactivity were compared to photochemical models, some with and some without simplified heterogeneous chemistry, to test the understanding of atmospheric oxidation as encoded in the model. In general, the agreement between the observed and modeled OH, HO2, and OH reactivity was within the combined uncertainties for the model without heterogeneous chemistry and the model including heterogeneous chemistry with small OH and HO2 uptake consistent with laboratory studies. This agreement is generally independent of the altitude, ozone photolysis rate, nitric oxide and ozone abundances, modeled OH reactivity, and aerosol and ice surface area. For a sunrise to midday flight downwind of a nighttime mesoscale convective system, the observed ozone increase is consistent with the calculated ozone production rate. Even with some observed-to-modeled discrepancies, these results provide evidence that a current measurement-constrained photochemical model can simulate observed atmospheric oxidation processes to within combined uncertainties, even around convective clouds. For this DC3 study, reduction in the combined uncertainties would be needed to confidently unmask errors or omissions in the model chemical mechanism.

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total nonmethane organic compounds, and PM1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM1 emission estimate (1530 ± 570 Gg yr-1) is over 3 times that of the NEI PM2.5 estimate and is also higher thanthe PM2.5 emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions.

The Portable (2.7 kg) Cavity-enhanced Absorption of Nitrogen Dioxide (PCAND) instrument for measuring in situ nitrogen dioxide (NO2) was developed using incoherent, broadband cavity-enhanced absorption spectroscopy (IBBCEAS). An LED light source centered at 408 nm was coupled to a cavity 15 cm in length, achieving an effective optical pathlength of ~520 m. Our precision was measured as 94 pptv (1 s). To date, we have flown this instrument on 3 balloon and 1 UAV test flights. This instrument records data to an SD card and outputs data (via an RS232 port) to external devices including a commercial radiosonde (iMet) for real-time data downlink. [ABSTRACT FROM AUTHOR]

Formaldehyde (HCHO) in the atmosphere is an intermediate product from the oxidation of methane and non-methane volatile organic compounds. In remote marine regions, HCHO variability is closely related to atmospheric oxidation capacity and modeled HCHO in these regions is usually added as a global satellite HCHO background. Thus, it is important to understand and validate the levels of satellite HCHO over the remote oceans. Here we intercompare three satellite retrievals of total HCHO columns (OMI-SAO (v004), OMPS-NPP SAO, and OMI BIRA) and validate them against in situ observations from the NASA Atmospheric Tomography Mission (ATom) mission. All retrievals are correlated with ATom integrated columns over remote oceans, with OMI SAO (v004) showing the best agreement. Three satellite HCHO retrievals and in situ ATom columns all generally captured the spatial and seasonal distributions of HCHO in the remote ocean atmosphere. Retrieval bias varies by latitude and season, but a persistent low bias is found in all products at high latitudes and the general low bias is most severe for the OMI BIRA product. Examination of retrieval components reveals slant column corrections have a larger impact on the retrievals over remote marine regions while AMFs play a smaller role. This study informs that the potential latitude-dependent biases in the retrievals require further investigation for improvement and should be considered when using marine HCHO satellite data, and vertical profiles from in situ instruments are crucial for validating satellite retrievals. [ABSTRACT FROM AUTHOR]

Tropopause-overshooting convection in the midlatitudes provides a rapid transport pathway for air from the lower troposphere to reach the upper troposphere and lower stratosphere (UTLS), and can result in the formation of above-anvil cirrus plumes (AACPs) that significantly hydrate the stratosphere. Such UTLS composition changes alter the radiation budget and impact climate. Novel in situ observations from the NASA Dynamics and Chemistry of the Summer Stratosphere (DCOTSS) field campaign are used in this study to examine UTLS impacts from AACP-generating overshooting convection. Namely, a research flight on 31 May 2022 sampled active convection over the state of Oklahoma for more than three hours with the NASA ER-2 high-altitude research aircraft. An AACP was bisected during this flight, providing the first such extensive in situ sampling of this phenomenon. The convective observations reveal pronounced changes in air mass composition and stratospheric hydration up to altitudes of 2.3 km above the tropopause and concentrations more than double background levels. Unique dynamic and trace gas signatures were found within the AACP, including enhanced vertical mixing near the AACP edge and a positive correlation between water vapor and ozone. Moreover, the water vapor enhancement within the AACP was found to be limited to the saturation mixing ratio of the low temperature overshoot and AACP air. Comparison with all remaining DCOTSS flights demonstrates that the 31 May 2022 flight had some of the largest tropospheric tracer and water vapor perturbations in the stratosphere and within the AACP. [ABSTRACT FROM AUTHOR]

The Geostationary Environmental Monitoring Spectrometer (GEMS) is a UV-visible spectrometer onboard the GEO-KOMPSAT-2B satellite launched into geostationary orbit in February 2020. To evaluate GEMS NO2 column data, comparison was carried out using NO2 vertical column density (VCD) measured using direct-sunlight observations by the Pandora spectrometer system at four sites in Seosan, South Korea, during November 2020 to January 2021. Correlation coefficients between GEMS and Pandora NO2 data at four sites ranged from 0.35 to 0.48, with root mean square errors (RMSEs) from 4.7 × 1015 molec. cm-2 to 5.5 × 1015 molec. cm-2 for cloud fraction (CF) < 0.7. Higher correlation coefficients of 0.62-0.78 with lower RMSEs from 3.3 × 1015 molec. cm-2 to 4.3 × 1015 molec. cm-2 were found with CF < 0.3, indicating the higher sensitivity of GEMS to atmospheric NO2 in less-cloudy conditions. Overall, GEMS NO2 column data tend to be lower than those of Pandora due to differences in representative spatial coverage, with a large negative bias under high-CF conditions. With correction for horizontal representativeness in Pandora measurement coverage, the correlation coefficients range from 0.69 to 0.81 with RMSEs from 3.2 × 1015 molec. cm-2 to 4.9 × 1015 molec. cm-2 were achieved for CF < 0.3, showing the better correlation with the correction than that without the correction. [ABSTRACT FROM AUTHOR]