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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Adaptation of an In Situ Ground-Based Tropospheric OH/HO2 Instrument for Aircraft Use

In-situ HO(x) (OH and HO2) measurements are an essential part of understanding the photochemistry of aircraft exhaust in the atmosphere. HO(x) affects the partitioning of nitrogen species in the NO(y) family. Its reactions are important sources and sinks for tropospheric ozone, thus providing a link between the NO(x) in aircraft exhaust and tropospheric ozone. OH mixing ratios are enhanced in aircraft wakes due to the photolysis of the HONO that is made close to the engine. Measurements of HO(x) in aircraft wakes, along with NO(x) measurements, thus provides a constraint on chemical models of the engine combustion and exhaust. The development of the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) is reported. We designed, developed, and successfully flew this instrument. It was part of the instrument complement on board the NASA DC-8 during SUCCESS, which took place in Kansas in April and May, 1996. ATHOS has a limit-of-detection for OH (S/N = 2) of 10(exp 5) OH molecules cm(exp -3) in less than 150 seconds. While this sensitivity is about 2-3 times less than the initial projections in the proposal, it is more than adequate for good measurements of OH and HO2 from the planetary boundary layer to the stratosphere. Our participation in SUCCESS was to be engineering test flights for ATHOS; however, the high-quality measurements we obtained are being used to study HO(x) photochemistry in contrails, clouds, and the clear air.

Brune, William H.↗
NASA NTRS1998

Atmospherically Related Studies of O(D-1) and O2 (b'Sigma(sub g, sup +)

For the third year of the grant, we propose to investigate the (beta)'(Sigma)(sub g, sup +). Our earlier value of 0.77 +/- 0.23, which has been used for a long time, should be updated, and the error limits reduced. Current measurements in J. Barker's group at the University of Michigan have assigned a value closer to 0.9, and we will conduct a new evaluation. The goals of this project are to investigate various aspects of the photochemistry of O('D) and O2(beta)'(Sigma)(sub g, sup +) that are of relevance to the photochemistry and energy balance of the terrestrial atmosphere. Over the last six months, we have obtained new sky spectra data files from the Keck telescope via Don Osterbrock at UC Santa Cruz, and now 120 hours of data have been accumulated. Thus, we have been able to make large signal/noise improvements of the O2(b'(Sigma)(sub g, sup +) - X(sup 3)(Sigma)(Sub g, sup -) Atmospheric Band data that we are collecting.

Slanger, Tom G.↗
NASA NTRS1998

Contrast Between 1992 and 1997 High Latitude Spring Haloe Observations of Lower Stratospheric HCl

HCl measurements from HALOE in the northern hemisphere during mid-May 1997 revealed vortex fragments in which the chlorine reservoir partitioning was strongly pushed toward HCl (approx. 90% HCl, approx. 10% ClONO2), similar to partitioning previously observed in the Antarctic vortex region. In contrast, observations of ClONO2 and HCl in the northern polar spring, 1992, and in other years, show these species established the balance typical for gas phase photochemical reactions in this region (approx. 60% HCl, approx. 40% ClONO2). Annually, chlorine reservoirs in the winter lower stratosphere polar vortex are converted to chlorine radicals via heterogeneous reactions on particle surfaces at very cold temperatures (less than about 200 K). As temperatures warm in spring, the heterogeneous processes become insignificant compared with gas phase reactions, and the chlorine reservoirs are reformed. Measurements through the northern winter/spring in 1992 show rapid formation of ClONO2, followed by steady loss of ClONO2 and increasing HCl. Although ClONO2 measurements are not available for 1997, the HCl increase in 1997 is observed to be much more rapid and the eventual HCl mixing ratio is about 50% greater than that of 1992. The observations are examined through comparison with the Goddard three-dimensional chemistry and transport model. This model utilizes winds and temperatures from the Goddard Earth Observing System Data Assimilation System and a complete integration scheme for stratospheric photochemistry. Analysis of the evolution of HCl and ClONO2 shows that the observed difference in the overall rate of HCl formation is explained by the sensitivity of the gas-phase chemistry to the ozone mixing ratio and the temperature. The results show that the model accurately simulates HCl and ClONO2 evolution during these two winters. Model validity is further supported by comparisons with O3 and reactive nitrogen species NO and NO2. This analysis provides a sensitive test of the lower stratospheric chlorine photochemistry, particularly because the analysis considers constituent evolution at a time when the HCl and ClONO2 are far from a photochemical stationary state.

Douglass, A. R.↗
NASA NTRS1998

EOS Interdisciplinary Investigation: Observational and Modeling Studies of Radiative, Chemical, and Dynamical Interactions in the Earth's Atmosphere

A 3-dimensional model of atmospheric dynamics and photochemistry has been developed from the primitive equations in isentropic coordinates. The model extends from the upper troposphere through the middle atmosphere and is driven by observed dynamical and chemical structure in the troposphere. The model's formulation is entirely spectral: Horizontal structure is represented in terms of vector Hough functions, which explicitly partition the motion into its rotational and divergent components. This formulation enables the model's computational performance to be increased dramatically by filtering high-frequency gravity waves, which do not affect PV conservation. Vertical structure is represented in terms of eigenfunctions that follow from the primitive equations in isentropic coordinates. The model's fully spectral formulation enables scale-selective dissipation, necessary for numerical stability, to be applied at 6th order-in all 3 coordinate directions. This feature leaves all but the shortest vertical scales undamped and, consequently, allows potential vorticity and chemical tracers to be conserved quite accurately, distinctly better than in the model's layered counterpart. These dynamical features are complemented by a basic but fairly complete treatment of gas phase photochemistry, which accounts for some 48 chemical species, diurnally-varying SW absorption by O2 and O3, and LW cooling calculated via a detailed band calculation of radiative transfer. Driven by observed tropospheric structure, the 3D model reproduces observed structure in the middle atmosphere, inclusive of transport by the Brewer-Dobson circulation and accompanying chemical variations. Calculated residual motion is consistent with diabatic cooling rates, poleward transport, and descent in the polar night derived from satellite measurements of chemical tracers made from LIMS, SAGE, and UARS. The model also reproduces the observed structure of chemical species like O3, HNO3, and ClO. At the same time, it provides a respectable 3D simulation of the wintertime increase of midlatitude total ozone, as well as its geographical structure observed by Nimbus-7 TOMS. The 3D model has been used to explore the origin of diabatic upwelling in the tropical lower stratosphere, which has been related to planetary wave absorption in the winter- time stratosphere, as well as to influences from tropospheric convection at the tropical tropopause.

Salby, Murry L.↗
NASA NTRS1997

Modeling and Data Analysis of SONEX Observations

Primary focus of the study is on the sources, photochemistry and transport of reactive nitrogen species, O3, as well as other O3 precursors such as NMHC and CO. Major objectives are: (1) Identify the major sources of NO(x) and quantify the contribution of each source to the NO(x) distribution in the free troposphere, particularly in the upper troposphere. (2) Understand the odd hydrogen photochemistry and the recycling of NO(x) in the free troposphere. (3) Evaluate the photochemical production and destruction of O3. A combination of modeling and data analysis/interpretation approach is used. We use a three-dimensional model and a box model to simulate, analyze, and interpret the observations. Both models are needed because they are complementary and each has its advantages and limitations. Proven analytical techniques, including correlation of NOx with various tracers and with different air masses, are applied to both observations and model results to deduce useful information toward accomplishing the objectives. In addition, the SONEX observations are compared and analyzed in a systematic way against other airborne experiments conducted over remote atmosphere, especially those from NASA GTE experiments, AASE 1 and 2, and SUCCESS.

Liu, Shaw C.↗
NASA NTRS2001

The NO(x)-HNO3 System in the Lower Stratosphere: Insights from In Situ Measurements and Implications of the J(HNO3)-[OH] Relationship

During the 1997 Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, simultaneous in situ observations of NOx and HOx radicals, their precursors, and the radiation field were obtained in the lower stratosphere. We use these observations to evaluate the primary mechanisms that control NOx-HNO3 exchange and to understand their control over the partitioning between NO2 and HNO3 in regions of continuous sunlight. We calculate NOx production (PNOx) and loss (LNOx) in a manner directly constrained by the in situ measurements and current rate constant recommendations, using approaches for representing albedo, overhead O3 and [OH] that reduce model uncertainty. We find a consistent discrepancy of 18% between modeled rates of NOx production and loss (LNOx = 1.18P(sub NOx)), which is within the measurement uncertainty of +/- 27%. The partitioning between NOx production processes is [HNO3 + OH (41 +/- 2)%; HNO3 + hv (59 +/- 2)%] and between NOx loss processes is [NO2 + OH, 90% to >97%; BrONO2 + H2O, 10% to <3%]. The steady-state description of NOx-HNO3 exchange reveals the significant influence of the tight correlation between the photolysis rate of HNO3 and [OH] established by in situ measurements throughout the lower stratosphere. Parametrizing this relationship, we find: (1) the steady-state value of [NO2](sub 24h-avg)/[HNO3] in the continuously sunlit, lower stratosphere is a function only of temperature and number density; and (2) the partitioning of NOx production between HNO3 + OH and HNO3 + hv is nearly constant throughout most of the lower stratosphere. We describe a methodology (functions of latitude, day, temperature, and pressure) for accurately predicting the steady-state value of [NO2](sub 24h-avg)/[HNO3] and the partitioning of NOx production within these regions. The results establish a metric to compare observations of [NO2](sub 24h-avg)/[HNO3] within the continuously sunlit region and provide a simple diagnostic for evaluating the accuracy of models that attempt to describe the coupled NOx-HOx photochemistry in the lower stratosphere.

Perkins, K. K.↗
NASA NTRS2003

Photochemical Studies of Chemistry in the Outer Solar System

The goal of the proposed science investigation is to gain a quantitative understanding of chemical processes and their coupling with atmospheric dynamics in the reducing atmospheres of the outer solar system, with a particular focus on Infrared Space Observatory (ISO) observations and future experiments such as the Cassini Mission to Saturn and Titan. The proposed work is divided into two related tasks. We have carried out a systematic comparison between atmospheric models for every giant planet and Titan, which employ a consistent set of photochemical reactions. Combined with recent observations of hydrocarbon species by ISO, this can provide the most rigorous test of our current understanding of the photochemistry of hydrocarbon in the outer solar system. The emphasis will be on the methyl radical (CH3), first detected by IS0 in the atmospheres of Saturn and Neptune (Bezard et al. 1998). CH3 is one of the most important radicals in the hydrocarbon photochemistry because it is the primary product of methane photolysis and plays an essential role in forming C2H6, the most abundant and stable C2 species. A fundamental understanding of the distribution of CH3 provides unique insights into the chemistry of hydrocarbons as well as comparative planetology.

Yung, Yuk L.↗
NASA NTRS2008

Mars Ozone Absorption Line Shapes from Infrared Heterodyne Spectra Applied to GCM-Predicted Ozone Profiles and to MEX/SPICAM Column Retrievals

We present the application of infrared heterodyne line shapes of ozone on Mars to those produced by radiative transfer modeling of ozone profiles predicted by general circulation models (GCM), and to contemporaneous column abundances measured by Mars Express SPICAM. Ozone is an important tracer of photochemistry Mars' atmosphere, serving as an observable with which to test predictions of photochemistry-coupled GCMs. Infrared heterodyne spectroscopy at 9.5 microns with spectral resolving power >1,000,000 is the only technique that can directly measure fully-resolved line shapes of Martian ozone features from the surface of the Earth. Measurements were made with Goddard Space Flight Center's Heterodyne instrument for Planetary Wind And Composition (HIPWAC) at the NASA Infrared Telescope Facility (IRTF) on Mauna Kea, Hawaii on February 21-24 2008 UT at Ls=35deg on or near the MEX orbital path. The HIPWAC observations were used to test GCM predictions. For example, a GCM-generated ozone profile for 60degN 112degW was scaled so that a radiative transfer calculation of its absorption line shape matched an observed HIPWAC absorption feature at the same areographic position, local time, and season. The RMS deviation of the model from the data was slightly smaller for the GCM-generated profile than for a line shape produced by a constant-with-height profile, even though the total column abundances were the same, showing potential for testing and constraining GCM ozone-profiles. The resulting ozone column abundance from matching the model to the HIPWAC line shape was 60% higher than that observed by SPICAM at the same areographic position one day earlier and 2.5 hours earlier in local time. This could be due to day-to-day, diurnal, or north polar region variability, or to measurement sensitivity to the ozone column and its distribution, and these possibilities will be explored. This work was supported by NASA's Planetary Astronomy Program.

Fast, Kelly E.↗
NASA NTRS2008

Probing the Distribution of Ozone on Mars

We present the application of infrared heterodyne line shapes of ozone on Mars to those produced by radiative transfer modeling of ozone profiles predicted by photochemistry-coupled general circulation models (GCM), and to contemporaneous column abundances measured by Mars Express SPICAM. Ozone is an important tracer of photochemistry in Mars' atmosphere, serving as an observable with which to test predictions of photochemical models. Infrared heterodyne measurements of ozone absorption features on Mars have been obtained at various Martian seasons from 1988 until present at the NASA Infrared Telescope Facility (IRTF) on Mauna Kea, Hawai'i [I]. The NASAiGoddard Space Flight Center spectrometers used were the Infrared Heterodyne Spectrometer (IRHS) [2, 3] and, since 2003, the Heterodyne Instrument for Planetary Wind and Composition (HIPWAC) [4]. A description the infrared heterodyne technique applied to ground-base observations of Martian ozone can be found in [I]. The most recent measurements on February 21-24 2008 UT at Ls=35deg were made by HIPWAC on or near the Mars Express orbital path with the goal of acquiring spectra that can be directly compared to nadir observations by SPICAM.

Fast, K. E.↗
NASA NTRS2009

Comparison of HIPWAC and Mars Express SPICAM Observations of Ozone on Mars 2006-2008 and Variation from 1993 IRHS Observations

Ozone is a tracer of photochemistry in the atmosphere of Mars and an observable used to test predictions of photochemical models. We present a comparison of retrieved ozone abundances on Mars using ground-based infrared heterodyne measurements by NASA Goddard Space Flight Center's Heterodyne Instrument for Planetary Wind And Composition (HIPWAC) and space-based Mars Express Spectroscopy for the Investigation of the Characteristics of the Atmosphere of Mars (SPICAM) ultraviolet measurements. Ozone retrievals from simultaneous measurements in February 2008 were very consistent (0.8 microns-atm), as were measurements made close in time (ranging from less than 1 to greater than 8 microns-atm) during this period and during opportunities in October 2006 and February 2007. The consistency of retrievals from the two different observational techniques supports combining the measurements for testing photochemistry-coupled general circulation models and for investigating variability over the long-term between spacecraft missions. Quantitative comparison with ground-based measurements by NASA'GSFC's Infrared Heterodyne Spectrometer (IRHS) in 1993 reveals 2-4 times more ozone at low latitudes than in 2008 at the same season, and such variability was not evident over the shorter period of the Mars Express mission. This variability may be due to cloud activity.

Fast, Kelly E.↗
NASA NTRS2008

An Overview of the NASA Spring/Summer 2008 Arctic Campaign - ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites)

ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) is a major NASA led airborne field campaign being performed in the spring and summer of 2008 at high latitudes (http://cloud1.arc.nasa.gov/arctas/). ARCTAS is a part of the International Polar Year program and its activities are closely coordinated with multiple U. S. (NOAA, DOE), Canadian, and European partners. Observational data from an ensemble of aircraft, surface, and satellite sensors are closely integrated with models of atmospheric chemistry and transport in this experiment. Principal NASA airborne platforms include a DC-8 for detailed atmospheric composition studies, a P-3 that focuses on aerosols and radiation, and a B-200 that is dedicated to remote sensing of aerosols. Satellite validation is a central activity in all these platforms and is mainly focused on CALIPSO, Aura, and Aqua satellites. Major ARCTAS themes are: (1) Long-range transport of pollution to the Arctic including arctic haze, tropospheric ozone, and persistent pollutants such as mercury; (2) Boreal forest fires and their implications for atmospheric composition and climate; (3) Aerosol radiative forcing from arctic haze, boreal fires, surface-deposited black carbon, and other perturbations; and (4) Chemical processes with focus on ozone, aerosols, mercury, and halogens. The spring deployment (April) is presently underway and is targeting plumes of anthropogenic and biomass burning pollution and dust from Asia and North America, arctic haze, stratosphere-troposphere exchange, and ozone photochemistry involving HOx and halogen radicals. The summer deployment (July) will target boreal forest fires and summertime photochemistry. The ARCTAS mission is providing a critical link to enhance the value of NASA satellite observations for Earth science. In this talk we will discuss the implementation of this campaign and some preliminary results.

Jacob, Daniel J.↗
NASA NTRS2011

Sulfur Chemistry in the Early and Present Atmosphere of Mars

Atmospheric sulfur species resulting from volcanic emissions impact the composition and chemistry of the atmosphere, impact the climate, and hence, the habitability of Mars and impact the mineralogy and composition of the surface of Mars. The geochemical/ photochemical cycling of sulfur species between the interior (via volcanism), the atmosphere (atmospheric photochemical and chemical processes) and the deposition of sulfuric acid on the surface of Mars is an important, but as yet poorly understood geochemical/ photochemical cycle on Mars. There is no observational evidence to indicate that Mars is volcanically active at the present time, however, there is strong evidence that volcanism was an important and widespread process on early Mars. The chemistry and photochemistry of sulfur species in the early and present atmosphere of Mars will be assessed using a one-dimensional photochemical model. Since it is generally assumed that the atmosphere of early Mars was significantly denser than the present 6-millibar atmosphere, photochemical calculations were performed for the present atmosphere and for the atmosphere of early Mars with assumed surface pressures of 60 and 350-millibars, where higher surface pressure resulted from enhanced atmospheric concentrations of carbon dioxide (CO2). The following sections include the results of earlier modeling studies, a summary of the one-dimensional photochemical model used in this study, a summary of the photochemistry and chemistry of sulfur species in the atmosphere of Mars and some of the results of the calculations.

Levine, Joel S.↗
NASA NTRS2016

The Effects of Consistent Chemical Kinetics Calculations on the Pressure-Temperature Profiles and Emission Spectra of Hot Jupiters

In this work we investigate the impact of calculating non-equilibrium chemical abundances consistently with the temperature structure for the atmospheres of highly-irradiated, close-in gas giant exoplanets. Chemical kinetics models have been widely used in the literature to investigate the chemical compositions of hot Jupiter atmospheres which are expected to be driven away from chemical equilibrium via processes such as vertical mixing and photochemistry. All of these models have so far used pressure-temperature (P-T) profiles as fixed model input. This results in a decoupling of the chemistry from the radiative and thermal properties of the atmosphere, despite the fact that in nature they are intricately linked. We use a one-dimensional radiative-convective equilibrium model, ATMO, which includes a sophisticated chemistry scheme to calculate P-T profiles which are fully consistent with non-equilibrium chemical abundances, including vertical mixing and photochemistry. Our primary conclusion is that, in cases of strong chemical disequilibrium, consistent calculations can lead to differences in the P-T profile of up to 100 K compared to the P-T profile derived assuming chemical equilibrium. This temperature change can, in turn, have important consequences for the chemical abundances themselves as well as for the simulated emission spectra. In particular, we find that performing the chemical kinetics calculation consistently can reduce the overall impact of non-equilibrium chemistry on the observable emission spectrum of hot Jupiters. Simulated observations derived from non-consistent models could thus yield the wrong interpretation. We show that this behaviour is due to the non-consistent models violating the energy budget balance of the atmosphere.

planets and satellites↗
NASA NTRS2017

Organic Haze as a Biosignature in Anoxic Earth-Like Atmospheres

Early Earth may have hosted a biologically mediated global organic haze during the Archean eon (3.8-2.5 billion years ago). This haze would have significantly impacted multiple aspects of our planet, including its potential for habitability and its spectral appearance. Here, we model worlds with Archean-like levels of carbon dioxide orbiting the ancient Sun and anM4Vdwarf (GJ 876) and show that organic haze formation requires methane fluxes consistent with estimated Earth-like biological production rates. On planets with high fluxes of biogenic organic sulfur gases (CS2, OCS, CH3SH, and CH3SCH3), photochemistry involving these gases can drive haze formation at lower CH4/CO2 ratios than methane photochemistry alone. For a planet orbiting the Sun, at 30x the modern organic sulfur gas flux, haze forms at a CH4/CO2 ratio 20% lower than at 1x the modern organic sulfur flux. For a planet orbiting the M4V star, the impact of organic sulfur gases is more pronounced: at 1x the modern Earth organic sulfur flux, a substantial haze forms at CH4/CO2 approx. 0.2, but at 30x the organic sulfur flux, the CH4/CO2 ratio needed to form haze decreases by a full order of magnitude. Detection of haze at an anomalously low CH4/ CO2 ratio could suggest the influence of these biogenic sulfur gases and therefore imply biological activity on an exoplanet. When these organic sulfur gases are not readily detectable in the spectrum of an Earth-like exoplanet, the thick organic haze they can help produce creates a very strong absorption feature at UV-blue wavelengths detectable in reflected light at a spectral resolution as low as 10. In direct imaging, constraining CH4 and CO2 concentrations will require higher spectral resolution, and R > 170 is needed to accurately resolve the structure of the CO2 feature at 1.57 microns, likely the most accessible CO2 feature on an Archean-like exoplanet.

Arney, Giada↗
NASA NTRS2019

Earth's Early Reduced Atmospheres

Earth’s early atmosphere evolved in response to cosmic impacts, photochemistry generated by the copious extreme ultraviolet radiation emitted by the young Sun, hydrogen escape, mineral redox buffering, the evolution of iron in the mantle, and the character of crustal weathering and subduction. No single chemical composition, surface pressure, or temperature was typical. After the biggest impacts the temperature likely rose above 3000 K and the atmosphere held rock vapor. As the atmosphere cooled its constituents rained out: first the silicates, then the geochemical volatiles (such as salt), and last the water. Depending on the size of the impact, cooling took thousands to millions of years. Between impacts the atmosphere was thick with gases like CO2, H2, and CH4 that do not condense at Earth but provide greenhouse warming that could easily have maintained surface temperatures in excess of 500 K. At some point the early atmosphere must have been conducive to the evolution of organic chemistry and the origin of life. It was therefore --- at times --- dominated by reduced gases like hydrogen and methane. Hydrogen-methane atmospheres are easily formed thermochemically after major impacts if H2O and CO2 were present on Earth in quantities consistent with their inventories on Earth today – the key is high pressure. Hydrogen-methane atmospheres slowly break down over millions of years by hydrogen escape and photochemistry. At first methane decomposes into tars and nitriles that precipitate, but later as the atmosphere grows more oxidized from hydrogen escape the methane oxidizes to CO and CO2, with a small fraction going to HCN. Impacts can also produce NH3 directly from N2 and H2O, which is expected to rain out with the H2O. As impacts grew infrequent the climate cooled in response to the fixing of CO2 as carbonate and carbonate subduction. Eventually the CO2 was mostly removed to the mantle and the surface mostly frozen.

Zahnle, Kevin↗
NASA NTRSDate not supplied

Validation of the Aeroplanets Model in a Present-Day Earth Simulation

We present a validation of the Aeroplanets/Aerochemistry model (Gronoff et al. 2012; Airapetian et al. 2016), a one-dimensional photochemistry model, with another one-dimensional photochemistry model implemented in Hu et al. 2016. Results from a simulation of the atmosphere of present-day Earth from both models were used in the validation. Realistic initial conditions and concentrations were used in the validation, including surface emissions of CO, CH4, NH3, N2O, NO, SO2, OCS, H2S, and H2SO4. As part of the validation, we compare the vertical profile of concentration of key chemical species, including O3, N2O, NO, NO2, HNO3, HO2, OH, and CH4. Our model was able to create vertical concentration profiles of these species that closely matched the results from Hu et al. 2016. With the successful validation, we plan to use the Aeroplanets model to explore the role of ions and aerosols, formed the interaction of solar energetic particles and the atmosphere of early Earth, in generating key greenhouse gas species and gas species that support the formation of molecules crucial for life.

Bradley Michael Hegyi↗
NASA NTRS2020

Global-scale distribution of ozone in the remote troposphere from ATom and HIPPO airborne field missions

Ozone is a key constituent of the troposphere, where it drives photochemical processes, impacts air quality, and acts as a climate forcer. Large-scale in situ observations of ozone commensurate with the grid resolution of current Earth system models are necessary to validate model outputs and satellite retrievals. In this paper, we examine measurements from the Atmospheric Tomography (ATom; four deployments in 2016–2018) and the HIAPER Pole-to-Pole Observations (HIPPO; five deployments in 2009–2011) experiments, two global-scale airborne campaigns covering the Pacific and Atlantic basins. ATom and HIPPO represent the first global-scale, vertically resolved measurements of O3 distributions throughout the troposphere, with HIPPO sampling the atmosphere over the Pacific and ATom sampling both the Pacific and Atlantic. Given the relatively limited temporal resolution of these two campaigns, we first compare ATom and HIPPO ozone data to longer-term observational records to establish the representativeness of our dataset. We show that these two airborne campaigns captured on average 53 %, 54 %, and 38 % of the ozone variability in the marine boundary layer, free troposphere, and upper troposphere–lower stratosphere (UTLS), respectively, at nine well-established ozonesonde sites. Additionally, ATom captured the most frequent ozone concentrations measured by regular commercial aircraft flights in the northern Atlantic UTLS. We then use the repeated vertical profiles from these two campaigns to confirm and extend the existing knowledge of tropospheric ozone spatial and vertical distributions throughout the remote troposphere. We highlight a clear hemispheric gradient, with greater ozone in the Northern Hemisphere, consistent with greater precursor emissions and consistent with previous modeling and satellite studies. We also show that the ozone distribution below 8 km was similar in the extra-tropics of the Atlantic and Pacific basins, likely due to zonal circulation patterns. However, twice as much ozone was found in the tropical Atlantic as in the tropical Pacific, due to well-documented dynamical patterns transporting continental air masses over the Atlantic. Finally, we show that the seasonal variability of tropospheric ozone over the Pacific and the Atlantic basins is driven year-round by transported continental plumes and photochemistry, and the vertical distribution is driven by photochemistry and mixing with stratospheric air. This new dataset provides additional constraints for global climate and chemistry models to improve our understanding of both ozone production and loss processes in remote regions, as well as the influence of anthropogenic emissions on baseline ozone.

ATom, aircraft profiles, Atlantic pollution, ozone↗
NASA NTRS2019

Integration of Airborne and Ground Observations of Nitryl Chloride in the Seoul Metropolitan Area and the Implications on Regional Oxidation Capacity During KORUS-AQ 2016

Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2on regional photochemistry in the Seoul metropolitan area (SMA) during the Korea–United States Air Quality Study (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested suburban region, respectively. Positive correlations between daytime Cl2 and ClNO2 were observed at both sites, the slope of which was dependent on O3 levels. The possible mechanisms are explored through box model simulations constrained with observations. The overall diurnal variations in ClNO2 at both sites appeared similar but the night-time variations were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were observed throughout the night at the TRF site. Significant levels of ClNO2 were observed at both sites for 4–5 h after sunrise. Airborne observations, box model calculations, and back-trajectory analysis consistently show that these high levels of ClNO2 in the morning are likely from vertical or horizontal transport of air masses from the west. Box model results show that chlorine-radical-initiated chemistry can impact the regional photochemistry by elevating net chemical production rates of ozone by ∼25 % in the morning.

Nitryl chloride (ClNO2)↗