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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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NASA NTRS2001

Characterizing the Influence of the General Circulation on Marine Boundary Layer Clouds

The seasonal and intraseasonal variability of boundary layer cloud in the subtropical eastern oceans are studied using combined data from the International Satellite Cloud Climatology Project (ISCCP) and the European Centre for Medium-Range Weather Forecasts (ECMWF) reanalysis. Spectral analysis reveals that most of the time variability of cloud properties occurs on seasonal to annual time scales. The variance decreases one to two orders of magnitude for each decade of time scale decrease, indicating that daily to monthly time scales have smaller, but non-negligible variability. The length of these dominant time scales suggests that the majority of the variability is influenced by the general circulation and its interaction with boundary layer turbulence, rather than a product of boundary layer turbulence alone. Previous datasets have lacked the necessary resolution in either time or in space to properly characterize variability on synoptic scales; this is remedied by using global satellite-retrieved cloud properties. We characterize the intraseasonal subtropical cloud variability in both hemispheres and in different seasons. In addition to cloud fraction, we examine variability of cloud optical thickness - cloud top pressure frequency distributions. Despite the large concentration of research on the variability of Northern Hemisphere (NH) regions during summer, it is noted that the largest amplitude intraseasonal variability in the NH regions occurs during local winter. The effect of intraseasonal variability on the calculation and interpretation of seasonal results is investigated. Decreases in seasonally averaged cloud cover, optical thickness and cloud top pressure from the May-through-September season to the November-through-March season are most apparent in the NH regions. Further analysis indicates that these changes are due to an increase in frequency, but a decrease in the persistence of synoptic events. In addition, changes in cloud top pressure and optical thickness characteristics from the summer to winter seasons indicate that the NH subtropics undergo a change in dynamic regime with season. This change appears in the cloud fields as a shift from the more commonly seen lower-altitude, thicker optical thickness clouds to higher-altitude, thinner clouds. The latter cloud-type is associated with the lower sea level pressure, upward vertical velocity phase of the synoptic wave. Intraseasonal changes in cloud properties in the Southern Hemisphere and NH summer are much smaller in amplitude. Although they also appear to be linked to changes in the large-scale dynamics, similarly to NH winter variations, the relationships are more ambiguous due to the small amplitudes and longer time scales. We attempt to interpret some of these relationships using the results of the Betts and Ridgway (1989) box model. However, these results cannot consistently explain the patterns when results from all regions are considered, implying that this model may not adequately explain all the processes involved in the variability.

Rozendaal, Margaret A.↗
NASA NTRS2001

Comparison of ER-2 Aircraft and POAM-III, MLS, and SAGE-II Satellite Measurements During SOLVE Using Traditional Correlative Analysis and Trajectory Hunting Technique

We compared the version 5 Microwave Limb Sounder (MLS) aboard the Upper Atmosphere Research Satellite (UARS), version 3 Polar Ozone and Aerosol Measurement-III (POAM-111) aboard the French satellite SPOT-IV, version 6.0 Stratospheric Aerosol and Gas Experiment 11 (SAGE-II) aboard the Earth Radiation Budget Satellite, and NASA ER-2 aircraft measurements made in the northern hemisphere in January-February 2000 during the SAGE III Ozone Loss and Validation Experiment (SOLVE). This study addresses one of the key scientific objectives of the SOLVE campaign, namely, to validate multi-platform satellite measurements made in the polar stratosphere during winter. This intercomparison was performed using a traditional correlative analysis (TCA) and a trajectory hunting technique (THT). Launching backward and forward trajectories from the points of measurement, the THT identifies air parcels sampled at least twice within a prescribed match criterion during the course of 5 days. We found that the ozone measurements made by these four instruments agree most of the time within 110% in the stratosphere up to 1400 K (approximately 35 km). The water vapor measurements from POAM-III and the ER-2 Harvard Lyman-alpha hygrometer and JPL laser hygrometer agree to within 10.5 ppmv (or about +/-10%) in the lower stratosphere above 380 K. The MLS and ER-2 ClO measurements agree within their error bars for the TCA. The MLS and ER-2 nitric acid measurements near 17-20 km altitude agree within their uncertainties most of the time with a hint of a positive offset by MLS according to the TCA. We also applied the AER box model constrained by the ER-2 measurements for analysis of the ClO and HN03 measurements using the THT. We found that: (1) the model values of ClO are smaller by about 0.3-0.4 (0.2) ppbv below (above) 400 K than those by MLS and (2) the HN03 comparison shows a positive offset of MLS values by approximately 1 and 1-2 ppbv below 400 K and near 450 K, respectively. It is hard to quantify the HN03 offset in the 400-440 K range because of the high sensitivity of nitric acid to the PSC schemes. Our study shows that, with some limitations (like HN03 comparison under PSC conditions), the THT is a more powerful tool for validation studies than the TCA, making conclusions of the comparison statistically more robust.

Danilin, M. Y.↗
NASA NTRS2002

Enhanced ClO from 10 to 12 km Near the Winter Polar Tropopause During SOLVE/THESEO-2000

Abundances of chlorine oxide have been measured in situ near the tropopause from the NASA DC-8 aircraft during the SOLVE/THESEO-2000 campaign. Significant abundances, averaging 15-20 parts per trillion, were observed throughout the lowermost stratosphere at high latitudes during winter. Mixing ratios of ClO generally increased with increasing ozone (the latter an indicator of stratospheric air) as has been observed at other latitudes and seasons. However, the ratio of ClO to inorganic chlorine ([ClO]/[Cl(sub y)]) was found to be largest in air characterized by low abundances of ozone (approximately l00-250). It was within this range of ozone values that cirrus clouds were also observed occasionally throughout the measurement period, although distinct enhancements of ClO were not commonly observed directly within cirrus clouds. Elevated abundances of ClO were also apparently observed in polar darkness. However, we attribute these measurements to OClO, a species that can also be detected by the DC-8 instrument under the conditions encountered during SOLVE/THESEO-2000. Using a photochemical box model constrained by daytime abundances of ClO, we infer that BrO mixing ratios in this region were approximately 2-4 ppt, consistent with previous measurements from balloon-borne remote sensors.

Toohey, Darin W.↗
NASA NTRS2002

In-Situ Measurements of HCN and CH3CN in the Pacific Troposphere: Sources, Sinks, and Comparisons with Spectroscopic Observations

We report the first in-situ measurements of hydrogen cyanide (HCN) and acetonitrile (CH3CN) from the Pacific troposphere (0-12 km) obtained during the NASA/Trace-P mission (Feb.-April, 2001). Mean HCN and CH3CN mixing ratios of 243 (+/-118) ppt and 149 (+/-56) ppt respectively, were measured. The in-situ observations correspond to a total HCN column of 4.4-4.9 x 10(exp 15) molec. cm(exp -2) and a CH3CN column of 2.8-3.0 x 10(exp 15) molec. cm(exp -2). This HCN column is in good agreement with available spectroscopic observations. The atmospheric concentrations of HCN and CH3CN were greatly influenced by outflow of pollution from Asia. There is a linear relationship between the mixing ratios of HCN and CH3CN, and in turn these are well correlated with tracers of biomass combustion (e.g. CH3Cl, CO). Relative enhancements with respect to known tracers of biomass combustion within selected plumes in the free troposphere, and pollution episodes in the boundary layer allow an estimation of a global biomass burning source of 0.8+/-0.4 Tg (N)/y for HCN and 0.4+/-0.1 Tg (N)/y for CH3CN. In comparison, emissions from automobiles and industry are quite small (<0.05 Tg (N)/y). The vertical structure of HCN and CH3CN indicated reduced mixing ratios in the MBL (Marine Boundary Layer). Using, a simple box model, the observed gradients across the top of the MBL are used to derive an oceanic flux of 6.7 x 10(exp -15) g (N) cm(exp -2)/s for HCN and 4.8 x 10(exp -15) g (N) cm(exp -2)/s for CH3CN. An air-sea exchange model is used to conclude that this flux can be maintained if the oceans are under-saturated in HCN and CH3CN by 23% and 17%, respectively. It is inferred that oceanic loss is a dominant sink for these nitrites, and they deposit some 1.3 Tg (N) of nitrogen annually to the oceans. Assuming reaction with OH radicals and loss to the oceans as the major removal processes, a mean atmospheric residence time of 4.7 months for HCN and 5.1 months for CH3CN is calculated. A global budget analysis shows that the sources and sinks of HCN and CH3CN are roughly in balance. There are indications that biogenic sources may also be present. Mechanisms involved in nitrate formation during combustion and removal in the oceans are poorly understood.

Singh, Hanwant B.↗
NASA NTRS2002

A Discussion of Upper Stratospheric Ozone Asymmetry and Ozone Trend Changes

Analyses from SAGE I/II version 6.0 data exhibit upper stratospheric ozone trends which are not significantly different from those in version 5.96 data. Trend calculations show larger downward trends at mid-high latitudes in the Southern Hemisphere than in the Northern Hemisphere, particularly in 1980s. There are also indications of decreasing downward trends with time from 1979 to 1999. We have used a chemical box model and the UARS measurements of long lived gases, CH4, H2O, NO(x), and temperature to show that, with a constant Cl(sub y) trend, a hemispheric ozone trend asymmetry of 1%/decade at 45 deg. around 43 km is expected due to the hemispheric differences of temperature and CH4 during late winter/early. Also ozone trends should have been approximately 1%/decade more negative from 1979-1989 than from 1989-1999 because of the chemical feedbacks. The model results further indicate that both the reported decrease in CH4 and the increase in H2O in HALOE measurements will result in a larger downward ozone trend and a decrease in the hemispheric ozone trend asymmetry.

Li, Jinlong↗
NASA NTRS1996

Balloon observations of organic and inorganic chlorine in the stratosphere: the role of HClO4 production on sulfate aerosols

Simultaneous observations of stratospheric organic and inorganic chlorine were made in September 1993 out of Fort Sumner, New Mexico, using JPL balloon-borne MkIV interferometer. Between 15 and 20 km, a significant fraction (20-60%) of the inorganic chlorine could not be accounted for by the sum of measured HCl, ClONO2, and HOCl. Laboratory measurements of the reaction of ClO radicals on sulfuric acid solutions have indicated that, along with HCl, small amounts of perchloric acid, HClO4, were formed. Very little is known about the fate of HClO4 in the stratosphere and we use a photochemical box model to determine the impact of this new species on the partitioning of inorganic chlorine in the stratosphere. Assuming that HClO4 is photochemically stable, it is shown that in the enhanced aerosol loading conditions resulting from Mt. Pinatubo's eruption, HClO4 could represent a significant reservoir of chlorine in the lower stratosphere, sequestering up to 0.2 ppbv (or 50%) of the total inorganic chlorine at 16 km. The occurrence of this new species could bring to closure the inorganic chlorine budget deficiency made apparent by recent ER-2 aircraft in situ measurements of HCl.

unmanned↗
NASA NTRS2004

Investigation of Polar Stratospheric Cloud Solid Particle Formation Mechanisms Using ILAS and AVHRR Observations in the Arctic

Satellite observations of denitrification and ice clouds in the Arctic lower stratosphere in February 1997 are used with Lagrangian microphysical box model calculations to evaluate nucleation mechanisms of solid polar stratospheric cloud (PSC) particles. The occurrences of ice clouds are not correlated in time and space with the locations of back trajectories of denitrified air masses, indicating that ice particle surfaces are not always a prerequisite for the formation of solid PSCs that lead to denitrification. In contrast, the model calculations incorporating a pseudoheterogeneous freezing process occurring at the vapor-liquid interface can quantitatively explain most of the observed denitrification when the nucleation activation free energy for nitric acid dihydrate formation is raised by only approx.10% relative to the current published values. Once nucleated, the conversion of nitric acid dihydrate to the stable trihydrate phase brings the computed levels of denitrification closer to the measurements. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0320 Atmospheric Composition and Sb~lctureC: loud physics and chemistry; 0340 Atmospheric Composition and Structure: Middle atmosphere-composition and chemistry

Irie, H.↗
NASA NTRS2007

Quantifying the Impact of the North American Monsoon and Deep Midlatitude Convection on the Subtropical Lowermost Stratosphere using in Situ Measurements

The chemical composition of the lowermost stratosphere exhibits both spatial and temporal variability depending upon the relative strength of (1) isentropic transport from the tropical tropopause layer (TTL), (2) diabatic descent from the midlatitude and northern midlatitude stratosphere followed by equatorward isentropic transport, and (3) diabatic ascent from the troposphere through convection. In situ measurements made in the lowermost stratosphere over Florida illustrate the additional impact of equatorward flow around the monsoon anticyclone. This flow carries, along with older stratospheric air, the distinct signature of deep midlatitude convection. We use simultaneous in situ measurements of water vapor (H2O), ozone (O3), total odd nitrogen (NOy), carbon dioxide (CO2), and carbon monoxide (CO) in the framework of a simple box model to quantify the composition of the air sampled in the lowermost stratosphere during the mission on the basis of tracer mixing ratios ascribed to the source regions for these transport pathways. The results show that in the summer, convection has a significant impact on the composition of air in the lowermost stratosphere, being the dominant source of water vapor up to the 380 K isentrope. The implications of these results extend from the potential for heterogeneous ozone loss resulting from the increased frequency and lifetime of cirrus near the local tropopause, to air with increased water vapor that as part of the equatorward flow associated with the North American monsoon can become part of the general circulation.

Weinstock, E. M.↗
NASA NTRS2007

The Role of Convection in Redistributing Formaldehyde to the Upper Troposphere Over North America and the North Atlantic during the Summer 2004 INTEX Campaign

Measurements of CH2O from a tunable diode laser absorption spectrometer (TDLAS) were acquired onboard the NASA DC-8 during the summer 2004 INTEX-NA (Intercontinental Chemical Transport Experiment - North America) campaign to test our understanding of convection and production mechanisms in the upper troposphere (UT, 6-12-km) over continental North America and the North Atlantic Ocean. Point-by-point comparisons with box model calculations, when MHP (CH3OOH) measurements were available for model constraint, resulted in a median CH2O measurement/model ratio of 0.91 in the UT. Multiple tracers were used to arrive at a set of UT CH2O background and perturbed air mass periods, and 46% of the TDLAS measurements fell within the latter category. At least 66% to 73% of these elevated UT observations were caused by enhanced production from CH2O precursors rather than direct transport of CH2O from the boundary layer. This distinction is important, since the effects from the former can last for over a week or more compared to one day or less in the case of convective transport of CH2O itself. In general, production of CH2O from CH4 was found to be the dominant source term, even in perturbed air masses. This was followed by production from MHP, methanol, PAN type compounds, and ketones, in descending order of their contribution. In the presence of elevated NO from lightning and potentially from the stratosphere, there was a definite trend in the CH2O discrepancy, which for the highest NO mixing ratios produced a median CH2O measurement/model ratio of 3.9 in the 10-12-km range. Discrepancies in CH2O and HO2 in the UT with NO were highly correlated and this provided further information as to the possible mechanism(s) responsible. These discrepancies with NO are consistent with additional production sources of both gases involving CH3O2 + NO reactions, most likely caused by unmeasured hydrocarbons.

Fried, Alan↗
NASA NTRS2016

Impacts of Brown Carbon from Biomass Burning on Surface UV and Ozone Photochemistry in the Amazon Basin

The spectral dependence of light absorption by atmospheric particulate matter has major implications for air quality and climate forcing, but remains uncertain especially in tropical areas with extensive biomass burning. In the September-October 2007 biomass-burning season in Santa Cruz, Bolivia, we studied light absorbing (chromophoric) organic or brown carbon (BrC) with surface and space-based remote sensing. We found that BrC has negligible absorption at visible wavelengths, but significant absorption and strong spectral dependence at UV wavelengths. Using the ground-based inversion of column effective imaginary refractive index in the range 305368nm, we quantified a strong spectral dependence of absorption by BrC in the UV and diminished ultraviolet B (UV-B) radiation reaching the surface. Reduced UV-B means less erythema, plant damage, and slower photolysis rates. We use a photochemical box model to show that relative to black carbon (BC) alone, the combined optical properties of BrC and BC slow the net rate of production of ozone by up to 18 and lead to reduced concentrations of radicals OH, HO2, and RO2 by up to 17, 15, and 14, respectively. The optical properties of BrC aerosol change in subtle ways the generally adverse effects of smoke from biomass burning.

UV absorption OMI↗
NASA NTRS2016

Formaldehyde Column Density Measurements as a Suitable Pathway to Estimate Near-Surface Ozone Tendencies from Space

In support of future satellite missions that aim to address the current shortcomings in measuring air quality from space, NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign was designed to enable exploration of relationships between column measurements of trace species relevant to air quality at high spatial and temporal resolution. In the DISCOVER-AQ data set, a modest correlation (r2 = 0.45) between ozone (O3) and formaldehyde (CH2O) column densities was observed. Further analysis revealed regional variability in the O3-CH2O relationship, with Maryland having a strong relationship when data were viewed temporally and Houston having a strong relationship when data were viewed spatially. These differences in regional behavior are attributed to differences in volatile organic compound (VOC) emissions. In Maryland, biogenic VOCs were responsible for approx.28% of CH2O formation within the boundary layer column, causing CH2O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH2O was observed. Box model simulations suggested that ambient CH2O mixing ratios have a weak diurnal trend (+/-20% throughout the day) due to photochemical effects, and that larger diurnal trends are associated with changes in hydrocarbon precursors. Finally, mathematical relationships were developed from first principles and were able to replicate the different behaviors seen in Maryland and Houston. While studies would be necessary to validate these results and determine the regional applicability of the O3-CH2O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near-surface air quality.

Surface Conditions from Column and Vertically Reso↗
NASA NTRS2017

BrO and Inferred Bry Profiles over the Western Pacific: Relevance of Inorganic Bromine Sources and a Bry Minimum in the Aged Tropical Tropopause Layer

We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box model to infer total gas-phase inorganic bromine (Br(sub y)) over the tropical western Pacific Ocean (tWPO) during the CONTRAST field campaign (January-February 2014). The observed BrO and inferred Bry profiles peak in the marine boundary layer (MBL), suggesting the need for a bromine source from sea-salt aerosol (SSA), in addition to organic bromine (CBry ). Both profiles are found to be C-shaped with local maxima in the upper free troposphere (FT). The median tropospheric BrO vertical column density (VCD) was measured as 1.6 x 10(exp 13) molec cm(exp -2), compared to model predictions of 0.9 x 10(exp 13) molec cm(exp -2) in GEOS-Chem (CBr(sub y) but no SSA source), 0.4 x 10(exp 13) molec cm(exp -2) in CAM-Chem (CBr(sub y) and SSA), and 2.1 x 10(exp 13) molec cm(exp -2) in GEOS-Chem (CBry and SSA). Neither global model fully captures the Cshape of the Br(sun y) profile. A local Br(sub y) maximum of 3.6 ppt (2.9-4.4 ppt; 95% confidence interval, CI) is inferred between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective tropical tropopause layer (TTL) to the aged TTL, gas-phase Br(sub y) decreases from the convective TTL to the aged TTL. Analysis of gas-phase Br(sub y) against multiple tracers (CFC-11, H2O/O3 ratio, and potential temperature) reveals a Br(sub y) minimum of 2.7 ppt (2.3-3.1 ppt; 95% CI) in the aged TTL, which agrees closely with a stratospheric injection of 2.6 +/- 0.6 ppt of inorganic Br(sub y) (estimated from CFC-11 correlations), and is remarkably insensitive to assumptions about heterogeneous chemistry. Bry increases to 6.3 ppt (5.6-7.0 ppt; 95% CI) in the stratospheric "middleworld" and 6.9 ppt (6.5-7.3 ppt; 95% CI) in the stratospheric "overworld". The local Br(sub y) minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-Chem, and suggests a more complex partitioning of gas-phase and aerosol Br(sub y) species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA-derived gas-phase Br(sub y) ) are needed to explain the gas-phase Br(sub y) budget in the upper free troposphere and TTL. They are also consistent with observations of significant bromide in Upper Troposphere-Lower Stratosphere aerosols. The total Br(sub y) budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas-phase Br(sub y) species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. Such simultaneous measurements are needed to (1) quantify SSA-derived Br(sub y) in the upper FT, (2) test Br(sub y) partitioning, and possibly explain the gas-phase Br(sub y) minimum in the aged TTL, (3) constrain heterogeneous reaction rates of bromine, and (4) account for all of the sources of Br(sub y) to the lower stratosphere.

Atmospheric Chemistry; bromine; troposphere; CONTR↗
NASA NTRS2018

Can Semi-Volatile Organic Aerosols Lead to Fewer Cloud Particles?

The impact of condensing organic aerosols on activated cloud number concentration is examined in a new aerosol microphysics box model, MATRIX-VBS. The model includes the volatility-basis set (VBS) framework coupled with the aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state) that resolves aerosol mass and number concentrations and aerosol mixing state. By including the condensation of organic aerosols, the new model produces less activated particles compared to the original model, which treats organic aerosols as non-volatile. Parameters such as aerosol chemical composition, mass and number concentrations, and particle sizes which affect activated cloud number concentration are thoroughly tested via a suite of Monte-Carlo simulations. Results show that by considering semi-volatile organics in MATRIX-VBS, there is lower activated particle number concentration, except in cases with low cloud updrafts, in clean environment at above freezing temperatures, and in polluted environments at high temperature (310K) and extremely low humidity conditions.

Gao, Chloe Y.↗
NASA NTRS2018

Profiles of Reactive Trace Gases over Remote Oceans During ATom

The Atmospheric Tomography (ATom) mission deployed an extensive gas and aerosol payload on the NASA DC-8 aircraft on four campaigns spanning each season. ATom systematically sampled the atmosphere from 0.2 to 12 kilometer altitude, from 85 degrees North Latitude to 65 degrees South Latitude, in both the Pacific and the Atlantic to provide detailed profiles of chemical composition over the remote oceans. We will present profiles of reactive trace species, such as O3, NOx, NOy, HOx, HCHO, and several other short-lived source gases. We will combine these measurements with results from a 0-D box model to show their utility in (1) evaluating gradients in latitude/season, (2) identifying contributions of pollution from long-range and convective transport, and (3) evaluating column measurements from remote sensing satellite instruments.

ISAF↗
NASA NTRS2020

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

The nonlinear chemical processes involved in ozone production (P(O3)) 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.

KORUS-AQ; formaldehyde; NOx; VOC; OMI; GeoTASO; oz↗
NASA NTRS2019

Exploring Oxidation in the Remote Free Troposphere: Insights From Atmospheric Tomography (ATom)

Earth's atmosphere oxidizes the greenhouse gas methane and other gases, thus determining their lifetimes and oxidation products. Much of this oxidation occurs in the remote, relatively clean free troposphere above the planetary boundary layer, where the oxidation chemistry is thought to be much simpler and better understood than it is in urban regions or forests. The NASA airborne Atmospheric Tomography study (ATom) was designed to produce cross sections of the detailed atmospheric composition in the remote atmosphere over the Pacific and Atlantic Oceans during four seasons. As part of the extensive ATom data set, measurements of the atmosphere's primary oxidant, hydroxyl (OH), and hydroperoxyl (HO2) are compared to a photochemical box model to test the oxidation chemistry. Generally, observed and modeled median OH and HO2 agree to within combined uncertainties at the 2σ confidence level, which is ~±40%. For some seasons, this agreement is within ~±20% below 6-km altitude. While this test finds no significant differences, OH observations increasingly exceeded modeled values at altitudes above 8 km, becoming ~35% greater, which is near the combined uncertainties. Measurement uncertainty and possible unknown measurement errors complicate tests for unknown chemistry or incorrect reaction rate coefficients that would substantially affect the OH and HO2 abundances. Future analysis of detailed comparisons may yield additional discrepancies that are masked in the median values.

atmosphere's primary oxidant, hydroxyl (OH), and h↗
NASA NTRS2022

Emission Factors and Evolution of SO2 Measured From Biomass Burning in Wildfires and Agricultural Fires

Fires emit sufficient sulfur to affect local and regional air quality and climate. This study analyzes SO2 emission factors and variability in smoke plumes from US wildfires and agricultural fires, as well as their relationship to sulfate and hydroxymethanesulfonate (HMS) formation. Observed SO2 emission factors for various fuel types show good agreement with the latest reviews of biomass burning emission factors, producing an emission factor range of 0.47–1.2 g SO2 kg^(−1) C. These emission factors vary with geographic location in a way that suggests that deposition of coal burning emissions and application of sulfur-containing fertilizers likely play a role in the larger observed values, which are primarily associated with agricultural burning. A 0-D box model generally reproduces the observed trends of SO2 and total sulfate (inorganic + organic) in aging wildfire plumes. In many cases, modeled HMS is consistent with the observed organosulfur concentrations. However, a comparison of observed organosulfur and modeled HMS suggests that multiple organosulfur compounds are likely responsible for the observations but that the chemistry of these compounds yields similar production and loss rates as that of HMS, resulting in good agreement with the modeled results. We provide suggestions for constraining the organosulfur compounds observed during these flights, and we show that the chemistry of HMS can allow organosulfur to act as an S(IV) reservoir under conditions of pH > 6 and liquid water content >10^(−7) g sm^(−3). This can facilitate long-range transport of sulfur emissions, resulting in increased SO2 and eventually sulfate in transported smoke.

Sulfur↗