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Kirk Ullmann

Publications and source records attributed to Kirk Ullmann.

12 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2024

Stratospheric Air Intrusions Promote Global-Scale New Particle Formation

New particle formation in the free troposphere is a major source of cloud condensation nuclei globally. The prevailing view is that in the free troposphere, new particles are formed predominantly in convective cloud outflows. We present another mechanism using global observations. We find that during stratospheric air intrusion events, the mixing of descending ozone-rich stratospheric air with more moist free tropospheric background results in elevated hydroxyl radical (OH) concentrations. Such mixing is most prevalent near the tropopause where the sulfur dioxide (SO 2 ) mixing ratios are high. The combination of elevated SO 2 and OH levels leads to enhanced sulfuric acid concentrations, promoting particle formation. Such new particle formation occurs frequently and over large geographic regions, representing an important particle source in the midlatitude free troposphere.

Jiaoshi Zhang↗
NASA NTRS2023

An Observation-Based, Reduced-Form Model for Oxidation in the Remote Marine Troposphere

The hydroxyl radical (OH) fuels atmospheric chemical cycling as the main sink for methane and a driver of the formation and loss of many air pollutants, but direct OH observations are sparse. We develop and evaluate an observation-based proxy for short term, spatial variations in OH (Proxy OH ) in the remote marine troposphere using unprecedented and comprehensive measurements from the NASA Atmospheric Tomography (ATom) airborne campaign. Proxy OH is a reduced form of the OH steady-state equation representing the dominant OH production and loss pathways in the remote marine troposphere, according to box model simulations of OH constrained with ATom observations. Proxy OH comprises only eight variables that are generally observed by routine ground- or satellite-based instruments. ProxyOH scales linearly with in situ [OH] spatial variations along the ATom flight tracks (median r 2 = 0.90, interquartile range = 0.80 – 0.94 across 2 km altitude by 20° latitudinal regions). We deconstruct spatial variations in Proxy OH as a first-order approximation of the sensitivity of OH variations to individual terms. Two terms modulate within-region Proxy OH variations—water vapor (H 2 O) and, to a lesser extent, nitric oxide (NO). This implies that a limited set of observations could offer a novel avenue for observation-based mapping of OH spatial variations over much of the remote marine troposphere. Both H 2 O and NO are expected to change with climate, while NO also varies strongly with human activities. We also illustrate the utility of Proxy OH as a process-based approach for evaluating inter-model differences in remote marine tropospheric OH.

Colleen B. Baublitz↗
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↗
NASA NTRS2022

Evaluating the Impact of Chemical Complexity and Horizontal Resolution on Tropospheric Ozone Over the Conterminous US With a Global Variable Resolution Chemistry Model

A new configuration of the Community Earth System Model (CESM)/Community Atmosphere Model with full chemistry (CAM-chem) supporting the capability of horizontal mesh refinement through the use of the spectral element (SE) dynamical core is developed and called CESM/CAM-chem-SE. Horizontal mesh refinement in CESM/CAM-chem-SE is unique and novel in that pollutants such as ozone are accurately represented at human exposure relevant scales while also directly including global feedbacks. CESM/CAM-chem-SE with mesh refinement down to ∼14 km over the conterminous US (CONUS) is the beginning of the Multi-Scale Infrastructure for Chemistry and Aerosols (MUSICAv0). Here MUSICAv0 is evaluated and used to better understand how horizontal resolution and chemical complexity impact ozone and ozone precursors over CONUS as compared to measurements from five aircraft campaigns, which occurred in 2013. This field campaign analysis demonstrates the importance of using finer horizontal resolution to accurately simulate ozone precursors such as nitrogen oxides and carbon monoxide. In general, the impact of using more complex chemistry on ozone and other oxidation products is more pronounced when using finer horizontal resolution where a larger number of chemical regimes are resolved. Large model biases for ozone near the surface remain in the Southeast US as compared to the aircraft observations even with updated chemistry and finer horizontal resolution. This suggests a need for adding the capability of replacing sections of global emission inventories with regional inventories, increasing the vertical resolution in the planetary boundary layer, and reducing model biases in meteorological variables such as temperature and clouds.

MUSICA↗
NASA NTRS2022

Photochemical Evolution of the 2013 California Rim Fire: Synergistic Impacts of Reactive Hydrocarbons and Enhanced Oxidants

Large wildfires markedly alter regional atmospheric composition, but chemical complexity challenges model predictions of downwind impacts. Here, we elucidate key facets of gas-phase photochemistry and assess novel chemical processes via a case study of the 2013 California Rim Fire plume. Airborne in situ observations, acquired during the NASA Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) mission, illustrate the evolution of volatile organic compounds (VOC), oxidants, and reactive nitrogen over 12 hours of atmospheric aging. Measurements show rapid formation of ozone and peroxyacyl nitrates (PNs), sustained peroxide production, and prolonged enhancements in oxygenated VOC and nitrogen oxides (NOX). Measurements and Lagrangian trajectories constrain a 0-D puff model that approximates plume photochemical history and provides a framework for evaluating key processes. Simulations examine the effects of 1) previously-unmeasured reactive VOC identified in recent laboratory studies, and 2) emissions and secondary production of nitrous acid (HONO). Inclusion of estimated unmeasured VOC leads to a 250% increase in OH reactivity and a 70% increase in radical production via oxygenated VOC photolysis. HONO amplifies radical cycling and serves as a downwind NOX source, although two different HONO production mechanisms (particulate nitrate photolysis and heterogeneous NO2 conversion) exhibit markedly different effects on ozone, NOX, and PNs. Analysis of radical initiation rates suggests that oxygenated VOC photolysis is a major radical source, exceeding HONO photolysis when averaged over the first 2 hours of aging. Ozone production chemistry transitions from VOC-sensitive to NOX-sensitive within the first hour of plume aging, with both peroxide and organic nitrate formation contributing significantly to radical termination. To simulate smoke plume chemistry accurately, models should simultaneously account for the full reactive VOC pool and all relevant oxidant sources.

SEAC4RS↗
NASA NTRS2021

Formaldehyde evolution in U.S. wildfire plumes during FIREX-AQ

Formaldehyde (HCHO) is one of the most abundant non-methane volatile organic compounds (VOCs) emitted by fires. HCHO also undergoes chemical production and loss as a fire plume ages, and it can be an important oxidant precursor. In this study, we disentangle the processes controlling HCHO by examining its evolution in wildfire plumes sampled by the NASA DC-8 during the FIREX-AQ field campaign. In nine of the twelve analyzed plumes, dilution-normalized HCHO increases with physical age (range 1 – 6 h). The balance of HCHO loss (mainly via photolysis) and production (via OH-initiated VOC oxidation) seems to control the sign and magnitude of this trend. Plume-average OH concentrations, calculated from VOC decays, range from –0.5 (± 0.5) × 10 6 to 5.3 (±0.7) × 10 6 cm -3 . The production and loss rates of dilution-normalized HCHO seem to decrease with plume age. Plume-to-plume variability in dilution-normalized secondary HCHO production correlates with OH abundance rather than normalized OH reactivity, suggesting that OH is the main driver of fire-to-fire variability in HCHO secondary production. Analysis suggests an effective HCHO yield of 0.33 (± 0.05) per VOC molecule oxidized for the 12 wildfire plumes. This finding can help connect space-based HCHO observations to the oxidizing capacity of the atmosphere and to VOC emissions.

Air quality↗
NASA NTRS2021

Rapid Cloud Removal of Dimethyl Sulfide Oxidation Products Limits SO 2 and Cloud Condensation Nuclei Production in the Marine Atmosphere

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of 60 DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth’s radiation balance and climate. Quantitative assessment of the impact of DMS emissions on CCN concentrations necessitates a detailed description of the oxidation of DMS in the presence of existing aerosol particles and clouds. In the unpolluted marine atmosphere, DMS is efficiently oxidized to hydroperoxymethyl thioformate (HPMTF), a stable intermediate in the chemical trajectory towards sulfur dioxide (SO 2 ) and ultimately sulfate aerosol (Veres et al. 2020). Using direct airborne flux measurements, we demonstrate that irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime (τ HPMTF < 2 hours) and terminates DMS oxidation to SO 2 in the cloudy marine boundary layer. When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO 2 production from DMS is reduced by 35% globally and near surface (0-3km) SO 2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for conversion of DMS to sulfate, while limiting new particle formation in the marine atmosphere and changing the dynamics of aerosol growth. This loss process potentially reduces the spatial scale over which DMS emissions contribute to aerosol production and growth and weakens the link between DMS emission and marine CCN production with subsequent implications for cloud formation, radiative forcing, and climate.

dimethyl sulfide↗
NASA NTRS2020

Missing OH Reactivity in the Global Marine Boundary Layer

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, throughout much of the free troposphere, the calculated OH reactivity was below the limit-of-detection for the ATom instrument used to measure OH reactivity, 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-1larger than the mean calculated OH reactivity. The missing OH reactivity, the difference between the measured and calculated OH reactivity, varied between 0 s-1to 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.

NASA Atmospheric Tomography (ATom)↗
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)↗