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Iraci, L. T.

Publications and source records attributed to Iraci, L. T..

Airborne Measurements and Emission Estimates of Greenhouse Gases and Other Trace Constituents From the 2013 California Yosemite Rim Wildfire

This paper presents airborne measurements of multiple atmospheric trace constituents including greenhouse gases (such as CO2, CH4, O3) and biomass burning tracers (such as CO, CH3CN) downwind of an exceptionally large wildfire. In summer 2013, the Rim wildfire, ignited just west of the Yosemite National Park, California, and burned over 250,000 acres of the forest during the 2-month period (17 August to 24 October) before it was extinguished. The Rim wildfire plume was intercepted by flights carried out by the NASA Ames Alpha Jet Atmospheric eXperiment (AJAX) on 29 August and the NASA DC-8, as part of SEAC4RS (Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys), on 26 and 27 August during its intense, primary burning period. AJAX revisited the wildfire on 10 September when the conditions were increasingly smoldering, with slower growth. The more extensive payload of the DC-8 helped to bridge key measurements that were not available as part of AJAX (e. g. CO). Data analyses are presented in terms of emission ratios (ER), emission factors (EF) and combustion efficiency and are compared with previous wildfire studies. ERs were 8.0 ppb CH4/(ppm CO2) on 26 August, 6.5 ppb CH4 (ppm CO2)1 on 29 August and 18.3 ppb CH4 (ppm CO2)1 on 10 September 2013. The increase in CH4 ER from 6.5 to 8.0 ppb CH4/(ppm CO2) during the primary burning period to 18.3 ppb CH4/(ppm CO2) during the fire's slower growth period likely indicates enhanced CH4 emissions from increased smoldering combustion relative to flaming combustion. Given the magnitude of the Rim wildfire, the impacts it had on regional air quality and the limited sampling of wildfire emissions in the western United States to date, this study provides a valuable dataset to support forestry and regional air quality management, including observations of ERs of a wide number of species from the Rim wildfire.

Yates, E. L.↗

Atmospheric Chemistry of Micrometeoritic Organic Compounds

Micrometeorites approx.100 m in diameter deliver most of the Earth s annual accumulation of extraterrestrial material. These small particles are so strongly heated upon atmospheric entry that most of their volatile content is vaporized. Here we present preliminary results from two sets of experiments to investigate the fate of the organic fraction of micrometeorites. In the first set of experiments, 300 m particles of a CM carbonaceous chondrite were subject to flash pyrolysis, simulating atmospheric entry. In addition to CO and CO2, many organic compounds were released, including functionalized benzenes, hydrocarbons, and small polycyclic aromatic hydrocarbons. In the second set of experiments, we subjected two of these compounds to conditions that simulate the heterogeneous chemistry of Earth s upper atmosphere. We find evidence that meteor-derived compounds can follow reaction pathways leading to the formation of more complex organic compounds.

Kress, M. E.↗

Heterogeneous Interactions of Acetaldehyde and Sulfuric Acid

The uptake of acetaldehyde [CH3CHO] by aqueous sulfuric acid has been studied via Knudsen cell experiments over ranges of temperature (210-250 K) and acid concentration (40-80 wt. %) representative of the upper troposphere. The Henry's law constants for acetaldehyde calculated from these data range from 6 x 10(exp 2) M/atm for 40 wt. % H2SO4 at 228 K to 2 x 10(exp 5) M/atm for 80 wt. % H2SO4 at 212 K. In some instances, acetaldehyde uptake exhibits apparent steady-state loss. The possible sources of this behavior, including polymerization, will be explored. Furthermore, the implications for heterogeneous reactions of aldehydes in sulfate aerosols in the upper troposphere will be discussed.

Michelsen, R. R.↗

Heterogeneous Chemistry Involving Methanol in Tropospheric Clouds

In this report we analyze airborne measurements to suggest that methanol in biomass burning smoke is lost heterogeneously in clouds. When a smoke plume intersected a cumulus cloud during the SAFARI 2000 field project, the observed methanol gas phase concentration rapidly declined. Current understanding of gas and aqueous phase chemistry cannot explain the loss of methanol documented by these measurements. Two plausible heterogeneous reactions are proposed to explain the observed simultaneous loss and production of methanol and formaldehyde, respectively. If the rapid heterogeneous processing of methanol, seen in a cloud impacted by smoke, occurs in more pristine clouds, it could affect the oxidizing capacity of the troposphere on a global scale.

Tabazadeh, A.↗

Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

Iraci, L. T.↗

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

Iraci, L. T.↗