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Stickel, Robert E.

Publications and source records attributed to Stickel, Robert E..

Influence of Ohio River Valley Emissions on Fine Particle Sulfate Measured from Aircraft over Large Regions of the Eastern United States and Canada during INTEX-NA

Aircraft measurements of fine inorganic aerosol composition were made with a particle-into-liquid sampler coupled to dual ion chromatographs (PILS-IC) as part of the NASA INTEX-NA study. The sampling campaign, which lasted from 1 July to 14 August 2004, centered over the eastern United States and Canada and showed that sulfate was the dominant inorganic species measured. The highest sulfate concentrations were observed at altitudes below 2 km, and back trajectory analyses showed a distinct difference between air masses that had or had not intercepted the Ohio River valley (ORV) region. Air masses encountered below 2 km with a history over the ORV had sulfate concentrations that were higher by a factor of 3.2 and total sulfur (S) concentrations higher by 2.5. The study's highest sulfate concentrations were found in these air masses. The sulfur of the ORV air masses was also more processed with a mean sulfate to total sulfur molar ratio of 0.5 compared to 0.3 in non-ORV measurements. Results from a second, independent trajectory model agreed well with those from the primary analysis. These ORV-influenced air masses were encountered on multiple days and were widely spread across the eastern United States and western Atlantic region.

Hennigan, Christopher J.↗

Laboratory Investigations of Stratospheric Halogen Chemistry

A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

Wine, Paul H.↗

Halogen and Sulfur Reactions Relevant to Polar Chemistry

It is widely hypothesized that catalytic cycles involving BrO(x) species play an important role in the episodic destruction of ground-level ozone which is observed in the springtime Arctic boundary layer, although the exact mechanism for production of BrO(x) radicals remains an open question [Barrie et al., Bottenheim et al.; Finlayson-Pitts et al., McConnell et al.] The critical evidence linking ozone depletion with BrO(x) chemistry is an observed negative correlation between ozone and filterable bromine [Bottenheim et al., Kieser et al.] In a recent field study of springtime Arctic boundary layer chemistry [Kieser et al.] ozone concentrations and ethane concentrations were found to be correlated; this observation suggests chlorine atoms (which react rapidly with ethane) may also be an important catalyst for ozone destruction under springtime Arctic conditions.

Wine, Paul H.↗

Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

Wine, Paul H.↗

Static second-order polarizability calculations for large molecular systems

A procedure to calculate all second-order polarizability tensor elements in static fields has been developed. The calculations are based on semiempirical Hamiltonians (MNDO) that include shaped electric fields. The technique has been applied to mono-, di-, and trisubstituted benzenes incorporating nitro, methyl, and primary and secondary amino groups.

Cardelino, Beatriz H.↗