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Thornton, J. A.

Publications and source records attributed to Thornton, J. A..

Anthropogenic Control over Wintertime Oxidation of Atmospheric Pollutants

Anthropogenic air pollutants such as nitrogen oxides (NO(x) = NO + NO(2)), sulfur dioxide (SO(2)), and volatile organic compounds (VOC), among others, are emitted to the atmosphere throughout the year from energy production and use, transportation, and agriculture. These primary pollutants lead to the formation of secondary pollutants such as fine particulate matter (PM(2.5)) and ozone (O(3)) and perturbations to the abundance and lifetimes of short-lived greenhouse gases. Free radical oxidation reactions driven by solar radiation govern the atmospheric lifetimes and transformations of most primary pollutants and thus their spatial distributions. During winter in the mid and high latitudes, where a large fraction of atmospheric pollutants are emitted globally, such photochemical oxidation is significantly slower. Using observations from a highly instrumented aircraft, we show that multi-phase reactions between gas-phase NO(x) reservoirs and aerosol particles, as well as VOC emissions from anthropogenic activities, lead to a suite of atypical radical precursors dominating the oxidizing capacity in polluted winter air, and thus, the distribution and fate of primary pollutants on a regional to global scale.

Haskins, J. D.↗

High Upward Fluxes of Formic Acid from a Boreal Forest Canopy

Eddy covariance fluxes of formic acid, HCOOH, were measured over a boreal forest canopy in spring/summer 2014. The HCOOH fluxes were bidirectional but mostly upward during daytime, in contrast to studies elsewhere that reported mostly downward fluxes. Downward flux episodes were explained well by modeled dry deposition rates. The sum of net observed flux and modeled dry deposition yields an upward gross flux of HCOOH, which could not be quantitatively explained by literature estimates of direct vegetative soil emissions nor by efficient chemical production from other volatile organic compounds, suggesting missing or greatly underestimated HCOOH sources in the boreal ecosystem. We implemented a vegetative HCOOH source into the GEOS-Chem chemical transport model to match our derived gross flux and evaluated the updated model against airborne and spaceborne observations. Model biases in the boundary layer were substantially reduced based on this revised treatment, but biases in the free troposphere remain unexplained.

forest↗

Formaldehyde Production from Isoprene Oxidation Across NOx Regimes

The chemical link between isoprene and formaldehyde (HCHO) is a strong, non-linear function of NOx (= 27 NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the Southeast U.S., we quantify HCHO production across the urban-rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly-emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1 - 2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9), while background HCHO increases by more than a factor of 2 (from 1.5 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D chemical box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models under-estimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or under-estimated hydroxyl radical concentrations. Moreover, we find that the total organic peroxy radical production rate is essentially independent of NOx, as the increase in oxidizing capacity with NOx is largely balanced by a decrease in VOC reactivity. Thus, the observed NOx dependence of HCHO mainly reflects the changing fate of organic peroxy radicals.

VOC↗

Substrate heating rates for planar and cylindrical-post magnetron sputtering sources

Results are presented for the substrate heating energy/atom required in the planar magnetron sputtering of Al, Cr, Ni, Cu, Mo, In, Ta, W, and Pt in Ar, as well as Al and Cr in O2. Data are also obtained for cylindrical magnetron sputtering of Nb, Ag, Ta, W, and Pb-Sn in Ar, and Mo sputtered in Ne, Ar, Kr, and Xe. Planar and cylindrical magnetron heating rates were comparable. Special experiments were conducted to examine the contributions to substrate heating of plasma species and ion neutralization and reflection at the cathode; the results obtained indicate that charged plasma species do not significantly contribute to the heating, but that neutralized and reflected ions play a significant role in the planar as well as cylindrical cases despite the differences in cathode geometry.

Thornton, J. A.↗