Search

Insoluble atmospheric aerosol, such as mineral dust, has been identified as an important contributor to the cloud droplet number concentration and indirect climate effect. However, empirically derived Frenkel–Halsey–Hill (FHH) water adsorption parameters remain the largest source of uncertainty in assessing the effect of insoluble aerosol on climate using the FHH activation theory (FHH-AT). Furthermore, previously reported FHH water adsorption parameters for illite and montmorillonite determined from water adsorption measurements below 100 % RH do not satisfactorily agree with values determined from FHH-AT analysis of experimental cloud condensation nuclei (CCN) measurements under supersaturated conditions. The work reported here uses previously reported experimental water adsorption measurements for illite and montmorillonite clays (Hatch et al., 2012, 2014) to show that improved analysis methods that account for the surface microstructure are necessary to obtain better agreement of FHH parameters between water adsorption and experimental CCN-derived FHH parameters.

Natural emissions of ozone-and-aerosol-precursor gases such as isoprene and monoterpenes are high in the southeastern US. In addition, anthropogenic emissions are significant in the southeastern US and summertime photochemistry is rapid. The NOAA-led SENEX (Southeast Nexus) aircraft campaign was one of the major components of the Southeast Atmosphere Study (SAS) and was focused on studying the interactions between biogenic and anthropogenic emissions to form secondary pollutants. During SENEX, the NOAA WP-3D aircraft conducted 20 research flights between 27 May and 10 July 2013 based out of Smyrna, TN. Here we describe the experimental approach, the science goals and early results of the NOAA SENEX campaign. The aircraft, its capabilities and standard measurements are described. The instrument payload is summarized including detection limits, accuracy, precision and time resolutions for all gas-and-aerosol phase instruments. The inter-comparisons of compounds measured with multiple instruments on the NOAA WP-3D are presented and were all within the stated uncertainties, except two of the three NO2 measurements. The SENEX flights included day- and nighttime flights in the southeastern US as well as flights over areas with intense shale gas extraction (Marcellus, Fayetteville and Haynesville shale). We present one example flight on 16 June 2013, which was a daytime flight over the Atlanta region, where several crosswind transects of plumes from the city and nearby point sources, such as power plants, paper mills and landfills, were flown. The area around Atlanta has large biogenic isoprene emissions, which provided an excellent case for studying the interactions between biogenic and anthropogenic emissions. In this example flight, chemistry in and outside the Atlanta plumes was observed for several hours after emission. The analysis of this flight showcases the strategies implemented to answer some of the main SENEX science questions.

The chemical link between isoprene and formaldehyde (HCHO) is a strong, nonlinear function of NOx (i.e., 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 photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, 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 ppbv ppbv−1), while background HCHO increases by a factor of 2 (from 1.6 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 steady-state 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 underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.

Mineral aerosol is of interest due to its physiochemical impacts on the Earth's atmosphere. However, adsorbed organics could influence the chemical and physical properties of atmospheric mineral particles and alter their impact on the biosphere and climate. In this work, the heterogeneous uptake of a series of small organic acids on the swelling clay, Na-montmorillonite, was studied at 212 K as a function of relative humidity (RH), organic acid pressure and clay mass. A high vacuum chamber equipped with a quadrupole mass spectrometer and a transmission Fourier transform infrared spectrometer was used to detect the gas and condensed phases, respectively. Our results show that while the initial uptake efficiency was found to be independent of organic acid pressure, it increased linearly with increasing clay mass. Thus, the small masses studied allow access to the entire surface area of the clay sample with minimal effects due to surface saturation. Additionally, results from this study show that the initial uptake efficiency for butanoic (butyric) acid on the clay increases by an order of magnitude as the RH is raised from 0% to 45% RH at 212 K while the initial uptake efficiency of formic, acetic and propanoic (propionic) acids increases only slightly at higher humidities. However, the initial uptake efficiency decreases significantly in a short amount of time due to surface saturation effects. Thus, although the initial uptake efficiencies are appropriate for initial times, the fact that the uptake efficiency will decrease over time as the surface saturates should be considered in atmospheric models. Surface saturation results in sub-monolayer coverage of organic acid on montmorillonite under dry conditions and relevant organic acid pressures that increases with increasing humidity for all organic acids studied. Additionally, the presence of large organic acids may slightly enhance the water content of the clay above 45% RH. Our results indicate that heterogeneous uptake of organic acids on swelling clay minerals provides an important irreversible heterogeneous sink for these species.