Saewung Kim

A new atmospherically relevant oxidant of sulphur dioxide

Atmospheric oxidation is a key phenomenon that connects atmospheric chemistry with globally challenging environmental issues, such as climate change, stratospheric ozone loss, acidification of soils and water, and health effects of air quality. Ozone, the hydroxyl radical and the nitrate radical are generally considered to be the dominant oxidants that initiate the removal of trace gases, including pollutants, from the atmosphere. Here we present atmospheric observations from a boreal forest region in Finland, supported by laboratory experiments and theoretical considerations, that allow us to identify another compound, probably a stabilized Criegee intermediate (a carbonyl oxide with two free-radical sites) or its derivative, which has a significant capacity to oxidize sulphur dioxide and potentially other trace gases. This compound probably enhances the reactivity of the atmosphere, particularly with regard to the production of sulphuric acid, and consequently atmospheric aerosol formation. Our findings suggest that this new atmospherically relevant oxidation route is important relative to oxidation by the hydroxyl radical, at least at moderate concentrations of that radical. We also find that the oxidation chemistry of this compound seems to be tightly linked to the presence of alkenes of biogenic origin.

Atmospheric chemistry of an Antarctic volcanic plume

[1] We report measurements of the atmospheric plume emitted by Erebus volcano, Antarctica, renowned for its persistent lava lake. The observations were made in December 2005 both at source, with an infrared spectrometer sited on the crater rim, and up to 56 km downwind, using a Twin Otter aircraft; with the two different measurement platforms, plume ages were sampled ranging from <1 min to as long as 9 h. Three species (CO, carbonyl sulfide (OCS), and SO2) were measured from both air and ground. While CO and OCS were conserved in the plume, consistent with their long atmospheric lifetimes, the downwind measurements indicate a SO2/CO ratio about 20% of that observed at the crater rim, suggesting rapid chemical conversion of SO2. The aircraft measurements also identify volcanogenic H2SO4, HNO3 and, recognized for the first time in a volcanic plume, HO2NO2. We did not find NOx in the downwind plume despite previous detection of NO2 above the crater. This suggests that near-source NOx was quickly oxidized to HNO3 and HO2NO2, and probably NO3� (aq), possibly in tandem with the conversion of SO2 to sulfate. These fast processes may have been facilitated by ‘‘cloud processing’’ in the dense plume immediately downwind from the crater. A further striking observation was O3 depletion of up to � 35% in parts of the downwind plume. This is likely to be due to the presence of reactive halogens (BrO and ClO) formedthrough heterogeneous processes in the young plume. Our analysis adds to the growing evidence for the tropospheric reactivity of volcanic plumes and shows that Erebus volcano has a significant impact on Antarctic atmospheric chemistry, at least locally in the Southern Ross Sea area.

Role of convection in redistributing formaldehyde to the upper troposphere over North America and the North Atlantic during the summer 2004 INTEX campaign

Measurements of formaldehyde (CH2O) from a tunable diode laser absorption spectrometer (TDLAS) were acquired onboard the NASA DC-8 aircraft during the summer 2004 INTEX-NA campaign to test our understanding of convection and CH2O production mechanisms in the upper troposphere (UT, 6–12 km) over continental North America and the North Atlantic Ocean. The present study utilizes these TDLAS measurements and results from a box model to (1) establish sets of conditions by which to distinguish “background” UT CH2O levels from those perturbed by convection and other causes; (2) quantify the CH2O precursor budgets for both air mass types; (3) quantify the fraction of time that the UT CH2O measurements over North America and North Atlantic are perturbed during the summer of 2004; (4) provide estimates for the fraction of time that such perturbed CH2O levels are caused by direct convection of boundary layer CH2O and/or convection of CH2O precursors; (5) assess the ability of box models to reproduce the CH2O measurements; and (6) examine CH2O and HO2 relationships in the presence of enhanced NO. Multiple tracers were used to arrive at a set of UT CH2O background and perturbed air mass periods, and 46% of the TDLAS measurements fell within the latter category. In general, production of CH2O from CH4 was found to be the dominant source term, even in perturbed air masses. This was followed by production from methyl hydroperoxide, methanol, PAN-type compounds, and ketones, in descending order of their contribution. At least 70% to 73% of the elevated UT observations were caused by enhanced production from CH2O precursors rather than direct transport of CH2O from the boundary layer. In the presence of elevated NO, there was a definite trend in the CH2O measurement–model discrepancy, and this was highly correlated with HO2 measurement–model discrepancies in the UT.

Atmospheric chemistry results from the ANTCI 2005 Antarctic plateau airborne study

One of the major goals of the 2005 Antarctic Tropospheric Chemistry Investigation (ANTCI) was to bridge the information gap between current knowledge of South Pole (SP) chemistry and that of the plateau. The former has been extensively studied, but its geographical position on the edge of the plateau makes extrapolating these findings across the plateau problematic. The airborne observations reported here demonstrate that, as at SP, elevated levels of nitric oxide (NO) are a common summertime feature of the plateau. As in earlier studies, planetary boundary layer (PBL) variations were a contributing factor leading to NO fluctuations. Thus, extensive use was made of in situ measurements and models to characterize PBL depths along each flight path and over broader areas of the plateau. Consistent with earlier SP studies that revealed photolysis of nitrate in surface snow as the source of NO x , large vertical gradients in NO were observed over most plateau areas sampled. Similar gradients were also found for the nitrogen species HNO3 and HO2NO2 and for O3. Thus, a common meteorological-chemical feature found was shallow PBLs associated with nitrogen species concentrations that exceeded free tropospheric levels. Collectively, these new results greatly extend the geographical sampling footprint defined by earlier SP studies. In particular, they suggest that previous assessments of the plateau as simply a chemical depository need updating. Although the evidence supporting this position comes in many forms, the fact that net photochemical production of ozone occurs during summer months over extensive areas of the plateau is pivotal.

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 studys 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.

Airborne observations reveal elevational gradient in tropical forest isoprene emissions

Isoprene dominates global non-methane volatile organic compound emissions, and impacts tropospheric chemistry by influencing oxidants and aerosols. Isoprene emission rates vary over several orders of magnitude for different plants, and characterizing this immense biological chemodiversity is a challenge for estimating isoprene emission from tropical forests. Here we present the isoprene emission estimates from aircraft eddy covariance measurements over the Amazonian forest. We report isoprene emission rates that are three times higher than satellite top-down estimates and 35% higher than model predictions. The results reveal strong correlations between observed isoprene emission rates and terrain elevations, which are confirmed by similar correlations between satellite-derived isoprene emissions and terrain elevations. We propose that the elevational gradient in the Amazonian forest isoprene emission capacity is determined by plant species distributions and can substantially explain isoprene emission variability in tropical forests, and use a model to demonstrate the resulting impacts on regional air quality.

Potential role of stabilized criegee radicals in sulfuric acid production in a high biogenic VOC environment

We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.