Whole air drawn from four heights within the high elevation (3,340 m asl), deep, winter snowpack at Niwot Ridge, Colorado, were sampled into stainless steel canisters, and subsequently analyzed by gas chromatography for 51 volatile inorganic and organic gases. Two adjacent plots with similar snow cover were sampled, one over bare soil and a second one from within a snow-filled chamber where Tedlar/Teflon-film covered the ground and isolated it from the soil. This comparison allowed for studying effects from processes in the snowpack itself versus soil influences on the gas concentrations and fluxes within and through the snowpack. Samples were also collected from ambient air above the snow surface for comparison with the snowpack air. Analyzed gas species were found to exhibit three different kinds of behavior: (1) One group of gases, i.e., carbon dioxide (CO₂), chloroform (CHCl₃), dimethylsulfide (CH₃)₂S, carbondisulfide (CS₂), and dichlorobromomethane (CHBrCl₂), displayed higher concentrations inside the snow, indicating a formation of these species and release into the atmosphere. (2) A second group of compounds, including carbon monoxide (CO), carbonyl sulfide (COS), the hydrocarbons methane, ethane, ethyne, benzene, and the halogenated compounds methylchloride (CH₃Cl), methylbromide (CH₃Br), dibromomethane (CH₂Br₂), bromoform (CHBr₃), tetrachloromethane (CCl₄), CFC-11, CFC-12, HCFC-22, CFC-113, 1,2-dichloroethane, methylchloroform, HCFC-141b, and HCFC-142b, were found at lower concentrations in the snow, indicating that the snow and/or soil constitute a sink for these gases. (3) For 21 other gases absolute concentrations, respectively concentration gradients, were too low to unequivocally identify their uptake or release behavior. For gases listed in the first two groups, concentration gradients were incorporated into a snowpack gas diffusion model to derive preliminary estimates of fluxes at the snow-atmosphere interface. The snowpack gradient flux technique was found to offer a highly sensitive method for the study of these surface gas exchanges. Microbial activities below this deep, winter snowpack appear to be the driving mechanism behind these gas sources and sinks. Flux results were applied to a simple box model to assess the potential contribution of the snowpack uptake rates to atmospheric lifetimes of these species.

We present data collected from a number of snow-covered environments including two polar locations (Summit, Greenland and the South Pole) and two mid-latitude regions (a remote site in northern Michigan, and Niwot Ridge, Colorado). At each site, concentrations of CH3 I and C2 H5 I were enhanced within the interstitial air near the snow surface, compared to levels in boundary layer air. Fluxes of CH3 Br from surface snow to the atmosphere were observed at each site except Niwot Ridge, where CH3 Br appeared to have a sink. The mid-latitude sites showed significant emissions of CH3 Cl, mostly originating at the ground surface and traveling up through the snow, while at the polar locations CH3 Cl emissions from firn air were relatively small. In general, methyl halide mixing ratios in firn air were significantly greater at Summit than at the South Pole, with Summit showing a strong diurnal cycle in the production of alkyl halides that was well correlated with actinic radiation and firn temperature. We suggest that the most likely route to alkyl halide formation is through an acid catalyzed nucleophilic substitution of an alcohol type function by a halide, both of which should be preferentially segregated to the quasi-liquid layer at the surface of the snow grains. A series of experiments using a snow-filled quartz chamber irradiated by natural sunlight allowed estimation of emission trends that were hard to measure in the natural snowpack. These static chamber experiments confirmed significant production of the primary alkyl halides, following the order CH3 Cl > CH3 Br > C2 H5 Cl > CH3 I > C2 H5 Br > C2 H5 I > 1 - C3 H7 Br > 1 - C3 H7 I. Our observations at all four locations, including polar and mid-latitude sites, imply that alkyl halide production may be associated with all surface snows. © 2007 Elsevier Ltd. All rights reserved.

The air quality in the outflow from Fort Worth, TX was studied in June 2011 at a location surrounded by oil and gas development in the Barnett Shale. The objectives of this study were to understand the major sources of volatile organic compounds (VOCs) and organic aerosols and explore the potential influence each VOC source had on ozone and secondary organic aerosol formation. Measurements of VOCs were apportioned between six factors using Positive Matrix Factorization (PMF): Natural Gas (25 ± 2%; ±99% CL); Fugitive Emissions (15 ± 2%); Internal Combustion Engines (15 ± 2%); Biogenic Emissions (7 ± 1%); Industrial Emissions/Oxidation 1(8 ± 1%); and Oxidation 2 (18 ± 2%). Reactivity calculations suggest the Biogenic and Oxidation 2 factors were the most likely VOC sources to influence local ozone. However, enough OH reactivity was calculated for factors related to the oil and gas development that they could incrementally increase O3. Three organic aerosol (OA) types were identified with PMF applied to high-resolution time-of-flight aerosol mass spectrometry measurements: hydrocarbon-like OA (HOA; 11% of mass) and two classes of oxidized OA (semi- and less-volatile OOA, SV and LV; 45% and 44%, respectively). The HOA correlated with the Internal Combustion Engine VOC factor indicating that a large fraction of the HOA was emitted by gasoline and diesel motors. The SV-OOA correlated with the oxidized VOC factors during most of the study, whereas a correlation between LV-OOA and the oxidized VOC factors was only observed during part of the study. It is hypothesized that SV-OOA and the oxidized VOC factors correlated reasonably well because these factors likely were separated by at most only a few oxidation generations on the oxidation pathway of organic compounds.

In support of future satellite missions that aim to address the current shortcomings in measuring air quality from space, NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign was designed to enable exploration of relationships between column measurements of trace species relevant to air quality at high spatial and temporal resolution. In the DISCOVER-AQ data set, a modest correlation (r ² = 0.45) between ozone (O₃) and formaldehyde (CH₂O) column densities was observed. Further analysis revealed regional variability in the O₃-CH₂O relationship, with Maryland having a strong relationship when data were viewed temporally and Houston having a strong relationship when data were viewed spatially. These differences in regional behavior are attributed to differences in volatile organic compound (VOC) emissions. In Maryland, biogenic VOCs were responsible for ~28% of CH₂O formation within the boundary layer column, causing CH₂O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH₂O was observed. Box model simulations suggested that ambient CH₂O mixing ratios have a weak diurnal trend (±20% throughout the day) due to photochemical effects, and that larger diurnal trends are associated with changes in hydrocarbon precursors. Finally, mathematical relationships were developed from first principles and were able to replicate the different behaviors seen in Maryland and Houston. While studies would be necessary to validate these results and determine the regional applicability of the O₃-CH₂O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near-surface air quality.

The Korea-United States Air Quality (KORUS-AQ) field study was conducted during May-June 2016. The effort was jointly sponsored by the National Institute of Environmental Research of South Korea and the National Aeronautics and Space Administration of the United States. KORUS-AQ offered an unprecedented, multi-perspective view of air quality conditions in South Korea by employing observations from three aircraft, an extensive ground-based network, and three ships along with an array of air quality forecast models. Information gathered during the study is contributing to an improved understanding of the factors controlling air quality in South Korea. The study also provided a valuable test bed for future air quality-observing strategies involving geostationary satellite instruments being launched by both countries to examine air quality throughout the day over Asia and North America. This article presents details on the KORUS-AQ observational assets, study execution, data products, and air quality conditions observed during the study. High-level findings from companion papers in this special issue are also summarized and discussed in relation to the factors controlling fine particle and ozone pollution, current emissions and source apportionment, and expectations for the role of satellite observations in the future. Resulting policy recommendations and advice regarding plans going forward are summarized. These results provide an important update to early feedback previously provided in a Rapid Science Synthesis Report produced for South Korean policy makers in 2017 and form the basis for the Final Science Synthesis Report delivered in 2020.