Jennifer Kaiser

Missing gas-phase source of hono inferred from zeppelin measurements in the troposphere

On a Zeppelin Nitrous acid (HONO) is an important atmospheric trace gas that acts as a precursor of tropospheric hydroxyl-radicals (OH), which is responsible for the self-cleansing capacity of the atmosphere and which also controls the concentrations of greenhouse gases, such as methane and ozone. How HONO is made is a mystery. Flying onboard a Zeppelin over the Po Valley in Northern Italy, Li et al. (p. 292) discovered HONO in the undisturbed morning troposphere, indicating that HONO must be produced there, rather than mixed from the surface. The high HONO concentrations are likely to have been formed by a light-dependent gas-phase source that probably consumed OH or HO2 radicals, which hints that the impact of HONO on the abundance of OH in the entire troposphere may be substantially overestimated. The tropospheric production of HONO from a light-dependent gas-phase source raises questions about its impact on OH. Gaseous nitrous acid (HONO) is an important precursor of tropospheric hydroxyl radicals (OH). OH is responsible for atmospheric self-cleansing and controls the concentrations of greenhouse gases like methane and ozone. Due to lack of measurements, vertical distributions of HONO and its sources in the troposphere remain unclear. Here, we present a set of observations of HONO and its budget made onboard a Zeppelin airship. In a sunlit layer separated from Earth’s surface processes by temperature inversion, we found high HONO concentrations providing evidence for a strong gas-phase source of HONO consuming nitrogen oxides and potentially hydrogen oxide radicals. The observed properties of this production process suggest that the generally assumed impact of HONO on the abundance of OH in the troposphere is substantially overestimated.

Conversion of hydroperoxides to carbonyls in field and laboratory instrumentation: Observational bias in diagnosing pristine versus anthropogenically controlled atmospheric chemistry

Atmospheric volatile organic compound (VOC) oxidation mechanisms under pristine (rural/remote) and urban (anthropogenically-influenced) conditions follow distinct pathways due to large differences in nitrogen oxide (NO_x) concentrations. These two pathways lead to products that have different chemical and physical properties and reactivity. Under pristine conditions, isoprene hydroxy hydroperoxides (ISOPOOHs) are the dominant first-generation isoprene oxidation products. Utilizing authentic ISOPOOH standards, we demonstrate that two of the most commonly used methods of measuring VOC oxidation products (i.e., gas chromatography and proton transfer reaction mass spectrometry) observe these hydroperoxides as their equivalent high-NO isoprene oxidation products – methyl vinyl ketone (MVK) and methacrolein (MACR). This interference has led to an observational bias affecting our understanding of global atmospheric processes. Considering these artifacts will help close the gap on discrepancies regarding the identity and fate of reactive organic carbon, revise our understanding of surface-atmosphere exchange of reactive carbon and SOA formation, and improve our understanding of atmospheric oxidative capacity.

Instrumentation and Measurement Strategy for the NOAA SENEX Aircraft Campaign as Part of the Southeast Atmosphere Study 2013

Natural emissions of ozone-and-aerosol-precursor gases such as isoprene and monoterpenes are high in the southeast of the US. In addition, anthropogenic emissions are significant in the Southeast 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 Southeast 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.

Airborne measurements of the atmospheric emissions from a fuel ethanol refinery

Ethanol made from corn now constitutes approximately 10% of the fuel used in gasoline vehicles in the U.S. The ethanol is produced in over 200 fuel ethanol refineries across the nation. We report airborne measurements downwind from Decatur, Illinois, where the third largest fuel ethanol refinery in the U.S. is located. Estimated emissions are compared with the total point source emissions in Decatur according to the 2011 National Emissions Inventory (NEI-2011), in which the fuel ethanol refinery represents 68.0% of sulfur dioxide (SO2), 50.5% of nitrogen oxides (NOx = NO + NO2), 67.2% of volatile organic compounds (VOCs), and 95.9% of ethanol emissions. Emissions of SO2 and NOx from Decatur agreed with NEI-2011, but emissions of several VOCs were underestimated by factors of 5 (total VOCs) to 30 (ethanol). By combining the NEI-2011 with fuel ethanol production numbers from the Renewable Fuels Association, we calculate emission intensities, defined as the emissions per ethanol mass produced. Emission intensities of SO2 and NOx are higher for plants that use coal as an energy source, including the refinery in Decatur. By comparing with fuel-based emission factors, we find that fuel ethanol refineries have lower NOx, similar VOC, and higher SO2 emissions than from the use of this fuel in vehicles. The VOC emissions from refining could be higher than from vehicles, if the underestimated emissions in NEI-2011 downwind from Decatur extend to other fuel ethanol refineries. Finally, chemical transformations of the emissions from Decatur were observed, including formation of new particles, nitric acid, peroxyacyl nitrates, aldehydes, ozone, and sulfate aerosol.

Response to Comment on “Missing gas-phase source of HONO inferred from Zeppelin measurements in the troposphere”

Ye et al. have determined a maximum nitrous acid (HONO) yield of 3% for the reaction HO2·H2O + NO2, which is much lower than the yield used in our work. This finding, however, does not affect our main result that HONO in the investigated Po Valley region is mainly from a gas-phase source that consumes nitrogen oxides.

Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and MCM v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γglyx of 2 × 10-3, and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0-0.8 μg m-3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (RGF = [GLYX]/[HCHO]), resulting from the suppression of δ-isoprene peroxy radicals (δ-ISOPO2). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of IEPOX peroxy radicals (IEPOXOO) with HO2. Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.

Emissions of Glyoxal and Other Carbonyl Compounds from Agricultural Biomass Burning Plumes Sampled by Aircraft

We report enhancements of glyoxal and methylglyoxal relative to carbon monoxide and formaldehyde in agricultural biomass burning plumes intercepted by the NOAA WP-3D aircraft during the 2013 Southeast Nexus and 2015 Shale Oil and Natural Gas Nexus campaigns. Glyoxal and methylglyoxal were measured using broadband cavity enhanced spectroscopy, which for glyoxal provides a highly selective and sensitive measurement. While enhancement ratios of other species such as methane and formaldehyde were consistent with previous measurements, glyoxal enhancements relative to carbon monoxide averaged 0.0016 ± 0.0009, a factor of 4 lower than values used in global models. Glyoxal enhancements relative to formaldehyde were 30 times lower than previously reported, averaging 0.038 ± 0.02. Several glyoxal loss processes such as photolysis, reactions with hydroxyl radicals, and aerosol uptake were found to be insufficient to explain the lower measured values of glyoxal relative to other biomass burning trace gases, indicating that glyoxal emissions from agricultural biomass burning may be significantly overestimated. Methylglyoxal enhancements were three to six times higher than reported in other recent studies, but spectral interferences from other substituted dicarbyonyls introduce an estimated correction factor of 2 and at least a 25% uncertainty, such that accurate measurements of the enhancements are difficult.

Modeling Ozone in the Eastern U.S. using a Fuel-Based Mobile Source Emissions Inventory

Recent studies suggest overestimates in current U.S. emission inventories of nitrogen oxides (NO x = NO + NO2). Here, we expand a previously developed fuel-based inventory of motor-vehicle emissions (FIVE) to the continental U.S. for the year 2013, and evaluate our estimates of mobile source emissions with the U.S. Environmental Protection Agencys National Emissions Inventory (NEI) interpolated to 2013. We find that mobile source emissions of NO x and carbon monoxide (CO) in the NEI are higher than FIVE by 28% and 90%, respectively. Using a chemical transport model, we model mobile source emissions from FIVE, and find consistent levels of urban NO x and CO as measured during the Southeast Nexus (SENEX) Study in 2013. Lastly, we assess the sensitivity of ozone (O3) over the Eastern U.S. to uncertainties in mobile source NO x emissions and biogenic volatile organic compound (VOC) emissions. The ground-level O3 is sensitive to reductions in mobile source NO x emissions, most notably in the Southeastern U.S. and during O3 exceedance events, under the revised standard proposed in 2015 (>70 ppb, 8 h maximum). This suggests that decreasing mobile source NO x emissions could help in meeting more stringent O3 standards in the future.