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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.

The sources and distribution of tropospheric nitrous acid (HONO) were examined using airborne measurements over the Southeast U.S. during the Southeast Nexus Experiment in June and July 2013. HONO was measured once per second using a chemical ionization mass spectrometer on the NOAA WP-3D aircraft to assess sources that affect HONO abundance throughout the planetary boundary layer (PBL). The aircraft flew at altitudes between 0.12 and 6.4 km above ground level on 18 research flights that were conducted both day and night, sampling emissions from urban and power plant sources that were transported in the PBL. At night, HONO mixing ratios were greatest in plumes from agricultural burning, where they exceeded 4 ppbv and accounted for 2–14% of the reactive nitrogen emitted by the fires. The HONO to carbon monoxide ratio in these plumes from flaming stage fires ranged from 0.13 to 0.52%. Direct HONO emissions from coal-fired power plants were quantified using measurements at night, when HONO loss by photolysis was absent. These direct emissions were often correlated with total reactive nitrogen with enhancement ratios that ranged from 0 to 0.4%. HONO enhancements in power plant plumes measured during the day were compared with a Lagrangian plume dispersion model, showing that HONO produced solely from the gas phase reaction of OH with NO explained the observations. Outside of recently emitted plumes from known combustion sources, HONO mixing ratios measured several hundred meters above ground level were indistinguishable from zero within the 15 parts per trillion by volume measurement uncertainty. The results reported here do not support the existence of a ubiquitous unknown HONO source that produces significant HONO concentrations in the lower troposphere.

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.

[1] Limitations in the chemical characterization of tropospheric organic aerosol (OA) continue to impede attempts to fully understand its chemical sources and sinks. To assess the role of organic nitrates in OA, we used a new thermal dissociation-laser induced fluorescence-based (TD-LIF) technique to obtain a high-time-resolution record of total aerosol organic nitrates (hereafter ΣANsaer) at the Bakersfield, CA supersite during the 2010 CalNex campaign. The TD-LIF measurements compare well with Fourier transform infrared measurements from collocated filter samples. These measurements show that ΣANs are a ubiquitous component of the OA with the –ONO2 subunit comprising on average 4.8% of the OA mass. Scaling this fraction by an estimate of the organic backbone mass yields an estimate that 17–23% of OA molecules contain nitrate functional groups. Measurements of both total ΣAN (gas + aerosol) and ΣANaer show that on average 21% of ΣANs are in the condensed phase, suggesting atmospheric organic nitrates have similar volatilities to analogous non-nitrate oxidized organic compounds. The fraction of ΣAN that is in the condensed phase increases with total OA concentration, providing direct evidence from the atmosphere that absorptive partitioning into OA has some control over the ΣAN phase partitioning. The specific molecular identity of the ΣAN is incompletely understood. Both biogenic hydrocarbons and long chain alkanes are calculated to be significant sources of low volatility nitrates in Bakersfield, and ultra performance liquid chromatography coupled to an electrospray ionization high-resolution quadrupole time-of-flight mass spectrometer measurements confirm the existence of particulate nitrooxy organosulfates derived from gas-phase oxidation of both isoprene and monoterpenes.