As part of the Deep Convective Cloud and Chemistry (DC3) experiment, the National Science Foundation/National Center for Atmospheric Research (NCAR) Gulfstream‐V (GV) and NASA DC‐8 research aircraft ...probed the chemical composition of the inflow and outflow of two convective storms (north storm, NS, south storm, SS) originating in the Colorado region on 22 June 2012, a time when the High Park wildfire was active in the area. A wide range of trace species were measured on board both aircraft including biomass burning (BB) tracers hydrogen cyanide (HCN) and acetonitrile (ACN). Acrolein, a much shorter lived tracer for BB, was also quantified on the GV. The data demonstrated that the NS had ingested fresh smoke from the High Park fire and as a consequence had a higher VOC OH reactivity than the SS. The SS lofted aged fire tracers along with other boundary layer ozone precursors and was more impacted by lightning NOx (LNOx) than the NS. The NCAR master mechanism box model was initialized with measurements made in the outflow of the two storms. The NS and SS were predicted to produce 11 and 14 ppbv of O3, respectively, downwind of the storm over 2 days. Sensitivity tests revealed that the ozone production potential of the SS was highly dependent on LNOx. Normalized excess mixing ratios, ΔX/ΔCO, for HCN and ACN were determined in both the fire plume and the storm outflow and found to be 7.0 ± 0.5 and 2.3 ± 0.5 pptv ppbv−1, respectively, and 1.4 ± 0.3 pptv ppbv−1 for acrolein in the outflow only.
Key Points
Lightning NOx is a key driver of ozone production in storm outflows
Storms can transport biomass burning emissions to the upper troposphere
Acrolein is shown to be a good tracer for fresh biomass burning emissions
Observations of C1‐C10 hydrocarbon mixing ratios measured by in situ instrumentation at the La Porte super site during the TexAQS 2000 field experiment are reported. The La Porte data were compared ...to a roadway vehicle exhaust signature obtained from canister samples collected in the Houston Washburn tunnel during the same summer to better understand the impact of petrochemical emissions of hydrocarbons at the site. It is shown that the abundance of ethene, propene, 1‐butene, C2‐C4 alkanes, hexane, cyclohexane, methylcyclohexane, isopropylbenzene, and styrene at La Porte were systematically affected by petrochemical industry emissions. Coherent power law relationships between frequency distribution widths of hydrocarbon mixing ratios and their local lifetimes clearly identify two major source groups, roadway vehicle emissions and industrial emissions. Distributions of most aromatics and long chain alkanes were consistent with roadway vehicle emissions as the dominant source. Air mass reactivity was generally dominated by C1‐C3 aldehydes. Propene and ethene sometimes dominated air mass reactivity with HO loss frequencies often greater than 10 s−1. Ozone mixing ratios near 200 ppbv were observed on two separate occasions, and these air masses appear to have been affected by industrial emissions of alkenes from the Houston Ship Channel. The La Porte data provide evidence of the importance of industrial emissions of ethene and propene on air mass reactivity and ozone formation in Houston.
Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. ...PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C5H8H+), acetaldehyde (m/z 45, CH3CHO+), and benzene (m/z 79, C6H6H+). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra.
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