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Abstract. Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured on board the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2, with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NOy) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of −296 ± 51 g kg−1, consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per parts per million by volume (ppmv) of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO2, NOy, and black carbon than with CO. More than half of the NOy in fresh plumes is NO2 with an R2 of 0.95 and a ratio of NO2 to NOy of 0.55 ± 0.05 ppbv ppbv−1, highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NOy to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol.

 

Abstract. Light absorbing organic carbon, or brown carbon (BrC), can be a significantcontributor to the visible light absorption budget. However, the sources ofBrC and the contributions of BrC to light absorption are not wellunderstood. Biomass burning is thought to be a major source of BrC.Therefore, as part of the WE-CAN (Western Wildfire Experiment for CloudChemistry, Aerosol Absorption and Nitrogen) study, BrC absorption data werecollected on board the National Science Foundation/National Center for Atmospheric Research (NSF/NCAR) C-130 aircraft as it intercepted smoke fromwildfires in the western US in July–August 2018. BrC absorptionmeasurements were obtained in near real-time using two techniques. The firstcoupled a particle-into-liquid sampler (PILS) with a liquid waveguidecapillary cell and a total organic carbon analyzer for measurements ofwater-soluble BrC absorption and WSOC (water-soluble organic carbon). Thesecond employed a custom-built photoacoustic aerosol absorption spectrometer(PAS) to measure total absorption at 405 and 660 nm. The PAS BrC absorption at 405 nm (PAS total Abs 405 BrC) was calculated by assuming the absorption determined by the PAS at 660 nm was equivalent to the black carbon (BC) absorption and the BC aerosol absorption Ångström exponent was 1. Data from the PILS and PAS were combined to investigate the water-soluble vs. total BrC absorption at 405 nm in the various wildfire plumes sampled during WE-CAN. WSOC, PILS water-soluble Abs 405, and PAS total Abs 405 tracked each other in and out of the smoke plumes. BrC absorption was correlated with WSOC (R2 value for PAS =0.42 and PILS =0.60) and CO (carbon monoxide) (R2 value for PAS =0.76 and PILS =0.55) for all wildfires sampled. The PILS water-soluble Abs 405 was corrected for thenon-water-soluble fraction of the aerosol using the calculated UHSAS(ultra-high-sensitivity aerosol spectrometer) aerosol mass. The correctedPILS water-soluble Abs 405 showed good closure with the PAS total Abs 405BrC with a factor of ∼1.5 to 2 difference. This differencewas explained by particle vs. bulk solution absorption measured by the PASvs. PILS, respectively, and confirmed by Mie theory calculations. DuringWE-CAN, ∼ 45 % (ranging from 31 % to 65 %) of the BrCabsorption was observed to be due to water-soluble species. The ratio of BrC absorption to WSOC or ΔCO showed no clear dependence on firedynamics or the time since emission over 9 h. 

Abstract. A closed-path quantum-cascade tunable infrared laserdirect absorption spectrometer (QC-TILDAS) was outfitted with an inertialinlet for filter-less separation of particles and several custom-designedcomponents including an aircraft inlet, a vibration isolation mountingplate, and a system for optionally adding active continuous passivation forgas-phase measurements of ammonia (NH3) from a research aircraft. Theinstrument was then deployed on the NSF/NCAR C-130 aircraft during researchflights and test flights associated with the Western wildfire Experiment forCloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) field campaign.The instrument was configured to measure large, rapid gradients in gas-phaseNH3, over a range of altitudes, in smoke (e.g., ash and particles), inthe boundary layer (e.g., during turbulence and turns), in clouds, and in ahot aircraft cabin (e.g., average aircraft cabin temperatures expected toexceed 30 ∘C during summer deployments). Important designgoals were to minimize motion sensitivity, maintain a reasonable detectionlimit, and minimize NH3 “stickiness” on sampling surfaces to maintainfast time response in flight. The observations indicate that adding ahigh-frequency vibration to the laser objective in the QC-TILDAS andmounting the QC-TILDAS on a custom-designed vibration isolation plate weresuccessful in minimizing motion sensitivity of the instrument during flight.Allan variance analyses indicate that the in-flight precision of theinstrument is 60 ppt at 1 Hz corresponding to a 3σ detection limitof 180 ppt. Zero signals span ±200, or 400 pptv total, withcabin pressure and temperature and altitude in flight. The option for activecontinuous passivation of the sample flow path with1H,1H-perfluorooctylamine, a strong perfluorinated base, preventedadsorption of both water and basic species to instrument sampling surfaces.Characterization of the time response in flight and on the ground showedthat adding passivant to a “clean” instrument system had little impact onthe time response. In contrast, passivant addition greatly improved the timeresponse when sampling surfaces became contaminated prior to a test flight.The observations further show that passivant addition can be used tomaintain a rapid response for in situ NH3 measurements over the duration of anairborne field campaign (e.g., ∼2 months) since passivantaddition also helps to prevent future buildup of water and basic species oninstrument sampling surfaces. Therefore, we recommend the use of activecontinuous passivation with closed-path NH3 instruments when rapid(>1 Hz) collection of NH3 is important for the scientificobjective of a field campaign (e.g., sampling from aircraft or anothermobile research platform). Passivant addition can be useful for maintainingoptimum operation and data collection in NH3-rich and humid environments orwhen contamination of sampling surfaces is likely, yet frequent cleaning isnot possible. Passivant addition may not be necessary for fast operation,even in polluted environments, if sampling surfaces can be cleaned when thetime response has degraded. 

Reactive nitrogen (N_r) within smoke plumes plays important roles in the production of ozone, the formation of secondary aerosols, and deposition of fixed N to ecosystems. The Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) field campaign sampled smoke from 23 wildfires throughout the western U.S. during summer 2018 using the NSF/NCAR C‐130 research aircraft. We empirically estimateN_rnormalized excess mixing ratios and emission factors from fires sampled within 80 min of estimated emission and explore variability in the dominant forms ofN_rbetween these fires. We find that reduced N compounds comprise a majority (39%–80%; median = 66%) of total measured reactive nitrogen (ΣN_r) emissions. The smoke plumes sampled during WE‐CAN feature rapid chemical transformations after emission. As a result, within minutes after emission total measured oxidized nitrogen (ΣNO_y) and measured totalΣNH_x(NH₃ + pNH₄) are more robustly correlated with modified combustion efficiency (MCE) than NO_xand NH₃by themselves. The ratio of ΣNH_x/ΣNO_ydisplays a negative relationship with MCE, consistent with previous studies. A positive relationship with total measuredΣN_rsuggests that both burn conditions and fuel N content/volatilization differences contribute to the observed variability in the distribution of reduced and oxidizedN_r. Additionally, we compare our in situ field estimates ofN_rEFs to previous lab and field studies. For similar fuel types, we findΣNH_xEFs are of the same magnitude or larger than lab‐based NH₃EF estimates, andΣNO_yEFs are smaller than lab NO_xEFs.

 

Wildfires are a major source of gas‐phase ammonia (NH₃) to the atmosphere. Quantifying the evolution and fate of this NH₃is important to understanding the formation of secondary aerosol in smoke and its accompanying effects on radiative balance and nitrogen deposition. Here, we use data from the Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) to add new empirical constraints on the e‐folding loss timescale of NH₃and its relationship with particulate ammonium (pNH₄) within wildfire smoke plumes in the western U.S. during summer 2018. We show that the e‐folding loss timescale of NH₃with respect to particle‐phase partitioning ranges from ∼24 to ∼4000 min (median of 55 min). Within these same plumes, oxidation of nitrogen oxides is observed concurrent with increases in the fraction ofpNH₄in each plume sampled, suggesting that formation of ammonium nitrate (NH₄NO₃) is likely. We find wide variability in how close ourin situmeasurements of NH₄NO₃are to those expected in a dry thermodynamic equilibrium, and find that NH₄NO₃is most likely to form in fresh, dense smoke plumes injected at higher altitudes and colder temperatures. In chemically older smoke we observe correlations between both the fraction ofpNH₄and the fraction of particulate nitrate (pNO₃) in the aerosol with temperature, providing additional evidence of the presence of NH₄NO₃and the influence of injection height on gas‐particle partitioning of NH₃.