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The impact of biomass burning (BB) on the atmospheric burden of volatile organic compounds (VOCs) is highly uncertain. Here we apply the GEOS-Chem chemical transport model (CTM) to constrain BB emissions in the western USA at ∼ 25 km resolution. Across three BB emission inventories widely used in CTMs, the inventory–inventory comparison suggests that the totals of 14 modeled BB VOC emissions in the western USA agree with each other within 30 %–40 %. However, emissions for individual VOCs can differ by a factor of 1–5, driven by the regionally averaged emission ratios (ERs, reflecting both assigned ERs for specific biome and vegetation classifications) across the three inventories. We further evaluate GEOS-Chem simulations with aircraft observations made during WE-CAN (Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption and Nitrogen) and FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality) field campaigns. Despite being driven by different global BB inventories or applying various injection height assumptions, the model–observation comparison suggests that GEOS-Chem simulations underpredict observed vertical profiles by a factor of 3–7. The model shows small to no bias for most species in low-/no-smoke conditions. We thus attribute the negative model biases mostly to underestimated BB emissions in these inventories. Tripling BB emissions in the model reproduces observed vertical profiles for primary compounds, i.e., CO, propane, benzene, and toluene. However, it shows no to less significant improvements for oxygenated VOCs, particularly for formaldehyde, formic acid, acetic acid, and lumped ≥ C3 aldehydes, suggesting the model is missing secondary sources of these compounds in BB-impacted environments. The underestimation of primary BB emissions in inventories is likely attributable to underpredicted amounts of effective dry matter burned, rather than errors in fire detection, injection height, or ERs, as constrained by aircraft and ground measurements. We cannot rule out potential sub-grid uncertainties (i.e., not being able to fully resolve fire plumes) in the nested GEOS-Chem which could explain the negative model bias partially, though back-of-the-envelope calculation and evaluation using longer-term ground measurements help support the argument of the dry matter burned underestimation. The total ERs of the 14 BB VOCs implemented in GEOS-Chem only account for half of the total 161 measured VOCs (∼ 75 versus 150 ppb ppm−1). This reveals a significant amount of missing reactive organic carbon in widely used BB emission inventories. Considering both uncertainties in effective dry matter burned (× 3) and unmodeled VOCs (× 2), we infer that BB contributed to 10 % in 2019 and 45 % in 2018 (240 and 2040 Gg C) of the total VOC primary emission flux in the western USA during these two fire seasons, compared to only 1 %–10 % in the standard GEOS-Chem.

Wildfires are a source of primary aerosols and precursors for secondary aerosols to the atmosphere. In this work, we discover that the evolution of these aerosols depends strongly on the coupled effects of dilution, photooxidation, and partitioning.

The Arctic is a climatically sensitive region that has experienced warming at almost 3 times the global average rate in recent decades, leading to an increase in Arctic greenness and a greater abundance of plants that emit biogenic volatile organic compounds (BVOCs). These changes in atmospheric emissions are expected to significantly modify the overall oxidative chemistry of the region and lead to changes in VOC composition and abundance, with implications for atmospheric processes. Nonetheless, observations needed to constrain our current understanding of these issues in this critical environment are sparse. This work presents novel atmospheric in situ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) measurements of VOCs at Toolik Field Station (TFS; 68∘38′ N, 149∘36' W), in the Alaskan Arctic tundra during May–June 2019. We employ a custom nested grid version of the GEOS-Chem chemical transport model (CTM), driven with MEGANv2.1 (Model of Emissions of Gases and Aerosols from Nature version 2.1) biogenic emissions for Alaska at 0.25∘ × 0.3125∘ resolution, to interpret the observations in terms of their constraints on BVOC emissions, total reactive organic carbon (ROC) composition, and calculated OH reactivity (OHr) in this environment. We find total ambient mole fraction of 78 identified VOCs to be 6.3 ± 0.4 ppbv (10.8 ± 0.5 ppbC), with overwhelming (> 80 %) contributions are from short-chain oxygenated VOCs (OVOCs) including methanol, acetone and formaldehyde. Isoprene was the most abundant terpene identified. GEOS-Chem captures the observed isoprene (and its oxidation products), acetone and acetaldehyde abundances within the combined model and observation uncertainties (±25 %), but underestimates other OVOCs including methanol, formaldehyde, formic acid and acetic acid by a factor of 3 to 12. The negative model bias for methanol is attributed to underestimated biogenic methanol emissions for the Alaskan tundra in MEGANv2.1. Observed formaldehyde mole fractions increase exponentially with air temperature, likely reflecting its biogenic precursors and pointing to a systematic model underprediction of its secondary production. The median campaign-calculated OHr from VOCs measured at TFS was 0.7 s−1, roughly 5 % of the values typically reported in lower-latitude forested ecosystems. Ten species account for over 80 % of the calculated VOC OHr, with formaldehyde, isoprene and acetaldehyde together accounting for nearly half of the total. Simulated OHr based on median-modeled VOCs included in GEOS-Chem averages 0.5 s−1 and is dominated by isoprene (30 %) and monoterpenes (17 %). The data presented here serve as a critical evaluation of our knowledge of BVOCs and ROC budgets in high-latitude environments and represent a foundation for investigating and interpreting future warming-driven changes in VOC emissions in the Alaskan Arctic tundra.

The evolution of organic aerosol (OA) and brown carbon (BrC) in wildfire plumes, including the relative contributions of primary versus secondary sources, has been uncertain in part because of limited knowledge of the precursor emissions and the chemical environment of smoke plumes. We made airborne measurements of a suite of reactive trace gases, particle composition, and optical properties in fresh western US wildfire smoke in July through August 2018. We use these observations to quantify primary versus secondary sources of biomass-burning OA (BBPOA versus BBSOA) and BrC in wildfire plumes. When a daytime wildfire plume dilutes by a factor of 5 to 10, we estimate that up to one-third of the primary OA has evaporated and subsequently reacted to form BBSOA with near unit yield. The reactions of measured BBSOA precursors contribute only 13 ± 3% of the total BBSOA source, with evaporated BBPOA comprising the rest. We find that oxidation of phenolic compounds contributes the majority of BBSOA from emitted vapors. The corresponding particulate nitrophenolic compounds are estimated to explain 29 ± 15% of average BrC light absorption at 405 nm (BrC Abs(405)) measured in the first few hours of plume evolution, despite accounting for just 4 ± 2% of average OA mass. These measurements provide quantitative constraints on the role of dilution-driven evaporation of OA and subsequent radical-driven oxidation on the fate of biomass-burning OA and BrC in daytime wildfire plumes and point to the need to understand how processing of nighttime emissions differs.

Wildfires are an important source of nitrous acid (HONO), a photolabile radical precursor, yet in situ measurements and quantification of primary HONO emissions from open wildfires have been scarce. We present airborne observations of HONO within wildfire plumes sampled during the Western Wildfire Experiment for Cloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) campaign. ΔHONO/ΔCO close to the fire locations ranged from 0.7 to 17 pptv ppbv

Wildfire emissions affect downwind air quality and human health. Predictions of these impacts using models are limited by uncertainties in emissions and chemical evolution of smoke plumes. Using hi...

Reactive nitrogen (Nr) 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 estimate Nr normalized excess mixing ratios and emission factors from fires sampled within 80 min of estimated emission and explore variability in the dominant forms of Nr between these fires. We find that reduced N compounds comprise a majority (39%-80%; median = 66%) of total measured reactive nitrogen (ΣNr) 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 (ΣNOy) and measured total ΣNHx (NH3 + pNH4) are more robustly correlated with modified combustion efficiency (MCE) than NOx and NH3 by themselves. The ratio of ΣNHx/ΣNOy displays a negative relationship with MCE, consistent with previous studies. A positive relationship with total measured ΣNr suggests that both burn conditions and fuel N content/volatilization differences contribute to the observed variability in the distribution of reduced and oxidized Nr. Additionally, we compare our in situ field estimates of Nr EFs to previous lab and field studies. For similar fuel types, we find ΣNHx EFs are of the same magnitude or larger than lab-based NH3 EF estimates, and ΣNOy EFs are smaller than lab NOx EFs.

During summer 2018, wildfire smoke impacted the atmospheric composition and photochemistry across much of the western U.S. Smoke is becoming an increasingly important source of air pollution for this region, and this problem will continue to be exacerbated by climate change. The Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption and Nitrogen (WE-CAN) project deployed a research aircraft in summer 2018 (22 July – 31 August) to sample wildfire smoke during its first day of atmospheric evolution using Boise, ID as a base. We report on measurements of gas-phase species collected in aircraft ascents and descents through the boundary layer. We classify ascents and descents with mean hydrogen cyanide (HCN) > 300 pptv and acetonitrile (CH3CN) > 200 pptv as smoke-impacted. We contrast data from the 16 low/no-smoke and 16 smoke-impacted ascents and descents to determine differences between the two data subsets. The smoke was transported from local fires in Idaho as well as from major fire complexes in Oregon and California. During the smoke-impacted periods, the abundances of many gas-phase species, including carbon monoxide (CO), ozone (O3), formaldehyde (HCHO), and peroxyacetyl nitrate (PAN) were significantly higher than low/no-smoke periods. When compared to ground-based data obtained from the Colorado Front Range in summer 2015, we found that a similar subset of gas-phase species increased when both areas were smoke-impacted. During smoke-impacted periods, the average abundances of several Hazardous Air Pollutants (HAPs), including benzene, HCHO, and acetaldehyde, were comparable in magnitude to the annual averages in many major U.S. urban areas.

A closed-path quantum-cascade tunable infrared laser direct absorption spectrometer (QC-TILDAS) was outfitted with an inertial inlet for filter-less separation of particles and several custom-designed components including an aircraft inlet, a vibration isolation mounting plate, and a system for optionally adding active continuous passivation for gas-phase measurements of ammonia (NH3) from a research aircraft. The instrument was then deployed on the NSF/NCAR C-130 aircraft during research flights and test flights associated with the Western wildfire Experiment for Cloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) field campaign. The instrument was configured to measure large, rapid gradients in gas-phase NH3, over a range of altitudes, in smoke (e.g., ash and particles), in the boundary layer (e.g., during turbulence and turns), in clouds, and in a hot aircraft cabin (e.g., average aircraft cabin temperatures expected to exceed 30 ∘C during summer deployments). Important design goals were to minimize motion sensitivity, maintain a reasonable detection limit, and minimize NH3 “stickiness” on sampling surfaces to maintain fast time response in flight. The observations indicate that adding a high-frequency vibration to the laser objective in the QC-TILDAS and mounting the QC-TILDAS on a custom-designed vibration isolation plate were successful in minimizing motion sensitivity of the instrument during flight. Allan variance analyses indicate that the in-flight precision of the instrument is 60 ppt at 1 Hz corresponding to a 3σ detection limit of 180 ppt. Zero signals span ±200, or 400 pptv total, with cabin pressure and temperature and altitude in flight. The option for active continuous passivation of the sample flow path with 1H,1H-perfluorooctylamine, a strong perfluorinated base, prevented adsorption of both water and basic species to instrument sampling surfaces. Characterization of the time response in flight and on the ground showed that adding passivant to a “clean” instrument system had little impact on the time response. In contrast, passivant addition greatly improved the time response when sampling surfaces became contaminated prior to a test flight. The observations further show that passivant addition can be used to maintain a rapid response for in situ NH3 measurements over the duration of an airborne field campaign (e.g., ∼2 months) since passivant addition also helps to prevent future buildup of water and basic species on instrument sampling surfaces. Therefore, we recommend the use of active continuous passivation with closed-path NH3 instruments when rapid (>1 Hz) collection of NH3 is important for the scientific objective of a field campaign (e.g., sampling from aircraft or another mobile research platform). Passivant addition can be useful for maintaining optimum operation and data collection in NH3-rich and humid environments or when contamination of sampling surfaces is likely, yet frequent cleaning is not possible. Passivant addition may not be necessary for fast operation, even in polluted environments, if sampling surfaces can be cleaned when the time response has degraded.

A closed-path quantum cascade tunable infrared laser direct absorption spectrometer (QC-TILDAS) was outfitted with an inertial inlet for filter-less separation of particles, a custom-designed aircraft inlet, a custom-built vibration isolation mounting plate, and a custom-built system for optionally adding active continuous passivation for gas-phase measurements of ammonia (NH3) from a research aircraft. The flight-ready instrument was then deployed on the NSF/NCAR C-130 aircraft during research flights and test flights associated with the Western wildfire Experiment for Cloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) field campaign. The flight-ready instrument was configured to measure large, rapid gradients in gas-phase NH3, over a range of altitudes, in smoke (e.g., ash and particles), in the boundary layer (e.g., during turbulence and turns), in clouds, and in a hot aircraft cabin. Important design goals were to minimize motion sensitivity, maintain a reasonable detection limit, and minimize NH3 stickiness on sampling surfaces to maintain fast time response in flight. The observations indicate that addition of a high frequency vibration to the laser objective in the QC-TILDAS and mounting the QC-TILDAS on a custom-designed vibration isolation plate were successful in minimizing motion sensitivity of the instrument during flight. Allan variance analyses indicate that the in-flight precision of the flight-ready instrument is 60 ppt at 1 Hz corresponding to a 3-sigma detection limit of 180 ppt. The option for active continuous passivation of the sample flow path with 1H,1H-perfluorooctylamine, a strong perfluorinated base, prevented adsorption of both water and basic species to instrument sampling surfaces. Characterization of the time response in flight and on the ground showed that adding passivant to a clean instrument system had little impact on the time response. In contrast, passivant addition greatly improved the time response when sampling surfaces became contaminated prior to a test flight. The observations further show that passivant addition can be a useful tool for maintaining a rapid response for in-situ NH3 measurements over the duration of an airborne field campaign (e.g., ∼2 months for WE-CAN test and research flights) since passivant addition also helps to prevent future build-up of water and basic species on instrument sampling surfaces. Therefore, we recommend the use of active continuous passivation with closed-path NH3 instruments when rapid (> 1 Hz) collection of NH3 is important for the scientific objective of a field campaign (e.g., measuring fluxes, sampling from aircraft or another mobile research platform). Passivant addition can be useful for maintaining optimum operation and data collection in NH3-rich/humid environments or when contamination of sampling surfaces is likely, yet frequent cleaning is not possible. Passivant addition may not be necessary for fast operation, even in polluted environments, if sampling surfaces can be cleaned when the time response has degraded.