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Using OH reactivity we assess the major daytime OH radical sinks in western U.S. wildfire plumes and other smoke impacted environments, testing their current model representation while providing a roadmap for future model development.

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.

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.

To better understand the effects of wildfires on air quality and climate, it is important to assess the occurrence of chromophoric compounds in smoke and characterize their optical properties. This study explores the molecular composition of light-absorbing organic aerosol, or brown carbon (BrC), sampled at the Missoula Fire Sciences laboratory as a part of the FIREX Fall 2016 lab intensive. A total of 12 biomass fuels from different plant types were tested, including gymnosperm (coniferous) and angiosperm (flowering) plants and different ecosystem components such as duff, litter, and canopy. Emitted biomass burning organic aerosol (BBOA) particles were collected onto Teflon filters and analyzed offline using high-performance liquid chromatography coupled to a photodiode array spectrophotometer and a high-resolution mass spectrometer (HPLC–PDA–HRMS). Separated BrC chromophores were classified by their retention times, absorption spectra, integrated absorbance in the near-UV and visible spectral range (300–700 nm), and chemical formulas from the accurate m∕z measurements. BrC chromophores were grouped into the following classes and subclasses: lignin-derived products, which include lignin pyrolysis products; distillation products, which include coumarins and flavonoids; nitroaromatics; and polycyclic aromatic hydrocarbons (PAHs). The observed classes and subclasses were common across most fuel types, although specific BrC chromophores varied based on plant type (gymnosperm or angiosperm) and ecosystem component(s) burned. To study the stability of the observed BrC compounds with respect to photodegradation, BBOA particle samples were irradiated directly on filters with near UV (300–400 nm) radiation, followed by extraction and HPLC–PDA–HRMS analysis. Lifetimes of individual BrC chromophores depended on the fuel type and the corresponding combustion condition. Lignin-derived and flavonoid classes of BrC generally had the longest lifetimes with respect to UV photodegradation. Moreover, lifetimes for the same type of BrC chromophores varied depending on biomass fuel and combustion conditions. While individual BrC chromophores disappeared on a timescale of several days, the overall light absorption by the sample persisted longer, presumably because the condensed-phase photochemical processes converted one set of chromophores into another without complete photobleaching or from undetected BrC chromophores that photobleached more slowly. To model the effect of BrC on climate, it is important to understand the change in the overall absorption coefficient with time. We measured the equivalent atmospheric lifetimes of the overall BrC absorption coefficient, which ranged from 10 to 41 d, with subalpine fir having the shortest lifetime and conifer canopies, i.e., juniper, having the longest lifetime. BrC emitted from biomass fuel loads encompassing multiple ecosystem components (litter, shrub, canopy) had absorption lifetimes on the lower end of the range. These results indicate that photobleaching of BBOA by condensed-phase photochemistry is relatively slow. Competing chemical aging mechanisms, such as heterogeneous oxidation by OH, may be more important for controlling the rate of BrC photobleaching in BBOA.

We present a comparison of fast-response instruments installed onboard the NASA DC-8 aircraft that measured nitrogen oxides (NO and NO2), nitrous acid (HONO), total reactive odd nitrogen (measured both as the total (NOy) and from the sum of individually measured species (SNOy)) and carbon monoxide (CO) in the troposphere during the 2019 Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign. By targeting smoke from summertime wildfires, prescribed fires and agricultural burns across the continental United States, FIREX-AQ provided a unique opportunity to investigate measurement accuracy in concentrated plumes where hundreds of species coexist. Here, we compare NO measurements by chemiluminescence (CL) and laser induced fluorescence (LIF); NO2 measurements by CL, LIF and cavity enhanced spectroscopy (CES); HONO measurements by CES and iodide-adduct chemical ionization mass spectrometry (CIMS); and CO measurements by tunable diode laser absorption spectrometry (TDLAS) and integrated cavity output spectroscopy (ICOS). Additionally, total NOy measurements using the CL instrument were compared with SNOy (= NO + NO2 + HONO + nitric acid (HNO3) + acyl peroxy nitrates (APNs) + submicron particulate nitrate (pNO3)). The aircraft instrument intercomparisons demonstrate the following: 1) NO measurements by CL and LIF agreed well within instrument uncertainties, but with potentially reduced time response for the CL instrument; 2) NO2 measurements by LIF and CES agreed well within instrument uncertainties, but CL NO2 was on average 10 % higher; 3) CES and CIMS HONO measurements were highly correlated in each fire plume transect, but the correlation slope of CES vs. CIMS for all 1 Hz data during FIREX-AQ was 1.8, which we attribute to a reduction in the CIMS sensitivity to HONO in high temperature environments; 4) NOy budget closure was demonstrated for all flights within the combined instrument uncertainties of 25 %. However, we used a fluid dynamic flow model to estimate that average pNO3 sampling fraction through the NOy inlet in smoke was variable from one flight to another and ranged between 0.36 and 0.99, meaning that approximately 0–24 % on average of the total measured NOy in smoke may have been unaccounted for and may be due to unmeasured species such as organic nitrates; 5) CO measurements by ICOS and TDLAS agreed well within combined instrument uncertainties, but with a systematic offset that averaged 2.87 ppbv; and 6) integrating smoke plumes followed by fitting the integrated values of each plume improved the correlation between independent measurements.

Description, While ozone increases rapidly in wildfire plumes, downwind its production rate slows dramatically as nitrogen oxide levels decline., Wildfires are a substantial but poorly quantified source of tropospheric ozone (O3). Here, to investigate the highly variable O3 chemistry in wildfire plumes, we exploit the in situ chemical characterization of western wildfires during the FIREX-AQ flight campaign and show that O3 production can be predicted as a function of experimentally constrained OH exposure, volatile organic compound (VOC) reactivity, and the fate of peroxy radicals. The O3 chemistry exhibits rapid transition in chemical regimes. Within a few daylight hours, the O3 formation substantially slows and is largely limited by the abundance of nitrogen oxides (NOx). This finding supports previous observations that O3 formation is enhanced when VOC-rich wildfire smoke mixes into NOx-rich urban plumes, thereby deteriorating urban air quality. Last, we relate O3 chemistry to the underlying fire characteristics, enabling a more accurate representation of wildfire chemistry in atmospheric models that are used to study air quality and predict climate.

Understanding the efficiency and variability of photochemical ozone (O3) production from western wildfire plumes is important to accurately estimate their influence on North American air quality. A set of photochemical measurements were made from the NOAA Twin Otter research aircraft as a part of the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) experiment. We use a zero-dimensional (0-D) box model to investigate the chemistry driving O3 production in modeled plumes. Modeled afternoon plumes reached a maximum O3 mixing ratio of 140 ± 50 ppbv (average ± standard deviation) within 20 ± 10 min of emission compared to 76 ± 12 ppbv in 60 ± 30 min in evening plumes. Afternoon and evening maximum O3 isopleths indicate that plumes were near their peak in NOx efficiency. A radical budget describes the NOx volatile - organic compound (VOC) sensitivities of these plumes. Afternoon plumes displayed a rapid transition from VOC-sensitive to NOx-sensitive chemistry, driven by HOx (=OH + HO2) production from photolysis of nitrous acid (HONO) (48 ± 20% of primary HOx) and formaldehyde (HCHO) (26 ± 9%) emitted directly from the fire. Evening plumes exhibit a slower transition from peak NOx efficiency to VOC-sensitive O3 production caused by a reduction in photolysis rates and fire emissions. HOx production in evening plumes is controlled by HONO photolysis (53 ± 7%), HCHO photolysis (18 ± 9%), and alkene ozonolysis (17 ± 9%).

New techniques have recently been developed and applied to capture reactive nitrogen species, including nitrogen oxides ( NO x = NO + NO 2 ), nitrous acid (HONO), nitric acid ( HNO3 ), and particulate nitrate ( p NO 3 - ), for accurate measurement of their isotopic composition. Here, we report – for the first time – the isotopic composition of HONO from biomass burning (BB) emissions collected during the Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) at the Missoula Fire Science Laboratory in the fall of 2016. We used our newly developed annular denuder system (ADS), which was verified to completely capture HONO associated with BB in comparison with four other high-time-resolution concentration measurement techniques, including mist chamber–ion chromatography (MC–IC), open-path Fourier transform infrared spectroscopy (OP-FTIR), cavity-enhanced spectroscopy (CES), and proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). In 20 “stack” fires (direct emission within ∼5 s of production by the fire) that burned various biomass materials from the western US, δ15N – NOx ranges from −4.3 ‰ to +7.0 ‰, falling near the middle of the range reported in previous work. The first measurements of δ15N –HONO and δ18O –HONO in biomass burning smoke reveal a range of −5.3 ‰ to +5.8 ‰ and +5.2 ‰ to +15.2 ‰, respectively. Both HONO and NOx are sourced from N in the biomass fuel, and δ15N –HONO and δ15N – NOx are strongly correlated ( R2=0.89 , p ), suggesting HONO is directly formed via subsequent chain reactions of NOx emitted from biomass combustion. Only 5 of 20 p NO 3 - samples had a sufficient amount for isotopic analysis and showed δ15N and δ18O of p NO 3 - ranging from −10.6 ‰ to −7.4 ‰ and +11.5 ‰ to +14.8 ‰, respectively. Our δ15N of NOx , HONO, and p NO 3 - ranges can serve as important biomass burning source signatures, useful for constraining emissions of these species in environmental applications. The δ18O of HONO and NO 3 - obtained here verify that our method is capable of determining the oxygen isotopic composition in BB plumes. The δ18O values for both of these species reflect laboratory conditions (i.e., a lack of photochemistry) and would be expected to track with the influence of different oxidation pathways in real environments. The methods used in this study will be further applied in future field studies to quantitatively track reactive nitrogen cycling in fresh and aged western US wildfire plumes.

Biomass burning (BB) is a major source of black carbon (BC), but comparing BC content of different smoke-impacted air masses may be uncertain if different measurement techniques are used to quantify the BC, or if non-BC fractions influence a given measurement. To investigate these potential issues, five instruments reporting BC were compared in well-mixed smoke during the FIREX laboratory campaign in 2016, including two filter-based absorption instruments; one in situ absorption instrument; a laser-induced incandescence instrument; and a thermal-optical instrument. BB aerosols were generated using fuels common to wildfires in the Western US in a relatively controlled environment, with BC concentrations ranging from roughly 10–100 μg m−3 (55 total fires). Applying the Bland-Altman graphical approach, systematic biases and proportional biases were identified between the selected reference instrument (in situ absorption) and the other four instruments. BC emission factors (EFBC) derived from the thermal-optical instrument, laser-induced incandescence instrument, and filter-based absorption instruments were, on average, 83%, 39% and 66%, greater than the in situ absorption instrument, respectively. To understand why these differences exist, principal component analysis combined with a K-means clustering algorithm was implemented to group different fires into three clusters based on several co-dependent fire-related parameters (modified combustion efficiency (MCE), single scattering albedo (SSA) at 870 nm, organic carbon/elemental carbon ratio (OC/EC ratio), and absorption Angstrom exponents (AAE)); clusters are nominally referred to as “Black”, “Mixed”, and “Brown” based on the mean SSA and AAE values for each. The best agreement among all instruments was observed for the “Black” cluster (mean EFBC ratio = 1.89, for the fires with mean SSA = 0.31 and AAE = 1.44); this agreement worsened for the “Mixed” (mean EFBC ratio = 2.94, for the fires with mean SSA = 0.80 and AAE = 1.92) and “Brown” clusters (mean EFBC ratio = 3.12, for the fires with mean SSA = 0.96 and AAE = 2.50), likely due to the increased presence of externally (or internally) mixed aerosols that altered the chemical and optical properties of the aerosols. In general, the discrepancies observed among the BC instruments from this work agree with or slightly exceed the ones from previous ambient and laboratory studies. Care should be taken when interpreting different BC measurements in BB smoke because large artifacts can occur due to co-emitted materials.

In mid-August through mid-September of 2017 a major wildfire smoke and haze episode strongly impacted most of the NW US and SW Canada. During this period our ground-based site in Missoula, Montana, experienced heavy smoke impacts for ∼ 500 h (up to 471 µg m−3 hourly average PM2.5). We measured wildfire trace gases, PM2.5 (particulate matter ≤2.5 µm in diameter), and black carbon and submicron aerosol scattering and absorption at 870 and 401 nm. This may be the most extensive real-time data for these wildfire smoke properties to date. Our range of trace gas ratios for ΔNH3∕ΔCO and ΔC2H4∕ΔCO confirmed that the smoke from mixed, multiple sources varied in age from ∼ 2–3 h to ∼ 1–2 days. Our study-average ΔCH4∕ΔCO ratio (0.166±0.088) indicated a large contribution to the regional burden from inefficient smoldering combustion. Our ΔBC∕ΔCO ratio (0.0012±0.0005) for our ground site was moderately lower than observed in aircraft studies (∼ 0.0015) to date, also consistent with a relatively larger contribution from smoldering combustion. Our ΔBC∕ΔPM2.5 ratio (0.0095±0.0003) was consistent with the overwhelmingly non-BC (black carbon), mostly organic nature of the smoke observed in airborne studies of wildfire smoke to date. Smoldering combustion is usually associated with enhanced PM emissions, but our ΔPM2.5∕ΔCO ratio (0.126±0.002) was about half the ΔPM1.0∕ΔCO measured in fresh wildfire smoke from aircraft (∼ 0.266). Assuming PM2.5 is dominated by PM1, this suggests that aerosol evaporation, at least near the surface, can often reduce PM loading and its atmospheric/air-quality impacts on the timescale of several days. Much of the smoke was emitted late in the day, suggesting that nighttime processing would be important in the early evolution of smoke. The diurnal trends show brown carbon (BrC), PM2.5, and CO peaking in the early morning and BC peaking in the early evening. Over the course of 1 month, the average single scattering albedo for individual smoke peaks at 870 nm increased from ∼ 0.9 to ∼ 0.96. Bscat401∕Bscat870 was used as a proxy for the size and “photochemical age” of the smoke particles, with this interpretation being supported by the simultaneously observed ratios of reactive trace gases to CO. The size and age proxy implied that the Ångström absorption exponent decreased significantly after about 10 h of daytime smoke aging, consistent with the only airborne measurement of the BrC lifetime in an isolated plume. However, our results clearly show that non-BC absorption can be important in “typical” regional haze and moderately aged smoke, with BrC ostensibly accounting for about half the absorption at 401 nm on average for our entire data set.

Formaldehyde (HCHO) is one of the most abundant non-methane volatile organic compounds (VOCs) emitted by fires. HCHO also undergoes chemical production and loss as a fire plume ages, and it can be an important oxidant precursor. In this study, we disentangle the processes controlling HCHO by examining its evolution in wildfire plumes sampled by the NASA DC-8 during the FIREX-AQ field campaign. In nine of the twelve analyzed plumes, dilution-normalized HCHO increases with physical age (range 1–6 h). The balance of HCHO loss (mainly via photolysis) and production (via OH-initiated VOC oxidation) controls the sign and magnitude of this trend. Plume-average OH concentrations, calculated from VOC decays, range from −0.5 (±0.5) × 106 to 5.3 (±0.7) × 106 cm−3. Plume-to-plume variability in dilution-normalized secondary HCHO production correlates with OH abundance rather than normalized OH reactivity, suggesting that OH is the main driver of fire-to-fire variability in HCHO secondary production. Analysis suggests an effective HCHO yield of 0.33 (±0.05) per VOC molecule oxidized for the 12 wildfire plumes. This finding can help connect space-based HCHO observations to the oxidizing capacity of the atmosphere.

Evaluating our understanding of smoke from wild and prescribed fires can benefit from downwind measurements that include both inert tracers to test production and transport and reactive species to ...

Total reactive nitrogen (Nr, defined as all nitrogen-containing compounds except for N2 and N2O) was measured by catalytic conversion to NO and detection by NO-O3 chemiluminescence together with individual Nr species during a series of laboratory fires of fuels characteristic of Western U.S. wildfires, conducted as part of the FIREX FireLab 2016 study. Data from 75 stack fires were analyzed to examine the systematics of nitrogen emissions. The Nr/total-carbon ratios measured in the emissions were compared with fuel and ash N/C ratios and mass to estimate that a mean (± std. dev.) of 0.68 (± 0.14) of fuel nitrogen was emitted as N2 and N2O. The remaining fraction of Nr was emitted as individual compounds: nitric oxide (NO), nitrogen dioxide (NO2), nitrous acid (HONO), isocyanic acid (HNCO), hydrogen cyanide (HCN), ammonia (NH3), and 44 nitrogen-containing volatile organic compounds (NVOCs). The relative difference between the total reactive nitrogen measurement, Nr, and the sum of measured individual Nr compounds had a mean (± std. dev) of 0.152 (± 0.098). Much of this unaccounted Nr is expected to be particle-bound species, not included in this analysis. A number of key species, e.g. HNCO, HCN and HONO, were confirmed not to correlate only with flaming or only with smoldering combustion when using modified combustion efficiency (MCE = CO2/(CO + CO2)) as a rough indicator. However, the systematic variations of the abundance of these species relative to other nitrogen-containing species were successfully modeled using positive matrix factorization (PMF). Three distinct factors were found for the emissions from combined coniferous fuels, aligning with our understanding of combustion chemistry in different temperature ranges: a combustion factor (Comb-N) (800–1200 °C) with emissions of the inorganic compounds NO, NO2 and HONO, and a minor contribution from organic nitro compounds (R-NO2); a high-temperature pyrolysis factor (HT-N) (500–800 °C) with emissions of HNCO, HCN and nitriles; and a low-temperature pyrolysis factor (LT-N) (3, the HT-N factor was dominated by NO2 and had HONO, HCN, and HNCO, and the LT-N factor was mostly NH3 with a slight amount of NO contributing. In both cases, the Comb-N factor correlated best with CO2 emission, while the HT-N factors from coniferous fuels correlated closely with the high temperature VOC factors recently reported by Sekimoto et al., (2018) and the LT-N had some correspondence to the LT-VOC factors. As a consequence, CO2 is recommended as a marker for combustion Nr emissions, HCN is recommended as a marker for HT-N emissions and the family NH3/particle ammonium is recommended as a marker for LT-N emissions.

The chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen-containing particles impact atmospheric chemistry, air quality, and ecological N deposition. Instruments that measure total reactive nitrogen (Nr = all nitrogen compounds except for N2 and N2O) focus on gas-phase nitrogen and very few studies directly discuss the instrument capacity to measure the mass of Nr-containing particles. Here, we investigate the mass quantification of particle-bound nitrogen using a custom Nr system that involves total conversion to nitric oxide (NO) across platinum and molybdenum catalysts followed by NO−O3 chemiluminescence detection. We evaluate the particle conversion of the Nr instrument by comparing to mass-derived concentrations of size-selected and counted ammonium sulfate ((NH4)2SO4), ammonium nitrate (NH4NO3), ammonium chloride (NH4Cl), sodium nitrate (NaNO3), and ammonium oxalate ((NH4)2C2O4) particles determined using instruments that measure particle number and size. These measurements demonstrate Nr-particle conversion across the Nr catalysts that is independent of particle size with 98 ± 10 % efficiency for 100–600 nm particle diameters. We also show efficient conversion of particle-phase organic carbon species to CO2 across the instrument's platinum catalyst followed by a nondispersive infrared (NDIR) CO2 detector. However, the application of this method to the atmosphere presents a challenge due to the small signal above background at high ambient levels of common gas-phase carbon compounds (e.g., CO2). We show the Nr system is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation using single-component, laboratory-generated, Nr-containing particles below 2.5 µm in size. In addition we show agreement with mass measurements of an independently calibrated online particle-into-liquid sampler directly coupled to the electrospray ionization source of a quadrupole mass spectrometer (PILS–ESI/MS) sampling in the negative-ion mode. We obtain excellent correlations (R2 = 0.99) of particle mass measured as Nr with PILS–ESI/MS measurements converted to the corresponding particle anion mass (e.g., nitrate, sulfate, and chloride). The Nr and PILS–ESI/MS are shown to agree to within ∼ 6 % for particle mass loadings of up to 120 µg m−3. Consideration of all the sources of error in the PILS–ESI/MS technique yields an overall uncertainty of ±20 % for these single-component particle streams. These results demonstrate the Nr system is a reliable direct particle mass measurement technique that differs from other particle instrument calibration techniques that rely on knowledge of particle size, shape, density, and refractive index.

Western wildfires have a major impact on air quality in the US. In the fall of 2016, 107 test fires were burned in the large-scale combustion facility at the US Forest Service Missoula Fire Sciences Laboratory as part of the Fire Influence on Regional and Global Environments Experiment (FIREX). Canopy, litter, duff, dead wood, and other fuel components were burned in combinations that represented realistic fuel complexes for several important western US coniferous and chaparral ecosystems including ponderosa pine, Douglas fir, Engelmann spruce, lodgepole pine, subalpine fir, chamise, and manzanita. In addition, dung, Indonesian peat, and individual coniferous ecosystem fuel components were burned alone to investigate the effects of individual components (e.g., duff) and fuel chemistry on emissions. The smoke emissions were characterized by a large suite of state-of-the-art instruments. In this study we report emission factor (EF, grams of compound emitted per kilogram of fuel burned) measurements in fresh smoke of a diverse suite of critically important trace gases measured using open-path Fourier transform infrared spectroscopy (OP-FTIR). We also report aerosol optical properties (absorption EF; single-scattering albedo, SSA; and Ångström absorption exponent, AAE) as well as black carbon (BC) EF measured by photoacoustic extinctiometers (PAXs) at 870 and 401 nm. The average trace gas emissions were similar across the coniferous ecosystems tested and most of the variability observed in emissions could be attributed to differences in the consumption of components such as duff and litter, rather than the dominant tree species. Chaparral fuels produced lower EFs than mixed coniferous fuels for most trace gases except for NOx and acetylene. A careful comparison with available field measurements of wildfires confirms that several methods can be used to extract data representative of real wildfires from the FIREX laboratory fire data. This is especially valuable for species rarely or not yet measured in the field. For instance, the OP-FTIR data alone show that ammonia (1.62 g kg−1), acetic acid (2.41 g kg−1), nitrous acid (HONO, 0.61 g kg−1), and other trace gases such as glycolaldehyde (0.90 g kg−1) and formic acid (0.36 g kg−1) are significant emissions that were poorly characterized or not characterized for US wildfires in previous work. The PAX measurements show that the ratio of brown carbon (BrC) absorption to BC absorption is strongly dependent on modified combustion efficiency (MCE) and that BrC absorption is most dominant for combustion of duff (AAE 7.13) and rotten wood (AAE 4.60): fuels that are consumed in greater amounts during wildfires than prescribed fires. Coupling our laboratory data with field data suggests that fresh wildfire smoke typically has an EF for BC near 0.2 g kg−1, an SSA of ∼ 0.91, and an AAE of ∼ 3.50, with the latter implying that about 86 % of the aerosol absorption at 401 nm is due to BrC.

Particle morphology is an important parameter affecting aerosol optical properties that are relevant to climate and air quality, yet it is poorly constrained due to sparse in situ measurements. Biomass burning is a large source of aerosol that generates particles with different morphologies. Quantifying the optical contributions of non-spherical aerosol populations is critical for accurate radiative transfer models, and for correctly interpreting remote sensing data. We deployed a laser imaging nephelometer at the Missoula Fire Sciences Laboratory to sample biomass burning aerosol from controlled fires during the FIREX intensive laboratory study. The laser imaging nephelometer measures the unpolarized scattering phase function of an aerosol ensemble using diode lasers at 375 and 405 nm. Scattered light from the bulk aerosol in the instrument is imaged onto a charge-coupled device (CCD) using a wide-angle field-of-view lens, which allows for measurements at 4–175∘ scattering angle with ∼ 0.5∘ angular resolution. Along with a suite of other instruments, the laser imaging nephelometer sampled fresh smoke emissions both directly and after removal of volatile components with a thermodenuder at 250 ∘C. The total integrated aerosol scattering signal agreed with both a cavity ring-down photoacoustic spectrometer system and a traditional integrating nephelometer within instrumental uncertainties. We compare the measured scattering phase functions at 405 nm to theoretical models for spherical (Mie) and fractal (Rayleigh–Debye–Gans) particle morphologies based on the size distribution reported by an optical particle counter. Results from representative fires demonstrate that particle morphology can vary dramatically for different fuel types. In some cases, the measured phase function cannot be described using Mie theory. This study demonstrates the capabilities of the laser imaging nephelometer instrument to provide realtime, in situ information about dominant particle morphology, which is vital for understanding remote sensing data and accurately describing the aerosol population in radiative transfer calculations.

Wildland fires in the western United States are projected to increase in frequency, duration, and size. Characterized by widespread and diverse conifer forests, burning within this region may lead to significant terpenoid emissions. Terpenoids constitute a major class of highly reactive secondary organic aerosol (SOA) precursors, with significant structure-dependent variability in reactivity and SOA-formation potential. In this study, highly speciated measurements of terpenoids emitted from laboratory and prescribed fires were achieved using two-dimensional gas chromatography. Nearly 100 terpenoids were measured in smoke samples from 71 fires, with high variability in the dominant compounds. Terpenoid emissions were dependent on plant species and tissues. Canopy/needle-derived emissions dominated in the laboratory fires, whereas woody-tissue-derived emissions dominated in the prescribed fires. Such differences likely have implications for terpenoid emissions from high vs low intensity fires and suggest that canopy-dominant laboratory fires may not accurately represent terpenoid emissions from prescribed fires or wildland fires that burn with low intensity. Predicted SOA formation was sensitive to the diversity of emitted terpenoids when compared to assuming a single terpene surrogate. Given the demonstrated linkages between fuel type, fire terpenoid emissions, and the subsequent implications for plume chemistry, speciated measurements of terpenoids in smoke derived from diverse ecosystems and fire regimes may improve air quality predictions downwind of wildland fires.

New techniques have recently been developed to capture reactive nitrogen species for accurate measurement of their isotopic composition. Reactive nitrogen species play important roles in atmospheric oxidation capacity (hydroxyl radical and ozone formation) and may have impacts on air quality and climate. Tracking reactive nitrogen species and their chemistry in the atmosphere based upon concentration alone is challenging. Isotopic analysis provides a potential tool for tracking the sources and chemistry of species such as nitrogen oxides (NOx = NO + NO2), nitrous acid (HONO), nitric acid (HNO3) and particulate nitrate (NO3−(p)). Here we study direct biomass burning (BB) emissions during the Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) laboratory experiments at the Missoula Fire Laboratory in the fall of 2016. An annular denuder system (ADS) developed to efficiently collect HONO for isotopic composition analysis was deployed to the Fire Lab study. Concentrations of HONO recovered from the ADS collection agree well with mean concentrations averaged over each fire measured by 4 other high time resolution techniques, including mist chamber/ion chromatography (MC/IC), open-path Fourier transform infrared spectroscopy (OP-FTIR), cavity enhanced spectroscopy (CES), proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF). The concentration validation ensures complete collection of BB emitted HONO, of which the isotopic composition is preserved during the collection process. In addition, the isotopic composition of NOx and NO3−(p) from direct BB emissions were also characterized. In 20 stack fires (direct emission within ~ 5 seconds of production by the fire) that burned various biomass materials, δ15N-NOx ranges from −4.3 ‰ to +7.0 ‰, falling near the middle of the range reported in previous work. The first measurements of δ15N-HONO and δ18O-HONO in biomass burning smoke reveal a range of −5.3 – +5.8 ‰ and +5.2 – +15.2 ‰ respectively. Both HONO and NOx are sourced from N in the biomass fuel and δ15N-HONO and δ15N-NOx are strongly correlated (R2 = 0.89, p

Chamber oxidation experiments conducted at the Fire Sciences Laboratory in 2016 are evaluated to identify important chemical processes contributing to the OH chemistry of biomass burning non-methane organic gases (NMOG). Based on the decay of primary carbon measured by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS), it is confirmed that furans and oxygenated aromatics are among the NMOG emitted from western United States fuel types with the highest reactivities towards OH. The oxidation processes and formation of secondary NMOG masses measured by PTR-ToF-MS and iodide clustering time-of-flight chemical ionization mass spectrometry (I-CIMS) is interpreted using a box model employing a modified version of the Master Chemical Mechanism (v. 3.3.1) that includes the OH oxidation of furan, 2-methylfuran, 2,5-dimethylfuran, furfural, 5-methylfurfural, and guaiacol. The model supports the assignment of major PTR-ToF-MS and I-CIMS signals to a series of anhydrides and hydroxy furanones formed primarily through furan chemistry. This mechanism is applied to a Lagrangian box model used previously to model a real biomass burning plume. The updated mechanism reproduces the decay of furans and oxygenated aromatics and the formation of secondary NMOG, such as maleic anhydride. Based on model simulations conducted with and without furans, it is estimated that furans contributed up to 10 % of ozone and over 90 % of maleic anhydride formed within the first 4 hours of oxidation. It is shown that maleic anhydride is present in a biomass burning plume transported over several days, which demonstrates the utility of anhydrides as tracers for aged biomass burning plumes.

The light-absorbing organic aerosol (OA) commonly referred to as “brown carbon” (BrC) has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various volatile organic carbon (VOC) precursors, NOx concentrations, photolysis time, and relative humidity (RH) on the light absorption of selected secondary organic aerosols (SOA). Light absorption of chamber-generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficient (MAC) value is observed from toluene SOA products formed under high-NOx conditions at moderate RH, in which nitro-aromatics were previously identified as the major light-absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organic nitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible (Vis) and ultraviolet (UV) light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.

Biomass burning is a large source of volatile organic compounds (VOCs) and many other trace species to the atmosphere, which can act as precursors to the formation of secondary pollutants such as ozone and fine particles. Measurements collected with a proton-transfer-reaction time-of-flight mass spectrometer during the FIREX 2016 laboratory intensive were analyzed with Positive Matrix Factorization (PMF), in order to understand the instantaneous variability in VOC emissions from biomass burning, and to simplify the description of these types of emissions. Despite the complexity and variability of emissions, we found that a solution including just two emission profiles, which are mass spectral representations of the relative abundances of emitted VOCs, explained on average 85 % of the VOC emissions across various fuels representative of the western US (including various coniferous and chaparral fuels). In addition, the profiles were remarkably similar across almost all of the fuel types tested. For example, the correlation coefficient r of each profile between Ponderosa pine (coniferous tree) and Manzanita (chaparral) is higher than 0.9. We identified the two VOC profiles as resulting from high-temperature and low-temperature pyrolysis processes known to form VOCs in biomass burning. High-temperature and low-temperature pyrolysis processes do not correspond exactly to the commonly used flaming and smoldering categories as described by modified combustion efficiency (MCE). The average atmospheric properties (e.g. OH reactivity, volatility, etc.) of the high- and low-temperature profiles are significantly different. We also found that the two VOC profiles can describe previously reported VOC data for laboratory and field burns. This indicates that the high- and low-temperature pyrolysis profiles could be widely useful to model VOC emissions from many types of biomass burning in the western US, with a few exceptions such as burns of duff and rotten wood.

The chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen (N)-containing particles impact atmospheric chemistry, air quality, and ecological N-deposition. Instruments that measure total reactive nitrogen (N r = all nitrogen compounds except for N 2 and N 2 O) focus on gas-phase nitrogen and very few studies directly discuss the instrument capacity to measure the mass of N r –containing particles. Here, we investigate the mass quantification of particle-bound nitrogen using a custom N r system that involves total conversion to nitric oxide (NO) across platinum and molybdenum catalysts followed by NO-O 3 chemiluminescence detection. We evaluate the particle conversion of the N r instrument by comparing to mass derived concentrations of size-selected and counted ammonium sulfate ((NH 4 ) 2 SO 4 ), ammonium nitrate (NH 4 NO 3 ), ammonium chloride (NH 4 Cl), sodium nitrate (NaNO 3 ), and ammonium oxalate ((NH 4 ) 2 C 2 O 4 ) particles determined using instruments that measure particle number and size. These measurements demonstrate N r -particle conversion across the N r catalysts that is independent of particle size with 98 ± 10 % efficiency for 100–600 nm particle diameters. We also show conversion of particle-phase organic carbon species to CO 2 across the instrument’s platinum catalyst followed by a non-dispersive infrared (NDIR) CO 2 detector. We show the N r system is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation using single component, laboratory generated, N r -containing particles below 2.5 µm in size. In addition we show agreement with mass measurements of an independently calibrated on-line particle-into-liquid sampler directly coupled to the electrospray ionization source of a quadrupole mass spectrometer (PILS-ESI/MS) sampling in the negative ion mode. We obtain excellent correlations (R 2 = 0.99) of particle mass measured as N r with PILS-ESI/MS measurements converted to the corresponding particle anion mass (e.g. nitrate, sulfate, and chloride). The N r and PILS-ESI/MS are shown to agree to within ~ 6 % for particle mass loadings up to 120 µg m −3 . Consideration of all the sources of error in the PILS-ESI/MS technique yields an overall uncertainty of ±20 % for these single component particle streams. These results demonstrate the N r system is a reliable direct particle mass measurement technique that differs from other particle instrument calibration techniques that rely on knowledge of particle size, shape, density, and refractive index.

Volatile and intermediate-volatility non-methane organic gases (NMOGs) released from biomass burning were measured during laboratory-simulated wildfires by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC) pre-separation with electron ionization, H3O+ chemical ionization, and NO+ chemical ionziation, an extensive literature review, and time-series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90 % of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR), broadband cavity enhanced spectroscopy (ACES), and iodide ion chemical ionization mass spectrometry (I-CIMS) where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R2, of > 0.8, including compounds that are not frequently reported by PTR-MS such as ammonia, hydrogen cyanide (HCN), nitrous acid (HONO), and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fire-integrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire.

Particle morphology is an important parameter affecting aerosol optical properties that are relevant to climate and air quality, yet it is poorly constrained due to sparse in situ measurements. Biomass burning is a large source of aerosol that generates particles with different morphologies. Quantifying the optical contributions of non-spherical aerosol populations is critical for accurate radiative transfer models, and for correctly interpreting remote sensing data. We deployed a laser imaging nephelometer at the Missoula Fire Sciences Laboratory to sample biomass burning aerosol from controlled fires during the FIREX intensive laboratory study. The laser imaging nephelometer measures the unpolarized scattering phase function of an aerosol ensemble using diode lasers at 375 nm and 405 nm. Scattered light from the bulk aerosol in the instrument is imaged onto a CCD using a wide-angle field-of-view lens, which allows for measurements at 4–175° scattering angle with ~ 0.5° angular resolution. Along with a suite of other instruments, the laser imaging nephelometer sampled fresh smoke emissions both directly and after removal of volatile components with a thermodenuder at 250 °C. The total integrated aerosol scattering signal agreed with both a cavity ring-down photoacoustic spectrometer system and a traditional integrating nephelometer within instrumental uncertainties. We compare the measured scattering phase functions at 405 nm to theoretical models for spherical (Mie) and fractal (Rayleigh-Debye-Gans) particle morphologies based on the size distribution reported by an optical particle counter. Results from representative fires demonstrate that particle morphology can vary dramatically for different fuel types. In some cases, the measured phase function cannot be described using Mie theory. This study demonstrates the capabilities of the laser imaging nephelometer instrument to provide real-time, in situ information about dominant particle morphology, which is vital for understanding remote sensing data and accurately describing the aerosol population in radiative transfer calculations.