Search for: All records

Abstract. Accurate representation of fire emissions is critical for modeling the in-plume, near-source, and remote effects of biomass burning (BB) on atmospheric composition, air quality, and climate. In recent years application of advanced instrumentation has significantly improved knowledge of the compounds emitted from fires, which, coupled with a large number of recent laboratory and field campaigns, has facilitated the emergence of new emission factor (EF) compilations. The Next-generation Emissions InVentory expansion of Akagi (NEIVA) version 1.0 is one such compilation in which the EFs for 14 globally relevant fuel and fire types have been updated to include data from recent studies, with a focus on gaseous non-methane organic compounds (NMOC_g). The data are stored in a series of connected tables that facilitate flexible querying from the individual study level to recommended averages of all laboratory and field data by fire type. The querying features are enabled by assignment of unique identifiers to all compounds and constituents, including thousands of NMOC_g. NEIVA also includes chemical and physical property data and model surrogate assignments for three widely used chemical mechanisms for each NMOC_g. NEIVA EF datasets are compared with recent publications and other EF compilations at the individual compound level and in the context of overall volatility distributions and hydroxyl (OH) reactivity (OHR) estimates. The NMOC_g in NEIVA include ∼4–8 times more compounds with improved representation of intermediate volatility organic compounds, resulting in much lower overall volatility (lowest-volatility bin shifted by as much as 3 orders of magnitude) and significantly higher OHR (up to 90 %) than other compilations. These updates can strongly impact model predictions of the effects of BB on atmospheric composition and chemistry. 

Rapid production of formic acid in biomass burning smoke is not captured by the Master Chemical Mechanism (MCM) nor simplified GEOS-Chem chemistry, likely due to missing secondary chemical production. 

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

Wildfire smoke contains numerous different reactive organic gases, many of which have only recently been identified and quantified. Consequently, their relative importance as an oxidant sink is poorly constrained, resulting in incomplete representation in both global chemical transport models (CTMs) and explicit chemical mechanisms. Leveraging 160 gas-phase measurements made during the Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE-CAN) aircraft campaign, we calculate OH reactivities (OHRs) for western U.S. wildfire emissions, smoke aged >3 days, smoke-impacted and low/no smoke-impacted urban atmospheres, and the clean free troposphere. VOCs were found to account for ∼80% of the total calculated OHR in wildfire emissions, with at least half of the field VOC OHR not currently implemented for biomass burning (BB) emissions in the commonly used GEOS-Chem CTM. To improve the representation of OHR, we recommend CTMs implement furan-containing species, butadienes, and monoterpenes for BB. The Master Chemical Mechanism (MCM) was found to account for 88% of VOC OHR in wildfire emissions and captures its observed decay in the first few hours of aging, indicating that most known VOC OH sinks are included in the explicit mechanisms. We find BB smoke enhanced the average total OHR by 53% relative to the low/no smoke urban background, mainly due to the increase in VOCs and CO thus promoting urban ozone production. This work highlights the most important VOC species for daytime BB plume oxidation and provides a roadmap for which species should be prioritized in next-generation CTMs to better predict the downwind air quality and health impacts of BB smoke. 

Abstract. In mid-August through mid-September of 2017 a major wildfire smoke and hazeepisode strongly impacted most of the NW US and SW Canada. During this periodour ground-based site in Missoula, Montana, experienced heavy smoke impactsfor ∼ 500 h (up to 471 µg m−3 hourly averagePM2.5). We measured wildfire trace gases, PM2.5 (particulate matter≤2.5 µm in diameter), and black carbon and submicron aerosolscattering and absorption at 870 and 401 nm. This may be the most extensivereal-time data for these wildfire smoke properties to date. Our range oftrace gas ratios for ΔNH3∕ΔCO and ΔC2H4∕ΔCO confirmed that the smoke from mixed, multiple sourcesvaried in age from ∼ 2–3 h to ∼ 1–2 days. Our study-averageΔCH4∕ΔCO ratio (0.166±0.088) indicated a largecontribution to the regional burden from inefficient smoldering combustion.Our ΔBC∕ΔCO ratio (0.0012±0.0005) for our groundsite was moderately lower than observed in aircraft studies (∼ 0.0015)to date, also consistent with a relatively larger contribution fromsmoldering 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 wildfiresmoke to date. Smoldering combustion is usually associated with enhanced PMemissions, but our ΔPM2.5∕ΔCO ratio (0.126±0.002)was about half the ΔPM1.0∕ΔCO measured in freshwildfire smoke from aircraft (∼ 0.266). Assuming PM2.5 isdominated by PM1, this suggests that aerosol evaporation, at least nearthe surface, can often reduce PM loading and its atmospheric/air-qualityimpacts on the timescale of several days. Much of the smoke was emitted latein the day, suggesting that nighttime processing would be important in theearly evolution of smoke. The diurnal trends show brown carbon (BrC),PM2.5, and CO peaking in the early morning and BC peaking in the earlyevening. Over the course of 1 month, the average single scattering albedo forindividual 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 beingsupported by the simultaneously observed ratios of reactive trace gases toCO. The size and age proxy implied that the Ångström absorptionexponent decreased significantly after about 10 h of daytime smoke aging,consistent with the only airborne measurement of the BrC lifetime in anisolated plume. However, our results clearly show that non-BC absorption canbe important in “typical” regional haze and moderately aged smoke, with BrCostensibly accounting for about half the absorption at 401 nm on average forour entire data set. 

Abstract. The evolution of organic aerosol (OA) and aerosol sizedistributions within smoke plumes is uncertain due to the variability inrates of coagulation and OA condensation/evaporation between different smokeplumes and at different locations within a single plume. We use aircraftdata from the FIREX-AQ campaign to evaluate differences in evolving aerosolsize distributions, OA, and oxygen to carbon ratios (O:C) between and withinsmoke plumes during the first several hours of aging as a function of smokeconcentration. The observations show that the median particle diameterincreases faster in smoke of a higher initial OA concentration (>1000 µg m−3), with diameter growth of over 100 nm in 8 h – despite generally having a net decrease in OA enhancementratios – than smoke of a lower initial OA concentration (<100 µg m−3), which had net increases in OA. Observations of OA and O:Csuggest that evaporation and/or secondary OA formation was greater in lessconcentrated smoke prior to the first measurement (5–57 min afteremission). We simulate the size changes due to coagulation and dilution andadjust for OA condensation/evaporation based on the observed changes in OA.We found that coagulation explains the majority of the diameter growth, withOA evaporation/condensation having a relatively minor impact. We found thatmixing between the core and edges of the plume generally occurred ontimescales of hours, slow enough to maintain differences in aging betweencore and edge but too fast to ignore the role of mixing for most of our cases. 

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 Evaluating our understanding of smoke from wild and prescribed fires can benefit from downwind measurements that include inert tracers to test production and transport and reactive species to test chemical mechanisms. We characterized smoke from fires in coniferous forest fuels for >1,000 hr over two summers (2017 and 2018) at our Missoula, Montana, surface station and found a narrow range for key properties. ΔPM_2.5/ΔCO was 0.1070 ± 0.0278 (g/g) or about half the age‐independent ratios obtained at free troposphere elevations (0.2348 ± 0.0326). The average absorption Ångström exponent across both years was 1.84 ± 0.18, or about half the values available for very fresh smoke. Brown carbon (BrC) was persistent (~50% of absorption at 401 nm) in both years, despite differences in smoke age. ΔBC/ΔCO doubled from 2017 to 2018, but the average across 2 years was within 33% of recent airborne measurements, suggesting low sampling bias among platforms. Switching from a 1.0 to a 2.5 micron cutoff increased the mass scattering and mass absorption coefficients, suggesting often overlooked supermicron particles impact the optical properties of moderately aged smoke. O₃was elevated ~6 ppb on average over a full diurnal period when wildfire smoke was present, and smoke‐associated O₃increases were highest (~9 pbb) at night, suggesting substantial upwind production. NO_xwas mostly local in origin. NO_xspurred high rates of NO₃production, including in the presence of wildfire smoke (up to 2.44 ppb hr⁻¹) and at least one nighttime BrC secondary formation event that could have impacted next‐day photochemistry.