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.
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Simulating the forest fire plume dispersion, chemistry, and aerosol formation using SAM-ASP version 1.0
Abstract. Biomass burning is a major source of trace gases andaerosols that can ultimately impact health, air quality, and climate.Global and regional-scale three-dimensional Eulerian chemical transportmodels (CTMs) use estimates of the primary emissions from fires and canunphysically mix them across large-scale grid boxes, leading to incorrectestimates of the impact of biomass burning events. On the other hand,plume-scale process models allow for explicit simulation and examination ofthe chemical and physical transformations of trace gases and aerosols withinbiomass burning smoke plumes, and they may be used to developparameterizations of this aging process for coarser grid-scale models. Herewe describe the coupled SAM-ASP plume-scale process model, which consists ofcoupling the large-eddy simulation model, the System for AtmosphericModelling (SAM), with the detailed gas and aerosol chemistry model, theAerosol Simulation Program (ASP). We find that the SAM-ASP version 1.0 modelis able to correctly simulate the dilution of CO in a California chaparralsmoke plume, as well as the chemical loss of NOx, HONO, and NH3within the plume, the formation of PAN and O3, the loss of OA, and thechange in the size distribution of aerosols as compared to measurements andprevious single-box model results. The newly coupled model is able tocapture the cross-plume vertical and horizontal concentration gradients asthe fire plume evolves downwind of the emission source. The integration andevaluation of SAM-ASP version 1.0 presented here will support thedevelopment of parameterizations of near-source biomass burning chemistrythat can be used to more accurately simulate biomass burning chemical andphysical transformations of tracegases and aerosols within coarser grid-scale CTMs.
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- NSF-PAR ID:
- 10211178
- Date Published:
- Journal Name:
- Geoscientific Model Development
- Volume:
- 13
- Issue:
- 9
- ISSN:
- 1991-9603
- Page Range / eLocation ID:
- 4579 to 4593
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The ocean’s major circulation system, the Atlantic Meridional Overturning Circulation (AMOC), is slowing down. Such weakening is consistent with warming associated with increasing greenhouse gases, as well as with recent decreases in industrial aerosol pollution. The impact of biomass burning aerosols on the AMOC, however, remains unexplored. Here, we use the Community Earth System Model version 1 Large Ensemble to quantify the impact of both aerosol types on the AMOC. Despite relatively small changes in North Atlantic biomass burning aerosols, significant AMOC evolution occurs, including weakening from 1920 to ~1970 followed by AMOC strengthening. These changes are largely out of phase relative to the corresponding AMOC evolution under industrial aerosols. AMOC responses are initiated by thermal changes in sea surface density flux due to altered shortwave radiation. An additional dynamical mechanism involving the North Atlantic sea-level pressure gradient is important under biomass-burning aerosols. AMOC-induced ocean salinity flux convergence acts as a positive feedback. Our results show that biomass-burning aerosols reinforce early 20th-century AMOC weakening associated with greenhouse gases and also partially mute industrial aerosol impacts on the AMOC. Recent increases in wildfires suggest biomass-burning aerosols may be an important driver of future AMOC variability.
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Abstract. Chamber oxidation experiments conducted at the Fire Sciences Laboratory in 2016 are evaluated to identify important chemical processes contributing to the hydroxy radical (OH) chemistry of biomass burning non-methane organic gases (NMOGs). 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 NMOGs 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 customized mechanism reproduces the decay of furans and oxygenated aromatics and the formation of secondary NMOGs, 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 h 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 markers for aged biomass burning plumes.more » « less
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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 Abs405) 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.
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Abstract The western U.S. wildfire smoke plumes observed by the upward-pointing Wyoming Cloud Lidar (WCL) during the Biomass Burning Fluxes of Trace Gases and Aerosols (BB-FLUX) project are investigated in a two-part paper. Part II here presents the reconstructed vertical structures of seven plumes from airborne WCL measurements. The vertical structures evident in the fire plume cross sections, supported by in situ measurements, showed that the fire plumes had distinct macrophysical and microphysical properties, which are closely related to the plume transport, fire emission intensity, and thermodynamic structure in the boundary layer. All plumes had an injection layer between 2.8 and 4.0 km above mean sea level, which is generally below the identified boundary layer top height. Plumes that transported upward out of the boundary layer, such as the Rabbit Foot and Pole Creek fires, formed a higher plume at around 5.5 km. The largest and highest Pole Creek fire plume was transported farthest and was sampled by University of Wyoming King Air aircraft at 170 km, or 2.3 h, downwind. It was associated with the warmest, driest, deepest boundary layer and the highest wind speed and turbulence. The Watson Creek fire plume intensified in the afternoon with stronger CO emission and larger smoke plume height than in the morning, indicating a fire diurnal cycle, but some fire plumes did not intensify in the afternoon. There were pockets of relatively large irregular aerosol particles at the tops of plumes from active fires. In less-active fire plumes, the WCL depolarization ratio and passive cavity aerosol spectrometer probe mass mean diameter maximized at a height that was low in the plume.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.5194/gmd-13-4579-2020
