Impact of Biomass Burning Organic Aerosol Volatility on Smoke Concentrations Downwind of Fires.

Biomass burning particulate matter (BBPM) affects regional air quality and global climate, with impacts expected to continue to grow over the coming years. We show that studies of North American fires have a systematic altitude dependence in measured BBPM normalized excess mixing ratio (NEMR; ΔPM/ΔCO), with airborne and high-altitude studies showing a factor of 2 higher NEMR than ground-based measurements. We report direct airborne measurements of BBPM volatility that partially explain the difference in the BBPM NEMR observed across platforms. We find that when heated to 40-45 °C in an airborne thermal denuder, 19% of lofted smoke PM1 evaporates. Thermal denuder measurements are consistent with evaporation observed when a single smoke plume was sampled across a range of temperatures as the plume descended from 4 to 2 km altitude. We also demonstrate that chemical aging of smoke and differences in PM emission factors can not fully explain the platform-dependent differences. When the measured PM volatility is applied to output from the High Resolution Rapid Refresh Smoke regional model, we predict a lower PM NEMR at the surface compared to the lofted smoke measured by aircraft. These results emphasize the significant role that gas-particle partitioning plays in determining the air quality impacts of wildfire smoke.

Remote Aerosol Simulated During the Atmospheric Tomography (ATom) Campaign and Implications for Aerosol Lifetime.

We investigate and assess how well a global chemical transport model (GEOS-Chem) simulates submicron aerosol mass concentrations in the remote troposphere. The simulated speciated aerosol (organic aerosol (OA), black carbon, sulfate, nitrate, and ammonium) mass concentrations are evaluated against airborne observations made during all four seasons of the NASA Atmospheric Tomography Mission (ATom) deployments over the remote Pacific and Atlantic Oceans. Such measurements over pristine environments offer fresh insights into the spatial (Northern [NH] and Southern Hemispheres [SH], Atlantic, and Pacific Oceans) and temporal (all seasons) variability in aerosol composition and lifetime, away from continental sources. The model captures the dominance of fine OA and sulfate aerosol mass concentrations in all seasons. There is a high bias across all species in the ATom-2 (NH winter) simulations; implementing recent updates to the wet scavenging parameterization improves our simulations, eliminating the large ATom-2 (NH winter) bias, improving the ATom-1 (NH summer) and ATom-3 (NH fall) simulations, but producing a model underestimate in aerosol mass concentrations for the ATom-4 (NH spring) simulations. Following the wet scavenging updates, simulated global annual mean aerosol lifetimes vary from 1.9 to 4.0 days, depending on species. Aerosol lifetimes in each hemisphere vary by season, and are longest for carbonaceous aerosol during the southern hemispheric fire season. The updated wet scavenging parameterization brings simulated concentrations closer to observations and reduces global aerosol lifetime for all species, indicating the sensitivity of global aerosol lifetime and burden to wet removal processes.

Airborne Emission Rate Measurements Validate Remote Sensing Observations and Emission Inventories of Western U.S. Wildfires.

Carbonaceous emissions from wildfires are a dynamic mixture of gases and particles that have important impacts on air quality and climate. Emissions that feed atmospheric models are estimated using burned area and fire radiative power (FRP) methods that rely on satellite products. These approaches show wide variability and have large uncertainties, and their accuracy is challenging to evaluate due to limited aircraft and ground measurements. Here, we present a novel method to estimate fire plume-integrated total carbon and speciated emission rates using a unique combination of lidar remote sensing aerosol extinction profiles and in situ measured carbon constituents. We show strong agreement between these aircraft-derived emission rates of total carbon and a detailed burned area-based inventory that distributes carbon emissions in time using Geostationary Operational Environmental Satellite FRP observations (Fuel2Fire inventory, slope = 1.33 ± 0.04, r2 = 0.93, and RMSE = 0.27). Other more commonly used inventories strongly correlate with aircraft-derived emissions but have wide-ranging over- and under-predictions. A strong correlation is found between carbon monoxide emissions estimated in situ with those derived from the TROPOspheric Monitoring Instrument (TROPOMI) for five wildfires with coincident sampling windows (slope = 0.99 ± 0.18; bias = 28.5%). Smoke emission coefficients (g MJ-1) enable direct estimations of primary gas and aerosol emissions from satellite FRP observations, and we derive these values for many compounds emitted by temperate forest fuels, including several previously unreported species.

Understanding the Evolution of Smoke Mass Extinction Efficiency Using Field Campaign Measurements.

Aerosol mass extinction efficiency (MEE) is a key aerosol property used to connect aerosol optical properties with aerosol mass concentrations. Using measurements of smoke obtained during the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign we find that mid-visible smoke MEE can change by a factor of 2-3 between fresh smoke (<2 hr old) and one-day-old smoke. While increases in aerosol size partially explain this trend, changes in the real part of the aerosol refractive index (real(n)) are necessary to provide closure assuming Mie theory. Real(n) estimates derived from multiple days of FIREX-AQ measurements increase with age (from 1.40 - 1.45 to 1.5-1.54 from fresh to one-day-old) and are found to be positively correlated with organic aerosol oxidation state and aerosol size, and negatively correlated with smoke volatility. Future laboratory, field, and modeling studies should focus on better understanding and parameterizing these relationships to fully represent smoke aging.

HCOOH in the remote atmosphere: Constraints from Atmospheric Tomography (ATom) airborne observations.

Formic acid (HCOOH) is an important component of atmospheric acidity but its budget is poorly understood, with prior observations implying substantial missing sources. Here we combine pole-to-pole airborne observations from the Atmospheric Tomography Mission (ATom) with chemical transport model (GEOS-Chem CTM) and back trajectory analyses to provide the first global in-situ characterization of HCOOH in the remote atmosphere. ATom reveals sub-100 ppt HCOOH concentrations over most of the remote oceans, punctuated by large enhancements associated with continental outflow. Enhancements correlate with known combustion tracers and trajectory-based fire influences. The GEOS-Chem model underpredicts these in-plume HCOOH enhancements, but elsewhere we find no broad indication of a missing HCOOH source in the background free troposphere. We conclude that missing non-fire HCOOH precursors inferred previously are predominantly short-lived. We find indications of a wet scavenging underestimate in the model consistent with a positive HCOOH bias in the tropical upper troposphere. Observations reveal episodic evidence of ocean HCOOH uptake, which is well-captured by GEOS-Chem; however, despite its strong seawater undersaturation HCOOH is not consistently depleted in the remote marine boundary layer. Over fifty fire and mixed plumes were intercepted during ATom with widely varying transit times and source regions. HCOOH:CO normalized excess mixing ratios in these plumes range from 3.4 to >50 ppt/ppb CO and are often over an order of magnitude higher than expected primary emission ratios. HCOOH is thus a major reactive organic carbon reservoir in the aged plumes sampled during ATom, implying important missing pathways for in-plume HCOOH production.

Global Measurements of Brown Carbon and Estimated Direct Radiative Effects.

Brown carbon (BrC) is an organic aerosol material that preferentially absorbs light of shorter wavelengths. Global-scale radiative impacts of BrC have been difficult to assess due to the lack of BrC observational data. To address this, aerosol filters were continuously collected with near pole-to-pole latitudinal coverage over the Pacific and Atlantic basins in three seasons as part of the Atmospheric Tomography Mission. BrC chromophores in filter extracts were measured. We find that globally, BrC was highly spatially heterogeneous, mostly detected in air masses that had been transported from regions of extensive biomass burning. We calculate the average direct radiative effect due to BrC absorption accounted for approximately 7% to 48% of the top of the atmosphere clear-sky instantaneous forcing by all absorbing carbonaceous aerosols in the remote atmosphere, indicating that BrC from biomass burning is an important component of the global radiative balance.

Efficient In-Cloud Removal of Aerosols by Deep Convection.

Convective systems dominate the vertical transport of aerosols and trace gases. The most recent in situ aerosol measurements presented here show that the concentrations of primary aerosols including sea salt and black carbon drop by factors of 10 to 10,000 from the surface to the upper troposphere. In this study we show that the default convective transport scheme in the National Science Foundation/Department of Energy Community Earth System Model results in a high bias of 10-1,000 times the measured aerosol mass for black carbon and sea salt in the middle and upper troposphere. A modified transport scheme, which considers aerosol activation from entrained air above the cloud base and aerosol-cloud interaction associated with convection, dramatically improves model agreement with in situ measurements suggesting that deep convection can efficiently remove primary aerosols. We suggest that models that fail to consider secondary activation may overestimate black carbon's radiative forcing by a factor of 2.

Strong impact of wildfires on the abundance and aging of black carbon in the lowermost stratosphere.

Wildfires inject large amounts of black carbon (BC) particles into the atmosphere, which can reach the lowermost stratosphere (LMS) and cause strong radiative forcing. During a 14-month period of observations on board a passenger aircraft flying between Europe and North America, we found frequent and widespread biomass burning (BB) plumes, influencing 16 of 160 flight hours in the LMS. The average BC mass concentrations in these plumes (∼140 ng·m-3, standard temperature and pressure) were over 20 times higher than the background concentration (∼6 ng·m-3) with more than 100-fold enhanced peak values (up to ∼720 ng·m-3). In the LMS, nearly all BC particles were covered with a thick coating. The average mass equivalent diameter of the BC particle cores was ∼120 nm with a mean coating thickness of ∼150 nm in the BB plume and ∼90 nm with a coating of ∼125 nm in the background. In a BB plume that was encountered twice, we also found a high diameter growth rate of ∼1 nm·h-1 due to the BC particle coatings. The observed high concentrations and thick coatings of BC particles demonstrate that wildfires can induce strong local heating in the LMS and may have a significant influence on the regional radiative forcing of climate.