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Wildfires have become larger and more frequent because of climate change, increasing their impact on air pollution. Air quality forecasts and climate models do not currently account for changes in the composition of wildfire emissions during the commonly observed progression from more flaming to smoldering combustion. Laboratory measurements have consistently shown decreased nitrogen dioxide (NO₂) relative to carbon monoxide (CO) over time, as they transitioned from more flaming to smoldering combustion, while formaldehyde (HCHO) relative to CO remained constant. Here, we show how daily ratios between column densities of NO₂versus those of CO and HCHO versus CO from the Tropospheric Monitoring Instrument (TROPOMI) changed for large wildfires in the Western United States. TROPOMI‐derived emission ratios were lower than those from the laboratory. We discuss reasons for the discrepancies, including how representative laboratory burns are of wildfires, the effect of aerosols on trace gas retrievals, and atmospheric chemistry in smoke plumes.

 

The impacts of wildfires along the wildland urban interface (WUI) on atmospheric particulate concentrations and composition are an understudied source of air pollution exposure. To assess the residual impacts of the 2021 Marshall Fire (Colorado), a wildfire that predominantly burned homes and other human-made materials, on homes within the fire perimeter that escaped the fire, we performed a combination of fine particulate matter (PM2.5) filter sampling and chemical analysis, indoor dust collection and chemical analysis, community scale PurpleAir PM2.5 analysis, and indoor particle number concentration measurements. Following the fire, the chemical speciation of dust collected in smoke-affected homes in the burned zone showed elevated concentrations of the biomass burning marker levoglucosan (medianlevo = 4147 ng g−1), EPA priority toxic polycyclic aromatic hydrocarbons (median Σ16PAH = 1859.3 ng g−1), and metals (median Σ20Metals = 34.6 mg g−1) when compared to samples collected in homes outside of the burn zone 6 months after the fire. As indoor dust particles are often resuspended and can become airborne, the enhanced concentration of hazardous metals and organics within dust samples may pose a threat to human health. Indoor airborne particulate organic carbon (median = 1.91 μg m−3), particulate elemental carbon (median = .02 μg m−3), and quantified semi-volatile organic species in PM2.5 were found in concentrations comparable to ambient air in urban areas across the USA. Particle number and size distribution analysis at a heavily instrumented supersite home located immediately next to the burned area showed indoor particulates in low concentrations (below 10 μg m−3) across various sizes of PM (12 nm–20 μm), but were elevated by resuspension from human activity, including cleaning. 

Abstract Wintertime episodes of high aerosol concentrations occur frequently in urban and agricultural basins and valleys worldwide. These episodes often arise following development of persistent cold-air pools (PCAPs) that limit mixing and modify chemistry. While field campaigns targeting either basin meteorology or wintertime pollution chemistry have been conducted, coupling between interconnected chemical and meteorological processes remains an insufficiently studied research area. Gaps in understanding the coupled chemical-meteorological interactions that drive high pollution events make identification of the most effective air-basin specific emission control strategies challenging. To address this, a September 2019 workshop occurred with the goal of planning a future research campaign to investigate air quality in Western U.S. basins. Approximately 120 people participated, representing 50 institutions and 5 countries. Workshop participants outlined the rationale and design for a comprehensive wintertime study that would couple atmospheric chemistry and boundary-layer and complex-terrain meteorology within western U.S. basins. Participants concluded the study should focus on two regions with contrasting aerosol chemistry: three populated valleys within Utah (Salt Lake, Utah, and Cache Valleys) and the San Joaquin Valley in California. This paper describes the scientific rationale for a campaign that will acquire chemical and meteorological datasets using airborne platforms with extensive range, coupled to surface-based measurements focusing on sampling within the near-surface boundary layer, and transport and mixing processes within this layer, with high vertical resolution at a number of representative sites. No prior wintertime basin-focused campaign has provided the breadth of observations necessary to characterize the meteorological-chemical linkages outlined here, nor to validate complex processes within coupled atmosphere-chemistry models. 

Abstract. Gas-phase atmospheric concentrations of peroxyacetyl nitrate (PAN),peroxypropionyl nitrate (PPN), and peroxymethacryloyl nitrate (MPAN) weremeasured on the ground using a gas chromatograph electron capture detector(GC-ECD) during the Southern Oxidants and Aerosols Study (SOAS) 2013 campaign(1 June to 15 July 2013) in Centreville, Alabama, in order to studybiosphere–atmosphere interactions. Average levels of PAN, PPN, and MPAN were169, 5, and 9 pptv, respectively, and the sum accounts for an average of16 % of NO_y during the daytime (10:00 to 16:00 localtime). Higher concentrations were seen on average in air that came to thesite from the urban NO_x sources to the north. PAN levelswere the lowest observed in ground measurements over the past two decades inthe southeastern US. A multiple regression analysis indicates that biogenicvolatile organic compounds (VOCs) account for 66 % of PAN formationduring this study. Comparison of this value with a 0-D model simulation ofperoxyacetyl radical production indicates that at least 50 % of PANformation is due to isoprene oxidation. MPAN has a statistical correlationwith isoprene hydroxynitrates (IN). Organic aerosol mass increases withgas-phase MPAN and IN concentrations, but the mass of organic nitrates inparticles is largely unrelated to MPAN.

 

Abstract. Recent studies have demonstrated that organic compounds can partition from the gas phase to the walls in Teflon environmental chambers and that the process can be modeled as absorptive partitioning. Here these studies were extended to investigate gas–wall partitioning of organic compounds in Teflon tubing and inside a proton-transfer-reaction mass spectrometer (PTR-MS) used to monitor compound concentrations. Rapid partitioning of C₈–C₁₄ 2-ketones and C₁₁–C₁₆ 1-alkenes was observed for compounds with saturation concentrations (c^∗) in the range of 3×10⁴ to 1×10⁷µgm⁻³, causing delays in instrument response to step-function changes in the concentration of compounds being measured. These delays vary proportionally with tubing length and diameter and inversely with flow rate and c^∗. The gas–wall partitioning process that occurs in tubing is similar to what occurs in a gas chromatography column, and the measured delay times (analogous to retention times) were accurately described using a linear chromatography model where the walls were treated as an equivalent absorbing mass that is consistent with values determined for Teflon environmental chambers. The effect of PTR-MS surfaces on delay times was also quantified and incorporated into the model. The model predicts delays of an hour or more for semivolatile compounds measured under commonly employed conditions. These results and the model can enable better quantitative design of sampling systems, in particular when fast response is needed, such as for rapid transients, aircraft, or eddy covariance measurements. They may also allow estimation of c^∗ values for unidentified organic compounds detected by mass spectrometry and could be employed to introduce differences in time series of compounds for use with factor analysis methods. Best practices are suggested for sampling organic compounds through Teflon tubing.

 

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. 

Abstract. Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenicemissions of organic compounds, constitutes a substantial fraction of themass of submicron aerosol in populated areas around the world andcontributes to poor air quality and premature mortality. However, theprecursor sources of ASOA are poorly understood, and there are largeuncertainties in the health benefits that might accrue from reducinganthropogenic organic emissions. We show that the production of ASOA in 11urban areas on three continents is strongly correlated with the reactivityof specific anthropogenic volatile organic compounds. The differences inASOA production across different cities can be explained by differences inthe emissions of aromatics and intermediate- and semi-volatile organiccompounds, indicating the importance of controlling these ASOA precursors.With an improved model representation of ASOA driven by the observations,we attribute 340 000 PM2.5-related premature deaths per year to ASOA, which isover an order of magnitude higher than prior studies. A sensitivity casewith a more recently proposed model for attributing mortality to PM2.5(the Global Exposure Mortality Model) results in up to 900 000 deaths. Alimitation of this study is the extrapolation from cities with detailedstudies and regions where detailed emission inventories are available toother regions where uncertainties in emissions are larger. In addition tofurther development of institutional air quality management infrastructure,comprehensive air quality campaigns in the countries in South and CentralAmerica, Africa, South Asia, and the Middle East are needed for furtherprogress in this area. 

Concentrations of atmospheric trace species in the United States have changed dramatically over the past several decades in response to pollution control strategies, shifts in domestic energy policy and economics, and economic development (and resulting emission changes) elsewhere in the world. Reliable projections of the future atmosphere require models to not only accurately describe current atmospheric concentrations, but to do so by representing chemical, physical and biological processes with conceptual and quantitative fidelity. Only through incorporation of the processes controlling emissions and chemical mechanisms that represent the key transformations among reactive molecules can models reliably project the impacts of future policy, energy and climate scenarios. Efforts to properly identify and implement the fundamental and controlling mechanisms in atmospheric models benefit from intensive observation periods, during which collocated measurements of diverse, speciated chemicals in both the gas and condensed phases are obtained. The Southeast Atmosphere Studies (SAS, including SENEX, SOAS, NOMADSS and SEAC4RS) conducted during the summer of 2013 provided an unprecedented opportunity for the atmospheric modeling community to come together to evaluate, diagnose and improve the representation of fundamental climate and air quality processes in models of varying temporal and spatial scales.

This paper is aimed at discussing progress in evaluating, diagnosing and improving air quality and climate modeling using comparisons to SAS observations as a guide to thinking about improvements to mechanisms and parameterizations in models. The effort focused primarily on model representation of fundamental atmospheric processes that are essential to the formation of ozone, secondary organic aerosol (SOA) and other trace species in the troposphere, with the ultimate goal of understanding the radiative impacts of these species in the southeast and elsewhere. Here we address questions surrounding four key themes: gas-phase chemistry, aerosol chemistry, regional climate and chemistry interactions, and natural and anthropogenic emissions. We expect this review to serve as a guidance for future modeling efforts.