Atmospheric Evolution of Brown Carbon from Wildfires in North America.

Atmospheric brown carbon (BrC) from wildfires is a key component of light-absorbing carbon that significantly contributes to global radiative forcing, but its atmospheric evolution and lifetime remain poorly understood. In this study, we investigate BrC evolution by synthesizing data from one laboratory campaign and four aircraft campaigns spanning diverse spatial scales across North America. To estimate initial conditions for evaluating plume evolution, we develop a method to parametrize the emission ratios of BrC and other species using commonly measured inert tracers, acetonitrile and hydrogen cyanide.

COVID-19 perturbation on US air quality and human health impact assessment.

The COVID-19 stay-at-home orders issued in the United States caused significant reductions in traffic and economic activities. To understand the pandemic's perturbations on US emissions and impacts on urban air quality, we developed near-real-time bottom-up emission inventories based on publicly available energy and economic datasets, simulated the emission changes in a chemical transport model, and evaluated air quality impacts against various observations. The COVID-19 pandemic affected US emissions across broad-based energy and economic sectors and the impacts persisted to 2021.

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.

Fuel-Type Independent Parameterization of Volatile Organic Compound Emissions from Western US Wildfires.

Volatile organic compounds (VOCs) emitted from biomass burning impact air quality and climate. Laboratory studies have shown that the variability in VOC speciation is largely driven by changes in combustion conditions and is only modestly impacted by fuel type. Here, we report that emissions of VOCs measured in ambient smoke emitted from western US wildfires can be parameterized by high- and low-temperature pyrolysis VOC profiles and are consistent with previous observations from laboratory simulated fires.

Sensitivity of northeastern US surface ozone predictions to the representation of atmospheric chemistry in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMMv1.0).

Chemical mechanisms describe how emissions of gases and particles evolve in the atmosphere and are used within chemical transport models to evaluate past, current, and future air quality. Thus, a chemical mechanism must provide robust and accurate predictions of air pollutants if it is to be considered for use by regulatory bodies. In this work, we provide an initial evaluation of the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMMv1.

Secondary Organic Aerosol Formation from Volatile Chemical Product Emissions: Model Parameters and Contributions to Anthropogenic Aerosol.

Volatile chemical products (VCP) are an increasingly important source of hydrocarbon and oxygenated volatile organic compound (OVOC) emissions to the atmosphere, and these emissions are likely to play an important role as anthropogenic precursors for secondary organic aerosol (SOA). While the SOA from VCP hydrocarbons is often accounted for in models, the formation, evolution, and properties of SOA from VCP OVOCs remain uncertain. We use environmental chamber data and a kinetic model to develop SOA parameters for 10 OVOCs representing glycols, glycol ethers, esters, oxygenated aromatics, and amines.

Linking gas, particulate, and toxic endpoints to air emissions in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM).

Chemical mechanisms describe the atmospheric transformations of organic and inorganic species and connect air emissions to secondary species such as ozone, fine particles, and hazardous air pollutants (HAPs) like formaldehyde. Recent advances in our understanding of several chemical systems and shifts in the drivers of atmospheric chemistry warrant updates to mechanisms used in chemical transport models such as the Community Multiscale Air Quality (CMAQ) modeling system. This work builds on the Regional Atmospheric Chemistry Mechanism version 2 (RACM2) and develops the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) version 1.

Influence of Wildfire on Urban Ozone: An Observationally Constrained Box Modeling Study at a Site in the Colorado Front Range.

Increasing trends in biomass burning emissions significantly impact air quality in North America. Enhanced mixing ratios of ozone (O) in urban areas during smoke-impacted periods occur through transport of O produced within the smoke or through mixing of pyrogenic volatile organic compounds (PVOCs) with urban nitrogen oxides (NO = NO + NO) to enhance local O production. Here, we analyze a set of detailed chemical measurements, including carbon monoxide (CO), NO, and speciated volatile organic compounds (VOCs), to evaluate the effects of smoke transported from relatively local and long-range fires on O measured at a site in Boulder, Colorado, during summer 2020.

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.

Ozone chemistry in western U.S. wildfire plumes.

Wildfires are a substantial but poorly quantified source of tropospheric ozone (O). Here, to investigate the highly variable O chemistry in wildfire plumes, we exploit the in situ chemical characterization of western wildfires during the FIREX-AQ flight campaign and show that O production can be predicted as a function of experimentally constrained OH exposure, volatile organic compound (VOC) reactivity, and the fate of peroxy radicals. The O chemistry exhibits rapid transition in chemical regimes.

Volatile chemical product emissions enhance ozone and modulate urban chemistry.

Decades of air quality improvements have substantially reduced the motor vehicle emissions of volatile organic compounds (VOCs). Today, volatile chemical products (VCPs) are responsible for half of the petrochemical VOCs emitted in major urban areas. We show that VCP emissions are ubiquitous in US and European cities and scale with population density.

Variability and Time of Day Dependence of Ozone Photochemistry in Western Wildfire Plumes.

Understanding the efficiency and variability of photochemical ozone (O) 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 O production in modeled plumes.

Observations Confirm that Volatile Chemical Products Are a Major Source of Petrochemical Emissions in U.S. Cities.

Despite decades of declining air pollution, urban U.S. areas are still affected by summertime ozone and wintertime particulate matter exceedance events.

Identifying Volatile Chemical Product Tracer Compounds in U.S. Cities.

With traffic emissions of volatile organic compounds (VOCs) decreasing rapidly over the last decades, the contributions of the emissions from other source categories, such as volatile chemical products (VCPs), have become more apparent in urban air. In this work, in situ measurements of various VOCs are reported for New York City, Pittsburgh, Chicago, and Denver. The magnitude of different emission sources relative to traffic is determined by measuring the urban enhancement of individual compounds relative to the enhancement of benzene, a known tracer of fossil fuel in the United States.

Oxygenated Aromatic Compounds are Important Precursors of Secondary Organic Aerosol in Biomass-Burning Emissions.

Biomass burning is the largest combustion-related source of volatile organic compounds (VOCs) to the atmosphere. We describe the development of a state-of-the-science model to simulate the photochemical formation of secondary organic aerosol (SOA) from biomass-burning emissions observed in dry (RH <20%) environmental chamber experiments. The modeling is supported by (i) new oxidation chamber measurements, (ii) detailed concurrent measurements of SOA precursors in biomass-burning emissions, and (iii) development of SOA parameters for heterocyclic and oxygenated aromatic compounds based on historical chamber experiments.

Urban Oxidation Flow Reactor Measurements Reveal Significant Secondary Organic Aerosol Contributions from Volatile Emissions of Emerging Importance.

Mobile sampling studies have revealed enhanced levels of secondary organic aerosol (SOA) in source-rich urban environments. While these enhancements can be from rapidly reacting vehicular emissions, it was recently hypothesized that nontraditional emissions (volatile chemical products and upstream emissions) are emerging as important sources of urban SOA. We tested this hypothesis by using gas and aerosol mass spectrometry coupled with an oxidation flow reactor (OFR) to characterize pollution levels and SOA potentials in environments influenced by traditional emissions (vehicular, biogenic), and nontraditional emissions (e.

Diurnal Variability and Emission Pattern of Decamethylcyclopentasiloxane (D) from the Application of Personal Care Products in Two North American Cities.

Decamethylcyclopentasiloxane (D) is a cyclic volatile methyl siloxane (cVMS) that is widely used in consumer products and commonly observed in urban air. This study quantifies the ambient mixing ratios of D from ground sites in two North American cities (Boulder, CO, USA, and Toronto, ON, CA). From these data, we estimate the diurnal emission profile of D in Boulder, CO.

Real-Time Studies of Iron Oxalate-Mediated Oxidation of Glycolaldehyde as a Model for Photochemical Aging of Aqueous Tropospheric Aerosols.

The complexation of iron(III) with oxalic acid in aqueous solution yields a strongly absorbing chromophore that undergoes efficient photodissociation to give iron(II) and the carbon dioxide anion radical. Importantly, iron(III) oxalate complexes absorb near-UV radiation (λ > 350 nm), providing a potentially powerful source of oxidants in aqueous tropospheric chemistry. Although this photochemical system has been studied extensively, the mechanistic details associated with its role in the oxidation of dissolved organic matter within aqueous aerosol remain largely unknown.

Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene.

We use a large laboratory, modeling, and field dataset to investigate the isoprene + O3 reaction, with the goal of better understanding the fates of the C1 and C4 Criegee intermediates in the atmosphere. Although ozonolysis can produce several distinct Criegee intermediates, the C1 stabilized Criegee (CH2OO, 61 ± 9%) is the only one observed to react bimolecularly. We suggest that the C4 Criegees have a low stabilization fraction and propose pathways for their decomposition.

Isoprene NO3 Oxidation Products from the RO2 + HO2 Pathway.

We describe the products of the reaction of the hydroperoxy radical (HO(2)) with the alkylperoxy radical formed following addition of the nitrate radical (NO(3)) and O(2) to isoprene. NO(3) adds preferentially to the C(1) position of isoprene (>6 times more favorably than addition to C(4)), followed by the addition of O(2) to produce a suite of nitrooxy alkylperoxy radicals (RO(2)). At an RO(2) lifetime of ∼30 s, δ-nitrooxy and β-nitrooxy alkylperoxy radicals are present in similar amounts.

Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation.

Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 μg m(-3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases.