Notable impact of wildfires in the western United States on weather hazards in the central United States.

Increased wildfire events constitute a significant threat to life and property in the United States. Wildfire impact on severe storms and weather hazards is another pathway that threatens society, and our understanding of which is very limited. Here, we use unique modeling developments to explore the effects of wildfires in the western US (mainly California and Oregon) on precipitation and hail in the central US. We find that the western US wildfires notably increase the occurrences of heavy precipitation rates by 38% and significant severe hail (≥2 in.) by 34% in the central United States. Both heat and aerosols from wildfires play an important role. By enhancing surface high pressure and increasing westerly and southwesterly winds, wildfires in the western United States produce (1) stronger moisture and aerosol transport to the central United States and (2) larger wind shear and storm-relative helicity in the central United States. Both the meteorological environment more conducive to severe convective storms and increased aerosols contribute to the enhancements of heavy precipitation rates and large hail. Moreover, the local wildfires in the central US also enhance the severity of storms, but their impact is notably smaller than the impact of remote wildfires in California and Oregon because of the lessened severity of the local wildfires. As wildfires are projected to be more frequent and severe in a warmer climate, the influence of wildfires on severe weather in downwind regions may become increasingly important.

Heterogeneous iodine-organic chemistry fast-tracks marine new particle formation.

The gas-phase formation of new particles less than 1 nm in size and their subsequent growth significantly alters the availability of cloud condensation nuclei (CCN, >30-50 nm), leading to impacts on cloud reflectance and the global radiative budget. However, this growth cannot be accounted for by condensation of typical species driving the initial nucleation. Here, we present evidence that nucleated iodine oxide clusters provide unique sites for the accelerated growth of organic vapors to overcome the coagulation sink. Heterogeneous reactions form low-volatility organic acids and alkylaminium salts in the particle phase, while further oligomerization of small α-dicarbonyls (e.g., glyoxal) drives the particle growth. This identified heterogeneous mechanism explains the occurrence of particle production events at organic vapor concentrations almost an order of magnitude lower than those required for growth via condensation alone. A notable fraction of iodine associated with these growing particles is recycled back into the gas phase, suggesting an effective transport mechanism for iodine to remote regions, acting as a "catalyst" for nucleation and subsequent new particle production in marine air.

From COVID-19 to future electrification: Assessing traffic impacts on air quality by a machine-learning model.

The large fluctuations in traffic during the COVID-19 pandemic provide an unparalleled opportunity to assess vehicle emission control efficacy. Here we develop a random-forest regression model, based on the large volume of real-time observational data during COVID-19, to predict surface-level NO2, O3, and fine particle concentration in the Los Angeles megacity. Our model exhibits high fidelity in reproducing pollutant concentrations in the Los Angeles Basin and identifies major factors controlling each species. During the strictest lockdown period, traffic reduction led to decreases in NO2 and particulate matter with aerodynamic diameters <2.5 µm by -30.1% and -17.5%, respectively, but a 5.7% increase in O3 Heavy-duty truck emissions contribute primarily to these variations. Future traffic-emission controls are estimated to impose similar effects as observed during the COVID-19 lockdown, but with smaller magnitude. Vehicular electrification will achieve further alleviation of NO2 levels.

Vapors Are Lost to Walls, Not to Particles on the Wall: Artifact-Corrected Parameters from Chamber Experiments and Implications for Global Secondary Organic Aerosol.

Atmospheric models of secondary organic aerosol (OA) (SOA) typically rely on parameters derived from environmental chambers. Chambers are subject to experimental artifacts, including losses of (1) particles to the walls (PWL), (2) vapors to the particles on the wall (V2PWL), and (3) vapors to the wall directly (VWL). We present a method for deriving artifact-corrected SOA parameters and translating these to volatility basis set (VBS) parameters for use in chemical transport models (CTMs). Our process involves combining a box model that accounts for chamber artifacts (Statistical Oxidation Model with a TwO-Moment Aerosol Sectional model (SOM-TOMAS)) with a pseudo-atmospheric simulation to develop VBS parameters that are fit across a range of OA mass concentrations. We found that VWL led to the highest percentage change in chamber SOA mass yields (high NOx: 36-680%; low NOx: 55-250%), followed by PWL (high NOx: 8-39%; low NOx: 10-37%), while the effects of V2PWL are negligible. In contrast to earlier work that assumed that V2PWL was a meaningful loss pathway, we show that V2PWL is an unimportant SOA loss pathway and can be ignored when analyzing chamber data. Using our updated VBS parameters, we found that not accounting for VWL may lead surface-level OA to be underestimated by 24% (0.25 µg m-3) as a global average or up to 130% (9.0 µg m-3) in regions of high biogenic or anthropogenic activity. Finally, we found that accurately accounting for PWL and VWL improves model-measurement agreement for fine mode aerosol mass concentrations (PM2.5) in the GEOS-Chem model.

Comparison between Spatially Resolved Airborne Flux Measurements and Emission Inventories of Volatile Organic Compounds in Los Angeles.

Los Angeles is a major hotspot for ozone and particulate matter air pollution in the United States. Ozone and PM2.5 in this region have not improved substantially for the past decade, despite a reduction in vehicular emissions of their precursors, NOx and volatile organic compounds (VOCs). This reduction in "traditional" sources has made the current emission mixture of air pollutant precursors more uncertain. To map and quantify emissions of a wide range of VOCs in this urban area, we performed airborne eddy covariance measurements with wavelet analysis. VOC fluxes measured include tracers for source categories, such as traffic, vegetation, and volatile chemical products (VCPs). Mass fluxes were dominated by oxygenated VOCs, with ethanol contributing ∼29% of the total. In terms of OH reactivity and aerosol formation potential, terpenoids contributed more than half. Observed fluxes were compared with two commonly used emission inventories: the California Air Resources Board inventory and the combination of the Biogenic Emission Inventory System with the Fuel-based Inventory of Vehicle Emissions combined with Volatile Chemical Products (FIVE-VCP). The comparison shows mismatches regarding the amount, spatial distribution, and weekend effects of observed VOC emissions with the inventories. The agreement was best for typical transportation related VOCs, while discrepancies were larger for biogenic and VCP-related VOCs.

Methane Emissions from Dairy Operations in California's San Joaquin Valley Evaluated Using Airborne Flux Measurements.

State inventories indicate that dairy operations account for nearly half of California's methane budget. Recent analyses suggest, however, that these emissions may be underestimated, complicating efforts to develop emission reduction strategies. Here, we report estimates of dairy methane emissions in the southern San Joaquin Valley (SJV) of California in June 2021 using airborne flux measurements. We find average dairy methane fluxes of 512 ± 178 mg m-2 h-1 from a region of 300+ dairies near Visalia, CA using a combination of eddy covariance and mass balance-based techniques, corresponding to 118 ± 41 kg dairy-1 h-1. These values estimated during our June campaign are 39 ± 48% larger than annual average estimates from the recently developed VISTA-CA inventory. We observed notable increases in emissions with temperature. Our estimates align well with inventory predictions when parametrizations for the temperature dependence of emissions are applied. Our measurements further demonstrate that the VISTA-CA emission inventory is considerably more accurate than the EPA GHG-I inventory in this region. Source apportionment analyses confirm that dairy operations produce the majority of methane emissions in the southern SJV (∼65%). Fugitive oil and gas (O&G) sources account for the remaining ∼35%. Our results support the accuracy of the process-based models used to develop dairy emission inventories and highlight the need for additional investigation of the meteorological dependence of these emissions.

Surface tension prevails over solute effect in organic-influenced cloud droplet activation.

The spontaneous growth of cloud condensation nuclei (CCN) into cloud droplets under supersaturated water vapour conditions is described by classic Köhler theory. This spontaneous activation of CCN depends on the interplay between the Raoult effect, whereby activation potential increases with decreasing water activity or increasing solute concentration, and the Kelvin effect, whereby activation potential decreases with decreasing droplet size or increases with decreasing surface tension, which is sensitive to surfactants. Surface tension lowering caused by organic surfactants, which diminishes the Kelvin effect, is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of surfactant molecules from the droplet bulk to the droplet-vapour interface. Here we present observational and theoretical evidence illustrating that, in ambient air, surface tension lowering can prevail over the reduction in the Raoult effect, leading to substantial increases in cloud droplet concentrations. We suggest that consideration of liquid-liquid phase separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, can explain the lack of concomitant reduction of the Raoult effect, while maintaining substantial lowering of surface tension, even for partial surface coverage. Apart from the importance of particle size and composition in droplet activation, we show by observation and modelling that incorporation of phase-separation effects into activation thermodynamics can lead to a CCN number concentration that is up to ten times what is predicted by climate models, changing the properties of clouds. An adequate representation of the CCN activation process is essential to the prediction of clouds in climate models, and given the effect of clouds on the Earth's energy balance, improved prediction of aerosol-cloud-climate interactions is likely to result in improved assessments of future climate change.

Ammonia emission abatement does not fully control reduced forms of nitrogen deposition.

Human activities and population growth have increased the natural burden of reactive nitrogen (N) in the environment. Excessive N deposition on Earth's surface leads to adverse feedbacks on ecosystems and humans. Similar to that of air pollution, emission control is recognized as an efficient means to control acid deposition. Control of nitrogen oxides (NOx = NO + NO2) emissions has led to reduction in deposition of oxidized nitrogen (NOy, the sum of all oxidized nitrogen species, except nitrous oxide [N2O]). Reduced forms of nitrogen (NHx = ammonia [NH3] + ammonium [NH4+]) deposition have, otherwise, increased, offsetting the benefit of reduction in NOy deposition. Stringent control of NH3 emissions is being considered. In this study, we assess the response of N deposition to N emission control on continental regions. We show that significant reduction of NHx deposition is unlikely to be achieved at the early stages of implementing NH3 emission abatement. Per-unit NH3 emission abatement is shown to result in only 60-80% reduction in NHx deposition, which is significantly lower than the demonstrated 80-120% benefit of controlling NOx emissions on NOy deposition. This 60-80% effectiveness of NHx deposition reduction per unit NH3 emission abatement reflects, in part, the effects of simultaneous reductions in NOx and SO2 emissions.

A Neural Network-Assisted Euler Integrator for Stiff Kinetics in Atmospheric Chemistry.

Atmospheric chemistry, characterized by highly coupled sets of ordinary differential equations (ODEs), is dynamically stiff owing to the fact that both fast and slow processes exist simultaneously. We develop here a neural network-assisted Euler integrator for the kinetics of atmospheric chemical reactions. We show that the integral kernel of the chemical reaction system can be represented by a neural network. The stiff kinetics of the atmospheric H2O2/OH/HO2 system, involving 3 species and 4 reactions, and a simplified air pollution mechanism, involving 20 species and 25 reactions, are developed here in detail as illustrations of the neural network Euler integrator. The algorithm developed accelerates the numerical integration of large sets of coupled stiff ODEs by at least one order of magnitude by avoiding the intensive linear algebra that is required in traditional stiff ODE solvers; moreover, the mechanism-specific neural network-assisted algorithm can be readily coupled to other modules in a three-dimensional atmospheric chemical transport model.

Process-Level Modeling Can Simultaneously Explain Secondary Organic Aerosol Evolution in Chambers and Flow Reactors.

Secondary organic aerosol (SOA) data gathered in environmental chambers (ECs) have been used extensively to develop parameters to represent SOA formation and evolution. The EC-based parameters are usually constrained to less than one day of photochemical aging but extrapolated to predict SOA aging over much longer timescales in atmospheric models. Recently, SOA has been increasingly studied in oxidation flow reactors (OFRs) over aging timescales of one to multiple days. However, these OFR data have been rarely used to validate or update the EC-based parameters. The simultaneous use of EC and OFR data is challenging because the processes relevant to SOA formation and evolution proceed over very different timescales, and both reactor types exhibit distinct experimental artifacts. In this work, we show that a kinetic SOA chemistry and microphysics model that accounts for various processes, including wall losses, aerosol phase state, heterogeneous oxidation, oligomerization, and new particle formation, can simultaneously explain SOA evolution in EC and OFR experiments, using a single consistent set of SOA parameters. With α-pinene as an example, we first developed parameters by fitting the model output to the measured SOA mass concentration and oxygen-to-carbon (O:C) ratio from an EC experiment (<1 day of aging). We then used these parameters to simulate SOA formation in OFR experiments and found that the model overestimated SOA formation (by a factor of 3-16) over photochemical ages ranging from 0.4 to 13 days, when excluding the abovementioned processes. By comprehensively accounting for these processes, the model was able to explain the observed evolution in SOA mass, composition (i.e., O:C), and size distribution in the OFR experiments. This work suggests that EC and OFR SOA data can be modeled consistently, and a synergistic use of EC and OFR data can aid in developing more refined SOA parameters for use in atmospheric models.

Computational Simulation of Secondary Organic Aerosol Formation in Laboratory Chambers.

In the atmosphere, certain volatile organic compounds (VOCs) undergo oxidation. Some of these oxidation products then condense into the particle phase. Oxidation products that transform into the particle phase by this route are termed secondary organic aerosol (SOA). Understanding the route by which particulate matter is formed from these reactions is a key challenge in atmospheric chemistry. The principal understanding of SOA formation is derived from studies in laboratory chambers, for which determination of the amount of SOA formed requires a rigorous, quantitative understanding of chamber phenomena. With computational simulation of the processes occurring within an environmental chamber, the extrapolation to atmospheric conditions can be assessed. Moreover, computational chamber modeling of secondary organic aerosol formation will become an integral part of experimental design and data analysis. Here, we present a comprehensive review of processes involved in laboratory chamber SOA formation with a focus on the coupling between different physicochemical processes and understanding that has recently emerged.

Multigeneration Production of Secondary Organic Aerosol from Toluene Photooxidation.

Photooxidation of volatile organic compounds (VOCs) produces secondary organic aerosol (SOA) and light-absorbing brown carbon (BrC) via multiple reaction steps/pathways, reflecting significant chemical complexity relevant to gaseous oxidation and subsequent gas-to-particle conversion. Toluene is an important VOC under urban conditions, but the fundamental chemical mechanism leading to SOA formation remains uncertain. Here, we elucidate multigeneration SOA production from toluene by simultaneously tracking the evolutions of gas-phase oxidation and aerosol formation in a reaction chamber. Large size increase and browning of monodisperse sub-micrometer seed particles occur shortly after initiating oxidation by hydroxyl radical (OH) at 10-90% relative humidity (RH). The evolution in gaseous products and aerosol properties (size/density/optical properties) and chemical speciation of aerosol-phase products indicate that the aerosol growth and browning result from earlier generation products consisting dominantly of dicarbonyl and carboxylic functional groups. While volatile dicarbonyls engage in aqueous reactions to yield nonvolatile oligomers and light-absorbing nitrogen heterocycles/heterochains (in the presence of NH3) at high RH, organic acids contribute to aerosol carboxylates via ionic dissociation or acid-base reaction in a wide RH range. We conclude that toluene contributes importantly to SOA/BrC formation from dicarbonyls and organic acids because of their prompt and high yields from photooxidation and unique functionalities for participation in aerosol-phase reactions.

Unexpected Oligomerization of Small α-Dicarbonyls for Secondary Organic Aerosol and Brown Carbon Formation.

Large amounts of small α-dicarbonyls (glyoxal and methylglyoxal) are produced in the atmosphere from photochemical oxidation of biogenic isoprene and anthropogenic aromatics, but the fundamental mechanisms leading to secondary organic aerosol (SOA) and brown carbon (BrC) formation remain elusive. Methylglyoxal is commonly believed to be less reactive than glyoxal because of unreactive methyl substitution, and available laboratory measurements showed negligible aerosol growth from methylglyoxal. Herein, we present experimental results to demonstrate striking oligomerization of small α-dicarbonyls leading to SOA and BrC formation on sub-micrometer aerosols. Significantly more efficient growth and browning of aerosols occur upon exposure to methylglyoxal than glyoxal under atmospherically relevant concentrations and in the absence/presence of gas-phase ammonia and formaldehyde, and nonvolatile oligomers and light-absorbing nitrogen-heterocycles are identified as the dominant particle-phase products. The distinct aerosol growth and light absorption are attributed to carbenium ion-mediated nucleophilic addition, interfacial electric field-induced attraction, and synergetic oligomerization involving organic/inorganic species, leading to surface- or volume-limited reactions that are dependent on the reactivity and gaseous concentrations. Our findings resolve an outstanding discrepancy concerning the multiphase chemistry of small α-dicarbonyls and unravel a new avenue for SOA and BrC formation from atmospherically abundant, ubiquitous carbonyls and ammonia/ammonium sulfate.

Emissions Measurements from Household Solid Fuel Use in Haryana, India: Implications for Climate and Health Co-benefits.

A large concern with estimates of climate and health co-benefits of "clean" cookstoves from controlled emissions testing is whether results represent what actually happens in real homes during normal use. A growing body of evidence indicates that in-field emissions during daily cooking activities differ substantially from values obtained in laboratories, with correspondingly different estimates of co-benefits. We report PM2.5 emission factors from uncontrolled cooking (n = 7) and minimally controlled cooking tests (n = 51) using traditional chulha and angithi stoves in village kitchens in Haryana, India. Minimally controlled cooking tests (n = 13) in a village kitchen with mixed dung and brushwood fuels were representative of uncontrolled field tests for fine particulate matter (PM2.5), organic and elemental carbon (p > 0.5), but were substantially higher than previously published water boiling tests using dung or wood. When the fraction of nonrenewable biomass harvesting, elemental, and organic particulate emissions and modeled estimates of secondary organic aerosol (SOA) are included in 100 year global warming commitments (GWC100), the chulha had a net cooling impact using mixed fuels typical of the region. Correlation between PM2.5 emission factors and GWC (R2 = 0.99) implies these stoves are climate neutral for primary PM2.5 emissions of 8.8 ± 0.7 and 9.8 ± 0.9 g PM2.5/kg dry fuel for GWC20 and GWC100, respectively, which is close to the mean for biomass stoves in global emission inventories.

Synergistic O3 + OH oxidation pathway to extremely low-volatility dimers revealed in ß-pinene secondary organic aerosol.

Dimeric compounds contribute significantly to the formation and growth of atmospheric secondary organic aerosol (SOA) derived from monoterpene oxidation. However, the mechanisms of dimer production, in particular the relevance of gas- vs. particle-phase chemistry, remain unclear. Here, through a combination of mass spectrometric, chromatographic, and synthetic techniques, we identify a suite of dimeric compounds (C15-19H24-32O5-11) formed from concerted O3 and OH oxidation of ß-pinene (i.e., accretion of O3- and OH-derived products/intermediates). These dimers account for an appreciable fraction (5.9-25.4%) of the ß-pinene SOA mass and are designated as extremely low-volatility organic compounds. Certain dimers, characterized as covalent dimer esters, are conclusively shown to form through heterogeneous chemistry, while evidence of dimer production via gas-phase reactions is also presented. The formation of dimers through synergistic O3 + OH oxidation represents a potentially significant, heretofore-unidentified source of low-volatility monoterpene SOA. This reactivity also suggests that the current treatment of SOA formation as a sum of products originating from the isolated oxidation of individual precursors fails to accurately reflect the complexity of oxidation pathways at play in the real atmosphere. Accounting for the role of synergistic oxidation in ambient SOA formation could help to resolve the discrepancy between the measured atmospheric burden of SOA and that predicted by regional air quality and global climate models.

Gas-Phase Reactions of Isoprene and Its Major Oxidation Products.

Isoprene carries approximately half of the flux of non-methane volatile organic carbon emitted to the atmosphere by the biosphere. Accurate representation of its oxidation rate and products is essential for quantifying its influence on the abundance of the hydroxyl radical (OH), nitrogen oxide free radicals (NO x), ozone (O3), and, via the formation of highly oxygenated compounds, aerosol. We present a review of recent laboratory and theoretical studies of the oxidation pathways of isoprene initiated by addition of OH, O3, the nitrate radical (NO3), and the chlorine atom. From this review, a recommendation for a nearly complete gas-phase oxidation mechanism of isoprene and its major products is developed. The mechanism is compiled with the aims of providing an accurate representation of the flow of carbon while allowing quantification of the impact of isoprene emissions on HO x and NO x free radical concentrations and of the yields of products known to be involved in condensed-phase processes. Finally, a simplified (reduced) mechanism is developed for use in chemical transport models that retains the essential chemistry required to accurately simulate isoprene oxidation under conditions where it occurs in the atmosphere-above forested regions remote from large NO x emissions.

Coupling Filter-Based Thermal Desorption Chemical Ionization Mass Spectrometry with Liquid Chromatography/Electrospray Ionization Mass Spectrometry for Molecular Analysis of Secondary Organic Aerosol.

Filter-based thermal desorption (F-TD) techniques, such as the filter inlet for gases and aerosols, are widely employed to investigate the molecular composition and physicochemical properties of secondary organic aerosol (SOA). Here, we introduce an enhanced capability of F-TD through the combination of a customized F-TD inlet with chemical ionization mass spectrometry (CIMS) and ultraperformance liquid chromatography/electrospray ionization mass spectrometry (UPLC/ESI-MS). The utility of F-TD/CIMS + UPLC/ESI-MS is demonstrated by application to α-pinene ozonolysis SOA for which increased filter aerosol mass loading is shown to slow the evaporation rates of deposited compounds. Evidence for oligomer decomposition producing multimode F-TD/CIMS thermograms is provided by the measurement of the mass fraction remaining of monomeric and dimeric α-pinene oxidation products on the filter via UPLC/ESI-MS. In situ evaporation of aerosol particles suggests that α-pinene-derived hydroperoxides are thermally labile; thus, analysis of particle-phase (hydro)peroxides via F-TD may not be appropriate. A synthesized pinene-derived dimer ester (C20H32O5) is found to be thermally stable up to 200 °C, whereas particle-phase dimers (C19H30O5) are observed to form during F-TD analysis via thermally induced condensation of synthesized pinene-derived alcohols and diacids. The complementary F-TD/CIMS + UPLC/ESI-MS method offers previously inaccessible insight into the molecular composition and thermal desorption behavior of SOA that both clarifies and expands on analysis via traditional F-TD techniques.

Synthesis of Carboxylic Acid and Dimer Ester Surrogates to Constrain the Abundance and Distribution of Molecular Products in α-Pinene and ß-Pinene Secondary Organic Aerosol.

Liquid chromatography/negative electrospray ionization mass spectrometry [LC/(-)ESI-MS] is routinely employed to characterize the identity and abundance of molecular products in secondary organic aerosol (SOA) derived from monoterpene oxidation. Due to a lack of authentic standards, however, commercial terpenoic acids (e.g., cis-pinonic acid) are typically used as surrogates to quantify both monomeric and dimeric SOA constituents. Here, we synthesize a series of enantiopure, pinene-derived carboxylic acid and dimer ester homologues. We find that the (-)ESI efficiencies of the dimer esters are 19-36 times higher than that of cis-pinonic acid, demonstrating that the mass contribution of dimers to monoterpene SOA has been significantly overestimated in past studies. Using the measured (-)ESI efficiencies of the carboxylic acids and dimer esters as more representative surrogates, we determine that molecular products measureable by LC/(-)ESI-MS account for only 21.8 ± 2.6% and 18.9 ± 3.2% of the mass of SOA formed from ozonolysis of α-pinene and ß-pinene, respectively. The 28-36 identified monomers (C7-10H10-18O3-6) constitute 15.6-20.5% of total SOA mass, whereas only 1.3-3.3% of the SOA mass is attributable to the 46-62 identified dimers (C15-19H24-32O4-11). The distribution of identified α-pinene and ß-pinene SOA molecular products is examined as a function of carbon number (nC), average carbon oxidation state (OS¯C), and volatility (C*). The observed order-of-magnitude difference in (-)ESI efficiency between monomers and dimers is expected to be broadly applicable to other biogenic and anthropogenic SOA systems analyzed via (-) or (+) LC/ESI-MS under various LC conditions, and demonstrates that the use of unrepresentative surrogates can lead to substantial systematic errors in quantitative LC/ESI-MS analyses of SOA.

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. We find that oxygenated aromatic compounds, including phenols and methoxyphenols, account for slightly less than 60% of the SOA formed and help our model explain the variability in the organic aerosol mass (R2 = 0.68) and O/C (R2 = 0.69) enhancement ratios observed across 11 chamber experiments. Despite abundant emissions, heterocyclic compounds that included furans contribute to ∼20% of the total SOA. The use of pyrolysis-temperature-based or averaged emission profiles to represent SOA precursors, rather than those specific to each fire, provide similar results to within 20%. Our findings demonstrate the necessity of accounting for oxygenated aromatics from biomass-burning emissions and their SOA formation in chemical mechanisms.

Unexpected rise of ozone in urban and rural areas, and sulfur dioxide in rural areas during the coronavirus city lockdown in Hangzhou, China: implications for air quality.

The outbreak of coronavirus named COVID-19, initially identified in Wuhan, China in December 2019, has spread rapidly at the global scale. Most countries have rapidly stopped almost all activities including industry, services and transportation of goods and people, thus decreasing air pollution in an unprecedented way, and providing a unique opportunity to study air pollutants. While satellite data have provided visual evidence for the global reduction in air pollution such as nitrogen dioxide (NO2) worldwide, precise and quantitative information is missing at the local scale. Here we studied changes in particulate matter (PM2.5, PM10), carbon monoxide (CO), NO2, sulfur dioxide (SO2) and ozone (O3) at 10 urban sites in Hangzhou, a city of 7.03 million inhabitants, and at 1 rural site, before city lockdown, January 1-23, during city lockdown, January 24-February 15, and during resumption, February 16-28, in 2020. Results show that city lockdown induced a sharp decrease in PM2.5, PM10, CO, and NO2 concentrations at both urban and rural sites. The NO2 decrease is explained by reduction in traffic emissions in the urban areas, and by lower regional transport in rural areas during lockdown, as expected. SO2 concentrations decreased from 6.3 to 5.3 µg m-3 in the city, but increased surprisingly from 4.7 to 5.8 µg m-3 at the rural site: this increase is attributed both to higher coal consumption for heating and emissions from traditional fireworks of the Spring Eve and Lantern Festivals during lockdown. Unexpectedly, O3 concentrations increased by 145% from 24.6 to 60.6 µg m-3 in the urban area, and from 42.0 to 62.9 µg m-3 in the rural area during the lockdown. This finding is explained by the weakening of chemical titration of O3 by NO due to reductions of NOx fresh emissions during the non-photochemical reaction period from 20:00 PM to 9:00 AM (local time). During the lockdown, compared to the same period in 2019, the daily average concentrations in the city decreased by 42.7% for PM2.5, 47.9% for PM10, 28.6% for SO2, 22.3% for CO and 58.4% for NO2, which is obviously explained by the absence of city activities. Overall, we observed not only the expected reduction in some atmospheric pollutants (PM, SO2, CO, NO2), but also unexpected increases in SO2 in the rural areas and of ozone (O3) in both urban and rural areas, the latter being paradoxically due to the reduction in nitrogen oxide levels. In other words, the city lockdown has improved air quality by reducing PM2.5, PM10, CO, and NO2, but has also decreased air quality by augmenting O3 and SO2.