Organic Aerosol Research Articles

Biogenic secondary organic aerosol participates in plant interactions and herbivory defense.

Biogenic secondary organic aerosols (SOAs) can be formed from the oxidation of plant volatiles in the atmosphere. Herbivore-induced plant volatiles (HIPVs) can elicit plant defenses, but whether such ecological functions persist after they form SOAs was previously unknown. Here we show that Scots pine seedlings damaged by large pine weevils feeding on their roots release HIPVs that trigger defenses in neighboring conspecific plants. The biological activity persisted after HIPVs had been oxidized to form SOAs, which was indicated by receivers displaying enhanced photosynthesis, primed volatile defenses, and reduced weevil damage. The elemental composition and quantity of SOAs likely determines their biological functions. This work demonstrates that plant-derived SOAs can mediate interactions between plants, highlighting their ecological significance in ecosystems.

Insights Into the Influence of Anthropogenic Emissions on the Formation of Secondary Organic Aerosols Based on Online Measurements

AbstractTo investigate the combined impacts of anthropogenic and biogenic emissions on the formation of secondary organic aerosols (SOA), SOA molecular tracers, their corresponding volatile organic compound precursors, and other air pollutants were measured online during the winter and summer seasons of 2022 in an industrial city, Zibo, China. The results indicate that the average concentrations of SOA tracers were 16.1 ± 9.8 ng m−3 in winter and 99.4 ± 57.2 ng m−3 in summer. During winter, anthropogenic SOA (ASOA, the sum of SOA derived from naphthalene and mono‐aromatic volatile organic compounds) dominated, whereas isoprene SOA (SOAI) prevailed in summer. Correlation analysis between SO42− and both SOAI and high‐order monoterpene SOA tracers (SOAM‐H) (R = 0.46–0.72, p < 0.001) revealed that higher aerosol acidity facilitated the formation of SOAI and SOAM‐H, with SO2 emissions playing a significant role in leading to higher acidity. Most biogenic SOA (BSOA) tracers exhibited a significant positive correlation with NO3−, particularly in winter, implying the remarkable influence of NOx emissions on BSOA formation. The levels of BSOA tracers increased with NH3, indicating that NH3 can enhance the formation of BSOA. In summer, SOA formation correlated with Ox (Ox = O3 + NO2), indicating the substantial impact of atmospheric oxidizing capacity on SOA formation. During winter, aerosol liquid water content (ALWC) correlated well with SOAI tracers (i.e., 3‐hydroxyglutaric acid (3‐HGA) and 3‐hydroxy‐4,4‐dimethylglutaric acid (3‐HDMGA)), and 2,3‐dihydroxy‐4‐oxopentanoic acid (DHOPA) (R > 0.5, p < 0.001), indicating the important contribution of aqueous‐phase formation of SOA. These findings underscore the significant role of anthropogenic pollutant emissions in the formation of ASOA and BSOA in urban environments.

Role of Organic Vapor Precursors in Secondary Organic Aerosol Formation: Concurrent Observations of IVOCs and VOCs in Guangzhou

AbstractSecondary organic aerosol (SOA) formed through the atmospheric transformation of organic vapors constitutes a significant portion of fine particulate matter or PM2.5. While recent laboratory studies underscore the importance of intermediate‐volatility organic compounds (IVOCs) as key precursors to SOA, field observations that recognize the role of both volatile organic compounds (VOCs) and IVOCs in SOA formation remain scarce. In this study, we conducted concurrent measurements of VOCs and IVOCs in ambient air at urban and suburban sites in Guangzhou during a PM2.5 pollution event in winter 2021. The results reveal that between 12:00–15:00 local time, the photochemically adjusted initial concentrations of VOCs at both sites were approximately 7 times higher than that of IVOCs. However, the SOA formation potential (SOAFP) of primary hydrocarbon IVOCs exceeded that of VOCs by over 3–4 times. Receptor modeling results further indicated that while ship emissions contributed to less than 10% of the C2–C22 primary hydrocarbons concentration (VOCs + primary carbonaceous IVOCs), they accounted for the most significant source (approximately 40%) of SOA formation. This study highlights the substantial role of IVOCs in SOA formation and emphasizes the importance of future PM2.5 pollution control measures targeting major IVOCs contributors, such as ship emissions in harbor cities.

Iron-Containing Seed Particles Enhance α-Pinene Secondary Organic Aerosol Mass Concentration and Dimer Formation.

Secondary organic aerosol (SOA) comprises the majority of submicron particles and is important for air pollution, health, and climate. When SOA mixes with inorganic particles containing transition metals (e.g., Fe), chemical reactions altering physicochemical properties can occur. Here, we study Fe's impact on the formation and chemical composition of SOA formed via dark α-pinene ozonolysis on either (NH4)2SO4 or Fe-containing (NH4)2SO4 seed particles and aged at varying relative humidities (RHs). Aerosol composition was determined using online extractive electrospray ionization mass spectrometry, providing high-resolution chemical and temporal identification of monomers and dimers in the SOA. At high RH, Fe's presence resulted in higher particulate SOA mass concentrations (117 ± 14 μg m-3) than those formed in its absence (70 ± 1 μg m-3). Enhanced mass is coupled with more dimers (C15-20's), attributed to Fenton-driven oligomerization reactions. Experiments with Fe3+-containing seeds showed similar chemical composition and enhanced SOA mass, suggesting a dark reduction pathway to form Fe2+ in the presence of SOA. Overall, Fe's presence at high RH lowers SOA volatility and enhances particulate organic mass and condensed phased reactions of higher volatility species that would normally not participate in SOA formation, which may be important when considering its formation in air quality and climate models.

Submicron Organic Aerosol Types in the Summertime Arctic: Mixing State, Geographic Distribution, and Drivers

AbstractDuring the 2017 summertime Arctic cruise observation campaigns, we measured over 290,000 individual submicron particles and clustered them into two inorganic classes (dominated by sea salt, accounting for 38.6% by number fraction) and five organic classes (dominated by natural and anthropogenic organics, 61.4%), presenting a distinct difference in geographic distribution. In the high Arctic and marginal ice zone (81.1–84.6°N) compared with the low Arctic (Chukchi Sea, Svalbard, and Iceland, <80°N), ocean‐derived organic aerosols were more prevalent (73.6% vs. 37.1%). Specifically, we found sharp contrasts in the geographic distributions of OC‐Ca (organics internally mixed with calcium, 29.0% vs. 9.4%) and OC‐S (organics internally mixed with sulfate, 3.2% vs. 21.4%). Utilizing an explainable machine learning technique, we inferred that OC‐Ca was driven by wind‐blown sea ice and/or sea ice floes and/or bubble bursting within sea ice leads under low wind speed conditions in the high Arctic, while OC‐S tended to associate with elemental carbon, sulfate, and higher temperatures, potentially originating from combustion emissions at low latitude regions.

Observational evidence reveals the significance of nocturnal chemistry in seasonal secondary organic aerosol formation

Oxidized Organic Aerosol (OOA), a major component of fine atmospheric particles, impacts climate and human health. Previous experiments and atmospheric models emphasize the importance of nocturnal OOA formation from NO3· oxidation of biogenic VOCs. This seasonal study extends the understanding by showing that nocturnal oxidation of biomass-burning emissions can account for up to half of total OOA production in fall and winter. It is the first to distinguish nocturnal OOA characteristics from daytime OOA across all seasons using bulk aerosol measurements. Summer observations of nocturnal OOA align well with regional chemistry transport model predictions, but discrepancies in other seasons reveal a common model deficiency in representing biomass-burning emissions and their nocturnal oxidation. This study underscores the significance of near-ground nocturnal OOA production, proposes a method to differentiate it using bulk aerosol measurements, and suggests model optimization strategies. These findings enhance the understanding and prediction of nighttime OOA formation.

Insight into wet scavenging effects on sulfur and nitrogen containing organic compounds in urban Beijing

Sulfur-containing organic compounds (SOCs) and nitrogen-containing organic compounds (NOCs) play critical roles in regulating the physical and chemical properties of organic aerosols (OA), while the understanding of them remains limited. Here, the high-resolution real-time measurements of submicron aerosols were conducted in urban Beijing, mainly to investigate wet scavenging effects on the potential formation and evolution mechanism of OA, especially SOCs and NOCs. OA composition transitioned from being primarily SOCs before wet processes to NOCs after wet processes. Further molecular fragments identification suggested SOCs mainly comprised glycolic acid sulfate formed by aqueous-phase processing during the entire observation, and aromatic- and monoterpene-derived SOCs formed by photochemical processing before snowfall. NOCs species were diverse and dominated by highly oxidized amides and amino acids mainly produced by photochemical processing. This study provided an in-depth insight into the potential formation and evolution pathways of SOCs and NOCs in OA in the urban atmosphere.

PM10 Organic Aerosol Fingerprints by Using Liquid Chromatography Orbitrap Mass Spectrometry: Urban vs. Suburban in an Eastern Mediterranean Medium-Sized Coastal City

This study compares the PM10 (particulate matter of diameter smaller than 10 μm) organic aerosol composition between urban and suburban stations in Heraklion, Crete, during winter 2024 in order to highlight the impact of local anthropogenic activities on urban atmospheric particulate matter pollution. Using an HPLC-ESI-MS Orbitrap analyzer (High Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometry) in full MS scan mode at a resolution of 140,000, 48 daily aerosol filter extracts were analyzed in both positive and negative modes, resulting in the detection of 2809 and 3823 features, respectively. Features with at least five times higher intensity in the urban environment compared to the suburban, and p < 0.05, were deemed significant. A correlation with black carbon (r > 0.6) was observed for 71% of significant urban features in positive mode. These features showed a predominance of low O:C ratios (<0.2) and the majority were classified as intermediate volatility organic compounds (IVOCs), indicating fresh primary emissions. A clear urban–suburban distinction was shown by PCA of positive mode features, unlike the negative mode features. Regarding the total intensity of the features, urban samples were on average 55% higher than suburban samples in positive mode and 39% higher in negative mode. This study reveals the molecular profile of locally emitted combustion related organics observed in positive mode in an urban environment.

Overlooked Trace Molecules in Organic Aerosol Revealed by Gas Chromatography-Orbitrap Mass Spectrometry.

Molecular characterization of organic aerosol (OA) is crucial for understanding its sources and atmospheric processes. However, the chemical components of OA remain not well constrained. This study used gas chromatography-Orbitrap mass spectrometry (GC-Orbitrap MS) and GC-Quadrupole MS (GC-qMS) to investigate the organic composition in PM2.5 from Xi'an, Northwest China. GC-Orbitrap MS identified 335 organic tracers, including overlooked isomers and low-concentration molecules, approximately 1.6 times more than GC-qMS. The "molecular corridor" assessment shows the superior capability of GC-Orbitrap MS in identifying an expansive range of compounds with higher volatility and oxidation states, such as furanoses/pyranoses, di/hydroxy/ketonic acids, di/poly alcohols, aldehydes/ketones, and amines/amides. Seasonal variations in OA composition reflect diverse sources: increased di/poly alcohols in winter are derived from indoor emissions, furanoses/pyranoses and heterocyclics in spring and summer might be from biogenic emissions and secondary formation, and amides in autumn are probably from biomass burning. Integrating partial least squares discriminant analysis (PLS-DA) and potential source contribution function (PSCF) models, the source similarities and differences are further elucidated, highlighting the role of local emissions and transport from southern cities. This study offers new insights into the OA composition aided by the high mass resolution and sensitivity of GC-Orbitrap MS.

Effects of Ammonia Mitigation on Secondary Organic Aerosol and Ammonium Nitrate Particle Formation in Photochemical Reacted Gasoline Vehicle Exhausts

Gaseous air pollutants emitted primarily by anthropogenic sources form secondary products through photochemical reactions, complicating the regulatory analysis of anthropogenic emissions in the atmosphere. We used an environmental chassis dynamometer and a photochemical smog chamber to conduct a parameter sensitivity experiment to investigate the formation of secondary products from a gasoline passenger car. To simulate the mitigation of ammonia emissions from gasoline vehicle exhausts assuming future emission controls and to allow photochemical oxidation and aging of the vehicle exhaust, ammonia was selectively removed by a series of five denuders installed between the vehicle and photochemical smog chamber. Overall, there were no differences in the formation of secondary organic aerosols and ozone with or without ammonia mitigation. However, the potential for ammonium nitrate particle formation was significantly reduced with ammonia mitigation. In addition, ammonia mitigation resulted in increased aerosol acidity due to nitric acid in the gas phase not being neutralized by ammonia and condensing onto the liquid particle phase, indicating a potentially important secondary effect associated with ammonia mitigation. Thus, we provide new insights into the effects of ammonia mitigation on secondary emissions from gasoline vehicle exhaust and into a potentially useful experimental approach for determining primary and secondary emissions.

Insights into chemical aging of urban aerosols over Delhi, India

Atmospheric particles can undergo aging as they are transported over long distances and mix with particles from other sources. This can lead to the accumulation of pollutants and the formation of complex aerosol mixtures with diverse chemical and physical properties. To investigate the process of aging in ambient atmosphere, 24h sampling of PM2.5 aerosol particles on Quartz microfiber filter with a tin substrate was carried out from November 2020 to March 2021 at CSIR-National Physical Laboratory, New Delhi (28°38'10″ N and 77°10′17" E), using fine particle sampler. Based on the observations of weather and meteorological parameters, a few episodic cases have been selected, and samples were analyzed at bulk and individual particle level. The objective of the present study is to investigate the aging characteristics of aerosols, enabling us to understand the mixing of aerosols (at both bulk and individual particle levels) and the variation in fresh and deformed (aged with other species) graphitic content in the episodic cases. The Raman Spectroscopy technique employed measures the intensity of graphitic (G band; around 1580 cm−1) and disordered graphitic (D band; around 1320 cm−1) content of aerosols. Individual particle microscopic observations reveal the occurrence of open chain fractals of black carbon in variable monomer sizes, sometimes agglomerated with metals like Cu, Cr, Ca etc., along with the presence of S- rich and organic aerosols while the Raman Spectrum (bulk sample analysis) highlights graphitic and disordered (when graphite interacts with other chemical species) graphitic intensities. Comparing the intensities of heavy haze and moderate haze with non-haze days (for comparison purpose, March 23, 2021 with the lowest PM2.5 concentration ∼ 62 μg/m3, has been considered as a non-haze day), it was observed that the intensities recorded on haze days were 45 to 200 times higher for the G band and 43 to 93 times higher for the D band; while for moderate haze days, the intensities were 4 to 61 times higher for the G band and 2 to 29 times higher for the D band. These findings suggest chemical processing of BC during haze days.

Long-term contributions of VOC sources and their link to ozone pollution in Bronx, New York City

Changes in energy and environmental policies along with changes in the energy markets of New York State over the past two decades, have spurred interest in evaluating their impacts on emissions from various energy generation sectors. This study focused on quantifying these effects on VOC (volatile organic compounds) emissions and their subsequent impacts on air quality within the New York City (NYC) metropolitan area. NYC is an EPA nonattainment region for ozone (O3) and likely is a VOC limited region. NYC has a complex coastal topography and meteorology with low-level jets and sea/bay/land breeze circulation associated with heat waves, leading to summertime O3 exceedances and formation of secondary organic aerosol (SOA). To date, no comprehensive source apportionment studies have been done to understand the contributions of local and long-range sources of VOCs in this area. This study applied an improved Positive Matrix Factorization (PMF) methodology designed to incorporate atmospheric dispersion and photochemical reaction losses of VOCs to provide improved apportionment results. Hourly measurements of VOCs were obtained from a Photochemical Assessment Monitoring Station located at an urban site in the Bronx from 2000 to 2021. The study further explores the role of VOC sources in O3 and SOA formation and leverages advanced machine learning tools, XGBoost and SHAP algorithms, to identify synergistic interactions between sources and provided VOC source impacts on ambient O3 concentrations. Isoprene demonstrated a substantial influence in the source contribution of the biogenic factor, emphasizing its role in O3 formation. Notable contributions from anthropogenic emissions, such as fuel evaporation and various industrial processes, along with significant traffic-related sources that likely contribute to SOA formation, underscore the combined impact of natural and human-made sources on O3 pollution. Findings of this study can assist regulatory agencies in developing appropriate policy and management initiatives to control O3 pollution in NYC.

Liquid phase transformation mechanism of β-caryophyllonic acid initiated by hydroxyl radicals and ozone in atmosphere

β-caryophyllonic acid (BCA), as an important precursor of aqueous secondary organic aerosols (aqSOA), has adverse effects on the atmospheric environment and human health. However, the key atmospheric chemical reaction process in which BCA participates in the formation of aqueous secondary organic aerosols is still unclear. In this study, the reaction mechanism and kinetics of BCA with ·OH and O3 were investigated by quantum chemical calculations. The initiation reactions between BCA and ·OH include addition and H-abstraction reaction pathways, subsequent intermediates will also react with O2, ultimately undergo a cracking reaction to generate small molecular substances. The reaction of BCA with O3 can generate primary ozone oxides and the Criegee Intermediates oIM3, subsequent main reaction products include keto-BCA, as well as other small molecule aqSOA precursors. The entire reaction process increases the O/C ratio of aqSOA in the aqueous phase and generates products of small molecules such as 4-formylpropionic acid, which plays an important role in the formation of aqSOA. At 298K, the transformation rate constants of BCA initiated by ·OH and O3 are 1.47 × 1010 M−1 s−1 and 3.16 × 105 M−1 s−1, respectively, the atmospheric lifetimes of BCA reacting with ·OH range from 0.86 h–5.40 h, while the lifetimes of BCA reacting with O3 range from 0.44 h–10.04 years. This suggests that BCA primarily reacts with ·OH. However, under higher O3 concentrations, its ozonolysis becomes significant, promoting the formation of aqSOA. According to the risk assessment, the toxicity of most transformation products (TPs) gradually decreased, but the residual developmental toxicity could not be ignored. In this paper, the atmospheric liquid phase oxidation mechanisms of sesquiterpene unsaturated derived acid were studied from the microscopic level, which has guiding significance for the formation and transformation of aqSOA in atmosphere.

Biogenic and Anthropogenic Secondary Organic Aerosols Become Fluorescent after Highly Acidic Aging.

Primary biological aerosol particles (PBAPs) and secondary organic aerosol (SOA) both contain organic compounds that share similar chemical and optical properties. Fluorescence is often used to characterize PBAPs; however, this may be hindered due to interferences from fluorophores in SOA. Despite extensive efforts to understand the aging of SOA under elevated particle acidity conditions, little is known about how these processes affect the fluorescence of SOA and thereby their interference with the measurements of PBAPs. The objective of this study is to investigate the fluorescence of SOA and understand the influence of acidity on the optical properties of organic aerosols and potential interference for the analysis of bioaerosols. The SOA was generated by O3- or OH-initiated oxidation of d-limonene or α-pinene, as well as by OH-initiated oxidation of toluene or xylene. The SOA compounds were then aged by exposure to varying concentrations of aqueous H2SO4 for 2 days. Absorption and fluorescence spectrophotometry were used to examine the changes in the optical properties before and after aging. The key observation was the appearance of strongly light-absorbing and fluorescent compounds at pH = ∼-1, suggesting that acidity is a major driver of SOA aging. The aged SOA from biogenic precursors (d-limonene and α-pinene) resulted in stronger fluorescence than the aged SOA from toluene and xylene. The absorption spectra of the aged SOA changed drastically in shape upon dilution, whereas the shapes of the fluorescence spectra remained the same, suggesting that the fluorophores and chromophores in SOA are separate sets of species. The fluorescence spectra of aged SOA overlapped with the fluorescence spectra of PBAPs, suggesting that SOA exposed to highly acidic conditions can be confused with PBAPs detected by fluorescence-based methods. These processes are likely to play a role in the atmospheric regions where high concentrations of H2SO4 persist, such as the upper troposphere and lower stratosphere.

Dynamic evolution of particulate and gaseous emissions for typical residential coal combustion

Residential coal combustion still accounts for half of the heating energy consumption in many developing countries. The dynamic variation during the combustion process importantly determines the combustion facility design and appropriate air quality assessment, which was omitted in conventional studies. This study investigated the emissions of particulate and gaseous pollutants during the combustion process for typical coal types using online monitoring. During the first pyrolysis stage with temperature climbing, the organic aerosols (OA) and gases reached peak concentration. The second fierce combustion stage had the highest temperature and produced the highest cumulative emissions, particularly a substantial amount of black carbon for coals with higher volatile content. Using higher-quality coals will undoubtedly reduce PM emissions, by a factor of 10 from bituminous to anthracite coal. However, more ultrafine particles (d < 0.1 μm) from cleaner coal may pose additional health risks. Anthracite and honeycomb coal had approximately twice the energy content and emitted more CO2 per unit mass of fuel and had more persistent SO2 emissions throughout the burnout stage. The oxygenation of OA and organic gases remained increased during combustion, suggesting the pyrolysis products underwent oxidation before being emitted. The investigation of the coal combustion process suggests the importance of reducing volatiles to control PM emissions, but the potential negative synergistic effects between PM reduction and increased carbon emissions should also be considered.

Responses of plant volatile emissions to increasing nitrogen deposition: A pilot study on Eucalyptus urophylla

Biogenic volatile organic compounds (BVOCs) significantly impact atmospheric chemistry, with emissions potentially influenced by nitrogen (N) deposition. The response of BVOC emissions to increasing N deposition remains debated. In this study, we examined Eucalyptus urophylla (E. urophylla) using three N treatments: N0, N50, and N100 (0, 50, and 100 kg N hm−2 yr−1 N addition). These treatments were applied to mature E. urophylla trees in a plantation subjected to over 10 years of soil N addition in southern China, a region with severe N deposition. Seventeen BVOCs were measured, with isoprene (36.99 %), α-pinene (38.80 %), and d-limonene (14.27 %) being the predominant compounds under natural conditions. Total BVOC emissions under N50 were nearly double those under N0 and N100, with leaf net CO2 assimilation identified as the most critical photosynthetic parameter. Isoprene and α-pinene emissions significantly increased under N50 compared to N0, while d-limonene emission decreased under N100. Stronger correlations for individual BVOCs under N50 and N100 compared to N0 might be due to differences in BVOC biosynthetic pathways and storage structures. The localized canopy-scale emission factors (EFs) under N50 were significantly higher than the default values in the Model of Emissions of Gases and Aerosols from Nature (MEGAN), suggesting the model might underestimate BVOC emissions from Eucalyptus in southern China under increased N deposition. Additionally, the secondary pollutant formation potentials of BVOCs were evaluated, identifying isoprene and monoterpenes as primary precursors of ozone and secondary organic aerosols. This study provides insights into the impacts of increased N deposition on BVOC emissions and their contribution to secondary atmospheric pollution. Updating localized BVOC EFs for subtropical tree species in southern China is crucial to reduce uncertainties in BVOC estimations under current and future N deposition scenarios.

Hygroscopic growth and activation changed submicron aerosol composition and properties in the North China Plain

Abstract. Aerosol hygroscopic growth and activation under high-relative-humidity (RH) conditions significantly influence the physicochemical properties of submicron aerosols (PM1). However, this process remains poorly characterized due to limited measurements. To address this gap, we deployed an advanced aerosol–fog sampling system that automatically switched between PM1, PM2.5 and total suspended particulate (TSP) inlets at a rural site in the North China Plain in the cold season. The results revealed that aerosol swelling due to water vapor uptake influenced aerosol sampling under high-RH conditions by shifting the cut-off size of impactors. At subsaturated high RH (&gt; 90 %), over 25 % of aerosol mass with dry diameters below 1 µm resided in supermicron ranges, while in supersaturated foggy conditions, more than 70 % of submicron aerosol migrated to supermicron ranges. Hygroscopic growth and activation particularly affected highly hydrophilic inorganic salts, shifting a significant number of submicron sulfate and nitrate particles to supermicron ranges, with 27 %–33 % at 95 % ≤ RH ≤ 99 % and more than 78 % under supersaturated foggy conditions. Moreover, more than 10 % of submicron biomass burning organic aerosols grew beyond 2.5 µm during fog events, while fossil-fuel-related organic aerosol (FFOA) remained dominantly in submicron ranges, suggesting inefficient aqueous conversion of FFOA. The two secondary organic aerosol (SOA) factors (OOA1 and OOA2) behaved differently under supersaturated conditions, with OOA2 exhibiting a higher activated fraction despite a lower oxygen / carbon ratio. A substantial increase in organic nitrate and organosulfur mass concentrations in activated droplets during fog events suggested aqueous conversions and formations of brown carbon with potential radiative impacts. Overall, our study highlights remarkably different cloud and fog processing behaviors between primary and secondary aerosols, which would benefit a better understanding of aerosol–cloud interactions under distinct atmospheric conditions.

Impact of Heatwaves and Declining NOx on Nocturnal Monoterpene Oxidation in the Urban Southeastern United States.

Nighttime oxidation of monoterpenes (MT) via the nitrate radical (NO3) and ozone (O3) contributes to the formation of secondary organic aerosol (SOA). This study uses observations in Atlanta, Georgia from 2011-2022 to quantify trends in nighttime production of NO3 (PNO3) and O3 concentrations and compare to model outputs from the EPA's Air QUAlity TimE Series Project (EQUATES). We present urban-suburban gradients in nighttime NO3 and O3 concentrations and quantify their fractional importance (F) for MT oxidation. Both observations and EQUATES show a decline in PNO3, with modeled PNO3 declining faster than observations. Despite decreasing PNO3, we find that NO3 continues to dominate nocturnal boundary layer (NBL) MT oxidation (FNO3 = 60%) in 2017, 2021, and 2022, which is consistent with EQUATES (FNO3 = 80%) from 2013-2019. This contrasts an anticipated decline in FNO3 based on prior observations in the nighttime residual layer, where O3 is the dominant oxidant. Using two case studies of heatwaves in summer 2022, we show that extreme heat events can increase NO3 concentrations and FNO3, leading to short MT lifetimes (<1 h) and high gas-phase organic nitrate production. Regardless of the presence of heatwaves, our findings suggest sustained organic nitrate aerosol formation in the urban SE US under declining NOx emissions, and highlight the need for improved representation of extreme heat events in chemistry-transport models and additional observations along urban to rural gradients.

Contrast in Secondary Organic Aerosols between the Present Day and the Preindustrial Period: The Importance of Nontraditional Sources and the Changed Atmospheric Oxidation Capability

Contrast in Secondary Organic Aerosols between the Present Day and the Preindustrial Period: The Importance of Nontraditional Sources and the Changed Atmospheric Oxidation Capability

Observed and CMIP6-model-simulated organic aerosol response to drought in the contiguous United States during summertime

Abstract. Drought events have been linked with the enhancements of organic aerosols (OAs), but the mechanisms have not been comprehensively understood. This study investigates the relationships between the monthly standardized precipitation–evapotranspiration index (SPEI) and surface OA in the contiguous United States (CONUS) during the summertime from 1998 to 2018. OA under severe drought conditions shows a significant increase in mass concentrations across most of the CONUS relative to non-drought periods, with the Pacific Northwest (PNW) and Southeast United States (SEUS) experiencing the highest average enhancement of 1.79 µg m−3 (112 %) and 0.92 µg m−3 (33 %), respectively. In the SEUS, a linear regression approach between OA and sulfate was used to estimate the epoxydiol-derived secondary organic aerosol (IEPOX SOA), which is the primary driver of the OA enhancements under droughts due to the simultaneous increase in emissions of biogenic volatile organic compounds (VOCs; such as isoprene and monoterpene) and sulfate. The rise in sulfate is mainly caused by the reduced wet deposition because of the up to 62 % lower precipitation amount. In the PNW, OA enhancements are closely linked to intensified wildfire emissions, which raise OA mass concentrations to be 4–8 times higher relative to non-fire conditions. All 10 Earth system models participating in the sixth phase of the Coupled Model Intercomparison Project (CMIP6) can capture the slopes between SPEI and OA in the PNW, with CESM2-WACCM and GFDL-ESM4 performing the best and worst in predicting the OA enhancement under severe droughts. However, all models significantly underestimate the OA increase in the SEUS, with Nor-ESM2-LM and MIRCO6 showing relatively better performance. This study reveals the key drivers of the elevated OA levels under droughts in the CONUS and underscores the deficiencies of current climate models in their predictive capacity for assessing the impact of future droughts on air quality.