Abstract As large wildfires become more frequent and severe in North America due to heightened fuel aridity and fire weather conditions driven by anthropogenic climate change, wildfire smoke has an increasingly important influence on air quality. Transported smoke can impact urban boundary layer ozone (O 3 ) directly, via the entrainment of O 3 formed in smoke, or indirectly, through the influence of pyrogenic volatile organic compounds (VOCs) and aerosols on local O 3 production. Widespread smoke impacts from the record‐breaking 2023 Canadian wildfire season coincided with the July–August 2023 Airborne Emissions and Reactions Observed from Megacities to Marine Areas (AEROMMA) aircraft‐based field campaign, which provided extensive in situ observations of urban chemistry in North American megacities. Vertically resolved trace gas and aerosol measurements from the August 2 AEROMMA research flight in Chicago indicated the entrainment of diffuse smoke from an aged, lofted wildfire plume into the urban boundary layer and were used to constrain a zero‐dimensional photochemical model and a radiative transfer model. We perturbed the models across a range of smoke densities and urban nitrogen oxide emissions and found net pyrogenic O 3 enhancements of 3–17 ppbv, with the largest contribution from transported smoke O 3 (65%–84%), followed by locally produced photochemical O 3 from smoke VOCs (18%–46%), and finally smoke aerosol shading (−12%–0%). Although these results are specific to the observed August 2 smoke plume and Chicago urban chemistry, the modeling framework presented could be applied to other smoke‐impacted locations to disentangle the various effects of wildfire smoke on urban O 3 .

The Asian Summer Monsoon (ASM) lofts air from polluted boundary layer regions to the upper-troposphere and lower-stratosphere. High concentrations of aerosols have been observed in ASM outflow, which influence climate by interacting with radiation and clouds and affecting atmospheric composition. Prior observations indicate that small particles form in ASM convective outflow. Laboratory and modelling studies hypothesise the importance of lofted ammonia in this process and growth of the particles to sizes where they can interact with radiation and clouds. Here we combine in-situ observation in ASM convective outflow with trajectory and Earth-system modelling to show the likely role of pollution in enhancing ASM outflow new particle formation. We show that the particles grow to sizes where they can interact with clouds and radiation, and are transported over large areas within the troposphere and stratosphere. New particle formation in Asian Summer Monsoon convective outflow is enhanced by lofted anthropogenic emissions. The particles formed grow to sizes where they can impact clouds and radiation and are transported in the troposphere and stratosphere.

Declining nitrogen oxide (NOx = NO + NO2) emissions have transformed oxidation pathways in urban atmospheres, with implications for air quality. Organic peroxy radicals (RO2), key intermediates in volatile organic compound oxidation, typically react with NO to form ozone (O3). Under lower-NO conditions, alternative RO2 fates, including isomerization forming highly oxidized organic molecules (HOMs), can enhance secondary organic aerosol (SOA) production. We combine aircraft observations over four major North American cities with geostationary satellite data to characterize isoprene-derived RO2 fate across urban environments. We infer RO2 bimolecular lifetimes (τbi) as a proxy for isomerization potential, finding longer τbi (17 ± 11 seconds) in New York, Chicago, and Toronto compared to Los Angeles (7 ± 6 seconds). Satellite measurements reveal that long τbi is widespread across urban North America, suggesting that declining NOx is likely to lead to greater HOM formation in urban regions. These findings indicate that atmospheric models omitting RO2 isomerization chemistry may incorrectly simulate organic oxidation and the subsequent oxidation state of volatile organic compounds and SOA.

Analysis of recent in situ data reveals a persistent mode of organic-rich aerosol particles in the stratosphere below 19 kilometers at nitrous oxide (N2O) > 270 parts per billion by volume, with a number geometric mean diameter of ~0.03 to 0.11 μm (0.08 to 0.2 μm in surface and 0.11 to 0.3 μm in volume). This mode, composed mostly of organic-rich particles transported from the troposphere, is poorly sensed by satellites and most balloon-borne optical measurements but dominates the surface area for heterogeneous reactions and the sink for condensable vapors. These small particles grow in size and decrease in concentration as they mix with older stratospheric air. A global chemistry-climate model fails to replicate the characteristics of these particles, suggesting that model improvements are necessary for accurate assessment of proposed geoengineering efforts.

Reactive halogens catalytically destroy O3 and therefore affect (1) stratospheric O3 depletion and (2) the oxidative capacity of the troposphere. Reactive halogens also partition into the aerosol phase, but what governs halogen-aerosol partitioning is poorly constrained in models. In this work, we present global-scale measurements of non-sea-salt aerosol (nSSA) bromine and iodine taken during the NASA Atmospheric Tomography Mission (ATom). Using the Particle Analysis by Laser Mass Spectrometry instrument, we found that bromine and iodine are present in 8 %–26 % (interquartile range, IQR) and 12 %–44 % (IQR) of accumulation-mode nSSA, respectively. Despite being commonly found in nSSA, the concentrations of bromine and iodine in nSSA were low but potentially important, at 0.11–0.57 pmol mol−1 (IQR) and 0.04–0.24 pmol mol−1 (IQR), respectively. In the troposphere, we find two distinct sources of bromine and iodine for nSSA: (1) a primary source from biomass burning and (2) a pervasive secondary source. In the stratosphere, nSSA bromine and iodine concentrations increased with increasing O3 concentrations; however, higher concentrations of stratospheric nSSA bromine and iodine were found in organic-rich particles that originated in the troposphere. Finally, we compared our ATom nSSA iodine measurements to the global chemical transport model GEOS-Chem (Goddard Earth Observing System); nSSA bromine concentrations could not be compared because they were not tracked in the model. We found that the model compared well to our ATom nSSA iodine measurements in the background atmosphere but not in the marine boundary layer, biomass burning plumes, or stratosphere.

Perchlorate is a toxic, regulated contaminant in drinking water. According to previous isotopic studies, much of the perchlorate deposited to the Earth's surface is formed in the atmosphere, with 36Cl suggesting a large contribution from the stratosphere. Here, we present measurements of perchlorate in stratospheric aerosol particles and confirm that the stratosphere is an important source of perchlorate, whereas we did not observe production in the troposphere. Mass mixing ratios of aerosol perchlorate in the stratosphere were 1 to 10 parts per trillion by mass (pptm), with the highest concentrations observed in summer and in the Southern Hemisphere. Almost all of the perchlorate is in biomass burning and nitrogen-rich particles, despite those types contributing only a few percent of the aerosol particles. Such particles are less acidic than the majority of sulfuric acid particles. If the formation of perchlorate is sensitive to acidity, then the injection of some materials for solar radiation modification might significantly increase the global production of perchlorate.

Stratospheric aerosol plays a significant role in the Earth's energy balance, primarily through its direct interaction with solar radiation. It is also an important chemical reactor that contributes to the multiphase chemistry of ozone destruction by halogen compounds. Sulfuric acid is the main chemical component of stratospheric aerosol, but the processes that control the composition and size of stratospheric particles remain uncertain. We report direct observations of the composition of individual particles of 0.12-1.2 mu m geometric diameter, sampled in situ in the high latitude lower stratosphere during February and March of 2023, at altitudes up to 19 km. Polar vortex air was frequently sampled, enabling an investigation into the nature of particles formed in air descending from the mesosphere and upper stratosphere. Over 90% of particles at the sampled sizes in very old polar vortex air contain metals from the ablation of meteors, suggesting that almost all sulfuric acid particles formed in such air grow onto meteoric smoke. Such particles contain extremely low levels of organic matter, typically less than about 0.3% by mass, and relatively high mass fractions of metals, around 5%-8%. These newly characterized "neat" meteoric-sulfuric particles gain additional sulfuric acid and organic compounds by coagulation with background stratospheric aerosol, forming "aged" meteoric-sulfuric particles, which are encountered throughout the stratosphere. On the basis of these observations, we estimate a meteoric iron flux into the Earth's atmosphere of about 0.3-1 Gg yr(-1).

The stratospheric aerosol layer plays an essential role in stratospheric chemical and radiative processes. Emissions of SO2 from small-to-midsized volcanic eruptions are typically introduced into the lower stratosphere, where a background aerosol already exists. The radiative and chemical consequences of these eruptive emissions depend in part upon the characteristics of these background particles, whose number originates from the troposphere. In-situ observations of sub-0.1 µm diameter particles in the upper troposphere/lower stratosphere are rare, but are of particular importance in understanding the contribution of upwelling ultrafine particles formed near the tropical tropopause and their subsequent evolution in the stratospheric (Brewer-Dobson) circulation. In the Stratospheric Aerosol processes, Budget and Radiative Effects (SABRE) mission from January to March 2023, we used three particle sizing instruments on the NASA WB-57 high-altitude aircraft to measure the size distribution of aerosol particles in the size range from 0.003 to ~4.0 μm in the lower stratosphere from middle to high latitudes at altitudes up to 19.6 km. The composition of individual aerosol particles >0.1 µm was also measured, along with O3, N2O, SF6 and OCS. Together, these measurements were used to investigate dynamical and chemical processes in the stratosphere that determine the evolution of the stratospheric aerosol as a function of stratospheric age up to several years. We observed a clear bimodal size distribution structure, with a small mode (< 0.1 μm diameter) originating from the troposphere and a larger mode (>0.2 µm diameter) originating from the photolysis of OCS (the classic Junge, or stratospheric, aerosol layer). These two modes evolve as a function of stratospheric age in a manner consistent with coagulation, condensation, and sedimentation. These are the first reported observations of the presence and evolution of this bimodal aerosol structure deep into the stratosphere. The small (tropospheric) particle mode provides a significant condensation sink at young stratospheric ages. SO2 from modest volcanic eruptions emitted into the lower stratosphere may condense on these smaller particles, reducing the amount of light scattering per unit mass. Proposed geoengineering efforts must also account for this tropospheric mode of particles. Models simulating aerosol processes in the stratosphere need to accurately represent tropospheric particles in the lower stratosphere and their evolution with stratospheric age.

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. The evolution of BrC absorption in the free troposphere is characterized as a function of hydroxyl radical (OH) exposure, yielding an effective photochemical rate constant of 9.7-1.6+4.8 × 10-12 cm3 molecule-1 s-1. The relatively slow reaction rate results in small BrC decay within the first few hours after emission, making it difficult to distinguish from source variability. This helps explain the absence of clear evolutionary trends in near-field studies. Assuming an OH concentration of 1.26 × 106 molecules cm-3, this rate constant corresponds to an e-folding lifetime of approximately 23 h. After extensive photooxidation (OH exposure ∼1012 molecules cm-3 s), 4 ± 2% of the emitted BrC persists, representing a recalcitrant fraction with potential long-term climate impacts. These results improve our understanding of BrC variability and photochemical processing and provide critical constraints for modeling its impacts on climate.

Aerosol optical depth (AOD) is a vital parameter in atmospheric research. Using observations of the Visible Infrared Imaging Radiometer Suite (VIIRS), onboard Suomi National Polar-orbiting Partnership (Suomi-NPP) and NOAA-20 satellites, National Oceanic and Atmospheric Administration (NOAA) produces near-real time AOD product with high pixel resolution (750 m), wide swath width (3,040 km), and a 16-day repeat cycle. Here we report the evaluation of the NOAA/VIIRS AOD using a comprehensive aerosol data set, derived from a global-scale, multi-seasonal airborne mission, the NASA Atmospheric Tomography Mission (ATom). This data set includes rich physical and chemical information, such as size distributions, chemical compositions, optical properties, and hygroscopicities of major aerosol types, including dust, sea salt, smoke, internally mixed sulfate/nitrate/organics particles (non-smoke), black carbon, etc. Globally, VIIRS AOD (Suomi-NPP and NOAA-20) shows good agreement with the ATom AOD in the moderate to high AOD range (>0.3), with respect to measurement uncertainties (orthogonal distance regression fitting slope: 1.5 +/- 0.2 for Suomi-NPP and 1.6 +/- 0.5 for NOAA-20; correlation coefficient: 0.85 for Suomi-NPP and 0.73 for NOAA-20). There is a persistent bias in the low AOD range (<0.3) on the order of 0.03, likely reflecting systematic errors on VIIRS and/or the ATom AOD product. & Aring;ngstr & ouml;m exponent reported by VIIRS shows excellent agreement with ATom results within expected uncertainties. Given the unique insights revealed by the ATom AOD and aerosol property data set, it is desirable to have ATom-like comprehensive payloads in future airborne satellite validation programs.

New particle formation in the free troposphere is a major source of cloud condensation nuclei globally. The prevailing view is that in the free troposphere, new particles are formed predominantly in convective cloud outflows. We present another mechanism using global observations. We find that during stratospheric air intrusion events, the mixing of descending ozone-rich stratospheric air with more moist free tropospheric background results in elevated hydroxyl radical (OH) concentrations. Such mixing is most prevalent near the tropopause where the sulfur dioxide (SO 2 ) mixing ratios are high. The combination of elevated SO 2 and OH levels leads to enhanced sulfuric acid concentrations, promoting particle formation. Such new particle formation occurs frequently and over large geographic regions, representing an important particle source in the midlatitude free troposphere.

Abstract. Reactive halogens catalytically destroy O3 and therefore affect (1) stratospheric O3 depletion, and (2) the oxidative capacity of the troposphere. Reactive halogens also partition into the aerosol phase, but what governs halogen-aerosol partitioning is poorly constrained in models. In this work, we present global-scale measurements of non-sea-salt aerosol (nSSA) bromine and iodine taken during the NASA Atmospheric Tomography Mission (ATom). Using the Particle Analysis by Laser Mass Spectrometry instrument, we found that bromine and iodine are present in 8–26 % (interquartile range, IQR) and 12–44 % (IQR) of accumulation-mode nSSA, respectively. Despite being commonly found in nSSA, the mass concentrations of bromine and iodine in nSSA were low, 0.11–0.57 pmol mol-1 (IQR) and 0.04–0.24 pmol mol-1 (IQR), respectively. In the troposphere, we find two distinct sources of bromine and iodine to nSSA: (1) a primary source from biomass burning, and (2) a pervasive secondary source. In the stratosphere, nSSA bromine and iodine mass increased with increasing O3 concentrations; however, higher concentrations of stratospheric nSSA bromine and iodine were found in organic-rich particles that originated in the troposphere. Finally, we compared our ATom nSSA iodine measurements to the global chemical transport model GEOS-Chem; nSSA bromine concentrations could not be compared because they were not tracked in the model. We found that the model compared well to our ATom nSSA iodine measurements in the background atmosphere, but not in the marine boundary layer, biomass burning plumes, or in the stratosphere.

AbstractBiogenic organic compounds in the surface ocean may significantly alter the cloud‐forming ability of sea spray aerosol and thereby affect the amount of solar radiation reaching the ocean surface. Estimates of the organic mass fraction of sea spray vary widely, and some results show a significant dependence on biological activity in the source seawater. We present airborne observations of the organic mass fraction of individual sea spray particles measured using the Particle Analysis by Laser Mass Spectrometry (PALMS) instrument during the Atmospheric Tomography (ATom) mission, which sampled a wide range of latitudes and altitudes over the remote Atlantic and Pacific Oceans across four seasons, from the marine boundary layer to the upper troposphere. The measured sea spray particles of about 0.15–0.7 μm dry diameter showed higher average organic mass fractions at smaller sizes, but values were low overall, with regional integrated submicron means almost always <10%. Atmospheric aging adds organics to sea spray particles, leading to higher mean organic mass fractions (sometimes exceeding 50%) in the free troposphere than in the marine boundary layer. The average submicron sea spray organic mass fractions are on the low end of previously reported values and show weak seasonal variability for most regions. These results imply that recent biological activity in the surface ocean has only weak control over how much organic matter is in nascent submicron sea spray particles over the remote oceans, in contrast to findings from some observational studies and global numerical simulations.

Diffusive condensation particle counters (CPCs) injecting the aerosol near the symmetry axis within a larger flow of a vapor-containing sheath gas have previously exhibited a size resolving power considerably lower than theoretically expected. We hypothesize that reexamining these in-struments with particles of improved uniformity in composition, size and shape should reveal a much better performance, well suited for high resolution particle sizing and basic heterogeneous nucleation studies. Accordingly, we investigate the performance of the Variable Supersaturation Condensation Particle Sizer (VSCPS) of Gallar et al. (2006) with an aerosol of uniform singly charged polyethylene glycol particles (3-9 nm diameter), produced by a bipolar electrospray, and size-selected by a differential mobility analyzer of high resolution. The condensation size res-olution obtained with n-butanol vapor almost triples that previously demonstrated for this instrument, exceeds that established for any other CPC, and can apparently be further increased. Flow and temperature field calculations of the maximal supersaturation in the VSCPS would enable basic heterogeneous nucleation studies, as well as high resolution sizing of neutral or charged particles.

Nucleation of ultrafine aerosols near the tropical tropopause, followed by transport throughout the stratosphere by the Brewer-Dobson circulation, is thought to be the primary source of stratospheric aerosol number concentration. However, depending on how rapidly the aerosols grow by condensation, many of the ultrafine particles generated by new particle formation (NPF) may be lost due to coagulation with accumulation-mode aerosols. In this study, we use recent high-altitude aircraft measurements of aerosol size distribution, along with microphysical calculations, to investigate this issue. Initial ultrafine and accumulation-mode size distributions are specified based on the aircraft measurements, and a bin microphysics model is used to simulate the evolution of the aerosol size distributions. Coagulation and condensation of gases such as sulfuric acid, ammonia, and nitric acid are included. Preliminary results indicate that for typical conditions, most of the ultrafine aerosols generated by NPF are removed by coagulation, resulting in a relatively small contribution to the total aerosol number concentration. We have used the model to investigate the sensitivities of total number concentration evolution to aerosol size distributions and condensation rates.

While formation and growth of particles in the troposphere have been extensively studied in the past two decades, very limited efforts have been devoted to understanding these in the stratosphere. Here we use both Cosmics Leaving OUtdoor Droplets (CLOUD) laboratory measurements taken under very low temperatures (205–223 K) and Atmospheric Tomography Mission (ATom) in situ observations of particle number size distributions (PNSDs) down to 3 nm to constrain nucleation mechanisms and to evaluate model-simulated particle size distributions in the lowermost stratosphere (LMS). We show that the binary homogenous nucleation (BHN) scheme used in most of the existing stratospheric aerosol injection (a proposed method of solar radiation modification) modeling studies overpredicts the nucleation rates by 3–4 orders of magnitude (when compared to CLOUD data) and particle number concentrations in the background LMS by a factor ∼ 2–4 (when compared to ATom data). Based on a recently developed kinetic nucleation model, which gives rates of both ion-mediated nucleation (IMN) and BHN at low temperatures in good agreement with CLOUD measurements, both BHN and IMN occur in the stratosphere. However, IMN rates are generally more than 1 order of magnitude higher than BHN rates and thus dominate nucleation in the background stratosphere. In the Southern Hemisphere (SH) LMS with minimum influence of anthropogenic emissions, our analysis shows that ATom-measured PNSDs generally have four apparent modes. The model captures reasonably well the two modes (Aitken mode and the first accumulation mode) with the highest number concentrations and size-dependent standard deviations. However, the model misses an apparent second accumulation mode peaking around 300–400 nm, which is in the size range important for aerosol direct radiative forcing. The bimodal structure of accumulation mode particles has also been observed in the stratosphere well above tropopause and in the volcano-perturbed stratosphere. We suggest that this bimodal structure may be caused by the effect of charges on coagulation and growth, which is not yet considered in any existing models and may be important in the stratosphere due to high ionization rates and the long lifetime of aerosols. Considering the importance of accurate PNSDs for projecting a realistic radiation forcing response to stratospheric aerosol injection (SAI), it is essential to understand and incorporate such potentially important processes in SAI model simulations and to carry out further research to find out what other processes the present models might have missed.

The Asian monsoon anticyclone transports aerosol and gas phase pollutants from the boundary layer to the upper troposphere and lower stratosphere, from whence they are transported out over the Western Pacific by eddy shedding. This significantly increases aerosol loading in the upper troposphere and maintains a layer of aerosol in the lowermost stratosphere with important implications for climate and stratospheric chemistry. Models show large spread in the spatial distribution and microphysical properties of aerosols transported by the Asian monsoon, and the chemical and radiative effects remain uncertain.In August 2022 we measured aerosol size distributions in Asian summer monsoon outflow from two aircraft, the NCAR GV and NASA WB57, as part of the Asian Summer Monsoon Chemical Climate Impacts Project (ACCLIP). On both aircraft we operated a Nucleation Mode Aerosol Size Spectrometer (NMASS, a custom battery of 5 condensation particle counters) and a modified Ultra-High Sensitivity Aerosol Spectrometer (an optical particle counter from Droplet Measurement Technologies) to measure size distributions from 3 to 1500 nm at 1 Hz time resolution.Here we use these data together with concurrently measured trace gases and reactive gases, and cloud properties, to quantify the transport of primary aerosol by the monsoon system, and the formation of secondary aerosol in the monsoon outflow. We show that new particle formation occurs in the upper troposphere in monsoon outflow and investigate its relation to lofting of condensable vapours and wet scavenging of larger aerosols by deep convection. We use data taken in the upper troposphere and lower stratosphere of the NASA Atmospheric Tomography Mission (ATom) to compare aerosol microphysical properties in the summer monsoon outflow with those in less anthropogenically influence air.

Aerosol forcing uncertainty represents the largest climate forcing uncertainty overall. Its magnitude has remained virtually undiminished over the past 20 years despite considerable advances in understanding most of the key contributing elements. Recent work has produced modest increases only in the confidence of the uncertainty estimate itself. This review summarizes the contributions toward reducing the uncertainty in the aerosol forcing of climate made by satellite observations, measurements taken within the atmosphere, as well as modeling and data assimilation. We adopt a more measurement‐oriented perspective than most reviews of the subject in assessing the strengths and limitations of each; gaps and possible ways to fill them are considered. Currently planned programs supporting advanced, global‐scale satellite and surface‐based aerosol, cloud, and precursor gas observations, climate modeling, and intensive field campaigns aimed at characterizing the underlying physical and chemical processes involved, are all essential. But in addition, new efforts are needed: (a) to obtain systematic aircraft in situ measurements capturing the multi‐variate probability distribution functions of particle optical, microphysical, and chemical properties (and associated uncertainty estimates), as well as co‐variability with meteorology, for the major aerosol airmass types; (b) to conceive, develop, and implement a suborbital (aircraft plus surface‐based) program aimed at systematically quantifying the cloud‐scale microphysics, cloud optical properties, and cloud‐related vertical velocities associated with aerosol‐cloud interactions; and (c) to focus much more research on integrating the unique contributions of satellite observations, suborbital measurements, and modeling, to reduce the persistent uncertainty in aerosol climate forcing.

Pyrocumulonimbus (pyroCb) are wildfire-generated convective clouds that can inject smoke directly into the stratosphere. PyroCb have been tracked for years, yet their apparent rarity and episodic nature lead to highly uncertain climate impacts. In situ measurements of pyroCb smoke reveal its distinctive and exceptionally stable aerosol properties and define the long-term influence of pyroCb activity on the stratospheric aerosol budget. Analysis of 13 years of airborne observations shows that pyroCb are responsible for 10 to 25% of the black carbon and organic aerosols in the "present-day" lower stratosphere, with similar impacts in both the North and South Hemispheres. These results suggest that, should pyroCb increase in frequency and/or magnitude in future climates, they could generate dominant trends in stratospheric aerosol.

Validation of remote sensing retrievals of aerosol microphysical and optical properties requires in situ measurements of the same properties. We present here an improved imaging nephelometer for measuring the directionality and polarization of light (i.e., polarimetry) scattered at two wavelengths (405 and 660 nm) with high temporal resolution. The instrument was designed for airborne deployment and is capable of ground-based measurements as well. The laser imaging nephelometer (LiNeph) uses two orthogonal detectors with wide-angle lenses and linearly polarized light sources to measure both the phase function, P11(θ), and degree of linear polarization, -P12/P11(θ). In this work, we will describe the instrument function and calibration, as well as data acquisition and reduction. The instrument was first deployed aboard the NASA DC-8 during the 2019 FIREX-AQ campaign. Here, we present field measurements of smoke plumes that show that the LiNeph has sufficient resolution for 0.24 Hz polarimetric measurements at two wavelengths, 405 and 660 nm, at integrated scattering coefficients ranging from 50–8000 Mm−1.