Dropsonde observations during the Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment.

The Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE) field campaign provides accurate data for aerosol characterization and trace gas profiles, and establishes knowledge of the relationships between aerosols and water. The dropsonde dataset provides an in situ characterization of the vertical thermodynamic structure of the atmosphere during 165 research flights by NASA Langley's King Air research aircraft between February 2020 and June 2022 and four test flights between December 2019 and November 2021. The research flights covered the western North Atlantic region, off the coast of the Eastern United States and around Bermuda and covered all seasons. The dropsonde profiles provide observations of temperature, pressure, relative humidity, and horizontal and vertical winds between the surface and about 9 km. 801 dropsondes were released, of which 796 were processed and 788 provide complete profiles of all parameters between the flight level and the surface with normal parachute performance. Here, we describe the dataset, the processing of the measurements, general statistics, and applications of this rich dataset.

Multi-campaign ship and aircraft observations of marine cloud condensation nuclei and droplet concentrations.

In-situ marine cloud droplet number concentrations (CDNCs), cloud condensation nuclei (CCN), and CCN proxies, based on particle sizes and optical properties, are accumulated from seven field campaigns: ACTIVATE; NAAMES; CAMP2EX; ORACLES; SOCRATES; MARCUS; and CAPRICORN2. Each campaign involves aircraft measurements, ship-based measurements, or both. Measurements collected over the North and Central Atlantic, Indo-Pacific, and Southern Oceans, represent a range of clean to polluted conditions in various climate regimes. With the extensive range of environmental conditions sampled, this data collection is ideal for testing satellite remote detection methods of CDNC and CCN in marine environments. Remote measurement methods are vital to expanding the available data in these difficult-to-reach regions of the Earth and improving our understanding of aerosol-cloud interactions. The data collection includes particle composition and continental tracers to identify potential contributing CCN sources. Several of these campaigns include High Spectral Resolution Lidar (HSRL) and polarimetric imaging measurements and retrievals that will be the basis for the next generation of space-based remote sensors and, thus, can be utilized as satellite surrogates.

Beyond the Ångström Exponent: Probing Additional Information in Spectral Curvature and Variability of In Situ Aerosol Hyperspectral (0.3-0.7 µm) Optical Properties.

Ångström exponents (α) allow reconstruction of aerosol optical spectra over a broad range of wavelengths from measurements at two or more wavelengths. Hyperspectral measurements of atmospheric aerosols provide opportunities to probe measured spectra for information inaccessible from only a few wavelengths. Four sets of hyperspectral in situ aerosol optical coefficients (aerosol-phase total extinction, σ ext, and absorption, σ abs; liquid-phase soluble absorption from methanol, σ MeOH-abs, and water, σ DI-abs, extracts) were measured from biomass burning aerosols (BBAs). Hyperspectral single scattering albedo (ω), calculated from σ ext and σ abs, provide spectral resolution over a wide spectral range rare for this optical parameter. Observed spectral shifts between σ abs and σ MeOH-abs/σ DI-abs argue in favor of measuring σ abs rather than reconstructing it from liquid extracts. Logarithmically transformed spectra exhibited curvature better fit by second-order polynomials than linear α. Mapping second order fit coefficients (a 1, a 2) revealed samples from a given fire tended to cluster together, that is, aerosol spectra from a given fire were similar to each other and somewhat distinct from others. Separation in (a 1, a 2) space for spectra with the same α suggest additional information in second-order parameterization absent from the linear fit. Spectral features found in the fit residuals indicate more information in the measured spectra than captured by the fits. Above-detection σ MeOH-abs at 0.7 µm suggests assuming all absorption at long visible wavelengths is BC to partition absorption between BC and brown carbon (BrC) overestimates BC and underestimates BrC across the spectral range. Hyperspectral measurements may eventually discriminate BBA among fires in different ecosystems under variable conditions.

Particulate Oxalate-To-Sulfate Ratio as an Aqueous Processing Marker: Similarity Across Field Campaigns and Limitations.

Leveraging aerosol data from multiple airborne and surface-based field campaigns encompassing diverse environmental conditions, we calculate statistics of the oxalate-sulfate mass ratio (median: 0.0217; 95% confidence interval: 0.0154-0.0296; R = 0.76; N = 2,948). Ground-based measurements of the oxalate-sulfate ratio fall within our 95% confidence interval, suggesting the range is robust within the mixed layer for the submicrometer particle size range. We demonstrate that dust and biomass burning emissions can separately bias this ratio toward higher values by at least one order of magnitude. In the absence of these confounding factors, the 95% confidence interval of the ratio may be used to estimate the relative extent of aqueous processing by comparing inferred oxalate concentrations between air masses, with the assumption that sulfate primarily originates from aqueous processing.

Coupling an online ion conductivity measurement with the particle-into-liquid sampler: Evaluation and modeling using laboratory and field aerosol data.

A particle-into-liquid sampler (PILS) was coupled to a flow-through conductivity cell to provide a continuous, nondestructive, online measurement in support of offline ion chromatography analysis. The conductivity measurement provides a rapid assessment of the total ion concentration augmenting slower batch-sample data from offline analysis and is developed primarily to assist airborne measurements, where fast time-response is essential. A conductivity model was developed for measured ions and excellent closure was derived for laboratory-generated aerosols (97% conductivity explained, R2 > 0.99). The PILS-conductivity measurement was extensively tested throughout the NASA Cloud, Aerosol and Monsoon Processes: Philippines Experiment (CAMP2Ex) during nineteen research flights. A diverse range of ambient aerosol was sampled from biomass burning, fresh and aged urban pollution, and marine sources. Ambient aerosol did not exhibit the same degree of closure as the laboratory aerosol, with measured ions only accountable for 43% of the conductivity. The remaining fraction of the conductivity was examined in combination with ion charge balance and found to provide additional supporting information for diagnosing and modeling particle acidity. An urban plume case study was used to demonstrate the utility of the measurement for supplementing compositional data and augmenting the temporal capability of the PILS.

Investigation of factors controlling PM2.5 variability across the South Korean Peninsula during KORUS-AQ.

The Korea - United States Air Quality Study (May - June 2016) deployed instrumented aircraft and ground-based measurements to elucidate causes of poor air quality related to high ozone and aerosol concentrations in South Korea. This work synthesizes data pertaining to aerosols (specifically, particulate matter with aerodynamic diameters <2.5 micrometers, PM2.5) and conditions leading to violations of South Korean air quality standards (24-hr mean PM2.5 < 35 µg m-3). PM2.5 variability from AirKorea monitors across South Korea is evaluated. Detailed data from the Seoul vicinity are used to interpret factors that contribute to elevated PM2.5. The interplay between meteorology and surface aerosols, contrasting synoptic-scale behavior vs. local influences, is presented. Transboundary transport from upwind sources, vertical mixing and containment of aerosols, and local production of secondary aerosols are discussed. Two meteorological periods are probed for drivers of elevated PM2.5. Clear, dry conditions, with limited transport (Stagnant period), promoted photochemical production of secondary organic aerosol from locally emitted precursors. Cloudy humid conditions fostered rapid heterogeneous secondary inorganic aerosol production from local and transported emissions (Transport/Haze period), likely driven by a positive feedback mechanism where water uptake by aerosols increased gas-to-particle partitioning that increased water uptake. Further, clouds reduced solar insolation, suppressing mixing, exacerbating PM2.5 accumulation in a shallow boundary layer. The combination of factors contributing to enhanced PM2.5 is challenging to model, complicating quantification of contributions to PM2.5 from local versus upwind precursors and production. We recommend co-locating additional continuous measurements at a few AirKorea sites across South Korea to help resolve this and other outstanding questions: carbon monoxide/carbon dioxide (transboundary transport tracer), boundary layer height (surface PM2.5 mixing depth), and aerosol composition with aerosol liquid water (meteorologically-dependent secondary production). These data would aid future research to refine emissions targets to further improve South Korean PM2.5 air quality.

Substantial Seasonal Contribution of Observed Biogenic Sulfate Particles to Cloud Condensation Nuclei.

Biogenic sources contribute to cloud condensation nuclei (CCN) in the clean marine atmosphere, but few measurements exist to constrain climate model simulations of their importance. The chemical composition of individual atmospheric aerosol particles showed two types of sulfate-containing particles in clean marine air masses in addition to mass-based Estimated Salt particles. Both types of sulfate particles lack combustion tracers and correlate, for some conditions, to atmospheric or seawater dimethyl sulfide (DMS) concentrations, which means their source was largely biogenic. The first type is identified as New Sulfate because their large sulfate mass fraction (63% sulfate) and association with entrainment conditions means they could have formed by nucleation in the free troposphere. The second type is Added Sulfate particles (38% sulfate), because they are preexisting particles onto which additional sulfate condensed. New Sulfate particles accounted for 31% (7 cm-3) and 33% (36 cm-3) CCN at 0.1% supersaturation in late-autumn and late-spring, respectively, whereas sea spray provided 55% (13 cm-3) in late-autumn but only 4% (4 cm-3) in late-spring. Our results show a clear seasonal difference in the marine CCN budget, which illustrates how important phytoplankton-produced DMS emissions are for CCN in the North Atlantic.

Take-off engine particle emission indices for in-service aircraft at Los Angeles International Airport.

We present ground-based, advected aircraft engine emissions from flights taking off at Los Angeles International Airport. 275 discrete engine take-off plumes were observed on 18 and 25 May 2014 at a distance of 400 m downwind of the runway. CO2 measurements are used to convert the aerosol data into plume-average emissions indices that are suitable for modelling aircraft emissions. Total and non-volatile particle number EIs are of order 1016-1017 kg-1 and 1014-1016 kg-1, respectively. Black-carbon-equivalent particle mass EIs vary between 175-941 mg kg-1 (except for the GE GEnx engines at 46 mg kg-1). Aircraft tail numbers recorded for each take-off event are used to incorporate aircraft- and engine-specific parameters into the data set. Data acquisition and processing follow standard methods for quality assurance. A unique aspect of the data set is the mapping of aerosol concentration time series to integrated plume EIs, aircraft and engine specifications, and manufacturer-reported engine emissions certifications. The integrated data enable future studies seeking to understand and model aircraft emissions and their impact on air quality.

Biofuel blending reduces particle emissions from aircraft engines at cruise conditions.

Aviation-related aerosol emissions contribute to the formation of contrail cirrus clouds that can alter upper tropospheric radiation and water budgets, and therefore climate. The magnitude of air-traffic-related aerosol-cloud interactions and the ways in which these interactions might change in the future remain uncertain. Modelling studies of the present and future effects of aviation on climate require detailed information about the number of aerosol particles emitted per kilogram of fuel burned and the microphysical properties of those aerosols that are relevant for cloud formation. However, previous observational data at cruise altitudes are sparse for engines burning conventional fuels, and no data have previously been reported for biofuel use in-flight. Here we report observations from research aircraft that sampled the exhaust of engines onboard a NASA DC-8 aircraft as they burned conventional Jet A fuel and a 50:50 (by volume) blend of Jet A fuel and a biofuel derived from Camelina oil. We show that, compared to using conventional fuels, biofuel blending reduces particle number and mass emissions immediately behind the aircraft by 50 to 70 per cent. Our observations quantify the impact of biofuel blending on aerosol emissions at cruise conditions and provide key microphysical parameters, which will be useful to assess the potential of biofuel use in aviation as a viable strategy to mitigate climate change.

Observational assessment of the role of nocturnal residual-layer chemistry in determining daytime surface particulate nitrate concentrations.

This study discusses an analysis of combined airborne and ground observations of particulate nitrate (NO3 - (p)) concentrations made during the wintertime DISCOVER-AQ study at one of the most polluted cities in the United States, Fresno, CA in the San Joaquin Valley (SJV) and focuses on development of understanding of the various processes that impact surface nitrate concentrations during pollution events. The results provide an explicit case-study illustration of how nighttime chemistry can influence daytime surface-level NO3 - (p) concentrations, complementing previous studies in the SJV. The observations exemplify the critical role that nocturnal chemical production of NO3 - (p) aloft in the residual layer (RL) can play in determining daytime surface-level NO3 - (p) concentrations. Further, they indicate that nocturnal production of NO3 - (p) in the RL, along with daytime photochemical production, can contribute substantially to the build-up and sustaining of severe pollution episodes. The exceptionally shallow nocturnal boundary layer heights characteristic of wintertime pollution events in the SJV intensifies the importance of nocturnal production aloft in the residual layer to daytime surface concentrations. The observations also demonstrate that dynamics within the RL can influence the early-morning vertical distribution of NO3 - (p), despite low wintertime wind speeds. This overnight reshaping of the vertical distribution above the city plays an important role in determining the net impact of nocturnal chemical production on local and regional surface-level NO3 - (p) concentrations. Entrainment of clean free tropospheric air into the boundary layer in the afternoon is identified as an important process that reduces surface-level NO3 - (p) and limits build-up during pollution episodes. The influence of dry deposition of HNO3 gas to the surface on daytime particulate nitrate concentrations is important but limited by an excess of ammonia in the region, which leads to only a small fraction of nitrate existing in the gas-phase even during the warmer daytime. However, in late afternoon, when diminishing solar heating leads to a rapid fall in the mixed boundary layer height, the impact of surface deposition is temporarily enhanced and can lead to a substantial decline in surface-level particulate nitrate concentrations; this enhanced deposition is quickly arrested by a decrease in surface temperature, which drops the gas-phase fraction to near zero. The overall importance of enhanced late afternoon gas-phase loss to the multiday build-up of pollution events is limited by the very shallow nocturnal boundary layer. The case study here demonstrates that mixing down of NO3 - (p) from the RL can contribute a majority of the surface-level NO3 - (p) in the morning (here, ~80%), and a strong influence can persist into the afternoon even when photochemical production is maximum. The particular day-to-day contribution of aloft nocturnal NO3 - (p) production to surface concentrations will depend on prevailing chemical and meteorological conditions. Although specific to the SJV, the observations and conceptual framework further developed here provide general insights into the evolution of pollution episodes in wintertime environments.

Surface dimming by the 2013 Rim Fire simulated by a sectional aerosol model.

The Rim Fire of 2013, the third largest area burned by fire recorded in California history, is simulated by a climate model coupled with a size-resolved aerosol model. Modeled aerosol mass, number, and particle size distribution are within variability of data obtained from multiple-airborne in situ measurements. Simulations suggest that Rim Fire smoke may block 4-6% of sunlight energy reaching the surface, with a dimming efficiency around 120-150 W m-2 per unit aerosol optical depth in the midvisible at 13:00-15:00 local time. Underestimation of simulated smoke single scattering albedo at midvisible by 0.04 suggests that the model overestimates either the particle size or the absorption due to black carbon. This study shows that exceptional events like the 2013 Rim Fire can be simulated by a climate model with 1° resolution with overall good skill, although that resolution is still not sufficient to resolve the smoke peak near the source region.

Airborne measurements of organosulfates over the continental U.S.

Organosulfates are important secondary organic aerosol (SOA) components and good tracers for aerosol heterogeneous reactions. However, the knowledge of their spatial distribution, formation conditions, and environmental impact is limited. In this study, we report two organosulfates, an isoprene-derived isoprene epoxydiols (IEPOX) (2,3-epoxy-2-methyl-1,4-butanediol) sulfate and a glycolic acid (GA) sulfate, measured using the NOAA Particle Analysis Laser Mass Spectrometer (PALMS) on board the NASA DC8 aircraft over the continental U.S. during the Deep Convective Clouds and Chemistry Experiment (DC3) and the Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS). During these campaigns, IEPOX sulfate was estimated to account for 1.4% of submicron aerosol mass (or 2.2% of organic aerosol mass) on average near the ground in the southeast U.S., with lower concentrations in the western U.S. (0.2-0.4%) and at high altitudes (<0.2%). Compared to IEPOX sulfate, GA sulfate was more uniformly distributed, accounting for about 0.5% aerosol mass on average, and may be more abundant globally. A number of other organosulfates were detected; none were as abundant as these two. Ambient measurements confirmed that IEPOX sulfate is formed from isoprene oxidation and is a tracer for isoprene SOA formation. The organic precursors of GA sulfate may include glycolic acid and likely have both biogenic and anthropogenic sources. Higher aerosol acidity as measured by PALMS and relative humidity tend to promote IEPOX sulfate formation, and aerosol acidity largely drives in situ GA sulfate formation at high altitudes. This study suggests that the formation of aerosol organosulfates depends not only on the appropriate organic precursors but also on emissions of anthropogenic sulfur dioxide (SO2), which contributes to aerosol acidity. KEY POINTS: IEPOX sulfate is an isoprene SOA tracer at acidic and low NO conditions Glycolic acid sulfate may be more abundant than IEPOX sulfate globally SO2 impacts IEPOX sulfate by increasing aerosol acidity and water uptake.

Microbiome of the upper troposphere: species composition and prevalence, effects of tropical storms, and atmospheric implications.

The composition and prevalence of microorganisms in the middle-to-upper troposphere (8-15 km altitude) and their role in aerosol-cloud-precipitation interactions represent important, unresolved questions for biological and atmospheric science. In particular, airborne microorganisms above the oceans remain essentially uncharacterized, as most work to date is restricted to samples taken near the Earth's surface. Here we report on the microbiome of low- and high-altitude air masses sampled onboard the National Aeronautics and Space Administration DC-8 platform during the 2010 Genesis and Rapid Intensification Processes campaign in the Caribbean Sea. The samples were collected in cloudy and cloud-free air masses before, during, and after two major tropical hurricanes, Earl and Karl. Quantitative PCR and microscopy revealed that viable bacterial cells represented on average around 20% of the total particles in the 0.25- to 1-µm diameter range and were at least an order of magnitude more abundant than fungal cells, suggesting that bacteria represent an important and underestimated fraction of micrometer-sized atmospheric aerosols. The samples from the two hurricanes were characterized by significantly different bacterial communities, revealing that hurricanes aerosolize a large amount of new cells. Nonetheless, 17 bacterial taxa, including taxa that are known to use C1-C4 carbon compounds present in the atmosphere, were found in all samples, indicating that these organisms possess traits that allow survival in the troposphere. The findings presented here suggest that the microbiome is a dynamic and underappreciated aspect of the upper troposphere with potentially important impacts on the hydrological cycle, clouds, and climate.

Identification of lubrication oil in the particulate matter emissions from engine exhaust of in-service commercial aircraft.

Lubrication oil was identified in the organic particulate matter (PM) emissions of engine exhaust plumes from in-service commercial aircraft at Chicago Midway Airport (MDW) and O'Hare International Airport (ORD). This is the first field study focused on aircraft lubrication oil emissions, and all of the observed plumes described in this work were due to near-idle engine operations. The identification was carried out with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF AMS) via a collaborative laboratory and field investigation. A characteristic mass marker of lubrication oil, I(85)/I(71), the ratio of ion fragment intensity between m/z = 85 and 71, was used to distinguish lubrication oil from jet engine combustion products. This AMS marker was based on ion fragmentation patterns measured using electron impact ionization for two brands of widely used lubrication oil in a laboratory study. The AMS measurements of exhaust plumes from commercial aircraft in this airport field study reveal that lubrication oil is commonly present in organic PM emissions that are associated with emitted soot particles, unlike the purely oil droplets observed at the lubrication system vent. The characteristic oil marker, I(85)/I(71), was applied to quantitatively determine the contribution from lubrication oil in measured aircraft plumes, which ranges from 5% to 100%.