SEARCH · Engineering Papers

Results for “Aerosol Acidity”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 271 records · Page 15

All sources NASA NTRS DOE OSTI

NASA NTRS1981

The formation and growth of sulfate aerosols in the stratosphere

The critical compositions, critical radii, and nucleation rates of sulfuric acid droplets formed through homogeneous heteromolecular nucleation process in the stratosphere under a variety of ambient conditions are calculated. Results are plotted as a function of H2SO4 concentration and H2O concentration so that characteristics of sulfate aerosols can be quickly estimated whenever environmental conditions are known. The effect of the uncertainty in the saturated vapor pressure of H2SO4 on the estimated properties of sulfate aerosols is elucidated. Plottings are presented that illustrate the relative importance of new particle formation by homogeneous nucleation vs growth by heteromolecular condensation on pre-existing nuclei in the stratosphere. The effects of ambient conditions, such as the concentrations of H2SO4 and H2O, the average stratospheric particle radius, and the number concentration of pre-existing nuclei on the relative importance of these two competing processes are discussed.

Yue, G. K.↗

DOE OSTI2024

Photoinitiated Reactions of Molecules and Radicals in Molecular Beams

The UV photochemistry of organic molecules is a fundamental process that governs reactions in the atmosphere, synthetic chemistry, processing of organic aerosols, and biological damage in living tissues. In many organic molecules, the ensuing evolution involves pathways that are in competition, giving rise to different products, isomerization, coupling to other electronic states, and secondary reactive collisions. Because photodissociation is usually fast (picoseconds to microseconds), these processes are far from equilibrium and are controlled by kinetic competition and dynamical forces. The work accomplished was focused primarily on the photochemistry of alpha-keto carboxylic acids, a group of acids produced from natural sources, which are implicated in aerosol formation and biological processes. In the atmosphere, they are destroyed mainly by solar radiation. Studying their photochemistry has been surprisingly difficult because of the complexity of their excited electronic states, and the effect of collisions and secondary reactions. The second project investigated the lifetime of excited electronic states of pyrazine and picoline and had both experimental and theoretical aspects. The work focused on a model molecule, pyruvic acid (PA), because it was hypothesized that it should be a good source of the unstable carbene, methylhydroxycarbene (MHC). PA has an internal hydrogen bond that controls the evolution of its decomposition. The decomposition was studied following excitation to two of its lowest excited states reached by laser irradiation at 351 and 193 nm. The photodissociation dynamics in the absence and presence of collisions was monitored and compared. Understanding the UV photochemistry requires the use of complementary experimental approaches. Two methods were enlisted, which together generated a comprehensive and detailed set of results: (i) The time-sliced velocity map imaging (SVMI) instrument at USC was exploited to determine kinetic energy release of fragments, fast dissociation timescales, and internal state distributions of fragments for which Resonance Enhanced Multiphoton Ionization (REMPI) schemes exist; and (ii) The multiplexed photoionization mass spectrometer (MPIMS) setup developed at the Sandia Combustion Research Facility was used for product discovery, achieved by exploiting tunable narrowband VUV radiation at the Advanced Light Source (ALS), and to follow in real time their subsequent unimolecular and bimolecular reactions. The experimental conditions ranged from collisionless molecular beams to study nascent products to flow reactors of variable pressures to study subsequent bimolecular reactions of the products. The goals stated above were successfully accomplished. By exciting PA to its lowest excited state, MHC was identified as the only primary product and its isomerization to vinylalcohol and acetaldehyde was directly observed in real time. Moreover, we reported the first bimolecular reaction of MHC, which was with acetaldehyde, and identified its reaction product. This paves the way for the study of other reactions of this important carbene intermediate. When excitation was carried out at 193 nm, which imparted much higher energy to PA, many more products were directly observed in real time, some deriving from three-body dissociation. Quantitative branching ratios and secondary reactions of radical products were also determined and analyzed. The studies of pyrazine and picoline focused on the second excited state of these molecules and showed (via ionization studies) that their excited states were very short lived (<100 fs) because of efficient couplings to lower electronic states via vibronic coupling. Theoretical work on modeling the absorption spectrum and decay mechanisms of the excited states are in progress in collaboration with theoreticians.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2003

Water-soluble Organic Components in Aerosols Associated with Savanna Fires in Southern Africa: Identification, Evolution and Distribution

During the SAFARI 2000 field campaign, both smoke aerosols from savanna fires and haze aerosols in the boundary layer and in the free troposphere were collected from an aircraft in southern Africa. These aerosol samples were analyzed for their water-soluble chemical components, particularly the organic species. A novel technique, electrospray ionization-ion trap mass spectrometry, was used concurrently with an ion chromatography system to analyze for carbohydrate species. Seven carbohydrates, seven organic acids, five metallic elements, and three inorganic anions were identified and quantified. On the average, these 22 species comprised 36% and 27% of the total aerosol mass in haze and smoke aerosols, respectively. For the smoke aerosols, levoglucosan was the most abundant carbohydrate species, while gluconic acid was tentatively identified as the most abundant organic acid. The mass abundance and possible source of each class of identified species are discussed, along with their possible formation pathways. The combustion phase of a fire had an impact on the chemical composition of the emitted aerosols. Secondary formation of sulfate, nitrate, levoglucosan, and several organic acids occurred during the initial aging of smoke aerosols. It is likely that under certain conditions, some carbohydrate species in smoke aerosols, such as levoglucosan, were converted to organic acids during upward transport.

Gao, Song↗

NASA NTRSDate not supplied

Surface-Enhanced Raman Spectroscopy (SERS) for Venus Atmospheric Characterization and Trace Organics Identification

The chemical composition of Venus’ clouds has attracted considerable attention since the first atmospheric probes entered the planet in the early 1980s. We know from these early studies that cloud aerosols consist of micron and submicron droplets of sulfuric acid (~85%) and water (~15%), but outstanding questions still exist regarding their trace chemical composition, especially the identity of the unknown UV absorber(s) and the possible presence of organic material (Spacek & Benner, 2021). Veritas and DaVinci will launch at the end of the decade to advance our understanding of Venus’ surface and atmosphere, however these missions are not designed to sample and analyze cloud aerosols at trace levels. Raman spectroscopy is an ideal candidate for characterizing aerosols and has a track record in studies of Earth’s atmosphere. Raman provides broad chemical screening of organic and inorganic molecules within seconds, and Raman instrumentation can be miniaturized to meet the stringent size, weight, and power (SWaP) constraints of an atmospheric probe while retaining sensitivity and specificity that allow spectral fingerprinting of compounds and functional groups. Raman alone is insufficient to characterize trace constituents however, as limits of detection are typically in the 10s to 100s of ppm at best for planetary Raman spectrometers. Surface-Enhanced Raman Spectroscopy (SERS), a method that utilizes nanoscale materials interacting with a sample to enhance weak Raman signals by orders of magnitude when probed by a laser, has the potential to drastically improve the sensitivity of a Raman instrument while adding little-to-no SWaP nor complexity to a scientific payload. We aim to de-risk SERS technology for rapid infusion in future planetary science missions by developing custom SERS substrates tailored towards Venus atmospheric exploration. We have developed SERS substrates consisting of nanotextured silver films and tested them on potential Venus-relevant organic compounds, with preliminary results indicating sub-ppm sensitivity. Additionally, we have planned tests to investigate durability, longevity, and other key characteristics that impact SERS substrate performance to prepare SERS technology for flight.

Venus↗

NASA NTRS1988

Regional aerosol chemistry of the Amazon Basin during the dry season

The distribution and chemical composition of the atmospheric aerosol over the Amazon Basin forest were determined during the 1985 July-August dry season, using data on the aerosol chemical constituent concentration collected during the NASA Global Tropospheric Experiment Amazon Boundary Layer Experiment 2A mission. The results of the analyses suggest that there is a remarkable compositional and spatial homogeneity of the atmospheric aerosol on an extensive regional scale. Particulate organic carbon is the dominant component of the atmospheric aerosol, exhibiting an average concentration of about 740 nmol/cu m in the mixed layer and about 220 nmol/cu m in free tropospheric air. Oxalate and SO4(2-) exhibited the greatest enrichment in the mixed layer, while Cl(-) showed essentially no enrichment. The aerosol in the Amazonian atmosphere is essentially acid-base neutral, primarily as a result of incorporation of NH(+), which is presumably derived from NH3 released by the forest ecosystem.

Talbot, R. W.↗

NASA NTRS1993

Atmospheric nuclei in the Pacific midtroposphere: Their nature, concentration, and evolution

An extensive flight series was carried out during May-June 1990 in the remote North and South Pacific free tropospheric aboard the NASA DC-8. Condensation nuclei counters and optical particle counters provided information on aerosol particles with diameters between 0.003 and 7.0 micrometers. Vertical profiles revealed aerosol layers to be a common feature of the free troposphere. Regions with highest aerosol mass tended to have the highest concentrations of surface-derived nuclei but the lowest concentrations of total nuclei. Regions with lowest aerosol mass tended to have the highest concentrations of the smaller 'ultrafine' condensation nuclei with diameters below 0.02 mircometers. Horizontal transects totaling over 35,000 km at about 9 to 10-km altitude exhibited variability of approximately 3 orders of magnitude in both aerosol mass and number concentrations over spatial scales ranging from 1 to 1000 km. At these altitudes an approximate inverse relationship between ultrafine concentrations and the surface area of the larger aerosol was evident. Regions having lowest aerosol mass were characterized by aerosol thermal volatility, indicative of a predominately sulfuric acid composition, and by very high concentrations of ultrafine nuclei, indicative of recent homogeneous nucleation. These conditions were frequently observed but were conspicuously evident above cloud over the intertropical convergence zone. The clean, free troposphere appears to be a significant source region for new tropospheric nuclei. A simplified model of the lifetime, coagulation, and cycling of these nuclei suggests that they constitute a source of cloud condensation nuclei in the lower troposphere.

Clarke, Antony D.↗

NASA NTRS1997

Biospheric Effects of the Chicxulub Impact and Their Role in the Cretaceous/Tertiary Mass Extinction

A comprehensive analysis of volatiles in the Chicxulub impact strongly supports the hypothesis that impact-generated sulfate aerosols caused over a decade of global cooling, acid rain, and disruption of ocean circulation, which contributed to the mass extinction at the Cretaceous/Tertiary (K/T) boundary. The crater size, meteoritic content of the K/T boundary clay, and impact models indicate that the Chicxulub crater was formed by a short period comet or an asteroid impact that released 0.7-3.4 x 10(exp 31) ergs of energy. Impact models and experiments combined with estimates of volatiles in the projectile and target rocks predict that over 200 gigatons (Gt) each of SO2 and water vapor, and over 500 Gt of CO2, were globally distributed in the stratosphere by the impact.

Pope, Kevin O.↗

NASA NTRS1996

Three-D Simulation of the Origin of the Pollutant Ozone Maxima in the Great African Plume: New Meteorology, New Chemistry for TRACE-A

Burning in South Central Africa is primarily responsible for the vast buildup of ozone in the mid-Atlantic noticeable in the Belem, Brazil, ozonesondes, and also visible in analyses using the Total Ozone Mapping Spectrometer (TOMS). We report on full-scale chemistry simulations for the SAFARI/TRACE-A field period of September-October, 1992. These observational programs provided a wealth of comparison data, including spectacular depictions of the vertical structure of ozone and particulate pollution over Africa, South America, and the Equatorial Atlantic [Browell JGR, 1996, submitted] above and below the NASA DC-8 airplane path. These depictions provide strict tests on the ability of a 3-d simulation and its controlling input parameters, most notably the biomass burning emissions strength. We use meteorology from MM5 used as a synoptic assimilation model and our own GRACES Global Regional Air Chemistry Event Simulator. This report will focus on the unique meteorology of the Equatorial Atmosphere around the Gulf of Guinea during the TRACE-A period, which we describe as "the opening of the gate," "the Great African Plume," and the "African Recirculatory System." We expect to assess whether the ozone observed is primarily "transported African smog," the standard view, or whether "re-$NO_[x)$-ification" of the Central Atlantic troposphere (reduction of nitric acid to active nitrogen oxides in clouds or aerosol) may be required for "extended intercontinental ozone production." A status report on a second nitrogen problem, "lower-tropospheric missing NO(y)," in which we find a serious imbalance in the $NO_ {x }$ and $NO_{y}$ budgets when compared with similar atmospheric tracers, will be given. An elaboration of the concepts set off by quotation marks in this abstract will be given in the talk.

Chatfeild, Robert↗

NASA NTRS1976

Stratospheric aerosols and climatic change

Generated primarily by volcanic explosions, a layer of submicron silicate particles and particles made of concentrated sulfuric acids solution is present in the stratosphere. Flights through the stratosphere may be a future source of stratospheric aerosols, since the effluent from supersonic transports contains sulfurous gases (which will be converted to H2SO4) while the exhaust from Space Shuttles contains tiny aluminum oxide particles. Global heat balance calculations have shown that the stratospheric aerosols have made important contributions to some climatic changes. In the present paper, accurate radiative transfer calculations of the globally-averaged surface temperature (T) are carried out to estimate the sensitivity of the climate to changes in the number of stratospheric aerosols. The results obtained for a specified model atmosphere, including a vertical profile of the aerosols, indicate that the climate is unlikely to be affected by supersonic transports and Space Shuttles, during the next decades.

Baldwin, B.↗

DOE OSTI2022

Pan-Arctic seasonal cycles and long-term trends of aerosol properties from 10 observatories

Even though the Arctic is remote, aerosol properties observed there are strongly influenced by anthropogenic emissions from outside the Arctic. This is particularly true for the so-called Arctic haze season (January through April). In summer (June through September), when atmospheric transport patterns change, and precipitation is more frequent, local Arctic sources, i.e., natural sources of aerosols and precursors, play an important role. Over the last few decades, significant reductions in anthropogenic emissions have taken place. At the same time a large body of literature shows evidence that the Arctic is undergoing fundamental environmental changes due to climate forcing, leading to enhanced emissions by natural processes that may impact aerosol properties. In this study, we analyze 9 aerosol chemical species and 4 particle optical properties from 10 Arctic observatories (Alert, Kevo, Pallas, Summit, Thule, Tiksi, Barrow/Utgiavik, Villum, and Gruvebadet and Zeppelin Observatory – both at Ny-Ålesund Research Station) to understand changes in anthropogenic and natural aerosol contributions. Variables include equivalent black carbon, particulate sulfate, nitrate, ammonium, methanesulfonic acid, sodium, iron, calcium and potassium, as well as scattering and absorption coefficients, single scattering albedo and scattering Ångström exponent. First, annual cycles are investigated, which despite anthropogenic emission reductions still show the Arctic haze phenomenon. Second, long-term trends are studied using the Mann–Kendall Theil–Sen slope method. We find in total 41 significant trends over full station records, i.e., spanning more than a decade, compared to 26 significant decadal trends. The majority of significantly declining trends is from anthropogenic tracers and occurred during the haze period, driven by emission changes between 1990 and 2000. For the summer period, no uniform picture of trends has emerged. Twenty-six percent of trends, i.e., 19 out of 73, are significant, and of those 5 are positive and 14 are negative. Negative trends include not only anthropogenic tracers such as equivalent black carbon at Kevo, but also natural indicators such as methanesulfonic acid and non-sea-salt calcium at Alert. Positive trends are observed for sulfate at Gruvebadet. No clear evidence of a significant change in the natural aerosol contribution can be observed yet. However, testing the sensitivity of the Mann–Kendall Theil–Sen method, we find that monotonic changes of around 5 % yr –1 in an aerosol property are needed to detect a significant trend within one decade. This highlights that long-term efforts well beyond a decade are needed to capture smaller changes. It is particularly important to understand the ongoing natural changes in the Arctic, where interannual variability can be high, such as with forest fire emissions and their influence on the aerosol population. To investigate the climate-change-induced influence on the aerosol population and the resulting climate feedback, long-term observations of tracers more specific to natural sources are needed, as well as of particle microphysical properties such as size distributions, which can be used to identify changes in particle populations which are not well captured by mass-oriented methods such as bulk chemical composition.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Weak influence of anthropogenic emissions on aerosol, cloud, and rain in the wet season of the Amazon rainforest

Anthropogenic emissions have been shown to affect new particle formation, aerosol concentrations, and clouds. Such effects vary with region, environmental conditions, and cloud types. In the wet season of Amazonia, anthropogenic emissions emitted from Manaus, Brazil, can significantly increase the cloud condensation nuclei (CCN) concentrations compared to the background of mainly natural aerosols. However, the regional response of cloud and rain to anthropogenic emissions in Amazonia remains very uncertain. Here, we aim to quantify how aerosol concentration, cloud, and rain respond to changes in anthropogenic emissions through parameterized new particle formation and primary aerosol emission in the Manaus region and to understand the underlying mechanisms. We ran the atmosphere-only configuration of the HadGEM3 climate model with a nested regional domain that covers most of the rainforest region (720 km by 1200 km with 3 km resolution) under scaled regional emissions. The 7 d simulations show that, in the areas that are affected by anthropogenic emissions, when aerosol and precursor gas emissions are doubled from the baseline emission inventories, aerosol number concentrations increase by 13 %. The nucleation rate that involves sulfuric acid and biogenic compounds generally increases with pollution levels. However, nucleation is suppressed very close to the pollution source, resulting in lower nucleation and soluble Aitken mode aerosol number concentrations. We also found that doubling the anthropogenic emission can increase the cloud droplet number concentrations ( N d ) by 9 %, but cloud water and rain mass mixing ratios do not change significantly. Even very strong reductions in aerosol number concentrations by a factor of 4, which is an unrealistic condition, cause only a 4 % increase in rain over the domain. If we assume our simulation has a fine enough grid resolution and an accurate representation of the relevant atmospheric processes, the simulated weak and non-linear response of cloud and rain properties to linearly scaled anthropogenic emissions suggests that the interactions among aerosol, cloud, and precipitation in the Amazonian convective environment are buffered by microphysical processes. It also implies that the convective environment is resilient to the changes in Nd that occur in response to localized anthropogenic aerosol perturbations.

Wang, Xuemei [University of Leeds (United Kingdom)↗

NASA NTRS1983

Biological particle analysis by mass spectrometry

An instrument that analyzes the chemical composition of biological particles in aerosol or hydrosol form was developed. Efforts were directed toward the acquisition of mass spectra from aerosols of biomolecules and bacteria. The filament ion source was installed on the particle analysis by mass spectrometry system. Modifications of the vacuum system improved the sensitivity of the mass spectrometer. After the modifications were incorporated, detailed mass spectra of simple compounds from the three major classes of biomolecules, proteins, nucleic acids, and carbohydrates were obtained. A method of generating bacterial aerosols was developed. The aerosols generated were collected and examined in the scanning electron microscope to insure that the bacteria delivered to the mass spectrometer were intact and free from debris.

Vilker, V. L.↗

NASA NTRS1987

Spectral radiometry and tropospheric aerosols: Report of panel

The term aerosols, as used here, refers to the haze, smoke, and dust that appear in the troposphere. The term does not refer to the hydrometeors in cumulus and stratus clouds but does include the sulfuric acid-water droplets which are assumed to predominate in the stratospheric aerosol layer. The aerosol properties that were measured from satellites and those which can be made in the near term (up to 1992) will be reviewed. The capabilities that will exist in the years 1992 to 2000, with implementation of EOS, are then discussed. Finally, a few words will be said concerning the potential for aerosol measurements for the decade after 2000.

Fraser, Robert S.↗

NASA NTRS1991

Condensational growth and trace species scavenging in stratospheric sulfuric acid/water aerosol droplets

Stratospheric aerosols play a significant role in the environment. The composition of aerosols is believed to be a liquid solution of sulfuric acid and water with numerous trace species. Of these trace species, ozone in particular was recognized as being very important in its role of shielding the environment from harmful ultraviolet radiation. Also among the trace species are HCl and ClONO2, the so called chlorine reservoir species and various oxides of nitrogen. The quantity of stratospheric aerosol and its particle size distribution determines, to a large degree, the chemistry present in the stratosphere. Aerosols experience 3 types of growth: nucleation, condensation, and coagulation. The application of condensation investigations to the specific problem of stratospheric aerosols is discussed.

Tompson, Robert V., Jr.↗

DOE OSTI2025

Influence of Gel Formation on the Heterogeneous Oxidation of Organic Aerosol

Recent work has shown that divalent cations can perturb the viscosity and phase state of oxygenated organic particles in unexpected ways, sometimes leading to the formation of gel states. Despite the prevalence of divalent cations and oxygenated organic molecules in atmospheric aerosol, particularly in marine environments, the influence of gel states on the reaction rates is not well established. Here, in this work, we measure and compare the impact of viscosity and gel formation on the ozonolysis chemistry of aerosol particles containing the unsaturated, oxygenated organic species ascorbic acid (AA). AA serves as an excellent proxy compound for highly oxidized molecules in the atmosphere. We measured the hygroscopic growth, phase state, viscosity, and water diffusion rate in binary particles containing AA and water and in ternary particles with an additional co-solute of either ammonium sulfate or CaCl 2 . These measurements reveal gel formation in particles mixed with CaCl 2 , as particles become rigid but allow for relatively rapid diffusion rates of water, consistent with previous observations of gel behavior. We measured the rate of ozonolysis of these particles under a range of relative humidity (RH) conditions, showing a clear decrease in the rate with decreasing RH, consistent with the increase in viscosity and slowed diffusion. Notably, we measured the rate of ozonolysis of particles existing in a gel state, showing that following an initial period of decay, the rate of reaction arrests, indicating that the organic material in the solid state is protected from the reaction. This work shows that viscous particles and gel particles exhibit different reactivity toward heterogeneous oxidants, with significant implications for how we understand the chemical evolution of aerosol particles in the atmosphere.

gels↗

NASA NTRSDate not supplied

Lessons from Earth Aerobiology for Venus Astrobiology

Venus’s clouds have often suggested as a possible habitat. The constraints governing putative airborne life in such a habitat in turn inform priorities and strategies for remote and in situ exploration, methods by which resulting biosignatures might be detected, exoplanet habitability assessment, and planetary protection concerns. Lessons drawn from studying Earth’s aerobiosphere can help improve this understanding. There are altitude ranges within Venus’s clouds in which temperature, pressure, particle size, and radiation appear to be within the limits of microbial life on Earth, and life cycles involving S- and Fe-based redox metabolism have been proposed. However, given the lack of a habitable surface reservoir, a long-term stable Venus aerobiosphere would require that the reproduction rate of the airborne microbes be faster than the settling rate of airborne microbes due to gravity, or eventually the population would be depleted; put another way, the mean generation time would need to exceed the mean residence time. This creates a joint constraint of aerosol dynamics, potential nutrient availability and energy influx, and bioenergetic costs such as desiccation and radiation damage. Even at an optimistic estimate of 75% H2SO4, Venus aerosol water activity (aw) is still ~0.02, far below the observed microbial growth limit of ~0.6. Long-term desiccation with brief spurts of repair and growth in response to transient water influx, such as from volcanism, is the most likely model for Earth-like life on Venus – a ‘desert bloom’ scenario. Several high-priority science goals – cloud aerosol composition, internal radiative flux, and aerosol residence time and circulation models – thus will also improve our understanding of Venus in an astrobiology context. In Earth’s troposphere, warm water clouds can carry 103 – 105 cells/mL, some metabolically active. However, Earth’s stratospheric sulfate aerosol layer may be a better analogue: supercooled sulfuric acidaerosols (acid weight fraction 0.6 – 0.85, 0.1 – 1 μm diameter, 0.1 – 1 cm-3) with little water activity, long residence times, high UV radiation, and only sporadic influx from surface particle sources. Though ‘hot spots’ can occur associated with tropospheric mixing, viable cells in stratospheric samples are rare (~102 cells/m3), and primarily inactive forms such as spores. It is not yet clear whether such bioaerosols are associated with sulfate aerosols or simply co-located, and reproduction in situ has not yet been observed. In this model of a sparse, largely dormant Venus ecosystem, a single transect on descent is likely to pass through a low-water, inactive region, missing potential signs of habitability or biosignatures. A targeted strategy would sample through an aerial region with some upwelling from surface sources, andtake multiple transects separated in time and space. This is compatible with other in situ science goals seeking to understand the dynamics and heterogeneities of Venus’s clouds.

Lower atmosphere↗

NASA NTRS2006

Temporal Variation of Aerosol Properties at a Rural Continental Site and Study of Aerosol Evolution through Growth Law Analysis

Aerosol size distributions were measured by a Scanning Mobility Particle Sizer (SMPS) onboard the CIRPAS Twin Otter aircraft during 16 flights at the Southern Great Plains (SGP) site in northern central Oklahoma as part of the Aerosol Intensive Operation period in May, 2003. During the same period a second SMPS was deployed at a surface station and provided continuous measurements. Combined with trace gas measurements at the SGP site and back-trajectory analysis, the aerosol size distributions provided insights into the sources of aerosols observed at the SGP site. High particle concentrations, observed mostly during daytime, were well correlated with the sulfur dioxide (SO2) mixing ratios, suggesting nucleation involving sulfuric acid is likely the main source of newly formed particles at the SGP. Aerosols within plumes originating from wildfires in Central America were measured at the surface site. Vertically compact aerosol layers, which can be traced back to forest fires in East Asia, were intercepted at altitudes over 3000 meters. Analyses of size dependent particle growth rates for four periods during which high cloud coverage was observed indicate growth dominated by volume controlled reactions. Sulfate accounts for 50% to 72% of the increase in aerosol volume concentration; the rest of the volume concentration increase was likely due to secondary organic species. The growth law analyses and meteorological conditions indicate that the sulfate was produced mainly through aqueous oxidation of SO2 in clouds droplets and hydrated aerosol particles.

Wang, Jian↗

DOE OSTI2023

New formation and fate of Isoprene SOA markers revealed by field data-constrained modeling

Particulate 2-methyltetrols (2-MT) and 2-methylglyceric acid (2-MG) are typically used to indicate the abundance of isoprene-derived secondary organic aerosols (SOA). However, their formation and fate are not fully understood. In this study, we showed that particulate 2-MT and 2-MG collected at multiple monitoring sites under a wide range of atmospheric and emission conditions, with concentrations spanning six orders of magnitudes, are well reproduced with an expanded isoprene-SOA scheme implemented into the Community Multiscale Air Quality (CMAQ) model. The scheme considers their three-phase (gas-aqueous-organic phase) partitioning, formation from acid-driven multiphase reactions, and degradation by OH radicals in the gas and aqueous phases. The model results reveal that a non-aqueous formation pathway or direct biogenic emission is needed to supplement the commonly assumed acid-driven multiphase reaction process to explain the observed 2-MT concentrations. This missing pathway contributes to 20–40% of 2-MT in areas with aerosol pH < 2 and more than 70% under less acidic conditions (pH~2–5), such as those encountered in the western US and China. The typical summertime gas-phase photochemical lifetimes of 2-MT and 2-MG are estimated to be 4–6 and 20–30 h, respectively, and their aqueous lifetimes are approximately 20–40 h. Our simulations show that predicted 2-MT is mainly influenced by its aqueous phase loss to OH, but 2-MG is more sensitive to gas phase OH loss due to the preferential partitioning of the two tracers in the aqueous and gas phases, respectively.

54 ENVIRONMENTAL SCIENCES↗