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At least 73 records · Page 4

Responses of gaseous sulfuric acid and particulate sulfate to reduced SO 2 concentration: A perspective from long-term measurements in Beijing

SO 2 concentration decreased rapidly in recent years in China due to the implementation of strict control policies by the government. Particulate sulfate ( p S O 4 2 - ) and gaseous H 2 SO 4 (SA) are two major products of SO 2 and they play important roles in the haze formation and new particle formation (NPF), respectively. We examined the change in p S O 4 2 - and SA concentrations in response to reduced SO 2 concentration using long-term measurement data in Beijing. Simulations from the Community Multiscale Air Quality model with a 2-D Volatility Basis Set (CMAQ/2D-VBS) were used for comparison. From 2013 to 2018, SO 2 concentration in Beijing decreased by ~81% (from 9.1 ppb to 1.7 ppb). p S O 4 2 - concentration in submicrometer particles decreased by ~60% from 2012–2013 (monthly average of ~10 μg·m - 3 ) to 2018–2019 (monthly average of ~4 μg·m - 3 ). Accordingly, the fraction of p S O 4 2 - in these particles decreased from 20–30% to <10%. Increased sulfur oxidation ratio was observed both in the measurements and the CMAQ/2D-VBS simulations. Despite the reduction in SO 2 concentration, there was no obvious decrease in SA concentration based on data from several measuring periods from 2008 to 2019. This was supported by the increased SA:SO 2 ratio with reduced SO 2 concentration and condensation sink. NPF frequency in Beijing between 2004 and 2019 remains relatively constant. Finally, this constant NPF frequency is consistent with the relatively stable SA concentration in Beijing, while different from some other cities where NPF frequency was reported to decrease with decreased SO 2 concentrations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anthropogenic extremely low volatility organics (ELVOCs) Govern the Growth of Molecular Clusters over the Southern Great Plains during the Springtime

New particle formation (NPF) and growth govern cloud condensation nuclei (CCN) concentrations in many regions. The mechanisms governing the nucleation of molecular clusters vary substantially in different regions of the atmosphere. Additionally, the growth of these clusters from ~2 to 20 nm sizes is often governed by the availability of extremely low volatility organic vapours (ELVOCs). While the pathways to ELVOC formation from the oxidation of biogenic monoterpenes with ozone is better understood, the chemical and mechanistic pathways for ELVOC formation from oxidation of anthropogenic organics are not well understood. We integrate measurements and three-dimensional regional model simulations with the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to understand the processes governing new particle formation and growth and secondary organic aerosol (SOA) formation during the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems (HI-SCALE) field campaign at the Southern Great Plains (SGP) observatory in Oklahoma, and contrast it with a site within the Bankhead National Forest (BNF), Alabama in Southeast USA, where 5-year long measurements will begin in 2024. Simulations show that nucleation rates are at least an order of magnitude higher at SGP compared to BNF during the springtime days (April 28 and May 14, 2016), largely due to lower H2SO4 concentrations at BNF, which are needed for nucleation. In addition, the larger CS at BNF (compared to SGP) increase the loss of molecular clusters by coagulation to pre-existing particles. Among the 8 different nucleation mechanisms in WRF-Chem, we find that the amine+H2SO4 nucleation mechanism dominates at the SGP site, while the pure organic ion induced nucleation mechanism dominates over BNF. Through various WRF-Chem sensitivity simulations, we find that anthropogenic ELVOCs are critical for explaining the growth of newly formed particles and the resulting number size distribution observed near the surface at the SGP site during the daytime. In addition, we show that treating organic particles as semisolid, with strong diffusion-limited uptake of organic vapours, brings model predictions into closer agreement with the observed evolution of particle size distribution. Simulations also predict that anthropogenic SOA, formed by the oxidation of aromatic volatile organic compounds (VOCs), is the dominant organic aerosol component at SGP, while biogenic SOA dominates particle composition at the BNF site in Southeast USA on these days.

Shrivastava, ManishKumar B.↗

Size-resolved Eddy-Covariance Particle Flux Measurement during the TRACER Campaign (Final Report)

The main goal of the TRacking Aerosol Convection interactions ExpeRiment (TRACER) campaign was to study aerosol–cloud interactions during deep convection over the Houston area. This project deployed a suite of instrumentation with the aim to (1) quantify turbulent vertical particle fluxes during at DOE-ARM sites, including TRACER, (2) assess hygroscopic growth factors and hygroscopicity parameters of the material driving modal aerosol growth during new particle formation and growth events, (3) derive turbulent aerosol mass fluxes using co-located Doppler LIDAR measurements, and (4) create quality-controlled PI data products to support future research utilizing data collected during the TRACER campaign. This report summarized the main findings from the deployments at two DOE-ARM sites. Briefly, we found that new particle formation may occur aloft, in a residual layer, near the top of the boundary layer. Small grown particles appear later due to downward mixing with daytime turbulence. The species that are responsible for aerosol modal growth had hygroscopicity parameters varying between 0.05 and 0.34. These values systematically depended on the wind sector, suggesting that the chemical composition of the precursors differed. This work demonstrated that lidar retrievals of the elastic backscatter and Doppler velocity can be used to obtain surface number emissions of particles with a diameter greater than 0.53 µm. During TRACER, emission particle number fluxes peaked near ∼ 100 cm−2 s−1. Multiple quality-controlled PI data products that will support future TRACER related science were generated and made publically available.

54 ENVIRONMENTAL SCIENCES↗

Cloud response to co-condensation of water and organic vapors over the boreal forest

Abstract. Accounting for the condensation of organic vapors along with water vapor (co-condensation) has been shown in adiabatic cloud parcel model (CPM) simulations to enhance the number of aerosol particles that activate to form cloud droplets. The boreal forest is an important source of biogenic organic vapors, but the role of these vapors in co-condensation has not been systematically investigated. In this work, the environmental conditions under which strong co-condensation-driven cloud droplet number enhancements would be expected over the boreal biome are identified. Recent measurement technology, specifically the Filter Inlet for Gases and AEROsols (FIGAERO) coupled to an iodide-adduct chemical ionization mass spectrometer (I-CIMS), is utilized to construct volatility distributions of the boreal atmospheric organics. Then, a suite of CPM simulations initialized with a comprehensive set of concurrent aerosol observations collected in the boreal forest of Finland during spring 2014 is performed. The degree to which co-condensation impacts droplet formation in the model is shown to be dependent on the initialization of temperature, relative humidity, updraft velocity, aerosol size distribution, organic vapor concentration, and the volatility distribution. The predicted median enhancements in cloud droplet number concentration (CDNC) due to accounting for the co-condensation of water and organics fall on average between 16 % and 22 %. This corresponds to activating particles 10–16 nm smaller in dry diameter that would otherwise remain as interstitial aerosol. The highest CDNC enhancements (ΔCDNC) are predicted in the presence of a nascent ultrafine aerosol mode with a geometric mean diameter of ∼ 40 nm and no clear Hoppel minimum, indicative of pristine environments with a source of ultrafine particles (e.g., via new particle formation processes). Such aerosol size distributions are observed 30 %–40 % of the time in the studied boreal forest environment in spring and fall when new particle formation frequency is the highest. To evaluate the frequencies with which such distributions are experienced by an Earth system model over the whole boreal biome, 5 years of UK Earth System Model (UKESM1) simulations are further used. The frequencies are substantially lower than those observed at the boreal forest measurement site (< 6 % of the time), and the positive values, peaking in spring, are modeled only over Fennoscandia and the western parts of Siberia. Overall, the similarities in the size distributions between observed and modeled (UKESM1) are limited, which would limit the ability of this model, or any model with a similar aerosol representation, to project the climate relevance of co-condensation over the boreal forest. For the critical aerosol size distribution regime, ΔCDNC is shown to be sensitive to the concentrations of semi-volatile and some intermediate-volatility organic compounds (SVOCs and IVOCs), especially when the overall particle surface area is low. The magnitudes of ΔCDNC remain less affected by the more volatile vapors such as formic acid and extremely low- and low-volatility organic compounds (ELVOCs and LVOCs). The reasons for this are that most volatile organic vapors condense inefficiently due to their high volatility below the cloud base, and the concentrations of LVOCs and ELVOCs are too low to gain significant concentrations of soluble mass to reduce the critical supersaturations enough for droplet activation to occur. A reduction in the critical supersaturation caused by organic condensation emerges as the main driver of the modeled ΔCDNC. The results highlight the potential significance of co-condensation in pristine boreal environments close to sources of fresh ultrafine particles. For accurate predictions of co-condensation effects on CDNC, also in larger-scale models, an accurate representation of the aerosol size distribution is critical. Further studies targeted at finding observational evidence and constraints for co-condensation in the field are encouraged.

54 ENVIRONMENTAL SCIENCES↗

Comparisons Between the Formation of Polar Stratospheric Clouds and Cirrus Clouds

Analyses of lidar data taken during the 1989 AASE I program show that polar stratospheric clouds most often contain frozen particles, but sometimes contain spherical, presumably liquid, particles. In this paper the mechanisms that lead to the freezing of particles, and to the formation of liquid particles will be discussed based largely upon analyses of existing data. For example, trajectory studies help shed light on the conditions that lead to particle freezing. During April of 1996 an experiment using the NASA DC-8 and ER-2 aircraft will be conducted over the central U.S. Some of the goals of the project are to better understand the mechanisms of cirrus cloud formation, and to investigate the properties of freezing nuclei in the upper troposphere. Results from this field program will be presented as they apply to the topic of ice crystal nucleation. Comparisons will be drawn between the mechanisms that lead to new particle formation in the polar stratosphere, and the mechanisms that lead to new particles formation in the upper troposphere.

Toon, Owen B.↗

Seasonal variations in composition and sources of atmospheric ultrafine particles in urban Beijing based on near-continuous measurements

Abstract. Understanding the composition and sources of atmospheric ultrafine particles (UFPs) is essential in evaluating their exposure risks. It requires long-term measurements with high time resolution, which are scarce to date. We performed near-continuous measurements of UFP composition during four seasons in urban Beijing using a thermal desorption chemical ionization mass spectrometer, accompanied by real-time size distribution measurements. We found that UFPs in urban Beijing are dominated by organic components, varying seasonally from 68 % to 81 %. CHO organics (i.e., molecules containing carbon, hydrogen, and oxygen) are the most abundant in summer, while sulfur-containing organics, some nitrogen-containing organics, nitrate, and chloride are the most abundant in winter. With the increase of particle diameter, the contribution of CHO organics decreases, while that of sulfur-containing and nitrogen-containing organics, nitrate, and chloride increases. Source apportionment analysis of the UFP organics indicates contributions from cooking and vehicle sources, photooxidation sources enriched in CHO organics, and aqueous/heterogeneous sources enriched in nitrogen- and sulfur-containing organics. The increased contributions of cooking, vehicle, and photooxidation components are usually accompanied by simultaneous increases in UFP number concentrations related to cooking emission, vehicle emission, and new particle formation, respectively, while the increased contribution of the aqueous/heterogeneous composition is usually accompanied by the growth of UFP mode diameters. The highest UFP number concentrations in winter are due to the strongest new particle formation, the strongest local primary particle number emissions, and the slowest condensational growth of UFPs to larger sizes. This study provides a comprehensive understanding of urban UFP composition and sources and offers valuable datasets for the evaluation of UFP exposure risks.

54 ENVIRONMENTAL SCIENCES↗

Spectro-Microscopic Analysis of Soot Particle Composition and Source Attribution

Ambient soot particles significantly impact Earth’s radiative balance, human health, and atmospheric visibility. Their microstructural properties depend on formation and aging mechanisms, which vary by emission source and atmospheric processes. Hence, accurately identifying sources of soot enhances our understanding of their physicochemical properties and atmospheric implications. This study used a multi-modal approach to characterize and attribute sources of submicron soot particles collected in Israel during new particle formation events, biomass burning episodes, and background atmospheric conditions. Synchrotron-based X-ray microscopy was used to map soot (elemental carbon), organic carbon, and inorganic species. Implemented atomic force microscopy showed highly diverse phase states, with soot consistently exhibiting a solid-like phase. Automated µ-Raman analysis was subsequently performed on ~690 particles, identifying three soot classes based on spectral features corresponding to the "Defect" (D) and "Graphite" (G) bands of soot. We applied two-peak and five-peak fitting approaches to deconvolute the “Defect” peaks (D1, D2, D3, and D4) and G band from average Raman, revealing varying degrees of graphitic order. The degree of graphitic order was determined from metrics such as the D3 peak area, often observed when soot was internally mixed with organic material. Raman spectral features, along with temporal variations in particle classes contributions, suggest that Particle Type 1 corresponds to traffic related soot and Particle Type 2 to less graphitic soot from biomass burning, while Particle Type 3 is associated with more heterogeneous particulate representative of soot-OC mixtures emitted during new particle formation and biomass burning episodes.

Rivera-Adorno, Felipe (ORCID:0000000273557999)↗

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)↗

Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO 2 ) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer

Dimethyl sulfide (DMS) is the major sulfur species emitted from the ocean. The gas-phase oxidation of DMS by hydroxyl radicals proceeds through the stable, soluble intermediate hydroperoxymethyl thioformate (HPMTF), eventually forming carbonyl sulfide (OCS) and sulfur dioxide (SO 2 ). Recent work has shown that HPMTF is efficiently lost to marine boundary layer (MBL) clouds, thus arresting OCS and SO 2 production and their contributions to new-particle formation and growth events. To date, no long-term field studies exist to assess the extent to which frequent cloud processing impacts the fate of HPMTF. Here, we present 6 weeks of measurements of the cloud fraction and the marine sulfur species methanethiol, DMS, and HPMTF made at the Atmospheric Radiation Measurement (ARM) research facility on Graciosa Island, Azores, Portugal. Using an observationally constrained chemical box model, we determine that cloud loss is the dominant sink of HPMTF in this region of the MBL during the study, accounting for 79 %–91 % of HPMTF loss on average. When accounting for HPMTF uptake to clouds, we calculate campaign average reductions in DMS-derived MBL SO 2 and OCS of 52 %–60 % and 80 %–92 % for the study period. Using yearly measurements of the site- and satellite-measured 3D cloud fraction and DMS climatology, we infer that HPMTF cloud loss is the dominant sink of HPMTF in the eastern North Atlantic during all seasons and occurs on timescales faster than what is prescribed in global chemical transport models. Accurately resolving this rapid loss of HPMTF to clouds has important implications for constraining drivers of MBL new-particle formation.

54 ENVIRONMENTAL SCIENCES↗

Examining the vertical heterogeneity of aerosols over the Southern Great Plains

Abstract. Atmospheric aerosols affect the global energy budget by scattering and absorbing sunlight (direct effects) and by changing the microphysical structure, lifetime, and coverage of clouds (indirect effects). Both aerosol direct and indirect effects are affected by the vertical distribution of aerosols in the atmosphere, which is further influenced by a range of processes, such as aerosol dynamics, long-range transport, and entrainment. However, many observations of these processes are based on ground measurements, limiting our ability to understand the vertical distribution of aerosols and simulate their impact on clouds and climate. In this work, we examined the vertical heterogeneity of aerosols over the Atmospheric Radiation Measurement (ARM) Southern Great Plains (SGP) using data collected from the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems (HI-SCALE) campaign. The vertical profiles of meteorological and aerosol physiochemical properties up to 2500 m above are examined based on the 38 flights conducted during the HI-SCALE campaign. The aerosol properties over the SGP show strong vertical heterogeneity and seasonal variabilities. The aerosol concentrations at the surface are the highest due to strong emissions at ground level. In general, the mode diameter of aerosols during summer (∼ 100 nm) is larger than that during spring (∼ 30 nm), a result of enhanced condensational growth due to enriched volatile organic compounds in summer. The concentration of aerosols below 30 nm in the boundary layer (BL) (e.g., below 1000 m) during spring is higher than that during summer, a result of the stronger new particle formation (NPF) events due to the reduced condensation sink in spring. In the BL, the size of the aerosols gradually increases with altitude due to condensational growth and cloud processing. However, the chemical composition of the aerosols remained similar, with organics and sulfates representing 59.8 ± 2.2 % and 22.7 ± 2.1 %, respectively, of the total mass in the BL. Through the vertical profiles of aerosol properties, we observed NPF events in the upper BL during 7 out of 38 research flights, where the newly formed particles continue to grow as they are mixed down to the surface. There is also an indication that deep convection brings aerosols from the free troposphere (FT) to the surface, where they grow to contribute to the cloud condensation nuclei (CCN). Overall, the vertical heterogeneity of aerosols over the SGP is influenced by aerosol dynamics (new particle formation, growth, and cloud processing) and transport processes (mixing in the BL, long-range transport, entrainment, and convective downward transport). Case studies showing the influence of these factors are discussed.

54 ENVIRONMENTAL SCIENCES↗

Aircraft-derived particle fluxes distinguish entrainment zone and decoupled layer nucleation in marine boundary layers

The vertical distribution of freshly nucleated aerosol particles in the marine boundary layer remains poorly constrained, limiting our ability to represent new particle formation in climate models. Here we characterize 3–10 nm particle events, termed small particle events (SPEs), by deriving their vertical turbulent fluxes from aircraft measurements during the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) campaign. To overcome stationarity limitations of traditional eddy covariance methods, we applied continuous wavelet transform analysis to data collected during June–July 2017 and January–February 2018 flights over the Azores. Our flux-based analysis revealed two distinct SPE scenarios with different vertical structures and spatial extents. The first featured nucleation in the entrainment zone, where free tropospheric air entrains into the boundary layer. The second showed nucleation in the decoupled layer, a stratified region between the well-mixed surface layer and cloud-topped upper boundary layer. In both cases, convergence of air masses from different layers diluted preexisting aerosol surface area to very low levels, creating conditions favorable for nucleation and generating strong downward particle fluxes. SPEs occurred in 15 % of flights, challenging prevailing theoretical expectations that new particle formation should rarely occur in marine boundary layers due to high condensation and coagulation sink capacity of sea spray aerosols. Aircraft-derived particle fluxes provide first observational constraints on the vertical location and source strength of likely nucleation regions in the remote marine boundary layer, improving aerosol source representations in climate models and reducing uncertainties in aerosol-cloud interactions.

Rasheeda Satheesh, Ajmal [North Carolina State Uni↗

Using aircraft measurements to characterize subgrid-scale variability of aerosol properties near the Atmospheric Radiation Measurement Southern Great Plains site

Abstract. Complex distributions of aerosol properties evolve in space and time as a function of emissions, new particle formation, coagulation, condensational growth, chemical transformation, phase changes, turbulent mixing and transport, removal processes, and ambient meteorological conditions. The ability of chemical transport models to represent the multi-scale processes affecting the life cycle of aerosols depends on their spatial resolution since aerosol properties are assumed to be constant within a grid cell. Subgrid-scale-dependent processes that affect aerosol populations could have a significant impact on the formation of particles, their growth to cloud condensation nuclei (CCN) sizes, aerosol–cloud interactions, dry deposition and rainout and hence their burdens, lifetimes, and radiative forcing. To address this issue, we characterize subgrid-scale variability in terms of measured aerosol number, size, composition, hygroscopicity, and CCN concentrations made by repeated aircraft flight paths over the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site during the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystem (HI-SCALE) campaign. Subgrid variability is quantified in terms of both normalized frequency distributions and percentage difference percentiles using grid spacings of 3, 9, 27, and 81 km that represent those typically used by cloud-system-resolving models as well as the current and next-generation climate models. Even though the SGP site is a rural location, surprisingly large horizontal gradients in aerosol properties were frequently observed. For example, 90 % of the 3, 9, and 27 km cell mean organic matter concentrations differed from the 81 km cell around the SGP site by as much as ∼ 46 %, large spatial variability in aerosol number concentrations and size distributions were found during new particle formation events, and consequently 90 % of the 3, 9, and 27 km cell mean CCN number concentrations differed from the 81 km cell mean by as much as ∼ 38 %. The spatial variability varied seasonally for some aerosol properties, with some having larger spatial variability during the spring and others having larger variability during the late summer. While measurements at a single surface site cannot reflect the surrounding variability of aerosol properties at a given time, aircraft measurements that are averaged within an 81 km cell were found to be similar to many, but not all, aerosol properties measured at the ground SGP site. This analysis suggests that it is reasonable to directly compare most ground SGP site aerosol measurements with coarse global climate model predictions. In addition, the variability quantified by the aircraft can be used as an uncertainty range when comparing the surface point measurements with model predictions that use coarse grid spacings.

54 ENVIRONMENTAL SCIENCES↗

Intense formation of secondary ultrafine particles from Amazonian vegetation fires and their invigoration of deep clouds and precipitation

New particle formation (NPF) in fire smoke is thought to be unlikely due to large condensation and coagulation sinks that scavenge molecular clusters. We analyze aircraft measurements over the Amazon and find that fires significantly enhance NPF and ultrafine particle (UFP < 50 nm diameter) numbers compared to background conditions, contrary to previous understanding. We identify that the nucleation of dimethylamine with sulfuric acid, which is aided by the formation of extremely low volatility organics in biomass-burning smoke, can overcome the large condensation and coagulation sinks and explain aircraft observations. We show that freshly formed clusters rapidly grow to UFP sizes through biomass-burning secondary organic aerosol formation, leading to a 10-fold increase in UFP number concentrations. Here, we find a contrasting effect of UFPs on deep convective clouds compared to the larger particles from primary emissions for the case investigated here. UFPs intensify the deep convective clouds and precipitation due to increased condensational heating, while larger particles delay and reduce precipitation.

54 ENVIRONMENTAL SCIENCES↗

Aerosol nucleation in the winter Arctic and Antarctic stratospheres

The formation rate of sulfuric-acid-water aerosol particles is calculated as a function of altitude for the conditions of the winter Arctic and Antarctic stratospheres. The theoretical results indicate that sulfate particle formation can occur in the polar winter stratosphere. Conditions for new particle formation are increasingly favorable as the altitude increases between 20 and 30 km because of the decrease in surface area of preexisting particles and increasing sulfuric-acid vapor supply. The theoretical predictions are consistent with observations of a high-altitude CN layer over Antarctica in the spring. Available vapor-pressure data indicate that ternary particles composed of sulfuric acid, nitric acid, and water are not thermodynamically stable under winter stratospheric conditions.

Hamill, Patrick↗