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Pressure and temperature dependence of the reaction NO2 + NO3 + M yields N2O5 + M

The pressure and temperature dependences of the reaction NO2 + NO3 + M which yields N2O5 + M are investigated by using the flash photolysis/visible absorption technique in which the pseudo-first-order decay of NO3 is monitored as a function of total pressure (20-700 torr), diluent gas (M = He and N2), and temperature (236-358 K). The reaction is found to be in the falloff region in the 20-700 torr pressure range with collision efficiencies increasing in the order He less than N2. Falloff parameters are obtained by fitting the experimental data to the falloff equation of Troe and co-workers. The expression for k1(N2 concentration, T) is obtained and compared with the evaluations presented in the NASA (DeMore, 1983) and CODATA (Baulch et al., 1982) reviews of kinetic data for atmospheric chemistry. Both evaluations are based on N2O5 thermal decomposition data coupled with estimates of the equilibrium constant. The significance of the reactions for atmospheric chemistry rests not only on their rates but on the extent to which they result in a permanent sink for NOX.

Kircher, C. C.↗

Atmospheric Research 2018 Technical Highlights

Atmospheric research in the Earth Sciences Division (610) consists of research and technology development programs dedicated to advancing knowledge and understanding of the atmosphere and its interaction with the climate of Earth. The Division’s goals are to improve understanding of the dynamics and physical properties of precipitation, clouds, and aerosols; atmospheric chemistry, including the role of natural and anthropogenic trace species on the ozone balance in the stratosphere and the troposphere; and radiative properties of Earth’s atmosphere and the influence of solar variability on the Earth’s climate. Major research activities are carried out in the Mesoscale Atmospheric Processes Laboratory, the Climate and Radiation Laboratory, the Atmospheric Chemistry and Dynamics Laboratory, and the Wallops Field Support Office. The overall scope of the research covers an end-to-end process, starting with the identification of scientific problems, leading to observation requirements for remote sensing platforms, technology and retrieval algorithm development; followed by flight projects and satellite missions; and eventually, resulting in data processing, analyses of measurements, and dissemination from flight projects and missions.

Highlights↗

Present State of Knowledge of the Upper Atmosphere 1996: An Assessment Report to Congress and the Environmental Protection Agency

This document is issued in response to the Clean Air Act Amendment of 1990, Public Law 101-549, which mandates that the National Aeronautics and Space Administration (NASA) and other key agencies submit triennial report to congress and the Environmental Protection Agency. NASA is charged with the responsibility to report on the state of our knowledge of the Earth's upper atmosphere, particularly the Stratosphere. Part 1 of this report summarizes the objectives, status, and accomplishments of the research tasks supported under NASA's Upper Atmosphere Research Program and Atmospheric Chemistry Modeling and Analysis Program for the period of 1994-1996. Part 2 (this document) presents summaries of several scientific assessments, reviews, and summaries. These include the executive summaries of two scientific assessments: (Section B) 'Scientific Assessment of Ozone Depletion: 1994'; (Section C) 'l995 Scientific Assessment of the Atmospheric Effects of Stratospheric Aircraft); end of mission/series statements for three stratospherically-focused measurement campaigns: (Section D) 'ATLAS End-of-Series Statement'; (Section E) 'ASHOE/MAESA End-of-Mission Statement'; (Section F) 'TOTE/VOTE End-of-Mission Statement'; a summary of NASA's latest biennial review of fundamental photochemical processes important to atmospheric chemistry 'Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling'; and (Section H) the section 'Atmospheric Ozone Research" from the Mission to Planet Earth Science Research Plan, which describes NASA's current and future research activities related to both tropospheric and stratospheric chemistry.

Kurylo, M. J.↗

TChem-atm v1.0

SAND2024-11300O TChem-atm is a software library that was developed to solve complex kinetic models for atmospheric chemistry applications. TChem-atm interface employs a hierarchical parallelism design to exploit the massive parallelism available from modern computing platforms. It also supports gas atmospheric chemistry applications, e.g., the energy exascale earth system model. TChem can be used as a box model or coupled with a climate model to compute the time evolution of gas tracer species. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Safta, Cosmin↗

Meteoric Material: An Important Component of Planetary Atmospheres

Interplanetary dust particles (IDPs) interact with all planetary atmospheres and leave their imprint as perturbations of the background atmospheric chemistry and structure. They lead to layers of metal ions that can become the dominant positively charged species in lower ionospheric regions. Theoretical models and radio occultation measurements provide compelling evidence that such layers exist in all planetary atmospheres. In addition IDP ablation products can affect neutral atmospheric chemistry, particularly at the outer planets where the IDPs supply oxygen compounds like water and carbon dioxide to the upper atmospheres. Aerosol or smoke particles from incomplete ablation or recondensation of ablated IDP vapors may also have a significant impact on atmospheric properties.

Grebowsky, Joseph M.↗

Trend Detection of Atmospheric Time Series: Incorporating Appropriate Uncertainty Estimates and Handling Extreme Events

This paper is aimed at atmospheric scientists without formal training in statistical theory. Its goal is to, 1) provide a critical review of the rationale for trend analysis of the time series typically encountered in the field of atmospheric chemistry; 2) describe a range of trend-detection methods; and 3) demonstrate effective means of conveying the results to a general audience. Trend detections in atmospheric chemical composition data are often challenged by a variety of sources of uncertainty, which often behave differently to other environmental phenomena such as temperature, precipitation rate, or stream flow, and may require specific methods depending on the science questions to be addressed. Some sources of uncertainty can be explicitly included in the model specification, such as autocorrelation and seasonality, but some inherent uncertainties are difficult to quantify, such as data heterogeneity and measurement uncertainty due to the combined effect of short- and long-term natural variability, instrumental stability, and aggregation of data from sparse sampling frequency. Failure to account for these uncertainties might result in an inappropriate inference of the trends and their estimation errors. On the other hand, the variation in extreme events might be interesting for different scientific questions, for example, the frequency of extremely high surface ozone events and their relevance to human health. In this study we aim to, 1) review trend detection methods for addressing different levels of data complexity in different chemical species; 2) demonstrate that the incorporation of scientifically interpretable covariates can outperform pure numerical curve fitting techniques in terms of uncertainty reduction and improved predictability; 3) illustrate the study of trends based on extreme quantiles that can provide insight beyond standard mean or median based trend estimates; and 4) present an advanced method of quantifying regional trends based on the inter-site correlations of multi-site data. All demonstrations are based on time series of observed trace gases relevant to atmospheric chemistry, but the methods can be applied to other environmental data sets.

Trace gas↗

Variability in Modelled Airborne Dust Mineralogy Derived from Global Soil Composition Uncertainties

Dust aerosols consist on a variety of minerals with different physic and chemical properties. As such, they interact with short and long wave radiation, potentially form clouds, act as nutrients modulating biogeochemical cycles, or influence atmospheric chemistry, differently. Most current state-of-the-art Earth System Models (ESMs) neglect the complexity in dust composition, mainly due to computational constraints, but also to the existing uncertainties in the size resolved composition of parent soils, the resulting distribution of minerals in airborne dust, and the scarcity of observations to constrain them. Within this work, we assess the variability of global dust composition due to uncertainties in the characterization of the parent soil mineralogy. To that end, we consider two available global soil mineralogy atlases, developed by Claquin et al. (1999) –C1999- and Journet et al. (2014) –J2014-, which represent respectively 8 and 12 relevant minerals for climate (namely: illite, smectite/montmorillonite, kaolinite, calcite, gypsum, hematite, quartz, and feldspars in C1999, and those plus chlorite, vermiculite, goethite, and mica in J2014). Thanks to a recently developed feature of the MONARCH atmospheric-chemistry model, we are able to explicitly resolve the minerals’ atmospheric cycle. Therefore, we define two global experiments to assess changes on airborne dust composition attributed to the soil mineralogy assumptions and provide a measure of their variability. We also perform a preliminary evaluation of the global mineralogy results against available observations of mineral fractions in surface dust concentration. Our results will inform the climate modelling community about the potential variability in dust composition, an aspect that will gain relevance as ESMs continue growing in complexity and new processes to better characterize aerosols’ forcing or biogeochemical cycles are added. Further observational constraints, such as those that will derive from the EMIT NASA mission on soil composition or the FRAGMENT experimental campaigns on airborne dust characterization, will be key in the near future to improve our understanding of the impact of dust mineralogy on fundamental climate features.

Dust aerosols↗

Laboratory Studies of Atmospheric Heterogeneous Chemistry

In the laboratory, ice films formed by freezing from the liquid or more frequently by deposition from the vapor phase have been used to simulate stratospheric cloud surfaces for measurements of reaction and uptake rates. To obtain intrinsic surface reaction probabilities that can be used in atmospheric models, the area of the film surface that actually takes part in the reaction must be known. It is important to know not only the total surface area but also the film morphology in order to determine where and how the surface is situated and, thus, what fraction of it is available for reaction. Information on the structure of these ice films has been obtained by using several experimental methods. In the sections that follow, these methods will be discussed, then the results will be used to construct a working model of the ice films, and finally the model will be applied to an experimental study of HC1 uptake by H_2O ice.

Keyser, L. F.↗

Identification of the acetaldehyde oxide Criegee intermediate reaction network in the ozone-assisted low-temperature oxidation of trans -2-butene

Uni- and bi-molecular reactions involving Criegee intermediates (CIs) have been the focus of many studies due to the role these molecules play in atmospheric chemistry. The reactivity of CIs is known to strongly depend on their structure. The reaction network of the second simplest CI, acetaldehyde oxide (CH 3 CHOO), is investigated in this work in an atmospheric pressure jet-stirred reactor (JSR) during the ozonolysis of trans-2-butene to explore the kinetic pathways relevant to atmospheric chemistry and low-temperature combustion. The mole fraction profiles of reactants, intermediates, and final products are determined by means of molecular-beam mass spectrometry in conjunction with single-photon ionization employing tunable synchrotron-generated vacuum ultraviolet radiation. A network of CI reactions is identified in the temperature region below 600 K, characterized by CI addition to trans-2-butene, water, formaldehyde, formic acid, and methanol. No sequential additions of the CH 3 CHOO CI are observed, in contrast with the reactivity of the simplest CI (H 2 COO) and the earlier observation of an extensive reaction network with up to four H 2 COO sequential additions (Phys. Chem. Chem. Phys., 2019, 21, 7341–7357). Experimental photoionization efficiency scans recorded at 300 K and 425 K and ab initio threshold energy calculations lead to the identification and quantification of previously elusive intermediates, such as ketohydroperoxide and hydroperoxide species. Specifically, the C 4 H 8 + O 3 adduct is identified as a ketohydroperoxide (KHP, 3-hydroperoxybutan-2-one, CH 3 C([double bond, length as m-dash]O)CH(CH 3 )OOH), while hydroxyacetaldehyde (glycolaldehyde, HCOCH 2 OH) formation is attributed to unimolecular isomerization of the CIs. Other hydroperoxide species such as methyl hydroperoxide (CH 3 OOH), ethyl hydroperoxide (C 2 H 5 OOH), butyl hydroperoxide (OOH), hydroperoxyl acetaldehyde (HOOCH 2 CHO), hydroxyethyl hydroperoxide (CH 3 CH(OH)OOH), but-1-enyl-3-hydroperoxide, and 4-hydroxy-3-methylpentan-2-one (HOCH(CH 3 )CH(CH 3 )C([double bond, length as m-dash]O)CH 3 ) are also identified. Detection of additional oxygenated species such as methanol, ethanol, ketene, and aldehydes suggests multiple active oxidation routes. Finally, these results provide additional evidence that CIs are key intermediates of the ozone-unsaturated hydrocarbon reactions providing critical inputs for improved kinetics models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compendium of NASA data base for the Global Tropospheric Experiment's Pacific Exploratory Mission West-A (PEM West-A)

This compendium describes aircraft data that are available from NASA's Pacific Exploratory Mission West-A (PEM West-A). PEM West is a component of the International Global Atmospheric Chemistry's (IGAC) East Asia/North Pacific Regional Study (APARE) project. The PEM- West program encompassed two expeditions to study contrasting meteorological regimes in the Pacific. Objectives of PEM West are to investigate the atmospheric chemistry of ozone over the northwest Pacific -- natural budgets and the impact of anthropogenic sources; and to investigate sulfur chemistry -- continental versus marine sulfur sources. PEM West-A was conducted in September 1991 during which the predominance of tropospheric air is from the mid-Pacific (marine) regions, but (at times) is modified/mixed with Asian continental outflow. PEM West-B was conducted during February 1994, a period characterized by maximum continental outflow. PEM-B data (not included) will become public domain during the Summer of 1995. PEM West-A flight experiments were based at Japan, Hong Kong, and Guam. This document provides a representation of NASA DC-8 aircraft data that are available from NASA Langley's Distributed Active Archive Center (DAAC), which include numerous data such as meteorological observations, modeling products, results from surface studies, satellite observations, and sonde releases.

Gregory, G. L.↗

A Comprehensive Chemistry Evaluation and Diagnostics Package for E3SM – ChemDyg Version 1.1.0

The Chemistry Evaluation and Diagnostics Package (ChemDyg) is an open-source tool designed for the Energy Exascale Earth System Model (E3SM) developed by the U.S. Department of Energy. ChemDyg facilitates routine evaluation, tailored development, and in-depth analysis of atmospheric chemistry through its modular architecture, allowing users to compare model outputs with observational data. Version 1.1.0 introduces a robust set of diagnostic capabilities, including climatology, time evolution of key tracers, diurnal and annual cycle analyses, and extensive budget diagnostics. These features help identify model discrepancies and enhance the representation of atmospheric chemistry in E3SM. Each self-contained diagnostic set includes dedicated scripts and documentation for ease of use. The interactive HTML output improves data accessibility, accelerating chemistry model development. Additionally, ChemDyg's flexible framework allows for customization, enabling users to create unique diagnostic sets for specific scientific contributions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The EOS-Aura Mission

The EOS-Aura atmospheric chemistry mission is scheduled for launch in June 2004. Aura is the third of the large EOS observatories. The spacecraft carries an international instrument payload that has a planned six year lifetime. The Aura mission will collect data to help answer stratospheric and tropospheric atmospheric chemistry questions. The mission has the following four major objectives: 1) Track the ozone layer to determine if it is recovering as predicted. The four Aura instruments, HIRDLS, OMI, MLS, and TES will measure ozone, key source, radical, reservoir, tracer gases, and aerosols. Aura's unique design allows for major ozone controlling gases to be measured within the same air mass within a few minutes. The OMI instrument will continue the trends fiom NASA's TOMS series. 2) Track tropospheric pollutant sources and measure tropospheric ozone precursors. Major pollution sources include urban, industrial and biomass burning regions. Tropospheric trace gases will be measured, using TES and OMI, at an average spatial resolution of about approximately 15 km with near global coverage. 3) Measure key upper tropospheric atmospheric constituents that influence climate. The Aura instruments will monitor O3, H2O, CO, cirrus ice, and aerosols. EOS-Aura will fly in a sun-synchronous polar orbit about 15 minutes behind Aqua and make near coincident and synergistic measurements with the EOS- Aqua, Cloudsat, OCO, PARASOL and Calipso missions. Aura launched July 15,2004.

Schoeberl, Mark R.↗

The EOS-Aura Mission

The EOS-Aura atmospheric chemistry mission is scheduled for launch in June 2004. Aura is the third of the large EOS observatories. The spacecraft carries an international instrument payload that has a planned six year lifetime. The Aura mission will collect data to help answer stratospheric and tropospheric atmospheric chemistry questions. The mission has the following four major objectives: 1) Track the ozone layer to determine if it is recovering as predicted. The four Aura instruments, HIRDLS, OMI, MLS, and TES will measure ozone, key source, radical, reservoir, tracer gases, and aerosols. Aura's unique design allows for major ozone controlling gases to be measured within the same air mass within a few minutes. The OMI instrument will continue the trends from NASA's TOMS series. 2) Track tropospheric pollutant sources and measure tropospheric ozone precursors. Major pollution sources include urban, industrial and biomass burning regions. Tropospheric trace gases will be measured, using TES and OMI, at an average spatial resolution of about approx. 15 km with near global coverage. 3) Measure key upper tropospheric atmospheric constituents that influence climate. The Aura instruments will monitor O3, H2O, CO, cirrus ice, and aerosols. EOS-Aura will fly in a sun-synchronous polar orbit about 15 minutes behind Aqua and make near coincident and synergistic measurements with the EOS-Aqua, Cloudsat, OCO, PARASOL and Calipso missions. Aura launched July 15,2004.

Schoeberl, Mark R.↗

Evaluation of a New Chemical Mechanism for 2-Amino-2-methyl-1-propanol in a Reactive Environment from CSIRO Smog Chamber Experiments

Amines are considered as an emerging class of atmospheric pollutants that are of great importance to atmospheric chemistry and new particle formation. As a typical amine, 2-amino-2-methyl-1-propanol (AMP) is one of the proposed solvents for capturing CO 2 from flue gas streams in amine-based post-combustion CO 2 capture plants, and it is expected to result in AMP emission and secondary products formation in the atmosphere. However, the current knowledge of its atmospheric chemistry and kinetics is poorly understood, particularly in a reactive environment. As such, in this work we used the CSIRO smog chamber to study the photo-oxidation of AMP in the presence of VOCs–NOx surrogate mixtures over a range of initial amine concentrations. O 3 formation was significantly inhibited when AMP was added to the surrogate VOCs–NOx mixtures, implying that AMP could alter known atmospheric chemical reaction pathways and the prevailing reactivity. Simultaneously, a large amount of AMP-derived secondary aerosol was formed, with a considerably high aerosol mass yield (i.e. ratio of aerosol formed to reacted AMP) of 1.06±0.20. Based on updated knowledge of its kinetics, oxidation pathways and product yields, we have developed a new mechanism (designated as CSIAMP-19) and integrated into the Carbon Bond 6 (CB6) chemical mechanism, and evaluated it against available smog chamber data. Compared with the existing AMP mechanism (designated as CarterAMP-08), the modified CB6 with CSIAMP-19 mechanism improves prediction against AMP–VOCs–NOx experiments across a range of initial AMP concentrations, within ±10% model error for gross ozone production. Our results contribute to scientific understanding of AMP photochemistry and to the development of the chemical mechanism of other amines. The updated AMP chemical reactions scheme can be further embedded into the chemical transport model for regional modelling scenarios where AMP-related emissions are of concern.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photochemistry of Saturn's Atmosphere: Hydrocarbon Chemistry and Comparisons with ISO Observations - 1

To investigate the details of hydrocarbon photochemistry on Saturn, we have developed a one-dimensional diurnally averaged model that couples hydrocarbon and oxygen photochemistry, molecular and eddy diffusion, radiative transfer, and condensation. The model results are compared with observations from the Infrared Space Observatory (ISO) to place tighter constraints on molecular abundances, to better define Saturn's eddy diffusion coefficient profile, and to identify important chemical schemes that control the abundances of the observable hydrocarbons in Saturn's upper atmosphere. From the ISO observations, we determine that the column 12 densities of CH3, CH3C2H, and C4H2 above 10 mbar are 4 (sup +2) (sub -1.5) x 10 (exp 13) cm (sup -2), (1.1 plus or minus 0.3) x 10 (exp 15) cm (exp -2), and (1.2 plus or minus 0.3) x 10 (exp 14) cm (sup -2), respectively. The observed ISO emission features also indicate C2H2 mixing ratios of 1.2 (sup +0.9) (sub -0.6) x 10 (exp -6) at 0.3 mbar and (2.7 plus or minus 0.8) x 10 (exp -7) at 1.4 mbar, and a C2H6 mixing ratio of (9 plus or minus 2.5) x 10 (exp -6) at 0.5 mbar. Upper limits are provided for C2H4, CH2CCH2, C3H8, and C6H2 sensitivity of the model results to variations in the eddy diffusion coefficient profile, the solar flux, the CH4 photolysis branching ratios, the atomic hydrogen influx, and key reaction rates are discussed in detail. We find that C4H2 and CH3C2H are particularly good tracers of important chemical processes and physical conditions in Saturn's upper atmosphere, and C2H6 is a good tracer of the eddy diffusion coefficient in Saturn's lower stratosphere. The eddy diffusion coefficient must be smaller than approximately 3 x 10 (exp 4) sq cm s (sup -1) at pressures greater than 1 mbar in order to reproduce the C2H6 abundance inferred from ISO observations. The eddy diffusion coefficients in the upper stratosphere could be constrained by observations of CH3 radicals if the low-temperature chemistry of CH3 were better understood. We also discuss the implications of our modeling for aerosol formation in Saturn's lower stratosphere-diacetylene, butane, and water condense between approximately 1 and 300 mbar in our model and will dominate stratospheric haze formation at nonauroral latitudes. Our photochemical models will be useful for planning observational sequences and for analyzing data from the upcoming Cassini mission.

Moses, Julianne I.↗

A review of coarse mineral dust in the Earth system

Mineral dust particles suspended in the atmosphere span more than three orders of magnitude in diameter, from <0.1 µm to more than 100 µm. This wide size range makes dust a unique aerosol species with the ability to interact with many aspects of the Earth system, including radiation, clouds, hydrology, atmospheric chemistry, and biogeochemistry. This review focuses on coarse and super-coarse dust aerosols, which we respectively define as dust particles with a diameter of 2.5–10 µm and 10–62.5 µm. We review several lines of observational evidence indicating that coarse and super-coarse dust particles are transported farther than previously expected and that the abundance of these particles is substantially underestimated in current global models. We synthesize previous studies that used observations, theories, and model simulations to highlight the impacts of coarse and super-coarse dust aerosols on the Earth system, including their effects on dust-radiation interactions, dust-cloud interactions, atmospheric chemistry, and biogeochemistry. Specifically, coarse and super-coarse dust aerosols produce a net positive direct radiative effect (warming) at the top of the atmosphere and can modify temperature and water vapor profiles, influencing the distribution of clouds and precipitation. In addition, coarse and super-coarse dust aerosols contribute a substantial fraction of ice-nucleating particles, especially at temperatures above –23 °C. They also contribute a substantial fraction to the available reactive surfaces for atmospheric processing and the dust deposition flux that impacts land and ocean biogeochemistry by supplying important nutrients such as iron and phosphorus. Furthermore, we examine several limitations in the representation of coarse and super-coarse dust aerosols in current model simulations and remote-sensing retrievals. Because these limitations substantially contribute to the uncertainties in simulating the abundance and impacts of coarse and super-coarse dust aerosols, we offer some recommendations to facilitate future studies. Overall, we conclude that an accurate representation of coarse and super-coarse properties is critical in understanding the impacts of dust aerosols on the Earth system.

54 ENVIRONMENTAL SCIENCES↗

Infrared observations of the Saturnian system from Voyager 1

Atmospheric chemistry analyses of Saturn based on Voyager 1 infrared spectral and radiometric data are presented, including characteristics of the planet's rings and of Titan and other satellites. Infrared spectra of Saturn indicate the presence of H2, CH4, NH3, PH3, C2H2, and C2H6, with the possibility of C3H4 and C3H8. The atmospheric thermal structure of the planet shows hemispheric asymmetries that are consistent with seasonally varying insolation response, with an extensive small-scale latitudinal structure. Atmospheric chemistries of Titan, and optical and thermal characteristics for the rings of Saturn, are also given.

Hanel, R.↗

Global biomass burning - Atmospheric, climatic, and biospheric implications

The present volume discusses the biomass burning (BMB) studies of the International Global Atmospheric Chemistry project, GEO satellite estimation of Amazonian BMB, remote sensing of BMB in West Africa with NOAA-AVHRR, an orbital view of the great Chinese fire of 1987, BMB's role in tropical rainforest reduction, CO and O3 measurements of BMB in the Amazon, effects of vegetation burning on the atmospheric chemistry of the Venezuelan savanna, an assessment of annually-burned biomass in Africa, and light hydrocarbon emissions from African savanna burnings. Also discussed are BMB in India, trace gas and particulate emissions from BMB in temperate ecosystems, ammonia and nitric acid emissions from wetlands and boreal forest fires, combustion emissions and satellite imagery of BMB, BMB in the perspective of the global carbon cycle, modeling trace-gas emissions from BMB, NO(x) emissions from BMB, and cloud-condensation nuclei from BMB.

Levine, Joel S.↗