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  1. Free, publicly-accessible full text available November 29, 2024
  2. Free, publicly-accessible full text available April 20, 2024
  3. Blum, Joel (Ed.)
    Atmospheric oxidation of isoprene yields large quantities of highly water-soluble isoprene epoxydiols (IEPOX) that partition into fogs, clouds, and wet aerosols. In aqueous aerosols, the acid-catalyzed ring-opening of IEPOX followed by nucleophilic addition of inorganic sulfate or water forms organosulfates and 2-methyltetrols, respectively, contributing substantially to secondary organic aerosol (SOA). However, the fate of IEPOX in clouds, fogs, and evaporating hydrometeors is not well understood. Here we investigate the rates, product branching ratios, and stereochemistry of organosulfates from reactions of dilute IEPOX (5–10 mM) under a range of sulfate concentrations (0.3–50 mM) and pH values (1.83–3.38) in order to better understand the fate of IEPOX in clouds and fogs. From these aqueous dark reactions of β-IEPOX isomers (trans- and cis-2-methyl-2,3-epoxybutane-1,4-diols), which are the predominant IEPOX isomers, products were identified and quantified using hydrophilic interaction liquid chromatography coupled to an electrospray ionization high-resolution quadrupole time-of-flight mass spectrometer operated in negative ion mode (HILIC/(−)ESI-HR-QTOFMS). We found that the regiochemistry and stereochemistry were affected by pH, and the tertiary methyltetrol sulfate (C5H12O7S) was promoted by increasing solution acidity. Furthermore, the rate constants for the reaction of IEPOX under cloud-relevant conditions are up to 1 order of magnitude lower than reported in the literature for aerosol-relevant conditions due to a markedly different solution activities. Nevertheless, the contribution of cloud and fog water reactions to IEPOX SOA may be significant in cases of lower aqueous-phase pH (model estimate) or during droplet evaporation (not studied). 
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  4. Abstract. Acidity, defined as pH, is a central component of aqueouschemistry. In the atmosphere, the acidity of condensed phases (aerosolparticles, cloud water, and fog droplets) governs the phase partitioning ofsemivolatile gases such as HNO3, NH3, HCl, and organic acids andbases as well as chemical reaction rates. It has implications for theatmospheric lifetime of pollutants, deposition, and human health. Despiteits fundamental role in atmospheric processes, only recently has this fieldseen a growth in the number of studies on particle acidity. Even with thisgrowth, many fine-particle pH estimates must be based on thermodynamic modelcalculations since no operational techniques exist for direct measurements.Current information indicates acidic fine particles are ubiquitous, butobservationally constrained pH estimates are limited in spatial and temporalcoverage. Clouds and fogs are also generally acidic, but to a lesser degreethan particles, and have a range of pH that is quite sensitive toanthropogenic emissions of sulfur and nitrogen oxides, as well as ambientammonia. Historical measurements indicate that cloud and fog droplet pH haschanged in recent decades in response to controls on anthropogenicemissions, while the limited trend data for aerosol particles indicateacidity may be relatively constant due to the semivolatile nature of thekey acids and bases and buffering in particles. This paper reviews andsynthesizes the current state of knowledge on the acidity of atmosphericcondensed phases, specifically particles and cloud droplets. It includesrecommendations for estimating acidity and pH, standard nomenclature, asynthesis of current pH estimates based on observations, and new modelcalculations on the local and global scale. 
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  5. Abstract

    Chemical processes in clouds and fogs can substantially alter atmospheric oxidant budgets and lead to aerosol mass formation. However, many regional and global models do not include detailed aqueous‐phase chemical mechanisms due to the (a) lack of complete understanding of the chemical processes and (b) computational burden of adding constituents. Current gas‐aqueous chemistry 0‐dimensional models were evaluated in a cloud‐chemistry box model intercomparison based on a mid‐September 2016 cloud chemistry event at Whiteface Mountain, New York. Multiphase mechanisms in the five participating models ranged from those appropriate for 3‐d models to highly complex with thousands of reactions. This study focused on oxidant levels in both phases and aqueous‐phase sulfate and organic acid formation. Comparison of gas‐phase‐only chemistry gives very similar oxidant predictions at night but shows significant differences during daytime with the hydroxyl radical (OH) variability of about an order of magnitude. The variability in the model results increases substantially with aqueous chemistry due to different Henry's Law constants, aqueous‐phase reaction rate constants, and chemical mechanisms. Using a prescribed liquid water content and pH value of 4.5, modeled aqueous OH, aldehyde, and organic acid concentrations differ by over an order of magnitude in daytime. Simulations were also conducted at a pH = 5.1, predicted variable pH, and with added transition metal ion chemistry. While we compare predicted and measured inorganic anions and water‐soluble organic carbon, we cannot do so for aqueous‐phase oxidant concentrations due to the lack of measurements. We highlight a need for recommended equilibrium and aqueous‐phase rate constants.

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  6. Concentrations of atmospheric trace species in the United States have changed dramatically over the past several decades in response to pollution control strategies, shifts in domestic energy policy and economics, and economic development (and resulting emission changes) elsewhere in the world. Reliable projections of the future atmosphere require models to not only accurately describe current atmospheric concentrations, but to do so by representing chemical, physical and biological processes with conceptual and quantitative fidelity. Only through incorporation of the processes controlling emissions and chemical mechanisms that represent the key transformations among reactive molecules can models reliably project the impacts of future policy, energy and climate scenarios. Efforts to properly identify and implement the fundamental and controlling mechanisms in atmospheric models benefit from intensive observation periods, during which collocated measurements of diverse, speciated chemicals in both the gas and condensed phases are obtained. The Southeast Atmosphere Studies (SAS, including SENEX, SOAS, NOMADSS and SEAC4RS) conducted during the summer of 2013 provided an unprecedented opportunity for the atmospheric modeling community to come together to evaluate, diagnose and improve the representation of fundamental climate and air quality processes in models of varying temporal and spatial scales.

    This paper is aimed at discussing progress in evaluating, diagnosing and improving air quality and climate modeling using comparisons to SAS observations as a guide to thinking about improvements to mechanisms and parameterizations in models. The effort focused primarily on model representation of fundamental atmospheric processes that are essential to the formation of ozone, secondary organic aerosol (SOA) and other trace species in the troposphere, with the ultimate goal of understanding the radiative impacts of these species in the southeast and elsewhere. Here we address questions surrounding four key themes: gas-phase chemistry, aerosol chemistry, regional climate and chemistry interactions, and natural and anthropogenic emissions. We expect this review to serve as a guidance for future modeling efforts. 
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