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The Critical Role of Synthetic Chemistry in Elucidating Mechanisms, Product...
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The Critical Role of Synthetic Chemistry in Elucidating Mechanisms, Product Identification, and Quantitation in Atmospheric Gas-Phase and Multiphase Chemistry of Volatile Organic Emissions

A special issue of Atmosphere (ISSN 2073-4433). This special issue belongs to the section "Air Quality".

Deadline for manuscript submissions: closed (15 June 2022) | Viewed by 10407

Special Issue Editors

Prof. Dr. Avram Gold

E-Mail Website
Guest Editor
Department of Environmental Sciences and Engineering, Gillings School of Global Public Health, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA
Interests: organic synthesis; reaction mechanisms; molecular structure determination; mechanisms of secondary organic aerosol formation
Prof. Dr. Jason Surratt

E-Mail Website
Guest Editor
Department of Environmental Sciences and Engineering, UNC Gillings School of Global Public Health, NC 27599, USA
Interests: atmospheric chemistry; chemical formation and evolution of secondary organic aerosol; analysis of gas- and aerosol-phase constituents to elucidate reaction pathways leading to fine organic aerosol

Special Issue Information

Dear Colleagues,

Considerable progress has been made towards elucidating the mechanisms of secondary organic aerosol (SOA) formation from the photochemical oxidation of volatile organic compounds (VOCs), both biological and anthropogenic in origin, and in identifying individual SOA components. A key factor in understanding SOA formation, composition, and behavior has been the availability of authentic standards serving as intermediates for verification of putative SOA formation pathways, structural verification of products, quantitation of SOA components, and assessment of both the analytical methodology and physicochemical properties of SOAs. Several examples taken from the investigation of the atmospheric chemistry of isoprene—an area of some familiarity to the editor—can exemplify the importance of synthetic chemistry. Synthesis of isoprene epoxydiols (IEPOX) established the putative IEPOX pathway as the major contributor to isoprene-derived SOA under low-NOx conditions and enabled structural confirmation of isoprene-SOA marker compounds. Availability of authentic isomeric isoprene hydroxyhydroperoxides (ISOPOOH) led to the revelation that field monitoring by gas chromatography and proton transfer reaction mass spectrometry degraded the first-generation ISOPOOH isomers, yielding methylvinylketone and acrolein, products associated with high-NOx chemistry, confounding the interpretation of isoprene oxidation pathways.

To date, the picture regarding all aspects of SOA research is far from complete, and continued advances in multiple areas will require the availability of authentic standards. The following, but by no means comprehensive list of topics includes reconciling low-volatility isoprene SOA with high concentrations of semi-volatile marker compounds as determined by widely applied analytical procedures; the extent of oligomeric species in terms of aerosol composition; the importance of hydroperoxides in initial accretion reactions and subsequent generation of ROS and other radical species in particles; the dependence of the quantitation of potentially labile aerosol components on analytical methodology; changes in aerosol composition and properties during aging; the interdependence of physicochemical properties of SOA on composition and environmental factors; identification of the nitrate ester contribution to SOA; mechanisms of formation and the identification and quantitation of organosulfates and implications for the atmospheric sulfur budget; the impact of climate change on the evolution of SOA properties; the composition of fine particulate matter and its impact on human health.

We invite contributions on synthetic efforts and the application of newly synthesized compounds to advancing our understanding of atmospheric processes affecting SOA.

Prof. Avram Gold
Prof. Jason Surratt
Guest Editors

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Keywords

  • Synthetic chemistry
  • Authentic standards
  • Putative intermediates
  • Putative SOA transients
  • Mechanisms of reactive uptake
  • Product quantitation

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Published Papers (3 papers)

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Research

12 pages, 2192 KiB  
Article
Condensed Phase Kinetic Studies of Hydroxynitrates Derived from the Photooxidation of Carene, Limonene, trans-Carveol, and Perillic Alcohol
by James I. Vesto, Addison B. McAlister, Kathryn A. Wright, Aaron Huang, Petra R. Baldwin, Emily J. McLaughlin Sta. Maria, Rebecca Lyn LaLonde and Anthony J. Carrasquillo
Atmosphere 2022, 13(4), 592; https://doi.org/10.3390/atmos13040592 - 6 Apr 2022
Cited by 2 | Viewed by 2845
Abstract
Organic hydroxynitrates (HNs) are key products of hydrocarbon oxidation in the atmosphere. Understanding the fate and processing of these molecules is critical due to their function in the sequestration of NOx species from the atmosphere and in the formation of secondary organic [...] Read more.
Organic hydroxynitrates (HNs) are key products of hydrocarbon oxidation in the atmosphere. Understanding the fate and processing of these molecules is critical due to their function in the sequestration of NOx species from the atmosphere and in the formation of secondary organic aerosol. However, the direct study of individual HNs’ reactivity has been largely hindered by the lack of authentic standards which has further limited the ability to deconvolute the role of structural features. Herein, we report the kinetic stabilities of six biogenic volatile organic compound-derived HN in acidified single-phase organic/water matrices. Lifetimes for tertiary HNs ranged from 15 min to 6.4 h, whereas secondary HN varied from 56 days to 2.1 years. Product analysis highlights the role that additional non-hydrolysis reactions have in the condensed phase conversion of HNs. This work provides the first evidence for the structural dependence of HN stability in bulk mixed media. Full article
(This article belongs to the Special Issue The Critical Role of Synthetic Chemistry in Elucidating Mechanisms, Product Identification, and Quantitation in Atmospheric Gas-Phase and Multiphase Chemistry of Volatile Organic Emissions)
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19 pages, 13156 KiB  
Article
Synthesis and Characterization of Atmospherically Relevant Hydroxy Hydroperoxides
by Peter Mettke, Anke Mutzel, Olaf Böge and Hartmut Herrmann
Atmosphere 2022, 13(4), 507; https://doi.org/10.3390/atmos13040507 - 22 Mar 2022
Cited by 7 | Viewed by 2991
Abstract
Hydroxy hydroperoxides are formed upon OH oxidation of volatile organic compounds in the atmosphere and may contribute to secondary organic aerosol growth and aqueous phase chemistry after phase transfer to particles. Although the detection methods for oxidized volatile organic compounds improved much over [...] Read more.
Hydroxy hydroperoxides are formed upon OH oxidation of volatile organic compounds in the atmosphere and may contribute to secondary organic aerosol growth and aqueous phase chemistry after phase transfer to particles. Although the detection methods for oxidized volatile organic compounds improved much over the past decades, the limited availability of synthetic standards for atmospherically relevant hydroxy hydroperoxides prevented comprehensive investigations for the most part. Here, we present a straightforward improved synthetic access to isoprene-derived hydroxy hydroperoxides, i.e., 1,2-ISOPOOH and 4,3-ISOPOOH. Furthermore, we present the first successful synthesis of an α-pinene derived hydroxy hydroperoxide. All products were identified by 1H, 13C NMR spectroscopy for structure elucidation, additional 2D NMR experiments were performed. Furthermore, gas-phase FTIR- and UV/VIS spectra are presented for the first time. Using the measured absorption cross section, the atmospheric photolysis rate of up to 2.1 × 10−3 s−1 was calculated for 1,2-ISOPOOH. Moreover, we present the investigation of synthesized hydroxy hydroperoxides in an aerosol chamber study by online MS techniques, namely PTR-ToFMS and (NO3−)-CI-APi-ToFMS. Fragmentation patterns recorded during these investigations are presented as well. For the (NO3−)-CI-APi-ToFMS, a calibration factor for 1,2-ISOPOOH was calculated as 4.44 × 10−5 ncps·ppbv−1 and a LOD (3σ, 1 min average) = 0.70 ppbv. Full article
(This article belongs to the Special Issue The Critical Role of Synthetic Chemistry in Elucidating Mechanisms, Product Identification, and Quantitation in Atmospheric Gas-Phase and Multiphase Chemistry of Volatile Organic Emissions)
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12 pages, 2938 KiB  
Article
Reactivity of a Carene-Derived Hydroxynitrate in Mixed Organic/Aqueous Matrices: Applying Synthetic Chemistry to Product Identification and Mechanistic Implications
by Addison B. McAlister, James I. Vesto, Aaron Huang, Kathryn A. Wright, Emily J. McLaughlin Sta. Maria, Gabriela M. Bailey, Nicole P. Kretekos, Petra R. Baldwin, Anthony J. Carrasquillo and Rebecca Lyn LaLonde
Atmosphere 2021, 12(12), 1617; https://doi.org/10.3390/atmos12121617 - 3 Dec 2021
Cited by 4 | Viewed by 3585
Abstract
β-hydroxynitrates (HN) are a major class of products formed during OH and NO3 initiated oxidation of terpenes. Their production contributes significantly to secondary organic aerosol (SOA) formation and NOx sequestration. However, studying the condensed phase reactions of this important class of [...] Read more.
β-hydroxynitrates (HN) are a major class of products formed during OH and NO3 initiated oxidation of terpenes. Their production contributes significantly to secondary organic aerosol (SOA) formation and NOx sequestration. However, studying the condensed phase reactions of this important class of molecules has been hindered by the lack of commercially available authentic standards. The goal of this work was to examine the influence of water concentration and solvent identity on product yields of a tertiary HN derived from 3-carene prepared in house. To assess the role of water on conversion chemistry, bulk-phase reactions were conducted in DMSO-d6, a non-nucleophilic solvent, with a gradient of water concentrations, and analyzed with 1H NMR. Product identifications were made by comparison with authentic standards prepared in house. Four major products were identified, including an unexpected diol produced from carbocation rearrangement, diol diastereomers, and trans-3-carene oxide, with varying yields as a function of water concentration. Product yields were also measured in two protic, nucleophilic solvents, MeOD-d4 and EtOD-d6. Finally, reactions with added chloride formed alkyl chloride products in yields approaching 30%. These results are among the first to highlight the complexities of nucleophilic reactions of hydroxynitrates in bulk, mixed aqueous/organic media and to identify new, unexpected products. Full article
(This article belongs to the Special Issue The Critical Role of Synthetic Chemistry in Elucidating Mechanisms, Product Identification, and Quantitation in Atmospheric Gas-Phase and Multiphase Chemistry of Volatile Organic Emissions)
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