Anthropogenic Sulfur Perturbations on Biogenic Oxidation

SO2 Additions Impact Gas-Phase OH Oxidation Products of α- And β-Pinene

Beth Friedman, Patrick Brophy, William Henry Brune, Delphine K. Farmer

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

In order to probe how anthropogenic pollutants can impact the atmospheric oxidation of biogenic emissions, we investigated how sulfur dioxide (SO2) perturbations impact the oxidation of two monoterpenes, α-and β-pinene. We used chemical ionization mass spectrometry to examine changes in both individual molecules and gas-phase bulk properties of oxidation products as a function of SO2 addition. SO2 perturbations impacted the oxidation systems of α-and β-pinene, leading to an ensemble of products with a lesser degree of oxygenation than unperturbed systems. These changes may be due to shifts in the OH:HO2 ratio from SO2 oxidation and/or to SO3 reacting directly with organic molecules. Van Krevelen diagrams suggest a shift from gas-phase functionalization by alcohol/peroxide groups to functionalization by carboxylic acid or carbonyl groups, consistent with a decreased OH:HO2 ratio. Increasing relative humidity dampens the impact of the perturbation. This decrease in oxygenation may impact secondary organic aerosol formation in regions dominated by biogenic emissions with nearby SO2 sources. We observed sulfur-containing organic compounds following SO2 perturbations of monoterpene oxidation; whether these are the result of photochemistry or an instrumental artifact from ion-molecule clustering remains uncertain. However, our results demonstrate that the two monoterpene isomers produce unique suites of oxidation products.

Original languageEnglish (US)
Pages (from-to)1269-1279
Number of pages11
JournalEnvironmental Science and Technology
Volume50
Issue number3
DOIs
StatePublished - Feb 2 2016

Fingerprint

Sulfur
Gases
sulfur
perturbation
oxidation
Oxidation
Monoterpenes
monoterpene
gas
biogenic emission
Oxygenation
oxygenation
Molecules
organic sulfur compound
Sulfur Dioxide
aerosol formation
Photochemical reactions
Peroxides
photochemistry
carboxylic acid

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Environmental Chemistry

Cite this

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title = "Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO2 Additions Impact Gas-Phase OH Oxidation Products of α- And β-Pinene",
abstract = "In order to probe how anthropogenic pollutants can impact the atmospheric oxidation of biogenic emissions, we investigated how sulfur dioxide (SO2) perturbations impact the oxidation of two monoterpenes, α-and β-pinene. We used chemical ionization mass spectrometry to examine changes in both individual molecules and gas-phase bulk properties of oxidation products as a function of SO2 addition. SO2 perturbations impacted the oxidation systems of α-and β-pinene, leading to an ensemble of products with a lesser degree of oxygenation than unperturbed systems. These changes may be due to shifts in the OH:HO2 ratio from SO2 oxidation and/or to SO3 reacting directly with organic molecules. Van Krevelen diagrams suggest a shift from gas-phase functionalization by alcohol/peroxide groups to functionalization by carboxylic acid or carbonyl groups, consistent with a decreased OH:HO2 ratio. Increasing relative humidity dampens the impact of the perturbation. This decrease in oxygenation may impact secondary organic aerosol formation in regions dominated by biogenic emissions with nearby SO2 sources. We observed sulfur-containing organic compounds following SO2 perturbations of monoterpene oxidation; whether these are the result of photochemistry or an instrumental artifact from ion-molecule clustering remains uncertain. However, our results demonstrate that the two monoterpene isomers produce unique suites of oxidation products.",
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Anthropogenic Sulfur Perturbations on Biogenic Oxidation : SO2 Additions Impact Gas-Phase OH Oxidation Products of α- And β-Pinene. / Friedman, Beth; Brophy, Patrick; Brune, William Henry; Farmer, Delphine K.

In: Environmental Science and Technology, Vol. 50, No. 3, 02.02.2016, p. 1269-1279.

Research output: Contribution to journalArticle

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