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Fresh versus Photo-recalcitrant Secondary Organic Aerosol: Effects of Organic Mixtures on Aqueous Photodegradation of 4-Nitrophenol
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    Fresh versus Photo-recalcitrant Secondary Organic Aerosol: Effects of Organic Mixtures on Aqueous Photodegradation of 4-Nitrophenol
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    • Tanner Braman
      Tanner Braman
      Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23185, United States
    • Lydia Dolvin
      Lydia Dolvin
      Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23185, United States
      More by Lydia Dolvin
    • Corey Thrasher
      Corey Thrasher
      Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23185, United States
    • Hongmin Yu
      Hongmin Yu
      Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23185, United States
      More by Hongmin Yu
    • Emma Q. Walhout
      Emma Q. Walhout
      Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23185, United States
    • Rachel E. O’Brien*
      Rachel E. O’Brien
      Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23185, United States
      *Email: [email protected]. Phone: 1-757-221-1858.
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    Environmental Science & Technology Letters

    Cite this: Environ. Sci. Technol. Lett. 2020, 7, 4, 248–253
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    https://doi.org/10.1021/acs.estlett.0c00177
    Published March 6, 2020
    Copyright © 2020 American Chemical Society

    Abstract

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    In the atmosphere, brown carbon (BrC) molecules can contribute to photochemistry and to the warming and evaporation of cloud droplets. The lifetimes of BrC molecules in these cloud droplets are not well constrained, especially considering the droplets can contain mixtures of organic and inorganic molecules. Here we investigated the kinetics of photodegradation for a representative brown carbon molecule, 4-nitrophenol (4NP), in aqueous solutions at low pH. Three different solutions were compared: one containing 4NP alone and the other two additionally containing either fresh or photo-recalcitrant (pre-photobleached) α-pinene secondary organic aerosol (SOA). Fresh SOA slightly accelerates the photodegradation compared to that with 4NP alone. In contrast, photo-recalcitrant SOA decelerates photodegradation, increasing the estimated atmospheric lifetime of 4NP by 4 h (from ∼11 h for BrC alone to ∼14 h when it is mixed with photo-recalcitrant SOA). Photo-recalcitrant SOA also shows minimal chemical changes after irradiation for 20 h in aqueous solution. These results suggest that, in contrast to fresh SOA, aqueous photo-recalcitrant SOA does not serve as a source of OH radicals when irradiated but may instead act as an OH radical scavenger. The presence of photo-recalcitrant SOA could have important effects on atmospheric lifetimes of organics in mixed aqueous systems.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.estlett.0c00177.

    • Additional text and figures giving extended methods, absorption changes with pH, arc lamp spectrum, absorption cross sections, browning of 4NP over time, replicate experiments, and absorption changes that occur in SOA solutions without BrC (PDF)

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    Environmental Science & Technology Letters

    Cite this: Environ. Sci. Technol. Lett. 2020, 7, 4, 248–253
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.estlett.0c00177
    Published March 6, 2020
    Copyright © 2020 American Chemical Society

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