Differences in Photosensitized Release of VOCs from Illuminated Seawater versus Freshwater Surfaces

Recent studies have shown that photochemical reactions occurring at the air–water interface are a source of volatile organic compounds (VOCs) to the atmosphere. We report here the photosensitized formation of VOCs from illuminated freshwater and seawater mimics containing nonanoic acid (NA) and/or Suwannee River natural organic matter (SRNOM). Under an atmosphere of air, the total blank-corrected steady-state concentration of VOCs formed from illuminated seawater coated with nonanoic acid is somewhat smaller than that formed from freshwater, suggesting some differences in photochemical pathways for the two substrates. The total blank-corrected steady-state concentration of VOCs more than doubles from both freshwater and seawater NA-coated surfaces under nitrogen compared to air. The addition of SRNOM as a photosensitizer induces some photochemistry from the seawater sample under air, but no chemistry is seen with freshwater or under nitrogen for either substrate. Adding SRNOM to the nonanoic acid-containing solutions roughly doubles the total steady-state concentration of VOCs emitted from both freshwater and seawater surfaces under air. The small differences in product formation for the two substrates imply some difference in the photochemical mechanisms operating in freshwater versus seawater, which may be due to the presence of halides and metals as well as pH differences between the two aqueous systems.