New Particle Formation and Growth from Dimethyl Sulfide Oxidation by Hydroxyl Radicals

• Dimethyl sulfide (DMS) is produced by plankton in oceans and constitutes the largest natural emission of sulfur to the atmosphere. In this work, we examine new particle formation from the primary pathway of oxidation of gas-phase DMS by OH radicals. We particularly focus on particle growth and mass yield as studied experimentally under dry conditions using the atmospheric simulation chamber AURA. Experimentally, we show that aerosol mass yields from oxidation of 50-200 ppb of DMS are low (2-7%) and that particle growth rates (8.2-24.4 nm/h) are comparable with ambient observations. An HR-ToF-AMS was calibrated using methanesulfonic acid (MSA) to account for fragments distributed across both the organic and sulfate fragmentation table. AMS-derived chemical compositions revealed that MSA was always more dominant than sulfate in the secondary aerosols formed. Modeling using the Aerosol Dynamics, gas- and particle-phase chemistry kinetic multilayer model for laboratory CHAMber studies (ADCHAM) indicates that the Master Chemical Mechanism gas-phase chemistry alone underestimates experimentally observed particle formation and that DMS multiphase and autoxidation chemistry is needed to explain observations. Based on quantum chemical calculations, we conclude that particle formation from DMS oxidation in the ambient atmosphere will most likely be driven by mixed sulfuric acid/MSA clusters clustering with both amines and ammonia.

Subject headings

NATURVETENSKAP  -- Geovetenskap och miljövetenskap -- Meteorologi och atmosfärforskning (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences -- Meteorology and Atmospheric Sciences (hsv//eng)

Keyword

atmospheric simulation chamber

dimethyl sulfide

growth rate

methanesulfonic acid

nucleation

photo-oxidation

Publication and Content Type

art (subject category)

ref (subject category)