A Role for 2-Methyl Pyrrole in the Browning of 4-Oxopentanal and Limonene Secondary Organic Aerosol

Environ Sci Technol. 2017 Oct 3;51(19):11048-11056. doi: 10.1021/acs.est.7b02293. Epub 2017 Sep 15.

Abstract

Reactions of ammonia or ammonium sulfate (AS) with carbonyls in secondary organic aerosol (SOA) produced from limonene are known to form brown carbon (BrC) with a distinctive absorption band at 505 nm. This study examined the browning processes in aqueous solutions of AS and 4-oxopentanal (4-OPA), which has a 1,4-dicarbonyl structural motif present in many limonene SOA compounds. Aqueous reactions of 4-OPA with AS were found to produce 2-methyl pyrrole (2-MP), which was detected by gas chromatography. While 2-MP does not absorb visible radiation, it can further react with 4-OPA eventually forming BrC compounds. This was demonstrated by reacting 2-MP with 4-OPA or limonene SOA, both of which produced BrC with absorption bands at 475 and 505 nm, respectively. The formation of BrC in the reaction of 4-OPA with AS and ammonium nitrate was greatly accelerated by evaporation of the solution suggesting an important role of the dehydration processes in BrC formation. 4-OPA was also found to produce BrC in aqueous reactions with a broad spectrum of amino acids and amines. These results suggest that 4-OPA may be the smallest atmospherically relevant compound capable of browning by the same mechanism as limonene SOA.

MeSH terms

  • Aerosols*
  • Aldehydes
  • Cyclohexenes*
  • Ketones
  • Limonene
  • Pyrroles
  • Terpenes*

Substances

  • Aerosols
  • Aldehydes
  • Cyclohexenes
  • Ketones
  • Pyrroles
  • Terpenes
  • Limonene
  • 4-oxopentanal