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Carbenium ion-mediated oligomerization of methylglyoxal for secondary organic aerosol formation.

Yuemeng JiQiuju ShiYixin LiTaicheng AnJun ZhengJianfei PengYanpeng GaoJiangyao ChenGuiying LiYuan WangFang ZhangAnnie L ZhangJiayun ZhaoMario J MolinaRenyi Zhang
Published in: Proceedings of the National Academy of Sciences of the United States of America (2020)
Secondary organic aerosol (SOA) represents a major constituent of tropospheric fine particulate matter, with profound implications for human health and climate. However, the chemical mechanisms leading to SOA formation remain uncertain, and atmospheric models consistently underpredict the global SOA budget. Small α-dicarbonyls, such as methylglyoxal, are ubiquitous in the atmosphere because of their significant production from photooxidation of aromatic hydrocarbons from traffic and industrial sources as well as from biogenic isoprene. Current experimental and theoretical results on the roles of methylglyoxal in SOA formation are conflicting. Using quantum chemical calculations, we show cationic oligomerization of methylglyoxal in aqueous media. Initial protonation and hydration of methylglyoxal lead to formation of diols/tetrol, and subsequent protonation and dehydration of diols/tetrol yield carbenium ions, which represent the key intermediates for formation and propagation of oligomerization. On the other hand, our results reveal that the previously proposed oligomerization via hydration for methylglyoxal is kinetically and thermodynamically implausible. The carbenium ion-mediated mechanism occurs barrierlessly on weakly acidic aerosols and cloud/fog droplets and likely provides a key pathway for SOA formation from biogenic and anthropogenic emissions.
Keyphrases
  • particulate matter
  • air pollution
  • human health
  • water soluble
  • risk assessment
  • climate change
  • molecular dynamics
  • wastewater treatment
  • genome wide
  • autism spectrum disorder
  • dna methylation
  • amino acid
  • aqueous solution