Revisiting the reaction of dicarbonyls in aerosol proxy solutions containing ammonia: the case of butenedial.

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From: Atmospheric Chemistry and Physics(Vol. 21, Issue 11)
Publisher: Copernicus GmbH
Document Type: Brief article
Length: 320 words

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Abstract :

Reactions in aqueous solutions containing dicarbonyls (especially the α-dicarbonyls methylglyoxal, glyoxal, and biacetyl) and reduced nitrogen (NH.sub.x) have been studied extensively. It has been proposed that accretion reactions from dicarbonyls and NH.sub.x could be a source of particulate matter and brown carbon in the atmosphere and therefore have direct implications for human health and climate. Other dicarbonyls, such as the 1,4-unsaturated dialdehyde butenedial, are also produced from the atmospheric oxidation of volatile organic compounds, especially aromatics and furans, but their aqueous-phase reactions with NH.sub.x have not been characterized. In this work, we determine a pH-dependent mechanism of butenedial reactions in aqueous solutions with NH.sub.x that is compared to α-dicarbonyls, in particular the dialdehyde glyoxal. Similar to glyoxal, butenedial is strongly hydrated in aqueous solutions. Butenedial reaction with NH.sub.x also produces nitrogen-containing rings and leads to accretion reactions that form brown carbon. Despite glyoxal and butenedial both being dialdehydes, butenedial is observed to have three significant differences in its chemical behavior: (1) as previously shown, butenedial does not substantially form acetal oligomers, (2) the butenedial/OH.sup.- reaction leads to light-absorbing compounds, and (3) the butenedial/NH.sub.x reaction is fast and first order in the dialdehyde. Building off of a complementary study on butenedial gas-particle partitioning, we suggest that the behavior of other reactive dialdehydes and dicarbonyls may not always be adequately predicted by α-dicarbonyls, even though their dominant functionalities are closely related. The carbon skeleton (e.g., its hydrophobicity, length, and bond structure) also governs the fate and climate-relevant properties of dicarbonyls in the atmosphere. If other dicarbonyls behave like butenedial, their reaction with NH.sub.x could constitute a regional source of brown carbon to the atmosphere.

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Gale Document Number: GALE|A664760087