Factors affecting the formation of alpha and beta polymorphs in glutaric acid aerosols

Dicarboxylic acids are prevalent in the atmosphere and frequently investigated by aerosol and atmospheric scientists. Glutaric acid, being a water-soluble dicarboxylic acid, is commonly used to model water activity in dicarboxylic acid aerosols. Different values associated with glutaric acid aerosols, specifically DRH and hygroscopic data, have been reported by several groups. We hypothesize that this variability is caused by its polymorphism. Glutaric acid exhibits dimorphism, meaning the molecule can form into two different types of crystal structures, an alpha and a beta polymorph. Glutaric acid naturally forms the beta polymorph, which is more stable. The alpha polymorph is the metastable phase. These polymorphs manifest themselves as a bimodal aerosol size distribution when analyzed by Scanning Mobility Particle Sizers or other aerosol mobility sizing methods. In this article, we discuss the formation of the nanoscale alpha glutaric acid polymorph generated from an aqueous glutaric acid solution. The formation of both polymorphs from an aqueous solution has not been documented elsewhere. We have found that the alpha polymorph forms at faster crystallization speeds, with a lower aqueous solution concentration and a lower solution flow rate into the atomizer. This identification of the presence of polymorphism in glutaric acid aerosols under common laboratory generation conditions could explain the variability present in studies associated with glutaric acid aerosols. Understanding the conditions at which the alpha polymorph is present will allow researchers to avoid it when using glutaric acid as a dicarboxylic acid standard and explain previously noted discrepancies.

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