Simultaneous Determination of Mono- and Dicarboxylic Acids, ω-Oxo-carboxylic Acids, Midchain Ketocarboxylic Acids, and Aldehydes in Atmospheric Aerosol Samples

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Abstract
This paper describes a method for the simultaneous determination of monocarboxylic acids (C6−C34), dicarboxylic acids (C2−C24), ω-oxo-carboxylic acids (C2−C9), ketocarboxylic acids (pyruvic and pinonic acid), and select aldehydes (glyoxal, methylglyoxal, and nonanal) in atmospheric particles. Quantification of these compounds gives information on important chemical characteristics of aerosols for source apportioning of aerosol organics and for studying atmospheric processes leading to secondary organic aerosol formation. These target analytes were determined as their butyl ester or butyl acetal derivatives using gas-chromatography mass spectrometry. The method is modified from a method described by Kawamura. Kawamura's original method involved a water extraction step, which practically restricted the method to the determination of only those compounds that are water-soluble. Our method eliminates the water extraction step and combines extraction and derivatization of the target compounds in one step. A mixture of hexane/butanol/BF3 simultaneously derivatizes the polar function groups (i.e., −COOH, −CO) and extracts the target analytes from the aerosol filter substrates. A prominent advantage of our method is improved recoveries for the more volatile analytes in the target compound classes as a result of eliminating the water evaporation step. Recoveries better than 66% were obtained for the target analytes, including the relatively volatile ones. This improvement for the light species has allowed detection of a new midchain ketocarboxylic acid, 4-oxopentanoic acid, which would have escaped detection by the Kawamura method because of its high susceptibility to evaporative loss. Examples are presented to demonstrate the use of this method in analysis of ambient aerosol samples.