Analysis and stability of aldehydes and terpenes in electropolished canisters

Aldehydes and terpenes are important classes of polar VOC contaminants for which few sampling and analysis methods have been validated. This study reports on the analysis, stability and recovery of seven aldehydes (butanal, pentanal, hexanal, heptanal, octanal, nonanal and benzaldehyde) and four terpenes (α-pinene, β-pinene, limonene and 3-carene) prepared at trace levels (3–5 ppb) and stored in electropolished stainless-steel canisters. Humidified air, humidified N2, and dry air were used to dilute three sets of canisters. A series of samples was withdrawn from each canister over a period of 16 days, and concentrations were determined by cryogenic preconcentration, gas chromatography and mass spectrometry. The VOCs were easily separated, but butanal and pentanal had high detection limits relative to the other compounds. While measurements were reproducible, concentrations decreased considerably in the first hour (19% in the humidified air-filled canister set), and losses continued over the measurement period, although at a slower rate. The estimated half-lives of aldehydes and terpenes were 18 d in humidified air-filled canisters, 24 d in humidified N2, and 6 d in dry air. Loss mechanisms and analytical considerations for the target compounds are discussed. Like other VOCs, the collection and storage of aldehydes and terpenes in canisters require humidification; however; the absolute accuracy of samples and standards of mixtures of aldehydes and terpenes stored in canisters may be limited.