Stability assessment of gas mixtures containing monoterpenes in varying cylinder materials and treatments.

Studies of climate change increasingly recognize the diverse influences exerted by monoterpenes in the atmosphere, including roles in particulates, ozone formation, and oxidizing potential. Measurements of key monoterpenes suggest atmospheric mole fractions ranging from low pmol/mol (parts-per-trillion; ppt) to nmol/mol (parts-per-billion; ppb), depending on location and compound. To accurately establish the mole fraction trends, assess the role of monoterpenes in atmospheric chemistry, and relate measurement records from many laboratories and researchers, it is essential to have good calibration standards. The feasibility of preparing well-characterized, stable gas cylinder standards for monoterpenes at the nmol/mol level was previously tested using treated (Aculife IV) aluminum gas cylinders at NIST. Results for 4 of the 11 monoterpenes, monitored versus an internal standard of benzene, indicated stability in these treated aluminum gas cylinders for over 6 months and projected long-term (years) stability. However, the mole fraction of the key monoterpene β-pinene decreased, while the mole fractions of α-pinene, d-limonene (R-(+)-limonene), p-cymene, and camphene (a terpene not present in the initial gas mixture) increased, indicating a chemical transformation of β-pinene to these species. A similar pattern of decreasing mole fraction was observed in α-pinene where growth of d-limonene, p-cymene, and camphene has been observed in treated gas cylinders prepared with a mixture of just α-pinene and benzene as the internal standard. The current research discusses the testing of other cylinders and treatments for the potential of long-term stability of monoterpenes in a gas mixture. In this current study, a similar pattern of decreasing mole fraction, although somewhat improved short-term stability, was observed for β-pinene and α-pinene, with growth of d-limonene, p-cymene, and camphene, in nickel-plated carbon steel cylinders. β-Pinene and α-pinene showed excellent stability at over 6 months in aluminum cylinders treated with a different process (Experis) than used in the original study.