Abstract. Chemical ionization mass spectrometry (CIMS) techniques have become
prominent methods for sampling trace gases of relatively low volatility.
Such gases are often referred to as being “sticky”, i.e., having
measurement artifacts due to interactions between analyte molecules and
instrument walls, given their tendency to interact with wall surfaces via
absorption or adsorption processes. These surface interactions can impact
the precision, accuracy, and detection limits of the measurements. We
introduce a low-pressure ion–molecule reaction (IMR) region primarily built
for performing iodide-adduct ionization, though other adduct ionization
schemes could be employed. The design goals were to improve upon previous
low-pressure IMR versions by reducing impacts of wall interactions at low
pressure while maintaining sufficient ion–molecule reaction times. Chamber
measurements demonstrate that the IMR delay times (i.e., magnitude of wall
interactions) for a range of organic molecules spanning 5 orders of
magnitude in volatility are 3 to 10 times lower in the new IMR compared to
previous versions. Despite these improvements, wall interactions are still
present and need to be understood. To that end, we also introduce a
conceptual framework for considering instrument wall interactions and a
measurement protocol to accurately capture the time dependence of analyte
concentrations. This protocol uses short-duration, high-frequency
measurements of the total background (i.e., fast zeros) during ambient
measurements as well as during calibration factor determinations. This
framework and associated terminology applies to any instrument and
ionization technique that samples compounds susceptible to wall
interactions.