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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. [ABSTRACT FROM AUTHOR]

Recent work has quantified the delay times in measurements of volatile organic compounds (VOCs) caused by the partitioning between the gas phase and the surfaces of the inlet tubing and instrument itself. In this study we quantify wall partitioning effects on time responses and transmission of multifunctional, semivolatile, and intermediate-volatility organic compounds (S/IVOCs) with saturation concentrations (C∗) between 10 0 and 10 4 µgm-3. The instrument delays of several chemical ionization mass spectrometer (CIMS) instruments increase with decreasing C∗ , ranging from seconds to tens of minutes, except for the NO3- CIMS where it is always on the order of seconds. Six different tubing materials were tested. Teflon, including PFA, FEP, and conductive PFA, performs better than metals and Nafion in terms of both delay time and transmission efficiency. Analogous to instrument responses, tubing delays increase as C∗ decreases, from less than a minute to >100 min. The delays caused by Teflon tubing vs. C∗ can be modeled using the simple chromatography model of Pagonis et al. (2017). The model can be used to estimate the equivalent absorbing mass concentration (Cw) of each material, and to estimate delays under different flow rates and tubing dimensions. We also include time delay measurements from a series of small polar organic and inorganic analytes in PFA tubing measured by CIMS. Small polar molecules behave differently than larger organic ones, with their delays being predicted by their Henry's law constants instead of their C∗ , suggesting the dominance of partitioning to small amounts of water on sampling surfaces as a result of their polarity and acidity properties. PFA tubing has the best performance for gas-only sampling, while conductive PFA appears very promising for sampling S/IVOCs and particles simultaneously. The observed delays and low transmission both affect the quality of gas quantification, especially when no direct calibration is available. Improvements in sampling and instrument response are needed for fast atmospheric measurements of a wide range of S/IVOCs (e.g., by aircraft or for eddy covariance). These methods and results are also useful for more general characterization of surface–gas interactions. [ABSTRACT FROM AUTHOR]

Losses of gas-phase compounds or delays on their transfer through tubing are important for atmospheric measurements and also provide a method to characterize and quantify gas–surface interactions. Here we expand recent results by comparing different types of Teflon and other polymer tubing, as well as glass, uncoated and coated stainless steel and aluminum, and other tubing materials by measuring the response to step increases and decreases in organic compound concentrations. All polymeric tubings showed absorptive partitioning behavior with no dependence on humidity or concentration, with PFA Teflon tubing performing best in our tests. Glass and uncoated and coated metal tubing showed very different phenomenology due to adsorptive partitioning to a finite number of surface sites. Strong dependencies on compound concentration, mixture composition, functional groups, humidity, and memory effects were observed for glass and uncoated and coated metals, which (except for Silonite-coated stainless steel) also always caused longer delays than Teflon for the compounds and concentrations tested. Delays for glass and uncoated and coated metal tubing were exacerbated at low relative humidity but reduced for RH >20 %. We find that conductive PFA and Silonite tubing perform best among the materials tested for gas-plus-particle sampling lines, combining reduced gas-phase delays with good particle transmission. [ABSTRACT FROM AUTHOR]