Advances in offline approaches for chemically speciated measurements of trace gas-phase organic compounds via adsorbent tubes in an integrated sampling-to-analysis system

Gas-phase organic compounds across a range of volatilities, including volatile organic compounds (VOCs), are key components of outdoor air, indoor spaces, and a variety of other anthropogenic and biogenic systems. The collection of offline samples on adsorbent-packed tubes for analysis on laboratory instrumentation has been in use for decades, but with limited sensitivities and compound coverage. We present and evaluate our integrated sampling-to-analysis system that enables offline detailed chemical characterization of multi-faceted organic mixtures at trace concentrations. Its capabilities extend across a diverse variety of VOCs with different molecular features, as well as intermediate and semivolatile organic compounds (I/SVOCs). Samples can be collected manually or via automated devices that have been applied in chamber, field, and aircraft platforms. The laboratory instrumentation can be coupled to both a high resolution mass spectrometer (MS) and a traditional quadrupole MS, though performance metrics presented in this study are determined via the traditional MS. We demonstrate capabilities for detailed chemical characterization and routine performance for a wide range of compound functionalities at sub-part per trillion (ppt) concentrations, and as low as <100 parts per quadrillion (ppq), yielding 3300 observed unique compound peaks in a single indoor air sample. These limits of detection and compound coverage were accomplished through a holistic optimization of the entire system and lifecycle of adsorbent tubes. We present our best practices for all aspects of tube production, handling, sampling, and analysis, and an examination of commercially-available materials and our custom adsorbent tubes using a diverse mix of VOC, IVOC, and SVOC standards, including difficult to measure analytes across a range of polarities and functionalities. In many aspects, the commercially-available materials and tube conditioners tested were insufficient for achieving low-ppt measurements.