Development of an In Situ Dual-Channel Thermal Desorption Gas Chromatography Instrument for Consistent Quantification of Volatile, Intermediate Volatility and Semivolatile Organic Compounds

Abstract

Abstract. Aerosols are a source of great uncertainty in radiative forcing predictions and have poorly understood health impacts. Most aerosol mass is formed in the atmosphere from reactive gas phase organic precursors, forming secondary organic aerosol (SOA). Semivolatile organic compounds (SVOCs) (effective saturation concentration, C*, of 10−1–103 μg m−3) comprise a large fraction of organic aerosol, while intermediate volatility organic compounds (IVOCs) (C* of 103–106 μg m−3) and volatile organic compounds (VOCs) (C* ≥ 106 μg m−3) are gas phase precursors to SOA and ozone. The Comprehensive Thermal Desorption Aerosol Gas Chromatograph (cTAG) is the first single instrument simultaneously quantitative for a broad range of compound-specific VOCs, IVOCs and SVOCs. cTAG is a two-channel instrument which measures concentrations of C5–C16 alkane equivalent volatility VOCs and IVOCs on one channel and C14–C32 SVOCs on the other coupled to a single High Resolution Time of Flight Mass Spectrometer, achieving consistent quantification across 15 orders of magnitude of vapor pressure. cTAG obtains concentrations hourly and gas–particle partitioning for SVOCs bihourly, enabling observation of the evolution of these species through oxidation and partitioning into the particle phase. Online derivatization for the SVOC channel enables detection of more polar and oxidized species. In this work we present design details and data evaluating key parameters of instrument performance such as I/VOC collector design optimization, linearity and reproducibility of calibration curves obtained using a custom liquid evaporation system for I/VOCs and the effect of an ozone removal filter on instrument performance. Example timelines of precursors with secondary products are shown and analysis of a subset of compounds detectable by cTAG demonstrates some of the analytical possibilities with this instrument.

Ground-based Investigation of HO<sub>x</sub> and Ozone Chemistry in Biomass Burning Plumes in Rural Idaho

“…Onboard the minAML, NO2 was measured with a CAPS monitor and VOCs with the Berkeley Comprehensive Thermal Desorption Aerosol Gas Chromatograph (cTAG) (Wernis et al, 2021). cTAG measures concentrations of VOCs, intermediate volatility organic compounds and semi-volatile organic compounds spanning an alkane-equivalent volatility range from C5 to C30 every hour via pre-concentration followed by thermal desorption and gas chromatography-time-of-flight mass spectrometry (GC-TOFMS).…”