&Amp;#173;­non-Targeted VOC Quantification Through the Simultaneous Coupling of an In-Situ Gas Chromatograph to Electron and Chemical Ionization Time-of-Flight Mass Spectrometers

Non-traditional VOC emissions, including emerging pollutants, air toxics, and volatile chemical products (VPCs) span a range of volatilities and molecular structures that impact their reactivity in the atmosphere and eventual fate. However, little is known their source apportionment, temporal behavior, and relative importance to health impacts along with ozone and SOA formation. With the need to characterize these emissions, comprehensive measurement techniques that capture the unexpected but are also highly specific to detail molecular structure and provide compound quantification are needed. The work presented in this study uses chemical ionization (CI) techniques (H3O+, NH4+, NO+, O2+) for the direct detection and quantification of VOCs considered to be hazardous air pollutants (HAPs). With our work, we show that the ionization patterns for these classes of compounds within each ionization scheme can be used to expand these methods to interpret unknown signals in complex environments. This detailed characterization was conducted by coupling in-situ gas chromatography (GC) to the CI-TOF-MS for pre-separation of the complex mixture. Our results show how the speciated data can be used to deconvolve the complexities of chemical ionization detection (including the presence of fragmentation, cluster formation, and mixed ionization schemes e.g. proton transfer, charge transfer, dehydration). To apply these methods to ambient atmospheric measurements we need to reconcile the need for both continuous isomer specific quantification and high time resolution data. To accomplish this, we simultaneously coupled the in-situ GC with both CI and electron ionization (EI) TOF-MS. Resulting in the generation of three data sets (GC-EI, GC-CI, and direct-CI data) that offer continuous GC quantification, universal detection of speciated organics (EI), speciated CI data to constrain interferences, and direct-CI data for high time resolution data. This instrument combination was deployed in Spring 2023 for a 4-week mobile laboratory campaign in a region of southeast Louisiana, US that is dense with petrochemical production and industrial activity, to quantify hazardous air pollutants to gauge exposure for the local population. The combination of the in-situ GC, EI-TOF-MS, PTR-TOF-MS was used to provide highly specific, quantitative data on VOCs considered to be air toxics in the area, while also acquiring high time resolution PTR-TOF data that allowed the characterization of different point sources and their variability over time-of-day and day-of-week.