Streamlined Untargeted Workflow for Priority and Unknown Pollutant Identification in Industrial Stack Particulate by GC-Orbitrap High Resolution Mass Spectrometry

Emerging Environmental Applications for High Resolution Mass Spectrometry
Oral Presentation

Prepared by A. Fornadel1, N. Warner2, K. Hope3
1 - Thermo Fisher Scientific, 3000 Lakeside Drive,, Suite 116N, Bannockburn,, IL 60015, IL, Bannockburn, United States
2 - Thermo Fisher Scientific, TFS, Hanna-Kunath-Straße 11,, Bremen, Non-U.S., Bremen, Germany
3 - Pacific Rim Laboratories, 19575 55 A Ave,, 55 A Ave, Surry, Non-U.S., BC V3S 8P8, Can, Canada


Contact Information: [email protected]; (443) 346-0728

ABSTRACT

The study investigates the chemical composition of particulate matter collected from industrial stack using a non-target analysis workflow combined with GC-high resolution accurate mass (HRAM) analysis. Monitoring atmospheric emissions from industrial activity is crucial for maintaining safe air quality and ensuring compliance with environmental regulations. The combustion of fuel in industrial processes produces various volatile and semi-volatile pollutants, including polycyclic hydrocarbons (PAHs) and polychlorinated dibenzodioxins/furans (PCDD/Fs), which are regulated internationally.
The particulate matter was collected from a waste incinerator stack using a sampling train as described in U.S. EPA Method 23. Samples were extracted with toluene using Soxhlet extraction, followed by sample cleanup using a tandem acid silica-carbon column. The extracts were then analyzed using a Thermo Scientific Orbitrap Exploris GC with full scan data acquisition at a resolution setting of 60,000. Both electron impact (EI) and positive chemical ionization (PCI) were used in the analysis.
Through the non-target analysis workflow in Compound Discoverer, the deconvolution of sample mass spectra was performed, followed by cross-referencing against nominal and in-house HRAM libraries. Several PAHs and chlorinated analogues of PAHs were identified with high confidence, supported by HRAM library matches and low mass error. The system's ability to switch rapidly from EI to PCI without venting the mass spectrometer allowed for the molecular ion confirmation of chlorophenanthrene and chloroanthracene.
Persistent organic pollutants (POPs) such as Polychlorinated biphenyls and brominated dibenzofurans were identified in the stack particulate. The isotopic pattern scoring combined with molecular ion confirmation provided further confidence in identifying these pollutants. The study's findings highlight the utility of GC-Orbitrap mass spectrometry for detecting persistent organic pollutants in emission stack samples, ensuring accurate monitoring and identification of harmful compounds in industrial emissions.