Multidimensional gas chromatography in combination with accurate mass, tandem mass spectrometry, and element-specific detection for identification of sulfur compounds in tobacco smoke

Highlights

• A method for identification of sulfur compounds in tobacco smoke is described.

• The method is based on LVI and selectable ¹D/²D GC–SCD/Q-TOF-MS with EI and PCI.

• Sequential heart-cuts of the 28 sulfur fractions were used with three detection modes.

• MS/MS of protonated molecule proved to be a useful tool for structure elucidation.

• Forty-one sulfur compounds were determined in the range of 10–740 ng mg TPM⁻¹.

Abstracts

A method is developed for identification of sulfur compounds in tobacco smoke extract. The method is based on large volume injection (LVI) of 10 μL of tobacco smoke extract followed by selectable one-dimensional (¹D) or two-dimensional (²D) gas chromatography (GC) coupled to a hybrid quadrupole time-of-flight mass spectrometer (Q-TOF-MS) using electron ionization (EI) and positive chemical ionization (PCI), with parallel sulfur chemiluminescence detection (SCD). In order to identify each individual sulfur compound, sequential heart-cuts of 28 sulfur fractions from ¹D GC to ²D GC were performed with the three MS detection modes (SCD/EI-TOF-MS, SCD/PCI–TOF-MS, and SCD/PCI–Q-TOF-MS). Thirty sulfur compounds were positively identified by MS library search, linear retention indices (LRI), molecular mass determination using PCI accurate mass spectra, formula calculation using EI and PCI accurate mass spectra, and structure elucidation using collision activated dissociation (CAD) of the protonated molecule. Additionally, 11 molecular formulas were obtained for unknown sulfur compounds. The determined values of the identified and unknown sulfur compounds were in the range of 10–740 ng mg total particulate matter (TPM) (RSD: 1.2–12%, n = 3).