Characterization of Pyrolysis Oils Using a Combination of GC×GC/TOFMS and GC/HRMS Analysis: The Impact of Data Processing Parameters

Human population growth and increasing transportation demands have led to rising global tire consumption and associated waste. In response, various material and energy recovery strategies, such as pyrolysis, have been developed to produce high-value-added products such as pyrolysis oils, which can be reused as materials or fuels. However, these oils often contain heteroatom-containing compounds (e.g., nitrogen, oxygen, sulfur) that can hinder their valorization and must therefore be identified and removed. To characterize heteroatomic compounds present in distillation fractions of pyrolysis oils, GC×GC/TOFMS and GC/HRMS were employed. For non-target analysis, data processing parameters were optimized using a Central Composite Design (CCD). The most influential parameters for GC×GC/TOFMS were the minimum number of mass-to-charge ratio (m/z) signals kept in the deconvoluted spectra (minimum stick count) and peak signal-to-noise ratio (S/N), while for GC/HRMS, optimization focused on the m/z S/N threshold, peak S/N, and total ion current (TIC). Under optimal conditions, 129 and 92 heteroatomic compounds were identified via GC×GC/TOFMS and GC/HRMS, respectively, within a single distillation fraction, with 57 compounds identified using both techniques. Notably, GC×GC/TOFMS exclusively identified 72 compounds, while there were only 5 unique to GC/HRMS. These results highlight the effectiveness of GC×GC/TOFMS in characterizing heteroatomic compounds in complex mixtures, while also underlining the complementary value of GC/HRMS.