The abundance and composition of matrix compounds in fire debris samples undergoing ignitable liquid residue analysis frequently leads to inconclusive results, which can be diminished by applying comprehensive two-dimensional gas chromatography (GC × GC). Method development must be undertaken to fully utilize the potential of GC × GC by maximizing separation space and resolution.. The three main areas to consider for method development are column selection, modulator settings and parameter optimization. Seven column combinations with different stationary phase chemistry, column dimensions and orthogonality were assessed for suitability based on target compound selectivity, retention, resolution, and peak shapes, as well as overall peak capacity and area use. Using Box-Behnken design of experimentation (DoE), the effect of modulator settings such as flow ratio and loop fill capacity were evaluated using carbon loading potential, dilution effect, as well as target peak amplitude and skewing effect. The run parameters explored for parameter optimization were oven programming, inlet pressure (column flow rate), and modulation period. Comparing DoE approaches, Box-Behnken and Doehlert designs assessed sensitivity, selectivity, peak capacity, and wraparound; alongside target peak retention, resolution, and shape evaluation. Certified reference standards and simulated wildfire debris were used for method development and verification, and wildfire debris case samples scrutinized for method validation. The final method employed a low polarity column (5% diphenyl) coupled to a semi-polar column (50% diphenyl) and resulted in an average Separation Number (SN) exceeding 1 in both dimensions after optimization. Separation Numbers of 18.16 for first and 1.46 for second dimension without wraparound for compounds with at least four aromatic rings signified successful separation of all target compounds from varied matrix compositions and allowed for easy visual comparison of extracted ion profiles. Mass spectrometry (MS) was required during validation to differentiate ions where no baseline separation between target compounds and extraneous matrix compounds was possible. The resulting method was evaluated against ASTM E1618 and found to be an ideal routine analysis method providing great resolution of target compounds from interferences and excellent potential for ILR classification within a complex sample matrix.
Keywords: Design of experiment (DoE); Fire Debris; GC × GC-TOFMS; ILR; Multidimensional Analysis; Response surface methodology (RSM).
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