Simple and cost-effective determination of polychlorinated biphenyls in insulating oils using an ionic liquid-based stationary phase and flow modulated comprehensive two-dimensional gas chromatography with electron capture detection.

In this article we describe a method using flow-modulated comprehensive two-dimensional gas chromatography with electron capture detector (FM-GC×GC-ECD) for the determination of polychlorinated biphenyls (PCBs) in complex transformer oils bypassing the need for sample preparation. A two-fold improvement in method development was attained. First, the solvation parameter model (SPM) was used to guide column selection. A highly cohesive ionic liquid-based phase (low l system constant), namely 1,12-di(tripropylphosphonium)dodecane bis(trifluoromethanesulfonyl)imide, was used in the primary stage leading to negligible retention of interfering aliphatic hydrocarbons, which are eluted in the first upper quadrant of the chromatogram. The resulting separation space was used to resolve the critical class of compounds, namely, PCBs and polyaromatic hydrocarbons. Second, a unique combination of column geometries and phase ratios enabled highly efficient reverse fill/flush flow modulation using very low pressure for auxiliary gas flow. The proof of concept method described herein exhibited linearities ranging from 0.990 to 0.994, limits of quantitation (LOQ) from 2.23 and 6.85 µg mL, precision below 5% relative standard deviation (RSD), and accuracy from 84.2% to 108.9% showcasing the potential of FM-GC×GC for routine analysis.