Forensic Investigations of Diesel Oil Spills in the Environment Using Comprehensive Two-Dimensional Gas...

Forensic investigations of oil spills aim to find the responsible source(s) of the spill. Oil weathering processes change the chemical composition of the spilled oil and make the matching of oil spill samples to potential sources difficult. Diesel oil spill cases are more challenging, because biomarkers recalcitrant to long-term weathering are absent. We developed and tested a new method for the analysis and matching of diesel oil spills using two-dimensional gas chromatography-high resolution mass spectrometry (GC × GC - HRMS) and 2D-CHEMSIC (2-Dimensional CHEMometric analysis of Selected Ion Chromatograms), an extension of the CHEMSIC method to GC × GC data. The 2D-CHEMSIC performs pixel-based analysis using chemometrics on concatenated sections of 2D extracted ion chromatograms to assess the overall chemical variability of the samples, with potential applications for matching spill-source pairs in forensic investigations. The method was tested on samples from a number of diesel oil spill cases, (i) distinguishing chemically similar source diesels, (ii) investigating weathering effects on spill samples to determine type and degree of weathering, and (iii) improving the matching of diesel oil spills affected by weathering. Positive matches for spill-source pairs were identified after excluding the signals from the hydrocarbons most susceptible to evaporation, and photo-oxidized spills were also matched due to the presence of unaffected hydrocarbons. Forensic diagnostics obtained by the 2D-CHEMSIC were validated by the conventional CEN-Tr method.