Enhanced analysis of weathered crude oils by gas chromatography-flame ionization detection, gas chromatography-mass spectrometry diagnostic ratios, and multivariate statistics.

Artificially weathered crude oil "spill" samples were matched to unweathered suspect "source" oils through a three-tiered approach as follows: Tier 1 gas chromatography-flame ionization detection (GC/FID), Tier 2 gas chromatography-mass spectrometry (GC/MS) diagnostic ratios, and Tier 3 multivariate statistics. This study served as proof of concept for a promising and new method of crude oil forensics that applies principal component analysis (PCA) and partial least squares discriminant analysis (PLSDA) in tandem with traditional forensic oil fingerprinting tools to confer additional confidence in challenging oil spill cases. In this study, weathering resulted in physical and chemical changes to the spilled oils, thereby decreasing the reliability of GC/FID and GC/MS diagnostic ratios in source attribution. The shortcomings of these traditional methods were overcome by applying multivariate statistical tools that enabled accurate characterization of the crude oil spill samples in an efficient and defensible manner.

Tiered approach to long-term weathered lubricating oil analysis: GC/FID, GC/MS diagnostic ratios, and multivariate statistics.

Frequent small-scale environmental releases of lubricating (lube) oils have deleterious effects on aquatic ecosystems. In the event of a spill, oil fingerprinting is critical to source attribution, clean-up procedures, and liability assignment. Oil forensic investigations are particularly challenging when oils are weathered over an extended period of time, as a large number of biomarkers become lost and the chemical composition changes significantly from its source. This study simulated an environmental case in which long-term weathered lube oil "spill" samples were matched to unweathered suspect "source" oils. While traditional oil fingerprinting techniques including GC/FID and GC/MS diagnostic ratios were insufficient for reliably attributing the source, a comprehensive and systematically tiered approach proved successful. The proposed methodology featured three tiers: Tier 1 GC/FID, Tier 2 GC/MS diagnostic ratios, and Tier 3 multivariate statistics. This novel approach provided environmental chemists with a powerful tool for dealing with an otherwise extremely challenging lube oil forensic investigation.