Extended characterization of petroleum aromatics using off-line LC-GC-MS

Characterization of crude oil remains a challenge for analytical chemists. With the development of multi-dimensional chromatography and high-resolution mass spectrometry, an impressive number of compounds can be identified in a single sample. However, the large diversity in structure and abundance makes it difficult to obtain full compound coverage. Sample preparation methods such as solid-phase extraction and SARA-type separations are used to fractionate oil into compound classes. However, the molecular diversity within each fraction is still highly complex. Thus, in the routine analysis, only a small part of the chemical space is typically characterized. Obtaining a more detailed composition of crude oil is important for production, processing and environmental aspects. We have developed a high-resolution fractionation method for isolation and preconcentration of trace aromatics, including oxygenated and nitrogen-containing species. The method is based on semi-preparative liquid chromatography. This yields high selectivity and efficiency with separation based on aromaticity, ring size and connectivity. By the separation of the more abundant aromatics, i.e. , monoaromatics and naphthalenes, trace species were isolated and enriched. This enabled the identification of features not detectable by routine methods. We demonstrate the applicability by fractionation and subsequent GC-MS analysis of 14 crude oils sourced from the North Sea. The number of tentatively identified compounds increased by approximately 60 to 150% compared to solid-phase extraction and GC × GC-MS. Furthermore, the method was used to successfully identify an extended set of heteroatom-containing aromatics ( e.g. , amines, ketones). The method is not intended to replace traditional sample preparation techniques or multi-dimensional chromatography but acts as a complementary tool. An in-depth comparison to routine characterization techniques is presented concerning advantages and disadvantages.