Fingerprint characteristics of refined oils and their traceability in the groundwater environment

Chemical fingerprinting is essential for identifying the presence and responding to oil spills that frequently contaminate the groundwater environment of refineries. In this study, crude oil and oil products from the atmospheric and vacuum distillation units of a refinery were analyzed by gas chromatography-mass spectrometry (GC-MS) to evaluate their chemical variability before and after refinery. A series of experiments involving evaporation and soil column penetration were conducted to simulate refined oil spilling into groundwater and determine appropriate characteristic ratios (CRs) for principal component analysis (PCA) for oil source identification. The simulated study demonstrated that all products had bell-shaped n-alkane distributions, with dominant peaks that remained unchanged or shifted towards longer chain lengths compared to the source oil. Similarly, naphthalene and dibenzothiophene series remained the main PAH components like the source oil. Ten relatively stable CRs were selected for PCA to identify different oil products through the simulated experiments. The chosen CRs were then utilized to identify the sources for two groundwater oil spills recently occurred, one that occurred in an oil depot area, and another near a continuous catalytic reforming unit in a refinery. This study showed that the components with long-chain n-alkanes (n ≥ C₁₈), pristane, phytane, and phenanthrene and dibenzothiophene series PAHs played an important role in the identification of refined oil products spilling into the groundwater environment. The selected CRs provide an effective tool for rapid and accurate identification of oil spills, especially for newly occurring spills in the groundwater environment, which can aid in developing appropriate response strategies.