Groundwater contamination source identification is challenging due to delayed detection and changes in fingerprints during transport. In this study, multiple methods were combined to characterize the sources of petroleum derivatives in groundwater near a subway station, where petroleum derivatives, including benzene, toluene, ethylbenzene, and xylene (BTEX), have been detected for over two decades. The techniques used included hydrochemistry, oil fingerprinting, compound specific C and H isotopes, and multivariate statistical and temporal trend analysis. An integrated interpretation differentiated two contamination zones. Zone 1, near the station, showed older contamination from middle distillates, based on low total petroleum hydrocarbon levels compared to the previously high concentrations, decreasing trends of BTEX, high mole fractions of xylene, and the presence of heavier hydrocarbons. Conversely, Zone 2, to the south, revealed high BTEX concentrations, high mole fractions of benzene, and lighter hydrocarbons, indicating more recent contamination from light distillates. Anaerobic biodegradation was revealed to occur in Zone 1 based on principal component analysis (PCA), δ13C and δ2H of BTEX, and increasing benzene/toluene but decreasing toluene/ethylbenzene with time. Meanwhile, benzene degradation appeared recalcitrant in Zone 2. This study demonstrated that oil fingerprints and mole fractions are valuable in distinguishing sources, while PCA and isotope analysis help assess contaminant fate in groundwater when access to potential sources was limited. Combined application of these techniques, along with site history, is expected to differentiate contamination sources in urban groundwater with multiple potential sources across times and locations.
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