Determination of Nonylphenol in Crude Oils and Petroleum Products by Liquid Chromatography–Mass Spectrometry: Implications for Sustainable Petroleum Refining

Nonylphenols (NPs), widely used as emulsifiers in petroleum production and refining, are compounds of environmental concern, with endocrine-disrupting effects. They can be released during oil extraction and processing, carried into petroleum products, and subsequently emitted during downstream applications such as combustion. Despite these potential pathways, information on their occurrence in petroleum streams remains limited, partly due to the lack of reliable methods for measuring NPs in complex petroleum matrices. In this study, we developed an analytical method combining normal-phase chromatography (NPC), solid-phase extraction (SPE), and liquid chromatography–Orbitrap high-resolution mass spectrometry (LC–Orbitrap-HRMS) for NP determination in crude oils and petroleum products. NPC was performed using alumina (5% water deactivation) as the stationary phase. The column was eluted sequentially with n-hexane, n-hexane/dichloromethane (4:1 and 1:1, v/v), dichloromethane, and dichloromethane/methanol (2:1, v/v). The first three fractions were discarded, and the remaining two fractions were combined and further purified using a C18 SPE cartridge to analysis. The method showed high recovery (82.8 ± 2.6%) and a low detection limit (1.0 ng/g) in crude oil. Application revealed widespread occurrence of NPs, with concentrations up to 784.4 ng/g in crude oils and up to 439.1 ng/g in refined fuels, indicating that these compounds can persist through refining and may be released during downstream use. These results demonstrate that the method is suitable for the routine monitoring of NPs in petroleum-related samples and provide a practical tool for supporting sustainable refining practices and improved environmental management in the upstream oil and gas sector.