Determination of Geochemically Important Sterols and Triterpenols in Sediments Using Ultrahigh-Performance Liquid Chromatography Tandem Mass Spectrometry (UHPLC-MS/MS)

A fast, sensitive, and selective ultrahigh-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method that is able to quantify geochemical biomarkers in sediment is described. A pool of 10 sterols, which can be used as biomarkers of autochthonous (cholesterol, cholestanol, brassicasterol, ergosterol), allochthonous (stigmasterol, beta-sitosterol, campesterol, and stigmastanol) and anthropogenic (coprostanol and epicoprostanol) organic matter (OM), and three triterpenols (lupeol, alpha-amyrin, and beta-amyrin) were chosen as the analytes. The method showed excellent analytical parameters, and, compared with the traditional GC-MS methods that are commonly applied for the analysis of sterols, this method requires no sample cleanup or derivatization and presents improved values for the LOD and LOQ. UHPLC can separate the diastereoisomers (epicoprostanol, coprostanol, and cholestanol) and the isomers (lupeol, alpha-amyrin, and beta-amyrin). The method was successfully applied for the quantification of the biomarkers, and thus, it was applied to assess the OM sources and the impacts of anthropogenic activities in sediments from different environments, such as Antarctica and other Brazilian systems (Continental Shelf, Sao Sebastiao Channel, and Santos Estuary). Unique profiles of the biomarkers were observed for the contrasting environments, and beta-amyrin and cholesterol were more predominant in the Santos Estuary and Antarctica samples, respectively. The sterol ratios indicated a higher level of sewage contamination in the Santos Estuary.