Biomarkers Profile of the Mysterious 2019 Oil Spill on the Northeast Coast of Brazil and Discrimination from Unreported Events

Abstract

In 2019, large amounts of oil reached the northeast coast of Brazil, causing damage to the environment and the local economy, especially in the state of Pernambuco. In order to correlate with possible sources, investigation was made of the geochemical biomarkers of the oils using "gold standard"forensic protocols from the European Committee for Standardization (CEN). The biomarkers study was improved by using gas chromatography-tandem mass spectrometry (GC-MS/MS), rather than the standard protocol that suggests use of the selected ion monitoring (SIM) method. Analysis was made of thirteen oil samples from the Pernambuco coast, in order to identify their degrees of similarity and the possible presence of oils from unreported spills. The use of eighteen diagnostic ratios and multivariate analysis revealed a cluster formed by eleven samples with biomarker distributions typical of oil from the 2019 spill. However, two samples had anomalous fingerprints, especially due to the absence of the 18α(H)-oleanane and 18β(H)-oleanane isomers. Both the CEN protocol applied for the classical biomarkers and a comprehensive Fourier transform mass spectrometry (FT-MS) analysis of polar compounds confirmed the dissimilarities between the samples. The findings suggested that these two oils could have originated from an event unrelated to the mysterious 2019 spill.