DOI: 10.6084/m9.figshare.27936252
title: Application of Bicadinane Biomarkers in Oil Spill Fingerprinting Studies Involving Southeast Asian Oils

description: Bicadinanes (C<sub>30</sub>H<sub>52</sub>) are a family of non-hopanoid, pentacyclic triterpane biomarkers whose utility in oil spill fingerprinting has, to our knowledge, not been previously explored. Owing to their derivation from <i>Diptocarpaceae</i> tree (dammar) resin, crude oils containing bicadinanes are geographically and temporally limited to Southeast Asian oils sourced from Oligocene or younger strata. Bicadinane-bearing oils produced from Southeast Asia, however, are shipped worldwide and thereby bicadinanes may be present in oils spilled both within and outside of Southeast Asia. Bicadinanes’ relative or absolute concentrations are readily measured using a standard oil spill identification analytical method (GC/MS-SIM) that routinely targets more conventional biomarkers (triterpanes, steranes, and aromatic steroids). In this study, the absolute concentrations of four bicadinane isomers (W, T, T1 and R) were measured in 42 tarballs collected from shorelines along the southern extent of the Straits of Singapore, an area with very high oil tanker and cargo vessel traffic. The tarballs’ specific origins are unknown but safely presumed to be derived from various unknown oil spills and/or oil seeps in the region. GC/FID was used to classify the tarball oils’ level of biodegradation (Levels 1, 4, and 6). The absolute concentration of total bicadinanes ranged from 7.5 to 208 µg/g and varied widely and independent of the level of biodegradation. The relative concentrations among the four bicadinane isomers (T &gt; W&gt;T1∼R; on average, 56% &gt; 20% &gt; 12% each) also showed no obvious or statistically significant trend with biodegradation for the samples studied. Thus, variations in both total and individual isomer concentrations are attributable to the tarballs’ multiple crude oil sources spilled or seeped in the study area. Diagnostic ratios (DRs) are critical components in oil spill identification protocols. A newly proposed DR of (W + T)/hopane varied widely (0.01 to 0.54) and also independently from the more conventionally used DR of 18α(H)-oleanane/hopane (oleanane/hopane; 0.04 to 0.42). Two newly proposed DRs among the four bicadinane isomers, W/T and T/(T1 + R), also varied among the 42 tarball oils studied (0.27 to 0.45 and 1.4 to 3.2, respectively). The variation in the (W + T)/hopane, oleanane/hopane, W/T and T/(T1 + R) ratios was unrelated to the level of biodegradation for the samples studied and exceeded the statistical criteria used in the CEN (2012) oil spill identification protocol (i.e., 95% repeatability limit) and thereby demonstrates these DRs’ utility in comparing and distinguishing among different crude oils containing bicadinanes – and, of course, between crude oils that do and do not contain bicadinanes. The additional specificity offered by bicadinanes argues they should be included as target analytes in oil spill identification studies throughout Southeast Asia or in other areas where Southeast Asian oils are believed to be present (shipped, handled, or used).