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AbstractBicadinanes (C30H52) 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 Diptocarpaceae 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 > W>T1∼R; on average, 56% > 20% > 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). [ABSTRACT FROM AUTHOR]

An experiment was designed to address the validity of the prescribed maximum allowable holding-time limit of 14 days when acidified at < 2 pH and maintained at 4°C to prevent significant loss of benzene, toluene, ethyl benzene, and xylenes (BTEX) in preserved water samples. Preservation methods prescribed by the United State Environmental Protection Agency were used as well as adaptions of that procedure to determine stability between 3 and 21 days. Water samples preserved at 4°C and pH of < 2 with hydrochloric acid did not result in unacceptable (> 15%) BTEX losses during the study as defined by procedures and statistical methods described by the American Society for Testing and Materials International. In addition, water samples preserved only with acid (pH < 2) at ambient temperatures (20-27°C) also provided acceptable results during the 21-day study. These results have demonstrated the acceptability of BTEX data derived from water samples exceeding the standard holding-time and/or temperature limits. [ABSTRACT FROM AUTHOR]