Do distributions of diamondoid hydrocarbons accumulated in oil-contaminated fish tissues help to identify the sources of oil?

Identifying the sources of environmental oil contamination can be challenging, especially for oil in motile organisms such as fish. Lipophilic hydrocarbons from oil can bioaccumulate in fish adipose tissue and potentially provide a forensic "fingerprint" of the original oil. Herein, diamondoid hydrocarbon distributions were employed to provide such fingerprints. Indices produced from diamondoids were used to compare extracts from fish adipose tissues and the crude and fuel oils to which the fish were exposed under laboratory conditions. A suite of 20 diamondoids was found to have bioaccumulated in the dietary-exposed fish. Cross-plots of indices between fish and exposure oils were close to the ideal 1:1 relationship. Comparisons with diamondoid distributions of non-exposure oils produced overall, but not exclusively, weaker correlations. Linear Discriminatory Analysis on a combined set of 15 diamondoid and bicyclane molecular ratios was able to identify the exposure oils, so a use of both compound classes is preferable.

Fish Fingerprinting: Identifying Crude Oil Pollutants using Bicyclic Sesquiterpanes (Bicyclanes) in the Tissues of Exposed Fish.

In the present study, we investigated the possibility of identifying the source oils of exposed fish using ratios of bicyclic sesquiterpane (bicyclane) chemical biomarkers. In the event of an oil spill, identification of source oil(s) for assessment, or for litigation purposes, typically uses diagnostic ratios of chemical biomarkers to produce characteristic oil "fingerprints." Although this has been applied in identifying oil residues in sediments, water, and sessile filtering organisms, so far as we are aware this has never been successfully demonstrated for oil-exposed fish. In a 35-day laboratory trial, juvenile Lates calcarifer (barramundi or Asian seabass) were exposed, via the diet (1% w/w), to either a heavy fuel oil or to Montara, an Australian medium crude oil. Two-dimensional gas chromatography with high-resolution mass spectrometry and gas chromatography-mass spectrometry were then used to measure selected ratios of the bicyclanes to examine whether the ratios were statistically reproducibly conserved in the fish tissues. Six diagnostic bicyclane ratios showed high correlation (r2 > 0.98) with those of each of the two source oils. A linear discriminatory analysis model showed that nine different petroleum products could be reproducibly discriminated using these bicyclane ratios. The model was then used to correctly identify the bicyclane profiles of each of the two exposure oils in the adipose tissue extracts of each of the 18 fish fed oil-enriched diets. From our initial study, bicyclane biomarkers appear to show good potential for providing reliable forensic fingerprints of the sources of oil contamination of exposed fish. Further research is needed to investigate the minimum exposure times required for bicyclane bioaccumulation to achieve detectable concentrations in fish adipose tissues and to determine bicyclane depuration rates once exposure to oil has ceased. Environ Toxicol Chem 2023;42:7-18. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Risk Assessment of Pesticide Mixtures in Australian Rivers Discharging to the Great Barrier Reef.

Rivers discharging to the Great Barrier Reef carry complex pesticide mixtures. Here we present a first comprehensive ecotoxicological risk assessment using species sensitivity distributions (SSDs), explore how risk changes with time and land use, and identify the drivers of mixture risks. The analyzed data set comprises 50 different pesticides and pesticide metabolites that were analyzed in 3741 samples from 18 river and creek catchments between 2011 and 2016. Pesticide mixtures were present in 82% of the samples, with a maximum of 23 pesticides and a median of five compounds per sample. Chemical-analytical techniques were insufficiently sensitive for at least seven pesticides (metsulfuron-methyl, terbutryn, imidacloprid, clothianidin, ametryn, prometryn, and thiamethoxam). The classical mixture concepts of concentration addition and independent action were applied to the pesticide SSDs, focusing on environmental threshold values protective for 95% of the species. Both concepts produced almost identical risk estimates. Mixture risk was therefore finally assessed using concentration addition, as the sum of the individual risk quotients. The sum of risk quotients ranges between 0.05 and 122 with a median of 0.66. An ecotoxicological risk (i.e., a sum of individual risk quotients exceeding 1) was indicated in 38.5% of the samples. Sixteen compounds accounted for 99% of the risk, with diuron, imidacloprid, atrazine, metolachlor, and hexazinone being the most important risk drivers. Analysis of land-use patterns in catchment areas showed an association between sugar cane farming and elevated risk levels, driven by the presence of diuron.