Parallel quantitation of salt dioctyl sodium sulfosuccinate (DOSS) and fingerprinting analysis of dispersed oil in aqueous samples.

In many jurisdictions, dispersants are included in contingency plans as a viable countermeasure that can help reduce the overall environmental impact of marine oil spills. When used, it is imperative to monitor the progression of dispersant and oil to assess their environmental fate and behaviour. Amphiphilic salt dioctyl sodium sulfosuccinate (DOSS) is the major effective component of the most commonly available dispersants, such as Corexit® EC9500A. Without proper sample preparation, dispersed oil in water samples could interfere with the accurate analysis of DOSS and easily contaminate the LC-MS system. In this work, solid phase extraction (SPE) weak anion exchange (WAX) cartridges were used to separate oil and DOSS in aqueous samples. DOSS was accurately determined by liquid chromatography coupled with a high resolution Orbitrap mass spectrometer (LC-HRMS). Oil fingerprinting analysis was conducted and total petroleum hydrocarbons (TPHs), polycyclic aromatic hydrocarbons (PAHs), and petroleum biomarkers were determined by gas chromatography-flame ionization detection (GC-FID) and mass spectrometry (GC-MS). This SPE-LC/GC-MS method was used for the analysis of oil-dispersant water samples containing a mixture of Corexit® EC9500A and a selection of crude oils and refined petroleum products. Nearly a 100% DOSS recovery was obtained for various oil-surfactant conditions. Parallel quantitation of oils with dispersants was achieved using this method. A portion of the TPH loss was possibly attributed to oil retained by the SPE column. Chemical fingerprints and diagnostic ratios of target compounds in recovered dispersed oil overall remain unchanged compared with those of all studied oils.

Differentiation of weathered chemically dispersed oil from weathered crude oil.

Oil fingerprinting is a crucial technology to trace the sources and behaviors of spilled oil. The use of dispersants enhances the stay of dispersed oil in a water column and changes the important properties of spilled oil. In case of fingerprinting of dispersed oil driven by dispersants, the fate and behaviors of biomarkers may be affected by the application of dispersants. Limited studies have investigated the statistical difference between fingerprinting of dispersed oil and non-dispersed oil using biomarkers, and the possible influence of the differences, if present. This study applied several principal component analyses (PCA) to differentiate weathered chemically dispersed oil from weathered crude (non-dispersed) oil using 103 diagnostic ratios of the same type of biomarkers and those of two types of biomarkers as input data. It showed that weathered chemically dispersed oil (CDO) can be differentiated from weathered crude oil (WCO) using specific diagnostic ratios that are affected by weathering. PCA analyses indicated the effects of the application of dispersants and weathering duration on weathering of biomarkers in CDO and WCO.

Discrimination and classification of extra virgin olive oil using a chemometric approach based on TMS-4,4'-desmetylsterols GC(FID) fingerprints of edible vegetable oils.

A single out-line HPLC-GC (FID) analytical method is applied to acquire the chromatographic fingerprint characteristic of the TMS-4,4'-desmetylsterol derivative fraction of several marketed edible vegetable oils in order to identify and discriminate the most valuable extra-virgin olive oils from the other vegetal oils (canola, corn, grape seed, linseed, olive pomace, peanut, rapeseed, soybean, sesame, seeds (non-specified composition but usually a blend of corn and sunflower) and sunflower). The natural structure of the preprocessed data undergoes a preliminary exploration using principal component analysis and heat map-based cluster analysis. A partial least squares-discriminant model is first trained from 53 oil samples (only 3 latent variables) and externally validated from 18 test oil samples. No classification errors are found and all the test samples are correctly classified. Additional classification models are also built in order to discriminate among vegetables-oil families and excellent results have been also achieved.

Chronic oiling of marine birds in California by natural petroleum seeps, shipwrecks, and other sources.

We assessed temporal and spatial patterns of chronic oiling of seabirds in California during 2005-2010, using data on: (1) live oiled birds reported to the Oiled Wildlife Care Network (OWCN) from throughout the state, and (2) dead oiled birds found during systematic monthly beached-bird surveys in central California. A mean of 245 (± 141 SD) live miscellaneous oiled birds (not associated with known oil spills) were reported to the OWCN per year, and 0.1 oiled dead birds km(-1) per month were found on beach surveys in central California. Chemical fingerprinting of oiled feathers from a subset of these birds (n=101) indicated that 89% of samples tested were likely from natural petroleum seeps off southern and central California. There was a pronounced peak during late winter in the number of oiled birds reported in southern California, which we theorize may be related to large storm waves disturbing underwater seeps.

Assessment of photochemical processes in marine oil spill fingerprinting.

Understanding weathering processes plays a critical role in oil spill forensics, which is based on the comparison of the distributions of selected compounds assumed to be recalcitrant and/or have consistent weathering transformations. Yet, these assumptions are based on limited laboratory and oil-spill studies. With access to additional sites that have been oiled by different types of oils and exposures, there is a great opportunity to expand on our knowledge about these transformations. Here, we demonstrate the effects of photooxidation on the overall composition of spilled oils caused by natural and simulated sunlight, and particularly on the often used polycyclic aromatic hydrocarbons (PAHs) and the biomarker triaromatic steranes (TAS). Both laboratory and field data from oil released from the Macondo well oil following the Deepwater Horizon disaster (2010), and heavy fuel-oil from the Prestige tanker spill (2002) have been obtained to improve the data interpretation of the typical fingerprinting methodology.