Reassessment of the hydrocarbons in Prince William Sound and the Gulf of Alaska : identifying the source using partial least squares

Since the Exxon Valdez oil spill in Prince William Sound, Alaska there has been much discussion regarding the clean-up and long term fate of the oil. There has also been debate regarding the origin of the background hydrocarbons present within Prince William Sound (PWS) and the Gulf of Alaska (GoA). There is evidence that background (pre-spill) hydrocarbons may come from either nearby coal deposits or from natural oil seeps and eroding source rocks in the region. This paper presented a study in which the multivariate statistical methodology of the Partial Least Squares (PLS) was used to reassess the percentage contribution of coal, seep oil, shales and rivers to the hydrocarbon loading in the GoA. Data was provided by researchers at the National Ocean and Atmospheric Administration (NOAA) and the Bowdoin College, for Exxon. The data was analysed using selected sites as sources in order to develop signatures. The signatures were based on 40 and 136 compounds respectively, including the polyaromatic hydrocarbon (PAH) and terpane biomarkers from the Exxon data. The key components describing the sources were fitted to the data for other sites around the GoA to determine the proportion of the variability described by each source. The large complex datasets can be used to develop complex fingerprints for sources rather than using relatively simplistic ratios between selected compounds. The results indicate that 30 per cent of the signature is common between each source and that the small PAHs are the best diagnostic compounds in the model for the oil signature and the large PAHs are good for coal. Naphthalene, methyl and dimethyl naphthalene are the best markers for the seep oil signature. For the pre-spill background, coals and shales are best defined by the larger PAHs such as perylene and benzo(ghi)perylene. In general, the average partitioning between the two sources across all the sampling sites within the region indicated that 53 per cent is attributable to the Exxon Valdez oil and 47 per cent to the pre-spill background, but significant variation can be seen in the wide geographic area. It was concluded that more studies are needed to analyse pure source materials to provide a good signature for each. 12 refs., 2 tabs., 6 figs