Geochemistry and fluxes of hydrocarbons to the Beaufort Sea shelf: A multivariate comparison of fluvial inputs and coastal erosion of peat using principal components analysis

Abstract

The allochthonous inputs of hydrocarbon to the Canadian Beaufort Shelf were studied by applying principal components analysis (PCA) to well-validated and rigorously blank-corrected samples. Incorporation of a wide range of perdeuterated n-alkanes and PAH into the analysis scheme ensured that only reliably quantified variables were used to interpret the hydrocarbon geochemistry. Application of PCA to Mackenzie River samples demonstrated a homogeneous system, from which we infer coupling or equilibrium between the river particulate hydrocarbons and the dissolved fraction. Particulate (particle size > 0.7 μm) hydrocarbon flux from the Mackenzie River is by far the most important terrestrially derived source of hydrocarbons to the Beaufort Sea. The Mackenzie River particulates have a distinct n-alkane signature which can be used to identify the riverine influence on the hydrocarbon geochemistry of the Beaufort Sea shelf. Based on one year's data, the flux of total alkanes is 440 ± 94 tonne/ a, and PAH is 49 ± 8 tonne/ a (uncertainties are one standard deviation of the sampling and analytical variation). The particulate flux exceeds the accompanying dissolved hydrocarbon flux by two orders of magnitude and has a strong seasonal cycle: winter contributes less than an estimated 0.6% of total annual flux. Deltaic silt from the western Mackenzie delta and the smaller amounts of detritus from coastal erosion of peat are minor hydrocarbon sources and contribute, in total, less than 10% to the budget for most alkanes. An important exception, with regard to shelf geochemistry, is the significant quantity of peat-derived higher plant n-alkanes.