Trace-metal enrichment mechanisms in Bakken Formation black shales, Williston Basin, North Dakota, USA

The Bakken black shales represent a unique sedimentary system characterized by high total organic carbon contents (TOC; Lower Bakken shale = 10.8 and Upper Bakken shale = 11.8 avg. wt%) and enrichment factors (EF) of various trace metals (TMs) such as Cu (6.2-7.7), Mo (219.7-237.8), Ni (9.4-10.2), U (20.6-29.3), V (9.9-14.2), and Zn (10.4-12.2) that are considerably higher than many other Devonian-Mississippian (D-M) black shales. In this study, raw distributions of elemental concentrations combined with bivariate and principal component analysis (PCA) were used to clarify processes that contributed to high TM EF values in the Bakken shales. Total organic carbon shares heavier PCA component loadings (>0.445) and stronger Pearson correlation coefficients (r) with Cu, Mo, Ni, U, V, and Zn than with pyrite-associated (As, Co, Fe, and S) elements, suggesting that organic matter (OM) played a primary role in the scavenging and accumulation of TMs in the sediments. Reducing conditions within bottom waters or sediment pore waters may have accelerated the accumulation of redox-sensitive Cu, Mo, Ni, V, and Zn introduced into the sediments via an OM detritus host and most likely played a secondary role in their enrichment. Deep-water renewal times for the Bakken have been estimated to be similar to 10-30 yrs. based on Mo/TOC results. The high TM EF values observed in the Bakken shales may reflect frequent resupply of TMs into basin waters, enhanced primary productivity that is necessary in scavenging TMs from the water column, the presence of H2S within sediment pore or bottom waters, or possibly secondary processes associated with basin-wide fluid and hydrocarbon migration. High TOC concentrations may be the result of a possible shallow water column (similar to 150 m), which would limit exposure time of OM to oxidation and degradation, coupled with intermittent fluctuations between dysoxic and anoxic/euxinic bottom-water redox conditions, the latter of which would reduce rates of OM degradation by benthic organisms.