Factors controlling enrichment of vanadium and nickel in the bitumen of organic sedimentary rocks

Abstract

Enriched concentrations of vanadium and nickel have been noted in a variety of naturally occurring organic substances including crude oils, asphalts, and organic matter in some sedimentary rocks. Vanadium and nickel concentrations in bitumens extracted from a variety of organic sedimentary rock types of different geological ages and geographical areas range from less than 0.2 to 4760 ppm and less than 7 to 1240 ppm, respectively. Vanadium concentrations showed a polymodal frequency distribution, while nickel concentrations showed a near-normal frequency distribution. The concentrations of these two metals showed no significant correlations with bitumen content, organic carbon content, or proportionality between bitumen and organic contents. Enriched vanadium and nickel concentrations greater than 100 ppm are only observed in bitumens that are associated with Type II and Type I kerogens. Conversely, bitumens associated with Type III kerogens contained vanadium and nickel concentrations less than 100 ppm. The high stability of vanadium and nickel in crude oils, asphalts, and bitumens suggest that they occur in tetrapyrrole complexes. These complexes may occur as free molecules or assimulated subunits in macromolecules because of their availability in anaerobic systems, small atomic radii, and favorable electron configurations. The potential for an organic sediment to be enriched in these two metals depends upon the amount of tetrapyrroles preserved in its organic matter. Tetrapyrrole preservation preferentially decreases in organic matter as exposure time to aerobic conditions increases. The potential for vanadium and nickel enrichment is therefore the highest in organic matter derived from algae that encountered anaerobic conditions early in their depositional history. Metallation of tetrapyrrole complexes appears to occur within sediments prior to their lithification, and interstitial waters are the most likely source for enriched concentrations of vanadium and nickel. The amount of metal enrichment in a sediment depends upon the diffusion of metal cations from its overlying water body, and this source is only effective as long as the sediment system remains open. The complete metallation of tetrapyrroles is most favorable under conditions of slow sedimentation rates, which would allow open sediment systems to be maintained for long durations.