Evaluation of the molybdenum isotope system as a petroleum tracer: The Phosphoria petroleum system, western U.S.A.

Abstract

The molybdenum (Mo) isotope composition of organic-rich mudrocks is used to infer paleo-ocean redox conditions but the potential of this isotope system as a petroleum tracer is uncertain. In this study, we measured the Mo isotope compositions of crude oils, asphaltene separates, and organic-rich source mudrocks (Meade Peak Member and Retort Member of the Permian Phosphoria Formation) for the Phosphoria petroleum system, western U.S.A. Crude oils from the Bighorn Basin have Mo concentrations of 0.01–0.39 μg/g that are significantly lower than Mo concentrations of 10–443 μg/g for the organic-rich mudrocks (2.4–16.6 wt% total organic carbon; TOC), suggesting inefficient transfer of Mo from source rock kerogen to oils. Asphaltene Mo concentrations are elevated (1.0–3.2 μg/g), indicating that asphaltene is an important host of Mo in the Phosphoria crude oils. However, statistically insignificant correlation between crude oil and asphaltene Mo concentrations as well as differences between the δ98Mo of some crude oils and their asphaltene separates (Δ98Moasphaltene–crude oil between −0.5‰ and +0.1‰) suggests other important hosts for Mo in the non-asphaltene fraction of the Phosphoria oils. The overall range of δ98Mo for fifteen Phosphoria crude oils and six asphaltene separates is 0.5–1.7‰ and 0.8–1.5‰, respectively. Crude oils unaltered by reservoir processes (biodegradation, water washing, thermochemical sulfate reduction) have δ98Mo of 1.1–1.4‰ whereas crude oils mildly affected by biodegradation and/or water washing span a wider range of δ98Mo (1.0–1.7‰). Five crude oils altered by thermochemical sulfate reduction (TSR), as indicated by higher δ34S, have lower δ98Mo (0.5–0.9‰), suggesting that TSR decreases the δ98Mo of crude oils via redox reactions and/or the introduction of external fluids containing isotopically light Mo into the oil reservoir. Biodegradation may cause variable δ98Mo in crude oils via kinetic isotope effects, microbial processes, or the recapture of isotopically distinctive Mo released from biodegraded oils elsewhere. A statistically significant inverse correlation between δ98Mo and δ34S for non-TSR altered oils may reflect a decrease in the δ98Mo of crude oils with increasing thermal maturity, perhaps associated with de-metalation reactions and/or formation of new organo-metal compounds. The δ98Mo of the unaltered crude oils falls within the range of δ98Mo for the Mo- and TOC-rich source rocks of the Retort and Meade Peake Members (1.0–2.0‰), suggesting the Mo isotope system has potential as an oil – source rock tracer. This application will have the most success in petroleum systems whose source rock(s) exhibit a narrow range of distinctive δ98Mo. Our study shows the Mo isotope system has promise as a petroleum tracer and potentially could be useful for studies on petroleum contamination in the environment.