Theoretical study on the reactivity of sulfate species with hydrocarbons

Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of HSO4- relative to SO42-. However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO4- is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as SO42-, aqueous calcium sulfate ([CaSO4](aq)), and aqueous magnesium sulfate ([MgSO4](aq)). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions (HSO4-) and/or magnesium sulfate contact ion-pairs ([MgSO4]CIP) rather than 'free' sulfate ions (SO42-) or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR.