Porphyrin protonation induces decoupling of trace metals in petroleum

The mechanism of migration of trace metals in petroleum systems is poorly understood, which limits our understanding of organic–inorganic interactions and their application in tracing oil sources. Based on a molecular model of metalloporphyrin, numerical simulations involving density functional theory have revealed that porphyrin protonation is associated with trace-metal decoupling in petroleum. Trace metals readily form covalent bonds with weakly protonated porphyrin N to form stable compounds. However, the metals may be decoupled at lower fluid pH owing to increased N protonation, which activates the formation of ionic bonds with O²⁻. The released metals may then be fixed in authigenic calcite cement (ACC) reservoirs through substitution of Ca. For Mg, Mn, and Fe, the decoupling order is Mg > Fe > Mn, whereas that for the substitution of Ca is Mn > Fe > Mg, reflecting the complexity of organic–inorganic interactions and indicating the potential application of metals in fingerprinting oil sources. This case study of the southern Junggar Basin, China, revealed that Mn, Fe, and Mg enrichment of ACC may provide indications of Paleozoic, Mesozoic, and Cenozoic petroleum systems, respectively, providing a potential new approach for the tracing of oil sources in petroleum basins.