Fixed-ammonium in clays associated with crude oils

The association of ammonium (NH₄⁺) silicates with organic-rich sedimentary environments has stimulated interest in the chemical cycle of N, and its possible application as an indicator of in situ organic maturation reactions or crude oil migration. Fixed-NH₄ in clay minerals was determined from three hydrocarbon occurrences of similar depositional environment but different ages, depth and thermal maturity, to determine whether anomalously high NH₄-substitution occurs near mature hydrocarbons. Results show higher fixed-NH₄ concentrations in marginally mature mudstones than in immature sediments. The highest fixed-NH₄ concentrations were found in clays from sandstone reservoirs containing migrated crude oil. Fixed-NH₄ in clays from Holocene oil seep sediments in the Gulf of Mexico continental slope, offshore Louisiana, averages 0.08 wt % and increases with depth in shallow cores (420 cm), reflecting an early diagenetic trend that is apparently not influenced by migrating crude oil. Programmed pyrolysis shows that the sediments are thermally immature (av. T_max = 419°C). High Hydrogen Index values (av. = 359 mg/g) are the result of biodegraded crude oil, and a high Oxygen Index (av. = 182 mg/g) reflects the presence of authigenic carbonate. Fixed-NH₄ averages 0.16 wt % in Wilcox Group (Eocene) mudstones enclosing two sandstone reservoirs at Fordoche Field, onshore Louisiana. In comparison to these mudstones, anomalously high NH₄-fixation appears to occur in reservoir clay minerals. Pyrolysis shows that the sediments are marginally mature for crude oil generation (av. T_max = 432°C). Average Hydrogen Index (187 mg/g) and Oxygen Index values (75 mg/g) are consistent with oil-prone Type II and Type III kerogen. Increased pyrolysis Production Index values and solvent extraction shows the presence of migrated crude oil. This suggests that a reaction which releases NH₃ during crude oil generation or migration is recorded by NH₄⁺ substitution in clays. Fixed-NH₄ and total organic carbon (TOC) at Fordoche Field show no statistically significant correlation, suggesting that NH₄⁺ substitution in clay minerals is not simply related to the amount of organic matter in the section, but is also influenced by the presence of crude oil. Once NH₄⁺ has been fixed in clays, it is a more stable hydrocarbon proximity indicator than pore fluid tracers, because it is less influenced by later chemical or geological changes.