New practical biodegradation proxies based on heteroatom compounds revealed by ESI (−) FT-ICR MS

Abstract

High-resolution mass spectrometry can be utilized to select specific proxies for the quantitative assessment of crude oil biodegradation degree, offering higher accuracy and convenience compared to conventional GC-MS methods. However, the current evaluation proxies are invalid for severely biodegraded crude oil. In this study, freshwater and saltwater lacustrine crude oils from the Liaohe Western Depression (Bohai Bay Basin) with varying degrees of degradation, were characterized using negative ion electrospray ionization [ESI (−)] Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results show that seven heteroatom classes were identified including N₁, N₁O₁, N₁O₂, O₁, O₂, O₃ and O₄. Certain differences exist in the abundance of heteroatom compounds in the nondegraded crude oils from the two origins, but both are dominated by N₁. The relative abundance of O₂ class species significantly increases, while the relative abundance of O₁ and N₁ class species decreases with an increase in the degree of biodegradation, reflecting the increase in the content of acid compounds as biodegradation products. O₂ class species become the predominant compound in the severe degradation stage. Biodegradation results in the enrichment of compounds with greater condensation, while the abundance of highly alkyl-substituted compounds decreases. The nitrogen-containing compound pairing proxies (DBE_12,13,15/DBE_9∼11-N₁) can be employed to assess the degree of biodegradation in crude oil under conditions of similar maturity. As the degree of biodegradation increases, the content of 2 ∼ 5-cyclic naphthenic acids increase, while the content of acyclic acids with weaker resistance to degradation decreases. The ratio of acyclic acids to 2 ∼ 5-cyclic naphthenic acids (Modified A/C Ratio 2) can effectively assess the biodegradation level of crude oils ranging from nondegraded to severe degradation. The O₂/(N₁ + O₁) Ratio reflects the formation of acids during the biodegradation process and exhibits a robust positive correlation with crude oil density and degradation degree. The new proxies provide higher precision and broader applicability compared to conventional methods, enabling quantitative evaluation of biodegradation levels. The application of ESI FT-ICR MS technology holds significant importance in the assessment of heavy oil and the exploration of its genetic mechanisms.