δ13C and δD Values of n-Alkanes from In-Reservoir Biodegraded Oils: Implications for Understanding the Mechanisms of Biodegradation and for Petroleum Exploration

This study investigates the magnitude and direction of stable C and H isotope shifts of n-C15–30 alkanes from biodegraded oils sourced from Type II (Oil suite S) and Type II/III (Oil suite H) kerogens. Compound-specific isotope data show a 2.0‰ 13C-enrichment and no D-enrichment of n-alkanes in the most biodegraded oil from sample suite S. Similarly, there is a 1.5–2.5‰ 13C-enrichment and no D-enrichment in Oil suite H. Overall, there is a <2.5‰ δ13C and <20‰ δD variability among individual n-alkanes in the whole sequence of biodegradation. N-alkanes from the least biodegraded Oil H samples are 2–4‰ 13C-enriched in comparison with the least biodegraded Oil S. However, there are no differences in the δD values of n-alkanes in these samples. Our indirect isotopic evidence suggests (1) a site-specific biodegradation process, most likely at position C-2 and/or C-3 or another site-specific process, and (2) a significant D/H exchange between organic compounds in the source rock and isotopically similar marine formation waters. We conclude that, unlike δD methodology, investigation of δ13C composition of n-alkanes has strong potential as a supplementary tool for oil–oil and oil–source-rock correlation even in biodegraded oils when n-alkanes are present.

Geochemical Characterization of Some Biodegraded Oils from the Niger Delta Basin, Nigeria

This study aimed to examine the compositional changes resulting from biodegradation, fathom the extent of degradation, and provide clues for interpreting the evolution and the overall effects on the quality of the oils. Ten oil samples from onshore-offshore fields were analyzed using gas chromatography (GC) and GC-mass spectrometry (GC-MS) methods. GC results indicate variable loss of low molecular weight (LMW) alkanes, besides the presence of unresolved complex mixture (UCM). Saturated, aromatic, resins, and asphaltenes (SARA) compositions and low saturate/aromatic ratio confirmed evidence of biodegradation. Biodegradation levels of the considered oils range from light to moderate, based on Peters and Moldowan scale. This influenced shifts in the ‘primary compositions’ of oils probably from paraffinic or paraffinic-naphthenic oils to aromatic-naphthenic oils. Total ion chromatograms of well 1 and 2 from Northern depobelt, show presence of LMW alkanes, co-existing side by side with UCM, suggesting multiple charges. However, biomarker fingerprints of the oils lack evidence of in-reservoir mixing of biodegraded and non-biodegraded oils. Nevertheless, the possibility of oil mixing cannot be excluded, because biodegradation is progressive and is ongoing. This study, shows the process has dramatically impacted the fluid properties, commercial worth, and economic producibility of the investigated oil accumulations in the basin.

Biodegradation influence on alkylphenanthrenes in oils from Bongor Basin, SW Chad

Oil samples from the Bongor Basin, SW Chad have been geochemically characterized to investigate the biodegradation influence on alkylphenanthrenes. Concentrations of C0–3-alkylphenanthrenes (C0–3Ps) increase markedly after level 6 biodegradation due to the removal of other vulnerable components, decrease sharply after level 7 biodegradation and approach to absence at level 8. Phenanthrene appears to have higher ability to resist biodegradation than C1–3Ps at certain biodegradation levels (≤level 7) due to demethylation, which has been inferred as a possible reaction process during biodegradation of the aromatic hydrocarbons. The enrichment of non-alkylated phenanthrene in biodegraded oils makes biodegradation assessment complicated on the basis of alkylphenanthrene distributions. Individual isomers in alkylphenanthrenes exhibit variable ability to resist biodegradation influence. While certain isomers do show higher ability to resist biodegradation than others, no uniform biodegradation sequence can be established. Meanwhile, the biodegradation susceptibility between hopanes and alkylphenanthrenes varies greatly in different samples. The biodegradation systematics of alkylphenanthrenes proves to be highly complex, which may be indicative of the multiple charges and mixing during biodegradation.

Effect of biodegradation processes on the composition and structure of asphaltenes in West Siberian oils

NMR spectroscopy in combination with elemental analysis was used to study asphaltenes in biodegraded oils from Cenomanian pools of West Siberia. The sampling depths vary from 680 to 1800 m, formation temperatures – from 40°C to 70°C. For comparison, we used the data on asphaltenes in non-biodegraded oils of different genotypes. Given that biodegraded oils are very heavy (density: 910-950 kg/m3), they are characterized by high boiling point temperatures (145-270°C). Due to the loss of hydrocarbon components, they have higher resin and asphaltene content (9-20%) compared to non-degraded samples. Elemental analysis of asphaltenes in biodegraded and unaltered oils of different genotypes revealed an increasing trend for oxygen content in the asphaltenes from biodegraded samples, which may result from the oxidation of structural blocks of asphaltenes during microbial oxidation. It was shown that the aromaticity of the moderately biodegraded terrestrial-aquatic Novoaganskaya samples tends to increase with a decrease in asphaltene saturation, suggesting that the redistribution of structural groups of asphaltenes may be caused by biodegradation processes. High saturation of asphaltenes in strongly biodegraded Gubkinskaya and Novoportovskaya oils, along with a high degree of substitution of aromatic compounds in asphaltenes in Gubkinkaya oils (terrestrial and aquatic-terrestrial genotype) can be attributed to the formation of asphaltenes during strong biodegradation of hydrocarbon components in these oils.