Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n-C₁₇/pristane and n-C₁₈/phytane ratios and loss of n-C₇, 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C₆ and C₇ cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as −16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as −39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65°–96°C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95°–130°C) which are much higher than the temperatures of known occurrences of biodegraded oil.