Besides
the kerogen composition, the amounts of generated bitumen play a major
role when assessing the petroleum retention and expulsion behavior
of a source rock. High-molecular weight (HMW) products dominate the
source rock extracts during early stages of generation in the total
organic carbon-rich, inefficiently expelling Mandal Formation. Such
gas chromatography-unresolvable, bituminous compounds have not yet
been structurally described. Based on 20 immature to peak-oil mature
whole rock samples from different locations of the Central Graben,
a compositional comparison of seven samples of different maturity
stages is drawn to the excellently expelling Posidonia Shale, Germany,
of similar maturity. Electrospray ionization negative Fourier transform
ion cyclotron resonance mass spectrometry allows the investigation
of the acidic heteroelemental interior of the in-source retained petroleum.
Rather than the quantities of bitumen, its composition seems to be
important for petroleum migration efficiency and fractionation. While
Posidonia Shale extracts contain slightly higher proportions of NSO
constituents than extracts of the Mandal Formation, they are dominated
by lower polar nitrogen compounds. Instead, Mandal Formation extracts
are strongly enriched in highly polar oxygen-containing (O
x
) compounds (O2–O6)
which are more aromatic but contain longer aliphatic chains than extracts
of the Posidonia Shale samples, thus increasing their molecular size
and the number of polar sites. In particular, it is the C16 and C18 aliphatic and C20 aromatic homologues
occurring in O2+ classes which most likely represent fatty
and aromatic acids linked with additional oxygen-functional groups.
We suggest that these features might be specific to the Mandal Formation
of the Central Graben and are related to complex interactions of geological/palaeogeographic
evolution, climate fluctuations, and biological input during Upper
Jurassic times. Consequently, the compositional features of petroleum
generated from the Mandal Formationhighly polar, large aromatic
core structures with long aliphatic chains attachedcontrol
its physical properties and cause interaction with polar phases, such
as the residual kerogen or clay minerals, and nonpolar phases in the
source rock.