Kerogen

Kerogen - a re-cap
complex, HMr, diseminated organic matter in sediments
operational definition: OM that is insoluble in non-polar solvents
(benzene/methanol, toluene, methylene chloride) and
nonoxidizing mineral acids (HCl and HF)
major starting material for most oil and gas generation
sediments are subjected to heating in the subsurface - oil
and gas is generated from the kerogen
most abundant form of organic carbon on earth (1000 x more
than coal)
made up from altered remains of marine and lacustrine
microorganisms, plants and animals - with differing amounts of
terriginous debris
 Re-cap contd
kerogen
~1% of OM originating from biological sources - forms after all
degradation processes discussed earlier in this course
structured, terriginous portions of kerogen have an elemental
composition similar to coal
may contain significant contributions from biopolymers altered
during degradation pathways
substantial incorporation of biological macromolecules that have
been transformed prior to and after burial
contains info about the depositional, geological, and geothermal
history of sediments
 Methodologies
Chemical and optical methods utilized
Kerogen does not migrate - so, sediment matrix and kerogen are
from same depositional and thermal history
microscopic methods - work well for structured kerogen
chemical methods - work well for amorphous OM (usually present in
greater abundance than structured)
- why do we want to know?
so we can find out the petroleum-generating potential
 Methods contd
No magic bullets
combination of chemical methods
chemical techniques provide
routine analyses in oil and gas exploration
information with regard to the origin and subsequent geological
history of kerogen
cant do both with one technique
 Screening for potential
Determination of total oil and gas generation potential directly linked
to availability of hydrogen rich linkages
how easy it is to release the CH moieties
Rock Eval pyrolysis - measures gas generating potential and
thermal maturation via Tmax (temp at which maximum
pyrolyzable OM evolves)
microscopic characterization
qualitative
proportions of woody OM, amorphous OM etc
measurement of the Thermal Alteration Index
fluorescence
vitrinite relectance (%Ro)
 Historical information
Can not be determined by Rock Eval/microscopic techniques
 Historical information
End member determination/ delineation
The more we know about the modern depositional environment - the
better it is to look at the past
Problems - when major depositional systems have changed
eg., ocean circulation patterns are different today than when most
of all oil was generated
>50% of worlds petroleum was generated in the Jurassic and
the Cretaceous
Chemical and optical properties tend to merge at higher maturities
GEOLOGICAL/STRATIGRAPHIC/SEDIMENTOLOGICAL
reconstruction likely gives a reasonable estimate of past
generation potential
Use multiple chemical/microscopic/geological techniques to understand
origin vs. maturation vs. biodegradation
 Kerogen Type
How to know more and more about less and less.....
elemental and isotopic analysis
average-bulk structure and composition of all OM in a given
sediment
qualitative, semi-quantitative, quantitative analysis
structural, spectral properties
degradative techniques
detailed characterization of well-defined subunits
pyrolysis-gas chromatography/mass spectrometry
chemical degradative schemes
Bulk gives us an average, details give us fine definition of only a very
small - possibly non-representative portion of the kerogen
 Which technique?
ask yourself what do I need to know - use the correct number of
techniques to find the answers
How much oil and gas will be generated?
most important process is hydrogen transport
how much elemental hydrogen is bonded to the kerogen?
Rock Eval pyrolysis
What geological processes have been involved in the kerogen
formation?
detailed chemical methods about the minor fractions of kerogen
Py-GC/MS coupled with microscopic techniques
 Different techniques
Elemental analysis
Determination of H/C and O/C atomic ratios
 Elemental Analysis
During thermal maturation/catagenesis, all kerogen types lose
hydrogen and oxygen containing functional groups
progression is towards the lower left hand corner of the following
plots
During low temp maturation/diagenesis ALL kerogens expel
hydrogen and oxygen predominantly as water and carbon dioxide
During high temperature maturation ALL kerogens expel
hydrocarbons (HC)
Purely chemical analysis
 Purely chemical analysis
Type I kerogen
paraffinic kerogens (produce light oils)
H/C > 1.25
O/C < 0.15
found in boghead coals and shales
contain abundant Botyococcus algae
derived from lacustrine sedimentation or tasmanite (marine
equivalent)
using this criteria some Persian Gulf Cretaceous limestones are
included as Type I
Type I - primarily oil prone on maturation - very rare
probably because the Type I curve merges with Type II during
maturation
can only be recognized at fairly low maturation levels <0.8% Ro
 Purely chemical analysis
Type I kerogen
paraffinic kerogens (produce light oils)
H/C > 1.25
O/C < 0.15
found in boghead coals and shales
contain abundant Botyococcus algae
derived from lacustrine sedimentation or tasmanite (marine
equivalent)
using this criteria some Persian Gulf Cretaceous limestones are
included as Type I
Type I - primarily oil prone on maturation - very rare
probably because the Type I curve merges with Type II during
maturation
can only be recognized at fairly low maturation levels <0.8% Ro
Purely chemical analysis
Type II Kerogens
original reference for Type II kerogens came from the Lower
Toarcian Shale of the Pris Basin
H/C < 1.3 (lower than Type I)
O/C ~ 0.03 - 0.18 (equivalent or greater than Type I)
organic-rich ancient and recent low-maturity marine sediments have
predominantly Type II kerogen associated with them
the reference kerogens generate a mix of oil and gas on maturation
immature analogs of the major kerogen types found in highly
productive oil and gas fields
Purely chemical analysis
Type II Kerogens
original reference for Type II kerogens came from the Lower
Toarcian Shale of the Pris Basin
H/C < 1.3 (lower than Type I)
O/C ~ 0.03 - 0.18 (equivalent or greater than Type I)
organic-rich ancient and recent low-maturity marine sediments have
predominantly Type II kerogen associated with them
the reference kerogens generate a mix of oil and gas on maturation
immature analogs of the major kerogen types found in highly
productive oil and gas fields
Purely chemical analysis
Type III kerogens
H/C < 1 (relatively low)
O/C ~ 0.03 - 0.3 (relatively high)
planktonic remains are virtually absent in reference Type III
samples
significant higher plant and woody material contributions
woody, coaly, vitrinitic or humic
Gas prone
Purely chemical analysis
Type III kerogens
H/C < 1 (relatively low)
O/C ~ 0.03 - 0.3 (relatively high)
planktonic remains are virtually absent in reference Type III
samples
significant higher plant and woody material contributions
woody, coaly, vitrinitic or humic
Gas prone
Purely chemical analysis
Type IV / Residual Type / Inertinite
H/C always < 0.5
maturation line near the bottom of the van Krevelan axis
Purely chemical analysis
Type II-S
high-sulfur (8-14%) type II kerogen
source for heavy sulfur oils from the onshore and offshore
Monterey Formation in California
generated at much lower maturities than observed for other
kerogens
distinguished from Type II due to the higher S/C
not visually different from Type II
Purely chemical analysis
Problems
Type II Systematic elemental analysis performed on a set of
amorphous kerogens from various origins has shown that,
although some of them belong to type II, the chemcial
composition of the amorphous kerogen may spread over the
entire van Krevelen diagram Tissot 1984
Type III although chemical determinations say wood or higher
plant from microscopic techniques it is not obvious that the
higher O/C comes from plant remains/fragments
 Much more to read
Chapter 14 of Organic Geochemistry (Engel and Macko) pp. 289-353
describes all different analytical techniques including
microscopic techniques
pyrolysis techniques
infrared spectroscopy
nuclear magnetic resonance spectroscopy (NMR)
Electron Spin Resonance (ESR) spectroscopy
Isotopic techniques
Pyrolysis -GC and Py-GCMS
Electron microscopy (diffraction)