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Organic Geochemistry of Petroleum System

Dr. SAMPEI, Yoshikazu


Professor, Department of Geoscience, Faculty of Science and Engineering, Shimane University,
E-mail:sampei@riko.shimane-u.ac.jp

1. Fundamentals of Organic Geochemistry


2. Origin and Formation of Petroleum
3. Maturity
4. Migration and Trap
5. Source Rock Evaluation
6. Oil-Source Rock Correlation and Biodegradation
7. Modeling
“ Petroleum Formation and Occurrence ”
“ The Biomarker Guide ”
“ Introduction to Organic Geochemistry ”
Contents

(19)Organic nitrogen and oxygen compounds (6)Biodegradation of n-alkane


Organic Geochemistry of Petroleum System (20)Biogenic methane (7)Biodegradation stage
(8)Biodegradation effect on sulfur&nitrogen contents and API

3. Maturity ------------------------------------------------------------(36)
(1)Diagenetic compositional changes in hydrocarbon 7. Modeling ----------------------------------------------------------(80)
(2)Diagenetic change in chemical structure of kerogen (1)Changes in %Ro under different heating rate
Dr. SAMPEI, Yoshikazu (3)Vitrinite Reflectance (2)Computer simulations based on kinetics of isomerization
Professor, Department of Geoscience, Faculty of Science and (3)Data set of kinetic parmeters
(4)Maturity indicator of biomarker
(4)Simulation results
(5)GC/MS SIM chromatogram of oil
Engineering, Shimane University, E-mail:sampei@riko.shimane-u.ac.jp (6)Relationship between two biomarker maturity indicators 1
(7)Relationship between two biomarker maturity indicators 2, 8. Reference ---------------------------------------------------------(84)
(8)Non-biomarker maturity indicators in postmature zone
(9)Respond range of maturity parameter
(10)Origin of methane
Contents
4. Migration and Trap ----------------------------------------------(46)
(1)Primary migration and secondary migration
(2)Porosity and fluid pressurek
1. Fundamentals of Organic Geochemistry ------------------------(4) (3)Porosity and permeability of reservoir rock
(1)Components of oil (4)Microfracturing system in primary migration
(2)Biomarker (5)Diffusion-controlled processes in primary migration
(3)Labeling system (6)Molecular solution in water
(4)Symbols of chemical structure (7)Molecular solution in gas
(5)Modifiers on chemical structure (8)Complex system for oil accumulation
(6)Stereo-isomer (9)Preferential expulsion
(7)Optical isomer
(8)Racemization
(9)Important analytical equipment : GC 5. Source Rock Evaluation -----------------------------------------(55)
(10)Important analytical equipment : GC/MS (1)Standard evaluation sheet for source rock potential
(11)Representative GC/MS result: Selected ion chromatogram (2)Source rock generative potential
(12)Representative GC/MS result: Full scan and mass chromatogram (3)TOC and S2 of shale
(4)Controlling factors of TOC
(5)S2-TOC plot
2. Origin and Formation of Petroleum --------------------------(16) (6)Lacustrine source rock evaluation
(1)Kerogen Type (7)Biomarker as organic source indicator
(2)Depositional environment of kerogen type (8)Biomarker as organic source indicator
(3)Caracterization of Kerogen: bulk composition (9)Age control of the C28/C29 steranes ratio
(4)Kerogen formation: classical and diagenetic path (10)Oxic-anoxic proxy
(5)Kerogen formation: new concept (11)Depositional environment indicator
(6)HI and OI (12)Origin indicator
(7)Van Krevelen diagram and HI-OI (13)Depositional indicator
(8)Rock Eval (14)Origin indicator 2
(9)Interpretation of Rock Eval (15)Origin indicator 3
(10)HI and H/C (16)Porphyrin
(11)Petroleum system (17)Souce rock potential and environmental change
(12)Crude oils characterization
(13)Crude oils characterization 2 6. Oil-Source Rock Correlation and biodegradation ---------(72)
(14)Hydrocarbon compositions (1)Tool for oil-source rock correlation
(15)Terpanes (2)Correlation by n-alkane
(16)Terpanes (3)Correlation by steranes and hopanes
(17)Aromatics (4)Correlation by steranes
(18)Organic sulfur compounds (5)Confidence of oil-source rock correlation
1. Fundamentals of Organic Geochemistry 1-(1) Components of oil
Asphaltens:
Higher molecular weight (500-1500)
NOS/polar compound; soluble in
CS2; insoluble in n-C6H8 or n-C5H10

Resins:
Higher molecular weight (less than
500) NOS/polar compound; soluble in
n-C6H8 or n-C5H10

Molecular sieve:
Separation based on molecular size by
e.g. zeolite; small molecules become
trapped in the crystal lattice.

Urea adduction:
Small molecules become adducted by
urea crystal (NH2CONH2); use to
concentrate e.g. steranes.
Tissot and Welte (1984)
1-(2) Biomarker
Useful tool to know:
Origin of organic matter; Depositional environment;
Maturity; Correlation between oils and source rock.

Steranes

Hopanes

Peters and Moldowan (1993)


1-(3)
Labeling system

Three-dimensional
structure

To know:
Maturity
(Origin)

Peters and Moldowan (1993)


1-(4)
Symbols of chemical structure

To depict the stereochemistry of


atoms

Single bond: on the sheet plane

Light gray bond and white


circle:
directe into page

→ the alpha (α) position


(The opposite side is beta (β) )

= Stereochemistry

Peters and Moldowan (1993)


1-(5)
Modifiers on chemical
structure

Homo-: one additional


carbon on sturucture.

bis=di
tris=tri
tetrakis=tetra
pentakis=penta
hexakis=hexa

Nor-: one less carbon on structure. Des-A: loss of A from structure. Iso-: methyl
shifted on structure. Neo-: methyl shifted from C18 to C17 on hopane.

R: asymmetric carbon that obeys convention in a clockwise direction.


S: asymmetric carbon that obeys convention in a anti-clockwise direction

Peters and Moldowan (1993)


1-(6)
Stereo-isomer.

Important concept to
understand maturity indicators
of biomarker

Changes to the mirror-image


structure by heated condition
(These two are so called
“enantiomers”)

These substituents form chiral


molecule.

Chiral molecule:
The name is given to a
substituent with an asymmetric
carbon at which optical
isomers may occur.
Peters and Moldowan (1993)
1-(7) Optical isomer

The stereo-isomer shown in the


previous page is an optical isomer,
which can perform a rotatory
polarization.

Clockwise direction “dextro-


rotatory”
“R (rectus or dextral)” or,
“D” or,
“+”

Anti-clockwise direction “levo-


rotatory”
“S (sinister)” or,
“L” or,
“−“
Peters and Moldowan (1993)
1-(8) Racemization:
Interconversion of
enatiomers is called
racemization.

Epimer
Enantiomer
Enentiomorph
Antimer
The biological epimer
20R-C29-5α, 14α, 17α(H)-sterane
changes to the geological epimer
20S-C29 5α, 14α, 17α(H)-sterane

The ratio of 20S/(20S+20R) rises from


0 to about 0.5 (equilibrium at 0.52-
0.55; seifert and Moldowan, 1986).

Peters and Moldowan (1993)


1-(9)
Important analytical equipment :
GC

GC:
The separation of mixtures of
compounds by partition between
a mobile gas phase and
stationary liquid phase is called
gas chromatography
(Miles,1994).

Capillary column is used to


separate components of oils and
rock extracts. .

Peters and Moldowan (1993)


Shimane Univ.

Peters and Moldowan (1993)


1-(10) GC/MS
The tandem system of GC linked to a mass
spectrometer; the most powerful analytical
technique in modern organic geochemistry.
Organic compounds → separated →transfered to
the ionizing chamber →accelerated → detected
in the electron multiplier
Positive ions of mass/charge ratio (m/z) are
impinge on the detector.
Analitical time: 1 or 2 hours
Shimane Univ. GC temp.: about 40 to 300 ºC.
1-(11)
Representative GC/MS result:

Selected ion monitoring (SIM)


is often used.

With 70eV electron impact


(EI) ionization

SIM is very sensitive.

Steranes and hopanes have specific fragment ions m/z=217 and m/z=191,
respectively.

These two ions are commonly used as routine biomarker analyses.

Peters and Moldowan (1993)


1-(12)
Full scan + mass chromatogram

“Full scan ” condition is not so


sensitive.

But “Full scan ” gives a detail


information to know organic
structure of unknown compound.

The detail information is “mass


chromatogram”.

Major fragment ion


& Mokecular ion

Peters and Moldowan (1993)


Representative GC/MS chart for steranes

m/z=217
m/z=217 5 9 C sterane 20R
28
C27 sterane 20R (ergostane)
(cholestane)
13
C29 sterane 20R
(stigmastane)
6
12
7 11 15
10 14
8 16
Diacholestane 20R 4 3
2
17 18
1

Unpublished data (Akita-oil)


Peak No. Name carbon number

1 A 13β,17α (H)-diacholestane 20R 27


2 B 13β,17α (H)-diacholestane 20S 27
3 C 5α,14α,17α(H)-24-norcholestane 20R 26
4 D 5α,14α,17α(H)-24-norcholestane 20S 26
5 E 5α,14α,17α(H)-cholestane 20R 27
6 F 5α,14α,17α(H)-cholestane 20S 27
7 G 5α,14β,17β (H)-cholestane 20R 27
8 H 5α,14β,17β (H)-cholestane 20S 27
9 I 5α,14α,17α (H)-24-methylcholestane 20R 28
10 J 5α,14α,17α (H)-24-methylcholestane 20S 28
11 K 5α,14β,17β (H)-24-methylcholestane 20R 28
12 L 5α,14β,17β (H)-24-methylcholestane 20S 28
13 M 5α,14α,17α (H)-24-ethylcholestane 20R 29
14 N 5α,14α,17α (H)-24-ethylcholestane 20S 29
15 O 5α,14β,17β (H)-24-ethylcholestane 20R 29
16 P 5α,14β,17β (H)-24-ethylcholestane 20S 29
17 Q 5α,14α,17α (H)-24-n-propylcholestane 20R 30
18 R 5α,14α,17α (H)-24-n-propylcholestane 20R 30
Representative GC/MS chart for hopanes

C30Hopane
m/z=191

C31Homohopane (S,R)

Tm C32(S,R)
C34 (S,R)
C33 (S,R) C (S,R)
35
Ts

Peters and Moldowan (1993) 36:Oleanane 31:Gammacerane


Peters and Moldowan (1993)
Precursors of steranes

Cholesterol

HO

Stigmasterol
HO

24α-ethylcholesta-5,22E-dien-3β-ol
As macerals (morphology) 2. Origin and Formation of Petroleum
2-(1) Kerogen Type
Kerogen: Insoluble; preserved in sedimentary rocks
Type-I
Type I (very oil prone): amorphous
hydrogen-rich; algal in anaerobic; especially lacustrine.

Type II (oil prone): herbaceous


comparatively hydrogen-rich; phytoplankton in
suboxic; especially marine.

Type III (gas prone):Woody&coaly


II hydrogen-poor & poly-aromatic; higher plants

III Type IV (inertinite) :Woody&coaly


oxidized and hydrogen-very-poor
Type II-S : amorphous
unusually high organic sulfur about 8-14% (atomic
S/C>0.04) and appear to begin to generate oil at lower
Shimazaki (1986) thermal exposure
Structural characteristics
of Kerogen

Killops and Killops (2005)


2-(2)
Depositional environment of kerogen type
Type I:
stratified freshwater lakes
Type II:
silled, deep-water basins on continental slope and rise
outer shelf O2-minimum layer under upwelling
Type III:
lagoonal, deltaic and coastal swamps
basins of restricted circulation on continental shelves

Type I
Type III Type III
Type II
Type II
500-2500m without supply of clay

Peters and Moldowan (1993)


2-(3) Bulk composition:
Van Krevelen diagram

Immature type I :
high H/C about 1.7 and low O/C about
0.05.

Immature type II :
medium H/C about 1.3 and medium
O/C about 0.1

Immature type III :


low H/C about 0.9 and high O/C about
0.2.

Tissot and Welte (1984)


2-(4) Kerogen formation:
classical and diagenetic path
Living organisms are composed
of:
Lignins
Carbo-hydrates
Proteins
Lipids
Macro-molecules to
Sugars
Amino acids
Fatty acids
Polymerized to
Humic acid
Kerogen

Tissot and Welte (1984)


Structural characteristics
of Lignin Killops and Killops (1993)

lignin

conifer wood broadleaf wood


2-(5) Kerogen formation:
new concept
Bio-macromolecules as lignins,
carbohydrates, proteins and lipids
are to humic substances.

Anoxic marine without Fe → hydrogen sulfides


Killops and Killops (2005) → organic sulfur → sulfur rich oil
2-(6) Rock Eval HI and OI
Rock Eval hydrogen index (HI: mgHC/gTOC)
and oxygen index (OI: mhCO2/gTOC) is
simulating the Van Krevelen diagram.
Immature type I:
high HI 900 and low OI 20
Immature type II:
medium HI 500 and medium O/C 50
Immature type III:
low HI 100 and high OI 100.

HI = S2/TOC

Example:
S2=4(mgHC/gRock)
TOC=2(%)
HI = 4/(2/100) = 200 (mgHC/gC)

Peters et al. (2005)


2-(7) Type I II III
Correlation between Van Krevelen H/C 1.6, 1.3, 0.9
diagram and modified Van Krevelen HI 800, 500, 100
diagram.
O/C 0.05 0.1 0.2
OI 20 50 200

Peters et al. (2005)


2-(8) Rock Eval

Anhydrous pyrolysis
Institute Francais du
Petrole (IFP)

Shimane Univ. About 100mg of


pulverized source rock
sample

Shimane Univ. Hydrocarbon detected by


FID (flame ionizetion
detector)

CO2 detected by TCD


(thermal conductivity
detector)

Tissot and Welte (1984)


2-(9) Interpretation of Rock Eval

First at 300ºC: the peak area S1

Second at 300-550ºC(25 ºC /min)


: the peak area S2

Carbon dioxide up to a temp. of


390ºC: the peak area S3

HI: S2/TOC
OI: S3/TOC
Tmax: ºC

<435 ºC (immature)
435 to 460 ºC (mature)
Tissot and Welte (1984) >460 ºC (post mature)
Whelan and Thompson-rizer
(1993)

C20H42 : H/C=2.1 2-(10) HI and H/C


Quantitative relationship
C12H18 : H/C=1.3
H/C = 0.0017HI + 0.5
C6H6 : H/C=1

C10H8 : H/C=0.8 O/C = 0.0036OI + 0.05.

C14H10 : H/C=0.71
2-(11) Petroleum system

Anoxic condition:
kerogen survives oxidation

Humic macro-molecule ( in diagenesis ) Heated with increasing depth


to release CO2 and H2O
Hydrocarbon ( in catagenesis )
Gas ( in metagenesis )

Peters et al. (2005)


2-(12)
Ternary
diagram
of oils
Biodegradation
Oxydation Paraffins
Water-washing Naphthenes
Aromatics
(&NOS)

Tissot and Welte Non-degradaded: Paraffins&aromatics


(1984)
Degradaded: heavy oils; aromatics &NOS and much sulfur >1 %
Biodegradation 2-(13)
Oxydation “Alteration”:
Water-washing
Biodegradation+
water washing:
Biodegradation Paraffins&Naphth
enes decrease.
only
Maturation:
aromatics+
Thermal maturation asphaltenes
decrease.

Aromatics:
absent in recent
sediments;
produced in the
early diagenesis;
decomposed in the
catagenetic
Tissot and Welte (1984)
2-(14)
Hydrocarbon compositions

Tissot and Welte (1984)


Based on boiling
temperature,
molecular weight
and absorption
affinity

alkanes (n-alkane)
iso-alkane
Cycloalkanes
mono-aromatics
di-aromatics
organic sulfur compounds poly-aromatics
organic nitrogen compounds
organic oxygen compounds.

Soxhlet extraction (Shimane Univ.)


2-(15)a
Terpanes

Sesterterpanes (C25):
Acyclic
Tricyclic
tetracyclic
head

Isoprene unit: diatom


building block for terpenoids

Peters et al. (2005)


2-(15)b
Terpanes

Triterpanes (C30):
Acyclic
Tricyclic

Peters et al. (2005)


2-(16)a Steranes

Peters et al. (2005)

Peters et al. (2005)


2-(16)b Hopanes

Peters et al. (2005)


2-(17)
Aromatics

Peters et al. (2005)


2-(18)a
Organic
sulfur
compounds

Peters et al. (2005)


2-(18)b
Organic
sulfur
compounds

low matured high


sulfur oil

Peters et al. (2005)


2-(18)a
Organic
nitrogen
compounds

pH control

Neutral nitrogen
Basic nitrogen

Peters et al. (2005)

Peters et al. (2005)


2-(18)b
Organic oxygen compounds

Mainly due to
biodegradation

1
2

DPEP –––(maturation)–––> Etio

Peters et al. (2005)


Chlorophyl-a

Suzuki, 2000 (鈴木 (2000) 監修,「生物図録」数研出版)


2-(20)
Biogenic methane

Peters et al. (2005)

Early stage of diagenesis by methanogenic


Methane formation
bacteria (methanogens) after working sulfate-
reducing bacteria

Deltaic and coastal swamps: Activity of methanogenic bacteria is high


because of abundance in organic acid (mainly acetate, indicating oxic
condition) and absence of sulfate-reducing bacteria.
Eubacteria: CH3COOH2 ---> CH4 + CO2
Archaebacteria: CO2+4H2 ---> CH4 + 2H2O
3. Maturity 3-(1)
Production and
decomposition of
hydrocarbon
Diagenesis; Catagenesis;
Metagenesis
(High molecular weight n-
alkanes decrease by
thermal degradation.)

Peak of oils at about 2500m:


an average on Mesozoic and
Paleozoic source rocks

The depth changes due to type of


kerogen, burial history and
geothermal gradient.
Tissot and Welte (1984)
3-(2) Diagenetic change in chemical
structure of kerogen

Characterized based on some common


fanctional groups.
“Infrared spectra”
Aliphatic bonds
C-H (2920 and 2855 cm-1),
CH2 (1375cm-1)
CH3 (1455 and 1375 cm-1)
Aromatic bonds
C-H (930-700 cm-1)
C=C (1630 cm-1)
Ketones, acid and esters
C=O (1710 cm-1)
These peaks decrease with increasing
diagenesis mostly by temperature.

Tissot and Welte (1984)


3-(3) Vitrinite reflectance
TypeIII&Humic coals Very popular maturation
indicator

Tissot and Welte (1984)

Ro (%): 0.5, 1.0, 1.5, 2.0 Based on the change in the


Tmax (℃): 435, 450, 470, 510 reflectance of polished virinite
particles
Measured on the polished vitrinite Increase with increasing time and
with oil at 546nm incident light temperature (by progressive
under microscope aromatization)

Abbreviations: Ro (o: in oil); %Ro; Rm (m: mean); Rmax; Rmin


3-(4) Maturity indicator of biomarker

22R and 22S C31-35 homohopanes


20R and 20S C29 sterane
C31 or C32 homohopanes
22S/(22S+22R) ratio: 0 to about 0.6

homohopanes
average equilibrium ratios
C31, C32, C33, C34, and C35 are 0.55, 0.58, 0.60, 0.62
Peters et al. (2005) and 0.59 (Zumberge, 1987)
3-(5) GC/MS SIM of oils
Biomarker: broken by thermal
cracking and aromatization
17α-hopane decreases with
increasing maturity
The less stable Tm decreases relative
Peters et al. (2005) to Ts with increasing maturity.
The C19-C29 tiricyclic terpanes can
be used as fingerprint.

C27 hopanes
Ts/Tm; Ts is C27 18α-trisnorhopane
(18α-22,29,30-trisnorhopane) and
Tm is C27 17α-trisnorhopane (17α-
22,29,30-trisnorhopane) and less
stable than Ts.

Peters et al. (2005)


3-(6) Maturity parameters
The ratio of 20S/(20S+20R)-
C29-steranes: a good linear
correlation with ßß(ßß+αα)-
C29-steranes

αα means:
C29- 14α, 17α(H)-sterane
ßß means:
C29- 14ß, 17ß (H)-sterane
Peters et al. (2005)

ßß(ßß+αα)-C29-steranes:
From near-zero to about 0.7
20R or 20S
(equilibrium at 0.67-0.71;
17α or 17ß seifert and Moldowan, 1986).

14α or 14ß
3-(7)
Different isomerization rate
(diagenesis to catagenesis)

In low maturity:
Hopane isomerization
increases faster than sterane.

In high maturity:
Hopane isomerization
increases more showly than
sterane.

Each maturity value does not


indicate the exactly same
stage of maturity under a
different heating rate
condition.

Peters et al. (2005)


Peters et al. (2005)

3-(8)
Aromatic compounds are useful
as a maturity indicator in
postmature zone.

Methylphenanthrene index (MPI):


Radke et al (1982), Radke (1988)
and Farrington et al (1988)

Based on the thermodynamic


stability; ß-position is more stable
than α-position.

MPI-3
Sampei et al. (1994)
Ro=0.79*MPI-3-0.30
(Ro=0.4-1.6).
Peters et al. (2005)
3-(9)
Range of maturity parameter
20S/(20S+20R) steranes,
22S/(22S+22R) hopanes:
up to 0.8 and 0.55 in %Ro
Dia/(Dia+Reg) steranes,
Ts/(Ts+Tm):
up to 1.4 in %Ro
(Dia/(Dia+Reg) steranes have a
disadvantage that is influenced
by depositional environment and
clay catalyst and Ts/(Ts+Tm)
depends on source.)
MA: mono-aromatic steroid
TA: triaromatic steroid
Etio: Etio-porphyrin is thermally
derived from DPEP,
DPEP:deoxo-phylloerythro-ethi-
prophyrin.
3-(10) Origin of methane Cross plots of δ13C to methane/total
biogenic or thermogenic hydrocarbon (C1/ΣCn)

Biogenic methane
δ13C about -60 to -80 ‰ vs PDB
very high C1/ΣCn more than 0.97

Thermogenic methane
δ13C more than -50 ‰ vs PDB
low C1/ΣCn down to 0.6.

δ13C value of methane increase


with increasing maturity by
thermal cracking up to -20 ‰ vs
PDB.

Tissot and Welte (1984)


4. Migration and Trap
4-(1)
Primary migration:
Migrate up or down to such a
porous and permeable carrier
rock as sand stone
The driving force is an internal
pressure due to inorganic and
organic transformations.

Secondary migration:
From the source rock through
permeable rocks along faults
and conduits to trap
Great migration distance in the
order of 100km unless special
big unconformity

Tissot and Welte (1984)


4-(2)
Porosity and fluid pressure

Interrelationship of:
Porosity of source rocks,
Fluid pressure,
Temperature,
Depth

Primary migration
efficiencies of between 5
and 80 % of available oil
are believed.

Tissot and Welte (1984)


4-(3)
Porosity and permeability
of reservoir rock

Reservoir rocks require


more than:

10 % (porosity) and
1 m-darcy (permeability).

Tissot and Welte (1984)


4-(4)
Microfracturing system in
primary migration

Many microfractures are


produced by overburden
pressure after petroleum
generation in catagenetic
stage.

Then, the microfractures connect to initial fractures to migrate


hydrocarbons.

Tissot and Welte (1984)


Tissot and Welte (1984)
4-(5)
Diffusion-controlled
processes in primary
migration

Hydrocarbons move
independently from places
of higher concentration to
places of lower
concentration.

For this diffusion system, important geological structures are:


fractures, fault, and interbedded siltstone lens.
Tissot and Welte (1984)
4-(6)
Molecular solution in water

One of possible transporting


mechanism of petroleum during
primary migration

Generally low molecular weight


hydrocarbons are more water-
soluble than high molecular
weight hydrocarbon.

For n-alkane, water-solubility


logarismically increases with
decreasing carbon number.

Aromatic compounds are more water-soluble than n-alkane.


High temperature increases water-solubility of hydrocarbon.
Molecular solution system in primary migration is important for low molecular
weight hydrocarbon.
4-(7)
Molecular solution in gas

Solubility of petroleum in gas


increases with increasing
pressure and temperature.

Tissot and Welte (1984)


4-(8) Complex system for oil accumulation

Large faults
make complex
for oil trap
system.

Major boundary fault


acts as primary
conduit for migration.

Tissot and Welte (1984)


4-(9) Preferential expulsion
Compositional fractionation
sometimes occurs due to
petroleum expulsion, which
is recognized by comparing
n-alkane distribution of
bitumens from thick and
thin source rock formations.

Thin source rocks easily


expelled light molecule n-
alkane. The lighter
molecular weight is, the
more hydrocarbon is
expelled, according to the
n-alkane distribution from
the thick ones.

Tissot and Welte (1984)


5. Source Rock Evaluation 5-(1)
Standard evaluation
sheet for source rock
potential

TOC,
Rock-Eval S1,S2
HI
OI
%Ro
Tmax
Biomarker compositions

For considering:
Kerogen type
Depositional
environment,
Hhydrocarbon potential
Maturity
Peters et al. (2005)
5-(2) Source rock generative potential

Peters and Moldowan (1993)

To assess the source rock generative potential, the most basic parameters are
TOC and S2.

More than 1% of TOC and 5mgHC/g-rock is a good source rock, and less than
0.5% of TOC and 2.5mgHC/g-rock is a poor source rock.
5-(3) TOC and S2 of shales

Peters et al. (2005)

Generally, many shales are not so rick in TOC and S2.


The peaks of TOC and S2 are sometimes about <1% and <2.5%.
Nevertheless, very high TOC and S2 more than 5% and 20mgHC/g-rock,
respectively, are occasionally interbedded in the shales and sand.
We need to know thickness, age, depositional environment, continuity and
maturity
5-(4) Controlling
factors of TOC

Primary productivity
Oxic-anoxic
condition
Sedimentation rate

Sedimentation rate is
often a key.

Ibach (1982)

Up to about 0.1mm/y
TOC increases with
increasing SD.

Over about 0.1mm/y


TOC decreases with
Ibach (1982) increasing SD.
5-(5)
S2-TOC plot

S2-TOC plot is a useful


evaluation diagram for
source rock. On this
diagram HI levels which
show kerogen type are
expressed as a linear line.

Source rocks are sometimes


plotted on the straight line
with an intercept zero,
indicating that the source
rock had deposited under
the same environment and
composed of same type
kerogen.
Peters et al. (2005)
5-(6)
Lacustrine source rock
evaluation

Coal deposits under the


condition with high
sediment+water influx and low
accommodation rate, i.e. in the
fluvial system with over filled.

Type I kerogen may deposit


under the condition with high
sediment+water influx and
high accommodation rate with
high primary productivity in
the balanced fill system
Peters et al. (2005)
5-(7) Biomarker as organic source indicator

Peters et al. (2005)

Steranes and hopane distributions are good indicators for organic source.
5-(8)
Biomarker as organic source
indicator 1

Ternary diagram of C27-C28-


C29-steranes shows origins of
organic matter;

C27-sterane is mainly from


phyto-plankton.

C28-sterane is mainly from


such specific plankton as
diatom.

C29-sterane is mainly from


Peters and Moldowan (1993)
land-plant.
5-(9)
Age control of the C28/C29
steranes ratio

Care should be paid for the


interpretation of C28/C29
steranes ratio.

Because C28/C29 sterane ratios


have changed during the last 600
Ma.

The ratio from marine source


rock with a little or no
terrigenous organic matter input
have increased from about 0.3 in
600Ma to 1.3 in 100 Ma

Peters et al. (2005)


5-(10) Oxic-anoxic proxy 1
Oxic-anoxic proxy: pristine/phytane (Pr/Ph) ratio.

High Pr/Ph ratios >3.0 indicate terrestrial organic matter input under oxic
conditions and low values <0.6 typify anoxic (Peters and Moldowa, 1993).

Peters et al. (2005)


5-(11) Depositional environment indicator

10*Gammacerane/(Gammacerane+Hopane) showing oxic-anoxic condition


according to salinity stratification .
(water-colum stratification, commonly due to hypersalinity)

Peters et al. (2005)


5-(12) Origin indicator

Highly branched isoprenoids


(HBI) are diatom markers
(Jurassic to Tertiary)
HBIs:
series of C20, C25, C30,C35

Peters et al. (2005)


Peters et al. (2005)

5-(13) Depositional indicator


Isoprenoid thiophenes:
Anoxic and iron-poor condition produce H2S
by sulfate reducing bacteria
Then H2S was incorporated into isoprenoids.
5-(14) Origin indicator 2

Irregular isoprenoid hydrocarbon


botryococcne (C34H70) is from
Botryococcus braunii.

A lacustrine alga accumurated


into boghead coal and torbanite

Peters et al. (2005)


5-(15) Origin indicator 3

Oreanane is from angiosperms


or flowering plants nearly
terrigenous mainly after
Cretaceous age.

Oleanane/(Oleanane+C30hopan
e) ratio:
Highly specific for higher plant
input

Peters et al. (2005)


Stanford Report, April 4, 2001
Mosses were the first plants to emerge
Geochemists find evidence that flowers may on land some 425 million years ago,
have evolved 250 million years ago followed by firs, ginkgoes, conifers and
several other varieties.
When flowering plants appeared on Earth ?

According to the fossil record, flowering plants


abruptly appeared out of nowhere about 130
million years ago.

"Flowering plants may have originated during


the Permian period, between 290 and 245
million years ago. We based our findings on an
organic compound called oleanane " says J.
Michael Moldowan, research professor of
geological and environmental sciences.
Gigantopterids, an extinct plant group that lived
Oleanane some 250 million years ago, may be the oldest
Oleanane is produced by many common relatives of roses, daffodils and other flowering
plants.
flowering plants as a defense against insects,
fungi and various microbial invaders. But the
Fossilized deposits of gigantopterids contain
chemical is absent in other seed plants, such oleanane – an organic chemical found in modern
as pines and gingkoes. flowering plants but absent in pines and other
seed plants.
Gigantopterids:
The oldest oleanane-producing seed plants, This drawing is a reconstruction of Vasovinea
concludes biologist David Winship Taylor of tianiia, a species of gigantopterid unearthered in
Indiana University Southeast. China in 1993.
http://www.stanford.edu/dept/news/report/news/april4/acsflowers-44.html
Artist: Hongqi Li/American Journal of Botany
5-(16) Porphyrin Organometallic derivatives
of the nucleus of the haemin
or chlorophyll molecule.

Iron and magnesium are


bonded to these
compounds.

While, during diagenesis


ion exchange takes place
in the nucleus, and nickel
and vanadium are
substituted.

Peters et al. (2005)


5-(17) Souce rock potential and environmental change

During transgressive, TOC and HI are high, and terrigenous input and
degradation are low.

Peters et al. (2005)


6. Oil-Source Rock Correlation and biodegradation

6-(1) Oil-Oil correlation:


Tool for oil-source rock n-alkane, aromatics, biomarker,
correlation isotope ratio
Oil-Source rock:
n-alkane, aromatics, biomarker,
isotope ratio
Oil-Gas:
light n-alkane, isotope ratio
Gas-Gas:
light n-alkane, isotope ratio
Gas-Source rock:
n-alkane, isotope ratio

Tissot and Welte (1984)


6-(2) Correlation by
n-alkane

n-Alkane distribution
is useful for
correlation.

Between bitumens
from source rock and
oils

Curiale (1993)
6-(3)
Correlation by steranes and
hopanes

Steranes and hopanes are the


most useful fingerprints.

Care should be paied to the


maturity.

Curiale (1993)
6-(4)
Correlation by steranes

Comparing the ternary


diagrams of sterane and
diasterane

Diasterane composition
reflects rock faces such as
clay stone.

Peters et al. (2005)


6-(5)
Confidence of oil-source
rock correlation

Under marine and


lacustrine environment,
the oil-source rock
correlation may be
known.

The gas – source rock


correlation is difficult
under deltaic and coal-
forming condition

Peters et al. (2005)


6-(6)
Biodegradation of n-alkane

n-Alkane is the most


sensitive to biodegradation.

Higher molecular n-alkanes


are easily broken in the first
stage of biodegradation

Peters et al. (2005)


6-(7)
Biodegradation stage

Hydrocarbon gases
→ n-alkanes
→ iso-alkanes
→ isoprenoids
→ aromatics
→ poly-aromatics
→ steranes&hopanes

Peters et al. (2005)


6-(8) Biodegradation effect on sulfur&nitrogen contents and API
Sulfur and nitrogen contents decrease about 4 and 0.6% to 1 and 0.1%,
respectively.
While, API increases from about 8 to 30

Peters et al. (2005)


7. Modeling 7-(1)
Changes in %Ro under different
heating rate

With increasing heating rate,


maturity of the peak of oil
window decreases:
%Ro=0.9 at <1ºC/Ma,
%Ro=0.75 at 1-2ºC/Ma,
%Ro=0.6 at 6ºC/Ma.

Therefore, computer simulation


is necessary for an accurate
discussion

Rullkotter (1993)
Geothermal gradient (℃/km)

Depending upon
1. thermal conductivity of rock strata,
2. heat flow
3. water movement

World average:25℃/km
5℃/km: ex. Andros Island in the Bahamas
90℃/km: ex. Walio oilfield in the Sarawati Basin, indonesia

Heatflow(Q) Q=k×ΔT
k:thermal conductivity
ΔT:geothermal gradient
1 (HFU: heatflow unit) = 0.42×10-5 (Wm-2)
World average: 0.63×10-5 (Wm-2)
7-(2) Kinetics of isomerization
Activation energy (E); Pre-exponential factor (A)
C: concentration of kerogen, C0: initial concentration of kerogen, k: rate constant,
t: time, A: pre-expornential factor, E: activation energy, R: gas constant 1.987
cal/deg, T: absolute temperature, q: heatig rate, (5) by Alexander et al. (1986)
C = C 0 e − kt (concentration chan ge) - - - - - - - -Sampei
- - - - - -and
- - - Suzuki
- - - - - -(2005)
------------- (1)

k = Ae − E / RT (A rrhenius equation) ----------------------- (2)

dT ∆T
=q ( = q)
dt ∆t ----------------------------------------------------------- (3)
A T − E / RT
q ∫T 0
k = e dT
---------------------------------------------------------- (4)
ART 2 − E / RT  RT RT 2  ---------------------------------------- (5)
k=( )e 1 − 2 ( E ) + 6 ( E ) 
qE

k1 = Ae − E / RT1 ; k 2 = Ae − E / R (T1 + ∆T ) ;⋅ ⋅ ⋅ ⋅ ⋅ ⋅ ⋅⋅; k n = Ae − E / R (T1 + ( n −1) ∆T ) ------------------------ (6)

C1 = C 0 e − k1 ∆t ; C 2 = C1e − k 2 ∆t ;⋅ ⋅ ⋅ ⋅ ⋅ ⋅ ⋅; C n = C n −1e − k n ∆t ----------------------------------- (7)

C n = C 0 e − ( k 1 + k 2 + ⋅⋅⋅⋅⋅⋅ + k n ) ∆t -------------------------------------------------------- (8)


7-(3) Data set of kinetic parmeters

Sampei and Suzuki (2005)


7-(4) Simulation results

Sampei and Suzuki (2005)


Sampei and Suzuki (2005)
Modeling of Burial History for the La Luna Formation(Well)
La Cira 1625K well, Colombia

Cretaceous

Age m.y
by PRA software
La Cira 1625K well, Colombia
Cretaceous

Age m.y

by PRA software