Professional Documents
Culture Documents
in Petroleum
Exploration
Geochemistry
in Petroleum
Exploration
Douglas w. Waples
BROWN AND RUTH LABORATORIES, INC.
DENVER, COLORADO
"
1985
622'.13
ISBN-l3: 978-94-010-8900-5
3. Petro-
85-105
e-ISBN-l3: 978-94-009-5436-6
DOl: 10.1007/978-94-009-5436-6
Series Editor
George deVries Klein
Department of Geology
University of Illinois at Urbana-Champaign
Consulting Editors
Michael A. Arthur
Graduate School of Oceanography
University of Rhode Island
Thomas W. C. Hilde
Department of Geophysics
Texas A(]i'M University
W. Stuart McKerrow
Department of Geology and Mineralogy
University of Oxford
J. Casey Moore
Earth Sciences
University of California-Santa Cruz,
Contents
Dedication
Preface
iv
ix
1. Introduction
1
Philosophy of Hydrocarbon Exploration
Formation of Oil and Gas
Applications to Hydrocarbon Exploration
Suggested Readings
2. Organic Facies
19
Introduction
Names and Structures
Stereochemistry and Isomers
Reactions
Isotopes
4. Kerogen
31
Introduction
Kerogen Formation
Kerogen Composition
Kerogen Maturation
Summary
Suggested Readings
43
Introduction
Compounds Present in Bitumen and Petroleum
vii
viii
6. Migration
63
Definitions
Primary Migration
Secondary Migration
Accumulation
Effects on Oil and Gas Composition
Significance for Exploration
Suggested Readings
10. Correlations
73
Introduction
Chemical Characterization for Correlations
Source-Rock Evaluation
Contamination and Weathering
Analytical Costs
Summary
Suggested Readings
7. Analytical Techniques
8. Source-Rock Evaluation
93
155
Introduction
Correlation Parameters
Correlation Parameters for Gases
Case Studies
Conclusions
Sugsested Readings
Practice Problems
Solutions to Practice Problems
181
121
Introduction
Construction of the Geological Model
Special Considerations About Burial-History Curves
Calculation of Maturity
205
Glossary
References
Index
225
217
189
Preface
This book is intended primarily as a textbook for geologists engaged in petroleum exploration. Its purpose is to
introduce the reader to organic geochemistry and to show
how to apply geochemistry advantageously in an exploration program. I have made the explicit assumption that
most readers will have a sound background in geology
but far less knowledge of, or interest in, chemistry. Because there is no need for an exploration geologist to be
an expert in organic chemistry, the amount of chemistry
used in the book is rather modest. It is, however, often
important for a geologist to understand some basic vocabulary.
The emphasis in this book is on applications of geo_chemistry to hydrocarbon exploration. Most of the analytical techniques are discussed only briefly, because
although a geologist should know what a gas chromatograph is, he or she is unlikely to be asked to repair
one. If more detailed knowledge does prove necessary, a
laboratory is the proper place to learn.
The strengths and weaknesses of the various analytical
techniques are discussed so that a geologist will be able to
anticipate pitfalls, cull bad data, and choose an appropriate analytical program. On-the-job experience will prove
invaluable in converting the basic information from this
text into a practical working knowledge.
The heart of the book, I hope, will be the examples
showing the application of geochemistry to common exploration problems. Practice problems (with answers)
are included at the end of several chapters so that the
reader can test his or her understanding of basic princiix
Chapter 1
Introduction
I ........
ATURE
(d,.g.,n.~
HYDROCARBONS
GENERATED---
DRY GAS
a::
:>
~
<{
a:
UJ
0..
~
ILl
~
z<{
~
~
PRIMARY
PRODUCT
STAGE
OIL
. . ATURE
(cal.genes
~)
CONDENSATE
~~~~~-t::W:E:T::G:A~S~'
~illIlIlIlI~~
l
IT"
1. INTRODUCTION
1984b.
overall geological model. Three main types of geochemical models (organic-facies, thermal-maturity, and
volumetric) exist at the present time; they will be dealt
with in chapters 2, 9, and 12, respectively.
Model-based approaches can be used at any stage of
exploration. In frontier areas, where data are sparse or
nonexistent, models are the only means we have of comparing one area with another. In immaturely explored
areas we will have some data with which to test and
refine our early models. Finally, use of models will help
develop entirely new plays even in mature areas.
Modeling should therefore be an essential part of any
exploration effort utilizing geochemistry. Models give us a
geological framework within which we can interpret analytical data, develop a future analytical plan, and analyze
the results in an exploration context. The successful application of geochemistry to exploration in the future will
rest heavily upon our ability to develop and apply intelligent geological-geochemical models; we shall set that as
an important goal for this text.
SUGGESTED READINGS
Demaison, G., 1984, The generative basin concept, in G. Demaison and R.]. Murris, eds., Petroleum Geochemistry and
Basin Evaluation: American Association of Petroleum
Geologists Memoir 35, Tulsa, American Association of Petroleum Geologists, pp. 1-14.
Demaison, G. and R.]. Murris, 1984, eds., Petroleum
Geochemistry and Basin Evaluation: American Association
of Petroleum Geologists Memoir 35, Tulsa, American Association of Petroleum Geologists, 426 pp.
Hunt,]. M., 1979, Petroleum Geochemistry and Geology: San
Francisco, Freeman, 617 pp.
Ourisson, G., P. Albrecht, and M. Rohmer, 1984, The microbial
origin of fossil fuels: Scientific American, August, pp. 44-51.
Tissot, B. P., 1984, Recent advances in petroleum geochemistry
applied to hydrocarbon exploration: Bulletin of the American
Association of Petroleum Geologists, v. 68, pp. 545-563.
Tissot, B. and D. H. Welte, 1978, Petroleum Formation and
Occurrence: Berlin, Springer-Verlag, 538 pp.
Waples, D. W., 1984, Modern approaches in source-rock
evaluation, in]. Woodward, F. F. Meissner, and]. 1. Clayton,
eds., Hydrocarbon Source Rocks of the Greater Rocky Mountain Region: Denver, Rocky Mountain Association of Geologists, pp. 35-49.
Chapter 2
Organic Facies
Toe
0
.1
.2
(%)
.3
.4
.5
100
200
u;
a:
w
w
I-
CARBONATE
SEDIMENTS
(64,000,000)
300
:I:
I-
a..
w
400
500
FOSSIL FUELS
(10,000)
600
2. ORGANlC FACIES
TERRESTRIAL
AQUEOUS
1.5 .7.0xlOO!.org. C/ year
13%
DESERT
STEPPE
GR ASS LAND
...
294 l / km'
"
fOREST
18%
8%
AGRICULTURE
ESTUARIES
ALGAL BEDS
REEfS
47%
...
...
2!>OO Ilkm'
2798 l / km'
...
46 %
...
6429 IIkm'
7927 IIkm'
20.000 l / km' ~
A partial listing of the many factors influencing productivity would include nutrient availability, light intensity,
temperature, carbonate supply, predators, and general
water chemistry. Each of these categories could in turn be
further subdivided. For example, nutrient availability
would depend on such factors as water-circulation patterns, orogeny and erosion, volcanism, paleoclimate, and
recycling by organic decay.
Nutrient availability is, in fact, one of the critical parameters governing productivity. Shallow-marine envi-
r.Jl
t:::J
California, Peru, Namibia, and northwest Africa that result from the movement, induced by the Coriolis force, of
surface waters away from these coasts. There is another
zone of seasonal upwelling off the Horn of Africa in the
Indian Ocean as a result of monsoonal winds that drive
surface waters away from the coast. All these areas exhibit high productivity when upwelling occurs.
Theoretical models have been developed to predict upwelling (and consequent productivity) in ancient seas
from input data on continental configurations, land
masses, wind- and water-circulation patterns, and paleoclimates (for example, Parrish, 1982; Parrish and Curtis, 1982). An example is shown in figure 2.4 for the
Aptian stage of the Early Cretaceous. The accuracy of the
models was tested by comparing predicted occurrences of
upwellings with rock facies known to be associated with
upwelling systems (organic-rich, phosphatic, glauconitic,
cherty). Parrish (1982) reported an encouraging correlation betwen predicted and reported occurrences of upwelling facies for the Paleozoic.
Such models are interesting, and may in fact prove
useful in future exploration efforts. There are, however,
some problems associated with their application. First,
productivity is probably not as important a factor as pres-
pwelling
FIGURE 2.4 Atmospheric circulation and upwelling patterns
in northern summers during the Maestrichtian (Late Cretaceous). Reprinted by permission of Elsevier Science Publishing
Company from Parrish and Curtis, 1982.
2. ORGANIC FACIES
water column, soils, and sediments is biological, and because most biological oxidation processes require
molecular oxygen (02 ), the simplest way to limit oxidation is to limit the supply of oxygen. All large organisms
require oxygen in order to live, although some species can
tolerate oxygen levels as low as 0.5 milliliters (mL) per
liter (L) (compared to about 6 mLIL in surface waters).
At lower levels of dissolved oxygen, many species disappear; the remaining individuals often become dwarfed in
an effort to survive in a hostile environment. At dissolvedoxygen levels below about 0.2 mLlL, essentially the only
viable organisms are those that we call anaerobesmicroorganisms that utilize materials like sulfate or nitrate ions instead of molecular oxygen as electron
acceptors in their metabolic processes.
We call the zone in which oxygen contents are high the
oxic zone; the zone where oxygen falls below 0.2 mLIL is
called the anoxic zone. Processes that occur in these two
zones are called aerobic and anaerobic, respectively. The
term dysaerobic has been used to describe processes occurring in the transitional zone (0.2-0.5 mLIL), and we
could coin the term dysoxic to describe the zone itself
The term "anoxic" literally means "having no oxygen,"
but because of the radical change in biota that occurs at
about 0.2 mLlL, its use in practice has been expanded to
include very low oxygen levels as well.
Anoxia is of tremendous importance in the preservation of organic matter in sediments, because when the
availability of oxygen is limited, diagenesis is restricted
to anaerobic processes. These anaerobic processes are
inefficient compared with aerobic diagenesis, and are
usually limited in scope by the availability of sulfate or
nitrate. Thus if anoxia can develop, preservation of organic matter will be much enhanced.
Anoxic sediments are not always easy to recognize,
because some of the commonly used indicators of anoxia
may be misleading. Anoxic sediments always contain ele-
10
/ {~
.........
....... ................ ....
.. .
..............................
,
D nsity
slratifi alion
.............................
.. ......... .............. .
Oz-poor
bottom
waters
2. ORGANIC FACIES
C..ontinental
Metel
I;S('
Continental
lope
11
Continental
shelr
Oxidized
(;tn to whitl'
- 2800- .
FIGURE 2.6 Schematic diagram showing the position of the
oxygen-minimum layer with respect to surface waters and
the sediment-water interface. Sediments deposited where the
OML intersects the sediment-water interface will be the least
oxygenated. If the OML is intensely developed, they will be
anoxic.
12
Contin!;'nwl
,;5('
C..ontinenwl Continc'nwl
shelf
, lop<'
+2~:~~:_~__:_:_~_~_~_:~~_~__
~_~~~_~_~_t_:_~_~_~~~~_~~~~~~~1.l
Sudan'
\\.111"
11,,\\
,'lIll1"III'""U'
- 400Expand!;'d Ol Minimum
lay!;''' < 0.2 rnL
- 800- 1200-
- 1600-
'
'
- 2000_ __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _- J
&hematic diagram of an expanded D.lygenminimum layer. Expansion upward permits low-oxy,gen bottom waters to move onto the broan expanses of continental
shelf and thereby increase the volume of low-oxy'~en sediment.
FIGURE 2.7
2. ORGANIC FACIES
13
Uifi.0.ti.i.ttGGttUU~:~~~:8{i:UM1:f:
............................................................
:::::::::::::::::::::::::::::::::::,\nw.it
01'
!>!l'" t (),::
in o,,!pnk matlt'!'
'~??}:~::;J:~Ji8:ilii08:8~[:I!:~
'-:-::::::UU/UH
CONTENT Of DISSOlVED
O:! .. WATR
. . - tilGti WATR
FLUX
FLUX
14
planktonic) origin is consumed more readily by organisms than are other types of organic material, because its
chemical components are digestible and provide precisely
the nutrients required by scavengers and predators. Nitrogen and phosphorus are in particular demand; their
virtual absence in much terrestrial organic material, especially in structural (woody) material, renders it of little
nutritional value. Furthermore, the phenolic components
present in lignin-derived terrestrial material are toxic to
many microorganisms, thus preventing extensive diagenesis of such material.
Any extensive organic diagenesis is therefore likely to
eliminate algal organic matter first. That material which
remains is dominantly of terrestrial origin, and may include woody, cellulosic, lignitic, cuticular, or resinous
material, all of which are chemically quite distinct from
each other. It may also contain very resistant organic debris derived from erosion of ancient rocks, forest fires,
and other oxidative processes.
Rapid Sedimentation and Burial. Rapid sedimentation and
burial can also enhance preservation. TOC values increase as sediment-accumulation rates increase (fig.
2.11), as a result of more rapid removal of organic material from the zone of microbial diagenesis.
Rapid burial can be accomplished by a high influx of
inorganic detritus, biogenic inorganic sediment, or organic material. Rapid deposition of inorganic detritus is
common in turbidites and in prodelta shales. The extremely high accumulation rates for biogenic carbonates
and siliceous sediments in zones of high productivity promote preservation of the associated algal protoplasm.
Coals also accumulate very rapidly and, with their high
concentrations of organic matter, provide an ideal means
of maintaining low-oxygen conditions.
Rapid settling of organic debris through the water column is also important, because extensive decomposition
occurs during its fall to the ocean floor. In fact, much of
the organic material that does reach the bottom in deep
waters arrives in relatively large fecal pellets, which set-
~
()
oI-
.,
t:I
W.8ALTIC
PERU
f::r0REGON
0 . 1 r-'-TTTn~-'-'OTnn'-~TT,"~-'-'TTmm
0.1
1
10
100
1000
2. ORGANIC FACIES
15
10
o
....
10
100
Dependence of TOC values on sediment-accumulation rates for three lithologies. The downturn in the curves
at high sediment-accumulation rates occurs where the effects
of dilution by mineral matter begin to outweigh the effects of
enhanced preservation by rapid burial. After Ibach, 1982, by
permission of the American Association of Petroleum
Geologists.
FIGURE 2.12
Virtually everyone has seen samples of both black, organic-rich rocks and oxidized, organic-lean shales. Despite their great and obvious differences, such facies are
often quite complexly interrelated.
Some workers have proposed that the common "black
shales" of mid-Cretaceous age (Aptian to Turonian) from
the North Atlantic were deposited during "oceanic anoxic
events." The detailed cores obtained as part of the Deep
Sea Drilling Project suggest, however, that these anoxic
facies represent only a small portion of the total sediment
deposited at any site during the mid-Cretaceous, and that
the anoxic events were interrupted by longer periods of
strong oxygenation.
Figure 2.13 shows a core of middle Cenomanian rocks
from a site in the North Atlantic. Laminated, black sediments containing more than 2% TOC and high proportions of marine algal material grade into gray-to-white,
bioturbated sediments that contain moderate to negligible
amounts of organic matter. The complex interbedding of
oxidizing and reducing facies suggests local control on
oxygen levels in the bottom waters during this time. It also
shows that cuttings samples from this sequence could not
possibly give a realistic picture of depositional conditions.
In most cases where well samples are analyzed, our con-
16
Geologit:al
pt'liods
Tel'lial"\'
100
CreWe ous
Junl -it'
200
TI'iassil'
Permian
300
400
500
rbonifer.
I'rindpal coal
rt'SOlllTl"S
lUI
~ 1.1
1.,llm~
.!uu
tI
.,!tltl
De\'onian
Silul'ian
OrdOl;eian
C:lmbl'ian
rocks throughout Phanerozoic time compared to transgressions ami regressions according to the sea-level curve of Vail
et al. (1977). Adaptedfrom Tissot (1979) by permission from
Nature, Vol. 277, pp. 464-465, figure 3. Copyright 1979
Macmillan Journals Limited.
2. ORGANIC FACIES
of oceanic- and atmospheric-circulation patterns. Consequently, such models are not yet of much practical value
for the distant past.
Preservation is best accomplished where oxygen is excluded from bottom waters. There are a number of mechanisms by which oxygen depletion may be fostered and
maintained, including stagnancy or near-stagnancy, a
strongly developed oxygen-minimum layer (often related
to high productivity), and rapid burial. It is often very
difficult to separate the influences of these various factors
in a particular depositional environment.
Rapid accumulation of sediment shortens the residence
time of organic matter in the zone of diagenesis and thus
promotes preservation. If the rapidly accumulating sediment is mainly clastic, however, dilution effects may lead
to lower TOC values in spite of enhanced preservation
rates. In biogenic sediments or coals, in contrast, where
sediment-accumulation rates are directly proportional to
organic-carbon-accumulation rates, dilution is far less
marked.
Because of its role in creating rocks with excellent hydrocarbon-source potential, anoxia in bottom waters is a
phenomenon whose effects we should learn to recognize
in ancient rocks. Some of the commonly applied criteria
are apt to be misleading, however. It is important to be
able to distinguish local anoxia or anoxia developed deep
within sediments from anoxia induced by anoxic bottom
waters. The most reliable criteria for bottom-water
anoxia are the preservation of fine depositional laminae,
and the presence of high TOC values coupled with the
occurrence of undegraded marine organic matter.
Anoxic events in the past were probably not as large in
scale or as long-lasting as some workers have suggested.
Although certain periods undeniably contain more than
their share of anoxic rocks, anoxic sediments were deposited discontinuously through time and space. Direct control of the anoxia was thus probably local, as a result of
high productivity or sluggish circulation. As in the modern oceans, such events were often interrupted for long
periods before anoxia was reinduced.
Models that integrate the concepts of organic richness
with depositional cycles and facies analysis will be valuable in the future for understanding hydrocarbon systems
in basins. To derive maximum value from geochemical
17
analyses, we should always strive to place the organicrich rocks in the larger context of basin evolution through
time and space.
SUGGESTED READINGS
Arthur, M. A. and J. H. Natland, 1979, Carbonaceous sediments in the North and South Atlantic: the role of salinity in
stable stratification of Early Cretaceous basins, in M. Talwani, W. Hay, and W. B. F. Ryan, eds., Deep Drilling Results
in the Atlantic Ocean: Continental Mar,'sins and Paleoenvironment: American Geophysical Union, pp. 375-401.
Cool, T. E., 1982, Sedimentological evidence concerning the
paleoceanography of the Cretaceous western South Atlantic
Ocean: Paleogeography, Paleoclimatology, Paleoecology, v.
39, pp. 1-35.
de Graciansky, P. c., G. Deroo, J. P. Herbin, L. Montadert, C.
Milller, A. Schaaf, andJ. Sigal, 1984, Ocean-wide stagnation
episode in the late Cretaceous: Nature, v. 308, pp. 346-349.
Dean, W. E., M. A. Arthur, and D. A. V. Stow, 1984, Origin
and geochemistry of Cretaceous deep-sea black shales and
multicolored claystones, with emphasis on Deep Sea Drilling
Project Site 530, southern Angola Basin, in W. W. Hay and
J. C. Sibuet, eds., Initial Reports of the Deep Sea Drilling
Project, Vol. LXXV: Washington, U.S. Government Printing
Office, pp. 819-844.
Demaison, G.J. and G. T. Moore, 1980, Anoxic environments
and oil source bed genesis: Bulletin of the American Association of Petroleum Geologists, v. 64, pp. 1179-1209.
Fischer, A. G. and M. A. Arthur, 1977, Secular variations in the
pelagic realm, in H. E. Cook and P. Enos, eds., Deep Water
Carbonate Environments: SEPM Special Publication 25,
Tulsa, pp. 19-50.
Jones, R. W. and G.J. Demaison, 1982, Organic faciesstratigraphic concept and exploration tool, in A. SaldivarSali, ed., Proceedings of the Second ASCOPE Conference and
Exhibition: Manila, ASCOPE, pp. 51-68.
Kirkland, D. W. and R. Evans, 1981, Source-rock potential of
evaporitic environment: Bulletin of the American Association
of Petroleum Geologists, v. 65, pp. 181-190.
Leggett, J. K., 1980, British Lower Palaeozoic black shales and
their palaeo-oceanographic significance: Journal of the
Geological Society, London, v. 137, pp. 139-156.
Pisciotto, K. A. and R. E. Garrison, 1981, Lithofacies and depositional environments of the Monterey Formation, California,
in R. E. Garrison and R. G. Douglas, eds., The Monterey Formation and Related Siliceous Rocks of California: SEPM
Pacific Section, pp. 97-122.
18
Chapter 3
Organic Chemistry
and Isotopes
INTRODUCTION
Anyone who uses petroleum geochemistry must be familiar with basic chemical terminology. The objective of this
chapter is to acquaint the reader with the names of common compounds and with several different conventions
for drawing their structures. This objective is very different from that of a normal course in organic chemistry, in
which one must also learn all the reactions of many
classes of compounds. The chemical reactions of interest
to us are very few and are discussed only briefly. This
chapter also includes a summary of the basic theory behind isotope effects.
All compounds containing carbon atoms, except carbon dioxide, carbonates, and metal carbides, are termed
organic. This usage is historical and does not imply that
all such compounds are necessarily derived from living
organisms. Organic chemistry is thus the study of carboncontaining compounds, and organic geochemistry
the study of organic compounds present in geological
environments.
NAMES AND STRUCTURES
HYDROCARBONS
In chemical terms a hydrocarbon is a compound containing only the elements carbon and hydrogen. Petroleum
and natural gas are themselves often referred to as "hydrocarbons," but that usage is incorrect from the chemist's point of view because those materials often contain
substantial amounts of nitrogen, sulfur, oxygen, trace
19
20
or
Methane
I
H-C-H
I
H
Cydohexane
H H
Ethane
H-C-C-H
H H
or
Methane
Ethane
Cydohexane
CH 3 (CH 2 )3 CH 3
n-pentane
n.pentane
Cydohexane
Name
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Abbreviations
CH 4
CzHG
C3 H 8
C4 H lO
CS HIZ
C6 H14
C7 H 16
CaH 18
CsHzo
ClO H 2Z
CH 4
CH 3 CH 3
CH:l CH zCH 3
CH 3 (CH zhCH:l
CH:l (CH zhCH 3
CH 3 (CHz)4 CH 3
CH 3 (CHzlsCH 3
CH:l ( CHZ)6 CH 3
CH 3 (CH2 hCH 3
CH 3 (CH zhCH 3
None
None
A
/V
AA
/VV
/"v"V'..
/VVV
~
/VVV'V
"c=c
H/
2-methylhexane
2,2,3-trimethylbutane
The term methyl, which we used earlier, is the adjectival form of the word methane. In the case of 2methylhexane (above) the basic structure is hexane; a
CH 3 (methyl) group is attached to the second carbon
atom. Other adjectival forms are made by dropping the
-ane ending and adding -yl (for example, ethyl and propyl).
Among the most important branched hydrocarbons in
organic geochemistry are the isoprenoids. Regular isoprenoids consist of a straight chain of carbon atoms with a
methyl branch on every fourth carbon. Isoprenoids ranging in length from six to forty carbon atoms have been
found in petroleum and rocks (table 3.2).
21
"H
Ethene
(Ethylene)
"c=c /
.H /
CH 3
"
Propene
(Propylene)
Cyclohexene
Isoprene
22
Name
Structure
Number of
Carbon
Atoms
Phytane
20
Pristane
19
Norpristane
18
17
16
+ H2C=CH 2
Ethene
catalyst
---~) H3 CCH 3
(3.1)
Ethane
Farnesane
15
squalane
30
Lycopane
40
Perhydroj3-Carotene
(j3-Carotane)
40
o
Benzene
Toluene
m-xylene
Naphthalene
23
o
Basic sterane
structure
Basic triterpane
structure
C30
C30
FIGURE 3.1 Basic structures of some typical cyclic and polycyclic hydrocarbons.
23
1984.
Naphthalene
Some aromatic molecules are very large. Polycyclic aromatic hydrocarbons (PAR) having fused ring structures
24
o
II
OH
PALMITIC ACID
(hexadecanoic acid)
Naphthenoaromatic hydrocarbons
OH
/V"V'VV'V
DODECYL ALCOHOL
R'
DPEP type
ETIO type
25
FIGURE 3.6 The propane molecule, showing actual bond angles of approximately 1090
FIGURE 3.5
Many nonhydrocarbon molecules common to living organisms are also present in sediments. Among these are
lignin, carbohydrates, and amino acids. Lignin is an important component of wood, providing much of the structural support for large land plants. It is a polymer
consisting of many repetitions and combinations of three
basic aromatic subunits having the structures shown
below.
Lignin subunits
26
co
H
Cis DECALIN
(both hydrogens alpha)
Cb
Trans DECALIN
(one hydrogen alpha, one beta)
FIGURE 3.9 Alpha (111111 ) and beta ( ~) attachments in decalin. A group attached in the alpha position at the ring
juncture points away from the viewer; in the beta position it
points toward the viewer.
FIGURE 3.7 Benzene, an aromatic molecule, has a planar
structure with bond angles in the ring of 120.
co
Cis DECALIN
H
H
Cis
Trans
Cis and trans isomers of 1,3-dimethylcyclohexane. The cis fonn has the two methyl groups on the same
side of the ring; the trans fonns on opposite sides.
Trans DECALIN
FIGURE 3.10 A second convention for showing the stereochemistry of hydrogen atoms attached to ring junctures.
Open circles indicate the hydrogen is below the plane of the
ring (alpha); black circles indicate it is in the beta position.
FIGURE 3.8
identical can differ stereochemically. For example, a compound like 1,3-dimethylcyclohexane can exist in a cis
form and a trans form (fig. 3.8). In a cis compound the
two groups are on the same side of a particular feature (in
this case the plane of the ring), whereas in the trans form
they are attached to opposite sides.
When several saturated rings are fused together, as in a
sterane molecule, groups attached at the ring junctures
can point either toward or away from the viewer. In one
convention these two geometries are indicated by a heavy
dark wedge or a dotted line, respectively (fig. 3.9). If nO
particular geometry is known or implied, a plain or
squiggly line is used. The position pointing away from the
viewer is called alpha (a); that pointing toward the
viewer is beta ((3).
A second convention uses circles to indicate the geometry of hydrogen atoms attached to ring junctures (fig.
3.10). Open circles indicate that the hydrogen is attached
27
FIGURE 3.11
(3.3)
REACTIONS
We need not worry about most of the reactions that organic molecules can undergo, because the majority occur
only in the laboratory. Relatively few take place in
sedimentary rocks.
28
ISOBUTANE
( 2-methylpropane)
n-BUTANE
FIGURE 3.12
isobutane.
3CH,CH,~
+ 6CH,
(3.5)
(3.6)
29
20R
,
FIGURE 3.14 Example of epimerization in steranes by removal and replacement of the hydrogen atom attached to C20. Reprinted by permission of Cambridge University Press
from Mackenzie and McKenzie, 1983.
"
TABLE 3.3
Element
Isotopic abundance
Carbon
12C
13C
lH
2H
32S
34S
14N
15N
ISOTOPES
Isotopes of an element differ only in the number of neutrons in the nuclei of the atoms; the number of protons and
electrons are the same. Many isotopes are unstable; their
rates of decay can in some cases be used as clocks for agedating ancient materials. The important isotopes in
petroleum geochemistry, however, are stable. For most
ordinary chemical purposes we consider the chemistries
of all isotopes of an element to be identical; in actuality,
however, there are small but important differences in
the reactions of these isotopes that make them useful
geochemical tools.
The elements ofinterest in isotopic analyses are carbon,
hydrogen, sulfur, and nitrogen, in decreasing order of
popularity. The particular isotopes measured are shown
in table 3.3. Stable isotopes are useful because the proportions of the two isotopes of each element vary from sample
to sample as a result of isotope effects.
There are actually two distinct types of isotope effects:
kinetic and equilibrium. Both effects arise because heavy
isotopes form stronger bonds than light isotopes. One
consequence of this difference is that heavy isotopes prefer
to be involved in as many bonds as possible, lighter
isotopes in as few as possible. This preference causes
separation of heavy and light isotopes any time an equilibrium is reached. For example, in the oceans carbon
dioxide is in equilibrium with various carbonate species.
Equation (3.7) shows that there will be a greater-thanaverage amount of the light isotope ct 2 e) in the carbon
Hydrogen
Sulfur
Nitrogen
=
=
=
=
=
=
=
=
98.8888
1.1112
99.985
0.015
95.00
4.22
99.63
0.37
Standard
%
%
PDB'
%
%
SMOW+
%
%
CD=!:
%
%
Atmos. N2
'POB is a marine limestone consisting of a belemnite from the Pee Dee FOl"ffiation of
the Cretaceous of South Carolina.
tSMOW is standard mean ocean water, distributed by the International Atomic
Energy Agency.
tCO is the mineral !roilite from the Canyon Diablo meteorite.
enriched in
12C
enriched in
(3.7)
13C
Although the influence of carbonate equilibria on organic-geochemical processes is important, the equilibrium isotope effect plays a far less important role than the
kinetic isotope effect in petroleum geochemistry. The kinetic isotope effect arises from a difference in the rates at
which two isotopes react. Light isotopes react faster than
heavy ones because their bonds are weaker. Thus any
process that is kinetically controlled (for example, the
reactions involved in hydrocarbon generation) will show
a kinetic isotope effect. All products will be enriched in
30
Marine
limestone
Nonmal'ine
limestone
1 Kerogen
_Oil
1 Ethane
1 Methane
Methane (biogenic)
-80
-70
I
-60
I
-50
-40
-30
OLlC
-20
-10
0100
teriaLs.
CRUDE OIL
+10
+20
eLl-Rich
error, and the difference 3 (delta) between the two samples is reported in parts per thousand (usually written as
0/00 and called permii). The formula for calculating 3 13C
is given in equation (3.8). The most common standards
for the various isotopes are listed in table 3.3.
(3.8)
5
FIGURE 3.16 Fractionation of carbon iBotopes during photosynthesis. The lighter carbon reacts faster, and thus is incorporated into organic matter preferentially (kinetic isotope
jfictJ. The heavier carbon preftrs to be in the form of carbonate, which is in equilibrium with carbon dioxide dissolved in natural waters (equilibrium isotope effect).
the light isotope compared to the original starting material, whereas any unreacted starting material will be enriched in the heavy isotope.
Isotope contents are normally reported as a ratio of the
heavy isotope to the .light isotope. Raw ratios are always
compared to a standard in order to minimize measuring
Chapter 4
Kerogen
INTRODUCTION
32
are mainly oil or gas, and how much oil or gas can be
expected.
The term kerogen was originally coined to describe the
organic matter in oil shales that yielded oil upon retorting. Today it is used to describe the insoluble organic
material in both coals and oil shales, as well as dispersed
organic matter in sedimentary rocks. As figure 2.1 shows,
the amount of organic matter tied up in the form ofkerogen is far greater than that in living organisms or in economically exploitable accumulations of coal, oil, and
natural gas.
Coals are a subcategory of kerogen. Humic coals are
best thought of as kerogens formed mainly from landplant material without codeposition of much mineral
matter. Algal (boghead) coals are formed in environments where the source phytoplankton lack both calcareous and siliceous skeletal components. Oil shales, in
contrast, have more mineral matter than algal coals, with
some of the inorganic matrix often being contributed by
the algae themselves. Coals and oil shales should therefore be viewed merely as sedimentary rocks containing
special types of kerogens in very high concentrations.
KEROGEN FORMATION
BIOGENIC MOLECULES
.0 1
;;;
a:
...ww
......
SMALLER FRAGMENTS
ii:
10 0
'"
CONDENSATION,
POL YMERIZATION
LIFE
-----If)
u;
w
Z
w
"Q
HUMIC SUBSTANCES
....
BIOCHEMICAL AND
CHEMICAL
DEGRADATION
:z:
..
MAJOR CONSTITUENTS
OF LIVING MATTER
III
100 0
10,00 c
ll'-METHANE
)}o;,
LOSS OF
CO 2 , H 2 0, NH3
---(1)---
KEROGEN
GAS
DEAr CARBON
u;
W
THERMAL
MATURATION
"....
..
----Z
w
CRACKING
...ciw
::E
occurring in the sediments, and if the sediments are depleted in heavy-metal ions (which is often the case in
nonelastic sediments but is seldom true in shales), large
amounts of sulfur may become incorporated into the
kerogen structure. The amount of sulfur contributed by
the original organic matter itself is very small. Carboncarbon double bonds, which are highly reactive, are converted into saturated or cyclic structures.
Kerogen formation competes with the destruction of
organic matter by oxidative processes. Most organic oxidation in sedimentary environments is microbially mediated. Microorganisms prefer to attack small molecules
that are biogenic, or at least look very much like biogenic
molecules. Geopolymers are more or less immune to bacterial degradation, because the bacterial enzyme systems
do not know how to attack them. In an oxidizing environment many of the small biogenic molecules will be attacked by bacteria before they can form geopolymers. In a
low-oxygen (reducing) environment, in contrast, the subdued level of bacterial activity allows more time for the
formation of geopolymers and, therefore, better organic
preservation.
Kerogens formed under reducing conditions will be
4. KEROGEN
TABLE 4.1
Maceral
Alginite
Exinite
Cutinite
Resinite
Liptinite
Kerogen Type
II
II
II
II
Vitrinite
III
Inertinite
IV
Original OM
Fresh-water algae
Pollen, spores
Land-plant cuticle
Land-plant resins
All land-plant lipids; marine
algae
Woody and cellulosic material
from land plants
Charcoal; highly oxidized or
reworked material of any
origin
33
ming, Utah, and Colorado. Extensive interest in those oilshale deposits has led to many investigations of the Green
River Shale kerogens and has given Type I kerogens much
more publicity than their general geological importance
warrants. Occurrences of Type I kerogens are limited to
anoxic lakes and to a few unusual marine environments.
Type I kerogens have high generative capacities for liquid
hydrocarbons.
Type II kerogens arise from several very different
sources, including marine algae, pollen and spores, leaf
waxes, and fossil resin. They also include contributions
from bacterial-cell lipids. The various Type II kerogens
are grouped together, despite their very disparate origins,
because they all have great capacities to generate liquid
hydrocarbons. Most Type II kerogens are found in marine
sediments deposited under reducing conditions.
Type III kerogens are composed of terrestrial organic
material that is lacking in fatty or waxy components. Cellulose and lignin are major contributors. Type III kerogens have much lower hydrocarbon-generative capacities
than do Type II kerogens and, unless they have small
inclusions of Type II material, are normally considered to
generate mainly gas.
Type IV kerogens contain mainly reworked organic debris and highly oxidized material of various origins. They
are generally considered to have essentially no hydrocarbon-source potential (but see Smyth, 1983, for a dissenting opinion).
Hydrogen contents of immature kerogens (expressed as
atomic HlC ratios) correlate with kerogen type (fig. 4.2).
In the immature state, Type I (algal) kerogens have the
highest hydrogen contents because they have few rings or
aromatic structures. Type II (liptinitic) kerogens are also
high in hydrogen. Type III (humic) kerogens, in contrast,
have lower hydrogen contents because they contain extensive aromatic systems. Type IV kerogens (not shown),
which mainly contain polycyclic aromatic systems, have
the lowest hydrogen contents.
Heteroatom contents of kerogens also vary with kerogen type. Type IV kerogens are highly oxidized and therefore contain large amounts of oxygen. Type III kerogens
have high oxygen contents because they are formed from
lignin, cellulose, phenols, and carbohydrates. Type I and
Type II kerogens, in contrast, contain far less oxygen because they were formed from oxygen-poor lipid materials.
34
(Do
Co
H
ICH2'lOCH3
ABC
ATOMIC HIC
1.65
1.28
0.84
ATOMIC OIC
0.06
0.10
0.13
OIL
OIL + GAS
GAS
HYDROCARBONS
CH3
Sulfur and nitrogen contents of kerogens are also variable and, in some cases, interrelated. Nitrogen is derived
mainly from proteinaceous material, which is destroyed
rapidly during diagenesis. Most high-nitrogen kerogens
were therefore deposited under anoxic conditions where
diagenesis was severely limited. Because lignins and carbohydrates contain little nitrogen, most terrestrially influenced kerogens are low in nitrogen.
Kerogen sulfur, in contrast, is derived mainly from sulfate that was reduced by anaerobic bacteria. High-sulfur
kerogens (and coals) are almost always associated with
marine deposition, because fresh waters are usually low
in sulfate. Sulfur is only incorporated into kerogens in
large quantities where sulfate reduction is extensive and
where Fe+ 2 ions are absent (organic-rich, anoxic,
marine, nonelastic sediments). Many high-sulfur kerogens are also high in nitrogen (for example, the Permian
Phosphoria and Miocene Monterey Formations).
Environmental interpretations based on sulfur contents
are not limited to organic sulfur. A plot of pyrite concentration versus Toe values can be used to determine depositional conditions (fig. 4.3).
The division of kerogens into Types I-IV on the basis of
chemical and hydrocarbon-generative characteristics has
2.5
2
Euxinic
(anoxic. H~S)
;0
~.
1.5
VJ
:$2
.5
0
Nonmarine
4
0
,~()
TOe
4. KEROGEN
been supported by another independent scheme for classifying kerogens using transmitted-light microscopy.
Kerogen types are defined by the morphologies of the
kerogen particles. In many cases the original cellular
structure is still recognizable, proving the origin of the
particle. In others the original fabric has disappeared
completely, forcing us to make assumptions about the
source organisms. Microscopic organic analysis has
reached a fairly high level of refinement and is often capable of assessing kerogen type with good accuracy.
The different types of kerogen particles are called macerals, a term taken from coal petrology. Macerals are
essentially organic minerals; they are to kerogen what
minerals are to a rock. The kerogen in a given sedimentary rock includes many individual particles that are often
derived from a variety of sources. Thus few kerogens consist of a single maceral type.
Maceral names were developed by coal petrologists to
describe, wherever possible, the materials from which a
maceral was derived. A list of the most common macerals
and their precursors is given in table 4.1.
It is possible to make a reasonably good correlation
between kerogen type based on chemical characteristics
and kerogen type based on visual appearance. The correspondence is not perfect, however, because there is not a
perfect biological separation of the various types of living
organic matter. The biggest problem comes in identifYing
Type III kerogen. What appears to be vitrinite (Type III
kerogen) by visual analysis may have chemical characteristics intermediate between Type II and Type III kerogens
because of the presence of small amounts of resin or wax.
KEROGEN MATURATION
lNfRODUCTION
35
36
Compound
Formula
CH4
CH4
/VVVV
0)
C1oH 22
CO
C lOH 20
C lOH 18
(X)
ClOH12
CO
ClORa
Hie
Atomic
HlC Ratio
1.43
4.0
2.2
2.0
1.8
1.2
0.8
o
+~
1.29
0.96
0.47
4. KEROGEN
37
PRINCIPAL PRODUCTS
OF
KEROGEN EVOLUTION
_
1!iO
C02 H20
Oil
GAS
u
J:
!:?
::!:
0
~
100
<
O!iO
Low matunty
0
010
020
ATOMIC OI C
FIGURE 4.5 Van Krevelen diagram showing maturation pathways for Types I, II, and III kerogens as traced by changes in
atomic HIC and OIC ratios. The shaded areas approximately
represent diagenesis, catagenesis, and metagenesis, successively. Reprinted by permission of the American Association
of Petroleum Geologists; adaptedfrom Tissot et al., 1974.
High maturity
38
DEPTH AND
TEMPERATURE
DIAGENESIS
.........
........
......
CATAGENESIS
......
TOTAL BITUMEN
GENERATED "
,,
BITUMEN
,,
,
MET AGENESIS
INCREASING
HYDROCARBON GENERATION
ken off the kerogen matrix. Some of these are hydrocarbons, while others are small heterocompounds. These
small compounds are much more mobile than the kerogen molecules and are the direct precursors of oil and
gas. A general name for these molecules is bitumen.
Bitumen generation occurs mainly during catagenesis;
during metagenesis the chief product is methane. If
neither expulsion from the source rock nor cracking of
bitumen occurred, there would be a large and continuous
build-up of bitumen in the rock as a result of catagenetic
decomposition of kerogen (fig. 4.7, dashed curve). What
actually occurs, however, is that some of the bitumen is
expelled from the source rock or cracked to gas, resulting
in lower bitumen contents in the source rock (fig. 4.7,
solid curve). Both curves are highly idealized, however,
because natural variations among samples cause much
scatter in experimental data.
Proportions of hydrocarbons in rock extracts increase
4. KEROGEN
3.000
4 .000
5 .000
6 .000
;;;
..
7.000
. .'
Q.
w 8 .000
Q
9 .000
. . ..
..
..
10.000
"
11.000
1.0
2 .0
3 .0
39
40
.4
RESINITE-
RICH
.0
<::::::::::
1.0
I
~ ~A~~T~~I~-~I~~?
a:
I-
GAS
______
I-
VITRINITE-RICH
~ OAS/PAIIAFFINIC~H
CONDENSATE
~"
----------,
---______
lIPTINITE-RICH
a:
a:
WAltY OIL
LIGHT PARAFFINIC ~
______G_A_S____________________________
HEAVY S-RICH.
ASPHALTIC OIL
::E
a:
c(
GAS
CLASTIC
SEDIMENTS
PARAFFINIC I
NAPHTHENIC CONDENSATE
-----=
~~~~C~H4~
GA8/PAIIAFFIN~ CH
GAS
::E
GAI/NAPHTHENIC CONDENSATE
1.4
1.2
<. . .
->
GAS / NAPHTHENIC
CONOENSATE~
PARAFFINIC/NAPHTHENIC OIL
H"
R.
>-
~
III:
~
l-
...c
:IE
...z
.50
:IE
.75
III:
I-
1.35
II
0
VERY RICH
ROCKS
0
0
GJ
V
2.00
a
MODERATELY
C
RICH
LEAN
ROCKS
ROCKS
LJ
"V
"V
In
CRACKING
OF LIQUID He
SUMMARY
41
Chapter 5
Bitumen, Petroleum,
and Natural Gas
INTRODUCTION
Petroleum obtained from reservoir rocks and bitumen extracted from fine-grained rocks have many similarities,
but they also exhibit many important differences. There is
no doubt that they are related; indeed, bitumen is almost
universally accepted as the direct precursor for petroleum. However, many unanswered questions remain
about the processes that transform bitumen into petroleum. Major compositional changes occur in going from
bitumen to petroleum, but we are not certain whether
they occur mainly within the source rock or during migration through the reservoir rock. We also do not know
how much of the change involves chemical reactions, and
how much is due to physical separation of chemical compounds having very different properties. The influence of
the lithologies of source and reservoir rocks on these compositional changes is poorly understood.
Both bitumens and petroleums exhibit a wide range of
compositions. As we shall see later in this chapter, much
of this variety is related to source-rock facies and the composition of the kerogens that generated the bitumens. Maturity also exerts control over bitumen and petroleum
composition. Reservoir transformations in some cases
greatly affect oil composition and properties.
Bitumen and petroleum compositions can also be used
as tools in correlating samples with each other. Such correlations, which are discussed in chapter 10, can be particularly useful in establishing genetic relationships
among samples. In order to understand bitumen and petroleum compositions and to use them for exploration,
43
44
Aromatic hydrocarbons
Resins (NSOs,
polars)
Asphaltenes
Fraction
Saturated hydrocarbons
n-alkanes
isoprenoids
other branched compounds
alicyclics, including steranes, diterpanes,
and triterpanes
simple aromatics
naphthenoaromatics
small sulfur-bearing compounds
porphyrins
fatty acids
asphaltenes
Biomarker
Precursor
porphyrins
steranes
triterpanes
diterpanes
large naphthenoaromatics
45
Biomarkers
N-ALKANES. n-Alkanes were among the first biomarkers to be studied extensively. Their high concentration in
bitumens and oils is best explained by their existence in
plant and algal lipids, and by their catagenetic formation
from long-chain compounds such as fatty acids and alcohols (fig. 3.3).
Another important indication of the origin of n-alkanes
is the distribution of individual homologs, or members of
the n-alkane series. For the most part n-alkanes present in
terrestrial plants have odd numbers of carbon atoms, especially 23,25,27,29, and 31 atoms. An example from a
Recent sediment containing much terrestrial organic material is shown in figure 5.1.
In contrast, marine algae produce n-alkanes that have
a maximum in their distribution at C-17 or C-22, depending upon the species present. The distributions are quite
sharp, and no preference for either odd- or even-carbon
homologs is evident (fig. 5.2).
46
27
U
Z
0
z
0
Z
::>
::>
It)
It)
>
UJ
>
;::
;::
...J
...J
'"
'"
10
20
30
10
<0
n-Alkane distribution in a Recent sediment containing organic material chiefly of terrestrial origin.
FIGURE 5.1
U
Z
22
::>
II
>
;::
-'
w
'"
10
<0
UJ
U
<.l
::>
It)
UJ
~
....
...J
Many sediments, of course, receive contributions of nalkanes from both terrestrial and marine sources. Their
n-alkane distributions reflect this mix (fig. 5.3).
Sediments are also known that exhibit a strong preference for n-alkanes having an even number of carbon
atoms (fig. 5.4). These n-alkanes are believed to be
formed by hydrogenation (reduction) of long-chain fatty
acids and alcohols having even numbers of carbon atoms.
(Among the acids and alcohols present in living organisms, even-carbon homologs predominate as strongly as
do the odd-carbon homologs among the n-alkanes.)
Even-carbon preferences occur principally in evaporitic
and carbonate sediments, where input of terrestrial nalkanes is minimal and diagenetic conditions are highly
reducing.
Carbon Preference Index, or CPI, was developed as a
measure of the strength of the odd-carbon predominance
in n-alkanes. The formula for calculating CPI follows.
'"
10
20
30
40
NUMBER OF CARBONATOMS
Distributio[ls of n-alkanes from two Recent sed iments in which marine algal material dominates.
CPI
23
24
+ 25 + 27 + 29 + 31
+ 26 + 28 + 30 + 32
+ 25 + 27 + 29 + 31 + 33
24 + 26 + 28 + 30 + 32
FIGURE 5.2
w
u
28
:>
CD
w
>
;::
-'
w
a:
'0
30
47
48
CHLOROPHYLL A
CaHill
H2c-otZ
VANADYL PORPHYRIN
HO
Many steps
1. Bitumens and crude oils with high contents of waxy nalkanes (those having more than 22 carbon atoms)
have a significant input of terrestrial plant material.
High-wax oils and bitumens are usually associated
with paralic or lacustrine rocks.
2. CPI values below 1.0 are associated with evaporites or
carbonates.
3. Isoprenoid ratios are indicators of diagenetic conditions.
4. Samples containing large amounts of a very few tricyclic diterpanes have a significant contribution from
land-plant resin.
5. Distributions of CZ7 to CZ9 steranes are useful for determining the type of organic matter contributing to a
sample.
ell ,
II
110
110
FIGURE 5.7
49
~JI
liD
Cholestl'rol
r:1'!{ostl'l'ol
B-sitoSll'1'01
C~~
C:~II
C!"
50
Ll'goswnc
hole lanc
C~7
C !II
FIGURE 5.8
OH OH
" /
"'\
""/
C~
H
OH OH
Tctl'ah.vdroxybacteriohopanc
C 29
FIGURE 5.9
C 30
Many step
strongly influenced by diagenetic conditions. For economic and environmental reasons, oils having more than
about 0.5% sulfur are designated as high-sulfur. Many
high-sulfur oils contain 1% sulfur or less, but in some
areas sulfur contents can reach 7% (Monterey oils from
the onshore Santa Maria area, southern California, for
example) or more. A few oils contain more than 10%
sulfur.
These high-sulfur bitumens and crude oils are derived
from high-sulfur kerogens. As we saw in chapter 4, sulfur
is incorporated into kerogens formed in nonelastic sedi-
FIGURE 5.10 Formation of extended hopanes from tetrahydroxybacteriohopane, a probable precursor. Also shown is
the epimerization at C-22 from the biogenic 22R configuration
to an eventual equilibrium mixture of 22R and the more stable 225. Reprinted by permission of Cambridge University
Press from Mackenzie and McKenzie, 1983.
51
positions of petroleum and bitumen. Low-maturity samples, including bitumens, oils, and solidified bitumens,
have fewer hydrocarbons and more NSO compounds,
and average molecular weights are higher. SIN ratios decrease with increasing maturity, although this parameter
is only measurable in oils that are rich in nitrogen. API
gravities are lower and viscosities are higher for lowmaturity oils than for oils generated later during
catagenesis.
Biomarkers
N-ALKANES.
n-Alkane
distributions
are
greatly
modified by thermal maturity. Chain lengths gradually
become shorter, and the original n-alkanes present in the
immature sample are diluted with new n-alkanes
generated during catagenesis. Because the newly
generated n-alkanes show little or no preference for either
odd- or even-carbon homologs, CPI values approach 1.0
as maturity increases (fig. 5.11).
n-Alkane distributions in bitumens and oils derived
from algae do not show the influences of maturity as
clearly because the original CPI values are already very
close to 1.0 (fig. 5.2). It is therefore often difficult to estimate maturity levels in pelagic rocks on the basis of nalkane profiles.
ISOPRENOIDS. Isoprenoid distributions also change
with maturity, though not as dramatically. As maturity
proceeds, phytane is generated faster than pristane, leading to a decrease in the pristane/phytane ratio (fig. 5.12).
Change in n-alkane distributions of coal extracts as a function of increasing maturity, measured by vitrinite reflectance. Reprinted with pennission from Radke et
al., 1980. Copyright 1980, Pergamon Press, Ltd.
FIGURE 5.11
52
MAHAKAM DELTA
410
..J
~ 430-
2100
cr
"
~440
-" ~
2100 ~
II
f'~
lOOO
460 11----.----,----.----1
1.5
20
25 0
10
15
20
-PRISTANE/PHYTANE RATIO-
MAHAKAM DELTA
410
!oJ
~ 045
..,~
I 420
..J
...w
cr
~
...':"4
~060
cr
.J
Z
ir
t-
;;:
2100 ]
:r
t-
o..
2700 ~
~"
]000
-; 090
cr
5
10
20 0
05
10
1.5
--PRISTANE/nCI7 RATIO-- -PHYTANE/nCI8 RATIO-+
Isoprenoid/n-alkane ratios as a function of burial depth and maturity in the Mahakam Delta, Kalimantan.
Reprinted by permission ofJohn Wiley & Sons, Ltd. from
Present trends in organic geochemistry in research on migration of hydrocarbons, by B. Durand, ed. by M. Bjorf'Y. Copyright 1983, John Wiley & Sons, Ltd.
FIGURE 5.13
53
",0
-OH-
HYDROGENATION
Sa, 14a, 17a(20R)
Regulm'
sterane
R ' \ - CATAGENESIS
R
1313, 17a(20 S or R)
Rearranged
sterane
FIGURE 5.14
another produce a variety of new steranes from the original5a, 14a, 17a (20R) steranes (fig. 5.14). Epimerization
at the C-20 position converts the biogenic 20R epimer into
a mixture of 20R and 20S. Because the 20S epimer can
convert back to 20R, once equilibrium has been reached
the ratio of 20R to 20S remains constant.
Epimerization can occur at several other sites as well.
Epimerization occurs almost simultaneously at the C-14
and C-17 positions to yield isoskeletal steranes (fig. 5.14).
The ratio of 14a, 17a steranes to 1413, 1713 steranes
(known as aa and 13~) is also an indicator of catagenesis.
At equilibrium the more stable 1313 form is favored.
54
HOPANE
MORETANE
17a(H), 21 /3(H)
1711(H), 21a(H)
FIGURE 5.15
hopane.
1983.
a number of different transformations as maturity indicators, each within its optimal range of validity. Specific
applications of biomarker transformations will be discussed in more detail in chapters 8 and 10.
RESERVOIR TRANSFORMATIONS
formations that can affect crude oils (reservoir transformations are not applicable to bitumen because, by
definition, the material in a reservoir is petroleum). Thermal processes occurring in reservoirs include cracking
and deasphalting. Nonthermal processes are water washing and biodegradation. Of these, cracking and biodegradation are by far the most important.
Cracking and Deasphalting. Cracking, which breaks large
55
56
TABLE 5.3
1 . GASES (Cl . C6) "
2 GOR (GAS/Oil RATIO) "
3 GASOLINE RANGE (C6 . C15) "
4 API GRAVITY iii
5 . VISCOSITY ,
6 CHANGES IN GROSS COMPOSITION OF CltCOMPOUNDS
alkanes
"
~romatics 1I
NSO's compounds ~
asphaUenes ,
7 SULPHUR CONTENT
Level of
Biodegradation
Compounds
Removed
Extent of
Biodegradation
1
2
3
None
Short n-alkanes absent
> 90% of n-alkanes
removed
Alkylcyclohexanes
absent; isoprenoids
reduced
Isoprenoids absent
Bicyclic alkanes absent
> 50% regular steranes
removed
Steranes altered; demethylated hopanes
abundant
Demethylated hopanes
predominate; diasteranes formed; no
steranes
Undergraded
Minor
Moderate
4
~
8 . NITROGEN CONTENT ~
9 V AND Ni
10 . OPTICAL ACTIVITY
alkanes ~
11 . POUR POINT 1I
6
7
12 . 613C
whole 011 ~
alkanes ~
aromallcs '" or ..
asphaUenes ..
13 . CHANGES IN Oil TYPES
paraffinic oil _ _ _ _ _ _ _ _ _
naphthenic Oils
condensates
aromalicnaphthenlc oils
naphthp.nlc condensates
light oils
aromatic-asphaltic oils
Moderate
Moderate
Extensive
Very extensive
Severe
Extreme
ical properties of crude oils. Reprinted by permission of Academic Press from Connan, 1984.
57
'\Illlllallr IIC
Mo Ih' Ill'''\'\'.
(kgl',;dtcl oj'ls
40
20
N 0 compound
(I 'ins + a ph(l\relll's)
58
Although bitumens and crude oils contain the same compounds, the relative amounts are quite different. Figure
5.20 compares the hydrocarbon contents (saturates +
aromatics) from bitumens with those for petroleums. In
the process of converting bitumen to petroleum, either the
NSO compounds are lost in large quantities, or they are
converted to hydrocarbons. In actuality, both processes
probably occur, although selective loss of nonhydrocarbons during expulsion is probably most effective in concentrating the hydrocarbons.
Bitumen composition depends strongly on the lithology
of the host rock (fig. 5.21). Carbonates contain bitumens
that are much richer in heterocompounds than are shales,
and their hydrocarbon fractions are more aromatic.
These differences are the result of the higher sulfur contents of kerogens in carbonates. Oils derived from carbonate sources are also richer in heterocompounds than oils
sourced from shales.
In discussing the presence or distribution of individual
compounds in bitumens, it is important to know the ma-
0.6
0.8
Sulfur
1.0
(%l
1.2
1.4
1.6
1.8
2.0
L-_~_~_--'---_---'-_~_--'
Increases in sulfUr content during biodegradation of oiLs from the Alaska North Slope. From Magoon and
FIGURE 5.19
Claypool, 1981.
Bitumens from
shales and siltstones
N = 1595
Crude oils
N = 2364
700
en
~ 600
~
~ 500
~ 200
en
:E 150
;;l
g300
200
s:
tl
..... 100
400
o+----.--~--~~
0.0
PERCENT HYDROCARBONS
FIGURE 5.20
Extract of
Source rock
Oil
Shale/sand
sequence
carbonate
sequence
~.:
.
..........
............. <II ..
.......... <II .... .
o Resins + asphalten
Aromali H
Saturated H
Natural gas contains -. many different compounds, although most of them are present only in trace quantities.
59
The principal components with which we shall be concerned are light hydrocarbons (methane through
butanes), CO2, H2S, and N 2.
Carbon dioxide and N2 are generally associated with
very hot reservoirs. CO2 is derived either by oxidation of
oil or gas or by decomposition of carbonates. The origin
of the CO2 can be determined easily by carbon-isotope
measurements: the very different isotopic compositions of
organic-carbon species and carbonates (fig. 3.16) are carried over into any CO2 derived from these materials. Nitrogen is thought to be an indicator of high levels of
maturity formed primarily by metagenetic transformation
of organic nitrogen and ammonia bound to clay minerals.
Hydrogen sulfide is usually derived from high-sulfur
kerogens or oils. These in turn are formed most readily in
carbonates. Thus sour gas is most common in carbonate
reservoirs or in places where the source rock was a carbonate. Smackover gas from the Gulf Coast is an example;
the source rock was probably the organic-rich basinal
Smackover facies, and the reservoirs are coarse-grained
nearshore facies. H2S could also be formed by the reaction
of hydrocarbons with sulfate in reservoirs, especially carbonates containing anhydrite.
Biogenic gas, most of which occurs at shallow depths,
but which can apparently form (or at least persist) at
depths of a few thousand meters, is very dry, containing
only trace amounts of hydrocarbons heavier than
methane. In contrast, the first gas produced during
catagenesis is quite wet. With increasing maturity, gas
again becomes progressively drier as a result of cracking
of the heavier hydrocarbons to methane (fig. 5.22).
Gas becomes increasingly heavier isotopically as gas
generation proceeds (fig. 5.22). Biogenic gas is isotopically very light, with 8 13C values ranging from about - 60
0/00 to 90 0/00 or so. The methane in catagenetic gases is
heavier (- 50 0/00 to - 30 0/00 or so), whereas late
(metagenetic) methane can be as heavy as -15 0/00.
Ratios of 8 13C values of the various hydrocarbon components of wet gases have been used as a paleothermometer
(Sundberg and Bennett, 1983).
Mixing of biogenic and thermal gases often occurs, especially in shallow reservoirs, Gases of mixed origin will
have properties intermediate between those of the
contributors.
Bacterial destruction of gas is rather rare, but can cause
60
IMMATURE
( d,a OI!I'I@S,S)
MATURE
(cat.genes l !!')
POST - MATURE
(met.lTllo, ph . Ii m)
SUGGESTED READINGS
FIGURE 5.22 Schematic diagram showing changes in gas
composition (wetness and 8 13C of methane) in the course of
gas generation. Reprinted by permission of the American Association of Petroleum Geologists from Rice and Claypool,
1981.
measurable changes in the composition when it does occur. Biodegraded gas is dry, because most of the heavier
components have been preferentially removed. As a result, any remaining heavy hydrocarbons will be unusually heavy isotopically.
SUMMARY
Bitumens and crude oils contain the same classes of compounds, but their relative concentrations are quite different. These differences are in some cases related to
differences in maturity; in other examples they are probably a result of preferential expulsion of hydrocarbons
from source rocks.
Individual compounds occur in quite variable proportions in bitumens. S~urce, diagenesis, and maturity all
exert control over these distributions. When source and
Albaiges,J. andJ. M. Torradas, 1974, Significance of the evencarbon n-paraffin preference of a Spanish crude oil: Nature,
v. 250, pp. 567-568.
Alexander, R., R. I. Kagi, G. W. Woodhouse, and J. K. Volkman, 1983, The geochemistry of some biodegraded Australian oils: Journal of the Australian Petroleum Exploration
Association (APEA), v. 23, pp. 53-63.
Aquino Neto, F. R., J. M. Trendel, A. Restle, J. Connan, and
P. A. Albrecht, 1983, Occurrence and formation of tricyclic
and tetracyclic terpanes in sediments and petroleums, in M.
BjorfllY, ed., Advances in Organic Geochemistry 1981:
Chichester, Wiley, pp. 659-667.
Connan, J., 1984, Biodegradation of crude oils in reservoirs, in
J. Brooks and D. Welte, eds., Advances in Petroleum
Geochemistry, Volume 1: London, Academic Press, pp. 299333.
Dembicki, H. Jr., W. G. Meinschein, and D. E. Hattin, 1976,
Possible ecological and environmental significance of the
predominance of even-carbon number C20 -C 30 n-alkanes:
Geochimica et Cosmochimica Acta, v. 40, pp. 203-208.
James, A. T. and B.J. Burns, 1984, Microbial alteration of subsurface natural gas accumulations: Bulletin of the American
Association of Petroleum Geologists, v. 68, pp 957-960.
Lewan, M. D., 1984, Factors controlling proportionality of van a-
61
Chapter 6
Migration
DEFINITIONS
Migration is the movement of oil and gas within the subsurface. Primary migration is the first phase of the migration process; it involves expulsion of hydrocarbons from
their fine-grained, low-penneability source rock into a
carrier bed having much greater penneability. Secondary
migration is the movement of oil and gas within this
carrier bed. Accumulation is the concentration of migrated hydrocarbons in a relatively immobile configuration, where they can be preserved over long periods of
time. Traps are the means by which migration is stopped
and accumulation occurs.
Each of these steps is quite distinct from the others. In
order to understand the complex sequence of events that
we call migration, we must look at each of these steps
separately. This chapter will not go into the physics and
chemistry of migration in detail, but will describe the
most widely held views on the dominant mechanisms of
primary and secondary migration and accumulation. Our
objective is to use this knowledge of migration processes
and the factors that influence them to predict where undiscovered hydrocarbon accumulations might be.
PRIMARY MIGRATION
MECHANISMS
64
given serious consideration by most petroleum geochemists: diffusion, oil-phase expulsion, and solution in gas.
Diffusion has been shown to be active on at least a
minor scale and over short distances in carefully studied
cores (Leythaeuser et al. 1984). Its importance is probably
limited to the edges of thick units or to thin source beds.
Furthermore, it is probably most effective in immature
rocks, where preexisting light hydrocarbons bleed out of
the rocks prior to the onset of significant generation and
expulsion.
The main problem with diffusion as an important
mechanism of migration is that diffusion is by definition a
dispersive force, whereas accumulation of hydrocarbons
requires concentration. Diffusion would therefore have to
be coupled with a powerful concentrating force to yield
accumulations of appreciable size. During intense hydrocarbon generation, any contribution by diffusion will be
overwhelmed by that from other expulsion mechanisms.
By far the most popular mechanism invoked today to
explain primary migration is expulsion of hydrocarbons
in a hydrophobic (oily) phase. There appear to be three
distinct ways in which oil-phase expulsion can occur.
One occurs most commonly as a result of microfracturing
induced by overpressuring during hydrocarbon generation. When the internal pressures exceed the shear
strength of the rock, microfracturing occurs, particularly
along lines of weakness such as bedding planes. Laminated source rocks may therefore expel hydrocarbons
with greater efficiency than massive rocks. Once the internal pressure has returned to normal, the microfractures
heal. The hydrocarbons within the pores then become
isolated again because of the impermeability of the waterwet source rocks to hydrocarbons, and overpressuring
commences anew. Many cycles of pressure buildup, microfracturing, expulsion, and pressure release can be
repeated.
An important implication of the microfracturing model
is that expulsion cannot take place until the shear strength
of the source rock has been exceeded. Based on empirical
evidence, Momper (1978) suggested that in most cases no
microfracturing or expulsion could occur until a threshold amount of bitumen had been generated in the source
rock. He proposed that the threshold value was about 15
barrels of bitumen peF acre-foot of source rock (equivalent to 50 million barrels per cubic mile for those of us
6. MIGRATION
65
66
6. MIGRATION
220 MILES - - - - - - - - - - - - - - - - 1
0
lW
W
.....
.....
15
</)
20
en
30
0
Z
::J
10
25
0 35
:t
1-
I- 40
45
Mature
Over mature
1001
64 MILES
0
IW
W
.....
.....
0
en
0
Z
en
1-
::J
:t
I-
Overmature
1001
V E ,2X
10
--------------~-l
67
68
ACCUMUlATION
INTRODUCTION
Most hydrocarbon traps are either structural or stratigraphic. The seal prevents vertical migration from the
reservoir rock into overlying strata, while the strucure or
lithologic change prevents lateral updip migration. Classical traps are well understood, and will not be covered
further here.
KINETIC TRAPS
lower permeability than the overlying sand. The lowpermeability sand thus creates a bottleneck to gas migration. Because gas generation is very rapid, the
low-permeability sands become filled with gas. Gas production is actually from the low-permeability sand
rather than from the high-permeability sands updip and
downdip. No traditional seal exists. Because the highpermeability sand updip allows gas to migrate rapidly
through, it remains water wet. Thus the Elmworth Field
exhibits a water-over-gas contact.
High rates of hydrocarbon generation can actually
create traps by causing tensile failure of source rocks that
have become overpressured as a result of hydrocarbon
generation. The Altamont Field in the Uinta Basin of
Utah and the Antelope Field in the Williston Basin of
North Dakota have been proposed as examples of kinetic
oil accumulations (Meissner, 1983). Fracturing associated with high rates of oil generation in the Green River
Shale has created a supergiant accumulation at Altamont.
The much smaller Antelope Field produces from the Mississippian Bakken Formation, a fractured shale that is
both source and reservoir. Much of the hydrocarbon storage at Antelope is apparently in silts and sands juxtaposed with the producible Bakken reservoir.
Many of the accumulations in Pliocene reservoirs in
southern California are also kinetic accumulations in a
slightly different sense. Cap-rocks in those fields are often
poor, and would be incapable of sealing accumulations
for long geologic periods. Because intense oil generation
is going on now, however, large accumulations have
formed despite high rates ofleakage (McCulloh, 1969a).
TAR-MAT TRAPS
Tar mats produced by biodegradation can create excellent seals. In cases where no other structural or stratigraphic trapping mechanism exists, tar mats may provide
the only possible means for retaining any hydrocarbons.
Accumulations beneath tar-mat seals are generally
biodegraded themselves, because the same conditions
that created the tar mat persist in the subsurface. Despite
the rarity of tar-mat seals, and the poor producibility of
the hydrocarbons they trap, tar-mat traps are worth discussing because they include the largest hydrocarbon accumulations known: those of the Athabasca Tar Sands
and the Orinoco heavy-oil belt.
6. MIGRATION
69
GAS HYDRATES
PARAFFINS
NAPHTHENES
z
o
AROMATICS
<
IE:
~
~
>IE:
<
o
z
o
o
NON-HYDROCARBONS
CARRIER ROCK
II)
SOURCE ROCK
70
mine the timing of generation, we will also have determined the timing of expulsion. A method for estimating
timing of hydrocarbon generation is discussed in chapter
9. (Obviously, cases like the Uinta Basin, where expulsion
probably occurred before generation, do not follow these
rules. It has not been shown, however, that hydrocarbons
expelled prior to the main phase of hydrocarbon generation form accumulations of economic interest.)
In using our understanding of secondary migration for
exploration, we want to determine the main pathways
and conduits through which migration occurs, the barriers that modi1)r the direction of migration and eventually
stop it, and the vertical and horizontal distances involved.
Conduits are determined by proximity to effective source
rocks and their permeabilities to hydrocarbons. Pathways, as we have seen, are determined by structural contours on the top of the carrier beds. Barriers can be
created by folding, by faulting, by decreases in permeability as a result offacies changes, or by the presence of tars.
Vertical-migration distances can be considerable, depending upon stacking of reservoirs, vertical faulting, and
the possibilities of combined vertical and lateral migration. Lateral-migration distances are strongly influenced
by tectonic and depositional histories of basins. Tectonically stable basins have the best potential for longdistance migration and supergiant accumulations.
Unstable basins seldom have depositional or tectonic continuities necessary for long-distance lateral migration to
occur.
In summary, as explorationists we have very pragmatic
interests in migration. We need to know when hydrocarbons moved, in what direction they moved, and how far
they moved. An understanding of the process of hydrocarbon generation coupled with good geological data
will permit us to predict the outcome of hydrocarbon
migration.
SUGGESTED READINGS
Demaison, G., 1984, The generative basin concept, in G. Demaison and R.J. Murris, eds., Petroleum Geochemistry and
Basin Evaluation: American Association of Petroleum
Geologists Memoir 35, Tulsa, American Association of Petroleum Geologists, pp. 1-14.
du Rouchet,J., 1981, Stress fields, a key to oil migration: Bulletin
71
Chapter 7
Analytical
Techniques
INTRODUCTION
74
three pieces of data: quantity, type, and maturity of organic matter present in the rock. There are a number of
methods available for answering these questions.
In the following sections the order in which I have
presented the analytical techniques is significant for two
reasons. First, many analyses require previous preparatol}' steps. The methods are therefore presented in a logical analytical sequence.
Secondly, cost is a major concern in any analytical program. We want to perform the minimum number of analyses that will allow us to answer our original questions.
Inexpensive analytical techniques should therefore be
used as preliminary screens to determine which samples
are suitable for more detailed and expensive analyses.
Use of screening procedures is recommended by most
laboratories, and their personnel are vel}' willing to assist
in avoiding unnecessary expenditures. However, an exploration geologist who is aware of the great monetary
savings that can be achieved through properly designed
screening programs can often make the screening procedure more cost-effective and more informative.
This chapter describes the analytical techniques and
instruments used in laboratol}' studies of organic materials. Discussions of the pros and cons of the various techniques, as well as interpretation of the analytical results,
are included in chapters 8 and 10.
CHEMICAL CHARACTERIZATION
FOR CORRELATIONS
BITUMEN AND OIL ANALYSES
tracted and the solvent removed, the next step is to separate the bitumen into fractions that differ in chemical
c~osition. Petroleum is handled like bitumen from this
point onward in the analytical scheme. The first step in
the separation procedure is precipitation and removal of
intractable asphaltenes upon addition of a large excess of
pentane. The asphaltenes are then filtered off and the
asphaltene-free bitumen or oil is recovered by evaporation of the pentane.
The technique most commonly used to separate the
asphaltene-free bitumen or crude oil into fractions is
called column chromatography. The principles of column chromatography (and indeed all chromatographic
techniques) are essentially the same as for chromatographic separation of compounds during migration, dis-
7. ANALYfICAL TECHNIQUES
Eluenl
Oil sample
75
Eluent
SO CPD '
.Adsorbent
Aromatic
....... Salurales
o
FIGURE 7.1 Column-chromatographic separation offractions
of bitumens or cruie oils. Saturated hydrocarbons move fastest, followed by aromatics and then bp NSOs.
8
n-Hexane is allowed to pass through the column until
the saturated hydrocarbons have all been eluted. The solvent and its dissolved hydrocarbons are collected as the
first column-chromatographic fraction. Aromatic hydrocarbons (along with some sulfur-bearing heterocompounds) are then collected in a second fraction eluted by
a slightly more polar solvent, benzene. A third fraction,
containing mainly NSO compounds, is eluted with
chloroform.
Although traditional column chromatography is still
the standard for the industry, a new variation, carried out
using a device called the Iatroscan, has been adopted by
some groups. The Iatroscan employs thin-layer chromatography in much the same way that column chromatography has been used. A thin layer of stationary phase is
coated on the outside of a capillary tube, and a tiny
amount of the bitumen or oil is spotted near one end of
the tube. The tube is then inserted vertically in a shallow
pan of solvent, with the spot near the bottom of the tube
but above the solvent level. The solvent climbs up the
tube, moving by capillary action through the stationary
phase. As it moves, it mobilizes some of the molecules,
just as in column chromatography. This time, however,
76
H\'drocarbon
d~(e('(or
He-7
Recordc,"
Gas Chromatography.
77
Prj
27
29
31
78
GAS CHROMATOGRAPH
(GC)
MASS SPECTROMETER
(MS)
/r------------~,
/r--------------------------~,
..
m / .217
t:
=---"7"""- ----,0 _ _
i'" . . . . . . . . -Z
II-
INJECTOR
COLUMN
(SEPARA TION)
(VOLA TllIZA TlON)
DETECTOR
SOURCE
QUADRUPOLE
ANALYZER
RECORDER
(ION SELECTION)
(ION
PRODUCTION)
and triterpanes can also be obtained, but gc/ms (discussed next) is far more valuable in that regard.
lar mlz value pass through the center of the chamber and
strike the detector (fig. 7.4). Ifwe know the field strength
at that moment, we can calculate the mlz value of that
ion. The detector response tells us how many such ions
were present.
As the field strength is varied rapidly during the analysis, ions with different mlz values are allowed to strike the
detector. The detector responses over the range of field
strengths employed are summed to yield a mass spectrum (fig. 7.5). The height of each bar is proportional to
the number of ions with that particular mlz value.
Mass spectra like the one shown in figure 7.5 are
mainly used to identity particular unknown compounds.
Once a compound has been identified, it is easy to recognize chemically similar compounds in other samples.
Most geochemists and geologists never have to work with
mass spectra; specialists identity the compounds once,
and then those identifications are used in future work.
What has proven much more useful for petroleum
geochemists seeking to apply gc/ms in exploration is the
knowledge that compounds with similar chemical structures have similar mass spectra. Thus steranes all have a
large mlz 217 peak, derived by the fragmentation pattern
shown in figure 7.6. Similarly, most triterpanes have a
Gas
7. ANALYTICAL TECHNIQUES
...
:"~
_'I: ",
:c
.,
-! :"
...
~v
. 1..1 1..1
~ ... \.1
.""
.1' ' =
~.
\.1
m/e 371
+R
m/e 217
TYPE OF COMPOUND
MOLECULAR ION
FRAGMENT ION
CHOLESTANE
(C27)
372
217
ERGOST ANE
(C28)
386
217
SITOSTANE
(C29)
400
217
'!
79
.. ; ..
:\'
... ..'v
80
RetentIon
_ _to
ISOPRENOIDS
,...,191
TRITERPANES
A 13 DEMETHYLA TEO
TRITERPANES
,.,.",211
STERANES
TRIAROMATIC STERANES
MONDAROMA TIC
STERANES
large m/z 191 peak (fig. 7.7). Triterpanes that have lost
the methyl group between the A and B rings by biodegradation give m/z 177 peaks (14 amu less than the normal
triterpanes, corresponding to loss of a CH z unit: fig. 7.7)
as well as 191 peaks. These three fragment ions, together
with those for monoaromatic and triaromatic steranes
(239 and 253, and 231, respectively), are the most important ones today for most gc/ms work.
One of the tricks of modern electronics allows us to
monitor selected m/z values during the entire gaschromatographic separation. For example, in figure 7.8 a
response by the mass spectrometer's detector occurs each
time a compound with a prominent m/z 191 ion is eluting
from the gas chromatograph. These ions usually have the
structure shown in figure 7.7, and are most commonly
derived from di-, tri-, or tetraterpanes. The trace obtained
by monitoring a single m/z value during an entire gaschromatographic run is called a mass chromatogram or
a mass fragmentogram (fig. 7.8).
Mass chromatograms can be used as fingerprints in
correlating samples. ,Alternatively, careful and detailed
analyses of the individual compounds can be made in
JWUJ:
i i i
81
82
J. K
G.H
C
B
o
I
INJECT
- - -1 - 15
KEROGEN ANALYSES
25
30
35
lIME (mins)
FIGURE 7.9 HPLC chromatogram of porphyrins from a sample ofgilsonite. Peaks A-G represent etioporphyrins; H-L
are DPEP porphyrins. Reprinted by permission ofJohn Wiley
& Sons, Ltd. from Petroporphyrin fingerprinting as a
geochemical marker, by A. Barwise and P. Park, ed. by M.
Bjoroy. Copyright 1983, John Wiley & Sons, Ltd.
characterize kerogens and kerogen concentrates for correlation with bitumens and oils. Among these are elemental analysis, isotope measurements, and pyrolysisgas chromatography.
Elemental Analysis. Elemental analysis measures the pro-
7. ANALYTICAL TECHNIQUES
are identical to those for bitumens and crude oils previously described. Pyrolysis-gas chromatography is discussed later in this chapter.
GAS ANALYSES
83
Sample
can
which is spontaneously released from the rock upon sitting) in a sealed can is to puncture the can with a needle
and withdraw a sample of the gas that has accumulated
above the water in the container (fig. 7.10). This gas is
then injected into a gas chromatograph for analysis of the
individual light hydrocarbons.
Adsorbed gases (those molecules not released from the
rock matrix upon standing) can be analyzed by pulverizing the rocks from which the headspace gas has been
removed and then extracting the newly evolved gases with
a syringe.
Some light-hydrocarbon analyses measure the very
small gas molecules (methane through butanes), whereas
others focus on pentanes and heavier molecules. The
lower-range hydrocarbons give us the wetness of the gas
and clues about its probable origin; the heavier hydrocarbons, which have many isomers, are used more as a
fingerprinting technique.
Carbon and hydrogen isotopes are also commonly
measured for gases. Most analytical procedures separate
the methane from the heavier hydrocarbons by gas
chromatography in order to measure the isotopic composition of the pure methane. Recently it has become more
popular to isolate ethane and propane as well and to
determine their isotopic compositions. The procedures
used are the same as those discussed for other isotopic
analyses.
84
o~
1I't.am
200~------r------''------'------~------/~
o...J
Rock sample
I
.
.. .,.. .
o.
>-
5i
~~~ve.. 1 ~~
'60
Z
w
~P~
Induction
/ 0
C)
rUl'll3Ce
Dell'ctol'
Recorderdigital
voltm(,ler
::::E
IX:
IL
"."
120
SOURCE-ROCK EVALUATION
QUANTITY OF ORGANIC MATERIAL
/~.
/.
80
/.
" 1.1.
IX:
. .-:.
. .. . v .. "
FIGURE 7.11
/ .
o
trap
. 0
>/
.I
/ "
00
40
BO
'20
'60
200
two distinct approaches to determining the type of organic matter in a sedimentary rock. Our objective in carrying out source-rock analyses is to determine the
hydrocarbon-generative potential of the kerogen. We can
Direct Method.
85
1 = Volatile hydrocarbons
2 = Hydrocarbon dedved
from kerogen pyrolysi
Recorder'
Temperature
programmer
FIGURE 7.13
~:u.<oI_-
Rock unplt'
86
TYPE I
:c
a:
RelenUon Time
7. ANALYTICAL TECHNIQUES
87
20
15
x
X
X
XX
XX
XX
XX
XX
XXXX
XXXX
XXXX
X XXXX
X XXXXX
X XXXXX X
X XXXXXXXX XXX
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
REFLECTANCE (%RO)
4.0
4.5
5.0
5.5
6.0
POPULATION GROUPS
POP.
COUNT
MIN. RO
MAX. RO
STD. DEV.
MEANRO
1
2
3
5
45
5
1.11
1.46
2.06
1.39
1.98
2.41
0.094
0.116
0.118
1.29
1.71
2.25
88
Linear
Semilog
'" (~
1.500
0
3.000
'3.000
l-
X
~
:z:
I-
A-
A-
OIl
o~
4.500
4.500
,
~
OIl
~I\o
,.0000L,.2,..........,,0..,.4-.....,,0~.6-.....,,0"':
.----:"11::.0......--:'1.":2.....-:"~......;~
VITRINITE REFLECTANCE (R.o/.)
6.000
.2
.3
.4
.5
.6 .7 .I.t 1.0
2.0
30
made on the same slides prepared for microscopic kerogen-type analysis. The darkening of kerogen particles
with increasing thermal maturity can be used as an indicator of maturity. In order to minimize differences in
color caused by changes in the type or thickness of the
kerogen particles, TAl measurements are carried out on
bisaccate pollen grains whenever possible. If no pollen
can be found, TAl values are estimated, with lower
confidence, from amorphous kerogen.
Each laboratory has reference slides so that microscopists can continually compare the color determinations
they are now making with those they and their colleagues
7. ANALYTICAL TECHNIQUES
most commonly from fossiliferous carbonates, by removing the mineral matrix with acetic or formic acid. Colors
of the specimens thus obtained are determined under a
binocular microscope and compared with standards. The
technique is simple and quick and can be done even by
inexperienced workers.
Electron-Spin Resonance (esr). Esr measurements are made
89
The main causes of contamination among samples obtained from wells are caving and adulteration by drillingfluid additives. Caving is not a problem for conventional
or sidewall cores, of course, but it can be devastating in
cuttings samples. Caved materials can often be recognized by careful picking of lithologies and comparison
with up-hole samples. In many cases, however, vitrinitereflectance measurements offer the best means of recognizing caving (see chap. 8). Caving is a particular
problem for coals, because of their friability; it can lead to
an overly optimistic assessment of the organic richness of
the section.
Drilling-fluid additives have been a severe headache for
petroleum geochemists for a long time. Contaminants of
particular notoriety are diesel fuel, walnut hulls and other
solid debris, and lignite from lignosulfonates. Fortunately, palynological analysis can usually detect the presence of lignosulfonates because of the unique pollen
assemblages present in the lignite. In such cases TOC
values will be raised and reflectance histograms will
show a large population near 0.5%. Walnut hulls and
other organic debris are also easy to detect microscopically, and can be removed prior to beginning the analytical sequence.
In contrast to solid additives, which affect only the
kerogen portion of the sample, diesel fuel affects both
kerogen and bitumen. It is capable of impregnating
sidewall and conventional cores as well as cuttings. TOC
values will be raised and vitrinite-reflectance values lowered by the presence of adsorbed diesel. Pyrolysis results
90
Analysis
Sample handling
TOC
Rock-Eval pyrolysis
Kerogen isolation
Microscopic kerogen evaluation, including TAl (requires previous kerogen
isolation)
Vitrinite reflectance (requires previous
kerogen isolation)
Elemental (CHNSO) analysis of kerogen
(requires previous kerogen isolation)
Bitumen extraction
Column chromatography (requires previous bitumen extraction)
Molecular sieving
Gas chromatography of saturated hydrocarbons (requires previous bitumen
extraction and column chromatography)
Gas chromatography-mass spectrometry
(requires previous bitumen extraction,
column chromatography, and molecular
sieving)
% Sulfur (may require previous treatments)
Carbon isotopes (may require previous
treatments)
Sulfur isotopes (may require previous
treatments)
Hydrogen isotopes (may require previous
treatments)
Headspace gas of canned cuttings
Gasoline-range hydrocarbons
5
18
28
25
50
70
ANALYTICAL COSTS
Price per
Sample ($US)*
50
50
65
35
75
400
50
50
65
80
20
75
'Prices are based on 1985 quotes on the basis of a fifty-sample job for Toe and
Rock-Eval, and for five-sample jobs for the other analyses. Smaller jobs may
command higher prices, especially for routine analyses. Larger jobs may earn
additional price reductions. Data interpretation is included in the prices.
91
There is now a high degree of competition among analytical seIVice companies for organic-geochemical business. Shopping around for the best possible prices can
result in substantial savings. Proper planning of the analytical program can also reduce costs greatly.
More detailed knowledge of most of these analytical
procedures would require hands-on laboratory experience. If your needs or interests dictate that you become
involved in analytical procedures, a laboratory is the best
place to learn.
SUGGESTED READINGS
Chapter 8
Source-Rock
Evaluation
93
94
Category of
Source Rock
Original
Source
Capacity"
Remaining
Source
Capacityt
Hydrocarbons
Generated
Possible
Potential
Effective
Nonsource
Go
Go
Go
none
unmeasured
Go
G
none
unmeasured
none
Go-G
none
CJ
900
~
CJ
750
...
0
Introduction.
A
A
bn
..
><
~
Q
600
450
--4'
i*V
-,*9-
~-
*.'*
*
c:
Q
>-
II
C!J
I>.
A
A
I>. AA
J~
-:'/.1
300
[]
.\
150 - .
A
e AI>.
eJeAI>.A
'
D 0
~_ o000
10/0'0
~.
00
0,
0 .......
50
100
IS0
--~. OXYGEN INDEX (mg C02/g TOC)
Q
*
A
INCREASING MATURATION
FIGURE 8.1 Modified van Krevelen diagram used for RockEval pyrolysis data, showing the maturation pathways of
Types I, II, r;nd III kerogens. Reprinted by permission of the
Societe des Editions Technip: figure 11 from the article entitled ''Methode rapide de caracterisation des roches meres,
de leur potentiel petrolier et de leur degre d'evaluation" by].
Espitalie et al., published in the Revue de l'Institut FraTlfais
du Petrole, vol. 32, no. 1,]an.-Feb. 1977.
8. SOURCE-ROCK EVALUATION
PRINCIPAL PRODUCTS
OF
KEROGEN EVOLUTION
~
I.SO
C02. H20
Oil
GAS
"'
:r
:E
0
I-
1.00
et
if"
,
s~
JC
U'
lk.
5.
OSO
010
020
,,
,
iii
II:
OM
ti
!
%
'OGO
5,
\ .,
...
~
II.
g
5, + S,
'000
""'-.
'-...... -
1000
0
0 .'
0 .2
O.S
0.0
OM
q
q..
1000
TMilI
'0.
2000
'0.
..
''0
"0"
lOOO
UO
0 .)
PRODUCTION INDEX
ATOMIC OIC
95
430'C
"0
'.0
TEMPERATURE ('CI
S3 is the most controversial parameter measured. Collection of carbon dioxide in the Rock-Eval is intentionally
stopped at a low temperature in order to avoid including
carbon dioxide produced by decomposition of carbonate
minerals. However, this tactic has not always proved successful. Samples containing carbonates often give spuriously high S3 values, especially ifTOC values are low. S3
values are ignored by many workers; if used, they should
always be interpreted carefully, particularly in carbonate
rocks.
Advantages and Disadvantages of Pyrolysis. The advantages
96
Isolated Kerogen
c
.2
c:
III
0
...J
III
.~
iii
Qj
s:
i'"
Whole Rock
a:
.;..~
I II
I I
I '
.1.l....4.L._
Heavy
Light PrO::lucts
PrOducts
Retention Time
1983.
quantity G all break it down into two parameters: quantity and type (quality) of organic matter. Each of these
parameters is measured separately; they are then combined to give an estimate ofG. Both microscopic kerogentype analysis and elemental analysis are normally
coupled with an independent determination of kerogen
quantity, such as Toe.
Advantages and Disadvantages of Indirect Methods
INTRODUCTION. One advantage of the
indirect
methods is that they give us a more complete picture of
the chemical composition and history of a kerogen, and
thus enable us to understand more fully the various
geochemical and geological processes that affect sourcerock quality. Another advantage is that we normally use
more than one indirect method, enabling us to compare
the results from several techniques and thus recognize
problem samples. Disadvantages are two: speed and cost
of the analyses are not as favorable as for pyrolysis, and
our analytical results do not tell us directly about hydrocarbon-generative capacity.
The indirect methods require that organic-carbon con-
8. SOURCE-ROCK EVALUATION
97
the section. In this case the average TOe of 0.5% is probably a fair appraisal of the overall section, but that figure is
really an average between two totally different lithologies:
much sand with no source potential, and a small amount
of shale with high Toe values. In order to evaluate the
source potential of the section realistically, it would be
necessary to focus on the shales, not on the average Toe
value for the entire section.
MICROSCOPIC KEROGEN-TYPE ANALYSES. There are
several problems in applying transmitted-light microscopy to kerogen analyses. The technique is undeniably
subjective, and results will vary from operator to
operator. Nevertheless, with careful attention to standards, an experienced worker can usually reproduce his
or her own earlier results with excellent precision. Differences between workers are often more a matter of semantics than substance.
A second problem is that when kerogens become very
mature, the particles become opaque and difficult to recognize. For this reason, visual kerogen analyses are not
reliable much beyond the oil window.
Thirdly, a kerogen particle may contain small amounts
of organic material that is quite different chemically from
the bulk of the particle. A woody particle could thus contain some plant wax or tiny globules of resinite that would
impart to it a significant hydrocarbon-generative capacity. If these tiny inclusions are not recognized microscopically, the whole particle would be condemned as a Type
III kerogen having no oil-source potential.
Finally, the diagenetically altered kerogen particles
(usually termed amorphous because of their lack of any
apparent structure) can be derived from various precursors. Their amorphous appearance masks their origin
and makes distinguishing amorphous oil-prone kerogen
from amorphous non-oil-prone kerogen difficult.
Fluorescence microscopy (carried out on specially
equipped microscopes) has been of some value in making
this important distinction. Oil-generative kerogens are
thought to fluoresce much more strongly than do non-oilgenerative kerogens. Fluorescence is useful in distinguishing between oil-prone amorphous kerogens derived
from lipid-rich organic matter and non-oil-prone amorphous kerogens formed by degradation of woody or cellulosic material. However, many samples having little or
no source potential contain large proportions of amor-
98
phous debris that fluoresces for reasons that are not yet
understood.
Despite our insights into possible problems with visual
kerogen analyses and our realization that the use of
fluorescence is vital to evaluating amorphous kerogens,
microscopic kerogen analysis has not had a good track
record. Powell and co-workers (1982) have shown that
there is a poor correlation between maceral type
(identified microscopically) and both hydrogen content
and pyrolysis yield. Visual kerogen analyses should therefore be used with extreme caution, preferably in conjunction with other measures of kerogen type.
ELEMENTAL ANALYSES. Elemental analysis of isolated
kerogens has proved to be a vel}' useful and reliable tool
for determining kerogen type. Its only real weakness is the
time and expense involved in isolating the kerogen. Equation (8.1), adapted from one published by Saxby (1980),
relates atomic HlC and O/C ratios to the hydrogen index
(H.I.):
H.I. = 667(HlC) - 570(O/C) - 333.
(8.1)
8. SOURCE-ROCK EVALUATION
20
15
x X
x
0.0
0.5
1.0
1.5
2.0
X
X
X X
XX X
2.5
3.0
3.5
REFLECTANCE (%RO)
X
4.0
4.5
5.0
5.5
POPULATION GROUPS
POP.
COUNT
MIN. RO
MAX. RO
STD. DEV.
MEANRO
1
2
3
1
10
1
1.78
2.59
4.27
1.78
3.80
4.27
0.379
1.78
3.35
4.27
A
FIGURE 8.5 Vitrinite-reflectance histograms of samples that
are difficult to interpret due to (A) lack of vitrinite,
COMMENTS
Indigenous
6.0
99
100
20
15
10
x
XX
XX
XX XXX X
XXX XXX X
xxxxxxxx X
X
X
X
X
XXX
xxxxxxxxxxxx xxxxx
x xxxxxxxxxxxxxxx x
0.0
0.5
1.0
1.5
2.0
REFLECTANCE (%RO)
2.5
3.0
POPULATION GROUl'S
POP.
COUNT
MIN. RO
MAX. RO
1
2
3
1
27
45
0.36
0.50
0.80
0.36
0.75
1.89
STD. DEV.
MEAN RO
0.073
0.244
0.36
0.67
1.1:3
COMMENTS
Inrligenous
B
FIGURE 8.5 Cont. (B) presence of large amounts of reworked
vitrinite that produce a second mode, and
8. SOURCE-ROCK EVALUATION
20
15
X
X
XXX
xxxx XXX
0.0
0.5
1.0
XX X
1.5
2.0
2.5
3.0
3.5
REFLECTANCE (%RO)
XX
XX
4.0
4.5
5.0
5.5
6.0
POPULATION GROUPS
POP.
COUNT
MIN. RO
MAX. RO
STD. DEV.
MEANRO
1
2
3
4
5
9
4
4
3
2
0.59
1.03
1.51
3.82
5.72
0.89
1.21
2.25
4.52
5.94
0.102
0.079
0.275
0.321
0.77
1.11
1.82
4.27
5.83
C
FIGURE 8.5 Cont. (C) low amounts ojvitrinite and caving,
where the indigenous population (known in this case to be
near 4% R,) is barely visible.
101
102
Pyrolysis T max.
Kerogen Fluorescence.
8. SOURCE-ROCK EVALUATION
103
10
20
5
00
O~--------~r---------~r---------~----------~O
Rtfltctan~
FIGURE 8.6 Change in esr signal intensity (paramagnetic susceptibility) of kerogen as a function of vitrinite reflectance in
the Douala Basin, Cameroon. The downturn at high maturity levels is typical of esr profiles. Reprinted by permission
of the Societe des Editions Technip from Marchand and
Conard, 1980.
dom been used as a maturity parameter because of complications in interpreting measured data. Marchand and
Conard (1980) commented that only the esr signal intensity is useful for source-rock applications; other parameters are too poorly understood to be of value. However,
even the signal intensity is influenced by factors other
than maturity (such as kerogen type) that make it difficult
to apply without supporting data from other techniques,
such as elemental analyses or pyrolysis. Signal intensity
increases strongly in the early stages of maturity, but then
levels out or even decreases during late catagenesis or
metagenesis (fig. 8.6). Application of esr data for maturity determinations would thus require analysis of enough
samples to create a profile.
(Xl
104
frequently used as a direct indicator of hydrocarbon generation. Concentrations of the various Cz to C8 species
have been found to increase by one to three orders of
magnitude during intense oil generation (fig. 8.7). Use of
light hydrocarbons requires detailed sampling throughout the section in order to establish a good data trend.
Summary. The feeling of most workers today is that there
8. SOURCE-ROCK EVALUATION
105
. ..
2
z
<C
(!)
a:
C>
'"z (!)
00
~.j
<C Z- 2
(.)0
OlD
a: a:
<C
>- (.)
J:
....
(.)
.;,
(.)
C>
1984.
Like pyrolysis, atomic HlC ratios measure the presentday status of the kerogen rather than its original chemical
composition. Atomic HlC ratios must therefore be corrected for the effects of maturation by using a van Krevelen diagram like that shown in figure 8.2. These
immature HlC ratios can then be used to calculate Go
according to equation (8.1).
INTERPRETATION OF SOURCE-ROCK DATA
QUANTITY OF ORGANIC MATERIAL
106
Source-Rock Implications
< 0.5%
0.5%-1.0%
1.0%-2.0%
> 2.0%
TIFEOFOR~CMATffiR
Microscopic kerogen-type analysis describes the proportions of the various macerals present in a sample. In interpreting these observations we normally divide these
macerals into oil-generative, gas-generative, and inert.
The oil-generative macerals are those of Type I and Type
II kerogens: alginite, exinite, resinite, cutinite, fluorescing
amorphous kerogen, etc. Gas-generative kerogen is
mainly vitrinite.
Inertinite is considered by most workers to have no
hydrocarbon-source capacity. Smyth (19B3), however,
has dissented from this pessimistic view, claiming, on the
basis of deductive reasoning, that at least some Australian
inertinites can generate significant amounts of oil. Nevertheless, the direct evidence for such a statement is rather
meager.
Pyrolysis results are normally reported in two ways.
Raw data (Sl, S2, and S3) are expressed in milligrams of
hydrocarbon or carbon dioxide per gram of rock sample.
As such these quantities are a measure of the total capacity of a rock to release or generate hydrocarbons or carbon dioxide. These raw data are then normalized for the
organic-carbon content of the sample, yielding values in
milligrams per gram of Toe. The normalized S2 and S3
values are called the hydrogen index and the o.zygen index, respectively. Because variations in TOe have been
removed in the normalizing calculation, the hydrogen index serves as an indicator of kerogen type.
Measured hydrogen indices must be corrected for maturity effects by using a modified van Krevelen diagram
(fig. B.l) as outlined above. Interpretation of hydrogen
indices for immature kerogens is straightforward (table
B.3). Hydrogen indices below about 150 mg He/g TOe
indicate the absence of significant amounts of oilgenerative lipid materials and confirm the kerogen as
mainly Type III or Type IV. Hydrogen indices above 150
reflect increasing amounts of lipid-rich material, either
from terrestrial macerals (cutinite, resinite, exinite) or
from marine algal material. Those between 150 and 300
contain more Type III kerogen than Type II and therefore
have marginal to fair potential for liquids. Kerogens with
hydrogen indices above about 300 contain substantial
amounts of Type II macerals, and thus are considered to
have good source potential for liquid hydrocarbons. Kero-
8. SOURCE-ROCK EVALUATION
107
TABLE 8.3
Hydrogen Index
(mg HClg TOe)
Principal
Product
Relative
Quantity
< 150
gas
oil + gas
oil
oil
oil
small
small
moderate
large
very large
....
110
~
.lo.
"-
150-300
300-450
450-600
> 600
lao
,.,-
.,?C:
f '"
",0
90
~~!fJ'J
i/oO}
.
f?ld:
60
",
0.
0.
TABLE 8.4
Atomic
Hie
Atomic
ole
Hydrogen
Index'
"
",'"
.:5
...J
<,,0'
0.06
0.08
0.09
0.10
0.11
0.12
0.14
0.16
0.18
0.20
700
622
550
477
405
332
254
176
98
20
UJ
<;3l;
",b
Cf)
oil
oil
oil
oil
oil
oil + (gas)
oil + gas
gas + (oil)
gas
(gas)
;Q'"
"'~ ~
40
0'1) o{>;
~o
>0..
()
,,/ 10
>
Product
,,'
,'t
iii
>...J
crPI
'" sJ
a:
1.60
1.50
1.40
1.30
1.20
1.10
1.00
0.90
0.80
0.70
....J:.
"I
70
is'''
/i
30
20
'0
11
13
15
17
108
vary from formation to formation. The correlation between TOC and hydrogen index is weakest in nonmarine
or paralic rocks containing large amounts of woody or
cellulosic material, because there is not always a direct
correlation between TOC and oxygen levels in the
sediment.
MATURITY
Vitrinite
Reflectance
Tmax
(%Ro)
Thermal
Alteration
Index (TAl)
(OC)
Conodont
Alteration
Index (CAl)
0.40
0.50
0.60
0.80
1.00
1.20
1.35
1.50
2.00
3.00
4.00
2.0
2.3
2.6
2.8
3.0
3.2
3.4
3.5
3.8
4.0
4.0
420
430
440
450
460
465
470
480
500
500+
500+
1
1
1
1.5
2
2
2
3
4
4
5
Pyrolysis
Bitumen Parameters. The Carbon Preference Index cannot be used as a reliable indicator of maturity; that is,
there is not a one-to-one correspondence between CPI
and maturity level. CPI values above 1.2 or below 0.8
traditionally have indicated immaturity. Values between
0.8 and 1.2 are not diagnostic, for reasons discussed in
chapter 5.
The ratio of DPEP to etio-type porphyrins has been
used upon occasion as a maturity parameter because
cracking of the exocyclic ring of DPEP species produces
etioporphyrins. The DPEP/etio ratio has been calibrated
to vitrinite reflectance (fig. 8.9), but Mackenzie (1984)
has suggested that the calibration is not universal.
A number of polycyclic biomarkers are used as indicators of bitumen maturity. The Methylphenanthrene Index-1 (MPI) of Radke et al. (1982) has been related to
vitrinite reflectance within the oil-generation window by
equation (8.2):
Ro = 0.60(MPI) + 0.37.
(8.2)
Most of the biomarker ratios used as maturity indicators involve steranes and triterpanes. Moretanes, which
are unstable triterpanes, can be used as a maturity indicator for immature samples. The presence of more than a
8. SOURCE-ROCK EVALUATION
100
90
109
13QH
Core 10
31H
R
80
I:
]. 70
e-
8.
60
~50
do 40
\J.l
30
20
10
JJ
re 37
29H
Tm
31H
~30M
O~-'--'--.~~-r
Retention time -
B.l0).
110
m Prudhoe Bay
o Ship Shoal
0
~ O~erthrusl Bell
Miscellaneous
Shale Bilumens
.. Green River Shale
Pyrolysales
I. 0
110. 21
111
. .... .JOO
Coryt
0.5
- - - - -
10
17(l (20RI
(IV)
Sa. (20R)
fill
--..-~. j
Rearr;,nged
Steranes
J1t-~J\~
'1"[ J.
)1
,.
1.,
Immature
Shale Extrac t
J~
t'lature
Shale [x"'"
"'-----
8. SOURCE-ROCK EVALUATION
111
OPERATOR.
"EU. NAME:
GEOCHEMICAL LOG
......
::a::
.......
LOC.HION:
T. 0
Turquot$'"
.3 00 I'T .
It..
zo ..
....
....
-....
.
"
...,
....
"'"
,100'
t.OOt
lS001
....
til
CONGLOMEJIA T
SANDSTONE
COAL
CASINO CEMENT
cJ
~ LIMESTONE
OOlOMfTE
CHEAT
lO( HALITE
~ ANHYORITE
IGNEOUS
VOLCANICS
M
M
8. SOURCE-ROCK EVALUATION
%Corg
.3
.6
.9
.1
.3
.5
.a
18000
QUANTITY
FIGURE 8.14 Geochemicallogfor the C.O.S. T. B-2 well,
offshore New Jersey.
FIGURE 8.13
QUALITY
MATURITY
t.3
113
114
ences in depositional environment. A modified van Krevelen diagram (fig. 8.15) shows that the foreset beds have
high oxygen indices and low hydrogen indices. They contain primarily Type III kerogen, from which the marine
organic material was removed by oxidative decay. The
bottomset beds, in contrast, have higher hydrogen indices
and lower oxygen indices as a result of preservation of
some marine organic matter. These bottomset beds therefore have much higher hydrocarbon-source potential.
Such scenarios are probably repeated in many settings
worldwide. For example, the Jurassic Kingak Shale and
Triassic Shublik Formation of the Ellesmerian Sequence
of the North Slope also show the same bottomset-foreset
relationships, with organic enrichment occurring in the
bottomset beds. The Gulf Coast may also be explained by
this model. Drilling in the Gulf Coast has only penetrated
foreset beds because the bottomset beds are buried very
deeply. Thus far no good candidates for source rocks have
been found in the oxidized foresets. The effective source
rocks for most of the Gulf Coast oil are probably the
deeply buried bottomset beds that we may never see .
900
600
tii
"0
.5
...
0
"0
'
300
Bottomsets
Foresets
/.
100
200
Oxygen index
:~oo
ORGANIC-FACIES DETERMINATIONS
8. SOURCE-ROCK EVALUATION
115
c,-c,
,.,-:-,
.........
,, Cn
The North Sea coal is a potential source rock for ga.s and
yields only small amounts of heavy hydrocarbons and n-alkanes. (B) The Kalimantan coal, which is a source for liquid
hydrocarbons in the Mahakam Delta, yields large amounts
of heavy n-alkanes. Reprinted by permission of the Societe des
Editions Technips from Durand and Parratte, 1982.
116
1000
2000
II)
II:
o
I
I
I
I
I
I
---
I
I
I
I
::I!
I
I
I
I
,
I
I
I
DIAGENESIS
:I
,-,.-
,,-
I
I
I
I
I
,,
,,
,I
I
I
,,I
I
I
I
I
,
,I
,
,
I
I
I
I
I
I
I
I
II-
,,
1.35
I
I
I
I
4000
1 0
I
I
,
,
3000
::c
D.
W
lee
I-
0.7
--- ,,-.I
IW
0.5
-,-,
-,I
I-
,I
I
I
I
I
I
I
I
,
,
I
,
,
,I
OIL GENERATION
"'' -1 ."" 1
MATURITY ANOMALIES
I.e.
2.0
3.0
".0
I
I
,I
,
,
PALEOCENE
I
I
I
,I
,
I
I
,I
I
I
,,
I
,I
I
I
EARLY TRIASSIC
I
I
I
I
I
I
I
I
I
I
I
GAS GENERATION
8. SOURCE-ROCK EVALUATION
1.100
\~
u oo
o~
, f' ..
~
INTRUS!VES
~,
J._
TERTIARY
~,.,
~r-
rt
~SOZOIC
",00
.J
[0
J._
!jjjNFORMlt S
uoo
'C
.1 .
' .. .. . 0
I..
Dow, 1977.
"' 7 "
10
~~
~
1\0 0
I..
.1
117
10 '
10
Effect of an igneous intrusion on vitrinite-reflectance values. Thermal effects are usually measurable to a
distance of about two sill thicknesses on either side of the
sill. Reprinted by pennission of Elsevier Science Publishing
Company from D:Jw, 1977.
FIGURE 8.19
Demaison, G. and R.
of Petroleum Geologists Memoir 35, Tulsa, American Association of Petroleum Geologists, 426 pp.
118
8. SOURCE-ROCK EVALUATION
119
3000
\
PAUOGEliE
5000
E
1;;
'".......
l!:
7000
9000
I~OOO
13,000
ITOP
<
I--f- TRANSITION
\]l:
.... 17
TOP
RlY
ZONE
~
0
'" '"
-'"
I.
::- I&""
'jbp LAn
_f.--S
I...
JURASSIC
15,000
30
5-0
10
TOTAL ORGANIC CARBON
(TOCI I'JJ
71.0
0.4
O.Z
VITRINITE REfUCTAHCE
(Roll'JJ
Depth (ft)
TAP
1000
1200
1500
2000
2300
2600
3000
3200
3400
3700
4000
4200
4800
5000
5200
5400
5700
2.0
2.0
2.0
2.0
2.0-2.5
2.0
2.3
2.3
2.0
2.0-2.5
2.2
2.5
2.5
2.0-2.5
2.6
2.5
2.5
2.6
GOOO
Ro
BitumenITOC
0.42
0.49
0.46
0.55
0.60
0.51
0.59
0.63
0.60
0.05
0.07
0.02
0.10
0.08
0.09
0.06
0.17
0.25
0.44
0.66
0.61
0.21
0.03
0.07
0.09
0.11
0.12
TOC
Well
Formation
(ft)
(wt %)
A
A
A
A
A
B
B
B
B
B
Kimmeridge Clay
8610
8625
8632
8651
8686
7967
7993
8015
8165
8174
6.2
7.1
8.9
4.4
10.3
1.4
1.5
1.3
1.2
1.0
Lower Jurassic
Rock-Eval
Hydrogen Index
(mg HClg TOC)
462
512
604
517
625
87
112
64
123
101
120
It is tempting to say that the Lower Jurassic shale is as immature as the Kimmeridge Clay, because it is buried less deeply.
The two wells are not close together, however, and may very
well have had quite different thermal histories. Thus presentday depth of burial should not be used as an indicator of
maturity.
high Production Indices and Sl yields, indicates that some hydrocarbon generation has occurred in Unit G. Maturity data
show the unit to be within the early to peak phase of oil
generation.
The uniformly high hydrogen indices may indicate a high
proportion of oil-generative kerogen in Unit G. However, the
lack of correlation between TOC values and hydrogen indices is
contrary to our expectations (see fig. 8.8). It is highly unusual to
find a rock with TOC near 0.5% with a hydrogen index near
400, because the extensive oxidation indicated by low TOC
values almost always results in loss of hydrogen-rich material.
We are therefore suspicious of the pyrolysis data in Unit G; there
could be problems with contamination or migration that might
be uncovered by further analyses. We therefore should be cautious in ascribing a high source potential to Unit G without
resolving the discrepancy between TOC and pyrolysis data.
The lower part of Unit B also has high TOC values, but pyrolysis yields indicate negligible remaining hydrocarbon-source
capacity. The very high maturity levels measured for those samples prove that we are already into the gas-generation window
in Unit B. In order to determine whether the rocks of Unit B
have in fact generated oil or gas we would have to determine the
type of kerogen originally present in the rocks. Microscopic
analysis would be about the only way to accomplish this feat on
such overmature samples. Alternatively, if we could find samples of Unit B from a similar facies from a less mature well
nearby we might be able to extrapolate those data to the Turquoise Well site.
A few sands from Unit D are also of interest to us because,
although they contain little organic matter, the high pyrolysis
yields (Sl, S2, and Production Indices) and low T max values
strongly suggest the presence of migrated hydrocarbons. Extracts from these rocks might profitably be submitted for correlation analyses.
Finally, the maturity profile shown on the Geochemical Log
requires further data and detailed interpretation. The trend
seems to be clearly defined; however, most ofthe data points are
from pyrolysis T max, which is not always a valid maturity indicator. The few vitrinite-reflectance values appear to corroborate
the T max data; however, the Geochemical Log does not include
any histograms or other statistics on the reflectance data. We
therefore should check the original data to verity that we have
confidence in the vitrinite values.
The maturity profile may contain a discontinuity across the
unconformity between the Triassic and Lower Cretaceous rocks
(between Units C and D). Such a dislocation would indicate
erosion between the Triassic and Cretaceous. More data points,
particularly from rocks immediately above and below the unconformity, are needed to verity the existence of such an event.
Chapter 9
Predicting Thermal
Maturity
INfRODUCTION
122
= Aexp( -Ea/RT)
(9.1)
..
'V
~
Q 0.05
5
-'
UJ
1:
I;;
::E
::; 0.01
.......
II:
TEMPERATURE ('C)
(1)=48
(5) = 56
(2) = 50
(6) = 58
(3) = 52
(7) = 60
(4) = 54
(8) = 62
Implementation of Lopatin's method begins with the construction of a burial-history curve for the oldest rock layer
of interest. An example is shown in figure 9.2, which was
constructed from the time stratigraphy for the Tiger well
AGE
100
80
60
123
IMY)
20
40
0
500
1000
1500
2000
:I:
....a.
2500
3000
3500
4000
my-old rock) in the Tiger well constructed from the timestratigraphic data given in table 9.1.
TABLE 9.1
Depth (m)
0
10
38
65
80
100
0
500
900
1800
2800
3700
124
AGE
100
80
AGE
(MY)
60
20
40
100
0
80
60
(MY)
40
20
500
500
1000
1000
1500
1500
2000
0(65,3700-1800)
2000
:r
:r
I-
I-
0.
Q.
2500
"'0
2500
"'0
0(38, 3700-900}
3000
3000
(10, 3700-500}o
PRESENT DAY,"
3500
3500
4000
4000
First step in the construction of the burial-history curve in figure 9.2. Plot the two points corresporuiing to
present-day depth of burial arui the rrwment of deposition of
the rock of interest.
FIGURE 9.3
AGE
100
80
0_
Third step in the construction of the burial-history curve in figure 9.2. Plot all the remaining control points
(age of the datum, thickness of rock presently separating it
from the 100-my-old rock).
FIGURE 9.5
(MY)
60
40
POSITION OF ROCK AT
SECOND TIME-CONTROL POINT
AGE
20
100
80
60
(MY)
40
20
500
500
1000
1000
1500
1500
(80. 3700-2800)
2000
i
:r
2000
l-
"'0
Q.
2500
3000
3000
3500
3500
4000
4000
FIGURE 9.4 Secorui step in the construction of the burial-history curve in figure 9.2. Plot the secorui time-control point,
corresporuiing to the next oldest datum (in this case, 80 my).
The depth of burial of the 100-my-old rock is given by the
thickness of rock that separates the two datums at the present time (900 m in this case).
:r
I-
0.
2500
:;
FIGURE 9.6 Family of burial history curves for the Tiger well
based on the time-stratigraphic data presented in table 9.1.
"'0
The next step is to provide a temperature history to accompany our burial-history CUIVe. The subsurface temperature must be specified for every depth throughout the
relevant geologic past. The simplest way to do this is to
compute the present-day geothermal gradient and assume that both the gradient and surface temperature have
remained constant throughout the rock's history. Suppose, for example, that the Tiger well was logged, and
that a corrected bottom-hole temperature of 1330 C was
obtained at 3800 m. Suppose further that local weather
records indicate a yearly average surface temperature of
190 C. Using these present-day data and extrapolating
them into the past, we can construct the temperature grid
shown in figure 9.7.
Where measured bottom-hole temperatures are not
available, maps of regional geothe. mal gradients can be
useful in estimating the gradient at a particular location.
In many poorly explored areas, temperature profiles will
be based largely on guesswork.
There are numerous other variations that can be employed in creating temperature grids. For example, we
can change surface temperatures through time without
altering the geothermal gradient (fig. 9.8). Causes for
such events could include global warming and cooling or
local climatic variations resulting from continental drift or
elevation changes.
AGE
100
80
(MY)
60
20
40
30".---------------------------------40----------------------------------50----------------------------------10-------___________________________ _
50
125
5.1. =ls e
500
1000
- - ________________________________ _
80" _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
1500
2000
90 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
100-----------_______________________ _
2500
110"-----------------------------------
3000
120" _ _ _ _ _ _
::i!
...>:"-
___________________________ _
3500
130"------- ___________________________ _
4000
FIGURE 9.7 Subsurface-temperature grid that assumes a constant surface temperature (190 G) and geothermal gradient
(3 GI1DO m) during the last 100 my. Isotherms are spaced
every 10 G for convenience in calculating maturity.
AGE
100
80
40
20~ _ _ _ _ _ _ _ _ _ _ _ _ _ ""''''''''''''''''
.",."'"
.",..",..",..",.
__ - -
.",.~
.o:_____________ .. .",.~
____________ ...........
.",.~~....
70!.. _ _ _ _ _ _ _ _ _ _ _ _ _ ~~.",.
.00:.. _ _ _ _ _ _ _ _ _ _ _ _ _ ....
.",.~~~
20
.",..",.;
.",..",.;;
;;.",.~"'"
""'~
_____ -
-_
----------_
----------------------------------------
_-.,..,.",..",.;,.
.",._-
--- __
130~ _ _ _ _ _ _ _ _ _ _ _ _ _
, .... .",.
.",.""'-
.",..",.
1000
1500
2000
_
-
__
.",.~ -~ ....
..o:.. _____________ ~~~~ ~~~~~~~~------------
110~ _ _ _ _ _ _ _ _ _ _ _ _ _ .",..",..",.
500
__
.",.~....
~ .... _ - - -
.....
.,.. .. __
.",......",..",.
~~~~~--~~'~
---------__-----------_
__
.",.~.",..",.
--------_
-------
.",.~_---
.",.""'.",."'"
.",.""'--
~~~~-~~~~~-------------
30:.. _ _ _ _ _ _ _ _ _ _ _ _ _ . .",..",.
ao~
(MY)
60
:I
...>:
Q.
2500
3000
3500
~~
4000
FIGURE 9.8 subsurface-temperature grid that assumes a constant geothermal gradient (3 GI100 m) but a variable surface
temperature during the last 100 my.
126
AGE
.00
80
(MY)
40
60
20
30-. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ,
.o .. _______________________________
~',
50-0 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ , \
o
500
: :-=- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =-~\
::: ===============================~\\\ \
1000
1500
III \ \
2000
:>
2500
:'Qu
,,\
100-_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ' , \
110- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
120- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
I\ I\ I\
:J:
t-
III
\ \ \
'II
\
"
"",,
,,,,
,,
,,
,
3000
\ ' 3500
,
4000
FIGURE 9.9 Subsurface-temperature grid that assumes a constant surface temperature but a geothermal gradient that
dropped dramatically during the last 10 my after being constant for 90 my.
AGE
100
80
60
(MY)
40
20
o
500
1000
1500
2000
!
:J:
I0.
2500
3000
3500
4000
UJ
In other cases the surface temperature remains constant, but the geothermal gradient varies in response to
heating or cooling events. The example in figure 9.9 represents a location at which rapid sediment accumulation
in the last ten million years has lowered the geothermal
gradient, resulting in subsurface temperatures that are
anomalously low compared to the "normal" ones that
dominated previously. More complicated temperature
histories (for example, fig. 9.10) are also possible. "Dogleg" gradients can be used to reflect changes in thermal
conductivities caused by variations in lithology (fig. 9.11).
There is no theoretical limit to the complexity that can
be introduced into our temperature histories. Given adequate data or an appropriate model on which to base
complex temperature reconstructions, we are limited only
by our own creativity. In most cases, however, the data
necessary for highly sophisticated temperature reconstructions are simply not available.
AGE (my)
20'
80
80
70
80
50
.0
30
20
'0
30'
.0 '
,000
$0 '
70 '
,..,
--- --
--
eo'
-- --
2000
Q)
.....E
eo '
3000
,.0 '
-- -- - --
.000
5000
,.0'
J:
.....
n.
80 '
'00'
...
III
Q)
eooo
127
128
AGE (my)
100
80
40
80
20
ORIGINAL\
THICKNE8S
=
1000
3000m
DEPOSITION
/RECOMMENCES
000
POST-EROSIONAL
THICKNESS
Q)
3000
..
-eL.n
=2000m
Q)
4000
::I:
I-
ER0810NAL
PERIOD
a..
W
000
by erosion during an
uplift event lastingfrom 70 mya to 60 mya. Individual burial-history curves remain parallel, but the distance between
the two lines which bracket the erosion decreases by 1000 m.
129
...w
9
iC
x
to-
G..
Juxtaposition of burial-history curves for hanging wall and footwall. Shaded area represents missing section.
FIGURE 9.13
WELL A.LPHA.
FIGURE 9.14
has occurred.
130
eoo
TIME (m.y.B.P.)
AGE (MY)
aoo
300
200
3QC
1000
~
W
W
L-..
2000
3000
.000 ~
J:
aooo
I-
It
4CXlO
60C
9<XXl
J: 12CXlO
ISOC
180 C
20000
.00
300
1SOoC
_. - - : 180C
- ----- -
210C
AGE (MY)
500
~ ------- ~- ~
'6CXlO
7000
eoo
9IJC
Q.
aooo
goC
200
hanging wall and footwall of thrust faults. Reprinted by permission of the American Association of Petroleum Geologists
from Edman and Surdam, 1984.
.00
'000
2000
3000
AGE (MYI
4000 ~
J:
SOOO
I-
60
" 000
20
LEV IE L~--'---++
a..
w
o
aooo
1000
- 1000
...
UI
>
UI
- 2000
....
c
en
UI
- 3000
....
UI
- 4000
..
II
:I:
~5000
Do.
UI
R~paSSive
131
margin -
o
-1
km
-3
-4
Subduction/Marginal Sea
-5
-6
-7
550
I
:t:fJ
I
300
I
Ma BP.
250
I
200
I
150
I
100
I
50
I
oI
132
AGE (MY)
100
80
60
40
20
o
500
50--____ _____________________________
1000
1500
2000
2500
::;
...'"-"
w
0
3000
3500
130-- - - _ _ - - _ _ _ _ _ _ _ _ _ - - - - - - - - - _ _ - - - - _ - -
4000
CALCULATION OF MATURITY
Temperature-Factor (-y)
30-40
40-50
50-60
60-70
70-80
80-90
90-100
100-110
110-120
120-130
130-140
140-150
150-160
160-170
-7
-6
-5
'1128
'164.
-4
'lt6
-3
-2
-1
0
1
2
3
'Is
16
32
5
6
%2
'14
%
1
2
4
8
64
his model by Waples (1980) and the successful application of Lopatin's method in numerous published examples have confirmed the general validity of Lopatin's
assumption.
In order to carry out maturity calculations conveniently, we need to define both a time factor and a temperature factor for each of the temperature intervals
shown in figure 9.19. Lopatin defined each time factor
simply as the length of time, expressed in millions of
years, spent by the rock in each temperature interval.
The temperature factor, in contrast, increases exponentially with increasing temperature. Lopatin chose the
100-110 C interval as his base and assigned to it an
index value n = O. Index values increase or decrease
regularly at higher or lower temperatures, respectively
(table 9.2). Because the rate of maturation was assumed
to increase by a factor of two for every 10 C rise in
temperature, for any temperature interval the temperature factor, which Lopatin called ,,{, was given by equation (9.2).
"{ =
2n
(9.2)
133
-----------------------------------
- soo
__ _ _
,"
,
_ ____________________________ ---, 0 0 0
60' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
_,:!t OO
0'-- ________________________________ _
.0' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
~20
00
0'
.0 ' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
-25 0 0
I J O' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
JO' - - _________________________________ _- 35 00
Temp.
Interval
Temp.
Factor
Time
Factor
30_40C
40_50
50_60
60_70
70_80
80_90
90_100
100-110
110-120
120-130
'1128
'164
7
7
6
6
7
12
12
18
12
6
'132
%6
Va
'I.
'/2
1
2
4
Interval
Total
TTl
TTl
.05
.11
.19
.38
.88
3.0
6.0
18.0
24.0
24.0
.05
.16
.35
.73
1.6
4.6
10.6
28.6
52.6
76.6
Time
(m.y.BP)
86
79
73
67
60
48
36
18
6
0
-4 000
Temperature factors (,,{actors) and time factors for the 100-my-old rock in the Tiger well.
FIGURE 9.20
134
I.
'" . .. ,
,,
AGE (MYBP)
4.
I.
,.
.., ..
I.
TTI=3.1
",
1000
\L
_________
4000
2000
4.
,..--, ,
,,
L-______________
3000
~~4
, ,
'.0;- -"\',, '-\
1'iO------------
_________________J
:)000
,iio- - ,
2000
1000
TTI=0.8
TTI=7.8
\
\
\
\
'000
I.
\
\
1000
I.
AGE ( MYBP )
4.
L-________________-L4
------- -- ---,
1000
'" .. .. ,
4.
I.
"
\
TTl " . , \
,------B
TTI=24.4
\
rectly related to the amount of time spent near the maximum burial depth and temperature. The calculated
maturity in figure 9.21D is by far the highest, because the
temperature reached and maintained at 4000 m was
much higher than that achieved in the examples where no
erosion occurred.
However, when important events occur early in the
history of a rock, their impact on maturity is much less.
For example, figure 9.22 illustrates two events that will
increase maturity: a higher geothermal gradient (fig.
9.22B) and extra burial preceding later uplift and erosion
(fig. 9.22C). However, the higher geothermal gradient
was only in force early in the rock's history when its
temperature remained low because of shallow burial.
Thus the TTl in figure 9.22B is only slightly higher than in
the control example (fig. 9.22A). One implication of this
exercise is that source-rock maturity in rifted basins,
3000
L-________________-k4 ~~----------~~-J
TABLE 9.4
135
Reflectance (Ra)
TTl
0.40
0.50
0.60
0.65
0.70
0.85
0.90
1.00
1.15
1.35
1.50
1.75
2.00
2.50
3.00
4.00
5.00
<1
3
10
15
20
40
50
75
110
180
300
500
900
2,700
6,000
23,000
85,000
Ra
Generation
0.40
3
10
15
20
50
75
180
900
0.50
0.60
0.65
0.70
0.90
1.00
1.35
2.00
TTl
r
1
oil
wet gas
dry gas
peak
late
136
.-.- AGE
,
,
J:
f
NON-DEPOSITIONAL
HIATUS
I-
a.
J:
I-
a..
\.
\.
WELL #1
\..
\ . MEASURED
\.
WELL #1
MATURITY
-+
FIGURE 9.24 Poor correlation between measured and predicted maturity data for Well # 1.
FIGURE 9.23
in the model were incorrect. This situation can arise easily when our present-day temperature data are poor or
when past events (such as igneous activity) created a thermal regime quite different from the present one. A second
explanation, which is the one we shall adopt in the present example, is that we have made a poor estimate of the
amount of erosional removal. In the case of Well #1, we
postulated a nonerosional hiatus. Because our calculated
maturity values were too low, it seems likely that substantial removal occurred during the time of the unconformity. The measured maturity level was therefore higher
than our model predicted. On the basis of these data we
can revise our geological model and include enough erosional removal (fig. 9.25) to bring measured and calculated maturities into agreement.
Because the effects of underestimating paleotemperature are about the same as the effects of underestimating
erosion, one might think that it would be difficult to decide which was the better explanation for discrepant
data. In practice, however, it is usually easy to distinguish
between the two possibilities on the basis oflocal geology.
For example, Magoon and Claypool (1983) chose
among three possible thermal histories by comparing predicted and measured maturities for the lnigok-1 well on
the Alaskan North Slope. The thermal history finally chosen (fig. 9.26) was rather complex but justified on the
+-AGE
::c
l-
n..
w
c
\j
WELL #1
Rifting
3.0
5.0
......
:;;
0
0
"-
"~
~ 4.0
2.0
3.0
300
200
M.Y.B.P.
137
100
138
TTl
Ro
.
.3
.5
1.0
1
~~~~UU~
1000
100
__-L-L~~UL__~~~LU~O
2000
4000
6000
~
J:
~
Q.
8000
2000
4000
6000
8000
10,000
12,000
14,000
10,000
-------
12,000
Oil generative
Oil generative
zone pred icted
from TTl
zone from
Vitrinite
_L __
reflectance
16,000
1
--------A
14,000
16,000
TIl
No
Expected Hydrocarbons
(80% Probability)
50
75
180
500
900
0.90
1.00
1.35
1.75
2.00
normal oil
normal-light oil
condensate-wet gas
wet gas
dry gas
139
The earliest application of Lopatin's method to exploration was published by Zieglar and Spotts (1978) in an
analysis of the hydrocarbon production and future potential of the Central Valley of California. Using the as-yetunpublished approach of Waples (1980), they drew isoTTl lines on burial-history curves to show the development of maturity through time and to compare the thermal histories of various depocenters within the basin (fig.
9.28).
The simplest way to put iso-TTl lines on burial-history
curves is to begin by selecting the TTl values of interest.
Useful TTl values might include those for the onset and
end of oil generation or those for the liquid deadline.
Then starting with the deepest horizon in the burialhistory-curve family and beginning with deposition of
that sediment and working toward th~ present, one calculates interval-TTl values and sums them until the desired
TTl value is reached. The point at which the desired TTl
was reached is marked on the burial-history curve. The
process is repeated for each member of the burial-historycurve family. Then all the points having the same TTl
value are connected with a line. If TTl values corresponding to the onset and end of oil generation are
plotted, the resulting maturity band (fig. 9.29) defines the
oil-generation window through time.
Figures like 9.29 have proven extremely useful, particularly in understanding the timing of hydrocarbon genera-
140
AGE (MYBP)
80
60
AGE (MYBP)
20
4()
80
4()
60
20
50" -
100' -
10
t:
15
20
Ii:
2
3
'" 5
:I:
Ii:
~
150" -
6
7
200' 25
8
9
250"-
10
'C
~ OIL
TEJON
DEPOCENTER
11
GENERATION
90
S\r,_
SO
70
60
SO
40
30
20
Tfu
r... 'c
n_,~,.,
1ft
rlu,1IIDIn rr/ ..
.~
IM/.,. rr /- . D
, f'rItr
C'$ArlJIO[,
CXI71,
rr/-
"I- I.'
rTl- ...
t.NC1:/tIOT.,
1S.,
,,
,,'.
1000
2000
3000
Ltqt.r '''''~
~ GAS
30
GENERATION
10
~1~t.2S'"~
BUTTONWIllOW
DEPOCENTER
CONDENSATE FORMATION
ACE CHYSP)
100
i!i
4000
6000
PECTEN'IA
11~-~_i:I~~~i:~~-~~~~l~~:~:-~-7~~::~~:~::::~~::::~:
. .
~~~~~
...
00
05
OS
10
1-0
E
...
IS
20 x
. " ." .
.......
........ ,
,
. " ....
" ......
'.
.. .' ..
. .... "
. .
PECTEN IA
00
1-5
_ .....
75
'
20
iLw
) -0
)0
) -5
) 5
'0
~~~~~l~l~~i~jl~jljI~:~I~~:~::::::-;~c:??::::~:~~::~:::::::~:~
~~~~4:...:..~;:..:....:...:...,;,:-,.:..:-,-::.~~,_=:,::':':.~~.:O~S::,~'
. . . . .. . : ".: ..... .... . ... ... .
:: : . . . :.:.0::S.. :.::;::/.;.!:A~.
'"
..........,
00
o~
MUSSEll
(PROJECTED)
NAUTl l US'1
(PROJECTED)
10
0 '5
10
...
:r
1~ "J-O
~~~.:~::i,~,~~~~'~O~.~S~%~'~'~ 20
0,5(% ':, ' ',' ': :
J~
..
. -.: ..:::"....
>...::
:".
..
':': . ' , ... ~~ : ',':'
....
....................
"..
..
A. . .
NARRA..... ATURK
t;0j
If;TI GELLIBRAND
MARL
MEPUNGA FM +
Y;l, GERRIP GP
vey,1983.
:',
4'0
~ LlMES10NE
1' 0
IS
!!!
~Mt.Rl
PECTEN -!A
;~~~~~~I1~~~~~!i~~~~~~~~~OO
15
4 '~
~ PORT CAMPBELL
, 5
PECTEN -I.
25 0::
w
' -0
141
10km
[8
SHERBROOK GP
OTWAY GP
]
l:
0::
\oJ
25 o
30
) -5
' 0
, 5
142
DEADLINES
One of the potentially most important applications ofthermal modeling to exploration is in predicting the oil deadline. The economics of oil and gas exploration are often
very different; indeed, gas is of no value at all in some
remote regions. Knowledge of oil deadlines (limits below
which economic accumulations are unlikely to occur) is
therefore very important in exploration.
Preservation deadlines can be easily shown on burialhistory curves, in plan view, or on cross sections, in the
same manner as hydrocarbon-generation limits. Even a
very preliminary estimate of the liquid-hydrocarbon
deadline can be extremely valuable in formulating a drilling program.
the concept of time into geology in an effective and unusual way. Frequently, in fact, the burial-history curves
themselves prove to be more interesting than the TTl
values. When maturity calculations are carried out by a
computer, the burial-history curves are often deemphasized compared to TTl values. Furthermore, when the
computer constructs a burial-history curve, the geologist
is not as involved and will not learn as much as if he or
she had constructed it by hand.
Computerization is desirable but, in my view, should
only be used after a geologist has mastered drawing the
burial-history curves and calculating and plotting maturity by hand. Thus prepared, the geologist will be able
to derive maximum benefit from data created by the
computer.
COMPUTERIZATION
143
T MAX
'F
'c
lO4/ToK
500
250
20
400
16
15
14
13
12
II
200
10
33
32
300
31
150
25
29
27
24
100
200
21
30
18
50
01
1.0
10
100
1000
1975.
144
LOM
RANK
Ro (",
"VM
HYDROCARBON
GENERATION
PALEOZOIC
400
300
2
LIGNITE
DIAGENETIC
METHANE
SU8 . C
BIT.
12
HIGH_
VOL.
10
BIT.
B
A
MV BIT.
:::c
40
35
2S -
ANTH.
1.5
20 -
IS -
10 -
16
18
1.0
30 -
SEMI ANTH .
0 .5 -
LV BIT .
14
-=--==
-== -=-
45
-=
-
S -
20
2.5
OIL
GAS
--=
-=
---
CONDENSATE
&
WET GAS
CATAGENETIC
METHANE
20
400
GEOLOGIC TIME ( M.Y.)
Correlation of LOM with various coal-rank parameters. Reprinted by permission of the American Association of Petroleum Geologists from Hood et al., 1975.
FIGURE 9.32
Burial-history curves and hydrocarbon generation at three locations in the Illizi Basin, Algeria, predicted
using the model of Tissot (1969). Reprinted by permission of
the World Petroleum Congresses from the Proceedings of the
Ninth World Petroleum Congress, Applied &ience Publishers,
from Tissot et al., 1975.
FIGURE 9.33
""c
TISSOT
Arrhenius plot showing why the various thermal models all seem to work adequately despite their furu1amental differences. Because the range of times and
temperatures we normally observe for oil generation in nature is narrow, the available data are tightly clustered. Consequently, it is possible to draw many very different lines
(representing the various models) through the data. Only if
we obtain new data that increase our range of time and temperature values will we be able to choose among these
models.
FIGURE 9.34
145
146
but for now the best model for each geologist is that
which is most practical.
POTENI'IAL PROBLEMS WITH
MATURITY CALCULATIONS
Models for predicting thermal maturity have been developed to aid in understanding the hydrocarbon-generation
and -preservation histories of sedimentary basins. Appli-
cations include defining the hydrocarbon-generation window, determining timing of generation, and defining
deadlines for liquid hydrocarbons. Calibration and much
testing of these models have shown them to be reliable
and accurate enough for routine use in exploration programs, both in frontier and maturely explored areas.
Some of the models employed are also capable of aiding the geologist in reconstructing the history of an area.
By comparing calculated maturity levels with measured
values, one can discover erroneous assumptions about
geologic or geothermal histories. Construction of burialhistory curves is usually enlightening.
The numerous published and unpublished maturity
models all appear to give satisfactory correlations with
measured data, despite substantial differences in the ways
in which they interchange time and temperature. We cannot yet say with certainty that one of the models is mathematically superior to the others. Choice of a suitable
model at the present time is best made on the basis of
availability, convenience, and integrability with geology.
Lopatin's methodology, with a variety of relatively minor
variations in the time-temperature interrelationship, is
the most widely used technique today.
Although maturity calculations are often carried out by
hand, the utility of the models can be increased by using
computers to perform calculations and plot the results.
One must guard against the computerized version becoming a "black box" technique, however. One can only take
full advantage of maturity-modeling technology by maintaining a sound geological foundation for the model. Output data will only be as good as the geological model
responsible for those data.
SUGGESTED READINGS
Bond, W. A., 1984, Application of Lopatin's method to determine burial history, evolution of the geothermal gradient, and
timing of hydrocarbon generation in Cretaceous source rocks
in the Sanjuan Basin, northwestern New Mexico and southwestern Colorado, in]. Woodward, F. F. Meissner, and]. L.
Clayton, eds., Hydrocarbon Source Rocks of the Greater
Rocky Mountain Region: Denver, Rocky Mountain Association of Geologists, pp. 433-447.
de Bremaecker,].-Cl., 1983, Temperature, subsidence, and hydrocarbon maturation in extensional basins: a finite element
147
Time-stratigraphic data:
Age (my)
o
2
38
65
80
100
Depth (m)
500
1200
2700
3000
4000
148
Temperature data:
Present-day average surface temperature:
Corrected BHT (4200 m):
Estimated surface temperature at end Cretaceous:
3. Calculate present-day ITl for a rock at 3000 m in the Beige
Well using both maximum and minimum scenarios for Tertiary
removal.
Time-stratigraphic data:
Age (my)
30
38
65
80
100
Depth (m)
300
1400
1700
3000
Depth (ft)
Tops
Age (my)
Period
Permian
Virgil
Missouri
Des Moines
Atoka
Morrow
Mississippian
Kinderhook
Sylvan
Arbuckle
230
280
288
296
304
309
320
340
425
470
Permian
L. Carboniferous
"
E. Carboniferous
Ordovician
7,000
8,000
11,000
13,000
18,500
21,000
23,000
25,500
27,500
Temperature data:
Present-day average surface temperature:
Corrected BHT (3000 m):
4. The Wtraviolet Well is spudded in Paleocene sediments. At a
depth of 1500 ft, micropaleontology indicates the rocks to be of
Maestrichtian age. The following Upper Cretaceous boundaries
are noted:
Maestrichtian-Campanian
Campanian-Santonian
Santonian-Coniacian
Coniacian-Turonian
Turonian-Cenomanian
1807 ft
2002 ft
2360 ft
2546ft
3017 ft
The Cenomanian is 480 ft thick and overlies 1000 ft of Kimmeridgian-age shale. Total depth is reached at 6120 ft in Middle
Jurassic rocks.
Evidence from related sections indicates that the Paleocene
was originally about 3000 ft thick and that no other Cenozoic
sediments were ever deposited. Total original thickness of the
Kimmeridgian is thought to be 1500 ft. It is also believed that
500 ft of Lower Cretaceous sediments were deposited before
uplift and erosion began.
Assuming a surface temperature of 100 C and a geothermal
gradient of 2 0 F/100 ft, draw a burial-history curve for the section penetrated and calculate maturity for the Kimmeridgian
shale.
20C
16
14
12
10
AGE (MY)
30C-
149
2000
40C50C60C-
4000
6000
70C80C_
8000
: I:
IQ.
90C100C-
10,000 ~
12,000
110C 120C-
14,000
130C-
16,000
140C18,000
Family of burial-history curves and subsurfacetemperature grid for the Black well.
FIGURE 9.35
exact age of that rock is not known, the curve cannot be taken
back to the time of deposition. Fortunately, however, the temperature during this period of uncertainty was very low and did
not affect maturity appreciably,
Calculation of maturity is now easy. Using the temperature
factors given in table 9.2, we find the TIl at 16,150 ft to be about
17.7.
2. The present-day temperature profile was constructed from
the present-day surface temperature of 15 C and the gradient of
3 C!l00 m (calculated from (141 - 15)/42). The spacing of the
10 isotherms is therefore 333 m, At the end of the Cretaceous
the gradient was the same as the present, but the surface temperature was 10 higher. In the absence of any more information, let us assume that cooling proceeded at a constant rate
from the end of the Cretaceous (65 mya) to the present. Furthermore, let us assume that during the Late Cretaceous the temperature did not change. With these assumptions we can construct
the subsurface-temperature grid shown in figure 9.36.
The family of five burial-history curves for the Red Well is
shown in figure 9.36 superimposed on the subsurfacetemperature grid. TIl values can now be calculated by defining
the length of time spent in each temperature interval. An ex-
150
AGE
80
TEMP.C
AGE (m.y.)
(m.y.)
40
60
20
30'
1000
1000
2000
2000
I
f-
I
f-
a..
a..
3000
3000
4000
4000
5000
5000
140 0
Family of burial-history curves and subsurfacetemperature grid for the Red well. lsomaturity line represents
the beginning of oil generation at TTl 10.
FIGURE 9.36
FIGURE 9.37 Burial-history curves for a 100-my-old rock, assuming two difforent erosional models (500 m or 2000 m of
removal) commencing 5 mya in the Beige well.
.08
.17
.39
.83
2.21
5.96
11.46
15.46
'V-Factor
Y,26
Ys<
%2
Y,6
Yo
Y4
Yz
Time
Factor (my)
10
6
7
7
11
15
11
4
Interval
TTl
.08
.09
.22
.44
1.38
3.75
5.50
4.00
Total
TTl
151
AGE (MV'
20
40
60
160
120
100
80
I~C ~__~~~~~~~-L~~~~~~~~~--~--~--~--L-~~-t
2O' C -
30' C -
1000
2000
40' C 3000
SO' C -
TTl 2.7
~
w
4000
6O"C -
TTl 4.9
5000
70' C 6000
6O' C -
Famill' Of burial-history curves and subsurfacetemperature grid for the Ultraviolet welL
FIGURE 9.38
152
AGE jMY)
480
420
360
300
240
180
120
60
0
0
20 C -
2000
30 C 4000
40 C 6000
SO 'C 6OC -
8000
70 C -
10,000
8O C -
12,000
SO' C -
14,000
1(xtc-
-....
X
....0
A.
16,000
II00C 18,000
120C20,000
130C 22 ,000
140' C -
24 ,000
lSO C 160C-
26,000
170C -
28,000
Family of burial-history curves and subsurfacetemperature grid for the Pink well,
FIGURE 9.39
AGE /MY)
480
420
J60
300
240
180
120
60
FIGURE 9.40
:r
t:w
153
154
AGE (MY)
300
200
100
O-r____~I~~~~l------~I------_i_
.,.,
'lI\
~,
~,
~,
~,
'lI\
~\
1000-
~,
~\
"',
2000-
'lI'
O~
.,
....'
,_,"-
IW
."
o ,
3000-
'(
:r
.... t:-
11.
W
: ~:Z
o ;::
II:
~
l-
5000-
::Ii
::Ii
/.
""
"
0{
\'
4000
,I"
0\
I-
,,"
::!:
~.,.,
~~\
(J)
a:
AGE
o~
...
'z
0
~'I
.~ ~:: V
/'
I'
C-
o ::;::
o '~C0
. . ._.
.,
\II
C
'<II(
-I
o~
I TRAPS
SOOO~----~----~~~--~--------;-
fXlST
Chapter 10
Correlations
INrRODUCTION
156
API
= - - -141.5
---- Specific gravity
131.5.
(10.1)
10. CORRELATIONS
157
-80
cfi
-100
- 120
<0
-140
-160
-1 80
-200
-32
-30
-28
26
158
Corbonotes
o Sid 0 . .
i
- 200
S1
119
918
- ISO
-100
-so
00 l %0 J
FIGURE 10.2 Difforences in hydrogen-isotopic compositions of
oils sourced from carbonates and shales. Reprinted by permission of E. Schweizerbar'sche Verlagsbuchhandlungfrom
Berner, 1982, Geol. Jahrbuch D67 (also in Schoell, 1984).
5. Compound classes, as determined by column or thinlayer chromatographic separation. The relative proportions of each compound class (saturated hydrocarbons,
aromatic hydrocarbons, resins, and asphaltenes) can give
indications about both source and maturity.
Low contents of hydrocarbons in an extract indicate
immaturity. Large proportions of hydrocarbons in an extract indicate either maturity, contamination by drillingfluid additives, or presence of migrated oil.
Most oils will contain more than 75% hydrocarbons
(fig 5.20). Certain oils formed at low levels of maturity
from sulfur-rich kerogens can have large amounts ofNSO
J~_
5 I
o
0'
o
o
chromatogram of light hydrocarbons removed from a powdered rock sample by hydrogen stripping.
Reprinted with permission from Schaefer and Leythaeuser,
1980. Copyright 1980, Pergamon Press, Ltd.
10. CORRELATIONS
,.
I
.~--.
SAT
"----.-.
AROM
- HET
-
Jurassic oils
North Sea
,,~
.,
ASPH
KERO
SPECIFIC PARAMETERS
159
-30
-28
-29
'0..
-27
-26
I) 13CI'DIJ [0/00]
Jurassic
x = -
2.53(B 13Csat)
+ 2.22(B 13Carom)
- 11.65,
(10.2)
I)
13CK
= 24.8 [0/00]
Schoell, 1981.
160
TABLE 10.1
Sediment Type
PristanelPhytane
1-3
Pr
>3
n-Cn
<1
oxidizing.
unr 'rlcted
Phi
In-C1B
10. CORRELATIONS
161
Gammacerane
~..,. f ' IU
l ..... . O.5G
10
re/ M
Oleanan
FIGURE 10.7 Chemical structures of gammace,rane and
oleanane, triterpanes derived from lacustrine and terrestrial
sources, respectively. Reprinted by permission of Academic
Press from MacKenzie, 1984.
162
RJrDfAS IHOAL
WI t TAlTEJIIIAHfa
1''''
""'0
HCIO
, ..0
10. CORRELATIONS
163
C~I
Regular hopane
C2 ' 1
C 2'1
Group I
mz 191
GI'OUp :J
/llIZ 191
(;I'OUp 2
mz 191
Group 4
nllz 191
Demelhylaled hopanes
C2iI
. ...
Four oil types in the San Jorge Basin, Argentina, as demonstrated by m/z 191 mass chromatograms. The
triterpanes of Group 1 oils have not been demethylated. The
oils of Groups 2 and 3 contain both regular and demethylated species, while those of Group 4 are fully biodegraded,
showing only the demethylated species. Reprinted with permission from Philp, 1983. Copyright 1983, Pergamon Press,
FIGURE 10.9
Ltd.
164
10':>
Inltlolly
Produced
,"_ __
Olde'
-. ,- , ~ 12C Depleted
M
10
Go~
Qaw
1"1
Go~
ZO E Of
U
+
N
U
Drt
MICROBIA.
ORIG I
10 3
I
I
1
Hlgne'
Hydroco r bons
Oepteled
10 2
Du"ng
Mlg'o ,on
-I.
I
/
*' "
0'>-,,::- ------
ZO E
10 1
OF
Crossplot of 8D and 013C of methane for natural gases, by which gases of various origins can be distinguished. Reprinted by permission of ErdOl und Kohle, Erdgas,
Petrochemie from &lwell, 1981.
FIGURE 10.12
THERMO,
CATALVTIC
OR IGI
-1.0
-50
-60
-70
-80
6 13eCHt. [%01
FIGURE 10.11 Diagramfor determining the origin of natural
gas using a crossplot of dryness (C 1 1(Cz + C3 ) versus fPC for
methane). Reprinted by permission of Academic Press from
&lwell, 1984; adapted from Bernard et al., 1976.
10. CORRELATIONS
165
R
WEST SEA HORSE.,
48 AP
...
....."'
%
.. 1
._-----l
lAKES ENTRANCE
a:
a:
..
mIl 217
'6 AP.
...o
tON
0-
ABUNDANCE
40
20
RETENT.ON Tllo!E(m.nul 1
Gas chromatograms of saturated hydrocarbonsfrom Lakes Entrance and West Sea Horse #1 oils,
Gippsland Basin, Australia. Reprinted by permission of the
Australian Petroleum Explnration Association from Alexander et al., 1983.
FIGURE 10.13
CASE STUDIES
BIODEGRADATION
1983.
However, the m1z 191 mass chromatogram shows no indication of demethylated hopanes (these could, in fact, be
detected better by m1z 177, but it is not available).
Biodegradation of the Lakes Entrance oil is therefore
probably at stage 7 (table 5.4).
In contrast, the West Sea Horse *1 oil shows signs of
only slight biodegradation (level 2 of table 5.4), as
evidenced by the slight depletion of n-alkanes below C20
That this depletion cannot be the result of evaporative loss
during sample work-up is shown by the presence of other
light components (fig. 10.13).
On the basis of the information provided, it is not possible to state with certain1y that the Lakes Entrance and
West Sea Horse *1 oils are related. Differences in the gas
chromatograms and mass chromatograms of the steranes
are explainable by biodegradation. The triterpane mass
chromatograms are rather similar and are therefore consistent with a common origin. Furthermore, one unusual
feature of the m1z 191 mass chromatograms of both oils
166
II
4-
LAKES ENTRANCE
R2
'" 1
" 10
mlz 191
ION
.... 11o. ....
ABUNDANCE
..,..:e
....
..
II
~.1
Ill. "
... n '" ,.
11
"
'V/I'\" .1J"
12
1
1\
The origin of the oils in the Michigan Basin has been the
focus of an interesting controversy in recent years. Oils
have been produced from Ordovician (Trenton), Silurian
(Niagara), and Devonian (Dundee and Lucas) reservoirs.
Vogler et al. (1981) decided on the basis ofn-alkane and
isoprenoid distributions (fig. 10.16) and carbon-isotope
profiles for individual n-alkanes (fig. 10.17) that the Ordovician and Devonian oils had a common source and
that the intervening Silurian oils had a different source,
probably in lagoonal facies adjacent to the reefs from
which they are produced.
Illich and Grizzle (1983) and Pruitt (1983) challenged
this interpretation, however. Using crossplots of gas
chromatographic data (figs. 10.18, 10.19, and 10.20),
they concluded that t\rree types of oils exist, with some
mixtures. Their hypothesis was greeted with more en-
FIGURE 10.15 m/z, 191 mass chromatograms of Lakes Entrance and West Sea Horse 1 oils, Gippsland Basin, Aus-
10. CORRELATIONS
167
I~r--------------------------r------------------------~r-------------------------~
NORTHVILLE
GRANT
26
OrdovIc Ian
Slkrlan
CPl. \.29
CPl.' O!>
BENTLEY
10
IZ
W
<.J
a:
0..
I~
20
2~
30
30
20
I~
20
-23
o Silurian (Nlaoara)
25
o Devonian
([)undee)
CD
~-27
>
/. -29
..0
-3'
-33
'2 '4 16 18 20 22 24 26 28 30 32
n-ALKANE
CARSON
NUMBER
4.O"'-----""T-----------,
.. DEVONIAN
AI.L SILURIAN
.. ORDOVICIAN
~ 30-
..
I/)
~ 2.0 -
.2I-
:z
I&J
'
... o.
1.0-
I r4
.
.. ...." ....
. .... .
"
"~""""'DUfilllOIfJ
,~
0.0 .0.0
~O
2' 0
4.0
--PERCENT ;p 20 (PHYTANE}----'
,O.O_-------""'T---------------------~
OCVO/OlIAN
~HRN SILURIAN
SOIITHRN SILURIAN
.. ORDOVICIAN
8 .0-}-_ _ _ _ _ _
/"
.
.
.....
.,
,~
,""'
SAGINAW(8(REAI..
......
..
"t/'
A ........ iltCli #tUN lOtJHO(c)
2 .0-
~O-t~~-r_~I~~~~~,~~-,~-~I~T-T-~r-,r-r-~~I~~~~~
0 .0
10.0
20.0
30.0
400
!}()D
600
loll"
FIGURE 10..20 Crossplnt of isoprenoid content versus n-alkane content for Michigan Basin oils. Reprinted with permission
from Illich and Grizzle, 1983. Copyright 1983, Pergamon Press, Ltd.
10. CORRELATIONS
SOURCE-ROCKOIL CORRELATIONS
169
is.
t.
is.
C. CURRANT AELC
16856 70lI0 111
is.
~,
30
I
"'lW.LUJJ~
30
11.1
.llllil.ll.J.l
D. CHAINMAN SHALE
ESU NO 2 (9497 ft )
is.li
is.
s:.
,j ~ L
c.-'
30
I
FIGURE 10.21 Gas chromatograms of saturated hydrocarbons from three oils (top) and three source-rock extracts (bottom) from the
Basin and Range province. Each oil correlates with the extract immediately below it. From Poole and Claypool (1984).
ROCK
CRUDE
OILS
EXTRACTS
TERPANES
C29
STERANES
::,.------=--~ ~-~
01.0
0.5
Uool
0.5
1.0
RGURE 10.22 Relative amounts of selected terpanes and steranes for oils (left) and rock extracts (right) from the Basin and
Range province. Peaks 1 and 2 are tricyclic terpanes; peaks 3 and 4 are the C-29 and C-30 hopanes, respectively; peaks 5 and
6, 8 and 9, and 10 and 11 are the pairs of 22S and 22R epimers of C-31, C-32, and C-35 extended hopanes, respectively; peak
7 is gammacerane; arut peaks A-D are the aa20S, ~~20R, ~~20S, and ao:2OR steranes, respectively, From Poole and Claypool
(1984).
172
1,9()()1II
Initially
Old . ,
25
JO
15
20
25
JO
15
15
20
- - - - - - - - CARBON NUIl8ER - - - - - - --
GAS CORRElATIONS
I
I
,,,
ZONE
,,
MICROBI AL
--- ,
10 2 .-
Hlghe'
Hydrocar bons
Ceplet ed
DUling
Migration
OF
b-
MIXING
,
I
,
,,
, -
-0---'::- --- ~
ZO E
,,
-:
I
I
ZO E
10 1
,,I
,
,
,,
I
ORIGI
10 3
-:
O~
OIL MATURITY
(,as
Gas
U
+N
U
<}::::::> P'nduced
10' <-
~~
.,
,,
,I
*~'
-:
THER MO'
CATALY IC
ORIGI
-1.0
1 I
-50
-60
M lxh.U ~ *
-70
-80
5 BeCHI. 1%01
FIGURE 10.24 Crossplot of gas dryness versus 5 13C value for
a gas from the Devonian black shales of the eastern United
States. The gas falls clearly within the range for thermally
generated gases, and cannot be biogenic.
10. CORRELATIONS
CONCLUSIONS
I recommend adopting the following philosophy in designing and executing a correlation study:
1. Both bulk and specific parameters should be employed.
2. The least-expensive analyses should be carried out
first; expensive ones may not be needed if the inexpensive ones show poor correlation.
3. Several different types of analyses should be used to
establish as strong a case as possible.
4. Biomarker techniques should be employed when possible.
5. An attempt should be made to explain discrepancies
on the basis of reservoir transformations, mixing,
biodegradation, migration, or contamination before
deciding that the correlation is negative.
6. A positive correlation is always circumstantial. Our
confidence in its correctness will depend upon the
number and type of parameters used. Negative correlations are usually made with more confidence than
positive ones.
7. Some samples have more distinguishing characteristics than others. Samples having unique features will
be easy to correlate, whereas samples having no distinguishing features will be hard to correlate, or they may
be "silent partners" in mixtures.
8. The success of correlations varies widely, as do the
parameters that happen to be useful in individual
cases. One must usually proceed by trial and error.
When correlations do work well, they can be very
valuable.
9. Correlations are only as good as the geological data we
put into them. A thorough understanding of local and
regional geology, especially the occurrences of possible
source rocks and postulated migration pathways, will
contribute greatly to the success of any correlation and
can often help avoid embarrassing mistakes.
173
SUGGESTED READINGS
Alexander, R., R. I. Kagi, G. M. Woodhouse, and J. K. Volkman, 1983, The geochemistry of some biodegraded Australian oils: Journal of the Australian Petroleum Exploration
Association (APEA), v. 23, pp. 53-63.
Barwise, A.J. G. and P.J. D. Park, 1983, Petroporphyrin
fingerprinting as a geochemical marker, in M. Bjor0y, ed.,
Advances in Organic Geochemistry 1981: Chichester, Wiley,
pp. 668-674.
Demaison, G. and R.J. Murris, 1984, eds., Petroleum
Geochemistry and Basin Evaluation: American Association
of Petroleum Geologists Memoir 35, Tulsa, American Association of Petroleum Geologists, 426 pp.
Fuex, A. N., 1977, The use of stable carbon isotopes in hydrocarbon exploration:Journal of Geochemical Exploration, v. 7,
pp. 155-188.
Mackenzie, A. S., 1984, Applications of biological markers in
petroleum geochemistry, inJ. Brooks and D. Welte, eds., Advances in Petroleum Geochemistry, Volume 1: London, Academic Press, pp. 115-214.
Mattavelli, L., T. Ricchiuto, D. Grignani, and M. Schoell, 1983,
Geochemistry and habitat of natural gases in Po Basin, northern Italy: Bulletin of the American Association of Petroleum
Geologists, v. 67, pp. 2239-2254.
Poole, F. G. and G. E. Claypool, 1984, Petroleum source-rock
potential and crude oil correlation in the Great Basin, in J.
Woodward, F. F. Meissner, andJ. 1. Clayton, eds., Hydrocarbon Source Rocks in the Greater ROCky Mountain Region:
Denver, Rocky Mountain Association of Geologists, pp. 179229.
Rice, D. D., 1983b, Application of organic geochemistry to hydrocarbon occurrence, in D. D. Rice and D. 1. Gautier, eds.,
Patterns of Sedimentation, Diagenesis, and Hydrocarbon Accumulation in Cretaceous Rocks of the Rocky Mountains:
SEPM Short Course Notes, No. 11, Tulsa, pp. 3.1-3.40.
Schoell, M., 1983, Genetic characterization of natural gases:
Bulletin of the American Association of Petroleum Geologists,
v. 67,pp. 2225-2238.
---,1984, Stable isotopes in petroleum research, inJ. Brooks
and D. Welte, eds., Advances in Petroleum Geochemistry,
Volume 1: London, Academic Press, pp. 215-245.
Snowdon, L. R., 1980, Resinite-a potential petroleum source in
the Upper Cretaceous/Tertiary of the Beaufort Mackenzie Basin, in A. D. Miall, ed., Facts and Principles of World Petroleum Occurrence: Canadian Society of Petroleum Geologists
Memoir 6, Calgary, Candian Society of Petroleum Geologists,
pp. 421-446.
174
1)
OAR(HI"r,
PRACTICE PROBLEMS
1. There are two types of crude oils (paraffinic and naphthenic)
in the Molasse Basin of Germany. Gas chromatograms are
shown in figure 10.25 and mlz 217 mass chromatograms in
figure 10.26. Is there a genetic relationship between oils of the
two types?
2. Do the Molasse Basin oils (see practice problem #1) correlate
with an extract of the Fischschiefer (fig. 10.27)?
3. Three light oils are obtained from slightly different depths
and reservoirs in three wells located about a mile apart in the
Gondwana Field. Determine whether all three oils are from a
common source. Data for the oils are compiled in table 10.2,
and gas chromatograms are shown in figure 10.28.
4. The South Hootchiekootchie Basin is a prolific oil-producing
region with many offShore wells. One day a large oil slick is
noted exactly equidistant from twelve producing wells. None of
the well operators will confess to having a leak in his system, but
the Department of the Interior demands satisfaction. Your job is
to identifY the culprit by organic-geochemical methods.
You first request a fresh sample of oil from each of the twelve
wells and from the least-weathered part of the oil slick. You then
ask that the following analyses be carried out on each of the
samples: gas chromatography of saturated hydrocarbons, carbon-isotope ratios on the topped crudes, porphyrin contents,
sulfur contents, and API gravities. Results of these analyses are
shown in table 10.3. Are these data sufficient to correlate the
spilled oil with a single well definitively? If not, what would you
do next? In retrospect, how would you critique your approach?
18
VELOEN
19
TE ISIN(i
n.(1C
l
I
v~
~'
to. CORRELATIONS
--'
I~'
.. .
r-o'
Iii"?
t o,
....
ASSLING
16
AMP~ ING
"----lJ~ ____
. . . . . . . . ~~ .-.~~
i . ... ~...,"',...............,f".t'
1~
rmf
f""I'l1
175
.
J ____
ASSERBURCi
__~,~J
lJ~,
ENOORF
16
AMPF ING
FIGURE 10.27 mlz 217 mass chromatograms for two Fischschiefer extracts (top) and two oils (bottom) from the German Molasse Basin. Reprinted with permission from Hufnagel et aI., 1980. Copyright 1980, Pergamon Press, Ltd.
177
to. CORRELATIONS
Depth (ft)
Reservoir age
API gravity (deg)
% Sulfur
CPI
& 13C whole oil (0/00)
& 13C saturates (0/00)
% saturated HC
% aromatic HC
Pristane/phytane
Blue
Well
Green
Well
8100
10,200
8700
L. Cret.
E. Cret.
Eocene
46.1
0.12
1.01
-26.1
-27.9
60.4
28.5
1.5
44.3
0.08
1.02
-27.0
-29.5
72.5
16.3
3.6
32.5
0.21
Aquamarine
Well
-26.6
-28.3
48.3
21.6
2.0
,. .,
..
-A
1.J
,.
..
II
t7
27
....
..
,~
23
"
'9
3'
3.
J~
Po.
17
'9
Il
"
. 16
....
...
18
' '16
chromatograms of saturated hydrocarbons from oils from the Gondwana Field: (A) Blue well, (B)
Green well, and (C) Aquamarine well.
FIGURE 10.28 Gas
178
TABLE 10.3
Geochemical data on twelve produced oils and a spill oil from the South Hootchiekootchie Basin
Production
Depth (ft)
Well
8100-8150
6763-6849
8460-8610
7998-8016
9001-9202
6887-6990
7421-7503
9023-9112
6810-7020
9100-9140
8321-8520
8169-8230
1
2
3
4
5
6
7
8
9
10
11
12
Spill oil
Producing Formation
API
Gravity
(oAP!)
Sulfur
C
A
30.5
27.5
34.5
19.7
31.8
29.7
25.7
24.3
28.1
36.1
24.3
21.2
12.7
0.8
0.3
0.1
0.7
1.3
1.2
1.7
2.2
0.1
0.2
1.7
0.6
3.7
C
C
C
C
C
B
A
D
D
C
1\ '3C of
topped Oil
(0/00 vs. PDB)
-26.7
-29.7
-27.9
-26.7
-28.0
-28.1
-26.4
-26.2
-30.1
-28.4
-27.2
-26.9
-25.7
Maximum
Porphyrins
in n-Alkane
Ni
Pr/n-C'7
Phln-C'8
PrlPh
CPI
Distribution
1.02
0.00
0.16
1.21
0.92
1.02
0.99
0.15
0.02
0.15
0.88
1.15
0.72
1.55
0.03
0.12
1.02
1.45
0.34
0.29
0.05
0.00
0.13
0.21
0.96
0.27
0.81
0.03
0.23
0.21
1.02
0.92
0.19
0.31
0.11
0.49
0.97
0.16
3.65
0.68
0.43
0.92
0.67
0.88
0.91
0.66
1.72
0.51
0.96
0.79
0.81
16.1
1.2
0.1
0.2
0.3
1.2
1.0
0.3
0.2
0.2
0.5
1.2
0.2
0.2
1.01
1.13
1.02
1.04
0.99
1.07
1.04
0.87
1.17
1.06
1.03
0.98
17
18
17
16
17
17
17
18
17
18
16
17
1
I
I
1
I
I
[BJ
1
1
I
1
1
:..
I.
I
05
0.2
DO: .. ~ '"
1
D~.
':1,00
D
0.1
0.05
0.02
0.01
~.D
-80
-0 .
""\:i ~.D
...
-70
~I.a
1
1
I.
1
1
1
:.
.,11./ :
1I
1
1
1
1
1
1
MolOSSQ
.1
I
I
Vigallo
l'"
I
1
1
1
-60
II
I
I
I
1
1
1
1
1
1
1
1
Medesano""
1
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1
1
.:
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t
-50
PlEISJOCENE
U.".PUOCENE
l PLIOCENE
... MESSINIAN
-40
-30
10. CORRELATIONS
179
After looking at all these data, it is apparent that only two oils,
numbers 7 and 8, are possible sources for the spill. Of these, oil
8 gives a closer fit, but there is not a clear choice between the
two.
The next logical step is to look at sterane and triterpane distributions by gc/ms. Given the low level of biodegradation experienced by the spilled oil, none of these parameters should have
been affected. If oils 7 and 8 are different, then we may be able
to determine which was responsible for the spill. On the other
hand, if they are identical, we would not be able to determine
which of the two was spilled.
This analytical program could have been improved slightly.
Measuring API gravity was a waste of money. In other respects,
however, the battery of analyses ordered was well designed. By
saving gc/ms for last, we could limit our applications of this
most expensive technique to only three samples instead of
thirteen.
180
Well
Production
Depth (ft)
1
2
3
4
5
6
7
8
9
10
11
12
8100-8150
6763-6849
8460-8610
7998-8016
9001-9202
6887-6990
7421-7503
9023-9112
6810-7020
9100-9140
8321-8520
8169-8230
producing Formation
API
Gravity
(oAPI)
30.5
27.5
34.5
19.7
31.8
29.7
25.7
24.3
28.1
36.1
24.3
21.2
12.7
A
C
C
C
C
C
B
A
D
D
Spill oil
NOTE:
Sulfur
l) 13C of
Topped Oil
(0/00 vs. PDB)
Ni
Prln-C '7
Phln-C '8
PrlPh
CPI
Maximum
in n-Alkane
Distribu tion
0.8
0.3
0.1
0.7
1.3
1.2
1.7
2.2
0.1
0.2
1.7
0.6
3.7
-26.7
-29.7
-27.9
-26.7
-28.0
-28.1
-26.4
-26.2
-30.1
-28.4
-27.2
-26.9
-25.7
1.02
0.00
0.16
1.21
0.92
1.02
0.99
0.15
0.02
0.15
0.88
1.15
0.72
1.55
0.03
0.12
1.02
1.45
0.34
0.29
0.05
0.00
0.13
0.21
0.96
0.27
0.81
0.03
0.23
0.21
1.02
0.92
0.19
0.31
0.11
0.49
0.97
0.16
3.65
0.68
0.43
0.92
0.67
0.88
0.91
0.66
1.72
0.51
0.96
0.79
0.81
16.1
1.2
0.1
0.2
0.3
1.2
1.0
0.3
0.2
0.2
1.01
1.13
1.02
1.04
0.99
1.07
1.04
0.87
1.17
1.06
1.03
0.98
17
18
17
16
17
17
17
18
17
18
16
17
Porphyrins
0.5
1.2
0.2
0.2
Boldface type indicates a definite negative correlation. Italic type indicates a probable negative correlation.
-50
80
f:
a.a..
0"
~
1.0
0;
~o
-55
~i;
.,.
40
60.
-60
20
I Spilamberto I
C2+ [pphJ
Chapter 11
Surface Prospecting
Because no reservoir seal is perfect, all hydrocarbon accumulations leak material to the surface (fig. 11.1). Although large seepages may be visible to the naked eye,
small, slow microseepages can only be detected with sensitive instruments. Many obvious seeps were used in the
early days of the petroleum industry as important aids to
exploration. More recently, however, interest has focused
on locating and utilizing minor seepages of hydrocarbons.
In an effort to improve exploration efficiency, a wide
variety of techniques for identifYing hydrocarbon microseepages has been developed over the years. Some of these
methods measure hydrocarbon fluxes directly; others
(mainly geophysical) detect the passage of hydrocarbons
indirectly, using inorganic products of chemical reactions
induced by the moving hydrocarbons. Most of these
methods are used at or very near the earth's surface
and therefore are referred to collectively as suifaceprospecting techniques.
One complicating factor in the interpretation of surface-prospecting data is that seeps are not always located
directly above accumulations, as figure 11.1 would suggest. If the seeping hydrocarbons encounter a fault or
permeable conduit, their vertical movement may develop
a significant lateral component as well. Furthermore, in
some cases a "halo" effect is noted (fig. 11.2), in which
the surface anomaly is seen to surround the actual accumulation. Halos are not completely understood; they
have been attributed both to plugging of diffusional path181
182
FIGURE 11.1 Cartoon depicting vertical movement of hydrocarbons from an imperfectly sealed reservoir. Hydrocarbons
or traces left by the hydrocarbons can be detected at or near
the surface.
36
t
30
6
R26e
FIGURE 11.2
i'LAw....
...V
3 -~
a:
u. 0
~
~
>
:2
~WE
183
POPULATION 3
V,OPULATION 2
2 r-~-+--~~-----+--+----------+-----~7.'------r----~--------~
...
/~
TRANSITION
'~
184
many light-hydrocarbon measurements emphasize ethane and heavier alkanes. Concentrations of light hydrocarbons are usually determined by collecting a syringe of
soil gas or by canning a sample of rock or soil and later
removing the headspace gas (chap. 7). Measurements are
carried out by gas chromatography.
The results of the analyses are then plotted on a map
showing sample locations, and contours are drawn.
Those areas having high concentrations of hydrocarbons
are considered to be of interest.
One of the main problems in interpreting all kinds of
surface-prospecting data is deciding which concentrations represent anomalies, and which are background. It
is imperative that this decision be made objectively and
that background be determined independently in each
area. It is not always correct to assume that the highest
values in an area represent anomalies. One way in which
anomalies can be identified objectively is by plotting the
raw data on probability paper. A Gaussian distribution of
the raw values, which might be expected if all samples
were from a single population, gives a straight line when
plotted on linear probability paper. If two or more data
populations exist, however, a separate line will appear for
each population (fig. 11.3). Inflection points occur between the populations and mark the approximate limiting
values for each population.
Unlike most other techniques, light-hydrocarbon analyses can be applied offShore as well as onshore. Lighthydrocarbon prospecting is less expensive than most
other regional high-grading techniques.
Onshore. Light-hydrocarbon surveys are carried out most
complicated and expensive than onshore and has therefore attracted a greater variety of innovative technologies.
The added expense of offshore surveys is often compensated by the larger exploration prizes being sought, however.
One technique commonly used in offshore surveys is
analogous to onshore sampling. Sediment samples are
obtained by piston coring or grab-sampling and are then
canned or frozen until gas analyses can be carried out.
Because biogenic methane is a much greater problem
in subaqueous sediments than in most soils, analytical
procedures must be able to separate small amounts
of heavier hydrocarbons from much larger quantities of
methane.
Evidence for thermogenic hydrocarbons in the North
Sea was obtained from gas-chromatographic data and
confirmed by carbon-isotope analyses (Faber and Stahl,
1984). The added expense of carbon-isotope measurements was probably not prohibitive in their study, given
the investment in obtaining the samples.
Another technique for measuring light-hydrocarbon
concentrations in offshore areas is to sample the bottom
water, where the concentrations of hydrocarbons reflect
the rates at which seepage is occurring directly below. In
the system developed by InterOcean Systems ("Sniffer"), a
device towed beneath a seismic vessel pumps water continuously to the ship, where hydrocarbon gases dissolved
in the water are analyzed by gas chromatography. This
system is rather expensive, because massive data reduction is done by computer. Three-dimensional contour
maps of hydrocarbon concentrations are provided.
The system offered by Hydrochem Surveys International is similar. The main difference between their tech-
185
High-wave-number magnetic anomalies detected in lowaltitude aeromagnetic surveys are thought to be indicative
of the presence of shallow accumulations of magnetite
formed as a result of reactions with seeping hydrocarbons. An oxidation-reduction reaction between hydrocarbons and ferric ( + 3) iron in the subsurface reduces the
iron to the ferrous (+2) state. The mobile Fe+ 2 species
move in water solution until they are oxidized back to
immobile Fe+ 3 near the surface. The resulting concentration of magnetite at shallow depths is responsible for the
observed magnetic anomaly.
Magnetic anomalies have been observed above the Cement Field in Oklahoma (Donovan et aI., 1979), the Bell
Creek Field in Montana (Dalziel and Donovan, 1984),
and in Alaska (Donovan et aI., 1984). Whether such
anomalies occur over most fields remains to be proved.
Although application of aeromagnetics to petroleum exploration is not yet fully developed, the relatively low expense of such surveys makes them attractive (Foote,
1984).
~C
186
The carbonate produced from oxidation of migrating hydrocarbons can decrease porosity and increase density of
the rocks in which it precipitates. If the host rocks are
poorly consolidated, the density contrast between cemented and uncemented surface material can be detected
and mapped using micro gravity surveys (McCulloh,
1969b).
Another application of carbonate minerals formed by
oxidation of hydrocarbons utilizes carbon-isotope ratios
of carbonate cements. Because carbonates formed by
oxidation of organic carbon have carbon-isotope ratios
similar to those of the hydrocarbons (fig. 3.16), hydrocarbon-derived cement is easily distinguished from inorganically derived carbonate (Donovan, 1974).
Carbon-isotope measurements on carbonate cements
would probably be used as a confirmatory tool rather
than for reconnaissance. The number of analyses and
expenses could thus be minimized.
INDUCED POLARIZATION UP)
an inexpensive reconnaissance technique where conditions are appropriate (Sternberg and Oehler, 1984).
SURFACE GAMMA-RAY MEASUREMENfS
Gallagher (1984) has promoted the use of iodine anomalies in petroleum exploration. Soil samples are taken from
a few inches below the surface and analyzed for total
iodine. Hydrocarbon accumulations are supposed to be
surrounded by a halo of high iodine concentrations.
Vegetation anomalies have been frequently used by
mineral explorationists as indicators of trace-element
deficiencies or excesses. Such anomalies can either be
visible to the naked eye (Richers et aI., 1982) or entail
abnormally high concentrations of certain elements in the
vegetation (Dalziel and Donovan, 1980). Although there
have been few applications to petroleum exploration,
with Landsat's ability to discern vegetation anomalies
there may in the future be more interest in using plant
abnormalities as indicators of hydrocarbon microseeps.
A variety of other surface-prospecting techniques has
been used in exploration. Some of these are discussed in a
review by Philp and Crisp (1982).
SUMMARY
Although direct-detection methods for hydrocarbons enable us to monitor present-day microseeps, there remain
many unresolved problems in applying the various techniques to exploration. Growing interest in using the
heavier hydrocarbons as more reliable indicators of seeps
indicates that, at least onshore, this approach may in the
187
Davidson, M.J., 1982, Toward a general theol}' of vertical migration: Oil and GasJournal,June 21, pp. 288-300.
Davidson, M.J., B. M. Gottlieb, and E. Price, eds., Unconventional Methods in Exploration for Petroleum and Natural
Gas III: Dallas, SMU Press.
Klusman, R. W. and K.J. Voorhees, 1983, A new development
in petroleum exploration technology: Mines Magazine,
March, pp. 6-10.
Philp, R. P. and P. T. Crisp, 1982, Surface geochemical methods
used for oil and gas prospecting-a review: Journal of
Geochemical Exploration, v. 17, pp. 1-34.
Chapter 12
Integrated Applications
to Exploration
190
1.0
">
III
C e
:z: 0
...
0
...
CL 1/1
>-
III
III
III
...
l-
III
IL
.1
::I
e
e
c
.1
.4
>C
.2
100
200
'00
191
Steps 2 through 5 require an understanding of the tectonic factors that controlled subsidence rates, lithology,
type of organisms, organic and inorganic diagenesis,
paleoclimate, structural development, and heat flow. The
more complete our understanding of a basin, or the closer
comparison we can draw between it and another, wellstudied basin, the more confidence we will have in our
model. Bois et al. (1982), Cohen (1982), and Harding
(1984) have all suggested ways in which general principles of basin analysis can be applied for exploration
purposes.
Building such complex models requires integration of
data from many different areas of geology, including plate
tectonics, paleontology, sedimentology, and structural
geology, as well as geochemistry. Such a project should
lend itself well to team efforts.
EXAMPLES
,~, :h_ 1
~
...............
OlC20)o
SC A LE IN
L S
FIGURE 12.2 Major structural ftatures of the East Texas Basin. Reprinted by permission of the SEPM from Siemers,
1981.
192
:".t'.
'-..
~'~
l':
.:
.,
:/
.,
\...
\
, r
'r
Arkansas
Louisiana
.. "
.. .~\
-.
"
'
~.
Most of the mature Eagle Ford shale occurs near or beyond the southern margin of the basin, where regional
dip has allowed deeper burial of the source rock. Longdistance migration is thus required in order for Eagle
Ford oil to have charged Woodbine sands.
Woodbine sands were deposited in a variety of environments, including channel-overbank facies in the far
north, meander-belt facies in the northern and central
parts of the basin, and channel-mouth-bar and coastalbarrier facies in the south. In the extreme south the
Woodbine shales out. Along the Angelina-Caldwell
Flexure the facies is thought to be shaley. Except where
shales predominate, there is probably excellent continuity
within the Woodbine sands, thus permitting long-
St."ilk in mill'!'.
10
:!O
:10
40
FIGURE 12.3 Woodbine oil and gas fields (dark areas) in the
East Texas Basin,
193
Arkansa
Loui iana
- ...
~
mer beds
o Probable
GP
ibl
194
\\
C]
o
o
-+-
s...d.. In nil,",
IO
ZONJ-W
Highcst
Good
Fair
FIGURE 12.6 Comparison of predicted areas for accumula-
Arkansa
Loui iana
\\
"w.lk
II
Oil
CI
Gas
SCSI
0.. .
Good
Fair
m
1:3
FIGURE 12.7
It)
HI 1I111t ....
.!u
tu
-'41
195
196
\.
IEiRASU
---....
1984.
197
."
IC
."
...
west (figs. 12.8-12.11) did not appreciably alter the distribution of trapping structures.
Accumulation of oil in the J Sandstone will occur
where oil transported from the kitchen encounters anticlinal structures (stratigraphic-trapping possibilities are
ignored in Tainter's study). Patterns of hydrocarbon migration through the J Sandstone can therefore be determined by juxtaposing figures 12.8-12.11 with figures
12.12 and 12.13. The migration pattern for the end of the
Tertiary is shown as -an example in figure 12.14.
FIGURE 12.11
198
'-
,0
':" \,5
:, ,,,
....
,...
~t
%J
8
~
\"
",
:;
CIII.,.MtI
. 1500
I100
I
....
-
...,
....
"'"
~I\Ch'DM Tf'uCkMu
>
C)
100'
C I SO'
One convenient way to approach the problem of calculating hydrocarbon volumes in a basin is to break. the
process of hydrocarbon accumulation into phases:
generation, expulsion, migration and entrapment, and
preservation. We shall address each of these phases in
turn. An example of a volumetric calculation carried out
according to this methodology can be found in Moshier
and Waples (1985).
The most useful ba~ic equation for hydrocarbon generation utilizes three common pieces of geochemical data
P,"oil,uc;lur.' Htth'
C I
~OO'
FIGURE 12.13
(12.1)
199
IEIRASU
Q)
,
Q
""now" 'rochtCho..
Ot!
Gil
FIGURE 12.14 Hydrocarbon-migration pathways in] Sandstone at end of Tertiary. See figure 12.10 for fur'ther details.
Reprinted by permission of the Rocky Mountain Association
of Geologists from Tainter, 1984.
FIGURE 12.15 Comparison of high-graded areas for future]Sarulstone exploration with actual productive fields in]
Sarulstone. Reprinted by permission of the Rocky Mountain
Association of Geologists from Tainter, 1984.
200
o 2~
085
062..---
"'-------'--'
010
Og~
0'0
O.$()
090
0 .8
1.0
vA l e
,2
2.111
THREE
TYPES
MAINLY- HUMIC
TO MIXED
OF
SOURCE ROCK :
MAINlY-KEROG .
TO KEROG . 8ACT.
KEROGENOUS
ALGAL
.....
.,
gg;;
06
1.0
0.62 +'-.l...._--'-_--'
DB
,.0
VR/E
'.2
(0.7)(0.24)(120)(0.35)
7.056 million barrels oil per
cubic mile of source rock.
(12.2)
Volume of gas
(0.7)(6)(0.96)(120)(0.07)
(12.3)
= 33.87
(12.4)
= 598.5
= 15.96
201
(12.6)
202
(12.7)
x (migration efficiency).
Finally, we must worry about preservation of oil in the
reservoir. Destruction can occur via either cracking or
biodegradation; the greatly different thermal regimes required in the two cases generally prevent both phenomena from occurring in a single sample. These factors
could be taken into account, using equation (12.8):
Oil preserved = (oiltrapped)(preseIVation factor).
(12.8)
The preservation factor for oil varies from 0 (total destruction by either biodegradation or cracking) to 1 (no
destruction). Total destruction would probably be best
defined as the absence of any producible oil. A preservation factor for gas could also be introduced if oxidation of
methane is anticipated.
Volumetric calculations are, in principle, simple to
carry out, but in practice they offer some complexities.
Among the potential difficulties are the following:
1. How can we predict accurately the oil-gas mix from a
particular source rock?
2. How certain are we of (a) the threshold for expulsion
and (b) expulsion efficiencies?
3. What are the factors that influence migration and trapping efficiencies, and how can we predict them?
4. How can we handle systems in which our geochemical
and geological parameters change significantly over
the area of interest?
The answers to the first two questions are poorly documented and could profit by additional research. However,
In order to achieve maximum effectiveness, the application of geochemistry to exploration should involve full
integration of geological and geochemical data. An excellent way to accomplish this objective is to develop integrated models that describe the complete hydrocarbon
system in the area of interest.
Some such models are primarily qualitative and descriptive, and can be applied using standard geological
techniques of mapping and construction of cross sections.
Other models are quantitative and mathematical. Probabilistic models are preferable to deterministic models for
routine exploration application.
Use of both qualitative and quantitative models is not
limited to maturely explored areas. Although studies in
areas from which much drilling data are available will
generally be more detailed and accurate than in areas
where data are sparse, application of models even in frontier areas will often permit important comparisons and
high-grading at an early stage of exploration. Considering
the very low cost of using such models, they can serve as a
very effective reconnaissance technique.
SUGGESTED READINGS
Bishop, R. S., H. M. Gehman,)r., and A. Young, 1983, Concepts
for estimating hydrocarbon accumulation and dispersion:
Bulletin of the American Association of Petroleum Geologists,
v. 67, pp. 337-348.
Demaison, G., 1984, The generative basin concept, in G. Demaison and R.). Murris,' eds., Petroleum Geochemistry and
Basin Evaluation: American Association of Petroleum
203
Geologists Memoir 35, Tulsa, American Association of Petroleum Geologists, pp. 1-14.
Demaison, G. and R.). Murris, 1984, eds., Petroleum
Geochemistry and Basin Evaluation: American Association
of Petroleum Geologists Memoir 35, Tulsa, American Association of Petroleum Geologists, 426 pp.
Moshier, S. o. and D. W. Waples, 1985, Quantitative evaluation
of Lower Cretaceous Mannville Group as source rock for Alberta's oil sands: Bulletin of the American Association of
Petroleum Geologists, v. 69, pp. 161-172.
Sluijk, D. and M. H. Nederlof, 1984, Worldwide geological experience as a systematic basis for prospect appraisal, in G.
Demaison and R.). Murris, eds., Petroleum Geochemistry
and Basin Evaluation: American Association of Petroleum
Geologists Memoir 35, Tulsa, American Association of Petroleum Geologists, pp. 15-26.
Tainter, P. A., 1984, Stratigraphic and paleostructural controls
on hydrocarbon migration in Cretaceous D and) Sandstones
of the Denver Basin, in). Woodward, F. F. Meissner, and). L.
Clayton, eds., Hydrocarbon Source Rocks of the Greater
ROCky Mountain Region: Denver, Rocky Mountain Association of Geologists, pp. 339-354.
Glossary
206
cf.
()t.
GLOSSARY
207
zene-methanol or chloroform) can elute many NSO compounds. Asphaltenes do not move easily through the column
and are not recovered by column chromatography. Column
chromatography is the first step in most bitumen analyses
because it separates the complex bitumen mixture into relatively homogeneous packages.
condensate: 1. material that exists in the gas phase under reservoir pressure-temperature conditions but which condenses to the liquid phase when brought to the surface. 2.
light oil, often any light-colored oil having an API gravity of
apprOXimately 45 or more.
conduit: a continuous migration pathway. Conduits can include coarse-grained rocks, fractured or jointed rocks, and
possibly active fault planes.
conjugated system: a series of alternating single and double
bonds between adjacent carbon atoms, as in the benzene
molecule.
Conodont Alteration Index: A maturity scale with values
ranging from 1 to 8 that is based on darkening of conodonts,
microfossils found in many Paleozoic rocks. It is most valid
and useful beyond peak oil generation.
cOITelation: comparison of gross or detailed chemical and
physical properties of two or more samples of organic matter
in an effort to compare their origins, diagenesis, catagenesis,
migration, and alteration.
CPI: see Carbon Preference Index.
cracking: 1. breakdoWn oflarge organic molecules into smaller
ones. It is a process usually associated with the formation of
condensates, gasoline-range hydrocarbons, and gas from oil.
2. thermal decomposition oflarge organic molecules, such as
kerogen and asphaltenes, to yield bitumen molecules of various sizes. In this usage it is similar to catagenesis.
cyclics: compounds having one or more rings in their structures. Most cyclic compounds in geological environments
have six-membered rings, although five-membered rings also
occur occasionally. Cyclic compounds can include alicyclics,
aromatics, and naphthenoaromatics.
cyclization: formation of cyclic structures by chemical reactions.
cycloalkanes: saturated hydrocarbons containing one or more
rings.
deadline: See hydrocarbon deadline.
decarboxylation: loss of a carboxyl group. Decarboxylation is
often induced by heating and liberates carbon dioxide.
delocalization: freedom of movement of electrons through a
conjugated system. Delocalization greatly increases the stability of a molecule compared to a nondelocalized analog. Delocalization also increases the stability of an ion formed from
a molecule containing delocalized electrons or of excited-
208
GLOSSARY
209
210
GLOSSARY
211
cal compounds. The compound is vaporized in the inlet system and then bombarded with large amounts of energy. The
energy knocks one electron out of some of the molecules,
forming ions with essentially the same mass as the original
compounds. These "molecular ions" can then decompose by
a number of pathways, depending upon the specific structures of the original compounds. A large number of fragment
ions are formed in this way. The ions are then accelerated into
a magnetic field whose intensity allows only certain masses to
pass through (the remainder being deflected to one of the
magnets). The intensity of the magnetic field is varied rapidly,
so that, in turn, ions of a wide range of mass-to-charge ratios
(mJz) can be detected. The pattern of ions passing through
the magnetic field is a fingerprint characteristic of the original
compound. This fingerprint is called the mass spectrum.
When coupled with a gas chromatograph, a mass spectrometer can also be used to look for ions having particular
characteristics. For example, most steranes easily form fragment ions having mJz 217. Thus, by scanning the entire gaschromatographic effluent for the presence ofmJz 217 ions, we
can detect any steranes that are present.
Mass spectrometers are also used to determine isotope
ratios. Because molecules containing heary isotopes are
heavier than normal, so are the ions formed in the mass
spectrometer. These differences can be detected easily and
exactly.
Mass spectrometry is used in fingerprinting, for maturity
determinations, and for environmental determinations. See
also gas chromatograph-mass spectrometer.
mass spectrum: the recording of the ions present and their
relative abundances in a sample that has been analyzed in a
mass spectrometer. See also mass spectrometer.
mature: having enough thermal maturity to be within the hydrocarbon-generation window.
maturity: the degree to which hydrocarbon generation has proceeded in a kerogen.
metagenesis: the late stages of thermal maturity when gas generation and cracking predominate.
methane hydrates: See gas hydrates.
Methylphenanthrene Index: ratio of several methylphenanthrenes, tricyclic aromatic molecules found in the aromatic
fractions of oils and bitumens. The index is related to vitrinite
reflectance by the empirical equation No = 0.60(MPI) +
0.37.
212
GLOSSARY
213
214
GLOSSARY
215
waters that are in contact with the oil. Water washing often
occurs in conjunction with biodegradation, and their effects
are not easily distinguishable.
wet gas: gas containing more than about 10/0 ethane, propane,
and other hydrocarbons heavier than methane.
zooplankton: tiny unicellular animals that feed on phytoplankton for their source of energy. They are not photosynthetic
organisms.
References
Alexander, R., R. I. Kagi, G. W. Woodhouse, and J. K Volkman, 1983, The geochemistry of some biodegraded Australian oils: Journal of the Australian Petroleum Exploration
Association (APEA), v. 23, pp. 53-63.
Altebaumer, F.J., D. Leythaeuser, and R. G. Schaefer, 1983,
Effect of geologically rapid heating on maturation and hydrocarbon generation in Lower Jurassic shales from NWGermany, in M. Bjor0Y, ed., Advances in Organic
Geochemistry 1981: Chichester, Wiley, pp. 80-86.
Anders, D. E. and P. M. Gerrlld, 1984, Hydrocarbon generation
in lacustrine rocks of Tertiary age, Uinta Basin, Utahorganic carbon, pyrolysis yield, light hydrocarbons, in J.
Woodward, F. F. Meissner, andJ. L. Clayton, eds., Hydrocarbon Source Rocks of the Greater ROcky Mountain Region:
Denver, Rocky Mountain Association of Geologists, pp. 513529.
Angevine, C. 1. and D. 1. Turcotte, 1983, Oil generation in overthrust belts: Bulletin of the American Association of Petroleum Geologists, v. 67, pp. 235-241.
Baker, R. A., H. M. Gehman,Jr., W. R.James, and D. A. White,
1984, Geologic field number and size assessments of oil and
gas plays: Bulletin of the American Association of Petroleum
Geologists, v. 68, pp. 426-437.
Barker, C. and P. A. Dickey, 1984, Hydrocarbon habitat in main
producing areas, Saudi Arabia: discussion: Bulletin of the
American Association of Petroleum Geologists, v. 68, pp.
108-109.
Barker, C. and M. K Kemp, 1982, Stability of natural gas at high
temperatures, deep subsurface: Bulletin of the American Association of Petroleum Geologists, v. 66, p. 545.
Barwise, A.J. G and P.J. D. Park, 1983, Petroporphyrin
fingerprinting as a geochemical marker, in M. Bjor0y, ed.,
217
218
REFERENCES
Duchscherer, W. Jr., 1981, Nongasometric geochemical prospecting for hydrocarbons with case histories: Oil and Gas
Journal, October 19, pp. 312-327.
- - - , 1982, Geochemical exploration for hydrocarbons-no
new tricks-but an old dog: Oil and Gas Journal, July 5, pp.
163-176.
- - - , 1984a, Discovery and development of KWB field-1:
Oil and Gas Journal, May 21, pp. 175-186.
- - - , 1984b, Discovery and development of KWB field-2:
Oil and GasJounial, May 28, pp. 143-151.
Durand, B., 1983, Present trends in organic geochemistry in
research on migration of hydrocarbons, in M. Bjor0Y, ed.,
Advances in Organic Geochemistry 1981: Chichester, Wiley,
pp. 117-128.
Durand, B. and M. Parratte, 1982, Oil potential of coals, a
geochemical approach: Institut Francais du Petrole, Ref.
30560, 16 pp.
Edman,J. D. and R. C. Surdam, 1984, Influence ofoverthrusting
on maturation of hydrocarbons in Phosphoria Formation,
Wyoming-Idaho-Utah Overthrust Belt: Bulletin of the American Association of Petroleum Geologists, v. 68, pp. 18031817.
Epstein, A. G.,J. B. Epstein, and L. D. Harris, 1977, Conodont
color alteration-an index to organic metamorphism: United
States Geological Survey Professional Paper 995, 27 pp.
Espitalie, J., J. L. Laporte, M. Madec, F. Marquis, P. Leplat,
J. Poulet, and A. Boutefeu, 1977, Rapid method of characterizing source rocks and their petroleum potential and degree
of maturity: Revue de l'Institut Francais du Petrole, v. 32, pp.
23-42 (in French).
Faber, E. and W. Stahl, 1984, Geochemical surface exploration
for hydrocarbons in North Sea: Bulletin of the American ASsociation of Petroleum Geologists, v. 68, pp. 363-386.
Foote, R. S., 1984, Significance of near-surface magnetic anomalies, in M.J. Davidson, B. M. Gottlieb, and E. Price, eds.,
Unconventional Methods in Exploration for Petroleum and
Natural Gas III: Dallas, SMU Press, pp. 12-24.
Furlong, K. andJ. D. Edman, 1984, Graphical approach to determination of hydrocarbon maturation in overthrust terrains:
Bulletin of the American Association of Petroleum Geologists,
v. 68, pp. 1818-1824.
Gallagher, A. V., 1984, Iodine: a pathfinder for petroleum deposits, in M.J. Davidson, B. M. Gottlieb, and E. Price, eds.,
Unconventional Methods in Exploration for Petroleum and
Natural Gas III: Dallas, SMU Press, pp. 162-173.
Gies, R. M., 1982, Origin, migration, and entrapment of natural
gas in Alberta Deep Basin: Part 2: Bulletin of the American
Association of PetroleUm Geologists, v. 66, p. 572.
Hagemann, H. W. and A. Hollerbach, 1983, The spectral
219
220
Paris Basin, France-II. Changes in aromatic steroid hydrocarbons: Geochimica et Cosmochimica Acta, v. 45, pp. 13451355.
Mackenzie, A. S. and D. McKenzie, 1983, Isomerization and
aromatization of hydrocarbons in sedimentary basins formed
by extension: Geological Magazine, v. 120, pp. 417-470.
MacLeod, M. K., 1982, Gas hydrates in ocean bottom sediments:
Bulletin of the American Association of Petroleum Geologists,
v. 66, pp. 2649-2662.
Magoon, L. B. and G. E. Claypool, 1981, Two oil types on North
Slope of Alaska-implications for exploration: Bulletin of the
American Association of Petroleum Geologists, v. 65, pp.
644-652.
- - - , 1983, Petroleum geochemistry of the North Slope of
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ed., Advances in Organic Geochemistry 1981: Chichester,
Wiley, pp. 28-38.
Marchand, A. andJ. Conard, 1980, Electron paramagnetic resonance in kerogen studies, in B. Durand, ed. Kerogen: Paris,
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Mattavelli, L., T. Ricchiuto, D. Grignani, and M. Schoell, 1983,
Geochemistry and habitat of natural gases in Po Basin, northern Italy: Bulletin of the American Association of Petroleum
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Maughan, E. K., 1984, Geological setting and some geochemistry of petroleum source rocks in the Permian Phosphoria Formation, in J. Woodward, F. F. Meissner, and J. L. Clayton,
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McCulloh, T. H., 1969a, Geologic characteristics of the Dos
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- - - , 1969b, Mass properties of sedimentary rocks and
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Meissner, F. F., 1978, Petroleum geology of the Bakken Formation, Williston Basin, North Dakota and Montana, in The
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- - - , 1983, Basic fracture theory and its applications to fractures found in foreland basins: Presented at Fourteenth Annual Petroleum Geology Symposium, Morgantown, W. Va.
Middleton, M. F. and D. A. Falvey, 1983, Maturation modeling
in Otway Basin, Australia: Bulletin of the American Association of Petroleum Geologists, v. 67, pp. 271-279.
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1982, Nuclear magnetic resonance: technique for direct nondestructive evaluation of source-rock potential: Bulletin of the
REFERENCES
221
222
REFERENCES
223
Index
Antrim Shale, 12
API gravity, 156
As correlation parameter, 155, 157, 179
Formula for calculating, 156
Relation to biodegradation, 56, 157
Relation to maturity, 51, 55, 157
Relation to sulfur content, 51, 157
Relation to wax content, 157
Argentina, 162-163
Aromatics, 22-24, 44-45, 206
Aromatization,27-28, 36,45, 59,206
Arrhenius equation, 122, 146,206
Arrhenius plot, 145
Asphaltenes, 24-25, 206
Non-biodegradability of, 57
Removal of, 44, 55, 74
Size of, 24, 44
Solubility of, 44, 55
Stacking of, 26, 37, 44
Structure of, 24-25
Sulfur in, 25, 44, 51, 157, 158-159
Athabasca Tar Sands, 55, 66, 68
Atlantic Ocean, 10, 11, 15-16
Austin Chalk, 191, 193
Australia, 13, 106, 115, 140-141, 162,
165-166
Bacteria
Aerobic,.9, 55, 205
Anaerobic, 9, 34, 55, 205-206
Cellular material of, 5, 33
D~struction of hydrocarbons by. See Biodegradation
Bactericides, 13, 14, 25, 83, 206
Bakken Shale, 12, 39, 65, 68
Baltimore Canyon, 111, 117, 118-119
Basin and Range, 169-171
Benzene, 22, 44, 45
Beta configuration, 26-27, 206
Big Horn Basin, 140, 157
225
226
Biodegradation, 55-60,89,206
Conditions required for, 55, 179
During migration, 55-56, 70
Effect on correlations, 156, 161-163, 179
Effect on isotope ratios, 56, 57, 60, 179
Effect on sulfur content, 56-58, 157, 169,
179-180
Examples of, 162-163, 165-166, 178, 179
Of gas, 59-60
Intensity of, 56-57, 160, 202
Of oil, 55-58
Biogenic gas, 2, 59-60, 164, 180
Accumulations of, 69, 156, 180
Deuterium in, 164
Dryness of, 59-60, 164, 180
Isotope ratios of, 59-60, 164, 180
Marine versus nonmarine, 164
And surface prospecting, 183, 184
Biogenic molecules, 206
Biogenic sediments, 14-15, 17
Biomarkers, 44-45, 206
Biopolymers, 25, 32, 206
Bioturbation, 9, 15
Bitumen, 2, 31, 38, 43-44, 206
Analysis of, 74-81
BitumenffOC ratios, 119-120
Column chromatography of, 74-75, 158
Comparison with oil, 58-60
Composition of, 43-60
Concentration in rocks, 38-39
Effect of contamination and weathering on,
89-90
Extraction of, 74
Fluorescence of, 89, 104
Generation of, 38-39
Maturity determinations from, 89, 103-104,
108-111,159-160
Non-indigenous, 120. See also Contamination
As precursor for oil, 43-44
Solidified, 64, 98
Black Sea, 11, 13
Black shale, 12, 15-16, 172
Boghead coal, 32, 206
Bond angles, 25-26
Botryococcus, 88
Bottomsetbeds, 10-11, 114
Branching, 21, 44
Brazil, 134
Buoyancy, 65-66,GB, 70
Burial rate. See Sedimentation rate
Burial-history curves, 123, 206
Construction of, 123-125
Effect of compaction on, 123, 125
Effect of faulting on, 128-130
Family of, 124-125
C1S + fraction, 74,206. See also Bitumen
CAl. See Conodont Alteration Index
Calcite-compensation depth, 15
California, 8, 9, 12,36,50,68, 139-140, 159,
161, 182
Canada, 55,66
Capillary-entry pressure, 65-66, 68, 206
Carbohydrates, 25, 32, 34
Carbon cycle, 5-6, 206
Carbon Preference Index, 46-47, 206. See also
n-Alkanes
Effect of source on, 45-47, 51, 103, 159160
As maturity indicator, 51, 59, 103, 108,
159-160
Carbon-Ratio Theory, 138
Carbonates
Isotope ratios in, 29-30, 186
Oils from, 157-158
Sedimentation rates in, 14-15
Sulfur in, 34, 58-59, 139
Carboxyl group, 24, 27, 206
Carrier beds, 3, 63
Caspian Sea, 11
Catagenesis, 2, 31, 32, 35-38, 206
Relation to oil generation, 35, 38
Catalysis, 207
In cracking, 55
In oil generation, 122
In pyrolysis, 96
Caving, 89, 97, 98, 101
Cellulose, 25, 33
Chainman Shale, 169-171
ChattanoogaShaie,12
Chemical reactions
Alkyl-group migration, 28, 51, 53
Aromatization, 27-28, 36,45,54, 206
Cracking, 28, 32, 36, 38,45,207
Cyclization,28, 32, 45,207
Decarboxylation, 27, 207
Disproportionation, 208
Epimerization, 28-29, 51, 53,208
Hydrogenation, 22, 27, 210
Isomerization, 28, 210
Oxidation, 9, 27-28, 45,212
Reduction, 27-28,213
Chemistry, 19-29
Chile, 11
China, 10
Chiorophyll, 24, 45, 47-48
Chromatography, 207. See also Column
chromatography; Gas chromatography;
Gas chromatography/mass spectrometry;
Thin-layer chromatography
Circulation of waters, 7-8, 10-13
And oxygen-minimum layer, 10
Restriction of, 10-13, 17
And upwelling, 7-8, 17
Cis, 26,207
Clathrates, 69, 207
Clays. See Catalysis
Coals
Algal, 32
Boghead, 32, 206
Caving problems with, 89
Composition of, 25, 115
Deposition of, 13, 14
Of different ages, 115
Elemental analysis of, 98
As kerogen, 32
Lipid-rich, 115
Pristanelphytane ratios in, 160, 172
Pyrolysis of, 98, 115
Pyrolysis-gas chromatography of, 115
Rank of, 37-38, 98, 108, 115, 138, 144
Sedimentation rates of, 14, 17
As source rocks for gas, 13, 115
As source rocks for oil, 13, 115, 172
Sulfur in, 34
Coastal-onlap curves, 16
Colombia, 12
Color
As indicator of anoxia, 9, 15-16
Estimating TOC from, 84
Colorado, 33
Column chromatography, 74-76,207
In correlations, 158-159
Condensate, 207
Deadline for, 139
Gravity of, 157
Origin of, 40-41, 55
Conduits, migration, 3, 63, 66-67, 172-173,
207
Conodont Alteration Index, 86, 89, 102, 108,
207
Correlation with vitrinite reflectance, 108
Contamination, 89-90, 97, 158
Coriolis force, 8
Correlations, 155-180, 207
Analytical techniques in, 74-83
Bulk parameters in, 155, 156-159
Case studies, 165-173
Difficulties in, 156, 162, 166, 173
Gas chromatography in, 157-158, 161
Gas-gas, 156, 164, 172, 174, 179-180
Gc/ms in, 161-163, 165-166, 169, 171,
174-176
Isoprenoids in, 160, 166-170, 172, 177-180
Isotopes in, 157, 159, 164, 166-167, 172,
177-180
Light hydrocarbons in, 157-158
n-Alkanes in, 159-160, 165-170, 172, 174,
177
Negative, 156, 173, 179
Oil-oil, 165-168, 172, 174-175, 177-180
Oil-source rock, 43-44, 86,169-171,174,
176,178-179
Philosophy of, 155-156, 173
Porphyrins in, 160-161, 178-180
Positive, 156, 173
INDEX
Correlations-Continued
Practice problems, 174-180
Specific parameters in, 155, 159-163
Steranes in, 161-163, 165, 169, 171, 174176
Sulfur in, 157, 169, 178-180
Trace metals in, 159
Triterpanes in, 161-163, 165-166, 169, 171
C.O.S.T. B-2 well, 111, 113
Costs
Analytical, 90
Of modeling, 203
Of swface prospecting, 184-187
CPr. See Carbon Preference Index
Cracking. See Chemical reactions; Oil
Cutinite, 33, 106, 115, 146
Cyanobacteria, 47
Cyclization,28,32,45,207
Cycloalkanes, 21, 23, 207
Cyclohexane, 20, 26
Cyclohexene, 21
Cyclothems, 12
D:J Sandstones, 196-199
Deadline for hydrocarbon preservation. See
Oil; Gas
Deasphalting, 55, 74, 156
Decarboxylation, 27, 207
Deep Sea Drilling Project, 15
Delocalization of electrons, 23, 207-208
Delta, use in isotope ratios, 30
AC method, 185-186
Deltas. See also Mahakam Delta
Migration in, 66, 172
Sedimentation in, 10-11, 14, 162
Density logs, estimating TOC values with, 84
Density stratification, 7, 10-13
Denver Basin, 196-199
Depositional environment. See Organic facies
Diagenesis, 2, 6, 32, 38, 208
Aerobic, 9, 205
Anaerobic, 9, 205-206
Of different types of organic matter, 14
Effect on biomarkers, 45-50
Effect on sulfur content, 50-51
Effect on TOC values, 6, 14-16, 105-106
Kerogen formation during, 32-33
Loss ofheterocompounds during, 24, 32
Prevention of, 9, 14, 17
Diasteranes, 53
Diatomite, 9
Diesel, as contaminant, 89-90
Diffusion, 64, 208
Dilution, 6-7, 14-15, 16-17
Diterpanes, 208
Aromatization of, 44
As biomarkers, 45, 49, 54
In correlations, 161
Diterpanes-Continued
227
Faulting
Effect on maturity calculations, 128-130
In migration, 66-67
Fecal pellets, 14
Fingerprinting, 80, 83, 156, 160,208
Fischschiefer, 174, 176, 178-179
Fluorescence, 208-209
Of bitumen, 89, 104
Ofkerogen, 86, 88, 97, 102
Fluvially dominated systems, 11-12, 13. See
also Deltas
Foreset beds, 11, 114
Formation-density logs, 84
Fractional conversion, 198-200
Fractures, 66, 172-173
Fragment ions, 78-80, 209
Fragmentogram, 80, 209
Free radicals, 38, 209
Fulvic acids, 32, 209
Functional group, 209
G,94
Determination of, 94-98
Go, 94
Estimation of, 105
Gabon, 10
Gamma-ray logs, in estimating TOC values,
84
Gamma-ray surveys, 186
Gammacerane, 161-162, 169, 171
Gas. See also Methane
Adsorbed, 83
Analysis of, 83, 184
Biodegradation of, 59-60
Biogenic. See Biogenic gas
Composition of, 59-60, 164
Correlation of. See Correlation, gas-gas
Deadline for, 139,209
Dry, 135, 139, 208. See also Methane
Generation of, 2, 32, 35, 38-41, 55, 59-60,
135. See also Methane
Headspace, 83
Hydrates, 69, 209
Isotopic composition of, 59-60, 83, 164,
184-185
Mixing of, 59, 164
Nonhydrocarbon, 59
Origin of, 164
Sour, 59
Wetness of, 59-60, 83, 164, 215
Gas chromatogram, 77, 209
Gas chromatograph, 76, 209
Gas chromatography, 76-78
Gas chromatography/mass spectrometry, 7880,104,209
Gc,76-78
Gclms, 78-80, 104
Geochemical logs, 111-113, 118-119
Geochemical Surveys, Inc., 185-186
228
Hydrocarbons-Continued
Saturated, 21
Separation of, 74-76
Unsaturated, 21. See also Hydrocarbons,
aromatic
Hydrocarbons, already generated, 94
Hydrochem Surveys International, 184-185
Hydrogen
Role in cracking, 27-28, 36
Hydrogen index, 95, 106, 210
Effect of maturity on, 95, 106
Interpretation, 36, 45, 59, 206
In volumetric calculations, 198-201
Hydrogenation, 22,27,210
Hydroxyl group, 25,210
INDEX
La Luna Limestone, 12
Lakes
Anoxia in, 10, 33
Evaporites in, 12
High-wax oils from, 49, 169-170
Stratification in, 10
Sulfate in, 51
Laminations
As indicators of anoxia, 9, 12, 15, 17
Role in expulsion, 64
Leco carbon analyzer, 84, 211
Light hydrocarbons. See also Gas
As maturity indicators, 104-105
In correlations, 157-158
Migration of, 181-182, 184
In surface prospecting, 183-185
Lignin, 13, 14, 25, 33, 34, 45, 211
Lignite, 89
Lignosuifonate, 89
Lipids, 33, 103, 106, 107,211
Liptinite, 33, 40, 146, 211
LaM method, 142-144, 146,211
Lopatin's method, 123-142,211. See also Maturity modeling
Application to exploration, 139-142
Application to preservation deadlines, 138139,142
Comparison with other models, 142-146
How to use, 123-133
Louisiana, 147
Lucas Fonnation, 166
M +,211. See also Molecular ion
mle, 78
mlz,78,211
Macerals, 33, 35, 211
Magnetite, 185
Mahakam Delta, 13, 52, 115, 172
Mass chromatogram. See Mass fragmentogram
Mass fragmentogram, 80, 109, 110, 209
Mass spectrometer, 78, 211
Mass spectrometry, 78-80. See also Gas
chromatography/mass spectrometry
For isotope ratios, 80
In porphyrin analyses, 81,160-161
In surface prospecting, 185
Mass spectrum, 78-79,211
Maturity, 211. See also Kerogen, maturation
of; Hydrocarbon generation
Anomalies, 116-117
Calculation of. See TIl; LaM
Effect of burial history on, 133-134, 150
Effect of igneous activity on, 117, 135, 136
Effect of time and temperature on, 35
Effect of uranium on, 117
Factors affecting, 133-1;)5
Irreversibility of, 35
Measured. See Maturity parameters
Maturity-Continued
Measurement of, 86-89, 98-104, 108-111,
160
Modeling of. See Maturity modeling
In volumetric calculations, 198-201
Maturity lines
On burial-history curves, 139-140, 142,
150, 153, 154
On cross sections, 140-142
Maturity modeling, 121-154
Accuracy of, 137-139
Application to exploration, 139-142
Computerization of, 142
Difficulties with, 146
Effect of erosion on, 116-117, 133-135,
136,150
Effect of faulting on, 128-130
Effect of igneous activity on, 135, 136
Examples of, 166, 191, 196-197
Practice problems, 147-154
Maturity models
Calibration of, 135-136, 137-138
Comparison of several, 1452-146
Maturity parameters
For bitumen, 38-39,89, 103-104, 108111
Correlation among, 108, 144
Interpretation of, 108-111, 116-117, 118120
For kerogen, 86-89, 98-103, 108
Measurement of, 86-89, 98-105, 160
Metagenesis, 2, 32, 35, 38, 164, 211
Metals, in oils, 104, 159, 160, 178-180
Methane. See also Gas
Biogenic, 2, 32, 59-60, 69,156,164, 172,
179-180, 183, 184
Fonnation by decarboxylation, 27
Hydrates of, 69
Isotope ratios of, 30, 172, 179-180
Metagenetic, 2, 59-60
Oxidation of, 27, 202
Structure of, 20
Thennogenic, 2, 32, 39-40, 59-60, 172,
179-180
Methanogens, 2, 164
Methyl group, 21
Migration of, 28, 51, 53
Methylphenanfurene Index, 108, 211
Michigan Basin, 143, 166-168
Microbes, 212. See also Bacteria
Microfracturing, 39, 64, 70, 212
Microorganisms. See Bacteria
Microscopy, 86-89
Fluorescent light, 86, 88, 89
Reflected light. See Vitrinite reflectance
Transmitted light, 35, 86, 88
Migration, 3, 63-71, 212. See also Accumulation
Biodegradation during, 55-56, 70
Carrier beds for, 3, 63
229
Migration-Continued
Direction of, 66, 140, 192-193, 196-197,
199
Distance of, 65-67, 70, 192-193, 199
Drainage area for, 66
Effects on source-rock evaluation, 120
Effects on hydrocarbon composition, 6970,109-110
Efficiency of, 3, 64, 65, 201-202
Examples of, 192-193, 199
Lateral, 66-67, 70
Long-distance, 66-67, 192-193
Mechanisms of, 63-66
Phase changes during, 70
Primary, 63-65, 69, 70. See also Expulsion
Role of faults in, 66-67
Role of hydrodynamics in, 66
Secondary,63,65-67,69-70, 213
Significance for exploration, 66-67, 70,
193-195, 197, 199
Tectonics in, 66-67, 193
Through fractures, 66, 172-173
Timing of, 70, 140, 179
Vertical, 66-67, 70, 172
Model-based geochemistry, 3-4, 189-203
Models
Application to exploration, 3-4, 189-203
Basin evolution, 190
Cost of, 203
Detenninistic, 189, 190, 202
Migration, 192-193, 196-197, 199
Organic facies, 4, 17, 114
Probabilistic, 190,202-203
Productivity, 8
Qualitative, 189, 190-199
Source rocks, 16, 114, 190
Thennal-maturity, 4, 121-154, 190
Upwelling, 8
Volumetric, 4, 189, 198-203
Molasse Basin, 174-176, 178-179
Molecular ion, 78-79, 212
Molecular sieving, 76, 77, 159, 212
Montana, 185
Monte Carlo simulation, 202-203
Monterey Fonnation, 9, 12, 34, 36, 50, 159,
161
Moretanes, 53-54,108-109,162
Mowry Shale, 12, 196
MPI, 108, 212
n-Alkanes, 20-21, 212
Algal sources for, 45-46, 51
Analysis of, 76-77
Biodegradation of, 56
As biomarkers, 45-47
In correlations. See Correlations
Even-carbon preference in, 46-47, 49
Lack of preference in, 45-46, 51
Maturity effects on, 51-52
230
n-Alkanes-Continued
Oil-Continued
Organic matter-Continued
Quantity of, 84
Resistant; 14
Reworked, 14, 33
Settling rates of, 14
Terrestrial, 6,9, 14,25,33,45,49,85,97,
103, 106, 108, 162, 172
Organic richness, 6-16
Orinoco Tar Belt, 55
Otway Basin, 140-141
Outcrop samples, 89
Overpressuring, 39, 64, 70
Overthrust Belt, 128
Oxic environments, 13-14, 15-16
Oxidation, 9, 27-28, 45, 212
Oxidizing agent, 27, 212
Oxygen
As heteroatom, 24
In kerogen, 33-34, 36-37
In organic matter, 24
In waters and sediments, 9, 13-16. See also
Oxygen-minimum layer; Anoxia
Oxygen index, 95, 106, 212
Oxygen-minimum layer, 10-13, 17,212
Development of, 10
Expansion of, 11-12
PAH, 23, 212
Paleotemperature, 125-127, 128, 130,
131
Paraffins, 20-22, 212
Paris Basin, 94, 95
PDB, 29, 212
Pentane, 74. See also n-Pentane
Permil,30,157,212
Peru, 8,11
Petrex,185
Phase changes, 70
Phenols, 14, 25, 33, 446
Phosphoria Formation, 12, 34, 93
Phosphorus, 14
Photic zone, 7, 10, 212-213
Photosynthesis, 5, 7, 10, 30
Phytane, 22, 48, 213. See also Pristanelphytane ratio
Phytoplankton, 5-6, 213. See also Algae
Plants, terrestrial, 5-6, 25, 33, 48,162-163
Plutons, 117
Po Basin, 174, 178-180
Polar compounds, 44
Pollen
In kerogens, 33, 86
TAl measurements from, 88
Polymers, 25, 32,213
Porphyrins, 24, 44, 213
Analysis of, 81-82
As biomarkers, 45, 47-48, 51
In correlations, 160-161, 178-180
Maturity effects on, 51, 104, 108-109
Migration effects on, 69
INDEX
Porphyrins-Continued
Nonbiodegradability of, 57
Source of, 47-48
Types of, 24, 51, 81, 108-109
V~iratiosin,47,51,81, 104, 160, 178180
Powder River Basin, 186
Preservation, 8-14. See also Diagenesis
Pristane, 22, 48, 213
Pristane/phytane ratio
As correlation parameter, 160, 166-170,
172, 177-180
Effect of maturity on, 51-52, 160
Environmental interpretation of, 47,160,
172
Production Index, 95, 213
Productivity, 6-8,16-17
As cause of anoxia, 17
In evaporitic environments, 12
Factors influencing, 7-8
High, 7-8, 11, 12
Modeling of, 8, 16-17
In pelagic environments, 7, 13
Relation to upwelling, 7-8, 11
Programmed-temperature chromatography,
77,213
Propane, 21, 83, 164
Propene, 21
Propylene, 21
Protein, 25, 32, 34
Pseudo-activation energy, 122, 132, 139, 142143, 144-145
Puente Formation, 12
Pycnocline, 10,213
Pyrite
And anoxia, 9, 15-16, 34, 186
In kerogen concentrates, 82-83
In nonmarine sediments, 34
Relation to TOC, 34
In surface prospecting, 186
Pyrolysis, 213
In determining kerogen type, 85-86
Hydrocarbons released during, 85-86
Interpretation of, 94-96, 102, 106-107
Rock-Eval, 85, 94-95, 102,213
Strengths and weaknesses of, 95-96
T max of. See T max
Pyrolysis-gas chromatography, 85-86, 96, 115
Ra, 87, 213
231
Source-rock evaluation-Continued
Philosophy of, 93-94, 117
Practice problems, 118-120
Soxhlet extractor, 74, 214
Spores
Color of. See Thermal Alteration Index
In kerogen, 33, 86
Stagnation, 10, 11, 17
Starch, 25
Steranes, 21, 23, 50, 214
Aromatized, 23-24, 49, 54,80, 109, 163
Biodegradation of, 56, 162-163, 165
As biomarkers, 45, 47-50, 53
In correlations. See Correlations
Effect of migration on, 109-110
Epimerization of, 28, 51, 53, 109
As environmental indicators, 48-49, 162163
Isoskeletal, 53
Mass fragmentograms of, 110, 165,175176
Mass spectra of, 78-80
Maturation of, 51, 53, 104, 108-111
Numbering in, 23
Rearranged, 53, 110
Stereochemistry, 25-29, 214
Steroids, 45, 47-49, 214
Sterols, 48-49,162,214
Stratification, 7, 10-13,214
Sudan, 10
Sugars, 25
Sulfate ion
Conversion to organic sulfur, 32, 34, 51, 57
In fresh waters, 13, 34, 51, 169
Role in diagenesis, 9, 186
Role in hydrocarbon oxidation, 27, 57, 59,
139, 163, 186
Sulfur
In asphaltenes, 25, 44, 51, 157
In carbonates, 34, 58-59, 139
As heteroatom, 24
Isotope ratios of, 29, 80, 157
In kerogen, 32, 34, 36, 39, 41, 50-51, 58,
59,135-136,158
Measurement of, 82-83
In oil, 36, 41, 47, 50-51, 56-59, 69, 157,
169, 179-180
Surface prospecting, 181-187
Carbonate cements in, 186
Cost of, 184-187
~C method in, 185-186
Gamma-ray surveys in, 186
Gravity surveys in, 186
Heavy hydrocarbons in, 185
Induced polarization in, 186
Iodine in, 186
Isotope ratios in, 184-185, 186
Light hydrocarbons in, 183-185
Magnetics in, 185
OflShore, 184-185
232
Surface prospecting-Continued
Onshore, 183-186
Philosophy of, 181-183, 186-187
Problems with, 181-183, 186-187
Validity of, 182, 186-187
Vegetation anomalies in, 186
T."IT., 109, 166
T max' 88, 95, 102
Correlation with vitrinite reflectance, 108
Difficulties with, 102, 108
TAl, 214. See also Thennal Alteration Index
Tar,66,68,214
Tar mats, 68
Tasmanites, 88, 102
Temperature
Correction of measured, 125, 146
History, 125-127, 128, 130, 131
In maturity calculations, 132-133
Temperature programming, 77
Terpanes, 39, 214. See also Diterpanes; Triterpanes
Terrestrial organic matter. See Organic matter
Terrestrial plants, 5-6, 25, 33, 48, 162-163
Texas, 137-138, 191-195
Thermal Alteration Index, 86, 214
Correlation with vitrinite reflectance, 108
Difficulties with, 102, 108
Measurement of, 88
Thin-layer chromatography, 75, 89, 158, 214
Thrusting, effect on maturity, 128-130
Time, in maturity calculations, 132-133
Time-Temperature Index of maturity. See TTl
Tissot-Espitalie model, 143-146
TOC values, 84, 214
Effect of diagenesis on, 6, 14-16, 105-108
Effect of sedimentation rate on, 14-15
As indicator of anoxia, 9, 17, 106
Interpretation of, 97, 105-106
Measurement of, 84, 97
Relation to hydrogen index, 107-108
As screening technique, 84, 90, 98, 106
In volumetric calculations, 198-201
Todilto Limestone, 12
Trans, 26,214
Transfonnation ratio, 95, 214
Transgressions, 11, 16
Transmitted-light microscopy, 35, 86, 88
Traps, 63, 68-69. See Accumulation
Classical, 68, 173
Gas-hydrate, 69
Kinetic, 68, 173
Stratigraphic, 68,70, 193-194, 197
Tar-mat, 68
Trenton Fonnation, 166-167
Triterpanes, 23, 214. See also Hopanes
Aromatization of, 23, 49, 54
As biomarkers, 48, 50
Biodegradation of, 56, 80,162-163,165166
In correlations. See Correlations
Demethylated, 80, 162-163, 165
As environmental indicators, 48, 50, 161162
Epimerization of, 50, 53, 109, 111
Mass fragmentograms of, 80, 109, 162, 163,
16610.14
Mass spectra of, 79-80, 162
Maturity effects in, 50, 53-54, 104, 108109,111
Origin of, 21, 45, 48, 50
Triterpenoids, 45, 48, 214
TTl, 123, 133, 214
Application to deadlines, 138-139
Calculation of, 132-133
Calibration of values, 135-138
Interpretation of, 135-138
Turbidites, 14
Tuwaiq Mountain Limestone, 12
Uinta Basin, 64, 68, 86
Ultraviolet spectroscopy, 81, 160
Unconformity. See Maturity, effect of erosion
on
United States. See also the indivdual states
Basin and Range, 169-171
East Coast offShore, 111, 113, 117, 118-119
Eastern, 172-173
Gulf Coast, 12, 59, 114, 137-138, 147
Midcontinent, 12, 148
Western, 12
Western Interior Seaway, 160