Geochemistry

in Petroleum
Exploration
 Geochemistry
in Petroleum
Exploration

Douglas w. Waples
BROWN AND RUTH LABORATORIES, INC.
DENVER, COLORADO

... ~ D. REIDEL PUBLISHING COMPANY

" A Member of the Kluwer Academic
Publishers Group
DordrechtIBostonILancaster

INTERNATIONAL HUMAN
RESOURCES DEVELOPMENT
CORPORATION
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For Bob Witters
and all other excellent teachers

Cover illustration: Core 13 from Hole 550 of Leg 80 of the Deep Sea
Drilling Project, Goban Spur, North Atlantic. Black, bioturbated clay-
stones of probable Turonian to Coniacian age grade upward into green
and finally red claystones, reflecting the gradual increase in bottom-
water oxygen content in the Late Cretaceous. The sequence is capped by
a white chalk turbidite. See also figure 2.13.

Cover and interior design by Outside Designs.

© 1985 by International Human Resources Development Corporation.

Softcover reprint of the hardcover 1st edition 1985
All rights reserved. No part of this book may be used or reproduced in
any manner whatsoever without written permission of the publisher
except in the case of brief quotations embodied in critical articles and
reviews. For information address: lHRDC, Publishers, 137 Newbury
Street, Boston, MA 02116.

Library of Congress Cataloging in Publication Data

Waples, Douglas, 1945-
Geochemistry in petroleum exploration.
Bibliography: p. 217.
Includes index.
1. Organic geochemistry. 2. Geochemical prospecting. 3. Petro-
leum-Geology. 4. Gas, Natural-Geology. 1. Title.
TN871.W28 1985 622'.13 85-105
ISBN-l3: 978-94-010-8900-5 e-ISBN-l3: 978-94-009-5436-6
DOl: 10.1007/978-94-009-5436-6

Published by D. Reidel Publishing Company

P.O. Box 17, 3300 AA Dordrecht, Holland in co-publication with
lHRDC
Sold and distributed in North America by IHRDC
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Geological Sciences Series

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 iv
Preface ix
1. Introduction 1
Philosophy of Hydrocarbon Exploration
Formation of Oil and Gas
Applications to Hydrocarbon Exploration
Suggested Readings

2. Organic Facies 5
The Carbon Cycle
Factors Influencing Organic Richness
Examples of Rich and Lean Sediments
General Models for Source-Rock Development
Summary
Suggested Readings

3. Organic Chemistry and Isotopes 19

Introduction
Names and Structures
Stereochemistry and Isomers
Reactions
Isotopes

4. Kerogen 31
Introduction
Kerogen Formation
Kerogen Composition
Kerogen Maturation
Summary
Suggested Readings

5. Bitumen, Petroleum, and Natural Gas 43

Introduction
Compounds Present in Bitumen and Petroleum

vii
viii

Factors Affecting Composition ofBitu1nen and Petroleum Factors Affecting Thermal Maturity
Comparison of Bitumen and Petroleum Interpretation of TTl Values
Natural Gas Applications to Hydrocarbon Preservation
Summary Applications to Exploration
Suggested Readings Comparison of Several Maturity Models
Potential Problems with Maturity Calculations
6. Migration 63 Conclusions
Definitions Suggested Readings
Primary Migration Practice problems
Secondary Migration Solutions to Practice Problems
Accumulation
Effects on Oil and Gas Composition 10. Correlations 155
Significance for Exploration Introduction
Suggested Readings Correlation Parameters
Correlation Parameters for Gases
7. Analytical Techniques 73 Case Studies
Introduction Conclusions
Chemical Characterization for Correlations Sugsested Readings
Source-Rock Evaluation Practice Problems
Contamination and Weathering Solutions to Practice Problems
Analytical Costs
Summary 11. Surface Prospecting 181
Suggested Readings Philosophy of surface Prospecting
Surface-Prospecting Techniques
8. Source-Rock Evaluation 93 Summary
Definition of Source Rock Suggested Readings
Principles of Source-Rock Evaluation
Interpretation of Source-Rock Data 12. Integrated Applications to Exploration 189
Examples of Source-Rock Evaluation Philosophy of the Model-Based Approach
Summary Qualitative Models of Hydrocarbon Systems
Suggested Readings Quantitative (Volumetric) Models
Practice Problems Summary
Solutions to Practice Problems Suggested Readings

9. Predicting Thermal Maturity 121 Glossary 205

Introduction
References 217
Construction of the Geological Model
Special Considerations About Burial-History Curves Index 225
Calculation of Maturity
Preface

This book is intended primarily as a textbook for geolo-

gists engaged in petroleum exploration. Its purpose is to
introduce the reader to organic geochemistry and to show
how to apply geochemistry advantageously in an explora-
tion 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. Be-
cause 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 vocab-
ulary.
The emphasis in this book is on applications of geo-
_chemistry to hydrocarbon exploration. Most of the analyt-
ical techniques are discussed only briefly, because
although a geologist should know what a gas chro-
matograph 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 appropri-
ate 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 ex-
ploration 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 princi-

ix
x
pIes of geochemical interpretation. My interpretations are
not guaranteed to be the very best possible; they could
serve as focal points for classroom discussions.
Because of its design as a textbook for independent
study, graduate courses, or short courses, this book is not
intended as a reference volume or encyclopedia. Readers
who want to delve more deeply into various aspects of
petroleum geochemistry should consult the primary liter-
ature that I have cited, or the reference volumes Petro-
leum Formation and Occurrence by Tissot and Welte
(1978) and Petroleum Geochemistry and Geology by Hunt
(1979).
The literature cited in this book represents only a tiny
fraction of that available. At the end of most chapters
there is a short list of recent articles that will be of general
interest to a nonspecialist. At the end of the book is a
longer list of references cited in the text or figure legends.
Many chemical and geochemical terms are italicized
where they are first introduced. These and many other
terms are defined more formally in the Glossary.
Developing the ability to apply organic geochemistry
intelligently and effectively in exploration is not difficult,
even if one does not have a strong chemistry background.
This text is designed to foster the development of those
skills. If after reading the book you can find ways to make
geochemistry work for you, then you and I will have
succeeded.
Chapter 1 Introduction

PHILOSOPHY OF HYDROCARBON EXPLORATION

There is no one magical technique that removes all risk in
hydrocarbon exploration, although we would all wel-
come such an advance. The most we can ask of the vari-
ous exploration technologies is that they lower our risk.
Given the poor success rates for new-field wildcats, this
goal is certainly reasonable and feasible. As we improve
our ability to apply science in an exploration context, the
savings in both money and time not wasted on dry holes
could be phenomenal.
Explorationists now have at their disposal a large arse-
nal of weapons to use against the elusive hydrocarbon.
Among these are the various traditional branches of geol-
ogy, global tectonics, seismic technology, remote tech-
niques (including satellite and airborne methods and
surface- prospecting), organic geochemistry, and inte-
grated basin analysis. In order to make its exploration
program as effective and competitive as possible, a mod-
ern oil company should utilize all of these technologies in
appropriate ways.
Applying available scientific data and methods in a
cost-effective manner always presents a challenge. Ide-
ally, the initial reconnaissance phases in a new area
should lead to inexpensive high-grading, because much
of the original area will subsequently be rejected. More
expensive techniques can be used later in the areas of
greatest interest.
We must also decide how the various exploration tech-
nologies can best be integrated to create an exploration
program that provides, at minimum cost, information of

1
2

maximum value for selecting acreage and drill sites. It is

beyond the scope of this text to discuss such a strategy in PRIMARY HYDROCARBONS
detail. I shall, however, attempt to demonstrate several STAGE PRODUCT GENERATED---
ways in which organic geochemistry can be integrated
into an exploration program.
Organic geochemistry has become a widely used tool in I ........
(d,.g.,n.~
ATURE
)
DRY GAS
hydrocarbon exploration conducted by many companies,
large and small, foreign and domestic. These exploration
applications are the result of recent technical and philo- w
I
sophical advances that have permitted direct utilization of a::
:>
~
geochemistry in evaluations of basins, plays, and pros- <{
a: OIL
pects. As a prerequisite to intelligent and effective appli- UJ

. . ATURE
0..
cation of organic geochemistry, we must understand not ~
ILl
only how oil and gas are formed in the subsurface, but ~
(cal.genes ~)

also how we can use this knowledge to locate new hydro- o

z<{
carbon reservoirs. We must therefore begin with a basic
CONDENSATE
l~~~~~-t::W:E:T::G:A~S~' ~illIlIlIlI~~
understanding of the process of hydrocarbon formation. ~
~

FORMATION OF OIL AND GAS

Proponents of the organic origin of oil and gas have given
us a general picture of how organic matter derived from
dead plants is converted to hydrocarbons. Although the
transformation process is very complex, with many de-
tails still poorly understood, it is known that organic de-
bris derived from plants and algae is best preserved in
fine-grained sediments deposited in the absence of oxy-
gen. This organic matter is modified by low-temperature
chemical and biological reactions (called diagenesis) that
occur during transport to and early burial in the deposi-
tional environment. Many of the chemical compounds
present in sediments are in fact derived from bacteria,
and were formed as dead organic matter was converted to
microbial tissues.
Most of this organic matter is transformed during
diagenesis into very large molecules, the largest of which
are called kerogen. These playa key role as the precursors
for oil and much natural gas.
The earliest stage of hydrocarbon generation occurs
during diagenesis (fig. 1.1). Certain microorganisms,
called methanogens, convert some ofthe organic debris to
biogenic methane. Formation of biogenic methane has
been recognized for a long time, but only within the last
few years have we realized that in many areas a large
portion of the natural-gas reserves are biogenic.
As burial depth increases, porosity and permeability
1 ST· . . ATURE. DRY GAS
(metamotpl"to l IT"
FIGURE 1.1 Generalized scheme for oil and gas generation as
a function of thennal maturity of source rocks. Reprinted by
pennission of the American Association of Petroleum Geolo-
gists from Rice and Claypool, 1981.
decrease, and temperature increases. These changes lead
to a gradual cessation of microbial activity, and thus even-
tually bring organic diagenesis to a halt. As temperature
rises, however, thermal reactions become increasingly
important. During this second transformation phase,
called catagenesis, kerogen begins to decompose into
smaller, more mobile molecules. In the early stages of
catagenesis most of the molecules produced from kerogen
are still relatively large; these are the precursors for petro-
leum, and are called bitumen (fig. 1.1). In the late stages
of catagenesis and in the final transformation stage, called
metagenesis, the principal products consist of smaller gas
molecules.
In recent years this relatively simple picture of hydro-
carbon generation has been complicated slightly by our

growing awareness that kerogens formed from different
kinds of organic matter, or under different diagenetic con-
ditions, are chemically distinct from each other. These
differences can have a significant effect on hydrocarbon
generation, as we shall see in chapter 4.
Once formed, oil and gas molecules can be expelled
from the source rock into more permeable carrier beds or
conduits. Migration through these conduits often leads to
traps, where hydrocarbon movement ceases and accumu-
lation occurs. Our present understanding of the details of
migration is far from complete, but we have learned to
trace migration pathways and compare migration effi-
ciencies from one area with those from another.
APPLICATIONS TO HYDROCARBON EXPLORATION
There are a number of important questions that organic
geochemistry can answer to help solve exploration prob-
lems. These include the following:
1. What was the original hydrocarbon-source potential of
a particular rock? Does it have any remaining source
potential at the present time?
2. What depositional environments are conducive to the
formation of kerogens having high hydrocarbon-
source potentials? Can we predict their occurrence?
3. Which types of kerogen are converted to oil? to gas?
4. What factors influence oil gravity and composition?
5. What thermal conditions are required for hydrocarbon
formation? Can we predict when and where genera-
tion has occurred?
6. Can we correlate several samples with each other to
decipher genetic relationships? Can we distinguish
biogenic methane from thermal methane?
7. Can we predict the direction, timing, and efficiency of
hydrocarbon migration in a particular area?
8. What conditions are required for hydrocarbons to be
preserved against the destructive forces of oxidation,
cracking, and biodegradation? Can we predict where
destruction will occur?
Because traditional applications of organic geochemistry
have been analysis-based, they are critically dependent
upon sample availability. As a consequence of drilling on
structural highs, however, sampling programs are inevi-
tably biased toward shallow and young samples. Thus
1. INTRODUCTION 3
FIGURE 1.2 Typical drilling pattern in many basins. The
deepest, rrwst mature rocks, and the rrwst basinal facies are
usually never penetrated. Reprinted by permission of the
Rocky Mountain Association of Geologists from Waples,
1984b.
our analyses miss the deepest rocks in a basin, and often
do not include the most basinal facies (fig. 1.2).
A second problem with the analysis-based approach is
that it generally lacks the ability to extrapolate measured
data through time and space. In theory, in order for an
analysis-based approach to be valid, we would need to
have enough data coverage in the area of interest to allow
interpolation between points, rather than requiring ex-
trapolation beyond data control. In many regions, partic-
ularly frontier areas, adequate data coverage is simply
impossible. By adopting the analysis-based approach in
such cases, we force ourselves to extrapolate meager mea-
sured data across large unsampled voids.
The only way to intelligently extrapolate (or even inter-
polate in many cases) is to adopt a model-based ap-
proach, in which a conceptual geological model is
developed for the area of interest. Such a model must take
both local measured data and data from analogous
geological settings into account, and must be continually
revised as new information becomes available. The model
can be based on all types of relevant data, including grav-
ity, magnetics, seismic, surface geology, subsurface geol-
ogy, paleontology, and geochemistry data. It may also
include whatever data are available in other areas that
were selected to serve as analogs.
Geochemical models form an important part of the
4

overall geological model. Three main types of geochem-

ical 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 com-
paring 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 ana-
lytical data, develop a future analytical plan, and analyze
the results in an exploration context. The successful appli-
cation of geochemistry to exploration in the future will
rest heavily upon our ability to develop and apply intelli-
gent 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. De-

maison and R.]. Murris, eds., Petroleum Geochemistry and
Basin Evaluation: American Association of Petroleum
Geologists Memoir 35, Tulsa, American Association of Petro-
leum 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 Associ-
ation 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 Moun-
tain Region: Denver, Rocky Mountain Association of Geolo-
gists, pp. 35-49.
Chapter 2 Organic Facies

THE CARBON CYCLE

Because oil and gas are generated from organic matter in
sedimentary rocks, we need to understand how this or-
ganic matter came to be preserved in the rocks. Preserva-
tion of organic material is actually a rare event. Most
organic carbon is returned to the atmosphere through the
carbon cycle (fig. 2.1); less than 1% of the annual photo-
synthetic production escapes from the carbon cycle and is
preserved in sediments. Oxidative decay of dead organic
matter is a highly efficient process mediated largely by
microorganisms.
Preservation of organic matter begins with photosyn-
thesis. Some of the organic material in sediments consists
of fragments of plants or algae that derived their ener-
gy from the sun. A large fraction, however, comprises
microbial tissue formed within the sediments by the
bacterial transformation of plant and algal debris.
Zooplankton and higher animals contribute relatively lit-
tle organic matter to sediments (fig. 2.1). The recently
discovered deep-sea ecosystems in the Pacific Ocean
that derive their energy from oxidation of sulfides in
hydrothermal vents are interesting but volumetrically
unimportant.
Despite the great imbalance in biomass between terres-
trial plants (450 billion metric tons [t]) and aquatic phy-
toplankton (5 billion t), the yearly productivity of both
groups is about equal (fig. 2.1), as a consequence of the
much more rapid reproduction of simple aquatic organ-
isms. Because of extensive oxidation of land-plant debris
in soils, however, much ofthe terrestrial organic material

5
6

Toe (%)

0 .1 .2 .3 .4 .5
0
••
•
100

200
6

u;
a:
w 300
I-
w
!
CARBONATE
SEDIMENTS :I: •• •
(64,000,000) I-
a.. 400

•••
w
0

••
500
FOSSIL FUELS
(10,000)

600

FIGURE 2.1 The carbon cycle. Numbers represent quantities

in billions of metric tons. Those in parentheses are stored
quantities; those without parentheses are yearly fluxes.
FIGURE 2.2 Decrease in TOC values with depth of burial,
Adapted from The carbon cycle by B. Bolin. Copyright © 1970
by &ientific American, Inc. All rights reserved. showing diagenesis of organic matter in oxic marine sedi-
ments. From Waples and Cunningham, 1985.

is already highly oxidized when it arrives in the sed-
iments.
Although some destruction of organic material occurs
during transport to the depositional environment, a great
deal of the oxidation of organic matter occurs within the
sediments themselves. Figure 2.2 illustrates a typical
diagenesis curve for organic carbon deposited in an
oxidizing pelagic environment. Total-organic-carbon
(TOe) values decrease monotonically through the first
300 meters (m) of burial before leveling out at about
0.1 %, suggesting that either depth or organic-carbon con-
tent eventually limits diagenesis. Depth could interfere
with microbial diagenesis when compaction reduces pore
sizes and nutrient fluxes in interstitial waters. On the
other hand, the low Toe values could indicate that the
remaining organic matter has no more nutritional value,
and that the microbes ,have given up trying to digest it.
Each factor may be dominant under different conditions.
Although oxidative decay destroys most of the yearly
production, over vast amounts of geologic time the small
fraction that escaped the carbon cycle has built up ex-
tremely large quantities of organic matter (20,000,000 bil-
lion t) dispersed in fine-grained sedimentary rocks. Only
a small fraction of this (10,000 billion t, or about 0.05%)
occurs in economic deposits of fossil fuels. When we con-
sider inefficiencies in discovery and recovery, only one
molecule out of about every one million successfully nego-
tiates the journey from living organism to the gasoline
pump.
FACTORS INFLUENCING ORGANIC RICHNESS
In order for organic-rich rocks to be formed, significant
amounts of organic matter must be deposited and pro-
tected from diagenetic destruction. The three primary fac-
tors influencing the amount of organic matter in a
sedimentary rock are productivity, preservation, and dilu-
 2. ORGANlC FACIES 7

TERRESTRIAL AQUEOUS

1.4·7.8xlO'°t. org. C/ year 1.5 .7.0xlO·O!.org. C/ year

"
4% 13% 18% 8% 47% 46 %

STEPPE ESTUARIES
DESERT GR ASS LAND fOREST AGRICULTURE ALGAL BEDS
REEfS

...
294 l / km'
... ...
2!>OO Ilkm' 2798 l / km'

...
... 6429 IIkm'
7927 IIkm'

20.000 l / km' ~

FIGURE 2.3 Global distribution of primary photosynthetic
productivity, showing the great variations among marine en-
vironments. Adapted from Huc, 1980, by permission of the
Societe des Editions Technip.
tion. Productivity is the logical place to begin our analysis,
because without adequate productivity, accumulation of
organic-rich sediments cannot occur.
PRODUCTIVITY
A partial listing of the many factors influencing produc-
tivity 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 pat-
terns, orogeny and erosion, volcanism, paleoclimate, and
recycling by organic decay.
Nutrient availability is, in fact, one of the critical pa-
rameters governing productivity. Shallow-marine envi-
rooments, where there is local recycling of nutrients from
decaying organisms and influx of fresh nutrients from
terrestrial sources, are therefore much more productive
than the open ocean (fig. 2.3).
In relatively unrestricted marine environments, water-
circulation patterns are particularly important for supply-
ing nutrients and thus controlling productivity. Bodies of
water naturally develop density stratification, with a pref-
erence for horizontal water movement within each den-
sity layer. Nutrients dissolved in waters below the photic
zone therefore go unutilized, because under normal cir-
cumstances they cannot move upward into the zone of
photosynthesis. Only where there is upwelling of subsur-
face waters can these nutrients return to the photic zone.
Upwelling occurs where bulk movement of surface wa-
ter away from a particular area allows deeper water to
ascend to replace it. If this deeper water is enriched in
nutrients, high photosynthetic productivity will occur at
the site of upwelling. In the modern world there are zones
of intense seasonal upwelling off the west coasts of
8

r.Jl
t:::J pwelling

California, Peru, Namibia, and northwest Africa that re- FIGURE 2.4 Atmospheric circulation and upwelling patterns
sult from the movement, induced by the Coriolis force, of in northern summers during the Maestrichtian (Late Creta-
surface waters away from these coasts. There is another ceous). Reprinted by permission of Elsevier Science Publishing
Company from Parrish and Curtis, 1982.
zone of seasonal upwelling off the Horn of Africa in the
Indian Ocean as a result of monsoonal winds that drive
ervation (Bralower and Thierstein, 1984). There are
surface waters away from the coast. All these areas ex-
many more organic-rich facies resulting from excellent
hibit high productivity when upwelling occurs.
preservation than from extremely high productivity. After
Theoretical models have been developed to predict up-
all, if on the average only 1% of organic matter is pre-
welling (and consequent productivity) in ancient seas
served, increasing preservation rates is a very efficient
from input data on continental configurations, land
way to increase organic richness. Secondly, the accuracy
masses, wind- and water-circulation patterns, and pa-
with which we can reconstruct continental positions,
leoclimates (for example, Parrish, 1982; Parrish and Cur-
paleoclimatic conditions, and all the other factors that
tis, 1982). An example is shown in figure 2.4 for the
influence upwelling loci is severely limited, especially in
Aptian stage of the Early Cretaceous. The accuracy of the
the Paleozoic. Parrish (1982) recognized this problem,
models was tested by comparing predicted occurrences of
and therefore allowed herself an inaccuracy of 5° in
upwellings with rock facies known to be associated with
evaluating the success of her predictions. Whether an ac-
upwelling systems (organic-rich, phosphatic, glauconitic,
curacy limit of 5° is acceptable, even in the earliest stages
cherty). Parrish (1982) reported an encouraging correla-
of exploration in a frontier area, is a question worth
tion betwen predicted and reported occurrences of up-
considering.
welling facies for the Paleozoic.
Such models are interesting, and may in fact prove
PRESERVATION
useful in future exploration efforts. There are, however,
some problems associated with their application. First, Introduction. The principal control (in my opinion) on or-
productivity is probably not as important a factor as pres- ganic richness is the efficiency of preservation of organic

matter in sedimentary environments. Three factors affect
the preservation (or destruction) of organic matter: the
concentration and nature of oxidizing agents, the type of
organic matter deposited, and the sediment-accumulation
rate. Of these, oxidizing agents are probably the most
crucial factor.
Anoxia. Because most of the oxidation occurring in the
water column, soils, and sediments is biological, and be-
cause most biological oxidation processes require
molecular oxygen (02 ), the simplest way to limit oxida-
tion 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 disap-
pear; the remaining individuals often become dwarfed in
an effort to survive in a hostile environment. At dissolved-
oxygen levels below about 0.2 mLlL, essentially the only
viable organisms are those that we call anaerobes-
microorganisms that utilize materials like sulfate or ni-
trate 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 oc-
curring 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 preserva-
tion 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 or-
ganic 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-
2. ORGANIC FACIES 9
vated TOC values (generally above 2% and always above
1%). However, many oxic sediments also contain large
amounts of organic matter, especially of woody origin.
TOC values alone must therefore be used with caution.
The presence of undegraded marine organic material is a
strong indication of anoxia, because marine organic mat-
ter is consumed preferentially by organisms. Its presence
in rocks therefore indicates that diagenesis was stopped
prematurely, most likely by an absence of oxygen.
Color is not a reliable indicator. All anoxic sediments
will be very dark gray or black when deposited. Many
black rocks, however, are not rich in organic carbon; they
often owe their dark color to finely divided pyrite or to
particular chert phases. Color should be used mainly as a
negative criterion: If a rock is not very, very dark, it cannot
represent an anoxic facies.
The presence of pyrite itself can also be deceptive. Al-
though pyrite does indeed form under anoxic conditions,
and its presence indicates that the anaerobic reduction of
sulfate ion did occur, there is no guarantee that anoxia
was present at the sea floor; it may well have developed
after burial. Furthermore, anoxia can be very local; in-
tense pyritization of benthic bivalves is testimony to the
fact that pyrite is not a good indicator of bottom-water
anoxia at the time of deposition.
Finally, anoxic sediments show preserved depositional
laminae on a millimeter or submillimeter scale. The lam-
inae prove that burrowing fauna were absent, and there-
fore that dissolved-oxygen levels were below 0.2 mLIL.
Conversely, the presence of bioturbation indicates that the
bottom waters were not anoxic, although stunted bur-
rows can be used as evidence of dysoxia.
However, depositional laminae are also preserved in
some fine-grained but organic-lean rocks. For example,
the diatomite from the Pliocene Sisquoc Formation at
Lompoc, California, is finely laminated but almost pure
white and devoid of organic matter. It seems likely, by
analogy with the underlying Monterey Formation, that
this diatomite was deposited under anoxic conditions and
was originally organic rich. The organic matter present
was oxidized subsequent to deposition, perhaps by per-
colating ground water. However, because the bulk per-
meabilities of the diatomites are very low, the mechanism
for this oxidation is far from clear.
The ultimate implications of anoxia for petroleum
10
/ {~
......... ....... ................ ....
.............................. .. .
, .............................
.. ......... .............. .
..... :::: ::::::: .... ~ penetrated (Angola, Gabon, Newark Graben System) .
D nsity
slratifi alion
FIGURE 2.5 Schematic diagram of density stratification in a
stagnant basin.
exploration are great; it has been estimated, in fact, that
most of the world's oil was generated from source beds
deposited under anoxic conditions. It therefore behooves
us to understand the conditions under which anoxia
develops.
STAGNANT BASINS. Truly stagnant basins are actually
quite rare; slow circulation or turnover of the water col-
umn occurs almost everywhere. Nevertheless, it is in-
structive to consider complete stagnation, particularly in
understanding lacustrine beds. If an isolated body ofwa-
ter is deep enough, and if the climate is subtropical or
tropical, then permanent density stratification will arise
as a result of temperature differences within the water
column (fig. 2.5). Depths in excess of200 m are required
to prevent mixing during storms, and warm climates are
necessary to avoid overturn caused by freeze-thaw cycles.
The cooler, denser waters remain at the bottom, leading
to the eventual development of a pycnocline (density in-
terface) which prevents interchange between the two lay-
ers. Lack of communication between the layers prohibits
replenishment of oxygen in the bottom layer. Therefore,
once the original oxygen has been consumed in oxidizing
organic matter, no more oxygen can enter, and both the
waters in the bottom layer and the underlying sediments
will become anoxic.
Marine basins are seldom isolated enough to fit well
into the stagnant-basin model, but limnic environments
often are. Among the ancient lake beds thought to have
been deposited in permanently stratified waters are the
well-known Green River Shale (middle Eocene, Wyo-
ming), the Elko Formation (Eocene/Oligocene, Nevada),
and strata from several basins in China. Lake deposits
associated with continental rifting, especially during the
Triassic along the margins of the developing Atlantic Ocean,
are anoxic in some of the places where they have been
Lakes in failed rifts can also contain organic-rich, anoxic
Oz-poor sediments. Large amounts of oil have been found in non-
bottom marine basins in the southern Sudan. The Precambrian
waters Nonesuch shale of the Keewanawan rift system stretching
from Wisconsin to Kansas is the site of an active new
hydrocarbon play. Lakes of the Rift Valley of East Africa
are excellent modern analogs receiving much attention
from both researchers and explorationists at the present
time.
OXYGEN-MINIMUM LAYER (OML). The oX)'gen-min-
imum layer (fig. 2.6) is a layer of subsurface water that
has a lower dissolved-oxygen content than the water lay-
ers either above or below. This oxygen minimum devel-
ops when the rate of consumption of oxygen within that
layer exceeds the rate of influx of oxygen to it. Consump-
tion of oxygen results from decay of dead organisms that
have sunk from the photic zone above. The oxygen-
minimum layer usually begins immediately below the
photic zone, where photosynthesis and turbulence can no
longer contribute oxygen to the water. The supply of fresh
oxygen is therefore limited to horizontal movement of
oxygen-bearing waters. However, because these horizon-
tally moving waters also lie within the oxygen-minimum
layer, the oxygen they can contribute is limited. Below the
OML oxygen levels again increase, as a result of dimin-
ished oxygen demand, since most organic matter was
destroyed within the overlying OML.
Although an oxygen-minimum layer exists virtually
everywhere in the ocean, its intensity varies greatly. In-
tensely developed OMLs occur in areas of high productiv-
ity and, to a lesser extent, in areas of poor circulation.
Wherever an intensely developed OML intersects the sedi-
ment-water interface, sediments will be deposited under
low-oxygen conditions (fig. 2.6). Any organic matter ar-
riving in those sediments will have an excellent chance to
escape oxidation.
Bottomset beds associated with prograding delta sys-
tems can be rich in organic matter if they are laid down
within a well-developed oxygen-minimum layer. In con-

C..ontinental
Metel I;S('
- 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.
trast, foreset beds within the same system are leaner in
organic matter because they are deposited above the
OML. Chapter 8 contains a more complete discussion of
bottomset and foreset facies from the Mesozoic of the
North Slope of Alaska.
There are other ancient and modern examples of or-
ganic-rich rocks deposited under anoxic or near-anoxic
conditions associated with OMLs. These include the mod-
ern Peru-Chile shelf (induced by high productivity asso-
ciated with upwelling) and various occurrences of black
sediments of Aptian to Turonian age in the North
Atlantic.
It has been proposed that at certain times in the past
(e.g., mid-Cretaceous, Late Jurassic, Late Devonian) the
world oceans were severely depleted in dissolved oxygen
(for example, Schlanger andJenkyns, 1976). This deple-
tion was probably the result of the complex interplay of
several factors, including paleoclimate and water circula-
tion. During those times the OML expanded both upward
and downward because of poor supply of oxygen to sub-
surface waters. In times like the mid-Cretaceous, when a
major transgression had greatly increased the continen-
2. ORGANIC FACIES 11
Continental I Continental
lope I shelr
Oxidized
(;tn to whitl'
tal-shelf area, an upward expansion of the OML led to a
tremendous increase in the surface area covered by
anoxic bottom waters (fig. 2.7). It is not coincidental that
these were times of deposition of large amounts of or-
ganic-rich rocks in many parts of the world.
RESTRICTED CIRCULATION
INTRODUCTION. Settings in which circulation is restricted
are much more common than stagnant basins. Further-
more, because of their connection with the open-marine
realm, those environments can also incorporate the fea-
tures of an oxygen-minimum-Iayer model.
SHALLOW SILLING. Circulation is often restricted by the
presence of a sill, the point of connection between the
restricted area and the open-marine environment. Where
the sill is shallow (fig. 2.8), the waters entering or leaving
the basin are near-surface. In an evaporitic environment
(Karabogaz in the Caspian Sea) there is a net flow of
water into the basin, whereas in a fluvially dominated
system (Black Sea) the net flow of surface water is out
over the sill. In either case, if the basin is deep enough,
permanent density stratification will develop, with the
bottom layer almost isolated from the open-marine wa-
ters. In actuality there is a lazy turnover of the bottom
waters, but it is too slow to disturb the anoxia which
develops in the bottom layer.
There are numerous examples of important organic-
rich source rocks that were deposited in shallowly silled
 12
Contin!;'nwl
,;5('
C..ontinenwl Continc'nwl
, lop<' shelf
+2~:~~:_~__:_:_~_~_~·_:~~_~__
~_~~~_~_~_t_:_~_~_~~~~_~~~~~~~1.l
- 400-
- 800- Expand!;'d Ol Minimum
lay!;''' < 0.2 rnL
- 1200-
- 1600-
- 2000-
_ __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _- J
'
'
FIGURE 2.7 &hematic diagram of an expanded D.lygen-
minimum layer. Expansion upward permits low-oxy,gen bot-
tom waters to move onto the broan expanses of continental
shelf and thereby increase the volume of low-oxy'~en sediment.
basins. These include the La Luna Limestone of
Venezuela and Colombia, the basinal Smackover Lime-
stone of the Gulf Coast, the Hanifa-Hadriya-Tuwaiq
Mountain Limestone of Saudi Arabia, the Shublik Forma-
tion ofthe North Slope of Alaska, the Paradox Member of
the Hermosa Formation of Utah, and the Phosphoria For-
mation of the western United States.
A shallow-sill model may also be applicable to epeiric
seas, such as those responsible for deposition of several
ancient sequences in the midcontinent region of the
United States (Cretaceous Mowry and Graneros shales,
Pennsylvanian Cyclothems, and Chattanooga-Wood-
ford-New Albany-Antrim-Bakken-Exshaw black shales
of Late Devonian-Early Mississippian age), and the Kim-
meridge Clay of the North Sea. Where shallow sills isolate
large portions of the epeiric sea from free circulatory ex-
change with the open ocean, anoxic sediments may be
deposited regionally.
Shallowly silled basins often yield evaporites, which
Kirkland and Evans (1981) showed could be excellent
hydrocarbon-source rocks. Evaporitic environments com-
bine the opportunity for abundant growth of algae with
ideal conditions for preservation. Nutrients are concen-
trated by evaporation, and grazers and predatory or-
ganisms are eliminated by the high salinities. High
productivity reduces oxygen levels, and high hydrogen-
I Sudan' \\.111"
,'lIll1"III'""U'
11,,\\
FIGURE 2.8 &hematic diagram of a shallowly silled basin,
Density stratification occurs if the basin is deeper than about
200 m, because water interchange affects mainly the surface
waters, As there is no good mechanism to bring oxy'~en into
the waters of the deep basin, sediments deposited there will
be low in oxy'~en,
sulfide concentrations create conditions poisonous to
predators. The result is often deposition of organic-rich
laminae within, or as lateral facies equivalents of, evapo-
rites. The Todilto Limestone Qurassic of New Mexico) is a
rare example of a lacustrine evaporite.
DEEP SILLING. If a sill is placed deeply enough' to intersect
the oxygen-minimum layer, and if that OML is intensely
developed, anoxia may develop by another mechanism.
Water entering the basin horizontally immediately above
the sill will be low in oxygen (fig. 2.9). There is therefore
no mechanism to bring oxygenated water into the bottom
of such a basin. The sediments deposited within such a
basin will be anoxic, and the organic matter within those
sediments will be well preserved.
A well-studied modern example is the Santa Barbara
Basin off the coast of southern California. Ancient exam-
ples include the Puente and Monterey formations
(Miocene) of southern California, the Eocene-age Krey-
enhagen Formation of the southern Great Valley of
California, and the organic-rich Mesozoic shales of the
North Slope of Alaska.
Not all deeply silled basins have the correct geometric
characteristics to become anoxic, however. If the sill
depth lies below the OML, the water entering over the sill
will be oxygenated, and preservation in the basinal sedi-
ments will not be enhanced (fig. 2.10). Several other ba-
sins in the Borderlands area near the Santa Barbara Basin

Uifi.0.ti.i.ttGGttUU~:~~~:8{i:UM1:f:
............................................................
:::::::::::::::::::::::::::::::::::,\nw.it· 01' !>!l'" t· (),::
... ::::::::::::::::::: ~:::~::::: :::::::::::::::::::::::::
':: :: Anoxic: :::. '~??}:~::;J:~Ji8:ilii08:8~[:I!:~
in o,,!pnk matlt'!' '-:-::::»::UU/UH
FIGURE 2.9 Schematic diagram of a deeply silled basin in
which the sill intersects the oX}'gen-minimum layer. Horizon-
tal movement of low-D.1:}:g'en water over the sill keeps the deep
basin sediments low in 0x:v..~en.
have poorly placed sills, and thus are not accumulating
anoxic sediments today.
DENSITY STRATIFICATION. Luz (1979) and Pratt (1984) have
suggested that geologically brief periods of density
stratification can be caused by cycles of high rainfall. In
this model, freshwater run-off forms a layer oflight water
above the denser marine waters below, as illustrated for
the Black Sea in figure 2.8. Oxygen thus cannot be in-
troduced to the lower water layer where sedimentation is
occurring.
The difference between this model and that for the
Black Sea is subtle. In the Black Sea the shallow sill pro-
vides the main restriction; freshwater run-off enhances
the isolation of the bottom waters. In the models of Luz
and Pratt, periods of high fluvial input are necessary be-
cause silling is not well developed.
COAL SWAMPS. Large amounts of organic material are
preserved in coal swamps as a result of the combined
effects of poor water circulation, high influxes of organic
matter, and diminished bacterial activity. Coal swamps
can develop under a variety of conditions in both marine
and nonmarine environments. Although circulation in
coal swamps is generally sluggish, the shallowness of the
swamps prevents the waters themselves from becoming
anoxic. Anoxia develops within the sediments rather than
in the water column. Phenolic bactericides derived from
lignin hinder bacterial decay in the water and throughout
the sediment column. Lack of sulfate in nonmarine
2. ORGANIC FACIES 13
CONTENT Of DISSOlVED O:! .. WAT£R
. . - tilGti WAT£R
FLUX
_----- lOW WATER
FLUX
FIGURE 2.10 Schematic diagram of a deeply silled basin in
which the sill is below the oX}'gen-minimum layer. The bot-
tom waters of the deep basin will thus be oX}'8enated.
swamps further prevents anaerobic microbial destruction
of the organic matter.
For many years coals have been considered to be plau-
sible source rocks for gas accumulations, but their poten-
tial for generating oil was thought to be small. As we
shall see in chapter 8, however, recent work suggests that
the old concept is probably partly in error; in some areas
(for example, the Gippsland Basin of Australia and the
Mahakam Delta of Kalimantan) coals have almost cer-
tainly functioned as effective source rocks for oil.
OXIC SETIINGS. Most depositional settings not spe-
cifically catalogued above will be more or less well oxy-
genated, and therefore will contain primarily oxidized
organic matter. Near-shore oxidizing facies sometimes
have high TOC values, but the organic material is almost
invariably woody. Abyssal sediments are notoriously low
in organic carbon as the result of the combined effects of
high oxygen levels in abyssal waters, very slow sedimen-
tation rates, and low productivity in the overlying pelagic
14

realm. The hydrocarbon-source potential of all of these

oxidizing facies is low, and more favorable for gas than
for oil. •
•
Type of Organic Matter. Organic matter of algal (phyto- 8
planktonic) origin is consumed more readily by organ-
isms than are other types of organic material, because its
~
() t:I W.8ALTIC
chemical components are digestible and provide precisely oI- • PERU

the nutrients required by scavengers and predators. Ni-

trogen and phosphorus are in particular demand; their ., f::r0REGON
o N.W .... FRIC ...

virtual absence in much terrestrial organic material, espe-
cially 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 dia-
genesis 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 in-
clude woody, cellulosic, lignitic, cuticular, or resinous
material, all of which are chemically quite distinct from
each other. It may also contain very resistant organic de-
bris 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 in-
crease as sediment-accumulation rates increase (fig.
2.11), as a result of more rapid removal of organic mate-
rial from the zone of microbial diagenesis.
Rapid burial can be accomplished by a high influx of
inorganic detritus, biogenic inorganic sediment, or or-
ganic material. Rapid deposition of inorganic detritus is
common in turbidites and in prodelta shales. The ex-
tremely high accumulation rates for biogenic carbonates
and siliceous sediments in zones of high productivity pro-
mote 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 col-
umn 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-
• l!:. ... RGENTINE B... SIN
• CENTR ... L P... CIFIC
0 . 1 r-'-TTTn~-'-'OTnn'-~TT,"~-'-'TTmm
0.1 1 10 100 1000
SEDIMENTATION RATE (eM/l000Y)
FIGURE 2.11 Dependence ofTOC on sedimentation rate.
Higher rates of burial and rerrwval from the zone of
diagenesis prorrwte preservation. After Muller and Suess,
1979, with permission. Copyright 1979, Pergarrwn Press, Ltd.
tle several orders of magnitude faster than individual
phytoplankton.
DILUfION
Although high sediment-accumulation rates enhance
preservation of organic matter, at very high accumulation
rates dilution may become a more important factor than
increased preservation (fig. 2.12). Dilution does not re-
duce the total amount of organic matter preserved, of
course, but it does spread that organic material through a
larger volume of rock. The net result is a reduction in
TOC values.
Dilution effects depend upon rock lithology (fig. 2.12).
Biogenic sediments, in which the organic and inorganic
materials arrive together, are not as strongly affected by
dilution. Shales, in contrast, show strong dilution effects
when accumulation rates are very high. Facies changes
from carbonates to shales may create large dilution effects
that can be wrongly interpreted as indicating changes in
oxygen levels.

10
!
o
o
....
1 10 100
SEDIMENT - ACCUMULATION RATE (M/MY)
FIGURE 2.12 Dependence of TOC values on sediment-accumu-
lation 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.
EXAMPLES OF RICH AND LEAN SEDIMENfS
Virtually everyone has seen samples of both black, or-
ganic-rich rocks and oxidized, organic-lean shales. De-
spite 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 sedi-
ments containing more than 2% TOC and high propor-
tions 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-
2. ORGANIC FACIES 15
FIGURE 2.13 Core 17 from Hole 550
of Leg 80 of the Deep Sea Drilling
Project, Goban Spur, North Atlantic.
Black, laminated, organic-rich sedi-
ments of middle Cenomanian age
grade cyclically into and out of dark,
slightly bioturbated sediments of
lower organic-carbon content, which
in tum grade into light-gray or
white, heavily bioturbated sediments
with low to very low TOC contents.
elusions about organic facies will be gross oversimplifi-
cations.
A second core from the same hole is slightly younger
(Turonian-Coniacian?). The sediments pictured in the il-
lustration on the cover were deposited below the calcite-
compensation depth, and thus contain no carbonate. The
resulting slow sediment-accumulation rates may have
contributed to increased oxidation of organic matter. The
core is black at the bottom and grades sequentially up-
ward into green and red. The white sediments near the
top of the core are chalky turbidites. These colors reflect
the dominant forms of iron in the sediments: black for
pyrite, green for Fe+ 2 , red for Fe+ 3 • TOC values correlate
perfectly with color; they decrease monotonically from
black to red, tracing the gradual increase in oxygen con-
tent of the bottom waters.
None of the sediments in the cover illustration are
particularly rich in organic matter. Even the blackest
samples, when examined carefully, were found to be
bioturbated. TOC values were mostly around 0.5% for the
black samples, with a maximum of 0.7% . Very little
marine organic matter was preserved. The black color is
16

Geologit:al H.I ' IU~ 1.,llm~

pt'liods I'rindpal coal rt'SOlllTl"S
~ lUI ~ 1.1 • .!uu tI .,!tltl
Principal prolific oil-source rocks

Tel'lial"\' Indol1l'Sia. Californi". Vl'lwzul'la. Cmlc,,~ulo

Norlh Anll'';t·a. far Casl
100 CreWe ous Middk Easi. C,II1<1da
N. AIlll'ril'tl. l ." R. China Mexico, Venezuela, Equador, Colombia
Junl -it' Middll' CaSI. Ml'lI.ko
200 l 5SI{. Asia. AuslI'"lia North: 'a. Middle East
TI'iassil' Mexiro. Siheria. Australi;l. C('nll'al Aloia
Permian (:ondw'II1<1. l S5R. China
West Tl'xas. Roc'''y Mountains
300 rbonifer. N. r\m 'rica. Luropa
Sahara. Volga-l nil
De\'onian C;lI1ada. \Vest T'lI.as
400
Silul'ian Sahara. \\'eSI Texas
OrdOl;eian
500
C:lmbl'ian

FIGURE 2.14 Occurrences of important source ami reservoir

probably due to finely divided pyrite formed after burial.
There is therefore no evidence to suggest that the local
waters were anoxic during the Coniacian. This particular
core may in fact record the end of the general tendency
toward low oxygen levels in the mid-Cretaceous North
Atlantic. Once again, only core samples could possibly
give us such delicate control in understanding organic
facies.
GENERAL MODELS FOR
SOURCE-ROCK DEVELOPMENf
In addition to the predictive models for upwelling based
on theoretical considerations, we have at our disposal
more empirical models to aid in our understanding of
organic-facies relationships. Chief among these is the
work on coastal-onlap curves and facies-wedge cycles by
researchers at Exxon (Vail et al., 1977; White, 1980).
These models provide a context within which we can
interpret observed rock sequences, and permit us to pre-
dict where organic-rich facies are likely to have been de-
posited. Combined with seismic stratigraphy (Vail et al.,
1977), these facies models can be of value, especially in
frontier areas.
A large proportion of the major source rocks around
rocks throughout Phanerozoic time compared to transgres-
sions 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.
the world were deposited during major transgressions,
particularly in shallow, restricted, shelf environments.
Good source rocks are thus often favorably juxtaposed
with reservoir rocks, which proliferate during regressive
events (fig, 2.14).
SUMMARY
There are three principal factors that affect the amount of
organic matter in sedimentary rocks: primary photosyn-
thetic productivity, effectiveness of preservation, and dilu-
tion by inorganic material. Of these, preservation is
generally the most important.
Productivity can be predicted by locating ancient sites
of marine upwellings. Our ability to make accurate pre-
dictions is limited, however, by uncertainties about exact
continental positions and configurations in the past, lack
of knowledge of sea-water chemistry and nutrient avail-
ability at those times, and a very imperfect understanding

of oceanic- and atmospheric-circulation patterns. Conse-
quently, such models are not yet of much practical value
for the distant past.
Preservation is best accomplished where oxygen is ex-
cluded from bottom waters. There are a number of mech-
anisms 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 sedi-
ment 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 hy-
drocarbon-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 depos-
ited discontinuously through time and space. Direct con-
trol of the anoxia was thus probably local, as a result of
high productivity or sluggish circulation. As in the mod-
ern 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 valu-
able in the future for understanding hydrocarbon systems
in basins. To derive maximum value from geochemical
2. ORGANIC FACIES 17
analyses, we should always strive to place the organic-
rich rocks in the larger context of basin evolution through
time and space.
SUGGESTED READINGS
Arthur, M. A. and J. H. Natland, 1979, Carbonaceous sedi-
ments in the North and South Atlantic: the role of salinity in
stable stratification of Early Cretaceous basins, in M. Tal-
wani, W. Hay, and W. B. F. Ryan, eds., Deep Drilling Results
in the Atlantic Ocean: Continental Mar,'sins and Paleoenvi-
ronment: 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 Associa-
tion 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 facies-
stratigraphic concept and exploration tool, in A. Saldivar-
Sali, 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 depo-
sitional environments of the Monterey Formation, California,
in R. E. Garrison and R. G. Douglas, eds., The Monterey For-
mation and Related Siliceous Rocks of California: SEPM
Pacific Section, pp. 97-122.
18

Pratt, L. M., 1984, Influence of paleoenvironmental factors on

preservation of organic matter in middle Cretaceous
Greenhorn Formation, Pueblo, Colorado: Bulletin of the
American Association of Petroleum Geologists, v. 68, pp.
1146-1159.
Rhoads, D. C. and]. W. Morse, 1971, Evolutionary and ecologic
significance of oxygen-deficient marine basins: Lethaia, v. 4,
pp.413-428.
Savrda, C. E., D.]. Bottier, and D. S. Gorsline, 1984, Develop-
ment of a comprehensive oxygen-deficient marine biofacies
model: evidence from Santa Monica, San Pedro, and Santa
Barbara Basins, California continental borderland: Bulletin
of the American Association of Petroleum Geologists, v. 68,
pp. 1179-1192.
Stutzer, 0., 1940, Geology of Coal: translated by A. C. Noe,
Chicago, University of Chicago Press.
Waples, D. W., 1983, Reappraisal of anoxia and organic rich-
ness, with emphasis on Cretaceous of North Atlantic: Bulletin
of the American Association of Petroleum Geologists, v. 67,
pp. 963-978.
Chapter 3 Organic Chemistry
and Isotopes

INTRODUCTION
Anyone who uses petroleum geochemistry must be famil-
iar with basic chemical terminology. The objective of this
chapter is to acquaint the reader with the names of com-
mon compounds and with several different conventions
for drawing their structures. This objective is very differ-
ent 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 be-
hind isotope effects.
All compounds containing carbon atoms, except car-
bon 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 carbon-
containing 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 contain-
ing only the elements carbon and hydrogen. Petroleum
and natural gas are themselves often referred to as "hy-
drocarbons," but that usage is incorrect from the chem-
ist's point of view because those materials often contain
substantial amounts of nitrogen, sulfur, oxygen, trace

19
20
metals, and other elements. In this chapter we restrict our
usage of the term hydrocarbon to the standard chemical
one; elsewhere in this book usage will vary, as it does in
the real world.
Examples of hydrocarbons are methane, ethane, and
cyclohexane, whose structures are shown below.
H H H
I I I pentane are equivalent:
H-C-H H-C-C-H
I I I
H H H
Methane Ethane Cydohexane
Each carbon atom is represented by a C; each hydrogen
atom by an H. The lines show the chemical bonds be-
tween the atoms.
In each of these compounds, and indeed in every
carbon compound (except a few highly unstable ones
created only in laboratories), every carbon atom forms
four bonds. Similarly, hydrogen always forms one bond;
oxygen and sulfur, two bonds; and nitrogen, three bonds.
Carbon atoms like to form bonds with each other, creat-
ing long chains and ring structures. This unique property
of carbon is responsible for the existence of literally mil-
lions of different organic compounds.
Writing the detailed structure of a simple molecule like
methane is no problem, especially if one has to do it only
occasionally. If one wants to draw large molecules, how-
ever, the explicit inclusion of every atom and every bond
becomes extremely tedious. Several different types of
shorthand have therefore developed to facilitate drawing
organic molecules.
One common convention is to represent all the hydro-
gen atoms attached to a given carbon atom by a single H,
using a subscript on the H to denote the total number of
hydrogens around that atom. The structures of methane,
ethane, and cyclohexane are thus represented by
or
Methane Ethane Cydohexane
We can make other logical simplifications for longer
carbon chains. The following representations of n-
or
CH 3 (CH 2 )3 CH 3
n-pentane
An even quicker shorthand that uses no letters at all
has evolved. Each carbon atom is represented by a point,
and carbon-carbon bonds are shown as lines connecting
those points. Hydrogen atoms and bonds to hydrogen
atoms are not shown at all. Because we know that each
carbon atom forms four bonds and each hydrogen atom
forms one bond, simple inspection shows how many hy-
drogen atoms each carbon atom must have. For example,
n-pentane and cyclohexane are represented by the line
structures shown below.
o
n.pentane Cydohexane
The zigzag configuration illustrated for n-pentane is
adopted to show clearly each carbon atom.
The simplest series of hydrocarbons has linear struc-
tures; these molecules are called n-alkanes or n-
paraffins. The letter n stands for nonnal, and indicates
that there is no branching in the carbon chain. We have
already encountered n-pentane; the names of the other
nine simplest n-alkanes and three ways of representing
each of them are given in table 3.1. Note that the name of
 3. ORGANIC CHEMISTRY AND ISOTOPES 21

TABLE 3.1 Names amI various ways of We have also seen that carbon atoms can be arranged
depicting the ten smallest n-alkanes in rings. These cyclic compounds (called naphthenes by
Name Abbreviations
geochemists) are named by counting the number of car-
bon atoms in the ring and attaching the prefix cyclo. Ex-
Methane CH 4 CH 4 None amples of cycloalkanes are shown in figure 3.1.
Ethane CzHG CH 3 CH 3 None Steranes are cycloalkanes that normally contain three
Propane C3 H 8 CH:l CH zCH 3 A 6-carbon rings and one 5-carbon ring (fig. 3.1). Triter-
Butane C4 H lO CH 3 (CH zhCH:l /V panes contain five or (infrequently) six rings. The rings
Pentane CS HIZ CH:l (CH zhCH 3 AA are designated A-F, and each carbon atom receives a
Hexane C6 H14 CH 3 (CHz)4 CH 3 /VV number, as shown in figure 3.2.
Heptane C7 H 16 CH 3 (CHzlsCH 3 /"v"V'.. All the compounds mentioned above are called
Octane CaH 18 CH:l ( CHZ)6 CH 3 /VVV saturated hydrocarbons or saturates, because they are
Nonane CsHzo CH 3 (CH2 hCH 3 ~ saturated with respect to hydrogen. That is, no more hy-
Decane ClO H 2Z CH 3 (CH zhCH 3 /VVV'V drogen can be incorporated into the molecule without
breaking it apart.
Another important group of hydrocarbons is the un-
each compound ends in -ane, as in "alkane." The first saturates, which, in contrast, are able to combine with
four names are irregular, but the prefixes denoting the additional hydrogen. Many unsaturated compounds have
number of carbon atoms in the other alkanes are derived carbon-carbon double bonds; these compounds are
from Greek numbers. called alkenes or olefins. Examples are ethene, propene,
Carbon atoms need not always bond together in a and cyclohexene, the structures of which are shown be-
linear arrangement. Branching can occur, giving rise to a low. They are named in a similar manner to the alkanes,
vast number of possible structures. For example, two of except that the ending -ene indicates the' presence of a
the many compounds offormula C7 H 16 are shown below. double bond.

2-methylhexane 2,2,3-trimethylbutane
H

H/
"c=c /
"H
Ethene
H H

.H /
"c=c /
Propene
"
CH 3

H
o
Cyclohexene
(Ethylene) (Propylene)

The term methyl, which we used earlier, is the adjec-

tival form of the word methane. In the case of 2- Another important alkene is isoprene, from which the
methylhexane (above) the basic structure is hexane; a isoprenoids, steranes, and triterpanes are formed.
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 pro-
pyl).
Among the most important branched hydrocarbons in
Isoprene
organic geochemistry are the isoprenoids. Regular iso-
prenoids consist of a straight chain of carbon atoms with a
methyl branch on every fourth carbon. Isoprenoids rang- Because alkenes are highly reactive, they do not long
ing in length from six to forty carbon atoms have been persist in geologic environments. In the laboratory they
found in petroleum and rocks (table 3.2). are readily converted to alkanes by the addition of hydro-
22

TABLE 3.2 Structures of some geochemically important isoprenoid hydrocarbons

Number of
Carbon
Structure Name Atoms

Phytane 20

Pristane 19

Norpristane 18

17

16

Farnesane 15

squalane 30

Lycopane 40

Perhydro-
j3-Carotene 40
(j3-Carotane)

gen in the presence of a catalyst. The hydrogenation of double bonds, but they actually have completely different
ethene to form ethane is shown below. chemical properties from alkenes and are unusually sta-
ble. Although they are unsaturated, they do not add hy-
catalyst drogen easily. Their stability permits aromatics to be
H2 + H2C=CH 2 ---~) H3 CCH 3 (3.1) important constituents of oils and sediments. Some typical
Ethene Ethane and important aromatic hydrocarbons are shown and
named below.

o
A variety of reactions, including hydrogenation, converts
alkenes to alkanes and cyclic compounds during
diagenesis.
Aromatics form an extremely important class of un-
saturated hydrocarbons. At first glance aromatics appear
to be nothing more than cyclic alkenes containing several Benzene Toluene m-xylene Naphthalene
 3. ORGANIC CHEMISTRY AND ISOTOPES 23

Basic sterane Basic triterpane

structure structure
±C30 ±C30

FIGURE 3.1 Basic structures of some typical cyclic and poly-

cyclic hydrocarbons.
23

FIGURE 3.2 Structures, carbon-numbering systems, and ring

Aromatics possess a system of alternating single and designations for steranes (top) and triterpanes (bottom). Re-
double bonds within a cyclic structure. A simplified nota- printed by permission of Academic Press from Mackenzie,
tion for drawing these molecules permits us to represent 1984.
the double-bond system by a circle within the ring. The
circle indicates that the electrons in the double bonds are
delocalized; that is, they are free to move throughout the are quite common. The extreme case is graphite, which is
cyclic system instead of being held between two particu- an almost-endless sheet of aromatic rings.
lar carbon atoms. It is this delocalization of electrons
which makes aromatic compounds very stable. The struc-
tures of two common light aromatic hydrocarbons are
shown below.

Polycyclic aromatic hydrocarbons

Toluene Naphthalene

Some compounds (called naphthenoaromatics) contain

Some aromatic molecules are very large. Polycyclic aro- both aromatic and naphthenic rings. Many naphthe-
matic hydrocarbons (PAR) having fused ring structures noaromatics are derived from steranes and triterpanes.
24

o
II
OH

PALMITIC ACID
(hexadecanoic acid)

Naphthenoaromatic hydrocarbons OH

The hydrocarbons we discussed earlier are relatively /V"V'VV'V

simple molecules. Although they are very important con- DODECYL ALCOHOL

stituents of petroleum, these compounds are quite differ-

ent from the majority of the organic molecules found in
FIGURE 3.3 Examples offatty acms and alcohoL, derived
living organisms. Most biological molecules are larger
from living organisms.
and more complex than the simple hydrocarbons; the
majority contain oxygen, nitrogen, phosphorus, sulfur, or
other elements. The hydrocarbons present in petroleum
are mostly the end products of extensive degradation of
biogenic molecules. In fact, some complex hydrocarbons
that are found in fossil organic material can be related
directly to individual biological precursors. Reactions that
convert biogenic molecules to hydrocarbons are discussed
later in this chapter.

NONHYDROCARBONS
Atoms other than hydrogen and carbon that occur in
petroleum, bitumen, and kerogen are called heteroatoms;
the compounds in which they occur are called heterocom-
pounds. Heterocompounds are also called NSO com-
pounds, because the most common heteroatoms are
nitrogen, sulfur, and oxygen. Fossil organic matter often
contains a wide variety of heterocompounds, of which
some are biogenic and others are formed during dia-
genesis. Many of the heterocompounds present in organ-
isms are converted to hydrocarbons during diagenesis
and catagenesis.
The heterocompounds present in fossil organic mate-
rial are difficult to isolate and identifY, but a few types of
molecules have been studied and used in geochemical
interpretations. Fatty acids, derived from natural fats,
oils, and waxes, were among the first NSO compounds to
be studied, but they are seldom used today. Those
molecules terminate in a carboxyl group (COOH). Closely
related are alcohols (fig. 3.3).
One of the most important classes ofNSO compounds is
the porphyrins. These molecules are structurally related
R'
DPEP type ETIO type
FIGURE 3.4 Examples of the principal types of porphyrins
present in petroleum and rock and sediment extracts.
to, and in most cases derived from, chlorophyll. There are
several different families of porphyrins present in oils and
bitumens; two important types are shown in figure 3.4.
Early work on porphyrins provided important evidence
about the organic origin of petroleum.
Many common NSO compounds are not directly re-
lated to biogenic precursors. Among the most important
NSO compounds are the asphaltenes, which are large,
highly aromatic materials of varying structure (fig. 3.5).
They have many characteristics in common with kerogen,
but asphaltene molecules are smaller and more aromatic
than most kerogens.

FIGURE 3.5 A portion of a typical asphaltene molecule.
Many nonhydrocarbon molecules common to living or-
ganisms are also present in sediments. Among these are
lignin, carbohydrates, and amino acids. Lignin is an im-
portant component of wood, providing much of the struc-
tural 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
Lignin monomers are linked together to form molecules
having molecular weights from 3000 to 10,000 atomic
mass units (amu). Upon decomposition lignin forms
phenolic compounds, which are aromatics having a hy-
droxyl group (OR) attached. Because phenols are potent
bactericides, lignin is rather resistant to degradation, and
thus tends to become concentrated as other organic mat-
ter is decomposed.
Carbohydrates include starch, sugars, and cellulose;
the latter is the most abundant organic compound in the
biosphere. Like lignin, it is an important constituent of
terrestrial organic matter. Although cellulose is quite re-
3. ORGANIC CHEMISTRY AND ISOTOPES 25
H H
H
H H
FIGURE 3.6 The propane molecule, showing actual bond an-
gles of approximately 1090 •
sistant to decomposition under some conditions, most
carbohydrates are attacked readily by microorganisms.
Lignin and cellulose are major constituents of humic
coals.
Amino acids are the building blocks of proteins. They
are rapidly metabolized by virtually all organisms, how-
ever, and thus are seldom preserved in sediments (excep-
tions occur in shell material and in bones, where small
amounts of preserved amino acids can be used to date
specimens).
STEREOCHEMISTRY AND ISOMERS
When we represent chemical structures on paper, we
usually depict them in two dimensions for the sake of
convenience. In some cases, however, it is desirable to
show a molecule in three dimensions, either to appreciate
subtle features of its structure, or to show how it differs in
some slight but detectable way from other molecules. The
way in which the atoms of a molecule are arranged in
space is called stereochemistry. There are many aspects
of stereochemistry that need not concern us here, but a
few are important. One is the general shape of molecules.
When a carbon atom forms four single bonds, the elec-
trons in these bonds like to stay as far apart as possible.
The four bonds are therefore arranged in a tetrahedron,
with a solid angle of lOgO between any two bonds. A
chain of three carbon atoms therefore is not linear, but
bends at an angle of lOgO (fig. 3.6). All n-alkanes thus
have a zigzag shape like our line representation of n-
pentane above. Because of internal rotational and vibra-
tional energies, however, the molecule is not static; rather
it twists and writhes in space like an agitated snake.
26
FIGURE 3.7 Benzene, an aromatic molecule, has a planar
structure with bond angles in the ring of 120°.
H H
H H
H
Cis Trans
FIGURE 3.8 Cis and trans isomers of 1,3-dimethylcyclohex-
ane. The cis fonn has the two methyl groups on the same
side of the ring; the trans fonns on opposite sides.
The configurations of molecules are therefore always
changing, and any single representation is an over-
simplification.
Cyclohexane is not a flat molecule because the require-
ment of 109° bond angles makes planarity impossible.
Aromatics, in contrast, are planar, because the introduc-
tion of a double bond changes the geometric require-
ments for bonding (fig. 3.7). The three bond angles about
a carbon atom involved in a double bond are each 120°,
and the bonds lie in a plane instead of a tetrahedron.
Polycyclic aromatics form large, flat sheets that stack
neatly, a phenomenon well known in asphaltenes and
graphite.
Molecules which in all other respects appear to be
co Cb
H
H
Cis ·DECALIN Trans ·DECALIN
(both hydrogens alpha) (one hydrogen alpha, one beta)
FIGURE 3.9 Alpha (111111 ) and beta ( ~) attachments in de-
calin. 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.
co Cis· DECALIN Trans· DECALIN
FIGURE 3.10 A second convention for showing the stereo-
chemistry 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.
identical can differ stereochemically. For example, a com-
pound 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 geome-
try of hydrogen atoms attached to ring junctures (fig.
3.10). Open circles indicate that the hydrogen is attached

FIGURE 3.11 Structural isomers of hexane (C6 H 14 ).
in the alpha position, and black circles indicate the beta
position. Models can be easily built from plastic kits in
order to observe the molecules in three dimensions and to
appreciate how a large change in molecular geometry
is often produced by a seemingly minor change in
stereochemistry.
Molecules that have the same chemical formula but a
different arrangement of atoms in space are called iso-
mers. Some isomers have different carbon skeletons (for
example, the two different compounds of formula CsH14
shown on p. 21), whereas others, as we have seen, involve
much more subtle differences. Many different types of
isomers are important in organic geochemistry. Light-
hydrocarbon analyses focus mainly on structural isomers
(fig. 3.11), whereas the most sophisticated analyses
utilize the multitude of stereoisomers present among the
polycyclic biomarkers. Biomarker stereochemistry will be
discussed further in chapters 5, 8, and 10.
REACTIONS
We need not worry about most of the reactions that or-
ganic molecules can undergo, because the majority occur
only in the laboratory. Relatively few take place in
sedimentary rocks.
3. ORGANIC CHEMISTRY AND ISOTOPES 27
Many chemical reactions involve both oxidation and
reduction. Oxidation occurs when an atom loses elec-
trons during the reaction, whereas reduction involves a
net gain of electrons. In the course of a chemical reaction,
the oxidizing agent gains electrons and is thereby re-
duced; the reducing agent loses electrons and becomes
oxidized. We are all familiar with some common oxida-
tive processes, such as combustion, rusting, or the brown-
ing of a sliced apple. Many other important oxidative
processes are operative in the geosphere.
Hydrocarbons can be oxidized in several ways.
Methane, for example, burns in the presence of oxygen to
yield carbon dioxide and water (eq. [3.2]).
(3.2)
Oxygen is the oxidizing agent in equation (3.2). Other.
materials, such as sulfate ion, can also function as oxidiz-
ing agents for hydrocarbons.
Oxidation can also occur when hydrogen is removed
from an organic molecule (eq. [3.3]).
o o
(3.3)
Reduction always accompanies oxidation. When
methane is oxidized by oxygen (eq. [3.2]), oxygen is re-
duced by methane. Reduction also occurs when hydrogen
is added to a double bond (eq. [3.1]). Hydrogen is ox-
idized in the process.
In many cases, where both the oxidizing agent and
reducing agent are organic, we are interested in the fates
of both materials. Decarboxylation (loss of a carboxyl
group) is one such process (eq. [3.4]). Methane is the
reduced product, and carbon dioxide the oxidized one.
(3.4)
Sometimes hydrocarbons function as both oxidizing
and reducing agents in the same reaction. For example,
cyclohexane can lose hydrogen and become oxidized; the
hydrogen released can be transferred simultaneously to
28

-
n-BUTANE ISOBUTANE
( 2-methylpropane)

FIGURE 3.12 Structural isomerization from n-butane to

isobutane.

FIGURE 3.13 Structural isomerization by methyl migration to

other hydrocarbon molecules to permit cracking (eq. form diasteranes from regular steranes.

o
[3.5]).

+ 3CH,CH,~ 0 + 6CH, (3.5)

tural isomerization, in which an alkyl group (usually
methyl) moves from one carbon to another. For example,
n-butane can become isobutane if the last methyl group in
n-butane moves over to the adjacent carbon atom (fig.
3.12). Methyl groups in complex molecules like steranes
Simultaneous oxidation and reduction reactions can
can also migrate, particularly from one ring junction to
also occur within a single molecule, as in equation (3.6).
another (fig. 3.13).
Cyclohexane is the oxidized product; propane, the re-

o
Another closely related isomerization is called epimeri-
duced one.
zation. Epimers are isomers that differ only in the
stereochemistry at one carbon atom. The two steranes in
+ figure 3.14 are epimers; the product is formed from the
(3.6) reactant by removal of a hydrogen atom followed by re-
turn of it or another hydrogen to the opposite side of the
molecule. Once again, the close relationship of the epi-
mers makes the reaction easy to study.
Formation of ring structures (cyclization: eq. [3.6]) is a
common occurrence during formation and transforma-
tion of kerogen. It is a favored process because it makes
substantial amounts of valuable hydrogen available for
other reactions. Cyclization is often followed by aromati-
zation (eq. [3.5]) in the transformation sequence.
Some important organic-geochemical reactions are not
oxidation-reduction reactions; others are only incidentally
involved in oxidation and reduction. Isomerization reac-
tions, in which one isomer is converted to another, are of
particular interest, because the close relationship of reac-
tant and product often makes the reaction relatively easy
to trace.
One important type of isomerization reaction is struc-
 3. ORGANIC CHEMISTRY AND ISOTOPES 29

20R

, "

FIGURE 3.14 Example of epimerization in steranes by re-

moval and replacement of the hydrogen atom attached to C- TABLE 3.3 Stable isotopes used in organic geochemistry
20. Reprinted by permission of Cambridge University Press
from Mackenzie and McKenzie, 1983. Element Isotopic abundance Standard

Carbon 12C = 98.8888 % PDB'

ISOTOPES 13C = 1.1112 %
Isotopes of an element differ only in the number of neu- Hydrogen lH = 99.985 % SMOW+
trons in the nuclei of the atoms; the number of protons and 2H = 0.015 %

electrons are the same. Many isotopes are unstable; their Sulfur 32S = 95.00 % CD=!:
34S = 4.22 %
rates of decay can in some cases be used as clocks for age-
Nitrogen 14N = 99.63 % Atmos. N2
dating ancient materials. The important isotopes in 15N = 0.37 %
petroleum geochemistry, however, are stable. For most
ordinary chemical purposes we consider the chemistries 'POB is a marine limestone consisting of a belemnite from the Pee Dee FOl"ffiation of
of all isotopes of an element to be identical; in actuality, the Cretaceous of South Carolina.
tSMOW is standard mean ocean water, distributed by the International Atomic
however, there are small but important differences in Energy Agency.
the reactions of these isotopes that make them useful tCO is the mineral !roilite from the Canyon Diablo meteorite.

geochemical tools.
The elements ofinterest in isotopic analyses are carbon,
hydrogen, sulfur, and nitrogen, in decreasing order of dioxide, whereas the carbonate species will show a
popularity. The particular isotopes measured are shown greater-than-average proportion of 13e.
in table 3.3. Stable isotopes are useful because the propor-
tions of the two isotopes of each element vary from sample CO 2 + H2 0 <z C01- + 2H+ (3.7)
to sample as a result of isotope effects. enriched in 12C enriched in 13C

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 equi-
librium 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-than-
average amount of the light isotope ct 2 e) in the carbon
Although the influence of carbonate equilibria on or-
ganic-geochemical processes is important, the equilib-
rium isotope effect plays a far less important role than the
kinetic isotope effect in petroleum geochemistry. The ki-
netic 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)

I I I I I I I I I I
-80 -70 -60 -50 -40 -30 -20 -10 o +10 +20
OLlC 0100 eLl-Rich

FIGURE 3.15 I) 13C ranges for various carbon-containing ma-

teriaLs.

CRUDE OIL
error, and the difference 3 (delta) between the two sam-
ples 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

Isotope ratios are useful because they can be measured

FIGURE 3.16 Fractionation of carbon iBotopes during photo-
synthesis. The lighter carbon reacts faster, and thus is incor-
porated into organic matter preferentially (kinetic isotope
£jfictJ. The heavier carbon preftrs to be in the form of car-
bonate, which is in equilibrium with carbon dioxide dis-
solved in natural waters (equilibrium isotope effect).
the light isotope compared to the original starting mate-
rial, whereas any unreacted starting material will be en-
riched 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
quite accurately, and because they vary measurably from
sample to sample. Figure 3.15 shows ranges of 3 13C
values for organic and inorganic carbon-containing mate-
rials. Organic carbon and atmospheric carbon dioxide
are isotopically very different, as a result of the kinetic
isotope effect operating during photosynthesis (fig. 3.16).
The various kinds of organic materials also differ isotopi-
cally (compare methane with petroleum, for example).
Finally, within each type of material the range of mea-
sured values is rather large. Isotope ratios therefore can
give a detailed, although often very complex and difficult-
to-interpret, summary of the origin and history of organic
matter. Chapter 7 discusses measurement of isotope ra-
tios, and chapter 10 shows how to interpret isotope data.
Chapter 4 Kerogen

INTRODUCTION
Kerogen is normally defined as that portion of the organic
matter present in sedimentary rocks that is insoluble in
ordinary organic solvents. The soluble portion, called
bitumen, will be discussed in chapter 5. Lack of solubility
is a direct result of the large size of kerogen molecules,
which have molecular weights of several thousand or
more. Each kerogen molecule is unique, because it has
patchwork structures formed by the random combination
of many small molecular fragments. The chemical and
physical characteristics of a kerogen are strongly in-
fluenced by the type of biogenic molecules from which the
kerogen is formed and by diagenetic transformations of
those organic molecules.
Kerogen composition is also affected by thermal-
maturation processes (catagenesis and metagenesis) that
alter the original kerogen. Subsurface heating causes
chemical reactions that break off small fragments of the
kerogen as oil or gas molecules. The residual kerogens
also undergo important changes, which are reflected in
their chemical and physical properties.
Kerogen is of great interest to us because it is the source
of most of the oil and some of the gas that we exploit as
fossil fuels. Diagenetic and catagenetic histories of a kero-
gen, as well as the nature of the organic matter from
which it was formed, strongly influence the ability of the
kerogen to generate oil and gas. A basic understanding of
how kerogen is formed and transformed in the subsurface
is therefore important in understanding how and where
hydrocarbons are generated, whether these hydrocarbons

31
32

are mainly oil or gas, and how much oil or gas can be
expected. BIOGENIC MOLECULES MAJOR CONSTITUENTS
LIFE
OF LIVING MATTER
The term kerogen was originally coined to describe the ------
organic matter in oil shales that yielded oil upon retort-
ing. Today it is used to describe the insoluble organic
;;;
.0 1
0 BIOCHEMICAL AND
CHEMICAL
DEGRADATION If)
u;
material in both coals and oil shales, as well as dispersed a: 1 w
...ww
.
Z
SMALLER FRAGMENTS
organic matter in sedimentary rocks. As figure 2.1 shows, w

0 "Q
CONDENSATION,
! 1 POL YMERIZATION
the amount of organic matter tied up in the form ofkero-
gen is far greater than that in living organisms or in eco- ......
:z: HUMIC SUBSTANCES

..
c 0 LOSS OF
nomically exploitable accumulations of coal, oil, and .... ll'-METHANE
CO 2 , H 2 0, NH3
natural gas.

)}o;,
ii: 10 0 KEROGEN ---(1)---
Coals are a subcategory of kerogen. Humic coals are '"
III u;
W

"....
Z
best thought of as kerogens formed mainly from land- 100 0 THERMAL w

plant material without codeposition of much mineral

matter. Algal (boghead) coals are formed in environ-
ments where the source phytoplankton lack both calcare-
ous 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 there-
fore be viewed merely as sedimentary rocks containing
special types of kerogens in very high concentrations.
KEROGEN FORMATION
The process of kerogen formation actually begins during
senescence of organisms, when the chemical and biolog-
ical destruction and transformation of organic tissues be-
gin (fig. 4.1). Large organic biopolymers of highly regular
structure (proteins and carbohydrates, for example) are
partially or completely dismantled, and the individual
component parts are either destroyed or used to construct
new geopolymers, large molecules that have no regular or
biologically defined structure. These geopolymers are the
precursors for kerogen but are not yet true kerogens. The
smallest of these geopolymers are usually called fulvic
acids; slightly larger ones, humic acids; and still larger
ones, humins. During the course of diagenesis in the wa-
ter column, soils, and sediments, the geopolymers be-
come larger, more complex, and less regular in structure.
True kerogens, having very high molecular weights, de-
velop after tens or hundreds of meters of burial.
The detailed chemistry of kerogen formation need not
concern us greatly. Diagenesis results mainly in loss of
water, carbon dioxide, and ammonia from the original
geopolymers (fig. 4.1). If anaerobic sulfate reduction is
10,00 c GAS
MATURATION
..
0
-----
...ciw
CRACKING
DEAr CARBON
::E
FIGURE 4.1 Transformation of organic material in sediments
and sedimentary rocks.
occurring in the sediments, and if the sediments are de-
pleted 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. Carbon-
carbon double bonds, which are highly reactive, are con-
verted into saturated or cyclic structures.
Kerogen formation competes with the destruction of
organic matter by oxidative processes. Most organic oxi-
dation in sedimentary environments is microbially me-
diated. 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 bac-
terial degradation, because the bacterial enzyme systems
do not know how to attack them. In an oxidizing environ-
ment many of the small biogenic molecules will be at-
tacked by bacteria before they can form geopolymers. In a
low-oxygen (reducing) environment, in contrast, the sub-
dued 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 33

TABLE 4.1 The four types of kerogen, the macerals ming, Utah, and Colorado. Extensive interest in those oil-
that they are composed of, and their organic precursors shale deposits has led to many investigations of the Green
Original OM
River Shale kerogens and has given Type I kerogens much
Maceral Kerogen Type
more publicity than their general geological importance
Alginite Fresh-water algae warrants. Occurrences of Type I kerogens are limited to
Exinite II Pollen, spores anoxic lakes and to a few unusual marine environments.
Cutinite II Land-plant cuticle Type I kerogens have high generative capacities for liquid
Resinite II Land-plant resins hydrocarbons.
Liptinite II All land-plant lipids; marine Type II kerogens arise from several very different
algae sources, including marine algae, pollen and spores, leaf
Vitrinite III Woody and cellulosic material waxes, and fossil resin. They also include contributions
from land plants from bacterial-cell lipids. The various Type II kerogens
Inertinite IV Charcoal; highly oxidized or are grouped together, despite their very disparate origins,
reworked material of any
because they all have great capacities to generate liquid
origin
hydrocarbons. Most Type II kerogens are found in marine
sediments deposited under reducing conditions.
Type III kerogens are composed of terrestrial organic
composed of fragments of many kinds of biogenic material that is lacking in fatty or waxy components. Cel-
molecules. Those kerogens formed under oxidizing con- lulose and lignin are major contributors. Type III kero-
ditions, in contrast, contain mainly the most resistant gens have much lower hydrocarbon-generative capacities
types of biogenic molecules that were ignored by microor- than do Type II kerogens and, unless they have small
ganisms during diagenesis. inclusions of Type II material, are normally considered to
generate mainly gas.
KEROGEN COMPOSITION Type IV kerogens contain mainly reworked organic de-
Because each kerogen molecule is unique, it is somewhat bris and highly oxidized material of various origins. They
fruitless to attempt a detailed discussion of the chemical are generally considered to have essentially no hydrocar-
composition of kerogens. Even if such a description were bon-source potential (but see Smyth, 1983, for a dissent-
possible, it would not be of great and direct significance ing opinion).
to exploration geologists. What is within our reach, and Hydrogen contents of immature kerogens (expressed as
ultimately of much greater practical value, is developing a atomic HlC ratios) correlate with kerogen type (fig. 4.2).
general method of describing gross kerogen composition In the immature state, Type I (algal) kerogens have the
and relating it to hydrocarbon-generative capacity. One highest hydrogen contents because they have few rings or
way that we can begin is by classifYing kerogens into a aromatic structures. Type II (liptinitic) kerogens are also
few general types. high in hydrogen. Type III (humic) kerogens, in contrast,
About a decade ago workers at the French Petroleum have lower hydrogen contents because they contain exten-
Institute developed a useful scheme for describing kero- sive aromatic systems. Type IV kerogens (not shown),
gens that is still the standard today. They identified three which mainly contain polycyclic aromatic systems, have
main types of kerogen (called Types I, II, and III). Subse- the lowest hydrogen contents.
quent investigations have identified Type IV kerogen as Heteroatom contents of kerogens also vary with kero-
well and have studied the chemical characteristics and gen type. Type IV kerogens are highly oxidized and there-
the nature of the organisms from which all types of kero- fore contain large amounts of oxygen. Type III kerogens
gens were derived (table 4.1). have high oxygen contents because they are formed from
Type I kerogen is quite rare because it is derived princi- lignin, cellulose, phenols, and carbohydrates. Type I and
pally from lacustrine algae. The best-known example is Type II kerogens, in contrast, contain far less oxygen be-
the Green River Shale, of middle Eocene age, from Wyo- cause they were formed from oxygen-poor lipid materials.
34

(A) ALGAL KEROGEN

ICH2'2CH3

(Do ATOMIC HIC

ABC
1.65 1.28 0.84

CoH ICH2'lOCH3 CH3

ATOMIC OIC

HYDROCARBONS
0.06

OIL
0.10

OIL + GAS
0.13

GAS

(B) L1PTINITIC KEROGEN (C) HUMIC KEROGEN

FIGURE 4..2 Schematic models of Types I, II, and III kerogens

Sulfur and nitrogen contents of kerogens are also vari- (A, B, and C, respectively) in the immature (diagenetic) stage.
able and, in some cases, interrelated. Nitrogen is derived Reprinted by permission of Elsevier Science Publishing Com-
pany from Dow, 1977.
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 car- 2.5
bohydrates contain little nitrogen, most terrestrially in-
fluenced kerogens are low in nitrogen. 2
Kerogen sulfur, in contrast, is derived mainly from sul- Euxinic
(anoxic. H~S)
fate that was reduced by anaerobic bacteria. High-sulfur ~

;0 1.5
kerogens (and coals) are almost always associated with
~.
marine deposition, because fresh waters are usually low ~

VJ
in sulfate. Sulfur is only incorporated into kerogens in :$2
1
0
large quantities where sulfate reduction is extensive and
where Fe+ 2 ions are absent (organic-rich, anoxic, .5
marine, nonelastic sediments). Many high-sulfur kero-
gens are also high in nitrogen (for example, the Permian Nonmarine
Phosphoria and Miocene Monterey Formations). 0
0 4
Environmental interpretations based on sulfur contents
are not limited to organic sulfur. A plot of pyrite concen- ,~() TOe

tration versus Toe values can be used to determine depo-

sitional conditions (fig. 4.3). FIGURE 4.3 Determination of depositional environments from
The division of kerogens into Types I-IV on the basis of pyrite-sulfur and TOC contents of sediments. Adapted from
chemical and hydrocarbon-generative characteristics has Berner and Raiswell, 1983.

been supported by another independent scheme for clas-
sifying 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 capa-
ble of assessing kerogen type with good accuracy.
The different types of kerogen particles are called mac-
erals, 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 sedimen-
tary rock includes many individual particles that are often
derived from a variety of sources. Thus few kerogens con-
sist 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 corre-
spondence 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 character-
istics intermediate between Type II and Type III kerogens
because of the presence of small amounts of resin or wax.
KEROGEN MATURATION
lNfRODUCTION
Very important changes, called maturation, occur when
a kerogen is subjected to high temperatures over long
periods of time. Thermal decomposition reactions, called
catagenesis and metagenesis, break off small molecules
and leave behind a more resistant kerogen residue (fig.
4.1). The small molecules eventually become petroleum
and natural gas.
By convention the term catagenesis usually refers to the
stages of kerogen decomposition during which oil and
wet gas are produced. Metagenesis, which occurs after
4. KEROGEN 35
catagenesis, represents dry-gas generation. Despite its
name, metagenesis is not equivalent to "metamorphism."
Metagenesis begins long before true rock metamorphism,
but it also continues through the metamorphic stage.
Although the terms catagenesis and oil generation are
often used synonymously, they are not precisely equiva-
lent. Catagenesis and hydrocarbon generation occur con-
currently, but they really represent different aspects of the
same process. Catagenesis refers to transformations of
kerogen molecules, whereas hydrocarbon generation fo-
cuses on the smaller product molecules. In this text we
shall use the terms somewhat interchangeably, especially
when we are discussing both aspects simultaneously. In
principle, however, they represent fundamentally differ-
ent perspectives. This chapter will focus on those changes
in the residual kerogen that accompany catagenesis. The
composition of the products (bitumen, oil, and gas) will
be discussed in chapter 5.
Kerogen maturation is not a reversible process-any
more than baking a cake is reversible. Furthermore, the
chemical process of maturation never stops completely,
even if drastic decreases in temperature occur. Chemical
reaction-rate theory requires that the rates of reactions
decrease as temperature decreases, but it also states that
at any temperature above absolute zero reactions will be
occurring at some definable rate. For practical purposes,
however, the rates of catgenesis are generally not impor-
tant at temperatures below about 70° C. Furthermore, in
most cases decreases of temperature in excess of about
20°-30° C due to subsurface events or erosional removal
will cause the rates of catagenesis to decrease so much
that the rate becomes negligible for practical purposes.
It is impossible to set precise and universal temperature
limits for catagenesis, because time also plays a role. Old
rocks will often generate hydrocarbons at significantly
lower temperatures than young rocks, simply because the
longer time available compensates for lower tempera-
tures. This complex interplay between the effects of time
and temperature on maturity is discussed in detail in
chapter 9.
EFFECTS OF MATURATION ON KEROGENS
Kerogen undergoes important and detectable changes
during catagenesis and metagenesis. Some of these
changes can be measured quantitatively, thus allowing us
36

TABLE 4.2 Atomic HIC ratios of some light hydrocarbons

Hie
Atomic
Compound Formula HlC Ratio 1.43

CH4 CH4 4.0

/VVVV C1oH 22 2.2
0) C lOH 20 2.0
CO C lOH 18 1.8
(X) 1.2
CO
ClOH12
ClORa 0.8 o
1.29
+~
to judge the extent to which kerogen maturation has
proceeded. The real reason for following kerogen
catagenesis, of course, is to monitor hydrocarbon genera-
tion. Although it is obvious that many measurable
changes in kerogens are related to hydrocarbon genera-
tion, it is also true that other changes in kerogen proper- 0.96
ties have little or nothing to do with it, and thus are not +
necessarily valid indicators of hydrocarbon generation.
We shall look now at the various techniques for estimat-
ing the extent of hydrocarbon generation from kerogen
properties and see how closely each of them is related to
hydrocarbon generation. 0.47
As we saw in chapter 3, the cracking of any organic
molecule requires hydrogen. The more hydrogen a kero-
gen contains, the more hydrocarbons it can yield during
cracking. Because many of the light product molecules
are rich in hydrogen (table 4.2), the residual kerogen FIGURE 4.4 Schematic view of changes in kerogen structure
gradually becomes more aromatic and hydrogen poor as and atomic HIC ratio and the hydrocarbons produced with
catagenesis proceeds (fig. 4.4). Thus the steady decrease increasing maturity.
in hydrogen content of a kerogen (usually measured as
the atomic hydrogen/carbon ratio [HlC]) during heating Nitrogen and sulfur are also lost from kerogens during
can be used as an indicator of both kerogen catagenesis catagenesis. Nitrogen loss occurs primarily during late
and hydrocarbon generation, provided that the hydrogen catagenesis or metagenesis, after hydrogen loss is well
content of the kerogen was known prior to the onset of advanced. In contrast, much of the sulfur is lost in the
catagenesis. earliest stages of catagenesis, as evidenced by low-
Figure 4.2 shows that the various kerogen macerals maturity, high-sulfur oils found in a number of areas,
have different hydrogen contents when they are imma- including the Miocene Monterey Formation of southern
ture, and that these hydrogen contents decrease with in- California.
creasing maturity. Figure 4.5, which is known as a van The most important implication of these chemical
Krevelen diagram, plots atomic HlC ratios of the three changes is that the remaining hydrocarbon-generative ca-
major kerogen types versus atomic OIC ratios. Both hy- pacity of a kerogen decreases during catagenesis and
drogen and oxygen are lost more rapidly than carbon metagenesis. All kerogens become increasingly aromatic
during catagenesis of all three kerogen types. and depleted in hydrogen and oxygen during thermal
 4. KEROGEN 37

PRINCIPAL PRODUCTS
OF
KEROGEN EVOLUTION
C02 H20
Oil
_ GAS
1!iO
u
J:
!:?
::!:
0 100
~
<

O!iO
Low matunty

0 010 020
ATOMIC OI C

FIGURE 4.5 Van Krevelen diagram showing maturation path-

ways for Types I, II, and III kerogens as traced by changes in
atomic HIC and OIC ratios. The shaded areas approximately High maturity
represent diagenesis, catagenesis, and metagenesis, succes-
sively. Reprinted by permission of the American Association
of Petroleum Geologists; adaptedfrom Tissot et al., 1974.

maturation (fig. 4.5). In the late stages of maturity, Types
I, II, and III kerogens will therefore be very similar chemi-
cally, possessing essentially no remaining hydrocarbon-
generative capacity.
Kerogen particles become darker during catagenesis
and metagenesis, much as a cookie browns during bak-
ing. There is a steady color progression yellow-golden-
orange-light brown-dark brown-black as a result of
polymerization and aromatization reactions. These reac-
tions are intimately related to important changes in the
chemical structure of kerogen, but they are not necessarily
identical with hydrocarbon generation. There is therefore
no necessary cause-and-effect relationship between kero-
gen darkening and hydrocarbon generation, and no
guarantee that a particular kerogen color always heralds
the onset of oil generation.
As kerogen matures and becomes more aromatic, its
structure becomes more ordered, because the flat aro-
matic sheets can stack neatly, much as asphaltene
molecules do (fig. 4.6). These structural reorganizations
FIGURE 4.6 Structural model of a Type II kerogen at low and
high levels of thermal maturity showing the increasing order
as aromatization proceeds and planar aromatic sheets begin
to aggregate.. Reprinted by permission of the Societe des Edi-
tions Technip: figure 2 from the article entitled "L'evolution
thermique de la matiere organique des sediments: applica-
tions d'une simulation mathematique" by B. TISSOT and J.
ESPITALIE, published in the Revue de l'Institut FraTifais du
Petrole, vol. 30, no. 5, Sept.-Oct. 1975.
bring about changes in physical properties of kerogens.
One property that is strongly affected, and which can be
used to gauge the extent of molecular reorganization, is
the ability of kerogen particles to reflect incident light
coherently. The more random a kerogen's structure, the
more an incident light beam will be scattered, and the
less it will be reflected.
Half a century ago coal petrologists discovered that the
percentage oflight reflected by vitrinite particles could be
correlated with coal rank measured by other methods.
38
DEPTH AND
TEMPERATURE
.........
INCREASING
BITUMEN
Because coal rank is merely a measure of coal maturity,
and because vitrinite particles also occur in kerogens, the
technique, called vitrinite reflectance, has been widely
and successfully applied in assessing kerogen maturity.
Cracking often produces free radicals, which are un-
paired electrons not yet involved in chemical bonds. Kero-
gens, especially highly aromatic ones, contain large
numbers of unpaired electrons. The concentration of free
radicals in a given kerogen has been found to increase
with increasing maturity. Free-radical concentrations can
be measured by electron-spin resonance (esr).
Kerogens often fluoresce when irradiated. The intensity
and wavelength of the fluorescence are functions of kero-
gen maturity.
The analytical procedures used in measuring changes
in kerogen properties with increasing maturity are out-
lined in chapter 7. Strong and weak points of each
method are discussed in chapter 8.
Some properties of kerogen change very little during
catagenesis. For example, carbon-isotopic compositions
of kerogens are affected little by maturation. Except for
darkening, the visual appearance of kerogen also does
not change during catagenesis: kerogen types are gener-
ally recognizable until the particles become black and
opaque, somewhat beyond the oil-generation window.
DIAGENESIS
........
...... CATAGENESIS
......
TOTAL BITUMEN
GENERATED "
,,
, \
,,
\
, MET AGENESIS
FIGURE 4.7 pint of bitumen generation as a function of ma-
turity (dashed line) compared to bitumen remaining in rock
(solid line). The difference between the two curves repre-
sents bitumen expelled from the rock or cracked to light
hydrocarbons.
HYDROCARBON GENERATION
As kerogen catagenesis occurs, small molecules are bro-
ken off the kerogen matrix. Some of these are hydrocar-
bons, while others are small heterocompounds. These
small compounds are much more mobile than the kero-
gen 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 39

as maturity increases. Figure 4.8 shows an unusually nice

3.000 trend for samples of Bakken Shale from a number of wells
in the Williston Basin. (Maturity increases regularly with
4 .000
depth in this area.) The homogeneity of the Bakken Shale
helps minimize data scatter.
It has become apparent in recent years that not all
5 .000
kerogens generate hydrocarbons at the same catagenetic
levels, as measured by parameters such as vitrinite reflec-
6 .000 tance. Given the significant chemical differences among
the various types of kerogens, this result is hardly surpris-
;;;
ing. The catagenetic levels at which a variety of kerogen
= 7.000

..
%
Q.
w 8 .000
. .' types generate hydrocarbons, as well as the types of prod-
ucts anticipated, are shown in figure 4.9.
Q
Resinite and sulfur-rich kerogens are able to generate
liquid hydrocarbons earlier than other kerogens because
9 .000
of the particular chemical reactions occurring in those
two materials. Resinite consists of polymerized terpanes
10.000
. . ..
.."
(ten-carbon isoprenoids) that can decompose easily by
.. reversing the polymerization process. Sulfur-rich kero-
gens decompose easily because carbon-sulfur bonds are
11.000
weaker than any bonds in sulfur-poor kerogens.
Effective generation of hydrocarbons requires that the
0 1.0 2 .0 3 .0 generated products be expelled from the source-rock ma-
HYDROCARBON NON HYDROCARBON trix and migrated to a trap. Timing and efficiency of ex-
pulsion depend on a number of factors, including rock
physics and organic-geochemical considerations. We
FIGURE 4.8 Ratio of hydrocarbons to nonhydrocarbons in
Bakken Shale extracts from a number of wells in the Willis- shall consider the latter briefly here.
ton Basin. Maturity generally increases with depth. Reprinted Many workers now believe that microfracturing of
by permission of the Rocky Mountain Association of Geolo- source rocks is very important for hydrocarbon expulsion
gists from Webster, 1984. (see chapter 6). Microfracturing is related to overpressur-
ing, which in tum is partly attributed to hydrocarbon
generation. Rich rocks will become overpressured earlier
than lean ones and thus will also expel hydrocarbons
earlier (fig. 4.10). In very lean rocks expulsion may occur
so late that cracking of the generated bitumen is competi-
tive with expulsion. In such cases the expelled products
will be mainly gas.
40

VITRINITE REFLECTANCE (%)

,
.4
,
.0 .1
I
1.0
I
1.2
I
1.4
I

<:::::::::: GAI/NAPHTHENIC CONDENSATE

~ RESINITE- {
~ RICH ~ ~A~~T~~I~-~I~~?
~
a: ~ OAS/PAIIAFFINIC~H

----------,
---- GAS
I- ______ ~ CONDENSATE ~"
: lIPTINITE-RICH [
a: ______ WAltY OIL LIGHT PARAFFINIC ~
a:
w
~ ~~~~C~H4~
I-
VITRINITE-RICH { ______G_A_S____________________________

GAS
GA8/PAIIAFFIN~ CH

HEAVY S-RICH. PARAFFINIC I

::E
o ASPHALTIC OIL NAPHTHENIC CONDENSATE

?
-----=
z

->
a:
c( GAS GAS / NAPHTHENIC C
::E ~ CONOENSATE~ H"
CLASTIC [
SEDIMENTS
<. . . PARAFFINIC/NAPHTHENIC OIL

FIGURE 4.9 Hydrocarbon-generation models from various

types of kerogens showing the type of liquid and gaseous
products generated at various vitrinite-reflectance values. Re-
printed by permission of ErdOl und Kohle, Erdgas, Pe-
R. 1 trochemie from Powell and Snowdon, 1983.
6
>-

I
II
~
III: 0
~
l- VERY RICH n
.50
c ROCKS 0
...c
:IE
0 0 SUMMARY
i
0
.75
0 MODERATELY a Kerogen begins to form during early diagenesis, when
:IE C
...z
III:
I GJ RICH
ROCKS
LEAN In large geopolymers are created from biological molecules.
0 LJ
ROCKS 0
The chemical composition and morphology of kerogen
I- 1.35
0 0 0 0
0 macerals depend both on the type of original organic mat-
~ V "V "V CRACKING
OF LIQUID He ter and on diagenetic transformations. Numerous methods
2.00
U exist for tracing the history of a kerogen and determin-
0 ing its original chemical and physical characteristics.
V Catagenesis of kerogen produces a more aromatic, hy-
drogen-poor, residual kerogen as well as small molecules
FIGURE 4.10 ExpuLsion-ofgenerated hydrocarbons from
that are the direct precursors for petroleum and natural
source rocks of varying organic richness as afunction of gas. Several methods exist for estimating the extent to
thermal maturity. which hydrocarbon generation has occurred in a given
 41

kerogen, but none of these measurements is closely linked

to the actual process of hydrocarbon generation. Thus,
although we know that oil generation does occur dur-
ing the phase we call catagenesis, we cannot always
define the limits of hydrocarbon generation with great
confidence.
The chemical composition of a kerogen controls the
timing of hydrocarbon generation and the type of prod-
ucts obtained. Kerogens formed from lipid-rich organic
material are likely to generate liquid hydrocarbons,
whereas those kerogens that contain few lipids will gener-
ate mainly gas. Kerogens formed from resinite will gener-
ate condensates or light oils quite early. High-sulfur
kerogens generate heavy, high-sulfur oils at low levels of
maturity. Other kerogens usually follow a more tradi-
tional model.
Source rocks that generate large amounts of hydrocar-
bons early are likely to expel those hydrocarbons early.
Candidates for early expulsion would be very organic-
rich rocks and those containing resinite or high-sulfur
kerogens. Conversely, those rocks that generate few hy-
drocarbons may not expel them until they have been
cracked to gas.

SUGGESTED READINGS

Berner, R. A. and R. Raiswell, 1983, Burial of organic carbon

and pyrite sulfur in sediments over Phanerozoic time: a new
theory: Geochimica et Cosmochimica Acta, v. 47, pp. 855-
862.
Dow, W. G., 1977, Kerogen studies and geochemical interpreta-
tions: Journal of Geochemical Exploration, v. 7, pp. 79-99.
Durand, B., ed., 1980, Kerogen: Paris, Editions Technip, 519 pp.
Hutton, A. c., A.J. Kantsler, A. C. Cook, and D. M. McKirdy,
1980, Organic matter in oil shales: Journal of the Australian
Petroleum Exploration Association (APEA), v. 20, pp. 44-67.
Powell, T. G. and L. R. Snowdon, 1983, A composite hydrocar-
bon generation model: Erdol und Kohle-Petrochemie
vereinigt mit Rennstoff-Chemie, v. 36, pp. 163-170.
Robert, P., 1981, Classification of organic matter by means of
fluorescence; application to hydrocarbon source rocks: Inter-
nationaljournal of Coal Geology, v. 1, pp. 101-137.
Staplin, F. L., 1969, Sedimentary organic matter, organic
metamorphism, and oil and gas occurrence: Bulletin of Cana-
dian Petroleum Geology, v. 17, pp. 47-66.
Waples, D. W., 1977, C!N ratios in source rock studies: Col-
orado School of Mines Mineral Industries Bulletin, v. 20, no.
5,7 pp.
Chapter 5 Bitumen, Petroleum,
and Natural Gas

INTRODUCTION
Petroleum obtained from reservoir rocks and bitumen ex-
tracted 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 petro-
leum. However, many unanswered questions remain
about the processes that transform bitumen into petro-
leum. 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 mi-
gration 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 com-
pounds having very different properties. The influence of
the lithologies of source and reservoir rocks on these com-
positional 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 com-
position of the kerogens that generated the bitumens. Ma-
turity 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 cor-
relations, which are discussed in chapter 10, can be par-
ticularly useful in establishing genetic relationships
among samples. In order to understand bitumen and pe-
troleum compositions and to use them for exploration,

43
44
however, we must separate the characteristics related to
kerogen composition from those related to the transfor-
mation of bitumen to petroleum and from those related to
changes occurring in reservoirs. This chapter will com-
pare and contrast bitumen and petroleum compositions
and examine the factors responsible for the observed
differences.
COMPOUNDS PRESENT IN BITUMEN
AND PETROLEUM
GENERAL CLASSES OF COMPOUNDS
Both bitumen and petroleum contain a very large number
of different chemical compounds. Some of these com-
pounds are present in relatively large quantities, while
others are only trace contributors. In order to investigate
the individual compounds present, we first separate a
crude oil or a bitumen into several fractions having dis-
tinct properties. The procedures used in carrying out such
separations are discussed in chapter 7.
Each of the fractions contains certain types of chemical
compounds. Table 5.1 lists the general classes of com-
pounds present in each of the fractions of crude oils and
bitumens. One fraction consists mainly of saturated hy-
drocarbons: n-alkanes, branched hydrocarbons (includ-
ing isoprenoids), and cyclics. Saturated hydrocarbons are
the most thoroughly studied of the components of petro-
leum and bitumen because they are the easiest to work
with analytically (see chapter 7).
A second fraction consists of aromatic hydrocarbons
and some light sulfur-containing compounds. Light aro-
matic hydrocarbons, like benzene and toluene, have been
studied in petroleums, but these compounds are lost from
bitumens during evaporation of the solvent used in ex-
tracting the bitumen from the rock. Heavier aromatic and
naphthenoaromatic hydrocarbons, particularly those de-
rived from diterpanes, triterpanes, and steranes, are more
commonly studied.
Most of the NSO compounds appear in the remaining
two fractions. The lighter of these fractions, variously
called po lars, NSOs, and resins, contains a wide variety
of small and medium-sized molecules with one or more
heteroatoms. Few of these heterocompounds have been
studied, although pqrphyrins, fatty acids, and some sul-
fur-bearing molecules have received attention.
TABLE 5.1 Four main fractions of bitumens and crude oils
and important compound cliLsses present in each
Fraction Important Compound Classes
Saturated hydro- n-alkanes
carbons isoprenoids
other branched compounds
alicyclics, including steranes, diterpanes,
and triterpanes
Aromatic hydro- simple aromatics
carbons naphthenoaromatics
small sulfur-bearing compounds
Resins (NSOs, porphyrins
polars) fatty acids
Asphaltenes asphaltenes
The final fraction contains very large, highly aromatic
asphaltene molecules that are often rich in heteroatoms.
Asphaltenes tend to aggregate into stacks because of their
planarity, and form complexes with molecular weights of
perhaps 50,000. The large sizes of asphaltene units ren-
der them insoluble in light solvents. Asphaltenes can thus
be removed from oils or bitumens in the laboratory or
refinery by adding a light hydrocarbon, such as pentane
or propane. Because of their molecular complexity and
heterogeneity, asphaltene molecules have not been
studied in detail.
SPECIFIC COMPOUNDS
Biomarkers. Many of the compounds and classes of com-
pounds that we find in crude oils and bitumens are called
biomarkers, an abbreviation for biological markers.
These compounds, which are derived from biogenic pre-
cursor molecules, are essentially molecular fossils. Many
types of biomarkers are listed in table 5.2. The most useful
biomarkers serve as indicators of the organisms from
which the bitumen or petroleum was derived, or of the
diagenetic conditions under which the organic matter
was buried. In a few cases specific precursor organisms
or molecules can be identified, whereas in other instances
we may be able to limit the possible precursors to only a
few species. In most cases, however, although we know
for certain that the biomarker molecule is biogenic, we

TABLE 5.2 Important classes of biomarkers
and their precursors
Biomarker Precursor
n-alkanes (> C-22) terrestrial plant waxes
n-alkanes (C-17, C-22) algal lipids
isoprenoids « C-20) various chlorophylls
isoprenoids (> C-20) lipids or chlorophyll of hypersaline
algae
porphyrins chlorophylls
steranes steroids
triterpanes bacterial triterpenoids
diterpanes hydrocarbons in plant resins
large naphtheno- steroids, triterpenoids
aromatics
are unable to use it as an "index fossil" for specific
organisms.
Among the biomarkers studied most frequently are the
n-alkanes, isoprenoids, porphyrins, steranes, triterpanes,
diterpanes, and naphthenoaromatics. The common mem-
bers of each of these compound classes and their signifi-
cance in interpreting source, diagenesis, maturation, and
reservoir transformations are discussed in a later section
of this chapter and in chapter 10. The reader interested
in more detailed treatment and extensive references is
referred to the excellent and comprehensive review by
Mackenzie (1984).
Other Compounds. Many other types of organic compounds
in crude oils and bitumens are not considered to be
biomarkers because they cannot be related directly to
biogenic precursors. They are, however, of biological ori-
gin, but their sources are simply no longer recognizable
due to diagenetic and catagenetic transformations.
Among the nonbiomarker compounds found in petro-
leum and bitumen are light aromatic hydrocarbons, such
as benzene, toluene, and the xylenes. They could be de-
rived from lignin but are also undoubtedly formed from
many other sources by aromatization or by cyclization
followed by aromatization. Many compounds containing
a benzene ring have one or more long-chain alkyl sub-
stituents; their origin is not known. Some polycyclic aro-
5. BITUMEN, PETROLEUM, AND NATURAL GAS 45
matics can be formed from steranes and triterpanes;
others may be the end products of extensive oxidation or
combustion of other types of organic material.
Small alkanes can be generated from a variety of pre-
cursors by cracking. Skeletal rearrangements occur easily,
giving a tremendous variety of isomers having no obvious
relation to their biological precursors.
Medium-sized alkanes having one or more methyl
branches are almost ubiquitous, although they are never
major components of oils or bitumens. They may be
biogenic hydrocarbons derived from plant or algal lipids
(and thus represent poorly understood biomarkers), or
they could be formed from n-alkanes by isomerization
processes.
With the exception of the porphyrins, fatty acids, and
alcohols, most NSO compounds are not biomarkers.
Heteroatoms react readily during diagenesis and cata-
genesis, forming many new compounds whose structures
bear no resemblance to biogenic structures. Few of these
compounds have been studied, and they will not be dis-
cussed further in this text.
FACTORS AFFECTING COMPOSITION
OF BITUMEN AND PETROLEUM
SOURCE AND DIAGENESIS
Biomarkers
N-ALKANES. n-Alkanes were among the first biomar-
kers 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 al-
cohols (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, es-
pecially 23,25,27,29, and 31 atoms. An example from a
Recent sediment containing much terrestrial organic ma-
terial 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, depend-
ing 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
W
W U
U
z Z
«
« 0
0
z Z
::>
::> It)
It)
« «
w
UJ >
> ;::
;:: «
«
...J
...J
W

'"
W

'"
10 20 30 <0 10 ·0

NUMBER OF CARBON ATOMS

FIGURE 5.1 n-Alkane distribution in a Recent sediment con- FIGURE 5.3 Distribution of n-alkanes in a Recent sediment
taining organic material chiefly of terrestrial origin. containing organic material of both marine-algal and terres-
trial origin.

Many sediments, of course, receive contributions of n-

w
U
Z
alkanes from both terrestrial and marine sources. Their
«
o
z
22
n-alkane distributions reflect this mix (fig. 5.3).
::> Sediments are also known that exhibit a strong prefer-
£II
«
w ence for n-alkanes having an even number of carbon
>
;::
«
atoms (fig. 5.4). These n-alkanes are believed to be
-'
w 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 organ-
10 <0
isms, even-carbon homologs predominate as strongly as
do the odd-carbon homologs among the n-alkanes.)
Even-carbon preferences occur principally in evaporitic
UJ and carbonate sediments, where input of terrestrial n-
U
z alkanes is minimal and diagenetic conditions are highly
«
<.l
z
::>
reducing.
Carbon Preference Index, or CPI, was developed as a
It)
«
UJ
~
.... measure of the strength of the odd-carbon predominance
« in n-alkanes. The formula for calculating CPI follows.
...J
w
'"
CPI
23 + 25 + 27 + 29 + 31
10 20 30 40
24 + 26 + 28 + 30 + 32
NUMBER OF CARBONATOMS
+ 25 + 27 + 29 + 31 + 33
24 + 26 + 28 + 30 + 32
FIGURE 5.2 Distributio[ls of n-alkanes from two Recent sed i-
ments in which marine algal material dominates. (23 represents the relative amount of the n-alkane having

w
u reduction occurs have high sulfur contents and high
z 28
«
o
Z
:>
CD
« ditions) and that have not experienced significant sulfate
w
>
;::
«
-'
w vary considerably, depending upon a number of factors
a:
'0 30
NUMBER OF CARBON ATOMS
flGURE 5.4 Distribution of n-alkanes in a rock extract from
a limestone deposited under evaporitic conditions. There is a
strong even-carbon priferenee.
23 carbon atoms, etc.) The average of two ranges is taken
to minimize bias produced by the generally decreasing n-
alkane concentrations with increasing number of carbon
atoms. If the number of odd- and even-carbon members
is equal, the CPI is 1.0. If odd-carbon homologs predomi-
nate, the CPI is greater than 1.0. However, because the
concentration of n-alkanes often decreases with increas-
ing carbon number, the lower-carbon homologs are given
more weight in the calculation. CPI values can therefore
deviate from 1.0 even when no preference is distin-
guishable by visual inspection of the distribution curve.
PORPHYRINS. Virtually all porphyrins come from
chlorophyll (fig. 5.5), a fact that limits their usefulness as
biomarkers. The magnesium ion of chlorophyll is lost
during early diagenesis and replaced by vanadyl (VA +2)
or Ni +2 in most cases. Two hydrogen atoms are removed
to give an alternating single-bond-double-bond system
around the periphery. The long isoprenoid side chain is
broken off, and numerous other reactions in and around
the ring system yield a wide variety of porphyrin
molecules.
Because porphyrins are usually derived from chlo-
rophylls, and because they are so susceptible to chemical
transformation, their .exact molecular structures are
mainly a function of diagenetic and catagenetic history.
5. BITUMEN, PETROLEUM, AND NATURAL GAS 47
Lewan (1984) has proposed that the ratio of vanadyl to
nickel porphyrins is dependent on diagenetic conditions.
Extracts or oils from anoxic sediments in which sulfate
ratios of vanadyl to nickel porphyrins. Extracts and oils
derived from sediments whose pH is above 7 (basic con-
reduction have low sulfur contents and V/Ni ratios that
that affect availability of Ni + 2 and va + 2 ions. In contrast,
acidic sediments in which sulfate reduction has not been
important have low contents of sulfur and very low ratios
of vanadyl to nickel porphyrins.
Unfortunately, the myriad reaction pathways involving
the carbon skeletons of chlorophyll and its daughter por-
phyrins are still only partly understood. They therefore
are not yet of much value as indicators of diagenetic
conditions.
ISOPRENOIDS. Chlorophyll a is also the source for most
phytane and pristane molecules, which are the two most
common isoprenoids (fig. 5.5). Other isoprenoids (table
3.2) are also of biogenic origin, although their specific
precursors are often not obvious. The Ci6 to Ci8 iso-
prenoids are probably also derived mainly from
chlorophyll a. Isoprenoids having fifteen carbon atoms or
fewer could come either from chlorophyll a or from bac-
terial chlorophylls that have the Ci5 isoprenoid instead of
C20 as a side chain. The origins of isoprenoids having
from 21 to 25 carbon atoms are not well understood,
although they seem to occur preferentially in evaporitic
sediments. The C30 and C40 isoprenoids are probably con-
tributed by some species of algae.
Isoprenoids are good indicators that bitumen and pe-
troleum are of biogenic origin, but, like porphyrins, are of
very limited value in assessing the contribution of any
particular organism. Their occurrences have been associ-
ated with specific depositional environments, however.
For example, the ratio of pristane to phytane has been
used as an indicator of oxygen levels during diagenesis;
high pristane/phytane ratios are thought to be associated
with oxidizing environments.
STERANES. Steroids, the biological precursors of the
steranes, are present in all organisms more advanced
than cyanobacteria (blue-green algae). Diagenesis con-
verts the steroid molecules to sterane hydrocarbons (fig.
48
CaHill H2c-otZ
VANADYL PORPHYRIN
5.6) through hydrogenation of double bonds and loss of
oxygen atoms. Despite these cosmetic changes, sterane
structures preserve most of the uniqueness of the precur-
sor steroids and can serve as effective biomarkers.
The main use of steranes as biomarkers derives from
the distribution of steroids in plants. The most common
steroids are the three sterols having 27,28, and 29 carbon
atoms (fig. 5.7), which are present in different propor-
tions in various organisms. During diagenesis these
sterols are converted to the corresponding regular
steranes (fig. 5.8). Thus the sterane distribution in a rock
extract reflects the relative inputs of the various types of
living organisms.
TRITERPANES. The triterpanes commonly found in oils
and bitumens come mainly from triterpenoids synthe-
sized by microorganisms. Triterpenoids occur only in low
abundance in most higher plants and have different struc-
tures than most triterpanes in sediments. Because of the
microbial synthesis of triterpenoids within sediments,
CHLOROPHYLL A
PRISTANE, C111 H"o
FIGURE 5.5 Biomarkers derived from the biogenic molecule
chlorophyll a.
triterpanes are important indicators of depositional envi-
ronments and diagenetic conditions.
The most common triterpanes are hopane (the thirty-
carbon namesake of the hopane series) and the C29
hopane (norhopane) (fig. 5.9). The precise precursors for
these two hydrocarbons are unknown, but their ubiquity
and high abundance suggest they may be formed from
several different triterpenoids. Other less common triter-
panes have been associated with specific types of source
material or depositional environments.
Some bacterial triterpenoids actually have 35 carbon
atoms rather than the 27 to 30 in the normal hopane
series. These extended triterpenoids are presumed to be
the precursors for the extended hopanes (C 31 to C3S ) often
found in extracts and oils (fig. 5.10). Hopanes containing
from 36 to 40 carbon atoms have also been reported, but
no source for them has yet been proposed.
 5. BI1UMEN, PETROLEUM, AND NA1URAL GAS 49

DITERPANES. Diterpanes are important constituents of

oils and extracts derived from fossil plant resin. In such
cases a few diterpanes may be the dominant individual
hydrocarbons present. Other diterpanes that are more
modest contributors to extracts and oils are not derived
from terrestrial plants.
NAPHTHENOAROMATICS. Because naphthenoaromat-
ics are often derived from steranes and triterpanes, they
HO
also are biomarkers. In general, however, they have lost
many of their unique stereochemical characteristics as a
result of catagenetic transformations and thus cannot be
Many steps related with certainty to specific precursors.
SUMMARY. Below is a brief summary of the most im-
portant data on the source and diagenesis of biomarkers:

1. Bitumens and crude oils with high contents of waxy n-

FIGURE 5.6 Diagenetic conversion of C2.9 sterols into steranes.
The process is ana/ogou.s for other steroids. Reprinted by
permission of Cambridge University Press from Mackenzie
and McKenzie, 1983.
alkanes (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 con-
ditions.
4. Samples containing large amounts of a very few tricy-
clic diterpanes have a significant contribution from
land-plant resin.
5. Distributions of CZ7 to CZ9 steranes are useful for deter-
mining the type of organic matter contributing to a
sample.

II ell ,
I

110 110
~
~JI
liD
Cholestl'rol r:1'!{ostl'l'ol B-sitoSll'1'01
C~~ C:~II C!"

FIGURE 5.7 Common sterols in living organisms.

50

hole lanc Ll'goswnc

C~7 C !II

FIGURE 5.8 Common steranes in rock extracts and oils.

OH OH
""/ " /
"'\
C~
H OH OH
Tctl'ah.vdroxybacteriohopanc

C 29 C 30

FIGURE 5.9 Structures of CZ-9 and C.Jo hopanes. 1 Many step

6. Triterpane distributions are sensitive to diagenetic

conditions.

More detailed discussions of the interpretation of source

and diagenesis based on biomarker distributions are
found in chapter 10.

Parameters Other Than Biomarkers. Sulfur contents are also

strongly influenced by diagenetic conditions. For eco-
nomic and environmental reasons, oils having more than FIGURE 5.10 Formation of extended hopanes from tetrahy-
about 0.5% sulfur are designated as high-sulfur. Many droxybacteriohopane, a probable precursor. Also shown is
high-sulfur oils contain 1% sulfur or less, but in some the epimerization at C-22 from the biogenic 22R configuration
areas sulfur contents can reach 7% (Monterey oils from to an eventual equilibrium mixture of 22R and the more sta-
ble 225. Reprinted by permission of Cambridge University
the onshore Santa Maria area, southern California, for Press from Mackenzie and McKenzie, 1983.
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-
 5. BITUMEN, PETROLEUM, AND NATURAL GAS 51

ments that accumulate where anaerobic sulfate reduction

is important. Most oils and bitumens derived from lacus-
trine or ordinary clastic marine source rocks will be low
in sulfur content, whereas those from euxinic or anoxic
marine source rocks will be high-sulfur.
Sulfur occurs predominantly in the heavy fractions of
oils and bitumens, particularly in the asphaltenes. High-
sulfur oils therefore have elevated asphaltene contents.
The high asphaltene contents, together with the high den-
sity of sulfur atoms, cause high-sulfur oils to be of low
API gravity. However, as we shall see later in this chap-
ter, not all low-gravity oils are rich in sulfur.

MATURITY

General Properties. Maturity has a great effect on the com-

positions of petroleum and bitumen. Low-maturity sam-
ples, including bitumens, oils, and solidified bitumens,
have fewer hydrocarbons and more NSO compounds,
and average molecular weights are higher. SIN ratios de-
crease 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 low-
maturity 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 esti-
mate maturity levels in pelagic rocks on the basis of n-
alkane profiles.
ISOPRENOIDS. Isoprenoid distributions also change
with maturity, though not as dramatically. As maturity
proceeds, phytane is generated faster than pristane, lead-
ing to a decrease in the pristane/phytane ratio (fig. 5.12).
NUMBER OF CARB()4 ATOMS
FIGURE 5.11 Change in n-alkane distributions of coal ex-
tracts as a function of increasing maturity, measured by vit-
rinite reflectance. Reprinted with pennission from Radke et
al., 1980. Copyright 1980, Pergamon Press, Ltd.
The magnitude of this change is small, however, and may
be lost in the natural variation occurring from sample to
sample.
During hydrocarbon generation, isoprenoid concentra-
tions increase more slowly than do n-alkane concentra-
tions. Thus the ratio of n-alkanes to isoprenoids increases
with increasing maturity (fig. 5.13).
PORPHYRINS. As maturity increases, alkyl groups in
porphyrins migrate rather freely about the central ring
structure and are exchanged with other molecules. Aver-
age molecular weights of porphyrins decrease with in-
creasing maturity, and there is a decrease in the ratio of
nickel to vanadyl porphyrins. Fundamental changes in
porphyrin structure also occur. DPEP-type porphyrins are
converted to etio-type porphyrins as the extra ring is bro-
ken during catagenesis (fig. 3.4). Nickel porphyrins react
faster than vanadyl.
STERANES. Maturation also brings about important
changes in sterane molecules. Epimerization reactions
and migration of methyl groups from one ringjuncture to
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-

FIGURE 5.12 Pristanelphytane ratios as a function of burial

depth and maturity in the Mahakam Delta, Kalimantan. Re-
printed by permission ofJohn Wiley & Sons, Ltd. from Pres-
ent trends in organic geochemistry in research on migration
of hydrocarbons, by B. Durand, ed. by M. Bjorf'Y. Copyright
1983, John Wiley & Sons, Ltd.

MAHAKAM DELTA

410 a b
!oJ
1
~ 045 I 420
..,~ ..J

...w
.J ...':"4
~
cr 2100 ]
g
~060 cr :r
t-
Z o..
ir 2700 ~
t-
;;:
~

~"
~
-; 090 ]000
cr

o 5 10 20 0 05 10 1.5
--PRISTANE/nCI7 RATIO-- -PHYTANE/nCI8 RATIO-+

FIGURE 5.13 Isoprenoid/n-alkane ratios as a function of bu-

rial depth and maturity in the Mahakam Delta, Kalimantan.
Reprinted by permission ofJohn Wiley & Sons, Ltd. from
Present trends in organic geochemistry in research on migra-
tion of hydrocarbons, by B. Durand, ed. by M. Bjorf'Y. Copy-
right 1983, John Wiley & Sons, Ltd.

",0
-OH-
HYDROGENATION
Sa, 14a, 17a(20R)
Regulm'
sterane
R
~ R ' \ - CATAGENESIS
Sa, 14a, 17a(2OS) Sa, 1413, 1713(20R)
Regular Isoskeletal
sterane
FIGURE 5.14 Catagenetic transformation of a regular sterane
into epimerized, isoskeletal, or rearranged steranes during
catagenesis.
another produce a variety of new steranes from the origi-
nal5a, 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.
5. BITUMEN, PETROLEUM, AND NATURAL GAS 53
R
1313, 17a(20 S or R)
Rearranged
sterane sterane
Migration of methyl groups across a ringjuncture leads
to rearranged steranes, also called dinsteranes. Dia-
sterane concentrations seem to be influenced by both
diagenetic and catagenetic effects, and may also be source
related.
TRITERPANES. Many catagenetic transformations of
triterpanes also involve thermally induced epimeriza-
tions. In the extended hopane series (Cell to C35 ), biogenic
22R epimers are eventually converted to an equilibrium
mixture of 22R and 22S epimers (fig. 5.10). In hopanes
having fewer than 31 carbon atoms, 22R and 22S epimers
do not exist, because carbon number 22 does not have
four different groups attached to it.
Another important maturation-induced change in
triterpanes is the loss of moretanes in the early stages of
54
MORETANE
1711(H), 21a(H)
catagenesis. Moretanes differ from hopanes in their
stereochemistry at C-21 (fig. 5.15).
DITERPANES. Tricyclic diterpanes derived from fossil
resin are quite unstable. They are formed during very
early catagenesis but are destroyed soon after formation.
Their presence is therefore an indication not only of a
resinite source, but also of a mild thermal history for the
sediment or oil. Their absence in mature samples there-
fore does not necessarily preclude a contribution by
resinite.
NAPHTIIENOAROMATICS. Aromatization of steranes
and triterpanes occurs stepwise as maturation proceeds.
Either ring A or ring C (fig. 3.2) is aromatized first; then
rings B and C (or A and B) are aromatized at essentially
the same time (fig. 5.16).
HOPANE
17a(H), 21 /3(H)
FIGURE 5.15 Structure of C30 rrwretane compared to C30
hopane.
FIGURE 5.16 Irreversible conversion of rrwnoaromatic
steranes to triaromatic steranes. Reprinted by permission of
Cambridge University Press from Mackenzie and McKenzie,
1983.
Aromatization of triterpanes also occurs, but has not
been studied in detail. Aromatized triterpanes are not
normally used in geochemical interpretations.
Both steranes and triterpanes are aromatized much
more rapidly if the host rocks contain anhydrite. Sulfate
oxidizes saturated hydrocarbons to aromatics and
naphthenoaromatics.
SUMMARY. The chemical transformations mentioned
earlier can often be used in correlations and in estimating
maturities of source rocks and oils. Epimerization and
other isomerization reactions occur at a variety oflevels of
thermal maturity, thus affording us the possibility of using

a number of different transformations as maturity indi-
cators, each within its optimal range of validity. Specific
applications of biomarker transformations will be dis-
cussed in more detail in chapters 8 and 10.
RESERVOIR TRANSFORMATIONS
Introduction. There are two main types of reservoir trans-
formations that can affect crude oils (reservoir transfor-
mations are not applicable to bitumen because, by
definition, the material in a reservoir is petroleum). Ther-
mal processes occurring in reservoirs include cracking
and deasphalting. Nonthermal processes are water wash-
ing and biodegradation. Of these, cracking and biodegra-
dation are by far the most important.
Cracking and Deasphalting. Cracking, which breaks large
molecules down into smaller ones, can convert a heavy,
heteroatom-rich oil into a lighter, sweeter one. Waxy oils
become less waxy. API gravities increase, and pour
points and viscosities decrease. When cracking is ex-
treme, the products become condensate, wet gas, or dry
gas.
Cracking is a function of both time and temperature, as
well as of the composition of the oil and the catalytic
potential of the reservoir rock. It is therefore impossible to
state that cracking always occurs at a certain depth or
reservoir temperature. Most oils, however, will be reason-
ably stable at reservoir temperatures below about 90° C,
regardless of the length of time they spend there. On the
other hand, a reservoir above 120° C will contain normal
oil only if the oil is a recent arrival.
Although the role of catalysis in hydrocarbon cracking
in reservoirs has not been proven, many workers suspect
that clay minerals are important facilitators of hydrocar-
bon breakdown. Catalytic effectiveness varies greatly from
one clay mineral to another, however, and our partial
understanding of this difficult subject is not of much prac-
tical use at the present time.
Cracking also brings about deasphalting, because as-
phaltene molecules become less soluble as the oil be-
comes lighter. Precipitation of asphaltenes in the reser-
voir will lower sulfur content and increase API gravity
appreciably.
Maturity of oils can be estimated using some of the
5. BITUMEN, PETROLEUM, AND NATURAL GAS 55
biomarker techniques mentioned above as well as by
light-hydrocarbon analyses. These applications will be
discussed in more detail in chapters 8 (as applied to
source rocks and bitumens) and 10.
Biodegradation and Water Washing. Water washing involves
selective dissolution of the most soluble components of
crude oils in waters that come in contact with the oils.
The smallest hydrocarbon molecules and the light aro-
matics, such as benzene, are the most soluble. The effects
of water washing are rather difficult to determine because
they do not affect the oil fractions that are most frequently
studied. Furthermore, in most cases the effects are quite
small because of the low solubilities of all hydrocarbons
in water. Finally, water washing and biodegradation of-
ten occur together, with the more dramatic effects of
biodegradation obscuring those of water washing.
Biodegradation is a transformation process of major
importance. Under certain conditions some species of
bacteria are able to destroy some of the compounds pres-
ent in crude oil, using them as a source of energy. The
bacteria responsible for biodegradation are probably a
mixture of aerobic and anaerobic strains. Only aerobic
bacteria are believed to actually attack hydrocarbons, but
anaerobes may consume some of the partially oxidized
byproducts of initial aerobic attack.
Because biodegradation changes the physical proper-
ties of oils, it can have serious negative financial implica-
tions. Heavily biodegraded oils are often impossible to
produce (Athabasca Tar Sands of Alberta, Canada, and
the Orinoco heavy oils of Venezuela, for example). Ifpro-
duction is physically possible, it may be expensive or un-
economic. It is therefore important to understand where
and why biodegradation occurs, and what its effects are
on oil composition.
Conditions required for biodegradation of crude oil in-
clude the presence of an oil-water interface (because the
microorganisms live in the water phase), an influx of
meteoric waters bringing nutrients and dissolved oxygen,
and temperatures below about 80° C. This upper tem-
perature limit has not been definitely proven, but evi-
dence for biodegradation at higher temperatures is not
compelling.
Biodegradation may actually begin during oil mi-
gration (provided required temperature and oxygen
56

TABLE 5.3 Classification of biodegraded crude oils according

1 . GASES (Cl . C6) "
to the severity of biodegradation
2· GOR (GAS/Oil RATIO) "
Level of Compounds Extent of
3· GASOLINE RANGE (C6 . C15) "
Biodegradation Removed Biodegradation
4· API GRAVITY iii
5 . VISCOSITY , 1 None Undergraded
6· CHANGES IN GROSS COMPOSITION OF CltCOMPOUNDS 2 Short n-alkanes absent Minor
alkanes "
~romatics 1I
3 > 90% of n-alkanes Moderate
NSO's compounds ~ removed
asphaUenes , 4 Alkylcyclohexanes Moderate
7· SULPHUR CONTENT ~ absent; isoprenoids
8 . NITROGEN CONTENT ~ reduced
9· V AND Ni , 5 Isoprenoids absent Moderate
10 . OPTICAL ACTIVITY ~ 6 Bicyclic alkanes absent Extensive
alkanes ~ > 50% regular steranes Very extensive
7
11 . POUR POINT 1I
removed
12 . 613C
whole 011 ~ 8 Steranes altered; de- Severe
alkanes ~ methylated hopanes
aromallcs '" or .. abundant
asphaUenes .. 9 Demethylated hopanes Extreme
13 . CHANGES IN Oil TYPES predominate; dia-
paraffinic oil _ _ _ _ _ _ _ _ _• naphthenic Oils
steranes formed; no
paraffinic or paraffmic·naphthenlc OIls_ aromalic·naphthenlc oils
steranes
paraffinic condensates • naphthp.nlc condensates
condensates • light oils
aromatic - intermediate oils _ _ _ _ _ • aromatic-asphaltic oils NOTE: Reprinted with pennission from J. K. Volkman, R. Alexander, R. I. Kagi,
and G. W. Woodhouse, 1983, Demethylated hopanes in crude oils and their appli-
cations in petroleum geology: Geochimica et Cosmochimica Acta, v. 47, table 2,
p. 792. Copyright 1983, Pergamon Press, Ltd.
FIGURE 5_17 Effects of biodegradation on chemical and phys-
ical properties of crude oils. Reprinted by permission of Aca-
demic Press from Connan, 1984. n-alkanes, presumably because their straight-chain
configurations allow the bacterial enzymes to work on
conditions are met), because oil-water interactions are them most efficiently. Also attractive to the "bugs" are
maximized then. Most biodegradation probably occurs long, alkyl side-chains attached to cyclic structures.
within reservoirs, however, since the length of time an oil After the n-alkanes and alkyl groups are consumed, the
spends in a reservoir is usually much longer than its bacteria begin to destroy compounds having only a single
transit time during migration. methyl branch or those having widely spaced branches.
Biodegradation can vary in intensity from very light to Then they move on to more-highly branched compounds,
extremely heavy. Because the chemical and physical such as the isoprenoids.
properties of an oil change dramatically in several pre- In the last stages of biodegradation, polycyclic alkanes,
dictable ways during biodegradation (fig. 5.17), biode- particularly some steranes and triterpanes, are attacked.
graded oils are easily recognized. Many basins have at There is once again a hierarchy of attack: first the regular
least a few biodegraded oils, and in some areas they are 20R steranes are degraded, then regular 22R hopanes,
epidemic. and, finally, other steranes and hopanes. The more simi-
Bacteria that consume petroleum hydrocarbons have lar a molecule's carbon skeleton is to those of naturally
strong preferences (fig. 5.17). Hydrocarbons are not their occurring steroids and triterpenoids, the more easily it
very favorite foods, and they eat them only because there will be degraded. Steranes and triterpanes having rear-
is nothing else available. The preferred hydrocarbons are ranged structures are therefore resistant to biodegrada-
 5. BITUMEN, PETROLEUM, AND NATURAL GAS 57

'\Illlllallr IIC

Mo Ih' Ill'''\'\'.
Nonmll crude oil (kgl',;dt·cl oj'ls

40 20 N 0 compound
(I 'ins + a ph(l\relll's)
Average gl'OSS compo ilion of 517 normal pl'odudbl(' ('Iudl' oils
aturated hydl'OCLlrbons ........................... 57.200
Aromatic hydJ'(x.'Lll'bons ............................ 28.600
NSO ........................................... 14.2%

FIGURE 5.18 Triangular diagram showing the compositions

of 636 crude oils. Biodegraded oils are considerably depleted
in saturated hydrocarbons compared to normal oils. Re-
printed by permission of Springer-Verlag from Tissot and
Welte, 1978.
tion. There is no evidence that bacteria can attack
porphyrins, asphaltenes, or other heavy NSO compounds
in petroleum.
Because the hierarchy of bacterial attack on crude oils
is well known, it is possible to assess the degree ofbiodeg-
radation by observing which compounds have been de-
stroyed. Table 5.3 shows a recently proposed scale for
estimating the intensity of biodegradation of an oil.
A few new compounds are formed during biodegrada-
tion, possibly as components of bacterial cells. These in-
clude a series ofdeme.thylated hopanes (table 5.3), which
are discussed in chapter 10.
Biodegradation changes the gross composition of oils
by removing saturated hydrocarbons. When the major
components of crude oils are plotted on a triangular dia-
gram (fig. 5.18), biodegraded oils are clearly distin-
guished from most normal oils. Biodegraded oils average
about 20% saturated hydrocarbons, compared to nearly
60% in normal oils. Relative proportions of aromatics and
NSO compounds increase as the saturates are removed
during biodegradation. Loss of saturated hydrocarbons
leads to a shift in carbon-isotope values of biodegraded
oils to less-negative values.
Sulfur contents of crude oils also increase as a result of
biodegradation. In a heavily biodegraded oil the sulfur
content may increase by a factor of two or three (fig.
5.19). Sulfur is undoubtedly concentrated in the oil by
selective removal of hydrocarbons, and may also be
added by bacterially mediated sulfate reduction.
58

COMPARISON OF BITUMEN AND PETROLEUM

Although bitumens and crude oils contain the same com-
pounds, 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
0.6
converted to hydrocarbons. In actuality, both processes
0.8 probably occur, although selective loss of nonhydrocar-
Sulfur
1.0
bons during expulsion is probably most effective in con-
(%l centrating the hydrocarbons.
1.2 Bitumen composition depends strongly on the lithology
1.4
of the host rock (fig. 5.21). Carbonates contain bitumens
that are much richer in heterocompounds than are shales,
1.6 and their hydrocarbon fractions are more aromatic.
1.8
These differences are the result of the higher sulfur con-
tents of kerogens in carbonates. Oils derived from carbon-
2.0 L-_~_~_--'---_---'-_~_--'
ate sources are also richer in heterocompounds than oils
sourced from shales.
In discussing the presence or distribution of individual
FIGURE 5.19 Increases in sulfUr content during biodegrada-
tion of oiLs from the Alaska North Slope. From Magoon and compounds in bitumens, it is important to know the ma-
Claypool, 1981.

Bitumens from Crude oils

shales and siltstones N = 2364
N = 1595

700
en
~ 600
~

~ 500
~ 200 en
s: tl 400
:E 150
;;l g300
..... 100
o 200
g
o+----.--~--~~
0.0 20.0 40.0 60.0 80.0 100.0
PERCENT HYDROCARBONS PERCENT HYDROCARBONS

FIGURE 5.20 Comparison of hydrocarbon contents of bitu-

mens and crude oiLs.
 5. BITUMEN, PETROLEUM, AND NATURAL GAS 59

The principal components with which we shall be con-

Extract of cerned are light hydrocarbons (methane through
Source rock Oil butanes), CO2, H2S, and N 2.
Shale/sand Carbon dioxide and N2 are generally associated with
sequence 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

o
measurements: the very different isotopic compositions of
carbonate
sequence
~.: ••.
..........
••••••••
. organic-carbon species and carbonates (fig. 3.16) are car-
ried over into any CO2 derived from these materials. Ni-
~
.... 4. .... <II . . . .

............. <II ..
.......... <II .... .
o Resins + asphalten
o Aromali H
© Saturated H
FIGURE 5.21 Compourul distributions in oils arul extracts
from both sarul/shale arul carbonate sequences. Reprinted by
permission of the World Petroleum Congresses from the Pro-
ceedings of the Eighth World Petroleum Congress, Applied &i-
ence Publishers, from Tissot arul Pelet, 1971.
turity level of the bitumen. Many of the compounds and
compound distributions in mature bitumens are essen-
tially indistinguishable from those in crude oils. Imma-
ture bitumens, in contrast, are very different from
petroleum.
For example, we have seen (fig. 5.1) that n-alkane dis-
tributions in immature samples often have very high CPI
values. Mature rocks and oils, in contrast, always have
CPI values near 1.0 (fig. 5.11). The normal range for oils
and mature extracts extends from about 0.9 to 1.2. Oils
with CPI values outside this range are very rare.
Other individual compounds follow this same trend.
The distributions of porphyrins, steranes, and triterpanes
can be either mature or immature in bitumens, but are
always at least marginally mature in crude oils. The use
of these types of compounds as maturity indicators will be
discussed in chapter 8.
NATURAL GAS
Natural gas contains -. many different compounds, al-
though most of them are present only in trace quantities.
trogen 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 car-
bonate. 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 car-
bonates 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 isotopi-
cally 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 compo-
nents of wet gases have been used as a paleothermometer
(Sundberg and Bennett, 1983).
Mixing of biogenic and thermal gases often occurs, es-
pecially 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)
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 As-
sociation of Petroleum Geologists from Rice and Claypool,
1981.
measurable changes in the composition when it does oc-
cur. Biodegraded gas is dry, because most of the heavier
components have been preferentially removed. As a re-
sult, any remaining heavy hydrocarbons will be un-
usually heavy isotopically.
SUMMARY
Bitumens and crude oils contain the same classes of com-
pounds, but their relative concentrations are quite differ-
ent. These differences are in some cases related to
differences in maturity; in other examples they are proba-
bly a result of preferential expulsion of hydrocarbons
from source rocks.
Individual compounds occur in quite variable propor-
tions in bitumens. S~urce, diagenesis, and maturity all
exert control over these distributions. When source and
diagenetic influences have been removed, the porphyrins,
steranes, triterpanes, and n-alkanes in mature bitumens
are found to be very similar to those in crude oils and
quite different from those in immature bitumens.
Oil compositions can also be strongly affected by reser-
voir transformations, including biodegradation, water
washing, cracking, and deasphalting. Many of the factors
that influence the composition of oils and bitumens are
well understood and predictable, and can be used to ob-
tain information about paleoecology, thermal history, and
reservoir conditions.
Gas composition is governed first of all by whether the
gas is of biogenic or thermal origin. Biogenic gas is al-
ways dry, whereas thermal gas may be wet or dry. Car-
bon-isotope ratios are good indicators of the source of gas;
biogenic gas is much lighter isotopically than thermal
gases. Other important components, such as CO 2 , N2 , and
H2 S, are indicative of high temperatures or sulfur-rich
source material.
SUGGESTED READINGS
Albaiges,J. andJ. M. Torradas, 1974, Significance of the even-
carbon 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. Volk-
man, 1983, The geochemistry of some biodegraded Austra-
lian 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. 299-
333.
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 sub-
surface 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

dium to nickel in crude oils: Geochimica et Cosmochimica

Acta, v. 48, pp. 2231-2238.
Mackenzie, A. S., 1984, Applications of biological markers in
petroleum geochemistry, inJ. Brooks and D. Welte, eds., Ad-
vances in Petroleum Geochemistry, Volume 1: London, Aca-
demic Press, pp. 115-214.
Milner, C. W. D., M. A. Rogers, and C. R. Evans, 1977, Petro-
leum transformations in reservoirs: Journal of Geochemical
Exploration, v. 7, pp. 101-153.
Orr, W. L., 1974, Changes in sulfur content and isotopic ratios
of sulfur during petroleum maturation-study of Big Horn
Basin Paleozoic oils: Bulletin of the American Association of
Petroleum Geologists, v. 50, pp. 2295-2318.
Palmer, S. E., 1984, Effect of water washing on C1S + hydrocar-
bon fraction of crude oils from northwest Palawan, Philip-
pines: Bulletin of the American Association of Petroleum
Geologists, v. 68, pp. 137-149.
Rice, D. D., 1980, chemical and isotopic evidence of the origins
of natural gases in offshore Gulf of Mexico: Transactions-
Gulf Coast Association of Geological Societies, v. 30, pp. 203-
213.
- - - , 1983a, Relation of natural gas composition to thermal
maturity and source rock type in Sanjuan Basin, northwest-
ern New Mexico and southwestern Colorado: Bulletin of the
American Association of Petroleum Geologists, v. 67, pp.
1199-1218.
- - - , 1983b, Application of organic geochemistry to hydro-
carbon occurrence, in D. D. Rice and D. L. Gautier, Patterns
of Sedimentation, Diagenesis, and Hydrocarbon Accumula-
tion in Cretaceous Rocks of the Rocky Mountains: SEPM
Short Course Notes No. 11, Tulsa, pp. 3.1-3.40.
Volkman, J. K., R. Alexander, R. I. Kagi, and G. W.
Woodhouse, 1983a, Demethylated hopanes in crude oils and
their applications in petroleum geochemistry: Geochimica et
Cosmochimica Acta, v. 47, pp. 785-794.
Volkman, J. K., R. Alexander, R. I. Kagi, R. A. Noble, and
G. W. Woodhouse, 1983b, A geochemical reconstruction of
oil generation in the Barrow Sub-basin of Western Australia:
Geochimica et Cosmochimica Acta, v. 47, pp. 2091-2105.
Chapter 6 Migration

DEFINITIONS
Migration is the movement of oil and gas within the sub-
surface. Primary migration is the first phase of the migra-
tion 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 mi-
grated hydrocarbons in a relatively immobile configura-
tion, 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 un-
discovered hydrocarbon accumulations might be.

PRIMARY MIGRATION

MECHANISMS
Many theories about primary migration (expulsion) have
been popular at various times, but those that have been
discounted will not be discussed here. Today there are
only three mechanisms of primary migration that are

63
64
given serious consideration by most petroleum geochem-
ists: 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 hydro-
carbon 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 genera-
tion. When the internal pressures exceed the shear
strength of the rock, microfracturing occurs, particularly
along lines of weakness such as bedding planes. Lam-
inated source rocks may therefore expel hydrocarbons
with greater efficiency than massive rocks. Once the inter-
nal pressure has returned to normal, the microfractures
heal. The hydrocarbons within the pores then become
isolated again because of the impermeability of the water-
wet source rocks to hydrocarbons, and overpressuring
commences anew. Many cycles of pressure buildup, mi-
crofracturing, 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 thresh-
old 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 (equiva-
lent to 50 million barrels per cubic mile for those of us
who have trouble with acre-feet). Although the exact
threshold value must vary considerably as a function of
rock lithology and other factors, Momper's value has been
widely accepted as a reasonable average.
Once the threshold has been exceeded, most of the hy-
drocarbons are expelled, but a large proportion of NSO
compounds and heavier hydrocarbons are left behind.
Thus inefficiency of expulsion is responsible for much of
the difference in composition of bitumen and petroleum
that we noted in chapter 5. Primary migration is unques-
tionably the most difficult part of the entire migration
process. Therefore the threshold must represent not only a
hurdle to be cleared by the bitumen before it can leave the
source rock, but also an "exit tax."
We can only estimate the fraction of the bitumen left in
the source rock during microfracture-induced expulsion.
By comparing the average hydrocarbon compositions of
bitumens and crude oils (approximately 50% and 90%,
respectively, from fig. 5.20), and assuming that expulsion
of hydrocarbons is ten times as efficient as expulsion of
NSO compounds, we can estimate that once the expulsion
threshold is reached the expulsion efficiency for bitumen
is about 50%. Of course, this approach is rather approxi-
mate, but it does give some idea of the efficiency of
expulsion.
A second way in which oil-phase expulsion can occur
is from very organic-rich rocks prior to the onset of strong
hydrocarbon generation. This expulsion process probably
releases internal pressures in the rock, but the mechanism
by which overpressuring is achieved is not understood.
The organic matter expelled consists mainly of lipids that
were present in the sediment during deposition and
diagenesis. Therefore, this early expulsion mechanism
seems to be limited to rocks having very high original
contents of lipids. Khavari-Khorasani (1984) has pro-
posed this mechanism to account for some of the
solidified bitumens in the Uinta Basin of Utah.
Finally, oil-phase expulsion can take place when bitu-
men forms a continuous network that replaces water as
the wetting agent in the source rock. Expulsion of hydro-
carbons is facilitated because water-mineral and water-
water interactions no longer need be overcome. This type
of expulsion is probably only operative in very rich source
rocks during the main phase of oil generation. Meissner
(1978) has proposed that continuous-hydrocarbon-phase

expulsion occurs from the Bakken Formation of the Wil-
liston Basin.
The third mechanism, expulsion of oil dissolved in gas,
requires that there be a separate gas phase. Such a phase
could only exist where the amount of gas far exceeded the
amount of liquid hydrocarbons; therefore, it would be
expected only in the late stages of catagenesis or in source
rocks capable of generating mainly gas. Because neither
case is of great general significance for petroleum forma-
tion, we conclude that solution in gas is a minor mecha-
nism for oil expulsion.
DISTANCE AND DIRECTION
The distances traversed by hydrocarbons during primary
migration are short. Primary migration is difficult and
slow, because petroleum is being forced through rocks
having low matrix permeabilities. As soon as easier paths
become available, they will be taken by the migrating
fluids. Thus primary migration ends whenever a perme-
able conduit for secondary migration is reached.
In most cases the distances of primary migration are
probably between 10 centimeters (cm) and 100 m. Sand
stringers within shale units can provide secondary-
migration conduits for hydrocarbons sourced in the
shales. Fracture and joint systems, particularly in brittle
carbonate and opal-chert source rocks, also make excel-
lent secondary-migration pathways. Massive, unfractured
source-rock units are relatively rare; where they do exist,
primary migration may be of poor efficiency. In most
cases hydrocarbons are generated within short distances
of viable secondary-migration conduits.
Because the driving force for microfracture-induced
primary migration is pressure release, hydrocarbons will
be expelled in any direction that offers a lower pressure
than that in the source rock. Because the source rock is
overpressured, expulsion can be lateral, upward, or
downward, depending upon the carrier-bed characteris-
tics of the surrounding rocks. Thus a source rock lying
between two sands will expell hydrocarbons into both
carrier beds.
SECONDARY MIGRATION
MECHANISM
Once hydrocarbons are expelled from the source rock in a
separate hydrocarbon phase into a secondary-migration
6. MIGRATION 65
x y
FIGURE 6.1 Retardation of buoyant movement as an oil
globule (diagram X) is deformed to fit into a narrow pore
throat (diagram V). The upward buoyant force is partly or
completely opposed by the capillary-entry pressure, the force
required to deform the oil globule enough to ellter the pore
throat. If the capillary-entry pressure exceeds the buoyant
force, secondary migration will cease until either the capil-
lary-entry pressure is reduced or the buoyant force is in-
creased. From Geology of Petroleum by A. Levorsen. W. H.
Freeman and Company. Copyright © 1967. All rights
reserved.
conduit, subsequent movement of the hydrocarbons will
be driven by buoyancy. Hydrocarbons are almost always
less dense than formation waters, and therefore are more
buoyant. Hydrocarbons are thus capable of displacing
water downward, and moving upward themselves. The
magnitude ofthe buoyant force is proportional both to the
density difference between water and hydrocarbon phase
and to the height of the oil stringer. Coalescence of
globules of hydrocarbons after expulsion from the source
rock therefore increases their ability to move upward
through water-wet rocks.
Opposing the buoyancy is capillary-entry pressure,
which is resistance to entry of the hydrocarbon globule or
stringer into pore throats. Whenever a pore throat nar-
rower than the globule is encountered, the globule must
deform to squeeze into the pore (fig. 6.1). The smaller the
pore throat, the more deformation is required. If the up-
ward force of buoyancy is large enough, the globule will
squeeze into the pore throat and continue moving up-
ward. If, however, the pore throat is very tiny or if the
buoyant force is small, the globule cannot enter, and be-
comes stuck until either the buoyant force or the capillary-
entry pressure changes. When hydrocarbons cease
moving, we say that accumulation has occurred.
This model is very simple, requiring only the existence
66
of two forces. Buoyancy promotes migration, whereas
capillary-entry pressure retards or stops it. A third
force-namely, hydrodynamic flow-can modif.Y hydro-
carbon movement, but it is not essential and does not
change our basic model. Ifwater is flowing in the subsur-
face in the same direction as hydrocarbons are moving by
buoyancy, then the rate of hydrocarbon movement should
be enhanced somewhat. In contrast, if bulk water move-
ment opposes the direction of buoyant movement, then
the rate of hydrocarbon transport will be retarded. These
modifications to the overall scheme are probably minor,
however.
DISTANCE AND DIRECTION
Secondary migration occurs preferentially in the direction
that offers the greatest buoyant advantage. Thus move-
ment within a confined migration conduit will be updip
perpendicular to structural contours whenever possible.
Where faulting or facies changes create impassible bar-
riers (capillary-entry pressure exceeds buoyant force),
migration may have to proceed at an oblique angle to
structural contours.
Within a massive sandstone, secondary migration will
occur both laterally and vertically. That is, hydrocarbons
entering the sand from an underlying source rock will
move toward the top of the sand even as they migrate
laterally updip. This fact has important implications for
tracing migration pathways through a thick conduit.
Structural contours on the top of the carrier bed will in
general be more useful than contours on its base, because
final control on migration direction will be exerted by the
upper part of the bed (assuming that no laterally continu-
ous shale breaks divide the carrier bed into two or more
separate systems).
Vertical migration can also occur across formations.
Stacked sands in a paleodelta, for example, can offer pos-
sible pathways (although sometimes rather tortuous
ones) for vertical migration. Unconformities also canjux-
tapose migration conduits, thus providing a potentially
very effective system for combined vertical and lateral mi-
gration. Faults may play an important role in vertical
migration, not only because they often juxtapose carrier
beds from different stratigraphic horizons, but also be-
cause an active fault or the brecciated zone adjacent to a
fault may itself have high permeability.
The question of long-distance migration has been
much discussed and disputed. I am of the opinion that
there is no a priori reason why secondary migration
cannot be a very-long-distance phenomenon. Indeed, the
largest hydrocarbon deposits known, including the
Athabasca Tar Sands of western Canada, the heavy oils in
the Orinoco Belt of Venezuela, and the Saudi Arabian
crude oils, all must have migrated long distances; other-
wise it is impossible to account for the incredible volumes
of hydrocarbons in place today.
The problem in discussing long-distance migration is
that such cases are rare. However, they are rare for very
good geological reasons: they occur in extremely stable
tectonic settings where major but gentle downwarping
has deposited and matured huge volumes of source rocks,
and has provided as carrier beds continuous blankets of
sand juxtaposed with these source rocks (fig. 6.2). The
absence of both tectonic and stratigraphic barriers per-
mits long-distance migration.
Most basins, however, are broken up tectonically and
have poor lateral continuity of carrier beds, as a result
of both tectonic disruption and facies changes related to
tectonic events. Lateral migration is therefore often sty-
mied, leading to smaller fault-bounded accumulations
and vertical migration (fig. 6.3).
Drainage area is one of the most important factors in-
fluencing the size of hydrocarbon accumulations. Long-
distance migration implies, by definition, large drainage
areas and chances for very large accumulations. Lack of
long-distance migration opportunities implies that super-
giant and giant accumulations are far less likely and that
exploration targets will be smaller.
It is possible to have lateral migrations of as much as a
few hundred kilometers in exceptional circumstances.
Much more common, however, are basins in which lat-
eral migration distances do not exceed a few tens of
kilometers (Sluijk and Nederlof 1984). Vertical migration
distances can also be considerable, although it should be
remembered that there are two fundamentally different
types of vertical migration. Migration updip within a sin-
gle stratum can accomplish a large amount of "vertical"
migration rather painlessly. Vertical migration across
stratigraphic boundaries is more difficult. Nevertheless,
distances of several thousand feet are not unheard of
(Sluijk and Nederlof, 1984). Price (1980) has discussed
the role of vertical migration in numerous basins and
believes it is a common and very important phenomenon.
 6. MIGRATION 67

220 MILES - - - - - - - - - - - - - - - - 1
0
l- S
W
W
..... 10
.....

-
15
0
</) 20
0
Z 25
« Mature
en 30
Over mature
::J
0 35
:t 1- 1001
I- 40
45

FIGURE 6..2 Cross section from north to south across the

Eastern Venezuela Basin showing minimal tectonic disrup-
tion and excellent possibilities for long-distance migration of
hydrocarbons out of the depocenter. The heavy oils of the
Orinoco Tar Belt within this basin represent about 1(J12 bar-
rels of hydrocarbons in place, testifying to the effectiveness of
long-distance migration.

64 MILES --------------~-l

I-
W
W
.....
.....
0
en 5
0
Z
« _ Overmature
en
::J
0 1- 1001
:t
I-
V E ·,2X

10

FIGURE 6.3 Cross section across the Rhine Graben of West

Germany showing the discontinuity of strata as a result of
extensional tectonism endemic to rift basins. Lateral migra-
tion is of necessity shoft-distance, and vertical migration be-
comes important. Accumulations are small because drainage
areas are small.
68
ACCUMUlATION
INTRODUCTION
In the old days, when migration was thought to occur
mainly in water solution, the process of hydrocarbon ac-
cumulation was somewhat mystical. Hydrocarbons had
to remain in solution until they reached the trap, at which
time they suddenly became immiscible with the water
and formed a separate hydrocarbon phase. Various
mechanisms for exsolution were proposed to explain how
all this was supposed to happen.
Today we believe that hydrocarbons migrate as a sepa-
rate phase. This model greatly simplifies the problem of
accumulation, because now accumulation can occur any-
where the buoyancy-driven movement of the hydrocarbon
phase is stopped or even strongly impeded. Barriers to
migration are provided by cap rocks having low per-
meabilities to hydrocarbons: that is, rocks whose capil-
lary-entry pressures are high enough to overcome
hydrocarbon buoyancy.
ClASSICAL TRAPS
Most hydrocarbon traps are either structural or strati-
graphic. The seal prevents vertical migration from the
reservoir rock into overlying strata, while the strucure or
lithologic change prevents lateral updip migration. Clas-
sical traps are well understood, and will not be covered
further here.
KINETIC TRAPS
Kinetic traps represent a fundamentally new concept in
trapping mechanisms for hydrocarbons. Meissner (1983)
and Gies (1982) have documented kinetic trapping of
both oil and gas in several basins, and it seems likely that
as this new concept is applied it will be found to be
operative in other areas as well.
The simple principle behind a kinetic trap is that hy-
drocarbons are supplied to the trap faster than they can
leak away. Seals in the traditional sense of the word may
not exist. This model requires, of course, that strong hy-
drocarbon generation and migration be going on today.
The Elmworth Field in the Alberta Deep Basin of Canada
is the prototype for kinetic gas accumulations. Gas
generated in the late-stages of kerogen catagenesis in the
Alberta Deep Basin is trapped in a sandstone having
lower permeability than the overlying sand. The low-
permeability sand thus creates a bottleneck to gas mi-
gration. Because gas generation is very rapid, the
low-permeability sands become filled with gas. Gas pro-
duction is actually from the low-permeability sand
rather than from the high-permeability sands updip and
downdip. No traditional seal exists. Because the high-
permeability 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 associ-
ated 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 Mis-
sissippian Bakken Formation, a fractured shale that is
both source and reservoir. Much of the hydrocarbon stor-
age at Antelope is apparently in silts and sands jux-
taposed 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 excel-
lent seals. In cases where no other structural or strati-
graphic 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 dis-
cussing because they include the largest hydrocarbon ac-
cumulations known: those of the Athabasca Tar Sands
and the Orinoco heavy-oil belt.

GAS HYDRATES
Formation of crystalline hydrates of natural gas provides
an extremely efficient trapping mechanism for natural
gas, especially methane. Gas hydrates form and are stable
under pressure-temperature regimes that occur at depths
of a few hundred meters below the sea floor in deep
water, and in zones of permafrost. The base of the gas-
hydrate zone forms a pronounced seismic reflector that
often simulates bottom contours and cuts across bedding
planes (MacLeod 1982). These gas hydrates, also called
clathrates, consist of a rigid lattice of water molecules that
form a cage within which a single molecule of gas is
trapped. Methane is by far the most commonly trapped
gas molecule, but clathrates large enough to accomodate
butane molecules are known.
One important feature of methane hydrates is that they
are much more efficient at storing methane than is liquid
pore water. Because hydrate zones are often hundreds of
meters thick, the quantities of gas in such accumulations
are huge.
A second characteristic is that gas hydrates form effec-
tive seals against vertical hydrocarbon migration. Forma-
tion of hydrates thus provides an important trapping
mechanism, because much of the methane trapped is
biogenic and was formed in young, unconsolidated sedi-
ments that would have no other means of retaining the
methane.
At the present time the vast potential of gas-hydrate
accumulations is just beginning to be recognized. The
technology necessary for producing these hydrocarbons
has not yet been developed, but in the future gas-hydrate
accumulations may be of great economic significance.
EFFECTS ON OIL AND GAS COMPOSITION
I have already suggested in chapter 5 that most of the
compositional changes seen between bitumens and nor-
mal crude oils occur during expulsion (primary migra-
tion) from the source rock. The polar (NSO) compounds
interact most strongly with both mineral surfaces and
water molecules, and thus are not expelled as efficiently
with the oil phase. Once expulsion has occurred, there
may be a chromatographic iffect during secondary mi-
gration (fig. 6.4; chrematography is discussed in more
detail in chapter 7). The polar molecules once again in-
6. MIGRATION 69
PARAFFINS
NAPHTHENES
z
o AROMATICS
~
<
IE:
~
~
>- NON-HYDROCARBONS
IE:
<
o
z
o
o CARRIER ROCK
w
II)
SOURCE ROCK
FIGURE 6.4 Proposed separation of petroleum components
during secondary migration as a result of chromatographic
effects. Polar compounds interact more strongly with
water and rock minerals and thus move more slowly than
hydrocarbons.
teract most strongly with interstitial water and mineral
surfaces, and thus get left behind as the oil globule or
stringer moves upward.
Numerous compositional changes in crude oils have
been attributed to chromatographic effects during migra-
tion. These include increase in API gravity, decrease in
NSO and sulfur content, decrease in nickel, vanadium,
and porphyrin content, and increase in saturated hydro-
carbons compared to aromatics. It has even been sug-
gested that some biomarker isomers migrate faster than
others. In my opinion, however, the control experiments
in natural settings necessary to establish the validity of
such statements have not yet been carried out; perhaps
they never can be. Many of the changes ascribed to sec-
ondary migration are probably better attributed to natu-
ral variations from sample to sample, to changes that
occurred during expulsion, or to changes dependent on
other poorly understood factors. I therefore do not
look for significant compositional changes in oils during
70
secondruy migration except when biodegradation or phase
changes occur.
Biodegradation has already been discussed in chapter
5, and need not be repeated here. Although most biodeg-
radation is traditionally ascribed to events occurring in
the reservoir, under favorable conditions it can probably
begin during migration.
Phase changes occur as a result of decreases in pres-
sure and temperature during migration. When the origi-
nal hydrocarbon phase contains large amounts of light
components, these changes in temperature and pressure
can cause separation of the original phase into a liquid
phase and a gas phase. The gas phase will, of course,
contain mainly light components, but it may also include
some heavier hydrocarbons dissolved in the gas. As soon
as two immiscible phases are formed, the lighter (gas)
phase will be far more buoyant than the liquid phase. It
will therefore migrate much faster and will also assume
the structurally high position in any reservoirs containing
both phases. When separation of a single hydrocarbon
phase into two phases occurs, both new phases will have
compositions that differ drastically from the original
phase. Many light oils (often called condensates) proba-
bly have such an origin.
SIGNIFICANCE FOR EXPLORATION
Explorationists who are reading about migration will
surely ask, "What does this mean for exploration?" From
their perspective the important aspects of primary migra-
tion are the nature of the hydrocarbons expelled (oil or
gas), the efficiency of expulsion, and the timing of expul-
sion. We have already stated that oil is expelled primarily
as a liquid phase; gas is presumably expelled as a gas
phase. Efficiency of expulsion of liquids has already been
estimated to be in the neighborhood of 50% after the
expulsion threshold has been reached. Efficiency of ex-
pulsion for hydrocarbons is apparently much higher than
for NSO compounds, leading to an enrichment of hydro-
carbons in the expelled liquid.
Timing of expulsion must be dealt with in a different
way. We already know two important facts about timing
from our previous discussion: expulsion based on mi-
crofracturing cannot occur before generation, and expul-
sion occurs concurrently with generation to relieve
generation-induced overpressuring. Thus if we can deter-
mine the timing of generation, we will also have deter-
mined 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 genera-
tion 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 bar-
riers 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. Path-
ways, as we have seen, are determined by structural con-
tours on the top of the carrier beds. Barriers can be
created by folding, by faulting, by decreases in permeabil-
ity as a result offacies changes, or by the presence of tars.
Vertical-migration distances can be considerable, de-
pending upon stacking of reservoirs, vertical faulting, and
the possibilities of combined vertical and lateral migra-
tion. Lateral-migration distances are strongly influenced
by tectonic and depositional histories of basins. Tectoni-
cally stable basins have the best potential for long-
distance migration and supergiant accumulations.
Unstable basins seldom have depositional or tectonic con-
tinuities necessary for long-distance lateral migration to
occur.
In summary, as explorationists we have very pragmatic
interests in migration. We need to know when hydrocar-
bons moved, in what direction they moved, and how far
they moved. An understanding of the process of hydro-
carbon 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. De-
maison and R.J. Murris, eds., Petroleum Geochemistry and
Basin Evaluation: American Association of Petroleum
Geologists Memoir 35, Tulsa, American Association of Petro-
leum Geologists, pp. 1-14.
du Rouchet,J., 1981, Stress fields, a key to oil migration: Bulletin
 71

of the American Association of Petroleum Geologists, v. 65,

pp.74-85.
Durand, B., 1983, Present trends in organic geochemistry in
research on migration of hydrocarbons, in M. Bjon~y, ed.,
Advances in Organic Geochemistry 1981: London, Wiley, pp.
117-128.
jones, R. W., 1981, Some mass balance and geological con-
straints on migration mechanisms: Bulletin of the American
Association of Petroleum Geologists, v. 65, pp. 103-122.
Meissner, F., 1978, Petroleum geology of the Bakken Formation,
Williston Basin, North Dakota and Montana, in The Economic
GeologY of the Williston Basin: Billings, Montana Geological
Society, pp. 207-227.
Momper, j. A., 1978, Oil migration limitations suggested by
geological and geochemical considerations, in Physical and
Chemical Controls on Petroleum Migration: AAPG Continu-
ing Education Course Note Series, No.8, Tulsa, American
Association of Petroleum Geologists, pp. B1-B60.
Pratsch,j.-C., 1982, Focused gas migration and concentration of
deep-gas accumulations: Erdol und Kohle-Erdgas-
Petrochemie vereinigt mit Brennstoff-Chemie, v. 35, pp. 59-
65.
Sluijk, D. and M. H. Nederlof, 1984, Worldwide geological ex-
perience as a systematic basis for prospect appraisal, in G.
Demaison and R.j. Murris, eds., Petroleum Geochemistry
and Basin Evaluation: American Association of Petroleum
Geologists Memoir 35, Tulsa, American Association of Petro-
leum Geologists, pp. 15-26.
Chapter 7 Analytical
Techniques

INTRODUCTION
Organic geochemistry and petroleum geochemistry have
always been analysis-based sciences. Proper application
of modem analytical technology has been critical to our
ability to describe the chemical composition offossil fuels
and kerogens, to predict source potential of sedimentary
rocks, to correlate samples with each other, and to under-
stand transformation processes like biodegradation.
Without these sophisticated analytical capabilities, petro-
leum geochemistry would still be in a very primitive state.
Organic-geochemical analyses are carried out with one
of two objectives in mind: to evaluate the hydrocarbon-
source potential of a rock, or to characterize a particular
sample chemically, perhaps for the purpose of attempting
a correlation with another sample. These two distinct ob-
jectives utilize different analytical techniques.
Describing a sample chemically is simply a matter of
amassing the largest possible amount of data about its
bulk chemistry and determining the identities and con-
centrations of specific compounds in the sample. Seldom
is anyone sample analyzed exhaustively. There is there-
fore considerable latitude in selecting the particular anal-
yses desired. Factors such as cost, availability, and the
chemical characteristics of the sample itself usually dic-
tate the course of action. In the following sections we shall
discuss most of the common techniques used in describ-
ing the chemistry of fossil organic matter.
Evaluation of hydrocarbon-source potential, in con-
trast, has become somewhat more standardized in recent
years. Any evaluation of source potential must provide

73
74
three pieces of data: quantity, type, and maturity of or-
ganic 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 prepara-
tol}' steps. The methods are therefore presented in a logi-
cal analytical sequence.
Secondly, cost is a major concern in any analytical pro-
gram. We want to perform the minimum number of anal-
yses 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 ex-
ploration geologist who is aware of the great monetary
savings that can be achieved through properly designed
screening programs can often make the screening proce-
dure more cost-effective and more informative.
This chapter describes the analytical techniques and
instruments used in laboratol}' studies of organic materi-
als. Discussions of the pros and cons of the various tech-
niques, as well as interpretation of the analytical results,
are included in chapters 8 and 10.
CHEMICAL CHARACTERIZATION
FOR CORRELATIONS
BITUMEN AND OIL ANALYSES
Extraction. The first step in analyzing bitumen or crude
oil is to obtain a sample of that material. Crude oils are
usually vel}' simple to deal with because they generally
arrive as a liquid in a sample bottle. The presence of a
water emulsion is the main problem that can occur. If the
emulsion does not break spontaneously upon standing,
distillation may be necessary to remove the water.
Bitumens, in contrast, require considerably more han-
dling before analyses can begin. The bitumen must first
be separated from the rock matrix and kerogen by some
sort of extractive process. The most commonly used ap-
paratus is a Soxhlet extractor, which provides clean sol-
vent continuously by. a redistillation process. Soxhlet
extractions are normally carried out for a considerable
length of time (typically 8 to 24 hours). The extracting
solvent is usually chloroform or dichloromethane.
Metallic copper is often added to remove elemental
sulfur, which could otherwise interfere with subsequent
analyses.
Because of the length of time required for Soxhlet ex-
tractions, geochemists have sought quicker methods of
obtaining bitumen. For a number of years ultrasound was
popular, but it is seldom used today. One successful alter-
native is a ''flow-blending'' system developed by Radke et
al. (1978), in which the solvent-rock mixture is stirred
rapidly. The method requires only ten minutes of extrac-
tion time and yields results comparable to those obtained
through exhaustive Soxhlet extraction. Despite its appar-
ent technical success, however, this method has not been
widely adopted.
Once the extraction is complete, the extraction solvent
must be removed by evaporation. Solvent evaporations
are carried out slowly at low temperatures in a flow of
inert gas. Despite these precautions, virtually all of the
extract molecules having fewer than ten carbon atoms are
evaporated with the solvent, and those having between
ten and fifteen carbon atoms will be partially removed.
For this reason the extract, or bitumen, is often referred to
as the "C15 +" extract. Its composition is therefore not iden-
tical with that of the bitumen as it exists in the rock, and
will differ sharply in the lower-molecular-weight range
from an oil, which has not suffered evaporative loss.
Column Chromatography. Once the bitumen has been ex-
tracted and the solvent removed, the next step is to sepa-
rate 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 evapora-
tion 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 col-
umn chromatography (and indeed all chromatographic
techniques) are essentially the same as for chromato-
graphic separation of compounds during migration, dis-

Increa ing time •
Eluenl
I I
Oil sample
.Adsorbent
o 8
FIGURE 7.1 Column-chromatographic separation offractions
of bitumens or cru£ie oils. Saturated hydrocarbons move fast-
est, followed by aromatics and then bp NSOs.
cussed in chapter 6. In column chromatography a glass
tube 20-50 cm in length is held in a vertical position and
filled with a sluny of silica gel or alumina suspended in a
hydrocarbon solvent like n-hexane (fig. 7.1). A small
amount of bitumen or petroleum is added to the top of the
column, and the solvent is allowed to run through by
gravity flow. The hydrocarbon solvent dissolves the
saturated hydrocarbons and carries them slowly along
with it down the column. The other more polar compo-
nents of the bitumen remain stationary or move much
more slowly than the saturates. Rates of movement de-
pend upon the relative affinities of bitumen molecules for
the solvent and for the stationary phase (alumina or silica
gel). Nonpolar molecules move rapidly because they have
little affinity for the highly polar stationary phase, but they
are very compatible with the nonpolar hexane. In con-
trast, polar molecules, including aromatic hydrocarbons
and NSO compounds, are held much more tightly by the
stationary phase and cannot be eluted from the column by
n-hexane.
7. ANALYfICAL TECHNIQUES 75
Eluent Eluent
I SO CPD '
.... ... Saturates
Aromatic
....... Salurales
n-Hexane is allowed to pass through the column until
the saturated hydrocarbons have all been eluted. The sol-
vent and its dissolved hydrocarbons are collected as the
first column-chromatographic fraction. Aromatic hydro-
carbons (along with some sulfur-bearing heterocom-
pounds) 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 chroma-
tography in much the same way that column chromatog-
raphy 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
He-7
the flow of both solvent and bitumen is upward. A series
of eluting solvents of increasing polarities is used to
mobilize all the compounds. The quantity of organic mat-
ter in each fraction is then determined by combustion to
carbon dioxide, which is measured.
The Iatroscan has proven very useful in quantifYing
quickly and inexpensively the relative amounts of mate-
rial present in each fraction. For many applications, how-
ever, larger quantities of each fraction are needed for
subsequent analyses; in these cases traditional column
chromatography is preferable.
Molecular Sieving/Urea Adduction. Molecular sievmg and
urea adduction are both used to separate n-alkanes from
branched and cyclic saturated hydrocarbons, including
isoprenoids. Both techniques are applied to the saturated-
hydrocarbon fraction obtained by column chromatog-
raphy. In molecular sieving the saturated-hydrocarbon
fraction is dissolved in a solvent like benzene or cyclohex-
ane and added to a batch of molecular sieves (synthetic
zeolites), which have crystalline structures that contain
holes just large enough for n-aIkanes to fit into. Other
saturated hydrocarbons and the solvent molecules are ex-
cluded because of their greater size. When the n-aIkanes
are all trapped in the holes in the crystals, the solvent
containing the branched and cyclic hydrocarbons is de-
canted. The n-alkanes are then replaced in their holes by
H\'drocarbon
d~(e('(or
Recordc,"
FIGURE 7.2 Schematic diagram of a gas chromatograph. The
white molecules are more volatile and thus have a shorter re-
tention time than the black molecules.
addition of an n-alkane solvent, and both n-alkanes and
branched-cyclic hydrocarbons are recovered by evapora-
tion of solvent from the two fractions.
Urea adduction functions in a similar manner. Both
urea adduction and molecular sieving are often used in
conjunction with gas chromatography or combined gas
chromatography-mass spectrometry (gc/ms; see the fol-
lowing sections) in order to simplifY the spectra and make
interpretation easier.
Gas Chromatography. Gas-chromatographic analyses are
usually carried out on the saturated-hydrocarbon frac-
tions of crude oils and bitumens. A gas chromatograph is
an oven containing a long, thin, coiled column of metal or
glass (fig. 7.2). One end of the column is attached to a
heated injection port, through which the sample to be
analyzed can be introduced onto the column. The other
end is attached to a detector that can monitor the passage
of the compounds out of the colunm after they have been
separated.
The column itself can be either a packed column or a
capillary; capillary columns are far more common today.
Packed colunms contain a porous solid support material
coated with a nonvolatile liquid (organic polymer). The

27
29
31
FIGURE 7.3 Gas chromatogram of saturated hydrocarbons
from an extract of a Inw-rank coal. Series of regularly spaced
peaks comprises n-alkanes. with Cm Ct 8 • CZ7• Czs• and C31
numbered. Also identified are pristane and phytane.
unidentified peaks from n-CZ7 to n-C33 are probably steranes
and triterpanes. Reprinted with permission from Radke et
al., 1980. Copyright 1980, Pergamon Press, Ltd.
much thinner capillary columns have no solid support;
the polymer is coated directly on the walls of the column.
At the beginning of an analysis the sample is injected
with a syringe into the hot injection port. The molecules
in the sample are vaporized rapidly and swept onto the
column by an inert gas flowing continuously through the
column. The components of the injected mixture separate
as a result of differences in vapor pressure above the liq-
uid phase and in solubility in the liquid phase. The rate of
movement of a particular molecule through the column
therefore depends upon how much time it spends in the
vapor phase (in which it can be swept along) and how
much time it spends immobilized in the liquid phase.
Heavy molecules generally move more slowly than light
ones, and polar molecules move more slowly than nonpo-
lar ones. During the analysis the oven can be gradually
heated to increase the volatility and mobility of the heavier
molecules. This gradual increase in column temperature,
which is called temperature programming, permits both
7. ANAL YfICAL TECHNIQUES 77
Prj
light and heavy components to pass through the column
in a reasonable length of time.
As the compounds emerge from the column they are
detected, and a signal proportional to their concentration
is recorded. The trace representing all the emerging com-
pounds is known as agas chromatogram (fig. 7.3). Each
peak. ideally represents a single compound, but some-
times two or more compounds emerge almost simulta-
neously, and their peaks overlap.
Identification of the compounds represented by the
various peaks is carried out by comparison of retention
times (times required for components to emerge from the
column) with authentic standards. Quantification is ac-
complished either by measuring peak. heights (if all peaks
in question are the same shape) or, more correctly, by
measuring the areas under the peaks using an automatic
integrator attached to the detector.
If overlapping between n-alkanes and other peaks of
interest is severe, the gas chromatogram can be simplified
by carrying out urea adduction or molecular sieving prior
to performing gas chromatography. In most cases, how-
ever, separation of n-alkanes is not necessary.
Gas chromatography of saturated hydrocarbons is
principally used to look at n-alkane and isoprenoid distri-
butions. In some cases useful information about steranes
78
GAS CHROMATOGRAPH
(GC)
/r------------~,
=---"7"""- ----,0 _ _
INJECTOR COLUMN
/
(SEPARA TION)
(VOLA TllIZA TlON) (ION
PRODUCTION)
and triterpanes can also be obtained, but gc/ms (dis-
cussed next) is far more valuable in that regard.
Gas Chromatography-Mass Spectrometry. Combined gas
chromatography-mass spectrometry requires a gas
chromatograph interfaced with a mass spectrometer (fig.
7.4). In such a system the gas chromatograph is utilized
only to separate the components before they enter the
mass spectrometer one by one.
The mass spectrometer is designed to characterize and
identifY chemical compounds by breaking them up into
electrically charged fragments (ions). Each compound's
fragmentation pattern, which is closely related to its
chemical structure, provides a unique fingerprint for that
compound.
Fragmentation of a molecule is initiated by hitting the
molecule with a large amount of energy, thus knocking an
electron out of the molecule. The molecular ion (M +)
produced by loss of this electron has the same mass as the
original neutral molecule but bears a single positive
charge. Molecular ions also can break apart to form
smaller charged fragments.
These various molecular and fragment ions are ac-
celerated in an arc by the magnetic field within the
evacuated mass-spectrometer chamber. The radius of the
arc depends upon both the mass/charge ratio (written mlz
or m/e) of the ion and the strength of the magnetic field.
For any given field strength only those ions with a particu-
MASS SPECTROMETER
(MS)
/r--------------------------~,
..
t:
m / .217
i'" . . . . . . . . --
Z
II-
SOURCE DETECTOR RECORDER
QUADRUPOLE
ANALYZER
(ION SELECTION)
FIGURE 7.4 Schematic diagram of a combined gas
chromatograph/mass spectrometer showing the detector re-
sponse when the system is set to monitor m/z, 217, afrag-
ment ion derived mainly from steranes.
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 analy-
sis, 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 spec-
trum (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 recog-
nize 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 struc-
tures 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
 7. ANALYTICAL TECHNIQUES 79

... -! :" ., :c ~
~. '! . .. ; ..

:"~ _'I: ", ... ~v . 1..1 1..1 ~ ... \.1

."" .1' ' = \.1 :\' ... ..'v

FIGURE 7.5 Mass spectrum of 28,30·bisnorhopane, showing

the molecular ion (M+) at 384 amu and the large fragment
ion with mlz 191, typical of triterpanes. Reprinted with per-
mission from Volkman et al., 1983c. Copyright 1983, Perga-
mon Press, Ltd.

m/e 371 +R m/e 217

R TYPE OF COMPOUND MOLECULAR ION FRAGMENT ION

H CHOLESTANE (C27) 372 217

ERGOST ANE (C28) 386 217

SITOSTANE (C29) 400 217

FIGURE 7.6 Principal frag;mentation pattern for steranes in a

mass spectrometer. The large fra,ljment ion includes rings A,
B, and C, and is the same for all three steranes shown (CZ7,
Cu , and CZ9) because they have identical structures in rings
A, B, and C.
80
ISOPRENOIDS
,...,191 ,.,.",211
TRITERPANES STERANES TRIAROMATIC STERANES
A 13 DEMETHYLA TEO MONDAROMA TIC
TRITERPANES STERANES
FIGURE 7.7 Common biomarkers and their characteristic
fragment ions.
large m/z 191 peak (fig. 7.7). Triterpanes that have lost
the methyl group between the A and B rings by biodegra-
dation 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 impor-
tant 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 gas-
chromatographic 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 gas-
chromatographic 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
RetentIon
_ _to
b JWUJ:
i i i
FIGURE 7.8 Typical m/z 191 mass fragmentogram from the
saturated-hydrocarbon fraction of a shale extract. Hopanes
are shaded in black with carbon numbers marked above. Re-
printed by permission of Academic Press from Mackenzie,
1984.
order to learn about source, diagenesis, maturity, and
biodegradation. These topics have been discussed to some
extent in chapter 5, and specific examples will be shown
in chapter 10.
Isotope Measurements. The most commonly measured
isotopes are of carbon, followed by hydrogen and sulfur,
and more distantly by nitrogen (table 3.3). Isotopic mea-
surements are made on a mass spectrometer specially
designed and set up to look at a single chemical com-
pound. In principle, however, the instrument operates in
a manner similar to the mass spectrometer described earlier.
In all cases the material whose isotopic composition is
to be measured is converted completely to a single com-
pound (for carbon, it is carbon dioxide; for hydrogen, it is
water; for sulfur, it is sulfur dioxide; and for nitrogen, it is
N z ). This material is then introduced into a mass spec-
 81

trometer, where the molecules are gently ionized to form

molecular ions. The only differences among the ions are
isotopic.
The relative amounts of each isotope are determined by
comparing the amounts of ions containing the heavy
isotope with those containing the light isotope. For ex-
ample, 13COZ has a mass of 45 amu, whereas 1ZCOZ is 44
amu. The quantities of each type can be measured vel}'
accurately by the mass spectrometer. The measured
values are then corrected statistically for random contri-
butions of minor isotopes of any other elements present in
the compound being measured. In the case of carbon
dioxide, a correction for 170 would be made.
Samples on which isotopic measurements are made are
always compared directly with reference samples, called
standards (table 3.3). The value reported is thus always
the difference between the isotope ratios of the sample
and the standard. The formula for calculating isotopic
values is given in equation (3.8).

Porphyrins. Porphyrin analyses are carried out by visible-

ultraviolet (UV) spectroscopy, high-performance liquid
chromatography (HPLC), or mass spectrometry. Nickel
and vanadyl porphyrins absorb UV-visible light of differ-
ent wavelengths, permitting an estimation of the relative
concentrations of those two classes of porphyrins. The
sample is dissolved in a suitable solvent and placed in a
visible-UV spectrometer. The spectrometer scans a range
of wavelengths, and intensity of absorption is recorded as
a function of wavelength.
Prior to HPLC and mass-spectrometric analysis, the
metal ions are removed from the porphyrin molecules
with methanesulfonic acid. HPLC, which is a form of
column chromatography performed under high pressure,
separates various groups of porphyrins. As they emerge
from the column, they are measured with a UV-visible
spectrometric detector, which yields a chromatogram
(fig. 7.9).
More detailed analyses of the fractions obtained by
HPLC can be achieved using a mass spectrometer, as
discussed earlier. Because of the complexity of the por-
phyrin mixtures, only the major components have been
identified.
82
G.H
o
C
B
- - -1 - -
15
INJECT
KEROGEN ANALYSES
Kerogen Isolation. All characterizations of kerogen begin
by separating the kerogen from the inorganic rock matrix.
After the rock is ground to a fine powder, carbonate min-
erals are removed by treatment with hydrochloric acid
(Hel). Silicates are then dissolved in hydrofluoric acid
(HF), leaving a kerogen concentrate consisting of kerogen
and small amounts of acid-resistant minerals like pyrite.
For most analytical purposes this kerogen concentrate is
sufficiently pure; however, for some further analyses
(such as sulfur content) the inorganic components must
be removed. Flotation in a heavy liquid like aqueous zinc
bromide generally separates the organic and inorganic
components, although some organic particles are lost be-
cause they adhere to pyrite crystals.
Only a few analytical techniques are commonly used to
J. K
I
- . ,.,- - ---.,--.:.- -=;,:::::===:::::;,
20 25 30 35
lIME (mins)
FIGURE 7.9 HPLC chromatogram of porphyrins from a sam-
ple 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 cor-
relation with bitumens and oils. Among these are ele-
mental analysis, isotope measurements, and pyrolysis-
gas chromatography.
Elemental Analysis. Elemental analysis measures the pro-
portions of the various chemical elements in a kerogen. By
far the two most commonly measured elements are car-
bon and hydrogen. Sulfur, oxygen, and nitrogen are also
frequently determined. All other elements are of essen-
tially no importance in the geochemistry of kerogens.

Measurements of carbon, hydrogen, and nitrogen can
be canied out easily on kerogen concentrates. Automated
instruments are available that combust the kerogen, col-
lect the carbon dioxide, water, and nitrogen oxides pro-
duced, reduce the nitrogen oxides to molecular nitrogen,
and pass those three gases sequentially into detectors
where the quantities are measured and the relative
amounts of each element are calculated. Results are gen-
erally reported both as weight percent of the kerogen con-
centrate and as ratios of the number of atoms of two
elements (for example, HlC and CIN).
Sulfur is also measured by combustion and detection of
the sulfur dioxide thus produced. Sulfur analyses must be
canied out on carefully isolated pure kerogens, however,
because even tiny amounts of ubiquitous pyrite can con-
fuse the results.
Oxygen analyses are canied out by high-temperature
pyrolysis in an inert atmosphere. The CO thus produced
is measured directly or converted into CO2 before analysis
by a variety of methods.
Other Analyses. Isotopic analyses performed on kerogens
are identical to those for bitumens and crude oils previ-
ously described. Pyrolysis-gas chromatography is dis-
cussed later in this chapter.
GAS ANALYSES
By far the most common methods of analyzing gases are
gas chromatography and isotope measurements; little
other information could be obtained from these simple
molecules. Because of their volatility, gases must be han-
dled quite differently from rock or oil samples. One criti-
cal consideration is that they be maintained in sealed
containers from the time of sampling. Gas samples at the
wellhead are collected in pressure bombs and can gener-
ally be stored with confidence for relatively long periods.
Rock samples from which adsorbed gases are to be re-
leased and measured must be placed in a sealed can,
usually with plenty of water inside, as soon as they are
brought to the surface. Bactericides are sometimes added
to prevent spurious results due to microbial transforma-
tions within the can, but many problems have been expe-
rienced with such additives. The shelf-lives of canned
cuttings are not long.
A common way to sample the headspace gas (that
7. ANALYTICAL TECHNIQUES 83
a Sample
can
FIGURE 7.10 Removal of headspace ga.s from a sealed can
containing wet cuttings.
which is spontaneously released from the rock upon sit-
ting) 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 pulveriz-
ing 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 hydrocar-
bons, 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 compo-
sition 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------''------'------~------/~

C) / 0
Rock sample o...J /

.
/
>- • o. / °
I ~~~ve.. 1 ~~ 5i '60 /

.. .,.. .
Z
~P~
. .-:.•
w / .
o
::::E /.
Dell'ctol' Recorder- o "." /~.
Induction trap digital
IX:
IL
120

. .. . v .. -
" ~ 0
rUl'll3Ce voltm(,ler o
W
" 1.1. •
z /.
~
IX: / "
~ 80 • ~ .I
FIGURE 7.11 Schematic diagram of a Leco carbon analyzer. W
o /
/
/
/
SOURCE-ROCK EVALUATION /
i . 0
/
u /
QUANTITY OF ORGANIC MATERIAL o /
>-
The amount of organic material present in sedimentary /
/
rocks is almost always measured as the total-organic- OO~V______- L______~______- L______~____- - J

40
carbon (TOe) content. This simple, quick, and inexpen- 00 BO '20 '60 200

sive analysis serves as the first and most important Toe (wI. %) DETERMINED FROM CORE ANALYSIS
screening technique in source-rock analysis. Analysis
normally requires about one gram of rock, but if the rocks FIGURE 7.12 Comparison of measured TOC values with TOC
contain abundant organic matter, much smaller amounts values estimated from formation-density logs. From
can be analyzed. Schmoker and Hester, 1983.
Toe analyses are usually run on a Leco carbon ana-
lyzer, which simply combusts a sample of powdered, car-
bonate-free rock at very high temperature in the presence TYPE OF ORGANIC MATERIAL
of a large excess of oxygen (fig. 7.11). All organic carbon
Screening. Because low-TOe samples are thought to have
is converted to carbon dioxide, which is trapped within
minimal hydrocarbon-source potential, they normally are
the instrument and then released into a detector when
not analyzed further. The cutoff point for disqualification
combustion is complete. The amount of carbon dioxide
varies, but it is normally between 0.5% and 1.0% TOe.
produced is proportional to the organic-carbon content of
Most laboratories now use the higher value as their cutoff,
the rock. Carbonate is removed from the preweighed rock
but exceptions are made, especially in organic-lean sec-
sample with hydrochloric acid prior to combustion, be-
tions where most of the samples fall below the minimum.
cause carbonate minerals would also decompose during
Those samples that are selected for further analyses are
combustion to yield carbon dioxide.
next studied to see what type of organic material they
There are ways to estimate organic richness when Toe
contain.
analyses cannot be made. Schmoker (1981), Charpentier
and Schmoker (1982), and Schmoker and Hester (1983)
have used gamma-ray logs, formation-density logs, and Direct and Indirect Measurements of Kerogen Type. There are
rock color to estimate Toe values with reasonably good two distinct approaches to determining the type of or-
success (fig. 7.12). These methods are limited to very rich ganic matter in a sedimentary rock. Our objective in car-
rocks, however (TOe. greater than about 4% in most rying out source-rock analyses is to determine the
cases), and therefore cannot be considered to be general. hydrocarbon-generative potential of the kerogen. We can
 7. ANAL ¥TICAL TECHNIQUES 85

do this directly by pyrolyzing the kerogen or whole rock

and measuring the quantity and type of hydrocarbons 1 = Volatile hydrocarbons
released, or we can accomplish it indirectly by measuring 2 = Hydrocarbon dedved
chemical and physical characteristics of the kerogen and from kerogen pyrolysi Recorder'
using these to predict the nature and quantity of hydro- S3 = C02 dedved from k rogcn
carbons that could be generated from the kerogen. The pyrolysi
advantages and disadvantages of both approaches will be
discussed in chapter 8.
Although all modern geochemical laboratories offer
and use both direct and indirect methods for kerogen
analysis, most people have gravitated toward the direct
(pyrolysis) methods. Indirect methods are still often used
to supplement the information derived from the pyrolysis
work, but seldom is modern source-rock evaluation car-
ried out solely on the basis of indirect methods.

Temperature ~:u.<oI_- Rock ·unplt'

Direct Method. The direct method utilizes high-tem-
perature pyrolysis, which mimics in the laboratory the
natural hydrocarbon-generation process occurring over
much longer spans of time at much lower temperatures in
the earth. The instrument of choice for pyrolysis has
proven to be the Rock-Eval, now in its third generation.
Other pyrolyzers operate according to similar principles.
In pyrolysis analyses a small amount of powdered rock
(typically 50-100 mg for the Rock-Eval) is heated slowly
in the absence of oxygen from a starting temperature of
250 0 C to a maximum temperature of 5500 C. (Pyrolysis is
not combustion; the exclusion of oxygen insures that only
thermal-decomposition reactions occur.) During the slow
heating, two slugs of hydrocarbons are released from the
rock. The first hydrocarbons, which come off at or slightly
above 2500 C, represent those hydrocarbons already pres-
ent in the rock. These hydrocarbons are analogous to the
solvent-extractable bitumen. The detector on the Rock-Eval
monitors the outflow of these hydrocarbons, producing
a peak (called Sl) on the recording paper (fig. 7.13).
As heating continues, the flow of preexisting hydrocar-
bons out of the rock diminishes. At temperatures above
350 C a second slug of hydrocarbons begins to emerge
0
(fig. 7.13). This flux reaches a maximum when the py-
rolysis temperature is somewhere between about 420 0
and 460 0 C, and then declines through the remainder of
the pyrolysis. This second batch of hydrocarbons (called
S2) represents those ..generated from the kerogen in the
pyrolyzer by thermal decomposition of the kerogen. It is
programmer
FIGURE 7.13 Schematic diagram of a Rock-Eval pyrolyzer.
taken as the most important indicator of the present-day
ability of the kerogen to generate hydrocarbons.
During the course of pyrolysis, carbon dioxide is also
released from the kerogen. This carbon dioxide is trapped
during pyrolysis and then released into a second detector
(peak S3) after all the hydrocarbon measurements are
complete (fig. 7.13). The amount of carbon dioxide given
offby the kerogen is supposed to be related to the amount
of oxygen in the kerogen. Because high oxygen contents
are related either to woody-cellulosic source material or
to strong oxidation during diagenesis, high oxygen con-
tent of a kerogen is a negative indicator of hydrocarbon-
source potential.
Most pyrolysis techniques do not look at individual hy-
drocarbons. When all the hydrocarbons produced during
pyrolysis are analyzed together, much valuable informa-
tion is lost. In an effort to make use of this information,
pyrolysis has occasionally been linked with gas
chromatography.
In pyrolysis-gas chromatography the hydrocarbons
86
TYPE I Green River Shale
Uinta Basin
:c
o
:•
a:
RelenUon Time
FIGURE 7.14 Pyrolysis-gas chromatograms derived from
Type I and Type III kerogens. Reprinted by permission of the
American Association of Petroleum Geologists from Dembicki
et al., 1983.
produced during pyrolysis (S2 peak) are collected until
pyrolysis is complete and then are injected onto a gc col-
umn. The individual compounds produced by pyrolysis
are separated in this way, and can be identified in the gas
chromatogram. Different kerogen types can be identified
by their distinctive pyrolysis-gas chromatograms (fig.
7.14). Furthermore, correlations between oils and kero-
gens can be attempted by comparing gas chromatograms
of oils with pyrolysis-gas chromatograms of kerogens.
The "Oil Show Analyzer" essentially combines Toe
measurements with Rock-Eval pyrolysis in a single instru-
ment. It is designed for rapid wellsite estimation of
source-rock potential where the results can be used in an
ongoing drilling program.
Indirect Methods
INTRODUCTION. In contrast to the direct pyrolytic
method for determining source potential, the indirect
methods appraise a kerogen's source potential by looking
at chemical and physical characteristics that are thought
to be related to the kerogen's source potential. The indi-
rect techniques most commonly employed are micro-
scopic analysis and elemental analysis.
MICROSCOPIC ANALYSIS. Studies of kerogen particles
under a microscope .in transmitted light have been an
integral part of organic geochemistry for nearly two de-
cades. Kerogen is concentrated or isolated as previously
described and mounted on a microscope slide. Use of
oxidizing agents, such as those employed by palynologists
to make palynomorphs more recognizable, should be
avoided.
A trained observer can readily and consistently distin-
guish a large number of different kerogen particles. Some
of these, such as spores, pollen grains, acritarchs, resin
globules, and cuticular material, can be easily related to
their biological precursors. Others which have been ex-
tensively transformed by diagenetic processes bear no
morphological resemblance to their precursors.
Fluorescence measurements are often made in order to
distinguish oil-prone amorphous kerogen (fluorescing)
from inert or gas-prone amorphous kerogen (nonfluo-
rescing). A special attachment on the microscope allows
the microscopist to irradiate the slide with ultraviolet
light. Measurements of the intensity of the fluorescent
light given off after irradiation are made over a range of
wavelengths in the visible region.
ELEMENTAL ANALYSIS. Methods of carrying out ele-
mental analysis have already been discussed earlier in
this chapter. By far the most important parameter for
source evaluation is the atomic we ratio of a kerogen.
Because hydrogen is the limiting reagent in hydrocarbon
formation (that is, hydrogen runs out before carbon), the
amount of hydrogen originally present sets an upper limit
to the amount of hydrocarbon a kerogen can yield. Its
only drawback as a routine tool for kerogen analyses is
the expense and time involved in obtaining kerogen
concentrates.
The indirect methods are useful and have continued to
play an important role in source-rock evaluation even
though they have been relegated to a support position by
the popularity of Rock-Eval pyrolysis. It is advisable to
include some elemental or microscopic kerogen analyses
to confirm pyrolysis results.
MATIJRITY OF ORGANIC MATERIAL
Introduction.A substantial number of techniques for
measuring or estimating kerogen maturity have been de-
veloped over the years. All the methods have strengths
and weaknesses, and none can be applied in all cases.
The most commonly used maturity parameters today are
spore color (Thermal Alteration Index, or TAl), vitrinite
reflectance, and pyrolysis temperature. Less commonly
used are fluorescence and conodont color (CAl).
 7. ANALYTICAL TECHNIQUES 87

20

15

x
X
X
XX
XX
XX
XX
XX
XXXX
5 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 4.0 4.5 5.0 5.5 6.0
REFLECTANCE (%RO)

POPULATION GROUPS

POP. COUNT MIN. RO MAX. RO STD. DEV. MEANRO

1 5 1.11 1.39 0.094 1.29

2 45 1.46 1.98 0.116 1.71
3 5 2.06 2.41 0.118 2.25

FIGURE 7.15 Histogram of vitrinite-reflectance values for a
cuttings sample. The single mode in the distribution curve
and the tight clustering about the mean value give a high
level of confidence to the interpretation. Statistics of the vari-
ous populations of reflectance values are included.
Vitrinite Rljlectance (R,,). Vitrinite-reflectancemeasure-
ments begin by isolating the kerogen with Hel and HF as
previously described, and then embedding the kerogen
particles in an epoxy plug. After the plug is polished, the
microscopist, using a special microscope, shines light on
an individual vitrinite particle. The fraction of the inci-
dent beam that is reflected coherently is measured with a
photomultiplier and recorded and stored automatically
on a computer. If enough vitrinite particles can be found,
between 50 and 100 measurements will be taken. At the
end of the analysis a histogram of the collected data is
printed, along with a statistical analysis of the data (fig.
7.15).
Results are reported as Ro values, where the 0 indicates
that the measurements were made with the plug im-
mersed in oil. Ra values, frequently reported by Soviet
workers, are measured in air and are quite different from
Ro values.
88

Linear Semilog

1.500

'" (~
~

,
0

'3.000
3.000 X
~ ~
:z:
~
1 l-
I- A-
A-
~
OIl
OIl 0
0

4.500
o~
4.500

6.000
~I\o
,.0000L,.2,..........,,0..,.4-.....,,0~.6-.....,,0"':
.•----:"11::.0......--:'1.":2.....-:"~......;~ .2 .3 .4 .5 .6 .7 .I.t 1.0 u 2.0 30
VITRINITE REFLECTANCE (R.o/.) VITRINITE REFLECTANCE (R.%'

FIGURE 7.16 Two ways ofplotting vitrinite reflectance versus

depth for a Louisiana Gulf Coast well. Semilog plots give
Reflectance values are normally plotted versus depth in straight lines if there are no unconformities or thermal
a well. If the reflectance scale is linear, the reflectance events. Reprinted by permission of Elsevier Science Publishing
profile is curved (fig. 7.16). When we use a log scale for Company from Dow, 1977.
vitrinite reflectance, however, the plot is a straight line.
Because extrapolation of a straight line is much easier, the made in the past. A careful worker can reproduce earlier
log scale is preferable for reflectance profiles. work with excellent precision, thus defusing to a large
degree the criticism that TAl is too subjective to be valid.
Thermal Alteration Index (TAl). TAl measurements are
made on the same slides prepared for microscopic kero- Pyrolysis Temperature rrma.d. The temperature at which the
gen-type analysis. The darkening of kerogen particles maximum rate of pyrolysis occurs (top ofthe S2 peak) has
with increasing thermal maturity can be used as an indi- been used as a maturity indicator. As maturity increases,
cator of maturity. In order to minimize differences in T max increases. T max is obtained automatically along with
color caused by changes in the type or thickness of the other pyrolysis data during Rock-Eval analysis.
kerogen particles, TAl measurements are carried out on
bisaccate pollen grains whenever possible. If no pollen Kerogen Fluorescence. Fluorescence measurements used for
can be found, TAl values are estimated, with lower maturity estimations are made on isolated kerogens or
confidence, from amorphous kerogen. polished sections on the same microscope used for other
Each laboratory has reference slides so that microsco- fluorescence studies. It is most reliable when applied to
pists can continually compare the color determinations tasmanites, botryococcus, and other individually iden-
they are now making with those they and their colleagues tifiable algal bodies.

Conodont Alteration Index (CAl). Conodonts are isolated,
most commonly from fossiliferous carbonates, by remov-
ing 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
on kerogens isolated by the procedures described earlier.
The kerogen concentrate is placed in a glass tube and
inserted in an esr spectrometer, which measures the abil-
ity of the sample to absorb energy of various wavelengths.
The output data normally consist of measurements of in-
tensity of absorption, width of the absorption peak, and
the wavelength of the absorbed energy.
Bitumen Analyses. Estimates of maturity of the bitumen
fraction can be made using data on n-alkanes, steranes,
triterpanes, and porphyrins obtained from gas chro-
matography, gc/ms, ms, or HPLC as described earlier.
Interpretation of these data is discussed in chapter 8.
Fluorescence of bitumen has also been used as a matu-
rity parameter. The technique for measuring bitumen
fluorescence is very similar to that for kerogens; the bitu-
men is dissolved and moved onto a microscope slide by
thin-layer chromatography, and the solvent is evaporated.
The fluorescence of the bitumen is then measured using a
fluorescence microscope.
CONTAMINATION AND WEATHERING
SURFACE SAMPLES
The types of contamination most frequently encountered
in surface samples are caused by living organic matter or
by spills of oil. Problems with living organic matter are
easily avoided by physically removing tiny plant roots and
other recognizable debris. Mold or other surface growth
may also be present. Hydrocarbon contamination is rare
except in the immediate vicinity of production or where
vehicles are used, and therefore should be easy to avoid.
Weathering, in contrast, is almost ubiquitous, and can
extend to depths of at least 3 m, even in rocks that seem to
have retained integrity- (Leythaeuser, 1973). Clayton and
Swetland (1978) have documented reductions in TOC
7. ANALYTICAL TECHNIQUES 89
and bitumen contents of up to 60% in some near-surface
rocks. Other samples showed no weathering effects, how-
ever. Oxygen contents of kerogens are increased substan-
tially, and vitrinite-reflectance values are often increased
by weathering. Biodegradation is not responsible for
weathering; apparently the loss of organic matter is a
nonbiological oxidative process.
Geochemical analyses on outcrop samples are often
valuable but, because of weathering and occasional prob-
lems with contamination, the results should always be
viewed with some skepticism. Source-rock evaluations
based on outcrop data are likely to be more pessimistic
than if the same samples had been obtained from a well.
WELL SAMPLES
The main causes of contamination among samples ob-
tained from wells are caving and adulteration by drilling-
fluid 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 recog-
nized by careful picking of lithologies and comparison
with up-hole samples. In many cases, however, vitrinite-
reflectance measurements offer the best means of recog-
nizing 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. Fortu-
nately, palynological analysis can usually detect the pres-
ence 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 microscop-
ically, and can be removed prior to beginning the analyt-
ical 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 low-
ered by the presence of adsorbed diesel. Pyrolysis results
90
TABLE 7.1 Approximate costs in 1985
of some common geochemical analyses
Analysis
Sample handling
TOC
Rock-Eval pyrolysis
Kerogen isolation
Microscopic kerogen evaluation, includ-
ing 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 previ-
ous bitumen extraction)
Molecular sieving
Gas chromatography of saturated hydro-
carbons (requires previous bitumen
extraction and column chromatog-
raphy)
Gas chromatography-mass spectrometry
(requires previous bitumen extraction,
column chromatography, and molecular
sieving)
% Sulfur (may require previous treat-
ments)
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
'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.
are likely to be overly optimistic, because some of the
diesel emerges as the S2 peak.
Bitumen analyses are complicated by the presence of
Price per
Sample ($US)* diesel. The total quantity of extract and the ExtracVTOe
ratio become meaningless. However, because diesel con-
5 tains mainly hydrocarbons having fewer than 20 carbon
18 atoms, steranes, triterpanes, and porphyrins should be
28 unaffected. Diesel contamination can be recognized, us-
25 ing gas chromatography, by the high concentrations ofn-
50 alkanes up to about ezo •
70 ANALYTICAL COSTS
There is a wide range of prices for the various analytical
50 techniques just discussed. Toe measurements cost in the
neighborhood of u.S. $15 apiece, whereas gc/ms analyses
50 each cost about u.s. $350. A cost-effective, properly de-
65 signed analytical program will have two features: (1) It
will begin with inexpensive analyses like Toe and use
35 them to screen the samples so that expensive analyses will
75 not be requested on inappropriate samples, and (2) It will
be planned stepwise so that the results of each screening
procedure can be evaluated before further analyses are
400 requested. Attention to these two principles can dramat-
ically lower analytical costs.
A substantial number of analytical companies are will-
ing to perform organic-geochemical analyses. Some large
50 concerns offer (or will subcontract) virtually any type of
analysis desired. Others are small and specialized. Prices
50
vary from company to company, and substantial savings
65 may be possible by shopping around for the best prices.
Volume discounts are also possible.
80 Typical prices as of 1985 for a number of common
geochemical analyses are compiled in table 7.1. This
20 table should be taken as a rough guide for preliminary
75 planning purposes only. For more up-to-date quotes, con-
tact one of the companies offering these services.
SUMMARY
Most of the analytical techniques described are well
developed and can be used with good to excellent
confidence. They form the backbone of traditional or-
ganic geochemistry. Other techniques are under develop-
ment and may become available for general use before
long.
 91

There is now a high degree of competition among ana-

lytical seIVice companies for organic-geochemical busi-
ness. Shopping around for the best possible prices can
result in substantial savings. Proper planning of the ana-
lytical program can also reduce costs greatly.
More detailed knowledge of most of these analytical
procedures would require hands-on laboratory experi-
ence. If your needs or interests dictate that you become
involved in analytical procedures, a laboratory is the best
place to learn.

SUGGESTED READINGS

Borman, S. A., 1982, ed., Instrumentation in Analytical

Chemistry, Volume 2: Washington, American Chemical Soci-
ety, 414 pp.
Durand, B., 1980, ed., Kerogen: Paris, Editions Technip, 519 pp.
Epstein, A. G.,). 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,).,). L. Laporte, M. Madec, F. Marquis, P. Leplat,).
Poulet, and A. Boutefeu, 1977, Rapid method of characteriz-
ing source rocks and their petroleum potential and degree of
maturity: Revue de l'Institut Fran~ais du Petrole, v. 32, pp.
23-42 (in French).
Hagemann, H. W. and A. Hollerbach, 1983, The spectral
fluorimetric analyses of the soluble organic matter applied to
hydrocarbon source rock evaluation, in M. Bjorj'ly, ed., Ad-
vances in Organic Geochemistry 1981: Chichester, Wiley, pp.
72-75.
Heroux, Y., A. Chagnon, and R. Bertrand, 1979, Compilation
and correlation of major thermal maturation indicators: Bul-
letin of the American Association of Petroleum Geologists, v.
63, pp. 2128-2144.
Robert, P., 1981, Classification of organic matter by means of
fluorescence: application to hydrocarbon source rocks: Inter-
national)ournal of Coal Geology, v. 1, pp. 101-137.
Staplin, F. L., W. G. Dow, C. W. D. Milner, D. I. O'Connor,
S. A.). Pocock, P. van Gijzel, D. H. Welte, and M. A. Yukier,
1982, How to Assess Maturation and Paleotemperatures:
SEPM Short Course Number 7, Tulsa, 289 pp.
Teichmiiller, M. and B. Durand, 1983, Fluorescence microscop-
ical rank studies on liptinites and vitrinites in peat and coals,
and comparison with results of Rock-Eval pyrolysis: Interna-
tional)ournal of Coal Geology, v. 2, pp. 197-230.
Chapter 8 Source-Rock
Evaluation

DEFINITION OF SOURCE ROCK

Much of modern petroleum geochemistry depends upon
accurate assessment of the hydrocarbon-source capabili-
ties of sedimentary rocks. Although the term source rock
is frequently used generically to describe fine-grained
sedimentary rocks, that usage is a bit too broad and loose.
I prefer to make the following distinctions:

Effective source rock: any sedimentary rock that has

already generated and expelled hydrocarbons.
Possible source rock: any sedimentary rock whose
source potential has not yet been evaluated, but which
may have generated and expelled hydrocarbons.
Potential source rock: any immature sedimentary rock
known to be capable of generating and expelling hydro-
carbons if its level of thermal maturity were higher.

It follows from these definitions that a particular

stratum could be an effective source rock in one place; a
potential source rock in a less-mature area; a possible
source rock in a nearby unstudied region; and might have
no source potential at all in a fourth area where important
facies changes had resulted in a drastically lower content
of organic matter. For example, the Phosphoria Forma-
tion of Wyoming and Idaho belongs to each of these
classifications in different areas (Claypool et aI., 1978;
Maughan, 1984).
The term "effective source rock" obviously encom-
passes a wide range of generative histories from earliest

93
94

TABLE 8.1 Categories of source rocks

-:'/.1
and their source capacities

Original Remaining CJ 900

Category of
Source Rock
Source
Capacity"
Source
Capacityt
Hydrocarbons
Generated ...
0

~ A I>. A
Possible Go unmeasured unmeasured CJ 750 - A A
I>. AA
Potential Go Go none ~
J~
Effective Go G Go-G bn I

Nonsource none none none .§. 600 --4'

A
II
'Go is not necessarily the same for all rocks.
><
~ i*V
-,*9-
~-

*.'*
tMeasured in the laboratory. Q
Z 450 -
*
maturity to overmaturity. When we analyze a rock sample
in the laboratory, we actually measure its remaining (or
Z
~
C!J
I
•
0 300 []
untapped) source capacity at the present day. This quan- c: \

150 - .
0
tity, which we can call G, is most meaningful if we can
compare it to the rock's original source capacity, Go. The
Q
>-
~
.\ A
I
D

difference between Go and G represents the hydrocarbons e AI>.

eJeAI>.A
already generated in the effective source rock. However, 0

we cannot measure Go directly for a sample that has al-

••'
10/0'0
~.
D 0

00
~_ o000
0, m
0 .......
ready begun to generate hydrocarbons; instead it must be 0 I
estimated by measuring G for a similar sample that is still Q50 100 IS0
immature. Go can only be measured directly for immature --~. OXYGEN INDEX (mg C02/g TOC)

*
source rocks, where G and Go are identical. Table B.1
summarizes this discussion. A GREEN RIVER SHALE

LOWER TOARCIAN, PARIS BASIN

PRINCIPLES OF SOURCE-ROCK EVALUATION
A SILURIAN DEVONIAN, SAHARA LIBYA
DETERMINATION OF REMAIMNG SOURCE CAPACITY (G)
• UPPER PALEOZOIC, SPITSBERGEN
We have noted that the quantity actually
Introduction.
measured in the laboratory is always G, the remaining
o UPPER CRETACEOUS, DOUALA BASIN

source capacity. Chapter 7 outlined direct and indirect • CRETACEOUS, PERSIAN GULF (OLIGOSTEGINES LIMESTONE)
approaches to the problem of determining G. Both ap- C UPPER JURASSIC, NORTH AQUITAINE
proaches have strong and weak points that will be dis-
cussed in the following sections. Y INCREASING MATURATION

The Direct (Pyrolysis) Method.In the direct method using
Rock-Eval pyrolysis, the measured S1 value represents
those hydrocarbons preexisting in the rock since deposi-
tion plus those generated in the subsurface. S2 represents
G, the remaining hydrocarbon-generative capacity. S3 is a
measure of the oxyg~n content of the kerogen.
Rock-Eval pyrolysis results are often plotted on a
FIGURE 8.1 Modified van Krevelen diagram used for Rock-
Eval 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 en-
titled ''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 95

if"
PRINCIPAL PRODUCTS iii OM
II:
OF
, W
ti \
•\
s~
KEROGEN EVOLUTION
!
•
JC
5.
~
C02. H20
Oil %
'OGO
• 5,

I.SO
_ GAS
...
~
II.
g
\ ., 5, + S,

u '000
•
"'
:r ""'-.
U'·
~
:E 1000
'-...... -
0 1.00 0 0 .' 0 .2 0 .) 0.0 O.S
I-

lk.
et PRODUCTION INDEX
, OM

OSO
0 010 020
ATOMIC OIC
FIGURE 8.2 Van Krevelen diagram showing variation in
atomic HIC and OIC ratios for immature Types I, II, and III
kerogens and the evolutionary paths for each kerogen type
during catagenesis. Reprinted by permission of the American
Association of Petroleum Geologists from Tissot et al., 1974.
modified van Krevelen diagram (fig. 8.1; compare with
figs. 4.6 or 8.2). Hydrogen index (peak S2 normalized for
TOC content) replaces atomic HlC ratio, and oxygen in-
dex (peak S3 normalized for TOC content) replaces
atomic O/C ratio in the original van Krevelen diagram.
Maturation pathways followed by kerogens are very
similar to those seen in van Krevelen diagrams, with the
oxygen index decreasing at the onset of maturation, fol-
lowed by a decrease in the hydrogen index during hydro-
carbon generation. In the late stages of maturity all
kerogens have low pyrolysis yields.
Since kerogen is converted to bitumen during hydrocar-
bon generation, with increasing maturity the S2 peak de-
creases and S1 increases. The ratio Sl/(S1 + S2), called
the Production Index or Transformation ratio, should
increase with increasing maturity, as shown in an un-
usually nice example from the Paris Basin (fig. 8.3). In
practice, however, natural variations from sample to sam-
ple and migration of hydrocarbons into and out of rocks
complicates this simple picture, preventing the Produc-
tion Index from being a reliable indicator of maturity.
q
1000
q.. TMilI
,,
, 2000
'0. .
'0.
..
''0•
"0"
lOOO
UO "0 •• 0 '.0
430'C TEMPERATURE ('CI
FIGURE 8.3 Increases in maturity in Toarcian Paper Shales
of the Paris Basin with increasing depth of burial, as
niflected in increases in the 81 peak, decreases in 82, increases
in the ratio 811(81 + 82), and increases in T max' Reprinted by
permisssion of the Societe des Editions Technip: figure 12
from the article entitled ''Methode rapicle de caracterisation
des roches meres, de leur potentiel petrolier et de leur degre
d'evaluation" by J. Espitalie et al., published in the Revue de
l'Institut Fral1fais du Petrole, vol. 32, no. 1, Jan.-Feb. 1977.
S3 is the most controversial parameter measured. Col-
lection 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 suc-
cessful. Samples containing carbonates often give spuri-
ously 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
of the direct (pyrolysis) method are that it is cheap and
quick, and it mimics the natural hydrocarbon-generation
process occurring in the subsurface. These features have
made pyrolysis very popular and valuable. There are,
96

kerogens often give pyrolysis results very different from

kerogens in contact with a mineral matrix (fig. 8.4).
The current feeling among many workers is that Rock-
Isolated Kerogen Eval pyrolysis probably works well in most cases, but in
samples where there is a significant catalytic effect by clay
minerals, pyrolysis data will underestimate the true
c
.2 source potential. Under pyrolysis conditions, clays appar-
~ ently foster conversion of some bitumen to a carbona-
c:
III 0
~
ceous residue that never reaches the detector. Under
0 ...J
C
0 natural conditions, where oil generation is occurring at
0
III s: much lower temperatures, the bitumen would be success-
i'"
.~
iii fully expelled.
Qj Whole Rock
a: One solution to pyrolysis problems, which are most
pronounced for shales that have certain clay-mineral
compositions and Toe values below 10/0, is to isolate a
few kerogens and pyrolyze them as spot checks on the
.;..~ I II I I I ' .1.l....4.L._ validity of whole-rock-pyrolysis data. This answer obvi-
Light PrO::lucts Heavy PrOducts ously adds to the analytical costs, however, and because
Retention Time
only spot-checking is done, some problems may escape
detection.
FIGURE 8.4 Comparison of pyrolysis-gas chromatograms
from whole-rock pyrolysis and isolated-kerogen pyrolysis of a
T)'pe III kerogen. Reprinted by permission of the American Indirect Methods. Indirect methods for calculating the
Association of Petroleum Geologists from Dembicki et al., quantity G all break it down into two parameters: quan-
1983. tity and type (quality) of organic matter. Each of these
parameters is measured separately; they are then com-
bined to give an estimate ofG. Both microscopic kerogen-
however, some important disadvantages to pyrolysis that
type analysis and elemental analysis are normally
make it dangerous to rely exclusively on that technique.
coupled with an independent determination of kerogen
One disadvantage is that pyrolysis itself tells us only
quantity, such as Toe.
about the present·day hydrocarbon-generative capacity of
a kerogen. If catagenesis has begun, the pyrolysis behav-
ior of the kerogen will be different than if it were still Advantages and Disadvantages of Indirect Methods
immature. Furthermore, pyrolysis averages the contribu- INTRODUCTION. One advantage of the indirect
tions of all macerals present in the sample being studied methods is that they give us a more complete picture of
and reveals no details about the chemical nature of the the chemical composition and history of a kerogen, and
kerogen or the types of organic matter that have formed it. thus enable us to understand more fully the various
Another disadvantage is that we cannot be sure that the geochemical and geological processes that affect source-
very high temperatures used in laboratory pyrolysis pro- rock quality. Another advantage is that we normally use
duce the same effects as the much lower temperatures more than one indirect method, enabling us to compare
acting over longer times in natural environments. 1\vo the results from several techniques and thus recognize
kerogens that behave similarly in the laboratory might act problem samples. Disadvantages are two: speed and cost
quite differently in subsurface environments. Further- of the analyses are not as favorable as for pyrolysis, and
more, any effects of mineral catalysts will probably be our analytical results do not tell us directly about hydro-
much greater in th~ laboratory than in the subsurface. carbon-generative capacity.
Removing mineral matter solves this problem; isolated The indirect methods require that organic-carbon con-

tent be measured independently. Measurement of Toe
values is straightforward (chap. 7), but the selection of
samples for Toe analysis presents some philosophical
problems. Let us look at these questions, and then at the
technical merits of both elemental analysis and micro-
scopic kerogen evaluation.
TOC ANALYSES. When Toe measurements are made
on core samples, it is customary to sample the particular
lithology of interest. The measured Toe value is therefore
not necessarily representative of the entire core, and re-
sults must be interpreted accordingly. More often, how-
ever, the samples submitted are cuttings, which may
contain mixtures of lithologies, including caved material
and contamination of various kinds. Prior to making Toe
measurements a technician should remove obvious con-
tamination and caving.
When more than one lithology is present, an important
philosophical decision must be made. If we are looking
for particular organic-rich units in order to evaluate their
source potential, then we will elect to hand-pick a sample
containing only that particular lithology. I personally pre-
fer this approach, because it gives the most accurate
evaluation of those rocks actually possessing most of the
source potential. The other approach is to measure the
TOe content of the unpicked sample in order to get an
overall appraisal of the whole section. The deficiency in
this approach is that if a small amount of excellent source
rock is diluted with a large amount of barren rock, the
overall average will be unduly pessimistic. Because both
philosophies are followed in different cases, one must be
aware how a sample was handled prior to analysis in
order to interpret data correctly. If you are the one re-
questing the analyses, make sure that you make your
wishes clear.
An example of the dramatic effect that dilution by bar-
ren material can have comes from a well in which nearly
100 cuttings samples had Toe values averaging about
0.5%, with a maximum of1.2%. One core was submitted
with the cuttings; a sample of black shale from it was
found to contain more than 4% TOe. It would be a great
coincidence if the one core analyzed contained the only
rich shale in the entire section. A much more likely expla-
nation is that many of the cuttings bags also contained
some organic-rich shale, but that volumetrically those
shales were overwhelmed by the large amount of sand in
8. SOURCE-ROCK EVALUATION 97
the section. In this case the average TOe of 0.5% is proba-
bly 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 micros-
copy to kerogen analyses. The technique is undeniably
subjective, and results will vary from operator to
operator. Nevertheless, with careful attention to stan-
dards, an experienced worker can usually reproduce his
or her own earlier results with excellent precision. Differ-
ences between workers are often more a matter of seman-
tics than substance.
A second problem is that when kerogens become very
mature, the particles become opaque and difficult to rec-
ognize. 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 con-
tain some plant wax or tiny globules of resinite that would
impart to it a significant hydrocarbon-generative capac-
ity. If these tiny inclusions are not recognized microscop-
ically, 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 precur-
sors. 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-oil-
generative kerogens. Fluorescence is useful in distin-
guishing between oil-prone amorphous kerogens derived
from lipid-rich organic matter and non-oil-prone amor-
phous kerogens formed by degradation of woody or cel-
lulosic 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 there-
fore be used with extreme caution, preferably in conjunc-
tion 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. Equa-
tion (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)
Saxby found that his equation worked for predicting oil
yields from both coals and oil shales during slow, low-
temperature pyrolysis. He cautioned, however, against
using it for samples containing large amounts of
inertinite.
NUCLEAR MAGNETIC RESONANCE (NMR). Miknis et
al. (1982) have used nmr to evaluate source potential by
distinguishing saturated-hydrocarbon portions of kerogen
from aromatic portions. No routine application of this
technique to exploration has yet been made, however.
One advantage of nmr is that it is nondestructive.
SUMMARY
Despite high expectations that accompanied the arrival of
the Rock-Eval a few years ago, the problem of evaluating
G has not yet been solved perfectly. Whole-rock pyrolysis
has severe limitations in some shales. Pyrolysis or elemen-
tal analysis of isolated kerogens is too expensive to be
used routinely, and visual kerogen-type analyses are not
vel}' reliable. Perhaps the most cost-effective solution in
the future will be to use TOC measurements as a prelimi-
nary screen, whole-rock pyrolysis as a second screen, and
kerogen pyrolysis, elemental analysis, or microscopic
analysis for more detailed studies of possible source-rock
intervals.
DETERMINATION OF MATURITY
Introduction. Knowing a rock's remaining source capacity
G solves only one part of the puzzle; it is also necessary to
know what level of thermal maturity is represented by
that particular G value. For example, if G is vel}' low, is it
because the rock never had a high initial source capacity,
or is it because the rock is "burned out" (i.e., overmature,
in which case virtually all the initial hydrocarbon-source
capacity has already been used up)? The exploration im-
plications of these two scenarios are, of course, vel}'
different.
Maturity can be estimated by several techniques de-
scribed in chapter 7. The strong and weak points of each
method are discussed below.
Vitrinite &iflectance (Ro). Vitrinite-reflectance techniques
were developed about a half centul}' ago for measuring
the rank of coals, in which the vitrinite maceral is usually
vel}' common. The method is based on the fact that with
increasing thermal stress, the reflectance value of vitrinite
increases.
There are, however, many problems with vitrinite
reflectance as applied to kerogens. In many rocks vitrinite
is rare or absent. Because what is present is often re-
worked, its maturity is not related to that of the rock in
which it is found. Reworked vitrinite is, in fact, far more
common in shales than in coals, leading to frequent
difficulties in establishing which vitrinite population is
indigenous. The ideal histogram of reflectance values (fig.
7.15) is therefore rather rare; more common are histo-
grams showing few vitrinite particles or multiple modes
as a result of first-cycle vitrinite contaminated with re-
worked vitrinite or caving of less-mature material from
up-hole (fig. 8.5). Such histograms are quite often difficult
or impossible to interpret, unless surrounding samples
help us determine the indigenous vitrinite population.
Other macerals or solidified bitumens can often be
misidentified as vitrinite. Because each maceral type in-
creases in reflectance in a slightly different way as ther-
mal stress increases, misidentification of macerals can
cause problems, even for experienced workers. The vari-
 8. SOURCE-ROCK EVALUATION 99

20

15

x X
X X X
x X X XX X X

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
REFLECTANCE (%RO)

POPULATION GROUPS

POP. COUNT MIN. RO MAX. RO STD. DEV. MEANRO COMMENTS

1 1 1.78 1.78 1.78

2 10 2.59 3.80 0.379 3.35 Indigenous
3 1 4.27 4.27 4.27
A

FIGURE 8.5 Vitrinite-reflectance histograms of samples that

are difficult to interpret due to (A) lack of vitrinite,
100

20

15

10

x
XX X
5 XX X
XX XXX X X
XXX XXX X X
xxxxxxxx X XXX
xxxxxxxxxxxx xxxxx
x xxxxxxxxxxxxxxx x x

0.0 0.5 1.0 1.5 2.0 2.5 3.0

REFLECTANCE (%RO)

POPULATION GROUl'S

POP. COUNT MIN. RO MAX. RO STD. DEV. MEAN RO COMMENTS

1 1 0.36 0.36 0.36

2 27 0.50 0.75 0.073 0.67 Inrligenous
3 45 0.80 1.89 0.244 1.1:3
B

FIGURE 8.5 Cont. (B) presence of large amounts of reworked

vitrinite that produce a second mode, and
 8. SOURCE-ROCK EVALUATION 101

20

15

5
x
X
X
XXX
xxxx XXX XX X X X XX XX

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
REFLECTANCE (%RO)

POPULATION GROUPS

POP. COUNT MIN. RO MAX. RO STD. DEV. MEANRO

1 9 0.59 0.89 0.102 0.77

2 4 1.03 1.21 0.079 1.11
3 4 1.51 2.25 0.275 1.82
4 3 3.82 4.52 0.321 4.27
5 2 5.72 5.94 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.
102
ous types of vitrinite themselves vary in composition and
may not all mature at the same rate.
Finally, vitrinite is thought by most people to be rather
unimportant in the oil-generation process. Changes in vi-
trinite reflectance therefore have little or nothing to do
with oil generation. Their application in assessing kero-
gen maturity may in fact be based on a coincidence that is
not always valid.
Despite its weaknesses, vitrinite reflectance is the most
popular technique today for estimating kerogen maturity.
In many areas it is easy to use and valuable. In other
rocks, however, paucity of first-cycle vitrinite renders vit-
rinite-reflectance measurements essentially worthless. In
all cases it is worthwhile to supplement vitrinite with
other measures of maturity; in some cases it is essential.
Thermal Alteration Index (TAl). Although TAl determina-
tions are subjective, use of careful standards and the same
type of palynomorph in each analysis greatly aids repro-
ducibility. TAl measurements are therefore often quite
accurate and correlate very well with results from other
techniques. The chief problems arise with inexperienced
workers, lack of proper standardization, or most com-
monly, the absence of spores and pollen in the samples.
\\'hen palynomorphs are absent, TAl values must be es-
timated from amorphous debris, which can vary greatly
in its chemical and physical properties. TAl values es-
timated from amorphous material are always suspect and
should be corroborated by other analyses.
Pyrolysis temperature is frequently used as
Pyrolysis T max.
a maturity indicator, because as the maturity of a kerogen
increases, the temperature at which the maximum rate of
pyrolysis occurs increases (fig. 8.3). The parameter T max
(temperature at which the S2 peak reaches its maximum)
has become a standard part of Rock-Eval output data.
Because T max is obtained at no extra cost when pyrolysis is
performed, it has become a popular analysis.
There are, however, some problems associated with
T max data and their interpretation. For example, T max is
dependent upon kerogen type. Because kerogen type usu-
ally varies from sample to sample in a well profile, T max
often does not show a regular progression with depth.
Isolated T max data are not trustworthy.
Kerogen Fluorescence.Fluorescence is most useful for kero-
gen-maturity determinations when measurements are
made on specific algal constituents, such as Tasmanites.
Such materials are quite rare in most samples, however.
Furthermore, most fluorescence disappears or becomes
useless as a maturity indicator rather early, at reflectance
levels of about 1%. Thus at the present time fluorescence
is a supplementary tool for corroborating maturity data
from other techniques. In the future its range of applica-
bility may be expanded. It is not yet generally available
on a commercial basis and is used by only a few
laboratories.
Conodont Alteration Index (CAl). Although conodonts are
composed of carbonate apatite, changes in conodont
color are apparently due to carbonization of inclusions of
small amounts of organic matter during catagenesis and
metagenesis. One advantage of CAl over other maturity
parameters is that because conodonts existed as early as
the Cambrian, they offer a means of measuring maturity
in rocks that do not contain pollen grains or vitrinite.
Furthermore, conodonts are plentiful in carbonate rocks,
where pollen and vitrinite are often absent. Thirdly, the
CAl scale is most sensitive at levels of maturity much
higher than can be measured by TAl, and thus helps
expand the range over which maturities can be mea-
sured. Finally, CAl is inexpensive and easy to measure
and, with the help of beautiful color charts published by
Epstein et al. (1977), can be carried out by inexperienced
personnel.
One disadvantage of CAl measurements is that CAl
values can be dramatically increased in the presence of
hot brines, leading to an inaccurate assessment of kero-
gen maturity. Other disadvantages overlap with some of
the advantages. Conodonts do not occur in rocks younger
than the Triassic, and thus are of no value in many areas.
They are normally isolated only from fossiliferous carbon-
ates. Large amounts (500 g) of sample are usually re-
quired, and even then many samples are barren. They are
not very sensitive indicators of maturity within the oil-
generation window, where most of the interest is. Fi-
nally, because the organic metamorphism displayed by
conodonts is not related to hydrocarbon generation
or destruction, CAl is only an indirect indicator of
hydrocarbon maturity.

20
00
O~--------~r---------~r---------~----------~O
FIGURE 8.6 Change in esr signal intensity (paramagnetic sus-
ceptibility) of kerogen as a function of vitrinite reflectance in
the Douala Basin, Cameroon. The downturn at high matu-
rity levels is typical of esr profiles. Reprinted by permission
of the Societe des Editions Technip from Marchand and
Conard, 1980.
Electron-Spin Resonance (esr). In recent years esr has sel-
dom been used as a maturity parameter because of com-
plications in interpreting measured data. Marchand and
Conard (1980) commented that only the esr signal inten-
sity is useful for source-rock applications; other parame-
ters 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 matu-
rity determinations would thus require analysis of enough
samples to create a profile.
8. SOURCE-ROCK EVALUATION 103
10
Rtfltctan~ (Xl
The first maturity indicator
Carbon Prtiference Index (CPI).
applied to sediments was the Carbon Preference Index, as
defined on page 46. Early investigations showed that im-
mature rocks often had high CPI values (> 1.5), whereas
those of oils were almost always below 1.2. This discovery
led to the use of CPI as an indicator of maturity. Later it
was realized that the decrease in CPI with increasing
maturity depends upon the type of organic matter origi-
nally present as well as on maturity. In particular, rocks
deposited in pelagic environments, in which the input of
terrestrial lipids was very limited, have low CPI values
even when immature.
Furthermore, in the last decade kerogen analyses have
replaced bitumen analyses as the routine procedure in
source-rock evaluation. As a result, fewer CPI determina-
tions are made now.
I do not encourage ordering CPI determinations solely
as maturity indicators. On the other hand, if gas
chromatography is performed for other reasons, CPI
values may be useful in confirming maturity data ob-
tained by other methods.
104

Polycyclic Biomarkers. A problem endemic to all kerogen-
maturity indicators is that they do not directly measure
hydrocarbon generation or changes in the bitumen frac-
tion. We must take a leap of faith that changes in the
kerogen are related to or indicative of hydrocarbon gener-
ation. Thus the application of gc/ms a few years ago to
measure the maturity of bitumens and oils directly from
their sterane and triterpane distributions was greeted
with great interest and expectations. When perfected,
these techniques were expected to replace to a large ex-
tent the kerogen-maturity indicators.
Unfortunately, actual application of gc/ms data to ma-
turity questions has proved more difficult than most
workers originally anticipated. Because the analyses are
expensive, they are not used by most laboratories on a
routine basis at the present time.
Some of the problems associated with biomarker-
derived maturities may disappear as our experience and
expertise in working with biomarkers increase. For ex-
ample, poor separation of peaks in a mass chromatogram
can lead to erroneous identification of compounds and
incorrect ratios of biomarkers. Migration of hydrocarbons
into rocks can create problems; if they are not recognized
as nonindigenous, eIToneous conclusions about maturity
may be drawn. The most serious problem, however, is
that the various biomarker ratios do not change in the
same sequence in all rocks. Mackenzie (1984) believes, in
fact, that accurate use of biomarkers as maturity parame-
ters will require basin-by-basin calibration.
Despite these difficulties, biomarkers can be used cau-
tiously for maturity estimations as well as correlations
wherever they are available. At the present time, how-
ever, they should still be viewed as a technology under
development and should be supported by other maturity
determinations.
Bitumen Fluorescence. Fluorescence of extractable organic
material has been used as a maturity parameter by
Hagemann and Hollerbach (1983), but it should still be
considered as a technique under development. Changes
in fluorescence wavelength within the oil window have
been noted, but no general correlation with other matu-
rity parameters has been carried out.
Light Hydrocarbons. Light-hydrocarbon concentrations are
frequently used as a direct indicator of hydrocarbon gen-
eration. 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 through-
out the section in order to establish a good data trend.
Summary. The feeling of most workers today is that there
is no single maturity indicator that tells the whole story
unerringly all the time. All the techniques discussed are
useful and probably reasonably accurate if the analytical
work is carefully done. The key to using maturity parame-
ters effectively lies in evaluating the measured data care-
fully (and sometimes with skepticism) and, whenever
possible, in obtaining more than one maturity parameter.

Porphyrins. Porphyrins are seldom used as maturity pa-

rameters, because the necessary technology is expensive
and still under development. Analyses are difficult, and
interpretation is not always straightforward. For mea-
surements to be most meaningful, nickel and vanadyl
species should be separated prior to analysis because of
their different rates of reaction.
 8. SOURCE-ROCK EVALUATION 105

2
z
<C
. ..
(!)
a:
o
C>
'"z (!)
00
~.j
<C Z- 2
(.)0
OlD
a: a:
c <C
>- (.)
J:
....
(.)
.;,
(.)
C>
E

DEPTH. FEET (M~FT';- 3.28)

FIGURE 8.7 Ratio ofCs-C7 (gasoline-range) hydrocarbons to

TOC versus depth of burial for lacustrine facies of the Uinta
Basin. The large increase in gasoline-range hydrocarbons in-
dicates the oil-generation window. From Anders and Gerrild,
1984.
ESTIMATION OF ORIGINAL SOURCE CAPACITY (Go)
Of the three major methods of determining kerogen type,
only microscopic analysis is relatively unaffected by matu-
rity. As long as kerogen particles are not completely
black, they can usually be identified with reasonable
confidence. The exception to this rule is with amorphous
material, where the fluorescence that enables us to distin-
guish between oil-prone and non-oil-prone disappears
toward the end of the oil-generation window.
Pyrolysis yields are, of course, strongly affected by ma-
turity. The most common method for taking maturity ef-
fects into account in evaluating pyrolysis data is to use a
modified van Krevelen diagram (fig. 8.1) to back-
calculate the original hydrogen index. This method works
fairly well if the kerogen is still within the oil-generation
window. It breaks down at high maturity levels, however,
because all kerogens have low pyrolysis yields. Without
additional information,. therefore, it is impossible to deter-
mine which maturation path brought it to that point.
Like pyrolysis, atomic HlC ratios measure the present-
day status of the kerogen rather than its original chemical
composition. Atomic HlC ratios must therefore be cor-
rected for the effects of maturation by using a van Kreve-
len 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
Almost all measurements of the amount of organic matter
present in a rock are expressed as TOC values in weight
percent of the dry rock. Because the density of organic
matter is about one-half that of clays and carbonates, the
actual volume percent occupied by the organic material is
about twice the Toe percentage. A fairly standard scale
has evolved for interpretation ofTOC values (table 8.2).
Those rocks containing less than 0.5% TOC are consid-
ered to have negligible hydrocarbon-source potential. The
amount of hydrocarbons generated in such rocks is so
small that expulsion simply cannot occur. Furthermore,
the kerogen in such lean rocks is almost always highly
oxidized and thus of low source potential.
106
TABLE 8.2 Indications of source-rock
potential based on Toe values
Toe Value (weight %) Source-Rock Implications
< 0.5% negligible source capacity
0.5%-1.0% possibility of slight source capacity
1.0%-2.0% possibility of modest source
capacity
> 2.0% possibility of good to excellent
source capacity
Rocks containing between 0.5% and 1.0% Toe are
marginal. They will not function as highly effective source
rocks, but they may expel small quantities of hydrocar-
bons and thus should not be discounted completely. Kero-
gens in rocks containing less than 1% TOe are generally
oxidized, and thus of limited source potential.
Rocks containing more than 1% TOe often have sub-
stantial source potential. In some rocks TOe values be-
tween 1% and 2% are associated with depositional
environments intermediate between oxidizing and reduc-
ing, where preservation of lipid-rich organic matter with
source potential for oil can occur. Toe values above 2%
often indicate highly reducing environments with excel-
lent source potential (see chapter 2).
Interpretation of Toe values therefore does not simply
focus on the quantity of organic matter present. A rock
containing 3% TOe is likely to have much more than six
times as much source capacity as a rock containing 0.5%
TOe, because the type of kerogen preserved in rich rocks
is often more oil-prone than in lean rocks. We therefore
use Toe values as screens to indicate which rocks are of
no interest t6 us (TOe < 0.5%), which ones might be of
slight interest (TOe between 0.5% and 1.0%), and which
are definitely worthy of further consideration (TOe >
1.0% ).
Many rocks with high Toe values, however, have little
oil-source potential, because the kerogens they contain
are woody or highly oxidized. Thus high Toe values are
a necessary but not sufficient criterion for good source
rocks. We must still determine whether the kerogen pres-
ent is in fact of goocl hydrocarbon-source quality.
TIFEOFOR~CMATffiR
Microscopic kerogen-type analysis describes the propor-
tions of the various macerals present in a sample. In inter-
preting 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. Never-
theless, 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 capac-
ity of a rock to release or generate hydrocarbons or car-
bon 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 in-
dex, respectively. Because variations in TOe have been
removed in the normalizing calculation, the hydrogen in-
dex serves as an indicator of kerogen type.
Measured hydrogen indices must be corrected for ma-
turity 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 oil-
generative 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 Source potential of immature

kerogens based on hydrogen indices

Hydrogen Index Principal Relative 110

....
(mg HClg TOe) Product Quantity ~
.lo.
"-
< 150 gas small lao
.,?C:
150-300 oil + gas small
f '"

/
300-450 oil moderate 90 ",0

450-600 oil large ,.,- ~~!fJ'J

i/oO}
.
2
> 600 oil very large ~ 60
",
....J:.

E
f?ld:

/
0. /
0.
"I
~ 70
crPI
TABLE 8.4 Prediction of hydrogen indices of '" sJ
~
,'t

"
.:5
,,'
",'"
immature kerogens based on atomic Hie and OIC ratios 0
...J <,,0'
,,/ 10
()
UJ
> ",b
<;3l;
,
~

Atomic Atomic Hydrogen Cf)

iii ~o 0'1) o{>;
Hie ole Index' Product >-
...J
;Q'" •
0
a: ~
"'~ ~
>- 40
1.60 0.06 700 oil 0.. is'''
/ /i
1.50 0.08 622 oil
30
1.40 0.09 550 oil
1.30 0.10 477 oil
20
1.20 0.11 405 oil
1.10 0.12 332 oil + (gas)
1.00 0.14 254 oil + gas '0

0.90 0.16 176 gas + (oil)

0.80 0.18 98 gas 5 11 13 15 17

0.70 0.20 20 (gas) ORGANIC CARBON, IN WEIGHT PERCENT

'Calculated according to equation (8.1), adapted from Saxby (1980).

gens with hydrogen indices above 600 usually consist of
nearly pure Type I or Type II kerogens. They have excel-
lent potential to generate liquid hydrocarbons.
Atomic Hie ratios of immature kerogens can be cor-
related with pyrolysis yields, using equation (8.1) (see
table 8.4), or can be interpreted directly. we ratios above
1.2 indicate very good to excellent potential for oil genera-
tion; most Type I and Type II kerogens fall in this range.
we ratios between 1.0 and 1.2 indicate fair to good po-
tential for liquid hydrocarbons. we ratios below 1.0 oc-
cur in kerogens where vitrinite or inertinite macerals are
dominant. Kerogens with atomic we ratios between 0.8
and 1.0 may have a modest potential fur generating oil,
FIGURE 8.8 Relationship between Toe and hydrogen index
for three formations containing Types I, II, and III kerogens.
From Clayton and Ryder (1984).
but gas in small amounts is likely to be the only product
from kerogens with we ratios below 0.8.
We have already seen that the type of organic matter
preserved depends upon the same factors that affect Toe
values. Samples having low Toe values therefore contain
mainly oxidized organic matter. In contrast, samples with
elevated Toe values often contain moderate to large pro-
portions of lipid-rich material having good hydrocarbon-
source potential. Typical relationships between Toe and
hydrogen index are shown in figure 8.8.
The empirical relationships shown in figure 8.8 will
108

vary from formation to formation. The correlation be- TABLE 8.5 Correlation of various kerogen-maturity
tween TOC and hydrogen index is weakest in nonmarine parameters with vitrinite-reflectance (Raj values
or paralic rocks containing large amounts of woody or
Vitrinite Thermal Pyrolysis Conodont
cellulosic material, because there is not always a direct Reflectance Alteration Tmax Alteration
correlation between TOC and oxygen levels in the (%Ro) Index (TAl) (OC) Index (CAl)
sediment.
0.40 2.0 420 1
0.50 2.3 430 1
MATURITY
0.60 2.6 440 1
Kerogen Parameters. Determination of the oil-generation 0.80 2.8 450 1.5
window in a particular section is the objective of most 1.00 3.0 460 2
maturity analyses performed on possible source rocks. A 1.20 3.2 465 2
second, less common application is to decide whether oil 1.35 3.4 470 2
will be stable in a given reservoir. The limits of the oil- 1.50 3.5 480 3
generation window vary considerably depending upon 2.00 3.8 500 4
the type of organic matter being transformed (fig. 4.10). 3.00 4.0 500+ 4
Nevertheless, for most kerogens the onset of oil-generation 4.00 4.0 500+ 5
is taken to be near 0.6% Ro. Peak generation is reached
near 0.9% Ro, and the end of liquid-hydrocarbon genera-
tion is thought to be at about 1.35% Ro. The ultimate limit
of oil stability is not known for certain, but in most cases Bitumen Parameters. The Carbon Preference Index can-
is probably not much above 1.5% Ro. not be used as a reliable indicator of maturity; that is,
Because vitrinite reflectance is the most popular there is not a one-to-one correspondence between CPI
method of determining maturity, most other maturation and maturity level. CPI values above 1.2 or below 0.8
parameters are related to Ro values (table 8.5). The corre- traditionally have indicated immaturity. Values between
lations among maturity parameters have been fairly well 0.8 and 1.2 are not diagnostic, for reasons discussed in
established, but there are still some minor variations from chapter 5.
one laboratory to another. The ratio of DPEP to etio-type porphyrins has been
It is particularly difficult to generalize about TAl values used upon occasion as a maturity parameter because
because the numerical values of TAl scales have not been cracking of the exocyclic ring of DPEP species produces
standardized among laboratories. Thus, if you are using etioporphyrins. The DPEP/etio ratio has been calibrated
TAl determinations determined by an analyticallabora- to vitrinite reflectance (fig. 8.9), but Mackenzie (1984)
tory, make sure that you have a copy of their equivalency has suggested that the calibration is not universal.
between TAl and Ro. The equivalency between TAl and A number of polycyclic biomarkers are used as indi-
Ro given in table 8.5 is not used by all laboratories. cators of bitumen maturity. The Methylphenanthrene In-
Although T max values are determined objectively, be- dex-1 (MPI) of Radke et al. (1982) has been related to
cause they vary with kerogen type as well as maturity, a vitrinite reflectance within the oil-generation window by
unified scale for comparing them with Ro values has not equation (8.2):
been adopted. Some laboratories put the onset of maturity
at 435° C; others use 440°. Ro = 0.60(MPI) + 0.37. (8.2)
Conodont Alteration Index (CAl) values ranging from
1 to 5 were tied loosely to vitrinite reflectance and fixed- Most of the biomarker ratios used as maturity indi-
carbon content of coals (table 8.5). CAl can actually mea- cators involve steranes and triterpanes. Moretanes, which
sure high-grade metqmorphism, with CAl of 8 reached in are unstable triterpanes, can be used as a maturity indi-
a marble. cator for immature samples. The presence of more than a

100
90
80
I:
]. 70
e- 60
8.
~50
do 40
\J.l
5 30
* 20
10
O~-'--'--.~~-r
0.2 0.4 0.6 0.8 1.0
Vitrinite refl lance ('!b Ro)
FIGURE 8.9 Decrease in proportion of DPEP porphyrins as a
function of increasing vitrinite rej1ectance. Reprinted by per-
mission ofJohn Wiley & Sons, Ltd. from Petroporphyrin fin-
gerprinting as a geochemical marker, by A. Barwise and P.
Park, ed. by M. Bjorf'Y. Copyright 1983, John Wiley & Sons,
Ltd.
trace of moretanes is a strong indicator of immaturity (fig.
B.l0).
Ratios of 20S to 20R steranes are useful up to early oil
generation, as are ratios of 22S to 22R triterpanes (fig.
B.l0). (Both of these parameters are expressed variously
as %S, S/(S + R), and SIR.) After the reversible R-S inter-
conversion reaches equilibrium, additional maturation
causes no change in the ratios, and the parameter ceases
to be of value. Equilibrium ratios of SIR are about 1 for
steranes and 1.5 for triterpanes.
Seifert and Moldowan (19Bl) developed a "maturation
line" for steranes by plotting two sterane ratios against
each other (fig. 8.11). Increasing distance from the origin
corresponds to increasing maturity. Deviation to the right
of the line was supposed to be related to migration, but
that idea has sparked much controversy. The value of
sterane epimers as maturity or correlation parameters is
often limited by poor resolution of overlapping peaks in
moderately to fully mature samples (fig. 8.12).
8. SOURCE-ROCK EVALUATION 109
13QH
Core 10
31H
R
JJ
re 37
29H
8
Tm
31H
8
R
~30M
Retention time -
FIGURE 8.10 Comparison ofmlz 191 mass chromatograms
for two Australian shale extracts. Core 10 is from an imma-
ture Cretaceous shale. Note that R predominates over S in the
extended hopanes, that Tm > T., and that the moretanes
(29M and 30M) are present in slightly more than trace con-
centrations. Core 37 is from a mature Jurassic shale, in
which S predominates over Rfor the extended hopanes, Ts >
Till> and the moretanes are reduced to very minor compo-
nents. Reprinted with permission from Volkman et al.,
1983b. Copyright 1983, Pergamon Press, Ltd.
Of particular value is the ratio of two C Z7 triterpanes
called T m and Ts . With increasing maturity T m is con-
verted irreversibly into Ts by migration of a single methyl
group (fig. 8.10). The T mlTs ratio is a good measure of
maturity at least up to peak oil generation, provided ana-
lytical problems (see Volkman et al. 1983b) can be
avoided. T mlTs ratios below about 1.0 indicate maturity.
Formation of mono- and triaromatic steranes can also
be applied to answer questions of maturity. The ratio of
triaromatic steranes to mono- plus triaromatics is the
most commonly used parameter. This ratio varies from a
to 1 as maturity increases from immature to peak oil gen-
eration (Mackenzie et aI., 1981; Mackenzie, 1984).
Because of the great need for reliable maturation pa-
rameters, especially for bitumens and oils, much effort
110

m • Prudhoe Bay
o Ship Shoal 0

~ O~erthrusl Bell
I. 0 • Miscellaneous
• Shale Bilumens
.. Green River Shale 110. 21
Pyrolysales

•
111
50. 120SH 1111
50. (20RI!! 11
. .... .JOO Coryt

0.5

- - - First Ordtr ((inelic Conversion

(Maturationl
- - - Geochromalography (Migr.tion l

10
17(l (20RI (IV)
Sa. (20R) fill

FIGURE 8.11 "Kinetic maturation line" used for estimating

maturity of bitumens and oils from sterane distributions. In-
creasing distance along the line from the origin corresponds
to greater maturity. Deviation from the line may be related to
migration. Reprinted with permission from Seifert and Mol-
dowan, 1981. Copyright 1981, Pergamon Press, Ltd.

Sterane BiomarkerS. ,-.-._,

j Regular
m/z 217 , ; Steranes Immature
, - - Shale Extrac t

--..-~. j Rearr;,nged
,J 1~ ·-·.; .-. .___
Isosteranes
Steranes
t'lature

J1t-~J\~ J~ Shale [x"'"

"'-----
'1"[ J. )1 ,. 1.,
••

FIGURE 8.12 Severe overlap of many peaks in sterane mass

chromatograms of mature samples can greatly complicate
quantitative analysis.
 8. SOURCE-ROCK EVALUATION 111

has been expended in attempting to establish definitive zone is of excellent oil-source quality, having Hic ratios
correlations between kerogen-maturation parameters, near 1.3. However, in this well the upper zone is very
such as vitrinite reflectance, and biomarker-maturation immature (Ra near 0.4%).
parameters. Mackenzie (1984) cautions strongly against The lower rich zone is much different. Although it may
this tendency, because of the completely different nature be marginally mature for oil generation (Ra near 0.6%),
of the chemical processes occurring in each case. He be- the quality of the kerogen is poor, as evidenced by the HlC
lieves there is no unique calibration of biomarker- ratios clustered around O.B. We therefore conclude that
maturity values that will serve for all basins. I believe he is the lower rich zone contains coaly material poor in hy-
correct, and that biomarker maturity measurements drogen, and, even if mature, it would generate mainly
should be viewed only as approximate indicators ofmatu- gas.
rity. At the present time (and probably in the future as We now turn our attention back to the upper rich zone.
well) they do not replace kerogen measurements but Even though these rocks are clearly immature at the B-2
rather supplement them. location, our data will still be valuable if we can postu-
late, perhaps on the basis of seisInic data, where these
same rocks might be buried deeply enough to have
EXAMPLES OF SOURCE-ROCK EVALUATION
generated hydrocarbons. Extrapolation of measured data
GEOCHEMICAL LOGS into unknown areas requires a new philosophy of organic
It is most useful to display geocheInical data for wells in a geochemistry, which is discussed in chapter 12.
log format. Many formats for such logs have been devel-
oped; a typical one is shown in figure B.13. Choice of
scales is dictated by the depth of the well, number of
samples analyzed, and the magnitude of the measured
values of each parameter. If a study involving several
wells is planned, it is wise to choose a single format and
scale that will accommodate data from all the wells.
The log form should include those data most relevant
for source-rock evaluation. Thus there should be a col-
umn for quantity of organic matter, at least one column
for type of organic matter, and at least one column for
maturity. Data pertaining mainly to correlation studies
are best displayed elsewhere.
The C.O.S. T. B-2 well, drilled off the New Jersey coast
near the Baltimore Canyon, was analyzed geochemically,
and the results were reported in a geocheInical-log format
(fig. B.14). Quantity of organic matter was measured as
TOC; type (quality) of organic matter was determined by
elemental analysis, with the measured HlC ratios cor-
rected for the effects of maturity; and maturity was mea-
sured as vitrinite reflectance (individual data points not
shown; only the trend is given).
Interpretation of data from the C.O.S. T. B-2 well is
facilitated by the log format, which has great visual im-
pact. It is immediately apparent from the TOC values that
there are two rich zt'mes in the well-between 3000 and
4000 ft, and between 10,500 and 13,500 ft. The upper rich
 HROWN &' 1\ TH IJ'JIORATORI OPERATOR.
"EU. NAME:
GEOCHEMICAL LOG LOC.HION:
T. 0
Turquot$'"

.3•• 00 I'T .

...... SOURCE BED POTENTIAL

.......
::a::
w
Q

It..

zo ..

....
....
-....
" .
...,
....

"'"
,100'

t.OOt

lS001

....
,
~ CONGLOMEJIA T£ cJ SHALE · Sll TSTONE lO( HALITE
til SANDSTONE ~ LIMESTONE ~ ANHYORITE 51 • f'N H.,droc.rbonl Pr ... n, In Rod. S3 • CO, Irom K"oven PyrolY111
• COAL OOlOMfTE M IGNEOUS 52 • HydrocarbOn. hom K.rogen Py,oI."" HydrQgen Ind•• • S2 1 TOe
CASINO CEMENT CHEAT M VOLCANICS
 8. SOURCE-ROCK EVALUATION 113

%Corg IMMAlURE HIe RATIO

.3 .6 .9 .1 .3 .5 .a t.3

18000

QUANTITY QUALITY MATURITY

FIGURE 8.14 Geochemicallogfor the C.O.S. T. B-2 well,

offshore New Jersey.

FIGURE 8.13 GeochemiCallogfor the Turquoise well, showing

results of source-rock analyses in a well-profile format.
Courtesy Brown arui Ruth Laboratories, Inc.
114

ences in depositional environment. A modified van Kreve-

900 len diagram (fig. 8.15) shows that the foreset beds have
high oxygen indices and low hydrogen indices. They con-
tain 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 there-
fore have much higher hydrocarbon-source potential.
600
Such scenarios are probably repeated in many settings
"0
tii worldwide. For example, the Jurassic Kingak Shale and
.5 Triassic Shublik Formation of the Ellesmerian Sequence
=
~
of the North Slope also show the same bottomset-foreset
"0
...
0 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
300 • foreset beds because the bottomset beds are buried very
Bottomsets

/ deeply. Thus far no good candidates for source rocks have

been found in the oxidized foresets. The effective source
Foresets
rocks for most of the Gulf Coast oil are probably the
/. deeply buried bottomset beds that we may never see .

••
100 200 :~oo
Oxygen index

FIGURE 8.15 Modified van Krevelen diagram of Cretaceous

Brookian-sequence rocks from the Alaskan North Slope
showing the difference in kerogen type between bottomset and
foreset facies. Courtesy Brown and Ruth Laboratories, Inc.

ORGANIC-FACIES DETERMINATIONS
Cretaceous rocks on Alaska's North Slope were deposited
as part of the Brookian Sequence, prograding from south
to north off the ancestral Brooks Range uplift. Prograding,
inclined foreset beds overlying flat-lying bottomsets are
evident on seismic profiles. The bottomset beds are
thought to have been deposited in quiet environments,
probably in an oxygen-deficient water mass. The foreset
beds, in contrast, were laid down in shallower, more
aerated waters.
Organic-geochemical data for these rocks illustrate the
differences in kerogen type resulting from those differ-
 8. SOURCE-ROCK EVALUATION 115

COALS AS SOURCE ROCKS

Coals have been traditionally discounted as effective
source rocks for oil accumulations because of the lack of
geographic correlation between oil fields and coal depos-
its. However, this generalization has two fallacies: most of
the coal fields originally studied were of Paleozoic age,
and the coals were of bituminous to anthracite rank.
Age of coals is important, because during the Paleozoic
the biota was quite different than during the Cenozoic.
Because some Cenozoic land plants are richer in resins
and waxes than Paleozoic plants, some Cenozoic coals
should have better potential for generating liquid hy-
drocarbons. The chemical differences between a coal
capable of sourcing mainly gas and a lipid-rich coal
responsible for oil generation is shown clearly by pyroly-
sis-gas chromatography (fig. 8.16).
Coal rank is also an important consideration in com- c,-c,
,.,-:-, .........
paring oil and coal occurrences, because the stability field ,, · Cn
•
for liquid hydrocarbons terminates at the lower end of the
bituminous coal rank. One would therefore not expect
bituminous or anthracite coals to be associated with oil
fields. To make a valid comparison we should instead
look for oil fields near lignites and subbituminous coals.
Tertiary coals have recently been found that have hy-
drogen indices as high as 350 mg HC/g TOC, corre-
sponding to an equal mixture of Type II and Type III
kerogens. These coals, which are found in a variety of
settings that includes Alaska, Indonesia, and Australia,
appear to contain large amounts of resinite and cutinite
capable of generating copious amounts of liquid hydro-
carbons. Coals have been implicated as source rocks for
oils in the Gippsland Basin of Australia, in the Mahakam
FIGURE 8.16 Pyrolysis-ga.s chromatograms of two coals. (A)
Delta of Kalimantan, and in several other basins in In- The North Sea coal is a potential source rock for ga.s and
donesia. Optimism about the oil potential of the unex- yields only small amounts of heavy hydrocarbons and n-al-
plored Norton Basin of Alaska is based largely on the kanes. (B) The Kalimantan coal, which is a source for liquid
presence of resinite-rich coals. 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

o o•

---
2 0.5 0.7 1 0 1.35 2.0 3.0 ".0
o
I
I
I
I
I
:I I
I
:
I
I

I I I
1000
I
I
--- ,,-.I
I
I
I ,,
I
I
,I
,-,- ,
I
,
.-
I
,
I
,, , PALEOCENE

2000
I
I
I-
,I I
I
I
I

-
I
II) I I-
,,-
I
,
I ,,I I
,I
II:
W ,
I-
W
lee
,
,
I
,
I -,-, I
I

-,-
3000
::I!
z
I
,I EARLY TRIASSIC

,I I
::c
I
,,
I I- ,,
I I
I-
D. 4000
I
I ,I I
I
W
I ,
I I I I I
C
I , I
I I I
I ,
I I ,I I

,
I I
I
I , I
, I
I
I
,
I
, ,
,
I I I I
I
I I ,I I I
I
I
I
I I I I I I
I
DIAGENESIS OIL GENERATION GAS GENERATION

"'•••' -1 ."" 1
I.e.

FIGURE 8.17 Vitrinite-reflectance profile for a well from the

MATURITY ANOMALIES
Although vitrinite-reflectance profiles usually give
straight lines when plotted on a semilog scale (fig. 7.16),
in some cases there are pronounced discontinuities in the
profiles, as in the example from the North Slope of Alaska
shown in figure 8.17. From the surlace down to about
3000 m the reflectance profile is fairly regular, reaching a
value of about 0.6% at 3000 m. Below 3000 m there is an
abrupt jump in reflectance to 1.3%.
We also note that the jump in reflectance corresponds
to a m~or biostratigraphic unconformity in which almost
the entire Mesozoic is missing. We therefore conclude
that the unconformity is erosional, and the jump in reflec-
tance is the result of maturation of Triassic rocks that
occurred prior to deposition of the overlying Paleocene
sediments.
Dow (1977) has suggested a method for estimating the
amount of removal in such cases. If enough data are
available to construct a reliable reflectance profile in the
Alaskan North Slope showing the effects on maturity of a
pronounced erosional unconformity.
section below the unconformity, that maturity line can be
extrapolated upward until it reaches the R" value im-
mediately above the unconformity (fig. 8.18). The amount
of upward extrapolation required (in fig. 8.18 it is 500 m)
represents the amount of removal.
Surlace rocks commonly have higher maturity levels
than we would expect, as a result of uplift and erosion.
Thus, by looking at reflectance values of outcropping
rocks and applying Dow's method (regressing the R"
value to about 0.25% at the preerosional surface), we can
often estimate the amount of removal in the most recent
erosional cycle.
Dow's methodology has been criticized, and results de-
rived from it should be regarded as estimates. Erosional
removal can probably be calculated more accurately us-
ing thermal modeling, as described in the next chapter.
 8. SOURCE-ROCK EVALUATION 117

o
•
\
,
,
\ !jjjNFORMlt S INTRUS!VES
\
\~ u oo
1.100
o~
~
[0

~ TERTIARY J._ ~

- ~,.,
J._
, f' ..

-
~r-

~ ~~
~
rt
'C
~SOZOIC
~, uoo
~
",00
I.. 1\0 0
.J .1 • .1 .• ' .. .. . 0 I.. U I J "' 7 " 10 10 ' 10
VITRINITE IIEFLECTANCE IR.%) VITRINITE REFLECTANCE 111.%1

FIGURE 8.18 Estimation of amount of erosional removal at
an uncorifonnity from vitrinite-reflectance profiles. Reprinted
by pennission of Elsevier Science Publishing Company from
Dow, 1977.
FIGURE 8.19 Effect of an igneous intrusion on vitrinite-reflec-
tance 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.

In other cases regular maturi1y profiles are interrupted
by anomalously high reflectance values caused by high
concentrations of uranium or, more commonly and more
dramatically, by igneous activi1y (fig. 8.19). Intrusives
generally affect maturi1y levels in rocks about one or two
sill thicknesses on either side of the sill. Plutons such as
the Baltimore Dome off the East Coast of the United States
can cause regional increases in maturi1y. It is thought that
unusually rapid maturation associated with igneous ac-
tivi1y affects vitrinite-reflectance values more than hydro-
carbon generation (Altebaumer et aI., 1983).
SUMMARY
Any source-rock evaluation should attempt to answer
three questions: What are the quanti1y, 1ype, and maturi1y
of the organic matter present in the rocks? Satisfactory
methods are available in most cases to answer all these
questions. In some areas one technique may fail com-
pletely or may be only-partially successful. Whenever pos-
sible, therefore, we should not rely on a single analytical
technique; rather, we should attempt to corroborate the
measured data by other analyses.
Interpretation of source-rock data on a basic level is
quite simple. With increasing experience one can also
learn to derive important information on thermal his-
tories, unconformities and erosional events, and organic
facies.
We should always attempt to extrapolate our measured
data over as large an area as possible. To do this intelli-
gently we must have the ability to develop regional mod-
els of organic facies (chap. 2) and thermal maturi1y
(chap. 9). The application of such models in an explora-
tion context is the subject of chapter 12.
SUGGESTED READINGS
Demaison, G. and R. J. Murris, 1984, eds. , Petroleum
Geochemistry and Basin Evaluation: American Association
of Petroleum Geologists Memoir 35, Tulsa, American Associ-
ation of Petroleum Geologists, 426 pp.
118

Dembicki, H. jr., B. Horsfield, and T. T. Y. Ho, 1983, Source Walker, A. L., T. H. McCulloh, N. F. Petersen, and R.j.
rock evaluation by pyrolysis gas chromatography: Bulletin of Stewart, 1983, Anomalously low reflectance of vitrinite in
the American Association of Petroleum Geologists, v. 67, pp comparison with other petroleum source-rock maturation in-
1094-1103. dices, from the Miocene Modelo Formation in the Los
Epstein, A. G., j. B. Epstein, and L. D. Harris, 1977, Conodont Angeles Basin, California, in C. M. Isaacs and R. E. Garrison,
color alteration-an index to organic metamorphism: United eds., Petroleum Generation and Occurrence in the Miocene
States Geological Survey Professional Paper 995, 27 pp. Monterey Formation, California: Los Angeles, SEPM, pp.
Espitalie, j., j. 1. Laporte, M. Madec, F. Marquis, P. Leplat, j. 185-190.
Poulet, and A. Boutefeu, 1977, Rapid method of characteriz- Waples, D. W., 1979, Simple method for source rock evaluation:
ing source rocks and their petroleum potential and degree of Bulletin of the American Association of Petroleum Geologists,
maturity: Revue de I'Institut Francais du Petrole, v. 32, pp. v. 63, pp. 239-245.
23-42 (in French).
Espitalie, j., M. Madec, and B. Tissot, 1980, Role of mineral PRACTICE PROBLEMS
matrix in kerogen pyrolysis. Influence on petroleum genera-
tion and migration: Bulletin of the American Association of 1. What data necessary for a complete source-rock evaluation
Petroleum Geologists, v. 64, pp. 59-66. are missing in the geochemical log (fig. 8.20) for a well in the
Espitalie,j.,j. F. Marquis, and I. Barsony, 1982, Geochemical Baltimore Canyon area, offshore East Coast United States?
logging: Institut Francais du Petrole Ref. 30820, 29 pp.
Horsfield, B., 1984, Pyrolysis studies and petroleum exploration,
2. What data necessary for a complete source-rock analysis of
in j. Brooks and D. Welte, eds., Advances in Petroleum
two jurassic formations encountered in the North Sea are miss-
Geochemistry, Volume 1: London, Academic Press, pp. 247-
ing from table 8.6?
298.
Huc, A. Y. andj. M. Hunt, 1980, Generation and migration of
hydrocarbons in offshore South Texas Gulf Coast sediments: 3. Combine the data from the Blue Well (table 8.7) to give a
Geochimica et Cosmochimica Acta, v. 44, pp. 1081-1089. coherent picture of thermal maturity in the section analyzed.
Mackenzie, A. S., R.1. Patience, j. R. Maxwell, M. Vanden- Explain how to resolve any apparent discrepancies.
broucke, and B. Durand, 1980, Molecular parameters of mat-
uration in the Toarcian shales, Paris Basin, France-I. 4. Analyze the source potential of the Turquoise Well, data for
Changes in the configurations of acyclic isoprenoid alkanes, which are given in the geochemical log shown in figure 8.13.
steranes and triterpanes: Geochimica et Cosmochimica Acta,
v. 44, pp. 1709-1721.
Mackenzie, A. S., C. F. Hoffinann, and j. R. Maxwell, 1981,
Molecular parameters of maturation in the Toarcian shales,
Paris Basin, France-III. Changes in aromatic steroid hydro-
carbons: Geochimica et Cosmochimica Acta, v. 45, pp. 1345-
1355.
Orr, W. L., 1983, Comments on pyrolytic hydrocarbon yields in
source-rock evaluation, in M. Bjoroy, ed., Advances in Or-
ganic Geochemistry 1981: Chichester, Wiley, pp. 775-787.
Powell, T. G., S. Creaney, and 1. R. Snowdon, 1982, Limitations
of use of organic petrographic techniques for identification of
petroleum source rocks: Bulletin of the American Association
of Petroleum Geologists, v. 66., pp. 420-435.
Robert, P., 1981, Classification of organic matter by means of
fluorescence: application to hydrocarbon source rocks: Inter-
nationaljournal of Coal Geology, v. 1, pp. 101-137.
Tissot, B. P., 1984, Recent advances in petroleum geochemistry
applied to hydrocarboh exploration: Bulletin of the American
Association of Petroleum Geologists, v. 68, pp. 545-563.
 8. SOURCE-ROCK EVALUATION 119

TABLE 8.7 Thermal-maturity data for the Blue Well

r--
1000 Depth (ft) TAP Ro BitumenITOC

j 1000 2.0 0.05

3000
\ 1200 2.0 0.07
5000
PAUOGEliE < 1500 2.0 0.02
ITOP \]l: I--f- TRANSITION ZONE
2000 2.0 0.10
~ d ~
E 7000 RlY
2300 2.0-2.5 0.08
.... 17 TOP 0
1;; '" '" 2600 2.0 0.09
'"....... 9000 -'" 3000 2.3 0.06
l!: I.
I~OOO - ::- I&""
'jbp LAn
I...
3200
3400
2.3
2.0
0.17
0.25
~ JURASSIC 3700 2.0-2.5 0.42 0.44
_f.--S
13,000 4000 2.2 0.49 0.66
4200 2.5 0.46 0.61
15,000 4800 2.5 0.55 0.21
10 30 5-0 O.Z 0.4 71.0 5000 2.0-2.5 0.60 0.03
TOTAL ORGANIC CARBON VITRINITE REfUCTAHCE
(TOCI I'JJ (Roll'JJ 5200 2.6 0.51 0.07
5400 2.5 0.59 0.09
5700 2.5 0.63 0.11
FIGURE 8.20 Geochemicallogfor a well in the Baltimore
Canyon area, offshore East Coast United States. GOOO 2.6 0.60 0.12

'TAl and Ro are interconverted according to table 8.5.

TABLE 8.6 Source-rock data for Jurassic

formations from two North Sea wells SOLUfIONS TO PRACTICE PROBLEMS

Rock-Eval
1. We have no measure of the type of organic matter present in
Depth TOC Hydrogen Index
(ft) (wt %) (mg HClg TOC) the section. The high-TOC rocks encountered between 10,000
Well Formation
and 13,000 ft would be of great interest, especially since they are
A Kimmeridge Clay 8610 6.2 462 at least marginally mature. However, we have no way of know-
8625 7.1 512 ing from the data presented whether they are an oil-prone facies
A
or coals capable of generating mainly gas.
A 8632 8.9 604
A 8651 4.4 517
2. We do not have measurements of the maturities of the rocks
A 8686 10.3 625
studied. The Kimmeridge Clay obviously has much better re-
B Lower Jurassic 7967 1.4 87
maining source capacity, as indicated by the veIY high TOC
B 7993 1.5 112
values and hydrogen indices. It veIY likely is still immature. The
B 8015 1.3 64 Lower Jurassic shale has a low remaining source potential, as
B 8165 1.2 123 evidenced both by the moderate TOC values and low hydrogen
B 8174 1.0 101 indices. The low hydrogen indices could, however, be the result
of overmaturity rather than poor original generative capacity.
The only way to determine whether the Lower Jurassic rocks
ever did have oil-source potential would be to know whether
these rocks are overmature. If they are, we could not evaluate
their original source potential without knowing what type of
kerogen they originally contained.
120
It is tempting to say that the Lower Jurassic shale is as imma-
ture 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 present-
day depth of burial should not be used as an indicator of
maturity.
3. Each of the three parameters is supposed to be related to
maturity. BitumenffOC ratios should increase in the oil-
generation window. We note that BitumenffOC ratios increase
dramatically between 3200 and 4800 ft. This increase might
mean that oil generation is occurring within this zone, but it
could also indicate the presence of contamination from drilling
fluids or be the result of migration of oil into these strata.
One clue in the data suggests that the bitumen in the 3200-
4800-ft zone is not indigenous: BitumenffOC ratios are much
higher than would be expected from oil generation alone. Bitu-
menffOC ratios in excess of about 0.2 usually indicate the pres-
ence of nonindigenous material.
The kerogen data indicate that no significant oil generation
has occurred in this section. TAl values reach only the begin-
ning of oil generation, even in the deepest rocks. Vitrinite-
reflectance values are consistent with the TAl data. Neither
parameter indicates sufficient maturity for oil generation in the
3200-4800-ft interval. We conclude, therefore, that the entire
section investigated is immature or marginally mature.
We should investigate the composition of the nonindigenous
bitumens from the 3200-4800-ft interval in order to determine
their origin. Gas chromatography and gc/ms would be the best
methods.
4. On the basis of our first screening technique, TOC, we find
four intervals within the Turquoise Well worthy of further con-
sideration as possible source rocks. The rest of the section is
extremely lean, with TOC contents less than 0.5%.
Unit I is the shallowest rock with high TOC values. Lithologic
description and pyrolysis values, however, indicate that the or-
ganic matter in Unit I is of terrestrial (coaly) origin. The low
hydrogen indices (100-150) indicate that these rocks have little
potential to generate liquid hydrocarbons. In any case, Unit I is
still immature.
The upper half of Unit H contains a much more oil-prone type
of organic matter, as shown by the high pyrolysis yields. Hydro-
gen indices in excess of 500 are indicative of marine organic
matter. Maturity parameters suggest that Unit H is at or near the
top of the oil-generation window.
Unit G includes a few elevated TOC values among more
numerous lean samples. The gradual decrease in hydrogen in-
dex downward through the unit, together with the relatively
high Production Indices and Sl yields, indicates that some hy-
drocarbon 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 cau-
tious 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 py-
rolysis yields indicate negligible remaining hydrocarbon-source
capacity. The very high maturity levels measured for those sam-
ples 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 sam-
ples of Unit B from a similar facies from a less mature well
nearby we might be able to extrapolate those data to the Tur-
quoise 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. Ex-
tracts from these rocks might profitably be submitted for corre-
lation 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 indi-
cator. 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 un-
conformity, are needed to verity the existence of such an event.
Chapter 9 Predicting Thermal
Maturity

INfRODUCTION
Measured maturity values for possible source rocks are
invaluable because they tell us much about the present
status of hydrocarbon generation at the sample location.
In most cases, however, measured maturity data are of
limited value in exploration. Part of this problem is a
consequence of the limitations we face in attempting to
obtain reliable maturity measurements. In some areas
there are no well samples available; indeed, in frontier
basins there may not be a single well within tens or hun-
dreds of miles.
Even in maturely explored basins the samples available
for analysis often do not give a representative picture of
maturity in the basin (fig. 1.2). Furthermore, maturity
measurements can only tell us about present-day maturity
levels. If our measurements indicate that a rock has al-
ready passed through the oil-generation window, we still
have no clue as to when oil generation occurred, nor do
we know at what depth or temperature it occurred. These
considerations are important when we want to compare
timing of generation, expulsion, and migration with tim-
ing of structure development or trap formation.
In order to circumvent these difficulties, methods have
been developed for calculating maturity levels where
measurements are not available. Among the most popu-
lar models are those ofTissot (1969), Lopatin (1971), and
Hood et al. (1975). They have been discussed elsewhere
(Waples, 1984a).
The common thread running through all these models
is the assumption that oil generation depends upon both

121
122

the temperature to which the kerogen has been heated

and the duration of the heating. This assumption is a
logical and defensible one, for it is in keeping with the
i
'V
~
..
predictions of chemical-kinetic theory. * The Arrhenius !
equation (eq. [9.1]) gives the exact dependence of the z
reaction-rate constant k on the activation energy Ea and Q 0.05
5
-'
the temperature T.
~
UJ

k = Aexp( -Ea/RT) (9.1) ~

1:
I;;
::E
The preexponential factor A is a constant, the exact value ::; 0.01
of which depends upon the particular reaction under con- .......
«
sideration, and R is the universal gas constant. II:

Several workers have calculated activation energies for TEMPERATURE ('C)

the process of oil generation. The values thus obtained for
Ea are in the range of 11,000 to 14,000 calories per mole
(cal/mol) (Tissot, 1969; Connan, 1974). Because activa-
tion energies in this range are far lower than one would
expect for the breaking of carbon-carbon or carbon-
oxygen bonds (40,000 to 60,000 cal/mol), many workers
have interpreted the low values of Ea as proof of the im-
portance of mineral catalysis in oil generation.
In one respect the catalysis hypothesis appears to be
reasonable, because catalysts lower activation energies by
providing alternative, lower-energy pathways. One prob-
lem with the catalyst idea, however, is that no known
catalysts are capable of lowering the activation energies
to 14,000 cal/mol. Most catalytic effects are far less
dramatic.
In 1975 Jiintgen and Klein presented a much more
plausible explanation for the low calculated values for
activation energies. They pointed out that hydrocarbon
generation involves the simultaneous occurrence of many
distinct reactions, and that the overall rate of hydrocarbon
generation should depend upon the sum of the rates of all
the parallel chemical reactions that produce hydrocarbon
molecules. When these individual reactions are summed,
and the overall reaction scheme is treated mathematically
as though it were a single reaction, the calculated activa-
tion energy turns out to be much lower than the activation
energy of any of the individual reactions (fig. 9.1). This
• Price (1982) has represented a minority opinion that time is of no
importance in hydrocarbon generation. I do not believe that such a
view is tenable in light of either empirical evidence or theoretical
considerations.
FIGURE 9.1 Rate of methane evolution from coalfor eight
parallel reactions (numbered curves) as afunction ofpyroly-
sis temperature during programmed-temperature pyrolysis.
A Gaussian distribution is assumed for the initial concentra-
tions of the eight reactants. The following activation energies
were assumed (kcallmol):
(1)=48 (2) = 50 (3) = 52 (4) = 54
(5) = 56 (6) = 58 (7) = 60 (8) = 62
AJactors are taken as 101S/min for each reaction. Curve L,
representing the sum of the eight parallel reactions, has a
pseudo-activation energy of 20 kcallmol and an AJactor of
1[Jl/min. After Jilntgen and Klein, 1975, by permission of Er-
dOL und Kohle, Erdgas, Petrochemie.
calculated activation energy is a mathematical construct
rather than a true activation energy. The calculated acti-
vation energy is thus best referred to as a "pseudo-
activation energy," because the low values do not actually
describe any single hydrocarbon-generating reaction.
If we accept that the Arrhenius equation (when
equipped with an appropriate pseudo-activation energy)
adequately describes the process of hydrocarbon genera-
tion, we must also accept that both time and temperature
play roles. These two factors are interchangeable: a high
temperature acting over a short time can have the same
effect on maturation as a low temperature acting over a
longer period. Nevertheless, early efforts to take both time
and temperature into account in studying the process of
hydrocarbon generation were only partially successful be-
cause of the mathematical difficulties inherent in allowing
 9. PREDICTING THERMAL MATURITY 123

both time and temperature to vary independently. In

1971, however, N.V. Lopatin in the Soviet Union de- AGE IMY)
100 80 60 40 20 0
scribed a simple method by which the effects of both time 0

and temperature could be taken into account in calculat-

ing the thermal maturity of organic material in sediments. 500

He developed a "Time-Temperature Index" of maturity 1000

(TTl) to quantifY his method.
Lopatin's original work was greeted with some en- 1500

thusiasm and much criticism in his homeland. Several of ~

the problems that subsequently surfaced could be attrib- 2000

:I:
....a.
uted to the poor quality of the data with which Lopatin 2500
w
c
originally calibrated his model. Despite a few minor
difficulties, however, Lopatin's basic idea has much 3000

merit, and it has been generally well received in the West.

Lopatin's method allows one to predict both where and 3500

when hydrocarbons have been generated and at what 4000

depth liquids will be cracked to gas. It has even been
suggested that maturity models are more accurate than
measured data for determining the extent of petroleum
generation (Yiikler and Kokesh, 1984). In addition, TTl
values have been used to estimate the extent of diagenesis
of inorganic minerals (Siever, 1983; Schmoker, 1984).
In this chapter you will learn how to carry out maturity
calculations using Lopatin's method and how to use
Lopatin's method in exploration. We shall also look at
some of the other maturity models that are available.
CONSTRUCTION OF THE GEOLOGICAL MODEL
One of the advantages of Lopatin's method is that the
required input data are very simple and easy to obtain.
We need data that will enable us to construct a time
stratigraphy for the location of interest and to specifY its
temperature history. Time-stratigraphic data are usually
available as formation tops and ages obtained by routine
biostratigraphic analysis of cuttings. If no well data are
available, a time stratigraphy can sometimes be con-
structed using seismic data, especially if the seismic
reflectors can be tied to well data. If no subsurface data
are available, estimates can be made, perhaps from thick-
nesses of exposed sections nearby.
BURIAL-HISTORY CURVES
Implementation of Lopatin's method begins with the con-
struction 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
FIGURE 9.2 Burial-history curve for the deepest datum (100-
my-old rock) in the Tiger well constructed from the time-
stratigraphic data given in table 9.1.
TABLE 9.1 Time-stratigraphic data for the Tiger Well
Age (my) Depth (m)
0 0
10 500
38 900
65 1800
80 2800
100 3700
(table 9.1). In the Tiger well, sediment has accumulated
continuously but at varying rates since deposition of the
oldest rock 100 million years ago (mya). Today the rock is
at a depth of 3700 m. The burial-history curve was con-
structed in the following way: two points, representing
the initial deposition of the sediment and its position to-
day, are marked on the age-depth plot (fig. 9.3).
The next step is to locate the first control point from the
time-stratigraphic data in table 9.1. Neglecting compac-
tion effects, by 80 mya the sediment had been buried to a
depth of 900 m (fig. 9.4). Using the other control points
from table 9.1, we can construct figure 9.5. Connecting
124

AGE (MY) AGE (MY)

100 80 60 40 20 0 100 80 60 40 20 0
0 0
' \ TIME OF DEPOSITION
500 500

1000 1000

1500 1500

2000
i 0(65,3700-1800)
2000 !
:r :r
I- I-
Q. 0.

2500 "'0 2500 "'0

0(38, 3700-900}

3000 3000
(10, 3700-500}o

PRESENT DAY," 3500 3500

4000 4000

FIGURE 9.3 First step in the construction of the burial-his- FIGURE 9.5 Third step in the construction of the burial-his-
tory curve in figure 9.2. Plot the two points corresporuiing to tory curve in figure 9.2. Plot all the remaining control points
present-day depth of burial arui the rrwment of deposition of (age of the datum, thickness of rock presently separating it
the rock of interest. from the 100-my-old rock).

AGE (MY) AGE (MY)

100 80 60 40 20 0 100 80 60 40 20 0
0 0

0_
500 500

POSITION OF ROCK AT
SECOND TIME-CONTROL POINT 1000 1000
(80. 3700-2800)
1500 1500

i :;
2000 2000
:r :r
l- I-
0. Q.

2500 "'0 2500 "'0

3000 3000

3500 3500

4000 4000

FIGURE 9.4 Secorui step in the construction of the burial-his-

tory curve in figure 9.2. Plot the secorui time-control point, FIGURE 9.6 Family of burial history curves for the Tiger well
corresporuiing to the next oldest datum (in this case, 80 my). based on the time-stratigraphic data presented in table 9.1.
The depth of burial of the 100-my-old rock is given by the
thickness of rock that separates the two datums at the pres-
ent time (900 m in this case).
 9. PREDICTING TIIERMAL MATURITY 125

the six dots in figure 9.S completes the burial-history

CUIVe already shown in figure 9.2. AGE (MY)

An of the shallower and younger horizons will have 100 80 60 40 20

30".----------------------------------
5.1. =ls e
burial-history CUIVes whose segments are parallel to those
500
of the oldest horizon (fig. 9.6). This geometry is a direct
consequence of ignoring compaction effects.
40·-----------------------------------
Burial-history CUIVes are based on the best information
50·-----------------------------------
50
0
- - ________________________________ _
1000

available to the geologist. In cases where biostratigraphic 10-------___________________________ _ 1500

.data are available and deposition has been reasonably 80" _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ::i!
2000
continuous, it is easy to construct burial-history CUIVes 90° _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ...>:"-
with a high level of confidence. In cases where biostrati-
graphic data are lacking or where the sediments have had
100°-----------_______________________ _ 2500 ~

complex tectonic histories, a burial-history CUIVe may 110"----------------------------------- 3000

represent only a rather uncertain guess. Nevertheless, if 120" _ _ _ _ _ _ ~ ___________________________ _

3500
constructed as carefully as the data permit,burial-history 130"------- ___________________________ _

CUIVes represent our best understanding of the geological 4000

history of an area.

TEMPERATURE HISTORY FIGURE 9.7 Subsurface-temperature grid that assumes a con-

The next step is to provide a temperature history to ac- stant surface temperature (190 G) and geothermal gradient
company our burial-history CUIVe. The subsurface tem- (3° GI1DO m) during the last 100 my. Isotherms are spaced
every 10° G for convenience in calculating maturity.
perature 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 as-
sume that both the gradient and surface temperature have
remained constant throughout the rock's history. Sup- AGE (MY)

pose, for example, that the Tiger well was logged, and 100 80 60 40 20 0
0
.",."'" .",.""'--
that a corrected bottom-hole temperature of 1330 C was 20~ _ _ _ _ _ _ _ _ _ _ _ _ _ ""'''''''''''''''' .",..",..",..",. --------_

obtained at 3800 m. Suppose further that local weather ~~~~-~~~~~-------------

-------
500
30:.. _ _ _ _ _ _ _ _ _ _ _ _ _ . .",..",. __ - - _ _

records indicate a yearly average surface temperature of .o:_____________ .. .",.~

.",.~
.",.~~....
.",.~~~
.",.~_--- --- __ 1000
190 C. Using these present-day data and extrapolating
them into the past, we can construct the temperature grid
ao~ ____________ ........... .",.~.",..",. __
---------- __

__-----------_
.",.""'.",."'"

.0.-______________ .;..... .",."'" . . .",. ",. 1500

shown in figure 9.7.
-----------
.",..",.;;

.",..",.; .",.~.... :I
Where measured bottom-hole temperatures are not 70!.. _ _ _ _ _ _ _ _ _ _ _ _ _ ~~.",. ;;.",.~"'" ~ .... _ - - - _
2000

available, maps of regional geothe. mal gradients can be • o________________ .... ~ ..... .,.. .. __
""'~

.",......",..",. --------- _ ...>:

Q.

-----------
w
useful in estimating the gradient at a particular location. .00:.. _ _ _ _ _ _ _ _ _ _ _ _ _ ....
~~~~~--~~'~
_____ - -_ -
2500 Q

In many poorly explored areas, temperature profiles will 100:.. _ _ _ _ _ _ _ _ _ _ _ _ ... ;.",. _-.,..,.",..",.;,.
.",._- ------------ __
3000
be based largely on guesswork. .",.~ -~ ....
110~ _ _ _ _ _ _ _ _ _ _ _ _ _ .",..",..",. .",.""'- .",..",. ----------- _

There are numerous other variations that can be em- ..o:.. _____________ ~~~~ ~~~~~~~~------------ 3500

ployed in creating temperature grids. For example, we 130~ _ _ _ _ _ _ _ _ _ _ _ _ _ , .... .",.

~~

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.
4000
FIGURE 9.8 subsurface-temperature grid that assumes a con-
stant geothermal gradient (3° GI100 m) but a variable surface
temperature during the last 100 my.
126

In other cases the surface temperature remains con-

AGE (MY)
stant, but the geothermal gradient varies in response to
.00 80 60 40 20 o
o heating or cooling events. The example in figure 9.9 rep-
30-. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ·,

.o .. _______________________________
, 500
resents a location at which rapid sediment accumulation
,
~',

50-0 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ , \
\ in the last ten million years has lowered the geothermal
gradient, resulting in subsurface temperatures that are
: :-=- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =- =-~\
,,\ \
1000
1500
anomalously low compared to the "normal" ones that
dominated previously. More complicated temperature
::: ===============================~\\\ \
100-_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ' , \

110- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
III \ \
I\ I\ I\
2000 :>
:J:
t-
histories (for example, fig. 9.10) are also possible. "Dog-
leg" gradients can be used to reflect changes in thermal
120- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ III
\ \ \ 2500 :'Qu conductivities caused by variations in lithology (fig. 9.11).
'II
" There is no theoretical limit to the complexity that can
"",,
\
be introduced into our temperature histories. Given ade-
,,,, 3000

quate data or an appropriate model on which to base

,, \ ' 3500
complex temperature reconstructions, we are limited only
,, , 4000 by our own creativity. In most cases, however, the data
, necessary for highly sophisticated temperature recon-
structions are simply not available.

FIGURE 9.9 Subsurface-temperature grid that assumes a con-

stant surface temperature but a geothermal gradient that
dropped dramatically during the last 10 my after being con-
stant for 90 my.

AGE (MY)
100 80 60 40 20 o
o

500

1000

1500

2000 !
:J:
I-
0.
UJ
2500 0

3000

3500

4000

FIGURE 9.10 Complex 'subsurface-temperature grid arising

from a variety of changes noted at the top of the diagram.
 9. PREDICTING TIlERMAL MATURITY 127

AGE (my)
80 80 70 80 50 .0 30 20 '0 0
20'
0

30'

.0 '
,000

$0 '

,..,
eo' -- -- 2000 ...
III
Q)
70 ' -- -- -- -- Q)

eo '
.....E
3000 J:
.....
80 ' n.
W
0
'00' -- -- .000

,.0 ' - - --
5000

,.0' eooo

FIGURE 9.11 "Dog-leg" geothermal gradient that arose as a

result of development of overpressuring (SNP) in a rruLSsive
shale section sandwiched between two sandy sections.
128

AGE (my)
100 80 80 40 20 o

ORIGINAL\ 1000
THICKNE8S
= 3000m
DEPOSITION

-
/RECOMMENCES
000

--
POST-EROSIONAL
THICKNESS eL.n
=2000m Q)
Q)
3000 E

..
ER0810NAL
. 4000
::I:
PERIOD I-
a..
W
0
000

FIGURE 9.12 Loss of 1000 m of section by erosion during an

SPECIAL CONSIDERATIONS ABOUT
BURIAL-HISTORY CURVES
The most common complicating factor in constructing
burial-history CUIVes is erosional removal. Erosion is indi-
cated in a burial-history CUIVe by an upward movement
of the curve. If deposition resumes later, the burial-history
CUIVe again begins to trend downward (fig. 9.12).
Whenever erosional removal occurs, the resultant thin-
ning of the section must be represented in the entire fam-
ily of burial-history curves. The individual segments of
each of the burial-history CUIVes in a family will remain
parallel, but the distances between them will be reduced
(fig. 9.12).
Faulting can be dealt with by considering the hanging
wall and footwall as separate units having distinct burial
histories. If part of the section is missing as a result of
faulting, burial-history CUIVes for both hanging wall and
footwall can be represented on a single diagram (fig.
9.13). If, however, some part of the section is repeated as
a result of thrusting. (fig. 9.14), two separate diagrams
should be used for the sake of clarity (fig. 9.15).
uplift event lastingfrom 70 mya to 60 mya. Individual bu-
rial-history curves remain parallel, but the distance between
the two lines which bracket the erosion decreases by 1000 m.
The effects of thrusting on thermal maturity are not
well understood. If thrusting is rapid compared to the rate
of thermal equilibration between thrust sheets, the move-
ment of hot rocks from the bottom of the overthrusted slab
over cool rocks at the top of the underthrusted slab will
affect organic maturation by causing important perturba-
tions in subsurface temperatures (Furlong and Edman,
1984). Studies by Edman and Surdam (1984) and
Angevine and Turcotte (1983) in the Overthrust Belt of
Wyoming indicate that a slow-equilibration model is
superior to a simple model invoking rapid thermal
equilibration (fig. 9.16). However, more work is required
before we will understand fully how thrusting influences
hydrocarbon generation and destruction.
Van Hinte (1978) has utilized "geohistory diagrams,"
which are similar to burial-history CUIVes (fig. 9.17).
Geohistory diagrams take sea level as the datum, how-
 9. PREDICTING THERMAL MATURITI 129

~
w
...w
9
iC
x
to-
G..
W
o

FIGURE 9.13 Juxtaposition of burial-history curves for hang-

ing wall and footwall. Shaded area represents missing sec-
WELL A.LPHA.
tion.

FIGURE 9.14 Repeated section in Well Alpha where thrusting

has occurred.
130

AGE (MY) TIME (m.y.B.P.)

eoo aoo 300 200

3Q°C
1000
~ 4CXlO
W 60°C
2000 W
L-..
9<XXl go·C · 9IJ·C
3000
Z

J: 12CXlO
.000 ~ ~ 1 ,
Q.
J: W ISO·C ~ ------- ~- ~ _ 1SOoC
I-
aooo It 0 '6CXlO
o 180· C - ----- - • _. - - : 180·C
aooo 20000 210·C
7000
t
Time of malar Ihrushng
of Absaroka p lole

FIGURE 9.16 Perturbation in subsurface-temperature grids in

AGE (MY)
hanging wall and footwall of thrust faults. Reprinted by per-
eoo 500 .00 300 200 .00
mission of the American Association of Petroleum Geologists
from Edman and Surdam, 1984.
'000

2000

3000
AGE (MYI " 000
4000 ~
60 20
J: LEV IE L~--'---++ a
SOOO
I-
a..
i
w
o
- 1000 ...
UI
aooo >
UI
....
- 2000 c
1000 UI
en
- 3000 ~
0
....
UI

..
- 4000 II

FIGURE 9.15 Burial-history curves for overthrusted (top) and :I:

underthrusted sheets in Well Alpha. For the sake of clarity ~5000

Do.
UI
0
two diagrams must be used because section is repeated
rather than missing as in figure 9.13.

FIGURE 9.17 Geohistory diagram (burial-history curve using

sea level as the datum).
 9. PREDICTING THERMAL MATURITY 131

R~paSSive margin -

-1

km
-3 Cambrian (Harlech Grits)
N. WALES
-4
Subduction/Marginal Sea

-5

-6

-7 550 :t:fJ 300 250 200 150 100 50 oI

I I I I I I I I
Ma B·P.

FIGURE 9.18 Geohistory diagram for north Wales showing

the complex pattern of isotherms when uplift occurs without tory diagrams can easily be misinterpreted. For example,
rapid erosion. Reprinted by permission of the Canadian Soci- in figure 9.17 the indicated rock subsided rapidly be-
ety of Petroleum Geologists from Siever and Hager, 1981. tween 40 and 10 mya, but despite the steepness of its
trajectory, very little overburden was added because of
sediment starvation in the basin.
ever, whereas burial-history curves use the sea floor.
Geohistory diagrams permit one to see clearly the water
depth as it evolves through time, and thus can be com-
bined with models for depositional environments and or-
ganic facies. They also allow one to assess relationships
between basin subsidence and sediment supply.
Geohistory diagrams are valuable and should be in-
cluded in the geochemical analysis of basins. They are not
as well suited as burial-history curves for assessing ther-
mal maturity, however, because it is more complicated to
develop a subsurface temperature grid where the datum
is sea level (fig. 9.18). Furthermore, in some cases geohis-
132

TABLE 9.2 Relation between rock temperature,

AGE (MY) the index value n, and the -y-Factor
100 80 60 40 20 o
Temperature Range (Oe) n Temperature-Factor (-y)
500
30-40 -7 '1128
50--____ _____________________________ 1000 40-50 -6 '164.
50-60 -5 %2
1500 60-70 -4 'lt6
::;
70-80 -3 'Is
2000
80-90 -2 '14
...'"-" -1
w 90-100 %
2500 0
100-110 0 1
3000 110-120 1 2
120-130 2 4
130°-- - - _ _ - - _ _ _ _ _ _ _ _ _ - - - - - - - - - _ _ - - - - _ - -
3500 130-140 3 8
140-150 4 16
4000
150-160 5 32
160-170 6 64

FIGURE 9.19 Juxtaposition of the burial-history curve and

simplest subsurface-temperature grid for the l00-my-old rock
in the Tiger well. Dots mark the beginning and end points of
each temperature interval.
CALCULATION OF MATURITY
Once the burial-history curves and temperature grids
have been constructed, we must put them together. Figure
9.19 shows the superposition of the simplest temperature
grid from figure 9.7 over the burial-history curve for the
oldest rock from the Tiger well (fig. 9.2). Intersections of
the burial-history curve with each isotherm are marked
with dots. These dots define the time and temperature
intervals that we shall use in our calculations. Tempera-
ture intervals are defined by isotherms spaced 10° C
apart. A Time interval is the length of time that the rock
spent in a particular temperature interval. Total maturity
is calculated by summing the incremental maturity added
in each succeeding temperature interval.
Now we can carry out the maturity calculations. Chem-
ical reaction-rate theory states that the rate of a reaction
occurring at 90° C (a reasonable average for oil genera-
tion) and having a pseudo-activation energy of 16,400 cal!
mol will approximately double with every 10° C increase
in reaction temperature. Lopatin (1971) assumed that the
rate of maturation followed this doubling rule. Testing of
his model by Waples (1980) and the successful applica-
tion of Lopatin's method in numerous published exam-
ples have confirmed the general validity of Lopatin's
assumption.
In order to carry out maturity calculations conve-
niently, we need to define both a time factor and a tem-
perature 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 exponen-
tially 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 tempera-
ture factor, which Lopatin called ,,{, was given by equa-
tion (9.2).
"{ = 2n (9.2)
The "{-factor thus reflects the exponential dependence of
maturity on temperature.
 9. PREDICTING THERMAL MATURITY 133

TABLE 9.3 Summary of a TTl calculation

for the 100-my-old rock in the Tiger Well

Temp. Temp. Time Interval Total Time

) ----------------------------------- - soo
Interval Factor Factor TTl TTl (m.y.BP)

__ _ _
,
_ ____________________________ ---, 0 0 0 30°_40°C '1128 7 .05 .05 86
," 60' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 40°_50° '164 7 .11 .16 79
0'-- ________________________________ _
_,:!t OO 50°_60° '132 6 .19 .35 73
,
.0' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~20 00
60°_70° %6 6 .38 .73 67
70°_80° Va 7 .88 1.6 60
0'
.0 ' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
80°_90° 'I. 12 3.0 4.6 48
-25 0 0
90°_100° '/2 12 6.0 10.6 36
100°-110° 1 18 18.0 28.6 18
I J O' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
110°-120° 2 12 24.0 52.6 6
JO' - - _________________________________ _- 35 00
120°-130° 4 6 24.0 76.6 0
-4 000

FIGURE 9.20 Temperature factors (,,{actors) and time fac-
tors for the 100-my-old rock in the Tiger well.
Multiplying the time factor for any temperature interval
by the appropriate 'Y-factor for that temperature interval
gives a product called the Time-Temperature Index of
maturity (TTl). This interval-TTl value represents the
maturity acquired by the rock in that temperature inter-
val. To obtain total maturity, we simply sum all the inter-
val-TTl values for the rock. Maturity always increases; it
can never go backward because interval-TTl values are
never negative. Furthermore, even if a rock cools down,
maturity continues to increase (albeit at a slower rate)
because 'Y is always greater than zero.
A good analogy can be drawn between oil generation
and baking. If we put a cake in a cold oven and turn the
oven on, the cake will bake slowly at first but will bake
faster and faster as the temperature rises. Ifwe turn off the
oven but leave the cake inside, baking will continue, al-
though at increasingly slower rates, as the oven cools
down. On the other hand, if we forget about the cake
when the oven is hot and let it burn, we cannot "unburn"
it, no matter how much or how rapidly we cool it down.
The first step in calculating TTl is illustrated in figure
9.20, where the time factors and 'Y-factors for each tem-
perature interval are shown on the burial-history CUIVe.
In table 9.3 interval-TTl values and total-TTl values up to
the present day are calculated.
It is also possible to determine the total-TTl value at
any time in the past simply by stopping the calculation at
that time. For example, ifwe wanted to know the TTl for
the 100-my-old rock in the Tiger well during the early
Oligocene (36 mya), we would add up the interval-TTl
values for the first 64 my of the rock's history. From the
calculation in table 9.3 we can see that 36 mya the total
TTl was 10.6.
FACTORS AFFECTING THERMAL MATURITY
Because maturity is affected by both baking time and
baking temperature, the specific burial history of a rock
can strongly affect its maturity. Figure 9.21 shows four of
the many paths by which an 80-my-old rock could have
reached a present burial depth of 3000 m. In figure 9.21A
the rock was buried at a constant rate for its entire 80-my
history. In figure 9.21B burial was very slow during the
first 70 my of the rock's existence, but quite rapid in
the last 10 my. Figure 9.21C shows rapid burial during
the first 20 my, followed by a nonerosional depositional
hiatus for the last 60 my. In Figure 9.21D 40 my of rapid
burial to a depth of 4000 m was followed by a hiatus
lasting 30 my and, finally, by 10 my of uplift and erosion.
TTl values differ appreciably among these four
scenarios. Maturities for the rocks in figure 9.21 are di-
134

I.

'" . .. ,
I. 4.
AGE (MYBP)

• o
I.

------- -- ---,
I. 4. •• I. I. 4.
AGE ( MYBP )

•
•
I •
•• 4. •
,,
,. ,..--, ,
.., ..
1000

,,
\ 1000

, ,
\

'" .. .. ,
\ ,iio- - ,
\
1000
'.0;- -"\',, '--
"
\ 2000
, \ \
\ \
TTI=3.1 ", TTI=0.8
'000
1'iO·------------ 3000
\
,-------
A
L-________________-L4 ••• ~
B _________________J
L-______________ A
~~4 ••• TTl· " . , \ B

\
• \
\ \
\ \
\ 1000 \
\ \
\ \
\ TTI=7.8 \ TTI=24.4
\ 2000 \
\ \
\ \
\L _________ \
:)000
\
\ ito" - - - - - - - - - - - - - 3000
\ I
C 4000
D \
\ I
I
TTl. :110 . 7
C
L-________________-k4 ••• ~~----------~~-J

FIGURE 9.21 Four possible burial-history curves for a rock

FIGURE 9.22 Important thermal events that occur early in a
of 80-my age that is presently buried to a depth of 3000 m. rock's history do not affect its maturity very much, as shown
TTl values were calculated assuming a constant geothermal
by three possible combinations of varying burial and geother-
gradient of 2° CI100 m and an average surface temperature mal history CA, B, and C). In contrast, the maturity in
of 19° C. model CD) is much higher because the thermal event (extra
burial) occurred when the rock was near its maximum
rectly related to the amount of time spent near the max- paleotemperature.
imum burial depth and temperature. The calculated
maturity in figure 9.21D is by far the highest, because the where high geothermal gradients are mainly present in
temperature reached and maintained at 4000 m was the early stages of basin evolution, will not be unusually
much higher than that achieved in the examples where no high unless the source rock was deposited during the very
erosion occurred. early rifting stage. Cohen (1985) has cited such an ex-
However, when important events occur early in the ample in the Reconcavo Basin of Brazil.
history of a rock, their impact on maturity is much less. Similarly, the additional burial that occurred in figure
For example, figure 9.22 illustrates two events that will 9.22C between 70 and 60 mya has not greatly affected
increase maturity: a higher geothermal gradient (fig. present-day maturity because subsequent burial to much
9.22B) and extra burial preceding later uplift and erosion greater depths and higher temperatures has swamped out
(fig. 9.22C). However, the higher geothermal gradient the slight increase in maturity resulting from that early
was only in force early in the rock's history when its event. A brief residence near 800 C obviously is not very
temperature remained low because of shallow burial. important compared to a longer time spent near 110 C. 0

Thus the TTl in figure 9.22B is only slightly higher than in Figure 9.22D shows, however, that burial to depths and
the control example (fig. 9.22A). One implication of this temperatures greater than present-day conditions, fol-
exercise is that source-rock maturity in rifted basins, lowed by erosion, will affect the maturity very strongly
 9. PREDICTING THERMAL MATURITY 135

(compare TTl of 109 in fig. 9.22D with 17.8 in fig. 9.22A). TABLE 9.4 Correlation of TTl values with vitrinite reflectance
Changes in the geothermal gradient when a rock is near
% Vitrinite
its maximum depth of burial will also influence maturity
Reflectance (Ra) TTl
strongly.
The effect of igneous intrusions is difficult to treat accu- 0.40 <1
rately with maturity models because our present models 0.50 3
have not been calibrated for such high temperatures. Fur- 0.60 10
thermore, there is substantial uncertainty about the tem- 0.65 15
peratures actually achieved in the sedimentary rocks and 0.70 20
the rate at which thermal anomalies decay. Nevertheless, 0.85 40
the effects of igneous events can be detected by finding 0.90 50
discrepancies between measured and predicted maturity 1.00 75
values. Kettel (1983), for example, deduced the existence 1.15 110
and shape of an ancient heat anomaly in the southern 1.35 180
North Sea by showing that vitrinite-reflectance values 1.50 300
were significantly higher than normal subsurface heating 1.75 500
could account for. 2.00 900
Bond (1984) has used Lopatin's method in a very 2.50 2,700
sophisticated manner to model maturation in the San 3.00 6,000
Juan Basin of New Mexico. The maturity history there has 4.00 23,000
been complicated greatly by an intense thermal event dur- 5.00 85,000
ing the Neogene and by many thousands of feet of uplift
and removal. Nevertheless, Bond was able to develop a NOTE: Reprinted, by pennission, from D. W. Waples, 1980, Time and temperature
in petroleum formation: application of Lopatin's method to petroleum exploration:
satisfactory model that fit the measured data. Bulletin of the American Association of Petroleum Geologists, v. 64, pp 916-926,
table 4.
INTERPRETATION OF TI'I VALUES
Uncalibrated TTl values obviously are of little value; to be
TABLE 9.5 Correlation of selected TTl values with
useful they must be compared in some way with mea- vitrinite-reflectance values and hydrocarbon generation
sured maturity values. Lopatin's (1971) original calibra-
tion was shown to be in error by Waples (1980), who TTl Ra Generation
proposed a revised version of the TTl-&., correlation (table
9.4). Subsequent work has not strongly questioned the 1 0.40 Condensate from resinite
TTl calibration within the oil-generation window, but
3 0.50
Katz et al.(1982) showed that beyond the oil-generation From S-rich kerogen
10 0.60

r
window Waples's correlation is probably incorrect. early
15 0.65
Other complicating factors have arisen. Recent investi-
20 0.70
gations that have improved our understanding of the oil peak
50 0.90
oil-generation window indicate that Waples's choice of
&., = 0.65% as the threshold for oil generation is almost
75
180
1.00
1.35
1 late
certainly too high. Moreover, different kerogen types have wet gas
900 2.00
different oil-generation thresholds (see the section Poten- dry gas
tial problems with Maturity Calculations). These various
problems must be dealt with before we can construct a
correlation between 'tTl and oil generation. Table 9.5
shows a proposed correlation between TTl and hydrocar-
136
.-.- AGE
,
f
,
J:
NON-DEPOSITIONAL I-
HIATUS a..
w \.
c
WELL #1
FIGURE 9.23 Initial proposed burial-history rrwdel for Well
# 1. The rrwdel includes an extensive nonerosional deposi-
tional hiatus.
bon generation based on our best present understanding
of catagenesis and hydrocarbon formation. The onset of
oil generation is shown to vary from about TIl = 1 for
resinite to TIl = 3 for high-sulfur kerogens to TIl = 10
for other 1)rpe II kerogens, to TIl = 15 for 1)rpe III
kerogens.
Where both TIl values and measured maturity data
are available, the two should always be compared. Such
comparisons can often teach us important, hitherto undis-
covered, facts about the geology of the area under consid-
eration. For example, suppose that for Well #1 we have
constructed the burial-history curve shown in figure 9.23.
This proposed burial history includes a depositional
hiatus but no erosional removal. When we compare our
calculated maturities with measured ones obtained from
well samples however, the correlation (fig. 9.24) is rather
poor, with calculated maturity values being consistently
lower than the measured ones. Assuming that the mea-
sured data are reliable, how can we explain the consistent
underestimation of maturity in our calculations?
In general, there are two possible explanations if cal-
culated maturities do. not agree with reputable measured
ones. One explanation is that the paleotemperatures used
\.
J:
\. WELL #1
I-
a. \..
W
C
\ . MEASURED
MATURITY -+
FIGURE 9.24 Poor correlation between measured and pre-
dicted maturity data for Well # 1.
in the model were incorrect. This situation can arise eas-
ily when our present-day temperature data are poor or
when past events (such as igneous activity) created a ther-
mal regime quite different from the present one. A second
explanation, which is the one we shall adopt in the pres-
ent 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 substan-
tial removal occurred during the time of the unconfor-
mity. 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 ero-
sional removal (fig. 9.25) to bring measured and cal-
culated maturities into agreement.
Because the effects of underestimating paleotempera-
ture are about the same as the effects of underestimating
erosion, one might think that it would be difficult to de-
cide 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 pre-
dicted and measured maturities for the lnigok-1 well on
the Alaskan North Slope. The thermal history finally cho-
sen (fig. 9.26) was rather complex but justified on the
 9. PREDICTING TIIERMAL MATURlTI 137

basis of specific events on the North Slope that affected

+-AGE geothermal gradients.
One important question is "How well should we ex-
pect measured and calculated maturities to agree?" In
the C.O.S. T. :#= 1 well, drilled off the Texas Gulf Coast,

,
samples were taken and analyzed carefully, and time-
::c stratigraphic and temperature data were determined with
l-
n.. a high level of confidence. There is nevertheless a discrep-
w
c ancy of about 1000 ft at both the top and bottom of the oil-

\j generation window between measured and calculated

WELL #1
FIGURE 925 Revised burial-history model for Well # 1 based
on the poor correlation with measured maturity data. The
hiatus has been reinterpreted as an erosional unconformity
in which a substantial amount of section was removed.
maturities (fig. 9.27). Why is the fit not better?
The vitrinite-reflectance values obviously form a very
nice trend, and thus appear at first to be high-quality
data. However, closer examination of the data indicates
that vitrinite was actually rather sparse in the well; no
more than 31 particles were analyzed in any sample, and
many samples contained fewer than 10 vitrinite particles.
We should therefore be cautious in ascribing the misfit
between measured and predicted maturities solely to
deficiencies in our thermal model. In fact, in many other
cases we easily obtain a near-perfect fit.

Rifting 3.0

5.0
:;; ......
§ 0
0
"- "-
~ 4.0 ~

2.0

3.0

300 200 100 o

M.Y.B.P.

FIGURE 9.26 Three possible thermal models for the Inigok-1

well, Alaskan North Slope. Case I represents a constant
geothermal gradient; Case II shows a gradual decrease in
gradient since the Carboniferous; and Case III, which gave
the best fit between measured and predicted maturities, is
approximately a combination of I and II. From Magoon and
Claypool (1983).
138

Ro TTl

.
100 1000
.3 .5 1.0 1
~~~~UU~ __-L-L~~UL__~~~LU~O

··
\
2000 2000

··.
·
4000 4000

.··
6000 6000
~
J:
~ 8000 8000
Q.
W
C
10,000 10,000

-------
12,000 12,000

Oil generative Oil generative

14,000 zone from 14,000
zone pred icted
Vitrinite from TTl

16,000
reflectance
_L __ 16,000
1
---------
A B

FIGURE 9.27 Comparison of measured vitrinite-reflectance

On the basis of a fair amount of experience, I consider
about 500 ft as the intrinsic accuracy of Lopatin's method.
If we accept such a limitation, then where reliable mea-
sured and calculated maturities do not agree within 500
ft, the original model should be modified to bring mea-
sured and calculated maturities within the acceptable
limits.
Skeptics might argue that an uncertainty of 500 ft is
unacceptably large, and maturity modeling is therefore of
little value. The obvious answer to this objection is that
we must use maturity modeling only where an error of
500 ft would be acceptable. For most applications such an
uncertainty is not a problem. After all, we live happily
with uncertainties about whether oil generation com-
mences at vitrinite-reflectance values of 0.5%, 0.6%, or
even 0.7%. We even blissfully ignore the uncertainty of
whether vitrinite reflectance is a valid measure of oil gen-
eration at all. Our doubts about thermal modeling are
really no more serious.
data with TTl values, and the oil-generation windows de-
lineated by each data set for the C.O.S. T. # 1 well, Texas
offshore Gulf Coast.
APPLICATIONS TO HYDROCARBON PRESERVATION
The preservation deadline for oil has been the subject of
investigation for many years. In 1915 David White pro-
posed his famous "Carbon-Ratio Theory," which showed
that the oil deadline correlates with coal rank. It follows
that if we can predict coal rank (itself a measure of ther-
mal maturity), we can predict the oil deadline. The poten-
tial of thermal modeling for this purpose is obvious.
Waples (1980) suggested the applicability of Lopatin's
method in defining hydrocarbon deadlines and proposed
TTl values for several deadlines. Further empirical work
suggests that a slight modification of those original esti-
mates is appropriate (table 9.6), but even these new
values are still somewhat uncertain. The deadlines pro-
posed in table 9.6 are expressed at the 80% confidence

TABLE 9.6 Hydrocarbon deadlines (80% confidence level)
correlated with vitrinite-reflectance and TTl values
Expected Hydrocarbons
(80% Probability)
TIl No
50 0.90 normal oil
75 1.00 normal-light oil
180 1.35 condensate-wet gas
500 1.75 wet gas
900 2.00 dry gas
level; that is, at higher TTl values heavier hydrocarbons
could occur, but these occurrences would be rather rare.
Despite the apparent success of Lopatin's method in
predicting oil deadlines, at least one important problem
remains. The kinetic parameters used by Lopatin were
defined in order to best describe the overall process of oil
generation, which comprises many distinct chemical
reactions. Many of the cleavage reactions in oil generation
involve carbon-heteroatom bonds, which have low acti-
vation energies compared to breaking carbon-carbon
bonds.
Cracking of crude oil, in contrast, includes a more ho-
mogeneous set of reactions, most of which involve cleav-
age of carbon-carbon bonds. One would therefore expect
the pseudo-activation energy for oil destruction to be
higher than that for oil generation. Furthermore, the tem-
peratures at which extensive cracking occurs are proba-
bly about 20° to 30° C higher than typical temperatures of
oil generation. The difference in kinetic parameters for
generation and destruction of oil requires that we use
different 'V-factors for the two processes.
The best solution to uncertainties about the appropri-
ateness of any of our thermal-maturity models for crack-
ing would be to select a new 'V-factor on the basis of
careful empirical studies of known hydrocarbon occur-
rences. Unfortunately, no such study has been published.
Until such research is carried out, the best we can do with
Lopatin's method is to utilize the same kinetic parameters
as for oil generation. We can take comfort in the fact
that, despite this important oversimplification, TTl val-
ues appear to correlate well with observed hydrocarbon
deadlines.
9. PREDICTING TIfERMAL MATURITY 139
Predicting the gas deadline is far more difficult because
destruction of methane is an oxidative process rather than
cracking. The rate of methane oxidation is therefore de-
pendent on the availability of suitable oxidizing agents as
well as on temperature. Oxidizing agents are apparently
rather rare in sands, but in carbonates there are often
substantial amounts of sulfate and elemental sulfur pres-
ent. Barker and Kemp (1982) have shown that methane in
the presence of anhydrite is unstable at high tempera-
tures. Furthermore, the economic dry-gas deadline is of-
ten controlled more by reservoir quality than by methane
stability. For these reasons there is little chance that matu-
rity calculations will be of value in locating the dry-gas
deadline.
APPLICATIONS TO EXPLORATION
MATURITY THROUGH TIME
The earliest application of Lopatin's method to explora-
tion was published by Zieglar and Spotts (1978) in an
analysis of the hydrocarbon production and future poten-
tial of the Central Valley of California. Using the as-yet-
unpublished approach of Waples (1980), they drew iso-
TTl lines on burial-history curves to show the develop-
ment of maturity through time and to compare the ther-
mal 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 burial-
history-curve family and beginning with deposition of
that sediment and working toward th~ present, one calcu-
lates 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-history-
curve family. Then all the points having the same TTl
value are connected with a line. If TTl values corre-
sponding 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, particu-
larly in understanding the timing of hydrocarbon genera-
140

AGE (MYBP) AGE (MYBP)

80 60 4() 20 0 80 60 4() 20 0
0 0
1
50" - 5
2
3
100' - 10
t:
:I:•
'" 5
~ 150" -
15
~
Ii: 6
20 ~
~ 7 200' - Ii:
8 25 !
9 250"- TEJON BUTTONWIllOW
30
DEPOCENTER DEPOCENTER
10 'C

~ OIL GENERATION 11 CONDENSATE FORMATION ~ GAS GENERATION

FIGURE 9.28 Hydrocarbon-generation histories in the deepest

parts of the Ttjon and Buttonwillow depocenters, southern
Great Valley, California. Reprinted by permission of the
ACE CHYSP)
American Association of Petroleum Geologists from Zieglar
100 90 SO 70 60 SO 40 30 20 10
and Spotts, 1978.

1000
tion. Their only weakness is that because each diagram
,
S\r,_ r... · '·c Tfu ,,'. represents a single place on the earth, a series of such
~1~t.2S'"~
n_,~,., 1ft
,, 2000
figures must be used if an area having a variety of matu-
I
• rlu,1IIDIn rr/ ..
, f'rItr
.~
IM/.,. rr /- ». D I
I
8 rity histories is being considered.
rr/-
"I- I.' 3000
• t.NC1:/tIOT., 1S., ~
• C'$ArlJIO[,
• CXI71, rTl- ... J
• "","1(}11, rTl .. 4'''0
i!i CROSS SECTION AND PIAN VIEW
'....,.11/_ 5U. J
Ltqt.r ••• '''''~
4000 Cross sections with isomaturity lines on them have been
mt 11 . ,e.. " .... ,e>
used to give a more regional picture of maturation. Figure
SOOO 9.30 shows isomaturity lines superimposed on cross sec-
tions across the Otway Basin, southeastern Australia, at
6000 four times from 60 mya to the present. The gradual move-
ment of maturity upward through the stratigraphic se-
FIGURE 9.29 Family of burial-history curves for a well in the
quence is clear. In such diagrams the possibilities for
Big Hom Basin, Wyoming, showing the evolution of the oil- migration of hydrocarbons at various times can be exam-
generation window through time. Tu = undifferentiated Ter- ined and correlated with structural events that regulate
tiary; tfu = Fort Union Formation; Km = Lance-Meeteetse migration pathways. TTl values can, of course, be con-
formations; Ki: = Cody-Frontier formations . Reprinted by toured instead of reflectance values.
permission of the Rocky Mountain Association of Geologists
from Hagen and Surdam, 1984.
 9, PREDICTING TIfERMAL MATURITY 141

PECTEN'IA
PECTEN ·IA
00
00

11~-~_i:I~~~i:~~-~~~~l~~:~:-~-7~~::~~:~::::~~::::~: 0·5

1·0
OS

1-0

1-5 E
... IS
_ ..... 20 x
. .
........ ,
. . " ." .
.......
.
iLw 20
x
. " .... ,
" ......
75 0 2·5 0::
w
.. .' .. . .... " ... '.
. .
'
) -0 )0
0

~~~~~ ) -5 ) 5

' -0 '·0
A , ·5
PECTEN -I.
A
C
--------:- ---- - 00
------ --------.. ------------ -
~-----
.
o~ NAUTl l US'1 MUSSEl·l

~~~~~l~l~~i~jl~jljI~:~I~~:~::::::-;~c:??::::~:~~::~:::::::~:~ (PROJECTED) (PROJECTED) PECTEN -!A

10

~~~~4:...:..~;:..:....:...:...,;,:-,.:..:-,-::.~~,_=:,::':':.~~.:O~S::,~'
15

10 ;~~~~~~I1~~~~~!i~~~~~~~~~OO ...
0 '5

1' 0
. . . . .. . : ".: ..... .... . ... ... . :r

:: : . . . :.:.0::S.. :.::;::/.;.!:A~.
1~ "-
'" IS ]
J-O !!! ~~~.:~::i,~,~~~~'~O~.~S~%~'~'~ 20 l:
0,5(% ':, ' ',' ': • : :', 0::
..........,
J~
. -.: ..:::"....
.. . ....... .... ...... .
>...:: :". 2·5 o \oJ

, . 4'0 ..
':': . ' , ... ~~ : ',':'
.. .... .................... .. ".. A. . . 3·0
,

:' :: ':'.: ;'. ....

4 '~ "
B
----- ' . , '.' :--.. : ','. ': :' .:-:-. :, ) -5

"""'~;'-"'-,~,-, .: ',:" : '.'::' ~, ,~~: , ' . :'

:- ,', '.' .. "~, ' ., ". " ~ : . ' ·0
, ·5
o

o 10km

~ PORT CAMPBELL
~ LlMES10NE
~
t;0j
NARRA..... ATURK
MARL
[8 SHERBROOK GP

If;TI GELLIBRAND
~Mt.Rl
D MEPUNGA FM +
Y;l, GERRIP GP
OTWAY GP

FIGURE 9,30 Isorejlectance lines on cross sections across the

Otway Basin of southeastern Australia calculated at four
different times: 60 mya (A), 40 mya (B), 20 mya (C), and
present-day (D), Reprinted by permission of the American
Association of Petroleum Geologists from Middleton and Fal-
vey,1983.
142
DEADLINES
One of the potentially most important applications ofther-
mal modeling to exploration is in predicting the oil dead-
line. 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 burial-
history 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 drill-
ing program.
COMPUTERIZATION
Virtually all the calculations and plots discussed thus far
can be carried out by a computer. Computerization
greatly speeds up the maturity-calculation process and
makes it possible to modifY the input data quickly and
easily. Numerous companies have developed their own
maturity-calculation programs, and some consulting
companies offer them for sale. Some of the programs are
more sophisticated than the basic program we have de-
scribed, and can include such features as decompaction.
Others are less flexible than hand calculations because
they limit the number of uplift events or changes in sub-
surface temperatures.
The main advantages of a computerized system are its
speed in calculating and plotting results and its ease in
making revisions in the geological or geothermal model.
These are important conveniences that make thermal
modeling more palatable to many geologists.
There are, however, some disadvantages to carrying
out maturity calculations entirely by computer. One po-
tential problem is that the technology can easily become a
"black box" to a geologist. If a geologist simply is required
to put in age, depth, and temperature data, he or she may
not understand at all how these data affect the calcula-
tions. This ignorance will lead to a lack of appreciation of
the factors affecting maturation.
The second problem is more severe. One of the main
benefits of carrying out maturity calculations using Lopa-
tin's method lies in the construction of the burial-history
curves themselves. These curves allow a geologist to bring
the concept of time into geology in an effective and un-
usual 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 deempha-
sized 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 matu-
rity by hand. Thus prepared, the geologist will be able
to derive maximum benefit from data created by the
computer.
COMPARISON OF SEVERAL MATURITY MODELS
Those wishing to carry out maturity calculations will have
at their disposal several alternative models from which to
choose. Lopatin's method is probably the most widely
used at the present time, but also available are several
other published models, as well as proprietary, unpub-
lished versions developed within individual companies.
The most readily accessible alternative model for most
geologists is the LOM (Level of Organic Metamorphism)
method developed by Shell (Hood et al., 1975). LOM
values are calculated by considering only the time that the
rock spent within 150 C of its maximum paleotempera-
ture. These time and temperature values are then used to
compute LOM from the nomograph shown in figure 9.31.
For example, a rock whose maximum paleotemperature
was 1200 C, and which spent 40 my between 105 0 and
1200 C, would have reached LOM = 10 at the present
day. The nomograph also shows the pseudo-activation
energy required to reach each LOM value (in this case
21,000 cal/mol). LOM values have been calibrated to vari-
ous measured maturity parameters (fig. 9.32). A LOM
value of 10 corresponds to Ro = 0.8%, near peak oil
generation.
LOM has an advantage over Lopatin's method in that
calculations are simpler, since one need not reconstruct in
detail the complete burial history of a rock. LOM there-
fore oversimplifies the influence of temperature on matu-
rity. In many cases this assumption is quite acceptable,
but in other cases it is not.
 9. PREDICTING TIIERMAL MATURITY 143

T MAX
'F 'c lO4/ToK
16
15
500
14
250
13
20 12

!
II
400
200
10
33
32
31
300 150 9

1
29

25 27

24
100
200

21

30

50 18

01 1.0 10 100 1000

EFFECTIVE HEATING TIME. MILLIONS OF YEARS

FIGURE 9.31 Nomograph used to calculate LOM by knowing

the maximum paleotemperature of a rock and its "effective
heating time," the length of time the rock spent within 15" C
of that temperature. One finds the effective heating time on
the x-axis and the maximum paleotemperature on the y-
axis. The LOM value and pseudo-activation enerff)! are found
at those coordinates. Reprinted by permission of the Ameri-
can Association of Petroleum Geologists from Hood et al.,
1975.
Probably the greatest weakness, however, is that a
geologist will miss out on many of the additional benefits
of using Lopatin's method. The LOM method does not
allow one to discuss timing of generation in any conve-
nient way. Furthermore, LOM does not require construc-
tion of a burial-history curve, itself a valuable learning
device. Despite these shortcomings, the LOM method
has achieved moderate popularity and appears to be
satisfactory.
The earliest published model for calculating the extent
of hydrocarbon generation is that developed at the French
Petroleum Institute (Tissot, 1969; Tissot and Espitalie,
1975). The Tissot-Espitalie model is highly mathematical,
fully computerized, and rather formidable. Application
thus far has been mainly by their French colleagues.
The advantages of the Tissot-Espitalie model are that,
because of its sophisticated mathematical foundation, it
may be the most accurate in assessing maturity. Further-
more, because the model assumes that the kinetics of oil
generation and destruction are different, in describing oil
destruction it is almost certainly superior to Lopatin's.
The Tissot-Espitalie model also allows timing of genera-
tion to be represented, although in a slightly different
format than Lopatin's model (fig. 9.33).
One of the model's main weaknesses is that geological
input is minimal. A geologist using the program is there-
fore unlikely to derive the benefits that come from con-
structing burial-history curves. A second problem is that
the model appears to underestimate maturity. Much
higher temperatures and longer geologic times are re-
quired for oil generation than in other models. Maturities
calculated by the Tissot-Espitalie model in the Michigan
Basin, for example, are much lower than those predicted
by other models (Nuon et al., 1984).
Advocates of the Tissot-Espitalie model have been
144

HYDROCARBON PALEOZOIC
LOM RANK "VM Ro (", GENERATION
o 400 300

2
LIGNITE
DIAGENETIC

4 METHANE

SU8 . C
6
BIT.
-
B

-=-
-
0 .5 -
45
8 C -

--==
HIGH_
VOL.
-
B
40
-
:::c
OIL

-== -=-
BIT. -
10
A ®
35 GAS
1.0
30 - -
MV BIT.
12 2S -
20 - 1.5 --= CONDENSATE
&
-=
LV BIT .
IS - WET GAS

14 SEMI - -= 20
-
ANTH . 10 -
-
--
- -
16
- 2.5 -
- CATAGENETIC
- --
- -
METHANE

ANTH. S -
18
- @
-
20

400 o
FIGURE 9.32 Correlation of LOM with various coal-rank pa- GEOLOGIC TIME ( M.Y.)
rameters. Reprinted by permission of the American Associa-
tion of Petroleum Geologists from Hood et al., 1975.
FIGURE 9.33 Burial-history curves and hydrocarbon genera-
tion at three locations in the Illizi Basin, Algeria, predicted
vocal in their criticism of Lopatin's method. Their main using the model of Tissot (1969). Reprinted by permission of
complaint is that Lopatin's assumption of a doubling of the World Petroleum Congresses from the Proceedings of the
reaction rate for each 10° C increase in temperature is Ninth World Petroleum Congress, Applied &ience Publishers,
unrealistic, since the actual activation energies are on the from Tissot et al., 1975.
order of 50,000 cal/mol rather than 15,000. This argu-
ment would be valid and telling if hydrocarbon genera-
tion were a homogeneous reaction, but the analysis of
Jiintgen and Klein discussed earlier (fig. 9.1) refutes their
claim. In fact, the Tissot-Espitalie model is vel}' similar to
Lopatin's, because Lopatin's model uses a single kinetic

""c
TISSOT
FIGURE 9.34 Arrhenius plot showing why the various ther-
mal models all seem to work adequately despite their furu1a-
mental differences. Because the range of times and
temperatures we normally observe for oil generation in na-
ture is narrow, the available data are tightly clustered. Con-
sequently, 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 tem-
perature values will we be able to choose among these
models.
parameter (equivalent to curve ~ in fig. 9.1), whereas the
Tissot-Espitalie model inputs each of the individual mem-
bers of the family (curves 1-8 in fig. 9.1).
The most unusual model published recently was devel-
oped at Gulf (Toth et al., 1983). Their work indicated that
changes in vitrinite reflectance in the North Sea were best
explained by a pseudo-activation energy of 50 cal/mol, a
value far too small for a bond-breaking chemical reac-
tion. This result suggests that increases in vitrinite reflec-
tance may be related to changes in the relative positions of
portions of the kerogen molecule rather than to chemical
reactions. Despite its oddness, the Gulf model has been
used with apparent success by its developers.
Most privately developed modelS with which I am
familiar are similar to Lopatin's method. Their main dif-
ferences involve the -particular ways in which they use
time and temperature in the maturation process. At the
9. PREDICTING THERMAL MATURITY 145
present time it is not possible to select one of the models
(Lopatin, LOM, Tissot-Espitalie, Gulf, unpublished) as
the best, either from a theoretical point of view or on the
basis of empirical data. The process of hydrocarbon gen-
eration is so complex and chemically variable that any
model will only be an approximate description of the
actual system.
All of the models mentioned worked adequately for
their developers within the data sets used to develop and
test those models. We may therefore assume that they also
will work well in the future for other data sets. The reason
that the various models, which differ substantially among
themselves in their descriptions of the kinetics of hydro-
carbon generation, can all work satisfactorily is that the
range of times and temperatures that occur in natural
settings is quite small: perhaps 70° C (from 70° to 140° C)
and generally from 5 to 50 million years. In determining
kinetic parameters in the laboratory, a chemist normally
tries to observe reaction rates over a much wider range of
conditions in order to distinguish as carefully as possible
between the contributions of the time and temperature
variables.
The small ranges of time and temperature data avail-
able from oil-generation studies mean that measured data
points cluster in a small area on an Arrhenius plot, which
is a typical device for determining reaction kinetics (fig.
9.34). Given the natural variations and experimental un-
certainties always associated with geological samples, the
data do not lend themselves to a unique interpretation.
There are in fact many ways that we can draw a straight
line through our data. Figure 9.34 shows schematically
how the various laboratories have selected a variety of
interpretations. Until we obtain data giving us a broader
range of times and temperatures, we shall be unable to
select a "best" model among those proposed.
The implications of this dilemma are fortunate for ex-
plorationists. Basically, whichever model one is using can
be defended on the basis of both theory and experimental
data, and therefore is acceptable. There is at the present
time no superior model; one should select a model on the
basis of availability, convenience, and ancillary features
(permitting discussion of timing, degree of integration
with geology, visual output, etc.). Perhaps at some time in
the future, one model will emerge as superior to the
others on the basis of its ability to explain measured data,
146
but for now the best model for each geologist is that
which is most practical.
POTENI'IAL PROBLEMS WITH
MATURITY CALCULATIONS
The most obvious errors in maturity calculations will
come from inaccuracies in time and temperature data. In
actuality, time data are seldom a problem. First, the de-
pendence of maturity on time is linear, so even a rather
large error in baking time will not produce a catastrophic
change in maturity. Secondly, we usually have excellent
control on rock ages through micropaleontology. Age
calls are often made within a million years, and can be
even better in Cenozoic rocks. Only in cases where mi-
cropaleontological dating was not or could not be carried
out might we anticipate possible problems with time.
Temperature, in contrast, is the single most important
cause of uncertainty and error in maturity calculations.
The sensitivity of maturity to temperature is clearly indi-
cated by the exponential dependence of maturity on tem-
perature predicted by the Arrhenius equation.
Furthermore, our uncertainties about the true values of
subsurface temperatures are much greater than about
time. Present-day subsurface temperatures are difficult to
measure accurately. Most logged temperatures are too
low and require correction. Various methods have been
developed for this pwpose (see Yiikler and Kokesh, 1984
for a brief discussion), but there is no guarantee of their
accuracy in any particular case.
Even ifwe could measure present-day subsurface tem-
peratures with perfect accuracy, however, we still would
have to extrapolate the present somehow into the past. In
many cases, where present-day temperatures are max-
imum paleotemperatures, even an inaccurate extrapola-
tion into the past may not cause significant problems. In
other cases, however, particularly where Paleozoic rocks
are involved, an accurate interpretation of the ancient
geothermal history may be critical. In such cases we
should be very careful about using predicted maturities
unless we have some independent confirmation of the
validity of our model from a comparison with measured
maturity data.
A question of some concern comes from the previously
mentioned fact that most of the maturity models treat all
types of kerogen identically. Despite experimental evi-
dence indicating that different kerogens decompose to
yield hydrocarbons at different levels of maturity (see
chapter 4), Lopatin's model, the LOM model, and the
unpublished models with which I am familiar do not
utilize different kinetic parameters for the various kerogen
types. The only published model that does consider differ-
ent reaction kinetics for the various kerogen types is that
of Tissot and Espitalie. This modification was possible
because of the algebraic nature of the Tissot-Espitalie
model, but it has not yet been adapted to graphical ap-
proaches like Lopatin's.
The Tissot-Espitalie model, therefore, has a clear
theoretical advantage over the others in considering oil
generation from different types of kerogen. However, the
practical implications of this theoretical advantage are
relatively modest, for two reasons. First, most oil is proba-
bly generated from Type II macerals. Type I kerogens are
very rare. Type III kerogen is common, but because the
woody and cellulosic components themselves generate lit-
tle oil, we need not worry much about them. (Most oil
derived from Type III kerogens probably comes from
Type II material within the Type III matrix.) The most
important distinction, therefore, would be among the ki-
netics of oil generation from the various Type II macerals
(resinite, exinite, cutinite, etc.). The Tissot-Espitalie
model does not make this distinction, and therefore fails
to make full use of its theoretical advantage.
Secondly, the other models are, in a crude but probably
satisfactory fashion, able to take different kerogen types
into consideration simply by adjusting the thresholds for
generation from different kerogen types (table 9.5). For
example, liptinite might begin to be strongly converted to
bitumen at TTl = 10, whereas an equal intensity of gener-
ation from resinite might be reached at TTl = 1. This ap-
proach distorts somewhat the theoretical foundation of
our chemical-kinetic approach, but it is probably accept-
able in a practical sense, given the other uncertainties
under which we labor. Thus, the problem of dealing with
different kerogen types can be addressed by all the mod-
els, albeit in different ways.
CONCLUSIONS
Models for predicting thermal maturity have been devel-
oped to aid in understanding the hydrocarbon-generation
and -preservation histories of sedimentary basins. Appli-

cations include defining the hydrocarbon-generation win-
dow, 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 pro-
grams, both in frontier and maturely explored areas.
Some of the models employed are also capable of aid-
ing 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 burial-
history 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 can-
not yet say with certainty that one of the models is mathe-
matically 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 becom-
ing a "black box" technique, however. One can only take
full advantage of maturity-modeling technology by main-
taining a sound geological foundation for the model. Out-
put 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 deter-
mine burial history, evolution of the geothermal gradient, and
timing of hydrocarbon generation in Cretaceous source rocks
in the Sanjuan Basin, northwestern New Mexico and south-
western Colorado, in]. Woodward, F. F. Meissner, and]. L.
Clayton, eds., Hydrocarbon Source Rocks of the Greater
Rocky Mountain Region: Denver, Rocky Mountain Associa-
tion of Geologists, pp. 433-447.
de Bremaecker,].-Cl., 1983, Temperature, subsidence, and hy-
drocarbon maturation in extensional basins: a finite element
9. PREDICTING TIiERMAL MATURITY 147
model: Bulletin of the American Association of Petroleum
Geologists, v. 67, pp. 1410-1414.
Edman,]. D. and R. C. Surdam, 1984, Influence of overthrusting
on maturation of hydrocarbons in Phosphoria Formation,
Wyoming-Idaho-Utah Overthrust Belt: Bulletin of the Amer-
ican Association of Petroleum Geologists, v. 68, pp. 1803-
1817.
Snowdon, L. R., 1979, Errors in extrapolation of experimental
kinetic parameters to organic geochemical systems: Bulletin
of the American Association of Petroleum Geologists, v. 63,
pp. 1128-1138.
van Hinte,]. E., 1978, Geohistmy analysis-application of mi-
cropalentology in exploration geology: Bulletin of the Ameri-
can Association of Petroleum Geologists, v. 62, pp. 201-222.
Waples, D. W., 1980, Time and temperature in petroleum for-
mation: application of Lopatin's method to petroleum explo-
ration: Bulletin of the American Association of Petroleum
Geologists, v. 64, pp. 916-926.
- - - , 1984a, Thermal models for oil generation, in]. Brooks
and D. Welte, eds., Advances in Petroleum Geochemistry,
Volume 1: London, Academic Press, pp. 7-67.
Zieglar, D. L. and]. H. Spotts, 1978, Reservoir and source bed
history of Great Valley, California: Bulletin of the American
Association of Petroleum Geologists, v. 62, pp. 813-826.
PRACTICE PROBLEMS
1. The Black Well was drilled off the Louisiana Gulf Coast. It
penetrated tOOO ft of Pleistocene sediments, 3500 ft of Pliocene,
and 11,000 ft of upper Miocene before being abandoned at
16,150 ft in the middle Miocene. The corrected bottom-hole
temperature was 2700 F. A plaUSible average surface tempera-
ture is 680 F. Construct a family of burial-history curves for the
well and calculate the present-day TTl at total depth.
2. Calculate present-day TTl at 3000 m in the Red Well, assum-
ing a constant geothermal gradient through time. Find when the
rock at 3000 m began to generate oil (TTl = 10). Determine
when each of the strata began to generate oil.
Time-stratigraphic data:
Age (my) Depth (m)
o o
2 500
38 1200
65 2700
80 3000
100 4000
148

Temperature data: 5. Analyze the timing of oil generation in the Pink Well, drilled
Present-day average surface temperature: in the Midcontinent region of the United States. The geothermal
Corrected BHT (4200 m): gradient was found to be 1.0 F/100 ft, and the surface tempera-
0

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.
ture today is about 590 F. Time-stratigraphic data are given in
the following table. No unconformities are recognized within
the Paleozoic. Erosional removal since the Permian probably
totals about 2000 ft.

Time-stratigraphic data: Tops Age (my) Period Depth (ft)

Age (my) Depth (m) Permian 230 Permian o
Virgil 280 L. Carboniferous 7,000
30 o Missouri 288 " 8,000
38 300 11,000
Des Moines 296
65 1400 13,000
Atoka 304
80 1700 18,500
Morrow 309
100 3000 21,000
Mississippian 320 E. Carboniferous
Kinderhook 340 23,000
Erosional removal is estimated to have begun about 5 mya and Sylvan 425 Ordovician 25,500
probably comprises between 500 and 2000 m. Arbuckle 470 27,500

Temperature data:
Present-day average surface temperature: 6. You have been asked to evaluate an undrilled prospect in a
Corrected BHT (3000 m): remote area that is available in an expensive farm-in deal. Be-
cause of the high operations cost, upper management has de-
4. The Wtraviolet Well is spudded in Paleocene sediments. At a cided that gas and condensate are not economical. Your
depth of 1500 ft, micropaleontology indicates the rocks to be of responsibility is to make a recommendation regarding the na-
Maestrichtian age. The following Upper Cretaceous boundaries ture of hydrocarbons that might be present in the prospect. The
are noted: fullowing geological summary is available to you.
"A regional study of the area suggests the probable presence
Maestrichtian-Campanian 1807 ft of a thin, rich, oil-prone source rock at about 4300-m depth near
Campanian-Santonian 2002 ft the prospect. The source rock is thought to be about 300 myoid.
Santonian-Coniacian 2360 ft
No other source rocks were noted. Highly fractured carbonates
Coniacian-Turonian 2546ft
Turonian-Cenomanian 3017 ft overlie the source rock; they are in turn overlain at 2750 m by a
sandstone of excellent reservoir quality. The reservoir is sealed
by a thick salt layer. No other reservoirs are anticipated.
The Cenomanian is 480 ft thick and overlies 1000 ft of Kim-
"The basin filled at a generally uniform rate from about 300
meridgian-age shale. Total depth is reached at 6120 ft in Middle
mya to 100 mya. At that time nearby orogenic activity caused the
Jurassic rocks.
first traps to be formed during a gradual 1200-m uplift lasting
Evidence from related sections indicates that the Paleocene
until 40 mya. From 40 mya to the present about 500 m of addi-
was originally about 3000 ft thick and that no other Cenozoic
tional burial occurred.
sediments were ever deposited. Total original thickness of the
"Nearby well control indicates that a geothermal gradient of
Kimmeridgian is thought to be 1500 ft. It is also believed that
3.650 c/100 m and a surface intercept of 150 C are reasonable for
500 ft of Lower Cretaceous sediments were deposited before
the area. The traps at the prospect location formed slightly prior
uplift and erosion began.
to the beginning of erosional removal in the basin and have
Assuming a surface temperature of 100 C and a geothermal
retained integrity to the present."
gradient of 2 0 F/100 ft, draw a burial-history curve for the sec-
tion penetrated and calculate maturity for the Kimmeridgian Utilizing the principles of hydrocarbon generation and pres-
shale. ervation, evaluate the prospect.

AGE (MY)
16 14 12 10
20°C
30°C-
40°C-
50°C-
60°C-
70°C-
80°C_
90°C-
100°C-
110°C -
120°C-
130°C-
140°C-
FIGURE 9.35 Family of burial-history curves and subsurface-
temperature grid for the Black well.
SOLUTIONS TO PRACTICE PROBLEMS
1. Because we have only a single bottom-hole tempera!W'e and
no information with which to reconstruct a detailed temperature
history of the Black well, it would be satisfactory to assume that
the present-day geothermal gradient is constant throughout the
section and that it has remained constant since the middle
Miocene. Calculation of the geothermal gradient gives 202° FI
16,150 ft, or 1.24° Fll00 ft. After converting to Celsius and in-
verting, we have a thickness of 1,442 ft for every 100 _C
temperature interval. These data permit construction of the sub-
surface-temperature grid (fig. 9.35).
The time-stratigraphic data permit a complete definition of
three horizons: the Pleistocene-Pliocene boundary, the Plio-
cene-upper Miocene boundary, and the boundary between up-
per Miocene and middle Miocene. Using the dates of 1.8, 5.0,
and 12.0 my for these three events, the three members of the
family of burial-history curves for the Black Well can be drawn
(fig. 9.35). A fourth burial-history curve corresponding to the
rock at total depth can also be partially drawn, but because the
9. PREDICTING THERMAL MATURITY 149
8 6 4 2
2000
4000
6000
8000 -
~
: I:
I-
Q.
10,000 ~
12,000
14,000
16,000
18,000
exact age of that rock is not known, the curve cannot be taken
back to the time of deposition. Fortunately, however, the tem-
perature 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 tem-
perature was 10° higher. In the absence of any more informa-
tion, let us assume that cooling proceeded at a constant rate
from the end of the Cretaceous (65 mya) to the present. Further-
more, let us assume that during the Late Cretaceous the temper-
ature 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 subsurface-
temperature grid. TIl values can now be calculated by defining
the length of time spent in each temperature interval. An ex-
150

AGE (m.y.) AGE (m.y.)

80 60 40 20

TEMP.·C 30'

1000 1000

2000 2000 E
E
I
I f-
f-
a.. a..
W
w
3000 0 3000 0

4000 4000
140 0

5000 5000

FIGURE 9.36 Family of burial-history curves and subsurface- FIGURE 9.37 Burial-history curves for a 100-my-old rock, as-
temperature grid for the Red well. lsomaturity line represents suming two difforent erosional models (500 m or 2000 m of
the beginning of oil generation at TTl 10. removal) commencing 5 mya in the Beige well.

3. Construction of the subsurface-temperature grid for the Beige

TABLE 9.7 Calculation of TTl at the present day
Well is simple because there are no changes in gradient or
for the rock now at 3000 m in the Red Well
surface temperature through time (fig. 9.37). Two burial-history
Temp. Interval curves are constructed in figure 9.37, corresponding to
Time Interval Total
eC) 'V-Factor Factor (my) TTl TTl minimum and maximum possible removals. The curves are
identical from 100 mya to 30 mya. Between 30 mya and 5 mya,
30-40 Y,26 10 .08 .08 when uplift and erosion began, they are different. In the case of
40-50 Ys< 6 .09 .17 minimum erosion only 500 m of sediment was deposited during
50-GO %2 7 .22 .39 those 25 my, whereas in the case of maximum erosion 2000 m
60-70 Y,6
had to be deposited. Removal began 5 mya in both cases; the
7 .44 .83
difference was the amount of removal.
70-80 Yo 11 1.38 2.21
Present-day TTl values reflect the differences in burial depth
80-90 Y4 15 3.75 5.96 and maximum paleotemperature for the two models. The max-
90-100 Yz 11 5.50 11.46 imum-erosion case has a TTl of 14.8 today, whereas the
100-110 1 4 4.00 15.46 minimum-erosion case is only 5.5.

4. Draw the temperature grid as in problem *1 after converting

ample of a calculation for the stratum now at 3000 m is given in
table 9.7.
The present-day TTl calculated from table 9.7 for the horizon
now at 3000 m is about 15.5. This horizon reached a TTl of 10,
corresponding to the onset of oil generation, about 8 mya (table
9.7 and fig. 9.36). The 4000-m horizon reached TTl 10 about 39
mya, while the rock now_at 2700 m has not quite reached matu-
rity (fig. 9.36).
Fahrenheit to Celsius; then consider the problem of the uncon-
formities. The last unconformity is at the surface, where
Paleocene sediments are exposed. Loss of 1500 ft of Paleocene
sediment has occurred in the last 55 my. In the absence of any
evidence to the contrary, it can be assumed that erosion has
occurred at a constant rate throughout that time interval. The
temperature and depth of burial therefore have also decreased
at a uniform rate.
 9. PREDICTING TIfERMAL MATURITY 151

AGE (MV'
160 120 100 80 60 40 20
I~C ~__~~~~~~~-L~~~~~~~~~--~--~--~--L-~~-t

2O' C - 1000

30' C -
2000

40' C -
3000 X
~
w
o
TTl -
SO' C - 2.7

4000

TTl -
6O"C - 4.9

5000

70' C -

6000

6O' C -

FIGURE 9.38 Famill' Of burial-history curves and subsurface-

temperature grid for the Ultraviolet welL
The first unconfonnity is also erosional. The section has lost
500 ft of Kimmeridgian and 500 ft of Lower Cretaceous. The
exact time interval represented by the lost Lower Cretaceous
rocks is not known, but this lack of knowledge is not serious
because all events occUlTed when the bed of interest (the Kim-
meridgian) was at a very low temperature.
Uplift in a basin is usually preceded by a slowing of the
subsidence and sediment-accumulation rates. Assume that the
Lower Cretaceous sediments were deposited at a slower rate
than the Kimmeridgian sediments. In this case a rate of 500 ft in
10 my was selected. If we also assume that erosion occurred at a
constant rate between 135 mya and 100 mya, the horizon lines
can be completed as shown in figure 9.38. The dashed line
represents the top of the uneroded Kimmeridgian.
TIl values can be calculated for the bottom and top of the
uneroded Kimmeridgian. None of the Kimmeridgian turns out
to be thermally mature; TIl values lie between 2.7 and 4.9 and
therefore correspond to vitrinite-reflectance values between
0.50% and 0.55% (table 9.4).
152

AGE jMY)

420 360 300 240 180 120 60 0

480
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
-....
X

....0
A.

1(xtc-
16,000

II00C -
18,000
120C-
20,000
130C -
22 ,000
140' C -

24 ,000
lSO· C -

160C- 26,000

170C - 28,000

FIGURE 9.39 Family of burial-history curves and subsurface-

5. The family ofburial-histOIY curves constructed from the data temperature grid for the Pink well,
is shown in figure 9,39, In order to discuss the timing of oil
generation, we must put isomaturity lines on the burial-history In the distant past the oil-generation window was deeper and
curves, Let us assume that the kerogen present is Type III, which hotter because the sediments had not been baked so long. The
probably begins to generate oil a bit later than 'JYpe II-say at unusually high temperatures (115 0 -140 0 C) and great depths of
Ro = 0.65% (TTl = 15). If the end of oil generation is taken as burial (18,000-22,500 ft) required for oil generation during the
TTl = 160, then these values define the oil-generation window, Late Paleozoic from the Sylvan Formation were a result of the
In order to draw the isomaturity lines, we merely find the points rapidity with which the overlying sediments were deposited.
on each burial-history curve where TTl is 15 and 160. Then we
connect all the TTl = 15 points with one line and all the TTl =
160 points with another (fig. 9.40).
It is evident from figure 9.40 that, at the present time, the
interval from 7600 ft to 14,000 ft is within the oil-generation
window. Temperatures in this interval range from 580 to 93 0 C.
The relatively low temperatures of the oil-generation window
are a direct consequence. of the long time that these sediments
have spent in the subsurface.
 9. PREDICTING THERMAL MATURITY 153

AGE /MY)
480 420 J60 300 240 180 120 60 o
20 C -

30C-

40C-

SO ' C -

6OC-

70 C -

8OC-

90 C - :r
t:w
IODC- o

110 C -

120' C -

130C-

140 C -

ISO C -

160C-

170 C-

FIGURE 9.40 Isomaturity lines superimposed on burial-his-

tory curves for the Pink well.
154

6. Burial-history curves for the source rock and reselVoir rock

AGE (MY) are shown in figure 9.41. The subsurface-temperature grid is
not shown. Maturities of both source and reselVoir were cal-
300 200 100 o AGE culated and isomaturity lines defining the oil-generation win-
O-r____~I~~~~l------~I------_i_
.,.,
~,

~,
'lI\
~,
~,
dow (TIl = 10 to TIl = 160) and liniit for condensate
preselVation (TIl = 500) drawn on the burial-history curves.
~, ~\ The source rock generated its oil around 200 mya, long before
1000- 'lI\
~\
~.,.,
- any trapping mechanism existed in the prospect. After trap for-
mation (liberally interpreted as starting as early as 120 mya) the
'lI'
~~\ O~
"',
....' only product being generated by the source rock was gas.
." Furthermore, the maturity of the reselVoir today is very high
(J)
a:
w
2000- ,_,"-
~ -
\
\ ,,"
0
,
- (TIl nearly 500), indicating that even if oil had somehow found
its way into the traps, it would not have been preselVed. Wet gas
., , .... t:-

,
I-
W is the most likely hydrocarbon product from the prospect. In
0'\ ..\ " ~I:..
o , \ 0 /. • ""

::!: " view of the economics of the play and the mandate from man-
3000-
agement, your recommendation would be to reject the farm-in
:r '( ,I" offer.
I- 0\ 0{
11. o \' - •
W

: ~:Z
o ,
o 4000
'z /' C-
o ;:: o~ 0 I'
W c ... ~ I
II:
~ o ::;:: ~'I
5000-
l-
e ! .~ ~:: V
::Ii o '~C0
::Ii . . ._. t ., \II
C
o '<II( -I
o~· o
SOOO~----~----~~~--~--------;-
I I I TRAPS fXlST

FIGURE 9.41 Burial,history curves arul isomaturity lines for

farm-in prospect, showing that oil generation in the source
rock predated trap formation by many tens of millions of
years arul that the maturity level of the reservoir rock today
is too high for oil to be preserved. This is therefore a gas
prospect.
Chapter 10 Correlations

INrRODUCTION
In order to identny source rocks and determine migration
pathways, it is often important to know whether two sam-
ples of organic material share a common origin. We
therefore frequently attempt to correlate samples by com-
paring their chemical and physical properties. Correla-
tions are easiest between materials of the same type (two
oils, for example), but they are also possible between
dissimilar samples (oils with kerogens or bitumens, bitu-
mens with kerogens). Correlations involving gases are
more difficult and will be treated separately in this
chapter.
Correlations are carried out by measuring and compar-
ing several characteristics of each sample. These charac-
teristics must be reasonably variable from sample to
sample but should be minimally (or at least predictably)
affected by transformations occurring during catagenesis
and migration, as well as in reservoirs.
Two fundamentally different types of characteristics
can be measured: bulk parameters and specific parame-
ters. Bulk parameters refer to properties of the whole
sample; sulfur content, API gravity, saturated-hydro-
carbon content, and pour point are examples. Because
they tend to be affected strongly by processes such as
migration, biodegradation, and cracking, bulk param-
eters have some important limitations as correlation tools.
Specific parameters, in contrast, measure in detail one
characteristic of a small fraction of the sample; they in-
clude, for example, the many types of biomarker ratios.
Specific parameters are sometimes strongly affected by a

155
156
small amount of contamination, biodegradation, or
mixing.
Bulk parameters are better for detecting transforma-
tions that affect the whole sample but generally are not
sensitive enough to be reliable positive correlation tools
without corroboration by specific parameters. It is there-
fore important to utilize both bulk and specific parame-
ters in correlation studies.
A human analog may be helpful in understanding the
difference between the two types of parameters. Blood
type is a bulk parameter for human beings, but it is vel}'
limited in its sensitivity because there are so few distinct
blood types. Fingerprints, in contrast, are extremely sensi-
tive because of their uniqueness, but they are not perfect
indicators because they are susceptible to alteration or
disguise.
Although the term fingerprinting is often applied in
correlations, its usage is overly optimistic. Most samples
of oils, for example, are reasonably similar, and no distin-
guishing parameter as definitive as the human fingerprint
is known. In making a positive correlation, therefore, we
are forced to build a case of probability based on a num-
ber of reasonably good positive correlations and no unex-
plainable negative correlations. This process is analogous
to building a case on circumstantial evidence in a court of
law. We cannot prove the correlation conclusively, but we
can make it vel}' plausible. It is thus vel}' important in any
correlation study to amass as many different pieces of
evidence as possible.
Negative correlations are more straightforward than
positive correlations. If two samples differ in a single bulk
parameter that cannot be explained on the basis of trans-
formations, then the samples do not correlate. Disagree-
ment in a single specific parameter is not as serious,
because of the possibilities of alteration or contamination.
However, a repeated pattern of disagreement on several
specific parameters indicates a negative correlation be-
tween the samples.
There are several factors that can make correlations
unusually difficult. Mixing of oils from different sources
can be difficult to detect. Transformations of oils in reser-
voirs by biodegradation, water washing, cracking, or
deasphalting also causes severe changes in some of the
chemical and physical properties of crudes (see chap. 5),
rendering some correlation parameters completely use-
less. In such cases the bulk parameters are often greatly
changed, forcing us to focus on those specific parameters
that are not affected (or are affected in predictable ways)
by the transformations.
Another problem can arise in correlating an oil with an
immature sample of a rock whose more mature equiva-
lent may have been the oil's source. If the correlation
attempt is to be meaningful, we must factor out the differ-
ence in maturity levels between oil and rock by selecting
parameters unaffected by maturation, or by backing out
the effects of maturity. This task is often vel}' difficult.
Finally, some samples simply have no distinguishing
characteristics. Such materials are vel}' difficult to corre-
late definitively with other samples, although occasionally
a negative correlation may be feasible. These samples
may be "silent partners," contributing to a mixture where
their presence is difficult to detect and the relative impor-
tance of their contribution impossible to estimate.
Despite these few drawbacks, correlation studies have
been vel}' useful in the past and will continue to grow in
popularity as biomarker and isotope techniques are fur-
ther refined. They have proven to be of aid in establishing
the source rocks for some oils, as well as in identifYing
contributions from multiple sources. Gas correlations
have shown conclusively that vast amounts of gas in many
commercial reservoirs are of biogenic origin. Correlation
studies should be undertaken wherever a better under-
standing of the relationships between individual reser-
voirs, or between source rocks and reservoirs, would be of
value in exploration.
CORRElATION PARAMETERS
BULK PARAMETERS
The most commonly measured bulk parameters include
the following:
1. API gravity, reported in degrees API (oAPI). API
gravity is a measure of density (or specific gravity).
Specific gravity and API gravity are related by equation
(10.1).
°API = - - -141.5
---- - 131.5. (10.1)
Specific gravity
 10. CORRELATIONS 157

The API gravity of pure water is 10°. A gravity less than

10° API indicates the oil is more dense than pure water. -80
Most normal oils have API gravities from 25° to 45°. Oils
-100
having API gravities less than about 20° are usually cfi
biodegraded, high in sulfur content, or both. Condensates
0 - 120
typically have gravities above 50° API. Viscosity and API <0
gravity are usually inversely related; however, high-wax
-140
oils can have high API gravities even when they are quite
viscous. -160
2. Sulfur content, expressed as weight percent. Most oils
are low-sulfur oils, containing less than 0.5% S. High- -1 80

sulfur oils are less common in general but abundant

-200
locally. They are thought to be sourced mainly from
nonclastic, organic-rich source rocks (chap. 5). Most of -32 -30 -28 ·26
the sulfur resides in the asphaltene fraction, incorporated
into the ring structures of large polycyclic aromatic
molecules. Sulfur content can be raised substantially dur-
ing biodegradation (fig. 5.19). FIGURE 10.1 Classification of oils by crossplotting 3D versus
3. Isotope ratios, measured by mass spectrometry and 313 C. Reprinted by pennission of Erdal und Kahle, Erdgas,
Petrochemie from Sehoell, 1981.
reported in permil (parts per thousand deviation from the
standard; see chap. 3). The isotope ratio most commonly
used is 13C/12C. The DIH ratio is occasionally used for oils,
majority of oils and kerogens fall in the range - 24 0/00 to
but it is much more common for gases. 3~p2S is some-
- 28 0/00, where the carbon-isotope ratios of the whole
times measured for high-sulfur samples.
oil are not particularly diagnostic.
Natural variations in isotope ratios are great enough
. Recently, with the increasing popularity of hydrogen-
and measuring precision is good enough to permit utili-
ISotOpe measurements, attempts have been made to com-
zation of isotopes in correlations. Approximate ranges of
b~e carbon and hydrogen isotopes to distinguish among
carbon-isotope values for several naturally occurring car-
OIls whose carbon-isotopic values are similar (fig. 10.1).
bonaceous materials were shown in figure 3.15. On the
These techniques are still under development, however.
average, oils are about 2 0/00 more negative (lighter) than
The causes of variations in hydrogen isotopes in particu-
kerogens. Bitumens are also about 2 0/00 more negative
lar are poorly understood. One useful generalization that
than the kerogens from which they were extracted. These
is beginning to emerge is that the deuterium content of
relationships suggest that isotopic fractionation occurs
oils sourced from carbonates is higher than for shale-
during catagenesis and that effects during expulsion and
sourced oils (fig. 10.2).
migration are far less pronounced. They also indicate that
Sulfur-isotope ratios are occasionally useful in correlat-
if an oil is isotopically heavier than the suspected source
ing oils, especially those that are high in sulfur content.
kerogen, the correlation is negative.
Interpretation of 8 3~ values is complex, however. Good
. Oils and kerogens derived from highly reducing evapo-
examples of correlations employing sulfur isotopes are
ntes are often quite heavy isotopically (values near - 20
from the Big Hom Basin (Orr, 1974) and the Williston
0/00 versus PDB), probably because they contain exclu-
Basin (Thode, 1981).
sively algal material. Waxy oils, in contrast, are some-
times isotopically light, having values more negative than 4. Gas chromatography, measured on either the light
- 30 0/00. Some Pr.ecambrian and Lower Paleozoic oils hydrocarbons or on the whole oil (fig. 10.3). Schaefer and
also have 8 13C values more negative than - 30 0/00. The Leythaeuser (1980) have recently developed a "hydrogen-
158

stripping" method for removing and analyzing light

hydrocarbons from rock samples, thus permitting source-
rock-oil correlations. Empirical peak-by-peak correla-
Corbonotes
o - S1 tions suggest similarities and differences.
Sid 0 . .
i
119
918
Various ratios of light hydrocarbons have been used as
correlation or maturity parameters because formation of
branched isomers increases as maturity increases. The
Heptane and Isoheptane Indices of Thompson (1983)
have been used to classifY extracts and oils according to
type and maturity.
5. Compound classes, as determined by column or thin-
layer chromatographic separation. The relative propor-
tions of each compound class (saturated hydrocarbons,
aromatic hydrocarbons, resins, and asphaltenes) can give
indications about both source and maturity.
- 200 - ISO -100 -so Low contents of hydrocarbons in an extract indicate
00 l %0 J immaturity. Large proportions of hydrocarbons in an ex-
tract indicate either maturity, contamination by drilling-
fluid additives, or presence of migrated oil.
FIGURE 10.2 Difforences in hydrogen-isotopic compositions of Most oils will contain more than 75% hydrocarbons
oils sourced from carbonates and shales. Reprinted by per- (fig 5.20). Certain oils formed at low levels of maturity
mission of E. Schweizerbar'sche Verlagsbuchhandlungfrom from sulfur-rich kerogens can have large amounts ofNSO
Berner, 1982, Geol. Jahrbuch D67 (also in Schoell, 1984).

J~_

5 I

o
•
0' o
o

FIGURE 10.3 Gas chromatogram of light hydrocarbons re-

moved from a powdered rock sample by hydrogen stripping.
Reprinted with permission from Schaefer and Leythaeuser,
1980. Copyright 1980, Pergamon Press, Ltd.
 10. CORRELATIONS 159

compounds and asphaltenes, however. Monterey oils of

,.
California are prominent examples.
SAT .~--.
I I
6. Other bulk parameters less commonly employed in-
clude infrared spectroscopy (IR; useful for distin-
-
AROM
- HET
"----.-. ,,~
Jurassic oils
North Sea

guishing aromatic and aliphatic C-H bonds in oils or

-
bitumens), trace-metal contents (Hitchon and Filby,
1984; Poole and Claypool, 1984), and pour point.
ASPH
-
.,
KERO '0..
SPECIFIC PARAMETERS -28 -27 -26
-30 -29
Most specific parameters utilize biomarkers or isotope
I) 13CI'DIJ [0/00]
ratios. They include the following:
c D E
1. Isotope profiles, measured on fractions obtained by
column chromatography or (much more rarely) on a
series of specific compounds, such as n-alkanes. B 13C
values of the successively more polar fractions become, in
theory, increasingly more negative. The source kerogen
should therefore be slightly more negative than the as-
phaltene fraction of a related bitumen or crude oil. Figure
10.4 shows an ideal case; in practice the isotopic values of
the four fractions often show much more scatter. Jurassic
Sofer (1984) has used carbon-isotope measurements on o
I) 13CK = 24.8 [0/00]
two fractions (saturates and aromatics) of a crude oil to
classifY it as high- or low-wax (interpeted by Sofer to be
terrestrially influenced or wholly marine). He employed FIGURE 10.4 Example of an unsuccessful source-rock-oil
an empirical equation (eq. [10.2]) to make the distinction correlation based on carbon-isotopic compositions offour
at about the 90% confidence level. fractions of the oils extrapolated back to predict the carbon-
isotopic value of the source kerogen. The proposed jurassic
source rock is far off the predicted value. Reprinted by Per-
x = - 2.53(B 13Csat) + 2.22(B 13Carom) - 11.65, (10.2) mission of ErdOl und Kohle, Erdgas, Petrochemie from
Schoell, 1981.
where ifX < 0.47 the oil is low-wax (wholly
marine), and ifX > 0.47 the oil is high-wax (terres-
trially influenced). It therefore should be used for correlations only between
samples of similar maturity. Because most oils have CPI
2. n-Alkane distributions, measured by gas chro- values near 1.0, the CPI is not a very good correlation tool
matography of the saturated-hydrocarbon fraction. More for oils.
accurate results can sometimes be obtained by separating The overall aspect of the n-alkane profile is more useful
n-alkanes from the branched and cyclic saturated hydro- for correlations, although it still presents difficulties. As
carbons by urea adduction or molecular sieving prior to maturity increases, chain lengths of n-alkanes become
gas-chromatographic analysis. In attempting to use n- shorter. Thus a mature, waxy crude oil or extract and a
alkane distributions for correlation purposes, it is neces- less-mature sample of the source rock from which it was
sary to factor out maturity effects if they hC).ve been derived will have very different n-alkane distributions (fig
unequal for the samples being compared. 5.11). Direct correlation is impossible; only a faint indica-
The Carbon Preference Index (CPO obtained by gas tion of the original wax contribution remains in the oil.
chromatography is affected both by source and maturity. Less-mature waxy crudes will have larger amounts of
160

TABLE 10.1 Useful generalizations about pristanelphytane

ratios as indicators of depositional environment

1
oxidizing.
Sediment Type PristanelPhytane unr •• 'rlcted

Anoxic marine sediments <1

Oxic marine sediments 1-3 Pr
Coals >3 n-Cn

heavy n-alkanes, and, by preserving more oftheir original red uc Ingtev .porltlc
character, they have a better chance to be correlated with
a source rock. In general, wholly marine samples are very
difficult to correlate by means of n-alkanes because they Phi
In-C1B
always look mature.
3. Isoprenoid distributions, also measured by gas FIGURE 10.5 Use of isoprenoid/n-alkane ratios as correlation
chromatography of the saturated-hydrocarbon fraction. parameters and indicators of biodegradation, maturity, and
More accurate results can be obtained by removing the n- organic facies.
alkanes by urea adduction or molecular sieving prior to
gas-chromatographic analysis. Most commonly used are
pristane/phytane ratios and C15 to C20 isoprenoid profiles, still reported from gas chromatograms, but they are not
both of which are mainly related to diagenetic history. used regularly for interpretation.
Pristane/phytane ratios (PrlPh) are useful correlation
4. Isoprenoidln-alkane ratios, obtained by gas
parameters, in part because they are believed to be sensi-
chromatography. Combining isoprenoid and n-alkane
tive to diagenetic conditions (Illich, 1983). Very high Prl
data provides valuable information on biodegradation,
Ph ratios are associated with terrestrially influenced
maturity, and diagenetic conditions. A good way to
sediments, including coals (table 10.1). Pr/Ph ratios sub-
display these data is by plotting pristaneln-C 17 versus
stantially below 1.0 are taken as indicators of highly re-
phytaneln-C 18 (chosen because each pair of compounds
ducing depositional environments.
elutes almost simultaneously from the gas chro-
However, the accuracy of these generalizations has
matograph)(fig. 10.5). The trend of higher Pr/Ph ratios as
been challenged at times. Pratt (1984) has shown that
oxygen content of bottom waters increases is along the
sediments from the Cretaceous Western Interior Seaway
line marked "depositional environment" in figure 10.5.
that were deposited under anoxic conditions have Pr/Ph
With increasing maturity n-alkanes are generated faster
ratios considerably above 1.0. Thus, we must temper our
than isoprenoids (fig. 5.13), resulting in a decrease in
environmental interpretations based on isoprenoid distri-
isoprenoidln-alkane ratios and regression along the line
butions with other geological data. Furthermore, because
toward the origin in figure 10.5. Biodegradation, in con-
Pr/Ph ratios decrease during catagenesis (fig. 5.12), we
trast, removes n-alkanes faster (table 5.4), increasing
must be careful not to overuse them as correlation
isoprenoidln-alkane ratios away from the origin in figure
parameters.
10.5.
Profiles of C15 through C20 isoprenoids have been used
for many years as correlation fingerprints, but because 5. Porphyrins, measured either by visible-ultraviolet
the mechanisms by which these compounds are formed spectroscopy, high-performance liquid chromatography
are not well understpod, the technique has remained (HPLC), or mass spectrometry. UV gives a measure of the
strictly empirical. Concentrations of these isoprenoids are relative amounts of vanadium and nickel porphyrins, a

~..,. f ' IU • 10 re/ M
l ..... . O.5G
FIGURE 10.6 Gas chromatogram of saturated hydrocarbons
in a sample containing large amounts of resinite. Reprinted
by permission of the Canadian Society of Petroleum Geolo-
gists from Snowdon, 1980.
parameter that can be used for correlation because of its
relationship to diagenetic conditions (see chap. 5).
Mass spectrometry and HPLC offer a detailed break-
down ofthe various classes of porphyrins present and can
be used for more detailed fingerprinting (fig. 7.9). How-
ever, given the dramatic changes in carbon skeletons and
substituents that occur in porphyrins as a result of mat-
uration, it is very difficult to correlate samples of different
maturities.
6. Polycyclic-hydrocarbon biomarkers, measured by
gclms of saturate and aromatic-hydrocarbon fractions.
These include diterpanes, triterpanes, and steranes. Diter-
panes are useful correlation parameters when resinite is
an important source contributor, because one or two di-
10. CORRELATIONS 161
Gammacerane
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.
terpanes may be the most dominant compounds present
in the entire sample (fig. 10.6). Other diterpanes are not
derived from terrestrial plants, however. We must there-
fore be careful to use only the appropriate diterpanes as
indicators of a resinite contribution.
Triterpanes have proven very valuable as correlation
parameters because they are sensitive to diagenetic condi-
tions, to biodegradation, and, in some cases, to the type of
organisms from which the organic matter is derived. The
ratio ofC 29 to C30 regular hopanes appears to be related to
depositional environment, with a predominance of C29
possibly indicating euxinic conditions.
Other less frequently encountered triterpanes are
thought to be of paleoecological significance. The uncom-
mon C28 hopane seems to be prevalent in rocks deposited
under anoxic or euxinic conditions. It has been found, for
example, in the Monterey Formation (Miocene of south-
ern California) and in some facies of the Kimmeridge Clay
of northern Europe. Its direct precursor is unknown but
presumed to be microbial. An unusual C27 hopane has
been identified in oils and their source rocks from the
Norwegian Continental Shelf and the North Sea. Gam-
macerane and oleanane (fig. 10.7) are thought to be asso-
162
RJrDfAS IHOAL
WI •• t TAlTEJIIIAHfa
1'''' ""'0 HCIO , ..0
FIGURE 10.8 Comparison of mass chromatograms for two
Australian oils. Triterpanes in the Fliruiers Shoal oil are only
slightly biodegra£led, as shown by the complement of hopanes
(labelled with H) and moretanes (M). Demethylated hopanes
(D) are less important constituents. The Mardie oil, in con-
trast, has lost all its hopanes and moretanes through de-
methylation. There is a perfect corresporuience between a
hopane or moretane in Fliruiers Shoal and a demethylated
molecule in Mardie. Reprinted with permission from Volk-
man et al., 1983a. Copyright 1983, Pergamon Press, Ltd.
ciated with lacustrine and certain deltaic sediments,
respectively. Gammacerane probably comes from a proto-
zoan, whereas oleanane is derived from terrestrial plants.
These unusual compounds facilitate both positive and
negative correlations.
At least one important type of triterpane is produced as
a result of biodegradation. C-25 norhopanes (hopanes
that have lost the methyl group containing carbon atom
number 25, located at the juncture between rings A and B
in fig. 3.3) are found only in severely biodegraded crudes.
These molecules are probably created by selective re-
moval of a single methyl group by bacteria. As a result of
this demethylation, those hopanes that used to produce a
strong mlz 191 peak now fragment to yield a 177 ion (fig.
7.7). Figure 10.8 shows the nearly perfect correspondence
between the mlz 191 mass chromatogram for a whole oil
and mlz 177 for a related but intensely biodegraded crude
(level 9 of table 5.4).
The relative proportions of normal and demethylated
hopanes have been used as an indicator of mixing of
biodegraded and normal crude oils (Philp, 1983; Alexan-
der et al., 1983; Volkman et al., 1983a). Philp (1983)
identified four oil types in the San Jorge Basin of Argen-
tina on this basis (fig. 10.9). Mixtures of biodegraded and
undegraded oils look very different from partially de-
graded oils because the latter show no changes in the
steranes and triterpanes.
Steranes are valuable correlation parameters because
of the direct dependence of C Z7' C Z8 ' and C Z9 regular-
sterane concentrations on their precursor C Z7 to C Z9 sterols
(see also chap. 5). C Z7 sterols dominate in marine organ-
isms, whereas C Z9 sterols are more common in terrestrial
plants. These relationships can be expressed in a triangu-
lar diagram (fig. 10.10), which allows one to estimate the
growth environment of the contributing organic matter.
Diagenesis apparently does not influence CZr-CZ9 sterane
contents.
In rocks and oils of pre-Silurian age, C Z9 steranes often
predominate over C Z7' despite the absence of land plants
prior to the Silurian. These data suggest that, prior to the
Silurian, some marine organisms contained more C Z9
steroids than C Z7 • It is also possible that these same
marine organisms could yield high C Z9 sterane concen-
trations in post-Silurian sediments. CZr-CZ9 sterane con-
centrations should therefore be used with care as an
indicator of paleoenvironment.
Interpretation of distributions of CZr-CZ9 steranes is
easy when the samples are thermally immature, but
within the oil-generation window a multitude of new
steranes is created by a variety of catagenetic reactions
that modifY the sterane molecules in very subtle ways (fig.
5.14). Sterane mass chromatograms (mlz 217) from ma-
ture bitumens or oils are therefore much more complex
than those for immature samples (fig. 8.12). The severe
overlap of the various peaks often makes it difficult to
obtain accurate measurements of the concentrations of
the regular steranes and reduces the value of steranes as
correlation and environmental parameters. The general
similarity of sterane profiles also makes the steranes
somewhat less useful than triterpanes.
Steranes are of less value where biodegradation is
 10. CORRELATIONS 163

C~I

Group I GI'OUp :J
Regular hopane C2 ' 1 mz 191 /llIZ 191

C 2'1
(;I'OUp 2 Group 4
mz 191 nllz 191

Demelhylaled hopanes
C2iI

. ...

FIGURE 10.9 Four oil types in the San Jorge Basin, Argen-
tina, 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 demethy-
lated species, while those of Group 4 are fully biodegraded,
showing only the demethylated species. Reprinted with per-
mission from Philp, 1983. Copyright 1983, Pergamon Press,
Ltd.

extreme because the regular steranes are destroyed

completely in the late stages of biodegradation. Other
steranes, however, are not affected by bacteria and thus
can be used for correlation.
Mono- and triaromatized steranes can be monitored by
rnIz 253 and 259 mass chromatograms, respectively.
These compounds are formed by the oxidation of ste-
ranes, perhaps facilitated by the presence of anhydrite.
Aromatization greatly reduces the usefulness of steranes
as biomarkers, but aromatized species can still be em- FIGURE 10.10 Triangular diagram for interpreting sterane
ployed in correlations or for maturity determinations (see distributions in terms of marine, terrestrial, and lacustrine
chap. 8). origin of the organic source material.
164

10':>

,"_ __ Olde' Inltlolly Drt Qaw •

• -. ,- , ~ 12C Depleted Produced 1"1
10 Go~ Go~
M
ZO E Of
U MICROBIA.
+

-
N ORIG I
U
10 3 I
I
I
U Hlgne' 1
Hydroco r bons r
Oepteled 1
Du"ng I
Mlg'o ,on I
I
-I.
10 2 I
I
/
/

ZO E *' " FIGURE 10.12 Crossplot of 8D and 013C of methane for natu-
10 1 OF 0'>-,,::- ------ ral gases, by which gases of various origins can be distin-
THERMO, guished. Reprinted by permission of ErdOl und Kohle, Erdgas,
CATALVTIC Petrochemie from &lwell, 1981.
OR IGI I I M.. lure ' ..

methane are referred to as dry gases. Dry gases are

-1.0 -50 -60 -70
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.
CORRElATION PARAMETERS FOR GASES
Gas correlation is much more difficult than oil correlation
because the much simpler gas molecules convey far less
information than do oil molecules. The only parameters
available for gas correlations are 8 13C, 8D, and wetness.
Carbon-isotope ratios are normally measured on
methane isolated from the gas mixture. Upon rare occa-
sions they are also determined for ethane and propane.
Hydrogen-isotope measurements are normally made only
for the methane.
Wetness is a measure of the proportion of hydrocar-
bons heavier than methane in the gas. Gases whose hy-
drocarbon fraction contains more than about 99%
-80 formed either by bacteria (in which case they are very
dry, because methanogens produce only minute amounts
of ethane and heavier hydrocarbons), by metagenesis of
kerogen, or by late cracking of oil and wet gas. Wet gases
are formed either by early cracking of oil or by
catagenesis of kerogen.
There is no way to distinguish among the various possi-
ble origins for either wet or dry gases on the basis of
hydrocarbon-composition alone. However, by combining
wetness data with carbon-isotope measurements, we can
easily distinguish between dry gases of biogenic and
metagenetic origins (fig. to.11). Rice (1983a) has even
suggested that thermal gases derived from marine and
nonmarine source rocks can be distinguished on the basis
of8 13C values, but there is much overlap between the two
populations.
Plotting 8D versus 8 13C for methanes offers another
way to qistinguish among gases of different origins. The
interpretation of such diagrams is not straightforward,
however, as shown by the two schemes in figure 10.12.
Application of hydrogen isotopes to natural gases is a
technology still under development.
 10. CORRELATIONS 165

R
WEST SEA HORSE.,
48 AP •

...
% .. 1 ._-----l 3

....."'
o

a: lAKES ENTRANCE

..
a: '6 AP. mIl 217
o
...o
0-
tON

w 4
Q ABUNDANCE

RETENTION T.ME ( ..... ' •• 1

o 20 40
RETENT.ON Tllo!E(m.nul •• 1

FIGURE 10.14 Partial m/z, 217 mass chromatograms of

FIGURE 10.13 Gas chromatograms of saturated hydrocar-
bonsfrom Lakes Entrance and West Sea Horse #1 oils,
Gippsland Basin, Australia. Reprinted by permission of the
Australian Petroleum Explnration Association from Alexan-
der et al., 1983.
CASE STUDIES
BIODEGRADATION
The Lakes Entrance oil (16 API, 36s-m depth, Tertiary
0
reservoir) and West Sea Horse *1 oil (48 API, 1400-m
0
depth, Cretaceous reservoir) from the Gippsland Basin of
Australia have very different chemical and physical prop-
erties (Alexander et al., 1983). Gas chromatograms ofthe
saturated-hydrocarbon fractions are shown in figure
10.13. Mass chromatograms are presented in figures
10.14 and 10.15. Could there be any genetic relationship
between these two oils?
From the gas chromatograms it is evident that the
Lakes Entrance oil is heavily biodegraded, with both n-
alkanes and isoprenoids completely destroyed. Biodegra-
dation has even affected the steranes (fig. 10.14), leading
to a decrease in the biologically produced sterane (peak
4) at the expense of the catagenetically produced steranes.
Lakes Entrance and West Sea Horse #1 oils, Gippsland Ba-
sin, Australia. Reprinted by permission of the Australian Pe-
troleum Explnration Association from Alexander et al.,
1983.
However, the m1z 191 mass chromatogram shows no in-
dication 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 possi-
ble 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 con-
sistent with a common origin. Furthermore, one unusual
feature of the m1z 191 mass chromatograms of both oils
166
weST se" HORse 4- I ..
e ....
II 7
" 10
mlz 191
~.1
Ill. "
ION
II
11
.... 11o. ....
'V/I'\" .1J"
... n '" ,. I
ABUNDANCE
RETENTION TIIiIIE(m l nul •• )
makes a strong case for a common origin: the high ratio of
peaks 6 to 5 (Tmffs) in figure 10.15 is unusual for a
mature oil such as West Sea Horse #1 seems to be. The
high Tmffs ratio could either indicate a low maturity, or
the Tm peak could include a contaminant (Volkman et
al., 1983b). In either case the ratio is a peculiar character-
istic that the oils share.
OIL-OIL CORRELATIONS
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 Or-
dovician 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-
,
..,..:e
LAKES ENTRANCE
R2
'" 1
"
12
1
1\
FIGURE 10.15 m/z, 191 mass chromatograms of Lakes En-
*
trance and West Sea Horse 1 oils, Gippsland Basin, Aus-
tralia. Reprinted by permission of the Australian Petroleum
Exploration Associationfrom Alexander et al., 1983.
thusiasm by exploration geologists, who had difficulties
accepting the migration of Ordovician oil through the
thick, basin-wide, seal-forming Silurian Salina salt.
The controversy has still not been resolved as of this
writing. Part of the difficulty has stemmed from unans-
wered questions about the maturity of Devonian black
shales in the basin. Few Devonian samples toward the
center of the basin have been analyzed. Modeling of ma-
turity (Nwm et al., 1984; Cercone, 1984) is complicated
by the great age of the rocks, uncertainty about paleoheat
flows in the basin, and lack of samples with which to
check the models. Proof that Devonian shales in the center
of the basin are in fact mature would be a strong indica-
tion of local sourcing for the Devonian oils (which, per-
haps significantly, are located in the center of the basin;
see Vogler et al., 1981).
Results of oil-correlation work in the Michigan Basin
show how difficult correlations can sometimes be and
how dependent the results of correlation attempts can be
on the particular analyses selected. Future work in the
Michigan Basin should include gc/ms studies of polycy-
clic-hydrocarbon biomarkers.
 10. CORRELATIONS 167

I~r--------------------------r------------------------~r-------------------------~
NORTHVILLE GRANT 26 BENTLEY
OrdovIc Ian Slkrlan
CPl. \.29 CPl.' O!>

10

I-
Z
W
<.J
a:
W
0..

I~ 20 2~ 30 20 30 I~ 20 ~

ALKANE CARBON NUMBER

FIGURE 10.16 n-Alkane and isoprenoid distributinns from

gas chromatograms of saturated hydrocarbons from typical
Ordovician, Silurian, and Devonian oils from the Michigan
6 Ordov ician (Trenton)
Basin. Reprinted with permissinnfrom Vogler et aI., 1981. -23
Copyright 1981, Pergamon Press, Ltd. o Silurian (Nlaoara)
o Devonian ([)undee)
·25

CD

.
~-27

>
/. -29

~
..0

-3'

-33

'2 '4 16 18 20 22 24 26 28 30 32
n-ALKANE CARSON NUMBER

FIGURE 10.17 Carbon-isotope profiles of individual n-alkanes

for typical examples of Ordovician, Silurian, and Devonian
oils from the Michigan Basin. Reprinted with permissinn
from Vogler et al., 1981. Copyright 1981, Pergamon Press, Ltd.
 4.O"'-----""T-----------,
.. DEVONIAN

1
• AI.L SILURIAN
.. ORDOVICIAN

~ 30-

~
I/) ..•
~
~ 2.0 -

.
. .... .
.. ...." ....
.2-
I- "
:z
I&J

~ 1.0- ... o. ' .

&"i".eN HT~r IIII'f'f"'J

I r4 J'00ft" UW'lIOIf M"l'"

"~""""'DUfilllOIfJ

0.0 .0.0 ,~ 2' 0 ~O 4.0

FIGURE 10.18 Triangular pint ofpristane, n-Cn. and n-CZ1
--PERCENT ;p 20 (PHYTANE}----'»
for Michigan Basin oils. Reprinted with permission from
Pruitt, 1983. Copyright 1983, Pergamon Press, Ltd.
FIGURE 10.19 Crossplnt of pristane versus phytane for
Michigan Basin oils. Reprinted with permission from Illich
and Grizzle, 1983. Copyright 1983, Pergamon Press, Ltd.

,O.O_-------""'T---------------------~

• OCVO/OlIAN
• ~H£RN SILURIAN
• SOIITH£RN SILURIAN
•
- .....•
.. ORDOVICIAN
8 .0-}-_ _ _ _ _ _ ~

.,
•
.
. •
,~

• • ,•""'
/"
SAGINAW(8(REAI.. •

...... 6

•
. ..
"t/'
A ........ iltCli #tUN lOtJHO(c)
2 .0-
6 "'001111 lOfTIIOIT IIMII'

~O-t~~-r_·~I~~~~~,~~-,~-~I~T-T-~r-,r-r-~~I~~~~~
0 .0 10.0 20.0 30.0 400 !}()D 600
PERCENT NORMAL PARAFFINS
I CN' t 1016 t 1017 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 169

SOURCE-ROCK·OIL CORRELATIONS oils are only moderately enriched in sulfur (less than
Oils are produced from several fields in the Basin and 0.7% ).
Range province of Utah and Nevada. Poole and Claypool One implication of this study is that oil generation from
(1984) have succeeded in classitying most of these oils the lacustrine source beds in the Basin and Range prov-
into two groups, based on numerous geochemical ince occurs at very low levels of maturity, probably as the
analyses. result of the combined effects of great richness of the
They also found excellent correlations between the two source rocks and high sulfur contents of the kerogens.
groups of oils and two very different types of source rock. This knowledge derived from the correlation studies
The Chainman Shale of Mississippian age was deposited should then be incorporated into future exploration mod-
in a marine basin. The Sheep Pass and Elko formations, els for the area.
in contrast, are of Paleogene age and represent lacustrine
facies.
The most useful analytical techniques for correlating
specifc oils and source rocks were gas chromatography
(fig. 10.21) and gc/ms (fig. 10.22). The Trap Spring oil,
for example, has a very similar gas chromatogram to that
from a mature sample of Chainman shale (fig. 10.21): Prl
Ph ratios are near 1.5, CPI values are near 1.0, and the
samples are low in heavy n-alkanes. Oils from the Eagle
Springs and Currant fields, in contrast, have PrlPh ratios
below 1.0, display even-carbon predominances, and con-
tain moderate to large amounts of heavy n-alkanes.
The most powerful arguments for the proposed source-
rock-oil correlations come from sterane and triterpane
distributions (fig. 10.22). The lacustrine rocks all contain
large amounts of gammacerane (peak 7 in fig. 10.22), an
indicator of lacustrine origin. Five of the oils analyzed,
including the previously mentioned Eagle Springs and
Currant oils, also contain large amounts of gam-
macerane.
These five oils correlate very well with the lacustrine
source rocks in other respects as well. All have more of
the 20R- than 20S-epimer of the C29 sterane (peaks D and
A in fig. 10.22), which indicates low maturity.
The remaining four oils shown in figure 10.22 correlate
well with the Chainman shale extracts. Gammacerane
contents of all samples are low; maturities are high, as
indicated by an excess of the C29 20S-epimer over the 20R-
epimer.
Surprisingly, sulfur contents of the lacustrine oils are
greater than 1%, with some biodegraded oils above 4%.
The unusual Rozel Point crude, which is asphaltic, highly
biodegraded, and produced from basalt, contains 12%
sulfur. The origin of the sulfur in the ancient lakes is an
interesting question. In contrast, the Chainman-sourced
 ~

B. EAGLE SPRINGS FIELD

ORAYCUTT NO. 45-36 f
(6064 . 6230 11 1 C. CURRANT AELC
A TRAP SPRING FIELD 16856 • 70lI0 111
ZUSSPAN NO. 24· 1
14910 . 4944 tt l
is.
t. I
is.
is.

~, I I I I I 30
I
30

"'lW.LUJJ~ .llllil.ll.J.l h ,j ~ L
11.1

F. SHEEP PASS FORMATION

ESU NO. 35-35 (6810 111
E. SHEEP PASS FORMATION
ESU NO. 35-35 16888 11)

D. CHAINMAN SHALE
ESU NO 2 (9497 ft ) ~
is.li
is.

s:.
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 EXTRACTS
C29

n
CRUDE OILS TERPANES STERANES

::,.------=--~ ~-~
0-
1.0
Uool D U
SHEEP PASS FORMATION
11810'
0.5

0.5

1.0
CHAINMAN SHALE 10,121'

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
I I I I

Old . , Initially
. ~:;: =~ 12C Dtplt t td <}::::::> P'nduced
10' <- Gas (,as -:

,,
M I ZONE O~ I

U ,
I

,,,
MICROBI AL
15 20 25 JO 15 20 25 JO 15 +N I

,,I
--- ,
ORIGI I

-
- - - - - - - - CARBON NUIl8ER - - - - - - -- U I
I ,
10 3 I
I ,
I
-:

U ,,
Hlghe' I
I
FIGURE 10.23 Distributions of n-alkanes and isoprenoids for Hydrocar bons I
MIXING
,
three oils from different depths in the Handil Field, Maha- Ceplet ed I I
DUling I I

,
kam Delta, Kalimantan. ZO E I
10 2 .-
Migration I
,I ,
,, ,,
~ ,
•, -
,, ~~
., ~
~

--
0---'::- --- -
ZO E *~'
OIL MATURITY ~

Three oils were recovered at different depths from the 10 1 b- OF -:

Hamill Field in the Mahakam Delta of Kalimantan. An
important question was "Do these oils represent a matu-
rity sequence, or are other factors responsible for the dif-
ferences in chemical composition?" Distributions of n-
alkanes and isoprenoids are shown in figure 10.23.
Although the data available for making this judgment
are rather scant, we can still make some useful comments
about the maturities and sources of the oils. The high Prj
Ph ratios of all three oils indicate similar sources, proba-
bly coals or paralic rocks containing a large amount of
terrestrial material. The two deepest oils contain large
amounts of heavy n-alkanes. The CPI and average chain
length of the n-alkanes decrease from the deepest sample
to the shallowest, suggesting that the deepest sample is
the least mature. Thus the oils form an inverse maturity
sequence, indicating that hydrocarbon accumulations are
controlled by possibilities for vertical migration.
GAS CORRElATIONS
Devonian black shales in the eastern United States contain
vast amounts of gas in fractured reservoirs. The source for
this gas has been a matter of some concern. Outcrops of
the black shales themselves in Ohio and Kentucky are rich
in organic matter (averaging well over 5% TOC) but are
thermally immature (reflectance values less than 0.6%).
Given the richness but immaturity of the hypothesized
source rocks, it was proposed that the gas was biogenic.
THER MO' •
CATALY IC
ORIGI 1 I M lxh.U ~ · *
I I 1 ! 1
-1.0 -50 -60 -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.
In an effort to test this hypothesis, a sample of the gas
was analyzed for wetness and carbon-isotopic composi-
tion, and the results were plotted (fig. 10.24). It is clear
from the low ratio of methane to heavier hydrocarbons
and the l) 13C value of the methane that the gas is not bio-
genic, but was generated instead by thermal processes.
The mystery of how immature rocks could generate
thermal gas is solved when we realize that by limiting our
black-shale analyses to outcrops, we missed the more-
deeply-buried, mature areas. It is therefore likely that ma-
ture equivalents of the exposed black shales do occur in
the subsurface, that they are the sources, and that updip
migration through the fracture network within the black

shales is responsible for the occurrence of commercial gas
accumulations in immature reservoirs. This model also
suggests that gas might be producible from deeper reser-
voirs, provided that traps (either traditional or kinetic: see
chap. 6) exist.
CONCLUSIONS
I recommend adopting the following philosophy in de-
signing and executing a correlation study:
1. Both bulk and specific parameters should be em-
ployed.
2. The least-expensive analyses should be carried out
first; expensive ones may not be needed if the inexpen-
sive 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 pos-
sible.
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 corre-
lations are usually made with more confidence than
positive ones.
7. Some samples have more distinguishing characteris-
tics than others. Samples having unique features will
be easy to correlate, whereas samples having no distin-
guishing 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.
10. CORRELATIONS 173
SUGGESTED READINGS
Alexander, R., R. I. Kagi, G. M. Woodhouse, and J. K. Volk-
man, 1983, The geochemistry of some biodegraded Austra-
lian 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 Associ-
ation of Petroleum Geologists, 426 pp.
Fuex, A. N., 1977, The use of stable carbon isotopes in hydro-
carbon 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., Ad-
vances in Petroleum Geochemistry, Volume 1: London, Aca-
demic Press, pp. 115-214.
Mattavelli, L., T. Ricchiuto, D. Grignani, and M. Schoell, 1983,
Geochemistry and habitat of natural gases in Po Basin, north-
ern 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., Hydrocar-
bon Source Rocks in the Greater ROCky Mountain Region:
Denver, Rocky Mountain Association of Geologists, pp. 179-
229.
Rice, D. D., 1983b, Application of organic geochemistry to hy-
drocarbon occurrence, in D. D. Rice and D. 1. Gautier, eds.,
Patterns of Sedimentation, Diagenesis, and Hydrocarbon Ac-
cumulation 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 Ba-
sin, in A. D. Miall, ed., Facts and Principles of World Petro-
leum Occurrence: Canadian Society of Petroleum Geologists
Memoir 6, Calgary, Candian Society of Petroleum Geologists,
pp. 421-446.
174

Volkman, J. K., R. Alexander, R. I. Kagi, and J. Rullkotter,

1983, GC-MS characterisation of C Z7 and Cza triterpanes in
sediments and petroleum: Geochimica et Cosmochimica 1) OAR(HI"r,
Acta, v. 47, pp. 1033-1040.

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 18 VELOEN

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 I
to identifY the culprit by organic-geochemical methods. n.(1C
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, car-
19 TE ISIN(i
bon-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 I
do next? In retrospect, how would you critique your approach? \
5. Gases are produced from many fields in the Po Basin ofItaly.
Reservoir ages range from Pleistocene to pre-Miocene, and
l v~
depths of production range from 170 m to 4,500 m. Maximum
I
~'
reservoir temperatures are about 75° C. Thermal-maturity data
indicate Ro values reach a maximum of about 0.6% at 5000-m
depth (Mattavelli et aI., 1984). , FIGURE 10.25 Gas chromato<'S'"ams of a paraffinic oil (top)
A plot of gas wetness versus & 13C of'methane (fig. 10.29) and two naphthenic oils (middle and bottom) from the Ger-
shows a wide range of compositions. What can we say about the man Molasse Basin. Reprinted with permission from Huf-
origin of the gases in the Po Basin? nagel et al., 1980. Copyright 1980, Pergamon Press, Ltd.
 to. CORRELATIONS 175

1~ ASSLING

16 AMP~ ING

.~l .l~. ,1.4

.. .
--'
I~'
~

• • r""J. .,.... . -,..-. .. r-o' Iii"? t o, .... i . ... ~...,"',...............,f".t'

"----lJ~ ____

. . . . . . . . ~~· .-.~~ rmf f""I'l1

FIGURE 10.26 m/z 217 mass chromatograms for a paraffinic

oil (top) ami a naphthenic oil (bottom)from the German
Molasse Basin. Reprinted with permission from Hufoagel et
al., 1980). Copyright 1980, Pergamon Press, Ltd.
 .
J ____ ASSERBURCi

__~,~J lJ~,

ENOORF

16 AMPF ING

FIGURE 10.27 mlz 217 mass chromatograms for two Fisch-

schiefer extracts (top) and two oils (bottom) from the Ger-
man Molasse Basin. Reprinted with permission from Huf-
nagel et aI., 1980. Copyright 1980, Pergamon Press, Ltd.
 to. CORRELATIONS 177

TABLE 10.2 Geochemical data for three oils

from the Gondwana Field

Blue
Well
Green
Well
Aquamarine
Well
,. .,
.. II
t7

Depth (ft)
Reservoir age
8100
L. Cret.
10,200
E. Cret.
8700
Eocene ..
,. 27
.
API gravity (deg) 46.1 44.3 32.5

..
% Sulfur
CPI
& 13C whole oil (0/00)
& 13C saturates (0/00)
0.12
1.01
-26.1
-27.9
0.08
1.02
-27.0
-29.5
0.21

-26.6
-28.3
-A 1.J 1
....
t~J LlI.I I' ! Jo li III III lL LII. Il 1 i I

% saturated HC 60.4 72.5 48.3

% aromatic HC 28.5 16.3 21.6
Pristane/phytane 1.5 3.6 2.0

,~
23 " '9 Po.
17

'9
"

J~
. 16

3'
....
3.

...
• 18 ' '16

FIGURE 10.28 Gas chromatograms of saturated hydrocar-

bons from oils from the Gondwana Field: (A) Blue well, (B)
Green well, and (C) Aquamarine well.
178

TABLE 10.3 Geochemical data on twelve produced oils and a spill oil from the South Hootchiekootchie Basin

Produc- API 1\ '3C of Porphyrins Maximum

Production ing For- Gravity % topped Oil in n-Alkane
Well Depth (ft) mation (oAP!) Sulfur (0/00 vs. PDB) Ni V Pr/n-C'7 Phln-C'8 PrlPh CPI Distribution

1 8100-8150 C 30.5 0.8 -26.7 1.02 1.55 0.81 0.68 1.2 1.01 17
2 6763-6849 A 27.5 0.3 -29.7 0.00 0.03 0.03 0.43 0.1 1.13 18
3 8460-8610 C 34.5 0.1 -27.9 0.16 0.12 0.23 0.92 0.2 1.02 17
4 7998-8016 C 19.7 0.7 -26.7 1.21 1.02 0.21 0.67 0.3 1.04 16
5 9001-9202 C 31.8 1.3 -28.0 0.92 1.45 1.02 0.88 1.2 0.99 17
6 6887-6990 C 29.7 1.2 -28.1 1.02 0.34 0.92 0.91 1.0 1.07 17
7 7421-7503 C 25.7 1.7 -26.4 0.99 0.29 0.19 0.66 0.3 1.04 17
8 9023-9112 B 24.3 2.2 -26.2 0.15 0.05 0.31 1.72 0.2 0.87 18
9 6810-7020 A 28.1 0.1 -30.1 0.02 0.00 0.11 0.51 0.2 1.17 17
10 9100-9140 D 36.1 0.2 -28.4 0.15 0.13 0.49 0.96 0.5 1.06 18
11 8321-8520 D 24.3 1.7 -27.2 0.88 0.21 0.97 0.79 1.2 1.03 16
12 8169-8230 C 21.2 0.6 -26.9 1.15 0.96 0.16 0.81 0.2 0.98 17
Spill oil 12.7 3.7 -25.7 0.72 0.27 3.65 16.1 0.2

SOLlITlONS TO PRACTICE PROBLEMS

1 1
1 I
I I
[]J 1. Gas chromatograms (fig. 10.25) indicate that the naphthenic

•
I 1
oil is strongly biodegraded, with the n-alkanes and isoprenoids
[BJ
1 1
1 1
t removed. The paraffinic oil, in contrast, appears to be unal-
:.
I 1
1
1 "'~ I • MolOSSQ
tered. Thus the oils could be related; in order to test that idea,
1
.,11./ :
m
.1
1
1 ·1 I we will have to look at biomarker parameters that would have
:..
I
1
I. II been unaffected by biodegradation.
1
1 I t
Mass chromatograms of the steranes (fig. 10.26) show no
I
1
1
1 l'" Vigallo
• DO: .. ~ '"
05 1 1
I
I significant differences between the paraffinic and naphthenic
1
~I.a 1
1 I
1 oils, indicating that (1) biodegradation has not yet strongly af-
0.2 ~.D 1 1 1 • PlEISJOCENE
fected the steranes, and (2) the oils could be related. This one
1 1 1
I
D~. • U.·".PUOCENE
0.1 ':1,00 D
I. 1
1 o l PLIOCENE piece of positive evidence should not be taken as proof, however.
·-0• •. • • 1I •
""\:i ~.D
• D Medesano""· ... MESSINIAN
Other techniques, such as analysis of mass chromatograms of
0.05
•
1
i
...
1 '" " "'OCENE
other fragment ions, should be utilized to strengthen the
.:
1 1 • PRE·"'OCENE
1
0.02 D 1
.... , mlgtol.d g05
correlation.
1
•-70
1
0.01
-80 -60 -50 -40 -30
2. The correlation between m1z 217 mass chromatograms of two
6 Be vs. poe [ppt] samples of Fischschiefer extract (fig. 10.27, top) and two
Molasse Basin oils (fig. 10.27, bottom) is vel}' poor. However,
the most obvious poor correlations are due to maturity differ-
FIGURE 10.29 Wetness versus carbon-isotopic composition
ences between the vel}' immature shale and the mature oils.
for natural gases from the Po Basin, Italy. Reprinted by per-
mission of the American Association of Petroleum Geologists These maturity-related differences themselves do not rule out a
from Mattavelli et al., 1983. mature Fischschiefer as the source.
Much more important in comparing these shales and oils are
parameters that do not change appreciably with maturity. The

relative proportions of the 50:,140:,170: 20R steranes (C Z7 to CZ9 )
are not affected by maturity. In the Fischschiefer CZ7 is by far the
largest peak, and CZ9 the smallest. In the oils, however, CZ7 is not
nearly as dominant. This difference casts doubt on even a ma-
ture Fischschiefer as the principal source for these oils.
Because of the great difference in maturities of the samples
being compared, even a negative correlation is somewhat uncer-
tain. Thus it would be advisable to strengthen these conclusions
with other analyses.
3. Some differences are apparent between the oils from the Blue
and Green wells. The close similarities of several independent
parameters (carbon isotopes, hydrocarbons, sulfur contents)
suggest that these two oils could have a similar source. The
substantially lower n-alkane content of the Green oil might indi-
cate a slight amount of biodegradation. The most striking differ-
ence, in the PrlPh ratios, cannot be attributed to biodegradation;
it might instead indicate some mixing. Alternatively, the two oils
could come from different sources, with high levels of maturity
in both oils being responsible for some of the gross similarities
(API gravity, hydrocarbon content, n-alkane distributions). The
substantial difference in the isotopic compositions of the
saturated hydrocarbons of the two oils further suggests a source
difference. Stronger evidence about the similarities and dis-
similarities of the Blue and Green oils would be furnished by gcl
ms analysis of biomarker hydrocarbons.
The oil from the Aquamarine well is clearly different from the
other two. However, all the tabulated properties except API
gravity and saturated-hydrocarbons are very similar to those of
the Blue oil. Biodegradation could be responsible for the ab-
sence of n-alkanes and the lower API gravity of the Aquama-
rine oil. Evidence for biodegradation at the depths of the
Aquamarine and Green oils is unusual, which suggests either
that geothermal gradients are quite low, or that biodegradation
took place when the reservoir was at a shallower, cooler depth.
In this latter case, migration into the reservoir would have oc-
curred prior to substantial amounts of additional burial.
The fact that such diverse parameters as carbon isotopes,
sulfur contents, and isoprenoid hydrocarbons are in agreement
indicates that there may be a genetic relationship between the
Blue and Aquamarine oils. Gc/ms should be used to test this
hypothesis.
4. The spilled oil has probably undergone a significant amount
of evaporation and biodegradation as a result of exposure to sea
water and air. Neither API gravity nor n-alkane analyses are
therefore very meaningful. Because pristane and phytane are
still present, the Pr/Ph ratio is valid. Even if they had been
10. CORRELATIONS 179
affected somewhat by biodegradation, the ratio should remain
unchanged. Sulfur content would probably have risen slightly
during biodegradation. The carbon-isotopic composition would
have become slightly heavier (less negative) as a result of the
loss of isotopically light alkanes and aromatics through biodeg-
radation and water washing. Porphyrin content would have
been increased as a consequence of the preferential loss of hy-
drocarbons. NW ratios would not have changed, however.
We can evaluate the data in table 10.3 in light of all these
facts. Data for oil samples from the wells that are definitely
incompatible with those of the spill oil are set in boldface type,
and all dubious correlations are in italic (table 10.4).
The PrlPh ratio of the spilled oil is 0.2. The oils having Pr/Ph
ratios above 1.0 do not correlate with the spill. The very high Prl
n-C 17 and Phln-C 16 ratios are the result of biodegradation and
thus cannot be used for correlation.
Because the NW ratio of the spilled oil is about 3, those oils
whose NW ratios are not near 3 can be eliminated. Further-
more, oils 2 and 9 are probably not the source of the spill
because their total porphyrin contents are too low.
Sulfur content of the spilled oil is higher than in any of the
possible source oils. Although sulfur will be concentrated as a
consequence of biodegradation, there are limits to how much
the sulfur content will increase. Certainly the low-sulfur oils
(less than 0.5% S) could not be the source. Those with less than
1% S are doubtful but should not be eliminated completely.
& 13C values of the various fractions of a crude oil seldom
differ by more than about 2 0/00. Thus even if the spilled oil had
lost all its saturated hydrocarbons, the isotopic composition of
the whole oil would not have changed by more than 2 0/00. The
most-negative value possible for the original spill oil is thus
-27.70/00.
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 distri-
butions by gc/ms. Given the low level of biodegradation experi-
enced 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

TABLE 10.4 Quality of correlations in geochemical parameters between a spill oil

and twelve produced oils from the South Hootchiekootchie Basin.
produc- API l) 13C of Porphyrins Maximum
Production ing For- Gravity % Topped Oil in n-Alkane
Well Depth (ft) mation (oAPI) Sulfur (0/00 vs. PDB) Ni V Prln-C '7 Phln-C '8 PrlPh CPI Distribu tion

1 8100-8150 C 30.5 0.8 -26.7 1.02 1.55 0.81 0.68 1.2 1.01 17
2 6763-6849 A 27.5 0.3 -29.7 0.00 0.03 0.03 0.43 0.1 1.13 18
3 8460-8610 C 34.5 0.1 -27.9 0.16 0.12 0.23 0.92 0.2 1.02 17
4 7998-8016 C 19.7 0.7 -26.7 1.21 1.02 0.21 0.67 0.3 1.04 16
5 9001-9202 C 31.8 1.3 -28.0 0.92 1.45 1.02 0.88 1.2 0.99 17
6 6887-6990 C 29.7 1.2 -28.1 1.02 0.34 0.92 0.91 1.0 1.07 17
7 7421-7503 C 25.7 1.7 -26.4 0.99 0.29 0.19 0.66 0.3 1.04 17
8 9023-9112 B 24.3 2.2 -26.2 0.15 0.05 0.31 1.72 0.2 0.87 18
9 6810-7020 A 28.1 0.1 -30.1 0.02 0.00 0.11 0.51 0.2 1.17 17
10 9100-9140 D 36.1 0.2 -28.4 0.15 0.13 0.49 0.96 0.5 1.06 18
11 8321-8520 D 24.3 1.7 -27.2 0.88 0.21 0.97 0.79 1.2 1.03 16
12 8169-8230 C 21.2 0.6 -26.9 1.15 0.96 0.16 0.81 0.2 0.98 17
Spill oil 12.7 3.7 -25.7 0.72 0.27 3.65 16.1 0.2

NOTE: Boldface type indicates a definite negative correlation. Italic type indicates a probable negative correlation.

5. Geothermal gradients, subsurface temperatures, and

maturities are all very low in the Po Basin. Thus, if thermally
generated gas is present in the reservoirs above 5000 m, it must
-50 80
have migrated vertically from more mature, older strata at
greater depths. Figure 10.29 indicates that most of the gases are
a.a..
~ f: 0"
0; •
predominantly biogenic, containing more than 99.8% methane,
and having B 13C values more negative than - 60 0/00. There is,

.
~ 60. however, a trend that is probably attributable to mixing ofther-
1.0 ~o •
-55
mal gas with the biogenic gas; it runs from the lower left toward
~i; •
.,. 40 the upper right in figure 10.29. Those gases with B 13C values
less negative than about - 50 0/00 are probably mainly thermo-
•
genic. Most of the thermogenic gases are from pre-Pliocene
I Spilamberto I
20
-60 rocks. The wettest, heaviest (purely thermogenic) gases are
those from the pre-Miocene.
V613CBacterial end member Mattavelli et al. (1983) have attempted to estimate the propor-
-63ppt tion of biogenic and thermogenic gases in reservoirs in the Po
1 2 3 4 5 Basin by plotting B 13C versus gas wetness (fig. 10.30). Whether
C2+ [pphJ
such a calibration curve could be used in other areas with some
confidence is not known.
FIGURE 10.30 Estimating relative proportions of biogenic and
thermal gas in the Spilamberto Field, Po Basin, Italy. Re-
printed by permission of the American Association of Petro-
leum Geologists from Mattavelli et al., 1983.
Chapter 11 Surface Prospecting

PHILOSOPHY OF SURFACE PROSPECTING

Because no reservoir seal is perfect, all hydrocarbon ac-
cumulations leak material to the surface (fig. 11.1). Al-
though large seepages may be visible to the naked eye,
small, slow microseepages can only be detected with sen-
sitive 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 hydrocar-
bons.
In an effort to improve exploration efficiency, a wide
variety of techniques for identifYing hydrocarbon micro-
seepages 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 suiface-
prospecting techniques.
One complicating factor in the interpretation of sur-
face-prospecting data is that seeps are not always located
directly above accumulations, as figure 11.1 would sug-
gest. 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 ac-
cumulation. Halos are not completely understood; they
have been attributed both to plugging of diffusional path-

181
182

FIGURE 11.1 Cartoon depicting vertical movement of hydro-

carbons from an imperfectly sealed reservoir. Hydrocarbons
or traces left by the hydrocarbons can be detected at or near
the surface.

ways immediately above the accumulation by mineral

diagenesis induced by hydrocarbon movement and to low
reservoir pressures.
All surface-prospecting techniques have claimed suc-
cess in some cases but have been totally inaccurate in
others. As a result of frequent overpromotion and misuse,
surface prospecting has earned a very bad name for itself
in some quarters. The basic concept of surface prospecting
remains sound, however. The main problems are devel-
oping technologies good enough to detect the anomalies.
36 30 In the future, surface prospecting will probably make
t 6 significant contributions to successful exploration.
R26e Anyone who wishes to use surface prospecting should
understand the theory, technology, and limitations of the
technique he or she is applying. There is at the present
FIGURE 11.2 Halo-shaped geochemical anomaly around the time no technique that has been shown to work well in all
Ten Section oil field, Kern County, California, detected by ~ C cases, and, given the wide variety of geological settings in
measurements. Reprinted with permission from the Oil and
Gas J Durnal from Duchscherer, 1982.
which exploration is carried out, it is unlikely that a
universally applicable technique will ever be developed.
Before selecting a surface-prospecting technique for
application in a particular area, investigate its track rec-
ord in that area, or at least under comparable geological
circumstances. If possible, listen to what customers say
 11. SURFACE PROSPECTING 183

3 -~
a:
i'°LAw....
u. 0
o 1 :2 3 ...V POPULATION 3

~WE ~

~
~
V,OPULATION 2
2 r-~-+--~~-----+--+----------+-----~7.'------r----~--------~
>

...
TRANSITION •••
'~

/~

PROBABILITY X < VALUE

FIGURE 11.3 Methodfor establishing the existence of two or

more distinct populations of data values by plotting raw
data (histogram, upper left) on probability paper. The three
populations are defined by distinct line segments connected
by a transition zone containing an inflection point. The in-
flection point approximately defines the limits of each popu-
lation.
about the various techniques being offered; they are likely
to be more objective than the contractors themselves.
Finally, remember that smface prospecting supple-
ments rather than replaces geology, geophysics, and geo-
chemistry. Surface-prospecting techniques are not magic
and can be most effectively employed if combined with
other good scientific work.
SURFACE-PROSPECTING TECHNIQUES
LIGHT HYDROCARBONS
Introduction. Light hydrocarbons have long been among
the most popular of surface-prospecting tools for several
reasons. First, as hydrocarbons they are closely related to
the accumulations being sought. Secondly, they are indi-
cators of present-day seep activity, and thus they imply the
presence of modem accumulations rather than ancient
ones that may have since disappeared. Finally, they are
easily collected and measured because they are both
mobile and volatile.
One important deficiency of light-hydrocarbon pros-
pecting is that methane, the dominant light hydrocarbon
in most samples, is normally useless for prospecting be-
cause so much biogenic methane of recent, nonpetroleum
origin emanates from sediments and soils. Any methane
derived from oil or thermal gas would be swamped out by
the biogenic component. In those relatively infrequent
cases where thermally generated methane predominates
in the seep, it could be identified only by carrying out
carbon-isotope determinations.
As a consequence of these difficulties with methane,
184
many light-hydrocarbon measurements emphasize eth-
ane and heavier alkanes. Concentrations of light hydro-
carbons 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 concentra-
tions 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 be-
tween the populations and mark the approximate limiting
values for each population.
Unlike most other techniques, light-hydrocarbon anal-
yses can be applied offShore as well as onshore. Light-
hydrocarbon prospecting is less expensive than most
other regional high-grading techniques.
Onshore. Light-hydrocarbon surveys are carried out most
conveniently and cheaply onshore, where access to soils is
easy. Most samplers penetrate the upper zone of possible
contamination by drilling, pounding, or augering a few
feet below the surface. There is no general agreement
about the distance of penetration necessary to avoid con-
tamination and problems with fluctuating water tables.
The optimal distance of penetration probably varies con-
siderably from area to area.
Richers et al. (1982) and Jones and Drozd (1983) per-
formed light-hydrocarbon analyses on soil-gas samples,
headspace gases, and adsorbed gases from soils. Both
groups found their largest anomalies along faults, sup-
porting the notion that light-hydrocarbon surveys provide
an excellent means of locating faults.
Of much more economic importance is whether light-
hydrocru:bon surveys can locate hydrocarbon accumula-
tions. According to Jones and Drozd (1983), only those
faults immediately above oil production showed high
concentrations of propane and butanes. Neither study
delved into the problem of using light-hydrocarbon sur-
veys to locate hydrocarbon accumulations not associated
with faults.
Qffshore. Light-hydrocarbon sampling offshore is more
complicated and expensive than onshore and has there-
fore attracted a greater variety of innovative technologies.
The added expense of offshore surveys is often compen-
sated by the larger exploration prizes being sought, how-
ever.
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 measure-
ments 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 con-
tinuously to the ship, where hydrocarbon gases dissolved
in the water are analyzed by gas chromatography. This
system is rather expensive, because massive data reduc-
tion is done by computer. Three-dimensional contour
maps of hydrocarbon concentrations are provided.
The system offered by Hydrochem Surveys Interna-
tional is similar. The main difference between their tech-

nique and InterOcean's is that Hydrochem analyzes those
samples high in methane for carbon-isotopic composition
in order to distinguish between biogenic and thermogenic
origins. Hydrochem claims that their surveys are much
less expensive than techniques that employ sediment
sampling. If marine seismic surveys are already planned,
the incremental cost of the light-hydrocarbon analysis
is modest.
HEAVY HYDROCARBONS
Until recently, analysis of heavy hydrocarbons was not
feasible for surface prospecting because the low vola-
tilities and mobilities of those molecules kept their con-
centrations below detection limits. In the last few years,
however, application of mass spectrometry has greatly
increased analytical sensitivity for heavy hydrocarbons.
In a technique patented by Petrex, vials are placed just
below the surface of the ground for a few days. The vials
contain a small wire made of a special metal alloy, one
end of which is coated with activated charcoal. Any hy-
drocarbons emanating from the earth during the collec-
tion period are adsorbed on the charcoal. The samples
are then retrieved and analyzed by inserting the wire
directly into the ionizing chamber of a mass spectrometer.
When an electrical current is passed through the wire, it
heats up almost instantaneously to the Curie point, a pre-
cise temperature characteristic of that particular alloy.
The adsorbed hydrocarbons are vaporized, ionized by the
mass spectrometer, and the ions recorded as the mass
spectrum of the mixture.
Petrex has found that both the total quantity of hydro-
carbons adsorbed and their molecular size are diagnostic
of whether hydrocarbons are accumulated in the underly-
ing strata. Furthermore, they claim to be able to distin-
guish oil from gas, as well as hydrocarbons that have
moved up a fault from those that have diffused through
unfaulted strata.
The fact that the Petrex technique measures hydrocar-
bons that have more than ten carbon atoms makes it very
attractive as an indicator of oil microseeps. Its stated abil-
ity to identifY accumulations unrelated to faults also dis-
tinguishes it from the light-hydrocarbon techniques.
Petrex claims to have had an excellent success rate in
exploration applications.
At the present time this technique can only be applied
11. SURFACE PROSPECTING 185
onshore. It is more expensive than light-hydrocarbon
analyses, with analytical costs alone running in excess of
$60 per sample. However, if an area of interest can be
clearly defined ahead of time, the Petrex method may
prove very useful in selecting drilling locations or in
choosing among several available structures (Klusman
and Voorhees 1983).
MAGNETICS
High-wave-number magnetic anomalies detected in low-
altitude aeromagnetic surveys are thought to be indicative
of the presence of shallow accumulations of magnetite
formed as a result of reactions with seeping hydrocar-
bons. An oxidation-reduction reaction between hydrocar-
bons 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 concentra-
tion of magnetite at shallow depths is responsible for the
observed magnetic anomaly.
Magnetic anomalies have been observed above the Ce-
ment 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 ex-
ploration is not yet fully developed, the relatively low ex-
pense of such surveys makes them attractive (Foote,
1984).
~C
The ~C method is a proprietary technique employed by
Geochemical Surveys, Inc. Neither the details of the ana-
lytical process nor the theory behind it have been fully
divulged, but it supposedly relies on detection of"abnor-
mal" carbonate species produced by migrating hydrocar-
bons. Soil samples are analyzed by pyrolysis, which
decomposes the carbonates and releases carbon dioxide
to a detector. Duchscherer (1982) claimed that 85% of
producing oil and gas fields show some sort of halo
anomaly.
The ~C method is moderately expensive. Duchscherer
(1981) stated that a survey encompassing 250,000 acres
(1000 km2 ) could be completed for U.S. $180,000, and he
186
made the point that surface prospecting is far cheaper
than reconnaissance seismic.
Geochemical SUIVeys, Inc. has had a long history of
exploration applications and claims a good rate of success
(e.g., Duchscherer, 1984a, b). Until recently, however,
secrecy about their method had hurt their credibility
among scientists. Further applications should help deter-
mine the effectiveness of the ac method compared to
other surface-prospecting techniques.
CARBONATE CEMENf
The carbonate produced from oxidation of migrating hy-
drocarbons can decrease porosity and increase density of
the rocks in which it precipitates. If the host rocks are
poorly consolidated, the density contrast between ce-
mented 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), hydro-
carbon-derived cement is easily distinguished from inor-
ganically 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)
IP measurements are predicated on the idea that shallow
electrical anomalies due to pyrite occur over leaking hy-
drocarbon reservoirs. An electrical current is passed into
the ground from a wire grounded at both ends, and the
potential that is set up is detected by a receiver located in
the middle of the array.
A number of simultaneous conditions must be met for
IP to work well. For example, pyrite formation requires
anoxic conditions where sulfate reduction and hydrocar-
bon oxidation occur. Apparently the proper combination
of circumstances is rather rare. Furthermore, false anom-
alies have been observed (Oehler and Sternberg, 1984).
Nevertheless, IP has definite exploration applications as
an inexpensive reconnaissance technique where condi-
tions are appropriate (Sternberg and Oehler, 1984).
SURFACE GAMMA-RAY MEASUREMENfS
Surface SUIVeys of gamma-ray intensity were carried out
in a sparsely drilled part of the Powder River Basin, and
the predictions of these sUIVeys were later evaluated by
drilling. Results seemed to indicate that the technique was
useful in distinguishing productive features from non-
productive ones (Curry, 1984).
Numerous questions remain about the best ways to
carry out gamma-ray sUIVeys. The various detectors have
different sensitivities to the principal gamma-ray emitters
(potassium, thorium, and uranium). Because the origins
of these three species are quite different, a better under-
standing of the movement of these elements in the subsur-
face would certainly help with future interpretation.
OTHER TECHNIQUES
Gallagher (1984) has promoted the use of iodine anoma-
lies 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 en-
able us to monitor present-day microseeps, there remain
many unresolved problems in applying the various tech-
niques 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

future supplant light-hydrocarbon surveys. For economic

reasons, offShore methods that permit detection of hydro-
carbons in the water column will probably replace analy-
sis of sediments.
Indirect methods that measure changes wrought by
migrating hydrocarbons in the past do not necessarily
indicate the presence of modern accumulations. Al-
though indirect methods have been used with some suc-
cess, we do not yet know whether such "fossil" indicators
are generally reliable as exploration tools.
All surface-prospecting techniques are highly empir-
ical, despite the grounding of most of them in sound
theory. The successful application of any surface tech-
nique is likely to be highly dependent upon local factors.
One important weakness of all surface-prospecting tech-
niques is that none is capable of specifYing whether a
leaking accumulation is deep or shallow or whether it
will be commercial. The magnitude of modern surface
anomalies is dependent upon rates of leakage, not on the
size of the accumulation. Any area with multiple pay
zones is likely to be difficult to evaluate by surface pros-
pecting, unless one is already committed to drilling to the
deepest possible reservoir.
With these cautions and limitations in mind, I strongly
recommend considering the use of surface prospecting
wherever it seems appropriate. Any data obtained there-
from should be used in conjunction with the best geology
and geophysics available. To ignore these traditional dis-
ciplines and rely mainly on surface techniques is not far
removed from using a divining rod.

SUGGESTED READINGS

Davidson, M.J., 1982, Toward a general theol}' of vertical mi-

gration: Oil and GasJournal,June 21, pp. 288-300.
Davidson, M.J., B. M. Gottlieb, and E. Price, eds., Unconven-
tional 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

PHILOSOPHY OF THE MODEL-BASED APPROACH

We have seen how to circumvent problems inherent in the
analysis-based geochemical approach by using models to
predict organic facies (chap. 2) and thermal maturity
(chap. 9). Even with such models, however, we still do
not have a scheme that is directly applicable in explora-
tion. For geochemistry to have maximum value for explo-
rationists, it must utilize a comprehensive model for the
entire hydrocarbon system under study. This model
should describe the locus and timing of hydrocarbon
generation, direction and efficiency of migration, prob-
able areas of entrapment, and potential for preservation
in a reservoir.
There are three fundamentally different ways to de-
scribe a hydrocarbon system. Qualitative models tell us
where hydrocarbon generation occurs, the pathways fol-
lowed by migrating hydrocarbons, and the areas where
accumulation and preservation are likely. The other two
types of models-deterministic and probabilistic-are
both quantitative. Deterministic models (Welte and YUk-
ler, 1981; Nakayama and Van Siclen, 1981; Ungerer et al.,
1984) seek to identifY and quantifY all variables in the
system and thus predict the behavior of the system by
establishing values or limits for each variable. They re-
quire large amounts of input data and therefore are
worthwhile only where extensive exploration has already
been carried out. If data are abundant, they may work
well and even have advantages, because properly for-
mulated deterministic models are well suited to describ-
ing the unique aspects of a basin.

189
190

tion as a mysterious process that, at our present state of

knowledge, cannot be described accurately by dissecting
1.0 it. It is therefore treated as a whole or as the result of two
">
! III
or three general factors, such as distance and difficulty.
Empirical data (the learning set) are used heavily in
C e .1
:z: 0 calibrating the model, so that some reasonable prediction
...
0
::I
e of overall migration efficiency can be obtained for any
0
.1 new case that bears a resemblance to a member of the
>-
...
CL 1/1

III learning set.

e
...
l-
e
c .4
Most users of mathematical models for hydrocarbon
III
C
III systems have elected to employ probabilistic models.
III
0
>C Bishop et al. (1983), Sluijk and Nederlof (1984), and
e .2 Baker et al. (1984) have discussed ways of applying such
IL

models in exploration. Retrospective analysis of drilling

results indicates that use of a probabilistic model could
o 100 200 '00 have significantly improved exploration efficiency (Mur-
RECOVERABLE OIL, MILLION BARRELS ris, 1984).

FIGURE 12.1 Example of data output using a probabilistic

model. Reprinted by permission of the Rocky Mountain Asso-
ciation of Geologists from Waples, 1984b.
Probabilistic models, in contrast, do not presume to
have identified all possible variables. They overcome
this limitation by fitting the model to a selected, well-
understood learning set before application to a new sys-
tem. Proponents of the probabilistic approach believe that
the effects of many unidentified or poorly understood vari-
ables can thus be taken into account indirectly.
Probabilistic models are so named because both input
and output data are presented as probability distributions
(fig. 12.1). This approach allows one to take the natural
heterogeneity of the system into account in the input data
and to select one's own confidence level in interpreting
the output data.
The fundamental differences between deterministic
and probabilistic models can be illustrated by looking at
migration. Deterministic models select a mechanism for
hydrocarbon migration and then attempt to quantity mi-
gration using mathematical equations describing fluid
flow. The equations are complex and give a precise de-
scription of the model, but there is no certainty that they
are actually relevant to migration.
The probabilistic approach, in contrast, treats migra-
QUALITATIVE MODELS OF HYDROCARBON SYSTEMS
METHODOLOGY
There are several logical steps that must be followed in
developing a qualitative geochemical model for the hy-
drocarbon systems of a basin:
1. Model the tectonic style and evolution of the basin
(e.g., Bois et al., 1982; Kingston et al., 1983a, b).
2. Model the distribution of source rocks in the basin
through time and space (e.g., North, 1979, 1980; see
also chap. 2 of this text).
3. Model maturity of source rocks through time and
space (see chap. 9).
4. Model deposition and diagenesis of carrier beds and
development of tectonically controlled permeability
zones (faults, fractures) through time and space.
5. Model effective migration pathways through time and
space on the basis of (a) distribution of mature source
rocks, (b) their juxtaposition with adequate carrier
beds or other migration pathways, and (c) structural
contours controlling direction and limiting extent of
migration (see chapter 6).
6. Model preservation of oil and gas based on thermal
considerations, biodegradation, and possible presence
of sulfate-rich reservoirs (see chaps. 5 and 9).
 12. INTEGRATED APPLICATIONS TO EXPLORATION 191

Steps 2 through 5 require an understanding of the tec-

tonic 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, well-
studied 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 prin-
ciples 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

East Texas Woodbine-Eagle Ford System. The East Texas Ba-

sin developed during the Permo-Triassic rifting of North
America from Africa and subsequent opening of the Gulf
of Mexico. It is dominated by extensional tectonics with
relatively minor restructuring by salt movement during
theJurassic and Early Cretaceous. The basin is bounded
on the east by the Sabine Uplift, a relative positive feature
that was most prominent in Cenomanian-Turonian
(Woodbine-Eagle Ford) time (mid-Cretaceous). The
western and northern limits of the basin are defined by
the Mexia-Talco Fault Zone, a tensional feature related
in complex and indirect ways to rifting. The approximate
southern boundary is the Angelina-Caldwell Flexure,
which coincides with the Edwards Reef Trend and is
thought to perhaps represent the ancient shelf-slope break
(fig. 12.2).
The most productive reservoir in the East Texas Basin
is the Woodbine sand: more than 7 billion barrels of
recoverable oil are trapped in Woodbine fields. The
largest of these, the East Texas Field, has itself produced
more than 5 billion barrels.
The East Texas Field is a classic stratigraphic trap,
with Woodbine sand pinching out erosionally on the west
flank of the Sabine Uplift (fig. 12.3). The Woodbine is
capped unconformably near the Sabine Uplift by im-
permeable Austin Chalk; elsewhere it is overlain con-
~
N
,~, :h_ 1 ...............
OlC20)o
SC A LE IN L£ S
FIGURE 12.2 Major structural ftatures of the East Texas Ba-
sin. Reprinted by permission of the SEPM from Siemers,
1981.
formably by Eagle Ford shale, which is generally
accepted as the principal source rock for the Woodbine
oil.
Maturity in the Eagle Ford is the primary concern from
a source-rock perspective, since the Eagle Ford generally
has very satisfactory source-rock character where it has
been studied. Results of maturity (TTl) modeling carried
out for 67 wells throughout the basin were found to be in
good agreement with available measured data. Because
of the tectonic and thermal stability of the basin since the
Early Cretaceous, there is an excellent correlation be-
tween present-day depth and maturity in the Eagle Ford.
The Eagle Ford is only marginally mature in most parts
of a modest trough that trends approximately north-
northeast along the axis ofthe basin (figs. 12.2 and 12.4).
192

.
Arkansas

:".t'.
'-..
~'~ . 'r Louisiana

I •, r

l': f .. " •••

.:
., .,
.
\...
\
.. .~\
'
-.
:/ ' , ' "" b':.:" •
• • ' 1-". .
~.
" , ~

St."ilk in mill'!'.
o 10 :!O :10 40

Most of the mature Eagle Ford shale occurs near or be-
yond the southern margin of the basin, where regional
dip has allowed deeper burial of the source rock. Long-
distance migration is thus required in order for Eagle
Ford oil to have charged Woodbine sands.
Woodbine sands were deposited in a variety of environ-
ments, 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 coastal-
barrier 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-
FIGURE 12.3 Woodbine oil and gas fields (dark areas) in the
East Texas Basin,
distance migration (fig. 12.5). In some areas Eagle Ford
sands may also provide long-distance migration conduits
or, more importantly, provide a means to move Eagle
Ford oil into the Woodbine pipeline.
Juxtaposition of a map of mature Eagle Ford source
rocks with a map of the areas where migration can occur
shows that there is plenty of opportunity for Eagle Ford oil
to enter the Woodbine plumbing system, particularly in
the vicinity of the Angelina-Caldwell Flexure (fig. 12.5).
Migration pathways can be traced perpendicular to struc-
tural contours in the Woodbine (not shoWn, but deduced

Arkansa
Loui iana
o Early oil generation
• utle oil generation
[!) Ga generation
FIGURE 12.4 Areas of mature Eagle Ford source rocks, based
on TTl calculations for 67 wells calibrated with measured
data.
from present-day structure on the base of the Austin
Chalk, which is an easy pick on logs). The relatively thin
Eagle Ford that separates the Woodbine from the Austin
does not introduce much error into this assumption, nor
does the use of present-day structure (although migration
was primarily a Tertiary phenomenon) because of the
tectonic stability of the basin.
Correspondence between predicted results from this
analysis and actual Woodbine accumulations is quite
good (fig. 12.6). Most of the Woodbine oil lies within the
high-graded areas through which the Eagle Ford-sourced
oil was expected to flow. The model accounts nicely for
the large East Texas Field , into which a large portion of
the hydrocarbons generated in the kitchen to the south
drained. Accumulatiohs on the west side of the basin are
much smaller because of more structural barriers in-
12. INTEGRATED APPLICATIONS TO EXPLORATION 193
- ...
~
mer beds - -- Mexia-Talco updip filUh zone
o Probable - Limits of source-rod. maludl)'
GP ibl
FIGURE 12.5 Migration pathways in the Woodbine for Eagle
Ford oil. Fair to excellent long-distance migration conduits
are likely within the shaded areas. Arrows show migration
directions perpendicular to dip in the Woodbine. Mature
Eagle Ford source rocks are outlined with a heavy line.
duced by both extensional faulting and halokinesis. The
Mexia-Talco Fault Zone usually forms an impenetrable
barrier to hydrocarbon migration, leading to accumula-
tions along the fault.
This analysis is very useful to an explorationist because
it suggests unproductive areas through which Woodbine
oils have migrated (fig. 12.7). The large, irregularly
shaped, "Best-oil" area in the middle is of particular
interest. Drilling in that area has been very sparse to date
because of an almost complete lack of structure in the
Woodbine. This absence of structural traps undoubtedly
was an important factor in permitting so much hydrocar-
bon to reach the East Texas Field. However, facies analy-
sis within the Woodbine suggests that stratigraphic traps
194

\\ -+- ,

s...d.. In nil,",
U IO ZONJ-W

C] Highcst

o Good

o Fair

FIGURE 12.6 Comparison of predicted areas for accumula-

tion of Woodbine oil with known Woodbine fieUls.

ought to be plentiful in that area. Because such large

volumes of oil have moved through the area, any strati-
graphic traps are likely to be full to the spill point.
Maturity calculations also predict that beyond the
Angelina-Caldwell Flexure preservation of oil in the
Woodbine is much less likely (fig. 12.7). This prediction
agrees with drilling- results beyond the Flexure, where
condensate is the principal product.
 12. INTEGRATED APPLICATIONS TO EXPLORATION 195

Arkansa
Loui iana

\\ • I

"w.lk HI 1I111t ....

II It) .!u tu -'41

Oil Gas

CI SCSI
m
0.. . Good 1:3
0 Fair

FIGURE 12.7 High-graded areas for wildcat exploration in

the Woodbine Fonnation.
196
\. ,
IEiRASU
FIGURE 12.8 Lack of maturity in mid-Cretaceous source
rocks at middle Maestrichtian time. Contour lines show
structure on] Sandstone; datum is top of Fox Hills Sand-
stone (Uppermost Cretaceous). Reprinted by permission of the
Rocky Mountain Association of Geologists from Tainter,
1984.
Denver Basin: J Sandstone. Tainter (1984) has analyzed
generation and migration patterns for oils reservoired in
the D and] Sands in the Denver Basin. The source beds
for these oils are a variety of mid-Cretaceous marine rocks
(Niobrara, Greenhorn, Mowry, etc.) of approximately
the same age as the reservoir rocks. TTl calculations
(checked with measured maturity data) showed that hy-
drocarbon generation in the deep part of the basin com-
menced at the beginning of the Eocene and continued
until cooling of the bqsin as a result of uplift in the late
---....
•
Aft. 01 .hluf. SOVfU ..... 110 ,
C I • SOO
FIGURE 12.9 Maturity in mid-Cretaceous source rocks from
middle Eocene to /ate Oligocene time. Contour lines show
structure on] Sandstone; datum is top of Dawson Arkose
(lower Eocene). Reprinted by permission of the ROCky Moun-
tain Association of Geologists from Tainter, 1984.
Pliocene. The evolution of the oil kitchen through time is
shown in figures 12.8-12.11.
Migration into D and] Sandstones requires that con-
tinuous sand bodies be in contact with mature source
rocks. Figure 12.12 shows the distribution and thickness
of the] Sandstone in the Denver Basin. The thickest sands
are assumed to have transported the majority of the oil.
Development of subtle structures within the] Sandstone
occurred by middle Campanian (Late Cretaceous) time
(fig. 12.13). Subsequent deepening of the basin toward the

FIGURE 12.10 Maturity in mid-Cretaceous source rocks at
end of Tertiary. Contour lines show structure on] Sandstone;
datum is top of Ogallala Formation (Pliocene). Reprinted by
permission of the Rocky Mountain Association of Geologists
from Tainter, 1984.
west (figs. 12.8-12.11) did not appreciably alter the dis-
tribution of trapping structures.
Accumulation of oil in the J Sandstone will occur
where oil transported from the kitchen encounters anti-
clinal structures (stratigraphic-trapping possibilities are
ignored in Tainter's study). Patterns of hydrocarbon mi-
gration through the J Sandstone can therefore be deter-
mined 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.
12. INTEGRATED APPLICATIONS TO EXPLORATION 197
I
IC
-
."
."
...
C
FIGURE 12.11 Maturity in mid-Cretaceous source rocks at
present day. Contour lines show structure on] Sandstone;
datum is sea level. Reprinted by permission of the Rocky
Mountain Association of Geologists from Tainter, 1984.
Predicted areas for occurrence of oil reservoirs in the J
Sandstone are compared with the fields that actually pro-
duce from the J Sandstone (fig. 12.15). The correspon-
dence is fairly good and undoubtedly could be improved
if stratigraphic trapping were taken into account. Use of
such a model could greatly reduce the areas under con-
sideration for future exploration.
198

'- ,0 ~t
':" \,5 : %J
:, ,,,
....
,... . ~
,
8

\"
",
:; • CIII.,.MtI

. 1500

I100
I
....
...,
-
....
"'"
• ~I\Ch'DM Tf'uCkMu > 100' C) P,"oil,uc;lur.' Htth'
C I • SO' C I • ~OO'

FIGURE 12.12 Sandstone isolith ofl Sandstone. Reprinted by FIGURE 12.13 Structure on] Sandstone at milklle Campanian
permission of the Rocky Mountain Association of Geologists time. Datum is top of Niobrara Formation (lower Campa-
from Tainter, 1984. nian). Reprinted by permission of the Rocky Mountain Asso-
ciation of Geologists from Tainter, 1984.

QUANTITATIVE (VOLUMETRIC) MODELS

BASIC EQUATIONS
One convenient way to approach the problem of calcu-
lating 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 gener-
ation utilizes three common pieces of geochemical data
(TOC, Rock-Eval pyrolysis yield, and maturity). As we
saw in chapter 8, all three parameters affect the quantity
of hydrocarbons that have already been generated. The
basic equation we can use to calculate hydrocarbon
volumes from these three pieces of data is given in equa-
tion (12.1):
Volume of HC == (k)(TOC)(HI)(f) (12.1)
TOC is expressed in weight percent; hydrogen index (HI)
is given in its normal units (that is, mg HC/g TOC), and
maturity is expressed as a fraction f between 0 (com-

FIGURE 12.14 Hydrocarbon-migration pathways in] Sand-
stone 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.
pletely immature) and 1 (fully mature). The value ofJis
equivalent to (Go - G)lGo • The value of the conversion
constant k is governed by the units desired for the hydro-
carbon volumes and by our assumptions about the densi-
ties of the source rock and hydrocarbons. If the volume
units desired are millions of barrels per cubic mile of
source rock, if the source rock is a shale with density 2.3
glee, and if the hydrocarbons correspond to an oil of 25°
API gravity (density = 0.9 g/cc), the value ofk is 0.7. If
the source rock is a limestone (density = 2.6 g/cc), the
value of k is about 0.7B.
Measured or calculated maturity values in TAl, R" or
12. INTEGRATED APPLICATIONS TO EXPLORATION 199
IEIRASU
A rU I Of bplof. hoft " I04'lly II)
Q) Aru l 01 [l.plor. UOft "'Oouly (It
""now" 'rochtCho..
, Ot!
Q Gil
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.
TTL units must be converted to the unitless scale in which
fractional conversion if) is expressed. Sluijk and Nederlof
(1984) have published a useful series of calibrations be-
tween Ro and J (fig. 12.16).
A sample calculation will make the procedure clear.
Suppose we have a proposed source shale whose mea-
sured Toe is 1.2%, whose hydrogen index was 120 when
the rock was immature, and whose present-day vitrinite-
reflectance value is 0.9%. From its hydrogen index, the
kerogen present in the shale appears to be Type III. Let us
assume further that Type III kerogen can generate about
20% oil and 80% gas (these proportions are mostly just a
200

rUCTION or POTENTIAL ULTI ..... TE YIELD _

085 o 2~ 010 Og~ 0'0 O.$() 090

062..--- "'-------'--'

0 .8

1.0

,2
vA l e

2.·111• • • •
THREE TYPES OF SOURCE ROCK :
MAINLY- HUMIC MAINlY-KEROG . KEROGENOUS
TO MIXED TO KEROG . 8ACT. ALGAL

fR"'CTION Of POTENT''' " ULTIMATE YIELD

.....
gg;;
.,
06 1.0
0.62 +'-.l...._--'-_--'

DB
,.0

'.2
VR/E

2 ••••••

ALL SOURCE ROCK TYPES

FIGURE 12.16 Curves showing the relationship between Ro

guess because precise proportions are not known). The
amount of organic carbon capable of generating oil is
thus 20% of the 1.2% TOe, or 0.24%. The remainder,
0.96%, is capable of generating only gas.
In order to calculate the volume of oil generated, we
use the relationship between f and R" for humic kerogen
from the upper left in figure 12.16. In this casef = 0.35.
Our calculated volume of oil in millions of barrels per
cubic mile is thus given by equation (12.2):
Volume of oil (0.7)(0.24)(120)(0.35)
7.056 million barrels oil per
cubic mile of source rock.
values and fractional conversion (f) of Types III (humic to
mixed), II (kerogenous to kerogenous bacterial), and I
(kerogenous algal) kerogens to oil (top, left to right) and gas
(bottom). Reprinted by permi.ssion of the American Associa-
tion of Petroleum Geologists from Sluijk and Nederlof, 1984.
The volume of gas generated is calculated in a similar
manner, except thatffor gas generation is determined to
be 0.07 from the lower graph in figure 12.16. Further-
more, if we want the volume of gas in billions of standard
(12.2) cubic feet per cubic mile of source rock, we must multiply
the constant k by about 6. Thus the calculated volume of
gas generated is

Volume of gas = (0.7)(6)(0.96)(120)(0.07) (12.3)
= 33.87 billion cubic feet gas per
cubic mile of source rock.
The question of generation is important, but expulsion
is critical in order for migration and accumulation to
occur. As we saw in chapter 6, Momper (1978) proposed
that a threshold value of 50 million barrels of hydrocar-
bons (oil or oil-equivalent) had to be generated in a
source rock before any expulsion could occur. We further
noted in chapter 6 that once this threshold is reached,
expulsion efficiency for oil is about 50%. Let us assume
that the expulsion efficiency for gas is higher-say 80%.
We can therefore calculate the volumes of hydrocarbons
expelled from any source rock.
For the rock cited earlier, the total volume of hydro-
carbon generated is 7 million barrels of oil and another
5.6 million barrels of oil-equivalent in gas (33.87 -;- 6).
Because the sum of these two quantities is not enough
to reach the expulsion threshold, no expulsion has yet
occurred.
In contrast, let us assume we have a rich shale contain-
ing 3.8% TOe that had a hydrogen index of 500 when
immature. The present Ro is 0.8% (f = 0.50). Let us
assume that this 1)rpe II kerogen generates 90% oil and
10% gas. What volumes of hydrocarbons have thus far
been generated and expelled?
The volume of oil generated is given by equation (12.4):
Volume of oil = (0.7)(3.8 x 0.9)(500)(0.5) (12.4)
= 598.5 million barrels oil per
cubic mile of source rock.
Because this quantity greatly exceeds the threshold, we
can assume that about 50%, or 300 million barrels of oil,
will have been expelled from each cubic mile of source
rock.
The volume of gas generated is given by equation
(12.5):
Volume of gas = (0.7)(6)(3.8 X 0.1)(500)(0.02) (12.5)
= 15.96 billion cubic feet gas per
cubic mile of source rock.
12. INTEGRATED APPLICATIONS TO EXPLORATION 201
If 80% of this gas is expelled, nearly 13 billion cubic feet
of gas will accompany each 300 million barrels out of the
source rock. This small amount of gas is probably not
enough to saturate the oil, and therefore it will move in
solution in the oil.
Once the volume of hydrocarbons expelled per unit of
source rock has been calculated, we must determine the
total volume of source rock available. This step requires
that we define our area of interest, usually as a drainage
area (see chapter 6). We then simply multiply the volume
of source rock in the drainage area times the volume of
hydrocarbons expelled per unit volume of source rock to
get the total volume of hydrocarbons expelled (eq.
[12.6]).
Total He volume = (He volume!cubic mile) (12.6)
X (cubic miles of source rock).
The problem of estimating source-rock volume is
mainly geological and can be addressed by a variety of
traditional geological and geophysical methods that help
us create source-rock isopachs. In carrying out such
volumetric calculations it may be necessary to divide the
source rock into packages within which the geochemical
properties (maturity, richness, kerogen type) remain
relatively constant. If several different packages are
present, the hydrocarbons contributed by each are simply
summed in the final step.
Once the total volume of hydrocarbons expelled from a
particular drainage area has been calculated, migration
and accumulation efficiencies must be factored in. 1)rpi-
cal values used by some workers (e.g., Barker and Dickey,
1984; Webster, 1984) are in the neighborhood of 5% to
10% for rich source rocks for the combined efficiencies of
expulsion and migration. We have already assumed that
expulsion efficiency for a rich rock is about 50%, and
have included that factor in our previous calculations.
Thus the general efficiency of secondary migration and
accumulation is probably in the neighborhood of 10%-
20%.
Sluijk and Nederlof (1984) showed that migration is a
process that has similar efficiencies in most systems, be-
cause they found a very poor correlation between their
202
ability to predict accumulation size and both migration
distance and difficulty. Thus migration efficiency proba-
bly varies within fairly narrow ranges (perhaps from 5%
to 30% for good source rocks) and cannot be predicted
well from first principles.
In order to calculate the volumes of hydrocarbons that
are successfully migrated and accumulated, we simply
multiply the volume expelled, obtained from equation
(12.6), by the proposed efficiency, given by equation
(12.7).
HC volume trapped = (HC volume expelled) (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 re-
quired in the two cases generally prevent both phenom-
ena 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 de-
struction by either biodegradation or cracking) to 1 (no
destruction). Total destruction would probably be best
defined as the absence of any producible oil. A preserva-
tion 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 trap-
ping 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 docu-
mented and could profit by additional research. However,
the values proposed in this chapter are probably accurate
enough to be useful. Factors influencing migration
efficiencies were discussed in chapter 6 but were not
quantified. Those discussions could become the basis for
quantification of migration and trapping efficiencies. Fi-
nally, inhomogeneous systems and systems where some
or all of the input parameters are poorly known are best
handled in a probabilistic model, which is discussed in
the next section.
PROBABILISTIC MODELS
The greatest advantage of probabilistic models is that they
take into account our uncertainties about the various fac-
tors involved in a volumetric calculation and allow us to
interpret the output data in a number of ways, depending
upon our needs. For example, suppose we have ten TOC
values for a proposed source rock in the area of interest,
but realize that these data are not a perfect summary of
the entire source-rock volume under consideration. If em-
ployed deterministically, the calculations discussed in the
preceding section would require that we calculate an av-
erage TOC from these data and apply that to the entire
source-rock volume.
The probabilistic method, on the other hand, permits
us not only to input all the raw data, but also to consider a
range of possible values for samples we have not ana-
lyzed. A probability distribution of TOC values is then
computed using a standard statistical approach. The
probability distribution is often shaped like the curve in
figure 12.1. The same process is repeated for each term in
the volumetric calculation (hydrogen index, maturity,
source-rock volume, expulsion and migration efficiencies,
and even the conversion constant if desired).
The volumetric calculation is then carried out using a
Monte Carlo approach. One value of each term is selected
randomly from the probability distribution, and the cal-
culation is performed. Then a second value for each term
is selected randOInly, and the calculation is repeated. This
process is repeated a large number of times (typically
1,000). The 1,000 calculated output values also form a
probability distribution like that shown in figure 12.1.
Anyone interpreting the output of a probabilistic model
is therefore not constrained to looking at a single "most
likely" output value. Instead, he or she can select what-
ever confidence level best suits his or her purposes. In the
 12. INTEGRATED APPLICATIONS TO EXPLORATION 203

example shown in figure 12.1, for example, there is only a Geologists Memoir 35, Tulsa, American Association of Petro-
6% probability that recoverable oil in the study area will leum Geologists, pp. 1-14.
exceed 200 million barrels, but a 60% probability that Demaison, G. and R.). Murris, 1984, eds., Petroleum
there will be at least 25 million barrels. Furthermore, Geochemistry and Basin Evaluation: American Association
of Petroleum Geologists Memoir 35, Tulsa, American Associ-
there is about a 99% probability of finding at least 3
ation of Petroleum Geologists, 426 pp.
million barrels. Such statistics are much more useful than Moshier, S. o. and D. W. Waples, 1985, Quantitative evaluation
a single average value in making exploration decisions. of Lower Cretaceous Mannville Group as source rock for Al-
Standard computer programs are available that can be berta's oil sands: Bulletin of the American Association of
adapted easily for Monte Carlo simulations. Probabilistic Petroleum Geologists, v. 69, pp. 161-172.
models are thus much more accessible for most explora- Sluijk, D. and M. H. Nederlof, 1984, Worldwide geological ex-
tion personnel than are the complicated, expensive, and perience as a systematic basis for prospect appraisal, in G.
generally proprietary deterministic programs. Demaison and R.). Murris, eds., Petroleum Geochemistry
and Basin Evaluation: American Association of Petroleum
Geologists Memoir 35, Tulsa, American Association of Petro-
SUMMARY
leum Geologists, pp. 15-26.
In order to achieve maximum effectiveness, the applica- Tainter, P. A., 1984, Stratigraphic and paleostructural controls
tion of geochemistry to exploration should involve full on hydrocarbon migration in Cretaceous D and) Sandstones
integration of geological and geochemical data. An excel- of the Denver Basin, in). Woodward, F. F. Meissner, and). L.
lent way to accomplish this objective is to develop inte- Clayton, eds., Hydrocarbon Source Rocks of the Greater
grated models that describe the complete hydrocarbon ROCky Mountain Region: Denver, Rocky Mountain Associa-
system in the area of interest. tion of Geologists, pp. 339-354.
Some such models are primarily qualitative and de-
scriptive, and can be applied using standard geological
techniques of mapping and construction of cross sections.
Other models are quantitative and mathematical. Prob-
abilistic 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 fron-
tier 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. De-
maison and R.). Murris,' eds., Petroleum Geochemistry and
Basin Evaluation: American Association of Petroleum
Glossary

a: alpha, a designation meaning that the indicated group in a

polycyclic compound is attached below the plane of the ring.
if. (3.
activation energy: the energy barrier over which molecules
must pass before a chemical reaction can occur. The higher
the barrier, the more energy the molecules must have. Raising
the temperature increases molecular energy and thus facili-
tates chemical reactions. See also pseudo-activation ener-
gy.
acyclic: having no rings.
aerobe: a bacterium that utilizes molecular oxygen for its meta-
bolic processes.
aerobic: 1. a process occurring in the presence of O2 , 2. bacte-
ria that are metabolically active in the presence of O2 ,
alginite: a kerogen maceral formed from algal material.
alicyclic: referring to saturated cyclic hydrocarbons.
aliphatic: referring to saturated hydrocarbons.
alkane: a saturated hydrocarbon. All carbon-carbon bonds
in alkanes are single bonds.
a1kene: an unsaturated hydrocarbon. At least one carbon-
carbon double bond is present.
alkyl: the adjective form of alkane, made by dropping -ane and
adding -yl. The same substitution can be made to convert the
names for specific alkanes (such as propane) to names for
attached groups (propyl).
amorphous organic matter: kerogen particles exhibiting no
distinctive morphology. Some amorphous organic material is
apparently of algal origin; other examples represent highly
degraded material of uncertain or perhaps eclectic origin.
amu: See atomic mass unit.
anaerobe: a microorganism that functions under anaerobic
conditions.
anaerobic: 1. a process that occurs in the absence of O2, 2. a

205
206
process that occurs where only very small amounts of O2 (less
than 0.1 mLlL water) are present. 3. bacteria that are active
under conditions where O2 is absent or very low.
anoxic: 1. conditions where O2 is absent. 2. conditions where
the concentration of O2 is very low (less than 0.1 mLlL water).
aromatic: an organic molecule having a cyclic system consist-
ing of alternating single and double bonds. Aromatic
molecules are unusually stable.
aromatization: the process of converting an alicyclic system
into an aromatic one. Aromatization is an oxidative process
that occurs during catagenesis and metagenesis.
AlThenius equation: an equation that relates the effects of
time and temperature to the rates of chemical reactions.
asphaltene: large organic molecules that are highly aromatic
and often relatively high in heteroatoms. They are found in
crude oils and bitumens and are apparently formed during
diagenesis and catagenesis, as well as in oil reservoirs as by-
products of cracking. Because of their large molecular sizes,
asphaltenes exhibit some of the behavior of kerogens and are
only sparingly soluble in petroleum.
atomic mass unit (amu): a mass approximately equal to that
of one neutron, used in describing the masses of atoms,
molecules, or ions.
p: beta, a designation meaning that the indicated group in a
polycyclic compound is attached above the plane of the ring.
cf. ()t.
bactericide: a chemical that kills bacteria.
biodegradation: destruction or alteration of crude oil or gas by
bacteria that consumes or transforms certain chemical com-
pounds as sources of energy.
biogenic: formed biologically, by an organism or within an
organism.
biogenic gas: dry gas (virtually pure methane) formed by
anaerobic microorganisms called methanogens.
biological markers: See biomarkers.
biomarkers: chemical compounds derived from specific
biological precursors. The transformation of precursor to
biomarker can often be traced directly, permitting the utiliza-
tion of biomarkers as environmental and maturity indica-
tors. Important biomarkers include n-alkanes, isoprenoids,
steranes, triterpanes, and porphyrins.
biopoiyIners: polymers created by enzymes. They have very
regular, predictable structures. cf. geopolymers.
bis: prefix meaning two.
bitumen: in a sedimentary rock, that portion of the organic
matter that is soluble in ordinary organic solvents, such as
benzene or chloroform. In practice, the lighter components of
the original extract ru:e lost during solvent evaporation. See
also C 15 +.
boghead coal: a coal formed mainly from algal material. It is
usually quite similar to oil-shale kerogen in chemical com-
position.
branched-cyclic fraction: saturated hydrocarbons from a
bitumen or crude oil from which the unbranched hydrocar-
bons (n-alkanes) have been removed.
burial-history curve: An age-depth plot that traces the burial
and tectonic history of a rock from the time of deposition to
the present day, using the sea bottom as the datum. cf.
geohistory diagram.
CAl: See Conodont Alteration Index.
C15 +: essentially the same as bitumen, so named because it con-
tains most of the compounds having 15 to 35 carbon atoms
that were present in the original sample. Compounds having
fewer than 15 carbon atoms are lost partially or completely
during evaporation of the extraction solvent. See also bitu-
men.
capillary cohmin: a very long, narrow-diameter tube often used
in gas chromatography. Because of the column's narrow diame-
ter, the stationary phase is coated directly on the walls of the
column. cf. packed colunm. See also gas chromatography.
capillary-entry pressure: the pressure that opposes the defor-
mation of a hydrocarbon globule and thus its movement into
a constricting pore throat. It retards migration and thus can
influence migration pathways and velocities. Capillary-entry
pressure is the force that ultimately leads to accumulation of
hydrocarbons.
carbon cycle: the cycle through which carbon moves from its
inorganic reservoirs in the atmosphere, in aqueous solution,
and in carbonate minerals to the biosphere via photosyn-
thesis, and finally back to the inorganic reservoirs via oxida-
tive decomposition.
Carbon Preference Index (CPI): the ratio ofn-alkanes having
odd numbers of carbon atoms to those having even numbers
of carbon atoms. CPI is calculated over a specified range of
carbon numbers, typically from 23 to 33. The CPI value de-
pends upon both the type and maturity of organic material.
carbonaceous: containing organic carbon or graphite.
carbonaceous residue: material that has a relatively high or-
ganic-carbon content compared to its content of hydrogen
and heteroatoms. Such residues are often the oxidized prod-
ucts of thermal-disproportionation reactions.
carboxyl: a functional group consisting of -COOH. The hydro-
gen in carboxyl groups is acidic.
catagenesis: thermal decomposition of large kerogen or as-
phaltene molecules into smaller molecules that then become
part of the bitumen fraction in the source rock. Catagenesis is
the stage of kerogen decomposition where oil generation oc-
curs. cf. diagenesis, metagenesis.

catalysis: the speeding-up of a chemical reaction by offering an
alternative pathway having a lower activation energy.
catalyst: a material that causes catalysis. Clay minerals are
probably the most important catalysts for hydrocarbon trans-
formations in the subsurface.
chlorin: a precursor molecule for a porphyrin. The difference is
that porphyrins have an aromatic structure, whereas chlorins
have one double bond less than a completely conjugated aro-
matic structure. Chlorophyll is a chlorin.
chromatograph: an instrument for performing chromatog-
raphy. See also gas chromatograph.
chromatography: separation of individual chemical com-
pounds or groups of compounds according to the velocities
with which they move through a stationary phase. The mix-
ture to be separated is introduced onto the stationary phase,
which has been saturated with a mobile (liquid or gas)
phase. The mobile phase is then passed through the station-
ary phase, and, depending upon the strength of the interac-
tions of the compounds in the mixture with both the
stationary and mobile phases, the mixture will separate into
individual components or groups of components. These sepa-
rated components can be collected, analyzed, or both at the
end of the chromatograph path. Common forms of chroma-
tography include gas chromatography (gc or glc), paper
chromatography, thin-layer chromatography (tic), column
chromatography, and high-pressure liquid chromatography
(hplc).
cis: a configuration in which two groups attached to a molecule
are on the same side of the molecule. cf. trans.
clathrate: a chemical compound in which a loose molecule
is trapped inside a crystalline network of surrounding
molecules, usually of a different compound. See also gas
hydrates.
coalification: 1. formation of coal from peat and lignite (brown
coal). 2. the subsequent increase in coal rank.
column chromatography: in petroleum geochemistry, chro-
matography carried out in a vertical column filled with a
stationary phase, such as silica gel or alumina, and a mobile
liquid phase, which initially is an aliphatic hydrocarbon like
n-hexane. The mixture to be separated is introduced at the
top of the column, and the liquid phase is allowed to flow
through the column by gravity into a collecting vessel at the
bottom. The liquid phase is continually replenished at the top
of the column. The saturated hydrocarbons quickly pass
through (elute from) the column. After a predetermined
amount of n-hexane has flowed through, a more-polar liquid
phase, usually benzene, replaces the n-hexane. The benzene
rapidly elutes the aromatic hydrocarbons, which are collected
in a second vessel. Successively more-polar solvents (ben-
GLOSSARY 207
zene-methanol or chloroform) can elute many NSO com-
pounds. 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 rela-
tively homogeneous packages.
condensate: 1. material that exists in the gas phase under re-
servoir pressure-temperature conditions but which con-
denses 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 in-
clude 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 vari-
ous sizes. In this usage it is similar to catagenesis.
cyclics: compounds having one or more rings in their struc-
tures. 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 reac-
tions.
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 stabil-
ity of a molecule compared to a nondelocalized analog. De-
localization also increases the stability of an ion formed from
a molecule containing delocalized electrons or of excited-
208
energy states of such a molecule or ion by spreading the
excess charge or energy (which represents a stress on the
system) over a greater number of atoms.
diagenesis: low-temperature transformations of organic matter
in sedimentary environments. Much diagenesis is biological,
mediated by macro- or microorganisms. Ordinary chemical
reactions may also contribute, especially in formation of
kerogen and asphaltene molecules. Diagenesis precedes oil
generation, but includes the formation of biogenic gas. cf.
catagenesis, metagenesis.
diffu.sion: the slow movement of material from an area of high
concentration or pressure to areas of low concentration or
pressure. It may be an ancillary mechanism for expulsion of
hydrocarbons from a source rock. Diffusion plays a role in
hydrocarbon movement in the subsurface, but as a dispersive
force cannot account for accumulation. It will in fact help
destroy accumulations because much leakage is diffusional.
disproportionation: conversion of a single starting material
into two products. One of the products will be oxidized rela-
tive to the starting material; the other will be reduced. The
process thus represents an internal oxidation-reduction (re-
dox) system. It is important in kerogen catagenesis and crack-
ing. The light hydrocarbon products are reduced and rich in
hydrogen, whereas the residue (asphaltics, dead carbon, etc.)
is oxidized and hydrogen poor.
diterpanes: hydrocarbons formed from two terpane (four iso-
prene) units. Many have three 6-member rings. They often
are derived from resinite.
double bond: a bond between two atoms in which four elec-
trons are shared instead of the normal two. The most com-
mon double bonds encountered in petroleum geochemistry
are carbon-carbon and carbon-oxygen. Double bonds are
stronger and of shorter length than single bonds.
dry gas: gas containing more than about 99% methane.
dysaerobic: a process occurring in a dysoxic environment.
dysoxic: an environment depleted in oxygen but not quite
anoxic.
effective source rock: See source rock.
electron-spin resonance: a technique for estimating maturity
of kerogen by measuring the number of unpaired electrons
(free radicals) in the kerogen. At higher maturity levels the
increased aromaticity stabilizes unpaired electrons.
elemental analysis: quantitative analysis of the various ele-
ments present in a sample. The elements most commonly
analyzed for in petroleum geochemistry are carbon and hy-
drogen; oxygen, sulfur, and nitrogen are next.
entry pressure: See capillary-entry pressure.
EOM: bitumen.
epimer: isomers that differ only in the configuration at one
carbon atom.
epimerization: the conversion of one epimer into the other.
equilibrium isotope effect: the effect derived from the fact that
the heavier isotopes of an element prefer to exist in more
oxidized compounds, the lighter isotopes in the more reduced
compounds. Thus, for any reversible reaction that has come
to equilibrium, the isotopic distribution among the compo-
nents is dependent on the relative stabilities of the compounds
rather than their rate of formation. In organic geochemistry
the equilibrium isotope effect is important primarily in the
carbon dioxide-carbonate equilibrium. cf. kinetic isotope
effect.
esr: See electron-spin resonance.
exinite: a kerogen maceral formed from pollen grains and
spores. The name comes from exine, the outer coating of such
a grain.
expulsion: movement of bitumen, petroleum, or gas through
the source rock and out into a migration conduit; also called
primary migration.
extraction: removal of bitumen from a rock matrix. Extraction
can be accomplished by solvent or by heat.
flO: See flame-ionization detector.
fingerprinting: comparison of detailed characteristics (usually
specific chemical compounds) of two or more samples for
correlation purposes. Parameters commonly used in fin-
gerprinting include isoprenoid and n-alkane distributions by
gas chromatography, gc/ms ofsterane and triterpane biomar-
kers, and isotope ratios.
fixed carbon: a parameter for measuring coal rank (maturity).
Fixed-carbon content is similar to percent carbon in kerogen.
Higher fixed-carbon values correspond to higher maturities.
flame-ionization detector (FID): a detector used in gas
chromatographs in which molecules emerging from the col-
umn are burned in a hydrogen flame, and the ions produced
are counted as a measure of the flux of material off the col-
umn.
fluorescence: radiation given off by a molecule when the
molecule descends from an electronically excited state to a
lower-energy state. If the wavelength of the emitted radiation
is in the visible region, the fluorescence will be apparent to
the eye. If not, it may be detectable by infrared or ultraviolet
sensors. The excited state was reached by absorbing radia-
tion from light shined on the molecule. Aromatic molecules
fluoresce well because of their capability to delocalize (sta-
bilize) the excess energy.
Fluorescence is a useful measure of organic-matter type
and maturity and of the presence of nonindigenous hydrocar-

bons. Longer wavelengths of fluorescent emissions indicate
higher maturities because of greater delocalization of energy
(and therefore greater stability). Fluorescence intensity de-
creases with maturity. Degraded amorphous material does
not fluoresce, whereas algal amorphous material fluoresces
strongly.
fragment ion: an ion formed within a mass spectrometer by
decomposition of the molecular ion.
&agmentogram: a trace obtained from a gc/ms instrument in
which all compounds that yield a fragment ion of a specified
mlz ratio are recorded, and all compounds that do not give a
fragment with that particular mlz value are ignored. The
detector response is directly proportional to the number of
fragment ions with the correct mlz ratio. The number offrag-
ment ions, in turn, depends upon the concentration of the
precursor molecule and the frequency with which the precur-
sor breaks down to yield that particular fragment ion.
free radical: An unpaired electron in a molecule.
fulvic acids: humic substances of relatively low molecular
weight that are soluble in both aqueous acid and base. cf.
hurnic acids, humin, kerogen.
functional group: any group of atoms containing a func-
tionality.
functionality: any portion of an organic molecule that is not a
carbon-carbon or carbon-hydrogen single bond. Examples
include double bonds and any heteroatom.
'Y.factor: temperature factor used in calculating TTl values
by Lopatin's method.
gas chromatogram: the output data in analog form from a gas
chromatograph.
gas chromatograph: an instrument for performing separation
of hydrocarbon mixtures. The mixture is introduced via sy-
ringe into the heated injection port, where it is vaporized
immediately. An inert gas, usually nitrogen or helium, flows
through the injection port and sweeps the vapor onto and
through the column, which is a narrow-diameter metal or
glass tube containing the stationary phase. The components of
the mixture partition between the stationary phase and the
mobile gas phase, depending on their volatility, affinity for the
stationary phase, and column temperature. More volatile,
less-polar components pass through most rapidly. The sepa-
rated components are detected, usually by a flame-ionization
(FID) or thermal-conductivity detector (TCD), and are re-
corded on a gas chromatogram, which is a record of detector
response as a function of time.
All components to be analyzed must be volatilized at the
injection-port temperature, or they will remain as a residue in
the injection port and eventually contaminate it. Gas chro-
GLOSSARY 209
matography therefore is usually carried out on hydrocarbon
fractions previously separated by column chromatography
from bitumen or petroleum.
In order to achieve a good separation of compounds having
both low and high boiling points, programmed-temperature
chromatography (PTC) is usually employed. The column
temperature starts out low, at 50° C or so, and is raised at a
predetermined rate by a temperature program in the
chromatograph's oven. If a low temperature were used
throughout, the heavier components would never emerge
from the column. If only a high temperature were used, the
light compounds would pass through the column so rapidly
that no separation would be achieved. If gases are to be ana-
lyzed, the column temperature will be low.
gas chromatograph-mass spectrometer (gc!ms): a se-
quential combination of these two instruments. The gas
chromatograph separates components, which then pass indi-
vidually into the mass spectrometer. Coupling the two in-
struments permits separation by gc and identification of
compounds by ms without human intervention, and thus
greatly increases sensitivity and accuracy.
gas deadline: See hydrocarbon deadline.
gas hydrates: solid crystals in which gas molecules are trapped
inside a cagelike network of ice molecules called a clathrate.
Molecules containing up to four carbon atoms (butanes) are
known to form gas hydrates, but methane hydrates are by far
the most common in nature. Gas hydrates are stable under
high-pressure, low-temperature conditions existing in many
areas below the sea floor or below permafrost. Extremely
large quantities of methane are thought to be trapped in hy-
drates.
gc: See gas chromatograph.
gc!ms: See gas chromatograph-mass spectrometer.
geohistOIY diagram: an age-depth plot tracing the burial and
tectonic histories of a rock from the time of deposition to the
present day. It differs from a burial-history curve in that the
datum is sea level rather than the sea floor, thus permitting
water depth to be shown at all times.
geopolymer: a polymer formed in the geosphere as the result of
chemical combination of small molecules. Their structure is
random, lacking almost completely the strict ordering of
biopolymers. Because of their irregular structures, they are
not susceptible to microbial attack. Geopolymers include
fulvic acids, humic acids, asphaltenes, and kerogens.
graphitization: the process leading to graphite, which is the
ultimate polycyclic aromatic material. Graphitization is what
happens to kerogen during metagenesis when aromatization
is very advanced.
210
halocline: See pycnocline.
HC: abbreviation for hydrocarbon or hydrocarbons.
heavy oil: oil or tar which has a low API gravity (less than
about 15° or 20°, depending on various factors, particularly
economic ones). Hea"}' oil can be fonned in two distinct
ways: by biodegradation (aided sometimes by water washing
or evaporation) of normal crude oils, and as oils generated
early from some sulfur-rich kerogens. if. tar.
herbaceous: organic material of land-plant origin, especially
that which is rich in lipid components. Herbaceous organic
matter is nonnally considered to have good oil-source poten-
tial.
heteroatoms: any atoms other than carbon and hydrogen
found in kerogen, petroleum, bitumen, or natural gas. The
most common heteroatoms are nitrogen, sulfur, and oxygen.
heterocompounds: chemical compounds containing one or
more heteroatoms. Heterocompounds are often called NSO
compounds because of their three dominant heteroatoms.
high-perfonnance liquid chromatography: a type of col-
umn chromatography perfonned under high pressure in or-
der to achieve a more efficient separation of compounds
within a particular class. It is most commonly used with por-
phyrins and sometimes with hydrocarbon biomarkers. It is
abbreviated HPLC.
homologs: compounds that are members of the same class but
which differ in the number of carbon atoms they contain. For
example, n-pentane and n-hexane are homologs, as are pris-
tane and phytane.
hopanes: pentacyclic triterpanes whose precursors occur in
some terrestrial plants and in many microorganisms. They
are useful indicators of depositional environment and thermal
maturity.
HPLC: See high-perfonnance liquid chromatography.
humic acids: humic substances of medium molecular weight
that are soluble in aqueous base but not acid. if. fulvic acids,
humin, kerogen.
humic substances: organic matter with a relatively low HlC
ratio, composed largely of woody and cellulosic material of
terrestrial origin. Humic substances generate a little oil and
some gas, but do not have high-generative capacities for hy-
drocarbons.
humin: humic material of high molecular weight that is insolu-
ble in both aqueous acid and base. if. fulvic acids, humic
acids, kerogen.
hydrates: See gas hydrates.
hydrocarbon deadline: maximum depth or temperature at
which oil or gas is present in economic quantities in a partic-
ular area.
hydrocarbons: 1. Chern: compounds containing only carbon
and hydrogen. 2. Geoi: oil and natural gas.
hydrogen index: an indication of the remaining hydrocarbon-
generative capacity of a kerogen, as measured by Rock-Eval
pyrolysis. Hydrogen index is expressed in mg HClg TOC. if.
oxygen index.
hydrogenation: the addition of hydrogen to a chemical com-
pound, usually by reaction with the electrons in a double
bond. Example: ethene (C2l4) + H2 ~ ethane (C2H6 ).
hydrophilic: literally, ''water-loving.'' Hydrophilic compounds
or functional groups are polar and miscible with water.
hydrophobic: literally, ''water-fearing.'' Hydrophobic com-
pounds are nonpolar and thus immiscible with water.
hydroxyl: a functional group consisting of - OH.
hypersaline: any water with a dissolved-salt content higher
than that of nonnal sea water.
immature: having insufficient thennal maturity to have gen-
erated significant amounts of hydrocarbons.
inertinite: a kerogen maceral consisting of highly oxidized,
often reworked organic matter of various possible origins. It is
chemically inert and has negligible remaining hydrocarbon-
source potential.
m: infrared.
isomerization: conversion of one isomer into another.
isomer: molecules having the same empirical fonnula but dif-
fering in the way the atoms are bonded to each other.
isoprene: a five-carbon alkene that is the basic unit from which
the various isoprenoids, both cyclic and acyclic, are fonned.
isoprenoids: hydrocarbons composed of isoprene units joined
together in a regular way. The head-to-tail pattern is most
common.
isotope profile: a plot of isotope values measured for several
fractions of a bitumen or an oil, or for members of a homolo-
gous series (n-alkanes, for example). The measured values
are generally presented in a graphical (profile) fonnat that
shows the trend among the fractions measured. Profiles are
useful in correlations.
isotopes: atoms of a single chemical element that differ in the
number of neutrons in their nuclei. Important isotopes in
petroleum geochemistry include hydrogen and deuterium (H
and D, or lH and 2H); 12C and 13C; and 32S and 34S.
kerogen: that portion of the organic matter present in a
sedimentary rock that is insoluble in common organic sol-
vents. Kerogen is fonned by polymerization of organic
molecules derived from dead organisms. Oil and gas fonn
from kerogen during catagenesis and metagenesis.
kinetic isotope effect: the effect derived from the fact that the
lighter isotopes of an element react more rapidly than the

heavier ones. Thus any irreversible reaction in which 100% of
the reactant has not yet been consumed will show an enrich-
ment of the light isotope in the products. if. equilibrium
isotope effect.
kinetics: the study of the rates at which chemical reactions
proceed, and the dependence of these rates on various factors,
such as time, temperature, pressure, and concentrations of
the reactants.
Leco carbon analyzer: an instrument in common use for
measuring TOC values by combustion of the organic carbon
and- subsequent measurement of the carbon dioxide pro-
duced.
lignin: highly aromatic organic polymer that forms the struc-
tural material of land plants. It has a very low potential to
source oil and only a slight potential for gas.
lipids: fatty, waxy, and oily materials derived from organisms.
These compounds are similar to, identical with, or the pre-
cursors for many petroleum hydrocarbons.
liptinite: a kerogen maceral made up of lipid components, in-
cluding exines, resins, cuticle, and marine-algal material. As
used by many workers the term liptinite is not as specific as
other maceral names.
LOM: Level of Organic Metamorphism; source-rock maturity
calculated by a method developed by the Shell Oil Company.
To calculate LOM one need only know a rock's maximum
paleotemperature and the length of time spent by the rock
near that temperature. if. Lopatin's method.
Lopatin's method: a method developed by N.V. Lopatin
(1971) for predicting thermal maturity of rocks from a de-
tailed knowledge of their burial and thermal histories. if.
LOM.
low-gray: term applied to the vitrinite population having the
lowest reflectance value. Except where caving has occurred,
the low-gray population should represent the indigenous,
first-cycle material.
M +: the molecular ion formed in a mass spectrometer. See
molecular ion.
m/z: ratio of mass to charge for an ion in a mass spectrometer.
The charge is virtually always + 1, so the mJz value is actually
the mass of the ion in amu.
macerals: the organic "minerals" that make up kerogen in the
same way that true minerals make up rocks. The various
types of kerogen macerals are formed from different types of
organic matter that have undergone different degrees of dia-
genetic transformation. Common macerals include alginite,
exinite, liptinite, vitrinite, and inertinite. Most kerogens con-
tain a mixture of maceral types.
mass spectrometer: an instrument used for identifYing chemi-
GLOSSARY 211
cal compounds. The compound is vaporized in the inlet sys-
tem 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 struc-
tures 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 spec-
trometer can also be used to look for ions having particular
characteristics. For example, most steranes easily form frag-
ment ions having mJz 217. Thus, by scanning the entire gas-
chromatographic 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 hy-
drocarbon-generation window.
maturity: the degree to which hydrocarbon generation has pro-
ceeded in a kerogen.
metagenesis: the late stages of thermal maturity when gas gen-
eration and cracking predominate.
methane hydrates: See gas hydrates.
Methylphenanthrene Index: ratio of several methylphenan-
threnes, 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.
micell: an aggregation of a few molecules in which the polar
portions of the molecules align themselves close together. The
nonpolar parts of the molecules can thus also lie near each
other. In a polar medium the polar parts of the micell are
212
pointed outward, interacting favorably with the medium,
while the nonpolar parts are together in the middle, protected
from the medium. In a nonpolar medium the roles would be
reversed. Oil could form micells, since most rocks are wetted
with polar water molecules, and oils do contain some polar
components in addition to nonpolar hydrocarbons. MicelI
formation would increase the compatibility of water and oil.
microbes: microscopic organisms such as bacteria and
methanogens. They play vel)' important roles in diagenesis.
microfractures: tiny fractures that open up temporarily as a
result of overpressuring in source rocks, at least partially in
response to hydrocarbon generation. Microfractures may be
important pathways for expulsion. Because they apparently
heal rapidly and without leaving a trace in most cases, mi-
crofractures are not well understood.
migration: movement of bitumen, oil, and gas in the subsur-
face. Migration includes expulsion (primal)' migration), sec-
ondary migration, accumulation, and leakage.
molecular ion: the ion formed in a mass spectrometer by the
initial loss of a single electron from a molecule. Its mass is
essentially the same as of the parent molecule. The molecular
ion can subsequently decompose to give fragment ions.
molecular sieves: zeolites used in the laboratol)' separation of
n-alkanes from branched and cyclic saturated hydrocarbons.
See also urea adduction.
moretanes: pentacyclic triterpanes that are not vel)' stable ther-
mally. Their presence is a good indicator of thermal immatu-
rity, although some oils sourced from rocks rich in high-sulfur
kerogens may still contain moretanes.
MPI: See Methylphenanthrene Index.
ms: See mass spectrometer.
n-alkanes: See normal alkanes.
naphthenes: saturated cyclic hydrocarbons.
naphthenoaromatics: compounds containing both saturated
and aromatic rings.
nmr: See nuclear magnetic resonance.
nor: prefix meaning without, indicating that a methyl group has
been lost from the base compound at the position indicated by
the preceding number.
normal alkanes: straight-chain alkanes (those having no rings
or branching). Also called n-alkanes.
NSO compounds: See heterocompounds.
nuclear magnetic resonance: a type of spectroscopic analysis
used in organic geochemistry to distinguish aliphatic carbon
atoms from aromatic ones. Application has been rather rare
but may increase in the future in kerogen studies.
oil deadline: See hydrocarbon deadline.
oil window: See oil-generation window and oil-pres-
ervation window.
oil-generation window: the range of depths, temperatures,
maturities, or, less commonly, times during which oil genera-
tion was or is occurring in a particular area.
oil-preservation window: the range of depths, temperatures,
or maturities at which oil is thermally stable in a particular
area.
Oil Show Analyzer: an instrument that performs both TOC
measurement and Rock-Eval pyrolysis in a single opera-
tion.
olefins: alkenes.
OM: abbreviation for organic matter.
OML: See oxygen-minimum layer.
organic: 1. a chemical compound containing one or more car-
bon atoms. However, carbonates and metal carbides are not
considered organic. 2. originating in or derived from an or-
ganism.
overmature: hydrocarbon generation has already occurred.
The term usually refers to oil generation.
oxidation: loss of electrons by an atom, ion, or molecule dur-
ing a chemical reaction.
oxidizing agent: a molecule, atom, or ion that promotes oxida-
tion in some other material. The oxidizing agent is itself re-
duced during the reaction. cf. reducing agent.
oxygen index: the amount of CO2 produced from kerogen dur-
ing Rock-Eval pyrolysis. Oxygen index is measured as mg
COz/g TOC and is supposed to be related to the oxygen con-
tent of the kerogen. cf. hydrogen index.
oxygen-minimum layer: layer of water within which the dis-
solved-oxygen content is lower than in the over- and underly-
ing water layers. It is caused by excessive demand for oxygen
by decaying organic matter falling from the photic zone
above.
packed column: a relatively large-diameter gas-chromato-
graphic column that is packed with a solid material upon
which the stationary phase is coated. cf. capillary column.
PAH: polycyclic aromatic hydrocarbon.
paraffins: alkanes.
PDB: Belemnites from the PeeDee Formation, Cretaceous of
South Carolina. PDB is the standard for comparing carbon-
isotope ratios.
permil: parts per thousand, written as 0/00. Used in expressing
the difference in isotope contents between a sample and the
standard.
Ph: abbreviation for phytane.
phenol: 1. a group of organic compounds containing a hydroxyl
(OH) group attached to an aromatic ring. 2. the simplest
member of the phenol family.
photic zone: the depth range within which photosynthesis oc-
curs in marine or lake waters. The thickness of the photic

zone is seldom greater than 200 m, and is limited by light
penetration, which in turn is limited by turbidity.
phytane: isoprenoid hydrocarbon containing 20 carbon atoms;
derived from the chlorophyll molecule.
phytoplankton: unicellular photosynthetic organisms that
mainly live in marine or lacustrine waters. They are responsi-
ble for approximately half of the annual photosynthetic pro-
ductivity on the earth. They are also called algae and include
coccolithophorids, diatoms, and dinoflagellates.
plankton: See phytoplankton and zooplankton.
polycyclic: having many rings in its chemical structure.
polytners: large molecules consisting of many small subunits.
Biopolymers have regular structures, whereas geopolymers
have irregular, unique structures formed from a wide variety
of subunits.
porphyrins: large, complex NSO compounds derived from
chlorophyll and_related molecules. There exist several homol-
ogous series of porphyrins that can be useful as biomarkers
and fingerprints.
possible source rock: See source rock.
post-mature: See ovennature.
potential source rock: See source rock.
Pr: abbreviation for pristane.
primary migration: See expulsion.
pristane: isoprenoid hydrocarbon haviqg 19 carbon atoms.
Production Index: See Transfonnation ratio.
programmed-temperature chromatography (PTC): gas
chromatography carried out beginning at a low temperature
and progressing to higher temperatures according to a prede-
termined temperature program. See also gas chromato-
graph.
pseudo-activation energy: a parameter used to describe the
average activation energy of a system consisting of numerous
different chemical reactions. See also activation energy.
PTC: See programmed-temperature chromatography.
pycnocline: a sharp density discontinuity between water layers,
caused either by thermal stratification (thermocline) or salin-
ity differences (halocline).
pyrobitumen: a term with various usages, but particularly a
bitumen that has lost its volatile components and solidified,
often with concurrent polymerization.
pyrolysis: heating a sample in the absence of oxygen to bring
about thermal-decomposition reactions. Pyrolysis (e.g., Rock-
Eval) is used to measure remaining hydrocarbon-generative
capacity of sedimentary rocks.
R: chemical designation for rectus (right), which indicates the
relative positions of the four groups bonded to a carbon atom.
There is not necessarily a correspondence between the R,S
system and the a,13 system.
GLOSSARY 213
R,,: vitrinite reflectance measured in air. This technique is used
mainly by Russian workers. Charts exist that convert Ra
values to Ro.
Ro: vitrinite reflectance measured in oil immersion. See also
vitrinite reflectance.
rank: See coal rank.
reducing agent: an atom, molecule, or ion that promotes re-
duction of another substance. The reducing agent is itself
oxidized in the process.
reduction: the gain of electrons by an atom, molecule, or ion
during a chemical reaction. if. oxidation.
reflectance: See vitrinite reflectance.
resinite: a kerogen maceral formed from fossil tree resin.
resins: NSO compounds that are smaller than asphaltenes.
retention time: the length of time a compound takes to come
out of a chromatographic column. Retention time will vary
greatly as chromatographic conditions (flow rate, tempera-
ture, nature of stationary and mobile phases, etc.) are
changed.
Rock-Eval: an instrument for carrying out pyrolysis of rocks
and sediments. The Rock-Eval is in common use throughout
the oil industry. Information on both kerogen type and matu-
rity can be obtained with it.
8: chemical designation for sinister (lift), which indicates the
relative positions of the four groups bonded to a carbon atom.
There is not necessarily a correspondence between the R,S
system and the a,13 system.
81: thermally extracted hydrocarbons obtained during Rock-
Eval analysis prior to the onset of true pyrolysis. These hydro-
carbons are roughly similar to bitumen or EOM. if. 82.
82: hydrocarbons generated by kerogen decomposition during
Rock-Eval pyrolysis. if. 81.
83: carbon dioxide released by kerogen decomposition during
Rock-Eval pyrolysis.
sapropel: an infrequently used term that is usually synonymous
with "amorphous material of algal origin." See also amor-
phous organic matter.
saturated: containing the maximum possible amount of hydro-
gen that can be accommodated in the molecular structure
without breaking single bonds.
saturated hydrocarbons: hydrocarbons containing no double
bonds.
secondary migration: movement of hydrocarbons through a
permeable conduit from the edge of a source rock to the site of
accumulation.
sill: the point in a restricted basin through which the deepest
waters enter into the basin.
single bond: a chemical bond in which two electrons are
shared. Most bonds are single bonds.
214
source rock: a much-used and rather ambiguous term. The
following specific usages are proposed here:
effective source rock: a rock that has actually generated and
expelled hydrocarbons.
potential source rock: a rock that could generate and expell
hydrocarbons if its level of thermal maturity were higher.
possible source rock: a rock under consideration as an ef-
fective or possible source rock but about which we do not yet
have enough data to make a determination.
Soxhlet: a device used for extracting bitumen from rock sam-
ples. Its design allows clean solvent to reflux continually
through the powdered rock sample while the extracted bitu-
men is accumulating in the reserve pot.
spectroscopy: various techniques for analyzing samples by
looking at a range of energies (wavelengths) given off or ab-
sorbed, or by observing a range ofions produced, as in mass
spectrometry.
spore darkening: See TAl.
steranes: tetracyclic saturated hydrocarbons derived from the
steroids present in all organisms. They are useful in determin-
ing maturity and the type of organic matter and can be of
value in fingerprinting.
stereochemistIy: the spatial arrangement of atoms in a
molecule.
steroids: biological precursors of steranes.
sterols: steroids containing an alcohol ( - OH) group.
stratification: development of nonmixing water layers of differ-
ent densities, as a result oftemperature or salinity differences.
TAl: Thermal Alteration Index, a measure of kerogen maturity
obtained by observing the color of bisaccate pollen grains in
transmitted light under a microscope.
tar: very heary, viscous oil formed either by biodegradation or
evaporation of a normal crude oil or by precipitation of as-
phaltenes in a reservoir as a result of cracking. if. heary oil.
TCD: thermal-conductivity detector, used to detect hydrocar-
bons as they emerge from a gas chromatograph.
terpanes: ten-carbon hydrocarbons containing two isoprene
units.
Thermal Alteration Index: See TAl.
thermal-conductivity detector: See TCD.
thermocline: See pycnocline.
thin-layer chromatography: chromatography carried out on
a thin layer of stationary phase spread out on a flat plate. The
mixture to be separated is placed in a spot on one edge of
the plate. The plate is then placed in a vertical position, with
the spot at the bottom, in a shallow tray of solvent (the mo-
bile phase). Upward movement of the solvent and mixture
is by capillary action..
Time-Temperature Index: See TTl.
TOC: total-organic-carbon content, in weight percent of dry
rock or sediment.
trans: arrangement in which two groups attached to a
molecule are on opposite sides. if. cis.
Transformation ratio: the ratio SlI(S1 + S2) derived from
Rock-Eval pyrolysis. High transformation ratios supposedly
indicate either the occurrence of catagenesis or contamination
by migrated fluids or drilling additives. Low ratios indicate
either immaturity or extreme overmaturity.
tris: prefix meaning three.
triterpanes: polycyclic (mostly pentacyclic) isoprenoid hydro-
carbons composed of three terpane units. They are useful in
maturity determinations and in interpreTanons of depositional
environments as well as in fingerprinting.
triterpenoids: biological precursors for triterpanes.
TTl: Time-Temperature Index of maturity calculated using
Lopatin's method.
unsaturated: able to accomodate more hydrogen in the
molecular structure by adding it to double bonds.
upwelling: the vertical movement of subsurface marine or lake
waters to the surface. Upwelling occurs where surface waters
are moved aside by water and wind currents. Nutrients are
brought into the photic zone by upwelling, and photosyn-
thetic productivity is greatly enhanced.
urea adduction: a method for separating n-alkanes from
branched and cyclic hydrocarbons, similar in principle to
molecular sieving.
UV: ultraviolet.
van Krevelen diagram: a diagram developed by the coal sci-
entist van Krevelen in which the atomic HlC ratio of a coal is
plotted against its atomic O/C ratio. The diagram distin-
guishes coals according to the combined effects of type of
organic matter and rank (maturity). Van Krevelen diagrams
have also been adopted in modified form (hydrogen index
versus oxygen index) for interpreting pyrolysis data of
kerogens.
vitrinite: a kerogen maceral formed from terrestrial plant mate-
rial, mainly of woody, cellulosic, or lignin origin, but which
also may contain minor amounts of waxy or resinous mate-
rial. Vitrinite is considered to have generative potential
mainly for gas, but if waxes or resins are significant con-
tributors, it may also generate oil or condensate.
vitrinite reflectance: a method of determining the maturity of
organic material by measuring the ability of tiny vitrinite par-
ticles in kerogen or coal to reflect incident light. The phenom-
enon of increasing reflectance was observed and utilized by
coal workers in the 1930s, and has been applied to kerogens
since about 1970. Application of vitrinite reflectance in deter-
mining kerogen maturity is more difficult than in measuring

coal rank for several reasons: the scarcity of vitrinite in many
kerogens, the abundance of reworked vitrinite in many sam-
ples, the lack of direct connection in most cases between oil
generation and changes in vitrinite, and the sensitivity of
vitrinite-reflectance values to contamination by migrated
bitumen.
water washing: the removal of the more soluble components
(light hydrocarbons and aromatics) of oil by dissolution in
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 phytoplank-
ton for their source of energy. They are not photosynthetic
organisms.
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Index
Accumulation, 3, 63, 64, 65, 68-69
Activation energy, 122, 139, 144-145,205
Aerobes, 9, 55, 205
AJaska, 11, 12,58, 114, 115, 116, 136-137,
185
AJberta Deep Basin, 68
AJcohols, 24, 45, 46
AJgae. See also Phytoplankton
Blue-green, 47
As contributors to kerogen, 33, 106
In evaporitic environments, 12
Fluorescence of, 88, 102
Lacustrine, 33
Marine, 33, 106
Sources for hydrocarbons, 2, 45, 47
AJgal material, 5, 14, 157
AJginite, 33, 106, 205
AJkanes, 20-22, 205. See also n-AJkanes
Alkenes,21-22,205
Alkyl groups, 21, 205
Biodegradation of, 56
Migration of, 28, 51, 53
AJphaconfiguration, 26-27, 205
Amino acids, 25
Anaerobes, 9, 34, 55, 205
Analytical procedures, 73-91
Costs of, 90
Philosophy of, 73-74, 90, 97,173
Planning of, 73-74, 90
Angola, 10
Anhydrite, 139, 163. See also Sulfate ion
Animals, 5
Anoxia, 9-13, 206. See also Anoxic sediments
Causes of, 10-13, 17
Implications for exploration, 9-10
Indicators of, 9, 15-17
Anoxic events, 11, 15, 17
Anoxic sediments
Examples of, 9-13, 15-16, 114
TOC values in, 9, 17, 106
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 Biodeg-
radation
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 Con-
tamination
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, 159-
160
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 227

Correlations-Continued Diterpanes-Continued Faulting

Practice problems, 174-180 Mass spectrum of, 80 Effect on maturity calculations, 128-130
Specific parameters in, 155, 159-163 Maturity effects in, 54 In migration, 66-67
Steranes in, 161-163, 165, 169, 171, 174- Relation to resinite, 49, 54, 161 Fecal pellets, 14
176 Double bonds, 21-23, 26, 27, 208 Fingerprinting, 80, 83, 156, 160,208
Sulfur in, 157, 169, 178-180 DPEP,24,51,108-109 Fischschiefer, 174, 176, 178-179
Trace metals in, 159 Drainage area, 66, 201 Fluorescence, 208-209
Triterpanes in, 161-163, 165-166, 169, 171 Drilling fluid additives, as contaminants, 89- Of bitumen, 89, 104
C.O.S.T. B-2 well, 111, 113 90, 158 Ofkerogen, 86, 88, 97, 102
Costs Dry gas, 208. See also Gas, dry; Methane Fluvially dominated systems, 11-12, 13. See
Analytical, 90 Dundee Formation, 166-168 also Deltas
Of modeling, 203 Dysaerobic, 9, 208 Foreset beds, 11, 114
Of swface prospecting, 184-187 Dysoxia, 9, 208 Formation-density logs, 84
CPr. See Carbon Preference Index Fractional conversion, 198-200
Cracking. See Chemical reactions; Oil Fractures, 66, 172-173
Cutinite, 33, 106, 115, 146 Eagle Ford Shale, 191-193 Fragment ions, 78-80, 209
Cyanobacteria, 47 East African Rift, 10 Fragmentogram, 80, 209
Cyclization,28,32,45,207 East Texas Basin, 191-194 Free radicals, 38, 209
Cycloalkanes, 21, 23, 207 Electron-spin resonance (esr), 38, 89, 103, Fulvic acids, 32, 209
Cyclohexane, 20, 26 208 Functional group, 209
Cyclohexene, 21 Elemental analysis, 82-83, 86, 98, 107, 208
Cyclothems, 12 Elko Formation, 10, 169, 171 G,94
EOM. See Bitumen Determination of, 94-98
Epimerization, 28-29, 51, 53,208 Go, 94
D:J Sandstones, 196-199 Epimers, 28, 208 Estimation of, 105
Deadline for hydrocarbon preservation. See Erosion Gabon, 10
Oil; Gas In constructing burial-history curves, 128, Gamma-ray logs, in estimating TOC values,
Deasphalting, 55, 74, 156 136,148,150-152,154 84
Decarboxylation, 27, 207 Effect on maturity, 116-117, 133-134, 136, Gamma-ray surveys, 186
Deep Sea Drilling Project, 15 148, 150-151 Gammacerane, 161-162, 169, 171
Delocalization of electrons, 23, 207-208 Estimation of amount, 116-117, 135, 150 Gas. See also Methane
Delta, use in isotope ratios, 30 Ethane, 20, 21, 22, 83, 164 Adsorbed, 83
AC method, 185-186 Ethene, 21, 22 Analysis of, 83, 184
Deltas. See also Mahakam Delta Ethylene, 21 Biodegradation of, 59-60
Migration in, 66, 172 EtiOporphyrins, 24, 51, 108-109 Biogenic. See Biogenic gas
Sedimentation in, 10-11, 14, 162 Evaporites Composition of, 59-60, 164
Density logs, estimating TOC values with, 84 Isoprenoids in, 47,160 Correlation of. See Correlation, gas-gas
Density stratification, 7, 10-13 Isotope ratios in, 157 Deadline for, 139,209
Denver Basin, 196-199 n-Alkanes in, 46-47, 49, 160 Dry, 135, 139, 208. See also Methane
Depositional environment. See Organic facies As source rocks, 12 Generation of, 2, 32, 35, 38-41, 55, 59-60,
Diagenesis, 2, 6, 32, 38, 208 Exinite, 33, 106, 146, 208 135. See also Methane
Aerobic, 9, 205 Expulsion, 3, 63-65, 208 Headspace, 83
Anaerobic, 9, 205-206 Diffusional, 63-64 Hydrates, 69, 209
Of different types of organic matter, 14 Direction of, 65 Isotopic composition of, 59-60, 83, 164,
Effect on biomarkers, 45-50 Distance of, 65 184-185
Effect on sulfur content, 50-51 Effect of richness on, 39-40, 64 Mixing of, 59, 164
Effect on TOC values, 6, 14-16, 105-106 Effect on oil composition, 64, 69-70 Nonhydrocarbon, 59
Kerogen formation during, 32-33 Efficiency of, 64, 65, 70, 201 Origin of, 164
Loss ofheterocompounds during, 24, 32 Gas-phase, 65 Sour, 59
Prevention of, 9, 14, 17 Mechanisms of, 63-65 Wetness of, 59-60, 83, 164, 215
Diasteranes, 53 Oil-phase, 64-65 Gas chromatogram, 77, 209
Diatomite, 9 Threshold for, 64, 201 Gas chromatograph, 76, 209
Diesel, as contaminant, 89-90 Timing of, 39-40, 64, 70 Gas chromatography, 76-78
Diffusion, 64, 208 Exshaw Shale, 12 Gas chromatography/mass spectrometry, 78-
Dilution, 6-7, 14-15, 16-17 Extraction, of bitumen, 74, 208 80,104,209
Diterpanes, 208 Gc,76-78
Aromatization of, 44 Facies-cycle wedges, 16 Gclms, 78-80, 104
As biomarkers, 45, 49, 54 Fats, 24. See also Waxes; Fatty acids Geochemical logs, 111-113, 118-119
In correlations, 161 Fatty acids, 24, 44, 45, 46 Geochemical Surveys, Inc., 185-186
228

Geohistory diagrams, 128, 130-131, 209 Hydrocarbons-Continued Ka1imantan, 13, 115, 172
Geopolymers, 32, 209 Saturated, 21 Kansas, 10
Geothennal gradient Separation of, 74-76 Karabogaz, 11
Calculation of, 125 Unsaturated, 21. See also Hydrocarbons, Keweenawan Rift, 10
Doglegs in, 126-127 aromatic Kentucky, 172
Effect on maturity, 134-135 Hydrocarbons, already generated, 94 Kerogen,2,31-41,210
In thrusted regions, 128, 130, 131 Hydrochem Surveys International, 184-185 Analysis of, 82-89, 97-103, 106-108
Variation through time, 125-128, 130-131, Hydrogen Aromaticity of, 34, 36-38, 98
134-135, 136-137 Role in cracking, 27-28, 36 Composition of, 33-35
Gennany, 174-176 Hydrogen index, 95, 106, 210 Concentrate of, 82, 86-89
Gippsland Basin, 13, 115, 165-166 Effect of maturity on, 95, 106 Darkening of, 37. See also Thennal Alter-
Graneros Shale, 12 Interpretation, 36, 45, 59, 206 ation Index
Graphite, 23, 26 In volumetric calculations, 198-201 Effect of source on, 31, 33-35
Graphitization, 209 Hydrogenation, 22,27,210 Elemental analysis of, 82-83, 86, 98, 107
Gravity of oil. See API gravity Hydroxyl group, 25,210 Flotation of, 82
Gravity surveys, in surface prospecting, 186 Fluorescence of, 86, 88, 97-98, 102
Green River Shale, 10, 33, 68, 86, 94 Iatroscan, 75-76 Fonnation of, 32-33
Greenhorn Fonnation, 196 Idaho, 93 Hydrocarbon generation from, 32, 38-41.
GuifCoast, 12,59,114,137-138, 147 Indonesia, 115 See also Catagenesis
Induced polarization, 186 Maturation of, 35-41. See also Catagenesis
Hadriya Fonnation, 12 Inertinite, 33, 98, 106, 107, 210 Maturity detenninations, 86-89, 98-104
Halo, geochemical, 181-182, 185, 186 Infrared spectroscopy, 159 Microscopic analysis of, 86-88, 97-102
Hanifa Limestone, 12 Interocean Systems, 184 Molecular size, 2, 31-32
Headspace gas, 83 Iodine, 385 Nitrogen in, 34, 36
Heptane Index, 158 Isoheptane Index, 158 Ovennature, 98
Hennosa Fonnation, 12 Isomerization, 28, 210 Oxygen in, 33-34, 36-37
Heteroatoms, 24, 210 Isomers, 25-27, 210 Pyrolysis of. See Pyrolysis
Heterocompounds, 24, 44, 210. See also NSO Isoprene, 21, 210 Pyrolysis-gas chromatography of, 85-86,
compounds Isoprenoidln-alkane ratios, 51-52, 160, 178- 96
High-grading, of exploration areas, 1 180 Quantity of, 84
High-perfonnance liquid chromatography Isoprenoids, 21-22, 39, 44, 210 Reflectance of. See Vitrinite reflectance
. (HPLC), 81-82, 160-161,210 Analysis of, 44, 76, 77 Source capacity of. See G; Go
Homologs,210 Biodegradation of, 56, 160 Structure of, 33-38
Hopane,48,50,54 As biomarkers, 45, 47 Sulfur in, 32, 34, 36, 39, 41, 50-51, 58, 59,
Hopanes, 48, 210. See also Triterpanes In correlations. See Correlations 135-136, 158
C27 ,161 Maturity effects on, 51 Kerogen type, 33-35
C2 8> 79, 161 Source of, 47 AJnorphous, 86,88,97-98, 102, 105, 106
C29 , 48, 50 Isotope fractionation, 29-30 Determination of, 84-86
C30 , 48, 50, 54 Isotope profiles, 159, 166-167,210 Effect on oil generation, 39-40, 135-136,
In correlations, 161-163 Isotope ratios 146, 152
Demethylated by biodegradation, 56, 161- Of bitumen, 157, 159 Fluorescence, 97-98, 102, 105, 106
163 Carbon,29-30,80-81,83, 157, 159, 164, Gas-prone, 86, 97, 106, 199-201
Extended,48,50,53 172,177-180,184,186 Herbaceous, 210
Maturation of, 53 Of carbonates, 29-30, 186 High-sulfur, 32, 34, 36, 39, 41, 50-51, 58,
Origin of, 48, 50 In correlations. See Correlations 59, 135-136, 158
Humic substances, 32, 210 Effect of biodegradation on, 56, 57, 179 Inert, 33, 86, 106. See also Inertinite
Hydrates, gas, 69, 210 Effect of migration on, 157 Oil-prone, 86,97, 106, 146,201
Hydrocarbon generation, 2, 38-41. See also Effect of source on, 158, 159 Relation to source potential, 106-107
Oil; Bitumen; Gas Of gas, 30, 59-60, 83, 157, 164, 172, 178, 180 TJpeI,33-34,37, 106-107, 146
Hydrocarbon-source capacity. See Source ca- Hydrogen,29,80,83, 157-158, 164 TJpeII,33-35,37, 106-107, 115, 136, 146,
pacity Interpretation of, 157-159, 164, 179-180 152,201
Hydrocarbons, 19-24,210 Ofkerogen, 30, 38, 157, 159 Type III, 33-35, 37, 106, 115, 136, 146,
Analysis of, 76-81 Maturity effects on, 38 152, 199
Aromatic, 22-24,44,45 Measurement of, 30, 80-81, 83 Type IV, 33, 106
Branched,21,44 Nitrogen, 29, 80 Kimmeridge Clay, 12, 119-120, 161
Cyclic, 21-24, 44 Ofoil,30,57,157-158, 177-180 Kinetics, 211
Light. See Light hydrocarbons; Gas Of plants, 30 Of oil destruction, 139, 143
Naphthenoaromatic, 23-24, 44, 49, 54 Sulfur, 29, 80,157 Of oil generation, 121-122, 139, 142-145
Polycyclic aromatic, 23, 45 . Table of, 29, 30 Kingak Shale, 114
Released during pyrolysis, 85-86 Isotopes, 29-30, 210 Kreyenhagen Fonnation, 12

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 Ma-
turity modeling
Application to exploration, 139-142
Application to preservation deadlines, 138-
139,142
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 fragmento-
gram
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, 108-
111
Correlation among, 108, 144
Interpretation of, 108-111, 116-117, 118-
120
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 Ac-
cumulation
Biodegradation during, 55-56, 70
Carrier beds for, 3, 63
INDEX 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, 69-
70,109-110
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

As maturity indicators, 172. See also Car- Cracking of, 32, 38-41, 55, 139, 143, 154, Quantity of, 84
bon Preference Index 156,164,202 Resistant; 14
Odd-carbon preference in, 45-47, 51 Deadline for, 108, 138-139, 142, 154 Reworked, 14, 33
Separation of, 44, 76 Deasphalting of, 55, 156 Settling rates of, 14
Terrestrial sources for, 45-46 Emulsions in, 74 Terrestrial, 6,9, 14,25,33,45,49,85,97,
n-Paraffins. See n-Alkanes Generation of. See Oil generation 103, 106, 108, 162, 172
n-Pentane, 20-21 Gravity. See API gravity Organic richness, 6-16
Namibia, 8 Heavy, 66,68,210 Orinoco Tar Belt, 55
Naphthalene, 22, 23 Immature, 158,169 Otway Basin, 140-141
Naphthenes, 21, 23 Isotope ratios in, 30, 56-57,157-159,177- Outcrop samples, 89
Naphthenoaromatics, 23-24, 44, 49, 54 180 Overpressuring, 39, 64, 70
Nevada, to, 169 Maturity of, 41, 55, 172 Overthrust Belt, 128
New Albany Shale, 12 Mixing of, 162-163 Oxic environments, 13-14, 15-16
New Jersey, 111, 113 Naphthenic, 40,174,178 Oxidation, 9, 27-28, 45, 212
New Mexico, 12, 135 Nitrogen in, 51, 56 Oxidizing agent, 27, 212
Newark Graben System, 10 Paraffinic, 40,174,178 Oxygen
Niagara Formation, 166-167 Pour point of, 55, 56, 159 As heteroatom, 24
Nickel. See Porphyrins, VlNi ratios in ReseIVoir transformations of, 55-58, 60 In kerogen, 33-34, 36-37
Niobrara Formation, 196 Sulfur in, 36, 41, 47, 50-51, 56-59, 69, 157, In organic matter, 24
Nitrate ion, 9 169,179-180 In waters and sediments, 9, 13-16. See also
Nitrogen Viscosity of, 55, 56 Oxygen-minimum layer; Anoxia
In gas, 59-60 Water washing of, 55, 156, 179, 215 Oxygen index, 95, 106, 212
As heteroatom, 24 Wax content of, 40, 49, 55, 157, 159 Oxygen-minimum layer, 10-13, 17,212
Isotope ratios of, 29, 80 Oil generation, 2, 32, 38-41 Development of, 10
In kerogen, 34, 36 Effect of kerogen type on, 39-40,135-136, Expansion of, 11-12
As nutrient, 14 146,152
In oil, 51, 56 Kinetics of, 122, 139, 142-146 PAH, 23, 212
In organisms, 24 Threshold for, 135-136, 138, 146, 152 Paleotemperature, 125-127, 128, 130,
Nmr, 98, 212 Timing of, 39, 139-141, 143-144, 150, 131
Nonhydrocarbons, 24-25 152-154 Paraffins, 20-22, 212
Nonesuch Shale, 10 Window for, 108, 137-138,212. See also Paris Basin, 94, 95
Norhopane, 48, 50 Oil generation, timing of PDB, 29, 212
Normal alkanes, 212. See also n-Alkanes Oil shales, 32, 98 Pentane, 74. See also n-Pentane
North Dakota, 68 Oil Show Analyzer, 86, 212 Permil,30,157,212
North Sea, 12, 115, 118, 119, 135, 145, 159, Oklahoma, 185 Peru, 8,11
161, 184 Oleanane, 161-162 Petrex,185
North Slope of Alaska, 11, 12, 58, 114, 116, Olefins, 21, 212 Phase changes, 70
136-137 OML. See Oxygen-minimum layer Phenols, 14, 25, 33, 446
Norton Basin, 115 Organic chemistry, 19-29 Phosphoria Formation, 12, 34, 93
Norway, 161 Organic compounds, 19-28, 212 Phosphorus, 14
NSO compounds, 24-25, 44, 45, 212 Hydrocarbons, 19-24 Photic zone, 7, 10, 212-213
Nuclear magnetic resonance, 98, 212 Isomers of, 25-27 Photosynthesis, 5, 7, 10, 30
Nutrients Names of, 19-25 Phytane, 22, 48, 213. See also Pristanelphy-
From algae, 14 Nonhydrocarbons, 24-25 tane ratio
In evaporitic environments, 12 Reactions of, 27-28. See also Chemical Phytoplankton, 5-6, 213. See also Algae
And productivity, 7, 16 reactions Plants, terrestrial, 5-6, 25, 33, 48,162-163
Recycling of, 7 Shapes of, 25-27 Plutons, 117
In upwellings, 7 Structures of, 19-27 Po Basin, 174, 178-180
Organic facies, 4, 5-18,114,160, Polar compounds, 44
Oceanic anoxic events, 11, 15, 17 161 Pollen
Ohio, 172 Organic matter. See also Kerogen In kerogens, 33, 86
Oil Algal, 5, 14, 157 TAl measurements from, 88
Accumulation of, 3, 63, 64, 65, 68, Determination of type, 84-86 Polymers, 25, 32,213
202 Diagenesis of. See Diagenesis Porphyrins, 24, 44, 213
Analysis of, 74-81 Dilution of, 6-7, 14-15, 16-17 Analysis of, 81-82
Biodegradation of, 55-58 Maturity of, 86-89 As biomarkers, 45, 47-48, 51
Comparison with bitumen, 58-59 Oxidation of. See Diagenesis In correlations, 160-161, 178-180
Composition of, 43-60, 69-70 Oxidized, 6, 14, 33,85, 105-107 Maturity effects on, 51, 104, 108-109
Correlation of. See Correlations PreseIVation of, 8-14. See also Diagenesis Migration effects on, 69

Porphyrins-Continued
Nonbiodegradability of, 57
Source of, 47-48
Types of, 24, 51, 81, 108-109
V~iratiosin,47,51,81, 104, 160, 178-
180
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, 142-
143, 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
Ra, 87, 213. See also Vitrinite reflectance
Rainfall, as cause of stratification, 13
Reconcavo Basin, 134
Reducing agent, 27, 213
Reduction, 27-28, 213
Reflectance. See Vitrinite reflectance
Reservoir rocks, deposition of, 16
Resin
Plant, 14, 33, 49, 115
Fossil, 33, 35, 86. See also Resinite
INDEX 231
Resinite, 33, 54, 97, 106, 115, 213 Source-rock evaluation-Continued
In coals, 115 Philosophy of, 93-94, 117
Geochemistry of, 39, 161 Practice problems, 118-120
Oil generation from, 39-41, 115, 135-136, Soxhlet extractor, 74, 214
146 Spores
Resins, as NSO compounds, 44, 213 Color of. See Thermal Alteration Index
Retention time, 77, 213 In kerogen, 33, 86
Richness, organic, 6-16 Stagnation, 10, 11, 17
Rift basins, 10, 134 Starch, 25
Rock-Eval, 85, 94-95, 98, 102, 213. See also Steranes, 21, 23, 50, 214
Pyrolysis Aromatized, 23-24, 49, 54,80, 109, 163
Biodegradation of, 56, 162-163, 165
Sl peak, 85, 94, 95, 106, 213 As biomarkers, 45, 47-50, 53
S2peak, 85-86, 88, 94-95,106,213 In correlations. See Correlations
S3 peak, 85, 94-95, 106,213 Effect of migration on, 109-110
Salinity, effect on circulation and preservation, Epimerization of, 28, 51, 53, 109
12-13 As environmental indicators, 48-49, 162-
San Jorge Basin, 162-163 163
Sanjuan Basin, 135 Isoskeletal, 53
Santa Barbara Basin, 12 Mass fragmentograms of, 110, 165,175-
Saturates, 21, 213 176
Saudi Arabia, 12, 66 Mass spectra of, 78-80
Screening procedures, 74, 84, 90, 98, 106 Maturation of, 51, 53, 104, 108-111
Sediment-accumulation rate, 14, 15, 17 Numbering in, 23
Sedimentation rate Rearranged, 53, 110
Effect on dilution, 14-15, 17 Stereochemistry, 25-29, 214
Etrect on preservation, 14-15, 17 Steroids, 45, 47-49, 214
In abyssal waters, 13 Sterols, 48-49,162,214
Seeps, 181-182 Stratification, 7, 10-13,214
Seismic, integration with geochemistry, 16, Sudan, 10
69,111,184 Sugars, 25
Sheep Pass Formation, 169-171 Sulfate ion
Shelf, continental, 11 Conversion to organic sulfur, 32, 34, 51, 57
Shublik Formation, 12, 114 In fresh waters, 13, 34, 51, 169
Sills Role in diagenesis, 9, 186
Igneous, 238 Role in hydrocarbon oxidation, 27, 57, 59,
Tectonic, 11-13,213 139, 163, 186
Single bond, 213 Sulfur
Sisquoc Formation, 9 In asphaltenes, 25, 44, 51, 157
Smackover Formation, 12, 59 In carbonates, 34, 58-59, 139
Sniffer, 184 As heteroatom, 24
Solid bitumen, 64, 98 Isotope ratios of, 29, 80, 157
Solvent extraction, 74 In kerogen, 32, 34, 36, 39, 41, 50-51, 58,
Solvent evaporation, 74, 76 59,135-136,158
Source capacity Measurement of, 82-83
Evaluation of, 73-74 In oil, 36, 41, 47, 50-51, 56-59, 69, 157,
Original. See Go 169, 179-180
Remaining. See G Surface prospecting, 181-187
Source rock, 3, 93-94, 214 Carbonate cements in, 186
Ages of, 16 Cost of, 184-187
Bitumen content of, 38-39 ~C method in, 185-186
Effective, 93, 214 Gamma-ray surveys in, 186
Models for deposition of, 16, 114, 190 Gravity surveys in, 186
Possible, 93, 214 Heavy hydrocarbons in, 185
Potential, 93, 214 Induced polarization in, 186
Source-rock evaluation, 93-120 Iodine in, 186
Analytical methods for, 84-89 Isotope ratios in, 184-185, 186
Direct method, 84-86, 94-96 Light hydrocarbons in, 183-185
Examples, 111-117 Magnetics in, 185
Indirect method, 86, 96-98 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; Triter-
panes
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, 80,162-163,165-
166
In correlations. See Correlations
Demethylated, 80, 162-163, 165
As environmental indicators, 48, 50, 161-
162
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, 108-
109,111
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
Upwelling, 7-8, 16,214
Uranium
As factor in maturation, 117
As gamma-ray source, 186
Urea adduction, 76, 77, 159, 214
Utah, 12,33,64,68, 169
Van Krevelen diagram, 36-37, 95, 105,214
Modified,94-95, 105, 106, 114,214
Vanadyl ion. See Porphyrins, V/Ni ratios in
Venezuela, 12, 55, 66-67
Visible-ultraviolet spectroscopy, 81, 160
Vitrinire, 33,35, 38,40, 106, 107,214
Vitrinite reflectance, 38, 87-88, 98, 214-215
Difficulties with, 89, 98-102, 116-117, 137
Effect of caving on, 89, 98, 101
Effect of contamination and weathering on,
89
Effect of erosion on, 116-117
Effect of igneous activity on, 117, 135
Histograms, 87, 98-101
Measurement of, 87
Profiles, 88, 116-117
Revvorked,98,100
Volumetric models, 4,189-190,198-203
Walnut hulls, 89
Water, circulation of. See Circulation of waters
Water washing, 55, 156, 179,215
Waxes
In coals, 115
In kerogens, 33, 35, 97
In oils, 40, 49, 55, 157, 159
In plants, 24, 33, 49
Weathering, 89
Western Interior Seaway, 160
Williston Basin, 39, 65, 68, 157
Wisconsin, 10
Wood. See Organic matter, terrestrial
Woodbine Fonnation, 191-195
Woodford Shale, 12
Wyoming, 10,33,93, 128, 140
Xylenes, 22, 45
Zooplankton, 5, 215