PETROLEUM

GEOCHEMISTRY

Dr. D. Satyanarayana
Visiting Professor, Delta Studies Institute &
Former Professor of Marine Chemistry
Andhra University, Visakhapatnam

2011

DAYA PUBLISHING HOUSE

Delhi - 110 035

iv

2011, D. SATYANARAYANA
ISBN 81-7035-675-X
ISBN 978-81-7035-675-2

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Acknowledgements

I am grateful to the following publishers, Authors/Editors of

books for according permission to use their published illustrations.
P M/S Academic Press, R.C. Selley. Elements of Petroleum
Geology (1998); J. Brooks (Ed). Organic Maturation Studies
and Fossil Fuel Exploration (1981).
P M/S Applied Science Publishers, G.D. Hobson (Ed).
Developments in Petroleum Geology, Vol. I (1977) and Vol.
II (1980).
P M/S Burgess Publishing Company, Douglas Waples.
Organic Geochemistry for exploration Geologists (1981).
P M/S Chapman & Hall, Steven A Tedesco. Surface
Geochemistry in Petroleum Exploration (1995).
P M/S Directorate General of Hydrocarbons (DGH). India
Petroleum Exploration and production Activities20052006.
P M/S Elsevier Publishers, E.C Donaldson (Ed). Enhanced
oil Recovery I : Fundamentals and analysis (1985).
P M/S Indian Petroleum Publishers, S.K. Biswas et al., (Eds).
Proceedings of 2nd Seminar on Petroliferous Basins of
India. Vol. I and Vol. II (1993); Lakshman Singh. Oil and
Gas Fields in India (2000).

vi

P M/S International Human Resource Development

Corporation (IHRD), Douglas, W. Waples. Geochemistry
in Petroleum Exploration (1985).
P M/S Kluwer Academic Publishers, M.D. Max (Ed). Natural
Gas Hydrates (2000).
P M/S SpringerVerlag, B.P Tissot and D.H. Welte.
Petroleum Formation and Occurrence (1984).
P M/S. Unwin Hyman Publishers, F.K. North. Petroleum
Geology, 2nd edition (1990).
P M/S Freeman and Company, J.M. Hunt. Petroleum
Geochemistry and Geology, 2 nd edition (1996); A.I.
Levorsen. Geology of Petroleum, 2nd edition (1967).
D. Satyanarayana

Foreword

Petroleum Geochemistry is a branch of Organic Geochemistry

that deals with the study of distribution, composition and
constitution of petroleum, its constituents and its precursors in
sedimentosphere at gross and molecular levels to define principles
of occurrence and origin of petroleum in sedimentary basins, the
ubiquitous natural habitats of economically attractive
accumulations.
The vicissitudes of basin evolutionary history of each
sedimentary basin are complex and no two points along dip or strike
theoretically have identical depositional conditions. No technique
of petroleum exploration is, therefore, equally sensitive and accurate
in space and time. Petroleum exploration and exploitation is thus
both knowledge and technology intensive and is essentially a
multidisciplinary task where an inadequacy of one discipline or
technique is covered by strengths of one or other discipline or
technique or set of disciplines or techniques. While geology and
geophysics are excellent in unraveling the types of rocks, their
physical attributes, structural attitudes and their distribution and
superposition in space and time in a basin, they are unable to deal
directly with aspects of origin, migration and accumulation of
petroleum.

viii

One of the imperatives of the industry is to have knowledge on

aspects of origin and occurrence of petroleum specific to each basin
or part thereof. This is essential to ensure reduction of risk in
petroleum exploration. Petroleum Geochemistry helps exploration
and development effort in each phase, right from reconnaissance
and stage of general assessment to the final stage of extraction of the
last producible content of hydrocarbons in a locale of accumulation,
by providing geochemical concepts and data sets on various aspects
of origin, migration and accumulation of petroleum specific to each
basin under exploration and development. Tremendous
developments have taken place in acquisition of petroleum
geochemical data since the nineteen sixties through availability of
robust equipments and methods of chemical analysis. It is now
possible to have practically real time geochemical data to be
integrated timely for making an exploration or development decision.
Synergy amongst Petroleum Geology, Petroleum Geochemistry
and Geophysics has become an accepted practice for laying down
risk based priorities in a portfolio of exploration and development
opportunities. The synergy also leads to working out manageable
investments to initialize an E&P activity with cash flows that can be
deployed for further exploration and development efforts while
assuring market competitive returns during the entire cycle of any
given exploration and development activity.
Dr. D. Satyanarayana of the Delta Studies Institute of Andhra
University has done yeomans service to Indian academia to bring
out a maiden Indian text book on Petroleum Geochemistry. This
book will be found useful to graduate and postgraduate students
taking courses in petroleum geology, petroleum exploration and
petroleum engineering. The book touches upon authentically all
aspects of petroleum geochemistry that are relevant to exploration
and development effort.
In India, Oil and Natural Gas Corporation commenced
undertaking petroleum geochemical studies in 1957 and established
formal laboratories in 1960. ONGC Limited has since 1963 best in
class research facilities in Petroleum Geochemistry at Keshav Dev
Malviya Institute of Petroleum Exploration (KDMIPE) along with a
strong Basin Studies Group at Dehradun. ONGC Limited also has,
since 1985, standard data acquisition laboratories in all operational
areas. Oil India has modern Petroleum Geochemistry laboratories

ix

since 1990. National Geophysical Research Institute has a National

Centre of Excellence in Surface Geochemical Prospecting backed by
Oil Industries Development Board and Director General
Hydrocarbons since 2001-02 which caters to the requirements of
geochemical data acquisition of various private sector oil companies
and DGH to help evaluate prospectively of various acreages and
exploration blocks. All private sector and joint venture major
upstream oil companies profusely integrate geochemical data in
exploration decision making. This book of Dr. Satyanarayana is
therefore has great practical value for the upstream petroleum
industry in general and especially for India where large acreages
still remain explored, where deep and ultra deep water exploration
has just begun and where the ageing oil fields are being operated for
maximizing recovery factors.
To students with enquiring and creative minds and aptitude
for innovation, the book surely would inspire to undertake basic
and applied research. Dr. Satyanarayana joins the illustrious
eminent academicians of the world, who brought out books born of
lecture notes meant to disseminate in depth knowledge of Petroleum
Geochemistry for geoscientists actively engaged in upstream
activities.
The book is going to be a prized possession of academia in
geosciences and of all the scientists and engineers of the upstream
petroleum industry who are desirous to contribute their mite towards
sustaining and augmenting global energy security through long
time availability of petroleum.
Kuldeep Chandra
Dehradun

Former Executive Director R&D ONGC Limited,

and
Chairman, Afro-Asian Association of Petroleum Geochemists

Preface

During the last three decades there has been a rapid progress in
petroleum geochemistry. The aim of this book is to cover the advances
in a comprehensive way providing a background for understanding
the basic concepts and principles. It is designed to develop principles
of petroleum geochemistry and emphasise its applications to
hydrocarbon exploration. Several geochemical and analytical
techniques are described along with their relative merits and
limitations so that an appropriate technique can be selected in a
particular exploration programme. Application of principles of
petroleum geochemistry to common exploration programmes are
lucidly brought out by introducing worked out examples and case
studies.
The book is written primarily for postgraduate students of earth
sciences and graduate students of engineering taking courses in
petroleum science or engineering. It is also useful for those working
in oil industry dealing with exploration and related fields. Each
geochemical concept is explained in detail prior to its application.
Adequate references are cited in the text. Exhaustive list of books,
memoirs, papers published in journals and proceeding of World
Congress, International Seminars and Symposia are included in the
bibliography for further reading. The contents are arranged in the
following sequence so as to interpret geochemical data of varied

xii

reliability and to unravel complex geochemical processes involved

in petroleum exploration and production.
P Role of petroleum geochemistry in prospect identification,
prioritisation and risk reduction in hydrocarbon
exploration and production. Composition, properties and
genetic classification of crude oil and natural gas.
P Occurrence of petroleum in sedimentary basinsBasin
type, classification and hydrocarbon richness. Resource
estimation and production potential of typical Indian
petroliferous basins of proven commercial production.
P The origin of Petroleum-Inorganic (abiogenic) and organic
(biogenic) theories and their relative merits and
limitations. Polymerisation theory of petroleum formation
and its implications.
P Geochemical processes involved in generation, migration
and accumulation of hydrocarbons in sedimentary basins.
Factors effecting them and optimum conditions for
commercial production of petroleum.
P Application of geochemical methods for the study of
organic maturation, evaluation of stratigraphic units and
distribution of organo facies for delineation of
hydrocarbon kitchens. Principles of source rock
evaluation. Typical examples and case studies.
P Geochemical surface prospecting of hydrocarbons to
identify anomalous areas that prioritise targets for future
exploration. Relative merits and limitations of surface
geochemical methods.
P Application of hydrogeochemical surveys in exploration.
Genetic indicators for delineation of oil wells. Role of oil
field waters in enhanced oil recovery operations, and
in situ oil degradation in reservoirs. Implications of scale
formation and corrosion in petroleum exploration and
production operations.
P Role of biomarkers for characterization and evaluation of
source organo facies and depositional environments.
Application of high resolution geochemical techniques
such as GC-MS, CF-IRMS, MRM-GC-MS for molecular level
studies involving thermal cracking of light oil and

xiii

condensates; oil-oil, oil-source rock correlations to

understand migration pathways; petroleum system and
paleodepositional environments at micro level.
P Geochemical modeling of hydrocarbon generation based
on kinetics of kerogen degradation. Integration of the model
with geological history of the basin to delineate prospective
areas. Validity of the model and its application for
evaluation of petroleum potential and determination of
timing of its formation for comparison with the age of
traps.
P Application of geochemical techniques to unconventional
petroleum resources such as shale gas and oil shale;
bituminous sands; basin centered (tight) gas sands; coal
bed methane (CBM); gas hydrates. Study of their
characteristics, depositional environments, resource
potential, exploration and production strategies, and
environmental concerns. Global and Indian
unconventional petroleum resources.
I acknowledge with thanks the authorities of Andhra University
for offering an honorary professorship in Delta Studies Institute
(DSI) which prompted me to write this book. It evolved from a series
of lectures delivered on petroleum geochemistry to the students of
M.Tech. Petroleum Exploration and discussions with several
distinguished visiting faculty members. I take this opportunity to
thank Prof. D. Rajasekhara Reddy, Director (DSI) for offering facilities,
and to Sri T. Karunakarudu and V. Jayasundar Reddy (Teaching
Assistants) for their assistance in the institute. My thanks are also
due to several visiting faculty of DSI and former scientists of ONGC
Sri P.V. Ramana Rao, GGM; Sri S.S. Yalamarty, GGM & Basin
Manager; Sri P.V. Ramana, G.G.M & Director, IRS; Sri G.S. Chari,
D.G.M; Sri B.V. Rao, D.G.M; Dr. P.V.L.P. Babu, D.G.M for their
encouragement.
I am particularly grateful to Dr. Kuldeep Chandra, Former
Executive Director, ONGC and President of Afro-Asian Association
of Petroleum Geochemists, for offering several constructive
suggestions and improving the quality of the text. I am very much
thankful and obliged for his kind gesture of writing the Foreword.

xiv

My special thanks are due to Prof. V.R.R.M. Babu, Former

Professor of Geology and Geoengineering; Prof. U. Muralikrishna,
Former Professor of Chemistry of Andhra University; Sri K. Ananta
Krishna, Former DGM, ONGC for critically going through the text
and offering valuable suggestions. I am thankful to Prof.
G.S.Roonwal, Former Professor of Geology, Delhi University; Dr.
V.V. Sarma, Scientist G, Regional Centre of NIO, Visakhapatnam;
Dr. I. Nageswara Rao, Research Scientist, School of Chemistry; Dr.
P. Prabhakar, Chief Chemist, ONGC for their assistance.
My special appreciation goes to Sri V. Hari Prasad and Sri M.
Santhosh Kumar, Technical Assistants of DSI, for diligently bringing
out the text including Tables and Figures.
D. Satyanarayana
Visiting Professor, Delta Studies Institute &
Former Professor of Marine Chemistry
Andhra University, Visakhapatnam

Contents

Acknowledgements
Foreword
Preface

v
vii
xi

1.

Introduction

2.

Composition and Properties of Petroleum

2.1.
2.2.
2.3.
2.4.

3.

Saturated Hydrocarbons
Unsaturated Hydrocarbons
Compounds with Hetero (NSO) Atoms
Natural Gases

7
14
18
20

2.5. Physical Properties of Crude Oils

2.6. Thermal Alteration of Oil in the Reservoir
2.7. Classification of Crude Oils

23
28
28

Occurrence of Petroleum in Sedimentary Basins

34

3.1. Definition of a Sedimentary Basin

3.2. Classification of Indian Petroliferous
Sedimentary Basins
3.3. Cambay Basin

34
40
48

xvi

3.4.
3.5.
3.6.
3.7.

Mumbai Offshore Basin

KrishnaGodavari (KG) Basin
Cauvery Basin
Assam-Arakan Basin

3.8. Rajasthan Basin

4.

Origin of Petroleum
4.1. Inorganic (abiogenic) Theory
4.2. Organic (biogenic) Theory

5.

6.

4.3. Conclusion
Hydrocarbon Generation, Migration and
Accumulation in Sedimentary Basins

55
64
70
74
85
90
90
95
97
98

5.1. The Carbon Cycle

5.2. Genesis of Petroleum

98
102

5.3.
5.4.
5.5.
5.6.

113
115
122
125

Migration and Accumulation of Hydrocarbons

Mechanism of Primary Migration
Secondary Migration
Accumulation and its Efficiency

Geochemical Methods in Petroleum Exploration

128

6.1.
6.2.
6.3.
6.4.

Isolation of Kerogen and Bitumen

Petrographic Methods
Geochemical Methods
Stable Isotope Analysis

128
129
135
138

6.5.
6.6.
6.7.
6.8.

Rock-Eval Pyrolysis Method

TimeTemperature Index (TTI)
Level of Organic Metamorphism (LOM)
Correlation Between Geochemical and
Petrographic Techniques

141
148
166
172

Source Rock Evaluation and Correlations

176

7.1. Principles of Source Rock Evaluation

7.2. Interpretation of Source Rock Data

176
181

xvii

8.

7.3. Quantitative Volumetric Estimation of Source

Rock Hydrocarbons in a Basin
7.4. Oil-oil and Oil-Source Rock Correlations
7.5. Alteration Processes of Crude Oil Composition
7.6. Oil-oil Correlations

189
193
197
200

7.7. Oil-Source Rock Correlations

7.8. Correlation Parameters for Gases
7.9. Case Studies

202
207
208

Surface Geochemical Prospecting of Hydrocarbons

8.1. Seepages
8.2. Surface Geochemical Prospecting
8.3. Categories of Surface Geochemical Methods

9.

Hydro Geochemistry of Oil Field Waters

9.1.
9.2.
9.3.
9.4.
9.5.

220
220
223
224
234

Types and Definitions of Oil Field Waters

Classification of Oilfield Waters
Physical Properties of Oil Field Waters
Chemical Composition of Oil Field Waters
Origin and Evolution

235
236
238
239
242

9.6. Genetic Relation to Evaporites

9.7. Patterns and Significance of Salinity Distribution
9.8. Role of Oil Field Waters in Enhanced Oil
Recovery (EOR) Operations
9.9. Oil Degradation in the Reservoir

243
244

10. Organic Geochemistry and Analytical Techniques

10.1.
10.2.
10.3.
10.4.
10.5.

Biomarkers
Specific Biomarkers
Use of Biomarkers
Analytical Techniques in Petroleum Exploration
Column Chromatography

10.6. Gas Chromatography (GC)

10.7. Mass Spectrometry

246
249
257
257
259
271
273
276
277
281

xviii

10.8. Spectroscopic Methods

10.9. Thermogravimetry (TG) and Differential
Thermal Analysis (DTA)
11. Geochemical Basin Modeling: Application
to Petroleum Exploration
11.1.
11.2.
11.3.
11.4.

Integrated Models of Hydrocarbon System

Qualitative Models of Hydrocarbon System
Quantitative Geochemical Models
Mathematical Model of Kerogen Degradation
and Hydrocarbon Generation
11.5. Application of the Model to Petroleum Exploration
12. Unconventional Petroleum Resources

284
291
294
294
295
296
297
308
314

12.1. Typical Unconventional Petroleum Systems

12.2. Basinal (Deep) Gas (Tight Gas) Sands
12.3. Shale Gas

314
315
316

12.4.
12.5.
12.6.
12.7.
12.8.

317
318
320
342
348

Oil Shale
Bituminous (Tar) Sands
Coal Bed Methane (CBM)
Gas Hydrates
Stability of Gas Hydrates

12.9. Detection of Gas Hydrates

12.10. Distribution of Gas Hydrates

352
357

Appendices

363

References

371

Bibliography

405

Author Index

417

Subject Index

425