Origin and Chemistry of Petroleum. Proceedings of the Third Annual Karcher Symposium, Oklahoma, May 4, 1979

119 Pages·1981·4.281 MB·English

by  Gordon Atkinson and Jerry J. Zuckerman (Eds.)

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Origin and Chemistry
of Petroleum
Proceedings of the Third Annual Karcher Symposium,
Oklahoma, May 4, 1979
Edited by
GORDON ATKINSON and JERRY J. ZUCKERMAN
Department of Chemistry, University of Oklahoma
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First edition 1981
British Library Cataloguing in Publication Data
Karcher Symposium (3rd: 1979: Oklahoma)
Origin and chemistry of petroleum.
1. Petroleum - Congresses
I. Title II. Atkinson, Gordon
III. Zuckerman, Jerry J
553.2*82 TN863 80-41824
ISBN 0-08-026179-5
In order to make this volume available as economically
and as rapidly as possible the authors * typescripts have
been reproduced in their original forms. This method
unfortunately has its typographical limitations but it is
hoped that they in no way distract the reader.
Printed in Great Britain by A. Wheaton & Co. Ltd., Exeter
FOREWORD
G. Eglinton
Organic Geochemistry Unit, University of Bristol,
Bristol BS8 ITS, UK
In this, the Proceedings of the Third Annual Karcher Symposium, it is
particularly appropriate that the subject should be "The Origin and
Chemistry of Petroleum". Dr. Clarence Karcher, who endowed the Uni­
versity of Oklahoma with the funds to run these symposia, was a pioneer
in the application of scientific principles to petroleum exploration.
I feel that he would be pleased and intrigued by the five lectures,
herein presented, all of which follow his example. The symposium was
held at the University of Oklahoma on May 4, 1979? an especially
appropriate venue in view of the importance of petroleum in the history
and development of Oklahoma. It brought together an interdisciplinary
group of chemists, geochemists and petroleum geologists to listen to
and exchange ideas with the guest speakers. This volume presents the
collected lectures, which are in part reviews of published work, as a
statement of our contemporary understanding of this most timely subject.
The central contemporary precept, which time and again is apparent in
the reasoning associated with the lectures presented here, is that
petroleum is generated from finely disseminated organic matter of bio­
logical origin entombed in deeply buried sediments. Generation of
petroleum begins when such sediments experience elevated temperatures
consequent upon increased depths of burial in the sedimentary column.
Once generated in these source rocks, the petroleum migrates by largely
little understood processes into porous reservoir rocks. Such forma­
tions, when located, may provide oil in sufficient quantities for
commercial production.
v
vi Foreword
In the first of the five papers, James Maxwell and his colleagues pre­
sent an overview of their work at Bristol in the rapidly-developing
field of molecular assessment of the thermal history of sediments.
After a brief introduction to the concept of biological marker com­
pounds and to the structural changes, including the stereochemical
conversions, which take place in them under the influence of the min­
eral matrix and time and temperature, they proceed to a detailed study
of the lower Toarcian sediments of the Paris Basin. These epiconti-
nental organic-rich shales of rather constant lithology dip from sur­
face exposures at their margins to a depth under Paris of approximately
3 km. They, therefore, provide a good test situation for the analysis
of organic matter, including acyclic isoprenoids, steranes, hopanes
and porphyrins, which ranges in maturity from relatively immature to
the oil generation zone. The molecular distributions and stereochem­
ical ratios show clear trends with burial depth that promise major
quantitative applications in petroleum exploration.
Meinschein and Huang further extend the reader's awareness of the ulti­
mate biological origin of the compounds present in petroleum with a
detailed exposition of their pioneering work on steroids, sterols and
stanols as ecological indicators. This approach is illustrated with
compositional data for the plankton and bottom sediments of the
Aransas River and the Gulf of Mexico. They then link this work on
Recent immature sediments to their analyses of the relatively mature
sterane distributions of petroleums of the Viking Formation in Canada
from which they infer that these petroleums, like most others, have
been formed from biological remnants deposited in near-shore or marine
environments. Hence, this one class of biological matter, the
steranes, provides diagenetic and catagenetic information (Chapter 1)
and paleoecological assessment (Chapter 2). Meinschein and Huang
conclude their article with a treatment of the solubility and Chroma­
tographie relationships underlying the concentration of petroleums and
gases into reservoirs.
Chapter 3, by John Hunt of Woods Hole Océanographie Institute, is short
but useful in that it describes results obtained with an important
technique for the characterization of petroleum source rocks in terms
of the quantity, types and maturation state of the organic matter
therein. The technique involves a sequence of thermal distillation
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viii Foreword
the elemental composition of the kerogen (insoluble organic debris),
the petroleum, the source potential and the content of molecular oxygen
incorporated into the system to calculate the amount of petroleum gen­
erated. Computer-based calibrations provide a set of parameters whose
values can be utilized in a simple equation. He illustrates this
empirical approach with 12 wells on the Scotian Shelf, off Nova Scotia.
His belief is that the limiting factor in obtaining petroleum will not
be finding it, but the economies of producing it from progressively
less accessible reservoirs.
In conclusion, these five Chapters link advances in the fundamental
organic chemistry of petroleum with new predictive approaches to the
search for oil resources. The Karcher symposium provides a landmark
in this fast developing area - even in simply bringing together these
five different approaches, this volume can serve to stimulate new re­
search. Thus, for example, one can see that the new diagenesis and
catagenesis parameters for assessing maturation described by Maxwell
and his colleagues in Chapter 1 could be utilized profitably in the
basin evaluation calculations of Weite, et al. and of Erdman. Further
it is clear that the detailed molecular analyses for both the soluble
fractions and the insoluble organic debris and the computer-based geo-
chemical and geophysical models can only improve in scope and sensi­
tivity and precision and - in consequence - in the scope offered for
better qualitative and quantitative assessment of the paleoenviron-
mental and burial histories of sediments. The implications go far
beyond the direct economic exploitation in petroleum exploration -
they bear on the fundamental roles of carbon in the earth1s crust
through geological time, as a reflection of the interplay of
biological, geochemical and geophysical processes.
Chapter 1
MOLECULAR CHANGES AND THE
MATURATION OF SEDIMENTARY
ORGANIC MATTER
A. S. Mackenzie, R. L. Patience and J. R. Maxwell
Organic Geochemistry Unit, University of Bristol,
Bristol BS8 ITS, UK
INTRODUCTION
One method for studying the sedimentary fate of organic matter is the
determination of the structures and distributions of compounds with an
obvious biological origin in sediments of all ages. In this approach -
the biological marker approach - it is envisaged that forming sediments
act as sinks for the natural products from algae, plants and other
organisms. Before reaching the sediments, this organic matter is ext­
ensively degraded by bacteria and other organisms, but a small propor­
tion of it becomes incorporated into the sediment, where further degra­
dation and alteration occur, for example by bacterial activity in the
sediment. These and other short term changes which occur before comp­
action and lithification are termed diagenetic changes. With increas­
ing depth of burial, the temperature rises and thermal and thermocata-
lytic reactions occur. A number of terms have been used to describe
these processes, but the term "maturation" is used here. Despite all
of these changes, the carbon skeletons of certain of the originally-
deposited natural products can be preserved in sedimentary rocks and
petroleum, either in whole or in part, as so called biological markers,
and their structures can be correlated witn likely precursor compounds
(e.g. Eglinton and Calvin, 1967).
At present a number of the methods used to determine the extent of
maturation of sedimentary organic matter rely extensively on measure­
ment of gross parameters. These methods have been used in petroleum
exploration studies and have been reviewed by Hood, et al. (1975)·
1
2 A. S. MACKENZIE, R. L. PATIENCE and J. R. MAXWELL
They include measurements of changes in (i) the reflectance of vitrin-
ite particles, (ii) colour and structure of organic debris - e.g.
plant pollen, (iii) electron spin resonance and infrared spectra of
kerogen, (iv) atomic H/C and 0/C ratios of kerogen, (v) the ratio of
solvent-extractable organic matter to total organic carbon (Hood, et
al., 1975, an(i references therein; Albrecht and Ourisson, 1969; Tissot,
et al., 1971, 1974-5 Ishiwatari, et al., 1977).
At the molecular level, a number of changes occur in the distributions
of hydrocarbons with increasing extent of maturation. These include
(i) a loss in the biological distribution, viz., the odd over even
preference, in n-alkanes (e.g., Bray and Evans, 1961; Philippi, 1965),
(ii) an increase in the relative abundance of n-alkanes as a result of
reactions such as decarboxylation and preferential generation from
kerogen (e.g., Albrecht and Ourisson, 1969), followed by a decrease in
n-alkane chain length and relative abundance of acyclic isoprenoid,
steroidal and triterpenoidal alkanes as a result of thermal cracking
of carbon-carbon bonds (e.g., Albrecht,et al., 1976), (iii) various
changes in the distributions of aromatic hydrocarbons (e.g., Tissot,
et al., 1971; Albrecht, et al., 1976). A variety of other reactions,
such as reduction of double bonds, are assumed to occur at various
stages on the maturation pathway, but these have not been studied in
detail. Recent extensions of a widely-used approach, determination of
the concentration and distribution of the Cp-C^ hydrocarbons formed by
thermal cracking, have shown the value of this method for determining
the extent of maturation in sediments (Thompson, 1979; Leythaeuser, et
al., 1979).
The transformations occurring within the structurally-specific biolog­
ical marker compounds have been examined in less detail, although such
studies are essential to determine their origins or, vice versa the
sedimentary fate of their precursor natural products. However, the
changes which occur in the configuration of the widely-occurring pent-
acyclic triterpanes of the hopane type are well documented. The pre­
ferred 17/#H,21/5H configuration (la) in the alkanes of immature sedi­
ments is lost in favour of the more stable 17/H,21/$H and 17/5H,21<xH
configurations (lb and II and Ic and III, respectively) presumably by
acid-catalysed epimerisation reactions (Ensminger, et al., 1974-5 Allan,
et al., 1977). In addition, the preferred configuration at C-22 (C-22R)
Maturation of Sedimentary Organic Matter 3
in extended (> 30 carbon atoms, e.g., I,R = Cpl·) is lost in favour
of mixtures of the R and S isomers, presumably because there is little
difference in stability between the two isomers at this position
(Ensminger, et al., 1974)· In a suite of related sediments from the
Paris Basin, these changes have been shown to occur with increasing
depth of burial (Ensminger, et al., 1977)· Thus, the triterpane dis­
tributions in mature sediments and petroleum are characterised by a
high relative abundance of hopanes with the stable 17<XH,21/6H configu­
ration (lb) in the range Cp^-CU,- with mixtures of the G-22 isomers in
the members >CU-, (e.g. II, R = CpRV) (e.g. Van Dorsselaer, et al.,
1974)· Similar changes appear to occur at the same positions in the
corresponding carboxylic acids (e.g. IV) (Ensminger, 1977)·
Va Vb
Among the acyclic isoprenoid alkanes, it has been shown that the pri-
stane in immature sediments is solely or mainly the 6(R), 10(S) (meso)
configuration (Va), which correlates with that of its presumed precur­
sor natural product, phytol (Vd) (Maxwell, et al., 1972; Patience, et
al., 1978). In contrast, mature sediments and petroleum are charact­
erised by a random mixture of the three possible isomers (Vabc) in a