A New North Sea Oil-Based Standard For Iatroscan Analysis

i ;
' Mobile and immobile migrated

hydrocarbons in the Embla Field,
i North Sea
o
Faculty of Applied Earth Sc%#c8 anfl Petroleum Engineering

The Norwegian University of Science and Technology
Trondheim, Norway ^
NTNU
I Dr. philos. thesis
DISCLAIMER
Portions of this document may be illegible

in electronic image products. Images are
produced from the best available original
document.
Mobile and immobile migrated hydrocarbons in
the Embla Field, North Sea
Sunil Bharat:
a thesis accepted by
The Faculty of Applied Earth Science and Petroleum Engineering
Norwegian University of Science and Technology (NTNU)

Trondheim, Norway
for public defense in partial fulfillment of the requirements for

the Norwegian academic degree
dr. philos
December, 1997
ISBN 82-7861-089-4
© by Sunil Bharati March 1998.
Printed in Norway
by Tapir, Trondheim.
To my mother andfather,
for always hoping
and to my wife,
for keeping that hope alive.
Contents i
Contents
Preface ........................................................................................................... v
Executive Summary .............................................................................. vii
Chapter 1:
Introduction 1
Chapter 2 : Paper 1
Identifying diverse oil families in the Greater Ekofisk area, North Sea.
Bharati, Hall and Bjor0y - under submission.
2.1 Abstract ........................................................................................ 7
2.2 Introduction .............................................................................. 8
2.3 Samples and methods ..................................................................... 8
2.4 Geological setting ..................................................................... 10
2.5 Maturity variations ..................................................................... 10
2.6 Source facies variations ............................................................ 15
2.7 The Greater Ekofisk oil families .................................................. 20
2.8 Conclusions .............................................................................. 22
2.9 Acknowledgments 23
2.10 References .............................................................................. 23
Chapter 3: Paper 2
Geochemical evaluation of the Embla field, Norwegian Continental Shelf - 1:
Occurrence and compositional variations of migrated hydrocarbons.
Bharati, Hall, Wagle and Bjorpy - under submission.
3.1 Abstract ........................................................................................ 25
3.2 Introduction .............................................................................. 26
3.3 Geological elements and field history ......................................... 27
3.4 Samples and methods ..................................................................... 31
3.5 Mineralogical composition of reservoir sandstones ...................... 33
3.6 Abundance of migrated hydrocarbons ......................................... 34
3.7 Variations in hydrocarbon composition across the field ............ 38
3.8 Molecular characteristics ............................................................ 40
3.9 Discussion......................................................................................... 45
3.10 Summary and conclusions ............................................................. 52
3.11 Acknowledgments ...................................................................... 53
3.12 References......................................................................................... 53
Norwegian University ofScience and Technology

ii Mobile and immobile migrated hydrocarbons in the Embla Field, North Sea
Chapter 4: Paper 3
Geochemical evaluation of the Embla field, Norwegian Continental Shelf - 2: Source,
infilling, and intra-reservoir communication.
Bharati, Hall, Wagle and Bjor0y - under submission.
4.1 Abstract ......................................................................................... 55
4.2 Introduction ................................................................................ 56
4.3 Geological background ............................................................. 56
4.4 Samples and methods ............................................................. 57
4.5 Maturity of the Embla oils ............................................................. 58
4.6 Source of the Embla oils ............................................................. 64
4.7 Possible filling directions ............................................................. 72
4.8 Trap boundaries and communication .......................................... 76
4.9 Field productivity: implications of OWC and bitumen occurrence .. 77
4.10 Summary and conclusions ............................................................. 78
4.11 Acknowledgments ...................................................................... 79
4.12 References ................................................................................ 80
Chapter 5: Paper 4
Solid reservoir bitumen in the Embla Field, Norwegian Continental Shelf -1:
Occurrence, development and morphotypes.
Bharati - under submission.
5.1 Abstract ........................................................................................ 83
5.2 Introduction .............................................................................. 84
5.3 Geological background ............................................................ 85
5.4 Reservoir bitumen: the less understood phase ..................... 87
5.5 Occurrence and types of bitumen in the Embla Field ............ 88
5.6 Morphotypes of Embla bitumen .................................................... 94
5.7 Minerals in inter-granular space .................................................. 100
5.8 Summary and conclusions 106
5.9 Acknowledgments ..................................................................... 106
5.10 References .............................................................................. 106
Chapter 6: Paper5
Solid reservoir bitumen in the Embla Field, Norwegian Continental Shelf -2:
Chemistry, structure and origin.
Bharati - under submission.
6.1 Abstract ......................................................................................... 109
6.2 Introduction ................................................................................ 110
6.3 Geological background ............................................................. 110
6.4 Samples and methods ............................................................. 110
6.5 Embla solid bitumen composition .......................................... Ill
6.6 The nature of carbon in the Embla bitumens ................................. 114
6.7 Internal structure of the bitumen phase 116
6.8 Timing of bitumen formation .................................................... 118
6.9 Causes of bitumen formation .................................................... 127
6.10 Paleo-oil emplacement and destruction in Embla: A hypothesis .... 131
6.11 Implications of solid bitumen in the Embla Field ....................... 132
Doctoral Dissertation by Sunil Bharati, 1997

Contents iii
6.12 Summary and conclusions 133

6.14 References ................................................................................ 134
Chapter 7: Paper 6
Calibration and standardization of Iatroscan (TLC-FTD) using standards derived from
crude oils.
Bharati, R0stum and L0berg -1994, Organic Geochemistry, v. 22, p. 835-862.
7.1 Abstract .......................................................................................... 141
7.2 Introduction ................................................................................. 142
7.3 Analytical procedures .............................................................. 144
7.4 Results and discussion .............................................................. 145
7.5 Summary and conclusions .............................................................. 167
7.7 References ................................................................................. 168
Chapter 8 : Paper 7
A new North Sea oil based standard for Iatroscan analysis.
Bharati, Patience, Mills and Hanesand -1997, Organic Geochemistry, v. 26, p. 49-57.
8.1 Abstract ......................................................................................... 171
8.2 Introduction ................................................................................ 172
8.3 Analytical procedures ............................................................. 172
8.4 Results and discussion ............................................................. 173
8.5 Conclusions 179
8.6 References ................................................................................ 180
Chapter 9: Paper 8
Elucidation of the Alum Shale kerogen structure using a multi-disciplinary approach.
Bharati, Patience, Latter, Standen and Poplett -1995, Organic Geochemistry, v. 23, p.
1043-1058.
9.1 Abstract .......................................................................................... 181
9.2 Introduction ................................................................................. 182
9.3 Samples and geology 182
9.4 Analytical methods 184
9.5 Results .......................................................................................... 185
9.6 Discussion ................................................................................. 193
9.7 Conclusions ................................................................................. 196
9.8 References ................................................................................. 196
—Q—Q—Q—Q—0~-0—"*0”"0——

Preface v
Preface
Statistically, this is yet another of more than hundred doctoral theses submitted to the
Norwegian University of Science and Technology (NTNU), however personally it is
gratifying. Not just because this thesis represents a finished product, but because the road to
this thesis was educating and it gave me an opportunity to make a contribution to science.
Petroleum is the principal source of energy and each one of us uses at least one of its derived
products daily; and it is likely that petroleum will maintain this status well beyond the next
decade. However, the net petroleum quantity is limited in nature and as our needs multiply,
our efforts must be directed towards utilizing this resource efficiently and prudently. An oil
explorationist has in addition, another paramount responsibility- that of finding more oil
reserves, particularly those which can be commercially developed. As most of the ‘easily’
identifiable fields in the current petroleum provinces of the world have already been
discovered, the current technology is directed more towards finding structures which were
relatively ‘invisible* until now. Another strategy being pursued today is to re-define past
discoveries using modem methods with a view to increasing their proven reserves and
improve recovery factor. Such a strategy requires a thorough understanding of the reservoir
system, the migration pathways and the source of the oil in question. Undoubtedly, such an
exercise demands a multi-disciplinary approach and application of new data.
The work reported in this thesis attempts to embrace this strategy using a wide variety of
organic geochemical data. The studied field, Embla, has proven to be an excellent example to
apply some of the newer ideas in Reservoir Geochemistry and has in addition provided a
sample set, unique to the North Sea in many ways. Although the Embla Field is in one of the
most prolific regions of the Norwegian Continental Shelf, the Central Graben, its petroleum
population is significantly different from neighbouring fields in more than one way. It is my
hope that the data generated and the conclusions reached in this study prove useful towards a
better understanding of the migrated hydrocarbons and form an effective database to plan
Embla’s future development. This was my ultimate goal of undertaking this work.
Achieving this goal has not been without impediments. While more than the last four years of
work has been immensely educating and rewarding, it was not without setbacks and
disappointments. Having a full-time job during this period (most of the reported work was
done in my private time) and no formal supervisor for this study slowed the progress. Not
being able to obtain proper and adequate funding and dependency on only private resources
was also a major setback. Fortunately, partial funding was obtained from three sources - The

vi Mobile and immobile migrated hydrocarbons in the Embla Field, North Sea
Norwegian Research Council (NFR), Phillips Petroleum Co. Norway and Amoco Norway. To
these organizations, I owe deepest thanks.
Philips Petroleum is especially thanked for providing samples and permission to publish. Its
co-venturers, including Fina Exploration Norway SCA, Norske Agip AS, Elf Petroleum Norge
AS, Norske Hydro Production AS, Statoil AS, Total Norge AS and Saga Petroleum AS are
also acknowledged for permission. My employer, Geolab Nor, is also thanked for giving
permission to pursue this study.. Last but not the least, I owe my gratitude to the Department
of Geology & Mineral Resources Engineering, NTNU for providing office facilities for more
than a year and constant support to complete my thesis.
Several people from various walks of life have played a major role in assisting me in one way
or the other to complete the task I had undertaken. First and foremost, I thank my parents for
making me capable of seeing this day and my wife, Sangeeta, who endured me uncondi
tionally. On the more professional front, my particular thanks to: Kare Vagle (Phillips
Petroleum) for constant interest and discussions; Joe Curiale (Unocal, USA) for reviewing
early drafts of papers 4 & 5, Richard Patience (Statoil) for reviewing early drafts of papers 2
& 3 and Chip Feazel (Phillips Petroleum) for final corrections; Peter B. Hall (Geolab Nor) for
sharing my thoughts and introducing new ideas; Malvin Bjor0y (Geolab Nor), Girish Saigal
and Idar Horstad (both Saga Petroleum) for several informal discussions and advice; Geolab
Nor staff (several geochemical analyses), Kjell Muller and Morten Raanes (SEM), Prof. John
Attard and Winfried Kuhn (NMR), Prof. Ragnvald H0ier and Sigmund Andersen (TEM), Ivar
R0mme (XRD) for assistance in analyses. Several figures were drawn by Anne Irene
Johannessen. I would also like to extend my sincere thanks to Prof. Elen Roaldset for
providing the appropriate platform to complete my work and taking interest in my work.
I apologize to my daughter, Shipra, for all those missed weekends and evenings.
Last, thanks to planet Earth, for providing both rocks and oil!
Sunil Bharati
Trondheim, Norway
December, 1997

Executive Summary vii
Executive Summary
Based on geochemical analyses of a suite of 68 oils from 16 fields of the Greater Ekofisk
area, Norwegian Continental Shelf, it became apparent that the Embla oils were outliers with
respect to composition and maturity. While most Greater Ekofisk oils are emplaced in
Cretaceous chalk reservoirs, the Embla oils besides being the most mature, are trapped in
Paleozoic sandstones. In addition to the oils becoming steadily more mature from Hod and
Valhall in the southeast to Albuskjell in the northwest, two principal source facies have played
a major role with respect to regional generation. The one which has sourced majority of the
Cretaceous chalk reservoired oils is isotopically light and the other which has sourced the pre-
Cretaceous sandstone reservoired oils is isotopically heavy and anomalously enriched in
isoprenoids.
A detailed investigation of the Embla reservoir and its petroleum population was carried out
with the following objectives: evaluate migrated hydrocarbons with respect to composition,
maturity, intra-reservoir communication, compartmentalization and filling history of the field;
characterize, map and explain the presence of immobile solid reservoir bitumen phase (paleo-
oil) and discuss its origin and implications on overall reservoir quality.
Wide-ranging geochemical investigations (XRD, RE, Iatroscan, GHM, GC, GC-MS, GC-
IRMS, bulk isotopes etc.) using a suite of >900 core samples and six oils from Embla,
revealed that the field is highly complex. The Embla reservoir, consisting of the Uppermost,
Upper and Lower Sandstones of yet unknown ages, contains two distinct types of oil, A and
B, although both the oils are very light. The Upper Sandstone, with well developed porosity, is
richer in hydrocarbons but also relatively non-homogenous, when compared to the Lower
Sandstone. This, in all likelihood, is due to extensive asphaltene-rich solid bitumen in the
latter. The two oil types differ slightly in composition and maturity, due to two kitchens
feeding the reservoir, although both oils are highly mature. Compositionally, the signature of
migrated petroleum changes both horizontally across the various traps and vertically with
increasing depth. This is particularly evident in the Lower Sandstone traps LSI and LS2, where
the relative non-hydrocarbon percentage increases dramatically with depth.
With regards to maturity, oil type A is slightly less mature than oil type B. This is based more on
the aromatic hydrocarbon based maturity ratios than on biomarker based ratios, as the latter are
considered less reliable due to high maturity of the oils. However, both oil populations have been
generated by the ‘abnormal’ Upper Jurassic organic facies, characterized by isotopically heavier
n-alkanes and in particular, anomalous enrichment of isotopically very heavy isoprenoids. The

viii Mobile and immobile migrated hydrocarbons in the Embla Field, North Sea
two oil charges are believed to have been from the west and/or north-west, where the kitchen for
the Embla oils is estimated to lie. Minimal or no mixing of the two oil charges has taken place in
the Embla reservoirs, suggesting that the individual traps have been well isolated prior to and
since oil emplacement. Generation and migration of Embla oils from the east (of Skrubbe Fault)
or locally occurring Upper Jurassic units is thought to be unlikely.
The data from the present study indicate that the Embla Field is highly compartmentalized and
the individual fault blocks are not in communication, either laterally or vertically. The fact that
during the last five years of production from Embla no pressure communication was observed,
supports this finding. Perhaps this is also the reason why the oil-water contacts (OWC) occur at
different depths in different traps, the difference being to the extent of about 200 m. The OWC is
found to be shallowest (estimated ‘oil down to’ 4325 m TVDSS) in well 21S (trap LSI) and
deepest (+4548 m TVDSS) in well 26S (trap LS2); in wells 23S/27S (trap UM2) it is estimated
to be in between (>4400 m TVDSS). The deep OWC in LS2 has serious implications with
respect to future exploration and opens up the possibility of more oil occurring NW and SE of
well 26S, provided the sand body with good reservoir properties extends in these directions.
Interference from oil-based mud contaminants is quite severe in nearly the entire core sample
suite, which has restricted detection of underlying differences in the Embla oil population. In
particular, the abundance data is thought to have been most adversely affected. While this
problem cannot be avoided in the case of Embla Field, it should not be overlooked or
underestimated. Neither should this problem become the reason for discarding all data or not
reaching rational conclusions which are based on established principles and previously
published works. It was possible to establish the gross differences based on a combination of
various techniques. The data from the present study suggests that the order of richness of various
traps is: UM2 (richest), US2, UM1, LS3, LSI and LS2 (relatively least rich).
The lower part of the reservoir, particularly the Lower Sandstone, has a high content of solid
reservoir bitumen (a condensed, dichloromethane insoluble and highly aromatic carbon
phase). This very high TOC, black and vitreous phase is at the present day emplaced as an ‘oil
cement’, reducing severely the bulk porosity and permeability of the host rock. Solid bitumen
also represents the immobile and permanently lost phase of migrated hydrocarbons. Extensive
NMR, SEM and TEM examination shows that a variety of morphotypes are present, each
having unique topographical properties, which are controlled more by the pore space geometry
than composition. The bitumen occurs in a variety of modes such as filled cavities, open vugs,
veins, fractures, carpet and disseminated. Each habitat of occurrence is characterized by
special and unique properties, which have become the basis of classifying the Embla bitumens
into different morphotypes, namely 1) massive (consisting of types A, B & C), 2) spheroidal,
3) rosette, 4) foliated (types A & B), 5) zygotic, 6) vein, 7) carpet and 8) disseminated.

Executive Summary ix
Further investigation of the pore space and related diagenetic minerals showed that some
minerals (barite and pyrite) are almost exclusively associated with the bitumen phase, perhaps
representing the aqueous phase of petroleum. Its insolubility in organic solvents, low H/C ratio
and high aromaticity indicate its condensed nature and large molecular size, although partially
contradicting data is obtained by Py-GC. More than 30% of all carbon in the Embla bitumen is
found to be aromatic ring carbon and aliphatic carbon is a minor component. Detailed
examination of bitumen samples by SEM and TEM indicates that the process of bitumen
solidification was slow, controlled and methodical and post-date all the major diagenetic
events such as kaolinite precipitation and quartz cementation. The actual cause of bitumen
formation is not entirely clear in the case of Embla, but deasphalting may have played an
important role. While the original precursor of the solid bitumens is believed to have been a
free-flowing and perhaps a ‘normal’ oil, its immediate precursor is thought to have been a
viscous phase, rich in asphaltic species and with limited mobility and limited labile
components. The present oil population is not related to the solid bitumen and represents an
entirely independent oil charge.
The top of the bitumen zone has been established in all five wells studied based on visual
examination of cores and pyrolysate compositions. Apparently, the depth of bitumen
occurrence is variable across the field and independent of oil water contacts and evidently the
overall bitumen abundance increases with increasing depth. Solid reservoir bitumen
occurrences are known to have detrimental effects on the overall reservoir properties. Proper
understanding and mapping of the such occurrences and the geochemical assessment and
filling history of the petroleum charge in the Embla Field has allowed a better understanding
of the recoverable reserves and future field development and production strategy.
New calibration and analytical methods (Iatroscan analysis and carbon characterization by
NMR) were also developed during the course of the study.
The TLC-FTD technique, using the Iatroscan instrument, has now become a widely used and
reliable method for characterization of solvents extracts and crude oils. Due to limited
reported research, a study was specifically aimed at identifying, separating, characterizing,
testing and developing a standard, derived from crude oil(s), that is well suited for
quantification purposes. This was performed successfully using a suite of 30 crude oils from
world-wide basins, ranging in maturity and composition. Response factors calculated from
crude oil based aliquots differed significantly from synthetically prepared standards, proving
thereby a greater validity of the former. Subsequently, based on the established method and
principles of the pilot study, a new Iatroscan calibration standard was made from the North
Sea Oil-1 from the Oseberg field, as this oil was chosen by the Committee for the Norwegian
Industry Guide to Organic Geochemical Analyses to serve as a standard for other analytical
techniques. The composition of the gravimetrically prepared standard was kept comparable to

X Mobile and immobile migrated hydrocarbons in the Embla Field, North Sea
the original oil. Employment of this standard by different laboratories has made the
comparison of inter-laboratory Iatroscan analyses data more reliable.
The second method tested during the course of the study and prior to analysis of Embla
samples, was characterization of organic carbon using 13C CP/MAS NMR technique. Using a
suite of some Scandinavian source rock kerogens, the nature of organic carbon was described
with respect to gross aromaticity, various carbon types and functional groups present in the
complex carbon structure. Describing and understanding the structural features of kerogen and
naturally occurring asphaltic molecules has historically been a difficult subject and to an
extent enigmatic, primarily due to analytical limitations to resolve the complex structures. The
NMR technique, as used in the study, has allowed a greater latitude towards understanding
and elucidating the structural elements that comprise kerogen and coals, or solid bitumen as in
the case of Embla, by way of semi-quantitatively assessing the carbon-carbon, carbon-
hydrogen and carbon-oxygen bonds.

Introduction 1
Chapter 1
Introduction
The North Sea, particularly the Central Graben, is the cornerstone of Norwegian petroleum
industry. The Central Graben, which is endowed with several major oil fields, is also the
region where Norwegian oil exploration activity was initiated in mid-60s, leading to discovery
of the first Norwegian oil field, Ekofisk, in 1969 (Feazel et al., 1990). Despite the discovery of
several major structures in the last three decades or so, active exploration for satellite fields
and reassessment of proven structures using modem technologies continues today. This is
important in the light of changed socio-economic conditions and increasing oil production
costs. However, proper understanding of the sub-sea structures and the fluids contained
therein requires synthesis of several types of data, which were regarded as independent of
each other until a few years ago. In addition, newer types of data sets are now recognized to
play a vital role in achieving a proper definition of oil & gas reservoirs. One such example is
organic geochemical data, particularly from the pay-zones and reservoir sections.
While Organic Geochemistry as a science was well established in the 1950s, it was mostly in
relation to source rocks (e.g. Hunt and Jamieson, 1956) and geared towards source potential
and maturity. Its application to reservoirs and their fluids, however, is relatively recent with
most of the pioneering work being done by England and co-workers (e.g. England and
Mackenzie, 1989). Reservoir Geochemistry has since been tested and applied by several
schools worldwide and is guided by one key observation that reservoir fluids (water and
petroleum) are often compositionally heterogeneous, both laterally across the field and
vertically down the reservoir. These variation trends can be, amongst other things,
extrapolated to the kitchen areas where the oil population is believed to have been generated.
Such an application gains significance particularly because wells are typically drilled in the
structural highs and not the basinal areas where the source rocks may be located. Moreover,
concepts such as a field’s filling history and migration pathways have become clearer with the
introduction of modem geochemical databases.
It is with this background that the present study was undertaken using more than 1000 core
samples from several wells and about 100 oils from several fields. The analytical techniques
applied include screening (TOC, Rock Eval, Iatroscan, thermal extraction-pyrolysis-gas
chromatography- TE-PY-GC, XRD), follow-up (liquid chromatography - MPLC, capillary gas
chromatography - GC, gas chromatography-mass spectrometry - GC-MS, compound specific

2 Mobile and immobile migrated hydrocarbons in the Embla Field, North Sea
isotope ratio-mass spectrometry - GC-IRMS, bulk 13C isotopes, elemental analysis, chemical
degradation) and optical (stereo microscopy, scanning electron microscopy - SEM,
transmission electron microscopy - TEM). The wide variety of this large geochemical database
is presented in this thesis in the form of eight papers, three of which are already published and
the rest are under submission.
The Greater Ekofisk region, with sixteen major oil fields, has been shown to comprise highly
variable oil families. This variation has been attributed to both source facies (Northam, 1985;
Forsberg et al., 1993) and maturity (Hughes et al., 1985; Bjor0y et al., 1994). As the number
and variety of oil samples available from this area far exceeds those typically encountered, the
Central Graben serves as a useful natural laboratory. However, most workers concentrated
mainly on the Cretaceous Chalk reservoired oils from the area, as these are the principal pay-
zones (Tor, Hod and Ekofisk Formations). Not much thought was given to the possibility of
pre-Cretaceous plays, mainly due to their greater depth in most regions. The general
conception was that if any petroleum was present in these deeper prospects, it would at best be
gas or gas/condensate. This view changed sometime in the late 1980s with the discovery of oil
in some Jurassic and pre-Jurassic clastic sequences.
Geochemical data on the pre-Cretaceous oils is scarce. It was with this idea that a pilot study
was undertaken to identify the different oil families in the Greater Ekofisk region, with
emphasis on comparison of Cretaceous Chalk reservoired oils to pre-Cretaceous sandstone
reservoired oils. The findings are reported in Paper 1 “Identifying diverse oil families in the
Greater Ekofisk area, Central Graben, Norwegian Continental Shelf’. While significant
maturity variations within the Cretaceous oils was reported earlier (Hughes et al., 1985;
Bjor0y et al., 1994), this paper addresses the issue from a slightly different perspective using
GC-IRMS fingerprinting. This study also revealed how different the Jurassic and pre-Jurassic
reservoired oils are from Cretaceous oils, from the point of view of not just maturity but also
the source facies. This pilot study formed the basis of studying the pre-Cretaceous reservoired
oils, particularly those from Embla where extensive coring was performed and which was
considered to be structurally complex.
The Embla Field is the only major field in the Central Graben with pre-Cretaceous reservoirs.
In addition, it has one of the deepest reservoirs of the region - exceeding 4 km. Several factors
are responsible for undertaking a detailed geochemical evaluation of the Embla Field: a) it was
relatively a new discovery, b) preliminary RFT data pointed towards the possibility of
compartmentalization, c) extensive core samples were available, including from those wells
which were only recently completed and d) it was different from neighbouring fields in most
respects. The basic geochemical data with respect to richness and composition is presented in
Paper 2 “Geochemical evaluation of the Embla field, Norwegian Continental Shelf - 1:
Occurrence and compositional variations of migrated hydrocarbons”. This paper also
Doctoral Dissertation by Simil Bharati, 1997

Introduction 3
covers the internal variations (laterally across the field and vertically down the reservoir)
observed in the signature of migrated hydrocarbons. The geochemical data is interpreted in the
light of available petro-physical data. As it was found that the migrated hydrocarbons in the
reservoir units are heterogeneous, a closer look into their maturity and possible source
variations was necessary. This aspect is addressed in Paper 3 “Geochemical evaluation of
the Embla field, Norwegian Continental Shelf - 2: Source, infilling, and intra-reservoir
communication”. In addition, this paper also discusses interpreted compartmentalization and
estimates the locations of oil-water contacts in various parts of the field based on geochemical
data. Various oil-charge scenarios and their implications are presented in the light of available
source rock data.
During the course of this study, another phenomenon was observed in sandstones of yet
undetermined age comprising the Embla reservoirs: extensive occurrence of solid reservoir
bitumen. Such an occurrence, particularly from the abundance point of view, has not yet been
reported in the North Sea. Initially, it was thought to be and termed ‘pyrobitumen’. All the
cores were re-examined with an aim to obtain a clearer picture and to re-sample portions
which were rich in solid bitumen. As this solid bitumen was insoluble in common organic
solvents, its characterization became limited to bulk and optical methods. The preliminary
examination of solid bitumen using mainly scanning electron microscopy (SEM) is presented
in Paper 4 “Solid reservoir bitumen in the Embla Field, Norwegian Continental Shelf -1:
Occurrence, development and morphotypes”. This paper also discusses current beliefs
about this less understood organic phase. Detailed examination of several samples from across
the field reveal that this is not a randomly present phase, but occurs in a methodical manner
and in a variety of forms, shapes and morphology. The sheer magnitude of its occurrence in
Embla demanded a closer look with regards to its chemistry, structure and origin. These
aspects, based mostly on available optical evidence and geological data are reported in Paper
5 “Solid reservoir bitumen in the Embla Field, Norwegian Continental Shelf -2:
Chemistry, structure and origin”. The bulk techniques used to understand this immobile
migrated hydrocarbon phase included pyrolysis-gas chromatography (PY-GC), elemental
analysis, nuclear magnetic resonance spectroscopy (NMR) and transmission electron
microscopy (TEM). Several possible causes for its emplacement are discussed and a possible
hypothesis on its origin presented, in light of observed evidence. Its implication on reservoir
quality and its relationship to the present mobile (producible) oil phase is also discussed.
During the course of this study, some newly established methods in geochemistry were also
utilized, namely Iatroscan and carbon type analysis using NMR. Although not directly related
to the main Embla sample set, these findings are reported in the last three papers. Their
relevance lies in the fact that data generated through these two techniques has proved to be of
immense use in reaching the conclusions the main Embla study.

The TLC-FTD technique, using the Iatroscan instrument, which constitutes separation and
quantification of a complex mixture such as crude oil or solvent extract, has recently become a
widely used and reliable method in the oil industry. Therefore its correct calibration is of great
importance, an aspect which was not adequately addressed. The first of the two papers on
Iatroscan, Paper 6 “Calibration and standardization of Iatroscan (TLC-FID) using
standards derived from crude oils”, mainly aims to develop a standard for correct
calibration of the instrument. This was achieved using a sample set of 30 crude oils from
several basins of the world, covering a wide range in maturity, API gravity, source rock type,
degree of biodegradation, reservoir rock type and composition. A reliable standard with a high
degree of reproducibility was thus created. Immediately thereafter, the Committee for the
Norwegian Industry Guide to Organic Geochemical Analyses (NIGOGA) decided that an oil
from the Oseberg Field (NSO-1) be used as a standard for analytical techniques such as liquid
chromatography, gas chromatography and gas chromatography-mass spectrometry. In light of
this development, it was logical to develop the new Iatroscan standard based on the Oseberg
oil. This is reported in the second Iatroscan related paper, Paper 7 “A new North Sea oil
based standard for Iatroscan analysis”. Since its development, the new Iatroscan standard
has been recognized as the only 'officially accepted' standard for all Iatroscan analyses.
Paper 8 “Elucidation of the Alum Shale kerogen structure using a multi-disciplinary

approach” applies the technique of carbon-type analysis of kerogens proposed by Mann et al.
(1991) and uses the Alum Shales from Sweden as a test case. This paper also demonstrates the
practical utility and validity of integrating data obtained from a variety of analytical techniques
to understand, elucidate and model kerogen* s complex chemical structure. Although this study
is only peripherally related to the main substance of the thesis and used isolated kerogens from
a Scandinavian source rock as the sample suite, the principles and methodology developed
proved to be useful in understanding the nature of carbon of the Embla solid reservoir
bitumens. This is paper is also included in this thesis for the sake of completion and to serve
as a ready reference on this subject to readers.
As it has been attempted to make each of the eight papers complete by itself and independent
of each other, each paper carries its own summary and conclusions. This thesis therefore has
no common conclusion at the end.

Introduction 5
References
Bjor0y, M., Hall, K. and Moe, R. P., 1994, Stable carbon isotope variation of n-alkanes in
Central Graben oils, Organic Geochemistry, v. 22, p. 355-381.
England, W. A. and Mackenzie, A. S., 1989, Geochemistry of petroleum reservoirs: Geologische

Rundschau, v. 78, p. 291-303.
Feazel, C. T., Knight, I. A. and Pekot, L. J., 1990, Ekofrsk Field-Norway, Central Graben,
North Sea, in E. A. Beaumont and N. H. Foster, eds., Structural Traps IV, Treatise of
Petroleum Geology, Am. Asso. of Pet. Geol., Tulsa: p. 1-26.
Forsberg, A., Gowers, M. B. and Holtar, E., 1993, Multi-disciplinary stratigraphic analysis of
the Upper Jurassic strata of the Norwegian Central Trough, in A. M. Spencer, ed., Generation,
accumulation and production of Europe’s hydrocarbons HI: Springer-Verlag, Berlin, p. 45-58.
Hughes, W. B., Holba, A. G., Miller, D. E. and Richardson, J. S., 1985, Geochemistry of Greater
Ekofisk oils, in B. M. Thomas et al„ eds., Petroleum Geochemistry in exploration of the
Norwegian Shelf: Graham & Trotman, London, p. 75-92.
Hunt, J. M. and Jamieson, G. W., 1956, Oil and organic matter in source rocks of petroleum:
AAPG Bulletin, v. 40, p. 477-488.
Mann, A. L., Patience, R. L. and Poplett, I. J. F., 1991, Determination of molecular structure
of kerogens using 13C NMR spectroscopy: I. Effects of variation in kerogen type: Geochimica
Cosmochimica Acta, v. 55, p. 2259-2268.
Northam, M. A., 1985, Correlation of northern North Sea oils: the different facies of their
Jurassic source, in B. M. Thomas et al., eds., Petroleum Geochemistry in exploration of the


Paper 1: Diverse oilfamilies in the Greater Ekofisk area, Central Graben, Norway 7
Chapter 2 : Paper 1
Identifying diverse oil families in the Greater Ekofisk area,

Central Graben, Norwegian Continental Shelf§
Sunil Bharati, Peter B. Hall and Malvin Bjor0y
Geolab Nor, N-7002 Trondheim, Norway
2.1 Abstract
The Central Graben in the North Sea is one of the most prolific petroleum basins of the world
and the cradle of Norwegian petroleum exploration and production. The many oil and
condensate fields that this area is endowed with, including Norway’s first commercial field,
Ekofisk, vary significantly with respect to petroleum composition and maturity. Using a
sample suite of 68 oils from 16 oil fields in the Central Graben area, the main compositional
and maturity differences between the Cretaceous chalk reservoired oils (found in majority of
the fields) to pre-Cretaceous sandstone reservoired oils (Embla and wells 19R and 3X) have
been exemplified. A wide-ranging geochemical database of whole oils (gas chromatography,
bulk carbon isotopes, compound specific isotope ratios and biomarkers) was used to meet the
objectives of the study. In addition to the oils becoming steadily more mature from Hod and
Valhall in the southeast to Albuskjell in the northwest, two principal source facies have played
a major role with respect to regional generation. The one which has sourced majority of the
Cretaceous chalk reservoired oils is isotopically light (represented by the Edda oil end-
member) and the other which has sourced the pre-Cretaceous sandstone reservoired oils is
isotopically heavy and anomalously enriched in isoprenoids (represented by the 3X oil end-
member). These data were also used to define the diverse oil families on a regional scale in the
study area.
5 Manuscript under submission to Marine and Petroleum Geology

2.2 Introduction
The discovery of Groningen in 1959, the giant gas field in the Netherlands, triggered oil
exploration in Norway and the first well in the North Sea was drilled a decade later (well 2/4-
IX by Phillips Petroleum). Due to technical problems, this well was abandoned and a second
well, the Phillips 2/4A-1X, was drilled immediately thereafter, which was the first discovery
well of Norway (Feazel et al, 1990). Since then, the Central Graben in the North Sea has
proved to be one of the most prolific petroleum basins of the world, with several giant
discoveries. This is primarily due to thick sections of Upper Jurassic shales, which are
considered to be the principal source of most petroleum systems in the region, being deeply
buried in this region (Cooper and Barnard, 1984). Varying depths of burial and organic facies
(Bailey et al., 1990) have generated oils differing from the composition and maturity point of
view. This aspect has been addressed to some extent by Hughes et al. (1985) using a suite of
30 chalk reservoired Greater Ekofisk oils. Bjor0y et al. (1994) have also studied the Central
Graben oils using primarily the GC-IRMS technique to conclude that internal differences
occur within the Cretaceous chalk reservoired oils.
The objective of this paper, however, is mostly to highlight the differences between the Creta
ceous chalk reservoired oils to pre-Cretaceous sandstone reservoired oils, in addition to identi
fying the diversity of oil families with respect to composition and maturity in the Greater
Ekofisk area. Only broad and regional properties and differences between the oils have been
considered, as it is not the aim of this study to highlight the fine and subtle differences within
a field, but discriminate one field from the other and model the oil families on a regional scale.
2.3 Samples and Analytical Methods
To meet the objectives of this study, we have used a suite of 68 oils from 16 oil fields (Table
1) - from Albuskjell in the north to Gert in the south, the latter being on the Norwegian-Danish
border (Figure 1).
Topped oils were deasphaltened using excess (lOx by volume) n-hexane, filtered and
separated into saturated and aromatic hydrocarbons and polar fractions using MPLC. Whole
oil aliquots were analyzed by:
1) Capillary gas chromatography using a Perkin Elmer Sigma 2000 GC equipped with FED
and FPD detectors and using a SE-54 column (25m, 0.20 mm i.d., 0.1 pm film thickness)
under pre-programmed temperature conditions (initial -10 °C for 2 min, then to 300°C at
4°C/min, final hold time 15 min).

Afcuskjen
Ekofisk
TommeBlen Gamma Ekofisk
EldfisJc Bravo
2/7-19R
Valhall
EMBLA
Figure 1: Map showing the location of the Greater Ekofiskfields included in this study.
2) Stable carbon isotope ratio measurement using a VG SIRA 10 mass spectrometer. Combus
tion is performed by a Carlo Erba EA 1108 element analyzer (This analysis was also
performed on saturated, aromatic and polar fractions).
3) Gas chromatography-isotope ratio-Mass spectrometry (GC-IRMS) using a VG Isochrom II
system interfaced to a Dani 8510 gas chromatograph fitted with a OV-1 column (50m, 0.32
mm i.d.). The GC was operated under pre-programmed temperature conditions (initial 50
°C for 2 min, then to 300°C at 4°C/min, final hold time 20 min). Isotope ratio calculations
were performed using CO2 as a reference gas.
4) Gas chromatography-Mass spectrometry (GC-MS) using a VG TS250 system interfaced to
a HP 5890 gas chromatograph, the latter fitted with a SE 54 column (40m, 0.22 mm i.d.).

The GC was operated under pre-programmed temperature conditions (for saturated

hydrocarbons: initial 45 °C to 150 °C at 35°C/min, then to 310°C at 2°C/min, final hold
time 15 min; for aromatic hydrocarbons: initial 50 °C to 310 °C at 5°C/min, final hold time
15 min; for). The mass spectrometer is operated in electron impact (El) mode at 70 eV, a
trap to current of 500 |iA and source temperature of 220°C.
5) A selected suite of saturated and aromatic hydrocarbon fractions (39) were also subjected
to gas chromatography (GC). A Perkin Elmer 8320 equipped with an FED and an OV1
column (25 m, 0.25 mm i.d.) was used for the saturated hydrocarbons with a temperature
program of 80-300°C at 4°C/min (final hold time 20 min). For the aromatic hydrocarbons, a
Varian 3400 equipped with a split injector, FID and FPD and SE54 column (25 m, 0.25
mm i.d.) was used. The temperature program was 40-290°C at 4°C/min (final hold time 10
min).
2.4 Geological setting
This has been described in detail in several previous publications (e.g. Van den Bark and
Thomas, 1981; Gowers and Saebpe, 1985; Fraser et al., 1993). Briefly, the Central Graben
comprises of a series of en echelon normal and strike slip faults initiated in the Triassic period
and active through the Mesozoic era. Graben subsidence continued during the Jurassic and
Early Cretaceous periods, along with associated fault inversions thus creating local highs and
basins. Halokinesis of thick Permian evaporites further complicated the structural and
sedimentological evolution of the graben. Restricted basinal conditions which prevailed during
the Late Jurassic period resulted in thick organic-rich shales (the Mandal / Farsund
Formations), the major petroleum source for the area. Widespread basinal subsidence during
the Late Cretaceous period accompanied by eustatic and climatic changes resulted in the
deposition of more than 1000 m thick chalk sequences, the major reservoir of the region.
Continued tectonic activity and ongoing halokinesis resulted in extensive remobilization,
redistribution and reworking of the chalks into the graben. The Maastricht!an / Danian age
Ekofisk and Tor Formations are the principal reservoir units of most of the oil fields in the
Greater Ekofisk area.
2.5 Maturity variations
The API gravity of the Greater Ekofisk Cretaceous oils vary significantly - from about 31-35°
in Hod and Valhall in the south to about 45-50° in Tommeliten and Albuskjell in the north
(Hughes et al., 1985; Bjorpy et al., 1994). These workers have also shown that there exists a
definite maturity trend in the Cretaceous reservoired oils across the region, although Bjor0y et
al. (1994) have stressed that some of the observed differences in the traditional geochemical
parameters are due to source facies differences.

The pristane/nCn and phytane/nCig ratios can be useful to assess maturity if all the oils are
sourced from the same source rock facies. However, different maturity trends will indicate
differences in depositional environments (Le Tran and Phillipe, 1993).
Table 1: Oil samples from the Greater Ekofisk region used in this study. The symbol in the oil
type column denotes the formationfrom which the sample has been obtained.
Field Well Code Type Field Well Code Type

1 No name * 2/7-19R 19R DST1 □ 35 Tommeliten Gamma ♦ 1/9-6 TG7 DST 4 §
2 No name * 2/7-3X 3X DST 18n 36 Edda ♦ 2/7-4 ED1 DST 5 §
3 Embla * 2/7-20X EMI DST 1 # 37 Edda ♦ 2/7-5X ED2 DST 3"
4 Embla * 2/7-21S EM3 DST 1 # 38 Eldfisk Bravo ♦ 2/7B-12 EB1 P.S. * §
5 Embla * 2/7-21S EM2 DST 3# 39 Eldfisk Bravo ♦ 2/7B-12 EB2 P S. * §
6 Embla * 2/7-26S EM5 DST 1 # 40 Eldfisk Bravo ♦ 2/7B-12 EB3 P.S. * §
7 Embla * 2/7-26S EM4 DST 2# 41 Eldfisk Bravo ♦ 2/7B-12 EB4 P.S. * §
8 Embla * 2/7-27S EM6 DST 1 # 42 Eldfisk Bravo ♦ 2/7B-10 EB5 P.S.'§
9 Albuskjell ♦ 1/6-1 AU DST 3* 43 Eldfisk Bravo ♦ 2/7B-12 EB6 P.S. * §
10 Albuskjell ♦ 1/6-3 AL2 DST 2* 44 Eldfisk Bravo ♦ 2/7B-3 EB7 PS." §
11 Albuskjell ♦ 1/6-A10 AL3 P.S.* 45 Eldfisk Bravo ♦ 2/7B-6 EBB P.S. * §
12 Albuskjell ♦ 1/6-A7 ALA P.S.* 46 Eldfisk Bravo ♦ 2/7B-6 EB9 P.S.*§
13 Tor ♦ 2/5-2 TOI DST 2* 47 Eldfisk Bravo ♦ 2/7B-9 EB10 P S. * §
14 Tor 2/5-4 TQ2 DST 1 * 48 Eldfisk Bravo ♦ 2/7B-9 EB11 P S. * §
15 S.E. Tor ♦ 2/5-5 SCI DST 3* 49 Eldfisk Bravo ♦ 2/7B-9 EB12 P S. * §
16 S.E. Tor ♦ 2/5-7 ST2 DST2§ 50 Eldfisk Bravo ♦ 2/7B-9 EB13 P.S.*§
17 Ekofisk ♦ 2/4-4AX EK1 DST 4 = 51 Eldfisk Bravo ♦ 2/7D-1B EB14 P.S.*§
18 Ekofisk ♦ 2/4B-3A EK2 P.S.* 52 Eldfisk Alpha ♦ 2/7A-10 EA1 P.S.*§
19 W. Ekofisk ♦ 2/4-5X WE1 P.S.* 53 Eldfisk Alpha ♦ 2/7A-11 EA2 P.S.§
20 W. Ekofisk ♦ 2/4D-1B WE2 P.S.§ 54 Eldfisk Alpha ♦ 2/7A-16A EA3 P.S.*§
21 Tommeliten Alpha ♦ 1/9-1 3M DST1B = 55 Eldfisk Alpha ♦ 2/7A-19 EA4 P.S.*
22 Tommeliten Alpha ♦ 1/9-1 TA2 DST 4* 56 Eldfisk Alpha ♦ 2/7A-2 EA5 P.S. =
23 Tommeliten Alpha ♦ 1/9-1 TA3 DST 5* 57 Eldfisk Alpha ♦ 2/7A-21 EA6 P.S.*§
24 Tommeliten Alpha ♦ 1/9-1 TA4 DST 8 § 58 Eldfisk Alpha ♦ 2/7A-23 EA7 P.S. * §
25 Tommeliten Alpha ♦ 1/9-2 TA5 DST 1 * 59 Eldfisk Alpha ♦ 2/7A-26 EA8 P S. * §
26 Tommeliten Alpha ♦ 1/9-2 TA6 DST 2 § 60 Eldfisk Alpha ♦ 2/7A-29 EA9 P S. * §
27 Tommeliten Alpha ♦ 1/9-3 TA7 DST 3* 61 Eldfisk Alpha ♦ 2/7A-29 EA10 P.S. * §
28 Tommeliten Alpha ♦ 1/9-3 TAB DST 4 § 62 Valhall ♦ 2/11-1 VA1 DST 4*
29 Tommeliten Gamma ♦ 1/9-4 TG1 DST 1 * 63 Valhall ♦ 2/8-6 VA2 DST 2 =
30 Tommeliten Gamma ♦ 1/9-4 TG2 DST 2* 64 Valhall ♦ 2/8A-1 VA3 P.S. =
31 Tommeliten Gamma ♦ 1/9-4 TG3 DST 3 § 65 Valhall ♦ 2/8A-4 VA4 P.S.*
32 Tommeliten Gamma ♦ 1/9-4 TG4 DST 4§ 66 Hod ♦ 2/11-2 HD1 DST 2 =
33 Tommeliten Gamma ♦ 1/9-6 TG5 DST 2A * 67 Hod ♦ 2/11-6A HD2 DST 1 =
34 Tommeliten Gamma ♦ 1/9-6 TG6 DST 3* 68 Gert 2/12-1 @11 DST2
* pre-Cretaceous, sandstone reservoired oils, ♦ most datafrom Bjor0y et al. (1994)

B - Jurassic, # - pre-Jurassic, * - Tor Fm., = - Hod Fm. and § - Ekofisk Fm.
In the case of the Greater Ekofisk oils, nearly all oils follow a single trend when these
parameters are plotted (Figure 2), although in some fields such as Eldfisk Bravo, Tommeliten
Alpha and Embla, there is a large internal spread. Accordingly, this may indicate that there is
Norwegian University of Science and Technology

one main source rock for these oils (with comparable relative distribution of isoprenoids and
n-alkanes) if the observed spread is mainly due to maturity variations. The large spread within
a field may be due to both maturity and source variations. Whether the discrimination between
3X and Edda oils (Figure 2) is due to maturity alone, will be seen later.
Phytane/nC18 Figure 2: Cross-plot of pristane/

GREATER EKOFISK OILS nCn versus phytane/ nCjs, calcu
latedfrom FID gas chromatograms
of whole oil samples.
*19R
*3X
OEM
AAL
0.4 • -
♦ TO
OST
• EK
* WE
+ TA
XTG
oVA
■ HD
TGT
Pristane / nC17
A better maturity-based discrimination is seen using the more reliable aromatic hydro carbons-
based parameters (Figure 3a and b). These ratios have been used successfully earlier (Hall et
al., 1985; Radke, 1987). Dimethylnaphthalene (DMNR) ratio (2,6 + 2,7 / 1,5
dimethylnaphthalenes) and methylphenanthrene (MP) based calculated vitrinite reflectance
(Rc = 0.6 MPI1 + 0.4, where 2MP/1MP < 2.65) are amongst the most reliable and widely used
maturity parameters. The main observations in Figures 3a and b are two fold: 1) first, there is a
clear trend in the maturity of the Greater Ekofisk Cretaceous oils, as noted by Bjor0y et al.
(1994), in that the Hod and Valhall fields in the south contain least mature oils, followed by
slightly more mature Eldfisk Alpha and Bravo and Ekofisk oils and finally most mature
Albuskjell and Tommeliten Gamma oils in the north. This sequence of increasing DMNR and
Rc values indicates different phases of hydrocarbon generation in Greater Ekofisk. The
observed spread in the pristane/nC17 values in the Eldfisk Bravo population (but relatively
constant DMNR) points supports the idea of different source facies feeding the field.
Interestingly, the maturity of the pre-Cretaceous sandstone reservoired 3X oil is comparable to
the least mature Cretaceous oils from Hod and Valhall. 2) the second and more important
observation from this study’s point of view is that while the other pre-Cretaceous oils (Embla
and 19R) are very mature (in fact the 19R oil is the most mature in the entire suite), the trend

Paper I: Diverse oilfamilies in the Greater Ekofisk area, Central Graben, Norway 13
of these oils is different compared to the general Cretaceous oils’ trend. This might suggest
that there are differences in the source facies sourcing these oils.
Dimethylnaphthalene Ratio (OMNR) Figure 3: a) Pristane/nCn, calcu

68 GREATER EKOFISK OILS
latedfrom FID gas chromatograms
of whole oil samples plotted
against dimethylnaphthalene ratio,
“Sea calculated from FPD gas
0E8 chromatograms of aromatic hydro
ED ED
★ 19R
carbon fractions, b) methyl-
*3X phenanthrene based calculated
— OEM
aAL
reflectance versus DMNR.
♦ TO
nST
• EK
* WE
+TA
XTG
OVA
<$> ■ HD
TGT
Pristane / nC17
Dimethylnaphthalene ratio (DMNR)
68 GREATER EKOFISK OILS
Pre-Cretaceous
Cretaceous Oils trend
Oils trend
★ 19R
Calculated Reflectance (Rc)
The biomarker data of the Greater Ekofisk oils is in agreement with the above findings. The
major triterpane (e.g. 17a trisnorhopane / 18a trisnomeohopane or Tm/Ts, C30 a|3 diahopane /
hopane) and sterane (e.g. C27 diasterane/sterane, %Cag aPP / (aaa+aPP) ethylcholestane,
%C29 acta 20S/20S+20R ethylcholestane) maturity ratios indicate similar trends when cross-

plotted. Two typical examples are shown in Figures 4 and 5. In both these cases, the Hod and
Valhall oils are least mature (equivalent to top oil window maturity), followed by Ekofisk,
Eldfisk Alpha, Eldfisk Bravo (peak oil generation maturity, Edda (at or just past peak oil
generation) and finally Albuskjell and Tommeliten Alpha (estimated near base oil window
maturity).
C27 diasterane / sterane Figure 4:17a trisnorhopane / 18a

GREATER EKOFISK OILS
trisnomeohopane (Tm/Ts) ratio
calculated from m/z 191 frag-
mentogram plotted against C27
diasterane/ sterane ratio calculated
from m/z 217fragmentogram.
★ 19R
$>3X
OEM
A AL
♦ TO
AST
• EK
* WE
0.4 “ -
-TG
XTA
OVA
■ HO
▼ GT
C2717a/18a hopane (Tm/Ts)
%C29 app / (aaa+app) Figure 5: %C29 aj3j8 / (aaa+

GREATER EKOFISK OILS aj5j3) ethylcholestane plotted
against %C29 aaa 20S/20S+20R
65 - ethylcholestane, both ratios calcu
-H- + -H® latedfrom m/z 217fragmentogram.
55 - *19R
<fc3X
OEM
A AL
♦ TO
AST
• EK
* WE
+ TG
XTA
OVA
■ HD
▼ GT
%C29 aaa 20S/20S+20R
Doctoral Dissertation by Stmil Bharati, 1997

Paper 1: Diverse oilfamilies in the Greater Ekojisk area, Central Graben, Norway 15
With regards to the pre-Cretaceous sandstone reservoired oils, oil from 3X is least mature
(estimated around peak oil generation stage, but more importantly perhaps only slightly less
mature than the Edda oils) and the Embla and 19R oils are estimated to be beyond the oil
window maturity i.e. in the condensate stage, as most of their data are either at maximum
values or become unreliable due to small yields.
2.6 Source facies variations
Based on FED gas chromatograms of whole oils, it is clear that all the Greater Ekofisk oils
have been generated in general from marine type II source rocks, as also noted by several
previous workers (e.g. Cooper and Barnard, 1984; Hughes, 1985). A few other workers have
postulated that differences occur within the Upper Jurassic source interval of the Central
Graben, which account for slightly different oil compositions and their evolution with
increasing maturity (e.g. Forsberg et al., 1993; Bjor0y et al, 1994; Bailey et al., 1990). Some
exemplary chromatograms are shown in Figure 6, which illustrates this point. While the most
obvious change with increasing maturity (a to d in Figure 6) is that the Cretaceous oils become
lighter and more front-end biased, an important point of distinction between the Cretaceous
and pre-Cretaceous oils is seen on comparing the oil from Edda (ED2) to the 3X oil, which
are of comparable maturity. The 3X oil is anomalously rich in isoprenoids, which accounts for
comparatively very high isoprenoids / n-alkane ratios (Figure 2). In addition, we believe that
given the maturity of the other pre-Cretaceous oils (19R and Embla oils, base oil window to
condensate stage), the pre-Cretaceous oils give higher isoprenoids/n-alkane ratios than
expected.
Going by the minor variations in pristane / phytane ratios (mostly ranging 1.3 - 1.6) and
limited carbon preference index (CPI) range (1.0 - 1.15), rather uniform depositional
conditions of the source rocks seems likely. However, a plot of stable carbon isotopic
compositions of saturated versus aromatic hydrocarbon fractions (Figure 7) shows a large but
systematic variation in the Greater Ekofisk oils’ data set. It has been shown that with
increasing thermal maturity, 12C is depleted (Chung et al. 1981; Lewan 1983). However,
maturity alone cannot explain the more than 4°/00 difference in 8 13C of the hydrocarbon
fractions (Figure 7), as it is larger than reported as the maximum variation due to maturity in a
single source rock (Chung et al., 1981). Therefore a significant part of the observed variation
must be inherited from the source. As an example, it has been seen that the oils from Edda
(EDI and ED2, Table 1) and well 2Z7-3X are of comparable maturity (roughly peak oil
generation stage, Figures 3a and 5), the 3X oil being perhaps only slightly less mature.
Nevertheless, the difference in 8 13C is about 3%o (Figure 7), which is considered to be too
large to be due to maturity difference.
#
Figure 6: Some exemplary whole oil FID gas chromatograms from the Greater Ekofisk area.
On left are oils from isotopically light source facies, while on the right are oils from
isotopically heavy facies. Maturity of oils increases from top to bottom. The numbers indicate
the number of carbon atoms in n-alkane, e.g. 15 indicates n-pentadecane; Pr-pristane, Ph-
phytane.

Bjor0y et al (1994) have also made similar observations on comparing the more mature Ula
Trend oils to Valhall and Eldfisk oils, the former being consistently richer in I2C. Another
important point to note in Figure 7 is that, all the pre-Cretaceous sandstone reservoired oils are
isotopically heavier (depleted in 12C) than the Cretaceous chalk reservoired oils. Its
implication is discussed later.
d13C Aromatic Hydrocarbons Figure 7: S13C of saturated hydro

GREATER EKOFISK OILS
carbons plotted versus 8 13C of
aromatic hydrocarbon, obtained
-25 -
from isotope analysis of bulk
fractions.
-26 -
•27 • • —— ■
•28-
* WE
OVA
d13C Saturated Hydrocarbons
2.6.1 Compound specific isotope analysis
This technique, using GC-IRMS, is very useful in highlighting subtle differences which are
otherwise ‘invisible’ within a sample set using a traditional geochemical approach. Its applica
tion has been demonstrated earlier (e.g. Bjor0y et al., 1991; 1994). Using isotope signatures of
C5-30 n-alkanes, Bjor0y et al (1994) showed that many of the Greater Ekofisk Cretaceous chalk
reservoired oils had a similar isotope profile despite differing maturities, suggesting thereby a
single source facies. Some representative examples of such oils are shown in Figure 8, where
the oil from Albuskjell is most mature and that from Hod least mature and the others (S. E.
Tor, Eldfisk and Ekofisk) being intermediate (see Figures 3-5 for maturity trends). The general
range of 8 13C for these oils in nCiô range is -29 to -27%o, but far greater variation (almost -
34 to -24%o) in the lighter end due to varying maturity.
However, there were a few oils (for example from Valhall and Tor) which were anomalous,
whose heavy isotopic signatures could not be explained by the observed maturity differences.
These oils are apparently similar to the pre-Cretaceous sandstone reservoired oils, perhaps
sourced mainly from the isotopically heavier facies, shown in Figure 9; however, as noted in

the previous section, unlike the other pre-Cretaceous oils, the Valhall and Tor oils do not have
anomalously high isoprenoid content (Figure 2).
delta 13C Figure 8: Compound

Isotopically Light Oils specific 8I3C plots of n-
alkanes of Cretaceous
reservoired oils sourced
from isotopically light
-26 -
facies (cf. Table 1 for
sample codes).
•27 — —
-28
Number of carbon atoms in n-alkane
delta 13C
Isotopically Heavy Oils
Figure 9: Compound
specific 5 13 C plots of n-
-25 - - alkanes of pre-Cretaceous
-&VA4 reservoired and two
Cretaceous reservoired
-26 -
oils sourced from isoto
pically heavy facies (cf.
Table 1 for sample codes).
-28 • —
In this group, oils from 19R and Embla are most mature (19R perhaps slightly more mature),
while the oil from 3X (interpreted as the end- member representative of the isotopically heavy
facies) is of lesser maturity (cf. Figures 3-5). When compared to the Cretaceous oils (Figure

8), the most striking difference is in 5 13C values in the nCig.go range, the pre-Cretaceous oils
being heavier by almost 3°/oo for a given maturity (compare for example Albuskjell to Embla
or Ekofisk to 3X).
Bjor0y et al. (1994) have also proposed that some of the oils from the Greater Ekofisk chalk
fields contain a mixture of the two facies, thereby implying that both, the isotopically heavy
and light source facies, have contributed to the present oil population in the reservoir. The
contribution from each facies however varies for different fields, an aspect that makes data
interpretation more difficult. Oils interpreted to be of mixed composition are plotted in Figure
10, along with the known end-members for reference, i.e. oil from 3X representing the
isotopically heavy facies and oil from Edda representing the isotopically light facies, both
these oils being of comparable maturity (cf. Figures 3-5). More oils from the Eldfisk Alpha
and Bravo fields were analysed than any other field in the present study (Table 1). While each
of these fields show systematic patterns in the isotopic signature (Bjor0y et al., 1994), there is
also a large variation. While some oils (particularly from Alpha south - EAS) show minimal
signs of mixing, the oils from Alpha north and Bravo exhibit signatures suggestive of mixing.
The best and most convincing sample indicating a significant contribution from the
isotopically heavy facies is EB8 (highlighted as a dotted plot in Figure 10).
delta 13C
Isotopically Mixed Oils
Figure 10: Compound
«**ED2' -flight end-member specific 813C plots ofn-
-25 -- alkanes of Cretaceous
reservoired oils sourced
from both isotopically
-26 -- *Heavy end-member
light and heavy facies.
The heavy (3X) and
-27 - light (Edda) end-
members are also
-28 - shown for reference (cf.
Table 1 for sample
codes).
-29 -
This oil is comparable to the Edda oil with respect to maturity (based on most gas
chromatography and biomarkers based maturity parameters) and 8 13C values of light to
medium range n-alkanes, but very heavy and similar to 3X oil towards the heavier end. In
contrast, the other Eldfisk Bravo oil plotted (EB4) does not show equally large contribution

from the isotopically heavy facies, plotting nearly in between the two end-members. Other oils
that are interpreted to be mixed are also shown, for example from Eldfisk Alpha north (BAN)
and Tommeliten Gamma.
2.7 The Greater Ekofisk oil families
From the above results, it is clear that we are dealing with two principle types of source facies:
1) isotopically light and 2) isotopically heavy. The isotopically heavy facies can perhaps be
further divided into two groups, namely one with anomalous isoprenoid enrichment and the
other with normal isoprenoid content (comparable to isotopically light facies), unless the latter
is due to mixing. Without doubt, several oil fields have been sourced from both the facies
resulting in mixed signatures. However, broad discrimination between all the 16 fields of this
study based on maturity, composition and isotopic signatures is possible and shown as a
cartoon in Figure 11.
Figure 11: A graphical

representation of the various
oil families in the Greater
Ekofisk area. Maturity is
based on GC and GC-MS
parameters and isotope
signature is based on whole
oil bulk measurements.
Light Whoile Oil bulk 513C Heavy
While the average maturity of an oil from a field has been estimated based on data presented
in Figures 3-5 (and shown plotted on the oil window scale), the isotope signature is the
average of bulk whole oil 8 13C measurements of all samples from that field (cf. Table 1).
While the vertical separation between fields is entirely due to maturity, the horizontal
separation is due to both maturity and source facies effects. This is due to the fact that the
plotted isotope values are bulk values, which includes the light end components, these being
more susceptible to maturity variations (Clayton, 1991). If for example, average values of just
nC15+ n-alkanes are plotted (cf. Figures 7-9), the horizontal separation would be greater and
primarily due to source effects.

Ratios based on closely eluting minor (and not necessarily identified) compounds in between
the major compounds, such as n-alkanes, during gas chromatography of whole oils have also
been used to group oils, using star diagrams (Kaufman et al., 1990; Halpem, 1995). The
choice of peaks for such an exercise is normally random, as long as the peak pairs are very
closely eluting, thereby implying of comparable molecular size and boiling point. This
approach was also employed using typical representative oils from each field. In cases where
the entire field could not be represented by a single oil, two end-members were used (e.g.
Eldfisk Alpha, Eldfisk Bravo, Embla and Tommeliten Alpha). The results of these 19 oils
using 10 ratios (using peak heights of 20 compounds in the nCs-io range, of which 2 are
unidentified) are shown in Figures 12a-d. The Edda oil is not included, as 3 of the 10 ratios
could not be computed. All ratios were subsequently normalized to standardize the plotting
scale.
All the pre-Cretaceous oils are plotted together (Figure 12a). The remaining Cretaceous oils
have been grouped merely on the basis of similarity of the star shapes and field criterion
(Figures 12b-d). Some systematic patterns can be seen in these plots. For example,
1) The star orientation of the pre-Cretaceous oils (except 3X) and the Cretaceous oils group 1
(except the outlier TA1) is roughly the same (NW-SE). All these oils are also most mature.
2) The star orientation of the Cretaceous oils groups 2 and 3 are roughly the same (NS). These
oils are also amongst the least mature.
This general change (from NS to roughly NW-SE orientation) may be due to increasing
maturity. Amongst the pre-Cretaceous oils, the 19R and Embla oils are similar while the 3X
oil appears very different, mostly due to ratios 2, 4, 6 and 7. Thompson (1987) and
Rovenskaya and Nemchencko (1992) have suggested that several light hydrocarbon
components are affected by thermal maturation, for example ethylbenzene / p, m-xylene (this
study’s ratio 7). It is thus likely that the differences that we see between 3X and the rest are
simply an artifact of 3X’s lower maturity. In the Cretaceous oils 1 group, oil TA1 is an outlier.
This may be due to a different source as this oil is from the Hod Formation, while all the
others are either from Tor or Ekofisk Formations (Table 1). With regards to VA4 oil in
Cretaceous oils group 2, which is different than the rest, closer examination shows that the
general star shape of VA4 is similar to the 3X oil. This is probably due to the fact that the
Valhall oil has been mainly sourced by the isotopically heavy facies, as shown above.
There are also some inconsistencies in the star diagram based groupings which must be ment
ioned. For example, the Tommeliten Gamma and Tor oils (TG5 and T02 respectively) were
also shown to be have a major component sourced from the isotopically heavy facies.
However, their star plots do not show any similarity to the 3X star. In summary, while several
star diagram based observations can be logically explained in the context of other data, a few
cannot be (unless the light hydrocarbons are mainly sourced by one facies and the heavier
homologues by the other).
1
22 Mobile and immobile migrated hydrocarbons in the Embla Field North Sea
Pre-Cretaceous Oils R1 Cretaceous Oils 1
'' WE2
- - TA1
Cretaceous Oils 2
H01
Figure 12: Star diagrams based on gas chromatography of whole oils. The ten ratios (Rl-
R10) used have been calculated using peak heights of closely eluting minor compounds.
2.8 Conclusions
Distinct differences are present between the pre-Cretaceous sandstone reservoired and
Cretaceous chalk reservoired oils. This difference is not due to the petrophysical properties’
differences between the two reservoirs types, but due to two distinctly different source facies
sourcing these oils. The oil from 3X represents the heavy facies end-member and the Edda oil
represents the lighter facies end-member, both oils being of comparable maturity but with
about 37oo difference in their isotopic composition. While the pre-Cretaceous oils (3X, 19R
and Embla) have been sourced by the isotopically heavy facies anomalously enriched in
isoprenoids, most of the Cretaceous oils (Albuskjell, S. E. Tor, Ekofisk, Eldfisk Alpha south
and Hod) have been sourced by isotopically lighter facies with a normal isoprenoid content.

Some Cretaceous chalk fields have also been sourced by the heavier facies (Valhall and Tor),
but the isoprenoid content in these oils is within the normal range. Based on compound
specific isotope analyses, it can be concluded that some fields (Eldfisk Bravo, Eldfisk Alpha
north and Tommeliten Gamma) contain mixed oils from the two facies. The degree of each
facies’ contribution is variable.
2.9 Acknowledgments
Many thanks to Norwegian Research Council, Phillips Petroleum Co., Norway and Amoco
Norway for partial financial assistance. The staff of Geolab Nor is thanked for assistance in
geochemical analyses and the Department of Geology, Norwegian University of Science and
Technology, Trondheim for support and encouragement
2.10 References
Bailey, N. J. L., Burwood, R., and Harriman, G. E., 1990, Application of pyrolysate carbon
isotope and biomarker technology to organofacies definition and oil correlation problems in
North Sea basins, in B. Durand and F. Behar, eds., Advances in Organic Geochemistry 1989,
Pergamon, Oxford, p. 1157-1172.
Bjor0y, M., Hall, K., Gillyon, P. and Jumeau, J., 1991, Carbon isotope variations in n-alkanes
and isoprenoids in whole oils: Chemical Geology, v. 93, p. 13-20.
Central Graben oils: Organic Geochemistry, v. 22, p. 355-381.
Chung, H. M., Brand, S. W. and Grizzle, P. L., 1981, Carbon isotope geochemistry of the
Paleozoic oils from the Big Horn Basin: Geochimica Cosmochimica Acta, v. 45, p. 1803-
1815.
Clayton, C. J., 1991, Effect of maturity on carbon isotope ratios of oils and condensates:
Organic Geochemistry, v. 17, p. 887-900.
Cooper, B. S. and Barnard, P. C., 1984, Source rocks and oils of the Central and Northern
North Sea, in G. Demaisson and R. J. Munis, eds., Petroleum Geochemistry and Basin
Evaluation, AAPG Memoirs 35, AAPG, Tulsa, p. 303-314.
Feazel, C. T., Knight, I. A. and Pekot, L. J., 1990, Ekofisk Field-Norway, Central Graben,
North Sea, in E. A. Beaumont and N. H. Foster, eds., Structural Traps IV, Treatise of
Petroleum Geology, Am. Asso. of Pet. Geol., Tulsa: p. 1-26.
Forsberg, A., Gowers, M. B. and Holtar, E., 1993, Multi-disciplinary stratigraphic analysis of the
Upper Jurassic strata of the Norwegian Central trough, in A. M. Spencer, ed., Generation, Accu
mulation and Production of Europe’s hydrocarbons: Springer-Verlag, Berlin, p. 45-58.

Fraser, A. J., Farnsworth, J. and Hodgson, N. A., 1993, Salt controls on basin evolution- Central
North Sea, in A. M. Spencer, ed., Generation, Accumulation and Production of Europe’s hydro
carbons: Springer-Verlag, Berlin, p. 59-68.
Gowers, M. B. and Saeb0e, A., 1985, On the structural evolution of the Central Trough in the
Norwegian and Danish sectors of the North Sea: Marine and Petroleum Geology, v. 2, p. 298-
318.
Hall, P. B., Schou, L. and Bjor0y, M., 1985, Aromatic hydrocarbon variations in North Sea
wells, in B. M. Thomas, ed., Petroleum Geochemistry in Exploration of the Norwegian Shelf:
Graham & Trotman, London, p. 293-301.
Halpem, H. I., 1995, Development and applications of light hydrocarbon based star diagrams:
Ekofisk oils, in B. M. Thomas et al., eds., Petroleum Geochemistry in exploration of the
Kaufman, R. L., Ahmed, A. S. and Elsinger, R. J., 1990, Gas chromatography as a development
and production tool for fingerprinting oils from individual reservoirs; applications in the Gulf of
Mexico: PR 8824, in Proceedings of Gulf Coast Section of the Society of Economic Paleontolo
gists and Mineralogists Foundation 9th Annual Research Conference, p. 263-282.
Lewan, M. D., 1983, Effects of thermal maturation on stable organic carbon isotopes as
determined by hydrous pyrolysis of Woodford shale: Geochimica Cosmochimica Acta, v. 47,
p.1471-1479.
Le Tran, K. and Phillipe, B., 1993, Oil and rock extract analysis, in M. L. Bordenave , ed.,
Applied Petroleum Geochemistry: Edition Technip, Paris, p. 72-394.
Radke, M., 1987, Organic Geochemistry of aromatic hydrocarbons, in J. Brooks and D. Welte,
eds., Advances in Petroleum Geochemistry- Vol. 2: Academic Press, London, p. 141-208.
Rovenskaya, A. S. and Nemchencko, N. N., 1992, Prediction of hydrocarbons in the west

Siberian basin: Bulletin Centres Research- Exploration & Production, Elf Aquitaine, v. 16, p.
285-318.
Thompson, K. F. M., 1987, Gas-condensate migration and oil fractionation in deltaic systems:
Marine and Petroleum Geology, v. 5, p. 237-246.
Van den Bark, E. and Thomas, O. D., 1981, Ekofisk: first of the giant oil fields in Western
Europe, AAPG Bulletin, v. 65, p. 2341-2363.

Paper 2: Embla Geochemistry: Occurrence & compositional variations of migrated HCs 25
Chapter 3 : Paper 2
Geochemical evaluation of the Embla field, Norwegian

Continental Shelf -1: Occurrence and compositional variations of
migrated hydrocarbons§
Sunil Bharati1, Peter B. Hall Rare Vagle2 and Malvin Bjor0y1
l- Geolab Nor, 7002 Trondheim, Norway;2- Phillips Petroleum Co., 4056 Tanager, Norway.
3.1 Abstract
The Embla Field, discovered in 1974 and located southwest of the Eldfisk Field, on the
Grensen Nose in Block 2/7, has been investigated in detail through geochemical analyses,
using 6 oils and 973 core samples from 8 exploratory wells drilled in the 1986-91 period. The
study comprises two parts and focuses on petroleum’s gross occurrence and compositional
variations (part 1) and source, maturity and intra-reservoir communication (part 2) of the
migrated hydrocarbons. The Embla Field is different from all the other neighbouring
(Cretaceous chalk) fields in that its reservoirs are pre-Cretaceous sandstones and relatively
most deeply buried. Oil-based mud, used during drilling all but one of the Embla wells, has
adversely affected most geochemical data, particularly the abundance data. However, despite
these limitations, gross differences are evident within the Embla oil population (both hori
zontally across the field and vertically down the reservoir) with respect to composition and
richness. The Embla reservoir, consisting of the Upper and Lower Sandstones, contains two
distinct types of oil, A and B, although both the oils are very light. The Upper Sandstone, with
well developed porosity, is richer in hydrocarbons but also relatively non-homogenous, when
compared to the Lower Sandstone. The lower part of the reservoir, particularly the Lower
Sandstone, has a high content of solid reservoir bitumen, which significantly diminishes the
overall reservoir properties. Relative productivity of some test intervals has been estimated by
using the geochemical data of the present study.
* Manuscript under submission to Marine and Petroleum Geology

3.2 Introduction
Until about the early 1980s, the principal focus of explorationists, particularly those involved
with geochemistry, was characterization of the rock matrix (petrophysical properties,
depositional environments, diagenesis etc.) and practically no efforts were made to understand
the fluids, particularly the one that is produced, namely oil. However, it is now commonly
recognized that many petroleum reservoirs are heterogeneous, not only with respect to
structural elements and petrophysical characteristics, but also composition, maturity and
communication of the oil contained therein. While the former aspects have been historically
identified and predicted using a variety of constantly evolving engineering and logging
techniques, measuring the fluid’s chemical disparities and linking them to other geological
data became the norm only in the last decade or so. Numerous studies have since focused on
understanding how the properties, fate and variations of the organic constituents, namely oil
and gas, affect heterogeneity (e.g. England et al., 1987; England, 1990). Several new methods
have therefore been developed to meet the changing needs and applications in petroleum
geochemistry (e.g. Bjorpy et al., 1990; Bjorpy et al., 1992; Horsfield and McLimans, 1984;
Kaufman et al., 1990; Latter and Aplin, 1995 and references therein; Leythaeuser and
Ruckheim, 1989). These techniques and approaches have been successfully used and reported
in several fields and basins, particularly in the North Sea, for example in the Eldfisk Field,
NOCS Block 2/7 (Stoddart et al., 1995; Hall et al., 1994; Bharati et al., 1997a).
In the Eldfisk Field, which lies east of the Skrubbe Fault and north-east of Embla (Figure 1),
Hall et al. (1994) showed that in addition to the Eldfisk Alpha and Bravo structures containing
petroleum of differing maturity, each structure contained sections rich in waxes which
diminishes vertical homogeneity of the oil column. In addition they showed that the field was
filled by two charges, each differing from the other in the stable carbon isotopic signature.
Stoddart et al. (1995) estimated the probable filling time, process and direction of the field.
Eldfisk Field is one of several oil-producing Paleocene/Cretaceous chalk fields in the Central
Graben, North Sea, that contain oils less mature than pre-Cretaceous reservoired oils in the
region, such as in Embla and well 2/7-19R (Bjorpy et al., 1994; Bharati et al., 1997a).
The objective of the present study is to conduct a detailed geochemical evaluation of the
Paleozoic sandstone reservoir of the Embla Field, particularly the petroleum contained therein,
in light of available geological data. In addition to basic characterization of hydrocarbons, this
study aims at understanding the filling mechanisms of the field and defining intra-reservoir
communication. While this paper assesses the gross occurrence and compositional variations
of migrated hydrocarbons, both horizontally across the field and vertically down the reservoir,
the second paper (Bharati et al., 1997b) addresses the aspects of source, maturity and
compartmentalization of the migrated hydrocarbons.

Paper 2: Embla Geochemistry: Occurrence & compositional variations ofmigrated HCs 27
Figure 1: Location Map showing Block 2/7 in the Norwegian Continental Shelf (NOCS) and
enlargement of the Embla Field with wells locations.
3.3 Geological elements and Field history
3.3.1 Regional setting
The Embla Field, an oil field, is located on the Grensen Nose in Block 2/7 to the south-west of
the Eldfisk Field on the downthrown side of the Skrubbe Fault (Figure 1). Regional thickness
variations in the Upper Permian and Mesozoic stratigraphic sections indicate that the Grensen
Nose was part of the Mid-North Sea High until subsidence in the Central Graben occurred
during the Late Cretaceous period (Gowers and Saebpe, 1985). Based on 3D seismic data,
Sears et al. (1993) suggested that much of the basement framework in the Central Graben was
created during the Caledonian orogeny which gave rise to NW-SE and NE-SW trending
diffuse shear zones, and that subsequent reactivation along these existing basement lineaments
occurred from Late Paleozoic to Cenozoic times. Fraser et al. (1993) suggested that the
mobilization of the Permian salt underlying the Central Graben has played a pivotal role in

influencing patterns of structure and sedimentation, including the preservation of coarse

clastic input to the basin in an arid continental environment.
3.3.2 Structure and Stratigraphy
The Embla Field has been interpreted as occurring in a westward dipping Paleozoic horst (Knight
et al., 1993). The structure is a faulted dome with long axis of the field oriented northwest -
southeast and bounded to the east by the Skrubbe Fault The field (about 19.4 km2 at Paleozoic
unconformity, OWC at 4387 m, based on data from well 2/7-9, resulting in an oil column of 354
m in this well) consists of a trap formed by a combination of structural and stratigraphic
elements. Intense faulting within the reservoir sections (based on both cores and seismic data
interpretation) indicates that there is a risk of reservoir compartmentalization. Both RFT and DST
production data indicate that horizontal and vertical barriers to fluid flow may exist, the latter also
indicating horizontal flow barriers in the form of faults or stratigraphical discontinuities (Knight
et al, 1993). Vertical flow barriers may include caliche layers, intercalated volcanic horizons and
the lacustrine mudstones separating the Upper and Lower Sandstones (Knight et al., 1993).
Petroleum properties also show some variations within the field, such as higher gas-oil ratios in
the eastern fault block, suggesting that the more deeply buried source to the east may have
contributed a greater gas component (Knight et al. 1993).
The pre-Cretaceous stratigraphy varies significantly between wells in the Embla Field. However,
well 2/7-26S has encountered the most complete sequence (Figure 2). The basement rhyolitic
unit, possibly of Devonian age, is overlain by Lower Devonian mudstones, upon which rests the
reservoir section. The Upper Jurassic Tyne Gp. unconformably overlies the Embla reservoir and
only a very thin Mandal Fm. mudstone is present high on the structure. Table 1 summarizes the
interpreted formation tops in the studied wells.
Table 1: Interpretedformation tops in meters TVDSS (rounded off to nearest meter, thickness in
parentheses) in the Embla Field.. * indicates theformation in which the well was terminated.
Formation 20X 21S 23S 25S 26S 27S

TyneGp. 4035 (36) 4034(12) 4115 (5) 4121(320) 4146(81) 4143 (6)
Uppermost Sandstone 4071(1731.. ..Absent . 4120* ' Absent Absent 4149*
Upper Sandstone Absent 4046(21) 4441 (12) 4227 (146)
Upper Mudstone 4244(145) " 4# (111) 4453* V 4373(6).
Lower Sandstone 4389 (65) 4178 (77) 4436(113)
Lower Mudstone 4454* 42S5%7Q): . .4540.019). . _
Rhyolite 4525* 4648*
Total Depth 4484 . 4688 4437 4528 4668 4423
Note: Exceptfor Tyne Gp. (Upper Jurassic) all otherformations are ofPaleozoic age.

Paper 2: Embla Geochemistry: Occurrence & compositional variations of migrated HCs 29
Figure 2: Generalized
DEPTH
SUBSEA PERIOD EPOCH GROUP LITHOLOGY stratigraphy of well 2/7-
Ox 26S.
M CLAY
HOLOCENE-
QUARTERNARY
ANHYDRITE
PLEISTOCENE
SAND
PUOCENE-
MIOCENE
CLAYSTONE
ANHYDRITE
HORDALAND
ROGALAND
SHETLAND
CRETACEOUS
KNOLL MUDSTONE
UPPER SAND
INDETERMINATE UNASSIGNED
LOWER SAND
UNASSIGNEO ■
DEVONIAN LATE MUDSTONE
INTERMEDIATE UNASSIGNED VOLCANICS
333 Reservoir lithofacies and diagenesis
The age of the reservoir remains unknown as the sequence is barren of microfossils, but the
current interpretation based on radiometric dating favours early Permian, Carboniferous and/or
late Devonian (Knight et al., 1993). The reservoir consists of three major sandstone intervals
(named as the Uppermost Sandstone, Upper Sandstone and Lower Sandstone) of braided fluvial
and alluvial fan origin separated by a lacustrine mudstone-siltstone sequence (Figure 3). The
Uppermost and Upper Sandstone, classified as a distal braided fluvial system, consists of fine to
medium-grained sandstones with occasional quartz pebbles, generally well sorted with graded
bedding in fining-upward cycles containing discontinuous clay laminae (average net porosity
14.8 %, permeability 0.05 - 10 mD, Knight et al. 1993). The Lower Sandstone unit, interpreted as
a channel fill system, can be divided into a lower section consisting of stacked debris flows and
an upper section consisting of braided pebbly sandstone with thin volcanic intercalations (average
net porosity 11.3 %, permeability 0.05 - 100 mD, Knight et al. 1993). The Lower Sandstone is
significantly coarser than the Upper Sandstone, and has significantly higher permeability than the
Upper Sandstone.

The reservoir has experienced a complex diagenetic history with repeated periods of porosity
loss and enhancement (Knight et al. 1993). Most of the effective porosity is secondary in origin,
in the form of intra-granular and mouldic pores due to partial and total grain dissolution
respectively. Minerals observed in fractures in cores have been interpreted as indicating periodic
invasions of hydrothermal fluids into the reservoir (Knight et al. 1993). A residual bitumen is
prominent in some sections of the wells. The most significant occurrences (that can be seen by
the naked eye) are in wells 2/7-26S and 2/7-20X, particularly in the lower part of the Lower
Sandstone; in 2Z7-21S. Abundant bitumen also occurs in a thin interval of rhyolite beneath the
reservoir (Bharati, 1997).
23S/27S
I Uppermost I
if/-- DST*1
.........1 I Uppermost!
D$T#1
DST«2[
DST#1
I
Figure 3: Generalized cross-section (roughly NW-SE) of the Embla Field below the base
Cretaceous unconformity (solid bars = cored intervals, open bars = DST intervals; distances
between the wells are at sub-sea level).
The total net thickness of the reservoir section varies from more than 317 m in 2/7-23 S to 98 m in
2/7-21S. The Uppermost Sandstone is very well developed in wells 23S/27S and 20X (317 and
173 mrespectively), but absent in the other wells. The Upper Sandstone is 146 min well 26S, but
due to erosional truncation only 21 m in well 21S and absent in the others (Figure 3). The Upper
Sandstone is most extensively cored in well 26S (solid bars on the right hand side of each well
in Figure 3). The Lower Sandstone is well developed in 3 wells and varies from 113 m in 26S to
65 min 2/7-20X (in the center of the structure). Wells 20X, 21S and 26S were drilled through

the base of the Lower Sandstone, while wells 23S/27S were terminated within the Uppermost
Sandstone (Figure 3). Present day reservoir temperature is 160°C and initial pressure recorded
was 841 bar. The reservoir is considered to be undersaturated with oil (API 42°) and variable
GOR (329 Sm3/Sm3, 1900 Scf/stb in the eastern block and 276 Sm3/Sm3 (1550 Scf/stb) in the
western block).
For simplicity, the Embla reservoir (shown as a cross-section in Figure 3) has been divided
into 7 sub-traps - two in the Uppermost Sandstone (namely UM1 and UM2), two in the Upper
Sandstone (namely US1 and US2) and three in the Lower Sandstone (namely LSI, LS2 and
LS3, schematically shown as an inset in Figure 3), with the two sandstones being separated by
a thick mudstone section. Another major consideration in horizontally defining these sub-traps
is the presence of faults within the Embla structure (Figure 1).
3.3.4 Exploration history
Well 2/7-09, drilled in 1974, discovered oil in the pre-Jurassic sandstones. The oil yield in this
sandstone, later identified as the Upper Sandstone interval of Embla, was only 36 Sm3 /day (-200
stock tank barrels of oil/day - STBOPD). This was considered to be low and a productivity of
about 320 Sm3 /day (-2000 STBOPD) was calculated to be possible for this sandstone. The next
well, 2/7-20X, was drilled in 1986 on an upthrown fault block from 2/7-09. DST flow rates of
566 Sm3 /day (-3500 STBOPD) were recorded from the Upper Sandstone (test intervals shown
as open bars on the left hand side of each well in Figure 3). Well 2/7-21S was drilled in 1989 to
test the south-easterly continuation of the Upper Sandstone. This well was deviated to the target
location at base Cretaceous, 1.2 kilometers south-east of the 20X wellhead. A DST of the Lower
Sandstone yielded up to 785 Sm3 /day (-5200 STBOPD), while a commingled test of both Upper
and Lower Sandstones yielded 1236 Sm3 /day. Well 2/7-23S was also drilled in 1989 to test the
northern continuation of the field. This well was deviated to the target location at base
Cretaceous, 1.2 kilometers north of the 20X wellhead. No tests could be performed due to
technical problems. In 1990/91, well 2/7-25S was drilled to a target location to the south-east (i.e.
beyond 2/7-21S), 2 kilometers from 2/7-20X. No reservoir was encountered, only -400 meters of
fine elastics of mostly Upper Jurassic age. Well 2/7-26S was drilled in 1991 to test the western
fault block from the 2/7-20X wellhead to the target location 350 m south of 2/7-09. The well has
similar stratigraphy to 2/7-20X. However, the sandstones have lower permeability than in the
other wells. DSTs proved only 223 Sm3 /day. Well 2/7-27S was drilled to a target location very
close to 2/7-23S, predominantly to perform a DST of the Lower Sandstone as this could not be
done in well 23S; a flow of 3660 STBOPD was recorded.
3.4 Samples and methods
Due to the prognosed geological and other complexities (Knight et al., 1993), extensive coring
was planned and carried out, resulting in a total recovery of 732 m of conventional core,

mostly covering the reservoir sections in 6 wells. All the geochemical analyses (Table 2) were
performed according to the procedures specified in the Norwegian Industry Guide to Organic
Geochemical Analyses (1993). Mineralogical composition of sandstones was established by
XRD analysis on a selected suite of 25 powdered whole rock samples, covering the entire
Upper and Lower Sandstone intervals.
Screening analyses (Total organic carbon and Rock Eval pyrolysis) were performed roughly
every 2 m in every well to obtain a general picture of migrated hydrocarbon richness and
source rock potential. Based on these results, a large suite of samples was characterized in
detail using Iatroscan (Bharati et al., 1994) to obtain mainly bulk compositional data of the
migrated hydrocarbons, in terms of both absolute and relative abundance of the 4 principal
fractions, namely saturated and aromatic hydrocarbons, resins 1 and resins 2 (this being
similar to asphaltenes). Concurrent to Iatroscan analysis, a new Iatroscan calibration method
was developed using a suite of natural crude oils (Bharati et al., 1994).
Detailed molecular characterization was achieved by thermal extraction-pyrolysis-GC using

GeoFina Hydrocarbon Meter (GHM, Bjorpy et al., 1992) on powdered rock samples and gas
chromatography (GC) of saturated and aromatic hydrocarbon (HC) fractions (obtained as a
result of solvent extraction followed by liquid chromatography, MPLC). In addition to the
reservoir section, several samples from potential source rocks were also analyzed from two
other wells (2/7-24 and 2/7-28). Table 2 summarizes the sampling and analytical details.
Table 2: Details of samples analyzedfrom the Embla Field, block NOCS 2/7. Wells 20X, 21S,
23S, 25S, 26S and 27S cover the reservoir sections (Uppermost, Upper and Lower
Sandstones, all core samples) while wells 24 and 28 contain mainly potential source rocks
(claystone cores and cuttings).
Well No. Screening1 Iatroscan 2 TE-PY-GC 3 MPLC/GC 4

20X 54 45 21 8
21S 68 67 22 8
23S 140 - 140 10
24 16 16 .. 10. . 7
25S 35 35 19 15
26S - 609 219 160 20 _
27S 37 37 11 7
28 13 13 : 9 5
Total 972 320 392 80
2- Comprises lithology description, Rock Eval and TOC. 2- Quantitative TLC-FID. 3 - Thermal
extraction-pyrolysis-gas chromatography. 4 - Liquid chromatography of maltenes / capillary
gas chromatography of saturated and aromatic hydrocarbons.

3.5 Mineralogical composition of reservoir sandstones
Based on XRD analysis results of a limited number of samples (for example only one sample
from the Upper Sandstone in trap US1), differences between the Uppermost/Upper and Lower
Sandstones are evident with respect to mineralogical composition (Figure 4). In general, the
quartz percentage is much lower in the Upper Sandstone, typically 50-60%) as compared to the
Lower Sandstone (typically >70%). But the most striking feature is the high percentage of
kaolinite (up to about 30% and conspicuously more abundant in the Upper Sandstone as
compared to the Lower Sandstone, Figure 4) and only trace amounts of illite, despite the depth of
the reservoir (> 4 km). This indicates that no kaolinite dissolution resulting in illite precipitation
could take place due to lack of potassium in the system, either from outside or locally through
feldspar dissolution. No feldspar is present in any of the samples and siderite, pyrite and
anhydrite are present only in trace amounts. Fe-dolomite / ankerite is present only in some
samples (up to over 40%), but absent in most of the samples; however, maximum dolomite was
detected in the Lower Sandstone of wells 23S and 26S.
Figure 4: Relative percentages of

the major minerals detected in
samples from the Uppermost and
Upper Sandstones (top) and the
Lower Sandstone (bottom) as
determined by XRD. n = number of
samples (in each trap). See Figure 3
for trap codes.
Quartz Kaolinite Illite Dolomite Siderite Pyrite Anhydrite

MINERAL

3.6 Abundance of Migrated Hydrocarbons
3.6.1 Mud contamination problem
Except for one well (27S) all the other wells of the main Embla structure (20X, 21S, 23S, 25S
and 26S) were drilled using oil based mud (OEM), the primary organic additive being diesel.
No mud sample was available for analysis, thereby limiting our knowledge about the chemical
composition of the additives. Under reservoir conditions (high pressure and temperature), drill
mud is known to penetrate the host rock and therefore has the potential of adversely affecting
subsequent organic geochemical analyses and the data obtained therefrom. Hydrocarbons are
generally found in the high porosity zones of the reservoir section and these are also the zones
which tend to be most affected by mud penetration. Analyses such as Rock Eval, Iatroscan,
extraction and gas chromatography are particularly prone to adverse effects. It is also easier to
detect contamination in compositional data than in abundance (richness) data.
In our case, samples available for the study were only from the reservoir interval and no
‘baseline’ sample was available to throw some light on the extent of contamination. However,
to minimize the problem, samples were collected only from the center of the core where mud
penetration is expected to be minimal. As porosity and hydrocarbon richness vary from well to
well and down a given well, estimating any standard value for contamination would be
erroneous and misleading. While this problem cannot be avoided in the case of Embla Field, it
should not be overlooked or underestimated. Neither should this problem become the reason
for discarding all data or not reaching rational conclusions which are based on established
principles and previously published works. We have exercised caution and borne this fact in
mind while interpreting the geochemical data and have attempted to mention this in the
relevant portions of the text. Wherever possible, we have also tried to highlight the problem by
comparing samples, particularly from wells 23S and 27S.
3.6.2 Uppermost Sandstone
This section is well developed in only three wells (20X and 23S/27S), but core samples are
available only from 23S and 27S. Trap UM2 (represented by well 23S) is laterally separated
from trap UM1 trap in the south by faults. In general, the free hydrocarbon abundance is higher
in 23S than 27S, clearly (overestimated) due to oil-based mud contamination in the former (well
27S was drilled using water based mud unlike all other wells). The degree of contamination,
however, varies from sample to sample, depending on the inherent petrophysical properties.
While the free hydrocarbon content varies about 2-4 mg/g rock in 27S, it is generally above 10
mg/g rock in 23S with a few exceptions (Figure 5). The top 60 m or so of the analyzed section is
relatively depleted (around 5 mg HC/g rock), although in absolute terms it is rich. Two zones
namely, 4559 - 4619 m and 4672 - 4703 m, are exceptionally rich in migrated hydrocarbons.
These zones also have the highest relative porosity (8-12 %, Figure 5) as compared to typical

porosity of 4-8 %, particularly in poor zones such as 4491 - 4499 m and 4546 - 4557 m Except
for such tight zones, no major barriers in UM2 are indicated. No core samples are available from
well 20X in trap UM1, but the Uppermost Sandstone was tested in this well and a main
drawdown flow of 3560 STBOPD was recorded.
Depth (MD m) TRAP US1 (Well 21S) Figure 5: Abundance of migrated

hydrocarbons (based on Rock Eval’s SI)
and porosity development in the Uppermost
and Upper Sandstone. Double arrows in the
center = poor and tight zones; solid bars =
perforated zonesfor testing.
3 6 9 12 5 10 15 20 25
S1 (mg HC/g rock) Porosity (H)
Depth (MD m) TRAP UM2 (Well 23S) Depth (MD m) TRAP US2 (Well 2BS)
44701-------- 4390-1------- -
4415-
4520-
4440-
4570-
4465-
4620-
4490-
4515-
■fTTrTTJTTTTJTTT 'I'1'I''1I' i rpr» ■ 11 m 111111 j 111

0 5 10 15 20 2= 8 12 16 20 10 20 30 40 10 15 20 25
S1 (mg HC/g rock) Porosity (%) SI (mg HC/g rock) Porosity (%)

3.6.3 Upper Sandstone
This section is best represented in well 26S and to a lesser extent in 21S, and therefore the
majority of the findings are based on samples from these two wells. In trap US2, which is
bounded by faults on all sides (Figure 1) and represented by well 26S, there is a rhythmic
distribution of porosity in that, while the average porosity is 10-15 %, there are alternating
zones (consisting of braided stream mudstones) with relatively lower porosity (around 5%).
There are also some ash layers present. As seen in Figure 5, this change accounts for relatively
lower migrated hydrocarbon (HC) content in these lower porosity zones (4397 - 4404 m, 4418
- 4427 m, 4448 - 4456 m, 4460 - 4470 m and 4515 - 4517 m; the 4460 - 4470 m interval is
predominantly siltstone). In addition to the indicated intervals (Figure 5), the DST # 2 in well
26S included 4311 - 4315 and 4387 - 4390 m intervals. While the average hydrocarbon
content in well 26S in the richer (and more porous) sections is about 15-20 mg HC/g rock, it
decreases to about 3-5 mg HC/g rock in the poorer sections. In absolute terms, however, the
latter figure is also regarded as good. With regards to trap US1, both the reservoir
development and sample coverage are rather poor in well 21S (Figure 5; the indicated test
interval is only part of the actual DST # 3 interval in the Upper Sandstone - 4309 - 4339 m).
Nevertheless, the average porosity (10-15 %) and the migrated hydrocarbon content (6-15 mg
HC/g rock) are in gross agreement with those of the 26S well, perhaps indicative of some
degree of reservoir uniformity in the Upper Sandstone section. All richness data quoted may be
only partially valid due to possible mud contamination.
3.6.4 Lower Sandstone
As in the case of the Upper Sandstone in well 26S (trap US2), the Lower Sandstone (trap LS3) is
also bounded by faults on all sides and vertically separated from trap US2 by a 63 m thick mud
stone section. Only the lower half of LS2 was cored, although nearly the entire section was perfo
rated and tested. The overall petroleum abundance in this trap is rich and varies from about 5-10
mg/g rock in the upper part (4669 - 4711 m), but decreases to about 2-5 mg/g rock in the lower
part (4711 - 4724 m). While there is little variation in the migrated HC abundance in LS2, there
are three major zones which are relatively tight (4690 - 4699,4702 - 4706 and 4715 - 4724 m), as
compared to the remaining interval which correspond to higher porosities (7-10%, Figure 6).
Two intervals, namely 4607 - 4653 and 4660 - 4698 m, were perforated and tested in LS2.
However the richest zones (with respect to hydrocarbon abundance) detected in this study in LS2
are 4669 - 4689, 4699 - 4702 and 4706 - 4711 m, with the first interval being the most
productive. No geochemical core data are available for the upper half of the trap, corresponding
to the perforated interval 4607 - 4653 m, but based on data from the core of lower half of the
trap, the upper and the lower halves are probably similar. In addition to the indicated intervals
(Figure 6), the DST # 1 in well 26S included 4607 - 4653 and 4660 - 4698 m intervals.
The free hydrocarbon content in LSI is generally in the 9-12 mg/g rock range in the upper part
(4457 - 4575 m in 21S), which is considered to be rich, but the content steadily decreases with

increasing depth (just about 1 mg HC/g rock in the 4650 - 4695 m interval, Figure 6). This also
corresponds with the porosity variations, with typical porosity in the upper part of 21S being 7 -
14%, but decreases (2 - 5%) with increasing depth. In addition, the overall hydrocarbon content
decreases from trap LSI in the south to trap LS2 northwards, again with corresponding decrease
in porosity to 3-7%. The 2 cored intervals of 20X in trap LS2 (one at the top and one at the
bottom of the Lower Sandstone) are both rich in solid bitumen occurrences (Bharati, 1997) but
highly depleted in detectable migrated hydrocarbons (typically only 0.5 - 1 mg HC/g rock).
Average porosity is 1-5% with a few exceptions, this being perhaps related to high content of
solid bitumen. In addition to the indicated intervals (Figure 6), the DST # 2 in well 21S
included 4448 - 4520 m interval.
Depth (MD m) TRAP LS3 (Well 26S) Depth (MD m) TRAP LS1 (Well 21S)
4457 ■«---------
4675-
4685"
4695-
4705"
4715-
5 10 15 2 4 6 8 10 12 14 3 6 9 12 15 10 15 20 25
S1 (mg HC/g rock) Porosity (%) SI (mg HC/g rock) Porosity (%)
Figure 6: Abundance of migrated hydrocarbons (based on Rock Eval’s SI) and porosity
development in the Lower Sandstone. Double arrows in the center = poor and tight zones;
solid bars = perforated zones for testing. The indicated perforated intervals in 23S are
extrapolatedfrom well 27S test (DST #1).

3.7 Variations in hydrocarbon composition across the field
3.7.1 Uppermost Sandstone
Very limited data are available in this section to monitor compositional variations as no core
samples are available from trap UM1. In addition, as no Iatroscan data are available for well
23S. Data from well 27S are used instead to exemplify UM2, keeping in mind the limited
number of samples due to lesser core coverage (Figure 7). The general hydrocarbon content is
about 80%, most of it being saturated hydrocarbons, but with conspicuous thin zones in the
entire analyzed interval consisting of non-hydrocarbon (asphaltenic) rich layers. This feature is
also seen in LS2 (well 26S), particularly in the lower half (which is known to contain solid
reservoir bitumen, Bharati, 1997), below 4625 m (Figure 8).
Depth (MD m) TRAP US2 (Well 26S) Depth (MD m) TRAP UM2 (Well 27S)
Relative % SAT/ARO Ratio Relative % SAT/ARO Ratio
Figure 7: Composition of migrated petroleum in the Uppermost and Upper Sandstone shown
as relative percentages of hydrocarbons (HC), resins (RES) and asphaltenes (ASP) as
determined by Iatroscan. The yield of saturated hydrocarbons relative to aromatic
hydrocarbons is shown as a ratio (SAT/ARO).

3.7.2 Upper Sandstone
Unlike abundance and porosity, no rhythmic nature is observed with respect to petroleum
composition in well 26S, representing trap US2 (Figure 7). In general, hydrocarbons comprise
more than 90% of the total extractable organic matter (EOM) content, the remainder being
non-hydrocarbons (NHC) in which resins and asphaltenes occur roughly in equal quantities.
As indicated by the very high (typically >20) saturated : aromatic hydrocarbons ratio
(SAT/ARO, relative percentage of saturated hydrocarbons / aromatic hydrocarbons), the major
portion of the hydrocarbons are saturated while only 2-4% are aromatic. However, saturated
hydrocarbon yield is prone to be affected by OEM contamination and therefore the actual
difference may not be so large, but we believe that the major trends are probably not so
severely affected; nevertheless the factor of limited reliability of the results must be kept in
mind. Some zones are anomalously enriched in non-hydrocarbons, particularly asphaltenes,
the most prominent being the siltstone interval from 4460 - 4470 m (Figure 7). Such intervals
are relatively rich in aromatic HCs too, as indicated by significantly lowered SAT/ARO ratio
(2-5) and on closer examination it can be seen that these intervals are also the poorest with
respect to abundance and porosity (cf. Figure 5). Trap US1, on the other hand, is significantly
different with respect to EOM composition in that only about 40-60% of the total is
hydrocarbons with SAT/ARO ratio of around 4. So, unlike in trap US2, EOM in trap US1
contains significant quantities of resins and asphaltenes (Figure 7).
The composition of EOM in the Lower Sandstone is highly variable, both down the hole and
across the field. While nearly 85-95% of EOM in trap LS3 consists of hydrocarbons
(SAT/ARO ratio ranges, 10-20, OEM effects as in the Upper Sandstone), some layers are
particularly asphaltenic and relatively rich in aromatic hydrocarbon moieties (Figure 8).
However, the vertical compositional change of the Lower Sandstone down the hole is best
seen in traps LSI and LS2 represented by wells 21S and 20X respectively. In both these wells,
the overall hydrocarbon content falls drastically with increasing depth from about 40-60% to
<15%. The fraction which correspondingly increases is the high molecular weight asphaltenic
material. This increase in the non-hydrocarbon content is also substantiated by relative
increase in the aromatic hydrocarbons at the cost of saturated counterparts (fall in SAT/ARO
ratio from 4-6 to <1, Figure 8). Comparing this to petroleum abundance data (cf. Figure 6),
particularly in well 21S, it becomes clear that the increase in asphaltenic content is concurrent
with overall decrease in abundance. In well 20X, apparently, the entire Lower Sandstone zone
(poor in migrated hydrocarbons in the first place) consists predominantly (up to 80%) of non-
hydrocarbons (Figure 8) and this supports the high amount of solid bitumen found here.

Depth (MD m) TRAP LS3 (Well 26S) Depth (MD m) TRAP LS1 (Well 21S)
4457 r
4705--
4715-
20 40 60 80 5 10 0 20 40 60 80 0 2 4 6 8 10
Relative % SAT/ARO Ratio Relative % SAT/ARO Ratio
Depth (MD m) TRAP LS2 (Well 20X)

4390
4400
4404
4408
4412
4492~
4497 =
4502
4507 U
4512 E
0 20 40 60 80 0 1 2 3
Relative % SAT/ARO Ratio
Figure 8: Composition of migrated petroleum in the Lower Sandstone shown as relative

percentages of hydrocarbons (HC), resins (RES) and asphaltenes (ASP) as determined by
Iatroscan. The yield of saturated hydrocarbons relative to aromatic hydrocarbons is shown as
a ratio (SAT/ARO).
3.8 Molecular characteristics
All core samples, except those from well 27S, are contaminated by oil-based mud (OBM)
additives to variable extent and therefore distinguishing between real and contaminant features in
some samples is difficult Problems associated with OBM contamination have recently received

some attention (Graas et al., 1997). Due to this, the usefulness of some techniques is limited, but
compositional variations which are considered to be real can be detected. Gas chromatography of
the saturated and aromatic hydrocarbon fractions has particularly proved to be of little use due to
the saturated hydrocarbon being drastically affected by OEM contamination and practically no
major compounds being detected in the aromatic hydrocarbon fraction. In addition, only a limited
number of samples were subjected to gas chromatography (Table 2). Thermal extraction gas
chromatograms (TE-GC) and pyrolysis-gas chromatograms (PY-GC, Bjor0y et al., 1992) have
therefore been used to highlight the main compositional variations in the cores. A typical
example of the effects of oil based mud (OEM) contamination (this sample is poor in migrated
hydrocarbons) is shown in Figure 9;. The dominant signature visible in the nCiz-n region is due
to additives in the OEM and masks the in-situ n-hydrocarbon signature. A few organic
components from OEM apparently adsorb to the mineral surfaces, that are sometimes difficult to
extract thermally, and are released during pyrolysis, as seen in Figure 9b. Fortunately, the in-situ
migrated hydrocarbon signature overrides the OEM effects if the samples are rich (discussed
below).
OBMccntamhaSon
i 15
jjijuJjiiiu- JbuAju_
Figure 9: Exemplary (a) thermal extraction gas chromatogram (TE-GC) and (b) pyrolysis gas
chromatogram (PY-GC) ofa sample severely contaminated by oil-based mud (OBM).
3.8.1 Uppermost and Upper Sandstone
As OBM contamination (the narrow envelope from nC# to nCig , cf. Figure 9) remains a
dominant feature in majority of the TE-GCs (common compounds present in OBM and in-situ
hydrocarbons co-elute), the real migrated hydrocarbon signature becomes maned (Figure lOa-c)
and difficult to interpret However, the in-situ hydrocarbons (nCig and higher) are detected in
several samples, in some cases up to nC#. Another significant feature of most of the TE-GCs is
the large ‘hump’ consisting of unresolved material (mostly aromatic, branched and cyclic hydro
carbons and non-hydrocarbons); part of the hump, however, represents contribution from OBM.
With regards to pyrolysate signatures, dominance of n-alkene/alkane homology (in the n-hydro-
carbon doublets in the PY-GC traces, the first peak of the doublet is n-alkene and the second
TT
'■’.0
Thermal Extracts Pyrolysates
Figure 10: TE-GC (left) and PY-GC (right) signatures from the Upper Sandstone traps US1
and US2 and Uppermost Sandstone trap UM2. Peak identification: To - toluene, Xy - xylene,
numbers indicate the number of carbon atoms in a straight chain; e.g. 15 is n-heptadecane in
TE-GC traces and n-heptadecene /heptadecane doublet in the PY-GC traces, Pr - pristane and
Ph - phytane.

peak is the corresponding n-alkane) from C4 to about C20 is clear, in some cases strong and in
others relatively weak, depending on the total asphaltene content (Figure lOd-f). Although n-
alkanes with more than 20-22 carbon atoms are detectable, they are only a minor component.
This is a fairly short range of pyrolysis products and typical of a light oil or condensate (Bjor0y et
al., 1992). In a few cases, some OEM contaminants are detected even in the PY-GC trace, where
these contaminants were not able to be totally thermally extracted (Figure lOf).
The results of trap UM2 are interesting from another point of view; while both wells 23S and
27S are practically at the same location, well 23S was drilled using OEM and well 27S was
not. Thus, comparing similar data from the two wells makes it possible to understand the
extent of OEM contamination. In general, the TE-GC and PY-GC data remain grossly similar
down to about 4330 m TVDSS (true vertical depth, sub-sea) and typical traces are shown in
Figure 11a and d. Although the thermal extracts are affected by OEM to varying degrees,
presence of migrated hydrocarbons is clearly evident. PY-GC signatures are nearly barren of
any detectable compounds. However, on comparing data from the 27S well, the real and truly
representative thermal extract signatures are seen (Figure lib) with a dominant gaussian
distribution of n-alkanes (nCis - nCgs). Clearly, contaminants from OEM severely impair the
in-situ signature. While the thermal extract composition remains grossly the same in the
samples below 4330 mTVDSS, the pyrolysate composition changes dramatically (Figure Ilf)
in that a strong n-hydrocarbon homology (as commonly obtained from mature type II source
rocks) becomes a common feature, which is the result of asphaltenic material in the sample
(solid bitumen) cracking at elevated temperatures (550°C), although no solid bitumen is seen
in the 23S cores, unlike Lower Sandstone cores of wells 20X, 21S and 26S.
TE-GCs of the two traps LSI and LS2 (wells 21S and 20X respectively) are fairly similar and
show similar changes with increasing depth. The top portion of the Lower Sandstone in these two
wells shows a comparable and unimodal distribution of n-alkanes in the thermal extracts from
nCw to nCgot with the maximum relative intensity occurring between nCie in and nCzo (Figure
12a). The difference in maxima may be related to porosity/permeability variations (e.g. higher
porosity in well 21S leading to greater loss of low molecular weight hydrocarbons). The
pyrolysate signatures of these two samples are also comparable, consisting predominantly of n-
alkene/alkane homologies (doublets) from C4 to about C20 and only n-alkanes (singlets) from C20
to at least C25. Despite the fact that the entire Lower Sandstone interval in well 20X is poor in
migrated hydrocarbons and dominantly consisting non-hydrocarbons, it is surprising to see the
‘oil’ like TE-GC signatures in the upper part samples (4396 -4411 m).
In contrast, the cores from the lower half of the Lower Sandstone in trap LSI (including
Devonian mudstone and rhyolite intervals of well 21S) exhibit one vital difference with regards
to thermal extract composition when compared to the upper half. The lower half samples are

Middle
UM2
Bottom
UM2
Figure 11: TE-GC (left) and PY-GC (right) signatures from the Uppermost Sandstone trap
UM2. a) and d): from the upper part of well 23S (drilled using OBM); b) and e):from the upper
part of well 27S (drilled using water based mud), c) and f) signatures representing the zone
below 4330 m.

significantly depleted in migrated hydrocarbons; consequently the OBM contamination becomes

prominent and the thermal extracts consist of a narrower range of in-situ n-alkanes (Figure 12b).
However, no major difference is observed with respect to the pyrolysate composition (Figure
12e) and even the lower half pyrolysales are characterized by a relatively narrow range of
products (C4 to about C20). However, a major change in pyrolysate composition is seen
horizontally across in trap LS3 (well 26S) where a rich distribution of heavier moieties is
apparent (Figure 12f), perhaps indicating thermal degradation of asphaltenes or pyrobitumen
contained in these samples. The thermal extract, on the other hand, clearly shows presence of
presence of migrated hydrocarbons in trap LS3 (Figure 12c).
3.9 Discussion
Having presented all relevant abundance and compositional data with regards to the Embla
sandstone core samples, it is quite clear that there exist variations, potentially large, in both
respects. What is not clear with certainty, due to apparent OBM contamination, is the extent of
these variations and the percentage by which, for example the richness data, have been
affected. Nevertheless, based on the observed data and inherent limitations, an attempt has
been made to synthesize the results and view them, on a field scale.
3.9.1 Comparison of the Uppermost Sandstone traps UM1 and UM2
Traps UM1 (well 20X) and UM2 (well 23S) are relatively shallow and contain no obvious solid
bitumen development is seen. However, there are chemical indications below 4330 m in 23S that
microscopic solid bitumen is present in the samples. Since the pyrolysate composition of most
solid bitumens is similar, it is likely that the bitumen is disseminated throughout most of the cores
in the lower parts of the Uppermost Sandstone in wells 23S/27S. The change in pyrolysis
products between the upper and lower parts of the Uppermost Sandstone may also mark a change
from more productive oil interval to less productive bitumen-filled intervals, which occurs at
different depths in different wells.
Another interesting comparison shown in Figure 13 is the effect of OBM contamination on the
saturated hydrocarbon GC signatures. While the core sample from well 27S shows the real in-situ
signature and composition of hydrocarbons in trap UM2 (a gaussian distribution and n-alkanes
traceable up to nCae, pristane:phytane ~1, Figure 13g), the 23S core sample from the same region
has a far larger unresolved hump, a much weaker n-alkane homology and even an altered pris-
tane:phytane ratio (Figure 13h), these being due to organic mud additives penetrating the host
rock and replacing the in-situ hydrocarbons.
3.9.2 Comparison of the Upper Sandstone traps US1 and US2
Trap US2, which is relatively more important in the present context due to extensive data
available, is bounded by faults on all sides and therefore may not be in communication with

Mobile and immobile migrated hydrocarbons in the Embla Field, North Sea
Figure 12: TE-GC (left) and PY-GC (right) signatures from the Lower Sandstone traps LSI
upper part (top), LS2 lower part (middle) and LS3 (bottom).

either trap TJM1 in the east or trap UM2 in the north, the faults probably serving as effective
horizontal flow barriers. The overall abundance of migrated hydrocarbons and porosity
development across the Upper Sandstone traps is comparable (typically 10-15 mg HC/g rock),
but clear differences exist with regards to the composition, particularly between traps US1 and
US2 (hydrocarbons are only 40-60% in the former and >90% in the latter, OBM effects?). Trap
US2 has several tight zones with intercalating high porosity (10-15%) zones rich in free,
extractable (and producible) hydrocarbons. In general, there is a slight decrease in petroleum
abundance and porosity in this trap with increasing depth, but the richest intervals are apparent
(Figure 5). DST # 2 in trap US2 consisted of seven intervals covering the entire Upper
Sandstone.
In well 26S, the logger’s depth was about 13 m deeper than the driller’s depth, the latter being the
same as measured depths in our case. Taking this anomaly into account, the relative productivity
from various perforated intervals is estimated (Table 3). Based on the available data of this study,
it seems that although there exist some compositional differences, the entire Uppermost and
Upper Sandstone interval contains migrated hydrocarbons and in practice can be considered as a
pay-zone, discounting the obvious tight and poor zones.
Table 3: Correlation of intervals rich in migrated hydrocarbons (Driller’s depth) as estimated by

geochemical evaluation to actual perforated intervals (Logger’s depth) in the Upper Sandstone
of trap US2 (represented by well 26S).
Perforated Corresponding interval rich Estimated Relative

Interval (m) in Migrated hydrocarbons Productivity
4311-4315 Not detected Poor
4387-4390 Not detected Poor
4396 - 4404 Not detected Poor
,4413-4422_,, ............. 4405^4418...........
4435 - 4454 4427 - 4448 . . High
4478-4521 4465 - 4495 & 4501 - 4515 High
4527 - 4540 4518 - 4533 High
Based on saturated hydrocarbon and whole oil compositions, the Uppermost Sandstone DST
#1 from 20X and Upper sandstone DST # 3 from 21S (trap US1) are very similar, but they
vary slightly when compared to Upper Sandstone DST #2 from 26S (trap US2) in that while
all are light-end biased (the US2 oil more strongly), the US2 oil from 26S is relatively lighter
(Figure 13, Table 4). This and other minor differences may be maturity related (discussed in
Bharati et al., 1997b). Given the similarity of oils from traps UM1 and US1 and considering
the up-dip position of US1, the oil in US1 may represent a spill-over from trap UM1 after
UM1 was saturated.

Figure 13: Composition of whole oils obtained from DST as determined by whole oil GC and satura
ted hydrocarbon fractions from selected core samples. Whole oil from traps a) US2, b) UM1 and c)
LSI. d) saturated HCfraction from trap LS2 (lower part of well 20X). Whole oilfrom traps e) LS3 and
f) UM2. Saturated HCfraction from traps g) UM2 (upper part) of well 27S and h) UM2 (upper part)
of well 23S (oil based mud used during drilling). Peak identification: numbers indicate the number of
carbon atoms in n-alkane; e.g. 15 indicates n-heptadecane. Pr - pristane and Ph - phytane.

3.9.3 Comparison of the Lower Sandstone traps LSI, LS2 and LS3
As with the Upper Sandstone, the three traps in the Lower Sandstone are separated from each
other by faults, which have a potential of functioning as barriers to lateral communication with
the adjacent traps. In addition, the Lower Sandstone is separated from the Uppermost or Upper
Sandstone by a thick mudstone sequence thus impeding vertical communication. Traps LSI,
LS2 and LS3 occur at different depths with LS3 being most deeply buried (about 258 m
TVDSS deeper with respect to LSI, Figure 3).
Table 4: Selected geochemical data ofEmbla oils from various sandstone intervals.
Sandstone —> Uppermost Upper * Lower

Trap -> UM1 UM2 US2 US1/LS1* LSI LS3
Well/DST -> 20X/M 27Sf#l 265/#2 215/#3 2 JS/#i 265/#7
% Saturated HCs 76.40 81.12 79.61 77.26 76.72 86.48
% Aromatic HCs 17.49 14,88 A. "16.96 10.52
% Non-HCs 6.09 4.00 4.08 5.57 6.33 3.01
SAT/ARO "437 " "&45"" "4.87 _ 4J50" 432 ' 832
Pristane/Phytane 1.26 1.48 1.34 1.32 1.32 1.43
Pristane/nCj7 0.43 0.44 0.50 0.45 <148 0.61
Phytane/nCig 0.39 0.35 0.44 0.39 0.41 0.48
CPI" " .UX) . 1.02 1.09 1. 103 103 L16
Isoheptane ratio 2.97 2.81 2.75 2.65 2.47 5.19
MPX/EB ratio ' 4.00 ~ &7b 3.82 3.60 3.23 438
* commingled test consisting ofDST #2 interval in the upper part of the Lower Sandstone and
the new Upper Sandstone interval (cf. Figure 3forDST intervals).
Geochemical data suggests that, with increasing depth, there is a decrease in migrated
hydrocarbon abundance. The cored interval in well 26S is in the lower half and is also the zone
with solid bitumen occurrences. Although the major portion of the EOM is saturated
hydrocarbons (generally around 80%) and non-hydrocarbons form only a minor percentage, trap
LS2 is tighter and less permeable than trap US2 due to extensive solid bitumen, which has
permanently destroyed substantial porosity and permeability. Consequently, the reservoir
capacity (current pore volume) and thereby net hydrocarbons in place is also reduced. This is
particularly evident (cf. Figures 6 and 7) on comparing traps LSI (well 21S, 4650 - 4693 m) and
LS2 (well 20X, both the cored intervals 4396 - 4411 and 4492 - 4510 m) to LS3 (well 26S, the
entire cored interval 4669 - 4726 m, but particularly below 4690 m). The relatively low flow
recorded during DST in these intervals support this observation (500 BOPD in DST # 1 of well
21S and 332 BOPD in DST # 1 of well 26S). It is therefore conceivable that the Lower
Sandstone in 20X will also yield similar production rates (no DST conducted).

No DST was conducted in the Lower Sandstone of 20X, so comparison of the compositions of
traps LSI and LS2 is restricted to DST # 1 and 2 from well 21S (LSI) and the saturated
hydrocarbon composition of 20X (LS2) core samples. When compared to the DST # 1 oil of
UM1 (Figure 13b), the LSI oil signature (Figure 13c) is nearly identical, as is the 20X saturated
GC signature (of a core chip, Figure 13d). Geochemical parameters such as pristane : phytane
ratio, CPI etc. of the 20X saturated hydrocarbon fractions are also similar to the LSI oil (Table
4).
Figure 14: Enlargement of

whole oil GC traces (nCio to
nCjs) from traps LSI (top)
and LS2 (bottom) represen
ting the two oil types, A and B
respectively. I to P represent
the peak pairs in the nCio.17
range used to highlight the
compositional differences
through star diagrams. nCll,
nC15, Pr and Ph are
undecane, pentadecane, prist
ane and phytane peaks
respectively.
rC11
Based on n-alkanes distribution, all the Embla reservoir oil samples are grossly similar (all are
light oils), except for some minor differences which may be maturity related (addressed in the
Bharati et al, 1997a), but source related organic facies differences must be examined. While the
major components of the oils (n-alkanes) do not exhibit and permit large discrimination, closer
examination of the minor components which occur nearly at the baseline of the chromatograms
present a better and distinct picture of possible compositional variations (Figure 14). Using such
minor components, star diagrams have been successfully used to highlight such differences

(Kaufman et al., 1990; Halpem, 1995). In the case of Embla oils, 32 peaks were chosen in the
nC? - nCn range and ratios calculated.
Apparently, subtle compositional differences occur in the Embla oils, particularly with respect to
relative abundance of these components. On plotting the calculated ratios as star diagrams
(Figure 15, shown as two plots to make interpretation easier), the six Embla DST oils plot as two
distinct populations (two different star shapes) - type ‘A’ consisting of oils from traps US1 and
LSI and type ‘B’ consisting of oils from traps US2, LS2 and LS3. While each of the oil types
consist of oils closely related to each other, it seems that the Embla reservoir consists of two oil-
type end-members: type ‘A’ represented by DST # lof well 20X (trap US1) and type ‘B’
represented by the DST #1 oil of well 26S (trap LS2). In the case of oils from traps US2 and
LS3, while both are very similar to the type ‘B’ end-member, half the ratios (C, D, E, F, G, K, M
and N) tend to be biased towards the type ‘A’ values. This suggests that the US2 and LS3 oils
while grossly being type ‘B\ have in addition a minor component of type ‘A* oil. Despite the
known similarity in maturity of all the Embla oils, these data indicate that two different sources
may be involved, possibly with different drainage areas. This aspect is discussed further in
Bharati et al. (1997b).
Increasing
C number
TRAPS US1/LS1
TRAP LS2
TRAP US2
TRAP LS3
Figure 15: Oil correlation star diagrams of the six Embla oils. Two distinct oil types are apparent,
type ‘A’ in traps US1, UM1.LS1 and LS2 shown as a dark band and type ‘B’ in traps US2, LS3 and
UM2. Oils in traps LSI and LS2 are interpreted to be the end-members.
The observation that DST # 1 from well 26S is different from the others, particularly with respect
to oils from wells 20X and 21S, is also supported by the findings of Li and Larter (unpublished
results) based on their pyrrolic nitrogen studies of the Embla oils. Apparently, unlike the other

oils, 26S DST # 1 is enriched in methyl- and dimethylcarbazoles and depleted in

benzocarbazoles, Based on this and other related organic nitrogen data, they concluded that this
was due to this oil being derived from a different kitchen. Another significant aspect with respect
to abundance and compositional variations in the Lower Sandstone is that, irrespective of
absolute richness differences, the deepest samples analyzed in 26S (base of LS2) and 23S (not
the base of UM2) are oil bearing. This is however not true in the case of trap LS1. While only the
4457 - 4576 m MD zone in 21S seems to be oil bearing, the entire Lower Sandstone in 20X is
devoid of any ‘producible’ hydrocarbons, although the top 15 m or so give residual oil signatures.
3.10 Summary and Conclusions
The Embla Field, a NW-SE oriented field of about 19.4 km2 at top Paleozoic, consists of three
reservoir units, the Uppermost, Upper and Lower Sandstones, separated vertically by a thick
mudstone facies. In addition, the reservoir section is intensely faulted, causing high risk for
compartmentalization, a feature partially evident in the EFT and DST data. Due to the known
geological complexities, extensive coring was conducted which served as a good database for
detailed geochemical assessment. Evidently, both hydrocarbon abundance and compositional
variations, generally agreeing with the petrophysical disparities, are present in the Embla Field. In
addition to periodic invasions of hydrothermal fluids into the reservoir causing repeated periods
of porosity loss and enhancement, there is a significant solid reservoir bitumen in the Lower
Sandstone. The Upper Sandstone in well 26S, rich in migrated hydrocarbons and with higher
porosity, is apparently more ‘rhythmic’ and non-homogenous with respect to hydrocarbon
richness and composition, as compared to the Lower Sandstone. However, the migrated
petroleum in the Upper Sandstone is richer in hydrocarbons relative to non-hydrocarbons, when
compared to the Lower Sandstone petroleum. This, in all likelihood, is due to extensive
asphaltene-rich solid bitumen in the latter. Compositionally, the signature of migrated petroleum
changes both horizontally across the various traps and vertically with increasing depth. This is
particularly evident in the Lower Sandstone traps LSI and LS2, where the relative non-
hydrocarbon percentage increases dramatically with depth. Interference from oil-based mud
contaminants is quite severe in nearly the entire core sample suite, which has restricted detection
of underlying differences in the Embla oil population. Nevertheless, it was possible to establish
the gross differences based on a combination of various techniques. The data from the present
study suggests that the order of richness of various traps is: UM2 (richest), US2, UM1, LS3, LSI
and LS2 (relatively least rich). However, it must be borne in mind that data from trap LS2 are far
less numerous and do not represent the entire trap vertically.
In addition, there are indications that the identified principal traps may not be in communication
with each other and represent two different oil populations. Also, the compositional and
molecular variations that we see may be related to maturity and/or different source facies. These
aspects, amongst others, are addressed in the second paper on the geochemical evaluation of the
Embla Field (Bharati et al., 1997b).

3.11 Acknowledgments
SB thanks Norwegian Research Council, Phillips Petroleum Co. Norway and Amoco Norway for
part financial assistance. The staff of Geolab Nor is thanked for assistance in geochemical
analyses and the Department of Geology, Norwegian University of Science and Technology,
Trondheim for logistics and encouragement Comments made by Richard Patience, Statoil and
Chip Feazel, Phillips Petroleum on earlier drafts improved the quality of this manuscript. The
authors acknowledge the following for permission to publish the paper. Phillips Petroleum Co.
Norway and co-venturers, including Fina Exploration Norway S.C.A., Norsk Agip AS, Elf
Petroleum Norge AS, Norsk Hydro Production AS, Statoil AS, TOTAL Norge AS and Saga
Petroleum AS. The authors further acknowledge that the interpretations and conclusions
presented herein do not necessarily reflect the opinions of the co-venturers.
3.12 References
Bharati, S., 1997, Solid reservoir bitumen in the Embla Field, Norwegian Continental Shelf -1:
Occurrence, development and morphotypes: AAPG Bulletin, (under submission).
Bharati, S., Rpstum, G. R. and L0berg, R., 1994, Calibration and standardization of Iatroscan
(1LC-FID) using standards derived from crude oils, Organic Geochemistry, v. 22, p. 835-862.
Bharati, S., Hall, P. B. and Bjorpy, M„ 1997a, Identifying diverse oil families in the Greater
Ekofisk area, Central Graben, Norwegian Continental Shelf: Marine and Petroleum Geology,
(under submission).
Bharati, S., Hall, P. B., Vagle, K. and Bjor0y, M., 1997b, Geochemical evaluation of the Embla
Field, Norwegian Continental Shelf- 2: Source, infilling, compartmentalization and intra-
reservoir communication: Marine and Petroleum Geology, (under submission).
Bjor0y, M., Hall, K. and Jameau, J., 1990, Stable carbon isotope ratio analysis on single comp
ounds in crude oils by direct GC-isotope analysis: Trends in Analytical Chemistry, v. 9, p. 331-
337.
Bjor0y, M., Hall, K., Hall, P. B. and Leplat, P., 1992, Detailed hydrocarbon analyzer for well site
and laboratory use: Marine and Petroleum Geology, v. 9, p. 648-665.
England, W. A., Mackenzie, A. S., Mann, D. M. and Quigley, T. M., 1987, The movement and
entrapment of petroleum in the subsurface: Journal of Geological Society, v. 144, p. 327-347.
England, W. A., 1990, The organic geochemistry of petroleum reservoirs: Organic Geochemistry,
v. 16, p. 415-425.

Fraser, A. J., Farnsworth, J. and Hodgson, N. A., 1993, Salt controls on basin evolution- Central
North Sea, in A. M. Spencer, ed., Generation, Accumulation and Production of Europe’s hydro
carbons: Springer-Verlag, Berlin, p. 59-68.
Gowers, M. B. and Sasbpe, A., 1985, On the structural evolution of the Central Trough in the
Norwegian and Danish sectors of the North Sea: Marine and Petroleum Geology, v. 2, p. 298-
318.
Graas, G. V., Dahlgren, S., Mills, N. and Sollie, F., 1997, The effects of drilling mud
contamination on the quality of geological measurements: The 18th International Meeting on
Organic Geochemistry 1997 Abstracts, Maastricht.
Hall, P. B., Stoddart, D., Bjor0y, M., Larter, S. R. and Brasher, J. E., 1994, Detection of
petroleum heterogeneity in Eldfisk and satellite fields using thermal extraction, pyrolysis-GC,
GC-MS and isotope techniques: Organic Geochemistry, v. 22, p. 383-402.
Halpem, H. I., 1995, Development and applications of light hydrocarbon based star diagrams:
Horsfield, B. and McLimans, R. K., 1984, Geothermometry and geochemistry of aqueous and
oil-bearing fluid inclusions from Fateh field, Dubai: Organic Geochemistry, v. 6, p. 733-740.
Kaufman, R. L., Ahmed, A. S. and Elsinger, R. 1,1990, Gas chromatography as a development

Knight, I. A., Allen, L. R., Copiel, J., Jacobs, L. and Scanlan, M. J., 1993, The Embla Field, in
J. R. Parker, ed., Petroleum Geology of Northwest Europe: The Geological Society, London,
p. 1433-1444.
Larter, S. R. and Aplin, A. C., 1995, Reservoir geochemistry: methods, applications and opportu
nities, in J. M. Cubitt and W. A. England, eds., The geochemistry of reservoirs: Geological
Society Special Publication 86, p. 5-32.
Leythaeuser, D. and Ruckheim, J., 1989, Heterogeneity of oil composition within a reservoir as a
reflectance of accumulation history: Geochimica et Cosmochimica Acta, v. 53, p. 2119-2123.
Norwegian Industry Guide to Organic Geochemical Analyses, 1993, Joint report by Statoil,
Norsk Hydro, Saga Petroleum, IKU, Geolab Nor and the Norwegian Petroleum Directorate.
Sears, R. A., Harbury, A. R., Protoy, A. J. G. and Stewart, D. J., 1993, Structural styles from the
Central Graben in the UK and Norway, in J. R. Parker, ed., Petroleum geology of northwest
Europe: The Geological Society, London, p. 1231-1243.
Stoddart, D. P., Hall, P. B., Larter, S. R., Brasher, J., Li, M. and Bjor0y, M., 1995, The reservoir
geochemistry of the Eldfisk Field, Norwegian North Sea, in J. M. Cubitt and W. A. England,
eds., The geochemistry of reservoirs: Geological Society Special Publication 86, p. 257-279.

Paper 3: Embla Geochemistry: Source, infilling, and intra-reservoir communication 55
Chapter 4: Paper 3
Geochemical evaluation of the Embla field, Norwegian

Continental Shelf - 2: Source, infilling, compartmentalisation and
intra-reservoir communication §
Sunil Bharati \ Peter B. Hall \ Rare Vagle2 and Malvin Bjorpy1
Geolab Nor, 7002 Trondheim, Norway;2- Phillips Petroleum Co., 4056 Tanager, Norway.
4.1 Abstract
In this paper, the second part of a larger study on geochemical evaluation of the migrated
hydrocarbons in the Embla Field, the aspects of source, maturity, intra-reservoir communi
cation (compartmentalisation) and filling history are reported. Based on the known geological
complexities (extensive faulting) and DST and RFT pressure data, it was suspected that the
potential of compartmentalisation in the Embla Field was high. It was seen in the first part that
the Embla field consists of two distinct oil populations, type A and B. In addition to the two
oil types differing slightly in composition, type A oil is slightly less mature than type B oil,
although both types are of base oil-window to condensate window maturity. By integrating all
geochemical and petrophysical data, trap boundaries and positions of oil-water contacts and
solid bitumen zones have been estimated in various parts of the field. Various Upper Jurassic
source facies are examined in light of the available data of this study and possible source
kitchens suggested. By incorporating neighbouring well data, various field charging scenarios
are discussed and filling directions suggested for Embla. As two different sources are
interpreted to have charged the Embla Field, the aspect of post-emplacement mixing is also
considered. The implications of discontinuous oil-water contact and solid reservoir bitumen
occurrence on overall field productivity and future exploration and development are reviewed.5
5 Manuscript under submission to Marine and Petroleum Geology

4.2 Introduction
This is the second of the two papers on geochemical evaluation of the Embla Field. The first
paper (Bharati et al., 1997a) assessed the occurrence and compositional variations of migrated
hydrocarbons in the main reservoir units of the Embla Field, namely the Paleozoic Upper and
Lower Sandstones. This paper addresses the aspects of source, maturity and
compartmentalization of the migrated hydrocarbons, both mobile that can be produced and
immobile, solid bitumen that cannot be produced. In addition, an attempt is made to postulate
the filling history of the reservoir. Geochemical appraisal of petroleum reservoirs with respect
to fluid molecular characteristics (oil composition and maturity or water composition) has
recently been carried out on some fields of the North Sea (e.g. Horstad et al., 1990; Larter et
al., 1991; Smalley at al., 1992; Hall et al., 1994; Mason et al., 1995). Most of these studies
have utilized chemical data of oils such as compositional and maturity variations, physical
properties etc. from different parts of the field to assess heterogeneity and barriers to fluid
flow, and to link these geochemical observations to geological data to address regional
migration routes and the filling history of the field. The fact that geochemical disparities are
present and can be monitored in an oil population of a field is largely developed from the
earlier works of England et al. (1987) and England and Mackenzie (1989), and is based on the
principle that lateral compositional variations in particular, acquired during the oil
emplacement process, are likely to be retained in the petroleum systems despite diffusive or
density-driven mixing, which attempt to establish equilibrium in the reservoir.
In the case of Embla evidently, both hydrocarbon abundance and compositional variations
correspond well with the petrophysical disparities, discounting for apparent oil based mud
(OMB) contamination (Bharati et al., 1997a). The Uppermost and Upper Sandstones, which have
higher porosity, are rich in migrated hydrocarbons and are apparently more ‘rhythmic’ and non-
homogenous with respect to richness and composition, compared to the Lower Sandstone. How
ever, the migrated petroleum in the Upper Sandstone is richer in hydrocarbons relative to non-
hydrocarbons, compared to the Lower Sandstone petroleum. This, in all likelihood, is partially
due to extensive asphaltene-rich solid bitumen in the latter. Compositionally, the signature of
migrated petroleum changes both horizontally across the various traps and vertically down the
reservoir. This is particularly evident in the Lower Sandstone traps LSI and LS2, where the
relative non-hydrocarbon percentage increases dramatically with depth. Interference from oil-
based mud contaminants is quite severe in nearly the entire core sample suite; however, it is
possible to establish the gross variations within the Embla reservoir.
4.3 Geological background
This has been covered in detail in Bharati et al, 1997a, but briefly the Embla Field, a NW-SE
oriented field of about 19.4 km2 at top Paleozoic, consists of three reservoir units, the Uppermost

sandstone (defined by traps UM1 in well 20X and UM2 in wells 23S/27S), Upper Sandstone
(traps US1 in well 21S and US2 in well 26S) and Lower Sandstone (traps LSI in well 21S, LS2
in well 20X and LS3 in well 26S), separated vertically by a thick mudstone facies. The reservoir
section is intensely faulted, potentially causing compartmentalisation, a feature which was
suspected on evaluating the RFT and DST data. Due to the known geological complexities,
extensive coring was conducted which served as a good database for detailed geochemical
assessment In addition to periodic invasions of hydrothermal fluids into the reservoir, causing
repeated periods of porosity loss and enhancement (Knight et at, 1993), there is considerable of
solid reservoir bitumen in the Lower Sandstone.
4.4 Samples and Methods
Of the initial suite of 973 samples from the Embla field (Bharati et al, 1997a), a selected
sample set was subjected to detailed analyses (Table 1), covering all the traps and taking into
account all the variations or similarities observed.
Table 1: Details of number of samples analysed from the Embla Field, block NOCS 2/7.
Wells 20X, 21S, 23S, 25S, 26S and 27S cover the reservoir sections (Upper and Lower
Sandstones, all core samples) while wells 24 and 28 contain mainly potential source rocks
(claystone cores and cuttings).
Well No. GHM-MS 1 GC-MS 2 Bulk 813C 3 GC-IRMS

4
20X 13 8 8 —
21S . 14. _ , 8 8
23S 29 10 10 -
24 5 .7.......... 7 —
25S 11 15 15 -
.......26S____ ........64.. , .20 _ .. _ . 20. _ -

27S 4 7 7 -
28 5 5 5 —
Oils - 6 6 6
Total 145 gri 86 6
7- Thermal extraction - mass spectrometry. 2- Gas chromatography - mass spectrometry.

3 - 8I3C of bulk separatedfractions (saturated and aromatic HCs, resins and asphaltenes).
4 - Compound specific gas chromatography - isotope ratio - mass spectrometry.
In addition, several oil samples from surrounding oil fields (Eldfisk Alpha, Eldfisk Bravo,
Albuskjell, 2/7-19R, 2/7-3X) were analysed for comparison and correlation. All analyses were
performed according to procedures specified in the Norwegian Industry Guide to Organic
Geochemical Analyses (1993). In addition to the reservoir section, several potential source

rocks samples were also analysed from three wells (2/7-24, 2/7-28 and 2/6-3). Thermal
extraction - Mass spectrometry (GHM-MS) (Bjorpy et al., 1991) was performed directly on
bulk powdered rock samples to obtain biomarker data. Conventional gas chromatography -
mass spectrometry (GC-MS) was also performed on a lesser number of samples using
separated hydrocarbon fractions (obtained by liquid chromatography) to obtain additional
biomarker data. Bulk 813C measurements were performed on all the 4 separated fractions
(saturated and aromatic hydrocarbons, resins and asphaltenes) and EOM to assess the source
and maturity variations in the migrated petroleum. Last, gas chromatography - isotope ratio -
mass spectrometry (GC-IRMS) was performed on all six oil samples to highlight the subtle
differences among the oils due to either maturity or source (Bjor0y et al., 1990; Bjor0y et al.,
1994; Bharati et al., 1997b), which otherwise would have been difficult to establish by the
above analytical techniques.
4.5 Maturity of the Embla oils
Given the gross composition of the Embla oils (light condensate-like oils, Bharati et al,
1997a), the likelihood of these being highly mature must be examined, in addition to
characterizing the source facies of these oils. Thompson (1987) used gasoline range and light
hydrocarbon based ratios (from whole oil gas chromatography) to characterize, define and
distinguish oil populations with respect to paraffinicity (n-heptane/methylcyclohexane),
aromaticity (e.g. toluene/n-heptane and meta + para-xylene/n-octane) and normality (n-
heptane/isoheptane). In addition, Rovenskaya and Nemchencko (1992) used the meta + para-
xylene/ethylbenzene ratio as a maturity indicator.
m,p-Xylene / Ethylbenzene Ratio Figure 1: Maturity based light

hydrocarbon ratios to highlight
XUM2
□US2
the internal differences within the
+USVLS1 Embla reservoir. Eldfisk and
Albuskiell Albuskjell data (after Bharati et
al., 1997b) and well 19R (DST
#1) are includedfor comparison.
Eldfisk
3 - —
isoheptane Ratio

Based on these ratios, Embla oils are apparently more mature than the Eldfisk oils, but less
mature than the Jurassic oil (DST #1) from well 2/7-19R (located about 8 km west of Embla,
Figure 1). Within the Embla oil population, the oil from trap LS2 (268/ DST #1) is an outlier,
perhaps indicating its higher maturity than the others. Toluene/n-heptane and n-heptane/methyl
cyclohexane ratios are affected by source maturity and reservoir alteration processes such as
evaporative fractionation, biodegradation, water washing etc. (Thompson, 1987) and, in the
case of the Embla oils, maturity is possibly the overriding factor, although minor spread away
from the maturity trend may be source facies related (Figure 2).
Toluene / n-heptane Figure 2: A cross-plot of light

TRAP
hydrocarbon ratios that are
XUU2 affected by both maturity and
OUS2
+US1/LS1 post-reservoiring secondary
processes.
Albuskjell
Eldfisk
i ' '—l 1 1—'—'—i—'—'—'—r~~i—1—'—'—'—

0 0.5 1 1.5 2
n-Heptane / methyl cyclohexane
Maturity estimation based on the sterane and teipane parameters is not feasible in the case of
Embla for two reasons: either because these parameters are not accurately measurable (due to low
concentrations) or the parameters have reached their maximum values. This is particularly
evident on comparing the m/z 163 mass fragmentograms of the Embla oil samples to Cretaceous
Chalk reservoired Eldfisk oils (Figure 3); the Embla oil contains dominantly steranes (mostly C27-
29 diasteranes) whereas the Eldfisk oil has in addition, a significant hopane content This is likely
due to higher maturity of the Embla oils, as hopanes (particularly the ap hopanes) are thermally
degraded before the steranes and only relatively more thermally stable hopanes such as C27.29
neohopanes and C30 diahopane remain (Moldowan et al., 1991). In addition, sterane parameters
in particular can show a decrease beyond a certain maturity level, and Waples and Machihara
(1991) suggest that the most useful ratio (%Cag acta 20S/20S+20R) is only effective in the 0.4 -
0.8% Ro range.

Steranes a) Embla Oil-m/z163 b) Eldfisk Oil-m/z163
Hopanes
Hopaoes
Figure 3: Examples ofm/z 163 mass chromatograms representing (a) Embla oils and (b) an
Eldfisk oilfor comparison.
In the case of Embla oils, the dominant terpanes are the most thermally stable C27-29 neohopanes
(so-called Ts compounds) and C29.31 diahopanes. The C29.35 ot|3 hopanes, ubiquitous in oil
window mature Upper Jurassic source rocks and oils, are virtually absent The maturity of these
oils is therefore considered to be base oil window to condensate window. Steranes of the Embla
oils are dominated by C27 and C29 diasteranes and C21-22 short side-chained steranes. The
abundance of C27 diasteranes is greater than C29 compounds. All the normal sterane maturity
parameters have reached their maximum values and may even yield spuriously low values.
Regular steranes, particularly acta compounds, are present in only trace amounts, again typical of
very high maturity oils. Therefore, while such parameters show that Embla oils are more mature
than other Greater Ekofisk oils, they fail to distinguish between the Embla oils.
However, aromatic hydrocarbon based maturity parameters are relatively more useful. For
example, based on a plot of two aromatic maturity parameters, dimethyl naphthalene ratio
(DMNR, Hall et al., 1985) and methyl phenanthrene index (MPI 1, Radke, 1988), a range of
maturities is evident for the Embla oils (Figure 4), although all the Embla oils are very mature, as
noted above (Rc > 0.9%, Table 2). Compared to the Embla oils, the Eldfisk and Albuskjell oils
are of much lower maturity (Bjorpy et al., 1994; Bharati et al., 1997b). However, the Jurassic oil
from well 19R is more mature than the Embla oils. A closer examination of methyl
dibenzothiophene (MDBT) based maturity ratios (Table 2, Figure 4b) shows that the oils in traps
LS2 and UM2 (DST #1 from 26S and 27S respectively) are more mature than the oils in traps
UM1 and LSI (oil from US2 also plots close to UM2 and LSI; this may be an analytical error).
Based on distinct compositional differences noted in the minor compounds (essentially non n-
alkanes) using star diagrams (Kaufman et al., 1990), Bharati et al. (1997a) have shown that the
Embla Field consists of two discrete oil populations - type ‘A’ (traps US1, LSI, UM1 and LS2)
and type ‘B’ (traps US2, LS3 and UM2).

Dimethylnaphthalene Ratio Figure 4: (a)

Methylphenanthrene index (MPI
1) against dimethyl-naphthalene
ratio (DMNR) and (b) 4/1 Methyl
dibenzothiophene (4/1 MDBT)
Albuskjell
against 3+2/1 Methyl dibenzo
3 " 'Eldfisk-Bravo-
thiophene (3+2/1 MDBT)
maturity parameters obtained by
gas chromatography of oils. For
comparison and correlation, data
for potential source rocks (wells
2/7-24, 255 and 28) are plotted in
1 - — (a).
Eldfis : Alpha Well 24
Well 28
Methylphenanthrene Index
3+2/1 Methyl dibenzothiophene Ratio

100
TRAP
XUM2
□ US2
+US1/LSI
▼ LSI
ALS3
*19R X A
to * +
t"
Albuskjell
Eldfisk
0.1
0.1 1 10
4/1 Methyl dibenzothiophene Ratio
Fine internal differences within the Embla oil population are also reflected in the overall distri
bution of hopanes. For example, while the hopane deficiency is common to all Embla oils when
compared to the Eldfisk oils, minor differences due to maturity and/or source are present, as seen
in m/z 191 and 217 mass chromatograms. For example, 29Ts is significantly higher in type ‘A’,
27aS diasterane relative to 28[5S diasterane higher in type ‘B* and 27PR relative to 29pS
diasterane higher in type ‘ B’ (Figure 5).

Embla Type ‘A’
Embla Type ‘B’
Eldfis
m/z 191 m/z217
Figure 5: M/z 191 (left) and 217 (right) mass fragmentograms showing the triterpane and
sterane compositions in Embla type ‘A’ (top) and ‘B’ (middle) oils and the Eldfisk oil
(bottom) for comparison.. Peak identifications: 27Ts - 18a trisnomeohopane , 27Tm - 17a
trisnorhopane, 30afi - a/3 hopane, 27d/3S - 20S j8a diacholestane, 29dpS - 20S Pa 24-ethyl
diacholestane and 29aaR - 20R aaa 24-ethyl cholestane.
The higher thermal maturity of Embla oils, particularly in relation to Eldfisk oils, is also evident
from aromatic biomarkers (Radke, 1988); for example high 3+2/9+1 methyl phenanthrene ratio

(based on m/z 192, a ratio value of about 1 indicates base oil window maturity), high 2,6 + 2,7/
1,5-dimethyl naphthalene ratio (based on m/z 156, a ratio value greater than 2 indicates high
maturity) and high 3+2/1 methyl dibenzothiophene (based on m/z 198, a ratio value of 2-3
indicates base oil window) for the Embla oils (Table 2). Closer examination of these ratios also
reveals that, compared to oils from traps LSI, LS2 and UM1 and US2, the ratios are generally
much higher (indicating relatively higher maturity) for oils from traps LS3, US2 and UM2, with
trap LS3 oil being most different
Table 2: Selected maturity related geochemical data of Embla oils based on gas
chromatography (upper half) and gas chromatography-mass spectrometry (lower half).
Up per Sandstone Lower Sandstone

Trap —> UM1 US2 US1/LS1* LSI** LS2 UM2
Well/DST-+ 20X/#1 265/#2 21S/#3 21S/#1 26S/#1 27S/#1
Dimethyl naphthalene 3.38 3.09 2.77 3.18 4.34 3.65
ratio (DMNR)
Methyl phenanthrene 0.99 0.98 0.89 0.9 1.21 1.11
Index(MPI) .
Calculated Vitrinite 6.99 0.99 0.93 0.94 1.13 1.07
reflectance (% Rc)
3+2/1 methyldibenzo- 5,9 6,10 8.0 5.0 14.03 14.01
thiophene (MDBTX_
4/1 methyldibenzo- 41 39.8 80 35 64.19 39.2
thiophene (MDBT)
29af3,/30aphopanes,„, .... 1.24 ..... 0.85 0.68 0.96 1.63
24/3 / 30ap hopane 3.41 2.52 2.66 2.99 5.56 >10
Cz/Cy diasteranes „ „ 2.16 .... __L77 1.9 1.84
3+2/9+1 methyl- 1.35 1.34 0.99 1.07 1.35 1.49
phenanthrene
2,6+2,7/1,5 dimethyl- 7/20 5.80 4.57 6.14 10.36 6.30
naphthalene..................
3+2/1 methyldibenzo- 3.77 6.50 3.58 3.13 7.00 5.44
thiophene
* co-mingled test consisting ofDST #2 interval in the upper part of the Lower Sandstone and
the new Upper Sandstone interval. ** test interval includes part ofLower Mudstone section.
Estimation of the petroleum maturity in the core samples is more difficult due to an additional
factor of oil-based mud (OEM) impregnation causing even lower biomarker yields. This has
particularly limited the employment of common hopane maturity parameters such as Tm/Ts and
30d/ 30d+30pa. Majority from sterane ratios is also affected by the same problem. Again,
aromatic hydrocarbon based data have proved to be useful. For example, a cross-plot of
dimethylnaphthalene ratio (DMNR) and methyl phenanthrene ratio (Kvaldheim et al., 1987)
indicates that there is a generally increasing maturity trend from trap LSI (well 21S ) on the crest,
to traps LS2 and UM2 (wells 26S in the west and 23S/27S in the north respectively), although

the data for individual wells are fairly widespread (Figure 6). This in general agreement with the
observed maturity trend based on the oil data (Figure 4).
3+2/1 Methyl phenanthrene Ratio Figure 6: Aromatic hydrocarbons

based maturity parameters,
calculated from gas chromato
graphy data of core samples.
Although the samples from well
27S belong to trap LS3, they have
been plotted separately, as this is
the only well in Embla which was
not drilled using oil-based mud
(OBM). All the other samples are
affected by OBM contamination
to varying degrees. Source rock
Eldfisk data from well 24 are also plotted
for comparison.
Dimethyl naphthalene ratio
4.6 Source of the Embla oils
Based on the above observations, the source of the Embla oils must be very mature, nearly at the
base of the oil-window for type II kerogens. In addition, the fact that the oils in traps LS2, US2
and UM2 are slightly different from the others in composition (Bharati et al, 1997a) and warrants
closer examination. A simple source facies (pristane/nCn) against maturity (dimethylnaphthalene
ratio) cross-plot (Figure 7) underlines this difference. While all the Embla oils plot outside the
main Greater Ekofisk trend, oil from trap LS2 is an outlier, suggesting that this oil (in well 26S
Lower Sandstone) was generated by a different source facies with higher maturity than the
others.
In addition, oils from traps UM1, LSI and US1 group more closely together and oil from UM2 is
intermediate (Figure 7). However, stable carbon isotope (8 13C) data for n-alkanes and branched
alkanes (obtained from GC-IRMS) clearly reiterate that there are two different oil populations in
the Embla field (Figure 8) - Type ‘A’ oil in traps US1 and LSI (well 21S) and trap UM1 (well
20X) with identical isotopic signatures and Type ‘B’ in traps US2, LS2 and UM2 (wells 26S and
23S/27S); this is the same grouping as that obtained by star diagrams (Bharati et al., 1997a). The
most marked difference is in the low molecular weight range (C5-15), in that type ‘B’ oils are
significantly heavier than type ‘A’ oils, an indication of type ‘B’ oils being more mature. Isotopic
signatures of n-alkanes heavier than about nCao are comparable for both the oil types. Perhaps the

oils from traps US1/LS1 (in well 21S) and trap LS2 (in well 26S) truly represent two different
source facies, but the observed difference could also be due to different maturities. As the
isotopic signature of US2 and UM2 oils is somewhat intermediate, these traps may have had a
minor contribution of type ‘A’ oil.
Figure 7: Pristane/nCn (a source

facies related parameter) vs.
DMNR (maturity related para
meter) of Embla and Eldfisk/
Albuskjell oils for comparison.
Both have different trends with
increasing maturity. Trap LS2
sample continues to plot as an
outlier.
The Upper Jurassic dark grey to black claystone sequence, the principal source rock in the
Central Graben (Cayley, 1987; Cooper and Barnard, 1984) is extensively developed across the
Skrubbe Fault east of the Embla dome (1791 and 159 m Mandal + Farsund Fms. in wells 2/7-24
and 2/7-28 respectively and 278 m Haugesund Fm. in 2/7-28). Wells 24 and 28 (located E-SE
and N-NE respectively with respect to Embla) are less than 2 km from the Embla dome but are
separated from the Embla dome by a major salt wall (Roberts et al., 1990). In addition, the Upper
Jurassic Tyne Gp. is well developed on the eastern flank of the Embla dome (ca 320 m thick
Mandal + Farsund Fms. in 2/7-25S, Bharati et al, 1997), but is also found as a thinner unit in the
other Embla wells (20X, 21S, 23S, 26S and 27S). The Upper Jurassic sequence is quite deeply
buried in wells 24 and 28 (Table 3), but most buried within the Embla dome (about 4120 m in
25S), although the depth of burial increases northwestward within the Embla dome. Lack of a
good sample set from within the Embla dome limits the evaluation of the Upper Jurassic source
rocks to wells 24 and 28, although it is unlikely that hydrocarbons generated in these areas could
have migrated to the Embla reservoir through the salt wall.

1
o
o
Jj
E
z
Figure 8: GC-IRMS based 813C data for individual alkanes in oils from the Embla Field. In branched
alkanes: I - iso; 2, 3, 4- position ofmethyl group; M - methyl; DM - dimethyl; C4 indicates the number of
carbon atoms in the parent molecule, e.g. iC4 - iso-propane, 3.6DMC8 - 3,6-dimethyloctane.

In addition, there is a significant difference in the Upper Jurassic facies of wells 24 and 28 (dark
grey to black claystones) and well 25S (claystone + sandstone + brecciated material). Therefore,
evidence for the source of hydrocarbons in pre-Jurassic sandstones of the Embla field is based
mostly on wells 24 and 28 and is only circumstantial.
Table 3: Selected richness, potential and maturity related geochemical data of the potential
source rocks (Upper Jurassic Tyne Group) based on Rock Eval, latroscan and saturated /
aromatic hydrocarbons gas chromatography. All data given as average values. Number of
samples in each case is given in parentheses.
Parameter Well —> 2/7-24 2/7-25S 2/7-28

Major lithology dark grey-black brownish grey dark grey-black
Claystone Claystone * Claystone
Net thickness (mTVD)....... _ -1791.... -320 Y . r-437................
Depth of occurrence (mTVDSS) 3173-4964 4120-4324 3296-3753
TOC(%) 1-9.4(49.___ 1,7(5)......... .. 14.2O0) .
Hydrogen index (mg HC/g TOC) 91-499(46) 63(9 473 (10)
Petroleumpotential (tngHC/g rock) 4-81.(46) 27(5) . 8009
Tmax (°C) 413 - 472(46) 429 (5) 447 (10)
Extractable organic matter (mg/g rock) _ 3.9:5,1901) .36.82(5) 41^2(9)
% Hydrocarbons in EOM 24-66 (11) 92.6 (5) 36.1 (9)
Saturated / Aromatic HC ratio _........ n-sjofL &29(9) _ _
% Non-hydrocarbons in EOM 34-76 (11) 7.4(5) 63.9 (9)
Pristane/Phytaneratio .................. „ W-WGL. 0-73 (%). .. _ 120(3) ...
Pristane / nCn ratio 0.35-0.57(4) 0.49 (2) 0^ (3)
PbyMs./nWatw........... ............ ... _ &30-P%#.. 0 48 (2) ........ 058 (3) ..........
Carbon preference index (CPI) 0.99 -1.08 (4) 1.14(3)
Vitrinite reflectance Ro (%) 0.98 -1.05 (4) 0.88 (2) 0.81 (3)
* includes intercalated sandstone and brecciated material.
The Upper Jurassic section in wells 24 and 28 is generally very rich in organic matter (Table 3)
and with a very rich petroleum potential, as a major portion of this section is within the oil
window. In well 24, the Mandal Fm. and the upper part of the Farsund Fm. (3150 - 4444 m) is
relatively the richest section, typically containing 4 - 10% organic carbon resulting in very rich
petroleum potential (up to 81 mg hydrocarbons/g rock). Hydrogen indices of about 200 - 500 mg
hydrocarbons/g TOC suggest a type II kerogen. The lower portion of Farsund Fm. in well 24
(below 4444 m) is relatively poor but with moderate petroleum potential (<10 mg hydrocarbons
/g rock). In well 28, however, a much greater variation is present While the upper portion of the
Farsund Fm. (3289 - 3342 m) is less rich (TOC 5 - 8%, hydrogen index 241-385 mg
hydrocarbons/g TOC, petroleum potential 8-36 mg hydrocarbons/g rock), the lower portion of
Farsund Fm. (3366 - 3446 m) is very rich (TOC 10 - 22%, hydrogen index 443-758 mg

hydrocarbons/g TOC, petroleum potential 55 - 131 mg hydrocarbons/g rock). The Haugesund

Fm in well 28, with a total thickness of 278 m, is also very rich in organic carbon (4 - 13% TOC)
with a rich petroleum potential (20 - 71 mg hydrocarbons/g rock) and high hydrogen indices (278
- 684 mg hydrocarbons/g TOC). Clearly, there is a major organic facies change occurring
vertically down and horizontally between the wells. However, very high EOM yields, as also
indicated by high SI yields during Rock Eval pyrolysis, suggest active generation taking place in
the Upper Jurassic sections of these wells at the present time.
Thermal extract and pyrolysate compositions clearly indicate an oil prone source rock and grossly
type II marine kerogen in the Mandal Fm., the upper part of Farsund Fm. and the Haugesund Fm
(Figure 9), with some minor differences (higher aromatic hydrocarbon species for instance) in
some samples due to increased terrestrial organic matter input Typically, a strong homology of
n-alkene /n-alkane doublets extending up to nC# is present and aromatic hydrocarbons are less
prominent in the pyrolysates, a signature quite typical of oil-prone mature, marine type II
kerogens (Bjor0y et al., 1992), but in the deeper section the pyrolysates are richer in lighter
components due to higher maturity (close to the base of oil-window - 1.0% Ro equivalent). The
deepest samples generate mostly gaseous components, suggesting that most of the potential has
been realized and only residual kerogen is present, this feature being more evident in well 24.
The thermal extracts are rich in n-alkanes with variable amounts of aromatic and branched hydro
carbons and the signatures indicate in-situ, active generation. Pristanezphytane ratio ranges 1.0 -
1.5 and the pristaneznCn and phytaneznCig ratios are generally within the ranges 0.34 - 0.47 and
0.31 - 0.40 respectively, indicating that the hydrocarbons have been generated in-situ from
mature marine kerogen. However, the lower part of the Farsund Fm in well 24, which is also
poorer in TOC, is quite different and with a higher terrestrial input (type n/E3 kerogen) and
consequently lower oil potential. In the case of well 28, the deeply buried Haugesund Fm is still
rich in organic carbon with high hydrogen indices, indicating that a significant portion of the
generative potential is unrealized.
The most conspicuous compositional difference, however, is seen in the very high TOC interval
(3366 - 3446 m) in the lower half of the Farsund Fm in well 28. Its thermal extracts have signifi
cantly higher abundance of light hydrocarbons and isoprenoids (Figure 9). Pristane/nCn and
phytane/nCig, for instance, are also consequently higher (0.63 and 0.81 respectively). The pyro
lysate signatures of these samples also show high abundance of tentatively identified isoprenoids,
including prist-l-ene, most probably due to anomalous enrichment of algal/ bacterial organic
matter (Freeman et al., 1990; Summons and Powell, 1987). Thus, in comparison to the previous
‘normal’ Upper Jurassic facies, the 3366 - 3446 m interval represents an ‘abnormal’ isoprenoid-
rich facies.

Figure 9: Representative thermal extract chromatograms (TE-GC) and pyrograms (PY-GC)

of the potential source rocks, a, b) Upper Jurassic Tyne Gp.- Mandal Fm. And c, d) Farsund
(upper part) and Haugesund Fms. in wells 2/7-24 and 28. Peak identification: T - toluene, X -
xylene, the numbers indicate the number of carbon atoms in a straight chain; e.g. 15 indicates
n-heptadeccme in TE-GC traces and the position of n-heptadecene/heptadecane doublet in the
PY-GC traces, Pr-pristane, Ph-phytane and P-prist-l-ene. V are isoprenoid pyrolysis
products.
Comparison of some key biomarker parameters from the Upper Jurassic source rocks (normal
facies) and Embla’s migrated petroleum data (Table 4) suggests that the Embla oils may not have
been generated by these source rocks, considering particularly the source facies dependent para
meters such as 29oc|l /30ajJ, 30d /30ajl, 28a(3 /30aj3 or C27 /C29 diasteranes, although most of
these parameters are also influenced by maturity (Peters and Moldovan, 1993).
On the other hand, other source facies dependent parameters such as the abundance of pristane
and phytane isoprenoids (also in relation to nCn and nCig respectively) and the 8 13C isotopic
signatures of the Embla oils are comparable to the source rock data (Figure 10). However,
while the pristane/nCn and phytane/nCig ratios of the Embla oils (generally 0.3 - 0.8) indicate
high maturity, they should have been lower than the observed values given the base oil
w :####'
window maturity of the oils; unless the facies that generated these oils was unusually rich in
isoprenoids, such as the 3366 - 3446 m ‘abnormal’ facies of well 28.
Table 4: Comparison of various Upper Jurassic source intervals (wells 24 and 28) and the two
Embla oil types with respect to organic facies* and thermal maturity using biomarker data The
‘abnormal’ FarsundFm. refers to the isoprenoid-rich interval.
Parameter Mandal + Up. ‘Abnormal’ Haugesund Embla type Embla type

Farsund Fms. Farsund Fm. Fm. ‘A’oil ‘B’ oil
27Tm/27Ts 0.61 1.05 0.32 - 0.09?
29ocp/30aP* 0.45 053 0.41 0.96 1.24
30d / 30ap * 0.05 0.03 0.22 2.48 2.94
28ocp/30ap* 0.02
0.05 0.06 053? -
24/3/30ap 0.04 0.05 0.17 3.02 4.04
%32apS 59.69 60.62 6050 - -
27dpS/27dj3S+27aaR 0.68 0.54 0.82 0.89 0.92
%20S C29 steranes 49.50 4753 54.71 58.25- 53.72
C27 / C29 diasteranes * 1.06 0.76 1.30 2.04 1.84
% aPP C29 steranes 0.53 059 . 0.60 0.68 0.65
While most of the Upper Jurassic section is past peak oil generation and up to the base oil
window maturity (Table 3), the source rock in question (the ‘abnormal’ facies) has not reached
base oil window maturity in the analysed wells. Finally, in addition to the similar isotopic data,
pristane:phytane ratios of the Embla oils (1.26 - 1.42, Bharati et al, 1997a) are comparable to
those of the Upper Jurassic source rocks (1.20 - 1.51). Clearly, there is some discrepancy in the
biomarker and other data of the present study. Similar discrepancy, but between biomarker and
carbon isotope data, was also observed in several North Sea oils by Northam (1985). However,
comparison of the Upper Jurassic terpane and sterane fingerprints (Figure 11) with the Embla
oils (Figure 5) reveals significant differences.
The sterane distribution of the ‘abnormal’ facies at maturities less than about 0.7% Ro equivalent
is distinctly different from the ‘normal’ facies (Figure 11). The main differences are in the
relative abundance of diasteranes and app steranes to regular ocaa steranes. At the same maturity
level, the ‘abnormal’ facies has less diasteranes and more app steranes relative to the regular
ocaa steranes than the ‘normal’ facies. This is pronounced at lower maturities (i.e. < 0.6% Ro)
and becomes less pronounced with increasing maturity. Examples of the ‘abnormal’ facies at
high maturity are difficult to identify (they might be present in wells NOCS 2/7-15, 2/6-2 and
2/5-6 in the north, unpublished results) since all the highly mature samples which we have
evaluated show similar sterane and hopane fingerprints, i.e. like those seen in the ‘normal’ facies
at high maturity.

Phytane/nC18 Figure 10: Comparison of a)

pristane / nCn and phytane /
■ UM1
XUM2 nCis ratios and b) S 13C of
' OUS2
0.8 - - +US3
saturated and aromatic hydro
■ TLS1 carbons of core samples from the
. A LS3
O Wen 24 Embla reservoir and source
. . »Well 28 rocks from wells 24 and 28. Well
27S core samples (which belong
to trap LS3) are plotted
separately to highlight the effects
of OBM on core samples.
0 0.2 0.4 0.6 0.8 1
Pristane/nC17
d13C Aromatic Hydrocarbons
-26-------
LSI(Up.hall)
-28 * -
d13C Saturated Hydrocarbons
Forsberg et al. (1993) identified several intervals of the Upper Jurassic Farsund and Haugesund
Fms. of the Central Graben which are very organic rich (with TOC > 10% and Rock Eval S2
reaching or exceeding 50 mg HC/g rock) and have low sonic velocities. These organic rich inter
vals occur in their sequence ‘B’ which does not correlate with the classical stratigraphy used in
the area; for instance the top of ‘B’ occurs within the Haugesund Fm. of well NOCS 2/8-3 and
within the Farsund Fm. of well 2/7-3. Very organic rich horizons have been identified in this
study in wells 2/7- 28 and 2/6-3 and thin sections of other wells. Some of these organic rich

sections have hydrocarbon compositions differed from the ‘normal’ organic rich Upper Jurassic
(i.e. as found in the Mandal Fm.). The most distinct differences are that, unlike the ‘normal’
facies, hydrocarbons in the ‘abnormal’ facies are isotopically heavy and acyclic isoprenoids are
both very abundant and isotopically extremely heavy. Isotopically heavy isoprenoids in other
source rocks have been used to indicate specific source organisms, e.g. photosynthetic bacteria
(Summons and Powell, 1987 - for isoprenoids coupled to a benzene ring) or algae (Freeman et
al., 1990). Other features of this ‘abnormal’ facies, at low maturity (i.e. < peak oil) are presence
of gammacerene as a minor component and low diasterane/regular sterane ratios, high app/aaa
and higher content of short side chains. At higher maturities, the biomarker differences probably
become less marked but we have no definite examples to demonstrate this.
In addition to Forsberg et al.’s (1993) observation about distinctly different and traceable Upper
Jurassic source sequences, Northam (1985) has also noted that, while the majority of Central
Graben oils were generated by the Upper Jurassic Kimmeridge clay or equivalent, different
organic facies of this common source occur in the basin. Therefore, the most likely source of the
Embla oils based on isotopic composition and relative isoprenoidm-alkane ratios (given that these
oils are very mature) is the one in which the ‘abnormal’ facies dominates, such as the lower
portion of the Farsund Fm. (3366-3446 m) in well 28. Unfortunately, the high maturity of the
Embla oils (base oil window to condensate window) makes it impossible to correlate confidently
the steranes and hopanes to any particular facies. This is because at high maturity, the controlling
factors on hopane and sterane abundance are expulsion processes and thermal effects rather than
source type (Sofer, 1988).
4.7 Possible Filling Directions
Taking into consideration all source rock and migrated hydrocarbon evidence, four different
scenarios with respect to generation emerge.
4.7.1 The Feda Graben kitchen
Despite excellent Upper Jurassic data from wells 24 and 28 in the Feda Graben (thick sections,
rich potential, type II marine kerogen, oil window maturity, active generation at the present time),
the unlikelihood of the generated oil migrating through the salt wall and the Skrubbe Fault into
Embla must be kept in mind. The deep Jurassic section of the Feda Graben has also been
proposed as a possible source of the Embla oils, particularly for the early oil charge which was
later cracked to residual bitumen (Knight et al., 1993). In addition, it was proposed that the
Eldfisk field was filled from the west via the Skrubbe fault before the fault was sealed (Hall et
al., 1994; Stoddart et al., 1995). It can therefore be envisaged that the Skrubbe fault may have
served as a conduit even for Embla, perhaps accounting for only part of the total charge.
However, this possibility is further weakened by the fact that the ‘abnormal’ facies in this area
has (based on well 28 data) not attained the required base oil window maturity to have generated
the Embla oils (Figure 12).

a b
Z76PS
29ooR
27Ts 2Hm
1
■ pi. .1 —i i*.. J
. i , f i, -i». »-it illJLlLu.
m/z191 m/z217
Figure 11: Exemplary terpane (m/z 191, left) and sterane (m/z 217, right) mass
fragmentograms of Upper Jurassic potential source rocks. Top- Farsund Fm. ‘normal’
organic facies (3348 - 3393 m); middle- Farsund Fm. ‘abnormal’ organicfacies (3417 - 3476
m); bottom- Haugesund Fm. Peak identifications: 27Ts - 18a trisnomeohopane, 27Tm - 17a
trisnorhopane, 30oft - oft hopane, 27df5S - 20S fia diacholestane, 29df3S - 2OS f$a 24-ethyl
diacholestane and 29aaR - 20R aaa 24-ethyl cholestane.

4.7.2 The local Embla kitchen
In the event that the thin Upper Jurassic sections found in the Embla wells 20X, 21S, 23S, 26S
and 27S were equally rich in type II organic matter (and rich in isotopically heavy isoprenoids)
and reached peak oil generation in the past, significant quantities of petroleum may have been
generated that could have been locally trapped in various Embla pre-Jurassic sandstones.
However, due to poor sample control and scarce data, this option remains inconclusive. In
addition, it has been noted by Bharati et al. (1997a) that the Embla reservoir comprises two
distinct oil populations. It is unlikely that a sufficient source facies change would occur within
the Embla dome to account for the observed compositional difference (Figure 12).
4.7.3 The deep Embla kitchen

The Upper Jurassic of the eastern flank of the Embla structure (immediately west of the Skrubbe
Fault and north-west of well 25S), an area where the Upper Jurassic is deeply buried, in fact
more deeply than in well 25S, could have (had) some generation potential. Limited volume of this
claystone (see Figure 1) may also be undermine this possibility. However, as no samples or data
are available to test, this option remains a speculation (Figure 12).
4.7.4 The western / northwestern kitchen
This may well be most important, especially in the light of documented compositional (Bharati et
al, 1997a) and maturity differences within the Embla oil population. In this case, at least two
sources likely fed the Embla reservoirs (from 2-3 km west of Embla or 10 km NW of Embla and
north of Ebba), particularly in trap LS2 and US2 (well 26S, Figure 12). In his study of the
generation and migration patterns of the central North Sea, Cayley (1987) has shown the
occurrence of deeply buried Upper Jurassic source rocks in the late oil/wet gas window, west /
north-west of Embla. Moreover, he observed that in the case of most Jurassic reservoired
hydrocarbons, the drainage areas are large in the deep graben (averaging >250 sq. km.) and more
limited in the graben margins (averaging 50-60 sq. km.).
Although there is limited data to fully assess the composition of the hydrocarbons in the Upper
Jurassic shales surrounding Embla, it has been shown that the Embla oils are most probably from
the isotopically heavy (i.e. depleted in 12C), isoprenoid-rich ‘abnormal’ source facies of the
Upper Jurassic section, rather than the more ‘normal’ and typical marine Upper Jurassic rocks of
the Central Graben (isotopically lighter and with less abundant isoprenoid content). A clear
differentiation between isoprenoid-rich and -poor oil sources is gained using an aromatic maturity
parameter (DMNR) versus a source + maturity parameter (pristane/nCn, Figure 7), which clearly
shows that the Embla oils (and Jurassic reservoired oils) lie in a separate maturity trend than most
of the Cretaceous chalk-reservoired oils. In addition, the Embla oils are more mature than any of
the chalk-reservoired oils. The maturity of the source kitchen(s) of the Embla oils is close to 1%
Ro or more, while in the case of most of the Chalk-reservoired oils it is less than 1% Ro (Figure
4). Furthermore, a trend of increasing maturity can be seen, from 25S in the south-east to

Figure 12: Three scenarios of interpreted oil charge movement and filling directions in the
Embla Field. Figures on top show the limits of the Embla Field at base-Cretaceous while
figures at the bottom are simplified and schematic cross-sections of the Embla reservoir units
(cf. Figure 13). Open arrows indicate type ‘A’ oil and the solid arrows represent type ‘B’ oil.
26S/27S in the north-west, from both core and oil data. Based on these observations and the
preceding discussion, we propose the most likely filling scenario shown in Figure 12. The field
was filled by two charges from the west and/or north-west The two charges (type ‘A’ and type
‘B’ oils) were from separate source kitchens, possibly with different drainage areas, with the type
’B’ oil kitchen being slightly more mature and differing slightly in the organic facies. However,
the organic facies of both the kitchens consists of isotopically heavy n-alkanes and is
anomalously rich in isotopically heavy isoprenoids. The points of entry of types ‘A’ and ‘B’ oils
are probably traps LSI and LS2 respectively (Figure 12). Based on the compositional and
maturity characteristics of the pre-Jurassic reservoired oil from well 19R (west of Embla), it is
possible that this was in the migration pathway and was filled after the Embla field was saturated.

4.8 Trap Boundaries and communication
Based on the 5 exploration wells drilled on the Embla dome (cf. Figure 12) and which penetrate
the Upper and Lower Sandstone reservoir section, six principal (UM2, US2, UM1, LS3, LSI
and US1) and one minor (LS2) traps were defined, based mostly on the structural elements
(faults) of the dome (cf. Figure 13), but also on geochemical characteristics. Geochemical data
show that there are two distinct oil composition populations (Bharati et al., 1997a), which also
vary slightly in maturity. Within each of the oil populations, there are weak maturity trends. Each
of the traps is isolated with respect to horizontal flow (faults) and vertical flow (mudstone
section), thus making them independent compartments. In this section, we attempt to address the
trap boundaries and assess the inter-trap or intra-reservoir communication.
23S/27S
I Uppermost I -i
: :(Uppermost]
0ST#1
DSTS1
DST81
Cretaceous unconformity. Solid bars on the right of each well indicate cored intervals while
the open bars on the left indicate perforated intervals for production testing. The bottom left
inset is a simplified graphical representation of the Embla Reservoir units. Interpreted oil-
water contacts (OWC) and base of bitumen-free zone are also indicated.
The horizontal barrier (the mudstone section sandwiched between the Upper and Lower Sand
stones) is present in all the wells, although its thickness varies. However, mudstone samples from
three wells (21S, 23S and 26S) show no presence of migrated hydrocarbons, although minor in-

situ generated bitumen is present This clearly suggests that the migrated hydrocarbons are not
‘leaking through* from below and that the Upper and Lower Sandstone are well isolated from
each other. Of all the faults at base Cretaceous level in the Embla dome which compartmentalize
the field, two NW-SE trending faults are most dominant (cf. Figure 12): one is the Skrabbe Fault
which defines the eastern limit of Embla, and the other in the center which divides Embla into
two halves. This latter NW-SE fault almost certainly serves as efficient barrier to horizontal flow,
given the observed compositional and maturity variations seen in traps US2/LS2 (west of the
fault) and UM1/LS1 (east of the fault). In addition, there are several roughly E-W trending faults
adding complexity. Some of these are certainly serving as barriers, such as the one between wells
23S and 20X (different oil types in traps UM1 and UM2). It is therefore conceivable that Embla
is effectively compartmentalized and little or no communication exists between the defined traps
UM1 and UM2 in the Uppermost Sandstone, US1 and US2 in the Upper Sandstone and LSI,
LS2 and LS3 in the Lower Sandstone. During the last five years of production, no pressure
communication has been observed between the various fault blocks.
4.9 Field Productivity: Implications of OWC and Bitumen Occurrence
Bharati et al. (1997a) noted that the upper part of trap LSI (core # 4,5 & 6 in well 21S) is clearly
oil-bearing, down to at least 4580 m MD, confirmed by DST # 2 results (5200 STBOPD).
However, the 4650 - 4693 m cored interval (core # 7,8 & 9) is definitely not oil-bearing. This
places the oil-water contact (OWC) in 21S between 4580 and 4650 m MD (4290 - 4359 m
TVDSS). In well 20X, none of the Lower Sandstone cored sections (core # 2 & 3 at top- 4372-
4386 m TVDSS; and core # 4 at bottom- 4467-4485 m TVDSS) are rich in migrated
hydrocarbons (generally 0.2 - 1 mg hydrocarbons/g rock) and typically more than 70% of the
total EOM is composed of non-hydrocarbons; this section therefore is comparable to the 4650 -
4693 m section (core # 7,8 & 9) of well 21S, despite indications of minor oil staining in the 4397
- 4411 m section (4372 - 4386 m TVDSS) in the former, based on TE-GC and saturated
hydrocarbon GC; perhaps this represents a transitional zone. Placing the OWC accurately is
therefore difficult in traps LSI and LS2. In such a case, using the term ‘oil down to’ may perhaps
be more appropriate. Accordingly, it is estimated that oil extends down to about 4325 m TVDSS
in well 21S and at the most down to 4370 m TVDSS in well 20X..
With regards to trap US2, except for some tight zones, the entire Upper Sandstone is oil-bearing
(Bharati et al., 1997a) and this is confirmed by DST # 2 results (2611 STBOPD). The Lower
Sandstone trap LS2 is relatively poor, but still considered to be an oil-bearing zone; but lower
porosity (4-10%) and permeability result in lower flow (332 STBOPD) during DST. Although
the overall reservoir properties deteriorate with depth in the Lower Sandstone, particularly below
4690 m MD, no clear indications are seen of water-bearing or non-oil bearing samples. The
Embla dome is divided into two halves by a major NW-SE trending fault, with the western block
downthrown (Figure 12). Well 26S (traps US2 and LS2) is the only well on the western half
while all the other wells are in the eastern half. The OWC in trap LS2 may therefore be deeper

than the prognosed base of the Lower Sandstone in 26S (4549 m TVDSS), as shown in Figure
13. This has very serious implications with respect to future exploration in the western half of the
field, provided it is established that the sand body continues NW and SE of 26S.
In trap UM2, the deepest core sample analysed (4718 m MD) is oil-bearing and no different than
the samples above (Bharati et al., 1997a). The OWC in this trap is therefore deeper than about
4400 m TVDSS.
Geochemical data therefore indicate different depths for OWC in different traps, suggesting dis
continuous OWC across the various fault blocks of the Embla field (Figure 13). This hypothesis
is further strengthened by the fact that no pressure communication has been observed across the
different fault blocks during the past about five years of production.
Bitumen occurrence is quite independent of the OWC in each of the traps. Bharati et al. (1997a)
established accurately the depths at which a bitumen zone starts in wells 20X, 23S and 26S,
while circumstantial evidence was found in well 21S. The top of the bitumen zone in 23S and
26S is at 4301 and 4344 m TVDSS respectively. In well 20X, while solid reservoir bitumen can
be visually identified from 4469 m TVDSS, chemical data suggest that minor bitumen exists in
the entire Lower Sandstone. Similarly, while cores # 4,5 & 6 (4282 - 4291 m TVDSS) in well
21S are bitumen free, cores # 7, 8 & 9 (4359 - 4379 m TVDSS) are bitumen bearing. Thus the
4291 - 4359 m zone could contain some bitumen. Based on well 26S data, the top of the bitumen
zone in wells 20X and 21S can be extrapolated to about 4344 m TVDSS (Figure 13). Clearly, the
Upper Sandstone is bitumen free in all the wells, but the Lower Sandstone is significantly
affected; the entire Lower Sandstone section in wells 20X and 26S is within the bitumen zone,
while the bottom halves in wells 21S and 23S are in the bitumen zone. Solid reservoir bitumen
development has a detrimental effect on the general productivity of a field (porosity loss, drastic
reduction in permeability, narrowing of pore throats, inhibiting of oil mobility etc., Bharati,
1997b; Lomando, 1992). This is the reason why we get such low flow rates (322 and 500
STBOPD) in wells 26S (DST #1) and 21S (DST # 1), rather than these sections being in the
water zone. This observation strengthens (and explains) the hypothesis that the OWC in trap LS2
may actually be deeper than the rest of the field. Detailed description on the occurrence,
composition and implications of solid reservoir bitumen of the Embla Field is covered elsewhere
(Bharati, 1997a,b).
4.10 Summary and Conclusions
The Embla Field, comprising of three reservoir units (Uppermost, Upper and Lower Sandstones)
separated by a thick mudstone unit, contains two different oil populations (type A & B), differing
slightly in composition and maturity. While both oil types are of base oil-window to condensate
window maturity and more mature than any of the chalk reservoired Greater Ekofisk oils, minor
internal maturity trends are evident within Embla. This is based more on the aromatic

hydrocarbon based maturity ratios than on biomarker based ratios, as the latter are. considered less
reliable Embla due to high maturity of the oils. However, both oil populations have been gene
rated by the ‘abnormal’ Upper Jurassic organic facies, characterized by isotopically heavier n-
alkanes and in particular, anomalous enrichment of isotopically very heavy isoprenoids. The two
oil charges are believed to have been from the west and/or north-west, where the kitchen for the
Embla oils is estimated to lie. Minimal or no mixing of the two oil charges has taken place in the
Embla reservoirs, suggesting that the individual traps have been well isolated prior to and since
oil emplacement Generation and migration of Embla oils from the east (of Skrabbe Fault) or
locally occurring Upper Jurassic units is thought to be unlikely.
The data from the present study indicate that the Embla Field is highly compartmentalized and
the individual fault blocks are not in communication. The fact that during the last five years of
production from Embla no pressure communication was observed supports this finding. Perhaps
this is also the reason why the oil-water contacts (OWC) occur at different depths in different
traps, the difference being to the extent of about 200 m. The OWC is found to be shallowest
(estimated ‘oil down to’ 4325 m TVDSS) in trap LSI and deepest (+4548 m TVDSS) in trap
LS2; in trap UM2 it is estimated to be in between (>4400 m TVDSS). The deep OWC in LS2 has
serious implications with respect to future exploration and opens up the possibility of more oil
occurring NW and SE of well 26S, provided the sand body with good reservoir properties
extends in these directions.
Residual solid reservoir bitumen occurrence is quite independent of the OWC and so also the
base of the bitumen-free zone is continuous across Embla. Although solid bitumen is easily
recognizable in several wells and samples, only chemical evidence exists in some cases. The
permanent reservoir damage caused by bitumen (significant reduction in porosity, permeability
and net reservoiring capacity) is thought to be the main cause of low flow rates recorded during
some of the Lower Sandstone DSTs.
SB thanks Norwegian Research Council, Phillips Petroleum Co. Norway and Amoco Norway for
part financial assistance. The staff of Geolab Nor is thanked for assistance in geochemical
analyses and the Department of Geology, Norwegian University of Science and Technology,
Trondheim for logistics and encouragement Comments made by Richard Patience, Statoil and
Chip Feazel, Phillips Petroleum on earlier drafts improved the quality of this manuscript The
authors acknowledge the following for permission to publish the paper Phillips Petroleum Co.
Norway and co-venturers, including Fina Exploration Norway S.CA., Norsk Agip AS, Elf
Petroleum Norge AS, Norsk Hydro Production AS, Statoil AS, TOTAL Norge AS and Saga
Petroleum AS. The authors further acknowledge that the interpretations and conclusions
presented herein do not necessarily reflect the opinions of the co-venturers.

4.12 References
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1: Occurrence, development and morphotypes: AAPG Bulletin, (under submission).
Bharati, S., 1997b, Solid reservoir bitumen in the Embla Field, Norwegian Continental Shelf -
2: Chemistry, structure and origin: AAPG Bulletin, (under submission).
Bharati, S., Hall, P. B., Vagle, K. and Bjor0y, M., 1997a, Geochemical evaluation of the Embla
Field, Norwegian Continental Shelf- 1: Occurrence and compositional variations of migrated
hydrocarbons: Marine and Petroleum Geology, (under submission).
Bharati, S., Hall, P. B. and Bjor0y, M., 1997b, Identifying diverse oil families in the Greater
(under submission).
Bjor0y, M., Hall, K., Hall, P. B., Leplat, P. and L0berg, R., 1991, Biomarker analysis of oils
and source rocks using a thermal extraction-GC-MS: Chemical Geology, v. 93, p. 1-11.
Bjor0y, M., Hall, K. and Jameau, J., 1990, Stable carbon isotope ratio analysis on single comp
ounds in crude oils by direct GC-isotope analysis: Trends in Analytical Chemistry, v. 9, p. 331-
337.
Bjor0y, M., Hall, K. and Hall, P. B., 1992, Detailed hydrocarbon analyzer for well site and
laboratory use: Marine and Petroleum Geology, v. 9, p. 648-665.
Cayley, G. T., 1987, Hydrocarbon migration in the central North Sea, in J. Brooks and K.
Glennie, eds., Petroleum geology of north-west Europe, Graham & Trotman, London, p. 549-
555.
Cooper, B. S. and Barnard, P. C., 1984, Source rocks and oils of the Central and Northern
North Sea, in G. Demaisson and R. J. Murris, eds., Petroleum Geochemistry and Basin
Evaluation, AAPG Memoirs 35, AAPG, Tulsa, p. 303-314.
England, W. A. and Mackenzie, A. S., 1989, Geochemistry of petroleum reservoirs: Geologische

Rundschau, v. 78, p. 291-303.
England, W. A., Mackenzie, A. S., Mann, D. M. and Quigley, T. M., 1987, The movement and
entrapment of petroleum in the subsurface: Journal of Geological Society, v. 144, p. 327-347.
Forsberg, A., Gowers, M. B. and Holtar, E., 1993, Multi-disciplinary stratigraphic analysis of
the Upper Jurassic strata of the Norwegian Central Trough, in A. M. Spencer, ed., Generation,
accumulation and production of Europe’s hydrocarbons HI: Springer-Verlag, Berlin, p. 45-58.

Freeman, K. H„ Hayes, J. M., Trendel, J. M. and Albrecht, P., 1990, Evidence from carbon
isotope measurements for diverse origins of sedimentary hydrocarbons: Nature, v. 343, p. 254-
256.
Hall, P. B., Schou, L. and Bjor0y, M., 1985, Aromatic hydrocarbon variations in North Sea
wells, in B. M. Thomas, ed., Petroleum Geochemistry in Exploration of the Norwegian Shelf:
Graham & Trotman, London, p. 293-301.
Hall, P. B., Stoddart, D., Bjor0y, M., Barter, S. R. and Brasher, J. E., 1994, Detection of
petroleum heterogeneity in Eldfisk and satellite fields using thermal extraction, pyrolysis-GC,
GC-MS and isotope techniques: Organic Geochemistry, v. 22, p. 383-402.
Horstad, I., Barter, S. R., Dypvik, H., Aagaard, P., Bj0mvik, A. M., Johansen, P. E. and
Ericksen, S., 1990, Degradation and maturity controls on oil field petroleum column
heterogeneity in the Gulfaks field, Norwegian North Sea: Organic Geochemistry, v. 16, p.
497-510.
Kaufman, R. L., Ahmed, A. S. and Elsinger, R. J., 1990, Gas chromatography as a development
Knight, I. A., Allen, L. R„ Copiel, J., Jacobs, L. and Scanlan, M. J., 1993, The Embla Field: ,
in J. R. Parker, ed., Petroleum Geology of Northwest Europe: The Geological Society,
London, p. 1433-1444.
Kvaldheim, O. M., Christy, A. A., Telnaes, N. and Bjorseth, A., 1987, Maturity determination
of organic matter in coals using the methyl-phenanthrene distribution: Geochimica et Cosmo-
chimica Acta, v. 51, p. 1883-1888.
Barter, S. R., Bj0rlykke, K. O., Karlsen, D. A., Nedkvitne, T., Eglington, T., Johansen, P. E.,
Leythaeuser, D„ Mason, P. C., Mitchell, A. W. and Newcombe, G. A., 1991, Determination of
petroleum accumulation histories: examples from the Ula field, Central Graben, Norwegian
North Sea, in A. T. Buller, E. Berg, O. Hjelmeland, J. Kleppe, O. Torsaeter and J. O. Aasen,
eds., North Sea oil & gas reservoirs, Graham & Trotman, London, p. 319-330.
Lomando, A. J., 1992, The influence of solid reservoir bitumen on reservoir quality: AAPG
Bulletin, v. 76, p. 1137-1152.
Mason, P. C., Burwood, R. and Mycke, B., 1995, The reservoir geochemistry and petroleum
charging histories of Paleogene-reservoired fields in the Outer Witch Ground Graben, in J. M.
Cubitt and W. A. England, eds., The geochemistry of reservoirs: Geological Society Special
Publication 86, p. 281-301.
Moldowan, J. M., Fago, F. J., Carlson, R. M. K., Schoell, M., Young, D. C., van Duyne, G.,
Cardy, J., Pillinger, C. T. and Watt, D. S., 1991, Rearranged hopanes in sediments and
petroleum: Geochimica et Cosmochimica Acta, v. 55, p. 3333-3353.

Norwegian Industry Guide to Organic Geochemical Analyses, 1993, Joint report by Statoil,
Norsk Hydro, Saga Petroleum, IKU, Geolab Nor and the Norwegian Petroleum Directorate.
Peters, K. E. and Moldovan, J. M., 1993, The Biomarker Guide; Interpreting molecular fossils
in petroleum and ancient sediments: Pentice Hall, New Jersey.
Radke, M., 1988, Application of aromatic compounds as maturity indicators in source rocks
and crude oils: Marine and Petroleum Geology, v. 5, p. 224-236.
Roberts, A. M., Price, J. D. and Olsen, T. S., 1990, Late Jurassic half graben control on the
siting and structure of hydrocarbon accumulations: UK/Norwegian Central Graben, in R. F. P.
Hardman and J. Brooks, eds., Tectonic events responsible for Britain’s oil and gas reserves,
Geological Society Special Publication 55, London, p. 229-257.
Rovenskaya, A. S. and Nemchencko, N. N., 1992, Prediction of hydrocarbons in the west

Siberian basin: Bulletin Centres Research- Exploration & Production, Elf Aquitaine, v. 16, p.
285-318.
Smalley, P. C., L0n0y, A. and Raheim, A., 1992, Spatial 87Sr/86Sr variations in formation
water and calcite from the Ekofisk chalk oil field: Implications for reservoir connectivity and
fluid composition: Applied Geochemistry, v. 3, p. 341-350.
Sofer, Z., 1988, Biomarkers and carbon isotopes of oils in the Jurassic Smackover Trend of
the Gulf Coast States, USA: Organic Geochemistry, v. 12, p. 421-432.
Stoddart, D. P., Hall P. B., Larter, S. R., Brasher, J., Li, M. and Bjor0y, M., 1995, The reservoir
geochemistry of the Eldfisk Field, Norwegian North Sea, in J. M. Cubitt and W. A. England,
eds., The geochemistry of reservoirs: Geological Society Special Publication 86, p. 257-279.
Summons, R ,E. and Powell, T. G., 1987, Identification of aryl isoprenoids in source rocks
and crude oils: Biological markers for the green sulphur bacteria: Geochimica Cosmochimica
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Thompson, K. F. M., 1987, Gas-condensate migration and oil fractionation in deltaic systems:
Marine and Petroleum Geology, v. 5, p. 237-246.
Waples, D. W. and Machihara, T., 1991, Biomarkers for geologists - A practical guide to the
application of steranes and triterpanes in petroleum geology: AAPG Methods in exploration
nr. 9, pp 91.

Paper 4: Embla reservoir bitumen: Occurrence, development and morphotypes 83
Chapter 5: Paper 4
Solid reservoir bitumen in the Embla Field, Norwegian

Continental Shelf -1: Occurrence, development and morphotypes §
Sunil Bharati
5.1 Abstract
Geochemical evaluation of the Embla Field, North Sea, revealed that solid reservoir bitumen is
quite widespread in the reservoir pre-Jurassic sandstones, particularly in the lower half of the
pay-zone. As solid reservoir bitumen, irrespective of the cause of its formation, has serious
and often adverse implications with respect to reservoir quality and overall field productivity,
a detailed study was undertaken of this immobile migrated hydrocarbon phase and is reported
in two parts. Due to Embla bitumen’s widespread occurrence, its optical characterisation
ranged from a centimeter to nanometer scale, using conventional stereo microscopy and
scanning electron microscopy respectively. In addition to uneven distribution of solid bitumen
in the Embla Field, its mode and frequency of occurrence seems to change with depth.
Examination of a variety of sandstone samples (from cavities, fractures, veins, vugs etc.)
shows that solid bitumen in Embla occurs in several forms and habitats, each with different
surface and topographical features. Based on this, eight different morphotypes (massive,
spheroidal, rosette, foliated, zygotic, vein, carpet and disseminated) are identified and
described. In addition, bitumen’s occurrence is discussed in relation to all the major minerals
observed in the inter-granular space.
5 Manuscript under submission to AAPG Bulletin
h
5.2 Introduction
Solid bitumen, either pre-oil or post-oil, resulting from solidification of once liquid and mobile
petroleum, has been observed in natural geological systems and reported almost since the mm
of the century (White, 1899; Bailey, 1927). However, in earlier years, attention was mainly
focused on surface or near surface deposits due to interests in mining bitumen. Later, on the
advent of sub-surface oil exploration, solid bitumen was observed in both siliciclastic and
carbonate reservoir rocks. Over the years, this essentially immobile petroleum phase has been
described, in addition to solid bitumen, as migrabitumen, pyrobitumen, dead oil, asphalt, solid
hydrocarbons etc. Because solid reservoir bitumen has several adverse effects on overall
reservoir quality and producibility, it has of late inculcated added interest among
explorationists. Several studies have been reported on its geochemical characteristics such as
composition and maturity (Rogers et al., 1974; Hunt, 1978; Curiale, 1986), origin (Curiale,
1986; Sassen, 1988; George et al., 1994), microscopic properties (Rizer, 1987, Landis and
Castano, 1994) and recently on its influence on overall reservoir quality (Dixon et al., 1989;
George et al., 1994; Lomando, 1992). Despite this attention to reservoir solid bitumen and its
implications on field productivity, our understanding of its origin, its accurate delineation in
the field and its actual sub-surface behaviour remains limited. Lomando (1992) has observed
that when present, reservoir bitumen can have as much control on reservoir quality as
carbonate and silica cements or authigenic clays. An aspect that must be added to this is that if
present, it represents a unique and specific geological event in the diagenetic history of the
sedimentary sequence; and therefore it has potential as a link between regional oil
generation/migration and local diagenetic history.
In this study, extensive solid reservoir bitumen in a deep pre-Jurassic sandstone reservoir in
the Norwegian North Sea is examined. This is also apparently the first major solid reservoir
bitumen occurrence reported in the region (the term ‘pyrobitumen’ is deliberately not used in
this article as it indicates heat-related phenomena and may be misleading). The study focuses
on geochemical and optical assessment of residual solid reservoir bitumen found in the Embla
Field, Norwegian Continental Shelf, and comprises two parts.
This paper describes the gross occurrence, development and different morphotypes of solid
bitumen observed in the Embla reservoir, while the second paper (Bharati, 1997) addresses the
chemical and structural aspects of this unique and immobile migrated hydrocarbon phase. In
addition, the second paper discusses the various possible origins in light of the optical and
chemical data obtained. The scale of observation in the study ranges from several centimeters
(in hand specimens) to tens of nanometers (under SEM) and finally a few angstroms (under
TEM).

5.3 Geological background
This has been covered in detail elsewhere (Bharati et al, 1997a; Knight et al, 1993) but some
aspects which are relevant in the present context are briefly covered here. The Embla Field,
interpreted as occurring in a westward dipping Paleozoic horst (Knight et al., 1993), is located on
the Grensen Nose in Block 2/7 southwest of the Eldfisk Field on the downthrown side of the
Skrubbe Fault, a Late Jurassic normal fault which was reactivated as an inverted fault during
Late Cretaceous (Figure 1). It is a NW-SE oriented field of about 19.4 km2 at base Cretaceous.
The pre-Cretaceous stratigraphy varies significantly between wells in the Embla Field. The
basement rhyolitic unit, possibly of Early Devonian age, is overlain by Upper Devonian mud
stones, upon which rests the reservoir section.
Figure I: Location Map showing Block 2/7 in the Norwegian Continental Shelf (NOCS) and
enlargement of the Embla Field showing the locations of the wells included in this study.
The reservoir section comprises three major pre-Jurassic sandstone intervals, the Uppermost,
Upper and Lower Sandstones (Figure 2), of braided fluvial and alluvial fan origin, separated by

an intervening mndstone/siltstone sequence deposited in a floodplain/ lacustrine setting. The age

of the reservoir remains unknown as the sequence is barren of microfossils, but the current
interpretation based on radiometric dating favours Early Permian, Carboniferous and/or late
Devonian (Knight et al., 1992). The Upper Jurassic Tyne Gp. unconformably overlies the Embla
reservoir and only a very thin Mandal Fm. mudstone is present high on the structure.
For simplicity, the Embla reservoir (shown as a cross-section in Figure 2) has been divided
into 7 sub-traps - two in the Uppermost Sandstone (namely UM1 and UM2), two in the Upper
Sandstone (namely US1 and US2) and three in the Lower Sandstone (namely LSI, LS2 and
LS3, schematically shown as an inset in Figure 3), with the two sandstones being separated by
a thick mudstone section. Another major consideration in horizontally defining these sub-traps
is the presence of faults within the Embla structure (Figure 1).
-[Uppermost]
I Uppermost!
0ST#1 {_
DSTJM
ti 1 -
Cretaceous unconformity (solid bars = cored intervals, open bars = DST intervals; distances
between the wells are at sub-sea level). Interpreted oil-water contacts (OWC) and base of
bitumen-free zone are also indicated.
The total net thickness of the reservoir section varies from more than 317 min 2/7-23S to only
about 98 min 2/7-21S. The Uppermost Sandstone is very well developed in wells 23S/27S and
20X (317 and 173 m respectively), but absent in the other wells. The Upper Sandstone is 146 m

in well 26S, but due to erosional truncation only 21 m in well 21S and absent in the others. The
Lower Sandstone is well developed in 3 wells and varies from 113 min well 26S to 65 min well
20X in the center of the dome. Wells 20X, 21S and 26S were drilled through the base of the
Lower Sandstone, while wells 23S/27S were terminated within the Uppermost Sandstone (Figure
3). Present day reservoir temperature is 160°C and initial pressure recorded was 841 bar. The
reservoir is considered to be under-saturated with oil (API 42°) and variable GOR (329 Sm3/Sm3,
1900 Scf/stb in the eastern block and 276 Sm3/Sm3 (1550 Scf/stb) in the western block).
The reservoir section is intensely faulted (Figure 1) potentially causing compartmentalisation, a

feature which was suspected on evaluating the RFT and DST data and established later by
geochemical assessment (Bharati et al., 1997b). Due to the known geological complexities,
extensive coring was conducted which provided a good database for detailed geochemical
assessment In addition to periodic invasions of hydrothermal fluids into the reservoir causing
repeated periods of porosity loss and enhancement (Knight et al., 1992), significant solid
reservoir bitumen formed in the Lower Sand. The present study includes core samples from five
exploration wells (NOCS 2/7-20X, -21S, -23S, -26S and -27S, Figure 2) which have
penetrated the reservoir units. Host rocks and isolated solid bitumen samples (chips and
polished thin sections) were examined by naked eye, stereo microscope, petrographical
microscope and scanning electron microscope (SEM).
5.4 Reservoir bitumen: the less understood phase
Solid bitumens have been classified as ‘pre-oil’ or ‘post-oil’ by Curiale (1986) depending on
the thermal maturity of the source rock and indirectly, the solid bitumen’s proximity to its
source rock. He has argued that such a differentiation overrides earlier classical generic
schemes (e.g. Hunt et al., 1954; Meyer and de Witt, 1990) because it takes into account the
thermal state of the source rock and migration distance of the expelled oil. While this approach
is logical for petroliferous basins and provides a way to differentiate from ‘bitumens’
associated with metal ore deposits (Parnell et al, 1993 and references therein), we still need to
appreciate and incorporate the related processes (of origin) in our usage.
In the petroleum exploration context, solid reservoir bitumen can therefore be best defined as
‘essentially immobile migrated petroleum which solidifiedfrom an originally mobile andfree-
flowing oil-phase due to one or more post-emplacement alteration processes’. As mentioned
earlier, the solid reservoir bitumen phase has been described in several ways over the past few
years, such as migrabitumen, pyrobitumen, dead oil, asphalt, solid hydrocarbons etc. However,
the emphasis on the term ‘solid’ and the process of ‘solidification’ must also be made, as it
will allow us to distinguish it from the commonly employed phrase - reservoir bitumen, a term
used for the fraction obtained on solvent extraction. In addition, its inherent property of being
‘totally immobile’ and fixed is of prime importance. In my opinion, it will be useful not to use
the term ‘pyrobitumen’ for any solid reservoir bitumen observed, unless it is established that

88 Mobile and. immobile migrated hydrocarbons in the Embla Field, North Sea
heat, in one form or the other, played a vital role in its formation. For example, it would be
meaningless to term a solid reservoir bitumen known to have formed due to biodegradation
followed by devolatilization as pyrobitumen. Curiale (1986) has also rightly pointed out that
since the advent of modem geochemical methods, our attention today is not only on the origin
of such materials, but also on their role and effects on petroliferous basins. While underlining
the severity of the effects of solid reservoir bitumen formation, Lomando (1992) observed that
the impact includes filling pores (reducing effective porosity), restricting pore throats
(reducing permeability) and changing wettability.
Keeping all these factors in mind, a simple term such as ‘oil cement’ or ‘cemented oil’ would
suffice, in line with commonly used terminologies, namely quartz cement or carbonate cement.
The various forms of oil cements could be envisaged as biodegraded oil cement or irradiated
oil cement etc., which would throw light on their origin. By proposing the term oil cement, it is
not intended to add yet another synonym, but to streamline its usage. Of course, the above is
applicable (and intended) only for petroleum reservoir systems (Curiale’s (1986) post-oil
category).
5.5 Occurrence and types of Bitumen in the Embla Field
While reservoir bitumen is rare in the Uppermost and Upper Sandstones, extensive bitumen is
seen in the Lower Sandstone of the Embla Field. Based on extensive geochemical analyses of
core samples, Bharati et al. (1997b) established the exact depth at which bitumen occurs in
three of the five wells, namely 23S/27S (4301 m TVDSS) and 26S (4344 m TVDSS). An
estimate (4344 m TVDSS) was made in wells 20X and 21S based on partial evidence (above
4372 m TVDSS in 20X and between 4291 - 4359 m TVDSS in 21S) and neighbouring well
core data. The base of bitumen-free zone was established by a combination of visual
examination of cored sections and chemical composition of pyrolysates (PY-GC). Apparently,
the base of the bitumen free zone is not continuous across the field (Figure 2) and is inde
pendent of the oil-water contact (Bharati et al., 1997b). Well 26S is the only well where solid
bitumen occurs in the Upper Sandstone.
Figure 3: (following page) Examples of the various modes of occurrences of the solid
reservoir bitumen, seen in core hand specimens from the Embla Field, Cavity bitumen, as
seen a) in a cross-section, b) along a fracture and c) with extensive barite (arrow)
association, d) Carpet bitumen, e) Disseminated bitumen (from well 23S).f) Fracture bitumen
(arrow), g) Vein bitumen, h) sample split along the vein, i) Another example of a fracture
bitumen, j) Vug bitumen. Scale bar = 2 cm.

m.
Another important feature of the Embla solid reservoir bitumen is that, from the depth when
the bitumen is first observed, it increases in abundance, distribution frequency and net volume
with increasing depth. There are indications that even the mode of occurrence changes from
disseminated at shallower depths to large vugs, cavities and fractures filled with solid bitumen
deeper in the field.
Examination of Embla core (hand) samples from the different wells shows that bitumen occurs
in a variety of forms (Figure 3). Based on this, the Embla solid bitumens are classified and the
assigned names are based on the modes of occurrences.
5.5.1 Cavity bitumen
This is most easily noticed (due to its sheer dimensions), quite abundant and generally occurs
in the deeper parts of the field. It is seen only in the coarse-moderate grain sandstones of wells
20X, 21S and 26S (most extensive in 26S) as filled, solid, black and vitreous bitumen mass, in
cavities ranging 2-3 mm to up to 5 cm across (Figure 3a). The cavities, especially large
cavities, are random-shaped and angular with sharp boundaries and comers, suggesting that
these were formed early, but post-compaction and possibly a result of tectonic activity. Criss
crossing bitumen healed fractures starting from and ending in the bitumen-filled cavities are
abundant and a common feature and are believed to have served as ‘feeders’ to the cavity.
Splitting a sample along a fracture and across a cavity reveals that most of the fracture plane is
lined by a thin sheet of bitumen, while the ‘cavity bitumen’ occurs as a solid mass (Figure 3b).
Except for very few exceptions, cavity bitumens are invariably associated with barite (Figures
3a and c).
In polished thin-sections, black and opaque bitumen exhibiting no special optical properties is
easily recognizable. Cavity bitumens in particular, show distinctive contraction fractures
(Figure 4a), which pinch out at the ends and are believed to be formed by reduction in volume
of the original petroleum phase (removal of lighter components and gas) during solidification.
Some of these contraction fractures are healed by barite (Figure 4c), the latter exhibiting
distinctive extinction under stage rotation. The contact between the bitumen and barite is
sharp.
5.5.2 Vein bitumen
This type is less abundant (perhaps due to difficulty in detection), nevertheless it is observed
in all wells. Veins up to 34 cm in length and 2 mm in width were observed in cores (part of a
vein shown in Figure 3g), which pinch out at one end and continue out of the core at the other.
By and large, bitumen healed veins are isolated entities with limited or no inter-connection,
although a single vein dividing into two veins was observed. On splitting the sandstone along
a vein (Figure 3h) to expose the bitumen phase, it is apparent that the rock wall(s) is(are) lined
by black and vitreous bitumen, with which barite is commonly associated (white spots in

Figure 4: Different modes of bitumen (Bi) occurrences in polished thin sections, seen as a
black phase, a) Cavity bitumen, b) Vein bitumen, c) Cavity bitumen associated with barite
(Ba), d) Fracture bitumen (arrow), e) Disseminated bitumen and j) Carpet bitumen (thick
white arrows). Ep = epoxy, Ka - kaolinite and Qd = detrital quartz grain. Scale bar in (e) is
100 p, all others 500 p..
'.'fv
Figure 3h). In thin sections, vein bitumen clearly differs from cavity bitumen in that the latter
has sharp contacts with the host rock and gives a ‘river-like’ appearance (Figure 4b). The
barite phase essentially occurs in contraction fractures of bitumen, but more importantly it
does not continue into the host rock.
5.5.3 Fracture bitumen
This type is more commonly seen in highly brecciated sandstone sections (Figures 3i and f),
but also in other sections which are fractured less extensively. Except for the visible black
colour, it has no other distinctive appearance in hand specimens and is readily recognizable as
randomly oriented, criss-crossing and inter-connected healed fractures in thin sections (Figure
4d). The width of bitumen-healed fractures rarely exceeds about 200 (X.
5.5.4 Disseminated bitumen
This type is restricted to the upper part of the bitumen zone of Embla (cf. Figure 2) and is
most extensive in well 23S. It is not recognizable as a distinct phase in hand specimens, except
for blackish colouration of the inter-granular material, as seen in the conglomeratic sandstone
of well 23S (Figure 3e). Even at high magnification in thin section, the bitumen phase is not
recognizable (Figure 4e), except for dense dark brown to black material in the pore space, the
latter feature being totally absent in bitumen-free zone samples.
5.5.5 Carpet bitumen
This is more rare and randomly seen in all sections of the wells, but is essentially restricted to
fine-grained, but not necessarily low porosity, sandstone facies. It occurs as a thin sheet of tiny
black particles along certain planes of weakness (micro-fractures?) and gives a powdery
appearance in hand-specimens (Figure 3d). In thin sections, it differs from dissipated bitumen
in that larger (generally up to about 100 p.) and relatively easily distinguishable black bitumen-
rich areas are seen (Figure 4f).
5.5.6 Vug bitumen
This is most rare, possibly restricted to fine grained sandstone facies and occurs as wall lining
in open vugs. It differs from cavity bitumen in that unlike cavity bitumen, which completely
fills all available cavity volume, in the case of vug bitumen, a significant portion of the vug
volume (towards the center) remains open (Figure 3j). In addition, the shape of vugs is very
different to cavities described above, in that the former are rounded and elongated in cross
section, pointing more towards being solution vugs rather than caused by tectonic activity.
Clearly, solid reservoir bitumen in the Embla Field occurs in a variety of modes, each habitat
differing from the other with respect to overall shape, volume, size, frequency, depth of occur
rence and host rock characteristics, the last factor perhaps of greater importance than is

Figure 5: Morphotypes ofEmbla solid reservoir bitumens: Massive a) type ‘A’, b) type ‘B’,c)
type ‘C\ d) Spheroidal and e) Rosette (details of the bottom flat and circular part is shown in
(f)from a different angle).

apparent. With so many variables determining the resulting bitumen types described above, it
is likely that there may even be other factors unique to each type than simply differing physical
forms on a macro scale, such as chemical properties, internal structure, origin, cause of
emplacement and even micro-scale physical differences. The micro-scale physical
characteristics are examined in this paper. The other factors are covered in the second part of
this work (Bharati, 1997).
Scanning electron microscopy (SEM) is a useful tool to study the topographical features and
elemental composition of mineral phases in geological samples (e.g. Pye and Krinsley, 1984;
Trewin, 1988) and it has also been used successfully in the past to characterize the carbon-rich
organic phase in sedimentary rocks, mostly kerogens and coals (e.g. Belin, 1992; Bishop et al.,
1992) but also solid bitumen (e.g. Lomando, 1992; George et al., 1994).
In the case of Embla samples, in addition to polished thin sections, whole rock chips (pre
washed with dichloromethane : methanol, 93:7 vol/vol) and untreated, randomly mounted
solid bitumen particles were studied using SEM (JEOL JXA-8900M for microprobe analysis
and elemental mapping; JEOL JSM-840 for topographical studies). Solid bitumen particles
from all possible modes of occurrence (cavity, vug, fracture and vein) were physically
removed from core samples to examine differences, if any. Solid bitumen was easily identified
by microprobe analysis equipped with a light element detector, as this organic phase contains
(in addition to relatively insignificant quantities of hydrogen, nitrogen, sulphur and oxygen)
only carbon from the SEM point of view.
5.6 Morphotypes of Embla bitumen
Some workers have tried to classify and name various bitumens based on features seen under
SEM. For example, based on topographical features, Lomando (1992) described six different
morphotypes of solid bitumen, namely droplet, carpet, peanut brittle (Jurassic Smackover
Formation), vesicular (Cretaceous sandstones of West Africa), digitate (Devonian, Western
Alberta) and pore cast. George et al. (1994), on the other hand, have classified their bitumen
suite from McArthur Basin (northern Australia) into five ‘types’ (I - V) based on the mode of
occurrence. In the present investigation, I have attempted to take into account both criteria,
i.e., mode of occurrence as well as topographical features. Apparently, distinct differences are
present in the topographical features of bitumens from different modes (Figures 5 and 6).
These are classified and named based on their appearance, and described in detail below.
5.6.1 Massive bitumen
This (Figure 5a-c) is found mostly in cavities, but also to a much lesser extent in the rock
mass where a (bitumen filled) cavity is not equally obvious. It is characterized by distinct
conchoidal fractures which in some cases are very strong (massive type ‘A’, Figure 5a), in

Figure 6: Morphotypes of Embla solid reservoir bitumens (contd.): Foliated a) type ‘A’ with
planarfolia, b) type ‘B’ with non-planarfolia, c) Zygotic, d) Zygotic- transitional, e) vein and
f) Carpet.

others moderate (massive type ‘B\ Figure 5b) or weak (massive type ‘C\ Figure 5c). It is
possible that the bitumen surface (failure surface) seen in these figures is actually along the
contraction fractures seen in thin sections. In between the ‘ridges’ caused by conchoidal
fracturing, the surface is smooth and unstructured.
5.6.2 Spheroidal bitumen
This (Figure 5d) is also found in cavities and vugs and is characterized by a distinct spherical /
globular shape. It is however possible that this too is essentially a massive type, but with very
strong and peculiar conchoidal fractures which result in a spherical shape when physical stress
is applied (such as the one caused by breaking).
5.6.3 Rosette bitumen
This type (Figure 5e), found in vugs, resembles in some manner spheroidal bitumen, but
differs by its ‘flowery’ shape. More importantly, one side of the bitumen particle (probably the
bottom) is different to the remaining body, in that it is flat, and an outward radial pattern is
seen. Examining this face in detail (Figure 5f) shows that radiating from almost a perfect
circular and flat area, which could be the point of attachment to the host rock, the bitumen
particle extends outwards in all directions. It is thus likely that the top surface seen in Figure
5e is the outermost limit of bitumen lining the vug wall.
5.6.4 Foliated bitumen
This type, found in small cavities, fractures and possibly veins, is very different from massive
bitumen in that the foliated bitumen does not exhibit any conchoidal fractures, although it is
massive in nature. The unique property of foliated bitumen is that it consists of a cluster of
parallel folia, either planar in nature (foliated type ‘A’, Figure 6a) or non-planar (foliated type
‘B’, Figure 6b). Several transitions between types A and B are expected to be present, but
were not observed.
5.6.5 Zygotic bitumen
This type (Figure 6c), found in rock matrix, perhaps in small (< 1 mm) cavities has a
characteristic ‘basket of eggs’ appearance with similar sized and ellipsoidal bitumen bodies
clustered in an outer bitumen shell. This feature in some cases is only seen moderately (Figure
6d), but at the same time it appears that this may be related to foliated type ‘B’ bitumen.
Comparing the shapes of the foliated type ‘B’ bitumen and zygotic bitumen shell (figures 6c
and d respectively), it seems possible that the foliated bitumen core consists of ‘zygotic’
bitumen bodies.

Figure 7: General view of cavity, disseminated and carpet bitumens in thin sections as seen
using SEM. a) cavity bitumen at 100X, c) disseminated bitumen at 100X and e) carpet
bitumen. Areas marked in a, c and e are enlarged in b, d andf respectively and were usedfor
elemental mapping.

5.6.6 Vein bitumen
This type (Figure 6e), exhibits a very different outer surface than any of the previously
described morphotypes. The top outer surface observed, in all probability, is the negative
mould of the rock surface, rather than a freshly broken surface of bitumen as was the case of
massive bitumens described above. The general shape (rounded in one direction and elongated
in the other) is indicative of the limited space available (except along the long axis of the vein)
for bitumen emplacement, unlike cavities and vugs. ‘Mud cracks’ like contraction fractures in
the bitumen phase are clearly visible (note the continuous contraction fracture along the spine
of the vein).
5.6.7 Carpet bitumen
This (Figure 6f) is typical of relatively fine-grained sandstones facies without any major
cavities and vugs, and is difficult to locate; perhaps it is rare too. Unlike the types described
above, this morphotype occurs as a thin sheet (estimated thickness <10 |i) over the rock
matrix. As seen in Figure 6f, a carpet of fine grained bitumen (in the upper half) covers books
of kaolinite which are exposed in the lower half of the photo.
5.6.8 Disseminated bitumen
This was most difficult to identify using the standard topographic or elemental analysis set up.
Samples suspected of containing disseminated bitumen (especially in well 23S as shown in
Figure 3e) failed to give any strong carbon signal for any identifiable particles in the pore
space, despite a weak but consistent carbon signal in the background. It seemed therefore that
the bitumen present in these samples (which was suspected from the pyrolysate compositions,
Bharati et al., 1997b; see also part 2 of this work, Bharati, 1997), must be particulate and
dispersed all over the pore space. Detailed and careful elemental mapping of an inter-granular
(detrital quartz) area was therefore performed using thin sections to establish whether any
carbon was present (and where). However, to test whether the technique would work, a known
cavity bitumen was mapped first for 8 elements aimed specifically at identifying all the major
mineral phases: C - for bitumen, Si - for quartz and kaolinite, Al - for kaolinite, Ba - for barite,
S - for barite and pyrite, Fe - for pyrite, Ca - for carbonates and K - for feldspars. These
mapped areas (a and b - cavity, c and d - dissipated and e and f carpet bitumen) are shown in
Figure 8: (following page) False colour images of elemental mapping for carbon (C), silicon
(Si), aluminium (Al), barium (Ba), sulphur (S), iron (Fe), calcium (Ca) and potassium (K) of
an area containing cavity bitumen (cf. Figure 7b). Bottom colour bars indicate the signal
intensity for each element. The bottom right image is a composite indicating the main phases,
namely bitumen (Bi, black), detrital quartz (Qd, green), barite (Ba, white) and kaolinite (Ka,
red/yellow).


100 Mobile and immobile migrated hydrocarbons in the Etnbla Field, North Sea
Figure 7, the general area with several detrital quartz grains and inter-granular pore space in
small magnification and the details of the mapped pore space in large magnification. As seen
in the elemental maps of the cavity bitumen (Figure 8), areas occupied by bitumen, quartz,
kaolinite and barite are successfully detected and mapped in the test area containing cavity
bitumen. False colours are automatically assigned depending on the signal intensities (white
strongest and black weakest), although the absolute values of each element’s scale vary. Later,
without changing the calibration, particularly from the point of view of detecting carbon, a
new area was mapped (Figure 7d), suspected to contain disseminated bitumen.
The inter-granular space between the three quartz detrital grains (measuring roughly 300x200
p.) evidently contains a significant area enriched in carbon, occurring with equal frequency in
the entire inter-granular space (Figure 9). Interestingly, the areas rich in carbon do not contain
kaolinite, suggesting that most of the disseminated bitumen is dispersed between the books of
kaolinite. No barite or pyrite is present in this mapped area. Similar elemental mapping was
also performed successfully in a sample containing carpet bitumen (cf. Figures 7e-f) to
confirm the presence of carbon.
Microprobe analysis of the other bitumen types did not give any information other than that all
types consist of carbon; hence from the elemental composition (as detected by SEM) point of
view, all morphotypes are alike. Consequently, the various morphotypes seen in the Embla
Field, may actually be attributes of the shape, volume and size of the pore space that the
petroleum phase occupied before solidification. However, this does not explain why for
instance, conchoidal fractures are so strongly seen in some and foliation in others or why some
morphotypes contain ellipsoidal bitumen bodies in the core and others don’t (differing stress
fields during solidification?). Clearly, other factors played an influential role during solid
bitumen formation. Defining areas in the field and zones down the wells which may be rich in
a given bitumen morphotype is thought to be useful, but was not possible in the present study
due to limited sample control and cost constraints.
5.7 Minerals in inter-granular space
It is clear from the evidence presented that solid bitumen is an important and major phase in
the inter-granular space of the Embla reservoir sandstones. However, in order to understand
the possible reasons for bitumen development and emplacement in the Embla Field, it is
Figure 9: (following page) False colour images of elemental mapping for carbon (C), silicon
(Si), aluminium (Al), barium (Ba), sulphur (S), iron (Fe), calcium (Ca) and potassium (K) of
an area containing disseminated bitumen (cf. Figure 7d). Bottom colour bars indicate the
signal intensity for each element. The bottom right image is a composite indicating the main
phases, namely bitumen (black/dark blue), detrital quartz (Qd, red) and kaolinite (Ka, yellow).


imperative to characterize the nature of the entire inter-granular space and not just the carbon
phase in it. This includes minerals, cement and present-day porosity. XRD analyses have
shown that the Embla reservoir sandstones contain, in addition to quartz (50-70%), kaolinite
as the dominant clay mineral (up to 35%) and illite only in trace amounts despite the depth of
the reservoir (4 km +; Bharati et al., 1997a). In addition, no feldspar is present and siderite,
pyrite and anhydrite are present in trace amounts; ankerite/dolomite is mostly absent, but in
some samples from the Lower Sandstone, it is as high as 40% (Bharati et al., 1997a). In the
following section, the nature of inter-granular space is examined using SEM, in light of these
findings.
5.7.1 Clay minerals
Kaolinite, as XRD analysis indicates (Bharati et al., 1997a), is very widespread and the only
authigenic clay mineral readily observed in all samples. It occurs as well developed pseudo-
hexagonal plates in curved vermicular stacks (Figure 10a). The hexagonal plates are only
partially etched, indicating that kaolinite has remained fresh and generally unaltered. In some
relatively fine-grained and tight sandstones however, which are rich in bitumen-healed
fractures and veins, the kaolinite phase seems to be closely associated only with the bitumen
phase as large clusters and not with the remaining host rock, which seems nearly barren of
kaolinite (Figure 10b). This is intriguing from the point of view of diagenesis of the host rock
and its subsequent porosity preservation. Illite, which greatly reduces the permeability of a
sandstone, is very rare and difficult to find in the samples. However, some examples of ran
domly oriented and intertwined wiry/fibrous illite were observed (Figure 10c) which indicate
only partial (and early stage) illitization. Smectite is the rarest form in the Embla sandstones
and is only occasionally found as a thin mixed clay layer (Figure lOd). In any case, had
smectite been present in the system as an early diagenetic product, it would have readily
converted into illite during burial. Bjprlykke et al. (1992) have noted that the absence of early
diagenetic smectite may indicate low silica content in the pore water due to low contents of
amorphous silica or volcanic fragments. Near absence of illite in the Embla reservoir
sandstones may also be indicative of early oil emplacement. This is discussed further in the
second part of this paper (Bharati, 1997).
5.7.2 Authigenic/overgrowth quartz
This is a common feature in most samples and is considered as one of the major mineral
phases in the pore-space. It occurs generally as intermediate, but occasionally in advanced
stage of quartz overgrowth cementation (Figure lOe), filling a significant portion of the total
porosity. In some cases, quartz overgrowths are in contact with adjacent euhedral quartz
overgrowths, showing how advanced the quartz cementation stage is.

Figure 10: Mineral phases in the inter-granular space of sandstones as seen using SEM. a)
Kaolinite in a rock chip, b) Kaolinite in thin section, closely associated with bitumen (black
area), c) Illite, d) Smectite, e) Authigenic quartz andf) Ankerite/dolomite.
Jito v,
5.7.3 Ankerite/Dolomite
This is rare in most samples, but readily seen in others as euhedral rhombic crystals (Figure
lOf). Bharati et al. (1997a) noted that while typically the overall ankerite/dolomite content is
very low in most samples, some samples have anomalously high content (up to over 40%).
No other major mineral phases are apparently present in the pore-space. However, some
mineral phases are almost exclusively associated with solid bitumen, such as:
5.7.4 Pyrite
In general, pyrite was detected only in trace amounts in the reservoir sandstones, but in
samples which have obvious bitumen occurrences, it was relatively more abundant (Bharati et
al., 1997a). SEM examination of thin sections show that pyrite invariably occurs within or in
immediate vicinity of the bitumen phase (Figure 11a and b) and is most commonly observed
associated with bitumen-healed fractures, veins and smaller cavities as circular masses
(framboids?), typically 100-500 pm across. Interestingly, while pyrite is common and in some
cases extensive in the bitumen phase, it is nearly absent or at best rare in the host rock.
Numerous studies have been reported on organically bound sulphur in kerogens, asphaltenes
and oils (Orr and Damste, 1990 and references therein) and although far fewer, even on
elemental sulphur in crude oils, but none on the association of mineral pyrite with migrated
hydrocarbons. This aspect is elaborated further in part 2 of this paper (Bharati, 1997).
5.7.5 Barite
As mentioned earlier, barite is commonly found within the bitumen phase, mostly filling
bitumen’s contraction fractures. This form appears to be massive and interconnected (Figure
11c), similar to hydrothermal vein fillings. In addition, barite is also found as perfect
orthorhombic prismatic crystals embedded in the bitumen mass (Figure lid). No association
of the two barite forms was found. The fact that prismatic euhedral barite is found as
inclusions in the bitumen mass indicates that the crystals were formed before bitumen
solidification.
Other minor and rarely seen mineral phases such as halite (Figure lie, could be from sea
water but could also be authigenic given the close proximity of Embla to salt diapirs) and an
unknown mineral phase (occurring as a thin sheet over bitumen, Figure 1 If) was also seen.
These, however, are not considered to have any bearing on the present study.

Figure 11: Mineral phases exclusively associated with bitumen, a) Pyrite (Py), occurring here
along a bitumen-healed vein (Bi), b) enlargement of the marked area in (a), c) Massive barite
(Ba), occurring in bitumen cooling/contraction fractures, d) Crystalline barite, occurring
embedded in the bitumen mass, e) Halite and f) An unknown mineral (seen rarely) occurring
as a thin sheet over bitumen.

5.8 Summary and conclusions
The Embla Field reservoirs consist of pre-Jurassic sandstones, and has a significant solid
bitumen development in its reservoir, particularly in the Lower Sandstone. However, bitumen
is not found in the entire reservoir column. The top of the bitumen zone has been established
in all five wells studied based on visual examination of cores and pyrolysate compositions.
Apparently, the depth of bitumen occurrence is variable across the field and evidently the
overall bitumen abundance increases with increasing depth. The bitumen occurs as a solid,
black and vitreous phase in a variety of modes such as filled cavities, open vugs, veins,
fractures, carpet and disseminated. Each habitat of occurrence is characterized by special and
unique properties, which have become the basis of classifying the Embla bitumens into
different morphotypes, namely 1) massive (consisting of types A, B & C), 2) spheroidal, 3)
rosette, 4) foliated (types A & B), 5) zygotic, 6) vein, 7) carpet and 8) dissipated. Elemental
mapping proved to be vital in recognizing dissipated bitumen. Microprobe analysis of the
other bitumen morphotypes does not provide any additional useful information other than that
all types primarily consist of carbon. It is therefore possible that the various morphotypes seen
in the Embla Field, may actually be attributes of the shape, volume and size of the pore space
that the petroleum phase occupied before solidification. However, this hypothesis cannot
explain some of the vital differences observed between the morphotypes. It is therefore
believed that there may be some other factors, yet unknown, that played an influential role
during solid bitumen formation. This aspect, in addition to chemical composition, internal
structure and timing of emplacement, is addressed in the second part of this work.
5.9 Acknowledgments
Many thanks to Phillips Petroleum Co. Norway for providing the samples and co-venturers,
including Fina Exploration Norway S.C.A., Norsk Agip AS, Elf Petroleum Norge AS, Norsk
Hydro Production AS, Statoil AS, TOTAL Norge AS and Saga Petroleum AS for permission to
publish. Thanks also to the Norwegian Research Council (NFR), Phillips Petroleum and Amoco
Norway for partial financial assistance. The Department of Geology, Norwegian University of
Science and Technology, Trondheim is thanked for support and encouragement Help from
Morten Raanes and Kjell Muller, SINTEF in operating the SEMs is acknowledged. The
manuscript benefited greatly from comments made by Joe Curiale, Unocal, on an earlier draft
Kare Vagle, Phillips, Norway is particularly thanked for taking constant interest and discussing
my results, which has improved the quality of this work.
5.10 References
Bailey, E. M., 1927, The chemistry and technology of the oil shales, in Oil shales of Lothians:
Memoirs of the Geological Survey, Scotland, p. 159-172.

Belin, S., 1992, Application of backscattered electron imaging to the study of source rock
microtextures: Organic Geochemistry, v. 18, p. 333-346.
Chemistry, structure and origin: AAPG Bulletin, (under submission).
Bharati, S., Hall, P. B., Vagle, K. and Bjor0y, M., 1997a, Geochemical evaluation of the
Embla field, Norwegian Continental Shelf -1: Occurrence and compositional variations of
migrated hydrocarbons: Marine and Petroleum Geology, (under submission).
Bharati, S., Hall, P. B., Vagle, K. and Bjor0y, M., 1997b, Geochemical evaluation of the
Embla field, Norwegian Continental Shelf - 2: Source, infilling, compartmentalisation and
intra-reservoir communication: Marine and Petroleum Geology, (under submission).
Bishop, A. N., Kearsley A. T. and Patience, R. L., 1992, Analysis of sedimentary organic
materials by scanning electron microscopy: the application of backscattered electron imagery
and light element x-ray microanalysis: Organic Geochemistry, v. 18, p. 431-446.
Bj0rlykke, K., Nedkvitne, T., Ramm, M. and Saigal, G. C., 1992, Diagenetic processes in the
Brent Group (Middle Jurassic) reservoirs of the North Sea: an overview, in, A. C. Morton, R.
S. Hazeldine, M. R. Giles and S. Brown (eds.), Geology of the Brent Group: Geological
Society Special Publication No. 61, London; p. 263-287.
Curiale, J. A., 1986, Origin of solid bitumens, with emphasis on biological marker results, in
D. Leythaeuser and J. Rullkotter (eds.), Advances in Organic Geochemistry 1985, p. 559-580.
Dixon, S. A., Summers, D. M. and Surdham, R. C., 1989, Diagenesis and preservation of
porosity in the Norphlet Formation (Upper Jurassic), southern Alabama: AAPG Bulletin, v.
73, p. 707-724.
George, S. C., Llorca, S. M. and Hamilton, P. J., 1994, An integrated approach for
determining the origin of solid bitumens in the McArthur Basin, northern Australia: Organic
Geochemistry, v. 21, p. 235-248.
Hunt, J. M., 1978, Characterization of bitumens and coals: AAPG Bulletin, v. 62, p. 301-303.
Hunt, J. M., Stewart F. and Dickey, P. A., 1954, Origin of hydrocarbons of Unita Basin, Utah:
Knight, I. A., Allen, L. Copiel, R. J., Jacobs, L. and Scanlan, M. J., 1993, The Embla Field, in
J. R. Parker, ed., Petroleum Geology of Northwest Europe: The Geological Society, London,
p. 1433-1444.
Landis, C. R. and Castano, J. R., 1994, Maturation and bulk chemical properties of a suite of
solid hydrocarbons: Organic Geochemistry, v. 22, p. 137-149.
Bulletin, v. 76, p. 1137-1152.

Meyer, R. F. and de Witt, W., 1990, Definition and world resources of natural bitumens: US
Geological Survey Bulletin 1944, p. 1-14.
Orr, W. L. and Damste, J. S. S., 1990, Geochemistry of sulphur in petroleum systems, in W.L.
Orr and C. M. White (eds.), Geochemistry of sulphur in fossil fuels: ACS symposium series
429, Washington, p. 2-29.
Parnell, J., Kucha, H. and Landais, P., 1993, Bitumens in ore deposits: Berlin, Springer-
Verlag, 520p.
Pye, K. and Krinsley, D. H., 1984, Petrographic examination of sedimentary rocks in the SEM
using backscattered electron detectors: Journal of Sedimentary Petrology, v. 54, p. 877-888.
Rizer, C. L. T., 1987, Some optical characteristics of solid bitumen in visual kerogen prepara
tions: Organic Geochemistry, v. 11, p. 385-392.
Rogers, M. A., McAlary, J. D. and Bailey, N. J. L., 1974, Significance of reservoir bitumens
to thermal maturation studies, Western Canada: AAPG Bulletin, v. 58, p. 1806-1824.
Sassen, R., 1988, Geochemical and carbon isotopic studies of crude oil destruction, bitumen
precipitation and sulphate reduction in the deep Smackover Formation: Organic Geochemistry,
v. 12, p. 351-361.
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(ed.) Techniques in sedimentology, Oxford, Blackwell, p. 229-273.
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284.

Paper 5: Embla reservoir bitumen: Chemistry, structure and origin 109
Chapter 6: Paper 5
Solid reservoir bitumen in the Embla Field, Norwegian

Continental Shelf -2: Chemistry, structure and origin§
Sunil Bharati
6.1 Abstract
Solid reservoir bitumen, which was found to be extensive in the Embla Field, particularly in
the lower portion of the pre-Jurassic sandstone pay-zone, occurs in a variety of modes
resulting in eight recognizable morphotypes, as described in the first part of this study. This
paper focuses, in addition to its chemical composition, on the internal structure and possible
mode of origin. As this unique immobile migrated hydrocarbon phase is insoluble in common
organic solvents, its chemical characterisation was limited to pyrolysis-gas chromatography
and other bulk chemical methods such as NMR and elemental analysis. This carbon-rich phase
(TOC up to 62%) is depleted in hydrogen (H/C 0.8-0.9) and enriched in aromatic hydrocarbon
structures (fa 68%), but gives contradictory PY-GC signature which indicates labile moieties
present in the bitumen mass. Examination using SEM shows the presence of some systematic
and partially ordered internal structure. Based on the various solid bitumen features observed,
particularly in relation to the inorganic minerals occurring in the pore-space, the relative
timing of bitumen’s emplacement is estimated. Various known causes of bitumen formation
are discussed and the most likely scenario in the case of Embla presented. Its implication on
reservoir quality and its relationship to the present mobile (producible) oil phase is also
discussed.
5 Manuscript under submission to AAPG Bulletin

6.2 Introduction
This is the second of two papers on geochemical and optical assessment of residual solid
reservoir bitumen found in the Embla Field, Norwegian Continental Shelf (Note: the term
‘pyrobitumen’ is deliberately not used in this article as it indicates heat-related phenomenon
and therefore may be misleading). The first paper assessed the gross occurrence, development
and different morphotypes of solid bitumen observed in the Embla reservoir, while this paper
addresses the chemical and structural aspects of this unique and immobile migrated
hydrocarbon phase in the main reservoir units of the Embla Field, namely the pre-Jurassic
Upper and Lower Sand.
Previous studies have attributed solid bitumen to result from one or more of three principal oil
alteration processes outlined by Tissot and Welte (1984): biodegradation (e.g. Deroo et al.,
1977; Connan, 1984), thermal alteration (e.g. Raymond and Murchisson, 1988) and
deasphalting (e.g. Dahl and Speers, 1985). In the present paper, these and several other
processes are discussed in an attempt to evaluate their validity and explain the observed form,
texture and structure of the Embla bitumens.
63 Geological background
This has been covered in detail in the first paper on the geochemical evaluation of the Embla
Field (Bharati et al, 1997a) and to some extent in part 1 of this paper (Bharad,1997). Briefly,
the Embla Field, a NW-SE oriented field of about 19.4 km2 at base Cretaceous, consists of three
pre-Jurassic reservoir units, the Uppermost, Upper and Lower Sandstone separated vertically by a
thick mudstone facies. The reservoir section is intensely faulted potentially causing compartmen-
talisation, a feature which was suspected when evaluating the RFT and DST data. Due to the
known geological complexities, extensive coring was conducted (Knight et al., 1992) which
provided a good database for detailed geochemical assessment. In addition to periodic invasions
of hydrothermal fluids into the reservoir causing repeated periods of porosity loss and
enhancement, there is significant solid reservoir bitumen formed in the Lower Sandstone.
6.4 Samples and Methods
Pure solid bitumen aliquots were obtained by physically scraping bitumen mostly from
cavities, vugs and veins in core samples of three wells, namely NOGS 2/7-20X, -21S and -
26S, using a scalpel and a diamond-tipped electrical vibrator. These were subsequently
analyzed for solubility (in dichloromethane : methanol (93:7 v/v), total organic carbon (TOC)
using LEGO CR12 instrument and composition (PY-GC using GHM instrument and bulk 813C
using VG SIRA 10 instrument). In addition, bitumen aliquots were analysed for elemental
composition (C, H, N, S and O) using EA 1110 element analyzer and U and Th using neutron
activation) and gross aromaticity and carbon types using solid state 13C NMR on a Bruker

MSL 300 instrument. Whole rock portions rich in bitumens as well as pure bitumen aliquots
were analysed for biomarker composition using GHM-MS. Whole rock polished thin sections
and slices covering the entire reservoir column were used for petrological and fluid inclusions
analyses respectively. Solid bitumen and whole rock samples were also examined using SEM
(JEOL JSM-840) to understand mineral inter-relationships and bitumen structure. Bitumen’s
internal structure was also studied using high resolution TEM (Philips CM 30).
6.5 EMBLA SOLID BITUMEN COMPOSITION
Of the 27 allochthonous solid bitumens described by Curiale (1986), only 5 have atomic H/C
< 0.90 (3 of them being impsonites) and all but one sample suite, namely uraniferous nodules
from Kiowa County, Oklahoma (consisting of 5 samples), are partially or wholly solvent
extractable. However, it must be noted that the three impsonites (two are from Page,
Oklahoma) had negligible solubility (0.5 - 2.7 %). The fact that the majority of Curiale’s
(1986) solid bitumen suite is soluble, allowed extensive chemical characterisation of the
bitumen phase via gas chromatography and mass spectrometry. The solid bitumen aliquots
recovered from the Embla sandstone cores are insoluble in common organic solvents, thus
severely limiting chemical characterisation of this organic phase using similar geochemical
techniques. However, some key parameters necessary to define and understand the carbon
phase could be measured (Table 1).
Insolubility of the studied solid bitumens clearly points towards the large molecular size and a
high degree of alteration/cross-linking, although it remains an organic carbon-rich phase
(comparable to some coals); but its low hydrogen indices and high Tmax suggest that it is not
presently very labile and represents a severely (thermally?) degraded material. This is
confirmed by high reflectance obtained (up to 1.27%) in oil immersion. Based on the
classification proposed by Cornelius (1987) and the atomic H/C and O/C ratios obtained for
the Embla bitumens, these could be classified as epi-impsonite, a bitumen phase with one of
the lowest H/C, the only other bitumen with lower H/C being Shungite (H/C about 0.1). The
strong possibility that the present bitumen phase resulted from a ‘normal’ migrated
hydrocarbon phase is indicated by the bulk carbon isotopic values (-25.35 to -27.74) slightly
heavier than the typical (post Jurassic) North Sea oils (Hughes et al., 1985; Bjor0y et al., 1994,
Bharati et al., 1997c). Northam (1985) has also noted, based on carbon isotope profiling, that
the 8i3C value of the residuum resulting from, for example oil cracking, becomes slightly (2-3
%o PDB) heavier as compared to the original whole oil. In comparison to most of the
conventional crude oils (H/C about 1.9), heavy oils (H/C about 1.6) or asphalt (H/C about 1.4,
Cornelius, 1987), the Embla bitumens with H/C of 0.77-0.90 represent a highly degraded stage
of migrated hydrocarbons.
Pyrolysis-gas chromatography using GHM provides very useful data in elucidating the
chemical composition and measuring the degree of present lability. Interestingly, the thermal

Mobile and immobile migrated hydrocarbons in the Embla Field, North Sea
20X/Host rock
26S/Host rock
20X/Bitumen
26S/Bitumen,

extracts (Figures la and b) and pyrolysate signatures (Figures le and f ) of bitumen-free host
rocks from wells 20X, 21S (in the central block, Figures la and e), 23S (in the northern block)
and well 26S (located in the western block, Figures lb and f) are very similar (see Figure 1 in
Bharati, (1997) for well locations).
Table 1: Selected physical and chemical properties of untreated solid reservoir bitumen
isolated (physically from cores, using a scalpel) from the Embla reservoir sandstones.
Parameter Value Nr. of samples

Colour and appearance (in host rock) Black, vitreous 18
Solubility (in dicMoromethane:methanol, 93:7 v/v) Insoluble 5
Total organic carbon (TOC) (%) 40 - 62.5 6
Hydrogen index (mg HC/g TOC) .......... .124-154 _ 6
Tmax (°C) 468 - 473 6
Reflectance (oil immersion, %) 114- 1.27 6
Atomic H/C 0.77 - 0.90 3
Atomic O/C 0.03-0.05 3
Atomic S/C 0.01 - 0.04 3
Atomic N/C 0.01 - 0.04 3
Ash content (weight %) 42-66 3
Uraniumcontent (ppm) __ 15-4.2_________ 8
Thorium content (ppm) <50 - <100 8
B#momatidty(%). ____________ .. _ 65-68% 3
Major carbon types ArC, ArCC, CH2 3
S13C(%oPDB) -25.35 to-27.74 12
However, the composition of bitumen pyrolysates from wells 20X or 21S (Figure lg) are very
different when compared to those from well 26S (Figure lh), although the signatures from
well 23S are comparable to those from 20X/21S. The most striking difference between the
20X/21S and 26S bitumen pyrolysates (Figures lg and h respectively) is in the type of
chemical moieties released on pyrolysis.
The bitumen samples from wells 20X and 21S have a greater abundance of labile
components, traceable up to nCgs, and a very strong homology of n-alkene/n-alkane doublets -
a signature very similar to that obtained from a type II kerogen (Barter and Senftie, 1985;
Figure 1: (previous page) Thermal extract (left) and pyrolysate (right) signatures of bitumen-
free host rocks (a and e from well 20X, b andffrom well 26S) and bitumen samples (c and g
from well 20X, d and h from well 26S). Peak identification: To - toluene, Xy - xylene, the
numbers indicate the number of carbon atoms in a straight chain; e.g. 15 indicates n-
heptadecane in TE-GC traces and the position of n-heptadecene Jheptadecane doublet in the
PY-GC traces, Pr - pristane and Ph - phytane.

Bjor0y et al, 1992). In contrast, the 26S bitumens lack all of the above characteristics and
instead produce mainly only gaseous and medium range compounds with n-alkanes being
comparatively insignificant, a signature comparable to that from type HE/TV kerogen. This
difference is not believed to be attributable to any difference in bitumen morphotype (as
described by Bharati, 1997), but related more to the location of the well and preservation
history of the bitumen phase in the given fault block. In the case of wells 23S and 27S, in
which no bitumen could be seen either by naked eye or under the microscope, presence of
disseminated bitumen was confirmed by elemental mapping (Bharati, 1997). In these wells,
while the thermal extract signatures remain essentially the same down the wells (Figures 2a-c),
the pyrolysate signatures change dramatically in samples from the bitumen-free zone to deeper
bitumen zone (Figures 2d-f). By and large, the pyrolysate signature of dissipated bitumen is
qualitatively comparable to the 20X and 21S bitumen samples.
However, irrespective of the internal compositional differences between the bitumens from
different locations, the common fact that all bitumen samples release components as seen in
the PY-GC signatures is in itself somewhat surprising, especially if compared to Curiale’s
(1986) pyrograms of the insoluble bitumens. In addition, the signatures are in some
contradiction to bulk pyrolysis and particularly elemental (H/C) data. Any sedimentary organic
material with an H/C of 0.8 or so would generally not be expected to produce a signature such
as in Figure lg. It is therefore imperative to elucidate and understand as to why this carbon
mass, initially thought to be nearly inert, gives contradictory data and whether labile
components are actually present. Direct analysis of solid bitumen to assess biomarker
composition (using GHM-MS) proved futile as no biomarkers were detected in the samples.
6.6 The nature of carbon in the Embla bitumens
Several studies have been conducted in which bulk aromaticity (fa) of natural organic matter
such as kerogen and solid bitumens has been measured using solid state 13C CP/MAS NMR
(e.g. Hatcher et al., 1981; Miknis et al., 1982; Soil! et al., 1985; Curiale, 1986). Recently, new
and far more enumerated applications of NMR were developed by Mann et al. (1991) and
Patience et al. (1991), whereby in addition to conventional fa determination, it allowed
quantitative estimation of individual carbon types that make up the sample’s molecular
structure. This technique was successfully employed to characterize the complex nature of
organic carbon in natural geological systems such as kerogens (Bharati et al., 1995). In the
present study, the methods and principles originally developed and employed for the study of
kerogens were utilized (with modifications) to characterize solid reservoir bitumens from
Embla, in order to predict the individual chemical moieties that make up the bitumen mass.
Apart from the fact that the Embla bitumens have a gross aromaticity of 65-68%, more than
30% of all carbon is found to be aromatic ring carbon (benzene =15%, naphthalene = 11% and

Bitumen-free
Zone
Transition
Zone
Bitumen
Zone
Figure 2: Typical thermal extract (left) and pyrolysate (right) signatures of bitumen-free zone
(a, d), transition zone (b, e) and dissipated bitumen bearing zone (c,f)from well 23S (trap
UM2). Peak identification: To - toluene, Xy - xylene, the numbers indicate the number of
carbon atoms in a straight chain; e.g. 15 indicates n-heptadecane in TE-GC traces and the
position of n-heptadecene / heptadecane doublet in the PY-GC traces, Pr - pristane and Ph -
phytane.
Norwegian University cf Science and Technology

phenanthrene/ anthracene == 5%) in addition to about 35% other aromatic carbon (Figure 3).
The estimates of 2-ring naphthalene and 3-ring anthracene/ phenanthrene were made on the
basis of bridgehead carbon amount. Of the aliphatic carbon types, methylene carbon (both
rigid and mobile CH2) is the dominant type (about 10%), suggesting that most of the aliphatic
carbon may be present in form of short alkyl chains (ethyl to butyl), particularly in light of the
fact that about 3% of the carbon is aliphatic methyl (CH3), the end member of an alkyl chain.
All the other aliphatic carbon types are present in sub-equal quantities (ca 2-4 % each, Figure
3). NMR data are in agreement with the elemental analysis data and confirm the condensed
and highly aromatic nature (high molecular weight) of the Embla bitumen mass (but perhaps
contradicts the pyrolysis data).
Relative % Figure 3: Results ofNMR analysis

Aromatic Species Sample B of isolated pure bitumen fraction.
Gross Aromaticity Relative percentages of the major
65%
aromatic moieties (hatched bars)
and aliphatic moieties (open bars)
Aliphatic Species are calculated from the deconvo
lution of the NMR spectrum, based
on chemical shift of each carbon
type.
Carbon Type
6.7 Internal structure of the bitumen phase
The Embla bitumens, which have been classified into several morphotypes (Bharati, 1997),
show distinct differences in the topographical features from different modes of occurrences
(cavities, vugs, veins and fractures). However, equally clear and discrete differences are not
observed in the internal structure of different morphotypes, although some bitumen masses
(extracted from cavities) show very interesting structural features when observed using a SEM
(Figures 4 and 5). In cross-sections (most probably along a contraction fracture), some
massive bitumen masses exhibit a systematic, outwardly radial ‘growth ring’ pattern (Figure
4a) which on higher magnification shows that the ‘rings’ or zonations are successive and equi-
spaced (about 1-1.5 |xm apart, Figure 4b). Further magnification (down to nm level, Figures 4c
and d) reveals another interesting aspect, namely the granular constitution of the bitumen

Figure 4: Internal structures observed in the Embla bitumens using SEM. a) general view of a
massive bitumen cross-section (wall) exhibiting ‘growth ring’ pattern. The arrow points to the
area enlarged in b) and the marked area in b) is enlarged in c) and d). e) Enlargement of a
foliated bitumen surface showing thinner folia f) general view of a freshly broken massive
bitumen surface, enlargements of which are shown in Figure 5.
BE!
mass. A significant point to note is the uniformity in size of the individual granules (mostly
ranging 80-100 nm). No compositional difference could be established between the dark grey
and light grey zones, but any compositional differences that might be present (which in all
probability would be differing N, S or O contents and/or the form in which these are bonded)
are beyond the detection capabilities of a SEM. In the case of foliated bitumen, individual
folium apparently consist of a bundle of thinner parallel folia (Figure 4e), each of these sub
folium again consisting of even thinner folia. These features suggest that the formation of
bitumen was slow, progressive and layer after layer.
High resolution TEM analysis was performed to examine the micotextural and structural fea
tures, particularly to understand the distribution of the basic structural units (BSU). Similar
work has been reported earlier for asphaltenes (Bonnamy et al., 1987), coal (Ross et al., 1991)
and bitumen (Cordal et al., 1990). In the present study, an attempt has been made to apply this
technique to solid reservoir bitumen from Embla using 002 dark field images. Transmission
electron micrographs show local molecular orientation (LMO) domains, about 30A across, in
the BSUs with weak planar preferred orientation. However, the gross degree of order (of the
aromatic ring stacks) is considered to be poor, but uniformly compact and the solid bitumen
carbon phase appears to be turbostratic in nature. Turbostratic carbon is essentially hard, non
graphic and baked carbon with small pores, usually quite uniformly distributed and intercon
nected and the plate alignment is short-range and the crystallites are much smaller (Murdi,
1996). Selected area electron diffraction (SAED) patterns clearly show broad and complete
002 rings and indicate the bitumen’s amorphous, but weakly ordered nature.
With regards to freshly broken cross-sectional surface features (ffactographs), two unrelated
examples were observed. A general view of one is shown in Figure 4f. Further magnification
(Figures 5a-c) reveals that the bitumen mass consists of several parallel horizontal layers
(Figure 5a) which are cross-connected by equi-spaced and thinner vertical layers (Figure 5b).
The horizontal layers on the other hand consist of a bundle of thinner horizontal layers (Figure
5c). Clearly, the process of bitumen formation must have been slow for such systematic and
recurrent features to be developed. The second example (Figures 5d-f) exhibits the ductile
nature of the bitumen mass very clearly. The fracture, which is across a bitumen particle
(Figure 5d) shows on enlargement the classic dimpled pattern of fine, equiaxed ductile shear;
this is very similar in nature and appearance to ductile shear rupture obtained in the titanium
alloy T1-6A1-4V (ASM Metals Handbook, 1992, page 447). Such fracture surfaces are
produced when the shearing is slow.
6.8 Timing of bitumen formation
In order to address and understand the processes involved which led to the formation of solid
bitumen in the Embla reservoir, it is imperative to first establish the relative timing of

Figure 5: Internal structures observed in the Embla bitumens using SEM (contd.). a)
enlargement of the area shown by the arrow in Figure 4f. b) and c) are enlargements of
different areas from a) to show details of the horizontal and vertical layers respectively, d)
example of another freshly broken bitumen surface - general view. The arrow points to the
area enlarged in e). The marked area in e) is enlarged inf).

formation of the major mineralogical phases observed in the inter-granular space (paleo-
porosity) in relation to each other, particularly with respect to bitumen. Burial history and
diagenesis play a crucial role in the evolution of the paleo and present petrophysical properties
of the pre-Jurassic reservoir sandstones. Realistic burial / temperature history modeling were
not performed in the Embla field successfully due to several limitations, such as: 1) unknown
exact age of the reservoir, 2) discontinuity and / or irregular present-day layer thickness, 3)
several unconfirmities and thickness of eroded sections unknown (presently only about 400 m
sediments to account for about 160 Ma), and 4) no neighbouring well data available to make
analogues or pseudo-wells. However, petrological and SEM observations have helped in
understanding the sequence of major geological events.
6.8.1 Diagenetic considerations
In general, the Embla reservoir sandstones are fine to medium grained (occasionally conglo
meratic) with moderate to good sorting (Figure 6a). Quartz cementation is generally extensive
and is reasonably advanced locally in a few zones, as overgrowth quartz (OG); forming Y-
junctions commonly observed. However, locally in some zones, authigenic quartz is totally
absent due to either hematitic cement (Figure 6c) or the presence of a thin dirty clay layer over
detrital grains (Figure 6d) preventing quartz overgrowth. Kaolinite is very well developed,
fresh in appearance and occurs as densely packed vermicular books (occasionally as
feldspathic pseudomorphs). Poikilotopic calcite cement exhibiting strong zonation is observed
sporadically. K-feldspar and illite are absent or, at best, very rare.
Absence of any feldspar and illite in the Embla sandstones indicate two important events: 1)
feldspar dissolution, which took place early and in an open system due to meteoric water
flushing, was total and kaolinite precipitation continued until the supply of A1 was eliminated;
at this stage the sediments are not expected to have been buried more than about 2 km. 2)
either the system was then closed preventing circulation of meteoric waters which could bring
in K, an essential component for illite formation, OR illite formation was arrested due to early
oil emplacement
Figure 6: (following page) Petro-micrographs of the Embla reservoir sandstones, a) typical

sandstone from a bitumen-free zone, blue epoxy indicates porosity, b) similar sandstone from
a dissipated bitumen-bearing zone. Note the reduced porosity, c) view of relatively rare
sandstone with hematitic cement (restricted to well 26S). d) example of sandstone with dirty
clay coating over detrital quartz grains; inset is enlargement of a typical grain surface with
brownish clay coating, e) overgrowth quartz seen engulfing books of kaolinite (shown by
arrows), f) relationship ofpoikilotopic calcite cement, quartz cement and bitumen, g) a large
mass of kaolinite occurring totally within the bitumen phase, h) black bitumen occurring in
kaolinite’s inter-book micro-porosity (shown by arrows). Abbreviations: Bi - bitumen, Qd -
detrital quartz, Qc - quartz cement, Ka - kaolinite. Scale bars: a, b, c, d, e, g and h = 500 pm,
f= 200 pm and inset in d) 100 pm.

•1^:1
I m
Sommer (1978), while studying the Brent Group sandstones from the North Sea argued that
authigenic illite would be formed during oil and water migration but not after oil emplacement
into the reservoirs. An observation supporting this hypothesis was made by Thomas (1986)
that in the Statfjord Formation and Brent Group of the Heimdal Field in the Viking Graben,
North Sea, illite was much more abundant below the oil-water contact than above. With
respect to the closed system possibility, it has been shown earlier that authigenic illite forms
primarily by dissolution of kaolinite and K-feldspar when present together (Bjprlykke, 1983),
generally in the temperature regime of 130-140°C (Ehrenberg and Nadeau, 1989). In the
absence of K-feldspar, however, kaolinite is stable to much higher temperatures, as would be
the case in Embla. In the Hild Field, where the K-feldspar concentration is very low, kaolinite
is still stable and illitization has not taken place even at temperatures of about 150-160°C
(Lpnpy et al., 1986). Illitization may thus also depend on locally available sources of K+ (few
meters scale) and therefore not totally controlled by the import of K+ from distant sources, as
noted by Bjprlykke et al. (1992). In the case of Embla, non-availability of a local K source for
illitization seems to be overriding, although other factors which hindered illite formation (such
as oil emplacement) may have played an additional role.
Although quantitative data with respect to quartz cement in the Embla sandstones is not
available in the present study, and despite the locally observed rather advanced stage of quartz
cementation, it is surprising to observe high porosity (generally 10-15% in the Upper
Sandstone and 8-12% in the Lower Sandstone, Bharati et al., 1997a) still preserved in these
sandstones. As quartz cementation played a decisive role in porosity reduction in Embla, the
fact that high porosity (than would be expected) is still preserved implies that more extensive
cementation was hindered by some factor. This factor may well be emplacement of the paleo-
oil just before or during the initial phases of quartz cementation, as suggested by several
workers (e.g. Sommer, 1978; Robinson and Gluyas, 1992). However, it must be remembered
that other factors such as the thin coating of detrital quartz grains by clayey/ chloritic material
(Figure 6d) have played an important role in porosity preservation, but only locally. Similar
phenomenon has been documented by several workers (e.g. Heald and Larese, 1974),
including in the deep reservoirs of the North Sea (Ehrenberg, 1993). However, no micro
crystalline quartz coating, which is also known to inhibit quartz cementation as reported by
Aase et al. (1996) in the Ula and Gyda oil fields, North Sea, was observed in the Embla
sandstones.
6.8.2 Mineral inter-relationships
Abundant examples of overgrowth (OG) quartz engulfing books of kaolinite are seen in thin
sections (Figure 6e). Excellent examples are seen under the SEM too (Figures 8a and b),
which clearly show that kaolinite pre-dates quartz cement. In fact, the trace amounts of illite
also pre-date OG quartz, as the latter engulf illite too (Figure 7c). Optically continuous
poikilotopic calcite cement was formed after quartz cementation was completed (see the

Figure 7: SEM views of the major mineral phases in relation to each other, a) OG quartz
engulfing kaolinite books, b) another excellent example (a cross section through a detrital
quartz grain and the overgrowth) of quartz cement engulfing kaolinite, c) OG quartz partially
engulfing fibrous and hairy illite, d) solid bitumen deposited on a detrital quartz grain surface
and through which OG quartz protrude outwards, e) a kaolinite mass partially engulfed by solid
bitumen; marked area is enlarged inf) to show the bitumen phase within kaolinite’s inter-book
micro-porosity. Abbreviations: Ka - kaolinite, Qc - quartz cement, Qd - detrital quartz, II - illite,
Bi- bitumen.

contact between calcite and quartz cements and calcite cement and detrital quartz in Figure
6f), but before any bitumen was emplaced, as bitumen is found sandwiched between calcite
cement and quartz (Figure 6f). The evidence of bitumen being emplaced after quartz
cementation was complete, is seen in Figure 7d, where bitumen is seen as a thick layer over
detrital quartz on which overgrowth had occurred. In addition, contraction features in the
bitumen phase are clearly visible in the form of micro-fractures. Examples of bitumen
engulfing kaolinite masses are also abundant (Figures 8e and f), confirming early kaolinite
precipitation (pre-dating bitumen). Another feature evident in Figures 8e and f and 6h is that
bitumen is present in kaolinite’s inter-book micro-porosity, pointing towards the high mobility
of the petroleum phase (paleo-oil) before solidifying (into bitumen).
Pyrite, which is nearly absent in the host rock and was observed to be associated only with the
bitumen phase (Bharati, 1997), is found deposited in-situ on solidified bitumen (Figures 9a
and b) as amorphous rounded masses (framboidal ?), indicating formation of pyrite after
bitumen was solidified and bitumen serving as a preferred nucleadon site. Unlike studies
focusing on organic sulphur compounds, examples of which are numerous (Damste and De
Leeuw, 1990 and references therein; Orr and Damste, 1990 and references therein),
association of mineral pyrite and migrated hydrocarbons is rarely discussed (e.g. Parnell et al.,
1994). In the case of Embla solid bitumens, whether the observed pyrite was formed at the
cost of organic sulphur compounds or is a result of reaction between iron monosulphide
precursor and H2S is difficult to establish. The former would be true in case the reservoir
contained H2S and reactive Fe was readily available, as this reaction would preferably precede
the reaction with organic compounds. This Fe could not have been from Fe-bearing feldspar,
as we know that all feldspar was dissolved to from kaolinite early in the diagenetic history;
and most Fe resulting from feldspar dissolution would have been removed by meteoric waters
as the system was open at this stage. On the other hand, sulphate (possibly also iron?) could
have been brought into the system at a later stage by associated groundwater and could have
easily been reduced to H2S at high temperatures through thermochemical sulphate reduction
mechanism, as proposed by Orr (1974) and shown by Sassen (1988).
Another major mineral phase associated only with solid bitumen is barite and this occurs in
two different forms. Crystalline barite (perfect orthorhombic prismatic elongated parallel to a
axis - about 500 pm long, Figure 8c) is found completely embedded within the bitumen mass,
which indicates that barite crystallization was completed before bitumen was solidified. In
fact, a mould of a barite crystal was also observed (Figure 8d), perhaps resulting from a barite
crystal being knocked off during sample preparation. Unlike previously observed aspects such
as contraction fractures or bitumen surrounding OG quartz etc., which are relatively partial or
indirect indications, this is the most convincing and direct evidence clearly verifying that the
present solid bitumen phase (now immobile and fixed) was at one stage mobile and free
flowing (perhaps even a normal oil). In contrast, another form of barite (amorphous, vein

Figure 8: SEM views of the major mineral phases in relation to each other (contdL.). a)
amorphous and massive pyrite deposited on solidified bitumen; the central portion is enlarged
in b) exposing the pyrite-free inner bitumen core, c) perfect orthorhombic barite crystal
embedded in the bitumen mass, d) a barite crystal mould left behind in the bitumen mass, e)
vein barite filling a contraction/cooling fracture in bitumen, f) same field as in e) but in BSI
mode to highlight the atomic number contrast between carbon and barium. Abbreviations: Py
- pyrite, Bi - bitumen, Ba - barite.
:%
filling) is also found in the contraction fractures of bitumen (Figures 9e and f). As the micro-
fractures in bitumen were a consequence of contraction due to volume reduction and loss of
light components, these were formed concurrent with solidification. Any mineral phase sealing
these fractures must therefore post-date bitumen formation.
Most studies of barite formation have focused on more massive accumulations, such as
concretions, bedded barite and ore deposits (e.g. Lange et al., 1983; Graber and Chafetz,
1990). Very few studies address authigenic barite found as a common accessory mineral in
sandstones (e.g. Breit et al., 1990), although it has the potential to be used to understand
diagenetic conditions. No studies have been reported relating barite to migrated hydrocarbons.
However, in the case of Embla, barite is almost exclusively associated with solid bitumen and
not present in the host sandstone. Otherwise barite as pore-filling cement or poikilotopic
cement or replacement of detrital grains would have been observed in the host sandstone (not
seen in the present study), as observed by Breit et al. (1990) in the Late Jurassic Morrison
Formation in Colorado Plateau. Both Ba and sulphate could have been derived from the
subjacent evaporite (east of Skrubbe fault, cf. Figure 1 in Bharati, 1997), provided the
solutions bearing these moved upward along the fault and laterally into permeable sandstones.
This implies that the Skrubbe fault was not a sealing fault, a feature which, if true, has
overriding implications with respect to reservoir infilling. In any case, it is clear that as
euhedral barite immediately preceded bitumen solidification, vein barite infilling must
therefore have proceeded immediately thereafter, and may not be an artifact of, for example,
mud additives during drilling.
More importantly, the presence of both pyrite and barite in the same system, supposedly
formed in a comparable geological time-frame, raises another significant question. Unlike
pyrite, which would form under reducing conditions, barite is formed under oxidizing
conditions. In addition, the fact that pyrite and barite are associated primarily within the
bitumen phase and are absent in the host rock suggests that their precursors were either part of
or associated with the paleo-oil or were a result of the paleo-oil destruction / bitumen
formation process. An extension of both these hypotheses is that iron, barium and sulphur
(sulphate?) were already present in the paleo-oil system in some form. In my opinion, neither
pyrite nor barite could be a result of any hydrothermal fluid activity in the rock, otherwise
these should have been present in equal amounts in the host rock too. This is not seen in the
present study (Figure 11, Bharati, 1997).
Parnell et al. (1994) suggested that hydrocarbon bearing fluids contain a major aqueous
component capable of transporting inorganic species. One likely scenario in the case of
Embla could be that the migrated hydrocarbon charge contained an aqueous component, which
was capable of retaining reactive ions needed for mineralization, such as SO4-, Fe++ and Ba**.
Subsequent to oil emplacement, the following sequence of reactions could have occurred:

PaperS: Embla reservoir bitumen: Chemistry, structure and origin 127
i) pre-bitumen solidification, at relatively stable conditions

Ba"1"1" + SO4*" —» BaSO# (euhedral barite) ...................... (1)
ii) post-bitumen solidification and formation of contraction fractures
Ba++ + S04- —» BaSC>4 (vein barite) (2)
S04" + 1.33 (CH2) + 0.66 H20 -> H2S + 1.33 C02 + 2 0ET ....... (3)
Fe++ + 2H2S -> 2 H2 + FeS2 (pyrite) ............................... (4)
Equation (3) above is adapted from Orr (1974) and represents the net reaction, involving a
series of more primitive reactions, where H2S acts as both a catalyst and a reaction product.
Therefore such thermochemical sulphate reduction by organic matter (in this case light gases)
can initiate with even small amounts of H2S.
Considering the above evidences, the following post-depositional sequence of events is

believed to have occurred:
1) (Total) feldspar dissolution / kaolinite precipitation, 2) insignificant illitizadon, 3) quartz
cementation, 4) paleo-oil emplacement, 5) euhedral barite formation, 6) paleo-oil destruction /
solid bitumen formation, 7) vein barite infilling, 8) amorphous pyrite deposition and finally 9)
present day oil emplacement.
6.9 Causes of bitumen formation
Curiale (1986) has, in his assessment of a suite of 27 solid bitumens, ascribed their origin
mainly to biodegradation and post-sourcing thermal alteration, in light of the original thermal
state of their source rock. Several other studies have been reported which link solid bitumen
formation to these processes ( e.g. Lomando, 1992; George et al., 1994). George et al. (1994)
in addition have suggested that solid bitumen formation is related to secondary porosity
generation in sandstones. Solid bitumens not related to deep burial or any external heating are
also known (cf. gilsonites, which are sourced from Eocene Green River Formation, Utah,
Tissot et al., 1978). In the case of Embla reservoir solid bitumen, however, considering all the
available data and the geological facts that are not available, it is difficult to elaborate on and
accurately assess the possible cause(s) of bitumen formation or to build on any one possibility.
Nevertheless, the feasibility of important crude oil alteration processes is discussed below
individually. To be able to properly address this aspect, however, the following facts about
Embla solid bitumen, based on available data, must be borne in mind:
1) Solid reservoir bitumen is not found in the entire reservoir column and is mostly restricted
to the lower part of the reservoir, and the overall bitumen abundance and size of individual
bitumen bodies increase with depth.

2) The depth at which bitumen starts to occur in the Embla field is different in different fault
blocks / wells, perhaps indicating that some faults were reactivated post-bituminization.
3) The mode in which bitumen starts to occur is different in different fault blocks, but it
appears that in the shallower depths, microscopic dissipated bitumen is most common.
4) Eight different bitumen morphotypes have been recognized, each having discrete
topographical features, but grossly similar composition. The different morphotypes may be
attributes of (and result from) the shape, volume and size of the pore space that the petroleum
phase occupied before solidification.
5) The immobile petroleum phase represented by solid bitumen today was (perhaps) in the
geologic past a very mobile and free-flowing oil phase and there are indications that it may
even have been a ‘normal’ oil phase comparable to other North Sea oils (but not necessarily
Jurassic sourced).
6) In general, most chemical data suggest that Embla solid bitumen is a highly condensed and
aromatic carbon mass (epi-impsonite), but PY-GC data of some samples indicates presence of
some labile components.
7) Pyrite and barite are associated almost exclusively with the bitumen phase and are conspi
cuously relatively absent elsewhere in the host rock.
8) Embla bitumen is amorphous, but several systematic / orderly features are present that point
towards some methodical process of formation.
9) Data indicate that the paleo-oil phase, represented by solid bitumen today, was entrapped
early, perhaps in the Paleocene/Eocene period. The entrapped paleo oil could have then leaked
as a result of tectonic activity during Miocene (inversion).
10) In all likelihood, the present oil population (light-medium oil, API gravity 42°) is unrelated
to solid bitumen and was reservoired after solid bitumen was formed.
6.9.1 Commonly recognized causes ofpetroleum alteration
Local heating, for example via igneous intrusions (sills, dikes and larger plutons), is widely
known to heat the neighbouring sediments rapidly and to accelerate the process of thermal
maturation of organic matter such as kerogen (Simoneit et al., 1981; Gilbert et al., 1985;
Clayton and Bostick, 1986; Raymond and Murchisson, 1988). In case bitumen or migrated
liquid hydrocarbons are present, these will also be significantly altered or completely
destroyed depending upon the extent and proximity of the heat source. While dikes are
commonly from a few centimeters to a few meters thick, a large percentage of sills are
typically over 50 m thick (Shiant Isles sill - 150 m, Palisades sill - 300 m; Hughes, 1982).
Bishop and Abbott (1995) suggest that the extent of thermal alteration is 70-140% of the
intrusion thickness. In the case of Embla, if an igneous intrusion is present at all, it should be a
sill below the Lower Sandstone in the western fault block (well 26S) where bituminization is
most severe and extensive. Given the thickness of the bitumen zone (>250 m), the intrusion
must be at least 200-300 m thick. However, no known igneous intrusion of this magnitude is
present below or in the vicinity of the Embla structure which could have caused destruction of

PaperS: Embla reservoir bitumen: Chemistry, structure and origin 129
the oil phase / formation of solid bitumen. Moreover, bitumen formation due to such heating
would be rapid, contra the slow and methodical formation suggested for the Embla bitumens.
Irradiation from primary radioactive minerals (e.g. uraninite, monazite), is also known to cause
thermal degradation of organic matter (kerogen or oils) over geologic times (Rouzuad et al.,
1980, Curiale et al., 1983). Cortial et al. (1990) suggest that solid bitumen is derived from
thermal alteration of crude oil due to closely associated uraninite ores in the 2000 Ma years
old Francevillian Series of Gabon. However, although they conclude ‘massive precipitation of
uranium’ and show, using TEM, carbon particles entirely invaded by uraninite crystals, they
report a uranium content of 10 ppm or less in their original samples; this is comparable to
average uranium content in most sedimentary rocks. Another similar study (Oh et al., 1990)
presents more convincing data in this respect (reported U content in kerogens 45-543 ppm). In
the case of Embla however (host rock age estimated between 245-360 Ma), both uranium (1.5-
4.2 ppm) and thorium are in insignificant quantities (Table 1) in isolated bitumens as well as
host sandstone, to be able to explain such dimensions of bitumen occurrence.
In the recent years, much work has been directed towards the kinetics of petroleum formation,
expulsion and destruction (e.g. lingerer et al., 1988; Burnham and Braun, 1990; Horsfield et
al., 1992; Pepper and Dodd, 1995) and it is now clear that the two interdependent variables
affected by burial (i.e. time and temperature) and heating rates are of paramount importance.
With regard to thermal cracking of oil, which is a frequently cited mechanism of solid bitumen
formation (e.g. Curiale, 1986; Levine et al., 1991), it follows that for an oil-pool to undergo
metagenetic cracking (as would be the case with Embla bitumens), the reservoir sediments
must be buried rapidly to significant depths after oil-emplacement and remain deeply buried
until all original oil is converted to gas-condensate / gas (may escape from the system) and
pyrobitumen (retained in the system), as seen in the Smackover Formation, Mississippi Salt
basin (Sassen, 1988). No such direct burial evidence is available for Embla.
Based on extrapolation of closed-system programmed temperature pyrolysis experimental data

to natural geological heating conditions, Horsfield et al. (1992) estimated that the onset of gas
generation as a result of oil cracking would occur between 160°C and 190°C. Similarly,
Pepper and Dodd (1995) in their extensive coverage of this phenomenon suggest that no oil-
cracking occurs up to 174°C, possibly even as high as 195°C. However, both studies conclude
that pyrobitumen is a significant product of the process, in addition to methane. Pepper and
Dodd (1995) are of the view that in-reservoir cracking has received undue importance in the
past and in addition suggest that the kinetics of the cracking process are highly dependent on
both the initial hydrogen index of the source rock and the composition of the ieservoired oil.
In the light of this discussion, for a normal oil population to be first reservoired and then
completely cracked to produce the solid bitumen that we see today in Embla, this would
require first a significant uplift of sediments from about 4 km, then oil emplacement and then

rapid re-burial again (to a temperature regime of about 205°C) to cause bituminization. No
such burial history evidence is available at present. Alternatively, thermal cracking could
occur locally due to heat not related to burial, but as discussed above no such known heat
source exists in or around Embla.
Biodegradation is one of the most common causes of oil-pool destruction and estimated more
than 20% of all world reserves has been affected by microbial degradation. Specific physico
chemical conditions are required for effective biodegradation to occur such as continuous
circulation of meteoric waters to ensure oxygen and nutrients replenishment, maximum
temperature of about 80°C (typically 20° to 60-75°C), presence of hydrocarbons and microbes
etc. (Connan, 1984). The effects of biodegradation are also generally well established and
predictable, the most common ones being reduction in the overall saturated hydrocarbons
content, consequently relative increase in polar compounds (increase in sulphur and nitrogen)
and in general oils become heavier and more viscous (but not solid). Several case studies with
varying degree of biodegradation have been reported (e.g. Deroo et al. 1977; Williams et al.,
1986; Michael et al., 1989; Horstad et al., 1992). Tricyclic terpanes are considered to be most
resistant to microbial degradation (Connan, 1984). In contrast, the Embla solid bitumens are
not anomalously rich in sulphur and nitrogen (Table 1), devoid of any biomarkers and 813C is
not heavy (Table 1). Moreover, even for any biodegradation to occur, especially extremely
extensive as would be the case with Embla paleo-oil, the reservoir sediments would be
required to be uplifted to significantly shallower depths, evidence for which is not presently
seen. Last, as solid bitumen in Embla is confined to deeper portions of the reservoir, it follows
that the present bitumen-free zone could not have been occupied by paleo-oil, but a thick gas-
cap, otherwise signs of solid bitumen (if it was a result of biodegradation) should have been
present in the entire reservoir column.
The processes of deasphalting and gravitational segregation of reservoired oil have also been
subjects of discussion (Evans et al., 1971; Hirschberg, 1984; Dahl and Speers, 1985), although
the mechanisms are not yet fully understood. While deasphalting requires considerable
quantities of dissolved gas in the oil pool, gravitational segregation is achieved by diffusive
movements of molecules of varying size in a tall oil column (Evans et al., 1971). While both
these processes would result in the sinking of heavier asphaltic molecules to the bottom of the
reservoir, resulting in, for example, tar-mats, they still cannot account for solid reservoir
bitumens. Moreover, most tar-mat occurrences (e.g. Wilhelms and Larter, 1994 and references
therein) are known to be from a few centimeters to a few meters in thickness with
compositionally sharply defined zones, unlike a broad and discontinuous >250 m bitumen
zone in Embla. However, Rogers et al. (1974) demonstrated that reservoir bitumens
(asphaltene precipitates) formed by deasphalting have carbon isotopic ratios similar to the
original oil, whereas residues formed by thermal alteration have significantly heavier ratios.
The Embla bitumens do not have particularly heavy ratios (Table 1) and are within the normal

ratios for most North Sea oils. Therefore, deasphalting, in some form, may be somewhat
important in the case of Embla.
Therefore despite several known processes, as discussed above, which can significantly alter
an oil pool with respect to composition and physical properties, none of these processes can
fully and convincingly explain the observed features in the Embla solid bitumens. Perhaps it is
the missing pre-Jurassic geological and diagenetic history that holds the key, or it may be
combination of two or more of the above processes. To assert anything more in this regard,
although important, would be speculation and unfounded at this juncture. However, a
hypothesis which meets most (but not all) requirements and explains most (but not all)
features is proposed, with the hope that further thinking on this line might one day provide the
right answer. While the original precursor of the Embla solid bitumens is believed to have
been a ‘normal’ mobile oil, the immediate precursor is most likely to have been a viscous and
asphaltic phase with limited mobility. This is the key to the proposed model.
6.10 Paleo-oil emplacement and destruction in Embla: A hypothesis
The paleo-oil charge was introduced into the Embla reservoir at an intermediate diagenetic
stage, possibly concurrent with the onset of quartz cementation at a depth more than about 3
km. The paleo-oil, possibly representing the first stage migration, is thought to have been
aromatic-intermediate in composition (sulphur > 1%, relatively rich in resins and asphaltenes,
Tissot and Welte, 1984), but mobile enough to enter the inter-kaolinite book microporosity; it
is possible, however, that oil saturation was low and dissolved gas content was high. Such an
oil could be generated from a marine source rock deposited in a reducing environment and the
high resin/asphaltene content could be due to immaturity of the oil.
Subsequent tectonism (uplift and subsidence) could have re-defined the pore geometry
(secondary large scale cavities, fractures etc. finding place) of the reservoir system As the
system was closed and being continuously buried, significant overpressures developed.
Reservoir overpressure and a long history of petroleum emplacement may also be the reason
for the high porosity preservation that we see today. Subsequent uplift and release of stress via
faulting possibly caused separation of solution gas which formed a thick gas cap; and leakage
of entrapped hydrocarbons, not necessarily in that order. Leakage, on the other hand, could be
selective with hydrocarbons being lost preferably over higher molecular weight asphaltic
species, causing therefore the residue to be resin/asphalt rich. Concurrently, the separating gas
phase initiated deasphalting, and continuous burial resulted in even more gas being generated
resulting in further displacement of a significant portion of the oil column. Alternatively, the
gas-flushing could have occurred as a second-stage migration into the system causing
deasphalting.

In either case, the paleo gas-oil contact (GOC) could well be imagined to be at about the
currently measured base of the bitumen-free zone. At this stage, the oil below the GOC is
believed to have been very viscous and enriched in resin/asphalt species. The process of
euhedral barite formation could also have started around this time. The reservoir system
remained buried at this level (estimated about 4.5 km or greater) and exposed to high
temperature regime causing further loss of light components (formation of contraction
fractures) and solidification. The process of thermochemical sulphate reduction started around
this time resulting in pyrite deposition. The gas-cap gas and solid bitumen’s associated light
components leaked from the system, making the reservoir rock available once again for oil
accumulation. We see this in form of post-Jurassic pooling of the present day oil population.
6.11 Implications of solid bitumen in the Embla Field
Based on the findings of Bharati et al. (1997a), evidently both hydrocarbon abundance and
compositional variations present in the Embla Field correspond well with the petrophysical
disparities. The Upper Sandstone, which has higher porosity, is rich in migrated hydrocarbons
and is apparently more rhythmic and non-homogenous with respect to richness and
composition, as compared to the Lower Sandstone. However, the migrated petroleum in the
Upper Sandstone is richer in hydrocarbons relative to non-hydrocarbons, when compared to
the Lower Sandstone petroleum. This, in all likelihood, is due to extensive asphaltene-rich
solid bitumen development in the latter. Compositionally, the signature of migrated petroleum
changes both horizontally across the various traps and vertically down the reservoir. This is
particularly true in the Lower Sand traps LSI and LS2, where the relative non-hydrocarbon
percentage increases dramatically with depth.
Solid bitumen in the Embla Field represents a lost and completely unrecoverable portion of the
migrated hydrocarbons. Apart from the obvious deterioration of the reservoir quality with
regard to permanently lost porosity, narrowing of pore throats and significant, decrease in
permeability in the bitumen zone, the formation and presence of solid bitumen has other
important implications. Due to its very nature, composition and despite cement-like
characteristics, both porosity (via neutron logs for example) and net ‘pay’ (via resistivity logs
for example) are overestimated. In addition to known heterogeneity and compartmentalization
(Bharati et al., 1997b), this phase adds to the complexity of the reservoir with regards to
optimal development of the field. Unfortunately, examination of rock material is the only
reliable method, so far, to map in detail the occurrence of solid reservoir bitumen. This means
that the presently understood extent of bitumen zone in the Embla Field may be
underestimated, given the number and locations of samples studied. While the Lower
Sandstone trap in well 26S (LS2) is clearly very poor, the prospects of the Lower Sandstone in
well 20X fault block (trap LS2) in the center of the field (which was not tested) remains
questionable. More so, despite the OWC in trap US2 being interpreted to be deeper than the
deepest core sample analysed (Bharati et al., 1997b), the productivity of the lower 100 m thick

reservoir column (of the total about 200+ m, cf. Figure 2, Bharati, 1997) which lies in the
bitumen zone, may be significantly lower than the upper bitumen-free zone. Unfortunately,
this is difficult to establish from DST, as the test interval covered nearly the entire zone
together.
6.12 Summary & Conclusions
The Embla bitumens have been classified into 8 different morphotypes based on textural and
topographical features as observed by SEM and may be attributes of the shape, volume and
size of the primary or secondary pore space that the petroleum phase occupied before
solidification. This very high TOC, black and vitreous phase is at the present day emplaced as
an ‘oil cement’, reducing severely the bulk porosity and permeability of the host rock. Its
insolubility in organic solvents, low H/C ratio and high aromaticity indicate its condensed
nature and large molecular size, although partially contradicting data is obtained by Py-GC.
More than 30% of all carbon in the Embla bitumen is found to be aromatic ring carbon and
aliphatic carbon is a minor component. Detailed examination of bitumen samples by SEM and
TEM indicate that the process of bitumen solidification was slow, controlled and methodical
and post-date all the major diagenetic events such as kaolinite precipitation and quartz
cementation. The barite and pyrite mineral phases, exclusively associated with bitumen, are
believed to represent the aqueous component of the migrated hydrocarbons.
The actual cause of bitumen formation is not entirely clear in the case of Embla, but
deasphalting may have played an important role (certainly not exclusively), at least in
providing the immediate precursor to solid bitumen. While the original precursor of the solid
bitumens is believed to have been a free-flowing and perhaps a ‘normal’ oil, its immediate
precursor is thought to have been a viscous and asphaltic species rich phase with limited
mobility and limited labile components. The present oil population is not related to the solid
bitumen and represents an entirely independent oil charge.
Many thanks to Phillips Petroleum Co. Norway for providing the samples and co-venturers,
including Fina Exploration Norway S.C.A., Norsk Agjp AS, Elf Petroleum Norge AS, Norsk
Hydro Production AS, Statoil AS, TOTAL Norge AS and Saga Petroleum AS for permission to
publish. Thanks also to Norwegian Research Council, Phillips Petroleum and Amoco Norway
for partial financial assistance. The Department of Geology, Norwegian University of Science
and Technology (NTNU), Trondheim is thanked for support and encouragement. The
following are gratefully acknowledged for assistance in conducting analyses: Morten Raanes
and Kjell Muller, SINTEF for SEMs, Prof. John Attard and Winfried Kuln, MR Center,
SINTEF for NMR and Prof. Ragnvald H0ier and Sigmund Andersen, Dept, of Physics,
NTNU for TEM. The manuscript benefited greatly from comments made by Joe Curiale,
■V; W: ■ A.
Unocal, USA on an earlier draft. Kare Vagle, Phillips, Norway is particularly thanked for
taking constant interest in my work and discussing my results openly, which has improved the
quality of this work.
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Paper 6: Calibration and standardization oflatroscan 141
Chapter 7: Paper 6
Calibration and standardisation of Iatroscan (TLC-FID) using

standards derived from crude oils
Sunil Bharati, Geir Arne R0stum and Rita L0berg
Geolab Nor, N-7002, Trondheim, Norway
Advances in Organic Geochemistry 1993

Org. Geochem. Vol. 22, No. 3-5, pp. 835-862, 1994
Pergaraon Copyright © 1994 Elsevier Science Ltd
0146-6380(94)00086-7 Printed in Great Britain. All rights reserved
0146-6380/94 S7.00 + 0.00
Calibration and standardization of Iatroscan (TLC-FID)

using standards derived from crude oils
Sunil Bharati, Ghr Arne Rgstum and Rita Loberg
Geolab Nor, P.O. Box 5740 Fossegrenda. 7002 Trondheim, Norway
Abstract—The TLC-FID technique, using the Iatroscan instrument, which constitutes separation and
quantification of a complex mixture into various compound classes, has recently become a widely used
and reliable method for characterisation of solvent extracts (particularly from reservoir rocks) and crude
oils. However, there has been only limited reported research conducted aimed at calibration of the
instrument and usage of standards which are relevant to the petroleum industry. This study is specifically
aimed at identifying, separating, characterising, testing and developing standards, derived from natural
crude oil(s), that are well suited and chromatographically pure for quantification purposes.
A sample set comprising of over 30 crude oils from various basins of the world was used. The oils range
widely in maturity, API gravity (8-46°), source rock type, degree of biodegradation, reservoir rock type
and relative compositions. Whole oils, maltenes and asphaltenes were initially screened using Iatroscan.
The process to identify suitable saturated hydrocarbons, aromatic hydrocarbons, polars and asphaltenes
for the purpose of making the standard(s) included MPLC, gas chromatography, column chromatography
and preparative thin-layer chromatography. Only about half the oils separate into 4 ‘clean* fractions
(saturated and aromatic hydrocarbons, resins and asphaltenes) resulting in 4 well defined peaks. Analysis
of the maltenes and asphaltenes shows that neither of the fractions is free of the other fraction. Pure
fractions of saturated and aromatic hydrocarbons, resins and asphaltene were isolated using a combination
of various analytical techniques and standards prepared. Compositional variations between the different
fractions was established using GC, Py-GC and GC-MS. Several synthetic standards were prepared and
tested for comparison and the implication of their use discussed. The Iatroscan TLC-FID instrument was
calibrated using data from naturally derived fractions/standard mixtures and a mathematical model
developed that could be used as the basis for calibration.
Key words—Iatroscan TLC-FID, petroleum, calibration, response factors, analytical accuracy, model,
natural standards, synthetic standards, oil fractions

Advances In Organic Geochemistry 1993

Org. Ceochem. Vol. 22, No. 3-5, pp. 835-862, 1994
Pergamon Copyright © 1994 Elsevier Science Ltd
0146-6380(94)00086-7 Printed in Great Britain. All rights reserved
0146-6380/94 S7.00 + 0.00
Calibration and standardization of Iatroscan (TLC-FID)

using standards derived from crude oils
Sunil B ha rati, Geir Arne Rostum and Rita Loberg
Geolab Nor, P.O. Box 5740 Fossegrenda, 7002 Trondheim, Norway
Abstract—The TLC-FID technique, using the Iatroscan instrument, which constitutes separation and
quantification of a complex mixture into various compound classes, has recently become a widely used
and reliable method for characterisation of solvent extracts (particularly from reservoir rocks) and crude
oils. However, there has been only limited reported research conducted aimed at calibration of the
instrument and usage of standards which are relevant to the petroleum industry. This study is specifically
aimed at identifying, separating, characterising, testing and developing standards, derived from natural
crude oil(s), that are well suited and chromatographically pure for quantification purposes.
A sample set comprising of over 30 crude oils from various basins of the world was used. The oils range
widely in maturity, API gravity (8-46"), source rock type, degree of biodegradation, reservoir rock type
and relative compositions. Whole oils, maltenes and asphaltenes were initially screened using Iatroscan.
The process to identify suitable saturated hydrocarbons, aromatic hydrocarbons, polars and asphaltenes
for the purpose of making the standard(s) included MPLC, gas chromatography, column chromatography
and preparative thin-layer chromatography. Only about half the oils separate into 4 ‘clean’ fractions
(saturated and aromatic hydrocarbons, resins and asphaltenes) resulting in 4 well defined peaks. Analysis
of the maltenes and asphaltenes shows that neither of the fractions is free of the other fraction. Pure
fractions of saturated and aromatic hydrocarbons, resins and asphaltene were isolated using a combination
of various analytical techniques and standards prepared. Compositional variations between the different
fractions was established using GC, Py-GC and GC-MS. Several synthetic standards were prepared and
tested for comparison and the implication of their use discussed. The Iatroscan TLC-FID instrument was
calibrated using data from naturally derived fractions/standard mixtures and a mathematical model
developed that could be used as the basis for calibration.
Key words—Iatroscan TLC-FID, petroleum, calibration, response factors, analytical accuracy, model,
natural standards, synthetic standards, oil fractions
INTRODUCTION
previous work involving the use of the TLC-FID
technique using Iatroscan have relied upon synthetic
The TLC-FID technique, using the Iatroscan instru compounds as standards to accomplish quantification.
ment, is fast becoming a widely practised and reliable There are even lesser reported studies specifically
method for qualitative and quantitative characteriz aimed at developing natural standards (standards
ation of solvent extracts (particularly from reservoir derived from natural crude oils or extracts) which are
rocks) and crude oils. TLC-FID generally constitutes well suited and chromatographically pure during
separation of a complex mixture, such as EOM or TLC for the purpose of calibrating the Iatroscan
crude oil into compound classes. Depending upon the TLC-FID instrument. Poirier et al. (1984), for ex
chromatographic requirement and the sensitivity of ample, have used natural extract fractions to calculate
the instrument, a natural organic mixture, such as a the relative response and Parish and Ackman (1985)
crude oil, is typically separated into 3, 4 or even 5 have addressed the problem of calibration. In addition,
fractions, each fraction itself, however, being a com different laboratories have different preferences with
plex mixture, though essentially all components of a regards to the choice of synthetic compounds that
fraction are of similar polarity and belong to the same they employ as standards. All these factors result in
compound class. Recently, there have been some poor and inaccurate inter-laboratory comparison of
publications highlighting the practicality and applica data.
tion of Iatroscan in the petroleum industry (Goutx The present study is specifically aimed at identify
et al., 1990; Karlsen and Larter, 1989, 1991; Poirier ing, separating, characterising, testing and developing
et al., 1984; Ray et al., 1982; Selucky, 1983; standards, derived from natural crude oil(s), that are
Yamamoto, 1988). However, these studies have well suited, easily accessible and chromatographically
limited focus towards calibration of the instrument pure, that can be applied to Iatroscan and which are
and standardization of elutionary procedures. Most relevant to the petroleum industry. The term ‘natural

I
& Table I. Details of oil samples used in the study {listed according to increasing API Gravity)
S. No. Sample Code Location Field/Basin Reservoir Agc/Lithology Source Age/Type API Gravity
1 1-04 Mongolia, Asia Tsagaanels ___ — cu8 *
2 2-05 Peru, S. America Jibaro/Maranon U. Cretaceous/Sandstone — 10.7
3 3-06 Peru, S. America San Jacinto/Maranon U. Cretaceous/Sandstone 11.4
4 4-27 U.S.A., N. America Monterey/Santa Maria Mioccnc/Shalc Miocene/Marine ca 14 •
5 5-07 Netherlands, Europe Helm/Broad Fourtecns L. Cretaceous/Sandstone L. Jurassic/Marine 17.4
18 6 6-08 Peru, S. America Shiviyacu/Maranon U. Crelaceous/Sandstonc — 20.6
7 7-28 Angola, W. Africa Malongo West/Congo L. Cretaceous/Sandstone L. Cretaceous/Lacustrine 20.8
8 8-09 Netherlands, Europe Hcldcr/Broad Fourtecns L. Cretaceous/Sandstone L. Jurassic/Marine 22.1
9 9-30 Angola, W. Africa Malongo South/Congo L. Crelaceous/Sandstonc L. Cretaceous/Lacustrine 23.4
10 10-10 Peru, S. America San Jacinto/Maranon U. Cretaceous/Sandstone — 23.7
II il-il Austria, Europe Matzen/Vicnna Tertiary/Sandstone U. Jurassic/Marine 24
12 12-12 Germany, Europe Ruhlcmoor-Valendis L. Cretaceous/Sandstone L. Oligoccnc/Marine 24.5
S u n il B harati e t a l.
13 13-13 Norway, Europe Troll/Horda Platform M-U. Jurassic/Sandstone U. Jurassic/Marine 26.8
14 14-26 Norway, Europe TroII/Horda Platform M-U. Jurassic/Sandstone U. Jurassic/Marine 27.5
IS 15-03 Norway, Europe Haltcnbankcn L. Jurassic/Sandstone L. Jurassic/Marine 28.4
16 16-31 Angola, W. Africa Malongo West/Congo L. Cretaceous/Sandstone L. Cretaceous/Lacustrine 29.9
17 17-14 Austria, Europe Matzen/Vicnna Triassic/Dolomite U. Jurassic/Marine 30.2
18 18-15 Peru, S. America Dorissa/Maranon U. Cretaceous/Sandstone — 3I./6
19 19-25 Turkey, Europe Selmo-Batman U. Cretaceous/Carbonate U. Cretaceous/Marine ca 32 •
Norwegian University o f Science and Technology
20 20-16 Norway, Europe Central Graben U. Jurassic/Sandstone U. Jurassic?/Hypcrsalinc? 33.5

21 21-17 Peru, S. America Shiviyacu/Maranon U. Cretaceous/Sandstone — 34
22 22-29 Angola, W. Africa Malongo North/Congo L. Crelaceous/Sandstonc L. Cretaceous/Lacustrine 34.2
23 23-18 Norway, Europe Snorrc/N. Viking Graben L. Jurassic/Sandstone U. Jurassic/Marine 37.1
24 24-19 Germany, Europe Eich/Konigsgartcn L. Crelaceous/Sandstonc L. Oligoccnc/Marine 38.6
25 25-20 Australia Challis/N. Browse Triassic/Sandstone U. Jurassic/Marine 39.5
26 26-21 Ai.strlaia Jabiru/N. Browse M. Jurassic/Sandstone U. Jurassic/Marine 42.3
27 27-22 Austria, Europe Adcrkiaa/Vienna Tertiary/Sandstone U. Jurassic/Marine 43.2
28 28-23 Norway, Europe Central Graben U. Jurassic/Silty Sandstone U. Jurassic/Marine 44.2
29 29-24 Norway, Europe Midgard/Sklinnubanken M. Jurassic/Argi. Sandstone U. Jurassic/Marine 44.6
30 30-01 Australia Tirrawarru/Coopcr Permian/Sandstone Permian/Fluvial Deltaic 45
31 31-02 Australia Patroclus/Enomanga Jurassic/Sandstone Permian/Fluvial Deltaic 46
•Actual API Gravity data for these oils not available. Data quoted are relative visual estimates.
Note: The serial numbers in column I are not the same as oil numbers referred to in the text and tables.
Calibration and standardization of Iatroscan 837
standards’ includes the four principle fractions of collected and processed either using an integrator or,
crude oil/solvent extract viz. saturated hydrocarbons, as in our case, using a data acquisition system such
aromatic hydrocarbons, resins and asphaltenes. For as Multichrom v2. Raw data is automatically con
this purpose, a sample set comprising 31 crude oils verted into mg/g rock units and relative percentages
from various basins/fields (onshore and offshore) of (see later). Although no whole rocks were analysed
the world (North America, South America, Europe, in the present study, the additional procedure related
West Africa, Asia and Australia) was used (Table 1, to their analyses is included in Appendix 1 for the
oils listed according to increasing API gravity). The benefit of the readers.
oils range widely in (1) maturity (low maturity to high The oils were deasphaltened using n-pentane, ex
maturity, but not condensate stage), (2) API gravity cept in the case of asphaltene solubility experiments.
(8'-46=), (3) source rock type (marine clastic, marine Four samples were selected for asphaltene solubility
carbonate, lacustrine, saline), (4) degree of bio tests (oils 5, 10, 16 and 19, which cover a wide range
degradation (none to strong), (5) reservoir rock type of API gravity) and each of these oils were subjected
(sandstone, siltstone and carbonate) and (6) relative to asphaltene precipitation using six different solvents
compositions. The final objective is to successfully viz. n-pentane (which is normally used), n-hexane,
isolate one fraction each of saturated hydrocarbons, n-heptane, n-octane, n-nonane and n-decane. The
aromatic hydrocarbons, NSO compounds and purpose was to monitor the dependence, if any, of
asphaltenes, pure from the TLC-FID point of view, asphaltene composition on the solvent chain length,
and gravimetrically prepare standards for Iatroscan which also implies increasing boiling point of the
calibration. In addition, an attempt has been made solvent. In addition, our intention was to investigate
to refine the existing procedure for analysis, which and review the compositions of asphaltenes result
includes a mathematical model to determine effective ing from precipitation using solvents other than
response factors and their relationships, which can be n-pentane, and to establish whether an asphaltene
easily and readily employed by other users. fraction can be obtained through conventional
precipitation method which is the same or close to
ANALYTICAL PROCEDURES the asphaltene fraction defined by TbC-FID. Such a
fraction would be expected to result in only one peak
Whole oil samples and individual fractions were on analysis using the Iatroscan, following the normal
analysed by Iatroscan at several stages during the elution procedure.
course of the study. The following procedure for Maltenes were separated into fractions (saturated
Iatroscan analysis (using Iatroscan MK-5) was found and aromatic hydrocarbons and polars) using MPbC
to be most suitable for analyses of a variety of as described by Radke et al. (1980) (each of the oils
samples and therefore recommended for general use was analysed with one parallel to increase the amount
(see also Karlsen and barter, 1989). In the case of of resulting fractions). However, one significant devi
oils, 4-5 mg of whole oil is accurately weighed into ation from the routine method was during collection
a 2 ml GC glass vial, 0.5 ml of solvent added and of the fractions. As the purpose in the present study
the vial sealed. After being dissolved in the solvent, was to obtain pure fractions using MPbC and not
oils can be analysed immediately. Prior to sample quantification, the initial and final cuts (about 10%
spotting, the chromarods (quartz Sill, silica gel each) of each of the fractions (saturated and aromatic
powder coated) are first activated by passing through hydrocarbons and resins) were discarded (which are
the FID flame (in the normal analysis mode—30 s/ normally collected) by closely monitoring the RI
scan). 2 pi sample is then spotted (using a 2 pi syringe) detector in the case of saturated hydrocarbons and
using preferably an auto-spotter (SES 3202/IS-01) u.v. detector in the case of aromatic hydrocarbons.
and continuously blowing the spot with nitrogen or This was done to ensure that minimal amounts of un
air to accomplish immediate drying and prevent band wanted components are present in a fraction. Selected
spreading. This results in sharper and narrower peaks. saturated and aromatic hydrocarbon fractions were
The development tanks containing the solvents are characterised by gas chromatography, while selected
lined with chromatographic paper on the inside back polar and asphaltene fractions were characterised by
and side walls, from top to bottom. The following pyrolysis-gas chromatography. The purity of the
elution procedure is used: 35 min in n -hexane (to two hydrocarbon fractions was tested using gas
separate saturated hydrocarbons), air dry for 2 min, chromatography-mass spectrometry, while the com
14 min in toluene (to separate aromatic hydrocarbons), position of the selected resin and asphaltene fractions
air dry for 2 min, 4 min in dichlorometane: methanol, was established using pyrolysis-gas chromatography-
93:7 v/v (to separate resins) and finally 90s at 60°C. mass spectrometry. The procedures followed were
Asphaltenes are retained at the spotting point. If it is according to the Norwegian Industry Guide (1993).
intended to separate mono- and diaromatic hydro However, the selection of ions for GC-MS was made
carbons from poly-aromatic hydrocarbons (Karlsen keeping in mind the primary objective of major con
and barter, 1991) then insert the step of elution using taminant identification. As the analysis was carried
cyclo-hexane for 14 min before eluting with toluene out in high resolution mode, the number of ions was
for 8 min. The samples are analysed and the data restricted to 10. However, in separate runs, a few ions

838 Sunil Bharati et al.
characteristic for biomarkers were also detected. The silica with F254 fluorescence activator). The elution
ions specified during GC-MS are listed in Appendix 2. procedure employed was the same as that of Iatroscan.
Similarly, the ions for Py-GC-MS were selected in The zone separation was checked using a u.v. detector
such a way so as to indicate the presence of saturated at 254 nm wavelength (cf. Plate 1) and portions with
hydrocarbons, aromatic hydrocarbons (mono-, di- different fractions scrapped using a spatula. The 4
and poly-aromatic) and the sulphur bearing thio silica gel fractions were then extracted using
phenes. Additionally, the selected masses would also DCM:MeOH (93:7 v/v), weighed and analysed by
indicate the type of hydrocarbons that have the maxi Iatroscan.
mum tendency to be retained in the polar fraction.
No significance was placed on masses specific to com RESULTS AND DISCUSSION
monly known biomarkers as these are not expected
to occur in these fractions, although m/z 163, 231 Composition of oils, asphaltenes and maltenes
and 253 were included to get a general picture of Preliminary screening of all oils using Iatroscan
their presence. The list of the masses specified during (Table 2) shows that the composition of the oils is
Py-GC-MS is presented in Appendix 3. highly variable, as is their total hydrocarbon (satur
In addition, whole oil samples and selected resin ated and aromatic) content. The relative percentage
fractions were analysed using preparative thin-layer of saturated hydrocarbons varies from about 3 to
chromatography (PTLC), the main objective of this 82%, aromatic hydrocarbons vary from about 13 to
being to purify the resin fractions by separating out 54%, resins vary from about 2 to 46% and asphalt
aromatic hydrocarbons from the resins. The oils and enes vary from about 0.1 to 26% (Table 2). Never
resin fractions from MPLC were first dissolved in di- theless, hydrocarbons are dominant in all the oils,
chloromethane and spotted along a straight line (as varying from about 76 to 98%, except for one oil
a band) on a ready-made TLC plate (Merck DC-A1 which has a total hydrocarbon content of only 42%
foil coated with silica gel 60, gel thickness 0.2 mm, relative to resins and asphaltenes. The quality of
10cm
Plate. 1. On left are the results of TLC development of various fractions from MPLC (saturated
hydrocarbons—SAT, aromatic hydrocarbons—ARO, resins—NSO and asphaltene—ASP and whole
oil—EOM). On right is the TLC development of the MPLC resin fraction, which splits into 2
zones—resins and aromatics. Zone 1 marks the line of sample spotting, where the asphaltenes are also
retained, Zone 2 is resins. Zone 3 is aromatic hydrocarbons and Zone 4 is saturated hydrocarbons which
cannot be detected by fluorescence.
T
Table 2. Relative percentages of separated fractions by Iatroscan Table 3. Relative percentages of separated fractions by Iatroscan
from whole oils from asphaltenes
Sat Aro Total Total Sat Aro Total Total
HC HC Resins Asph HC Polars HC HC Resins Asph HC Polars
Oil No. % % % % % % Oil No. % % % % •/. %
1 72.8 25.3 1.6 0.3 98.1 1.9 1 40.0 50.0 10.0 40.0 60.0
2 82.2 13.9 1.6 2.3 96.1 3.9 2 64.7 35.3 100.0
3 77.3 21.1 1.3 0.3 98.4 1.6 3 15.4 28.8 55.8 15.4 84.6
4 62.3 19.3 11.8 6.6 81.6 18.4 4 11.5 17.4 71.1 11.5 88.5
5 19.7 39.7 15.9 24.7 59.4 40.6 5 71.4 28.6 100.0
6 23.7 38.8 10.9 26.6 62.5 37.5 6 5.1 4.9 90.0 5.1 94.9
7 34.1 54.2 8.0 3.7 88.3 11.7 7 32.4 67.6 100.0
8 34.2 42.8 8.7 14.3 77.0 23.0 8 100.0 100.0
9 44.6 45.2 6.5 3.7 89.8 10.2 9 37.8 62.2 100.0
10 46.4 40.5 6.7 6.4 86.9 13.1 10 32.8 67.2 100.0
11 49.8 42.3 7.2 0.7 92.1 7.9 11 49.5 50.5 100.0
12 33.4 44.3 17.6 4.7 77.7 22.3 12 14.8 10.3 34.0 40.9 25.1 74.9
13 53.0 42.2 3.5 1.3 95.2 4.8 13 49.2 50.8 100.0
14 64.3 31.1 3.7 0.9 95.4 4.6 14 45.0 55.0 100.0
15 58.3 34.8 5.4 1.5 93.1 6.9 15 37.4 62.6 100.0
16 56.2 34.2 6.8 2.8 90.4 9.6 16 6.4 19.9 73.7 6.4 93.6
17 56.5 37.4 4.7 1.4 93,9 6.1 17 42.7 57.3 100.0
18 62.5 31.1 5.0 1.4 93.6 6.4 18 25.9 9.6 41.2 23.3 35.5 64.5
19 70.0 25.7 2.3 2.0 95,7 4.3 19 27.3 72.7 100.0
20 61.3 35.4 2.9 0.4 96.7 3.3 20 53.3 16.4 26.6 3.7 69.7 30.3
21 78.5 20.0 1.4 0.1 98.5 1.5 21 32.4 56.8 10.8 32.4 67.6
22 78.3 19.3 2.2 0.2 92.6 2.4 22 53.7 35.2 11.1 53.7 46.7
23 59.3 35.7 4.5 0.5 95.0 5.0 23 17.0 59.1 23.9 17.0 83.0
24 76.3 22.2 1.2 0.3 98.5 1.5 24 100.0 100.0
25 47.5 44.2 6.1 2.2 91.7 8.3 25 8.9 9.6 30.6 50.9 18.5 81.5
26 57.0 37.3 5.3 0.4 94.3 5.7 26 45.5 54.5 100.0
27 2.9 39.3 46.5 11.3 42.2 57.8 27 — — — 100.0 — 100.0
28 56.8 19.4 12.7 11.1 76.2 23.8
29 42.6 33.5 18.3 5.6 76.1 23.9
30 66.4 22.6 10.1 0.9 89.0 11.0
31 50.1 33.2 13.9 2.8 83.3 16.7 individual fractions in these oils to separate into
distinct groups within the given time for separation
(35 and 14 min for hydrocarbons and 4 min for non
chromatography is generally good with the 4 fractions hydrocarbons), and the restricted length available for
(saturated hydrocarbons, aromatic hydrocarbons, separation/elution (10 cm).
resins and asphaltenes) giving 4 prominent peaks Deasphalting of oils shows that except for a few
[Fig. 1(a)], except in a few cases where a continuum oils, most oils contain asphaltenes in the range 1-4%
between the two hydrocarbon fractions [Fig. 1(b)] by weight. However, in case of several oils, a sub
or a continuum between the two non-hydrocarbons stantial portion of the asphaltene remained locked
[Fig. 1(c)] fractions is present. This is attributable to within the filter and was impossible to remove even
the composition of these oils and the inability of the by repeated washing using either dicholoromethane
Fig. 1. TLC-F1D chromatograms of whole oils, (a) A typical oil sample with 4 prominent peaks
representing 4 major components viz. saturated hydrocarbons (SAT), aromatic hydrocarbons (ARO),
resins (POL) and asphaltenes (ASPH). (b) An oil sample with a continuum between the 2 hydrocarbon
fractions, SAT and ARO. (c) An oil sample with a continuum between the 2 non-hydrocarbon fractions,
POL and ASPH.

840 Sunil Bharati et a!.
0 10 0 10 0 10
abed
Fig. 2. TLC-FID chromatograms of asphaltenes, (a) An asphaltene fraction containing significant
amounts of hydrocarbons (SAT and ARO). (b) A typical asphaltene fraction consisting mainly of resins
(POL) and asphaltenes (ASPH). (c) Chromatogram of an asphaltene with least amount of other
components, (d) A typical asphaltene from low API gravity oils, exhibiting a strong continuum between
the 2 non-hydrocarbon components, POL and ASPH.
or dichloromethane: methanol (93:7 v/v). This loss then it would mean that the fraction resulting from
is even more significant for oils rich in asphaltenes conventional pentane precipitation, which we com
(more than 10% by weight) such as oils 4, 5, 6, 8, 10 monly refer to as asphaltene, is compositionally
and 27. The analysis of asphaltenes using Iatroscan the same as the asphaltene defined by the Iatroscan
(Table 3) shows that none of the pentane precipitated technique. Apparently, asphaltenes precipitated by
asphaltene fractions result in pure “asphaltene” n-pentane are compositionally different to the frac
fractions from the TLC-FID point of view, as also tion defined as asphaltene by Iatroscan. The pentane
documented earlier (Karlsen and barter, 1991). Several precipitated asphaltene nearly always consists of two
of the asphaltene fractions analysed (such as from oils principle fractions—resins and asphaltenes (Table 3).
1,2,3,20,21,22,23 and 24) give a misleading picture It must also be noted that accurate integration of
(Table 3) due to very low absolute concentrations the resin and asphaltene peaks from Iatroscan is
of all the components and therefore their data are not possible in the case of some samples due to the
considered to be insignificant/unreliable. However,
in several others, the asphaltene precipitated by Table 4. Relative percentages of separated fractions by Iatroscan
«-pentane from oils such as 4, 6, 12, 16, 18 and 25, from mallenes
continue to retain substantial amounts of hydro Sat Aro Resins Asph Total Total
Oil No. HC HC HC Polars
carbons, and their chromatograms show up to 4
distinct peaks [e.g. Fig. 2(a)]. It seems though that 1 77.6 20.4 1.7 0.3 98.0 2.0
2 87.6 10.1 1.8 0.5 97.7 2.3
saturated hydrocarbons have a greater tendency of 3 78.7 19.9 IJ 0.1 98.6 1.4
being retained in the pentane precipitated asphaltenes, 4 54.7 9J 16.4 19.6 64.0 36.0
5 24.7 48.8 16.4 19.6 64.0 36.0
relative to aromatic hydrocarbons (Table 3). In most 6 28.9 57.9 12.9 0.3 86.8 13.2
of the samples, however, the pentane precipitated 7 30.9 54.8 13.4 0.9 85.7 14.3
asphaltene splits into mainly resins and asphaltenes, 8 40.0 49.9 9.5 0.6 89.9 10.1
9 42.5 45.3 11.6 0.6 87.8 12.2
as shown in Fig. 2(b). In none of the samples did 10 49.6 41.5 8.4 0.5 91.1 8.9
the pentane precipitated asphaltene fraction result in 11 54.2 35.1 10.4 0.3 89.3 10.7
only one (asphaltene) peak [example with the most 12 34.0 43.0 19.5 3.5 77.0 23.0
13 58.1 32.6 8.8 0.5 90.7 9.3
prominent asphaltene peak relative to resins is shown 14 69.9 22.9 6.7 0.5 92.8 7.2
in Fig. 2(c)]. Iatroscan separation of asphaltenes from 15 61.2 31.5 6.7 0.6 92.7 7.3
16 58.8 28.4 10.4 2.4 87.2 12.8
nearly all of the low API gravity oils, which are also 17 58.2 33.5 7.7 0.6 91.7 8.3
generally the richest in asphaltenes (Table 3), results 18 62.7 28.4 8.3 0.6 91.1 8.9
in a continuum between the resins and asphaltenes 19 74.4 20.9 4.2 0.5 95.3 4.7
20 73.8 20.6 5.1 0.5 94.4 5.6
[e.g. Fig. 2(d)]. This is indicative of either compos 21 82.2 15.5 2.0 0.3 97.7 2.3
itional similarity between the resins and asphaltenes 22 83.5 12.0 3.4 1.1 95.5 4.5
of these oils or inability of the components to separate, 23 64.5 30.0 4.4 1.1 94.5 5.5
24 71.0 16.5 3.5 9.0 78.5 12.5
as no overloading of samples occurred. 25 52.9 37.0 7.8 2.3 89.9 10.1
Had the pentane precipitated asphaltene fraction 26 82.6 13.9 2.9 0.6 96.5 3.5
27 — 37.9 59.6 2.5 37.9 62.1
resulted in only one peak on analysis using Iatroscan,

0 10 0 10
8 b c d
Fig. 3. TLC-FID chromatograms of maltenes. (a) A typical maltene fraction, rich in hydrocarbon
components SAT and ARO. (b) A maltene fraction with a dominant saturated hydrocarbon peak (SAT),
(c) A maltene fraction with a dominant aromatic hydrocarbon peak (ARO). (d) A maltene fraction with
significant amounts of non-hydrocarbons present (POL and ASPH).
continuum, and the data therefore can be quite (174°C) and consequently limited capacity of the
erroneous. Based on the results and the above rota-vapour to remove the solvent.
considerations, asphaltenes from oils 4, 5, 7, 8, 10, 16 From the qualitative point of view, both the
and 19 are thought to have the best potential for use asphaltenes and maltenes of each oil are composition-
as standards. ally very similar, resulting in nearly identical TLC-
Iatroscan analysis of maltenes (Table 4) show that FID chromatograms for a given oil, for all solvents
hydrocarbons are the most abundant species, typically
between 90 and 98% and generally over 77% of the
total maltene fraction [Fig. 3(a)], except for one Table 5. Asphaltene solubility experiment: gravimetric weights of
resulting maltenes and asphaltenes using different solvents
sample (sample 27). The composition of the hydro
Oil Asp Mall Asp Malt Loss
carbons however, is highly variable with saturated Sample (mg) (mg) (mg) <%) (%) (%)
hydrocarbons occurring in the range of about Pentane
25-81% [Fig. 3(b) shows a sample rich in saturated Oil 5 47.3 8.1 33.8 17.12 71.46 11.42
hydrocarbons] with one exception (no saturated Oil 10 45.8 4.1 36.8 8.95 80.35 10.70
Oil 16 45.5 1.0 37.4 2.2 82.20 15.60
hydrocarbons detected in sample 27) and aromatic Oil 19 47.7 0.9 34.0 1.89 71.28 26.83
hydrocarbons ranging about 10-57% of the total Hexane
content [Fig. 3(c) shows a sample rich in aromatic Oil 5 48.1 9.5 34.1 19.75 70.89 9.36
hydrocarbons]. Resins or polar compounds are in Oil 10 41.9 3.3 35.9 7.88 85.68 6.44
Oil 16 51.5 0.3 43.5 0.58 84.47 14.95
most cases minor components (generally 1-8%) but Oil 19 49.5 0.8 37.5 1.62 75.76 22.62
occur in larger amounts in a few samples (10-16%) Heptane
[Fig. 3(d) shows a sample rich in resins]. One exception Oil 5 55.8 11.4 40.2 20.43 72.04 7.53
is sample 27 which contains about 59% resins. Oil 10 46.6 3.7 39.1 7.94 83.91 8.15
Oil 16 59.0 0.5 50.0 0.85 84.75 14.40
Asphaltenes, which ideally should not be detected Oil 19 49.6 0.7 13.9* 1.41 — —
in maltenes, occur in all maltenes although their
percentage is small—ranging about 0.1-3%, with Oil 5 41.7 8.1 21.5 19.42 51.56 29.02
3 exceptions (oils 4, 5 and 24). Oil 10 61.0 4.5 50.4 7.38 82.62 10.0
Oil 16 51.2 0.3 41.0 0.59 80.08 19.33
Oil 19 48.7 1.1 14.9* 2.26 — —
Asphaltene solubility lest
Nonane
Table 5 shows the results of the asphaltene solu Oil 5 61.2 12.5 37.5 20.42 61.27 18.31
bility experiment and the amount of asphaltene yields Oil 10 45.2 29.8 35.8+ 79.20
Oil 16 53.5 3.6 42.1 6.73 78.69 14.58
by using 6 different solvents. Apparently, there is little Oil 19 48.6 0.5 32.9 1.03 67.70 31.27
change in the relative yields of asphaltenes from each
of the 4 oils when different solvents are used; this Oil 5 51.4 108.3+ 143.5+
is also true for maltenes [Fig. 4(a-d)]. Data for Oil 10 46.5 36.6+ 267.5+
Oil 16 47.3 2.2 95.3+ 4.65
n-decane is incomplete/erroneous due to difficulties Oil 19 48.8 6.3 98.5+ 12.91 — —
encountered during solvent evaporation, these being •Loss during separating asphaltene from oil.
attributable to very high boiling point of n-decane t Impossible to evaporate the solvent completely.

Paper 6: Calibration and standardization qflatroscan 149
842 Sunil Bharati et at.
(a) SAMPLE 5 (c) SAMPLE 16
---♦ ~ — — *♦ —
♦ Asphaltene
■ Maltene
SAMPLE 10 SAMPLE 19
80 —~
♦ — —
-----♦
40 —
20 -
Carbon atoms in solvent (n-alkane)

Fig. 4. Relative percentages of asphaltene and maltene yields for 4 different oils (samples 5, 10, 16 and
19) on deasphaltening using n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane.
except n-decane. Maltenes resulting from n-pentane material (Table 6), even after the solvent removal
up to n-nonane contain mainly hydrocarbons, but procedure [Fig. 5(b)]. This effect is also noticed in the
also noticeable amounts of resins and asphaltenes case of asphaltenes, as asphaltenes resulting from
[Fig. 5(a)], In the case of n-decane, significant amount n-pentane up to n-nonane precipitation are nearly
of the solvent is apparently retained with the sample free of any saturated hydrocarbons [Fig. 5(c)] while
0 10 0 10
bed
Fig. 5. Iatroscan analysis of maltene and asphaltene fractions resulting from deasphaltening of oils using
various solvents. Typical chromatograms showing (a) representative maltene of n-pentane to n-nonane
precipitation, (b) maltene of n-decane precipitation, (c) representative asphaltene of n-pentane to
n-nonane precipitation and (d) asphaltene of n-decane precipitation.

Calibration and standardization of Iatrcscan 843
Table 6. Asphaltene solubility experiment: results of TLC-FID analyses of mallcnc and asphaltene
fractions—relative percentages of separated fractions
Maltenes Asphaltenes
Sample Sat% Aro% Pot% Asp% Sat% Aro% Pol% Asp%
Pentane
Oil 5 24.8 62.7 11.9 0.6 26.6 73.4
Oil 10 46.7 49.9 3.3 0.1 45.6 54.4
Oil 16 58.8 33.0 7.5 0.7 52.9 47.1
Oil 19 71.6 24.5 3.8 0.1 — — 50.6 49.4
Hexane
Oil 5 24.8 63.4 11.3 0.6 27.4 75.8
Oil 10 44.9 49.5 5.2 0.4 37.1 62.9
Oil 16 55.9 35.4 7.7 1.0 68.6 31.4
Oil 19 69.0 27.1 3.7 0.2 — — 54.1 45.9
Heptane
Oil 5 24.7 65.8 9.2 0.4 24.2 75.8
Oil 10 47.2 48.2 4.4 0.2 32.7 67.3
Oil 16 55.2 36.3 7.6 0.9 78.4 21.6
Oil 19 74.8 20.2 4.8 0.2 — — 66.1 33.9
Oil5 27.7 57.4 14.6 0.3 4.0 10.5 28.5 57.0

Oil 10 41.6 53.4 4.8 0.2 40.2 59.8
Oil 16 56.0 35.1 8.1 0.8 82.5 17.5
Oil 19 73.0 20.3 6.5 0.2 — — 68.1 31.9
Nonane
OilS 21.7 63.3 14.6 0.4 32.8 67.2
Oil 10 45.1 49.1 5.3 0.4 45.1 54.9
Oil 16 58.6 30.9 9.5 1.0 75.0 25.0
Oil 19 72.5 23.0 4.2 0.3 — — 55.8 44.2
OilS 68.2 27.6 3.8 0.3 51.5 15.7 32.8

Oil 10 71.6 26.1 2.1 0.2 70.8 8.7 10.5 10.0
Oil 16 87.5 9.4 2.6 0.5 78.3 9.4 11.2 11.1
Oil 19 86.1 12.7 1.1 0.1 73.9 — 16.0 10.1
the asphaltene fraction resulting from n -decane has a 22 and 30) were selected for fresh deasphalting and
conspicuous saturated hydrocarbon peak [Fig. 5(d)]. separation of maltenes into fractions using MPLC
Apparently, no significant compositional differences (Radke et al., 1980). The selection was made on the
are obtained by using solvents other than that basis that at least about two “clean and pure” (from
normally used (n -pentane), except for n -decane. In TLC-FID point of view) fractions each of saturated
any case, this exercise was not helpful in obtaining hydrocarbons, aromatic hydrocarbons, resins and
a “purer” asphaltene fraction from the TLC-FID asphaltenes would be obtained from these oils. The
point of view. compositions of the oils and the relative percentages
of the various fractions are shown in Table 7,
Conventional MPLC separation although one must bear in mind that the data of
Based on the results obtained from whole oil Table 7 are not completely representative of the true
and maltene analyses, 7 samples (oils 1, 5, 7, 16, 19, composition, due to discarding of the initial and final
Table 7. Composition and relative percentages of chromatographic fractions from MPLC

Oil Sat Pol Asp Total Loss* Loss* Sal Pot Asp
Sample (mg) (mg) (mg) (mg) (mg) (mg) (mg) (%) (%) <%) (%) (%)
Oil 1 94.6 34.9 18.0 0.9 13.0 66.8 27.8 29.4 52.2 27.0 1.3 19.5
la 101.8 39.9 13.8 1.1 7.0 61.8 40.0 39.3 64.5 22.4 1.8 11.3
Oil 5 91.8 15.6 19.8 13.5 22.0 70.9 20.9 22.8 22.1 27.9 19.0 31.0
5a 104.9 21.5 23.4 15.5 25.1 85.5 19.4 18.5 25.1 27.4 18.1 29.4
Oil 7 107.2 38.1 23.9 15.0 9.8 86.8 20.4 19.0 43.9 27.5 17.3 11.3
7a 109.3 32.4 27.9 14.6 11.4 86.3 23.0 21.0 37.6 32.3 16.9 13.2
Oil 16 93.4 41.9 17.9 9.8 1.5 71.1 22.3 23.9 58.9 25.2 13.8 2.1
16a 105.3 47.3 19.7 14.1 2.1 83.2 22.1 21.0 56.8 23.8 16.9 2.5
Oil 19 95.7 52.4 13.4 3.6 1.8 71.2 24.5 25.6 73.6 18.8 5.1 2.5
19a 97.2 54.5 13.4 3.0 3.6 74.5 22.7 23.4 73.2 18.0 4.0 4.8
Oil 22 96.3 49.8 7.8 1.8 1.4 60.8 35.5 36.9 81.9 12.8 3.0 2.3
22a 98.1 49.8 7.8 2.1 1.4 61.1 37.0 37.7 81.5 12.8 3.4 2.3
Oil 30 111.5 515 18.9 15.6 3.1 90.1 21.4 19.2 58.3 21.0 17.3 3.4
30a 126.7 59.4 26.1 19.1 3.7 108.2 18.45 14.6 54.9 24.1 17.6 3.4
•The loss indicated includes the inherent loss related to the MPLC technique (estimated 5-10%) +Ioss due to discardation of 10% each
of the initial and final cuts of the saturated and aromatic hydrocarbon and resin fractions (cf. analytical procedures).

844 Sunil Bharati el al.
Table 8. Results of TLC-F1D analysis of chromatographic fractions clean and contain insignificant or no aromatic hydro
from MPLC: relative percentages of separated fractions carbons and/or resins as impurities [an example
Sat Aro Pol Asp shown in Fig. 6(a)]. In the case of oils 16, 19 and
MPLC fraction Sample (%) (%) <%) (%)
22, where 99-100% of the material is reported as
Saturated Oil I 99.0 0.5 0.5 —
hydrocarbons Oil 5 94.0 5.3 0.7 — saturated hydrocarbons, there seems to be a substan
Oil 7 67.4 32.3 0.3 — tial portion of saturated hydrocarbons which tends to
Oil 16 99.7 0.3 elute in the aromatic hydrocarbon region, the latter
Oil 19 100.0
Oil 22 100.0 being “dragged” forward as shown in Fig. 6(b). The
Oil 30 81.8 15.9 2.3 — dragged material is suspected to be mainly saturated,
Aromatic Oil 1 7.1 91.8 1.1 — but weakly aromatic in nature, possibly involving
hydrocarbons Oil 5 — 98.0 1.9 0.1 compounds such as alkyl benzenes with long alkyl
Oil 7 — 98.3 1.7
Oil 16 97.6 2.4 chains. In some of the saturated hydrocarbon frac
Oil 19 99.5 0.5 tions, however, there is a distinct separation into
Oil 22 99.2 0.8 saturated and supposedly “weakly aromatic” saturated
Oil 30 1.1 96.9 2.0 —
hydrocarbon portions (oils 7 and 30) [Fig. 6(c)].
Resins Oil 1 63.9 36.1 ___
OilS 68.2 31.8 — Aromatic hydrocarbon fractions from MPLC are
Oil 7 70.3 29.7 relatively free of saturated hydrocarbons, except
Oil 16 61.7 38.3 for oils 1 and 30 where minor amounts of saturated
Oil 19 64.3 35.7
Oil 22 48.4 51.6 hydrocarbons can be observed (Table 8). However,
Oil 30 — 66.7 33.3 — all the aromatic hydrocarbon fractions obtained by
Asphaltenes Oil 1 40.1 52.9 6.7 0.3 MPLC contain minor amounts of resins (0.5-2%)
OilS 100.0 [Fig. 7(a)]. In the case of resins obtained by MPLC,
Oil 7 15.7 19.6 51.8 12.9
Oil 16 54.2 45.8 all the fractions split into two distinct peaks during
Oil 19 56.2 43.8 Iatroscan analysis, with one eluting as an aromatic
Oil 22 76.2 16.0 7.5 0.3
Oil 30 — 31.6 — 68.4 hydrocarbon peak and the other as the resin peak
[Fig. 7(b)]. As this bimodality occurred in all fractions
and the qualitative results for all the resin fractions
cuts of each fraction (cf. analytical procedure for are very similar, it is believed that this is either due
MPLC). Nevertheless, some general and relative to the separation procedure adopted during MPLC,
differences in the oil compositions are apparent. Oils where the elution of aromatic hydrocarbons may not
1, 7, 16, 19, 22 and 30 are relatively rich in hydro be complete, or that some of the aromatic hydro
carbons; oils 5,1, 16 and 30 are rich in resins; while carbon and resin species are closely related with
oils 1, 5 and 7 are rich in asphaltenes. The purity of respect to their structure and polarity. If the latter is
all the resulting fractions (7 samples each of saturated true, then clearly the small differences in their physical
hydrocarbon, aromatic hydrocarbon, resin and properties are detected by TLC-FID elution, but
asphaltene fractions) was established using Iatroscan, apparently not by the MPLC elution procedure.
the results of which are presented in Table 8. Except The results for the asphaltene fractions are of vari
for the saturated fractions from oils 5, 7 and 30, able quality (Table 8). In most cases, the contamin
the other saturated hydrocarbon fractions are rather ation is rather significant in form of minor amounts
a b c
Fig. 6. Iatroscan analysis of saturated hydrocarbon fractions obtained by MPLC separation, (a) A pure
saturated hydrocarbon fraction, (b) Saturated hydrocarbons slightly contaminated by aromatic hydro
carbons. (c) Saturated hydrocarbons contaminated by "weakly aromatic” compounds.

Fig. 7. Examples showing TLC-F1D chromatograms of (a) a pure aromatic hydrocarbon, (b) a typical
resin and (c) a relatively pure asphaltene fraction.
of hydrocarbons or resins. However, asphaltene frac More importantly, the principle resin peak does not
tions from oils 5, 19 and 30 are rich in asphaltenes, split into 2 components and the resulting fraction
as also noted earlier, the latter two being contamin is considered to be clean and uncontaminated. The
ated by resins. One asphaltene however, apparently second fraction (NSO-ARO), however, also contains
gives good results (oil 5) and as seen in Fig. 7(c), a dominant component, apparently resins but which
no hydrocarbons or resins seem to be present as should to be of a different composition, and some
contaminants. hydrocarbons [Fig. 8(b)]. Nevertheless, this exercise
suggests that the resin fraction resulting from MPLC
Preparative thin-layer chromatography (PTLC) and which splits into two distinct components on
As noted above, all the resin fractions resulting Iatroscan analysis, can be further separated into two
from MPLC separation split into two peaks on fractions on a preparative scale, as shown in Plate 1.
Iatroscan analysis, one peak indicative of aromatic For comparison, the results of TLC separation of all
hydrocarbons and the other of resins. The selected the fractions and whole oil using a TLC plate are also
resin fractions for preparative TLC were from oils 5 shown in Plate 1.
and 16, and each resin fraction resulted in 2 fractions Subsequent separation of all oils using preparative
(aromatic hydrocarbons or NSO-ARO and “pure” TLC plates and the same elution procedure as
resins or NSO-NSO). The resulting pure resin employed in Iatroscan, shows that the four principle
fraction (NSO-NSO) is characterised by a dominant fractions separate well and the u.v. detector (254
resin peak and a minor asphaltene peak [Fig. 8(a)]. and 356 nm) showed three distinct zones contain
ing aromatic hydrocarbons, resins and asphaltenes
(saturated hydrocarbons do not fluoresce) (Plate 1).
Analysis of the four principle fractions from MPLC
showed that the saturated hydrocarbons separated
into two zones—one of major saturated hydrocarbons
and one of minor aromatic hydrocarbons. The
aromatic hydrocarbons separate into two fractions—
one major aromatic hydrocarbons and one minor
resins, and perhaps one minor saturated hydrocarbon
zone, but this is difficult to establish as saturated
hydrocarbons are not possible to detect on a u.v.
detector. The resin fraction clearly separates into 2
equally dominant fractions—aromatic hydrocarbons
and resins. Finally, the asphaltenes separate into
mainly asphaltenes and minor resins, aromatic hydro
carbons and probably minor amounts of saturated
hydrocarbons.
Composition and purity of the separated fractions
Fig. 8. Iatroscan analysis of the separated resin fractions
using preparative-TLC. (a) The pure resin fraction Gas chromatography of the 5 saturated hydro
(NSO-NSO) and (b) an impure resin fraction (NSO-ARO). carbon fractions (from oils 1, 5, 16, 19 and 30) which

GC of Saturated Hydrocarbons
I
6 On
> 1000
E 100
80 -
S unil B harati el a t .
Time (minutes) Time (minutes)
S
Cc
ijjJlA A A .A A M *i
20 30 40 50
Time (minutes)
Fig. 9. Gas chromatograms of selected saturated hydrocarbon fractions from oil I (a), 5 (b). 16 (c) and 19 (d).
QC of Aromatic Hydrocarbons
£ 160
Calibration and standardization of latroscan

480 -
E 420
c 390

S
Fig. I0. Gas chromatograms of selected aromatic hydrocarbon fractions from oil 7 (a), 16 (b), 19 (c) and 22 (d).
Paper 6„• Calibration and standardization oflatroscan 155
848 Sunil Bharati et al.
were thought to have the best potential of being used (a)

Saturated Hydrocarbons
as standards indicates that there are significant differ
ences in the composition and maturity of these oils.
Intensity type
Oil 1 [Fig. 9(a)] is relatively rich in lighter n-alkane
components, probably due to its slightly higher 0 Maximum
maturity; oil 5 [Fig. 9(b)] is moderate to strongly □ General
biodegraded; oil 16 [Fig. 9(c)] is unusually rich in
isoprenoids relative to the n-alkanes (probably to do
with an unusual source); oil 19 [Fig. 9(d)] is relatively
rich in heavier n -alkane components with n-C15
being the most abundant alkane; and oil 30 is mildly
biodegraded. The isoprenoid content in oil 19 is also
higher, indicating a lower maturity, though not as 77 83 91 97 99 106 134 142 163 183
high a content as in oil 16.
Aromatic Hydrocarbons
Gas chromatography of the 4 aromatic hydro
carbon fractions which were thought to have best
potential of being used as standards also indicates
significant compositional differences. Oil 7 [Fig. 10(a)]
is biodegraded and is depleted in diaromatic hydro
carbons; oil 16 [Fig. 10(b)] is very rich in diaromatic-
and depleted in triaromatic hydrocarbons; while oils
19 [Fig. 10(c)] and 22 [Fig. 10(d)] are relatively rich
in diaromatic, but also have significant triaromatic
hydrocarbon moieties. In addition, oil 19 is more
mature than oil 22 (indicative from the higher 2-
methylnaphthalene/l-methylnaphthalene ratio in oil 77 83 91 97 99 106 134 142 163 183
19). FPD traces of the 4 aromatic hydrocarbon
fractions show that only oils 7 and 16 contain traces
of dibenzothiophene, with an apparent difference in Fig. 11. Summarized results of GC-MS analysis of the
maturity between the two. hydrocarbon fractions. Relative maximum intensities of
It is important to understand as to which of 10 major ions in (a) saturated hydrocarbon fraction and
the aromatic hydrocarbon species have the greatest (b) aromatic hydrocarbon fraction.
tendency to be retained as contaminants in the
saturated hydrocarbon fraction and vice-versa. This various types of molecules present in the fraction.
semi-quantitative and qualitative assessment was Apparently, Cl-benzene, the basic aromatic ring
achieved by analysing selected saturated and aromatic structure with a methyl group, seems to be the most
hydrocarbon fractions using the GC-MS technique. abundant aromatic hydrocarbon species present.
The objective of semi-quantitative assessment and The aromatic hydrocarbon fraction on the other
contaminant identification was especially significant hand is dominated by short-chain methylated
in light of the conventional methods adopted for benzenes, but relatively smaller amounts of some C4-
separating fractions (MPLC). Therefore the alkylbenzene are also present. Amongst the saturated
purest/least contaminated saturated and aromatic hydrocarbon species, n-alkanes and isoprenoids seem
hydrocarbon fractions amongst all the oils considered to be nearly equally distributed [Fig. 11(b)], in addi
in the study, were chosen for this exercise. tion to methyl cyclic alkanes (m/z 97). Unlike the
The saturated hydrocarbon fraction is rich in n- saturated hydrocarbon fraction, which contains
alkanes, but the cyclo-alkane moieties are evidently practically no dibenzothiophenes, the aromatic
also abundant (m/z 83 and 97), although long hydrocarbon fraction retains some dibenzothiophene
chains of alkylbenzenes are also detected in m/z 83 moieties, this being observed in the m/z 198 frag
[Fig. 11(a)]. In addition, isoprenoids are also present mentogram. On comparing Figs 11(a) and 11(b), it
in significant proportions. However, based on m/z 91 seems that the aromatic hydrocarbons have a greater
and 106, alkylbenzenes are not present in large tendency to retain saturated hydrocarbon species
amounts, contrary to expectations as alkylbenzenes than vice-versa. However, the limitations of this
with long chains were thought to be the most likely observation must be borne in mind, as the conclusion
contaminants in the saturated hydrocarbon fraction. is based on the analysis of only two samples.
These observations are apparent in Fig. 11(a), where The 2 asphaltenes selected for making the
the absolute intensities of the 10 major ions are standards differ significantly in the composition of
plotted. The figure shows the maximum intensity in a their thermal extracts. While oil 5 is strongly bio
fragmentogram and the general (most common) in degraded [Fig. 12(a)], oil 19 has a bimodal distribution
tensity in that fragmentogram. This semi-quantitative of n-alkanes [Fig. 12(b)], Their pyrolysates, however,
approach indicates the relative abundances of the are quite similar in composition [Figs 12(c) and (d)]

TE-GC of Asphaltenes PY-GC of Asphaltenes
Calibration and standardization of Iatroscan

30 40 SO 60 30 40 so
Fig. 12 Gas chromatograms of thermal extracts and pyrolysates of 2 asphaltenes. Thermal extract of asphaltene from (a) oil 5 and (b) oil 19. Pyrolysatc of asphaltene
from (c) oil 5 and (d) oil 19.
Paper 6 : Calibration and standardization oflatroscan
TIC of Resins TIC of Asphaltenes
25 30 35 50 65 60 65 60 65
10 15 20 26 30 35 40 46 50 55 60 65 70 10 15 20 25 30 35 40 45 50 66 60 65 70
Fig. 13. Results of PY-GC-MS analysis of resins and asphaltenes. Total Ion Chromatograms (TIC) of (a) resin from oil 16, (b) resin from oil 22,
(c) asphaltene from oil 5 and (d) asphaltene from oil 16. Peak identification: V—toluene; ▼—n-hydrocarbon doublets; ♦—alkylcyclohcxancs;
157
■—methylphenanthrcne; #—alkylnaphthalcncs; J—nC18 doublet; —internal standard.
4
and are indicative of a marine source. Py-GC of Ion Chromatograms (TIC) of the two asphaltene
resins did not give any conclusive results. fractions are shown in Figs 13(c) and (d).
Py-GC-MS of selected resin and asphaltene
Identification, isolation and purification of selected
fractions allowed to assess the presence of any hydro
fractions for standard
carbons, if any, that might have been retained in these
fractions after MPLC separation. The resin fraction Based on the findings this far, 4 oils covering
of oil 16 contains only traces of n -hydrocarbons, as practically the entire API gravity range, were selected
is indicative by the generally imperceptible homology for re-separation into fractions. Preliminary analyses
in mjz 97 and 99, although m/z 99 does exhibit indicated that one or more of these oils could be
presence of some n-alkanes. Alkylbenzenes are successfully used to isolate pure fractions, which
present, but are believed to occur in small amounts. could be further used to calibrate Iatroscan via
Alkylnaphthalenes are more prominent relative to prepared standards. Four parallels of each of the four
alkyl-phenanthrenes. Dibenzothiophenes and other oils, oil 5, oil 16, oil 19 and oil 22, were subjected to
substituted derivatives are also present. No significant MPLC in order to get large amounts of each fraction
biomarkers were recorded. Compared to the resin from each oil. At this stage, we had 4 fractions x 4
from oil 16, the resin fraction from oil 22 is much parallels for each oil. Each of the four fractions
more depleted in most of the hydrocarbon species, from these oils were later mixed and re-run through
although the latter contains a stronger n-alkane the MPLC system to purify and clean the fractions.
homology, as observed in m/z 99, perhaps indicative This ultimately resulted in one large portion each of
of the presence of more saturated hydrocarbons. saturated hydrocarbon, aromatic hydrocarbon, resin
Most alkylbenzenes are of low molecular weight and asphaltene fractions for each of the 4 oils. On
and are not interpreted to be significant. The results analyzing these fractions using the Iatroscan, it was
for other ions are similar, but these compounds found that the aromatic fraction of all the oils was
are present in low concentrations. The Total Ion contaminated by substantial amounts of resin species,
Chromatograms (TIC) of the two resin fractions are a problem which had also been observed earlier. The
shown in Figs 13(a) and (b). 4 aromatic hydrocarbon fractions were run through
The 2 asphaltenes seem to be considerably different MPLC twice more to remove the resins.
in composition. While oil 5 asphaltene is rich in short- The typical TLC-FID chromatograms of the final
and medium-length alkyl chains, oil 16 asphaltene pure fractions (saturate and aromatic hydrocarbons,
is depleted in these moieties (mjz 97 and 99). Oil 5 resins and asphaltenes) used in Iatroscan calibration
asphaltene is also relatively rich in alkylbenzenes. and the standard are shown in Figs 14(a-d). Clearly,
Alkylnaphthalenes, however, seem to be equally the fractions are uncontaminated with only traces of
prominent in both the asphaltenes, in contrast to unwanted components. However, as the four saturated
alkylphenanthrenes which are more conspicuous in hydrocarbon and aromatic hydrocarbon fractions
the oil 5 asphaltene. Dibenzothiophenes are depleted differed significantly from each other with respect to
in oil 16 asphaltene relative to oil 5 asphaltene. These density and composition, individual response factors
results perhaps indicate that oil 16 may be generally were calculated to see if the response factors were
richer in branched/cyclo hydrocarbons. The Total affected by these parameters. Each of the fractions
M
j t= J l
0 10 0 10
abed
Fig. 14. TLC-FID chromatograms of "pure” isolated fractions obtained by a combination of repeated
MPLC and preparative-TLC. (a) Saturated hydrocarbons, (b) aromatic hydrocarbons, (c) resins and
(d) asphaltenes.

852 Sunil Bharati ei at.
(a) Saturated HC (C) Resins
3.0
(d) Asphaltenes
Sample amount (pi)

Fig. 15. Dependence of calculated response factors of Iatroscan on oil's composition and density. Plot
of response factor versus sample amount from 4 different oils for (a) saturated hydrocarbons, (b) aromatic
hydrocarbons, (c) resins and (d) asphaltenes.
of the four oils (one heavy—API gravity around 10°, As seen in Fig. 15(a), the response factors of the
two medium—API gravity around 30° and one light four saturated hydrocarbon fractions vary signifi
—API gravity more than 40°) were analysed by cantly (from about 2000 to 4500). Closer examination
Iatroscan 3-5 times, using different sample amounts of the results reveals that the variation is not random,
each time (0.5-5 pi of the same solution), and but is controlled by at least two factors. Saturated
response factors calculated in each case using the hydrocarbons from the heavy oil have the greatest
equation shown below. response factor, while those from a light oil have the
Response factor (RJ = least. Compositionally, the saturated hydrocarbons
from the heavy oil are strongly biodegraded, those
Peak area (A )/Samp!e amount (A/) from the first medium oil (plotted as solid squares)
The results are shown in Figs 15(a-d). are very rich in isoprenoids, those of the second
Dietz (1967) has shown earlier that relative sensi medium oil are rich in medium to heavy range
tivity for the flame ionization detector (FID) is quite n-alkanes and lastly those from the light oil are rich
different for hydrocarbons and non-hydrocarbons. in low molecular weight n-alkanes (cf. Fig. 9).
While most straight chain, branched and cyclo alkanes In case of the aromatic hydrocarbons [Fig. 15(b)],
have similar FID sensitivities (close to 1.0), aro the variation in response factor is from about 4000
matic hydrocarbons tend to be very slightly lower for the lightest oil to about 6500 for the heaviest oil.
(0.98-1.02). However, non-hydrocarbons (resins and With regards to the compositional variation between
asphaltenes), which have heteroatoms such as N, S the four aromatic hydrocarbons, the heavy oil is bio
and O, have much lower FID sensitivities and the degraded, as noted above, the first medium oil (plotted
values vary appreciably. Alcohols, for example, vary as solid squares) is richer in alkylnaphthalenes relative
from 0.23 to 0.85; acids, from 0.01 to 0.65 etc. (Dietz, to triaromatics, while the second medium oil and the
1967). The variation in the sensitivity value depends light oil are relatively rich in triaromatics (cf. Fig. 10).
mainly on type of compound, number of heteroatoms, In case of the resins and asphaltenes, the trend is
molecular weight etc. (Dietz, 1967; Drushel, 1983). opposite to those of the two hydrocarbon groups

Calibration and standardization of Iatroscan
Response Factor (Thousands)
Light Oil
Medium Oil
Heavy Oil
* SAT HC ARO HC S NSO *ASP
API Gravity C)
Fig. 16. Relationship of oil density (API gravity) and Iatroscan detector response (Response factor) for
the 4 principle fractions of oil viz. saturated hydrocarbons, aromatic hydrocarbons, resins and asphaltenes.
The API gravity is inversely proportional to detector response in case of the 2 hydrocarbon fractions
(as indicated by the negative slope of the 2 solid linear regression trends) and directly proportional in case
of the 2 non-hydrocarbon fractions (as indicated by the positive slope of the 2 dashed linear regression
trends).
[Figs 15(c) and (d)]. Unlike the hydrocarbons, the nearly parallel to each other, although unlike the
response factors of the heavy oil fractions are lower hydrocarbons their response factors increase with
than those of their lighter counterparts. The signifi increasing API gravity.
cance of this reversal is not exactly clear, but it is As response factors cannot be calculated for every
suspected that it may be related to lower carbon and unit of the API gravity, and there is no unique
hydrogen contents/greater ionization efficiency of the response factor for a given fraction either, the whole
components in the heavier oil’s resin and asphaltene suite of oils has been divided into three principle types
fractions. for simplicity—heavy (API gravity 10-24°), medium
(API gravity 24-35°) and light (API gravity 35° and
Calibration of Iatroscan and testing of prepared above). The American Petroleum Institute defines an
standard oil as heavy if it has an API gravity of 20° or lower.
Clearly, the present results indicate that there However, in our case (Fig. 16), the response factor of
cannot be one unique response factor for a given the polar fraction is lower than that of the saturated
fraction to calibrate Iatroscan. Parrish and Ackman hydrocarbon fraction until about 24°, but then crosses
(1985) had also observed variations in the Iatroscan’s over and is subsequently greater than the saturated
FID response, on analysing marine lipids. It is hydrocarbons. This point was therefore taken as the
controlled to a large extent by the oil’s API gravity boundary between the heavy and medium oils. It is
(which can be expressed mathematically) and the not known, however, whether this fact is of any
gross composition of the fraction (which is a subjective significance or not. Considering the results plotted in
aspect and cannot be expressed mathematically). In Fig. 16, it is assumed that if each of the 4 fractions
Fig. 16, the API gravity of the 4 oils is plotted against have 3 different response factors according to the type
the average response factor of each of the 4 fractions of oil (one each for heavy, medium and light oils),
of each of the 4 oils. The variation of the response calibration of Iatroscan will be reasonably good. The
factors in case of each of the four fractions is mathematical model developed to derive these factors
more apparent here. While the calculated response is exemplified below.
factors decrease with increasing API gravity for the The slopes of the two hydrocarbon trends are
two hydrocarbons, it increases for the two non- negative while those of the two non-hydrocarbons
hydrocarbon fractions. Moreover, there is a remark are positive. Ideally (typically for single synthetic
able similarity between the two hydrocarbon fractions compounds and theoretically for a mixture of similar
as regards to their response factor progression with compounds),
increasing API gravity (the two linear regression R' = A/M (1)
trends—solid lines are parallel to each other).
Similarly, the linear regression trends of the two non where = response factor, A = peak area, M -
hydrocarbon fractions (the two dotted lines) progress sample amount.

Fig. 17. TLC-FID chromatograms of prepared standards, (a) A natural standard based on a medium oil
(Standard A), (b) A natural standard based on a light oil (Standard B). (c) A synthetic standard comprising
several synthetic components (GEOS).
But in the present case, The correction constants can be obtained for each
Rc = A/M + C, (2) fraction through linear regression, using the slope
of the trend and the applicable a in equations (5), (6),
where C =f(o), a being the API gravity of the oil. (7) and (8). An example for saturated hydrocarbons
This is similar to the linear regression equation is shown below:
y = a + bx (3) C,(SAt)= —53.3 x 17= —906
where a is a constant and b is the slope. where 17 is the assumed representative of the a Range
.'. equation (2) can be written as [10.24].
ReÂ/M+bxo (4) CysAT) = —53.3 x 29= —1546
The derived equations for the 4 components in where 29 is the assumed representative of the a Range
Fig. 16 are: 124.351
Saturated hydrocarbons. CjtsA-n = -53.3 x 42 = -2238
R&sat) — 5292 + (—53.3 x <r) (5) where 42 is the assumed representative of the a Range
[35,50],
Aromatic hydrocarbons.
Using the correction constants, the response factor
^ciarO) = 7328 + (—47.3 x <r) (6) (RJ of a given fraction for each oil type can be
calculated using equations (5), (6), (7) and (8), as
Polars.
shown below for saturated hydrocarbons as an
7!c<pol) — 5393 + (34.6 x <r) (7) example [the equation employed in this case is
Asphaltenes. equation (5)].
= 5292 - 906 = 4386
•RctAspj = 9781 + (66.3 x o) (8)
Rcm = 5292 — 1546 = 3746
Equation (4) above can be considered to be the basic
“Correction Equation". This can theoretically have Ad. = 5292 - 2238 = 3054
infinite number of forms for every given o, but for
Similarly, the other correction constants and
simplicity we will consider 3 principle forms suitable
for heavy oils, medium oils and light oils. The 3 response factors can be calculated for the other
fractions and each type of oil. These were calculated
equations can be written as.
and are shown in Table 9.
P.H = A/M + C„ 10<<r<24 (9) According to the table below, we have a total of
4 fractions x 3 oil types i.e. 12 response factors for
RcU = A/M + C2, 24<<r <35 (10) use and calibration. It must be noted, however, that
Rcl_ = A/M + C3, 35 < ff < 50 these are response factors of the FID used to analyze
(11)
the samples in the present study, and they will not be
where C„ C2, C3 are “Correction Constants". necessarily the same for other users. However, the

Calibration and standardization of latroscan 855
Table 9. (a) Calculated correction constants (C)

Standard A
Sat Aro Pol Asp
1127 Fraction
C, -906 -804 588
C. -1546 -1371 1003 1923 O SAT
C, -2238 -1987 1453 2785 x ARO
♦ POL
(b) Calculated response factors (Re) A ASP
Sat Pol Asp
Heavy oil (£,„) 4386 6524 5981 10908
Medium oiH^m) 3746 5957 6396 11704
Light oil (RcL) 3054 5341 6846 12566
Average (Bulk) (%*) 3729 5941 6408 11726
relationship of the response factors to each other is

more likely to remain the same, if the same standard
is used to calibrate the instrument. Therefore, for
Standard B
other users, the 2 tables below (Table 10) could be
used to extrapolate the response factors from the
given standard, which is based on a medium oil.
The relationships in Table 10(a) below are derived
directly from the data in Table 9(b). A closer examin
ation of these relationships reveals that in relation to
the medium oil values, both the hydrocarbon fractions
of heavy and light oils have a rather constant relation
ship (1.17 to 1.1 times and 0.82 to 0.9 times respect
ively) and both the non-hydrocarbon fractions of
heavy and light oils also have a constant relationship 0.5 1.0 1.5 2.0 2.5 3.0
(0.93 times 1.07 times respectively). This further
Sample Amount (jil)
strengthens the interpretation that these variations are
not random, but are controlled by distinct factors). Fig. 18. Calibration curves for the 2 natural standards. A
and B. (a) Plot of sample amount versus peak area of the
The user may utilise either Table 10(a) or 10(b) to 4 individual components of Standard A. (b) Plot of sample
extrapolate response factors from the given medium amount versus peak area of the 4 individual components of
oil based standard. Standard A. Standard B. Note the linearity of peak-area progression
Two standards have been prepared using topped with increasing sample amount in case of each component
oils, for calibrating latroscan and subsequent use. in both the standards.
The strength of the solutions in both cases was aimed
in the range 10-15 mg oil/ml solvent, as it has been Standard A is primarily made from a medium oil
found through experience that this is the ideal range and is rich in polars and asphaltenes. In contrast,
to ensure adequate individual component amounts, Standard B is primarily from a light oil and contains
good separation and to avoid overloading. The minor polars and practically no asphaltenes. The
solvent chosen to dissolve the standards was toluene chromatograms of these two standards are shown
instead of commonly used dichloromethane, due to in Figs 17(a-b). These two standards were analysed
toluene’s greater stability (higher boiling point) under by latroscan using 5 parallels, with different sample
ambient conditions. amounts each time. The sample amount varied from
0.5 to 3/xI in each case. Calibration curves were
Table 10. (a) Relationship of response factors (Rc) of a fraction with drawn and are shown in Figs 18(a-b), where it can be
respect to medium oil observed that the peak area progression is rather
Sat Aro Pol Asp
Heavy oil (R<H) 1.17p l.lq 0.93r 0.93s
Table 11. Composition and quantitative data for the two prepared
Medium oil(^M) P q r standards
Light oil(/?tL) 0.82p 0.9q 1.07r 1.07s
Peak Corrected Response
p. q. r and s arc the user's calculated response factors based on
area factor Amount
prepared Standard A.
Fraction uVs uVs (cf.Table9(b)] /il (%)
(b) Relationship of response factors (/^) of a type of oil w.r.t.
Standard A
saturated hydrocarbons
Saturated HC 45792 48332 3746 12.90(60.37)
Heavy oil Medium oil Light oil Aromatic HC 20847 20727 5957 3.48(16.29)
<*c) (*cM> uw Polars 26794 26177 6396 4.09(19.14)
% Asphaltenes 10645 10599 11704 0.90(4.2)
Saturated HC y
Aromatic HC l.49x l.59y 1.75z Standard B
Polars 1.36x 1.71y 2.24z Saturated HC 42018 45537 3054 14.91 (84.96)
Asphaltenes 2.49x 3.l2y 4.1 Iz Aromatic HC 10266 10022 5341 1.88(10.71)
Polars 4284 5100 6846 0.74(4.22)
x is the user's calculated response factor for saturated hydrocarbon
Asphaltenes 236 312 12566 0.02(0.11)
fraction based on prepared Standard A.

Table 12. List of compounds used to prepare various synthetic standards. The figures indicate the percentage of the compound used in a standard
Standard Name
Compound SATI MODI I POLY l POLY2 AROI NSOI NS02 NS03 NS04 NS05 NS06 NS07 NS08 NS09 NSOIO NSOll NSOI2 NSOI3 NSOI4 ASP:
1. Hexadecanc 41.4
2. Docosane 26.9
3. Hcxacosanc 19.7
4. Triaconlanc 5.5
5. Hexalriaconlane 3.8
6. 2,3-dimcthylnaphthalcnc 12.1 8.3
S u n il B h a r a t j el al.
7. M-dicyclohcxylbenzcne 39.8 27.1
8. Naphthalene 24.1 16.4
9. Biphenylene 7.5 5.1
10. 2-mcthylnaphthalene 16.5 11.3
II. 1,3-dimelhylanthracenc 49.6

12. Phcnanthrcnc 50.4 100 31.8
I 13. Thenoic acid 20.2 46.8 28.6 38.5 25.6

14. Dibcnzolhiophcnc 12.7 29.5 26.7
I 15.
16.
l-benzothiophcnc
Stearic acid
9.8
20.1
23.7 17.8
15.7 19.6 13.1 33.6 100
17. Stearyl alcohol 18.2 22.5 21.7 14.5 33.1 100 75
18. Stearamidc 19.0 12.8 20.1 13.4 33.3 100
19. Bcrbcrinc sulphate 71.4 55.5 49 33.4 25 25 100
8$
consistent in the case of all the four principle frac Saturated hydrocarbons. Squalane is the most
tions—saturated hydrocarbons, aromatic hydrocar commonly used synthetic compound for the purpose
bons, polars and asphaltenes. of calibration and quantification of saturated hydro
Corrected peak areas, based on linear regression, carbons. We, however, chose to use a mixture of
were used to calculate the fraction amounts. The 5 different n-alkanes ranging widely in the carbon
response factors used to derive the individual com chain-length (nC16 to nC36) to prepare the saturated
ponent amounts are derived from Table 9(b). The hydrocarbon standard, SAT1 (Table 12). The TLC-
case for 2 p\ sample amounts for both the standards FID chromatogram is shown in Fig. 19(a). Iatroscan
is shown below in Table 11 and taken as correct, analysis of SAT1 gave very good results with one
as this is the sample amount (sample dissolved in dominant peak. This was therefore the only standard
solvent) that is applied on the chromarods. made for saturated hydrocarbons.
Aromatic hydrocarbons. The standard for mono-
Synthetic standards and diaromatic hydrocarbons (MODI1), which was a
Table 12 shows the details of the synthetic mixture of 5 compounds (Table 12), resulted in one
standards (total 21 basic standards) prepared in the sharp peak on Iatroscan analysis [Fig. 19(b)]. In
present study. One basic criterion that was followed addition, a combination of MODI 1 components and
while making these standards was that in each a poly-aromatic hydrocarbon (phenanthrene) (AROl)
standard, the distribution of components should be resulted in two well defined peaks on Iatroscan
as close as possible to the distribution commonly analysis [Fig. 19(c)].
encountered in the natural samples. A total of 19 Asphaltene. The criteria for selecting a compound
compounds, most of which occur naturally in solvent which could serve as a natural asphaltene equivalent
extracts and/or crude oils, was chosen with objective were simple: (1) the molecule should be large, (2) the
of obtaining response factors as close as possible to molecule should be polar, (3) the molecule should con
natural mixtures. The first stage in synthetic standard tain nitrogen, sulphur and oxygen. Berberine sulphate
analysis included mainly establishing the correct (MW = 822, formula = CWH42N20,5S) was selected
combination of various compounds which are and the standard ASP1 and ASP2 (a much diluted
compatible with each other in a solution. This was version of ASP1) analysed by Iatroscan. The results
therefore a more qualitative objective. The second were good with one dominant peak at the spotting
stage consisted of making a mixture of all the point [Fig. 19(d)].
compatible compounds, with at least one compound Resins. Making the right synthetic standard for
representative of each of the principle fraction type, resins was the most difficult task in the entire syn
and calibrating Iatroscan and deriving the response thetic standard study. Up to 14 different mixtures
factors. The qualitative assessment and compound (Table 12) had to be made to reach the right com
compatibility findings are described below for each position of the resin standard. Initially, the criteria
fraction type. was to include at least one compound containing
C Jrrî C . . 1
10 cm 0 10 cm 0
a b C d
Fig. 19. TLC-FID chromatograms of synthetic standards, (a) Synthetic standard SAT1, comprising
5 n-alkanes with varying carbon chain-length (C16-C36). (b) Synthetic standard MODI1, comprising
5 different mono- and diaromatic hydrocarbon components, (c) Synthetic standard AROl, comprising
MODI1 and a poly-aromatic hydrocarbon (phenanthrene). (d) Synthetic standard ASP I, comprising a
single compound, berberine sulphate, which is thought to be comparable to a natural asphaltene molecule
with regards to polarity and elution characteristics during chromatography.
Doctoral Dissertation by Simil Bharati, 1997

10 cm 0 10 cm 0 10 cm
b C d
10 cm o io cm 0 10 0 10 cm
e f h
Fig. 20. Results of Iatroscan analysis of the various synthetic resin standards. TLC-F1D chromatograms
of (a) NSOl, comprising 6 different components, including 2 acids, an alcohol, an amide and 2 thiophenes,
(b) NS02, comprising 3 components- thenoic acid and 2 thiophenes, (c) NSOS, comprising ASPl and CIS
acid, alcohol and amide, (d) NS06, comprising thenoic acid and Cl8—acid, alcohol and amide, (e) NS07,
comprising NSQ6 and ASP1. (f) NSOS, comprising only the 3 CIS components—acid, alcohol and amide,
(g) NSOl 1, comprising only CIS amide and (h) NS014, comprising CIS amide and bcrberinc sulphate
(ASP1).
nitrogen, sulphur and oxygen and at the same time, NS06 and NS07 were analysed, but contrary to
maintaining the individual molecular weight low. expectations NS06 resulted in two peaks [Fig. 20(d)]
NSOl standard was made, but on analysis, the and NS07 in three peaks [Fig. 20(e)). This clearly
mixture split into three peaks with one peak eluting indicated that the combination of stearic acid, stearyl
as an aromatic hydrocarbon [Fig. 20(a)). NS02 alcohol and stearamide is also not compatible. This
(made to identify the incompatible component) split was evident from NSOS analysis [Fig. 20(f)], where
into two distinct components [Fig. 20(b)] and there three components gave three peaks. NS09, NSO10
fore abandoned. NS03, NS04 and NSOS, which and NSOl 1 were analysed to identify the incompat
consisted of similar compounds mixed with berberine ible component. All the three gave reasonably good
sulphate, and which were expected to give 2 peaks single peaks, but stearamide [Fig. 20(g)] seemed to be
each, gave variable results. While NS03 resulted in most consistent in its retention time. A combination
two peaks, thenoic acid did not elute as much as it of these three components with berberine sulphate
should have; NS04 gave only one peak; and NSOS (NS012, NS013 and NS014) confirmed that stear
seemed to have worked well with the combined CIS- amide was most compatible with the asphaltene
acid, alcohol and amide peak separating very well component, berberine sulphate [Fig. 20(h)],
from the berberine sulphate peak [Fig. 20(c)). This led This concluded the qualitative and compatibility
us to believe that perhaps the two benzothiophenes assessment of the selected synthetic compounds and
are the problematic components. To ascertain this, the final standard mixture GE03, which comprised


Table 13. Calibration results of the Synthetic Standard GE03 {based on 10 parallels of 2pl)
Mean Area Amount Amount
Fraction Area SD (%) (%) (pgi
Saturated Hydrocarbons 14727 962 37.51 41.8 4.32 3409
Mono + Diaromatic Hydrocarbons 4842 399 12.72 24.5 2.532 1912
Poly-aromatic Hydrocarbons 3917 282 9.98 9.3 0.96 4080
Resin 8035 688 21.13 14.7 1.52 5286
Asphaltene 6961 531 18.79 9.6 0.996 6989
SAT I, AROl, NSOl I and ASP2 was analysed. The use the bulk response factors CR,B) and calculate the
resulting TLC-FID chromatogram is shown in Fig. fraction amounts (Amount 2). The fraction amounts
17(c). Clearly, the 13 compounds used in GE03 are resulting by employing ReB in Case 1 should be quite
compatible and stable in each other’s presence, with close to the actual values of the standards calculated
one peak each of saturated hydrocarbons, mono- using Rat, and which are shown in Table 11. This
+ diaromatic hydrocarbons, polyaromatic hydro is because are closest to RM. Next, the response
carbons, resins and asphaltene. The new GE03, factors for light oil (i?cL) are used and the fraction
which was subsequently made using fresh chemicals amounts calculated (Amount 3). Finally, the response
with the purpose of calibrating Iatroscan and deriv factors derived from the GE03 synthetic standard
ing response factors, comprised of the following: (Rcs from Table 13) are used and the individual
saturated hydrocarbons 40%, aromatic hydrocar fraction amounts calculated (Amount 4). The results
bons 35%, resin component 15% and asphaltene are presented below in Table 14.
component 10%. Ten parallels of 2pi spotting were From Table 14 the following conclusion can be
analysed to establish reproducibility and obtain opti made. The first general effect of using a single set of
mum peak areas. Table 13 above summarizes the bulk response factors is that the quantity of fractions
findings. The implications of the calculated response in heavy oils are overestimated and those in light oils
factors from synthetic standards (R^) are discussed are underestimated. This means, for example, that the
in the next section. concentration of a heavy oil solution is reported as
21.43 and 13.69 mg/ml instead of 19.55 and 11.89 mg/
Validity of oil type dependent calculated response ml respectively, an overestimate of about 10-12%.
factors Likewise, the light oil solution which should have a
The calculated response factors as shown in concentration of 24.37 and 16.32 mg/ml is reported as
Table 9(b) apparently indicate potentially large 21.43 and 13.69 mg/ml respectively, an underestimate
differences in the resulting quantitative data when of about 12%. In addition, it must be borne in mind
these factors are used. It is intended in this section that even the figures quoted in the above table are
to demonstrate the actual differences that will be likely to be slightly erroneous (say about ±5%) and
obtained if only a single set of bulk response factors therefore the true error due to use of bulk response
are used instead of calculated response factors with factors could be in the range of about 18%, which is
oil type dependence. The test is performed for heavy undoubtedly a high percentage.
and light oils' response factors, keeping the average However, the relative percentages are less affected
bulk response factors constant. In the first case, we and tend to remain rather constant, except in the
assume that Standards A and B are heavy oils and use case of saturated hydrocarbons where the variation
the corrected areas to calculate the fraction amounts is about +9% for Standard A, which is relatively
using the heavy oil response factors i.e. and this depleted in saturated hydrocarbons, and +3% for
will give Amount 1 for both the standards. Next we Standard B, which is rich in saturated hydrocarbons.
Table 14. Comparison of quantitative data obtained by using different response factors (R^, Rea> RcL and R&) and Standards A & B
peak data
Area Amount 1 Amount 2 Amount 3 Amount 4
Fraction mVs PH%) *== M(%) pk%> Res p\(%)
Case 1: Standard A data
Sat. HC 48332 4386 11.02(56) 3729 12.96(60) 3054 15.83(65) 3409 14.18(51)
Aro. HC 20727 6524 3.18(16) 5941 3.49(16) 5341 3.88(16) 2996* 6.92(25)
Polars 26177 5981 4.38(22) 6408 4.08(19) 6846 3.82(16) 5286 4.95(18)
Asphalt. 10599 10908 0.97(5) 11726 0.90(4) 12566 0.84(3) 6989 1.52(6)
Total 19.55 (99) 21.43(99) 24.37(100) 27.57(100)
Case Z* Standard B data
Sat. HC 45537 4386 10.38 (81) 3729 12.21 (83) 3054 14.91 (85) 3409 13.36(75)
Aro. HC 10022 6524 1.54(12) 5941 1.69(11) 5341 1.88(11) 2996* 3.34(19)
Polars 5100 5981 0.85(7) 6408 0.80(5) 6846 0.74(4) . 5286 0.96(5)
Asphalt. 312 10908 0.03(0) 11726 0.02(0) 12566 0.02(0) 6989 0.04(0)
Total 12.80(100) 14.72(99) 17.55(100) 17.70(100)
Note: Response factor types: = heavy oil, Rc6 = bulk (average). R,L = light oil and R& = synthetic standard.
•Average of mono + diaromatic and poly-aromatic hydrocarbons.

860 Sunil Bharati el al.
Oils with high proportions of polars are also likely to This inability is believed to be primarily due to their
be adversely affected with the variation being about inherent composition. However, a few oils covering a
±8%. wide API gravity range were found to be suitable and
Assuming that most oils would fall in the category were later used to calibrate Iatroscan and prepare
of medium oils, the use of bulk response factors will standards. As expected, the most problematic frac
most commonly not bring about any significant tions were the non-hydrocarbons, due to mainly two
change in the quantitative data. On the other hand, reasons. One reason was the limited amounts of these
the use of bulk response factors, would result in an fractions obtained from the oils, and second being the
underestimation of saturated hydrocarbons in heavy- difficulty in obtaining pure, uncontaminated fractions.
and hydrocarbon-depleted oils which could be This problem was eventually minimised through
crucial. Similarly, an overestimation of saturated repeated separation and parallel analyses.
hydrocarbons in hydrocarbon depleted light oils is A major finding of this study is that the response
also critical, though this case is less likely to occur. factors of the separated fractions from oil are not
With regard to the use of bulk response factors in unique for all oils, but are instead greatly dependent
the analysis of solvent extracts from reservoir rocks, on the composition of the fraction and the API gravity
the degree of inaccuracy should be minimal as the of the oil. It will therefore be highly erroneous to use
majority of the extracts would in any case fall in the a single response factor for, say saturated hydro
category of medium oils. This is, however, not equally carbons, without taking into account the API gravity
applicable to extracts from source rocks, as source of the oil. For the sake of simplicity, a set of 3
rocks are much more likely to be rich in high molecular response factors for each of the 4 fractions, have been
weight non-hydrocarbon species, such extracts being derived which are suitable for heavy oils, medium oils
comparable to low API gravity oils. In general, and light oils, these being defined as RcH, R^M and
therefore, the use of bulk response factors for rock &L-
extracts could be substantially erroneous, since for Examples of two standards, A (rich in polars and
rock extracts it is not only the relative percentage asphaltenes) and B (lean in polars and asphaltenes
data that is important, but also the net yield data. nearly absent), have been prepared through this study
Yields obtained by using response factors derived for use in the petroleum industry. A mathematical
from synthetic standards (R^) are even more model has been developed to derive response factors
erroneous than those obtained by using bulk response and their relationships to the given standard have
factors. The net saturated hydrocarbon yield is grossly been described. These can be readily employed by
overestimated for heavy and medium oils (28 and different Iatroscan users. The use of these standards
9% respectively), while slightly underestimated for and the proposed mathematical model will ensure
light oil. Aromatic hydrocarbons are most adversely realistic inter-laboratory data comparison and
affected by using R^.The net yield is almost doubled, standardization of the Iatroscan technique in the
irrespective of the type of oil, and this is the principle petroleum industry.
reason for highly erroneous relative percentages. Based on the results obtained in the present study
Resins are overestimated for all types of oils, the and bearing in mind the various limitations/problems
medium and low API gravity samples being the most encountered, we recommend the following:
affected. Asphaltenes are also highly overestimated
(up to 80% for light oils), despite employing a large 1. Further work must be performed to better
molecule such as berberine sulphate as an asphaltene understand the dependability of response factors
standard. Apparently, the response of berberine on API gravity and composition of the oil.
sulphate is closer to the natural aromatic hydro More data points are required in this paper’s
carbon fraction from a light oil. All these factors Figs 16 and 17, to make the proposed model
contribute to the highly inaccurate relative percent better and subsequently derive more reliable
ages for a given extract or oil sample, regardless and correct response factors. This will require
of its composition and API gravity, if synthetic further MPLC separations of oils, GC of
standards response factors are used for calibration hydrocarbon fractions and Iatroscan analyses.
and quantification. 2. The concentration of the solution that will be
used to spot samples on the chromarods must
SUMMARY AND CONCLUSIONS
be 10-15 mg oil/ml solvent, to ensure good
chromatography and avoid overloading. In the
Of the 31 oils world wide that were used in the case of whole rocks, SI data from Rock-Eval
study, only a few were found suitable for the purpose should be used to determine the rock weight,
of preparing standards and calibrating the Iatroscan but if nothing is known then 3g should be
TLC-FID instrument. For the remaining oils, the dissolved in 5 ml solvent.
primary reason for not qualifying as Iatroscan Stan 3. An amount of 2 pi solvent containing the
dard precursors was their inability to separate into 4 sample should be spotted on the rod as a general
distinct and clean fractions, which were chromato- practice, preferably using an auto-spotter, to
graphically pure from the TLC-FID point of view. avoid band-spreading and to ensure good

chromatography. Blowing the spotting point pp. 77-85. Norwegian Petroleum Society, Graham &
continuously using nitrogen has been found Karlsen Trotman, London.
D. and barter S. (1991) Analysis of petroleum
to be very effective in quickly removing the fractions by TLC-FID—applications to petroleum
solvent, and should be routinely practised. reservoir description. Org. Geochem. 17, 603-617.
4. As n-pentane precipitated asphaltene fraction Norwegian Industry Guide to Organic Geochemical
is compositionally not at all comparable to the Analyses (1993) 3rd edition. Jointly published by Statoil,
Norsk Hydro, Saga Petroleum, Geolab Nor, IKU and
fraction hitherto referred to as asphaltene in the Norwegian Petroleum Directorate.
TLC-FID technique, we propose the use of Poirier M. A., Rahimi P. and Ahmed S. M. (1984) Quanti
the terms Resin 1 for resins (synonymous to the tative analysis of coal derived liquids residues by TLC
resin or NSO fraction from MPLC) and Resin 2 with flame ionisation detection. J. Chromatogr. Sci. 22,
116-119.
for the fraction hitherto referred to as asphaltene Radke M„ Willsch H. and Welle D. H. (1980) Preparative
in the TLC-FID technique. Resin 2 will therefore hydrocarbon group type determination by automated
essentially comprise of heavier, high molecular medium pressure liquid chromatography. Anal. Chem. 56,
weight and large molecules of NSO compounds, 2538-2546.
relative to Resin 1. Adoption of the terms Resin Ray J. E„ Oliver K. M. and Wainwright J. C. (1982) The
application of the Iatroscan TLC technique to the analysis
1 and Resin 2 will also minimize confusion when of fossil fuels. In Pelroanalysis 81, IP Symposium,
the quantitative data from MPLC is compared London, 361-388. Heyden and Son, London.
to quantitative data from Iatroscan. Selucky M. L. (1983) Quantitative analysis of coal derived
5. Synthetic compounds should not be used as liquids by thin layer chromatography with flame ionisation
detection. Anal. Chem. 55, 141-143.
standards for quantification purposes, as Yamamoto Y. (1988) Analysis of heavy oils by thin-layer
response factors derived from them result in chromatography with flame ionisation detection. Sekiyu
highly erroneous data for real samples. Gakkaishi 31, 351-362.
6. Natural standards (such as the prepared Stan
dards A and B of the present study) should be
used for calibration and subsequently should
be routinely analysed (say once a fortnight or
APPENDIX 1
after every 100 analyses) and the individual
response factors updated accordingly, as the Whole rock (cuttings, core-chips, side wall cores) is crushed
response/sensitivity of any FID alters with time using either a mill or a pestle and mortar to fine particle size.
If the sample is a shale, then the particle size should be
and usage. 65 pm or finer. If the sample is a loosely packed sandstone,
7. Bulk response factors must not be used as these then it is sufficient that all the individual sand grains are free
are likely to give erroneous results. Different and finer crushing does not improve the results. About 2 g
response factors for heavy oils, medium oils of whole rock is accurately weighed in a 8 ml glass vial with
screw cap (cap with a Teflon lining inside), and 2.0 ml of
and light oils must be used instead, which can solvent (dichloromethane: methanol, 93:7 v/v) is added and
be easily calculated and applied by the users. the vial sealed immediately. The sample is allowed to be
extracted for 48-72 h (preferably 72 h if the sample is a
shale), with vigorous agitation 4-5 times a day. If the rock
Acknowledgements—Many thanks to the following oil is very rich in EOM (the colour is dark brown), then an
companies (arranged in alphabetical order) for oil samples: additional 1 ml solvent can be added after one day. After
BEB Erdgas und Erdol GmbH, BHP Petroleum Pty. Ltd, this stage, the procedure is the same as in the case of oils.
Chevron/Cabinda Gulf Oil Company Limited, Mobil
Turkey, Norsk Hydro, OMV Aktiengcsellschaft, Occidental
Petroleum Corporation of Peru, SANTOS Ltd, Saga
Petroleum a/s, Unocal Netherlands B.V., Geolab Nor; and
Norsk Hydro, Saga Petroleum a/s, and Statoil for financial APPENDIX 2
support. F. Behar and D. Karlsen are thanked for critical
List of Ions Specified During GC-MS of Saturated
comments and improving the quality of the manuscript.
and Aromatic Hydrocarbons
m/z Compound
REFERENCES 1- 77 —benzene
2. 83 —cyclo-alkanes
Dietz W. A. (1967) Response factors for gas chromato- 3. 91 —Cl-alkylbenzcnes
graphic analyses. J. Gas Chromatogr. 5, 68-71. 4. 97 —rt-alkcnes/mclhylcyclic-hexancs
Dmshel H. V. (1983) Needs of the chromatographer— 5. 99 —n-alkanes
detectors. 7. Chromatogr. Sci. 21, 375-384. 6. 106 —alkylbcnzcnes
Gout* M., Germ C. and Bertrand J. C. (1990) An applica- 7. 134 —C4-alkylbcnzcncs
tion of Iatroscan thin-layer chromatography with flame 8. 142 —mcthylnaphthalenes
ionization detection—lipid classes of microorganisms as 9. 163 —tcrpancs
biomarkers in the marine environment. In Advances in 10. 183 —isoprenoids
Organic Geochemistry 1989 (Edited by Durand B. and It. 177 —dcmcthylatcd triterpanes
Behar F), pp. 1231-1237. Pergamon Press, Oxford. 12. 191 —triterpanes
Karlsen D. and Latter S. (1989) A rapid correlation method 13. 198 —dibenzothiophenes
for petroleum population mapping within individual 14. 217 —slerancs
petroleum reservoirs: applications to petroleum reservoir 15. 231 —triaromatic steranes
description. In Correlation in Hydrocarbon Exploration, 16 253 —mono-aromatic steranes

APPENDIX 3 6. 134 —C4-atkyIbenzcncs

7. 142 —mcthylnaphthalenes
List of Ions Specified During PY-GC-MS of Resins 8. 156 —C2-naphthalene$
and Asphaltenes 9. 163 —terpanes
10. 170 —C3-naphtha!cncs
miz Compound 11. 192 —methylphenantbrcnes
I. 77 —benzene 12. 198 —dibenzothlophenes
2. 91 —Cl-benzcnc (toluene) 13. 206 —C2-phenanthrenes
3. 97 —n-alkenes 14. 212 —C2-dibcnzothiophenes
4. 99 —w-alkanes 15. 231 —triaromatic stcranes
5. 106 —alkylbenzenes 16. 253 —mono-aromatic stcranes


Paper 7: A New North Sea oil based standardfor Iatroscan 171
Chapter 8: Paper 7
A new North Sea oil-based standard for Iatroscan analysis
Sunil Bharati \ Richard Patience 2, Nigel Mills 3 and Trend Hanesand 4
1 - Geolab Nor, N-7002, Trondheim, Norway

2 - Statoil, N-4035 Stavanger, Norway
3 - Saga Petroleum, Sandvika, Norway
4 - Norsk Hydro, Oslo, Norway
Org. Geochem. Vol. 26, No. 1/2, pp. 49-57. 1997

Pergamon © 1997 Elsevier Science Ltd
All rights reserved. Printed in Great Britain
PH: 50146-6380(96)00152-0 0146-6380/97 sn.oo + o.oo

SUNIL BHARATI1, RICHARD PATIENCE", NIGEL MILLS’ and
TROND HANESAND4
'Geolab Nor, P.B. 5740 Fosscgrenda, N-7002 Trondheim, Norway, "Statoil, N-4035 Stavanger,
Norway, ’Saga Petroleum, P.B. 490, N-1301 Sandvika, Norway and 'Norsk Hydro, P.B. 200,
N-1321 Stabekk, Norway
Abstract—The TLC-F1D technique using the Iatroscan is a fast and cost-effective way to obtain quan
titative data on the composition of crude oils and solvent extracts of rocks. However, its accuracy
depends on correct calibration of the instrument using standards based on crude oil, since the use of
synthetic standards had resulted in erroneous response factors. In the present study, a North Sea deas--
phaltcncd oil from the Oseberg field (NSO-1) was fingerprinted and separated into saturated hydrocar
bons, aromatic hydrocarbons and polars on a large scale, using preparative TLC. These fractions were
later mixed to provide a standard, which was used to calibrate Iatroscan and monitor the responses of
the individual fractions. This standard has been shown to be stable for routine use and will, if adopted,
render inter-laboratory data comparisons more reliable. © 1997 Elsevier Science Ltd
Key words—Iatroscan response factors, standard for Iatroscan, Oseberg oil, preparative TLC

Org. Geochem. Vol. 26, No. 1/2, pp. 49-57, 1997

Pergamon 0 1997 Elsevier Science Ltd
All rights reserved. Printed in Great Britain
PII: 80146-6380(96)00152-0 0M6-6380/97 $17.00 + o.oo

SUNIL BHARATI', RICHARD PATIENCE2, NIGEL MILLS’ and
TROND HANESAND*
'Geolab Nor, P.B. 5740 Fossegrenda, N-7002 Trondheim, Norway, ’Statoil, N-4035 Stavanger,
Norway, ’Saga Petroleum, P.B. 490, N-1301 Sandvika, Norway and ‘Norsk Hydro, P.B. 200,
N-1321 Stabekk, Norway
Abstract—The TLC-FID technique using the Iatroscan is a fast and cost-effective way to obtain quan
titative data on the composition of crude oils and solvent extracts of rocks. However, its accuracy
depends on correct calibration of the instrument using standards based on crude oil, since the use of
synthetic standards had resulted in erroneous response factors. In the present study, a North Sea deas-
phaltened oil from the Oseberg field (NSO-I) was fingerprinted and separated into saturated hydrocar
bons, aromatic hydrocarbons and polars on a large scale, using preparative TLC. These fractions were
later mixed to provide a standard, which was used to calibrate Iatroscan and monitor the responses of
the individual fractions. This standard has been shown to be stable for routine use and will, if adopted,
render inter-laboratory data comparisons more reliable. © 1997 Elsevier Science Ltd
Key words—Iatroscan response factors, standard for Iatroscan, Oseberg oil, preparative TLC
INTRODUCTION pounds were isolated using preparative TLC

(PTLC) with the aim of preparing a standard mix
The thin-layer chromatography-flame ionization
ture for calibrating Iatroscan. Deasphaltened oil
detection (TLC-FID) technique using the Iatroscan
was used in this study, as specified in the
instrument is now recognized as an efficient, fast
Norwegian Industry Guide to Organic Geochemical
and cost-effective way to obtain quantitative data
Analyses (1993). Each isolated fraction was purified
on the composition of crude oils and solvent
by PTLC, then tested for purity using TLC-FID
extracts (Ray et al., 1982; Karlsen and Latter, 1989;
and gas chromatography, prior to mixing. Each
Bharati et al., 1994). Sampling for analysis can be
fraction was individually calibrated so that its
easily performed on a millimetre to meter scale to
Iatroscan response factor could be applied routi
map lateral and vertical heterogeneity in a well,
nely. A standard was then prepared for other users,
field or reservoir unit. Complex organic mixtures
by mixing weighed amounts of the separated frac
such as crude oils, or solvent extracts of sediments
tions.
are easily separated into 3, 4 or 5 compound
classes, depending on the objectives of the study,
each compound class having, however, a different
ANALYTICAL PROCEDURES
response factor.
Previous studies (Bharati et al., 1994) indicated Topped and deasphaltened oil (2.135 g) was sep
that if synthetic standards were employed to cali arated by PTLC using 10 plates (Merck; 1 mm silica
brate the Iatroscan instrument, the resulting re gel with 254 nm fluorescence activator). About
sponse factors were not satisfactory which 200 mg of sample was applied to each plate and
suggested that only crude oil based standards eluted successively with n-hexane (45 min), toluene
should be used for quantification. In the light of (23 min) and dichloromethane/methanol (93:7 v/v,
this, it was logical to develop a new Iatroscan stan 3 min) affording saturated hydrocarbons (Rf 0.64-
dard based on the oil (selected by the Committee 0.87), aromatic hydrocarbons (Rf 0.47-0.62) and
for the Norwegian Industry Guide to Organic polar compounds (Rf 0.25-0.38). Fractions were
Geochemical Analyses) from the Oseberg field, scraped from the plate and recovered by extracting
North Sea, (called North Sea Oil-1) to serve as a with dichloromethane/methanol (93:7 v/v), then
standard for other analytical techniques such as analysed using the Iatroscan as described by
liquid chromatography, gas chromatography and Bharati et al. (1994). Further purification of the
gas chromatography-mass spectrometry. fractions (ARO 1 and POL 1) was done by repeat
In our study, the North Sea Oil-1 (NSO-1) was PTLC analysis which gave fractions ARO 2 and
fingerprinted to understand the basic characteristics POL 2, respectively.
of the oil and more importantly, saturated hydro Quality control at a molecular level of the two
carbons, aromatic hydrocarbons and polar com hydrocarbon fractions was performed using gas

Whole oil-NSO-1
c U
E 800 y =
5 700
y r,
400 -
300 t I I
SO
Time (minutes)
Fig. 1. Gas chromatogram of NSO-1 (whole oil) on a column (40 m; i.d. 0.25 mm, film thickness
0.3 pm) coated with SE 54, temperature programmed from —10 to 300°C at 4°C/min, final hold at
300°C for 20 min. Peak identification example: nC6 denotes normal hexane.
chromatography (GC). Whole oil GC was per cessing. The samples were analysed in multiple ion
formed in conjunction with GC-MS for basic detection mode (MID) with a scan cycle time of ap
characterization and fingerprinting. GC-MS was proximately 1.1 s. Although GC-MS analysis was
performed on saturated and aromatic hydrocarbons not performed quantitatively, the amounts of satu
using a VG TS250 mass-spectrometer interfaced to rated and aromatic hydrocarbon samples injected
a HP 5890 GC. The GC was fitted with a fused were similar, so that the variations in the signal
silica SE 54 column (40 m, i.d. 0.25 mm, film thick intensities are easily comparable.
ness 0.3 pm) directly into the ion source. Carrier
gas was helium. The GC oven was programmed
RESULTS AND DISCUSSION
from 45-150°C at 35°C/min, after which the rate
was 5°C/min up to 310°C, where the column was NSO-1, with an API gravity of 32.8°, is a mature
held isothermally for 15 min. The MS was operated oil from a marine source rock with a low content of
in electron impact (El) mode at 70 eV, a trap cur terrestrially derived organic matter (OM). The com
rent of 500 pA and a source temperature of 220°C. position of the oil is dominated by light- and med
The data system used was a VGPDP11/73 for ium-range hydrocarbons, with the overall n-alkane
acquiring data and a Vax station 3100 for peak pro distribution being distinctly light-end biased (Fig. 1).
Table 1. Selected geochemical parameters of NSCM based on gas chromatographic analysis of the
saturated and aromatic hydrocarbons
Parameter Value
1 Pristane/nC17 0.51
2 Pristane/phytanc (Pr/Ph) 1.56
3 Phytane/nClB 0.39
4 Carbon Preference Index (CPI) 1.10
5 nC17/nC17 + nC27 0.91
6 Dimethylnaphthalene ratio (DMNR) 1.79
7 2/1 •methylphenanthrenc (2/1MP) 0.94
8 Methylphenanthrene index (MPI) 0.70
9 Calculated vitrinite reflectance (/y 0.82
10 Dibenzothiophene/phenanthrene (DBT/P) 0J8
11 4/1-metbyIdibenzotiiiophene (4/1MDBT) 3.60
12 3 + 2/1-metbyldibenzo thiophene (3 + 2/1MDBT) 0.91

NSO-I-Saturated fraction m/z 191 3.1E6.

2.9E6
2.8E6
2.6E6
• 2.2E6
% 50 -I.5E6
-UE6
9.2B5
7.7E5
•6.2B5
•4.6E5
-3.1B5
0.0E0
45:00 50:00 55:00 1:00:00 1:05:00 1:10:00 1:15:00 1:20:00 1:25:00 1:30:00 1:35:00 1:40:00
Time
NSO-l-Saturated fraction m/z 217
5.9E5
5.5B5
5.2E5
4.9E5
4.6E5
4.2E5
3.9E5
3.6E5
% 50- 3.3E5
2.9E5
2.6E5
2.3E5
.2.0E5
-1.6E5
-1.3E5
-6.5E4
•O.OEO
50:00 1:00:00 1:05:00 1:10:00 1:15:00 1:25:00
Fig. 2. (a) Tritcrpane distribution (m/z 191) and (b) stcrane distribution (m/z 217) in NSO-1. Both the
fragmcntograms are obtained by GC-MS analysis of the saturated hydrocarbon fraction. Identification of
important peaks: (a) In m/z 191: A, 18a(H>22t29,30-trisnomeohopanc (Ts); B, 17o(H)-22^9,30-trisnorho-
pane (Tm); Z, 17o(H)t21^(H)-28,30*bisnorhopane; C, 17«(H),210(H)-3O-norhopane; D, 17^(H)^la(H>
30-norhopane; E, 17o(H),21/?(H)-hopanc; F, 17/?(H),21a(H)-hopane; JI, 17a(H),2l/J(H)t22S-bishomoho-
pane; J2, 17oc(H)k21^(H)>22J?-bishomohopane; and Q, C24H44tricyclic terpane. (b) In m/z 217: a,
13/7(H),l 7o(H),20(.S)-diacbolestane; b, 130(H),17o(H),2(W-diacholc$tane; c, 13e(H),170(H),2O(S)-dia-
cholestane; d, 13o(H), 170(H),2O(/?)-diacholestane; h, 24-ethyt-130(H),17o(H),2O(S)-diacholestane; k, 24-
ethyl-130(H), 17o(H),20(Jt)-diacholestane; !, 24-ethy!-13o(H),170(H),2O(Jt>diacholestane; n, 24-cthyl-
I3o(H),170(H),2O(S>diacholestane; q, 24-cthyl-5o(H),14«(H), 17a(H),20(S)-cholestane; r, 24-ethyl-
5o(H), 140(H), 170(H),20(A)-cholestane; s, 24-ethyl-So(H), 140(H), 170(H),2O(S)<hoIestans and t, 24-
ethyl-5o(H), 14o(H), 17o(H),20(/Z)-cho!estane.

52 Sunil Bharati el at.
Table 2. Selected geochemical parameters based on tritcrpane and

Parameter Value
1 17e(H)-22,29.30-trisnorhopane/18a(H)-22,29,30-tranomeohopanc (Tm/Ts) 0.85
2 17e(H),21/i(H)-30-norhopanc/17ir(H)12I/l(H)-hopane 0.45
3 15a-mcthyM7a(H)-27-norhopane/17a(H),21/?(H)-hopanc 0.09
4 CuHutricyclic terpane/17a(H),21/J{H)-hopane 0.03
5 17^(H)^la(H)*30*norhopane + 17^(H)21a(H>hopanc/17e(H)2iP(H)-30-norhopane + !7a(H)21/l(H)-hopane 0.15
6 17a(H),21^(H),22S/I7a(HWI«H)22K + 225-bishomohopane 57.96
7 13P(H).17a(H),20(S>diacholestane/13^(H).17a(HU0(S)-diacholcstanc + 5a(H),!4a(H),17e(H),20yi)-cho!cstanc 0.78
8 % 24ethyl-5a(H),14a(H),17a(H)^0(S)-cholestane 46.10
9 X 27 diasteranes/X 29 diasterancs 0.92
10 % 24^thyl 5a(H).l4f(H).17f(H)jO(A) and 20(SKholestane 61.0
A predominantly marine OM source for the oil is were reproducible, giving uniform FID responses.
indicated by the low pristane to phytane ratio (Pr/ Analysis of the saturated hydrocarbons fraction
Ph) and the low carbon preference index (CPI) with varying amounts of sample (ca. 3-44 pg) gave
values (Table 1). The triterpane and sterane distri a correlation coefficient of 0.998 (n = 15, Fig. 4a).
butions (Fig. 2) and the parameters derived from Similar analyses of the aromatic hydrocarbons frac
these data (Table 2), also clearly indicate a predo tion (ca. 7-86 pg) gave a correlation coefficient of
minantly marine OM source of NSO-1. 0.997 (n = 15), while the polar fraction (ca. 1-
30 pg) gave a correlation coefficient of 0.998
Separation of NSO-1 maltene fraction (n = 17) on linear regression (Fig. 4b and c, re
Examination of a developed PTLC plate at spectively). These results clearly indicate the stab
254 nm clearly revealed the separated fractions. ility of the responses of each of the fractions:
Table 3 shows the yields of the three fractions. Fig. 4(b) also shows the percentage of the total
Analysis by TLC-FID showed that the SAT 1 frac area eluting as polars in the various aromatic hy
tion was virtually pure (Fig. 3). The ARO 1 fraction drocarbon analyses. Apparently, power regression
was, however, contaminated with polar compounds of the peak area that elutes as polars shows that
(about 11% by weight), whilst the POL 1 fraction the relative amount of sample material eluting as
was relatively clean, but split into two closely elut “polars” decreases with increasing sample amount
ing peaks. However, a second round of PTLC using applied. The reason and significance of this is not
ARO 1 and POL 1 fractions removed much of the entirely clear. In general, the relative peak area elut
unwanted material in each of these fractions, result ing as polars is about 6-10% of the total ARO 2
ing in much purer fractions, ARO 2 and POL 2, re fraction (when the injection consists of about 20-
spectively (Fig. 3). The SAT 1 and POL 2 fractions 82 pg), which should be seen as an addition to the
were, as a result of further PTLC separation, nearly actual area due to the POL 2 fraction in the mixed
100% pure, but about 10% of ARO 2 continued to standard (see the next section).
consist of polar material which was impossible to Gas chromatographic analyses of the two hydro
remove even after two further purification steps by carbon fractions (Figs 5 and 6) do not give any in
PTLC. dication of cross-contamination.
Analyses by GC-MS of SAT 1 and ARO 2, indi
Analysis of the isolated fractions cated only trace levels of contamination, based on
Iatroscan analyses of the three fractions (SAT 1, fragmentograms m/z 57, 91, 92, 99, 106, 142, 191,
ARO 2 and POL 2) which were to be used to pre 198, 217 and 253. While the saturated hydrocarbons
pare the standard mixture showed that the results fraction has only traces of alkylbenzenes, the arc-
Table 3. Yields of various fractions from the total amount of 2.135 g maltene spotted on 10 PTLC plates. Only the SAT 1, ARO 2 and
POL 2 fractions were used in the standard mixture
Fraction Yield (mg) Rr Yield (%)
1 Saturated HC (SAT 1) 1191.2 0.64-0.87 59.10
2 Aromatic HC (ARO 1) 747.7 0.75-0.99 (purified further)
3 Aromatic HC (ARO 2) 651.6 0.75-0.99 3233
4 Polars (main) (POL 1) 50.6 0.67-1 (purified further)
5 Polars (main) (POL 2) 36.0 0.67-1 1.79
6 SAT/ARO boundary 69.6 nd 3.45
7 ARO/POL boundary 20.6 nd 1.02
8 Polars (secondary) 24.6 nd 121
9 Spot (material not eluted) 22.0 — 1.09
Total quantified 2015.6 100.00
nd, not

A new North Sea oil-based standard for Iatroscan analysis 53
SAT 1 ARO 2 POL 2
cm cm cm
(a) (b) (c)
Fig. 3. TLC-FID chromatograms of the separated and pure fractions from PTLC; (a) saturated hydro
carbons (SAT 1), (b) aromatic hydrocarbons (ARO 2) and (c) polar compounds (POL 2). These frac
tions were subsequently used to prepare the standard mixture.
matte hydrocarbons fraction is dominated by alkyl- This suggests that in the 10 repeat analyses, while
benzenes (signal intensity 42 times stronger than in there was about 6% variation in the actual amounts
the saturated hydrocarbons) and alkylnaphthalenes quantified, there is much less variation in the rela
(signal intensity more than 100 times stronger than tive percentages of the fractions, indicating human
in the saturated hydrocarbons); only traces of n- error during sample application, rather than the
alkanes, triterpanes and steranes were detected in reproducibility of the Iatroscan. With regard to the
the aromatic hydrocarbon fraction. amounts quantified in the standard mixture, the
saturated hydrocarbons were calculated to be
Preparation of the standard 20.63 pg in a 2-p\ injection, compared with the
theoretically calculated 20.46 pg. The aromatic
As a result of 10 repeat analyses of the NSO-1
hydrocarbons are slightly underestimated (reported
maltene fraction by Iatroscan, the percentages of
as 8.89 pg compared with the theoretically calcu
saturated and aromatic hydrocarbons and polar
lated 9.84 pg) and the polar compounds are over
compounds were found to be 59, 31.2 and 9.8, re
spectively (Fig. 7a). Accordingly, a standard was estimated (reported as 2.?1 pg compared with the
prepared by weighing the PTLC fractions to give a theoretically calculated 0.96 pg). Closer examination
mixture with a roughly similar composition, of these variations reveals that this is due to the
namely: 65.46% SAT 1, 31.47% ARO 2 and 3.07% contribution of ARO 2 to the polars.
POL 2 (Fig. 7b). The reason for using such a low It has been shown that, depending on the amount
amount of POL 2 was the limited quantity obtained applied, some of the ARO 2 fraction elutes as
(Table 3). With the prepared standard having a polars. It is also known that the total amount of
concentration of 15.63 pg/pl, a typical injection of the ARO 2 fraction in a 2-pl injection is 9.84 pg.
2 pi will theoretically contain 31.26 pg maltene, con Using the power regression equation, it is estimated
sisting of 20.46 pg saturated hydrocarbons, 9.84 pg that for this amount, about 11% of the total aro
aromatic hydrocarbons and 0.96 pg polars. matic area will elute as polars, indicating that the
Repeat analyses of the prepared standard mixture area reported for aromatic hydrocarbons (55460)
(Fig. 7b and Table 4) show that the standard devi represents only 89% of the total area or 89% of
ation in the actual amounts is greater (6, 6.7 and 9.84 pg, which is 8.75 pg. This calculated amount
7.7%, respectively) than the standard deviation in (8.75 pg) is close to the actual aromatic hydro
the compositional percentages (1.8, 4.8 and 7.3). carbon amount reported for the prepared standard

54 Sunil Bhaiati et al.
(a) Calibration of saturated hydrocarbons

250
♦ SAT 1
200
150
100
80
2 6 10 14 18 22 26 30 34 38 42 46
(b) Calibration of aromatic hydrocarbons
♦ Polar area * Total ARO 2 area * Polar area %

500-
500-
-10 a
300-
T ....
18 26 34 42 50 58 66
(c) Calibration of polar compounds
POL 2
250-
200- -
11 13 15 17 19 21 23 25 27 29 31
Amount applied (#ig)
Fig. 4. Cross-plots of sample amount vs. corresponding FID response, (a) Saturated hydrocarbon frac
tion (SAT 1). Fifteen samples were analysed with varying amounts (3.2-44.66 pg). The resulting re
sponse factor using the equation y *=* a + bx is 4017. (b) Aromatic hydrocarbon fraction (ARO 2).
Fifteen samples were analysed with varying amounts (7.6-85.66 pg). The resulting response factor using
the equation y = a + bx is 6235. (c) Polar compounds (POL 2). Seventeen samples were analysed with
varying amounts (1.2-30 pg). The resulting response factor using the equation y =* a + bx is 8352.

SAT 1-NSO-l
■5 600
Time (minutes)
Fig. 5. Gas chromatogram of saturated hydrocarbon fraction (SAT 1) on a column (25 m; i.d. 0.25 mm,
film thickness 0.3 /ml) coated with OV1, temperature programmed from 80-300°C at 4°C/min and held
at 300°C for 20 min. Peak identification example: nCu denotes normal penladecanc.
ARO 2-NSO-l
360 -
> 280
g 240
Time (minutes)
Fig. 6. Gas chromatogram of aromatic hydrocarbon fraction (ARO 2) on a column (40 m; i.d.
0.25 mm, film thickness 0.3 pm) coated with SE 54, temperature programmed from 40-290°C at 4°C/
min and held at 290°C for 20 min. GC equipped with both FID and FPD detectors. Peak identification
key to isomers: MN, mcthylnaphthalene; EN, ethylnaphthalene; DMN, dimethylnaphthalene; TMN,
trimethylnaphthalene; P, phenanthrene and MP, methylphcnanthrene. The numerical prefixes denote
the position of the alkyl group.

(a) (b)
Fig. 7. TLC-FID chromatogram of (a) NSO-1 maltene and (b) the gravimetrically prepared standard
using the separated fractions obtained by PTLC. The percentages of saturated hydrocarbons, aromatic
hydrocarbons and polars are 59, 31.2 and 9.8, respectively in NSO-1 maltene and 65, 28 and 7, respect
ively in the gravimetrically prepared standard.
(8.89 pg). Had all of the 9.84 pg eluted as aromatic 7.0% polars (reported as 2.21 pg), all with a 2-pl
hydrocarbons, the area would have been 62315. injection.
Therefore, in the total area of 18569 reported for CONCLUSIONS
the polars in the prepared standard, a significant
portion (6855) is due to material from the AR02 The standard mixture of saturated and aromatic
fraction eluting as polars. Therefore, despite the hydrocarbons and polar compounds prepared from
fact that the theoretical percentages of SAT 1, the maltene fraction of the Oseberg oil NSO-1, has
been shown to give reproducible results and can be
ARO 2 and POL 2 in the prepared standard are
considered as a normal oil from the North Sea, and
65.46, 31.47 and 3.07, respectively, during analysis,
can be easily and successfully employed to calibrate
the standard’s composition obtained will be:
the Iatroscan. In addition, the composition of the
65.0% saturated hydrocarbon (reported as prepared standard is close to the actual composition
20.63 pg), of the maltene fraction of Oseberg oil. Further, on
28.0% aromatic hydrocarbon (reported as TLC-FID analysis, the composition of the prepared
8.89 pg) and standard mixture is found to be nearly the same as
Table 4. Results of 10 repeat Iatroscan analyses of the prepared standard using the same amount (2 pi) each time. The response factors
used are 4017, 6235 and 8352 for saturated hydrocarbons, aromatic hydrocarbons and polars, respectively, these being the new response
factors based on the standard mixture prepared from the NSCM maltene
Saturated hydrocarbons Aromatic hydrocarbons Polars

Peak area Pg (%> Peak area Pg (%) Peak area Pg <%)
Mean 82876 20.63 (65) 55460 8.89 (28) 18569 Z21 (7)
SD 4976 1.24 (1.15) 3733 . 0.60 (135) 1382 0.17 (0.51)
SD (•/,) 6 6 (1.8) 6.7 6.7 (4.8) 7.4 7.7 (73)

its theoretically calculated composition, when the Organic Geochemistry 1993 (Edited by Telntes N„ Graas
response factors calculated from the three individ G. and 0ygard K.), Org. Geochem. 22, 835-862.
Pergamon, Oxford.
ual fractions are used. Karlscn D. and Latter S. (1989) A rapid correlation
Employment of this standard by different labora method for petroleum population mapping within indi
tories will make the comparison of inter-laboratory vidual petroleum reservoirs: applications to petroleum
Iatroscan analyses more reliable; now even more reservoir description. Correlation in Hydrocarbon
important since Norwegian oil companies and the Exploration, pp. 77-85. Norwegian Petroleum Society,
Norwegian Petroleum Directorate have decided to Graham and Trotman, London.
Ray J. E., Oliver K. M. and Wainwright J. C. (1982) The
use quantified crude oil and extract compositional
application of the Iatroscan TLC technique to the
data from Iatroscan rather than from MPLC. analysis of fossil fuels. In Petroanalysis 81, IP
Symposium, London, pp. 361-388. Hcyden and Son,
London.
REFERENCES
The Norwegian Industry Guide to Organic Geochemical
Bharati S„ Rerstum G. and Lorbcrg R. (1994) Calibration Analyses, 3rd edition, 1993 (A joint publication by
and standardization of Iatroscan (TLC-FID) using Statoil, Saga Petroleum, Norsk Hydro, IKU, Geolab
standards derived from crude oils. In Advances in Nor and the Norwegian Petroleum Directorate).
OG 26/1-2—C

Paper 8: Elucidation of the Alum Shale kerogen structure 181
Chapter 9: Paper 8
Elucidation of the Alum Shale kerogen structure using a multi

disciplinary approach
Sunil Bharati \ Richard Patience 2, Steve Larter 3, Guy Standen 4 and Iain Poplett5
1 - Geolab Nor, N-7002, Trondheim, Norway

2 - Statoil, N-4035 Stavanger, Norway
3 - NRG, Drummond Building, University ofNewcastle, U.K.
4 - School of Chemistry, University ofBristol, U.K.
5 - BP Research, Sunbury on Thames, U.K.
Ort. Ctockm. VoL 23. No. 11 12. pp. 1043-1058. 1995

Copyright f 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0146-6380 95 S9.50 - 0.00
Elucidation of the Alum Shale kerogen structure using a

multi-disciplinary approach
SUNIL BHARATI'. RICHARD L. PATIENCE-*. STEVE R. LARTER.''
GUY STANDENt and IAIN J. F. POPLETP
'Geolab Nor. PO Box 5740 Fossegrcnda. 7002. Trondheim. Norway. :BP Research. Chertsey Road.
Sunburv on Thames. Middlesex TW16 7LN. U.K. 'NRG. Drummond Building. The University.
Newcastle upon Tyne NE1 7RU. U.K_. 'Organic Geochemistry Unit. School of Chemistry.
University of Bristol. Bristol BS8 ITS. U.K.
(Received 28 February 1994: returned for revision 7 July 1995: accepted 30 November 19951
Abstract—The significance and validity of integrating data obtained from a variety of analytical techniques
to understand, elucidate and model kerogen's complex chemical structure is reported here using
degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (l*C CP'MAS NMR)
and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging
in maturity from immature to post-mature with respect to petroleum generation, were studied and were
chosen for their simple geological history, uniform organic matter type and high organic carbon content.
The Alum Shale kerogens. which primarily consist of algal organic matter, liberate low molecular weight
gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic adds on chemical
oxidation. "C NMR spectroscopy shows that the Alum Shale kerogens arc anomalously rich in
oxygen-bearing functional groups (such as C * O. ArCO. CHO. CH.O). most of which apparently remain
intact within the kerogen macro-molecule (KMM) through the diagenetic and catageoetic stages.
Fragments released by different degradative techniques are quantified and the aromatidty (f«). O/C and
relative proportions of various carbon types estimated by l$C NMR. A synthesis of these data has allowed
us to better understand the chemistry of the Alum Shale kerogen. Copyright © 1996 Elsevier Science Ltd
Key words—kerogen structure. pyrolysis-GC. chemical oxidation. nC NMR, aromaticity. Alum Shale

Org. Grochrm. Vo!. 23. No 11 12. pp. 1043-1058. 1995

Copyright C 1996 Elsevier Science Ltd
Pergamon 0146-6380(95)00089-5 Printed m Great Britain. All rights reserved
0146-6380 95 S9.50 - 0.00
Elucidation of the Alum Shale kerogen structure using a

multi-disciplinary approach
SUNIL BHARATI1. RICHARD L. PATIENCE-*. STEVE R. LARTER.1
GUY STANDEN4 and IAIN J. F. POPLETT
'Geolab Nor. PO Box 5740 Fossegrenda. 7002. Trondheim. Norway. :BP Research. Chcrtsey Road.
Sunbury on Thames. MiddlesexTW16 7LN. U.K. ’NRG. Drummond Building. The University.
Newcastle upon Tyne NE1 7RU. U.K.. ’Organic Geochemistry Unit. School of Chemistry.
University of Bristol. Bristol BS8 ITS. U.K.
tReceived 28 February 1994: relumed for revision 7 July 1995: accepted 50 November 19951
Abstract—The significance and validity of integrating data obtained from a variety of analytical techniques
to understand, elucidate and model kerogen's complex chemical structure is reported here using
degradauve (open and closed system pyrolysis, chemical oxidation), non-degradativc f’C CP'MAS NMR)
and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging
in maturity from immature to post-mature with respect to petroleum generation, were studied and were
chosen for their simple geological history, uniform organic matter type and high organic carbon content.
The Alum Shale kerogens. which primarily consist of algal organic matter, liberate low molecular weight
gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical
oxidation. "C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in
oxygen-bearing functional groups (such asC « O. ArCO. CHO, CH,0). most of which apparently remain
intact within the kerogen macro-molecule (KMM) through the diagcnetic and catagcnetic stages.
Fragments released by different degradative techniques are quantified and the aromaticity (f.). 01C and
relative proportions of various carbon types estimated by l’C NMR. A synthesis of these data has allowed
us to better understand the chemistry of the Alum Shale kerogen. Copyright © 1996 Elsevier Science Ltd
Key words—kerogen structure. pyrolysis-GC. chemical oxidation. "C NMR. aromaticity. Alum Shale
INTRODUCTION than one technique. While their work throws new

Several studies have been conducted in the past, using light on essential differences between different
a variety of techniques, aimed at elucidating the kerogen types, our understanding of kerogen's
structure of kerogens. The most common degradative complex chemical structure is still restricted, partly
techniques have been chemical degradation (e.g. due to the size and complexity of the kerogen
Simoneit and Burlingame. 1973; Vitorovic. 1980; macromolecules and because models developed using
Mycke and Michaelis. 1986) and pyrolysis (e.g. one set of samples may not apply to other samples of
Latter and Douglas. 1982). Non-degradative tech similar kerogen 'type'.
niques included infrared spectroscopy (e.g. Robin In this paper, we have applied a variety of
and Rouxhet, 1976; Rouxhet et al.. 1980). nuclear techniques, such as pyrolysis-gas chromatography,
magnetic resonance (e.g. Miknis et al., 1982; Solli ”C CP/MAS NMR and chemical degradation, to
et al., 1985; Mann et a/.. 1991) and electron investigate the Cambrian Alum Shales from southern
microscopy (e.g. Oberlin et al., 1974. 1980). While Sweden and Norway. This shale (Andersson et al.,
such studies have made a significant contribution to 1985) is interesting from the point of view of its
our understanding of the kerogen macromolecule, simple geological history (Thickpenny, 1987), uni
there remains a lot that is not known about its form organic matter type (Bharati, 1989; Bharati and
structure, primarily because most of these studies Larter. 1991) and unusual chemistry (Dahl et al.,
have attempted to address the problem based on a 1988; Lewan and Buchardt, 1989; Bharati et al., 1992;
single technique resulting in a narrow and incomplete Horsfield et al., 1992). The sample suite used in this
understanding. Behar and Vandenbroucke (1987) study is from southern Sweden and Norway.
however proposed structural models of the three
principal kerogen types based on data from more SAMPLES AND GEOLOGY
The present study used seven outcrop samples (2
•Present address: Statoil. 4035 Stavanger, Norway.
tPresent address: 7 New Row. Tanyard Lane. Steyning, W. samples are from the same location) of Alum Shale
Sussex. UK. (Late Cambrian) (Fig. 1). It consists of a black

Paper 8: Elucidation ofthe Alum Shale kerogen structure 183
1044 Sunil Bharati el el.
NORWAY SWEDEN
Stockholm •'
Gatsberg
Gotland
Legend
1. Pilstorp
2. GoMSter
3. Kvamtorp
4. Trolmen Cambro-SUurtan
5. Rokstorp sediments
6. KrekHng Malmo\
I Cambrian AX*n Shale
.Bornholm
Cambrian Alum Shales In

Southern Scandinavia
Fig. 1. Map of southern Scandinavia showing the Alum Shale Formation exposures and the locations of
the samples included in the present study.
laminated shale and mudstone facies, 10-60 m thick, to maximize uniformity in sample age and organic
with large amounts of organic matter (typically facies. The Alum Shale, which is today found
10-12% TOC). The unit represents a long period of as erosional outliers in several parts of Scandinavia
very slow epi-continental deposition (3-10 mm /1000 (Fig. 1), is not at present a recognized petroleum
years; Thickpcnny, 1987) in a paleo-basinal area of source rock, although its exploitation dates back
perhaps several thousand square kilometres; it is to the beginning of this century (Andersson et al.,
uniquely enriched in trace elements, especially 1985). More details about the geology of the
uranium and vanadium (Andersson et al., 1985). The Alum Shale and of the samples studied can be found
formation rests on the Balto-Scandian Platform in Andersson et al. (1985) and Bharati (1989)
(a gneissic Precambrian basement), that was an area respectively.
of great stability during the Late Cambrian Some Alum Shale outliers in southern Sweden are
(Andersson et al., 1985). The samples used in this capped by Permian dolerite sills (present thickness
study are restricted to the Peltura scarabaeoides up to ca. 60 m; Dahlman and Gee, 1977), for example
(Westergird, 1922) stratigraphic zone (2-9 m thick) in the Billingen area (location 5 in Fig. 1). The

Elucidation of the Alum Shale kerogen structure 1045
Table 1 Screening analyses data for the Alum Shales

Sample Location Sample TOC HI 01 HC ■ V: Ro bit ;: Vol F * Vol. NF ' Matuntx *
number code1 I'.i tppmi (•-.) Cel (*et
1 Gosseter GOS-2-86 22 439 10 1.05 8" 0.36 28 3 Immature

Palstorp PALO-86 12 402 16 1.01 130 0.25 19 5 Immature
3 Gosseter GOS-5-86 15 329 19 ixr 110 0.34 0 6 Immature
4 Trolmen TR-6 12 269 35 0.98 68 0.41 12 Earlx mature
5 Kvamtorp K5-86 19 22? 23 0.99 113 0.34 23 20 Earlx mature
6 Rokstorp SK-3-86 13 152 7 0 76 58 0 45 1 12 Late mature
Krekling KR-21 12 0 5 0.08 4.83 0 32 Post mature
'See Fig. I. Samples 1 and 3 arc from the same location. -"From Bharati (19891. 'From Horsfield ct at. (19931.1 Volume of fluorescing
macerals ' Volume of non-fluorcscmg maccrals as related lo total rock volume (Bharati and Barter. 19911. • Estimated with respect to
oil generation for Type II kerogcns.
thermal influence of these dolerite sills has probably achieved using a Micro PDP 11 53 (Digital) and VG's
been variable in different areas, although no attempt Multichrom v3.4 software. Quantitation used peak
was made in the present study to describe this areas related to the peak area of the internal
variation. standard.
The samples discussed in this paper are from
southern Sweden (Palstorp. Gosseter. Kvamtorp. Solid state L‘C CP'MAS NMR
Trolmen and Rokstorp) and Norway (Krekling) Measurements were made using a Broker MSL 300
(Fig. 1). As the age of the Alum Shale proscribes the instrument at 75.47 MHz. An independent f. (f, is the
presence of higher plant derived vitrinite. maturation degree of aromaticity) measurement was made from
was based on bituminite reflectance which varied standard CP/MAS spectra recorded at 25.47 MHz on
from 0.3 to about 4.0% (Bharati and Latter. 1991). a Broker MSL 100 spectrometer, to check the carbon
The Pilstorp and Gosseter samples are thermally type analysis. A detailed description of this technique
immature, the Trolmen and Kvamtorp samples are is given by Mann et al. (1991). Briefly, average
early mature, while the Rokstorp sample has a base molecular structures were obtained by a carbon "type"
of oil-window maturity. The organic matter in the analysis technique that involved the fitting of the
Oslo area (the Krekling sample) is graphitic in nature simulated spectrum to the dipolar dephased spec
and is over-mature (Table I). trum. and then the deconvolution of the standard
CP/MAS spectrum into individual carbon type
ANALYTICAL METHODS resonances (Appendix 1). using chemical shift data
obtained from standard compounds. All chemical
Total organic carbon (TOC) was measured using a
shifts were measured relative to the methine carbon
LECO CR12 carbon analyzer. Samples were pow
resonance of solid adamantane. which is 38.56 ppm
dered. treated with 10% HC1 to remove carbonate
relative to TMS. The distribution of each chemical
carbon, washed with distilled water and oven dried
shift histogram for every carbon type was subjected
(60:C. 12 h). Bulk pyrolysis, using powdered whole
to a moment analysis to yield a mean chemical shift
rock aliquots, was performed using Rock-Eval as
described by Espitalie et al. (1977). Kerogen and a median width.
The individual carbon types applied in the carbon
concentrates were prepared by treatment of the
type analysis of "C NMR spectra (Appendix 1) are
sample with 37% HC1 followed by 48% HF.
based on the model developed by Mann et al. (1991)
Quantitative-pyrolysis—gos chromatography (Q-Py- of carbon types likely to be present in coals and
GCi kcrogens and uses about 140 reference compounds
identified from the literature (e.g. Bremser et al.,
The kerogen concentrates were ultrasonically
1981). Criteria for selection and subsequent treatment
extracted with DCM'MeOH (93:7 v/v) prior to
of chemical shifts are described in Trewhella et al.
pyrolysis. Poly para-t-butyl styrene was used as
(1986), as are the limitations of this approach. The
internal standard (1% by weight). A known amount
distribution of each chemical shift histogram for
of standard was added to an accurately weighed
every carbon type was subjected to a moment analysis
kerogen sample suspended in a solvent and
to yield a mean chemical shift and a median width.
ultrasonically mixed before Q-Py-GC analysis
The additional carbon types were given a chemical
(barter and Senftle, 1985) using a Varian 3700 gas
shift from the updated data-base and a median width
chromatograph equipped with a CDS 100 pyrolyser.
equal to those of similar groups. The chemical shift
A DB-1 bonded phase column (length = 30 m;
distribution was assumed to be Gaussian.
l.D. = 250 pm: film thickness = 1 pm) was tempera
ture programmed from —50 C (held at —50" for
Ruthenium tetroxide oxidation
5 min) to 300"C at a rate of 4'C/min (held at 300"C
for 15 min) using helium as carrier gas. Pyrolysis was The oxidation was carried out according to
carried out at 800"C for 20 s. Data acquisition, Standen and Eglinton (1992). A sample of kerogen
processing, peak integration and quantitation were (10-25 mg) was mixed with acetonitrile/chloroform

(2:1: 0.3 ml. containing 2.5 mg Ru (IV) oxide) and to the average value of organic carbon in source rocks
water. Five internal standards ((I) d, succinic acid. (2) (2.16% in shales and 0.67% in carbonates) (Tissot
1.1 -cyclohexanediacetic acid. (3) n-octadccylsuccinic and Welle. 1984). Optical analysis of the Alum Shales
acid. (4) <L cholestane and (5) hexatriacontane] were has shown that organic macerals occupy as much as
added plus periodic acid (0.3 ml. 50% solution in 40% of the total rock volume (Bharati and Larter.
water). After agitation (12h at 45'C). the organic 1991) (Table 1).
layer was removed and washed twice using 4:1 Rock-Eval analyses show a progressive decrease in
diethylether dicholoromethane. Particulates, water the hydrogen index (HI), from 439 in sample 1 from
and iodine were removed on a Celite magnesium Gosseter in south Sweden to 0 mg hydrocarbon g
sulphate column impregnated with saturated thiosul organic carbon in sample 7 from Krckling in Oslo
phate solution. After final solvent extraction, the area (Table 1). Preliminary evaluation of Rock-Eval
sample was concentrated and methylated (1.5% v v data suggested the Alum Shale kerogen to be ‘Type
sulphuric acid and 5% v v tetrahydrofuran in II' (Espitalie et al.. 1977). Petrographic investigations
methanol: 50:C for 6 h). Methyl esters were extracted (Bharati. 1989: Bharati and Larter. 1991) clearly
with 9:1 hexane/diethylether (3 times). The organic show that the kerogen (principally alginite at an
layer was dried on a Celite column, concentrated immature stage) remains nearly uniform, irrespective
(using N-) and dichloromethane was added prior to of the hydrogen richness and the location of the
GC analysis. Blanks were also run over identical time sample. The organic facies variation therefore is
periods, permitting subsequent corrections in the minimal for the series and the fall in HI for
calculations. These contained mostly trace amounts organic-rich samples indicates an increase in thermal
of plasticizers and n-alkancs (Standen. 1992). maturity.
Gas chromatography was performed using a Bharati et al. (1992) and Bharati and Latter (1991)
Varian 3400 gas chromatograph. An OV1 column suggested earlier that the present Alum Shale sample
was used (length - 50 m: od — 0.32 mm: film suite is a natural maturation series—varying from
thickness = 0.17 pm) and temperature programmed immature (equivalent vitrinite reflectance < 0.5%) to
from 40;C (hold time 1 min) to 300:C (hold time post-mature (equivalent vitrinite reflectance > 1.2).
30 min) at a rate of 4:C/min. Hydrogen was used as The changes in the fluorescence properties of
carrier gas and nitrogen as the make-up gas. alginites. the progressive fall in HI (Table 1)
Data were acquired using a Minichrom Data accompanied by a progressive increase in the
System (v 1.51 software) and quantification was bituminite reflectance (‘R. Bit* in Table 1) support
accomplished using peak area integration in relation this conclusion.
to n-octadecylsuccinic acid. Peaks were identified by The Alum Shale solvent extract yields are rather
gas chromatography-mass spectrometry using a low compared with other rich source rocks contain
Varian 3400 GC interfaced to a Finnigan Mat TSQ ing Type II kerogen. The extracts are depleted in
70 mass spectrometer (ionizing energy 70 eV; ion hydrocarbons, with resins and asphaltenes typically
source temperature 150"C: I scan s for m:z 50-550). comprising more than 75% of the total extract
An ICIS data system was used to acquire and process (Bharati, 1989). The hydrocarbon extracts contain
the information. Identification and quantification of almost double the amount of aromatic hydrocarbons,
compounds used the procedure of Boucher et at. compared with saturated hydrocarbon (Bharati.
(1990). 1989). These findings differ from those of Tissot and
Welle (1984) for other mature source rocks
Microscopy containing Type II kerogens and are in general
Whole rock samples were mounted (parallel and agreement with the results reported by Dahl et al.
perpendicular to bedding) in epoxy blocks and (1988) and Lewan and Buchardt (1989).
polished using Struer's Planapol;Pcdamax-2. The
Quantitatice-prrolvsis-gas chromatography (Q-Py-
samples were examined with a Zeiss Photomicro
OCJ
scope III. linked to an HP 9816S computer.
Reflectance measurements were made (oil immersion) This method was used to obtain data on compound
at 546 nm wavelength. The data were acquired and types liberated on pyrolysis. A typical pyrogram
processed using the Zeiss Coflex software. Fluor resulting from 800'C flash pyrolysis of an Alum Shale
escence was measured using blue light excitation kerogen (sample 1) is shown in Fig. 2 while Table 2
(395-440 nm) and spectral measurements were made summarizes pyrolysis data for all samples. All the
using a continuous grating interference filter from 400 kerogens release, qualitatively, very similar py-
to 700 nm. rolysates, resulting in similar pyrogram fingerprints,
irrespective of thermal maturity and hydrogen
RESULTS content, except for the post-mature sample 7, which
is nearly graphitized and which has a hydrogen index
Organic matter input and maturity of 0 mg HC/g TOC (Table 1).
The seven Alum Shale samples have TOC values Gases (Ci-Cj) dominate the pyrolysates with
ranging from 10% to 22% (Table 1). This contrasts methane, ethane and ethene being most abundant

Elucidation of the Alum Shale kcrogen structure 1047
2000-1
C1C2
1800-
1600"
1400*
1200-
1000-
Retention time (minutes)

Fig. 2. A typical 800 C flash pyrolysis chromatogram of Alum Shale kerogen. Identification of peaks:
C1C2 = methane + ethane: C4 = n-propane: CS = n-pentanc: B = benzene: T = toluene: C8 = n-octane:
STY = styrene: C3B = C3-alkvlbenzenc: S = internal standard: 2MN — 2-methylnaphlhalcnc: 1MN = 1-
mcthylnaphthalcne.
(Fig. 2 and Fig. 3a). In the oil fraction (C._). the than n-Cio in the oil fraction occur only in
pyrolysate is relatively enriched in low molecular insignificant amounts. The abundance of branched
weight compounds with aromatic hydrocarbons and cyclic alkancs/alkenes is far more conspicuous in
(mainly alkylbenzcnes and alkylnaphthalenes) occur the oil fraction than are the paraffins, although the
ring in substantial quantities (about 10-15 and former are still in far lower concentrations than the
3-6 mg/g TOC respectively: Table 2. Fig. 3b). There alkylbenzcnes (Table 2 and Fig. 2). The average
is no dominant n-alkanc-ene homology in the oil gas/oil ratio (equivalent to GOR). calculated as the
fraction: in fact, concentrations heavier than n-Cio total Ci-C< yield divided by the total C<. yield, for
were so low that accurate peak integration was not the Alum Shale pyrolysates generally is 0.50 or
possible. Hangers el al. (1994) reported the yield of higher, except for sample 7 (Table 2). This is very
alkylbenzcnes from the Kimmeridgc Blackstone high for algal Type II kerogens. which normally
Band kerogen (Type II) to be about 15 mg/g TOC yield low (~0.2) gas oil ratios from pyrolysates
using Py-GC. Type I kerogen (Guttenberg) gave a (Bharati. 1989). This consistency in the pyrolysates is
lower alkylbcnzcne yield (about 8 mg/g TOC) and a surprising, given the changes in the kerogens
sulphur-rich Type II-S kerogen (Monterey) a higher maturity levels and suggests little change in their
yield (about 18 mg/g TOC). This suggests that for chemical composition while realizing that the
Alum Shale kerogens. it is perhaps the lack of identified components represent only about 10-15%
n-alkanes/encs that is the more significant and of the TOC.
exceptional, rather than the apparent large amounts The only major change observed in the pyrolysates
of alkylbenzcnes (see Fig. 2). Other paraffins lighter is yields which decrease with decreasing kerogen
Table 2. Quantitative pyrolysis (Q-Py-GC) summary data in mg-g TOC and relative percentage (in brackets)
Sample A <%) B (%> C(%) DC/.) E (%) F<%> G (•/.) H (%) I* Je K* L* M*
1 52.0(34) 39.5(26) 9.3 (6) 8.2(5) 20.7(14) 15.1(10) 4.2 (3) 3.8(2) 99.7 23.0 107.5 188.6 0.57
2 54.1 (39) 33.4(25) 8.6(6) 5.3(4) 16.0(12) 11.6(8) 3.1(2) 5.9(4) 92.8 20.6 100.7 201.4 0.50
3 60.7(37) 41.0(25) 10.1 (6) 7.7(5) 21.7(13) 14.2(8) 4.4(3) 5.8(3) 109.4 24.4 118.2 210.7 0.56
4 54.3 (32) 41.8(25) 13.0(8) 8.8 (5) 24.9(15) 16.1 (10) 4.0(2) 4.6(3) 104.9 24.7 129.6 259.0 0.50
5 66.4(35) 53.6 28) 14.2(7) 7.0(4) 25-203) 17.0(9) 4.2(2) 4.6(2) 127.0 25.9 155.0 276.3 0.56
6 35.3 (37) 23.5(25) 6.2(6) 4.6 (5) 11.3 02) 8.6(9) 2.0(2) 3.4(4) 63.3 14.0 76.4 124.3 0.61
7 1.2(23) 0.7(14) 0.2(4) 0.2(4) 0.3(5) 1.4(25) 0.3(5) 1.1(20) 2.2 2.8 8.4 21.7 0.39
Explanation for columns: A * methane + ethane + ethene: B — n-hydrocarbons (C3-C5): C — branched hydrocarbons (gas fraction):
D ■ n-hydrocarbons (C6-C10); E-branched hydrocarbons + NSOs .(oil fraction): F - benzene + alkylbcnzcne: G»indene +
alkylindenes: H — naphthalene + alkylnaphthalenes: I — £ n-hydrocarbons (n-alkanes + n-alkenes. Ci-C10): J ■ E aromatic
hydrocarbons (benzenes + tndenes + naphthalenes): K * total gas (C1-C5): L — total oil <C6 + ): M * gasoil ratio (GOR) (kg/kg).
•Data from Bharati ei al. (1992).

a: Aliphatic, Branched and Non-hydrocarbons
mg/g TOC Gofl
□ C1C2 EC3-10n-HC 0NHC«BHC ♦GOB
b: Aromatic hydrocarbons
mgtg TOC GOB
□Al.bOT BAUnd DAl.nip *B«n A kid XNjp ♦GOB
Fig. 3. Behaviour of aliphatic hydrocarbons, non-hydrocarbons and branched hydrocarbons (top) and
aromatic hydrocarbons (bottom) resulting from the pyrolysis of Alum Shale kerogens of increasing
maturity (sample I—immature to sample 7—post-mature). Identification of species:
CIC2 " methane + ethene + ethane: C3-10 n-HC = C>w n-hydrocarbons: NHC + BHC = non-hydro-
carbons + branched hydrocarbons: GOR — Gas:oil ratio: Al.bcn = alkylbcnzcnes: Al.ind = alkylindencs:
Al.nap — alkylnaphthalenes: Ben = benzene: Ind = indenc: Nap = naphthalene.
hydrogen content, implying increasing thermal (1985) noted that alginites generate n-alkane/ene-rich
maturity. The pyrolysate composition is very unusual or in some cases mixed n-, branched or cyclic
for Type 11 algal-dominated marine kerogens, and alkane/ene-rich pyrolysatcs. Sporinites, like vitrinites,
contrasts strongly with other typical Type II marine generate aromatic pyrolysatcs dominated by alkyl-
kerogens such as the Toarcian Shales of the Paris benzenes. alkylnaphthalenes and alkylphenols,
Basin (e.g. Tissot and Welte, 1984; Bharati, 1989). whereas Type II marine kerogens generally produce
Latter and Douglas (1980) and Latter and Senftle long chain n-alkanes/enes (Latter and Senftle, 1985).

Elucidation of the Alum Shale kerogen structure 1049
Nevertheless, type II kerogens can be chemically

heterogeneous such as those from Kimmeridge Clay.
Antrim. Tasmanian Cannel Coal and Penetang
(Tegelaar and Noble. 1994). Alum Shale kerogens.
which are type II on other criteria (e.g. Rock-Eva!
data) and which are rich in petrographically defined
alginite. produce gas/condensate and aromatic
hydrocarbon-rich pyrolysates from open system
pyrolysis (Fig. 2. Table 2). This accords with previous
data for an immature Alum Shale kerogen (sample 1
of this study) which, when subjected to micro-scale
artificial maturation, generated hydrocarbons similar
in chemical composition to the flash pyrolysates
(Horsfield et al.. 1992).
NMR Spectroscopy
for explanation of symbols)
The list of the various carbon types, their structures

and the symbols used to describe them is shown in
Appendix 1. In general, the data obtained for samples
1 and 2 (immature) and 4 (early mature) are very
similar (Table 3). All three samples have similar
degrees of aromaticity (f,). which are somewhat
higher than expected for immature or early mature"
Type II kerogens (Patience et al.. 1992). The only
I
slight difference between the three is that sample 1 has

Tabic 3. NMR data for selected Alum Shale kerogens (see Appendix
higher relative abundances of ArCC (branched

aromatic moieties).
Sample 7 (post-mature) gave no NMR signal
implying that the structure is so highly condensed
("graphitized"). that there are no protons sufficiently
close to a l5C atom for cross-polarization to be
effected.
Oxygen-containing carbon types (C = O, COOR,
ArCO, CHO and CHxO). The relative abundances of
the above carbon types (Table 3) are higher compared
to other "aquatic" (lacustrine or marine) kerogens
with similar f. values (Mann et al.. 1991; Patience
et al., 1992). This is especially true of C = O, COOR,
CHO and CHxO. which is unusual (ArCO is about
average). Other kerogens often have one or two
carbon types in greater abundance (e.g. CHO and
CHxO in aquatic kerogens, ArCO for coals, COOR
and ArCO for inertinitic kerogens—Patience, unpub
lished results), but the Alum Shale samples arc the
only samples to have been analyzed where all the
oxygen-containing carbon types are so abundant. As
i a result, O/C ratios based on NMR data are also
elevated (Table 4). In general, an increase in the O/C
2352 I ratio will reduce petroleum potential even if f.
remains constant (Miknis et al., 1982). This high
oxygen content cannot be attributed to oxidation of
SSS-- I
a the organic matter during deposition or weathering
since fresh pyrite was observed during petrographic
analyses (Bharati, 1989).
*333 i Aromatic carbon types (ArCC, ArCsC, ArCff).
I? Kerogens 1,2 and 4 have aromatic structures which
more closely resemble those of coals in NMR terms
(with ArCH > ArCC) (Table 3) than algal/bacterial
kerogens deposited in aquatic environments
(ArCC & ArCH) (Mann et al., 1991; Patience et al.,


Table 4 Elemental dau for the kerogen samples from chemical shift data, thus a number of ratios
Sample HC oc H C: Aliphatic carbon have been calculated (Table 3). in order to infer
1 1.1(1 0.15* 1.05 82.9 support for rings or chains. The ratios (Patience
2 1.26 0.155 1.01 68.1
4 1 13 0.166 0.9$ 41.2 et at.. 1992) are explained below.
6 1.01 0.114 0.76 364 CH; CH*al: this is the sum of all methylene groups
n.d. n.d 0 0$ 0 divided by the methyl groups attached to other alkyl
n.d = no dau. Ratios from NMR data.- From elemental analysis carbon atoms (i.e. the methyl in toluene would not be
(after Horsfield et at.. 1991). mg g rock (calculated! (after included here, but comes under CH-ar). This gives an
Horsficld et at.. 19911.
approximate idea of chain length (in qualitative terms
only) as the higher the value, the longer the average
1992). even though a terrestrial source is impossible chain length is likely to be. Unfortunately, it can also
given their age and given petrographic observations mean a high proportion of ring methylenes, not chain
of abundant alginites (Bharati and Latter. 1991). methylenes. It is subject to measurement error, since
However, they do not have the high ArCO values CH.al is usually small and the smaller the value, the
(5-10%) [see above] associated with coals (Mann higher the relative error.
ei a!.. 1991). CH:r CH;m: this is the ratio of rigid (CH.-r) to
Sample 6 (late mature) differs from the above 3 mobile (CH;m) methylenes (in NMR terms). All
samples in that it has a much higher f, value (Table 3) cyclohexyl ring methylenes are rigid, as are many
and higher ArCAC and slightly higher ArCH values chain methylenes, the latter depending on the mode
indicating that the aromatic structure is relatively of "packing" of the chains, or on chain length (shorter
more condensed and less alkylated. Despite this chains, especially cross-links, are more likely to be
increased condensation. ArCH is still greater than rigid). Therefore, an increase in this ratio can mean
ArCAC. and the aromatic structure is not as either an increase in rings relative to chains or a
condensed as "normal" aquatic kcrogens (Fig. 4). In different packing arrangement for the chains, or
fact, samples 1. 2 and 4 have aromatic structures shorter/cross-linking chains.
which are similarly condensed to coals, whilst sample CH;rnvCH;{C2): this is the ratio of rigid and
6 is intermediate between coals and "normal* aquatic mobile methylenes (CH-rm) relative to methylene
kerogens (Fig. 4 and Mann ei al.. 1991). Otherwise, adjacent to a terminal methyl (CH=(C2)). This should
sample 6 differs from other aquatic kerogens in give similar information to CHi/CHjal. It is also
exactly the same ways as the less mature Alum Shales subject to error in that CH:(C2) can have a small
(see below). value.
Alkyl carbon types (C. CH. CH;. CH>ar and CH.ICH: The ratio of methylenes to methines will
CHtal). In all of our kerogens analyzed to date, the be low when the kerogen contains either abundant
dominant alkyl carbon type is CH;. In this respect, acyclic isoprenoids or other branched chain com
the Alum Shale kerogens do not differ from the other pounds. or abundant fused alicyclic ring systems (e.g.
aquatic kerogens (Table 3). NMR cannot distinguish steranes.'hopancs). In both cases, it indicates a
between acyclic ("chain") and alicyclic ("ring") carbons reduction in the relative abundances of n-alkanes.
For the Alum Shale kerogens. the two parameters
with consistently large differences compared to other
S*mpi$ Type aquatic kerogens are CH-r/CH:tn (very much higher)
lets B inert * Alum Shales and CH:/CH (much lower) (Fig. 5). These trends are
internally consistent, although there is more than one
explanation for the differences. Firstly, the Alum
Shale kerogens could be enriched in rigidly packed
branched chain compounds (this would explain both
ratios); secondly, there could be a greater abundance
of fused alicyclic (ring) compounds (this also explains
both ratios); thirdly, there may be shorter and/or
cross-linked chains (rigidimobiie ratio goes up)
combined with either of the first two possibilities.
These possibilities will be discussed later in the light
AromebeHy (It) (%} of the data from chemical degradation.
In summary, the four Alum Shale kerogens
Fig. 4. Degree of aromatic ring condensation (ArCAC.'fa)
versus aromaticity (fa) for the Alum Shale kerogens and analysed 1, 2, 4 and 6 are unique. Compared to
other representative kerogen types. The dotted line is the "normal" aquatic kerogens, they have higher than
linear regression trend for the aquatic kerogens. the thin average O/C ratios (Table 4) and higher concen
solid line for coals and the dashed line for the inert kerogens. trations of oxygen-containing functional group
Note that the Alum Shales (solid stars) plot at or near the concentrations (except ArCO). The aromatic struc
regression trend for coals. Data considered for aquatic
kerogens. coals and inert kerogens are unpublished ture resembles that of coals, i.e. a greater abundance
(Patience). of protonated rings and less ring junction carbon.

Rim Chemical degradation

Chemical degradation was used to obtain struc
tural information on the aliphatic portion of the
kerogens. Oxidative degradation converts the kero
gen into soluble, identifiable and structurally
significant fragments, the amount of conversion
depending on the inherent properties of individual
kerogens. Generally, an oxidizing agent attacks
kerogen at. or next to. carbon atoms bearing a
functional group. Oxidation of kerogen with RuO,
results essentially in (1) degradation of aromatic rings
(toluene for instance will convert into acetic
acid + CO:). (2) Conversion of alcohols into alde
Ktogtn Typ• hydes. ketones or acids (depending on the position of
Fig. 5. Relative abundances of CH:r'CH:m and CH.-'CH in the OH group). (3) Conversion of aldehydes into
the Alum Shale Icerogens (average of samples 1. 2.4 and 6) acids. (4) Conversion of alk-l-enes into aldehydes
and other representative kerogen types based on NMR and,or ketones. However, aliphatic and alicyclic
analysis. Aquatic kerogens represent Types Id-11: coals portions remain intact. Acids are therefore the most
represent Type III kerogen: inert material represents Type
IV kerogen. Data considered for aquatic kerogens. coals and important products from the point of view of kerogen
inert kerogens is unpublished. structure reconstruction. These reactions have been
reviewed by Standen (1992).
In the present study, a total of 91 compounds were
except that the Alum Shales' phenolic content (and identified and quantified after RuO, oxidation: they
the degree of aromaticity) is too low for coals. The accounted for roughly 99% of the total integrated
alkyl structure is characterized by an unusual peak area. A typical chromatogram is shown in
combination of mostly rigid methylenes, which are Fig. 6. The quantified data normalized to TOC
present in lower than normal abundance relative to and also in relative percentages are presented in
‘branching" (ring or chain) carbons (CH). The fifth Table 5 and graphically in Fig. 7 for the seven
sample (sample 7) is so graphitizcd that no direct Alum Shale kerogens. Identification (Table 6) of
structural information could be obtained. individual acids and their isomers was achieved using
2- 400-
Retention time (minutes)

Fig. 6. A typical chromatogram (expanded along the time axis to show the major jieaks) of the
organic material resulting from ruthenium tetroxidc oxidation of the Alum Shale kerogens. Identification
of peaks: I = methylpentanoic acid. 2 = hexanoic acid. 3 = butanedioic acid. 4 - methylbutanedtoic
add 5 = pcntanedioic add + octanoic add. 6 = dimethylbutanedioic add. 7 = methylbutanedtoic acid.
8 - nonanoic add. 9 = hcxanedioic add. 10 = mcthylhexancdioic acid. 11 = hcptancdioic
add. 12 = methylheptancdioic acid. 13 = octanedioic add. 14 = nonanedioic acid. 15-decanedioicacid.
16 = undccanedioic add + pristane. 17 = hcxadccanoic add (palmitic add) and 18 = octadecanoic
add (stearic add).

Table 5 Abundance of compounds liberated b> the ~ Alum Shale kerogens b> RuOl otidalion Values in both mg g TOC and *» lin brackets i
NMA BMA NDA BDA ARA ALI
Sample mg g TOC Co) mg g TOCCo) mg g TOC Col Ratio 1 Rauo 2 Ratio 3 Ratio 4 Ratio 5
1 2".l (14) 16.0(08) 66 4(35) 68.6(37) 5." (3) 3.5 (2) 0.41 1.70 0.97 0.29 0 19
16.4(14) 10.1 (08) 40.6 (34) 44.5(3") 4.9 (4) 2.9(2) 040 1.61 0.91 0.29 0 19
3 25.3(131 1".2(I0) 57.8(33) 65 9(3") 6.5(4) 3.7(2) 044 1.4? 0.88 0.30 0.21
4 19.9(15) 13.7(10) 48." (36) 45.3 (33) 54(4) 2.4(2) 0.41 1.45 1.0" 0.29 0.23
< 22.4(15) 16 " (11) 38.9(26) 58.5(40) -"(<) 3.1 (2) 0.58 1.34 0.66 0.3" 0.22
6 23.6(1") 20.0(15) 364(26) 48.3(35) 3.3 (2) 5.4(4) 0.65 1.18 0 75 0.39 0.29
14.61351 9.5(22) 8.1 (19) 6.6(16) 1.0(2: 2 1 (5) 1.79 1.53 1.22 0.60 0.59
Explanation for columns: NMA « normal monocarboxs lie acids: BN1A - branched monocarboxvlic aads lalll: NDA = normal dicarboxxlic
acids. BDA - branched dicarbovlic acids lalll. ARA = alkxl mono-aromaiics IDA and TA1: ALI = normal alkanes, ratio
I = NMA NDA: ratio 2 = NMA BMA: ratio 3 = NDA BDA. ratio 4 = NMA NMA 4- NDA: ratio 5 = BMA BMA - BDA
target compound analysis (TCAl and reverse library product. Differences between the samples with
search of GC-MS data (Boucher et al.. 1990). All the respect to the relative distribution of constituents are
compounds fall in six major categories, which are: I) insignificant apd no major change in the trend is
normal monocarboxylic acids (NMA). 2) branched observed between branched monocarboxylic acids
monocarboxvlic acids (BMA). 3) normal dicarboxylic substituted with one. or two. methyl groups with
acids (NDA). 4) branched dicarboxylic acids (BDA). increasing maturity.
5) monoaromatic di- + tricarboxylic acids (ARA) Normal dicarboxylic acids (NDA). These com
and 6) normal aliphatic hydrocarbons (ALI). pounds. resulting from chemical degradation of the
All samples yielded similar constituents in compar Alum Shale kerogens are second in abundance
able proportions, suggesting consistency in the (generally 26-35%) (Table 5). Despite their greater
aliphatic portion of Alum Shale kcrogens. irrespec abundance with respect to the monocarboxylic acids,
tive of location: this accords with the lack of variation the two are similar, in that the NDA distribution is
in the pyrolysates. Clearly, four of the categories also characterized by relative high abundances of low-
NMA. BMA. NDA and BDA dominate the molecular weight diacids ( < Ci2). in contrast to other
products, accounting for more than 90% of the total marine kerogen samples. Additionally, except for an
yield (Table 5). Amongst these four acid types, the apparent fall in the yield, there is no other major
dicarboxylic acids and especially the branched difference between the samples of varying maturity
dicarboxylic acids, occur in greater quantities in (Table 5). Another striking feature of the distribution
nearly the entire maturity range (Fig. 7). Only in the is the sharp fall in the yield of NDAs longer than C»
post-mature sample (sample 7). are the two (Fig. 8c). indeed, those with 10 or more carbon atoms
monocarboxylic acids. NMA and BMA. more occur in insignificant quantities compared to the
abundant. lighter counterparts. Pentanedioic and hexanedioic
Normal monocarboxylic acids {NMA). This group acids (peaks 5 and 9 respectively in Fig. 6) are the
of compounds typically represent 13-17% of the total predominant NDA's.
acid product. Their distribution (Fig. 8a) is typically Branched dicarboxylic acids (BDA). These are
characterised by relatively high abundances of low important compounds, as far as the chemical
molecular weight acids (derived from < Ci: alkyl degradation of the Alum Shales is concerned, and
chains), compared to other marine kerogens plus occur in largest quantities—typically 33-40% of the
abundant palmitic and stearic acid. There is a sharp total content (Table 5). In samples 1. 2. 3 and 4, the
fall in abundance of NMAs with more than 9 carbon relative concentrations of BDA and NDA are
atoms, after which there is an even-carbon number comparable: their distributions, and changes due to
predominance. The distribution of components in the maturity, arc similar to other acid fractions i.e. BDAs
NMA group is comparable in all samples, irrespective too are characterized by low molecular weight
of maturity (Fig. 8a). compounds, with very few differences between the
Branched monocarboxylic acids (BMA). The samples (Fig. 8d). Methylbutanedioic acid (peak 4 in
distribution of branched monocarboxylic acids Fig. 6) consistently occurs in largest quantity in all
(Fig. 8b) is very similar to that of NMAs in that it the samples, except in sample 7. A significant feature
is characterized by relatively high abundances of low of the BDA distribution is that compounds with a
molecular weight acids (C,-C«) compared to other methyl branch are at least twice as abundant as their
marine kerogens. No BMA was detected with more dimethyl (or ethyl) counterparts (e.g. methylbutane
than 9 carbon atoms in a chain. Methylpcnianoic dioic acid » dimethylbutanedioic acid and so on)
acid is the most abundant acid, with one of the (Fig. 8d). However, the overall abundance of both
isomers being prominent (more than 50%) (peak 1 in methyl- and dimethyl branched acids systematically
Fig. 6). A striking feature is that the abundance of falls with increasing carbon number.
methylpcnianoic acid seems to increase with increas The normal aliphatic hydrocarbons (ALI) and the
ing maturity (Fig. 8b), suggesting that a pentyl chain monoaromatic di- and tri-carboxylic acids (ARA)
may be relatively a more important generation comprise about 2-5% and 5-7%, respectively

Mi* Bi* NO* B* «*0 *Ut Bit BU SOI lOi

*e»7fc»
TOC
Mi*Bi*NO*BW*mO*lKBilBi2B)l KB
HO* BJA *HO *Ut Bil
AdiTjf
m&BTOC
, BOA AHO ALK MM MC *01 *0*

AcHTyp*
Fig. 7. Absolute yields in mg/g TOC of the principle add types in the 7 oxidized Alum Shale kcrogens.
Abbreviations used are: NMA = normal carboxylic adds: BMA = branched carboxylic acids;
NDA * normal dicarboxylic adds; BDA = branched dicarboxylic adds; ARO = alkyl mono-aromatics;
ALK = normal alkanes: BM l » mono-alkyl monocarboxylic adds; BM2 = di-alkyl monocarboxylic
acids; GDI = mono-alkyl dicarboxylic acids; BD2 =* di-alkyl dicarboxylic acids. Hatched bars indicate
acid types which are not discussed separately in the text.

Table 6. List of branched monocarboxvlic and dicarboxxlic acids isomers identified and quantified using TCA
and reverse library search, during RuO* oxidation of Alum Shale kerogens Normal acids detected and
identified are not listed below, but monocarboxvlic acids ranged from hexanoic through hexacosanoic acids
and dicarboxxlic acids ranged from butanedioic through hcxadecancdioic acids. (For an explanation of
abbreviations of the parent groups, refer to Fig. 8)
Parent Group Isomers
Branched nwnoiurhuwhc acids IBM A i
Mec; 2-. 5- and 4-methvlpentanoic acid
ElC5 2-cthxlpentanoic acid and 1 unspecified
DiMcC5 2.2-. 2.4. and 3.5-dimeihylpcntanoic acid
MeC6 2* and 3-methvlhexanoic acid and 1 unspecified
DiMeC6 2.4- and 3.3-dimethylhexanoic acid
DiMeC 2.4- and 3.3-dimcthylheptanoic acid
DiMeCS 2.6-dtmeihyloctanoic acid
DiMcC9 2.6-dimcthx Inonanoic acid
Branched dicarho.whc acids (BDA l
McC4 3-methylbutanedioic acid
DiMeC4 2.2-dimethylbutanedtoic acid and 1 unspecified
MeC5 3 and 2-methylpentanedioic acid
DiMeCS 3.3- and 2J-dtmethylpentanedtoic acid and 1 unspecified
MeC6 2- and 3-methx Ihexanedioic acid and 1 unspecified
DiMeC6 2.4- and 3.3-dimethvlhexanedioic acid
MeO 2-. 3-. 4- and 5-methylheptanedioic acid
DiMeC? 3.4-dimethylheptanedioic acid
MeC8 2- and 3-methx loctanedioic add and 1 unspecified
(Table 5) of the total oxidation products and are not coherent, general picture of the chemical composition
believed to be of any significance. Only normal of the Alum Shale kerogens. both at immature and
C.o-Cii (not Cu) alkanes were identified and more mature stages.
quantified. At the relatively immature stage represented by-
In summary. RuO, oxidation data provides the sample 1. ”C NMR data show that the kerogen has
following information: (a) the structures released are a higher degree of aromaticity (f, = 44.5%). com
predominantly of low molecular weight, whether pared to normal marine kerogens (f, = 27 to 33%:
normal or branched compounds: (b) dicarboxylic Patience et al., 1992). Furthermore, both NMR and
acids arc more abundant than monocarboxylic acids: Py-GC (open and closed systems) analyses indicate
(c) the branched acids arc relatively abundant that the aromatic part of the structure consists largely
compared to the normal acids and the carbon number of monoaromatic and to a lesser extent diaromatic
distribution is not compatible with an origin from moieties (the former nearly twice as abundant than
fused cyclohexylaromatic compounds: (d) the distri the latter). The solvent extracts are also relatively
butions of compounds within the four compound enriched in aromatic hydrocarbons (Bharati, 1989).
classes show distinct (not readily explicable) patterns, NMR also demonstrates that the kerogen contains
which change little as the samples become increas an unusually high proportion of carbon atoms
ingly mature: (c) the relative abundance of the bonded to oxygen (C = O, COOR, CHO and
dicarboxylic acids as a group decreases with sample CHxO. particularly the latter two) and that these
maturity unlike the monocarboxylic acids: (f) no elements represent an atypical distribution of
cyclic acids were identified: (g) no acyclic isoprenoid oxygen-containing functional groups, not attribu
acids were identified; (h) the distributions observed table to oxidation of the organic matter during
are somewhat atypical as compared to other marine deposition or by weathering at outcrop. In addition.
kerogens analyzed previously (Standen. 1992): (i) the ArCH species are more abundant than ArCAC,
average yield of identifiable components is about implying benzenoid structures are more abundant
15% with respect to TOC, indicating only partial than naphthalenes. Surprisingly, given the deposi-
kerogen degradation. tional model for the Alum Shale (low sedimentation
rate in an epicontinental basin. Thickpenny, 1987),
no sulphur-containing compounds were found in the
DISCUSSION
pyrolysates.
The aliphatic part of the structure of sample 1
Chemistry of the Alum Shale kerogens consists (from chemical degradation, NMR and
The data presented above and elsewhere (Bharati, Py-GC) of short, n- and branched alkyl chains
1989: Bharati and Larter. 1991; Bharati et at., 1992 (typically 1-6 carbon atoms but generally not
and Horsfield et al., 1992), derives from various exceeding 10 carbon atoms). A high proportion of the
techniques, namely: three pyrolysis methods (Rock- aliphatic chains appear to be cross-linked as the
Eval, flash pyrolysis-GC and closed vessel pyrolysis); abundance of branched components is much higher
extract analysis: fluorescence microscopy; solid state than in normal marine kerogens, although acyclic
"C NMR and ruthenium tetroxide oxidation. This isoprenoid structures are much reduced. The low
section attempts to integrate these data to give a more abundance of longer chain n-alkyl acids indicates

Elucidation of the Alum Shale kerogen structure
MeCS OUMCS OU«C7 OiUtCa OWC9

BtenebeP AaP Type
Acid Type fCeroon Number!
McC4 OiMdOA M.CS OUtoCS M.C8 CKUCS M»C7 IXU.C7 UeC»

Brtnched Add Type
Add Type (Csrbon Number)
Fig 8. Relative abundances of major individual species of (a) normal monocarboxylic adds (NMA). (b)
branched monocarboxylic adds (BMA). (c) normal dicarboxylic adds (NDA) and (d) branched
dicarboxylic adds (BDA). Note the high abundance of palmitic add and stcanc acid m the NMA figure.
Explanation of abbreviations in the branched add types: Me, El and DiMc stand for methyl, ethyl and
dimethyl respectively and indicate the type of alkyl group attached to the acid. C5. <-6. C7. t-8 ana ty
represent the length of the carbon chain m the parent ion. So MeCS would mean mcthylpentanotc acid.
For the number of isomers in each of the branched add types, see Table 6.
why n-alkanes/cnes are not generated in significant escence to no visible range fluorescence without the
amounts on pyrolysis. The chemistry of sample 1 is, orange/dark orange transition (Bharati and Latter,
therefore, completely atypical of other marine 1991)), and closed vessel pyrolysis, where ‘inert’
kerogens, even though fluorescence studies show kerogen (i.e. non-convertible by Rock-Eval and flash
abundant well-preserved algal organic matter with Py—GC) appeared to be formed in substantial
‘characteristic* yellow fluorescence. Although proportions (Horsfield et al., 1992). The small
samples 2 and 4 are more mature than sample 1 proportion of aliphatic structures in the immature
(Bharati and Latter, 1991), their chemical structures Alum Shale kerogen remains essentially unchanged
are to all intents and purposes, similar to that of the with maturation, in that its yield from pyrolysis and
latter. chemical degradation remains near constant irrespec
The more mature sample 6 shows a relatively small tive of the sample’s maturation state.
increase in aromaticity compared to samples 1,2 and Overmature sample 7 appears to consist entirely of
4, from NMR analysis, but the flash pyrolysates are inert kerogen, with a sufficiently hydrogen-depleted
qualitatively similar. However, there appears to be a structure such that no data could be obtained from
significant increase in aromatic ring condensation NMR and very little from pyrolysis. This also helps
during maturation, as suggested by Horsfield el al. to support the concept of a kerogen structure
(1992). This is also demonstrated by NMR data, containing mono- and diaromatic rings when
fluorescence microscopy (conversion of yellow fluor immature, but which subsequently condenses on

thermal maturation. Only the peripheral and recognizable maccrals. However, our present under
non-fused kerogen sub-structures may then continue standing of marine algae, from the point of view of
to generate (the same distribution of) products. kerogen geochemistry is largely based on post-Cam
These observations lead us to propose that the brian shales. Possibly the chemistry of the biota that
dominant features of the Alum Shale kerogen existed in the Cambrian sea in which Alum Shales
macro-molecule (KMM) include (a) fairly abundant were deposited was highly unusual, unparalleled in
primary mono-aromatic rings (f„ = 42-57%). linked subsequent geological epochs, as suggested earlier by
together in such a way so as to result in "easy" Bharati and Latter (1991). These shales were
condensation, (b) an aliphatic structure consisting of deposited in very stable conditions and have not
short branched alkyl and to a lesser extent n-alkyl experienced any major tectonic movements, except
chains, (c) high proportions of oxygen occur in the perhaps on a minor scale in the Oslo region. They
form of aliphatic alcohols, ethers and some esters and have not been deeply buried and arc thought to have
carboxyl compounds. These three principle types are been at or near the surface through geological times
believed to be linked together to form the KMM. (Andcrsson et al.. 1985: Thickpenny. 1987). The
such that short alkyl chains arc perhaps linked, via sediments probably originated from the surrounding
ether or ester groups. This possibility seems to satisfy metamorphicvolcanic areas which were rich in
most of our data. metals, especially uranium which is present in the
The similarity of the data obtained using different Alum Shales in anomalously high concentration (up
analytical methods, irrespective of the location and to several hundred ppm) (Andcrsson et al.. 1985:
maturity of the sample in an estimated 2000 sq.km. Lewan and Buchardt. 1989: Bharati. 1989: Buchardt
Alum Shale basin, suggests that the KMM consists of and Lewan. 1990). Lewan and Buchardt (1989)
chemically similar sub-units from the periphery to the suggested that the organic matter in the Alum Shale
core. With progressive thermal degradation, part of is damaged due to radiation, and that radiation has
this sub-unit is released and the remainder undergoes caused intense cross-linking of alkyl chains. How
internal reorganization such that the initially ever. Horsfield et al. (1992) found no good
‘producible" (labile) components ultimately become correlation between Alum Shale kerogen properties
involatile, an observation made during simulated and uranium contents suggesting radiation damage
maturation of the least mature Alum Shale kerogen was not the sole factor.
(Horsfield et at.. 1992). Ring condensation, and an Some of the results of this study (high abundance
increase in aromaticity, are perhaps processes closely of cross-linked short alkyl chains, low abundance of
associated only with late/extreme maturation in the long n-alkyl chains) may be explained by the
case of the Alum Shales, in contrast to other marine radiation hypothesis, while several others (high
sediments (Patience et at., 1992). While oxidation and oxygen content, absence of thiophenes, high aro
pyrolysis indicate minor chemical changes prior to maticity. extensive formation of "dead" carbon on
the onset of high maturity, petrography indicates maturation) are perhaps due to the unusual chemistry
distinct progressive physical changes, such as an of the Alum Shale algae and its subsequent diagenesis
increase in bitumen reflectance and decrease in (Bharati and Latter. 1991 and Horsfield et al.. 1992).
alginite fluorescence intensity. Interestingly, the overall pyrolysatc composition of
Pelet (1980) has suggested that a major part of a the Cerdanya kerogen from the Tertiary Catalan
kerogen's oxygen is lost during diagenesis, while the lacustrine oil shale as reported by Sinninghe Damstc
hydrogen content mainly decreases during the et al. (1993) and Hangers et al. (1994). is remarkably
catagenesis stage. However, the data obtained for the similar to the Alum Shale pyrolysatc composition.
Alum Shale kerogens suggest that most of the Due to only minor differences observed in the
oxygen remains intact within the KMM. even as alkylbenzene distribution in Cerdanya and Alum
products are generated and expelled with increasing Shale pyrolysates. Hangers et al. (1994) deemed it
maturity. This is unusual, keeping in mind the unlikely that radiation-induced aromatization played
chemical models suggested for Type I. II and III an important role in the development of Alum Shale
kerogens by Behar and Vandenbroucke (1987). It kerogen. On the other hand, the existence of biota
seems that with increasing maturity, the overall with unique and/or unexplained compositions (aro
chemistry of the Alum Shales and sub-unit structures matic biopolymers) has been observed, as for the
remains the same, except for the more condensed freshwater algae Pediastrum (Sinninghe Damste
nature and reduced size of the individual building et al.. 1993) and Gloeocapsomorpha derived alginite
blocks. (Fowler, 1992). Thus, the precursors of Alum Shale
alginite might have been markedly different in
Possible origin and fate of the Alum Shale kerogens composition from those in other Cambrian seas, or
Perhaps these differences between the Alum Shale in later geological periods. In any case, this study
and "typical" Type II kerogens relate to the origin of presents other chemical peculiarities associated with
the former. Given the Cambrian age of the Alum the Alum Shale kerogen which are not readily
Shale, a terrestrial organic contribution can be ruled explained by Lewan and Buchardt's (1989) hypoth
out. Marine algae are the only petrographically esis.

Elucidation of the Alum Shale kerogen structure
Buchardt B. and Lewan M. D. (1990) Reflectance of

CONCLUSIONS
utnnitc like macerals as a thermal maturity index
The Alum Shale kerogen has been shown to be in the Cambro-Ordovician Alum Shale of Southern
unusual with respect to composition and maturation Scandinavia. AAPG Bull. 74, 394-406.
Dahl J.. Hallberg R. and Kaplan 1. R. (19881 Effects of
products, but it must be borne in mind that our irradiation from uranium decay on extractable organic
knowledge and data about classical 'Type II" matter in the Alum Shales of Sweden. Org. Geochem. 12.
kerogens. and alginites. is largely based upon 559-571.
post-Ordovician (.generally Mesozoic) land-plant Dahlman B. and Gee D. G. (19*7) Ovcrsikt over
organic matter, the only exception being the Billingen-Falbvgdens geologi. bil.l i Betonkande ai
Billingenutredningen-Statensoficntliga utredmnar 1977.4".
Ordovician kukersites. Results of the present study 219-255. Stockholm, lndustndepartcmentct.
suggest to us the possibility that the principal Espitalie J.. Laporte J. L.. Madoc M.. Marquis F..
biological input to the Cambrian Alum Shales is Lepat P. and Pavlet J. (1977) Mcthodc rapide de
different from that of 'normal" alginites because of caractcrisation des roches meres, de leur potential
petrolier et de leur degre d evolution. Inst. Fr. Pet. Ret.
the gross amount, and composition, of the generated
32. 23-43.
petroleum. While some aspects of the kerogen Fowler M. G. (1992) The influence of Gloeocapsomorpha
structure may be explained by radiation damage of pr'tsca on the organic geochemistry of oils and
the primary organic matter, several other features are organic-rich rocks of Late Ordovician age from Canada.
probably related to an alternative chemistry of the In Early Organic Evolution: Implications tor Mineral and
Energy Resources (Edited by Schidlowski M.) Spnnger-
biota (algae) that existed in the Alum Shale basin Verlag. Berlin. 336-356.
during Cambrian times. Hangers W. A.. Sinninghe Damste J. S. and De LceuwJ. W.
This study also demonstrates the need to develop (1994) Geochemical significance of alkylbenzene distn-
further analytical techniques, particularly related to butions in flash pyrolysates of kerogens. coals
and asphaltenes. Geochim. Cosmochim. Acta 58. 1759-
high resolution optical methods, selective kerogen
1775.
pruning and ways to isolate pruned fractions for Horsfield B.. Bharati S.. Lamer S. R.. Leistner F.. Littkc R..
further chemical characterisation. Only then can Schenk H. J. and Dypvik H. (1992) On the atypical
more 'complete' data on kerogens be generated to petroleum generating characteristics of alginite in Ihe
enable us to derive any viable and true structural and Cambrian Alum Shale. In Early Organic Evolution:
Implications for Mineral and Energy Resources (Edited by
molecular models of the kerogen macro-molecule. Schidlowski M.) Springer. Berlin. 257-266.
Lamer S. R. and Douglas A. G. (1980) A pyrolysis-gas
Associate Editor—J. S. Sinnmghe Damste # chromatographic method for kerogen typing. In
Advances in Organic Geochemistry 1979 (Edited by
Acknowledgements—SB thanks Professor H. Dypvik Douglas A. G. and Maxwell J. R.) Pergamon Press.
(Department of Geology. University of Oslo) for providing London. 579-584.
the samples. SB and SL thank BP Norway for financial Lamer S. R. and Douglas A. G. (1982) Pyrolysis methods
support. GS thanks BP and NERC for a CASE studentship. in Organic Geochemistry: An Overview. J. Anal. Appl.
Walter Michaelis and an anonymous referee are thanked for Pvrolvsis 4, 1-19.
suggestions to improve the quality of the paper. Lamer S. R. and Senftle J. T. (1985) Improved kerogen
typing for petroleum source rock analysis. Nature 318,
277-280.
REFERENCES Lewan M. D. and Buchardt B. (1989) Irradiation of organic
Andersson A.. Dahlman B.. Gee D. G. and SnSlI S. matter by uranium decay in the Alum Shale. Sweden.
(1985) The Scandinavian Alum Shales. Swedish Geo. Geochint. Cosmochim. Acta 53, 1307-1322.
Survey 56 Mann A. L.. Patience R. L. and Poplctt 1. J. F. (1991).
Behar F. and Vandenbroucke M. (1987) Chemical Determination of molecular structure of kerogens using
modelling of kerogens. Org. Geochem. 11, 15-24. ”C NMR spectroscopy: I. Effects of variation in kerogen
Bharati S. (1989) Physical and chemical evolution of source type. Geochim. Cosmochim. Acta 55, 2259-2268.
rocks and source rock kerogens of algal origin. Cand. Miknis F. P.. Netzel D. A.. Smith J. W.. Mast M. A. and
Scient. thesis. Dept, of Geology. University of Oslo. Marie! G. E. (1982) " C NMR measurements of the
310 pp. genetic potential of oil shales. Geochim. Cosmochim. Acta
Bharati S. and barter S. (1991) Origin, evolution and 46, 977-984.
petroleum potential of a Cambrian source rock: Mycke B. and Michaelis W. (1986) Molecular fossils from
Evidences from an organic petrographic study. In Organic chemical degradation of macromolccular organic matter.
Geochemistry—Advances and Applications in the Natural In Advances in Organic Geochemistry 1985 (Edited by
Environment (Edited by Manning D. A. C.). Manchester Leythaeuser D. and Rullkotter, J.) Pergamon. Oxford,
University Press. U.K.. 141-143. 847-858.
Bharati S.. Latter S. and Horsfield B. (1992) The unusual Oberlin A.. Boulmier J. L. and Durand B. (1974) Electron
source potential of the Cambrian Alum shale in microscope investigation of the structure of naturally and
Scandinavia as determined by quantitative pyrolysis artificially metamorphosed kerogen. Geochim. Cos
methods. In Generation. Accumulation and Production of mochim. Acta 38, 647-649.
Europe's Hydrocarbons II. Special publication of the Oberlin A.. Boulmier J. L. and Villey M. (1980) Electron
E.A.P.G. (Edited by Spencer A. M.) Springer (Heidel microscopic study of kerogen microtexture. Selected
berg) 103-110. criteria for determining the evolution path and evolution
Boucher R. J.. Eglinton G.. Robinson N. and Standcn G. stage of kerogen. In Kerogen (Edited by Durand B.)
(1990) Analysis of trace organic compounds in Aquatic Technip, Paris. 191-241.
sediments. Analytical Proc. 27, 118-120. Patience R. L.. Mann A. L. and Poplctt 1. J. F. (1992)
Bremser W.. Ernst L.. Frauke B.. Gcrhards R. and Hardt Determination of molecular structure of kerogens using
A. (1981) Carbon-13 NMR Spectral data. Verlag-Chemie »C NMR spectroscopy: 11. The effects of thermal

maturation on kcrogcns from marine sediments. Geochim. Standen G. (1992) Carbon skeletal typing of sedimentary
Cosmochim. Acta 56. 2725-2742. organic matter. Ph D. thesis. University of Bristol. U.K.
Pclct R. (1980) Evolution gcochimique de la matierc Standen G. and Eglmton G. (1992) A much modified and
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Robin P. L. and Rouxhct P. G. (1976) Contribution des biologically derived macromolecules: Ruthenium tetrox-
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d'absorption infrarouge des kerogcncs situees a 1710. Tegclaar E. W. and Noble R. A. (1994) Kinetics of
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Rouxhct P. G.. Robin P. L. and Nicaisc G. (1980) structure of kerogen as revealed by pyrolysis-gas
Characterization of kcrogcns and their evolution by chromatography. Org. Geochem. 22. 543-574.
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Technip. Pans. 163-190. tional environment of the Scandinavian Alum Shales:
Simoneit B. R. and Burlingame A. L. (1973) Carboxylic Sedimcntological and geochemical evidence. In Marine
acids derived from Tasmanian tasmanitc by extractions Clastic Sedimentology (Edited by Leggett J. K. and Zuffa
and kerogen oxidations. Geochim. Cosmochim. Acta 37. G. G.) Graham and Trotman. 156-171.
592-610. Tissot B. P. and Welle D. H. (1984) Petroleum Formation
Sinninghc Damstc J. S.. De Las Hcras F. X. C.. van Bergen and Occurrence (second edition). Springer. New York.
P. F. and de Lecuw J. W. (19931 Characterisation of 699 pp.
Tertiary Catalan lacustrine oil shales: Discovery of Trewhella M. J.. Poplett 1. J. F. and Gnnt A. (1986)
extremely organic sulphur nch type I kcrogcns. Geocliem. Structure of Green River oil shale kerogen: determination
Cosmochim. Acta 57, 389-415. using solid state '-'C NMR spectroscopy. Fuel 55.
Solti H.. Schou L.. Krane J.. Skjetne T. and Lcplat P. (1985) 202-204.
Characterization of sedimentary organic matter using Vitorovic D. (1980) Structure elucidation of kerogen by
nuclear magnetic resonance and pyrolysis techniques. In chemical methods. In Kerogen (Edited by Durand B.)
Petroleum Geochemistry in Exploration of the Norwegian Technip. Paris. 301-338.
Shelf. (Edited by Thomas B. M. et at.) Graham and Westergard A. H. (1922) Sweden's Olenid Shales. SGU 18,
Trotman. 309-317. 241.
APPENDIX I
Description of the carbon types quantified by NMR. in terms of functionality, structure and symbol used
(Patience et a!.. 1992).
FUNCTIONALITY STRUCTURE SYMBOL
OH '.w
o
o
CARBONYL
CARBOXYL - E3-OOR/H COOR
PHENOL (6P° AlCO
BRANCHED AROMATIC AlCC
BRDGEHEAO
AROMATIC
PROTONATEO
AROMATIC
m AlC*C
AlCH
OXY-METHINE CHO
OXY-METHYLENE c-TO-o—C/H CH.0
OXY-METHYL CH.0
0
1
QUATERNARY
ALIPHATIC c-gj-c C
c
METH1NE
METHYLENE (CJ)
V
c-TO-ch,
CH
CH,(C2)
METHYLENE c-ro-c CH.
CH.ll
ALIPHATIC METHYL /CH-®
AROMATIC METHYL igr03 CH,irom

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for public defense in partial fulfillment of the requirements for

Norwegian University ofScience and Technology

Doctoral Dissertation by Sunil Bharati, 1997

6.12 Summary and conclusions 133

Norwegian University ofScience and Technology

Norwegian University ofScience and Technology

Doctoral Dissertation by Sunil Bharati, 1997

Norwegian University ofScience and Technology

Doctoral Dissertation by Sunil Bharati, 1997

Norwegian University ofScience and Technology

Doctoral Dissertation by Sunil Bharati, 1997

Norwegian University ofScience and Technology

Doctoral Dissertation by Simil Bharati, 1997

Norwegian University ofScience and Technology

Paper 8 “Elucidation of the Alum Shale kerogen structure using a multi-disciplinary

Doctoral Dissertation by Sunil Bharati, 1997

England, W. A. and Mackenzie, A. S., 1989, Geochemistry of petroleum reservoirs: Geologische

Norwegian University ofScience and Technology

Doctoral Dissertation by Sunil Bharati, 1997

Identifying diverse oil families in the Greater Ekofisk area,

Sunil Bharati, Peter B. Hall and Malvin Bjor0y

Geolab Nor, N-7002 Trondheim, Norway

5 Manuscript under submission to Marine and Petroleum Geology

Norwegian University ofScience and Technology

2.3 Samples and Analytical Methods

Doctoral Dissertation by Sunil Bharati, 1997

TommeBlen Gamma Ekofisk

Norwegian University ofScience and Technology

The GC was operated under pre-programmed temperature conditions (for saturated

2.4 Geological setting

2.5 Maturity variations

Doctoral Dissertation by Sunil Bharati, 1997

Field Well Code Type Field Well Code Type

* pre-Cretaceous, sandstone reservoired oils, ♦ most datafrom Bjor0y et al. (1994)

Norwegian University of Science and Technology

Phytane/nC18 Figure 2: Cross-plot of pristane/

Doctoral Dissertation by Sunil Bharati, 1997

Dimethylnaphthalene Ratio (OMNR) Figure 3: a) Pristane/nCn, calcu­

Dimethylnaphthalene ratio (DMNR)

68 GREATER EKOFISK OILS

Calculated Reflectance (Rc)

Norwegian University ofScience and Technology

C27 diasterane / sterane Figure 4:17a trisnorhopane / 18a

C2717a/18a hopane (Tm/Ts)

%C29 app / (aaa+app) Figure 5: %C29 aj3j8 / (aaa+

%C29 aaa 20S/20S+20R

Doctoral Dissertation by Stmil Bharati, 1997

2.6 Source facies variations

Norwegian University ofScience and Technology

Doctoral Dissertation by Sunil Bharati, 1997

d13C Aromatic Hydrocarbons Figure 7: S13C of saturated hydro­

d13C Saturated Hydrocarbons

Dimethylnaphthalene Ratio (OMNR) Figure 3: a) Pristane/nCn, calcu

d13C Aromatic Hydrocarbons Figure 7: S13C of saturated hydro