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Ziegs, V. (2013) Development of a compositional kinetic model for primary and secondary petroleum generation from Lower Cretaceous Wealden Shales, Lower Saxony Basin, Northern Germany. Master thesis, Freiberg University of Mining and Technology, Freiberg, p. 82.
Technische Universität BERGAKADEMIE FREIBERG
Development of a compositional kinetic model for primary and secondary petroleum generation from Lower Cretaceous Wealden Shales, Lower Saxony
Basin, Northern Germany
by: Volker Ziegs
Master studies in Geosciences (M.Sc.)
Freiberg University of Mining and Technology Supervisors: Prof. Dr. Brian Horsfield, GFZ Potsdam
Prof. Dr. Norbert Volkmann, TU Freiberg
Potsdam, 2013-04-29
Selbständigkeitserklärung
Hiermit versichere ich an Eides statt, dass die vorliegende Arbeit eigenhändig und nur
unter Zuhilfenahme der angegebenen Quellen geschrieben wurde.
Potsdam, den 29.04.2013
………………………
Volker Ziegs
I
ACKNOWLEDGEMENTS
First of all, I would like to thank Prof. Brian Horsfield for providing this interesting topic and
giving me the chance to write my master thesis at the GFZ Potsdam. In particular, I owe a
special thanks to Dr. Nicolaj Mahlstedt for the excellent supervision, his patience with a
never-stop-asking master student, the fruitful discussions and his exhilarating mind which
made some days easier. Further, I want to express my gratitude to Ferdinand Perssen for
technical guidance, support and for smaller or bigger hints during the lab work.
ExxonMobil is gratefully acknowledged for providing the samples.
I want to express my gratitude to Soumaya Abbassi and Stephan Reinert who shared all
the ups and downs during the process of acquisition, understanding and writing all the
new knowledge, findings and results. However, I am grateful to the whole staff team of
section 4.3., Organic Geochemistry of the GFZ for the outstandingly friendly working
atmosphere.
I deeply want to thank my parents who have never stopped believing in me, for their love,
support and encouragement in bad times, as well as my friends who have been there
when I needed them.
II
TABLE OF CONTENTS
1 INTRODUCTION .......................................................................................................................................1
1.1 Gas Shales: an unconventional petroleum system .....................................................................1
1.2 Gas Shales in the U.S. ................................................................................................................4
1.3 Gas Shales in Europe .................................................................................................................6
1.4 Aim of this thesis .........................................................................................................................7
2 REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN ...............................................................8
2.1 Tectonical setting ........................................................................................................................8
2.2 Depositional setting and palaeogeographical situation ............................................................ 11
3 SAMPLES AND METHODOLOGY ....................................................................................................... 16
3.1 Origin of data & sample set ...................................................................................................... 16
3.2 Characterization of the organic matter ..................................................................................... 17
3.2.1 Organic petrography ................................................................................................................................ 17 3.2.1 Rock-Eval pyrolysis ................................................................................................................................. 18
3.2.1.1 Immature well EX-A .................................................................................................................. 18
3.2.1.2 Late and overmature wells EX-C and EX-B ................................................................................ 20
3.3 Analytical program .................................................................................................................... 21
3.3.1 Geochemical characterization ................................................................................................................. 21 3.3.1.1 TOC / Rock-Eval pyrolysis .......................................................................................................... 21
3.3.1.2 SRA – source rock analyzer ....................................................................................................... 23
3.3.2 Thermovaporization (Tvap-GC-FID) ........................................................................................................ 23 3.3.3 Open pyrolysis (Py-GC-FID) .................................................................................................................... 25 3.3.4 MSSV (Micro-Scale-Sealed-Vessel)-closed system pyrolysis (MSSV-Py-GC-FID) ................................. 25
4 RESULTS .................................................................................................................................................. 27
4.1 Molecular characterization of generated products ................................................................... 27
4.1.1 Composition of free hydrocarbons ........................................................................................................... 27 4.1.2 Bulk chemical kerogen composition ........................................................................................................ 31
4.2 Lability of the organic matter (bulk kinetics) ............................................................................. 37
III
4.3 PhaseKinetics approach ........................................................................................................... 42
4.3.1 Phase behaviour prediction ..................................................................................................................... 43 4.3.2 Compositional description of activation energy distribution ..................................................................... 46 4.3.3 PVT analysis using phase envelopes ...................................................................................................... 48
4.4 Compositional Kinetic approach ............................................................................................... 52
4.4.1 Evolution of boiling ranges during MSSV pyrolysis .................................................................................. 53 4.4.2 The conservative evaluation approach (after Dieckmann et al., 1998) .................................................... 57 4.4.3 The refined evaluation (after Erdmann & Horsfield, 2006) ....................................................................... 59 4.4.4 The GOR-Factor model ........................................................................................................................... 61 4.4.5 Prediction to geological heating rates ...................................................................................................... 68
4.5 Implications for gas-in-place (GIP) ........................................................................................... 71
5 CONCLUSION .......................................................................................................................................... 74
5.1 Future research ........................................................................................................................ 76
6 REFERENCES .......................................................................................................................................... 77
7 APPENDIX ............................................................................................................................................... 83
7.1 Index of Appendix ..................................................................................................................... 83
IV
LIST OF FIGURES
Fig. 1 Polar shale-gas risk plot with various visual and chemical assessments of organic matter conversion or
thermal maturity (Jarvie et al., 2007) ...................................................................................................................... 3
Fig. 2 Natural gas production (in tcf) in the U.S. classified by source, from 1990 to 2040 (EIA, 2013) ................... 4
Fig. 3 Annual shale gas production of the U.S. (in tcf) for the major Gas Shale systems (EIA, 2011) ...................... 4
Fig. 4 Major shale gas plays in the U.S. showing source rocks and their related basins (www.eia.gov,
updated May, 9th
2011) ........................................................................................................................................... 5
Fig. 5 Depositional facies of the LSB in Berriasian and Barremian, from Doornenbal (2010) ................................. 9
Fig. 6 Representative burial history of the Lower Saxony Basin, from Bruns et al. (2013b) .................................. 10
Fig. 7 Palaeogeographical map of NW Germany showing the distribution of different sedimentary facies and
the area of the well location, after Elstner & Mutterlose (1996) .......................................................................... 11
Fig. 8 Fluorescing Botryococcus algae in sample G010304 (Well EX-A, depth: 923.50 m), from Rippen et al.
(submitted) ............................................................................................................................................................ 17
Fig. 9 TOC / Rock-Eval plots for well EX-A (pseudo-van-Krevelen diagram, HI vs. Tmax, S2 vs. TOC) ...................... 19
Fig. 10 TOC / Rock-Eval data (pseudo-van-Krevelen diagram, HI vs. Tmax, S2 vs. TOC) for late and overmature
wells EX-C and EX-B ............................................................................................................................................... 20
Fig. 11 Schematic configuration of a pyrolysis-GC oven used for MSSV analysis .................................................. 24
Fig. 12 Tvap-GC traces of samples from early mature (a), late mature (b), and overmature (c) wells at
different stratigraphic intervals and depths .......................................................................................................... 30
Fig. 13 Representative chromatogram of open-system pyrolysis measurement showing the predicted
composition of the first formed petroleum from immature samples of well EX-A; filled dots represent n-
alkanes, empty dots mark n-alkenes and small hexagons represent aromatic components; numbered peaks
denote chain lengths of n-alk-1-ene and n-alkane doublets ................................................................................. 31
Fig. 14 Open-system pyrolysis-GC data for typing of the molecular kerogen structure and petroleum type
organofacies of immature samples of well EX-A using the ternary diagrams of (a) Horsfield, 1989, (b)
Eglinton et al. 1990 and (c) Larter, 1984 ............................................................................................................... 33
Fig. 15 Representative chromatograms for late and overmature samples, originating from uppermost,
marine-influenced horizon of well EX-B that are affected by a “carryover” effect and stemming from lower
situated deep lacustrine depth interval unaffected by the “carryover” effect; filled dots represent n-alkanes,
empty dots mark n-alkenes and small hexagons represent aromatic components; numbered peaks denote
chain lengths of n-alk-1-ene and n-alkanes; B = benzene, T = toluene; EB = ethylbenzene, mpX = meta,para-
xylene, oX = ortho-xylene, N = naphthalene .......................................................................................................... 34
Fig. 16 Generalized reaction pathway for the formation of n-alkenes and n-alkanes in open-system
pyrolysates (after (Kiran & Gillham, 1976; Schenk et al., 1997a)) ......................................................................... 34
V
Fig. 17 Open-system pyrolysis-GC data for typing of the molecular kerogen structure and petroleum type
organofacies of overmature samples of well EX-B using the ternary diagrams of (a) Horsfield, 1989, (b)
Eglinton et al., 1990 and (c) Larter, 1984 .............................................................................................................. 36
Fig. 18 Open-system pyrolysis-GC data for typing of the molecular kerogen structure and petroleum type
organofacies of late mature samples of well EX-C using the ternary diagrams of (a) Horsfield, 1989, (b)
Eglinton et al., 1990 and (c) Larter, 1984 .............................................................................................................. 36
Fig. 19 Activation energy distribution of immature marine and lacustrine samples with frequency factor A
(1/s) ....................................................................................................................................................................... 38
Fig. 20 Computed generation rate curves and transformation ratio curves for a geological heating rate of
3°C/Ma for G010283, G010305, G010316 and G010351 ...................................................................................... 40
Fig. 21 Physical properties of representative early mature Wealden Shale samples originating from different
depositional environments plotted in Psat vs. B0 diagram (upper left), Psat vs. GOR (upper right) and GOR as
well as Psat vs. TR representing maturity (lowermost diagrams) ........................................................................... 45
Fig. 22 Activation energy distributions of four immature Wealden Shale samples with integrated
compositional information .................................................................................................................................... 46
Fig. 23 Phase envelopes of the petroleum generated primarily at different transformation ratios from the
immature Wealden Shale samples of marine (G010283) and lacustrine (others) origin, additionally showing
the PT conditions within the early to overmature wells EX-A, EX-B and EX-C ....................................................... 49
Fig. 24 Total MSSV C1+ pyrolysis yields for temperatures up to 605°C at 3 different heating rates (0.7, 2 and 5
K/min) for samples G010283 and G010351; top: Absolute yields, bottom: yields normalized to highest yield .... 53
Fig. 25 Product evolution curves of samples G010283 and G010351 at representative heating rates (5 K/min
for G010283 and 0.7 K/min for G010351) for boiling ranges C1-5, C6-14 and C15+ as well as Total C1+ yields from
closed-system MSSV pyrolysis ............................................................................................................................... 54
Fig. 26 GC-fingerprints of lacustrine sample G010351 at a heating rate of 0.7 K/min to exemplify the
compositional evolution from offset of petroleum generation (90% TR, top) to 525°C (bottom) ......................... 56
Fig. 27 (a) "Conservative approach" (based on Dieckmann et al. (1998)) vs. (b) "Refined approach" (based on
Erdmann & Horsfield (2006)), after Mahlstedt (2012) .......................................................................................... 57
Fig. 28 MSSV pyrolysis yields for bulk petroleum (C1+), primary oil (C6+) and Total gas as well as calculated
primary and secondary gas, normalized to the maximum C1+ yield. The approximated spline functions for the
respective compound classes and boiling ranges are derived from open-system SRA measurements for the
marine and lacustrine Wealden Shale samples exemplified at heating rates of 0.7 K/min using the
conservative approach of Dieckmann et al. (1998) and 5 K/min using the refined approach after Erdmann &
Horsfield (2006) ..................................................................................................................................................... 60
Fig. 29 Measured MSSV pyrolysis data for boiling ranges C1+, C6+ and C1-5 normalized to the maximum C1+
yield and fitted spline curves for calculated primary and secondary gas generation using three different
heating rates (0.7, 2.0 and 5.0 K/min), compared to normalized SRA curve. Temperature shifts for boiling
ranges can be taken from Table 13. ...................................................................................................................... 62
VI
Fig. 30 Comparison of the approximated spline curves for secondary gas yields using the conservative and
refined approach as well as the Factor-GOR model .............................................................................................. 63
Fig. 31 GOR development throughout kerogen conversion to petroleum (1) using MSSV-closed-system data
(triangles) and (2) derived from the temperature shift of open-system SRA spline curves in the Factor-GOR
model ..................................................................................................................................................................... 65
Fig. 32 Activation energy distributions and normalized measured and calculated generation rate curves for
C1+, C6+, primary and secondary gas formation for samples G010283 (left) and G010351 (right) ........................ 67
Fig. 33 Computed transformation ratio curves (top) and generation rate curves (bottom) as a function of
temperature at a geological heating rate of 3°C/Ma for samples G010283 (left) and G010351 (right) ............... 70
Fig. 34 Computed transformation ratio curves and generation rate curves as a function of temperature at a
geological heating rate of 3 K/Ma for samples G010283 and G010351 compared to literature data (Pepper &
Dodd, 1995) ........................................................................................................................................................... 70
VII
LIST OF TABLES
Table 1 Stratigraphic chart of the Lower Saxony Basin ......................................................................................... 13
Table 2 Depth intervals and depositional environments of the investigated mature and immature wells .......... 16
Table 3 Measured vitrinite reflectances (VR) for investigated wells (Rippen et al., submitted) ............................ 17
Table 4 Kinetic parameters (activation energies and frequency factors) for four immature samples .................. 39
Table 5 Calculated temperatures and vitrinite reflectances for a geological heating rate of 3°C/Ma.................. 39
Table 6 Temperatures of corresponding TR for artificial maturation at a heating rate of 0.7 K/min ................... 42
Table 7 Methane correction factors (C1/C2-5) for four immature samples of well EX-A ........................................ 44
Table 8 Physical properties of representative immature Wealden Shale samples ................................................ 45
Table 9 Petroleum generation potentials of single gaseous compounds and defined liquid boiling ranges for
4 selected, immature samples ............................................................................................................................... 47
Table 10 End temperatures for closed-system MSSV pyrolysis experiments at samples G010283 and
G010351 using three different heating rates ........................................................................................................ 52
Table 11 Absolute yields of the “Free HC correction” and its relative amounts to the maximum MSSV C1+
yield. In comparison, yields from open-system Tvap-GC-FID measurements are recorded. .................................. 62
Table 12 Gas-to-oil ratio from open-system pyrolysis displaying the primary composition of generated
hydrocarbons from samples of immature well EX-A ............................................................................................. 63
Table 13 Temperature shifts of spline curves of primary oil, primary gas and secondary gas at three different
heating rates for both samples, marine G010283 and lacustrine G010351 .......................................................... 64
Table 14 Total product amounts derived from Rock-Eval S2 for measured and calculated boiling ranges of
samples G010283 and G010351 ............................................................................................................................ 65
Table 15 Kinetic parameters, activation energies EA and frequency factor A for SRA bulk petroleum (C1+),
MSSV C6+ as well as primary and secondary C1-5, derived from generation rate curves, calculated using three
heating rates (0.7, 2.0 and 5.0 K/min) ................................................................................................................... 67
Table 16 Temperatures and calculated vitrinite reflectances for the predicted Tmax and TR's at a geological
heating rate of 3°C/Ma for G010283 (left) and G010351 (right) .......................................................................... 68
VIII
ABBREVIATIONS
A Frequency factor
CEBS Central European Basin system
EA Activation energy
FID Flame ionization detector
GC Gas chromatography
GOR Gas-to-oil ratio
HC Hydrocarbon(s)
K Kelvin
LEK Lehrstuhl für Geologie, Geochemie und Lagerstätten des Erdöls und der Kohle
LSB Lower Saxony Basin
Ma Million years
min Minute
MSSV Multi-scale sealed vessel
OM Organic matter
PT Pressure-temperature
PVT Pressure-volume-temperature
Py Pyrolysis
RWTH Rhein-Westpfälische Technische Hochschule Aachen
s Second
SRA Source rock analyzer
tcf Trillion cubic feet (~28.3x109 m³)
Tmax Temperature of maximum petroleum generation
TOC Total organic carbon
TR Transformation ratio
Tvap Thermovaporization
VR Vitrinite reflectance
INTRODUCTION
1
1 Introduction
1.1 Gas Shales: an unconventional petroleum system
Gas shales are an unconventional source for natural gas and have become an
increasingly important market changer, especially in the U.S. To economically produce
significant amounts of hydrocarbons, gas shales need to be fractured or fracced by
hydraulic stimulation (Frantz & Jochen, 2005) to liberate gas molecules. Shale gas
systems are described as a continuous organic-rich source rock that combines the
petroleum system elements of “source rocks, reservoir rocks and seal rocks in one
lithological formation that generates, charges and seals petroleum in juxtaposed, organic-
lean intervals” (Jarvie et al., 2007; Jarvie, 2012). Curtis (2002) defined shale gas plays
with emphasis on the organic matter component as “continuous-type biogenic […],
thermogenic or combined biogenic-thermogenic gas accumulations characterized by
widespread gas saturation, subtle trapping mechanisms, seals of variable lithology and
relatively short hydrocarbon migration distances.”
Generally, shale is the Earth’s most common sedimentary rock (Frantz & Jochen,
2005) and composed of consolidated particles of clay minerals, quartz or calcite whose
grain sizes range between clay (2 µm) and silt (0.063 mm). Because of this grain size
distribution, porosity Φ is variable (from <10 to 30% for consolidated shales) and
permeability k mostly ultra-low (nD to some mD).
To evaluate shale gas plays by their productivity, system characteristics (e.g. rock
properties) and the organic matter component are the major subjects of investigation
(Jarvie et al., 2007; Curtis et al., 2008). On the one hand, mineralogical composition is
one of the key parameters to characterize the best well (Bowker, 2003) as it directly
controls the brittleness and therefore fraccability of a shale. E.g., the Barnett Shale
produces best from zones with 45% quartz (brittle mineral) and 27% clay (ductile mineral)
(Bowker, 2003). According to Curtis et al. (2008), and in terms of system characteristics,
the thickness of the shale formation and pore pressures also contribute to the productivity
of a play.
On the other hand, and of higher relevance for the present thesis, shale gas plays
are assessed based on generative properties related to the organic matter component.
INTRODUCTION
2
The gas itself can be biogenic or thermogenic in origin whereas biogenic gas accounts
for as much as 20% of the worldwide gas reserves (Rice & Claypool, 1981). Biogenic
gas, predominantly methane, is produced at shallow depths and low temperatures
(usually < 80°C) in a two-step process including (1) generation of CO2 and H2 by non-
methanogenic bacteria and (2) reduction of CO2 by methanogenic bacteria into CH4 and
(formation) water. It can be distinguished from thermogenic methane using its δ13C value
and the ratio of methane to higher chain hydrocarbons (C1/C2-5) (Martini et al., 1998).
Thermogenic gas is generated thermochemically by cracking as a function of
temperature and hence maturity, either primarily from kerogen degradation (usually
>80°C) at early to high maturity stages or secondarily from degradation of retained oil
compounds at higher maturity stages (usually >150°C) (Dieckmann et al., 1998). The
assessment of kinetic parameters of primary and secondary cracking reactions is the
subject of this thesis and will be presented in detail later. According to Jarvie et al. (2007)
the continuous, thermogenic gas shale plays (in the U.S.) can be subdivided into (1) high-
thermal-maturity shales (e.g. Barnett Shale), (2) low-thermal-maturity shales (e.g. New
Albany Shale), (3) mixed lithology intraformational systems containing sands, silts and
shales (e.g. Haynesville Shale), (4) interformational shales where gas is generated in
mature and stored in less mature horizons, and (5) systems that combine conventional
and unconventional shale plays (e.g. Woodford Shale and Bakken Shale, Kuhn et al.,
2012). Additionally, mixed biogenic-thermogenic originated systems exist (e.g. Antrim
Shale).
Shale gas is stored by multiple mechanisms including free gas in fractures and
intergranular pores created either by organic matter decomposition (organic porosity) or
other diagenetic or tectonic processes (Jarvie et al., 2007), dissolved gas in the residual
kerogen and bitumen (Martini et al., 1998; Curtis, 2002) as well as sorbed gas on the
internal surfaces of clay minerals or the organic matter (Jenkins & Boyer II, 2008).
Sorption of oil at mineral surfaces and organic matter is also one reason why oil is
retained in the rock and available for secondary cracking. Organic richness (TOC),
kerogen type and thermal maturity influence the sorptive capacity of the organic matter,
hence the petroleum expulsion efficiency PEE (Pepper, 1992; Jarvie et al., 2007), and
therefore the amount of retained oil available for secondary cracking which are important
properties to evaluate gas-in-place (GIP) (Jarvie et al., 2007; Jarvie, 2012).
INTRODUCTION
3
The previously described
characteristics of the rock and OM
components are key parameters for
the assessment of shale gas plays
and can be plotted in various polar
plots mostly comprising five
parameters. Jarvie et al. (2005);
Jarvie et al. (2007) concentrated on
visual and chemical parameters of
organic matter conversion as key
factors for gas flow rates and hence
productivity (economic assessment)
of low-permeability shale gas systems (Fig. 1). The authors used vitrinite reflectances,
transformation ratio as well as gas composition and the proportion of high molecular
weight compounds within thermally extractable (free) organic matter. Based on the
previously described organic and anorganic parameters, Jarvie (2012) defined thresholds
for the best producing areas in the Barnett Shale pursuing them to a global scale:
marine shales, commonly type II OM (HIo: 250–800 mg/g)
organic-rich source rocks (>1.00 wt.% TOC)
gas window maturity (>1.4% Roe)
low oil saturations (<5% SO)
significant silica content (>30%) with some carbonate
contain non-swelling clays
<1000 nD permeability
<15% porosity, more typically about 4 - 7%
GIP values >100 bcf/section
>45 m of organic-rich mudstone
slightly to highly overpressured
very high first-year decline rates (>60%)
consistent or known principal stress fields
drilled away from structures and faulting
continuous mappable systems
As one part of gas shale assessment, and with emphasis on the organic matter
component, this thesis deals with the characterization of OM and its (primary) conversion
into oil as well as secondary cracking mechanisms of oil to gas (see Chapter 1.4).
Fig. 1 Polar shale-gas risk plot with various visual and
chemical assessments of organic matter conversion or
thermal maturity (Jarvie et al., 2007)
INTRODUCTION
4
1.2 Gas Shales in the U.S.
Shale gas has evolved into an important resource for the USA, accounting for more
than 14% of produced gas by the end of 2004 (EIA, 2011). It is predicted to increase to
49% of the total U.S. natural gas production in 2035, corresponding to 13.6 tcf/yr (EIA,
2012). This development is possible due to exploration activity which started around 15
years ago motivated by increasing gas prices and caused by new technologies such as
hydraulic stimulation, horizontal drilling and improved completion technologies (Frantz &
Jochen, 2005). Hence, shale gas is the largest contributor to production growth (Fig. 2)
and the US passes from a net importer to a net exporter of natural gas (EIA, 2012).
Estimated proved (reserves) and unproved (resources) shale gas plays amount to a
combined 542 tcf (15 bn. m³), out of a total U.S. resource of 2,203 tcf. (62 bn m³) (EIA,
2012). Curtis (2002) estimated shale gas resources of the U.S. ranging between 497 to
783 tcf (14 to 22 bn. m³).
U.S. shale gas was, in the 1990’s, produced from five shale formations (Fig. 4) when
these formations became economically exploitable (Curtis, 2002). The Devonian Antrim
Shale in the Michigan basin and the Devonian Ohio Shale in the Appalachian basin were
the first productive formations, which together accounted for 84% of the shale gas
production in 1999. Within the last decade, the Devonian New Albany Shale (Illinois
Basin), the Mississippian Barnett Shale (Fort Worth Basin) and the Cretaceous Lewis
Shale (San Juan Basin) have been explored and developed, steadily increasing in annual
Fig. 2 Natural gas production (in tcf) in the U.S.
classified by source, from 1990 to 2040 (EIA, 2013)
Fig. 3 Annual shale gas production of the U.S. (in
tcf) for the major Gas Shale systems (EIA, 2011)
INTRODUCTION
5
gas production. Over recent years, and constituting the “Shale Gas Revolution” starting in
2006 (Fig. 3), Marcellus Shale (Appalachian basin), Woodford Shale (Arkoma Basin,
Ardmore Basin, Anadarko Basin), Eagle Ford Shale (Western Gulf Basin), Fayetteville
Shale (Arkoma Basin) and the Haynesville-Bossier Shale (Texas-Louisiana Salt Basin)
as well as Bakken Shale (Williston Basin) (Fig. 4) became major contributors to the
natural gas production of the U.S. (Fig. 3). Nevertheless, the Barnett Shale is still the most
active play (Curtis, 2002; Frantz & Jochen, 2005). These formations exhibit a wide range
in key assessment parameters: thermal maturity, sorbed-gas fraction, reservoir thickness,
TOC content and volume of gas-in-place (Curtis, 2002).
Fig. 4 Major shale gas plays in the U.S. showing source rocks and their related
basins (www.eia.gov, updated May, 9th
2011)
INTRODUCTION
6
1.3 Gas Shales in Europe
Europe consumes more than 18.0% of the world wide produced natural gas,
whereas it contributes just 8.5% to the world wide gas supply (BP, 2012). As of today, it
holds only 3.0% of the global gas reserves (BP, 2012). That means Europe is highly
dependent on gas imports from outside Europe, mainly from the Russian Federation, the
Middle East and Algeria by pipeline or LNG. An increase in local production could reduce
this economic and political dependency on natural gas imports.
In Europe, significant shale gas potentials (624 tcf) have been estimated accounting
for 10% of the global technically recoverable shale gas resources (6,622 tcf) (BP, 2012).
In comparison to the U.S., there is limited shale gas experience in Europe. The
experiences from U.S. gas shale systems are not directly applicable to Europe because of
the strong compartmentalization of the geological setting as compared to the large
sedimentary basins in the U.S. (www.gas-shales.org) and to heterogeneities tied to facies
evolution both, laterally and vertically. Furthermore, the production turns out to be difficult
due to the higher density of population in Europe (Horn & Engerer, 2010). Nevertheless,
there are potential source rocks investigated within the GASH project.
The GASH project is the first interdisciplinary, multinational research initiative for
evaluation and development of European gas shales, initiated and “steered” by the GFZ
German Research Centre for Geosciences Potsdam and sponsored by national and
international companies (Bayerngas, ExxonMobil, GDF Suez, Marathon Oil, Respol,
Statoil, Schlumberger, Total, Vermillion and Wintershall). 25 national and state geological
surveys, research institutes as well as universities from Germany, France, the
Netherlands and the U.K. contribute to the research in a regional and reservoir scale.
The scientific goals of the project were to understand how and where gas was
formed and is now located in Europe applying numerical modelling, process simulations
and laboratory analyses. For shale gas, key issues are thus to predict gas-in-place (GIP)
and to quantify those geological, petrophysical and geomechanical properties which most
affect delivery of gas to the wellbore. For this purpose, the Cambrian Alum Shale, the
Upper Jurassic Posidonia Shale, the Lower Cretaceous Wealden Shale and
Carboniferous black shale from the UK have been used as natural laboratories (Bernard
et al., 2012; Hartwig et al., 2012; Mahlstedt & Horsfield, 2012; Bruns et al., 2013b; a). As
reviewed by Schulz et al. (2010), the Silurian shale in Poland and Upper Jurassic black
shales in the Vienna basin have been tested for their shale gas potential and productivity.
INTRODUCTION
7
Also, black shales of Lower Carboniferous age in the Dnepr-Donez basin as well as of
Oligocene/Miocene age in the Pannonian basin hold a significant gas potential (Schulz et
al., 2010). Furthermore, some shales in Northern Germany possess different shale gas
potential, e.g. the Namurian Alum Shale (Kerschke et al., 2012) occurs with a high
potential whereas the Zechstein carbonate possesses too low maturities for a commercial
shale gas potential (Hartwig & Schulz, 2010).
1.4 Aim of this thesis
This thesis forms part of the GASH project and deals with the prediction of timing
and amounts of petroleum generated from Wealden Shales of different lithological origin
within three vertical wells in the Lower Saxony Basin. Kinetic parameters for primary and
secondary hydrocarbon formation as well as the phase behaviour of the generated fluids
as a function of maturity and organic matter type have to be assessed. Preliminary
considerations include Rock-Eval measurements to estimate genetic potential and
maturity of the gas shales as well as kerogen typing and assessing amounts of free
hydrocarbons using the open pyrolysis and thermal extracts, respectively. The timing of
petroleum formation is determined using open-system SR Analyzer which is later
compared to closed-system-MSSV pyrolysis investigating the composition and kinetics of
generated products in terms of PhaseKinetic and compositional kinetic approaches. One
important goal is to improve present compositional models or develop new and/or more
convenient ones.
REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN
8
2 Regional Geology of the Lower Saxony Basin
The Lower Saxony Basin (LSB) is the most important oil province of Germany as
well as the oldest oil-producing basin in the world, with first production starting as early as
1864. It can be regarded as a well-investigated sedimentary basin with a dense grid of
reflection seismic lines and several thousands of drilled wells (Betz et al., 1987).
Economically important petroleum source rocks are Upper Carboniferous coals as well as
Jurassic and Cretaceous shales such as the Toarcian Posidonia Shale and the Berriasian
Wealden Shale, respectively. Numerous small to medium sized reservoir rocks exist
containing predominantly oil. Only a few are mainly gas-bearing (Betz et al., 1987).
2.1 Tectonical setting
The LSB is a WNW-ESE trending trough located in northwestern Germany as one of
many sub-basins within the Central European Basin System (CEBS) (Fig. 5). For a
comprehensive understanding of the tectonic evolution of the LSB, the latter must be
regarded in the larger-scaled context of the CEBS. The CEBS extends W-E directional
from England to Poland and N-S directional from Norway to the midlands of Germany.
The crustal basement of the CEBS developed by terrane amalgamation on the
Precambrian Baltic and East European Craton during Precambrian and Palaeozoic times
(Maystrenko et al., 2008). The CEBS started in the Upper Carboniferous as a foreland
basin which evolved in front of the Variscides with high sedimentation rates. Flexural
extension and an increased sediment load accounted for 70% of subsidence on the one
hand, whereas on the other hand increased rock densities and reduced rock volumes
induced by metamorphic alterations of the lower crust during latest Carboniferous to Early
Permian times caused around 30% of (exponential) subsidence (Brink, 2005). Ziegler
(1990) stated that thermal relaxation of the lithosphere and sedimentary loading were the
most important factors for subsidence during Permian times. When passing from Upper
Permian to Triassic times extensional conditions set in. The basin changed into an
intracontinental basin resulting in the evolution of several sub-basins, the Northern and
Southern Permian Basin as well as the Polish Trough. The Triassic was dominated by a
general plate re-configuration initiating the breakup of Pangea (Ziegler, 1990). This
REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN
9
development was accompanied by a Late Jurassic to Early Cretaceous rifting and the
formation of the LSB.
The LSB is bordered by the Pompeckj Block in the north, the Gifhorn Trough in the east,
the Rheinish Massif in the south and the East Netherland High in the west (Fig. 5)
(Petmecky et al., 1999). Bruns et al. (2013b) concluded, based on observable thickness
variations and the general basin structure, that the LSB must have been a large,
asymmetric and internally faulted graben. The Kimmeridgian (Upper Jurassic) was a
phase of rapid subsidence (Fig. 6) (Petmecky et al., 1999) while adjacent blocks and
highs underwent intense elevation and reactivation of Permo-Carboniferous fault systems
trending along the Hercynian NW-SE faults (Betz et al., 1987). The inversion the LSB that
followed in the Late Cretaceous led to an erosion of large amounts of Cretaceous and
locally older strata of up to 6700 m (Fig. 6) (Bruns et al., 2013b). Inversion induced by a
general plate re-organization in the course of the Alpine orogeny (Adriasola Muñoz, 2006)
was most intensive in the former basin centre. This process culminated during Early
Campanian times when major anticlinorial crests were eroded (Betz et al., 1987) and was
then replaced by a general uplifting until the end of the Cretaceous (Kockel et al., 1994).
During the Late Campanian, Maastrichtian and Danian times sedimentation recommenced
by transgression induced inundation of parts of the LSB. A second inversion during mid-
Fig. 5 Depositional facies of the LSB in Berriasian and Barremian, from Doornenbal (2010)
REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN
10
Paleocene times, the Laramide phase associated with the Pyrenean tectonic pulse (de
Jager, 2003), again affected sediments of the LSB (Betz et al., 1987). Marginal erosion of
Tertiary clastics, caused by a northwards tilting of the LSB during the Oligocene and the
Miocene, was followed by minor sedimentation during the Quaternary (Petmecky et al.,
1999). Due to a missing Cenozoic differential subsidence of the LSB it can be assumed
that the basin achieved thermal and isostatic equilibrium as a consequence of its inversion
(Betz et al., 1987).
Fig. 6 Representative burial history of the Lower Saxony Basin,
from Bruns et al. (2013b)
REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN
11
2.2 Depositional setting and palaeogeographical situation
Again, the evolution of the CEBS will be considered as a whole. Oldest sediments
known in Northern Germany are Devonian and Lower Carboniferous carbonates and
clastics (Brink et al., 1992) of unknown thickness (Betz et al., 1987). The substratum of
the LSB and the adjacent Pompeckj Block is made of Late Carboniferous sediments
unconformably overlaying basal sediments (Betz et al., 1987).
Small coal seams in Upper Namurian strata indicate a change in depositional
environment from marine during the Devonian to partly terrestrial during the Namurian
(Hedemann et al., 1984).
A large number of coal seams and dispersed coaly organic matter are characteristic
for Westphalian sediments (Scheidt & Littke, 1989) comprising the most important source
rocks for gaseous hydrocarbons in central Europe (Littke et al., 1995). These coal seams
are part of deltaic systems with fluvial and marine influences and occur as interbeddings
in silt- and sandstones (Senglaub et al., 2005).
Fig. 7 Palaeogeographical map of NW Germany showing the distribution of
different sedimentary facies and the area of the well location, after Elstner &
Mutterlose (1996)
REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN
12
Stephanian and Rotliegend sediments are mainly deposited in the northern part of
the LSB. Rotliegend sandstones act as an important gas reservoir. Further Upper
Carboniferous and Lower Permian sediments are not believed to be present in the LSB
(Petmecky et al., 1999).
The Zechstein consists of cyclical sequences of carbonate, anhydrite and salt
indicating shallow marine conditions with evaporitic events. These chemical, marine
sediments are continuously deposited in the CEBS and act, with thicknesses over more
than 1000 m, as an important seal for hydrocarbon gas within Rotliegend sediments and
Zechstein carbonates. Their base is the deepest, regionally correlative seismic reflection
horizon in the LSB (Betz et al., 1987). The lower density of salt causes halotectonics,
thus, these deposits are important for the later evolution of the LSB.
Red-coloured clastic rocks characterize sediments of the Lower Triassic which, in
northwestern Germany, is up to 1500 m thick. The Buntsandstein environment comprises
terrestrial lacustrine and fluviodeltaic deposits that are covered with Upper Buntsandstein
salts and anhydrites, forming another significant reservoir for hydrocarbons. During the
Middle Triassic the North German Basin was connected to the Tethys via the Carpathian
and Burgundy Gate which led to the deposition of shallow marine carbonate sediments,
the Lower and Upper Muschelkalk, with intercalations of evaporates in the Middle
Muschelkalk (Petmecky et al., 1999). The Late Triassic was a time of falling sea levels
and increasing salinity. Clastics, the Keuper, were transported from the northern
mountains (Betz et al., 1987) into tidal flats, sabkha and playa lake environments
(Stollhofen et al., 2008).
In Rhaetian times, the evolution of the CEBS was substantially influenced by a re-
establishment of epicontinental marine conditions within the basin. Deposited sediments
are mainly marine shales, including the organic-rich (Lower Jurassic) Toarcian black
shales (Posidonia Shale), marls, carbonates and sands (Senglaub et al., 2005). An
increase of sandy intercalations and several tectonically induced (Betz et al., 1987)
transgressive-regressive cycles indicate a general shallowing of the water depth within the
Middle Jurassic (Petmecky et al., 1999). Clastic influx into the basin decreased during the
Late Callovian and Oxfordian and led to the deposition of dominantly open marine shales
and to a minor extent to carbonates (Betz et al., 1987; Petmecky et al., 1999).
REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN
13
The North German Basin became thoroughly re-shaped
during the Upper Jurassic (Malmian) (Bruns et al., 2013b)
whereas crustal stretching as well as divergent wrenching led to
the formation of several sub-basins of which the LSB was one. In
coexistence with this development, the Pompeckj Block became
uplifted above base level and the longstanding marine
connection between the Northwest European Basin and the
South German Franconian Platform became closed (Betz et al.,
1987). When passing into Kimmeridgian times the area of the
LSB was affected by a major tectonic pulse that resulted in a
regional erosional unconformity (Betz et al., 1987) marking the
final differentiation of the LSB in horst and graben structures
(Petmecky et al., 1999) with lateral thickness variations.
The transition from late Jurassic to Early Cretaceous
times was dominated by a regression causing an isolation of
sedimentary basins throughout northern Europe (Mutterlose &
Bornemann, 2000). The depositional environment of the LSB
during Early Cretaceous times was mainly a shallow marine one.
Nevertheless, some terrestrial sediments, confined to the
uppermost Jurassic/lowermost Cretaceous, can be found
(German Wealden; Petmecky et al., 1999).
The evolution of the Lower Saxony Basin coincides with those of the CEBS. The
following palaeogeographical and lithological descriptions are exclusively limited to the
development of the LSB.
The Berriasian (lowermost Cretaceous) can be subdivided into two
lithostratigraphic units: a lower Münder Formation and an upper Bückeberg Formation
(= German Wealden; Elstner & Mutterlose, 1996). During the Berriasian the so called
“Wealden facies” developed within a basin of 280 km E-W extension and about 80 km N-
S extension with only sporadic connection to the ocean (Berner, 2011). The term
“Wealden” has been applied, with reference to “The Weald” region in southern England, to
non-marine sequences of Upper Jurassic to Lower Cretaceous ages all over the world.
The typical “Wealden facies” can be referred to as consisting of lacustrine sediments in
the basin centre interfingering with fluvial sediments towards the basin margin. Marine
intercalations are of minor importance (Pelzer et al., 1992). Generally, the LSB is
dominated by non-marine, siliciclastic sediments deposited under brackish-lacustrine
Priabanian
Bartonian
Lutetian
Ypresian
Thanetian
Seelandian
Danian
Maastrichtian
Campanian
Santonian
Coniacian
Turonian
Cenoman
Albian
Aotian
Barremian
Hauterivian
Valanginian
Berriasian
Tithinian
Kimmeridgian
OxfordianJura
ssic
Late
Jurr
asic
Pal
eoge
ne
Eoce
ne
Pal
eoce
ne
Cre
tace
ou
s
Late
Cre
tace
ou
sEa
rly
Cre
tace
ou
s
Table 1 Stratigraphic
chart of the Lower Saxony
Basin
REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN
14
conditions that replaced marine conditions at the Jurassic-Cretaceous transition. The
basin consists of western, central and eastern parts (Fig. 7) which underwent differential
subsidence and can furthermore be subdivided according to facies distributions and
different sedimentation rates (Nebe, 1999). The central basin contains up to 700 m of
fluvial-lacustrine mudstones (Elstner & Mutterlose, 1996; Mutterlose & Bornemann, 2000)
comprising freshwater ostracods and coals (Doornenbal, 2010). The western part is
dominated by Neomiodon limestone and mudstones. Sandstones and limestones
consisting of shell detritus (Neomiodon) occur along the northern and southern rims.
Within the basin a general trend of grain coarsening towards the east can be observed
culminating in a domination of sandstones, siltstones, silty claystones, and single coal
seams (Elstner & Mutterlose, 1996). The thick, massive sandstone of the ‘Wealden main
sandstone’ in the ‘Teutoburger Wald’ area is considered to be a distal part of a fan
transporting material from the south into the basin.
The Bückeberg Formation contains no macrofossils, but agglutinated foraminifera
at certain intervals and ostracods of both brackish and freshwater affinities throughout the
basin (Elstner & Mutterlose, 1996). Because of this, ostracod assemblages are the best
suited biostratigraphical indicator, e.g. for salinity changes. Throughout the basin, brackish
and freshwater conditions are obtained but several short-lived marine ingressions are
documented. Brackish water conditions dominate during earliest Berriasian sedimentation
(Münder Formation). A lacustrine freshwater facies was predominantly deposited in the
upper Wealden 3 & 4 (mid-Berriasian) whereas Wealden 5 & 6 display the presence of
freshwater to brackish water conditions which developed to a full marine environment
during mid-Valanginian times indicated by Platylenticeras beds (Elstner & Mutterlose,
1996).
Lower Cretaceous sedimentation of dark-coloured clastic sediments showing partly
high amounts of organic matter lasted until the Barremian and earliest Aptian times. From
the Early Aptian on, a change from clastic to more open marine depositional environments
occurred. Later, light coloured marls predominated.
Late Cretaceous sedimentation within the LSB continued with deposition of
carbonates of varying thicknesses due to eustatic sea level rises inducing a regional
transgression and a drastic reduction in clastic influx (Betz et al., 1987). Late Cretaceous
and Danian chalks partially exceeding 1500 m of thickness were deposited but are deeply
truncated along the LSB margins and removed by erosion. During the latest Turonian,
tectonic activity led to slumping and deposition of turbidites within chalks of the southern
margins of the LSB (Betz et al., 1987). Inversion caused erosion of large amounts of
REGIONAL GEOLOGY OF THE LOWER SAXONY BASIN
15
Cretaceous and locally older sediments (Petmecky et al., 1999). In the LSB erosion
stopped at Buntsandstein layers. Inversion lasted until Campanian times so that the
sedimentary record of the Upper Cretaceous is almost lost (Senglaub et al., 2005).
Northwards tilting of the LSB induced a slight burial and sedimentation of relatively
thin sands and clays of deltaic and shallow marine environment in the Paleocene and
Eocene (Petmecky et al., 1999). These sediments were partly removed by denundation
(Betz et al., 1987) and are only present in the south of the basin. During Eocene and
Oligocene, the basin was flooded repeatedly due to tectonically induced regional sea
level changes. During the Miocene and Pliocene only minor transgressions occurred.
Quaternary sediment thickness increases northwards but stays generally low (Bruns et al.,
2013b).
SAMPLES AND METHODOLOGY
16
3 Samples and methodology
3.1 Origin of data & sample set
Within the GASH project, 292 samples from Wealden core material were provided
by ExxonMobil. Samples originate from three wells in the central part of the Lower Saxony
Basin, EX-A, EX-B and EX-C (Fig. 7) exhibiting different stages of maturity. Each well has
been subdivided in distinct depth intervals characterized by different depositional
environments ranging from deep lacustrine in the lower parts of the wells to deep
marine/marine influenced in the upper parts (Table 2). Total Organic Carbon (TOC)
content measurements and Rock-Eval analyses (S1, S2, S3, HI, OI, PI, Tmax) have been
applied to all samples by the subcontractor Applied Petroleum Technology A/S (APT),
Norway to assess organic matter quality, richness and maturity. Organic petrography and
random vitrinite reflectance (VRr) measurements (Table 3) were performed on 97 samples
revealing that well EX-A is thermally immature to early mature with vitrinite reflectances
between 0.76 and 0.81% R0. VR’s of well EX-C range from 1.5 - 1.6% R0 (very late
mature) to 1.95% R0 (overmature). Overmature well EX-B shows an average mean
vitrinite reflectance of 2.3% R0. 40 samples have been investigated using open-system
thermal analysis (Thermovaporisation, Tvap) and open-system pyrolysis GC-FID to
measure amounts and compositions of already generated as well as “generatable”
petroleum. 12 samples were taken from well EX-A and 14 samples from wells EX-B and
EX-C.
depth [m] thickness [m]
top 831
bottom 850
top 910
bottom 928
top 966
bottom 998
top 1029
bottom 1058
deep lacustrine 32
deep lacustrine 29
EX-A
deep marine 19
sublitoral lake 18
depth [m] thickness [m]
top 980
bottom 1003
top 1150
bottom 1186
top 1285
bottom 1350
top 1560
bottom 1578
deep
lacustrine18
deep
lacustrine65
deep
lacustrine36
EX-B
marine
influenced23
depth [m] thickness [m]
top 604
bottom 617
top 709
bottom 728
top 828
bottom 890
top 920
bottom 942
deep
lacustrine62
lake plain 22
marine
influenced19
EX-C
marine
influenced13
Table 2 Depth intervals and depositional environments of the investigated mature and immature wells
SAMPLES AND METHODOLOGY
17
3.2 Characterization of the organic matter
3.2.1 Organic petrography
Petrographically orientated microscopy and maceral analysis was performed at
RWTH Aachen on selected samples from well EX-A, -C, -B. Data is provided in Rippen et
al. (submitted) and can be found in the appendix (Table A 1).
Samples from well EX-A are taken from depths between 831.5 m and 1058 m. They
contain predominantly liptinites in the form of finely dispersed alginites (lamalginites) and
large bodies of Botryococcus algae (telaginites, Fig. 8), which indicates a brackish-
lacustrine depositional environment. An average vitrinite reflectance of ~0.78% Ro
indicates an early to medium stage of maturity at onset of the oil window supported by
intense fluorescence colours. Taking into account the strong fluorescence, high HI values
(next sub-chapter), as well as the assumption that the presence of resedimented vitrinites
cannot be ruled out, measured vitrinite reflectance should be seen as a maximum.
Vitrinite reflectances (VR) of samples from well EX-B and EX-C range from 2.2 to
2.4% R0 (EX-B) and 1.5% R0 at a depth of 613 m to 1.93% R0 at a depth of 921 m for well
EX-B (Table 3) indicating the presence of highly overmature organic matter in well EX-B
and late mature to overmature organic matter in the wet gas window (EX-C). This
anomalously strong increase in VR over an interval of only 300 m was explained by
(Lüders et al., 2012) as being caused by hot hydrothermal solutions circulating at the base
Table 3 Measured vitrinite reflectances (VR) for
investigated wells (Rippen et al., submitted)
Fig. 8 Fluorescing Botryococcus algae in sample
G010304 (Well EX-A, depth: 923.50 m), from Rippen
et al. (submitted)
well GFZ no.depth
(m)
vitrinite
reflectance
(%)
revised VR
(%)
G010302 919.26 0.76
G010321 997.34 0.81
G010369 613.11 1.60 1.5
G010389 727.97 1.74
G010390 827.80 1.62
G010416 919.10 1.92
G010418 921.24 1.95 1.93
G010450 991.20 2.20
G010456 996.80 2.21
G010516 1297.37 2.40
G010524 1332.27 2.24
G010535 1339.85 2.30
EX-B
EX-C
EX-A
SAMPLES AND METHODOLOGY
18
of the investigated succession. Maceral analysis shows that the organic matter in both
wells is dominated by a solid bitumen matrix (pyrobitumen) indicating very high levels of
kerogen conversion at the bottom of the well. For example and according to Dieckmann et
al. (1998), formation of gaseous hydrocarbons from the secondary cracking of C6+
compounds at elevated thermal stress levels leads concomitantly to the formation of
pyrobitumen (coke). Furthermore, only small amounts of liptinites have been detected in
well EX-C and Botryococcus algae do not occur anymore. However, in well EX-B, a high
abundance of vitrinites and inertinites are an indicator for significant input of terrigenous
organic matter. In comparison to samples from well EX-A, vitrinites and inertinites are
more abundant and are classified as semifusinites.
3.2.1 Rock-Eval pyrolysis
TOC and Rock-Eval data has been gained for 292 samples from three wells. The
following data, figures and diagrams have already been described in Rippen et al.
(submitted). Here, source rocks are characterized on the basis of geochemical
parameters published in Peters (1986).
3.2.1.1 Immature well EX-A
Rock-Eval pyrolysis data for samples of well EX-A are given in the appendix (Table
A 2). Four samples from each depth interval have been investigated in greater detail by
different kinetic approaches – G010283, G010305, G010316 and G010351. Further
investigated samples are marked using black symbols in Fig. 9.
The total organic carbon (TOC) contents are heterogeneously distributed over the
well and even within single intervals ranging from 0.33 to 17.5%. According to Peters
(1986) an average value of 3.99% indicates a good to very good organic matter richness.
Samples from the uppermost, deep marine and the lowermost, deep lacustrine interval
show poor to very good TOC contents. In contrast, samples from the sublitoral lake facial
and deep lacustrine intervals lying in between the former ones exhibit very good TOC
values throughout the whole sequence. Each of the four further investigated samples
exhibits the highest TOC content and genetic potential within its respective interval (9 to
17.5%). Interestingly and as can be seen on the S2 vs. TOC diagram (Fig. 9), samples
SAMPLES AND METHODOLOGY
19
with very good TOC contents (>2%) predominantly plot in the kerogen type I field whereas
samples with lower TOC values rather plot in the fields for kerogen type II, II/III, and III.
High TOC contents therefore correlate with high HI values exceeding 600 mg HC/g TOC.
The generative potential is also connected to the TOC content and can be found in the
lowermost, deep lacustrine interval (sample G010351). S1 values are low by ranging
between 0.01 and 3.53 mg/g rock, as can be expected for immature source rocks. Yields
above 1 mg/g rock can be observed for samples with very good TOC contents and
extremely elevated HIs (>700 mg HC/g TOC). Tmax values that also can be used to assess
the maturity of a source rock (Fig. 9) (Van Krevelen et al., 1951; Jüntgen & van Heek,
1968; Espitalié et al., 1977) range between 429°C (for the marine sample G010283)
indicating the onset of oil generation and >446°C indicating maturity stages well above
directly measured ones (0.78% R0). Nevertheless, it is known that very homogeneous
type I organic matter tends to have elevated Tmax values, even at low maturity stages
(Tissot & Espitalie, 1975; Tissot et al., 1978).
Fig. 9 TOC / Rock-Eval plots for well EX-A (pseudo-van-Krevelen diagram, HI vs. Tmax,
S2 vs. TOC)
SAMPLES AND METHODOLOGY
20
3.2.1.2 Late and overmature wells EX-C and EX-B
Samples from wells EX-C and EX-B are late to overmature (EX-B: 2.2 - 2.4% R0,
EX-C: 1.6 - 1.9% R0) and should therefore exhibit a low petroleum generation potential
(low S2, HI, S3, OI) and very high Tmax values. Nevertheless, in Fig. 10 (HI vs. Tmax) one
can see that Tmax values range between 300 and 600°C and that S2 yields (0.51 -
12.2 mg/g) and elevated HI’s (39 - 211 mg HC/g TOC) indicate a hydrocarbon generation
rest-potential of the organic matter in the upper two horizons of wells EX-C and EX-B.
This controversy can be explained by a carryover effect, i.e. a carryover of S1 products
into the S2 temperature range. The broad range in Tmax values is also caused by carried
over S1 products and/or low signal-to-noise-ratios (Peters, 1986) because the highest
point of the S2 trace is automatically picked by the evaluation software. Thus it can be
stated that Tmax is a quite unreliable maturity indicator in these generally overmature wells
because S2 does not always develop a clear maximum.
TOC contents in both of the wells possess an average organic matter richness of
2.7% ranging between 0.5% and 17.4%. A general decrease of average TOC content with
maturity can be observed for the three wells as the organic matter was thermally
degraded to hydrocarbons which were subsequently expelled from the source rock. The
residual organic matter is composed of so-called “dead carbon”.
Fig. 10 TOC / Rock-Eval data (pseudo-van-Krevelen diagram, HI vs.
Tmax, S2 vs. TOC) for late and overmature wells EX-C and EX-B
SAMPLES AND METHODOLOGY
21
3.3 Analytical program
Bulk Kinetics and PVT-compatible PhaseKinetics were applied to four immature
samples from different depth intervals of well EX-A using open system pyrolysis (SRA) at
three different heating rates and closed-system-MSSV-pyrolysis with a heating rate of
0.7 K/min. Additionally, kinetic parameters of primary and secondary gas formation were
determined for two of these samples using closed-system-MSSV-pyrolysis at three
different heating rates (0.7, 2 and 5 K/min). One sample from the deep marine interval
(847.27 m) and one sample from the upper deep lacustrine interval (972.57 m) have been
chosen to get a clear distinction between different organofacies.
In addition to the named methods and for completeness, principles of Rock-Eval
pyrolysis as well as open-system pyrolysis GC-FID will be shortly explained in the
following.
3.3.1 Geochemical characterization
3.3.1.1 TOC / Rock-Eval pyrolysis
TOC content measurements and Rock-Eval pyrolysis were employed to determine
genetic potential and maturity of the organic matter. Directly measured parameters are
TOC (%), three distinctive peaks S1, S2, and S3 (mg/g sample), and Tmax (°C). For this
purpose, a Rock-Eval 6 Instrument (Behar et al., 2001) was used by the subcontractor
Applied Petroleum Technologies (APT) A/S, Norway following the procedure described in
NIGOGA, 4th edition (Weiss, 2000). Jet-Rock 1 was run every tenth sample as an external
standard. Furthermore, there was no necessity of pre-treatment of samples before loading
the apparatus.
For TOC analysis a LECO SC-632 was used. Sample material was finely ground
and treated with diluted HCl (HCl:water 1:9) at 60°C to remove inorganic carbon. After
reaction was apparently finished some HCl (HCl:water 1:1) was added to ensure that
inorganic carbon is completely converted. Afterwards, samples have been rinsed with
water for removing HCl and dried. The crushed powder was then inserted into the LECO
combustion oven for analysis at 1350°C. A flow of oxygen was needed to fully convert
SAMPLES AND METHODOLOGY
22
material to CO2. The TOC (in wt-%) was calculated using carbon dioxide concentrations
measured by an IR detector.
For Rock-Evaluation ~100 mg of pulverized sample material is weighted into
stainless steel crucibles. After placing them in the Rock-Eval 6 instrument, a temperature
program can be started which, in a first step, isothermally holds the samples at 300°C for
3 minutes. In a second step, the pyrolysis device heats up to 650°C at a heating rate of
25°C per minute, followed by the cooling down of the combustion oven for the next run.
The whole process is conducted under inert atmosphere using a helium flow that
transports generated bulk organic compounds and CO2 to a flame ionization detector or
thermal conductivity detector, respectively.
The S1 peak is recorded during the isothermal 300°C temperature step and
represents vaporized free hydrocarbons that have been generated until the present
maturity stage and still remain in the source rock. The S2 peak represents pyrolysis
products generated from kerogen degradation during the non-isothermal heating interval
as well as the very heavy portion of free hydrocarbons (n-C40+) whose boiling point
exceeds 300°C. Tmax is the temperature where the S2 peak reaches its maximum and can
be named a maturity indicator. It can be used to calculate the vitrinite reflectance applying
the following empirical formula (Jarvie et al., 2001) that, however, delivers unreliable
results for type I kerogens because these kerogens possess mostly only a single
activation energy and frequency factor (Jarvie et al., 2001):
(1)
The S3 peak represents CO2 released and trapped during pyrolysis in the
temperature range 300 to 390°C and is detected by a thermal conductivity detector (TCD).
S1, S2 and S3 are, together with TOC, used to calculate the parameters HI, OI and
PI. HI, the hydrogen index, represents the quantity of organic compounds from S2 relative
to TOC and is calculated by normalizing S2 to TOC [(S2·100)/TOC], it correlates with the
H/C of a rock sample. OI, the oxygen index is defined as (S3·100)/TOC and is
proportional to the O/C ratio. To gain additional information about the maturity of a sample
or the presence of its contaminants the PI (production index) can be calculated by
S1/(S1+S2).
SAMPLES AND METHODOLOGY
23
3.3.1.2 SRA – source rock analyzer
Measurements were performed for four samples to establish bulk kinetic parameters
during conversion from kerogen to petroleum. Whole rock samples were measured by
non-isothermal pyrolysis at four different heating rates (0.7, 2, 5, 15 K/min) using a Source
Rock Analyzer (SRA-TPH/IR) from Humble Instruments. 2.2 to 29.9 mg of sample
amount, depending on heating rate and organic matter richness, were weighted into small
vessels and heated to temperatures as high as 640°C. Generated bulk petroleum
products are transported to an FID (flame ionization detector) by a constant helium flow
(50 mL/min). Gained raw data was computed to discrete activation energy distributions
(Behar et al.) with a single variable frequency factor (A in 1/s) by using KINETICS2000
and KMOD® (Burnham et al., 1987). For reliable timing predictions slow heating rates (≤5
K/min) were chosen to avoid problems with the heat transfer between sample and inert
gas flow and/or within the sample itself if heated too fast (Schenk & Dieckmann, 2004).
The heating rate variation should be broad enough to ensure correct iteration of the
mathematical model and calculation of frequency factors.
3.3.2 Thermovaporization (Tvap-GC-FID)
To measure the composition and amount of free hydrocarbons in naturally or
artificially matured source rock samples, thermovaporization (Tvap-GC) is used as a
standard measurement. Here, ~10 mg of crushed sample material was weighted and filled
into a small, on one side closed glass capillary tubes of approximately 40 µl volume with a
bore diameter of 1.0 mm and a flexure of 120°. In a first step, the glass tube was filled with
pre-cleaned quartz sand and the sample material was placed in the elbow portion of the
tube. After cleaning the interior with thermally cleaned glass wool and filling the tube with
quartz sand to reduce the remaining “air”-volume to a minimum, the tube was closed by a
hydrogen flame. Such small sample amounts are used to detect the precise sample
temperature of the aliquot with the thermocouple.
SAMPLES AND METHODOLOGY
24
For the analytical procedure,
a pyrolysis-gas chromatograph
from AGILENT Instruments has
been used (AGILENT GC 6890A
Chromatograph). The system
comprises a purpose-built sample
holder, a programmable pyrolysis
furnace, a heated on-off split, a
trap that can be cooled
cryogenically, a heated transfer
zone, a gas chromatograph and
an analytical unit (flame ionization
detector, FID) (Fig. 11).
The Tvap-MSSV tube was
loaded into the liner which was
then closed. A five-minute purge
at 300°C was used to thermally mobilize the free hydrocarbons within the sample and to
clean the outer surface of the tube. Meanwhile, effluents were vented via the on-off split
(Horsfield et al., 1989), the trap was cooled down to -178°C by nitrogen filled in a DEWAR
vessel and the software was fed with information about sampleID, sample weight, the
used method, temperature and heating rate. After closing the system with an on-off split,
the system pressure had to reach 20 psi. The tube was now cracked using the piston, and
the temperature program of the GC oven was started. Sample products were flushed by a
helium flow (30 mL/min) to the cooled trap where they condensed. Methane was not
properly trapped by this configuration but nevertheless recorded by the FID in an early
peak. When removing the nitrogen cooling vessel after 10 minutes, the trap was heated
up to 300°C ballistically. Hydrocarbons fixed in the trap were released via a 50 m x
0.32 mm capillary column (J&W Scientific HP-Ultra 1 [Dimethylpolysiloxan-phase], 0.52
µm film thickness). Products were detected using a flame ionization detector (FID) and
displayed as an electric current response in pA. n-Butane has been used as an external
standard. Prominent hydrocarbons have been identified with the aid of reference
chromatograms and manually quantified with “AGILENT ChemStation offline” software by
peak area integration.
Fig. 11 Schematic configuration of a pyrolysis-GC oven used
for MSSV analysis
SAMPLES AND METHODOLOGY
25
3.3.3 Open pyrolysis (Py-GC-FID)
Non-isothermal open-system pyrolysis was utilized for characterization of the
macromolecular structure of the kerogen by qualification and quantification of generated
primary organic compounds (Horsfield, 1989). Analyses have been performed on the
residual material of 40 early mature and late to overmature samples of the Wealden Shale
directly after Tvap-GC-FID using the same equipment and procedure. The only difference
is the pyrolysis, i.e. heating the residues to a final temperature of 600°C at a rate of
50 K/min. The pyrolysate was again transported to the cryogenic trap from where it was
liberated to the Agilent GC 6890A gas chromatograph as described before.
3.3.4 MSSV (Micro-Scale-Sealed-Vessel)-closed system pyrolysis
(MSSV-Py-GC-FID)
Non-isothermal MSSV-closed system pyrolysis is a micro-analytical method to
artificially mature sedimentary organic matter and to qualify and quantify primary oil and
gas generation. It provides the possibility to determine primary and secondary reaction
kinetics for prediction to geological heating rates.
This technique developed by Horsfield et al. (1989) consists of two sequential steps:
(1) artificial maturation of small aliquots of the original samples in a closed glass tube to
distinct end temperatures and (2) investigation of the generated products qualitatively and
quantitatively on a molecular level by gas chromatography.
Small one-sided closed glass capillary tubes of approximately 40 µl volume with a
bore diameter of 1.0 mm and a flexure of 120° were used to carry the weighted sample
material. The MSSV glass tube was filled with quartz sand and, depending on the
calculated end temperature, 5.0 to 15.5 mg of sample material into the elbow portion of
the tube. The tube was closed by a hydrogen flame. For end temperatures exceeding
600°C quartz-glass tubes had to be used because of the too low melting point of
“standard” glass. Sample aliquots were artificially matured in a pyrolysis oven consisting
of a massive, cylindrical metal block acting as a circular sample holder. A central heating
cartridge provided a very homogeneous temperature field throughout the core which is
controlled by a thermocouple introduced into one sample holder. The pyrolysis oven for
temperatures <600°C is able to accommodate 29 glass liners, each of which can carry
SAMPLES AND METHODOLOGY
26
one small glass tube. The high temperature pyrolysis oven is able to give space for up to
10 samples. For the PhaseKinetics approach, a heating rate of 0.7 K/min was applied to
four immature samples with calculated end temperatures for distinct transformation ratios
given in Table 6. For the determination of primary and secondary cracking kinetics, three
different heating rates, 0.7, 2.0 and 5.0 K/min, have been applied to two selected
immature samples. The heating rates must be sufficiently low to ensure correct
temperature measurements and sufficiently different to derive a reasonable starting value
of frequency factor A (in 1/s) from the shift of peak generation temperatures
(Sundararaman et al., 1992; Schenk & Horsfield, 1993).
After removal of the tubes from the pyrolysis oven, the samples were transferred to
the previously described gas chromatograph GC 6890A from AGILENT instruments and
analysed as described for Thermovaporisation (subchapter 3.3.2). Results are given in the
appendix (Table A 5 and A 6).
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
27
4 Results
4.1 Molecular characterization of generated products
4.1.1 Composition of free hydrocarbons
The samples were investigated by thermovaporization to describe the composition
of free hydrocarbons. 12 samples of immature well EX-A have been evaluated as well as
14 samples of each overmature well EX-B and EX-C. In Fig. 12 representative GC-traces
of each interval are shown. Yields of boiling ranges and single compound yields for all
investigated samples are given in the appendix (Table A 3).
Each of the 4 chromatograms displayed in Fig. 12 represents one stratigraphic
interval of well EX-A. The composition of free hydrocarbons is strongly dominated by
intermediate to long chained aliphatic hydrocarbons and possibly represents in-situ first-
formed products (Rippen et al., submitted) within the different organofacies. Thermal
extracts of samples from the deep marine interval (831 - 850 m) comprise, as a major
fraction, aliphatic hydrocarbons which exhibit a maximum for intermediate chain-length
around n-C13 or n-C14. This is characteristic for oils derived from marine kerogens
(Horsfield, 1989) whereas a slight odd-over-even carbon numbers preference of those n-
alkanes is frequently associated with non-marine sediments containing Botryococcus
alginites (Horsfield, 1989). Aromatic, cycloparaffinic and sulfur-containing compounds
occur in considerable amounts with benzene as a major aromatic component. In contrast,
thermal extracts of samples from the three other horizons show strong emphasis on long-
chained n-alkanes with maxima around n-C23-25, which is characteristic for oils from a
lacustrine source rock (Tegelaar & Noble, 1994). These long-chained homologues are
derived from precursors that would generate waxy hydrocarbons under geological
conditions (Horsfield et al., 1994). Interestingly, the thermal extracts from the three
lacustrine influenced intervals differ in their n-alkane distribution pattern from each other.
The sample from the upper lacustrine horizon (966 - 997 m) shows a strong emphasis on
long-chained n-alkanes (from n-C15 to n-C29) with only minor amounts of non-aliphatic
compounds, while the samples of the sublitoral (910 - 928 m) and lower lacustrine
horizons (1029 - 1058 m) exhibit also intermediate-chained n-alkanes with aromatic
components and cycloparaffins in considerable concentrations. Furthermore and
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
28
concerning general low yields of gaseous and light hydrocarbon compounds, a gas loss
during sampling and sample storage can never be excluded.
Low amounts of light hydrocarbons, as observed for the thermal extract of the upper
lacustrine interval, might be explained by several scenarios besides differences in
kerogen precursor structures. One could be an early expulsion of light petroleum
compounds from its source and retention of heavy-ends in the shale. Another theory
addresses post-generation alteration processes, which includes biodegradation of
preferentially intermediate alkyl-chains, or possibly water washing having an impact on
preferentially light hydrocarbons (Milner et al., 1977; di Primio & Horsfield, 2006).
Generally, biodegradation is indicated by elevated sulphur contents or a low ratio of n-
paraffins to naphthalenes and branched paraffins (Milner et al., 1977). Both of these
effects cannot be detected in Tvap-GC traces and yields of samples from the immature
well. On the other hand, very low amounts of the gasoline fraction (C1-5) and high yields of
the C15+ compounds or a lack in light aromates such as benzene or toluene (present in
samples of well EX-A, shown in the appendix, Table A 3) point to effects of water
washing. As open pyrolysis yields (next chapter) light aromatic compounds as well as high
amounts of products in the gasoline range for the same samples discussed observations
could point to alteration of possibly in-situ formed petroleum by water washing.
Late mature to overmature well EX-C contains paraffinic, waxy (and thermally
degraded) oil in its upper, marine influenced intervals (709 - 729 m), i.e. Tvap products
are dominated by intermediate- to long-chained aliphatic components (Fig. 12). Gaseous
compounds are present in only minor amounts, but again, a gas loss during sampling is
possible. In the deep lacustrine intervals (828 - 942 m) free hydrocarbons consist of short-
to intermediate-chained aliphatic compounds (<n-C16) whereas the n-alkanes
concentration does consistently decrease with increasing carbon number. Aromatic
components occur in considerable concentrations which do also decrease with increasing
molecular weight. Thermal extracts of samples from the overmature (VR = 1.93% R0) lake
plain interval (920 - 942 m) exhibit a domination of short-chained gaseous hydrocarbons
together with benzene and toluene as major aromatic compounds. Intermediate-chained
aliphatic components with a maximum at n-C12-13 occur only in low concentrations and not
in all cases.
Free HC in the overmature well EX-B (VR = 2.24 - 2.4% R0) exhibit almost the same
composition than those from the respective organofacies of well EX-C, even though
overall yields are somewhat lower (Table A 3). In samples of the marine influenced
interval (981 - 1003 m) intermediate-chained aliphatic compounds dominate over minor
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
29
amounts of aromatic compounds. But aromatic compounds occur in relatively higher
amounts than in the respective organofacies of well EX-C which indicates a slightly higher
degree of thermal degradation of petroleum in well EX-B. In the deep lacustrine intervals
different Tvap-GC fingerprints have been detected. The samples of the upper lacustrine
horizon (1150 - 1186 m) comprises short- to intermediate-chained aliphatics with different
concentrations of intermediate-chained compounds whereas the lowermost deep
lacustrine horizons (1560 - 1578 m) comprise mainly intermediate-chained components
(<n-C14) with very low and varying amounts of gaseous and aromatic or cycloparaffinic
components.
Both wells (EX-C and EX-B) show the same, very interesting trend with depth. The
upper intervals are intermediate to long alkyl-chain dominated whereas the lower intervals
tend to be short alkyl-chain dominated. Interestingly, the thermal maturity of the organic
matter, as indicated by measured VR in the upper interval of overmature well EX-B is
higher than the thermal maturity of organic matter in the lowermost depth interval of well
EX-C. This indicates that the observed trend cannot be purely related to the secondary
cracking of retained petroleum as a function of depth/maturity. In this context, Lüders et al.
(2012) suggested that the steep and partly not linear maturity gradients might be
explained by hydrothermal solutions with different thermal energies circulating in the
geological formations of the different wells, thereby influencing the composition and
maturation of the organic matter.
Generally it should be stated that it is not easily possible, or at least out of the scope
of this thesis, to clarify whether the detectable free petroleum products are in-situ
generated and/or alterated by postgeneration processes or migrated. A deeper insight in
this topic is provided in the last chapter (4.5) when compositional and physical properties
can be included in the interpretation.
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
30
Fig. 12 Tvap-GC traces of samples from early
mature (a), late mature (b), and overmature (c)
wells at different stratigraphic intervals and
depths
(a) (b)
(c)
min20 40 60 80 100
pA
0
200
400
600
800
1000
1200
1400
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\WEALDEN\CHROMMS\G010362A.D)
EX-C (upper, marine influenced)
14
29
min20 40 60 80 100
pA
0
200
400
600
800
1000
1200
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\WEALDEN\CHROMMS\G010396C.D\..\G010396C.D)
EX-C (deep lacustrine)
14
min20 40 60 80 100
pA
0
100
200
300
400
500
600
700
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\WEALDEN\CHROMMS\G010521A.D)
EX-B (middle, deep lacustrine)
13
min20 40 60 80 100
pA
0
500
1000
1500
2000
2500
3000
3500
4000
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\TVAPOP~1\G010450A.D\..\G010450A.D)
EX-B (marine influenced)
14
20
min20 40 60 80 100
pA
0
100
200
300
400
500
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\TVAPOP~1\G010492A.D\..\G010492A.D)
EX-B (upper, deep lacustrine)
12
9
min20 40 60 80 100
pA
10
15
20
25
30
35
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\TVAPOP~1\G010281A.D\..\G010281A.D)
EX-A (deep marine)
14
23
9
min20 40 60 80 100
pA
20
40
60
80
100
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\TVAPOP~1\G010305A.D)
EX-A (sublitoral lake)
15
25
9
min20 40 60 80 100
pA
10
20
30
40
50
60
70
80
90
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\TVAPOP~1\G010316A.D\..\G010316A.D)
EX-A (deep lacustrine)
23
15
min20 40 60 80 100
pA
10
20
30
40
50
60
70
80
90
FID1 A, (C:\DOKUME~1\NICK\EIGENE~1\GASH\TVAPOP~1\G010349A.D\..\G010349A.D)
EX-A (deep lacustrine)
23
15
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
31
4.1.2 Bulk chemical kerogen composition
Open system pyrolysis-gas chromatography was conducted to gain additional
information on the macromolecular structure of the labile organic matter. Covering all
different organofacies of the Wealden Shale, 40 samples have been investigated including
12 samples from immature well EX-A, and 14 samples from overmature wells EX-B and
EX-C, respectively. Yields of boiling ranges and single compounds are given in the
appendix (Table A 4).
The pyrolysates of samples from immature well EX-A comprise dominantly
intermediate to long, straight-chained aliphatic hydrocarbons which show the, for open-
system pyrolysis conditions characteristic, distribution of n-alkane/n-alkene doublets (Fig.
13). With increasing carbon number concentrations of alkanes and alkenes continuously
decrease, whereas for some samples a second maximum can be observed for higher
carbon numbers. The pyrolysates display a slight predominance of odd n-alkanes in the
range from C9 to C21. As Tvap-GC traces of samples from well EX-A show, this often
occurs in the n-alkane distributions of fluviodeltaic/lacustrine associated waxy crude oils
(Horsfield, 1997) and has also been documented in pyrolysates from algal kerogens (Goth
et al., 1988; Horsfield et al., 1994). As expected for type I kerogen, cycloalkanes, aromatic
and sulphur-containing compounds occur in only minor amounts, whereas phenolic
compounds are extremely scarce.
Fig. 13 Representative chromatogram of open-system pyrolysis measurement showing the predicted
composition of the first formed petroleum from immature samples of well EX-A; filled dots represent n-alkanes,
empty dots mark n-alkenes and small hexagons represent aromatic components; numbered peaks denote
chain lengths of n-alk-1-ene and n-alkane doublets
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
32
The characterization of organic matter of (immature) source rocks is conducted by
using three ternary diagrams in which aliphatic, aromatic as well as sulphur- and oxygen-
bearing compounds are compared with each other. Horsfield (1989, 1997) employs the
total gas fraction (C1-5) versus intermediate (n-C6-14) and long-chained (n-C15+) n-alkyl
chains to relate the pyrolysate composition to the petroleum fluid type generated under
natural conditions. Based on this chain length distribution five organofacies fields were
classified (Fig. 14a): gas condensate, paraffinic-naphthalenic-aromatic (PNA) high-wax oil,
PNA low wax oil, paraffinic high-wax oil, and paraffinic low-wax oil generating types. All
investigated samples generate pyrolysates which plot within the “paraffinic high-wax oil”-
field, whereas the wax content is highly variable within single depth intervals. The
kerogen, as the precursor for this type of pyrolysate, is mainly made up of preserved outer
cell walls of the lacustrine micro algae Botryococcus braunii (compare chapter organic
petrography, 3.2.1) which are composed of long, unbranched, aliphatic hydrocarbons
(Berkaloff et al., 1983) with chain lengths up to C31 (Largeau et al., 1984). This kind of
organic matter is usually deposited in a lacustrine environment under anoxic conditions
requiring a stable stratified water column controlled by salinity and temperature gradients
(Horsfield, 1997). Higher wax contents are generally linked to organic matter deposited
under more anoxic conditions (Sachsenhofer, 1994).
In the ternary diagram developed by Larter (1984) the aquatic or terrestrial origin of
organic matter can be deduced by the relative proportions of phenol, n-octene and m,p-
xylene (Fig. 14c). Phenol is an aromatic compound which occurs predominantly in
pyrolysis products of terrestrial derived organic matter. m,p-Xylene is an isomer of
dimethylbenzene which provides a good estimate of a sample’s aromaticity because it is
less influenced by pyrolytic decomposition reactions than other typically occurring
aromates (Larter, 1978; Larter & Douglas, 1980) such as benzene or toluene (Larter,
1978). After Stout & Boon (1994) these compounds originate from pyrolytic degradation of
lignin, sporopollenins and polycarboxylic acids. Muscio & Horsfield (1996) propose
aromatization and condensation reactions involving primary aromatic structures and
possibly cross-linked moieties as origin of aromatic structures. n-Octene is used to
represent aliphatic moieties within kerogen. Due to the absence of phenolic precursor
structures and the overall aliphatic nature of the lacustrine Wealden Shale alginate
pyrolysates of all samples plot along the n-C8:1–m,p-xylene axis within the field for organic
matter of aquatic origin with a strong emphasis on n-alkanes.
Eglinton et al. (1990) used 2,3-dimethylthiophene, o-xylene and n-C9:1 to assess the
organic sulphur content and to differentiate between predominant kerogen types (Fig.
14b). This allows the discrimination of depositional conditions between a marine or
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
33
hypersaline sedimentary environment and freshwater lacustrine or terrestrial
environments, whereas kerogens deposited in freshwater conditions yield only small
sulphur quantities (Eglinton et al., 1990). High-sulphur kerogens originating from clay-poor
environments yield alkylthiophene isomers as major compounds (Eglinton et al., 1992)
which are formed during early diagenesis by intermolecular sulphur incorporation
reactions involving functionalized lipids and H-sulfides (Sinninghe Damste & De Leeuw,
1990). Only low relative portions of sulphur-containing compounds were generated during
thermal degradation of kerogen to petroleum under open-system pyrolysis conditions.
Regarding thiophenes, the kerogen structure is dominated by 2-n-alkylthiophenes as can
be expected for type I kerogens (Horsfield, 1997). 2,3-, 2,4- and 2,5-dimethylthiophenes
occur in varyingly low amounts in the pyrolysates (Table A 4). These branched isomers
occur typically in type III kerogens indicating a slightly terrestrial influx (Eglinton et al.,
1990) that likely was transported by fluviodeltaic systems located in the eastern part of the
LSB (see Fig. 7).
Fig. 14 Open-system pyrolysis-GC data for typing of the molecular kerogen structure and petroleum type
organofacies of immature samples of well EX-A using the ternary diagrams of (a) Horsfield, 1989, (b) Eglinton
et al. 1990 and (c) Larter, 1984
n-C15+ 80%
C1-5
100%
80% n-C6-14
Paraffinic OilLow Wax
Paraffinic OilHigh Wax
P-N-A OilLow Wax
P-N-A OilHigh Wax
Gas andCondensate
terrestrial
Type IV
aquatic
0 20 40 60 80 100Phenol
100
80
60
40
20
0
n-C
8:1
100
80
60
40
20
0
m,p
-Xyl
ene
aromatic
aliphatic
intermediate
high-sulphur
0 20 40 60 80 100n-C9:1
100
80
60
40
20
0
o-Xylen
e
100
80
60
40
20
0
2,3-
DM
-Thio
phen
e
(a) (b) (c)
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
34
Open-system pyrolysis-GC-FID fingerprints of
samples from late and overmature wells EX-C and
EX-B, respectively, reveal a domination of short-
chained aliphatic compounds as well as aromatic
compounds, an expected feature for this stage of
maturation (Fig. 15, bottom). Benzene, toluene as
well as m,p-xylene and o-xylene are common
components in pyrolysates (Larter & Douglas,
1980; Muscio et al., 1994) and represent aromatic
moieties within the kerogen. Therefore and in
deeper parts of the profile, pyrolysates indicate a
highly degraded kerogen structure exhibiting very
high GOR’s. C6+ aliphatic compounds are scarce
and aromatics such as benzene and toluene occur
in low absolute amounts. This induces a relative
high aromaticity which can be explained by the elimination of labile functional groups
during increasing thermal stress leading to aromatization and polycondensation of the
residual kerogen during petroleum generation (Tissot & Welte, 1978). Nevertheless, in the
Fig. 15 Representative chromatograms for late and overmature samples, originating from uppermost, marine-
influenced horizon of well EX-B that are affected by a “carryover” effect and stemming from lower situated deep
lacustrine depth interval unaffected by the “carryover” effect; filled dots represent n-alkanes, empty dots mark n-
alkenes and small hexagons represent aromatic components; numbered peaks denote chain lengths of n-alk-1-
ene and n-alkanes; B = benzene, T = toluene; EB = ethylbenzene, mpX = meta,para-xylene, oX = ortho-xylene,
N = naphthalene
Fig. 16 Generalized reaction pathway for
the formation of n-alkenes and n-alkanes in
open-system pyrolysates (after (Kiran &
Gillham, 1976; Schenk et al., 1997a))
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
35
upper horizons of both wells, intermediate to long straight-chained aliphatic compounds
are present (n-alkanes) showing maximum peak heights between n-C14 and n-C23 (Fig.
15, top). As single long chained n-alkenes are missing, these compounds can be
identified as free hydrocarbons which are carried over into the higher temperature range
(corresponding to S2 peak). That means that at 300°C some high molecular weight
components could not be vaporized and measured during Tvap-GC, but are detected
during pyrolysis. If the detected aliphatic hydrocarbons would have been generated under
open-system pyrolysis conditions, n-alkane/n-alkene doublets would have been formed.
For instance, during thermal decomposition of polymethylene precursors, carbon-carbon
bonds are cracked while forming an alkene and an alkane with a radical (Fig. 16). Hence,
two reactions are possible: A new alkene and radical are formed by isomerization
decomposition, or an n-alkane is formed by intermolecular H-transfer. In any case and
during thermal cracking under open-system pyrolysis conditions, the hydrogen pressure is
not sufficient to saturate all radicals, and thus n-alkenes are necessary complementation
to their respective n-alkanes. If they are missing in a pyrolysate in which high n-alkane
yields are detected, the n-alkanes can be viewed as previously already present
compounds. A further indicator for the existence of a carryover of free hydrocarbons into
the S2 temperature range are higher S1 yields for the respective samples from the upper
intervals compared to S1 yields of samples from the lower intervals (Table A 2), as well as
the presence of waxy, aliphatic material within the thermal extracts (Tvap) of the former
(Fig. 15).
Information is limited when characterizing the kerogen structure of late and
overmature samples on a molecular level using the ternary diagrams of (Larter, 1984);
Horsfield (1989) and Eglinton et al. (1990), because the labile, H-rich part of kerogen is
already converted to “dead” carbon and petroleum that has partially left the source rock.
This is reflected by pyrolysates of most samples plotting in the field of type IV (inert
kerogen) in Fig. 17c and Fig. 18c. Samples with higher amounts of carried over aliphatic
components still plot in the aquatic area using n-alkenes as input data. Considering the
ternary diagram for resolving the petroleum type organofacies (Horsfield, 1989), carryover
effects can be neglected by conducting only n-alkenes instead of n-alkenes and n-alkanes
for the characterization (Fig. 17a and Fig. 18a). In course of this modification, source
rocks exhibiting VR = 2.4% R0 have a rest-potential to generate gas and aromatic
hydrocarbons during artificial pyrolysis as well as natural maturation, with compositions
plotting in the “Gas and Condensate”-field of Horsfield (1989, 1997).
MOLECULAR CHARACTERIZATION OF GENERATED PRODUCTS
36
In conclusion, it can be said that immature samples from well EX-A generate an
intermediate- to long-chained aliphatic hydrocarbons dominated petroleum with minor
amounts of aromatic and sulphur-bearing compounds indicating an algal precursor
organism (Botryococcus braunii) deposited in a lacustrine environment. The inferred
petroleum type is characterized as paraffinic, high wax oil. Labile kerogen within samples
from late and overmature wells EX-B and EX-C is composed of short-chained aliphatic
hydrocarbons acting as “bridge structures” for aromatic compounds. Pyrolysis would infer
gas and condensate generation upon natural maturation. Samples of the uppermost
horizons of these wells are influenced by a carryover effect which can be identified by the
occurrence of n-alkanes but absence of n-alkenes of higher molecular weight.
Fig. 17 Open-system pyrolysis-GC data for typing of the molecular kerogen structure and petroleum type
organofacies of overmature samples of well EX-B using the ternary diagrams of (a) Horsfield, 1989, (b)
Eglinton et al., 1990 and (c) Larter, 1984
n-C15+ 80%
C1-5
100%
80% n-C6-14
Paraffinic OilLow Wax
Paraffinic OilHigh Wax
P-N-A OilLow Wax
P-N-A OilHigh Wax
Gas andCondensate
terrestrial
Type IV
aquatic
0 20 40 60 80 100Phenol
100
80
60
40
20
0
n-C
8:1
100
80
60
40
20
0
m,p
-Xyl
ene
aromatic
aliphatic
intermediate
high-sulphur
0 20 40 60 80 100n-C9:1
100
80
60
40
20
0
o-Xylen
e
100
80
60
40
20
0
2,3-
DM
-Thio
phen
e
(a) (b) (c)
n-alkenes
Fig. 18 Open-system pyrolysis-GC data for typing of the molecular kerogen structure and petroleum type
organofacies of late mature samples of well EX-C using the ternary diagrams of (a) Horsfield, 1989, (b)
Eglinton et al., 1990 and (c) Larter, 1984
n-C15+ 80%
C1-5
100%
80% n-C6-14
Paraffinic OilLow Wax
Paraffinic OilHigh Wax
P-N-A OilLow Wax
P-N-A OilHigh Wax
Gas andCondensate
terrestrial
Type IV
aquatic
0 20 40 60 80 100Phenol
100
80
60
40
20
0
n-C
8:1
100
80
60
40
20
0
m,p
-Xyl
ene
aromatic
aliphatic
intermediate
high-sulphur
0 20 40 60 80 100n-C9:1
100
80
60
40
20
0
o-Xylen
e
100
80
60
40
20
0
2,3-
DM
-Thio
phen
e
(a) (b) (c) n-alkenes
LABILITY OF THE ORGANIC MATTER (BULK KINETICS)
37
4.2 Lability of the organic matter (bulk kinetics)
The bulk kinetic approach has been used to determine the kinetic parameters of
primary bulk petroleum generation from kerogen using non-isothermal open-system
pyrolysis, i.e. the Source-Rock-Analyzer (SRA). Results of four immature source rock
samples (marine influenced sample G010283, and lacustrine samples G010305,
G010316 and G010351) were used to extrapolate generation characteristics to a
geological heating rate of 3°C/Ma, as a basic input for the PhaseKinetics approach (di
Primio & Horsfield, 2006), and as a spline approximation for compositional kinetics (only
samples G010283 and G010351).
The complex composition of kerogen as described by Behar & Vandenbroucke
(1987) and the manifold reactions going on during conversion of kerogen to petroleum
requires simplification by applying a gross kinetic concept in which molecular precursors
of oil and gas are replaced by so called bulk petroleum potentials. On-going reactions are
considered to follow a first-order kinetic scheme and the Arrhenius Law (eq. (2); (van
Heek & Jüntgen, 1968; Schenk et al., 1997b).
Arrhenius law: (2)
Thus, kinetic parameters describing hydrocarbon generation consist of an activation
energy distribution and a pre-exponential frequency factor A. The used mathematical
routine has been described by Schaefer et al. (1990). It is based on kinetic analysis of the
gross hydrocarbon formation rate versus temperature:
∑
(
)
∫ (
)
k – Constant of reaction velocity (rate constant) A – Pre-exponential or frequency factor EA – Activation energy [J/mol] R – Universal gas constant (8.314 J/mol) T – Absolute temperature [K]
(3)
LABILITY OF THE ORGANIC MATTER (BULK KINETICS)
38
For calculation of kinetic parameters Kinetics2000 software is used. In a first step,
measured “pyrolysis generation rate curves” are normalized to their maximum values
yielding a Tmax for each linear heating rate. In a second step, hydrocarbon generation
kinetic parameters are calculated by applying a discrete activation energy distribution
model consisting of n = 25 or fewer parallel reactions with activation energies Ei regularly
spaced by 1 kcal/mol and a single frequency factor A. For practical reasons, the pre-
exponential factor A is assumed the same for all reactions (Ungerer & Pelet, 1987), with
the consequence that single reactions commence in the order of increasing activation
energies at increasingly high temperatures (Tissot & Espitalie, 1975; Ungerer, 1990).
The best fit between measured and calculated formation rates were attained for the
four investigated samples with activation energy distributions (EA) and single pre-
exponential factors (A) displayed in Fig. 19 as well as in Table 4. All data clearly reflect
the origin of the organic matter within the distinct stratigraphic and organic facies. Marine
influenced sample G010283 shows a typical marine influenced signature (Tegelaar &
Noble, 1994) by displaying a broad (more or less Gaussian-curve shaped) activation
Fig. 19 Activation energy distribution of immature marine and lacustrine samples with frequency factor A (1/s)
LABILITY OF THE ORGANIC MATTER (BULK KINETICS)
39
energy distribution with values ranging
between 44 and 64 kcal/mol. The main
energy at 55 kcal/mol accounts for 45% of
the total kerogen to petroleum conversion
reaction. Furthermore, the frequency factor
of 3.84E+14 s-1 is the lowest of the here
investigated samples (Table 4).
Although comparison of kinetic parameters
from literature with kinetic parameters of
sample G010283 is equivocal it can be said
that kinetic parameters of sample G010283
are within the range of those of a worldwide
marine source rock collection published in
Tegelaar & Noble (1994) and Braun et al.
(1991). Activation energies of their sample
set, which comprises sulphur-poor marine
organic matter stemming from type II
kerogens of Bakken, Woodford, Barnett
Shale as well as Kimmeridge Clay, range
between 48 and 63 kcal/mol whereas
frequency factors range between 7.7E+13
and 1.2E+15 s-1. These types of organic
matter are similar to the kerogen structure
of sample G010283 which is dominated by
intermediate-chained aliphatic
hydrocarbons with low abundance of
aromatic or sulphur compounds (see
chapter 4.1.2). Consequently and assuming
a geological, linear heating rate of 3°C/Ma,
kerogen to hydrocarbon conversion in the
marine influenced Wealden Shale sample
is, with a Tmax as well as a TR50% of 148.4°C
(Table 5), less stable than kerogen to hydrocarbon conversion in the more lacustrine
influenced Wealden samples, but geological Tmax values resemble the S-poor, marine
sample set of Tegelaar & Noble (1994). Here Tmax values range between 142 and 150°C.
The geological prediction is also comparable to thermally more instable lacustrine
Table 4 Kinetic parameters (activation energies and
frequency factors) for four immature samples
GFZ sample number G010283 G010305 G010316 G010351
Specificsslow rates slow rates slow rates slow rates
A (sec-1
) 3.84E+14 5.30E+15 1.12E+15 2.07E+15
E (kcal/mol) % % % %
40
41
42
43
44 0.05
45 0.04
46 0.09
47 0.20
48 0.11
49 0.52 0.02
50 0.28
51
52 1.18 0.26
53 1.60
54 19.34
55 45.51
56 13.09
57 12.09
58 1.36 98.23
59 2.98 96.87
60 95.73
61 0.96 1.53 1.18
62 0.09 1.72 1.91
63 2.26
64 0.51
65 0.23
66
67 0.03
68
69
70
71
72 0.02
Table 5 Calculated temperatures and vitrinite
reflectances for a geological heating rate of 3°C/Ma
10% TR 50% TR 90% TR geologic Tmax
Ro-% Ro-% Ro-% Ro-%
Bulk G010283 0.788 0.960 1.241 0.960
Bulk G010305 1.106 1.303 1.461 1.341
Bulk G010316 1.021 1.207 1.363 1.244
Bulk G010351 1.085 1.275 1.434 1.313
boiling
rangesample
10% TR 50% TR 90% TR geologic Tmax
°C °C °C °C
Bulk G010283 133.2 148.4 165.4 148.4
Bulk G010305 156.8 168.6 176.9 170.5
Bulk G010316 151.9 163.5 171.6 165.6
Bulk G010351 155.5 167.2 175.4 169.1
boiling
rangesample
LABILITY OF THE ORGANIC MATTER (BULK KINETICS)
40
samples (AP24, GOVT) published in Braun et al. (1991) exhibiting Tmax between 147 and
149°C.
The more lacustrine influenced Wealden Shale samples (G010305, G010316 and
G010351) clearly show a typical lacustrine activation energy distribution which is
dominated by one single EA (here between 58 and 60 kcal/mol) accounting for at least
96% of the total kerogen to petroleum conversion reaction. The narrow EA distribution
results from the homogeneous composition of the algae derived organic matter precursor
material comprising only a limited range of chemical bonds. The preserved algae
biopolymer occurring in cell walls of various lacustrine algae (de Leeuw & Largeau, 1993;
Tegelaar & Noble, 1994) is the main precursor for lacustrine type I kerogens. As revealed
from organic petrography Botryococcus braunii is the dominant algae type in the
investigated samples. The conversion rate is higher than for marine samples, which can
be noticed by a much steeper slope of the transformation ratio rate curve (Fig. 19).
Furthermore, lacustrine samples exhibit higher frequency factors (1.12E+15 to
5.30E+15 s-1) as well as elevated onset temperatures (152 - 157°C) and peak petroleum
generation temperatures (T50% = 165 - 170.5°C) for a hypothetical geological heating rate
of 3°C/Ma. Tmax values range between 165.6°C and 170.5°C (see Table 5). These kinetic
predictions are mostly in accordance with previously published data for the bulk kinetics of
lacustrine oils derived from type I kerogens (Braun et al., 1991; Horsfield et al., 1994;
Tegelaar & Noble, 1994). Predictions to geological heating rates for Wealden Shale
samples result in thermally stabilities which are inconsiderably higher than predictions for
most of the lacustrine kerogens poor in sulphur and aromatic compounds compiled by
these authors. Green River Shale samples (e.g. from wells Brotherson 1-23B4 and
Fig. 20 Computed generation rate curves and transformation ratio curves for a geological heating rate of
3°C/Ma for G010283, G010305, G010316 and G010351
LABILITY OF THE ORGANIC MATTER (BULK KINETICS)
41
Government 33-4) from Uinta Basin (Braun et al., 1991) and Pematang samples
(Indonesian Brown Shale, (Tegelaar & Noble, 1994)) exhibit maximal generation
potentials (Tmax) ranging between 147 and 165°C. Nevertheless, in the case of a
Tasmanian Cannel Coal (Tegelaar & Noble, 1994) composed of the algae Botryococcus
braunii even higher primary petroleum generation temperatures can be reached (Tmax =
180°C). In a related context, Behar et al. (1995) have shown that thermal alteration
products of different Botryococcus braunii races possess different thermal stabilities, e.g.
race L produces less stable compounds than race B.
PHASEKINETICS APPROACH
42
4.3 PhaseKinetics approach
The PhaseKinetics approach was used to develop compositional kinetic schemes
with which one is able to predict the phase behaviour of natural petroleum generated from
different organofacies. It combines data from open- and closed-system pyrolysis
techniques, i.e. open-system bulk kinetic and closed-system compositional kinetic
information, and integrates it in a compositional kinetic model which allows the prediction
of hydrocarbon physical properties at different thermal stress levels (di Primio & Horsfield,
2006). Phase behaviour is commonly described using a stored fluid’s specific properties
such as gas-oil-ratio (GOR in Sm³/Sm³), formation volume factor (FVF or B0 in m³/Sm³), or
saturation pressure (Psat in bar). One should keep in mind, that a correct prediction of
natural fluid properties is made difficult by the fact that bulk composition of unaltered
natural petroleum fundamentally differs from the composition of kerogen pyrolysates,
irrespective of crude oil, kerogen type or pyrolysis condition (Larter & Horsfield, 1993;
Horsfield, 1997). Crude oils are hydrocarbon-rich systems, whereas pyrolysates are
composed of higher portions of polar and aromatic components (Urov, 1980; Castelli et
al., 1990).
Four immature samples from each stratigraphic interval of well EX-A underwent
artificial closed-system maturation using a non-isothermal heating rate of 0.7 K/min to
distinct temperatures representing certain kerogen to hydrocarbon transformation ratios
(TRs of 10%, 30%, 50%, 70% and 90%). End temperatures (Table 6) were directly
derived from the 0.7 K/min SRA bulk petroleum pyrolysis evolution curve. Generated
hydrocarbons of each TR-level were then gas-chromatographically analysed as described
in the chapter “MSSV-Py-GC-FID” (3.3.4).
sample ID10% TR
[°C]
30% TR
[°C]
50% TR
[°C]
70% TR
[°C]
90% TR
[°C]
G010283 368.7 388.3 401.6 413.3 432.4
G010305 390.4 408.3 417.8 426.0 437.3
G010316 389.5 408.7 418.1 426.3 437.3
G010351 394.7 411.6 421.0 429.3 440.2
Table 6 Temperatures of corresponding TR for artificial maturation at a
heating rate of 0.7 K/min
PHASEKINETICS APPROACH
43
4.3.1 Phase behaviour prediction
The calculation of petroleum phase behaviour on the basis of EOS (equation of
state) is best performed using a compositional resolution containing seven compounds of
the gas range (C1, C2, C3, i-C4, n-C4, i-C5, n-C5), a pseudo C6 (corresponding to all
compounds eluting after n-C5 until n-C6) and a C7+ fraction (containing all compounds
eluting after heptane including the latter) (di Primio & Horsfield, 2006).
The description of the cumulative fluid composition at different transformation ratios
was processed using PVTsim© 17 by Calsep A/S. Here, the gas range is defined based
on analytical results obtained from MSSV closed-system pyrolysis measurements and the
liquid range is defined based on a mathematical extrapolation of the C7+ properties.
Iteration of molecular composition has been applied until GOR did not change anymore,
mostly two or three runs were appropriate. The original GOR’s from MSSV measurements
were used as a starting point and converted to volumetric data by a single stage flash.
Simulation has been applied for a reservoir temperature of 100°C which is an empirical
standard temperature when no burial model for the investigation area is available.
The C7+ fraction definition was used to calculate a distribution of components
representing the total liquid phase di Primio & Horsfield (2006). “This C7+ characterization
consists of representing the hydrocarbons with 7 or more carbon atoms by a reasonable
number of pseudo-components, whereby a logarithmic relationship between the molar
concentrations zN of a given fraction and the corresponding carbon number, CN, for
CN>7 is assumed” (Pedersen et al., 1989). The C7+ fraction is additionally characterized
by molecular weight and density. The molecular weight of the C7+ fraction is gained from
the GC hump by subdividing it into boiling ranges according to n-alkane pseudo
components (see below) and using the average molecular weight of the resolved
compounds as representatives of the respective hump range. A so called C+ factor (of 0.8)
was applied to the molecular weights to level them down to empirical values between 230
and 260 mol-% (di Primio, personal communication). The C7+ density was attained by a
linear, molecular weight-density correlation of natural petroleum fluids from the North Sea
which is believed by di Primio & Horsfield (2006) to be valid for black oils in general. For
simplification, the C7+ fraction, consisting of more than 200 compounds, was subdivided
into six pseudo compounds (C7-15, C16-25, C26-35, C36-45, C46-55, and C56-80) by a lumping
procedure, a minimum that is required for satisfactory calculation of phase behaviour (di
Primio & Horsfield, 2006). Physical properties remain the same for each pseudo
PHASEKINETICS APPROACH
44
compound, only molecular portions change depending on the samples original
composition.
The gas compositions of
pyrolysates consistently lack
methane, which is the
component with the highest
impact on the phase
behaviour (Psat is mainly
controlled by gas dryness).
Therefore and according to
di Primio & Horsfield (2006), only the composition, and not the GOR, requires correction.
The gas composition was corrected by assuming increasing ratios of methane to wet gas
(C1/C2-5) for increasing degrees of kerogen transformation. This was done by shifting the
Psat-B0 trends of source rock pyrolysates to behave as straight lines as can be adopted
from the linear correlation between Psat-GOR and Psat-B0 for genetically related petroleum
fluids. The correction procedure affects almost exclusively Psat. Correction values for
(C1/C2-5) can be found in Table 7.
Several diagrams can be used to illustrate the development of physical fluid properties
during kerogen to oil conversion. In Fig. 21 a clear differentiation according to the
investigated sample’s origin is revealed. The marine influenced sample G010283 is
separated from the 3 other samples stemming from the sublitoral lake facies (G010305)
and the deep lacustrine facies (G010316 and G010351).
Marine influenced sample exhibits typical marine petroleum generating characteristics
yielding black oil with GOR’s ranging from 75 to 103 Sm³/Sm³ and a Psat between 113 and
150 bar, both properties progressively increasing with kerogen conversion level.
Lacustrine influenced samples exhibit lower GOR’s (34-58 Sm³/Sm³) (Fig. 21, Table 8)
which remain more or less uniformly low for increasing transformation ratios. Similarly, Psat
shows lowered values between 79 and 115 bar. It can be seen in the GOR and B0 plot
(Fig. 21) that the generated fluids range within a very limited area which is a typical
behaviour for homogeneously structured kerogens of lacustrine origin (see discussion in
Horsfield (1989)).
Table 7 Methane correction factors (C1/C2-5) for four immature samples
of well EX-A
10% TR 30% TR 50% TR 70% TR 90% TR
G010283 1.35 1.32 1.33 1.34 1.38
G010305 1.23 1.21 1.24 1.23 1.24
G010316 1.22 1.20 1.20 1.20 1.23
G010351 1.22 1.22 1.21 1.22 1.25
sample no.gas correction factor
PHASEKINETICS APPROACH
45
Fig. 21 Physical properties of representative early mature Wealden Shale samples originating from different
depositional environments plotted in Psat vs. B0 diagram (upper left), Psat vs. GOR (upper right) and GOR as
well as Psat vs. TR representing maturity (lowermost diagrams)
G010283
10 30 50 70 90
GOR 75.00 78.70 82.60 87.50 102.50
Bo 1.29 1.29 1.30 1.31 1.36
Psat 112.91 129.97 135.01 144.54 149.68
TR G010305
10 30 50 70 90
GOR 33.60 40.00 50.10 50.60 55.80
Bo 1.14 1.16 1.20 1.19 1.21
Psat 78.58 93.53 99.42 109.31 114.48
TR
G010316
10 30 50 70 90
GOR 45.20 41.30 42.80 43.00 53.00
Bo 1.17 1.16 1.17 1.16 1.20
Psat 101.83 93.48 99.29 101.65 108.74
TR G010351
10 30 50 70 90
GOR 43.20 46.30 46.20 49.60 58.10
Bo 1.18 1.18 1.17 1.18 1.22
Psat 87.11 99.77 106.35 111.16 115.32
TR
Table 8 Physical properties of representative immature Wealden Shale samples
PHASEKINETICS APPROACH
46
4.3.2 Compositional description of activation energy distribution
A first predictive compositional model was developed on the basis of the open-
system activation energy distribution (Fig. 19) and the closed-system molar compositions
of C1-6 single components and C7+ compounds. Molar compositions are listed in Table 9
and the compositional kinetic models are shown in Fig. 22. The integration of PVT data
sets was done by multiplying molecular fractions calculated by PVTsim© with the
molecular weights of the respective compounds and predefined boiling ranges as well as
normalizing distributed potentials to the total potential of each pseudo-compound. For
potentials up to 20% kerogen conversion, the compositional information of the 10% TR
MSSV-end temperature was applied. For potentials between 20 and 40% kerogen
conversion, the 30% TR MSSV-end temperature molecular composition was assigned,
etc. The composition of generated petroleum results from adding the distributed potentials
of the single activation energies.
Fig. 22 Activation energy distributions of four immature Wealden Shale samples with integrated compositional
information
PHASEKINETICS APPROACH
47
The compositional model confirms
the previously determined results showing
a clear separation between the marine
sample G010283 and the three lacustrine
influenced samples G010305, G010316
and G010351. As previously discussed,
sample G010283 exhibits a typical marine
energy distribution characterised by a
main activation energy accounting for
~48% of the bulk reaction, which indicates
a compositionally more heterogeneous
kerogen structure. In contrast, lacustrine
samples show a single dominant
activation energy indicating the presence
of a very homogeneous, mainly
polymethylene-like kerogen (Behar &
Vandenbroucke, 1987) composed of a
limited number of chemical C-C bonds
(Claxton et al., 1993). But compositional
differences between the marine and
lacustrine samples are also observable
(Table 9).
All the investigated samples produce paraffinic high-wax oil containing a very minor
proportion of gaseous hydrocarbons. The marine sample G010283 comprises 88 wt-%
liquid fraction and 12 wt-% gaseous hydrocarbons of a wet gas composition to which
methane accounts for one-third. The highest potentials are achieved in the C7-35 fraction
but the heavy C15+ fraction represents more than half of the compositional portion. The
lacustrine sample G010351 is composed of only 8.0 to 8.7 wt-% gas and has therefore a
higher proportion of liquids (91.3 - 92 wt-%). However, the distinct generative potentials
within the liquid fraction differ from the lacustrine composition. The lighter liquids (C6-14)
account less whereas the heavier, waxy portions increased and make up nearly two-
thirds. Particularly, the potentials of the C26+ fractions are elevated compared to the
marine sample causing the lower values in GOR, Psat and B0.
Table 9 Petroleum generation potentials of single
gaseous compounds and defined liquid boiling ranges
for 4 selected, immature samples
G010283 G010305 G010316 G010351
n -C1 3.80 2.50 2.40 2.62
n -C2 2.18 1.31 1.25 1.30
n -C3 2.29 1.75 1.72 1.88
i -C4 0.23 0.09 0.09 0.12
n -C4 1.47 1.31 1.27 1.39
i -C5 0.73 0.18 0.17 0.19
n -C5 1.02 1.14 1.09 1.19
n -C6 3.71 3.65 3.50 3.62
C7-15 27.28 23.61 24.26 24.20
C16-25 25.40 24.74 25.09 24.93
C26-35 15.60 17.22 17.22 17.04
C36-45 8.52 10.64 10.50 10.34
C46-55 4.36 6.15 5.99 5.87
C56-80 3.40 5.71 5.44 5.31
Gas 11.73 8.29 7.99 8.69
Oil 88.27 91.71 92.01 91.31
C1 3.80 2.50 2.40 2.62
C2-5 7.93 5.78 5.59 6.07
C6-14 30.99 27.26 27.76 27.82
C15+ 57.28 64.45 64.25 63.49
potentials [wt-%]
PHASEKINETICS APPROACH
48
4.3.3 PVT analysis using phase envelopes
Characterizing physical properties of a reservoir fluid as well as changes in volume
and phase state occurring during production are the main applications of PVT analysis
based on fluid composition (di Primio et al., 1998). The phase behaviour has, amongst
others, been described by pressure vs. temperature diagrams displaying phase envelopes
(Fig. 23). Pressure-temperature (PT) conditions for which a fluid occurs in a saturated
two-phase state can be found within the phase envelopes, whereas outside the envelopes
reservoir fluids occur in an undersaturated phase of either liquid or gas (di Primio &
Horsfield, 2006). The phase envelope is subdivided into a bubble point curve and a dew
point curve which meet at the critical point. The bubble point curve is defined as the
border between gas phase and a supracritical liquid while the dew point curve marks the
separation from a liquid phase to a supracritical gas phase. The critical point characterizes
PT-conditions where all three states occur contemporaneously. The maximum pressure
above which no gas can be formed regardless of temperature is called cricondenbar. The
maximum temperature above which no liquid can be formed regardless of pressure is
called cricondentherm.
Compositional data used for PVT analysis was taken from the corrected fluid composition
consisting of gaseous phase components and liquid phase pseudo-compounds as
described in the former paragraph. The predicted phase envelopes of cumulative fluids
generated from Wealden Shale rock samples at five transformation ratios were calculated
using PVTsim© and are displayed in Fig. 23. One can see that the shape of the phase
envelopes strongly depends on the composition of the fluids and thus on maturity or
precursor origin; the quantity of light hydrocarbons dissolved in the liquid phase (GOR)
has the largest influence. Thus, “loaf-shaped” phase envelopes, which are characteristic
for black oils, can be observed for all investigated samples, whereas the phase envelopes
of the lacustrine samples are “flatter” than those of the marine sample G0102893. This
can be explained by a higher GOR of the latter.
PHASEKINETICS APPROACH
49
Cricondentherm and critical point are influenced by molecular weight and density of
the C7+ fraction. High molecular weights (see Table 9) and densities result in a high
cricondentherm, a low GOR and a low Psat, a feature observable for the lacustrine
samples G010305, G001316 and G010351. All lacustrine samples show similar PT-
characteristics with similar cricondenbar (137 - 144 bar) and cricondentherm values
(~571°C) as well as more or less similar critical points ranging between 401 and 481°C
and 90 and 148 bar. A differentiation between physical properties of lacustrine samples
and the marine influenced sample G010283 is easily made based on the compositional
differences in composition due to differences in depositional and organic facies as well as
homogeneity of kerogen and the generated hydrocarbons. Sample G010283 exhibits
phase envelopes with bubble point curves extending to a higher saturation pressure
(180 bar) and a dew point curve which is characterized by a lower temperature (535°C).
Fig. 23 Phase envelopes of the petroleum generated primarily at different transformation ratios from the
immature Wealden Shale samples of marine (G010283) and lacustrine (others) origin, additionally showing
the PT conditions within the early to overmature wells EX-A, EX-B and EX-C
PHASEKINETICS APPROACH
50
This is consistent with the slightly higher GOR of the generated hydrocarbons induced by
differences in the organic matter structure of petroleum precursors (di Primio et al., 1998).
In general and with increasing maturity a systematic decrease in cricondentherm
and increase in cricondenbar can be expected for type-II and type-III kerogens, as well as
a shift of the critical point towards higher pressures and lower temperatures (di Primio et
al., 1998). Interestingly, for the present sample set critical points move towards higher
pressures but not progressively to lower temperatures with increasing maturity. Both,
temperature and pressure values are partly increasing with maturity. Some samples show
at least a “crossover area” in which critical points move first to higher temperatures before
decreasing to lower ones while they steadily increase in pressure. It seems that due to the
specifications of conversion of homogeneously distributed, lacustrine type-I kerogen (di
Primio et al., 1998) observations are only a rule of thumb. Maturation of a type-I kerogen
proceeds within a limited temperature interval in which the OM (mainly Botryococcus
braunii) is converted into petroleum at a very fast rate (Fig. 20). The modelled cumulative
composition (Fig. 22, Table 9) consists to 96 - 98% (for lacustrine samples, Table A 5) of
the fluid composition measured at 90% kerogen conversion (TR). Thus, the gas
composition as well as the GOR does not change significantly throughout maturation as it
does for more heterogeneous kerogen types II and III (Kuhn et al., 2010). Consequently,
the shape of the phase envelope for a type I kerogen mainly depends on the origin and
heterogeneity of the organic matter.
Assuming standard linear PT gradients for a sedimentary basin, 10 bar/km
(hydrostatic pressure) and, in case of the LSB, 36°C/km (Bruns et al., 2013b; a), phase
states at the present depths of the four intervals (Table 2) of the generated hydrocarbons
from the early mature well EX-A can be derived using the phase envelopes in Fig. 23.
Deep marine interval of well EX-A are situated in a depth ranging from 831.5 to 850.5 m
(Table 2) where a pressure of 82 - 82 bar prevails. Thus, and compared to the phase
envelope, the generated hydrocarbons from the marine kerogen of a composition similar
to sample G010283 occur in the depth of its bubble point when assuming a transformation
ratio of 10% which is comprehensible at a vitrinite reflectance of 0.78% R0. Therefore,
when produced or raised by a geological uplift the petroleum of this formation occurs in a
two-phase state of coexisting oil and gas. As the sublitoral lake facial and lacustrine
samples (G010305, G001316 and G010351) are deeper situated (909.5 to 1058 m) and
containing a slightly different kerogen composition to the marine one, with more flattened
phase envelopes, the pressure is slightly increased (89 - 91 bar for G010305, 95 - 98 bar
for G010316 and 101 - 104 bar for G010351). Thus, the generated hydrocarbons clearly
occur in a single-state as undersaturated oil with dissolved gas. If raised to shallower
PHASEKINETICS APPROACH
51
depths by production or uplift, and assuming a composition that corresponds to 10% TR,
the oil and gas phases would separate from each other in a depth of 550 m, 744 m and
622 m for the respective compositions from samples G010305, G010316 and G010351.
One can assume that petroleums generated from the late and overmature wells EX-
C and EX-B contain the same compositions, and thus physical properties, as
hydrocarbons from the marine and lacustrine samples of well EX-A do. Thus, and if not
cracked to gas, these fluids should be trapped somewhere in the hydrocarbon system of
the LSB occurring in a phase state in dependence of the depth of the trapping formation.
But more precise statements can only be made by integrating the PVT and compositional
data into a 1D geological model with a subsidence history for the Lower Saxony Basin,
e.g. as Bruns et al. (2013a, 2013b) did.
COMPOSITIONAL KINETIC APPROACH
52
4.4 Compositional Kinetic approach
Non-isothermal closed-system MSSV-pyrolysis gas chromatography was used for
the determination of kinetic parameters of kerogen to petroleum conversion (primary
cracking/formation) and oil to gas conversion (secondary cracking/formation) for two
selected immature samples from different stratigraphic levels and organic facies of well
EX-A to receive kinetic models indicative for the kerogen type within each organofacies.
Sample G010283 originates from the marine influenced depth interval, sample G010351
originates from the lowermost deep lacustrine interval (1050 m, Table 2).
In a first step cumulative petroleum generation curves are developed for the three
heating rates 0.7, 2.0, and 5.0 K/min by investigating total product yields of 67
subsamples heated to temperatures given in Table 10. The possibility and mathematical
Temp [°C] 0.7 K/min 2.0 K/min 5.0 K/min
395
410
420
425
430
440
445
450
455
460
465
475
480
500
505
525
530
550
555
575
580
600
605
Temp [°C] 0.7 K/min 2.0 K/min 5.0 K/min
370
385
390
395
400
405
415
420
430
435
445
450
465
470
475
480
500
505
525
530
550
555
575
580
600
605
Table 10 End temperatures for closed-system MSSV pyrolysis experiments at
samples G010283 and G010351 using three different heating rates
COMPOSITIONAL KINETIC APPROACH
53
basis to calculate specific frequency factors and activation energies for the generation of
individual compounds, compound groups, boiling fractions or secondary gas species was
already formulated in Jüngten (1964); Jüntgen & van Heek (1968) and Schaefer et al.
(1990). The resulting chromatograms and concentrations of single gaseous components
and liquid boiling fractions (C6, C7, ..., C30+) can be found in the appendix (Table A 6). Fig.
26 shows representative GC fingerprints from the lacustrine sample at a heating rate of
0.7 K/min and different temperatures representing conversion stages (90% TR at
440.2°C) and at an elevated temperature of 525°C.
4.4.1 Evolution of boiling ranges during MSSV pyrolysis
Fig. 24 Total MSSV C1+ pyrolysis yields for temperatures up to 605°C at 3 different heating rates (0.7, 2 and 5
K/min) for samples G010283 and G010351; top: Absolute yields, bottom: yields normalized to highest yield
COMPOSITIONAL KINETIC APPROACH
54
In Fig. 24 cumulative evolution curves of Total MSSV C1+ products generated during
artificial maturation of two selected Wealden Shale samples (G010283, G010351) at 3
different heating rates (0.7, 2 and 5 K/min) are shown. All evolution profiles are shifted
towards higher temperature with increasing heating rate which is in accordance with non-
isothermal kinetics (van Heek & Jüntgen, 1968). During petroleum generation kerogen is
converted into liquid (C6+) and gaseous (C1-5) hydrocarbons which is translated into a
progressive increase of Total C1+ MSSV pyrolysis yields until a cumulative product plateau
is reached. The temperature for which the cumulative plateau is reached should also be
shifted to higher values with increasing heating rates. Due to an erroneously too low yield
at 480°C for the 5 K/min heating rate, the cumulative plateau is reached earlier than for
the 2 K/min heating rate for sample G010283. After reaching maximum yields, product
amounts slightly decrease at enhanced temperatures (above calculated temperatures of
90% TR) indicating domination of secondary cracking processes over primary generation
processes besides formation of coke (Dieckmann et al., 1998). Absolute maximum yields
range between 39.1 and 55.1 mg/g for the marine sample G010283 and 150.7 and
178.6 mg/g for the lacustrine sample G010351, but not directly depending on the heating
rate. Maximum absolute product yields do not follow the observation of Dieckmann et al.
(2000a) on marine type II kerogens that maximum yields decrease with increasing heating
rates.
Considering distinct boiling ranges (C1-5, C6-14 and C15+) (Fig. 25) it becomes clear
that heavier components (C15+ compounds) are the first MSSV-pyrolysis products
generated during kerogen conversion. Lower molecular weight components of the C6-14
boiling range are generated later and reach their maximum yields at temperatures about
15 - 20°C higher. Nevertheless, precise temperature ranges cannot be given because
Fig. 25 Product evolution curves of samples G010283 and G010351 at representative heating rates (5 K/min
for G010283 and 0.7 K/min for G010351) for boiling ranges C1-5, C6-14 and C15+ as well as Total C1+ yields
from closed-system MSSV pyrolysis
COMPOSITIONAL KINETIC APPROACH
55
temperature intervals between the single measurements are too widely spaced. Maximum
product yields for distinct boiling ranges at different heating rates are approximately the
same (±8 mg/g sample), which is a prerequisite for kinetic modelling (Dieckmann et al.,
2000a). The temperatures for the cumulative maximum product yields range from 430 to
470°C (increasing with heating rate) for the C15+ boiling range of both, the marine-
influenced and deep lacustrine sample. The cumulative apex is reached about 10°C
higher in the case of the lacustrine sample (G010351) which is caused by a more
homogeneously composed kerogen structure inducing a higher thermal stability.
Maximum C6-14 boiling range yields are measured between 450 and 500°C with the same
temperature difference between samples G010283 and G010351. The temperature shifts
to higher temperatures with increasing heating rates. The apices of the cumulative
generation curves mark the temperatures where primary generation processes are
overcompensated by secondary cracking processes. C15+ components are cracked to
hydrocarbons of lighter molecular weight, most likely to predominantly C6-14 compounds,
but also to early secondary gas and coke (Mahlstedt, 2012). C6-14 compounds are cracked
to secondary gas and a carbonaceous residue (coke). This is expressed by a continuous
decrease of product amounts.
The slope of the decrease of C6+ compounds is initially steep and subsequently flat,
a process related to the composition of the primary liquid products. During cracking of
primary hydrocarbons its composition changes from aliphatic to aromatic and thus H/C
ratios decrease. At temperatures for which slopes rapidly change (510 to 535°C
depending on the heating rate) only aromatic components are left over for cracking. This
is demonstrated in Fig. 26 by differences in MSSV gas chromatograms at 440.2°C and
525°C. In the latter, aromatic structures dominate the hydrocarbon composition whereas
aliphatic species (>C4) are totally depleted. The slope changes because aromatic ring
structures are not converted to secondary gas (methane [and wet gas]) as easily as
longer chained alkanes (Mahlstedt, 2012).
COMPOSITIONAL KINETIC APPROACH
56
Generation of gaseous hydrocarbons (C1-5) already starts at about 400°C and
reaches its apex at about 500-530°C for the lacustrine sample G010351 and at about 525-
550°C for the marine sample G010283 (Fig. 25). After reaching maximum product
amounts, yields do not decrease to the same extent as observed for higher molecular
components; yields remain at a cumulative plateau. The steadily ongoing cracking
process of C6+ compounds generates secondary gas which is itself cracked from wet gas
to dry gas. A very low decrease in absolute product yields indicates the formation of coke
during cracking of wet gas to methane (Erdmann & Horsfield, 2006).
Based on two compositional models published by Dieckmann et al. (1998) as well
as Erdmann & Horsfield (2006) a new approach has been developed which aims to
optimize secondary gas amount prediction and thus yields more realistic kinetics of oil and
gas formation. In the following two sub-chapters the two approaches will be introduced
first, before, in a third sub-chapter, the new approach will be explained.
Fig. 26 GC-fingerprints of
lacustrine sample
G010351 at a heating
rate of 0.7 K/min to
exemplify the
compositional evolution
from offset of petroleum
generation (90% TR, top)
to 525°C (bottom)
COMPOSITIONAL KINETIC APPROACH
57
4.4.2 The conservative evaluation approach (after Dieckmann et al.,
1998)
The conservative evaluation approach is based on Dieckmann’s assumption that the
generation of secondary gas starts when the formation of primary liquids (C6+) has ended,
an assumption deduced from comparing multistep open- and closed-system pyrolysis
product yields of a Posidonia as well as a Duvernay Shale sample comprising immature,
marine type II organic matter. He showed that the degradation of C6+ compounds under
closed-system-MSSV-pyrolysis conditions commences when liquid hydrocarbon
generation in open-system reaches its cumulative plateau (Sweeney et al., 1987;
Schaefer et al., 1990; Horsfield et al., 1992), and thus no significant overlap between
primary and secondary gas formation occurs. Secondary gas yields can be calculated
from the degradation of MSSV C6+ compounds (Fig. 27a, Fig. 28). Assuming, for reasons
of hydrogen balance, that only 70% of cracked liquid compounds are converted to gas
and 30% are converted into pyrobitumen (coke), Dieckmann et al. (1998) derived the
following formula:
(a) (b)
Fig. 27 (a) "Conservative approach" (based on Dieckmann et al. (1998)) vs. (b) "Refined approach" (based on
Erdmann & Horsfield (2006)), after Mahlstedt (2012)
COMPOSITIONAL KINETIC APPROACH
58
[ ] (4)
0.7 is the average conversion factor which is estimated from the formula
(5),
where n represents the average H/C ratio of all C6+ compounds, m represents the average
H/C ratio of the secondary gas and u equals the average H/C ratio of pyrobitumen. This
yields
(6)
and a conversion factor of
(7).
The conversion factor fc is 0.7 when assuming n = 2.2 (average of hexane and
triacontane), m = 3.2 (average of methane and pentane) and u = 0.2. The assumed
average compositions can be adapted to different scenarios (Erdmann & Horsfield, 2006)
whereas fc=0.7 can be seen as the result of a maximum conversion scheme.
The amount of primary gas can be easily calculated by subtracting calculated
secondary gas yields from Total MSSV gas yields using the following formula:
(8)
Cumulative yield curves for boiling ranges and compound classes using the
conservative approach are shown in Fig. 28 and a comparison to the refined approach
(see next subchapter 4.4.3) is given there.
M6+max = maximum of C6+ evolution curve at temperature Tk M6+ res = residual amount of liquid hydrocarbons at elevated temperature Tx Msec.gas = resulting amount of secondary gas at temperature Tx
COMPOSITIONAL KINETIC APPROACH
59
4.4.3 The refined evaluation (after Erdmann & Horsfield, 2006)
The spline curve maxima of C6+ generation in the conservative approach were
approximated to the maximum amounts of the closed-system C6+ data yielding different
amounts at each heating rate (e.g. 0.872, 0.773 and 0.797 at 0.7, 2 and 5 K/min for
sample G010351, respectively) and producing different product evolution curve shapes
and slope. Thus, secondary gas amounts are underestimated and primary gas amounts
are overestimated. In contrast to Dieckmann’s observations for source rocks comprising
type II kerogen of paraffinic character, Erdmann & Horsfield (2006) pointed out that
secondary cracking overcompensates primary cracking when comparing open- versus
closed-system pyrolysis yields of samples from the Draupne and Heather Formation. They
showed that the open-system C6+ compounds-yield curve still increases while the MSSV
C6+ compounds-yield curve already decreases (Fig. 27b) but cumulative yield curves of
both, open and closed system pyrolysis show an excellent agreement up to temperatures
of the decrease in the closed system. This is an indicator for the overlapping of primary
and secondary product generation, which means that oil to gas cracking starts before
primary oil generation has ended. This, as stated earlier, leads to an underestimation of
secondary gas amounts by ~13% (G010283) to ~23% (G010351) and slightly more
instable kinetic predictions when using the conservative approach.
In the refined approach, the amount of C6+ compounds available for cracking to
secondary gas is the difference between open- and closed-system pyrolysis yields (Fig.
27b). Based on formula (4) Erdmann & Horsfield (2006) published a modified formula (9)
replacing the MSSV C6+ product amount at the cumulative maximum (M6+max[Tk]) with the
amount of observed primary C6+ products in an open system for any temperature Tx
greater than Tk (of formula 4).
[ ] (9)
The corresponding primary gas contents from closed-system Py-GC can now be
calculated again using formula (8) and compared to open-system primary gas yields (red
spline curve in Fig. 28). Results are in good agreement with regard to onset, increase and
end of generation although the calculated primary gas curve shows somewhat higher
yields than during open-system pyrolysis (Fig. 28). This indicates a still existing slight
underestimation of secondary gas yields probably due to secondary gas generation
starting before the C6+ maximum is reached in closed pyrolysis (Erdmann & Horsfield,
COMPOSITIONAL KINETIC APPROACH
60
2006). Thus, amounts of primary gas in the closed system are calculated to be lower
using the refined approach but are still overestimated in comparison to the open-system
measurements (red line in Fig. 28, right side). Furthermore, calculations of primary gas
yields and its kinetic predictions for geological heating rates are still in high dependence of
calculated secondary gas yields (see formula [8]) and thus the measured C6+ amounts.
Potential errors of measurement using the closed system pyrolysis affect in a higher
multitude to kinetic predictions than do for the Factor-GOR model presented in the
following chapter.
It is necessary to note that Dieckmann et al. (1998) and Erdmann & Horsfield (2006)
fitted the spline curves manually by tracing the closed-system data and interpolating to a
spline curve. When applying the conservative and refined approaches to pyrolysis data
from Wealden Shale in this thesis, spline approximations has been used as described in
the next chapter.
Fig. 28 MSSV pyrolysis yields for bulk petroleum (C1+), primary oil (C6+) and Total gas as well as calculated
primary and secondary gas, normalized to the maximum C1+ yield. The approximated spline functions for the
respective compound classes and boiling ranges are derived from open-system SRA measurements for the
marine and lacustrine Wealden Shale samples exemplified at heating rates of 0.7 K/min using the
conservative approach of Dieckmann et al. (1998) and 5 K/min using the refined approach after Erdmann &
Horsfield (2006)
G010351 0.7 K/min
G010283 0.7 K/min
G010351 5 K/min
G010283 5 K/min
conservative refined
COMPOSITIONAL KINETIC APPROACH
61
4.4.4 The GOR-Factor model
The newly developed GOR-Factor model approach reduces uncertainties
concerning primary and secondary product amount predictions by combining the
assumption that secondary gas is subsequently generated from the thermal degradation
of C6+ compounds with increasing temperatures (Dieckmann et al., 1998) and the findings
that thermal degradation of C6+ compounds starts before oil generation has come to an
end, and thus the primary C6+ yields are more comparable to open-system yields than to
those determined in the closed-system (Erdmann & Horsfield, 2006).
As a major simplification for the fitting procedure, directly measured SRA bulk
petroleum curves were introduced as a spline approximation for the normalized MSSV
C1+ cumulative yield curve (Fig. 29) based on the previously described assumption of
Erdmann & Horsfield (2006) and used as input data for the kinetic calculations. The SRA
bulk petroleum curves fit well to the normalized MSSV C1+ cumulative yield curves for all
samples and heating rates. In close relation, Schenk & Horsfield (1993) and Dieckmann et
al. (2000b) already demonstrated that cumulative generation of total generated
hydrocarbons and timing of C1+ formation, respectively, are independent of pyrolysis
conditions. Therefore, bulk petroleum generation under open- and closed-system
conditions can be described by similar kinetic parameters leading to identical geological
timing predictions. The excellent match of both MSSV and SRA data points to the
accuracy of the temperature measurement of the open-system SRA and the analytical
precision of the MSSV method (except sample G010283 at a heating rate of 0.7 K/min).
To attain a better fit of the open- and closed system yield curves, an amount closely
comparable to measured open-system Tvap-GC-FID yields is subtracted from each
MSSV C1+ data point (Table 11). This is called “free HC correction”. The
heterogeneously composed marine sample G010283 has a bigger need for correction,
with deviations of the correction from highest yields ranging between 2.7 and 6.2% (Table
11), whereas deviations for the homogenously composed lacustrine sample G010351
account for less than 1%. Slightly higher yields from MSSV pyrolysis at lower
temperatures are assumed to result from free HC as the HC correction indicates yields
closely comparable to Tvap yields.
COMPOSITIONAL KINETIC APPROACH
62
Table 11 Absolute yields of the “Free HC correction” and its relative amounts to the maximum MSSV C1+
yield. In comparison, yields from open-system Tvap-GC-FID measurements are recorded.
G010351
free HC
correction[µg/g]
max. MSSV
C1+ yield
[µg/g]
Tvap C1+
yield [µg/g]
deviation (of MSSV from
SRA) [%]
sec C1-5, 0.7 925 149774 0.62
sec C1-5, 2.0 0 178625 0.00
sec C1-5, 5.0 162 163507 0.10
1355
G010283
free HC
correction[µg/g]
max. MSSV
C1+ yield
[µg/g]
Tvap C1+
yield [µg/g]
deviation (of MSSV from
SRA) [%]
sec C1-5, 0.7 2839 45796 6.20
sec C1-5, 2.0 1852 53237 3.48
sec C1-5, 5.0 1035 38084 2.72
2154
Fig. 29 Measured MSSV pyrolysis data for boiling ranges C1+, C6+ and C1-5 normalized to the maximum C1+
yield and fitted spline curves for calculated primary and secondary gas generation using three different heating
rates (0.7, 2.0 and 5.0 K/min), compared to normalized SRA curve. Temperature shifts for boiling ranges can
be taken from Table 13.
G010283 G010351
COMPOSITIONAL KINETIC APPROACH
63
As already described in the refined
approach the calculation of secondary gas
yields by degradation of C6+ compounds used
to be problematic due to the fact that MSSV-
pyrolysis employed three heating rates
producing different product evolution curve
shapes and different maximum C6+ yields
resulting in too low secondary gas yields and thus too high primary gas yields (Fig. 28).
Thus, the derivation of kinetic parameters from secondary gas yields predicted too
unstable conditions within the reservoir using the conservative approach (Fig. 30). For the
lacustrine sample G010351 both measured data and spline show an excellent match up to
90% TR. At higher temperatures, the maximum yield of liquid components measured by
closed-system MSSV pyrolysis is lower than the cumulative plateau of the open-pyrolysis
SRA curves (according to observations of Erdmann & Horsfield (2006)). The open-system
approximated spline curve suggests that C6+ amounts generated under closed-system
conditions underestimate closed-system yields by up to 13% for the lacustrine sample and
up to 29% for the marine sample. This discrepancy of open- and closed-system
measurements is highest at a heating rate of 2 K/min for both samples, lacustrine and
marine originated. Furthermore, the cumulative plateau of open-system “spline” yields of
C6+ compounds is reached at slightly higher temperatures than temperatures of maximal
MSSV-closed-system measurements indicating that C6+ degradation starts before C6+
generation has come to an end (compare Erdmann (1999)), which can be viewed as the
main reason for the underestimation of primary C6+ input (and consequently secondary
gas yields) using closed-system data only (conservative approach). Therefore, the new
GOR model applies the bulk
petroleum SRA curve as a spline
approximation for primary oil and
primary gas. The spline curve is
multiplied by a factor and
temperature shifted for fitting to
directly measured MSSV data of
both, primary C1-5 and primary C6+.
The fitting factor is derived from
the open-system pyrolysis GOR.
During open-system pyrolysis,
hydrocarbons are only generated
Fig. 30 Comparison of the approximated spline curves for
secondary gas yields using the conservative and refined
approach as well as the Factor-GOR model
Gas to Oil
Ratio (%)
Oil
content
Gas
content
cumulative
GOR
G010283 0.875 0.125 14.3
G010351 0.872 0.128 14.7
Table 12 Gas-to-oil ratio from open-system
pyrolysis displaying the primary composition of
generated hydrocarbons from samples of
immature well EX-A
COMPOSITIONAL KINETIC APPROACH
64
primarily by kerogen to oil and gas transformation processes (Berner et al., 1995;
Dieckmann et al., 2000b). In contrast to the closed-system configuration, products are
immediately transported towards the trap (see chapter 3.3.3), and are not exposed to
higher temperatures which are necessary for secondary cracking processes. Therefore,
the gas-to-oil ratio obtained from open-system measurements for the respective samples
can be applied to approximate closed-system cumulative evolution curves by factorizing
the SRA spline curve (Fig. 29). The employed factors for primary C6+ and C1-5 are
displayed in Table 13. The cumulative open-system derived GOR’s of both samples do
not differ considerably from each other (0.125 for G010283 and 0.128 for G010351). Both
samples contain type I kerogen but are deposited in slightly different environments.
Although a uniform GOR derived from the open-
system pyrolysis is applied to the SRA bulk petroleum
curve, the Factor-GOR model imitates an increasing
GOR typical for subsequent conversion of petroleum
from kerogen (Schenk et al., 1997b). This GOR
development is caused by the temperature shift of C6+
generation rate curve to lower temperatures and the
shift of the primary gas spline curve to higher
temperatures. The best solution for all three heating
rates was a negative temperature shift of 0.25°C
(G010283) and 1.5°C (G010351) for the generation
curve of the C6+ boiling range products and a positive
shift of 2°C (G010283) and 9°C (G010351) for the primary formation of gaseous
compounds (Table 13). The spline curve for primary gas shows an excellent fit with
measured MSSV C1-5 Totals at low conversion rates until the secondary gas generation
overcompensates primary gas generation and both, open- and closed-pyrolysis yields,
diverge (Fig. 29).
Fig. 31 shows the development of the GOR derived from MSSV data served as
input for the PhaseKinetics approach as well as for the Factor-GOR model on the one
hand. On the other hand, the circles represent the GOR simulated by the temperature
shift of the spline curves for C6+ and C1-5 derived from open-system pyrolysis. It becomes
obvious that the GOR induced by the temperature shift using the new model increases
more linearily and smooth which is, first, in accordance with the GOR development for
lacustrine samples (di Primio & Horsfield, 2006) and second, comprehensible because the
spline curves are very smooth and are not subject of high measurement variations or
errors (comparable to Fig. 29, G010283, 0.7 K/min). Therefore, the GOR model appears
Temperature
shift [°C]G010283 G010351
prim C6+ 0.25 1.5
prim C1-5 2 9
sec C1-5, 0.7 61.0 50.0
sec C1-5, 2.0 61.25 50.5
sec C1-5, 5.0 61.5 50.75
Table 13 Temperature shifts of spline
curves of primary oil, primary gas and
secondary gas at three different
heating rates for both samples, marine
G010283 and lacustrine G010351
COMPOSITIONAL KINETIC APPROACH
65
to be realistic and in
accordance with the general
understanding of gas
generated subsequently to
oil (Pepper & Corvi, 1995;
Pepper & Dodd, 1995).
Based on the
statement of Erdmann &
Horsfield (2006) that
secondary gas amounts
are still slightly
underestimated due to
higher primary gas yields
determined by closed-system pyrolysis and compared to the open-system, the workflow
for determination and calculation of primary and secondary gas amounts has been
modified. In the refined model, primary gas has been calculated using formula (8) leading
to a high dependency of primary gas yields on calculated secondary gas yields and thus
to different kinetic predictions. On the other hand, secondary gas yields using the Factor-
GOR model are calculated by subtracting primary gas yields obtained in the open-system
from measured MSSV Total gas yields which is more based on measured data:
(10)
The spline curve is again
approximated by multiplication of the
SRA bulk petroleum curve using a
Factor to convert the SRA curve
which is based on the empirical
formula of Erdmann & Horsfield (2006)
for the calculation of secondary gas
amounts (equation [9]). The factor is
calculated by multiplication of the
difference of the normalised, single-
step open-system C6+ yield (oil
content, Table 12) and the normalized
MSSV generation product amount at highest temperatures (Table 10) by the conversion
Table 14 Total product amounts derived from Rock-Eval
S2 for measured and calculated boiling ranges of samples
G010283 and G010351
Total product amounts
[mg/g sample]Rate factor
C1+ 58.27 1.000
C6+ 50.97 0.875
prim C1-5 7.30 0.125
sec C1-5 29.83 0.512
C1+ 116.19 1.000
C6+ 101.29 0.872
prim C1-5 14.90 0.128
sec C1-5 56.64 0.487
Boiling range
G0
10
28
3G
01
03
51
Fig. 31 GOR development throughout kerogen conversion to
petroleum (1) using MSSV-closed-system data (triangles) and (2)
derived from the temperature shift of open-system SRA spline curves
in the Factor-GOR model
COMPOSITIONAL KINETIC APPROACH
66
factor 0.7 (according to Dieckmann et al. (1998)). The obtained secondary gas factor is,
as denoted in Table 14, 0.512 for sample G010283 and 0.487 for sample G010351. At
highest MSSV temperatures (575, 600, and 605°C for 0.7, 2.0 and 5.0 K/min,
respectively), some C6+ compounds still exist in the pyrolysates (usually simple aromatics
such as benzene, toluene, naphthalene and some trimethylbenzene isomers as can be
taken from the GC traces of MSSV-closed pyrolysis measurements, see also Fig. 29),
which indicates that secondary gas generation has not entirely come to its end.
In a last step, the secondary gas spline curves were shifted towards higher
temperatures to fit best with calculated secondary gas yields. Applied temperature shifts
for each heating rate are given in Table 13. Shifts are chosen to be very narrow, i.e.
almost similar, for both samples G010283 and G010351, differing by only 0.25-0.5°C to
each other. This results in relatively stable kinetic parameters and thus a relatively stable
prediction for geological heating rates (which will be discussed later in greater detail).
Broader shifts would have resulted in more instable geological predictions, whereas an
identical temperature shift for each heating rate would have resulted in very stable
configuration at high geological temperatures.
Subsequent kinetic analysis using KINETC2000 and KMOD© software (Burnham et
al., 1987) on the basis of first-order kinetics (van Heek & Jüntgen, 1968) was applied after
the same principles as in the bulk kinetic approach (chapter 4.2). Resulting potential-
versus-activation-energy distributions and single frequency factors for primary oil, primary
gas and secondary gas, i.e. kinetic parameters, are given in Table 15 for both samples,
whereas curve fit and activation energy distributions are shown in Fig. 32.
COMPOSITIONAL KINETIC APPROACH
67
Fig. 32 Activation energy distributions and normalized measured and calculated generation rate curves for
C1+, C6+, primary and secondary gas formation for samples G010283 (left) and G010351 (right)
Table 15 Kinetic parameters, activation energies EA
and frequency factor A for SRA bulk petroleum (C1+),
MSSV C6+ as well as primary and secondary C1-5,
derived from generation rate curves, calculated using
three heating rates (0.7, 2.0 and 5.0 K/min)
GFZ sampe number G010283 G010283 G010283 G010283
Method SRA MSSV MSSV MSSV
FractionC1+ C6+ primary C1-5
secondary C1-
5
Frequency factor A (s-1) 3.84E+14 2.35E+14 3.78E+14 6.61E+15
E (kcal/mol) % % % %
44 0.05 0.09 0.04
45 0.04 0.02 0.02
46 0.09 0.17 0.14
47 0.20 0.15 0.07
48 0.11 0.32 0.29
49 0.52 0.50 0.26
50 0.28 0.48
51 0.12
52 1.18 3.18 0.03
53 1.60 5.36 4.01 0.03
54 19.34 44.70 9.48 0.07
55 45.51 24.18 47.61 0.11
56 13.09 11.26 16.60 0.14
57 12.09 5.79 13.37 0.25
58 1.36 1.32 2.46 0.39
59 2.98 1.65 3.04 0.21
60 0.12 0.27
61 0.96 0.68 0.82
62 0.09 0.38 4.27
63 8.81
64 0.51 0.50 48.92
65 0.54 13.43
66 15.45
67 1.83
68 3.99
69 0.01
70 1.12
71 0.30
72 0.16
73
74 0.49
GFZ sampe number G010351 G010351 G010351 G010351
Method SRA MSSV MSSV MSSV
FractionC1+ C6+ primary C1-5
secondary C1-
5
Frequency factor A (s-1) 2.07E+15 2.22E+15 2.36E+15 2.46E+16
E (kcal/mol) % % % %
50
51
52
53
54
55
56
57
58
59 96.87 100.00
60 95.60
61 1.18
62 1.91 2.94
63 1.40
64
65
66
67 0.03 95.81
68 0.06
69 2.08
70 2.11
COMPOSITIONAL KINETIC APPROACH
68
4.4.5 Prediction to geological heating rates
Generation rate curves for primary C6+, primary gas and secondary gas derived from
MSSV pyrolysis are compared to bulk petroleum generation rate curves derived from
open-system SRA pyrolysis as shown in Fig. 29. The approximated spline curves for the
aforementioned compound classes at three different heating rates (0.7, 2.0 and 5.0 K/min)
act as input data for the determination of respective kinetic parameters necessary for
extrapolation of reactions to geological conditions. The same mathematical procedure and
software (KINETICS2000 and KMOD© software, (Burnham et al., 1987)) as for bulk
kinetics is used (see chapter 4.2). Subsequent kinetic analysis on basis of the kinetic
parameters (Table 15 and Fig. 32) resulted in prediction of temperatures and vitrinite
reflectances of geological Tmax, onset, middle and offset of primary and secondary product
generation for a linear heating rate of 3°C/Ma (Table 16). The predicted transformation
ratio curves and generation rate curves for geological heating conditions are presented in
Fig. 33.
For a geological heating rate of 3°C/Ma, secondary gas generation starts at 182°C
for the marine-influenced sample G010283 and 196.5°C for the lacustrine sample
G010351 (Table 16). At these temperatures, primary generation of bulk petroleum (from
SRA) as well as primary “oil” and gas (from MSSV) has already come to an end (90% TR)
for both samples (165°C for G010283 and 175°C for G010351). Maximum secondary gas
10% TR 50% TR 90% TR geologic Tmax
°C °C °C °C
C1+ 133.2 148.4 165.4 148.4
C6+ 131.4 146.7 163.7 146.7
primary C1-5 134.5 150.0 167.2 150.4
secondary C1-5 182.2 198.1 215.7 198.5
boiling range
10% TR 50% TR 90% TR geologic Tmax
%R0 %R0 %R0 %R0
C1+ 0.788 0.960 1.241 0.960
C6+ 0.773 0.935 1.211 0.935
primary C1-5 0.800 0.987 1.275 0.994
secondary C1-5 1.570 1.954 2.434 1.965
boiling range
10% TR 50% TR 90% TR geologic Tmax
°C °C °C °C
C1+ 155.5 167.2 175.4 169.1
C6+ 154.9 166.5 174.2 168.7
primary C1-5 161.9 173.8 182.3 175.7
secondary C1-5 196.5 208.9 217.7 210.9
boiling range
10% TR 50% TR 90% TR geologic Tmax
%R0 %R0 %R0 %R0
C1+ 1.085 1.275 1.434 1.313
C6+ 1.074 1.261 1.412 1.305
primary C1-5 1.182 1.405 1.572 1.439
secondary C1-5 1.911 2.250 2.494 2.300
boiling range
Table 16 Temperatures and calculated vitrinite reflectances for the predicted Tmax and TR's at a geological
heating rate of 3°C/Ma for G010283 (left) and G010351 (right)
COMPOSITIONAL KINETIC APPROACH
69
generation (Tmax) is calculated to take place at 198.5°C (G010283) and 211°C (G010351),
or expressed in vitrinite reflectances at 1.97% R0 and 2.30% R0, respectively. These
kinetic predictions (Fig. 33) are in accordance with previously published data for oil to gas
cracking. Pepper & Dodd (1995) conducted an extensive literature review pointing out oil
cracking parameters for different scenarios taking into account kerogen type, petroleum
composition and cracking environment. For intra-source cracking of high molecular weight
oil a Tmax of 173°C was predicted (Quigley et al., 1987; Mackenzie & Quigley, 1988;
Quigley & Mackenzie, 1988) which is considerably less stable than the cracking reactions
of both of the investigated Wealden Shale samples. Considering cracking kinetics for a
‘type I’ oil showing Tmax at 191.5°C (Table 2 in Pepper & Dodd (1995)) and for a C14+ oil
(Tmax=200°C (Ungerer & Pelet, 1987; Behar et al., 1988; Forbes et al., 1991)) which is
comparable to the composition of petroleums generated from Wealden Shales (see
chapter 4.1.2 “open pyrolysis” and 4.3.1 “phase behaviour”) the present results become
more reasonable (compare also Fig. 34). These kinetic predictions are calculated for a
heating rate of 3°C/Ma and assuming a single frequency factor and activation energy EA.
Furthermore, Schenk et al. (1997a) calculated for Total gas formation from a type I oil
generated from the lacustrine Tualang Formation that cracking to gas culminates at
Tmax = 222°C for in-reservoir conditions and a heating rate of 3°C/Ma (Fig. 34). Oil-to-gas
cracking under reservoir conditions turns out to give thermally more stable kinetics than
oil-to-gas cracking under intra-source conditions possibly related to a catalytic effect
involving high-molecular organic materials such as residual kerogen (Schenk et al.,
1997a) and different clay minerals such as montmorillonite or kaolinite (Espitalié et al.,
1984; Dembicki Jr, 1992). Nevertheless, with increasing TOC (above 2%), these effects
are minimized. Therefore and as TOC values for the two investigated Wealden Shale
samples are consistently high (roughly ≥10%), and high amounts of homogeneous “oil”
remaining within the closed system are generated upon pyrolysis, the present kinetic
calculation rather resemble in-reservoir cracking kinetics.
Fig. 33 also displays the geological predictions for primary C6+ and C1-5 generation.
The predicted formation of oil and gas derived from MSSV pyrolysis is enveloped by the
bulk petroleum generation derived from SRA. Due to the applied temperature shifts (Table
13) primary gas (134.5 - 167.2°C) occurs to be formed 3.1 to 3.5°C later (~100 m deeper)
than primary oil (131.4 - 163.7°C, Tmax = 146.7°C) for sample G010283. For sample
G010351, primary gas (161.9 - 182.3°C) is formed 7.0 to 8.1°C later (~250 m deeper)
than primary oil (154.9 - 174.2°C, Tmax = 168.7°C). Kinetic predictions seem to be in
accordance observations of Tegelaar & Noble (1994) who stated that peak oil generation
derived from lacustrine lamalginites occurs for vitrinite reflectances around 1.0% R0.
COMPOSITIONAL KINETIC APPROACH
70
In contrast, Telalginites (e.g. Botryococcus braunii) generate at higher temperatures and
maturities than other types of aliphatic kerogens with peak oil generation occurring about
150 - 160°C at a heating rate of 1°C/Ma (Tegelaar & Noble, 1994) which corresponds to
Tmax which is about 5°C higher at a heating rate of 3°C/Ma. It can be speculated that the
lacustrine sample G010351 consists of higher amounts of Botryococcus alginate than the
marine sample.
Fig. 33 Computed transformation ratio curves (top) and generation rate curves (bottom) as a function of
temperature at a geological heating rate of 3°C/Ma for samples G010283 (left) and G010351 (right)
Fig. 34 Computed transformation ratio curves and generation rate
curves as a function of temperature at a geological heating rate of 3
K/Ma for samples G010283 and G010351 compared to literature data
(Pepper & Dodd, 1995)
IMPLICATIONS FOR GAS-IN-PLACE (GIP)
71
4.5 Implications for gas-in-place (GIP)
Assuming that both of the here investigated samples, the deep marine sample
G010283 and the deep lacustrine sample G010351, represent the variety in composition
of organic matter in the investigated subsurface horizons of late and overmature wells EX-
C and EX-B, the kinetic predictions for the immature samples can be used to compare
predicted maturity conditions and hydrocarbon amounts and compositions to measured
data of the overmature wells.
Maturities have been investigated by the LEK team of RWTH Aachen and can be
found in Table 3. They range between 1.60% R0 at 613 m depth and 1.95% R0 at 921 m
depth in the late mature well EX-C and they range between 2.20% R0 at 991 m depth and
2.40% R0 at 1297 m depth in the overmature well EX-B. These maturities correspond to
temperatures of 184°C and 198°C in well EX-C and 207°C and 215°C in well EX-B,
respectively, applying the maturity-temperature trend of the kinetic descriptions (Fig. 33).
Well EX-C possesses a steep maturity gradient which can be transferred to a temperature
gradient of 4.6°C/100 m. This is rather high compared to the normal gradient of 3.6°C/100
m for the LSB (Bruns et al., 2013b). The maturity development in well EX-B also shows a
discrepancy in that the highest measured vitrinite reflectance is not found in the lowest
vertical horizon (Table 3). Rapidly varying and increasing maturity trends within the LSB
were explained by a combination of deep burial of individual blocks, high heat flux during
the Upper Jurassic to Cretaceous subsidence and subsequent uplift and erosion during
the Upper Cretaceous by Petmecky et al. (1999); Brink (2002); Brink (2005) and Adriasola
Muñoz (2006) for gaseous hydrocarbons from Carboniferous Wealden coals. But this
generation history cannot be applied to Lower Cretaceous Wealden Shales investigated
here. Stadler & Teichmüller (1971) and Giebeler-Degro (1986) proposed a magmatic
intrusion in Lower Cretaceous times to be responsible for elevated maturities. But as the
tectonic history of the LSB is quite unclear, another, previously discussed reason can be
assumed. Hydrothermal solutions circulating at the base of wells EX-B and EX-C might
have influenced the maturation of products in-place (Lüders et al., 2012). The present
maturity data can be interpreted to support the last theory as no distinct maturity trend
(neither normal nor inverse) can be detected.
Generated hydrocarbons in the matured wells EX-B and EX-C are, as already
described in chapter 4.1.1, dominated by intermediate- to long-chained aliphatic
components with minor amounts of aromates and substantial gas loss in the upper,
marine influenced intervals, whereas the lower, lacustrine intervals contain short- to
IMPLICATIONS FOR GAS-IN-PLACE (GIP)
72
intermediate-chained aliphatic compounds (<C14) with varying amounts of predominantly
wet gases and significant portions of aromatic components (see Fig. 12 and Table A 3).
Transferring the kinetic predictions of both samples of well EX-A to the maturities of wells
EX-B and EX-C, a cumulative composition can be predicted that should have been
generated up to the present maturity stages. At the onset of secondary cracking of
primary products originating from lacustrine type I kerogens (1.6% R0 for a marine
composition and 1.9% R0 for a lacustrine composition), the oil available for cracking
should still be present in major amounts, with decreasing amounts when proceeding to
Tmax of the cracking process (1.9 and 2.25% R0 for marine and lacustrine compositions,
respectively) but increasing amounts of (secondary) gas. Reaching the offset of
secondary cracking, almost the entire primary oil amounts should be depleted and
gaseous hydrocarbons should dominate the GC fingerprints.
Comparing the present maturity stages with the compositional predictions, it
becomes clear that primary generation of oil and gas has almost come to an end for
samples from both wells. In contrast, secondary reactions have been developed quite
different for both wells and compositional kinetic predictions of deep marine sample
G010283 and lacustrine sample G010351. For the late mature well EX-C, the onset of
secondary cracking has just occurred in the upper horizons when considering an organic
matter composition similar to that of the marine influenced sample G010283 (Table 9).
The more homogeneously composed organic matter of sample G010351 is shown to be
more stable and secondary cracking is calculated to set in at about 1.9% R0, almost the
same VR value as measured in the lower part of well EX-C. Thus and assuming similar
organic matter compositions throughout well EX-C, significant amounts of (retained or
unexpelled) long and intermediate straight-chained aliphatic compounds should be still
detected. This is, as previously discussed, only the case for the upper intervals, but not
the lower intervals which might hint to the impact of fluids affecting in-place petroleum
amounts and composition.
Secondary gas generation in the overmature well EX-B has, based on kinetic
predictions, exceeded its maximum for organic matter with an initial composition similar to
that of the deep marine sample G010283 and has nearly come to an end (offset VR of
2.43% R0). Assuming organic matter with an initial composition similar to that of lacustrine
sample G010351, generation of secondary cracking products is at its climax
(Tmax = 2.30% R0). Keeping this in mind retained or unexpelled long and intermediate
straight-chained aliphatic compounds should be already severely degraded but still
detectable in comparably low amounts. This is, again, only the case for the upper interval,
but not for the lower intervals which are almost barren of free petroleum products. The
IMPLICATIONS FOR GAS-IN-PLACE (GIP)
73
impact of fluids affecting in-place petroleum amounts and composition can again be
assumed.
Taking everything into consideration, free hydrocarbons remaining in the upper,
marine influenced intervals of matured wells and predicted compositions at the present
maturity stages are in accordance with each other, which cannot be stated for the lower,
lacustrine intervals. Maturity as indicated by vitrinite reflectance measurements does not
reflect the cumulative compositions present in the successions of both wells. Furthermore,
and as a consequence of the measured VR in both wells, it is likely that the VR trends are
not an effect of maturation by thermal stress. It can be assumed that the present
hydrocarbons in the late and overmature wells are either not in-situ generated and
migrated into the source rock of the Wealden Shale formation, or hydrothermal solutions
circulating at the base of both wells have influenced the composition of the residual
organic matter as well as their maturity trends (Lüders et al., 2012). The latter theory is
supported by the not linearly increasing maturity trend with depth (see chapter 3.2.1)
which points to hydrothermal activity in different horizons with different strength or reaction
of the organic matter to the heat source.
In the end, absolute bulk petroleum yields (Table 14) as well as amounts of primary
oil, primary gas and secondary gas can be calculated providing input parameters for 3D-
geological modelling. The respective fraction rate factors (Table 14) are multiplied with the
S2 yield from Rock-Eval pyrolysis to receive bulk petroleum amounts (in mg/g sample).
For secondary gas the arithmetical average of the particular rate factors of each heating
rate was taken (0.512 for marine sample G010283 and 0.487 for lacustrine sample
G010351). The total product amounts are dependent on the TOC content, the type and
origin of OM. As expected, the lacustrine sample G010351 exhibiting the highest TOC
(17.5%) generates more oil and gas (the double amount) than the marine sample
G010283 also consisting of type I kerogen. Hence, also the double amount of secondary
gas is generated by the sample of lacustrine origin (56.64 mg/g sample compared to
29.83 mg/g sample).
CONCLUSION
74
5 Conclusion
The main goal of the present thesis was to characterize primary and secondary
hydrocarbon formation processes from immature to early mature Wealden Shale samples
using artificial maturation under closed-system pyrolysis conditions. A new approach was
developed to assess relevant compositional kinetic parameters. Furthermore, the physical
state of hydrocarbon products generated throughout primary thermal evolution was
predicted using the previously published PhaseKinetics approach.
In a first screening step, the genetic potential and maturity of the Wealden Shale
samples were investigated applying Rock-Eval pyrolysis and organic petrographical
methods on samples of three wells, early mature OM containing well EX-A (VR = 0.8% R0),
late maturity staged well EX-C (1.5 - 1.9% R0) and overmature well EX-B (2.2 - 2.4% R0).
The lithological successions of all wells contain OM of type I originating from a lacustrine
depositional environment and mainly composed of (Botryococcus) aligintes (early mature),
vitrinites and inertites (higher maturity) but also coke as a result of oil formation and
cracking. Generated petroleums are of a paraffinic high-wax type dominated by long-
chained aliphatic compounds in all depth intervals of the immature succession but being
alterated to shorter chain lengths by hydrothermal solutions in the lower intervals of both
of the matured successions. The samples for the deeper investigations in terms of kinetic
modelling were chosen by highest TOC (9.15 - 17.5% TOC) values in each succession of
the early mature well EX-A to exclude effects of the anorganic matrix on the alteration of
the organic matter.
Kinetic modelling with an emphasis on compositional modelling was conducted
integrating previously determined bulk kinetic and PhaseKinetic parameters. The PVT
data consistently discriminate between petroleums generated from marine and lacustrine
origin. The fluids exhibit low GOR’s below 100 Sm³/Sm³ that do not significantly change
throughout the kerogen conversion which is a typical feature for type I kerogens. The
other fluid physical parameter as Psat and B0 do also range within a limited area which is a
typical behaviour for homogeneously structured kerogen of lacustrine origin. All of the
samples possess high generation potentials for heavy components (C7+) whereas the
lacustrine samples are more pronounced on very heavy fractions (C14-45) compared to
marine samples. This is also reflected in the phase envelopes which are more “loaf-
shaped” for lacustrine compositions, and hence lacustrine originated petroleums separate
at lower depths. For the assessment of amounts and primary kerogen to petroleum and
CONCLUSION
75
secondary oil-to-gas cracking, the new compositional model was established based on
two approaches developed by Dieckmann et al. (1998) and Erdmann & Horsfield (2006).
The new approach is called GOR-model and combines data from open- and closed-
system pyrolysis. As input parameter normalized generation rate curves determined from
open-system SRA bulk petroleum measurements are used and applied to closed-system
MSSV data as a spline approximation. The normalization of identically shaped SRA
curves eliminates errors in secondary gas yield predictions, which occurred using
Dieckmann’s approach. Furthermore, the factors applied to temperature shifted SRA
curves for fitting MSSV C6+ and Total gas data are derived from the open-system pyrolysis
GC-FID GOR of the respective samples. Secondary gas amounts are calculated by
subtracting yields of the (primary) gas spline curve from MSSV Total gas at respective
temperatures. The factor for the secondary gas spline curve, also based on the SRA
curve, is determined for every sample at each heating rate by multiplying the difference of
the normalised, single-step open-system C6+ yield and the normalized MSSV generation
product amount at the highest temperatures with the conversion factor of 0.7. The spline
curves are then used as input data for the calculation of kinetic parameters of primary and
secondary petroleum generation, which in turn are used to extrapolate formation
processes to geological heating conditions (3°C/Ma). Kinetic parameter for the marine
sample exhibit a broader range of activation energies with a main EA of 54 kcal/mol for
primary oil generation, 55 kcal/mol for primary gas, and 64 kcal/mol for secondary gas.
Lacustrine generation parameters are slightly more stable and exhibit one major EA
accounting for nearly 100% (59 kcal/mol for oil, 60 kcal/mol for primary gas and
67 kcal/mol for secondary gas). Predictions to geological conditions have been applied for
two samples stemming from a deep marine (G010283) and a deep lacustrine environment
(G010351); both comprising type I kerogen. The predicted generation rate curves for
primary compound classes obtained from MSSV closed pyrolysis fit very well under the
bulk generation rate curves obtained from closed-system SRA. This is a positive feature
for the accuracy of the model. According to the geological predictions, generation of
secondary gas reaches its Tmax at 198.5°C (1.97% R0) for the marine sample G010283
and at 211°C (2.30% R0) for the lacustrine sample G010351, whereas cracking of
lacustrine organic matter occur within a shorter temperature interval (resulting in a steeper
transformation ratio curve). The kinetic findings for secondary cracking are in accordance
with previously published data for the cracking of type I oils, indicating that the applied
new modelling approach covers relevant degradation reactions and can be viewed as
being valid.
CONCLUSION
76
5.1 Future research
In a very next step, kinetic data could be integrated in a 3D-geological model of
either the entire LSB or its sub-basins. Subsurface conditions and burial history could be
analysed as well as structure and extent of potential petroleum plays of the Lower
Cretaceous Wealden Shales. According to Lüders et al. (2012) and to get a better insight
into subsurface processes leading to the present composition of organic matter, more
research focus should be placed on compositional changes induced by hydrothermal
fluids circulating in lithological formations of e.g. wells EX-B and EX-C.
77
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83
7 Appendix
7.1 Index of Appendix
Table A 1 Organic petrography of investigated wells ...................................................................................... 84
Table A 2 TOC and Rock-Eval ........................................................................................................................... 85
Table A 3 Tvap-GC-FID (single components of free HC) ................................................................................... 92
Table A 4 Open-system pyrolysis GC-FID (primary products) .......................................................................... 95
Table A 5 Closed-system-MSSV pyrolysis GC-FID (PhaseKinetics) .................................................................. 107
Table A 6 Closed-system pyrolysis GC-FID (compositional kinetic) ................................................................ 110
TABLE A 1 ORGANIC PETROGRAPHY OF INVESTIGATED WELLS
84
Table A 1 Organic petrography of investigated wells
TABLE A 2 TOC AND ROCK-EVAL
85
Table A 2 TOC and Rock-Eval
EX-ATop-
DepthS1 S2 S3 Tmax PP PI HI OI TOC
sampleID m mg/g mg/g mg/g °C mg/g wt ratiomg HC/
g TOC
mg CO2/
g TOC%
G010269 831.5 0.01 0.44 0.19 424 0.45 0.02 89 38 0.5
G010270 832.1 0.02 0.41 3.30 430 0.43 0.05 90 724 0.46
G010271 832.3 0.02 0.38 1.06 424 0.40 0.05 82 229 0.46
G010272 833.3 0.06 3.64 1.06 428 3.70 0.02 212 62 1.72
G010273 834.7 0.04 1.85 0.91 430 1.89 0.02 168 83 1.1
G010274 835.1 0.05 2.67 0.63 427 2.72 0.02 193 46 1.38
G010275 836.0 0.06 5.15 1.12 427 5.21 0.01 283 62 1.82
G010276 836.6 0.21 23.21 1.45 429 23.42 0.01 544 34 4.27
G010277 837.4 0.20 53.68 0.95 439 53.88 0.00 740 13 7.25
G010278 838.1 0.03 0.63 2.75 437 0.66 0.05 121 529 0.52
G010279 838.7 0.03 0.75 0.28 430 0.78 0.04 108 40 0.69
G010280 839.2 0.04 2.27 1.52 432 2.31 0.02 179 120 1.27
G010281 840.8 0.30 64.74 0.64 443 65.04 0.00 720 7 8.99
G010282 842.9 0.24 40.53 0.64 438 40.77 0.01 695 11 5.83
G010283 847.3 0.55 58.27 2.76 429 58.82 0.01 637 30 9.15
G010284 847.8 0.04 0.91 0.49 426 0.95 0.04 98 53 0.93
G010285 848.9 0.10 7.70 1.43 436 7.80 0.01 352 65 2.19
G010286 849.3 0.23 51.00 0.73 440 51.23 0.00 656 9 7.77
G010287 850.2 0.19 13.60 1.56 424 13.79 0.01 314 36 4.33
G010288 850.4 0.08 3.99 1.03 425 4.07 0.02 182 47 2.19
G010289 909.5 0.62 41.96 1.73 437 42.58 0.01 704 29 5.96
G010290 910.2 1.01 82.15 2.17 444 83.16 0.01 822 22 10
G010291 911.1 0.89 28.61 1.03 441 29.50 0.03 767 28 3.73
G010292 911.7 0.81 27.02 1.64 438 27.83 0.03 606 37 4.46
G010293 912.5 0.78 34.73 1.66 441 35.51 0.02 768 37 4.52
G010294 913.5 1.19 51.99 1.50 441 53.18 0.02 839 24 6.2
G010295 913.9 1.23 44.81 1.01 443 46.04 0.03 850 19 5.27
G010296 914.5 1.11 17.20 1.39 435 18.31 0.06 623 50 2.76
G010297 915.9 0.31 12.43 1.46 438 12.74 0.02 628 74 1.98
G010298 916.5 0.33 28.98 1.34 440 29.31 0.01 763 35 3.8
G010299 917.0 3.53 30.33 0.89 438 33.86 0.10 800 23 3.79
G010300 918.0 1.01 53.44 2.79 432 54.45 0.02 733 38 7.29
G010301 918.9 0.10 11.14 1.33 440 11.24 0.01 549 66 2.03
G010302 919.3 0.43 27.89 1.79 433 28.32 0.02 596 38 4.68
G010303 920.4 0.14 6.74 1.69 438 6.88 0.02 438 110 1.54
G010304 923.5 0.28 48.34 1.18 442 48.62 0.01 832 20 5.81
G010305 923.7 0.93 91.48 1.47 446 92.41 0.01 775 12 11.8
G010306 925.9 0.27 13.24 2.06 430 13.51 0.02 507 79 2.61
G010307 926.4 0.08 2.71 2.27 433 2.79 0.03 271 227 1
G010308 927.3 0.06 2.43 2.32 433 2.49 0.02 252 241 0.96
G010309 928.3 0.04 1.29 1.95 438 1.33 0.03 193 292 0.67
G010310 966.4 0.04 3.68 2.35 444 3.72 0.01 394 252 0.93
G010311 967.3 0.11 15.61 1.02 439 15.72 0.01 635 41 2.46
G010312 967.8 0.24 10.13 0.79 434 10.37 0.02 618 48 1.64
G010313 968.8 0.39 43.21 1.38 443 43.60 0.01 818 26 5.28
G010314 969.8 0.49 18.46 0.68 436 18.95 0.03 491 18 3.76
G010315 970.3 3.02 12.70 0.61 435 15.72 0.19 784 38 1.62
G010316 972.6 1.17 102.90 1.68 449 104.07 0.01 762 12 13.5
G010317 972.8 1.22 67.73 1.50 437 68.95 0.02 730 16 9.28
G010318 974.4 1.77 8.43 1.10 435 10.20 0.17 615 80 1.37
G010319 974.6 1.10 57.82 1.44 440 58.92 0.02 716 18 8.07
G010320 992.3 1.07 86.84 0.52 448 87.91 0.01 762 5 11.4
G010321 994.1 0.44 43.46 0.71 446 43.90 0.01 866 14 5.02
deep
mar
ine
subl
itor
al la
kede
ep la
cust
rine
TABLE A 2 TOC AND ROCK-EVAL
86
Table A 2 continued
EX-ATop-
DepthS1 S2 S3 Tmax PP PI HI OI TOC
sampleID m mg/g mg/g mg/g °C mg/g wt ratiomg HC/
g TOC
mg CO2/
g TOC%
G010322 994.9 0.33 29.79 0.78 437 30.12 0.01 669 18 4.45
G010323 996.4 0.18 18.58 0.90 436 18.76 0.01 628 30 2.96
G010324 997.3 0.26 20.15 1.16 433 20.41 0.01 566 33 3.56
G010325 997.8 0.12 9.36 1.25 437 9.48 0.01 523 70 1.79
G010326 1029.2 0.48 26.74 1.41 429 27.22 0.02 646 34 4.14
G010327 1029.7 0.06 8.09 1.22 444 8.15 0.01 509 77 1.59
G010329 1031.0 0.56 77.87 0.93 448 78.43 0.01 763 9 10.2
G010330 1031.7 0.03 1.74 0.82 440 1.77 0.02 347 163 0.5
G010331 1031.9 0.04 3.19 0.97 441 3.23 0.01 336 102 0.95
G010332 1032.6 0.87 101.07 1.05 449 101.94 0.01 749 8 13.5
G010333 1033.6 0.25 15.95 0.85 436 16.20 0.02 604 32 2.64
G010334 1034.5 0.03 1.29 1.29 436 1.32 0.02 196 196 0.66
G010335 1036.9 0.06 2.68 1.27 440 2.74 0.02 412 195 0.65
G010336 1037.3 0.16 17.35 2.06 438 17.51 0.01 558 66 3.11
G010337 1038.4 0.71 89.86 0.60 448 90.57 0.01 731 5 12.3
G010338 1039.2 0.06 4.76 0.74 440 4.82 0.01 378 59 1.26
G010339 1040.1 0.11 3.48 0.84 437 3.59 0.03 466 112 0.75
G010340 1040.8 0.65 32.25 1.37 429 32.90 0.02 685 29 4.71
G010341 1042.6 0.06 6.58 0.45 440 6.64 0.01 463 32 1.42
G010342 1043.5 0.74 115.84 0.99 453 116.58 0.01 757 6 15.3
G010343 1043.9 0.07 3.08 0.76 441 3.15 0.02 259 64 1.19
G010344 1044.6 0.04 4.08 0.76 441 4.12 0.01 441 82 0.93
G010345 1045.2 0.09 2.96 0.82 426 3.05 0.03 196 54 1.51
G010346 1045.6 0.51 33.51 1.14 423 34.02 0.01 586 20 5.72
G010347 1046.0 0.03 1.01 0.57 428 1.04 0.03 215 122 0.47
G010348 1046.4 0.15 10.22 0.72 435 10.37 0.01 541 38 1.89
G010349 1048.0 0.21 40.01 0.62 442 40.22 0.01 752 12 5.32
G010350 1048.5 0.02 0.45 1.07 442 0.47 0.04 135 320 0.33
G010351 1050.1 0.82 116.19 0.54 452 117.01 0.01 664 3 17.5
G010352 1051.3 0.23 28.18 0.72 438 28.41 0.01 5317 136 0.53
G010353 1051.7 0.22 27.35 0.77 439 27.57 0.01 716 20 3.82
G010354 1052.4 0.04 2.53 0.76 441 2.57 0.02 405 122 0.63
G010355 1053.6 0.02 0.32 1.38 433 0.34 0.06 91 391 0.35
G010356 1054.4 0.12 7.66 0.63 437 7.78 0.02 483 40 1.58
G010357 1055.0 0.34 43.16 0.45 440 43.50 0.01 793 8 5.44
G010358 1055.3 0.13 7.96 0.67 437 8.09 0.02 410 35 1.94
G010359 1055.8 0.03 2.39 0.46 439 2.42 0.01 371 71 0.64
G010360 1056.6 0.16 16.32 0.76 439 16.48 0.01 729 34 2.24
G010361 1058.0 0.74 75.68 0.91 446 76.42 0.01 728 9 10.4
dee
p la
cust
rin
e
TABLE A 2 TOC AND ROCK-EVAL
87
Table A 2 continued
EX-BTop-
DepthS1 S2 S3 Tmax PP PI HI OI TOC
sampleID m mg/g mg/g mg/g °C mg/g wt ratiomg HC/
g TOC
mg CO2/
g TOC%
G010441 980.5 0.09 0.51 0.92 315 0.6 0.15 80 144 0.64
G010442 983.2 0.2 0.74 0.91 307 0.94 0.21 62 76 1.2
G010443 984.9 0.12 0.59 0.34 468 0.71 0.17 67 38 0.88
G010444 985.8 0.21 0.91 1.22 371 1.12 0.19 86 115 1.06
G010445 986.3 1.71 2.82 1.78 461 4.53 0.38 59 37 4.79
G010446 987.7 0.31 1.03 0.49 392 1.34 0.23 86 41 1.2
G010447 988.9 0.7 1.85 0.54 375 2.55 0.27 84 25 2.19
G010448 989.6 0.76 1.89 0.28 358 2.65 0.29 89 13 2.13
G010449 990.4 1.02 2.23 0.2 320 3.25 0.31 77 7 2.9
G010450 991.2 4.27 5.94 0.95 472 10.21 0.42 83 13 7.12
G010451 992.4 0.96 1.48 0.82 453 2.44 0.39 46 25 3.22
G010452 993.0 1.4 2.25 0.58 453 3.65 0.38 61 16 3.67
G010453 995.3 1.14 2.3 0.26 345 3.44 0.33 108 12 2.13
G010454 996.0 0.57 2.01 1.88 395 2.58 0.22 130 121 1.55
G010455 996.6 1.29 1.9 0.58 457 3.19 0.4 41 13 4.58
G010456 996.8 1.39 2.28 0.48 459 3.67 0.38 41 9 5.5
G010457 997.2 0.18 0.72 0.69 450 0.9 0.2 62 59 1.16
G010458 1000.6 1.05 1.64 0.82 460 2.69 0.39 39 20 4.18
G010459 1002.0 0.09 0.53 0.77 310 0.62 0.15 65 94 0.82
G010460 1002.9 0.1 0.54 0.81 486 0.64 0.16 66 99 0.82
G010461 1006.0 0.11 0.57 0.3 489 0.68 0.16 76 40 0.75
G010462 1007.1 0.06 0.45 0.6 491 0.51 0.12 69 92 0.65
G010463 1008.6 0.08 0.48 0.26 490 0.56 0.14 62 34 0.77
G010464 1009.1 0.07 0.44 0.44 492 0.51 0.14 60 60 0.74
G010465 1010.0 0.1 0.54 0.81 491 0.64 0.16 56 84 0.97
G010466 1010.9 0.16 0.7 1.25 504 0.86 0.19 61 108 1.16
G010467 1012.0 0.05 0.41 0.38 487 0.46 0.11 70 65 0.59
G010468 1013.5 0.04 0.37 0.36 490 0.41 0.1 70 68 0.53
G010469 1015.9 0.09 0.52 0.45 484 0.61 0.15 62 54 0.84
G010470 1150.1 0.26 0.76 0.6 489 1.02 0.25 36 28 2.12
G010471 115.0 0.14 0.61 0.87 514 0.75 0.19 47 66 1.31
G010472 1152.4 0.14 0.61 0.93 530 0.75 0.19 39 60 1.56
G010473 1153.0 0.43 1.24 0.65 525 1.67 0.26 48 25 2.61
G010474 1154.4 0.17 0.66 1.65 491 0.83 0.2 11 28 5.82
G010475 1155.1 0.11 0.55 0.89 314 0.66 0.17 94 152 0.59
G010476 1155.7 0.66 1.55 1.19 528 2.21 0.3 74 57 2.1
G010477 1157.1 0.18 0.71 1.12 484 0.89 0.2 12 19 5.84
G010478 1157.4 0.3 0.82 0.8 488 1.12 0.27 35 34 2.36
G010479 1158.9 0.13 0.69 1.53 528 0.82 0.16 16 35 4.42
G010480 1159.7 0.11 0.56 1.31 525 0.67 0.16 48 113 1.16
G010481 1160.3 0.16 0.64 1.63 599 0.8 0.2 25 65 2.51
G010482 1160.9 0.28 0.78 0.91 300 1.06 0.26 20 24 3.83
G010483 1161.7 0.09 0.52 0.4 504 0.61 0.15 30 23 1.72
G010484 1162.4 0.17 0.66 0.79 492 0.83 0.2 27 33 2.4
G010485 1163.3 0.12 0.63 0.89 462 0.75 0.16 23 33 2.72
G010486 1164.1 0.1 0.54 0.6 321 0.64 0.16 53 59 1.01
G010487 1164.9 0.09 0.52 0.52 324 0.61 0.15 13 13 3.97
G010488 1165.9 0.08 0.53 2.97 551 0.61 0.13 26 146 2.03
G010489 1166.7 0.14 0.61 1.09 313 0.75 0.19 15 27 3.99
G010490 1167.3 0.17 0.69 1.09 310 0.86 0.2 28 44 2.47
G010491 1169.2 0.1 0.57 0.14 319 0.67 0.15 38 9 1.5
G010492 1170.5 0.38 1.37 0.64 533 1.75 0.22 18 8 7.53
G010493 1171.4 0.07 0.45 0.48 511 0.52 0.13 30 32 1.52
mar
ine
infl
uen
ced
-d
eep
lacu
stri
ne
TABLE A 2 TOC AND ROCK-EVAL
88
Table A 2 continued
EX-BTop-
DepthS1 S2 S3 Tmax PP PI HI OI TOC
sampleID m mg/g mg/g mg/g °C mg/g wt ratiomg HC/
g TOC
mg CO2/
g TOC%
G010494 1172.8 0.07 0.45 0.37 501 0.52 0.13 30 25 1.5
G010495 1173.7 0.08 0.49 1.06 482 0.57 0.14 17 37 2.9
G010496 1174.5 0.32 1.41 2.14 582 1.73 0.18 64 97 2.2
G010497 1175.6 0.02 0.38 0.86 483 0.4 0.05 40 92 0.94
G010498 1176.7 0.08 0.49 0.63 321 0.57 0.14 14 18 3.45
G010499 1176.3 0.1 0.66 0.19 597 0.76 0.13 24 7 2.79
G010500 1177.6 0.06 0.46 0.58 485 0.52 0.12 22 28 2.09
G010501 1178.4 0.27 0.77 0.5 475 1.04 0.26 32 21 2.37
G010502 1179.4 0.05 0.42 0.88 490 0.47 0.11 24 50 1.77
G010503 1180.4 0.05 0.39 0.43 581 0.44 0.11 21 23 1.85
G010504 1182.1 0.07 0.46 0.54 482 0.53 0.13 19 22 2.47
G010505 1183.1 0.3 0.8 0.95 478 1.1 0.27 33 40 2.4
G010506 1183.6 0.07 0.47 0.9 490 0.54 0.13 20 38 2.35
G010507 1184.8 0.15 0.64 0.47 484 0.79 0.19 33 24 1.95
G010508 1185.6 0.04 0.41 0.95 489 0.45 0.09 32 73 1.3
G010509 1285.3 0.51 1.07 0.49 600 1.58 0.32 40 18 2.66
G010510 1286.0 0.08 0.5 0.77 296 0.58 0.14 28 43 1.81
G010511 1287.0 0.26 0.76 0.7 601 1.02 0.25 29 26 2.65
G010512 1288.0 0.12 0.68 0.27 315 0.8 0.15 30 12 2.23
G010513 1289.3 0.32 0.81 0.76 315 1.13 0.28 48 45 1.7
G010514 1289.9 0.09 0.59 0.85 600 0.68 0.13 13 19 4.44
G010515 1296.6 0.13 0.61 1.28 280 0.74 0.18 24 51 2.53
G010516 1297.4 0.08 0.52 0.62 600 0.6 0.13 9 11 5.56
G010517 1298.7 0.1 0.55 0.5 316 0.65 0.15 15 14 3.6
G010518 1299.1 0.23 0.73 0.32 283 0.96 0.24 38 16 1.95
G010519 1299.5 0.01 0.19 0.29 593 0.2 0.05 44 67 0.43
G010520 1300.0 0.09 0.52 0.43 308 0.61 0.15 26 21 2.01
G010521 1301.0 0.17 0.65 0.4 291 0.82 0.21 26 16 2.49
G010522 1301.7 0.06 0.43 2.25 601 0.49 0.12 12 64 3.54
G010523 1302.1 0.07 0.57 0.76 297 0.64 0.11 63 83 0.91
G010524 1332.3 0.11 0.57 0.7 600 0.68 0.16 7 9 7.85
G010525 1332.7 0.22 0.73 0.32 600 0.95 0.23 8 4 8.94
G010526 1333.0 0.29 0.82 0.13 286 1.11 0.26 30 5 2.77
G010527 1333.3 0.04 0.34 0.31 599 0.38 0.11 14 12 2.5
G010528 1334.0 0.38 0.93 0.83 279 1.31 0.29 14 12 6.75
G010529 1334.5 0.14 0.61 0.35 322 0.75 0.19 38 22 1.6
G010530 1335.2 0.04 0.37 0.29 599 0.41 0.1 17 14 2.14
G010531 1336.0 0.22 0.76 0.14 284 0.98 0.22 12 2 6.35
G010532 1336.9 0.29 0.81 0.51 300 1.1 0.26 27 17 2.96
G010533 1337.8 0.11 0.55 1.24 304 0.66 0.17 14 31 4.05
G010534 1338.3 0.07 0.47 0.41 600 0.54 0.13 7 6 6.35
G010535 1339.9 0.13 0.61 0.41 298 0.74 0.18 9 6 6.91
G010536 1340.2 0.12 0.58 0.32 277 0.7 0.17 25 14 2.34
G010537 1340.9 0.32 0.82 0.7 290 1.14 0.28 30 25 2.76
G010538 1341.4 0.24 0.78 0.46 596 1.02 0.24 56 33 1.4
G010539 1344.4 0.18 0.67 0.21 289 0.85 0.21 13 4 5.31
G010540 1346.4 0.2 0.7 0.29 293 0.9 0.22 38 16 1.85
G010541 1347.8 0.22 0.72 0.54 280 0.94 0.23 22 16 3.34
G010542 1348.6 0.18 0.68 0.97 598 0.86 0.21 25 36 2.72
G010543 1349.6 0.03 0.3 0.15 597 0.33 0.09 17 8 1.79
dee
p la
cust
rin
ed
eep
lacu
stri
ne
TABLE A 2 TOC AND ROCK-EVAL
89
Table A 2 continued
EX-BTop-
DepthS1 S2 S3 Tmax PP PI HI OI TOC
sampleID m mg/g mg/g mg/g °C mg/g wt ratiomg HC/
g TOC
mg CO2/
g TOC%
G010544 1560.4 0.07 0.55 0.41 307 0.62 0.11 38 28 1.45
G010545 1561.4 0.23 0.75 0.28 299 0.98 0.23 14 5 5.31
G010547 1564.0 0.07 0.51 1.42 601 0.58 0.12 13 37 3.85
G010548 1564.8 0.05 0.44 0.45 598 0.49 0.1 13 13 3.39
G010549 1565.6 0.03 0.53 0.69 308 0.56 0.05 113 147 0.47
G010550 1565.7 0.16 0.68 0.95 255 0.84 0.19 16 22 4.32
G010551 1566.6 0.09 0.52 0.44 309 0.61 0.15 9 8 5.56
G010552 1567.7 0.04 0.4 0.67 513 0.44 0.09 24 41 1.64
G010553 1568.5 0.12 0.67 0.41 254 0.79 0.15 49 30 1.38
G010554 1569.4 0.09 0.52 0.63 284 0.61 0.15 17 21 3.06
G010555 1570.5 0.05 0.42 0.66 314 0.47 0.11 15 24 2.76
G010556 1570.9 0.13 0.61 0.81 281 0.74 0.18 27 36 2.25
G010557 1572.5 0.08 0.48 0.81 600 0.56 0.14 16 27 3.01
G010558 1573.5 0.06 0.52 0.79 277 0.58 0.1 50 75 1.05
G010559 1574.2 0.14 0.62 0.21 277 0.76 0.18 19 6 3.24
G010560 1574.6 0.11 0.56 0.3 281 0.67 0.16 19 10 2.93
G010561 1577.3 0.12 0.59 0.26 317 0.71 0.17 23 10 2.53
G010562 1577.9 0.07 0.46 0.19 309 0.53 0.13 24 10 1.9
dee
p la
cust
rin
e
TABLE A 2 TOC AND ROCK-EVAL
90
Table A 2 continued
EX-CTop-
DepthS1 S2 S3 Tmax PP PI HI OI TOC
sampleID m mg/g mg/g mg/g °C mg/g wt ratiomg HC/
g TOC
mg CO2/
g TOC%
G010362 604.3 1.21 4.17 0.36 408 5.38 0.22 211 18 1.98
G010363 608.8 2.54 7.01 0.47 444 9.55 0.27 188 13 3.72
G010364 609.9 2.06 5.07 0.85 441 7.13 0.29 184 31 2.76
G010365 610.4 1.81 4.34 0.61 453 6.15 0.29 135 19 3.21
G010366 610.8 2.95 5.58 0.27 447 8.53 0.35 149 7 3.74
G010367 611.5 0.58 1.37 2.37 451 1.95 0.3 130 226 1.05
G010368 611.6 1.31 3.29 0.51 449 4.6 0.28 150 23 2.19
G010369 613.1 4.85 12.2 0.44 449 17.05 0.28 189 7 6.45
G010370 613.4 0.23 1.01 0.15 383 1.24 0.19 128 19 0.79
G010371 614.6 2.38 6.63 0.17 443 9.01 0.26 189 5 3.5
G010372 615.8 0.17 0.81 0.16 430 0.98 0.17 109 21 0.75
G010373 616.4 0.18 0.84 0.2 448 1.02 0.18 106 25 0.8
G010374 617.0 0.65 1.82 0.94 453 2.47 0.26 110 57 1.66
G010375 708.9 0.41 1.14 1.3 417 1.55 0.26 130 148 0.88
G010376 709.4 0.61 1.74 0.67 425 2.35 0.26 132 51 1.32
G010377 709.8 1.26 3.1 0.63 428 4.36 0.29 144 29 2.16
G010378 710.6 4.29 8.72 0.66 440 13.01 0.33 203 15 4.29
G010379 711.5 0.65 1.69 0.44 378 2.34 0.28 151 39 1.12
G010380 712.7 1.08 2.64 0.83 419 3.72 0.29 174 55 1.52
G010381 713.2 0.79 2.02 0.49 406 2.81 0.28 155 38 1.3
G010382 715.0 1.13 2.65 1.41 418 3.78 0.3 217 116 1.22
G010383 715.9 2.48 4.83 2.53 425 7.31 0.34 231 121 2.09
G010384 716.7 0.09 0.53 0.33 453 0.62 0.15 111 69 0.48
G010385 717.8 1.21 3.23 0.37 413 4.44 0.27 156 18 2.07
G010386 718.3 0.82 2.39 2.11 429 3.21 0.26 130 115 1.84
G010387 719.1 0.48 1.45 1.12 415 1.93 0.25 115 89 1.26
G010388 720.8 0.97 1.92 0.71 464 2.89 0.34 100 37 1.92
G010389 728.0 3.07 5.46 2.15 472 8.53 0.36 89 35 6.13
G010390 827.8 0.82 1.31 0.77 466 2.13 0.38 32 19 4.09
G010391 828.0 0.26 0.77 0.93 465 1.03 0.25 58 70 1.32
G010392 829.3 0.61 1.22 0.43 461 1.83 0.33 37 13 3.34
G010393 831.2 0.55 1.29 0.62 474 1.84 0.3 28 13 4.64
G010394 831.4 0.45 0.91 0.65 463 1.36 0.33 33 24 2.73
G010395 833.3 0.38 0.89 1.33 471 1.27 0.3 40 60 2.23
G010396 834.9 0.55 1.1 1.14 470 1.65 0.33 32 33 3.47
G010397 854.3 0.62 1.52 0.69 489 2.14 0.29 24 11 6.33
G010398 854.9 0.22 0.72 1.03 446 0.94 0.23 38 54 1.91
G010399 855.8 1.12 1.82 0.61 472 2.94 0.38 25 9 7.14
G010400 856.2 0.31 0.85 0.6 505 1.16 0.27 52 37 1.64
G010401 857.2 0.72 1.71 1.97 520 2.43 0.3 28 32 6.17
G010402 858.3 0.43 1.01 2.12 501 1.44 0.3 38 80 2.64
G010403 877.1 0.35 0.92 1.08 506 1.27 0.28 39 46 2.34
G010404 877.8 0.34 0.9 0.59 505 1.24 0.27 36 24 2.48
G010405 878.3 0.32 0.84 0.67 470 1.16 0.28 33 27 2.51
G010406 878.5 0.39 0.88 0.73 465 1.27 0.31 34 28 2.57
mar
ine
infl
uen
ced
mar
ine
infl
uen
ced
dee
p la
cust
rin
e
TABLE A 2 TOC AND ROCK-EVAL
91
Table A 2 continued
EX-CTop-
DepthS1 S2 S3 Tmax PP PI HI OI TOC
sampleID m mg/g mg/g mg/g °C mg/g wt ratiomg HC/
g TOC
mg CO2/
g TOC%
G010407 880.4 0.35 0.87 0.76 473 1.22 0.29 33 29 2.65
G010408 881.2 0.23 0.74 1.53 508 0.97 0.24 43 88 1.74
G010409 882.1 0.35 0.86 0.83 475 1.21 0.29 41 39 2.12
G010410 883.3 0.55 1.19 1.57 508 1.74 0.32 37 49 3.19
G010411 884.6 0.18 0.67 1.22 514 0.85 0.21 37 67 1.82
G010412 885.7 0.14 0.6 1.85 509 0.74 0.19 41 125 1.48
G010413 887.2 0.2 0.8 4.28 442 1 0.2 43 229 1.87
G010414 888.3 0.11 0.54 1.03 517 0.65 0.17 38 72 1.43
G010415 889.7 0.17 0.66 0.78 482 0.83 0.2 31 37 2.13
G010416 919.9 0.14 2.9 0.31 541 3.04 0.05 22 2 12.9
G010417 920.8 0.11 0.95 0.54 532 1.06 0.1 29 16 3.29
G010418 921.2 0.24 4.13 1 554 4.37 0.05 24 6 17.4
G010419 922.1 0.02 0.32 0.28 533 0.34 0.06 32 28 1
G010420 923.1 0.02 0.29 7.48 548 0.31 0.06 39 995 0.75
G010421 924.0 0.06 0.55 0.43 546 0.61 0.1 27 21 2.06
G010422 924.8 0.05 0.39 9.27 496 0.44 0.11 64 1515 0.61
G010423 926.0 0.1 0.54 0.96 517 0.64 0.16 41 72 1.33
G010424 926.5 0.07 0.46 0.18 589 0.53 0.13 21 8 2.23
G010425 927.7 0.16 0.68 1.31 597 0.84 0.19 15 30 4.41
G010426 929.3 0.17 0.74 1.78 501 0.91 0.19 15 35 5.07
G010427 930.2 0.03 0.3 1.08 563 0.33 0.09 31 111 0.98
G010428 931.1 0.03 0.36 0.37 529 0.39 0.08 31 31 1.18
G010429 932.0 0.11 0.59 1.12 598 0.7 0.16 14 27 4.15
G010430 933.0 0.04 0.37 0.51 498 0.41 0.1 32 45 1.14
G010431 933.6 0.09 0.63 0.41 277 0.72 0.13 100 65 0.63
G010432 934.5 0.29 0.9 0.78 487 1.19 0.24 13 12 6.67
G010433 935.4 0.18 0.74 1.76 600 0.92 0.2 11 26 6.77
G010434 936.5 0.06 0.5 1.08 539 0.56 0.11 96 208 0.52
G010435 937.0 0.03 0.31 1.37 574 0.34 0.09 27 119 1.15
G010436 937.3 0.02 0.29 3.79 547 0.31 0.06 38 503 0.75
G010437 938.5 0.03 0.38 1.11 550 0.41 0.07 32 94 1.18
G010438 939.5 0.04 0.39 0.36 495 0.43 0.09 82 76 0.47
G010439 940.6 0.05 0.45 0.57 574 0.5 0.1 26 33 1.71
G010440 941.6 0.13 0.68 2.16 599 0.81 0.16 10 33 6.5
lake
lain
dee
p la
cust
rin
e
TABLE A 3 TVAP-GC-FID (SINGLE COMPONENTS OF FREE HC)
92
Table A 3 Tvap-GC-FID (single components of free HC)
EX-A
G010276
G010277
G010281
G010283
G010299
G010300
G010302
G010305
G010316
G010346
G010349
G010351
Konz. C1-5 (µg/mg) 0.068 0.075 0.065 0.101 0.037 0.064 0.078 0.087 0.027 0.060 0.055 0.155
Konz. Methane (µg/mg) 0.010 0.005 0.003 0.007 0.001 0.002 0.004 0.004 0.001 0.006 0.002 0.004
Konz. C2-5 (mg/g) 0.059 0.071 0.062 0.095 0.036 0.062 0.074 0.084 0.026 0.054 0.053 0.151
Konz. C6-14 (g/mg) 0.270 0.241 0.405 0.690 0.296 0.336 0.429 0.787 0.170 0.484 0.352 1.170
C6-14 Resolved 0.154 0.179 0.257 0.379 0.141 0.164 0.217 0.534 0.101 0.308 0.195 0.724
C6-14 Hump 0.116 0.063 0.148 0.311 0.155 0.172 0.212 0.253 0.069 0.175 0.157 0.446
Konz. C15+ (µg/mg) 0.292 0.280 0.797 2.226 5.841 3.093 2.670 7.211 2.557 2.389 3.090 6.394
C15+ Resolved 0.057 0.080 0.154 0.183 3.039 0.602 0.338 0.863 0.329 0.511 0.259 0.451
C15+ Hump 0.234 0.200 0.644 2.044 2.802 2.491 2.332 6.348 2.228 1.878 2.831 5.942
Konz.Gesamt (µg/mg) 0.630 0.597 1.268 3.017 6.174 3.493 3.177 8.086 2.754 2.933 3.498 7.719
C6+ 0.562 0.522 1.203 2.916 6.137 3.429 3.099 7.998 2.727 2.873 3.443 7.563
C6+ Resolved 0.211 0.259 0.411 0.562 3.180 0.766 0.555 1.397 0.429 0.820 0.454 1.175
C6+ Hump 0.351 0.263 0.792 2.354 2.957 2.663 2.544 6.601 2.298 2.053 2.989 6.388
C2+ 0.620 0.592 1.264 3.011 6.173 3.491 3.173 8.082 2.753 2.927 3.496 7.714
n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
TOC 4.27 7.25 8.99 9.15 3.79 7.29 4.68 11.80 13.50 5.72 5.32 17.50
S1 0.21 0.20 0.30 0.55 3.53 1.01 0.43 0.93 1.17 0.51 0.21 0.82
S2 23.21 53.68 64.74 58.27 30.33 53.44 27.89 91.48 102.90 33.51 40.01 116.19
S3 1.45 0.95 0.64 2.76 0.89 2.79 1.79 1.47 1.68 1.14 0.62 0.54
HI 544 740 720 637 800 733 596 775 762 586 752 664
OI 34 13 7 30 23 38 38 12 12 20 12 3
Tmax 429 439 443 429 438 432 433 446 449 423 442 452
PI 0.009 0.004 0.005 0.009 0.104 0.019 0.015 0.010 0.011 0.015 0.005 0.007
S1+S2 23.42 53.88 65.04 58.82 33.86 54.45 28.32 92.41 104.07 34.02 40.22 117.01
Konz.Gesamt (mg/g rock) 0.63 0.60 1.27 3.02 6.17 3.49 3.18 8.09 2.75 2.93 3.50 7.72
RE/ Konz. gesamt 36.85 89.85 51.07 19.31 4.91 15.30 8.78 11.31 37.36 11.43 11.44 15.05
Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
branched + cyclo Alkanes 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates / n -C6+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates / n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates/n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity (Aromates+
Phenols) / n -C6+
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/n -C6+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols /n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols / n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols / n -C9-11 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
m,p -Cresol / m,p -Xylol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
m,p-Cresol / n -C10 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes / n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
branched+cyclo Alkanes / n -
C6-14
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
GOR 0.121 0.145 0.054 0.035 0.006 0.019 0.025 0.011 0.010 0.021 0.016 0.021
Gas Wetness (C2-5)/(C1-5) 0.859 0.934 0.949 0.933 0.971 0.965 0.946 0.958 0.954 0.905 0.966 0.971
GOR resolved 0.323 0.291 0.158 0.181 0.012 0.084 0.141 0.062 0.063 0.073 0.122 0.132
mono-Aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
di-aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
di/mono-Aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes/Mono-Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/ Konzgesamt [%] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C6:1-14:1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15:1+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
C1-5/S2 0.293 0.141 0.101 0.174 0.121 0.120 0.281 0.095 0.026 0.178 0.138 0.134
TABLE A 3 TVAP-GC-FID (SINGLE COMPONENTS OF FREE HC)
93
Table A 3 continued
EX-B
G010449
G010450
G010453
G010454
G010473
G010474
G010478
G010492
G010521
G010524
G010525
G010550
G010555
G010557
Konz. C1-5 (µg/mg) 0.055 0.073 0.023 0.019 0.053 0.030 0.013 0.058 0.033 0.042 0.022 0.005 0.012 0.012
Konz. Methane (µg/mg) 0.000 0.001 0.001 0.002 0.001 0.001 0.000 0.001 0.001 0.002 0.003 0.001 0.001 0.001
Konz. C2-5 (mg/g) 0.054 0.072 0.022 0.018 0.052 0.029 0.013 0.058 0.032 0.040 0.019 0.004 0.011 0.011
Konz. C6-14 (g/mg) 0.458 1.828 0.957 0.249 0.537 0.219 0.113 0.289 0.261 0.102 0.248 0.087 0.034 0.088
C6-14 Resolved 0.345 1.560 0.771 0.206 0.481 0.185 0.076 0.223 0.171 0.074 0.154 0.058 0.028 0.052
C6-14 Hump 0.112 0.268 0.186 0.043 0.056 0.034 0.037 0.066 0.090 0.028 0.093 0.029 0.006 0.036
Konz. C15+ (µg/mg) 0.779 3.579 1.256 1.016 0.074 0.102 0.065 0.069 0.115 0.294 0.056 0.077 0.026 0.085
C15+ Resolved 0.497 2.473 0.809 0.713 0.010 0.004 0.002 0.005 0.015 0.005 0.003 0.002 0.001 0.002
C15+ Hump 0.282 1.107 0.447 0.303 0.064 0.098 0.063 0.064 0.100 0.290 0.053 0.076 0.025 0.083
Konz.Gesamt (µg/mg) 1.292 5.480 2.236 1.285 0.664 0.351 0.191 0.416 0.410 0.439 0.326 0.168 0.072 0.186
C6+ (mg/g rock) 1.237 5.407 2.213 1.265 0.610 0.321 0.179 0.358 0.377 0.397 0.303 0.164 0.060 0.174
C6+ Resolved 0.842 4.032 1.580 0.919 0.490 0.189 0.078 0.228 0.187 0.079 0.157 0.060 0.029 0.054
C6+ Hump 0.394 1.375 0.633 0.347 0.120 0.132 0.101 0.130 0.190 0.318 0.146 0.104 0.031 0.119
C2+ (mg/g rock) 1.291 5.479 2.235 1.283 0.662 0.350 0.191 0.416 0.408 0.437 0.322 0.168 0.071 0.185
n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
TOC (%) 2.90 7.12 2.13 1.55 2.61 5.82 2.36 7.53 2.49 7.85 8.94 4.32 2.76 3.01
S1 (mg/g rock) 1.02 4.27 1.14 0.57 0.43 0.17 0.30 0.38 0.17 0.11 0.22 0.16 0.05 0.08
S2 (mg/g rock) 2.23 5.94 2.30 2.01 1.24 0.66 0.82 1.37 0.65 0.57 0.73 0.68 0.42 0.48
S3 (mg/g rock) 0.20 0.95 0.26 1.88 0.65 1.65 0.80 0.64 0.40 0.70 0.32 0.95 0.66 0.81
HI (mg HC/g TOC) 77 83 108 130 48 11 35 18 26 7 8 16 15 16
OI (mg CO2/g TOC) 7 13 12 121 25 28 34 8 16 9 4 22 24 27
Tmax (°C) 320 472 345 395 525 491 488 533 291 600 600 255 314 600
PI 0.314 0.418 0.331 0.221 0.257 0.205 0.268 0.217 0.207 0.162 0.232 0.190 0.106 0.143
S1+S2 (mg/g rock) 3.25 10.21 3.44 2.58 1.67 0.83 1.12 1.75 0.82 0.68 0.95 0.84 0.47 0.56
Konz.Gesamt (mg/g rock) 1.292 5.480 2.236 1.285 0.664 0.351 0.191 0.416 0.410 0.439 0.326 0.168 0.072 0.186
RE/ Konz. gesamt 1.727 1.084 1.029 1.565 1.869 1.878 4.287 3.291 1.586 1.300 2.242 4.040 5.860 2.580
Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
branched + cyclo Alkanes 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates / n -C6+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates / n -C6-14
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates/n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity (Aromates+
Phenols) / n -C6+
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/n -C6+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols /n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols / n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols / n -C9-11 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
m,p -Cresol / m,p -Xylol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
m,p -Cresol / n -C10 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes / n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
branched+cyclo Alkanes / n -
C6-14
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
GOR 0.04 0.01 0.01 0.02 0.09 0.09 0.07 0.16 0.09 0.11 0.07 0.03 0.20 0.07
Gas Wetness (C2-5)/(C1-5) 0.992 0.986 0.973 0.919 0.976 0.961 0.985 0.989 0.957 0.954 0.856 0.856 0.923 0.915
GOR resolved 0.06 0.02 0.01 0.02 0.11 0.16 0.16 0.26 0.18 0.53 0.14 0.08 0.41 0.23
mono-Aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
di-aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
di/mono-Aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes/Mono-Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/ Konzgesamt [%] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C6:1-14:1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15:1+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
C1-5/S2 2.455 1.228 0.998 0.966 4.299 4.560 1.550 4.250 5.121 7.369 3.047 0.667 2.816 2.564
TABLE A 3 TVAP-GC-FID (SINGLE COMPONENTS OF FREE HC)
94
Table A 3 continued
EX-C
G010362
G010363
G010366
G010369
G010380
G010383
G010385
G010389
G010396
G010397
G010399
G010416
G010417
G010418
Konz. C1-5 (µg/mg) 0.052 0.026 0.068 0.015 0.009 0.022 0.011 0.010 0.054 0.129 0.153 0.023 0.184 0.171
Konz. Methane (µg/mg) 0.001 0.001 0.001 0.000 0.000 0.001 0.000 0.000 0.002 0.002 0.002 0.001 0.001 0.003
Konz. C2-5 (mg/g) 0.052 0.025 0.068 0.014 0.008 0.021 0.011 0.010 0.052 0.127 0.151 0.022 0.183 0.168
Konz. C6-14 (g/mg) 0.587 1.016 1.458 1.009 0.362 0.571 0.280 1.283 0.877 1.358 1.618 0.125 0.842 0.140
C6-14 Resolved 0.426 0.797 1.087 0.736 0.269 0.468 0.223 1.121 0.734 1.246 1.473 0.082 0.730 0.120
C6-14 Hump 0.161 0.220 0.372 0.273 0.093 0.103 0.058 0.162 0.143 0.111 0.146 0.042 0.112 0.019
Konz. C15+ (µg/mg) 1.664 2.755 3.449 5.140 1.487 3.447 1.348 1.840 0.104 0.268 0.169 0.191 0.219 0.046
C15+ Resolved 0.864 1.563 1.903 2.752 0.783 2.281 0.857 1.252 0.023 0.046 0.051 0.004 0.015 0.013
C15+ Hump 0.800 1.192 1.546 2.388 0.704 1.167 0.492 0.588 0.081 0.222 0.118 0.186 0.204 0.033
Konz.Gesamt (µg/mg) 2.304 3.798 4.976 6.163 1.857 4.041 1.640 3.133 1.035 1.754 1.940 0.338 1.245 0.356
C6+ (mg/g rock) 2.251 3.772 4.908 6.148 1.849 4.019 1.629 3.123 0.981 1.626 1.787 0.315 1.062 0.186
C6+ Resolved 1.290 2.360 2.990 3.487 1.052 2.749 1.079 2.373 0.757 1.292 1.523 0.086 0.746 0.134
C6+ Hump 0.961 1.411 1.918 2.661 0.797 1.270 0.550 0.750 0.224 0.333 0.264 0.229 0.316 0.052
C2+ (mg/g rock) 2.303 3.797 4.976 6.163 1.857 4.040 1.640 3.133 1.033 1.753 1.938 0.337 1.244 0.353
n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
TOC (%) 1.98 3.72 3.74 6.45 1.52 2.09 2.07 6.13 3.47 6.33 7.14 12.90 3.29 17.40
S1 (mg/g rock) 1.21 2.54 2.95 4.85 1.08 2.48 1.21 3.07 0.55 0.62 1.12 0.14 0.11 0.24
S2 (mg/g rock) 4.17 7.01 5.58 12.20 2.64 4.83 3.23 5.46 1.10 1.52 1.82 2.90 0.95 4.13
S3 (mg/g rock) 0.36 0.47 0.27 0.44 0.83 2.53 0.37 2.15 1.14 0.69 0.61 0.31 0.54 1.00
HI (mg HC/g TOC) 211 188 149 189 174 231 156 89 32 24 25 22 29 24
OI (mg CO2/g TOC) 18 13 7 7 55 121 18 35 33 11 9 2 16 6
Tmax (°C) 408 444 447 449 419 425 413 472 470 489 472 541 532 554
PI 0.225 0.266 0.346 0.284 0.290 0.339 0.273 0.360 0.333 0.290 0.381 0.046 0.104 0.055
S1+S2 (mg/g rock) 5.38 9.55 8.53 17.05 3.72 7.31 4.44 8.53 1.65 2.14 2.94 3.04 1.06 4.37
Konz.Gesamt (mg/g rock) 2.304 3.798 4.976 6.163 1.857 4.041 1.640 3.133 1.035 1.754 1.940 0.338 1.245 0.356
RE/ Konz. gesamt 1.810 1.846 1.121 1.980 1.421 1.195 1.970 1.743 1.063 0.866 0.938 8.574 0.763 11.592
Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
branched + cyclo Alkanes 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates / n -C6+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates / n -C6-14
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity Aromates/n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromaticity (Aromates+
Phenols) / n -C6+
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/n -C6+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols /n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols / n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols / n -C9-11 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
m,p -Cresol / m,p -Xylol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
m,p -Cresol / n -C10 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes / n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
branched+cyclo Alkanes / n -
C6-14
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
GOR 0.02 0.01 0.01 0.00 0.00 0.01 0.01 0.00 0.05 0.08 0.09 0.07 0.17 0.92
Gas Wetness (C2-5)/(C1-5) 0.990 0.964 0.993 0.990 0.977 0.971 0.981 0.993 0.959 0.987 0.990 0.964 0.994 0.982
GOR resolved 0.04 0.01 0.02 0.00 0.01 0.01 0.01 0.00 0.07 0.10 0.10 0.27 0.25 1.28
mono-Aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
di-aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
di/mono-Aromatics 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Thiophenes/Mono-Aromates 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Phenols/ Konzgesamt [%] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C6-14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C6:1-14:1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n -C15:1+ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
C1-5/S2 1.248 0.373 1.226 0.119 0.329 0.454 0.343 0.176 4.888 8.471 8.384 0.795 19.318 4.132
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
95
Table A 4 Open-system pyrolysis GC-FID (primary products)
Format ion/ B asin
GFZ no . G 0 1 0 2 7 6 G 0 1 0 2 7 7 G 0 1 0 2 8 1 G 0 1 0 2 8 3 G 0 1 0 2 9 9 G 0 1 0 3 0 0 G 0 1 0 3 0 2 G 0 1 0 3 0 5 G 0 1 0 3 1 6 G 0 1 0 3 4 6 G 0 1 0 3 4 9 G 0 1 0 3 5 1
n C1 mg/ g T OC 9.37 11.00 8.01 10.29 3.91 9.63 8.60 10.74 13.50 9.13 6.33 10.06
n C2:1 mg/ g T OC 3.33 7.66 6.66 4.65 3.88 3.53 3.90 10.81 18.96 4.10 5.24 9.59
n C2 mg/ g T OC 8.29 10.68 9.11 7.95 4.14 7.77 7.35 11.62 13.12 7.35 7.42 11.05
n C3 mg/ g T OC 12.48 16.22 14.69 11.60 8.48 10.92 11.22 19.81 28.81 11.44 12.40 18.56
I-C4 mg/ g T OC 0.33 0.21 0.17 0.28 0.12 0.31 0.26 0.18 0.21 0.30 0.17 0.21
n C4:1 mg/ g T OC 5.26 7.83 6.75 4.89 4.13 5.14 5.57 10.63 14.60 5.03 6.06 8.80
n C4 mg/ g T OC 4.02 4.74 5.18 3.21 3.48 3.49 3.97 4.86 5.90 3.40 4.04 4.91
I-C5 mg/ g T OC 0.73 0.40 0.44 0.77 0.29 1.04 0.74 0.38 0.47 0.78 0.38 0.33
n C5:1 mg/ g T OC 2.67 4.94 4.78 2.41 3.09 2.43 3.10 6.76 8.87 2.32 3.87 5.73
n C5 mg/ g T OC 2.53 3.37 3.21 2.05 2.12 2.36 2.71 3.62 4.26 2.14 2.80 3.40
(2,2 DM Pentan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
cy-C5 mg/ g T OC 0.23 0.33 0.33 0.26 0.17 0.26 0.22 0.39 0.51 0.22 0.28 0.37
2-M -C5 mg/ g T OC 0.53 0.33 0.30 0.41 0.19 0.51 0.44 0.19 0.31 0.50 0.25 0.27
2-Butanone mg/ g T OC 0.32 0.28 0.34 0.38 0.17 0.45 0.30 0.36 0.36 0.32 0.28 0.31
3-M -C5 mg/ g T OC 0.17 0.10 0.10 0.13 0.07 0.14 0.13 0.10 0.10 0.14 0.10 0.12
n C6:1 mg/ g T OC 3.50 7.33 7.48 3.39 5.05 3.47 4.58 10.90 14.03 3.14 6.35 9.56
n C6 mg/ g T OC 2.13 3.22 3.14 1.68 2.01 1.89 2.44 3.62 4.03 1.70 2.68 3.23
M -Cy-C5 mg/ g T OC 0.33 0.48 0.51 0.35 0.29 0.40 0.38 0.68 0.90 0.34 0.47 0.64
(2,4 DM Pentan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
(2,2,3 DM Butan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzol mg/ g T OC 1.11 3.16 1.63 0.77 0.78 0.85 1.42 3.06 3.30 1.15 0.79 0.85
Thiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
cy C6 mg/ g T OC 0.21 0.31 0.32 0.23 0.18 0.17 0.27 0.28 0.59 0.25 0.30 0.35
2 M C6 mg/ g T OC 0.27 0.16 0.17 0.18 0.09 0.00 0.20 0.09 0.14 0.30 0.13 0.09
2,3 DM Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,1 DM Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3 M C6 mg/ g T OC 0.23 0.12 0.16 0.12 0.04 0.14 0.19 0.10 0.20 0.20 0.08 0.12
1, cis, 3 DM Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1, trans, 3 DM cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,2,4 Tri M Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C7:1 mg/ g T OC 2.43 5.11 5.37 2.23 3.51 2.34 3.33 7.44 9.31 2.04 4.33 6.38
n C7 mg/ g T OC 2.15 3.36 3.33 1.64 2.16 1.88 2.60 3.96 4.43 1.65 2.96 3.50
M -Cy-C6 mg/ g T OC 0.32 0.39 0.50 0.34 0.35 0.40 0.44 0.55 0.92 0.35 0.36 0.54
1,1,3 Tri M cy Pentan
+ 2,2 DM Hexanmg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
E Cy Pentan mg/ g T OC 0.19 0.30 0.29 0.19 0.18 0.22 0.23 0.36 0.48 0.19 0.15 0.36
2,5 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,4 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,trans, 2, cis, 4 Tri M Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3,3 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1, trans, 2, cis, 3 Tri M Cy Pentanmg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,3,4 Tri M Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Toluol mg/ g T OC 1.82 2.91 1.64 1.55 1.11 1.34 1.93 2.79 3.32 1.65 1.35 1.71
2-M -Thiophen mg/ g T OC 0.63 0.33 0.39 0.60 0.32 0.70 0.77 0.32 0.41 0.93 0.40 0.23
3-M -Thiophen mg/ g T OC 0.44 0.69 0.57 0.45 0.42 0.43 0.45 0.78 1.34 0.44 0.51 0.55
n C8:1 mg/ g T OC 1.80 4.07 4.21 1.58 2.80 1.72 2.72 5.75 7.26 1.46 3.47 5.00
n C8 mg/ g T OC 1.92 3.21 3.24 1.30 2.07 1.54 2.43 3.77 4.11 1.33 2.81 3.29
E Benzol mg/ g T OC 0.60 0.75 0.49 0.47 0.37 0.54 0.61 0.81 0.91 0.50 0.39 0.47
E Thiophen mg/ g T OC 0.26 0.20 0.15 0.20 0.09 0.20 0.26 0.14 0.26 0.25 0.15 0.17
2,5 DM Thiophen mg/ g T OC 0.16 0.22 0.18 0.26 0.19 0.26 0.26 0.08 0.24 0.32 0.10 0.06
meta, para Xylol mg/ g T OC 1.53 1.21 0.94 1.18 0.63 1.23 1.32 1.23 1.56 1.25 0.91 1.07
2,4 DM Thiophen mg/ g T OC 0.33 0.31 0.33 0.19 0.22 0.19 0.28 0.31 0.51 0.18 0.31 0.35
2,3 DM Thiophen mg/ g T OC 0.33 0.17 0.14 0.25 0.13 0.29 0.31 0.15 0.31 0.27 0.26 0.29
Styrol mg/ g T OC 0.44 0.73 0.57 0.42 0.37 0.37 0.49 0.78 0.82 0.49 0.38 0.42
ortho Xylol mg/ g T OC 0.80 1.04 0.64 0.70 0.50 0.65 0.79 0.95 1.18 0.76 0.63 0.66
n C9:1 mg/ g T OC 1.48 3.62 3.89 1.27 2.59 1.43 2.48 5.16 6.36 1.16 3.10 4.53
n C9 mg/ g T OC 1.47 2.84 2.89 1.07 1.84 1.28 2.04 3.25 3.67 1.05 2.41 2.99
2-Propylthiophene mg/ g T OC 0.22 0.39 0.21 0.16 0.18 0.12 0.24 0.34 0.34 0.20 0.20 0.16
PropylBenzol mg/ g T OC 0.31 0.33 0.30 0.25 0.21 0.30 0.35 0.38 0.50 0.23 0.28 0.42
2E5M Thiophen mg/ g T OC 0.32 0.20 0.19 0.26 0.17 0.30 0.00 0.24 0.34 0.32 0.23 0.17
TM B mg/ g T OC 0.69 0.59 0.46 0.54 0.30 0.53 0.63 0.58 0.79 0.60 0.48 0.55
EX-A - Wealden Shale - Lower Saxony Basin
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
96
Table A 4 continued
GFZ no . G 0 1 0 2 7 6 G 0 1 0 2 7 7 G 0 1 0 2 8 1 G 0 1 0 2 8 3 G 0 1 0 2 9 9 G 0 1 0 3 0 0 G 0 1 0 3 0 2 G 0 1 0 3 0 5 G 0 1 0 3 1 6 G 0 1 0 3 4 6 G 0 1 0 3 4 9 G 0 1 0 3 5 1
1,3,5TM Benzol mg/ g T OC 0.25 0.15 0.12 0.22 0.09 0.19 0.30 0.17 0.22 0.22 0.14 0.16
Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1E-2-M Benzol mg/ g T OC 0.53 0.47 0.32 0.42 0.23 0.34 0.41 0.48 0.53 0.37 0.33 0.32
2,3,5-TriM Thiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,2,4-TriM Benzol mg/ g T OC 0.75 0.46 0.36 0.43 0.22 0.47 0.45 0.42 0.68 0.55 0.33 0.34
n C10:1 mg/ g T OC 1.59 3.93 4.39 1.36 3.01 1.49 2.63 5.88 7.29 1.14 3.54 5.36
n C10 mg/ g T OC 1.43 2.84 2.95 1.01 1.85 1.15 2.07 3.27 3.71 0.92 2.37 3.03
1,2,3TM Benzol mg/ g T OC 0.43 0.25 0.16 0.24 0.18 0.24 0.33 0.33 0.49 0.20 0.17 0.21
ortho Chresol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M eta, Para Chresol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C11:1 mg/ g T OC 1.48 3.63 4.05 1.25 2.80 1.41 2.44 5.13 6.21 1.12 3.41 4.88
n C11 mg/ g T OC 1.31 2.84 3.01 0.97 1.97 1.23 1.96 3.38 3.72 0.94 2.60 3.34
E Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.21 0.13 0.20 0.19 0.30 0.44 0.23 0.00 0.00
E Phenol mg/ g T OC 0.53 0.26 0.25 0.43 0.14 0.37 0.36 0.27 0.32 0.30 0.17 0.25
DM Phenol mg/ g T OC 0.00 0.62 0.43 0.31 0.25 0.29 0.38 0.61 0.52 0.32 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Naphtalin mg/ g T OC 0.34 0.71 0.32 0.28 0.20 0.28 0.30 0.63 0.59 0.33 0.28 0.29
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzothiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C12:1 mg/ g T OC 1.52 3.51 4.00 1.13 2.82 1.41 2.16 4.69 5.85 1.03 3.42 4.49
n C12 mg/ g T OC 1.49 2.77 3.19 0.92 2.24 1.25 1.85 3.36 4.08 0.87 2.98 3.42
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -E-Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -E-Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -Benzothiophen (1) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2 M Naphtalin mg/ g T OC 0.52 0.55 0.40 0.38 0.29 0.34 0.42 0.40 0.65 0.40 0.35 0.36
n C13:1 mg/ g T OC 1.43 3.21 3.91 1.03 2.82 1.40 2.09 4.15 5.01 0.92 3.41 4.04
1 M Naphtalin mg/ g T OC 0.47 0.45 0.37 0.40 0.28 0.34 0.48 0.45 0.49 0.27 0.27 0.00
n C13 mg/ g T OC 1.59 3.06 3.49 1.01 2.39 1.34 2.10 3.23 3.93 0.97 3.16 3.34
n C14:1 mg/ g T OC 1.58 2.95 3.66 1.04 2.91 1.31 2.54 4.06 4.90 1.03 3.53 4.23
n C14 mg/ g T OC 1.67 2.88 3.11 0.98 2.31 1.28 2.03 3.08 3.85 0.99 3.06 3.45
DM Naphtalin mg/ g T OC 0.82 0.63 0.55 0.57 0.39 0.56 0.61 0.62 0.77 0.63 0.50 0.54
?2 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?3 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C15:1 u. ?4 mg/ g T OC 1.19 2.54 3.11 0.78 2.43 1.02 1.76 3.62 4.49 0.75 2.88 4.07
?5 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C15 mg/ g T OC 1.48 2.69 2.98 0.81 2.17 1.06 1.78 3.15 3.83 0.82 2.79 3.53
?6 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Naphtalin mg/ g T OC 0.24 0.18 0.22 0.23 0.13 0.16 0.19 0.21 0.23 0.21 0.21 0.24
TM Naphtalin mg/ g T OC 0.21 0.35 0.28 0.23 0.27 0.21 0.20 0.29 0.28 0.18 0.21 0.24
TM Naphtalin mg/ g T OC 0.12 0.26 0.27 0.12 0.20 0.15 0.18 0.36 0.44 0.10 0.27 0.41
n C16:1 mg/ g T OC 1.13 2.50 2.96 0.81 2.45 1.04 1.55 3.58 4.32 0.82 2.98 4.03
n C16 mg/ g T OC 1.20 2.50 2.74 0.76 2.08 0.98 1.47 2.97 3.73 0.74 2.69 3.54
Isopropyl-DM -Naphtaline mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C17:1 mg/ g T OC 0.89 2.11 2.65 0.71 2.29 0.88 1.40 3.19 3.79 0.67 2.66 3.80
n C17 mg/ g T OC 1.09 2.31 2.60 0.68 2.07 0.92 1.40 2.85 3.66 0.65 2.63 3.60
Pristan mg/ g T OC 0.10 0.25 0.20 0.07 0.15 0.07 0.08 0.25 0.35 0.04 0.22 0.25
Te-M -Naphtaline mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Prist-1-en mg/ g T OC 0.09 0.00 0.00 0.20 0.10 0.42 0.24 0.09 0.00 0.11 0.00 0.00
n C18:1 mg/ g T OC 0.77 1.87 2.42 0.52 2.17 0.71 1.32 2.92 3.36 0.60 2.43 3.36
n C18 mg/ g T OC 1.01 2.21 2.50 0.55 2.03 0.75 1.33 2.74 3.42 0.68 2.54 3.39
Phytan mg/ g T OC 0.16 0.23 0.24 0.07 0.18 0.10 0.15 0.26 0.36 0.10 0.24 0.30
n C19:1 mg/ g T OC 0.74 1.68 2.10 0.47 2.01 0.64 1.14 2.53 2.82 0.57 2.13 2.97
n C19 mg/ g T OC 0.97 2.07 2.25 0.49 1.96 0.71 1.22 2.55 3.03 0.63 2.30 3.06
? M -(Phenantrene/Anthracene) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?7 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
97
Table A 4 continued
GFZ no . G 0 1 0 2 7 6 G 0 1 0 2 7 7 G 0 1 0 2 8 1 G 0 1 0 2 8 3 G 0 1 0 2 9 9 G 0 1 0 3 0 0 G 0 1 0 3 0 2 G 0 1 0 3 0 5 G 0 1 0 3 1 6 G 0 1 0 3 4 6 G 0 1 0 3 4 9 G 0 1 0 3 5 1
?8 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C20:1 mg/ g T OC 0.69 1.49 1.90 0.43 1.89 0.55 1.01 2.24 2.35 0.53 1.90 2.61
n C20 mg/ g T OC 0.92 1.81 2.06 0.47 1.86 0.61 1.08 2.30 2.62 0.62 2.10 2.76
?9 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?10 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C21:1 mg/ g T OC 0.63 1.31 1.75 0.40 1.87 0.46 0.99 2.12 2.08 0.46 1.79 2.36
n C21 mg/ g T OC 0.88 1.65 1.95 0.41 1.85 0.51 1.03 2.22 2.45 0.51 1.99 2.54
TM Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C22:1 mg/ g T OC 0.63 1.26 1.81 0.35 1.93 0.47 1.01 2.15 2.05 0.43 1.79 2.34
n C22 mg/ g T OC 0.82 1.47 1.89 0.35 1.84 0.44 0.98 2.15 2.29 0.49 1.93 2.41
Isopropyl-M -Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?11 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C23:1 mg/ g T OC 0.55 1.03 1.57 0.31 1.79 0.40 0.89 1.87 1.67 0.35 1.53 1.97
n C23 mg/ g T OC 0.78 1.41 1.94 0.35 1.91 0.43 0.97 2.13 2.11 0.46 1.85 2.31
n C24:1 mg/ g T OC 0.61 0.94 1.53 0.31 1.74 0.39 0.81 1.78 1.44 0.34 1.50 1.79
n C24 mg/ g T OC 0.77 1.24 1.76 0.32 1.82 0.39 0.90 2.02 1.84 0.42 1.71 2.04
n C25:1 mg/ g T OC 0.46 0.70 1.19 0.28 1.53 0.34 0.71 1.47 1.06 0.32 1.24 1.47
n C25 mg/ g T OC 0.80 1.02 1.62 0.32 1.74 0.38 0.81 1.84 1.40 0.41 1.52 1.79
n C26:1 mg/ g T OC 0.43 0.42 0.87 0.26 1.31 0.32 0.61 1.12 0.66 0.30 0.92 1.10
n C26 mg/ g T OC 0.74 0.76 1.24 0.32 1.53 0.39 0.76 1.53 1.07 0.42 1.33 1.56
n C27:1 mg/ g T OC 0.35 0.30 0.66 0.23 1.00 0.26 0.50 0.80 0.45 0.27 0.73 0.83
n C27 mg/ g T OC 0.73 0.55 1.05 0.32 1.33 0.36 0.66 1.16 0.74 0.40 1.08 1.18
n C28:1 mg/ g T OC 0.30 0.28 0.53 0.22 0.92 0.22 0.45 0.66 0.34 0.24 0.66 0.68
n C28 mg/ g T OC 0.55 0.37 0.73 0.27 1.20 0.27 0.55 0.83 0.49 0.34 0.84 0.81
n C29:1 mg/ g T OC 0.21 0.17 0.42 0.17 0.70 0.21 0.37 0.46 0.24 0.20 0.47 0.54
n C29 mg/ g T OC 0.48 0.24 0.49 0.23 0.79 0.27 0.46 0.57 0.33 0.33 0.63 0.61
n C30:1 mg/ g T OC 0.15 0.10 0.22 0.13 0.52 0.14 0.24 0.29 0.16 0.18 0.29 0.36
n C30 mg/ g T OC 0.30 0.20 0.40 0.19 0.62 0.21 0.35 0.46 0.26 0.28 0.43 0.45
n C31:1 mg/ g T OC 0.08 0.06 0.12 0.09 0.34 0.14 0.18 0.18 0.09 0.12 0.19 0.20
n C31 mg/ g T OC 0.23 0.13 0.28 0.16 0.51 0.22 0.29 0.30 0.20 0.23 0.36 0.33
n C32:1 mg/ g T OC 0.03 0.05 0.08 0.04 0.23 0.10 0.08 0.13 0.06 0.08 0.12 0.15
n C32 mg/ g T OC 0.14 0.09 0.20 0.10 0.41 0.19 0.25 0.23 0.16 0.18 0.29 0.25
n C33:1 mg/ g T OC 0.02 0.02 0.06 0.04 0.17 0.05 0.08 0.10 0.05 0.05 0.09 0.13
n C33 mg/ g T OC 0.07 0.06 0.11 0.07 0.29 0.09 0.16 0.16 0.10 0.14 0.22 0.17
n C34:1 mg/ g T OC 0.01 0.01 0.04 0.01 0.12 0.03 0.06 0.07 0.03 0.05 0.08 0.09
n C34 mg/ g T OC 0.06 0.05 0.10 0.04 0.24 0.10 0.15 0.13 0.09 0.11 0.14 0.17
n C35:1 mg/ g T OC 0.02 0.01 0.04 0.00 0.12 0.03 0.06 0.07 0.03 0.05 0.09 0.09
n C35 mg/ g T OC 0.03 0.03 0.07 0.00 0.19 0.05 0.10 0.11 0.06 0.09 0.17 0.14
n C36:1 mg/ g T OC 0.01 0.00 0.03 0.00 0.14 0.00 0.10 0.04 0.02 0.02 0.05 0.08
n C36 mg/ g T OC 0.02 0.02 0.06 0.00 0.30 0.00 0.08 0.07 0.06 0.03 0.10 0.13
n C37:1 mg/ g T OC 0.00 0.00 0.01 0.00 0.10 0.00 0.02 0.07 0.03 0.02 0.04 0.10
n C37 mg/ g T OC 0.01 0.00 0.03 0.00 0.17 0.00 0.05 0.09 0.05 0.05 0.08 0.11
n C38:1 mg/ g T OC 0.00 0.00 0.02 0.00 0.11 0.00 0.02 0.04 0.01 0.02 0.03 0.06
n C38 mg/ g T OC 0.01 0.00 0.01 0.00 0.17 0.00 0.05 0.06 0.03 0.02 0.09 0.06
n C39:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.06 0.00 0.00 0.03 0.01 0.03 0.03 0.03
n C39 mg/ g T OC 0.01 0.00 0.00 0.00 0.17 0.00 0.00 0.05 0.02 0.03 0.06 0.04
Konz. C1-5 mg/ g T OC 61.1 80.2 71.5 58.6 41.0 57.2 58.2 94.1 126.7 56.3 59.6 85.4
Konz. M ethane mg/ g T OC 9.4 11.0 8.0 10.3 3.9 9.6 8.6 10.7 13.5 9.1 6.3 10.1
Konz. C2-5 mg/ g T OC 51.7 69.2 63.5 48.3 37.1 47.6 49.6 83.4 113.2 47.1 53.3 75.4
Konz. C6-14 mg/ g T OC 143.7 170.2 179.0 128.5 121.8 135.4 151.4 200.3 237.8 126.1 163.4 184.0
C6-14 Resolved mg/ g T OC 101.0 136.0 135.9 81.8 90.1 87.6 109.1 162.6 199.2 81.3 122.4 144.8
C6-14 Hump mg/ g T OC 42.7 34.2 43.1 46.8 31.8 47.8 42.2 37.6 38.6 44.8 41.0 39.2
Konz. C15+ mg/ g T OC 195.8 205.8 303.3 280.5 283.5 301.8 278.3 369.2 294.1 283.8 349.6 396.8
C15+ Resolved mg/ g T OC 41.5 65.8 80.8 25.5 81.9 32.0 50.9 96.7 96.9 27.6 83.5 99.0
C15+ Hump mg/ g T OC 154.3 140.0 222.5 255.0 201.6 269.8 227.4 272.5 197.2 256.3 266.1 297.7
Konz.Gesamt mg/ g T OC 400.6 456.2 553.8 467.6 446.3 494.4 487.9 663.6 658.6 466.2 572.6 666.2
C6+ mg/ g T OC 339.5 376.0 482.3 409.0 405.3 437.2 429.7 569.5 531.9 410.0 512.9 580.8
C6+ Resolved mg/ g T OC 142.5 201.8 216.7 107.2 172.0 119.6 160.0 259.4 296.1 108.8 205.8 243.8
C6+ Hump mg/ g T OC 197.0 174.2 265.6 301.7 233.3 317.6 269.6 310.1 235.8 301.1 307.1 336.9
C2+ mg/ g T OC 391.2 445.2 545.8 457.3 442.4 484.8 479.3 652.9 645.0 457.1 566.2 656.2
n -C6-14 mg/ g T OC 32.0 64.4 69.3 24.9 47.1 28.8 44.5 84.1 101.8 23.5 59.6 78.0
n -C15+ mg/ g T OC 24.0 41.7 55.2 13.7 57.2 17.7 32.2 64.2 65.7 16.5 56.5 72.2
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
98
Table A 4 continued
GFZ no . G 0 1 0 2 7 6 G 0 1 0 2 7 7 G 0 1 0 2 8 1 G 0 1 0 2 8 3 G 0 1 0 2 9 9 G 0 1 0 3 0 0 G 0 1 0 3 0 2 G 0 1 0 3 0 5 G 0 1 0 3 1 6 G 0 1 0 3 4 6 G 0 1 0 3 4 9 G 0 1 0 3 5 1
TOC 4.27 7.25 8.99 9.15 3.79 7.29 4.68 11.8 13.5 5.72 5.32 17.5
S1 0.21 0.2 0.3 0.55 3.53 1.01 0.43 0.93 1.17 0.51 0.21 0.82
S2 23.21 53.68 64.74 58.27 30.33 53.44 27.89 91.48 102.9 33.51 40.01 116.19
S3 1.45 0.95 0.64 2.76 0.89 2.79 1.79 1.47 1.68 1.14 0.62 0.54
HI 544 740 720 637 800 733 596 775 762 586 752 664
OI 34 13 7 30 23 38 38 12 12 20 12 3
Tmax 429 439 443 429 438 432 433 446 449 423 442 452
PI 0.01 0.00 0.00 0.01 0.10 0.02 0.02 0.01 0.01 0.01 0.01 0.01
S1+S2 23.42 53.88 65.04 58.82 33.86 54.45 28.32 92.41 104.07 34.02 40.22 117.01
Konz.Gesamt mg/ g r ock 17.11 33.08 49.79 42.78 16.92 36.04 22.83 78.31 88.90 26.67 30.46 116.59
RE/ Konz. gesamt 1.36 1.62 1.30 1.36 1.79 1.48 1.22 1.17 1.16 1.26 1.31 1.00
Aromates mg/ g T OC 10.96 13.65 8.70 8.39 5.79 8.21 10.35 13.30 15.97 9.09 7.22 7.95
Phenols mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thiophenes mg/ g T OC 2.71 2.50 2.15 2.36 1.72 2.49 2.58 2.36 3.75 2.90 2.16 1.99
branched + cyclo Alkanes mg/ g T OC 2.47 2.52 2.67 2.21 1.56 2.23 2.50 2.75 4.15 2.49 2.12 2.85
Aromaticity Aromates / n -C6+ 0.20 0.13 0.07 0.22 0.06 0.18 0.13 0.09 0.10 0.23 0.06 0.05
Aromaticity Aromates / n -C6-14 0.34 0.21 0.13 0.34 0.12 0.28 0.23 0.16 0.16 0.39 0.12 0.10
Aromaticity Aromates/n -C15+ 0.46 0.33 0.16 0.61 0.10 0.46 0.32 0.21 0.24 0.55 0.13 0.11
Aromaticity (Aromates+ Phenols)
/ n -C6+0.20 0.13 0.07 0.22 0.06 0.18 0.13 0.09 0.10 0.23 0.06 0.05
Phenols/n -C6+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Phenols /n -C6-14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Phenols / n -C15+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Phenols / n -C9-11 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
m,p -Cresol / m,p -Xylol 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
m,p-Cresol / n -C10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thiophenes / n -C6-14 0.08 0.04 0.03 0.09 0.04 0.09 0.06 0.03 0.04 0.12 0.04 0.03
branched+cyclo Alkanes /
n -C6-140.08 0.04 0.04 0.09 0.03 0.08 0.06 0.03 0.04 0.11 0.04 0.04
GOR 0.18 0.21 0.15 0.14 0.10 0.13 0.14 0.17 0.24 0.14 0.12 0.15
Gas Wetness (C2-5)/ (C1-5) 0.85 0.86 0.89 0.82 0.90 0.83 0.85 0.89 0.89 0.84 0.89 0.88
GOR resolved 0.43 0.40 0.33 0.55 0.24 0.48 0.36 0.36 0.43 0.52 0.29 0.35
mono-Aromatics mg/ g T OC 8.81 11.31 7.06 6.75 4.63 6.70 8.55 11.21 13.48 7.47 5.81 6.77
di-aromatics mg/ g T OC 2.15 2.34 1.64 1.63 1.15 1.51 1.81 2.10 2.49 1.62 1.40 1.19
di/mono-Aromatics 0.24 0.21 0.23 0.24 0.25 0.23 0.21 0.19 0.18 0.22 0.24 0.18
Phenols/Aromates 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thiophenes/M ono-Aromates 0.31 0.22 0.31 0.35 0.37 0.37 0.30 0.21 0.28 0.39 0.37 0.29
Phenols/ Konzgesamt [%] % 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n -C6-14 mg/ g T OC 15.17 27.01 28.35 10.57 18.83 12.84 19.51 30.90 35.54 10.41 25.04 29.58
n -C15+ mg/ g T OC 14.13 22.86 29.06 7.19 29.25 9.34 16.87 32.67 34.04 9.06 29.84 36.98
n -C6:1-14:1 mg/ g T OC 16.81 37.35 40.96 14.31 28.30 15.99 24.98 53.16 66.21 13.05 34.56 48.47
n -C15:1+ mg/ g T OC 9.90 18.87 26.11 6.56 27.96 8.37 15.35 31.52 31.61 7.45 26.61 35.20
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
99
Table A 4 continued
Format ion/ B asin
GFZ no . G 0 1 0 4 4 9 G 0 1 0 4 5 0 G 0 1 0 4 5 3 G 0 1 0 4 5 4 G 0 1 0 4 7 3 G 0 1 0 4 7 4 G 0 1 0 4 7 8 G 0 1 0 4 9 2 G 0 1 0 5 2 1 G 0 1 0 5 2 4 G 0 1 0 5 2 5 G 0 1 0 5 5 0 G 0 1 0 5 5 5 G 0 1 0 5 5 7
n C1 mg/ g T OC 3.42 5.66 3.34 8.05 8.87 0.67 2.93 3.69 0.94 0.70 0.60 0.11 0.41 0.42
n C2:1 mg/ g T OC 0.92 1.25 0.72 0.82 1.06 0.12 0.79 0.33 0.10 0.07 0.10 0.13 0.06 0.09
n C2 mg/ g T OC 1.45 2.24 1.58 2.39 2.55 0.19 0.46 0.99 0.19 0.11 0.04 0.06 0.04 0.02
n C3 mg/ g T OC 2.30 2.92 2.38 2.52 1.91 0.21 0.85 0.61 0.40 0.16 0.10 0.03 0.13 0.14
I-C4 mg/ g T OC 0.07 0.08 0.10 0.09 0.08 0.01 0.03 0.02 0.01 0.00 0.00 0.00 0.00 0.00
n C4:1 mg/ g T OC 1.03 1.06 1.30 1.09 0.41 0.04 0.10 0.10 0.12 0.06 0.02 0.01 0.03 0.03
n C4 mg/ g T OC 0.57 0.74 0.63 0.60 0.38 0.03 0.18 0.10 0.08 0.03 0.02 0.01 0.02 0.03
I-C5 mg/ g T OC 0.11 0.15 0.10 0.19 0.08 0.01 0.07 0.03 0.03 0.02 0.00 0.00 0.02 0.03
n C5:1 mg/ g T OC 0.35 0.50 0.39 0.51 0.08 0.01 0.04 0.02 0.04 0.02 0.01 0.00 0.03 0.03
n C5 mg/ g T OC 0.31 0.55 0.30 0.40 0.12 0.01 0.04 0.03 0.01 0.00 0.00 0.01 0.02 0.01
(2,2 DM Pentan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
cy-C5 mg/ g T OC 0.02 0.03 0.01 0.02 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00
2-M -C5 mg/ g T OC 0.04 0.05 0.12 0.07 0.03 0.00 0.02 0.01 0.01 0.00 0.00 0.00 0.00 0.00
2-Butanone mg/ g T OC 0.01 0.02 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3-M -C5 mg/ g T OC 0.02 0.03 0.04 0.04 0.02 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C6:1 mg/ g T OC 0.33 0.48 0.44 0.61 0.05 0.01 0.02 0.02 0.01 0.01 0.00 0.00 0.00 0.00
n C6 mg/ g T OC 0.25 0.49 0.26 0.35 0.07 0.01 0.02 0.02 0.01 0.00 0.00 0.00 0.00 0.00
M -Cy-C5 mg/ g T OC 0.03 0.05 0.03 0.04 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
(2,4 DM Pentan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
(2,2,3 DM Butan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzol mg/ g T OC 0.40 0.42 0.52 0.47 0.17 0.04 0.20 0.09 0.14 0.06 0.04 0.06 0.04 0.06
Thiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
cy C6 mg/ g T OC 0.03 0.04 0.03 0.04 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2 M C6 mg/ g T OC 0.03 0.02 0.07 0.05 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,3 DM Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,1 DM Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3 M C6 mg/ g T OC 0.02 0.04 0.03 0.04 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1, cis, 3 DM Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1, trans, 3 DM cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,2,4 Tri M Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C7:1 mg/ g T OC 0.20 0.34 0.24 0.38 0.02 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00
n C7 mg/ g T OC 0.24 0.49 0.25 0.34 0.05 0.01 0.01 0.02 0.00 0.00 0.00 0.00 0.00 0.00
M -Cy-C6 mg/ g T OC 0.01 0.02 0.03 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,1,3 Tri M cy Pentan
+ 2,2 DM Hexanmg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
E Cy Pentan mg/ g T OC 0.01 0.02 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,5 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,4 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,trans, 2, cis, 4 Tri M Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3,3 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1, trans, 2, cis, 3 Tri M Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,3,4 Tri M Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Toluol mg/ g T OC 0.51 0.55 0.61 0.69 0.43 0.06 0.20 0.14 0.09 0.05 0.03 0.02 0.03 0.06
2-M -Thiophen mg/ g T OC 0.05 0.05 0.05 0.07 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3-M -Thiophen mg/ g T OC 0.04 0.07 0.08 0.10 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C8:1 mg/ g T OC 0.13 0.26 0.14 0.24 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C8 mg/ g T OC 0.26 0.49 0.34 0.42 0.04 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00
E Benzol mg/ g T OC 0.11 0.12 0.13 0.14 0.04 0.00 0.02 0.02 0.01 0.00 0.00 0.00 0.01 0.01
E Thiophen mg/ g T OC 0.01 0.00 0.05 0.05 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,5 DM Thiophen mg/ g T OC 0.01 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
meta, para Xylol mg/ g T OC 0.32 0.33 0.34 0.46 0.15 0.01 0.06 0.06 0.03 0.01 0.01 0.00 0.01 0.01
2,4 DM Thiophen mg/ g T OC 0.03 0.04 0.03 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,3 DM Thiophen mg/ g T OC 0.02 0.03 0.05 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Styrol mg/ g T OC 0.05 0.03 0.06 0.06 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
ortho Xylol mg/ g T OC 0.15 0.13 0.20 0.20 0.06 0.01 0.03 0.02 0.02 0.01 0.01 0.00 0.01 0.01
n C9:1 mg/ g T OC 0.10 0.20 0.11 0.23 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C9 mg/ g T OC 0.17 0.35 0.17 0.23 0.02 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00
2-Propylthiophene mg/ g T OC 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
PropylBenzol mg/ g T OC 0.05 0.05 0.06 0.06 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2E5M Thiophen mg/ g T OC 0.03 0.02 0.04 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM B mg/ g T OC 0.15 0.14 0.20 0.19 0.04 0.01 0.05 0.02 0.03 0.01 0.00 0.01 0.02 0.03
EX-B - Wealden Shale - Lower Saxony Basin
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
100
Table A 4 continued
GFZ no . G 0 1 0 4 4 9 G 0 1 0 4 5 0 G 0 1 0 4 5 3 G 0 1 0 4 5 4 G 0 1 0 4 7 3 G 0 1 0 4 7 4 G 0 1 0 4 7 8 G 0 1 0 4 9 2 G 0 1 0 5 2 1 G 0 1 0 5 2 4 G 0 1 0 5 2 5 G 0 1 0 5 5 0 G 0 1 0 5 5 5 G 0 1 0 5 5 7
1,3,5TM Benzol mg/ g T OC 0.05 0.05 0.06 0.06 0.02 0.00 0.03 0.02 0.01 0.01 0.00 0.00 0.00 0.00
Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1E-2-M Benzol mg/ g T OC 0.07 0.07 0.09 0.10 0.01 0.00 0.01 0.01 0.02 0.00 0.00 0.00 0.00 0.00
2,3,5-TriM Thiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,2,4-TriM Benzol mg/ g T OC 0.12 0.12 0.17 0.17 0.04 0.00 0.03 0.01 0.01 0.00 0.00 0.00 0.00 0.00
n C10:1 mg/ g T OC 0.07 0.15 0.06 0.14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C10 mg/ g T OC 0.13 0.32 0.14 0.19 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,2,3TM Benzol mg/ g T OC 0.03 0.02 0.04 0.04 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
ortho Chresol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M eta, Para Chresol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C11:1 mg/ g T OC 0.11 0.20 0.13 0.22 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C11 mg/ g T OC 0.12 0.36 0.14 0.18 0.02 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00
E Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
E Phenol mg/ g T OC 0.03 0.05 0.06 0.06 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Naphtalin mg/ g T OC 0.09 0.08 0.09 0.14 0.06 0.01 0.04 0.02 0.02 0.01 0.01 0.00 0.00 0.01
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzothiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C12:1 mg/ g T OC 0.09 0.20 0.10 0.21 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C12 mg/ g T OC 0.12 0.59 0.12 0.17 0.01 0.00 0.04 0.00 0.01 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -E-Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -E-Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -Benzothiophen (1) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2 M Naphtalin mg/ g T OC 0.08 0.11 0.08 0.11 0.03 0.00 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n C13:1 mg/ g T OC 0.05 0.13 0.04 0.13 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1 M Naphtalin mg/ g T OC 0.04 0.08 0.05 0.07 0.02 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n C13 mg/ g T OC 0.14 0.99 0.14 0.21 0.01 0.00 0.10 0.00 0.01 0.00 0.00 0.00 0.00 0.00
n C14:1 mg/ g T OC 0.04 0.10 0.04 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C14 mg/ g T OC 0.13 1.43 0.11 0.19 0.00 0.00 0.06 0.00 0.01 0.00 0.00 0.00 0.00 0.00
DM Naphtalin mg/ g T OC 0.08 0.22 0.10 0.11 0.02 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00
?2 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?3 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C15:1 u. ?4 mg/ g T OC 0.03 0.09 0.03 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?5 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C15 mg/ g T OC 0.13 1.91 0.10 0.18 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?6 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Naphtalin mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Naphtalin mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Naphtalin mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C16:1 mg/ g T OC 0.02 0.07 0.02 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C16 mg/ g T OC 0.12 2.02 0.08 0.15 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Isopropyl-DM -Naphtaline mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C17:1 mg/ g T OC 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C17 mg/ g T OC 0.10 2.02 0.06 0.13 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Pristan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Te-M -Naphtaline mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Prist-1-en mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C18:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C18 mg/ g T OC 0.07 1.98 0.05 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Phytan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C19:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C19 mg/ g T OC 0.04 1.94 0.04 0.08 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
? M -(Phenantrene/Anthracene) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?7 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
101
Table A 4 continued
GFZ no . G 0 1 0 4 4 9 G 0 1 0 4 5 0 G 0 1 0 4 5 3 G 0 1 0 4 5 4 G 0 1 0 4 7 3 G 0 1 0 4 7 4 G 0 1 0 4 7 8 G 0 1 0 4 9 2 G 0 1 0 5 2 1 G 0 1 0 5 2 4 G 0 1 0 5 2 5 G 0 1 0 5 5 0 G 0 1 0 5 5 5 G 0 1 0 5 5 7
?8 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C20:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C20 mg/ g T OC 0.04 1.75 0.04 0.08 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?9 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?10 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C21:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C21 mg/ g T OC 0.06 1.51 0.06 0.07 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C22:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C22 mg/ g T OC 0.13 1.24 0.12 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Isopropyl-M -Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?11 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C23:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C23 mg/ g T OC 0.21 1.02 0.20 0.07 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C24:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C24 mg/ g T OC 0.22 0.80 0.21 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C25:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C25 mg/ g T OC 0.18 0.62 0.18 0.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C26:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C26 mg/ g T OC 0.11 0.44 0.11 0.23 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C27:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C27 mg/ g T OC 0.06 0.29 0.04 0.23 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C28:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C28 mg/ g T OC 0.03 0.16 0.01 0.14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C29:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C29 mg/ g T OC 0.01 0.07 0.00 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C30:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C30 mg/ g T OC 0.00 0.02 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C31:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C31 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C32:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C32 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C33:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C33 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C34:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C34 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C35:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C35 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C36:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C36 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C37:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C37 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C38:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C38 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C39:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C39 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Konz. C1-5mg/ g T OC 13.15 18.16 15.20 20.78 17.16 1.66 6.64 6.64 2.63 1.51 1.02 0.47 1.03 1.07
Konz. M ethane mg/ g T OC 3.42 5.66 3.34 8.05 8.87 0.67 2.93 3.69 0.94 0.70 0.60 0.11 0.41 0.42
Konz. C2-5mg/ g T OC 9.73 12.50 11.86 12.73 8.29 0.99 3.71 2.95 1.69 0.81 0.43 0.36 0.61 0.65
Konz. C6-14 mg/ g T OC 16.95 26.44 21.41 25.13 2.95 0.59 2.02 1.02 0.97 0.39 0.24 0.32 0.25 0.39
C6-14 Resolved mg/ g T OC 13.51 21.32 18.45 22.11 2.88 0.45 2.01 0.99 1.03 0.44 0.25 0.18 0.29 0.40
C6-14 Hump mg/ g T OC 3.44 5.12 2.96 3.03 0.07 0.15 0.02 0.03 0.00 0.00 0.00 0.13 0.00 0.00
Konz. C15+ mg/ g T OC 11.30 48.87 8.66 13.77 1.43 1.55 1.21 0.25 0.88 2.31 0.31 1.77 1.11 1.24
C15+ Resolved mg/ g T OC 3.47 28.71 3.35 5.14 0.12 0.01 0.07 0.05 0.04 0.04 0.01 0.00 0.00 0.00
C15+ Hump mg/ g T OC 7.83 20.16 5.31 8.64 1.31 1.54 1.14 0.20 0.83 2.27 0.29 1.77 1.11 1.24
Konz.Gesamt mg/ g T OC 41.39 93.47 45.27 59.69 21.53 3.81 9.87 7.91 4.48 4.21 1.56 2.56 2.38 2.71
C6+ mg/ g T OC 28.25 75.31 30.08 38.91 4.38 2.14 3.24 1.27 1.85 2.70 0.54 2.09 1.35 1.63
C6+ Resolved mg/ g T OC 16.97 50.03 21.81 27.24 2.99 0.46 2.08 1.04 1.07 0.47 0.27 0.18 0.29 0.40
C6+ Hump mg/ g T OC 11.27 25.28 8.27 11.66 1.38 1.69 1.15 0.24 0.78 2.22 0.28 1.91 1.07 1.23
C2+mg/ g T OC 37.97 87.81 41.94 51.64 12.66 3.13 6.94 4.23 3.54 3.51 0.97 2.45 1.97 2.29
n -C6-14mg/ g T OC 2.68 7.58 2.99 4.55 0.33 0.04 0.33 0.10 0.08 0.03 0.02 0.00 0.00 0.00
n -C15+mg/ g T OC 1.56 17.99 1.35 1.94 0.01 0.00 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
102
Table A 4 continued
GFZ no . G 0 1 0 4 4 9 G 0 1 0 4 5 0 G 0 1 0 4 5 3 G 0 1 0 4 5 4 G 0 1 0 4 7 3 G 0 1 0 4 7 4 G 0 1 0 4 7 8 G 0 1 0 4 9 2 G 0 1 0 5 2 1 G 0 1 0 5 2 4 G 0 1 0 5 2 5 G 0 1 0 5 5 0 G 0 1 0 5 5 5 G 0 1 0 5 5 7
TOC 2.9 7.12 2.13 1.55 2.61 5.82 2.36 7.53 2.49 7.85 8.94 4.32 2.76 3.01
S1 1.02 4.27 1.14 0.57 0.43 0.17 0.3 0.38 0.17 0.11 0.22 0.16 0.05 0.08
S2 2.23 5.94 2.3 2.01 1.24 0.66 0.82 1.37 0.65 0.57 0.73 0.68 0.42 0.48
S3 0.2 0.95 0.26 1.88 0.65 1.65 0.8 0.64 0.4 0.7 0.32 0.95 0.66 0.81
HI 77 83 108 130 48 11 35 18 26 7 8 16 15 16
OI 7 13 12 121 25 28 34 8 16 9 4 22 24 27
Tmax 320 472 345 395 525 491 488 533 291 600 600 255 314 600
PI 0.31 0.42 0.33 0.22 0.26 0.20 0.27 0.22 0.21 0.16 0.23 0.19 0.11 0.14
S1+S2 3.25 10.21 3.44 2.58 1.67 0.83 1.12 1.75 0.82 0.68 0.95 0.84 0.47 0.56
Konz.Gesamt mg/ g r ock 1.20 6.66 0.96 0.93 0.56 0.22 0.23 0.60 0.11 0.33 0.14 0.11 0.07 0.08
RE/ Konz. gesamt 1.86 0.89 2.39 2.17 2.21 2.98 3.52 2.30 5.83 1.73 5.22 6.14 6.39 5.89
Aromates mg/ g T OC 2.24 2.50 2.73 3.01 1.13 0.16 0.71 0.44 0.39 0.18 0.11 0.10 0.11 0.19
Phenols mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thiophenes mg/ g T OC 0.21 0.21 0.32 0.38 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
branched + cyclo Alkanes mg/ g T OC 0.22 0.29 0.37 0.32 0.10 0.01 0.05 0.03 0.02 0.01 0.01 0.00 0.00 0.00
Aromaticity Aromates / n -C6+ 0.53 0.10 0.63 0.46 3.31 3.57 2.04 4.19 4.56 4.80 4.97 - - -
Aromaticity Aromates / n -C6-14 0.84 0.33 0.91 0.66 3.39 3.68 2.16 4.49 4.84 5.17 5.30 - - -
Aromaticity Aromates/n -C15+ 1.44 0.14 2.01 1.55 131.15 122.41 37.01 63.57 78.16 66.13 79.05 - - -
Aromaticity (Aromates+ Phenols) /
n -C6+0.53 0.10 0.63 0.46 3.31 3.57 2.04 4.19 4.56 4.80 4.97 - - -
Phenols/n -C6+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 - - -
Phenols /n -C6-14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 - - -
Phenols / n -C15+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 - - -
Phenols / n -C9-11 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 - - -
m,p -Cresol / m,p -Xylol 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 - 0.00 0.00
m,p-Cresol / n -C10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 - - -
Thiophenes / n -C6-14 0.08 0.03 0.11 0.08 0.18 0.00 0.00 0.00 0.00 0.12 0.00 - - -
branched+cyclo Alkanes /
n -C6-140.08 0.04 0.12 0.07 0.31 0.33 0.16 0.29 0.26 0.20 0.29 - - -
GOR 0.47 0.24 0.51 0.53 3.92 0.77 2.05 5.21 1.42 0.56 1.88 0.23 0.76 0.66
Gas Wetness (C2-5)/ (C1-5) 0.74 0.69 0.78 0.61 0.48 0.59 0.56 0.44 0.64 0.54 0.42 0.76 0.60 0.61
GOR resolved 0.77 0.36 0.70 0.76 5.73 3.63 3.19 6.40 2.45 3.18 3.85 2.57 3.57 2.69
mono-Aromatics mg/ g T OC 1.95 2.01 2.42 2.58 1.00 0.15 0.64 0.39 0.36 0.16 0.10 0.09 0.10 0.18
di-aromatics mg/ g T OC 0.29 0.49 0.31 0.43 0.13 0.01 0.07 0.05 0.03 0.02 0.01 0.00 0.00 0.01
di/mono-Aromatics 0.15 0.24 0.13 0.17 0.13 0.08 0.12 0.13 0.08 0.13 0.12 0.02 0.03 0.03
Phenols/Aromates 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thiophenes/M ono-Aromates 0.11 0.10 0.13 0.15 0.06 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00
Phenols/ Konzgesamt [%] % 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n -C6-14mg/ g T OC 1.56 5.51 1.67 2.29 0.23 0.03 0.27 0.07 0.05 0.02 0.01 0.00 0.00 0.00
n -C15+mg/ g T OC 1.52 17.79 1.30 1.84 0.01 0.00 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n -C6:1-14:1mg/ g T OC 1.12 2.07 1.32 2.26 0.11 0.02 0.06 0.03 0.03 0.02 0.01 0.00 0.00 0.00
n -C15:1+mg/ g T OC 0.05 0.19 0.05 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
103
Table A 4 continued
Format ion/ B asin
GFZ no . G 0 1 0 3 6 2 G 0 1 0 3 6 3 G 0 1 0 3 6 6 G 0 1 0 3 6 9 G 0 1 0 3 8 0 G 0 1 0 3 8 3 G 0 1 0 3 8 5 G 0 1 0 3 8 9 G 0 1 0 3 9 6 G 0 1 0 3 9 7 G 0 1 0 3 9 9 G 0 1 0 4 1 6 G 0 1 0 4 1 7 G 0 1 0 4 1 8
n C1 mg/ g T OC 5.00 6.88 4.22 7.48 5.01 6.58 9.54 5.58 2.83 3.54 14.10 1.90 8.16 7.97
n C2:1 mg/ g T OC 1.33 1.64 1.31 1.85 1.11 1.41 1.47 1.28 0.60 0.66 1.08 0.16 1.18 0.46
n C2 mg/ g T OC 2.67 3.96 2.01 3.47 2.75 2.44 3.88 2.31 1.03 1.20 2.79 0.51 2.67 1.35
n C3 mg/ g T OC 4.36 5.73 3.62 4.53 4.64 3.16 6.09 3.17 1.18 1.29 1.45 0.28 2.29 0.64
I-C4 mg/ g T OC 0.13 0.21 0.11 0.15 0.23 0.08 0.45 0.09 0.04 0.05 0.08 0.01 0.09 0.04
n C4:1 mg/ g T OC 2.12 2.27 1.58 1.95 3.16 1.28 3.62 1.13 0.29 0.34 0.24 0.07 0.56 0.12
n C4 mg/ g T OC 1.13 1.98 1.12 1.61 1.11 0.88 1.49 1.02 0.25 0.31 0.21 0.05 0.43 0.07
I-C5 mg/ g T OC 0.13 0.21 0.14 0.18 0.25 0.13 0.43 0.10 0.04 0.05 0.03 0.01 0.06 0.01
n C5:1 mg/ g T OC 0.64 1.16 0.76 1.05 0.90 0.82 0.84 0.51 0.07 0.10 0.02 0.01 0.16 0.01
n C5 mg/ g T OC 0.65 1.28 0.76 1.08 0.64 0.70 0.93 0.71 0.11 0.14 0.03 0.01 0.18 0.02
(2,2 DM Pentan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
cy-C5 mg/ g T OC 0.03 0.08 0.04 0.08 0.03 0.04 0.05 0.03 0.00 0.01 0.01 0.00 0.01 0.00
2-M -C5 mg/ g T OC 0.10 0.17 0.07 0.14 0.30 0.11 0.35 0.08 0.02 0.02 0.01 0.00 0.04 0.00
2-Butanone mg/ g T OC 0.01 0.02 0.01 0.02 0.02 0.02 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00
3-M -C5 mg/ g T OC 0.04 0.08 0.04 0.05 0.08 0.05 0.15 0.04 0.01 0.01 0.01 0.00 0.02 0.00
n C6:1 mg/ g T OC 0.81 1.29 0.79 1.11 1.28 1.05 0.86 0.56 0.06 0.10 0.01 0.01 0.13 0.00
n C6 mg/ g T OC 0.65 1.17 0.68 0.92 0.68 0.66 0.89 0.61 0.08 0.11 0.01 0.01 0.11 0.00
M -Cy-C5 mg/ g T OC 0.07 0.13 0.08 0.13 0.08 0.06 0.12 0.05 0.01 0.01 0.01 0.00 0.02 0.00
(2,4 DM Pentan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
(2,2,3 DM Butan) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzol mg/ g T OC 0.94 0.70 0.35 0.43 0.78 0.56 0.50 0.64 0.35 0.28 0.32 0.09 0.38 0.20
Thiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
cy C6 mg/ g T OC 0.06 0.11 0.06 0.10 0.09 0.05 0.10 0.03 0.01 0.01 0.01 0.00 0.01 0.00
2 M C6 mg/ g T OC 0.11 0.05 0.04 0.02 0.22 0.06 0.31 0.04 0.01 0.00 0.00 0.00 0.01 0.00
2,3 DM Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,1 DM Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3 M C6 mg/ g T OC 0.06 0.09 0.04 0.07 0.10 0.05 0.18 0.04 0.01 0.01 0.00 0.00 0.02 0.00
1, cis, 3 DM Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1, trans, 3 DM cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,2,4 Tri M Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C7:1 mg/ g T OC 0.50 0.93 0.54 0.82 0.67 0.72 0.62 0.37 0.03 0.06 0.00 0.00 0.08 0.00
n C7 mg/ g T OC 0.76 1.24 0.68 0.88 0.71 0.66 0.89 0.59 0.06 0.08 0.01 0.00 0.10 0.00
M -Cy-C6 mg/ g T OC 0.08 0.05 0.09 0.05 0.08 0.06 0.07 0.05 0.01 0.00 0.01 0.00 0.01 0.00
1,1,3 Tri M cy Pentan
+ 2,2 DM Hexanmg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
E Cy Pentan mg/ g T OC 0.03 0.06 0.04 0.07 0.03 0.03 0.04 0.02 0.00 0.00 0.00 0.00 0.01 0.00
2,5 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 1.07 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,4 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,trans, 2, cis, 4 Tri M Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3,3 DM Hexan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1, trans, 2, cis, 3 Tri M Cy Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,3,4 Tri M Pentan mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Toluol mg/ g T OC 1.11 0.95 0.68 0.63 1.73 0.68 0.36 0.78 0.37 0.28 0.59 0.08 0.47 0.31
2-M -Thiophen mg/ g T OC 0.07 0.00 0.08 0.07 0.32 0.05 0.22 0.03 0.01 0.03 0.00 0.00 0.00 0.00
3-M -Thiophen mg/ g T OC 0.17 0.00 0.13 0.03 0.19 0.14 0.29 0.05 0.01 0.02 0.00 0.00 0.00 0.00
n C8:1 mg/ g T OC 0.29 0.71 0.40 0.65 0.38 0.56 1.21 0.26 0.01 0.04 0.00 0.00 0.05 0.00
n C8 mg/ g T OC 0.75 1.18 0.66 0.77 1.07 0.65 0.36 0.51 0.04 0.06 0.00 0.00 0.06 0.00
E Benzol mg/ g T OC 0.29 0.30 0.19 0.19 0.36 0.17 0.22 0.20 0.03 0.04 0.04 0.01 0.05 0.02
E Thiophen mg/ g T OC 0.00 0.06 0.00 0.03 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,5 DM Thiophen mg/ g T OC 0.00 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
meta, para Xylol mg/ g T OC 0.55 0.67 0.42 0.45 0.85 0.39 0.96 0.30 0.06 0.09 0.28 0.04 0.18 0.12
2,4 DM Thiophen mg/ g T OC 0.08 0.11 0.05 0.05 0.23 0.06 0.15 0.03 0.00 0.00 0.00 0.00 0.00 0.00
2,3 DM Thiophen mg/ g T OC 0.05 0.10 0.04 0.06 0.17 0.05 0.25 0.04 0.00 0.01 0.00 0.00 0.00 0.00
Styrol mg/ g T OC 0.08 0.08 0.07 0.07 0.10 0.10 0.07 0.13 0.00 0.02 0.00 0.00 0.00 0.00
ortho Xylol mg/ g T OC 0.34 0.32 0.24 0.19 0.49 0.21 0.49 0.20 0.05 0.05 0.07 0.01 0.08 0.03
n C9:1 mg/ g T OC 0.23 0.53 0.33 0.54 0.31 0.45 0.24 0.20 0.01 0.02 0.00 0.00 0.03 0.00
n C9 mg/ g T OC 0.44 0.85 0.50 0.63 0.44 0.44 0.58 0.39 0.03 0.04 0.00 0.00 0.03 0.00
2-Propylthiophene mg/ g T OC 0.14 0.00 0.10 0.00 0.00 0.08 0.00 0.07 0.00 0.00 0.00 0.00 0.00 0.00
PropylBenzol mg/ g T OC 0.09 0.14 0.07 0.07 0.19 0.08 0.19 0.02 0.01 0.01 0.01 0.00 0.01 0.00
2E5M Thiophen mg/ g T OC 0.06 0.00 0.05 0.00 0.00 0.05 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00
TM B mg/ g T OC 0.36 0.34 0.21 0.21 0.55 0.20 0.61 0.14 0.01 0.02 0.04 0.01 0.04 0.01
EX-C - Wealden Shale - Lower Saxony Basin
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
104
Table A 4 continued
GFZ no . G 0 1 0 3 6 2 G 0 1 0 3 6 3 G 0 1 0 3 6 6 G 0 1 0 3 6 9 G 0 1 0 3 8 0 G 0 1 0 3 8 3 G 0 1 0 3 8 5 G 0 1 0 3 8 9 G 0 1 0 3 9 6 G 0 1 0 3 9 7 G 0 1 0 3 9 9 G 0 1 0 4 1 6 G 0 1 0 4 1 7 G 0 1 0 4 1 8
1,3,5TM Benzol mg/ g T OC 0.10 0.09 0.07 0.08 0.16 0.07 0.18 0.04 0.01 0.01 0.03 0.01 0.03 0.01
Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1E-2-M Benzol mg/ g T OC 0.21 0.18 0.12 0.08 0.32 0.11 0.29 0.11 0.02 0.02 0.01 0.00 0.02 0.01
2,3,5-TriM Thiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,2,4-TriM Benzol mg/ g T OC 0.31 0.26 0.17 0.16 0.52 0.17 0.58 0.10 0.03 0.02 0.04 0.01 0.05 0.01
n C10:1 mg/ g T OC 0.15 0.45 0.26 0.51 0.18 0.40 0.11 0.15 0.01 0.01 0.00 0.00 0.01 0.00
n C10 mg/ g T OC 0.42 0.82 0.47 0.62 0.44 0.43 0.55 0.35 0.02 0.03 0.00 0.00 0.02 0.00
1,2,3TM Benzol mg/ g T OC 0.07 0.18 0.04 0.09 0.22 0.04 0.17 0.03 0.01 0.01 0.01 0.00 0.01 0.00
ortho Chresol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M eta, Para Chresol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C11:1 mg/ g T OC 0.18 0.56 0.34 0.52 0.50 0.46 0.41 0.19 0.00 0.01 0.00 0.00 0.01 0.00
n C11 mg/ g T OC 0.39 0.76 0.44 0.64 0.42 0.41 0.53 0.34 0.02 0.02 0.02 0.00 0.02 0.00
E Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
E Phenol mg/ g T OC 0.12 0.13 0.07 0.06 0.18 0.07 0.17 0.03 0.00 0.00 0.01 0.00 0.01 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Naphtalin mg/ g T OC 0.24 0.20 0.10 0.10 0.17 0.13 0.20 0.13 0.04 0.04 0.15 0.02 0.06 0.07
DM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzothiophen mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C12:1 mg/ g T OC 0.11 0.56 0.32 0.51 0.41 0.48 0.26 0.17 0.00 0.01 0.00 0.00 0.00 0.00
n C12 mg/ g T OC 0.39 0.79 0.42 0.64 0.37 0.41 0.46 0.34 0.01 0.02 0.00 0.00 0.01 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -E-Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -E-Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenol mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
M -Benzothiophen (1) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2 M Naphtalin mg/ g T OC 0.23 0.25 0.16 0.16 0.31 0.12 0.32 0.09 0.00 0.01 0.10 0.01 0.03 0.04
n C13:1 mg/ g T OC 0.16 0.40 0.23 0.48 0.19 0.36 0.12 0.11 0.00 0.00 0.00 0.00 0.00 0.00
1 M Naphtalin mg/ g T OC 0.14 0.18 0.10 0.09 0.15 0.06 0.16 0.07 0.00 0.01 0.05 0.00 0.01 0.02
n C13 mg/ g T OC 0.47 0.92 0.50 0.65 0.42 0.51 0.52 0.33 0.01 0.01 0.00 0.00 0.01 0.00
n C14:1 mg/ g T OC 0.14 0.37 0.22 0.44 0.00 0.34 0.10 0.10 0.00 0.00 0.00 0.00 0.01 0.00
n C14 mg/ g T OC 0.43 0.89 0.47 0.63 0.44 0.50 0.46 0.31 0.02 0.01 0.00 0.00 0.01 0.00
DM Naphtalin mg/ g T OC 0.31 0.29 0.21 0.19 0.48 0.20 0.40 0.11 0.01 0.01 0.02 0.00 0.01 0.01
?2 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?3 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C15:1 u. ?4 mg/ g T OC 0.11 0.31 0.17 0.39 0.14 0.31 0.07 0.07 0.00 0.00 0.00 0.00 0.00 0.00
?5 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C15 mg/ g T OC 0.46 0.91 0.46 0.61 0.48 0.50 0.53 0.29 0.02 0.01 0.00 0.00 0.00 0.00
?6 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TM Naphtalin mg/ g T OC 0.09 0.00 0.06 0.00 0.00 0.07 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00
TM Naphtalin mg/ g T OC 0.06 0.00 0.05 0.00 0.00 0.03 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00
TM Naphtalin mg/ g T OC 0.05 0.00 0.03 0.00 0.00 0.04 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00
n C16:1 mg/ g T OC 0.07 0.30 0.13 0.38 0.17 0.26 0.15 0.06 0.00 0.00 0.00 0.00 0.00 0.00
n C16 mg/ g T OC 0.40 0.79 0.39 0.51 0.46 0.46 0.67 0.24 0.01 0.00 0.00 0.00 0.00 0.00
Isopropyl-DM -Naphtaline mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C17:1 mg/ g T OC 0.05 0.09 0.08 0.25 0.10 0.21 0.11 0.04 0.00 0.00 0.00 0.00 0.00 0.00
n C17 mg/ g T OC 0.35 0.62 0.33 0.35 0.65 0.40 1.16 0.19 0.00 0.00 0.00 0.00 0.00 0.00
Pristan mg/ g T OC 0.04 0.00 0.04 0.00 0.00 0.07 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00
Te-M -Naphtaline mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Prist-1-en mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C18:1 mg/ g T OC 0.25 0.00 0.04 0.18 0.00 0.12 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00
n C18 mg/ g T OC 0.02 0.58 0.22 0.30 0.77 0.25 1.53 0.14 0.00 0.00 0.00 0.00 0.00 0.00
Phytan mg/ g T OC 0.00 0.00 0.02 0.00 0.00 0.03 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n C19:1 mg/ g T OC 0.00 0.00 0.01 0.15 0.00 0.08 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n C19 mg/ g T OC 0.21 0.79 0.16 0.27 1.13 0.22 1.78 0.18 0.00 0.00 0.00 0.00 0.00 0.00
? M -(Phenantrene/Anthracene) mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?7 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
105
Table A 4 continued
GFZ no . G 0 1 0 3 6 2 G 0 1 0 3 6 3 G 0 1 0 3 6 6 G 0 1 0 3 6 9 G 0 1 0 3 8 0 G 0 1 0 3 8 3 G 0 1 0 3 8 5 G 0 1 0 3 8 9 G 0 1 0 3 9 6 G 0 1 0 3 9 7 G 0 1 0 3 9 9 G 0 1 0 4 1 6 G 0 1 0 4 1 7 G 0 1 0 4 1 8
?8 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C20:1 mg/ g T OC 0.00 0.00 0.03 0.14 0.00 0.07 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n C20 mg/ g T OC 0.20 1.02 0.15 0.26 1.49 0.22 1.89 0.28 0.00 0.00 0.00 0.00 0.00 0.00
?9 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
DM Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?10 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C21:1 mg/ g T OC 0.00 0.00 0.02 0.13 0.00 0.07 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00
n C21 mg/ g T OC 0.14 1.26 0.12 0.22 1.73 0.19 1.91 0.38 0.00 0.00 0.00 0.00 0.00 0.00
TM Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C22:1 mg/ g T OC 0.00 0.00 0.02 0.10 0.00 0.07 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00
n C22 mg/ g T OC 0.10 1.43 0.10 0.20 1.69 0.17 1.68 0.44 0.00 0.00 0.00 0.00 0.00 0.00
Isopropyl-M -Phenantrene mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
?11 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C23:1 mg/ g T OC 0.00 0.00 0.01 0.09 0.00 0.04 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n C23 mg/ g T OC 0.08 1.53 0.09 0.19 1.50 0.15 1.35 0.44 0.00 0.00 0.00 0.00 0.00 0.00
n C24:1 mg/ g T OC 0.00 0.00 0.00 0.09 0.00 0.02 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00
n C24 mg/ g T OC 0.07 1.49 0.08 0.18 1.17 0.15 0.97 0.35 0.00 0.00 0.00 0.00 0.00 0.00
n C25:1 mg/ g T OC 0.00 0.00 0.00 0.07 0.00 0.02 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n C25 mg/ g T OC 0.05 1.42 0.05 0.15 0.87 0.11 0.66 0.24 0.00 0.00 0.00 0.00 0.00 0.00
n C26:1 mg/ g T OC 0.00 0.00 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C26 mg/ g T OC 0.05 1.16 0.05 0.13 0.59 0.10 0.41 0.17 0.00 0.00 0.00 0.00 0.00 0.00
n C27:1 mg/ g T OC 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C27 mg/ g T OC 0.05 1.01 0.03 0.11 0.34 0.07 0.22 0.11 0.00 0.00 0.00 0.00 0.00 0.00
n C28:1 mg/ g T OC 0.00 0.00 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C28 mg/ g T OC 0.05 0.70 0.02 0.09 0.16 0.06 0.10 0.07 0.00 0.00 0.00 0.00 0.00 0.00
n C29:1 mg/ g T OC 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C29 mg/ g T OC 0.06 0.52 0.03 0.08 0.07 0.05 0.04 0.04 0.00 0.00 0.00 0.00 0.00 0.00
n C30:1 mg/ g T OC 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C30 mg/ g T OC 0.06 0.36 0.05 0.09 0.03 0.06 0.02 0.02 0.00 0.00 0.00 0.00 0.00 0.00
n C31:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C31 mg/ g T OC 0.04 0.25 0.06 0.10 0.01 0.06 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00
n C32:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C32 mg/ g T OC 0.03 0.16 0.06 0.11 0.00 0.07 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C33:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C33 mg/ g T OC 0.01 0.10 0.06 0.12 0.00 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C34:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C34 mg/ g T OC 0.01 0.05 0.04 0.11 0.00 0.12 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C35:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C35 mg/ g T OC 0.00 0.03 0.03 0.10 0.00 0.14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C36:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C36 mg/ g T OC 0.00 0.01 0.01 0.09 0.00 0.11 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C37:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C37 mg/ g T OC 0.00 0.00 0.00 0.07 0.00 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C38:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C38 mg/ g T OC 0.00 0.00 0.00 0.07 0.00 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C39:1 mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n C39 mg/ g T OC 0.00 0.00 0.00 0.06 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Konz. C1-5mg/ g T OC 24.01 31.03 19.49 26.37 30.97 21.31 42.56 18.60 7.29 8.68 20.89 3.24 17.49 10.96
Konz. M ethane mg/ g T OC 5.00 6.88 4.22 7.48 5.01 6.58 9.54 5.58 2.83 3.54 14.10 1.90 8.16 7.97
Konz. C2-5mg/ g T OC 19.01 24.15 15.27 18.89 25.96 14.73 33.02 13.02 4.46 5.15 6.79 1.34 9.33 2.99
Konz. C6-14 mg/ g T OC 47.85 58.91 35.03 36.23 85.54 36.76 84.10 21.22 2.61 4.02 2.59 0.67 4.41 1.25
C6-14 Resolved mg/ g T OC 38.54 47.03 28.05 28.37 68.27 30.27 69.40 17.86 2.56 2.75 2.55 0.59 3.75 1.15
C6-14 Hump mg/ g T OC 9.31 11.87 6.99 7.86 17.27 6.49 14.70 3.36 0.05 1.27 0.04 0.08 0.66 0.10
Konz. C15+ mg/ g T OC 32.40 85.13 32.06 48.92 62.98 51.27 51.63 15.79 1.45 3.61 1.64 1.22 4.38 0.36
C15+ Resolved mg/ g T OC 9.17 32.49 7.85 12.40 27.86 13.45 27.89 7.10 0.12 0.09 0.28 0.04 0.09 0.16
C15+ Hump mg/ g T OC 23.24 52.64 24.21 36.53 35.12 37.82 23.74 8.70 1.33 3.51 1.36 1.18 4.29 0.20
Konz.Gesamt mg/ g T OC 104.26 175.07 86.58 111.52 179.49 109.33 178.29 55.61 11.36 16.31 25.12 5.13 26.28 12.56
C6+ mg/ g T OC 80.25 144.04 67.10 85.15 148.52 88.03 135.73 37.01 4.06 7.63 4.23 1.89 8.79 1.61
C6+ Resolved mg/ g T OC 47.71 79.53 35.90 40.76 96.13 43.72 97.30 24.96 2.69 2.84 2.83 0.63 3.84 1.31
C6+ Hump mg/ g T OC 32.55 64.52 31.20 44.39 52.39 44.31 38.44 12.05 1.37 4.79 1.40 1.26 4.95 0.30
C2+mg/ g T OC 99.26 168.19 82.36 104.04 174.48 102.75 168.76 50.03 8.52 12.77 11.03 3.23 18.12 4.59
n -C6-14mg/ g T OC 7.28 14.42 8.27 11.95 8.91 9.49 9.18 5.89 0.42 0.64 0.08 0.05 0.71 0.03
n -C15+mg/ g T OC 2.88 16.89 3.11 6.71 13.55 5.21 15.23 3.87 0.04 0.02 0.00 0.00 0.01 0.00
TABLE A 4 OPEN-SYSTEM PYROLYSIS GC-FID (PRIMARY PRODUCTS)
106
Table A 4 continued
GFZ no . G 0 1 0 3 6 2 G 0 1 0 3 6 3 G 0 1 0 3 6 6 G 0 1 0 3 6 9 G 0 1 0 3 8 0 G 0 1 0 3 8 3 G 0 1 0 3 8 5 G 0 1 0 3 8 9 G 0 1 0 3 9 6 G 0 1 0 3 9 7 G 0 1 0 3 9 9 G 0 1 0 4 1 6 G 0 1 0 4 1 7 G 0 1 0 4 1 8
TOC 1.98 3.72 3.74 6.45 1.52 2.09 2.07 6.13 3.47 6.33 7.14 12.9 3.29 17.4
S1 1.21 2.54 2.95 4.85 1.08 2.48 1.21 3.07 0.55 0.62 1.12 0.14 0.11 0.24
S2 4.17 7.01 5.58 12.2 2.64 4.83 3.23 5.46 1.1 1.52 1.82 2.9 0.95 4.13
S3 0.36 0.47 0.27 0.44 0.83 2.53 0.37 2.15 1.14 0.69 0.61 0.31 0.54 1
HI 211 188 149 189 174 231 156 89 32 24 25 22 29 24
OI 18 13 7 7 55 121 18 35 33 11 9 2 16 6
Tmax 408 444 447 449 419 425 413 472 470 489 472 541 532 554
PI 0.22 0.27 0.35 0.28 0.29 0.34 0.27 0.36 0.33 0.29 0.38 0.05 0.10 0.05
S1+S2 5.38 9.55 8.53 17.05 3.72 7.31 4.44 8.53 1.65 2.14 2.94 3.04 1.06 4.37
Konz.Gesamt mg/ g r ock 2.06 6.51 3.24 7.19 2.73 2.29 3.69 3.41 0.39 1.03 1.79 0.66 0.86 2.19
RE/ Konz. gesamt 2.02 1.08 1.72 1.70 0.97 2.11 0.88 1.60 2.79 1.47 1.01 4.39 1.10 1.89
Aromates mg/ g T OC 5.30 5.05 3.14 3.11 7.28 3.18 5.62 2.97 0.99 0.90 1.77 0.30 1.44 0.86
Phenols mg/ g T OC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thiophenes mg/ g T OC 0.57 0.32 0.44 0.23 1.11 0.43 0.90 0.24 0.02 0.05 0.00 0.00 0.00 0.00
branched + cyclo Alkanes mg/ g T OC 0.58 0.82 0.50 0.70 1.02 0.50 2.45 0.38 0.09 0.10 0.07 0.02 0.13 0.02
Aromaticity Aromates / n -C6+ 0.52 0.16 0.28 0.17 0.32 0.22 0.23 0.30 2.16 1.36 23.33 6.59 2.01 29.42
Aromaticity Aromates / n -C6-14 0.73 0.35 0.38 0.26 0.82 0.34 0.61 0.50 2.34 1.40 23.33 6.59 2.03 29.42
Aromaticity Aromates/n -C15+ 1.84 0.30 1.01 0.46 0.54 0.61 0.37 0.77 27.86 42.72 - - - -
Aromaticity (Aromates+ Phenols) /
n -C6+0.52 0.16 0.28 0.17 0.32 0.22 0.23 0.30 2.16 1.36 23.33 6.59 2.01 29.42
Phenols/n -C6+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Phenols /n -C6-14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Phenols / n -C15+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 - - - -
Phenols / n -C9-11 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
m,p -Cresol / m,p -Xylol 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
m,p-Cresol / n -C10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thiophenes / n -C6-14 0.08 0.02 0.05 0.02 0.12 0.05 0.10 0.04 0.05 0.09 0.00 0.00 0.00 0.00
branched+cyclo Alkanes /
n -C6-140.08 0.06 0.06 0.06 0.11 0.05 0.27 0.06 0.22 0.15 0.86 0.34 0.19 0.61
GOR 0.30 0.22 0.29 0.31 0.21 0.24 0.31 0.50 1.80 1.14 4.94 1.71 1.99 6.82
Gas Wetness (C2-5)/ (C1-5) 0.79 0.78 0.78 0.72 0.84 0.69 0.78 0.70 0.61 0.59 0.33 0.41 0.53 0.27
GOR resolved 0.50 0.39 0.54 0.65 0.32 0.49 0.44 0.75 2.71 3.06 7.38 5.12 4.55 8.39
mono-Aromatics mg/ g T OC 4.38 4.13 2.58 2.57 6.17 2.68 4.55 2.57 0.94 0.82 1.44 0.26 1.32 0.72
di-aromatics mg/ g T OC 0.92 0.92 0.56 0.54 1.11 0.50 1.07 0.40 0.05 0.07 0.32 0.04 0.12 0.14
di/mono-Aromatics 0.21 0.22 0.22 0.21 0.18 0.19 0.24 0.16 0.05 0.09 0.22 0.15 0.09 0.19
Phenols/Aromates 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thiophenes/M ono-Aromates 0.13 0.08 0.17 0.09 0.18 0.16 0.20 0.09 0.02 0.07 0.00 0.00 0.00 0.00
Phenols/ Konzgesamt [%] % 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n -C6-14mg/ g T OC 4.71 8.62 4.83 6.37 4.99 4.66 5.24 3.78 0.29 0.38 0.05 0.02 0.39 0.02
n -C15+mg/ g T OC 2.40 16.20 2.59 4.58 13.15 3.93 14.90 3.58 0.03 0.02 0.00 0.00 0.01 0.00
n -C6:1-14:1mg/ g T OC 2.57 5.80 3.45 5.58 3.93 4.83 3.94 2.10 0.14 0.25 0.03 0.02 0.32 0.01
n -C15:1+mg/ g T OC 0.47 0.70 0.51 2.14 0.40 1.28 0.32 0.29 0.00 0.00 0.00 0.00 0.00 0.00
TABLE A 5 CLOSED-SYSTEM-MSSV PYROLYSIS GC-FID (PHASEKINETICS)
107
Table A 5 Closed-system-MSSV pyrolysis GC-FID (PhaseKinetics)
G010283 – 0.7 K/min
PhaseKinetics
10% TR
368.7°C
30% TR
388.3°C
70% TR
413.3°C
50% TR
401.6°C
90% TR
432.4°C
G010305 – 0.7 K/min
PhaseKinetics
10% TR
390.4°C
30% TR
408.3°C
70% TR
426.0°C
50% TR
417.8°C
90% TR
437.3°C
C15+ C15+
TABLE A 5 CLOSED-SYSTEM-MSSV PYROLYSIS GC-FID (PHASEKINETICS)
108
G010316 – 0.7 K/min PhaseKinetics
10% TR
389.5°C
30% TR
408.7°C
70% TR
426.3°C
50% TR
418.1°C
90% TR
437.3°C
G010351 – 0.7 K/min PhaseKinetics
10% TR
394.7°C
30% TR
411.6°C
70% TR
429.3°C
50% TR
421.0°C
90% TR
440.2°C
C15+ C15+
TABLE A 5 CLOSED-SYSTEM-MSSV PYROLYSIS GC-FID (PHASEKINETICS)
109
Table A 5 cumulative compositions from PhaseKinetic simulation
10 30 50 70 90
n -C1 26.73 27.93 28.67 29.64 31.75
n -C2 8.34 8.60 8.91 9.15 9.28
n -C3 5.57 6.03 6.27 6.57 7.12
i -C4 0.41 0.51 0.50 0.52 0.47
n -C4 2.75 2.95 3.08 3.16 3.43
i -C5 2.06 1.64 1.25 1.04 0.81
n -C5 1.46 1.61 1.72 1.78 1.94
n -C6 5.42 5.65 5.19 5.19 5.25
C7-15 28.55 24.91 24.54 23.21 22.67
C16-25 12.03 11.94 11.76 11.44 10.49
C26-35 4.30 4.89 4.82 4.84 4.14
C36-45 1.54 2.01 1.98 2.04 1.63
C46-55 0.55 0.82 0.81 0.86 0.65
C56-80 0.28 0.51 0.50 0.56 0.38
TRG010283(mol-%) 10 30 50 70 90
n -C1 17.40 19.54 21.94 22.43 23.58
n -C2 5.28 5.82 6.37 6.42 6.60
n -C3 4.28 4.75 5.37 5.58 5.98
i -C4 0.23 0.24 0.24 0.24 0.24
n -C4 2.52 2.90 3.18 3.26 3.40
i -C5 0.70 0.55 0.47 0.44 0.37
n -C5 1.76 2.07 2.27 2.35 2.39
n -C6 5.46 5.84 6.15 5.88 6.39
C7-15 31.96 28.77 28.67 26.59 25.72
C16-25 16.77 15.72 14.45 14.40 13.75
C26-35 7.58 7.41 6.25 6.72 6.33
C36-45 3.42 3.50 2.70 3.14 2.92
C46-55 1.55 1.65 1.17 1.47 1.34
C56-80 1.10 1.25 0.78 1.09 0.98
G010305(mol-%)
TR
10 30 50 70 90
n -C1 21.04 19.80 20.39 20.49 22.85
n -C2 6.28 5.93 5.97 5.96 6.32
n -C3 5.38 5.09 5.25 5.34 5.96
i -C4 0.41 0.30 0.27 0.23 0.24
n -C4 2.80 2.76 2.94 2.99 3.33
i -C5 0.69 0.50 0.43 0.37 0.36
n -C5 1.80 1.91 2.07 2.11 2.31
n -C6 4.66 5.59 5.60 5.79 6.21
C7-15 28.39 29.22 27.99 27.37 26.72
C16-25 15.35 15.66 15.40 15.30 14.10
C26-35 7.15 7.23 7.31 7.40 6.41
C36-45 3.33 3.34 3.47 3.58 2.91
C46-55 1.55 1.54 1.65 1.73 1.32
C56-80 1.16 1.13 1.26 1.35 0.95
G010316(mol-%)
TR
10 30 50 70 90
n -C1 19.95 21.16 21.38 22.33 24.12
n -C2 5.99 6.26 6.24 6.05 6.36
n -C3 5.13 5.37 5.41 5.87 6.30
i -C4 0.39 0.35 0.33 0.33 0.31
n -C4 2.67 2.92 3.03 3.27 3.52
i -C5 0.66 0.52 0.48 0.43 0.39
n -C5 1.71 2.00 2.12 2.29 2.44
n -C6 5.35 5.55 5.54 5.76 6.20
C7-15 31.65 28.47 26.94 26.13 25.77
C16-25 15.47 15.03 14.96 14.48 13.55
C26-35 6.47 6.83 7.18 6.93 6.13
C36-45 2.71 3.11 3.45 3.32 2.77
C46-55 1.13 1.41 1.65 1.59 1.26
C56-80 0.72 1.01 1.28 1.23 0.89
G010351(mol-%)
TR
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
110
Table A 6 Closed-system pyrolysis GC-FID (compositional kinetic)
G010283 – 0.7 K/min 450°C
475°C
500°C
525°C
550°C
575°C
C15+
T
B
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
111
Table A 6 continued
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
112
Table A 6 continued
G010283 – 2.0 K/min
10% TR
384.0°C
30% TR
406.1°C
70% TR
431.2°C
50% TR
419.1°C
90% TR
450.4°C
475°C
500°C
525°C
550°C
575°C
600°C
C15+ C15+
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
113
Table A 6 continued
G010283 – 5.0 K/min
10% TR
397.0°C
30% TR
420.2°C
70% TR
446.3°C
50% TR
433.7°C
90% TR
465.6°C
480°C
505°C
530°C
555°C
580°C
605°C
C15+ C15+
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
114
Table A 6 continued
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
115
Table A 6 continued
G010351 – 0.7 K/min 450°C
475°C
500°C
525°C
550°C
575°C
C15+
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
116
Table A 6 continued
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
117
Table A 6 continued
G010351 – 2.0 K/min
10% TR
411.3°C
30% TR
429.2°C
70% TR
448.7°C
50% TR
439.5°C
90% TR
460.6°C
475°C
500°C
525°C
550°C
575°C
600°C
C15+ C15+
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
118
Table A 6 continued
G010351 – 5.0 K/min
10% TR
425.0°C
30% TR
443.3°C
70% TR
463.8°C
50% TR
454.1°C
90% TR
476.7°C
480°C
505°C
530°C
555°C
580°C
605°C
C15+ C15+
TABLE A 6 CLOSED-SYSTEM PYROLYSIS GC-FID (COMPOSITIONAL KINETIC)
119
Table A 6 continued
GOR_T-Shift
kg/kg kg/kg Sm³/Sm³
10% TR 0.0701 0.0706 43.20
30% TR 0.0765 0.0738 46.30
50% TR 0.0846 0.0705 46.20
70% TR 0.0970 0.0810 49.60
90% TR 0.1190 0.1049 58.10
G010351GOR_PhasekineticsGOR_T-Shift
kg/kg kg/kg Sm³/Sm³
10% TR 0.1263 0.0794 75.00
30% TR 0.1291 0.0852 78.70
50% TR 0.1320 0.0989 82.60
70% TR 0.1359 0.1127 87.50
90% TR 0.1412 0.1565 102.50
G010283GOR_Phasekinetics