Development of a compositional kinetic model for primary ...

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


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


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)

http://www.eia.gov/

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.

http://www.gas-shales.org/

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


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)


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)


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)


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).


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


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


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


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


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


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


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


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)


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


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


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).


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.


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


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


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


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


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.


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


EX-B (upper, deep lacustrine)

12

9

min20 40 60 80 100

pA

10

15

20

25

30

35


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


EX-A (deep lacustrine)

23

15

min20 40 60 80 100

pA

10

20

30

40

50

60

70

80

90


EX-A (deep lacustrine)

23

15


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


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


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).


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)


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))


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).


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.


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



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


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



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)


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)


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


°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


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


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


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


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


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


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


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-%]


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.


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


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


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


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


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


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).


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)


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)


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


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,


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


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.


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


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


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


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


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.


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


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


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


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


°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


%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


°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


%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)


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.


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


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


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


86

Table A 2 continued

EX-ATop-



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


87

Table A 2 continued

EX-BTop-



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

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Table A 2 continued

EX-BTop-



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

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Table A 2 continued

EX-BTop-



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

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Table A 2 continued

EX-CTop-



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

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Table A 2 continued

EX-CTop-



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

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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


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


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


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


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 -C6-14

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


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 / 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


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



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



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


96

Table A 4 continued


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



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


97

Table A 4 continued


?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


98

Table A 4 continued


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


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


+ 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


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


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



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


100

Table A 4 continued


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


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



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


101

Table A 4 continued


?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+ 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


102

Table A 4 continued


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 - - -


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



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


103

Table A 4 continued

Format ion/ B asin


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


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


+ 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


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



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


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



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


104

Table A 4 continued


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


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


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




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


105

Table A 4 continued


?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+ 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+ 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


106

Table A 4 continued


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 -C6-14 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 / 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


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



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+


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+


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


111

Table A 6 continued


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+


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+


114

Table A 6 continued


115

Table A 6 continued

G010351 – 0.7 K/min 450°C

475°C

500°C

525°C

550°C

575°C

C15+


116

Table A 6 continued


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+


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+


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

Development of a compositional kinetic model for primary ...

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