Professional Documents
Culture Documents
Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem
a r t i c l e
i n f o
Article history:
Received 6 July 2010
Received in revised form 26 January 2011
Accepted 28 January 2011
Available online 3 February 2011
a b s t r a c t
We carried out a laboratory rate study to elucidate and quantify the effects of time and pressure on vitrinite reectance (VR). A series of conned system maturation experiments was conducted at 400 C and
at pressures of 2, 10 and 20 kbar. Experiments were performed on dry (no water added) xylite of swamp
cypress and involved run lengths from 0 s to 25 days.
At 400 C, our experimental results demonstrate pressure and heating time to be important variables
that promote VR increase and therefore the maturation of Type III organic material. VR increases with
time at each investigated pressure. Despite rapid initial kinetics, the increase in VR decelerates with time
at each pressure. When VR < 1.44%, increasing pressure reduces the rate of VR increase and hence retards
the initial VR enhancement with time. The retarding effect of pressure on VR increase diminishes with
enhancing VR. The retardation of VR increase is insignicant for geological maturation at 400 C because
a VR of 1.44% is attained in only a few hours. When VR > 1.44%, increasing pressure counteracts the
deceleration of VR increase with time and thus greatly enhances the increase in VR with time. Evidently,
vitrinite maturation takes place rapidly in a dry conned system and does not require addition of water to
occur. The strong effect of the experimental heat-up on VR is obvious even for very short experiments and
must be corrected in kinetic analysis. The evolution of VR with heating time (t) and pressure (P) at 400 C
from an initial VR of 0% is well described by our new power law rate equation
nP;400 C
where the exponent n(P, 400 C) and the rate constant k(P, 400 C) increase with pressure. We regard this
kinetic formulation as a step toward a general equation describing VR evolution as a function of time, pressure and temperature for Type III organic matter. The potential of the power law formalism to model VR
from any starting VR and for complex metamorphic and heating time histories is shown by making explicit
directions on how to use such a kinetic equation.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Metamorphic organic petrology aims to identify, understand
and quantify processes and factors responsible for the formation
and transformation of organic geomaterials and their associated
physical and chemical properties. In particular, it is devoted to
the study of metamorphism and maturation in low to very low
temperature metamorphic terranes. There are many reasons for
this, but all are ultimately related to hydrocarbon exploration
and a fuller understanding of the Earths geodynamic evolution.
It is very difcult to carry out metamorphic studies in terranes consisting mostly of low temperature metasedimentary rocks because
Corresponding author. Tel.: +49 (0)61 51 16 65 41; fax: +49 (0)61 51 16 40 21.
E-mail address: rlebayon@geo.tu-darmstadt.de (R. Le Bayon).
0146-6380/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2011.01.011
341
of Type III organic matter occurs in dry systems. This result will
be compared to a series of hydrous (water added) conned maturations in a further communication in order to identify whether
added water has an effect on VR.
While the effect of temperature on vitrinite reectance has been
well constrained, the inuence of time remains controversial. On
the one hand, it has been argued (e.g., Price, 1983; Ritter, 1984;
Barker, 1989, 1991) that vitrinite reectance evolution is stabilized
rapidly at geological timescales within only 10 years. On the
other hand, both the effective heating time and temperature have
been recognized as important (Lopatin, 1971; Hood et al., 1975;
Waples, 1980; Burnham and Sweeney, 1989; Sweeney and
Burnham, 1990; Hunt et al., 1991; Waples et al., 1992). These early
studies were supported by recent experiments (Huang, 1996; Dalla
Torre et al., 1997; Ernst and Ferreiro Mhlmann, 2004) showing
that, whereas time is important, the major variable that determines VR over geological time intervals is host rock temperature.
Based on these assumptions, several eld and experimentally calibrated models using Arrhenius kinetics were developed to predict
the evolution of vitrinite reectance (Waples, 1980; Burnham and
Sweeney, 1989; Larter, 1989; Suzuki et al., 1993; Huang, 1996;
Dalla Torre et al., 1997; Ernst and Ferreiro Mhlmann, 2004). However, improved understanding of the effect of time on vitrinite
reectance is still needed.
Although considerable efforts have been directed toward
understanding and quantifying the effect of temperature, oxygen
fugacity and starting material upon VR evolution, the effect of pressure on Type III organic matter maturation remains largely unknown. Despite the probable importance of pressure on VR
evolution, all of our information comes either from limited experiments with inconsistent results (Chandra, 1965; Hryckowian
et al., 1967; Goodarzi, 1985; Mastalerz et al., 1993; Hill et al.,
1994) or from controversial estimates from eld studies. Estimates
based on paleometamorphic conditions are poorly constrained in
vitrinite bearing terranes and their surrounding silico-calcic rocks
(e.g., Bostick, 1974; Diessel et al., 1978; Kisch, 1987; Dalla Torre
et al., 1994, 1996). Conicting observations in sedimentary basins
document both enhanced (Law et al., 1989; Hunt, 1996) and retarded (McTavish, 1978; Hao et al., 1995, 2007) VR proles with
the onset of overpressure (for a recent review, see Carr (2000)
and references therein). In general, pressure has been widely regarded as having little inuence on the maturation of Type III organic matter, at least when compared to temperature and
heating time (e.g., Teichmller and Teichmller, 1979; Stach
et al., 1982; Murchison et al., 1985; Huang, 1996; Ernst and Ferreiro Mhlmann, 2004). In summary, considerable confusion exists
about the pressure effect on vitrinite maturation. The lack of clear,
reliable information on the inuence of pressure on VR is surprising if one considers the strong pressure dependence of the well
known graphitization process from experimental studies (e.g., Bonijoly et al., 1982) and the importance of pressure as metamorphic
agent in most geological settings. Knowledge and accurate determination of the pressure effect on VR evolution kinetics is needed
to gain insight into and quantify the diverse processes that span organic metamorphic petrology. Thus, it is essential to experimentally investigate the inuence of pressure on VR evolution rates.
In addition to pressure, the effect of experimental heat-up to
reach the desired run temperature on the material during articial
maturation is still unknown. The experimental heat-up is the rapid
increase in run temperature from room temperature to the desired
nal run temperature (i.e., 400 C). To date, most of the existing
experimental studies on maturation of organic material do not
consider the possible inuences of experimental heat-up on vitrinite reectance (e.g., Huang, 1996; Ernst and Ferreiro Mhlmann,
2004). Dalla Torre et al. (1997) state that experimental heat-up
has no effect on VR as long as the nal temperature is reached in
342
<30 min. This is in contrast with the kinetic study of Huang (1996),
which predicts that VR strongly changes between 300 and 400 C
with run duration as short as 15 min. A stringent experimental
evaluation of heat-up effect on vitrinite maturation is needed.
Our main goal in this work is to elucidate and quantify the effects of time and pressure on vitrinite reectance in dry (no water
added) systems. Furthermore, this experimental study aims to assess the effects of dry maturation and experimental heat-up to the
nal temperature on VR. The research consists of a series of maturation experiments on organic matter at 400 C in a dry, conned
system at 2, 10 and 20 kbar for various run times. A kinetic analysis
of the experimental results was carried out to quantify and understand the evolution of measured vitrinite reectance as a function
of heating time and pressure. We formulated a pressure-dependent
empirical rate equation for the evolution of vitrinite reectance at
400 C and evaluated the pressure dependence of the rate law
parameters to fully assess the effect of pressure on the kinetics of
VR evolution. We provide explicit directions on how to use the
power law formalism to model VR for any starting VR and complex
metamorphic and heating time histories.
It is of special interest to formulate such a VR rate equation because it provides a step toward a general equation that describes
VR evolution as a function of time, pressure and temperature.
The advantage of this VR rate equation is that it does not require
complete understanding of the complex chemical reactions that
regulate vitrinite maturation. This general empirical kinetic equation will be elaborated in a future report. This VR rate equation will
be a useful tool to model the VRTt conditions in vitrinite bearing
sedimentary basins and to estimate the PTt conditions in vitrinite bearing metamorphic terranes occurring in various tectonic
settings (e.g., exhumed subducted terranes, collided terranes in
orogenic wedges). This will aid to gain insight into geodynamic
evolution of sedimentary and metamorphic terranes. Moreover,
this future general empirical kinetic equation will help to improve
hydrocarbon generation modeling in sedimentary basins.
2. Experimental and analytical procedures
Fig. 1. Photograph (a) and photomicrograph (b) (reected light) of the starting
material that consists of swamp cypress (Taxodioidea taxodium). The cellular
microstructure displays the cell walls consisting of telinite that surround the
inlling of the cell lumens. This xylite sample is Middle Eocene in age.
in the swamp forests and hummocks of the Wulfersdorf paleoecosystem and only rare stems and branches are found (Lenz and Riegel, 2001). The sample was stored at ambient conditions and
untreated before the experiments.
The xylite sample displays a recognizable cellular microstructure (Fig. 1b) in which cell walls consisting of telinite surround
structureless inllings of the cell lumens. The xylite sample lacks
liptinite macerals, such as resinite, sporopollenite, chlorophyllinite,
cutinite and bituminite that are known to suppress vitrinite reectance due to their high hydrogen content (for a recent review, see
Carr (2000) and references therein). Ernst and Ferreiro Mhlmann
(2004) recently conrmed vitrinite reectance suppression in
huminite by bituminite and resinite impregnation in their experimental study. In addition, the Wulfersdorf swamp cypress stems
show no oxidation and are very poor in other hydrogen rich plant
constituents, such as resin, wax and tannin. Furthermore, no algal
agglomerates occur in the sample bearing paleoecosystem. This
observation is important because algal agglomerates could suppress vitrinite reectance of the neighboring telinite due to their
high hydrogen contents (e.g., Stach et al., 1982; Carr, 2000).
We measured a low atomic H/C ratio of 1.27 0.03 in the immature xylite sample. This conrms the hydrogen poor nature of the
starting material. A vitrinite reectance VR = 0.167 0.020% was
measured in the starting material, indicating that the initial vitrinite/organic matter was extremely immature prior to the experiments. This allows the investigation of the largest possible VR
range because maturation prior to the experiment does not interfere with our results. This xylite sample of swamp cypress is an
ideal botanical, chemical and physical (low VR) starting material
on which to perform articial vitrinite maturation experiments.
The botanical origin and low H/C ratio of the sample indicate Type
III organic matter in the van Krevelen terminology. This type of organic matter is a good natural gas source, but is less productive of
oil (e.g., Stach et al., 1982; Taylor et al., 1998).
2.3. Experimental methods
The use of a high pressure piston-cylinder apparatus and coldseal pressure vessels to carry out the vitrinite maturation experiments is based on the ndings of Lewan et al. (1979), Monthioux
et al. (1985), Monthioux (1988), Horseld et al. (1989), Landais
et al. (1989), Lewan (1993) and Vandenbroucke et al. (1993) that
natural maturation of organic matter can be reproduced by laboratory experimentation only if conducted in conned systems (i.e., in
sealed gold or platinum capsules under external pressure, with or
without water). These workers found that organic matter heated
under fully conned laboratory conditions follows the same evolution path of H/C versus O/C atomic ratios as the natural coalication. In contrast, open system (under vacuum or inert gas) and
closed system (in sealed glass tubes and with water) maturation
studies do not yield geochemical data compatible with natural
systems.
2.3.1. High pressure piston-cylinder experiments
Experiments at pressures of 10 and 20 kbar with temperature of
400 C were conducted using the end loaded high pressure pistoncylinder apparatus of the Institut fr Geowissenschaften, Abt.
Petrologie und Geochemie, J.W. Goethe-Universitt, Frankfurt am
Main, Germany. We used Pt capsules and NaCl pressure-medium
assemblies (Fig. 2) in a 12.7 mm diameter piston-cylinder pressure
vessel. The capsules consisted of a cylinder and two lids manufactured from platinum tubes and sheets. The Pt lids were fabricated
by folding the rims of the Pt disks (3.6 mm diameter and 0.2 mm
thickness) at 90 by stamping the disks in a steel die. A Pt lid
was electric arc welded into one end of a Pt tube (57 mm long,
3.03 mm outer diameter and 0.2 mm wall thickness). The capsule
Pt70Rh30/Pt94Rh6 (type B)
thermocouple
Mullite thermocouple pipe
Pyrophyllite ring
Steel plug
BN ring
Crushable alumina ring
NaCl cylinder
Upper NaCl sleeve
Lower NaCl sleeve
Pressure
medium
Pt capsule
Graphite cylinder
Graphite disk
Furnace
10 mm
Fig. 2. Cross-section of the piston-cylinder assembly.
343
body was then annealed, hydraulically pressed to obtain a at bottomed capsule and cleaned prior to the introduction of the dry
starting material. The swamp cypress xylite was gently disaggregated to coarse and ne particles (0.11.0 mm in length,
0.1 mm thick) in an agate mill prior to loading into the Pt capsules. No water was added to the capsule. The xylite was lled
and pressed into the capsule almost to the rim. The depth to the
rim must be sufcient to house the second Pt lid. The rim of the
capsule was then crimped down over the rim of the inserted lid
and hydraulically pressed to cold seal the capsule rather than to
weld it. This avoids potential thermal alteration of the charge.
The cold sealed capsule (45 mm long after closure) was placed
vertically in a NaCl assembly acting as sample holder and pressure
medium. NaCl was chosen as pressure medium because it has good
isotropic mechanical behavior at the experimental temperature of
400 C. We machined all NaCl components by hydraulically pressing dried NaCl of 99.99% purity at a maximum of 8 kbar in steel
dies to reach at least 95% of the density of crystalline NaCl. Each
assembly consisted of a NaCl outer cylinder, a graphite heater
and an upper and a lower inner NaCl sleeve (Fig. 2). The lower inner NaCl sleeve housed the run capsule and the upper sleeve
housed the thermocouple. A cylindrical graphite resistance furnace
was used as heater. A graphite disk was added at the bottom of the
lower NaCl sleeve and graphite cylinder to improve formation of a
reliable heating circuit through the cell. The sample assembly was
placed in the tungsten carbide core of the pressure cell. The entire
assembly and thermocouple plate were then added to the pistoncylinder apparatus. To control run temperature, a Pt70Rh30Pt94Rh6
(type-B) thermocouple was inserted axially into the assembly and
located at a distance of 0.6 0.03 mm above the at top of the Pt
capsule. Thermocouple wires were placed inside a two-bore mullite pipe to isolate them from electric contact with the thermocouple plate and sample assembly. Experiments were pressurized to
the desired run pressure at room temperature and then heated to
400 C at a rate of 50 C/min. This led to a heat-up time of
<8 min. Temperature ramp rate and temperature during the experiment were controlled automatically via a programmable EUROTHERM power controller. Temperature was held constant to
within 1 C during experiments. Temperatures reported in this
experimental study are uncorrected for potential thermal gradients in the capsule. Stated values are thought to be accurate to
1 C. Pressure was kept constant for the duration of the experiment by manual adjustment if necessary. Pressure is considered
to be accurate to 1 kbar. Run conditions were maintained for 0 s
to 25 days. Experiments were quenched in <10 s by switching off
the power to the heater whilst maintaining quasi run pressure.
Afterwards, pressure was decreased in 30 min.
2.3.2. Cold-seal pressure vessel experiments
Several unsuccessful attempts were made to perform experiments at 2 kbar and 400 C using the high pressure piston-cylinder
apparatus: The run capsules exploded. To overcome this problem,
an alternative experimental method was used for low pressure
experiments. Experiments at a xed pressure of 2 kbar were conducted in cold-seal pressure vessels in the hydrothermal laboratory of the Geological and Environmental Sciences Department of
Stanford University, California. The xylite was loaded into gold capsules. Run capsules were placed in cone-in-cone cold-seal pressure
vessels (Kerrick, 1987) connected to a water pressure reservoir, a
Heise bourdon tube gauge and an air driven hydraulic pump. Prior
to beginning this study, each autoclave and thermocouple assembly was temperature calibrated against the melting point of NaCl
at 1 atm. After pressurization of an experimental sample to 2 kbar
aqueous uid pressure, the vessel was placed in a nichrome wound
resistance furnace and externally heated to the desired temperature using an electronic proportional temperature regulator
344
345
Table 1
Experimental maturation conditions and results.a
Run no.
Methodb
P (bar)
t0 (s)
rVR(P, 400 C, t )
Source
GE-V4
GE-V3
GE-V8
GE-V12
GE-H28
GE-F30
GE-H30
GE-F27
GE-H27
RLB-e43
RLB-e30
RLB-e39
RLB-e22
RLB-e33
RLB-e16
RLB-e42
RLB-e41
RLB-e40
RLB-e27
RLB-e05
RLB-e19
RLB-e44
RLB-e84
RLB-e35
RLB-e26
RLB-e02
RLB-e06
RLB-e03
RLB-e08
RLB-e07
RLB-e04
RLB-e36
RLB-e01
CSPV
CSPV
CSPV
CSPV
CSPV
CSPV
CSPV
CSPV
CSPV
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
HPPC
2000
2000
2000
2000
2000
2000
2000
2000
2000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
0
900
3600
86,400
1,555,200
2,505,600
2,505,600
4,320,000
4,320,000
0
100
240
900
900
3600
3600
8100
18,000
86,400
432,000
432,000
2,160,000
0
900
900
3600
3600
18,000
18,000
86,400
432,000
432,000
2,160,000
0.745
0.753
1.176
1.624
2.041
2.086
2.068
2.116
2.191
0.669
0.666
0.683
0.864
0.862
1.066
0.952
1.262
1.386
1.695
2.098
2.017
2.561
0.504
0.681
0.706
0.860
0.883
1.129
1.130
1.879
2.326
2.130
3.360
0.044
0.039
0.042
0.048
0.057
0.094
0.058
0.072
0.075
0.034
0.037
0.047
0.053
0.038
0.041
0.054
0.078
0.031
0.060
0.037
0.031
0.057
0.027
0.033
0.023
0.024
0.036
0.039
0.048
0.034
0.018
0.053
0.051
137
442
100
101
100
34
100
41
100
239
173
116
278
100
500
500
223
263
100
167
161
235
500
136
115
100
100
137
500
100
200
100
105
c
c
c
d
d
d
d
d
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
a
Notations: P, pressure; t0 , experimental effective heating time; VR(P, 400 C, t0 ), measured vitrinite reectance after an experimental effective heating time t0 at 400 C and
pressure P; rVR(P, 400 C, t0 ), standard deviation of VR(P, 400C, t0 ); N, number of measurements.
b
HPPC, high pressure piston-cylinder apparatus experiments; CSPV, cold-seal pressure vessel experiments.
c
Results of this study.
d
Results of Ernst and Ferreiro Mhlmann (2004).
346
3.0
2.5
2.0
1.5
2 kbar
1.0
0.5
: VR heat-up (2 kbar,400 C)
r 2 = 0.997
0.0
2.5
2.0
1.5
10 kbar
1.0
0.5
: VR heat-up (10 kbar,400 C)
r 2 = 0.996
0.0
0
10
20
30
40
50
60
10
t' (days)
2.5
2.0
20 kbar
1.5
1.0
r2
1.2
3.0
0.5
20
25
30
1.3
c
VR (P, 400 C, t' ) (%)
4.0
3.5
15
t' (days)
: VR
= 0.995
heat-up
1.1
1.0
0.9
0.8
: 10 kbar
0.7
: 2 kbar
(20 kbar,400 C)
0.6
0.0
0
10
15
20
25
30
t' (days)
1000
2000
3000
4000
t' (s)
Fig. 4. Vitrinite reectance VR as a function of experimental effective heating time t0 at 400 C and (a) 2 kbar, (b) 10 kbar and (c) 20 kbar. The curves are the least-squares best
0
ts to the data using the power law equation VR(P, 400 C, t0 ) = VR(P, 400 C, 0) + (k0 (P, 400 C) t0 )n (P, 400 C) (Eq. (1)). The heat-up vitrinite reectance VRheat-up(P, 400 C) (star) is
shown at each investigated pressure for information but is excluded from this kinetic t. VR data similar to their respective starting vitrinite reectance VRheat-up(P, 400 C) are
neither plotted nor considered into this kinetic t (see text). The error bars are one standard deviation rVR(P, 400 C, t0 ). (d) VR(P, 400 C, t0 ) of the shorter experimental effective
heating times t0 as a function of t0 at 400 C and 2 and 10 kbar. VR(P, 400 C, t0 ) plateaus that indicate short activation time before VR increases from the starting vitrinite
reectance VRheat-up(P, 400 C) are clearly visible.
347
4. Kinetic analysis
4.1. Empirical rate equation for VR evolution
In order to quantify and understand the relationship between
vitrinite reectance, pressure and time, we performed a kinetic
analysis of the experimental results. This analysis will be a useful
tool for extrapolating vitrinite reectance to geological situations
via an empirical rate equation.
C
where VR(P, 400 C, t ) is the vitrinite reectance value after effective heating time t0 (s), VR(P, 400 C, 0) is the original vitrinite reectance at t0 = 0, k0 (P, 400 C) is the rate constant with dimensions
[time]1 and n0 (P, 400 C) is the dimensionless exponent at a given
pressure P and 400 C. The exponent n0 (P, 400 C) has no signicance in terms of stoichiometries of the chemical reaction mechanisms. The experimental VR data were weighted assuming the
uncertainties in measured VR given in Table 1. Eq. (1) provides a satisfactory description of our VR data as all ts yield correlation coefcients r2 > 0.995 (Table 2). In Table 2, we provide the magnitudes
of VR(P, 400 C, 0), k0 (P, 400 C) and n0 (P, 400 C) that were determined at each run pressure P by tting the experimental VR data
(Table 1) to Eq. (1). We plotted the three isobaric least squares
regression curves in VR(P, 400 C, t0 ) versus t0 diagrams (Fig. 4ac).
Table 2
Vitrinite reectances at effective heating time t0 = 0 VR(P, 400 C, t0 = 0), rate constants k0 (P, 400 C) and power law exponents n0 (P, 400 C) at pressures P and 400 C.a
P (bar)
n0 (P, 400 C)
rn (P, 400 C)
r2
2000
10,000
20,000
1.426 10+2
6.390 101
2.788 101
2.030
6.078 101
6.250 102
6.675 10+160
6.678 1023
6.558 1013
1.790 10+308
5.648 1022
5.014 1013
9.586 104
9.477 102
2.584 101
3.848 105
2.694 102
1.521 102
0.997
0.996
0.995
a
Notations: rVR(P, 400 C,
correlation coefcient.
t0 =0),
400 C),
400 C),
348
Table 3
Experimental maturation conditions and results after corrections of the effective heating time.a
Run no.
P (bar)
t (s)
rVR(P, 400 C, t)
ln t (t in s)
ln VR(P, 400 C, t)
GE-V8
GE-V12
GE-H28
GE-F30
GE-H30
GE-F27
GE-H27
RLB-e22
RLB-e33
RLB-e16
RLB-e42
RLB-e41
RLB-e40
RLB-e27
RLB-e05
RLB-e19
RLB-e44
RLB-e35
RLB-e26
RLB-e02
RLB-e06
RLB-e03
RLB-e08
RLB-e07
RLB-e04
RLB-e36
RLB-e01
2000
2000
2000
2000
2000
2000
2000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
10,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
20,000
820
83,620
1,552,420
2,502,820
2,502,820
4,317,220
4,317,220
470
470
3170
3170
7670
17,570
85,970
431,570
431,570
2,159,570
915
915
3615
3615
18,015
18,015
86,415
432,015
432,015
2,160,015
1.176
1.624
2.041
2.086
2.068
2.116
2.191
0.864
0.862
1.066
0.952
1.262
1.386
1.695
2.098
2.017
2.561
0.681
0.706
0.860
0.883
1.129
1.130
1.879
2.326
2.130
3.360
0.042
0.048
0.057
0.094
0.058
0.072
0.075
0.053
0.038
0.041
0.054
0.078
0.031
0.060
0.037
0.031
0.057
0.033
0.023
0.024
0.036
0.039
0.048
0.034
0.018
0.053
0.051
6.709
11.334
14.255
14.733
14.733
15.278
15.278
6.153
6.153
8.061
8.061
8.945
9.774
11.362
12.975
12.975
14.585
6.819
6.819
8.193
8.193
9.799
9.799
11.367
12.976
12.976
14.586
4.443
4.120
3.892
3.870
3.879
3.856
3.821
4.751
4.754
4.541
4.654
4.372
4.279
4.077
3.864
3.904
3.665
4.989
4.953
4.756
4.730
4.484
4.483
3.974
3.761
3.849
3.393
Notations: P, pressure; t, corrected effective heating time; VR(P, 400 C, t), measured vitrinite reectance at the corrected effective heating time t, 400 C and pressure P;
C
3
400 C
3.5
bar
20 k
3.0
10 kbar
2.5
2.0
2 kbar
1.5
1.0
0.5
20 kbar
r 2 = 0.994
10 kbar
r 2 = 0.997
2 kbar
r 2 = 0.997
0.0
0
10
20
30
40
50
t (days)
Fig. 5. Variation in vitrinite reectance VR(P, 400 C, t) with corrected effective
heating time t at 400 C and 2, 10 and 20 kbar (Table 3). The curves are the
least-squares best ts to the data using the power law equation VR(P, 400 C, t) =
(k(P, 400 C) t) n(P, 400 C) (Eq. (2)). The error bars are one standard deviation
rVR(P, 400 C, t).
where n(P, 400 C) is the slope and n(P, 400 C) ln k(P, 400 C) is the
normalization constant of the straight line ln VR(P, 400 C, t) versus
ln t. The straight lines are calculated using Eq. (3) at 2, 10 and
20 kbar, using the best estimates for the constants n(P, 400 C)
and k(P, 400 C) given in Table 4. Results of these calculations are
presented in Fig. 6. Fig. 6 is a ln VR(P, 400 C, t) versus ln t plot that
gives a set of three lines of ln VR(P, 400 C, t) evolution with ln t at
three different pressures. The pairs (ln VR(P, 400 C, t), ln t) (Table 3)
are found to lie on or close to the straight lines shown in Fig. 6. This
graphic check demonstrates that the variables ln VR(P, 400 C, t) and
ln t are linearly related. This result conrms the use of our power
law equation (Eq. (2)) to describe the evolution of vitrinite reectance with time at different pressures and 400 C. In addition, this
linear Eq. (3) and its plot in Fig. 6 are useful because they show that
both short (65 days) and long (>5 days) duration experiments are
important to quantify VR evolution with heating time. Furthermore,
this kinetic analysis shows that VR evolution is continuous with
heating time.
We are now in a position to discuss the VR magnitude and
kinetics because Eqs. (2) and (3) and their related VRt data
349
2000
10,000
20,000
a
31
30
9.541 10
1.648 1019
2.782 1014
Notations: rk(P,
400 C),
2
3.337 10
1.523 1019
7.894 1015
400 C),
5h
1d
5d
25 d 100 d
4.0
3.0
2 kbar
2.5
2.0
4.0
1.5
ar
b
2k
1.2
ar
kb
1.0
10
ar
r 2 20 kbar = 0.994
kb
0.8
r 2 10 kbar = 0.997
20
ln VR (P, 400 C, t)
400 C
5.0
r 2 2 kbar = 0.997
10
ln t ( t
0.997
0.997
0.994
10 kbar
4.5
4.460 10
3.780 103
3.101 103
20 kbar
3.5
3
7.120 10
1.282 101
2.062 101
t
3
15
min min 1 h
r2
rn(P, 400 C)
n(P, 400 C)
12
14
0.6
16
in s)
C1
4
Taking the natural logarithm of Eq. (4) for graphic convenience
and using k(P, 400 C)1 VR(P, 400 C, t)n(P, 400 C) in place of t from
a rearrangement of Eq. (2), we obtain by rearranging and
simplifying
2.5
4.0
10
20
kb
400 C
10
ar
10
10
10
15
20
t nP;400
1.0 1.44
5
r
ba
2k
C
0.6
ar
kb
VR (%)
0.4
10
P (bar)
25
6
lnVR (VR in %)
Fig. 7. Double-logarithmic plot of the variation in the rate at which VR(P, 400 C, t)
increases with time versus VR at 400 C and 2, 10 and 20 kbar. The lines are
calculated using the equation ln (dVR(P, 400 C, t)/dt) = ln (n(P, 400 C) k(P,400 C))
+ (1 n(P, 400 C)1) ln VR(P, 400 C, t) (Eq. (5)) and the best estimates for the
constants n(P, 400 C) and k(P, 400 C) given in Table 4. ln VR(P, 400 C, t) is given by
Eq. (3). The three lines intersect at VR = 1.44% and dVR(P, 400 C, t)/
dt = 7.00 106 % s1.
0.30
400 C
0.25
n (P, 400 C)
350
0.20
0.15
0.10
0.05
r 2 = 0.999
0.00
0
10
15
20
25
P (kbar)
Fig. 8. Variation in power law exponent n(P, 400 C) with pressure at 400 C
(Table 4). The solid line is the least-squares best t to the data using the linear
equation n(P, 400 C) = n(0, 400 C) + BP (Eq. (6)). The error bars in n(P, 400 C) are
one standard deviation rn(P, 400 C). The error bars in pressure are 25 bar at 2 kbar
and 1 kbar at 10 and 20 kbar.
kP; 400 C CP D
Initially, the power law exponent was considered to be independent of pressure (Dalla Torre et al., 1997) and temperature (Huang,
1996; Dalla Torre et al., 1997; Ernst and Ferreiro Mhlmann, 2004).
In contrast, we have previously noted that the power law exponent
n(P, 400 C) increases with pressure. Therefore, it is of particular
interest to analyze the inuence of pressure on this variable.
Accordingly, we plot n(P, 400 C) (Table 4) versus pressure in
Fig. 8: A regular increase in the power law exponent with pressure
is evident. This graphically points out the linear pressure dependence of this exponent. We best t all the data in Fig. 8 to quantify
the variation of the power law exponent n(P, 400 C) as a function of
pressure P by least squares to a linear relation expressed as
7
D
1
ln kP; 400 C ln C D ln P
k (P, 400 C) 10 14 (s 1 )
400 C
r 2 = 0.995
0
0
10
15
20
25
P (kbar)
P (kbar)
2
20
30
20
400 C
40
10
14
10
19
10
30
50
60
70
k (P, 400 C) (s 1 )
10
r 2 = 0.995
80
Fig. 9. (a) Variation in the rate constant k(P, 400 C) as a function of pressure at
400 C (Table 4). The solid curve is least-squares best t to the data using the power
law equation k(P, 400 C) = C PD (Eq. (7)). The error bars in k(P, 400 C) are one
standard deviation rk(P, 400 C). The error bars in pressure are 25 bar at 2 kbar and
1 kbar at 10 and 20 kbar. (b) Double-logarithmic plot of the rate constant k(P,
400 C) versus P at 400 C. The solid line is the calculated linear equation ln k(P,
400 C) = ln C + D ln P (Eq. (8)).
with Eq. (8), using the best estimates for the constants C and D given
above. A plot of this calculated straight line and of the negative retrieved ln k(P, 400 C) data versus ln P is shown in Fig. 9b. This plot
displays a good t of the data to the calculated straight line (Eq. (8))
inasmuch as the pairs (ln k(P, 400 C), ln P) lie on or close to this
straight line. This graphic check validates the linear relationship between ln k(P, 400 C) and ln P. Therefore, the use of a power law
equation (Eq. (7)) is conrmed to describe the increase in the rate
constant k(P, 400 C) with P at 400 C. The pressure sensitivity demonstration of the rate constant k(P, 400 C) is of interest because it
further makes apparent the pressure contribution to the VR evolution rate Eq. (2).
4.4. The pressure sensitive VR evolution rate equation discussion
Having dened the pressure dependence of the power law exponent n(P, 400 C) and the rate constant k(P, 400 C), we are now in a
position to make explicit the pressure effect on the VR evolution
kinetics. In this regard, we insert Eqs. (6) and (7) in Eq. (2) to get
CBP
10
10
lnP (P in bar)
351
where the rate constant k(P, T) and the power law exponent n(P, T)
are both pressure and temperature dependent. This stems from the
demonstration that VR evolution is characterized by a power law
rate equation dependent on pressure (this study) and temperature
(Huang, 1996; Dalla Torre et al., 1997 and Ernst and Ferreiro Mhlmann, 2004). Furthermore, the kinetic parameters associated to this
power law formalism are pressure (this study) and temperature
dependent (Huang, 1996; Dalla Torre et al., 1997 and Ernst and
Ferreiro Mhlmann, 2004). The power law equation quantifying
VR evolution (e.g., our isothermal VR evolution rate Eq. (9)) is retrieved and formulated for a starting VR equal to 0% at t = 0. Consequently, the power law formalism with its associated rate constant
k and power law exponent n must be used to calculate VR only for a
starting VR equal to 0%. In nature, vitrinite precursors have reectance ranging between 0.1 and 0.2%. In addition, the starting
VR can display higher values resulting from one or several maturation events. However, the power law formalism (Eq. (10)) permits
the evaluation of VR attained after any heating time theating at PT
conditions (i.e., P2T2) different from the previous ones (i.e.,
P1T1) (Fig. 10) from any starting VR once a correction for heating
time is performed. For such VR estimation, we have to proceed in
two steps. First, we dene the heating time tstarting necessary at
P2T2 to increase VR from 0% to any starting VR previously reached
at P1T1 (i.e., VR(P1, T1)) (Fig. 10) with the power law Eq. (10) rearranged as
11
352
t starting + t heating
t starting
VR
t heating
P2 T2
3.0
t
: VR t evolution at conditions P2 T2
0 :0starting VR equal to 0%
1
VR (2 kbar,400 C, t )
(%)
a
2.5
2.0
1.5
1.0
2 kbar
0.5
: EASY%Ro
0.0
0
10
20
(%)
40
50
60
3.0
2.5
2.0
1.5
1.0
10 kbar
0.5
: EASY%Ro
0.0
0
10
15
20
25
30
t (days)
4.0
(%)
30
t (days)
12
VR (20 kbar,400 C, t )
nP2 ;T 2
VRP2 ; T 2 kP2 ; T 2 t heating t starting
3.5
3.0
2.5
2.0
1.5
1.0
20 kbar
0.5
: EASY%Ro
0.0
0
10
15
20
25
30
t (days)
Fig. 11. Comparison of VR modeled with EASY%Ro to VR obtained with experiments
(Table 3) as a function of effective heating time t at 400 C and (a) 2 kbar, (b) 10 kbar
and (c) 20 kbar. The gray thick curves are VR evolution with time modeled with
EASY%Ro at 400 C. The light curves are the least-squares best ts to the data using
the power law Eq. (2) that are displayed in Fig. 5. The error bars are one standard
deviation rVR(P, 400 C, t).
at 400 C despite the VR plateau calculated with our rate Eq. (9) for
geological heating times (613) at 2 kbar and 400 C that approximates the VR calculated with the equation of Barker and Pawlewicz
(1986). Nevertheless, Ernst and Ferreiro Mhlmann (2004) show
that the VR increase at 2 kbar and 200 C is stabilized rapidly with
heating time. Their long duration laboratory results demonstrate
that at constant PT conditions, a quasi-threshold VR value is
attained in a geologically insignicant time and thereafter VR
increases progressively more slowly with continued heating. Thus,
the equation of Barker and Pawlewicz (1986) might be relevant at
very low temperature conditions where the effects of time and
pressure should be less pronounced on the VR evolution rates.
Larter (1989) provided a VR equation based on the concentration of phenols released from vitrinite at different maturities during pyrolysis. A serious limitation of this approach is that the
amounts of phenols released from organic matter are easily quantied only in the range 0.45% < VR < 1.6%. Another equation is the
EASY%Ro method (Burnham and Sweeney, 1989; Sweeney and
Burnham, 1990), based on the rate of cracking of the most important volatile products from vitrinite. The generation of these compounds is described by a rst order Arrhenius equation and the
procedure follows the basic work of Karweil (1956) and improvements by Tissot and Espitali (1975). The use of both of the chemistry based VR equations is limited for high pressure conditions
because they do not consider the important pressure effect on VR
demonstrated in this study. It is of interest to compare the well
known kinetic model of VR evolution EASY%Ro with the experimental VR obtained in this study at 400 C. We calculate VR evolution
with time at 400 C with EASY%Ro and plot it in the experimental
VR(P, 400 C, t) versus t diagrams (Fig. 11). The rate model EASY%Ro
of Sweeney and Burnham (1990) provides VR that are higher than
the 2 kbar experimental data and lower than the 20 kbar runs. The
disparities between the model and the laboratory maturation are
less at 10 kbar: VR calculated with EASY%Ro are slightly lower than
the experimental VR. It is obvious that the upper temperature limit
is reached at 400 C for the use of EASY%Ro. This argues for a strict
use of EASY%Ro for temperature T 400 C. In addition, the disparities between modeled and experimental maturation change with
increasing pressure. It shows the importance to include pressure
as a parameter controlling the maturation in kinetic model of VR
evolution. We believe that our kinetic experiments on vitrinite
maturation may aid in model (e.g., EASY%Ro) improvement. However, the phenol kinetic and the popular EASY%Ro methods are useful tools to calibrate and model VR at very low temperature and
when the pressure effects on VR evolution rates can be neglected,
i.e., at very low pressure conditions.
This discussion points out several limitations in the already
existing VR equations and demonstrates the strength of experimentally derived empirical VR rate equation to model VR evolution.
5. Summary
The experimental results demonstrate that VR increases with
heating time at 400 C and at each investigated pressure. Despite
rapid initial kinetics, a deceleration of VR increase with time takes
place at each pressure. A variation in pressure effects on VR increase
kinetics is found. When VR < 1.44%, increasing pressure decreases
the rate of VR increase and hence retards the initial VR enhancement. Consequently, the lower pressure, the higher are the initial
VR magnitude and evolution kinetics. Nevertheless, the retarding
effect of pressure on VR increase diminishes with enhancing VR.
However, a VR of 1.44% is rapidly attained (only a few hours) at
400 C. Therefore, the retardation of VR increase is insignicant
for geological maturation at 400 C. When VR > 1.44%, increasing
pressure reduces the deceleration of VR enhancement with time
353
and thus results in a larger VR increase with time at 400 C. Obviously, heating time and pressure promote VR increase and the maturation of Type III organic material at 400 C. In addition, Type III
organic matter maturation is shown to rapidly occur in a dry conned system and does not require added water. Finally, a strong effect of the experimental heat-up on VR is identied and quantied,
even on experiments of very short duration. This information is
important because the experimental heat-up effect must be corrected in kinetic analysis.
The evolution of vitrinite reectance with time and pressure
at 400 C from an initial VR value of 0% is accurately described
by our new power law rate equation VR(P, 400 C, t) =
(k(P, 400 C) t)n(P, 400 C), where the exponent n(P, 400 C) increases linearly with pressure and the rate constant k(P, 400 C)
that obeys a power law equation with pressure, increases with
pressure. This VR evolution rate equation with its associated power
law exponent n(P, 400 C) and rate constant k(P, 400 C) accounts
for our experimental observations. In particular, this equation describes the expected increase in VR with time inasmuch as n(P,
400 C) > 0. Nevertheless, this equation calls for a deceleration of
VR increase with time because n(P, 400 C) < 1. Furthermore, the
VR power law rate equation shows the observed pressure effects
on VR evolution kinetics. Increasing pressure results in the lesser
deceleration of VR enhancement with time because n(P, 400 C) increases with pressure. With increasing pressure, the power law
rate equation displays the initial VR increase retardation when
VR < 1.44% and the larger VR increase with time when VR > 1.44%.
We regard our kinetic formulation as a step toward a general
equation describing VR evolution as a function of time, pressure
and temperature for Type III organic matter. Such VR rate equation
is empirical and based on VR measured after experimental maturation of vitrinite under various pressure, temperature and heating
time conditions. Our rate equation is not based on chemical kinetics because the chemical reactions in organic matter/vitrinite maturation are complex. We show the potential of the power law
formalism to model VR from any starting VR and for complex metamorphic and heating time histories by making explicit how to use
such a kinetic equation. The power law formalism is a simple and
fast algorithm to simulate VRPTt evolution. This is an advantage
to model large-scale sedimentary basins and metamorphic terranes. Kinetic models that do not consider the effects of effective
heating time, pressure and experimental heat-up to reach the desired run temperature may not accurately account for the evolution of vitrinite reectance in natural systems. Despite these
advances, signicant insights into VR evolution kinetics may
emerge through future experimental studies at different temperatures or/and in wet (water added) conned systems.
Acknowledgements
This research was supported by the Deutsche Forschungsgemeinschaft (DFG) Grant BA 3527/1-1. We thank T. Kautz for help in
the high-pressure lab, V. Bullatov for technical discussions during
machining of the piston-cylinder assemblies, W. Pttmann for analyzing the chemistry of the xylite sample, M. Dolezych for supplying the original xylite and S. Weinbruch for a check of the
manuscript. The manuscript greatly beneted from detailed comments by A. Burnham, R. Hill and an anonymous reviewer. R. Littke
provided useful reviews on an earlier draft of this paper.
Associate EditorKen Peters
References
rkai, P., Ferreiro Mhlmann, R., Suchy, V., Balogh, K., Sykorov, I., Frey, M., 2002.
Possible effects of tectonic shear strain on phyllosilicates: a case study from the
354
355
Underwood, M.B., Shelton, K.L., McLaughlin, R.J., Laughland, M.M., Solomon, R.M.,
1999. Middle Miocene paleotemperature anomalies within the Franciscan
Complex of northern California: thermo-tectonic responses near the
Mendocino triple junction. Geological Society of America Bulletin 111, 1448
1467.
van Krevelen, D.W., 1953. Physikalische Eigenschaften und chemische Struktur der
Steinkohle. Brennstoff-Chemie 33, 167182.
Vandenbroucke, M., Behar, F., San Torcuato, A., Rullkter, J., 1993. Kerogen
maturation in a reference kerogen type II series: the Toarcian shales of the
Hills Syncline, NW Germany. Organic Geochemistry 20, 961972.
Waples, D.W., 1980. Time and temperature in petroleum formation: application of
Lopatins method to petroleum exploration. American Association of Petroleum
Geologists Bulletin 64, 916926.
Waples, D.W., Kamata, H., Suizu, M., 1992. The art of maturity modelling. Part 1:
nding a satisfactory geologic model. American Association of Petroleum
Geologists Bulletin 76, 3148.
Wenger, L.M., Baker, D.R., 1987. Variations in vitrinite reectance with organic
facies examples from Pennsylvanian cyclothems of the mid-continent, USA.
Organic Geochemistry 11, 411416.
Wolf,
M.,
1978.
Inkohlungsuntersuchungen
im
Hunsrck,
Rheinishe
Schiefergebirge. Zeitschrift fr der Deutschen Geologischen Gesellschaft 129,
217227.