Org. Geochem. Vol. 24, No. 2, pp.

233-241, 1996
Pergamon Copyright © 1996ElsevierScienceLtd
Printed in Great Britain.All rights reserved
PII: S0146-6380(96)00032-0 0146-6380/96$15.00+ 0.00

Experimental study of vitrinite maturation: effects of temperature,

time, pressure, water, and hydrogen index
WUU-LIANG HUANG
Exxon Production Research Company, P.O. Box 2189, Houston, TX 77252-2189, U.S.A.

Abstract--Lignite samples were artificially matured in sea water over a wide range of temperature and
time (250~50°C and up to 305 days) in a confined-pressure system. The reflectance evolution of
vitrinite-like macerals in the run products was found to fit an empirical power law rate model. These
experiments confirm that the evolution of vitrinite reflectanceis controlled more by temperature than time.
The empirical model is reasonably consistent with the kinetic model of Burnham and Sweeney (1989)
implying that the mechanism for vitrinite reflectancedevelopment at the experimental conditions may not
differ significantlyfrom that in nature. This simple rate equation is particularly useful to incorporate into
the algorithm of a basin modeling program. Additional experiments confirm that the evolution rate of
reflectance of vitrinite depends highly on the original hydrogen content (as measured by hydrogen index)
in its precursor materials. Other factors such as water pressure, fluid chemistry, fluid flow, the presence
ofoil or Type I organic matter and methane or CO_,partial pressures were found to play only minor roles
in the development of vitrinite reflectance. Copyright © 1996 Elsevier Science Ltd

Key words--vitrinite reflectance, confined pressure pyrolysis, lignite, kinetics, thermal history, artificial
maturation, hydrogen index

INTRODUCTION bration by directly measuring the evolution rate of

The measurement of vitrinite reflectance in source
rocks has been used widely as an indicator of organic
maturation. Although this technique, in general, can
estimate the level of organic metamorphism of a
source rock, failures of this technique have been
reported in some field examples. Therefore, many
petroleum geochemists are seeking to improve the
technique or to integrate it with other independent
maturity indicators for a more accurate maturity
estimate.
One limitation or pitfall of using vitrinite
reflectance to estimate maturation is attributed to
an over-simplified assumption that the change in
vitrinite reflectance is only a function of the
time-temperature exposure of source rocks. The
effect of other factors, such as hydrogen content of
the starting lignite (measured by the hydrogen index,
HI), the type of associated organic or mineral matrix
as well as fluid characteristics (e.g,, pH, Eh and
salinity), on the development of vitrinite reflectance is
poorly understood. In addition, the actual role of
time in the development of vitrinite reflectance has
been the subject of controversy (e.g., Price, 1983;
Ritter, 1984). Other limitations include the lack of
experimentally calibrated kinetic models for quanti-
tatively predicting vitrinite reflectance. Burnham and
Sweeney (1989), Larter (1989), Sweeney and Burn-
ham (1990) and Suzuki et al. (1993) derived chemical
kinetic models from the chemical kinetics of vitrinite
maturation, which can indirectly predict the evol-
ution of vitrinite reflectance. Experimental cali-
vitrinite is necessary since the reflectance evolution is
not a sole function of chemical change but is also
related to the structural heterogeneity of vitrinite
(Khavari Khorasani and Michelsen, 1994).
The evolution of optical properties of coals during
artificial maturation in dry and open systems in
nitrogen or inert gas atmosphere has been reported
previously (e,g., Chandra and Taylor, 1975; Pearson
and Creaney, 1981; Goodarzi, 1984). Others (e.g.,
Rohrback et al., 1984; Monthioux, 1986; Lewan,
1985) attempted to measure vitrinite reflectance of
solid pyrolyzates using hydrous pyrolysis conditions,
which are believed to better simulate natural
conditions. These experiments, however, were not
designed specifically for the study of vitrinite
reflectance, and therefore, do not contain systematic
or kinetic information on the evolution of reflectance.
This study focuses on experiments at hydrous
conditions and aims at a systematic study of the
development of vitrinite reflectance from a lignite by
artificial maturation, with special emphasis on the
quantification of vitrinite reflectance evolution as a
function of time, temperature, and other factors. This
study first determines the vitrinite reflectance change
with time over a wide range of temperature to
evaluate the role that time and temperature play.
Next the reflection data are fitted to an empirical rate
expression. The results, when compared with a
previous proposed field-calibrated models (Burnham
and Sweeney, 1989), will be used to examine the
validity of laboratory simulation of the development
of vitrinite reflectance in nature. Experiments were

233
234 Wuu-Liang Huang

also run to identify factors other than time and Table 1. Experimental data used to model kinetic expression for
vitrinite maturation
temperature that can significantly enhance or retard
Temperature Pressure Time
the change in vitrinite reflectance. The effects of Run no. (C) (bar) (days) Re %
oxidation states of coals on their reflectance evolution 861 300 500 0.05 0.64
have been studied previously (Pearson and Creaney, 831 300 500 0,334 0.77
1981). Monthioux (1986) reported some data of the 768 300 500 2 0.91
769 300 500 10 1.05
effect of water pressure on the development of 771 300 500 20 1.1
reflectance of humic coals during artificial matu- 745 300 500 35 1.13
ration. Recently, Seewald and Eglinton (1994) have 744 300 500 47 1.09
738 300 500 60 1.13
studied the effect of inorganic reactions on the 719 300 500 80 1.32
development of vitrinite reflectance (Re or %Re). 702 300 500 95 1.21
746 300 500 305 1.42
860 350 500 0.02 0.85
828 350 500 0.042 0.97
799 350 500 0.124 1.07
EXPERIMENTAL PROCEDURE 674 350 500 0.67 1.22
664 350 500 5 1.52
Most of the runs were carried out using a lignite 736 350 500 5 1.41
(% Re = 0.31; HI = 130) from the Penn State coal 668 350 500 10 1.55
688 350 500 15 1.66
Sample Bank, Three additional starting lignites 727 350 500 25 1.76
with different hydrogen indices (HI in mg/g C,,~) 827 400 500 0.021 1.28
798 400 500 0.042 1.36
and maturity (HI = 86, %Re = 0.32,; HI = 260, 657 400 500 0.21 1.52
%Re = 0.60; and HI = 322, %Re = 0.57) were also V1 400 500 I 1.79
used to study the effect of lignite composition. The 671 400 500 2 1.89
711 400 500 4 1.96
experimental solution used was mainly sea water 572 400 500 5 1.97
(Standard Sea-Water P99, Institute of Oceanographic 571 400 500 15 2.13
Sciences, Wormley, Godalming, Surrey, U.K.). Some 573 400 500 30 2.27
V6 400 500 62 2.25
runs used distilled water, acidic solution (0.017 mg/kg 697 450 500 0.67 2.15
of acetic acid in sea water), basic solution (1 M 705 450 500 0.834 2.19
708 450 500 I 2.2
NaHCO3 in sea water), oxygenated sea water (3 wt% 660 450 500 5 2.53
H202) and sea water containing a concentrated Green 722 450 500 23 2.65
River kerogen (18.5 wt% of solid) or Monterey oil
(50 wt% of liquid).
Three major experimental setups were used in this
study. The first set of the experiments was performed
for the kinetic study. Samples were heated isother- sample was heated to the desired temperatures using
mally at 250, 300, 350, 400, and 450c'C and at a a heating rate of ~ 10~'C/min while the pressure was
constant pressure of 500 bars up to 305 days (Table 1) controlled at a constant level. The heating time
using cold-seal pressure vessels (Huang et al., 1986). (30-40 min) required to reach experimental tempera-
The starting lignite powder (25-50 mg, < 40 #m tures is relatively short compared with the run time
grain size) with sea water at a fluid/solid mass ratio (in days) and, therefore, is neglected in calculating the
of 1:1 was electric-arc sealed in a gold capsule (2 cm rate of vitrinite maturation. The experiment was
length, 3 mm diameter, and 0,25 mm wall thickness), terminated by tilting the pressure vessel and dropping
The capsule was then loaded into a cold-seal pressure the capsule into a cooling chamber. The vessel was
vessel and pressurized using argon. The merits of then opened, and the capsule removed, cleaned, and
using a deformable gold capsule are to minimize the weighed. The capsule was punctured near the top
free vapor space within the sample (so-called confined with a hypodermic needle and dried at 50'~C in
system, Monthioux et al., 1985; Monthioux, 1988) vacuum for 20 rain before storing in a desiccator.
and to adjust the sample pressure to equal the Additional confined-pressure experiments were
externally applied pressure during the experiments. performed using the same setup to study the effects
The confining systems experiments for kinetic study of pressure, water activity, and the hydrogen
were mainly conducted at conditions with sea water composition of lignite. These included runs at higher
in the capsule. The confined pressure pyrolysis has pressures (2000 bar), runs without addition of water,
proven to simulate a better natural maturation runs with diluted water activity, and runs with three
process (Monthioux, 1988). other lignite samples having different HI. Exper-
High-pressure experiments were performed in iments to simulate low water activity were conducted
standard size (1' O.D. and 0.25" I.D.) cold-seal using a dry lignite sample in an unsealed gold capsule
pressure vessels equipped with a rapid-quench device pressurized in argon. The sample was directly in
(Huang et al., 1986). A ceramic filler rod was contact with argon during the experiment.
introduced to reduce the temperature gradient within A second set of experiments was performed to
the capsules. The temperature gradient was less than study the effects of the solution chemistry and the
l°C/cm. Temperatures were accurate to + 5~C. The presence of other organic matter. The experiments
 Experimental study of vitrinite maturation
were carried out using a confined pyrolysis similar
to the first set. Each sample, containing 150 mg of
lignite, was loaded with the desired solution (I 50/A)
and/or other solids in gold capsules which were
bound together and placed in a large gold bag
for Dickson-type experiments (Seyfried et al., 1979;
Huang et al., 1986). This design ensures identical
pressure and temperature conditions for runs with
different samples and is ideal for comparing the
variation of pyrolyzates due to the change of starting
lignites and solutions. The experiments were carried
out at 300°C and 500 bar for 10 days.
In order to test the effect of the partial pressure of
gases (e.g., methane and CO2) likely present in source
rocks on the vitrinite maturation kinetics, a third
set of experiments was designed to incorporate
gas into the sample container. This experimental
setup is essentially similar to that of hydrous
pyrolysis (Lewan, 1985). In our experiments we have
introduced different types of gases in the vapor space
of pressure vessels. Experiments were carried out at
300~'C and the vapor pressure of water with
additional partial pressure of methane, CO2 or argon
using 25 ml rigid sample containers (Titanium Parr
vessels, Huang and Longo, 1992). In each exper-
iment, 300 mg of the starting vitrinite sample with 5
ml of sea water were loaded in a Part vessel. Methane
(15 bar), carbon dioxide (15 bar) or argon (15 and 204
bar) were then individually introduced into the vapor
space of the vessel before heating. The total pressure
at the run temperatures is 99 bar for the CO2 run,
98.6 bar for the methane run and 100 bar or 290 bar
for the argon runs. Inside each Parr vessel, a
controlled run using a sealed gold capsule with
starting vitrinite and sea water (1:1 mass ratio) was
also loaded to ensure that the runs with and without
gas partial pressure were performed at identical
temperatures and total pressures for better compari-
son.
In addition, an experiment was carried out in a
fluid-flow pressure vessel in order to study the effect
of fluid flow on the development of vitrinite
reflectance. A cylinder hole with an inside diameter of
0.476 cm and a depth of 2.54 cm was drilled in a
Berea sandstone plug of 1.27 cm O.D., 5.08 cm long.
The hole was filled with lignite sample powder (240
mg) accompanied by a sealed gold capsule containing
lignite powder (25 mg) and distilled water (25/al). The
gold capsule is a controlled run simulating a non-flow
condition. The sandstone plug was placed in the
pressure vessel and distilled water continuously
flowed through at a rate of 1.5 ml/h at 275°C and 177
bar of pore pressure for 7 days.
After each experiment, the solid vitrinite powder
was recovered, polished and the reflectance measured
in random orientation under an oil immersion
objective lens using a standard technique (Bostick,
1979). In general, about 70-80 grains or areas of
vitrinite-like macerals in each polished sample were
measured to generate a mean which is the reported
235
vitrinite reflectance of the run products. The typical
variation of observations for each sample is within
+ 0.1%Ro.
EXPERIMENTAL RESULTS AND DISCUSSION
Kinetic studies o f vitrinite maturation
The results from experiments using a lignite
(%Ro = 0.31; HI = 130) in sea water as the starting
material show that the vitrinite reflectance (%Ro)
progressively increases with time at constant tem-
perature and pressure and that the higher the reaction
temperature for a similar period of run time, the
faster the rate of vitrinite change and the higher the
final Ro value (Fig. 1 and Table 1). The results also
reveal that the rate of Ro change is faster in the initial
stage than in the later stage of an experiment at each
temperature, suggesting that the major effect of time
on vitrinite maturation occurs only at the early stage.
This conclusion is consistent with the observations
found in natural samples from sedimentary basins
that temperature overwhelmingly dominates the
vitrinite kinetics when the time is longer than a few
million years (Price, 1983).
The experimental rate data at each temperature
were found to fit best to an empirical equation in the
form:
Ro=kt" (1)
where Ro is the vitrinite reflectance, k is a rate
parameter, t is time and n is a constant at that
temperature. This study suggests that the overall rate
of vitrinite change does not follow a first-order
kinetic law although the individual parallel organic
reactions may proceed at first-order kinetic rates
(Sweeney and Burnham, 1990). Instead it can be
described better using a power rate law. The reaction
mechanism
3 n
I .o . k
-- /1
/
2It . J /
" ~ a oo°c ,,, t
'r-
°'sr~ . . . . . Sea Water k
¢
0 20 40 60 80 100
Time (Days)
Fig. 1. Experimental results showing vitrinite change as a
function of time at various temperatures. The different
symbols indicate different temperatures, and curves were
calculated using an empirical rate model of the form of
Ro = kt".
236 Wuu-Liang Huang
- 10.8

oo! f _ . / 0 0 °C

-11 0C

~ o Ln k " ~
(in sec.)

=
-0.2'
t -4"~-i ~o~oo°c~
~'-'~oo~c~f
~
....
RO " k t n
-11.6 ~*e
In Ro - I n k + n l n t
40.4
n , 0.078
-0.6 _ ~ i__--~- -12 ~ ~
-4 -2 0 2 4 6 1.3 1.5 1.7 1.9
In t ( d a y s )
1/T x 1000 ° K
Fig. 2. A logarithm plot of the experimental data shows a Fig. 3. Experimental data showing that the temperature
good fit of the data to the proposed rate model. dependence of the rate parameter (k) is consistent with the
Arrhenius relationship.

behind the power rate law is not clear. Judging from
the complexity of the vitrinite composition and
reactions, the empirical fit of the overall rate to the
power law does not offer significant clues about the
reaction mechanism.
Equation (1) can be rewritten by taking logarithms
as:
In Ro = In k + n In t
Plotting this equation on a In Ro vs In t diagram gives
a straight line with a slope of value n. The plotting
of our data for this type of diagram shows a good fit
of the data to straight lines (Fig. 2). Linear regression
of the data shows that these lines have slightly
different slopes (Table 2) for different temperatures
with a mean at 0.078. The variation of the slopes,
however, is within experimental uncertainty. For a
first approximation, the model therefore assumes that
the slope (n value) is independent of temperature. The
kinetic parameters, k, for different temperatures were
calculated using linear regression with constant slope
(0.078).
The dependence of Ro on the temperature by
assuming the relationship (k = Ae "' 7-)can be written
as:
Ro = A e "' Tt"
where A and m are constants and T is temperature in
degrees Kelvin.
Taking the logarithm of the Arrhenius equation
gives:
Ink= -m/T+lnA
The plot of our data on a In k vs 1/T diagram reveals
a linear relationship (Fig. 3), suggesting that the
experimentally determined rate is consistent with the
Arrhenius relationship. The m and A values can be
obtained from least squares linear regression. The
kinetic parameters which best fit the experimental
data are 2578 for m and 32.57 (s 0o78)for A. Equation
(3) can therefore be used as an empirical rate model
(2) for vitrinite maturation if an appropriate field
calibration is done.
In order to extrapolate the high-temperature
experimental data to low-temperature field con-
ditions, it is assumed that there is no significant
change in the n value. The accuracy of the rate model
for predicting vitrinite maturation at diagenetic
conditions, therefore, depends on the validity of this
assumption. The %Ro values calculated from the
experimentally derived rate expression and par-
ameters (Equation (3)) are systematically ~ 0.2 units
lower than those calculated from the widely accepted
model (Easy %Ro, Burnham and Sweeney, 1989). The
cause of this offset is not clear. It probably related to
the initial maturity of the starting lignite used in the
experiments. It may be due also to the effect of early
diagenesis (biogenic and chemical process) of natural
samples which could not be mimicked in our
(3) experimental conditions. Morrow and lssler (1993)
found that the Easy %R~, kinetics predict slightly
higher vitrinite reflectance values in strata of low to
medium maturity. If this observation is generally
true, the offset of vitrinite reluctance ( % R o ) between
the present study and field data may be less
(4) than 0.2%. This suggests that the rate of vitrinite

Table 2. The rate parameters calculated from experimental data using linear regression by assuming
a power rate law (In R . , = n t + In k')
Temperature ( C ) n In k' (s) k (s) r-" n In k (s) k (s)
300 0.085 - 1.155 0.315 0.97 0.078 - t.041 0.353
350 0.090 -0.710 0.492 0.98 0.078 -0.640 0.527
400 0.076 -0.337 0.714 0.95 0.078 -0.356 0.700
450 0.062 -0,088 0.916 0.96 0.078 -0.103 0.902
In = natural logarithm, R,, = vitrinite reflectance (%), n = slope, k' = rate parameter, r = correlation
coefficient, k = adjusted rate parameter using a mean value of n (0.078).
 Experimental study of vitrinite maturation 237

~2.5 ~ ThisStudy / " ~ y

--- BurnhamandSweeney / / / ,',~ I 2.5 ........... "1"7~;o~-""
2.0 09a9) ~ , ~ 1"0°_ I 2.01 ."
0-1°C/my~,"/ ,,~C/myfJ I "'°

1.5 / Z * ~ / 1.5 " ~ " "1"50"°-C'

C----Z125o,
1.0 ,.0 . . . . . . .
100oc

"E o.5 0.5 ~ ....... -r~;;6---

o " o , , , , , I-B
0 50 100 150 200 250 0 50 100 150 200 250 300
Temperature °C Time (my)
Fig. 4. Comparison of the development of vitrinite reflectancebetween the present model (Equation (5b);
solid curves) and the model of Easy %Ro (dashed curves). (A) Ro vs temperature at heating rates of 0.1
and 1000°C/millionyear. (B) Ro vs time at constant temperatures from 75°C to 175°C.

reflectance development at experimental conditions is
similar to that found in nature. However, to improve
the present model, the calculated Ro from the
empirical Equation (3) was adjusted by an offset of
0.2%Ro. The adjustment is acceptable if we take the
experimental errors and the uncertainty of tempera-
ture extrapolation from experimental to natural
conditions into account.
The refined equation is:
Ro = B + Ae-'~'~t"
or
Ro = 0.2 + 32.57 exp( -- 2578/T)t °°78
where Ro=vitrinite reflectance (%), B = o f f s e t
(e.g. 0.2%Ro), T = temperature (degree Kelvin) and
t = time (s). After adjustment, Equation (5b) predicts
the development of vitrinite reflectance at a rate
reasonably consistent with that calculated from the
previous kinetic model (Burnham and Sweeney, 1989;
Sweeney and Burnham, 1990) over a wide range of
However, for more accurate prediction of organic
maturation, particularly at high maturity (%Ro
> 1.5), the parameters (B, A, m and n in Equation
(5)) require calibration using a wide variety of field
data.
Effects o f other geological parameters
Experiments were also performed to study the
effects of starting lignite composition (in terms of HI),
pressure, water activity, pH, Eh of pore fluids, fluid
(5a) flow, presence of kerogen or oil and the partial
pressure of methane or CO2 on the development of
vitrinite reflectance. The results show that the higher
(5b) the original hydrogen index, the slower the rate of
vitrinite reflectance change, particularly at the early
stage of maturation (%Ro < 1; Fig. 5). This effect
becomes less pronounced with increasing maturation.
The rate parameter k (s) at 300°C for HI = 86, 130,
260 and 322 mg/g Cots are, respectively, 0.345, 0.353,
0.325 and 0.291. This study experimentally confirms
1.2

geological heating rates from 0.1°C/my to 10°C/my

(Fig. 4a). The agreement between these two models
is good for the reflectance range up to 1.5%Ro values
and the heating rate between 0.1°C/my and 10°C/my,
0.8
whereas a significant discrepancy exists for higher Ro
or faster heating rate. Figure 4b shows a similar
comparison by plotting the Ro evolution matured ~r 0.6

under isothermal conditions as a function of time. . ? 3o0 I

The diagram also shows the duration within which
the time variable becomes insignificant. For example,
at a constant temperature of 100°C, 80% of the Ro 0.2 I r I J I I J I J I I
change occurs within first 10 million years (my) of 0 1 2 3 4 5 6 8 9 10 11 t2
maturation, whereas the remaining 20% of the Time (Days)
change takes another 300 my to complete. This Fig. 5. Experimental results showing the effect of hydrogen
simple equation (Equation (5b)), to a first approxi- index on the rate of vitrinite change during artificial
mation, can be used to substitute for the complex maturation of three lignites with different hydrogen index
kinetic model (Easy %Ro) to calculate vitrinite (HI) at 300°C and 500 bar. Symbols: circles = runs with
starting lignite of HI 86; triangles = runs with starting
maturation within sedimentary basins. This simple lignite of HI 260; squares = runs with starting lignite of HI
rate equation is particularly easy to incorporate into 322. The open symbols indicate the Ro of the three starting
the algorithm of a basin modeling program. lignites.
238
sea Water O_,1~ - - / - ~ /
=o
1.5
~ l~ry but isolated
(sealedcapsule)
from Argon
~ o p e n to argon
f (opencapsule)
350°C,
® 0.5
"E
Starting
lignite
>
Time (Days)
Fig. 6. Experimental data comparing results in hydrous
confining system, anhydrous confining system and anhy-
drous open to argon gas system on the rates of vitrinite
reflectance change. Symbols: solid circles = runs with sea
water in closed system; solid squares = runs with no added
water in closed system (but some water may release during
lignite maturation); open circles = runs with no added water
and samples in contact with Ar gas.
the close correlation between the high original
hydrogen index of vitrinite-like macerals and their
reflectance suppression found in natural samples
(Hutton and Cook, 1980; Price and Baker, 1985;
Wenger and Baker, 1987; Raymond and Murchison,
1990; Lo, 1993).
The results also show that vitrinite reflectance
increases at a much slower rate in the system open to
argon (Fig. 6) than under closed hydrous conditions.
The experiments were conducted using a lignite
sample with no added water in unsealed gold capsules
loaded in a pressure vessel using argon as the pressure
medium. Two special conditions used in these
experiments likely account for the retardation of
reflectance evolution: (1) the unsealed capsules may
allow the pyrolysis products to leave the system
(i.e. in an open system) and (2) the contact of the
sample with a large amount Ar gas may dilute
the partial pressure of the products in the system. The
retardation rather than enhancement of the reaction
in the open system suggests that the pyrolysis
products, most likely water, can be involved in the
maturation of vitrinite. Although the low water
activity that occurred in the experiments may not be
encountered in nature and the proposed retardation
mechanism has not been confirmed, future study in
this direction may warrant the unveiling of an actual
mechanism which will be useful for identifying
conditions causing suppression of vitrinite reflectance
found in a natural system. The role of Ar in the
organic maturation was also noticed but interpreted
using a different mechanism by Landais et al. (1994)
who emphasized the role of the pressurizing medium
(e.g. argon) in the hydrostatic pressure effect during
organic maturation.
In contrast, the vitrinite reflectance in runs with no
added water in closed capsules (i.e. sample is isolated
Wuu-Liang Huang
from Ar gas) under a confining pressure at 500 bar
(Fig. 6) increases at a rate only slightly lower than
those in runs with added water in closed capsules. It
seems that water or other pyrolysis products
generated during the early stage of lignite pyrolysis in
closed capsules is sufficient to maintain their activities
to allow vitrinite reflectance to change at a rate
similar to that at hydrous confining conditions. This
500 bars interpretation is consistent with experiments per-
formed on Woodford kerogen by Landais et al.
(1994) which show that excess water in confining
pyrolysis experiments does not significantly influence
organic matter maturation. However, Hill et al.
(1994) showed that confined pressure (similar to the
dry, closed system in this study) has some effect on
the development of vitrinite reflectance. The depar-
ture of water pressure (and perhaps, water activity)
from total pressure in these experiments may affect
the rate of vitrinite evolution.
The results, however, show that there is no
significant difference on the rate of vitrinite
reflectance change as the water pressure increases
from 100 to 500 to 2000 bar. Several runs at 300"C
show that the rates of vitrinite development at 500
and 2000 bar water pressures are similar (within the
experimental uncertainty) over a range of maturity up
to % Ro = 1.4 (Fig. 7). The experiments at 100
bar water pressure (see Fig. 9) also show negligible
pressure effect. These results are consistent with
the artificial maturation data that show water
pressure playing a minor role in vitrinite development
(Monthioux, 1986) and in the generation kinetics
of Bakken shale kerogen (Freund et al., 1993).
However, Price and Wenger (1992) and Carr (1991)
reported that pressure can drastically delay kerogen
maturation. McTavish (1979) and recently, Hao et al.
(1995) reported a significant retardation of the
evolution of vitrinite reflectance in overpressure
zones. However, because the retardation of organic
maturation in overpressure zones does not always
occur, Hao et al. (1995) used the concept of threshold
pressure (e.g. 1077 bar) proposed by Price and
Wenger (1992) to explain these observations. Our
21 . . . . . ]
f
500 bars
o= i Je ..... -
~c O0 b a r s
= S e a Water
"~ 0.5~.. 300"C
'~i) S a ir~g Ro
L _ _ =
I~I 0 50 100 150 200 250 300
Time (Days)
Fig, 7. Experimental results showing the effect of pressure.
Symbols: solid circles = runs at 500 bar; solid squares =
runs at 2000 bar.
 Experimental study of vitrinite maturation
experimental results show that no significant retar-
dation occurs at pressures up to 2000 bar water
pressure which are about twice the maximum
overpressure reported in Hao et al. (1995). Khavari
Khorasani and Michelsen (1994), on the other hand,
show that the pressure imposed on the vitrinite in
shale is mainly lithostatic and negligibly different
between normal and overpressure zones. Therefore,
the observed difference in the vitrinite evolution
between these two zones (Hao et al., 1995) may not
be ascribed to the effect of pressure.
It seems that there is still a considerable
discrepancy concerning the role of pressure in the
kinetics of vitrinite maturation in the literature. This
discrepancy may be attributed to the compositional
variation of the studied organic matter or the
different reaction mechanism dominating in artificial
vs natural maturation. It may also reflect our lack of
understanding in the maturation process of organic
matter. Landais et al. (1994) have reviewed and
systematically studied the effects of pressure on
organic matter maturation. These authors found that
the pressure effect on organic maturation is much
more complicated than previously thought. Hill et al.
(1994) also experimentally found that pressure affects
coal maturation. Both of these studies conducted
experiments in a dry, confined-pressure system in
contrast to the hydrous, confined-pressure system of
the present study. More systematic studies of a
variety of kerogens and coals either from naturally or
artificially matured samples are required to resolve
the problem.
Other diagenetic parameters simulated in these
experiments, such as fluid chemistry (pH and Eh),
fluid flow and the presence of oil or other types of
kerogen, appear to have no significant effect on the
vitrinite kinetics. Figure 8 shows that %Ro for all
runs, except those with a higher hydrogen index and
low water activity, increases from 0.31 to near 1.02 at
the end of each experiment. The slight variation of
1.2
Lignite matured at 300 °C and 500 bars for 10 days
1.1
d 1
O11 H202 NeHCO3 2000
0.g bars [ ]
Typa-I Acetic 500 High
kerogen acid bars Hie
~" 0,8
"~ 0.7 All runs with sea water
Dry
argon
o.e
Geological Parameters
Fig. 8. Comparison of the effect of different geologicfactors
on vitrinite reflectance change after heating the lignite
sample at 300°C and 500 bar for 10 days. The length of
boxes indicates the standard deviation of the individual
vitrinite measurements for each run product.
239
All runs at 300°(; and vapor pressure (84 bars)
plus
1.6
Methane CO2 Argon Argon
d 15 bars 15 bars 15 bars 204 bars
1.2
Oo 0o 0~ e~
~_ 0.8
c 0.4
:~
Fig. 9. Experimental results showing the effect of different
gases. Symbols:solid circles = runs with gas partial pressure
as indicated; open squares = control runs with sample
isolated in gold capsules without contact with the gas.
%Ro values around 1.02 is within the uncertainty of
the experiments. In contrast, Seewald and Eglinton
(1994) experimentally showed that the presence of
dissolved Mg can significantly enhance the rate of
vitrinite reflectance change. They attribute this
effect to the acidity of the studied solution resulting
from dissolved Mg. Their interpretation of the
effect of solution pH is not consistent with the results
from the present study. Further detailed study is
required to understand fully the effects of solution
chemistry.
The results based on limited data show that fluid
flow does not significantly affect the rate of vitrinite
reflectance change, The results show that the
reflectance of vitrinite (%Ro) in run products at
275°C in 7 days evolves from 0.31, respectively, to
0.75 and 0.82 at dynamic flow (1.5 ml/h) and static
conditions.
The results from gas charged experiments (Fig. 9)
also show that the partial pressures of CH4, CO2 and
argon have no significant effect on vitrinite reflec-
tance change. This has been tested experimentally up
to 15 bar of CH, and CO, pressures and up to 204
bar of argon pressure. The results from runs with
argon suggest that in the presence of sufficient water,
in contrast with the low water activity experiments
(Fig. 6), argon does not contact directly with the
sample and, therefore, does not significantly lower
the activity to the degree where retardation can occur.
S U M M A R Y AND C O N C L U S I O N S
An empirical rate expression for the evolution of
vitrinite reflectance as a function of temperature and
time has been derived experimentally by directly
measuring the reflectance change of an immature
lignite (HI = 130). The evolution rates of vitrinite
reflectance, which are rapid in early stages and
drastically slower in later stages, can be modeled
using a power law rate expression. This observation
confirms that the development of vitrinite reflectance
240 Wuu-Liang Huang
is controlled more by t e m p e r a t u r e t h a n time. The
empirical model is reasonably consistent with the
previously reported model which was derived
indirectly from the chemical kinetic reaction of
organic t r a n s f o r m a t i o n ( B u r n h a m a n d Sweeney,
1989) a n d has been verified by some field testing
( M o r r o w a n d lssler, 1993). This implies that the
m e c h a n i s m for vitrinite reflectance d e v e l o p m e n t at
experimental conditions may not differ significantly
from those f o u n d in nature. The rate expression,
therefore, m a y be used to calculate vitrinite
reflectance for c o n s t r a i n i n g basin thermal history
models if the kinetic parameters are calibrated
properly against a wide variety of field data.
This simple rate e q u a t i o n is particularly easy to
incorporate into the algorithm of a basin modeling
program.
This study has experimentally confirmed that the
original HI of vitrinites can determine significantly
the evolution rate of their reflectance. The results
d e m o n s t r a t e the i m p o r t a n c e of characterizing the
c o m p o s i t i o n o f the original, i m m a t u r e vitrinite for a
m o r e accurate prediction of organic m a t u r a t i o n using
Ro. However, it appears that other diagenetic
parameters, such as water pressure, m e t h a n e a n d CO2
partial pressures, fluid chemistry and the presence of
oil or other types of kerogen, do not significantly
affect the rate of vitrinite reflectance change. This
confirms t h a t the evolution o f vitrinite reflectance,
unlike inorganic reactions, is not significantly affected
by the fluid conditions.
Acknowledgements--The permission to publish this paper
granted by Exxon Production Research Company is
appreciated. The author wishes to thank his colleague G. A.
Otten for assistance in the hydrothermal laboratory and
Karl Schwab of Geo-Strat Inc. for the measurements of
vitrinite reflectance. The lignite samples were kindly
supplied by our colleagues D. J. Curry and H. B. Lo. The
critical reviews of the paper by D. J. Curry and E. J.
Novotny of Exxon Production Research Company, R. W.
Stanton of U. S. Geological Survey, and an anonymous
reviewer are greatly appreciated.
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