Geochimica et Cosmochimica Acta, Vol. 62, No. 9, pp.

1599 –1617, 1998

Copyright © 1998 Elsevier Science Ltd
Pergamon Printed in the USA. All rights reserved
0016-7037/98 $19.00 1 .00
PII S0016-7037(98)00000-0

Laboratory and theoretical constraints on the generation and composition of natural gas
JEFFREY S. SEEWALD,* BRYAN C. BENITEZ-NELSON, and JEAN K. WHELAN
Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543, USA

(Received September 12, 1996; accepted in revised form January 20, 1998)

Abstract—Hydrous pyrolysis experiments were conducted at 125 to 375°C and 350 bars to constrain factors
that regulate the generation and relative abundance of hydrocarbon and nonhydrocarbon gases during thermal
maturation of Monterey, Eutaw, and Smackover shale. Thermogenic gas was generated at temperatures as low
as 125°C and increased in abundance with increasing temperature. The relative abundance of individual
hydrocarbons varied substantially in response to increasing time and temperature reflecting the chemical
processes responsible for their formation. The hydrocarbon fraction of low maturity gas produced via primary
cracking of kerogen was composed predominantly of methane. With increasing thermal maturity, the onset of
bitumen generation produced longer-chain hydrocarbons causing a decrease in the relative abundance of
methane. At high levels of thermal maturity, the absolute and relative abundance of methane increased due to
decomposition of bitumen.
In all experiments at all temperatures, carbon dioxide was the most abundant volatile organic alteration
product. Carbon dioxide was produced directly from kerogen at low thermal maturity and via the decompo-
sition of bitumen and/or kerogen at high thermal maturity. During early stage alteration, kerogen likely
represents the dominant source of oxygen in carbon dioxide while at high thermal maturities water may
represent an abundant and reactive oxygen source. Hydrogen released during the disproportionation of water
is likely consumed during hydrocarbon generation. Theoretical reaction path modeling suggests that the
precipitation of calcite may effectively remove carbon dioxide from natural gas if a source of Ca is available
within the rock. Thus, carbon dioxide-rich natural gas may be relatively pristine while methane-rich natural
gas may reflect the occurrence of secondary reactions involving inorganic sedimentary components.
Kinetic analysis of the experimental data indicates a narrow range of activation energies for the generation
of C1-C4 hydrocarbons from the Monterey, Smackover, and Eutaw shales. Carbon dioxide generation from the
Monterey and Eutaw shales is accounted for by a substantially broader range of activation energies.
Application of these data to predict gas formation at temperatures and time scales typical of subsiding
sedimentary basins suggests that C1-C4 generation is restricted to relatively high temperatures while carbon
dioxide generation occurs at both low and high thermal maturities. Thus, in contrast to the bulk of C1-C4
generation which is predicted to occur after peak bitumen generation, production of carbon dioxide will occur
before, during, and after the generation of liquid hydrocarbons. Copyright © 1998 Elsevier Science Ltd

1. INTRODUCTION products are often obscured. Laboratory heating experiments

Thermal maturation of sedimentary organic matter involves
numerous chemical transformations that result in the produc-
tion of volatile hydrocarbon and nonhydrocarbon alteration
products. In addition to forming economic deposits, thermo-
genic gases influence many geologic processes associated with
the transport and accumulation of petroleum in sedimentary
basins. In particular, carbon dioxide, a quantitatively important
component of natural gas, not only represents a major contam-
inant from an economic perspective, but also influences reser-
voir porosity and permeability during sediment diagenesis due
to its weak acid properties and the ability to form carbonate
minerals. Understanding fundamental processes that regulate
the generation of organically derived gaseous products is there-
fore essential to constrain factors influencing the accumulation
of oil and gas in sedimentary basins.
Field studies have provided us with a wealth of data regard-
ing the occurrence and composition of natural gas. Because
natural systems are inherently complex, processes that regulate
the timing, amounts, and composition of organic alteration
*Author to whom correspondence should be addressed (jseewald@
whoi.edu).
1599
are an effective tool for constraining organic alteration pro-
cesses under well-constrained physical and chemical condi-
tions. The generation of oil and natural gas has been studied
using a variety of laboratory techniques including open-system
dry pyrolysis (Espitalié et al., 1977; Burnham et al., 1987),
closed-system dry pyrolysis (Monthioux et al., 1985; Schenk
and Horsfield, 1993), and closed-system hydrous pyrolysis
(Lewan, 1993a). The generation rates and composition of or-
ganic alteration products are highly dependent on the simula-
tion technique employed. In particular, hydrous pyrolysis ex-
periments have demonstrated that in addition to influencing the
amounts and composition of liquid hydrocarbons, the presence
of liquid water plays an important role in the generation of
volatile organic alteration products (Lewan, 1993b, 1997). The
reasons for this are numerous and likely include changes in
reaction mechanism and the possible role of water as a source
of hydrogen and oxygen for the formation of organic alteration
products such as methane and carbon dioxide (Hoering, 1984;
Siskin and Katritzky, 1991; Helgeson et al., 1993; Lewan,
1993a,b, 1997; Price, 1993; Seewald, 1994, 1996; Stalker et al.,
1994). Because, liquid water is an abundant phase in almost all
sedimentary basins and is generally present in petroleum res-
ervoirs during the conversion of oil to natural gas, it is essential
1600 J. S. Seewald, B. C. Benitez-Nelson, and J. K. Whelan

that the role of water during the thermal maturation of sedi-

mentary organic matter to produce volatile alteration products
such as methane and carbon dioxide be considered.
Except for a few notable exceptions (Andresen et al., 1994;
Lewan, 1997), hydrous pyrolysis studies have focused on con-
straining the generation of hydrocarbons from kerogen and
have provided only limited data for the generation of organi-
cally derived carbon dioxide. Quantification of carbon dioxide
generation during hydrous pyrolysis is complicated by the fact
that multiple sources and sinks for carbon dioxide may exist.
For example, determination of organically derived carbon di-
oxide must account for dissolution of inorganic carbonate min-
erals during an experiment. Alternatively, carbon dioxide may
precipitate as carbonate minerals if sufficiently high dissolved
concentrations are attained. Moreover, due to the high solubil-
ity of carbon dioxide in water, underestimates of carbon diox-
ide production may be obtained from chemical analysis of the
gas phase alone during hydrous pyrolysis (Lewan, 1997). Ac-
cordingly, experiments conducted during this study were de-
signed to circumvent these problems and provide data con-
straining the generation of organically derived carbon dioxide
and low molecular weight volatile hydrocarbons as a function
of time and temperature. These data are used to develop chem-
ical and kinetic models that account for the generation and
composition of thermogenic gases in sedimentary basins.

2. METHODS
2.1. Sample Description and Preparation
Samples of Monterey, Eutaw, and Smackover shales were utilized
for this study (Table 1). The Monterey Shale is a Miocene sediment
collected at an outcrop in Naples Beach, California, USA. The sample
is an unweathered lenticularly laminated organic-rich (20.6 wt% TOC)
claystone that is thermally immature (bitumenite reflectance 5 0.25%
expressed as Ro). The Eutaw Shale is a Cretaceous sediment obtained
from core cuttings recovered at a depth interval of 3011 to 3021 m from
the Hampton/Nelson Ball well in Pike County, Mississippi, USA. It is
a quartz-rich, organic lean shale (0.97 wt% TOC) with measured
vitrinite reflectance of 0.45% Ro, a hydrogen index of 60, and a Tmax
of 428°C. The Smackover Shale is a Jurassic sediment obtained from
core cuttings recovered at a depth of 3260 m from the Amareda Scotch
Well #1 in Clark County , Alabama, USA. This shale is also quartz-rich
and organic-lean (0.92 wt% TOC) with a measured vitrinite reflectance
of 0.52% Ro, a hydrogen index of 67, and a Tmax of 439°C. Based on
the hydrogen index, Tmax values, and petrographic observations, or- not produce detectable amounts of low molecular weight hydrocarbons
ganic matter in the Eutaw and Smackover shales is predominantly of indicating the effective removal of sorbed gases.
terrigenous origin that corresponding to a type-III kerogen (Espitalié et
al., 1984). Elemental analysis indicates that the Monterey Shale con- 2.2. Experimental Apparatus and Conditions
tains type II-S kerogen (Table 1).
In this study our primary goal was to constrain the rate and extent of Except for experiment MS15, all experiments were conducted in 316
chemical reactions responsible for the generation of gaseous products. stainless steel tubing reactors with a 20 cm3 internal volume (Fig. 1).
Accordingly, to minimize physical processes associated with expulsion The tubing reactor permits fluid samples to be withdrawn from the
of produced gases, the starting rocks were ground in a disc mill until the pipe-bomb at the temperature and pressure of an experiment allowing
entire sample passed through a ,125 mm sieve. To remove existing fluid chemistry to be monitored as a function of time. The experiments
hydrocarbons, ground samples of the Eutaw and Smackover shales described here are in many ways similar to the hydrous pyrolysis
were Soxhlet extracted in a 93:7 dichloromethane/methanol mixture for experiments described by Lewan (1993a) in that bulk rocks are heated
48 h while the Monterey Shale was sequentially extracted by sonic in the presence of excess liquid water, but there are important differ-
disruption for 9 min in methanol, a 1:1 mixture of dichloromethane/ ences. For example, in our experiments the reactor vessel is filled
methanol, and dichloromethane. Except for experiments MS1 and completely with liquid water precluding the existence of a vapor
MS2, all starting ground shale samples were treated with 10% hydro- headspace. In addition, to minimize the possibility that the amounts of
chloric acid at 40°C for 2 h following solvent extraction to remove generated gases would exceed their aqueous solubility and form a
inorganic carbonate minerals. Coulometric analysis for inorganic car- separate phase, only 1.0 g of bulk rock was used for each experiment
bon following this treatment revealed carbonate was completely re- resulting in fluid/rock mass ratios considerably higher than those typ-
moved. Thus, carbon dioxide generated during the experiments is ically associated with conventional hydrous pyrolysis. The measured
organic in origin and not the result of carbonate mineral dissolution. concentrations of gases remained below their aqueous solubilities at the
Sonication of the ground, solvent-extracted, and acid-treated rocks in conditions of all experiments (Bonham, 1978; Price, 1981; Bowers and
water at 90°C for 15 min while purging with a helium carrier gas did Helgeson, 1983; Johnson et al., 1992). Although the presence or
 Generation and formation of natural gas
Fig. 1. Tubing reactor utilized for this study.
absence of an oil phase could not be determined during an experiment,
the high fluid/rock mass ratios employed minimized the potential for
the formation of such a phase due to the relatively high solubility of oil
in water at the temperatures of these experiments (Price, 1981), espe-
cially for the organic-lean Smackover and Eutaw shales. In each
experiment it was assumed that all gases were present as dissolved
species in the aqueous phase allowing determination of the absolute
amounts generated from analyses of the aqueous phase alone. The
absence of a vapor headspace in our experiments is important since
reactions are limited to those involving aqueous species and solid
phases. In contrast, conventional hydrous pyrolysis may involve reac-
tions occurring in oil, water, gas, and solid phases.
Prior to heating, the tubing reactor was evacuated with a vacuum
pump and partially filled with Ar-purged distilled water to ensure that
the rock was wet during the 30 min heat-up process. Once at the desired
temperature, the tubing reactor was completely filled with water and
pressurized to 350 bars. Because the specific volume of water increases
with increasing temperature at constant pressure, the fluid/rock mass
ratio was lower in the high-temperature experiments. Temperature was
monitored (62°C) with a thermocouple at each end of the tubing
reactor to ensure there were no thermal gradients. Experiments utilizing
the Monterey and Smackover shales were conducted isothermally for
approximately 170 h. In contrast, the Eutaw Shale investigation was
conducted by maintaining the tubing reactor at a constant temperature
for a selected period of time before rapidly increasing the temperature
to a new value. At each temperature condition gas generation was
monitored as a function of time.
During the course of an experiment, fluid samples were withdrawn
into glass gas-tight syringes and analyzed for the concentration of
dissolved gases. An internal 10 mm steel mesh filter ensured particle
free fluids. Pressure was maintained during the sampling process by
1601
pumping Ar-purged distilled water into one end of the tubing reactor
while the fluid sample was removed from the opposite end. The
sampling process was performed rapidly (1 to 2 min) to avoid dilution
of the fluid samples with the freshly injected water. The absolute
amounts of generated gases in subsequent samples were corrected for
gases removed during earlier sampling events.
Experiment MS15 differed substantially from those described above
and was intended to preclude precipitation of carbonate minerals that
could act as a sink for organically derived carbon dioxide. Instead of
containing deionized water as the starting fluid, this experiment con-
tained 55 g of a Na-Mg-Cl fluid of seawater salinity (Table 3). In
addition, 1.52 g of Monterey Shale and 0.51 g of finely ground pure
quartz were added to the reaction cell. The Mg-rich fluid and quartz
result in the maintenance of low in-situ pH conditions as a result of talc
precipitation according to the reaction:
3Mg 11 1 4SiO 2~qtz)14H2O(l)5Mg3Si4O10(OH)2(s)16H1 (1)
(Saccocia and Seyfried, 1991). By maintaining low in-situ pH, the
solubility of calcite is considerably enhanced according to the reaction:
Ca 11 1 H 2CO 3~aq)5CaCO3(s)12H1 (2)
relative to the deionized water experiments. Experiment MS15 was
conducted at 225 to 375°C and 350 bars in a similar fashion to the
Eutaw Shale experiment in that temperature was maintained at a
constant value before incremental increases at selected time intervals.
Because the critical point of the saline fluid used in experiment MS15
is 407°C (Bischoff and Rosenbauer, 1985) this experiment was con-
ducted under subcritical conditions.
Owing to the low pH and corrosiveness of the high chlorinity fluids
in experiment MS15, a chemically inert Au and Ti flexible-cell hydro-
thermal apparatus was used (Seyfried et al., 1987). This equipment also
allows external control of pressure ensuring a single liquid phase inside
the reaction cell. An important difference compared to the tubing
reactor experiments, however, is that water is pumped into the pressure
vessel volume surrounding the reaction cell to maintain pressure during
sampling. Accordingly, the reaction cell fluid is not diluted during
sampling. However, as result of fluid sampling, the fluid/rock mass
ratio decreases during the experiment.
2.3. Analytical Procedures
Fluid samples were analyzed for the dissolved concentra-
tions of carbon dioxide, C1-C4 hydrocarbons, H2, and H2S.
Dissolved carbon dioxide and C1-C4 hydrocarbons were ana-
lyzed by injecting fluid samples into a purge and trap apparatus
interfaced directly to a gas chromatograph equipped with flame
ionization and thermal conductivity detectors. The fluid sam-
ples were acidified with 1 mL of 25 % phosphoric acid in the
purge cell to ensure complete evolution of dissolved carbon
dioxide. Separation of gases in the gas chromatograph was
achieved with either a porapak-Q packed column or a po-
raplot-Q megabore capillary column. Following a headspace
extraction, dissolved H2 concentrations were determined in
selected experiments using a gas chromatograph equipped with
a thermal conductivity detector and a 5 Å molecular sieve
packed column. Dissolved H2S was determined gravimetrically
by acidifying the fluid sample with 25 % phosphoric acid and
precipitating the evolved H2S as Ag2S in a 3 wt% AgNO3
solution. The concentrations of dissolved Na, Ca, K, Mg, and
Cl in experiment MS15 were analyzed by ion chromatography.
Careful accounting of all fluid removed and added to the
tubing reactor allowed the absolute amounts of generated prod-
ucts to be calculated from the dissolved concentrations, tubing
reactor volume, and the mass of rock in each experiment. The
specific volumes of water at the temperature and pressure of
each experiment were calculated using the equation of state of
1602 J. S. Seewald, B. C. Benitez-Nelson, and J. K. Whelan
 Generation and formation of natural gas
Haar et al. (1980). Analytical uncertainties are estimated to be
,5 % for all dissolved species.
After completion of each experiment the liquid reactants
were removed by sequentially pumping 30 mL of methanol and
dichloromethane through the tubing reactor at room tempera-
ture. The solid reactants were then removed from the tubing
reactor, dried in air at 40°C, and solvent extracted by sonic
disruption as described above. This extract was combined with
the tubing reactor rinses and back-extracted with distilled H2O.
The combined extract, referred to here as total bitumen, in-
cludes expelled oil and differs from bitumen measured during
conventional hydrous pyrolysis which is limited to products
retained in the source rock (Lewan, 1993a). Quantification of
the total bitumen extract from the Monterey Shale experiments
was performed by thin-layer chromatography with flame ion-
ization detection (TLC-FID) according to the methods of
Karlsen and Larter (1991). The TLC-FID technique is not
particularly precise and accuracy suffers due to uncertainties
1603
associated with the choice of standards. This is especially true
for analysis of bitumen containing abundant asphaltenes since
FID response is strongly dependent upon asphaltene composi-
tion. Accordingly, uncertainties associated with these data are
estimated at approximately 30 %. Insufficient bitumen extract
from the Eutaw and Smackover shale experiments precluded
this analysis.
Elemental analyses (CHNSO) were performed on all starting
rocks and solid alteration product. Inorganic carbonate was
determined on a Coulometrics carbon analyzer. Because inor-
ganic carbon abundances were below detection (,0.03 wt%) in
all starting rocks and alteration products, total organic carbon
(TOC) is equivalent to the total carbon determined by elemen-
tal analysis. The starting rock and solid alteration products for
the Monterey Shale experiments were demineralized by HCl
and HF acid digestions (Eglinton and Douglas, 1988) to isolate
kerogen. The isolated kerogens from all experiments except
MS15 were treated with CrCl2 and HCl to remove iron sulfides
(Canfield et al., 1986; Acholla and Orr, 1993) before being
analyzed for their elemental composition. Similar kerogen iso-
lations for the Eutaw and Smackover shales were not possible
owing to the low organic matter content of these rocks.
3. RESULTS
3.1. Volatile Products and Generated Bitumen
Thermal maturation of organic-bearing sedimentary rocks is
characterized by the generation of gaseous alteration products,
the extent and rate of which are strongly dependent on time and
temperature (Tables 2–5; Figs. 2–5). For example, the amount
of dissolved methane generated during heating of Monterey
Shale for 170 h increased from 0.0036 mmole/g TOC at 125°C
to 2.9 mmole/g TOC at 375°C. Continued reaction at 375°C
resulted in the eventual generation of 5.8 mmole/g TOC meth-
ane after 1875 h. Production of methane during heating of the
Smackover and Eutaw shales showed a similar temperature
dependence, although at a given temperature and reaction time
the absolute amounts of methane were considerably less than
1604 J. S. Seewald, B. C. Benitez-Nelson, and J. K. Whelan

Fig. 2. Amounts of low molecular weight organically derived alteration products generated as a function of time and
temperature during hydrous pyrolysis of Monterey Shale for 170 h (symbols). The dashed lines indicate predicted gas
generation during the experiments using a parallel reaction model and kinetic parameters retrieved from the experimental
data (see text).

the Monterey Shale. The absolute abundance of ethane, pro-

Fig. 3. Amounts of low molecular weight organically derived alter-
ation products generated as a function of time and temperature during
Monterey Shale experiment MS15 (symbols). The dashed lines indicate
predicted gas generation during the experiments using a parallel reac-
tion model and kinetic parameters retrieved from the experimental data
(see text).
pane, and butane also increased with increasing temperature,
but remained below that of methane in all experiments.
Variations in the absolute abundance of C1-C4 hydrocarbons
were accompanied by large changes in their relative abundance
in the hydrocarbon fraction of generated gas (Fig. 6). During
heating of Monterey Shale, methane abundance constituted
approximately 90 mole % of the C1-C4 hydrocarbons at 125 to
200°C before systematically decreasing to values as low as 58
mole % at 325°C. At temperatures .325°C, the relative abun-
dance of methane increased to a final value of 68 mole % after
1875 h of reaction at 375°C. Almost identical variations in the
relative abundance of methane with respect to C1-C4 hydrocar-
bons were observed during the Eutaw Shale experiment except
that the initial decrease in wt% methane did not occur until a
temperature of 325°C. Because bitumen in the initial shales
used for these experiments was removed by solvent extraction
prior to heating, generation of methane-rich gas at low temper-
atures prior to the onset of bitumen generation is consistent
with derivation via the primary cracking of kerogen. Subse-
quent decreases in mole % methane are likely associated with
the generation of bitumen containing high molecular weight
 Generation and formation of natural gas 1605

Fig. 4. Amounts of low molecular weight organically derived alteration products generated as a function of time and
temperature during hydrous pyrolysis of Smackover Shale for 170 h (symbols). The dashed lines indicate predicted gas
generation during the experiments using a parallel reaction model and kinetic parameters retrieved from the experimental
data (see text).

compounds. Indeed, decreases in the wt% methane during the
Monterey Shale experiments coincided with the onset of bitu-
men generation which increased substantially at 200°C and
peaked at 275°C (Fig. 7). Although bitumen generation was not
quantitatively monitored during the Eutaw Shale experiments,
Fig. 5. Amounts of low molecular weight organically derived alter-
ation products generated as a function of time and temperature during
hydrous pyrolysis of Eutaw Shale (symbols). The dashed lines indicate
predicted gas generation during the experiments using a parallel reac-
tion model and kinetic parameters retrieved from the experimental data
(see text).
the decrease in wt% methane at 325°C suggests higher tem-
peratures may be required for peak bitumen generation. The
rate of petroleum generation has been shown to correlate pos-
itively with kerogen S content (Hunt et al., 1991). Thus, lower
temperatures for bitumen generation from the Monterey Shale
are consistent with its relatively high S content.
In contrast to the Monterey and Eutaw shales, gas generation
during the low temperature Smackover Shale experiments was
characterized by lower mole % methane in the hydrocarbon
fraction (Fig. 6). With increased temperature, however, the
relative abundance of methane increased continuously reaching
a value of 82 mole % at 360°C. The absence of a methane-rich
gas in the low-temperature Smackover Shale experiments may
reflect a compositional difference in the kerogen due to varia-
tions in the sources of organic matter in these sediments and/or
variations in their digenetic histories prior to collection.
The relative abundance of methane in the hydrocarbon frac-
tion increased continuously during maturation at temperatures
.325°C in all experiments indicating the production of meth-
ane-rich gas at high thermal maturity. The progression with
increasing temperature from a system generating predomi-
nantly bitumen to one producing gas is also reflected in the
sharp increase in the gas/bitumen volume ratio at 275°C (Fig.
7). Decreases in the TOC content of the Monterey Shale at
temperatures .325°C account for only a minor fraction of the
carbon contained in the generated gas suggesting decomposi-
1606 J. S. Seewald, B. C. Benitez-Nelson, and J. K. Whelan

Fig. 6. Relative abundance of organically derived methane and carbon dioxide as a function of temperature and/or time
hydrous pyrolysis of (a) Monterey Shale, (b) Smackover Shale, and (c) Eutaw Shale. All data points for the Monterey and
Smackover Shale represent gas composition after 170 h of heating except for the 1875 h labeled Monterey Shale data
connected by dashed lines.

tion of bitumen is primarily responsible for generation of low
molecular weight hydrocarbons. The decrease in the abundance
of bitumen at temperatures .275°C during the Monterey Shale
experiments (Fig. 7) supports such a model. This decrease
primarily reflects lower abundances of polar material (Nelson
et al., 1995) indicating production of the low molecular weight
species via the decomposition of asphaltenes and resins. A
more detailed discussion of the bitumen extracts and solid
alteration products from the Monterey Shale experiments is
provided in Nelson et al. (1995).
Carbon dioxide was unequivocally the dominant gaseous
alteration product released to aqueous solution during all ex-
periments. Because inorganic carbonate was removed from the
starting rock samples prior to each experiment, the generated
carbon dioxide was entirely organic in origin. In general, the
amounts of carbon dioxide released to solution increased with
 Generation and formation of natural gas
Fig. 7. Gas/bitumen volume ratio (a) and amount of total bitumen
generated (b) as a function of temperature during hydrous pyrolysis of
Monterey Shale for 170 h.
increasing time and temperature and are consistent with results
from previous hydrous pyrolysis experiments (Cooles et al.,
1987; Burnham et al., 1992; Barth and Nielsen, 1993; Andresen
et al., 1994, 1995). Some of the experiments, however, were
characterized by carbon dioxide abundances that demonstrated
nonsystematic variations with respect to time and temperature.
For example, heating of the Smackover Shale at 250 and 325°C
produced almost identical carbon dioxide abundances while
heating of Monterey Shale at 325°C during experiments MS5
and MS13 produced carbon dioxide abundances that were
almost identical to experiment MS11 at 300°C. These nonsys-
tematic variations were not reflected in the abundances of
hydrocarbon gases measured in the same samples suggesting
carbonate mineral precipitation may be responsible for removal
of carbon dioxide from solution. Relatively erratic trends in the
abundance of carbon dioxide as a function of time and temper-
ature or cases where carbon dioxide decreases with increasing
temperature are common during hydrous pyrolysis (Andresen
et al., 1994; Burnham et al., 1992; Cooles et al., 1987) and
suggests that precipitation of carbonate minerals such as calcite
and/or siderite may be a common phenomenon.
There was no indication of carbonate mineral precipitation
during experiment MS15. Changes in fluid composition during
this experiment are consistent with the generation of acidity
according to reaction 1. Dissolved Mg concentrations de-
creased at temperatures .275°C and measured pH (25°C)
varied from 2.91 to 3.52 (Table 3). Accordingly, low pH likely
1607
precluded carbonate mineral precipitation resulting in system-
atic increases in dissolved carbon dioxide as a function of time
and temperature. The measured concentrations at 325°C were
not substantially greater during experiment MS15 relative to
MS5 and MS13 suggesting that carbonate precipitation was not
extensive during the latter two experiments.
During experiments MS1 and MS2 in which inorganic car-
bonate was not removed from the starting sediment, measured
carbon dioxide abundances were less than or the same as in
experiments conducted at lower temperatures (Fig. 2). This
result is opposite to what one might predict considering the
potential for carbonate minerals initially present in the sedi-
ment to dissolve. In the presence of carbonate minerals, how-
ever, the abundance of carbon dioxide in solution will be
regulated by the solubility of minerals such as calcite (CaCO3)
and siderite (FeCO3), provided kinetic constraints do not pre-
clude equilibration with the fluid. Apparently, during these
experiments, pH and the activities of dissolved Ca11 and/or
Fe11 resulted in lower dissolved carbon dioxide abundances.
In addition to saturated hydrocarbons, significant quantities
of alkenes were generated at all temperatures for all rocks. In
general, the abundance of alkenes increased with increasing
temperature. In contrast to the saturated hydrocarbons, how-
ever, the abundance of alkenes decreased with continued reac-
tion at constant temperature, except during the 125°C experi-
ments in which their abundance remained constant. These
results indicate that ethene, propene, and n-butene are unstable
at the concentrations generated during these experiments at
temperatures $150°C. That the alkene abundance at 125°C
remained constant while the abundance of alkanes increased
may suggest that the alkenes were being generated but degra-
dation reactions were occurring at a similar rate. These data are
consistent with the results of Tannenbaum and Kaplan (1985)
who suggested that alkenes are initially produced in small
quantities under dry or hydrous conditions but represent an
unstable intermediate during the formation of petroleum.
Total dissolved H2S concentrations during the Monterey and
Eutaw shale experiments generally increased with increasing
temperature. At temperatures #225°C dissolved H2S concen-
trations were too low for gravimetric determination, but H2S
was detectable by odor in all experiments. The H2S concentra-
tion was not determined during the Smackover Shale experi-
ments but a strong H2S odor in all fluid samples indicated its
presence. The absolute abundance of total dissolved H2S was
likely regulated by the solubility of iron sulfides such as pyrite
and/or pyrrhotite owing to the rapid dissolution-precipitation
kinetics for these minerals under hydrothermal conditions (See-
wald and Seyfried, 1990). Pyrite was abundant in the unheated
Monterey Shale and persisted along with newly formed pyr-
rhotite in the thermally altered rocks. Sources of S during these
experiments include diagenetic pyrite and organic matter. Al-
though it is not possible to quantitatively determine the relative
contributions from these two sources, the amounts of H2S
released to solution at 350, 360, and 375°C for the Monterey
Shale are 13, 19 and 27 mg/g rock, respectively. These values
exceed the amount of S present as diagenetic pyrite in the
starting rock (10.5 mg/g rock as H2S) and provide evidence for
the release of organically bound S to solution.
Dissolved H2 concentrations were determined in selected
fluid samples from the Monterey Shale experiments and in
1608 J. S. Seewald, B. C. Benitez-Nelson, and J. K. Whelan
Fig. 8. Van Krevelen diagram showing compositional evolution of
kerogen with increasing thermal maturity (adapted from Hunt, 1996).
The solid circles show changes in kerogen composition during hydrous
pyrolysis of Monterey Shale.
samples from the 325 and 360°C phases of the Eutaw Shale
experiment. During the Monterey Shale experiments the dis-
solved H2 concentrations showed a systematic increase with
increasing temperature, except for experiment MS5 at 325°C.
This experiment was the first experiment conducted in a new
tubing reactor and the relatively high dissolved H2 concentra-
tions may reflect disproportionation of water during oxidation
of the stainless steel tubing reactor. Similarly, the Eutaw Shale
experiment was also conducted in a new tubing reactor and the
relatively high dissolved H2 concentrations at 325°C may re-
flect oxidation of the reactor walls. Continued reaction at con-
stant temperature resulted in decreasing dissolved H2 concen-
trations.
3.2. Solid Alteration Products
In general, the bulk sediments were characterized by de-
creases in TOC, consistent with the generation of hydrocarbons
(Table 1). The N and S content of the Monterey bulk sediment
also decreased. Analyses of the Monterey Shale isolated kero-
gens reveal increasing C and decreasing O and H contents with
increasing temperature.
Examination of Table 1 reveals a minor but significant initial
increase in the TOC content of the solid products during low
temperature maturation of the Monterey Shale. Because the
sediment represents the only source of C present during the
experiments, this increase likely reflects dissolution of noncar-
bon sediment components. Mass balance calculations indicate
that this increase requires dissolution of approximately 15 wt%
of the inorganic material present.
4. DISCUSSION
Conventional models that account for the timing and com-
position of thermogenic organic alteration products are to a
large extent based on compositional trends for kerogen that
occur in response to increased maturation (Tissot and Welte,
1984; Hunt, 1996). In general, early stage kerogen maturation
is characterized by large decreases in the O/C ratio due to loss
of O-bearing carboxyl, carbonyl, and methoxy functional
groups, with only minor decreases in the H/C ratio (Fig. 8).
With continued burial and heating the O/C ratio remains con-
stant as the supply of labile oxygen is exhausted, while the
onset of hydrocarbon generation results in large decreases in
the H/C ratio. Because it is generally assumed that kerogen
represents the only source of oxygen and hydrogen available
for incorporation in organic alteration products, production of
O-bearing compounds such as carbon dioxide is generally
viewed as being limited to the early phases of kerogen matu-
ration prior to peak oil generation (Tissot and Welte, 1984;
Ungerer, 1990; Cooles et al., 1986; Barker, 1990).
Variations in the compositional evolution of kerogen during
the Monterey Shale experiments were generally consistent with
maturation trends in nature (Table 1; Fig. 8). Large decreases in
the kerogen O/C ratio were observed in the relatively low-
temperature experiments with only a minor decrease in the H/C
ratio, while maturation at relatively high temperatures resulted
in only minor decreases in O/C ratio and substantially greater
decreases in the H/C ratio. The results of this study, however,
suggest that changes in kerogen composition may not accu-
rately reflect the timing of carbon dioxide generation. Al-
though, significant quantities of carbon dioxide were generated
during rock maturation at low temperatures, carbon dioxide
continued to be a major organic matter alteration product in the
experiments at high temperatures. Thus, experimental evidence
suggests that organically derived carbon dioxide was generated
before, during, and after peak hydrocarbon generation.
Comparison of results for carbon dioxide evolution during
hydrous and dry pyrolysis reveals a critical role for water
during organic matter maturation. Heating of isolated Monterey
Shale kerogen during closed-system dry experiments resulted
in a maximum carbon dioxide yield of approximately 2.3
mmole/g TOC after heating at 375°C for 24 h with no further
increases at temperatures as high as 500°C (Tomic et al., 1995).
This amount of carbon dioxide was observed during our ex-
periments after heating at only 250°C for 24 h and is consid-
erably lower than the maximum carbon dioxide production of
8.0 mmole/g TOC at 375°C. The difference in carbon dioxide
yields is greater than can be accounted for by differences in the
oxygen content of the initial kerogens used for each study and
suggests that water may be contributing oxygen for carbon
dioxide production in our experiments. Thus, greater yields and
generation at higher thermal stress suggest additional and/or
different reactions are responsible for the production of carbon
dioxide in the presence of water relative to dry systems.
Mass balance calculations can be used to constrain sources
of oxygen for carbon dioxide production. These calculations
 Generation and formation of natural gas
Fig. 9. Plot of oxygen released from kerogen (white bars) and
oxygen measured in solution as carbon dioxide during hydrous pyrol-
ysis of Monterey Shale (black bars) as a function of temperature.
indicate that changes in the oxygen content of kerogen during
the experiments are sufficient to account for the quantities of
carbon dioxide generated during heating of Monterey Shale at
125 to 360°C (Fig 9). At 375°C, however, the amount of
oxygen as carbon dioxide exceeded that released from the
kerogen by 7.4 % after 1875 h. This oxygen deficit represents
a minimum value, however, since the generation of other
O-bearing alteration products such as water, carboxylic acids,
and bitumen were not considered in these calculations. In
particular, organically derived water has been shown to con-
sume approximately 30 % of organic oxygen during confined
pyrolysis of type II and III kerogens (Monthioux et al., 1985;
Monthioux, 1988; Behar et al., 1992).
Additional sources of oxygen during the experiments include
added water and inorganic rock components. Considering the
low ferric iron content of the Monterey Shale and thermody-
namic barriers to reducing ferrous iron and aluminosilicate
minerals, oxygen derived directly from these sources is not
available for the formation of O-bearing organic alteration
products. Accordingly, water is indicated as an important
source of oxygen for the formation of carbon dioxide during
organic matter maturation. This conclusion is consistent with
the results of other hydrous pyrolysis studies that have impli-
cated water as a source of oxygen in organic alteration products
at temperatures $300°C (Stalker et al., 1994; Lewan, 1997).
Carbon dioxide generation at high temperature may occur
directly from kerogen or via the decomposition of bitumen.
Because heating of Monterey Shale at temperatures .325°C
was not accompanied by decreases in the oxygen content of
kerogen (Fig. 9), production of carbon dioxide directly from
kerogen at these temperatures requires incorporation of wa-
ter-derived oxygen. Requisite oxygen for the generation of
carbon dioxide during the decomposition of bitumen could
be derived from oxygen present in bitumen and/or water.
1609
Laboratory experiments have documented the reaction of
individual hydrocarbons with water to produce oxygenated
alteration products such as ketones and alcohols at temper-
ature conditions similar to those employed during this study
(Leif and Simoneit, 1995; Seewald, 1996). These com-
pounds decompose to form carbon dioxide with continued
heating (Seewald, 1996). Involvement of water and carbon
dioxide during maturation of petroleum was suggested by
Helgeson et al. (1993) after a theoretical evaluation of
petroleum compositions. Thus, in the presence of water,
decomposition of petroleum at elevated temperatures and
pressures may not be limited to the production of short-chain
hydrocarbons and a C-rich residual as invoked by traditional
models (Tissot and Welte, 1984; Hunt, 1996), but may
involve the production of significant quantities of carbon
dioxide.
Utilization of water-derived oxygen during the production of
O-rich alteration products would necessarily result in the re-
lease of hydrogen. Formation of saturated hydrocarbons via the
termination of alkyl radicals or the saturation of alkenes to form
alkanes is likely responsible for the consumption of water-
derived hydrogen during maturation of organic matter. The
incorporation of water-derived hydrogen in hydrocarbons is a
facile process at elevated temperatures (Hoering, 1984; Stalker
et al., 1994). In particular, results of redox-buffered hydrother-
mal experiments have demonstrated the reaction of alkenes
with water to form alkanes (Seewald, 1994, 1996). Alkenes, a
known product during the pyrolysis of sedimentary organic
matter under dry and aqueous conditions (Tannenbaum and
Kaplan, 1985; Esser and Schwochau, 1991), were present in the
early stages of these experiments and showed decreasing abun-
dance with increasing time, even at temperatures as low as
150°C. This trend is consistent with the production of alkenes
as an unstable reaction intermediary during the thermal matu-
ration of kerogen and bitumen, and subsequent saturation to
form alkanes.
The possibility that water may represent a source of oxygen
and hydrogen for the formation of carbon dioxide and hydro-
carbons has important implications for the generation of natural
gas in sedimentary basins. Because water is ubiquitous in most
sedimentary basins, predictive models may underestimate the
gas potential of sedimentary organic matter if they assume
hydrogen and oxygen in organic alteration products are derived
from kerogen only. It is unlikely that hydrogen availability
represents the limiting factor during the initial generation of
liquid hydrocarbons because cleavage of relatively intact kero-
gen fragments to produce high molecular weight saturated
alteration products requires only minor amounts of hydrogen.
With increasing thermal maturation, however, hydrogen de-
mands increase as organic transformations result in a decrease
in the average carbon chain length of hydrocarbons and asso-
ciated increases in the H/C ratio. Thus, inclusion of water as a
reactant during organic transformations will greatly increase
estimates for the amount of carbon dioxide and hydrocarbon
gas that can be generated deep within a sedimentary basin.
Comparison of compositional trends observed during the
experiments with observations from nature show both similar-
ities and differences. The evolution of the hydrocarbon fraction
of natural gas from being almost entirely composed of methane
at shallow depths to containing higher abundances of C2-C7
1610 J. S. Seewald, B. C. Benitez-Nelson, and J. K. Whelan
hydrocarbons at greater sediment depths has been well docu-
mented (Claypool and Kvenvolden, 1983; Hunt, 1996). This
trend is generally attributed to the dilution of methane-rich
biogenic gas with relatively methane-poor thermogenic gas
produced at depth as temperature increases (Claypool and
Kvenvolden, 1983; Whelan, 1979; Whelan and Sato, 1980).
Our experiments, however, demonstrate that at low thermal
maturity, the hydrocarbon fraction of thermogenic gas gener-
ated directly from kerogen may also be methane-rich contain-
ing approximately 90 mole % methane (Fig. 6). Accordingly,
the amount of thermogenic methane in relatively shallow sed-
iments may be greater than existing models would predict.
Although the experiments demonstrate that methane-rich gas
is generated at low thermal maturities, it is clear that the
majority of volatile organically derived alteration products are
formed at higher temperatures. The onset of bitumen generation
during the experiments is accompanied by substantial increases
in the relative amounts of C21 hydrocarbons. The composition
of this gas is consistent with many natural gases associated with
oil suggesting similar maturation processes in natural systems
(Price, 1995; Hunt, 1996; Price and Schoell, 1995). Increases in
the relative abundance of methane at high thermal maturities
during the experiments are also consistent with compositional
trends observed in natural systems (Rice et al., 1988; Hunt,
1996). Despite these similarities, dry gas that is abundantly
present in many natural gas deposits (Mango et al., 1994) was
not produced during the experiments. Numerous other experi-
mental studies have demonstrated the persistence C21 hydro-
carbons at temperatures in $400°C (Tomic et al., 1985; Do-
miné, 1991; Behar et al., 1992; Horsfield et al., 1992; Esser and
Schwochau, 1991; Price and Schoell, 1995). Taken together,
these results demonstrate the stability of C21 hydrocarbons at
temperatures considerably higher than those typically associ-
ated with the generation of natural gas. Thus, classical models
for the generation of dry-gas via the degradation of longer-
chain hydrocarbons by purely thermal processes in which suf-
ficient energy is available to result in cleavage of all C-C bonds
(Tissot and Welte, 1984; Barker, 1990; Ungerer, 1990) may not
be appropriate.
The apparent inability of a purely thermal model to account
for the generation of dry gas has been noted previously and
resulted in a variety of new models to explain its origin and
composition (Mango et al., 1994; Price, 1995; Price and
Schoell, 1995; McNeil and BeMent, 1996). It has been sug-
gested that natural gas contains a significant amount of C21
hydrocarbons at the site of generation, as is observed during
laboratory experiments, but fractionation processes during ex-
pulsion and migration produce enrichment in methane to pro-
duce dry gas. Other researchers have focused on chemical
processes during generation. For example, Mango et al. (1994)
have proposed that under dry and damp conditions, the catalytic
activity of transition metals present in the Monterey Shale
effectively lowers the stability of hydrocarbons and increases
the specificity of decomposition reactions with respect to meth-
ane. In the presence of excess water, however, they observed a
large decrease in the specificity of the catalyst with respect to
methane. Although transition metal catalysis cannot be un-
equivocally demonstrated during our experiments, the latter
observation is consistent with the results of our Monterey Shale
experiments that show production of substantial C21 hydrocar-
bons during the decomposition of bitumen in the presence of
excess water.
McNeil and BeMent (1996) have hypothesized that forma-
tion of an almost pure methane gas occurs from residual kero-
gen after the majority of oil has been generated and expelled. In
their model, alkyl groups attached to aromatic moieties in
kerogen are preferentially cleaved between the first and second
carbon atoms leaving a methyl group behind. Reattachment of
the cleaved alkyl radical to the aromatic ring structure and
subsequent cleavage of the methyl group results in generation
of a methane-rich gas. Such a process may account for the
increases in the relative abundance of methane at temperatures
greater than peak bitumen generation during the experiments,
although a dry gas is never obtained because bitumen is not
expelled in our closed-system experiments. The continued pro-
duction of gas containing substantial quantities of C21 hydro-
carbons at high temperatures, however, suggests that the
amount of methane formed from kerogen is subordinate to the
total hydrocarbon gas formed during the decomposition of
bitumen in a closed system.
4.1. Kinetic Modeling
Data for the generation of volatile hydrocarbons and carbon
dioxide from hydrous pyrolysis experiments can be used to
constrain kinetic models that predict the extent and timing of
hydrocarbon generation in sedimentary basins. In general, these
models are based on reactions governed by first order reaction
kinetics and the Arrhenius equation, but vary significantly with
respect to the number of reactions that are used to describe
hydrocarbon generation (Lopatin, 1971, 1976; Waples, 1980;
Lewan, 1985; Braun and Burnham, 1990; Ungerer, 1990; Hunt
et al., 1991; Sweeney et al., 1995). Thermal maturation of
kerogen to produce oil and gas is an inherently complex pro-
cess involving numerous sequential and parallel reactions. Ac-
cordingly, even the most complex kinetic models represent
gross simplifications of naturally occurring processes. None-
theless, they represent effective tools for petroleum exploration
and predicting the geochemical evolution of sedimentary ba-
sins.
The Arrhenius equation may be written as follows:
k 5 A o exp~ 2 E a/RT) (3)
where k is the reaction rate constant, Ao is the pre-exponential
factor, Ea is the activation energy, R is the ideal gas constant,
and T is temperature in Kelvin. This relationship allows data
collected during high temperature short-term experiments to be
extrapolated to the relatively low temperatures and long reac-
tion times that typically exist in sedimentary basins. We con-
sidered applying a single activation energy model such as that
employed by Lewan (1985) in this study, but examination of
gas generation trends for our experiments revealed that it would
not be appropriate. The rate of gas generation for a reaction that
is first order with respect to the generation potential can be
described by the relationship:
dX/dt 5 k 2 kX (4)
where k is the rate constant defined by Eqn. 3, t is time, and X
is the fraction of the maximum amount of gas generated for a
 Generation and formation of natural gas
given rock (Lewan, 1985). Equation 4 indicates that at a given
temperature and pressure, the rate of gas generation is directly
proportional to the gas generation potential remaining in a rock.
Accordingly, for a single activation energy to be appropriate for
our experiments, decreases in the gas generation rate should
reflect decreases of identical magnitude in the gas generation
potential. During the experiments presented here gas generation
rates decreased by .50 % at a given temperature. Subsequent
increases in temperature, however, resulted in order of magni-
tude increases in the amount of gas generated indicating only
minor decreases in the gas generation potential had occurred at
the lower temperature. These data clearly indicate that gas
generation rates do not reflect the generation potential and are
not consistent with a single first order reaction model.
The trends observed during our experiments are consistent
with a parallel reaction model. Accordingly, we used the com-
puter code KINETICS (Braun and Burnham, 1990) to deter-
mine kinetic parameters for the generation of total low molec-
ular weight hydrocarbons (SC1-C4) and carbon dioxide. This
code can fit an average pre-exponential factor and the relative
percent of reaction associated with a given activation energy
for up to 25 first order parallel reactions. The mathematical
optimization algorithms used by KINETICS require a suffi-
ciently large experimental dataset to fully constrain all kinetic
parameters. The large number of experiments conducted as a
function of time and temperature for the Monterey Shale al-
lowed a unique solution to be obtained. This was not the case,
however, for the relatively sparse experimental datasets for the
Smackover and Eutaw shales. Consequently, to reduce the
number of unknowns, pre-exponential factors for gas genera-
tion from these rocks were assumed to be identical to those
calculated for the Monterey Shale. It is important to realize,
however, that the calculated activation energies are highly
dependent upon this assumption. For example, a one log unit
decrease in the assumed pre-exponential factor produces a 3
kcal/mole decrease in the calculated activation energy values.
For the present analyses, weighting factors for the input data
were normalized to account for differences in the number of
data points at a given temperature. In addition, to ensure that
relative uncertainties in the data were equally accounted for
during the regression analyses the weighting factors were
scaled to be inversely proportional the absolute amount of gas
generated during a given experiment. Retrieval of kinetic pa-
rameters for each shale was performed on an absolute scale
after normalizing the amount of gas generated at a given
temperature to the maximum generated at the highest temper-
ature. A 2 kcal/mole spacing between consecutive values of
activation energies was used for all calculations.
Due to the potential for carbonate mineral precipitation dur-
ing the experiments, data used for the kinetic analyses of
organically derived carbon dioxide were carefully selected. For
the Monterey shale, data from experiments MS1 and MS2 at
225 and 275°C, respectively, were excluded from the kinetic
analysis because inorganic carbonate was not removed from the
starting rocks. Data from experiments MS5 and MS13 con-
ducted at 325°C were also excluded because of anomalously
low carbon dioxide abundances, a likely result of carbonate
mineral precipitation. Despite the exclusion of these data, car-
bon dioxide generation at 225, 275, and 325°C during heating
of the Monterey shale is well constrained by experiment MS15,
1611
during which the potential for carbonate mineral precipitation
was minimized by fluid-talc-quartz equilibrium. For the Eutaw
Shale, the entire carbon dioxide data set was used in the kinetic
analyses. Due to the sparseness and erratic nature of the Smack-
over Shale data set for carbon dioxide generation, kinetic
parameters were not retrieved.
The retrieved kinetic parameters (Table 6) accurately predict
generation of SC1-C4 hydrocarbons and carbon dioxide during
the experiments (Figs. 1–5). For the Monterey shale a preex-
ponential factor of 1.12 3 1016s21 and a distribution of acti-
vation energies from 56 to 66 kcal/mole accounts for the
majority of low molecular weight hydrocarbon generation, with
the maximum percent of reaction accounted for by a value of
66 kcal/mole. These values are within the range expected for
degradation reactions likely to produce natural gas (Ungerer,
1990). Using a pre-exponential factor of 1.12 3 1016s21, a
similar activation energy distribution was retrieved for the
Eutaw Shale while most of the SC1-C4 hydrocarbons generated
from the Smackover Shale could be accounted for by an acti-
vation energy distribution ranging from 56 to 62 kcal/mole.
Because methane and other low molecular weight hydrocar-
bons were still being generated at the termination of these
experiments, reactions characterized by even higher activation
energies may have contributed significant hydrocarbon gases
had temperature been increased or the experiments conducted
for longer duration. Thus, the slightly higher calculated activa-
tion energies for SC1-C4 generation from the Monterey and
Eutaw shales relative to the Smackover Shale may reflect the
fact that the former experiments attained higher thermal matu-
rity in terms of time and/or temperature.
In contrast to low molecular weight hydrocarbon generation,
carbon dioxide generation during heating of Monterey Shale is
best accounted for by a substantially wider activation energy
distribution that varies from approximately 34 to 60 kcal/mole
and a pre-exponential factor of 3.2 3 1013s21. The calculated
activation energy distribution for carbon dioxide generation
from the Eutaw Shale assuming a pre-exponential factor iden-
tical to that of the Monterey Shale is characterized by a simi-
1612 J. S. Seewald, B. C. Benitez-Nelson, and J. K. Whelan
larly wide range that varies from 36 to 56 kcal/mole. The broad
activation energy distribution suggests a more diverse set of
reactions are responsible for the generation of carbon dioxide
relative to SC1-C4 hydrocarbons. For example, it is likely that
carbon dioxide production associated with low activation en-
ergy values is due to the cleavage of O-bearing functional
groups directly from the kerogen macromolecule while that
associated with high activation energies may reflect reaction of
organic compounds with water.
Comparison of the kinetic parameters retrieved here with
previous studies shows both agreement and disagreement.
Knauss et al. (1992) derived individual Gaussian distributions
of activation energies for the generation of methane, ethane,
propane, and butane from hydrous pyrolysis experiments ex-
amining the New Albany Shale. Their results indicate distribu-
tions centered on a value 55 kcal/mole for the generation of all
gases. The lower activation energies may be due to their as-
sumption of a lower pre-exponential factor of 1 3 1014 and the
fact that the maximum temperature during their experiments
was only 330°C, substantially lower than the experiments pre-
sented here. Pre-exponential factors and central activation en-
ergies estimated by Barth et al. (1989) from hydrous pyrolysis
data of Kimmeridge source rocks indicate slightly lower values
than those obtained here and may also be the result of lower
maximum thermal maturities.
There is a striking similarity of our results with those of
Horsfield et al. (1992), who used confined anhydrous pyrolysis
experiments to retrieve kinetic parameters for the generation of
SC1-C4 hydrocarbons during the degradation of a relatively
immature crude oil from the North Sea. Their data yield a
pre-exponential factor of 1.1 3 1016 s21 and an activation
energy distribution from 66 to 70 kcal/mole with the maximum
percent of reaction accounted for by a value of 66 kcal/mole.
The consistency of these results suggests that similar reactions
are responsible for the generation of low molecular weight
hydrocarbons in both sets of experiments. That the rate of
SC1-C4 generation in our experiments is characterized by sim-
ilar rates despite occurring via a two-step process involving the
generation of bitumen from kerogen and its subsequent degra-
dation to form low molecular weight hydrocarbons suggests the
degradation of bitumen is the rate-limiting step that dominates
the timing and extent of gas generation.
The relative timing of oil and gas generation are more readily
apparent when the kinetic parameters retrieved from experi-
mental data are applied to temperature and time conditions
typical of petroleum producing sedimentary basins. Gas gen-
eration curves for a heating rate of 8°C/My indicate that the
bulk of SC1-C4 production is restricted to 160 to 230°C for the
Monterey and Eutaw shales while generation from the Smack-
over Shale ceases at approximately 200°C (Fig. 10). These
temperatures are considerably higher than the 60 to 160°C
temperature range typically invoked for the oil window (Tissot
and Welte, 1984; Hunt, 1996). As has been previously noted
(Sweeney et al., 1987; Horsfield et al., 1992), the chemical
reactions responsible for oil generation may be temporally and
spatially isolated from those responsible for degradation and
are not characterized by a continuous transition. This is espe-
cially true in case of the S-rich Monterey shale for which oil
generation is predicted to be complete at 100°C for a heating
rate of 8°C/My (Hunt et al., 1991).
Predicted trends for the generation of organically derived
carbon dioxide at geologic heating rates are substantially dif-
ferent than those indicated for the hydrocarbon fraction of
natural gas. Carbon dioxide generation is predicted to occur
continuously from low temperatures typical of early diagenesis
to temperatures as high as 220°C (Fig. 10). Thus, organically
derived carbon dioxide production is not restricted to diage-
netic processes that proceed peak hydrocarbon generation as is
commonly assumed but can be expected to occur during and
beyond the oil window as oil degrades to natural gas deep
within a basin.
Although there are several laboratory studies reporting
carbon dioxide generation during hydrous pyrolysis (Cooles
et al., 1987; Barth et al., 1989; Burnham et al., 1992; Barth
and Nielsen, 1993; Andresen et al., 1994, 1995; Lewan,
1997), there are relatively few kinetic models that allow
extrapolation to natural conditions. Barth and Nelson (1993)
report kinetic data retrieved from hydrous pyrolysis of Kim-
meridge source rocks that were not treated to remove inor-
ganic carbonate. Similar experiments by Andresen et al.
(1994) utilizing the same rocks, but with inorganic carbonate
removed, reveals considerably lower carbon dioxide yields
suggesting carbonate dissolution may have occurred to a
significant extent during the experiments of Barth and Nel-
son (1993). Accordingly, their kinetic model likely predicts
carbon dioxide generation from both organic and inorganic
sources and direct comparison with our kinetic model for
organically derived carbon dioxide is not appropriate.
Burnham et al. (1992) estimated activation energies ranging
from 44 to 48 kcal/mole for organically derived carbon dioxide
generation during hydrous pyrolysis of a series of source rocks
from the Maracaibo Basin using an assumed pre-exponential
factor of 3 3 1013. Their model predicts generation of organ-
ically derived carbon dioxide commences at 80°C and ceases at
140°C, considerably lower than our kinetic data predicts (Fig.
10). However, because inorganic carbonate was not removed
from their initial source rocks, Burnham et al. (1992) were
forced to assume that carbon dioxide generated at high tem-
perature during their experiments was inorganic in origin while
that generated at low temperature was organic in origin. Based
on this assumption, high-temperature carbon dioxide was ex-
cluded from their kinetic analysis. Generation of carbon diox-
ide at high thermal maturities during the experiments presented
here suggests that such an assumption may not be valid. More-
over, it is likely that carbonate mineral dissolution and/or
precipitation was occurring at all temperatures during their
experiments precluding unequivocal determination of the
amounts of organically derived carbon dioxide as a function of
time and temperature.
Extrapolation of experimental results to constrain natural gas
generation in nature suggests both hydrocarbons and carbon
dioxide are likely to be generated during the degradation of oil
and kerogen deep within a sedimentary basin. It is important to
remember that the maximum predicted temperatures for gas
generation (approximately 230°C) are directly constrained by
the time and temperature conditions of the experiments used to
constrain the kinetic models. Significant carbon dioxide and
methane production were still occurring at the termination of
the experiments indicating that the maximum gas potential of
the organic matter had not been exhausted. Thus, it is likely that
 Generation and formation of natural gas 1613

Fig. 10. Predicted gas generation curves for (a) SC1-C4 hydrocarbons and (b) carbon dioxide from the Monterey,
Smackover, and Eutaw shales in a hypothetical basin characterized by a heating rate of 8°C/My. The kinetic parameters in
Table 6 and the computer code KINETICS (Braun and Burnham, 1990) were used for the construction of this diagram. Also
shown for comparison is the generation curve for carbon dioxide predicted using the kinetic parameters of Burnham et al.
(1992) applied to the generation potential determined during the Monterey Shale experiments.

in nature, carbon dioxide and methane production may continue
deep within a basin to temperatures in excess of 230°C.
4.2. Controls on the Abundance of Carbon Dioxide in
Natural Systems
The abundance of carbon dioxide in natural gas shows large
and systematic variations with values ranging from 0 to 100
mole %. In many cases, carbon dioxide abundances are char-
acterized by a strong positive correlation with increasing tem-
perature (Smith and Ehrenberg, 1989; Franks and Forester,
1984; Lundegard and Land; 1986; James, 1990). In general, the
majority of reported carbon dioxide abundances in natural gas
are ,10 mole % (Franks and Forester, 1984; Lundegard and
Land, 1986; Jenden et al., 1988a,b; Smith and Ehrenberg, 1989;
Poulson et al., 1995), considerably lower than the minimum
value of 47 mole % observed during hydrous pyrolysis of the
Monterey, Eutaw, and Smackover shales (Fig. 6). The relative
abundance of carbon dioxide decreased systematically with
increasing thermal maturity during the experiments and it is
likely that lower mole % carbon dioxide values may have been
observed had the experiments been of longer duration. How-
ever, even if all sedimentary organic matter remaining at the
end of each experiment were to form methane with continued
reaction, the large amounts of carbon dioxide generated earlier
preclude attainment of relative carbon dioxide abundances as
low as those observed in the majority of natural gas samples.
Thus, comparison of experimental data with natural gas com-
1614 J. S. Seewald, B. C. Benitez-Nelson, and J. K. Whelan
positions suggests that carbon dioxide is being removed from
thermogenic gas in natural systems by secondary processes.
Sinks for carbon dioxide in sedimentary basins include pref-
erential dissolution in aqueous pore fluids and subsequent mi-
gration, and/or precipitation as carbonate minerals. Although it
is likely that the former may occur to a significant extent, it
cannot adequately account for the strong correlation of relative
carbon dioxide abundance with subsurface temperature. Con-
vincing arguments have been made to suggest that this trend
results from the control of carbon dioxide partial pressures
(PCO2) by thermodynamic equilibrium involving feldspar, clay,
and carbonate minerals (Smith and Ehrenberg, 1989; Hutcheon
and Abercrombie, 1990; Hutcheon et al., 1993). Smith and
Ehrenberg (1989) suggest that at shallow levels within a sedi-
mentary basin where temperatures are ,120°C, precipitation of
carbonate minerals will occur while at deeper levels, where
temperatures exceed 120°C, dissolution of sedimentary carbon-
ate will occur. This model is based on the assumption that
carbon dioxide generation is an early stage phenomenon that
produces excess carbon dioxide at shallow levels while at
deeper levels the carbon dioxide potential of kerogen is ex-
hausted and dissolution of sedimentary carbonate occurs to
maintain saturation with respect to calcite. Continuous carbon
dioxide generation before, during, and after peak bitumen gen-
eration during the experiments presented here, however, sug-
gests that carbon dioxide partial pressures may remain above
those required to maintain saturation with calcite even at rela-
tively high levels of thermal maturity, provided there is suffi-
cient TOC content in the sediments. Evidence in support of this
concept is provided by relatively depleted d13C values for
carbon dioxide gas and carbonate cements in some basins that
indicate an organic origin at both shallow and deep levels
(Franks and Forester, 1984; Smith and Ehrenberg, 1989). In the
Texas Gulf Coast, Franks and Forester (1984) report d13C
values for carbonate cements that decrease systematically with
depth as temperature increases to values as high as 210°C,
consistent with increased generation of organically derived
carbon dioxide at depth. Thus, field data provide evidence for
carbon dioxide generation and removal from natural gas as
calcite at shallow and deep levels within a sedimentary basin.
A requirement of the above hypothesis, however, is that suffi-
cient Ca from noncarbonate sources such as aluminosilicate
minerals exists within the rock to form calcite.
To test the above hypothesis we conducted a series of the-
oretical reaction path calculations using the EQ3NR/EQ6 com-
puter code (Wolery, 1992; Wolery and Daveler, 1992) and a
thermodynamic database generated at 350 bars using
SUPCRT92 (Johnson et al., 1992). The goal of these calcula-
tions was to evaluate within a thermodynamic framework the
amounts of noncarbonate Ca required to effectively remove
carbon dioxide as calcite from natural gas. The calculations
involved reacting a hypothetical rock containing 10 wt% K-
feldspar and varying amounts of plagioclase and quartz, with a
Na-Ca-Cl fluid of seawater salinity at 200°C and 350 bars. A
plagioclase composition of 0.3 mole fraction anorthite
(CaAl2Si2O8) was used for these calculations. An initial fluid/
rock mass ratio of 0.32 was chosen which corresponds to an
initial porosity of approximately 10 %. Because kerogen cannot
be treated within a thermodynamic framework, CO2(g) was
added to the system as an additional reactant. The maximum
Fig. 11. Predicted alteration mineral assemblage as a function of rock
total organic carbon content during reaction of a seawater salinity fluid
with a hypothetical rock initially containing 30 wt% plagioclase (mole
fraction anorthite 5 0.3), 10 wt% K-feldspar, and 60 wt% quartz at
200°C and 350 bars. See text for model details.
amount of carbon dioxide generated during hydrous pyrolysis
of Monterey shale (8.0 mmole CO2/g TOC) was used to di-
rectly relate the carbon dioxide quantities to sedimentary TOC
contents.
Variations in the predicted mineralogy as a function of
increasing TOC are shown in Fig. 11. In the absence of carbon
dioxide (0 wt% TOC), anorthite is thermodynamically unstable
and prehnite is predicted as the only calcic phase. Upon intro-
duction of TOC and its associated carbon dioxide to the system,
calcite formation commences almost immediately. Owing to
the low solubility of calcite, PCO2 values in equilibrium with the
stable alteration assemblage consisting of K-feldspar, albite,
muscovite, prehnite, calcite, quartz assemblage are buffered at
0.25 bars (Fig. 12). Continued increases in TOC result in the
destruction of prehnite as Ca is cycled into calcite. Low PCO2
values are maintained until prehnite is exhausted as a reactant,
at which point calcite formation ceases and carbon dioxide
accumulates in solution. Because the amount of prehnite
present is directly limited by the availability of Ca present in
the initial plagioclase, buffering of PCO2 due to calcite precip-
itation continues to higher TOC contents for rocks containing
greater amounts of plagioclase. These calculations suggest that
in many sedimentary basins associated with the production of
oil and natural gas, typical plagioclase abundances are suffi-
cient to facilitate calcite formation and PCO2 buffering in all but
the most organic-rich source rocks. For example, a rock con-
taining 30 wt% plagioclase would require a TOC content .4
wt% to exceed the PCO2 buffer capacity (Fig. 12). Moreover,
this TOC content represents a minimum value since in natural
systems kerogen may not have attained thermal maturation
levels equivalent to those reached during the 375°C phase of
the Monterey Shale experiment which was used as the input
constraint for carbon dioxide potential during these calcula-
tions.
Considering the abundance of Ca in sedimentary rocks, it is
 Generation and formation of natural gas
Fig. 12. Predicted PCO2 in equilibrium with a hypothetical rock
containing varying amounts of plagioclase (solid isopleths), 10 wt%
K-feldspar, and 60 wt% quartz at 200°C and 350 bars as a function of
rock total organic carbon content. A plagioclase composition of 0.3
mole fraction anorthite was used for the construction of this diagram.
See text for model details.
likely that calcite precipitation will influence the composition
of most natural gas samples resulting in carbon dioxide abun-
dances that are substantially lower than those observed during
hydrous pyrolysis experiments. Widespread carbonate precip-
itation in response to thermogenic carbon dioxide production,
however, will not necessarily result in the production of calcite-
rich rocks that are easily identifiable. Complete precipitation of
thermogenic carbon dioxide in a rock containing 4 wt% TOC
will produce only 3.31 wt% calcite which corresponds to 0.39
wt% carbonate-C. This relatively low carbonate abundance
would be indistinguishable from that in numerous marine sed-
imentary rocks that have not experienced thermogenic carbon
dioxide production.
Results of hydrous pyrolysis experiments and model calcu-
lations indicate that the formation of CO2-rich natural gas does
not require the addition of carbon dioxide from an external
source such as igneous activity or by other processes such as
thermochemical sulfate reduction (Krouse et al., 1988). In
rocks characterized by high TOC and/or low plagioclase abun-
dance the buffering capacity of the rock will be exceeded, and
PCO2 will be characterized by relatively high values. Thus, the
results of laboratory experiments in conjunction with reaction
path modeling suggests that organically derived pristine natural
gas is CO2-rich and that secondary reactions involving inor-
ganic sedimentary rock components may be required to pro-
duce methane-rich gas observed in most deposits.
5. SUMMARY
Laboratory experiments represent an effective means to con-
strain processes responsible for organic transformations that
occur in sedimentary basins. Results of hydrous pyrolysis ex-
periments involving Monterey, Smackover, and Eutaw shales
indicate that large and systematic variations in the composition
of natural gas occur in response to changes in the reactions
1615
responsible for its production. Carbon dioxide is the dominant
volatile organic alteration product during the heating of rocks
under hydrous conditions and represents an important alteration
product during the decomposition of bitumen and kerogen in
the presence of water. Requisite oxygen for carbon dioxide
formation is likely derived from kerogen at low maturities and
the disproportionation of water at high maturities. Hydrogen
released during the disproportionation of water is likely con-
sumed by hydrocarbon formation.
Kinetic analyses of the experimental results suggest gener-
ation of SC1-C4 hydrocarbons from the Monterey, Smackover,
and Eutaw shales can be accounted for by a narrow range of
activation energies while carbon dioxide production is charac-
terized by a substantially broader distribution. Application of
retrieved kinetics parameters to times and temperatures typical
of subsiding sedimentary basins indicates that generation of
volatile hydrocarbons is restricted to relatively high thermal
maturities while carbon dioxide generation occurs at both low
and high thermal maturities. Thus, in contrast to the bulk of
C1-C4 generation which is predicted to occur following peak
bitumen generation, production of carbon dioxide is predicted
to occur before, during, and after the generation of liquid
hydrocarbons.
Theoretical reaction path modeling can be used to place
constraints on sinks for carbon dioxide in natural systems.
Calculations suggest that precipitation of calcite is an effective
means to remove carbon dioxide from natural gas provided Ca
is available in the rock. Because generation of carbon dioxide
may continue to high thermal maturities, precipitation of or-
ganically derived carbonate cements is likely at deep levels
within sedimentary basins. Thus, the experimental results in
conjunction with theoretical modeling suggest that high relative
carbon dioxide abundances are not anomalous but may be
characteristic of pristine natural gas, while low carbon dioxide
abundance may be indicative of secondary reactions that results
in the precipitation of carbonate minerals.
Acknowledgments—The authors would like to thank Dr. Michael Le-
wan for providing the Monterey Shale sample and the Louisiana Basin
Research Group for the Smackover and Eutaw shale samples. Organic
petrographic analyses by Lorraine Eglinton are gratefully appreciated.
Thoughtful reviews by Alan Burnham, Ian Hutcheon, and an anony-
mous reviewer substantially improved this manuscript. Funds for this
project were provided by U.S. Department of Energy grant numbers
DE-FGO2-86ER13466, DE-FGO2-92ER14232, and DE-FGO2-
97ER14746 and by Gas Research Institute contract numbers 5088-260-
1746 and 5091-260-2298.
Editorial handling: J. T. Senftle
Accepted for publication after revision: G. Faure
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