Atomic H/C Ratio of Kerogen as an Estimate of Thermal

Maturity and Organic Matter Conversion1

D. K. Baskin2

ABSTRACT of the spent kerogen offer exploration geologists a

quick estimate of oil expulsion volumes. Based on
In recent years, the atomic H/C (hydrogen to car- hydrous pyrolysis experiments, measured H/C
bon) ratio of kerogen as a way to assess the quality of ratios, and calculated original TOC (total organic
organic matter in source rocks has been overlooked carbon) values, first-order volumetric approxima-
in favor of the more easily determined Rock-Eval tions were made on three basins containing mature
hydrogen index. Rock-Eval pyrolysis provides fast, source rocks. Results compared favorably with pub-
inexpensive, quantitative (mg HC/g rock) data with- lished approximate-oil-in-place estimates for the
out requiring kerogen isolation from the rock. Williston basin (Bakken shale), Los Angeles basin
Because of the general scatter in the data, many (Nodular shale), and the Illinois basin (New Albany
source rock interpreters consider Rock-Eval pyroly- Shale).
sis to be a screening analysis. In this paper I describe
the benefits of using H/C ratios in source rock evalu-
ations and present new correlations between atomic INTRODUCTION
H/C ratios and thermal maturity, organic matter con-
version, and expulsion volumetrics. For the past 20–25 yr, petroleum geochemists
Atomic H/C ratios of pyrolyzed kerogens have have successfully applied routine analytical meth-
been correlated to the extent of thermal conver- ods to qualitatively describe source rock proper-
sion of organic matter for both type I and type II ties, including determining the amount, quality,
kerogens. The excellent agreement between stoi- and thermal maturity of the organic matter in the
chiometric calculated hydrogen and carbon loss to rock. More recently, there has been a strong
observed losses from hydrous pyrolysis maturation emphasis on the quantitative assessment of hydro-
experiments suggests that kerogen H/C ratios are carbon generation and expulsion. Current explo-
excellent indicators of thermal maturity for end- ration risks demand a more complete assessment of
member kerogen types. These data also offer a how much kerogen has been converted to oil
method to estimate percent organic matter conver- and how much oil has been expelled from mature
sion, provided that both the initial and present H/C source rocks. This information is critical to explo-
ratios of the kerogen are known. Present H/C ratios ration, basin modeling, and prospect evaluation
can be measured, and initial H/C ratios can be rea- programs.
sonably estimated, from microscopic organic analy- The purpose of this paper is to reacquaint geo-
sis of kerogen. For oil-prone source rocks, typical chemists with the benefits of using kerogen H/C
immature type I kerogens have H/C ratios of (hydrogen to carbon) ratios in source rock evalua-
1.35–1.50, whereas type II kerogens have H/C tions, and to suggest that the ratios be used in con-
ratios of 1.20–1.35. junction with Rock-Eval pyrolysis to better evaluate
Correlations of the amount of expelled oil in the generative history of source rocks. The discus-
hydrous pyrolysis experiments to atomic H/C ratio sion focuses on the use of atomic H/C ratios of kero-
gen as a tool to determine organic matter maturity,
©Copyright 1997. The American Association of Petroleum Geologists. All
and to make rapid estimates of organic matter con-
rights reserved. version. In addition, in this paper I briefly discuss
1 Manuscript received July 13, 1995; revised manuscript received
correlations between oil expulsion volume derived
September 17, 1996; final acceptance March 20, 1997.
2Chevron Petroleum Technology Company, 1300 Beach Blvd., La Habra, from published hydrous pyrolysis experiments and
California 90631. the H/C ratio of the spent kerogen. These correla-
I gratefully acknowledge the management of Chevron Petroleum tions can be used as screening information to give
Technology Company for permission to publish. Special thanks are extended
to B. Katz, L. Snowdon, R. W. Jones, D. Wavrek, K. Peters, and M. McCaffrey, exploration geologists a quick approximation of
who suggested numerous ways to improve this paper. amount of oil expelled (bbl/ac-ft) from a mature

AAPG Bulletin, V. 81, No. 9 (September 1997), P. 1437–1450. 1437

1438 H/C Ratio to Assess Organic Matter

source rock, and are not meant as a substitute for and frequency factor to determine the rate of
more rigorous basin modeling approaches. kerogen breakdown with temperature. These vari-
Several methods for evaluating the extent of ables are usually deter mined from multiple
kerogen conversion have been discussed in the lit- isothermal heating experiments of whole rock or
erature. The Rock-Eval method compares hydro- isolated kerogen. In addition, a time-temperature
gen index (HI) of a mature source rock to an esti- history of the source rock must be reconstructed
mated HI of its immature equivalent (Larter, 1985; for the basin. This is accomplished through the
Schmoker, 1994). The decrease in HI with maturity solution of an energy conservation equation with
reflects the portion of the organic matter that has appropriate boundary conditions. Variations in
been converted to petroleum. The British Petroleum heat flow, burial history interpretations, and paleo-
(BP) method is an extension of the HI method, but surface temperatures affect kinetically derived
uses an algebraic scheme to determine the amount conversion indices.
of petroleum already generated (Cooles et al., 1986).
The ratio of the generated petroleum to the total
petroleum potential (Rock-Eval S2) is a measure of DISCUSSION
conversion. Both methods require immature equiva-
lents of the mature rock samples for geochemical Source Rock Evaluation
comparison. Such samples commonly are not avail-
able. Furthermore, estimating initial HI or S2 values To evaluate the generative potential and genera-
of immature source rocks can be risky because tive history of a source rock, the quantity, quality,
organic matter of a given quality can generate a wide and thermal maturity of the organic matter must be
range of pyrolysis responses due to varying rock known. The criteria for poor, good, and excellent
properties (Espitalié et al., 1980). source rocks have evolved with time. Adapted and
Kerogen conversion can also be modeled kinet- simplified from Peters and Cassa (1994), recog-
ically using the Arrhenius equation, assuming nized source rock evaluation parameters used
first-order reaction rates (Lewan, 1985). The throughout the petroleum industry are summarized
Arrhenius equation requires an activation energy in Table 1.

Table 1. General Source Rock Evaluation Parameters*

Quantity of Organic Matter

Organic Matter Bitumen Hydrocarbons
Wt.% TOC Rock-Eval S2 Wt.% of Rock ppm Rock ppm Rock
Poor <0.50 <1.0 <0.05 <500 <300
Fair 0.5–1.0 1.0–5.0 0.05–0.10 500–1000 300–600
Good 1.0–2.0 5.0–10.0 0.10–0.20 1000–2000 600–1200
Very good 2.0–4.0 10.0–20.0 0.20–0.40 2000–4000 1200–2400
Excellent >4.0 >20.0 >0.40 >4000 >2400

Quality of Organic Matter

Hydrogen Index
Atomic H/C (mg HC/g TOC) Rock-Eval S2/S3
Gas <0.80 <100 <3
Gas and Oil 0.80–1.0 100–200 3–5
Oil and Gas 1.0–1.2 200–350 5–10
Oil >1.2 >350 >10

Maturity of Organic Matter

HC Generation Maturation Generation
Stage Ro (%) TAI Tmax (°C) Bitumen/TOC mg EOM/g TOC Rock-Eval PI
Immature <0.60 <2.5 <430 <0.05 <50 <0.10
Beginning 0.60 2.5–2.6 430–435 0.05–0.10 50–150 0.10–0.15
Peak 0.90 2.9–3.0 445–450 0.15–0.25 150–250 0.15 -0.25
Post >1.20 >3.2 >460 <0.05 <50 <0.20
*Organic matter quantity and quality are maturation dependent. TOC = total organic carbon; TAI = thermal alteration index based on spore coloration index;
Rock-Eval PI (production index) = S1/(S1+S2), HC = hydrocarbon; EOM = extractable organic matter.
 Baskin 1439

The quantity of organic matter in a rock is indi- has been an emphasis on chemically characterizing
rectly evaluated by measuring the rock’s total depositional settings of source rocks. Efforts have
organic carbon (TOC) content (in wt. %), because been made to establish criteria for the degree of
it is difficult to reliably separate and quantify organic matter preservation by determining the rel-
organic components from the rock’s matrix. For ative oxicity during deposition (Wenger and Baker,
example, the weight of kerogen isolated from 1986). Biomarker analyses have been particularly
powdered rock by wet chemistry is generally inac- useful in this area (Moldowan et al., 1986; Peters
curate due to residual mineral matter such as fine- and Moldowan, 1993).
ly dispersed pyrite. Depending on maturity and
quality, the amount of organic matter in a rock
approximately equals 1.25 × TOC. The minimum Organic Matter Conversion
amount of organic carbon needed to generate
commercial amounts of oil has been somewhat In any scheme for estimating volume of generat-
arbitrarily set at 0.5 wt. % (Tissot and Welte, 1984; ed oil, the initial hydrocarbon potential of the rock
Cornford, 1986); however, on a worldwide basis, and the degree of organic matter conversion must
most effective source rocks have average TOC val- be known. To establish the original generative
ues in excess of 2.0 wt. %. potential of the rock, the initial quantity of TOC
The quality of organic matter is usually deter- and quality of the kerogen must be determined. In
mined from Rock-Eval pyrolysis data and common- a spent source rock, both the original TOC and the
ly supported with microscopic organic analysis. original kerogen quality must be reconstructed. It
The Rock-Eval is a commercially available pyrolysis is also necessary to know the fraction of the kero-
instrument that, together with the organic carbon gen that has already been converted to oil.
content of the rock, may be used to assess the qual-
ity of organic matter (Espitalié et al., 1977).
Although Rock-Eval instrumentation varies, com- H/C Ratio vs. Hydrogen Index
monly measured data include the amount of The most significant factor regarding the capaci-
volatile organic compounds in the rock (S1), the ty of source rocks to generate petroleum is the
amount of hydrocarbon compounds generated amount of hydrogen in the kerogen (Waples, 1981;
from thermal cracking of the kerogen (S2), and the Hunt, 1996). The rationale is simple. Hydrogen-rich
amount of carbon dioxide generated from the kero- organic matter commonly generates more oil than
gen (S 3). Normalizing the S 2 and S 3 values to the hydrogen-poor organic matter because oil is rich in
amount of organic carbon gives calculated hydro- hydrogen. After the available hydrogen in the kero-
gen (mg HC/g TOC) and oxygen indices (mg CO2/g gen is depleted, generation ceases regardless of the
TOC). These parameters are interpreted as analogs amount of remaining carbon. Thus, rocks that con-
of atomic H/C vs. O/C (oxygen to carbon) plots of tain abundant hydrogen-rich organic matter are
Van Krevelen (Espitalié et al., 1977). Kerogen quali- good potential source rocks. The two most com-
ty can also be directly evaluated by its atomic H/C mon approaches for evaluating the amount of
ratio, provided the maturity is known ( Jones and hydrogen in kerogen are the atomic H/C ratio and
Edison, 1978; Durand, 1980). the Rock-Eval hydrogen index (HI).
The thermal maturity of organic matter is com- The atomic H/C ratio of kerogen is the pre-
monly derived from Rock-Eval T max . T max is the ferred measure of kerogen quality in source rocks
pyrolysis temperature (°C) at the maximum rate of (Jones, 1987) and the standard to which other
kerogen conversion. Rock-Eval Tmax data should be organic matter quality indicators are compared.
interpreted in conjunction with microscopic analy- Following the footsteps of coal chemists, Tissot et
sis data, such as vitrinite reflectance (Ro) and spore al. (1974) classified three kerogen types, primarily
coloration changes (Jones, 1987). The atomic H/C on the basis of their atomic H/C ratios. Jones and
ratio of the kerogen is also a reliable maturation Edison (1978) documented the reliability of H/C
parameter provided that the type (quality) of organ- ratios as a consistent indicator of kerogen quality.
ic matter is known. The type of organic matter is Jones and Demaison (1982), recognizing that large
usually derived independently from microscopic differences existed between pyrolytic HI data and
organic analysis (Jones, 1987). H/C ratios, defined organic facies and associated
In addition to determining the quantity, quality, source potential primarily in terms of the H/C
and thermal maturity of the organic matter, an inte- ratio of the kerogen rather than pyrolytic yields.
grated study of petroleum generation includes the Jones and Demaison noted that organic facies B
vertical and lateral distribution of the source beds, (type II organic matter), which is the source for
changes in organic facies within the source rock, most of the world’s oil, characteristically has
and the drainage area that has reached thermal atomic H/C ratios between 1.2 and 1.4 when it is
maturity (Demaison, 1984). More recently there immature (Table 2).
1440 H/C Ratio to Assess Organic Matter

Table 2. Generalized Geochemical Characteristics of Organic Facies*

Organic Facies Product Atomic H/C Rock-Eval HI Rock-Eval OI

A (lacustrine) Oil >1.40 700–1000 10–40
B (marine) Oil 1.20–1.40 350–700 20–60
B-C (mix) Oil + Gas 1.00–1.20 200–350 40–80
C (humic) Gas + Oil 0.70–1.00 50–200 50–150
D (inert) Some Gas <0.70 <50 20–200
*H/C = atomic H/C ratio at immaturity is about 0.50% Ro; HI = hydrogen index (mg HC generated/g TOC) × 100; OI = oxygen index (mg CO2 generated/g
TOC) × 100.

Published H/C ratio data for known shale, car- (mg HC/g rock) data from the rapid pyrolysis of
bonate, and phosphatic source rocks with type II whole-rock samples (Peters, 1986). Organic matter
kerogen support Jones and Demaison’s (1982) quality can be interpreted from calculated hydro-
observation (Table 3). These rocks are thermally gen and oxygen indices, which are analogs of the
immature, contain more than 90% oil-prone organ- H/C and O/C ratios of Van Krevelen (Espitalié et al.,
ic matter, and have H/C ratios between 1.2 and 1.4. 1977). However, integrating atomic H/C ratios and
Comparable H/C ratios for these kerogens are Rock-Eval hydrogen indices is difficult (Orr, 1981;
observed because the initial organic matter compo- Katz, 1983; Jones, 1987). For example, Katz and
nents were similar (algal and bacterial) and were Pheifer (1986) showed data on the source potential
deposited under similar depositional conditions of various Cretaceous–Jurassic black shales in the
(euxinic and reducing). Nevertheless, H/C ratios Atlantic Ocean. Katz and Pheifer provided both
are less frequently used, compared to Rock-Eval HI, H/C and HI data for the same rocks (Figure 1),
because H/C data are more costly and time con- which showed that samples with H/C ratios of
suming to generate. In addition, the kerogen isola- between 1.2 and 1.4 (14% difference) have HI val-
tion procedure can precipitate hydrated silicates ues that range between 150 and 650 mg HC/g TOC
that release hydrogen during combustion, resulting (75% difference). Grabowski (1984) published H/C
in anomalously high H/C values (Whelan and and HI data for a variety of rock samples from the
Thompson-Rizer, 1993). Silica-gel contaminants can Cretaceous Austin Chalk of south-central Texas
be identified microscopically and removed by addi- (Figure 2). His data showed HI values that differ by
tional hot hydrochloric acid treatments, whereas as much as 67% (180–540 mg HC/g TOC) for imma-
fluosilicates are inert to further acid treatments. ture oil-prone kerogens with atomic H/C ratios of
Rock-Eval pyrolysis is the workhorse for source between 1.2 and 1.4. Katz and Elrod (1983) pre-
rock evaluation in the petroleum industry today. sented H/C and HI data for samples from the
The analysis provides fast, inexpensive, quantitative Miocene Monterey Formation (Figure 3). Again,

Table 3. Typical Atomic H/C Ratios for Known Source Rocks With Type II Kerogen

Source Unit Atomic H/C* Reference

Austin Chalk, Texas 1.2–1.3 Grabowski (1984)
Bakken Shale, North Dakota 1.23 Jones (1980)
Bone Valley phosphate, Florida 1.2–1.25 Powell et al. (1975)
Cenomanian Shale, offshore Senegal 1.20 Jones (1987)
Devonian shales, western Canada 1.21–1.26 Powell (1984)
Kingak Shale, Alaska 1.2–1.3 Magoon and Claypool (1984), Burwood et al. (1988)
Kimmeridgian Clay, North Sea 1.22–1.35 Jones (1987), Ebukanson and Kinghorn (1985)
Monterey Shale, California 1.2–1.4 Katz and Elrod (1983), Orr (1986),
Peters et al. (1990), Baskin and Peters (1992)
Phosphoria Retort Shale, Wyoming 1.2–1.3 Claypool et al. (1978), Lewan (1985)
Sunniland Limestone, Florida 1.2–1.3 Palacas et al. (1984)
Toarcian Shale, France 1.20–1.26 Tissot et al. (1974), Durand (1980), Jones (1987)
Tuwaiq Mountain, Middle East 1.2–1.4 Ayers et al. (1982), Jones (1985)
Woodford Shale, Oklahoma 1.27 Lewan (1985)
*H/C = atomic hydrogen to carbon ratio for immature, oil-prone (>90% amorphous) kerogen.
 Baskin 1441

Figure 1—Data from Katz and

Pheifer (1986) from samples
showing a large variation in
hydrogen index values (200–600
mg HC/g TOC) for organic matter
with atomic H/C ratios of between
1.2 and 1.4.

there is greater than 50% variation in HI values Upper Jurassic shale in the Viking Graben and the
(300–650 mg HC/g TOC) for about an 11% differ- Cretaceous Toolebuc Formation in Australia,
ence in H/C ratios (1.25–1.4). Other examples respectively. Geochemists recognize that imma-
showing large differences in HI values compared to ture, well-preserved oil-prone organic matter
H/C ratios for the same samples are common (e.g., always shows high H/C ratios, whereas the corre-
Crossey et al., 1986; Burwood et al., 1988; Scott sponding rocks do not always have high pyrolytic
and Hussain, 1988). yields.
Discrepancies between HI and H/C ratio mea- Accurate assessment of the initial kerogen quali-
surements have also been discussed by Horsfield ty is a prerequisite for conversion calculations.
and Douglas (1980), Peters (1986), Larter (1988), Based on variations in HI of 350–700 mg HC/g TOC
and others. The general consensus is that com- (50% difference) compared to variations in H/C
pared to the atomic H/C ratio, Rock-Eval HI values ratios of 1.2–1.4 (14% difference) for immature oil-
can underestimate kerogen quality (Orr, 1981). The prone type II organic matter (organic facies B), the
observed discrepancies can be attributed mainly to atomic H/C offers a more reliable approach to
mineral matrix effects (particularly in organic lean reconstruct the initial kerogen quality in spent or
rocks), bitumen contamination, and type of analy- mature source rocks (Table 2). Furthermore, organ-
sis (pyrolysis vs. combustion). Moreover, experi- ic petrologists can reliably estimate the atomic H/C
mental error for Rock-Eval analysis is approximately ratio of a kerogen from the distribution and type of
±10% (Orr, 1981; D. Jarvie, 1996, personal commu- organic matter components observed under the
nication), whereas analytically, H/C ratios can be microscope (Jones and Edison, 1978). The proce-
reproduced within ±0.05 (Chevron data). For oil- dure is demonstrated in Figure 4, which uses the
prone kerogens with initial H/C ratios of between Van Krevelen diagram for determining the H/C
1.0 and 1.5, this represents an analytical error of ratios of individual organic matter components at
about ±3–5%. any maturity. In this example, microscopic determi-
Whether isolating the kerogen prior to Rock-Eval nations indicate a vitrinite reflectance of 0.5% Ro,
analysis improves results is unclear. For example, and organic matter component distributions of 20%
Orr (1981), Katz (1983), Crossey et al. (1986), and amorphous algal, 65% vitrinitic, and 15% inertinitic
Peters (1986) cited examples where isolated kero- material. The sum of H/C ratios of the organic con-
gens show higher Rock-Eval HI values than the cor- stituents yields an estimated H/C of about 0.90. For
responding whole rocks; however, Huc et al. more mature samples, it is relatively easy to recon-
(1985) and Boreham and Powell (1987) found little struct the initial H/C value once the maceral distri-
difference in whole-rock and isolated-kerogen bution is known. Moreover, predicted H/C ratios
Rock-Eval HI values for organic matter from an usually compare within ±0.10 of analytically
1442 H/C Ratio to Assess Organic Matter

Figure 2—Data from Grabowski

(1984) on generation and
migration of petroleum from
the Austin Chalk, south-central
Texas, showing large variations
in hydrogen index (100–540 mg
HC/g TOC) for organic matter
with atomic H/C ratios of
between 1.2 and 1.4.

derived values (Peters and Cassa, 1994). Thus, it is in hydrogen and carbon in proportions equivalent
preferable to reconstruct the original H/C rather to those found in its products. Typical H/C ratios
than the HI for estimating initial kerogen quality in for oils worldwide are about 1.8–1.85 (Saxby et al.,
source rocks. 1986; Hunt, 1996). Ignoring minor amounts of
early methane generation, these data suggest that
the kerogen loses about 185 atoms of hydrogen for
H/C Ratio as an Estimate of Conversion every 100 atoms of carbon (H/C = 1.85) during the
Any model for calculating the volume of oil main phase of liquid generation; about 300 atoms
expelled from a mature source rock must include of hydrogen per 100 atoms of carbon (H/C = 3.0)
an estimate of the degree of kerogen conversion. during the wet-gas phase; and about 400 atoms of
For this paper, conver sion is defined as the hydrogen per 100 atoms of carbon (H/C = 4.0) dur-
amount of convertible carbon compared to the ing dry-gas generation. The results of these stoi-
total carbon. Failure to accurately estimate extent chiometric calculations are shown in Figure 5,
of conversion can result in underestimates of the where organic carbon loss (in weight percent) is
amount of oil generated from mature source rocks. plotted against the atomic H/C ratio of the depleted
Carbon loss during maturation depends partly on kerogen for three kerogen types. The carbon loss
kerogen quality. Type I kerogens are capable of gen- pathway for each kerogen type is a function of the
erating and expelling significantly more oil than initial atomic H/C of the kerogen.
type II or type III kerogens. Typical conversion per- The amount (in percent) of conversion can be
centages for each kerogen type have been pub- approximated by dividing the carbon loss (evaluated
lished by Dow (1977), Saxby et al. (1986), Behar by the current H/C ratio) by the maximum carbon
and Vandenbroucke (1987), Daly and Edman loss for the mature kerogen (defined by the family of
(1987), Raiswell and Berner (1987), Larter (1988), curves corresponding to the original H/C ratio). For
and Hunt (1996). The consensus is that at full matu- example, a typical type II kerogen with an initial H/C
rity (end of dry-gas generation), type I kerogen ratio of 1.26 (0% carbon loss) and a current H/C ratio
loses 80–85% of its organic carbon, type II loses of 1.0 (about 33% carbon loss) should have generat-
45–60% of its organic carbon, and type III loses ed about 70% (33/46) of its capacity (Figure 5). Type
10–20% of its organic carbon. I organic matter, with its higher initial H/C ratio
Following the scheme of Dow (1977) and Daly (1.59), converts about 90% of its total capacity at an
and Edman (1987), weight percent carbon loss of H/C ratio of 1.0. Ultimate petroleum yields are pro-
the kerogen can be theoretically calculated by portional to the initial amount of TOC and the initial
assuming that the kerogen is continuously depleted hydrogen content of the kerogen.
 Baskin 1443

Figure 3—Data from Katz and

Elrod (1983) of Miocene–Pliocene
organic matter from DSDP Site
467, offshore California, showing
relatively uniform kerogen H/C
ratios of 1.25–1.4 for rocks with
large differences in hydrogen
index values of 300–600 mg
HC/g TOC.

Whether the relationship between decreasing Dung (1989) showed a strong (almost linear) corre-
H/C ratios and weight percent carbon loss deter- lation between Fischer assay conversion yields and
mined from stoichiometric calculations holds dur- the atomic H/C ratio of Australian oil-shale kero-
ing natural maturation is uncertain; however, atom- gens (type I and type I–III mixes). Figure 8 plots his
ic H/C ratios and weight percent carbon loss values data for atomic H/C and percent conversion for
determined from hydrous pyrolysis and Fischer two oil-prone kerogens (type I and type II) from
assay experiments are in good agreement with sto- hydrous pyrolysis experiments. This strong positive
ichiometrically derived values for end-member correlation suggests that percent kerogen conver-
kerogen types and mixtures. Hydrous pyrolysis sion is directly related to the initial H/C ratio of the
experiments attempt to simulate the natural gen- kerogen.
eration of petroleum from source rocks in the lab- Thus, for exploration geologists who want a
oratory by heating samples in a closed system in quick estimate of conversion, the amount of car-
the presence of water (Lewan, 1985; Peters et al., bon lost at any given maturation can be approxi-
1990). Compared to open pyrolysis methods such mated by comparing the measured H/C ratio to the
as Rock-Eval, hydrous pyrolysis generates oils that kerogen’s estimated initial H/C ratio derived inde-
are compositionally similar to natural crudes. pendently from microscopic organic analysis. As
Fischer assay is a material mass balance that previously discussed, the initial H/C of a kerogen
involves heating 100 g of crushed shale at 500°C can be reasonably estimated, particularly for well-
for 1 hr (Hunt, 1996). preserved (nonoxidized) type II kerogens where
Figure 6 compares weight percent carbon loss initial H/C ratios are almost always between 1.20
and H/C values for a theoretical type II kerogen and and 1.35.
a Monterey type II kerogen subjected to hydrous
pyrolysis, both with an initial H/C ratio of 1.27.
Likewise, Figure 7 shows weight percent carbon Example
loss plotted against theoretical H/C ratios for an The Institute of Petroleum and Organic
immature type I kerogen (H/C = 1. 59) and for mea- Geochemistry at the Nuclear Research Center
sured H/C ratios from the hydrous pyrolysis of a (KFA) in Julich completed a comprehensive study
Green River shale sample (type I) with an initial on the generation and migration of petroleum from
H/C ratio of 1.59. In both cases, the high degree of the lower Toarcian (Jurassic) organic-rich Posidonia
correlation suggests decreasing atomic H/C ratios Shale in northern Germany (Rullkötter et al., 1988).
accurately reflect carbon loss from the kerogen Four shallow holes were drilled in nearby Hils syn-
resulting from hydrocarbon generation. Moreover, cline in close proximity to a deep-seated intrusive.
1444 H/C Ratio to Assess Organic Matter

Figure 4—Typical Van Krevelen

diagram showing how to estimate
H/C ratio of kerogen from
maceral composition and
thermal maturity. VR = vitrinite
reflectance (in percent), TAI =
thermal alteration index based
on spore coloration, OM = organic
matter. H/C ratio estimate is
the sum of the weighted H/C
contributions of each maceral
type. For example, a sample with
a measured vitrinite reflectance
of 0.50%, and weighted H/C values
for 20% type II, 65% type III, and
15% type IV organic components,
yields an estimated H/C value for
the kerogen of 0.875.

Samples from each core showed increasing levels mathematically converted to barrels of oil per acre
of thermal maturity with depth. The purpose of foot (bbl/ac-ft) simply by multiplying the S2 value
the study was to derive organic matter mass bal- by 22. The constant 22 is approximate and
ance calculations for hydrocarbon generation depends on values chosen for grain density of the
based on this natural experiment and excellent rock and specific gravity of the oil. Until hydrous
sample control. pyrolysis experiments were routine, there was no
Posidonia kerogen is classified as type II. reasonable alternative to the Rock-Eval S2 parame-
Detailed microscopic and sedimentological data ter as a guide for volumetric calculations; however,
show no evidence of changing depositional condi- Rock-Eval pyrolysis data only provide information
tions or kerogen quality over the sampled area. about the remaining generative capacity of a rock
Thus, the differences in geochemical properties are and give no direct information about expulsion.
directly related to thermal maturation (Littke et al., During pyrolysis, the rapid heating rate (25°C/min)
1988). The atomic H/C ratio of the least mature and flushing of the pyrolysates by a carrier gas con-
kerogen at the Wenzen borehole (Ro = 0.48%) was tribute to more efficient expulsion than occurs in
measured at 1.25–1.28. At the more mature nature. Organic geochemists recognize these phe-
Dielmissen borehole (Ro = 0.68%), the H/C values nomena and understand that volumetrics derived
measured 1.14–1.15. Based on these data and cor- only from Rock-Eval S 2 data likely overestimate
relations in Figure 5, about 38% of the convertible hydrocarbon yields.
organic carbon has been generated as oil or gas. Hydrous pyrolysis experiments offer an alterna-
This estimate is in good agreement with conversion tive to Rock-Eval pyrolysis for obtaining volumetric
estimates based on mass balance calculations estimates. Hydrous pyrolysis generates in-situ bitu-
where one-third of the kerogen reacts before reach- men (extractable), sorbed bitumen (rinsed from
ing an Ro of 0.70% (Rullkötter et al., 1988). rock surface), and floating oil during the artificial
maturation of a source rock. Hydrous pyrolysis
results of type I, type II, and type III kerogens have
QUANTITATIVE EXPULSION ESTIMATES been published by various workers. Huizinga et al.
(1988) measured yields for the type I Green River
Determining the volume of oil expelled from a shale. Lewan (1985) published pyrolysis results for
mature source rock is speculative at best. The two type II kerogens, the Permian Phosphoria shale,
Rock-Eval S2 parameter in milligrams of hydrocar- and the Mississippian–Devonian Woodford Shale.
bon per gram of rock (mg HC/g rock) can be Likewise, Peters et al. (1990) and Peters and
 Baskin 1445

Figure 5—Calculated organic

carbon loss for typical kerogen
types plotted against H/C ratio
of depleted kerogen, assuming a
decrease in H/C of 1.85 for oil,
3.0 for wet gas, and 4.0 for dry
gas (methane). Wet-gas and
dry-gas generation begin below
H/C 1.0 and 0.75, respectively.
OM = organic matter.

Moldowan (1991) published hydrous pyrolysis Figure 9 also suggests that the type II kerogens
results for type II kerogens from the Miocene subjected to hydrous pyrolysis have similar expul-
Monterey phosphatic and siliceous shale members. sion characteristics, apparently independent of
Hydrous pyrolysis results were also published on lithology. In general, type II kerogen with an ini-
the type III North Dakota lignite by Teerman and tial H/C ratio of about 1.25 expels 60–65 bbl oil/
Hwang (1991). acre-ft/TOC at maturity (H/C = 0.50). Moreover,
A quick estimate of how much oil was expelled this value is not unique to hydrous pyrolysis.
from a mature source rock can be made from Harwood (1977) published results of sealed-tube
hydrous pyrolysis data. Rather than express vol- pyrolysis experiments performed on a variety of
ume of expelled oil in terms of experimental tem- kerogen types. He also monitored the elemental
peratures, it can be expressed as a function of composition before and after each pyrolysis.
kerogen maturity (H/C). In an attempt to do this, Comparing the weight of bitumen generated to
the total amount of expelled oil (sorbed plus the H/C ratio of the kerogen, Harwood showed
float), normalized to the TOC content of the rock, that the type II kerogen from the Napo Shale in
has been plotted against atomic H/C ratio for each Ecuador, with an initial H/C ratio of 1.28, yielded
kerogen type (Figure 9). Several noteworthy fea- about 65 bbl oil/acre-ft/TOC when thermally
tures appear on this plot. For example, the yield of mature. This is supporting evidence that the
oil normalized to TOC appears to be directly pro- expulsion capacity of oil-prone source rocks is
portional to initial hydrogen content (H/C) of the largely controlled by initial kerogen (H/C) quality,
kerogen. This is not unexpected, because percent initial amount of TOC, and the degree of thermal
conversion is also related to the kerogen’s initial maturity of the rock. In general, both hydrous and
H/C ratio. The Green River shale (H/C = 1.59) sealed-tube pyrolysis experiments suggest that
expels almost twice as much liquid during matura- well-preserved type II kerogen generates and
tion per unit of organic matter as does a typical expels 60–65 bbl oil/acre-ft/TOC when it is fully
type II kerogen (H/C = 1.25). The North Dakota mature (H/C = 0.50).
lignite (type III) has a low initial H/C ratio and a Figure 9 also shows a lag in the H/C ratio
low yield per TOC. The high TOC content associat- between kerogen conversion and liquid expul-
ed with coals suggests that coals might generate sion. Type II kerogen with a current H/C ratio of
substantial amounts of petroleum. However, vitri- 1.0 should have transformed 75–80% of the reac-
nite and inertinite usually dominate coals, and tive carbon to petroleum (Figure 5); however,
these macerals have high absorptive capacities Figure 9 suggests that much of the generated
that prevent most of the generated petroleum from petroleum is still in the rock at this maturity.
migrating out of the rock (Hunt, 1996). Thus, initially there is not a linear decrease in
1446 H/C Ratio to Assess Organic Matter

Figure 6—Kerogen H/C ratio

plotted against theoretical
weight percent carbon loss and
measured carbon loss from the
hydrous pyrolysis of Monterey
Shale type II kerogen. High
degree of correlation suggests
the H/C ratio of spent kerogen
accurately reflects carbon loss
during maturation.

H/C ratio (type II kerogen) vs. the amount of maturity of the kerogen are from the literature, as
expelled oil. The sharp initial drop in the H/C ratio well as the approximate volume of mature source
for type II kerogens vs. the amount of liquid being rock. Dow (1974) estimated that about 10 billion
expelled reflects generated bitumen that is saturat- bbl of oil were expelled from mature Bakken
ing the pore space of the rock prior to expulsion. shale in the Williston basin. TOC values for the
Correlations between the atomic H/C ratio of Bakken average about 11 wt. %, according to
the kerogen and the amount of expelled oil can Webster (1984). H/C ratios of 1.23 for immature
be used as a fir st approximation of the total kerogen and 0.83 for mature kerogen have been
expulsion capacity, the remaining expulsion reported by Jones (1980). The volume of mature
capacity, and the amount of oil already expelled, source rock in the basin is estimated to be about
provided that the type of kerogen, the TOC, and 60 mi 3 (Dow, 1974; Webster, 1984). Based on
the atomic H/C ratio of the kerogen are known. expulsion parameter s derived from hydrous
Examples for three general cases are given in pyrolysis correlations (Figure 9), mature Bakken
Table 4. For immature samples, the approach is source rocks have expelled about 65 billion bbl of
straightforward, because the total expulsion oil in this basin. In contrast, Webster (1984) cal-
capacity and the remaining expulsion capacity culated from Rock-Eval data that mature Bakken
are the same. For samples that are significantly sediments generated more than 100 billion bbl of
mature, identifying the initial kerogen type allows oil. To account for the 10 billion bbl of oil indicat-
a good estimation of its initial H/C ratio. From ed by Dow (1974), Webster suggests that only
this information, the initial TOC can be recon- about 10% of the generated hydrocarbons were
structed using correlations between H/C and car- expelled from the source rock. More likely, most
bon loss (Figures 6, 7). Amount of expelled oil of the oil was lost during relatively unobstructed
and the remaining expulsion capacity of the rock updip migration that reflects the geometry of the
can be estimated from Figure 9. Williston basin. In any event, expulsion volumet-
rics based on Rock-Eval are somewhat high and
suggest that Rock-Eval pyrolysis may overestimate
Examples petroleum generation.
The Los Angeles basin in southern California
Volumetric estimates using the above approach contains about 25 billion bbl of oil in place
were made on three basins containing mature (Jones, 1980). The estimated volume of mature or
source rocks, and the results were compared with postmature source rock (Nodular shale and equiv-
approximate-oil-in-place estimates for each basin. alents) is about 200 mi3, and TOC values for these
Information about the quality, quantity, and thermal rocks average about 4.0 wt. % (Jones, 1980).
 Baskin 1447

Figure 7—Atomic H/C ratio

plotted against theoretical
weight percent carbon loss
and measured carbon loss from
hydrous pyrolysis of Green
River shale type I kerogen.
The high degree of correlation
suggests the H/C ratio of spent
kerogen accurately reflects
carbon loss during maturation.

Initial H/C ratios are estimated to be 1.25, and In the Illinois basin, an estimated 4 billion bbl of
mature H/C ratios are about 0.95. Volume of oil in place has been generated by mature New
expelled oil calculated using correlations from Albany Shale sediments (Barrows and Cluff, 1984).
Figure 9 is about 53 billion bbl. Unlike the Deep in the basin, the average thickness of the
Williston basin, where long-distance migration is mature source rock is about 100 ft, with TOC val-
a factor, much less oil has been lost during short- ues averaging about 3.0 wt. %. H/C ratios at maturi-
distance migration in the Los Angeles basin. ty in this basin are about 1.0 (Barrows and Cluff,

Figure 8—Strong positive

correlation between atomic
H/C ratio and percent carbon-
to-oil conversion determined
from Fischer assay analyses.
Data from type I and type I–III
kerogen mixes from Australian
oil shales (Dung, 1989) and from
hydrous pyrolysis of type I Green
River shale and type II Monterey
Shale.
1448 H/C Ratio to Assess Organic Matter

Figure 9—Correlation between

atomic H/C ratio of spent kerogen
and volume of expelled oil
determined from hydrous
pyrolysis experiments of
known source rocks for the
three kerogen types. Plot
suggests that at full maturity
(H/C = 0.5), type I organic matter
can generate and expel about
100 bbl oil/acre-ft/TOC, and
type II organic matter can
generate and expel
60–65 bbl oil/acre-ft/TOC.

1984). The volume of mature type II source facies is however, compared to the Rock-Eval hydrogen
estimated to be about 100 mi3. From these data, an index, kerogen H/C ratios better define original
estimated 25 billion bbl of oil was expelled, which is organic matter quality and are good indicators of
a reasonable amount considering that 10–15% of the thermal maturity for end-member kerogen types.
oil expelled is accounted for as oil in place. Used in conjunction with Rock-Eval pyrolysis, kero-
gen H/C ratios greatly contribute to source rock
evaluation and can offer the geologist a quick esti-
CONCLUSIONS mate of maturity, conversion, and volumetrics.
Organic matter conversion can be estimated
Atomic H/C ratios of kerogen have been under- from hydrogen and carbon loss from the kerogen
valued as a source rock parameter in favor of the during maturation. From hydrous pyrolysis data,
more easily generated Rock-Eval hydrogen index; the atomic H/C ratio of the pyrolyzed organic

Table 4. Generalized Examples of Possible Expulsion Histories of Source Rock With Type II Organic Matter*

Measured Original Initial H/C Expulsion Capacity Expelled Oil Remaining Capacity
Parameters TOC Ratio (bbl/ac-ft) (bbl/ac-ft) (bbl/ac-ft)
Example 1
Type II OM
H/C = 1.25 4.0 1.25 240 0 240
TOC = 4.0

Example 2
Type II OM
H/C = 0.80 4.2 1.25 250 160 90
TOC = 2.5

Example 3
Type II OM
H/C = 0.60 3.0 1.25 180 150 30
TOC = 1.5
*OM = organic matter; TOC = total organic carbon.
 Baskin 1449

matter correlates to percent carbon loss for both Special Publication 38, p. 35–46.
type I and type II kerogens. From this relationship, Daly, A. R., and J. D. Edman, 1987, Loss of organic carbon from
source rocks during thermal maturation (abs): AAPG Bulletin,
the amount of organic matter lost due to genera- v. 71, p. 546.
tion can be estimated knowing the current H/C Demaison, G. J., 1984, The generative basin concept, in G. J.
ratio of the kerogen and the initial quality of the Demaison and J. R. Murris, eds., Petroleum geochemistry and
organic matter. The initial quality of the organic basin evaluation: AAPG Memoir 35, p. 1–14.
Dow, W. G., 1974, Application of oil correlation and source rock
matter usually can be independently determined data to exploration in the Williston basin: AAPG Bulletin, v. 58,
from microscopic organic analysis. p. 1253–1262.
Data from hydrous pyrolysis experiments offer Dow, W. G., 1977, Kerogen studies and geological interpretations:
the geologist a quick approximation to quantitative Journal of Geochemical Exploration, v. 7, p. 79–99.
estimates of generation, conversion, and expulsion. Dung, N. G., 1989, Pyrolysis behavior of Australian oil shales in a
fluidized bed reactor and in a material balance modified Fischer
Expulsion estimates derived from hydrous pyrolysis assay retort: Fuel, v. 68, p. 1570–1579.
data and kerogen H/C ratios may be better than Durand, B., 1980, Kerogen, insoluble organic matter from sedi-
those derived from Rock-Eval pyrolysis because mentary rocks: Paris, Editions Technip, 519 p.
hydrous pyrolysis directly measures the amount of Ebukanson, E. J., and R. F. Kinghorn, 1985, Kerogen facies in the
major Jurassic Murdoc formations of southern England and the
oil expelled from a mature source rock. implications on the depositional environments of their precur-
Volumetric estimates using the approach sors: Journal of Petroleum Geology, v. 8, p. 435–462.
detailed in this paper were made on three basins Espitalié, J., J. Laporte, M. Madec, F. Marquis, P. Leplat, J. Paulet,
containing mature source rocks; the results are and A. Boutefeu, 1977, Rapid method for characterizing the
comparable to published estimates of approximate petroleum potential and degree of evolution of source rocks:
Revue de l’Institut Français du Pétrole, v. 32, p. 23–42.
oil in place. For the Williston basin (Bakken shale), Espitalié, J., J. Madec, and B. Tissot, 1980, Role of mineral matter
Los Angeles basin (Nodular shale), and the Illinois in kerogen pyrolysis: influence on petroleum generation and
basin (New Albany Shale), the percent conversion migration: AAPG Bulletin, v. 64, p. 58–66.
and volume of expelled oil were estimated from Grabowski, G. J., 1984, Generation and migration of hydrocarbons
in Upper Cretaceous Austin Chalk, south-central Texas, in J. G.
kerogen H/C ratios, average TOC values, and Palacas, ed., Petroleum geochemistry and source rock potential
hydrous pyrolysis yields. The estimates appear to of carbonate rocks: AAPG Studies in Geology 18, p. 97–115.
be reasonable approximations for the volume of Harwood, R. J., 1977, Oil and gas generation by laboratory pyroly-
expelled oil found in each basin. sis of kerogen: AAPG Bulletin, v. 61, p. 2082–2102.
Horsfield, B., and A. G. Douglas, 1980, The influence of minerals
on the pyrolysis of kerogens: Geochimica et Cosmochimica
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chemistry, in L. B. Magoon and W. G. Dow, eds., The ABOUT THE AUTHOR
petroleum system—from source to trap: AAPG Memoir 60,
p. 93–117.
Peters, K. E., and J. M. Moldowan, 1991, Effects of source, thermal
maturity, and biodegradation on the distribution and isomeriza- David Baskin
tion of hopanes in petroleum: Organic Geochemistry, v. 17, David Baskin is a staff research
no. 1, p. 47–61.
Peters, K. E., and J. M. Moldowan, 1993, The biomarker guide:
geologist with Chevron Petroleum
interpreting molecular fossils in petroleum and ancient sedi- Technology Company in La Habra,
ments: Englewood Cliffs, New Jersey, Prentice Hall, 363 p. California. He completed a B.S.
Peters, K. E., J. M. Moldowan, and P. Sundararaman, 1990, Effects degree in geology from San Jose
of hydrous pyrolysis on biomarker thermal maturity parame- State University in 1967 and attend-
ters—Monterey phosphatic and siliceous members: Organic ed graduate school at San Jose and
Geochemistry, v. 15, p. 249–265. California State University at
Powell, T. G., 1984, Some aspects of hydrocarbon geochemistry of Fullerton. Starting in 1972, his
a Middle Devonian barrier-reef complex, western Canada, in early research work focused on
J. G. Palacas, ed., Petroleum geochemistry and source rock
potential of carbonate rocks: AAPG Studies in Geology 18, organic petrology, source rock
p. 45–61. evaluation, and petroleum systems. Since 1989, he has
Powell, T. G, P. J. Cook, and D. M. McKirdy, 1975, Organic geo- concentrated on geochemistry applications to reservoir
chemistry of phosphorites—relevance to petroleum genesis: production and development using oil fingerprinting
AAPG Bulletin, v. 59, p. 618–632. techniques.