Chapter 11

Total Organic Carbon (TOO Analysis

Daniel M. Jarvie
Humble Instruments & Services
Humble, Texas, U.S.A.

INTRODUCTION

MODEL OF ORGANIC CARBON

To help in understanding the derivation of the
organic carbon content of a sediment sample, a
descriptive model is presented in Figure 1, which
illustrates the distribution of carbon in organic carbon
(Espitalie et al., 1984). In a given volume of sediment
sample, only a very small percentage of the volume is
from organic carbon. Because TOC values are reported
in weight percent carbon, a TOC value of 1 wt. %
means that in 100 g of sediment sample, there is 1 g of
organic carbon. This is illustrated in Figure 1 by the
small square in the lower right corner of the larger
square representing an aliquot of sediment.
The TOC value consists of three components: the
carbon in extractable organic matter (EOM carbon),
convertible carbon, and a residual carbon fraction. The
latter two are incorporated into the kerogen of a
sediment.
The EOM carbon is composed of the carbon
contained in the oil and gas already formed. It is
derived from the products of thermal cracking of
kerogen and the directly incorporated biological
markers. The EOM carbon is generally a very small
fraction of the TOC. In a typical shale or carbonate
sample, the EOM carbon fraction is less than 1% of the
TOC itself. However, in reservoir rocks, this percentage
may be much higher.
The second component of the TOC content is the
convertible carbon contained in the kerogen. Kerogen
is the complex structure into which the originally
deposited organic matter is transformed through
diagenesis (Tissot and Welte, 1984; Hunt, 1979). The
convertible carbon represents the remaining potential of a
sediment sample to generate oil or gas.
The residual carbon component is also part of the
kerogen and represents the organic carbon present in a
form that has no potential to generate oil or gas due to its
chemical structure and composition. This is because its
highly condensed chemical structure has very little
hydrogen per unit of organic carbon.

Total organic carbon (TOC) is a measurement of the

organic richness of sedimentary rocks. Its utility for
screening potential petroleum source rocks is based on
the source of known petroleum reserves. This source is
organic matter derived from a variety of biological
origins which has been deposited and buried through
geological time (Tissot and Welte, 1984; Hunt, 1979).
While some constituents of petroleum are directly
incorporated into petroleum (biological markers or
biomarkers), the bulk of petroleum is formed from the
thermal decomposition of organic matter through time.
The reactions resulting from increased thermal stress
yield the large variety of carbon-containing compounds
of which oil and gas are composed. Since the oil or gas
potential of a formation is related to its carbon content,
TOC analysis is typically the first screening analysis
completed to evaluate the general potential of a
formation to generate hydrocarbons. Additional
analyses confirm the source potential and elucidate
source characteristics such as the level of thermal
exposure (maturity) and the likelihood of oil, gas, or a
mixture of the two being generated (kerogen type).
Organic carbon is distinguished from inorganic
carbon by its derivation. Organic carbon is derived
from biogenic matter, whereas inorganic carbon is
derived from mineral matter. Inorganic carbon is an
oxidized form of carbon often combined with calcium,
magnesium, or other elements commonly found in
carbonate rocks.
Carbon constitutes 75-95 wt. % of hydrocarbons by
molecular weight, with an average value near 83 wt. %.
The nonhydrocarbon organic constituents of petroleum
(nitrogen, sulfur, and oxygen containing compounds)
and the bulk of the asphaltene fraction as well as the
bitumen and kerogen of petroleum source rocks also
contain high percentages of organic carbon.
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SEDIMENT
SAMPLE
ORGANIC
/ - " " CARBON
r
*"*.
GAS/OIL
EOM
CARBON

KEROGEN
CONVERTIBLE
CARBON

RESIDUAL
CARBON

TOTAL ORGANIC CARBON

Figure 1. Model of organic carbon distribution in a

sediment sample. TOC is the weight percent total organic
carbon in a sediment sample. The carbon constituents of
the TOC are the extractable organic matter (EOM), the
remaining potential to generate hydrocarbons
(convertible), and the nonreactive carbon having no
potential to yield hydrocarbons (residual). (Adapted and
modified from Espitalie et al., 1982.)

In summary, the EOM carbon is that portion of the

organic carbon representing what has been generated
but not expelled, whereas the convertible carbon
represents the remaining hydrocarbon generation
potential. Not all organic carbon can yield petroleumlike products, and the residual carbon describes that
fraction. Whether a sedimentary deposit has oil, gas, or
limited potential is largely due to the chemical
composition of the convertible carbon fraction.

ANALYTICAL METHODS
There are several analytical methods for deteirniriing
TOC, but the two most common are the Leco
combustion method and the combined pyrolysis
oxidation method of Rock-Eval.

Leco Method
The Leco method requires approximately 1 g (~0.5
teaspoon) of pulverized rock. To remove inorganic
carbon in the form of carbonates, chemical treatment of
the sample is required prior to analysis. To achieve
this, the sample is carefully soaked in hydrochloric acid
(HC1) for 12-16 hours with intermittent stirring. At the
end of this time or when the dissolution of carbonates is
observed to be complete (no effervescence with stirring
or additional acid), the sample is rinsed free of the HC1
solution by using water, filter paper, and a filtering

flask. The sample on the filter paper is then allowed

to dry.
Calibration of the Leco Carbon Analyzer is achieved
using a steel standard of known carbon content. The
instrument is blanked to subtract any effect of the
combustion crucible, filter paper, and catalyst. The
carbon in the sample is oxidized to carbon dioxide,
which is detected by either an infrared (IR) detector or a
thermal conductivity detector (TCD). An IR detector is
specific for carbon dioxide, whereas a TCD will
respond to other compounds, such as sulfur dioxide
and water, which may inflate the TOC value if not
properly removed.
The operation of the Leco is basically straightforward, but there are some important chemical and
operational facts to be aware of. First, in Recent
sediments, part of the organic carbon may be
hydrolyzed and lost in the water rinse (Peters and
Simoneit, 1982). Second, a high-carbon switch must be
activated if a high response is recorded across the
detector from high TOC samples analyzed at too high a
weight (often this is only caught by observing the realtime response of the instrument). Third, ineffective
trapping of sulfur compounds and water inflates the
response of instruments with TCDs.
Carbonate carbon can be determined by the Leco
method by completing two analyses. Both the total
carbon content and total organic carbon content are
determined, and the difference is the total carbonate
carbon.

Rock-Eval/TOC Method
The Rock-Eval/TOC method combines Rock-Eval
pyrolysis and an oxidation cycle. Approximately 100
mg (about the volume of a pencil eraser) is required per
analysis. No prior chemical treatment is required, as
the processing steps eliminate carbonate carbon interference. The first portion of the TOC is obtained from
the normalized carbon content of the Rock-Eval Si peak
(free hydrocarbons or thermal extract) and S2 peak
(kerogen cracking or pyrolyzate peak). The normalized
Si and S2 values are equivalent to the EOM carbon and
the convertible carbon, respectively. (These are jointly
referred to as pyrolysis carbon by Espitalie et al., 1984.)
The Si and S2 values are normalized by multiplying by
0.083, which is derived from the average weight percent
of carbon in hydrocarbons and by conversion from
milligrams of hydrocarbon per gram of rock or parts
per thousand (%o) to parts per hundred (%).
The residual portion of the TOC is obtained from the
oxidation of the sample in a second oven following
pyrolysis. This portion of the TOC yield is referred to
as residual carbon (the S4 value converted to %, i.e.,
times 0.10) (Espitalie et al., 1984). There is no carbonate
interference since the sample was essentially decarbonated by thermal decomposition in the pyrolysis
oven. The EOM and convertible carbon are summed

11. Total Organic Carbon (TOC) Analysis

GAS/OIL
EOM
CARBON
S1

KEROGEN
CONVERTIBLE
CARBON

RESIDUAL
CARBON
S4

S2
nee

KC

TOTAL ORGANIC CARBON

Figure 2. Relationship of Rock-Eval data relative to the

model of TOC. Si and S2 are derived from the Rock-Eval
pyrolysis process, whereas S 4 is derived from the RockEval oxidation process, (ncc = normalized carbon
content; 0.083 wt. % for Si and S2; 0.1 wt. % for S4.)
(Adapted and modified from Espitalie et al., 1982.)

with the residual carbon to obtain the TOC value based

on instrument calibration against a known rock
standard. The Rock-Eval/TOC relationships are
summarized in Figure 2, which illustrates the
relationship of various Rock-Eval measurements to the
TOC model.
A key advantage of the combined Rock-Eval/TOC
method is the availability of both TOC and pyrolysis
data nearly simultaneously, which together permit a
screening assessment of maturity, kerogen type, and
organic richness.
Care must be exercised when operating the RockEval/TOC system to ensure that (1) the instrument is
accurately calibrated for both S2 (pyrolysis) and S4
(oxidation) because two separate calibration curves are
required for high TOC (>10%) samples, and that (2) the
sample was not dropped prior to oxidation by the
automatic sampler. Nonlinear responses for the
oxidation oven may result in low TOC values and high
hydrogen indices (S2 x 100/TOC). Samples with TOC
values greater than 10% should be evaluated for TOC at
reduced sample weights and longer oxidation times.
Dropped samples due to instrumentation malfunction
can be readily discerned because the EOM plus
convertible carbon will equal the TOC, i.e., the residual
carbon is not included in the computation.
Overall, variability in TOC analysis largely results
from sample preparation techniques and variations in
instrumentation as well as from operational and
calibration differences. To cross-check accuracy, known
rock standards of varying organic carbon content and
maturity should be included with unknown samples.
In addition to these chemical methods, there has
been some success determining potential source
intervals by utilizing the data obtained from conventional well logging techniques (see Herron, Chapter 13,
this volume). Schmoker (1981) described a technique to
predict TOC from gamma ray logs. However, the

115

technique was not universal and required local

calibration. Meyer and Nederlof (1984) used gamma
ray, density, and resistivity log responses to compute
organic rich intervals mathematically. Passey et al.
(1990) have used an overlay of the sonic transit time
curve on a resistivity curve to predict TOC in the
Alberta basin. The curves overlay one another in
organic-lean intervals, but separate in organic-rich or
reservoir intervals. By first calibrating the separation
against TOC and maturity, they were able to obtain a
TOC versus depth profile from well logs only.
Reservoir intervals were distinguished by a gamma ray
curve and were eliminated from the analysis.
The principal limitation of these methods at the
present time is the requirement to calibrate each field or
basin with laboratory-derived TOC values. This
technology will grow in accuracy and use in the coming
years.

INTERPRETATION
The convertible carbon of any kerogen ultimately
yields hydrocarbons, and an inert carbon residue as
hydrogen is depleted. Even the leanest TOC sediment
will generate a minute quantity of hydrocarbons as a
result of thermal maturation. The key question is
whether a sediment contains sufficient organic carbon of
the right type (oil or gas prone) and maturity to generate
and expel hydrocarbons resulting in commercial
accumulations. Of course, this requires a definition of
what is commercial, which may vary considerably
depending on location and operator.
TOC data only answer the sufficiency question,
whereas other analyses are required to determine
kerogen type and maturity. Other factors affecting
realization of an effective source rock are the chemical
and physical characteristics of the mineral matrix
during generation and expulsion, its position relative to
carrier beds, and the size of economic fields (Jones,
1981). Therefore, samples with adequate TOC content
should be evaluated in greater detail by pyrolysis,
microscopy, pyrolysis-gas chromatography, extraction-gas chromatography, and so forth as necessary to
determine their true source potential.
There is a tendency to choose a lower TOC value for
carbonates than for shales in qualifying potential source
rocks. This is based primarily on the interpretation of
data from Gehman (1962), which showed that
carbonates have a higher concentration of hydrocarbons per unit TOC than shales. However, Jones
(1984) interpreted this data differently and stated that
Gehman's data may simply infer that potential source
rocks have a higher concentration of hydrocarbons per
unit TOC than nonsource rocks. In assessing published
TOC data for potential carbonate and shale source
rocks, Jones (1984) indicated that the minimum TOC

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values are approximately the same for carbonates and

shales.
A highly descriptive table of TOC values for shales
and carbonates is often used, as shown in Table la
(Peters, 1986). However, a simple qualitative approach
may also be appropriate because the TOC is only the
initial assessment of the petroleum-generating
capability of a potential source rock. This approach is
summarized in Table lb.
When evaluating source potential, it is important to
consider the TOC value and the TOC composition. The
quantity (TOC) along with the kerogen type (oil or gas
proneness) more accurately describe source potential.
For example, a 4 wt. % TOC sample with 50 wt. % oilprone kerogen effectively has a 2 wt. % oil-prone
organic carbon content (Cornford, 1986).
In addition, the geologist needs to consider the
volume of source rock available to supply the hydrocarbons necessary to fill a trap. A volumetric model of
hydrocarbon generation and expulsion can be used, as
shown by Cooles et al. (1986).

Consideration of Kerogen Type

The derivation of the originally deposited organic
matter affects both the quantity and quality of the
hydrocarbons generated. This is due to the concentration of the originally deposited organic matter, its
chemical composition, and its preservation as a result of
sedimentation rates and environmental conditions
during deposition (Tissot and Welte, 1984; Dow, 1978;
Demaison et al., 1984; Cornford, 1986).
Kerogen type is often defined by petroleum
geochemists using the elemental composition of
kerogen in terms of hydrogen and oxygen content
relative to carbon content. Type I kerogens have a high
atomic ratio of hydrogen to carbon and a low atomic
ratio of oxygen to carbon. Type EI kerogens are just the
opposite, and type II kerogens are intermediate
between types I and HI. Palynologists describe kerogen
types I, II, and HI as algal-amorphous, herbaceous, and
woody, respectively (Hunt, 1979).
Elemental analysis of kerogens to determine atomic
ratios has largely been replaced by a common screening
technique used to describe kerogen type derived from
Rock-Eval and TOC data. The Rock-Eval S2 peak is
normalized against TOC to derive the hydrogen index
(HI) (S2 x 100/TOC). The hydrogen index has been
correlated to atomic hydrogen/carbon ratios by
Espitalie et al. (1977). Hydrogen index is simply an
indication of the hydrogen content per unit of organic
carbon. It is essentially the availability of hydrogen per
unit TOC that reveals whether a source rock has oil,
mixed oil/gas, gas, or limited hydrocarbon potential.
For example, coals have a very high organic carbon
content but yield primarily gas upon thermal decomposition. This is due to the structure and composition of
the organic matter and, concomitantly, to the lack of

Table 1. Classic interpretations of TOC content in

sediments (based on early oil window maturity)
1)
Generation
Potential
Poor
Fair
Good
Very good
Excellent

TOC in Shales
(wt. %)
0.0-0.5
0.5-1.0
1.0-2.0
2.0-5.0
>5.0

TOC in Carbonates
(wt. %)
0.0-0.2
0.2-0.5
0.5-1.0
1.0-2.0
>2.0

M
Inadequate
Marginal
Adequate

TOC (wt. %)
0.0-0.5
0.5-1.0
>1J)

hydrogen, i.e., coals are hydrogen poor. Oil shales,

which are also organic rich, yield primarily oil because
of their structure and composition, i.e., they are
hydrogen enriched.
In a type I source rock, the percentage of oil-prone
convertible carbon in TOC is high (generally greater
than 70 wt. %), illustrating its high potential to generate
oil (Figure 3a). Such a source rock is hydrogen rich (HI
> 700) and yields a higher concentration of paraffinic
(waxy) hydrocarbons than do kerogen types II or III
(Hunt, 1979; Tissot and Vandenbroucke, 1983).
Type II source rocks contain between 30 and 70 wt.
% convertible carbon in TOC (Figure 3b). Those with a
higher percentage of convertible carbon have more oil
than gas potential. They have a lower hydrogen
content than type I source rocks (HI = 300-700) and
yield a complex mixture of liquid hydrocarbons (Hunt,
1979).
Type III source rocks have a lower potential to
generate hydrocarbons than either type I or II source
rocks. Being hydrogen poor (HI < 300), type HI source
rocks yield primarily gaseous hydrocarbons. The
percentage of convertible carbon contained in the TOC
is less than 30 wt. % (Figure 3c). The TOC content is
primarily residual carbon, which has no potential for
hydrocarbons.
Thus, although TOC content is important, it must be
evaluated in the context of kerogen type and is only one
indication of the potential to generate hydrocarbons.
Effect of Thermal Maturation o n T O C
Value
With increasing thermal maturation, the free
hydrocarbon content (EOM carbon) increases while the
kerogen (convertible carbon) content decreases due to
conversion to oil or gas (Figure 4a and b). Oil-prone
convertible carbon (hydrogen rich) cracks more
completely under lower thermal stress than gas-prone
convertible carbon (hydrogen poor) due to differences
in cracking kinetics. Ultimately, kerogen is cracked

11. Total Organic Carbon (TOC) Analysis

(a)

TYPE I

EOM
CARBON

CONVERTIBLE CARBON

117

RESIDUAL
CARBON

\
(b)

EOM
CARBON

CONVERTIBLE CARBON

RESIDUAL
CARBON

\\
\
(c)

EOM
CARBON

CONVERTIBLE CARBON

RESIDUAL
CARBON

EXPaLED HYDROCARBONS

(b)

TYPE li

(c)

TYPE III

Figure 3. Distribution of organic carbon in different

kerogen types, (a) In a type I (oil-prone) source rock, the
convertible carbon predominates, (b) In a type II (oil/gasprone) source rock, the convertible and residual portions
are approximately equal although variable depending on
oil or gas predominance, (c) In a type III (gas-prone)
source rock, the residual carbon predominates. (Note:
circle size would vary depending on TOC content)

completely to hydrocarbons and a carbon-rich,

hydrogen-poor residue. Because of the conversion of
convertible carbon to EOM carbon and the expulsion of
gaseous and liquid hydrocarbons, the TOC value of a
sediment decreases (Figure 4c).
TOC values without maturity data (such as Rock-

Figure 4. Effect of thermal maturation on a given volume

of organic carbon, (a) With increasing thermal maturity,
the initial EOM and convertible carbon amounts are
changed as a result of generation, (b) The EOM carbon
increases at the expense of the convertible carbon, (c)
With expulsion, the original TOC value is decreased by
the amount of carbon contained in the expelled EOM
carbon fraction. The residual carbon increases slightly
with maturation.

Eval T max or vitrinite reflectance) are insufficient to

screen potential source rocks. If the rock has a very
high potential (i.e., it has a high TOC and contains oilprone organic matter), but it is immature, few hydrocarbons will have been generated, none expelled, and
no commercial reserves accumulated. Of course,
downdip or hotter locations may be more mature and
could supply traps if a migration pathway is available.
On the other hand, if a very high TOC value is
determined in a very mature rock, the TOC is almost
entirely residual carbon, the convertible carbon having
been exhausted in the generation process. In such a
case, the timing of generation and trap formation, the
availability of carrier beds, and hydrocarbon preservation are the important questions to be addressed.

Organic Richness Contour Mapping

A contour map of TOC values of potential source
units is useful in the first phase of analyzing the
geochemical potential of a prospect to yield hydrocarbons. Acquisition of TOC data from available well
samples or outcrops can be used to construct organic
richness maps (e.g., see Webster, 1984). Ideally,
samples from possible source horizons gathered at a
variety of horizontal and vertical grid points should be
analyzed. Organic richness maps of various horizons
will delineate prospective source rocks. When overlaid
with additional screening data such as Rock-Eval
pyrolysis data, the best oil or gas prospects may be
assessed. For example, isomaturation (Tmax), isopotential (TOC and S2), isogeneration (transformation

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Jarvie

ratio), and organic facies (HI) contour maps with

geological maps may delineate the best targets for oil
or gas.

Mass Balance Model

Cooles et al. (1986) have proposed an algebraic
scheme for computing the amounts of petroleum
generated and expelled which is based on a mathematical model of TOC. Their model is similar to the
simple model of this paper. However, the terminology
is different, as the convertible carbon is called reactive
carbon, which is further subdivided into oil- and gasprone fractions (labile and refractory carbon, respectively). Their model can be used to assess the
petroleum generation and expulsion efficiencies of
potential source rocks. In addition, computation of
original TOC and HI can be achieved for input into
quantitative basin modeling programs.
A key assumption in their model is that the residual
carbon (their inert carbon), i.e., the carbon having no
potential to generate hydrocarbons, remains constant

during the main phase of petroleum generation.

Burnham (1989) has stated that while this assumption is
good for type II and HI sources (less than 10-20% error),
it is poor for type I (50% error). In fact, most
exploration targets involve kerogen types II and HI.

CONCLUSION
Measurement of TOC is the first step toward
assessing the potential of a sediment to generate hydrocarbons. Sufficient organic carbon is required to yield
commercial quantities of petroleum. However, this
carbon must be present in a form that can be converted
to petroleum. Thus, TOC data should be utilized to
choose prospective source rocks for additional
screening analysis, such as kerogen type and maturity
assessments. These data together can then be used to
evaluate the effective source potential of a sediment
and the utility of additional detailed analyses of
samples.