T
Total Organic Carbon (TOC)
Joseph A. Curiale
Geochemical Advisory Services, Sugar Land, TX, USA
Definition
Total organic carbon (TOC) content, as used in the petroleum
geosciences, is a measure of the mass of organically bound
carbon in a geological sample relative to the mass of the
sample. Most commonly abbreviated as TOC and expressed
as a percentage value – for example, % organic carbon within
a rock – total organic carbon measurements are fundamental
to petroleum geochemistry and indispensable for source rock
analysis and interpretation.
Introduction
This article will discuss analytical and modeling methods for
assessing total organic carbon in solid geological samples and
will briefly address applications and interpretation of TOC
values in petroleum geoscience. TOC percentages in geolog-
ical samples, and specifically in sedimentary rocks being
evaluated for their petroleum source rock potential, can be
determined through laboratory measurement of individual
samples or estimated through numerical modeling at the
regional scale. Analytical measurements are appropriate and
necessary for samples which are physically available in suf-
ficient amounts for laboratory assessment. Modeled TOC
values can be developed from first principles of biological
production, transport to the site of deposition, and long-term
preservation in the sediment column. Although analytical
determinations are highly accurate, model values must be
considered when samples are unavailable and/or when it is
desired to determine the evolution of TOC through time.
Numerical modeling assessments of TOC and initial
# Springer International Publishing AG 2017
R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_3-1
(depositional) TOC, referred to as TOCo, are particularly
valuable when results can be validated at the regional scale
by comparing modeled values to measured values.
Analytical Measurement
Our focus in this section will be on automated instrumental
methods for quantitative TOC measurement, as these have
largely replaced wet oxidation methods of TOC determina-
tion in recent sediments and sedimentary rocks. Qualitative
(e.g., infrared and other spectroscopic), semiquantitative
(e.g., assessment by inference and calculation, such as TOC
deduction from organic matter volume estimates), and
deconvolution (e.g., using electric logs) methods for TOC
estimation are not considered here. Common high-throughput
approaches for quantitative measurement of TOC in the
starting sample involve either the combustion or the pyrolysis
of organic matter, which creates one or more carbon-
containing species that is then measured by specialized detec-
tion systems (Jarvie 1991). Various standard methods have
been devised for TOC and total organic matter measurement
in recent and lithified sediments, including ASTM approaches
(e.g., Schumacher 2002 and references therein). This article
will focus on the most common direct and indirect approaches
used in petroleum geoscience.
Direct analysis of TOC involves the oxygen-mediated
combustion of organic matter in approximately 0.1–0.3
grams of starting sample (Fig. 1). The sample is treated
initially to remove inorganic carbon prior to instrumental
analysis. Various levels of treatment, usually involving
hydrochloric acid or phosphoric acid, are employed to remove
carbonate-bound carbon from the sample. The organic carbon
remaining in the treated sample is then combusted quantita-
tively to carbon dioxide and carbon monoxide (the latter can
subsequently be converted catalytically to carbon dioxide
prior to detection) in a carbon analyzer at temperatures of
1200–1400  C. Generated total carbon dioxide is then
2 Total Organic Carbon (TOC)
Total Organic Carbon (TOC),
Fig. 1 Total organic carbon is
measured on a small, powdered,
homogenous rock sample
following acid treatment to
remove the carbon bound as
carbonate. Values are commonly
reported as grams organic carbon
per gram rock, given as a
percentage
measured through thermal conductivity detection or non-
dispersive infrared detection. Depending on the detection
system, the carbon dioxide-containing effluent may be subject
to selective trapping prior to carbon measurement. TOC
values are calculated through the use of external standards
and are reported on a dry-weight basis as a carbonate-free
carbon mass percentage of starting material. For example, a
typical petroleum source rock might have 2%, 5%, or 10%
total organic carbon. Modern instruments for direct carbon
measurement often possess the simultaneous ability to mea-
sure other elements as well (e.g., sulfur, nitrogen).
The most common indirect method of TOC analysis
involves, prior to a final oxidation step, pyrolytic analysis of
the more labile component of organic matter in the starting
sample. Approximately 0.1 g of untreated sample is heated to
550  C or 600  C in the absence of oxygen and commonly in a
flow of helium (Jarvie 1991). The hydrocarbons and non-
hydrocarbons volatilized in this step, along with those created
from pyrolysis of heavy hydrocarbons and kerogen, are quan-
tified with a flame ionization detector. After this initial
oxidant-free heating episode, the sample is oxidized at ele-
vated temperature, and the carbon-containing effluent is
quantified. Suitable conversion coefficients are used to con-
vert pyrolysis yield to carbon mass, and these coefficients
vary as a function of the type of organic matter in the sample
(Fujine 2014). The calculated value for carbon derived from
the pyrolysis yield – the so-called convertible fraction – is
then summed with the residual carbon amount from oxidation
to generate the TOC of the sample. Although multiple com-
mercial instruments are available for assessing TOC indi-
rectly in this manner, the concepts used in the analyses and
computations are similar.
Indirect TOC determination as measured through com-
bined pyrolysis oxidation is a multistep process and therefore
is likely subject to greater error than purely oxidative (direct)
determination of acid-treated samples. Additionally, as noted
above, conversion coefficients in the combined pyrolysis-
oxidation method vary as a function of organic matter type,
a concern not present in direct analysis. For this reason, many
interpreters prefer to use TOC data generated from the direct
oxidation method. Nevertheless, the indirect methods elimi-
nate the need for prior removal of carbonate carbon, resulting
in the ability to process a greater number of samples per unit
time. Furthermore, whereas the direct method provides a
single parameter – TOC – the indirect method, using current
instrumentation, provides pyrolytic data in addition to TOC
data, including hydrocarbon yields from pyrolysis over pro-
grammed temperature ranges. For this reason, the indirect
method is gradually surpassing the direct method and may
ultimately become the technique of choice.
The accuracies of analytical methods for TOC measure-
ment are a function of instrument quality and known carbon
standards in the case of both direct (full oxidative) and indi-
rect (pyrolytic/oxidative) measurements. As noted earlier, an
additional influence to consider when assessing measurement
accuracy in the case of the fully oxidative method is the
efficiency of removal, prior to instrumental analysis, of the
carbon bound as carbonates. In practice, commercially avail-
able standards are used to assess accuracy, and blanks are run
regularly. Analytical precision for both direct and indirect
analysis types is usually less than 5–10% relative, as deter-
mined through repeated analysis of homogenized aliquots.
Given the wide lateral and stratigraphic variation in carbon
content within a sedimentary rock unit, this analytical preci-
sion level is minor compared to the wide range of natural
variation in TOC.
Computational Approaches for Determination of Initial
TOC (TOCo)
Instrumental measurement of TOC is necessary for determin-
ing potential and effective source rock characteristics, as
noted previously, whereas numerical modeling of deposi-
tional TOC is critical when samples are unavailable (see the
next section). However, it is often useful to compute initial, or
Total Organic Carbon (TOC)
depositional, TOC from the present-day TOC of petroleum
source rocks. This value, commonly designated TOCo, can be
computed with varying degrees of certainty. The techniques
for doing so generally utilize present-day TOC values modi-
fied according to various assumptions about the process and
rate of loss of organic carbon through time. Several authors
have proposed various methods (Tyson 2006; Jarvie 2012,
2014; Curiale and Curtis 2016), most of which back-
extrapolate (retrodict) TOCo from kerogen type and present-
day level of thermal maturity. For example, present-day TOC
levels within a single source rock unit of 0.82 and 4.31 at
thermal maturity levels of Ro = 1.9% and 0.6%, respectively,
may both extrapolate back to a retrodicted TOCo value of
5.0%. It is this value which would be used for this source unit
in resource assessments and as input to, or validation of, the
numerical models discussed in the next section.
As reviewed in Curiale and Curtis (2016), estimates to
back-calculate TOCo by accounting for the effect of thermal
maturity are useful if organofacies or starting maceral distri-
butions (or general kerogen type) are known. Straightforward
efforts include the use of a TOC-maturity relationship based
on a representative set of source rock measurements within a
single unit in a basin. In such an approach, an equation in
which maturity is the independent variable and TOC is the
dependent variable is used to compute TOCo. Essentially,
TOCo is retrodicted as the TOC value occurring at deposi-
tional levels of thermal maturity. More complex approaches
include the use of additional parameters, such as initial hydro-
gen index, fitted to various nomograms (Jarvie 2012).
Although methods for TOCo assessment are useful in
resource assessment, the geochemical community has not
yet centralized on a single, acceptable approach. Indeed, as
noted by Curiale and Curtis (2016, p. 16), “. . .all approaches
seeking to determine initial/depositional TOC. . ., while per-
haps comforting to the explorationist, are heavily laden with
assumptions, most of which are difficult or impossible to
validate.” Thus, caution is urged.
Numerical Modeling Approaches
The importance of total organic carbon information in the
petroleum geosciences has led to extra-analytical methods
of assessment, most particularly those involving numerical
modeling using various geologic, tectonic, and climatic
inputs. As petroleum exploration has moved to more and
larger frontier areas, and particularly as the evaluation of
organic matter in deepwater sediments became critical, the
absence of access to source rock material has made modeling
of organic carbon, and organic matter deposition in general,
critical to success. Established models for this purpose have
met with varying levels of success, although modeling accu-
racy is expected to increase as knowledge of earth history and
general petroleum systems increases.
3
Physical and chemical inputs controlling the deposition
and preservation of organic carbon in a marine setting have
been known for decades, although appropriate use of these
inputs for successful model predictions still remains under
discussion. Fundamentally, initial production of organic mat-
ter, dominantly in the photic zone of the marine water column,
must be preserved during transport through the water column
and after taking up residence in unconsolidated sediments.
Dilution of sedimented organic matter with mineral matter
and biogenic inorganic remains will reduce the proportion of
organic carbon (on a mass of carbon to total mass of sediment
basis) and, therefore, becomes a critical element in any
numerical model. Thus, estimates of parameters such as pro-
duction rate, accumulation rate and burial efficiency, and the
rate of change of these parameters through time are key inputs
to any numerical model for organic carbon accumulation
(Tyson 1994). Parameterizing a numerical model with these
inputs has been attempted by several workers (see Mann and
Zweigel 2008 and references therein), and it is now possible
to retrodict regional TOC distributions at past geologic times
with varying degrees of success.
These forward-directed (first principle) numerical models
may also be supplemented with modeled estimates of past
earth conditions – e.g., using paleogeographic and various
paleoenvironmental assumptions – and used in a concerted
fashion to retrodict temporal and spatial deposition of
organic-rich sediments. In this way, we can indirectly assess
TOC levels at time of deposition (Peters et al. 2008; Bohacs
et al. 2010 and references therein). Retrodiction approaches of
this type are available within the petroleum industry and from
commercial vendors, although their routine use is inconsistent
from company to company and vendor to vendor. As with
forward-directed numerical models, these too have met with
varying degrees of success.
A common approach of paleogeographic-paleoclimate
carbon depositional modeling begins by addressing a specific
geologic timeslice. A paleoclimate model is typically run
using landform distributions derived from a paleotectonic
model appropriate to the timeslice. Paleoclimate outputs
(e.g., upwelling intermittence through time; seabottom cur-
rent and intensity; monthly rainfall patterns) and paleogeo-
graphic inferences (e.g., shore-to-shore distance as a proxy
for oxic conditions in the water column) are employed to infer
settings likely to promote organic matter production and
preservation. Analytical methods of TOC assessment can be
used when representative samples of the geologic unit are
available, and results of these analyses can be used to validate
the output of paleogeographic-paleoclimatic modeling.
Origin and Applications
Total organic carbon values are used extensively in the petro-
leum geosciences, and the TOC concentration in recent sed-
iments and sedimentary rocks is a fundamental and primary
4 Total Organic Carbon (TOC)
Total Organic Carbon (TOC), Table 1 Source rock interpretation guidelines based on initial (depositional) total organic carbon – TOCo – are
shown here for various ranges. As noted in the text, TOCo alone is unable to assess source rock potential properly. As shown in this figure, kerogen
type and thermal maturity, among other parameters, are also necessary (Hunt 1996)
TOCo
range
(%) Potential interpretation
0–1% Little to no petroleum-generative potential
1–5% Poor to fair petroleum-generative potential, if
organic matter type is appropriate
>5% Good to excellent petroleum-generative
potential, if organic matter type is appropriate
parameter in organic matter assessment. This section will
briefly describe the development and fate of total organic
carbon concentration levels in recent sediments and petro-
leum source rocks. More details may be found in other entries
of this encyclopedia.
Organic matter (OM) in sedimentary systems, including its
carbon content as well as secondary elements such as hydro-
gen, oxygen, nitrogen, and sulfur, originates in living systems
native to the water column (autochthonous OM) and to sur-
rounding land surfaces (allochthonous OM). As noted in the
previous section, this organic matter is scavenged as it settles
through the marine or lacustrine water column and often
partially oxidized at the water-sediment interface. These phe-
nomena, supplemented with sedimentary dilution by inor-
ganic material, yield the TOC levels observed in recent
sediments (Tissot and Welte 1984).
Once this recent sediment TOC content is established, it
then becomes the baseline level – i.e., initial TOC, or
TOCo – from which petroleum source rock potential is
assessed.
Diagenetic and catagenetic changes which occur during
sediment burial, including microbial utilization of organic
carbon and loss of organic carbon due to generation of petro-
leum and its expulsion from the sediment, gradually reduce
the organic carbon content. (Exceptions can also occur. For
example, TOC of coarse-grained reservoir rocks can increase
when petroleum accumulates in the pore space of these
rocks.) Knowledge of this reduction is useful in assessing
past and present capacity of a sedimentary rock to generate
and expel petroleum and thus has extensive application in
petroleum geoscience (Hunt 1996).
Total organic carbon levels necessary for the generation of
petroleum are a continuing subject of discussion, and several
workers have proposed ranges useful for source rock assess-
ment. Interpretations based on these ranges require several
factors to be considered, including postdepositional loss of
TOC due to generation and expulsion of petroleum. Table 1
provides guidelines for interpretation of present-day TOC as a
determinant of present-day petroleum source rock potential. It
is important to consider that these ranges are only broad
Comments
Some workers consider 0.5% as minimum TOCo for gas-prone effective source
rocks
Minimal values for effective source rock occurrence in this range of TOCo depend
on kerogen type and lithology
An excellent range for marine and some lacustrine depositional environments;
greatly elevated TOCo values commonly encountered in terrigenous depositional
setting may show good gas-prone potential but poor oil-prone potential
averages, and interpretations made by geochemists will vary
as a function of kerogen type, thermal maturity, geological
history, and several other factors (Hunt 1996). Indeed, it is
widely understood that the use of just the TOC value as a
source rock assessment tool is foolhardy – at a minimum,
measures of organic matter quality and thermal maturity are
required for this purpose.
Summary
Total organic carbon concentration in recent sediments and
sedimentary rocks is a fundamental measurement used in
petroleum geoscience. Its quantitative derivation through ana-
lytical measurement on a per-sample basis or numerical
modeling at the local and regional scale provides a starting
point (TOCo) for the assessment of petroleum source rock
capacity, thermal maturity evolution, and surface adsorption
characteristics of sedimentary rocks. These applications make
accurate determination of TOC a key requirement of all
petroleum system evaluations.
Cross-References
▶ Basin and Petroleum System Modeling
▶ Hydrocarbons: Origin
▶ Petroleum Exploration
▶ Petroleum Geochemistry
▶ Petroleum Source Rocks
▶ Petroleum System
▶ Programmed Pyrolysis
▶ Total Organic Carbon: Calculations from Well Logs
▶ Total Organic Carbon: Estimation of Initial TOC
Total Organic Carbon (TOC)
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