Org. Geochem. Vol. 11, No. 1, pp. 15-24, 1987 0146-6380/87 $3.00+0.

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Printed in Great Britain. All rights reserved Copyright © 1987 Pergamon Journals Ltd

Chemical modelling of kerogens

F. BEHAR and M. VANDENBROUCKE
Institut Fran~ais du Pftrole, l ~ , Avenue de Bois-Prfau, 92506 Rueil-Malmaison, France

(Received 28 January 1986; accepted 19 July 1986)

A~tract--Models of kerogens belonging to the three classical Types have been represented at the
following evolution stages:
--beginning of diagenesis (sensu-stricto),
--beginning of catagenesis,
----end of catagenesis.
Chemical models are drawn, using analytical data obtained on natural samples: elemental analysis,
electron microscopy, 13C NMR, thermogravimetry, functional analysis and pyrolysis.
In order both to get a statistical representation and make comparisons easier, the same molecular weight
of about 25,000 has been chosen for the different models of kerogens at the beginning of the diagenesis
stage.

Key words: kerogens, chemical models, organic matter types, diagenesis, catagenesis, metagenesis

INTRODUCTION This paper aims to propose chemical models built

Kerogen is that fraction of sedimentary organic
matter which is insoluble in usual organic solvents
(Durand, 1980). It can be considered as a mixture of
complex macromolecules deriving from organic re-
mains. As burial of sediments increases, kerogen
undergoes evolution, leading to lighter molecules on
the one hand, and to a condensed residue on the
other hand. Composition of kerogen depends on
both the origin of the initial organic matter, and the
evolutionary stage (Tissot et al., 1974). These authors
classify kerogens into three main types, the evolution
of which can be related to successive steps. During
diagenesis, there is mainly a decrease in oxygen
content, then during catagenesis, there is mainly a
decrease in hydrogen content (Pelet, 1980).
Up to fairly recent times, characterization of ker-
ogen in sedimentary basins was done mainly by bulk
analyses (Rock-Eval pyrolysis, elemental analysis,
IR, N M R etc.). It was often difficult to make a
distinction between chemical features due to the
nature of the initial organic matter and its evolution
stage. As the amount and composition of the oils
formed during the kerogen evolution depend on its
chemical composition, it is necessary to know it as
best as possible.
Recent works on degradative techniques such as
chemical degradation (Chappe et al., 1980; Simoneit
and Burlingame, 1973; Micke and Michaelis, 1986),
and pyrolysis (Van de Meent et al., 1980; Larter and
Douglas, 1982; Nip et al., 1986; Behar and Pelet,
1985) allow a better insight into kerogen structure. It
is now possible to build structural models more
detailed than those proposed for instance in Oberlin
et al., 1980).
15
on a number of analytical data which are discussed
below. However, these models have only a statistical
significance taking into account the whole data, and
the real structure of kerogens is probably much more
complex than shown on the pictures.
MAIN CHEMICAL FEATURES OF NATURAL
SERIES OF KEROGENS
The main features of the three types of kerogens as
described in the literature (a review can be found for
instance in Tissot and Welte, 1978 and in Durand,
1980) can be summarized as follows:
Type I
Type I is quite rare and covers very different
biochemical entities such as lacustrine deposits from
Green River shales for instance, in which the bacte-
rial reworking is preponderant, or algal mats such as
coorongite. The main features of these deposits is
their high aliphaticity and hydrogen index. However,
other chemical characteristics such as chain lengths
can differ from one sample to another even in a same
geological series. The kerogen model proposed here
is based on the most aliphatic sample of the upper
marker of the Green River formation in the Uinta
basin (Tissot et al., 1978), which shows some struc-
tural differences with other samples of the Green
River shales examined for instance by Robinson
(1969) or Young and Yen (1977).
At the beginning of the diagenesis stage, this
kerogen is very rich in long aliphatic chains (more
than C40). The oxygen content, mainly in the form of
ether groups, is fairly low.
16 F. BEHARand M. VANDENBROUCKE
Along with thermal evolution, breaking of
carbon-carbon bonds leads to the genesis of a great
amount of paraffinic oil and gas. At the same time,
cyclization occurs in the residue, and the small num-
ber of polyaromatic nuclei which are left can undergo
reorientation to a large extent. The resulting structure
is formed of quasi parallel layers of aromatic con-
densed tings, fairly similar to that of graphite.
Type H
The model is based on Toarcian shales of the Paris
Basin (Tissot et al., 1971) and Lias e shales from
Germany.
At the beginning of the diagenesis stage, the carbon
skeleton of kerogen contains mainly cyclic structures,
with few condensed nuclei. Most side chains have less
than 20 carbon atoms. They are linked to rings by
oxygen and nitrogen containing functional groups,
mainly esters and amide links.
During diagenesis, amide nitrogen disappears,
being either consumed by microorganisms or in-
corporated in aromatic heterocycles, which are
thermodynamically very stable (Schmitter and
Arpino, 1983).
On the beginning of catagenesis, oxygen content
has decreased, due to the loss of CO and CO 2 from
esters and H20 from alcohols. There is no major
change in the carbon skeleton, except aromatization
related to sulfur incorporation and to nitrogen and
oxygen losses.
Oil production during the catagenesis stage leads
STRUCTURE I-a: H/C = 1,64
Fig. l(a)
to naphthenoaromatic compounds, with high sulfur
content. The oil potential is quite high due to the low
condensation of aromatic nuclei, which enables them
to be soluble in the oil phase.
Residual polyaromatic structures undergo reor-
ganization, but to a lesser extent than in Type I
kerogen.
Type III
The model is based on organic matter from deltaic
series of the Douala basin (Albrecht et al., 1976) and
of the Mahakam delta (Combaz and de Matharel,
1978).
At the beginning of the diagenesis stage, kerogen
carbon skeleton is formed mainly from polycyclic
structures containing numerous oxygenated func-
tional groups: phenols, quinones, aromatic acids.
Some linear carbon chains around C30 resulting from
land plants cuticular waxes are present.
Condensation of polyaromatic structures occurs
during evolution by elimination of oxygen. Oil poten-
tial is low and can be related to the loss of the linear
carbon chains, leading to production of paraffinic oil
such as Type I kerogen. The main part of the carbon
content is still in the residual kerogen as polyaromatic
domains, the reorientation of which is very limited, as
few carbon structures are eliminated. This leads to
the formation of a microporous solid in which the
hydrocarbons formed during catagenesis are partly
trapped and cannot be expelled until they are cracked
into gas.
O/C = 0,06 MW = 21 187
 Chemical modelling of kerogens 17

STRUCTURE I-c: R/C = 0,83 O/C = 0,013 MW = 4 024

Fig. l(b)

Fig. 1. Chemical models for Type I kerogen: (a) beginning of diagenesis; (b) end of catagenesis.

DETERMINATION OF BASIC PARAMETERS
OF KEROGEN MODELS
Types and evolution stages of kerogens
We have represented in Figs 1-3 the three classical
types of kerogens (Tissot et al., 1974) for the follow-
ing evolutionary stages:
--beginning of diagenesis, but excluding early di-
agenesis during which the influence of micro-
organisms is predominant (Structures a);
--beginning of catagenesis. Organic matter has lost
the major part of oxygen--containing groups. Oil
is beginning to form (Structures b);
--end of catagenesis. Kerogen has lost a large part of
its hydrogen and has undergone aromatization and
some structural rearrangement. Liquid hydro-
carbons do not form anymore (Structures c).
However, as Type I has a low oxygen content, the
second stage almost overlaps the .first one: then
structure b was not represented for that type.
The first step of each type of kerogen is built on
the same number of carbon atoms (about 1500,
giving an initial molecular weight higher than
20,000). It should be possible to account for the
major part of bulk analyses (elemental analysis,
thermogravimetry, NMR) with a lower molecular

STRUCTURE II-a: H/C = 1,34 U/C = 0,196 P,'IW = 25815

Fig. 2(a)

O.G. II/|--B
18 F. BEHAR and M. VANDENBROUCKE

STRUCTURE II-b: H/C = 1,25 0/C = 0.089 MW = 19860

Fig. 2(b)
STRUCTURE II-c: H/C = 0,73 0/C = 0,026 MW = 7 949

Fig. 2(c)
Fig. 2. Chemical models for Type II kerogen: (a) beginning of diagenesis; (b) beginning of catagenesis;
(c) end of catagenesis.

weight. For instance, asphaltenes which have a mol-
ecular mass as low as a few thousands (Speight and
Moschopedis, 1979) show a great structural similarity
with kerogens (Behar and Pelet, 1985). However we
prefer to use a higher molecular weight so as not to
increase too much the content of biomarkers such as
chlorophyll, hopanoids, etc. in kerogens. Moreover,
molecular orientation of aromatic clusters at the end
of catagenesis cannot be represented if the carbon
number is too low. The initial carbon amount chosen
here should be high enough to obtain a statistical
model of reasonable complexity. But this does not
imply any hypothesis on the real structure of the
macromolecules building the kerogen, their mol-
ecular masses being in a continuum, as those of con-
stituents of oil. Furthermore, incorporation of some
specific biostructures in kerogen (cuticles, mem-
branes, etc.) introduces probably some heterogeneity
in its composition.
When reorganization of aromatic clusters occurs, it
is no longer possible to discuss the structure of
kerogen in terms of size, as long distance orientation,
similar to that in crystals or polymers, appears.
Incorporation of geochemical markers
Chemical and thermal degradation have shown
that geochemical markers are present in kerogens:
 Chemical modelling of kerogens 19

STRUCTURE Ill-a: R/C = 1,06 O/C = 0.281 MW = 26 176

Fig. 3(a)
STRUCTURE Ill-b: H/C = 0,98 O/C = 0,138 MW = 18030

Fig. 3(b)
20 F. BEHAR and M. VANDENBROUCKE

STRUCTURE Ill-c: H/C = 0,67 O/C = 0,059 MW = 13226

Fig. 3(c)
Fig. 3. Chemical models for Type III kerogen: (a) beginning of diagenesis; (b) beginning of catagenesis;
(c) end of catagenesis.

- - c a r b o n number of alkyl chains depends on the
organic matter type (Tissot et al. 1977). Long
normal chains (more than C40) and some iso and
anteiso alkanes are characteristic of bacteria
(Chappe et al., 1980). Even or uneven predom-
inances are associated to cuticular waxes of higher
plants;
--porphyrins are also present and undergo thermal
evolution during diagenesis (Baker and Louda,
1983);
--steroids and hopanoids are differently linked to
kerogen according to the position of their func-
tional groups (Huc, 1978; Hoering, 1984; Micke
and Michaelis, 1986). These markers undergo
progressive aromatization and isomerization de-
pending on the position of the linkage (Spykerelle,
1975; Behar and Pelet, 1986).
CHEMICAL PARAMETERS USED IN THE
MODEL DESIGN
et al., 1983). The proportion of aromatic carbon in
the models is given in Table 2. It increases along with
the evolutionary stage, and for the same stage, from
Type I to Type III.
Relative content o f naphthenic and paraffinic carbon.
IR spectrometry on natural kerogens does not allow
an accurate quantitation of naphthenic and paraffinic
carbon. 13C N M R allows only a balance between the
aromatic and the saturated (linear plus cyclic) car-
bon. So the relative content of naphthenic and
paraffinic structures in the saturated moieties was
estimated from data obtained by mass spectrometry
on saturates derived from natural extracts (Hood and
O'Neal method, in Tissot and Welte, 1978).
The relative contents of naphthenic and aliphatic
carbon in the models are shown in Table 2. These
data correlate with the predominance of aliphatic
structures in natural extracts of Type I and III, Type
II being richer in naphthenic structures.

Elemental analysis
/ ~ / 1 I" .
The atomic ratios H/C and O/C of the models
have been plotted on a Van Krevelen diagram
(Fig. 4). We have chosen these data to match those
I , ~ Oli zone ......... •
of natural series defined previously according to the 10 ~ .... --- a

evolutionary stage. _ ii ,.

In Table 1, the elemental composition, the number I C . -- --} . . . . . . . . . . . . . . . . . . . .

| , .
of carbon atoms, the molecular weights and the
carbon losses between the successive stages are 054)L-.,,~j~./--Gos
; zone
reported for each model. These carbon losses corre- I~.~
I~ ~
spond to data obtained by thermogravimetric anal-
yses on the natural samples (Durand-Souron, 1980).

Structural distribution o f carbon

O~ OIF I 012 I ol O~
ATOMIC RATIO O/C
Aromaticity. We have used structural data on Fig. 4. Position of kerogen models in a Van Krevelen
natural kerogens measured by 13C N M R (Dereppe diagram.
 Chemical modelling of kerogens 21

Table 1. Elemental analysis (atomic ratio), molecular weights and carbon losses of
kerogen models
Kerogen C Carbon loss
model H/C O/C N/C S/C atoms M.W. (%)
Type l - - a 1.64 0.060 0.003 0.001 1439 21,187
c 0.83 0.013 0.003 0.003 305 4024 79
Type I I - - a 1.34 0.196 0.041 0.003 1 5 0 5 25,815
b 1.25 0.089 0.012 0.018 1 2 8 5 19,860 15
c 0.73 0.026 0.014 0.019 569 7949 62
Type I I l - - a 1.06 0.281 0.015 0.001 1 4 4 3 26,176
b 0.98 0.138 0.016 0.004 1 2 1 5 18,959 16
c 0.67 0.059 0.009 0.006 948 13,226 34

Average size o f polyaromatic nuclei. Data obtained Distribution o f functional groups

by electron microscopy on natural kerogens show A review of functional groups analyses on natural
that the maximal size for polyaromatic domains is ten samples can be found for instance in Schnitzer and
rings (Oberlin et al., 1980), at least when these Khan (1978) for humic acids, in Vitorovic (1980) for
domains can be observed. Furthermore these anal- kerogens and in Van Krevelen (1961) for coals. IR
yses indicate that the size of polyaromatic clusters spectroscopy and 13C N M R allow also quantitative
does not increase appreciably along with catagenesis. estimation of functional groups.
The mean number of rings in the aromatic domains These data show that the major functional groups
of our models is given in Table 2. This mean number in kerogens at a low evolutionary stage are oxygen-
must follow the H/C ratios (Oberlin et al., 1980), so containing ones, and that their relative amounts
a slight increase occurs from diagenesis to end of depend on the type of the organic matter. The main
catagenesis, and from Type I to Type III. functional groups are ethers in Type I, esters in Type
Molecular orientation o f aromatic clusters. Oberlin II, phenols, quinones and aromatic acids in Type III.
et al. (1980) have also shown that the aromatic Nitrogen containing groups, mainly in the form of
clusters in natural kerogens undergo reorganization amide links, occur, particularly in Type II kerogens.
during the catagenesis/metagenesis transition and However amide links disappear very early in the
become more or less parallel. The extent of the diagenesis stage.
orientation depends on the type of organic matter. During diagenesis, oxygen is eliminated from func-
For Type I, it is around 500 A, for Type II around tional groups in the form of water and carbon
200/~, and for Type III around 50 /~,, beyond the monoxide and dioxide (Vandenbroucke et al., 1986).
catagenesis zone. This can be explained by the possi- Some groups such as esters and ethers are more
bility of reorientation of residual aromatic clusters resistant than the others to thermal degradation.
during thermal evolution: the more chains and rings Besides the oxygen elimination, sulfur, which is a
are released, the greater is the ability to move for the by-product of bacterial reworking of the organic
remaining carbon structures. matter during deposition, is incorporated in the
In the models, some orientation of aromatic clus- kerogen by cyclization and aromatization processes
ters is represented at the end of catagenesis. However, (Tissot and Welte, 1978). These sulfur compounds
the choice of a same initial carbon number, together are later on released in oils in the form of alkylthio-
with the data on carbon losses, prevents a complete phenes (Ocampo et al., 1987) and benzothiophenes
representation of orientation for Type I and Type II (Castex et al., 1974). At the beginning of the cata-
kerogens. For Type III, the residual carbon number genesis stage, a part of oxygen and all remaining
allows this representation, in agreement with obser- nitrogen are incorporated as heterocycles in the
vations on microporosity of corresponding natural kerogen. At the end of the catagenesis stage, hetero-
kerogens. elements are present only in very stable compounds.

Table 2. Structural distributions of carbon in kerogen models

Average size
Kerogen Aliphatic C Naphthenic C Aromatic C of polyaromatic
model (%) (%) (%) domains~
Type I - - a 74 12 14 1.9
c 36 -- 64 3.8
Type I I - - a 51 19 30 2.8
b 45 14 41 3.1
c 28 -- 72 4.5
Type I l I - - a 38 13 49 3.0
b 34 6 60 3.4
c 19 -- 81 5.7
~Number of rings.
Table 3. D i s t r i b u t i o n o f f u n c t i o n a l g r o u p s in k e r o g e n m o d e l s . T h e first figure is the a m o u n t o f each f u n c t i o n a l g r o u p in the structure. T h e figure in brackets is the o x y g e n p e r c e n t a g e related to the total o x y g e n
in the k e r o g e n m o d e l

OH OH 0 -- C ~'~'' 0
,
--C -- 0 + C--N +
[ \o. \o °~ ° " + --N.--
OH ~ - - S--S-- +
--NH 2

Type I--a 9 -- 2 -- 44 14 -- -- 1 5 -- 2 --
(10) (5) (51) (33) (1)
c . . . . 2 -- -- -- 2 1 1 -- --
,<
(50) (50)

Type ll--a 43 20 15 7 52 45 9 31 2 4 2 2 26
(15) (7) (10) (5) (17) (31) (3) (11) (1)
b 1 5 3 1 33 27 1 -- 12 16 22 1 --
(1) (3) (5) (1) (29) (48) (1) (10)
c . . . . 9 -- -- -- 6 8 11 -- --
(60) (40)
Type III--a 26 102 4 48 80 16 48 6 7 14 2 -- 2
(6) (25) (2) (23) (20) (8) (12) (2) (2)
b 1 54 -- 6 46 14 10 -- 17 18 5 -- 1
(1) (32) (7) (27) (17) (6) (10)
c . . . . 19 -- -- -- 37 9 6 -- --
(34) (66)
 Chemical modelling of kerogens
Sulfur and nitrogen are found only in heterocycles;
one part of oxygen can also be found in ether links.
There data have been combined with elemental
analyses in the models of kerogens proposed here.
The resulting distribution of functional groups and
heterocycles is given in Table 3.
CONCLUSION: ITEMS OPEN TO DISCUSSION
The bonding position of particular molecules such
as some steroids, triterpenoids, waxes, is fairly well
known. However, this is not true for the major part
of the molecules constituting kerogen. So the distri-
bution of functional groups on aromatic domains
and the position of side chains in our models have
only a statistical value. Specific degradative methods
should give a better insight in the position of these
chemical bonds.
Bonds between polyaromatic nuclei have been
represented only as covalent, C - C or C-hetero-
element bounds. Probably there are other types of
bonds such as hydrogen bonds, pi electron inter-
actions, Van der Waals forces, physical adsorption
and steric entrapment (Pelet et al., 1986). However,
they have not been taken into account because we
ignore what is their relative proportion in kerogen.
Studies on unsaturates released by pyrolysis of ker-
ogen are actually in progress to determine the relative
content of covalent bonds (Behar et al., 1987).
Models presented in this paper try to satisfy much
of the present data concerning kerogens in the litera-
ture. Nevertheless they have only a statistical value
and do not infer any hypothesis on the molecular size
and homogeneity of the main types of kerogens, as it
was discussed previously.
Acknowledgements--Studies done in IFP by Geochemistry
and Analytical Physics Departments have largely con-
tributed to a better insight in kerogen structures. We
thank particularly R. Pelet and B. Durand for fruitful
discussions and helpful criticisms. The help of C. Leblond
and E. Deroze for calculations and drawing was highly
appreciated.
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