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

00
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 on a number of analytical data which are discussed
matter which is insoluble in usual organic solvents below. However, these models have only a statistical
(Durand, 1980). It can be considered as a mixture of significance taking into account the whole data, and
complex macromolecules deriving from organic re- the real structure of kerogens is probably much more
mains. As burial of sediments increases, kerogen complex than shown on the pictures.
undergoes evolution, leading to lighter molecules on
the one hand, and to a condensed residue on the
MAIN CHEMICAL FEATURES OF NATURAL
other hand. Composition of kerogen depends on SERIES OF KEROGENS
both the origin of the initial organic matter, and the
evolutionary stage (Tissot et al., 1974). These authors The main features of the three types of kerogens as
classify kerogens into three main types, the evolution described in the literature (a review can be found for
of which can be related to successive steps. During instance in Tissot and Welte, 1978 and in Durand,
diagenesis, there is mainly a decrease in oxygen 1980) can be summarized as follows:
content, then during catagenesis, there is mainly a
Type I
decrease in hydrogen content (Pelet, 1980).
Up to fairly recent times, characterization of ker- Type I is quite rare and covers very different
ogen in sedimentary basins was done mainly by bulk biochemical entities such as lacustrine deposits from
analyses (Rock-Eval pyrolysis, elemental analysis, Green River shales for instance, in which the bacte-
IR, N M R etc.). It was often difficult to make a rial reworking is preponderant, or algal mats such as
distinction between chemical features due to the coorongite. The main features of these deposits is
nature of the initial organic matter and its evolution their high aliphaticity and hydrogen index. However,
stage. As the amount and composition of the oils other chemical characteristics such as chain lengths
formed during the kerogen evolution depend on its can differ from one sample to another even in a same
chemical composition, it is necessary to know it as geological series. The kerogen model proposed here
best as possible. is based on the most aliphatic sample of the upper
Recent works on degradative techniques such as marker of the Green River formation in the Uinta
chemical degradation (Chappe et al., 1980; Simoneit basin (Tissot et al., 1978), which shows some struc-
and Burlingame, 1973; Micke and Michaelis, 1986), tural differences with other samples of the Green
and pyrolysis (Van de Meent et al., 1980; Larter and River shales examined for instance by Robinson
Douglas, 1982; Nip et al., 1986; Behar and Pelet, (1969) or Young and Yen (1977).
1985) allow a better insight into kerogen structure. It At the beginning of the diagenesis stage, this
is now possible to build structural models more kerogen is very rich in long aliphatic chains (more
detailed than those proposed for instance in Oberlin than C40). The oxygen content, mainly in the form of
et al., 1980). ether groups, is fairly low.
15
16 F. BEHARand M. VANDENBROUCKE

Along with thermal evolution, breaking of to naphthenoaromatic compounds, with high sulfur
carbon-carbon bonds leads to the genesis of a great content. The oil potential is quite high due to the low
amount of paraffinic oil and gas. At the same time, condensation of aromatic nuclei, which enables them
cyclization occurs in the residue, and the small num- to be soluble in the oil phase.
ber of polyaromatic nuclei which are left can undergo Residual polyaromatic structures undergo reor-
reorientation to a large extent. The resulting structure ganization, but to a lesser extent than in Type I
is formed of quasi parallel layers of aromatic con- kerogen.
densed tings, fairly similar to that of graphite.
Type III
Type H The model is based on organic matter from deltaic
The model is based on Toarcian shales of the Paris series of the Douala basin (Albrecht et al., 1976) and
Basin (Tissot et al., 1971) and Lias e shales from of the Mahakam delta (Combaz and de Matharel,
Germany. 1978).
At the beginning of the diagenesis stage, the carbon At the beginning of the diagenesis stage, kerogen
skeleton of kerogen contains mainly cyclic structures, carbon skeleton is formed mainly from polycyclic
with few condensed nuclei. Most side chains have less structures containing numerous oxygenated func-
than 20 carbon atoms. They are linked to rings by tional groups: phenols, quinones, aromatic acids.
oxygen and nitrogen containing functional groups, Some linear carbon chains around C30 resulting from
mainly esters and amide links. land plants cuticular waxes are present.
During diagenesis, amide nitrogen disappears, Condensation of polyaromatic structures occurs
being either consumed by microorganisms or in- during evolution by elimination of oxygen. Oil poten-
corporated in aromatic heterocycles, which are tial is low and can be related to the loss of the linear
thermodynamically very stable (Schmitter and carbon chains, leading to production of paraffinic oil
Arpino, 1983). such as Type I kerogen. The main part of the carbon
On the beginning of catagenesis, oxygen content content is still in the residual kerogen as polyaromatic
has decreased, due to the loss of CO and CO 2 from domains, the reorientation of which is very limited, as
esters and H20 from alcohols. There is no major few carbon structures are eliminated. This leads to
change in the carbon skeleton, except aromatization the formation of a microporous solid in which the
related to sulfur incorporation and to nitrogen and hydrocarbons formed during catagenesis are partly
oxygen losses. trapped and cannot be expelled until they are cracked
Oil production during the catagenesis stage leads into gas.

STRUCTURE I-a: H/C = 1,64 O/C = 0,06 MW = 21 187

Fig. l(a)
 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 --end of catagenesis. Kerogen has lost a large part of
OF KEROGEN MODELS its hydrogen and has undergone aromatization and
some structural rearrangement. Liquid hydro-
Types and evolution stages of kerogens carbons do not form anymore (Structures c).
We have represented in Figs 1-3 the three classical
However, as Type I has a low oxygen content, the
types of kerogens (Tissot et al., 1974) for the follow-
second stage almost overlaps the .first one: then
ing evolutionary stages:
structure b was not represented for that type.
--beginning of diagenesis, but excluding early di- The first step of each type of kerogen is built on
agenesis during which the influence of micro- the same number of carbon atoms (about 1500,
organisms is predominant (Structures a); giving an initial molecular weight higher than
--beginning of catagenesis. Organic matter has lost 20,000). It should be possible to account for the
the major part of oxygen--containing groups. Oil major part of bulk analyses (elemental analysis,
is beginning to form (Structures b); 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 masses being in a continuum, as those of con-
ecular mass as low as a few thousands (Speight and stituents of oil. Furthermore, incorporation of some
Moschopedis, 1979) show a great structural similarity specific biostructures in kerogen (cuticles, mem-
with kerogens (Behar and Pelet, 1985). However we branes, etc.) introduces probably some heterogeneity
prefer to use a higher molecular weight so as not to in its composition.
increase too much the content of biomarkers such as When reorganization of aromatic clusters occurs, it
chlorophyll, hopanoids, etc. in kerogens. Moreover, is no longer possible to discuss the structure of
molecular orientation of aromatic clusters at the end kerogen in terms of size, as long distance orientation,
of catagenesis cannot be represented if the carbon similar to that in crystals or polymers, appears.
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 Incorporation of geochemical markers
imply any hypothesis on the real structure of the Chemical and thermal degradation have shown
macromolecules building the kerogen, their mol- 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 et al., 1983). The proportion of aromatic carbon in
organic matter type (Tissot et al. 1977). Long the models is given in Table 2. It increases along with
normal chains (more than C40) and some iso and the evolutionary stage, and for the same stage, from
anteiso alkanes are characteristic of bacteria Type I to Type III.
(Chappe et al., 1980). Even or uneven predom- Relative content o f naphthenic and paraffinic carbon.
inances are associated to cuticular waxes of higher IR spectrometry on natural kerogens does not allow
plants; an accurate quantitation of naphthenic and paraffinic
--porphyrins are also present and undergo thermal carbon. 13C N M R allows only a balance between the
evolution during diagenesis (Baker and Louda, aromatic and the saturated (linear plus cyclic) car-
1983); bon. So the relative content of naphthenic and
--steroids and hopanoids are differently linked to paraffinic structures in the saturated moieties was
kerogen according to the position of their func- estimated from data obtained by mass spectrometry
tional groups (Huc, 1978; Hoering, 1984; Micke on saturates derived from natural extracts (Hood and
and Michaelis, 1986). These markers undergo O'Neal method, in Tissot and Welte, 1978).
progressive aromatization and isomerization de- The relative contents of naphthenic and aliphatic
pending on the position of the linkage (Spykerelle, carbon in the models are shown in Table 2. These
1975; Behar and Pelet, 1986). data correlate with the predominance of aliphatic
structures in natural extracts of Type I and III, Type
CHEMICAL PARAMETERS USED IN THE II being richer in naphthenic structures.
MODEL DESIGN

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 23

Sulfur and nitrogen are found only in heterocycles; thioph~nique dans les p~troles et les extraits de roche.
one part of oxygen can also be found in ether links. Analyse par spectromrtrie de masse et chromatographie
en phase gazeuse. Rev. Inst. Fr. Pbt. XXXIX(I), 3-40.
There data have been combined with elemental Chappe B., Michaelis W. and Albrecht P. (1980) Molecular
analyses in the models of kerogens proposed here. fossils of archaebacteria as selective degradation products
The resulting distribution of functional groups and of kerogen. In Advances in Organic Geochemistry 1979
heterocycles is given in Table 3. (Edited by Douglas A. G. and Maxwell J. R.), pp.
265-274, Pergamon Press, Oxford.
CONCLUSION: ITEMS OPEN TO DISCUSSION Combaz A. and De Matharel M. (1978) Organic sedimen-
tation and genesis of petroleum in Mahakam delta,
The bonding position of particular molecules such Borneo. Am. Assoc. Pet. Geol. Bull. 62, 1684-1695.
Dereppe J. M., Boudou J. P., Moreaux C. and Durand B.
as some steroids, triterpenoids, waxes, is fairly well (1983) Structural evolution of a sedimentologically
known. However, this is not true for the major part homogeneous coal series as a function of carbon content
of the molecules constituting kerogen. So the distri- by solid state ~3C NMR. Fuel 62, 575-579.
bution of functional groups on aromatic domains Durand B. (1980) Kerogen (Edited by Durand B.), Technip,
Paris.
and the position of side chains in our models have Durand-Souron C. (1980) Thermogravimetric analysis and
only a statistical value. Specific degradative methods associated techniques applied to kerogens. In Kerogen
should give a better insight in the position of these (Edited by Durand B.), pp. 143-161. Technip, Paris.
chemical bonds. Hoering T. C. (1984) Thermal reactions of kerogen with
Bonds between polyaromatic nuclei have been added water, heavy water, and pure organic substances.
Org. Geochem. 5(4), 267 278.
represented only as covalent, C - C or C-hetero- Huc A. Y. (1978) Geochimie organique des schistes
element bounds. Probably there are other types of bitumineux du Toarcien du Bassin de Paris. Thrse de
bonds such as hydrogen bonds, pi electron inter- Doctorat-rs-Sciences, Universit6 Louis Pasteur, Stras-
actions, Van der Waals forces, physical adsorption bourg, France.
Larter S. R. and Douglas A. G. (1982) Pyrolysis methods
and steric entrapment (Pelet et al., 1986). However, in organic geochemistry: an overview. J. Anal. Appl.
they have not been taken into account because we Pyrol. 4, 1 19.
ignore what is their relative proportion in kerogen. Micke B. and Michaelis W. (1986) Molecular fossils from
Studies on unsaturates released by pyrolysis of ker- chemical degradation of macromolecular organic matter.
ogen are actually in progress to determine the relative In Advances in Organic Geochemistry 1985. Org. Geochem.
10(4,~), 847-858.
content of covalent bonds (Behar et al., 1987). Nip M., Tegelaar E. W., De Leeuw J. W. and Schenck
Models presented in this paper try to satisfy much P. A. (1986) Analysis of recent and fossil plant cuticles by
of the present data concerning kerogens in the litera- Curie point pyrolysis-mass spectrometry and Curie point
ture. Nevertheless they have only a statistical value pyrolysis-gas chromatography-mass spectrometry: recog-
nition of a new highly aliphatic biopolymer. In Advances
and do not infer any hypothesis on the molecular size
in Organic Geochemistry 1985. Org. Geochern. 10(445),
and homogeneity of the main types of kerogens, as it 769-778.
was discussed previously. Oberlin A., Boulmier J. L. and Villey M. (1980) Electron
Acknowledgements--Studies done in IFP by Geochemistry microscopic study of kerogen microtexture. Selected crite-
and Analytical Physics Departments have largely con- ria for determining the evolution path and evolution stage
of kerogen. In Kerogen (Edited by Durand B.), pp.
tributed to a better insight in kerogen structures. We
thank particularly R. Pelet and B. Durand for fruitful 191 241. Technip, Paris.
Ocampo R., Callot H., Valisolalo Y., Schmid J. C., Connan
discussions and helpful criticisms. The help of C. Leblond
J. and Albrecht P. (1985) Identification and geochemical
and E. Deroze for calculations and drawing was highly
significance of polar porphyrins and sulphur components
appreciated. in geochemical organic matter. Oral communication, 12th
International Meeting on Organic Geochemistry, J/ilich.
REFERENCES
Pelet R. (1980) Evolution grochimique de la mati~re or-
Albrecht P., Vandenbroucke M. and Mandengue M. (1976) ganique. In Kerogen (Edited by Durand B.), pp. 475-499.
Geochemical studies on the organic matter from the Technip, Paris.
Douala basin (Cameroon)~I: Evolution of the extrac- Pelet R., Behar F. and Monin J. C. (1986) Resins and
table organic matter and the formation of petroleum. asphaltenes in the generation and migration of petroleum.
Geochim. Cosmochim. Acta 40, 791-799. In Advances in Organic Geochemistry 1985. Org. Geochem.
Baker E. W. and Louda J. W. (1983) Thermal aspects in 10(1-3), 481-498.
chlorophyll geochemistry. In Advances in Organic Geo- Robinson W. E. (1969) Kerogen of the Green River for-
chemistry 1981 (Edited by Bjoroy M. et al.), pp. 401-421. mation. In Organic Geochemistry--Methods and Results
Wiley, Chichester. (Edited by Eglinton G. and Murphy M. T. J.), Springer,
Behar F. and Pelet R. (1985) Pyrolysis-gas chromatography Berlin.
applied to organic geochemistry. Structural similarity Schmitter J. M. and Arpino P. J. (1983) Possible origin and
between kerogens and asphaltenes from related extracts fate of methyl quinolines and methylbenzo/h/quinolines
and oils. J. Anal. Appl. Pyrol. 8, 173-187. from crude oils. In Advances in Organic Geochemistry
Behar F. and Pelet R. (1986) A new technique for oil-source 1981 (Edited by Bjoroy M. et al.), pp. 802 812. Wiley,
rock and oil/oil correlation. Preprints ACS, Geochem. Chichester.
Div., Miami Meeting, April 1985. In press. Schnitzer M. and Khan S. U. (1978) Soil Organic Matter,
Behar F., Vandenbroucke M. and Pelet R. (1987) Char- Elsevier, Amsterdam.
acterization and quantification of saturates entrapped Simoneit B. R. and Burlingame A. L. (1973) Carboxylic
inside the kerogen network. 13th International Meeting on acids derived from Tasmanian tasmanite by extractions
Organic Geochemistry, Venice, 21-25 September. and kerogen oxidations. Geochim. Cosmochim. Acta 37,
Castex H., Roucach6 J. and Boulet R. (1974) Le soufre 595~10.
24 F. BEHAR and M. VANDENBROUCKE

Speight J. G. and Moschopedis S. E. (1979) Some obser- Tissot B., Deroo G. and Hood A. (1978) Geochemical study
vations on the molecular "nature" of petroleum as- of the Uinta basin: formation of petroleum from the
phaltenes. Preprints ACS, Petroleum Chem. Div., Wash- Green River formation. Geochim. Cosmochim. Acta 42,
ington, September. 1469-1485.
Spyckrerelle C. (1975) Constituants aromatiques de srdi- Vandenbroucke M., Behar F. and Georgakopoulos A.
ments. Thrse de Doctorat-rs-Sciences, Universit6 Louis (1986) Application of some pyrolysis techniques to humic
Pasteur, Strasbourg, France. substances from marine sediments. Int. Humic Substances
Tissot B., Califet-Debyser Y., Deroo G. and Oudin J. L. Society 2nd Int. Conf. (Edited by Hayes M. H. and Swift
(1971) Origin and evolution of hydrocarbons in early R. S.), University of Birmingham.
Toarcian shales, Paris basin, France. Am. Assoc. Pet. Van de Meent D., Brown S. C., Philp R. P. and Simoneit
Geol. Bull. 55, 2177-2193. B. R. (1980) Pyrolysis--high resolution gas
Tissot B., Durand B., Espitalie J. and Combaz A. (1974) chromatograph~,--mass spectrometry of kerogens and
Influence of nature and diagenesis of organic matter in the kerogen precursors. Geochim. Cosmochim. Acta 44,
formation of petroleum. Am. Assoc. Pet. Geol. Bull. 58, 999-1013.
499-506. Van Krevelen (1961) Coal. Elsevier, Amsterdam.
Tissot B., Pelet R., Roucache J. and Combaz A. (1977) Vitorovic D. (1980) Structure elucidation of kerogen by
Utilisation des alcanes comme fossiles grochimiques indi- chemical methods. In Kerogen (Edited by Durand B.), pp.
cateurs des environnements grologiques. In Advances in 301-338. Technip, Paris.
Organic Geochemistry 1975 (Edited by Campos R. and Young D. K. and Yen T. H. (1977) The nature of straight-
Gofii J.), pp. 117 154, Enadimsa, Madrid. chain aliphatic structures in Green River kerogen. Geo-
Tissot B. and Welte D. H. (1978) Petroleum Formation and chim. Cosmochim. Acta 41, 1411-1417.
Occurrence. Springer, Berlin.