Organic Geochemistry 30 (1999) 1509±1516

www.elsevier.nl/locate/orggeochem

A natural pyrolysis experiment Ð hopanes from

hopanoic acids?
Barry Bennett, Geo€rey D. Abbott*
Department of Fossil Fuels and Environmental Geochemistry (Postgraduate Institute), NRG: Drummond Building,
The University, Newcastle upon Tyne, NE1 7RU, UK

Abstract
The formation or generation of hopanes are important processes during both the natural heating of organic-rich
sediments and laboratory pyrolysis experiments. Molecular maturity parameters as well as the amounts (ng/g rock) of
the C31 hopanes and C30±C32 hopanoic acids were quanti®ed in a Jurassic silty shale horizon (Isle of Skye, Scotland) as
a function of distance from an igneous intrusion. The maturity pro®les of the homohopanes and the hopanoic acids are
comparable. There is also a correlation between the decreasing amounts of C30±C32 hopanoic acids and concomitant
increases in C29±C31 hopanes suggesting that free hopanoic acids could be one potential source of hopanes in this
particular horizon. Other possible sources could include hopanoic acids that are bound into the macromolecular frac-
tion. # 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Hopanoic acids; Hopanes; Contact metamorphism; Decarboxylation; Thermal maturation

1. Introduction between this maturity parameter and the release or

Naturally occurring hopanoids from most bacteria
have the same C-22 stereochemistry (Rohmer and Our-
isson, 1976; Zundel and Rohmer, 1985a,b; Neunlist and
Rohmer, 1985; Neunlist et al., 1988). Following deposi-
tion of these molecules into recent sediments this ste-
reochemistry is largely retained (e.g. Philp, 1985) and
there is a probable rapid degradation of the poly-
functionalised side chains of all the bacteriohopane
derivatives (Rohmer et al., 1992). With increasing burial
depth, and associated temperature rise, the side chain R-
con®guration, preferred in immature sediments, converts
gradually to a C-22 epimeric mixture Ð this process is
tracked by calculating a biomarker maturity parameter
from GC±MS, e.g. the 17a, 21b(H) 22S/(22S+22R) C31
homohopane parameter (22S/(22S+22R)) which is
given by the peak area of the 22S epimer relative to the
sum of itself and the peak area of its 22R counterpart in
the m/z=191 mass chromatogram (e.g. Peters and
Moldowan, 1993). We have investigated the relationship
* Corresponding author. Tel.: +44-191-222-6605; fax: +44-
191-222-5431.
E-mail address: geo€.abbott@newcastle.ac.uk (G.D. Abbott).
0146-6380/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S0146-6380(99)00122-9
generation and concomitant degradation of free homo-
hopanes in a siltstone horizon intruded by a dolerite
dyke (Bishop and Abbott, 1993). This igneous intrusion
is particularly interesting because the e€ects of a rela-
tively large temperature change are recorded by the
changing molecular distributions within a sediment of
constant organic matter type. We suggested that the
macromolecular and/or functionalised fractions of sedi-
mentary organic matter can act as sources for the
release or generation, of these free biomarkers based
upon a kinetic scheme derived during a prior study on
the hydrous pyrolysis of a vitrinite kerogen (Abbott et
al., 1990). Hydrous pyrolysis studies on an immature
marl from the Vena del Gesso Basin (northern Italy)
have indicated that biomarker generation may be con-
sidered as consisting of two discrete steps (Koopmans et
al., 1996, 1997). The ®rst is a partial decomposition of
kerogen to yield a polar-rich bitumen which contains
the biomarkers as bound moieties. These bound bio-
markers are then released from the polar fraction as free
hydrocarbons. Oxygenated compounds are important
components of the polar fraction.
Concern about global resources and climate has led to
a need for the development of energy sources other than
1510 B. Bennett, G.D. Abbott / Organic Geochemistry 30 (1999) 1509±1516
fossil fuels. Direct conversion of biomass into liquid
fuels, rich in hydrocarbons, is one such alternative. The
removal of chemically bound oxygen is one of the pri-
mary aims during the production of biofuel because this
will increase its hydrocarbon content. If we use petro-
leum generation as a natural analogy to biomass pyr-
olysis then if we can understand the mechanisms for the
release of hydrocarbons from the polar fraction during
thermal maturation, this may help us to ®nd out the best
methods for producing energy-rich biofuels. One poten-
tial source of saturated hopanoids, such as homo-
hopanes, in the functionalised fraction of organic matter
is the class of compounds termed hopanoic acids.
The molecular characterization and sedimentary
occurrence of hopanoic acids is well established (e.g.
Quirk et al., 1984; Ja€e et al., 1988). In sediments, C28±
C36 hopanoic acids occur with the following con®gura-
tions at the C-17 and C-21 chiral centres; 17b, 21b(H)
(abbreviated to bb); 17a, 21b(H) (abbreviated to ab)
and 17b, 21a(H) (abbreviated to ba). The bb stereo-
chemistry is inherited from the presumed precursors
namely bacteriohopanetetrol and related tetrafunctional
biohopanoids (e.g. Rohmer et al., 1992). In young and
immature sediments the bb (22R)-con®guration dom-
inates: C32 bb (22R)-occurs as the most abundant
hopanoic acid compound in recent sediments (e.g. Quirk
et al., 1984; Innes et al., 1997), Albian±Aptian carbo-
naceous marls (Barnes et al., 1979) and Cretaceous
black shales (Ohkouchi et al., 1997). The increasing
amounts of ba (22R)- and (22S)-as well as the ab (22R)-
and (22S)-isomers relative to the bb (22R)-con®guration
during burial maturation have been the focus of a
number of studies (e.g. Ja€e and Gardinali, 1990).
Similar generation pro®les were observed for the C30 ab
hopanes and the total hopanoic acids with increasing
burial depth in the Maracaibo Basin (Ja€e et al., 1992).
Therefore, this paper reports a study on the relation-
ship between the hopanes and hopanoic acids during
contact metamorphism. Hopanoic acids and hopanes
were quanti®ed by combined gas chromatography±mass
spectrometry. Changes in molecular maturity para-
meters, as well as in the amounts of these compounds,
were then measured relative to the emplacement of an
igneous intrusion into a Jurassic silty shale horizon in the
Dun Caan shale member of the Bearreraig Sandstone
Formation (Isle of Skye, Scotland). Finally, the defunc-
tionalisation of hopanoic acids is considered as a possible
process by which hopanes are formed in these sediments.
2. Experimental
2.1. Samples
Samples from a Jurassic silty shale horizon in the
Dun Caan shale member of the Bearreraig Sandstone
Formation (Isle of Skye, Scotland) were collected over a
distance interval ranging from 0.1 m to 1.24 m from a
dolerite dyke (0.9 m thickness). Based on ®ndings from
our prior study (Bishop and Abbott, 1993), the posi-
tions of these samples were carefully chosen so that the
changing isomeric distributions of both the hopanoic
acids and the hopanes could be analysed through and
beyond the e€ective ``oil window'' as a function of
increasing distance from the contact of the igneous
intrusion with the sedimentary horizon. Some of the
sediment samples from Bishop and Abbott (1993) have
been reanalysed but we have also included samples at
di€erent distances from the dyke contact which were not
investigated in the earlier study.
2.2. Extraction and fractionation
Authentic standards, 5b-cholanic acid and 5a-[2,2,
4,4-d4]-cholestane with a side chain (20R)-con®guration
(d4-cholestane), were added in known amounts to the
powdered rock prior to extraction to enable quanti®ca-
tion of the hopanoic acids and hopanes, respectively.
About 100 g of powdered rock was extracted with
dichloromethane/methanol (93:7, v/v) in a soxtherm
apparatus. The extract was then evaporated to dryness
and then separated into neutral and acidic fractions
using the method described by McCarthy and Duthie
(1962). The acidic fraction was then treated with freshly
distilled diazomethane to form the methyl esters of the
hopanoic acids. These methyl esters were then separated
from the acidic fraction by thin layer chromatography
(TLC) using diethyl ether/light petroleum ether (10:90,
v/v) as the developer. The hopanes were separated from
the neutral fraction by TLC using light petroleum ether
as the developer.
2.3. Gas chromatography
Gas chromatography (GC) was carried out on a
Carlo Erba Mega Series 5160 instrument ®tted with an
air-cooled on-column injector and a ¯ame ionization
detector. The hopanoic acids and hopanes were sepa-
rated using a fused silica capillary column (30 m0.32
mm i.d.) coated with a phenylmethylsilicone bonded
stationary phase (HP-5, ®lm thickness 0.25 mm). The
carrier gas was hydrogen. The oven temperature was
held at 50 C for 2 min and then programmed at a rate
of 4 C/min to 300 C at which it was held for 30 min. A
Multichrom (VG Data Systems, Micro VAX 2000) data
handling system was used to acquire and process the
GC data.
2.4. Gas chromatography±mass spectrometry
Gas chromatography±mass spectrometry (GC±MS)
was carried out on a Hewlett±Packard 5890 GC directly
 B. Bennett, G.D. Abbott / Organic Geochemistry 30 (1999) 1509±1516 1511

coupled to a Hewlett±Packard 5970B single quadru- 3.2. Maturity parameters and homohopane
pole mass spectrometer (electron voltage 70 eV, mass quanti®cation
range m/z 50±550, cycle time 1.2 s) with helium as
carrier gas. The GC was ®tted with a fused silica Changes in the 17b, 21b(H)/(17, 21b(H)+17b, 21
capillary column (25 m0.2 mm i.d.) coated with a 5% (H)+17b, 21b(H)) C31 (22R)-homohopane parameter
phenylmethylsilicone bonded stationary phase (HP-5, [bb/(ab+ba+bb)] are plotted as a function of distance
®lm thickness 0.11 mm). The oven temperature was from the dyke contact in Fig. 2a. bb/(ab+ba+bb)
programmed from 40 C (2 min) to 150 C at 10 C/min,
150±220 C at 6 C/min and ®nally 220±300 C (30 min)
at 4 C/min.
The peak areas of the hopanes and hopanoic acids
were measured during GC±MS analysis by integration
using MASS LAB. Sample suites were analysed in single
batches on the same day to minimise variations which
could arise from drift in mass spectral responses. The
hopanes were quanti®ed using the internal standards
method described in our earlier study (Bishop and
Abbott, 1993).

2.5. Identi®cation and quanti®cation of hopanoic acids

Hopanoic acids were identi®ed by comparison with Fig. 1. EOM versus distance from the dyke contact. Shaded
published mass spectra and GC±MS distributions (e.g. area represents the e€ective ``oil window''.
Ja€e et al., 1988). Their amounts (ng/g rock) were
determined from peak areas in the m/z=191 mass
chromatogram compared to the area response of the
internal standard (cholanic acid methyl ester) in the
m/z=217 trace. Response factors for the individual
isomers were not corrected relative to that of the
internal standard, therefore, the amounts (ng/g rock)
are not absolute measurements. Co-elution of C31 bb
(22R)- and C32 bb (22R)-hopanoic acids ruled out
quanti®cation of these particular components using
only the m/z=191 mass chromatogram. Instead the
abundance of the m/z=191 fragment ion for each of
these epimers was calculated based on the relative
intensities of the m/z=191 to the m/z=249 ions for
the C31 bb (22R)-epimer and the m/z=191 to the m/z
263 ions for the C32 ba (22R)-hopanoic acids (van
Dorsselaer, 1975).

3. Results and discussion

3.1. Bulk geochemical characteristics

The distances of the samples from the dyke contact

are given as percentages of dyke thickness (% d.t.). The
principal zone of extractable organic matter (EOM)
generation is characterized by the signi®cant increase of
the EOM at about 50% d.t. and by its subsequent
decrease to a background level at about 25% d.t. as the
dyke contact is approached (Fig. 1). This zone is termed
the e€ective ``oil window'' below and is denoted by the Fig. 2. Plots of (a) bb/(ab+ba+bb) in C31 (22R)-hopanes and
shaded area both in Fig. 1 and the subsequent distance- (b) the amounts of (22R)- C31 ab (*), ba (&) and bb (
)
related pro®les. hopanes (ng/g rock) versus distance from the dyke contact.
1512 B. Bennett, G.D. Abbott / Organic Geochemistry 30 (1999) 1509±1516

decreases gradually between 138% d.t. and 98% d.t. It

then falls dramatically from 0.4 to zero between 98%
d.t. and 52% d.t. This decrease in the bb/(ab+ba+bb)
maturity parameter is a consequence of the decreasing
amounts of the C31 bb (22R)-con®guration, down to a
level below the limit of detection at 52% d.t., and the
concomitant increases to maxima in the amounts of the
ba (22R)- and ab (22R)-con®gurations between 100%
d.t. and 50% d.t. (Fig. 2b). Fig. 2b shows that sig-
ni®cant amounts of the C31 ba (22R)- and C31 ab (22R)-
con®gurations are still present well beyond the point at
which C31 bb (22R)- cannot be detected. Also the max-
imum amounts of the C31 ba (22R)- and C31 ab (22R)-
epimers generated as the dyke is approached are a
number of times larger than the amount of the free bb
(22R)-homohopane present in the unheated, distal sam-
ples. These results suggest that some of the ab and ba
con®gurations can come from a source, or even multiple
sources, other than the free bb (22R)-homohopane. The
most likely candidates are species bound to a macro-
molecular component, such as the kerogen and asphal-
tene fractions, as well as functionalised molecules in the
resin (NSO), aromatic hydrocarbon and unsaturated
hydrocarbon fractions of organic matter (Abbott et al.,
1990; Bishop and Abbott, 1993).
Changes in the 22S/(22S+22R) 17, 21b(H) homo-
hopane parameter [22S/(22S+22R)] are plotted as a
function of distance from the igneous intrusion in Fig.
Fig. 3. Plots of (a) 22S/(22S+22R) for C31 hopanes and (b) the
3a. 22S/(22S+22R) increases from its background value amounts of (22R)-(~) and (22S)-(&) C31 ab hopanes (ng/g
of 0.13 at 75% d.t. to a maximum value of 0.53 at 31% rock) versus distance from the dyke contact.
d.t. whereupon it inverts as the dyke contact is approa-
ched. Fig. 3b shows that the increase in 22S/(22S+22R)
is controlled by the relative rates of generation and present in only very small amounts and, therefore, we
degradation of the 22R- and 22S-epimers, although have focused on the quantitatively signi®cant C30±C32
direct con®gurational isomerization could also be a homologues in this study. The isomeric distributions of
contributory process. The same explanation was argued the C30±C32 hopanoic acids are presented as a function
for the changes in 22S/(22S+22R) measured in another of relative distance from the dyke in Fig. 4. These are
study on samples from this horizon (Bishop and Abbott, dominated by the thermodynamically less stable bb
1993) as well as a more recent study on an adjacent compounds for the samples furthest from the intrusion.
carbonate concretionary horizon (Farrimond et al., From 93% d.t. to 47% d.t. the amounts of the ab and
1996). ba isomers rise relative to those of the bb series which is
The generation of hopanes requires a source which very close to or below the limit of detection at 47% d.t.
has been suggested above as being one or both of the However, as the dyke contact is approached (22% d.t.)
macromolecular and functionalised components of the immature bb series reappears to dominate these dis-
sedimentary organic matter (e.g. Abbott et al., 1990; tributions. These changes in the distributional features
Bishop and Abbott, 1993). In this study we have of the hopanoic acids are comparable to those observed
explored the possibility that hopanoic acids may be as a function of burial depth in rock samples taken from
functionalised precursors to the hopanes. The occur- the Maracaibo Basin in Venezuela (Ja€e and Gardinali,
rence and distributions of the hopanoic acids before and 1990).
through the oil window are described below.
3.4. Maturity parameters and hopanoic acid
3.3. Hopanoic acid distributions quanti®cation

The carbon number distribution of the hopanoic The total amounts of hopanoic acid isomers are
acids in these sediments ranged from C30 to C35. How- plotted versus % d.t. for the C30 (Fig. 5a), C31 (Fig.
ever, the C33±C35 hopanoic acids are either absent or 5b), and C32 (Fig. 5c) homologues. For each of these
 B. Bennett, G.D. Abbott / Organic Geochemistry 30 (1999) 1509±1516 1513

Fig. 4. Partial mass chromatograms of the C30 (m/z=235), C31 Fig. 5. Amounts (ng/g rock) of (a) C30, (b) C31 and (c) C32
(m/z=249) and C32 (m/z=263) hopanoic acids at di€erent dis- hopanoic acids versus distance from the dyke contact.
tances from the dyke contact.

three carbon numbers, the hopanoic acids are most

abundant (i.e. C30, 40 ng/g; C31, 160 ng/g and C32,
800 ng/g) in the sample furthest from the dyke contact
(138% d.t.). The amount of each homologue then pro-
gressively decreases as the contact is approached.
The maturity parameter comprising 17b, 21b(H)/
(17, 21b(H)+17b, 21(H)+17b, 21b(H)) for the
hopanoic acids with the side chain (22R)-con®guration
[HA-bb/(bb+ba+ab)] for each of the above three
hopanoic acid carbon numbers decreases gradually
between about 150 and 100% d.t. and then falls rapidly
to zero at about 50% d.t. from the intrusion (Fig. 6).
Over this distance interval (150±50% d.t.), these pro®les
are very similar to that of the bb/(bb+ba+ab) para-
meter for the C31 (22R)-hopane presented in Fig. 2a.
There is then an apparent reappearance of the bb iso- Fig. 6. Plots of HA-bb/(ab+ba+bb) in C30 (&), C31 (*) and C32
mers, especially for the C32 homologue, between 50% (
) (22R)-hopanoic acids versus distance from the dyke contact.
d.t. and the dyke contact (Figs. 4 and 6). The amounts
of these particular isomers are, however, very small in of the indigenous biomarkers that were present when
this distance interval (Figs. 5 and 7) although the bb the dyke ®rst intruded into the sediment. Ja€e and
isomers at 22% d.t. are clearly present in the mass Gardinali (1990), however, have also detected a simi-
chromatograms shown in Fig. 4. The alternative expla- larly immature distribution of hopanoic acids in some
nation for this immature signal is that it is the result of mature sediment extracts from the Maracaibo Basin in
post-depositional ingress. This ingress may be present Venezuela which they ascribed to the secondary genera-
throughout the horizon but becomes apparent close to tion of tightly bound immature acids from geopolymeric
the dyke contact as a result of the thermal degradation material at elevated maturities.
1514 B. Bennett, G.D. Abbott / Organic Geochemistry 30 (1999) 1509±1516
Fig. 7. Amounts (ng/g rock) of ab (*), ba (&) and bb (
)
(22R)-epimers for the (a) C30, (b) C31 and (c) C32 hopanoic
acids versus distance from the dyke contact.
There is a C-22 epimeric mixture for all of the ab, ba
and bb isomers of the C30 hopanoic acids throughout
the sample suite (Figs. 4 and 8a). This is because the
formation of the (22S)-con®guration from the (22R)-
con®guration is a facile process for the C30 homologue
due to the enolization of the carboxylic acid group
adjacent to C-22 (Ja€e et al., 1988). HA-22S/(22S+22R)
was also measured for the ab and the ba series for the
C31 (Fig. 8b) and C32 (Fig. 8c) homologues. In contrast
to those for the C30 isomers these values vary sig-
ni®cantly throughout the aureole. Both the C31 and C32
ab HA-22S/(22S+22R) parameters (Figs. 8b and c,
respectively) start to increase from background levels of
about 0.1 at about 75% d.t. and then rise to a maximum
of about 0.5 at 33% d.t. For the C32 homologues an
inversion in this maturity parameter is then observed as
the dyke contact is approached from 33% d.t. These
changes follow the same distance-related pro®le descri-
bed by the 22S/(22S+22R) homohopane maturity
parameter presented in Fig. 3a.
The four pro®les for the amounts of the C31 and C32
ab hopanoic acid epimers (Fig. 9b and c) reveal that the
increases in the C31 and C32 ab HA-22S/(22S+22R)
Fig. 8. Plots of HA-22S/(22S+22R) for the (a) C30, (b) C31
and (c) C32 hopanoic acids versus distance from the dyke con-
tact.
parameters occur for the same samples in which there
are overall decreases in the amounts of the (22R)- and
(22S)-con®gurations with decreasing distance from the
dyke. From about 75% d.t. the amounts of the (22R)-
con®gurations dip towards the dyke contact. There are
small rises in the amounts of the (22S)-epimers between
about 75 and 59% d.t. for both the C31 and C32 homo-
logues which could be the result of either con®gura-
tional isomerization or are due to generation of the free
acids from hopanoic acids which are bound to a high-
molecular-weight fraction (e.g. kerogen) of organic
matter. All four pro®les then decrease close to or below
the limit of detection at 29% d.t.
3.5. Relationship of hopanes to hopanoic acids
If the amounts of the free hopanoic acids are summed
over the C30±C32 carbon number range, these decrease
from 1000 ng/g at 143% d.t. down to 100 ng/g at
50% d.t. The integrated amounts of the C29±C32 hopanes
increase from 780 ng/g at 143% d.t. to 2280 ng/g at
50% d.t. (Fig. 10). This indicates that there is a correla-
tion between the decreasing amounts of hopanoic acids
 B. Bennett, G.D. Abbott / Organic Geochemistry 30 (1999) 1509±1516
Fig. 9. Amounts (ng/g rock) of (a) C30, (b) C31* and (c) C32*
(22R)-(~) and (22S)-(&) epimers of ab hopanoic acids versus
distance from the dyke contact. *C31 and C32 (22S)-amounts5.
Fig. 10. Total amounts (ng/g rock) of C30-C32 hopanoic acids
(&) and C29-C32 hopanes (&) versus distance from the dyke
contact.
and the concomitant increase in the hopanes suggesting
that hopanes may be formed by decarboxylation of the
hopanoic acids as the dyke contact is approached. This
does not rule out other sources which may be con-
tributing to hopane generation including the possibility
that some of the precursor hopanoic acids are not only
present in the free form but may also be bound into the
macromolecular fraction. These are either released as
free acids or they may be defunctionalised during the
1515
release process itself to form the hopanes. It has also
been suggested that homohopanes can be formed via
sulphurisation of the bacteriohopane derivatives and
subsequent desulphurisation/side chain cleavage (KoÈster
et al., 1997). Further work is needed to clarify the
mechanism of the defunctionalisation process, however,
transformations of carboxylic acids into saturated
hydrocarbons with the loss of one carbon atom have
been reported in the literature (Barton et al., 1980).
4. Conclusions
1. The gradual changes in the isomeric composition of
the homohopanes, caused by the heating e€ects of a
dolerite dyke on a silty shale horizon, suggest that
the ab and ba (22R)-homohopanes, as well as the
C31 ab (22S)-con®guration, are generated or formed
from a source, or even multiple sources, other than
the bb (22R)-homohopane. The most likely candi-
dates are species bound to a macromolecular com-
ponent, such as the kerogen and asphaltene
fractions, as well as functionalised molecules in the
resin (NSO), aromatic hydrocarbon and unsatu-
rated hydrocarbon fractions of organic matter
(Abbott et al., 1990; Bishop and Abbott, 1993).
2. The changes in the maturity pro®le of the bb/
(ab+ba+bb) parameter for the homohopanes
and the HA-bb/(bb+ba+ab) parameters for
both the C31 and the C32 homologues of the
hopanoic acids are comparable over the distance
interval 138±50% d.t.
3. The changes in the HA-22S/(22S+22R) para-
meters for the C31 and C32 hopanoic acids each
follow the same distance-related pro®le described
by the 22S/(22S+22R) homohopane maturity
parameter.
4. Free hopanoic acids could be a potential source of
hopanes as the dyke contact is approached. Addi-
tional sources could include hopanoic acids that are
bound into the macromolecular fraction and then
are either released as free acids or are defunctiona-
lised during the release process itself to form the
hopanes. Further studies on decarboxylation
mechanisms in sediments may shed new light on
better methods for producing energy-rich biofuels.
Acknowledgements
We thank Norsk Hydro a.s. for funding this work. We
also thank Andy Bishop (Texaco, Houston) for the col-
lection of samples and Patrick Wehrung (Universite Louis
Pasteur, Strasbourg) for providing hopanoid standard
compounds. Technical assistance by Paul Donohoe
1516 B. Bennett, G.D. Abbott / Organic Geochemistry 30 (1999) 1509±1516
(Newcastle University) for the GC±MS analyses as well
as by Christine Jeans and Barbara Brown (Newcastle
University) for preparation of the Figures is gratefully
acknowledged. We also thank Paul Farrimond (New-
castle University) for commenting on a draft of this
manuscript. We are particularly grateful to Martin
Koopmans, Rolando di Primio and Jùrgen Bojesen-
Koefoed for their constructive reviews which helped us
to improve this manuscript.
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