ALKANE BIOMARKERS.

GEOCHEMICAL SIGNIFICANCE AND

APPLlCA TION IN OIL SHALE GEOCHEMISTRY
F.J. GONZALEZ-VILA
Instituto de Recursos Naturales y Agrobiologia, C.S.I.e.
P.O. Box 1052
41080-Sevilla
Spain
ABSTRACT. The application of alkane biomarkers for source, palaeoenvironmental
reconstruction, maturity and biodegradation of sedimentary organic matter is briefly
reviewed. Data on the extractable biomarker composition of a Spanish oil shale, as well
as some considerations on future work in biomarker geochemistry are also included.
1. Biomarkers. Concept and Applications
la spite of the progress made in the last decades, understanding the origin and fate of
organic compounds in Nature still remains an intriguing and difficult task. However,
the concept of using organic compounds as measures of events and processes in the
natural worId is now widely accepted and applied in a wide range of disciplines.
The organic substances present in recent and ancient sediments are thought to reflect
the source inputs and the environmental conditions, including microbial activity, at the
time of deposition. A restricted number of these organic substances, the so-called
molecular fossils or biological markers (biomarkers for short), are molecules directly
inherited from the organisms living at the time of deposition which have been preserved
without subsequent alteration, or with only minor changes, so that their basic carbon
skeleton remains intact (1,2)
The term biomarker stems therefore from the similarity of certain chemical structures
in the sedimentary record to precursor molecules which occur in unique biosynthetic
products of specific groups of organisms in the natural environment. Compounds whose
biological origin is uncertain but whose structural specificity makes them useful as
correlation parameters in source diagnosis are also referred to as biomarkers. Small
changes in the structures of these biomarkers are due to microbial transformations in
the water column and in recent sediments or chemical reactions during diagenesis in
ancient sediments. It should be emphasized that, although the inputs contributing to the
51
C. Snape (ed,). Compostion. ami Conversion af Oil Shales, 51
1995 Kluwer Academic Publishers, Printed in Nether/ands.
52
sedimentary organic matter are deduced from the presence of specific biomarkers, their
absence does not necessarily imply that the biosynthetic precursors and the
corresponding biota were not present in the depositional environment.
The biomarker approacb, i.e. isolation and recognition of biomarkers from different
environmeots, constitutes a powerfu) too) in many areas of geocbemistry. Tbe use of
biomarkers has moved from an academic pursuit (assessement of the nature of the
different organic inputs ioto a sedimeot, reconstruction of paleo-environments, study
of the processes of early diagenesis and tbermal maturation, etc) to a highly applied
analytical technique in technological fields sucb as petro)eum and gas exploration, based
mainly on the determination of source, maturity, migration and biodegradation of
bydrocarbons. In all cases, conclusions based on biomarker distribution data are
stronger than those based on any single compound or class of compounds.
2. ExtractioD,IsolatioD and AnaJysis of Biomarkers
Biomarker determinations provide a chal)enge for the analytical cbemist. In general. the
biomarkers of greatest interest are present in relatively low concentrations in crude oils
and rock extracts, whicb are complex mixtures of organic compounds.
Extraction of biomarkers from sediments and oils is. normalIy accomplisbed by
conventional solid-liquid extraction procedures using different solvents or mixtures ot
tbem in Soxhlet apparatus. Over recent years new extraction techniques based on the
use of ultrasonic agitation ()) and supercritical fluids lO) have been developed. The
supercritical fluid extraction (SFE) seems to bave a promising future, since it
considerable advantages regarding extraction time and elimination of environmentai
bazards.
Afier removal of asphaltenes, insoluble in n-pentane, the extracts are
fractionated into saturated, aromatic and polar components by adsorptior.
chromatograpby on column or on modern solid phase extraction cartridges .
Then-alkanes are usually tbe most abundant compounds in the saturated fractions L);
crude oils and rock extracts, and sometimes it is necessary to remove them as ar
analytical step to effectively enhance the concentration of other more specifi,
biomarkers, such as branched and cyclic alkanes. Many concentration techniques hay,
been used quite effectively. Amongst tbem tbe clatration with urea and the use o
molecular sieves seem to be the most useful to separate n-alkanes from thei:
brancbed/ cyclic congeners.
The most common methods for detection and identification of biomarkers in comple:
are the computerised Gas Chromatography-Mass Spectrometry (GC-MS
systems, which became readily available and are today indispensable for routine analysi
of crude oils and sediment extracts (6). Relatively different new techniques, such as GC
MS-MS and Supercritical Fluid Chromatography (SFC)-MS have introduced a numbe
of alternative methods for tbe analysis of stereoisomers and high molecular weigt
biomarkers.
55
3.Geochemical Significance of tbe Various Molecular Classes of Hydrocarbons
Found in Sediment Extracts and Petroleum
A coroprehensive review of all the areas of biomarker geochemistry which have
undergone a number of important reevaluations in the past decade (2.1-10) is beyond the
scope of this reporto Rather this chapter will essentially comprise an overview of
existing data (taken froro the aboye monograpbs, and only recent references to illustrate
trends and developments are included) on those aspects of alkane biomarker distribution
which relate lO the type of organic matter, the depositional environment, the thermal
maturity and indications for biodegradation. Another useful application of biomarkers
in oil exploration are the oil-oil and oil-source rocks correlations, as well as the
determination of relative migration distances of expelled hydrocarbons. Structures
marked throughout the text with Roman numbers are presented in Appendix l.
3.1. NORMAL ALKANES
N-alkanes are trace constituents of biologicallipids. However, these compounds have
excellent preservation characteristics and may therefore be regarded as biomarkers. The
most common application of n-alkanes is to infer the source of the organic materiaL
Input of terrigenous source material is indicated by a strong predominance of high
molecular weight odd-numbered alkanes (n-C
n
, n-C
29
and n-C
ll
), which are associated
with leaf waxes. Marine algae are known to produce lower molecular weight n-alkanes
with maximum at n-C
I1
and without any odd or even chain length preference.
Freshwater algae synthesize longer chain length n-alkanes, with a predomiilance similar
to that in higher land plants. Studies of bacteria have shown them to produce n-alkanes
in the n-CI, to n-Cn region with no marked odd/even preference.
The distribution of n-alkanes have been used to nter specific depositional
environment of source rocks. For example, the occurrence of n-alkane distributions with
an even-number preference is usually assumed to reflect evaporitic facies or marine
carbonate environments (10.11). This is probably a function of the highIy reducing nature
of the depositional environment which causes reduction rather than decarboxylation of
the biologically-4erived even carbon numbered fatty acids (12). The observation of
even/odd predominance in well-oxygenated systems has prompted other authors to
suggest a possible bacterial autochthonous origin for these alkanes (13.14).
Maturity and biodegradation can also influence the distribution of n-alkanes. Thus,
as maturity increases the odd/even or evenlodd predominance decreases. Bacterial
degradation of crude oils causes progressive removal of n-aIkanes beginning from the
low molecular weight homologues.
3.2. BRANCHED ALKANES
3.2.1. Monomethyl branched alkanes. These compounds occur mainIy as the iso- (2-
methyl) and anteiso- (3-methyl) alkanes, and derive from plant waxes (C
2
,-C
31
with an
54
odd chain predominance) or bacteria (Cn-C,. iso, C
n
and C
lI
anteiso).
Mid-chain branched alkanes, in particular methyl heptadecanes (C,s), with the meth:
substituent at C7 7 or C
s
have been proposed as biomarkers of cyanobacteria and henl
possibly of hypersaline environments (15,16)
3.2.2. Acyclic lsoprenoids. These compounds are known constituents of plants, animo
tissues and bacterial cell walls and have been reported in all classes of geologic,
samples. The phytol side chain of chlorophyl1-a accounts for the widespread occurrenc
of acyclic isoprenoids in the biosphere. They are chemically formed from variOl
combinations of C, isoprene units (1) through three main types of linkages : head-to-ta
(the most conunon, and include compounds such as pristane C,,(ll), phytane C2Q(III) 3D
homologues up to C.,), tail-to-tail (squalane, perhydro-.6-carotane, lycopane, etc), an
head-to-head (Cn-C) typical of thermophiJic and other archaebacteria).
Isoprenoids, and in particular the ratio of pristane to pbytane, have been widely use
to obtain information on depositional enviroomeots 00 the premise that both pristar
and phytane are derived from phytol. Diagenesis of CM phytol produces by reductic
and dehydratioo in C2Q phytane io highIy reducing conditions, whereas in less anox
conditions oxidation and decarboxylation prevail yielding C,9 pristane. However, sorr
important limitations 00 the use of the pristane/phytane ratio as ao indicator for oxyge
levels have arisen (,,17), and should be taken into consideration before using th;
parameter.
Since most Recent hypersaline eovirooments are characterised by reducing o n d i t i o n ~
the pristane/phytane ratio has also beeo suggested as an iodicator for salinity (',
Specific acyclic isoprenoids associated with particular eovirooments, such as the regul.
C
25
isoprenoid and botryococcane (IY), have been reported bydifferent authors (9).
3.3. MONOCYCLlC ALKANES
It is assumed that n-alkylcyclohexanes and n-alkyl,methylcyc1ohexanes arise fror
cyclization of biologically-derived fatty acids (19). Tbeir distribution in crude oils an
sediment extracts follows normally the n-alkane distribution with a large odd over eve
carbon number predominance.
Alkyl cyclohexanes with isoprenoid side chains are probably derived frol
carotenoids, which are abundant in algae and some higher plants, or are generated fror.
bacterial reworking of previously sedimented acyclic isoprenoids (10). The distributi0
and catagenesis of cycloalkanes in oils has been recently reviewed (21).
3.4. BICYCLlC ALKANES (SESQUITERPENOIDS)
These compounds have been identified in fossil resins, sediments and petroleum (22). Th,
two main types of bicycloalkanes identified are the drimanes (y) and the eudesmane
(Yl), The latter are believed to be derived from eudesmanol, an alcohol found preser
in higher plants, whereas drimanes are though to be derived from the degradation ("
polycyc1ic alkane precursors in bacteria and appear to be ubiquitous. The larg
55
number of isomers present in the samples a1so raises the possibility of stereochemical
interconversion as a result of diagenesis and maturation.
3.5. TRICYCLIC ALKANES.DITERPENOIDS AND TRICYCLYC TERPANES
The presence of diterpenoid hydrocarbons in fossil fuels and sediments is a very strong
indication of a terrigenous input lo tbe oils or source rocks, since tbese structures are
predominant constituents of higher plant resins and supportive tissues, especially in
conifers. The skeletal structure types found in fossil fuels consist primarily of
derivatives of the abietane (YII), pimarane (VIII) and Iabdane (!X) series.
Another series of tricyclic aIkanes commonly found in marine sediments and erude
oils is the homologous series of extended tricyelic terpanes (X) in the range from C,H}4
to C
4
,H
86
, and possibly higher. Tbey are not reported to be found in terrestrial souree
rocles or oils derived from terrigenous source material. Different natural precursors,
such as the tricycIobexaprenol, formed anaerobically from an ubiquitous eell
eonstituent, hexapreool, have been proposed for this series (23).
The trieycIie terpane distribution can be related to the nature of the depositional
environment. Thus, oils source from carbonate souree rocks usually show a dominant
C
23
homologue (24). 00 the otber hand, several autbors have proposed the potential use
of trieyclic terpanes as a maturity indicator in the lower maturity levels on the basis of
the variation in the relative amount of trieycIie terpanes to hopanes (23), and ehanges
observed in tbe isomers stereochemistry (26). Tricyclie terpanes are especially useful io
correlating nondegraded to biodegraded crude oils since they survive even severe
biodegradation processes (24).
3.6. TETRACYCLIC ALKANES
3.6.1. Non-Suroidal Tetracycc Terpanes. Tbe main types oftetracyelic alkanes found
io sediment and crude oils originate from different sources: a) kaurane (XI), beyerane
(XlI) and pbyIlocladane (Xill) are produced by diagenesis of tetracyclic alkenes
characteristics of conifer resios; b) tbe series of 4,5-secotriterpanes (XIV) is thought to
be formed from plant derived pentacycIic triterpenoids by thermal cracking, and e) the
17,21-secohopanes. (XY) and 8,14-secohopanes (XVI) derived from pentaeycIic
hopanoids by cleavage oftbe 17(21) and 8(14) bonds respectively, taking place either
by microbial activity during early diagenesis or by tbermocatalytic degradation of
hopanes (21).
Tetracyclic terpanes are usually present in a series from C
2
to C
21
Differences in
probable precursors of tetracyclic and tricyclic terpanes malees the ratio of ~
tetracyclic terpane over ~ tricyclic terpane a source parameter (l).
3.6.2. Steroidal Tetracyclanes. Sleranes. Steranes cornmoniy found in mature sediments
and crude oils are derived via diagenesis from sterols (XYID which are widely
dispersed in plants and mierorganisms, with the en and C
2B
sterols most abundant in
marine organisms and the ~ sterols in higher plants (2B). C
lO
4-desmethylsterols oceur
56
in marine invectebrates and marine algae (11), and 4-methylsterols are significantl
present in dinoflagellates (29).
Generally specific information on the organisms which relies on the position L
double bonds and functional groups will be lost, prior to oil generation. However, mo'
of the diagnostic information available from steranes in fossil fuel studies is mainJ
based on the stereochemical complexity of their basic skeleton, which is ofien retaine
and is observed in sediment extracts and oils.
Biomarker maturity determinations are generally based upon changes in steranes an
triterpanes (7). Sterols generally contain a 5,6 double bond and occur naturally as tt.
20R epimer with the 14a(H), 17a(H) configuration. As diagenesis progresses the doub
bond is hydrogenated and a new epimeric center with a mixture of 5a(H) and 58(H)
formed with a predominance of the 5a(H) epimer due to its greater thermal stabilir;
As the level of maturity increases the 148(H),178(H) isomers are formed as a mixtur
of the 20R and 20S epimers.
Sorne low molecular weight steranes, such as ~ I pregnane and en homopregnar.
(XYill) have been used as indicators of hypersaline and carbonate environments (JO 1
Many parameters involving the complex sterane distribution for source, deposition
environment, maturation, migration and biodegradation indicators have been proposc
(2.1.32). However, some cautions concerning the use of some indicators has be.:
enphasized by different authors (33.3<). In Table 1 the most widely used parameters al
summarized (2)
Diasteranes (XIX) present in oils and source rocks in relatively low abundances L
formed by acid-clay-catalyzed rearrangement of regular steranes, and therefore can t
used for depositional environment determinations.
3.7. PENTAeyeLIe ALKANES
3.7.1. Hopane-type triterpanes (XX). These constitute the group of triterpanes me
extensively used in biomarker studies. Their naturally occurring precursors, diplopte;
and e" tetrahydroxyhopane, are widely distributed among bacteria, blue-green alga-
sorne grasses and lichens and several feros (2).
Diagenesis and maturation of organic material containing the precursors leads
defunCtionalization and change ofthe biological178(H),216(H) stereochemistry to t
thermodynamically more stable 17a(H),216(H) configuration. At the same tim
formation of another series of hopane analogs, known as moretanes (XXI), with te
17.6(H),21a(H) configuration occurs.
The e
31
and higher homologues can occur as either 22S and 22R epimers due lO t
chical center at position en. Increasing maturation leads to mixtures of 22S and 2:
(naturally occurring) epimers with an equilibrium ratio of approximately 3:2. The rat
of the ~ 17a(H)-hopane (Tm), over the ~ 18a(H) (Ts), more resistant to therrr.
maturation than Tm, is used as a maturity parameter of oil and source rocks samplt
Most of the samples show the presence of regular hopanes from e
27
to e", with t
absence of the en homologue. The detection of this compound in a few notar
exceptions have been associated with the specific environment of deposition, such
fable 1.- SlJIIDary of biomarkers parameters based on steranes and triterpanes that have been used in petrole\lll stmies, (Philp, 1985).
* tricyclic terpanes (%)
* change in paraffin ooncentration plus increase in sterane and triterpane ooncentration
* C 9 + C
30
primary terpanes I C
2l
+ C 8 seoondary terpanes
* rm)' 18a(H)-22,29,30 trlsnorhopane (Ts)
* 56(H) steranes I 17a(H) hopanes
* 176(H),216(H) / 176(H),216{H) + 178(H),21a(H) + 17a(H),216(H) hopanes
* 22R / 22R + 22S 17a(H),216(H)-homohopanes
* 208 / 208 + 20R 136(H),17a(H)-diacholestane
* 248 / 248 + 24R (20R)-24-methyl-aaa-cholestane
* 20R / 20R + 208 -24-ethyl-aaa-cholestane
* a86 / a86 + aaa (20R + 20S) 24-ethylcholestane
* aaa-c
28
steranes / aaa-C
29
steranes
* aaa-C steranes / aaa-C
29
steranes
* Sao + a86 (20R) / aaa (20R) C
29
steranes
* 136(H),17a(H)(208) / aaa (20R) C
27
+ C 8 + C
29
steranes
* Boa (20R)-C28 + a86 (20R+20S)-C
28
+ (20R+20S)-C
29
/ aaa (20R)-C
28
steranes
* C
27
trlaromatic steranes I C
27
triaromatic + C
28
monoaromatic steranes
* C
21
monoaraoatic steranes I C
2l
triaromatic + C
28
monoaromatic steranes
* C
26
triaromatic steranes I C
20
triaromatic t C
27
triaromatic steranes
* preferential removal of C
27
-208 diasterane over 20R eplmer
* preferential removal of regular steranes over diasteranes
* 17a(8)-C
30
bopanes / 178(8)-(C
29
+ C
lO
) IOOretanes
* 17a(8)/178(H)-trisnorhopanes

Source
Migratlon/Maturation
Source/Maturation
Source IMa tura tiOll
Migration in comon sources
Maturation
Maturation
Maturation
Maturation
IIaturation
Maturation
Source
Source
Hlgration
Hlqration
Source
Maturatlon/aromatlzatlon
Maturation/bond breaking
IIaturation/bond breaking
Blodegradation
Blodegradation
Source rocks by pyrol ysis
Source rocles by pyrol ysis
aaa, aB6, B68, Sao refer to the stereochetnlstry of the H atOlll at the 5, 14 and 17 positions, respectively, of tbe regular steranes
Ul
-.1
58
mat structures formed by sulphide oxidizing bacteria in upwelling areas (35,36).
In evaporite facies the enhanced reducing character of the environmeots leads h
greater preservation of the hopane side chain during diageoesis. In hypersaline settin
the occurrence of e,. andlor e
l5
hopanes lS characteristic and are found in higt
concentrations than the other homohopanes (30). A very strong predominance of (
hopanes has been reported 10 occur in samples derived from peats and coals. This r.
been attributed to decarboxilation of en hopanoic acids wruch are abundant in su
samples. High cooceotrations of moretanes have also been noted in them and res
from the direct input of mor etanol and moretaoone into the sediment from land pi
sources.
Hopanes having an additionaI methyI substituent in ring A have been reported .
numerous authors 10 occur in crude oils and sediments, most of them deposited
carbonate and/or hypersaline environments. Summons and Jahnke (37) have recem
shown that the most commonly reported methylhopanes are 2-methylhopanes. The ml
significant parameters involving the hopanes are also iocluded in Table 1 (2).
3.7.2. Non-hopane type triterpanes. Lupanes (XXII), oleananes (XXlll), feman
(XXlY) and ursanes (XXV) biomarkers characteristic of plant triterpenoids have be:c
frecuently found in coals and oils derived from terrigenous source materials. Tht
precursors are widely distributed in higher plants. e3Q bicadinanes (XXVI) found in 01
have been shown to be characteristic cracking products of angiosperm fossil resins. Tr
18a(H)-0Ieanane has been observed in a number of deltaic sediments and crude oi
related to them (2-4,31,31). The biogenic precursors of oleanane are presumed to be oleaner
triterpeooids such as 6-amyrin, which are associated with high1y specialized terrigenOl
plants.
The origin of gammacerane (XXYlJ), peotacyclic triterpane, ofien used as
indicator for salinity, is still unclear. TetrahymanoI, the only pentacyclic triterpeno
fouod in protozoa and fungus, is the only knowo poteotiaI biological precursor ,
ganunacerane (39). As Gammacerane is preseot in many sampIes from varioL
enviroomeots, its use as a biomarker for salinity is oot based on its occurrence, b
rather 00 its relative abundance (31).
3.8. HEXAeyeLIe HOPANOID ALKANES
e
31
-C
35
bexacyclic hopanoid alkanes (XXVIII) have beeo used as an indicator for anOXl
paIeoeovironmeots (40,41). These authors have suggested that hexacyclic alkanes wer
derived from bacteriohopanetetrol (e
35
) precursors through cyclisatioo of the side chai
of extended hopanoids during earIy diagenesis.
The hexacyclic hopanes are very resistant to bacterial attack and may be very useft:
for defining palaeoenvironments and biodegradation degree of source rocles and oils
59
4. Use of Biomarkers in Oil Shale Geochemistry. Case study of the Puertollano
(Spain) Oil Shale
For many years organic-geochemical studies were largely limited to tbe most
economically important organic materials found buried in tbe Eartb, namely coals, oil
shales and petroleum. Oil shales have a special geochemical interest botb as potential
source rocles and as an energy resource in tbemselves, altbough most oil shale mining
projects are currently non-viable commercially.
OH shales are a complex group of rocles which were deposited in a wide range of
sedimentary environments and have a wide range of largely alginite-dominated maceral
assemblages. According to a recent classification of oil shales as regards to tbeir relative
abundance of macerals (42), tbey overlap witb botb coals and petroleum source rocles so
tbat any classification of oil shales has to take tbese otber types into account. In tbis
context tbe use of biomarker distribution as an alternative to tbe precise classification
of tbe different types of oil shales might be taken into consideration.
Bitumens are present in some oH sbales such as tbe Green River Formation of tbe
U .S.A. and tbe Irati Formation of Brazil. The bitumens can impregnate and may
partially replace some macerals (43). Past work on tbe biomarkers in oil shale has
involved characterization of tbe biomarkers in bitumen and determination of tbe mannec
in which tbeir quantity varied witb deptb and otber characteristics of tbe sbale witbin
a given coreo Many outstanding worles on tbe application of biomarkers foc source
rocles-oil correlations have been carried out on tbese sedimentary rocles (44).
To show tbe utility for oil shale geochemistry of tbe biomarker approach, we have
taken as specific case study the Puertollano deposit, tbe most important in tbe lberian
Pennsula, which until now has been only partially characterized from tbe geochemical
viewpoint (45).
Table 3 shows tbe composition of tbe alipbatic extractable hydrocarbon fraction of
tbis deposito Experimental metbods were similar to tbose recently used for
characterization of peat and cOO deposits (46).
The hydrocarbon distribution in tbe Puertollano OH Shale is dominated by n-alkanes,
n-alkylcyclohexanes, n-aIkyl,metbylcyclohexanes and mid-chain monomethyl alkanes.
The cyclohexanes showed a distribution very similar to tbat of n-alkanes suggesting a
common origino Triterpenoid distributions showed a major contribution of bacterially
derived hopanoids. The compounds identified comprised C
n
-C
3
, hopanes (no C
u
), ~ 7 -
C,2 8, 14-secohopanes, ~ - C 2 ring-D aromatized 8,14-secohopanes, C,2-C3'
benzohopanes and a C,I hexacyclic saturated hopane. The conifer and angiosperm
derived material is expressed in two different groups of diagenetic compounds.
Diterpenoid compounds as abietane, norabietane, simonellite, retene and tbe
sesquiterpenoid cadalene are characteristics of tbe conifer resios, whereas tbe terpanes
with oleanane and ursane skeleton are characteristics of angiosperms. It is concluded
from tbese results tbat tbe Puertollano oH shale has been formed in a lacustrine
environment witb significant input of higher plant derived organic material.
Some parameters, 50ch as a) tbe abundance of tbe ~ and C
30
primary terpanes
relative to tbe otber members of the series, b) tbe ratio of 176(H),21a(H)-moretane
Table 2.-Hain series of compounds detected in the saturated fraction of the Puertollano Oil Shale extracts.
Series Range Hain 0/00
1
Structure
2
canponent
n-alkanes ClJ-C
39
C
23
420
iso-alkanes C
16
-C
32
20
anteiso-alkanes C
16
-C
32
20
mid-chain methyl alkanes (16-
C
32
40
acyclic isoprenoids C
15
-C
20
C
19
70 I,Ir
n-alkyl-cyclohexanes C
13
-C
28
80
methyl-n-alkyl-cyclohexanes C
18
-C
28
80
bicyclic terpanes C
H
-C
I6
C
16
40 V,VI
diterpanes C
19
-C
20
35 VII, VIII, IX
tricyclic triterpanes C
19
-C
28
C
23
40 XI -XVII
tetracyclic terpanes C
24
C
24
10
tetracyclic 17,21 secohopanes
C ~
C
24
10 XV
8,14 secohopanes
C
27
- 30
5 XVI
id. ring-D aromatized C
27
-C
31
C
29
5
steranes C
27
-C
29
10 XVII-XIX
pentacyclic hopanes C
27
-C
35
C
30
100 XX
benzohopanes
C3(35
C
32
10
hexacyclic hopanes
31
C
31
5 XXVIII
(1) relative abundan ces
(2) Roman numbers refers to the structures shown in Appendix 1 61
lO 17a(H),21B(H)-hopane (0.37), c) the predominance of Tm over Ts, and d) the
predominance ofthe occuring aaR isomers over the maturation induced BB-
isomers in \be mixture of regular and rearranged steranes are indicative of the low
maturity level of this oil shale and the absence of biodegradation.
5. Future Work 00 Biomarkers
The promising future seen for biomarkers by Eglinton two decades ago (47) in basis lO
the development of a oumber of applications has been largely realized. Today, oow that
many of the molecular methods and ftndings have been adsorbed by the industry
(common use of the so-called "biomarker strategy" in exploration studies), the interest
in biomarkers has again moved to new applications and extensions of the basic
molecular organic geochemical approach. Thus, biomarkers have been applied in the
study of recent sediments, to marine sciences, archaeologica1 chemistry, biogeochemical
ecology, biomolecular paleontology, molecular stratigraphy, etc.
Important progress in biomarkers geocbemistry is expected from future investigations
on nonhydrocarbon polar fractions and in particular suIphur biomarkers having well
established structural relationships with known precursors (41). It has been noted,
however, that the "natural sulphurization" during the early stages of diagenesis may
lead lO selective removal ofthe specific hydrocarbon biomarker precursor, and therefore
to biased palaeoenvironmental reconstruction
Of especial interest at present is the use of biomarkers in environmental and pollution
studies, since these compounds provide information on the chemica1 and biologica1
degradation of organic molecules in modero environments. Improved abilities to
monitor and control waste disposal from modero demands, ranging from the disposal
of sewage to improved understanding of landfill waste disposal should be included.
Biomarkers have also been useful for frngerprinting the source of oil spills and other
organic wastes and tracing the source of this pollution.
A particular goal is lO link the patterns of the geologica1 record to the behaviour of
the atmosphere, increasing our understanding of the fundamental causes of climate
change. An outstanding precedent of these investigations is the use of biomarkers from
certain marine aIgae for paleoclimatic reconstructions based on their ability to synthesize
long chain unsaturated ketones with the degree of unsaturation depending on
the ocean water temperature (").
The interest in biomarkers depends on the distribution of biocbemical precursors in
presentIy living organisms. It should be emphasized, however, that knowledge of the
distribution of different precursors in contemporaneous organisms is still insufficient.
Progress in this field and consequentIy in biomarkers geochemistry are dependent 00
the development and improvement of new technologies and novel analytica1 schemes
to study the complex mixtures of chemica1s in geologica1 samples.
Good examples foc the oew frontiers in biomarker geochemistry are the recent
identification of biomarkers of high molecular weigbts ( > C
40
) by using higb-
temperature capillar gas chromalOgraphy ('2), and the development of reliable
62
instruments for determination of carbon isotopie eompositions of individual eomponents
of oils and rock extracts (53), which seem to be a useful para meter in the eorrelation of
oil to oil or oil to source rock and as indicator to identify the precursor of biomarkers.
5. Acknowledgement
I thanks the Spanish Direccion General de Investigacion Cientfica y Tecnica (Project
PB91-0074) for subsidizing this work. Dr .1. C. Del Rio gave invaluable encouragement
and advice.
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APPEltOIX 1
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