Directory UMM :Data Elmu:jurnal:O:Organic Geochemistry:Vol31.Issue12.Dec2000:

Organic Geochemistry 31 (2000) 1545±1559
www.elsevier.nl/locate/orggeochem

Origin of perylene in ancient sediments and its
geological signi®cance
Chunqing Jiang a,*, Robert Alexander a, Robert I. Kagi a, Andrew P. Murray b
a

Australian Petroleum CRC/Centre for Petroleum and Environmental Organic Geochemistry, School of Applied Chemistry, Curtin University
of Technology, GPO Box U 1987, Perth, WA 6001, Australia
b
Woodside Australian Energy, 1 Adelaide Tce, Perth, WA 6001, Australia

Abstract
The distributions of polycyclic aromatic hydrocarbons (PAHs) in sediments of three Upper Triassic to Middle Jurassic
sedimentary sequences from the Northern Carnarvon Basin, Australia have been investigated. Perylene was found to be a
major PAH component in the top Lower to base Middle Jurassic sediments that are immature or at low maturity. Its depth/
age pro®les are not related to the combustion-derived PAHs that have been believed to be produced during ancient vegetation ®res before deposition. This suggests a diagenetic origin for perylene. The concentration of perylene in the sediments
is proportional to the amount of terrestrial input, decreasing with distance from the source of land sediments. Its carbon
isotope composition is slightly heavier than higher-plant derived PAHs, but still in the range of the terrestrially sourced
PAHs including higher-plant PAHs and combustion-derived PAHs as suggested previously. Fungi are proposed to be the

major precursor carriers for perylene in sediments based on the facts that (1) perylenequinone structures have been previously suggested to be the natural precursors for perylene; (2) perylenequinone pigments exist in many fungal bodies; (3)
fungi have played an important role during geological processes. # 2000 Published by Elsevier Science Ltd. All rights
reserved.
Keywords: PAHs; Perylene; Fungi; Terrestrial origin; Northern Carnarvon Basin

1. Introduction
Perylene (I) has been found widely in Recent marine
sediments (Orr and Grady, 1967; Aizenshtat, 1973;
Wakeham et al., 1979; Louda and Baker, 1984; Wilcock
and Northcott, 1995), lake sediments (La¯amme and
Hites, 1978; Ishiwatari et al., 1980; Wakeham et al.,
1980; Gschwend and Hites, 1981; Tan and Heit, 1981;
Gschwend et al., 1983; Kawamura et al., 1987; FernaÂndez et al., 1996; Soma et al., 1996), river sediments
(Hites et al., 1980) and peats (Gilliland et al., 1960;
Aizenshtat, 1973; Venkatesan, 1988). Although it has
been reported from fossil crinoids (Blumer, 1960,
1962a,b, 1965; Thomas and Blumer, 1964), oil shales
(Aizenshtat, 1973; Garrigues et al., 1988; Golovko et al.,
1991; Jacob et al., 1991), bituminous coals (White and
* Corresponding author at present address: Geological Survey of Canada (Calgary), 3303-33rd Street N.W., Calgary, AB,

Canada T2L 2A7. Fax: +1-403-262-7159.
E-mail address: ess-cal- cjiang@x1.nrcan.gc.ca (C. Jiang).

Lee, 1980; Garrigues et al., 1988; Lu and Kaplan, 1992)
and immature crude oils (Golovko et al., 1991; Lu and
Kaplan, 1992), data on its occurrence in ancient sediments are far less than for the Recent ones. Several
conclusions about perylene have been drawn mainly
based on the studies of its presence in Recent sediments.
Firstly, perylene (I) is a diagenetic product derived
from its natural precursors via post-deposition transformation during early diagenesis. Compared with other
unsubstituted PAHs, only trace or small amounts of
perylene are produced during combustion or by abnormal thermal exposure of organic materials, probably
due to its thermodynamic instability (Kawka and
Simoneit, 1990; Jenkins et al., 1996; Simoneit and Fetzer, 1996) or its greater reactivity (Dewar, 1952; Clar,
1972; Zander, 1983). Unlike those combustion-derived
unsubstituted PAHs including ¯uoranthene (II), pyrene
(III), benzo[a]anthracene (IV), benzo¯uoranthenes (V),
benzo[e]pyrene (VI) and benzo[a]pyrene (VII) which
occur in both water-borne particulates and sediments
(Kawamura et al., 1987) and whose concentrations

0146-6380/00/$ - see front matter # 2000 Published by Elsevier Science Ltd. All rights reserved.
PII: S0146-6380(00)00074-7

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C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

change irregularly with depth in Recent sediments, perylene is detected only in sediments but not water particulates (Kawamura et al., 1987), and its concentration
increases rapidly with burial depth (Orr and Grady,
1967; Brown et al., 1972; Aizenshtat, 1973; Ishwatari et
al., 1980; Wakeham et al., 1980; Gschwend et al., 1983;
Wilcock and Northcott, 1995; FernaÂndez et al., 1996).
This indicates that perylene is not carried and deposited
in the sediments, but formed after deposition.
Secondly, the natural precursors of perylene could be
the structurally related perylenequinones and their derivatives, which are kinds of black pigments widely present in modern plants (Britton, 1983), insects (Cameron
et al., 1964), fungi (Thomson, 1971; Hardil et al., 1989;
Stierle et al., 1989; Wu et al., 1989; Hashimoto et al.,
1994) as well as crinoids (Rideout and Sutherland, 1985;

De Riccardis et al., 1991). Perylene and the structurally
related oxygen containing compounds have been found
together in a Jurassic fossil crinoid from Switzerland
(Blumer, 1960, 1962a,b, 1965; Thomas and Blumer,
1964), in marine sediments from the Gulf of California
(Louda and Baker, 1984) as well as in soil samples from
around Lake Harun, Japan (Ishiwatari et al., 1980). The
reduction of these pigments in the laboratory did give
rise to related aromatic hydrocarbons.
Thirdly, the presence of perylene in more than trace
amounts (e.g. 0.010 ppm) is a palaeo-environmental
marker for syn- and post-depositional anoxia. Since
quinone compounds are sensitive to oxidization, its
preservation in sediments requires a reducing environment (Aizenshitat, 1973). For all of those Recent sediments and that fossil crinoid in which perylene is
present, strongly reducing conditions were indicated by
either the redox potential of sediments or the presence
of reduced inorganic materials in the samples (Blumer,
1965; Orr and Grady, 1967; Aizenshtat, 1973; Wakeham
et al., 1979, 1980; Hites et al., 1980; Tan and Heit, 1981;
Louda and Baker, 1984; Silliman et al., 1998). In addition, the transportation and sedimentation of perylene

precursors should be rapid enough to prevent its degradation before deposition (Orr and Grady, 1967;
Aizenshtat, 1973; Louda and Baker, 1984).
However, there is no agreement yet as to whether
perylene precursors are of terrestrial or aquatic sources.
Although high concentrations of perylene have been
detected in diatomaceous sediments (Wakeham et al.,
1979; Hites et al., 1980; Venkatesan, 1988), the presence
or the uncertainty about the presence of terrestrial
organic matter in these sediments makes the proposal of
diatoms as a major source of perylene unconvincing. On
the other hand, a terrestrial source including plants,
fungi and insects has been proposed to be a major, if not
the only, source of perylene precursors in sediments
(Aizenshtat, 1973; Tan and Heit, 1981; Tan et al., 1996).
The latter is also supported by the presence of perylene in
sediments from Lake Harun, Japan (Ishiwatari et al.,

1980), in terrigenous peats (Gilliland et al., 1960;
Aizenshtat, 1973; Venkatesan, 1988, and references
therein), in bituminous Kentucky coal (White and Lee,

1980), in Tertiary coals and source rocks from Mahakam
Delta, Indonesia (Garrigues et al., 1988), in Late Cretaceous Rocky Mountain coals, USA, in Eocene and Cretaceous Latrobe coals from Gippsland Basin, Australia,
as well as in Eocene brown coal from east-central Texas
(Lu and Kaplan, 1992). A recent study of the distribution
of perylene in two sediment cores from Lake Ontario by
Silliman et al. (1998) shows that there are no strong correlations between perylene and land or aquatic sources
of organic matter. In this paper, we will report the unusual
occurrence of perylene in some Jurassic sediments from
the Northern Carnarvon Basin, Australia. Its possible
major source and geochemical signi®cance are discussed.

2. Samples and geological setting
Rock samples investigated are from the Upper Triassic to Middle Jurassic sequences of the Delambre-1,
Brigadier-1 and Gandara-1 wells located in the Northern Carnarvon Basin, Western Australia (for location
see Jiang et al., 1998). The depositional environment in
this area during the Late Triassic was ¯uvio-deltaic
(Bradshaw et al., 1988; Hocking, 1988; Blevin et al.,
1994). Mudstone and sandstone are the major sediments, with occasional occurrence of coals. Early
Jurassic times saw deposition in mainly shallow marine
environments and mudstone is the major lithology for

the three wells. The Middle Jurassic section is a thick
set of siltstones/sandstones with occasional occurrence
of mudstones and is considered to be deposited under
non-marine/¯uviatile conditions at Delambre-1. Mainly
mudstones were deposited at Brigadier-1 and Gandara-1
in shallow marine depositional environment (Apthorpe,
1994). The Upper Triassic to Middle Jurassic sediments
in the study area are believed to have experienced only
mild thermal history as shown in Fig. 1.

3. Experimental
Full details of experimental procedures have been
given elsewhere (Jiang et al., 1998). Finely ground shaly
rock samples were extracted ultrasonically for 2 h with
dichloromethane. Silica gel column chromatography
separation of extracts was performed to obtain the aliphatic, aromatic and polar fractions. GC/MS analyses of
aromatic fractions of sedimentary extracts were carried
out on a Hewlett-Packard 5890 Series II GC coupled to a
Hewlett-Packard 5971 series Mass Selective Detector
(MSD) operating in total ion acquisition mode. Automatic cool-on-column injection was employed into a

50m0.25mm0.25mm J&W BP-5 capillary column.

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

1547

Fig. 1. Maturity levels of the three sedimentary sequences.

Helium was used as carrier gas. The GC temperature
program was 60 C(1 min)(@3 C/min)!300 C(30 min).
Compounds were identi®ed by comparison of mass
spectra and by matching retention times with those of
reference compounds available in this laboratory or published previously. PAH recovery estimate and quanti®cation were achieved by using both internal standards
(deuterated PAHs) and a normalization standard (m-terphenyl). Recoveries for the ®ve internal standards were
7090% for naphthalene-d8, 8496% for acenaphthened10, 8595% for phenanthrene-d10, 8598% for chrysene-d12 and 7090% for perylene-d12.

4. Results and discussion
4.1. The occurrence of perylene in the studied sediments
Fifty-eight aromatic fractions of sediment extracts
from the three Upper Triassic to Middle Jurassic

sequences were subjected to detailed GC/MS analysis.
Shown in Fig. 2 are selected partial total ion chromatograms (TICs), demonstrating the GC behaviours of the
various aromatic hydrocarbons. In all of these ancient
sediments, methylnaphthalenes are the most abundant
PAHs based on the TICs of the aromatic fractions. For
5three-ring PAHs, the unsubstituted PAHs are always
more abundant than their alkyl derivatives (Jiang,
1998). A combustion source as the result of ancient
vegetation ®res has been attributed to most of the
unsubstituted PAHs including ¯uoranthene (II), pyrene
(III), benzo[a]anthracene (IV), benzo¯uoranthenes (V),
benzopyrenes (VI and VII) and indeno[123-cd]pyrene
(VIII), and probably phenanthrene (IX) as well as chrysene (X) in the sediments (Jiang, 1998; Jiang et al.,
1998). Shown in Fig. 3 are the summed mass chromatograms of m/z (178+202+228+252+276) for selected
sediment samples of this study, demonstrating the relative distribution of 5three-ring unsubstituted PAHs.
Perylene (I) is one of the most prominent individual

1548
C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

Fig. 2. Typical total ion chromatograms of aromatic fractions for sediments from the Delambre-1 well (1: naphthalene-d8; 2: naphthalene; 3: 2-methylnaphthalene; 4: 1-methylnaphthalene; 5: acenaphthene-d10; 6: cadalene; 7: phenanthrene-d10; 8: phenanthrene; 9: ¯uoranthene; 10: pyrene; 11: m-terphenyl; 12: retene; 13: benzo[a]anthracene; 14: chrysened12; 15: chrysene; 16: benzo¯uoranthenes; 17: benzo[e]pyrene; 18: benzo[a]pyrene; 19: perylene-d12; 20: perylene; 21: indeno[123-cd]pyrene; 22: benzo[ghi]perylene. Deuterated
compounds were used as internal standards in the concentrations of 0.40 ppm of dry sediments; m-terphenyl was used as a normalization standard in the concentration of 0.42 ppm
of sediments).

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

PAHs in the aromatic fractions of some sediments (Figs.
2 and 3); the relative importance of perylene varies with
the age of sample. It is much more abundant than those
combustion-derived PAHs in the sediments from the top
Lower Jurassic to base Middle Jurassic interval such as
sediment samples 3052.5 m and 3547.5 m in the Delambre-1, 2975.5 m in the Brigadier-1 and 3092 m in the
Gandara-1 (Fig. 3). Perylene is present in very low concentrations relative to other unsubstituted PAHs in the
Upper Triassic sediments. Quanti®cation results for
selected sediment samples from the Delambre-1 well
also indicate that perylene is most abundant in the
sediments from the middle section of the Lower to
Middle Jurassic (0.161±0.669 ppm for 3817.5±3052.5 m
of Delambre-1) and least abundant in the Upper Triassic sediments (0.008±0.102 ppm) (Table 1 in Jiang et al.,
1998). It is clear that perylene is much more abundant in

the sediments of this study than in the Upper Jurassic
Swiss fossil crinoid sample (0.002 ppm of dry sediments:
Thomas and Blumer, 1964). The occurrence of perylene
in these ancient sediments is at a similar level to some
Recent sediments (Orr and Grady, 1967; Wakeham et
al., 1979, 1980; Tan and Heit, 1981; Soma et al., 1996).
Shown in Fig. 4 are the m/z 252 mass chromatograms
of the samples typical of relevant depth intervals for the
three sedimentary sequences. The abundance of perylene relative to benzopyrenes varies with depth/time,
and this does not seem to be maturity dependent. In
sediments from the depth intervals 2632.5±3907.5 m for
Delambre-1, 2875.5±3375.5 m for Brigadier-1 and 29503412 m for Gandara-1 which all range in age from
Toarcian (Lower Jurassic) afterward, perylene is more
abundant than both benzo[e]pyrene and benzo[a]pyrene.
Perylene is present at lower concentrations than benzopyrenes in sediments from deeper sections (Upper
Triassic and base Lower Jurassic), and exists only in
traces in some of these sediments. In the 2557.5 m sample from Delambre-1 which is the shallowest sediment
available in this study, perylene is also less abundant
than benzopyrenes. This means the relative distribution
of benzopyrenes and perylene (m/z 252 in Fig. 4) is
mainly related to the source of organic materials in the
sediments rather than maturity.
Aromatic GC/MS analysis for Upper Jurassic source
rocks from the Northern Carnarvon Basin also showed
lower concentration of perylene (I) than both benzo[e]pyrene (VI) and benzo[a]pyrene (VII). This has been
shown in the m/z 252 mass chromatograms for two
representative sequences (Fig. 5). It can therefore be
concluded, based on the distribution pattern of m/z 252
mass chromatograms, that perylene predominates over
benzopyrenes in the top Lower Jurassic to base Middle
Jurassic sediments (i.e. equivalent horizons of 2632.5±
3907.5 m of Delambre-1, 2875.5±3375.5 m of Brigadier1 and 2950±3412 m of Gandara-1), and is less abundant
than benzopyrenes in the sediments from the Upper

1549

Triassic, base Lower Jurassic, top Middle Jurassic, and
Upper Jurassic sections in the Northern Carnarvon
Basin. It seems that, as indicated by the results of many
studies on PAHs in Recent sediments (Venkatesan,
1988, and references therein), the abundant occurrence
of perylene in ancient sediments is also not a ubiquitous
phenomenon. The source of organic input into the sediments and the post-depositional processes must have
played an important role.
4.2. Perylene being a diagenetic product
Combustion processes do not seem to be the major
contributor to the occurrence of abundant perylene in
the sediments, especially the middle section of Lower to
Middle Jurassic sediments of this study. The depth pro®les of benzo[e]pyrene, typical of the distributions of the
combustion-derived PAHs in the studied sediments
(Jiang, 1998; Jiang et al., 1998), are shown together with
those of perylene in Fig. 6. As in Recent sediments of
various geological settings (Wakeham et al., 1980; Tan
and Heit, 1981; Wilcock and Northcott, 1995; FernaÂndez
et al., 1996; Tan et al., 1996), the occurrence of perylene
in the Upper Triassic to Middle Jurassic sequences of the
Northern Carnarvon Basin also does not follow that of
the combustion-derived PAHs. Therefore, the combustion process is not expected to be responsible for such
high abundance of perylene as in the Lower to Middle
Jurassic sediments from the Northern Carnarvon Basin
where perylene is more abundant than combustionderived PAHs. Even for the Upper Triassic and base
Lower Jurassic sections where only background levels of
perylene exists, combustion is not a major source since
its distribution in these sections doest not follow combustion-derived PAHs either vertically or laterally. It is
reasonable to conclude that the major source of perylene
in the sediments of this study is not combustion related
but formed during post-depositional processes.
It has long been established that naphthalene with
Friedel±Crafts reagents such as aluminium trichloride
yields in the ®rst instance binaphthalene, which undergoes further loss of hydrogen to give perylene (Campbell
and Andrew, 1979). Data analysis showed that neither a
positive nor a negative relationship exists between the
distributions of naphthalene and perylene. Furthermore,
there was no binaphthalene (m/z 254) detected in the
sediments. Therefore, they do not appear to share a
genetic relationship. This excludes the sedimentary coupling of naphthalene as a source of any signi®cance for
perylene in these ancient sediments.
It can be seen that the top Lower Jurassic to base
Middle Jurassic sediments containing abundant perylene (Figs. 3 and 4) are immature or at low maturity as
indicated by their Tmax ( C) data from Rock-Eval analysis and vitrinite re¯ectance values [Ro(%)] (Fig. 1).
Listed in Table 1 are the sediment samples from other

1550

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

Fig. 3. Summed mass chromatograms m/z (178+202+228+252+276) showing the distribution of unsubstituted PAHs for selected
samples from the three wells (P: phenanthrene; An: anthracene; Fla: ¯uoranthene; Pyr: pyrene; BaAn: benzo[a]anthracene; Chry:
chrysene and triphenylene; B¯as: benzo¯uoranthenes; BePy: benzo[e]pyrene; BaPy: benzo[a]pyrene; Pery: perylene; InPy: indeno[123cd]pyrene; Bpery: benzo[ghi]perylene).

1551

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559
Table 1
Geochemical and geological information of the samples in which perylene is more abundant than benzopyrenes
Locality
Well

Depth (m)

A-1
DA-1
DO-1
DO-1
O-1
P-1
SA-1
SO-1
WA-1
Mayneside-1
Mayneside-1
Mayneside-1
Volador-1
Volador-1
Volador-1
Volador-1
Volador-1
Volador-1
Julia Creek
GNK-67
GNK-67
GNK-67
Maniguin-2

2412
920
1898
2702
1195
3325
1405
1542
590
2970
3000
3050
3033
3315
3405
3498
3573
3675

a

1114
1351
1514
2268

Age
Lower Cretaceous
Middle Jurassic
Upper Triassic
Lower Cretaceous
Lower Cretaceous
Cretaceous
Cretaceous
Cretaceous
Cretaceous
Cretaceous
Upper Cretaceous
Upper Cretaceous
Upper Cretaceous
Upper Cretaceous
Upper Cretaceous
Upper Cretaceous
Cretaceous
Middle Miocene
Middle Miocene
Lower Miocene
Miocene

basin, country
Carnarvon, Australia
Carnarvon, Australia
Carnarvon, Australia
Carnarvon, Australia
Carnarvon, Australia
Carnarvon, Australia
Carnarvon, Australia
Carnarvon, Australia
Carnarvon, Australia
Eromanga, Australia
Eromanga, Australia
Eromanga, Australia
Gippsland, Australia
Gippsland, Australia
Gippsland, Australia
Gippsland, Australia
Gippsland, Australia
Gippsland, Australia
Queensland, Australia
S. Sumatra, Indonesia
S. Sumatra, Indonesia
S. Sumatra, Indonesia
SE Luzon, Philippines

Lithology
Sand-/silt-stone
Sandstone
Siltstone
Siltstone
Siltstone
Sand-/silt-stone
Reservoir
Shale
Shale
Shale
Sandstone
Sandstone
Siltstone
Siltstone

Maturity levela
0.19
0.07
0.21
0.23
0.36
0.31
0.12
0.15
0.43
Low maturity

CPI:
CPI:
Ro:

Oil shale
Shale
Shale
Shale
Coal

Ro:

0.15
0.23
2.27
0.21
2.31
0.70%
0.28
0.17
0.14
0.36
0.66%

Unless otherwise stated in the table, values are for the maturity parameter C29 aaa steranes 20S/(20S+20R).

wells of the Northern Carnarvon Basin, and from other
Basins that exhibit higher abundances of perylene than
benzopyrenes. They are also at low maturity stage. This
means the sedimentary formation of perylene occurs
during diagenesis. Studies on the PAH distributions in
Recent sediments also support this viewpoint (Orr and
Grady, 1967; Brown et al., 1972; Aizenshtat, 1973;
La¯amme and Hites, 1978; Ishwatari et al., 1980;
Wakeham et al., 1980; Gschwend et al., 1983; Louda
and Baker, 1984; Wilcock and Northcott, 1995; FernaÂndez et al., 1996).
4.3. Major precursor carriers of perylene related to
terrestrial input
It is evident that the major source of perylene in the
Upper Triassic to Middle Jurassic sediments from the
Northern Carnarvon Basin is terrestrially dependent.
Shown in Fig. 6 are the depth pro®les of perylene (I),
benzo[e]pyrene (VI) and cadalene (XII) relative to the
microbe-derived 1,3,6,7-tetramethylnaphthalene (1367TeMN; XIII, van Aarssen et al., 1996; Jiang et al., 1998)
for the three sedimentary sequences from the Northern
Carnarvon Basin. Combustion marker benzo[e]pyrene
and higher-plant derived cadalene are indicators for terrestrial input to the sediments (Jiang et al., 1998).
Although the depth pro®le of perylene does not follow
those of benzo[e]pyrene and cadalene, the maximum relative concentration of perylene, like the terrestrial markers,

decreases from Delambre-1 well to Brigadier-1 and Gandara-1 wells. Geological study showed that the depositional environment during the late Early Jurassic to Middle
Jurassic was shallow-marine to ¯uvial-deltaic at Delambre1 and was shallow-marine at Brigadier-1 and Gandara-1
(Apthorpe, 1994). This means the concentration of perylene in the sediments is proportional to the amount of
terrestrial materials, suggesting that the major origin of
perylene is related to the input of terrigenous materials.
There are two possible sources for perylene which
may be related to the input of terrigenous materials in
the aquatic environments. One is the terrestrial organic
materials themselves. These may include land plants and
other associated terrestrial organisms such as fungi and
insects. The other source is from aquatic organisms
whose growth is dependent upon the terrestrial materials deposited in an aquatic environment. Among the
aquatic organisms, diatoms have been implied by some
authors (Wakeham et al., 1979; Hites et al., 1980; Venkatesan, 1988) to be a possible source for perylene in
Recent diatomaceous sediments. However, diatoms do
not seem to be a major potential source of perylene in
our samples which are of Late Triassic to Middle Jurassic age. Firstly, Cretaceous diatoms are the oldest
diatoms known at present (Strelnikova, 1974; Tissot and
Welte, 1984), and no fossil diatoms have been reported
in the Triassic and Jurassic sedimentary sequences of
this study. Secondly, structures of perylene have not
been reported in diatoms up to this time. Thirdly,

1552

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

Fig. 4. Partial mass chromatograms m/z 252 showing the relative distribution of benzo¯uoranthenes (B¯as), benzopyrenes (BePy,
BaPy) and perylene (Pery) for representative sediments from the three wells.

diatoms do not seem to be a potential precursor source
for perylene even in Recent sediments. Crinoids,
another type of aquatic organism containing perylene
related structures can also be excluded as the major
precursor carriers for perylene. This is because (1) no
fossil crinoid remains have been reported from the
Upper Triassic and Jurassic sediments from the Northern Carnarvon Basin; (2) the concentration of perylene
in the Upper Jurassic Swiss fossil is much lower than in
the Jurassic sediments of this study; and (3) the structure of compound XX isolated from modern crinoids by
Rideout and Sutherland (1985) and De Riccardis et al.
(1991) is far more complex than perylene, and perylene
is expected to be only a minor product of their reduction
reactions. On the other hand, fungi communities colonizing the aquatic environment as parasites, symbionts
and saprobes (Kohlmeyer and Kohlmeyer, 1979; Hyde,
1996) are a possible contributor of perylene in the
Lower to Middle Jurassic sediments of this study.
4.4. The major precursors for perylene being terrigenous
The precursors of perylene are most likely the structurally related perylenequinones and associated deriva-

tives, and higher plants, fungi and insects are the most
likely carriers of these precursors. Considering that
fungi are predominantly terrestrial, with less than 2% of
the species being aquatic (Ingold and Hudson, 1993),
and that the diversi®cation of insects in the marine
environment is very limited (Gullan and Cranston,
1994), it can be said reasonably that these three kinds of
organisms, live or dead, are generally of terrestrial anity. Therefore, a high abundance of perylene in these
ancient sediments is suggested to be an indicator for
terrestrial input. Data from GC±ir±MS analysis of aromatic fractions of samples from the 3367.53727.5 m
interval of Delambre-1 well performed at the Australian
Geological Survey Organization seem to support this.
The stable carbon isotope composition of perylene
(ÿ23.63 to ÿ23.96%) is in the same range as aromatic
land plant biomarkers (ÿ24.88 to ÿ26.64% for cadalene; ÿ24.46 to % ÿ25.90% for retene and ÿ24.63 to
ÿ25.22% for simonellite) and combustion-derived
PAHs (ÿ23.19 to ÿ24.19% for benzo[a]pyrene and
benzo[e]pyrene).
The suggestion that perylene in the Upper Triassic to
Middle Jurassic sediments of the Northern Carnarvon
Basin, especially in the top Lower to base Middle

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

1553

Fig. 5. Partial mass chromatograms m/z 252 showing the relative distribution of benzo¯uoranthenes (B¯as), benzopyrenes (BePy,
BaPy) and perylene (Pery) for selected Upper Jurassic sediments from the Northern Carnarvon Basin.

Jurassic sediments where it is very abundant, is mainly
of terrigenous origin seems reasonable if one considers
the following facts:
1. Perylene concentration in the sediments: Quanti®cation results (Jiang et al., 1998) show that the
sample from 3457.5m of the Delambre-1 well
contains perylene in highest abundance (0.669
ppm). The total organic carbon (TOC) of this
sample is 1.85%, which means the content of total
organic matter in the sediments should be in the
range of 2.18 to 2.74% if 1.181.48 are taken as
the conversion factors for computation of total
organic matter from TOC (Tissot and Welte,
1984).
Therefore,
perylene
is
about
0.00240.0031% (or 2431 ppm) of the total
sedimentary organic material in the Delmabre-1
3457.5 m sample.
2. Perylenequinone pigment concentration in fungi and

insects: The contents of binaphtyl and binaphthyl
(XV) in fungus Daldinia concentrica were reported
to be 0.394 and 0.016% of its dry body (Hashimoto et al., 1994). Perylenequinone pigments
(XIX) from insect species Aphididae were isolated
in the yields of 0.3 to 1% of the live insect weight
(Cameron and Todd, 1967).
The occurrence of fungi in geological settings has
been a ubiquitous phenomenon (Moore, 1969; Tissot
and Welte, 1984; Truswell, 1996; Walker, 1996). For
example, possible ancestors of higher fungi Ascomycetes, to which the perylenequinone and binaphthyl
containing Daldinia concentrica and Elsinoe belong
(Lousberg et al., 1969; Bougher and Syme, 1998), have
been reported from a silici®ed peat deposit of Triassic
age from the Antartica (White and Taylor, 1988). Taking into account the contents of perylenequinone pigments in fungi, it is reasonable to suggest that fungi may

1554

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

Fig. 6. Lateral change of the concentrations of perylene, benzo[e]pyrene and cadalene relative to 1,3,6,7-tetramethylnaphthalene for
Delambre-1 to Brigadier-1 and Gandara-1 wells.

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

1555

Fig. 7. Summed mass chromatograms m/z (178+202+228+252) showing the relative distribution of unsubstituted PAHs in a Miocene coal sample (2268 m depth) from Maniguin-2 well, Maniguin Island, the Philippines.

have been the major precursor carriers for perylene in
these ancient sediments, and also for perylene in Recent
sediments. The application of fungal spores and their
fruiting bodies in biostratigraphy and palaeoclimatic
interpretations is not yet well known (Kalgutkar, 1997).
Their importance in geological studies has been recognized probably only in the past two decades, as spores
of fungi were not discussed in the Handbook of Palynology published in 1969 (Erdtman, 1969). Therefore, it
is not surprising that there has been no report on the
presence of fungal remains in the sediment samples from
the three wells in this study, which were drilled during
1979±1981. However, it has been suggested that deltaic
sediments provide substrates for the activity of saprophytic fungi (Traverse, 1988).
The proposal that fungi may be the major precursor
carriers for peryelene in sediments can be supported by
the geochemical study of a Miocene coal sample from
the Maniguin Island, Philippines. Perylene was found to
be a prominent unsubstituted PAH in the aromatic fractions from this coal sample (Fig. 7). The m/z 252 mass
chromatogram showing the relative distribution of ®vering PAHs (Fig. 7) is very similar to some of the sediments from the Jurassic section of the Northern Carnarvon Basin (Figs. 3 and 4), with perylene being much
more abundant than benzopyrenes. Palynological examination revealed that fungal remains are the second most
abundant palynomorphs after large cuticular fragments
of unknown plant anity, and are more abundant than
fern spores and angiosperm pollen (Murray et al., 1997).

5. Conclusions
Unusually high abundance of perylene has been
detected in some Lower Jurassic to Middle Jurassic
sediments from the Northern Carnarvon Basin. It is
believed that perylene is mainly of terrigenous source
based on the facts that its lateral distribution in the
study area is consistent with terrestrial markers and that
its isotope composition is in the same range as terrestrial
markers. Its natural precursors are possibly the perylenequinone pigments which have been found in higher
plants, fungi and insects. Fungi are likely the major
precursor carriers for perylene in sediments considering
their content of perylenequinone pigments and their
geological signi®cance. The abundant occurrence of
perylene in sediments may be an indicator of the contribution of fungi to the formation of sedimentary
organic matter in terms of both their alteration to other
organisms and the accumulation of their bodies in the
sediments.

Acknowledgements
CJ acknowledges the ®nancial supports of his PhD
study by Curtin University of Technology and Australian Petroleum Cooperative Research Centre. We
thank Mr. G. Chidlow for assistance with GC±MS analysis. Drs. Z. Aizenshtat and P. Garrigues are thanked
for their constructive reviews of the manuscript.

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C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

Appendix. Molecular structures cited in the text

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

References
Aizenshtat, Z., 1973. Perylene and its geochemical signi®cance.
Geochimica et Cosmochimica Acta 37, 559±567.
Apthorpe, M., 1994. Towards an Early to Middle Jurassic
palaeogeography for the North West Shelf: a marine perspective. In: Purcell, P.G., Purcell, P.R. (Eds.), The Sedimentary Basins of Western Australia, Proceedings of the
Western Australian Basins Symposium, Perth, Western Australia, 1994, pp. 201±210.
Blevin, J.E., Stephenson, A.E., West, B.G., 1994. Mesozoic
structural development of the Beagle Sub-basin Ð implications for the petroleum potential of the Northern Carnarvon
Basin, In: Purcell, P.G., Purcell, P.R. (Eds.), The Sedimentary Basins of Western Australia, Proceedings of the Western
Australian Basins Symposium, Perth, Western Australia,
1994, pp. 479±496.
Blumer, M., 1960. Pigments of a fossil echinoderm. Nature 188,
1100±1101.
Blumer, M., 1962a. The organic chemistry of a fossil Ð I. The
structure of the fringelite pigments. Geochimica et Cosmochimica Acta 26, 225±227.
Blumer, M., 1962b. The organic chemistry of a fossil Ð II.
Some rare polynuclear hydrocarbons. Geochimica et Cosmochimica Acta 26, 228±230.
Blumer, M., 1965. Organic pigments: their long-term fate. Science 149, 722±726.
Bougher, N.L., Syme, K., 1998. Fungi of Southern Australia,
University of Western Australia Press, Perth.
Bradshaw, M.T., Yeates, A.N., Beynon, R.M., Brakel, A.T.,
Langford, R.P., Totterdell, J.M., Yeung, M., 1988. Palaeogeographic evolution of the North West Shelf region. In:
Purcell, P.G., Purcell, P.R. (Ed.), The North West Shelf,
Australia, Proceedings of Petroleum Exploration Society of
Australia Symposium, Perth, 1994, pp. 29±54.
Britton, G., 1983. The Biochemistry of Natural Pigments.
Cambridge University Press.
Brown, F.S., Baedecker, M.J., Nissenbaum, A., Kaplan, I.R.,
1972. Early diagenesis in reducing fjord, Saanich Inlet, British Columbia Ð III. Changes in organic constituents of
sediment. Geochimica et Cosmochimica Acta 36, 1185±1203.
Cameron, D.W., Todd, L., 1967. Aphid pigments. In: Taylor,
W.I., Battersby, A.R. (Eds.), Oxidative Coupling of Phenols.
Edward Arnold Publishers Ltd., London.
Cameron, D.W., Cromartie, R.I.T., Todd, L., 1964. Colouring
matters of the Aphididae. Part XVI. Reconsideration of the
structure of the Erythroaphins. Journal of Chemical Society,
48±50.
Campbell, N., Andrew, H.F., 1979. Polycyclic aromatic compounds with four or more (usually six-membered) fused carbocyclic ring systems. In: Co€ey, S. (Ed.), Rodd's Chemistry
of Carbon Compounds: Volume III Ð Aromatic
Compounds Ð Part H, 2nd Edition. Elsevier Scienti®c Publishing Company, Amsterdam, pp. 211±311.
Clar, E., 1972. The Aromatic Sextet. John Wiley & Sons, New
York.
De Riccardis, F., Iorzzi, M., Minale, L., Riccio, R., De Forges,
B.R., Debitus, C., 1991. The gymnochromes: novel marine
brominated phenanthroperylene-quinone pigments from
stalked crinoid Gymnocrinus richeri. Journal of Organic
Chemistry 56, 6781±6787.

1557

Dewar, M.J.S., 1952. A molecular orbital theory of organic
chemistry. VI. Aromatic substitution and addition. Journal
of American Chemical Society 74, 3357±3363.
Erdtman, G., 1969. Handbook of Palynology, An Introduction
to the Study of Pollen Grains and Spores. Hafner Publishing
Co, New York.
FernaÂndez, P., Vilanova, R., Grimalt, J.O., 1996. PAH distributions in sediments from high mountain lakes. Polycyclic
Aromatic Compounds 9, 121±128.
Garrigues, P., Parlanti, E., Lapouyade, R., Bellocq, J., 1988.
Distribution of methylperylene isomers in selected sediments.
Geochimica et Cosmochimica Acta 52, 901±907.
Gilliland, M.R., Howard, A.J., Hamer, D., 1960. Polycyclic
hydrocarbons in crude peat wax. Chemistry & Industry,
1357±1358.
Golovko, A.K., Mozzhelina, T.K., Serebrennikova, O.V., 1991.
Distribution of perylene hydrocarbons in oils and rocks of
West Siberia. In: Manning, D.A.C. (Ed.), Organic Geochemistry: Advances and Applications in the Natural Environment, Extended Abstracts of the 15th International
Meeting on Organic Geochemistry, Manchester University
Press, Manchester, pp. 190±192.
Gschwend, P.M., Hites, R.A., 1981. Fluxes of polycyclic aromatic hydrocarbons to marine and lacustrine sediments in
the northeastern United States. Geochimica et Cosmochimica Acta 45, 2359±2367.
Gschwend, P.M., Chen, P.H., Hites, R.A., 1983. On the formation of perylene in Recent sediments: kinetic models.
Geochimica et Cosmochimica Acta 47, 2115±2119.
Gullan, P.J., Cranston, P.S., 1994. The Insects: An Outline of
Entomology. Chapman & Hall, London.
Hardil, C.M., Hallock, Y.F., Clardy, J., Ken®eld, D.S., Strobel, G., 1989. Phytotoxins from Alternaria cassiae. Phytochemistry 28, 73±75.
Hashimoto, T., Tahara, S., Takaoka, S., Tori, M., Asakawa,
Y., 1994. Structures of a novel binaphthyl and three novel
benzophenone derivatives with plant-growth inhibitory
activity from the fungus Daldinia concentrica. Chemical &
Pharmaceutical Bulletin 42, 1528±1530.
Hites, R.A., La¯amme, R.E., Windsor Jr, J.G., Farrington,
J.W., Deuser, W.G., 1980. Polycyclic aromatic hydrocarbons
in an anoxic sediment core from the Pettaquamscutt River
(Rhode Island, U.S.A.). Geochimica et Cosmochimica Acta
44, 873±878.
Hocking, R.M., 1988. Regional geology of the northern Carnarvon Basin. In: Purell, P.G., Purcell, P.R. (Ed.), The North
West Shelf, Australia, Proceedings of Petroleum Exploration
Society of Australia Symposium, Perth, 1998, pp. 97±114.
Hyde, K.D., 1996. Marine fungi. In: Fungi of Australia,
Volume 1B, Introduction Ð Fungi in the Environment.
Australian Biological Resources Study, Canberra, pp. 39±64.
Ingold, C.T., Hudson, H.J., 1993. The Biology of Fungi, 6th
Ed. Chapman & Hall, London.
Ishiwatari, R., Ogura, K., Horie, S., 1980. Organic geochemistry of a lacustrine sediment (Lake Haruna, Japan). Chemical Geology 29, 261±280.
Jacob, J., Alawi, M., Grimmer, G., 1991. Perylene and related
polycyclic aromatic compounds in Jordanian oil shale. Polycyclic Aromatic Compounds 2, 13±17.
Jenkins, B.M., Jones, A.D., Turn, S.C., Williams, R.B., 1996.
Emission factors for polycyclic aromatic hydrocarbons from

1558

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

biomass burning. Environmental Science and Technology 30,
2462±2469.
Jiang, C., 1998. Polycyclic Aromatic Hydrocarbons and their
Geochemical Signi®cance. Application to Sediments from
the Northern Carnarvon Basin. PhD thesis, Curtin University of Technology, Australia.
Jiang, C., Alexander, R., Kagi, R.I., Murray, A.P., 1998.
Polycyclic aromatic hydrocarbons in ancient sediments and
their relationships to palaeoclimate. Organic Geochemistry
29, 1721±1735.
Kalgutkar, R.M., 1997. Fossil fungi from the lower Tertiary
Iceberg Bay Formation, Eukeka Sound Group, Axel Heiberg
Island, Northwest Territories, Canada. Review of Palaeobotany and Palynology 97, 197±226.
Kawamura, K., Ishiwatari, R., Ogura, K., 1987. Early diagenesis of organic matter in the water column and sediments:
microbial degradation and resynthesis of lipids in Lake Haruna. Organic Geochemistry 4, 251±264.
Kawka, O.E., Simoneit, B.R.T., 1990. Polycyclic aromatic
hydrocarbons in hydrothermal petroleums from Guaymas
Basin spreading centre. Applied Geochemistry 5, 1727.
Kohlmeyer, J., Kohlmeyer, E., 1979. Marine Mycology, the
Higher Fungi. Academic Press, New York.
La¯amme, R.E., Hites, R.A., 1978. The global distribution of
polycyclic aromatic hydrocarbons in recent sediments. Geochimica et Cosmochimica Acta 42, 289±303.
Louda, J.W., Baker, E.W., 1984. Perylene occurrence, alkylation and possible sources in deep-sea sediments. Geochimica
et Cosmochimica Acta 48, 1043±1058.
Lousberg, R.J.J., Salemink, C.A., Weiss, U., Batterham,T.J.,
1969. Pigments of Elsinoe species. Part II. Structure of elsinochromes A, B, and C. Journal of Chemical Society, 219±
1225.
Lu, S., Kaplan, I.R., 1992. Diterpanes, triterpanes, steranes,
and aromatic hydrocarbons in natural bitumens and pyrolysates from di€erent humic coals. Geochimica et Cosmochimica Acta 56, 2761±2788.
Moore, L.R., 1969. Geomicrobiology and geomicrobiological
attack on sedimented organic matter. In: Eglinton, G., Murphy M.T.J. (Eds.), Organic Geochemistry: Methods and
Results. Springer-Verlag, Berlin.
Murray, A.P., Sosrowidjojo, I.B., Alexander, R., Kagi, R.I.,
Norgate, C., Summons, R.E., 1997. Oleananes in oils and
sediments: evidence of marine in¯uence during early
diagenesis? Geochimica et Cosmochimica Acta 61, 1261±
1276.
Orr, W.L., Grady, J.R., 1967. Perylene in basin sediments o€
Southern California. Geochimica et Cosmochimica Acta 31,
1201±1209.
Rideout, J.A., Sutherland, M.D., 1985. Pigments of marine
animals. XV. Bianthrones and related polyketides from
Lamprometra palmata gyges and other species of crinoids.
Australian Journal of Chemistry 38, 793±808.
Silliman, J.E., Meyers, P.A., Eadie, B.J., 1998. Perylene: an
indicator of alteration processes or precursor materials?
Organic Geochemistry 29, 1737±1744.
Simoneit, B.R.T., Fetzer, J.C., 1996. High molecular weight
polycyclic aromatic hydrocarbons in hydrothermal petroleums from the Gulf of California and Northeast Paci®c
Ocean. Organic Geochemistry 24, 1065±1077.
Soma, Y., Tanaka, A., Soma, M., Kawai, T., 1996. Photo-

synthetic pigments and perylene in the sediments of southern basin of Lake Baikal. Organic Geochemistry 24, 553±
561.
Stierle, A., Cardellina, J.H., Strobel, G.A., 1989. Phytotoxins
from Alternaria alternata, a pathogen of spotted knapweed.
Journal of Natural Products 52, 42±47.
Strelnikova, N.I., 1974. Diatoms of the Cretaceous Period. In:
Simonsen R. (Ed.), Proceedings of Third Symposium on
Recent and Fossil Marine Diatoms, 9 Ð 13 September, Kiel.
J. Cramer, FL-9490 Vaduz, pp. 311±322.
Tan, Y.L., Heit, M., 1981. Biogenic and abiogenic polynuclear
aromatic hydrocarbons in sediments from two remote Adirondack lakes. Geochimica et Cosmochimica Acta 45, 2267±
2279.
Tan, Y.L., Kong, A., Monetti, M., 1996. Biogenic polycyclic
aromatic hydrocarbons in an Alaskan arctic lake sediment.
Polycyclic Aromatic Compounds 9, 185±192.
Thomas, D.W., Blumer, M., 1964. The organic chemistry of a
fossil Ð III. The hydrocarbons and their geochemistry.
Geochimica et Cosmochimica Acta 28, 1367±1477.
Thomson, R.H., 1971. Naturally Occurring Quinones. Academic Press, New York.
Tissot, B.P., Welte, D.H., 1984. Petroleum Formation, Occurrence: a New Approach to Oil and Gas Exploration, 2nd
Edition. Springer-Verlag, Berlin.
Traverse, A., 1988. Palaeopalynology. Unwin Hyman, Boston.
Truswell, E.M., 1996. The fossil record of the fungi in Australia
and the Australian region. In: Fungi of Australia, Volume
1A, Introduction Ð Classi®cation. Australian Biological
Resources Study, Canberra, pp. 321±340.
van Aarssen, B.G.K., Alexander, R., Kagi, R.I., 1996. The
origin of Barrow Sub-basin crude oils: a geochemical correlation using land-plant derived biomarkers. The APPEA
Journal 36, 465±476.
Venkatesan, M.I., 1988. Occurrence and possible sources of
perylene in marine sediments Ð a review. Marine Chemistry
25, 1±27.
Wakeham, S.G., Scha€ner, C., Giger, W., Boon, J.J.,
De Leeuw, J.W., 1979. Perylene in sediments from the
Namibian Shelf. Geochimica et Cosmochimica Acta 43,
1141±1144.
Wakeham, S.G., Scha€ner, C., Giger, W., 1980. Polycyclic
aromatic hydrocarbons in recent lake sediments Ð II.
Compounds derived from biogenic precursors during early
diagenesis. Geochimica et Cosmochimica Acta 44, 415±
429.
Walker, J., 1996. Biogeography of fungi with special reference
to Australia. In: Fungi of Australia, Volume 1A,
Introduction Ð Classi®cation. Australian Biological Resources Study, Canberra, pp. 263±320.
White, C.M., Lee, M., 1980. Identi®cation and geochemical
signi®cance of some aromatic components of coal. Geochimica et Cosmochimica Acta 44, 1825±1832.
White, J.F., Taylor, T.N., 1988. Triassic fungus from Antarctica with possible Ascomycetous anities. American Journal
of Botany 75, 1495±1500.
Wilcock, R.J., Northcott, G.L., 1995. Polycyclic aromatic
hydrocarbons in deep cores from Mangere Inlet, New Zealand.
New Zealand Journal of Marine & Freshwater Research 29,
107±116.
Wu, H., Lao, X., Wang, Q., Lu, R., 1989. The Shiraiachromes:

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559
novel fungal perylenequinone pigments from Shiraia Bambusicola. Journal of Natural Products 52, 948±951.
Zander, M., 1983. Physical and chemical properties of poly-

1559

cyclic aromatic hydrocarbons. In: Bjoresth, A. (Ed.), Handbook of Polycyclic Aromatic Hydrocarbons. Marcel Dekker,
New York, pp. 1±20.