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Origin of perylene in ancient sediments and itsgeological signi®cance

Chunqing Jiang a,*, Robert Alexander a, Robert I. Kagi a, Andrew P. Murray b

aAustralianPetroleumCRC/Centre forPetroleumandEnvironmentalOrganicGeochemistry,School ofAppliedChemistry,CurtinUniversity

of Technology, GPO Box U 1987, Perth, WA 6001, AustraliabWoodside 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 amajor PAH component in the top Lower to baseMiddle Jurassic sediments that are immature or at lowmaturity. Its depth/age pro®les are not related to the combustion-derived PAHs that have been believed to be produced during ancient vege-tation ®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 carbonisotope composition is slightly heavier than higher-plant derived PAHs, but still in the range of the terrestrially sourcedPAHs 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 pre-viously 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 marinesediments (Orr and Grady, 1967; Aizenshtat, 1973;Wakeham et al., 1979; Louda and Baker, 1984; Wilcock

and Northcott, 1995), lake sediments (La¯amme andHites, 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; FernaÂ n-dez 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 hasbeen 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

Lee, 1980; Garrigues et al., 1988; Lu and Kaplan, 1992)

and immature crude oils (Golovko et al., 1991; Lu andKaplan, 1992), data on its occurrence in ancient sedi-ments are far less than for the Recent ones. Severalconclusions 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 trans-

formation during early diagenesis. Compared with otherunsubstituted PAHs, only trace or small amounts ofperylene are produced during combustion or by abnor-

mal thermal exposure of organic materials, probablydue to its thermodynamic instability (Kawka andSimoneit, 1990; Jenkins et al., 1996; Simoneit and Fet-

zer, 1996) or its greater reactivity (Dewar, 1952; Clar,1972; Zander, 1983). Unlike those combustion-derivedunsubstituted PAHs including ¯uoranthene (II), pyrene(III), benzo[a]anthracene (IV), benzo¯uoranthenes (V),

benzo[e]pyrene (VI) and benzo[a]pyrene (VII) whichoccur 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.

PI I : S0146-6380(00 )00074-7

Organic Geochemistry 31 (2000) 1545±1559

www.elsevier.nl/locate/orggeochem

* Corresponding author at present address: Geological Sur-

vey of Canada (Calgary), 3303-33rd Street N.W., Calgary, AB,

Canada T2L 2A7. Fax: +1-403-262-7159.

E-mail address: ess-cal- [email protected] (C. Jiang).

change irregularly with depth in Recent sediments, per-ylene is detected only in sediments but not water parti-culates (Kawamura et al., 1987), and its concentrationincreases rapidly with burial depth (Orr and Grady,

1967; Brown et al., 1972; Aizenshtat, 1973; Ishwatari etal., 1980; Wakeham et al., 1980; Gschwend et al., 1983;Wilcock and Northcott, 1995; FernaÂ ndez et al., 1996).

This indicates that perylene is not carried and depositedin the sediments, but formed after deposition.Secondly, the natural precursors of perylene could be

the structurally related perylenequinones and their deri-vatives, which are kinds of black pigments widely pre-sent 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 foundtogether 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 fromaround Lake Harun, Japan (Ishiwatari et al., 1980). The

reduction of these pigments in the laboratory did giverise to related aromatic hydrocarbons.Thirdly, the presence of perylene in more than trace

amounts (e.g. 0.010 ppm) is a palaeo-environmentalmarker for syn- and post-depositional anoxia. Sincequinone compounds are sensitive to oxidization, itspreservation in sediments requires a reducing environ-

ment (Aizenshitat, 1973). For all of those Recent sedi-ments and that fossil crinoid in which perylene ispresent, strongly reducing conditions were indicated by

either the redox potential of sediments or the presenceof 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 addi-tion, the transportation and sedimentation of peryleneprecursors should be rapid enough to prevent its degra-

dation 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 beendetected in diatomaceous sediments (Wakeham et al.,

1979; Hites et al., 1980; Venkatesan, 1988), the presenceor the uncertainty about the presence of terrestrialorganic matter in these sediments makes the proposal of

diatoms as a major source of perylene unconvincing. Onthe other hand, a terrestrial source including plants,fungi and insects has been proposed to be a major, if notthe 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 insediments from Lake Harun, Japan (Ishiwatari et al.,

1980), in terrigenous peats (Gilliland et al., 1960;Aizenshtat, 1973; Venkatesan, 1988, and referencestherein), in bituminous Kentucky coal (White and Lee,1980), in Tertiary coals and source rocks fromMahakam

Delta, Indonesia (Garrigues et al., 1988), in Late Cretac-eous Rocky Mountain coals, USA, in Eocene and Cre-taceous Latrobe coals from Gippsland Basin, Australia,

as well as in Eocene brown coal from east-central Texas(Lu andKaplan, 1992). A recent study of the distributionof perylene in two sediment cores from Lake Ontario by

Silliman et al. (1998) shows that there are no strong cor-relations between perylene and land or aquatic sourcesof organic matter. In this paper, we will report the unusual

occurrence of perylene in some Jurassic sediments fromthe Northern Carnarvon Basin, Australia. Its possiblemajor source and geochemical signi®cance are discussed.

2. Samples and geological setting

Rock samples investigated are from the Upper Trias-sic to Middle Jurassic sequences of the Delambre-1,Brigadier-1 and Gandara-1 wells located in the North-

ern Carnarvon Basin, Western Australia (for locationsee Jiang et al., 1998). The depositional environment inthis area during the Late Triassic was ¯uvio-deltaic

(Bradshaw et al., 1988; Hocking, 1988; Blevin et al.,1994). Mudstone and sandstone are the major sedi-ments, with occasional occurrence of coals. EarlyJurassic times saw deposition in mainly shallow marine

environments and mudstone is the major lithology forthe three wells. The Middle Jurassic section is a thickset of siltstones/sandstones with occasional occurrence

of mudstones and is considered to be deposited undernon-marine/¯uviatile conditions at Delambre-1. Mainlymudstones were deposited at Brigadier-1 and Gandara-1

in shallow marine depositional environment (Apthorpe,1994). The Upper Triassic to Middle Jurassic sedimentsin the study area are believed to have experienced onlymild thermal history as shown in Fig. 1.

3. Experimental

Full details of experimental procedures have beengiven elsewhere (Jiang et al., 1998). Finely ground shaly

rock samples were extracted ultrasonically for 2 h withdichloromethane. Silica gel column chromatographyseparation of extracts was performed to obtain the ali-

phatic, aromatic and polar fractions. GC/MS analyses ofaromatic fractions of sedimentary extracts were carriedout on a Hewlett-Packard 5890 Series II GC coupled to aHewlett-Packard 5971 series Mass Selective Detector

(MSD) operating in total ion acquisition mode. Auto-matic cool-on-column injection was employed into a50m�0.25mm�0.25mm J&W BP-5 capillary column.

1546 C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559

Helium was used as carrier gas. The GC temperatureprogram 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 pub-lished previously. PAH recovery estimate and quanti®ca-tion were achieved by using both internal standards

(deuterated PAHs) and a normalization standard (m-ter-phenyl). Recoveries for the ®ve internal standards were70�90% for naphthalene-d8, 84�96% for acenaphthene-

d10, 85�95% for phenanthrene-d10, 85�98% for chry-sene-d12 and 70�90% for perylene-d12.

4. Results and discussion

4.1. The occurrence of perylene in the studied sediments

Fifty-eight aromatic fractions of sediment extractsfrom the three Upper Triassic to Middle Jurassic

sequences were subjected to detailed GC/MS analysis.Shown in Fig. 2 are selected partial total ion chromato-grams (TICs), demonstrating the GC behaviours of thevarious aromatic hydrocarbons. In all of these ancient

sediments, methylnaphthalenes are the most abundantPAHs based on the TICs of the aromatic fractions. For5three-ring PAHs, the unsubstituted PAHs are always

more abundant than their alkyl derivatives (Jiang,1998). A combustion source as the result of ancientvegetation ®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 chry-sene (X) in the sediments (Jiang, 1998; Jiang et al.,1998). Shown in Fig. 3 are the summed mass chroma-tograms of m/z (178+202+228+252+276) for selected

sediment samples of this study, demonstrating the rela-tive distribution of 5three-ring unsubstituted PAHs.Perylene (I) is one of the most prominent individual

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

C. Jiang et al. / Organic Geochemistry 31 (2000) 1545±1559 1547

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-methyl-

naphthalene; 5: acenaphthene-d10; 6: cadalene; 7: phenanthrene-d10; 8: phenanthrene; 9: ¯uoranthene; 10: pyrene; 11: m-terphenyl; 12: retene; 13: benzo[a]anthracene; 14: chrysene-

d12; 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).

1548

C.Jianget

al./

Organic

Geochem

istry31(2000)1545±1559

PAHs in the aromatic fractions of some sediments (Figs.2 and 3); the relative importance of perylene varies withthe age of sample. It is much more abundant than thosecombustion-derived PAHs in the sediments from the top

Lower Jurassic to base Middle Jurassic interval such assediment samples 3052.5 m and 3547.5 m in the Delam-bre-1, 2975.5 m in the Brigadier-1 and 3092 m in the

Gandara-1 (Fig. 3). Perylene is present in very low con-centrations relative to other unsubstituted PAHs in theUpper Triassic sediments. Quanti®cation results for

selected sediment samples from the Delambre-1 wellalso indicate that perylene is most abundant in thesediments from the middle section of the Lower to

Middle Jurassic (0.161±0.669 ppm for 3817.5±3052.5 mof Delambre-1) and least abundant in the Upper Trias-sic 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 JurassicSwiss 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 someRecent sediments (Orr and Grady, 1967; Wakeham etal., 1979, 1980; Tan and Heit, 1981; Soma et al., 1996).

Shown in Fig. 4 are the m/z 252 mass chromatogramsof the samples typical of relevant depth intervals for thethree sedimentary sequences. The abundance of per-

ylene relative to benzopyrenes varies with depth/time,and this does not seem to be maturity dependent. Insediments from the depth intervals 2632.5±3907.5 m forDelambre-1, 2875.5±3375.5 m for Brigadier-1 and 2950-

3412 m for Gandara-1 which all range in age fromToarcian (Lower Jurassic) afterward, perylene is moreabundant than both benzo[e]pyrene and benzo[a]pyrene.

Perylene is present at lower concentrations than benzo-pyrenes in sediments from deeper sections (UpperTriassic and base Lower Jurassic), and exists only in

traces in some of these sediments. In the 2557.5 m sam-ple from Delambre-1 which is the shallowest sedimentavailable in this study, perylene is also less abundantthan benzopyrenes. This means the relative distribution

of benzopyrenes and perylene (m/z 252 in Fig. 4) ismainly related to the source of organic materials in thesediments rather than maturity.

Aromatic GC/MS analysis for Upper Jurassic sourcerocks from the Northern Carnarvon Basin also showedlower concentration of perylene (I) than both benzo[e]-

pyrene (VI) and benzo[a]pyrene (VII). This has beenshown in the m/z 252 mass chromatograms for tworepresentative sequences (Fig. 5). It can therefore be

concluded, based on the distribution pattern of m/z 252mass chromatograms, that perylene predominates overbenzopyrenes in the top Lower Jurassic to base MiddleJurassic sediments (i.e. equivalent horizons of 2632.5±

3907.5 m of Delambre-1, 2875.5±3375.5 m of Brigadier-1 and 2950±3412 m of Gandara-1), and is less abundantthan benzopyrenes in the sediments from the Upper

Triassic, base Lower Jurassic, top Middle Jurassic, andUpper Jurassic sections in the Northern CarnarvonBasin. It seems that, as indicated by the results of manystudies on PAHs in Recent sediments (Venkatesan,

1988, and references therein), the abundant occurrenceof perylene in ancient sediments is also not a ubiquitousphenomenon. The source of organic input into the sedi-

ments and the post-depositional processes must haveplayed 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 inthe sediments, especially the middle section of Lower toMiddle 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 withthose of perylene in Fig. 6. As in Recent sediments of

various geological settings (Wakeham et al., 1980; Tanand Heit, 1981; Wilcock and Northcott, 1995; FernaÂ ndezet al., 1996; Tan et al., 1996), the occurrence of perylene

in the Upper Triassic to Middle Jurassic sequences of theNorthern Carnarvon Basin also does not follow that ofthe combustion-derived PAHs. Therefore, the combus-

tion process is not expected to be responsible for suchhigh abundance of perylene as in the Lower to MiddleJurassic sediments from the Northern Carnarvon Basinwhere perylene is more abundant than combustion-

derived PAHs. Even for the Upper Triassic and baseLower Jurassic sections where only background levels ofperylene exists, combustion is not a major source since

its distribution in these sections doest not follow com-bustion-derived PAHs either vertically or laterally. It isreasonable to conclude that the major source of perylene

in the sediments of this study is not combustion relatedbut 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 under-goes further loss of hydrogen to give perylene (Campbelland Andrew, 1979). Data analysis showed that neither a

positive nor a negative relationship exists between thedistributions of naphthalene and perylene. Furthermore,there was no binaphthalene (m/z 254) detected in the

sediments. Therefore, they do not appear to share agenetic relationship. This excludes the sedimentary cou-pling 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 per-ylene (Figs. 3 and 4) are immature or at low maturity as

indicated by their Tmax (�C) data from Rock-Eval ana-lysis and vitrinite re¯ectance values [Ro(%)] (Fig. 1).Listed in Table 1 are the sediment samples from other


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[123-

cd]pyrene; Bpery: benzo[ghi]perylene).


wells of the Northern Carnarvon Basin, and from otherBasins that exhibit higher abundances of perylene thanbenzopyrenes. They are also at low maturity stage. This

means the sedimentary formation of perylene occursduring diagenesis. Studies on the PAH distributions inRecent 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; Fer-naÂ ndez 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 theNorthern 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 themicrobe-derived 1,3,6,7-tetramethylnaphthalene (1367-TeMN; XIII, van Aarssen et al., 1996; Jiang et al., 1998)

for the three sedimentary sequences from the NorthernCarnarvon Basin. Combustion marker benzo[e]pyreneand higher-plant derived cadalene are indicators for ter-restrial input to the sediments (Jiang et al., 1998).

Although the depth pro®le of perylene does not followthose of benzo[e]pyrene and cadalene, the maximum rela-tive concentration of perylene, like the terrestrial markers,

decreases from Delambre-1 well to Brigadier-1 and Gan-dara-1 wells. Geological study showed that the deposi-tional environment during the late Early Jurassic toMiddle

Jurassic was shallow-marine to ¯uvial-deltaic at Delambre-1 and was shallow-marine at Brigadier-1 and Gandara-1(Apthorpe, 1994). This means the concentration of per-

ylene in the sediments is proportional to the amount ofterrestrial materials, suggesting that the major origin ofperylene is related to the input of terrigenous materials.

There are two possible sources for perylene whichmay be related to the input of terrigenous materials inthe aquatic environments. One is the terrestrial organicmaterials themselves. These may include land plants and

other associated terrestrial organisms such as fungi andinsects. The other source is from aquatic organismswhose growth is dependent upon the terrestrial materi-

als deposited in an aquatic environment. Among theaquatic organisms, diatoms have been implied by someauthors (Wakeham et al., 1979; Hites et al., 1980; Ven-

katesan, 1988) to be a possible source for perylene inRecent diatomaceous sediments. However, diatoms donot seem to be a major potential source of perylene in

our samples which are of Late Triassic to Middle Jur-assic age. Firstly, Cretaceous diatoms are the oldestdiatoms known at present (Strelnikova, 1974; Tissot andWelte, 1984), and no fossil diatoms have been reported

in the Triassic and Jurassic sedimentary sequences ofthis study. Secondly, structures of perylene have notbeen reported in diatoms up to this time. Thirdly,

Table 1

Geochemical and geological information of the samples in which perylene is more abundant than benzopyrenes

Locality

Well Depth (m) Age basin, country Lithology Maturity levela

A-1 2412 Carnarvon, Australia 0.19DA-1 920 Lower Cretaceous Carnarvon, Australia Sand-/silt-stone 0.07DO-1 1898 Middle Jurassic Carnarvon, Australia Sandstone 0.21DO-1 2702 Upper Triassic Carnarvon, Australia Siltstone 0.23O-1 1195 Lower Cretaceous Carnarvon, Australia Siltstone 0.36P-1 3325 Carnarvon, Australia 0.31SA-1 1405 Lower Cretaceous Carnarvon, Australia Siltstone 0.12SO-1 1542 Cretaceous Carnarvon, Australia Sand-/silt-stone 0.15WA-1 590 Cretaceous Carnarvon, Australia Reservoir 0.43Mayneside-1 2970 Cretaceous Eromanga, Australia Shale Low maturityMayneside-1 3000 Cretaceous Eromanga, Australia ShaleMayneside-1 3050 Cretaceous Eromanga, Australia ShaleVolador-1 3033 Upper Cretaceous Gippsland, Australia Sandstone 0.15Volador-1 3315 Upper Cretaceous Gippsland, Australia Sandstone 0.23Volador-1 3405 Upper Cretaceous Gippsland, Australia Siltstone CPI: 2.27Volador-1 3498 Upper Cretaceous Gippsland, Australia Siltstone 0.21Volador-1 3573 Upper Cretaceous Gippsland, Australia CPI: 2.31Volador-1 3675 Upper Cretaceous Gippsland, Australia Ro: 0.70%Julia Creek Cretaceous Queensland, Australia Oil shale 0.28GNK-67 1114 Middle Miocene S. Sumatra, Indonesia Shale 0.17GNK-67 1351 Middle Miocene S. Sumatra, Indonesia Shale 0.14GNK-67 1514 Lower Miocene S. Sumatra, Indonesia Shale 0.36Maniguin-2 2268 Miocene SE Luzon, Philippines Coal Ro: 0.66%

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


diatoms do not seem to be a potential precursor source

for perylene even in Recent sediments. Crinoids,another type of aquatic organism containing perylenerelated structures can also be excluded as the major

precursor carriers for perylene. This is because (1) nofossil crinoid remains have been reported from theUpper Triassic and Jurassic sediments from the North-ern Carnarvon Basin; (2) the concentration of perylene

in the Upper Jurassic Swiss fossil is much lower than inthe Jurassic sediments of this study; and (3) the struc-ture 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 peryleneis expected to be only a minor product of their reduction

reactions. On the other hand, fungi communities colo-nizing the aquatic environment as parasites, symbiontsand saprobes (Kohlmeyer and Kohlmeyer, 1979; Hyde,

1996) are a possible contributor of perylene in theLower to Middle Jurassic sediments of this study.

4.4. The major precursors for perylene being terrigenous

The precursors of perylene are most likely the struc-turally related perylenequinones and associated deriva-

tives, and higher plants, fungi and insects are the most

likely carriers of these precursors. Considering thatfungi are predominantly terrestrial, with less than 2% ofthe species being aquatic (Ingold and Hudson, 1993),

and that the diversi®cation of insects in the marineenvironment is very limited (Gullan and Cranston,1994), it can be said reasonably that these three kinds oforganisms, live or dead, are generally of terrestrial a�-

nity. Therefore, a high abundance of perylene in theseancient sediments is suggested to be an indicator forterrestrial input. Data from GC±ir±MS analysis of aro-

matic fractions of samples from the 3367.5�3727.5 minterval of Delambre-1 well performed at the AustralianGeological Survey Organization seem to support this.

The stable carbon isotope composition of perylene(ÿ23.63 to ÿ23.96%) is in the same range as aromaticland plant biomarkers (ÿ24.88 to ÿ26.64% for cada-

lene; ÿ24.46 to % ÿ25.90% for retene and ÿ24.63 toÿ25.22% for simonellite) and combustion-derivedPAHs (ÿ23.19 to ÿ24.19% for benzo[a]pyrene andbenzo[e]pyrene).

The suggestion that perylene in the Upper Triassic toMiddle Jurassic sediments of the Northern CarnarvonBasin, especially in the top Lower to base Middle

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.


Jurassic sediments where it is very abundant, is mainlyof terrigenous origin seems reasonable if one considersthe 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 wellcontains perylene in highest abundance (0.669ppm). The total organic carbon (TOC) of this

sample is 1.85%, which means the content of totalorganic matter in the sediments should be in therange of 2.18 to 2.74% if 1.18�1.48 are taken as

the conversion factors for computation of totalorganic matter from TOC (Tissot and Welte,1984). Therefore, perylene is about0.0024�0.0031% (or 24�31 ppm) of the total

sedimentary organic material in the Delmabre-13457.5 m sample.

2. Perylenequinone pigment concentration in fungi and

insects: The contents of binaphtyl and binaphthyl

(XV) in fungus Daldinia concentrica were reportedto be 0.394 and 0.016% of its dry body (Hashi-moto et al., 1994). Perylenequinone pigments

(XIX) from insect species Aphididae were isolatedin 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; Tissotand Welte, 1984; Truswell, 1996; Walker, 1996). Forexample, possible ancestors of higher fungi Ascomy-

cetes, to which the perylenequinone and binaphthylcontaining Daldinia concentrica and Elsinoe belong(Lousberg et al., 1969; Bougher and Syme, 1998), havebeen reported from a silici®ed peat deposit of Triassic

age from the Antartica (White and Taylor, 1988). Tak-ing into account the contents of perylenequinone pig-ments in fungi, it is reasonable to suggest that fungi may

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.


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.


have been the major precursor carriers for perylene inthese ancient sediments, and also for perylene in Recentsediments. The application of fungal spores and theirfruiting bodies in biostratigraphy and palaeoclimatic

interpretations is not yet well known (Kalgutkar, 1997).Their importance in geological studies has been recog-nized probably only in the past two decades, as spores

of fungi were not discussed in the Handbook of Paly-nology published in 1969 (Erdtman, 1969). Therefore, itis not surprising that there has been no report on the

presence of fungal remains in the sediment samples fromthe three wells in this study, which were drilled during1979±1981. However, it has been suggested that deltaicsediments provide substrates for the activity of sapro-

phytic 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 fromthe Maniguin Island, Philippines. Perylene was found tobe a prominent unsubstituted PAH in the aromatic frac-

tions from this coal sample (Fig. 7). The m/z 252 masschromatogram showing the relative distribution of ®ve-ring PAHs (Fig. 7) is very similar to some of the sedi-

ments from the Jurassic section of the Northern Carnar-von Basin (Figs. 3 and 4), with perylene being muchmore abundant than benzopyrenes. Palynological exami-nation revealed that fungal remains are the second most

abundant palynomorphs after large cuticular fragmentsof unknown plant a�nity, and are more abundant thanfern spores and angiosperm pollen (Murray et al., 1997).

5. Conclusions

Unusually high abundance of perylene has beendetected in some Lower Jurassic to Middle Jurassic

sediments from the Northern Carnarvon Basin. It isbelieved that perylene is mainly of terrigenous sourcebased on the facts that its lateral distribution in the

study area is consistent with terrestrial markers and thatits isotope composition is in the same range as terrestrialmarkers. Its natural precursors are possibly the peryl-

enequinone pigments which have been found in higherplants, fungi and insects. Fungi are likely the majorprecursor carriers for perylene in sediments consideringtheir content of perylenequinone pigments and their

geological signi®cance. The abundant occurrence ofperylene in sediments may be an indicator of the con-tribution of fungi to the formation of sedimentary

organic matter in terms of both their alteration to otherorganisms and the accumulation of their bodies in thesediments.

Acknowledgements

CJ acknowledges the ®nancial supports of his PhDstudy by Curtin University of Technology and Aus-tralian Petroleum Cooperative Research Centre. We

thank Mr. G. Chidlow for assistance with GC±MS ana-lysis. Drs. Z. Aizenshtat and P. Garrigues are thankedfor their constructive reviews of the manuscript.

Fig. 7. Summed mass chromatograms m/z (178+202+228+252) showing the relative distribution of unsubstituted PAHs in a Mio-

cene coal sample (2268 m depth) from Maniguin-2 well, Maniguin Island, the Philippines.


Appendix. Molecular structures cited in the text


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