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 aAustralian Petroleum CRC/Centre for Petroleum and Environmental Organic Geochemistry, School of Applied Chemistry, Curtin Universityof Technology, GPO Box U 1987, Perth, WA 6001, Australia bWoodside 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 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 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 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 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; FernaÂn-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 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
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 sedi-ments 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 trans-formation during early diagenesis. Compared with other unsubstituted PAHs, only trace or small amounts of perylene are produced during combustion or by abnor-mal therabnor-mal exposure of organic materials, probably due to its thermodynamic instability (Kawka and Simoneit, 1990; Jenkins et al., 1996; Simoneit and Fet-zer, 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
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* 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.
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 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 environ-ment (Aizenshitat, 1973). For all of those Recent sedi-ments 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 addi-tion, the transportation and sedimentation of perylene precursors 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 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.,
of 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 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 Trias-sic to Middle JurasTrias-sic sequences of the Delambre-1, Brigadier-1 and Gandara-1 wells located in the North-ern Carnarvon Basin, WestNorth-ern 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 sedi-ments, 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
Helium was used as carrier gas. The GC temperature program was 60C(1 min)(@3C/min)!300C(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 were 7090% for naphthalene-d8, 8496% for
acenaphthene-d10, 8595% for phenanthrene-d10, 8598% for
chry-sene-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 chromato-grams (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 chry-sene (X) in the sediments (Jiang, 1998; Jiang et al., 1998). Shown in Fig. 3 are the summed mass chroma-tograms ofm/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. 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-chrysene-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.
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et
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Organic
Geochemistry
31
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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 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 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 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 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 them/z252 mass chromatograms of the samples typical of relevant depth intervals for the three sedimentary sequences. The abundance of per-ylene 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 2950-3412 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 benzo-pyrenes 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 sam-ple 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 ofm/z252 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 Brigadier-1 and 2950±34Brigadier-12 m of Gandara-Brigadier-1), and is less abundant than benzopyrenes in the sediments from the Upper
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 sedi-ments 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 combus-tion 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 combustion-derived 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 com-bustion-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 under-goes 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 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 theirTmax(C) data from Rock-Eval
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; Fer-naÂndez 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 (1367-TeMN;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 ter-restrial 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 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 to Middle Jurassic was shallow-marine to ¯uvial-deltaic at Delambre-1 and was shallow-marine at Brigadier-Delambre-1 and Gandara-Delambre-1 (Apthorpe, 1994). This means the concentration of per-ylene 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 materi-als deposited in an aquatic environment. Among the aquatic organisms, diatoms have been implied by some authors (Wakeham et al., 1979; Hites et al., 1980; Ven-katesan, 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 Jur-assic 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,
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 0.19 DA-1 920 Lower Cretaceous Carnarvon, Australia Sand-/silt-stone 0.07 DO-1 1898 Middle Jurassic Carnarvon, Australia Sandstone 0.21 DO-1 2702 Upper Triassic Carnarvon, Australia Siltstone 0.23 O-1 1195 Lower Cretaceous Carnarvon, Australia Siltstone 0.36 P-1 3325 Carnarvon, Australia 0.31 SA-1 1405 Lower Cretaceous Carnarvon, Australia Siltstone 0.12 SO-1 1542 Cretaceous Carnarvon, Australia Sand-/silt-stone 0.15 WA-1 590 Cretaceous Carnarvon, Australia Reservoir 0.43 Mayneside-1 2970 Cretaceous Eromanga, Australia Shale Low maturity Mayneside-1 3000 Cretaceous Eromanga, Australia Shale
Mayneside-1 3050 Cretaceous Eromanga, Australia Shale
Volador-1 3033 Upper Cretaceous Gippsland, Australia Sandstone 0.15 Volador-1 3315 Upper Cretaceous Gippsland, Australia Sandstone 0.23 Volador-1 3405 Upper Cretaceous Gippsland, Australia Siltstone CPI: 2.27 Volador-1 3498 Upper Cretaceous Gippsland, Australia Siltstone 0.21 Volador-1 3573 Upper Cretaceous Gippsland, Australia CPI: 2.31 Volador-1 3675 Upper Cretaceous Gippsland, Australia Ro: 0.70% Julia Creek Cretaceous Queensland, Australia Oil shale 0.28 GNK-67 1114 Middle Miocene S. Sumatra, Indonesia Shale 0.17 GNK-67 1351 Middle Miocene S. Sumatra, Indonesia Shale 0.14 GNK-67 1514 Lower Miocene S. Sumatra, Indonesia Shale 0.36 Maniguin-2 2268 Miocene SE Luzon, Philippines Coal Ro: 0.66%
a Unless otherwise stated in the table, values are for the maturity parameter C29
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 North-ern 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 struc-ture of compoundXXisolated 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 colo-nizing 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 struc-turally 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 aro-matic 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 toÿ23.96%) is in the same range as aromatic
land plant biomarkers (ÿ24.88 to ÿ26.64% for
cada-lene; 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
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 fungusDaldinia concentricawere reported to be 0.394 and 0.016% of its dry body (Hashi-moto et al., 1994). Perylenequinone pigments (XIX) from insect speciesAphididaewere 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 Ascomy-cetes, 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). Tak-ing into account the contents of perylenequinone pig-ments in fungi, it is reasonable to suggest that fungi may
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 recog-nized probably only in the past two decades, as spores of fungi were not discussed in the Handbook of
Paly-nologypublished 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 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 from the Maniguin Island, Philippines. Perylene was found to be a prominent unsubstituted PAH in the aromatic frac-tions from this coal sample (Fig. 7). Them/z252 mass chromatogram 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 much more abundant than benzopyrenes. Palynological exami-nation revealed that fungal remains are the second most abundant palynomorphs after large cuticular fragments of unknown plant anity, 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 peryl-enequinone 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 con-tribution 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 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 thanked for their constructive reviews of the manuscript.
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