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Pergamon 0146-6380 95)00058-SOrg. Geochem. Vol. 23, No. 9, pp. 837-843, 1995

Copyright 0 1995 Elsevier Science LtdPrinted in Great Britain. All rights reserved

Ol46-6380195 $9.50 + 0.00

Identification of bicadinanes in Jurassic organic matter from theEromanga Basin Australia

CARIM ARMANIOS, ROBERT ALEXANDER, IMAM B. SOSROWIDJOJO andROBERT I. KAGI

Australian Petroleum CRC at Centre for Petroleum Environmental Organic Geochemistry, CurtinUniversity of Technology, G.P.O. Box U 1987, Perth, WA 6001, Australia

(Recei ved 5 Jul y 1994; evi sed 3 August 1994; accept ed 29 June 1995)

Abstract-Cis-cis-trans and trans-trans-frans-bicadinanes were identified in a Jurassic crude oil and twoJurassic rocks from the Eromanga Basin, Australia, after the branched and cyclic alkane fractions hadbeen enriched in bicadinanes using ultrastable Y molecular sieves. These biomarkers have previously beenreported only from angiosperms and their occurrence in Jurassic samples may indicate the early evolutionof flowering plants in this basin.

Key wsords-bicadinanes, biomarkers, angiosperms, Jurassic. molecular sieves, liquid chromatography,Eromanga Basin, Australia, age of angiosperms

INTRODUCTION

Bicadinanes have been reported to occur in Tertiarysedimentary organic matter from Southeast Asia(Grantham et al ., 1983; van Aarssen et al., 1990a;Alam and Pearson, 1990; Sosrowidjojo et al., 1994).Although a range of bicadinane isomers has beenreporte d to occur in crude oil (van Aarssen et ul .,1992), the three major isomers are cis-cis-trans-bicadinane (I; Cox et al., 1986), truns-truns-truns-bicadinane (II; van Aarssen et al., 1990b) andbicadinane R of unknown structure. The origin ofthese and related compounds has been associatedwith dammar resins (Grantham et al., 1983) from theextant angiosperm Dipt erocurpuceue (van Aarssener nl., 199 0a). This plant produ ces copiou s resincontaining a polycadinene which is repor ted to de-polyme rize upon th ermal stress to form bicadinanesalong w ith a range o f cadinanes and polycadinanes(van Aarssen et al ., 1991). Because Dipt erocurpuceaeonly occurs in rocks of Oligocene or younger age(Muller, 1981; Bande and Prakash, 1986; Lakhanpaland Guleria, 1986 ), bicadinanes have been used asage-specific biomarkers.

However, Di pt erocurpaceue is not the only an-giosperm from which sedimentary bicadinanes can bederived. A polysesquiterpene, reported to occur in thefruits of ancient representativ es of Masti xioid cor-nuceue (Crelling et al. 1991; Meuzelaar et al ., 1991),has also been show n to contain a similar polycadi-nene precursor (van Aarssen et al., 1994). The occur-rence of these fossil fruits in the Eocene Messel oilshale and Eocene Dorset rocks (Chandler, 1962;Collinson, 1983), which were deposited in a region of

cooler climates than those of Southeast Asia, suggeststhat bicadinane precursors were not restricted totropical conditions. Although dammar resins appearto be the major precursors of sedimentary bicadi-nanes so far reported, other angiosperms have pro-duced bicadinanes thus extending the age range oftheir precursors back to at least Eocene and possiblyto Early Cretaceous times when angiosperms firstevolved (Stewart and Rothwell, 1993).

Recent evidence suggests a pre-Cretaceous evol-ution of angiosperms. Based on studies of extantprimitive angiosperms and of Jurassic fossils withangiosperm-like leaf and woo d characteristics, othertheories have been proposed for the time and place oforigin of flowering plants. Lar ge concentrations ofliving primitive angiospe rms found in southeas ternAsia, northern Australia and the southw estern Pacificsuggest that angiosperms originated in these areasduring Jurassic or earlier times (e.g. Bailey, 1949;Axelrod, 1952, 1960; Takhtajan, 1969). More re-cently, the possibility of a pre-Creta ceous origin forthe angisperms has been established (cf Palmer,1994). Based on calculations of molecular clocks inthe DN A of living plants (Martin et al ., 1989; Craneet al ., 1989) and on cladistic hypotheses that linkangiospe rms with extinct Triassic plants such asBennet t it al es and Gnetal es (cf. Crane, 1993), it wasconcluded that the plant lineage that led to theflowering plants must have diverged from these Trias-sic plants more than 230 million years ago. Furthersupport has come from Cornet (1993) who reportedthe presence of a single small leaf and two flowersof Punnanlika triassica in a Late Triassic blackshale in North Carolina. In this note we report the

837

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838 Carim Annanios et al.occurrence of very low levels of bicadinanes in The samples used in this study were obtained fromJurassic samples from the Eromanga Basin, the Westbourne Formation of Jurassic age (Fig. 2)Australia. (Green et al., 1989). The core samples from T hargo-mindah- were a mudstone and a siltstone, both dark=

& &

grey in colour. The Corona-l DST 1 sample was ahigh wax crude oil. Geochemical parameters for each*,& sample are given in Table 1.

/& = A = Reagent sI II All solvents u sed were distilled and blanks wereanalysed to ensure no contamination of sieves and

solvents by bicadinanes.EXPERIMENTAL

Geologi cal set t ing and samples Extract ion and separat ion of branched and cycli cThe Eromanga Basin is located near the centre alk ane fract ions

of the Australian continent (Fig. 1). Basin infill Thargom indah-2 core samp les (2 g) wer e groundoccurre d mainly during Jurassic and Early Creta- and then exhaustively extract ed usingceous times under a fluvialjacustrine depositional dichlorom ethane (30 mL ) to obtain the solublesetting (e.g. Bowering and Harrison, 1982; Price organic matter (SOM ). The branched and cyclicet al ., 1985). alkanes w ere then obtained using previously reporte d

EROMANGA BASIN : : : : : : : : : : : : : : : :................................................................................................................................................................................Qi. j j : : : : : : : : : : : :

259. . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . , : ~: : / . . . . . . . . : ~: :. . . . . . . . . . . . . . . . ......................... . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. A. . . . . . . . . . . . . . . . .. . . .e- w. _ v. - . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . .1 . . . . . . . . . . . . . . . . . . . . . . . .: &j &h&&J al f aI, :1 1 1 111 /. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .: : : : : :

. . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . .

.lOOkm. .

Fig. 1. Map of the Eromanga Basin and the underlying Coop er Basin in eastern Australia. Stipple patterndenotes part of the Eromang a Basin.

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Bicadinanes from the Eromanga Basin. Australia 839

AGE

-240

II LITHOSTRATIGRAPI-IY

AI 2 Mackunda Fm -5 \bodnadatta7 Alkm~&Fm nolahur:Fm \Cooriklana sst

~ Bulldog shale Wallumbilla Fm

Wyandra sstCadna-Owie Fm

Hooraysst

-It-- +?zirkhead FmYg Hutton sst5\

Basal Jurassic shale unit

Nappamerri Fm Cooper

BASINNAME

DEPTH m) TOTOP OF

FORMATION

38610-799

-845

I

8-5.2 6-236

- 932- 1012

-1162

- 1259

Fig. 2. Stratigraphy of the Eromanga Basin (after Price et al., 1 985) showing the location of the crudeoil and rock samples.

liquid chromatographic techniques (cf. Armanioset a l ., 1992 . In brief, the crude oil or SOM waschromatographed on a silicic acid column usingn-pentane as the eluent. A non-retained fractioncontaining alkane s and monoaromatic hydrocarbonswas collected and then further treated with ZSM-5molecular sieves to remove the n-alkanes, methy-lalkane and alkycyclohexane components. Finally,medium performance liquid chromatography

(MPLC ) using silica gel was used to remove themonoaromatic compounds, leaving an alkanefraction rich in polycyclic compo nents.

Enrichment of bicadi nanes using mol ecular sieves

Liquid chromatography using US-Y molecularsieves was based on a previously reported procedure(Armanios et al., 1992). The column was tightly drypacked with the sieve powder and then washed with

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840 Carim Armanios et al.Table 1. Selected geochemical maturity paramet ers for samples. (a) Peters and Mod owan , 1993; (b) Alexander el al., 1985;

(c) Radke and Welte, 1983Corona- I Thargomindah-2 Thargomindah-2

Maturity parameters DST I 1240.53 m 1242.51 mTOC (%) 0.75 0.69SOM (%) 0.033 0.034SOM/TOC 0.044 0.049

nax 445 439Sl 0.04 0.04s2 - 0.40 0.55PI 0.09 0.07R, (%) 0.62 0.62Ts/Ts t Tm 0.15 0.17 0.13(fla/Sa + c$) hopane 0.10 0.26 0.22(22S/22S t 22R) hopane 0.58 0.59 0.59(2OS/2OS t 20R) sterane 0.45 0.47 0.48DNR-I 1.6 2.0 1.9TNR-I 0.41 0.42 0.46MPI 0.33 0.28 0.22R, 0.60 0.57 0.53TOC (%ttotal organic carbonSOM (%+soluble organic matter7,,,-tempera ture corresponding to the S2 maxima rock eval pyrolysis ( C)PI-production index (SljSl t S2)& (%)--vitrinite reflectanceTs/Ts + Tm-22,29,30-trisnorneohopane/22,29,30-trisnorneohopane t 22,29,30-trisnorhopane(ba//?a + afi) hopane-flu-hop ane/fia-hopane + afi-hopane(22S/22S + 22R) hopane-22s afi-homohopane/22S ab-homohopane t 22R afl-homohopane(2OS/2O S + 2OR) sterane-20s ethylcholestane/20S ethylcholestane + 20R ethylcholestaneDNR-I-2,6 DMN + 2,7 DMN/I,S DMN (DMNaimethylnaphthalene)TNR-l-2,3,6 TMN/l,4,6 TMN t 1,3,5 TMN (TMN-trimethylnaphthalene)MPI-I .5 (2MP t 3 MPjP t I MP + 9 MP) (P-phenanthrene, MP-methylphenanthrene)

Oil onset

0.054. I435445

0.10.6a0.560.30.60.51.5b0.5b0.30.6

R,--o.6 MPI t 0.4

two bed volumes of n-pentane. The branched andcyclic alkane fraction was introduced onto thecolumn and allowed to stand for 2 min, after whichthe column was eluted w ith n-pentane at the rate of1 drop every 10 s using compressed nitrogen. GC-M Sanalyses reported here were carried out on the firsteluted fraction (200 p L).Gas chromatography-mass spectromet ry

The analysis of branched and cyclic alkane frac-tions by GC-M S was carried out using a Hewlett-Packard 589 0 Series II gas chromatograph connectedto a HP 597 1 mass selective detector operating at70 eV. The gas chromatograph was equipped with a40 m x 0.18 mm i.d. fused silica capillary columncoated with a DB-1 stationary phase (J W . Heliumwas used as the carrier gas at a linear flow velocity of27 cm/s. The oven was programmed from 7 0 to 280Cat 4C/min.

RESULTS AND DISCUSSIONMolecular sieve chromatography

The branched and cyclic alkane fractions from thecrude oil and the two rocks were chromatographedusing US-Y molecular sieves to enrich the bicadi-nanes. The ability of this technique to unmask traceamounts of bicadinanes in a crude oil has beendemonstrated previously (Armanios et af., 1994).Figure 3 shows a comparison of m/z 412 masschromatograms for the branched and cyclic alkanesfrom the crude oil and rocks before sieving and inFraction 1 from the sieve column. The bicadinanes

were identified based on their m/z 412 parent ion andm/z 369 ion fragment responses, as well as theirretention times. The mass chromatograms for theunsieved alkane fractions show that the presence ofbicadinanes is equivocal, e.g. note the weak responsefor trans-trans-trans-bicadinane (T). The mass chro-matograms of Fraction 1, however, show clear evi-dence for the presence of bicadina nes in these Jurassicsamples. The bicadinanes, totally excluded from thesieve channels (Armanios et al ., 1994), were selec-tively enriched and separated from other coelutingcomponents in Fraction 1. The removal of interferingcomponents reduced the chemical background noise,thus improving the detection limits for the traceamounts of bicadinanes present in the samples.Possibil it y of sample contaminati on

The issue of contamination of the samples duringlaboratory processes or from migrating fluids in thesubsurface has been addressed. Blank experimentswere carried out in parallel with those for extractionand fractionation of the sedimentary hydrocarbons.No significant contamination was observed in thechromatograms from these blank experiments. In thecase of the Thargom indah-2 rock samples, the matu-rities of the bound and soluble hydrocarbons havebeen compared in order to detect contamination of i nsitu hydrocarbons by more mature migrating hydro-carbon fluids. Table 1 shows Ro ck-Eva1 T,,, andProduction Index (PI) values. These, together withthe vitrinite reflectance value of 0.62, indicate that thebound organic matter has a maturity correspondingto initial oil formation. The biomarker and aromatic

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Bicadinanes from the Eromanga Basin Australia 841

N

~JRAat~SmiCn Rhoc ~,1240.53 m ~

Fraction 1R

JURASSIC ROCKThargomindah 2, 1242.51 m

Fraction 1R

42 44 46 48 50Retention time (rain)

Fig. 3. Partial m z 412 mass chromatog rams of the branched and cyclic alkane fractions from a Jurassiccrude oil and two Jurassic rocks showing the relative abundance of the bicadinanes before sievingcompared with that in Fraction I from the sieve column.

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842 Carim Armanios et al.maturity data obtained from the soluble hydrocar-bons show that they too are from a similar maturityzone. These results, together with the SOM/TOCvalues, are consistent with uncontaminated in situhydrocarbons.

In the case of the Corona-l crude oil, it is criticalthat it was derived from source rocks of Jurassic ageand not from Late Cretaceous or younger source. TheJurassic Westbourne Formation, from which thecrude oil was obtained, overlies basement rocks andhas a temperature of 88.5 C at its base. The data inTable 1 indicate a very low maturity source rock forthis crude oil and are consistent with a source fromwithin the Westbourne Formation. The depth at thebase of Late Cretaceous Winton Formation at thislocation (Fig. 2) is only 236m (temperature 39C)and is too immature to be a source of crude oil. Weare therefore confident that the Corona-l crude oilrepresents hydrocarbons of Jurassic age.Origin of bicadinanes

The very low concentrations of bicadinanes inthese Jurassic samples, which predate the widespreadoccurrence of angiospe rms, can be interpreted in twoways . First, older plants may have contributed bicad-inane precursors to sediments. H ence, although poly-cadinenes originating from angiosperm resins are themain precursors of the bicadinanes in Tertiary andyounger rocks, other plant types that extend furtherback into the sediment record may also have beencapable of producing these compounds. Alterna-tively, the bicadinanes in the Jurassic of the Ero-manga Basin originated from angiosperms similar tothe primitive extant an giosperm s in the nearby n orth-east Queensland rainforests. The large concentrationof primitive extant species of flowering plants in thisregion has led to suggestions that angiosperms origi-nated in this region during pre-C retaceou s times(e.g. Takhtajan, 1969). Combined with other evidencethat angiosperms diverged from more primitiveplants as early as the Triassic (Martin et al., 1989;Crane et al., 1989; Cornet, 1993), a Jurassicangiosperm is a possible source fo r these bicadinanes.Associate Editor--J. Curiale

Acknowledgements-The authors wish to thank Mr PeterGreen of the Queensland Geological Survey for geologicaldata. Mr Carim Armanios acknowledges receipt of anAustralian Postgraduate Research Award and Mr Imam B.Sosrowidjojo wishes to thank the Australian InternationalDevelopment Assistance Bureau for financial support.

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