Organic

Geochemistry
Organic Geochemistry 35 (2004) 937–957
www.elsevier.com/locate/orggeochem

Geochemistry of oil in fluid inclusions in a middle

Proterozoic igneous intrusion: implications for the source
of hydrocarbons in crystalline rocks
a,* b,1 c,2 b,1
A. Dutkiewicz , H. Volk , J. Ridley , S.C. George
a
School of Geosciences and Institute of Marine Science, University of Sydney, Sydney, NSW 2006, Australia
b
CSIRO Petroleum, P.O. Box 136, North Ryde, NSW 1670, Australia
c
Department of Earth and Planetary Sciences, Macquarie University, Sydney, NSW 2109, Australia
Received 18 December 2003; accepted 23 March 2004
(returned to author for revision 19 February 2004)
Available online 30 April 2004

Abstract

The ca. 1280 Ma dolerite sill within the Mesoproterozoic Roper Group in the Roper Superbasin, Australia,
contains evidence for at least two episodes of hydrocarbon migration represented, respectively, by solid bitumen
with a ketone-rich extract, and a mixture of a high maturity gas-condensate and a lower maturity oil within oil-
bearing fluid inclusions. The ketone isomers are formed by flash pyrolysis of kerogen during the intrusion of the
dolerite sill [Org. Geochem. 21 (1994) 829] and represent the first and oldest phase of hydrocarbon migration. The
gas condensate and oil were subsequently trapped as a mixture within fluid inclusions at diagenetic temperatures
and pressures of around 110 °C and 250 bars, significantly after cooling of the sill and likely during the Neo-
proterozoic reactivation of the Roper Superbasin. Either (1) these fluids migrated together and mixed in the res-
ervoir or (2) an earlier oil charge was flushed by a later condensate charge and the oil-condensate mixture was
trapped within single fluid inclusions. Oil inclusions occur chiefly within albitised zones of labradorite laths within
the dolerite matrix, and within transcrystalline microfractures cutting vein calcite and rarely vein quartz. Oil in-
clusions trapped in the vein calcite are accompanied by hypersaline Ca/Mg brines. Gas chromatography–mass
spectrometry of oil extracted from inclusions within the dolerite matrix shows that the oil is non-biodegraded and
was therefore trapped relatively quickly within the host minerals. Trace amounts of biomarkers indicate that the
inclusion oil is of a biogenic origin and excludes any abiotic processes that are apparent sources of hydrocarbons in
many crystalline rocks. Monomethylalkanes, pentacyclic terpanes chiefly comprising hopanes and diahopanes, and
very low concentrations of steranes and diasteranes indicate input from cyanobacterial organic matter with a minor
contribution from eukaryotes. The hydrocarbons are likely derived from Proterozoic source rocks such as the
directly overlying Velkerri Formation and/or the underlying Barney Creek Formation from the McArthur Group.
The study has implications for the source of hydrocarbons in non-sedimentary rocks and suggests that fluid in-
clusions can be used not only to distinguish between biogenic and abiogenic sources of hydrocarbons but also to

*
Corresponding author. Fax: +61-2-9351-0184.
E-mail addresses: adriana@geosci.usyd.edu.au (A. Dutkiewicz), Herbert.Volk@csiro.au (H. Volk), John.Ridley@geo.unibe.ch (J.
Ridley), Simon.George@csiro.au (S.C. George).
1
Fax: +61-2-94908197.
2
Present address: Institute of Geological Sciences, University of Bern, Baltzerstrasse 1-3, CH-3012, Bern, Switzerland. Fax: +41-31-
631-4843.

0146-6380/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2004.03.007
938 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
provide critical information about the composition of the biomass, fluid migration events, and conditions under
which hydrocarbons in different geological settings are trapped.
Ó 2004 Elsevier Ltd. All rights reserved.
Keywords: Precambrian oil; Oil inclusions; Biomarkers; Roper Group; Roper Superbasin; Dolerite
1. Introduction
Where igneous and metamorphic rocks host methane
and higher-order hydrocarbons, their exact origin in
many instances remains controversial. The possibility of
an abiogenic origin has sometimes been evoked, for
example, through post-magmatic Fischer–Tropsch re-
actions (e.g., Szatmari, 1989; Ettner et al., 1996; Salvi
and Williams-Jones, 1997; Potter et al., 1998), outgas-
sing of the primordial mantle (e.g., Gold, 2001) or res-
peciation of a primary carbonic fluid (e.g., Kogarko
et al., 1987). Notable occurrences which have been ex-
plained through abiogenic origins include: (1) hydro-
carbon gas inclusions in Ilimaussaq igneous complex in
southern Greenland (Konnerup-Madsen et al., 1979), (2)
methane and higher hydrocarbons in granite and dol-
erite intrusions at Siljan, Sweden (Jeffrey and Kaplan,
1988), (3) hydrocarbon gas seeps in the Zambales
Ophiolite, Philippines (Abrajano et al., 1988), (4) hy-
drocarbon inclusions containing saturated and unsatu-
rated aliphatics in pegmatite quartz in granite at Strange
Lake, Canada (Salvi and Williams-Jones, 1997), (5)
methane-bearing fluid inclusions in alkaline igneous in-
trusions of the Kola igneous province (Potter et al.,
1998) and (6) methane and higher hydrocarbons in
fractures in crystalline rocks of the Canadian shield
(Sherwood Lollar et al., 2002). In contrast, a widespread
occurrence of bitumen in basement rocks in Scandinavia
and gas-condensate inclusions with alkane homologues
up to C15 in the crystalline basement in South Norway
(Munz et al., 2002) and numerous complex hydrocar-
bons in granite plutons in the British Isles (Parnell, 1988)
have been attributed to overlying sedimentary source
rocks and have been derived from the thermal decom-
position of organic matter. Solid bitumens within a
dolerite dyke at Oklo in Gabon (Mossman et al., 2001)
have similarly been interpreted to be the products of oil
migration from surrounding sedimentary rocks. A
comprehensive list of hydrocarbon occurrences associ-
ated with igneous rocks can be found in Schutter
(2003a).
Extractable organic matter and oil are relatively
uncommon in early Precambrian rocks due to low
concentrations of total organic carbon in ancient
source rocks, breakdown of hydrocarbons under
metamorphic conditions and loss of hydrocarbons
over time (e.g., Hunt, 1996). However, where present
their molecular and isotopic composition not only
allows distinction between biogenic and abiogenic
sources, but can give important information about the
ancient biomass and about oil migration. It has re-
cently been documented that some ancient oils have
been preserved for billions of years within fluid in-
clusions in Archaean and Proterozoic sandstones and,
although low in abundance, are sufficiently pristine to
yield biomarkers and information about the timing
and conditions of entrapment (Dutkiewicz et al., 1998,
2003a). Furthermore, survival of complex hydrocarbons
is evident within fluid inclusions at temperatures up to
300 °C (Dutkiewicz et al., 2003b). Therefore, preserva-
tion of hydrocarbons in fluid inclusions should be pos-
sible in crystalline rocks, a large proportion of which are
of Proterozoic age.
Here, we report on the discovery and composition of
abundant oil inclusions in a Middle Proterozoic dolerite
sill that was intruded into a sedimentary sequence
known to contain oil shows such as bitumen and oil
seeps (e.g., George et al., 1994). We use a combination
of inclusion petrography, microthermometry and mo-
lecular characterisation, including biomarker analysis of
the inclusion oils to demonstrate that this magmatic
rock hosted oil is biogenic and was trapped on migration
through the sill after cooling. We further use biomarkers
to constrain the source rocks of the oil and the nature of
the source biomass and suggest that a similar approach
can be used to distinguish between biogenic and abio-
genic sources of hydrocarbons, particularly in rocks
which no longer contain oil or gas in the pore spaces or
have no obvious association with conventional source
rocks or a fracture network. Our fluid inclusion ap-
proach can also provide a better understanding of pe-
troleum systems associated with crystalline rocks,
particularly in terms of the timing, entrapment condi-
tions and migration pathways, which are still poorly
understood.
2. Geological setting
The marine sedimentary succession of the ca. 1430
Ma Roper Group (Jackson et al., 1986; Powell et al.,
1987) from the intracratonic Roper Superbasin, Aus-
tralia (Fig. 1) is one of the oldest and least deformed and
least metamorphosed hydrocarbon-bearing Proterozoic
sequences in the world. This study investigates a dolerite
sill within the Roper Group sequence, which is likely
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957 939

Fig. 1. (a) Geological map of the Roper Superbasin showing the location of the Friendship-1 and Borrowdale-2 wells (after Pietsch
et al., 1991). (b) Stratigraphy of the Roper Basin and the Friendship-1 core (after Summons et al., 1988). Absolute ages are from
McDougall et al. (1965), Kralik (1982), Jackson et al. (1999), Jackson et al. (2000) and Page and Sweet (1998).
940 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
part of a widespread intrusive suite dated at 1280 Ma
(McDougall et al., 1965) emplaced into pre-existing
fractures during an extension event. The sill is directly
overlain by Velkerri Formation shales with total organic
carbon (TOC) levels of up to 8% (Jackson and Raiswell,
1991; Warren et al., 1998) and is underlain by Bessie
Creek Sandstone (Fig. 1) where a distinct contact
metamorphic fabric (‘‘baking’’ texture) induced by the
intrusion is evident (Dutkiewicz et al., 2003a). Oil shows
and bitumen have been observed in the Bessie Creek
Sandstone and in the dolerite (Ledlie and Torkington,
1988; Ledlie et al., 1988; George et al., 1994), and live oil
has been observed to seep out of the marine Velkerri
Formation shale (Powell et al., 1987), which has been
the subject of several geochemical studies (Jackson et al.,
1986; Summons et al., 1988; Warren et al., 1998; George
and Ahmed, 2002). Solid bitumens in the sill form thin
linings to fracture surfaces and amorphous coverings to,
and intimate mixtures with, host minerals of the fracture
walls. They are non-fluorescing under UV excitation
(George et al., 1994). Hydrocarbon extracts of a fracture
hosting this solid bitumen show the presence of an un-
usual suite of saturated ketone isomers formed most
likely by flash pyrolysis during intrusion of the dolerite
sill (George and Jardine, 1994). The extract was rich in
polar compounds with n-alkanes only 3–4 times more
abundant than the ketones (George and Jardine, 1994).
Different extract fractions, including asphaltenes, polar
compounds, aromatic hydrocarbons and aliphatic hy-
drocarbons, all have d13 C values between )31‰ and
)33‰ (George et al., 1994) and fall within the range
expected for organic matter derived from kerogens
(Lewan, 1986) and crude oils generated from organic
matter (Yeh and Epstein, 1981). No results of biomarker
analyses were published in George et al. (1994). Further
hydrocarbon shows include oil inclusions in post-meta-
morphic quartz-filled micro-fractures in the Bessie Creek
Sandstone (Dutkiewicz et al., 2003a; Volk et al., 2003).
These were trapped at relatively low temperatures of

60 °C and contain a range of biomarkers derived
mainly from prokaryotic organic matter.
Deformation of the Roper Group is mild on a re-
gional scale (Rawlings, 1999). Structural inversion post-
dates an east–west extension that was accompanied by
the intrusion of the dolerite sills and pre-dates devel-
opment of the Neoproterozoic to Palaeozoic Arafura
Basin (Powell et al., 1987; Haines et al., 1999; Rawlings,
1999). The inversion event may be related to the as-
sembly of Rodinia ca. 1300–1000 Ma (Dalziel, 1992).
The deformation resulted in structural reactivation,
wrench-faulting, steepening of earlier faults and mild
folding. The region has been essentially stable, experi-
encing slow erosion since deformation (Haines et al.,
1999) and much of the present structural grain in the
region is due to the Mesoproterozoic inversion event
(Sweet et al., 1999).
Burial history analysis of the Roper Group (Jackson
et al., 1988) suggests that the Velkerri Formation
reached its maximum burial at around 1400 Ma, with
estimated burial temperatures of about 75 °C. Soon after
burial the sequence experienced steady uplift until about
500 Ma, followed by a period of relative stability
punctuated by four minor uplift and burial events in the
Phanerozoic (Jackson et al., 1988).
3. Materials and methods
The dolerite sill was sampled from the drill core
Friendship-1, collected in 1988 by Pacific Oil & Gas Pty
Ltd. to test the petroleum prospectivity of the Upper
Roper Group (Fig. 1). Friendship-1 is located about 30
km NNE of Borrowdale-2, which was the subject of an
earlier fluid inclusion study (Dutkiewicz et al., 2003a).
Both wells penetrated complete sections of the Bessie
Creek Sandstone, the dolerite sill and the Velkerri For-
mation. The dolerite sill at Friendship-1 was penetrated
between 262.5 and 362.2 mKB (metres below kelly
bushing), and between 434.5 and 526.47 mKB at Bor-
rowdale-2. Correlations between Friendship-1 and Bor-
rowdale-2 are based on consistent stratigraphic
relationships, lithology and petrography.
Eight doubly polished, 100-lm thick sections of the
dolerite sill from depths of 272.2–272.4 mKB and two
ordinary thin sections were examined using an optical
microscope equipped with transmitted, reflected and
epifluorescent light, by scanning electron microscopy
(Philips SEM 505 and Philips SEM XL30) including
backscattered electron-dispersive spectroscopy (EDS)
and X-ray mapping. Microthermometry of 220 oil and
aqueous fluid inclusions was carried out on a Linkham
heating-freezing stage calibrated using synthetic H2 O
and CO2 inclusions. In order to avoid stretching and
leakage of fluid inclusions caused by expansion of ice,
heating runs were conducted before the cooling runs as
recommended by Goldstein and Reynolds (1994).
In order to specifically target fluid inclusion oil and
its molecular markers, a fresh sample of the dolerite with
no calcite veins or solid bitumen was selected from ap-
proximately the same depth as the one used in the
George and Jardine (1994) study. Determination of the
molecular composition of oil inclusions was carried out
using the methods similar to those described in George
et al. (1998). A sub-sample was lightly crushed into
granule and very coarse sand-sized fractions and cleaned
in hydrogen peroxide, hot Aqua Regia and hot chromic
acid. This treatment removed any calcite that was
present initially, but most of the dolerite matrix minerals
were preserved during this procedure, including feldspar
and quartz that host oil inclusions. The cleaned fraction
(17.5 g) was then crushed under dichloromethane (off-
line crushing) and the extracted fluid inclusion oil, which
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
was comprised of the co-mingled contents of fluid in-
clusions from the dolerite matrix minerals, was analysed
by gas chromatography–mass spectrometry (GC–MS)
on a Hewlett–Packard 5890 gas chromatograph inter-
faced to a VG AutospecQ Ultima mass spectrometer.
Single ion monitoring (SIM), metastable reaction mon-
itoring (MRM) and magnet scanning modes of detection
were used. Before the inclusion fluids were extracted by
off-line crushing, system blank experiments using the
same experimental conditions and glassware (including
the same amount of solvent) were carried out in order to
determine the extent of any hydrocarbon contribution
from the crushing cylinder and any carry-over from
previously analysed samples or general laboratory
background. System blanks that were deemed to be
sufficiently clean were acquired one day prior to crush-
ing of the dolerite fraction, and the sample was subse-
quently crushed using exactly the same glassware. Low
molecular weight compounds are not retained during
sample workup using the off-line crushing method.
Therefore, the molecular composition of low molecular
compounds was assessed using a direct on-line crushing
method in a Quantum MSSV-1 Thermal Analysis Sys-
tem inlet mounted onto the same GC–MS system that
was used to analyse the liquid off-line extracts. Liberated
compounds were thermally extracted in a helium flow at
300 °C and focussed in a cryogenic trap prior to GC
separation (George et al., 1998). Whereas the off-line
crushing method is advantageous for the analysis of
traces of C12þ hydrocarbons such as biomarkers, the on-
line method yields complementary information on the
gasoline range hydrocarbon distribution of fluid inclu-
sion oils (e.g., Ruble et al., 1998; Volk et al., 2002). On-
line crushing coupled with gas chromatography has been
successfully used to examine the gasoline range hydro-
carbons in fluid inclusions in Phanerozoic (Jensenius
and Burruss, 1990; Wiggins et al., 1993; Tseng et al.,
1999; Volk et al., 2000, 2003) and Middle Proterozoic
rocks (Newell et al., 1993; Mauk and Burruss, 2002).
4. Oil Inclusions in the dolerite sill
The dolerite sill is generally unaltered. Fresh dolerite
is composed of ophitic augite, labradorite laths, ilmen-
ite, quartz, minor apatite, andesine and scattered pat-
ches of granophyric quartz–K-feldspar intergrowth.
Pyroxene is rimmed by hornblende in some sections of
rock. At least two phases of hydrothermal alteration are
recognised. Incipient to pervasive spilitic alteration is
marked by chlorite, leucoxene and recrystallisation of
primary plagioclase and granophyric K-feldspar to al-
bite. Incipient alteration is often marked by patchy re-
placement of labradorite plagioclase by albite (Fig. 2). A
near-vertical quartz–calcite–chlorite vein is intersected
approximately 10 m below the sill top. The vein is up to
941
1 cm thick, wavy, varicated and variegated, and over-
prints patches of spilitic altered dolerite. It is rimmed by
a 2–3 mm thick, pink-coloured zone of bleached wall-
rock composed of clay-dusted alkali feldspar, quartz
and fine hematite plates. The vein walls are largely
coated with zoned drusy euhedral quartz crystals that
grew into open- or fluid-filled space from nuclei on the
walls. Inclusions outline up to four growth zones al-
though crystals with a single growth zone are most
common (Fig. 3). The youngest growth zone of quartz is
in all cases more irregular and is either intergrown with
the coarse calcite vein infill or is embayed by calcite
(Fig. 3). Vein calcite infill is coarse-grained and is in-
tergrown with fine chlorite. Calcite deformation twins,
planar microfaults and chlorite-lined stylolitic seams
indicate one or more phase of deformation after vein
infill (Fig. 3).
Three types of fluid inclusions are recognised in the
dolerite as determined by petrography and microther-
mometry. Most of the fluorescing oil-bearing fluid in-
clusions are hosted within just two minerals: vein calcite
and plagioclase crystals (Fig. 3).
4.1. Type 1
Fluid inclusions that form clusters within the core of
and along growth faces of drusy vein quartz (Fig. 3(d)).
These inclusions are aqueous and no primary fluorescent
oil-bearing inclusions occur within the growth zones. All
inclusions are extremely small, usually
5 lm in longest
dimension and rarely exceed 10 lm. Most contain water
and gas and occasionally an unidentified and likely ac-
cidental solid phase. The gaseous phase usually com-
prises
10% of the total inclusion volume; however, the
gas content varies from 0 vol% (single phase inclusions)
to
90 vol%. Some of the gas bubbles are mobile at
room temperature.
4.2. Type 2
Fluid inclusions within extensive, sub-parallel trans-
crystalline microfractures cutting the calcite crystals,
calcite twins and rarely euhedral quartz crystals bor-
dering the vein (Fig. 3(c)–(h)). These trails cut the
growth zones and hence post-date entrapment of Type 1
inclusions. They include both oil inclusions (Type 2a)
and coeval aqueous inclusions (Type 2b). Type 2a fluid
inclusions contain oil and gas and occasionally water
(up to 15 vol%) and/or bitumen. They are irregular,
oval, spherical, sub-spherical, rectangular or square in
shape and are notably larger (around 10–20 lm in long
dimension) than oil-bearing fluid inclusions in the pla-
gioclase. Virtually all of these oil-bearing fluid inclusions
have blue fluorescence (yellow-fluorescing individuals
are rare) and occasionally have a yellow tinge in trans-
mitted light. Coeval Type 2b aqueous fluid inclusions
942 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957

Fig. 2. Photomicrograph and elemental maps of altered labradorite in Friendship-1 dolerite. Bright areas indicate enrichment in a
particular element, dark areas indicate depletion. (a) Abundant blue-fluorescing oil-bearing fluid inclusions within alteration zones in a
labradorite lath. White arrow indicates the edge of a triangle-shaped alteration zone and serves as a reference point for backscattered
SEM and elemental map images. UV excitation. (b) Backscattered electron image showing alteration zones within labradorite lath.
White arrow indicates the same location as in (a). (c) Elemental map showing distribution of Ca. Note that altered zones are poor in
Ca. (d) Elemental map showing distribution of Al. Altered zone contains slightly less Al than the rest of the crystal. (e) Elemental map
showing distribution of K. The labradorite crystal and its alteration zones are poor in K. Surrounding minerals show a granophyric
texture with K-rich areas most likely due to K-feldspar intergrowth. (f) Elemental map showing distribution of Mg. A fracture cutting
the length of the labradorite lath appears to be rich in Mg. The labradorite alteration zones are poor in Mg. (g) Elemental map showing
distribution of Na. Note that the alteration zones in the labradorite crystal are relatively rich in Na. (h) Elemental map showing Si
distribution. Labradorite alteration zones show a slight enrichment compared to the rest of the crystal. The brightest, Si-rich area is
probably quartz most of which forms a granophyric texture with intergrown K-feldspar (lower right).
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957 943

Fig. 3. Photomicrographs of Friendship-1 dolerite fluid inclusions. (a,b,c,e,g) UV-epifluorescence; (d,f,h) transmitted light. (a,b)
Clusters of small oil-bearing fluid inclusions within alteration zones in labradorite laths of the dolerite matrix. The majority of oil
inclusions have blue fluorescence. (c,d) Vein calcite (Cal) post-dating euhedral quartz (Q) and its overgrowth. Note the presence of
chlorite (Chl) within the calcite crystals. Calcite and quartz crystals are cut by a microfracture containing blue-fluorescing oil-bearing
fluid inclusions. In addition, the quartz crystal contains abundant tiny primary non-fluorescing inclusions which are dominantly
aqueous in composition. (e,f) Abundant blue-fluorescing oil inclusions within transcrystalline microfractures cutting calcite crystals
(Cal), calcite deformation twins and part of the quartz crystal (Q). (g,h) Euhedral quartz crystals (Q) lining the wall of the vein and
containing abundant aqueous fluid inclusions but no oil-bearing fluid inclusions. Quartz is post-dated by vein calcite (Cal) which is in
turn post-dated by stylolitic vein chlorite. Microfractures containing abundant blue-fluorescing oil-bearing fluid inclusions cut the vein
calcite and chlorite.
944 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
are usually sub-rectangular to rectangular in shape and
about 10 lm in longest dimension and contain water and
gas (water vapour?). The vein is also known to contain
fracture-hosted solid bitumen (George et al., 1994) but it
was not apparent in our samples and may therefore be
localised in occurrence.
4.3. Type 3
Fluid inclusions within clusters and discontinuous
trails of up to 30 individuals within matrix altered zones
of labradorite laths (Figs. 2(a) and 3(a) and (b)) and
rarely andesine, augite and quartz. Hydrocarbon inclu-
sions in the plagioclase laths are very small (10 lm or less)
and contain oil and generally between
10–40 vol% gas.
Gas bubbles are frequently mobile at room temperature.
Individual clusters often comprise oil inclusions with
blue, yellow and occasionally orange fluorescence col-
ours, although clusters with a single fluorescence colour
(e.g., blue or yellow) also occur. Poor sealing properties
of the host feldspar within some alteration zones may
have resulted in a fluorescence colour change (e.g., Munz,
2001). The characteristics of the yellow and orange
fluorescing inclusions, including the more variable in-
clusion sizes, ragged shapes similar to those described in
Munz (2001) and variable gas-oil ratios, suggest that
these are more likely than the blue fluorescent individuals
to have undergone leakage, stretching or modification
due to imperfect sealing within the mineral host. The near
uniform blue fluorescence colour of inclusions in micro-
fractures in more robust minerals such as vein calcite and
quartz supports this interpretation. X-ray mapping of
several labradorite laths reveals that the oil inclusions are
generally restricted to zones which are relatively poor in
calcium and aluminium and rich in sodium and silica
(Fig. 2), indicating albite composition. Rare, small (10
lm or less) coeval aqueous inclusions are associated with
the oil-bearing inclusions; however, most of these aque-
ous inclusions appear to define different fluid inclusion
trails and are hence interpreted to be unrelated to the oil
migration event. Although feldspars tend to be water-
wet, roughened and dissolved surfaces are often oil-wet
(Fassifihri et al., 1992) and will preferentially trap hy-
drocarbon phases.
5. Fluid inclusion microthermometry
All of the measured oil and aqueous fluid inclusions
in the dolerite homogenise to a liquid and were thus
trapped in the liquid phase. There is a broad range of
overlapping homogenisation temperatures (TH ) for the
three inclusion populations (Fig. 4), suggesting that en-
trapment of these fluids in the different host minerals
occurred at similar temperatures, well within the limits
of diagenesis.
5.1. Type 1 inclusions
Because of their extremely small size, only 40 fluid
inclusions were suitable for microthermometric mea-
surements. All of these inclusions were located in the
main growth zone of vein quartz and are interpreted to
have been trapped during the growth of the quartz
crystals. TH values for aqueous fluid inclusions in the
vein quartz fall in a wide range from 95 to >160 °C
(Fig. 4), the latter being the maximum for our heating
experiments due to leakage of some inclusions at that
temperature. Quantitative statistics on this relatively
small data set are of limited value, as the maximum
homogenisation temperature has not been measured and
it is possible that the distribution contains more than
one mode. Most of the aqueous fluid inclusions showed
persistent metastability on heating from a supercooled
state, particularly for inclusions which homogenised at
relatively low temperatures, with final ice melting taking
place above 0 °C. For stable inclusions, however, ice
melting temperatures are quite high and define a uni-
modal distribution ranging from )1.3 to )0.3 °C
(Fig. 4). These temperatures correspond to salinities of
0.5–2.2 wt% NaClequiv: (Oakes et al., 1990) and indicate a
slightly brackish waters much different from the hy-
persaline brine associated with subsequent vein calcite
fracturing and oil migration.
5.2. Type 2 inclusions
A total of 127 coeval oil and aqueous fluid inclusions
was measured in transcrystalline microfractures in the
vein calcite. Type 2a oil inclusions homogenised between
33 and 124 °C, while the Type 2b aqueous inclusions
homogenised at the expected higher temperatures (e.g.,
Munz, 2001) between 74 and 135 °C (Fig. 4). After su-
percooling to about )90 °C, the first melt in the aqueous
fluid inclusions generally occurred around )62 °C, sug-
gesting a calcium and/or magnesium-rich brine. Ice
melting temperatures (TM;ice ) show a distinct bimodal
distribution (Fig. 4) with the first mean of )30  1 °C
corresponding to a salinity of 26 wt% NaClequiv: and the
second mean of )18  0.5 °C corresponding to a salinity
of 20 wt% and NaClequiv: (Oakes et al., 1990).
5.3. Type 3 inclusions
In view of the likelihood of post-entrapment modi-
fication, most microthermometric measurements on
Type 3 inclusions in alteration zones in the feldspar were
made on blue-fluorescing oil inclusions of similar size
and phase ratios which form small clusters of individuals
and appear to have been adequately sealed within the
feldspar crystals. TH values of these inclusions range
from 56 to 127 °C and show a large scatter (Fig. 4). The
range may be the result of imperfect sealing, stretching,
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957 945

10 >160 35

9 Type 1 Aqueous Inclusions

Type 1 Aqueous Inclusions 30 in Vein Quartz
8 in Vein Quartz
7 25

Frequency
6
Frequency

20
5
15
4

3 10
2
5
1

0 0
0 20 40 60 80 100 120 140 160 180 200 -35 -30 -25 -20 -15 -10 -5 0
(a) TH (oC) (b) TM,ice (oC)

25 6

Type 2a Oil Inclusions Type 2b Aqueous Inclusions

5
20 in Vein Calcite in Vein Calcite

4
Frequency
Frequency

15

10
2

5
1

0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
(c) TH (oC) (d) TH (oC)

7 9

Type 2b Aqueous Inclusions 8 Type 3 Oil Inclusions

6
in Vein Calcite in Feldspar
7
5
6
Frequency

Frequency

4 5

3 4

3
2
2
1
1

0 0
-35 -30 -25 -20 -15 -10 -5 0 0 20 40 60 80 100 120 140 160
(e) TM,ice (oC) (f) TH (oC)

Fig. 4. Histograms of microthermometric analyses on fluid inclusions in Friendship-1 dolerite. TH , homogenisation temperature; TM;ice ,
melting temperature of ice. All inclusions homogenised to a liquid. Inclusion types are discussed in the text.

heterogeneous trapping, necking down or simply trap- and averaging about 25 °C are determined. The repro-
ping at different temperatures. The last explanation ducibility of TH measurements indicates that the range of
seems ruled out as the modes are not apparent in the TH values is not caused by leakage or stretching of the
measurements of individual clusters, for which ranges of inclusions during the heating and cooling experiments.
homogenisation temperature of between 10 and 40 °C If stretching or leakage did occur in the geological
946 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957

environment, then the relatively restricted range of
temperatures indicates that the TH values are relatively
small overestimates of the actual trapping conditions,
and that the trapping temperatures would have fallen
within the diagenetic range of temperatures.
6. Molecular composition of inclusion oil
The fluid inclusion petrography shows that the frac-
ture hydrocarbon extract analysed by George and Jar-
dine (1994) would have included solid bitumen and
inclusion oil hosted in fracture calcite. In order to sim-
plify interpretation of the geochemical data, a sample
lacking calcite-quartz veining was chosen. However, as a
precaution any potential calcite-hosted inclusions were
removed from the sample by treatment with acids, so the
inclusion oil analysed in this study was derived only
from mainly feldspar and rare andesine, augite and
quartz oil-bearing fluid inclusions in the dolerite matrix.
The off-line fluid inclusion oil extract is extremely rich,
yielding more than 464 times the amount of n-alkanes (587
ng C12 –C32 n-alkanes/g minerals crushed) compared to the
system blank and the final outside rinse (Fig. 5(A)). Low
molecular weight n-alkanes (C8 –C13 ) are much more
abundant than C15–32 n-alkanes, indicating a dominant
condensate composition in the inclusions. This is con-
firmed by the results from the on-line crushing (Fig. 6),
which show high amounts of C5 –C9 hydrocarbons, espe-
cially n-alkanes, with a maximum at n-C6 . Other abun-

Fig. 5. Partial mass chromatograms (A–H) for the Friendship-1 fluid inclusion oil and the corresponding system blanks, which were
drawn to the same scale as the fluid inclusion oil chromatograms using the internal standard. n-Alkanes and the internal standard
(squalane) are shown in the m=z 85 mass chromatogram of the inclusion oil (A) and the corresponding system blank (B). Total ion
chromatograms (not shown) are very similar to the m=z 85 partial mass chromatograms. Monomethylalkanes are expanded in the
partial m=z 85 mass chromatogram (C); MN, methylnonanes; MD, methyldecanes; MUD, methylundecanes; MDD, methyldodecanes
and MTD, methyltridecanes. (D) Pentacyclic triterpane distribution in the inclusion oil (m=z ¼ 191:2); Ts, C27 18a(H),22,29,30-tris-
norneohopane; Tm, C27 17a(H),22,29,30-trisnorhopane; C29 ab, 17a(H),21b(H)-30-norhopane; C29 Ts, 18a(H)-30-norneohopane; C30 *,
C30 17a(H)-diahopane; C29 ba, 17b(H),21a(H)-30-norhopane; C30 ab, 17a(H),21b (H)-hopane; C30 ba, 17b(H),21a(H)-hopane; C31–33 ab
22S and R, 17a(H),21b (H)-homo-, bishomo-, and trishomohopane (22S and R). (E) System blank corresponding to the pentacyclic
triterpane distribution. (F) Alkylnaphthalenes in the inclusion oil (added m=z ¼ 142:1 þ 156:1 þ 170:1); MN, methylnaphthalenes; EN
and DMN, ethyl- and dimethylnaphthalenes; and TMN, trimethylnaphthalenes. (G) System blank corresponding to alkylnaphthalene
distribution. (H) Alkylphenanthrenes in the inclusion oil (m=z ¼ 178:1, 192.1 and 206.1) and corresponding system blanks (below); P,
Phenanthrene; MP, methylphenanthrenes; EP and DMP, ethyl- and dimethylphenanthrenes. Chromatograms under respective m=z
traces show system blank scaled by using the internal standard.
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957 947

Fig. 6. Total ion chromatogram (TIC), (A) and partial mass chromatograms (B–D) from the on-line crushing of the Friendship-1 fluid
inclusion oil sample (C5 –C9 range). (B) m=z ¼ 57 partial mass chromatogram, showing mainly normal alkanes (nCx) and some
branched alkanes. (C) m=z ¼ 55 partial mass chromatogram, emphasising the cyclic alkanes. (D) Added m=z ¼ 78 þ 91 partial mass
chromatogram, showing benzene and toluene. Other peak abbreviations: iC5, iso-pentane; MP, methylpentane; MCP, methylcyclo-
pentane; MH, methylhexane; DMP, dimethylpentane; DMCP, dimethylcyclopentane; MCH, methylcyclohexane; MHe, methylhep-
tane; DMCH, dimethylcyclohexane.

dant hydrocarbons in the m=z 85 partial mass chromato-
gram are monomethylalkanes, particularly methylnon-
anes, methyldecanes, methylundecanes (MUD) and
methyldodecanes (MDD; Fig. 5(A)). Expansion of the
m=z 85 mass chromatogram in the range of MUD and
MDD (Fig. 5(B)) shows that mid-chain methylated iso-
mers (e.g., 4-, 5- and 6-MUD) are of similar abundance as
the terminal isomers such as 2- and 3-MUD.
Alkylcyclohexanes and methylalkylcyclohexanes are
abundant, and their abundance maximises at C12 and
C11 , respectively, and attenuates rapidly with increasing
carbon number. This is consistent with observations of
Hoffmann et al. (1987) who showed that alkylcyclo-
hexane profiles typically follow n-alkane profiles. Care-
ful examination of magnet scan data failed to detect any
ketones in the inclusion oil. The lack of a hump of an
unresolved complex mixture in the m=z 85 mass chro-
matogram and the presence of n-alkanes is good evi-
dence that unlike the overlying Velkerri Formation
(Warren et al., 1998) and most solid bitumens with the
Roper Group (George et al., 1994), the inclusion oil has
never been affected by biodegradation and was thus
trapped relatively quickly within the host minerals.
Aromatic compounds including alkylbenzenes, alkyl-
naphthalenes, alkylphenanthrenes, alkylbiphenyls and
alkyldibenzothiophenes are present in the inclusion oil
and were detected in much higher abundances than in
the corresponding system blanks (Fig. 5). The C2 –C4
alkylbenzenes (87%) are significantly more abundant
than C1 –C5 alkylnaphthalenes (9.3%), C1 –C3 alkylphe-
nanthrenes (3.1%), C1 –C2 alkylbiphenyls (0.5%) and C1 –
C2 alkyldibenzothiophenes (0.1%). This very marked low
molecular weight predominance in the distribution of
aromatic compound classes corroborates low-molecular
weight dominated n-alkane and n-alkylcyclohexane dis-
tributions and is consistent with a gas condensate com-
position of at least some of the analysed oil inclusions.
The low content of dibenzothiophene and alkyldibenzo-
thiophenes relative to alkylphenanthrenes (Table 2) is
consistent with a provenance from a low sulphur source
rock. In the C7 hydrocarbons of the Friendship-1 inclu-
sion oil, there is a strong preference for isoalkanes (3-RP),
with low alkylcyclopentanes (5-RP) and toluene + meth-
ylcyclohexane (6-RP). Based on the interpretative scheme
of ten Haven (1996), this is strong evidence against any
terrestrial component and may be indicative of a lacus-
trine depositional environment.
6.1. Biomarkers
Trace amounts of biomarkers were detected in the
Friendship-1 inclusion oil, but not in the system blank,
where they are either entirely absent or in much lower
abundances relative to the internal standard (Fig. 5(D)
948 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
and (E)). Bicyclic sesquiterpanes including two C14 iso-
mers, drimane, three rearranged C15 isomers and ho-
modrimane were detected. The lower molecular weight
C14 isomers are much more abundant than drimane (a
C15 isomer) and homodrimane (a C16 isomer; Table 1).
C23 tricyclic and C24 tetracyclic terpanes are much less
abundant than pentacyclic terpanes (Table 1), and other
tricyclic terpanes are below detection limit. Pentacyclic
terpanes present include Ts, Tm, C29 and C30 hopanes
and moretanes, C31 –C34 homohopanes, C30 diahopane
and gammacerane (Fig. 5(D)). C30 ab hopane is the
most abundant hopane detected. The presence of
gammacerane was confirmed by MRM. Furthermore,
C13 –C16 acyclic isoprenoids are of very low abundance,
and norpristane, pristane and phytane (C18 –C20 acyclic
isoprenoids) are virtually absent. The m=z 205 mass
chromatogram indicates the presence of C31 and C32 2a-
methylhopanes, giving a signal about half that of the
corresponding hopanes in this chromatogram. Trace
amounts of C27 –C29 steranes and diasteranes were de-
tected by SIM and MRM analysis.
6.2. Thermal maturity
Hopane/moretane ratios and homohopane 22S=
ð22S þ 22RÞ ratios are at or near equilibrium values
(Table 1) and the Ts/Tm ratio (1.4) is consistent with
an oil window maturity for the inclusion oil. C29 ster-
anes are more abundant than C27 and C28 steranes,
steranes are more abundant the diasteranes, and C29
sterane maturity parameters also support a mid oil
window maturity (Table 1).
Table 1
Biomarker parameters for the Friendship-1 inclusion oil
Parameter
Drimane/homodrimane
C14 bicyclic sesquiterpanes/(drimane + homodrimane)
C23 tricyclic terpane/C30 ab hopane
C24 tetracyclic terpane/C30 ab hopane
C24 tetracyclic terpane/(C24 tetracyclic terpane + C23 tricyclic terpane)
Ts/Tm{
C29 Ts/C29 ab hopane{
C30 */C30 ab hopane
C30 hopane ab=ðab þ baÞ
C31 ab 22S=ð22S þ 22RÞ{
Gammacerane/C30 ab hopane{
C29 ab hopane/C30 ab hopane
C31 ab hopane/C30 ab hopane
C27 :C28 :C29 abb steranes
C29 ba diasteranes/(aaa þ abb steranes){
C29 aaa 20S=ð20S þ 20R) steranes{
C29 abb=ðabb þ aaa) steranes{
For hopane abbreviations see Fig. 5. All ratios were calculated from SIM data (m=z 123, 191, 218), except for those marked { which
were calculated from MRM data.
Molecular distributions of the aromatic compounds
appear to be primarily controlled by thermal maturity.
In order to assess the level of thermal maturity of
the inclusion oil, aromatic ratios of the inclusion oil
(Table 2) can be compared to published values from
three different wells intersecting the middle Velkerri
Formation at different maturity stages (George and
Ahmed, 2002). In the inclusion oil, there is a marked
shift from high maturities based on lower molecular
weight parameters to lower maturities based on higher
molecular weight parameters. For example, the meth-
ylnaphthalene ratio (2.1; Fig. 5(F)) is similar to the
deeper sections of the middle Velkerri Formation in the
McManus-1 well, which reached the late oil window
(George and Ahmed, 2002). The dimethylnaphthalene
ratio-1 (5.0) is similar to the shallower sections of the
middle Velkerri Formation in McManus-1, and trim-
ethylnaphthalene ratios are similar to the deeper sections
of the middle Velkerri Formation in the Walton-2 well
(peak oil window). The methylphenanthrene index 1
(0.76; Fig. 5(E)) is similar to the middle Velkerri For-
mation in the Shea-1 well, which is in the peak oil
window (George and Ahmed, 2002), and a calibration
(Radke and Welte, 1983) of the methylphenanthrene
index 1 with vitrinite reflectance (0.86% Rc ) supports this
maturity level. Other maturity parameters such as those
based on alkylbiphenyls and alkyldibenzothiophenes
also mostly support a peak oil window maturity, except
for the dimethylphenanthrene ratio which is anoma-
lously low (Table 2). These aromatic maturity data re-
flect two different maturity fluids in this inclusion
sample, a low molecular weight dominated fluid (C11 )
Value
3.0
4.5
0.21
0.12
0.36
1.4
0.30
0.07
0.90
0.57
0.08
0.60
0.69
25:33:42
0.31
0.43
0.51
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957 949

Table 2
Aromatic compound parameters for the Friendship-1 inclusion oil
Parameter Value
Methylnaphthalene ratio (MNR: 2-MN/1-MN) 2.1
Ethylnaphthalene ratio (ENR: 2-EN/1-EN) 2.8
Dimethylnaphthalene ratio (DNR-1) 5.0
Trimethylnaphthalene ratio (TNR-1) 0.69
Trimethylnaphthalene ratio (TNR-2) 0.72
Tetramethylnaphthalene ratio-1 (TeMNr-1) 3.3
Trimethylnaphthalene ratio (TMNr) 0.78
Tetramethylnaphthalene ratio (TeMNr) 0.87
Pentamethylnaphthalene ratio (PMNr) 0.78
Methylphenanthrene index (MPI-1) 0.76
Calculated vitrinite reflectance (Rc ) 0.86
Methylphenanthrene distribution fraction (MPDF) 0.42
Methylphenanthrene ratio (MPR; 2-MP/1-MP) 0.97
Dimethylphenanthrene ratio (DPR) 0.10
Methylbiphenyl ratio (MBpR: [3-MBp/2-MBp]) 7.1
Dimethylbiphenyl ratio (DMBpR-x) 6.7
Dimethylbiphenyl ratio (DMBpR-y) 9.7
Phenanthrene/dibenzothiophene 13.1
Methyldibenzothiophene ratio (MDR: 4-MDBT/1-MDBT) 6.0
Dimethyldibenzothiophene ratio (DMDR) 1.16
DNR-1 ¼ [2,6- + 2,7-DMN]/1,5-DMN; TNR-1 ¼ 2,3,6-TMN/[1,4,6- + 1,3,5-TMN]; TNR-2 ¼ [2,3,6- + 1,3,7-TMN]/[1,4,6- + 1,3,5 +
1,3,6-TMN]; TeMNr-1 ¼ (2,3,6,7-TeMN/1,2,3,6-TeMN); TMNr ¼ 1,3,7-TMN/[1,3,7 + 1,2,5-TMN]; TeMNr ¼ 1,3,6,7-TeMN/[1,3,6,7 +
1,2,5,6-TeMN]; PMNr ¼ 1,2,4,6,7-PMN/[1,2,4,6,7 + 1,2,3,5,6-PMN]; MPI-1: 1.5  [3-MP + 2-MP]/[P + 9-MP + 1-MP]; Rc ¼ [0.6  MPI-
1 + 0.4] (Radke and Welte, 1983); MPDF ¼ [3-MP + 2-MP]/R MPs; DPR ¼ [3,5 + 2,6-DMP + 2,7-DMP]/[1,3 + 3,9 + 2,10 + 3,10-DMP +
1,6 + 2,9 + 2,5-DMP]; DMBpR-x ¼ 3,5-DMBp/2,5-DMBp; DMBpR-y ¼ 3,30 -DMBp/2,30 -DMBp; DMDR ¼ 4,6-DMDBT/[3,6 + 2,6-
DMDBT].

with a high maturity and a higher molecular weight
dominated fluid (C13þ ) with a lower maturity.
Low molecular weight hydrocarbons (C1 –C9 ) are
abundant in the Friendship-1 inclusion oil (Fig. 6). The
C5 –C9 range of these is dominated by n-alkanes, other
isomers that could be identified include methylalkanes,
dimethylalkanes, alkylcyclopentanes, alkylcyclohexanes
and aromatic hydrocarbons. Ratios based on some of
these compounds are given in Table 3. Benzene and
toluene are of very low abundance relative to n-alkanes
(Fig. 6(D), Table 3) and only traces of furan and
methylfurans could be identified. These data suggest no
significant contribution of water soluble compounds
dissolved in aqueous fluid inclusions to the low molec-
ular weight hydrocarbons of the inclusion oil, as is
sometimes found in samples dominated by aqueous in-
clusions (Ruble et al., 1998). Based on parameters H and
I (Table 3), the Friendship-1 inclusion oil has a very high
maturity, ‘‘supermature’’ according to Thompson
(1983). This interpretation is based not only on the
dominance of n-C7 over other C7 isomers (n-C7 repre-
sents nearly 50% of all C7 hydrocarbons; Table 3), but
also on the dominance of monomethylalkanes over
dimethylcyclopentanes (parameter I). The K1 parameter
is near unity (0.96), and the 2,4-/2,3-dimethylpentane
ratio is 0.89, which corresponds to a calculated oil
generation temperature (TC , Table 3) of 138 °C. This
value is higher than 95% of oils in the original calibra-
tion set (Bement et al., 1995) and is indicative of gen-
eration in the late oil window, hence consistent with
the maturity parameters of low weight aromatic
compounds.
7. Discussion
7.1. History of oil migration
The presence of an unusual suite of saturated ketone
isomers in the co-extract of solid bitumen and calcite-
hosted oil-bearing fluid inclusions (George and Jardine,
1994), but their absence in the inclusion oil studied here
suggests that the ketones were present either in the solid
bitumen or in oil-bearing fluid inclusions within the vein
minerals, but not in oil-bearing fluid inclusions trapped
in the feldspar, quartz, andesine and augite of the dol-
erite matrix. Although it is possible based on the geo-
chemical evidence that some of the ketone-containing oil
was trapped in calcite-hosted oil-bearing fluid inclu-
sions, petrographic and geochemical data suggest that
this is unlikely. The differences between the earlier geo-
chemical data and those of this study indicate at least
two phases of hydrocarbon migration during the ther-
mal history of the dolerite sill. A history with multiple
950 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957

Table 3
Low molecular weight hydrocarbon parameters for the Friendship-1 inclusion oil
Parameter Value
i-C5 /n-C5 1.2
Benzene/n-C6 0.03
Toluene/n-C7 0.03
(n-C6 +n-C7 )/(cyclohexane + MCH) 8.1
Heptane value (H) 49.5
Isoheptane value (I) 5.4
n-C7 /MCH 4.6
Cyclohexane/methylcyclopentane 0.73
n-C7 /2-MH 4.5
n-C7 /methylcyclopentane 6.2
3-Methylpentane/benzene 6.3
MCH/toluene 8.1
3-Methylpentane/n-C6 0.21
Benzene/toluene 2.1
Methylcyclopentane/MCH 0.73
K1 (2-MH + 2,3-DMP)/(3-MH + 2,4-DMP) 0.96
2-MH/3-MH 0.92
2,4-DMP/2,3-DMP 0.89
TC (°C) 138
K2 (3,3-DMP + 2,3-DMP + 2,4-DMP + 2,2-DMP)/(2-MH + 3-MH + 1,1-DMCP + c-1,3-DMCP + t-1,3-DMCP) 0.26
N2 /P3 (1,1-DMCP + c-1,3-DMCP + t-1,3-DMCP)/(3,3-DMP + 2,3-DMP + 2,4-DMP + 2,2-DMP) 0.77
% n-C7 of total C7 49.6
% 3RP (3,3-DMP + 2,3-DMP + 2,4-DMP + 2,2-DMP + 2-MH + 3-MH) 61.1
% 5RP (1,1-DMCP + c-1,3-DMCP + t-1,3-DMCP + t-1,2-DMCP + ECP) 14.6
% 6RP (MCH + toluene) 24.2
FI oil ratios derived from FID-equivalent data. MCH, methylcyclohexane; MH,P methylhexane; DMP, dimethylpentane; DMCP,
dimethylcyclopentane; ECP, ethylcyclopentane. Heptane value (H) ¼ 100  n-C7 / cyclohexane through to methylcyclohexane.
Isoheptane value (I) ¼ (2-MH + 3-MH)/(c-1,3) + t-1,3) + t-1,2-DMCP). TC ¼ 140 + [15  (ln {2,4-DMP/2,3-DMP})] (Bement et al.,
1995; Mango, 1997).

episodes of oil migration is supported by the petro-
graphic observations and microthermometric data.
The first and oldest phase of migration involved ke-
tone-rich pyrolytically-derived oil and most likely oc-
curred during or soon after flash maturation of the
overlying organic-rich Velkerri Formation ca. 1280 Ma
(McDougall et al., 1965) as the sequence was intruded
by the dolerite sill (George and Jardine, 1994). The oil
would have migrated along fractures and vesicles in the
cooling sill, where it would have experienced further
thermal degradation to form solid bitumen in fractures
and veins of the dolerite (George and Jardine, 1994).
High heating rates may have also increased expulsion
efficiency by producing higher pressures and subsequent
stress fracturing in the source rock (Y€
ukler and Wallace,
1990). Schutter (2003b) notes that oil may also migrate
into igneous rocks which attain lower vapour pressures
as they cool and that its movement may be further en-
hanced by igneous volatiles and hydrothermal fluids.
Textural relationships and TH measurements indi-
cate that the majority of oil inclusions were trapped
during events post-dating the fracture bitumen after
the dolerite had cooled substantially towards diage-
netic temperatures. The highest TH values are found in
primary aqueous fluid inclusions in growth bands of
the vein quartz and imply minimum temperatures of
trapping of about 130 °C. These temperatures are
significantly higher than temperatures at maximum
burial of the sequence and indicate that quartz pre-
cipitated as the dolerite sill was cooling. The absence
of primary oil-bearing fluid inclusions in the vein
quartz suggests that the initial phase of oil migration
ceased between the formation of the ketone-rich solid
bitumen and crystallisation of vein quartz, and was
relatively short-lived and short-ranged. Evidently fluid
conduits between the source rock and the dolerite sill
were closed during the post-intrusive cooling of the
host sequence and may have only been opened again
during the Neoproterozoic reactivation of the Roper
Superbasin.
Type 3 oil inclusions in albitised zones of matrix
feldspar were trapped during or after spilitic alteration
of the dolerite and albitisation of the feldspar. Albiti-
sation is a fairly common diagenetic and low-tempera-
ture hydrothermal process in sedimentary and igneous
rocks (Petersson and Eliasson, 1997; Ehrenberg and
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
Jakobsen, 2001), where it usually leads to enhanced
porosity and increased reservoir capacity (James, 1995).
Dissolution porosity, however, is controlled by the de-
gree of albitisation (Boles, 1982) such that only the
partially albitised plagioclases have intracrystalline po-
rosity (as is the case at Friendship-1) compared to
completely albitised plagioclases which lack porosity
altogether. The altered zones in the Friendship-1 dolerite
are not associated with obvious microfractures and can
be explained by the style of replacement similar to that
recorded by Hirt et al. (1993) along sub-microscopic en
echelon (0 0 1) and (1 1 0) cleavages. Empirical observa-
tions and modelling suggest that albitisation occurs at
temperatures between 100 and 150 °C (i.e., during dia-
genesis) (Boles, 1982; Baccar et al., 1993) and even as
low as 60 °C under low pCO2 conditions (Baccar et al.,
1993). The oil inclusions display a mean TH of 104  13
°C, so trapping temperatures were likely within the
range typically associated with albitisation. As the var-
iability of fluorescence colours is within inclusions of
one assemblage of inclusions of this type, it is attributed
to compositional changes due to partially poor sealing
of feldspars (Munz, 2001) rather than compositional
changes due to different source inputs or hydrocarbon
maturities (George et al., 2001).
Type 2 fluid inclusions trapped in transcrystalline
micro-fractures cutting the vein calcite, along with
some oil inclusions within feldspar alteration zones,
record the lowest TH values and texturally represent
the most recent fluid flow event in the dolerite sill
involving hydrocarbon fluids. Although these fractures
cut calcite crystal boundaries, they only rarely extend
from the vein calcite into dolerite matrix minerals, due
to high contrasts in physical properties between these
different mineral phases (Groshong, 1988). The TH
values of oil and coeval aqueous fluid inclusions show
similar distributions with means of 79  19 and 110 
16 °C, respectively. The TH of the aqueous inclusions
is taken as a good estimate of the entrapment tem-
peratures (Nedkvitne et al., 1993). Entrapment pres-
sures were most likely around 250 bars (Dutkiewicz
et al., 2003a). Entrapment of the oil was in the liquid
phase. The location, petrography and microthermo-
metric behaviour of these inclusions is strikingly sim-
ilar to those described for the underlying Bessie Creek
Sandstone (Dutkiewicz et al., 2003a; Volk et al., 2003)
and they are thus interpreted to be recording the same
migration event. In both cases the inclusions occur in
extensive sub-parallel transgranular or transcrystalline
microfractures, the oil inclusions display a similar size
and a uniform blue fluorescence colour and coeval
aqueous inclusions trap at least two populations of
hypersaline magnesium and/or calcium-rich brines,
which may have been accessed at similar times from
different pockets of fluids during formation of an ex-
tensive fracture network (e.g., McNutt et al., 1990).
951
Evidently, this phase of oil migration took place once
all the porosity was destroyed by vein-filling minerals
and the dolerite was fractured during the Neoprote-
rozoic reactivation event which also caused extensive
deformation in the underlying Bessie Creek Sandstone
(Dutkiewicz et al., 2003a; Volk et al., 2003). The
temperatures of entrapment inferred for these fracture
hosted oil inclusions and the inclusions in feldspar are
generally lower than those of aqueous fluid inclusions
within the vein quartz, suggesting that entrapment
temperatures decreased over time perhaps as a result
of the sill cooling and structural reactivation of the
Roper Superbasin in the Neoproterozoic (e.g., Powell
et al., 1987).
7.2. Source of the oil
The geochemical, petrographic and microthermo-
metric data from fluid inclusions in Friendship-1, in
combination with the earlier isotope data (George et al.,
1994), strongly support a biogenic origin for the oil and
exclude any abiotic processes that are apparent sources
of hydrocarbons in many non-sedimentary rocks (e.g.,
Potter and Konnerup-Madsen, 2003). The textural re-
lationships and fluid inclusion microthermometry indi-
cate that oil inclusion entrapment occurred at diagenetic
temperatures and significantly after cooling of the sill.
By far the strongest evidence for biogenic origins comes
from the presence of biomarkers (molecular fossils),
traces of which have been preserved in the fluid inclu-
sions for over one billion years.
The high abundance of n-alkanes, alkylcyclohexanes,
methylalkylcyclohexanes and monomethylalkanes, and
the low abundance of acyclic isoprenoids including
pristane and phytane in the Friendship-1 fluid inclusion
oil are typical of Proterozoic oils and sediments in gen-
eral (e.g., Fowler and Douglas, 1987; Summons et al.,
1988), and are similar to the Borrowdale-2 fluid inclu-
sion oil from the underlying Bessie Creek Sandstone
(Dutkiewicz et al., 2003a; Volk et al., 2003), as well as
hydrocarbon extracts from associated solid bitumens
(George et al., 1994) and source rocks, including the
overlying Velkerri Formation (e.g., Summons et al.,
1988). The overall C13þ geochemistry of the oil is similar
to hydrocarbon extracts from the overlying Velkerri
Formation shale. Biomarkers in the Friendship-1 fluid
inclusion oil are dominated by hopanes, derived mainly
from the membrane lipids of prokaryotes (Ourisson
et al., 1987). The high content of monomethylalkanes
likely indicates a cyanobacterial lipid input (Summons
et al., 1988), but these are somewhat lower in abundance
relative to n-alkanes than in either Borrowdale-2 fluid
inclusions (Dutkiewicz et al., 2003a; Volk et al., 2003)
or in bitumen and source rock extracts from the
Roper Superbasin (Summons et al., 1988). This likely
reflects the high thermal maturity of the dolerite-hosted
952 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
inclusion oil. Another marker for cyanobacterial input is
the presence of 2a-methylhopanes, which have been re-
lated to cyanobacterial oxygenic photosynthesis (Sum-
mons et al., 1999). The small amount of gammacerane
that is present is indicative of a source rock deposited
under highly reducing conditions within a stratified water
column (Sinninghe Damst
e et al., 1995). Unlike the
Borrowdale-2 fluid inclusion oil from the underlying
Bessie Creek Sandstone, very small amounts of steranes
and diasteranes are present in the Friendship-1 fluid in-
clusion oil. These are dominated by C29 steranes, with
low relative amounts of C27 steranes and diasteranes
most likely derived from eukaryotes. Although high C29 /
C27 sterane ratios are generally associated with a terres-
trial contribution of organic matter to Upper Palaeozoic
and younger source rocks (Huang and Meinschein,
1979), high ratios have also been found in early Palaeo-
zoic and Precambrian rocks deposited prior to the evo-
lution of land plants (Grantham, 1986; Wang and Philp,
1997; H€ old et al., 1999; Arouri et al., 2000). In addition,
C27 –C29 steranes have been found in a wide range of
Proterozoic and Archaean rocks (Summons and Walter,
1990; Brocks et al., 2003, 1999), including the Barney
Creek, Velkerri and McMinn formations from the
McArthur Basin (Summons et al., 1988; Summons and
Walter, 1990), which show variations in the relative
abundance of C29 isomers. In Precambrian rocks, ster-
anes have been interpreted to be derived from sterols of
eukaryote cell membranes (Summons and Walter, 1990)
although the exact phylogenetic position of these eu-
karyotes remains unknown (e.g., Brocks et al., 2003), as
does the cause of relative abundances of steranes in
Proterozoic and Archaean rocks. Significantly, the Vel-
kerri Formation is known to contain abundant acrit-
archs, including the distinctive protist Tappania (Javaux
et al., 2001). Overall composition and maturity param-
eters derived from the molecular composition of the
Friendship-1 inclusion oil are indicative of analysis of a
mixture. Low molecular weight (C11 ) parameters such
as the gasoline range hydrocarbons (H, I, TC ) and the
methylnaphthalene ratio indicate a high maturity,
probably in the late oil generation window (about 1.3%
vitrinite reflectance equivalent [VRE]). In contrast,
higher molecular weight parameters (C13þ ) including
most biomarker, trimethylnaphthalene, alkylphenanth-
rene, alkylbiphenyl and alkyldibenzothiophene ratios
indicate a lower maturity, in the peak oil generation
window (
0.8% VRE). The very strong dominance of
C5 –C13 n-alkanes in the Friendship-1 inclusion oil is
typical of a condensate composition, and this is also in-
dicated by the much higher abundance of alkylbenzenes
(C8 –C10 ) compared to other aromatic hydrocarbons.
Higher molecular weight hydrocarbons are certainly
present in the inclusion oil, but in significantly lesser
abundance. There are three plausible explanations for
this interpreted mixture. First, separate condensate or
high maturity light oil was trapped in some inclusions,
and a different and probably earlier charge of oil gener-
ated in the peak oil window was trapped in other inclu-
sions. Second, condensate or high maturity light oil
picked up a tail of lower maturity oil during migration,
and this mixture was trapped in inclusions. Third, an
earlier oil charge was flushed by a later condensate or
high maturity light oil with the oil-condensate mixture
trapped in inclusions (Aplin et al., 2000). Based on geo-
chemistry alone, it is not possible to distinguish these
three possibilities. Microthermometric experiments,
however, on 220 fluid inclusions failed to identify phase
changes consistent with the presence of a discrete gas-
condensate phase within individual fluid inclusions
(Munz et al., 2002; Teinturier et al., 2002; Grimmer et al.,
2003). Therefore, fluid inclusion oil in the dolerite at
Friendship-1 is interpreted to contain a mixture of gas-
condensate and peak-oil window mature oil.
The composition of these phases, including the bio-
marker content of the inclusion oils, indicates that the
fluids have likely been expelled from Precambrian source
rocks. There is no evidence for contamination of this
fluid inclusion oil by Phanerozoic-derived hydrocar-
bons. The exceptionally organic rich marine Velkerri
Formation (Warren et al., 1998) reached oil window
maturities in more deeply buried sections of the Roper
Superbasin in the Middle Proterozoic (George and Ah-
med, 2002) and also supplied oil to the underlying Bessie
Creek Sandstone (Dutkiewicz et al., 2003a). Less mature
Velkerri Formation sediments contain steranes and di-
asteranes with a similar distribution as the inclusion oil
(Summons et al., 1988), although these could not be
detected in more mature Velkerri Formation sediments.
Alternative source rocks, including the McMinn and
Barney Creek Formation sediments, contain more C27
steranes than C29 steranes, and have a high relative
abundance of diasteranes (Summons et al., 1988). These
specific biomarker comparisons, together with organic
richness and proximity to the dolerite sill of the Velkerri
Formation, suggest that this is the most likely source of
the Friendship-1 fluid inclusion oil. However, it is diffi-
cult to assess if and to what extent, alternative and more
mature organic-rich formations in the Roper Superbasin
with a similar source character to the Velkerri Forma-
tion, such as the Palaeoproterozoic Barney Creek
Formation (Summons et al., 1988) contributed to the
gas-condensate range proportion of the fluid inclusion
oils. One line of evidence is the C7 hydrocarbon ring
preference, dominated by isoalkanes (3-RP), which in-
dicates a lacustrine depositional environment, based on
the interpretative scheme of ten Haven (1996). As the
Barney Creek Formation was deposited in a lacustrine
or lagoonal setting 1690 Ma and has total organic car-
bon (TOC) contents of up to 10% (Summons et al.,
1988), this could well be the source of the gas-conden-
sate. Based on Rock-Eval pyrolysis, the maturity of the
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
Barney Creek Formation ranges from marginally ma-
ture to overmature (Summons et al., 1988), and thus
may have expelled gas or gas-condensates. Interestingly,
there is no evidence of lacustrine sourcing in the higher
molecular weight portion of the Friendship-1 inclusion
oil, which is consistent with only expulsion of
C13
hydrocarbons.
An alternative explanation is that the gas-conden-
sate, together with the ketone-rich fraction and the high
maturity oil was derived from the Velkerri Formation. If
this were the case, then the C7 hydrocarbon source data
would have to be assumed to be misleading. The low-
ermost section of the Velkerri Formation closest to the
dolerite intrusion would have experienced the greatest
thermal effect resulting in formation of ketones, which
were preserved as solid bitumen within the dolerite sill.
However, the effects of thermal stress decrease rapidly
with distance from the intrusion, and the zone of alter-
ation on either side of an intrusion is usually twice the
thickness of the intrusive body (Saxby and Stephenson,
1987; Raymond and Murchison, 1991). Consequently,
the composition and maturity of hydrocarbons gener-
ated by pyrolysis induced by igneous intrusions will vary
with distance from the heat source and thus mimic
metagenesis and catagenesis stages of burial-driven
petroleum generation. It is possible, therefore, that the
gas-condensate was generated in parts of the Velkerri
Formation that were not hot enough to form pyrolysis
products but were hotter than sections that experienced
a temperature regime driven by burial-induced heating
alone. Migration of both oil generated by burial heating,
and from sill-influenced sections of the Velkerri For-
mation would have occurred during or following the
Neoproterozoic reactivation of the Roper Superbasin,
whereas true pyrolysis products were limited to an early
oil charge transformed to solid bitumen by thermal py-
rolytic alteration of a Velkerri-derived oil. This ther-
mally solidified oil would be restricted to the hot dolerite
sill, although pyrolysed oils have the potential to be
preserved in fluid inclusions (Volk et al., 2002). Absence
of gas-condensate in the Bessie Creek Sandstone fluid
inclusions may be due to migration being fairly short-
range and controlled by permeability differences be-
tween the dolerite and the underlying sandstone and the
total volume of migrating hydrocarbon. Future work
analysing hydrocarbon extract from different levels
within the Velkerri Formation should help to discern the
exact source of the hydrocarbons.
7.3. Implications for the source of hydrocarbons in
crystalline rocks
A list of hydrocarbon occurrences in and associated
with igneous rocks recently compiled by Schutter
(2003a) clearly illustrates that these are quite common,
yet overlooked settings for petroleum which occasionally
953
occur in commercially viable accumulations (Koning,
2003; Schutter, 2003a). Reservoir rocks may be basalts,
andesites, rhyolites, syenites, granites, gneisses and mica-
schists and even kimberlites (Schutter, 2003a), with pe-
troleum products ranging from oil (light and heavy) and
gas to bitumen. However, as Schutter (2003b) points out,
igneous rocks and source rocks are rarely considered
together in a petroleum system context. As these oc-
currences form one of the last frontiers for petroleum
exploration, it is crucial to understand the source of
hydrocarbons, their migration paths and their emplace-
ment conditions. In order to address some of these issues
we recommend, a fluid inclusion approach especially in
rocks where the fluids are no longer present in the pore
spaces but residues of solid bitumen or graphite remain.
The molecular composition of fluid inclusions should
also be used, especially where carbon isotope data are
equivocal or where the evidence for abiogenic hydro-
carbons is largely circumstantial. Although compound-
specific isotope studies may distinguish between biogenic
and abiogenic sources of hydrocarbons (Sherwood Lol-
lar et al., 2002), molecular geochemistry of petroliferous
fluids can provide additional information not only on
the detailed composition of the trapped hydrocarbons
but also on their maturity, their origin and the compo-
sition of the biomass from which the petroleum was
derived. Petrography and microthermometry of fluid
inclusions can provide information on the timing of
entrapment of fluids, the temperature and pressure
conditions of trapping and information on any coeval
gases and liquids. A better understanding of petroleum
occurrences in non-sedimentary rocks may lead to more
accurate predictions where they occur, insights into the
diversity of the primordial biosphere and the nature of
life in hot environments.
8. Summary and conclusions
1. A Mesoproterozoic dolerite sill had a complex fluid
migration history, with trapping of several phases
of hydrocarbon migration, both during the actual in-
trusive episode (ca. 1.3 Ma) and also during the sub-
sequent cooling of the sill.
2. Solid bitumens represent the oldest hydrocarbon mi-
gration event and preserve an unusual suite of ketone
isomers generated during flash maturation of the
overlying Velkerri Formation source rock (George
and Jardine, 1994).
3. Hydrocarbons within oil inclusions trapped in doler-
ite matrix minerals and vein minerals represent a later
episode of hydrocarbon migration, probably at dia-
genetic conditions.
4. Oil inclusions occur in clusters in albitised zones of
labradorite crystals and in transcrystalline fractures
cutting vein calcite and rarely vein quartz.
954 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
5. The oil in the fluid inclusions was trapped in the liquid
phase at around 110 °C and 250 bars, most likely dur-
ing the Neoproterozoic reactivation and uplift stage of
the Roper Superbasin and involved a mixture of gas-
condensate and a mature oil and was, at least partly,
accompanied by hypersaline Ca/Mg brines.
6. GC–MS analysis shows that the inclusion oil is non-
biodegraded and has a composition similar to other
Proterozoic oils and sedimentary organic matter.
There is geochemical evidence for the presence of a
very mature, light condensate fluid and a peak oil-
window maturity oil. Petrographic evidence does
not suggest a trapping of these fluids in discrete fluid
inclusion assemblages and mixing of the hydrocarbon
phases predated trapping.
7. Biomarkers (mainly hopanes, monomethylalkanes,
alkylcyclohexanes and traces of steranes) point to a
source rock dominated by prokaryotic cyanobacterial
organic matter with a small contribution from eu-
karyotes. This rules out an abiotic origin for the in-
clusion oil.
8. The most likely source rocks include the directly
overlying Velkerri Formation and the deeper ca. 1.6
Ga Barney Creek Formation from the underlying
McArthur Group, which may have contributed the
higher maturity gas-condensate.
9. Oil inclusions provide pristine data on the composi-
tion of the Earth’s early biosphere and can lead to
a better understanding of poorly-understood petro-
leum systems associated with crystalline rocks.
Acknowledgements
We thank the Northern Territory Geological Survey
for access to samples and reports; Robinson Quezada
for help with gas chromatography-mass spectrometry
analysis; Tom Bradley for thin section preparation; the
Electron Microscopy Unit at Sydney University for as-
sistance with SEM analysis. We are grateful to Robert
C. Burruss and Colin Barker for their careful and con-
structive reviews of this paper. This research was sup-
ported by an Australian Research Council fellowship
and grant to A. Dutkiewicz.
Associate Editor – Rolando di Primio
References
Abrajano, T.A., Sturchio, N.C., Bohlke, J.K., Lyon, G.L.,
Poreda, R.J., Stevens, C.M., 1988. Methane–hydrogen gas
seeps, Zambales Ophiolite, Philippines: deep or shallow
origin? Chemical Geology 71, 211–222.
Aplin, A.C., Larter, S.R., Bigge, M.A., Macleod, G., Swar-
brick, R.E., Grunberger, D., 2000. Confocal microscopy of
fluid inclusions reveals fluid-pressure histories of sediments
and an unexpected origin of gas condensate. Geology 28,
1047–1050.
Arouri, K., Conaghan, P.J., Walter, M.R., Bischoff, G.C.O.,
Grey, K., 2000. Reconnaissance sedimentology and hydro-
carbon biomarkers of Ediacarian microbial mats and
acritarchs, lower Ungoolya Group, Officer Basin. Precam-
brian Research 100, 235–280.
Baccar, M.B., Fritz, B., Mad
e, B., 1993. Diagenetic albitization
of K-feldspar and plagioclase in sandstone reservoirs:
thermodynamic and kinetic modeling. Journal of Sedimen-
tary Petrology 63, 1100–1109.
Bement, W.O., Levey, R.A., Mango, F.D., 1995. The temper-
ature of oil generation as defined with C7 chemistry
maturity parameter (2,4-DMP/2,3-DMP ratio). In: Grimalt,
J.O., Dorronsoro, C. (Eds.), Organic Geochemistry: Devel-
opments and Applications to Energy, Climate, Environment
and Human History. A.I.G.O.A. Donostia-San Sebastian,
pp. 505–507.
Boles, J.R., 1982. Active albitization of plagioclase, Gulf Coast
Tertiary. American Journal of Science 282, 165–180.
Brocks, J.J., Buick, R., Summons, R.E., Logan, G.A., 2003. A
reconstruction of Archean diversity based on molecular
fossils from the 2.78 to 2.45 billion-year-old Mount Bruce
Supergroup, Hamersley Basin, Western Australia. Geochi-
mica et Cosmochimica Acta 67, 4321–4335.
Brocks, J.J., Logan, G.A., Buick, R., Summons, R.E., 1999.
Archean molecular fossils and the early rise of eukaryotes.
Science 285, 1033–1036.
Dalziel, W.D., 1992. On the organization of American plates in
the Neoproterozoic and the breakout of Laurentia. Geology
Today 2, 237–241.
Dutkiewicz, A., Rasmussen, B., Buick, R., 1998. Oil preserved
in fluid inclusions in Archaean sandstones. Nature 395, 885–
888.
Dutkiewicz, A., Volk, H., Ridley, J., George, S., 2003a.
Biomarkers, brines, and oil in the Mesoproterozoic, Roper
Superbasin, Australia. Geology 31, 981–984.
Dutkiewicz, A., Ridley, J., Buick, R., 2003b. Oil-bearing CO2 –
CH4 –H2 O fluid inclusions: oil survival since the Palaeopro-
terozoic after high temperature entrapment. Chemical
Geology 194, 51–79.
Ehrenberg, S.N., Jakobsen, K.G., 2001. Plagioclase dissolution
related to biodegradation of oil in Brent Group sandstones
(Middle Jurassic) of Gullfaks Field, northern North Sea.
Sedimentology 48, 703–721.
Ettner, D.C., Lindblom, S., Karlsen, D., 1996. Identification
and implications of light hydrocarbon fluid inclusions from
the Proterozoic Bidjovagge gold-copper deposit, Finnmark,
Norway. Applied Geochemistry 11, 745–755.
Fassifihri, O., Robin, M., Rosenberg, E., 1992. Wettability of
reservoir rock at the pore scale-contribution of cryoscan-
ning electron-microscopy. Revue de l’Institut Francais du
Petrole 47, 685–701.
Fowler, M.G., Douglas, A.G., 1987. Saturated hydrocarbon
biomarkers in oils of late Precambrian age from Eastern
Siberia. Organic Geochemistry 11, 201–213.
George, S.C., Ahmed, M., 2002. Use of aromatic compound
distributions to evaluate organic maturity of the Proterozoic
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
middle Velkerri Formation, McArthur Basin, Australia. In:
Keep, M., Moss, S.J. (Eds.), Proceedings of the Petroleum
Exploration Society of Australia Symposium, The Sedimen-
tary Basins of Western Australia 3, pp. 253–270.
George, S.C., Jardine, D.R., 1994. Ketones in a Proterozoic sill.
Organic Geochemistry 21, 829–839.
George, S.C., Lisk, M., Eadington, P.J., Quezada, R.A., 1998.
Geochemistry of a palaeo-oil column: Octavius 2, Vulcan
Sub-basin. In: Purcell, P.G., Purcell, R.R. (Eds.), Proceed-
ings of Petroleum Exploration Society of Australia Sympo-
sium, The Sedimentary Basins of Western Australia 2, pp.
195–210.
George, S.C., Llorca, S.M., Hamilton, P.J., 1994. An integrated
analytical approach for determining the origin of solid
bitumens in the McArthur Basin, northern Australia.
Organic Geochemistry 21, 235–248.
George, S.C., Ruble, T.E., Dutkiewicz, A., Eadington, P.J.,
2001. Assessing the maturity of oil trapped in fluid
inclusions using molecular geochemistry data and visually-
determined fluorescence colours. Applied Geochemistry 16,
451–473.
Gold, T., 2001. The Deep Hot Biosphere: the Myth of Fossils
Fuels. Copernicus Books, Heidelberg, Germany. 243 pp.
Goldstein, R.H., Reynolds, T.J., 1994. Systematics of Fluid
Inclusions in Diagenetic Minerals. SEMP Short Course 31.
Society for Sedimentary Geology, Tulsa, Oklahoma, USA,
pp. 199.
Grantham, P.J., 1986. The occurrence of unusual C27 and C29
sterane predominance in the two types of Oman crude oil.
Organic Geochemistry 9, 1–10.
Grimmer, J.O.W., Pironon, J., Teinturier, S., Mutterer, J.,
2003. Recognition and differentiation of gas condensates
and other oil types using microthermometry of petroleum
inclusions. Journal of Geochemical Exploration 78–79, 367–
371.
Groshong, R.H., 1988. Low-temperature deformation mecha-
nisms and their interpretation. Geological Society of
America Bulletin 100, 1329–1360.
Haines, P.W., Rawlings, D.J., Sweet, I.P., Pietsch, B.A., Plumb,
K., Madigan, T.L., Krassay, A.A., 1999. Blue Mud Bay-
1:250 000 Geological Map Series. Explanatory Notes, SD
53-7. Australian Geological Survey Organisation and
Northern Territory Geological Survey, Darwin.
Hirt, W.G., Wenk, H.-R., Boles, J.R., 1993. Albitization of
plagioclase crystals in the Stevens sandstone (Miocene), San
Joaquin Basin, California, and the Frio Formation (Oligo-
cene), Gulf Coast, Texas: a TEM/AEM study. Geological
Society of America Bulletin 105, 708–714.
Hoffmann, C.F., Foster, C.B., Powell, T.G., Summons, R.E.,
1987. Hydrocarbon biomarkers from Ordovician sediments
and fossil cells of the alga Gloeocapsomorpha prisca Zalessky
1917. Geochimica et Cosmochimica Acta 51, 2681–2697.
H€
old, I.M., Schouten, S., Jellema, J., Sinninghe Damst
e, J.S.,
1999. Origin of free and bound mid-chain methyl alkanes in
oils, bitumens and kerogens of the marine, Infracambrian
Huqf Formation (Oman). Organic Geochemistry 30, 1411–
1428.
Huang, W.Y., Meinschein, W.G., 1979. Sterols as ecological
indicators. Geochimica Cosmochimica Acta 43, 739–745.
Hunt, J.M., 1996. Petroleum Geochemistry and Geology. W.H.
Freeman, New York. 743 pp.
955
Jackson, M.J., Powell, T.G., Summons, R.E., Sweet, I.P., 1986.
Hydrocarbon shows and petroleum source rocks in sedi-
ments as old as 1.7  109 years. Nature 322, 727–729.
Jackson, M.J., Raiswell, R., 1991. Sedimentology and carbon-
sulphur geochemistry of the Velkerri Formation, a mid-
Proterozoic potential oil source in northern Australia.
Precambrian Research 54, 81–108.
Jackson, M.J., Southgate, P.N., Page, R.W., 2000. Gamma-ray
logs and U-Pb zircon geochronology – essential tools to
constrain lithofacies interpretation of Palaeoproterozoic
depositional systems. In: Grotzinger, J.P., James, N.P.
(Eds.), Carbonate Sedimentation and Diagenesis in the
Evolving Precambrian World. SEMP Special Publication
67, pp. 23–41.
Jackson, M.J., Sweet, I.P., Page, R.W., Bradshaw, B.E., 1999.
The South Nicholson and Roper Groups: evidence for the
early Mesoproterozoic Roper Superbasin. In: Bradshaw,
B.E., Scott, D.L. (Eds.), Integrated Basin Analysis of the Isa
Superbasin using Seismic, Well-log and Geopotential Data:
an Evaluation of the Economic Potential of the Northern
Lawn Hill Platform. AGSO Record 1999/19, Canberra.
Jackson, M.J., Sweet, I.P., Powell, T.G., 1988. Studies on
petroleum geology and geochemistry, Middle Proterozoic,
McArthur Basin Northern Australia I: petroleum potential.
Australian Petroleum Exploration Association Journal 28,
283–302.
James, R.A., 1995. Application of petrographic image analysis
to the characterization of fluid-flow pathways in a highly-
cemented reservoir: Kane Field, Pennsylvania, USA. Jour-
nal of Petroleum Science Engineering 13, 141–154.
Javaux, E.J., Knoll, A.H., Walter, M.R., 2001. Morphological
and ecological complexity in early eukaryotic ecosystems.
Nature 412, 66–69.
Jeffrey, A.W.A., Kaplan, I.R., 1988. Hydrocarbons and inor-
ganic gases in the Gravberg-1 well, Siljan Ring, Sweden.
Chemical Geology 71, 237–255.
Jensenius, J., Burruss, R.C., 1990. Hydrocarbon–water inter-
actions during brine migration: evidence from hydrocarbon
inclusions in calcite cements from Danish North Sea oil
fields. Geochimica et Cosmochimica Acta 54, 705–713.
Kogarko, L.N., Kosztolanyi, C., Ryabchikov, I.D., 1987.
Geochemistry of the reduced fluid in alkali magmas.
Geochemistry International 24, 20–27.
Koning, T., 2003. Oil and gas production from basement
reservoirs: examples from Indonesia, USA and Venezuela.
In: Petford, N., McCaffrey, K.J.W. (Eds.), Hydrocarbons in
Crystalline Rocks. Geological Society Special Publication
214, pp. 83–107.
Konnerup-Madsen, J., Larsen, E., Rose-Hansen, J., 1979.
Hydrocarbon-rich fluid inclusions in minerals from the
alkaline Ilimaussaq intrusion, South Greenland. Bulletin de
Mineralogie 102, 642–653.
Kralik, M., 1982. Rb-Sr age determinations on Precambrian
carbonate rocks of the Carpentarian McArthur Basin,
Northern Territory, Australia. Precambrian Research 18,
157–170.
Ledlie, I.M., Torkington, J., 1988. Friendship-1, EP 5, McAr-
thur Basin. Northern Territory Well Completion Report.
CRAE Report No. 303624, Pacific Oil & Gas Pty. Ltd.
Ledlie, I.M., Weste, G., Torkington, J., 1988. Borrowdale-1
and 2, EP 5, McArthur Basin, Northern Territory. Well
956 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
Completion Report. CRAE Report No. 303625, Pacific Oil
& Gas Pty. Ltd.
Lewan, M.D., 1986. Stable carbon isotopes of amorphous
kerogens from phanerozoic sedimentary rocks. Geochimica
et Cosmochimica Acta 50, 1583–1591.
Mango, F.D., 1997. The light hydrocarbons in petroleum – a
critical review. Organic Geochemistry 26, 417–440.
Mauk, J.L., Burruss, R.C., 2002. Water washing of proterozoic
oil in the midcontinent rift system. American Association of
Petroleum Geologists Bulletin 86, 1113–1127.
McDougall, I., Dunn, P.R., Compston, W., Webb, A.W.,
Richards, J.R., Bofinger, V.M., 1965. Isotopic age determi-
nations on precambrian rocks of the carpentaria region,
northern territory, Australia. Geological Society of Austra-
lia Journal 12, 67–90.
McNutt, R.H., Frape, S.K., Fritz, P., Jones, M.G., MacDon-
ald, I.M., 1990. The 87 Sr/86 Sr values of Canadian shield
brines and fracture minerals with applications to ground-
water mixing, fracture history and geochronology. Geochi-
mica et Cosmochimica Acta 54, 205–215.
Mossman, D.J., Gauthier-Lafaye, F., Jackson, S., 2001. Car-
bonaceous substances associated with the paleoproterozoic
natural fission reactors of Oklo, Gabon: paragenesis,
thermal maturation and carbon isotopic and trace element
compositions. Precambrian Research 106, 135–148.
Munz, I.A., 2001. Petroleum inclusions in sedimentary basins:
systematics, analytical methods and applications. Lithos 55,
195–212.
Munz, I.A., Yardley, B.W.D., Gleeson, S.A., 2002. Petroleum
infiltration of high-grade basement, South Norway: pres-
sure–temperature–time–composition (P–T–t–X) constraints.
Geofluids 2, 41–53.
Nedkvitne, T., Karlsen, D.A., Bjørlykke, K., Larter, S., 1993.
Relationship between reservoir diagenetic evolution and
petroleum emplacement in the Ula field, North Sea. Marine
and Petroleum Geology 10, 255–270.
Newell, K.D., Burruss, R.C., Palacas, J.G., 1993. Thermal
maturation and organic richness of potential petroleum
source rocks in Proterozoic Rice Formation, North Amer-
ican Mid-continent rift system, Northeastern Kansas.
American Association of Petroleum Geologists Bulletin
77, 1922–1941.
Oakes, C.S., Bodnar, R.J., Simonson, J.M., 1990. The system
NaCl-CaCl2 -H2 O: I. The ice liquidus at 1 atm total pressure.
Geochimica et Cosmochimica Acta 54, 603–610.
Ourisson, G., Rohmer, M., Poralla, K., 1987. Prokaryotic
hopanoids and other polyterpenoid sterol surrogates. An-
nual Review of Microbiology 41, 301–333.
Page, R.W., Sweet, I.P., 1998. Geochronology of basin phases
in the western Mount Isa Inlier, and correlation with the
McArthur Basin. Australian Journal of Earth Sciences 45,
219–232.
Parnell, J., 1988. Migration of biogenic hydrocarbons into
granites: a review of hydrocarbons in British plutons.
Marine and Petroleum Geology 5, 385–396.
Petersson, J., Eliasson, T., 1997. Mineral evolution and element
mobility during episyenitization (dequartzification) and
albitization in the postkinematic Bohus granite, southwest
Sweden. Lithos 42, 123–146.
Pietsch, B.A., Rawlings, D.J., Creaser, P.M., Kruse, P.D.,
Ahmad, M., Ferenczi, P.A., Findhammer, T.L.R., 1991.
Bauhinia Downs SE53-3. Northern Territory Geological
Survey, Darwin.
Potter, J., Konnerup-Madsen, J., 2003. A review of the
occurrence and origin of abiogenic hydrocarbons in igneous
rocks. In: Petford, N., McCaffrey, K.J.W. (Eds.), Hydro-
carbons in Crystalline Rocks. Geological Society Special
Publication 214, pp. 151–173.
Potter, J., Rankin, A.H., Treloar, P.J., Nivin, V.A., Ting, W.,
Ni, P., 1998. The preliminary study of methane inclusions in
alkaline igneous rocks of the Kola igneous province, Russia:
implications for the origin of methane in igneous rocks.
European Journal of Mineralogy 10, 1167–1180.
Powell, T.G., Jackson, M.J., Sweet, I.P., Crick, I.H., Boreham,
C.J., Summons, R.E., 1987. Petroleum Geology and Geo-
chemistry, Middle Proterozoic McArthur Basin. Bureau of
Mineral Resources. Report Number 1987/48.
Radke, M., Welte, D.H., 1983. The methylphenanthrene index
(MPI); a maturity parameter based on aromatic hydrocar-
bons. In: Bjorøy, M. et al. (Eds.), Advances in Organic
Geochemistry 1981. Wiley, Chichester, pp. 504–512.
Rawlings, D.J., 1999. Stratigraphic resolution of a multiphase
intracratonic basin system: the McArthur Basin, northern
Australia. Australian Journal of Earth Sciences 46, 703–723.
Raymond, A.C., Murchison, D.G., 1991. The relationship
between organic maturation, the widths of thermal aureoles
and the thickness of sills in the Midland Valley of Scotland
and Northern England. Journal of the Geological Society of
London 148, 215–218.
Ruble, T.E., George, S.C., Lisk, M., Quezada, R.A., 1998.
Organic compounds trapped in aqueous fluid inclusions.
Organic Geochemistry 29, 195–205.
Salvi, S., Williams-Jones, A.E., 1997. Fischer–Tropsch synthe-
sis of hydrocarbons during sub-solidus alteration of the
Strange Lake peralkaline granite, Quebec/Labrador, Can-
ada. Geochimica et Cosmochimica Acta 61, 83–99.
Saxby, J.D., Stephenson, L.C., 1987. Effect of an igneous
intrusion on oil shale at Rundle (Australia). Chemical
Geology 63, 1–16.
Schutter, S.R., 2003a. Occurrences of hydrocarbons in and
around igneous rocks. In: Petford, N., McCaffrey, K.J.W.
(Eds.), Hydrocarbons in Crystalline Rocks. Geological
Society Special Publication 214, pp. 35–68.
Schutter, S.R., 2003b. Hydrocarbon occurrence and explora-
tion in and around igneous rocks. In: Petford, N., McCaf-
frey, K.J.W. (Eds.), Hydrocarbons in Crystalline Rocks.
Geological Society Special Publication 214, pp. 7–33.
Sherwood Lollar, B., Westgate, T.D., Ward, J.A., Slater, G.F.,
Lacrampe-Couloume, G., 2002. Abiogenic formation of
alkanes in the Earth’s crust as a minor source of global
hydrocarbon reservoirs. Nature 416, 522–524.
Sinninghe Damst
e, J.S., Kenig, F., Koopmans, M.P., K€ oster,
J., Schouten, S., Hates, J.M., de Leeuw, J.W., 1995.
Evidence for gammacerane as an indicator of water column
stratification. Geochimica et Cosmochimica Acta 59, 1895–
1900.
Summons, R.E., Jahnke, L.L., Hope, J.M., Logan, G.A., 1999.
2-Methylhopanoids as biomarkers for cyanobacterial oxy-
genic photosynthesis. Nature 400, 554–557.
Summons, R.E., Powell, T.G., Boreham, C.J., 1988. Petroleum
geology and geochemistry of the Middle Proterozoic
McArthur Basin, Northern Australia: III. Composition of
 A. Dutkiewicz et al. / Organic Geochemistry 35 (2004) 937–957
extractable hydrocarbons. Geochimica et Cosmochimica
Acta 52, 1747–1763.
Summons, R.E., Walter, M.R., 1990. Molecular fossils and
microfossils of prokaryotes and protists from proterozoic
sediments. American Journal of Science 290-A, 212–244.
Sweet, I.P., Brakel, A.T., Rawlings, D.J., Haines, P.W., Plumb,
K.A., Wygralak, A.S., 1999. Mount Marumba, Northern
Territory-1:250 000 Geological Map Series. Explanatory
Notes, SD 53-6. Australian Geological Survey Organisation
and Northern Territory Geological Survey, Darwin.
Szatmari, P., 1989. Petroleum formation by Fischer–Tropsch
synthesis in plate tectonics. American Association of
Petroleum Geologists Bulletin 73, 989–998.
Teinturier, S., Pironon, J., Walgenwitz, F., 2002. Fluid inclu-
sions and PVTX modelling: examples from the garn
formation in well 6507/2-2, Haltenbanken, Mid-Norway.
Marine and Petroleum Geology 19, 755–765.
ten Haven, H.L., 1996. Applications and limitations of
Mango’s light hydrocarbon parameters in petroleum corre-
lation studies. Organic Geochemistry 24, 957–976.
Thompson, K.F.M., 1983. Classification and thermal history of
petroleum based on light hydrocarbons. Geochimica et
Cosmochimica Acta 47, 303–316.
Tseng, H.-Y., Burruss, R.C., Onstott, T.C., Omar, G., 1999.
Palaeofluid-flow circulation within a Triassic rift basin:
evidence from oil inclusions and thermal histories. Geolog-
ical Society of America Bulletin 111, 275–290.
Volk, H., Dutkiewicz, A., George, S., Ridley, J., 2003. Oil
migration in the Middle Proterozoic Roper Superbasin,
957
Australia: evidence from oil inclusions and their geochem-
istries. Journal of Geochemical Exploration 78–79, 437–441.
Volk, H., Horsfield, B., Mann, U., Such
y, V., 2002. Variability of
petroleum inclusions in vein, fossil and vug cements:
geochemical study in the Barrandian Basin (Lower Palaeo-
zoic, Czech Republic). Organic Geochemistry 33, 1319–1341.
Volk, H., Mann, U., Burde, O., Horsfield, B., Such
y, V., 2000.
Petroleum inclusions and residual oils: constraints for
deciphering petroleum migration. Journal of Geochemical
Exploration 701, 307–311.
Wang, H.D., Philp, R.P., 1997. Geochemical study of potential
source rocks and crude oils in the Anardako Basin,
Oklahoma. American Association of Petroleum Geologists
Bulletin 81, 249–275.
Warren, J.K., George, S.C., Hamilton, P.J., Tingate, P., 1998.
Proterozoic source rocks: sedimentology and organic char-
acteristics of the Velkerri Formation, Northern Territory,
Australia. American Association of Petroleum Geologists
Bulletin 82, 442–463.
Wiggins, W.D., Harris, P.M., Burruss, R.C., 1993. Geochem-
istry of post-uplift calcite in the Permian Basin of Texas and
New Mexico. Geological Society of America Bulletin 105,
779–790.
Yeh, H.W., Epstein, S., 1981. Hydrogen and carbon isotopes of
petroleum and related organic matter. Geochimica et
Cosmochimica Acta 45, 753–762.
Y€
ukler, M., Wallace, G., 1990. The effect of heating rate on
kerogen maturation and oil generation. American Associ-
ation of Petroleum Geologists Bulletin 74, 796.