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Geochimica et Cosmochimica Acta 72 (2008) 2510–2533

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Late Palaeozoic hydrocarbon migration through the Clair

field, West of Shetland, UK Atlantic margin
Darren F. Mark a,b,*, Paul F. Green c, John Parnell a, Simon P. Kelley d,
Martin R. Lee e, Sarah C. Sherlock d
a
Department of Geology & Petroleum Geology, Meston Building, Meston Walk, University of Aberdeen, Aberdeen, AB24-3UE, UK
b
NERC Argon Isotope Facility, Scottish Universities Environmental Research Centre, Rankine Avenue, Scottish Enterprise Technology
Park, East Kilbride, G75-0QF, UK
c
Geotrack International Ltd, 37 Melville Road, Brunswick West, Vic. 3055, Australia
d
Centre for Earth, Planetary, Space and Astronomical Research (CEPSAR), Department of Earth Sciences, Open University,
Walton Hall, Milton Keynes, MK7-6AA, UK
e
Department of Geographical and Earth Sciences, Lilybank Gardens, University of Glasgow, Glasgow, G12-8QQ, UK

Received 9 July 2007; accepted in revised form 28 November 2007; available online 26 February 2008

Abstract

Geochemical analysis of bitumen- and hydrocarbon-bearing fluid inclusions from the Devonian-Carboniferous Clair field
indicates that the reservoirs contain a mixture of oils from different marine and lacustrine sources. Reconstruction of the Clair
field oil-charge history using fluid inclusion petrography show that oil-charging occurred at times of K-feldspar, quartz and
calcite cementation. Temperature–composition–time data yielded from the integration of fluid inclusion microthermometry
with high-resolution Ar–Ar dating, date hydrocarbon-bearing K-feldspar overgrowths at 247 ± 3.3 Ma. These data show that
in order for oil to be trapped within primary fluid inclusions in K-feldspar overgrowths, hydrocarbon migration throughout
the UK Atlantic margin must have been taking place during the Late Palaeozoic and as such, current industry oil-play models
based solely on oil charging from Jurassic-Cretaceous marine sources are clearly incomplete and need revision. Apatite fission
track analysis and vitrinite reflectance data were used to reconstruct thermal burial histories and assess potential oil genera-
tion from Middle Devonian lacustrine source rocks. Thermal history data from wells along The Rona Ridge adjacent to the
Clair field show that the Palaeozoic section was heated to greater than 100 °C at some time between 270 and 230 Ma, con-
firming that Devonian source rocks were mature and expelling oil during the Late Palaeozoic at the time that authigenic K-
feldspar overgrowths were growing in the Clair field.
Ó 2008 Elsevier Ltd. All rights reserved.

1. INTRODUCTION rately constrain the timing of hydrocarbon generation and

The West of Shetland (WOS) region of the UK Atlantic
margin has been of exceptional interest for its hydrocarbon
prospectivity. Petroleum system analysis has failed to accu-
* timing of hydrocarbon migration throughout the margin,
Corresponding author. Address: NERC Argon Isotope Facil-
ity, Scottish Universities Environmental Research Centre, Rankine
Avenue, Scottish Enterprise Technology Park, East Kilbride,
G75-0QF, UK. Fax: +44 1355229898.
E-mail address: d.mark@suerc.gla.ac.uk (D.F. Mark).
whilst studies (Scotchman et al., 1998; Holmes et al.,
1999) have shown the presence and effectiveness of hydro-
carbon source rocks in the adjacent Faeroe-Shetland Basin
(FSB), determination of the amounts, type and timing of
hydrocarbon generation have been problematical. A critical
issue upon which exploration and appraisal depend is the
and although a series of models show postulated timings
of oil generation and expulsion (Iliffe et al., 1999; Lamers
and Carmichael, 1999; Carr and Scotchman, 2003; Scotch-
man et al., 2006), it is very difficult to determine absolute

0016-7037/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.gca.2007.11.037
 Hydrocarbon migration through the Clair field 2511

dates for oil generation, expulsion and migration. Mark
et al. (2005) using temperature–composition–time data
determined from authigenic K-feldspar (Mark et al.,
2006) managed to directly date hydrocarbon migration, res-
ervoir charging and reservoir breach within the UK Atlan-
tic margin to within 3 Ma.
Hydrocarbon generation is dependant upon burial-re-
lated increases in temperature, but may also be affected
by pulses of hot fluid flow, evidence for which is widespread
across the UK Atlantic margin (Parnell et al., 2005). The
hydrocarbon source rocks for a large portion of oil shows
throughout WOS are Middle Jurassic and Kimmeridge
Clay Formation (KCF) equivalent facies that reside in the
FSB (Bailey et al., 1987). Industry models suggest that oil
generation within the FSB began during the Aptian-Albian
(115 Ma) transition with WOS reservoir-charging taking
place since the Late Cretaceous (Carr and Scotchman,
2003; Scotchman et al., 2006). Although pre-Mesozoic
source rocks have been considered as viable hydrocarbon
sources within the WOS region (Scotchman et al., 1998),
a lack of geochemical evidence (i.e. the absence of Devo-
nian biomarkers) in reservoirs has resulted in rejection of
the hypothesis (Scotchman et al., 1998).
The study described in this paper was undertaken in or-
der to determine the timing of the first oil-charge event
throughout the WOS region. Using core samples from with-
in the WOS region, the Devonian-Carboniferous Clair field
(block 206; Fig. 1), we applied the methodology developed
by Mark et al. (2005, 2006) to determine temperature–com-
position–time (TXt) data from authigenic K-feldspar to
reconstruct the oil-charge history of the Clair reservoir.
Apatite fission track analysis (AFTA) and vitrinite reflec-
tance (VR) data were also utilised to provide a regional
framework for understanding the thermal history and
hydrocarbon generation history of Orcadian Basin lacus-
trine facies throughout Caithness, Orkney and Shetland
and the adjacent offshore region.
1.1. Clair field
The Devonian-Carboniferous reservoired Clair field is
located 75 km west of the Shetland Isles (Fig. 1) within a
remnant of the Devonian Orcadian Basin. The reservoir is
800 m thick and overlies a NE-SW trending ridge (The
Rona Ridge) of metamorphic basement (Fig. 1). The reser-
voir is composed of Upper ORS–Lower Carboniferous aeo-
lian–fluviatile–lacustrine red-bed facies (Allen and Mange-
Rajetzky, 1992) deposited between 330 and 380 Ma. The
two lower cycles of the Clair Group are separated from
the upper cycle by an important field-wide unconformity.

Fig. 1. (A) Map showing regional extent of the Devonian Orcadian Basin (palaeogeographical reconstruction modified from Duncan and
Buxton, 1995) and position of the Clair field and Beatrice field relative to mainland Scotland. (B) Area enlarged from (A) showing Clair field
outline and sample well locations relative to the field. (C) Cross-section (line of section from previous panel) showing fractured nature of the
Devonian-Carboniferous reservoir and well locations relative to field structure.
2512 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533
Late Cretaceous shales unconformably overlie the Carbon-
iferous strata and seal the reservoir. The Clair field is dom-
inated by two main structural sets, NE-SW oblique faults
which truncate The Rona Ridge and ENE-WSW normal
fault segments. Due to the extensively cemented nature of
the reservoir, open fractures that trend NNW-SSE and
WNW-ESE are integral to the field’s reservoir potential
(Coney et al., 1993). The reservoirs contain an estimated
3–5 billion barrels of undersaturated oil in place (Scotch-
man et al., 1998).
Rooney et al. (1998) and Scotchman et al. (1998) used
gas-chromatography, biomarkers, and compound specific
isotope analysis to demonstrate that the low API gravity
(22–26°) Clair hydrocarbons are a mixture of different oils
that originated from various sources. The origin of an oil
accumulation is difficult to establish when the oil is a mix-
ture from multiple sources, or when more than one episode
of charging is involved, but these studies identified two
main groups. The first oil is heavy, extensively degraded,
and originated from type I non-marine, lacustrine kerogens
at low maturities. The second oil is relatively undegraded
and was generated from a more refractory type II/III kero-
gen from a KCF equivalent source rock. The first oil was
deposited in a more oxic environment with a stronger ter-
restrial input than the second oil. Preliminary geochemical
data based on isotopic signals of n-alkanes generated by
hydropyrolysis (hypy) of asphaltenes (Russell et al., 2004)
isolated from Clair crudes that are most tightly bound to
the oil stained cores (well 206/8-8 and 206/8-7), show that
there is at least one additional group of oils within the Clair
reservoir and potentially several more. It is not known if the
isolated fraction is representative of the first oil charge to
enter the Clair reservoir; it is however representative of
the first oil to be bound to the reservoir detritus (Russell
et al., 2004). The n-alkanes generated by the asphaltene
hypy for both the oil and the reservoir cores are signifi-
cantly lighter than would be expected if, as currently be-
lieved, the early charges were solely sourced from the
Jurassic-Cretaceous source rocks in the FSB. The prelimin-
ary data suggest that oil from pre-Jurassic terrestrial
sources has contributed to the charging history of the Clair
reservoir.
A similar story charting exploration-discovery unfolded
with respect to the Beatrice oil field within the Inner Moray
Firth (Fig. 1). Although assumed to be charged with oil
from Jurassic-Cretaceous sources, geochemical analysis of
bitumens within the Beatrice field reservoir showed that
Beatrice-oil could not have been generated solely from
KCF source rocks (Peters et al., 1989). The oil is in fact a
mixture of products derived from effective Devonian lacus-
trine facies and Middle Jurassic source rocks. Recognition
of effective Devonian source rocks in the Inner Moray Firth
has many implications for regional hydrocarbon explora-
tion strategies within areas surrounding the Orcadian Ba-
sin, notably the UK Atlantic margin. For example, the
realisation that Devonian source rocks have passed through
the oil window during the Late Palaeozoic, Mesozoic and
Cenozoic, raises the possibility that if such source rocks
are as extensive offshore as suspected, hydrocarbons might
be found in very old trap structures throughout regions
where Jurassic source rocks are still immature. Fractured
crystalline basement found on Orcadian basin boundary
highs, such as that found throughout the Clair field (The
Rona Ridge), also becomes a much more prominent explo-
ration target throughout the UK Atlantic margin.
1.2. Orcadian basin
In the north of Scotland collapse of over-thickened Cal-
edonian lithosphere following the Scandian episode of the
Caledonian Orogeny resulted in normal reactivation of Cal-
edonian thrust zones culminating in northwest–southeast
extension. Rifting produced many linked half-graben basins
that are collectively known as the Devonian Orcadian Ba-
sin. The Orcadian Basin extends from the borders of the
Moray Firth in the south to Shetland in the north and Nor-
way in the east (Fig. 1). Offshore reconstruction of the Or-
cadian Basin boundaries is extremely poor and currently
based on lithological data from wells that have penetrated
Devonian sedimentary rocks. On average, the Orcadian Ba-
sin contains a 3–4 km fill of Devonian continental deposits
that are collectively termed the Old Red Sandstone (ORS).
Broadly the ORS can be divided into three groups: Lower,
Middle and Upper. Lower ORS conglomeratic facies
unconformably reside on metamorphic basement and were
deposited by alluvial fans that developed at fault scarps
along basin margins (Trewin, 1989). Middle ORS facies at
Caithness and Orkney are dominated by a thick sequence
of organic-rich cyclic lacustrine deposits, whereas in Shet-
land and Moray Firth, fluvial sedimentary rocks predomi-
nate. The fluvial sediments are punctuated by numerous
lacustrine intervals reflecting periodic lake transgression
across surrounding alluvial plains (Trewin, 1989). The most
widely developed of the lacustrine intervals is the Achanar-
ras horizon which contains distinctive fish fauna and due to
its wide regional extent, is the key to basin-wide correlation
(Hillier and Marshall, 1992). Upper ORS facies are domi-
nantly fluvial deposits that were deposited by braided river
system that flowed from the southwest (Trewin, 1989).
Middle ORS organic-rich lacustrine facies are of great
interest as potential hydrocarbon source rocks especially
in the Orkney and Caithness regions. Several studies have
mapped present day maturation distributions of organic-
rich lacustrine sedimentary rocks throughout the Orcadian
Basin in an attempt to understand basin evolution and as-
sess potential for hydrocarbon generation. These studies
(Parnell, 1985; Irwin and Meyer, 1990; Hillier and Mar-
shall, 1992; Duncan and Buxton, 1995) have shown an ex-
treme range in maturity across the Orcadian Basin where
VR values (records of maximum palaeotemperature) range
from 0.5% to 10.5% Ro (Hillier and Marshall, 1992). Within
this range in maturity, the overall pattern is one of sharply
juxtaposed regions of high and low maturity.
Rift basins such as the Orcadian Basin are characterised
by high but variable geothermal gradients and above aver-
age levels of organic maturation at shallow depths. For
example, Tertiary rocks buried between 300 and 1500 m
in the Rhynie Graben witness present day geothermal gra-
dients that range between 30 and 90 °C km 1 and have VR
values of 0.8% Ro (Roberts, 1985). In basins with normal
 Hydrocarbon migration through the Clair field 2513

levels of heat flow (i.e. 20–30 °C km 1), 0.8% Ro would
correspond to burial depths of approximately 5000 m (Rob-
erts, 1985). With generally high geothermal gradients, re-
gions within the Orcadian Basin must have undergone
very early maturation. Reservoired hydrocarbons which
have been baked in situ by Permian dykes in Orkney (Astin,
1990) suggest that oil generation and migration had already
occurred by Late Carboniferous times (290 Ma), the dyke
swarms themselves having little effect on maturation. Direct
evidence for the timing of cooling is provided in Caithness
and Orkney by AFTA (well 12/16-1) which reveal that cool-
ing from palaeotemperatures in excess of 110 °C began dur-
ing the Late Carboniferous (Green et al., 1995). This study
also confirms that geothermal gradients at this time were
elevated.
2. SAMPLE DESCRIPTION
The samples used for fluid inclusion work during this
study come from wells 206/8-8, 206/8-7, and 206/8-1a
(Fig. 1). Baron et al. (2008) provides a comprehensive
description of samples from well 206/8-8, 206/8-7 and
206/8-1a and a summary is presented here. Rock samples
are pale orange-colored subarkosic sandstones. Most of
the detrital grains are quartz and feldspar with rare lithic
fragments (although the presence of abundant lithic frag-
ments was noted by Pay et al., 2000, this was not evident
in samples analysed throughout his study). All samples con-
tain various clay minerals including smectite, chlorite, illite
and kaolinite as well as calcite, quartz, K-feldspar, fluorite,
pyrite and marcasite cements. Clay minerals and calcite are
the dominant cementing phases. Quartz and K-feldspar ce-
ments mainly occur as overgrowths on detrital quartz and
K-feldspar grains, respectively (Fig. 2). Quartz overgrowths
occasionally contain small inclusions of K-feldspar cement
at the contact between detrital quartz grains and their over-
growths. This relationship suggests that K-feldspar cemen-
tation predated quartz overgrowths. In all samples
authigenic quartz and K-feldspar pre-date calcite cementa-
tion but post-date deposition of clay cements. Calcite ce-
ments are coarsely-crystalline and in places envelop
detrital grains, producing a poikilitopic texture. Based on
cathodoluminescence properties, calcite veins and cements
can be divided into two types: (1) dull to moderately or-
ange-luminescing calcite (C1) which is slightly ferroan in
composition; and (2) bright orange-luminescing calcite
(C2) which is non-ferroan (Fig. 2). C1 always predates C2
(Fig. 2). Small deformation bands (up to 1 cm) are com-
posed of fine angular detrital grains whose sizes are signif-
icantly smaller than in the surrounding rock. Detrital grains
with fractured overgrowths occur within some of the defor-
mation bands, indicating that K-feldspar and quartz

Fig. 2. (A) Transmitted light photomicrograph showing a K-feldspar overgrowth (arrow) enveloping a detrital feldspar grain (well 206/8-8,
1950 m). (B) SEM-SE image showing authigenic quartz overgrowth (white arrow) developing on a detrital quartz grain that is enveloped by
illite (black arrow; well 206/8-7, 2048.75 m). (C) Cold-CL image showing fracture-fill relationship between ferroan-rich C1 calcite and C2
calcite (well 206/8-7, 2025.5 m). (D) TEM image showing subgrain structure of K-feldspar overgrowth at sub-micron scale. A dislocation-rich
(semi-coherent) boundary (arrow) separating two subgrains (well 206/8-8, 2134.75 m).
2514 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533
cementation pre-dated their formation. The deformation
bands are cemented by unbrecciated C1, indicating that
the deformation bands pre-dated C1 precipitation. Veins
filled by C2 also cross-cut, and clearly post-date, the defor-
mation bands.
3. METHODS
3.1. Fluid inclusion petrography and microthermometry
Hundred micrometers thick doubly polished fluid inclusion
wafers were characterised using a standard Nikon ECLIPSE E600
microscope fitted with an ultra-violet (UV) light source. Microth-
ermometry was performed using a calibrated (associated error,
±1 °C) Linkam TH-600 fluid inclusion stage with a heating rate of
10 °C/min 1 and employing standard methods (Shepherd et al.,
1985). The fluid inclusions had consistent sizes and shapes of va-
pour bubbles and vapour–liquid ratios (Goldstein, 2001). Inclu-
sions that showed stretching were excluded from the study (Munz,
2001). Aqueous fluid inclusions occur coevally with hydrocarbon
inclusions and therefore are gas saturated and require no correlated
pressure correction (Hanor, 1980). Homogenization temperatures
(Th) are therefore indicative of the true temperatures of fluid
entrapment. Final ice melting temperature (Tm) measurements,
which are dependent on the quantity of salt present in solution,
were determined using a heating rate of 1 °C/min 1. Salinities were
estimated using the methods of Bodnar (1993).
3.2. Ar–Ar geochronology
In addition to conducting fluid inclusion analysis and mic-
rothermometry (Parnell et al., 1999), the natural radiogenic decay
of 40K to 40Ar in K-feldspar permits high resolution Ar–Ar age
determination (Mark et al., 2005). Integration of fluid inclusion
analysis and microthermometry with UV laser ablation Ar–Ar
dating (Kelley et al., 1994) will yield TXt data (Mark et al., 2006).
TXt data can constrain the timing, duration, temperature and
composition of fluid flow (Mark et al., 2007), providing that the
Ar-isotope system has not been thermally disturbed (Lee and
Parsons, 2003).
Despite the fact that previous investigations (Hagen et al., 2001)
have yielded meaningful Ar–Ar ages for authigenic K-feldspar, it
has been suggested that authigenic K-feldspar does not quantita-
tively retain Ar at low temperatures (Lee and Parsons, 2003).
Therefore, the retentiveness of authigenic K-feldspar with respect
to Ar had to be quantified in detail in order to support the Ar–Ar
data. The microstructures of authigenic K-feldspar overgrowths
were characterised by high-resolution imaging including transmis-
sion electron microscopy (TEM), and Ar-loss was modelled with
respect to subgrain structure and Ar diffusion using reconstructed
thermal histories.
Prior to irradiation, a 100 lm thick doubly polished fluid
inclusion wafer was cleaned ultrasonically in methanol and
deionised water. The sample was cadmium shielded and irradiated
for 50 h in the Canadian McMaster reactor. Neutron flux was
monitored with biotite standard GA1550 (98.8 ± 0.5 Ma; Renne
et al., 1998); a calculated J value of 0.01175 ± 0.00006 was used. A
New Wave Research UP-213 nm pulsed Nd-YAG laser (266 nm)
with a 12 lm spot size was used for Ar-extraction. Extracted gases
were cleaned using three SAES AP10 getters, two operated at
450 °C and the other at room temperature. A MAP 215-50 noble
gas mass spectrometer analysed Ar-isotope compositions. The data
were corrected for blanks, mass spectrometer discrimination, 37Ar
decay and reactor induced interferences. Quoted Ar–Ar errors are
2r and include a 0.5% error assigned to the J value. Reactor
induced correction factors used were: (39Ar/37Ar)Ca = 0.00065,
(36Ar/37Ar)Ca = 0.000264, (40Ar/39Ar)K = 0.0085.
Mark et al. (2005, 2006) provide further details concerning the
integration of fluid inclusion and Ar–Ar data.
3.3. Apatite fission track analysis
The principles involved in using AFTA to constrain thermal
histories in sedimentary basins are described in detail elsewhere
(Green et al., 1989a,b, 2001, 2002, 2004; Parnell et al., 1999, 2005).
In brief, optical microscope analysis of radiation damage features
in detrital apatite grains separated from clastic units allows deter-
mination of the maximum temperature to which a sedimentary unit
has been heated (up to a maximum of around 110–120 °C,
depending on apatite composition) and the time at which the
sample began to cool from that palaeothermal maximum. Inte-
gration of AFTA and VR data allows extension of the thermal
history constraints to higher palaeotemperatures.
Definition of the variation of palaeotemperature with depth
provides insights into mechanisms of heating and cooling, distin-
guishing between heating due to deeper burial, elevated basal heat
flow and lateral flow of hot fluids (Bray et al., 1992). Linear pal-
aeotemperature profiles provide direct constraints on palaeogeo-
thermal gradients and extrapolation to an appropriate palaeo-
surface temperature allows determination of the corresponding
amounts of removed section required to explain the observed pal-
aeotemperatures (Green et al., 2004; Japsen et al., 2005; Holford
et al., 2005).
It is important to appreciate that it is very uncommon for fis-
sion track ages to directly indicate the timing of a discrete cooling
event. Rather, the fission track age represents an integrated mea-
sure of the balance between the production of tracks by sponta-
neous fission and the reduction in track length due to the thermal
history. In order to extract thermal history constraints from the
data, a forward modelling approach is used to define the range of
histories for which predicted parameters (fission track age and the
distribution of track lengths and their variation with wt.% Cl) are
consistent with measured data. It is however, not possible to extract
explicit thermal history solutions directly from AFT data because
of the high degree of redundancy in the data—i.e. many histories
result in the same measured age and length parameters. Instead, we
focus on determining the maximum palaeotemperature and the
onset of cooling, using an approach based on likelihood theory
similar to that described by Gallagher (1995) to define best-fit
values and corresponding 95% confidence intervals.
3.4. Vitrinite reflectance
VR based on the increasing reflectance of organic macerals
with increasing temperature, is commonly used in hydrocarbon
exploration as an indicator of thermal maturity (Tissot and Welte,
1984). VR data can be used to provide independent estimates of
maximum palaeotemperatures, through knowledge of the reaction
kinetics, thereby providing a useful complement to the informa-
tion derived from AFTA. A VR value of 0.7% corresponds clo-
sely to total annealing of fission tracks in apatite (Duddy et al.,
1994).
In recent years it has become apparent that VR data generated
by different analysts are not equivalent (see discussion in Green
et al., 2002). We find a high degree of consistency between thermal
history interpretations from AFTA and VR data generated using
an approach (Cook, 1982) recommended by the International
Commission on Organic and Coal Petrography (www.iccop.org).
This involves measurement of maximum reflectance under oil
(Romax) in polished thick sections, with identification of the
indigenous vitrinite population being made on textural grounds.
 Hydrocarbon migration through the Clair field
These data then enable an independent assessment to be made of
the possible presence of reworked vitrinite populations from pet-
rographic evidence, as well as allowing identification of material
introduced by caving from higher levels in the borehole. The data
presented here were generated using the ICCOP potocols.
In contrast, VR data encountered in hydrocarbon industry re-
ports are often based on measurements of random reflectance
(Rorand) in strewn slides of organic concentrates, with the indige-
nous vitrinite population often identified by inspection of histo-
grams of measurements and separation into perceived sub-
populations. This approach tends to give lower values compared to
measurement of Romax as described above (see Green et al., 2002
for further discussion). Therefore, in converting VR data to max-
imum palaeotemperatures it is essential to use a kinetic model
which is appropriate to the analytical approach adopted. Experi-
ence in a variety of different settings suggests that the Romax ap-
proach described above yields estimates of maximum
palaeotemperature that are highly consistent with those from
AFTA, if the Burnham and Sweeney (1989) algorithm for the ki-
netic response of VR is used.
4. RESULTS
The focus of this study is determination of TXt data
from authigenic K-feldspar via the integration of fluid
inclusion petrography and microthermometry with high-
resolution Ar–Ar dating. Hence, only a detailed description
of the authigenic K-feldspar is presented below. A brief
summary of the petrography of the quartz and calcite ce-
ments is given in Section 2, and readers are directed to Bar-
on et al. (2008) for further detailed descriptions.
4.1. Authigenic K-feldspar
Samples contain 20 to 40 lm K-feldspar overgrowths
that are developed around detrital grains of plagioclase
and K-feldspar (Fig. 2). The overgrowths are untwinned
and in optical discontinuity with the enveloped detrital
grain. Complex extinction patterns when viewed in trans-
mitted light between cross polarisers suggest that the over-
growths are composed of slightly misorientated subgrains.
Diffraction contrast TEM imaging shows that K-feldspar
overgrowths are composed of mosaics of misaligned sub-
grains separated by dislocation-rich boundaries and
micropores (Fig. 3). Subgrains are finely mottled and have
consistent sizes of between 1 and 2 lm and so are compara-
ble to subgrains reported in previous investigations (Wor-
den and Rushton, 1992; Lee and Parsons, 2003; Mark
et al., 2005).
4.2. Fluid inclusion petrography and microthermometry
Both aqueous and hydrocarbon inclusions occur in all
samples analysed. Hydrocarbon fluid inclusions occupy pri-
mary settings (the fluid was entrapped during mineral
growth) within K-feldspar overgrowths (Fig. 3), quartz
overgrowths, C1 cement and veins, C2 veins, but not C2 ce-
ment, suggesting that during C2 precipitation fluid predom-
inantly migrated through open fracture systems rather than
inter-granular pore networks. Hydrocarbon inclusions are
mainly 2-phase (liquid and vapour), range in size from 2
to 50 lm and have high volumetric proportions (0.90–
2515
0.97) of liquid. Most hydrocarbon inclusions fluoresce in
UV light. These inclusions were confirmed as hydrocar-
bon-bearing by freezing to less than 80 °C. The dominant
fluorescence colour of the hydrocarbon inclusions is yel-
low–orange, with subordinate quantities of blue- and
white-fluorescing inclusions also occurring. Only blue-fluo-
rescing primary hydrocarbon inclusions occur within K-
feldspar overgrowths. These inclusions are believed to be
representative of the first recorded oil charge to enter the
Clair Group. Primary aqueous fluid inclusions occur coev-
ally with the hydrocarbon fluid inclusions. Aqueous inclu-
sions are two-phase (liquid and vapour), range in size
from 2 to 10 lm and have high volumetric proportions
(0.90–0.97) of liquid. The complete fluid inclusion microth-
ermometric results are summarised in Table 1 and Fig. 3.
Blue-, yellow–orange-, white-, and non-fluorescing hydro-
carbon inclusions within authigenic quartz and calcite yield
very similar Th values. Th values of primary aqueous inclu-
sions hosted in quartz overgrowths range from 111.3 to
170.5 °C. Th values determined from fluid inclusions within
K-feldspar overgrowths, which are considered from petro-
graphic evidence to pre-date entrapment of the quartz-
hosted inclusions, are slightly lower. These values range
from 90.2 to 116.3 °C. Th values of primary inclusions
hosted in C1 cements and veins range from 129.4 to
170.0 °C. Th values of primary inclusions hosted in C2 ce-
ments and veins are slightly lower, ranging from 118.6 to
159.4 °C. The average Th values of the majority of the
hydrocarbon fluid inclusions are lower than the associated
coeval aqueous fluid inclusions. The range of salinities of
the aqueous inclusions indicates that mixing of fluids with
differing compositions occurred during diagenesis. The low-
er salinity aqueous fluids are similar in composition to
meteoric (<0.5 wt.% NaCl) and/or marine (3.5 wt.% NaCl)
waters. The higher salinity aqueous fluid is typical of basi-
nal brines, whose salinity has been derived from extensive
water–rock interactions or precipitated directly from deep
saline fluids. Rare 3-phase inclusions that are filled by a
hydrocarbon liquid phase, an aqueous liquid phase and a
vapour phase, occur within primary and secondary settings
in K-feldspar, quartz and calcite cements and fractured
detrital grains in the Clair reservoir. The proportions of
oil, vapour and aqueous liquid within the 3-phase inclu-
sions is extremely variable. The volumes of oil contained
within fluid inclusions ranges from 3% to 74% (n = 31) total
inclusion volume. The extreme variability indicates that the
precipitating fluid was not a homogenous mix of oil and
water, but a heterogeneous fluid (Goldstein, 2001). At
Earth surface conditions (pressure and temperature) oil
and aqueous fluids do not readily mix and hence a suite
of fluid inclusions containing oil and aqueous fluids would
possess variable oil–water ratios.
4.3. Ar–Ar geochronology
Ar–Ar ages determined from detrital feldspar grains
range from 424 ± 19 to 1743 ± 428 Ma (n = 5). Variability
in the detrital feldspar ages is potentially due to a combina-
tion of factors: (1) significant replacement of the detrital
grains by feldspar that crystallized later and at lower tem-
2516 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533

Fig. 3. (A) Transmitted light fluid inclusion photomicrograph. Primary 2-phase aqueous fluid inclusion (arrow) trapped within a K-feldspar
overgrowth (OG) that is enveloping a detrital feldspar grain. (B) Enlargement of (A). Both the liquid and vapour phases within the fluid
inclusion are clearly visible. (C) Transmitted light fluid inclusion photomicrograph. Primary 2-phase oil inclusion (arrow) trapped within a K-
feldspar overgrowth. (D) UV light photomicrograph. Oil inclusion from (C) enlarged and clearly showing a blue fluorescence (arrow). (E)
Cross-plot showing total aqueous fluid inclusion data set for Clair reservoir; temperature of fluid entrapment (homogenization temperature)
versus fluid salinity (converted from final ice melting temperature). Plot shows salinity of meteoric water, sea water, and basinal brines relative
to the data. Clearly mixing of fluids from different reservoirs is required to produce the distribution observed.

peratures; (2) potential Ar-loss from subgrained micro-
structures within the feldspar crystal; (3) extraction of Ar
gas from the detrital grains via laser ablation in volumes
too small to yield reliable ages (Table 2) and (4) real varia-
tion in source ages. Ar–Ar ages from optically identifiable
K-feldspar overgrowths (Table 2) range from 230 ± 70 to
283 ± 58 Ma (n = 9). Owing to the small size of the over-
growths it was extremely difficult to extract sufficiently large
volumes of argon from them to ensure a mass spectrometer
signal greater than 10 times that of the blank levels (Mark
et al., 2006) which would minimise analytical error. These
potential analytical difficulties are the source of the large er-
rors associated with most of the K-feldspar overgrowth Ar–
Ar ages in Table 2. Although only small amounts of Ar gas
were extracted from some K-feldspar overgrowths, the ratio
of 40Ar to 39Ar is clearly consistent regardless of gas vol-
umes (Table 2). The data yield a weighted mean of
247.7 ± 3.3 Ma (2r, mean square weighted deviation of
0.73). Scatter within the K-feldspar overgrowth Ar–Ar data
set may also be attributed, to a lesser degree, to ablation of
populations of subgrains of different size ranges, as deter-
mined from TEM imaging (Fig. 2). The temperature at
which Ar-loss occurs is directly related to subgrain size,
with Ar closure temperatures being lower for the smaller
subgrains. For example, an ablation area containing ten
2 lm subgrains and only two 1 lm subgrains would poten-
tially yield a slightly older Ar–Ar age than an ablation area
containing ten 1 lm subgrains and two 2 lm subgrains be-
cause more Ar will be lost from the sample with the greater
ratio of small to large subgrains.
4.4. AFTA and VR
AFTA and VR data from samples of four wells in the
vicinity of the Clair field (206/8-8, 1750 m; 206/8-7,
2075 m; 206/10-2, 366–2918 m; 206/9-2, 658–2429 m;
 Hydrocarbon migration through the Clair field 2517

Table 1
Fluid inclusion microthermometric data from primary inclusions
Well Depth (m) Authigenic mineral phase Homogenization temperature (°C) Salinity (wt.% NaCl eq.)
H/C n Aq n
206/8-7 2000 K-feldspar 88.1-96.7 20 93.2–111.5 12 4.03–6.59
Quartz 107.3–134.8 6 118.4–144.6 7 0.53–2.41
Calcite (C1c) 133.6–144.2 4 140.6–163.4 3 1.4–3.23
Calcite (C1v) 148.7–167.8 8 135.3–161.9 6 2.57–4.65
Calcite (C2c) — 0 118.6–143.5 7 2.07–3.87
Calcite (C2v) 121.3–154.6 5 120.8–149.3 6 2.41–4.03
206/8-la 2041.4 K-feldspar 94.3–108.7 11 90.2–116.3 14 3.06–6.01
Quartz 105.4–143.2 8 111.3–151.6 6 0.71–1.91
Calcite (C1c) 128.3–156.1 6 148.5–163.2 8 1.74–4.03
Calcite (C1v) 136.7–162.8 4 143.9–170.0 7 2.24–5.26
Calcite (C2c) — 0 124.6–148.2 9 1.91–3.73
Calcite (C2v) 128.6–141.9 7 119.3–151.4 8 2.57–4.65
206/8-8 2134.75 K-feldspar 94.5–99.6 6 90.5–101.2 11 6.06–6.74
Quartz 132.5–148.6 8 139.8–170.5 7 1.57–4.80
Calcite (C1c) 138.7–151.2 5 148.3–164.9 6 1.91–3.23
Calcite (C1v) 132.4–153.2 7 138.6–161.4 5 2.74–4.8
Calcite (C2c) — 0 126.3–159.4 5 1.05–3.39
Calcite (C2v) 119.7–137.6 6 124.8–143.3 5 2.9–4.49
206/8-8 2158.5 K-feldspar 78.6-101.4 18 93.7–108.2 12 4.49–7.02
Quartz 137.3–151.4 6 123.6–144.5 6 2.07–2.9
Calcite (C1c) 124.6–144.8 7 133.3–156.8 4 1.91–4.03
Calcite (C1v) 134.6–159.1 5 129.4–155.3 6 1.4–3.26
Calcite (C2c) — 0 141.4–153.8 6 1.74–3.87
Calcite (C2v) 125.3–140.0 4 130.9–137.4 5 2.74–5.11
206/8-8 2160.85 K-feldspar 84.5–97.9 19 93.6–104.8 7 5.56–6.74
Quartz 134.5–155.5 4 134.2–165.1 6 2.57–4.03
Calcite (C1c) 132.9–146.0 6 128.4–151.5 5 1.05–2.41
Calcite (C1v) 141.1–163.2 5 145.8–163.4 5 1.91–3.55
Calcite (C2c) — 0 136.2–155.7 7 1.91–2.57
Calcite (C2v) 130.6–145.2 3 138.4–149.2 8 2.9–5.28
Salinity calculated using equations of Bodnar (1993). Homogenization occurred via bubble point transition. H/C, hydrocarbon-bearing
inclusion data; Aq, aqueous fluid inclusion data; x, no fluid inclusions present.

Fig. 1) are summarised in Tables 3 and 4, respectively. Fis-
sion track ages and mean track lengths are plotted against
depth and present-day temperature in Fig. 4. The variation
of stratigraphic age with depth is also shown for each well,
together with the variation in fission track age and mean
track length predicted from the default thermal history sce-
nario in each well. As explained in more detail elsewhere
(Green et al., 2004; Parnell et al., 2005), this represents
the situation in which all sedimentary units are currently
at their maximum post-depositional temperatures, and
forms the basis for extraction of information on the palae-
o-thermal history from the AFTA and VR data.
Measured fission track ages in samples of Mesozoic and
Cenozoic units in the 206/9-2 and 206/10-2 wells are older
than respective stratigraphic ages, showing that these sam-
ples are dominated by tracks formed prior to deposition of
the host sediments. In most of these samples, the AFTA
data show no definite evidence of post-depositional heating,
and provide only an upper limit to the maximum post-
depositional palaeotemperature (Table 3). However, in
two samples from the Late Cretaceous section in well
206/10-1, mean track lengths are more than 2 lm less than
the values predicted from the respective default thermal his-
tories, and detailed assessment shows that the track length
data in these samples can only be explained if these samples
have been hotter in the past. In contrast, fission track ages
measured in all samples from the Palaeozoic section in these
four wells are younger than the respective stratigraphic age
and are also significantly less than the values predicted from
the respective default thermal history, as are the mean track
lengths in most cases. These observations show that the
data cannot be explained by the default thermal history sce-
nario, and therefore the sampled sedimentary units must
have been hotter than the present-day temperatures at some
time after deposition.
4.4.1. Thermal history constraints from AFTA and VR
Maximum palaeotemperatures attained by each sample
and the time at which the sample began to cool from that pal-
aeo-thermal maximum have been determined using proce-
dures explained in detail elsewhere (Green et al., 2004;
Parnell et al., 2005), with results summarised in Table 4.
Two episodes of cooling can be resolved from the data in most
samples from the Palaeozoic section. Resolution of multiple
2518 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533

Table 2
Ar–Ar isotopic data for K-feldspar overgrowths (OG), detrital grains (DG), hybrid analyses (Hy) and average blanks (1012 cm3 STP)
40 39 38 37 36 40
Well & depth (m) Sample No Ar ArK ArCl ArCa Ar Ar*/39Ar Age (Ma) ±
206/8-7 (2000) OG1 37.493 1.201 0.008 0.181 0.076 12.601 249.1 39.1
206/8-7 (2000) OG2 181.247 14.524 0.206 0.000 0.000 12.480 246.9 3.5

Average blank (n = 3) 7.535 0.076 0.004 0.004 0.013 — — —

206/8-8 (2134.75) OG3 20.899 1.772 0.000 0.609 0.000 11.805 233.8 39.2
206/8-8 (2134.75) OG4 16.888 1.163 0.000 2.503 0.000 14.495 283.1 57.9
206/8-8 (2134.75) OG5 40.186 3.083 0.059 1.835 0.000 13.034 256.5 22.4
206/8-8 (2134.75) OG6 33.810 2.562 0.055 1.415 0.000 13.195 259.4 19.9
206/8-8 (2134.75) OG7 8.526 0.735 0.034 1.684 0.000 11.595 229.9 70.5
206/8-8 (2134.75) OG8 12.827 0.907 0.013 0.239 0.000 14.112 276.1 56.1

Average blank (n = 7) 7.732 0.063 0.105 2.495 0.008 — — —

206/8-la (2041.4) OG9 20.761 1.613 0.050 0.021 0.000 12.879 253.6 20.2
206/8-8 (2134.75) Hy1 17.363 1.096 0.055 0.441 0.000 15.817 307.3 29.1
206/8-8 (2134.75) Hy2 41.332 2.071 0.034 0.109 0.000 19.970 379.6 23.5
206/8-8 (2134.75) Hy3 52.744 2.633 0.109 0.441 0.000 20.041 381.7 24.0

Average blank (n = 4) 6.817 0.076 0.059 2.575 0.004 — — —

206/8-7 (2000) DG1 385.186 4.498 0.063 0.475 0.000 85.603 1253.4 12.8
206/8-7 (2000) DG2 90.980 4.024 0.097 0.290 0.000 22.619 424.1 19.3

Average blank (n = 3) 7.505 0.118 0.071 2.352 0.008 — — —

206/8-8 (2134.75) DG3 6.296 0.164 0.021 2.873 0.000 38.694 675.7 159.2
206/8-8 (2134.75) DG4 12.050 0.088 0.046 0.017 0.000 138.835 1743.6 428.0

Average blank (n = 3) 5.947 0.227 0.092 2.848 0.004 — — —

206/8-la (2041.4) DG5 13.570 0.584 0.000 1.142 0.000 23.166 433.8 54.1

Average blank (n = 2) 6.397 0.181 0.101 0.386 0.008 — — —

episodes in this way depends on the annealing of tracks
formed subsequent to the onset of cooling in an
early cooling episode. The extraction of thermal history infor-
mation from AFTA data in this way is illustrated in Fig. 5.
Comparison of the thermal history constraints derived
from each AFTA sample in Table 4 shows that results from
all samples from the Palaeozoic section in all four wells are
consistent with cooling from maximum palaeotemperatures
above 100 °C at some time in the interval 270–230 Ma (Late
Permian to Early Triassic). Similarly, estimates for the tim-
ing of the later cooling episode from all AFTA samples in
the 206/8-7, 206/8-8 and 206/10-1 wells, as well as two sam-
ples from the 206/9-2 well are consistent with cooling begin-
ning at some time between 25 and 10 Ma (Miocene). In
contrast, the three deepest samples from the Palaeozoic sec-
tion in well 206/9-2 suggest a distinct cooling episode began
between 150 and 50 Ma (Table 4).
Maximum palaeotemperatures derived from VR data in
the 206/9-2 and 206/10-1 wells are also listed in Table 4. No
VR data are available from the 206/8-7 and 206/8-8 wells.
Palaeotemperature constraints from both AFTA and VR
data in the 206/9-2 and 206/10-1 wells are plotted against
depth in Fig. 6, where it is clear that throughout each well
the maximum palaeotemperatures estimated from AFTA
are highly consistent with those from VR data in adjacent
samples.
Maximum palaeotemperatures between 100 and
125 °C derived from VR data in the Palaeozoic section in
both wells are highly consistent with those from AFTA cha-
racterising the Late Permian to Early Triassic palaeo-ther-
mal episode, confirming that the Palaeozoic section in
these wells cooled from maximum post-depositional palae-
otemperatures in this episode (i.e. any hydrocarbon source
rocks within this section reached their maximum maturity
levels in this episode). AFTA and VR data are available
only over a limited depth range in these two wells, and from
only single samples in the 206/8-7 and 206/8-8 wells, but
overall the available constraints for this episode in the
206/9-2 and 206/10-1 wells are consistent with linear pro-
files, as illustrated in Fig. 6. The form of these profiles sug-
gests that a major contribution to heating in this episode
was due to deeper burial, possibly combined with some de-
gree of elevated basal heat flow (see later discussion).
AFTA data in most post-Palaeozoic samples provide
only upper limits to the magnitude of Miocene palaeotem-
peratures, but in two samples from the 206/10-1 well
Table 3
AFTA sample details and apatite fission track age and track length data summary for samples from four WOS wells
Sample Depth Stratigraphic Present temperature qD (106 qs (106 qi (106 Fission track ± (Ma) P(v2) (%)d Mean track l ± (lm)e
(m) age (Ma)a (°C) tracks/cm2)b tracks/cm2)b tracks/cm2)b age (Ma)c ength (lm)
206/8-8
RD87-1 1750 385–330 69 1.145 (1779) 2172 (1352) 2.026 (1261) 226 22.7 <1 (20) 11.26 0.14 (100)
206/8-7
RD87-2 2075 385–330 73 1.147 (1779) 1.151 (791) 1.205 (828) 190 19.5 <1 (20) 10.71 1.52 (100)
206/9-2

Hydrocarbon migration through the Clair field

GC540-89 1088 65–57 40 1.413 (1091) 0.962 (285) 1.235 (366) 208.2 17.9 <1 (15) 12.27 0.18 (74)
GC540-97 1798 363–323 65 1.417 (1091) 1.817 (884) 2.561 (1246) 290.4 10.5 21 (20) 10.52 0.17 (108)
GC540-98 1943 363–323 70 1.42 (1091) 2.187 (1211) 3.104 (1719) 289.5 9.5 <1 (20) 10.99 0.14 (111)
GC540-99 2195 409–363 78 1.423 (1091) 1.636 (1193) 2.687 (1960) 264.5 8.2 <1(20) 10.08 0.18 (112)
GC540-101 2345 >540 84 1.426 (1091) 1.408 (416) 2.443 (970) 116.6 7.9 <1 (20) 9.73 0.20 (100)
GC540-102 2429 >540 86 1.43 (1091) 0.732 (283) 2.109 (815) 94.8 7.3 24 (20) 9.25 0.22 (109)
206/10-1
GC540-109 1105 65–57 22 1.389 (1091) 0.439 (164) 0.559 (209) 206.3 22.6 39 (17) 11.42 0.36 (24)
GC540-112 1341 74–65 40 1.383 (1091) 2.169 (1104) 2.176 (1108) 259.8 14.1 27 (20) 12.76 0.14 (102)
GC540-119 1981 87–74 57 1.378 (1091) 2.306 (1164) 2.746 (1386) 218.8 11.4 <1 (17) 11.51 0.17 (82)
GC540-122 2188 89–74 63 1.372 (1091) 1.608 (508) 2.431 (768) 172.2 11.4 <1 (20) 10.53 0.26 (75)
GC540-123 2217 89–87 64 1.367 (1091) 2.299 (311) 3.178 (430) 187.3 15.3 17 (7) 9.71 0.49 (33)
GC540-126 2339 409–290 67 1.361 (1091) 1.269 (594) 1.595 (747) 204.8 13.2 <1 (20) 10.32 0.17 (100)
GC540-127 2454 409–290 70 1.356 (1091) 1.423 (590) 2.85 (1182) 128.8 7.8 <1 (18) 9.77 0.20 (107)
GC540-129 2067 409–290 75 1.35 (1091) 1.324 (708) 2.028 (1085) 167.2 9.8 <1 (20) 9.59 0.23 (104)
GC540-130 2918 409–290 82 1.344 (1091) 0.673 (339) 1.585 (799) 108.8 7.9 <1 (20) 10.56 0.19 (100)
NB, All analytical details are as described by Green (1986), with the exception that some thermal neutron irradiations show a significant flux gradient, in which case the appropriate value of PD
was determined by linear interpolation through the grains.
a
Stratigraphic ages taken from composite log. All numerical values for stratigraphic ages assigned following (Harland et al., 1989).
b
Numbers in parentheses show the number of tracks counted.
c
Central age (Galbraith and laslett, 1993) used for samples containing significant spread in single grain ages, otherwise pooled age and conventional (Poisson) error (Green, 1981). Ages
calculated using CN-5 reference glass with zeta values (Hurford and Green, 1982) value of 380.4 ± 5.7 for samples RD87-1,2 and 384.6 ± 5.5 for GC540 samples.
d
Numbers in parentheses show the number of grains counted.
e
Numbers in parentheses show the number of track lengths measured.

2519
Table 4

2520
Thermal history interpretation summary of AFTA and VR data in samples from four WOS samples
Sample Depth Stratigraphic Present Measured Paleozoic & Mesozoic episodes Cenozoic episodes
(m) age (Ma)a temperature VR (%)b Max palaeo- Onset of cooling Max palaeo- Onset of cooling
(°C)
temperature (°C)c from AFTA (Ma) temperature (°C)c from AFTA (Ma)
206/8-8
RD87-1 1750 385–330 69 – 90–125 325–160 75–90 160–0
206/8-7
RD87-2 2075 385–330 73 – 100–110 300–215 85–95 100–0
206/9-2

D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533

GC540-86.1 658 35–23 25 0.3 (25) – – <50 –
GC540-87.1 756 57–35 29 0.29 (25) – – <50 –
GC540-89 1088 65–57 40 – – – <95 90–0
GC540-89.1 1116 65–57 41 0.36 (20) – – 59 –
GC540-90.1 1256 74–65 46 0.41 (6) – – 66 –
GC540-92.1 1378 74–65 50 0.5 (5) – – 83 –
GC540-94.1 1500 74–65 54 0.56 (5) – – 93 –
GC540-95.1 1588 98–74 57 0.52 (5) – – 86 –
GC540-96.1 1646 89–74 59 0.61 (10) – – 100 –
GC540-97.1 1783 363–323 64 0.64 (1) 106 – – –
GC540-97 1798 363–323 65 – 95–105 270–120 80–90 50–0
GC540-98 1943 363–323 70 – 100–110 270–200 80–90 120–0
>120 310–230
GC540-99 2195 409–363 78 – 90–100 160–50 – –
GC540-100.1 2286 409–363 82 0.78 (2) 125 – – –
>110 400–200
GC540-101 2345 >540 84 – 90–105 150–50 – –
>100 500–200
GC540-102 2429 >540 86 – 90–100 150–110 – –
206/10-1
GC540-105.1 671 65–2 14 0.23 (25) – – <50 –
GC540-107.1 792 65–2 22 0.29 (20) – – <50 –
GC540-108.1 1006 65–57 25 0.3 (26) – – <50 –
GC540-109.1 1076 65–57 31 0.34 (26) – – 53 –
GC540-109 1105 65–57 22 – – – <100 post-depositional
GC540-109.2 1158 65–57 33 0.33 (14) – – 50 –
GC540-110.1 1177 74–65 35 0.36 (27) – – 59 –
GC540-112.1 1280 74–65 35 0.33 (26) – – 50 –
GC540-112 1341 74–65 40 – – – <85 post-depositional
GC540-112.3 1402 74–65 38 0.43 (8) – – 72 –
GC540-114.1 1554 74–65 41 0.48 (12) – – 80 –
GC540-116.1 1682 74–65 46 0.47 (21) – – 79 –
GC540-118.1 1878 87–74 49 0.49 (7) – – 81 –
GC540-119.1 1978 87–74 54 0.55 (8) – – 91 –
GC540-119 1981 87–74 57 – – – <105 post-depositional
GC540-119.2 2051 87–74 57 0.54 (11) – – 90 –
(continued on next page)
 Hydrocarbon migration through the Clair field 2521

from AFTA (Ma)

(GC540-122 and -123) which provide a discrete range of
Onset of cooling palaeotemperatures in this episode, these are highly consis-
tent with those defined by VR data in adjacent samples (Ta-
ble 4). While there is no timing constraint on the rest of the

50–10
palaeotemperatures defined by VR data in Mesozoic and
50–0

70–0

30–0

25–0

40–0
Cenozoic units, it seems reasonable to assume that all these
–
–

–
–

–
palaeotemperatures represent the Miocene cooling episode
defined from AFTA. These palaeotemperatures, together
Cenozoic episodes

with Miocene values defined by AFTA data in the Palaeo-

temperature (°C)c

zoic section, clearly define arcuate profiles in Fig. 6, sugges-

Max palaeo-

tive of heating due to passage of hot fluids through the

Mesozoic section (cf. Ziagos and Blackwell, 1986). The re-
80–100

95–105
80–90

80–90

85–95

85–95
sults from the 206/9-2 well have been discussed previously
88
94

91

81

by Duddy et al. (1998) who proposed a similar interpreta-

–

–
–

– tion, and reported similar observations from the nearby

205/23-1 well, while the results from well 206/10-1 were re-
ported by Green et al. (1999). Further evidence for palaeo-
from AFTA (Ma)
Onset of cooling

thermal effects due to passage of hot fluids during Cenozoic

times in the WOS region has been presented by Parnell
Stratigraphic ages taken from composite log. All numerical values for stratigraphic ages assigned following (Harland et al., 1989).

et al. (1999, 2005), so such an interpretation is consistent

270–120

270–180

300–50

with regional evidence.

Paleozoic & Mesozoic episodes

>100

Mesozoic palaeotemperatures are identified from AFTA

–
–
–
–
–
–

–
–

only in the deepest samples from the 206/9-2 well. These

palaeotemperatures are interpreted as representing an inter-
mediate cooling episode during the long period of time rep-
temperature (°C)c

resented by the top-Palaeozoic unconformity in these wells

Max palaeo-

(Carboniferous to Late Cretaceous). The most likely expla-

nation for their recognition only in the 206/9-2 well is that
105–115
95–105

90–110

Thermal history interpretation has been carried out using methods outlined by Green et al. (2001).

while this cooling episode affected the Palaeozoic section in

>100
104

111

all four wells, its effects have been overprinted by the Late
99
97
–
–
–
–
–
–

Miocene hot fluid-related heating in the other three wells.

Thus, we interpret this episode as a regional cooling event
experienced by the Palaeozoic section along The Rona
Measured
VR (%)b

Ridge.
0.53 (1)
0.57 (4)

0.55 (7)

0.49 (6)

0.63 (1)

0.59 (1)

0.67 (1)
0.6 (2)

4.4.2. Thermal history reconstruction

–

Using the methods outlined by Bray et al. (1992), we

have estimated the range of palaeogeothermal gradients
temperature

and amounts of additional burial on the top-Palaeozoic

unconformity in the 206/9-2 and 206/10-1 wells that are
Present

Numbers in parentheses show the number of fields measured.

consistent with the Late Permian to Early Triassic palaeo-

(°C)

59
61
63
62
64
63
67
66
70
70
72
75
74
82

temperature constraints derived from AFTA and VR data

in these wells. Results are illustrated in Fig. 7. Given the
similarity between the palaeotemperatures characterising
this episode in the 206/8-7 and 206/8-8 wells and those at
Stratigraphic

similar levels in the other two wells, together with the sim-
age (Ma)a

409–290
409–290
409–290
409–290
409–290
409–290
409–290
409–290

ilarity of the geological setting of each well, we suggest that

87–74
89–87
89–74
89–74
89–74
89–74

a common interpretation is likely to apply to all four wells.

On the basis of results from Fig. 7, we favour an interpre-
tation of the Late Permian to Early Triassic palaeotemper-
atures in terms of deeper burial by around 2 km of
additional section, corresponding to a palaeogeothermal
Depth

2109
2167
2188
2207
2217
2316
2339
2444
2454
2533
2600
2067
2682
2918

gradient of 40 °C/km. This section must have been of

(m)

Carboniferous to Permian age, subsequently removed by

exhumation beginning in the interval 270–230 Ma.
Table 4 (continued)

The Mesozoic palaeotemperatures defined in the 206/9-2

GC540-120.1
GC540-122.1
GC540-122.1
GC540-122.3

GC540-125.1

GC540-127.1

GC540-128.1
GC540-129.1
GC540-129.1
GC540-129.2

well are interpreted as representing an intermediate phase

GC540-123

GC540-126

GC540-127

GC540-130

of cooling prior to the onset of Late Cretaceous deposition,

Sample

although we note that previous studies in the region have

revealed Early Cretaceous palaeo-thermal effects attributed
b
c
a
2522 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533

Fig. 4. Fission track age and mean track lengths in samples from four WOS wells, plotted against depth and present-day temperatures. Also
shown for each well are the variation of stratigraphic age with depth, and the pattern of fission track age and mean track length predicted from
the default thermal history for each well, for apatites containing 0.0–0.1, 0.4–0.5, 0.9–1.0 and 1.5–1.6 wt% Cl. The default thermal history is
the history that would pertain if all units in each well are currently at their maximum post-depositional palaeotemperatures, which provides an
initial reference for interpreting the AFTA data in terms of likely palaeo-thermal effects. Present-day temperatures in each well were calculated
on the basis of corrected BHT values, as explained by Parnell et al. (2005).
 Hydrocarbon migration through the Clair field 2523

Fig. 5. Thermal history solutions are extracted from the AFTA data by comparing modelled parameters from a range of thermal history
scenarios with measured values to define the range of conditions (maximum palaeotemperature and onset of cooling) for which the predictions
match the measured data within 95% confidence limits. The default thermal history for each sample provides the basic framework for this
analysis, with episodes of heating and cooling added as required in order to obtain a good match. An acceptable thermal history solution
should match both the measured fission track age and length distribution for the sample as well as the variation of these parameters with wt.%
Cl within each sample, as shown.

to hot fluid movements (Parnell et al., 1999), so this alterna- the Mesozoic and Cenozoic section due to hot fluid move-
tive explanation should also be borne in mind. ments during the Miocene are shown schematically in
The corresponding reconstructed thermal histories are Fig. 8. Note that since heating in this episode is attributed
illustrated in Fig. 8. The effects of transient heating within to transient fluid movements, the timescale of heating was
2524 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533

Fig. 6. Palaeotemperature profiles in wells 206/9-2 and 206/10-1 derived from the AFTA and VR data in each well (palaeotemperatures are
listed in Table 4). The convex profiles defining the Cenozoic palaeotemperatures suggest that heating was due to the flow of hot fluids. In
contrast, Late Palaeozoic palaeotemperatures in each well can be described by linear profiles, consistent with heating due to a combination of
deeper burial and elevated basal heat flow.

probably much shorter than assumed in estimating the pal-
aeotemperatures quoted in Table 4, and for this reason the
real palaeotemperatures are likely to have been much high-
er than the quoted values. As a rough ‘‘rule of thumb”, each
order of magnitude increase in heating rate corresponds to
a 10 °C increase in the palaeotemperature required to pro-
duce a given degree of annealing (Green et al., 1989b).
4.4.3. Comparison of fluid inclusion and AFTA temperatures
Fluid entrapment temperatures at the time for K-feld-
spar authigenesis within the Palaeozoic section in wells
206/8-7 and 206/8-8 are consistent with temperatures deter-
mined from AFTA. Fluid inclusion homogenization tem-
peratures range from 90.2 to 116.3 °C (Table 1) and
temperatures from AFTA and VR range from 90 to
125 °C (Table 4). This high degree of consistency between
all three techniques strongly suggests that K-feldspar
cementation and entrapment of the inclusions occurred at
or close to the Late Palaeozoic palaeo-burial maximum.
In contrast, fluid inclusion homogenization tempera-
tures from 111.3 to 170.5 °C for inclusions within quartz
cement (Table 1) and values of 129.4 to 170 °C and 118.6
to 159.4 °C for the first and second phase of calcite cements
(Table 1) are much higher than the maximum palaeotem-
peratures derived from AFTA and VR data within the Pal-
aeozoic section (Table 4). Similar observations have been
reported in a number of studies of Paleogene and Mesozoic
sandstones from the UK Atlantic margin (Parnell et al.,
1999; Green et al., 1999; Parnell et al., 2005) and can be
understood in terms of the rapid timescale of heating due
to localised movements of hot fluids (Ziagos and Blackwell,
1986), producing transient heating effects which are too
rapid to produce a detectable effect on the AFTA and VR
systems (Parnell et al., 2005).
Kinetic modelling of fission track annealing and VR
evolution (Parnell et al., 2005) shows that fluids with tem-
peratures up to 200 °C and pulse durations less than
10 5 Ma have no detectable effect on AFTA or VR data,
but are recorded and preserved by fluids entrapped in
inclusions. The precipitation of both quartz and calcite ce-
ment have been linked to periods of rifting and magmatic
activity within the UK Atlantic margin (Wycherley et al.,
2003).
5. DISCUSSION
5.1. TXt data
Laser ablation Ar–Ar dating of authigenic K-feldspar
cement containing characterised fluid inclusions allows inte-
gration (Mark et al., 2006) of the fluid inclusion microther-
mometric and Ar–Ar geochronological data sets (Fig. 9).
The integrated data shows that the timing of K-feldspar
authigenesis in all three wells was similar, as was the salinity
of the precipitating fluids. However, fluid entrapment tem-
peratures were greater in well 206/8-1a than in well 206/8-8
and 206/8-7 (Fig. 9). The simplest and most reasonable
explanation for this range of fluid entrapment temperature
is that the rocks in 206/8-1a had undergone enhanced burial
and subsidence relative to those in 206/8-7 and 206/8-8,
 Hydrocarbon migration through the Clair field
Fig. 7. From the variation of Late Palaeozoic palaeotemperatures
with depth in the 206/9-2 and 206/10-1 (Figure 6, Table 4), the
range of palaeogeothermal gradients and corresponding amounts
of additional burial (subsequently removed by erosion) can be
defined (Bray et al., 1992). Higher palaeo-gradients correspond to
lower amounts of removed section, and vice versa, resulting in a
hyperbolic ellipsoid of allowed (at the 95% confidence level) values
for each well, as shown by the shaded zones.
producing higher temperatures in line with the geothermal
gradient.
5.2. Ar-loss and excess Ar
Ar–Ar data show that K-feldspar authigenesis occurred
at 247 ± 3.3 Ma. As K-feldspar subgrains commonly leak
Ar at low temperatures (Lee and Parsons, 2003), the possi-
bility that the Ar–Ar data does not represent K-feldspar
growth, but records a later thermal resetting or closure
age must be considered. In order to test the Ar–Ar ages
for thermal resetting, a thermal history derived from the
AFTA and fluid inclusion microthermometric data (well
206/8-7) was entered into a piecewise linear Ar-diffusion
Fig. 8. Reconstructed thermal histories for the 206/9-2 and 206/10-1 wells, based on the AFTA and VR data in each well. See text for details.
2525
model (Wheeler, 1996). No excess Ar was inputted into
the model. Spherical subgrains with radii of 1 lm and
500 nm, sizes determined from TEM, were tested
(Fig. 10). The Ar-diffusion model shows that the 2 lm sub-
grains are reset from 247 to 238 Ma, a 9 Ma difference, and
1 lm subgrains are reset from 247 to 222 Ma, a 25 Ma dif-
ference. The TEM results do not permit the ratio of large to
small subgrains within each laser ablation area to be deter-
mined due to petrographic scaling issues. However, the like-
lihood is that ablation areas contained varying ratios of 2
and 1 lm subgrains. Assuming a 1:1 ratio of 2 and 1 lm
subgrains we can estimate an overall resetting of Ar–Ar
ages by approximately 17 Ma, giving true growth ages of
the K-feldspar overgrowths in the Clair well of 264 Ma.
Relative to the individual Ar–Ar error for each data point,
the maximum effect of Ar-loss from subgrains on the indi-
vidual determined mineral growth ages is not significant.
Furthermore, because the high temperature fluid pulses re-
corded by fluid inclusions in authigenic quartz, calcite ce-
ment and calcite veins have not been recorded by the
AFTA, these episodes are inferred to have started rapidly
and to have been short-lived (Parnell et al., 2005). The
Ar-diffusion model uses the integrated AFTA-fluid inclu-
sion thermal history for which periods of 0.5 Myr have been
assigned to represent the duration of the fluid pulse events
at 90 and 60 Ma (timing discussed later). If the duration
of the fluid pulses were shorter than 0.5 Myr, for example
in the order of 0.1 Myr, then the Ar–Ar ages would only
have been reset by 3 to 4 Ma, assuming a 1:1 ratio of 2–
1 lm subgrains.
Ablation volumes contained varying numbers of fluid
inclusions. From visual two-dimensional analysis and
mathematical conversion to three-dimensions (Mark
et al., 2005), it has been estimated that the K-feldspar over-
growths contain between 0.1 and 1% (by volume) fluid
inclusions. Crustal fluids typically contain excess Ar con-
centrations that range from 0.01 to 1 ppm (Kendrick
et al., 2002), thus it is possible to estimate the contribution
of excess Ar to measured ranges in Ar–Ar ages of the K-
feldspar overgrowths, and approximation for a ‘worse case
2526 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533
Fig. 9. TXt cross-plot showing fluid inclusion homogenization temperature data versus Ar–Ar age for both aqueous- and oil-bearing fluid
inclusions in K-feldspar overgrowths. Salinity data for individual aqueous fluid inclusions is referenced to the data points.
scenario’ is required. Assuming that all ablation areas con-
tain 1% (by volume) fluid inclusions and the fluid trapped
within the inclusions contains 1 ppm excess Ar, the growth
age would be increased by 1.29 Ma (Mark et al., 2005).
Hence, in summary, due to the absence of data describ-
ing fluid episode durations (for which we modelled a worst
case scenario) and considering the possible effects of fluids
trapped within fluid inclusions containing 1 ppm excess
Ar, the true age of the K-feldspar overgrowths lies between
247 and 264 Ma. The variation in Ar–Ar age is still well
within the analytical error of the individual Ar–Ar ages
(Table 2). It is important to note that the K-feldspar over-
growth Ar–Ar age, 247 Ma, is the minimum age of feldspar
precipitation and potential effects from thermal Ar-loss and
excess Ar would increase the K-feldspar overgrowth age.
5.3. Authigenesis
Authigenic K-feldspar was precipitated within the reser-
voir between 247 and 264 Ma. Fluid entrapment temper-
atures determined from aqueous inclusions (Table 1) show
that the precipitating fluids were of moderate temperature
(90 to 116 °C) and moderate salinity (3 to 7 wt.% NaCl
eq.). The thermal history curve for well 206/8-7 (Fig. 5)
shows that determined fluid entrapment temperatures are
approximately in line with temperatures determined from
AFTA. A simple temperature-burial depth conversion,
assuming an elevated continental rift basin geothermal gra-
dient of 30–90 °C km 1 (Roberts, 1985), indicates that the
Clair Group was buried to between 1.14 and 3.43 km
(assuming an arithmetic mean value for Th). These esti-
mates of burial depth are also compatible with the predic-
tions of recent computer modelling that shows K-feldspar
authigenesis takes place at burial depths of 1 to 3 km
(Makowitz et al., 2006). Marine waters (3.5 wt.% NaCl)
are insufficiently saline to account for the measured salini-
ties of inclusions within the K-feldspar overgrowths. This
implies that basinal brines occupied pore spaces within
the Clair reservoir at the time of K-feldspar cementation.
With respect to K-feldspar authigenesis, the critical
experiments describing isochemical pore fluid evolution
were performed by Orville (1963). Orville measured the
composition (Na:K ratio) of 2 M brines (typical oilfield flu-
ids) in equilibrium with alkali feldspars at 2 kbar PH2O. The
experiments most relevant to diagenesis are the low-temper-
ature runs down to 450 °C and although these tempera-
tures are higher than those witnessed during diagenesis, it
has been shown that extrapolation to low temperatures
and pressures more consistent with diagenesis is possible
(Kastner and Siever, 1979). In low temperature runs, two
feldspars (albite and K-feldspar, typical of an arkose) were
stable due to the alkali feldspar solvus and this is an appro-
priate comparison to the subarkose rocks found within the
Clair Group. For a large range of bulk feldspar composi-
tions the Na:K ratio in the fluid is buffered (fixed) by ion
exchange of alkali metals between the brine and the feld-
spar. The result is that fluids at lower temperatures have
higher Na:K ratios than at higher temperatures and so, as
the fluid cools it becomes more sodic and it does this by dis-
solving albite and precipitating K-feldspar, even though the
fluid has an extremely high Na:K ratio already. If the fluid
is heated it becomes more potassic, so it precipitates albite
in place of K-feldspar. Albitization is a common process
that occurs in the deeper parts of sedimentary basins (Lee
and Parsons, 2003). This isochemical mechanism shows
that there is no need to transport large amounts of Al2O3
and SiO2 around the system, a local Na–K replacement
reaction can operate effectively enough to account for depo-
sition of authigenic K-feldspar. The consistency between
palaeo-fluid temperatures determined from AFTA and
VR data and temperatures calculated directly from fluid
inclusion microthermometry, have been attributed to burial
and heating due to the regional geothermal gradient, not
flushing of hot fluids. This observation is consistent with
 Hydrocarbon migration through the Clair field 2527

Fig. 10. Ar loss (DIFFARG) model showing the response of 1 and 2 lm subgrains to a reconstructed thermal history. DIFFARG is a
forward projection model, 0 Ma corresponds to 247 Ma and 247 Ma corresponds to present day. (A) Thermal history determined from AFTA
(Fig. 5) and fluid inclusion data (Table 1) against which K-feldspar subgrain Ar-retention is tested. The two spikes at 90 and 60 Ma are
discussed in text. (B) Cross-plot showing modelled Ar concentration gradient in a typical 2 lm subgrain. (C) Cross-plot showing that 2 lm
subgrains are reset from 247 Ma on the time axis to 238 Ma on the apparent age axis. The subgrains have potentially been reset by 9 Ma. (D)
Cross-plot showing modelled Ar concentration gradient in a typical 1 lm subgrain. (E) Cross-plot showing that 1 lm subgrains are reset from
247 Ma on the time axis to 222 Ma on the apparent age axis. The subgrains have potentially been reset by 25 Ma. See text for further
discussion.

an isochemical reaction controlling pore fluid composition
as proposed above.
Precipitation of authigenic quartz followed K-feldspar.
Fluid entrapment temperatures determined from aqueous
inclusions (Table 1) suggest that the temperatures of the
precipitating fluids ranged from moderate to high (111
to 170 °C) and salinities were low (0.5 to 4 wt.% NaCl
eq.). Although Aplin et al. (1993) suggest it is unusual for
quartz cementation to occur within reservoirs at low tem-
peratures and fluid salinities, numerous studies since have
clearly demonstrated that these processes can occur over
a wide range of burial depths, temperatures, pressures
and fluid salinities (Walderhaug, 1994; Worden and Morad,
2000 and references within). Thermal histories (Fig. 8) show
that the Clair wells never reached burial temperatures as
high as indicated by the fluid inclusions. Anomalously
high-temperature fluids may have mediated diagenesis in
other basins of the WOS region and are the likely sources
of high fluid temperatures in the Clair field (Green et al.,
1999; Parnell et al., 1999; Wycherley et al., 2003). Migration
of hot fluids within WOS could be related to either Late
Jurassic-Early Cretaceous rifting or Tertiary magmatism
(Nadin et al., 1997; Clift, 1999; Dean et al., 1999; Naylor,
1999). Deformation that produced the deformation bands
within the Clair reservoir post-dates quartz cementation
and has been confidently related to Late-Cretaceous fault-
ing (85 to 65 Ma; Coney et al., 1993). The data shows that
quartz cementation occurred prior to deformation, proba-
bly during Cretaceous rifting (90 Ma). Although hot fluid
pulses were migrating through the region, the low solubility
of silica at diagenetic temperatures and the large fluxes of
water correspondingly required to transport sufficient silica
to support continued authigenesis (108 cm3 water passing
through each cm2 of rock; Worden and Morad, 2000), a lo-
cal source of silica is more likely than large-scale transport
from elsewhere in the basin. The replacement of K-feldspar
2528 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533
by kaolinite and/or illite yields quartz (Harris and Fullagar,
1989), as does the illitization and chloritization of smectite
(Boles and Franks, 1979), pressure dissolution within
quartz-rich sandstones (Bjorkum, 1996; Oelkers et al.,
2000) and dissolution of amorphous silica (Vagle et al.,
1994; Hendry and Trewin, 1995). Any or all of these pro-
cesses may have been catalysed or enhanced by invasion
of the Clair Group by pulses of hot fluids.
Two phases of calcite authigenesis and calcite veining
followed quartz cementation, the first ferroan-rich. Fluid
entrapment temperatures determined from C1 aqueous
inclusions (Table 1) show that the precipitating fluids ran-
ged from moderate to high temperatures (129 to 170 °C)
and low to moderate salinities (1.4 to 5.2 wt.% NaCl
eq.). Fluid entrapment temperatures determined from C2
aqueous inclusions (Table 1) show that the precipitating flu-
ids ranged from moderate to high temperatures (118 to
160 °C) and low to moderate salinities (1 to 5.3 wt.%
NaCl eq.). Because deformation bands contain unbrecciat-
ed C1 cement, calcite authigenesis commenced post-defor-
mation. Thermal histories show that the Clair field never
reached burial temperatures of 160–170 °C (Fig. 8) and
without stable oxygen isotope the source of the fluid that
precipitated C1 and C2 can not be determined. Pay et al.
(2000) and Baron et al. (2008) show that calcite comprises
up to 30% of the whole rock composition of Clair reservoir
sands and thus requires an extensive source of carbonate.
However, because source material for calcite is limited
within the WOS, it is likely that either intrusion of a gabbro
pluton at 68 Ma (Hitchen and Ritchie, 1987) and/or ter-
tiary magmatic activity (60 Ma; Clift, 1999) induced ba-
sin-scale fluid migration. The extensive fracture network
within block 206 may have directed the fluids into the Clair
reservoir where calcite was precipitated. A change in com-
position (ferroan to non-ferroan) probably reflects exhaus-
tion of the iron source or change in Eh of the fluids.
5.4. Oil inclusion fluorescence
Oil inclusion fluorescence colours have been used as a
qualitative guide for the thermal maturity of migrating oils
(Stasiuk and Snowdon, 1997; Bradshaw et al., 1998; O’Reil-
ly et al., 1998) and are directly related to oil density (API
gravity; Stasiuk and Snowdon, 1997; Parnell et al., 1999).
Studies have shown that oil inclusions of higher API gravity
and maturity fluoresce in the blue end of the visible spec-
trum, whereas those of lower API gravity and maturity
fluoresce in the red region (McLimans, 1987; Bodnar,
1990). Largely the relationship is based on observations
made concerning the fluorescence properties of crude oils
(Downare and Mullins, 1995; Ralston et al., 1996). Aro-
matic compounds are the main fluorescing components of
oil and although fluorescence in the first instance depends
on chemical composition, which is primarily controlled by
maturity, several other processes can affect chemical com-
position (George et al., 1997). Numerous studies have dem-
onstrated that oils fractionate during adsorption onto
charged mineral surfaces, leading to enrichment in polar
compounds relative to the true parent oil composition
(Pang et al., 1998). Support for a trapping control comes
from work on synthetic fluid inclusions (Palmer et al.,
1999), in which trapping of single oil in the laboratory pro-
duced oil inclusions of variable fluorescence colours. This
work revealed the presence of blue-fluorescing inclusions
with small quantities of red-, yellow-, and orange-fluoresc-
ing inclusions. The commonly invoked explanation for this
phenomenon is a local generation of subordinate low matu-
rity oil, with main charge high maturity oil represented by
the dominant inclusion population (Lisk et al., 1993; Lisk
and Eadington, 1994). The effects of trapping fractionation
may potentially vary for different mineral hosts and contin-
ues to be investigated (George et al., 2001; Oxtoby, 2001).
O’Brien et al. (1996) used samples collected from the Timor
Sea to show that water washing of oil samples in reservoirs
produces molecular and gross fractionation of oils, lower-
ing specific gravity and therefore also altering the fluores-
cence properties of the oil. Another potential control on
the fluorescence properties of oil is the biodegradation of
hydrocarbons prior to entrapment. Bailey et al. (1973) dem-
onstrated that biodegradation decreases the aliphatic/aro-
matic hydrocarbon ratio and increases the proportion of
polar compounds. Any aliphatic/aromatic ratio changes
would affect UV fluorescence emission colour. The poten-
tial fluorescence characteristics of oil inclusions can also
be influenced by inorganic fluorescence from the host min-
eral. Trace amounts of transition metals and rare earth ele-
ments in mineral hosts may contribute to inorganic
fluorescence which could be a further control on the fluo-
rescence character of oils inclusions (Wang et al., 1997; Bez-
ouska et al., 1998).
The presence of hydrocarbon fluid inclusions with differ-
ent fluorescence colours (yellow, orange, blue, white) en-
trapped coevally in quartz and calcite in the Clair field is
thus open to interpretation. However, the multiple fluores-
cence colours coupled with crush-leach analysis on hydro-
carbon fluid inclusions from the Clair field (Scotchman
et al., 1998), which showed the presence of oils of varying
API gravity, suggests that mixing of hydrocarbons of differ-
ent maturities from different sources (Bailey et al., 1987;
Rooney et al., 1998; Scotchman et al., 1998) was occurring.
The effect of oil emplacement on authigenesis rates with-
in sandstones has been debated over previous years, partic-
ularly with reference to the retardation of quartz
precipitation during oil emplacement (Walderhaug, 1994;
Bjorkum et al., 1998; Worden et al., 1998; Marchand
et al., 2001). The presence of oil-filled fluid inclusions within
primary settings in feldspar, quartz and calcite cement with-
in samples from the Clair reservoir, suggest that cementa-
tion continued after oil emplacement. However, these
occurrences only indicate that oil was present within the
reservoir during authigenesis and it is not possible to deter-
mine if cementation rate was inhibited during oil emplace-
ment from the study data.
5.5. Hydrocarbon charging
Hydrocarbon charging in the Clair field was synchro-
nous with K-feldspar, quartz and calcite cementation. The
data records only episodes of oil-charging that were accom-
panied by pore fill cementation or veining. Current under-
 Hydrocarbon migration through the Clair field
standing concerning charging of the Clair field is based on
models that show multi-stage charging from the Jurassic-
Cretaceous source rocks that reside to the NW in the
FSB (Bailey et al., 1987; Rooney et al., 1998; Scotchman
et al., 1998; Carr and Scotchman, 2003; Scotchman et al.,
2006). It is important to note that K-feldspar overgrowths
contain only blue fluorescing hydrocarbons, and this is
interpreted to represent the first recorded oil charge event
in the Clair field. However, as K-feldspar overgrowths con-
tain primary hydrocarbon fluid inclusions and precipitated
between 247 and 264 Ma, data clearly indicate that hydro-
carbon generation, migration and accumulation within the
UK Atlantic margin must have occurred prior to deposition
of the Jurassic-Cretaceous source rocks in the FSB. Thus an
oil-mature Palaeozoic source rock must have been present
within the WOS region whilst K-feldspar authigenesis was
occurring.
The only Palaeozoic source rocks identified within the
region are the Devonian Middle ORS, East Greenland
Upper Carboniferous and Upper Permian. The Upper
Permian marine black shales deposited in the Zechstein
sea (256–248 Ma) would have been immature at the time
of oil entrapment. Lacustrine shales deposited during the
Westphalian (315–305 Ma) are a feasible source rock.
AFTA data and geochemical modelling (Clift and Turner,
1998) show sediments offshore East Greenland began to
cool from 90 to 100 °C at approximately 280 Ma. However,
considering their distance from the Clair reservoir, the time
for maturation, generation and expulsion of hydrocarbons,
and the time for migration from source to trap, the Carbon-
iferous East Greenland source does not appear to be a
strong candidate for supply of the oil-charge at 264–
247 Ma. The Devonian ORS lacustrine deposits are the only
sensible option remaining and the timing of thermal matu-
ration is a much more attractive option when compared to
the East Greenland source rocks. Thermal models recon-
structed from AFTA and VR data (well 206/9-2 and 206/
10-1; Fig. 8) show that ORS sedimentary rocks WOS were
heated to a maximum of 130 °C during burial, temperatures
high enough to push organic-rich lacustrine facies into the
oil window (Trewin, 1989). Although palaeogeographic
reconstructions of Middle ORS strata offshore Shetland is
poor, the presence of Middle ORS lacustrine facies through-
out the Orkney and Shetland Isles show that potential
Devonian source rocks were deposited throughout the re-
gion, relatively close to the Clair field. Two previously pub-
lished thermal burial histories (Astin, 1990; Parnell et al.,
1998) also show that Devonian lacustrine facies throughout
Orkney (150 km south from the Clair field; Fig. 1) entered
the oil window between 350 and 340 Ma, remaining oil-ma-
ture until between 300 and 280 Ma. Furthermore, Clift and
Turner (1998) conducted a detailed AFT study throughout
the Scottish Highlands, Orkney and Shetland Isles. Mod-
elled geothermal histories for samples from Orkney and
Shetland showed cooling from temperatures in excess of
110 °C at 350 Ma, to approximately 80 °C by 200 Ma.
The data supports the hypothesis put forward in this man-
uscript that oil was generated from the Devonian source
rocks north of the British Isles and charged the Clair reser-
voir during the Early Permian.
2529
Current petroleum system models for WOS are therefore
incomplete and a source rock was generating oil during the
Late Palaeozoic. In the absence of geochemical data from
the oil entrapped within the inclusions that reside in K-feld-
spar overgrowths, it is not possible to directly correlate the
oil charge to a source rock. However, the timing of thermal
maturation of Middle ORS lacustrine facies throughout
Orkney and Shetland is consistent with the TXt data deter-
mined from K-feldspar overgrowths in the Clair field.
Hydrocarbon charging of the Clair reservoir at the time
of K-feldspar authigenesis can be linked to maturation of a
Palaeozoic source rock as discussed above. However,
charging of the reservoir at times of quartz and calcite
cementation and veining, show from the fluorescence char-
acters of the oil in the fluid inclusions and geochemical
analysis of bitumens (Rooney et al., 1998; Scotchman
et al., 1998), that mixing of oil from different sources had
occurred. Hydrocarbon charging of the Clair field during
quartz and calcite cementation and veining is compatible
with the standard model depicting hydrocarbon genera-
tion-migration from a Jurassic source throughout the UK
Atlantic margin (Bailey et al., 1987). Thermal burial history
modelling using stratigraphical and VR data from well
206/5-1 (Mark et al., 2005), the closest well to the Clair
field that contains Late Jurassic-Early Cretaceous source
rocks, shows that they became early oil mature (0.5–0.7%
Ro) at 120 Ma. The Late Jurassic source rocks were
exhausted with respect to oil generation at 70 Ma,
whereas Early Cretaceous source rocks have remained oil
mature up to modern day (Mark et al., 2005). As source
rocks in the FSB have remained oil-mature from 120 Ma
to modern day, the degree of thermal maturity has in-
creased with continued burial and subsidence over time
(Bailey et al., 1987). Increased thermal maturity and mixing
of hydrocarbons from multiple Devonian and Jurassic
source rocks can account for variability in oil-inclusion
fluorescence and geochemistry (Rooney et al., 1998; Scotch-
man et al., 1998).
6. CONCLUSIONS
The TXt data presented here show that oil was gener-
ated, then migrated throughout the UK Atlantic margin
during the Late Palaeozoic. Thermal history data suggest
that Middle ORS Devonian source rocks within the region
were oil-mature prior to the Permian and their maturation
could account for the presence of oil inclusions within K-
feldspar overgrowths in the Clair field between 264 and
247 Ma. From the TXt data it is not possible to determine
if oil was trapped and accumulating in the Clair field during
the Late Palaeozoic, or whether the Clair field and The
Rona Ridge actually acted as migration pathways.
K-feldspar authigenesis occurred in the Late Palaeozoic
during peak burial of the Devonian-Carboniferous red-bed
sediments. Calculated temperatures of precipitating fluids
are commensurate with temperatures predicted by the re-
gions geothermal gradient and are not a product of flushing
of hot fluids throughout the margin. Quartz and calcite
authigenesis occurred during the Mesozoic and Cenozoic,
respectively. Authigenesis was related to transient heating
2530 D.F. Mark et al. / Geochimica et Cosmochimica Acta 72 (2008) 2510–2533
by pulses of hot fluid. Thermal history data show that inter-
mittent flow of hot fluid throughout the UK Atlantic mar-
gin was responsible for complex diagenetic sequences in
Tertiary reservoirs, and occurred during both the Cenozoic
and Mesozoic. These events were presumably related to epi-
sodic rifting of the UK Atlantic margin.
In summary, this study shows that by integrating TXt
data into a regional model incorporating thermal con-
straints from AFTA and VR data, it is possible to develop
complex oil-show models. The novel determination of TXt
data through analysis of authigenic K-feldspar represents a
powerful tool for reconstructing palaeo-fluid flow within
sedimentary basins and should find many applications in
regional exploration, especially as hydrocarbon resources
continue to dwindle during the 21st Century.
ACKNOWLEDGMENTS
This work was supported by the Natural Environment Re-
search Council (3220/GL021/ RGA0782). We thank John Still
and James Schwanethal for technical assistance. We are also grate-
ful to A. Craven for access to the FIB-TEM facilities in Glasgow
University and C. How for help with microscope operation. Asso-
ciate Editor E.H. Oelkers is thanked for comments leading to
improvement of this manuscript. Two reviewers, I. Scotchman
and H. Shaw are also thanked for detailed reviews, comments
and constructive suggestions.
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