Organic Geochemistry 40 (2009) 87–110

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

Origin of petroleum in the Neoproterozoic–Cambrian South Oman Salt Basin

E. Grosjean a,*, G.D. Love a,1, C. Stalvies b, D.A. Fike a, R.E. Summons a
a
Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA
b
Newcastle Research Group, University of Newcastle, Newcastle upon Tyne NE1 7 RU, UK

a r t i c l e i n f o a b s t r a c t

Article history: The South Oman Salt Basin (SOSB) is host to the world’s oldest known commercial deposits. Most of the
Received 3 December 2007 South Oman oils have been proven to be associated with the source rocks of the Neoproterozoic to Cam-
Received in revised form 25 August 2008 brian Huqf Supergroup, but the assignment of oils to specific Huqf intervals or facies has been hampered
Accepted 5 September 2008
by the geochemical similarity of the organic matter across the entire Huqf sequence, possibly as a con-
Available online 10 October 2008
sequence of limited change in the local palaeoenvironment and biota over the time of its deposition. This
study was conducted to establish improved correlations between organic-rich rock units and reservoir
fluids in the SOSB through detailed molecular and isotopic analysis of the Huqf Supergroup, with special
emphasis directed towards understanding the Ara carbonate stringer play.
Unusual biomarkers, tentatively identified as A-norsteranes, show distinctive patterns among carbon-
ate stringer oils and rocks different from those observed in Nafun sediments and Ara rocks from the Athel
basin. These putative A-norsteranes form the basis for new oil-source correlations in the SOSB and pro-
vide for the first time geochemical evidence of a self-charging mechanism for the carbonate stringer play.
The paucity of markers specific to the Nafun Group (Shuram, Buah and Masirah Bay formations) con-
founds attempts to quantify their respective contributions to Huqf oil accumulations. Nafun inputs can
only be determined on the basis of subtle differences between Nafun and Ara biomarker ratios. The most
useful geochemical characteristics delineating Nafun Group organic matter from Ara Group intra-salt
source rocks included: low relative abundance of mid-chain monomethyl alkanes (X-compounds); low
relative abundance of gammacerane, 28,30-dinorhopane, 25,28,30-trinorhopane and 2-methylhopanes;
low C22T/C21T and high C23T/C24T cheilanthanes ratio values. Based on these parameters, molecular evi-
dence for major contributions of liquid hydrocarbons from Nafun Group sediments (Shuram, Buah and
Masirah Bay formations) is lacking. Our results suggest that the majority of SOSB hydrocarbon accumu-
lations originate from within the Ara group, either from the carbonate stringers or from the package of
sediments that comprises the Thuleilat, Athel Silicilyte and U shale formations. Subtle aspects of the com-
position of some carbonate stringer and post-salt Huqf oils could suggest some degree of sourcing from
the Nafun rocks but stronger evidence is needed to confirm this.
Crown copyright Ó 2008 Published by Elsevier Ltd. All rights reserved.

1. Introduction ized by carbon isotope values near 30‰ and C27-dominated ster-
anes. Both oil types show conspicuous mid-chain monomethyl
The South Oman Salt Basin (SOSB) is an unusual petroleum-pro- alkanes, trivially named ‘‘X compounds”, considered characteristic
ducing domain as it is host to the world’s oldest known commer- of Precambrian-Cambrian source rocks (Fowler and Douglas, 1987;
cial oil deposits. Two major oil types, the ‘Huqf’ and the ‘Q’ oils, Summons et al., 1988a,b; Bazhenova and Arefiev, 1997). As the or-
were recognized over 20 years ago and are clearly distinguished ganic matter (OM) within the Huqf source rocks displays similar
on the basis of carbon isotopic composition and sterane carbon characteristics to the Huqf oils, a straightforward correlation has
number distributions (Grantham, 1986; Grantham et al., 1987). been established between these oils and the Huqf Supergroup
The Huqf oils have abnormally low carbon isotope ratio values (Grantham, 1986; Grantham et al., 1987; Terken et al., 2001). On
[typically 36‰ VPDB (Vienna Pee Dee Belemnite)] and a strong the other hand, the origin of the Q oils, clustered to the north of
predominance of C29 steranes, in contrast to the Q oils character- the SOSB and in the basins to the north, is a matter of speculation
as the source rock remains unproven. A Precambrian source for the
* Corresponding author. Present address: Geoscience Australia, GPO Box 378, latter was proposed on the basis of the mid-chain monomethyl al-
Canberra, ACT 2601, Australia. Tel.: +61 2 6249 9017; fax: +61 2 6249 9961. kane presence and of their spatial and stratigraphic distributions
E-mail addresses: Emmanuelle.Grosjean@ga.gov.au, egrosjea@bigpond.net.au (Grantham et al., 1987).
(E. Grosjean).
1
Studies to date have established the uniqueness of Oman’s old
Present address: University of California Riverside, 900 University Avenue,
Riverside 92521, USA. Huqf petroleum systems. However, they have not provided suffi-

0146-6380/$ - see front matter Crown copyright Ó 2008 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2008.09.011
88 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

cient resolution to unequivocally unravel specific source to charge 2. Geological setting

relationships needed to determine which, if any, carbonate reser-
voirs in the Huqf Precambrian–Cambrian Ara (Reinhardt et al., 2.1. Stratigraphy and age constraints
1998; Al-Siyabi, 2005) are self-charged and whether and where
older high quality, pre-Ara Precambrian source rocks of the Nafun The South Oman Salt Basin, located at the southeastern edge of
group have contributed significantly to the charge. These are key the Arabian Peninsula, is developed on Pan-African basement and
questions which have a direct impact on the exploration of inter- contains a Neoproterozoic–Early Cambrian sedimentary succes-
and pre-Ara plays in the Oman salt basins. Improved correlations sion known as the Huqf Supergroup (Gorin et al., 1982; Loosveld
between organic-rich rock units and reservoir fluids in the SOSB et al., 1996). The Huqf Supergroup begins with a thick siliclastic
would help establish the volumetric contributions of potential unit (the Ghadir Manqil Fm. of the Abu Mahara Group), followed
Ara and Nafun source rocks to the existing accumulations and pro- by two clastic-carbonate cycles (the Masirah Bay and Khufai, and
vide a framework for basin modelling to reduce charge risk and en- the Shuram and Buah formations of the Nafun Group) and termi-
hance prospectivity. nated by the chert-carbonate evaporite succession of the Ara
The assignment of ‘Huqf’ oils to specific Huqf intervals or facies Group (Grotzinger et al., 2002; Fig. 1). Recent studies provide a
is hampered by an overall geochemical homogeneity of the OM detailed sedimentological framework of the Masirah Bay (Allen
across the whole Huqf sequence, possibly a consequence of limited and Leather, 2006), the Shuram (Le Guerroué et al., 2006a,b)
biological diversity or limited environmental evolution over the and the Buah (Cozzi et al., 2004; Cozzi and Al-Siyabi, 2004) for-
time of deposition. Biomarker analysis of oils and rocks using gas mations of the Nafun Group. Initial U/Pb geochronology, stable
chromatography–mass spectrometry (GC–MS) methods with isotope chemostratigraphy, palaeontology and geological inter-
selected ion monitoring (SIM) have largely failed to unambigu- pretation identified the Ghadir Manqil Fm. as a Sturtian age (ca.
ously and conclusively type oil to source rock intervals because 723 Ma) glacio-marine diamictite (Brasier et al., 2000) and car-
of the remarkable uniformity of the sterane and triterpane bonates and shales within the A4 unit of the Ara Group as being
distributions. deposited at the Neoproterozoic–Cambrian boundary at ca.
In order to improve our understanding of SOSB petroleum sys- 542 Ma (Amthor et al., 2003). New geochronological constraints
tems, a detailed organic geochemical study has been performed (Bowring et al., 2007) indicate that the Huqf Supergroup was
via thorough analysis of selected South Oman oils and Huqf rock deposited on basement rocks of ca. 840 to 810 Ma age and that
samples. Conventional organic geochemical methods commonly two glacial episodes are recorded at ca. 713 and < 645 Ma. Ash
applied to Phanerozoic petroleum systems are not necessarily beds in the basal Ara Group (A0 carbonate) record an age of ca.
optimal for such a study owing to the exceptionally old and unu- 547 Ma for carbonate rocks that occur above strata marked by
sual OM. Accordingly, we sought to identify geochemical indices pronounced negative ( 12‰) to positive excursion (+4‰) in car-
tailored to these particular petroleum systems. Special emphasis bon isotope composition of carbonates. Further overlying Ara
was directed towards the understanding of the Huqf oils origin. strata contain ash beds within the basal A3C unit (ca. 543 Ma),
While the Q oils geochemistry is briefly presented, the under- the upper A3C unit (ca. 542 Ma) and the basal A4C unit (ca.
standing of their charge is the focus of a companion paper where 541 Ma), which approximates the Ediacaran–Cambrian boundary
new findings about their potential source rocks are presented. in Oman. The 16‰ carbon isotope excursion occurs within the

Stratigraphy Stratigraphic Data

Age S'group Group Formation
Andam Cambrian
Mahatta
Miqrat Fauna
Haima

Humaid
Amin
Haradh
Nimr
Cambrian

13
Karim δ C‰
Dhahaban -10 +10
A6
Al Noor
A5
Ara
A4 U/Athel/Thuleilat 541 Ma
A0 - A3 Birba
Cloudina

Buah
Huqf
Neoproterozoic

Shuram
Nafun
< 580 Ma
Khufai

Masirah Bay
c. 635 Ma
Abu
Ghadir Manqil
Mahara
Crystalline Basement c. 800-850 Ma

Fig. 1. Generalized stratigraphic column for Neoproterozoic and Early Cambrian strata of SOSB (modified from Amthor et al., 2005).
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 89

Shuram Fm., which has a firm maximum age of ca. 620 Ma, pro- 2.2. Palaeogeography
vided by the age of two detrital zircons in the basal part of the
unit. The ‘Shuram’ excursion is a useful marker for global chemo- A detailed description of the palaeogeography and stratigraphy
stratigraphic correlation (Halverson et al., 2002, 2005; Condon of the Ara group is provided by Amthor et al. (2005) and Schröder
et al., 2005). Furthermore, patterns in sulfur isotopes (sulfate and Grotzinger (2007). Briefly, during deposition of the Ara group,
and pyrite) and carbon isotopes (carbonate and organic carbon) the SOSB was subdivided into three separate palaeogeological do-
through the Nafun and Ara sequences indicate that these mains: two platforms, the North and South Carbonate Platforms,
sediments were deposited during the period in which the separated by a deeper stratified basin (Athel Sub-basin; Fig. 2) with
Ediacaran ocean became fully oxygenated (Fike et al., 2006). water depth potentially of several hundred meters in the deeper

Fig. 2. Map of Oman showing main tectonic elements, positions of the salt basins and the structural setting of the South Oman Salt Basin (modified from Bowring et al., 2007).
90 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

depocentres (Mattes and Conway Morris, 1990; Amthor et al., 3.2. Biomarker analysis
1998). The carbonate platforms consist of a cyclic succession of
up to seven carbonate units, or ‘stringers’, each sandwiched within Gas-chromatography (GC) was carried out with a Hewlett–
sulfate and halite evaporites (Mattes and Conway Morris, 1990). Packard 6890 chromatograph in splitless injection mode, equipped
The tectono-eustatic evaporite–carbonate cycles are termed A0 to with a flame ionization detector (FID; 300 °C) and a Chrompack
A6 from bottom to top. In the basin centre, the stratigraphic equiv- CPSil-5CB fused silica column (60 m  0.32 mm i.d., 0.25 lm film
alent of the A4C unit consists of two organic-rich shale units, the U thickness). He was used as carrier gas. Typical temperature pro-
Shale Fm. and the Thuleilat Fm., bracketing the unique siliceous gramme was 60 °C (held 2 min) to 100 °C (10 °C/min) and to
rocks of the Athel Silicilyte (aka Al Shomou Silicilyte; Amthor 315 °C (4 °C/min; held 30 min). Alkanes such as n-alkanes, pristane
et al., 2005; Schröder and Grotzinger, 2007). Towards the eastern (Pr), phytane (Ph) and monomethyl alkanes (MMAs) were quanti-
flank, stringers form an almost continuous carbonate platform fied using 3-methylheneicosane (ai-C22) as internal standard.
due to salt withdrawal. Full scan gas chromatography–mass spectrometry (GC–MS) was
The rocks deposited within the Ara Group are commonly carried out either with a Hewlett–Packard 5973 mass spectrometer
called intra-salt rocks, whereas rocks deposited before, including connected to a Hewlett–Packard 6890 gas chromatograph
those of the Nafun Group, are referred to as pre-salt rocks. Here- equipped with a Chrompack CPSil-5CB fused silica column
after, Ara source rocks deposited in the Athel Basin are referred (60 m  0.32 mm 0.25 lm film thickness), or with a Autospec Ulti-
to as Athel intra-salt rocks, as opposed to the Ara carbonate ma mass spectrometer connected to a Hewlett–Packard 6890 gas
stringers. chromatograph (J&W Scientific DB-1 column, 60 m  0.25 mm
i.d., 0.25 lm film thickness). Samples were injected in pulsed split-
2.3. Oil occurrences less mode. The oven was programmed from 60 °C (held 2 min) to
150 °C at 10 °C/min and at 3 °C/min to 315 °C (held 24 min). Mass
Oils typed to the Huqf Supergroup source rocks, the so-called spectra were produced at 70 eV and He was the carrier gas. For de-
Huqf oils, are found within a number of structures in the Ara car- tailed GC–MS analysis of steranes and hopanes, samples were ana-
bonate stringers, in the intra-salt Athel Silicilyte and in reservoirs lyzed using the Autospec Ultima mass spectrometer operated in
of the Cambrian Haima and Permo-Carboniferous Haushi groups, the metastable reaction monitoring (MRM) mode (same GC condi-
particularly along the eastern flank of the SOSB (Al-Marjeby and tions as for full scan mode). Biomarkers such as steranes, hopanes
Nash, 1986; Konert et al., 1991) and, as a result, are sub-divided and cheilanthanes, were detected using 26 individual precursor–
according to their reservoirs in carbonate stringer oils, silicilyte oils product transitions sampled over a cycle of ca. 1.2 s and were
and post-salt Huqf oils (also referred to as Eastern Flank oils), quantified using d4-aaa-ethylcholestane (D4) as internal standard
respectively. In contrast, Q oils occur mostly in Central Oman but without taking into account response factors. Biomarker ratios
can also be found in the northernmost part of the SOSB. Where used in this study were obtained from MRM GC–MS analysis.
encountered in the same well, Q oils occur in reservoirs that overlie Principal components analysis (PCA) and hierarchical cluster
those of the Huqf oils. analysis (HCA) were conducted using the Pirouette software (Inf-
ometrix Corporation).
3. Methods
4. Samples
3.1. Bulk analysis
4.1. Rocks
Rock-Eval parameters (Hydrogen Index HI, Oxygen Index OI
and Tmax) as well as total organic carbon (TOC) were deter- In total, 46 source rocks were provided (Table 1); 17 Nafun
mined using a Vinci Rock-Eval 6 apparatus according to estab- Group rocks, including 4 Masirah Bay Fm., 9 Shuram Fm. and 4
lished procedures (Espitalié et al., 1985). Samples were Buah Fm. samples, were analyzed. With respect to the Ara intra-
crushed and extracted with a mixture of dichloromethane salt section, 14 Athel intra-salt rocks, comprising 5 U Shale Fm., 5
(DCM) and MeOH (9:1, v/v) using a Dionex Accelerator Solvent Athel Silicylite, 4 Thuleilat Fm. samples and 15 carbonate stringers
Extractor ASE-200 operated under 1000 psi at 100 °C. Asphalt- (1  A1C, 2  A2C, 5  A3C, 5  A4C, 2  A5C) are reported in de-
enes were precipitated out from the resulting organic extracts tail. Most of the samples were composites of cuttings taken over
(bitumens) and from the oils using n-pentane. In asphaltene- several 10 s of meter intervals in order to homogenize and, there-
free fractions (maltenes) derived from bitumens, elemental sul- by, more completely characterize the geochemistry of the source
fur was removed with activated copper pellets. The maltenes rock formation. The exceptions were carbonate stringer samples
were fractionated on a silica gel column, eluting successively and Buah Fm. sample OMR020 where only core material was
with hexane, hexane/DCM (8:2, v/v) and DCM/MeOH (7:3, v/v) available.
to give, respectively, alkanes, aromatic hydrocarbons and resins.
Branched and cyclic alkanes were separated from n-alkanes by 4.2. Oils
treatment with silicalite. Ca. 10 mg of alkanes, in a minimum
volume of n-pentane were placed on a 3 cm bed of activated, In total, 54 South Oman oils (6 Q oils and 48 Huqf oils) were
crushed silicalite lightly packed into a Pasteur pipette. The examined. Huqf oils included 7 silicilyte oils, 15 post-salt Huqf oils
non-adduct (SNA), containing branched and cyclic alkanes, was and 26 carbonate stringer oils from A1C to A6C stratigraphic unit.
eluted using pentane (4 ml). Table 2 summarizes their bulk properties.
Bulk carbon isotope analysis was carried out using an elemental
analyzer coupled to a Finnigan Delta Plus XP according to standard 5. Source rock evaluation: overview
sealed tube combustion techniques (Sofer, 1980). Results (d13C val-
ues) are reported relative to the Vienna Peedee Belemnite (VPDB) Bulk geochemical parameters are given in Table 1. High TOC
standard. Hydropyrolysis of solvent-extracted samples were rocks with petroleum source potential have been recognized in
achieved according to the procedure described by Love et al. the intra-salt and pre-salt sections of the Huqf Supergroup for
(1997). some time (Mattes and Conway Morris, 1990). In the Athel basin,
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 91

Table 1
Rock-Eval data and bulk carbon isotopic composition of alkane and aromatic hydrocarbon fractions of rocks (TOC, total organic carbon; HI, Hydrogen Index; OI, Oxygen index).
13 13
Formation MIT ID Well code Well HID Depth (m) TOC (%wt) HI OI Tmax (°C) dSats dAros
A1C OMR039 Ds 105417284148270 2997 1.22 339 47 429 35.6 35.6
A2C OMR034 Bn 105518042847200 4204 1.9 451 46 435 35.3 35.1
A2C OMR042 Sb 105518121015410 2399 1.19 352 42 437 36.0 36.1
A3C OMR028 Bi 105518051934160 2927 0.53 314 106 428 NA NA
A3C OMR035 Bn 105518042847200 3790 0.19 276 329 440 33.2 34.7
A3C OMR036 Bn 105518042847200 3789 0.4 321 124 435 NA NA
A3C OMR037 Bn 105518042847200 3787 0.72 358 121 423 34.1 34.7
A3C OMR038 Bn 105518042847200 3785 0.13 325 505 440 NA 34.7
A4C OMR029 Br 105518061900350 2930 0.95 274 69 423 34.5 34.7
A4C OMR030 Br 105518061900350 2928 0.57 338 99 425 34.0 34.4
A4C OMR031 Br 105518061900350 2928 1.06 253 87 424 34.4 34.6
A4C OMR032 Br 105518061900350 2920 0.56 303 98 429 NA NA
A4C OMR033 Bb 105518052021340 3009 1.92 482 33 434 34.3 34.4
A5C OMR040 Om 105518022220500 2853 1.05 332 93 419 NA NA
A5C OMR041 Om 105518022220500 2851 0.44 338 168 419 34.8 34.9
Buah OMR002 Am 105518431952210 2345–2375 1.6 278 33 426 NA 38.4
Buah OMR017 Sa 105618284827160 1569–1602 2.3 339 20 433 38.7 39.5
Buah OMR020 Ta 105518505500411 4411 3.1 411 4 443 NA 37.4
Buah OMR149 At 105518471651420 2016–2019 11.0 NA NA NA 37.4 37.7
Masirah Bay OMR016 Ru 105618074334180 3125–3143 1.7 419 58 431 33.5 34.1
Masirah Bay OMR027 Za 105619334013330 2280–2295 3.8 338 45 425 32.0 31.2
Masirah bay OMR153 Ss 105720133211290 4230–4385 0.4 NA NA NA NA NA
Masirah Bay OMR157 Th 105518260443550 2895–2910 4.9 NA NA NA NA NA
Shuram OMR010 Mb 105518381457000 2628 2724 2.5 397 11 437 35.0 34.5
Shuram OMR026 Za 105619334013330 1905 1940 3.4 639 20 429 34.0 35.2
Shuram OMR099 At 105518471651420 2379 1.5 NA NA NA 37.0 36.6
Shuram OMR150 At 105518471651420 2053–2121 1.3 NA NA NA 36.4 36.7
Shuram OMR151 At 105518471651420 2424.5 2447 3.0 NA NA NA NA 35.1
Shuram OMR152 At 105518471651420 2449–2452 3.6 NA NA NA 35.7 35.0
Shuram OMR154 Tu 105619363441090 2247.5–2249.6 NA NA NA NA NA 38.2
Shuram OMR155 Th 105518260443550 2350–2435 2.4 NA NA NA 35.4 37.2
Shuram OMR156 Th 105518260443550 2685–2740 3.9 NA NA NA 34.8 34.7
Silicylite OMR004 At 105518471651420 1198 1425 3.4 569 31 423 35.9 36.5
Silicylite OMR012 Ma 105518120745470 2104–2120 3.4 550 36 424 37.2 37.4
Silicylite OMR013 Ma 105518120745470 2240–2352 2.3 592 37 420 37.1 36.5
Silicylite OMR023 Th 105517095822260 1551–1602 4.3 579 23 423 36.9 37.7
Silicylite OMR024 Th 105517095822260 1628–1742 2.6 690 33 424 35.6 35.8
Thuleilat shale OMR003 At 105518471651420 1000–1102 8.0 560 17 425 36.2 37.9
Thuleilat shale OMR011 Ma 105518120745470 2068–2084 10.4 600 11 433 36.3 37.3
Thuleilat shale OMR021 Th 105517095822260 1417.5–1483 6.4 574 21 429 36.5 38.1
Thuleilat shale OMR022 Th 105517095822260 1520 1547 2.5 454 25 422 37.1 37.7
U shale OMR005 At 105518471651420 1425–1527 3.5 337 26 419 35.2 35.6
U shale OMR006 At 105518471651420 1527–1650 4.9 378 19 425 35.3 36.3
U shale OMR007 At 105518471651420 1773–1872 5.7 312 22 430 36.3 37.6
U shale OMR014 Ma 105518120745470 2420 2460 6.4 559 20 429 34.3 34.8
U shale OMR025 Th 105517095822260 1751–1833 4.0 506 22 425 33.9 34.2

the Ara Group contains rocks of the Athel (Al Shomou) Silicilyte 6. Source rock geochemistry
(TOC 3–4%; HI 400–700) and U shale formations (TOC 5–15%; HI
300–700) that are reputed to be ‘world class’ (Terken et al., 6.1. Bulk carbon isotopic composition
2001). A re-examination of Athel intra-salt rocks also identifies
the Thuleilat Fm. as an excellent source rock, with TOC between Bulk d13C values for the saturated and aromatic hydrocarbon
5 and 15% and HI values around 600 mg HC/g org. C on average. fractions of the rocks show overall depleted values (Table 1), typi-
In the carbonate domains of the intra-salt section the occurrence cal of Precambrian rocks (Andrusevich et al., 1998). The carbon iso-
of organic-rich horizons is limited. Typical TOC for carbonate topic character of hydrocarbons from the individual Huqf
stringers is around 1%. TOC values >1% in some carbonate stringers formations is fairly variable, in particular within the Nafun Group,
were found to be caused by the presence of migrated residual oil oscillating between the relatively heavy values of the Masirah Bay
(Paul Taylor, personal communication), however the carbonate Fm. (reaching 31‰ for saturates and aromatics) and the exceed-
stringer rocks presented in this study do not show this character. ingly light values of the Buah samples (ca. 39‰; Table 1). The
Samples at the top salt A6C (Dhahaban Fm.) have values up to 8% saturated and aromatic hydrocarbon d13C values from the Thuleilat
and an HI average of 600, i.e. attributes of a high quality source Fm. form a tight cluster around 37‰, whereas a fairly wide range
rock (Terken and Frewin, 2000). A screening of pre-salt rocks re- of values ( 34‰ to 37‰) is observed within the Shuram and U
vealed the occurrence of high quality, oil-prone source rocks in shale formations (Table 1). The saturates and aromatics of the
the Nafun Group, more particularly in the Lower and Upper Masi- Athel Silicilyte bitumens have values very close to those of the
rah Bay (TOC 1–10%; HI 400–700), the Lower and Upper Shuram Thuleilat Fm, with an average of 36.5‰.
(TOC 2–5%; HI 200–600) and the Buah (TOC 2%; HI 300–600) for- The lower carbonate stringers A1C and A2C exhibit d13Csats and
mations (Paul Taylor, personal communication). Those with the d13Caros values slightly lighter than those of the upper horizons
widest distribution are from the Lower Shuram and Upper Masirah A3C–A5C (Table 1). Overall, the carbonate stringer hydrocarbons
Bay formations. have slightly heavier average d13C values than the time-equivalent
 92
Table 2
API data, bulk carbon isotopic composition and relevant MRM biomarker ratios for the oils. (Biodeg., biodegradation rank; PS Huqf, Post-salt Huqf oil; NA, not available. Biomarkers were measured from specific MRM transitions and the
following ratios were calculated: 22T/21T = C22 tricyclic terpane/C21 tricyclic terpane; 24T/23T = C24 tricyclic terpane/C23 tricyclic terpane; GA/30H = gammacerane/C30 ab-hopane; 35H/34H = (C35 ab-hopanes 22S + 22R)/(C34 ab-
hopanes 22S + 22R); TNH/(Ts + Tm) = 25,28,30-trinorhopane/(Ts + Tm); DNH/30H = 28,30-dinorhopane/C30 ab-hopane; 2MH/3MH = 2a-methyl C30 hopane/3b-methyl C30 hopane; 2MHI: 2-methylhopane index = 2-methyl C30 hopane/
(2-methyl C30 hopane + C30 hopane)  100).
Stratigraphy MIT ID Well ID Field Min. depth API 13d 136ATOS Biodegr. 22T/ 24T/ GA/ 35H/ TNH/ DNH/ 2MH/ 2MHI
(m) Sats 21T 23T 30H 34H (Ts+Tm) 30H 3MH
A1C OMO005 105417294105520 DHAHABAN SOUTH 2926.1 51.7 35.6 35.7 0 0.3 0.39 0.15 1.73 0.02 0.23 1.74 6.74

E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

A1C OMO040 105518011119180 KAUKAB 3163 32.6 NA 35.2 0 0.33 0.51 0.15 1.36 0.01 0.09 1.34 7.79
A2C OMO033 105418330226010 SAKHIYA 4793 34.7 NA 33.3 0 0.41 0.48 0.17 1.46 0.10 0.21 1.07 5.14
A2C OMO034 105418380655030 RABAB 4356 48.5 34.2 33.7 0 0.44 0.49 0.17 1.37 0.07 0.14 1.00 4.85
A2C OMO049 105417365600000 HARWEEL DEEP 3746.3 60 35.7 35.2 0 0.44 0.42 0.15 1.65 0.04 0.20 2.01 7.14
A2C OMO053 105417295308420 GHAFEER 4330.04 37.1 35.1 34.4 0 0.41 0.40 0.16 1.56 0.06 0.16 1.29 5.66
A2C OMO055 105418300002430 ZALZALA 4916 39.1 34.2 33.0 0 0.36 0.46 0.14 1.40 0.04 0.21 1.51 5.59
A2C OMO056 105418340256100 FAYROUZ 4472 51.5 34.9 34.1 0 0.38 0.58 0.13 1.44 0.13 0.21 1.42 5.18
A2C OMO057 105417295829310 DAFAQ 5096 39.8 34.7 34.0 0 0.36 0.48 0.17 1.46 0.04 0.13 1.49 6.47
A3C OMO031 105417365600000 HARWEEL DEEP 311054 22.5 35.2 35.0 0 0.241 0.49 0.22 1.62 0.11 0.24 1.46 7.41
A3C OMO039 105418591443090 DURRA 2952.6 35 34.8 34.6 0 0.43 0.39 0.22 1.81 0.20 0.28 1.92 7.76
A3C OMO041 105518011119180 KAUKAB 2779.5 29.1 35.0 34.9 0 0.45 0.39 0.21 1.89 0.23 0.26 1.84 7.63
A3C OMO051 105417355604421 SARMAD 3651 32.6 35.4 35.2 0 0.39 0.45 0.19 6.71 0.10 0.18 1.47 6.71
A3C OMO052 105417275338150 GHAFEER 4339 35.7 34.9 34.0 0 0.41 0.43 0.17 1.56 0.03 0.09 1.24 5.62
A4C OMO006 105518042847200 BIRBA NORTH 3680.8 50 34.9 34.7 0 0.46 0.43 0.19 1.77 0.15 0.24 1.99 8.51
A4C OMO016 105518061802480 BIRBA 2790.4 30.5 34.7 34.7 0 0.45 0.43 0.24 1.97 0.20 0.33 1.61 8.12
A4C OMO036 105518061721330 BIRBA SOUTH 2576.78 46.8 34.5 34.8 0 0.42 0.41 0.19 1.72 0.26 0.31 1.82 8.04
A4C OMO038 105518051934160 BIRBA 2832.81 28 34.4 34.8 0 0.38 0.39 0.21 1.76 0.24 0.32 1.87 8.06
A4C OMO058 105518052416051 BUDOUR 3219 51.5 35.2 34.9 0 0.41 0.41 0.16 1.62 0.31 0.38 2.64 10.24
A4C+A3C OMO045 105518022220500 OMRAAN 3178.1 30.9 34.7 34.7 0 0.39 0.40 0.20 1.79 0.19 0.31 1.71 7.29
A5C OMO015 105620080139160 SU WAI HAT 3715.8 49.7 35.9 34.5 0 0.50 0.38 0.14 1.98 0.02 0.15 2.66 9.21
A5C OMO037 105518022220500 OMRAAN 2840.13 30.7 34.8 34.6 0 0.40 0.42 0.22 1.77 0.20 0.31 2.07 8.22
A5C OMO043 105418430658140 HAWMYAT 3933 28.2 34.6 34.7 0 0.30 0.53 0.12 1.30 0.49 0.16 2.56 8.09
A5C OMO054 105417335655201 SARMAD 3742 33.4 35.2 34.8 0 0.39 0.43 0.18 1.65 0.10 0.19 1.68 7.56
A6C OMO035 105418330316080 ANDHUR 3442.72 28.3 34.8 34.3 0 0.43 0.41 0.19 1.61 0.12 0.21 1.81 8.18
A6C OMO059 105417205122490 QASHOOB 4819 32.3 36.1 35.7 0 0.26 0.59 0.17 0.98 0.06 0.30 1.74 9.57
PS Huqf OMO002 105619282116100 MUKHAIZNA NORTH 844.3 16.3 35.4 35.7 1 0.59 0.36 0.21 2.89 0.1 0.19 1.79 8.15
PS Huqf OMO003 105417263411030 JAZAL 878.1 27.8 33.9 34.1 0 0.49 0.38 0.20 1.98 0.10 0.20 0.79 4.94
PS Huqf OMO004 105518574204450 NIMR 880.9 biodegraded 35.4 36.0 4 0.01 0.151 0.15 1.71 0.01 0.15 1.52 7.04
PS Huqf OMO007 105619260135090 JALMUD NORTH 1060.7 25.9 34.8 35.6 0 0.44 0.46 0.16 1.99 0.01 0.06 1.81 7.39
PS Huqf OMO008 105618074334180 RUNIB 795.5 25 36.2 36.2 36 1 0.41 0.49 0.151 1.60 0.1 0.15 1.61 5.50
PS Huqf OMO009 105618164010550 NUWAR 1497.8 1497.81 35.8 36.7 2 0.58 0.33 0.26 2.0 0.03 0.19 2.09 10.08
PS Huqf OMO010 105518160817390 MARMUL 894.3 22.1 35.5 35.9 1 0.45 0.45 0.20 2.03 0.01 0.19 1.67 8.34
PS Huqf OMO011 105518533910250 NIMR 929.6 20.6 35.2 35.7 4 0.41 0.01 0.12 1.55 0.01 0.12 1.68 6.43
PS Huqf OMO013 105618204222150 SAHAM 1059.2 3.4 35.3 36.1 2 6.1 0.48 0.26 1.84 0.02 0.14 1.40 10.24
PS Huqf OMO014 105619001739100 GHUFOS 1131.4 28.1 36.1 36.7 1 0.68 0.31 0.42 2.59 0.04 0.24 2.00 13.56
PS Huqf OMO022 105518260537100 THAMOUD 1385 biodegraded 35.9 36.1 0 0.54 0.39 0.22 1.82 0.04 0.23 2.18 9.72
PS Huqf OMO023 105618164728380 REIHAN 1312 21 35.7 36.4 1 0.51 0.46 0.14 1.77 0.02 0.09 1.48 6.37
PS Huqf OMO024 105518140623080 MARMUL 915.3 21.4 35.8 35.9 0 0.52 0.44 0.21 1.79 0.01 0.20 1.88 9.48
PS Huqf OMO026 105518271257290 MAURID 1129 biodegraded 35.7 35.9 1 0.61 0.36 0.26 1.99 0.02 0.30 2.40 10.36
PS Huqf OMO028 105618305524220 THURAYAH 1438 13.7 35.0 36.9 0 0.58 0.33 0.21 2.16 0.01 0.06 1.80 6.89
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 93

Athel intra-salt bitumens. This difference has been attributed to a

10.92
10.99
9.71
3.65
4.27
5.77
5.48

12.08
12.01
11.07

10.70
3.30
5.04
shallower water column over the platform limiting carbon assimi-
lation and, therefore, leading to less 13C depletion (Gelin et al.,
1999).

2.26
2.29
1.98
2.58

2.11
0.26
0.31
0.36
0.24
0.44

2.09
0.50

NA
6.2. Molecular composition

0.11
0.13
0.12
0.11
0.12
0.96
0.74
0.76
0.48
0.72

1.07

0.20
0.10

Biomarker ratios measured from specific MRM transitions are

given for each individual rock sample as supplementary informa-
tion in Table S1. Averaged ratios for each formation are shown in
0.14

02.11
0.12

0.12

0.01
0.01
0.02
0.01
0.04
0.08
0.09
0.08

Table 3.
0.1

6.2.1. Normal and branched alkanes

GC traces of the alkane fractions from representative rock sam-
2.581

1.92
1.61
1.54
1.91
1.34
1.48
1.76
1.47
1.68
1.78
0.19
0.4

ples are shown in Fig. 3. Pr/Ph values are well below 0.8, with the
exception of Masirah Bay sample OMR027 and Buah sample
OMR020. These low values reflect anoxic conditions during deposi-
0.24
0.18
0.25
0.18
0.18
0.23
0.84
0.56
0.81
0.78
0.65
0.61

0.20

tion as well as saline to hypersaline conditions associated with car-

bonate and evaporite deposition (Peters et al., 2005). All Huqf
Supergroup rocks contain characteristic mid chain MMAs (origi-
0.720

00.540

nally designated X-compounds; Grantham et al., 1987) and their

0.41
0.42
0.38
0.41
0.41
0.81
0.79
0.76
0.79
0.74

0.2

relative abundance is enhanced in the range C20–C24 and drops sig-

nificantly above C24 (Fig. 3). However, on average, mid chain MMAs
tend to be relatively more abundant in Ara samples than in the Na-
0.49
0.39
0.54
0.38
0.49
0.49
0.32
0.28
0.28
0.27
0.29
0.36

0.2

fun rocks (Fig. 3 and Table 3). The exact origin of these branched
alkanes is uncertain. A bacterial source has been suggested, as
mid-chain methyl alkanes are present in cyanobacteria (Gelpi
0
0
0
4

0
0
0
0
4
0
0
0
0

et al., 1970; Paoletti et al., 1976) and modern cyanobacterial mats

(de Leeuw et al., 1985; Robinson and Eglinton, 1990). Mid-chain
30.7

35.4
30.9

33.8
34.7
30.6

34.9
34.1
34.9
35.5
31.4
31.8

branched fatty acids in symbiotic bacteria living in sponges are also

31

potential precursors (Thiel et al., 1999). However, none of these

modern precursors gives rise to distributions exactly comparable
to those in Oman bitumen and kerogen pyrolyzates in terms of
36.4
35.3
35.4
33.7
35.1
34.4
34.7
30.5
31.8
32.4
31.2
31.3
30.3

chain length and branching loci (Höld et al., 1999), leaving open
the question of their source.

6.2.2. Steranes
biodegraded

condensate

Sterane distributions in Huqf rocks present numerous features

peculiar to rocks of such age. One of the most distinctive character-
47.2
46.5
46.9
51.5
45.6
47.3
41.8
28.3
45.8
43.5
41

istics is the predominance of C29 steranes, constituting on average

70% of the C27–C29 steranes for all the Huqf rock samples. It is
remarkable that this feature occurs throughout the Huqf Super-
930.2

3653.3
600.5

1951.2
1708.4

group from the Masirah Bay Fm. rocks at the base of the Nafun
3771

4081
4239
4258

3992

4023
1273
2304

to near the top of the Ara Group (Fig. 4a) in the A5 stringer. Such
C29-sterane dominated distributions have been observed in Neo-
proterozoic geological samples worldwide (Fowler and Douglas,
SU WAI HAT

ALSHOMOU
ALSHOMOU
ALSHOMOU

1987; Summons and Powell, 1992; Peters et al., 1995) and are
ZAULIYAH
KATHEER

AL NOOR
AL NOOR
AL NOOR

AL NOOR
GHUFOS
ANZAUZ
MISFAR

attributed to green algae (Grantham and Wakefield, 1988), which

synthesize primarily C29 steroids (Volkman, 2003) and must have
been important primary producers at the time. The broad age dis-
tribution of C29 sterane dominance even extends down into the
105518294129271
105518253847270
105518253847270
105518284147440
105518294113410
105518253827320
105519521853130

105518294140380
105520552128510
105619004226110
105619001739100
105620080139160
105620203140130

glaciogene Ghadir Manqil Fm. (data not shown). This unit most
likely predates the Acraman impact event in Australia and first
appearance of abundant C29 steranes recorded in sediments of
the Centralian Superbasin (McKirdy et al., 2006).
The C29 sterane predominance aside, sterane distributions
across the Huqf Supergoup share other remarkable features. The
C30 desmethylsterane distributions are characterized by the con-
comitant presence of 24-n-propylcholestanes and 24-isopropyl-
cholestanes in all Huqf rock samples (Fig. 5). Empirical data
OMO044
OMO046
OMO048
OMO021
OMO025
OMO029
OMO019
OMO012
OMO018

OMO050
OMO030
OMO020
OMO001

suggest 24-n-propylcholestanes are derived from marine

chrysophyte algae and are diagnostic for marine depositional
environments (Moldowan et al., 1990). On the other hand, 24-
isopropylcholestanes have been shown to predominate over
24-n-propylcholestanes in Late Proterozoic and Early Cambrian
Silic.
Silic.
Silic.
Silic.
Silic.
Silic.
Silic.

sediments and oils, which is hypothesized to reflect the radiation

Q
Q
Q
Q
Q
Q
94 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

of sponges, as their sterol precursors occur in sponges of the class

19C (lg/g
Demospongiae (McCaffrey et al., 1994). Huqf rocks show 24-isopro-
TOC) pylcholestanes/(24-isopropyl + 24-n-propylcholestanes) propor-

1.25
0.09
0.09
0.07
0.03
0.02
0.07
0.06

0.06
0.08
0.03
0.05

0.70
tions varying between 36% and 94%, with a total average of 58%
for the whole set of rocks (Fig. 4b).
19B (lg/g

C26 steranes, occurring as both 27-norcholestanes and 21-nor-

TOC)

cholestane and excluding 24-norcholestanes (Fig. 5), comprise a

1.24
1.84
1.46

1.42
0.82
0.45

1.31
2.69
0.89
1.09

1.07
2.01

2.05
large proportion (on average 6%) of the total C26–C29 steranes
and likely reflect a combination of biological inputs specific to this
19A (lg/g

period of time. Relative concentrations of 21-norcholestane have

TOC)

been shown to increase with maturity (Moldowan et al., 1991)

0.34
0.43
0.35
0.17
0.12
0.34
0.28

0.22
0.37
0.16
0.25
0.45
0.36
but may also be related to OM deposition under hypersaline condi-
Averages of relevant MRM biomarker ratios for each Huqf formation. Refer to Table 2 for biomarker ratios (X-22: mid-chain C22 MMAs; n-22: linear C22 alkane; Tet = C24 tetracyclic terpane).

tions (Guzmán-Vega et al., 1997). The relative abundance of 21-

norcholestane vs. 27-norcholestanes is the highest for carbonate
Hopanec
Sterane/

stringers (Table 3).

0.66
0.79
0.71
0.85
0.78
0.77
0.71

0.89

0.91
0.96
0.89
0.93
1.08

C30 ring-A methyl sterane distributions are largely dominated

by 3b-methylstigmastanes in all the Huqf rocks (Fig. 5). This pre-
0.25

0.27
0.45
0.48
0.32
0.32

0.22

0.22
0.22
0.25
0.23

0.23
0.30

ponderance over methyl steranes alkylated at C-2 and C-4 is char-

Tet/
23T

acteristic of Late Proterozoic and Paleozoic geological samples

(Summons and Powell, 1987, 1992). However, it is also significant
24T/

0.47
0.46
0.56
0.43

0.45
0.51

0.31
0.27
0.24
0.28
0.41
0.35
0.50
23T

that trace levels of 4-methylsteranes, including dinosteranes and

24-ethyl-4-methylcholestanes were identified in all the samples
and there is no evidence to suggest that their presence is due to
22T/

0.25
0.46
0.34
0.42
0.35

0.31

0.68
0.79

0.76
0.46
0.40

0.80

0.60
21T

contamination from geologically younger hydrocarbons.

Sterane distributions are fairly similar across the different Huqf
29dia/

0.16
0.21

0.11
0.08
0.06
0.07

0.09

0.03
0.02
0.03
0.03
0.03
0.03

formations and the main distinctive feature is a low diasterane

stb

content in Ara rocks (Fig. 5 and Table 3), which are carbonates,
2MHI

5.42

7.17
6.27
3.69
7.78
5.58

7.65

10.36
7.98
9.13
11.85
11.89
9.50

or otherwise starved of clastic input, compared to the Nafun sam-

ples which are from a predominantly clastic sequence. This accords
with observations for much younger petroleum provinces such as
2MH/

those of the California Borderland basins (Brincat and Abbott,

3MH
1.45
2.54
2.14

1.93
1.54

2.43
0.84

3.45
2.78

1.68
2.26
1.01

2.90

2001).
X-24/

6.2.3. Hopanes
n-24
0.35
0.65
0.48
0.36

0.51
0.39

0.67
0.81
0.46
0.81
1.12
0.30

0.60

The distributions throughout the Huqf Supergroup are generally

characterized by relatively high C35 hopane abundance (Fig. 6), as
X-22/

illustrated by the averaged C35 hopane/C34 hopane (35H/34H) val-

Steranes/Hopanes = Sum (C27–C29 ba diasteranes, aaa and abb steranes)/Sum (C27–C35 hopanes).
n-22

0.62
0.45
0.67
0.51
0.56
0.41

0.77
0.98
0.64
0.81
0.46
0.81
0.30

ues in Table 3. However, compared to Nafun rock samples, Ara

samples (Athel intra-salt rocks and carbonate stringers included)
21-nor/27-

display, on average, higher C35/C34 hopane values, consistent with

more reducing depositional conditions (Peters and Moldowan,
0.12

0.11

0.19
0.14
0.09

0.09
0.09
0.06
0.10
0.08

0.06
0.08
0.08
nora

1991). Highly reducing environments are also suggested by the

substantial content of 28,30-dinorhopane (DNH) and 25,28,30-tri-
0.14
0.12
0.14

0.13

0.11
0.18
0.21
0.16
0.23
0.19
0.09

0.06

0.09
30H

norhopane (TNH) in these rocks. These two compounds, typical of

GA/

petroleum source rocks deposited under anoxic, or euxinic, condi-

tions (Curiale et al., 1985; Mello et al., 1988; Brincat and Abbott,
21-nor/27-nor = 21-norcholestane/(27-norcholestanes aaa + abb).
35H/

1.52
1.42
1.58
1.47
1.43
1.31

1.62
1.93

1.84
1.77
1.09

1.80
2.00
34H

2001), are best detected and quantified using the MRM transitions
384 ? 191 Da and 370 ? 177 Da (Fig. 6). Within the intra-salt sec-
tion, ratios of 28,30-dinorhopane to C30 hopane (DNH/30H) and
DNH/
TNH
6.77
5.52
4.84
7.19

6.21
5.48

3.49
1.34
1.94
2.28
4.61
3.49
4.60

TNH/(Ts + Tm), used to assess the relative abundances of 28,30-

29 dia/st = C29 ba diasteranes/(aaa + abb steranes).

dinorhopane and 25,28,30-trinorhopane, are by far the highest in

(Ts + Tm)

the Athel Silicilyte and Thuleilat Fm. samples, whereas they appear
to be at an intermediate level in the U Shale Fm. and carbonate
TNH/

1.46
0.11

0.45
0.69
0.16
0.41
0.01
0.02
0.02
0.02
0.03
0.02
0.02

stringers (Fig. 7a). The silicilyte samples show the highest absolute
abundances for DNH and TNH, culminating at 77 and 176 ng/g
DNH/

TOC, respectively. In contrast, ratios DNH/30H and TNH/(Ts + Tm)

0.78
0.75
0.56
0.27
0.41
0.05
0.08
0.07
0.09
0.06
0.08
0.06

0.20
30H

are extremely low for all Nafun bitumens (Table 3). Unfortunately,
although 28,30-dinorhopane and 25,28,30-trinorhopane discrimi-
Ara total (Athel & carbonate
Nafun w/out Shuram/Buah

nate the Nafun rock samples from the Ara samples quite remark-
Shuram w/out anomalies

ably, their application in oil-source correlation has been limited

Buah w/out anomalies

Carbonate stringers

due to their high sensitivity to maturity. They are thought not to

be bound to the kerogen, occurring rather as free hydrocarbons
Athel intra-salt
Thuleilat shale

stringers)
Masirah Bay

(Noble et al., 1985) and, as a consequence, their relative abundance

Formation

anom.

tends to diminish markedly with increasing maturity (Moldowan

Silicilyte
Shuram
Table 3

U shale
Nafun

and Seifert, 1984). The fact that 28,30-dinorhopane and 25,28,30-

Buah

c
b
a

trinorhopane did not appear to be incorporated into kerogen led

 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 95

Fig. 3. GC traces of total alkanes of representative rocks: (a) Thuleilat Shale, (b) Silicilyte, (c) Carbonate Stringer (CS) A3C, (d) Shuram and (e) Masirah Bay. Linear alkanes are
indicated by their carbon number. Each X-peak represents coelution of several MMAs branched at different positions: e.g. X-24 is a mixture of 11- and 12-methyltricosane.
STD, internal standard 3-methylheneicosane; Pr, pristane; Ph, phytane; i-16, C16 isoprenoid alkane.

to the suggestion they are products of early diagenetic bacterial ninghe Damsté et al., 1995), is present in all the Huqf rock bitu-
reworking (Curiale et al., 1985) and possibly synthesized by sulfur mens but tends to be in greater proportion in Ara samples than
oxidizing bacteria (Williams, 1984). in Nafun rocks and, in particular, in carbonate stringers, the Athel
Gammacerane, a biomarker for water column stratification silicilyte and the Thuleilat shale, suggesting elevated salinity in
commonly induced by hypersalinity (Moldowan et al., 1985; Sin- the original water column for these rocks (Fig. 7b).
96 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

A5C
a b
A4C

A3C

A2C

A1C

Thuleilat

Silicilyte

U Shale

Buah

Shuram

Masirah
Bay

0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
%C29 steranes %i-C30/(i-C30+n-C30)

Fig. 4. (a) % C29 steranes and (b) % i-C30/(i-C30 + n-C30) for all Huqf rock formations. % C29 steranes = [C29 ba diasteranes, aaa and abb steranes]/[(C27 + C28 + C29) ba
diasteranes, aaa and abb steranes]  100. % i-C30/(i-C30 + n-C30) = 24-isopropylcholestanes (aaa + abb)/[(24-isopropyl- + 24-n-propylcholestanes) (aaa + abb]  100.

C31 to C36 A-ring methylated hopanes are present in Huqf rocks Despite a concerted search, the diaryl isoprenoid isorenieratane,
as 2a-methylhopanes and 3b-methylhopanes (Fig. 6). Proportions derived from anoxygenic photosynthetic sulfur bacteria (Chlorobi-
of 2a-methylhopanes relative to 3b-methylhopanes vary quite sig- aceae) and therefore often associated with euxinic basins (Brocks
nificantly among Huqf rock samples: the Masirah Bay and Buah and Summons, 2003), was not detected in any aromatic fractions,
formations show the highest 3b-methylhopane to 2a-methylho- including Raney Ni-desulfurised aromatic fractions and hydropyr-
pane ratio values (Fig. 7c), whereas they are lowest for the Ara olysis products. However, short chain 2,3,6-aryl isoprenoids (along
samples from the silicilyte and the Thuleilat Fm. and for some with 2,3,4-) could be found in trace levels. The significant concen-
pre-salt Shuram rock samples. On average, the ratio of 2a-meth- trations of 28,30-dinorhopane and 25,28,30-trinorhopane in Ara
ylhopanes to 3b-methylhopanes for all Ara samples is 2.3, as op- rocks, together with relatively high abundances of C35 hopanes
posed to 1.9 for Nafun samples (Table 3). An inversely and gammacerane, all indicate that these rocks were deposited in
proportional trend is observed for the 2a-methylhopane index a periodically or permanently stratified basin characterized by an-
(2-MHI = C30 2-methylhopane/(C30 2-methylhopane + C30 ho- oxic or euxinic bottom waters. On the other hand, evidence from
pane)), a potentially useful tracer for cyanobacterial input to sedi- the patterns of sulfur isotopes in coeval pyrite and carbonate-asso-
mentary OM (Summons et al., 1999). ciated sulfate in the Huqf sediments shows that the ocean feeding
water into the restricted environment of the SOSB became progres-
6.2.4. Cheilanthanes sively oxygenated during the deposition of the entire Nafun Group
Huqf bitumens contain tricyclic terpanes (cheilanthanes) with (Fike et al., 2006).
C23 predominant. However, distributions across the respective for-
mations are variable, as shown by C22 tricyclic terpane/C21 tricyclic 6.3. Ara versus Nafun geochemical character: summary
terpane (22T/21T), 24T/23T (Fig. 7d) and 26T/25T ratios. On aver-
age, Athel intra-salt rocks show high 22T/21T combined with low One of the aims of this study was to identify geochemical attri-
24T/23T values, whereas the opposite trend is observed for most butes discriminating the Nafun sediments from the Ara sediments
of the Nafun rocks, with some exceptions in the Shuram and Buah in order to better understand and predict their respective contribu-
formations. Carbonate stringer samples have values intermediate tions to the oil accumulations. To achieve this goal, the selection of
between these two end members (Fig. 7d). The relative proportion a reliable and pristine sample set was absolutely critical and ex-
of the C24 tetracyclic terpane when compared to cheilanthanes also treme care was taken regarding the choice of the rocks. However,
fluctuates across the Huqf Supergroup, with values of C24 tetracy- during the course of the study, it became clear that contamination
clic to C23 tricylic slightly higher in Nafun rocks than Ara intra-salt of Huqf rocks and, in particular, some from the Nafun Group, was a
rocks (Table 3). cause for concern. Several samples had to be removed from the ini-
tial Nafun set due to contamination with Phanerozoic hydrocar-
6.2.5. Aromatic hydrocarbons bons, most likely from drilling fluids used during coring (Stalvies,
Aromatic fractions were analyzed using GC–MS with selected personal communication). While Phanerozoic staining of Huqf
ion monitoring in order to target specific compound classes such rocks is relatively easy to identify thanks to their distinct hydrocar-
as aromatic steroids, aromatic hopanoids and aryl isoprenoids. bon biomarker assemblages, cross contamination between differ-
Monoaromatic, triaromatic and methyl triaromatic steroids and ent Huqf formations, if it occurs, is obviously a much more subtle
benzohopanes were detected but none were useful in distinguish- problem to pinpoint.
ing Nafun from Ara rocks. In particular, the ratio of 3-methyl/4- Several Nafun rocks from the Shuram and Buah formations
methyl C29 triaromatic steroid developed in previous unpublished (OMR149, OMR150, OMR099 from well At; OMR154 from well Tu;
studies by Kohnen and Nederlof (Paul Taylor, personal communi- OMR155 from well Th) display features very similar to Ara intra-salt
cation) did not confirm its potential as a discriminating parameter rocks (Fig. 7 and Table S1) and consequently, unique characteristics
given that we found there was significant overlap in this parameter for these formations are extremely difficult to identify. Several pos-
between Ara and Nafun rocks. sible explanations could account for these data including:
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 97

a OMR016 b OMR037
Masirah Bay Carbonate stringer A3C
αββ
C30 ring A-methyl C30 ring A-methyl 3β-Me
414 → 231 414 → 231
100 18 100 13 αααS αααR
3β-Me 3β-Me
% %

0 0
i-αββ

n-αββ
C30 C30 i-αββ
i-αααS

i-αααR
100 414 → 217
100 414 → 217
i-αααS

n-αααR
i-αααR n-αααS
6 2
%
%

0 0
αββ αββ
C29
C29 100 400 → 217
100
400 → 217 αααS αααR αααS αααR
100
100
% βαS %
βαR

0
C28 αββ C28 αββ
386 → 217 386 → 217
100 100
αααS

34 αααR 21

αααS
βαS αααR
% βαR %

0 0
C27 C27
αββ αββ
372 → 217 αααR 372 → 217
100 29 αααS 100 26
αααR
βαS αααS
βαR
% %

0 0
C26 27-nor C26 27-nor
358 → 217 358 → 217
21-nor

100 100 7
9 27-nordia
21-nor

αααR
% %

0 0
Time Time

Fig. 5. MRM chromatograms showing distributions of C26–C30 steranes of (a) Masirah Bay OMR016 and (b) CS rock A3C OMR037 (carbon number, specific transition and
relative intensity shown). ba, aaa and abb denote 13b (H),17a (H)-diasteranes, 5a (H),14a (H),17a (H)- and 5a (H),14b (H),17b (H)-steranes, respectively. S and R define the
stereochemistry at C-20. 21-nor: 21-norsterane; 27-nor: 27-norsteranes; 27-nordia: 27-nordiasteranes; n- and i- in 414 ? 217 Da indicate n-propylcholestanes and
isopropycholestanes, respectively. 3b-Me in 414 ? 231 Da denotes 3b-methylsteranes.

(1) These particular Nafun samples were compromised by cav- raising doubts about the validity of these particular strati-
ing of cuttings from organic-rich Ara units higher in the sec- graphic assignments. Indeed, Buah in well At presents a clastic
tion during drilling of wells At, Th and Tu, or low angle lithology rather than being a carbonate unit and the Shuram
faulting led to structural repetition of the Ara Fm. in these unit does not display the generic negative carbon isotopic
wells. excursion.
(2) They represent intersection of Ara-like facies in the Nafun Despite the incoherencies observed in the Shuram and Buah
that preceded their wider appearance in the overlying unit. biomarker character, trends opposing Ara and Nafun rocks can be
clearly identified when average values of parameters within
At this point, we cannot resolve these, although we note that respective formations are considered (Table 3). The geochemical
deeper Nafun rocks from wells At (OMR152, 2449 m) and Th characteristics that delineate Ara source rocks include: low Pr/Ph
(OMR156, 2685 m and OMR157, 2895 m) do not show Ara char- values; high relative abundance of mid-chain MMAs; high C35 ho-
acteristics. Hydropyrolysis of kerogens of the suspicious Shuram panes/C34 hopanes, high relative abundance of gammacerane,
and Buah rocks would be needed in order to decipher whether 28,30-dinorhopane, 25,28,30-trinorhopane and 2-methylhopanes;
cross-contamination effectively happened or not. A structural low diasteranes; cheilanthanes ratios 22T/21T > 0.35 and 23T/
repeat and thickening of the Thuleilat–Silicilyte–U Shale pack- 24T < 0.50. In contrast, the geochemical attributes characterizing
age due to low angle faulting could also account for some of Nafun Group OM are: low abundance of mid-chain MMAs; low va-
the observed inconsistencies. A close examination of the At well lue for C22/C21 tricyclic terpanes combined with elevated value of
log suggests that samples identified as Shuram (OMR150 and C24/C23 tricyclic terpanes; low 2-methylhopane index combined
OMR099) and Buah (OMR149) do not show the lithological, with higher 3-Me/2-Mehopane ratio; low abundances of 21-nor-
geochemical and well log attributes typical of these formations, steranes; low gammacerane/C30 hopane ratio; elevated
98 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

OMR016 OMR037
a Masirah Bay b Carbonate stringerA3C
C30H m/z 191 C29H m/z 191
100 100 100
C29H C30H
C31H

29,30-DNH
C31H

C29Ts
Tm C32H
% Ts S C32H S
Tm C33H 28,30 R C33H C34H C35H
R SR C34H C35H S
S -DNH γ R
γ R S S Ts SR S S R
R R R
0

3βMe-C30H C30 methylhopanes

3βMe-C30H
100 C30 methylhopanes
426 → 205 426 → 205
2αMe-C30H 9
9
2αMe-C30H
%

0
Crosstalk 28,30-DNH
C28 C28
28,30-DNH

of C29H
100
384 → 191 Crosstalk 384 → 191
29,30 9 29,30 of C29H 15
-DNH Crosstalk -DNH
% of C29Ts

0
C27 C27
TNH
Ts 370 → 177 370 → 177
100
2 6

Tm
%
TNH

Tm
Ts
0
Time Time

Fig. 6. MRM chromatograms showing 370 ? 177, 384 ? 191, 426 ? 205 Da transitions and m/z 191 SIM chromatotogram for (a) Masirah Bay OMR016 and (b) CS rock A3C
OMR037 (carbon number, specific transition and relative intensity shown). H: ab-hopane; DNH: dinorhopane;c: gammacerane; TNH: 25,28,30-trinorhopane; 2a-Me-C30H:
2a-methyl C30 hopane. S and R define the stereochemistry at C-22.

abundances of the C24 tetracyclic terpane and diasteranes com- case, A-ring contraction is a feature of sterols in some sponges
pared to Ara Group sediments. (Minale and Sodano, 1974; Bohlin et al., 1980, 1981). Short chain
Ara characteristics are particularly pronounced for the Athel A-norsteranes have, however, never been described. For simplifica-
Silicilyte and Thuleilat Fm. samples, whereas Nafun biomarker tion and clarity purposes, we name hereafter these tetracyclic
character is best represented in the Masirah Bay samples. Carbon- compounds A-norsteranes, although this structural assignment re-
ate stringer rocks and U Shale samples appear, on average, to stand quires proof.
in between these two end members. These contrasts between Ara While A-norsteranes were detected in all the Oman rocks, par-
and Nafun group sediments are accentuated when the suspicious ticular isomers within C19, C20 and C26 A-norsterane distributions
Shuram and Buah are removed from consideration, as shown by appear to be specific to the carbonate stringer rocks. In the alkane
averages of parameters excluding these samples in Table 3. fractions of carbonate stringer bitumens, the distributions of C19 A-
norsteranes, revealed by m/z 203 chromatograms, show three dif-
6.4. Novel biomarkers in Huqf rock samples ferent isomers denoted 19A, 19B and 19C with the relative abun-
dance 19B > 19C > 19A (Fig. 9a). Importantly, this pattern is also
Tetracyclic compounds characterized by a base peak at m/z 203 observed in the hydropyrolyzates of the carbonate stringer rocks
in their mass spectra occur pervasively in the alkane fractions of (Fig. 9b), implying that these compounds are covalently bound to
Oman rock samples. Molecular ions M+. at m/z 260, 274 and 358 the kerogen and so cannot be attributed to staining or migration
indicate the occurrence of C19, C20 and C26 series respectively. contamination. A systematic analysis of A-norsteranes in the free
The C19 components are readily detected using either MRM or and kerogen-bound aliphatic fractions of other Huqf source rock
SIM GC–MS, whereas the C20 and C26 homologues are better de- facies (Stalvies et al., unpublished results) shows that the 19C iso-
tected using the specificity of MRM analysis by means of the tran- mer is virtually absent from Nafun rock samples (Masirah Bay,
sitions 274 ? 203 Da and 358 ? 203 Da, respectively. The mass Shuram and Buah Fm.; Fig. 10a) as well as from Athel Basin in-
spectra are similar to those of steranes, with the m/z 217/218 tra-salt rocks (i.e. U Shale Fm./Athel Silicilyte/Thuleilat Fm.;
shifted to m/z 203/204 and m/z 149 to m/z 135 (Fig. 8). Although Fig. 10b). Concentrations of the C19 A-norsteranes 19A, 19B and
further research is needed to rigorously establish the structures 19C normalized to TOC were calculated for bitumens from carbon-
of these compounds, their diagnostic and common fragment ions ate stringers, Nafun Group and Athel Intra-salt source rocks (Tables
at m/z 203 and 135 suggest that they are norsteranes missing a S1 and 3). Averaged abundances clearly show that isomers 19A and
methylene unit from the A ring, whether by loss of the angular 19B are of the same order of magnitude across the whole sample
methyl or contraction of the ring, i.e. either 19-norsteranes or A- set, whereas the distinctive 19C isomer is about 10 times more
norsteranes respectively. Sedimentary A-norsteranes have been re- abundant in carbonate stringer rocks than in Nafun and Athel in-
ported only rarely. C26–C28 A-norsteranes were detected in Creta- tra-salt rocks. Similarly, specific isomers of C20 and C26 A-norster-
ceous black shales of Italy (van Graas et al., 1982) and structural anes exclusively occur in carbonate stringer bitumens and are
studies revealed that they contained a steroid-based skeleton with essentially absent from Nafun and Athel intra-salt rock samples
a five carbon A-ring. Interestingly, and perhaps significantly in this (Fig. 11).
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 99

a b
1.60 2.50

2.30
1.40
2.10
1.20
1.90
DNH/30H

35H/34H
1.00
1.70

0.80 1.50

1.30
0.60
1.10
0.40
0.90
0.20
0.70

0.00 0.50
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80 2.00 2.20 2.40 2.60 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
TNH/(Ts+Tm)
TNH/(Ts+Tm GA/30H
c d 1.00
1.80

1.60
0.80
1.40
3MH/2MH

1.20
0.60
22T/21T

1.00

0.80
0.40
0.60

0.40 0.20

0.20

0.00 0.00
0 2 4 6 8 10 12 14 16 18 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80
2MH index 24T/23T

A1C A2C A3C A4C

0.80
A5C Buah Masirah Bay Shuram

Silicilyte Thuleilat U Shale

0.60

Fig. 7. Crossplots of selected biomarker ratios for Huqf source rocks. Refer to Table 2 for biomarker ratios.

203
100
19C
67
81
260

55
95

%
245

135
121
108
148
164
189
217
231
0
60 80 100 120 140 160 180 200 220 240 260 280 300 320 340

Fig. 8. Mass spectrum of putative C19 A-norsterane 19C.

100 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

a A3C CS rock 19B Free HC

260 → 203
19C
19A

51.00 52.00 53.00 54.00 55.00 56.00 57.00 58.00 59.00

b 19B Kerogen

19A 19C

51.00 52.00 53.00 54.00 55.00 56.00 57.00 58.00 59.00

Fig. 9. MRM chromatograms 260 ? 203 Da showing distributions of C19 A-norsteranes in (a) free alkane fraction and (b) kerogen-bound alkanes of a A3C CS rock.

a b 19B OMR003
19B OMR149
m/z 203 Buah m/z 203 Thuleilat Shale

19C
19A 19C 19A

19B OMR154 19B OMR012

Shuram Silicilyte

19C
19A 19C 19A

19B 19B OMR014

OMR153
MasirahBay U Shale
19A 19C
19C 19A

22 24 26 28 30 32 34 36 38 4
40 42 44 22 24 26 28 30 32 34 36 38 40 42 44
Time Time

Fig. 10. Partial m/z 203 chromatograms showing distribution of C19 A-norsteranes in alkane fractions (a) of pre-salt rocks and (b) of Athel intra-salt rocks.

7. Oil geochemistry GC of the oil alkanes shows that more than half of the post-salt
Huqf oils (10 of 15) and 2 of 6 Q oils are affected by biodegradation,
Table 2 shows bulk properties for the oils as well as key bio- evident through the loss of n-alkanes and acyclic isoprenoids and
markers ratios obtained from MRM GC–MS. The fluid properties the presence of an unresolved complex mixture (Peters et al.,
of the oils vary significantly. Silicilyte oils are all characterized by 2005). The degree of biodegradation varies from moderate to se-
API gravity higher than 45°, whereas post-salt Huqf fluids tend to vere [biodegradation ranks based on the Peters and Moldowan
be quite heavy, with API between 3.4° and 29.1°. The API gravity (1993) scale listed in Table 2]. Mild biodegradation is recognized
of carbonate stringer oils is highly variable between 22.5° and by high Pr/C17 and Ph/C18 ratios, arising from the preferential bac-
51.5°. terial degradation of n-alkanes (Connan, 1984). Post-salt Huqf oils
Bulk carbon isotopic data (Table 2) were obtained on the satu- Nimr OMO004 as well as Q oils Misfar and Ghufos are the most al-
rated and aromatic hydrocarbon fractions of the oils. Fig. 12a tered and show virtually complete removal of n-alkanes and iso-
shows the familiar distinction of Q and Huqf oils based on the ster- prenoids. The relatively high proportion of C29 steranes (49%,
ane carbon number distribution and carbon isotopic compositions. Fig. 12a) and the very low abundance of C35 hopanes (Table 2) in
Within Huqf oils, bulk carbon isotopes of carbonate stringer oils Q oil Misfar result from the preferential degradation of C27 relative
span a wide range of values from 33‰ to 35.7‰. Silicilyte oils to higher C-number steranes and of C35 hopanes relative to lower
form a tighter group around 35‰. Post-salt Huqf oils are on aver- C-number hopanes (Peters et al., 2005). Homologous series of 25-
age lighter than silicilyte and carbonate stringer oils, clustering norhopanes were not detected even in the most severely biode-
around 36‰, with the exception of Jazal-1 at 34‰ (Table 2). graded oils. Significantly, none of the carbonate stringer oils and
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 101

274 → 203 358 → 203

100
OMR028 OMR028 *
CS rock A3C
* * CS rock A3C
* Crosstalks of

% * C27 steranes

OMR023 OMR023
100
Silicilyte Silicilyte
%

100
OMR026 OMR026
Shuram Shuram
%

Kaukab Kaukab
100 A3C CS oil A3C CS oil *
* *
% * *
0
32 33 34 35 36 37 38 39 40 41 48 49 50 51 52 53 54 55 56 57 58 59 60
Time Time

Fig. 11. MRM chromatograms for (a) 274 ? 203 Da and (b) 358 ? 203 Da showing distributions of C20 and C26 A-norsteranes, respectively, for rocks CS A3C OMR028,
silicilyte OMR023, Shuram OMR026 and for CS oil Kaukab A3C.

silicilyte oils shows signs of biodegradation. Silicilyte hydrocar- HCA were applied to MRM GC–MS-derived biomarker ratios and
bons have condensate-like API gravity values and are all character- used to delineate the oils into major families as well as to verify
ized by an extremely low biomarker content, challenging the some of the distinctive characteristics of the rocks (data not
acquisition of reliable sterane and hopanes measurement from shown). Biomarker ratios related to maturity were not considered
conventional GC–MS. However, MRM GC-MS allows the detection for this exercise. PCA was used to identify 20 biomarker ratios that
limit to be reduced and enabled us to measure reproducible bio- best account for the overall variability in the data. These were sub-
marker data for these oils. sequently used to construct the cluster analysis in Fig. 14. Four
Maturity-biomarker parameters such as 20S/(20S + 20R) and compositional oil groupings can be distinguished and a map of
20S abb/(abb + aaa) C29 steranes reach near end-point values resulting oil families is shown in Fig. 15:
(on average 0.53 and 0.59, respectively) indicating that SOSB oils
have been generated at the peak stage of oil generation. Further (1) Family A consists of silicilyte oils exclusively.
differentiation of the oils’ maturity is obtained from Ts/(Ts + Tm) (2) Family B is composed mainly of post-salt Huqf oils with two
and diasterane/sterane ratios (Fig. 12b). Silicilyte oils appear to carbonate stringer oils (Dhahaban South A1C and Kaukab
be the most mature, with Ts/(Ts + Tm) values close to unity, consis- A1C). Within Family B, two sub-clusters appear.
tent with their high API gravity. Q oils have also a relatively high (3) Family C is made up of carbonate stringer oils, with the
maturity and post-salt Huqf oils and carbonate stringer oils are exception of post-salt Huqf oil Ghufos and clusters into
generally the least mature (early to peak oil window). However, two major sub-groupings CI and CII, which are mainly geo-
carbonate stringer oils display a broad range of thermal maturity, graphically controlled. Indeed, CI is composed of carbonate
which becomes even more apparent when their reservoir depths stringer oils from the Birba field or geographically close,
are evaluated (Fig. 13). whereas CII consists primarily of carbonate stringer oils
As previously found, Huqf oils consisting of post-salt oils, silic- located in the southwestern part of the SOSB (Fig. 15). It
ilyte and carbonate stringer oils have very similar patterns of bio- appears that the pressure regime does not influence the
marker hydrocarbons. The predominance of C29 steranes is groupings, as normally-pressured A2C oils Rabab/Sakhiya/
pervasive, as are high concentrations of C35 hopanes, 28,30-dino- Fayrouz/Zalzala cluster separately from normally-pressured
rhopane and 25,28,30-trinorhopane (Fig. 12). This apparent simi- A4C oils Budour and Birba North.
larity has obscured many of the more subtle features that might (4) Family D is comprised entirely of Q oils.
reflect more specific oil-source relationships. Distinct features dis-
played by Q oils in contrast to Huqf oils, include: much higher
abundances of gammacerane, 28,30-dinorhopane (Fig. 12c) and 8. Oil-source rock correlations
3-methylhopanes (Fig. 12d), as well as high C24/C23 and low C22/
C21 cheilanthanes ratios (Fig. 12f). 8.1. Silicilyte oils
The use of statistical analysis applied to biomarker data is
essential to identify those geochemical parameters that best ac- The silicilyte oils are very mature and so are characterized by
count for the variability in the entire data set and enable oil family API gravity above 45° and a very low biomarker content. Biomarker
relationships to be accurately and robustly established. PCA and analysis with conventional GC–MS does not allow their detection
102 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

% 29 steranes
a 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 b
-28 1.00

Q oils
-30
0.80
Misfar
maturity

Ts/(Ts+Tm)
-32
"Huqf" oils
δ13C aros

0.60

-34

0.40
Clastic input
-36

0.20
-38

-40 0.00
0.00 0.05 0.10 0.15 0.20 0.25 0.30
dia/(dia+reg) 27 steranes

c 1.20 d 4.50

4.00
1.00
3.50

3MH/2MH
0.80 3.00
DNH/30H

2.50
0.60
2.00

0.40 1.50

1.00
0.20
0.50

0.00 0.00
0.00 0.10 0.20 0.30 0.40 0.50 2 4 6 8 10 12 14
TNH/(Ts+Tm) 2MH index

e 1.40 f 0.80

1.20 0.70

0.60
1.00
22T/21T

0.50
x-24/n-24

0.80
0.40
0.60
0.30
0.40
0.20

0.20 0.10

0.00 0.00
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
x-22/n-22 24T/23T

Huqf oil Q oil A1C oil A2C oil

A3C oil A4C oil A3C+A4C oil A5C oil

A6C oil sil. oils

Fig. 12. Cross plots of selected biomarker parameters for SOSB oils. Refer to Table 2 for biomarker ratios. X-22: Mid-chain C22 MMAs; n-22: linear C22 alkane; dia/(dia + reg)
27 steranes = C27 diasteranes/(C27 regular steranes + C27 diasteranes).

and requires the sensitivity of a magnetic sector instrument using However, clues about their origin are provided by a few matu-
MRM for precise quantification. Most of the biomarker distribu- rity-independent parameters. The partial chromatogram generated
tions in these oils reflect the high degree of maturity and are there- from the MRM transition 260 ? 203 Da reveals the lack of isomer
fore of limited use for correlation purposes. Maturity has also 19C in the C19 A-norsteranes distributions of silicilyte oils, which
affected bulk carbon isotopic values of silicilyte oils, shifting them rules out the carbonate stringers as a source (Fig. 16a). Several cri-
towards heavier values and compromising their utility as a corre- teria indicate that silicilyte oils are mainly derived from Athel in-
lation tool. tra-salt rocks: they have high concentrations of mid-chain MMAs
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 103

Ts/(Ts+Tm) (Fig. 12e), relatively high gammacerane contents (GA/30H = 0.21

0.00 0.20 0.40 0.60 0.80 1.00 on average) as well as a high proportion of C35 hopanes relative
500 to C34 hopanes (Table 2). Additionally, silicilyte oils are among
Huqf oil the SOSB oils showing the highest 2-methylhopane index values,
which are associated with high 2-methylhopanes relative to 3-
Q oil methylhopanes, as observed for Athel intra-salt rocks (3MeH/
1500
2MeH 0.4 on average for silicilyte oils and Athel intra-salt rocks;
A1C oil
Fig. 12d).
Depth below surface (m)

The high relative abundance of 25,28,30-trinorhopane and

A2C oil
2500 28,30-dinorhopane, characteristic of the Athel intra-salt rocks, is
A3C oil
not a feature of silicilyte oils due to their elevated maturity
(Fig. 12c). Athel intra-salt rocks are in contrast immature, as shown
Kaukab A1C
A4C oil by Tmax values (Table 1) and triaromatic steroid index values (data
3500
not shown). This discrepancy in thermal history reflects sample
A3C+A4C oil availability within the silicilyte oils since virtually all are found
in deep reservoirs (between 3500 and 4000 m). In contrast, the
4500 A5C oil maximum depth for the Athel intra-salt rocks analyzed is
2300 m. The ratio of 28,30-dinorhopane to 25,28,30-trinorhopane
A6C oil (DNH/TNH) is useful for circumventing the problem of maturity
differences between rocks and oils, since it remains unaffected
5500 sil. oils
during maturation (Peters et al., 2005). Silicilyte oils have on aver-
age a DNH/TNH value of 2.3, a close match with the average exhib-
ited by Athel intra-salt rocks (Table 3), providing additional
Fig. 13. Plot of Ts/(Ts + Tm) vs. reservoir depth for all SOSB oils.
evidence for their correlation.

1.0 0.8 0.6 0.4 0.2 0.0

AL NOOR OMO050 Sil.
AL NOOR OMO044 Sil.
AL NOOR OMO030 Sil. Family A:
AL SHOMOU OMO046 Sil.
AL SHOMOU OMO048 Sil. Silicilyte oils
AL NOOR OMO025 Sil.
AL SHOMOU OMO029 Sil.
THURAYAH OMO028 Huqf
MAURID OMO026 Huqf
THAMOUD OMO022 Huqf
NUWAR OMO009 Huqf
MARMUL OMO024 Huqf B
MARMUL OMO010 Huqf
DHB STH OMO005 A1C
SAHAM OMO013 Huqf
MUKZNA NTH OMO002 Huqf
REIHAN OMO023 Huqf Family B
JALMUD NTH OMO007 Huqf
JAZAL OMO003 Huqf B
NIMR OMO011 Huqf
RUNIB OMO008 Huqf
NIMR OMO004 Huqf
KAUKAB OMO0040 A1C
GHUFOS OMO014 Huqf
OMRAAN OMO037 A5C
OMRAAN OMO045 A4C+A3C
BIRBA NTH OMO006 A4C C
BIRBA OMO038 A4C
BIRBA STH OMO036 A4C
BIRBA OMO016 A4C
KAUKAB OMO041 A3C
DURRA OMO039 A3C
SUWAIHAT OMO015 A5C
BUDOUR OMO058 A4C
QASHOOB OMO059 A6C Family C
ANDHUR OMO035 A6C
GHAFEER OMO052 A3C
GHAFEER OMO053 A2C
DAFAQ OMO057 A2C C
SARMAD OMO054 A5C
SARMAD OMO051 A3C
HWL DEEP OMO031 A3C
HWL DEEP OMO049 A2C
HAWMYAT OMO043 A5C
FAYROUZ OMO056 A2C
RABAB OMO034 A2C
SAKHIYA OMO033 A2C
ZALZALA OMO055 A2C
GHUFOS OMO021 Q
ZAULIYAH OMO019 Q
KATHEER OMO020 Q
ANZAUZ OMO018 Q
Family D:
SUWAIHAT OMO012 Q Q oils
MISFAR OMO001 Q

Fig. 14. Cluster analysis dendogram showing principal oil families in the SOSB.
104 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

55˚0'0"E 56˚0'0"E

Anzauz Q

Oil families
Zauliyah Q
Group A
Group B I
Group B II
Group C I
Group C II
20˚0'0"N Group D Suwaihat A5C Suwaihat Q
20˚0'0"N

Katheer Q

Mukhaizna North
PS Huqf
Ghufos
PS Huqf
Misfar Q Ghufos Q

Jalmud North
PS Huqf
19˚0'0"N
19˚0'0"N
Thurayah
PS Huqf

Reihan
PS Huqf
Al Noor Al Noor Nimr OMO004 Runib
OMO044 Sil. OMO025 Sil. PS Huqf PS Huqf
Al Noor Al Noor Saham-1
OMO030 Sil. OMO050 Sil. PS Huqf
Al Shomou Al Shomou
OMO046 Sil. OMO048 Sil. Nimr OMO011 Nuwar-1
Al Shomou PS Huqf PS Huqf
Birba North OMO029 Sil.
A4C
Omraan
A3C+A4C Budour A4C
Omraan A5C
Birba OMO016
A4C Birba OMO038 A4C
Birba South A4C
Durra A3C
Marmul OMO010 Maurid
Kaukab PS Huqf PS Huqf
Rabab Hawmyat
AndhurA2C A3C Kaukab
A5C A1C
A6C Thamoud
Zalzala A2C Marmul OMO024 PS Huqf
Fayrouz A2C PS Huqf
18˚0'0"N Sakhiya A2C
Dafaq A2C 18˚0'0"N
Sarmad A5C
HD A3C Sarmad A3C
Qashoob Ghafeer A2C
A6C Ghafeer
A3C

Dhahaban South A1C

0 20 40 60 80 Kilometers
Jazal PS Huqf

55˚0'0"E 56˚0'0"E

Fig. 15. Location map of oils coded by family as identified by hierarchical cluster analysis of biomarker compositions.

Further discrimination between Athel intra-salt rocks samples high quality. However, this scenario is challenged by the fact that
has proven difficult. However, we note that among other close sim- the stringers are (or were previously), fully encased in salt, with
ilarities, mid-chain MMAs are especially abundant in the Athel no tangible access to regional oil charge, with the exception of
Silicilyte and Thuleilat Fm samples, in comparison with the U some of the lower stringer units which, from drilling results,
Shale. grounded on Nafun rocks. An example of this is the Kaukab A1C
accumulation. Isolation of stringers in the salt has, in fact, led geol-
8.2. Carbonate stringer play ogists to favour a self-charging mechanism with the carbonate
stringers acting both as source rock and reservoir. Yet, the apparent
The origin of the charge for carbonate stringer accumulations is lack of source rock potential, based on low TOC relative to other
highly conjectural and two main mechanisms have been proposed. units in the carbonate stringers, as well as the absence of unequiv-
A first charging model involves the contribution of source rocks ocal geochemical evidence supporting this hypothesis has up to
from the Nafun Group which, by all standards, are of exceedingly now undermined the self-sourcing scenario.
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 105

260 → 203
a OMO025
Al Noor
19B
100
Silicilyte oil
19C
19A
%

0
32.0 32.5 33.0 33.5 34.0 34.5 35.0 35.5 36.0 36.5 37.0 37.5
Time
b 19B
OMO023
100
Reihan
Post-salt
%
Huqf oil 19C
19A

0
32.0 32.5 33.0 33.5 34.0 34.5 35.0 35.5 36.0 36.5 37.0 37.5
Time

Fig. 16. MRM chromatograms 260 ? 203 Da showing distributions of C19 A-norsteranes in alkane fractions of (a) Al Noor silicilyte oil (OMO025) and (b) Reihan post-salt
Huqf oil.

The putative A-norsteranes, described in section 6.4, shed 8.3. Mixed accumulations in the carbonate stringers
light on the source of the carbonate stringer oils. The C19 A-nor-
sterane pattern, with the 19C isomer in significant abundance Carbonate stringer oils with low relative abundance of iso-
along with isomers 19A and 19B, observed in carbonate stringer mers 19C (Kaukab A1C, Suwaihat A5C, Qashoob A6C and Dhah-
rocks, is present in virtually all produced carbonate stringer oils aban South A1C, inset Fig. 18) might be interpreted as partially
from each stratigraphic interval (Fig. 17). The 19C/19A and 19B/ produced from Nafun rocks, since mixing of a carbonate stringer
19A ratios enable a clear distinction between the carbonate charge and a pre-salt charge would lead to a dilution of C19 A-
stringer rocks and oils and Nafun rocks/Athel intra-salt rocks, norsterane 19C relative to isomers 19A and 19B in the resulting
as illustrated in Fig. 18. Furthermore, the C20 and C26 A-norstera- accumulation. Of these oils, Kaukab A1C and Dhahaban South
ne distributions in the carbonate stringer oils mimic those of the A1C did not fall into the main carbonate stringer family C in
carbonate stringer bitumens, and contain A-norsterane isomers the hierarchical cluster analysis dendrogram (Fig. 14) and are
that are missing from pre-salt and Athel intra-salt rocks found in reservoirs with potential access to Nafun sediments.
(Fig. 11). This efficient discrimination of carbonate stringer rocks Within carbonate stringer sub-cluster CII, Qashoob stands out
and oils from pre-salt and Athel intra-salt rocks through A-nor- as an outlier (Fig. 14). Such statistical outliers can result from
sterane distributions provides strong and novel evidence that the mixing of sources representing different end members or
the carbonate stringer oils are predominantly self-sourced. In- unrecognized source rocks. A mixed character for these crudes
deed, the fact that concentrations of isomers 19A and 19B are is evident from examination of their biomarker ratios, which re-
of the same order of magnitude in carbonate stringers and Nafun veals discrepancies from the average values presented by car-
rocks indicates that any significant input of C12 + hydrocarbons bonate stringer oils. Kaukab A1C, Dhahaban South A1C,
from the latter in carbonate stringer oil accumulations should Suwaihat A5C and Qashoob A6C share characteristics with Nafun
be evident through dilution of compound 19C compared to rocks while exhibiting typical carbonate stringer oil features as
19A and 19B, which is rarely the case. illustrated in Table 4. Kaukab A1C is also one of the oils with
Additional lines of evidence adding weight to the proposal that a thermal maturity off the trend observed for carbonate stringer
carbonate stringer oils are self-sourced can be summarized as oils (Fig. 13). The thermal maturity of Kaukab A1C as revealed by
follows: Ts/(Ts + Tm) appears to be higher than predicted from its reser-
voir depth, suggesting a pre-salt contribution for this oil rather
 The trend of increasing thermal maturity with depth displayed than entirely local sourcing. Compound-specific hydrogen isoto-
by the Ts/Tm ratio plotted against reservoir depth in the carbon- pic data confirm this (data not shown).
ate stringers (Fig. 13) provides additional indirect confirmation Deciphering the input from pre-salt rocks in the carbonate
of local sourcing for the majority of these accumulations, as stringer oils via the lack of a specific marker for the pre-salt section
opposed to migration from deeper rocks. is not trivial. The possibility that these apparently conflicting ratios
 Statistical cluster analysis based on biomarker ratios, which did may result from local variations in the composition of the carbon-
not include the discriminating A-norsteranes 19C/19A ratio, ate stringers producing these outliers cannot be ruled out at this
clearly showed that the bulk of the carbonate stringer oils clus- stage.
ter separately from the other oils in the SOSB as a distinct oil
grouping (Fig. 14). 8.4. Post-salt Huqf oils
 Biomarker distributions within free and kerogen-bound ali-
phatic fractions of carbonate stringer rocks show strong similar- Of the post-salt Huqf oils analyzed, few show the 19C norstera-
ities to those of carbonate stringer oils. Details will be reported ne isomer, precluding significant charge from carbonate stringers
elsewhere (Stalvies et al., unpublished results). to the Phanerozoic reservoirs (Figs. 16b and 19). One notable
106 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

19B
m/z 203 OMO035
Andhur A6C

19C
19A

19B
OMO037
Omraan A5C
19C

19A

19B
OMO036
Birba South A4C

19A 19C

19B OMO051
Sarmad A3C

19C
19A

19B OMO052
Ghafeer A2C

19C
19A

19B OMO005
Dhahaban South A1C

19A
19C

22 24 26 28 30 32 34 36 38 40 42 44

Time

Fig. 17. Partial m/z 203 chromatograms showing distribution of C19 A-norsteranes in alkane fractions of carbonate stringer oils.

exception is the Jazal sample, which also shows relatively heavy The challenge for understanding Eastern Flank reservoir charge
d13C values ( 33.9‰ for saturates and 34.1‰ for aromatics) is in reliably assessing the contribution of Nafun rocks and Athel
when compared with the rest of post-salt Huqf oils. The relatively Basin intra-salt rocks, respectively. Difficulties arise from the lack
abundant 19C A-norsterane, along with carbon isotopic composi- of specific biomarkers for the pre-salt section, which could contrib-
tions similar to those of carbonate stringer oils suggest that the Ja- ute subtly to any oil, and from the variability in the biomarker
zal accumulation has a strong carbonate stringer input. character within given Nafun formations (cf. Section 6.3). Average
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 107

5.00

4.50 A1C oil

A2C oil
4.00 A3C oil
A4C oil
3.50 A4C+A3C oil
A5C oil
3.00 A6C oil
Masirah Bay
19C/19A

Shuram
2.50
Buah
Carbonate stringer
Thuleilat shale
2.00 oils and rocks Silicylite
U shale
1.50 A1C
A2C
1.00 A3C
A4C
0.50 A5C
Pre-salt and Athel
intra-salt rocks
0.00
2 3 4 5 6 7 8
19B/19A

1.00

0.90
Dhahaban Sth A1C
0.80

0.70

0.60
19C/19A

Qashoob A6C
0.50

0.40

0.30
Suwaihat A5C
0.20 Kaukab
A1C
0.10

0.00
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
19B/19A

Fig. 18. Plot of 19C/19A vs. 19B/19A for all Huqf rocks and carbonate stringer oils.

Table 4
Summary of biomarker characteristics exhibited by selected post-salt Huqf and carbonate stringer oils (Refer to Table 2 for ratios; MMAs: mid-chain monomethyl alkanes)

Oil Stratigraphy Pre-salt characteristics Intra-salt characteristics

Nuwar PS Huqf High GA/30H, high 22T/21T, low 23T/24T, high 2MHI
Maurid PS Huqf High GA/30H, high 22T/21T, low 23T/24T, high 2MHI,
high DNH/30H
Mukhaizna PS Huqf High 35H/34H, high 22T/21T, low 23T/24T
North
Ghufos PS Huqf High 35H/34H, high 22T/21T, low 23T/24T, high 2MHI
Runib PS Huqf Low GA/30H, low 35H/34H Low 22T/21T, high 23T/24T Low 2MHI
Nimr PS Huqf Low GA/30H, low 35H/34H Low 22T/21T, high 23T/24T
Kaukab A1C Low 35H/34H, low GA/30H Low DNH/30H, low TNH/(Ts + Tm), High 2MHI, high MMAs
low 22T/21T, high 23T/24T
Dhahaban A1C Low TNH/(Ts + Tm), low GA/30H High 22T/21T, low 23T/24T
Suwaihat A5C Low GA/30H, low TNH/(Ts + Tm) High 2MHI, high 2MH/3MH High 22T/21T, low 23T/24T
Qashoob A6C Low 35H/34H, low 22T/21T, high 23T/24T High 2MHI, high DNH/30H

trends for the potentially opposing Athel intra-salt and Nafun rocks (Table 2). This alone indicates that the latter contribute predomi-
summarized in Table 3 are used here to detect respective inputs. nantly to accumulations in the Phanerozoic reservoirs of the East-
Briefly, the most useful parameters were relative abundance of ern Flank. Bulk carbon isotopic compositions also tend to support a
C35 hopanes, gammacerane, MMAs, 28,30-dinorhopane and main Athel intra-salt charge for the post-salt Huqf oils: the latter
25,28,30-trinorhopane, proportion of 2a-methylhopanes relative are characterized by 13C-depleted saturated and aromatic hydro-
to 3b-methylhopanes, 2-methylhopane index, and 22T/21T and carbon fractions in comparison with other SOSB oils (Fig. 12a, Table
24T/23T ratios. 2), in spite of the fact that most of these oils are affected by biodeg-
Post-salt Huqf oils have on average high relative abundances of radation, which is known to shift d13C towards heavier values.
gammacerane and high 35H/34H values at levels comparable only With the exception of Jazal, bulk d13C values of saturated hydrocar-
with those observed for Thuleilat Fm. and Athel Silicilyte samples bon fractions in post-salt Huqf oils form a very tight cluster from
108 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110

1.80

1.60

Jazal
1.40
PS Huqf oils
Carbonate stringers
1.20
Masirah Bay

Shuram
19C/19A

1.00

Buah
0.80
Thamoud Thuleilat shale
0.60
Silicylite

0.40
U shale

0.20

0.00
0.00 0.05 0.10 0.15 0.20 0.25 0.30
19C/(19A+19B)

Fig. 19. Plot of 19C/19A vs. 19B/19A for Huqf rocks and post-salt Huqf oils.

34.8‰ to 36.2‰, which corresponds best to the range of values would have been lost. Apparently, relatively recent salt movement
exhibited by Thuleilat Fm. and Athel Silicilyte rocks, even more so has allowed some leakage from the Athel sub-basin, accounting for
if the effects of biodegradation are considered. the oils now found in the Phanerozoic Eastern Flank reservoirs.
However, the degree to which these formations contribute to
Eastern Flank reservoirs is variable. Some post-salt Huqf oils 9. Conclusions
including Mukhaizna North, Nuwar, Ghufos and Maurid show a
strong Athel intra-salt character as suggested from a combination A new geochemical basis has been established for oil source
of biomarker ratios (Table 4). Ghufos is the only post-salt Huqf correlation in the South Oman Salt Basin. Novel steroidal biomark-
oil clustering with carbonate stringer oils. However, the low rela- ers, as well as the more commonly used steroids and triterpenoids
tive abundance of 19C A-norsterane in this oil rules out charging show secular and palaeoenvironmental changes through the Nafun
from carbonate stringers. The clustering of post-salt Huqf Ghufos and Ara Groups of the Huqf Supergroup, which helped establish
with carbonate stringer oils reflects its affinity with the Ara charac- reliable oil-source correlations.
ter. In contrast, Runib, Nimr OMO004 and Nimr OMO011 appear to The source rocks that are positively identified as contributing
have a Nafun affinity. The difference in biomarker character of to significant hydrocarbon accumulations comprise the Ara car-
these two sets of post-salt Huqf oils is revealed in the cluster anal- bonate stringers and the Athel sub-basin sediments (U, Thuleilat
ysis dendrogram (Fig. 14) where Mukhaizna North, Nuwar and and Athel Silicilyte). The relative abundances of novel com-
Maurid cluster as a separate sub-grouping (Family BI) from Runib, pounds interpreted as being A-norsteranes were found to be
Nimr OMO004 and Nimr OMO011 oils (Family BII) (Fig. 14). Runib, invaluable for distinguishing carbonate stringer bitumens, kero-
Nimr OMO004 and Nimr OMO011 oils cluster with Kaukab A1C, gens and their derived oils from other kinds of SOSB hydrocar-
which also showed strong pre-salt affinities. It is therefore feasible, bons. The patterns of C19 A-norsteranes suggest that the bulk
but not proven, that the oils clustering as family BII have some of the carbonate stringer oils are self sourced. This key finding
component of Nafun hydrocarbons. is supported by additional independent geochemical data includ-
The apparent absence of abundant hydrocarbon deposits or ing, especially, the ranking of maturity derived from C27 hopa-
even residual oil derived from Nafun rocks, which are by any mea- noids and present day burial depth. The C19 A-norsteranes are
sure very good source rocks, is perplexing. Previous workers have accompanied by C20 counterparts and probable precursors with
suggested (Paul Taylor, personal communication) that there was intact side chains, readily detected by M+ ? 203 Da fragmenta-
a potential disjunction between hydrocarbon generation and tion reactions in GC–MS–MS.
emplacement of traps or seals. The demonstration herein that vir- Deciphering and quantifying inputs from Nafun rocks to oil
tually all the SOSB hydrocarbons originate from within the Ara (i.e. accumulations has proved challenging, with the lack of specific
intra-salt) sequence, either in carbonate stringers or within the markers for the pre-salt section. The most useful geochemical
Athel sub-basin, offers verification of this. Oil generation from characteristics delineating Nafun Group organic matter from Ara
OM within the salt sequence will be slower and occur later than Group intra-salt source rocks include: low relative abundance of
for the Nafun rocks due to the insulating properties of the evapo- mid-chain monomethylalkanes (X-compounds); low relative
rite minerals. The carbonate mineral matrix of most Ara sediments abundance of gammacerane, 28,30-dinorhopane, 25,28,30-trino-
also helps suppress catagenesis over long geological times rhopane and 2-methylhopanes; low C22T/C21T and high C23T/
(> 540 Ma), compared to clastic source rocks which would have C24T cheilanthane ratios. Based on these parameters, Ara source
generated lighter oil and more gas. Moreover, apart from the lower rocks were found to be the predominant source for Huqf oils.
stringers, many intra-salt reservoirs are subject to significant over- Subtle aspects of the composition of some carbonate stringer
pressure, further retarding catagenesis. Hydrocarbons generated and post-salt Huqf oils could suggest some degree of sourcing
and reservoired within the salt could, therefore, be retained until from the Nafun rocks but stronger evidence is needed to confirm
geologically more recent times, while those generated outside this.
 E. Grosjean et al. / Organic Geochemistry 40 (2009) 87–110 109

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