Magmatically driven hydrocarbon generation and fluid

flow in the Namibe Basin of Angola

Edoardo Fiordalisi1, Bart van Dongen1, Julian Moore2,
Nathan Rochelle-Bates1, Vladimir A. G. Machado3, Richard Dixon4,
Ian Sharp5 and Stefan Schröder1*
1
Department of Earth and Environmental Sciences, University of Manchester, Manchester
M139PL, UK
2
Applied Petroleum Technology, Conwy LL32 8FA, UK
3
Centro de Pesquisa e Desenvolvimento, Sonangol, Rua Rainha Ginga 29/31, C.P. 1316,
Luanda, Angola
4
BP Exploration, Sunbury-on-Thames TW16 7LN, UK
5
Exploration Technology, Equinor ASA, PO Box 7200, 5020 Bergen, Norway
EF, 0000-0003-0978-9231
*Correspondence: stefan.schroeder@manchester.ac.uk

Abstract: Magmatic activity can severely alter the thermal structure of a sedimentary basin, with variable
effects on the petroleum system. The Namibe Basin of Angola (Cretaceous South Atlantic rift) contains
well-exposed magmatic and petroleum system elements and allows integrated assessment of how magmatic
activity can modify the petroleum system. The basin was affected by syn-rift and post-rift magmatic events,
and bitumen is observed within both the Pre- and Post-Salt stratigraphical sections. In the Pre-Salt, fluorescent
bitumen has a lacustrine signature and is associated with calcite and quartz cements. Onshore Pre-Salt units are
thermally immature, and therefore the source rock that generated the Pre-Salt bitumen is likely located offshore.
Hydrocarbons migrated or re-migrated via magmatically driven fluids, reaching the present-day onshore. Closer
to magmatic units, non-fluorescent pyrobitumen was instead observed, evidencing hydrocarbon cracking pro-
cesses following emplacement. In the Post-Salt, bitumen is in situ and shows marine-like signatures compatible
with an immediate Post-Salt source rock depositional environment. In the immediate Post-Salt, units with very
high total organic carbon values (TOC; up to 13.8%) and excellent source rock properties (hydrogen index
.600 mgHC g−1 TOC) have reached thermal maturation. Within the Namibe Basin these Post-Salt source
units lie in proximity to major Turonian–Coniacian–Santonian volcanic centres and associated shallow intru-
sions, which are likely to have caused thermally forced maturation processes and generation of the Post-Salt
hydrocarbons. This paper demonstrates the importance of an integrated field, petrographic and geochemical
approach in unravelling the influence of magmatic activity on basin thermal structure and petroleum systems.

Magmatic activity can have multiple effects on the
thermal structure of a basin and its petroleum system
elements, and can positively or negatively affect the
hydrocarbon prospectivity in such sedimentary
basins (Fig. 1; Senger et al. 2017). Heat generated
by igneous intrusions can cause rapid forced thermal
maturation of immature source rocks, with this pro-
cess being highly dependent on the duration and tem-
perature regime of the magmatic activity, intrusion
thickness and the distance of the organic-rich units
from the intrusions (Stagpoole and Funnel 2001;
Aarnes et al. 2010; Muirhead et al. 2017, 2018;
Senger et al. 2017). The impact of magmatic intru-
sions on organic matter is defined by aureoles
typically varying between 30 and 250% of the
intrusion thickness (Aarnes et al. 2010; Senger
et al. 2017). Therefore, while source rock forced
maturation processes often occur at a local scale,
hundred-metre-thick intrusions and/or high densi-
ties of intrusive bodies could potentially lead to the
generation of significant hydrocarbon volumes
(Muirhead et al. 2017, 2018). Furthermore, exten-
sive magmatic activity can enhance source rock mat-
uration at a basin scale by increasing the regional
heat flow (Mørk and Bjorøy 1984; Senger et al.
2017). Negative effects of magmatic activity on
source rocks include over maturation of sections in
direct contact with the intrusions, or sections that
had already reached maturation via conventional
burial processes, leading to a loss of total organic

From: Kilhams, B., Holford, S., Gardiner, D., Gozzard, S., Layfield, L., McLean, C., Thackrey, S. and Watson, D. (eds)
The Impacts of Igneous Systems on Sedimentary Basins and their Energy Resources.
Geological Society, London, Special Publications, 547,
https://doi.org/10.1144/SP547-2023-44
© 2024 The Author(s). This is an Open Access article distributed under the terms of the Creative Commons Attribution
License (http://creativecommons.org/licenses/by/4.0/). Published by The Geological Society of London.
Publishing disclaimer: www.geolsoc.org.uk/pub_ethics
 E. Fiordalisi et al.
Fig. 1. Effects of magmatic activity on the petroleum
system. (a) Petroleum system not affected by magmatic
activity. (b) Petroleum system affected by magmatic
activity, with igneous intrusions cracking a previous oil
accumulation into gas and causing forced maturation
processes within shallower source rocks. Source:
modified from Senger et al. (2017).
carbon (TOC) and hydrocarbon generating potential
(Mørk and Bjorøy 1984; Lindgren and Parnell 2006;
Rohrman 2007; Senger et al. 2017; Muirhead et al.
2018). Magmatic activity can finally have drastic
effects on in-place hydrocarbon accumulations,
cracking oil into gas and pyrobitumen, or via mag-
matically driven fluids displacing and re-migrating
the in-place hydrocarbons (Bump et al. 2017, 2018).
Site-specific studies are often needed to assess
whether magmatic activity relates to an overall
exploration risk or opportunity (Senger et al.
2017). The Namibe Basin of Angola, the focus of
this study, is an underexplored rift basin within the
South Atlantic hydrocarbon province, where the
effects of magmatic activity had a significant impact
on the petroleum system evolution, affecting source
rock maturation and the preservation/remobilization
of existing hydrocarbon accumulations (Bump et al.
2017, 2018). The basin was characterized by multi-
ple phases of syn- and post-rift magmatic activity
and contains significant onshore bitumen occur-
rences at several localities along the basin strike,
which are evidence of a working petroleum system
within the magmatically influenced basin. Magmatic
and petroleum system elements are well exposed at
several localities along the basin strike, and the igne-
ous geochronology has improved significantly in
recent years (Renne et al. 1996; Jerram et al.
2019). This makes the Namibe Basin an ideal
study area to identify, characterize and link micro-
to basin-scale observations and understand interrela-
tionships between geological processes within mag-
matically influenced basins. The origin of the
bitumen in the Namibe Basin was therefore investi-
gated via an integrated field, petrographic and geo-
chemical study to assess the impact of magmatic
activity on source rock maturation and hydrocarbon
remobilization and preservation, highlighting when
these processes are likely to represent exploration
risks or opportunities.
Geological setting and petroleum system
The Namibe Basin of southern Angola formed in the
Early Cretaceous as part of the South Atlantic rift
(Moulin et al. 2010). The basin boundaries are repre-
sented by the Benguela Fracture Zone to the north
and by the Walvis Ridge to the south (Fig. 2a).
Onshore, a basin bounding fault separates the basin
fill from the crystalline basement eastwards
(Fig. 2b; Gindre-Chanu et al. 2015; Schröder et al.
2016). The Namibe Basin shares tectonostratigraph-
ical similarities with the other South Atlantic basins
of the African and Brazilian margins, characterized
by ‘Pre- and Post-Salt’ sequences, separated by
Aptian evaporites (Fig. 2c; Brownfield and Char-
pentier 2006). The oldest unit of the Namibe Basin
Pre-Salt sequence is the early syn-rift Bero Volcanic
Complex (BVC), unconformably overlying the Pre-
cambrian granitic basement (Fig. 2c; Marsh and
Swart 2018). The BVC represents the northern
extension of the c. 134 Ma Paraná–Etendeka igneous
province, and is characterized by tholeiitic basalts
and quartz latites, interlayered with volcaniclastic
and fluvial/aeolian sandstones (Gindre-Chanu
et al. 2016; Marsh and Swart 2018). The BVC under-
went significant faulting and tilting as part of the
main South Atlantic rift event, followed by erosion
creating an incised topography on the BVC (Gindre-
Chanu et al. 2016; Sharp et al. 2016). Spring and
lacustrine carbonates, and fluvio-deltaic to marginal
marine siliciclastic units were deposited during a sag
phase with further significant crustal thinning and
subsidence (Fig. 2c; Gindre-Chanu et al. 2015,
2016; Sharp et al. 2016; Jerram et al. 2019). These
are overlain by Mid-Aptian evaporites, resulting
from the establishment of marine and hypersaline
conditions in the basin (Fig. 2c; Grosdidier et al.
1996; Braccini et al. 1997; Gindre-Chanu et al.
2015, 2016). The Post-Salt sequence in the Namibe
Basin was mostly deposited under passive margin
conditions. Late Aptian–Early Albian mixed marine
carbonates and siliciclastic units are unconformably
overlain by Albian to Early Coniacian coarse-
grained siliciclastic units (Fig. 2c; Gindre-Chanu
 Namibe Basin petroleum system

Fig. 2. Namibe Basin structural setting and onshore stratigraphy. (a) Namibe Basin location within the African
margin. (b) Digital elevation model showing structural trends (red) and basin bounding fault (black) in the Namibe
Basin. Orientation of structural lineaments for the southern, central and northern parts of the basin is indicated by rose
diagrams. The main study localities are also indicated. (c) Namibe Basin onshore stratigraphy. Source: (a) modified
from Comin-Chiaramonti et al. (2011) and Strganac et al. (2014); (b) modified from Rochelle-Bates et al. (2020); (c)
modified from Jerram et al. (2019).

et al. 2015; Sharp et al. 2016; Swart et al. 2016; Jer-
ram et al. 2019). The siliciclastics and carbonate
rocks have been intruded by and interbedded with
alkaline volcanics of varying compositions within
the Salinas to Bentiaba Formations (Fm; Fig. 2c;
Sharp et al. 2016; Swart et al. 2016; Jerram et al.
2019). The volcanic events have been well con-
strained with geochronology and biostratigraphical
controls and can be shown to start at c. 91 Ma in
the northern periphery of the Namibe Basin and
young southwards, with the Bentiaba Fm within
the main part of the Namibe Basin yielding ages
between 88 and 81 Ma (Sharp et al. 2012, 2016;
Strganac et al. 2014; Swart et al. 2016; Jerram
et al. 2019; Rochelle-Bates et al. 2020). Even older
volcanic pulses of c. 100 Ma are seen in the Kwanza
Basin further north (Jerram et al. 2019), which
reflects widespread Post-Salt alkaline magmatic
activity that affected the conjugate margins of
Angola and Brazil during this time window, creating
the Peri Atlantic Alkaline Igneous Province (Matton
and Jébrak 2009). Post-Salt magmatic activity in the
Namibe Basin is also associated with renewed exten-
sional faulting and the local development of spring
mound carbonates, evidence of magmatically driven
fluid flow (Fig. 2c; Sharp et al. 2012; Swart et al.
2016; Jerram et al. 2019; Fiordalisi et al. 2021a).
This magmatically driven fluid flow also affected
Pre-Salt units, as testified by calcite veins formed
during the period of Late Cretaceous magmatic
activity that are observed within Pre-Salt carbonates
(Rochelle-Bates et al. 2020). Younger siliciclastic
units of Campanian, Maastrichtian and Cenozoic
age were deposited in a shallow marine to fluvial
 E. Fiordalisi et al.

setting (Fig. 2c; Sharp et al. 2016; Swart et al. 2016;
Jerram et al. 2019), before Late Cenozoic uplift
(Green and Machado 2015).
Onshore organic-rich units are present within
Pre-Salt siliciclastics and immediately below the
evaporites, while in the Post-Salt, laterally extensive
organic-rich units are mainly observed directly over-
lying the evaporites (Fiordalisi et al. 2021b; Fig. 2c).
Bitumen occurs across the whole basin strike within
the Pre- and Post-Salt units, including the BVC, Pre-
Salt carbonates and the carbonate/siliciclastic units
directly overlying the evaporites (Fig. 2c).
Samples and methods
Sampling
12° 32′ E; Fig. 2b). Main sedimentary and volcanic
units were described, with a particular focus on bitu-
men occurrences and mudstone units, which could
have been potential source rocks (Fig. 3). All bitu-
men, bitumen-bearing rock phases and potential
source rock intervals identified from Pre- and Post-
Salt units were sampled using a geological hammer.
Samples were then wrapped into aluminium foil and
placed in sample bags. Samples were processed in
the laboratory to remove the outer weathered sur-
faces or to expose fresh rock areas that could be
later subsampled, before undergoing a series of pet-
rographic and geochemical analyses (Fig. 4). This
was done using a combination of metallic tools
such as a circular saw, hammer, chisel and spatula.
No water was used in the sample cleaning process.

Sampling was carried out at seven localities along
the basin strike, near Bero (15° 08′–15° 11′ S,
12°14–12° 18′ E), Mariquita (14° 46′ S, 12° 20′
E), Cangulo (14° 33′–14° 34′ S, 12° 21′–12° 22′
E), Chapeu Armado (14° 26′–14° 28′ S, 12° 21′–
12° 22′ E), Inamangando (14° 03′ S, 12° 23′–12°
24′ E), Caranjamba (13° 59′–14° 01′ S, 12° 30′–
12° 32′ E) and Lucira (13° 53′–13° 56′ S, 12° 31′–
Petrography, isotopes and trace elements
Petrographic analyses in transmitted, reflected and
ultraviolet (UV) light were carried out on ten thin-
sections of bitumen-bearing rock phases in order to
define the bitumen optical properties and its paragen-
esis in relation to the associated rock phases. Analy-
ses were carried out using a Nikon Eclipse LV100N

Fig. 3. Field location maps. The location of the maps is indicated in Figure 2b (red box). The maps show details for
the Bero and Chapeu Armado areas, two of the main field localities of this study. Location of the outcrops where Pre-
and Post-Salt mudstones and bitumen samples were collected is indicated. Source: Google Earth image, 2023 Landsat/
Copernicus; 2021 CNES/Airbus and Maxar Technologies (Bero); 2021 Maxar Technologies (Chapeu Armado).
 Namibe Basin petroleum system

Fig. 4. Methodology flowchart. The flowchart shows the sample types (orange) and the analyses performed (pale
blue). TL, transmitted light; RL, reflected light; UV, UV light; CL, cathodoluminescence; TOC, total organic carbon;
Py-GCMS, pyrolysis gas chromatography mass spectrometry; GC-FID, gas chromatography flame ionization
detection; GCMS, gas chromatography mass spectrometry.

POL polarizing microscope, fitted with a CoolLED
pE-300-W microscope illuminator at the University
of Manchester. Cathodoluminescence (CL) was
also carried out on the same thin-sections at the Uni-
versity of Liverpool using a CITL Mk5-2 attached
Nikon Eclipse Ci microscope (254 μA and 8.4 kV
beam operating conditions).
Carbon (δ 13Ccal) and oxygen (δ 18Ocal) stable iso-
tope analyses were carried out on 12 powdered sam-
ples micro-drilled from carbonate fracture-fill phases
and their carbonate host-rocks. Prior to analysis,
powdered samples were solvent-cleaned from bitu-
men using a solution of dichloromethane/methanol
(9:1 v/v) in an ultrasonic bath. Isotopic analyses
were conducted at the University of Liverpool fol-
lowing sample preparation procedures described by
McCrea (1950) and Swart et al. (1991). CO2 mass
ratios (m/z 45/44, 46/44) were measured using a
dual-inlet VG SIRA 10 mass spectrometer. Resultant
values were adjusted for temperature-dependent
kinetic oxygen isotope fractionation associated
with the carbonate–phosphoric acid reaction
(Friedman and O’Neil 1977). All data are reported
as delta values with respect to the international
Vienna Peedee Belemnite (V-PDB) carbon and oxy-
gen isotope reference scales. Estimated analytical
precision is better than +0.1‰ for both carbon
and oxygen delta values. A calcite fractionation
diagram (Wostbrock et al. 2020) was used in order
to estimate δ 18Ofluid (‰ Vienna Standard Mean
Ocean Water, V-SMOW) based on the measured
δ 18Ocal (‰ V-PDB) and assuming temperatures
between 100 and 150°C, comparable to temperature
ranges recorded in the onshore Namibe Basin during
Late Cretaceous magmatic activity (Fiordalisi et al.
2021a).
Trace-element (Sr, Mn, Fe) concentrations were
obtained from nine powdered samples micro-drilled
from carbonate fracture-fill phases and their matrix
host-rocks, and solvent-cleaned from bitumen using
a solution of dichloromethane/methanol (9:1 v/v) in
an ultrasonic bath. Powdered samples were digested
in 5 ml of HNO3 for 24 hours and diluted in 100 ml
of water so that the final HNO3 concentration was
 E. Fiordalisi et al.
2% w/v. Analyses were carried out at the University
of Manchester using a Perkin-Elmer Optima 5300
dual view inductively coupled plasma atomic emis-
sion spectrometer (ICP-AES). Relative standard
deviations were commonly below 2%.
TOC, Rock-Eval pyrolysis and pyrolysis gas
chromatography mass spectrometry
TOC and Rock-Eval pyrolysis analyses were carried
out on powdered mudstone samples to evaluate their
source rock potential. Samples were powdered using
an agate mortar and pestle set. TOC analyses were
conducted on 34 samples using a Coulomat 702
instrument at Oxford University. For each sample,
two splits (one of which was previously furnaced
in ventilated conditions at 420°C overnight to free
the organic compounds) were separately heated to
1220°C in a pure oxygen atmosphere and the
released CO2 was detected. The measurement on
the two sample splits respectively corresponds to
the total carbon (TC) and total inorganic carbon
(TIC), and the TOC was obtained by subtraction.
Samples with TOC .0.5% were analysed for Rock-
Eval pyrolysis at Applied Petroleum Technology
(APT) laboratories in Oslo. Rock-Eval pyrolysis
was carried out on six samples using a Rock-Eval
6 instrument. Samples were heated at a temperature
of 300°C for 3 minutes, after which the temperature
was increased by 25°C per minute until it reached
650°C.
Pyrolysis gas chromatography mass spectrome-
try (py-GCMS) was carried out on 12 bitumen sam-
ples to obtain bitumen fingerprints from their
pyrolysates. Analyses were conducted using an Agi-
lent GC/MSD System interfaced to a CDS-5200
pyroprobe at the University of Manchester. Bitumen
was placed into a clean fire-polished quartz and
pyrolysed at 600°C at which it was held for 20 sec-
onds. The resulting material was transferred via a
heated transfer line to an Agilent 7980A GC fitted
with a Zebron ZB-5MS column (5% diphenyl-
dimethylpolyolsiloxane; 30 m, 0.25 mm internal
diameter, 0.25 µm film thickness) coupled to an Agi-
lent 5975 MSD single quadrupole mass spectrometer
in electron ionization mode (scanning a range of m/z
50 to 650 at 2.7 scans per second; ionization energy:
70 eV). The pyrolysis transfer line and rotor oven
temperatures were set at 350 and 325°C, respec-
tively, the heated GC interface at 350°C, the electric
ionization source at 230°C and the mass spectrome-
try (MS) quadrupole at 150°C. Helium was used as
the carrier gas, and the samples were introduced in
split mode (split ratio: 20:1; constant flow of 20 ml
min−1, gas saver mode active). The oven was pro-
grammed from 40°C (held for 5 minutes) to 320°C
at 5°C min−1 and held at this temperature for 10
minutes. Compounds were identified using the
National Institute of Standards and Technology data-
base and by comparison with spectra from
the literature.
Extraction, asphaltene removal,
fractionation and gas chromatography
Extraction of organic matter was carried out at APT
on five samples, from both Pre-Salt and Post-Salt
units, in order to extract the bitumen from the kero-
gen and rock mineral components. A Soxtec Tecator
instrument was used for organic matter extraction.
Crushed samples were weighed in thimbles, boiled
for 1 hour and rinsed for 2 hours in 80 cc of dichloro-
methane with 7% (v/v) methanol. Copper blades
activated in concentrated hydrochloric acid were
added to the extraction cups so that free sulfur
reacted with the copper. An aliquot of 10% of the
extract was transferred to a pre-weighed bottle and
evaporated to dryness. The amount of extractable
organic matter was calculated from the weight of
this 10% aliquot.
Asphaltene removal and medium pressure liquid
chromatography (MPLC) fractionation were con-
ducted at APT on extracted organic matter from
two selected bitumen samples, from the Pre- and
Post-Salt, respectively, in order to isolate and assess
the relative proportions of saturate, aromatic, polar
and asphaltene fractions. Extracts were evaporated
almost to dryness before a small amount of dichloro-
methane (three times the amount of the extracted
organic matter) was added. Pentane was added in
excess (40 times the volume of extracted organic
matter and dichloromethane). The solution was
stored for at least 12 hours in a dark place before it
was filtered/centrifuged and the weight of the
asphaltenes measured. MPLC was used in order to
isolate the saturate, aromatic and polar fractions,
according to a system described by Radke et al.
(1980). Approximately 30 mg of deasphalted
organic matter diluted in 1 ml hexane was injected
into a sample loop. The solvents used to isolate the
fractions were hexane and dichloromethane. The sat-
urate fraction was isolated by collecting the hexane
that went through the sample loop, a pre-column
and a main column filled with deactivated Kieselgel
100 and LiChroprep Si 60, while the aromatic frac-
tion was isolated by collecting the hexane that back
flushed the pre-column. The polar fraction was
finally isolated by collecting dichloromethane that
back flushed the pre-column. Solvents from all frac-
tions were removed by using a Turbovap unit, while
the fractions were transferred to pre-weighed vials,
dried and weighed.
Gas chromatography flame ionization detection
(GC-FID) analyses of extracted organic matter and
 Namibe Basin petroleum system
saturate fractions were carried out on five and two
samples, respectively, in order to obtain bitumen fin-
gerprints from their extracted organic matter. Analy-
ses were conducted at APT, and an HP7890A
instrument was used. The capillary column was an
Agilent CP-Sil-5 CB-MS, 30 m long, with an inter-
nal diameter of 0.25 mm and a film thickness of
0.25 µm. C20D42 was used as an internal standard.
The temperature programme started at 50°C (for
one minute), followed by a temperature increase of
4°C per minute until 320°C, which was held for
25 minutes.
Gas chromatography mass spectrometry
(GCMS) analyses of hydrocarbon saturated and aro-
matic fractions were carried out on two bitumen sam-
ples, from the Pre- and Post-Salt, respectively, in
order to identify the source, maturity and
biodegradation-dependent biomarkers. Analyses
were carried out at APT using a Thermo Scientific
TSQ Quantum XLS instrument. The instrument
was tuned to a resolution of 0.4 mass units, and
data were acquired in selected ion recording (SIR)
mode. The column used was a 60 m CP-Sil-5
CB-MS with an internal diameter of 0.25 mm and
a film thickness of 0.25 µm. D4-27ααR was used as
an internal standard in order to quantify saturated
compounds. D8-Naphthalene, D10-Biphenyl, D10-
-Phenanthrene and D12-Chrysene were used as inter-
nal standards for the quantification of the aromatic
compounds. The temperature programme started
at 50°C (for 1 minute), followed by a temperature
increase of 20°C per minute until 120°C, and 2°C
per minute until 320°C, which was held for
20 minutes.
Results
Bitumen and potential source rock
occurrences
Potential source rock mudstones were observed
within the Pre- and Post-Salt intervals. Pre-Salt mud-
stones are interbedded with coarser grained sandy
units within the Tumbalunda Fm and were also
observed directly below the Bambata Fm evaporites.
In all occurrences, thicknesses range from c. 2 to
10 m (Fig. 5a–c). The mudstones show grey,
brown and green colours, are fissile and stratified
in layers ,1 to 40 cm thick. Below the evaporites,
mudstones are often interbedded with centimetric
evaporite and carbonate beds. Pre-Salt mudstones
are observed at multiple localities along the basin
strike, including Bero, Cangulo, Caranjamba and
Lucira.
Post-Salt mudstone units are mostly observed in
the Gaio Fm directly overlying evaporites, showing
grey to dark brown colorations and common paper
shale fabrics. Overall thicknesses are between c. 5
and 15 m, with ,1 to 20 cm thick beds (Fig. 5d–f).
More calcareous components occur as ,1 mm
thick laminae to centimetre/decimetre-scale inter-
beds. Gaio Fm mudstones were observed across
the whole basin strike, but the best developed
paper shale fabrics occur in the central part of the
basin between Cangulo and Chapeu Armado. Youn-
ger mudstone intervals are local, with thicknesses of
up to 10 m. These occurrences cannot be correlated
across multiple localities and are typically siltier.
Bitumen occurrences show a significant variabil-
ity along the basin strike (Figs 3, 6, 7, 8). At Bero
(Fig. 3), decametre-thick BVC exposures are highly
fractured. Fracture strike is variable, with a dominant
orientation north–south to NW–SE, and fracture
widths are ,1 to c. 15 cm. Open fractures are typi-
cally narrower and are cross-cut by cemented
veins. Cement phases observable at the field scale
include gypsum, calcite, silica and bitumen. Calcite,
silica and bitumen are normally associated within the
same veins (Type 2), which in turn cross-cut
gypsum-filled veins (Type 1; Fig. 6a). Calcite is typ-
ically layered, with individual layers between 20 µm
and 1 mm thick. Crystals are mostly blocky, com-
monly elongated parallel to veins, and often twinned
(Fig. 6b). Calcite layers are brecciated and are cross-
cut by silica, which occupies the innermost position
within fracture fills, occurring as microcrystalline to
blocky mosaics or as ,500 µm chalcedony bands
(Figs 6b–e & 8a). Bitumen is observed sealing cal-
cite breccia and also occurring as inclusions within
silica mosaics or interlayered with chalcedony
bands, showing a bright yellow to orange fluores-
cence (Figs 6b–e & 8a).
Bitumen is also observed in the Cangulo Fm Pre-
Salt carbonates at Bero (Fig. 3), within fenestral/
vuggy porosity, millimetre-thick stratabound calcite
veins and thinner subvertical fractures, showing
bright to dark orange fluorescence (Fig. 7a–d). In
the calcite veins, at least two generations of bladed
to blocky crystals are recognized, with growth axes
perpendicular to veins, while bitumen occurs as
inclusions within the earlier crystal generation or in
the intercrystalline porosity (Figs 7c, d & 8b). Simi-
lar bitumen occurrences within Pre-Salt carbonates
are also observed at Cangulo and Chapeu Armado
(Fig. 3), although bitumen here is non-fluorescent
and characterized by blue fluorescing inclusions
(Fig. 7e, f).
Bitumen is also widely observed in the Post-Salt
Gaio Fm, where it has been extensively observed at
the Cangulo and Chapeu Armado localities (Fig. 3).
Minor occurrences are at Caranjamba. Bitumen in
the Post-Salt shows a much more in situ setting,
occurring within or at a short distance from the
above-described mudstone units. Post-Salt bitumen
can occur as stratabound lamination, in vuggy
 E. Fiordalisi et al.

Fig. 5. Namibe Basin onshore mudstones. (a–c) Immediate Pre-Salt mudstones interbedded with centimetric paler
carbonate and evaporite beds at Caranjamba. (d–f) Immediate Post-Salt paper shales at Cangulo. Mudstones appear
much darker once the weathered surfaces have been removed (c, f).

porosity or inside ,1 to 3 cm thick local jigsaw-like
fractures, often as inclusions within gypsum veins
(Fig. 9a–f). Bitumen shows a dull brown fluores-
cence and can include dispersed orange fluorescing
organic matter particulates (Fig. 9f). Interconnection
between stratabound bitumen occurrences and bitu-
men in vugs/fractures is often observed (Fig. 9e, f).
Carbonate luminescence, isotopes and trace
elements
The calcite cements within the Pre-Salt units vary
from non-luminescent to bright red/orange/yellow
luminescent, with crystal zonations sometimes
observed (Fig. 10a–f). Where veins occur in the car-
bonates, luminescence of the host matrix and of the
associated cement crystals is similar.
Calcite oxygen isotopic values are relatively con-
sistent and vary between −7.21 and −5.12‰ V-
PDB, while carbon isotopes vary between −15.66
and +7.76‰ V-PDB, showing clustering based on
sample locality/stratigraphical interval (Table 1;
Fig. 10g). In particular, calcite negative carbon val-
ues are observed within the stratabound veins of
the Cangulo Fm at Chapeu Armado and within the
BVC fractures at Bero, while positive carbon values
are observed within the stratabound veins of the
Cangulo Fm at Bero. No significant differences in
isotopic composition are observed between the cal-
cite host-rock and cement phases (Table 1; Fig. 10g).
Concentrations of carbonate trace elements, as
determined by ICP-AES, are as follows: Sr,
162–346 ppm; Mn, 167–11 396 ppm; Fe, 704–
20 457 ppm. Sr shows an inverse correlation with
Mn and Fe, resulting in L-shaped trends of decreas-
ing Sr and increasing Mn/Fe. Mn and Fe show great
variability based on sample stratigraphical interval
and locality (Table 1; Fig. 11a, b). Levels of Sr are
higher within some carbonate matrix samples,
while cement phases include the highest Mn and
Fe concentrations (Table 1; Fig. 11a, b).
 Namibe Basin petroleum system

Fig. 6. Bitumen occurrences within the Pre-Salt Bero Volcanic Complex at Bero. (a) Gypsum vein (Type 1)
cross-cut by a fracture (Type 2) filled with calcite and silica. The dashed white line indicates the ‘Type 2’ fracture
development, while the red box shows the ‘Type 2’ fracture fill, with calcite (white) mostly occupying the outer parts
of the fracture fill, while silica (dark grey) occupies the innermost part. (b, c) Bright yellow-orange fluorescing
bitumen filling/sealing truncations within calcite layers. (d, e) Bright yellow-orange fluorescing bitumen within
chalcedony bands. (c, e) UV light.

TOC and Rock-Eval pyrolysis
Most of the observed mudstone intervals show low
TOC values of ,0.5% (Table 2). Higher values
were occasionally observed within the Pre-Salt
Tumbalunda Fm, showing TOC values of up to
1.6%, and within the paper shales of the Gaio Fm
in the immediate Post-Salt, showing values of up
to 13.8% (Table 2; Fig. 12a). The Pre-Salt mudstones
show variability in Rock-Eval parameters, with S1
values of 0.1–1.6 mgHC g−1 rock, S2 values of
0.4–6.8 mgHC g−1 rock, production index (PI) val-
ues of 0.19–0.23 and hydrogen index (HI) values
of 35–433 mgHC g−1 TOC (Table 2; Fig. 12a, b).
Values in the Post-Salt are consistently higher,
with S1 values of 6.1–17.9 mgHC g−1 rock, S2
values of 45.5–84.5 mgHC g−1 rock, PI values of
0.12–0.24 and HI values of 576–684 mgHC g−1
TOC (Table 2; Fig. 12a, b). Pre-Salt samples show
Tmax values of 423–424°C, while in the Post-Salt
Tmax ranges between 429 and 437°C (Table 2;
Fig. 12b).
Py-GCMS
Py-GCMS analyses indicate significant unresolved
complex mixtures (UCM) and series of n-alkanes
commonly ranging from ,n-C10 to .n-C30
(Fig. 13a, b). Pre-Salt bitumen samples all show a
bimodal n-alkane distribution with a dominance of
the n-C22 to n-C28 homologues, while Post-Salt bitu-
men shows distributions with a dominance of the
n-C11 and n-C13 homologues and a more gradual
decrease in compound abundance (Fig. 13b). Pre-
Salt bitumen also shows pristane (Pr) over phytane
(Ph) ratios of between 0.83 and 1.49, lower than
 E. Fiordalisi et al.

Fig. 7. Bitumen occurrences within the Pre-Salt Cangulo Fm. (a, b) Cangulo Fm carbonates at Bero. Arrow 1
indicates stratabound calcite veins, arrow 2 indicates subvertical fractures, while 3 indicates an area characterized by
fenestral/vuggy porosity (hammer handle on the right-hand side of (b) for scale). (c, d) Bright to dark orange
fluorescing bitumen within stratabound calcite veins in the Cangulo Fm carbonates at Bero. (e, f) Non-fluorescent
bitumen with blue fluorescing inclusions within stratabound veins in the Cangulo Fm carbonates at Cangulo. (d, f )
UV light.

those observed within Post-Salt bitumen, which
range between 1.77 and 1.92 (Table 3). The n-alkane
distributions are characterized by no visible odd
v. even carbon predominance, with the carbon pref-
erence index (CPI-1) values varying between 0.95
and 1.03 (Table 3). These parameters could not be
calculated for all the analysed samples owing to
enhanced UCM humps and/or very low compound
abundances.
Extraction, fractionation, GC-FID and
GCMS
Extracted organic matter (EOM) values were
between 3.6 and 4.2 g EOM kg−1 rock for Pre-Salt
bitumen samples, and between 23.4 and 680.6 g
EOM kg−1 rock for the Post-Salt bitumen (Table 3).
EOM of Pre-Salt bitumen is dominated by polar
compounds and asphaltenes, accounting for 45.3
and 31.4% of the EOM, with moderate alkane
(21.4%) and minor aromatic contributions (1.9%;
Table 3). EOM of Post-Salt bitumen is also domi-
nated by polar compounds and asphaltenes (respec-
tively, 28.6 and 61.5% of the EOM), while alkane
and aromatic compounds account for 8.9 and 1.0%
of the EOM (Table 3). Traces from GC-FID analyses
were characterized by a UCM hump; however, an
n-alkane bimodal distribution pattern can be identi-
fied for the Pre-Salt bitumen, with a relatively high
concentration of n-C27 to n-C31 compounds, while
the Post-Salt bitumen does not seem to be character-
ized by a bimodal shape (Fig. 13c). GC-FID analyses
on the saturate fractions indicate the presence of sub-
stantial amounts of pristane and phytane resulting in
Pr/Ph ratios of 1.48 and 1.77 for the Pre- and Post-
 Namibe Basin petroleum system
Fig. 8. Pre-Salt fracture fill paragenesis. (a) Vein
within the Bero Volcanic Complex, where brecciated
calcite layers are disrupted by silica, occupying the
innermost part of the vein. Bitumen seals the calcite
breccia, also occurring as inclusions within silica. (b)
Calcite veins within the Cangulo Fm, showing an
earlier generation of bladed calcite crystals (1), and a
later generation characterized by blocky crystals (2).
Bitumen occurs as inclusions within the earlier calcite
generation and in the intercrystalline porosity.
Salt bitumen, respectively, while CPI-1 ratios for the
two bitumen types were 1.05 and 1.78 (Table 3).
GCMS analyses allowed identification of several
source, maturity and biodegradation-dependent
biomarkers. Pre-Salt bitumen shows significantly
higher gammacerane, β-carotane and bisnorhopane
concentrations (13 864, 1044 and 6646 ng g−1,
respectively) if compared to the Post-Salt bitumen
concentrations (589, 197 and 2327 ng g−1, respec-
tively), while no oleanane was detected in both
bitumen types (Table 3; Fig. 14a). All the maturity-
dependent biomarker parameters such as Ts/Tm,
C29Ts/C29αβ and the aromatic methylphenanthrene
index (MPI-1) and methylphenantrene ratio (MPR)
show consistently higher values for the Pre-Salt bitu-
men (Fig. 14b, c).
Finally, biodegradation was assessed using
25-norhopane/hopane ratio fractions. These frac-
tions, in relation to the C29 and C30 hopanes, show
values of 0.23 and 0.16 for the Pre-Salt bitumen,
and 0.45 and 0.25 for the Post-Salt bitumen
(Table 3; Fig. 15).
Discussion
Bitumen quality and biodegradation
The presence of a significant UCM and norhopanes
in the analysed bitumen samples indicates severe
levels of biodegradation (Wenger et al. 2002; Figs
13 & 15), which had a major impact on the transfor-
mation of what originally were Pre- and Post-Salt
oils into bitumen (Curiale 1986; Gentzis and Good-
arzi 1990). Anaerobic and aerobic biodegradation
can be expected in surface samples, and a different
degree of exposure to meteoric processes at surface
might have caused the slightly higher biodegradation
level in the Post-Salt bitumen (Fig. 15). Severe levels
of biodegradation often affect concentrations of
n-alkanes and isoprenoids, such as pristane and phy-
tane (Wenger et al. 2002). However, these com-
pounds were still identified in the present study,
suggesting that biomarkers identified via GCMS
analyses (e.g. Fig. 14), generally more resistant to
biodegradation, were preserved despite biodegrada-
tion of the bitumen (Wenger et al. 2002). Results
from GC-FID analyses did not allow a thorough
interpretation owing to relatively low compound
concentrations if compared to the UCMs, especially
in the more degraded Post-Salt bitumen (Fig. 13c).
Py-GCMS overall showed better preserved n-alkane
distributions for both Pre- and Post-Salt bitumen
samples (Fig. 13b), likely owing to the contribution
of the asphaltene fraction, releasing non-degraded
compounds during pyrolysis. The higher relative
asphaltene content (Table 3) and lower fluorescence
(Fig. 9f) of the Post-Salt bitumen might relate to the
fact that it was generated within an earlier maturity
window (Bertrand et al. 1986; Sanei 2020). How-
ever, it is likely that the pressure changes experi-
enced by the petroleum during generation and
migration have also played a role in accounting for
the observed differences (Sanei 2020).
Oil-source correlation
The different n-alkane distributions in the Pre- and
Post-Salt bitumen suggest that the oils were gener-
ated from two different source rock types. The bimo-
dal n-alkane distributions for the Pre-Salt bitumen
(Fig. 13b, c), skewed towards heavier (n-C23–
n-C31) homologues, can be indicative of a significant
input of terrigenous waxy epicuticular material
(Eglinton and Hamilton 1967). However, similar dis-
tributions can also be observed in lacustrine oils, as
lacustrine algae can also be rich in heavier n-alkanes
(Gelpi et al. 1970; Moldowan et al. 1985). Pr/Ph
ratios below 2 (Table 3) likely exclude significant
terrigenous contributions in the source rock deposi-
tional environment (Powell and McKirdy 1973).
 E. Fiordalisi et al.

Fig. 9. Bitumen in the Post-Salt Gaio Fm. (a–c) Field views of stratabound bitumen (a, Chapeu Armado), bitumen
within a jigsaw fracture network (b, Chapeu Armado) and a satin spar vein (c, indicated by the arrow, Caranjamba)
containing bitumen inclusions. (d–f) Micrometric views of stratabound bitumen and its interconnection with fracture
networks. Orange fluorescing organic matter particulates are also occasionally visible (indicated by arrows in (f );
UV light).

The absence of oleanane (deriving from angio-
sperms) in both Pre- and Post-Salt bitumen types
(Table 3) would also exclude significant higher
plant contributions (Whitehead 1973; Grantham
et al. 1983; Ten Haven and Rulkötter 1988),
although angiosperms were not prominent until the
Late Cretaceous (Moldowan et al. 1994). A lacus-
trine origin for the Pre-Salt bitumen is further sup-
ported by the relatively high β-carotane and
gammacerane abundances (Table 3; Fig. 14a),
whose combination suggests that the Pre-Salt bitu-
men was likely generated within an anoxic lacustrine
depositional environment with a stratified water col-
umn resulting from hypersaline conditions at depth
(Hall and Douglas 1983; Jiang and Fowler 1986;
Fu et al. 1990; Irwin and Meyer 1990; Sinninghe
Damsté et al. 1995). A relatively anoxic source
rock depositional environment for the Pre-Salt bitu-
men is also supported by a relatively high
bisnorhopane concentration (Burwood et al. 1995)
and low Pr/Ph ratios (Didyk et al. 1978; Table 3).
This interpretation agrees with the low levels of
botryococcane (Table 3), which typically relates to
lacustrine freshwater-brackish conditions (Moldo-
wan and Seifert 1980; McKirdy et al. 1986).
Combined, this suggests that the Pre-Salt bitu-
men was likely generated by a Bucomazi Fm equiv-
alent, a well-known Neocomian–Barremian prolific
regional source unit in Angola, the deposition of
which has previously been related to hypersaline/
anoxic settings (Burwood et al. 1995). Bucomazi
Fm equivalent units are not present onshore owing
to their erosion/non-deposition (Gindre-Chanu
et al. 2016; Sharp et al. 2016; Jerram et al. 2019),
but they are likely to be present offshore, where
deep syn-rift graben are observed just off the present-
day coast (Koch et al. 2013; Cunha et al. 2019). Pre-
Salt Aptian mudstones, equivalent to those observed
 Namibe Basin petroleum system

Fig. 10. Luminescence and isotopic composition of Pre-Salt calcite. (a–f) Transmitted light and CL views of calcite
from different Pre-Salt stratigraphical units and localities. (g) Cross-plot between δ 13Ccal and δ 18Ocal.

onshore within the Aptian Tumbalunda Fm, are
unlikely to have contributed to the generation of
the Pre-Salt bitumen, despite the fact that they spor-
adically show good TOC and source rock properties
(Fig. 12). The deposition of Aptian mudstones might
still have occurred within a saline environment, espe-
cially in the immediate Pre-Salt, owing to marine
incursions testified by the alternation with evaporitic
layers (Gindre-Chanu et al. 2016). However, the
Aptian depositional setting was likely relatively
shallow and more oxygenated, as also evidenced
by carbonate interbeds in the immediate Pre-Salt
(Fig. 5b), which disagrees with the reducing charac-
ter of the Pre-Salt oil discussed above.
In contrast, the smoother and more unimodal
n-alkane distribution pattern in the Post-Salt bitumen
may be more indicative of a marine origin (Mello
et al. 1988; Fig. 13b). Lower levels of β-carotane,
gammacerane and higher Pr/Ph ratios exclude a
saline lacustrine origin for the Post-Salt bitumen
(Table 3; Fig. 14a) and suggest a more oxic source
rock depositional environment. The absence of
botryococcane from the Post-Salt bitumen further
excludes a freshwater lacustrine origin, therefore
ruling out the possibility that the Post-Salt bitumen
was generated by a lacustrine source rock. The
immediate Post-Salt mudstones of the Gaio Fm,
showing excellent TOC and source rock properties
in the Namibe Basin (Table 2; Fig. 12), might be a
good candidate for the generation of the Post-Salt
bitumen. These mudstones are age-equivalent to
the regional Binga Fm, deposited in a shallow marine
carbonate-dominated environment (Burwood 1999).
The lack of oleanane (Table 3) would exclude signif-
icant contributions from younger marine source units
(Burwood 1999; Schoellkopf and Patterson 2000).
Oil maturity and hydrocarbon generation
processes
Maturity-dependent saturated biomarker parameters
indicate that the Pre- and Post-Salt hydrocarbons
were generated at the boundary between the early
and peak oil windows (Fig. 14b), corresponding to
a source rock vitrinite reflectivity (VR) value of c.
0.8% (Dow 1977; Senftle and Landis 1991; Dem-
bicki 2009). Aromatic biomarker maturity
 E. Fiordalisi et al.

Fe (ppm)

20 457
20 093

1328
1802
1054
1704

2652
3203
704
Mn (ppm)

10 676
10 794
11 396
9463

5801
167
245
308
299
Sr (ppm)

162
168

346
285
214
222

182
197
220
δ 18Ocal (‰ V-PDB)

−7.21
−7.17
−7.05
−6.18
−6.22
−6.10
−6.16
−6.45
−6.24
−5.98
−5.22
−5.12
δ 13Ccal (‰ V-PDB)

−15.66
−13.18
−15.03
−9.06
−8.67
−9.11
7.48
6.01
6.76
7.65
3.75
7.76

Fig. 11. Trace elements in Pre-Salt calcite. Sr shows an

inverse correlation with (a) Mn and (b) Fe, resulting in
L-shaped trends (indicated by the arrows) of decreasing
Sr and increasing Mn/Fe. Mn and Fe show great
Host matrix
Host matrix

Host matrix

variability based on sample stratigraphical interval

Cement
Cement
Cement

Cement
Cement
Cement
Cement

Cement
Cement

and locality.
Table 1. Isotopic and elemental data for calcite within Pre-Salt units

Phase

parameters suggest slightly higher thermal maturity

values than the saturated biomarkers (Fig. 14c), indi-
Stratigraphic sequence

cating that the Pre- and Post-Salt bitumen were gen-

erated within late (VR .1.0%) and peak (0.8% ,
VR ,1.0%) oil windows, respectively. However,
preservation of the bimodal n-alkane distributions
Pre-Salt

would exclude generation at late maturity stages,

considering that the heavier normal alkanes would
be cracked to lighter products during maturation
(Plummer 2020), suggesting that, in the present
study, the aromatic maturity parameters cause an
Cangulo

overestimation of the thermal maturity.

BVC

Pre-Salt source rocks in the onshore Namibe

Fm

Basin are all immature, having Tmax values of

,435°C (Table 2; Fig. 12b; Peters 1986). This is
consistent with the limited regional burial undergone
Chapeu Armado

by the onshore sedimentary units (Fiordalisi et al.

2021a), meaning that the Pre-Salt hydrocarbons
Locality

that were transformed to bitumen must have been

Bero

generated within more deeply buried Pre-Salt sec-

tions offshore. This agrees with a correlation of the
 Namibe Basin petroleum system

Table 2. TOC and Rock-Eval data

Locality Fm Stratigraphic TOC S1 (mgHC S2 (mgHC Tmax PI (wt HI (mgHC

sequence g−1 rock) g−1 rock) (°C) ratio) g−1 TOC)

Bero Tumbalunda Pre-Salt ,0.1

0.3
,0.1
,0.1
,0.1
0.0
0.1
0.3
Gaio Post-Salt 0.2
,0.1
,0.1
Mariquita Bentiaba 0.1
0.0
Cangulo Tumbalunda Pre-Salt ,0.1
1.6 1.6 6.8 424 0.19 433
Gaio Post-Salt 7.3 6.1 45.5 437 0.12 620
Chapeu 7.1 15.1 48.9 437 0.24 684
Armado 13.8 17.9 84.5 429 0.18 611
10.9 13.2 62.6 435 0.17 576
Caranjamba Tumbalunda Pre-Salt 0.0
0.1
0.1
0.2
,0.1
,0.1
Gaio Post-Salt 0.1
Mariquita ,0.1
Inamangando Gaio 0.0
,0.1
Lucira Tumbalunda Pre-Salt 0.2
1.1 0.1 0.4 423 0.23 35
Gaio Post-Salt ,0.1
0.1
0.3

TOC, total organic carbon; PI, production index; HI, hydrogen index.

Pre-Salt oil to Bucomazi-like source intervals depos-
ited within deep grabens offshore (Brownfield and
Charpentier 2006).
In contrast, source rocks identified in the imme-
diate Post-Salt section onshore have reached ther-
mal maturity, showing Tmax values of .435°C,
compatible with VR values of .0.6% (Peters
1986; Table 2; Fig. 12b). Thermal maturity values
for these source rocks are comparable to the Post-
Salt bitumen thermal maturity (Fig. 14b), suggest-
ing that the source rocks in the immediate Post-Salt
section onshore likely generated the oil from which
the Post-Salt bitumen derived. This correlation is
supported by the geochemical compatibility of the
Post-Salt bitumen with immediate Post-Salt Binga-
type source rocks, its spatial proximity to those
source intervals, along with its in situ setting, con-
firming that the hydrocarbons were generated
onshore.
Maturation of Post-Salt source rocks cannot be
the result of burial as this process should result in a
lower maturity than the older, immature, Pre-Salt
units (Fig. 12b). Therefore, maturation of Post-Salt
source rocks in the onshore Namibe Basin could
only be the result of local thermal anomalies related
to the impact of individual Coniacian–Santonian
magmatic intrusions. This is confirmed by the fact
that mature Post-Salt source rocks were identified
in the Cangulo–Chapeu Armado area, which was
clearly affected by Post-Salt magmatic activity
(Fig. 3).
Timing of paragenesis
The bitumen observed within the Pre- and Post-Salt
stratigraphical units was all likely emplaced from
Albian times onwards. The Pre-Salt bitumen in the
BVC at Bero occurs within veins (Type 2) cross-
 E. Fiordalisi et al.
Fig. 12. Cross-plots of TOC and Rock-Eval parameters. (a) Cross-plot between TOC and pyrolysis potential yield
(S2). Interpretation lines from Dembicki (2009). (b) Cross-plot between Tmax and hydrogen index. Interpretation lines
from Bordenave (1993) and Huc (2013).
cutting gypsum veins (Type 1; Fig. 6a). This implies
that the emplacement of the bitumen observed in the
Pre-Salt, along with the other phases associated with
bitumen (calcite and silica), occurred after evaporites
started being remobilized during and after the depo-
sition of the overlying Albian units (Gindre-Chanu
et al. 2015). Some of the fractures could have ini-
tially formed during Pre-Salt tectonic activity, as
suggested by their similar orientation to rift trends
in the basin (Fig. 2b). However, those fractures and
trends were exploited again in the Post-Salt, enlarged
and filled with bitumen, calcite and silica. Calcite
predated silica as it occupies outer positions within
vein fills and is cross-cut by silica (Fig. 8a). The
identification of at least two calcite generations, crys-
tal zonation and different degrees of calcite lumines-
cence (Figs 8b & 10a–f) indicate that the calcite
precipitated as part of multiple fluid circulation
events. Similar luminescence between the carbonate
host-rock and fracture fill suggests that the carbonate
host matrix may have been affected by fluid circula-
tion too, undergoing fabric-preserving recrystalliza-
tion processes. The bitumen was likely emplaced
as part of multiple pulses during calcite and silica
precipitation as it is variously observed within calcite
and silica phases. However, hydrocarbon remobili-
zation processes from calcite into silica could also
have occurred.
Stratabound calcite veins within Pre-Salt carbon-
ates containing bitumen-stained bladed crystals per-
pendicular to the vein orientation, similar to those
observed in this study (Figs 7 & 8b), have been
related to Coniacian–Santonian magmatic activity
(Rochelle-Bates et al. 2020). The presence of silica
cement would also point towards a magmatically
active setting and hydrothermal activity, as silica
requires relatively high temperatures in order to be
taken into solution (Fiordalisi et al. 2021a). There-
fore, it is likely that most of the fluid flow circulation
and bitumen emplacement observed in the Pre-Salt
occurred during the Turonian–Coniacian–Santonian
magmatic events, as these are the only proven Post-
Salt magmatic events in the basin (Jerram et al. 2019;
Rochelle-Bates et al. 2020). The bitumen observed
within the Post-Salt was also emplaced within the
evaporite remobilization time window, as bitumen
and gypsum are often found associated within the
same fractures (Fig. 9c). The identification of forced
maturation processes within the immediate Post-Salt
source rocks as a direct cause for the generation of
the Post-Salt bitumen would necessarily constrain
the timing of this process within the Coniacian–San-
tonian magmatic activity.
Nature of fluids and hydrocarbon
by-products
The negative oxygen isotopes measured in calcite
(δ 18Ocal) in this study (Table 1; Fig. 10g) are compat-
ible with a variety of fluid types. However, hypothet-
ical fluid temperatures between 50 and 150°C,
comparable to temperatures recorded in the onshore
Namibe Basin during Late Cretaceous magmatic
activity (Fiordalisi et al. 2021a), suggest that the flu-
ids from which the calcite precipitated had oxygen
isotopic compositions (δ 18Ofluid) between c. 0 and
+10‰ V-SMOW (Wostbrock et al. 2020;
 Namibe Basin petroleum system

Fig. 13. Pyrolysis gas chromatography mass spectrometry (Py-GCMS) and gas chromatography flame ionization
detection (GC-FID) data. (a, b) Total ion current (a) and 57 m/z trace (b) pyrograms of Pre- and Post-Salt bitumen
showing the presence of significant unresolved complex mixtures (UCM), pristane and phytane and C10 to C33
n-alkanes (represented by open circles with numbers indicating carbon chain length). Pre-Salt bitumen shows a
bimodal n-alkane distribution pattern with maxima at the C13 and C25 homologue, while Post-Salt bitumen shows a
unimodal n-alkane distribution pattern with a maximum at the C13 homologue. (c) Chromatograms of the saturate
fraction of Pre- and Post-Salt bitumen. Despite significant UCM, a bimodal n-alkane distribution can be observed in
the Pre-Salt bitumen. IS, internal standard.

Fig. 16). These isotopic compositions are compatible
with significant contributions from fluids of mag-
matic origin, typically showing positive δ 18O values
(Sheppard 1986; Grove et al. 2017; Teboul et al.
2019), although contributions from other fluid
types such as formation waters or modified infiltrated
waters cannot be excluded (Hudson 1977). L-shaped
trends of decreasing Sr and increasing Mn and Fe
(Fig. 11) support fluid types with different redox
conditions contributing to the fluid circulation during
Late Cretaceous magmatic activity. In particular, the
highest Mn and Fe concentrations would be indica-
tive of more reducing fluids (Tucker and Wright
1990). Fluids that circulated through fractures and
those that affected the host matrix were broadly sim-
ilar within the same locality, as indicated by similar
isotopic compositions between the matrix and
cement phases (Fig. 10g). However, some variation
in trace-element concentrations between the matrix
and cement phases, still within the same locality,
suggests that variability in fluid redox conditions
also occurred at a local scale (Fig. 11).
The positive calcite δ 13C values (Fig. 10g) are
likely indicative of bacterial methanogenesis pro-
cesses, as they would be derived from the residual,
isotopically enriched organic matter from which
methane is generated (Hudson 1977; Siegel et al.
1987; Budai et al. 2002). The fact that these heavy
carbon values are observed in the samples that
have higher Sr and lower Mn and Fe concentrations
(Figs 10g & 11) suggests that the methanogenetic
bacteria had access to near-surface, infiltrated fluids
(Budai et al. 2002). Thermochemical generation of
methane may have contributed to some of the light-
est carbon isotope values observed, especially in the
samples from the Chapeu Armado area (Fig. 10e–g)
that was particularly affected by magmatic activity
(Fig. 3). In magmatic areas such as Chapeu Armado
and Cangulo, non-fluorescent bitumen (Fig. 7e, f) is
likely the product of Pre-Salt oil being cracked into
 E. Fiordalisi et al.

Table 3. Bitumen geochemical data

Locality . Bero Cangulo Chapeu Armado

Formation . BVC Cangulo Gaio

Stratigraphic sequence . Pre-Salt Post-Salt

Pr/Ph 0.83* 0.96* 1.49*/1.48† 1.80* 1.92* 1.77*/1.77†

CPI-1 1.03* 0.98* 1.00*/1.05† 1.03* 0.95* 0.98*/1.78†
EOM (g EOM/kg rock) 3.6 4.2 680.6 168.6 23.4
alkane wt% EOM 21.4 8.9
aromatic wt% EOM 1.9 1.0
polars wt% EOM 45.3 28.6
asphaltenes wt% EOM 31.4 61.5
β-carotane (ng g−1) 1044‡ 197‡
bisnorhopane (ng g−1) 6646‡ 2327‡
oleanane (ng g−1) 0‡ 0‡
gammacerane (ng g−1) 13 864‡ 589‡
botryococcane (ng g−1) 17‡ 0‡
Ts/Tm 0.33‡ 0.26‡
C29Ts/C29αβ 0.21‡ 0.19‡
MPR 1.50‡ 1.11‡
MPI-1 0.66‡ 0.48‡
C29αβ25nor/(C29αβ25nor + C29αβ) 0.23‡ 0.45‡
C30αβ25nor/(C30αβ25nor + C30αβ) 0.16‡ 0.25‡

CPI-1 = 2(n-C23 + n-C25 + n-C27 + n-C29)/[n-C22 + 2(n-C24 + n-C26 + n-C28) + n-C30].

EOM, extracted organic matter.
Ts/Tm = C27Ts/C27Tm.
MPR = 2MP/1MP.
MPI-1 = 1.5(3MP + 2MP)/(1MP + 9MP + P).
*Data from py-GCMS.
†
Data from GC-FID of the saturate fraction.
‡
Data from GCMS.

gas, as also indicated by blue fluorescing inclusions,
which have been previously related to fluorescence
blueshifts within oil undergoing cracking processes,
before being completely transformed into pyrobitu-
men (Ping et al. 2017, 2019). The methane generated
as part of the cracking processes may therefore have
contributed to the formation of calcite crystals with
isotopically light carbon (Hudson 1977).
Source rock maturation and fluid flow
model
Oil/source correlations based on source type and
maturity-dependent biomarkers suggest that the bitu-
men within the onshore Pre-Salt section was likely
generated by a Bucomazi-like source rock within
offshore grabens, which is further supported by the
fact that Pre-Salt onshore source rocks are thermally
immature. Offshore source rocks underwent higher
burial processes, although magmatic activity is likely
to have significantly contributed to source rock mat-
uration, presumably by a number of processes such
as contact metamorphism (localized to areas of
intruded source rock), advective heating associated
with hydrothermal fluids and enhanced regional geo-
thermal gradient. Quantitatively assessing the rela-
tive influences of these processes is however
extremely difficult. Lack of well constraints in the
Namibe Basin makes offshore basin and petroleum
system models uncertain, especially regarding the
timing for hydrocarbon generation. Models from
the adjacent Benguela Basin have indicated that
hydrocarbon generation in that basin took place
within the syn-rift heat spike (Bump et al. 2018).
Eventually, during the Late Cretaceous magmatic
event, Pre-Salt source rocks would have all reached
full maturation, while oil accumulations would
have been displaced or cracked into gas (Bump
et al. 2018). A similar scenario could have occurred
in the Namibe Basin, with oil being generated by
Pre-Salt source rocks owing to sediment burial
within graben and rift-related high-temperature
regimes. Some of this oil could have then been dis-
placed from traps by fluids released or mobilized
by Late Cretaceous magmatic activity, eventually
reaching the present-day onshore (Fig. 17a). Off-
shore regional faults are mostly antithetic (Koch
et al. 2013; Cunha et al. 2019) and therefore unlikely
to have accommodated a significant eastward fluid
 Namibe Basin petroleum system
Fig. 14. Cross-plots of source and maturity-dependent
biomarkers and biomarker parameters. (a) Cross-plot
between β-carotane and gammacerane concentrations.
(b) Cross-plot between Ts/Tm and C29Ts/C29αβ.
Interpretation lines from Petersen et al. (2016). (c)
Cross-plot between methylphenantrene ratio (MPR) and
methylphenanthrene index (MPI-1). Interpretation lines
from Radke et al. (1986) and Rezouga et al. (2012).
migration towards the present-day onshore. Lateral
eastward migration likely occurred via Pre-Salt
permeable units, creating connectivity between the
Fig. 15. Cross-plot of biodegradation-dependent
biomarker ratios, e.g. C30αβ 25nor/(C30αβ 25nor +
C30αβ) plotted against C29αβ 25nor/(C29αβ 25nor +
C29αβ). Interpretation lines based on Wenger et al.
(2002).
offshore deep grabens and the more proximal sedi-
mentary units observed today onshore, although
some migrating hydrocarbons could have been
re-trapped along the migration pathway (Fig. 17b–
d). Lateral migration within Pre-Salt units was con-
strained by the overlying salt where present, which
acted as a seal and prevented fluids from migrating
upwards. Magmatic fluids and formation waters
also likely migrated alongside hydrocarbons. Even-
tually, infiltrated waters could have contributed to
the local fluid circulation, as indicated by the wide
range of trace-element concentrations (Fig. 11) and
possible oxygen fluid isotopic compositions
(Fig. 16). Closer to the Late Cretaceous magmatic
bodies, such as in Chapeu Armado and Cangulo
(Fig. 3), hotter temperatures would have cracked
the Pre-Salt oil into gas, producing non-fluorescent
pyrobitumen and blue fluorescing inclusions (Figs
7e, f & 17e).
Post-Salt hydrocarbons were generated owing to
forced maturation processes within onshore source
rocks in the immediate Post-Salt near Late Creta-
ceous magmatic dykes (Fig. 17f). This was mostly
observed in the magmatic Cangulo/Chapeu Armado
areas (Fig. 3), where mature Post-Salt source rocks
were observed. Post-Salt hydrocarbon fluids mostly
remained in place or underwent short intraforma-
tional migration via locally formed fracture net-
works, often along with remobilized evaporitic
fluids (Fig. 9).
Implications for hydrocarbon prospectivity
Magmatic activity in sedimentary basins is linked to
a wide range of exploration opportunities and risks
(Senger et al. 2017). Magmatic activity during the
Pre- and Post-Salt phases likely increased geother-
mal gradients regionally, accelerating maturation
processes of source rocks undergoing burial. This
Fig. 16. Calcite fractionation diagram (Wostbrock et al.
2020). Green area represents the δ 18Ocal (‰ V-PDB)
range for the values measured in this study.
Hypothetical temperatures between 50 and 150°C are
chosen based on temperature ranges recorded in the
onshore Namibe Basin during Late Cretaceous
magmatic activity (Fiordalisi et al. 2021a).
 E. Fiordalisi et al.

Fig. 17. Examples of interaction processes between Late Cretaceous magmatic activity and the petroleum system in
the Namibe Basin. (a) Magmatically driven fluids displacing a previous Pre-Salt oil accumulation, with the trap now
filled with CO2. The former oil accumulation was likely charged from the underlying source units. (b) Remobilized
hydrocarbons now charging eastward traps. (c) Hydrocarbons migrating towards the present-day onshore, exploiting
permeable Pre-Salt conduits. Magmatically driven fluids are also migrating alongside hydrocarbons. (d)
Hydrocarbons charging Pre-Salt traps in the present-day onshore (e.g. Bero). (e) Hydrocarbon cracking and formation
of pyrobitumen closer to active magmatic dykes (e.g. Cangulo and Chapeu Armado). (f ) Forced maturation of
Post-Salt source rocks near dykes due to contact metamorphism processes (e.g. Cangulo and Chapeu Armado). (g)
Offshore Post-Salt source rocks still possibly immature. (h) Offshore Post-Salt source rocks potentially reaching
maturation under the influence of magmatic sills, with the potential for charging overlying Post-Salt reservoirs. (i)
Intrusive network favouring fluid migration from the Pre-Salt into the Post-Salt section, with deeper magmatically
driven fluids potentially displacing shallower Post-Salt hydrocarbon accumulations.

study provides evidence for a Pre-Salt lacustrine
source rock that generated hydrocarbons, possibly
before or during the Coniacian–Santonian magmatic
event. This hydrocarbon generation process would
have occurred regionally within grabens where
thick Pre-Salt sediment packages were deposited
(Fig. 17). There is no evidence for regionally exten-
sive hydrocarbon generation from Post-Salt units.
These source rocks reached maturity only locally
onshore, in areas affected by Late Cretaceous mag-
matic and hydrothermal activity. If similar Post-Salt
source rocks were present offshore, they could have
generated hydrocarbons over a much more extensive
area owing to the combination of more enhanced
burial processes and magmatic temperatures acceler-
ating maturation (Fig. 17g, h). Thicknesses of
between 3 and 5 km are reported for the offshore
Namibe Basin Post-Salt sequence, making an explo-
ration play underpinned by the excellent immediate
Post-Salt source rocks, or any other younger source
rock, totally viable for the basin (Koch et al.
2013). Magmatic activity can also relate to a series
of exploration risks, including oil cracking into gas
and pyrobitumen closer to the intrusions, and hydro-
carbon remobilization via magmatically driven fluids
(Fig. 17a). Intrusive networks could act as fluid
migration pathways, favouring migration of fluids
through impermeable units (Galland et al. 2023).
In this scenario, shallower Post-Salt hydrocarbon
accumulations could also have been displaced by
deeper magmatically driven fluids (Fig. 17i). How-
ever, traps along the hydrocarbon re-migration path-
ways may be associated with a lower charge risk
(Fig. 17b).
Conclusions
• This study demonstrates the importance of
integrated field, petrographic and geochemical
analyses for characterizing the complexity of a
magmatically influenced petroleum system.
 Namibe Basin petroleum system
• Bitumen within Pre-Salt units has a hypersaline
and anoxic lacustrine signature and was likely
sourced by a Bucomazi-equivalent source rock
offshore. Magmatic activity is likely to have sig-
nificantly contributed to source rock maturation
by enhancing the regional geothermal gradient.
• Late Cretaceous magmatically driven fluids were
responsible for migrating or re-migrating the gen-
erated hydrocarbons to the present-day onshore
locations, as suggested by the isotopic signatures
of bitumen-bearing calcite veins. However, some
hydrocarbons might have also been trapped/
re-trapped along the migration/re-migration
pathways.
• Near magmatic dykes, Pre-Salt oil was cracked to
gas, as revealed by petrographic analyses under
UV light showing the presence of non-fluorescent
pyrobitumen and blue fluorescing inclusions.
• Bitumen within the Post-Salt shows a more
marine-like signature, compatible with an imme-
diate Post-Salt Binga-type source rock.
• The Post-Salt bitumen was likely generated
onshore via source rock forced maturation pro-
cesses owing to local thermal anomalies related
to the impact of individual magmatic intrusions.
The combination of more enhanced burial pro-
cesses and magmatic temperatures accelerating
maturation could make this a viable play offshore.
Acknowledgements This publication contains work
conducted during a PhD study undertaken as part of the
Natural Environment Research Council (NERC) Centre
for Doctoral Training (CDT) in Oil & Gas. BP and Equinor
provided samples and logistical support, and are further
thanked for permission to publish. Steve Crowley carried
out isotopic analyses at the University of Liverpool, while
Steve Wyatt carried out TOC analyses at Oxford Univer-
sity. Luz Gomis-Cartesio (Equinor) is thanked for provid-
ing assistance during fieldwork. The authors would finally
like to thank the reviewers D.A. Jerram and D.K. Muirhead
for their comments, which greatly improved the quality of
this manuscript.
Competing interests The authors declare that they
have no known competing financial interests or personal
relationships that could have appeared to influence the
work reported in this paper
Author contributions EF: conceptualization
(equal), data curation (lead), formal analysis (lead), investi-
gation (lead), methodology (equal), visualization (lead),
writing – original draft (lead), writing – review & editing
(lead); BVD: methodology (equal), visualization (support-
ing), writing – review & editing (supporting); JM: method-
ology (equal), visualization (supporting), writing – review
& editing (supporting); NR-B: conceptualization (support-
ing), investigation (supporting), writing – review & editing
(supporting); VAGM: conceptualization (equal),
investigation (supporting), writing – review & editing (sup-
porting); RD: conceptualization (equal), investigation (sup-
porting), writing – review & editing (supporting); IS:
conceptualization (equal), investigation (supporting), writ-
ing – review & editing (supporting); SS: conceptualization
(equal), funding acquisition (lead), investigation (support-
ing), methodology (equal), supervision (lead), validation
(lead), writing – review & editing (supporting).
Funding The PhD was funded by NERC (grant num-
ber NE/M00578X/1) and the University of Manchester.
BP provided additional funding.
Data availability All data generated or analysed
during this study are included in this published article.
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