Organic Geochemistry 69 (2014) 2635

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

Contact metamorphism of organic-rich mudstones and carbon release

around a magmatic sill in the Basque-Cantabrian Basin, western
Pyrenees q
Luis M. Agirrezabala a,, Albert Permanyer b, Isabel Surez-Ruiz c, Carmen Dorronsoro d
a

Estratigraa eta Paleontologia Saila, Euskal Herriko Unibertsitatea UPV/EHU, 644 P.K., 48080 Bilbo, The Basque Country, Spain
Departament de Geoqumica, Petrologia i Prospecci Geolgica, Universitat de Barcelona, Mart i Franqus s/n, 08028 Barcelona, Catalonia, Spain
Instituto Nacional del Carbn INCAR (CSIC), Francisco Pintado Fe 26, 33011 Oviedo, Spain
d
Kimika Aplikatua Saila, Euskal Herriko Unibertsitatea, 1072 P.K., 20080 Donostia, The Basque Country, Spain
b
c

a r t i c l e

i n f o

Article history:
Received 16 October 2013
Received in revised form 15 January 2014
Accepted 21 January 2014
Available online 31 January 2014

a b s t r a c t
Recent studies have documented the expulsion of methane and oil to the Albian paleoseabed in the Basque-Cantabrian Basin. They interpret that hydrocarbon generation and expulsion were triggered by seismically recorded magmatic intrusions which metamorphosed organic-rich host sediments. An outcrop
within the basin was selected to investigate organic matter evolution and sediment degassing due to
an igneous body. This intrusion is a 5 m thick Late Albian basaltic sill that intruded mudstones of the
Black Flysch Group, near Gorliz (north Iberia). Vitrinite and bitumen reectance proles and metamorphic mineral distribution in the overburden indicate that the sill produced a thermal effect that increases
toward the intrusion, dening a 2 m thick (minimum) contact aureole.
Geochemical proles of TOC, S1, S2, HI and PC show a gradual decrease toward the sill indicating
organic carbon loss and increase in the thermal maturity of the organic matter in the same direction. Concordantly, gas chromatograms show a loss of n-alkanes and a predominance of the shorter chain length
homologues adjacent to the sill. Tmax and PI (S1/S1 + S2) values increase toward the sill which suggests
an increase in the thermal stress and in the extent of kerogen pyrolysis, respectively.
Organic carbon loss in the aureole was the result of carbon devolatilization and formation of CO2 and
CH4 gases. The newly formed CO2 reacted with pore waters to precipitate 13C depleted carbonate minerals in the aureole and in sill fractures. CH4 escaped from the aureole via hydrofractures to the paleoseabed, where methane-derived authigenic carbonates were formed.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Magmatic intrusions in sedimentary basins constitute local
thermal anomalies which affect the organic matter contained within sediments and rocks. The contact metamorphism of organic rich
sediments by magmatic intrusions creates a progressive increase in
vitrinite reectance, loss of organic carbon, generation of hydrocarbons (oil and gas), remineralization of organic carbon and formation of graphite as distance to the igneous intrusions decreases
(e.g. Clayton and Bostick, 1986; Meyers and Simoneit, 1999; Aarnes
et al., 2010, among others). In many cases, it leads to release of 12C
enriched gases (and bitumen) to the seabed or the atmosphere (e.g.
Simoneit et al., 1978; Svensen et al., 2004; Ganino and Arndt,
q
This study was presented at the 26th IMOG Meeting, Tenerife, September 16
20th, 2013.
Corresponding author. Tel.: +34 946015425; fax: +34 946013500.
E-mail address: l.agirrezabala@ehu.es (L.M. Agirrezabala).

http://dx.doi.org/10.1016/j.orggeochem.2014.01.014
0146-6380/ 2014 Elsevier Ltd. All rights reserved.

2009), which can support chemosynthetic seaoor biological communities and promote the precipitation of authigenic carbonates
depleted in 13C (e.g. Lizarralde et al., 2011).
In the Basque-Cantabrian Basin, recent multidisciplinary studies have documented the formation of methane-derived authigenic
carbonate deposits and associated chemosymbiotic fossil fauna,
which indicates the expulsion to the seabed of low temperature
hydrothermal uids rich in hydrocarbons (methane and oil) during
the Late Albian (Agirrezabala, 2009, 2013; Agirrezabala and
Dinars-Turell, 2013; Agirrezabala et al., 2013). A positive geochemical correlation based on similar carbon isotope ratio values
between solid bitumen (pyrobitumen) lls in the authigenic carbonates and host sediment organic matter indicates an Albian
source for expelled hydrocarbons (Agirrezabala et al., 2008). In
addition, buried, highly reective seismic structures just below
the studied deposits are interpreted as magmatic intrusions which
would have provoked contact metamorphism of the organic matter
contained in the Albian host sediments and the expulsion of oil rich

L.M. Agirrezabala et al. / Organic Geochemistry 69 (2014) 2635

uids and thermogenic methane to the paleoseabed (Agirrezabala

and Dinars-Turell, 2013; Agirrezabala et al., 2013). The aims of
this paper are to determine the impact of an Albian magmatic sill
intrusion on adjacent organic rich mudstones of the Black Flysch
Group (Souquet et al., 1985) at the Gorliz locality and to assess
the possible carbon release from the contact aureole as a mechanism for documented Albian uid expulsion. Preliminary data suggest that methane rich uids were expelled to the paleoseabed
above the sill (Agirrezabala, 2013).

2. Geological setting
The Mesozoic Basque-Cantabrian Basin originated by rifting related to the Cretaceous opening of the Bay of Biscay and the eastward drift of the Iberian plate (Montadert et al., 1974). During the
mid-Cretaceous, the basin and the overall Pyrenean region were affected by extreme crustal thinning and stretching (Pedreira et al.,
2003, 2007; Garca-Mondjar et al., 2004; Jammes et al., 2009),
with the occurrence of submarine volcanism and magmatic intrusions (Rossy, 1988; Castaares et al., 2001; Fernndez-Mendiola
and Garca-Mondjar, 2003). Coevally, in the northern margin of
the basin oil and thermogenic methane were expelled to the seabed promoting the formation of authigenic carbonates and development of chemosymbiotic fauna (Agirrezabala, 2009;
Agirrezabala et al., 2013).
At the village of Gorliz (northern Iberia) the Larragan laccolith
and subordinate minor planar intrusions of Late Albian age are intruded into a sub-vertical succession composed of two organic rich

27

lithostratigraphic units, i.e. the deltaic Monte Grande Formation

(Robles et al., 1988) and the deep water turbiditic Black Flysch
Group (Souquet et al., 1985) (Fig. 1). Highly discordant (53) clastic
dykes occur above the stratigraphic interval intruded by magmatic
bodies. These clastic dykes terminate either at the base of or within
a sedimentary wedge (Mariarri unit) composed of greywackes,
polymictic breccias and 13C depleted (up to o13C = 38.7) authigenic carbonates (Fig. 1B); these deposits onlap the lower contact
of the wedge toward the crest of the laccolith and show a convergent stratal conguration in the same direction. Detailed data from
the clastic dykes and the sedimentary wedge are unpublished but
preliminary main results have been presented by Agirrezabala
(2013); a more detailed description and interpretation of these
deposits are presented in Supplementary material (Table S1 and
Figs. S1 and S2). The dykes have been interpreted as conduits of
overpressured, methane rich uids and uidized ows which
reached the paleoseabed, where extruded breccias were deposited
and methane-derived authigenic carbonates precipitated. The sedimentary wedge is interpreted as growth deposits which record
forced folding in response to forcible emplacement of the Larragan
laccolith. Thus, the lower contact of the sedimentary wedge would
correspond to the paleoseabed at the intrusion times (Late Albian)
and, therefore, a depth of ca. 150 m can be estimated for the sill
emplacement.
Among the magmatic bodies of the Gorliz succession, we selected a clearly exposed intrusion at the base of a sea-cliff in order
to collect samples adjacent to the sill. The selected intrusion is a
subordinate arm of the Larragan laccolith and constitutes a 5 m
thick, EW trending, basaltic sill which intrudes into mudstones

Fig. 1. (A) Simplied geological map of the north-central Basque-Cantabrian Basin, with the location of the study section near the village of Gorliz. (B) General stratigraphic
column of the Monte Grande Formation and Black Flysch Group intruded by magmatic bodies at the Gorliz section, with indication of the study interval.

28

L.M. Agirrezabala et al. / Organic Geochemistry 69 (2014) 2635

Fig. 2. (A) Outcrop of the studied sub-vertical basaltic sill and host mudstones of the Black Flysch Group. The 9.86 m thick sampled mudstone interval shown in Fig. 3 is
indicated. Back pack for scale (low center). For location see Fig. 1B. (B) Close up photograph of veins crossing the basaltic sill and lled with angular fragments of mudstone
(m) and basalt (b) and carbonate cements (c). Coin for scale (23 mm). (C) Photomicrograph of (B) showing a vein lled with mudstone fragments (m) and spar calcite (c)
cement.

of the Black Flysch Group (Figs. 1B and 2A). Internally, the sill is
crossed at high angles by veins that are several meters long and
< 10 cm thick and are lled with carbonate cements (sparry calcite
and saddle dolomite) and fragments of mudstone and host basalt
(Fig. 2B and C). The veins pinch out very rapidly and disappear
within the overburden mudstones near the sill contacts.
3. Samples and methods
A total of 16 samples of mudstones were collected along a
9.86 m thick interval above the sill intrusion (Fig. 2A; Table 1). In
addition, 4 carbonate veins into the sill were sampled (Fig. 2B
and C; Table 2). 42 thin sections corresponding to all mudstone
and carbonate vein samples were examined under plane-polarized
and cross-polarized transmitted light microscopy. In addition, Xray diffraction (XRD) of all mudstone samples was carried out
using an automated PANalytical Xpert PRO diffractometer (PANalytical, Einhoven, The Netherlands) at the Euskal Herriko Unibertsitatea. Identied metamorphic minerals are shown in Table 1.
All mudstone samples were microscopically characterized using
reected white light, polarized light and blue-violet excitation
(Fig. 3). For this purpose they were prepared for microscopic analysis according to the ISO7404/2 (2009) standard. Vitrinite and bitumen reectance measurements were taken in a Leica MPV Combi
Microscope following the procedures described in the ISO 7404/5
(2009) standard; results are shown in Table 1 and plotted in
Fig. 4. Polarized light combined with a 1k retarder plate was used
during the petrographic analysis of the more mature samples using
a Leica DM 4500P microscope. For the less mature samples, uorescence microscopy was employed using blue light excitation

using the same equipment. Photomicrographs were taken also

using a camera and Leica software to capture and analyze images.
All of the mudstone samples were submitted for Rock-Eval
pyrolysis following the procedure described by Espitali et al.
(1985a,b, 1986). Total organic carbon (TOC) was analyzed with
the carbon module coupled to the Rock Eval-I. Results are shown
in Table 1 and most of them are plotted in Fig. 4.
Soluble organic matter (bitumen) was extracted from four mudstone samples using a Soxhlet apparatus with a mixture of dichloromethane and methanol (2:1). After concentration, the extracts
were hydrolyzed and fractionated by silicaalumina column chromatography. The aliphatic hydrocarbons were separated by elution
with n-hexane. The saturated hydrocarbon fraction was eluted
with isohexane and the aromatic hydrocarbons with dichloromethane. Samples were analyzed by gas chromatography (GC). A
gas chromatograph Agilent Technologies 6890N (HP-5 capillary
column, 30 m  0.32 mm i.d.  0.25 lm lm thickness, He carrier
gas) equipped with a ame ionization detector and a splitless
injector was used. The column was heated from 70320 C, at a
rate of 6 C/min. Chromatograms are shown in Fig. 5. In addition,
in three of the four samples carbon isotopic determination on saturated and aromatic hydrocarbon fractions was performed using a
Thermo Finnigan 1112 elemental analyzer coupled to a Finnigan
Mat Delta C mass spectrometer. The reference materials were USGS
24 graphite, IAEA-CH6 saccharose, IAEA-CH7 polyethylene, and
NBS-22 oil. The 13C/12C ratio is reported in o notation and o13C
is referenced to PDB (Pee Dee Belemnite). Obtained results are
shown in Fig. 5.
Carbonates from 4 mudstone samples and 4 carbonate veins
within the sill were selected for oxygen and carbon isotope

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L.M. Agirrezabala et al. / Organic Geochemistry 69 (2014) 2635

Table 1
Data from mineral, organic and Rock-Eval analyses for mudstones above the magmatic sill.

a
b

Sample

Thicknes Metam.
VRo
(% s.t.)
mineral phasesa (%)

BRo
(%)

TOC
(wt%)

MAR-39
MAR-42
MAR-43
MAR-44
MAR-45
MAR-46
MAR-47
MAR-48
MAR-49
MAR-50
MAR-51
MAR-52
MAR-53
MAR-54
MAR-55
MAR-56

0.4
3.8
6.2
9.8
12.8
18.0
24.4
36.2
42.4
55.2
71.2
95.8
105.6
113.6
147.6
197.2

4.97
4.62
5.65
4.85
4.68
2.67
2.32
2.67
1.96

0.92
0.40
ndb
0.78
0.97
0.99
1.27
1.21
1.05
1.26
ndb
ndb
1.24
1.13
1.19
ndb

ch,e,d,c,l,g
ch,e,d,c,g
ch,e,d,c,g
ch,e,d,c,g
ch,d,c,e,g
ndb
ch,d,c,e
ch,d,e,c
ch,e,d,c
ch,e

5.04
4.57
4.55
4.63
4.42
2.20
2.08
1.66
1.56
1.55
1.55
1.49
1.45
1.46
1.43
1.40

Rock-Eval
TOC (wt%) S1 (mg/g) S2 (mg/g) S3 (mg/g) PI S1/(S1 + S2) Tmax (C) HI (mg/g) OI (mg/g) PC (mg/g)
0.53
0.18
0.35
0.38
0.71
0.93
1.26
1.15
0.97
1.22
1.06
1.25
1.13
1.08
1.11
1.14

0.03
0.03
0.03
0.02
0.03
0.05
0.08
0.10
0.06
0.08
0.07
0.10
0.08
0.09
0.09
0.10

0.01
0.01
0.07
0.03
0.07
0.07
0.24
0.42
0.38
0.49
0.43
0.62
0.53
0.46
0.54
0.57

0.12
0.11
0.07
0.02
0.15
0.02
0.01
0.00
0.02
0.08
0.08
0.11
0.02
0.24
0.01
0.04

0.75
0.75
0.30
0.40
0.30
0.41
0.25
0.23
0.14
0.14
0.14
0.13
0.13
0.16
0.14
0.15

348
ndb
322
356
477
391
540
510
505
488
490
480
481
489
490
482

1
5
5
7
9
7
19
36
39
40
40
48
46
42
48
50

22
61
20
5
21
2
0
0
2
6
7
8
1
22
0
3

0
0
0
0
0
0.01
0.02
0.04
0.03
0.04
0.04
0.05
0.05
0.04
0.05
0.05

Metamorphic mineral phases: ch = chlorite; d = dolomite; c = calcite; e = epidote; l = larnite; g = graphite.

n.d. = Not determined.

Table 2
Stable carbon and oxygen isotope values for carbonates from the contact aureole and
veins.
Sample

Mineral

Aureole
MAR-39
MAR-43
MAR-45
MAR-49

Dolomite + calcite
Dolomite + calcite
Dolomite + calcite
Dolomite + calcite

Veins
MAR-57
MAR-58
MAR-59
MAR-60

Calcite
Calcite
Calcite
Calcite

o13C (VPDB)

o18O (VPDB)

6.04
5.63
5.47
6.54

7.54
6.66
7.40
7.23

8.97
9.60
9.82
10.13

10.10
7.16
7.44
8.20

analyses. Stable carbon and oxygen isotopes were analyzed at the

Leibniz Laboratory for Radiometric Dating and Stable Isotope Research (Kiel) by using a Kiel IV connected to a ThermoFinnigan
MAT 253 mass spectrometer. Carbon dioxide to be analyzed in
the mass spectrometer is released from the carbonates by reaction
with 99% phosphoric acid at a constant temperature of 75 C. The
reaction time was 18 min, which is sufcient also for complete
reaction of dolomite. The standard external error (precision) for
carbonate standard material was better than 0.1 for d18O values and 0.06 for d13C values. Results are reported with respect
to the Vienna PeeDee belemnite (V-PDB) scale. Daily runs on international (e.g., NBS20, NBS19 and NBS18) and laboratory internal
carbonate standards, including a dolomite standard, were performed for calibration and quality control. The measurements of
bulk sediments reect a combination of the isotopic compositions
of the different carbonate minerals (e.g., calcite and dolomite) and
their percentage in the sediment. Isotopic data are shown in
Table 2.

4. Results and discussion

4.1. Characteristics of sediments adjacent to the igneous sill
Petrographic and XRD analyses show that the main detrital
minerals in the mudstones are quartz, feldspar, mica, kaolinite
and illite; low concentrations of heavy minerals and framboidal
pyrite are also present, although the latter is absent close to the
intrusion. Adjacent to the sill, mudstones have a granular texture

with metamorphic minerals, i.e. chlorite, epidote, larnite and carbonates (dolomite and calcite) (Table 1), indicating that the duration of the thermal pulse from the 5 m thick igneous sill was
long enough for mineral reactions to occur as a response to contact
metamorphism. The presence of larnite mineral (stable in the
range of 520670 C; www.mindat.org) at the sill contact (0.4% sill
thickness, s.t.) indicates that the highest temperatures occurred
adjacent to the intrusion, whereas disappearance of epidote at
55% s.t. suggests lower thermal conditions (200 C; Aarnes
et al., 2010).
4.2. Organic components and vitrinite and bitumen reectance proles
Organic components identied in mudstone samples far away
from the sill (P 42% s.t.) using reected white light are vitrinite,
inertinite and hydrocarbons. These hydrocarbons are extremely
scarce, transparent in reected white light and they are only observable in uorescence mode showing an orange color (Fig. 3A and
B). These hydrocarbons could have been formed either by contact
metamorphism and subsequent migration of generated hydrocarbons outward from the aureole or by burial maturation of the organic matter. In mudstones closer the sill (< 42% s.t.),
petrographic components are vitrinite, inertinite and solid bitumen (pyrobitumen). Pyrobitumens occur in cracks, fractures, and
between carbonate minerals (Fig. 3D). These pyrobitumens were
derived from the hydrocarbons that were generated by cracking
of the kerogen in the rocks under the thermal inuence of the magmatic body. In the samples closest (6 13% s.t.) to the sill, the occurrence of graphitic and coke particles (Fig. 3C, E and F), organic
particles with devolatilization vacuoles (Fig. 3G), highly reective
vitrinites (Fig. 3H), and pyrobitumens (by losing their lighter components, such as more hydrogenated liptinitic components) conrm the strong inuence of a high thermal gradient.
A common way of estimating the aureole width adjacent to
magmatic intrusions is based on vitrinite reectance proles, and
occasionally on solid bitumen reectance measurements. The results of mean random reectance measurements of vitrinite
(VRo) and bitumen (BRo) from mudstones overlying the sill studied
are shown in Table 1 and plotted in Fig. 4. The background vitrinite
reectance values of the mudstones away from the sill (> 42% s.t.)
range between 1.40% and 1.56% VRo. These values represent the
baseline of post-intrusion (Late Albian-Tertiary) burial effect
(Gmez et al., 2002), which superimposes on the original prole
at the time of the intrusion (Albian); taking into account the

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L.M. Agirrezabala et al. / Organic Geochemistry 69 (2014) 2635

Fig. 3. Photomicrographs of organic components in mudstone samples. (A) Mineral grains and hydrocarbons (arrow) only visible in uorescence. Sample at 147% s.t. (MAR55). (B) Same eld as (A) with hydrocarbon exhibiting yellow color uorescence between the grains (arrow). (C) Highly evolved organic particle strongly anisotropic (arrow).
Sample at 12% s.t. (MAR-45). (D) Solid bitumen (pyrobitumen). Sample at 9% s.t.(MAR_44). (E) Vitrinite particle showing anisotropy and coke texture. Polarized light using 1k
retarder plate. Sample at 9% (MAR-44). (F) Same eld as (E) with the particle rotated 90. (G) Organic particle strongly affected by thermal stress showing anisotropy and
degasication vacuoles. Sample at 3.8% s.t. (MAR-42). (H) Vitrinite particle. Notice its high reectance which demonstrates the strong thermal stress close to the sill. Sample
at 3.8% s.t. (MAR-42).

shallow depth of the intrusion (ca. 150 m), a pre-intrusion VRo value of 0.25% can be estimated for host sediments (Hunt, 1996).
The vitrinite reectance prole shows an initial increase at 40%
s.t., followed by a gradual increment toward the sill, reaching a
maximum of 5.04 %VRo nearest (0.4% s.t.) the intrusion. These
reectance values dene a contact aureole 40% s.t. and indicate a
strong thermal effect of the intruded magma on the organic material. The maximum reectance value suggests temperatures as high
as 600 C at the sill contact (Bostick, 1971), in concordance with
the temperature indicated by the larnite mineral at the contact.

Contact aureoles are typically one intrusion width and usually

vary between 30% and 200% of the intrusion thickness (compilation by Aarnes et al., 2010, and references therein). The thickness
variability is interpreted as a consequence of several factors, for
example intruded magma temperature, different uid systems,
background maturation, and degree of compaction (e.g. Raymond
and Murchison, 1988; Barker et al., 1998). In this study, the present-day aureole width of 40% s.t. must be considered as a minimum of the original (Albian) aureole width, because it is
overlapped by post-intrusion, regional background burial

L.M. Agirrezabala et al. / Organic Geochemistry 69 (2014) 2635

31

Fig. 4. Lithological log, samples and organic geochemical proles (vitrinite (VRo) and bitumen reectances (BRo), TOC, S1, S2, Pyrolyzed Carbon PC, Tmax, HI and OI) of
mudstones above the sill. Plotted values are listed in Table 1. Note that as vitrinite and bitumen reectances, Tmax and OI increase towards the sill, TOC, S1, S2, Pyrolyzed
Carbon and HI decrease. See text for discussion.

reectance values (1.4%; Gmez et al., 2002). Taking into account

that igneous sill intruded unconsolidated muddy sediments at a
depth of ca. 150 m based on the stratigraphic depth below the contemporaneous paleoseabed (base of the Mariarri unit; see Fig. 1B
and Supplementary material Table S1), and that they were overlaid
by a thick Upper CretaceousTertiary sedimentary succession (ca.
3500 m, Gmez et al., 2002), contact aureole compaction must
have been signicant. In addition to post-intrusion compaction,
dissipation of thermal energy via heating and evaporation of pore
uids in unconsolidated sediments could also explain the relatively
thin contact aureole (e.g. Raymond and Murchison, 1988, 1991;
Murchison and Raymond, 1989). In the study case, the sill intruded
into shallow mudstones (ca. 150 m), which would have been relatively unconsolidated and probably with a large volume of pore
water at that time. As such, the thermal effect from the intrusion
on the surrounding muddy sediments could have been moderate.
The occurrence of solid bitumens is limited to within the contact aureole (< 42% s.t.) and their reectance shows a general increase toward the contact from 1.96% BRo at 42% s.t. to 4.97% BRo
closest to the contact, showing a similar trend to the vitrinite
reectance prole (Fig. 4). Solid bitumen responds to increased
heating much like vitrinite, and bitumen reectance can be used
to assess thermal history (e.g. Robert, 1988; Barker and Bone,
1995; among others). Results suggest that oil was formed almost

instantaneously by contact metamorphism of organic material

and that the generated oil was severely affected by the high temperature conditions within the aureole. These high temperature
conditions provoked a secondary cracking, oil cracking with gas
(CH4 among other minor gases) generation and leaving an enriched
(in carbon) organic component: the solid hydrocarbon or pyrobitumen. The occurrence of the solid bitumen only within the contact
aureole also indicates that the oil did not migrate outward from the
aureole, perhaps due to rapid solidication of the bitumen induced
by the thermal stress.
4.3. Total organic carbon
Total organic carbon analyses for the mudstone samples are given in Table 1 and plotted in Fig. 4. The results indicate that samples farther from the sill (> 24% s.t.) have TOC values between 1.2%
and 1.0% (average 1.1%). These organic carbon concentrations are
similar to background values of the Black Flysch Group at other
localities (Agirrezabala et al., 2008, 2013; Agirrezabala, 2009). At
24% s.t., the organic matter prole shows progressive decrease in
TOC toward the sill, reaching a minimum value of 0.4% at 3% s.t.,
before undergoing a small reversal. Intrusive heating has destroyed
the organic matter in the contact aureole mudstones, reaching a
maximum organic carbon loss of 64% with respect to background

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L.M. Agirrezabala et al. / Organic Geochemistry 69 (2014) 2635

sill contact could not escape. In the present study, some products
of pyrolysis produced within the inner aureole were clearly immobilized as graphitized or coked particles (Fig. 3C, E and F).
4.4. Rock-Eval pyrolysis
Rock-Eval analyses for the mudstones are shown in Table 1 and
selected parameters (S1, S2, Tmax, HI, OI and Pyrolyzed Carbon
that corresponds to carbon content of hydrocarbons volatilized
and pyrolyzed during the analysis) are plotted in Fig. 4. The hydrocarbon genetic potentials (S1 + S2, 0.50.7 mg/g) and Hydrogen Index values (HI, 4050 mg/g) distant from the sill indicate poor oil
source rock potential. Rock-Eval results support a high thermal
stress and destruction of hydrocarbons within the contact aureole,
which is more pronounced as the sill is approached. S1 values
(hydrocarbons/weight of rock) decrease from 0.1 mg/g distant
from the sill to 0.02 mg/g close to it. The S2 values (pyrolytic
hydrocarbons/weight of rock) decrease from a mean 0.53 mg/g value far from the contact to 0.01 mg/g close to the sill. Similarly,
Pyrolyzed Carbon values drop to zero near the sill (Fig. 4).
The Tmax values increase from a background level of 490 C distant from the sill to 540 C at 24% s.t. The Tmax values of samples
closer to the sill (6 18% s.t.) have not been taken into account because they show S2 peaks lower than 0.2 mg/g and, therefore,
Tmax values can be unreliable (Espitali et al., 1985a,b, 1986).
The production index (S1/S1 + S2) yields a background value of
ca. 0.14 distant the sill and exhibits an initial increase at 36% s.t.
reaching a value of 0.75 close the sill. The gradual increase in both
Tmax and the production index values toward the sill reects the
increasing degree of pyrolysis of kerogen due to thermal stress
(George, 1992). Hydrogen index values gradually change from a
background value of 4050 mg/g to lower values toward the magmatic body (minimum value of 1 mg/g at the contact) due to thermal alteration (Fig. 4). The overall very low oxygen index values
show a signicant increase near the sill (up to 61 mg/g) (Fig. 4).
This suggests hydrothermal oxidation of the organic matter during
heating by the intrusion, which is consistent with the occurrence of
CO2 derived carbonate in the contact aureole (see Section 4.6).
4.5. Gas chromatography and organic carbon isotopes

Fig. 5. Chromatograms, pristane/phytane ratios and carbon isotope ratios of

saturated and aromatic hydrocarbon fractions from mudstones sampled at different
distance from the sill (105%, 42%, 18% and 0.4% s.t.). C20 and C28 n-alkanes are
marked with their carbon number for orientation.

concentrations. A signicant decrease in the concentration of organic carbon in deposits heated by igneous intrusions is common
in other examples (Saxby and Stephenson, 1987; Bishop and Abbott, 1995; Cooper et al., 2007; Svensen et al., 2007; Aarnes
et al., 2011b). Unlike these examples, in which TOC values decrease
with increased proximity to the igneous intrusion, in the present
case the concentrations are at their lowest not at the contact but
at 3% s.t. (Fig. 4). This pattern is similar to that described in a coal
seam by Meyers and Simoneit (1999), who propose two alternative
interpretations: (i) cracking and reorganization of the organic matter during heating; or (ii) heating may have been so rapid that the
products of thermal degradation of the organic matter close to the

Gas chromatography of hydrocarbons extracted from four mudstone samples (105%, 42%, 18% and 0.4% s.t.) was carried out. Extracted aliphatic hydrocarbon fractions from the four samples are
scarce, especially the sample closest to the magmatic sill. The
changes in the composition of the aliphatic hydrocarbons with
increasing proximity to the sill are evident in the gas chromatograms (Fig. 5). The sample with the lowest rank (105% s.t.) is dominated by low molecular weight n-alkanes, with maxima at n-C20.
The mudstone sample closest to the aureole outer boundary (42%
s.t.) has a greater proportion of n-alkanes, with a maximum at
n-C29. In the sample at 18% s.t., the most abundant n-alkane is
n-C20 but there is also a smaller, secondary maximum at n-C28.
At the sill contact (0.4% s.t.), the mudstone sample has a very
low n-alkanes concentration, with maxima around n-C20. Gas chromatograms of the aliphatic hydrocarbons show a noticeable loss of
n-alkanes adjacent to the sill as well as a shift in the carbon number distribution to a predominance of the shorter chain-length
homologues (Fig. 5), which are typical features of thermal stress
closest to igneous intrusions (e.g. Schiener and Perregaard, 1981;
Clayton and Bostick, 1986; George, 1992). The pristane-to-phytane
ratios (Pr/Ph) are low and show little variation in the four mudstone samples (between 0.43 and 0.75; Fig. 5), although the peaks
are difcult to measure because they are very small, especially
those of the high rank samples.

L.M. Agirrezabala et al. / Organic Geochemistry 69 (2014) 2635

Carbon isotopes of saturated and aromatic hydrocarbon fractions extracted from the three samples nearest to the intrusion
(42%, 18% and 0.4% s.t.) yield dissimilar o13C values (Fig. 5). The
more distant two samples, with less thermal alteration, show similar isotopic results with o13Csat values of 27.7 and o13Caro values between 23.1 and 23.2. However, the sample at the
contact (0.4% s.t.) shows results markedly less negative, with
o13Csat and o13Caro values of 20.3 and 21.2, respectively.
The values of the two more distant samples are close to those reported for both Black Flysch mudstones unaffected by contact
metamorphism and pyrobitumen lls at the Mutriku locality, a site
48 km to the east (Agirrezabala et al., 2008). These characteristics
suggest that the thermal impact of the intrusion in the mudstones
of the middle-outer aureole did not affect the isotopic ratios of the
extracted organic material signicantly and that little to no isotopic fractionation took place during hydrocarbon formation. Only
the sample affected by the most severe thermal stress at the sill
contact shows relative 13C enrichment in the extracted hydrocarbon fractions, although it is possibly an analytical artifact due to
the small amount of extracted hydrocarbons. Many published
studies document small, if any, carbon isotope fractionation of kerogen and bitumen (Do13C 6 1.5) with increasing thermal effect,
and there is no consensus on the direction of the fractionation
(Faure, 1986; Schoell et al., 1990; Andresen et al., 1995; Whiticar,
1996; Grcke et al., 2009).

33

analyzed here (Table 2). An organically derived CO2 source for

carbonates precipitated in thermally altered, organic rich sediments has been also proposed by other authors. Saxby and Stephenson (1987) found carbonate minerals in the contact aureole
of an oil shale, where samples closest to the magmatic sill had
o13C values of  10.5. Meyers and Simoneit (1999) similarly
noted that in a coal seam affected by an igneous intrusion calcite
occurs only in the samples closest to the intrusion and had a
o13C value of 12.7.
The o18O values of the aureole carbonates and vein calcites
range between 6.6 and 10.1 ( 8.2 average value). These
relative light oxygen values indicate that the carbonate formed at
high temperatures probably as a result of the intrusion heating
event. Although other alternatives are possible for calcite 18O
depletion (e.g. inux of meteoric waters or recrystallization during
burial diagenesis), as the calcite is associated with saddle dolomite,
a paleothermometer indicative of temperatures higher than 60
80 C (Radke and Mathis, 1980), it is proposed that carbonate minerals were formed from CO2 rich waters heated by the sill intrusion. As soon as temperatures within the contact aureole near
the intrusion cooled sufciently to allow the onset of aqueous circulation, the weathering of the sill and adjacent mudstones provided calcium to allow precipitation of 13C depleted calcite in
fractures of the warm to hot basalt intrusion.
4.7. Aureole degassing and overpressure

4.6. Carbonate isotopic characterization

Analysed carbonate samples from the sill aureole and the veins
are depleted in both 13C and 18O compared with sea water values
(Table 2). The aureole carbonates yield o13C values ranging between 5.4 and 6.5 ( 5.9 mean value), and vein carbonates show more negative o13C values between
8.9 and
10.1 ( 9.6 mean value). These data suggest that the carbon
of the carbonate minerals had an organic source from the alteration of organic matter. Contact aureoles in organic-rich shales
and coals are usually dominated by CH4 and CO2 uids derived
from the thermal alteration of the organic matter (e.g. Hunt,
1996; Meyers and Simoneit, 1999; Aarnes et al., 2010). The CO2
thus produced has o13C values typically between
8 and
12 (Hunt, 1996), which are close or similar to those values obtained for the carbonates. This fact, together with the carbonate
mineral distribution being constrained to the contact aureole and
veins, suggests that thermogenic CO2 was retained within the
aureole and sill fractures by reaction with metamorphic uids
and precipitation of 13C depleted calcite and dolomite. A magmatic
CO2 source for the carbonates is unlikely as it usually has less depleted o13C values (around 3; Hoefs, 1997) than the carbonates

These characteristics indicate a strong thermal impact on sediment minerals and organic matter present in the 2 m thick (40%
s.t.) contact aureole. Low TOC values and Rock-Eval parameters
in the aureole samples indicate loss of carbon in the organic material. Organic rich shales and coals affected by igneous intrusions
typically show a similar carbon loss, which is interpreted as the
consequence of devolatilization of carbon from organic material
(Svensen et al., 2007; Aarnes et al., 2010). The carbon gases thus
formed are dominated by CH4 and CO2 in the case of organic rich
mudstones (e.g. Conolly and Cesare, 1993; Aarnes et al., 2010,
2011a,b). In addition to gases, small amounts of oil were formed
as indicated by the presence of solid bitumens (Fig. 6A). Thermal
metamorphism of clay rich sediments comprised mainly of hydrous minerals would have generated relatively large amounts of
H2O (e.g. Kerrick and Connolly, 2001) (Fig. 6A).
In sedimentary rocks heated by magma intrusions, signicant
uid overpressure occurs as a consequence of pore uid expansion,
boiling (at depths < 1 km), and generation of uids by organic matter decomposition and mineral dehydration. In the Black Flysch
mudstones affected by the intrusion, rapid gas (CH4 and CO2) and
water generation likely facilitated overpressure buildup as the

Fig. 6. Schematic model of the degassing and uid producing processes occurring in the contact aureole at Gorliz. (A) At an early stage, prograde contact metamorphic
reactions produces CH4, CO2 and oil from sedimentary organic matter and H2O from mineral dehydration. (B) At a later stage, CO2 reacts with pore waters to form carbonate
minerals in the aureole and sill fractures; generated oil becomes bitumen (pyrobitumen) in the aureole; CH4 and H2O escape from the aureole upward along hydrofractures to
the paleoseabed, where methane derived authigenic carbonates precipitate (Agirrezabala, 2013).

34

L.M. Agirrezabala et al. / Organic Geochemistry 69 (2014) 2635

permeability of un-fractured mudstones are very low (Brace, 1980)

(Fig. 6A). The pressure buildup resulted in hydrofracturing and uidization of the overburden recorded by the clastic dykes and
extrudites above the magmatic sill (Fig. 1B and Supplementary
material Table S1 and Figs. S1 and S2) (Agirrezabala, 2013). Also,
the occurrence of sedimentary material in the veins within the
magmatic sill (Fig. 2) is here suggested to be the result of overpressure and subsequent fracturing and uidization of sediments in the
contact aureole. Svensen et al. (2010) interpret sandstone dykes intruded in igneous sills as result of high pressure gradients and sediment uidization during magma solidication.
CO2 produced in the aureole reacted with pore water to form
13
C depleted carbonate minerals that precipitated in situ and
within the fractures that cross the sill (Fig. 6B). Overpressure-induced hydrofractures above the sill (Supplementary material
Fig. S1) provided escape conduits for the aureole CH4 and H2O
(Fig. 6B). Along these hydrofractures a mixture of water-charged
uidized sediments and CH4 was channelled up to reach the
paleoseabed, where extrudite deposits and authigenic carbonates
were formed coevally to the sill emplacement (Agirrezabala,
2013). The high depletion in 13C (up to o13C 38.7) and the petrologic characteristics of the authigenic carbonates indicate that
they are the by-product of microbial activity that causes anaerobic oxidation of methane (AOM) (Boetius et al., 2000). A presentday analogue for this Cretaceous case is the deep-water Guaymas
Basin (Gulf of California) where similar processes including sill
intrusions, metamorphism of organic-rich sediments, formation
and expulsion to the seabed of thermogenic methane, and methane-derived authigenic carbonate formation at the seaoor have
been reported (Lizarralde et al., 2011).
5. Conclusions
The thermal effect of the Late Albian, 5 m thick magmatic sill
caused contact metamorphism of the host mudstones and strong
alteration of the organic matter contained in the aureole sediments. Vitrinite and bitumen reectance proles indicate increasing thermal alteration toward the sill and a 2 m thick (40% s.t.)
contact aureole. Nevertheless, the original (Albian) aureole could
have been thicker than the present-day aureole record due to the
post-intrusion effects of compaction and burial reectance overlapping. Geochemical and petrographic results indicate an increasing loss of carbon from the organic matter toward the sill. Organic
carbon loss within the aureole would have been the result of carbon devolatilization and formation of thermogenic CH4 and CO2
gases and oil. Generated uids facilitated overpressure buildup in
the aureole, which resulted in hydrofracturing and uidization of
the overburden and formation of clastic dykes. Generated CO2 reacted with pore waters to form 13C depleted carbonate minerals
within the aureole itself and in the sill fractures. Thermogenic
CH4 escaped from the aureole along overpressure-induced hydrofratures (clastic dykes) to the paleoseabed, where methane-derived
authigenic carbonate deposits were formed.
Acknowledgements
Agirrezabala and Dorronsoro acknowledge support from the
Euskal Herriko Unibertsitatea (projects EHU2011-46 and IT63113), and Permanyer thanks nancial support from the Ministerio
de Ciencia e Innovacin (Project CGL2010-15887). M. Carracedo
and I. Gil-Ibarguchi are thanked for their help in the determination
of metamorphic minerals. Susan Rimmer and one anonymous reviewer are thanked for their useful and constructive comments.
Associate EditorJoe Curiale

Appendix A. Supplementary material

Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.orggeochem.2
014.01.014.
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