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Insights from fluid inclusions, thermal and PVT modeling for paleo-burial and
thermal reconstruction of the Córdoba petroleum system (NE Mexico)

Article  in  Marine and Petroleum Geology · April 2011

DOI: 10.1016/j.marpetgeo.2010.01.020

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Marine and Petroleum Geology xxx (2010) 1–23

Contents lists available at ScienceDirect

Marine and Petroleum Geology

journal homepage: www.elsevier.com/locate/marpetgeo

Insights from fluid inclusions, thermal and PVT modeling for paleo-burial and
thermal reconstruction of the Córdoba petroleum system (NE Mexico)
Helga Ferket a, b, *, Nicole Guilhaumou c, François Roure a, Rudy Swennen d
a
Institut Français du Pétrole, 1 et 4 Avenue de Bois-Préau, 92852 Rueil-Malmaison Cedex, France
b
Instituto Mexicano del Petróleo, Eje Central Lazaro Cárdenas 152, Col. San Bartolo Atepehuacán, 07730 México D.F., Mexico
c
Museum National d’Histoire Naturelle, LMCM/UMR 7202-Case 52-57, Rue Cuvier, 75231 Paris, France
d
Katholieke Universiteit Leuven, Geologie, Celestijnenlaan 200E, Bus 02408, 3001 Heverlee, Belgium

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

Article history: Carbonate reservoirs in the Córdoba petroleum system (NE Mexico) passed through a multiphase
Received 3 September 2009 deformation history complicating the petroleum geology. The area evolved from passive margin and
Received in revised form foreland setting to Laramide fold and thrust belt (FTB) that was subsequently buried below the Tertiary–
19 January 2010
Quaternary Veracruz Basin, which in turn underwent transpressional deformation. Reconstruction of
Accepted 27 January 2010
Available online xxx
paleo-burial (erosion) and paleo-thermicity through the different zones of the FTB and adjacent foreland
is a challenging task since classical calibration tools fail to discriminate between several kinematic and
thermal models. In this study results from detailed diagenetic and fluid inclusion (FI) analyses on
Keywords:
Thrust belt carbonates from the western part of the Córdoba Platform helped constraining paleo-thermicity.
Fluid inclusion Combined microthermometry, synchrotron FTIR analyses and PVT modeling of cogenetic hydrocarbon-
Diagenesis aqueous FI allowed also calculation of absolute pressures. Thermal modeling exercises calibrated with
Geothermal gradient organic maturity parameters, bottom-hole temperatures or temperatures from FI demonstrate that
PVT modeling without controlling also paleo-erosion the model results may be misleading.
Córdoba Platform Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction The petroleum system of the Córdoba Platform–Veracruz Basin

Petroleum exploration in complex areas such as fold and thrust
belts (FTB) requires a dynamic view on the regional kinematic
evolution. Reconstruction of paleogeothermal gradients in their
associated foreland basins based on maturity indicators of organic
matter (e.g. Ro, Tmax) generally yield good results. FTB, on the other
hand, often pass through a multiphase kinematic evolution, for
which sedimentary/tectonic load and erosion can rarely be fully
controlled. Lacking this ‘burial’ parameter, thermal modeling
exercises in FTB lead to ambiguous results for ancient heat flow.
Extrapolation of erroneous values for burial and temperature may
lead to failing prediction of petroleum prospects. The key question
is: How can the independent parameters P (pressure as function of
burial history) and T (temperature as function of heat flow or
geothermal gradient) be controlled in order to validate a kinematic
model?
* Corresponding author at: Vlaamse Instelling voor Technologisch Onderzoek
(VITO), unit SCT, Boeretang 200, B2400 Mol, Belgium. Tel.: þ32 14 33 56 26; fax:
þ32 14 32 11 86.
E-mail address: helga.ferket@vito.be (H. Ferket).
in eastern Mexico is complicated by multiple potential sources and
timings of petroleum migration in a context of multiphase defor-
mation and fluid flow. As the other segments of the Sierra Madre
Oriental farther to the north (Pottorf et al., 1996; Yurewicz et al.,
1997; Gray et al., 2001; Alzaga-Ruiz et al., 2009a,b), the Córdoba–
Veracruz area progressively changed from passive margin and
foreland setting towards an active FTB, and became subsequently
uplifted and unroofed in post-Laramide times, its erosional products
being transferred eastward to the Veracruz Basin, the latter then
being affected by transpressional deformation (Meneses-Rocha
et al., 1997; Rojas, 1999; Prost and Aranda-Garcia, 2001; Ortuño-
Arzate et al., 2003). A multidisciplinary study was set up in order to
better constrain the structural evolution, the kinematic history,
reservoir evolution and petroleum system of the Córdoba Platform
and adjacent Veracruz Basin (Ortuño-Arzate et al., 2003; Roure et al.,
2009, in press; Gonzalez-Mercado et al., submitted for publication).
Although several stages in the diagenetic evolution of the reservoirs
were documented in previous studies (Ferket et al., 2003a,b, 2004,
2006), details on the migrating hydrocarbon (HC) fluids, trapping
conditions and subsequent alteration of HC were lacking. Such
information can be obtained when the related (HC–H2O) fluids are
preserved in minerals as fluid inclusions (FI) during successive

0264-8172/$ – see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpetgeo.2010.01.020

Please cite this article in press as: Ferket, H., et al., Insights from fluid inclusions, thermal and PVT modeling for paleo-burial and thermal...,
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2 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23

phases. Since mineral (carbonate) precipitation slows down (or
stops) with decreasing H2O content (Feazel and Schatzinger, 1985),
the early HC-trapping and alteration conditions are not commonly
recorded in coeval mineral precipitates. This study presents detailed
analytical results of multiple generations of aqueous and HC-FI that
are representative of trapping and post-trapping conditions. More-
over, some generations of aqueous and HC-FI are cogenetic, allowing
besides paleo-temperatures and compositions also paleo-pressures
(and thus burial) to be calculated.
Fluid inclusion data can add valuable information only when it
is clear what (i.e. what timing, what fluids, primary, secondary,
altered phases, .) we are measuring. A calibration data set with
paleo-temperatures (and pressures where available) was compiled
based on diagenetic research combined with microthermometric
and SFTIR analyses. These analytical results were used as input for
PVT modeling. The independent estimates for paleo-temperature
and paleo-burial are linked to the deformation agenda by unrav-
eling the paragenetic relationships between diagenetic phases. The
crosscutting relationships between diagenetic features and
different sets of stylolites are of significant value for constraining
the timing of events. Bed-parallel stylolites (BPS) result from
vertical compaction during initial burial. Layer-parallel shortening
stylolites (LPSS) form under increasing compressional stress and
under high angle to bedding, mainly prior to folding.
The compiled data set was used to calibrate thermal modeling,
i.e. constrain heat flow and paleo-burial scenarios, and conse-
quently to test the kinematic model. This study shows that the
formerly accepted kinematic model presented by Ortuño-Arzate
et al. (2003) had underestimated the amount of erosion and ‘Lar-
amide’ burial. This burial might relate to both flysch sedimentation
in an ancient foredeep and tectonic stacking.
2. Geological setting
The Córdoba Platform originated during the Cretaceous as an
isolated carbonate platform in the petroleum-rich circum-Gulf of
Mexico province and became part of the Sierra Madre Oriental FTB
during Laramide orogeny. Thin-skinned thrust sheets are exposed
to the west where they are partly overthrust by unrooted tectonic
slices of the former Zongolica Basin (Fig. 1). Towards the east the

Fig. 1. Geological map of the Córdoba Platform and Veracruz Basin showing the locations of exploration boreholes and outcrops studied (A–F).

Please cite this article in press as: Ferket, H., et al., Insights from fluid inclusions, thermal and PVT modeling for paleo-burial and thermal...,
Marine and Petroleum Geology (2010), doi:10.1016/j.marpetgeo.2010.01.020
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H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23 3

outcropping thrust sheets of the Córdoba Platform Buried thrust front with oil fields
SW NE
Sierra San J. de Gracia Sierra Atoyac 4
3
Peñuela 2
A 1
0
1
2
3
4
5
6
7
8

Paleozoic basement Orizaba Fm. Atoyac Fm. klippes Zongolica Basin Quaternary
0 2 4 km
L. Cretaceous Guzmantla Fm. U. Cretaceous and Tertiary Veracruz Basin paleoseeps
Paleocene flysch

Fig. 2. Structural cross-section through the Córdoba Platform and Veracruz Basin along the transect indicated in Fig. 1. The fluid inclusion data used to calibrate thermal models in
this study comes from Orizaba Formation dolomites of the Sierra San José de Gracia (especially from the cored borehole A) and from Guzmantla Formation limestones of the Sierra
Atoyac and Sierra San José de Gracia (where an exhumed and biodegraded oil reservoir crops out at Peñuela).

thrust belt culminates in a stack of duplexes constituting the
tectonic front (Rojas, 1999; Ortuño-Arzate et al., 2003). The latter
domain is unconformably overlain by Tertiary to Quaternary sedi-
ments of the Veracruz Basin (Fig. 2). This basin underwent further
transpressional deformation during the Miocene. The carbonate
reservoirs in the buried tectonic front zone host oil and gas fields
that were largely exploited in the last decades. Furthermore, the
Veracruz Basin hosts a series of thermo- and biogenic gas fields (e.g.
Jennette et al., 2003). The western, presently outcropping, part of
the FTB (Fig. 1) is considered as uneconomic, although the existence
of an ancient petroleum system with weathered oil seeps and
reservoir analogues has been put forward (Ferket et al., 2003B).
Several diagenetic products discussed in the present paper also
relate to an ancient (syn-Laramide) phase of petroleum migration
in this part of the platform.
Based on biomarker analysis results and on analogy with
neighbouring regions, potential source rock intervals are postu-
lated to occur within the Jurassic (Tepexilotla Formation), the Late
Cretaceous (Orizaba and Maltrata Formations) and within the
Tertiary succession (Paleocene, Eocene, Oligocene, Miocene and
Pliocene, e.g. Gonzalez-Garcia and Holguin-Quinones, 1992; Hol-
guin et al., 1994; Serrano Bello et al., 1996; Escalera-Alcocer et al.,
1997; Holguı́n-Quiñones and Román-Ramos, 1997; Rodriguez et al.,
1997; Guzmán Vega et al., 2001; Fig. 3). The major reservoir hori-
zons are situated within the Late Cretaceous Orizaba (dolomite and
limestone), Guzmantla (limestone) and San Felipe (limestone
breccia) Formations and in Tertiary sandy intercalations (mainly
Miocene; Fig. 3). The major seals are Maastrichtian to Paleocene
flysch layers and Tertiary argillaceous intervals. Laramide defor-
mation progressively affected the Córdoba Platform from Late-
Paleocene to Mid-Eocene, resulting in faulted anticlinal structures
(Fig. 2). Some of these acted as petroleum traps, while other similar
structures have not accumulated significant amounts of hydrocar-
bons. In the Veracruz Basin, both structural (as a result of Oligo-
cene–Miocene transpressional deformation) and stratigraphic (e.g.
channel) traps occur. The multiphase deformation history of the
area involving a variety of diagenetic processes that have impacted
the reservoirs, as well as the several potential source rocks and
various phases of migration largely complicate the Córdoba–Vera-
cruz petroleum system.

Fig. 3. Chronostratigraphic chart for the study area (FTB ¼ fold and thrust belt).

Please cite this article in press as: Ferket, H., et al., Insights from fluid inclusions, thermal and PVT modeling for paleo-burial and thermal...,
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4 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23
This paper focuses on the ancient petroleum system in the
western part of the FTB because very interesting information could
be gathered there from diagenetic and fluid inclusion studies. It is
unclear whether ancient oil seeps in this part of the platform had
a source similar to that in the eastern petroleum system. Sources
might be situated within the Cretaceous platform series or in the
currently allochthonous organic-rich Jurassic series of the Zongol-
ica unit (Fig. 1; Ortuño-Arzate et al., 2003), which has been thrust
on top of the Córdoba Platform during the Laramide orogeny, but
was initially deposited in the ancient Zongolica Basin, located west
of the Córdoba Platform.
Data on ancient geothermal gradients in the study area are
lacking in literature. However, data about the present thermicity
are available from petroleum research.
 Microthermometric analyses on HC-FI in the Veracruz Basin
(EPTG internal report) show that most of the data from deeper
than 2 km fit a gradient between 10 and 20  C/km.
 Bottom-hole temperatures (BHT) generally give an underesti-
mation of the real formation temperature as a result of
incomplete equilibration of the logging devices (Tissot and
Welte, 1984). Correction methods (e.g. regression techniques
such as the Horner method, Dowdle and Cobb, 1975; Deming,
1989; Hermanrud et al., 1990) require multiple measure-
ments in single wells and/or multiple measurements at a fixed
depth. Since sufficient measurements from a same well are
lacking, data from different wells have been plotted together
for similar geological domains and a 15% correction was used to
reflect better the actual formation temperatures (in concor-
dance to other regions where different methods were used;
Ortuño-Arzate, personal communication). From the depth–
temperature plot of these corrected data a low present-day
geothermal gradient can be deduced for the entire area
(Ferket, 2006). Most data from boreholes in the exposed Cór-
doba Platform and tectonic front area fit a gradient between 15
and 20  C/km.
 Reconstruction of the ancient thermal evolution was also
attempted by studying the degree of maturity of organic matter
and by Rock-Eval pyrolysis analyses. 2-D Thrustpack thermal
modeling in the Córdoba Platform required a constant surface
temperature of 15  C and a basal heat flow of 30 mW/m2 to fit
bottom-hole temperatures and measured maturity data
(Ortuño-Arzate et al., 2003).
Several reasons can be invoked to explain the remarkably low
values of paleogeothermal gradients:
1) thick, little stretched continental crust below the Córdoba
Platform and cooling down of the area after arrest of opening of
the Gulf of Mexico (thermal subsidence);
2) absence of major basement-involved faulting below the plat-
form during Gulf of Mexico and subsequent Laramide and post-
Laramide tectonic deformation reduces the likelihood for
circulation of deep, hot fluids through the platform;
3) an extensive, telogenetic karst system and west to east
topography-driven flow through the platform contributed also
to cooling of the subsurface;
4) rapid Neogene sedimentation in the Veracruz Basin;
5) apparently, the present magmatic activity in the region (in the
Trans-Mexican Volcanic Belt) does not significantly affect the
thermicity of the reservoir rocks in the study area.
Maturity data from wells in the exposed platform area are high
mature for Lower and Middle Cretaceous intervals. The ancient
geothermal gradients during Laramide deformation may have been
Please cite this article in press as: Ferket, H., et al., Insights from fluid inclusions, thermal and PVT modeling for paleo-burial and thermal...,
Marine and Petroleum Geology (2010), doi:10.1016/j.marpetgeo.2010.01.020
higher than the present gradients (see points 3 and 4) and care
should thus be taken when using present-day BHT to calibrate
thermal models. However, because of the same reasons as
mentioned for the present low values (except for 3 and 4), a rela-
tively low value may be expected also for the time of reservoir
formation. The timing of development of petroleum systems in the
study area also suggests a low value of the ancient geothermal
gradient. In addition, the depth of recent petroleum kitchens (e.g.
Maltrata Formation source rocks), which otherwise would have
matured in an earlier stage, gives another indirect evidence of a low
paleogeothermal gradient in the area (Ortuño-Arzate et al., 2003).
R0 and Tmax values versus depth show a change in gradient
marking the transition from pre-Laramide to post-Laramide time.
There are two possible explanations: either considering this change
as the result of a normal depth-dependent curvature (Suggate,
1998), or concluding that a different gradient applied during the
Mesozoic than during Neogene. When plotting data sets of other
wells that cover both periods, a similar, depth-independent, change
can be noticed between pre- and post-Laramide. However, lacking
independent estimates on paleo-burial/erosion makes it difficult to
confirm such change.
3. Analytical techniques
Cathodoluminescence microscopy (CL) was performed on
a Technosyn Cold Cathodoluminescence Model 8200 Mark II
instrument under 16–20 kV gun potential and 350–600 mA beam
current, 0.05 Torr vacuum and 5 mm beam width. Fluorescence
microscopy was performed on a ZEISS Axioskop incident-light
fluorescence microscope under blue excitation range (l ¼ 450–
490 nm). Stable isotope analyses were performed at the University
of Erlangen (Germany). Carbonate powders were reacted with 100%
phosphoric acid (r > 1.9, Wachter and Hayes, 1985) at 75  C in an
online carbonate preparation line (Carbo-Kiel – single sample acid
bath) connected to a Finnigan Mat 252 mass-spectrometer. All
values are reported in per mil relative to V-PDB by assigning a d13C
value of þ1.95& and a d18O value of 2.20& to NBS19. Oxygen
isotopic compositions of dolomites were corrected using the frac-
tionation factors given by Rosenbaum and Sheppard (1986).
Reproducibility was checked by replicate analysis of laboratory
standards and is better than 0.02& for d13C and 0.03& for d18O
(1s). Note that in this study only an analytical fractionation
correction has been applied for the dolomite oxygen isotopic
values. Although Land (1980) suggested omitting the analytical
correction, the existing different procedures between several
laboratories open the way to different interpretations. An addi-
tional thermodynamic fractionation (0.5 to 3&; Major et al.,
1992; Matthews and Katz, 1977; Zheng, 1999) between dolomite
and calcite should further be taken into account when comparing
their respective d18O values or when interpreting their fluid
sources.
Fluid inclusion microthermometric measurements were per-
formed on a Linkam heating–cooling stage and the precision is
about 1  C for Th and about 0.2  C for Tm. In the perspective of PVT
modeling, the changes in vapor-to-liquid ratio during progressive
heating were registered for the concerned HC-FI in order to obtain
an independent approximation of the fluid system. Synchrotron
FTIR in situ microanalyses and mapping of HC and aqueous FI were
performed at the ESRF (Grenoble) and in ANKA IR beam line
(Gasharova et al., 2003) according to the procedure described in
Guilhaumou et al. (1998). Quantitative analysis is obtained from
internal calibration of hydrocarbon following the procedure
described in Guilhaumou et al. (2004) for determination of CH4
content and alkane EQU. In calcite host minerals the spectra and
mapping corresponding to CH4 and alkanes in the stretching area
 ARTICLE IN PRESS

H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23 5

(3200–3600 cm1) are obtained by subtraction of the matrix
recorded in the same conditions by fitting matrix thickness on the
CO3dpeak at 2507 cm1 (Guilhaumou et al., 2004; Guilhaumou
and Dumas, 2005).
4. Assembling a data set for model calibration: diagenetic
research
In order to obtain independent information on paleo-burial,
erosion and paleo-temperatures which can be used to calibrate
basin models, unraveling and characterizing the diagenetic
processes that successively affected the reservoirs through time is
a prerequisite. This study focuses on the western part of the Córdoba
Platform where an extensive data set could be gathered. Samples
come mainly from outcrops in the vicinity of Córdoba, but a few
exploration boreholes in this outcropping zone have also been
sampled (Fig. 1). The following descriptions document the diagen-
esis of the Orizaba Formation dolomite in the Córdoba area and the
Guzmantla Formation limestone in the Atoyac anticline and the
Peñuela paleoseep thereby allowing to define two calibration sets
for constraining ancient heat flow and burial in 1) a footwall block
and 2) presently outcropping thrust sheets (Table 1 and Fig. 2).
4.1. Diagenesis of the Orizaba Formation dolomite
The paragenesis of the dolomites in the western platform (Fig. 4)
revealed: 1) an early burial history with dolomitization and
evaporite-related diagenesis, 2) an early compressional sequence of
fracturing with precipitation of different cements and with petro-
leum migration, 3) a late phase of thermochemical sulfate reduc-
tion (TSR) in the deepest intervals and 4) telogenetic meteoric
diagenesis in outcrops. Mineral cement phases that we present are
abbreviated as follows: anhydrite (A), calcite (C), dolomite (D),
fluorite (F), quartz (Q), pyrite (Py), chalcopyrite (CP), sulfur (S).
Relative timing is constrained by crosscutting relationships
between cement phases and stylolites. Bed-parallel stylolites (BPS)
record burial compaction and layer-parallel shortening stylolites
(LPSS) testify of tectonic compression. BPS are expected to form
starting from 800 m burial or more (Machel, 1990; Railsback, 1993)
and LPSS mainly prior to (and possibly continuing simultaneous
with) folding of the strata (e.g. Andrews and Railsback, 1997;
Whitaker and Bartholomew, 1999).
4.1.1. Early burial diagenesis
4.1.1.1. Description. The geometric distribution of the dolomite host
rock shows a stratabound, massive occurrence with intercalations of
some limestone and partly dolomitized limestone. Macroscopically,
two types of matrix dolomite can be differentiated: fine-crystalline
dolomite and medium- to coarse-crystalline dolomite. The latter
occurs mainly in cemented rudist molds that often display some
matrix porosity (7%; visual estimate) and in dolomite nodules.
Under plane-polarized light, the matrix of the fine-crystalline
dolomite consists of non-planar-A dolomite and that of the
coarser dolomite displays a planar-S texture and is characterized by
zoned crystals displaying a cloudy core and transparent cement rim.
The early burial history starts with precipitation of dolomicrite
and gypsum (Fig. 4). Anhydrite nodules developed locally. Bio-
moldic and vuggy dissolution affected the lime- and/or dolostones
prior to the precipitation of planar dolomite cement (D1), which
filled up partly the remaining porosity. Under cath-
odoluminescence (CL), most dolomite crystals display a uniformly
dull red luminescence, which characterizes also the cloudy core of
zoned crystals. The transparent cement rim displays fine dull and
bright luminescent zonations, which vary in color between green,
purple and yellow. Locally, anhydrite and dolomite were replaced
by silica before intense lithification of the sediments. Finally,
pressure-solution led to development of BPS and to recrystalliza-
tion of dolomite (Fig. 4).

Table 1
Overview of the diagenetic phases used for calibration of thermal modeling (see text for descriptions). CL ¼ cathodoluminescence, FI ¼ fluid inclusions, Th ¼ homogenization
temperature, Tm ¼ final melting temperature, P ¼ pressure, HC ¼ hydrocarbons, TSR ¼ thermochemical sulfate reduction.

Cement phase Petrography Stable isotopes FI Interpretation

(& PDB)
Diagenesis in Orizaba Formation dolomite
Dolomite (D2) Zoned with cloudy core and transparent rims; d18O 3.5 to 6.0, Primary FI: H2O–NaCl, Th (center) Burial
in (breccia-) veins; CL: dull red luminescent d13C þ3.7 to þ0.2 50–60  C, Th (rim) 70–80  C
Fluorite (F) Cubic crystals with a bitumen coating on free Secondary FI: Non-fluorescent, H2O– Hot saline fluid
faces, often corroded before precipitation of NaCl, Th 110–155  C, Tm 5.7 to 9.1  C preceding HC-trapping
calcite; in (breccia-) veins; CL: extinguishing in reservoirs i.e. peak
blue to non-luminescence Laramide burial
Quartz (Q) Euhedral cement in breccia-vein, postdating D2 Primary FI: i) HC–(H2O), Th 90–105  C, Trapping and early
and F and preceding C1, intergrown with solid 35–40 mol% CH4, C7–C8 alkane post-trapping
bitumen and containing blue fluorescent H2O equivalent; ii) H2O–NaCl–(CH4–HC), Th conditions at high
–HC FI 140–150  C, Tm 8.1 to 8.3  C. temperature and
Secondary FI: iii) HC, Th 75–85  C, pressure
35–55 mol% CH4, C6–C7 alkane (200 bar < P < 350 bar),
equivalent; iv) H2O–NaCl, Th 70–80  C, i.e. peak Laramide
Tm 0.6 to 1.7  C burial
Calcite (C1a) Replacive after anhydrite, neomorphic, d18O 16.7 to 5.0, At least partly secondary: H2O–NaCl, TSR-related phase
megacrystals after corrosion phase; associated d13C 18.0 to 2.5 Th 71–110  C and 45–75  C, Tm 3.3
with sulfides and pyrobitumen; CL: non- to þ0.0  C
luminescent
Calcite (C1b) Common cement phase in veins; after corrosion d18O 11.9 to 3.5, Primary FI: H2O–NaCl, Th 45–66  C, Post-Laramide
phase; CL: sector-zoned dull luminescent d13C 2.4 to þ1.9 Tm w0.0  C denudation and cooling
phase

Diagenesis in Guzmantla Formation limestone

Calcite (C3) Common cement phase in post-BPS/pre-LPSS d18O 5.0 to 13.0, Primary FI: H2O–NaCl, Th 40–65  C, Early syn-Laramide
breccia-veins. CL: non/dull luminescent d13C þ1.0 to þ2.5 Tm 0.8 to 1.9  C
Calcite (C4) Post-LPSS veins containing biodegraded oil and d18O 6.0 to 8.6, Primary-pseudosecondary: HC (no Syn- or early
yellow fluorescent HC-FI d13C 0.9 to þ1.6 water!), Th 55.5–89  C, 10–17 mol% CH4, post-Laramide
C9–C12 alkane equivalent

Please cite this article in press as: Ferket, H., et al., Insights from fluid inclusions, thermal and PVT modeling for paleo-burial and thermal...,
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6 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23
EOGENETIC
Cretaceous
evaporite precipitation
dissolution (biomoldic + evaporite
nodules)
matrix dolomitization + dolomite
cement in pores (D1)
silicification of anhydrite nodules
recrystallization of D1
BPS
fracturing - brecciation
dolomite cement (D2, in veins and Φ)
anhydrite cement (A, in veins)
fluorite cement (F, in veins)
fracturing - brecciation
dissolution
LPSS
oil migration
silica remobilization & quartz (Q)
alteration of oil (bitumen)
DL (SZ) calcite cement (C1,
in veins and Φ)
local recrystallization of dolomite
matrix to BYL dolomite (D3)
elemental sulfur (S)
iron sulfides (pyrite, chalcopyrite)
fracturing
dissolution
calcite cement (C2, in Φ)
Fig. 4. Paragenesis of the diagenetic phases in the Orizaba Formation dolomites; see text for explanation. (BPS ¼ bed-parallel stylolites; LPSS ¼ layer-parallel shortening stylolites;
F ¼ porosity).
Observation of mm- to cm-scaled (oblate) spherical nodules,
occurring as isolated nodules or in clusters displaying chicken
wire structure, is common in some intervals. These nodules may
be filled with corrotopic or ‘pile of bricks’ textured anhydrite,
especially in the lowest part of the formation. Under CL, the
anhydrite cement shows a short-lived bright blue luminescence,
which subsequently quenches to non-luminescence. Microscopic
fluorite cement occurs locally intergrown with anhydrite.
Although these phases could be late-diagenetic, gypsum and/or
anhydrite should have been present in the sedimentary environ-
ment and the observed anhydrite nodules probably formed after
replacement or recrystallization of original gypsum nodules. In the
chicken wire structures, a thin rim of dolomicrite is present
between and around the nodules. These nodules possess
a concentric structure, which may develop an irregular (reniform)
morphology. This morphology suggests concentric outward
growth with soft sediment squeezed between the nodules
explaining the chicken wire pattern. Therefore, the formation of
the nodules is interpreted as early diagenetic (Arbey, 1980;
Swennen and Viaene, 1986).
Stable oxygen and carbon isotope analyses of all studied dolo-
mite matrices (including D1 cement) give a range of values
respectively between 0.96 and 3.47& V-PDB and þ1.56 and
þ3.55& V-PDB (Fig. 5). Lighter oxygen isotope fractions around
3& V-PDB relate to coarser-crystalline matrices and to some D1
dolomite-cemented biomolds. Here, possibly contamination with
the D2 dolomite phase (see below), which precipitated also in
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TIME
MESOGENETIC TELOGENETIC
Paleocene Eocene Recent
D1
?
BPS
D2
A
F
LPSS ?
Q
sulphate reduction
C1a & b
Thermochemical
D3
S
Py + CP
C2
moldic pores, may have occurred. D1 cement sampled from chicken
wire nodular facies displays an isotopic signature within the same
range as the dolomite host rock.
Isolated nodules or chicken wire structures are often now
composed also of silica. The outer rim generally is made of length-
slow chalcedony (i.e. lutecite variety or moganite; Heaney and Post,
1992) with radiating fibrous and spherulitic habits. The interior of
the nodules often shows larger spherulitic textures made of quartz,
which occur intergrown with microcrystalline anhedral quartz and
euhedral mosaic quartz. Some nodules consist completely of quartz
with crystal size increasing centripetally. The silica phases typically
possess undulose extinction. Pseudomorphs after lath-shaped
anhydrite crystals can locally be present. Furthermore, the quartz
crystals often contain micro-inclusions of anhydrite. This indicates
that the silica formed as a replacive phase after anhydrite (West,
1979). Since some nodules display a poikilotopic texture with
brown dolomite crystals incorporated in the silica phase or show
dolomite ‘ghosts’, the silicification of anhydrite nodules, at least
locally, must postdate dolomitization.
A wispy yellow luminescence pattern (Plate 1A and B) affects
both the original uniformly dull red and well-zoned dolomites.
Such texture is typical of recrystallization (Nielsen et al., 1994). The
timing of this event is unclear. Nevertheless, since the wispy
pattern can be recognized in all studied localities and in all cores, it
was most likely related to a regional process, such as burial
recrystallization. The dolomite matrix and D1 cement were affected
by BPS development prior to local brecciation of the strata as
 ARTICLE IN PRESS
H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23
18 O temperature effect
-2 0 -18 -16 -14
C1b
dolomite matrix and
cements (D1)
dolomite in nodules (D1)
dolomite cement in veins (D2)
calcite cement (C1)
Fig. 5. Stable isotope plot with values expressed in & versus PDB-standard. Cenomanian marine reference box according to DNAG, Scholle and Arthur (1980) and Norris et al.
(2001). HC ¼ hydrocarbons.
evidenced by cut off pressure-solution seams (i.e. in laminated
lithologies) at the edges of dolomite breccia fragments.
4.1.1.2. Discussion. Evidence for episodes of subaerial exposure is
found in pedogenetic textures (Ferket, 2004) and in the dissolution
of bioclasts and evaporite nodules, which were subsequently filled
with planar dolomite (D1) cement. The isotopic composition of the
dolomite (D1) falls within the range of calcite in equilibrium with
Cenomanian marine water. However, a negative d18O shift (0.5 to
3&; see above) should be accounted for as thermodynamic
fractionation correction. The overall characteristics argue for early
dolomitization by a marine-related fluid, with or without an
evaporative component. Isotopic (re)equilibration during subse-
quent burial (and meteoric) diagenesis can explain more depleted
d18O values, which is in line with burial progressive recrystalliza-
tion indicated by the widespread wispy CL pattern of dolomite
(Nielsen et al., 1994). Because also overlying and intercalated
limestone strata are typical of restricted lagoonal environments,
a seepage-reflux model (e.g. Jones et al., 2002; Purser et al., 1994;
Simms, 1984) is invoked to explain host rock dolomite formation.
The common occurrence of length-slow silica in nodular anhy-
drite facies relates to silica precipitation in sulfate-rich pore water
(Heaney, 1995; Heaney and Post, 1992). A logical source could relate
to mobilization of silica as a result of clay diagenesis and from
bentonite and biogenic silica-rich layers, such as some presently
chert-rich (testifying of unstable silica precursor) intervals that
occur in the Orizaba and underlying Tamaulipas formations.
4.1.2. Diagenesis related to Laramide deformation
4.1.2.1. Description. After BPS development several fracturing and
brecciation episodes affected the rocks (Fig. 4). The created
porosity, as well as the residual porosity in nodular vugs and bio-
molds, was (partly) filled by successive mineral cement phases.
Open macroporosity related to intercrystalline and moldic porosity
and to partly cemented crackle to mosaic float-breccias rises locally
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7
marine 4
D2 D1
2
0
- 12 - 10 -8 -6 -4 -2 0 2 4
C1a -2
C1a
-4
-6
oxidation of HC
-8
-10
-12
-14
C1b
-16
-18
13 C
-2 0
to 15% (visual estimate). The first fracturing event (f1) led to
straight fractures and breccias made up of mainly perpendicular
fractures. The infilling cement is dolomite (D2), which may be
succeeded by anhydrite (A; Plate 1E) and/or fluorite (F) cement. A
second fracturing phase (f2) cuts through earlier fractures and
developed as anastomosing fractures and breccias. Older fractures
(f1) were partly reused and locally their infilling cements (D1, A, F)
were corroded/dissolved before calcite (C1; Plate 1C, D and F)
precipitated. Calcite locally also replaced former cements, as indi-
cated by lath-shaped calcite in anhydrite nodules; Plate 1F. The C1
calcite is volumetrically the most important cement phase among
the post-BPS vein cements and has been split up in C1a and C1b
based on spatial distribution (related to burial depth), geochemical
characteristics and mineral associations. The peculiar characteris-
tics of calcite cement C1b are described in Section 4.1.3 where
several observations indicative of thermochemical sulfate reduc-
tion (TSR) are grouped. Oil migration took place, most probably,
before precipitation of C1 and after LPSS development. In one
borehole (well A, Fig. 2) euhedral quartz cement (Q) preceding C1
has been recognized in dolomite breccias. This quartz contains
several generations of aqueous and hydrocarbon inclusions and
revealed to be a crucial phase documenting the P–T conditions
during petroleum migration. The details of this Q cement are dis-
cussed in Section 4.1.4.
D2 is a limpid (in plane-polarized light), dull red to non-
luminescent dolomite cement occurring in f1 veins and breccias
in the dolostone. Brown dolomite crystals with a similar lumines-
cence as D2 and displaying wavy extinction and slightly curved
crystal faces (i.e. saddle dolomite texture) are locally present in
breccia-veins (Plate 1E). These saddle dolomites are succeeded by
precipitation of anhedral to ‘pile of bricks’ anhydrite cement (A). D2
cement shows a stable isotopic signature that is similar to the host
rock or may be more depleted in oxygen (as low as 6& V-PDB)
and carbon (as low as þ0.23& V-PDB; Fig. 5). The ‘saddle dolomite’
cement also possesses a d18O value around 6.0& V-PDB. Th
 ARTICLE IN PRESS

8 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23

Plate 1. Diagenetic phases in the Orizaba Formation dolomites. A/and B/view under cathodoluminescence, C/, D/and F/stained thin sections under transmitting light view, E/view
under crossed polars. Labels refer to phases described in the text and other figures. A/dolomite matrix displaying red and yellow wispy luminescence and locally showing relicts of
well-zoned D1 cement. The crosscutting veins are filled with red luminescent D2 dolomite and sector-zoned C1a calcite cement. B/red and yellow wispy luminescent dolomite (D1)
matrix cut by a breccia-vein filled with red luminescent D2, blue luminescent F and dull luminescent C1a cements. C/dolomite matrix cut by a breccia-vein filled with D2, F and C1a
cements and by bitumen. D/detail of a vein fill showing corrosion of D2 cement prior to precipitation of C1a. E/detail of a vein fill showing corrotopic anhydrite (A) cement and
saddle dolomite D2. F/Detail of vug fill in dolomite showing lath-shaped C1a crystals containing remnants of the former anhydrite (A) cement which they replace (For interpretation
of the references to color in this figure legend, the reader is referred to the web version of this article).

measurements from primary fluid inclusions (FI) in D2 fall between
50 and 60  C in the center of the crystals with higher temperatures
(70–80  C) towards the rims (Fig. 6C).
Locally, minor blue luminescent fluorite cement (F) is present in
the D2 veins and breccia (Plate 1B and C). The F cement contains
secondary trails with bi-phase aqueous–gaseous FI. A constant
vapor-to-liquid (V/L) ratio of 10% characterizes the majority (>90%)
of the inclusions. Other FI display higher gas content. Some cases of
necking down leading to larger bubbles could be identified.
Therefore, only the 10% V/L ratio-inclusions were considered to
reflect true homogenization (Th) values. Th shows a bimodal
distribution between 110 and 145  C and between 145 and 155  C
(Fig. 6A). Th values above 180  C, some of which measured in FI with
slightly higher V/L ratios, probably relate to leakage or necking
down. Final melting temperatures (Tm) vary between 5.7 and
9.1  C (Fig. 6B). Although several fluorite crystals contain
a bitumen coating, no hydrocarbon FI was identified by fluores-
cence within the F crystals.
Dull luminescent (sector-zoned) calcite cement (C1a) occurs as
fracture- and matrix-filling cement. Fine veins with fills of D2 (at
the vein walls) and C1a (in the center) crosscutting the dolomite
rock are common and indicate reuse of f1 fractures (Plate 1A).
Fine and thicker anastomosing calcite veins and breccia-veins (i.e.
cemented crackle to mosaic float-breccia) cut locally through
older (D2, A and/or F cemented) veins and relate to fracturing
event f2. Where brecciation of the matrix has occurred, C1a
cement is present also in intercrystalline pores and in residual
porosity within D1- and D2-cemented molds. A dissolution phase
preceded the precipitation of C1a cement (Fig. 4). Cubic F crystals
commonly show broken or corroded edges and broken pieces
float in the C1a cement (Plate 1B). Some D2–C1a cemented
breccias also show partial dissolution of D2 crystals before
precipitation of the C1a cement (Plate 1D). C1a cement in veins
and breccias reveals a more or less linear trend in isotopic
composition from host rock-like values towards depleted d18O
(11.88& V-PDB) and d13C (3.33& V-PDB) values (Fig. 5).
However, the least depleted d18O vein value of 2.91& V-PDB can
be explained by (dolomite) matrix contamination since both
phases could not be separated from each other. Consequently, the
range in oxygen values for the C1a cement should be narrowed to
more depleted signatures. A fluorescence study of the C1a cement
did not allow to identify any hydrocarbon inclusions. Fluid
inclusion study of C1a cement from veins in the Tlacuiloltécatl
Anticline outcrops revealed a dominance of small mono-phase
aqueous FI and a small percentage (about 10%) of bi-phase
aqueous–gaseous FI. Inclusions that appear scattered in

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H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23 9

A 13 B 8
12
11 secondary FI in fluorite 7 secondary FI in fluorite
10
6
9
frequency

frequency
5
7
6 4
5
3
4
3 2
2
1
1
0 0
110 115 120 125 130 135 140 145 150 155 >180 -9.5 -9 -8.5 -8 -7.5 -7 -6.5 -6
T h (°C) T m (°C)

C D2 center D C1a sample 1

7 8
D2 rims C1a sample 2
6 7
frequency

5 6

frequency
4 5
3 4
2 3
1 2
0 1
50 60 70 80 0
45 50 55 60 65
T h (°C)
T h (°C)
E F
8 C1b 4 C1b
type 1 type 1
7
type 2 type 2
6 3
frequency
frequency

4 2

2 1

0 0
-3,5 -3 -2,5 -2 -1,5 -1 -0,5 0
40 50 60 70 80 90 100 110
T h (°C) T m (°C)

Fig. 6. Histograms summarizing microthermometric results on fluid inclusions (FI) in different diagenetic phases (see text for description) from the Orizaba Formation dolomites.
Th ¼ homogenization temperature; Tm ¼ final melting temperature of ice.

inclusion-rich bands (e.g. sample 1; Fig. 6D) or occur in clear
growth zones (e.g. sample 2) were interpreted as primary FI.
Inclusions that are present along trails and rhombic-shaped to
irregular FI that are aligned along twin planes were interpreted as
secondary FI. The size of the studied FI varies between 3 and
10 mm. A constant V/L ratio characterizes the bi-phase primary FI.
Microthermometric analyses on two samples (1 and 2), which
possess d18O values of 9.32 and 10.18& V-PDB respectively,
revealed Th between 47 and 63  C (1) and between 45 and 66  C
(2; Fig. 6D) respectively. Final melting temperatures (Tm) could be
measured only in two FI, which give values of 0.2 and 0.5  C
respectively. The difficulty to measure Tm relates to the disap-
pearance of the vapor bubble after Th measurements and to
common metastable measurements (above 0  C), even with very
slow heating. Larger secondary FI, in which a vapor bubble was
created by artificial stretching, possess Tm values around 0  C.
Unfortunately, the paragenetic relationships between vein
cements and LPSS could not be established. Dolomite subjected to
layer-parallel shortening results in recrystallization (e.g. changes in
stoichiometry and increasing crystal size), rather than in macro-
scopic pressure-solution features.
4.1.2.2. Discussion. Increasing burial during platform sedimenta-
tion and Late Maastrichtian to Early Paleocene flysch deposition led
to the development of BPS and to higher confining pressures (pc) in
the rocks. From the Maastrichtian onwards, the Laramide hinter-
land underwent tectonic deformation and the foreland gradually
became affected by horizontal compression. The Paleocene transi-
tional stress field, where the main principal stress s1 had to switch
between vertical and horizontal, created a situation of relatively
low differential stresses (Ds). As a consequence, less well-oriented
fractures and breccias developed in that period. The driving force
for extensional fracturing under low Ds and high pc must be
hydrofracturing (Ferket et al., 2004). Two phases of fracturing–
brecciation (f1 and f2) were distinguished in the dolostones of the
western part of the Córdoba Platform. The first infilling cement
after f1 is the dull red to non-luminescent dolomite (D2), which
shows d13C values close to the host rock and d18O values that are

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10 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23
more depleted with respect to the host rock. The CL pattern and the
local ‘saddle dolomite’ morphology support that the isotopic
depletion can best be explained by a temperature fractionation
effect. However, saddle dolomite morphology cannot be used to
give a minimum temperature estimate (e.g. Searl, 1989).
The volumetrically minor F cement phase contains only
secondary FI. The elevated Th values (110–155  C), which are
minimum estimates for the real trapping temperatures testify
involvement of hot fluids. These fluids are not necessarily in
thermal equilibrium with the surrounding reservoir rocks.
However, large discrepancies are not expected, since a high
permeability and short migration distance are required to maintain
a thermal anomaly in the circulating fluid. Tm values in the F cement
indicate a saline fluid of 8.81–12.96 wt% eq. NaCl (Bodnar, 1993),
which corresponds with about 3–4 times the salinity of seawater.
Therefore, fluorite and anhydrite cement in the post-BPS veins
likely precipitated from a fluid that interacted with evaporites and/
or from high salinity formation water. Since no hydrocarbons are
present in the FI, while the F crystals often show a bitumen coating,
the measured secondary FI are interpreted to reflect thermal
conditions just before oil migration. With the inferred high values
oil expulsion should have started already in the source intervals.
Nevertheless, migration of oil requires a minimum saturation of
early produced hydrocarbons in the source rocks, which in turn
depends on the quantity and distribution of organic matter.
The (sector-zoned) dull luminescent calcite cement (C1a), which
possesses stronger depleted d18O and d13C values, precipitated in f2
fractures and in older veins after corrosion of crystal faces of
infilling cements. The dull luminescent CL pattern, isotopic deple-
tion and Th measurements indicate precipitation at slightly
elevated temperature (Th 45–66  C). However, oxygen isotopic
depletion could relate also to a meteoric-derived fluid component.
If the two measured Tm values (0.5  C corresponds with a mete-
oric-dominated fluid) are representative for the precipitating
fluid, the hypothesis of slightly heated (evolved) meteoric water is
the most plausible. The depletion in d13C cannot be explained by
a simple temperature fractionation effect. It could relate to incor-
poration of isotopically light CO2 from oxidation of hydrocarbons.
This is supported by the common observation of intergrown
bitumen between the C1a cement. Possibly, the corrosion phase
affecting D2 and F crystals before C1a precipitation relates to
organic acid-bearing fluids associated with oil migration. This
corrosion, the change towards calcite mineralogy (in a dolomite
host rock), the depleted isotopic signature with respect to the host
rock and the Tm and Th results indicate non-equilibrium precipi-
tation (with regard to the host rock) from a meteoric fluid under
relatively shallow burial conditions. Its origin, most probably, can
be placed into a context of post-Laramide denudation, cooling,
meteoric influx and topographic-driven flow. Topography-driven
meteoric water circulation could have had a different effect at the
different locations depending on burial depth and degree of
compaction during the Laramide phase. An alternative explanation
for a negative d13C value in the C1a cement could also relate to
incorporation of soil-derived light CO2. The latter process, however,
can only be invoked in case of some near-surface samples and does
not apply to deeper intervals, such as the footwall blocks.
4.1.3. Thermochemical sulfate reduction
A number of petrographic observations can be grouped together
that are interpreted to relate to thermochemical sulfate reduction
(TSR; Fig. 4). The involved diagenetic phases comprise: precipita-
tion of megacalcite crystals (C1b) with an isotopic signature typical
of TSR, insoluble bitumen, recrystallization of dolostone matrix into
bright yellow luminescent dolomite (D3) and precipitation of
elemental sulfur (S), pyrite (Py) and chalcopyrite (CP). These
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features are limited to the deepest dolomite–anhydrite intervals in
footwall blocks.
4.1.3.1. Description. Coarse (mm to cm scale) euhedral crystals of
dull to non-luminescent sector-zoned calcite cement (C1b; Plate
1F) occur intergrown with lath-shaped anhydrite crystals in
oblate spherical molds, chicken wire structures and breccia. These
‘megacalcite’ crystals locally display ‘pile of bricks’ textures sug-
gesting that they are pseudomorphs after anhydrite. Moreover,
intergrown anhydrite crystals are affected by corrosion where they
are in contact with this calcite phase. C1b precipitated also in
intercrystalline pores in the dolomite matrix. Within these intervals
it develops a poikilotopic texture with ‘floating’ dolomite rhom-
bohedra (phases D1 and D2) in C1b cement. However, not all pores
have been cemented, leaving appreciable open macroporosity.
Anhydrite-replacing C1b in nodular structures and breccia from the
lower interval of the C1A borehole displays a linear trend between
a much depleted in d18O (16.68& V-PDB) and slightly depleted in
d13C (2.39& V-PDB) end-member and a less depleted in d18O
(6.68& V-PDB), but strongly depleted in d13C (16.55& V-PDB;
Fig. 5) end-member.
Two series of bi-phase FI could be distinguished in the C1b
cement based on a different Th range, next to numerous mono-
phase FI. A first group (henceforth called type 1) is characterized
by mainly rounded to rhombohedral shapes with a constant V/L
ratio of 20%. The vapor bubble generally starts to move only with
heating above 50  C or higher. A second group (henceforth called
type 2) is characterized by subangular rhombic-shaped FI with
a constant vapor-to-liquid ratio of about 10% and a mobile vapor
bubble at room temperature. However, transient forms between
type 1 and type 2 inclusions also occur and distinction based on
morphology is not always univocal. Both types are present next to
each other in FI-rich zones and are roughly aligned following
crystal cleavage directions. Although neither of both types occurs
along clear secondary trails, the morphology of the type 2 FI could
reflect a secondary generation in analogy to rhombic-shaped
secondary FI along cleavage planes in many other studied calcite
veins. Similar interpretation of such FI is reported by Muchez and
Slobodnik (1996). Apart from these FI, scarce bi-phase FI with
a high gas volume are present mainly along trails with oblate
mono-phase FI. In addition, during heating, many mono-phase FI
obtained a vapor bubble and some bi-phase FI developed a larger
(up to 90% bulk volume) bubble (i.e. they were stretched). FI where
stretching could be observed, were not used for Th measurements.
The Th ranges between 71 and 110  C (type 1) and between 45 and
75  C (type 2; Fig. 6E). Eutectic temperatures could not be identified
and final melting temperatures (Tm) could be measured only in
a small number of FI (n ¼ 13 for type 1 and n ¼ 3 for type 2) as
a result of common metastability. The Tm varies between 3.3 and
0.6  C (type 1) and between 1.6 and 0  C (type 2; Fig. 6F).
In the higher intervals insoluble bitumen is present locally in
vugs, in intercrystalline pores, in fractures, along stylolites and in
D2–F–C1a cemented breccia (Plate 1C). In these breccias, the
bitumen occurs as coating on F crystal faces and intergrown
between the C1a cement. Irregular, convex contacts between the
bitumen and the C1a crystals may have resulted from an original
liquid phase. Under fluorescent light, the bitumen appears as non-
fluorescing to green-yellowish filamentous aggregates. In the
lowest intervals, scarce, non-fluorescing solid bitumen occurs along
crystal boundaries in dolomite chicken wire nodules and in open
pores in the partly cemented nodular molds and breccias.
In the lower part of the Orizaba Formation, intercrystalline
anhydrite and small anhydrite nodules, which are replaced partly
by calcite and silica phases, are present. Here, pyrite (Py) and
chalcopyrite (CP) locally occur as replacive cement, in the
 ARTICLE IN PRESS
H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23
dolomite–anhydrite matrix and along shear planes. In these inter-
vals, blue-green chalcedony locally has replaced anhydrite along
shear planes. This suggests at least some late-diagenetic silica
remobilization (Fig. 4). Locally, shear planes are coated with
elemental sulfur (S). Furthermore, planar-E dolomite (D3) in these
intervals displays bright yellow luminescence (which is generally
interpreted as iron-poor and which is attested by non-staining of
potassium ferricyanide) or possesses zoned dolomite crystals with
bright yellow luminescent cores and orange luminescent rims. The
co-occurrence of iron sulfides and assumed iron-poor dolomite and
the absence of this type of dolomite (D3) elsewhere point towards
a likely genetic relationship.
4.1.3.2. Discussion. The strongly depleted d18O values of the C1b
cement must be attributed to precipitation at elevated tempera-
ture. The trend towards strongly depleted d13C values indicates
oxidation of organic material. Considering the petrographic char-
acteristics with pseudomorphic textures after anhydrite, the
development of megacrystalline cement, the occurrence of
elemental sulfur, microscopic (chalco)pyrite and solid bitumen,
together with the important burial depth points out TSR (Machel,
2001 and references therein). The linear isotopic trend for the
calcite cement is explained by varying contribution of (in)organic
carbon and different degrees of host rock buffering during precip-
itation. In addition, the observation of iron sulfides, next to iron-
poor recrystallized D3 dolomite also support TSR.
TSR requires organic matter, which probably arrived in a liquid
state and reacted with the SO2 4 from anhydrite. The paragenetic
timing of TSR thus indicates also the timing of oil migration in the
western part of the platform, which can be placed between the
precipitation of F and C1 cement in a Laramide or early post-
Laramide context. Subsequently, oxidation of oil took place
together with sulfate reduction. The formation of HS together with
Fe2þ (and Cu2þ) released from clay mineral (e.g. bentonite horizon)
diagenesis gave rise to the local formation of pyrite (and some
chalcopyrite). Additional evidence for hydrocarbon migration can
be found also in shallower intervals, where solid bitumen occurs in
partly cemented breccia and in exhumed oil reservoirs, such as the
Peñuela paleoseep (Ferket et al., 2003A). These hydrocarbons also
were oxidized, hereby losing their characteristic fluorescence and
converting into filamentous aggregates. However, the latter
degradation is assumed to have taken place at lower temperatures
and shallower burial, probably by atmospheric oxygen.
Results from microthermometric analyses of bi-phase FI in the
C1b calcite cement indicate a low salinity (0.83–5.32 wt% eq. NaCl)
that probably corresponds with evolved meteoric-dominated
water. Th values fall in a wide range (45–110  C). Moreover, these
temperatures are too low to explain TSR (Machel, 2001). Although
no unambiguous genetic interpretation of the fluid inclusions could
be made based on petrographic criteria, a secondary origin would
be in line with their compositional characteristics and with their
distribution along cleavage planes (cfr. Muchez and Slobodnik,
1996). In this case, the FI reflect conditions of the post-Laramide
cooling stage. The Th and Tm spreads reflect two different main
episodes (i.e. types 1 and 2, Fig. 6E and F).
4.1.4. Quartz cement in borehole A
4.1.4.1. Description. The quartz (Q; Plate 2A–C) found in a thrust
footwall block cut by well A (Fig. 2) is of particular interest, since it
possesses both primary and secondary HC and/or aqueous FI. As
such, it reveals crucial information on the early trapping and post-
trapping conditions. Some crystal faces contain a coating of pyro-
bitumen (insoluble in organic solvents). In addition, some of this
bitumen occurs intergrown within the Q crystal (Plate 2D).
Furthermore, this crystal contains some solid inclusions with
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11
a rhombic cleavage, probably calcite or dolomite (Plate 2E). Para-
genetically, the quartz precipitation can be placed after phases D2
and F and concurrent with HC migration and alteration.
The quartz shows (i) clear growth zones formed by bi-phase HC-
FI, (ii) virtually isolated, but probably primary, aqueous (þminor HC
quantities) FI and (iii) secondary trails of pure HC and (iv) HC–free
water-FI. Several trails are oriented parallel to the rhombic faces of
carbonate inclusions, while primary growth zones follow the
hexagonal shape of the quartz. In the neighborhood of impurities
(e.g. carbonate inclusions), primary HC-FI may be large (Plate 2F).
Locally, immiscible oil droplets occur in water in HC–H2O FI (Plate
2G).
Nearly all HC-FI show a high (around 30%) vapor-to-liquid ratio
and a dark patch of precipitated asphaltenes (Plate 2F and H). All
HC-FI show a light-blue fluorescence, indicating high mature
aliphatic (Guilhaumou et al., 1990) petroleum. Most FI are elon-
gated and rounded to irregular in shape. The aqueous inclusions
have very small gas-to-liquid ratios (<5%).
i) Homogenization temperatures (Th) of primary HC-FI vary
between 90 and 105  C. Freezing–heating experiments reveal
the presence of complex solid phases, locally of CO2 precipi-
tation and/or carbonate nucleation. Furthermore, Synchro-
tron Fourier Transform Infrared (SFTIR; e.g. Guilhaumou et al.,
1998, 2000) analyses confirm the presence of little CO2 and
carbonate phases in some primary HC-FI (Figs. 7 and 8).
Primary HC-FI contain variable proportions of water. SFTIR
analyses indicate a methane content of 35–40 mol% for
measurements in mainly liquid phase and mainly gas bubble
respectively. Alkane equivalents correspond with C7–C8 for
the liquid and C5–C6 for the gas-dominated part.
ii) Primary aqueous (-HC) inclusions display homogenization
temperatures between 140 and 150  C. After freezing, small
quantities of clathrate prevail until þ17 to þ20  C, indicating
the presence of methane. The latter was confirmed also by
SFTIR analyses (Fig. 9). These analyses revealed also the
presence of traces of dissolved light aliphatic HC. Melting
temperatures are between 8.1 and 8.3  C, corresponding
with a salinity of 11.81–12.05 wt% eq. NaCl.
iii) Secondary HC-FI show Th values between 75 and 85  C. Their
CH4 content according to SFTIR analyses is about 35–55 mol%
for liquid or vapor-dominated phases respectively. Alkane
equivalents correspond with C6–C7. Molecular water is
almost absent (Fig. 10). Nevertheless, an OH-peak may be
observed in some spectra corresponding to water incorpo-
rated within the quartz matrix around the FI.
iv) Secondary aqueous inclusions possess Th values between 70
and 80  C and Tm values varying from 1.7 to 0.6  C, indi-
cating a salinity of 1.05–2.9 wt% eq. NaCl (i.e. diluted seawater
or changed meteoric water).
4.1.4.2. Discussion. The assemblage formed by 4 generations of FI in
the quartz reflects a sequence of fluid flow events. Primary HC (i)
and water (ii) FI indicate the former presence of a bi-phase, partly
immiscible fluid at the time of trapping. Some HC-FI contain vari-
able proportions of H2O and the water-FI form clathrates and show
a small contribution of aliphatic HC in their SFTIR spectra. There-
fore, both phases (i þ ii) must have been in contact originally.
Differential mixing with water might explain differences in
homogenization temperatures for the HC-FI (i). Secondary HC-FI
show higher CH4 contents and virtually no molecular H2O with
respect to the primary HC-FI. Th values are slightly lower, but alkane
equivalents are similar. Generation-(iii) FI, consequently, do not
differ much from the first (primary) trapped inclusions and
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12 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23

Plate 2. Fluid inclusion (FI) study in quartz (Q). A/to D/view under binocular, A/breccias-vein cutting through the dolomite matrix, filled with mainly dolomite and bitumen. B/detail
of photograph A showing quartz and calcite in the remaining pores, C/isolated quartz crystal showing euhedral shape, D/detail of the quartz crystal illustrating the solid bitumen
intergrown within the quartz matrix, E–H/transmitting light view, E/detail of a carbonate inclusion intergrown within the quartz matrix and clustering of FI at its borders, F/detail of
an HC-FI showing different phases: liquid HC, gaseous HC, water containing oil droplets and asphaltenes, G/detail of the oil droplets in the water phase of the FI shown in
photograph F, H/detail of a typical primary HC-FI showing the presence of asphaltenes.

probably formed under comparable conditions not long after the
latter phase and by the end of quartz precipitation. The secondary
water-FI (iv) might have formed later, during further cooling of the
reservoir and by circulation of diluted water (w1–3 wt% eq. NaCl)
through the reservoirs that were formerly filled with HC and saline
water (w12 wt% eq. NaCl). The presence of such saline water in the
oil-impregnated reservoirs is in line with the salinity measured
from aqueous FI in fluorite.
The trapped HC are high mature aliphatics (light-blue fluores-
cence) and are rich in gas (CH4, CO2). In addition, residual pyrobi-
tumen occurs as coating or incorporated within the quartz or
calcite matrix. These observations indicate relatively high temper-
atures. Asphaltenes are present in most HC-FI giving evidence of
disequilibrium trapping conditions. Carbonate inclusions could not
be specified further. If they are composed of calcite, a calcite
cementation phase should be placed before (or in parallel with)

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H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23 13

Fig. 7. A) SFTIR spectrum for the mainly gas phase (bubble) of a primary hydrocarbon
(HC) þ H2O fluid inclusion (FI) in the well A-quartz cement. The scale of absorbance
values is arbitrary in the shown example. This analysis reveals the presence of aliphatic
HC, CH4, molecular H2O and OH diffused in the quartz matrix around the FI, and of
dissolved CO2 in HC. B) SFTIR spectrum for the liquid phase of the FI in (a) revealing the
presence of aliphatic HC, molecular H2O and OH diffused in the quartz matrix around
the FI.
Fig. 8. A) SFTIR spectra for the liquid (lower curve) and gas (upper curve) phases of
a primary hydrocarbon (HC) þ H2O fluid inclusion (FI) in the well A-quartz. The scale of
absorbance values is arbitrary in the shown example. This analysis reveals the pres-
ence of aliphatic HC, few molecular H2O and gaseous CO2. Some bands between 2850
and 3000 cm1 corresponding with a CaCO3 phase, partly overlap the HC spectrum. B)
SFTIR spectra for the liquid phase of a primary HC (þH2O) FI. The scale of absorbance
values is arbitrary. This analysis illustrates the abundance of H2O in some HC-FI.

quartz precipitation. Alternatively, it could be dolomite from the

preceding and surrounding D2 phase.

4.1.5. Telogenetic diagenesis

4.1.5.1. Description. A different type of calcite cement (C2) that is
characterized by well-zoned non- and bright yellow luminescence,
locally occurs in dolostones from outcrop samples. This C2 cement
is present in dissolution vugs (geodes) in C1-cemented veins, in
microveins cutting through older D2 and C1 veins, along shear
planes and in scattered patches within the dolomite matrix. The
precipitation of C2 must thus follow a phase of fracturing and
dissolution. The restriction of C2 to outcrops, its occurrence in
geodes and crosscutting relationships with many of the formerly
mentioned diagenetic phases suggest a telogenetic origin by
meteoric fluid infiltration (Fig. 4).

4.1.5.2. Discussion. The CL-zonations can best be explained by

changing redox conditions, which probably relate to variations in
influx rate of meteoric water and therefore, stagnation of the Fig. 9. SFTIR spectra of liquid and gas phases from a primary H2O fluid inclusion (FI) in
meteoric lens in terms of its redox (e.g. Kaufmann et al., 1999). the well A-quartz. Note the presence of aliphatic hydrocarbons (HC) and few CH4
Cements with similar characteristics commonly occur in the detected only in the vapor phase.

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14 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23

signature and Tm values (Table 1) measured in the C3 cement

Fig. 10. SFTIR spectra for the liquid and vapor phases of two secondary hydrocarbon
fluid inclusions (HC-FI) illustrating the absence of molecular water, an OH-peak from
water inside the quartz matrix and CH4 (more abundantly present than in the primary
FI) in the gas bubble. Absorbance values correspond to common scale.
exposed limestones of the Guzmantla Formation (e.g. Ferket et al.,
2003B).
4.2. Diagenesis of the Guzmantla limestone
Results of diagenetic studies on samples of the Guzmantla
Formation limestone have been published earlier by Ferket et al.
(2003a,b, 2006). Primary FI in calcite (C3) filling post-BPS/pre-
LPSS breccia-veins display Th values between 40 and 65  C
(Fig. 11A). This type of veins is commonly observed in the reservoir
limestones. They were interpreted as hydrofractures expelling
fluids under the increasing compressional stress. The isotopic
indicate a meteoric component which can be explained by periodic
emersion of a forebulge that led also to local karstification (Ferket
et al., 2003a, 2006, Roure et al., 2009).
An exhumed oil reservoir analogue has been studied in detail in
the Peñuela Quarry (Fig. 2), where differentially bitumen-
impregnated strata crop out. For the detailed diagenesis of the
limestone in the Peñuela Quarry, the reader is referred to Ferket
et al. (2003b). New FI results from this site are presented here.
HC-FI were found in some calcite (C4)-cemented fractures that
postdate the formation of LPSS and can thus be related to the syn-
or post-Laramide stage. These veins contain viscous (biodegraded)
oil and abundant coffee-colored HC-bearing biphasic FI. The latter
FI display bright yellow fluorescence (Plate 3B–D) and are charac-
terized by rather homogeneous V/L ratios of 10%. The calcite crystals
comprise a more transparent nucleus with virtually no primary FI,
followed by a speckled zone containing aqueous and HC-FI and
finally succeeded by a dark inclusion-rich rim containing numerous
HC-FI (Plate 3A). The center of the crystals may display large HC-FI
that occur as isolated features or along pseudosecondary trails
(Plate 3C). The bulk of the HC-FI is concentrated along crystal
margins, although some smaller crystals are completely charac-
terized by a dense FI distribution (Plate 3A and B).
The described growth pattern of FI zones in the vein-calcite
indicates that the HC-FI are mainly primary to pseudosecondary FI
and formed in the late stage of calcite precipitation. SFTIR analyses
revealed low mature oil (mean CH4 content of 10–17 mol%; C9–C12
alkane equivalents) and the absence of molecular H2O in the HC-FI,
which is rather exceptional (Fig. 12). The homogeneous aspects of
the HC-FI in the crystal rims, as well as the absence of water in that
zone, suggest that the latest stage of calcite precipitation occurred in
an oil-dominated environment, such like an oil-filled reservoir. Th
values vary between 55.5 and 89  C (Fig. 11B). These should be
regarded as minimum temperatures and a correction is needed to
know the trapping, i.e. precipitation temperature. The elevated
temperatures, together with the deduced paragenetic position of oil
migration before major karstification of the limestone (late Eocene
to Present; Ferket et al., 2003B) give evidence of a Laramide timing of
oil migration and trapping.
5. Thermal and pressure modeling
5.1. First thermal modeling results
Based on maturity data and results from diagenesis and FI study,
a numerical modeling exercise has been performed with GENTECT
(complex tectonics module of GENEX; IFP) in order to better
characterize ancient thermicity of the Córdoba Platform. First,
maturity trends based on all available data sets were analyzed.
These data, together with other basin parameters were used to

25 C3 veins C4 veins
sample 1 8
20 7
6
frequency

sample 2
frequency

15 5
4
10 3
5 2
1
0 0
40 45 50 55 60 65 70 60 70 80 90 >90
Th (°C) Th (°C)

Fig. 11. Histograms summarizing microthermometric results on fluid inclusions in diagenetic phases from the Guzmantla Formation limestone (see text for descriptions).
Th ¼ homogenization temperature.

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H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23 15

Plate 3. Hydrocarbon fluid inclusions (HC-FI) in vein-calcite (C4) from the Peñuela paleoseep. A/transmitting light view, the FI are concentrated along crystal borders while the
nucleus of the calcite crystals is rather limpid, B–D/view under fluorescent light. B/concentration of fluorescing FI along some crystal borders, C/trails of fluorescing FI crossing
crystal borders thus indicating a secondary origin of these FI, D/detail of a typical pseudosecondary HC-FI from the Peñuela-calcite C4.

determine the heat flow at the base of the sediments. Once an
appropriate fit of the data is reached, burial temperature curves can
be calculated for a chosen horizon. At this point, diagenetic results
can be applied to approve the model and to test kinematic
parameters. However, the results depend on the applied conceptual
model (with a balanced kinematic evolution implying assumed
amounts of flysch deposition, tectonic stacking and erosion). In our
first thermal modeling exercises, the model of Ortuño-Arzate et al.
(2003) was used as input.
Both R0- and Tmax versus depth diagrams indicate a different
gradient for the pre- to syn-Laramide (steeper) than for the post-
Laramide (weaker) period. This might result from the typical

Fig. 12. SFTIR mapping of a primary hydrocarbon fluid inclusion (HC-FI) in the Peñuela vein-calcite. Right: aliphatic HC, i.e. CH2-CH3 chain in HC-FI; left: mapping of the
CO3-signature of calcite matrix (band at 2526 cm1) is shown for comparison (ESRF, Grenoble).

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16 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23

A B
0 0
hanging wall hanging wall
Orizaba Fm. Orizaba Fm.
1 TYPE II - 10.0% 1 TYPE II - 10.0%

thr ust Tamaulipas Fm. th ru st Tamaulipas Fm.

Depth (km)

Depth (km)
2 2
footwall footwall
Orizaba Fm. Orizaba Fm.
3 TYPE II - 10.0% TYPE II - 10.0%
3

Tamaulipas Fm. Tamaulipas Fm.

4 4

5
40 0 44 0 48 0 52 0 56 0 60 0 64 0 68 0 4 00 4 40 4 80 5 20 5 60 6 00 6 40 6 80
Rock-Eval Temperature Tmax (°C) Rock-Eval Temperature Tmax (°C)

Fig. 13. Tmax versus depth diagram for well A calculated by GENTECT for a constant heat flow at the base of the sediments of respectively: A) 30 mW/m2, B) 50 mW/m2 and
considering ‘‘slow erosion’’ (i.e. effective stacking load) and generally accepted amounts of erosion (Ortuño-Arzate et al., 2003). Cubes give measured maturity values.

shape of a coalification curve deflecting after a linear evolution and
then steepening with higher burial (Suggate, 1998) or it might be
due to different heat flow during Cretaceous and Tertiary times.
Bottom-hole temperatures represent actual cool anomalies in the
Veracruz Basin and Córdoba Platform which have been interpreted
in relation to large-scale fluid flow (Ferket, 2004). Therefore, the
present-day data set has not been used to calibrate the models.
The GENTECT module was run several times for different heat
flow values assuming generally accepted amounts of erosion
(Ortuño-Arzate et al., 2003). Fig. 13 illustrates the maturity evolu-
tion for constant heat flow values of 30 mW/m2 and 50 mW/m2
respectively in well A. Since no Tertiary strata occur in this well and
the post-Laramide history is marked by erosion, a constant heat
flow has been used for the whole simulation. This simplification
allows easier evaluation of the effects of other parameters. More-
over, simulations making use of a variable heat flow for pre- and
post-Laramide time did not lead to significant differences in
temperature evolution, the maturity signature being almost
entirely determined by conditions at peak burial. Comparison of
these diagrams shows that a constant heat flow of 30 mW/m2 does
not allow a satisfactory fit. A value of 50 mW/m2 is needed to
explain actual maturity.
The following diagrams (Fig. 14) illustrate the fit of FI data (Th,
i.e. minimum trapping temperatures) onto calculated burial
curves for the concerned intervals, based on the simulations with
30 mW/m2 and 50 mW/m2 respectively. The width of the boxes
corresponds to paragenetic timing, the height with the range in Th
values. A heat flow of 50 mW/m2 is needed to explain measured
paleo-temperatures. Note that in these simulations no synde-
formational erosion has been taken into account. This means that
the studied Córdoba profile (Fig. 2) would have formed by ‘rapid’
thrusting (i.e. velocity of thrust emplacement exceeding the
amount of erosion) leading to effective increase in thickness of
the section (scenario A; Fig. 14 and D). Alternatively, the structure
might have resulted from ‘slow’ continuous thrusting, whereby
erosion keeps pace with thrust migration (scenario B; Fig. 15A and
B). In the latter situation, total thickness of the section would
never have increased. In scenario A, Th values fit quite well the
predicted temperature evolution. Moreover light oil and gas
would have been produced from about 75–55 Ma with a peak
around/after 60 Ma, which is in line with the observed HC-FI in
quartz and calcite. The box for the telogenetic history seems to
misfit the predicted temperature evolution. However, it should be
noticed that 1) post-Laramide lowering of the heat flow was
neglected; 2) Th gives only minimum estimates and 3) the effect
of topography-driven flow was not taken into account (‘cool’
bottom-hole temperatures). The simulation of scenario B shows
several problems. First, peak temperatures during the Laramide
phase cannot be explained with the considered conditions. Only
limited HC production is predicted and significant migration of oil
(e.g. Peñuela reservoir) becomes difficult to explain. Yet more
decisive for comparison between both scenarios is the Th range of
HC-FI from vein-calcite in the Peñuela Quarry (Fig. 15B). Fluo-
rescence and SFTIR analyses confirmed the absence of H2O in
these FI pointing out entrapment in an already differentiated oil
reservoir. Therefore, Th values (60–85  C) indicate significant
burial on top of the upper thrust sheet of the Córdoba structure
(Fig. 2). Scenario B cannot explain such temperatures, since major
erosion would have occurred before entrapment of oil.
Although the above exercise seems to allow determination of
basal heat flow and discrimination between kinematic scenarios,
the results still depend on current estimates of burial/erosion. Even
with balanced cross-sections, equilibrated kinematic models and
good maturity data it is possible to give an alternative solution
fitting the same data set, using lower heat flow and higher burial.
Such overburden could be attributed to additional allochthonous
thrust units and/or to early molasses/flysch deposition in a fore-
deep basin behind the forebulge. The type of burial cannot be
distinguished by thermal modeling. The only exclusive argument
that could allow distinction between different hypotheses is
absolute pressure indicators. Such data may be obtained, for
instance, from FI experiments.
5.2. PVT modeling of fluid inclusions
In order to further interpret the FI results discussed above, and
in order to determine paleo-pressures, bubble point curves and
isochores of the involved fluid systems need to be determined. The
bubble point curve and isochores for primary and secondary HC-FI
were calculated using a PVT software based on HC composition and
progressive decrease of the vapor bubble during heating.
The liquid vapor curve and isochoric P–T path (Fig. 16) have been
calculated using the software developed at the IFP (Ungerer and
Batut, 1997; Mougin, 1999) and validated on Pakistani samples
from Baluchistan by Guilhaumou et al. (2000) and Benchilla et al.
(2003). The first version of the software using EOS to do PVT iter-
ative calculations has been adapted to take into account only the
semi-quantitative composition derived from SFTIR micro-
spectrometry as analytical data (instead of GCMS analyses), and the
liquid vapor volume ratio at room temperature measured by

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H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23 17

A B
System System
uC P E O M P uC P E O M P
Series Series
T O G C M P T O G C M P
200 200

thrust

thrust

TSR
180 180

160 F Q 160 F
Q

TSR
140 140
Temperature (°C)

Temperature (°C)
120 120
C1 C1
100 100
D2 D2
80 80

60 60

40 40

20 20

0
expulsion HC
0
120 100 80 60 40 20 0 120 100 80 60 40 20 0
Time (Ma) Time (Ma)

C D
System uC P E O M P System uC P E O M P
Series T O G C M P P Series T O G C M P P
200 200
thrust

thrust
180 180

160 160

140 140
Temperature (°C)

Temperature (°C)

120 120

100
C4 100 C4
80 80
C3 C3
60 60

40 40

20 20

expulsion HC
0 0
120 100 80 60 40 20 0 120 100 80 60 40 20 0
Time (Ma) Time (Ma)

Fig. 14. A) and B): Calculated burial curves for the middle part of the Orizaba Formation in the footwall of the structure cut by well A. A constant heat flow at the base of the
sediments of 30 mW/m2 (A) and 50 mW/m2 (B) was respectively applied. C) and D): Calculated burial curves for the middle part of the Guzmantla Formation in the hanging wall of
the structure cut by well A. A constant heat flow at the base of the sediments of 30 mW/m2 (C) and 50 mW/m2 (D) was respectively applied. Boxes indicate Th values from FI study
within diagenetic phases in the concerned interval. Note that no pressure correction has been applied and Th values thus give minimum estimates for the formation temperature.
Note that the kinematic scenario behind these figures considers ‘‘slow erosion’’ (i.e. effective stacking load) and generally accepted amounts of erosion (Ortuño-Arzate et al., 2003).

microscopy. Other models were developed by Aplin et al. (1999) aromatic percentage of 25% corresponding to alkane equivalent
and a similar approach has been developed by Thiery et al. greater than C5 (data base, Montel, 1993).
(2000). In this second version of the model, we tried to be closer
to the experimental data currently obtained by in situ non- 5.2.1. Quartz from well A
destructive analyses. We introduce the alkane equivalent i.e. CH2/CH3 Alkane equivalents and CH4 percentages obtained from
ratio, the experimental percentage of CO2 and CH4 and a fixed SFTIR analyses were used to constrain the model. Although cogenetic

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18 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23

A B
System uC P E O M P System uC P E O M P
Series T O G C M Series
200 T O G C M s P
200

th ru st

thr ust
180 180

160
F Q
160

TSR
140 140
Temperature (°C)

Temperature (°C)
120 120
C1
100 100
C4
80 D2 80
C3
60 60

40 40

20 20
very little very little
expulsion HC expulsion HC
0 0
120 100 80 60 40 20 0 120 100 80 60 40 20 0
Time (Ma) Time (Ma)

Fig. 15. Resulting burial curves after application of a different kinematic scenario (‘‘rapid erosion’’) as used in Fig. 14 and a constant heat flow at the base of the sediments of 50 mW/
m2. Fig. 14B and D represent a scenario with ‘rapid’ thrusting (i.e. velocity of thrust emplacement exceeding amount of erosion) leading to effective increase in thickness of the
section. Fig. 15 alternatively considers the structure as having resulted from ‘slow’ continuous thrusting, whereby erosion keeps pace with thrust migration. In such situation, total
thickness of the section would never have increased. Note that no pressure correction has been applied and Th values thus give minimum estimates for the formation temperature.

HC- and water-FI are present, which allows accurate pressure
estimation, the actual procedure is not evident. Strictly speaking,
the isochores of the system H2O–NaCl–CH4 should be used for the
water-FI. This is a complex system and methane equivalents should
be known.
Nevertheless, the PVT modeling allows determining a minimum
and maximum value for the pressure at trapping. The minimum
value for primary FI (i) is between 175 and 210 bar, i.e. the value
where the isochores cross the bubble point curve. Contribution of
CO2 in the system has little effect on the minimum pressure. An
upper estimate can be obtained by considering 150  C (i.e. Th for
cogenetic water-FI) as a realistic temperature for quartz precipita-
tion. Note that the pressure correction for aqueous FI is expected to
be limited because of their CH4 content (Hanor, 1980; Goldstein and
Reynolds, 1994). The isochores of the HC system at 150  C intersect
at a pressure of 350 bar. Pressure determinations in similar systems
are documented in literature by Thiery (2006) who calculated
a pressure of 329 bar for a water–HC fluid (0.13 mol% CH4) at a Th of
145  C. Guillaume et al. (2003) report H2O–NaCl (4 mol% eq. NaCl)
and HC-FI with Th values of 145  C and 112  C respectively whereby
the isochores of aqueous inclusions at 145  C intersect the isopleths
of a H2O–NaCl–CH4 system with 0.071 mol CH4 at 220 bar.
Alternatively, the measured dissociation temperature (Td 17–
20  C) of CH4-clathrate in the cogenetic aqueous FI would indicate
a dissociation pressure of 150–220 bar in a pure H2O–CH4 system.
However, the measured amount of NaCl (w10 wt%) and the pres-
ence of other alkanes (detected by FTIR in very low amounts) act as
inhibitors for CH4-clathrate. This implies that the Td may be shifted
to lower values at the same pressure (Sloan, 1998). Taking into
account this incertitude, the pressure values corresponding with
the measured Td probably give an underestimation, corroborating
high pressures in the system (Diamond, 2003).
In conclusion, we can consider trapping conditions for the
primary FI at 140–150  C and 200 bar minimum. Real trapping
pressure might extend until 350 bar. Secondary HC-FI (iii) formed
under similar conditions, confirming the hypothesis that they were
trapped shortly after quartz cementation.
The (minimum) values for trapping pressure and hence paleo-
burial are much higher (4–5 km) than what the current kinemat-
ical model of the region considers as maximum burial (Ortuño-
Arzate et al., 2003). Two important lessons can be learnt from
these results: 1) hydrofracturing (see Section 4.1.2 and already
proven indirectly; Ferket et al., 2004) was the common fracturing
process during the main compressional period and 2) additional
burial must be taken into consideration in the western part of the
Córdoba Platform in order to explain pressure and maturity data.
Because maintaining an anomalously high topography for a long
time is unrealistic, it is more likely that a foredeep developed at the
current location of the Córdoba Platform and farther north along
the eastern front of the Sierra Madre Oriental, in response to
hinterland deformation and foreland flexuring (Alzaga-Ruiz et al.,
2009a,b; Roure et al., 2009, in press; Gonzalez-Mercado et al.,
submitted for publication). Without pressure data, a completely
different and otherwise consistent model could be validated,
invoking a 50 mW/m2 heat flow gradient and less burial (Fig. 14).
Therefore, the analyzed FI data are crucial for the understanding of
the region.
5.2.2. Calcite from the Peñuela paleoseep
PVT modeling based on measurements of decreasing volume of
the vapor bubble of FI with progressive heating and on results from
SFTIR analyses reveal a minimum pressure between 105 and
185 bar (Fig. 17). The reason for this high variability in pressure
values is not clear. Possibly, cyclic fracturing with different degrees
of overpressuring is responsible for the variation. Furthermore, the
minimum pressure is extremely high, given the position of the
Peñuela outcrop in an upper thrust sheet. Without appreciable
overburden (about 4 km or more) such pressures cannot be

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H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23 19

A 3,00E-01 B 300
Model 1 phase envelope 1
Experimental data Isochore 1
2,50E-01 Model 2 250 phase envelope 2
Isochore 2

Pressure (bar)
2,00E-01 200
% vol gas

1,50E-01 150

1,00E-01 100

5,00E-02 50

0,00E+00 0
0 20 40 60 80 100 120 -250 -150 -50 50 150 250 350
Temperature (°C) Temperature (°C)
C 4,00E-01 D 300
Model phase envelope
3,50E-01 Experimental data Isochore
250
3,00E-01

Pressure (bar)
200
2,50E-01
% vol gas

2,00E-01 150

1,50E-01
100
1,00E-01
50
5,00E-02

0,00E+00 0
0 10 20 30 40 50 60 70 80 -250 -150 -50 50 150 250 350
Temperature (°C) Temperature (°C)
E 0,45 F 300
Experimental data phase envelope
0,4 Model
Isochore
250
0,35

0,3
Pressure (bar)

200
% vol gas

0,25
150
0,2

0,15 100
0,1
50
0,05

0 0
0 20 40 60 80 100 120 140 -250 -150 -50 50 150 250 350
Temperature (°C) Temperature (°C)

Fig. 16. PVT modeling for primary (A–D) and secondary (E–F) hydrocarbon fluid inclusions (HC-FI) in the well A-quartz cement. The left column represents the gradual decrease in
volume % of the gas-to-liquid ratio during progressive heating, which forms together with the SFTIR results, the base for subsequent isochors calculation. The right column
represents the output of the model, providing phase envelopes and isochors for the concerned HC system.

explained. PVT modeling in the Peñuela area thus confirms the high
pressure values for the western Córdoba Platform.
Unfortunately, no cogenetic water-FI are present to intersect Th
with hydrocarbon isochores. As a consequence, no pressure
correction can be made for the Th values. However, the calculated
isochores are steep and even with a significant pressure correction
no huge increase in temperature would be obtained. Therefore, in
this present case, the actual Th values are rather representative of
real trapping temperature.
5.3. Discussion and new thermal modeling
GENTECT simulations taking into account a constant heat flow
of 30 mW/m2 in combination with a high tectonic load of 4.5 km
on top of the present topography also allow a good explanation
of observed maturity, diagenesis and FI measurements (Figs. 18
and 19). In this model, the homogeneous oil-FI in calcite C4
from the Peñuela paleoseep should have formed later during
post-Laramide cooling (Fig. 19B). Such timing for trapping would
not be unreasonable, since a minimum time is needed for the
reservoir to reach its structural position and subsequently, to fill
and differentiate the reservoir. Remember the exceptional nature
of the HC-FI (homogeneous entrapment and absence of molec-
ular H2O).
Without PVT modeling of the FI from the well A-quartz and
Peñuela-calcite, no distinction between different kinematic models
would be possible. The calculated pressures between 200 and
350 bar for the considered interval of well A and minimal pressures

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20 H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23

3,00E-01 300
Model phase envelope
Isochore
Experimental data phase envelope 2
2,50E-01 250
Model 2 Isochore 2

Pressure (bar)
2,00E-01 200
% vol gas

1,50E-01 150

1,00E-01 100

5,00E-02 50

0,00E+00 0
0 10 20 30 40 50 60 70 80 90 -250 -150 -50 50 150 250 350
Temperature (°C) Temperature (°C)

1,80E-01 300
Model phase envelope
1,60E-01 Isochore
Exerimental data 250 phase envelope 2
1,40E-01 Model 2 Isochore 2

Pressure (bar)
1,20E-01 200
% vol gas

1,00E-01
150
8,00E-02
6,00E-02 100
4,00E-02
50
2,00E-02
0,00E+00 0
0 20 40 60 80 100 120 -200 -100 0 100 200 300 400
Temperature (°C) Temperature (°C)

2,00E-01 300
Model phase envelope
1,80E-01 Experimental data
Isochore
250
1,60E-01
Pressure (bar)

1,40E-01
200
1,20E-01
% vol gas

1,00E-01 150
8,00E-02
100
6,00E-02
4,00E-02
50
2,00E-02
0,00E+00 0
0 10 20 30 40 50 60 70 80 90 -200 -100 0 100 200 300 400

Temperature (°C) Temperature (°C)

Fig. 17. PVT modeling results for primary hydrocarbon fluid inclusions (HC-FI) in calcite from the Peñuela paleoseep.

0
between 105 and 185 bar for the Peñuela setting are in favour of hanging wall Orizaba Fm.
TYPE II - 10.0%
a model with 30 mW/m2 heat flow and thick (4.5 km) flysch
Depth (Km)

thrust Tamaulipas Fm.

deposition in a foredeep prior to Laramide thrusting. Furthermore, 2 footwall
Orizaba Fm.
these pressures indicate that fluids were overpressured (wlitho- TYPE II - 10.0%
static gradient) during the Laramide phase.
Tamaulipas Fm.
The above discussed exercises have several consequences for 4
the understanding of the petroleum system. Hypothesis 1 with
the interpretation of a changed geothermal gradient (Fig. 14B and
D) engenders an earlier maturation of source rocks, i.e. starting 6
400 440 480 520 560 600 640 680
before and reaching its peak during the Laramide phase. Petro-
leum maturation reaches the gas window in the footwall block Rock-Eval Temperature Tmax (°C)
and a wide oil–gas zone is installed in this block. The hanging wall Fig. 18. Tmax versus depth diagram for well A calculated by the GENTECT program for
block, however, only reaches the oil window. These results are in a constant heat flow of 30 mW/m2 at the base of the sediments and thick overburden
good agreement with the observed hydrocarbons. Hypothesis 2 as calculated from the PVT modeling. Cubes indicate measured maturity values.

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H. Ferket et al. / Marine and Petroleum Geology xxx (2010) 1–23 21

A B
System uC P E O M P System uC P E O M P
Series T O G C M P Series T O G C M t P
200 200

thrust

thrust
TSR
180 180

160 F 160
Q
Temperature (°C)

Temperature (°C)
140 140

120 120
C1
100 100
C4
80
D2
80
C3
60 60

40 40

20 20
expulsion HC expulsion HC
0 0
120 100 80 60 40 20 0 120 100 80 60 40 20 0
Time (Ma) Time (Ma)

Fig. 19. Calculated burial curves for A) the middle part of the Orizaba Formation in the footwall of the structure cut by well A and B) the middle part of the Guzmantla Formation in
the hanging wall of the structure cut by well A. A constant heat flow of 30 mW/m2 in combination with a high tectonic load (after PVT modeling) was applied. Boxes indicate Th
values from FI study within diagenetic phases in the concerned interval. Expulsion of hydrocarbons (HC) is predicted around 58 Ma. Note that no pressure correction has been
applied and Th values thus give minimum estimates for the formation temperature. In case of the HC-FI from the Peñuela paleoseep this correction is expected to be significantly
higher, while for the HC-FI in the well A-quartz it is expected to be minor (see text for discussion).

with the interpretation of a high tectonic load (Fig. 19) predicts
maturation during and after the main Laramide phase (peak
w58 Ma). The footwall block reaches lower maturity values with
respect to hypothesis 1, namely within the oil and oil–gas zone.
The hanging wall block attains higher maturity up to the oil–gas
zone.
6. Conclusion
Microthermometric results from FI formed at different diage-
netic stages in the reservoir history helped, in combination with
organic maturity parameters, to calibrate thermal modeling exer-
cises in the Laramide FTB of NE Mexico. Present-day bottom-hole
temperatures display a ‘cool’ anomaly, which can be explained by
fluid flow. Therefore, thermal models should not be calibrated with
this data set. Despite the good fit of various data the calibrated
thermal model is still ambiguous since it is based on presupposi-
tions about paleo-burial and erosion in the operated kinematic
model.
The occurrence of cogenetic HC- and water-FI for which also
SFTIR analyses and PVT modeling were performed allowed to
calculate minimum and maximum values for the Laramide burial
in the western part of the Córdoba Platform. The calculated
pressures indicate that paleo-burial was much larger than
previously assumed. The results put forward that late Cretaceous
to Paleocene hinterland deformation engendered foreland flex-
uring with installation of a thick flysch basin in this part of the
platform. Foreland flexuring during the latest-Cretaceous was
recognized already by the presence of a paleo-karst on top of an
emerged forebulge (Ferket, 2004; Ferket et al., 2003a, 2006).
Paleo-erosion of the ancient flysch basin in the western part of
the Córdoba Platform can now be constrained to about 4.5 km
and the basal heat flow at that time would have been around
30 mW/m2.
Acknowledgments
The main part of the diagenetic research was carried out during
a PhD at the University of Leuven (Belgium) and subsequent
investigations and modeling were performed during a joint post-
doctoral project between IMP and IFP. We thank IMP, in particular
Salvador and Felipe Ortuño-Arzate, and Pemex (Exploration and
Production, Veracruz, Mexico) for their kind support. We are
grateful to Pascal Mougin for the thermodynamic modeling and to
Biliana Gasharova and Y.L. Mathis at the Institute for Synchrotron
Radiation, Forschungeszentrum, Karlsruhe (ANKA), and Marine
Cotte at the ESRF (Grenoble) for their helpful assistance at the FTIR
beam line.
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