Clays diagenesis and fluid migration, new information for a 3D modeling of
fluid circulation in the Llanos Basin of Colombia
GONZALEGONZALEZ*, Felipe (IFPEN/UPMC); MORETTI, Isabelle (IFPEN); GUICHET Xavier (IFPEN); KOHLER, Eric
(IFPEN); FRANCE-LANORD, Christian (CRPG-CNRS); RODRIGUEZ German (CEPCOLSA) and MORA, Andres (ICP).
Copyright 2012, ACGGP.
This paper was selected for presentation by an ACGGP Technical Committee following review
of information contained in an abstract submitted by the author(s).
Abstract
The increasing of hydrocarbon production in the Llanos
Basin of Colombia (LBC) confirms that its petroleum system
is rather well understood, however, question marks remain
concerning the fluid migration pathways and the large
water/oil ratio within the producting fields. To have a better
understanding of the water origin and of the fluid circulation,
formation water have been sampled and analysed. The low
salinity values of the formation waters (sampled in the
hydrocarbon producing wells) were historically interpreted as
the result of a dilution of the saline connate waters with the
fresh meteoric waters. New analytical data of stable isotopes,
measured on rivers and formation waters, allow us to highlight
areas where indeed meteoric waters infiltrate within the basin.
However the stable isotopic data (δD, δ18O) suggest a third
source of water in the north-westward deepest part of the
LCB. We link it with the diagenetic evolution of the clay
minerals; indeed the LCB infilling is for a large part shally and
the smectite – illite transition release fresh water (Gonzalez et
al., 2011). XRD and CEC data acquired on six wells confirm
the occurrence of this transformation in the LBC over the last
couple of Myr and allow us to propose a kinetic reaction for
since transformation taken into account the thermal evolution
already calibrated in the nuemericla model. The quantity of
water due to this dehydration is far to be negligible.
Finally, to check the consistency of the data, 3D basin
modeling of formation fluid circulation in the LBC were
carried out taking into account the water expelled by clays
diagenesis as well as the meteoric water infiltration. The
model allows us to predict the ratio of mixing between the
waters of various origins
Llanos Basin of Colombia
The so called Llanos Basin of Colombia (LBC) is a flat
topography of around 200000 km2. Isolated to the East by the
foothills of the Eastern Andes Cordillera, limited to the South
by the Guaviare river, Vaupes basement and the Macarena
Sierra (with some Cretaceous and Tertiary outcrops), to the
East by the Precambrian Guyana Shield and to the North by
Venezuela (figure 1).
A Northwest dipping monocline of a siliciclastic sequence
pinching-out eastward, unconform over Paleozoic sediments
and Precambric basement.
75°W 70°W 65°W
10°N
Venezuela
a
ller
rdi
er
Riv
5°N
Guyana
Co
ta
Me
rn
Shield
ste
Ea
iver
Guaviare R
0°
Figure 1. Llanos Basin boundary (black line), Topography and
fluvial system of the Llanos Basin. White squares: distribution
of wells sampled for cuttings. Blue circles: Samples of fluvial
water distribution. Red circles: Distribution of wells where
formation water were collected.
Late Cretaceous formations consist on marine deposits
(including the Gacheta Fm, main source rock), they pinch out
eastward. The Paleocene is represented by the Barco-Cuervo
Fms, and the Eocene by the fluvial deposits of Mirador Fm.
which is the main oil producer reservoir in the LCB. The
Oligocene and Eocene formations correspond to the deltaic
system of the Carbonera Fm, interlayered shales and
sandstones differentiated as members C1-C8 (shales and
sandstones). The Middle Miocene transgression is presented
by a regional flooding surface, Leon Fm. (a regional seal) and
the current deposits are the mollase of the Guayabo Fm.
(figure 2).
A complete analyse of the petroleum system could be
found in (Moretti et al., 2009a), to resume: most of the
sandstones are potential reservoirs and all the shale have
organic content. Eastward all the series pinchout, especially
the cretaceous source rocks but migration from the mature
area located north-westward near the Cordillera in continuous
since at least the Middle Miocene. The traps located on the
migration pathway (essentially small offset normal faults) are
often charged in HC. Discoveries have been also done in
sedimentary traps, channels in the Carbonera Fms as well as
pinchout of the reservoir beds eastward. Due to the shallow
depth of the reservoirs in the thin part of the foreland east and
southward the oil is often biodegraded and °API could be as
low as 10°. North and westward the reservoirs contain a
2 Clays diagenesis and fluid migration, new information for a 3D modeling of hydrocarbon and water circulation of the Llanos Basin of Colombia
mixture of oil coming from the various source rocks and the
initial HC that arrived when the reservoirs was shallow before
the Guayabo deposit were biodegraded .
Biodegradation took place at the contact between water
and oil if the temperature of the reservoir remained low (less
than 80°C). In addition with the high water cut the existence
of this process increases the need of a good understanding of
the water flow in the Llanos. We approached that issue by
collecting new data (sampling + analyses) on both fluid and
rock and by modelling the 3D fluid flow within the Llanos
with the aim to take into account both the water and the HC
flows. Waters have been sampled in various producing fields
as well as in rivers (Figure 1), systematic measurements of
temperature, pH, O, D isotopes and chemical major elements
have been done. Some gas samples have been also carefully
taken for noble gas isotope analyses (not presented here). The
burial history as well as the temperature versus time and the
source rock characteristics are known from previous studies
(Moretti et al., 2009a) and so will not be discussed further
more in this paper.
NEOGENE
PALEOGENE
CRETACEOUS
Figure 2. Stratigraphic Column showing the main elements
of the petroleum system.
Formation water
Salinity of the water produced in the HC fields is low,
previous studies (Person et al, 2012; Gomez et al 2009;
Villegas et al, 2004) defined the hydrodynamics of the basin
as an active groundwater flow system of meteoric water
recharge topography driven, with different flow patterns for
the pre-carbonera units and for the Carbonera reservoirs.
Recharge is supposed to take place east- and southward. Due
to the increase of the salinity in some Cretaceous reservoirs
near the compressive front as well as the pressure regime,
charge from the Eastern Cordillera is precluded. However,
taken into account the geometry of the series, an active
recharge of meteoric water downdip to the Mirador Fm. means
that shale units of Carbonera Fm. and of the Leon Fm. are
permeable enough (or fracturated) to allow hydraulic
comunication with the surface (Villegas et al, 2004). Such an
hypothesis is poorly compatible with the fact that shale
formations represent an important volume in the clastic
sequence and are proven to act also as top seals in the
petroleum system.
The low salinity values of formation waters (often less
than 4000mg/L) are so interpreted as the result of a flush of
meteoric water, suggesting a dissolution of salinity in the the
connate water (the water preserved initially in a sedimentary
deposit) of the marine and deltaic deposits (up to 35000
mg/L). can we be more qualitative ?
Water modifies its isotopic composition by an additional
supply of fluid into the reservoir. As a result, the δD and δ18O
isotopic composition of formation water can give us
information about preservation, evolution, origins and mixing
of the current formation water.
Meteoric water influence
Stable isotopes of hydrogen δD and oxygen δ18O, are trace
element in water and present a natural abundance of about
0.015% and 0.24% respectively.
Seawater is the largest reserve of water in the earth and
represents the stable isotopic composition reference of
δD:δ18O 0,0:0,0 (‰) defined as the Standard Mean Ocean
Water (SMOW) (figure 3).
δD and δ18O stable isotope values in meteoric water can
vary with some local conditions as large rivers transporting
water over long distances, small drainages, precipitation,
evaporation and seasonal variations.
Stable Isotope Composition of Fluvial and Formation Water
Samples in the Llanos Basin of Colombia
SMOW
0
L
W
LM
-20
δ2H / VSMOW (‰)
-40
-60
L Fluvial Samples
-80
GM
W
Tertiary Samples
Cretaceous Samples
González Uribe et al, 2007
-100
-12 -9 -6 -3
δ18O / VSMOW (‰)
0 3 6
Figure 3. δD/δ18O ratio of fluvial and formation water samples
(Gonzalez et al, Geofluids in press; González Uribe et al,
2007). Note the influence of isotopic traces of meteoric water
in some fomation waters (Tertiary and Cretaceous) and the
shift of the LMWL with an increase of δ18O values.
SPE GONZALEZ ET AL. 3

δD/δ18O ratio of meteoric waters varies localy in a direct South North

relation to evaporation/precipitation in natural waters at same Eastern Cordillera
environmental condtion. Isotopic behavior synthesized as the
0 km.
Global Meteoric Water Line (GMWL) is expressed as: Fresh water 1

δD = 8 δ18O + 10‰, (Eq. 1) Saline water Brackish water

100°C 3
Basement 110°C
0 50 100 km. 4

For this study, 18 rivers of the Llanos fluvial system and

(‰
(‰)
end

VSMOW
-5
r tr
17 samples of formation waters were collected, filtered

VSMOW
h wate
ckis
d bra
(through a 0.45 µm milipore) and stored in-situ to preserve the h an -8
Fres

d18O
d18O
Tertiary sample
stable isotopes composition, avoid loss of water vapour and Cretaceous sample
-10

isotopic exchange with the surroundings. 910000 960000 1010000

North (m)
1060000 1110000

δD/δ18O ratio of the Llanos rivers, allow us to define a
local meteoric water line (LMWL) as reference of fluvial
waters. Isotopic ratio of δD/δ18O of Formation waters that fits
with the LMWL, highlights the distribution of reservoirs
influenciated by meteoric water. They are located in the south
and south east in shallow reservoirs.
Distribution of stable isotopes influenciated by meteoric
water decreases in depth and the increasing δ18O values
deviate from the LMWL. These formation waters that trend
away from the LMWL toward positive values (δ18O values of
clay minerals are between +10 to +30 per mil, Savin &
Epstein, 1970a, 1970b) can be associated to clay dehydration
and isotopic exchange with clay mineral during burial, linked
with the smectite to illite mineral transition in shale formations
(figure 3).
Diagenesis
Figure 4. South-North cross section, west of the LBC. A projection
of formation waters samples (in blue: formation waters influenced by
meteoric water, in red: formation waters enriched in δ18O) with a plot
of δ18O values northward for brackish salinities of formation water.
Note the increase of δ18O values in depth.
Geochemical analysis of Clay Diagenesis
Illite to smectite mineral transition is one of the most
important reactions during shale diagenesis. It could be used
as geothermometer to constrain the thermal evolution of
sedimentary basins and correlated with vitrinite reflectance
data. They could be associated to an enhance of hydrocarbon
migration and to supply additional water to the reservoirs (Eq.
2) (Henry & Bourlange, 2004; Hillier et al, 1995; Huang et al,
1993; Colten-Bratley, 1987; Bruce, 1984).

Diagenesis modifies the geochemical characteristics of Smectite + K + → illite + xSiO2 + nH 2 O (Eq. 2)

formation fluids through fluid-rock interactions controlled by
increase of temperature and pressure, allowing an exchange
between the water-rock during thermal evolution. These
processes include organic matter maturity and smectite to illite
mineral transition, sources of hydrocarbon and interlayer
water release into carrier beds and reservoirs.
Oxygen is the most abundant element in rock minerals,
contained in a 46.6% in weight. Interlayer water in clay
minerals with swelling properties (smectites) re-equilibrates
rather quickly with the environment in few days at room
temperature (Savin & Epstein, 1970a, 1970b) and exchange
easily isotopes with water. Water-rock exchanges during
diagenesis produce an increase the δ18O concentration in
formation waters, shifting the δD/δ18O ratio toward positive
values of δ18O according to the increasing of temperature in
depth (figure 3 and 4).
Formation waters without a meteoric water influence shift
from the LMWL, present an exponential increase in δ18O
concentrations in depth toward the Northwest deep reservoirs
in the LBC, where the low salinity values suggest a source of
fresh water linked with the water-rock exchange (figure 4).
Loss of interlayer water of smectite minerals in depth
during burial represents an additional source of fresh water
into the formation water fluid system (Yang, 2000; Elliot &
Matisoff, 1996; Abercrombie et al, 1994; Colten-Bratley,
1987; Burst, 1969). Illite to smectite mineral transition
describes the dehydration states of smectite in depth.
Clay minerals are a dominant component of shales.
Smectites are hydrated clays formed by weathering of silicates
minerals in soils and sediments at surface with cation
exchange capacity (CEC) properties. Estimations of CEC in
total rock is an indirect measurement to calculate the smectite
w% in shales. Observed CEC reduction with depth represents
the decrease of smectite proportion during burial. It
corresponds to the evolution modifying diagenetically the
smectite mineral structure in illite followed by the release of
its interlayer water.
To define the distribution of %smectite in total rock and
quantify the smectite to illite mineral transition in depth, 13
cutting samples of shaly formations at different depths of six
wells were collected, cleaned and analyzed.
Powder of total rock shale cuttings were immersed and
stirred in an alcoholic solution of tetramethylammonium
(TMA), molecules absorbed by minerals with swelling
4 Clays diagenesis and fluid migration, new information for a 3D modeling of hydrocarbon and water circulation of the Llanos Basin of Colombia

properties (smectites) in order to quantify the reduction of %illite %Sm total rock (Swy-2 ref.) Compaction : Water release
0 50 100 0 20 40 60 80 100 0,0 0,2 0,4 0,6 0,8 1,0
CEC during dehydration of clays in depth. Results were 0

obtained with Fourier Transform Infra-red Spectometry

(FTIR) measurments which allow to quantify smectite 1000

proportions in each sample and are calibrated with a synthetic

SWy-2 equivalent (Wyoming montmorillonite) to define a 2000

Depth (m)
Leon Fm Top
%Smectite (figure 5). The use of TMA and FTIR allows to
3000 Carbonera Fm Top
deconvolve the effect of other minerals that have a cation

Smectite Swy-2 25%

Smectite Swy-2 50%

Smectite Swy-2 75%

Smectite Swy-2 100%

exchange capacity (by adsorption, micellization ...).
4000
X-ray diffraction (XRD) analysis of oriented clay fraction Mirador Fm Top
(< 2µm) in a vapour of ethylen glycol (EG) at 60°C, is a 5000
Gacheta Fm Top

technic that allow diffrenciate the swelling properties of

smectites and identify the smectite content in the interlayered
mineral illite/smectite (I/S) and subsequently, the smectite to
illite mineral transition of I/S in depth (figure 5).
Smectite to illite modeling
Numerous studies on smectite to illite reaction in natural
environments and synthetic clays (Berger et al., 1997; Velde
& Lanson, 1993; Pollastro, 1985; Velde & Vasseur, 1992;
Withney & Northrop, 1988), have showed the reaction in
terms of the evolution of relative proportions of smectite in I/S
during the subsidence and thermicity rate versus time. The
reaction produce a reduction of smectite abundance in the I/S
interstratified minerals, this reaction highlight the depth which
a potential source of diagenetical water could be expelled to
the reservoirs product of an release of the water contained in
the smectite structure (figure 5 and 6).
Kinetic modeling of the smectite to illite mineral transition
can be described as:
Figure 5. Well cuttings analysis of 6 wells (figure 1) and
modeling. (a) I/S transition observed data in XRD-EG clay
minerals and modeled curve (Eq. 3). (b) Variation of
%smectite equivalent SWy-2 (Wyoming) in total rock,
reduction of CEC in depth. (c) Interlayer water release versus
water expelled by compaction in depth, taking into account he
lithological change and by dehydration of smectite.
3D Modeling
Numerical simulation methods have became a strong tool for
testing and defining scenarios of conceptual models. Now we
are able to define which the main issues to solve are and we
have an strong data base of new geochemical characterization
analysis of formation water to be synthesized and calibrated in
a basin modeling to determine the sources of fresh water,
quantify the volumes of waters, timing of intervention of each
source and mix.

∂[ Smectite]  − Ei 
[Smectite]
East

= Ai exp (Eq. 3) A
∂t  RT  B
Guayabo Fm
t: time, Ai: Kinetic constant, Ei: Activation Energy, R: North
Leon Fm
Perfect gas constant, T: temperature.
South

The reaction depends on the potassium available (eq. 2) %Sm

and chemical composition of smectite. For a release of
interlayer water, smectite layers may be transformed in illite
during a global substitution of Al3+ by Si4+ in the tetrahedral
layer without predicting the nature of the reaction, energy to
break the Si-O bound in the silica tetrahedron corresponds to
14 Kcal/mol, value used to fit the model the kinetic reaction
with the smectite to illite mineral transition observed. Kinetic
constant used is 10-10 m2/mol/s.
Quantity of water release depends on the initial hydration
state of smectite before diagenesis. Based on new geochemical
information of clay analysis a scenario of interlayer water
release for the llanos show an potential supply between 2000-
4000 m in depth (figure 5), a reaction that takes place in the
last couple of Mys (based in Gonzalez et al, 2011).
West
Figure 6. A. Composition: Low salinity and Cl- Family.
Isotope stable: d18O Influence. Clay diagenesis: illitization
>70%.Temperature: > 80°C. B. Composition: Low salinity
and HCO3- Family. Stable Isotopes: Meteoric Influence. Clay
diagenesis: Smectite hydrated. Temperature: < 80°C.
Modeling show a 3D distribution of the smectite to illite
mineral transition where the additional diagenetic water is
released into the reservoirs between 2000-4000 m.
SPE GONZALEZ ET AL.
Discussion
Water plays a major role in all the processes in earth crust
as result of water-rock interaction and is the main medium of
transport of components both surface and underground. Stable
isotopes of δD and δ18O of formation waters give us
information about preservation of connate water, mix with
meteoric water and diagenetic influence during water-rock
exchange.
Based on the LMWL reference for the Llanos, the δD/δ18O
ratios of formation waters allow us highlight the zone
influenced by meteoric water at the south and southeast of the
basin. Same data allow us to show that this influence
decreases in depth in reservoirs where low salinity values are
not related with a meteoric water flushing.
Diagenesis of formation waters result in an increase of
δ18O during water-rock exchange. The modeling of the
diagenetic reactions can be used to better define the fluid
circulation evolution into the reservoirs throughout its thermal
evolution history.
Variations of mineral composition in depth show a
correlation between both an increasing curve of %illite and a
depleted %smectite SWy-2 equivalent in depth (figure 5). This
is in agreement with a reaction mineral of a dehydration of
smectite by diagenetical process.
Organic matter maturity and smectite to illite mineral
transition are correlable diagenetical reactions and constrained
to the thermal evolution during burial history in a sedimentary
basin, resulting in hydrocarbon and interlayer water release
into the reservoirs.
Conclusions
δD and δ18O values of formation waters of the LBC show
that influence of meteoric water decrease with depth and
stable isotopes traces allow us to delimit the area of meteoric
waters reach the reservoirs.
Illite and smectite content, evolution of the I/S versus
depth measured on shale cuttings in the LBC as well as stable
isotope data of formation water at different temperatures and
depths allow us identify a 3th source of water linked with the
smectite dehydration during diagenesis due to the smectite
dehydration in the western and northwester deepest zones of
the LBC.
Smectite to illite transition takes place at the LBC and
explain for a part the low salinity. In the LBC, our new data
show that the maximum of the water expelled by the smectite
illite transition took place around 3km depth and we can so
precise the kinetic of the reaction within the LBC. This depth
is shallower that the one we have got, based on literature
based a priori kinetic parameters for the reaction in our first
model (Gonzalez et al., 2011). It may be explained by the
specific (rather fast) sedimentation rate in the LBC.
5
Acknowledgements
The sampling of the water within the producing fields has
been possible thanks to the help of various operating
companies (Ecopetrol, Cepcolsa, ICP). We also thank
Caroline Guilmette from the CRPG at Nancy who did part of
the stable isotopes analysis. The integration of data has been
done with GOCAD and the basin modeling with TEMIS.
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