Journal of Petroleum Science and Engineering 122 (2014) 384395

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Journal of Petroleum Science and Engineering

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

Impact of cation type and concentration in injected brine

on oil recovery in sandstone reservoirs
Ramez A. Nasralla n, Hisham A. Nasr-El-Din
Texas A&M University, College Station, TX, USA

art ic l e i nf o a b s t r a c t

Article history: Low salinity waterood has a high potential to improve oil recovery. However, the optimum water
Received 15 March 2013 chemistry for waterooding is still not well known, and the dominant mechanisms are debated. In the
Accepted 31 July 2014 present work, the effect of cation type and concentration in the injected water on the oil recovery to
Available online 7 August 2014
identify the optimum water salinity and composition was studied by performing coreood experiments.
Keywords: In addition, zeta potentials at oil/brine and rock/brine interfaces were measured to examine the impact
oil recovery of brine composition on electrical double layer expansion and investigate if it is one of the dominate
waterooding mechanisms. Furthermore, ionic exchange tests were conducted to improve the understanding of the
water chemistry rock/brines interactions.
zeta potential
Berea sandstone cores were used for waterooding and ion exchange experiments; all coreood
cation exchange
experiments were performed at high-pressure/high-temperature (HP/HT) conditions. Different concen-
coreood
trations of NaCl, CaCl2, and MgCl2 solutions were tested with two crude oils of different compositions
and properties. Ion concentrations in the core efuent uids were analyzed for both waterooding and
ionic exchange tests. The zeta potential was measured for solutions of oil/brine, and solid/brine; the
solids were Berea sandstone, quartz, feldspar, and four types of clays.
This work contributes to the understandings of the impacts of double layer expansion on oil recovery
during waterooding. Zeta potential results showed that Na changes the electrical charge at both oil/
brine and rock/brine interfaces to highly negative, which results in higher repulsive forces between the
two interfaces, and hence wettability alteration. Moreover, waterood experiments with NaCl solutions
improved oil recovery signicantly compared to CaCl2 and MgCl2. These results showed that there seems
to be a correlation between zeta-potential and oil recovery which implies that double-layer expansion
could be a primary mechanism of oil recovery by low salinity waterood. This study demonstrates that
cation type has a signicant impact on oil recovery, and it could be more dominant than the effect of
total salinity of the injected brines. These ndings can help in screening the brines that have higher
potentials for oil recovery improvement.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction comprehensive experimental work showed the success of low salinity

Waterooding is applied intensively worldwide to improve oil
recovery. It was demonstrated that water chemistry has a signicant
impact on oil recovery in sandstone reservoirs on coreood and elds
scales (Morrow and Buckley, 2011). Several eld trials proved the
efciency of low salinity water in improving oil recovery (Webb et al.,
2004; Robertson, 2007; Lager et al., 2008). Vledder et al. (2010)
observed a reduction in water cut due wettability change when low
salinity water was injected in Omar eld, Syria. In addition, a
n
Correspondence to: Petroleum Engineering Department, Texas A&M University,
College Station, Texas, USA.
E-mail addresses: Ramez.Nasralla@shell.com (R.A. Nasralla),
Hisham.nasreldin@pe.tamu.edu (H.A. Nasr-El-Din).
water in both secondary and tertiary recovery modes (Zhang et al.,
2007; Agbalaka et al., 2009) but sometimes for only one or the other
(Zhang and Morrow, 2006). In some other studies, tertiary oil recovery
improvement was never observed, but low salinity water improved
secondary oil recovery signicantly (Rivet et al., 2010; Nasralla et al.,
2011). However, Skrettingland et al. (2011) proved that low salinity
water might not be efcient in certain cases when the rock wetting
conditions are optimal, such that seawater injection is already ef-
cient. There is less evidence of the low salinity water effect available in
literature on carbonate reservoirs. However, signicant responses of
diluted seawater during secondary and tertiary coreoods were
presented by Yousef et al. (2011), and the response on eld scale
was conrmed by single well chemical tracer tests (Yousef et al., 2012).

http://dx.doi.org/10.1016/j.petrol.2014.07.038
0920-4105/& 2014 Elsevier B.V. All rights reserved.
 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395
Nomenclature
CBM coalbed methane
Cp centipoise
FB formation brine
HP/HT high-pressure/high-temperature
ICP-OES inductively coupled plasma optical emission
spectrometry
OOIP original oil in place
The possible risk of low salinity waterood is the potential to
cause formation damage in sandstone because of the presence of
clays. Therefore, it is important to take into consideration forma-
tion damage when designing low salinity brines. Scheuerman and
Bergersen (1990), (1989) developed diagrams that dened forma-
tion damage regions based on the ionic strengths of the brines
which can be used to design brines that are safe to inject.
However, these charts were developed based on single phase
waterood experiments, while on eld scale oil saturation cannot
go below residual saturation which can reduce the risk of forma-
tion damage as oil can coat some of the clays present in the
reservoir.
Although, low salinity waterooding showed a high potential
to increase oil recovery in most of the lab work and eld trials, the
success of low salinity waterooding application on a eld scale is
still uncertain due to the lack of understanding the underlying
mechanisms, which means the optimum salinity and conditions
are unknown. Most researchers agree that injecting low salinity
water creates a wetting state more favorable for oil recovery. The
remaining oil saturation decreases by low salinity waterooding
due to the wettability alteration that affects the microscopic
distribution and ow of uids in porous media. Different mechan-
isms have been proposed for wettability alteration by low salinity
water; however, the primary mechanisms are still debated.
McGuire et al. (2005) attributed the oil recovery increase to the
in-situ surfactant generation (saponication) by ooding with low
salinity water. Lager et al. (2006) suggested that multi-component
ionic exchange between the mineral surface and the invading
brine is the primary mechanism underlying the improved recov-
ery. Tang and Morrow (1999) explained the wettability alteration
with the assumption that heavy polar components of crude oil
adsorb onto particles at pore walls to give mixed-wet nes, and
brine chemistry has an effect on the forces needed to strip these
particles from the pore walls. Pu et al. (2008) suggested that
interstitial dolomite crystals play a role in low salinity recovery
mechanisms; there was no tertiary oil recovery by coalbed
methane (CBM) water in dolomite-free cores. Anhydrite dissolu-
tion was suggested as the primary mechanism for recovery of
residual oil by low salinity water from reservoir cores, which are
rich in anhydrite cement (Pu et al., 2010). Ligthelm et al. (2009)
suggested that the main mechanisms of wettability alteration
were cation exchange and expansion of the electrical double layer.
Rock wettability depends on the stability of water lm between
rock surface and crude oil (Hirasaki, 1991). The stability of water
lms is a function of the electrical double-layer repulsion that
results from surface charges at the solid/water and water/oil
interfaces. If these two interfaces have similar charges, a repulsive
electrostatic force will occur that keeps the disjoining pressure
high and maintains a thick water lm; this produces a water-wet
rock surface (Dubey and Doe, 1993). Sandstone is negatively
charged above the pH of 2 (Menezes et al., 1989). Crude oils are
positively charged at a low pH range (26) and negatively charged
at higher pH values (Takamura and Chow, 1985; Buckley et al.,
385
PV pore volume
RF recovery factor
Swi irreducible water saturation
TDS total dissolved solids, mg/l
Greek symbols
zeta potential (mV)
1989). Nasralla et al. (2013) investigated the effect of electrical
charges at the oil/brine interfaces on the wettability of mica
surfaces. Low salinity water altered the wettability towards more
water-wet at different pressures and temperatures. Lowering the
water salinity changed the charges at the oil/brine and rock/brine
interfaces to more negative, which resulted in increasing the
repulsive forces between the oil/brine and solid/brine interfaces,
and hence wettability alteration. The authors used the contact
angle technique for wettability evaluation, and zeta potential to
estimate the surface charge at oil/brine interface. Hassenkam et al.
(2012) performed an atomic force microscopy study to measure
the adhesion forces between carboxylic acid and sandstone; they
noticed reduction in the adhesion forces with low salinity brines.
The authors attributed this effect mainly to the DLVO theory.
Zeta potential is the potential at the shear plane of the
electrical double-layer. The magnitude of the zeta potential is
related to the surface charge at the oil/brine and mineral/brine
interfaces, and the thickness of the double layer. The ionic strength
of water affects the surface charge of sandstone and clay particles
(Kia et al., 1987; Alotaibi et al., 2011). Zeta potentials of three
different clays (kaolinite, illite, and chlorite) were determined in
distilled water by Hussain et al. (1996); kaolinite was the most
negative clay for the whole pH range. Furthermore, the surface
charge of solids is affected by the cation type. It was found that
Ca2 and Mg2 reduced the magnitude of zeta potential of Berea
sandstone and made it close to zero more effectively than Na
ions (Farooq et al., 2011). The zeta potential of kaolinite with
monovalent cations was more negative at 10  2 M concentrations
at almost all pH values compared to the values obtained with fresh
water, whereas, the zeta potential of kaolinite decreased (became
less negative) with an increase in divalent cation concentration
(Yukselen and Kaya, 2003). Moreover, the effect of brine salinity at
the interface between oil and brine was reported by Buckley et al.
(1989) using different concentrations of NaCl. Low ionic strength
of NaCl solutions resulted in a stronger negative charge of the
brine/oil interface compared to high ionic strength. It is evident
that electrokinetic charges of both oil/brine and rock/brine inter-
faces are signicantly affected by the ionic strength of the water.
The chemistry of water used for water ooding is a dominant
parameter in determining the oil recovery factor. Most of the
experimental work in the literature focused on reducing the brine
salinity, and not much attention was paid to the role of cation
types in the injected brine. Thus, the main objectives of this study
are studying the effect of cation type, and concentration in the
injected water on oil recovery, in addition to understanding the
working mechanisms for improving oil recovery by manipulating
the water chemistry. Therefore, several sets of experiments were
conducted. First, coreood experiments were run on different
concentrations of NaCl, CaCl2, and MgCl2 solutions to conrm that
there is a signicant effect of the cation type on oil recovery
improvement. Second, zeta potential measurements were con-
ducted at oil/brine and solid/brine interfaces by testing several
single-cation solutions against crude oils, Berea sandstone, and
386 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395

clays. Finally, ionic exchange tests were run by injecting a single-
cation brine into dry cores to study brine/rock interactions.
2. Experimental studies
2.1. Materials
Berea sandstone cores were used for water ooding, and ionic
exchange tests. Ten short cores (56 in.) were drilled from the
same rock block to be used for waterooding experiments, in
addition to three other dry cores that were used to study the
brine/rock interaction. The mineralogy of the Berea sandstone
block used in this study is given in Table 1. The porosity and brine
permeability of Berea sandstone cores were measured using a
coreood apparatus at ambient temperature (Table 2). For the zeta
potential measurements at the rock/brine interface, four different
types of clays, quartz, and feldspar (Anorthoclase, alkali feldspar)
were used. These minerals were obtained from Wards Natural
Science Company.
Two types of crude oils (A and B) were used for saturating the
cores and for the zeta potential measurements at the oil/brine
interface as well. The properties of the crude oils are given in
Table 3. All oil samples were centrifuged at 5000 rpm, and then
ltered through a sandstone core plug to remove any particles that
may damage the core. Waterooding experiments and ionic
exchange tests were conducted by injecting synthetic solutions
2.2. Zeta potential ()
Zeta potentials were measured for oil/brine and solid/brine
interfaces using the ZetaPALS technique (Phase Analysis Light
Scattering). The instrument uses HeNe laser as a light source,
and it measures the electrophoretic mobility of charged colloidal
suspensions. All the measurements were conducted at 77 1F.
Samples of oil/brine and solid/brine were prepared using the
procedure proposed by Zhang (2006). The solutions of oil/brine
were prepared at a volume ratio of 1:5, while the solid/brine
samples were prepared by adding 10 g/l of solids powder to the
brine. The brines used in these measurements were NaCl, CaCl2,
and MgCl2 at concentrations of 2000; 10,000; and 50,000 mg/l.
Two crude oils were used with the brines to prepare emulsions
between the oil and brine. Berea sandstone, quartz, feldspar, and
four different types of clays (illite, kaolinite, montmorillonite, and
chlorite) were crushed using a ceramic mortar and pestle. A sieve
of size 90 mm was employed to obtain very ne particles to be
added to the solutions to measure zeta potential at solid/brine
interface. Each solution was mixed by the sonication method using
a sonic probe. The probe tip was placed nearly 0.5 in. into the
solution and set at a constant rate for 1 min. Then, the solution
was kept overnight to ensure the stability of oil/brine emulsions. If
Table 3
Properties of crude oils.
Property Crude oil (A) Crude oil (B)

of NaCl, CaCl2, and MgCl2 at different concentrations. These 3

Density at 77 1F, g/cm 0.886 0.828
solutions were prepared by adding chemical reagents (salts) to Density at 212 1F, g/cm3 0.820 0.753
deionized water. The cores that were used for ionic exchange tests Viscosity at 77 1F, cp 32.2 20.4
were dry before injecting the brine, whereas, the cores used for Viscosity at 212 1F, cp 3.7 2.6
Acid number, mg KOH/g 0.18 0.11
water ooding experiments were saturated initially by the forma-
Base number, mg HCl/g 1.65 0.62
tion brine (FB), 174,000 mg/l, and crude oil to simulate real water
ooding scenarios in the eld. Table 4 gives the composition of the
formation brine. These brines were prepared using deionized
Table 4
water and reagent grade chemicals. Concentration of key ions in the formation brine.

Table 1 Concentration
Ion (mg/l)
Mineralogy of Berea sandstone cores.

Mineral BSS Na 54,400

(wt%) Ca2 10,600
Mg2 1,610
QuartzSiO2 85.0 Cl  107,000
FeldsparKAlSi3O8 6.4 HCO3 176
Calcite(CaCO3) 2.8 SO24  370
IlliteKAl2(Si3Al)O10(OH)2 2.0 TDS (mg/ 174,156
KaoliniteAl2Si2O5(OH)4 3.8 l)

Table 2
Properties for Berea sandstone core plugs.

Core ID Diameter Length Bulk volume Porosity Permeability Swi Saturating oil Brine injected
(in.) (in.) (cm)3 (vol%) (mD) (%)

1AL 1.46 4.99 137.3 18.2 111.1 27.8 Crude (A) 2,000 mg/l NaCl
2AL 1.46 5.01 138.1 17.7 137.7 24.8 Crude (A) 2,000 mg/l CaCl2
3AL 1.46 5.01 138.0 17.9 97.5 25.4 Crude (A) 2,000 mg/l MgCl2
4AL 1.47 5.54 153.7 17.6 100.5 31.6 Crude (A) 10,000 mg/l NaCl
5AL 1.46 5.58 153.8 17.9 106.5 32.3 Crude (A) 10,000 mg/l CaCl2
6AL 1.47 5.59 154.4 17.7 94.5 33.5 Crude (A) 50,000 mg/l NaCl
7AL 1.46 5.58 153.8 17.7 98.2 32.4 Crude (A) 50,000 mg/l CaCl2
1NP 1.46 5.59 154.0 17.7 88.2 25.6 Crude (B) 50,000 mg/l NaCl
2NP 1.47 5.55 153.3 18.0 91.2 26.8 Crude (B) 50,000 mg/l CaCl2
3NP 1.47 5.59 154.4 17.7 97.8 25.8 Crude (B) 50,000 mg/l MgCl2
1D 1.47 6.07 168.8 19.9 135.2 0.0 50,000 mg/l NaCl
2D 1.47 6.05 168.3 19.3 126.3 0.0 50,000 mg/l CaCl2
3D 1.47 6.04 168.0 19.1 129.9 0.0 50,000 mg/l MgCl2
 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395 387

the solution was cloudy, it should be diluted in the original brine

as the laser beam used to measure zeta potential cannot detect the
mobility of particles in cloudy uids. A sample of 4 mm of the
solution was transferred to a cuvette, and a parallel plate electrode
was placed into the cuvette to run the zeta potential measure-
ments. Five runs were conducted for each sample, and the average
reported zeta potential was taken. In addition, pH was measured
using a pH meter for each solution as zeta potential is pH-
dependent.

2.3. Core preparation and experimental procedure

For the waterooding experiments, the Berea sandstone cores

were dried, weighed, and then saturated with the formation brine
Fig. 1. A schematic diagram of coreood setup.
under vacuum. The core was placed inside the core holder, and the
formation brine was injected at a low ow rate of 0.1 cm3/min for
5PV to ensure that the core was fully saturated with water. Then, Table 5
core permeability to brine was measured at different rates (0.5, 1, pH of the oil/brine emulsions at 77 1F.
and 2 cm3/min). The weight of the saturated cores was measured,
and the core porosity was calculated from the weight difference Brine Crude (A)/brine Crude (B)/brine
before and after saturation. Dead crude oil was injected for at least 2,000 mg/l NaCl 5.75 4.65
5PV at different ow rates (0.1, 0.25, 0.5, and 1 cm3/min). Oil 10,000 mg/l NaCl 4.97 4.99
injection was stopped after 5PV only when there was no more 50,000 mg/l NaCl 6.03 5.9
water production for at least 1PV to ensure that the irreducible 2,000 mg/l CaCl2 5.12 4.74
10,000 mg/l CaCl2 4.38 4.59
water saturation was reached. The initial water and oil saturations
50,000 mg/l CaCl2 4.73 4.54
were calculated using the volumetric and the weight methods. All 2,000 mg/l MgCl2 5.48 4.96
short cores were aged in the oven at 212 1F for two weeks. The 10,000 mg/l MgCl2 4.56 4.67
three long cores were aged at the same temperature for one 50,000 mg/l MgCl2 4.41 4.26
month and at room temperature for 2 months. Afterwards, the
core was reloaded again in the core holder for waterooding tests.
3. Results and discussion
The efuent uid was collected to calculate the recovery factor,
and to study the interactions between the brine and rock by
3.1. Zeta potential ()
measuring the concentration of key cations using the Inductively
Coupled Plasma Optical Emission Spectrometry (ICP-OES).
The charges at the interfaces of oil/brine and rock/brine were
For cation exchange tests, the cores were dried and weighed.
estimated using the zeta potential technique to understand the
The core was placed in the holder, and 5 pore volumes of the
relation between electric double layer and oil recovery, where zeta
tested brine were injected to saturate the core and measure the
potential is measured at the slip plane in the electrical double
permeability at ambient temperature. Then, the oven was heated
layer. Charges at oil/brine and rock/brine interfaces are the main
up to 212 1F and the injection was continued. Core efuent
factor that controls the stability of the water lm surrounding the
samples were collected to measure Na , Ca2 , Mg2 , and SO24 
rock, and hence the rock wettability. A stable water lm, which is
concentrations. The ICP-OES was used to measure the concentra-
bound by the two interfaces of oil/brine and solid/brine, results in
tion of these cations, whereas sulfate ion concentration was
a water-wet rock, while developing an unstable water lm may
measured by a spectrophotometer that measures the precipitation
alter the wettability towards oil-wetness. Injecting water with a
of sulfate ions caused by adding barium chloride solutions to the
different salinity than the formation brine would cause changes of
sample. After the experiment was nished, the core was weighed
the charges at both oil/brine and rock/brine interfaces and, as a
again to calculate the porosity.
result, the electric double layer thickness would change, which
could improve or suppress the oil recovery.
2.4. Coreood set-up Emulsions of crude oils (A) or (B) with 2000; 10,000; and
50,000 mg/l of NaCl, CaCl2, and MgCl2 solutions were created to
The coreood apparatus consisted of a core holder, two measure the zeta potential at the oil/brine interface. Since zeta
accumulators, a syringe pump, a hydraulic pump, and an oven as potential is pH dependent, the pH was measured after preparing
depicted in Fig. 1. The core holder was placed inside the oven to the emulsion and reported in Table 5. The obtained pH values of
simulate the reservoir temperature; all the experiments were the emulsions were due to mixing the brines with oils. It is
conducted at 212 1F. The uids were stored in stainless steel important to note that the pH during the coreood might be
accumulators at room temperature, and they were injected into different than the reported pH for zeta potential as the volume
the core using an ISCO syringe pump. Heating coils were used to ratios of water to oil are different and combined effect of rock and
heat uids ahead of the core face. A hydraulic pump was used to oil on brine pH. In addition, pH in real reservoirs could be different
apply an overburden pressure on the core by injecting hydraulic due to different conditions such as presence of CO2. Figs. 2 and 3
oil in the bank between the core holder internal surface and show the zeta potential at the oil/brine interface for crude oils
rubber sleeve that cased the core. The overburden pressure and (A) and (B), respectively. The results show that the charge at the
core outlet pressure were controlled by pressure regulators. The oil/brine interface is negative for both crude oils with all solutions,
overburden pressure was kept constant at 1000 psi and the outlet except 50,000 mg/l CaCl2. It is evident that zeta potential is
pressure at 500 psi. The pressure drop between the core inlet and signicantly affected by the cation type and the concentration.
outlet was measured by a differential pressure transducer. A Sodium cations resulted in the most negatively charged compared
compact fraction collector was used to collect the efuent samples. to calcium and magnesium at 2000; 10,000; and 50,000 mg/l.
388 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395
Fig. 2. Impact of cation type and concentration on zeta potential at oil/brine
interface for crude oil (A).
Fig. 3. Impact of cation type and concentration on zeta potential at oil/brine
interface for crude oil (B).
Nevertheless, calcium cations changed the zeta potential at the oil/
brine interface to positive at 50,000 mg/l, while at 10,000 mg/l
CaCl2 the charge at oil/brine was negative but very close to zero.
Electrical charges at the oil/brine interfaces were almost the same
with 2000 mg/l CaCl2 and MgCl2 for crude (A). Moreover, reducing
the concentration of CaCl2 had a signicant effect on changing the
oil/brine charge. Generally, reducing the salinity in the solution
resulted in a change in the charge of the oil/brine interface to more
negative, which shows the signicant effect of water salinity on
the expansion of the electrical double layer.
The zeta potential of solid/brine was measured for Berea
sandstone with different brines; the results are shown in Fig. 4.
It is demonstrated that both cation type and concentration affect
zeta potential signicantly. Sodium chloride solutions with Berea
sandstone showed strongly negative charges unlike calcium
chloride and magnesium chloride. Calcium chloride solutions of
50,000 mg/l resulted in positive charges on Berea sandstone
particles, while the rock zeta potential with magnesium chloride
was weakly negative at the same concentration. As clays play an
important role in determining the surface charge of sandstones,
the same measurements were repeated by replacing Berea sand-
stone with different types of clays: illite, kaolinite, montmorillo-
nite, and chlorite (Fig. 5). It is evident that all types of clays have a
similar behavior to Berea sandstone. The highest negative charge
was obtained with 2000 mg/l NaCl. Furthermore, 50,000 mg/l of
NaCl resulted in a negative charge with a higher magnitude when
compared to 2000 mg/l of CaCl2 and MgCl2 with all types of clays.
This shows that the cation type has a dominant effect on the
electrical double layer. The zeta potential of kaolinite with all
concentrations of CaCl2 and MgCl2 were positive, except for
2000 mg/l MgCl2. However, sodium chloride solutions at different
concentrations showed negative charges with kaolinite. Zeta
potentials on kaolinite and chlorite were almost zero with
2000 mg/l CaCl2. The reduction of cation concentration decreased
the positive charges and increased the magnitude of the charge for
Fig. 4. Impact of cation type and concentration on zeta potential at Berea
sandstone/brine interface.
negatively charged surfaces. Moreover, the reduction in salinity of
some solutions changed the zeta potential from positive to
negative. This was noted for illite and chlorite with CaCl2 and
kaolinite and chlorite with MgCl2.
The effects of brine salinity and cation type on the zeta
potential of quartz and feldspar were studied as well (Fig. 6).
The zeta potential at the surfaces of quartz and feldspar became
more negative with the reduction of cation concentration and with
NaCl solutions compared to CaCl2 and MgCl2. Quartz showed
positive charges with 50,000 mg/l CaCl2 and MgCl2, while feldspar
surfaces were positive with 50,000 mg/l and 10,000 mg/l CaCl2
and MgCl2. It is obvious that the zeta potential of quartz and
feldspar behave similarly to Berea sandstone and clays. However,
all tested clays showed greater responses to the change of cation
type and concentration compared to quartz and feldspar. This
demonstrates that clays have a more dominant contribution than
quartz and feldspar in changing the electrical charges of sandstone
rock when manipulating the water chemistry. Therefore, clays may
play a signicant role in improved oil recovery by low salinity
waterooding. Table 6 gives pH values of all brine/rock suspen-
sions. The uncertainty of the zeta potential measurements for both
oil/brine and brine/rock was estimated by calculating the standard
error of the different runs conducted on the same sample; the
standard error varied from 0.3 to 2.8%.
The repulsive or attractive forces between oil and rock surfaces
are functions of the sign and magnitude of the charges at oil/brine
and rock/brine interfaces. If the two interface charges have the
same sign, it results in repulsive forces and vice versa. Further-
more, the higher the magnitude of the charge, the greater the
forces are. Crude oil can stick to the rock surface in the presence of
connate water (high salinity water) because of the weak electrical
charges caused by formation brine, which results in attractive
forces between the oil and rock. In addition, the oil organic
materials can be adsorbed by clays in sandstone reservoirs
(Austad et al., 2010). Changing the electrical charges to highly
negative at oil lm and rock surface by manipulating water
chemistry increases the repulsive forces between rock and oil
and provides a greater potential for the oil to be detached from the
rock and be swept by the imposed ow. Therefore, injection of
NaCl solutions has a higher potential to improve oil recovery than
CaCl2 and MgCl2 at the same concentration. A high concentration
of NaCl might result in higher oil recovery compared with low
concentrations of CaCl2 or MgCl2. In addition, a lower concentra-
tion of sodium chloride is more favorable for oil recovery enhance-
ment due to the higher repulsive forces. However, the efciency of
oil recovery by the injection of NaCl solutions may be lowered due
to the mixing of the injected solution with divalent cations from
formation brine, which affects the potential of NaCl to change the
zeta potential to highly negative. Increasing the repulsive forces
alters the rock wettability towards water-wet as a result of a stable
 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395 389

Fig. 5. Zeta potential at the solid/brine interface for various types of clays against different concentrations of NaCl, CaCl2, and MgCl2.

Fig. 6. Zeta potential at the solid/brine interface for quartz and feldspar against different concentrations of NaCl, CaCl2, and MgCl2.

Table 6
pH of solid/brine suspensions at 77 1F.

Brine pH

Berea sandstone Kaolinite Illite Chlorite Montmorillonite Quartz Feldspar

2,000 mg/l NaCl 7.68 4.4 7.32 6.31 9.71 5.78 5.99
10,000 mg/l NaCl 8.94 4.17 7.87 7.14 8.77 5.8 5.89
50,000 mg/l NaCl 8.77 4.13 8.28 6.85 8.4 5.68 5.24
2,000 mg/l CaCl2 6.79 4.05 6.46 5.75 8.26 5.72 5.82
10,000 mg/l CaCl2 7.23 4.05 7.06 6.45 7.28 5.68 5.75
50,000 mg/l CaCl2 6.75 4.07 6.77 6.18 7.54 5.41 5.47
2,000 mg/l MgCl2 6.27 4.15 6.54 6.45 8.93 5.8 6.17
10,000 mg/l MgCl2 7.7 3.97 7.28 6.16 7.86 5.77 6.09
50,000 mg/l MgCl2 7.58 3.98 7.3 6.1 7.66 5.52 5.81

and thick water lm surrounding the rock surfaces. However, the dominant mechanism of oil recovery, wettability alteration is not
wettability alteration is the result of low salinity water ooding the cause of improved oil recovery by low salinity waterooding,
due to increasing the water lm stability by higher repulsive but the mechanism is the detachment of the oil from the rock
forces. Moreover, assuming that the electrical charge change is the surface as a result of the repulsive forces.
390 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395

The zeta potential is a function of the temperature. The mea- stabilized at nearly 2.3 psi at the end of experiment. Core 3AL was
surement of zeta potential could not be conducted at the coreood ooded by 2000 mg/l MgCl2 solution for 12PV. The oil recovery
experiment conditions because the setup was run at atmospheric and pressure drop are shown in Fig. 9. After the injection of 3PV,
pressure and the uids would have evaporated at high tempera- 80% of OOIP was recovered.
tures. Some attempts in the literature were made to study the effect
of temperature on zeta potential for different minerals and oils.
3.4. Impact of cation type on secondary oil recovery
Rodrguez and Araujo (2006) studied kaolinite; Ramachandran and
a Somasundaran (1986); and Dai and Chung (1995) investigated
A comparison between the three coreood experiments con-
Bitumen. There is good evidence in the literature to prove that the
ducted on cores saturated with crude oil (A) is shown in Fig. 10.
zeta potential becomes more negative with an increase in the
Sodium chloride solution had the highest recovery factor, whereas
temperature for both rock/brine and oil/brine solutions. At high
CaCl2 had the lowest recovery factor. The oil recovery was
temperatures, the surface hydroxyl groups become more ionized
improved by 8% of OOIP by injecting NaCl instead of CaCl2 at the
due to the release of H from the rock surface, which makes the
same concentration by weight. It shows that the cation type in the
zeta potential more negative, and consequently, increases the value
injected brine plays a signicant role in oil recovery process,
of the zeta potential (Schembre and Kovscek, 2005). Therefore, at
although all the injected brines contained low salinity (less than
212 1F, the zeta potential would be more negative for all the
5000 mg/l). These ndings agree with the expected repulsive
solutions measured in the present work. However, based on the
forces, evaluated by zeta potential measurements, between oil/
measurements from the literature, the trends of the zeta potential
with cation type or cation concentration would be the same, which
means NaCl solutions would have stronger negative charges com-
pared to CaCl2 and MgCl2, and the zeta potential would become
more negative with the reduction of ion concentration.

3.2. Oil recovery by coreood experiments

Waterooding experiments were conducted on Berea sand-

stone cores. The cores were saturated with formation brine at
connate water saturation and crude oil. Three concentrations
(2000; 10,000; and 50,000 mg/l) of solutions were used for
waterooding to run different sets of experiments for comparison
purposes between NaCl, CaCl2, and MgCl2 in secondary recovery
modes. All the experiments were conducted at a temperature of Fig. 8. Oil recovery and pressure drop for experiment with injection of 2000 mg/l
212 1F, a back pressure of 500 psi, and the injection rate was CaCl2 in core #2AL saturated with crude oil (A).
constant at 0.5 cm3/min.

3.3. Recovery of crude oil (A) by 2000 mg/l brines

Sodium chloride solution at 2000 mg/l was injected in core

1AL. Fig. 7 shows the oil recovery versus injected pore volume and
the pressure drop across the core. The recovery factor was 85% of
original oil in place (OOIP) after the injection of 6PV. The injection
was stopped after 13PV as no more oil was recovered during the
injection of the last 5PV. Since the injected brine has a lower
viscosity than the oil, the pressure dropped from 5 to 1.7 psi after
injection of the rst pore volume due to the displacement of oil by
water. Later, the pressure drop stabilized around 2 psi.
The same procedure was followed on core 2AL by injecting
2000 mg/l CaCl2 to investigate the impact of Ca2 on oil recovery. Fig. 9. Oil recovery and pressure drop for experiment with injection of 2000 mg/l
MgCl2 in core#3AL saturated with crude oil (A).
Flooding the core with 2000 mg/l CaCl2 recovered 77% of OOIP
after 3PV as depicted in Fig. 8. The pressure drop decreased and

Fig. 7. Oil recovery and pressure drop for experiment with injection of 2000 mg/l Fig. 10. Comparison of oil recovery for experiments of injection of NaCl, MgCl2, and
NaCl in core #1AL saturated with crude oil (A). CaCl2 at 2000 mg/l in cores saturated with crude oil (A).
 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395
Fig. 11. Comparison of oil recovery for experiments of injection of NaCl and CaCl2
solutions at 10,000 mg/l in cores saturated with crude oil (A).
Fig. 12. Comparison of oil recovery for experiments of injection of NaCl and CaCl2
solutions at 50,000 mg/l in cores saturated with crude oil (A).
brine and solid/brine interfaces. The charges at both interfaces of
oil/brine and solid/brine became more negative when sodium
chloride was used. This resulted in greater repulsion forces, and
hence the electrical double layer expanded and oil recovery
increased as shown by coreood experiments.
Two coreood experiments were conducted at the same condi-
tions on cores saturated with crude oil (A) by injecting 10,000 mg/l
of NaCl and CaCl2. Fig. 11 gives the comparison between these two
coreood experiments. Injection of 10,000 mg/l NaCl solution
improved oil recovery by 11% of OOIP compared to 10,000 mg/l
CaCl2 solution. This demonstrates the efciency of NaCl solution in
oil recovery improvement. Furthermore, the higher oil recovery by
10,000 mg/l NaCl compared to 10,000 mg/l CaCl2 could be related to
the observations of the zeta potential, which showed highly negative
charges at both the oil/brine and brine/solid interfaces by NaCl.
Highly negative charges at rock and oil interfaces increase the
repulsive forces between the oil and rock surface, which might
result in higher oil recovery, as it was noted with 10,000 mg/l NaCl.
Injection of 50,000 mg/l NaCl solution produced higher oil recovery
than 50,000 mg/l CaCl2 as depicted in Fig. 12. This demonstrates that
Na is more favorable for oil recovery improvement than divalent
cations. These observations match with what was reported by
Ligthelm et al. (2009). The authors ran imbibition tests on Berea
sandstone rock using different concentrations of NaCl, CaCl2, and
MgCl2. NaCl solutions showed the highest oil recovery and the most
water-wet surfaces, which agrees with the results of coreood
experiments shown in the present paper. In addition, Brown and
Neustadter (1980) performed contact angle measurements which
showed that divalent cations altered the rock wettability toward
intermediate to oil-wet condition. This demonstrates the effect of
cation type on wettability alteration and supports the ndings of the
presented coreood data.
391
Fig. 13. Comparison of oil recovery by injection of NaCl and CaCl2 solutions at
2000; 10,000; and 50,000 mg/l in cores saturated with crude oil (A).
Fig. 14. Comparison of oil recovery for experiments of injection of different
solutions at 50,000 mg/l in cores saturated with crude oil (B).
All recovery factors of crude oil (A) obtained by injection of
different concentrations of NaCl and CaCl2 are summarized in
Fig. 13 in an ascending order. This comparison aims to show the
dominant parameter between cation type and cation concentra-
tion since both of them have an impact on oil recovery. Fig. 13
shows that the lowest oil recovery factors were achieved by the
three concentrations of CaCl2. Furthermore, injection of
50,000 mg/l NaCl solution (high salinity) recovered more oil than
2000 mg/l CaCl2 solution (low salinity). For the presented cases in
this study, the impact of cation type in the injected brine is more
dominant than the impact of cation concentration.
These results of oil recovery factors agree with the zeta
potential measurements; zeta potential of 50,000 mg/l NaCl
showed higher negative charges at solids surfaces compared to
2000 mg/l CaCl2. The match between coreood experiments and
the zeta potential results validates that the change of electrical
zeta potential at oil/brine and rock/brine by low salinity water may
be one of the involved mechanisms of improving oil recovery by
low salinity water or when the water chemistry is manipulated.
Three coreood experiments were conducted on Berea sand-
stone cores saturated with crude oil (B) to study the effect oil type
on the improvement of oil recovery caused by changing the cation
type. Sodium, calcium, and magnesium were tested in these
experiments by ooding 50,000 mg/l of the cation chloride solu-
tions into different cores to show their effects on oil recovery.
Fig. 14 shows the recovery factor of the three experiments.
Injection of 50,000 mg/l MgCl2 solution did not show an increase
in oil recovery compared to CaCl2 solution. Whereas, almost 16%
incremental oil recovery was achieved by injection of NaCl at the
same weight concentration. This result highlights the high poten-
tial of NaCl to improve oil recovery signicantly with different
types of crude oils.
It is important to note that the coreood experiments pre-
sented in the current study are of a qualitative nature and they are
392 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395

only for comparison purposes to show how the composition of

injected water may play a signicant role in the process of oil
recovery. Waterooding may show high oil recovery factors on the
core scale as it was reported by other authors as well (Zhang et al.,
2007; Pu et al., 2008). However, one may not expect the high oil
recovery factors on the eld scale by waterooding. This could be
due to the large level of heterogeneity in real reservoirs unlike lab
cores, and usually only one or two pore volumes are injected in
the eld.

3.5. Ion exchange

Core efuent samples of waterooding experiments and dry

core tests were analyzed to investigate the rock/brine interaction. Fig. 16. Concentrations of Na , Ca2 , Mg2 , and SO24  in the core efuent samples
after injection of 50,000 mg/l CaCl2 in core #2NP saturated with crude oil (B).

3.6. Analysis of cores saturated with oil and brine

The analysis of the experiments of the injection of 50,000 mg/l

NaCl, CaCl2, and MgCl2 in cores saturated with crude oil (B) and
formation brine is presented. Efuent uid from the core 1NP
during injection of 50,000 mg/l NaCl was analyzed. Ion concentra-
tions versus pore volume injected are shown in Fig. 15. The core was
originally saturated with formation brine, which contained different
cations and anions, therefore, the injected NaCl solution mixed with
the formation brine. This can be indicated from the high concen-
trations of all cations noted during the rst pore volume of injection
and the steep drop of the concentration with continuous injection.
The sodium concentration in the efuent uid dropped from
50,000 mg/l, which is close to the concentration of sodium in
formation brine, to nearly 20,000 mg/l, which equals the concen-
tration of sodium ions in the 50 mg/l NaCl since the concentration
of chloride ions is around 30,000 mg/l as the molecular weight of
chloride is greater than sodium. Interactions between the sodium
chloride solution and rock minerals might take place during the
injection, but it cannot be investigated from the behavior of Na
ions in efuent uid as injected water contained Na ions in the
order of thousands of milligrams per liter, while the interaction
could be in the order of tens or hundreds only. Sulfate ions at the
rst pore volumes injected were high due to the mix between the
injected water (sulfate free) and formation brine that contained
sulfate, and then the concentration was decreasing as an indication
of the continuous dilution of the connate water until it reached zero
after 8PV. The rate of ion concentrations drop of Ca2 and Mg2
was much less after 8PV. This could be evidence of an interaction
between injected brine and rock by leaching cations from the rock
minerals and replacing them with Na .
The same analysis was conducted on the efuent sample of
core 2NP during the ooding of 50,000 mg/l CaCl2, as depicted in
Fig. 16. The concentration of Ca2 was constant due to the
continuous injection of CaCl2 solution. Nevertheless, other ion
Fig. 17. Concentrations of Na , Ca2 , Mg2 , and SO24  in the core efuent samples
after injection of 50,000 mg/l MgCl2 in core #3NP saturated with crude oil (B).
concentrations were high initially, and then they decreasing due to
the mix and dilution between formation brine and injected CaCl2
solution. Sulfate ions dropped to zero after less than 3PV of
injection. Sodium ion reached 60 mg/l at the end of the experi-
ment, and magnesium stabilized at 10 mg/l. Fig. 17 shows the
efuent uid ion concentration for the injection of 50,000 mg/
l MgCl2 into core 3NP. The shapes of the ion concentration curves
are similar to the previous two tests. Sulfate took 7PV to reach to
zero. Sodium and calcium ions stabilized at the end of experiment
at 90 mg/l, and magnesium concentration was constant.
The connate water could be displaced from the core as a bank
ahead of the ooding front (Nielsen et al., 2000), or by mixing and
dispersion (Lake, 1989; Jerauld et al., 2008), and that would
explain why it is required to inject several pore volumes to dilute
the connate water. The mixing between the connate water and the
injected brine depends on the rock wettability (Wang, 1988). There
could be a high degree of mixing in water-wet and mixed-wet
rocks because the water is well connected. Salter and Mohanty
(1982) studied the dispersion coefcient in Berea sandstone, and
they found that it increases linearly with the injection velocity. In
addition, some of the cations might have been adsorbed on the
rock surface during the saturation of the cores with formation
brine due to the interaction between rock and uid. These cations
might be leached from the rock when the core is ooded by brine,
which has a different salinity than the connate water, after it
mixed with connate water. Later, the injected brine started to
leach cations from the rock minerals. Leaching adsorbed cations
from the rock may explain the high concentration of ions in the
efuent uid after the rst PV was injected.

3.7. Analysis of dry cores

Fig. 15. Concentrations of Na , Ca2 , Mg2 , and SO24  in the core efuent samples To conrm the cation exchange between the injected brine and
after injection of 50,000 mg/l NaCl in core #1NP saturated with crude oil (B). rock, brines were injected into dry cores of Berea sandstone so the
 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395
impact of interaction between injected water and formation brine
on efuent uid was eliminated. Sodium chloride, magnesium
chloride, and calcium chloride solutions at 50,000 mg/l were
injected in three different cores. All tests were run at 500 psi
and 212 1F. Concentration versus pore volume injected is shown in
Fig. 18 for the experiment of 50,000 mg/l NaCl injected into core
1D. As the solution of sodium chloride was being injected,
concentrations of sodium ions were constant at a concentration
less than 50,000 mg/l since the chloride ions contribute to the
weight of salts added to the solution, whereas the measured
concentration of the efuent uid was for sodium ions only.
Although the injected water did not contain any calcium or
magnesium, the efuent had a high concentration of calcium
and a lower concentration of magnesium. Calcium concentration
was constant around 60 mg/l, and magnesium was about 9 mg/l. In
addition, the efuent uid contained sulfate, but the concentration
was decreasing with injected pore volumes. These results demon-
strate that there are interactions between the injection brine and
the rock which result in cation exchange. Due to the absence of
calcium and magnesium ions in the injected brine, it is proven that
the ions in the efuent uid were leached from the rock by
replacing them with sodium. Furthermore, the constant concen-
tration of calcium and magnesium ions in the efuent uid proves
that there is an equilibrium concentration at which the injected
brine cannot leach any more cations. The source of leached ions
are mainly clays for Mg2 and calcite for Ca2 , as the clays in the
cores used in this study do not contain montmorillonite, which is
the only clay type that contains Ca2 .
Fig. 19 shows the concentration of ions in the efuent uid for
the experiment of ooding 50,000 mg/l CaCl2. Similarly, calcium
concentration was constant as it was injected in core 2D. The
results show evidence of leaching sodium and magnesium ions by
the injected calcium chloride from the rock surface. However, the
amount of leached sodium ions by CaCl2 injection is less than
Fig. 18. Concentrations of Na , Ca2 , Mg2 , and SO24  in the core efuent samples
after injection of 50,000 mg/l NaCl in dry core #1D.
Fig. 19. Concentrations of Na , Ca2 , Mg2 , and SO24  in the core efuent samples
after injection of 50,000 mg/l CaCl2 in dry core #2D.
393
Fig. 20. Concentrations of Na , Ca2 , Mg2 , and SO24  in the core efuent samples
after injection of 50,000 mg/l MgCl2 in dry core #3D.
calcium ions that was obtained by NaCl injection. Furthermore, the
concentration of sulfate in the efuent uid became zero after only
2PV of injection, but with NaCl injection it took 4PV to reach zero.
This shows that sodium has a higher capacity to leach ions from
the rock surface compared to calcium.
Injection of 50,000 mg/l MgCl2 solution resulted in leaching
some ions from the rock surface of core 3D (Fig. 20). The
concentration of calcium in the efuent uid was around
100 mg/l, which is higher than injection of 50,000 mg/l NaCl. This
can be interpreted by the interaction of Mg2 with calcite, which
results in a dolomitization process, which is the replacing of Ca2
in calcite by Mg2 to form dolomite. Sodium ion concentrations in
efuent uid were much lower than calcium; sodium ions were
about 15 mg/l. Sulfate ions were observed in the efuent uid, but
they reached zero after 3PV of injection which indicated that the
concentration of minerals having sulfate in Berea sandstone core
was very low.
The indication of higher concentrations of ions in the efuent
uid than the injected ions proves that the observed ions in
efuent uid in waterooding experiments during oil displace-
ment are leached from the rock surface, which proves the multi-
ionic exchange by low salinity water. However, these observations
cannot demonstrate that MIE is one of the mechanisms of oil
recovery improvement as it can be only an effect of low salinity
water injection and not a cause of extra oil production. More
investigation is required to examine if MIE can contribute to oil
recovery.
4. Conclusions
The effects of cation type and concentration in the injection
water on oil recovery were investigated. Coreood experiments
were conducted on Berea sandstone cores by injecting different
concentrations of NaCl, CaCl2, and MgCl2 solutions at 212 1F. In
addition, cation exchange tests were run to understand the
interactions between the injected brines and rock. Zeta potentials
at oil/brine and rock/brine interfaces were measured using the
zeta potential technique to examine the effect of cations on the
repulsive forces between oil and rock and relate them to oil
recovery. Based on the results obtained, the following conclusions
can be drawn:
1. Injection of sodium chloride solution has a higher potential for
improving oil recovery compared to the injection of calcium
chloride and magnesium chloride at the same concentrations.
Therefore, treatment of seawater by removal of multivalent
cations is recommended to increase the oil recovery by water-
ooding. However, the modied brine composition should be
suitable for the reservoir to not cause any formation damage.
394 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395
2. The studied cases show that cation type has a signicant
impact on oil recovery, and it could be more dominant than
the effect of cation concentration in the injected brine. There-
fore, optimizing oil recovery by low salinity waterooding is
not only a function of the total dissolved salts in the injected
water, but also the composition and ratios of the cations in
the brine.
3. Injection of single cation brine leaches cations from the rock
surface by replacing them with the cations in the solution,
which proves the interaction between rock and brines.
4. Water chemistry has a signicant impact on the zeta potential
for both oil/brine and rock/brine. Sodium chloride changed the
charges at the oil/brine and rock/brine interfaces to highly
negative.
5. The changes of electrical charge by sodium ions could increase
the repulsive forces between the oil/brine and rock/brine
interfaces, which may result in the expansion of the
double layer.
6. The match between the zeta potential results and coreood
observations suggests that the double layer expansion caused
by the change of zeta potential by low salinity water could be
one of the dominant mechanisms that control oil recovery by
manipulating the injected water chemistry.
Acknowledgments
The authors would like to acknowledge Garrick Brugeyroux for
his help with the experimental work and Kristina Hansen for
proofreading this paper. This work was supported by Texas A&M
University, The Texas Engineering Experiment Station of Texas
A&M University, and The Crisman Institute for Petroleum
Research. We would like to thank Saudi Aramco Company for
partially funding this project and ConocoPhillips Company for
providing the crude oil samples.
References
Agbalaka, C.C., Dandekar, A.Y., Patil, S.L., et al., 2009. Coreooding studies to
evaluate the impact of salinity and wettability on oil recovery efciency.
Transp. Porous Media 76 (1), 7794.
Alotaibi, M.B., Nasralla, R.A., Nasr-El-Din, H.A., 2011. Wettability studies using low-
salinity water in sandstone reservoirs. SPE Reservoir Eval. Eng. 14 (6), 713725.
Austad, T., RezaeiDoust, A., Puntervold, T., 2010. Chemical mechanism of low
salinity water ooding in sandstone reservoirs. In: Paper SPE 129767 Presented
at the SPE Improved Oil Recovery Symposium, Tulsa, 2428 April.
Brown, C.E., Neustadter, E.L., 1980. The wettability of oil/water/silica systems with
reference to oil recovery. J. Candian Pet. Tecnol. 19 (3), 100110.
Buckley, J.S., Takamura, K., Morrow, N.R., 1989. Inuence of electrical surface
charges on the wetting properties of crude oils. SPE Reservoir Eng. 4 (3),
332342.
Dai, Q., Chung, K.H., 1995. Bitumen-sand interaction in oil in sand processing. Fuel
74 (12), 18581864.
Dubey, S.T., Doe, P.H., 1993. Base number and wetting properties of crude oils. SPE
Reservoir Eng. 8 (3), 195200.
Farooq, U., Tweheyo, M.T., Sjblom, J., et al., 2011. Surface characterization of model,
outcrop, and reservoir samples in low salinity aqueous solutions. J. Dispersion
Sci. Technol. 32 (4), 519531.
Jerauld, G.R., Lin, C.Y., Webb, K.J., Seccombe, J.C., 2008. Modeling low-salinity
waterooding. SPE Reservoir Eval. Eng. 11 (6), 10001012.
Hassenkam, T., Mathiesen, J., Pedersen, C. et al. 2012. Observation of the low salinity
effect by atomic force adhesion mapping on reservoir sandstones. In: Paper SPE
154037 Presented at The Improved Oil Recovery Symposium, Tulsa, Oklahoma,
USA, 1418 April.
Hirasaki, G.J., 1991. Wettability: fundamentals and surface forces. SPE Form. Eval. 6
(2), 217226.
Hussain, S.A., Demirci, S., Ozbayoglu, G., 1996. Zeta potential measurements on
three clays from Turkey and effects of clays on coal otation. J. Colloid Interface
Sci. 184 (2), 535541.
Kia, S.F., Fogler, H.S., Reed, M.G., et al., 1987. Effect of salt composition on clay
release in Berea sandstones. SPE Prod. Eng. 2 (4), 277283.
Lager, A., Webb, K.J., Black, C.J.J. et al. 2006. Low salinity oil recovery-an experi-
mental investigation. In: Paper SCA2006-36 Presented at the Society of Core
Analysts, Trondheim, Norway, 1216 September.
Lager, A., Webb, K.J., Black, C.J.J. et al. 2008. LoSal enhanced oil recovery: evidence
of enhanced oil recovery at the Reservoir Scale. In: Paper SPE 113976 Presented
at the SPE/DOE Improved Oil Recovery Symposium, Tulsa, Oklahoma, USA, 19
23 April.
Lake, L.W., 1989. Enhanced Oil Recovery. Prentice-Hall, London, pp. 175181.
Ligthelm, D.J., Gronsveld, J., Hofman, J.P. et al. 2009 Novel waterooding strategy by
manipulation of injection brine composition. In: Paper SPE 119835 Presented at
EUROPEC/EAGE Conference and Exhibition, Amsterdam, The Netherlands, 811
June.
McGuire, P.L.Chatham, J.R., Paskvan, F.K. et al, 2005. Low salinity oil recovery: an
exciting new EOR opportunity for Alaskas North Slope. In: Paper SPE 93903
Presented at the SPE Western Regional Meeting, Irvine, California, USA, March
30April 1.
Menezes, J.L., Yan, J., Sharma, M.M. 1989. The mechanism of wettability alteration
due to surfactants in oil-based muds. In: Paper SPE 18460 Presented at the SPE
International Symposium on Oileld Chemistry held in Houston, TX, USA,
February 810.
Morrow, N., Buckley, J., 2011. Improved oil recovery by low-salinity waterooding. J.
Pet. Technol. 63 (5), 106112.
Nasralla, R.A., Alotaibi, M.B., Nasr-El-Din, H.A. 2011. Efciency of oil recovery by low
salinity water ooding in sandstone reservoirs. In: Paper SPE 144602 Presented
at the SPE Western North American Regional Meeting held in Anchorage,
Alaska, USA, 711 May.
Nasralla, R.A., Bataweel, M.A., Nasr-El-Din, H.A., 2013. Investigation of wettability
alteration by low salinity water in sandstone rock. J. Can. Pet. Technol. 52 (2),
144154.
Nielsen, C.M., Olsen, D., Bech, N. 2000. Imbibition processes in fractured chalk core
plugs with connate water mobilization. In: Paper SPE 63226 Presented at the
SPE Annual Technical Conference and Exhibition, Dallas, Texas, 14 October.
Pu, H., Xie, X., Yin, P., Morrow, N.R. 2008. Application of coalbed methane water to
oil recovery by low salinity waterooding. In: Paper SPE 113410 Presented at
the SPE/DOE Symposium on Improved Oil Recovery, Tulsa, Oklahoma, 2023
April.
Pu, H., Xie, X., Yin, P., Morrow, N.R. 2010. Low-salinity waterooding and mineral
dissolution. In: Paper SPE 134042 Presented at the SPE Annual Technical
Conference and Exhibition, Florence, Italy, 1922 September.
Ramachandran, R., Somasundaran, P., 1986. Effect of temperature on the interfacial
properties of silicates. Colloids Surf. 21, 355369.
Rivet, S., Lake, L.W., Pope, G.A. 2010. A coreood investigation of low-salinity
enhanced oil recovery. In: Paper SPE 134297 Presented at the SPE Annual
Technical Conference and Exhibition, Florence, Italy, 1922 September.
Robertson, E.P. 2007. Low-salinity waterooding to improve oil recoveryhistorical
eld evidence. In: Paper SPE 109965 Presented at the SPE Annual Technical
Conference and Exhibition, Anaheim, California, USA, 1114 November.
Rodrguez, K., Araujo, M., 2006. Temperature and pressure effects on zeta potential
values of reservoir minerals. J. Colloid Interface Sci. 300 (2), 788794.
Salter, S.J., Mohanty, K.K. 1982. Multiphase ow in porous media: I. Macroscopic
observations and modeling. In: Paper SPE 11017 Presented at SPE Annual
Technical Conference and Exhibition, New Orleans, Louisiana, USA, 2629
September.
Schembre, J.M., Kovscek, A.R., 2005. A mechanism of formation damage at elevated
temperature. ASME Trans. J. Energy Res. Technol. 127 (3), 171180.
Scheuerman, R.F., Bergersen, B.M., 1990. Injection-water salinity, formation pre-
treatment, and well-operations uid-selection guidelines. J. Pet. Technol. 42 (7),
836845.
Scheuerman, R.F., Bergersen, B.M. 1989. Supplement to SPE 18461, Guidelines for
Selecting Pretreatment and Well-Operations Fluids. SPE-21298-MS.
Skrettingland, K., Holt, T., Tweheyo, M.T., et al., 2011. Snorre low salinity water
injectioncore ooding experiments and single well eld pilot. SPE Reservoir
Eval. Eng. 14 (2), 182192.
Takamura, K., Chow, R.S., 1985. The electric properties of the bitumen/water
interface Part II. Application of the ionizable surface-group model. Colloids
Surf. 15, 3548.
Tang, G.Q., Morrow, N.R., 1999. Inuence of brine composition and nes migration
on crude oil/bine/rock interactions and oil recovery. J. Pet. Sci. Eng. 24, 99111.
Wang, F.H.L., 1988. Effect of wettability alteration on water/oil relative permeability,
dispersion, and owable saturation in porous media. SPE Reservoir Eval. Eng. 3
(2), 617628.
Webb, K.J., Black, C.J.J., Al-Ajeel, H. 2004. Low salinity oil recoverylog-inject-log.
In: Paper SPE 89379 Presented at the SPE/DOE Symposium on Improved Oil
Recovery, Tulsa, Oklahoma, 1721 April.
Vledder, P., Fonseca, J.K., Wells, T., et al. 2010. Low salinity water ooding: proof of
wettability alteration on a Field Wide Scale. In: Paper SPE 129564 Presented at
the SPE Improved Oil Recovery Symposium, Tulsa, Oklahoma, 2428 April.
Yousef, A.A., Al-Saleh, S.H., Al-Kaabi, A., 2011. Laboratory investigation of the impact
of injection-water salinity and ionic content on oil recovery from carbonate
reservoirs. SPE Reservoir Eval. Eng. J. 14 (5), 578593.
Yousef, A.A., Liu, J.S., Blanchard, G.W.et al. 2012. Smartwater ooding: industrys
rst eld test in carbonate reservoirs. In: Paper SPE 159526 Presented at the
SPE Annual Technical Conference and Exhibition, 810 October, San Antonio,
Texas, USA.
Yukselen, Y., Kaya, A., 2003. Zeta potential of kaolinite in the presence of alkali,
alkaline earth and hydrolyzable metal ions. Water Air Soil Pollut. 145, 155168.
 R.A. Nasralla, H.A. Nasr-El-Din / Journal of Petroleum Science and Engineering 122 (2014) 384395 395

Zhang, D.L., 2006. Surfactant-Enhanced Oil Recovery Process for a Fractured, Oil-
Wet Carbonate Reservoir (Ph.D. Dissertation). Rice University, Houston, Texas.
Zhang, Y., Morrow, N.R. 2006. Comparison of secondary and tertiary recovery with
change in injection brine composition for crude oil/sandstone combinations. In:
Paper SPE 99757 Presented at the SPE/DOE Symposium on Improved Oil
Recovery, Tulsa, Oklahoma, 2226 April.
Zhang, Y., Xie, X., Morrow, N.R. 2007. Waterood performance by injection of brine
with different salinity for reservoir cores. In: Paper SPE 109849 Presented at the
SPE Annual Technical Conference and Exhibition, Anaheim, California, 1114
November.