Laboratory Investigation of the Impact of
Injection-Water Salinity and Ionic Content
on Oil Recovery From Carbonate Reservoirs
Ali A. Yousef, Salah Al-Saleh, Abdulaziz Al-Kaabi, and Mohammed Al-Jawfi, Saudi Aramco
Summary
The impact of brine salinity and ion composition on oil recov-
ery has been an area of research in recent years. Evidence from
laboratory studies, supported by some field tests targeting mainly
sandstones, has distinctly shown that injecting low-salinity water
has a significant impact on oil recovery. Although the potential for
carbonates has not been thoroughly investigated, some reported
studies have excluded carbonates from this effect. The main
objective of this paper is to investigate the potential of increased
oil recovery by altering the salinity and ionic composition of
the injection water for carbonate reservoirs, define the recovery
mechanisms, and eventually transform the emerged trend to full-
fledged reservoir technology.
This paper presents the results of different laboratory studies
to investigate the impact of salinity and ionic composition on
oil/brine/rock interactions and draws conclusions on potential
recovery mechanisms. Also, it provides a laboratory coreflooding
study conducted using composite rock samples from a carbonate
reservoir to investigate the impact of salinity and ionic composi-
tion on oil recovery. The experimental parameters and procedures
were well designed to reflect the reservoir conditions and current
field injection practices, including reservoir pressure, reservoir
temperature, and salinity and ionic content of initial formation
water and current types of injected water.
The experimental results revealed that substantial tertiary oil
recovery beyond conventional waterflooding can be achieved by
altering the salinity and ionic content of field injected water. The
new emerged trend is distinct from what has been addressed in
previous reported studies on topics of low-salinity waterflooding
for sandstones or seawater injection into high-temperature chalk
reservoirs. On the subject of recovery mechanisms, the results
showed that altering the salinity and ionic composition of the
injected water has a significant impact on the wettability of the rock
surface. Also, nuclear-magnetic-resonance (NMR) measurements
indicated that dilution of seawater can cause a significant alteration
in the surface relaxation of the carbonate rock and also can enhance
connectivity among pore systems because of rock dissolution. The
results, observations, and interpretations addressed in this study
provided compelling evidence to suggest that the key mechanism
for the emerged trend is wettability alteration.
Introduction
Waterflooding, by all measures, has been the most successful
method for recovering oil from reservoirs. The key grounds for
the success of waterflooding include
1. Water is an efficient injectant for displacing oil of light to
medium gravity.
2. Water is relatively easy to inject into oil-bearing formations.
3. Water is available and, most importantly, inexpensive.
4. Waterflooding involves much lower capital investment and
operating costs, leading to favorable economics compared to
enhanced-oil-recovery methods.
Copyright © 2011 Society of Petroleum Engineers
This paper (SPE 137634) was accepted for presentation at the SPE Canadian Unconventional
Resources and International Petroleum Conference, Calgary, Alberta, Canada, 19–21
October 2010, and revised for publication. Original manuscript received 11 September 2010.
Revised manuscript received 1 June 2011. Paper peer approved 23 June 2011.
578
The target of any waterflood reservoir management is prin-
cipally to maximize the ultimate oil recovery. The attention has
been given historically to improve the volumetric sweep efficiency
through a number of technologies and practices such as in-fill
drilling, multilateral wells, improved reservoir characterization,
high-resolution reservoir simulation, and advanced monitoring and
surveillance. Because waterflooding has been viewed as a physi-
cal process to maintain reservoir pressure and drive oil toward the
producing wells, less attention has been given to the role of the
chemistry of the injection water and its impact on oil recovery.
In recent years, extensive research has shown that tuning salinity
and ionic composition of the injected water can favorably affect
oil/brine/rock interactions, alter rock wettability, enhance micro-
scopic displacement efficiency, and eventually improve waterflood
oil recovery. One emerged trend targeting sandstone reservoirs has
shown that injecting low-salinity water can improve oil recovery
significantly.
Tuning the salinity and ionic composition of the injection
water is relatively new and currently in the research and develop-
ment stage. There have been a few field trials and pilots, all in
sandstones. The initial results are promising. While many recov-
ery mechanisms are proposed, many questions and uncertainties
still remain with respect to the oil-recovery mechanisms and the
role of the injection-water chemistry. The potential for carbonate
reservoirs has not been investigated thoroughly and some of the
reported studies have excluded carbonates from this effect (Lager
et al. 2006; RezaeiDoust et al. 2009).
Through its upstream research arm (the Advanced Research
Center), Saudi Aramco has initiated a research program called
“SmartWater Flood” to explore the potential of increasing oil
recovery by tuning the injection-water properties [e.g., salinity,
ionic composition, interfacial tension (IFT), and viscosity]. Sev-
eral Saudi Aramco reservoirs have natural waterdrives augmented
by peripheral water-injection programs since the mid-1950s. The
produced water is reinjected. A string of development of the injec-
tion system has been implemented over the past 60 years. This has
resulted in unique water-injection infrastructure, considered today
the largest in the world. Currently, the primary source of the injec-
tion water is seawater. The potential of obtaining incremental oil
recovery through tuning the injected-water properties is significant,
considering the current injection-water facilities as well as the large
oil resources of the Saudi Arabia.
This paper provides first a review on general trends that have
emerged in the literature related to injection-water chemistry and
then presents the results of laboratory studies to investigate the
impact of salinity and ionic composition on oil/brine/rock inter-
actions. Afterward, the study provides a laboratory coreflooding
study conducted using composite rock samples from a carbonate
reservoir to investigate the impact of salinity and ionic composi-
tion on oil recovery.
Historical Background
The idea of injecting low-salinity water into petroleum reservoirs
has been addressed since the 1960s. Bernard (1967) demonstrated
that injection of fresh water both in secondary and tertiary modes
can increase oil recovery from sandstone cores containing clays;
he also stated that fresh waterflooding is usually accompanied by
reduction in permeability and the development of a relatively high
October 2011 SPE Reservoir Evaluation & Engineering
 TABLE 1—BASIC PETROPHYSICAL PROPERTIES FOR ROCK SAMPLES
Sample # Length (cm) Dia. (cm) Air K (md)
A 3.87 3.80 1.0
B 3.88 3.80 2.0
pressure drop. However, this work clearly did not capture the atten-
tion of the petroleum industry. The research work of Jadhunandan
(1990) pointed out one more time that injecting low-salinity water
into sandstone core samples can affect oil recovery. Extensive
research efforts (Jadhunandan and Morrow 1995; Yildiz and Mor-
row 1996; Tang and Morrow 1997; Tang and Morrow 1999; Tang
and Morrow 2002; Zhang and Morrow 2006; Zhang et al. 2007)
have developed this idea into an emerging trend. The research
efforts of Webb et al. (2005a), Lager et al. (2006), and Lager
et al. (2007) have confirmed and validated the new trend through
reservoir-conditions coreflood experiments. Lager et al. (2007)
reported that the average increase in oil recovery from more than
20 reservoir coreflood experiments was approximately 14%. The
laboratory results were confirmed by field tests including log-
inject-log and different single-well chemical-tracer tests (Webb
et al. 2004; McGuire et al. 2005; Lager et al. 2008).
The efforts in the past 2 decades have been devoted to
understanding recovery mechanisms of low-salinity waterflood-
ing. Although different mechanisms have been proposed, many
questions and uncertainties remain. Subsequently, it is well docu-
mented that the effect of low salinity is related to the presence of
clay minerals (Tang and Morrow 1999; Lager et al. 2006), and
consequently, it is generally accepted that the effect is caused
by wettability alteration of clay minerals. The main mechanisms
proposed for wettability alteration include fines migration (Tang
and Morrow 1999), pH increase leading to IFT reduction (McGuire
et al. 2005), multi-ion exchange (Lager et al. 2006), and double-layer
expansion (Liegthelm et al. 2009; RezaeiDoust et al. 2009). Lager et
al. (2006) showed that a pH increase and fines migration are symp-
toms of low-salinity effect rather than potential mechanisms. Most
recently, Berg et al. (2009) provided direct experimental evidence
indicating multi-ion change and/or double-layer expansions are the
potential mechanisms for low-salinity waterflooding.
The effect of low-salinity-water injection has been observed
in both secondary and tertiary modes. However, the recent work
by Loahardjo et al. (2008) showed that secondary low-salinity
recovery using restored cores should not be attributed only to low-
salinity effect. To confuse matters more, Rivet (2009) conducted
a string of coreflood experiments using long cores to investigate
the effect of low-salinity waterflooding on oil recovery, residual-oil
saturation, and relative permeability. The most interesting result
is that tertiary low-salinity recovery was never observed in these
coreflood experiments.
On the basis of what has been published so far in the literature,
the mechanisms are linked mainly to the presence of clay minerals,
oil composition, the presence of formation water with high concen-
tration of divalent cations (i.e., Ca2+, Mg2+), and a salinity level of
the low-salinity water in the range of 1,000 to 5,000 ppm.
Another research trend that recently emerged is that inject-
ing seawater rather than any other type of water will improve oil
recovery from chalk reservoirs (Austad et al. 2005; Strand et al.
2006; Zhang and Austad 2006; Zhang et al. 2007; Austad et al.
2008). Alteration to the injection-water composition can impact
rock wettability and eventually provide additional oil recovery.
This effect is attributed to the reactivity of key seawater ions
(SO42–, Ca2+, Mg2+) that have the capability to change rock surface
charges, release adsorbed carboxylic oil components from the rock
surface, alter rock wettability, and eventually improve oil recovery.
Webb et al. (2005b) investigated the impact of the sulfate ion on
the imbibition capillary pressure curve and saturation changes
using two identical chalk cores. Sulfate-free formation water was
used as initial water saturation in both cores, and seawater and
sulfate-free formation water were used as imbibing fluids. The
results showed that seawater was able to alter the wettability of the
October 2011 SPE Reservoir Evaluation & Engineering
Brine K (md) Porosity (%) Target Study
– – Wettability Study
– – Wettability Study
chalk core sample to more water-wet state. This trend has so far
been demonstrated through spontaneous-imbibition tests in which
spontaneous-imbibition oil recovery showed a significant depen-
dence on temperature—the higher the temperature, the higher the
oil recovery. The conditions necessary to trigger this effect on the
basis of reported studies include oil with high polar components,
sulfate-free formation water, temperature greater than 90°C, and a
high concentration of key seawater ions in the injected water.
On the basis of published research work (Austad et al. 2005;
Strand et al. 2006; Zhang and Austad 2006; Zhang et al. 2007;
Austad et al. 2008), different mechanisms for wettability alteration
have been proposed, including surface-charge alteration by adsorp-
tion of SO42– with coadsorption of Ca2+ on chalk-rock surface, and
substitution of Ca2+ on chalk-rock surface by Mg2+ because of an
increase in ion reactivity at higher temperature. During imbibitions
of seawater into a chalk rock sample, it is proposed that sulfate
ion (SO42–) will adsorb on a positively charged chalk surface.
Consequently, the bond between a negative oil component and the
rock surface will deteriorate. Because of a decrease in the positive
surface charge, more Ca2+ ions will be able to attach to the rock
surface allowing the release of negatively charged oil component.
As temperature increases, this effect becomes more pronounced
and this represents one explanation of the correlation between oil
recovery and temperature observed in spontaneous-imbibition tests
(Strand et al. 2006). Also, it is proposed that at higher temperatures,
these ions become more reactive with the chalk-rock surface. This
will induce the substitution of Ca2+ on rock surface for Mg2+.
Most recently, another research effort has argued with sur-
face-charge-alteration mechanisms, as described earlier. Hiorth
et al. (2010) investigated how water chemistry affects surface
charge and rock dissolution in a pure calcium carbonate rock by
constructing and applying a chemical model that couples bulk
aqueous and surface chemistry and also addresses mineral pre-
cipitation and dissolution. The developed chemical model was
used to predict temperature dependence of oil recovery reported
in spontaneous-imbibition experiments (Zhang and Austad 2006;
Zhang et al. 2007; Austad et al. 2008). The results indicated that
the surface-charge alteration cannot explain the observed increase
in spontaneous oil recovery caused by seawater imbibition and/or
temperature. Because the precipitation/dissolution model was able
to predict temperature dependence of oil recovery with imbibing
fluids, mineral dissolution was proposed as a controlling factor in
the reported spontaneous-imbibition data.
Experimental Materials
Rock-Samples Selection and Preparation. The rock material was
selected from a carbonate reservoir. Core plugs (1-in. in diameter
and 1.5-in. in length) were cut from whole cores. Different labora-
tory tests were performed to select consistent rock samples in terms
of petrophysical properties as well as rock types; this includes
routine core analysis, X-ray computerized tomography (CT) scan,
and NMR T2 distribution. Routine core analysis was first conducted
to measure the dimensions, air permeability, porosity, and pore vol-
ume of core plugs. The core plugs were then CT scanned to screen
out any core with fractures or permeability barriers. Afterward,
saturation cores with field connate water were NMR analyzed to
sort core samples into composites with similar rock types. Table 1
lists petrophysical properties of the selected rock samples for a
recovery-mechanism study. Also, two composite core sets were
selected for coreflooding study. Tables 2 and 3 list the petrophysi-
cal properties of the selected cores for both composites.
A rock sample from the targeted reservoir was crushed to
determine the main rock components. X-ray diffraction (XRD)
technique was used to identify the chemical composition of
579
 TABLE 2—BASIC PETROPHYSICAL PROPERTIES FOR CORE PLUGS USED IN THE FIRST COREFLOODING EXPERIMENTS

Sample # Length (cm) Diameter (cm) Air Permeability (md) Brine Permeability (md) Porosity (%)

1 4.04 3.81 51.00 35.00 22.10

2 4.25 3.81 78.50 53.80 20.80
3 4.02 3.80 71.90 45.71 28.90
4 3.93 3.80 47.60 30.55 28.70
Total/Avg 16.24 3.80 59.8 39.6 25.1

TABLE 3—BASIC PETROPHYSICAL PROPERTIES FOR CORE PLUGS USED IN THE SECOND COREFLOODING
EXPERIMENTS

Sample # Length (cm) Diameter (cm) Air Permeability (md) Brine Permeability (md) Porosity (%)

5 3.94 3.81 110.96 74.34 22.57

6 4.16 3.81 88.72 59.44 27.73
7 3.83 3.81 109.35 73.26 24.97
8 3.77 3.81 96.28 64.51 25.65
9 4.02 3.81 109.33 73.25 26.60
10 3.93 3.81 97.40 65.26 20.36
Total/Avg 23.65 3.81 102.0 68.3 24.65

29,000 ppm), 10-times diluted (approximately 6,000 ppm), 20-

TABLE 4—GEOCHEMICAL ANALYSIS FOR MAJOR
SOURCES OF WATER times diluted (approximately 3,000 ppm), and 100-times diluted
(approximately 600 ppm).
Field Connate The effect of salinity, as well as ion composition, on the
Ions Water (ppm) Seawater (ppm) physical properties (density and viscosity) of prepared waters was
studied. The density and viscosity properties were measured at a
Sodium 59,491 18,300
reservoir temperature of 212°F. Table 5 shows the density and
Calcium 19,040 650 viscosity of different water types.
Magnesium 2,439 2,110 Reservoir-Oil Samples. Reservoir-oil samples were used in
Sulfate 350 4,290 this study. Crude-oil filtration was conducted to remove solids
Chloride 132,060 32,200
and contaminants to reduce any experimental difficulties during
coreflood experiments. In this work, live oil was used that was
Carbonate 0 0 recombined from an oil/gas separator such that the experimental
Bicarbonate 354 120 conditions closely resembled reservoir conditions. The composi-
Total dissolved solids 213,734 57,670 tion of crude oil, total acid number, and other oil properties are
listed in Table 6.

crushed materials. The crushed material is composed of approxi-
mately 80% calcite, 13% dolomite, 6% anhydrite, and less than
1% quartz.
Fluid Properties. Brines. Different brines were used in this study,
including field connate water, injection seawater, and different
dilution versions of injection seawater. All brines were prepared
from distilled water and reagent grade chemicals on the basis of
geochemical analysis of field water samples. Table 4 depicts the
geochemical analysis and the corresponding chemical concentra-
tions for each type of brine. For experimental work described
later, seawater had a salinity of approximately 57,600 ppm, and
initial connate water is very saline with salinity of 213,000 ppm
by weight.
The salinity of the injection seawater (Table 4) is almost
double the typical salinity of ocean seawater. Other dilute versions
of seawater were also prepared by mixing with different vol-
umes of deionized water, including twice diluted (approximately
Methods, Equipment, and Procedures
Mechanism Study. Wettability alteration always has been pro-
posed as the driving mechanism for improved oil recovery by
altering the salinity and ionic composition of the injected water.
During waterflooding, different forces control fluid flow in porous
media including viscous, capillary, and gravity forces. Capillary
forces are the most dominant at the end of the waterflooding and
create what we refer to as the residual-oil saturation. To mobi-
lize the residual oil, a significant reduction in capillary forces is
required. Capillary forces are a function of fluid/fluid, and fluid/
rock interactions. IFT measurements between oil and water and
rock-wettability measurements (i.e., contact angle) are typically
used to measure these interactions.
IFT Measurements. IFT measurements were conducted using
reservoir live oil and different-salinity slugs of injection seawater
(Tables 4 and 6). All measurements were carried out at reservoir
conditions, which are the same conditions at which coreflood experi-
ments will be conducted. We used a high-temperature/high-pressure

TABLE 5—DENSITY AND VISCOSITY OF DIFFERENT WATER TYPES AT 212°F

20 Times
Field Twice 10 Times Diluted 100 Times
Property Connate Water Seawater Diluted Seawater Diluted Seawater Seawater Diluted Seawater
3
Density (g/cm ) 1.1083 1.0152 0.9959 0.9812 0.9782 0.9779
Viscosity (cp) 0.476 0.272 0.242 0.232 0.212 0.193

580 October 2011 SPE Reservoir Evaluation & Engineering

 TABLE 6—RESERVOIR FLUID PROPERTIES OF OIL
SAMPLES
Component Amount
Saturates 39.17%
Aromatics 48.30%
Resins 7.04%
Asphaltenes 5.50%
Total Acid Number 0.25 mg KOH/g oil
Saturation pressure, psia at 212°F 1,804
Gas/oil ratio, SCF/STB 493
Stock tank oil gravity °API at 60°F 30.0
3
Dead oil density at room temperature, lb/ft 54.50
Dead oil viscosity at room temperature, cp 14.59
pendent-drop instrument to measure IFT values. Fig. 1 shows a
schematic of the experimental equipment used in this study. The
main parts of the instrument are the IFT chamber cell, the hand
pump for injection of oil or water, a vibration-free table, needle,
temperature-control system, lamp, transfer cells, pressure transduc-
ers with digital display, and a fully automated imaging system.
The imaging system allows a direct digitization of the drop image
with the aid of a video frame grabber of a digital camera. IFT
measurements were calculated from drop shape by the Young-
Laplace equation.
To determine the IFT between fluids, we used a pendent-drop
tensiometry (Fig. 2). A small oil drop is injected upwards at the tip
of a stainless-steel needle immersed in the brine. The experimental
procedure is described in Appendix A.
Contact-Angle Measurements at Reservoir Conditions. Con-
tact angle is considered one of the most common methods to
quantify rock wettability. It was used in this study to address the
impact of injecting different-salinity slugs of seawater on carbon-
ate-rock wettability. The general conventional classification of
contact angle is (Anderson 1986) water-wet, 0° to approximately
75°; intermediate-wet, 75° to approximately 115°; and oil-wet,
115° to approximately 180°.
The pendent-drop instrument (Fig. 2) was also used to mea-
sure the contact angle of carbonate-rock samples with live oil and
different-salinity slugs of seawater at reservoir conditions. Fig. 3
shows a diagram of the contact-angle chamber used in the test. To
obtain an insight on the impact of injection of different-salinity
slugs of field seawater on rock-sample wettability, it is critical to
measure contact-angle values using the same procedure at which
the coreflood experiments will be conducted. For the same rock
sample, the measurements were conducted in a sequential mode:
field connate water, regular seawater, twice-diluted seawater, 10-
times-diluted seawater, 20-times-diluted seawater, and eventually
100-times-diluted seawater.
Oil
Brine
Fig. 2—Injection of oil drop upward at the needle tip in brine
solution.
October 2011 SPE Reservoir Evaluation & Engineering
Monitor &
Camera IFT Cell Brine Cell
Computer
Control Box
Live Oil Water Bath
Cylinder Quizix Pump
Fig. 1—System setup for IFT measurements at reservoir
conditions.
Besides the procedure used in conducting contact-angle mea-
surements, another important step is the selection and cleaning of
rock-plate samples. The samples were obtained from tight-rock
samples characterized by very low permeability (approximately
2-md air permeability) to avoid oil-drop imbibition in the rock
plate while making the measurement. Also, rock plates were then
washed with distilled water and ethanol. To restore rock wettabil-
ity, rock plates were first aged in connate water, and then aged in
the field oil for 6 weeks. The experimental procedure followed is
described in Appendix B.
Coreflooding Study. Two coreflood experiments were conducted
to investigate the impact on oil recovery of altering the salinity
and ionic composition of the injection water. The objective of the
second coreflood experiment is to confirm and validate results of
the first coreflood experiment.
Determination of Pore Volume and Initial Water Saturation
(Swi). The pore volume of cores, original oil in place, and connate-
water saturation of selected composite core plugs were determined
using a centrifuge apparatus. The procedure for preparation of each
core was as follows:
1. Measure dry weight of the core sample.
2. Saturate core plug under vacuum for 5 to 7 days with field
connate water to achieve ionic equilibrium with the core samples.
3. Measure wet weight.
4. Determine pore volume by weight difference and the density
of field connate water at room temperature.
5. Centrifuge each core plug at 5,000 rev/min for 12 hours to drain
the water in the pores and establish the initial water saturation.
6. Measure weight of centrifuged core sample.
7. Determine weight difference (Step 4 and Step 6) to esti-
mate initial water saturation by using the density of field connate
water.
Rock Plate
Oil Drop
Needle
Fig. 3—A diagram for contact-angle chamber.
581
 TABLE 7—PORE-VOLUME DETERMINATION AND WATER-SATURATION RESULTS FOR FIRST COMPOSITE CORES

Wet Wt. After Fluid

Wet Liquid 5,000 RPM for Difference Produced Remaining Swi
3 3 3
Sample # Dry Wt. (g) Wt. (g) Wt. (g) PV (cm ) 12 Hours (g) Wt. (g) Fluid (cm ) in Rock (c m ) (%)

2 101.53 110.76 9.23 8.08 102.78 7.98 6.98 1.09 13.5

3 81.22 92.48 11.26 9.85 82.19 10.29 9.01 0.85 8.6
4 81.95 93.93 11.98 10.48 82.76 11.17 9.78 0.71 6.8
1 92.88 102.26 9.38 8.21 94.22 8.04 7.04 1.17 14.3
10.4
Total/Avg. 36.63 32.80 3.82
4
*PV = 36.63 cm3, OOIC = 32.82 cm3, Average Swi = 10.44%

Inlet Outlet

Tables 7 and 8 list the pore volume and the Swi for two com-
posite core plugs. For the first composite-core set, the total pore
volume was 36.63 cm3, the original oil in cores (OOIC) was 32.80
cm3, and the average Swi was 10.44%. For the second composite-
core set, the total pore volume for the composite was 63.51 cm3,
the OOIC was 54.37 cm3, and the average Swi was 14.40%. The
position of each core plug in the composite sample is ordered by
a harmonic arrangement. The diagrams in Tables 7 and 8 show the
core plugs arrangement.
Coreflooding Apparatus. The coreflooding apparatus used in
this research work is custom designed to perform experiments
with composite-core plugs to evaluate oil recovery using water-
flooding or any other type of injectants at reservoir conditions.
A diagram of the coreflooding apparatus is depicted in Fig. 4. The
main components of the apparatus are an oven, a stainless-steel
core holder, fluid accumulators, a differential-pressure array, two
Quizix pumps, a backpressure regulator (BPR), a confining-pres-
sure module, and a three-phase separator.
The flooding system is capable of handling temperatures up to
150°C, pore pressures up to 9,500 psi, and overburden pressures
up to 10,000 psi. Volumes of oil and different-salinity brines are
supplied from high-pressure floating-piston accumulators, oper-
ated by external high-pressure pumps. Oil and brine injection was
accomplished through a Quizix pump connected by a set of valves
ahead of the core holder. System pressure is maintained by a BPR
at the core outlet and measured by absolute- and differential-pres-
sure transducers; and these data are registered by a computer-based
data-acquisition- and -control board. The coreflooding apparatus is
equipped with a three-phase separator, used to measure the recovered
oil during waterflooding. The separator is placed inside the oven
in a mounting bracket and operates at reservoir pressure and
temperature. The three-phase separator with a two-bore pattern is
primarily used for phase-level measurement of the oil/water and
gas/oil interfaces at test pressure and temperature.
Experimental Procedures. The coreflooding apparatus was
used to mimic reservoir conditions during a waterflood experiment.
The experimental procedure is given in Appendix C.
Impact of Injection-Water Chemistry on Carbonate Rock
Samples. A laboratory NMR instrument was used in the current
research study to investigate the impact of tuning the salinity and
ionic content of the injection water on carbonate-rock samples used
in the coreflooding study. The objective of these measurements is
not to infer rock wettability by NMR, but to determine the impact
of injecting different-salinity slugs of seawater on pore geometry
or pore-size distribution, and also reactivity of field connate water
with carbonate rock surface.
NMR Technique. NMR has emerged as a rapid, nondestruc-
tive, and noninvasive measurement technique for both laboratory
and field applications. There have been considerable efforts made
in the last few decades to understand the NMR properties of flu-
ids in a porous medium. It has been documented that a number
of rock properties of practical interest are correlated with NMR
amplitude and relaxation times (Borgia et al. 1991; Kenyon 1992;
Howard 1998; Bryar and Knight 2003). These include pore-size
distribution, porosity, permeability, rock wettability, hydraulic
permeability, pore fluids identification, and others. As a result
of those laboratory studies, novel bench-type NMR instruments

TABLE 8—PORE-VOLUME DETERMINATION AND WATER-SATURATION RESULTS FOR SECOND COMPOSITE CORES

Wet Wt. After Fluid

Wet Liquid 5,000 RPM for Difference Produced Remaining Swi
3 3 3
Sample # Dry Wt. (g) Wt. (g) Wt. (g) PV (cm ) 12 Hours (g) Wt. (g) Fluid (cm ) in Rock (c m ) (%)

5 91.20 102.72 11.52 10.08 92.65 10.07 8.81 1.27 12.6

6 89.39 103.45 14.06 12.31 91.45 12.00 10.50 1.80 14.7
7 83.21 95.19 11.98 10.48 84.00 11.19 9.79 0.69 6.6
8 82.75 94.85 12.10 10.59 85.05 9.80 8.58 2.01 19.0
9 87.60 100.69 13.09 11.46 89.91 10.78 9.43 2.02 17.6
10 94.25 104.07 9.82 8.59 95.79 8.28 7.25 1.35 15.7
Total 63.51 54.37 9.15 14.40
*PV = 63.51 cm3, OOIC = 54.37 cm3, Average Swi = 14.40%

Inlet Outet

582 October 2011 SPE Reservoir Evaluation & Engineering

 Fig. 4—Schematic of the coreflooding apparatus.
have been designed to measure/infer petrophysical properties for
reservoir-rock samples.
In general, the T2 relaxation rate of proton nuclear spins in
a fluid sample in a porous rock can be described as (Kenyon
1992):
1 1 S D
+  + (G e ) ,
2
= . . . . . . . . . . . . . . . . . . . . . . . (1)
T2 T2 B V 12
where T2B–1 is the relaxation rate of the bulk fluid, S/V is the surface-
area-to-volume ratio of the pores, and  is the surface relaxivity.
Surface relaxivity () is a geochemical property describing the
capacity of the grain surface to enhance relaxation, and it generally
increases with the concentration of paramagnetic impurities on a
surface (e.g., Mn2+, Fe3+) (Foley et al., 1996; Bryar et al., 2000).
The product  (S/V) is referred to as T2 relaxation rate at the surface
and reflects the effect of both pore geometry and geochemistry or
water chemistry on the pore surface. The third term describes the
T2 relaxation rate because of diffusion in a magnetic-field gradient
(Callaghan 1991). D is the molecular self-diffusion of the water, G
is the magnetic-field gradient,  is the gyromagentic ratio of the
hydrogen nucleus, and e is the echo time, a constant parameter
for the measurement. Relaxation in rock samples with negligible
magnetic-field gradients is dominated by surface relaxation, in
which case the expression for T2–1 is simplified to
Fig. 5—Image of the laboratory NMR system.
October 2011 SPE Reservoir Evaluation & Engineering
1 S
=  , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)
T2 V
In porous rocks, the rock grains usually vary in size and
typically have different pore systems that lead to an effective
distribution of pore sizes and, accordingly, a distribution of NMR
relaxation times.
The Apparatus. The NMR system used is the Maran DRX 2
MHz (Fig. 5), which has a 2-MHz permanent magnet with a 1D
electromagnetic-gradient coil. NMR T2 distributions were deter-
mined using a BDR inversion scheme in which the amplitude of
the decay signal can be fit by a sum of decaying exponentials and
the corresponding amplitudes form T2 distribution.
Experimental Procedure. NMR T2 measurements were con-
ducted for all rock samples used in the coreflooding study before
and after smart waterflooding. Different post-test NMR runs were
conducted for each rock sample to confirm and validate NMR
response. For NMR measurements before smart waterflooding,
NMR tests were conducted with cleaned rock samples fully satu-
rated by field connate water. After smart waterflooding, NMR tests
were conducted after cleaning all core samples with solvent and
restoring saturation with field connate water. In other words, both
NMR tests (before and after coreflooding test) were conducted
with cores at Sw = 1. The cleaning process used in this work is the
Soxhlet method in which toluene was injected until the effluent
was transparent, followed by injection of methanol.
Results and Observations
Mechanism Study. IFT Measurements. Fig. 6 shows different
IFT measurements of the reservoir live oil with field connate water,
regular seawater, and then different diluted versions of seawater.
The general trend is that as the salinity of the injection water
decreases, and the IFT decreases. The significant reduction in IFT
(approximately six units) was observed only when field connate
water was replaced by regular seawater. However, different diluted
versions of seawater showed an insignificant effect on IFT. Because
the measurement was repeated several times and the trend is still
the same, this suggests that injection of different-salinity slugs of
seawater has an insignificant impact on the IFT, and consequently
on fluid/fluid interactions.
Contact-Angle Measurements at Reservoir Conditions. Fig. 7
shows real images for wettability measurements using connate water,
seawater, and different-salinity slugs of seawater. All measurements
583
 42.0

Test-1

40.0 Test-2

Test-3
38.0
Test-4

IFT, dyne/cm
36.0

34.0

32.0

30.0
100-Times- 20-Times- 10-Times- Twice- Connate
Seawater Water
Diluted Diluted Diluted Diluted
Seawater Seawater Seawater Seawater

Fig. 6—IFT measurements of reservoir live oil with connate water, injection seawater, and different diluted versions of seawater.
The measurements were conducted at reservoir conditions.

were monitored over a period of 2 days to accurately determine
the impact of each type of water on rock wettability. In this test,
the contact angle with field connate water is approximately 90°,
indicating intermediate wettability of the rock sample. Regular
seawater did not affect the contact angle even after 2 days, as
depicted in Fig. 7. We observed a significant change in the con-
tact angle with twice-diluted seawater; the angle changed from
approximately 90° to 80°, which indicates that the rock becomes
more water-wet. With 10-times-diluted seawater, the contact angle
further altered from approximately 80° to 69° and now the rock is
in the water-wet zone. Less alteration has been observed with 20-
times-deluted seawater, and almost no significant modification has
been seen with 100-times-diluted seawater. This test suggests that
injecting different-salinity slugs of field seawater can significantly
change rock wettability toward a water-wet state.
The test was repeated with new rock-plate samples (Fig. 8).
The trend is very similar, in which twice-diluted and 10-times-
diluted seawater showed significant changes to rock wettability.
This confirmed and validated that injecting different-salinity slugs
of seawater has a significant impact on rock wettability, and ulti-
mately has the potential to provide additional oil recovery, as will
be demonstrated in coreflood experiments.
The results of two more tests, as shown in Fig. 8, also illustrated
that regular seawater is able to change rock wettability toward the
water-wet state. This suggests that injecting seawater into com-
posite cores provided more oil recovery compared with the use of
other sources of water, such as formation water.
Coreflooding Study. First Reservoir-Condition Coreflood Exper-
iment. In the coreflood experiment, five different-salinity slugs

φ o = 90 φo = 90 φo = 99.1
φ w = 90 φ w = 90 φw = 80.9

Connate water Seawater: 60 kppm Twice-Diluted Seawater: 30 kppm

Water angle:90 Water angle:90 Water angle:80.9

φ o = 111 φ o = 117 φ o = 117.8

φ w = 69 φ w = 63 φ w = 62.2

10-Times-Diluted Seawater: 6 kppm 20-Times-Diluted Seawater: 3 kppm 100-Times-Diluted Seawater: 0.6 kppm
Water angle:69.2 Water angle:63 Water angle:62.2

Fig. 7—Images of contact-angle measurements of carbonate rock samples with reservoir live oil and connate water, injection
seawater, and different dilution versions of seawater. The measurements were conducted at reservoir conditions.

584 October 2011 SPE Reservoir Evaluation & Engineering

 100
95 Test 1
90 Test 2
Intermediate-wet Zone
85

Contact Angle
Test 3
80
75
70
65
Water-wet zone
60
55
50
Field Twice- 10-Times- 20-Times- 100-Times-
UTMN
Connate 100% Q
Seawater 50%
DilutedQ 10% Q
Diluted 5%Q
Diluted 1% Q
Diluted
Water Seawater Seawater Seawater Seawater

Water Types
Fig. 8—Different tests for contact-angle measurements of carbonate-rock samples with reservoir live oil and connate water, injec-
tion seawater, and different dilution versions of seawater. The measurements were conducted at reservoir conditions.

of seawater were injected one after another, starting with regular
seawater and ending with 100-times-diluted seawater. Table 9
shows a summary of the first coreflood experiment. Figs. 9 and
10 show the cumulative oil recovery in terms of OOIC and the
pressure-drop profile for all injected slugs. Also, the injection-rate
profile is depicted in each of these figures.
Synthetic seawater first was injected in the composite core
set, and this type of water represents a replication of current
water injected in the reservoir. The cumulative oil production by
regular seawater with salinity of 57,600 ppm was approximately
22.05 cm3, and the corresponding cumulative oil recovery was
approximately 67.04% of OOIC; this slug targets mobile oil in

TABLE 9—SUMMARY OF THE FIRST COREFLOODING EXPERIMENT

Slug Type Phase Type Oil Recovery (% OOIC) Residual Oil Saturation, Sor (% PV)
Regular Seawater Secondary 67.04 29.5
Twice Diluted Tertiary 6.99 23.3
10 Times Diluted Tertiary 9.12 15.1
20 Times Diluted Tertiary 1.63 13.5
100 Times Diluted Tertiary 0.00 13.5
Final 84.97 13.46
The Slug of Regular Seawater Secondary 67.00 29.5
Different-Salinity Slugs of Seawater Tertiary 17.94 13.5
*PV = 36.82 cm3, OOIC = 32.82 cm3, Average Swi = 10.44%

100 40
Seawater
90 TotalSalinity
Cumulative Oil Recovery (% OOIC)

57,600 ppm
80
Injection Rate, cm3/min

30
70

60 10 20 100
Twice Times Times Times
50 Diluted Diluted Diluted Diluted 20

40

30
10
20

10

0 0
0 10 20 30 40 50

Cumulative Water Injected (No. Composite Core Pore Volume)

Fig. 9—Oil-recovery curve of the first coreflood experiment. The blue curve represents the amount of oil produced in terms of
OOIC through all injected salinity slugs of seawater (all salinities, and the red curve represents the injection-rate profile imple-
mented during the coreflood experiment.

October 2011 SPE Reservoir Evaluation & Engineering 585

 40 40
Seawater
TotalSalinity
35
57,600 ppm

Injection Rate, cm3/min

30 30

Pressure Drop, psi

10 20 100
25 Twice
Times Times Times
Diluted
Diluted Diluted Diluted
20 20

15

10 10

0 0
0 10 20 30 40 50
Cumulative Water Injected (No. Composite Core Pore Volume)

Fig. 10—Pressure-drop curve of the first coreflood experiment. The dark blue curve represents the pressure drop across the
composite core through all injected slugs of seawater (salinities), and the red curve represents the injection-rate profile imple-
mented during the coreflood experiment.

the composite core and represents the secondary oil production or
recovery. The bulk of the oil was recovered during the first two
pore volumes of water injected. Injection of seawater was contin-
ued until there was no more oil produced. To ensure that all mobile
oil was recovered, the injection rate is increased to 2 cm3/min and
then to 4 cm3/min before dropping back to 1 cm3/min. As depicted
in Fig. 9, no more oil was produced during this practice and this
confirmed that what was left in the core composite was residual oil
that cannot be produced or extracted by regular seawater. Also, this
injection practice was implemented for each slug in this coreflood
experiment.
The injection of twice-diluted seawater with a lower salinity
of 28,800 ppm followed, and after injection of approximately 0.5
to 0.7 pore volumes of this new type of water, a substantial incre-
mental of oil (approximately 2.3 cm3) was produced, equivalent to
approximately 7% incremental oil recovery beyond conventional
seawater flooding. This was followed by injecting 10-times-diluted
seawater with a salinity of 5,700 ppm. Even with this slug, higher
incremental oil recovery up to 10% of OOIC was obtained, equiva-
lent to 3 cm3 of additional oil. Next, 20-times-diluted seawater
with a salinity of 2,880 ppm was injected. A small increase in
oil recovery of approximately 1.6% of OOIC (equivalent to 0.6
cm3) was observed. Finally, no additional oil production/recovery
was observed with an injection of 100-times-diluted seawater.
Therefore, the total incremental oil recovery, beyond conventional
waterflooding, is approximately 18% by stepwise reduction of
salinity and ion content of seawater. This incremental oil undoubt-
edly represents a tertiary oil recovery.
The most dominant effect in the pressure-drop curves (Fig. 10)
is the major jumps induced by changing the injection rate at the
end of each slug. The general trend is that as the salinity of sea-
water decreases, the pressure drop across the composite core also
decreases. Because the oil left in the composite cores at the end of
regular-seawater injection is residual oil, the pressure drop at this
moment also reflects the capillary forces. Therefore, constant reduc-
tion of pressure drop with injection of different diluted versions of
seawater is another indication of alteration of brine/oil/rock interac-
tions. This is also consistent with contact-angle measurements.
Confirmation and Validation of Smart-Waterflooding Poten-
tial. Another coreflood experiment was conducted at reservoir con-
ditions using new composite-rock samples to confirm and validate
the substantial tertiary oil recovery observed with different-salinity
slugs of seawater. Table 10 shows a summary of this coreflood
experiment. Figs. 11 and 12 illustrate the cumulative oil recovery
in terms of OOIC and the pressure-drop profile, respectively, for
all injected slugs.
The trend of cumulative oil recovery and of the pressure profile
is consistent with the previous coreflood experiment with seawater.
The results show that the secondary oil recovery was approxi-
mately 74% with regular seawater; this targets mobile oil in the
composite-core plugs. The additional oil recovery beyond second-
ary recovery was approximately 8.5% with twice-diluted seawater,

TABLE 10—SUMMARY OF THE SECOND COREFLOODING EXPERIMENT

Slug Type Phase Type Oil Recovery (% OOIC) Residual Oil Saturation, Sor (% PV)

Regular Seawater Secondary 74.12 22.1

Twice Dilute d Tertiary 8.48 14.9
10 Times Dilute d Tertiary 9.95 6.4
20 Times Dilute d Tertiary 0.95 5.4
100 Times Dilute d Tertiary 0.00 5.4
Final 93.65 5.43

The Slug of Regular Seawater Secondary 74.12 22.1

Different-Salinity Slugs of Seawater Tertiary 19.53 5.4
*PV = 63.42 cm3, OOIC = 54.28 cm3, Average Swi = 14.4%

586 October 2011 SPE Reservoir Evaluation & Engineering

 100 20
Seawater
90 Total Salinity
57,600 ppm

Cumulative Oil Recovery (% OOIC)

80

Injection Rate, cm3/min

15
70

60 10 20 100
Twice Times Times Times
50 Diluted Diluted Diluted Diluted 10

40

30
5
20

10

0 0
0 5 10 15 20 25 30 35 40 45 50

Amount of Water Injected (No. Composite Core Pore Volume)

Fig. 11—Oil-recovery curve of the second coreflood experiment. The blue curve represents the amount of oil produced in terms
of OOIC through all injected slugs of seawater (all salinities), and the red curve represents the injection-rate profile implemented
during the coreflood experiment. Substantial tertiary oil recovery can be achieved by stepwise salinity and ionic-content reduc-
tion of injection seawater.

approximately 10% with 10-times-diluted seawater, approximately
1% with 20-times-diluted seawater, and none with 100-times-
diluted seawater. Therefore, the total incremental oil recovery,
beyond conventional waterflooding, is 19% by stepwise reduction
of salinity and ion content of injection seawater.
The outcome of this new coreflood experiment confirmed and
validated the substantial additional oil recovery observed with
previous coreflood experiment.
Impact of Injection-Water Chemistry on Carbonate-Rock
Samples. The carbonate reservoir targeted in this study typically
consists of different pore systems, including macropores and differ-
ent micropore types (Type 1, 2, 3) (Clerke et al. 2008; Cantrell and
Hagerty 2003). NMR response, for water-saturated carbonate-rock
samples usually indicates these pore systems at different T2 values.
Stated simply, small pores or micropores will have small T2 values
and large pores (macropores) will have large T2 values. Fig. 13
shows T2 distribution for a carbonate-rock sample characterized by
bimodal pore-size distribution. The first peak represents micropore
distribution, and the second represents the macropore distribution.
Fig. 14 shows the NMR T2 distribution results for rock samples
before and after the first coreflood experiment. Different post-test
NMR runs were conducted for each rock sample to confirm and
validate NMR signals.
One important observation from these results is the apparent
shift in the position of T2 distributions between NMR results before
and after the test for all rock samples. All rock samples exhibited
fast surface relaxation (shorter T2 times) after injecting different-
salinity slugs of seawater, although rock samples were saturated in
both cases with field connate water. This was also the case with all

20 30
Seawater
Total Salinity
57,600 ppm 25
Injection Rate, cm3/min

15
Pressure Drop, psi

10 20 100 20
Twice
Times Times Times
Diluted
Diluted Diluted Diluted
10 15

10
5
5

0 0
0 5 10 15 20 25 30 35 40 45 50
Amount of Water Injected (No. Composite Core Pore Volume)

Fig. 12—Pressure-drop curve of the second coreflood experiment. The dark blue curve represents the pressure drop across
the composite core through all injected slugs of seawater (all salinities), and the red curve represents the injection-rate profile
implemented during the coreflood experiment.

October 2011 SPE Reservoir Evaluation & Engineering 587

 1.0 are overlapped; this is more obvious with rock samples used in the
first coreflood experiment (Fig. 14). One explanation is that the
Macro Pores apparent averaging of the underlying pore-size distribution indicates
0.8 that the connectivity between macropore and micropore systems is
Normalized Ampitude

significantly enhanced, a phenomenon known as pore coupling in

0.6
0.4
0.2
0.0
1 10 100
T2 Time (µ
Fig. 13—Example of NMR T2 distribution for a carbonate-rock
sample fully saturated with connate water.
rock samples used in the second coreflood experiment (Fig. 15).
One feasible explanation is a significant increase in rock-sample
surface relaxivity () because of flooding rock samples by different
diluted versions of seawater. Because NMR results were conducted
using the same saturated water (field connate water), an increase
in surface relaxivity reflects an increase in the capacity of pore
surface to enhance the relaxation of excited protons.
Another important observation is that the NMR T2 relaxations
for micropore systems (peaks at shorter T2 distribution) look as if
disappeared or damped, compared with T2 distributions before an
NMR test. Actually, the fast-relaxing protons in micropores (shorter
T2 times) and slow-relaxing ones in macropores (longer T2 times)
NMR application (Grunewald and Knight 2009). Improving the
connectivity between micropores and macropores can be attributed
to microscopic dissolution triggered by injecting different-salinity
slugs of seawater, or to a salinity gradient initiated because the initial
Micro Pores
water residing in the micropores systems—in our case, field con-
nate water—is not easily replaced by subsequent slugs of seawater.
To verify the modification of the connectivity further, more NMR
measurements, such as diffusivity, must be conducted.
A different explanation for such changes in NMR results
depicted in Figs. 14 and 15 could also be associated with the
1000 10000 100000 1000000 10000000 cleaning process rather than changes in water composition. To
µ-seconds)
investigate this possibility, we conducted NMR tests for a new
set of rock samples before and after subjecting these cores to a
cleaning process using toluene and methanol. Fig. 16 depicts NMR
T2 distribution for two rock samples before and after the cleaning
process. The results clearly indicated that the cleaning process
has an insignificant effect on NMR T2 distributions, and hence
proved that changes in water composition are the main cause for
significant alteration in NMR T2 distributions for all carbonate-
rock samples.
The main conclusion of the NMR study is that the salinity and
ionic composition of the injection water have a significant impact
on carbonate-rock surface relaxation and connectivity among dif-
ferent pore systems.
Discussions
The most significant and exciting observation that needs to be
highlighted is the incremental oil recovery reported in this research
work. Varying the salinity of seawater provided substantial increase

6000 8000
Sample #2 Sample #4 Prior Test
7000
5000 Prior Test

6000
4000
5000 Post Test
Ampitude

Different Runs
Ampitude

Post Test
3000 Different Runs 4000

3000
2000

2000
1000
1000

0 0
1 10 100 1000 10000 100000 1000000 10000000 1 10 100 1000 10000 100000 1000000 10000000
µ-seconds)
T2 Time (µ µ-seconds)
T2 Time (µ
8000
6000
Sample #3 Prior Test Sample #1 Prior Test
7000
5000
6000

Post Test 4000 Post Test

5000 Different Runs
Different Runs
Ampitude

Ampitude

4000 3000

3000
2000
2000

1000
1000

0 0
1 10 100 1000 10000 100000 1000000 10000000 1 10 100 1000 10000 100000 1000000 10000000
µ-seconds)
T2 Time (µ µ-seconds)
T2 Time (µ

Fig. 14—NMR T2 distribution for rock samples before and after the first coreflood experiment.

588 October 2011 SPE Reservoir Evaluation & Engineering

 7000 10000
Sample #5 Prior Test Sample #6 Prior Test
9000
6000
8000
5000 7000
Post Test Post Test
Different Runs 6000
Ampitude

Different Runs

Ampitude
4000
5000
3000
4000

2000 3000

2000
1000
1000

0 0
1 10 100 1000 10000 100000 1000000 10000000 1 10 100 1000 10000 100000 1000000 10000000
µ-seconds)
T2 Time (µ µ-seconds)
T2 Time (µ
9000 8000
Sample #7 Prior Test Sample #8 Prior Test
8000
7000
7000
6000
6000 Post Test
5000 Post Test
Run
Ampitude

Different Runs

Ampitude
5000
4000
4000
3000
3000

2000 2000

1000 1000

0 0
1 10 100 1000 10000 100000 1000000 10000000 1 10 100 1000 10000 100000 1000000 10000000
µ-seconds)
T2 Time (µ µ-seconds)
T2 Time (µ
9000 6000
Sample #9 Prior Test Sample #10
8000
5000 Prior Test

7000

6000 4000
Post Test
Ampitude

Different Runs
Ampitude

5000 Post Test

3000 Different Runs
4000

3000 2000

2000
1000
1000

0 0
1 10 100 1000 10000 100000 1000000 10000000 1 10 100 1000 10000 100000 1000000 10000000

µ-seconds)
T2 Time (µ µ-seconds)
T2 Time (µ

Fig. 15—NMR T2 distribution for rock samples before and after the second coreflood experiment.

in oil recovery up to approximately 18 to 19%, beyond conven-
tional waterflooding. The recovery-mechanism study indicated
that altering the salinity and ionic composition of seawater has
a significant impact on rock wettability or fluid/rock interactions
(Fig. 8). Therefore, it can be concluded that reducing the salinity
of seawater has a significant effect on brine/oil/rock interactions
and rock wettability. This will consequently enhance microscopic
displacement efficiency and provide substantial tertiary oil recov-
ery from carbonate-composite core plugs.
The impact on IFT measurements or fluid/fluid interactions is
negligible (Fig. 6), and this implies that diluting seawater primarily
affects fluid/rock interactions. As suggested by NMR measurements
(Figs. 14 and 15), diluting seawater is able to cause a significant
alteration in the surface relaxation of the carbonate rock and the
connectivity among pore systems because of rock dissolution.
It is important at this stage to address how the observed trend
(smart waterflooding) in this study is different from what has been
reported in the literature. In low-salinity waterflooding proposed
for sandstone reservoirs, the effect of low-salinity flooding has
been associated with wettability alteration of clay minerals, which
typically exist in sandstones, toward a water-wet state (Tang and
Morrow 1999; Lager et al. 2006). Because of the lack of clay min-
erals in carbonate reservoirs and also in our case, this mechanism
cannot explain the substantial oil recovery observed in the cur-
rent coreflood experiments. Also, different reported studies have
excluded the potential of diluting seawater for carbonate reservoirs
because of lack of clay minerals (Lager et al. 2006; RezaeiDoust
et al. 2009).
Another recently emerged research trend states that injecting
seawater rather than any other type of water will improve oil

October 2011 SPE Reservoir Evaluation & Engineering 589

 2100
New Sample #1
Carbonate Rock
1800
1500
Prior Cleaning Process
Post Cleaning Process
Ampitude
1200
900
600
300
0 0
1 10 100 1000 10000 100000
µ-seconds)
T2 Time (µ
Fig. 16—The impact of the cleaning process on NMR T2 distribution for two carbonate-rock samples.
recovery from chalk reservoirs (Austad et al. 2005; Strand et al.
2006; Zhang and Austad 2006; Zhang et al. 2007; Austad et al.
2008). This effect is attributed to the reactivity of key seawater
ions (SO42–, Ca2+, Mg2+) that has the capability to change rock
surface charges, release adsorbed carboxylic oil component from
the rock surface, alter rock wettability, and eventually improve oil
recovery. Most recently, a reported study (Fathi et al. 2010) argued
that diluting seawater will decrease oil recovery from chalk-rock
samples. These discrepancies between our research findings and
the reported study are attributed to major differences in rock types
and characteristics, initial connate-water composition, reservoir
fluids, experimental procedures and conditions, as well as injection
practices. On the basis of their research work (Fathi et al. 2010),
the potential of diluting seawater in terms of oil recovery was
exclusively demonstrated through spontaneous-imbibition tests
using crude oil with high acidic content (acid number = 1.90 mg
of KOH/g), sulfate-free formation water, and chalk core samples
characterized by very low permeability of 1 to 3 md and high
porosity of 40 to 45%.
In this research work, we have addressed the impact of diluting
seawater through dynamic-displacement experiments on capillary
forces, typically dominant at the end of the conventional water-
flooding. The new recovery method/process uses a sequential
injection of different diluted versions of injection seawater. It is
established that the residual-oil saturation in carbonate cores may
vary with an increasing injection rate, and this observation can
be attributed to capillary end effects, wide pore-size distribution,
core-scale heterogeneity, or complex wettability (Kamath et al.,
2001; Mohanty and Miller 1991). Because little consideration has
been given to this detail in the literature addressing oil-recovery
measurements using coreflood experiments, different injection
practices were implemented in this work to ensure that the residual
oil is attained ahead of the injection of any tertiary slug. This is a
crucial step to accurately examine the impact of injecting differ-
ent diluted versions of seawater on the residual-oil saturation, and
eventually on oil recovery.
The results reported in this study clearly indicated a significant
potential for this new recovery method in carbonate reservoirs. The
recovery-mechanism study confirmed that altering injection-water
salinity and ionic content is able to alter the rock wettability toward
a more water-wet state. The significant alteration was observed
with twice-diluted seawater and also 10-times-diluted seawater,
where these two slugs provided substantial additional oil recover-
ies. The effect of smart waterflooding in a secondary mode was not
addressed in this work. Current research activities are dedicated to
examine the potential of this process in this recovery mode. This
will be the subject of future publications.
All evidence gathered during this research work indicated that
smart waterflooding is a new research trend, different from what
has been proposed in the literature on the topics of low-salinity
590
1400
New Sample #2
Carbonate Rock
1200
1000 Prior Cleaning Process
Post Cleaning Process
Ampitude
800
600
400
200
1000000 10000000 1 10 100 1000 10000 100000 1000000 10000000
µ-seconds)
T2 Time (µ
waterflooding for sandstone reservoirs and injection of seawater in
chalk reservoirs. This does not imply that there are no similarities
among these research trends; however, each trend will need certain
conditions to trigger its effect in terms of additional oil recovery.
Conclusions
We reported on a new recovery method/process for carbonate
reservoirs, tagged “smart waterflooding,” to improve or enhance
oil recovery through altering the salinity and ionic composition
of injection seawater. This was demonstrated so far through well-
tailored coreflooding experiments using composite cores from
one of the Saudi Arabian carbonate reservoirs. The experimental
parameters and procedures were well designed to reflect reser-
voir conditions and current field injection practices, including
reservoir pressure, reservoir temperature, initial reservoir connate
water (salinity of 200,000 ppm), and synthetic brines for injection
seawater. The method consists of a sequential injection of vari-
ous diluted versions of regular seawater. Different practices were
implemented to ensure ahead of the injection of any tertiary slug
that the residual oil is attained through specific injection practices.
The additional oil recovery was approximately 7 to 8.5% with
twice-diluted seawater, approximately 9 to 10% with 10-times-
diluted seawater, and approximately 1 to 1.6% with 20-times-
diluted seawater, all in terms of the OOIC. The following are the
primary research findings:
• The results revealed that altering the salinity of injection seawa-
ter has a substantial potential to obtain additional incremental
oil recoveries.
• Tertiary oil production was triggered after injection of 0.5 to 0.7
pore volumes of a new type of water.
• The recovery-mechanism study confirmed that altering the salin-
ity and ionic content of the injection water is able to alter the
rock wettability toward a more water-wet state. The significant
alteration was observed with twice-diluted seawater and also
with 10-times-diluted seawater, where these two slugs provided
substantial additional oil recoveries.
• The contact-angle measurements also highlighted that injection
of seawater is capable of changing rock wettability toward a
water-wet state. This suggests that injecting seawater has a
potential to provide high oil recovery compared with the use of
other sources of water, such as formation water.
• The recovery-mechanism study also demonstrated that smart
waterflooding has irrelevant impact on IFT measurements, com-
pared to contact-angle measurements. This implies that diluting
seawater mainly affects fluid/rock interactions.
• The constant reduction of pressure drop across composite cores
with injection of different diluted versions of seawater is another
indication of alteration of brine/oil/rock interaction, indicated by
contact-angle measurements.
October 2011 SPE Reservoir Evaluation & Engineering
• NMR results indicated that injecting different-salinity slugs of
seawater in carbonate-core samples is able to cause a significant
alteration in the surface relaxation of the carbonate rock and is
also able to enhance connectivity among pore systems because
of rock dissolution. This suggests one approach to wettability
alteration.
• The results, observations, and interpretations addressed over
the past 3 years provided compelling evidence that the driving
mechanism for substantial oil recovery observed in this study is
wettability alteration; as indicated by the NMR results, this can be
triggered by alteration of surface charges of a carbonate rock.
• All evidence gathered during this research work indicated that
smart waterflooding is a new research trend, different from what
has been proposed in the literature on the topics of low-salinity
waterflooding for sandstone reservoirs and injection of seawater
in chalk reservoirs. This does not imply that there are no similari-
ties among these research trends, but each trend will need a certain
condition to trigger its effect in terms of additional oil recovery.
Nomenclature
D = molecular self-diffusion of the water
G = magnetic-field gradient
S/V = surface-area-to-volume ratio of the pores
Swi = initial water saturation
T2 = relaxation rate
T2B = relaxation rate for the bulk fluid
 = gyromagentic ratio of the hydrogen nucleus
e = echo time
 = surface relaxivity
Acknowledgments
The authors would like to thank the Saudi Aramco for granting
permission to present and publish this paper. The authors would
also like to thank the management of EXPEC ARC.
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Appendix A: Experimental Procedure for
IFT Measurements
The experimental procedure followed is described below:
1. Run a calibration test by placing the stainless-steel ball inside
an empty IFT cell.
2. Set up the image system to be ready to take a picture.
3. Select the calibration option and run the program to adjust
the horizontal/vertical apex ratio.
4. Remove the ball from the IFT cell, and fix the position of
the camera.
5. Inject connate water into the IFT cell to full level.
6. Set temperature at reservoir value using temperature control
to obtain temperature equilibrium inside the whole cell.
7. Inject brine into the cell to increase the pressure inside the
cell to reservoir pressure.
8. Inject recombined live oil through the bottom needle to
obtain a stable oil drop on the top of the needle inside the cell.
9. Take a digital photograph at reservoir temperature and pressure.
10. Run the image drop program to calculate IFT values.
592
11. Remeasure the IFT values after 12 hours.
12. The procedure was then repeated with regular seawater and
twice-diluted, 10-times-diluted, 20-times-diluted, and 100-times-
diluted seawater.
Appendix B: Experimental Procedure for
Contact-Angle Measurements
The experimental procedure followed is described below:
1. Prepare carbonate-rock plates.
2. Saturate rock plates with field connate water.
3. Age rock-plate samples in field oil.
4. Clean rock plate, and mount it to the upper needle using
epoxy.
5. Place the plate inside the chamber cell at a suitable position
to be seen in the image system (Fig. 3).
6. Inject field connate water into the contact-angle cell.
7. Set the temperature and pressure of the cell to reservoir
conditions.
8. Raise the bottom needle to be close to the plate.
9. Place an oil droplet on the surface of the rock plate.
10. Move the bottom needle down carefully.
11. Run the program on contact-angle-measurement mode.
12. Monitor the contact angle between the oil/brine/solid inter-
faces over 2 days.
13. Inject regular seawater, and repeat the above procedure.
14. The procedure was then repeated with twice-diluted, 10-
times-diluted, 20-times-diluted, and 100-times-diluted seawater.
Appendix C: Experimental Procedure for
Coreflooding Experiments
The experimental procedure followed is described below:
1. All accumulators of the coreflooding apparatus are first filled
with injected fluids, including dead oil, live oil, and brines.
2. The three-phase separator is checked and calibrated to deter-
mine the oil production during waterflooding accurately.
3. The composite-core plugs are assembled, wrapped with
Teflon®, placed into a rubber sleeve, and loaded into the core
holder.
4. Confining pressure of 4,500 psi is maintained on the composite-
core plugs by filling the core holder confining annulus.
5. The composite-core-plug pore pressure is initiated by setting
up the backpressure regulator at 200 psi.
6. Dead oil is flushed through the composite-core plug at
backpressure conditions to displace gas and ensure complete fluid
saturation.
7. Dead-oil flushing is maintained until the pressure drop
across the composite-core plug is stabilized. This process takes
1 to 2 weeks.
8. The oven is switched on, and the temperature is set to the
reservoir temperature of 212°F.
9. The composite-core plug is aged at reservoir temperature
with repeated dead-oil flushes. This process takes 1 to 2 weeks,
and it ends when the pressure drop across the composite-core plug
is stabilized.
10. The pore pressure of the composite-core plug is set at res-
ervoir pressure through the backpressure regulator.
11. Live oil is injected into the composite-core plug to displace
the dead oil.
12. For aging purposes and to restore the original wettability
of the composite-core plug, one pore volume of live oil is flushed
for 1 to 2 weeks until the pressure drop is stabilized.
13. Conduct seawater flooding while monitoring the amount
of oil produced, the pressure drop across the composite, and the
injection rate of the seawater as a function of time.
14. Water was injected at a constant rate of approximately 1
cm3/min until no more oil was produced.
15. The injection rate was increased to 2 cm3/min and then to
4 cm3/min to ensure that all mobile oil was produced.
16. The twice-diluted seawater was then injected into the core
sample, following the same injection procedure as described in
the preceding steps.
October 2011 SPE Reservoir Evaluation & Engineering
 17. The injection procedure was then repeated with 10-times-
diluted, 20-times-diluted, and 100-times-diluted seawater.
SI Metric Conversion Factors
bbl × 1.589873 × 10–1 = m3
ft × 3.048 × 10–1* = m
ft3 × 2.831685 × 10–2 = m3
*Conversion factor is exact.
Ali Yousef is a petroleum engineering specialist and a Focus
Area Champion of SmartWater Flood at Saudi Aramco’s
Advanced Research Center (EXPEC ARC). email: ali.yousif.11@
aramco.com. He joined Saudi Aramco in 1994. Since joining
Aramco, he has been involved in applied research projects
on improved oil recovery/enhanced oil recovery, field-scale
waterflooding performance optimization, and reservoir model-
ing and simulation. Currently, he is leading a group of scientists,
engineers and technicians to develop new water flooding-
based technologies that can increase oil recovery from petro-
leum reservoirs. He has written more than 35 technical papers
October 2011 SPE Reservoir Evaluation & Engineering
and reports and has several patents. Yousef holds a BS degree
in chemical engineering from King Fahd University of Petroleum
& Minerals (KFUPM) and MS and PhD degrees in petroleum
engineering from the University of Texas at Austin. Salah Al-
Saleh is laboratory coordinator of SmartWater Flood at Saudi
Aramco’s Advanced Research Center (EXPEC ARC). He joined
Saudi Aramco in 1988, and has worked on petrophysics labo-
ratory studies and special core analyses. He has more than 20
years of experience in design and conduct special laboratory
techniques. He is coauthor of several technical papers, reports,
and patents. Abdulaziz O. Al-Kaabi is chief technologist of res-
ervoir engineering technology at Saudi Aramco’s Advanced
Research Center (EXPEC ARC). Before joining Saudi Aramco in
2002, Al-Kaabi was associate professor of petroleum engineer-
ing at King Fahd University of Petroleum & Minerals (KFUPM).
He has more than 28 years of combined academic and
industry experience. He holds BS and MS degrees from KFUPM
and a PhD degree from Texas A&M, all in petroleum engi-
neering. Mohammed Al-Jawfi is senior laboratory technician
of SmartWater Flood at Saudi Aramco’s Advanced Research
Center (EXPEC ARC). He joined Saudi Aramco in 1993 and has
worked in different upstream laboratory functions including
PVT, and formation damage.
593