SPE-180138-MS

Understanding the Chemical Mechanisms for Low Salinity Waterflooding

Changhe Qiao, Russell Johns, and Li Li, Pennsylvania State University

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Europec featured at 78th EAGE Conference and Exhibition held in Vienna, Austria, 30 May – 2 June 2016.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Low salinity water (LSW) is reported to improve oil recovery (IOR) significantly in sandstone and
carbonate core experiments. Ranges of IOR vary significantly depending on the chemical composition of
brine, oil and cores. We previously developed a process-based and predictive model that explicitly
includes the chemical interactions between crude oil, brine, and the carbonate surface that alter rock
wettability. In this research, we improve the developed model to include explicitly the acid/base
interaction and ion-binding interaction of crude oil adsorption.
The wettability alteration is quantified by the surface concentrations of adsorbed carboxylic acids,
which is a result of aqueous and surface reactions. The total concentrations of aqueous and surface species
are varied individually and together over a large range while precipitation constraints are also included.
The wettability is for a variety of brine compositions used in experiments.
The wettability depends strongly on the concentration of Ca2⫹, Mg2⫹ and SO42⫺, as well as the total
salinity. Including the acid/base interaction can explain the wettability alteration trend when Ca2⫹, Mg2⫹
and SO42⫺ concentrations are significant. Including the ion-binding through Ca2⫹ can better explain the
wettability alteration trend when diluted formation water or seawater is injected. We can reproduce the
wettability alteration trend reported in experiments from different sources by combining the acid/base and
ion-binding mechanisms and considering the irreversibility of the carboxylic adsorption reactions.

Introduction
Low salinity waterflooding has been known to improve oil recovery beyond conventional waterflooding
(Yildiz and Morrow 1996, Lager et al. 2008). For clay-rich sandstone reservoirs, decreasing the total
salinity and divalent cations improves displacement efficiency in coreflooding experiments (Tang and
Morrow 1999). For carbonate reservoirs, experiments show that concentrations of specific ions and
salinity can impact oil recovery depending on rock mineralogy (Yousef et al. 2011, Austad et al. 2012).
Many studies indicate that surface potential determining ions (PDIs) such as Mg2⫹, Ca2⫹, SO42⫺ and
CO32⫺ affect the oil recovery during spontaneous imbibition (Zhang et al. 2007, Austad et al. 2008, Strand
et al. 2008, Fathi et al. 2010, Heberling et al. 2011). Mg2⫹ and SO42⫺ have been found to be particularly
effective in altering the surface wettability (Zhang et al. 2007, Karimi et al. 2015). An increase in SO42⫺
concentration leads to improved oil recovery in both chalk and limestone, but not dolomite (Fathi et al.
2 SPE-180138-MS

2010, Austad et al. 2012, Chandrasekhar and Mohanty 2013b, Shariatpanahi et al. 2016) while Ca2⫹ has
minor or negative impacts (Fathi et al. 2010, Chandrasekhar and Mohanty 2013a).
Deionized water, diluted formation water and seawater, however, were reported to improve oil
recovery in limestone and dolomites (Yousef et al. 2011, Austad et al. 2012, Romanuka et al. 2012,
Shariatpanahi et al. 2016). This is different from the effects of the PDIs because the concentrations of PDIs
are small or zero in such cases. Mahani et al. (2015) proposed that the mechanisms underlying low salinity
waterflooding is related to surface potential decrease. One interesting set of coreflooding experiments by
Shehata et al. (2014) shows that oil recovery can be improved by injection of deionized water after
seawater injection, and vice versa. The IOR is believed to be caused by a sudden change of brine ionic
composition while no detailed explanation is provided.
In addition to seawater and diluted seawater, injection of chemically tuned seawater was found to
significantly improve oil recovery. It is likely that increasing the sulfate and magnesium concentration will
enhance this process while calcium may decrease the wettability alteration effect. Since the PDIs have
different impacts on the wettability alteration, an optimum concentration of PDIs could lead to higher oil
recovery. Fathi et al. (2011) proposed that decreased NaCl combined with increased SO42-gives the best
oil recovery. MgSO4 solution was also reported to give the best oil recovery by Alshakhs and Kovscek
(2015). Anhydrite dissolution has been found to improve the oil recovery but a smaller salinity leads to
a smaller solubility of anhydrite (Austad et al. 2012). In general, the interactions among different ions tend
to compete with each other in interacting with rock surfaces. There is no general principle that can be used
to understand and predict conditions that maximize IOR.
In previous research, a novel multiphase reaction network was proposed to predict the wettability
alteration in carbonates using the interfacial reactions (Qiao et al. 2015). The reaction network reproduced
the sensitivity of wettability alteration with respect to different ionic composition and NaCl level. The
mineral dissolution was also considered to buffer the solution composition (Qiao et al. 2016). In this
research, we improve the carboxylic acid adsorption mechanism by explicitly considering the acid/base
interaction and the ion binding interaction. The calculated wettability indices are consistent with exper-
imental results from different sources.
Methodology

The mineral surface is naturally water wet if the mineral has not been contacted by crude (Morrow et
al. 1986). At the reservoir pressure and temperature, the polar components in crude oil can adsorb on the
mineral surface, which leads to wettability alteration to oil wettability or mixed wettability. With either
diluted or chemically tuned water injection, the wettability alteration is widely accepted as the main
mechanism for the improved oil recovery (Buckley and Liu 1998, Austad et al. 2008, Alotaibi et al. 2010,
Yousef et al. 2011, Mahani et al. 2015). Polar crude oil components adsorption is believed to be the reason
for the oil-wet surface. To understand the wettability alteration during LSW, we need to understand the
mechanisms of crude oil adsorption and desorption.
Crude Oil Adsorption Mechanisms
Adsorption occurs at the interface between the surface and solution in a two-dimensional structure
(Goldberg 2013). If the adsorption accumulates to an extent that leads to a three-dimensional structure,
precipitation occurs. The main polar crude oil component that adsorb on mineral surface is the carboxylic
group, denoted as (⫺COO⫺). The extent of crude carboxylic adsorption depends on several factors
including brine composition, crude oil composition and rock surface mineralogy. Both the mineral surface
and the crude oil surface have coexisting positive and negative charges. Adsorption occurs between
discrete, oppositely charged sites and can happen even when the net charges of the mineral and crude oil
surfaces are the same (Buckley et al. 1998). The net potential of a surface therefore cannot determine the
adsorption of crude oil components.
SPE-180138-MS 3

There are four main categories of crude/brine/rock interactions identified in experiments, including
polar interactions, surface precipitations, acid/base interactions and ion binding (Buckley and Liu 1998).
Polar interaction occurs when water is absent between oil and rock, which can be excluded for low salinity
waterflooding. Surface precipitation happens when the crude oil contains significant amounts of large
molecules such as asphaltenes and resin. This mechanism can be excluded when oil contains little
asphaltenes. The acid/base interactions and ion binding are assumed to dominate the interaction between
crude oil and mineral surfaces in most low salinity waterflooding scenarios.
Acid/Base Interactions The acid/base interaction denotes the process when polar functional groups of
the mineral and crude oil surfaces as acids and bases that obtain or release hydrogen ion. The polar
component adsorption includes two steps:
1. Collapse of the water film. The stability of water film calculation can only determine if the
wettability alteration from water wet to oil wet occurs.
2. Ionized acidic and basic sites influence adsorption. At this stage, crude oil components at the
oil/brine interface can adsorb on the solid surface. For calcite, most adsorption happens when the
anionic carboxylic acids adsorb onto the positively charged rock surface sites.
The dependency on pH is an important indication that acid/base interaction happens. This mechanism
was verified by experimental observation that both the calcite surface and the crude oil surface have strong
pH-dependent surface potential (Alshakhs and Kovscek 2015, Mahani et al. 2015). This process is
reversed when carboxylic acids desorb.
Ion Binding Different surface sites can attract the same multi-valent ion. For example, Ca2⫹ can adsorb
on the calcite surface site ⬎CO3⫺ and become ⬎CO3Ca⫹. On the other hand, Ca2⫹ can adsorb on crude
oil surface site ⫺COO⫺ and become ⫺COOCa⫹. For sandstones, ion binding is shown to be an important
mechanism (Rezaeidoust et al. 2011). However, this mechanism has not been considered in modeling the
LSW in carbonates. Ion binding happens when the same multivalent ion such as Ca2⫹ links between the
calcite surface site and crude oil surface site.

Surface Complexation Modeling

Surface complexation models (SCMs) describe the surface chemical reactions and can correlate the
surface properties with the aqueous concentrations and crude oil properties. Surface complexation models
have been used to match the surface zeta potential and surface charge (Pokrovsky and Schott 2002, Brady
et al. 2012, Goldberg 2013, Qiao et al. 2014). Surface reactions occur rapidly and are typically considered
in equilibrium. SCMs are systematic tools to describe the surface interactions with many parameters.
Calcite/Water Interface and Crude Oil/Water Interface Carbonates mineral surfaces have two surface
sites, ⬎CO3H and ⬎MeOH, where Me represents any divalent metal element. In chalk and limestone,
⬎CaOH exists while ⬎CaOH and ⬎MgOH coexist for dolomites. Here we only consider ⬎CaOH and
⬎CO3H. ⬎CaOH can obtain a hydrogen ion and become positively charged ⬎CaOH2⫹, or lose a
hydrogen ion and become negatively charged ⬎CaO-. ⬎CO3H can lose a hydrogen ion and become
negatively charged ⬎CO3⫺. The possible surface species include ⬎CO3H, ⬎CO3⫺, ⬎CO3Me⫹,
⬎MeOH, ⬎MeO⫺, ⬎MeOH2⫹, ⬎MeCO3⫺, ⬎MeSO4⫺ (Pokrovsky et al. 2000, Pokrovsky and Schott
2002, Brady et al. 2012). The total surface site densities for ⬎CO3H and ⬎CaOH are 4.1 ␮mol/m2
(Pokrovsky and Schott 2002).
The crude oil surface sites include -N and ⫺COOH (Brady et al. 2015). The acid number and base
number of the crude oil determine the surface site density. Carboxylic group (⫺COOH) can lose a
hydrogen ion and become negatively charged (⫺COO⫺); the nitrogen base group (⫺N) can obtain a
hydrogen ion and become positively charged (⫺NH⫹). When pH is greater than 5.7, ⫺COO⫺ dominates
the crude oil surface. The formation water in carbonates usually have high pH values; therefore, we only
4 SPE-180138-MS

consider the surface sites formed by the carboxylic group. The possible surface species are ⫺COOH,
⫺COO⫺ and ⫺COOMe⫹. Here we fix the surface site density for crude oil surface at 6 ␮mol/m2 (Brady
and Krumhansl 2012). The reactions are listed in Table 1.

Table 1—Surface reactions and equilibrium constants. Except CO2 and CO3, other reaction equilibrium constants are
from Qiao et al. (2016)
Number Reactions log Keq

Oil/water interface reactions

01 ⫺COOH ↔ ⫺COO⫺ ⫹ H⫹ ⫺5.00
02 ⫺COOCa⫹ ↔ ⫺COO⫺ ⫹ Ca2⫹ ⫺1.20
03 ⫺COOMg⫹ ↔ ⫺COO⫺ ⫹ Mg2⫹ ⫺1.30
Solid (Calcite) / water interface reactions
C1 11.80
C2 ⫺3.25
C3 6.00
C4 ⫺5.10
C5 ⫺3.40
C6 ⫺3.40
Calcite-water / oil-water interface reaction
C01 ⫺5.90
C02 ⫺5.90
C03 ⫺5.90
Aqueous-phase reactions
A1 H20 ↔ H⫹ ⫹ OH⫺ 12.24
A2 10.27
A3 ⫺6.43
A4 ⫺2.46
A5 ⫺0.77
A6 2.61
A7 CaCl⫹ ↔ Ca2⫹ ⫹ Cl⫺ ⫺0.54
A8 MgCl⫹ ↔ Mg2⫹ ⫹ Cl⫺ -0.74
Mineral dissolution/precipitation reactions
M1* 0.58
M2* ⫺5.34

*mineral dissolution/precipitation reactions are only included in Austad et al. (2012) as other experiments did not indicate or excluded the possibility of mineral
reactions.

Adsorption and Desorption of Crude Oil Component Unlike the surfactant adsorption, adsorption of
crude oil components cannot be modeled as a solute in either oil or water phases because the adsorbing
species exists almost exclusively at the oil/brine interface (Buckley and Liu 1998). Here we consider two
adsorption mechanisms explicitly. The acid/base interaction between positive charge on calcite surface
and negative charged sites on crude oil surface is denoted as ⬎CaOH2-COO, which is formed by:
(1)

The ion binding by calcium ions is denoted as ⬎CO3Ca(⫺COO),

(2)

It is also possible that Mg2⫹ bridges the two surfaces, as follows

(3)
SPE-180138-MS 5

Our previous modeling work considers the acid/base interaction (1) as the main reason for crude oil
adsorption (Qiao et al. 2014; Qiao et al. 2016). The present work includes both the acid/base and
ion-binding mechanisms. Reactions (2) and (3) are the new reactions added to the multiphase reaction
network for the first time. Other aqueous reactions and mineral reactions can be found in Table 1.
With SCMs, there are two methods to quantify the wettability. One method is the calculation of
disjoining pressure (Alshakhs and Kovscek 2015). This method utilizes DLVO (Derjaguin, Landau,
Verwey and Overbeek) theory and reconstructing contact angle from surface zeta potential. This method
assumes that the crude oil and solid surface does not directly contact. Another method uses the surface
concentration of adsorbed carboxylic acids to quantify wettability alteration (Qiao et al. 2014). With this
method, the crude oil adsorption equilibrium is tuned due to the lack of thermodynamic database. In this
research, we use the second approach to reproduce experimental results from literature.
Speciation Calculation We have nr equilibrium correlations for the reactions listed in Table 1, where nr
is the number of reactions. The reaction equilibrium law uses a constant capacity model where the surface
potential is assumed constant. One example of the reaction equilibrium law for reaction (O1) is:

where aH⫹ is the activity of hydrogen ion. With ns species, we need ns ⫺ nr other equations to complete
the system. The concentrations given in experiments provide ns ⫺ nr ⫺ 1 constraining equations. In
theory, pH can be calculated from charge balance. However, with this approach the pH is very sensitive
to ion concentrations and can have large errors due to measurement inaccuracy. Therefore, pH is used as
an input in this work. With the surface complexation model and the measured concentrations of major
species, we can solve for the concentration of each individual species.

Results and Discussion

In the following, we use four sets of brine composition as input for the above SCMs while keeping the
same set of reaction parameters. A summary of the equilibrium reactions and the equilibrium constants
are in Table 1.
Mahani et al. (2015). Wettability alteration upon exposure to low salinity brine was examined by
continuous monitoring of the contact angle. Formation water (FW), seawater (SW), 25-times-diluted
seawater (25dSW) and 25dSW equilibrated with calcite (25dSWEQ) were used. In the experiments, all
contact angles were first measured in FW, and then the brine was replaced with SW, 25dSW and
25dSWEQ. Contact angle measurements shows that SW, 25dSW and 25dSWEQ can decrease the contact
angle, altering wettability of the calcite surface. Therefore, the adsorbed carboxylic group for FW should
be larger than SW, 25dSW and 25dSWEQ.
We use the same brine composition used in the experiments to perform speciation calculation. The
concentrations of the adsorbed carboxylic group in different forms are shown in Figure 1. Figure 1 shows
that ⬎CO3Ca-COO concentration decrease from FW to other brines. There is no such trend for
⬎CaOH2-COO and ⬎CO3Mg-COO. Figure 1 also indicates that ⬎CO3Ca-COO is the dominant surface
species.
6 SPE-180138-MS

Figure 1—Calculated adsorbed carboxylic acid for brine in Mahani et al. (2015).

Table 2—Brine compositions used in experiments in Mahani et al. (2015). Unit of concentration is mol/kg water.
FW SW 25dSW 25dSWEQ

HCO3ⴚ 0.0027 0.0029 0.0001 0.0002

Clⴚ 3.1496 0.6800 0.0272 0.0272
SO42ⴚ 0.0024 0.0353 0.0014 0.0014
Mg2ⴙ 0.1353 0.0674 0.0027 0.0027
Ca2ⴙ 0.3625 0.0127 0.0005 0.0006
Naⴙ 2.1695 0.5828 0.0233 0.0233
Kⴙ 0.000 0.0124 0.0005 0.0005
pH* 6.9 8.0 7.5 9.2
Total Ionic Strength 3.6615 0.8636 0.0346 0.0347

Yousef et al. (2011). A set of coreflooding experiments shows stepwise incremental oil recovery during
successive injection of field connate water (FCW), seawater (SW), two-times-diluted seawater (2dSW),
ten-times-diluted seawater (10dSW) and 20-times-diluted seawater. The adsorbed carboxylic group
should therefore decrease in the following order: FW, SW, 2dSW, 10dSW, and 20dSW. The same brine
composition (shown in Table 3) is used in batch speciation calculations.

Table 3—Brine composition used in experiments in Yousef et al. (2010). Unit of concentration is mol/kg water.
FCW SW 2SW 10SW 20SW

HCO3ⴚ 0.0058 0.002 0.001 0.0002 0.0001

Clⴚ 3.7200 0.907 0.453 0.0907 0.0453
SO42ⴚ 0.0036 0.0438 0.0219 0.00438 0.00219
Mg2ⴙ 0.1016 0.0879 0.044 0.00879 0.00439
Ca2ⴙ 0.4760 0.0163 0.0081 0.00163 0.00082
Naⴙ 2.5800 0.7957 0.398 0.07957 0.04980
Kⴙ 0.000 - 0
pH* 6.9 8 8 8 8
Total Ionic Strength 4.3153 1.1484 0.5740 0.1148 0.0624
SPE-180138-MS 7

The calculated concentration of the adsorbed carboxylic group in different forms are shown in Figure
2. The ⬎CO3Ca-COO dominates the adsorbed carboxylic group and decreases stepwise with the dilution
of seawater, while ⬎CaOH2-COO increase from SW to 20dSW.

Figure 2—Calculated adsorbed carboxylic acid for brine in Yousef et al. (2010).

Austad et al. (2012). Coreflooding experiments showed that injection of diluted formation water and
seawater in tertiary mode could improve oil recovery. 100-times-diluted formation water (100dFW) and
10-times-diluted seawater (10dSW) can lead to a more water-wet condition than formation water (FW)
and seawater (SW) for limestone cores. Therefore, the adsorbed carboxylic group should decrease from
FW to 100dFW, and from SW to 10dSW. We used the same brine composition in Table 4 in the speciation
calculation.

Table 4 —Brine composition used in experiments in Austad et al. (2012). Concentration is in mol/kg water.
FW SW 100FW 100SW

HCO3ⴚ 0.003 0.003 0.00003 0.0003

Clⴚ 3.643 0.662 0.03643 0.0662
SO42ⴚ 0.000 0.032 0.00000 0.0032
Mg2ⴙ 0.076 0.059 0.00076 0.0059
Ca2ⴙ 0.437 0.010 0.00437 0.0010
Naⴙ 2.62 0.594 0.0262 0.0594
Kⴙ 0 0 0 0
pH* 6.9 8 7 8
Total Ionic Strength 4.1590 0.8315 0.0416 0.0832

Figure 3 shows the calculated concentration of the adsorbed carboxylic group. The ⬎CO3Ca-COO
concentration is lower in 100dFW than in FW. Similarly, ⬎CO3Ca-COO concentration is lower in 10dSW
than in SW. Other forms of carboxylic adsorption do not show such a trend. ⬎CO3Ca-COO is the most
dominant form.
8 SPE-180138-MS

Figure 3—Calculated adsorbed carboxylic acid for brine in Austad et al. (2012).

Fathi et al. (2010). Spontaneous imbibition tests showed that when using different versions of synthetic
seawater the oil recovery can be improved significantly. Valhall brine (VB), seawater (SW), seawater
depleted in salt (SW0NaCl), SW0NaCl with four-levels-of-SO42⫺ (SW0NaCl4SO4) and SW0NaCl with
four-levels-of-Ca2⫹ (SW0NaCl4Ca) are used in spontaneous imbibition experiments. The results indicate
that the oil recovery is from small to large following such sequence: VB, SW, SW0NaCl and
SW0NaCl4SO4. The brine composition in Table 5 is used. We performed speciation calculations using
these brine compositions.

Table 5—Brine compositions used in experiments in Fathi et al. (2010). Concentration is in mol/kg water.
FW SW SW0NaCl SW0NaCl4SO4 SW0NaCl4Ca

HCO3ⴚ 0.0090 0.0020 0.0020 0.0020 0.0020

Clⴚ 1.0700 0.5250 0.1260 0.1260 0.1193
SO42ⴚ 0.0000 0.0240 0.0240 0.0960 0.0240
Mg2ⴙ 0.0080 0.0450 0.0450 0.0450 0.0450
Ca2ⴙ 0.0290 0.0130 0.0130 0.0130 0.0520
Naⴙ 1.0000 0.4500 0.0500 0.1940 0.0500
Kⴙ 0.0050 0.0100 0.0100 0.0100 0.0100
pH* 8.4 8.4 8.4 8.4 8.4
Total Ionic Strength 1.1160 0.6580 0.2580 0.4740 0.2580

The calculated surface concentration of adsorbed carboxylic acid is shown in Figure 4. ⬎CaOH2-COO
concentration decrease from VB to SW0NaCl4SO4. Concentrations of ⬎CO3Ca-COO decreases from VB
to SW however does not decrease further with removal of NaCl and addition of SO42⫺.
SPE-180138-MS 9

Figure 4 —Calculated adsorbed carboxylic acid for brine in Fathi et al. (2010).

Discussion of Chemical Mechanisms. The chemical mechanisms for wettability alteration using
modified seawater has been well documented to be related with PDIs (Zhang et al. 2006, Zhang et al.
2007, Strand et al. 2008, Austad et al. 2012). For chalk, sulfate is adsorbed on the chalk surface while
Ca2⫹ and Mg2⫹ are adsorbed in the crude oil surface. The carboxylic group is desorbed from the chalk
surface, due to the competition of sulfate for the chalk surface sites, and the competition of Ca2⫹ and
Mg2⫹ for the crude oil surface sites. However, a number of cases showed that diluted formation water and
seawater can alter wettability in the absence of PDIs. Here we performed speciation calculation for the
cases where PDIs is considered significant (Fathi et al. 2010, Austad et al. 2012) and the cases where PDIs
are considered insignificant (Yousef et al. 2011, Mahani et al. 2015).
As shown in Figures 1-4, different forms of the adsorbed carboxylic group have different tendencies.
⬎CaOH2-COO, which corresponds to the acid/base interaction mechanism, decreases as SO42⫺ concen-
tration increases and as NaCl concentration decreases (Figure 4). The sensitivity of this mechanism has
been discussed in Qiao et al. (2015) and is consistent with the PDIs mechanism as proposed by Austad
et al. (2008).
The carboxylic group adsorption via ion-binding through Ca2⫹, however, does not show much
correlation with SO42⫺ concentration. Instead, with dilution of the injection water, the ⬎CO3Ca-COO
concentration decreases, which is consist with Yousef et al. (2011) and Mahani et al. (2015).
The carboxylic group adsorption during coreflooding or contact angle measurement is irreversible, as
many experiments noted that high temperature and several weeks of aging is required for the crude oil to
adsorbed on the calcite surface (Austad et al. 2012). This indicates that the wettability alteration depends
on the initial condition (i.e. the formation water) and we should only allow carboxylic group desorption.
Namely, reactions (CO1), (CO2) and (CO3) are irreversible and only reaction towards the right is allowed.
Therefore, we can use the following to indicate water wettability

where [] represent these concentrations of surface species using the smaller of the calculated values
with formation water and with the injection water. For example,
10 SPE-180138-MS

where [⬎ CaOH2 ⫺ COO]SW,eq is the surface concentration from the calculation when all reactions are
assumed to be at equilibrium. The calculated wettability index for the cases considered in this paper are
shown in Figure 5. The calculated water wet indexes are consistent with the experimental observations.
Conclusion

Figure 5—Calculated wettability index for different brines. (A) Mahani et al. (2015). (B) Yousef et al. (2011). (C) Austad et al. (2012). (D)
Fathi et al. (2010), where SW1, SW2 and SW3 denote SW0NaCl, SW0NaCl4SO4 and SW0NaCl4Ca, respectively.

In this study, we propose a novel surface complexation model that explicitly considers the acid/base
interaction and ion binding interaction between crude oil and calcite surface. The new model reproduced
the wettability alteration trend for carbonate cores for both chemically tuned seawater and diluted
formation water. The major findings are as follows:
● The acid/base interactions shows great sensitivity with respect to Ca2⫹, Mg2⫹ and SO42⫺
concentrations.
● Diluted formation water or seawater can reduce the ion-binding through Ca2⫹. The ion-binding
mechanism is sensitive to the dilution of formation water and seawater.
● The combination of the acid/base and ion-binding mechanisms, which are irreversible desorption
reactions, can reproduce the observed wettability alteration trends from various types of water
compositions.

Acknowledgments
This research was supported by the Enhanced Oil Recovery Consortium (EORC) at the EMS Energy
Institute at the Pennsylvania State University. Dr. Russell T. Johns is Chair of the Petroleum and Natural
Gas Engineering program at The Pennsylvania State University. He also holds the Foundation CMG Chair
SPE-180138-MS 11

in Fluid Behavior and Rock Interactions and the Victor and Anna Mae Beghini Faculty Fellowship in
Petroleum and Natural Gas Engineering at The Pennsylvania State University.

References
Alotaibi, M. B., Azmy, R. and Nasr-El-Din, H. A. 2010. Wettability Challenges in Carbonate Reservoirs. Paper presented
at the SPE Improved Oil Recovery Symposium Tulsa, Oklahoma, USA, 24-28 April.
Alshakhs, M. J. and Kovscek, A. R. 2015. Understanding the Role of Brine Ionic Composition on Oil Recovery by
Assessment Of Wettability From Colloidal Forces. Advances in colloid and interface science.
Austad, T., Madland, M., Puntervold, T. and Korsnes, R. 2008. Seawater in Chalk: An EOR and Compaction Fluid. SPE
Journal 11 (04).
Austad, T., Shariatpanahi, S. F., Strand, S., Black, C. J. J. and Webb, K. J. 2012. Conditions for a Low-Salinity Enhanced
Oil Recovery (EOR) Effect in Carbonate Oil Reservoirs. Energy & Fuels 26 (1): 569 –575. http://dx.doi.org/10.1021/
ef201435g
Brady, P. V. and Krumhansl, J. L. 2012. A Surface Complexation Model of Oil-Brine-Sandstone Interfaces at 100° C: Low
Salinity Waterflooding. Journal of Petroleum Science and Engineering 81 171–176.
Brady, P. V., Krumhansl, J. L. and Mariner, P. E. 2012. Surface Complexation Modeling for Improved Oil Recovery. Paper
presented at the SPE Improved Oil Recovery Symposium Tulsa, Oklahoma, USA, 14-18 April.
Brady, P. V., Morrow, N. R., Fogden, A., Deniz, V. and Loahardjo, N. 2015. Electrostatics and the Low Salinity Effect
in Sandstone Reservoirs. Energy & Fuels 29 (2): 666 –677.
Buckley, J. and Liu, Y. 1998. Some Mechanisms of Crude Oil/Brine/Solid Interactions. Journal of Petroleum Science and
Engineering 20 (3): 155–160.
Fathi, S. J., Austad, T. and Strand, S. 2010. ⬙Smart Water⬙ as a Wettability Modifier in Chalk: The Effect of Salinity and
Ionic Composition. Energy & fuels 24 (4): 2514 –2519.
Goldberg, S. 2013. Surface complexation modeling. Reference Module in Earth Systems and Environmental Sciences.
Heberling, F., Trainor, T. P., Lützenkirchen, J., Eng, P., Denecke, M. A. and Bosbach, D. 2011. Structure and Reactivity
of The Calcite-Water Interface. Journal of colloid and interface science 354 (2): 843–857.
Karimi, M., Al-Maamari, R. S., Ayatollahi, S. and Mehranbod, N. 2015. Mechanistic Study of Wettability Alteration of
Oil-Wet Calcite: The Effect Of Magnesium Ions in The Presence and Absence of Cationic Surfactant. Colloids and
Surfaces A: Physicochemical and Engineering Aspects 482 403–415.
Lager, A., Webb, K., Black, C., Singleton, M. and Sorbie, K. 2008. Low Salinity Oil Recovery-An Experimental
Investigation1. Petrophysics 49 (01).
Mahani, H., Keya, A. L., Berg, S., Bartels, W.-B., Nasralla, R. and Rossen, W. R. 2015. Insights into the Mechanism of
Wettability Alteration by Low-Salinity Flooding (LSF) in Carbonates. Energy & Fuels 29 (3): 1352–1367. http://
dx.doi.org/10.1021/ef5023847
Morrow, N. R., Lim, H. T. and Ward, J. S. 1986. Effect of Crude-Oil-Induced Wettability Changes on Oil Recovery. SPE
Formation Evaluation 1 (01): 89 –103.
Pokrovsky, O. and Schott, J. 2002. Surface Chemistry and Dissolution Kinetics of Divalent Metal Carbonates. Environ-
mental science & technology 36 (3): 426 –432.
Pokrovsky, O. S., Mielczarski, J. A., Barres, O. and Schott, J. 2000. Surface Speciation Models of Calcite and
Dolomite/Aqueous Solution Interfaces and Their Spectroscopic Evaluation. Langmuir 16 (6): 2677–2688. http://
dx.doi.org/10.1021/la980905e
Qiao, C., Johns, R. and Li, L. 2016. Modeling Low-Salinity Waterflooding in Chalk and Limestone Reservoirs. Energy
& Fuels http://dx.doi.org/10.1021/acs.energyfuels.5b02456
Qiao, C., Li, L., Johns, R. T. and Xu, J. 2014. A Mechanistic Model for Wettability Alteration by Chemically Tuned Water
Flooding in Carbonate Reservoirs. Paper SPE-170966 presented at the SPE Annual Technical Conference and
Exhibition Amsterdam, The Netherlands, 27-29 October. http://dx.doi.org/10.2118/170966-MS
Qiao, C., Li, L., Johns, R. T. and Xu, J. 2015. A Mechanistic Model for Wettability Alteration by Chemically Tuned
Waterflooding in Carbonate Reservoirs. SPE Journal 20 (04): 767–783. http://dx.doi.org/http://dx.doi.org/10.2118/
170966-PA
RezaeiDoust, A., Puntervold, T. and Austad, T. 2011. Chemical verification of the EOR mechanism by using low
saline/smart water in sandstone. Energy & Fuels 25 (5): 2151–2162.
Romanuka, J., Hofman, J., Ligthelm, D. J., Suijkerbuijk, B., Marcelis, F., Oedai, S., Brussee, N., van der Linde, H., Aksulu,
H. and Austad, T. 2012. Low Salinity EOR in Carbonates. Paper presented at the SPE Improved Oil Recovery
Symposium Tulsa, Oklahoma, USA, 14-18 April. http://dx.doi.org/10.2118/153869-MS
12 SPE-180138-MS

Shariatpanahi, S., Hopkins, P., Aksulu, H., Strand, S., Puntervold, T. and Austad, T. 2016. Water Based EOR by
Wettability Alteration in Dolomite. Energy & Fuels.
Shehata, A. M., Alotaibi, M. B. and Nasr-El-Din, H. A. 2014. Waterflooding in Carbonate Reservoirs: Does The Salinity
Matter? SPE Reservoir Evaluation & Engineering 17 (03): 304 –313.
Strand, S., Puntervold, T. and Austad, T. 2008. Effect of Temperature on Enhanced Oil Recovery From Mixed-wet Chalk
Cores by Spontaneous Imbibition and Forced Displacement Using Seawater. Energy & Fuels 22 (5): 3222–3225.
Tang, G.-Q. and Morrow, N. R. 1999. Influence of Brine Composition And Fines Migration on Crude Oil/Brine/Rock
Interactions and Oil Recovery. Journal of Petroleum Science and Engineering 24 (2): 99 –111.
Yildiz, H. O. and Morrow, N. R. 1996. Effect of Brine Composition on Recovery of Moutray Crude Oil by Waterflooding.
Journal of Petroleum science and Engineering 14 (3): 159 –168.
Yousef, A., Al-Saleh, S. and Al-Kaabi, A. 2011. Laboratory Investigation of the Impact of Injection-Water Salinity and
Ionic Content on Oil Recovery From Carbonate Reservoirs. SPE REE 14 (05).
Zhang, P., Tweheyo, M. T. and Austad, T. 2006. Wettability Alteration and Improved Oil Recovery in Chalk: The Effect
of Calcium in the Presence of Sulfate. Energy & fuels 20 (5): 2056 –2062.
Zhang, P., Tweheyo, M. T. and Austad, T. 2007. Wettability Alteration and Improved Oil Recovery by Spontaneous
Imbibition of Seawater into Chalk: Impact of the Potential Determining Ions Ca 2⫹, Mg 2⫹, and SO 4 2⫺. Colloids
and Surfaces A: Physicochemical and Engineering Aspects 301 (1): 199 –208.