Produced-Water-Chemistry History
Matching Using a 1D Reactive
Injector/Producer Reservoir Model
O. Vazquez, Heriot-Watt University; R. McCartney, Oilfield Water Services Limited; and
E. Mackay, Heriot-Watt University
Summary
Understanding connectivity between injection and production
wells is valuable information for reservoir management. Typically,
connectivity might be evaluated by use of downhole-pressure
information or by injecting tracers into the reservoir. A less-estab-
lished but inexpensive technique is to history match produced-
water compositions. For example, previous studies with this
method have identified barriers to flow in reservoirs. Information
on connectivity is also beneficial to scale management, particu-
larly that in which sulfate (SO4) -rich seawater is injected into res-
ervoirs containing formation water rich in divalent cations [i.e.,
barium (Ba), strontium (Sr), calcium (Ca)], because, in these cases,
the sulfate mineral-scaling conditions in production wells are a
function of the physical properties of the flow paths connecting the
injection and production wells (Wright et al. 2008).
In this study, we have considered this latter relationship from a
reverse perspective and explored the potential of history matching
produced-water compositions to understand the physical properties
of flow paths connecting injection and production wells for reser-
voirs under seawater flood. We have performed this history match-
ing with a 1D reactive transport model connecting an injector and a
producer through a number of noncommunicating layers character-
ized by permeability, porosity, and height (completion interval)
(Vazquez et al. 2009). The model simulates the injection of sea-
water, the mixing of the seawater with reservoir-formation brine,
and the subsequent deposition of sulfate scales (barium and cal-
cium sulfate among others) in the reservoir under equilibrium and
kinetic conditions. The results of interest are the predicted pro-
duced-water compositions over time from the model, similar to the
approach presented by McCartney et al. (2012); Tjomsland et al.
(2010); and Wright et al. (2008).
The model has been used to demonstrate the way in which pro-
duced-water compositions vary as the physical properties of the
layers between the wells are modified, and, particularly, the way in
which they vary in the presence of thief zones. Finally, a stochastic
method was applied—in particular a particle-swarm-optimization
(PSO) algorithm—for the automatic history matching of actual
produced-water compositions from individual wells in fields under
seawater flooding. The results are promising and show that this
technique can provide valuable information about the nature of
interwell connectivity.
Introduction
Mineral-scale precipitation is a significant problem in the oil and
gas industry. In field-development processes, oilfield scales can
precipitate at different stages: during drilling, if drilling mud
reacts with formation water; during completion, if completion
fluid is also incompatible with formation water; and, generally the
most damaging (because of the high-volume throughput and mass
of deposition), during the commingled production of incompatible
brines, such as seawater and formation brine.
Copyright V
C 2013 Society of Petroleum Engineers
This paper (SPE 164113) was accepted for presentation at the SPE International
Symposium on Oilfield Chemistry, The Woodlands, Texas, USA, 8–10 April 2013, and
revised for publication. Original manuscript received for review 19 February 2013. Revised
manuscript received for review 29 July 2013. Paper peer approved 30 July 2013.
November 2013 SPE Production & Operations
Seawater flooding is a common procedure in oil-producing
reservoirs to maintain the reservoir pressure, to sweep oil, and,
thus, to improve recovery. Injected seawater and formation brine
can be incompatible such that mixed scaling may result, resulting
primarily in deposit of sulfate scales. The scaling risk is assessed
during field appraisal or development, and subsequently managed
during production. Generally, the scaling risk is determined by
the simple mixing of seawater and formation brines. However, the
produced-water composition usually does not coincide with the
composition of a simple mixture of seawater and formation brine
because when seawater is injected and transported within the for-
mation, a number of geochemical reactions occur (Braden and
McLelland 1993; Mackay 2003; Mackay and Jordan 2003;
Mackay et al. 2003; Mackay et al. 2006; McCartney et al. 2005;
Paulo et al. 2001; Petrovich and Hamouda 1998; Sorbie and
Mackay 2000). Among the geochemical reactions that may occur
in a reservoir under seawater flooding, sulfate mineral precipita-
tion is possibly the most predominant (i.e., barite, anhydrite, and
celestite). It has also been reported that ion exchange is another
geochemical reaction (Mackay et al. 2006; McCartney et al.
2007), and that ion exchange may be a competitive multicompo-
nent process (Appelo and Postma 1999). Other authors (Houston
et al. 2006; Petrovich and Hamouda 1998) proposed dolomitiza-
tion as a possible mechanism for loss of magnesium (Mg) from
the produced water, despite the fact that dolomite is more likely
to precipitate over geological time scales (Sorbie and Mackay
2000).
The main purposes of this paper are, first, to present a 1D reac-
tive transport modeling program with PHREEQC (Parkhurst and
Appelo 1999), a geochemical model with the original title pH-
REdox-EQuilibrium. The program has evolved to include the
capability to model kinetic reactions and 1D transport (Parkhurst
and Appelo 1999), connecting an injector and a producer through
a number of noncommunicating layers characterized by perme-
ability, porosity, and height (see Fig. 1), with a similar approach
proposed previously, in which the reservoirs consist of noncom-
municating geological layers (Vazquez et al. 2009). This approach
is similar to the methodology suggested by Tjomsland et al.
(2010) to interpret produced water using a reactive transport
model, with the Geochemist’s workbench (Bethke 2005). The
same assumptions are adopted in this model, which considers the
mixing of injected water (seawater) and reservoir-formation brine,
during which a number of geochemical reactions are considered
(i.e., the precipitation and dissolution of sulfate and carbonate
minerals and competitive ion exchange).
Second, we seek to identify the sulfate-mineral-precipitation
envelope, which identifies the ion-concentration boundaries
involved in a precipitation reaction. Third, we seek to study the
effect of communicating layers between the injector and the pro-
ducer, and fourth, we seek to describe a stochastic method, in par-
ticular a PSO algorithm, for the automatic history matching of
actual produced-water compositions from individual wells in fields
under seawater flooding.
1D Reactive Transport Model
A description of the 1D reactive transport model that connects an
injector and a producer can be found in Fig. 1. The flow between
369
Injector
Q1
Q2
Q3
Q4
Fig. 1—1D reactive transport model connecting an injector and
a producer through a number of noncommunicating layers.
the wells is through a number of noncommunicating layers char-
acterized by permeability, porosity, and height (completion inter-
val) (Vazquez et al. 2009). The layer flow rate (QL) is calculated
by use of Eq. 1 (Vazquez et al. 2012), where N is the number of
layers, K is the layer permeability, and H is the layer height. This
expression calculates the partitioning of flow in a layered system
with no communication, where each layer is at the same differen-
tial pressure.
K L  HL
QL ¼ QT  PN : . . . . . . . . . . . . . . . . . . . . . . ð1Þ
i¼1 Ki  Hi
The model considers the injection of seawater, the consequent
mixing with reservoir-formation brine, and the subsequent disso-
lution/precipitation of sulfate and carbonate minerals and multi-
component competitive ion exchange. Although other reactions
might occur, such as dissolution of feldspar or clay mineral pre-
cipitation, their effect on the produced-water composition is likely
to be minimal (McCartney et al. 2012). The model uses the
PHREEQC thermodynamic database to simulate a number of
reactions and processes (Parkhurst and Appelo 1999). The model
considers each layer individually, and then the total produced-
water composition is calculated on the basis of the layer pro-
duced-water composition and flow rate by use of Eq. 2. The fol-
lowing mineral salts are allowed to precipitate/dissolve: barite,
anhydrite, celestite, calcite, and dolomite. The following ions may
be involved in ion-exchange processes: sodium (Na), potassium
(K), Ba, Sr, Ca, and Mg.
P
Ql  CIon
CIon
T ¼ lP l
: . . . . . . . . . . . . . . . . . . . . . . . . . ð2Þ
l QL
1D vs. 3D Reservoir Model
When attempting to find a match using a 1D model, describing
the communication between an injector and a producer proves, as
shown later, not to be a trivial problem. A 1D model is useful to
study specifically the interaction of a single producer with corre-
sponding communicating injectors, which may give a good esti-
mate of the dominant reactions occurring in the reservoir. The
main advantage of this approach is that it is much faster to run
than a 3D reservoir model.
Interpolating the same kind of calculations to reservoir scale is
a greater challenge computationally. Conventional reservoir his-
TABLE 1—FIELD CASE 1 COMPOSITION OF SEAWATER AND
FORMATION WATER
Seawater Formation Water
SO4 2,960 0
Ba 0 220
370
Producer 250
200
K1, H1
Ba Mixing
150
Ba, ppm
–14
Ba k = 1 × 10
K2, H2 –14
Ba k = 5 × 10
100 –13
Ba k = 1 × 10
K3, H3 50 Ba Equilibrium
0
K4, H4 0 20 40 60 80 100
Seawater Percentage
Fig. 2—Ba-concentration return profile vs. seawater fraction.
tory matching considers primary fluid rates and bottomhole pres-
sure, which, depending on the scenario, can make it a challenge to
find a well-matched model. Including geochemical reactions in an
already complex exercise in which one of the most-limiting fac-
tors is computational time creates an almost unfeasible computa-
tional problem. However, rather than immediately attempting to
find a match using a 3D reservoir model, running this type of cal-
culation in one dimension as an intermediate step might provide
valuable information in identifying which reactions occur, and
how they might be described.
One of the advantages of using a 3D reservoir model is the
possibility to predict where scaling might occur; this aspect has
been studied in another publication (Vazquez et al. 2013a). Sea-
water breakthrough was included in a conventional reservoir his-
tory matching as an extra constraint, which was determined by the
produced-water chemistry. This technique predicts spatially and
temporally the mixing front of the seawater and formation water.
This approach did not include any geochemical reactions; the aim
for the future will be to combine this type of study with the 1D
results to study two aspects: the predominant geochemical reac-
tions and water (injected and formation) flow paths.
Sulfate-Mineral-Precipitation Envelopes
The model described in the preceding sections was used to iden-
tify the precipitation envelope of sulfate minerals. The precipita-
tion envelope is the area between two curves (see Fig. 2): the top
curve describing the final composition after simple mixing of
formation and injected seawater, and the bottom curve, represent-
ing the composition of produced water in equilibrium with the
sulfate mineral of interest. The model was also used to investigate
the effect of precipitation kinetics on the produced-water
composition.
Fig. 2 shows an example of the results of barium sulfate
(BaSO4) precipitated in a single layer. The injected-seawater and
formation-water compositions are described in Table 1. It can be
seen that when BaSO4 precipitation is instant, the produced-water
Ba concentration drops sharply and follows the “equilibrium line”
as seawater breakthrough occurs and the seawater percentage
increases. However, when the rate of precipitation is reduced, the
Ba-concentration profile approaches the mixing line, more so at
the slowest precipitation rates (Mackay 2003). This demonstrates
that trends in produced-water Ba concentrations might be used to
understand the kinetics of scale deposition in a reservoir or well
(i.e., instantaneous vs. slow). This cannot be used to infer accu-
rately the kinetics of reaction in a reservoir, because that depends
on many factors, such as residence time, reservoir temperature,
and pressure. It also demonstrates the way in which the model
may be used to help explain the causes of trends in produced-
water Ba concentrations.
Flow Paths Between the Injector and the
Producer
Generally, reservoirs are not a single uniform formation with ho-
mogeneous physical properties, but, instead, they consist of the
November 2013 SPE Production & Operations
 Injector Producer
IW FW
IW FW
Fig. 3—Schematic of seawater flooding of a two-layer 1D model
(IW 5 injected water; FW 5 formation water).
interbedding of several layers with different physical properties,
such as porosity and permeability. Therefore, communication
between injectors and producers is likely to take place along a
number of flow paths (i.e., geological layers), and seawater break-
through may occur at different times because injected seawater
may flow faster in some layers than in others. Consequently, the
produced-water composition is determined by the mixing of dif-
ferent waters being produced from each layer.
A description of the study case is illustrated in Fig. 3, which
consists of two layers, each with the same porosity and height.
The total production rate was set to 1,000 B/D, and the injected-
seawater and formation-water composition are described in Table
1. For the sake of simplicity, only barite is allowed to precipitate,
with instantaneous kinetics.
A number of models with different layer flow-rate partitioning
were considered, in particular 10:90 (10% of total flow rate to top
layer and remaining 90% to bottom layer), 20:80, 30:70, 40:60,
and 50:50, and were determined by the layer permeability ratio.
The results showed that the produced-water Ba-concentration pro-
file depends significantly on the flow partitioning (see Fig. 4)
(apart from the 50:50 case, which is essentially a single homoge-
neous layer, resulting in a profile similar to that shown in Fig. 2).
It is clear that just after seawater breakthrough occurs in Layer 1,
the Ba concentration drops. Then, for some time, the Ba profile
remains at the same level, as the concentration of Ba is supported
by formation water produced from Layer 2 (the layer being pro-
duced at a lower rate), in which seawater breakthrough has not yet
occurred. During this period, the seawater percentage gradually
increases in Layer 1, giving the plateau in Fig. 4. The greater the
difference between layer flow rates, the longer, in terms of
increase in seawater percentage, the characteristic “plateau” lasts.
Then, at some point, each profile experiences another sharp drop
as a result of the seawater breakthrough occurring in Layer 2.
From this point onward, the Ba concentration approaches zero
because in both layers, seawater has fully mixed with the forma-
tion water and all available Ba has precipitated as BaSO4. The
Ba-concentration profiles can be explained with Eq. 3, where the
total concentration of Ba results from the mixing of the effluent
from each layer at a fixed time, C1(t) and C2(t), respectively, and
Q1 and Q2 are the layer flow rates.
250
200
150
Ba, ppm
100
50
0 1995), which would have shown similar results, but PSO has al-
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Years
Fig. 5—Ba-concentration return profile vs. time (years) with dif-
ferent flow-rate distributions (two layers).
November 2013 SPE Production & Operations
250
200
Mixing Line
Ba, ppm
150 10:90
20:80
100 40:60
30:70
50 50:50
0
0 20 40 60 80 100
Seawater Percentage
Fig. 4—Ba-concentration return profile vs. seawater fraction
with different flow-rate distributions (two layers).
C1 ðtÞ  Q1 þ C2 ðtÞ  Q2
CBa ðtÞ ¼ : . . . . . . . . . . . . . . . . ð3Þ
Q1 þ Q2
Fig. 5 shows the Ba-concentration profiles vs. time. For exam-
ple, in the 20/80% case, the first Ba drop occurs at approximately
0.12 years, at which time seawater breaks through in Layer 1 (the
most permeable layer). The second Ba drop takes four times as
long, occurring after 0.5 years. This can be explained by the fact
that the flow rate in Layer 2 is four times slower than it is in Layer
1, and, because the pore space in both layers is the same, seawater
will travel four times slower. This demonstrates that trends in pro-
duced-water Ba concentrations can be diagnostic of the physical
conditions in the flow paths connecting the injection and produc-
tion wells. Again, it also demonstrates how the model may be
used to help explain the causes of trends in produced-water Ba
concentrations.
Optimization Algorithm
Produced-water-chemistry history matching is an inverse prob-
lem, aiming to find a model (i.e., a combination of parameters
describing a number of geochemical reactions, such as the differ-
ence between the simulated and observed results being mini-
mized; Tavassoli et al. 2004). This may be attempted by varying
the parameters by hand until a match is obtained; however, this
might be extremely time consuming and onerous. This exercise
can be automated using an optimization algorithm, which will try
to find the combination of parameters that results in a good
match—the match is described mathematically by the misfit func-
tion. Then, the problem becomes a minimization of the misfit
function.
Among all the different types of optimization algorithms, sto-
chastic algorithms are more well-suited to this type of real-life
complex problem, in which the functional relationship between
the input variables and the misfit function is not clear, than deter-
ministic search approaches (Vazquez et al. 2013b). There is a
great variety of stochastic methods divided between local-search
and population-based methods. The hill-climber algorithm has
been used previously for the automatic isotherm matching with
very good results (Vazquez et al. 2013b). However, population-
search algorithms have been widely used in reservoir history
10:90
matching because of their flexibility in accommodating difficult
real-life problems. For the problem stated in this paper, a popula-
20:80
40:60
tion-based search is more appropriate because of the complexity
of the problem and the high number of parameters defining the
30:70
problem, rather than a local search. Other population-based search
50:50
algorithms would have been appropriate, such as the genetic algo-
rithm (Goldberg 1989) or differential evolution, (Storn and Price
ready shown its applicability to the problem. It is not the purpose
of this paper to compare the difference in performance of different
algorithms.
The PSO algorithm was first proposed by Kennedy and Eber-
hart (1995). It is a stochastic algorithm inspired by the flight of
371
 250 2,000
1,800
200 1,600
1,400
SO4, ppm
150 1,200
Ba, ppm
1,000
100 800
600
50 400
200
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Seawater Percentage
Fig. 6—Field Case 1 observed vs. simulated Ba- and SO4-con-
centration return profile vs. seawater fraction.
flocks of birds, which is very applicable to complex real-case
problems (Mohamed et al. 2010a; Onwubolu and Babu 2004).
This algorithm has been used effectively to find well-history-
matched reservoir models (Mohamed et al. 2010a; 2010b). PSO is
a set of agents (particles) described by a simple law of motion, in
which each particle’s motion is updated iteratively to maintain the
balance between exploration and exploitation in search of local
minima. The velocity of each particle is updated on the basis of
pbest (the best solution the particle has seen) and gbest (the best so-
lution across the entire population). The main computational steps
are described in the following steps, as previously described by
Mohamed et al. (2010a):
Step 1. Initialize the algorithm with a population of particles
of N models, randomly generated from the parameter space, in
which each particle is assigned a random velocity.
Step 2. Evaluate the fitness for every particle.
Step 3. Find pbest and gbest.
Step 4. Update the velocity of each particle i using Eq. 4.
vkþ1
i ¼ w  vki þ c1i  r1  ðpbesti  xki Þ
; . . . . . . . . . . . . ð4Þ
þ c2i  r2  ðgbestk  xki Þ
where vki is the velocity of particle i at iteration k; xki is the posi-
tion of particle i at iteration k; w is the inertia parameter; r1 and r2
are the random numbers in range [0,1]; and c1i and c2i are the
acceleration terms determined in each iteration as follows:
xkþ1
i ¼ xki þ vkþ1
i : . . . . . . . . . . . . . . . . . . . . . . . . . . . ð5Þ
Step 5. Repeat Steps 2 through 5 until the maximum number
of iterations is reached or another stopping criterion is met. The
fitness of each particle is calculated using the conventional L1
norm Base 10; see Eq. 6.
Ns X
X Ntj
 
M¼ logðOij  Sij Þ; . . . . . . . . . . . . . . . . . . . ð6Þ
j¼1 i¼1
where Ns is the number of observed ions in the produced water,
Ntj is the number of samples, O is the observed ion concentration,
and S is the equivalent simulated value, commonly known as the
misfit function, in which maximum fitness corresponds to the low-
est misfit value. Various parameters may be varied to yield a
match, including saturation index (SI), dispersivity, layer perme-
ability, and porosity.
Field Cases
The PSO algorithm described in the preceding section was applied
to two different field cases. In both cases, produced-water compo-
sitions were provided. Generally, produced-water composition is
recorded vs. production time. Although time could be tracked in
the model, there is not a clear method to synchronize both actual
and simulated times. Because the simulation time depends on the
production flow rate and the model is a simplification of the reser-
voir model, the authors consider that it is more appropriate to
372
TABLE 2—FIELD CASE 2 COMPOSITION OF SEAWATER AND
FORMATION WATER
Ba Observed
Seawater Formation Water
Ba Simulated
SO4 Observed
pH 8 6
SO4 Simulated
Na 10,890 55,000
K 388 530
Ca 428 22,000
Mg 1,368 1,700
Ba 0 1,200
Sr 8 1,600
SO4 2,650 0
Cl 19,700 125,000
Alkalinity 135 228
compare simulated and observed profiles vs. seawater fraction,
because there is no need to track time and, therefore, no need to
make any assumptions about water-production rates. The seawater
fraction was calculated on the basis of Cl– concentration, because
it is expected to display a linear behavior with respect to seawater
percentage and is considered to be a conservative ion (Braden and
McLelland 1993). Information about the field cases was very lim-
ited. Because there were no well logs available, a single layer was
assumed for both cases, and, because there was no evidence of a
thief zone (i.e., a highly permeable layer producing only seawater
and the others formation water), for the sake of simplicity, a sin-
gle layer may be the most reasonable assumption.
Field Case 1. Data for this case were limited; only the concentra-
tions of Cl, Ba, and SO4 ions in the produced water were available.
The formation-water composition can be found in Table 1. Sea-
water percentage was calculated using Cl, as shown previously.
The interwell distance between injector and producer was 2000 m.
Only barite precipitation/dissolution and formation dispersivity
were considered. Dispersivity is a characteristic of the porous me-
dium and can be thought of as the degree of mixing. One layer was
assumed, because the produced concentration profile did not seem
to show any resemblance to the generic profiles shown in Fig. 4.
Results of the automatic produced-water history matching can be
found in Fig. 6. The algorithm suggested a dispersivity value of
14.5 m, which could be interpreted as a low degree of mixing. This
is in reasonable agreement with reported dispersivity values from
field measurements (just under the reported range of between 20
and 100 m) (Arya et al. 1988; Mahadevan et al. 2003). The excel-
lent fit displayed in Fig. 6 could, in part, be a result of the limited
number of constituents used in the history-matching process,
which simplifies the problem.
Field Case 2. For the second field case, a full produced-water
composition was available (see Table 2), making history matching
much more challenging. The well was known to be part of a car-
bonate reservoir formation, which suggests high reactivity, where a
considerable amount of Ca and bicarbonate occur as a result of pH
changes. As in Field Case 1, there is no indication of thief zones
from the produced-water concentration profiles; therefore, only
one layer was assumed for the history-match exercise. Because of
the suspected high reactivity and formation composition and on the
basis of an evaluation of the produced-water analyses, the follow-
ing dissolution/precipitation reactions were considered likely to be
occurring in the reservoir: BaSO4, CaSO4 (as anhydrite), SrSO4,
CaCO3, and MgCa(CO3)2.
At the reservoir temperature (approximately 110 C) and con-
ditions, the solubility of gypsum is higher than that of anhydrite
as a function of seawater percentage, in which gypsum would
hardly precipitate (see Fig. 7). Also, ion exchange was assumed
where Na, K, Ba, Ca, Sr, and Mg may be involved, assuming
the presence of clay minerals, which will act as the exchanger sur-
face (Appelo 1994). The calculations were performed at 110 C,
November 2013 SPE Production & Operations
 1.0 SI_Anhydrite SI_Barite = 0.0, SI_Anhydrite = 0.0, SI_Celestite = 0.0
SI_Gypsum
Ca_Observed Ba_Observed SO4_Observed Mg_Observed
Sr_Observed Ca_Simulated Ba_Simulated SO4_Simulated
Mg_Simulated Sr_Simulated
0.5
3,000 30

0.0
SI = log(IAP/K)
2,500 25

Ba_SO4_Mg_Sr, ppm
–0.5 2,000 20

Ca, 10 ppm
1,500 15

3
–1.0

1,000 10
–1.5
500 5

–2.0
0.0 0.2 0.4
% Seawater
Fig. 7—Field Case 2 anhydrite and gypsum SI vs. seawater frac-
tion. (IAP 5 ionic-activity product.)
and the dispersivity was set to 50 m; the latter was a reasonable
value for the reservoir (medium degree of mixing), and trial cal-
culations showed that varying this parameter did not result in an
improved fit between the observed and simulated produced-water
compositions.
Initial calculations using the PSO algorithm provided a reason-
able match to the variations in produced-water composition vs.
seawater percentage (see Fig. 8), suggesting that the following
sulfate-precipitation reactions might be involved: BaSO4, CaSO4,
and SrSO4. Mg is also clearly involved in some geochemical
processes. The results suggested that dolomite precipitation would
not explain the Mg-concentration profile, and that Mg was more
likely to be controlled by ion-exchange processes (see Fig. 9),
because the simulated Mg is much higher than the observed.
These initial calculations did not provide a good match for
SO4 concentrations at high seawater percentages, and it is sus-
pected that this was because the sulfate-bearing minerals had
higher solubility than that used in the initial calculations. Thus,
the calculations were repeated using the same reactions but
adjusting the SI [SI¼log(IAP/K)] at which these minerals precipi-
tated in the reservoir. This resulted in an improved match between
the simulated and observed produced-water compositions (Fig.
10). This match required precipitation to occur at saturation indi-
0.6 0.8 1.0 0 0
0.0 0.2 0.4 0.6 0.8 1.0
% Seawater
Fig. 8—Field Case 2 observed vs. simulated Mg- and Sr-concen-
tration return profile vs. seawater fraction; SI for barite, anhy-
drite, and celestite is zero.
ces for barite, anhydrite, and celestite of 0.7, 0.2, and 0.4, respec-
tively. The changes in solubility of these three minerals are
necessary to account for the extra SO4 available. This is equiva-
lent to increasing the slight solubility of these minerals. The need
to increase the solubility of these minerals might reflect the dis-
crepancy in pressures between the model and the actual reservoir.
The model was run at 1 atmosphere, but the reservoir pressure
would be several hundred bar and the solubility of sulfate-bearing
minerals increases with increasing pressure. Although the thermo-
dynamic database includes only the temperature effect, not the
pressure, the results are in agreement with the solubility changes
as a function of pressure (Blount and Dickson 1973; Fan et al.
2012; Yuan and Todd 1991), where the solubility increases with
pressure.
Conclusions
A 1D, multilayer, reactive transport model connecting one injec-
tor and one producer has been developed to explore the factors
controlling produced-water compositions and to demonstrate the
type of subsurface information that can be obtained from this data
set.

No Exchange, SI_Barite = 0, SI_Anhydrite = 0, SI_Celestite = 0,

SI_Dolomite = 0 SI_Barite = 0.7, SI_Anhydrite = 0.2, SI_Celestite = 0.4
Ca_Observed Ba_Observed SO4_Observed Mg_Observed Ca_Observed Ba_Observed SO4_Observed Mg_Observed
Sr_Observed Ca_Simulated Ba_Simulated SO4_Simulated Sr_Observed Ca_Simulated Ba_Simulated SO4_Simulated
Mg_Simulated Sr_Simulated Mg_Simulated Sr_Simulated

3,000 30 3,000 30

2,500 25 2,500 25
Ba_SO4_Mg_Sr, ppm
Ba_SO4_Mg_Sr, ppm

2,000 20 2,000 20
Ca, 10 ppm
Ca, 10 ppm

1,500 15 1,500 15
3
3

1,000 10 1,000 10

500 5 500 5

0 0 0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
% Seawater % Seawater

Fig. 9—Field Case 2 observed vs. simulated Mg- and Sr-concen- Fig. 10—Field Case 2 observed vs. simulated Ca-concentration
tration return profile vs. seawater fraction; no cation exchange, return profile vs. seawater fraction; SI for barite, anhydrate, and
SI for barite, anhydrite, celestite, and dolomite is zero. celestite is 0.7, 0.2, and 0.4, respectively.

November 2013 SPE Production & Operations 373

 The model has been used to generate a BaSO4 precipitation
envelope, which is the area between the mixing curve and equilib-
rium precipitation curve. This can be easily generalized to any
other geochemical reactions. Simulations undertaken using the
model have shown that trends in produced-water Ba concentra-
tions could be used to understand the kinetics of scale deposition
in a reservoir or well (i.e., instantaneous vs. slow kinetics). This
should be taken with caution, because it does not provide an accu-
rate measurement of precipitation kinetics in the reservoir. It may
be used to estimate how fast the reaction might be; if it follows
the mixing curve, most likely the well has been inhibited, because
the reaction would have already occurred in the reservoir. How-
ever, there could be situations in which an injector is close to a
producer, so the residence time will be short, and the reaction
might be under kinetic conditions.
The model was also used to simulate the presence of a thief
zone in a two-layer reservoir, and the results showed that a very
characteristic profile can be expected under these conditions, in
which two drops in Ba concentration occur coinciding with sea-
water breakthrough in each of the layers. Resulting from barite pre-
cipitation caused by the commingling of formation and seawater, it
could be masked if the well were treated with scale inhibitors.
Again, this demonstrated that produced-water Ba concentrations
can be diagnostic of the physical conditions along the flow paths
connecting the injection and production wells.
Finally, we presented a method for automatic produced-water-
chemistry history matching: a PSO algorithm that is a stochastic
search method very appropriate for this complex real problem.
The method was applied successfully to two field cases. These
cases demonstrate that the trends in produced-water compositions
over time could provide information on the dispersivity along the
flow paths connecting the injection and production wells and the
reactions occurring in the reservoir, as previously shown by
McCartney et al. (2012); Tjomsland et al. (2010); and Wright
et al. (2008). The results from these field cases show the way in
which the PSO algorithm can be used to obtain this information
from produced-water analyses.
Although only an initial study, it is clear that interpretation
and history matching of produced-water compositions over time
has the potential to provide additional information on downhole
and reservoir conditions, in which the combination of reactive-
transport-modeling tools and optimization algorithms can be used
to help obtain valuable information about the reservoir.
Nomenclature
c1i ;c2i ¼ acceleration terms, dimensionless
CIon ¼ ion concentration, M/L3, ppm
HL ¼ layer height, L, ft
i ¼ particle
IAP ¼ ionic activity product
k ¼ reaction rate, mol/L/s
K ¼ solubility product
KL ¼ layer permeability, L2, md
M ¼ misfit, dimensionless
N ¼ number of layers
Ns ¼ number of observed ions in the produced water
Ntj ¼ number of samples
Oij ¼ observed data, M/L3, ppm
QL ¼ layer flow rate, L3/t, B/D
QT ¼ total flow rate, L3/t, B/D
r1, r2 ¼ random number in the range [0,1]
Sij ¼ simulation data, M/L3, ppm
t ¼ time
vki ¼ velocity of particle i at iteration k, dimensionless
w ¼ inertia parameter, dimensionless
xki ¼ position of particle i at iteration k, dimensionless
Acknowledgments
The authors thank the Flow Assurance and Scale Team at Heriot-
Watt University for their support. The following companies are
374
thanked for sponsorship of the FAST4 Joint-Industry Project:
Baker Petrolite, BG Group, BP, BWA Water Additives, Cham-
pion, Chevron, Clariant, ConocoPhillips, Equion, GALP, Halli-
burton, MIS, MWV, Nalco, Petrobras, Petronas, PTT Research &
Technology, REP, Shell, Statoil, Talisman, Thermphos, and Total.
We would like to thank David Parkhurst, Tony Appelo, and Scott
Charlton, who developed PHREEQC, which was used for all geo-
chemical calculations in this paper, and Tony Appelo in particular
for useful discussions.
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Oscar Vazquez is a research associate at the Heriot-Watt Uni-
versity Institute of Petroleum Engineering, where his research
interests include the modeling of all aspects of scale squeeze
treatments and reservoir history matching by use of pro-
duced-water chemistry. For the past 8 years, he has worked
on oilfield scale, developing and applying flow models to
design and optimize scale squeeze treatments, and more
recently including produced-water chemistry to improve con-
ventional reservoir history matching. Vazquez has authored or
coauthored more than 20 publications related to scale-
squeeze-treatment modeling. He holds a BS degree in mathe-
matics from the University Autonoma of Madrid, Spain; an MS
degree in mathematical modeling from East Anglia University,
UK; and an MS degree in information technology and a PhD
degree in petroleum engineering from Heriot-Watt University,
UK.
Ross McCartney is principal consultant for and owner of Oil-
field Water Services Limited. He has 33 years of experience (27
as a consultant) in the oil, nuclear, and geothermal industries
working on the acquisition and use of water analyses to under-
stand well and reservoir conditions in deep subsurface envi-
ronments. McCartney holds a BS degree in geology from the
University of Nottingham, UK, and a PhD degree in hydro-
chemistry from the Camborne School of Mines. He currently
serves on the SPE Scale Conference and Scale Workshop
committees and was Chair of the 2009 SPE Applied Technol-
ogy Workshop on Scale.
Eric Mackay holds the Foundation CMG Chair in Reactive
Flow Simulation in the Institute of Petroleum Engineering at
Heriot-Watt University, where he has worked since 1990. His
research interests include the study of fluid flow in porous
media, such as the flow of oil, gas, and water in subsurface
geological formations. Mackay has authored or coauthored-
more than 100 publications related primarily to maintaining oil
production in the face of mineral-scale deposition, but since
2005, he has also worked on carbon capture and storage. He
is involved in projects identifying methods for calculating
secure carbon dioxide storage potential in saline formations
and depleted hydrocarbon reservoirs. In addition to his
research interests, Mackay is involved in extensive consultancy
activities, delivers short courses for the oil industry, and is a
technical editor for a number of journals. He has also taught
reservoir simulation to the residential and distance-learning MS
degree classes at Heriot-Watt University since 1990. Mackay
holds a BS degree in physics from the University of Edinburgh
and a PhD degree in petroleum engineering from Heriot-Watt
University.
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