Applied Geochemistry 148 (2023) 105510

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Effect of boiler feed water composition on inorganic scaling in

once-through steam generators estimated using a Monte Carlo
modelling approach
Yury I. Klyukin a, b, *, Bernhard Mayer a, Benjamin Tutolo a
a
Department of Geoscience, University of Calgary, Calgary, Alberta, Canada
b
Yukon Geological Survey, Yukon Government, Whitehorse, Yukon, Canada

A R T I C L E I N F O A B S T R A C T

Editorial handling by Prof. M. Kersten Once-through steam generators (OTSGs) produce steam required to recover hydrocarbons from oil sand deposits.
OTSGs generate steam at high pressure and temperature, using boiler feed water (BFW) derived from produced
Keywords: water, recycled condensate boiler blowdown (BBD), and small amounts of make-up water sourced from local
Once through steam generator groundwater. During the OTSG operation cycle, BFW undergoes significant physical and chemical changes,
Oil sands
which can cause varying degrees of mineral (scale) precipitation, depending on the BFW quality. Scaling has
Steam generation
negative impacts on OTSG performance and has in the past resulted in OTSG tube leaks.
Boiler feed water
Scale In this study, we performed thermodynamic simulations using a Monte Carlo approach with the objective of
Modelling determining how the composition of the BFW and the steam quality affect scaling. We used 3 different scenarios,
Silicate minerals characterized by low, intermediate, and high iron-to-BFW ratios to represent various situations of BFW inter­
action with OTSG pipes. Within each scenario, BFW compositions were randomly assigned within industry-
relevant variations of variables including steam quality, pH, and concentrations of SiO2(aq), Mg2+, Ca2+,
Fe2+, Cl− , HCO−3 , K+, Na+, SO2−
4 and O2 and were allowed to precipitate scales according to thermodynamically
controlled solubilities of minerals as they were heated and boiled. Our results show that inorganic scale in OTSGs
is composed mostly of aegirine and various Mg and Mg/Ca silicates. We show that the concentrations of dissolved
Si, Mg, and Fe available for interaction with BFW are the main factors controlling the mass and mineralogy of
scale, whereas the total dissolved solids (TDS) and Ca concentrations within typical chosen operating limits have
negligible impact on the scale mass in OTSGs. The modelling results further indicate that efforts to minimize the
concentration of Mg in BFW to very low levels (<0.01 mg/kgBFW) show great promise for minimizing inorganic
scale formation in OTSGs. Our equilibrium modelling revealed that steam quality has little impact on the total
mass of inorganic scale formed in OTSGs because most of the mineral precipitation occurs at temperatures below
250 ◦ C, before boiling starts. However, this finding may not be fully valid if strong kinetic barriers prevent
process waters from achieving equilibrium via scale precipitation, especially at lower temperatures. Moreover,
because nucleated minerals may be transported through the OTSG without precipitating on the piping walls,
increasing steam quality reduces the capacity of BBD to carry over crystallized mineral phases in suspension.

1. Introduction via high temperature-pressure steam generated in Once Through Steam

Oil sands are one of the largest global reservoirs of petroleum
products. Their extraction at depths >70 m relies primarily on thermal
recovery methods including Steam Assisted Gravity Drainage (SAGD)
and Cyclic Steam Stimulation (CSS) (CAPP, 2019; Rui et al., 2018). In
both methods, viscosity of the hydrocarbons is lowered by thermal en­
ergy and in some cases by solvents. Thermal energy is usually supplied
Generators (OTSGs) (Godfrey et al., 2020; Gwak and Bae, 2010). OTSGs
are designed to generate significant volumes of steam, typically
consuming about 150 m3/h of boiler feed water (BFW), while converting
~80 mass % of this water to steam (Devon NEC Corporation, 2010). As
BFW moves through the OTSG units, it undergoes significant
geochemical and volumetric changes. In response to temperature in­
creases and boiling, as well as geochemical interaction with the

* Corresponding author. Yukon Geological Survey, Yukon Government, Whitehorse, Yukon, Canada.
E-mail address: yury.klyukin@yukon.ca (Y.I. Klyukin).

https://doi.org/10.1016/j.apgeochem.2022.105510
Received 5 August 2022; Received in revised form 4 November 2022; Accepted 7 November 2022
Available online 22 November 2022
0883-2927/© 2022 Elsevier Ltd. All rights reserved.
Y.I. Klyukin et al.
passivation layer of OTSG piping typically composed of magnetite,
Fe3O4 (Godfrey et al., 2020), varying amounts of minerals may precip­
itate from the BFW, depending on its quality. This mineral precipitation,
which is often referred to as scaling or fouling in the industrial literature,
decreases the efficiency of OTSGs and may ultimately cause OTSG tube
failure leaks. While mineral precipitation cannot be completely avoided
without incurring unrealistically high BFW treatment costs, OTSG op­
erators mitigate the potentially significant costs of OTSG failure leaks by
conditioning the BFW using various chemical water treatment ap­
proaches (Pedenaud et al., 2005) to meet industry-recommended BFW
specifications as well as by scheduling mechanical cleaning of the tubes,
commonly referred to as “pigging”.
The operational cycle of an OTSG from BFW to steam generation and
remaining condensate called boiler blowdown (BBD) is described in
detail in Klyukin et al. (2022) and is only briefly reiterated here for
context. OTSGs work with conditioned BFW pre-heated to >120 ◦ C
(Gwak and Bae, 2010) and generally utilize operating pressures between
~11 and 17 MPa. The operational cycle of current OTSGs is designed
such that ~80% of BFW is converted to steam (Devon NEC Corporation,
2010), leaving the rest as condensate (referred to as boiler blowdown,
BBD). BFW entering the OTSG consists of two main components: (1)
treated recycled water, which is comprised of produced water from oil
sand reservoirs and recycled BBD; and (2) make-up water, which is
typically derived from groundwater. BFW treatment approaches are
designed to adjust its composition to match the specifications suggested
by OTSG vendors (Fig 1A, and Table 1 in Klyukin et al. (2022)). Lime
softening based treatments, which are the subject of this work, are
focused on lowering the concentrations of free and emulsified oil, SiO2,
hardness and iron (Bridle, 2005; Pedenaud et al., 2005). However,
treatment procedures may leave some aqueous components unmodified,
and some of these dissolved constituents may ultimately contribute to
scale formation.
Previous research has examined mineralogical phases in the scale of
OTSGs and chemical compositions of BFW. For example, Thimm and
Kwasniewski (2008) published a method to estimate the rate of mineral
formation following empirical calculations. Luo et al. (2012) experi­
mentally investigated variations in scale mineralogy in response to
constraining the concentrations of Mg and Ca in BFW. Klyukin et al.
(2022) characterized the chemical and mineralogical compositions of
inorganic scale samples obtained from OTSGs used in hydrocarbon
production in Northeastern Alberta, Canada. Mineralogical analyses
revealed that scale samples were mineralogically similar between
different operators, and were dominated by Mg-, Na-, Fe-, and
Ca-inosilicates such as for example aegirine (NaFe3+Si2O6), pectolite
(Ca2NaH(SiO3)3), lizardite (Mg3Si2O5(OH)4), and serpentine group
(D2-3(Si2O5)(OH)4, where D = Mg, Fe, Ni, Mn, Al, Zn). To better
constrain the conditions leading to precipitation of these minerals in
OTSGs, these authors employed volumetric and thermodynamic models
that were able to reproduce the observed minerals, thereby improving
the understanding of thermodynamic and chemical parameters of BFW,
such as water composition and pH along the operational envelope of
OTSGs (Klyukin et al., 2022).
The objective of the present work was to use this geochemical
equilibrium model and a Monte-Carlo approach to explore the effect that
variable BFW compositions and steam quality have on inorganic scale
formation in OTSGs. The goal was to predict the predominant minerals
that precipitate in OTSGs and to determine the main factors controlling
inorganic scaling. The obtained novel insights should be highly valuable
for operators in their quest to minimize inorganic scaling in OTSGs.
2. Methods
Geochemical model. We used BFW compositions specified in the
work of Peramanu et al. (2014) as a reference composition (Fig. 1A).
With this BFW, we were able to reproduce mineral phases found in
samples recovered from OTSGs operations in hydrocarbon production
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Applied Geochemistry 148 (2023) 105510
facilities in Northeastern Alberta (Klyukin et al., 2022). In the study
presented here, we utilize the same model formulation, and performed
thermodynamic calculations using the Geochemist’s Workbench version
15.0.0 (Bethke et al., 2018), with a custom thermodynamic database for
minerals, created using the DBCreate software package (Kong et al.,
2013). The mineral pectolite (NaCa2Si3O8(OH)), observed in scale
(Klyukin et al., 2022) does not have experimentally constrained ther­
modynamic data needed to model its behavior. Hence, we assume that
pectolite behaves similarly to the well characterized mineral wollas­
tonite (CaSiO3). These two minerals belong to the same mineral group,
and while their chemistries are distinct, they have similar composition
and crystal structures and form in comparable hydrothermal settings
(Buerger and Prewitt, 1961; Weisenberger et al., 2014). It is important to
point out that our model did not include phosphorus, since its concen­
tration is not included in OTSG specifications (Gwak and Bae, 2010;
Klyukin et al., 2022; Pedenaud et al., 2005). However, phosphate min­
erals were identified in a few previously studied OTSG scale samples
(Klyukin et al., 2022). Their formation maybe associated with
phosphorus-containing additives used by some operators in water
treatment.
The model simulates the BFW solution as an open system at vapor-
saturated pressure. During the simulations, temperature, HCO−3 , and
H2O mass are manipulated to simulate heating and boiling (Klyukin
et al., 2022). The system is allowed to reach a new equilibrium state
following each temperature increment. Temperature in the simulation
runs rises from 25 ◦ C to first boiling at 320 ◦ C with pressure ~11.3 MPa,
then steam is generated as temperature is decreased to 315 ◦ C to
simulate temperature change in response to pressure decrease during
boiling due to pressure loss in the OTSG radiation section tubes. At the
same time, the H2O mass fraction is lowered to match steam quality
estimates and HCO−3 concentrations to mimic HCO−3 partitioning to the
steam as CO2. The resulting liquid after steam removal is cooled to 25 ◦ C
and represents the BBD (Fig. 1B).
To evaluate the effect of varying BFW compositions, Monte-Carlo
style simulations were performed in a stepwise manner using a Python
script, which interacted with the React module of the Geochemist’s
Workbench (GWB) by sending the incoming parameters and tracking the
output. Interaction between a Python script and GWB was achieved
using GWBPlugin (Bethke, 2021). This component of the GWB software
package is designed to link the functionality of core GWB components
with custom developed models in multiple programming languages. In
this study, BFW composition ± mineral phases were sent to the React
module at each step (initialization, heating, boiling, BBD cooling) to
simulate how the system changes in response to temperature and
composition adjustments. Once calculations were complete, the output
was redirected as an input to the React module.
At first, an unequilibrated BFW composition was randomly gener­
ated from data ranges shown in Fig. 1A within the operational envelope,
and Fe2+ either in dissolved state or as a specified mass of magnetite
(Fe3O4). Magnetite is used as the Fe-bearing medium in the system to
mimic the interaction between BFW and the magnetite-containing
passivation layer on OTSG piping. Selected ranges for BFW dissolved
constituents representative for industry adopted compositions (range
and reference composition, see Fig. 1A) were used in the Monte-Carlo
model, such that possible upsets in water quality, and possible varia­
tions in pH, steam quality and aqueous components of BFW were
considered. This compositional envelope was selected to explore how
inorganic scale formation responds to changes in concentrations of SiO2
and TDS (total dissolved solids) in BFW, hardness, pH, and the steam
quality achieved in OTSGs.
Three different scenarios with different Fe-to-water ratios were
modelled (Fig. 1), with each scenario iterated 1000 times with randomly
assigned BFW compositions:
1) No magnetite introduced into the system, and Fe concentration of
0.05 mg/l assigned to match the reference composition of BFW
Y.I. Klyukin et al.
Fig. 1. Compositional range of BFW, used in Monte Carlo simulations (top) and
procedural steps of geochemical model, developed to simulate scale and water
composition within operating envelope of OTSG.
(Fig. 1). This scenario focused on describing mineral phases in cases
where BFW is not interacting with OTSG tubing.
2) Magnetite introduced in BFW water in a 1:1 mass ratio, and the
magnetite remains a component of the system throughout the
modeling run. This case was selected to represent an end-member in
which BFW is fully equilibrated with the magnetite-containing
passivation layer of OTSG tubing at each moment of the BFW-
mineral system evolution.
3) Limited amount of magnetite introduced upon initialization and
after reaching equilibrium the remaining magnetite is removed. The
mass of introduced magnetite was set such that Fe could reach
concentrations of up to 0.4 mg/l, measured in BBD according to
Peramanu et al. (2014). This intermediate scenario with BBD-defined
Fe content is likely the closest approximation of actual bulk OTSG
systems currently operating in Northeastern Alberta.
After simulations, some runs resulted in extremely low pH (<5) of
BBD. Such cases are unlikely to be observed under standard operating
conditions. As shown by Weagle and Maltman (2012), the pH of BBD
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Applied Geochemistry 148 (2023) 105510
increases relative to BFW in response to thermal decomposition of
HCO−3 . HCO−3 decomposes to CO2, which migrates into the steam phase,
while OH− remains in the liquid phase causing pH to increase. In our
modelling, some of the runs must have initiated with both low pH and
low concentrations of HCO−3 in initial BFW, and hence there was insuf­
ficient buffer capacity to generate OH− through thermal decomposition.
This resulted in the pH decrease, which is to our knowledge not observed
in OTSG operations. To focus on more realistic scenarios, we set a cut-off
condition for successful runs such that those with pHBBD ≤ 5 (approxi­
mately 10% of all runs) were excluded from further mineralogical and
geochemical analyses. To analyze how scaling was affected by variations
in SiO2(aq), Mg2+, and Fe2+ concentrations, we employed K-means
clustering. K-means clustering is a machine learning technique that
permits grouping of similar observations by partitioning them in pre­
defined amount of clusters. Observations are then grouped (clustered)
around nearest mean (otherwise referred as cluster center/centroid).
This method was used with a total of 5 clusters initialized, vectorizing
observations according to the following parameters: the initial concen­
tration of SiO2(aq), Mg2+, magnetite in BFW, and scale mass at the end
of the boiling step at 315 ◦ C, when the mass of scale reaches its peak.
K-means clustering analysis was applied only to runs in scenarios with
limited magnetite, because runs in this scenario closely approximate
conditions in OTSGs.
3. Results
3.1. Geochemical characteristics of the BFW and its link with scale mass
We closely analyzed geochemical parameters of the scenario in
which the Fe content was mediated through the addition of low amounts
of magnetite (Fig. 2A), comparing it with the results of other scenarios.
In this analysis, all variables initialized at the start of the simulation
(steam quality, pH, TDS, SiO2(aq), Mg2+, Ca2+, Fe2+/magnetite, Cl− ,
HCO−3 , K+, Na+, SO2−4 , O2) were evaluated against their influence on the
total scale mass precipitating at the end of boiling (Appendix A). In a Fe-
rich scenario, scale mass is controlled strictly by SiO2 concentrations in
BFW (red points in Fig. 2A). In scenarios with limited Fe supply (BBD-
defined Fe content) and without magnetite, however, the mass of scale is
not linked to SiO2 concentrations in BFW (Fig. 2A, black and blue dots),
suggesting that both SiO2 concentrations and access to Fe play a key role
in scaling in OTSGs.
In general, the pH of the BFW increases compared to starting con­
ditions during the operational cycle, resulting in alkaline BBD (Fig. 2B).
However, our model indicated an inflection point at pH of ~8.2, below
which pH drops below the initial value, with some runs in magnetite-
free and BBD-defined Fe concentration scenarios reaching a pH < 5.
We considered these results to be unrealistic for standard operating
conditions, and did not include them in further results interpretation.
For the scenario with BBD-defined Fe content, K-mean cluster anal­
ysis indicated a significant link between the concentrations of SiO2 and
Mg in BFW (Fig. 3), while the averaged scale mass in all clusters was
roughly the same (~0.8 ± 0.3 mg/kgBFW, Fig. 4A). The correlation be­
tween SiO2 and Mg is most likely caused by equilibration of BFW after
initialization during the first step (Fig. 1B): a higher content of Mg
lowers the amount of SiO2 remaining in the BFW after equilibrating.
While these clusters are similar in scale mass, there is a significant
change in pH (Fig. 4D) and Mg and SiO2 concentrations (Fig. 4C, E):
those with higher SiO2 are characterized by higher pH and lower Mg
content. Our modelling shows no influence of the concentrations of Ca,
total dissolved solids (TDS), or steam quality on scale formation (Fig. 4G
and H and Appendix A).
Comparison of these clusters with data extracted from the magnetite-
free and excess magnetite scenarios shows that the mass of scale changes
significantly between scenarios (Fig. 4A). In the scenario with low Fe
concentration, the scale mass is below 0.4 mg/kgBFW, in the BBD-defined
Fe content scenario the mass of scale ranged from 0.4 to 1.4 mg/kgBFW
Y.I. Klyukin et al. Applied Geochemistry 148 (2023) 105510

Fig. 2. A) dependence of the maximum scale mass, observed at 315 ◦ C in each

run (horizontal axis) as a function of sio2 concentration in BFW. Color of the
points indicate which water-to-MAGNETITE (iron) scenario was used; B) ph
changes of equilibrated BFW, as it start (horizontal axis), until BBD discharged
and cooled to 25 ◦ C. (For interpretation of the references to color in this figure
legend, the reader is referred to the Web version of this article.)

Fig. 3. Results of the K-mean cluster analysis for all runs in scenario with
limited mass of magnetite provided to the system. Large points indicate cen­
troids of each cluster. Note log. horizontal scale for concentration of Mg in BFW,
while the scale for vertical axis, indicating dissolved SiO2 in BFW is linear.
Fig. 4. Compositional ranges (average and standard deviation) for all three
scenarios. Note that for scenario with constrained mass of magnetite provided,
compositional ranges estimated for each cluster. Concentrations of sio2aq, Ca,
and Mg (C, E, AND H) and ph (D) indicated at the start in black, and at the end
of the run in red. Note that in these cases left and right axes have different
scales. (For interpretation of the references to color in this figure legend, the
reader is referred to the Web version of this article.)

4
Y.I. Klyukin et al. Applied Geochemistry 148 (2023) 105510

with minor variations between the groups. In the scenario with excessive
amounts of magnetite, the scale mass is well above 10 mg/kgBFW
(Fig. 4A).
3.2. Changes in pH
In modelling runs with a starting pH below ~8.2, pH decreased after
simulation, resulting in pH of BBD ranging from 2 to 6 at room tem­
perature. While we did not include these runs in the analysis in this
paper, the raw data and results are reported in Appendix B raw data.
For most of the runs with starting pH > ~8.2, at the start of the simu­
lations pHin-situ of the BFW decreases during heating, reaching its min­
imum values at temperatures ranging from 150 to 250 ◦ C (Fig. 5A–E).
Compared to its initial value, pH decreases between 1.0 and 1.5 units.
Further heating increases pH slightly, until the initial boiling tempera­
ture is reached. During boiling as the temperature slightly decreases, in
the mineral/Mg-rich cluster 1 (Fig. 5E), pHin-situ decreases slightly, while
in other clusters pHin-situ either remains constant or increases slightly
(Fig. 5A–D). Subsequently, as BBD cools down for runs with initial pH
>~8.2, pHin-situ increases by ~3 units (Fig. 5A–E), resulting in an overall

Fig. 5. pH (on the left side of the figure) and mineral phases (on the right) plotted against the temperature. Selected runs have the composition closest to estimated
centroids of K-mean clusters (Fig. 3). Light and dark purple zones indicate changes in conditions of the model, corresponding to boiling and BBD cooling, respectively.
For pH, the grey dashed line indicates pH changes in reference run investigated and described by Klyukin et al. (2022). (For interpretation of the references to color in
this figure legend, the reader is referred to the Web version of this article.)

5
Y.I. Klyukin et al.
pH increase of 1–2 units compared to the starting conditions (Fig. 2B).
3.3. Mineralogical composition of the scale
3.3.1. Formation of aegirine
One of the most abundant mineral phases modelled in scale is
aegirine (NaFe3+Si2O6), sometimes also referred to as acmite (Fig. 5).
This mineral dominates the scale, and previous research had linked
aegirine formation with Si concentrations in the BFW (Bridle, 2005;
Gwak and Bae, 2010; Klyukin et al., 2022). In our work, for the scenario
with excess magnetite, total scale mass is linearly related with SiO2
concentration in BFW (Fig. 2B (red dots), note log scale for horizontal
axis), resulting in a markedly increasing mass of scale as SiO2 concen­
trations increase. However, in the scenarios with limited (BBD-defined)
or no magnetite addition, the concentration of SiO2 in BFW does not
show a correlation with total scale mass, and total scale mass decreased
by 1-2 orders of magnitude (Fig. 2A, black and blue dots) compared to
the scenario with excessive magnetite irrespective of SiO2
concentrations.
3.3.2. Mg silicates
Runs with minimal distance from cluster centroids in Fig. 3 (mean of
the cluster, outlined colored dots) were selected to identify the mineral
phases forming as temperature changes (Fig. 5). From cluster 1 to cluster
5, the concentration of Mg decreases and SiO2(aq) is increasing in BFW
(Fig. 3). This change in BFW composition is reflected in a decrease of
mineral phase diversity by orders of magnitude between clusters.
Aegirine is a dominating mineral phase in clusters 2–5, and forms at low
temperatures, consuming available iron, which is hosted in hematite.
Experimental studies have confirmed formation of aegirine at temper­
atures as low as 130 ◦ C (Decarreau et al., 2004; Redhammer et al.,
2019), in sets of experiments with synthesis time as high as 200 h.
As the Mg concentration in BFW decreases (Fig. 3), the Mg silicate
mineral diversity in the scale also decreases: cluster 1, which has the
highest Mg concentration in BFW, resulted in the following sequence of
Mg silicates forming as heating and boiling progress: talc, antigorite,
lizardite and tremolite (Fig. 5J). The same sequence of minerals appears
in lesser mass in cluster 2 (Fig. 5I). In cluster 3, only antigorite and
tremolite were observed (Fig. 5H), while in clusters 4 and 5, the only Mg
silicate present is tremolite during the heating and boiling steps (Fig. 5F
and G).
Minerals forming during the cooling of BBD were found to be quite
similar to minerals formed during heating and boiling. The main dif­
ference is the formation of andradite, a Ca–Fe silicate mineral, which has
not been observed in scale samples from various OTSG operations
(Klyukin et al., 2022). Notably, however, those authors did not sample
minerals precipitating from BBD.
Aegirine is most abundant and accounts for most of the scale mass at
the end of the boiling step at 315 ◦ C in the scenario with a limited mass
of magnetite provided to the system (Fig. 6). From all the minerals
present, only aegirine accommodates Fe in its structure, while other
silicate minerals accommodate Mg or Mg–Ca, although limited
isomorphic admixture of Fe on the Mg position is also possible.
Tremolite and wollastonite are also present in each cluster, with
tremolite abundance decreasing as Mg concentrations in BFW decrease
from cluster 1 to cluster 5. Other minerals found in scale include talc,
antigorite, lizardite and monticellite, but their abundance and mass also
decrease as the Mg concentration in BFW decreases from cluster 1 to
cluster 5.
4. Discussion
Our modelling results demonstrate that the concentrations of TDS
and Ca do not influence the scale mass in OTSGs. Instead, the concen­
trations of dissolved Si, Mg, and Fe (or its proxy, the mass of magnetite
added during the simulations) are the main factors controlling the mass
6
Applied Geochemistry 148 (2023) 105510
and mineralogy of scale in OTSGs. Importantly, while concentrations of
Ca and Mg are comparable upon initialization of the runs (Fig. 1A), and
while concentrations of both elements decreased significantly during the
runs (Fig. 4E and H), the correlation between scale mass and Mg con­
centrations is significantly stronger than the correlation between scale
mass and Ca concentrations (Appendix A, all 3 scenarios).
Silicate minerals present in scale were only observed at temperatures
>100 ◦ C. Below this temperature, hematite (Fe2O3) was present in some
runs but was consumed to form aegirine at higher temperatures. The
most common scale mineral is aegirine (NaFe3+Si2O6), followed by Mg
silicate minerals: talc (Mg3Si4O10(OH)2), minerals of serpentine sub­
group (antigorite-lizardite (Mg4Si2O5(OH)4)), and the Mg/Ca silicate
mineral tremolite (□Ca2Mg5Si8O22(OH)2 where □ indicates a vacancy
in the crystal structure). The only mineral that accommodates Ca but not
Mg is wollastonite (CaSiO3). However, this mineral’s abundance is
minor compared to other mineral phases (Fig. 5F–J), and Ca concen­
trations have only a minor effect on scale formation in runs from clusters
with extremely low Mg and high Si concentrations (clusters 4 and 5,
Fig. 6). The role of Ca and Mg on scaling is confirmed experimentally in
work by Luo et al. (2012) that showed that for both Ca and Mg below 10
ppb, scaling decreased compared to a reference case even with SiO2(aq)
up to 300 mg/l.
Other minerals, which could accommodate Ca but not Mg, belong to
the phosphate group; these have been observed in some of the recovered
scale samples (Klyukin et al., 2022). While we did not include P in our
simulations because its concentration is not stated in OTSG specifica­
tions, it is important to note that the presence of P in BFW will result in
the formation of Ca-bearing phosphate minerals such as hydroxylapa­
tite. These minerals will serve as a sink for dissolved Ca in the BFW,
linking Ca and P concentration with scale mass. Our model also did not
include Al, since its solubility in BFW is extremely low and Al concen­
tration in BFW/BBD is not stated in OTSG specifications (Gwak and Bae,
2010; Klyukin et al., 2022; Pedenaud et al., 2005). However, Al carried
into OTSGs as suspended particles can increase total Al concentration in
BFW and cause precipitation of tectosilicates, which were observed in a
subset of the samples described by Klyukin et al. (2022): sodalite, and
minerals of the plagioclase subgroup. However, because tectosilicates in
the investigated samples were sparsely distributed and did not represent
a significant portion in scale overall, we did not consider Al behavior
here.
Aegirine is the dominant mineral in scenarios with excess magnetite
and in BBD-defined Fe concentration. In the case of excess of magnetite,
the formation of aegirine has a strong positive link with SiO2(aq) con­
centration, resulting in a markedly increasing mass of scale as SiO2
concentrations increase (Fig. 2 (red dots) note log scale for scale mass).
In other scenarios, only the deficiency of Fe constrains the formation of
aegirine, while SiO2 either precipitates in Mg/Mg–Ca silicates or re­
mains in solution (Fig. 4). Constraining Mg to very low concentrations
(e.g., <0.005 mg/kgBFW, Fig. 4E) forces dissolved SiO2 to remain in the
BFW and BBD solutions, even when SiO2 concentrations in BFW reach
extreme values of ~400 mg/kgBFW in some runs (Fig. 4C). This finding
suggests that lowering Mg concentrations in BFW to very low levels
(<0.01 mg/kgBFW) may be an approach for minimizing scale formation
in OTSGs, as discussed by others (Bridle, 2005).
Magnetite formation on the internal lining of OTSG tubing is well
known and aided through the addition of oxygen scavengers to BFW
ensuring a reducing environment ((Godfrey et al., 2020) and references
therein). The resulting passivation layer protects the steel tubing from
corrosion. Previous research on steam-impacted oil field pipes (Gallup
and Hinrichsen, 2008; Khatib et al., 1992) reported Fe mobilization from
magnetite through a reaction with OH− at high pH by forming ferrite
(FeO−2 ), hypoferrite (FeO2− -
2 ) and Fe hydroxide (Fe(OH)4) ions. These
authors suggested that the formation of these ions preceded the forma­
tion of aegirine scale from solution. Our modelling results do not
contradict these findings, but indicate that in the entire range for dis­
solved O2 concentrations and pH ranges (Fig. 1), magnetite (Fe3O4) is
Y.I. Klyukin et al. Applied Geochemistry 148 (2023) 105510

Fig. 6. Mass of each mineral (vertical axis) plotted against total scale mass (horizontal axis), presented at 315 ◦ C at the end of the boiling, for all runs within scenario
with limited mass of magnetite provided to the system.

7
Y.I. Klyukin et al.
oxidized to hematite (Fe2O3) either partially in the case of the excessive
magnetite scenario, or entirely in other scenarios (Appendix B, Raw
data) at 25 ◦ C. Once the temperature reaches 120–200 ◦ C, hematite in
the presence of dissolved Na and Si is converted to hydrothermal
aegirine, similar to experimental results reported by Decarreau et al.
(2004). Conversion of magnetite to hematite could be achieved through
solid state recrystallization with intermediate formation of a poorly
characterized metastable phase, referred to in the literature as maghe­
mite (Fe2O3 (Cornell and Schwertmann, 2003),). This mineral phase has
a structure similar to that of magnetite and can mimic its appearance,
while most of the iron occurs in 3+ (oxidized) valence state. We spec­
ulate that the metastable phase maghemite (Fe2O3) is present as either
an intermediate step in the oxidation of magnetite to hematite or can be
formed directly during formation of the passivation layer instead of
magnetite.
Instability of magnetite in scenarios with low mineral-to-water ratio
(scenarios without magnetite and with BBD-defined Fe content), as
demonstrated in this study (Fig. 5J), are also confirmed by oxygen
fugacity data. Redox state in many geologic systems is quantified by the
magnetite-hematite buffer. Stabilization of magnetite at temperatures
below 150 ◦ C is possible only at extremely oxygen-deprived conditions,
as shown in the work by French and Eugster (1965). For example, the
partial pressure of O2 (pO2) needed to stabilize magnetite at 150 ◦ C is
around 1 × 10− 50 MPa, and at lower temperatures it decreases even
further. It is highly unlikely that such low concentrations of dissolved
oxygen in water are achieved under OTSG operating conditions,
prompting the formed magnetite to presumably reside in a metastable
state. As shown in Appendix A, the concentrations of dissolved oxygen in
BFW are changing significantly between scenarios, showing lower con­
centrations in the scenario where magnetite is introduced. Thus in sce­
narios with BBD-defined Fe content and excess of magnetite, dissolved
oxygen is linked with overall scaling, presumably through contributing
to hematite formation and later to formation of aegirine. Additionally,
experiments under hydrothermal conditions show rapid transitions be­
tween magnetite and hematite even in the absence of molecular O2
(Otake et al., 2007). OTSGs are characterized by high
water-to-magnetite ratio because a high amount of BFW (about 150 m3
of BFW per hour) is passing through magnetite-coated piping. Our re­
sults indicate that, at these conditions, magnetite is susceptible to
recrystallization to more water-soluble iron oxides, in addition to direct
effects of corrosion at elevated temperatures (Pietralik, 2012).
Our equilibrium-based modelling results suggest that steam quality
has little impact on the mass of inorganic scale formed in OTSGs. The
main reason for this finding is that most of the minerals precipitate from
the BFW prior to boiling at temperatures between 150 and 200 ◦ C by
formation of aegirine and Mg/Mg–Ca silicates (Fig. 5, Appendix B, Raw
data). The only mineral that forms according to our simulations during
boiling is wollastonite, but its contribution to scale is of minor impor­
tance, given that its maximum mass is about one order less than those of
aegirine and other minerals (Fig. 6). However, our simulations operate
as if the system is equilibrated at each temperature increment and hence
do not account for kinetics of the involved processes and ignore possible
flow impacts in the OTSGs. While our equilibrium modelling revealed
that steam quality has little impact on the total mass of inorganic scale
formed in OTSGs since most of the minerals grow from the BFW prior to
boiling at temperatures between 150 and 200 ◦ C, this finding may not be
fully valid if strong kinetic barriers prevent minerals from nucleating
during the relatively brief residence of waters in the OTSGs. Further­
more, increasing steam quality does ultimately concentrate aqueous
components in BBD, and this results in favorable conditions for scaling
down the line, where BBD is cooled off or reused.
5. Conclusions
This modelling study investigated how a wide range of BFW com­
positions and steam quality affect inorganic scale precipitation in
8
Applied Geochemistry 148 (2023) 105510
OTSGs. Our simulations indicate that inorganic scale formed in OTSGs is
compositionally dominated by aegirine and Mg and Mg/Ca silicates
(Fig. 6). The precipitation of Mg and Mg/Ca silicates occurs exclusively
from aqueous components dissolved in BFW, while the Fe required for
the formation of aegirine is derived from the iron oxide layer on OTSG
tubing with minor contribution from BFW. Our simulations indicate that
aegirine formation is preceded by recrystallization of magnetite in the
passivation layer to more soluble iron oxides such as hematite or
metastable maghemite. The industry is well aware of the necessity to
stabilize magnetite (Godfrey et al., 2020) and deploys oxygen scaven­
gers in BFW for this purpose. Our simulations demonstrate that, at dis­
solved O2 concentrations ranging from 0.001 to 0.05 mg/l (while
industry standard for dissolved O2 in BFW specified as <0.01 mg/l),
magnetite is stable only in scenarios with high iron-to-water ratios
(magnetite to water mass ratio 1:1). In this scenario, a small fraction of
magnetite recrystallizes to hematite, thereby reducing dissolved oxygen
to concentrations at which the remaining magnetite remains stable.
Scenarios with low iron-to-water ratios are more realistic for OTSGs
given the high BFW throughput. In this scenario, recrystallization of
magnetite to metastable maghemite or more soluble hematite is more
likely. At higher temperatures, these iron oxides are subsequently
consumed to form aegirine and inorganic scale.
A key finding of our modelling study is that the concentrations of
TDS and Ca in BFW have an inferior role in the scale growth in OTSGs.
The concentrations of dissolved Si, Mg, and access to Fe are the major
factors controlling the mass and mineralogy of scale in OTSGs. In
particular, the concentration of Mg in BFW was found to control the
extent of formation of Mg and Mg/Ca silicates, which together can ac­
count for more than a half of the mineral phases in inorganic scale by
mass in clusters 1 and 2 (Figs. 5 and 6). In other clusters, scale consists
predominantly (~80%) of aegirine. Na required to form aegirine along
with Fe and SiO2(aq) is abundant in BFW, but lowering its concentration
is currently not pursued in water treatment. While low Na concentra­
tions could control aegirine formation, Na concentrations would need to
be lowered by at least 4 to 5 orders of magnitude to have an effect on the
mass of aegirine, making this approach extremely challenging.
In scenarios with limited Fe in BFW (magnetite-free runs and BBD-
mediated Fe content in BFW), we show that, while an inverse relation
between Mg and SiO2(aq) concentrations exists, it does not influence the
overall scale mass (Fig. 4). Finally, only a single silicate phase (wollas­
tonite) can incorporate Ca without including Mg, but wollastonite
occurrence is minute compared to aegirine and Mg–Ca silicates in sim­
ulations with Mg above 0.01 mg/kgBFW (Figs. 4 and 6). Our results
strongly indicate that efforts to minimize the concentration of Mg in
BFW to very low levels (<0.01 mg/kgBFW) can help to minimize inor­
ganic scale formation in OTSGs.
Current BFW specifications frequently refer to total hardness as a key
parameter that combines both Mg and Ca concentrations into a single
parameter (reported as CaCO3) (Gwak and Bae, 2010; Klyukin et al.,
2022; Zeng et al., 2007). Our study results reveal that minimizing the
concentrations of Mg in BFW is of key importance for minimizing
inorganic scaling in OTSGs, while controlling Ca concentrations is less
relevant. Hence, continued reliance on total hardness as a BFW speci­
fication may lead to incorrect predictions of scaling factors. Instead, our
study reveals that future efforts should be focused on minimizing Mg
concentrations in BFW.
Declaration of competing interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Benjamin Tutolo reports financial support was provided by Natural
Sciences and Engineering Research Council of Canada. Bernhard Mayer
reports financial support was provided by Canada’s Oil Sands Innova­
tion Alliance.
Y.I. Klyukin et al. Applied Geochemistry 148 (2023) 105510

Data availability and Engineering Research Council of Canada (NSERC) through Collab­
orative Research and Development (CRD) grant number 532379- 2018
Data will be made available on request. and a Discovery Grant (number RGPIN-2018-03800) to BMT, and by
Canada’s Oil Sands Innovation Alliance (COSIA). The authors are
Acknowledgments grateful to Michael Nightingale for a discussion of the results of the
simulations, and COSIA industry partners for review of a draft manu­
Financial support for this work was provided by the Natural Sciences script and constructive feedback.

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi.org/10.1016/j.apgeochem.2022.105510.

Appendix 1, cross correlation between mass of scale at peak temperature and selected parameters of BFW at start, 25 ◦ C

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Y.I. Klyukin et al. Applied Geochemistry 148 (2023) 105510

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