Fuel 309 (2022) 122040

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Full Length Article

Spill behaviours of pipeline-transportable processed bitumen products in

fresh water
Qin Xin , Lindsay J. Hounjet *, Austin Hartwell
Natural Resources Canada, CanmetENERGY Devon, 1 Oil Patch Drive, Devon, AB T9G 1A8, Canada

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

Keywords: Bitumen extracted from Canada’s oil sands resources is an abundant, unconventional crude oil used to produce
Bitumen liquid fuels. To permit its transportation by transmission pipelines from production sites to upgraders and re­
Petroleum fineries, the highly-viscous bitumen must first be blended with up to 50 vol% of light oil (“diluent”) to produce a
Partial upgrading
diluted bitumen (DB) with sufficiently low viscosity and density. Diluents occupy substantial pipeline capacity,
Oil spill
and are relatively expensive, so Canada is developing “partial upgrading” processes to reduce the diluent content
Aquatic behaviour
Environmental impact of pipeline-transportable bitumen products. Such processes lower bitumen’s density and viscosity by removing
some portion of its heaviest, asphaltene-rich fraction by, for instance, solvent-induced separation and/or ther­
mochemical conversion. Thus, processed bitumen products (PBPs) require less diluent to meet specifications for
transmission pipeline transportation. We compare the minimum diluent content requirements of several PBPs
meeting such specifications for density (≤ 940 kg/m3 at 15.0 ◦ C) and viscosity (≤ 350 cSt at a pipeline tem­
perature of 10.6 ◦ C, selected on the basis of DB viscosity measurements). In this work, PBPs meeting pipeline
transportation specifications are prepared by visbreaking and/or solvent-deasphalting of bitumen followed by
dilution with 32–47 wt% less diluent than the corresponding unprocessed DB. Public concern about environ­
mental risks associated with spillage of emerging PBPs during transportation has spurred investigations of these
products’ interactions with water. With little currently known about their aquatic behaviours, we evaluate the
emulsification and dispersion tendencies of pipeline-transportable PBPs after mixing these with fresh water
following a reported protocol, and compare these results with those for DB, bitumen-derived synthetic crude (SC)
oil, and conventional crude (CC) oil. The characteristics of floating water-in-oil emulsions are shown to depend
upon the oil’s asphaltene content and thermochemical process history. At high mixing energy, dispersed oil
content within the water column is seen to increase with oil resin-to-asphaltene ratio. In the aquatic system
employed, oil content of the water column is greatest for SC, followed by solvent-deasphalted products and DB,
followed by only-vis-broken product and CC. These results may aid in the development of oil spill behaviour
models and response plans needed for transporting PBPs.

1. Introduction
Over the past decade, increasing pipeline transportation of diluted
bitumen (DB) and emerging processed bitumen products (PBPs) has
raised concerns about the potential impacts of their spillage, especially
into sensitive aquatic environments, and how such impacts may
compare with those of more familiar, lighter products [1], including
conventional crude (CC) and synthetic crude (SC) oils. Such concerns
have inspired studies of DB behaviour in water under a range of con­
ditions [1–10]. Yet few reports have considered the aquatic behaviours
of PBPs [11–13].
Canada’s oil sands region contains the third largest proven oil
reserve in the world, representing a vast energy resource [14]. The
bitumen produced from this landlocked region is a heavy type of crude
oil which is too viscous to be transported by transmission pipelines from
production sites to upgraders and refineries. In order to reduce the bi­
tumen’s viscosity so that it can flow through these pipelines, it is
currently blended with a lighter hydrocarbon-based oil (or “diluent”) to
produce diluted bitumen (DB). Diluent types include condensates, syn­
thetic crude oil, or other light oils. As with other crude oils, DB must
meet the following specifications in order to be transported by trans­
mission pipelines: density ≤ 940 kg/m3 at 15.0 ◦ C, kinematic viscosity

* Corresponding author.
E-mail address: Lindsay.Hounjet@NRCan-RNCan.gc.ca (L.J. Hounjet).

https://doi.org/10.1016/j.fuel.2021.122040
Received 23 July 2021; Received in revised form 14 September 2021; Accepted 16 September 2021
Available online 2 October 2021
0016-2361/Crown Copyright © 2021 Published by Elsevier Ltd. All rights reserved.
Q. Xin et al.
≤ 350 cSt at pipeline temperature, and total olefin content ≤ 1.0 wt% 1-
decene equivalent [15]. In general practice, the diluent content of DB is
separated at refineries by distillation and pipelined back to bitumen
production sites for reuse. The diluent content of DB, which may
approach 50 vol% when transported in cold winter months, occupies
considerable pipeline capacity, effectively restricting the rate at which
bitumen can be transported, and presenting a bottleneck to production.
The need to minimize the diluent contents of pipeline-transportable
bitumen products has inspired “partial upgrading” processes [16],
which either remove or convert some of bitumen’s heaviest, least
valuable components to yield a product with significantly reduced
density and viscosity [17]. If either the density or viscosity of the
product still exceeds the specified threshold, then some smaller portion
of diluent must be added to yield a pipeline-transportable PBP. The
heaviest bitumen components (asphaltenes) are undesirable not only
because they impart high density and viscosity, but also because of their
high concentrations of “impurity” elements, including nitrogen, sulfur,
oxygen, and various metals [18]. If such heavy components are included
within a product transported through pipeline to a downstream refinery,
then they will ultimately be removed by energy-intensive upgrading and
refining processes [19].
The physical removal of bitumen’s heaviest components may be
achieved by “solvent-deasphalting” processes [20], whereby a light
paraffinic solvent (such as pentane) is first added to precipitate
asphaltenes from the maltenic supernatant. After separating the pre­
cipitate from the supernatant, solvent is removed from the latter to
afford solvent-deasphalted (SD) bitumen having reduced density and
viscosity. Alternatively, bitumen can be heated to convert its heavy
components into lighter ones. Such thermochemical processes perma­
nently reduce bitumen’s density and viscosity by cracking larger hy­
drocarbon molecules into smaller ones, including undesirable olefins
[21]. Although high-temperature cracking processes also generate un­
desirable coke that may contribute to fouling, lower-temperature “vis­
breaking” processes offer reduced operating and capital costs, generate
minimal coke, and optimize the recovery of lighter visbroken (VB)
products [22].
Appropriate response to oil spilled into an aquatic environment de­
pends on the specific geographical and hydrological context of the spill
site [4]. For instance, an oil spill into a riverine environment with water
flowing rapidly through narrow banks would present considerably
different response challenges than a surface spill into the middle of a
large, deep, relatively calm lake [4]. It is worth mentioning that offshore
and coastal environments also each present their own unique spill
response challenges, along with the possibility of alternative response
measures, including applications of spill treating agents, such as
chemical dispersants and shoreline cleaning agents, respectively.
Choosing the best response options and implementing these in the most
environmentally appropriate manner can minimize adverse impacts. In
relatively calm inland waters, the preferred response option offering the
least adverse impacts is booming and skimming, which may be
employed to contain and recover oil afloat at the water’s surface [23].
Such recovery may be impeded if the slick forms a stable water-in-oil
(w/o) emulsion that consists mostly of water [1], or if large portions
of the slick are lost, for instance, by evaporation, dissolution, dispersion,
or sinking. When oil is spilled into waters containing significant con­
centrations of suspended fine mineral particulates, oil droplets in the
water column may adhere to these relatively dense sediment particles
[8], sink, and become less responsive to resurfacing upon dredging [4].
Informed response to spills of a wide variety of light through heavy
petroleum products transported by pipeline requires understanding how
these products’ unique properties may predetermine their behaviours in
freshwater systems into which they may be introduced. Thus, the
composition of spilled petroleum greatly influences the efficacy of
various response options. For instance, the volatile proportion of DB,
attributable exclusively to its diluent content, greatly influences the
extent to which oil dissipates from a spill site by evaporation,
2
Fuel 309 (2022) 122040
dissolution, and dispersion [4]. When spilled, a product containing less
diluent should have less of an impact on air quality than a product
containing more diluent, thereby enabling safer and earlier response to
spillage of the former. The need to reduce diluent contents of such
products becomes even more apparent when considering that diluents
tend to contain significant concentrations of acutely toxic and volatile
aromatic compounds, including benzene, toluene, ethylbenzene, and
xylene (BTEX) [24], which may be especially hazardous to humans and
animals if released into inland aquatic environments [25]. On the other
hand, heavy asphaltenes and their interfacially-active subfractions [26],
stabilize water-in-oil (w/o) emulsions having high water contents (e.g.,
60–90 wt%) [27], which can impede spilled oil recovery efforts [28].
The formation of stable w/o emulsions may preclude the applicability of
oil spill treating agents, such as dispersants used to remediate offshore
spills [29]. After significant weathering on the surface of water,
asphaltene-reduced PBPs are more likely to remain buoyant than DB
with higher asphaltene content. The greater density of weathered DB
would likely render the oil more prone to sinking or submerging, which
could greatly impede its recovery. Thus, PBPs spilled into water may be
more amenable to recovery by booming and skimming. Owing to their
reduced heavy content, spilled PBPs are also likely to be more responsive
to washing from shorelines upon which they may become stranded.
Since PBPs’ contents of both heavy (asphaltene) and light (diluent)
components are lower than those of unprocessed DB, their intermediate
fractions, which contain polycyclic aromatic hydrocarbons (PAHs), are
likely to be greater. Therefore, PBP spillage into water may release
higher aqueous concentrations of PAHs attributable to chronic toxicity
when compared to unprocessed DB. However, to our knowledge at the
time of writing, aquatic toxicity data for PBPs have not been reported.
From both economic and environmental perspectives, the production of
PBPs may reduce costs associated with bitumen upgrading/refining,
pipeline transportation, and the persistence of oil spilled into aquatic
environments.
We have previously examined the intrinsic physical and chemical
properties of various PBPs, as well as the stability of their w/o emulsions
that form in various water types [12,13]. In the current report, we
expand upon these studies by comparing the minimum required diluent
content of DB with those of three PBPs, specifically solvent-deasphalted
diluted bitumen (SD-DB), visbroken diluted bitumen (VB-DB), and
visbroken then solvent-deasphalted diluted bitumen (VB-SD-DB), at
threshold pipeline transportation specifications. We also examine the
behaviours of DB, PBPs, SC and CC oils in a fresh water system at various
mixing energies following a reported protocol [30]. The water content of
the resulting w/o emulsion is determined gravimetrically, and results
are related to oil asphaltene content. The oil content of the water column
is also determined by its solvent extraction, isolation, gravimetric
quantification, and analysis by high-temperature simulated distillation
to correct for evaporative loss of the volatile oil fraction incurred during
isolation. Oil dispersion tendency is then related to oil resin-to-
asphaltene content ratio.
2. Materials and methods
2.1. Materials
The solvents, n-pentane (HPLC-grade) and dichloromethane
(CH2Cl2; 99.9 %) were purchased from VWR Canada and used as
received. The CC oil, Alberta Mixed Sweet Blend, was obtained from
pipelines in the Edmonton area and used as received. The bitumen was
produced from the Athabasca oil sands region in Alberta. The selected
SC oil, a fully-upgraded bitumen product, was supplied by an upgrader
in Alberta, and used as received. The original, undiluted bitumen was
used to prepare DB and the three PBP types: SD-DB, VB-DB, and VB-SD-
DB. All oils studied were refrigerated when not in use to prevent evap­
oration of volatile components. As illustrated in Fig. 1, a bitumen sample
was subjected to a solvent deasphalting process to yield SD bitumen.
Q. Xin et al.
Fig. 1. Flow chart illustrating the preparation of DB and three PBPs (VB-DB, SD-DB, and VB-SD-DB).
Another bitumen sample was subjected to a continuous, pilot-scale,
visbreaking process, from which VB bitumen was collected with ~ 16
wt% vacuum residue conversion. A portion of the VB bitumen was
subjected to fractional distillation to remove its volatile fraction boiling
< 204 ◦ C (3.4 wt%), and the resulting VB residue was subjected to
solvent deasphalting to yield VB-SD residue. The VB-SD residue was
reconstituted with the volatile fraction to the same proportion as within
VB bitumen (3.4 wt%), yielding VB-SD bitumen. The diluent, used in this
work to prepare DB and the three PBPs, consisted of distillate (boiling <
204 ◦ C) isolated from Access Western Blend DB as per an American
Standards for Testing and Materials (ASTM) method [31a]
2.2. General methods
Density measurements were performed using a densitometer at 20.0,
25.0 and 30.0 ◦ C as per an ASTM method [31b]. Viscosity measurements
were performed using a Brookfield viscometer at 20.0, 25.0 and 30.0 ◦ C
as per an ASTM method [31c]. High-temperature simulated distillation
(HTSD) analysis was performed according to an ASTM method [31d] on
an Agilent gas chromatograph with Analytical Control software.
Elemental analyses were performed to determine sample contents of C,
H, N, and S using an Elementar Analyzer as per an ASTM method [31e].
Oxygen (O) contents were determined using an Elementar Oxygen
Analyzer via an in-house method whereby the sample was pyrolyzed
under a stream of He, and evolved CO2 was quantified via gas chro­
matography using a thermal conductivity detector. The reported
elemental data were normalized with respect to total CHNSO content.
Total acid numbers (TANs) were measured using an ASTM method
[31f], as modified by the Canadian Crude Quality Technical Association.
[32] Total base numbers (TBNs) were measured using an ASTM method
[31g]. Total olefin contents were measured via a user-modified variant
of the proton nuclear magnetic resonance (1H NMR) spectroscopic
analysis method developed by the Canadian Association of Petroleum
Producers [33]. Contents of saturates, aromatics, resins, and asphaltenes
3
Fuel 309 (2022) 122040
(SARA) subfractions were determined by a user-modified variant of an
ASTM method [31h]. The reported SARA subfractions data were cor­
rected for loss by normalizing with respect to the total recovered mass of
all SARA subfractions.
2.3. Bitumen solvent-deasphalting process
The role of the solvent-deasphalting process is illustrated in Fig. 1. A
pre-weighed jar was charged with a known exact mass of ca. 300 g of
bitumen boiling ≥ 204 ◦ C, then approximately 5 volumes of n-pentane
were added (5 mL/g bitumen). The mixture was blended with an
impeller in a closed system at 1250 RPM for 1 h to ensure complete
mixing. The mixture was left undisturbed for 18–24 h to allow the
precipitate to settle from the supernatant. The supernatant was then
separated from the precipitate by filtration through a 0.45 µm filter
paper. The supernatant was transferred to a pre-weighed round-bottom
flask before removing its solvent content using a rotary evaporator with
final operating conditions of 60 ◦ C and 45 mbar for 3 h. The flask was left
to cool to ambient temperature and then re-weighed to determine the
recovery of SD bitumen boiling ≥ 204 ◦ C (77 wt%). The solvent content
of the asphaltene-rich precipitate was removed by evaporation, then the
jar containing the dry solid was re-weighed to determine recovery of
rejected, asphaltene-rich solid (23 wt%). The above solvent deasphalt­
ing procedure was then also applied to VB bitumen, which yielded VB-
SD bitumen (71 wt%) and rejected asphaltene-rich solid (29 wt%).
2.4. Dilution of processed bitumen
For each type of processed bitumen, the minimum diluent content
required to meet pipeline transportation specifications was first deter­
mined as follows. Four samples of each undiluted processed bitumen
type (SD, VB, and VB-SD bitumens) were obtained. These samples were
blended with different amounts of diluent, such that the diluent content
of the PBPs was either ca. 0, 5, 12.5, or 25 wt%. The variably-diluted
Q. Xin et al. Fuel 309 (2022) 122040

PBP samples of each type were then analyzed for density (ρ) and kine­ volume of water column. Results from triplicate experiments were used
matic viscosity (μ) at three temperatures (e.g., 20, 25, and 30 ◦ C). For to calculate the mean oil content of the water column and its standard
each diluted PBP type, linear relationships of ρ versus T and ln(μ) versus deviation. The water content within the buoyant w/o emulsion was
T− 1 were plotted (R2 ≥ 0.97 in all cases) and used to extrapolate or determined by comparing the emulsion’s total mass with that of the
interpolate density and viscosity values at other temperatures. For each fresh oil originally added to the jar less the mass of oil transferred to the
PBP type at each temperature, linear relationships of ρ versus diluent water column.
content and ln(μ) versus diluent content were also established (R2 ≥ 0.95
in all cases). These relationships were then used to calculate the mini­ 3. Results and discussion
mum required diluent content for each diluted PBP type needed to meet
the pipeline transportation specifications for both density (≤940 kg/m3 3.1. Properties of pipeline-transportable petroleum products
at 15 ◦ C) and viscosity (≤350 cSt at pipeline temperature) at the
threshold of either. The diluent content, density, and kinematic viscosity data for DB, the
Diluted PBPs at or near threshold specifications were then prepared three PBPs, SC and CC oils are listed in Table 1. Compared to the other
to target interpolated minimum required diluent contents. A pre- oils, CC has the lowest density, lowest viscosity, highest saturates con­
weighed jar was charged with undiluted, processed bitumen (either tent, and lowest aromatics content. Studies of this same CC source
VB, SD, or VB-SD bitumen, BP ≥ 204 ◦ C), the mass of which was then (Alberta Mixed Sweet Blend) can be found in cited references
recorded. A mass of diluent (BP < 204 ◦ C) was then added and recorded. [12,25,30]. The SC is produced by applying a series of upgrading
The mixture was manually homogenized for 60 s before sealing the jar techniques to fully remove bitumen’s vacuum residue fraction (boiling
tightly. The exact diluent content of the diluted PBP (either SD-DB, VB- ≥ 524 ◦ C) [21]. As a result, the fully-upgraded SC product is asphaltene-
DB, or VB-SD-DB) was then determined gravimetrically. free, and among the bitumen-derived products, it has the lowest density,
lowest viscosity, highest saturates content, and lowest aromatics con­
2.5. Oil/water mixing experiments tent. The DB has a diluent content of 23.8 wt% and meets the specified
pipeline threshold viscosity (350 cSt) at 10.6 ◦ C. Compared to the DB,
Petroleum products were mixed with fresh water according to a re­ each PBP requires substantially less diluent at either threshold density or
ported protocol [30], which was expanded in the current work to viscosity, whichever is limiting. For SD-DB, a minimum required diluent
include variable mixing energy and fresh water of a different composi­ content of 16.3 wt% is found to be sufficient to meet the same threshold
tion (see Supplementary Material for details). Each of the six petroleum viscosity as DB (350 cSt at 10.6 ◦ C), while VB-DB requires a minimum
products studied (DB, SD-DB, VB-DB, VB-SD-DB, SC, or CC) was inde­ diluent content of 14.1 wt% to meet the limiting threshold density (940
pendently mixed with fresh water (pH = 8.1, conductivity = 0.33 mS/ kg/m3 at 15.0 ◦ C). Subjecting the VB residue to solvent deasphalting
cm, total dissolved solids = 300 mg/L) at a high mixing energy via rotary further reduces the minimum required diluent content of the VB-SD-DB
agitation at 48 RPM in triplicate experiments. In order to gauge the ef­ product to 12.5 wt% at the limiting threshold density. Thus, the mini­
fect of mixing energy on the aquatic distribution of petroleum in this mum required diluent contents needed for these petroleum products to
system, the VB-DB, VB-SD-DB and CC oils were also each mixed with meet the threshold pipeline specifications decrease in the order: DB >
fresh water in triplicate experiments at a medium mixing energy (32 SD-DB > VB-DB > VB-SD-DB.
RPM), and a low mixing energy (12 RPM). The rotary agitation speed Compared to DB, SD-DB contains 32 wt% less diluent, VB-DB con­
used for high mixing energy experiments (48 RPM) was chosen to be tains 41 wt% less diluent, and VB-SD-DB contains 47 wt% less diluent at
similar to those employed in previous studies [30,8]. Medium (32 RPM) the limiting threshold specification. It should be noted that VB-DB and
and low (12 RPM) mixing energy speeds were chosen based on results of VB-SD-DB near the threshold density have viscosities (202 and 166 cSt at
exploratory tests, which generally revealed significant differences in oil 10.6 ◦ C, respectively) significantly lower than the threshold viscosity.
distributed among the water column and floating w/o emulsion.
For each mixing experiment, a 600 mL aliquot of fresh water was
Table 1
added to a glass jar having an internal volume of 2.5 L. A 30.0 mL aliquot
Physical and chemical data for the petroleum products studied.
of oil was added to the water in the jar to form a 5 mm-thick layer of
floating oil. The jar was sealed with a lid, then secured to a rotary Property DB SD- VB- VB-SD- SC CC
DB DB DB
agitator within a Memmert IPP750 environmental chamber at 15 ◦ C,
and left undisturbed for 4 h to allow for thermal equilibration of the Minimum Required 23.8 16.3 14.1 12.5 – –
mixture with its surroundings. [30] Each jar was rotated end-over-end at Diluent Content (wt
%)
either 12, 32, or 48 RPM for 12 h. After rotary agitation, the mixture in Measured Diluent 23.8 17.0 14.6 13.0 – –
the jar was immediately poured into a 1 L separatory funnel, which was Content (wt %)
left undisturbed for 60 min. The water column that formed beneath the Density, ρ at 15.0 ◦ C (kg/ 922 930 940 939 877 825
floating w/o emulsion was then drained into a second 1 L separatory m3)
Kinematic viscosity, μ at 350 292 202 166 20 7
funnel, and the mass of the isolated water column was determined. The
10.6 ◦ C (cSt)
total mass of w/o emulsion remaining both in the first separatory funnel Element Content C 83.5 83.7 83.7 83.9 86.8 85.3
and on the walls of the jar was determined gravimetrically. A 39.6 g (wt %) H 11.3 11.4 11.2 11.1 12.8 13.6
mass of NaCl was added to the isolated water column to reduce the N 0.4 0.3 0.4 0.3 0.1 0.1
solubility of oil in the aqueous phase. Oil was extracted from the water S 4.1 3.9 3.9 3.7 0.1 0.7
O 0.7 0.8 0.7 1.0 0.0 0.3
column using at least 3 × 100 mL aliquots of CH2Cl2 until the aqueous TAN (mg KOH/g) 2.0 2.0 1.2 1.0 < 0.1
phase appeared colourless. The organic extract was subjected to rotary 0.1
evaporation to remove the solvent along with some volatile oil fraction. TBN (mg KOH/g) 3.2 N.D. N.D. N.D. N.D. 0.7
The residual heavy oil fraction (boiling ≥ ca. 200 ◦ C) was then analyzed Olefins (wt % 1-decene) < < 0.5 1.1 1.3 < <
0.5 0.5 0.5
for its boiling point distribution by HTSD gas chromatographic analysis.
Saturates (wt %) 33.3 36.9 33.3 29.1 60.5 67.9
Under the assumption that oil within the water column was composi­ Aromatics (wt %) 39.9 44.1 33.0 50.7 34.2 21.8
tionally similar to fresh oil, boiling point distribution data for the Resins (wt %) 13.3 14.7 18.9 18.7 5.2 9.1
recovered heavy oil fraction were compared with those of the fresh oil, Asphaltenes (wt %) 13.5 4.3 14.8 1.5 0.1 1.2
which enabled quantification of the volatile oil fraction lost during re­ Resins-to-Asphaltenes 1.0 3.4 1.3 12.5 87.0 7.6
Ratio
covery, and in turn, the total mass of oil extracted from the known

4
Q. Xin et al.
Conversely, SD-DB near the threshold viscosity has a density (930 kg/m3
at 15.0 ◦ C) slightly lower than the threshold density. The density and
viscosity of the lighter SC and CC oils fall far below the threshold
specifications, and are included in Table 1 for comparison with DB and
PBPs.
Beyond the utility of partial upgrading processes for decreasing
diluent usage associated with bitumen transportation, there are addi­
tional benefits for mitigating environmental risks associated with the
spillage of diluent-reduced PBPs. For example, the light fraction of DB (e.
g., boiling < 204 ◦ C), attributable exclusively to diluent, contains all of
DB’s BTEX components (BP ≤ ca. 140 ◦ C), which are volatile, water-
soluble, bioavailable, and acutely toxic [25]. Reducing an oil’s diluent
content therefore reduces its BTEX content proportionally. In the event
of spillage, it follows that the risk of acute toxicity impacts should be
lower for oils containing less diluent. The BTEX contents of DB, Red­
water Condensate (a type of diluent), and CC are reported as 0.7, 3.9,
and 2.5 wt%, respectively [24]. It should be noted that many diluents
used by the petroleum industry also contain significant fractions boiling
≥ 204 ◦ C, which enhance phase compatibility with bitumen. For
instance, Redwater Condensate contains ca. 15 wt% of the fraction
boiling ≥ 204 ◦ C [24]. The SC oil used in this work, which itself may be
used as diluent within “synbit”, contains ca. 88 wt% of this same
fraction.
Chemical data for the six petroleum products studied are also pro­
vided in Table 1. Heteroatom (N, S, and O) contents are the highest for
DB and the lowest for SC oil, the latter of which is a fully upgraded
“sweet” bitumen-derived product (≤0.1 wt% S) that has undergone
hydrotreating processes to effectively remove heteroatoms. Interest­
ingly, the heteroatom contents of PBPs are not significantly lower than
those of the unprocessed DB, although to some small extent this obser­
vation may be explained by the lower diluent contents of PBPs (diluent
has very low heteroatom concentrations). The CC oil has much lower
heteroatom contents than DB and PBPs, although CC heteroatoms con­
tents are somewhat greater than those of SC oil. The observation that the
heteroatom contents of CC are substantially lower than those of DB is
consistent with DB’s greater capacity to neutralize bases and acids, as
evidenced by a comparison of these oils’ TAN and TBN data, respec­
tively. As has been previously observed, bitumen solvent deasphalting
has no significant effect on TAN [12], as both DB and SD-DB have TANs
of 2.0 mg KOH/g. This observation suggests that the asphaltene sub­
fraction removed from bitumen does not contain a significant portion of
bitumen’s organic acids that contribute to TAN. Interestingly, the TANs
of the visbroken products (1.0–1.2 mg KOH/g) are significantly lower
than that of DB. Visbreaking processes are known to thermally convert
organic acids into non-acidic species by decarboxylation with the loss of
CO2 [22]. Carbon-carbon bond breaking caused by visbreaking also
releases olefins and diolefins. Studies show that these compounds,
especially conjugated diolefins, are highly susceptible to condensation
reactions that effect deposits of carbonaceous matter and/or gum, which
cause fouling of downstream processing units [34]. Indeed, the olefin
contents of VB-DB and VB-SD-DB are expectedly higher than that of DB,
and slightly exceed the content allowable for pipeline transportation [2]
(≤1.0 wt% 1-decene equivalent) [33]. Mild hydrotreating may be
needed to reduce these products’ olefin contents to within pipeline
specifications [35,36].
The effectiveness of the solvent deasphalting process using a
pentane-to-bitumen ratio (p:b) of 5 mL/g can be assessed by comparing
the SARA-asphaltenes content of DB (13.5 wt%) with those of SD-DB and
VB-SD-DB, listed in Table 1. Interestingly, VB-SD-DB has a substantially
lower SARA-asphaltenes content (1.5 wt%) than SD-DB (4.3 wt%). It has
been previously demonstrated that visbreaking increases the aroma­
ticity of the asphaltenes subfraction [22]. From these observations, it
can be surmised that the increased aromaticity of asphaltenic molecules
caused by visbreaking decreases their overall solubility in n-pentane,
which may in part explain why VB-SD-DB has a significantly lower
asphaltenes content than SD-DB. Indeed, the solvent deasphalting of VB
5
Fuel 309 (2022) 122040
bitumen using p:b = 5 mL/g has yielded a greater proportion of rejected
asphaltene-rich solid (29 wt%) than did the solvent deasphalting of
unprocessed bitumen (23 wt%), an observation consistent with this
rationale. Moreover, the SARA-asphaltenes content is somewhat higher
in VB-DB (14.8 wt%) than in DB (13.5 wt%). Although the solvent
deasphalting of VB bitumen has incurred a substantial loss of
asphaltene-rich solid, there is a trade-off in that VB-SD-DB, among the
PBPs, is considered to have the highest overall quality from the
perspective of subsequent refining operations [17,37]. Interestingly,
among the petroleum products studied in this work, VB-SD-DB also has
the greatest aromatics subfraction content, representing about half of its
mass. Because SD-DB and VB-SD-DB have lower asphaltene contents
than DB, they may be anticipated to form less stable w/o emulsions [26].
Moreover, because these SD products also have lower diluent contents,
they may also undergo less evaporation and be more amenable to re­
covery than DB in the event of a spill into water.
The boiling point distributions of the petroleum products are illus­
trated in Fig. 2. Two red horizontal lines, corresponding to temperatures
of 204 ◦ C and 524 ◦ C at atmospheric pressure, have been included in the
graph to separate the “light” (boiling < 204 ◦ C), “gas oil” (boiling
204–524 ◦ C), and “vacuum residue” (boiling > 524 ◦ C) fractions. The SC
oil is a fully-upgraded bitumen product, almost completely devoid of the
heaviest vacuum residue fraction, having the narrowest distribution
among the products studied, as evidenced by the horizontal approach of
its curve in the gas oil region. Compared to the other oils, the unique
shape of the SC curve reflects its lower contents of both light and vac­
uum residue fractions. Conversely, the CC curve has a more consistent
slope than that of SC over the entire temperature range, and yet these
two oils share similarly low density and viscosity. Although the slope of
the CC curve in the gas oil region is comparable with those of DB and
PBPs, its curve is right-shifted to reflect that CC is a lighter oil.
Compared to DB, the reduced diluent contents of SD-DB and VB-SD-
DB are apparent in the region representing the light fraction. The
different shapes of the curves for SD-DB and VB-SD-DB within the light
fraction region can be attributed to VB-SD-DB’s inclusion of a volatile
fraction generated during visbreaking. Although VB-DB also contains
less diluent than DB, the generation of volatile components during vis­
breaking has rendered the curves of these petroleum products coinci­
dentally similar in the region representing the light fractions. When
examining the intermediate gas oil fraction, the curves of DB and PBPs
seem to have similar slopes. Among all products, DB is seen to contain
the greatest vacuum residue fraction (41 wt%). Comparing the distri­
bution of DB with that of SD-DB reveals that solvent deasphalting
removes a significant portion (7 wt%) of DB’s heaviest components
retained under conditions equivalent to 720 ◦ C.
3.2. Oil emulsification behaviour
An improved understanding of oil emulsification tendencies in
aquatic systems is needed to better inform the development of oil spill
behaviour models, environmental impact and risk assessments, and best
practices for spill preparedness and response. In the event of an oil spill
in water, the formation of stable w/o emulsions affects the applicability
of various spill response options, including the containment and re­
covery of spilled oil, and the application of spill treating agents [11].
Petroleum asphaltenes are known to stabilize w/o emulsions [26–28]. A
study of over 400 different crude oils has found that those forming
“stable” w/o emulsions have final water contents of 60–80 wt% after
one week at rest, while those considered “unstable” have final water
contents of 0–12 wt% [27].
To compare w/o emulsification tendency, petroleum products were
individually mixed with fresh water of one composition via rotary
agitation according to a reported protocol [30]. Notably, inland waters
across Canada differ considerably in their concentrations of various
dissolved ions, pH, and contents of dissolved organic matter. For
example, a Canadian lake impacted by mine drainage was found to
Q. Xin et al.
Fig. 2. Boiling point distributions of petroleum products.
contain dissolved iron concentrations as high as 20 g/L in the lower
portion of the water column [38], while waters in many boreal lakes are
of low salinity with high contents of dissolved organic matter [8]. Water
salinity, pH [30], and concentrations of various polyvalent metal cations
[39], such as Ca2+, Mg2+ and Fe3+ are well known to affect the forma­
tion and stability of w/o emulsions. The water used in the current work
had characteristics (see Table S15) typical of those found in Alberta’s
rivers. Fig. 3 shows that the water content of the floating w/o emulsion
produced at high mixing energy increases with the oil asphaltenes
content within the series of petroleum products studied. The w/o
emulsions formed with DB, SD-DB, VB-SD-VB, SC, and CC have generally
been found to conform to the shape of the jar in a uniform layer after
mixing. Interestingly, the w/o emulsion formed with VB-DB is visibly
distinct from those formed with other oils. After mixing with water, VB-
Fig. 3. Effect of oil asphaltene content on emulsification. Error bars represent
standard deviations from triplicate experiments performed at high mixing en­
ergy (rotary agitation speed of 48 RPM).
6
Fuel 309 (2022) 122040
DB has consistently formed a highly voluminous, free-floating, amor­
phous, semi-solid w/o emulsion within the jar. The VB-DB also has the
highest water content (88 ± 1 wt%) among the petroleum products
studied. It appears that the thermochemically-altered asphaltenes sub­
fraction of VB-DB affects this oil’s emulsification behaviour. The
aforementioned increase in asphaltenes aromaticity observed after vis­
breaking [13] may have contributed to VB-DB’s very different emulsi­
fication behaviour compared to the other products, although the
rationale for this difference is not fully understood at present. After
removing most of the thermochemically-altered asphaltenes from VB
bitumen by solvent deasphalting, the emulsification behaviour of the
VB-SD-DB product improves greatly, with its floating oil layer exhibiting
much greater uniformity and somewhat reduced water content (74 ± 6
wt%), which is similar to those of DB (83 ± 2 wt%), SD-DB (79 ± 2 wt%)
and CC (75 ± 10 wt%), and far greater than that of SC (29 wt%), which
does not form a stable w/o emulsion, as is evident by its low water
content.
As shown in Fig. 3, the water content of the w/o emulsion increases
logarithmically with oil asphaltenes content. When comparing SC and
CC with similarly low viscosities (20 cSt and 7 cSt, respectively), the
order-of-magnitude difference in their asphaltene contents appears to
result in very different water contents of their w/o emulsions. The fact
that CC has ten times greater asphaltenes content than SC appears to
help stabilize the water-in-CC emulsion to a much greater extent than
that of the “unstable” water-in-SC emulsion. Although VB-SD-DB and CC
have very different viscosities (166 cSt and 7 cSt, respectively), the
similarity of their w/o emulsions’ water contents reflects these oils’
similar asphaltene contents.
It should be noted that inferences drawn from comparisons of
bitumen products’ characteristics and aquatic behaviours are valid only
for products originating from a single bitumen source. In this work, we
show that mixing solvent deasphalted products with fresh water gen­
erates w/o emulsions having only slightly lower water contents than
those of the corresponding unprocessed diluted bitumen. Previous
studies using bitumen from different sources (Cold Lake Blend DB [12]
and Western Canadian Select DB [13]) have revealed much more dra­
matic reductions in water contents of w/o emulsions upon solvent
deasphalting [12] or visbreaking followed by solvent deasphalting [13].
In those previous studies, however, the viscosities of solvent deasphalted
products were up to an order of magnitude lower than those of their
respective, unprocessed diluted bitumen products, making the com­
parison of their aquatic behaviours less relevant to spills of products
Q. Xin et al.
transported by pipeline [12,13]. In the current study, the viscosities of
DB (350 cSt), SD-DB (292 cSt), VB-DB (202 cSt) and VB-SD-DB (166 cSt
at 10.6 ◦ C) are less variable than in the previous studies, and the density
or viscosity of each oil is close to its specified threshold for pipeline
transportation. Thus, the aquatic behavioural comparison presented in
this work is considerably more relevant than those of previous works
with respect to the spillage of petroleum products transported by
transmission pipelines. In the current work, the oil’s tendency to
disperse into the water column is also evaluated systematically by
following an established protocol [30].
3.3. Oil dispersion behaviour
In the event of an oil spill affecting an aquatic environment, the
tendency for oil to disperse into the water column can influence its
exposure to subsurface organisms and also its removal by natural
biodegradation processes [1]. Previous reports on oil behaviour in
various water types have demonstrated that the DB content of the water
column is the greatest in fresh water that is free of suspended sediment
particles [12,13]. In Canada, aquatic environments most likely to be
affected by the spillage of DB and PBPs from pipelines consist of fresh
water. Therefore, in this work, DB, PBPs, SC and CC oils have each been
mixed with sediment-free fresh water to compare their aquatic behav­
iours. We have also studied the effect of mixing energy on the oil content
of the water column.
Fig. 4 reveals, as expected, that the oil content of the water column
increases with mixing energy for the products tested (VB-DB, VB-SD-DB,
and CC). This observation can be explained by considering that a higher
mixing energy generates smaller oil droplets in the water column, which
are slower to resurface than larger droplets, as per Stokes’ Law [40]. At a
lower mixing energy (12 RPM), the oil content of the water column is
low and similar for all oil types (<1 g/L). At a moderate mixing energy,
the oil content of the water column begins to depend on the oil type,
with CC exhibiting lower oil content of the water column (<1 g/L) than
the VB-DB and VB-SD-DB (~1–3 g/L). A possible factor contributing to
this observation is that CC has a much lower density than each of the
other oils studied, which would result in a faster resurfacing of its
dispersed droplets. At a high mixing energy, the oil content of the water
column decreases in the following order: SC (~8 g/L) > VB-SD-DB ~ SD-
DB ~ DB (4–7 g/L) > VB-DB (~2 g/L) > CC (~1 g/L).
With constant oil–water interfacial tension, increasing oil viscosity
tends to decrease its tendency to break up into smaller, more stable
water-dispersed droplets in response to supplied mixing energy [41,42].
Fig. 4. Effect of mixing energy on oil content of the water column. Error bars
represent standard deviations from triplicate experiments.
7
Fuel 309 (2022) 122040
Although the viscosity of DB (ca. 350 cSt at 10.6 ◦ C) is more than twice
that of VB-SD-DB (166 cSt), these two oils, along with SD-DB, give rise to
similar oil contents of the water column. Among DB and PBPs, the oil
content of the water column produced with VB-DB is by far the lowest.
The VB-DB is different from the other PBPs in that it contains a signifi­
cant fraction of thermochemically-altered asphaltenes, which could
account for its dramatically different behaviour. The relatively high
stability of the w/o emulsion formed with VB-DB appears to explain its
relatively low tendency to disperse into the water column. Oil trapped
within this highly stable w/o emulsion may be less available to disper­
sion. Consistent with observations made in a previous study, thermally-
processed bitumen products containing altered asphaltenes tend to
disperse less than those that do not [13]. In that same study, the mixing
of synthetic crude oil with fresh water, under conditions nearly identical
to those of the current work, also led to a high SC content of the water
column, in accordance with the instability of its w/o emulsion [13].
Fig. 5 demonstrates a proposed relationship between the average oil
content of the water column and oil resins-to-asphaltenes (r/a) content
ratio among the five bitumen-derived products. This observation is
consistent with those of others, who have reported that the oil r/a ratio
influences the electrical properties of the oil–water interface [42]. Their
previous work found that oils with higher r/a ratios (>3.0) gave rise to
oil-in-water (o/w) dispersions having interfaces with large zeta poten­
tials, wherein oil droplets resist coalescence to stabilize water-dispersed
oil. [43] Indeed, DB and VB-DB have low r/a ratios of 1.0 and 1.3,
respectively, consistent with the lower oil contents of their water col­
umns when compared to those of VB-SD-DB and SC, having r/a ratios of
12.5 and 81.7, respectively. This trend is, however, not applicable to CC
with r/a = 7.6, which has a significantly different chemical composition
from any of the bitumen-containing products, and also very different
density and viscosity, as described above. Among the bitumen-sourced
products (all except CC) presented in Fig. 5, the oil content of the
water column correlates roughly with oil r/a ratio.
In this work, the DB content of the water column is found to be ca.
5.2 g/L, while that of CC is only ca. 1.2 g/L. A previous study compared
the dispersion behaviour of a different type of diluted bitumen (Cold
Lake Blend DB) in a softer fresh water type (previously, [M2+] = 18 mg/
L; currently, [M2+] = 62 mg/L; M = Ca, Mg), but under otherwise
identical conditions. That study found the oil content of the softer water
Fig. 5. Oil resins-to-asphaltenes ratio versus dispersion tendency. Error bars
represent standard deviations from triplicate experiments at high mixing energy
(48 RPM).
Q. Xin et al.
column to be more than an order of magnitude lower, at 0.18 g/L, while
CC (Alberta Mixed Sweet blend, also used in the current work) content of
the water column was only slightly lower, at 0.82 g/L [30]. Water
chemistry data for the harder water type used in this work are provided
within the Supplementary Material. The extent to which water hardness
impacts the aquatic behaviour of oil is the subject of an on-going
investigation.
4. Limitations
Petroleum products transported by pipelines differ tremendously,
both in terms of their composition (see Table 1 for example) and aquatic
behaviour. Experimental results corresponding to a petroleum product
obtained from a specific sampling source/location and time should
never be attributed to any similar product, or even one having the same
identity if sampled from a different source or at a different time. The
extent to which experimental results obtained for a given product may
be considered to generally represent any related product requires careful
consideration of how the two products compare in terms of their
composition as determined by standardized analytical protocols. Ulti­
mately, however, any evidence-based understanding of how composi­
tional differences between petroleum products may affect their aquatic
behaviour requires systematic experimental comparisons.
5. Conclusions
In this work, knowledge gaps and concerns about how transmission
pipeline-transportable PBPs may behave when spilled into freshwater
environments are addressed by comparing PBP aquatic behaviours with
those of the corresponding, unprocessed DB, CC, and SC oils. Vis­
breaking and/or pentane-solvent deasphalting significantly reduces the
amount of diluent needed to transport bitumen products by pipelines.
Solvent deasphalting and visbreaking processes improve the quality of
pipeline-transportable bitumen products from the perspective of sub­
sequent refining operations. However, the olefin contents of visbroken
products may need to be reduced further via hydrotreating to permit
their pipeline transportation. Compared to unprocessed DB, the SD-DB
requires 32 wt% less diluent, VB-DB requires 41 wt% less diluent, and
VB-SD-DB requires 47 wt% less diluent. In a freshwater system, under
high-energy mixing conditions, SD-DB and VB-SD-DB products are
similar to DB in terms of both their w/o emulsification and o/w
dispersion behaviours. In the event of their spillage, PBPs will undergo
less evaporative loss than DB as a result of their lower diluent contents.
Compared to DB and CC, VB-DB (not solvent-deasphalted) forms a
highly stable, voluminous, semi-solid w/o emulsion, and so may be less
amenable to recovery by booming and skimming processes, and less
responsive to dispersant applications than either DB, SD-DB, or VB-SD-
DB. At a high mixing energy, the resins-to-asphaltenes ratios of
bitumen-sourced products are found to correlate positively with oil’s
tendency to disperse. These results may be used to inform policy-making
decisions pertaining to the transportation of bitumen-sourced products.
Future work will examine the aquatic behaviours of PBPs in a range
of water types with varying salinity, pH, hardness, suspended sediment,
and natural organic matter contents. The stability of water-dispersed
PBPs will also be investigated by varying the post-mixing settling
period prior to determining the oil content of the water column.
Notably, the emulsion tests performed using the rotary agitation are
closed systems, which do not allow for the evaporation of the light
fraction during mixing. Nevertheless, the results presented herein offer
insight into oil emulsification and dispersion tendencies. Future work
will also examine the effects of evaporation on petroleum products’
aquatic behaviour by mixing in an open system.
CRediT authorship contribution statement
Qin Xin: Conceptualization, Writing – original draft, Writing -
8
Fuel 309 (2022) 122040
review & editing, Supervision, Project administration. Lindsay J.
Hounjet: Conceptualization, Investigation, Writing - review & editing,
Visualization, Project administration. Austin Hartwell: Investigation,
Writing – original draft.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work received funding from the Government of Canada’s Safe
and Secure Shipping program. We would like to acknowledge the
Standard Analytical Laboratory at CanmetENERGY Devon for perform­
ing physical and chemical analyses of petroleum samples, Dr. Yi Zhang
and Dr. Mohamed Ali for providing visbroken bitumen products, and
Drs. Heather D. Dettman and Stanislav R. Stoyanov for insightful
discussions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2021.122040.
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