Environmental Modelling and Software 111 (2019) 432–443

Contents lists available at ScienceDirect

Environmental Modelling & Software

journal homepage: www.elsevier.com/locate/envsoft

Integrating organic chemical simulation module into SWAT model with T

application for PAHs simulation in Athabasca oil sands region, Western
Canada
Xinzhong Du, Narayan Kumar Shrestha, Juyne Wang∗
Athabasca River Basin Research Institute (ARBRI), Athabasca University, Alberta, Canada

A R T I C LE I N FO A B S T R A C T

Keywords: An integrated watershed model is a key tool for assessing the fate and transport of organic chemicals. We
SWAT model developed and integrated an organic chemical simulation module into Soil Water Assessment Tool (SWAT)
Organic chemical simulation model and used it for Polycyclic Aromatic Hydrocarbons (PAHs) simulation in Muskeg River Watershed in
Three-phase partition Athabasca oil sands region, Western Canada. The model uses a three-phase partition process to simulate the
Polycyclic aromatic hydrocarbons (PAHs)
chemicals partitioning to Dissolved Organic Carbon (DOC) in both soil water and streams. The simulation
performances for Phenanthrene and Pyrene loads for a period of 2015–2017 were assessed to be of ‘satisfactory’
quality. The model simulation results indicated that the summer season is the hot moment and the rainfall-runoff
event is the driving force for the PAHs transport in the watershed. The developed simulation module could be a
useful modeling tool to simulate and asess the pathway, fate and transport of organic chemicals at the watershed
scale.

1. Introduction
Organic chemicals can cause local and regional losses of freshwater
biodiversity and ecosystem services. Of the 223 chemicals monitored
globally, pesticides, tributyltin, polycyclic aromatic hydrocarbons
(PAHs), and brominated flame retardants were the major contributors
to the chemical risk (Malaj et al., 2014). Particularly, organic chemicals
can impair the designated water use if their concentrations exceed
water quality standards. They can be exported to stream and other
water bodies by point source or transport from landscape environment.
Oil sands are found in about 70 countries and the largest deposits of oil
sands exist in Canada and Venezuela, with smaller resources in Russia,
Europe and the U.S (Hirsch et al., 2005). The oil production in oil sands
region could pose threat to the local environment. The Athabasca oil
sands (or tar sands) are large deposits of bitumen or extremely heavy
crude oil, located in northeastern Alberta, Canada, which have been
subject of various environmental studies since Suncor Energy Inc. began
its operation in 1967 (Evans et al., 2016). Since then, the oil sands
industry has expanded exponentially and there are environmental
concerns from the industry activities associated with surface mining, in-
situ recovery and upgrading of bitumen (Kurek et al., 2013). Kelly et al.
(2009) conducted an independent and accessible assessment of the
loading of polycyclic aromatic compounds (PAC) to the Athabasca
River and its tributaries and found that the oil sands industry is a far
greater source of regional PAC contamination than previously realized
due to substantial loadings of airborne PAC. They pointed out that
controls on waterborne PAC are critical because concentrations at tri-
butary mouths and at one site on the Athabasca river are already within
the range toxic to fish embryos (Kelly et al., 2009). Moreover, Kelly
et al. (2010) found that oil sands industry substantially increases the
loadings of toxic metal elements to the Athabasca river and its tribu-
taries via air and water pathways and recommended a detailed long-
term monitoring to distinguish the sources of the contaminates and
control the potential impacts. Collectively, these industrial activities
yield significant landscape disturbance and habitat loss and lead to the
controversy water quantity and quality issues (Kurek et al., 2013).
Monitoring methods for organic chemicals have been conducted to
assess the impact on water quality, indentify pollution source and
evaluate the efficiency of pollution mitigation technique (Bourgeault
and Gourlay-France, 2013; Imfeld et al., 2009; Morandi et al., 2015).
However, it is very expensive and time-consuming to conduct an in-
tensive and long term monitoring program (Du et al., 2016). On the
other hand, an integrated watershed model is a cost-effective and
powerful tool for quantitatively predicting the fate and transport of
organic chemicals in both terrestrial and aquatic environments at the
watershed scale to support environmental exposure and risk

∗
Corresponding author.
E-mail address: junyew@athabascau.ca (J. Wang).

https://doi.org/10.1016/j.envsoft.2018.10.011
Received 9 March 2018; Received in revised form 23 October 2018; Accepted 26 October 2018
Available online 30 October 2018
1364-8152/ © 2018 Elsevier Ltd. All rights reserved.
X. Du et al. Environmental Modelling and Software 111 (2019) 432–443

phases. The SWAT model used a two phases (dissolved and particular
Software availability
phases) partitioning for pesticides modeling and the impact of dissolved
organic carbon (DOC) on chemical partitioning has not been included
Name of software SWAT organic chemical simulation module
(Ligaray et al., 2017). The partitioning of organic chemicals to DOC was
DeveloperXinzhong Du
indicated to be important in determining the bioavailability, fate,
Contact address 1 University Dr, Athabasca, AB T9S 3A3 Canada
transformation and transport of the chemicals (Tronczynski, 1992).
and E-mail: xinzhong.du@gmail.com
Therefore, the organic chemicals partitioning to DOC has to be modeled
Year first available 2018
to better represent the chemical partition process. Ligaray et al. (2016)
Program language FORTRAN
used SWAT to model PAHs at the watershed scale and the partitioning
Availability Contact developer by E-mail
of PAHs to DOC in the soil was included to have a three phases parti-
tioning simulation. Later, they used the same approach to model the
pesticide in the Pagsanjan-Lumban Basin, Philippines with three phases
assessments, pollution control, planning and decision making (Chen
partitioning. However, the chemical partitioning to DOC in the water
et al., 2017). Therefore, models have been used for simulation of PAHs
column is not considered. In our study, the organic chemicals parti-
in the main stream of lower Athabasca river using one-dimensional
tioning to DOC in soil layers and water column were both simulated. In
(Shakibaeinia et al., 2017) and two-dimensional (Kashyap et al., 2017)
addition, organic chemical load that is transported to the stream by the
hydrodynamic and transport models. However, while these models
groundwater has not been simulated by previous modeling studies.
were successful to represent the organic chemical processes in the river
Organic chemicals like PAHs have been detected in the groundwater
system, they were lack of description of the transport of the chemicals
aquifers in different regions (Brindha and Elango, 2014; MacKay and
from terrestrial to aquatic environment.
Gschwend, 2001) and thus it is possible that groundwater flow can
A watershed-scale model, the Soil and Water Assessment Tool
contain organic chemicals and transports the chemicals to the stream
(SWAT) (Arnold et al., 2012) has been widely used for simulating
and other water bodies. Therefore, the organic chemical load trans-
streamflow (Shrestha et al., 2017; Zhang et al., 2008), water tempera-
ported by groundwater flow should be modeled to improve the existing
ture (Du et al., 2017), sediment and nutrient loads (Jha et al., 2004) on
model by considering the contribution from groundwater flow to the
different temporal and spatial scales. The SWAT model is also able to
total organic chemical load. For this region, the oil sands land is the
simulate the pesticides, which is one of specific organic chemicals and it
main feature and activities that has not been taken into account in the
has been used for modeling pesticides in different watersheds (Chen
existing hydrological models. Therefore, oil sands land is explicitly
et al., 2017; Fohrer et al., 2014; Larose et al., 2007). However, organic
depicted as a land use type to setup a SWAT model and the hydro-
pollutants are not limited to the pesticides. A module should also be
logically closed-circuited areas are characterized in SWAT model of this
able to simulate other organic chemicals such as PAHs and naphthenic
study. The Athabasca oil sands region is located in the cold climatic
acids. Understanding the fate and effects of organic chemicals at the
region where snowmelt and rainfall runoff could export the organic
watershed scale requires an understanding of partitioning behavior
chemicals from landscape to the aquatic environment and an integrated
both in the soil and water column. The partitioning process of the or-
modeling study is helpful for understanding the roles of different hy-
ganic chemical can be very important in governing the environment
drological process in pollutants transport at watershed scale. No studies
fate and transport and the toxicity of the chemicals. From the modeling
have been reported about modeling organic chemicals at a watershed
perspective, partitioning process has to be simulated before the trans-
scale for both terrestrial and aquatic environments in cold climate
port process since it determines the fractions of different chemical

Fig. 1. Location of Muskeg River Watershed with observed stations (a) and the landuse map (b). OSHO and OSHC refer to the hydrological closed and open oil sands
land, respectively.

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X. Du et al.
condition like Athabasca oil sands region. This study tried to address
the gap to have a watershed scale PAHs simulation at Muskeg river
watershed in Athabasca oil sands region by developing and integrating
an organic chemical simulation into SWAT model.
The goals of this study are twofold. Firstly, we aim to develop an
organic chemical simulation module and to integrate it into the widely
used, SWAT model to provide a modeling a tool for simulating the fate
and transport of organic chemicals at the watershed scale. Secondly, the
developed model is used for watershed-scale PAHs modeling in
Athabasca oil sands region to understand and assess the pathway, fate
and transport of organic pollutants at watershed scale in this region.
2. Materials and methods
2.1. Study area
The Muskeg River Watershed (MRW) is located in the Athabasca oil
sands region in lower part of Athabasca River Basin of northern Alberta,
within the Regional Municipality of Wood Buffalo. The river is a tri-
butary to the Athabasca River and drains an extensive area of boreal
forest wetlands. The area of the MRW is about 1433 km2 and there are
several major tributaries including Jackpine, Muskeg and Wapasu
creeks. The MRW is underlain by mineable oil sands which are very
important to the economics of Alberta. The MRW contains four oper-
ating oil sands mines, which have modified the watershed landuse
composition dramatically (Eum et al., 2016). The land change area
related to oil sands development in 2015 in the MRW is 238.9 km2
accounting for 16.7% of the total watershed area. Streamflow is mon-
itored at the station of Muskeg river near Fort Mckay (station number:
07DA008) and can be downloaded from Environmental Canada and
climate change website. Moreover, sediment and water quality con-
centration (such as nutrients, metals and organic chemicals) are also
monitored in this station. Fig. 1a shows the location and extent of MRW
and the observed stations.
2.2. Soil and water assessment tool (SWAT)
SWAT model is watershed scale model developing for modeling the
impact of land management practices on water, sediment and agri-
cultural chemical yields (like nutrients and pesticides) in large complex
Fig. 2. The regression between log (DOC load) and log (streamflow).
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Environmental Modelling and Software 111 (2019) 432–443
watersheds with varying landuse and soil conditions over long periods
of time (Neitsch et al., 2011). The hydrological processes in SWAT
model include canopy interception, infiltration, surface runoff, lateral
flow, snowmelt flow, evapotranspiration, deep percolation, baseflow
and water routing in the aqutic systems. In addition, soil erosion for
each HRU is simulated by Modified Universal Soil Loss Equation
(MUSLE) and sediment routing is model by simulating sediment de-
position and degradation using different model options. In addition,
nutrient, pesticides and bacterial are also modeled by simulating the
chemical fate transport processes in both landscape and aquatic en-
vironments. More detailed description of SWAT model processes is
available from Neitsch et al. (2011).
2.3. DOC simulation in SWAT model
DOC concentrations in soil water and water column are needed to
simulate a three-phase partitioning for organic chemicals. For DOC
concentration in soil water, we used the organic matter (OM) and a
parameter as the fraction of DOC to calculate the concentrations of
different layers (Ligaray et al., 2016). The equation of soil DOC con-
centration was given as:
Cdoc, sol = fdoc⋅OM (1)
where Cdoc,soil is the DOC concentration in soil water (mg/L), fdoc is the
fraction of DOC (model parameter) and OM is the concentration of
organic matter (mg/L). Using SWAT parameters, OM was determined
by dividing the mass of soil organic carbon in soil organic matter with
the soil water content (Ligaray et al., 2016). Here, we used the SWAT-C
model (Zhang et al., 2013), which already has been incorporated into
SWAT code, to simulate the soil organic carbon cycle in soil layers and
the mass of soil organic carbon at each daily time step are from SWAT-C
simulation. Then, the DOC concentration in soil water was estimated
based on the simulated organic carbon mass and the parameter fdoc.
In order to simulate three-phases partitioning in the streams, a
simple regression model based on streamflow was used to estimate the
DOC concentrations in the stream. The exploratory data analysis and
inspection of the residuals suggest a linear model that relates log load to
log streamflow (Runkel et al., 2004) as:
Log (Load) = a0 + a1⋅Log (flow) (2)
X. Du et al. Environmental Modelling and Software 111 (2019) 432–443

where Load is the observed daily DOC load in the streams (kg/day), flow such as suspended solids, biological material, and sometimes dissolved
is the observed daily streamflow (m3/s) and ao and a1 are the two or colloidal organic material. Multiple phase partitioning (dissolved in
coefficient need to be estimated. The linear regression between ob- water, sorbed to DOC, and sorbed to solids) is simulated in the soil
served log load and log streamflow using the 22 DOC measurements layers. Sorption reactions are usually fast relative to other
from 2015 to 2017 (Table S1) was showed in Fig. 2. Once ao and a1 environmental processes, and linear equilibrium partitioning is
were estimated, the DOC load can be estimated by the exponential assumed in this module. The fraction of different chemical phases is
equation from equation (2) and then the DOC concentrations are esti- calculated as:
mated by the estimated DOC load and the streamflow simulated by
Cd, soil 106θ
SWAT. It's worth mentioning that the coefficients ao and a1 have to be fd, soil = =
CT , soil Rsoil (3)
re-calibrated using the observed data if it is applied in a different wa-
tershed.
Cp, soil kp, soil dsoil
fp, soil = =
2.4. Organic chemical simulation module in SWAT CT , soil Rsoil (4)

The organic chemical simulation module models the movement and
fate of the organic pollutants at a watershed scale including the pro-
cesses both in the landscape and aquatic system. The landscape routine
simulates the degradation and transport of the organic chemical in the
soil layers of HUR units in SWAT. The aquatic routine receives the
chemical loads simulated by the landscape routine and models the
transport and fate of organic chemicals in the stream and other water
bodies (lake or reservoir) from upstream to downstream.
2.4.1. Organic chemical processes in the landscape
Fig. 3 shows the main processes modeled for the organic chemical
processes in the landscape unit. The landscape routine models the
chemical processes including partition, decay and transport to the
aquatic system. The modeled transport processes consist of chemical
amount removed by soil erosion, surface runoff, lateral flow and
groundwater. In addition, the leaching of dissolved and DOC sorbed
chemical from upper layer to the underlying layer is also simulated.
2.4.1.1. Organic chemical partitioning in soil layers. Partitioning also
called sorption is the bonding of dissolved chemicals onto solid phases,
Cdoc, soil kdoc, soil⋅θ⋅Cdoc, soil
fdoc, soil = =
CT , soil Rsoil (5)
Rsoil = 106θ + kdoc, soil θ⋅Cdoc , soil + kp, soil dsoil (6)
where CT,soil is total concentration of the organic chemical in soil layers
(ug L−1), fd,soil is the fraction of dissolved phase in soil layers, fp,soil is the
fraction of solid sorbed phase in soil layers, fdoc,soil is the fraction of DOC
sorbed phase in soil layers, Cdoc,soil is DOC concentration in soil water
simulated by the incorporated DOC simulation module (mg L−1), kp,soil
is partition coefficient for soil solids (L kg−1), kdoc,soil is the DOC
partition coefficient (L kg−1), dsoil is the density of soil solid in soil
layers (mg L−1), θ is the soil water content expressed as a fraction of
total soil volume. The density of soil solid dsoil (mg/L) in each soil layer
can be calculated by soil bulk density, which is a SWAT soil property
parameter. Soil water content θ can be calculated by the simulated soil
moisture. Because the partitioning of organic chemical is dependent
upon on the amount of organic matter in the soil, the soil solids
partition coefficient kp,soil input to the model is normalized for soil
organic carbon content:

Fig. 3. Representation of main processes modeled for the organic chemical processes in the terrestrial system.

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X. Du et al.
orgC
kp , soil = koc⋅
100
where koc is the soil solid partition coefficient normalized for soil
carbon content and orgC is the organic carbon content in the soil layers.
koc and kdoc,soil are the two parameters for organic chemical partition
process in the soil. Once the partition is simulated, the amounts and
concentrations of different chemical phases are determined and then
the transport processes for different phases are modeled via different
transport pathways.
2.4.1.2. Organic chemical decay in soil layers. The reaction processes in
soil layers include degradation, photolysis, hydrolysis, volatilization
and extra reaction. In this simulation module, these reactions are
lumped together using a first-order decay equation to calculate the
total amount of chemical reactions in each soil layer. For each
simulation time step, the landscape routine calculates the decay
amount and mass changes of the chemicals in soil layers. This decay
process of chemicals, whether they are dissolved or adsorbed to
particles, is modeled using the same equation and decay rate.
Chemical decay amount in soil layers is computed as:
msoil, dec, t = kdec, soil, t [fd, soil + fdoc, soil + fp, soil ]⋅msoil, t
where msoil,dec,t is chemical decay amount in the soil layers (g ha−1
day−1) on a given day, kdec,soil,t is the decay rate for organic chemical in
the soil layers (day−1), msoil is the total chemical amount in soil layers
(g ha−1), which is the model state variable in soil layers. The decay rate
is related to the half-life as follows
0.693
kdec, soil =
t1/2, s
where t1/2,s is organic chemical half-life in the soil (d−1), which is a
model parameter for the simulation module.
2.4.1.3. Organic chemical transport and leaching in soil layers. The
landscape routine simulates organic chemicals’ movement into stream
network or other water bodies via sediment, surface runoff, lateral
subsurface flow and groundwater flow. Chemicals transported by
surface runoff, lateral subsurface flow and groundwater flow are
considered as dissolved and DOC-sorbed phase. Sediment transport of
chemicals is considered as particular phase. In addition, dissolved and
DOC-sorbed chemicals moving into underlying soil layers by leaching
(or percolation) are simulated. The chemical amounts contained in
surface runoff, lateral flow and percolation are estimated as products of
mobile water volume and the average concentration of dissolved phase
and DOC-sorbed in the soil layer. The particular phase chemicals
transported with sediments is simulated with a loading function of
SWAT, which is also used to calculate particular nutrient loads. The
loading function can estimate daily particular phase chemicals loss
based on the concentration of particular phase chemicals in the top soil
layer, the sediment yield, and the enrichment ratio, which is the
concentration of particular chemicals in the sediment divided by that
in the soil. The equations for organic chemical transport processes are
as below:
1) Deposition
A user-defined flux rate is used to describe the atmospheric de-
position of the organic chemicals. The atmospheric deposition is added
to the top soil layer, which is given as
matm = 10−2L0
where matm is the deposition amount of organic chemical on a given day
(g/ha) and L0 is areal deposition rate of the organic chemical (ug m−2
day−1), which is a model parameter needs to be estimated by model
calibration.
Environmental Modelling and Software 111 (2019) 432–443
2) Particular organic chemical transported by the sediment
(7)
Organic chemicals attached to soil particles may be transported by
sediment through soil erosion process to the main channel. This phase
of organic chemical is associated with sediment loading from SWAT
HRU unit and changes in sediment loading will impact the loading of
particular phase chemicals. The amount of organic chemicals trans-
ported with sediment to the stream is calculated using the loading
function as follows (Neitsch et al., 2011):
sed
msoil, sed = Cp , sed⋅ ⋅ξcon: sed
areahru (11)
where msoil,sed is the amount of sorbed chemical transported from the
top soil layer on a given day (g/ha), Cp,sed is the concentration of or-
ganic chemical on sediment in the top soil (g/metric ton), sed is the
sediment yield on a given day (metric tons), areahru is the HRU area
(ha), and ξcon:sed is chemical enrichment ratio. The enrichment ratio is
defined as the ratio of the concentration of sorbed chemical transported
with sediment to the concentration in the top soil layer. In SWAT, en-
richment ratio can be calculated for each storm event using empirical
equation, or be defined as a parameter that is used for all storm events
(8) during simulation period. In this study, enrichment ratio is a user-define
parameter which can be estimated by model calibration. The con-
centration of particular chemical on sediment Cp,sed (g/ton) in the top
soil can be calculated from partitioning concentration in the top soil
layer:
Cp , soil
Cp , sed = 10−3⋅
sol _bd (12)
where Cp,soil (ug/L) is the solid chemical concentration in top soil layer
(9)
based on equilibrium partitioning, sol_bd is soil bulk density (g/cm3) of
the soil layer, which is the soil parameter in SWAT.
3) Dissolved and DOC sorbed organic chemical transported by runoff
components
In order to calculate the chemical amounts transport by surface
runoff and lateral flow, the concentration of organic chemical (dis-
solved and DOC sorbed) in mobile water is first calculated as:
Orgchmcon, mobile
=
(
Orgchmly⋅(fd, soil + fdoc, soil)⋅ 1 − exp ( −wmobile
SATly ))
wmobile (13)
where Orgchmcon,mobile is the organic chemical concentration in the
mobile water including the dissolved and DOC sorbed phase (g/ha/
mm), Orgchmly is the total amount of organic chemical in the soil layer
(g/ha), fd,soil and fdoc,soil are the fractions of the dissolved and DOC
sorbed phase chemical calculated by the partitioning process. Then,
transported chemical loads are calculated by multiplying surface runoff
and lateral flow volumes simulated by SWAT and the concentration in
mobile water. In addition, the dissolved and DOC sorbed organic che-
micals could be moved downwardly to lower soil layers by the leaching
processes and the percolation water volume simulated by SWAT and the
retardation factor were used for the leaching simulation. The equations
used for simulating the chemical leaching can be found from equations
S1 to S12 in the supplementary material.
In addition to the chemical transport by surface runoff and lateral
flow, the dissolved and DOC sorbed chemicals can leach into the
shallow aquifer and be transported to the stream by the groundwater
flow. A constant concentration of chemical concentration in the
(10)
groundwater flow is used to calculate the chemical load transported
with groundwater flow:
mgwf = congwf ⋅Qgw⋅10−5 (14)
where mgwf is the chemical amount transported by groundwater flow
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X. Du et al.
(g/ha), congwf is the chemical concentration in groundwater which is a
model parameter subject to model calibration (ng/L) and Qgw is
groundwater flow (mm) simulated by SWAT.
2.4.2. Organic chemical simulation in aquatic system
The aquatic routine of organic chemical simulation module models
the transport and transformation of the organic chemicals in stream and
other water bodies. The aquatic routine assumes a well-mixed layer of
water overlying a bed sediment layer. Fig. 4 illustrates the processes
included in the aquatic routine. The processes simulated in the aquatic
routine include chemical partitioning in the water and sediment layer,
chemical decay in both water and sediment layer, chemical diffusion
between water and sediment layer, settling of particular chemical into
sediment layer, resuspension from sediment layer to water column and
chemical transport with inflow and outflow.
2.4.2.1. Chemical partitioning process in water column. Three phase
partitioning (dissolved in water, sorbed to DOC, and sorbed to solids)
is simulated in water column. Linear equilibrium partitioning is
assumed in the water column and the fractions of different chemical
phases is calculated as:
Cd, water 106
fd, water = = t1/2, w
CT , water Rwater
Cp, water kp, water Sedcon
fp, water = =
CT , water Rwater
Cdoc, water kdoc, water⋅DOCcon, water
fdoc, water = = Δmwater = min − mout − mwtr , dec − mwtr , stl + msed, rsp ± mdif
CT , water Rwater
Rwater = 106 + kdoc, water⋅DOCcon, water + kp , waterSedcon
where fd,water is the fraction of dissolved phase in water column, CT,water
is total concentration of organic chemical in water column (ug L−1),
fp,water is the fraction of solid sorbed phase in water column, Cp,water is
the concentration of particular organic chemical in water column (ug
L−1), kp,water is the partition coefficient for suspend solids in water
column (L kg−1), Sedcon is the suspend sediment concentration in water
Fig. 4. The major processes simulated for organic chemicals in aquatic system.
Environmental Modelling and Software 111 (2019) 432–443
column simulated by SWAT (mg L−1). fdoc,water is the fraction of DOC
sorbed phase in water column, Cdoc,water is the concentration of DOC
sorbed organic chemical in water column (ug L−1), kdoc,water is the DOC
partition coefficient in water column (L kg−1) and DOCcon,water is DOC
concentration in water column (mg L−1) simulated by the DOC
simulation module. kp,water and kdoc,water are two parameters for
organic chemical partitioning processes in the water column.
2.4.2.2. Organic chemical decay and transport processes in water
column. The reaction processes in water column include degradation,
photolysis, hydrolysis, volatilization and extra reaction. In this study,
these reactions are lumped together using a first-order decay equation
to calculate the total amount of chemical reactions in the water column.
Chemical reaction amount in water column is computed as:
m wtr , dec, t = kdec, wtr , t (fd, water + fdoc, water + fp, water )⋅mwater (19)
where mwtr,dec,t is chemical decay amount in the water column, kdec,wtr,t
is decay rate for organic chemical in water column (d−1) and mwater is
total chemical amount in the water column (ug). The decay rate in
water column is related to the half-life as follows:
0.693
kdec, wtr =
(20)
(15)
where t1/2,w is organic chemical half-life in the water column (d−1),
which is a model parameter for the simulation module.
(16) The mass balance for organic chemical in water column is calcu-
lated as:
(17)
(21)
(18)
where Δmwater,is the change in chemical mass in the water column (mg),
min is the chemical amount added to the water column via inflow (mg),
mout is the chemical amount removed via outflow (mg), mwtr,dec is the
amount of organic chemical removed from the water via decay (mg),
mwtr,stl is the amount of organic chemical removed from the water due
to settling (mg), msed,rsp is the amount of organic chemical added to the
water from resuspension from the sediment layer and mdif is the amount
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X. Du et al.
of organic chemical transferred between the water and sediment layer
by diffusion.
The particular phase organic chemical might be removed from the
water column by settling which transfers organic chemicals from the
water to the sediment layer. The amount of chemical that is removed
from the water via the settling is calculated as:
vstl
mwtr , stl = ⋅fp, water⋅mwater⋅TT
depth (22)
where mwtr,stl is the settling amount of the particular organic chemical
(mg), vstl is the settling velocity (m/day) which is a model parameter,
depth is the water depth simulated by SWAT routing routine (m), fp,water
is the fraction of organic chemical in the particular phase calculated by
the partition process, mwater is the amount of organic chemical in the
water and TT is the flow travel time (days).
2.4.2.3. Organic chemical processes in the sediment layer. In order to
simulate the interaction (resuspension and diffusion) between water
column and the sediment layer, the organic chemical processes in the
sediment layer underlying the water column are simulated. The
chemical amount in the sediment is increased through addition of
mass by settling and diffusion from the water. The chemical amount in
the sediment is reduced by resuspension, decay and diffusion into the
overlying water column and the burial. The mass balance for organic
chemical in the sediment layer is calculated as:
Δmsed = mwtr , stl − msed, dec − msed , rsp − msed , bur ± mdif (23)
where Δmsed is the change in organic chemical mass in the sediment
layer (mg), mwtr,stl is the amount of organic chemical added to the
sediment layer from the setting of particular chemical in the water
column, msed,dec is the sediment decay amount (mg), msed,rsp is the
amount of organic chemical removed from sediment layer via
resuspension (mg), msed,bur is the amount of organic chemical
removed via burial and mdif is the amount of organic chemical
transferred between the water and sediment layer by diffusion. The
amount of organic chemical that is removed from sediment layer via
decay process is calculated as:
msed, dec = kdec, sed⋅msed (24)
where msed,dec is the amount of organic chemical removed from
sediment layer by the decay process (mg), kdec,sed is the rate constant
for chemical decay in the sediment (mg) and msed is the amount of
organic chemical in the sediment layer (mg). The decay rate constant is
related to the sediment half-life:
0.693
kdec, sed =
t1/2, sed (25)
where t1/2,sed is the sediment half life for organic chemical which is a
model parameter subject to model calibration. In addition, the
equations for calculating resupension, sediment burial and diffusion
between the water and sediment layer can be found from equation S12
to S15 in the supplementary material.
2.5. SWAT model setup
Spatial and meteorological data are needed for setting up the SWAT
model in the MRB. The required spatial datasets are a digital elevation
model (DEM), landuse and soil data maps. The DEM data was obtained
from Geospatial Data Extraction of Natural Resources Canada with the
resolution of 0.75 arc second (18.7m*18.7m). The 30m*30m landuse
map from AAFC (http://www.agr.gc.ca/atlas/landu) and oil sands land
map (http://www.rampalberta.org/data/map/mapdata.aspx) from
Regional Aquatics Monitoring Program (RAMP) were used to create
landuse map of MRW. The 1:1 million scale soil map from the
Agriculture and Agri-Food Canada (AAFC) were used as model input to
build soil database. The DEM was used to delineate subbasin and stream
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Environmental Modelling and Software 111 (2019) 432–443
networks and 30 subbasins were delineated in the MRW. A slope map is
derived from the DEM and divided into 3 groups (breaks at 1.2% and
3.9%) to define the HRU. 10 different landuse classes and 6 different
soil types were defined for setting up the model. In addition, a threshold
of 5%, 5% and 5% for land use, soil and slope, respectively, were used
to definite HRUs and a total of 362 HRUs were obtained. As to me-
teorological input data, daily precipitation, maximum and minimum air
temperature were obtained from 2 stations recorded by Environmental
Canada and Climate Change. Solar radiation, relative humidity, and
wind speed data at 5 stations recorded by Climate Forecast System
Reanalysis (Dile and Srinivasan, 2014) were also used as model input.
In addition, we also defined 5 elevation bands in each subbasin to en-
able the model simulate snow melt processes in a distributed way and
adjust the precipitation and temperature according to the elevation
differences with weather gauge station.6
2.6. SWAT modification for oil sands land
The oil sands mines and tailing ponds constructed in the MRW are
now dramatic features of the watershed landscape. The changes to the
landscape by oil sands development indirectly affect the natural pat-
terns of water and pollutants movement. To reflect the oil sands impact
on MRW, oil sands lands are defined as the landuse type to setup SWAT
model. Specifically, the oil sands land map from RAMP was overlapped
with the AAFC landuse map to define oil sands in the landuse classifi-
cations. Fig. 1b shows the landuse distribution in the MRW and two
types of oil sands landuses were defined according the different hy-
drological features. If the oil sands areas have no natural exchange of
water with the rest of the watershed (e.g., tailings ponds), they are
designated as “hydrologically closed-circuited”. If the Oil sands areas
have natural exchange of water with the rest of the watershed, they are
designated as “not hydrologically closed-circuited”. In the MRW, there
are 73.7 km2 “hydrologically closed-circuited oil sands” area and
146.7 km2 “not hydrologically closed-circuited” which account for
4.9% and 9.8% percentage of the total watershed area, respectively.
There are 101 HRUs for oil sands area for SWAT setup in the MRW and
30 of them are “hydrologically closed-circuited”. Since there is no hy-
drological interaction between hydrologically closed oil sands area and
the rest of watershed, the SWAT model was modified to reflect this
unique feature. Specifily, the water yield (surface runoff, lateral flow
and groundwater flow), sediment and organic chemical loads of hy-
drologically closed oil sands HRU are not routed to the stream. As such,
3 SWAT original subroutines and 1 organic chemical subroutine were
modified for hydrologically closed oil sands HRUs.
2.7. Model calibration and validation
Since the PAHs observed data are only available for a period of
2015–2017, we calibrated and validated the streamflow, sediment and
PAHs simulations using the same time period on a daily time scale. As
such, the year of 2016 was selected as the calibration period because
the PAHs measurements covered the whole year from January to
December. The years of 2015 and 2017 were selected as the validation
period as there were only 10 measurements during the validation
period (7 measurements in 2015, from May to December and 3 mea-
surements in 2017, from January to March). A three-year warm-up
period (2012–2014) was used to attenuate the impact of initial condi-
tions on the model simulations. First, daily streamflow data (station
number: 07DA008) at the outlet station collected from Environmental
Canada and Climate Change was used for the streamflow calibration
and validation. The observed sediment and two PAHs (Phenanthrene
and Pyrene) concentrations at the outlet station and the sampling dates
were showed in Table S1. Those concentrations were obtained from the
RAMP monitoring datasets and were measured once a month from June
2015 to March 2017. There were 20 measurements for sediment con-
centration with an average concentration of 3.6 mg/L, and there were
X. Du et al. Environmental Modelling and Software 111 (2019) 432–443

22 measurements for Phenanthrene (Phe) and Pyrene (Pyr) with the
average concentrations of 1.6 and 0.8 ng/L, respectively. The observed
daily streamflow from 2015 to 2017 range from 0.15 to 14.4 m3/s and
the streamflow of the 22 PAHs sampling dates range from 0.18 to
14.4 m3/s, which indicates that the measured PAHs concentration could
represent the PAHs variability that may exist in the MRW from 2015 to
2017. We used the measured sediment and PAHs concentrations and
the daily observed streamflow of the same day to estimate the loads.
Next, the estimated periodic loads were used for sediment and PAHs
calibration and validation. The model calibration was then conducted
by combining the automatic calibration using SWAT-CUP (Abbaspour,
2013) and manual calibration in the following. First, the parameter
sensitivity analysis results were obtained by the global sensitivity
analysis algorithm of SWAT-CUP. For automatic calibration, SUFI-2
algorithm from SWAT-CUP was used based on 2000 simulations with
the defined parameter rages. Then, we manually adjusted the one or
two most sensitive parameters based on the ‘best parameter set’ from
the automatic calibration to get better model performance statistics. We
found that manually adjusting the most sensitive parameters after the
automatic calibration was very useful to improve the model perfor-
mances. Since the new parameters added for organic chemical simu-
lation module are not in the SWAT-CUP parameter list, we ‘borrowed’
SWAT pesticide parameters to perform PAHs parameters calibrations in
SWAT-CUP. Specifically, we wrote the scripts ‘PAH parameters equal to
the pesticide parameters’ in the code and used the columns of pesticides
in ‘output.rch’ file to output PAHs simulation results. Then, we com-
piled an .exe file based on the organic chemical module code to replace
the original ‘swat.exe’ file in SWAT-CUP directory. The pesticide
parameters and pesticide column number in output.rch file were used
to setup SUFI-2 project for PAHs calibrations in SWAT-CUP. So, when
pesticide parameters are changed in SWAT-CUP, the PAHs parameter
values and simulation results will change accordingly. We admitted that
this is not a direct way to facilitate the automatic calibration in SWAT-
CUP but is able to indirectly perform the PAHs automatic calibration
and sensitivity analysis. In this study, the root mean square error
(RMSE) was used as the objective function and the model parameters
were calibrated to minimize the value of RMSE during the calibration
period (Du et al., 2014). In addition, percentage biases (PBIAS), coef-
ficient of determination (R2) and Nash-Sutcliffe efficiency (NSE) were
also used as the measures of model performance (Zhang et al., 2013).
The objective function RMSE and the model performance measures are
defined as:
n t t 2
∑t = 1 (ysim − yobs )
RMSE =
n (26)
n
t t
∑t = 1 (ysim − yobs )
PBIAS = n t
× 100%
∑t = 1 yobs
2
n t t
⎛ ∑t = 1 (ysim − ysim)⋅(yobs − yobs ) ⎞
R2 = ⎜ ⎟⎟
⎜ ∑n (y t − ysim)2⋅ ∑n (y t − ysim)2
⎝ t = 1 sim t = 1 sim ⎠ (28)
n
t
∑t = 1 (yobs t
− ysim )2
NSE = 1 −
n
∑t = 1 t
(yobs − yobs )2 (29)
where ytsim
is the simulated value at a time unit t, ytobs
is the observed
value at a time unit t, n is the total data number, ysim is the mean
observed value for the simulated period, and yobs is the mean simulated
value of the simulated period. PBIAS measures the average tendency of
the simulated data to be larger or smaller than the observed data and is
sensitive to the systematic error (Chen et al., 2017). R2 ranges from 0 to
1 and represents the proportion of the total variance in the observed
data that is explained by the model (Zhang et al., 2013). NSE ranges
from negative infinity to 1 and assesses how well the model-to-data plot
fits the 1:1 line. In addition, we also assessed the model simulations
based on the performance evaluation criteria for watershed models
summarized by Moriasi et al. (2015), which evaluates the model per-
formance from ‘unsatisfactory’ to ‘very good’ based on the range of
values of chosen goodness of fit statistics. As to model uncertainties
analysis, the 95% prediction uncertainty band obtained from SUFI-2
algorithm was used to quantify the simulation uncertainties. The si-
mulation uncertainties were assessed by the P-factor and R-factor (Chen
et al., 2017). The P-factor is the percentage of the observed data
bracketed by the uncertainty band and the R-factor is the normalized
width of the band.
3. Results and discussion
3.1. Hydrological calibration and streamflow simulation
To accurately simulate the transport of organic chemicals, the hy-
drological processes simulated by the SWAT model should confirm to
actual hydrological cycle of the watershed. Therefore, it is imperative to
perform the hydrologic calibration before calibrating the organic che-
micals. A total of 25 parameters were used for streamflow calibration
and the parameter ranges and calibrated values of the top 10 most
sensitive parameters were showed in Table 1. The parameter CN2 (SCS
curve number for moisture condition II) was found to be the most
sensitive parameter, which controls the surface runoff yield and the
water amount infiltrating into the soil layers. Moreover, the parameter
SURLAG, which controls the surface runoff routing in the subbasin
scale, was found to be the second most sensitive parameter, which in-
dicates that the surface runoff is the important hydrological process in
the MRW. Two snowmelt parameters (SFTMP and SMTMP) were also
among the top 10 sensitive parameters list, further validating the need
to accurately represent snow-related process in such a cold climate
(27) region watershed. This is indeed expected in such a cold region wa-
tershed because snowmelt is the dominant hydrological process in the
spring season. Other sensitive parameters include the parameters

Table 1
Top 10 sensitive hydrological parameters with sensitive rankings, the ranges and calibrated values.
Parameter name Description Unit Parameter range Calibrated values Sensitivity ranking

r__CN2.mgt SCS runoff curve number for moisture condition II none −0.25–0.25 0.15 1
v__SURLAG.hru Surface runoff lag time days 0–24 0.02 2
v__PLAPS.sub Precipitation lapse rate mm/km −1000–1000 −205 3
v__SFTMP.bsn Snow fall temperature °C -5–5 −4.6 4
r__CH_K2.rte Effective hydraulic conductivity in main channel alluvium mm/hr −0.25–0.25 0.22 5
v__GW_DELAY.gw Groundwater delay time days 0–500 214.5 6
v__REVAPMN.gw Threshold depth of water in the shallow aquifer for "revap" to occur mm 0–500 143.7 7
v__SMTMP.bsn Snow melt base temperature °C -5–5 4.2 8
v__ESCO.hru Soil evaporation compensation factor none 0–1 0.05 9
r__HRU_SLP.hru Average slope steepness m/m −0.25–0.25 0.24 10

*v = parameter value is replaced by given value. r = parameter value is multiplied by 1 ± a given value.

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affecting the processes of channel routing (CH_K2), groundwater flow per PBIAS and NSE values. However, the simulation performance for
(GW_DELAY and REVAPMN) and evaporation (ESCO). The model per- the validation period was of ‘unsatisfactory’ quality as per R2, PBIAS
formance statistics for daily streamflow are shown in Table 2. The and NSE values in which the sediment load was clearly overestimated.
comparison between simulated and observed daily steamflow was This was partially caused by the overestimation of streamflow during
shown in Fig. 5a. The visual plot indicated that the SWAT hydrology the validation period. Furthermore, limited number of data available to
model could provide acceptable simulation results as the simulated use for sediment calibration and validation (only 20 measurements)
streamflow tend to follow a similar trend to the observed data and are also played a significant role. Only 10 daily sediment loads were
capable to fairly capture both the diurnal as well as the seasonal var- available during calibration period (2016), which ranged from 0.03 to
iations. As per Moriasi et al. (2015) evaluation criteria, the quality of 16.2 ton/day. Similarly, only10 daily sediment loads were available
daily stream flow is of ‘satisfactory’ quality based on R2 value during validation period (2015 and 2017), which ranged from 0.03 to
(R2 > 0.5). Based on the NSE values, the daily flow simulations of the 1.3 ton/day. It is clear that the sediment loads used for calibration were
calibration and whole period were evaluated as ‘satisfactory’ but ‘un- much larger than those used for validation. Therefore, the sediment
satisfactory’ for the validation period. However, the NSE value (0.41) of loads during the validation period were overestimated since the para-
the validation period is much greater than the mean NSE value (0.13) of meters were tuned to capture those much larger sediment loads ob-
daily streamflow simulation applications summarized by Moriasi et al. served during the calibration period. Ideally, the observation data used
(2015). In addition, the performance rating during the calibration for model calibration should include the data observed during different
period is of ‘very good’ quality based on the PBIAS value (−1.1%). streamflow conditions such as those during low flow, normal flow and
However, a high PBIAS value (+54.2%) during the validation period high flow condition. Such data would ensure a more robust model ca-
points to the ‘unsatisfactory’ quality of the model simulation. It is in- libration and validation. However, in our case, the observed sediment
deed true that there could be conflicting performance ratings during and PAHs data in the MRW were rather limited because the RAMP
calibration and validation periods, as pointed out by Chen et al. (2017) water quality-monitoring program in Athabasca oil sands region only
when using SWAT model as different goodness-of-fit statistics tend to started from June 2015 and the water quality measurements are only
capture distinct aspects of model performances. Furthermore, such collected at the monthly frequency. As to sediment load simulation
overestimation of daily streamflow during the validation period was uncertainties (Table 3), 70% of the measured data were bracketed by
mainly caused by the overestimation of low/base flow season in the the 95% uncertainty band during the simulation period (2015–2017)
year of 2017, however, the low flow of the years 2015 and 2016 were and R factor (0.76) was also less than 1.
simulated quite well (Fig. 5a). As the groundwater flow is the dominant
runoff component in such low flow seasons, we aimed to adjust the 3.3. Model simulation for two PAHs in Muskeg river watershed
groundwater parameters heuristically to match the streamflow hydro-
graph in the low flow season of the year 2017, and such low flow can be The periodic daily PAHs loads at the watershed outlet were used for
only matched when the groundwater flow was adjusted as zero. This calibrating and validating the organic chemical simulation module. 19
indicates possible unreliable observations and points to the need of PAHs related parameters with sensitive ranking, their parameter ranges
using more streamflow data for hydrological calibration; however, in and optimized values were shown in Table 5. Of all, the most sensitive
order to keep the calibration and validation period of streamflow same parameter was found to be the deposition rate, which is the pollution
as to that of PAH, we used the streamflow data from for the years source parameter determining the amount of the PAHs depositing to the
2015–2017. The statistics for streamflow simulation uncertainties were top soil layers. The second most sensitive parameter was found to be the
showed in Table 3. On average, 45% of the variation in streamflow was percolation coefficient for the PAHs transported by surface runoff,
bracketed by the 95% uncertainty band and R-factor (0.75) was less which further highlights the importance of the surface runoff as the
than 1, suggesting acceptable thickness of the band. pathway of the PAHs in the MRW. Besides these two most sensitive
parameters, 4 other parameters affecting the PAHs interactions between
3.2. Sediment load simulation water column and sediment layer were ranked from third to sixth,
which equally reflect the importance of interactions between water
After the streamflow calibration and validation, the sediment load column and sediment layer for the PAHs fate and transport in the MRW.
was calibrated and validated since sediment directly affects the trans- In addition, the DOC partition coefficient in water column was ranked
port amount of particular organic chemicals. 9 sediment related para- as seventh most sensitive parameter, which indicates the necessity to
meters were chosen for model calibration. The sensitivity ranking and simulate the PAH partitioning to the DOC. The model performance
calibrated values of these parameters were shown in Table 4. The
parameter PRF_BSN is found to be the most sensitive sediment para- Table 2
meter, which determines the maximum amount of sediment that can be Model performance statistics and uncertainty analysis for streamflow, sediment
transported through a reach. The second and third most sediment and PAHs loads.
parameters were other two parameters used for calculating the trans- Variables Periods RMSE PBIAS (%) R2 NSE
ported maximum sediment load through a reach. Overall, the reach
sediment routing parameters (ranking from first to fifth) were found to Streamflow Calibration (2016) 2.3 −1.1 0.54 0.52
be more sensitive than the soil erosion parameters (ranking from sixth Validation (2015 and 2017) 1.6 54.2 0.60 0.41
Calibration and Validation 1.9 25.7 0.57 0.52
to ninth). This indicates that the sediment routing process in the reach
(2015–2017)
is more influential in the MRW than the upland soil erosion and Sediment Calibration (2016) 2.9 −18.1 0.74 0.65
transport processes. Various researchers, e.g. Shrestha and Wang Validation (2015 and 2017) 2.0 81.9 0.02 −1.97
(2018) and Zabaleta et al. (2014), etc also reported similar findings. Calibration and Validation 2.1 −8.5 0.74 0.67
(2015–2017)
The model performance statistics of sediment load was shown in
Phenanthrene Calibration (2016) 0.5 −18.3 0.76 0.71
Table 2 and the comparison between the simulated and observed daily Validation (2015 and 2017) 0.2 55.2 0.50 −1.50
sediment load was shown in Fig. 5b. The simulation performance of Calibration and Validation 0.4 −5.8 0.73 0.71
sediment load for the whole simulation period (2015–2017) was found (2015–2017)
to be of ‘good’ quality while considering the R2 (0.74), of ‘very good’ Pyrene Calibration (2016) 0.4 −28.8 0.79 0.63
Validation (2015 and 2017) 0.1 42.0 0.45 −0.70
while considering the PBIAS (−8.5%) value and of ‘satisfactory’ while
Calibration and Validation 0.3 −16.8 0.73 0.64
considering the NSE (0.67) value. The simulation performance for the (2015–2017)
calibration period was of ‘good’ quality as per R2 and of ‘satisfactory’ as

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Fig. 5. The comparisons of simulated and observed daily flow (a), sediment load (b) and PAHs loads (c and d).

Table 3 NSE (0.71) values and PBIAS (−5.8%) values. The simulation perfor-
Model uncertainties statistics for streamflow, sediment and PAHs loads simu- mance of Phe load for the calibration period was rated to be of ‘very
lations during the simulation period (2015–2017). good’ quality as per R2 and NSE values and of ‘good’ quality as per
Variables Number of samplings R-factor P-factor PBIAS value. The simulation performance of Phe load for the validation
period was rated to be of ‘satisfactory’ quality as per R2 but of ‘un-
Streamflow 1096 0.45 0.75 satisfactory’ as per PBIAS and NSE values. The simulation performance
Sediment 20 0.70 0.76
of Pyr load for the whole simulation period (2015–2017) was found to
Phenanthrene 22 0.77 0.91
Pyrene 22 0.77 0.84 be of ‘very good’ quality as per R2 (0.73) and of ‘good’ quality as per
NSE (0.64) and PBIAS (−16.8%) value. The simulation performance of
Pyr load during the calibration period was rated to be of ‘very good’ as
statistics of the PAHs loads were shown in Table 2 and the comparisons per R2, of ‘very good’ as per NSE value, and of ‘satisfactory’ quality as
between the simulated and observed daily PAHs loads were showed in per PBIAS value. Similar to Phe load simulation performance for the
Fig. 5c and d. In this study, as already depicted, the performance eva- validation period, the Pyr load simulation was also of ‘satisfactory’
luation criteria for nutrient simulation, as summarized by Moriasi et al. quality as per R2 but of ‘unsatisfactory’ as per NSE and PBIAS values.
(2015) were used to assess the PAHs simulation performance. The si- The Phe and Pyr loads were overestimated during the validation period
mulation performance of Phe load for the whole simulation period and such overestimation was partially caused by the overestimations of
(2015–2017) was found to be of ‘very good’ quality as per R2 (0.73) and both streamflow and sediment load, as pointed out in the previous

Table 4
Sediment parameters with sensitive rankings, the ranges and calibrated values.
Parameter name Description Unit Parameter range Calibrated values Sensitivity ranking

v__PRF_BSN.bsn Peak rate adjustment factor for sediment routing in the main channel none 0–2 0.48 1
v__SPCON.bsn Linear parameter for calculating the maximum amount of sediment that none 0.0001–0.01 0.0006 2
can be reentrained during channel sediment routing
v__SPEXP.bsn Exponent parameter for calculating sediment reentrained in channel none 1.0–1.5 1.36 3
sediment routing
v__CH_COV2.rte Channel cover factor none −0.001–1.0 0.34 4
v__CH_COV1.rte Channel erodibility factor none −0.05–0.6 0.36 5
v__USLE_P.mgt USLE equation support practice none 0–1 0.86 6
v__USLE_K(1).sol USLE equation soil erodibility (K) factor in top soil layer 0.013(ton m2hr)/(m3- 0–0.65 0.08 7
ton cm)
v__ADJ_PKR.bsn Peak rate adjustment factor for sediment routing in the subbasin none 0.5–2.0 1.04 8
v__LAT_SED.hru Sediment concentration in lateral flow and groundwater flow mg/L 0–5000 0.06 10

*v = parameter value is replaced by given value.

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Table 5
Phenanthrene and Pyrene parameters with the ranges, calibrated values and sensitivity ranking.
Parameter name Description Unit Parameter range Calibrated values Sensitivity ranking

Phe Pyr Phe Pyr Phe Pyr

2
dep_vol Deposition rate ug/m /day 0–0.14 0.10 0.05 1 1
perco_chm Percolation coefficient none 0–1 0.42 0.36 2 2
sedchm_act Depth of active sediment layer m 0–1 0.02 0.02 3 3
chem_mix Diffusion rate between water and sediment layer m/day 0–0.1 0.10 0.10 4 4
chem_rsp Resuspension rate for sediment layer m/day 0–1 0.58 0.58 5 5
sedchm_bry Sediment burial velocity m/day 0–0.1 0.02 0.02 6 6
Log (kdoc_water) DOC partition coefficient in water column L/kg 2.4–4 2.9–48 3.15 3.74 7 7
hl_water Half-life in water column days 16.5–27.5 53.3–88.8 24.3 78.3 8 18
Log (kp_soil) Soil soils partition coefficient L/kg 3.9–6.5 4.4–7.3 4.64 5.2 9 8
sedchm_rea Sediment decay rate day−1 0–0.1 0.07 0.07 10 9
chm_gwcon Chemical concentration in groundwater flow ng/L 0–1.21 0–0.52 1.02 0.35 11 10
Log (kdoc_soil) DOC partition coefficient in soil layers L/kg 2.9–4.9 3.4–5.6 3.14 3.6 12 12
chm_solcon Chemical concentration in soil layers ng/g 0.51–1.52 0.1–0.3 0.65 0.13 13 11
chem_stl Settling rate in water column m/day 0–10 2.07 2.1 14 13
hl_soil Half-life in the soil days 127.5–212.5 531–885 202.7 844 15 15
rf_chem Retardation factor none 3–6 3.55 3.6 16 16
fdoc Faction of DOC in soil organic matter none 0.01–0.95 0.07 17 19
Log (kp_water) Soils partition coefficient in water column L/kg 2.3–3.9 2.6–4.4 2.60 2.93 18 14
enr Enrichment ratio for particulate chemicals none 1.0–4.0 3.58 3.6 19 18

* The initial partition coefficients were determined based on the literatures (Burkhard, 2000; Krauss and Wilcke, 2001) and the ranges were obtained by adjusting the
initial values by ± 25%. The initial values of chemical half-life in different domains were from (Daly et al., 2007) the ranges were obtained by adjusting the initial
values by ± 25%. The ranges of the deposition rate were obtained from the field measurement in the region (Cho et al., 2014). The initial values of PAHs con-
centrations in the soil were obtained from the field measurements in the region conducted by Environmental Canada and Climate Change (http://donnees.ec.gc.ca/
data/species/assess/plant-health-and-contaminants-oil-sands-region/?lang=en) and the ranges obtained by adjusting the initial values by ± 50%. The upper limit of
PAHs concentrations in groundwater flow were determined by the measured concentrations in the low flow season.

sections. As identified for the sediment load, the overestimation was
also caused by the limited data available to be used for PAHs calibration
and validation since the loads used for the calibration were much larger
than those used during the validation period. In addition, the peak
values of the PAH loads on June 22, 2016 were severely underestimated
(Fig. 5) and this caused underestimations of streamflow and sediment
on this very day. As a continuous model with daily step, the SWAT
model would underestimate streamflow, sediment, and chemical loads
for the days with short intense storm events. Our results are consistent
with other studies conduction in the MRW. For instance, Eum et al.
(2016) used the VIC (Variable Infiltration Capacity) model to simulate
streamflow in the MRW and results showed similar underestimation of
the peak flows during high flow seasons. In addition, we also check the
impact of peak values in 2016 on the PAHs model performances during
calibration period in 2016. Specifically, we compared the model per-
formances statistics of the observed data excluding peak values with
original performances statistics with the peak values. The results
showed that the model performances statistics deteriorated a lot when
the peak values were excluded for calculating model performances
statistics. For example, the NSE values decreased to 0.30 and 0.40 for
Phe and Pyr simulation and R2 decreased to 0.37 and 0.41. This is
because the ‘best parameter set’ was calibrated by including the peak
values and the parameter values were obtained towards matching the
peak values. Even though the model underestimated the peaks, the peak
values were still useful to constraint the model and parameter values.
For uncertainty analysis, 77% of the observed Phe and Pyr loads were
bracketed by the 95% uncertainties bands (Table 3) and the R-factors
were both less than 1, suggesting acceptable thickness of the bands.
In addition to daily PAHs loads, we also simulated monthly and
annual PAHs loads to further analyze the characteristics of the PAHs
fate and transport in the MRW. The annual Phe loads for the years
2015–2017 were found to be 139.9, 194.6 and 202.7 g/year, respec-
tively. The annual Pyr loads for the years 2015–2017 were found to be
70.7, 98.5 and 103.5 g/year, respectively. The PAHs loads in the years
2016 and 2017 were much larger than that of 2015 because these two
year were relatively wet years compared to 2015. For the monthly
PAHs loads, the maximum PAH loads would be delivered in June,
accounting almost 40 and 20 g Phe and Pyr. In addition, the summer
season (June to September) accounted for 65.2% and 66.2% of the
annual Phe and Pyr loads. This indicates that the summer season is the
hot moment for PAHs transport in the MRW.
4. Conclusion
An organic chemical simulation module was developed and in-
tegrated into one of the widely used watershed model – the Soil and
Water Assessment Tool (SWAT) to simulate the fate and transport
processes of the organic chemicals at watershed scale. The chemical
module considers three-phase portioning process by simulating che-
micals portioning to Dissolved Organic Carbon (DOC) in soil water and
streams. We demonstrated the module's capability by simulating the
dynamics of the two Polycyclic Aromatic Hydrocarbons (PAHs) in a
cold climate region watershed (Muskeg River Watershed) in the
Athabasca oil sands region of Western Canada, where the organic
chemicals pose a threat to the water quality status of receiving waters.
The hydrological and sediment dynamics were first calibrated and va-
lidated before PAHs calibrations using daily streamflow and periodic
daily sediment loads for a period of 2015–2017 at the watershed outlet.
The simulation performances for the PAHs loads for the whole simu-
lation period (2015–2017) were assessed as ‘satisfactory’. However, the
simulation performances in the validation period showed conflicting
results. The model simulation results indicate that the summer season is
the hot moment for the PAHs transport mainly driving by the intense
rainfall-runoff events in this season. The developed simulation module
could be a useful modeling tool to simulate the fate and transport of
organic chemicals at a watershed scale; however, more model appli-
cations are required to further verify the model capability in other
climatic regions of the world. Currently, the DOC simulations in soil
water and streams are the simplifications of the complex carbon cycle
processes in the watershed. Therefore, a process based watershed-scale
DOC model coupling with SWAT organic chemical simulation module
holds the potential to further improve the simulations of chemical
partitioning processes and fate and transport in the watershed.

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X. Du et al.
Acknowledgements
The authors would like to thank the Alberta Economic Development
and Trade for the Campus Alberta Innovates Program Research Chair
(No. RCP-12-001-BCAIP).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.envsoft.2018.10.011.
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