water

Article
Enhanced Two Dimensional Hydrodynamic and
Water Quality Model (CE-QUAL-W2) for Simulating
Mercury Transport and Cycling in Water Bodies
Senlin Zhu 1 ID
, Zhonglong Zhang 2, * and Xiaobo Liu 3
1 State Key Laboratory of Water Resources and Hydropower Engineering Science, Wuhan University,
Wuhan 430072, China; senlinzhu@whu.edu.cn
2 LimnoTech, Environmental Laboratory, Engineer Research and Development Center, Davis, CA 95616, USA
3 China Institute of Water Resources and Hydropower Research, Beijing 100038, China; Lxb78@126.com
* Correspondence: zhonglong.zhang@erdc.dren.mil; Tel.: +1-(601)-4219661

Received: 21 July 2017; Accepted: 21 August 2017; Published: 28 August 2017

Abstract: CE-QUAL-W2 (W2) is a widely-used two-dimensional, laterally averaged, longitudinal/

vertical, hydrodynamic and water quality model. This model was modified and enhanced to
include a mercury (Hg) simulation module for simulating Hg transport and cycling in water
bodies. The Hg simulation module in W2 is able to model the physical and biochemical processes
including adsorption and desorption of Hg species on multi-solids, settling and resuspension,
sediment burial of adsorbed Hg, diffusive exchange between water column and sediment layer,
volatilization, and biogeochemical transformations among Hg species. This paper describes the Hg
simulation module, W2 model validation and its application to the Xiaxi River, China, a historical
Hg contaminated water body. The W2 model was evaluated using the Xiaxi River data collected in
2007 and 2008. Model results show that W2 was able to predict the total Hg and methylmercury
concentrations observed for the Xiaxi River. The Xiaxi River W2 model also provides a foundation
for the future investigations of Hg contamination in the Xiaxi River. This application demonstrated
the W2 model capability in predicting complex transport and cycling of Hg species in water bodies.

Keywords: CE-QUAL-W2; Mercury; Methylmercury; cycling; Mercury simulation module

1. Introduction
CE-QUAL-W2 (W2) is a two-dimensional (2D), laterally averaged, longitudinal/vertical,
hydrodynamic and water quality model for simulating surface water bodies. Lateral averaging
assumes lateral variations in velocities, temperatures, and constituents are negligible. This model
has been continuously developed and maintained by the U.S. Army Corps of Engineers (USACE)
and Portland State University since late 80s [1,2]. Since its first release in 1986, the W2 model has
been successfully applied to hundreds of rivers, lakes, reservoirs and estuaries throughout the world
for thermal and water quality investigations [3–8]. U.S. governmental agencies including USACE,
U.S. Bureau of Reclamation (USBR), U.S. Geological Survey (USGS), U.S. Environmental Protection
Agency (USEPA), and Tennessee Valley Authority (TVA) as well as numerous states, county, and local
agencies have used this model as a management tool to evaluate the impacts of point and nonpoint
pollution sources including organic wastes, nutrients, and temperature in water bodies. The W2
model has also been applied in China [6]. Cole and Wells [2] presented the model theory, fundamental
equations, and application guidelines. The model complexity has increased significantly with the
increasing complexity of water quality and management issues since its release. The latest version of the
W2 model can simulate the complete eutrophication process in water bodies, including carbon, nitrogen
and phosphorous cycles, multiple algae, epiphyte and macrophyte species, dissolved oxygen, etc.

Water 2017, 9, 643; doi:10.3390/w9090643 www.mdpi.com/journal/water

Water 2017, 9, 643 2 of 22

Additionally, a benthic sediment diagenesis module was integrated into the model to compute the
sediment-water exchange fluxes of nutrients and sediment oxygen demand [9].
Mercury (Hg) is a global, persistent, and bioaccumulative toxic contaminant. Its organic form,
methylmercury (MeHg), is the most biologically active and toxic form of Hg. It can accumulate in
organisms within the food chain, such as fish, posing a risk to wildlife and humans [10–12]. Several
models have been developed to simulate the transport and fate of Hg in aquatic environments.
These models include the MCM [13], MERC4 [14], SERAFM [15], and WASP [16,17]. Although W2 is
a powerful tool and can simulate up to 32 water quality constituents, the current W2 model does not
have capability of simulating Hg transport and cycling in water bodies.
To effectively evaluate both the potential for harmful bioaccumulation and proposed measures
to mitigate that harm, the spatial and temporal distribution of Hg within a water body should be
characterized as completely as possible. There has been a need to bring the W2 to the state-of-art and
adding Hg modeling capability. In this study, a Hg simulation module was developed and incorporated
into the W2 model. With this enhancement, W2 model can directly simulate the transport and cycling
of three Hg species in water bodies. After a series of model testing and validation studies, the enhanced
W2 model was applied to the Xiaxi River for further evaluation of the model performance. The Xiaxi
River, which drains the Hg mining area in Wanshan County, has been contaminated by numerous
Hg tailings. Wanshan County, located in Guizhou Province, south-western China, was identified as
a heavy Hg contamination site. The largest conglomeration of Hg mines and refining plants in China
is located in this area [18]. Enhanced W2 model with a newly developed Hg simulation module was
applied to the Xiaxi River. Besides evaluating the W2 performance, model results of this application
were intended to provide insight into the long-term fate of MeHg and Total Hg (THg) along the
river and the relative importance of different processes in Hg cycling. This application can also be
used as a management tool to quantify the sources of Hg contamination, the distribution of Hg,
the influence of changing environmental conditions, and long-term mitigation of Hg contamination
within the watershed.

2. Hg Simulation Module within CE-QUAL-W2

One of the major concerns of Hg and its impact on the environments is its transformation to MeHg.
Speciation plays a major role in determining the bioavailability of Hg species for MeHg transformation
and toxicity of Hg to living organisms. Speciation also influences transport of Hg within and between
environmental media [19–22]. Hg0 and HgII are the major chemical forms of Hg input into the
environment from anthropogenic or natural sources [20]. During the biogeochemical cycling of Hg,
MeHg can be produced. Hg biogeochemical cycle involves three species and multi-phases in nature.
The Hg simulation module in the W2 model was designed to simulate three primary Hg species
of environmental concern: Hg0, HgII, and MeHg. Hg0 is assumed to exist in the dissolved phase
and only in the water column. HgII and MeHg are simulated for the water column and sediment
layer. The three Hg species and their kinetic equations implemented in the Hg simulation module are
described in detail in Zhang and Johnson [23], and briefly summarized here.
Hg0 is slightly water soluble and has a high Henry’s Law constant [24]. Hg0 constitutes
very little of the total mercury in the surface water but may provide a significant pathway for the
volatilization of Hg from surface waters. In the Hg simulation module, Hg0 is assumed to exist in
the dissolved phase and only in the water column. MeHg and HgII exist in both the water column
and the sediment layer and may distribute in dissolved phase and sorbed with dissolved organic
carbon (DOC), particulate organic matter (POM), and inorganic solids. Physical and biochemical
rate processes simulated in the Hg simulation module include: (1) adsorption and desorption of
Hg species; (2) volatilization; (3) atmospheric deposition; (4) diffusive exchange between the water
column and sediment layer; (5) deposition and re-suspension; (6) sediment burial of adsorbed Hg;
(7) biogeochemical transformations among the three species. Figure 1 provides an overview of the
Water 2017, 9, 643 3 of 22
Water 2017, 9, 643 3 of 23

model
model representation of the
representation of theHg
Hgspecies
speciesand
andtheir
theirprocesses.
processes.Table
Table1 1lists
liststhe
thesymbols
symbols and
and definitions
definitions of
of concentrations of Hg species computed in the Hg simulation
concentrations of Hg species computed in the Hg simulation module.module.

Air-Water Interface External Loading

Volatilization
Hg0
Water Column

Depth h
Demethylation
MeHg HgII
Methylation

Resuspension

Resuspension
Diffusion

Deposition
Deposition

Diffusion
DOC
Muti-Solids
Water-Sediment Interface

Demethylation
Benthic Sediment

MeHg HgII

Depth h2
Methylation
Burial Burial
DOC
Muti-Solids

Figure 1.
Figure Conceptual representation
1. Conceptual representation of
of Hg
Hg speciation
speciation and
and processes
processes modeled
modeled in
in the
the W2
W2 model.
model.

Table 1.
Table List of
1. List of concentrations
concentrations of
of Hg
Hg species
species computed
computed in
in the
the W2
W2 model.
model.

Symbol
Symbol Definition
Definition Units
Units
Hg0
Hg0 Hg0 concentration in water
Hg0 concentration in water ngng·L
·L−1
−1

HgII
HgII Concentration of of
Concentration total
totalHgII
HgIIin
inwater
water ngng·L
−
·L −11

HgII
HgIId d Concentration of of
Concentration dissolved
dissolvedHgII
HgII in
in water
water ·L−1 −1
ngng·L
HgII
HgIIdoc
doc Concentration
Concentration of of
DOCDOCadsorbed
adsorbed HgII
HgII in
inwater
water ·L−1 −1
ngng·L
HgIIpom Concentration of POM adsorbed HgII in water ng·L−1 −1
HgIIpom Concentration of POM adsorbed HgII in water ng·L
HgIIpt Total concentration of solids adsorbed HgII in water ng·L−1 −1
HgII
HgIIptspt Total concentration of solids adsorbed HgII in
Total concentration of solids adsorbed HgII in waterwater ngng·L
·g−1
HgII
HgII2 pts Total concentration of solids adsorbed
Concentration of total HgII in sediment HgII in water ng·g
ng·L−1
−1

HgIIdp2
HgII 2 Concentration of of
Concentration total HgII in
dissolved sediment
HgII in pore water −
ngng·L
·L −11

HgII
HgIIdocp2
dp2 Concentration
Concentration of of DOC adsorbed
dissolved HgII inHgII in pore
pore waterwater ·L−1 −1
ngng·L
HgII
HgIIpom2
docp2
Concentration
Concentration of of
DOCPOMadsorbed
adsorbed HgII
HgII in
in sediment
pore water ·L−1 −1
ngng·L
HgIIpt2 Total concentration of solids adsorbed HgII in sediment ng·L−1 −1
HgIIpom2 Concentration of POM adsorbed HgII in sediment ng·L
HgIIpts2 Total concentration of solids adsorbed HgII in sediment ng·g−1
HgII
MeHg pt2 Total concentration of solids adsorbed
Concentration of total MeHg in water HgII in sediment ngng·L
·L−1
−1

HgIIpts2
MeHg Total concentration
Concentration of solids MeHg
of dissolved adsorbed HgII in sediment ngng·g
in water ·L − 1 −1
d
MeHg
MeHg doc Concentration
Concentration of of DOC
total adsorbed
MeHg MeHg in water
in water ·L−1 −1
ngng·L
MeHg
MeHg pom
d
Concentration
Concentration of of POM adsorbed
dissolved MeHgMeHg in water
in water ·L−1 −1
ngng·L
MeHgpt Total concentration of solids adsorbed MeHg in water ng·L−1 −1
MeHgdoc Concentration of DOC adsorbed MeHg in water ng·L
MeHgpts Total concentration of solids adsorbed MeHg in water ng·g−1
MeHg
MeHg2 pom Concentration of POM adsorbed MeHg
Concentration of total MeHg in sediment in water ng·L
ng·L−1
−1

MeHg
MeHg pt
dp2
Total concentration
Concentration of solids MeHg
of dissolved adsorbed MeHg
in pore waterin water ngng·L
·L − 1 −1

MeHg
MeHg pts Total concentration
Concentration of solids
of DOC adsorbed
adsorbed MeHgMeHgin porein water ngng·g
water ·L − 1 −1
docp2
MeHg
MeHg pom2
2 Concentration
Concentration of of POM
total adsorbed
MeHg MeHg in sediment
in sediment ·L−1 −1
ngng·L
MeHg
MeHg pt2
dp2
Concentration
Concentration of of solids adsorbed
dissolved MeHgMeHg in porein water
sediment ·L−1 −1
ngng·L
MeHgpts2 Concentration of solids adsorbed MeHg in sediment ng·g−1 −1
MeHgdocp2 Concentration of DOC adsorbed MeHg in pore water ng·L
MeHgpom2 Concentration of POM adsorbed MeHg in sediment ng·L−1
The sediment
MeHgpt2 layer represents the
Concentration upperadsorbed
of solids mixed layer
MeHg and may be on theng·L
in sediment order−1 of several
centimeters MeHg
thick pts2due toConcentration
bioturbation of
and mixing.
solids Suspended
adsorbed MeHg sediments,
in sedimentwith Hgng·gbound
−1 to them,
are deposited to and eroded from the sediment bed. Depending upon ambient concentrations of
The sediment layer represents the upper mixed layer and may be on the order of several
centimeters thick due to bioturbation and mixing. Suspended sediments, with Hg bound to them,
Water 2017, 9, 643 4 of 22

Hg species, the suspended sediments lost or gained to the water column become a source or sink
for Hg. Once deposited, sediments coalesce to form an unconsolidated layer of variable, but often
shallow depth. This active layer of sediments may undergo continual bioturbation, or mixing by
organisms, so that sediments and Hg are distributed evenly throughout. Deeper sediment is considered
biologically inactive, and a static repository for sediments and Hg as they are buried.
As represented in Figure 1, the transport and cycling of Hg species in a water body is a complex
interaction of various physical, chemical, and biochemical processes. The physical and biochemical
processes modeled in the Hg simulation module are reasonably well documented in Zhang and
Johnson [23]. The three Hg species and their kinetic source and sink equations implemented in the W2
model are briefly summarized here.

2.1. Hg Partitioning
Hg species may be present in different phases in aquatic environments. In the Hg simulation
module, Hg0 is assumed in the dissolved phase, HgII and MeHg are allowed to be partitioned
among the dissolved phase and DOC, and solids adsorbed phases. Solids can be assigned to abiotic
mineral solids, detrital, or various classes or size categories of solids. Under equilibrium partitioning,
HgII and MeHg are assumed to be instantly exchangeable between the dissolved and adsorbed phases.
The fractions of each phase are functions of the partition coefficients and the concentrations of DOC,
POM and inorganic solids. The linear equilibrium partitioning fractions of HgII and MeHg based on
a total volume basis in the water column are calculated as follows.

106
f d (i ) = (1)
R (i )

Kdoc (i ) × DOC
f doc (i ) = (2)
R (i )
K pom (i ) × POM
f pom (i ) = (3)
R (i )
K pn (i ) × mn
f pn (i ) = (4)
R (i )
N
R(i ) = 106 + Kdoc (i ) × DOC + K pom (i ) × POM + ∑ K pn (i) × mn (5)
n =1

Sediment HgII and MeHg are also allowed to be partitioned among dissolved, DOC, POM and
inorganic solids sorbed phases. The partitioning fractions of HgII and MeHg in the sediment layer are
identically calculated as that for the water column.

106 φ
f d2 (i ) = (6)
R2 ( i )

Kdoc2 (i ) × φ × DOC2
f doc2 (i ) = (7)
R2 ( i )
K pom2 (i ) × POM2
f pom2 (i ) = (8)
R2 ( i )
K pn2 (i ) × mn2
f pn2 (i ) = (9)
R2 ( i )
N
R2 (i ) = 106 φ + Kdoc2 (i ) × φ × DOC2 + K pom2 (i ) × POM2 + ∑ K pn2 (i) × mn2 (10)
n =1

The symbols in Equations (1)–(10) are defined in Table 2.

Water 2017, 9, 643 5 of 22

Table 2. Definition of symbols used in Equations (1)–(15).

Symbol Definition Units

CL cloud cover /
DOC dissolved organic carbon in water mg·L−1
DOC2 dissolved organic carbon in pore water mg·L−1
fd fraction of dissolved phase in water /
fdoc fraction of DOC adsorbed phase in water /
fd2 fraction of dissolved phase in sediment /
fdoc2 fraction of DOC adsorbed phase in sediment /
fpom fraction of POM adsorbed phase in water /
Fpom2 fraction of POM adsorbed phase in sediment /
fpn fraction of inorganic solid “n” adsorbed phase in water /
fpn2 fraction of inorganic solid “n” adsorbed phase in sediment /
h water depth m
h2 sediment layer thickness m
Hg00 air concentration of Hg0 ng·L−1
i either HgII or MeHg /
I0 solar radiation at the water surface W ·m−2
I0pht light intensity when kpht is measured W ·m−2
k12 Hg0 oxidation rate in water d−1
kd21 photoreduction rate of dissolved HgII in water d−1
kdoc21 photoreduction rate of DOC adsorbed HgII in water d−1
kd23 methylation rate of dissolved HgII in water d−1
kdoc23 methylation rate of DOC adsorbed HgII in water d−1
kd31 photolytic degradation rate of dissolved MeHg in water d−1
kdoc31 photolytic degradation rate of DOC adsorbed MeHg in water d−1
kd32 demethylation rate of dissolved MeHg in water d−1
kdoc32 demethylation rate of DOC adsorbed MeHg in water d−1
kd32-2 dissolved MeHg demethylation rate in sediment d−1
kso42 sediment sulfate reduction rate d−1
KH Henry’s law constant Pa·m3 ·mol−1
Kdoc equilibrium partition coefficient for DOC in water L·kg−1
Kdoc2 equilibrium partition coefficient for sediment DOC L·kg−1
Kpom equilibrium partition coefficient for POM in water L·kg−1
Kpom2 equilibrium partition coefficient for sediment POM L·kg−1
Kpn equilibrium partition coefficient for inorganic solids in water L·kg−1
Kpn2 equilibrium partition coefficient for sediment solids “n” L·kg−1
KSO4 half-saturation constant for the effect of sulfate on methylation mg-O2 ·L−1
LHgII atmospheric deposition rates of HgII µg·m−2 ·d−1
LMeHg atmospheric deposition rates of MeHg µg· m−2 ·d−1
mn inorganic solid “n” concentration in water mg·L−1
mn2 inorganic solid “n” concentration in sediment mg·L−1
MeHg0 air concentration of MeHg ng·L−1
POM particulate organic matter in water mg L−1
POM2 particulate organic matter in sediment mg·L−1
rmso4 ratio of sediment methylation rate and sulfate reduction rate L·mg−1
R universal gas constant Pa·m3 ·mol−1 ·K−1
SO42 sediment pore water sulfate concentration mg-O2 ·L−1
SSHg0 source/sink terms of Hg0 in water µg·L−1 ·d−1
SSHgII source/sink terms of HgII in water µg·L−1 ·d−1
SSMeHg source/sink terms of MeHg in water µg·L−1 ·d−1
SSHgII2 source/sink terms of HgII in sediment µg·L−1 ·d−1
SSMeHg2 source/sink terms of MeHg in sediment µg·L−1 ·d−1
Twk water temperature K
Y12 Hg0 oxidation yield coefficient g ·g−1
Y21 HgII photoreduction yield coefficient g ·g−1
Y23 HgII methylation yield coefficient g ·g−1
Y31 MeHg photolytic degradation yield coefficient g ·g−1
Y32 MeHg demethylation yield coefficient g ·g−1
φ porosity /
λmax maximum light extinction coefficient m−1
vv-Hg0 volatilization velocity of Hg0 m ·d−1
vv-MeHg volatilization velocity of MeHg m ·d−1
vb sediment burial velocity m ·d−1
vpn settling velocity of inorganic solid “n” m ·d−1
vrn sediment resuspension velocity of solid “n” m ·d−1
vsom settling velocity of POM m ·d−1

2.2. Hg Transformations and Kinetic Equations

The oxidation, reduction, methylation and demethylation transformations of Hg species are
assumed to be widespread in aquatic environments. Since some of the reaction processes have not been
Water 2017, 9, 643 6 of 22

well understood and defined, Hg transformation reactions are simulated using first order rate kinetics.
These reactions may act on Hg depending on the speciation and partitioning of Hg. To account for this,
the base rate of reaction is modified by the fraction of Hg dissolved in the aqueous phase, complexed
with DOC, and adsorbed to abiotic and biotic particles. As represented in Figure 1, major processes
simulated in the Hg simulation module also include partitioning of HgII and MeHg, particulate
settling, resuspension and burial, sediment-water diffusion, and volatilization. Meanwhile, Hg species
can be transported together with water, DOC, and suspended solids. The total internal source and sink
terms of three species in the water column are calculated as follows.

vv− Hg0
 
Hg00
SS Hg0 = − Hg0 − − k12 × Hg0
h K H /( R × Twk ) | {z }
| {z } Hg0 oxidation
Hg0 volatilization
I 1 − e−λmax ×h  
+1.33 0 (1 − 0.56CL ) k d21 × f d− HgI I + k doc21 × f doc− HgI I HgI I × Y21
I0pht λmax × h (11)
| {z }
HgI I reduction
I 1 − e−λmax ×h  
+1.33 0 (1 − 0.56CL ) k d31 × f d− MeHg + k doc31 × f doc− MeHg MeHg × Y31
I0pht λmax × h
| {z }
MeHg photolytic degradation

!
L HgI I N
1
SS HgI I =
h }
−
h ∑ v pn × f pn− HgI I + vsom × f pom− HgI I HgI I
| {z n =1
HgI I atmospheric deposition
| {z }
HgI I settling
vm h    i
+ f d− HgI I2 + f doc− HgI I2 HgI I2 /φ − f d− HgI I + f doc− HgI I HgI I
|h {z }
HgI I sediment−water trans f er
I 1 − e−λmax ×h  
−1.33 0 (1 − 0.56CL ) k d21 × f d− HgI I + k doc21 × f doc− HgI I HgI I
I0pht λmax × h
| {z } (12)
HgI I reduction !
  1 N
− k d23 × f d− HgI I + k doc23 × f doc− HgI I HgI I + ∑ vrn × f pn− HgI I2 HgI I2 + k|12 × Hg0 × Y12
| {z } h n =1 {z }
HgI I methylation
| {z } Hg0 oxidation
HgI I re−suspension
I 1 − e−λmax ×h  
+1.33 0 (1 − 0.56CL ) k d32 × f d− MeHg + k doc32 × f doc− MeHg MeHg × Y32
I0pht λmax × h
| {z }
MeHg demethylation

!
L MeHg 1 N
h n∑
SS MeHg = − v pn × f pn− MeHg + vsom × f pom− MeHg MeHg
h }
| {z =1
MeHg atmospheric depostion
| {z }
MeHg settling
vm h    i
+ f d− MeHg2 + f doc− MeHg2 MeHg2 /φ − f d− MeHg + f doc− MeHg MeHg
|h {z }
! sediment−water trans 
MeHg f er
1 N vv− MeHg

MeHg0
h n∑
+ vrn × f pn− MeHg2 MeHg2 − MeHg −
=1 h K H /( RTwk )
| {z } | {z }
MeHg volatilization
MeHg re−suspension (13)
I 1 − e−λmax ×h  
−1.33 0 (1 − 0.56CL ) k d31 × f d− MeHg + k doc31 × f doc− MeHg MeHg
I0pht λmax × h
| {z }
 MeHg photolytic degradation 
+ k d23 × f d− HgI I + k doc23 × f doc− HgI I HgI I × Y23
| {z }
HgI I methylation
I 1 − e−λmax ×h  
−1.33 0 (1 − 0.56CL ) k d32 × f d− MeHg + k doc32 × f doc− MeHg MeHg
I0pht λmax × h
| {z }
MeHg demethylation
Water 2017, 9, 643 7 of 22

Hg settles through water column and deposits to or erodes from benthic sediments. Within the
sediment bed, biotic and abiotic reactions can result in methylation, demethylation, and reduction,
just as in the water column. However, because of varying environmental conditions, the rate of
these reactions can vary dramatically from those in the water column. The sediment layer in the Hg
simulation module is assumed to have constant properties including the thickness, volume, porosity,
and bulk density. Only HgII and MeHg are simulated for the sediment layer. Concentrations of Hg
species are expressed in terms of mass per unit volume of total sediments (ng·L−1 ). The total internal
source and sink terms of HgII and MeHg in the sediment layer are calculated as follows.
! !
N N
1 1
SS HgI I2 =
h2 ∑ v pn × f pn− HgI I + vsom × f pom− HgI I HgI I −
h2 ∑ vrn × f pn− HgI I2 HgI I2
n =1 n =1
| {z } | {z }
HgI I depostion HgI I erosion
vb N
h2 n∑
− ( f pn− HgI I2 + f pom− HgI I2 ) HgI I2 + k d32−2 × f d− MeHg2 × MeHg2 × Y32
=1 | {z }
MeHg demethylation
(14)
| {z }
HgI I burial
vm h    i
− f d− HgI I2 + f doc− HgI I2 HgI I2 /φ − f d− HgI I + f doc− HgI I HgI I
h
|2 {z }
HgI I sediment−water trans f er
SO42
−k so42 × × SO42 × rmso4 × f d− HgI I2 × HgI I2
KSO4 + SO42
| {z }
HgI I methylation

! !
N N
1 1
SS MeHg2 =
h2 ∑ v pn × f pn− MeHg + vsom × f pom− MeHg MeHg − h2 ∑ vrn × f pn− MeHg2 MeHg2
n =1 n =1
| {z } | {z }
MeHg deposition MeHg erosion
vm h    i
− f d− MeHg2 + f doc− MeHg2 MeHg2 /φ − f d− MeHg + f doc− MeHg MeHg
h
|2 {z }
MeHg sediment−water trans f er
(15)
v N
− b ( ∑ f pn− MeHg2 + f pom− MeHg2 ) MeHg2 − k d32−2 × f d− MeHg2 × MeHg2
h 2 n =1 | {z }
| {z } MeHg demethylation
MeHg burial
SO42
+k so42 × × SO42 × rmso4 × f d− HgI I2 × HgI I2 × Y23
KSO4 + SO42
| {z }
HgI I methylation

The symbols in Equations (11)–(15) are defined in Table 2.

Within the sediment layer, dissolved species migrate downward or upward through percolation
and pore water diffusion. The sediment-water flux of dissolved Hg species included in Equations (12)
to (15) is the product of effective mass transfer velocity and the difference between bulk fluid
concentrations on either side of the interface. The mass transfer velocity between each modeled
species in the sediment layer and the water column is calculated in the W2 model. The following four
equations are included in the Hg simulation module for calculating the sediment-water transfer of
dissolved Hg species: (1) Thibodeaux et al. [25]; (2) Di Toro et al. [26]; (3) Boyer et al. [27]; and (4)
Schink and Guinasso [28].
1
vm = z2 1
(16)
D ρ K + vms b b d2

vm = 0.19φ( MW )2/3 (17)

φ 3 Dm
vm = (18)
zl

u∗ ( Dm /ν)2/3
vm = 8.64 × 104 (19)
24
Water 2017, 9, 643 8 of 22

where Db is biodiffusion coefficient representing particle diffusivity (m2 ·d−1 ), ρb is sediment bulk
density (g·cm−3 ), vm is user-defined sediment-water transfer velocity (m·d−1 ), z2 is sediment
bioturbation layer thickness (m), MW is molecular weight of Hg species (g·mol−1 ), Dm is molecular
diffusion coefficient (m2 ·d−1 ), zl is pore water diffusion layer thickness (0.01 m), u* is flow shear
velocity along the bed, which is approximately 10 percent of the mean velocity of flow (m·s−1 ), v is
kinematic viscosity of water (m2 ·d−1 ).

2.3. Enhanced CE-QUAL-W2 Model

The W2 model uses fixed computation grids with a static bathymetric surface onto which
longitudinal segments and vertical layers are mapped; the hydrodynamic and water quality
computations are performed at the intersections of these segments and layers. A direct coupling
between hydrodynamic and water quality simulations is implemented in W2 model. The 2D water
quality component computes the transport and fate of constituents with their kinetic reaction rates
expressed in source and sink terms. The general 2D water quality transport and mass balance equation
of W2 model is written as follows [2].

∂( BΦ) ∂(UBΦ) ∂(WBΦ) ∂( BDx (∂Φ/∂x )) ∂( BDz (∂Φ/∂z))

+ + − − = q Φ B + SΦ B (20)
∂t ∂x ∂z ∂x ∂z

where Φ is laterally averaged constituent concentration (g·m−3 ), B is control volume width (m), U and
W are longitudinal and vertical velocities respectively (m·s−1 ), Dx is longitudinal temperature and
constituent dispersion coefficient (m2 ·s−1 ), Dz is vertical temperature and constituent dispersion
coefficient (m2 ·s−1 ), qΦ is lateral inflow or outflow mass flow rate of constituent per unit volume
(g·m−3 ·s−1 ), SΦ is laterally averaged source/sink term (g·m−3 ·s−1 ).
The sources/sinks for each water quality state variable in the W2 model are separated into two
arrays, one contains boundary sources/sinks, and the other one contains internal sources/sinks due to
kinetic interactions. Figure 2 provides the overall flow chart of the W2 model solving the transport
and mass balance of three Hg species.
Water 2017, 9, 643 9 of 22
Water 2017, 9, 643 10 of 23

Figure 2. Flow chart of the W2 model solving the transport and mass balance of three Hg species.
Figure 2. Flow chart of the W2 model solving the transport and mass balance of three Hg species.
3. Enhanced CE-QUAL-W2 Model Validation and Evaluation
3. Enhanced CE-QUAL-W2 Model Validation and Evaluation
A comprehensive validation of the newly developed Hg simulation module in the W2 model
A comprehensive
would validation
require an extensive testingof thevalidation.
and newly developed Hgenhanced
In this study, simulationW2module
model wasin the W2 model
validated
would require
through an extensive
a series testing
of case studies andand validation.
a real In this study,
world application. The Hgenhanced W2
simulation modeldeveloped
module was validated
here includes
through a seriessimilar
of caseHg cycling
studies processes
and as WASP
a real world model. The
application. TheWASP model is also
Hg simulation capable
module of
developed
simulating the transport and cycling of three Hg species (Hg0, HgII and MeHg)
here includes similar Hg cycling processes as WASP model. The WASP model is also capable of in water bodies.
The model
simulating theresults generated
transport from WASP
and cycling were
of three Hgfirst used (Hg0,
species to validate individual
HgII and MeHg) Hginprocesses
water bodies.
simulated in the W2 model. This model validation was designed to assure that the algorithms and
The model results generated from WASP were first used to validate individual Hg processes simulated
formulations are implemented correctly in the enhanced W2 model. The enhanced W2 model was
in the W2 model. This model validation was designed to assure that the algorithms and formulations
also applied to the Xiaxi River in Wanshan County, China. Wanshan County in east Guizhou
are implemented correctly in the enhanced W2 model. The enhanced W2 model was also applied to
the Xiaxi River in Wanshan County, China. Wanshan County in east Guizhou Province has a long
history of Hg mining and processing. Multi million tons of calcine from the roasted ore was deposited
Water 2017, 9, 643 10 of 22

in this area from 1949 to early 1990s [29]. Approximately 4.4 g Hg per kg of calcines were detected
in Wanshan County [30]. Although Hg mining and retorting activities have been banned since 2001,
the field investigation found the Hg leak from historic deposits of calcines and Hg contamination in
the Xiaxi River was detected. The application of enhanced W2 model to the Xiaxi River was intended,
in part, to evaluate the merit of the W2 model for simulating the transport and cycling of Hg species in
a water body.

3.1. Model Validation through Comparing WASP Model Results

In this study, an equivalent segment was set up for W2 and WASP. The two models were run with,
to the extent possible, a consistent set of kinetic coefficients and parameters, initial conditions, fluxes
from the water column and water column concentrations. A user defined sediment-water transfer
velocity was used in both models because different approaches are included. The same Hg partitioning
coefficients on solids were specified for the water column and sediment layer due to the limitation of
the WASP model. In the W2 model, the impact of sulfate reduction on methylation rate in the sediment
layer is simulated, which has been reported in many literatures [31–34]. However, the WASP model
does not simulate the impact of sulfate on the methylation. In the test case, sulfate reduction rate in
W2 was specified to ensure that the same methylation rate (kd23_2 = 0.01 d−1 in Table 3) was used in
both models. The WASP model simulates the demethylation from MeHg to HgII in the water column
process through a bacterial degradation process, but this process is simulated in the W2 model through
a photolytic degradation. Therefore, light impacts on the demethylation in this test case were ignored
in the W2 model. The photolytic degradation of MeHg has been reported in many literatures [35–37].
Meanwhile, WASP model always needs to be coupled with other hydrodynamic models for water
quality investigations, such as EFDC [38,39].
In this test case, the water column was set as 100 m long, 10 m wide with an average of 2.5 m
deep. The water temperature was set as 25 ◦ C. The solar radiation was set as 500 W·m−2 , and light
extinction coefficient was 1.0 m− 1 . Both inorganic and organic solid classes were simulated in both
models. The suspended concentrations of silt and fines, sand and organic matter were defined as
20, 50 and 15 mg·L−1 respectively. The bottom sediment layer was made up of four solid classes
with a fixed porosity of 0.7, on average, 83.33% sand, 10.71% silt and fines, and 5.96% organic matter.
The sediment temperature was set as 20.0 ◦ C. The settling velocities for silts and fines, and organic
matter were respectively set as 0.5, 1.2 and 0.3 m·d−1 . The resuspension velocities for silts and fines,
and organic matter were set as 1.1 × 10−4 , 8.0 × 10−5 and 9.0 × 10−4 m·d−1 . Burial velocity was
set as 5.03145 × 10−6 m·d−1 . The sediment-water transfer velocity was specified as 0.0864 m·d−1 .
The initial concentrations of Hg0, HgII and MeHg in the water column were defined as 1.0, 10.0 and
0.0 ng·L−1 , and the initial concentrations of HgII and MeHg in the sediment layer were specified
as 50.0 and 0.0 ng·g−1 . Most of data in this test case was based on observed data in Lake Taihu in
China [40]. The other water quality parameters are given in Table 3. These parameters were estimated
from literature values provided by Knightes et al. [17], Allison and Allison [41] and Muresan et al. [42].
Both W2 and WASP models were ran with a fixed time step of 0.1 days for a year simulation period.

Table 3. List of water quality parameters used in the test cases.

Variable Units Value

Kp-HgII L·kg−1 2.0 × 103 (Silt and fine), 1.0 × 103 (Sand)
Kpom-HgII L·kg−1 1.0 × 104
Kp-MeHg L·kg−1 1.0 × 103 (Silt and fine), 0.5 × 103 (Sand)
Kpom-MeHg L·kg−1 0.5 × 104
KH-Hg0 atm·m3 ·mol−1 0.0071
vv-Hg0 m ·d−1 0.8
Hg00 ng·L−1 0.0
k12 d−1 0.001
Y12 g ·g−1 1.0
kd21 d−1 0.01
Water 2017, 9, 643 11 of 22

Table 3. Cont.

Variable Units Value

Water 2017, 9, 643 12 of 23
Y21 g ·g−1 1.0
Water 2017, 9, 643I0pht W ·m−2 100.0 12 of 23
kd23Y21 g·g−1d−1
1.0 0.002
Y23 I0pht W·mg−2·g−1
100.0 1.07
Y21 g·g−1 −1
1.0
kd32kd23 d−1 d 0.002 0.04
I0pht
kd23_2 W·md−2−1
100.0 0.01
Y23 g·g−1 1.07
kd31kd23 d−1 d−1
0.002 0.01
kd32 d−1 0.04
Y31 Y23 g·g−1g·g−1
1.07 0.93
kd23_2
kd32_2 d−1 −10.01
kd32 d−1 d 0.04 0.005
Y32 kkd23_2
d31 d−1
−1
d g·g
0.01
−1
0.01 0.93
Y31 g·g −1 0.93
kd31 d −1 0.01
kd32_2 d−1 0.005
Y31 g·g−1 0.93
The test case study
Y32 was g·g
used−1 to validate
0.93 the performances of the W2 model with respect
kd32_2 d−1 0.005
to various aspects such
Y32 as multi-phase
g·g −1 partitioning,
0.93 methylation,
demethylation transformations,
The test casetransfer.
and sediment-water study was Figure
used to validate
3a,b show the performances
the comparison of the ofW2W2 model
andwith respect
WASP to
computed
various
The aspects
test such
case as multi-phase
study was used topartitioning,
validate themethylation,
performances demethylation
of the W2 transformations,
model with respect and
to
concentrations of HgII in the water column and sediment layer. Figure 4a,b show W2 computed
sediment-water
various aspects transfer.
such Figure 3a,b show the
as multi-phase comparison of W2 andtransformations,
WASP computed
HgII internal flux by each process. partitioning,
Initially, totalmethylation, demethylation
concentration of HgII in the water and column
concentrations of HgII in the water column and sediment
sediment-water transfer. Figure 3a,b show the comparison of W2 and WASP layer. Figure 4a,b show W2 computed
computed
increased mainly
HgII internal fluxby the sediment
by ineach resuspension, since this flux remained at a high column(nearly
level
concentrations
− 1 − 1 of HgII theprocess. Initially,
water column andtotal concentration
sediment of HgII
layer. Figure 4a,binshow
the W2watercomputed
L ·internal
·increased
1.8 ngHgII d mainly), even
fluxbyby
though
theeach HgIIresuspension,
sediment
process.
settling increased this gradually
sinceconcentration
Initially, total flux remained during
of HgII
the
at ainhigh simulation
thelevel
water(nearly
column1.8period.
Total concentration
ng·L −1·d−1), even of HgII
though in the
HgII water
settling column
increased reached
gradually the equilibrium
during the after
simulation
increased mainly by the sediment resuspension, since this flux remained at a high level (nearly 1.8 20 days.
period. In
Totalthis test
concentration
case, HgII
ng·L settling
−1 ·d ), even
−1 of HgII
andthough in the
resuspension water column reached
were increased
HgII settling the two main the equilibrium
internal
gradually after
sinkthe
during 20 days.
andsimulation In this
source inperiod. test
the water case,
Totalcolumn.
HgII settling
concentration
Hg0 oxidation, and
HgII resuspension
of reduction,
HgII in the waterwere
HgII the two
column
methylation main
reached and internal
the sink and
equilibrium
sediment-water source
after in theIn
20 days.
transfer water column.
this were
rates test case,
relatively
Hg0 oxidation, HgII reduction, HgII methylation and sediment-water transferinrates were relatively
small. HgII
Totalsettling and
concentration resuspension
of HgII werein the thesediment
two main internal
layer was sink and stable
more source forthethewater column.period.
simulation
small.
Hg0 Total
oxidation, concentration
HgII of
reduction, HgII
HgIIin the sediment
methylation layer
and was more
sediment-water stable for
transferthe simulation
rates were period.
relatively
The sediment layer become a large storage reservoir for Hg.
The sediment layer become a large storage reservoir for Hg.
small. Total concentration of HgII in the sediment layer was more stable for the simulation period.
The sediment layer become a large storage reservoir for Hg.
WASP W2 60 WASP W2
100 HgII2 (ng g-1)
HgIIpts (ng g-1) 50
WASP W2 60 WASP W2
80
100
HgIIpts (ng g-1) 40
50 HgII2 (ng g-1)
60
80 30
HgII HgII

HgII HgII

40
40
60 20
30 HgIId2 (ng L-1)
HgII (ng L-1)
20
40 10
20
(ngLL-1-1) )
HgII d(ng HgIId2 (ng L-1)
200 100
0 60 (ng
HgII 120 ) 180(day) 240
L-1Time 300 360 0 60 120 180 240 300 360
0 d 0 Time (day)
0 60 120 180
(a) 240 300 360 0 60 120 (b)
180 240 300 360
Time (day) Time (day)

Figure 3. W2 and WASP (a) computed HgII distributed concentrations in the (b)water column (a) and the
Figure 3. W2 and WASP computed HgII distributed concentrations in the water column (a) and the
sediment
Figure layer
3. W2 (b): HgII (concentration of total HgII in water); HgIId (concentration of dissolved
sediment layer (b):and
HgII in water);
WASP
HgII computed HgII
(concentration distributed
of total HgII inconcentrations
water); HgIIin the water columnof(a)dissolved
(concentration and the HgII
pts (total concentration of solids adsorbed HgII indwater); HgII2 (concentration of
sediment layer HgII
(b): HgII (concentration of total HgII in water); HgIId (concentration of dissolved
in water);
totalHgII
HgII pts (total concentration
in sediment); of solids adsorbed HgII in water); HgII2 (concentration of total
d2 (concentration of dissolved HgII in sediment).
HgIIconcentration
HgII in water); HgIIpts (total of solids adsorbed HgII in water); HgII2 (concentration of
HgII in sediment); HgIId2 (concentration of dissolved HgII in sediment).
total HgII in sediment); HgIId2 (concentration of dissolved HgII in sediment).
2 60
Hg0 oxidation HgII settling
2 40
60
1 HgII reduction HgII methylation
L d )

HgII deposition HgII methylation

-1 d-1)-1 -1

Hg0 oxidation HgII settling

20
L d )

HgII resuspension Sediment-water transfer 40 HgII resuspension Sediment-water transfer

-1 d-1)-1 -1

1 HgII reduction HgII methylation HgII deposition

HgII burial HgII methylation
0 200
FluxL(ng

HgII resuspension Sediment-water transfer HgII resuspension Sediment-water transfer

FluxL(ng

0 60 120 180 240 300 360 0 60

HgII burial120 180 240 300 360
0 Time (day) -20
0 Time (day)
Flux (ng

-1 0
Flux (ng

60 120 180 240 300 360 0 60 120 180 240 300 360
Time (day) -40
-20 Time (day)
-1
-2 -60
-40

-2 (a) -60 (b)

(a) HgII internal fluxes in the water column (a) and (b)
Figure 4. W2 computed the sediment layer (b).
Figure 4. W2 computed HgII internal fluxes in the water column (a) and the sediment layer (b).
Figure 4. W2
Figure computed
5a,b show theHgII internalof
comparison fluxes in the
W2 and watercomputed
WASP column (a) and the sediment
concentrations layerin(b).
of MeHg the
water column and sediment layer. Figure 6a,b show W2 computed MeHg internal
Figure 5a,b show the comparison of W2 and WASP computed concentrations of MeHg in the flux by each
process.
Figure
water MeHg
5a,b
columnshow main
and thesource was
comparison
sediment from
layer. ofthe methylation
W26a,b
Figure andshow
WASP
W2ofcomputed
HgII in theMeHg
computed water internal
column.flux
concentrations Settling
ofbyMeHgand in the
each
process. MeHg main source was from the methylation of HgII in the water column. Settling
water column and sediment layer. Figure 6a,b show W2 computed MeHg internal flux by each process. and
Water 2017, 9, 643 12 of 22

MeHg Water
main2017,
source
9, 643 was from the methylation of HgII in the water column. Settling and resuspension 13 of 23
were not the dominant
Water 2017, 9, 643
processes affect the fate of MeHg in the water column. In the sediment
13 of 23
layer,
resuspension
mainWater
sources of643
2017, 9,
were not the dominant processes affect the fate of MeHg
MeHg come from MeHg deposition from water column and HgII methylation. in the water column. In the
13 of 23 It is
sediment layer,
resuspension weremain
not sources of MeHg
thesources
dominant come from
processes MeHgfate deposition from water column and HgII
important to understand the of MeHg in affect
orderthe of MeHg
to control in the
the production waterofcolumn.
MeHg In in the
the water
methylation.
resuspension
sediment It is
were
layer, important
mainnotsources
the toofunderstand
dominant
MeHg thefrom
processes
come sources
affect of fate
the
MeHg MeHgof in order
MeHg
deposition from intowater
control
the water the
column production
column. In the
and HgII
column and sediment layer and reduce the environmental risk.
of MeHg in the water column and sediment layer and reduce the environmental risk.
sediment layer,
methylation. main
It is sourcestoofunderstand
important MeHg come thefrom MeHg
sources deposition
of MeHg from
in order water column
to control and HgII
the production
methylation. It iswater
of MeHg in the important
columntoand
understand
sediment the sources
layer of MeHg
and reduce in order to
the environmental
WASP
control
risk. the
W2
production
0.8 WASP W2 0.2
of MeHg in the water column and sediment layer and reduce the environmental risk.
0.8 MeHgpts (ng g-1)
WASP W2 0.2 WASP W2
0.6 0.15
0.8 WASP
MeHgpts (ng g-1) W2 0.2 WASP W2
0.15 MeHg2 (ng g-1)

MeHgMeHg
0.6
MeHgMeHg

0.4 0.1 MeHgd2 (ng L-1)

MeHg
MeHg (ngLg-1-1))
pts (ng
0.6 0.15 MeHg2 (ng g-1)
0.4 0.1
0.05 MeHgd2 (ng L-1)
0.2
MeHg -1)
MeHgd(ng
(ngLL-1 MeHg2 (ng g-1)

MeHg
)
MeHg

0.4 0.1 MeHgd2 (ng L-1)

0.20 0.050
MeHg (ng L-1-1)
0.2 0
d (ng L 180
60MeHg120 ) 240 300 360 0.05
0 60 120 180 240 300 360
0 Time (day) 0 Time (day)
MeHg -1
0 60 d (ng L180
120
) 0 60 120 180 240 300 360
(a)(day) 240 300 360
Time 0 (b)
Time (day)
0
0 5. 60 120WASP 180 computed
240 300 0 60 120 180 240 300 360
Figure W2 and (a)
Time (day) MeHg360 (b)
distributed concentrations in the water
Time (day) column (a) and
Figure 5. W2 and WASP computed MeHg distributed concentrations in the water column (a) and
the sediment layer (b):
(a) MeHg (concentration of total MeHg in water); MeHg d (concentration of
Figure 5. layer
the sediment W2 and WASP
(b): MeHgcomputed MeHg distributed
(concentration of total concentrations
MeHg in in the(b)
water); water
MeHg column (a) and
(concentration of
d
dissolved MeHg in water); MeHgpts (total concentration of solids adsorbed MeHg in water); MeHg2
the sediment layer (b): MeHg (concentration of total MeHg in water); MeHgd (concentration of
dissolved
FigureMeHg
5. W2 in water);
and WASP MeHg
computed
pts (total
MeHg concentration
distributed of solids adsorbed
concentrations in the MeHg
water in water);
column
(concentration of total MeHg in sediment); MeHgd2 (concentration of dissolved MeHg in sediment). (a) MeHg
and 2
dissolved MeHg in water); MeHgpts (total concentration of solids adsorbed MeHg in water); MeHg2
(concentration
the sedimentof total
layerMeHg in sediment);
(b): MeHg MeHg
(concentration (concentration
ofd2total of dissolved
MeHg in water); MeHgd MeHg in sediment).
(concentration of
(concentration of total MeHg in sediment); MeHgd2 (concentrationMeHg
0.03 MeHg in water); MeHgpts (total concentration of solids
ofdeposition
dissolved MeHg inMeHg sediment).
resuspension
dissolved MeHgadsorbed
burial MeHg in MeHg
water); MeHg2
demethylation
0.4 Sediment-water transfer HgII methylation
(concentration
0.03
0.02 of total MeHg in sediment); MeHg d2 (concentration
MeHg of dissolved
deposition MeHg in
MeHg sediment).
resuspension
HgII methylation MeHg settling MeHg burial MeHg demethylation
0.4
L d )

d L) -1 d-1)

Sediment-water transfer HgII methylation

d-1) -1 d-1) -1 -1

MeHg photoreduction MeHg demethylation

0.02
0.01
0.03 MeHg resuspension
HgII methylation
Sediment-water transfer
MeHg settling
0.2 MeHg deposition MeHg resuspension
MeHg burial MeHg demethylation
0.4
-1

MeHg photoreduction MeHg demethylation

Time (day) Sediment-water transfer HgII methylation
FluxL (ng

d-1)L (ng

0.010
0.02
MeHg resuspension Sediment-water transfer 0.2
-1

Time (day)
Flux

HgII methylation MeHg settling

0 60MeHg photoreduction
120 180 240MeHg 300 360
Time (day) 0
L-1 (ng

L-1 (ng

demethylation
0
-0.01
0.01 MeHg resuspension Sediment-water transfer 0.2 0 60 120 180 240 300 360
Time (day)
Flux

Flux

0 60 120 180 240 300 360 0

Time (day)
Flux (ng

Flux (ng

-0.01
-0.02
0 -0.2 0 60 120 180 240 300 360
0 Time (day)
0 60 120 180 240 300 360
-0.02 (a) -0.2 0 60 120 (b)180 240 300 360
-0.01
(a) MeHg internal fluxes in the water column (a) and
Figure 6. W2 computed (b)the sediment layer (b).
-0.02 -0.2
Figure 6. W2 computed MeHg internal fluxes in the water column (a) and the sediment layer (b).
Figure W2 computed
To6.investigate (a)
MeHg internal
individual fluxes in the water
Hg transformations, solid column
sorption, (b) the sediment
(a) settling,
and layer and
resuspension, (b).
sediment-water
To investigatetransfer processes
individual Hg were turned off. Figure
transformations, 7a,b
solidcolumn show settling,
sorption, dissolvedresuspension,
concentrations of
Figure 6. W2 computed MeHg internal fluxes in the water (a) and the sediment layer (b). and
HgII and MeHgtransfer
sediment-water in the water column.
processes wereFigure
turned8a,b show
off. Figure Hg 7a,b
transformation
show fluxesconcentrations
dissolved respectively. W2 of
To investigate individual Hg transformations, solid sorption, settling, resuspension, and
predicted
HgII Toand concentrations
investigate
MeHg individual
in the waterof HgIIHgand
column. MeHg8a,b are consistent
transformations,
Figure solid with WASPsettling,
sorption, model
fluxesresults. Dissolved
resuspension, and
sediment-water
HgII was
transfer
lost by its
processes
reduction
were
and
turned
methylation
off.inshow
Figure
the
Hg7a,b
water
transformation
show dissolved
column. In the
respectively.
concentrations
meantime, MeHg
W2
was
of HgII
predicted concentrations
sediment-water transfer of HgII and
processes wereMeHg
turnedareoff.
consistent
Figure with
7a,b WASPdissolved
show model results. Dissolved
concentrations of
and MeHggainedin the
and water
reachedcolumn.the peakFigure 8a,b
around show Hg
50 days, transformation
then decreased fluxes
by itsrespectively.
demethylation W2 predicted
and
HgII was lost by its reduction and methylation in the water column.
HgII and MeHg in the water column. Figure 8a,b show Hg transformation fluxes respectively. W2 In the meantime, MeHg was
concentrations of HgIIThe
photoreduction. and MeHgcase are consistent with WASP model results.and Dissolved HgII was lost by
gained
predicted and reached above
concentrations theof peak studies 50
HgII around
and MeHg
indicate
days,
are
that
then the
consistent
algorithms
decreased
with WASP by its
model
formulations
demethylation were
and
results. Dissolved
its reduction
correctlyand methylation
implemented
photoreduction. in
Thereduction in
the
above case the water
enhanced W2 column.
model. In the meantime, MeHg was gained and reached
HgII was lost by its and studies indicate
methylation that
in the the column.
water algorithms andmeantime,
In the formulationsMeHg were was
the peak around
correctly 50
gained 10and reached days,
implemented then
in
the the decreased
enhanced
peak around by
W2 its demethylation
model.
50 days, then and
decreased photoreduction.
by its The
demethylation above
and case
WASP W2 0.3 WASP W2
studies indicate that the algorithms and formulations were correctly
photoreduction. The above case studies indicate that the algorithms and formulations were implemented in the enhanced
108 WASP 0.3
W2 model. in theW2 WASP W2
) L-1)
HgII (ng L )

correctly implemented enhanced W2 model. 0.2

L-1) (ng L-1) -1

86
) (ng L(ng
-1

1064 0.2
0.3
WASP W2 WASP W2
L-1MeHg

0.1
842
MeHg

0.1
HgII (ng HgII

0.2
620 0
MeHg (ng

0 60 120 180 240 300 360 0 60 120 180 240 300 360
40 Time (day) 0 Time (day)
0.1
0 60 120 180 240 300 360 0 60 120 180 240 300 360
2 (a)(day)
Time (b) (day)
Time
0 Figure 7. W2 and WASP 0 concentrations
(a) computed (a) HgII and (b) MeHg (b)in the water column.
0 60 120 180 240 300 360 0 60 120 180 240 300 360
Figure 7. W2 andTime
WASP(day)
computed (a) HgII and (b) MeHg concentrationsTime
in the(day)
water column.
(a) (b)
Figure 7. W2 and WASP computed (a) HgII and (b) MeHg concentrations in the water column.
Figure 7. W2 and WASP computed (a) HgII and (b) MeHg concentrations in the water column.
Water 2017, 9,
Water 2017, 9, 643
643 13
14 of 22
23
Water 2017, 9, 643 14 of 23
0.02 HgII methylation
0 0.02 MeHg demethylation
HgII methylation
0 0 60 120 180 240 300 360
0.01 MeHg
MeHg photoreduction
demethylation

) d-1)
-0.02 Time
300 (day)
) d-1)

0 60 120 180 240 360 MeHg photoreduction

0.01

-1-1
-0.02 Time (day)
-1-1

-1 dL
-0.04 0
-1 dL

(ng
(ng

0 0 60 120 180 240 300 360

(ng L
-0.04
(ng L

FluxFlux
-0.06 Hg0 oxidation
FluxFlux

-0.01 0 60 120 180 240 300 360

-0.06 HgII reduction
Hg0 oxidation Time (day)
-0.08 -0.01
HgII
HgII methylation
reduction Time (day)
-0.08 -0.02
-0.1 HgII methylation
-0.02
-0.1 (a) (b)
(a) (b)
Figure 8. W2 computed (a) HgII and (b) MeHg concentrations and internal fluxes in the water
column.
Figure 8.8.W2
Figure W2computed
computed
(a)(a) HgII
HgII andand (b) MeHg
(b) MeHg concentrations
concentrations and internal
and internal fluxes
fluxes in in the
the water water
column.
column.
3.2. Application and Evaluation of the Enhanced W2 Model
3.2. Application and Evaluation of the Enhanced W2 Model
3.2. Application and Evaluation of the Enhanced W2 Model
3.2.1. Study Area
3.2.1. Study Area
3.2.1. Study Area
The Xiaxi
The Xiaxi River
River isis located
located inin Wanshan
Wanshan County,
County, Guizhou
Guizhou Province,
Province, China.
China. This
This river
river has
has been
been
The
influenced Xiaxi
by River
the is located
world-famous in Wanshan
Wanshan HgCounty,
mining,Guizhou
which Province,
is one of China.
the This
thirteen
influenced by the world-famous Wanshan Hg mining, which is one of the thirteen large and super river
large has
and been
super
influenced
large-scale by
Hg the world-famous
mines located Wanshan
within the Hg
Guizhou mining, which
Province, is
China.one of the
Figure 9thirteen
shows
large-scale Hg mines located within the Guizhou Province, China. Figure 9 shows the extent of the large
the and
extent super
of the
large-scale
Xiaxi
Xiaxi River,Hg
River, and
and mines
its locatedin
its location
location within
in the Guizhou
Guizhou
Guizhou Province.Province,
Province. The Hg
The China.
tailingsFigure
Hg tailings 9 shows the
are distributed
are distributed extent of the
throughout
throughout the
Xiaxi River,
headwater and
reachesitsoflocation
the in
Xiaxi Guizhou
River. DueProvince.
to the The
high Hg tailings
geochemical are distributed
background of
headwater reaches of the Xiaxi River. Due to the high geochemical background of Hg in this area and throughout
Hg in this the
area
headwater
and
high high reaches
Hg of thecoal
emissions
Hg emissions from Xiaxi
from River.
coal Due to the
combustion
combustion using high
using
Hg geochemical
Hg
enriched coals as background
enriched coals wellof
well asasfrom asHgfrom
mining inactivities,
this area
mining
and high
activities, Hg
Hg emissions
contamination from
in coal
this combustion
area has using
become
Hg contamination in this area has become a concern [43–46]. a Hg enriched
concern [43–46].coals as well as from mining
activities, Hg contamination in this area has become a concern [43–46].

Figure 9. Map
Figure 9. Map of
of the
the Xiaxi
Xiaxi River
River watershed
watershed and
and sampling
sampling sites.
sites.
Figure 9. Map of the Xiaxi River watershed and sampling sites.
Water 2017, 9, 643 15 of 23
Water 2017, 9, 643 14 of 22
Water samples were respectively collected at the eight sampling sites in the watercourse
(Figure 9) during moderate and high flow periods in 2007 and 2008 [47,48]. Concentrations of THg,
Water samples were respectively collected at the eight sampling sites in the watercourse (Figure 9)
dissolved mercury (DHg), MeHg and total suspended solids (TSS) were measured in the laboratory
during moderate and high flow periods in 2007 and 2008 [47,48]. Concentrations of THg, dissolved
for all collected samples. The collection, storage, and preservation techniques of samples complied
mercury (DHg), MeHg and total suspended solids (TSS) were measured in the laboratory for all
with the USEPA Method 1631. Figure 10 shows the distribution of 2008’s observed THg
collected samples. The collection, storage, and preservation techniques of samples complied with the
concentrations in the watercourse of the Xiaxi River system. The THg concentrations were much
USEPA Method 1631. Figure 10 shows the distribution of 2008’s observed THg concentrations in the
higher along the Xiaxi River and then decreased rapidly downstream from the source. Based on
watercourse of the Xiaxi River system. The THg concentrations were much higher along the Xiaxi
observed data collected in 2007 and 2008, the THg concentrations ranged in the surface water from
River and then decreased rapidly downstream from the source. Based on observed data collected in
4.5 to 2100 ng·L−1 [47,49]. The THg concentrations in the benthic sediments ranged from 1.1 to 360
2007 and 2008, the THg concentrations ranged in the surface water from 4.5 to 2100 ng·L−1 [47,49].
mg·kg−1 [49].
The THg concentrations in the benthic sediments ranged from 1.1 to 360 mg·kg−1 [49].

Figure 10. Spatial distribution of THg concentrations along the watercourse of Xiaxi River.
Figure 10. Spatial distribution of THg concentrations along the watercourse of Xiaxi River.

3.2.2.Model
3.2.2. ModelDevelopment
Developmentand
andCalibration
Calibration
TheW2
The W2model
model was
was applied
applied to to the
the mainstem
mainstemXiaxi XiaxiRiver
Riverfrom
fromthe
theheadwater
headwater until thethe
until outlet of the
outlet of
watershed
the watershed(Figure 9). The
(Figure mainstem
9). The mainstemriverriver
is about 17 km
is about 17long. The Xiaxi
km long. RiverRiver
The Xiaxi is across the whole
is across the
watershed
whole and has
watershed andbeen
has the
beenmain
the concern of Hgof
main concern contamination. Table Table
Hg contamination. 4 listed the geometry
4 listed of the
the geometry
Xiaxi River reaches and major tributaries. The Xiaxi River W2 model mainly
of the Xiaxi River reaches and major tributaries. The Xiaxi River W2 model mainly consists consists of reaches R320,
of
R410, R180 and R20 (Figure 9). River reaches R450 and R500 were treated as Hg
reaches R320, R410, R180 and R20 (Figure 9). River reaches R450 and R500 were treated as Hg contaminated sources,
and R50 and R440
contaminated wereand
sources, treated
R50 asanduncontaminated
R440 were treatedsources. The plan view ofsources.
as uncontaminated the Xiaxi River
The planW2 model
view of
gridXiaxi
the is shown
Riverin W2
Figure 11. The
model gridXiaxi River was
is shown discretized
in Figure 11. with
The fifty-three
Xiaxi River horizontal segmentswith
was discretized with
∆x ranging
fifty-three from 338.8
horizontal to 468.7 m.
segments with The
Δxaveraged
ranging water depthtowas
from 338.8 0.5m.
468.7 m. The
The averaged
vertical layer
waterthickness
depth
was set up with 0.25 m.
was 0.5 m. The vertical layer thickness was set up with 0.25 m.

Geometryofofthe
Table4.4.Geometry
Table theXiaxi
XiaxiRiver
Riverreaches
reachesand
andmajor
majortributaries.
tributaries.

Reach Number
Reach Number Reach
Reach NameName Length
Length
(m)(m) Slope
Slope RemarkRemark
1 1 R450 R450 646646 0.17301
0.17301 Hg tailing
Hg tailing
2 2 R500 R500 2675
2675 0.04434
0.04434 Hg tailing
Hg tailing
3 3 R320 R320 4687
4687 0.02238
0.02238 Mainstem Mainstem
4 4 R410 R410 3388
3388 0.02766
0.02766 Mainstem Mainstem
5 R180 6813 0.01000 Mainstem
6 5 R20 R180 6813
2017 0.01000
0.01000 Mainstem Mainstem
7 6 R440 R20 2017
5688 0.01000
0.03769 Mainstem Tributary
8 7 R50 R440 5688
7353 0.03769
0.02745 TributaryTributary
8 R50 7353 0.02745 Tributary
Water 2017, 9, 643 16 of 23

Water 2017, 9, 2017,

Water 643 9, 643 16 of15
23of 22

Figure 11. W2
Figure computation
11. computation
W2 grid
computation plan
grid view
planview for
viewfor the
for the mainstem
the mainstem XiaxiRiver.
mainstem Xiaxi River.
Figure 11. W2 grid plan Xiaxi River.

The The inputs used for the Xiaxi River W2model

model include external
external loads, initial and boundary
The inputs
inputs used
used for
for the
the Xiaxi
Xiaxi River
River W2W2 model include
include external loads,
loads, initial
initial and
and boundary
boundary
conditions, and water quality parameters. The input data were assembled based on field data
conditions,
conditions, and
and water
waterquality
qualityparameters.
parameters.TheThe
inputinput
data were
data assembled
were based on
assembled field on
based datafield
collected
data
collected during the project period (2007–2008), outputs generated from other models, and
during
collectedthe project period
duringBecause (2007–2008),
the project period outputs generated from other models, and literatures. Because
literatures. Xiaxi River lacks(2007–2008), outputsmonitoring,
routine hydrological generatedthefrom other model
HEC-HMS models,wasand
Xiaxi River
literatures. lacks routine hydrological monitoring, the HEC-HMS model was used to compute
used to compute the stream flow [18] and fed into the W2 model. Xiaxi River inflow discharges forwas
Because Xiaxi River lacks routine hydrological monitoring, the HEC-HMS model the
stream flow
used toreaches [18]
compute and
the
R450, fed intoand
stream
R500, R50 the R440
flow W2 model.
[18] and
are Xiaxi
fed
shown intoRiver inflow
the W2
in Figure discharges
model.
12a,b. for reaches
Xiaxi River inflowR450, R500, R50
discharges for
and R440 are shown in Figure 12a,b.
reaches R450, R500, R50 and R440 are shown in Figure 12a,b.
4 R500 R450

4 3.5 R500 R450

3.5 3
Flow discharge (m3/s)

3 2.5
Flow discharge (m3/s)

2.5 2

1.5
2
1
1.5
0.5
1
0
0.5 10/13/2006 2/10/2007 6/10/2007 10/8/2007 2/5/2008 6/4/2008 10/2/2008 1/30/2009
Date

0 (a)
10/13/2006 2/10/2007 6/10/2007 10/8/2007 2/5/2008 6/4/2008 10/2/2008 1/30/2009
Date
(a)

Figure 12. Cont.

Water 2017, 9, 643 16 of 22
Water 2017, 9, 643 17 of 23
Water 2017, 9, 643 17 of 23

18 R440 R50
18 R440 R50
16
16
14
14
3/s)

12
3/s)

12
(m(m

10
discharge

10
discharge

8
8
Flow

6
Flow

6
4
4
2
2
0
0
10/13/2006 2/10/2007 6/10/2007 10/8/2007 2/5/2008 6/4/2008 10/2/2008 1/30/2009
10/13/2006 2/10/2007 6/10/2007 10/8/2007Date2/5/2008 6/4/2008 10/2/2008 1/30/2009
Date
(b)
(b)
Figure 12. Xiaxi River inflow discharges for reaches R500 and R450 (a) and R440 and R50 (b)
Figure 12.
Figure 12. Xiaxi
Xiaxi River
River inflow
inflow discharges
discharges for
for reaches
reaches R500
R500 and
and R450
R450 (a)
(a) and
and R440
R440 and
and R50
R50 (b).
(b)
Two suspended solids (fine and coarse solids) were simulated to characterize the partitioning
Two suspended solids (fine and coarse solids) were simulated to characterize the partitioning
and Two
distribution
suspended of solids
HgII (fine
and and
MeHg along
coarse thewere
solids) river. The fine
simulated to solids represent
characterize particles with
the partitioning and
and distribution of HgII and MeHg along the river. The fine solids represent particles with
corresponding particle diameter of 0.01 mm, and the coarse solids represent particles
distribution of HgII and MeHg along the river. The fine solids represent particles with corresponding with
corresponding particle diameter of 0.01 mm, and the coarse solids represent particles with
corresponding
particle diameter particle
of 0.01diameter
mm, andof the0.1 mm.solids
coarse Figurerepresent
13 shows the solids
particles withgrading curves particle
corresponding of four
corresponding particle diameter of 0.1 mm. Figure 13 shows the solids grading curves of four
diameter of 0.1 mm. Figure 13 shows the solids grading curves of four sampling sites in theofriver.
sampling sites in the river. Fine solids account for 88.5% of the TSS. The boundary conditions TSS
sampling sites in the river. Fine solids account for 88.5% of the TSS. The boundary conditions of TSS
and THg were calculated based on the following linear regression relationships developed
Fine solids account for 88.5% of the TSS. The boundary conditions of TSS and THg were calculated by Lin et
and THg were calculated based on the following linear regression relationships developed by Lin et
al. [18].
based
al. [18].on the following linear regression relationships developed by Lin et al. [18].
TSS  25.79 Q (R450 and R500) (21a)
TSS
TSS = 25.79 Q ((R450
25.79Q R450 and
andR550 )
R500) (21a)
(21a)
TSS  0.637Q (R440 and R50) (21b)
TSS
TSS=0.637 Q ((R440
0.637Q R440 and
andR50 )
R50) (21b)
(21b)
[THg
[ THg]]]RR450 =1435
450  Q
1435Q + 71
71 (21c)
(21c)
[THg R 450  1435Q  71 (21c)
[THg
[ THg]] 500 =2496
(21d)
(21d) Q +592
2496Q 592
[THg ]RRR500
(21d) 500  2496Q  592
3 −1 TSS is total suspended solids (mg·L− 1 THg is the total
where Q
where Q isis the
the stream
stream flow (m·3s·s−1),), TSS
flow(m is total suspended solids (mg·L−1),), THg is the total
where Q is the
concentration ·stream
L−1).). flow (m ·s ), TSS is total suspended solids (mg·L ), THg is the total
− 1 3 −1 −1
concentration (ng
(ng·L
concentration (ng·L−1).
100
100
less

90
less

90
diameter

80
diameter

80
(%)

70
(%)

70
value
with

60
value
with

60
particles

50
a certain
particles

50
a certain

40
40
of of
than

30
Percentage
than

30
Percentage

20
20
10
10
0
0 100 10 1
100 Diameter
10 (μm) 1
Diameter (μm)
Figure 13. Solids grading
Solids grading curves
grading curves for
curves for the
for the watercourse of
the watercourse
watercourse of Xiaxi River
River
Figure 13.
Figure 13. Solids of Xiaxi
Xiaxi River
Water 2017, 9, 643 18 of 23
Water 2017, 9, 643 17 of 22
Based on available observed data, the Xiaxi River W2 model was calibrated in several steps.
First, the manning’s roughness coefficient ‘n’ was calibrated so that simulated discharge
Based on available observed data, the Xiaxi River W2 model was calibrated in several steps.
approximated observed flow discharge [18]. The final manning’s roughness coefficient ‘n’ was set
First, the manning’s roughness coefficient ‘n’ was calibrated so that simulated discharge approximated
as 0.035. Next, the settling velocities of fine and coarse particles were calibrated, and simulated TSS
observed flow discharge [18]. The final manning’s roughness coefficient ‘n’ was set as 0.035. Next,
approximated observed TSS concentrations along the river. In the Hg simulation module, the
the settling velocities of fine and coarse particles were calibrated, and simulated TSS approximated
partitioning coefficients and transformation rates for HgII and MeHg were calibrated through a
observed TSS concentrations along the river. In the Hg simulation module, the partitioning coefficients
sensitivity analysis. Finally, the W2 model performance was evaluated by root mean square error
and transformation rates for HgII and MeHg were calibrated through a sensitivity analysis. Finally,
(RMSE) and relative error (RE).
the W2 model performance was evaluated by root mean square error (RMSE) and relative error (RE).
0.5
" 1 n 2 #0.5
RMSE   1  n (CM  CO )i
2
(22a)
RMSE =  n ∑ i 1 (C M − CO )i (22a)
n i =1
 n

 n CM  CO i  

RE  100  ii∑
1 | C M − CO |i
=1 n
 (22b)
 
RE = 100 · 
 (C ) (22b)

n
 i ∑ o


1 ( Co ) 
i =1

where is the
where CCM is the modeled
modeled concentration
concentration (ng
(ng·L
·L−1 for Hg and
for Hg and mg
mg·L
·L−1 for
−1
for TSS),
−1
TSS), C
COO is the observed
is the observed
M
concentration (ng·L−1
− 1for Hg and mg·L −1
−for
concentration (ng·L for Hg and mg·L for TSS).1 TSS).

3.2.3. Results
3.2.3. and Discussion
Results and Discussion
Figure 14
Figure 14 presents
presentsthe
thecomparison
comparisonofofW2
W2simulated
simulated flow
flow discharge
discharge andand simulated
simulated datadata
[18][18] at
at the
the mouth
mouth ofXiaxi
of the the Xiaxi
River.River. The average
The average error iserror
0.12 is
m 0.12
3 m /s. flood
3
/s. High High events
flood events
mainlymainly tookduring
took place place
the summer time (June to August), which were consistent with observed rainfall events. The The
during the summer time (June to August), which were consistent with observed rainfall events. W2
W2 model
model was was
ableable to reproduce
to reproduce observed
observed hydrodynamic
hydrodynamic results
results inriver.
in the the river.

60 W2 HEC-HMS

50
Flow discharge (m3/s)

40

30

20

10

0
10/10/2006 2/7/2007 6/7/2007 10/5/2007 2/2/2008 6/1/2008 9/29/2008 1/27/2009 5/27/2009
Date

Figure 14. Comparison of W2 modeled and observed flow discharge.

discharge.

After the
After the hydrodynamics
hydrodynamics was was calibrated,
calibrated, the
the W2
W2 model
model waswas further
further calibrated
calibrated for
for suspended
suspended
solids. The
solids. The modeled
modeled TSSTSS concentrations
concentrations were
were compared
compared withwith observed
observed data
data in Table 5.
in Table 5. The
The results
results
show that the RMSE for TSS is 0.10 mg·L −1 in 4 September 2007, and the relative error is 10%. For the
− 1
show that the RMSE for TSS is 0.10 mg·L in 4 September 2007, and the relative error is 10%. For the
TSS in
TSS in 88 August
August 2008,
2008, the
the RMSE
RMSE isis0.081
0.081mgmgLL−−11,, and
and the
the relative
relative error is 2.62%.
error is 2.62%. The
The RMSE
RMSE and and RE
RE
values ininhigh
values highflow
flow period
period are are
much much
lowerlower thaninthat
than that in moderate
moderate flow The
flow period. period. The RE
RE value value
increased
when TSS concentration decreased, especially when TSS concentration is lower than 1.0 mg·L1.0
increased when TSS concentration decreased, especially when TSS concentration is lower than −1 .
mg·Lsettling
The
−1 . The velocities
settling velocities of fine
of fine and andparticles
coarse coarse particles
with 5 mwith 5 m·d
·d−1 and
−1
25 mand
d−25 m d used
1 were −1 wereinused in the
the model.
model.
Water 2017, 9, 643 18 of 22

Table 5. Comparison of modeled and observed TSS values.

TSS (mg·L−1 ) TSS (mg·L−1 )

W2 model
4 September 2007 8 August 2008
Segment No.
Modelled Observed Modelled Observed
5 1.75 1.7 4.26 4.4
22 0.7 0.76 1.95 2
36 0.55 0.44 2.15 2.2
51 0.55 0.7 2.14 2.1

The partitioning coefficient of Hg on inorganic solids has a wide range in literatures. Allison
and Allison [41] provided a range of 102 –106 L·kg−1 . From a study of several Wisconsin lakes
conducted by Rice et al. [50], the partitioning coefficient of Hg ranged from 8 × 104 to 3.4 × 105 .
Suggested values for both methylation and demethylation rates are 10−5 –10−2 d−1 [41]. Methylation
rate ranged between 0.01 to 0.09 d−1 in a clear lake in Wisconsin [51]. Studies by Carroll et al. [52]
and Oremland et al. [53] indicated that methylation rates in Carson River ranged between 0.0025 and
0.011 d−1 and demethylation rates ranged between 0.12 and 0.55 d−1 . A sensitivity analysis was
performed using a range of partitioning coefficient (Kd ) and methylation/demethylation rate (M/D).
W2 modeled DHg and MeHg concentrations with a range of values of Kd and M/D are presented in
Tables 6 and 7. Based on the sensitivity analysis, the partitioning coefficients of Hg on fine and coarse
solids were set to 106 and 104 L·kg−1 . The methylation and demethylation rates were set to 0.01 and
0.1 d−1 in this study.

Table 6. Relative errors (%) of modeled DHg with different values of Kd (L·kg−1 ).

Kd for Fine Solids/Kd for Coarse Solids 102 103 104 105 106
104 33.47 30.95 29.54 29.26 32.79
105 29.16 26.30 24.68 24.37 27.97
106 18.53 14.23 11.75 12.29 15.42
107 39.06 35.03 32.67 32.20 38.84

Table 7. Relative errors (%) of modeled MeHg with different M/D rates (d−1 ).

M/D 10−2 10−1 1

10−1 15.98 28.45 25.06
10−2 11.81 9.93 13.37
10−3 12.20 14.14 19.53
10−4 12.69 14.65 20.18
10−5 14.27 16.10 20.24

Figure 15 presents the comparisons of W2 computed Hg concentrations (THg, DHg and

MeHg) and observed data along the mainstem Xiaxi River from tailings during September 2007
and August 2008. The concentrations of THg, DHg and MeHg decreased rapidly along the river.
The model predicted concentrations of Hg species were reasonable well when compared with observed
data. The RMSE and RE values of modeled THg were 13.0 ng·L−1 and 7.7% in September 2007,
and 19.0 ng·L−1 and 7.2% in August 2008. The RMSE and RE values of modeled DHg were 3.8 ng·L−1
and 9.0% in September 2007, and 10.0 ng·L−1 and 13% in August 2008. The RMSE and RE values of
modeled MeHg were 0.07 ng·L−1 and 7.4% in September 2007, and 0.09 ng·L−1 and 11% in August
2008. The particulate fractions took account of more than 75% of THg concentrations for all sampling
sites, and the MeHg concentration dissolved in water was much lower than THg.
Water 2017, 9, 643 19 of 22
Water 2017, 9, 643 20 of 23

800 Observed THg on Sep. 4 2007

Modeled THg on Sep. 4 2007
700
Observed THg on Aug. 8 2008
600 Modeled THg on Aug. 8 2008
500
THg (ng/L)

400
300
200
100
0
5 10 Distance (km) 15 20
(a)
200 Observed DHg on Sep. 4 2007
Modeled DHg on Sep. 4 2007
Observed DHg on Aug. 8 2008
150 Modeled DHg on Aug. 8 2008
DHg (ng/L)

100

50

0
5 10 Distance (km) 15 20
(b)
1.6 Observed MeHg on Sep. 4 2007
Modeled MeHg on Sep. 4 2007
1.4
Observed MeHg on Aug. 8 2008
1.2 Modeled MeHg on Aug. 8 2008
MeHg (ng/L)

1
0.8
0.6
0.4
0.2
0
5 10 Distance (km) 15 20
(c)
Figure 15.
Figure 15. Comparison
ComparisonofofW2
W2 modeled
modeled andand observed
observed Hg concentrations:
Hg concentrations: (a) (b)
(a) THg, THg, (b) (c)
DHg, DHg, (c)
MeHg.
MeHg.
4. Summary and Conclusions
4. Summary and Conclusions
The Hg simulation module has been developed and incorporated into the 2D hydrodynamic and
The Hg simulation module has been developed and incorporated into the 2D hydrodynamic
water quality model CE-QUAL-W2. The enhanced W2 model was tested and validated against WASP
and water quality model CE-QUAL-W2. The enhanced W2 model was tested and validated against
mercury model. The model results indicated that the enhanced W2 model was well designed, and the
WASP mercury model. The model results indicated that the enhanced W2 model was well designed,
algorithms and formulations were correctly implemented. Application of the enhanced W2 model
and the algorithms and formulations were correctly implemented. Application of the enhanced W2
to the Xiaxi River, a river course in Wanshan Hg mining area of Guizhou Province, China, further
model to the Xiaxi River, a river course in Wanshan Hg mining area of Guizhou Province, China,
evaluated the capability of the enhanced W2 model to simulate the transport and cycling of Hg in
further evaluated the capability of the enhanced W2 model to simulate the transport and cycling of
water bodies. The enhanced W2 model was able to reproduce observed TSS, THg, DHg and MeHg.
Hg in water bodies. The enhanced W2 model was able to reproduce observed TSS, THg, DHg and
THg, DHg and MeHg concentrations decreased rapidly downstream from the source and stabilized at
MeHg. THg, DHg and MeHg concentrations decreased rapidly downstream from the source and
lower levels, which is likely due to high association of Hg to solids and the rapid settlement of these
stabilized at lower levels, which is likely due to high association of Hg to solids and the rapid
solids. The source control of Hg discharge is the key to reduce the Hg contamination along the Xiaxi
settlement of these solids. The source control of Hg discharge is the key to reduce the Hg
River. This application demonstrated the W2 model capability in predicting complex transport and
contamination along the Xiaxi River. This application demonstrated the W2 model capability in
predicting complex transport and cycling of Hg species in water bodies. When more observed data
become available, the robustness of the Xiaxi River W2 model will be further calibrated and
Water 2017, 9, 643 20 of 22

cycling of Hg species in water bodies. When more observed data become available, the robustness of
the Xiaxi River W2 model will be further calibrated and validated. The current model can also be used
to perform scenarios analysis and quantify the best management practice for the XiaXi River.

Acknowledgments: This study was supported by NSFC (51479219) and Program for Innovative Research Team
of IWHR. The authors thank Yan Lin in Norwegian Institute for Water Research for providing Xiaxi River flow
and mercury dataset. The pertinent comments by the two reviewers were fully acknowledged here.
Author Contributions: Senlin Zhu performed the model programming, data analysis and calculation;
Zhonglong Zhang and Xiaobao Liu lead the model development and supervised the study.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Martin, J.L. Application of two-dimensional water quality model. J. Environ. Eng. 1988, 114, 317–336.
[CrossRef]
2. Cole, T.M.; Wells, S.A. CE-QUAL-W2: A Two-Dimensional, Laterally Averaged, Hydrodynamic and Water Quality
Model, Version 3.71; Portland State University: Portland, OR, USA, 2011.
3. Kim, Y.; Kim, B. Application of a 2-dimensional water quality model (CE-QUAL-W2) to the turbidity
interflow in a deep reservoir (Lake Soyang, Korea). Lake Reserv. Manag. 2006, 22, 213–222. [CrossRef]
4. Debele, B.; Srinivasan, R.; Parlange, J.Y. Coupling upland watershed and downstream waterbody
hydrodynamic and water quality models (SWAT and CE-QUAL-W2) for better water resources management
in complex river basins. Environ. Model. Assess. 2008, 13, 135–153. [CrossRef]
5. Afshar, A.; Kazemi, H.; Saadatpour, M. Particle swarm optimization for automatic calibration of large scale
water quality model (CE-QUAL-W2): Application to Karkheh reservoir, Iran. Water Resour. Manag. 2011, 25,
2613–2632. [CrossRef]
6. Ma, J.; Liu, D.; Wells, S.A.; Tang, H.; Ji, D.; Yang, Z. Modeling density currents in a typical tributary of the
Three Gorges Reservoir, China. Ecol. Model. 2015, 296, 113–125. [CrossRef]
7. Noori, R.; Yeh, H.-D.; Ashrafi, K.; Rezazadeh, N.; Bateni, S.M.; Karbassi, A.; Kachoosangi, F.T.; Moazami, S.
A reduced-order based CE-QUAL-W2 model for simulation of nitrate concentration in dam reservoirs.
J. Hydrol. 2015, 530, 645–656. [CrossRef]
8. Brown, C.A.; Sharp, D.; Collura, T.C. Effect of climate change on water temperature and attainment of
water temperature criteria in the Yaquina Estuary, Oregon (USA). Estuar. Coast. Shelf Sci. 2016, 169, 136–146.
[CrossRef]
9. Zhang, Z.; Sun, B.; Johnson, B.E. Integration of a benthic sediment diagenesis module into the two
dimensional hydrodynamic and water quality model—CE-QUAL-W2. Ecol. Model. 2015, 297, 213–231.
[CrossRef]
10. Keating, M.H.; Mahaffey, K.R.; Schoeny, R.; Rice, G.E.; Bullock, O.R. Mercury Study Report to Congress;
Volume I. Executive Summary. 1997. Available online: https://www3.epa.gov/airtoxics/112nmerc/
volume1.pdf (accessed on 1 July 2017).
11. US EPA (U.S. Environmental Protection Agency). Guidance for Assessing Chemical Contaminant Data for
Use in Fish Advisories Volume 2 Risk Assessment and Fish Consumption Limits. 2000. Available online:
https://www.epa.gov/sites/production/files/2015-06/documents/volume2.pdf (accessed on 1 July 2017).
12. EFSA (European Food Safety Authority). EFSA Provides Risk Assessment on Mercury in Fish: Precautionary
Advice Given to Vulnerable Groups, Press Release. 18 March 2004. Available online: https://www.efsa.
europa.eu/fr/press/news/contam040318 (accessed on 1 July 2017).
13. Hudson, R.J.M.; Gherini, S.A.; Watras, C.J.; Porcella, D.S. Modeling the biogeochemical cycle of mercury
in lakes: The mercury cycling model (MCM) and its application to the MTL study lakes. In Mercury
Pollution—Integration and Synthesis; Lewis Publishers: Ann Arbor, MI, USA, 1994; pp. 473–523.
14. Martin, J.L. MERC4: A Mercury Transport and Kinetics Model (beta 1.0); U.S. Environmental Protection Agency,
Center for Exposure Assessment Modeling: Athens, GA, USA, 1992.
15. Knightes, C.D. Development and test application of a screening-level mercury fate model and tool for
evaluating wildlife exposure risk for surface waters with mercury-contaminated sediments (SERAFM).
Environ. Model. Softw. 2008, 23, 495–510. [CrossRef]
Water 2017, 9, 643 21 of 22

16. Wool, T.A.; Ambrose, R.B.; Martin, J.L.; Comer, E.A. Water Quality Analysis Simulation Program (WASP),
Version 6, User’s Manual; U.S. Environmental Protection Agency: Athens, GA, USA, 2006.
17. Knightes, C.D.; Sunderland, E.M.; Barber, M.C.; Johnston, J.M.; Ambrose, R.B. Application of ecosystem-scale
fate and bioaccumulation models to predict fish mercury response times to changes in atmospheric
deposition. Environ. Toxicol. Chem. 2009, 28, 881–893. [CrossRef] [PubMed]
18. Lin, Y.; Larssen, T.; Vogt, R.D.; Feng, X.B.; Zhang, H. Modelling transport and transformation of mercury
fractions in heavily contaminated mountain streams by coupling a GIS-based hydrological model with
a mercury chemistry model. Sci. Total Environ. 2011, 409, 4596–4605. [CrossRef] [PubMed]
19. Turner, D.R. Speciation cycling of arsenic, cadmium, lead and mercury in natural waters. In Lead, Mercury,
Cadmium and Arsenic in the Environment; John Wiley & Sons Ltd.: Hoboken, NJ, USA, 1987; pp. 175–186.
20. Stein, E.D.; Cohen, Y.; Winer, A.M. Environmental distribution and transformation of mercury compounds.
Crit. Rev. Environ. Sci. Technol. 1996, 26, 1–43. [CrossRef]
21. Jackson, T.A. Long-range atmospheric transport of mercury to ecosystems, and the importance of
anthropogenic emissions: A critical review and evaluation of the published evidence. Environ. Rev. 1997, 5,
99–120. [CrossRef]
22. Morel, F.M.M.; Kraepiel, A.M.L.; Amyot, M. The chemical cycle and bioaccumulation of mercury. Annu. Rev.
Ecol. Syst. 1998, 29, 543–566. [CrossRef]
23. Zhang, Z.; Johnson, B.E. Aquatic Contaminant and Mercury Simulation Modules Developed for Hydrological and
Hydraulic Models; ERDC/EL TR-16-8; US Army Engineer Research and Development Center: Vicksburg, MS,
USA, 2016.
24. Schroeder, W.H.; Munthe, J. Atmospheric mercury—An overview. Atmos. Environ. 1998, 32, 809–822.
[CrossRef]
25. Thibodeaux, L.J.; Valsaraj, K.T.; Reible, D.D. Bioturbation-driven transport of hydrophobic organic
contaminants from bed sediment. Environ. Eng. Sci. 2001, 18, 215–223. [CrossRef]
26. Ditoro, D.M. Sediment Flux Modeling; Wiley-Interscience: New York, NY, USA, 2001.
27. Boyer, J.M.; Chapra, S.C.; Ruiz, C.E.; Dortch, M.S. RECOVERY: A Mathematical Model to Predict the Temporal
Response of Surface Water to Contaminated Sediments; U.S. Army Corps of Engineers Waterways Experiment
Station: Vicksburg, MS, USA, 1994.
28. Schink, D.R.; Guinasso, N.L. Modelling the influence of bioturbation and other processes on calcium
carbonate dissolution at the sea floor. In The Fate of Fossil Fuel CO2 in the Oceans; Plenum Press: New York,
NY, USA, 1977; pp. 375–399.
29. Feng, X.; Qiu, G. Mercury pollution in Guizhou, Southwestern China—An overview. Sci. Total Environ. 2008,
400, 227–237. [CrossRef] [PubMed]
30. Qiu, G.L.; Feng, X.B.; Wang, S.F.; Shang, L.H. Mercury and methylmercury in riparian soil, sediments,
mine-waste calcines, and moss from abandoned Hg mines in east Guizhou province, southwestern China.
Appl. Geochem. 2005, 20, 627–638. [CrossRef]
31. King, J.K.; Michael, S.F.; Lee, R.F.; Jahnke, R.A. Coupling mercury methylation rates to sulfate reduction
rates in marine sediments. Environ. Toxicol. Chem. 1999, 18, 1362–1369. [CrossRef]
32. Gilmour, C.C.; Elias, D.A.; Kucken, A.M.; Brown, S.D.; Palumbo, A.V.; Wall, J.D. Sulfate-reducing
bacterium Desulfovibrio desulfuricans ND132 as a model for understanding bacterial mercury methylation.
Appl. Environ. Microbiol. 2011, 77, 3938–3951. [CrossRef] [PubMed]
33. Achá, D.; Hintelmann, J.; Yee, J. Importance of sulfate reducing bacteria in mercury methylation and
demethylation in periphyton from Bolivian Amazon region. Chemosphere 2011, 82, 911–916. [CrossRef]
34. Shao, D.; Kang, Y.; Wu, S.; Wong, M.H. Effects of sulfate reducing bacteria and sulfate concentrations on
mercury methylation in freshwater sediments. Sci. Total Environ. 2012, 424, 331–336. [CrossRef] [PubMed]
35. Zhang, T.; Hsukim, H. Photolytic degradation of methylmercury enhanced by binding to natural organic
ligands. Nat. Geosci. 2010, 3, 473–476. [CrossRef] [PubMed]
36. He, F.; Zheng, W.; Liang, L.; Gu, B. Mercury photolytic transformation affected by low-molecular-weight
natural organics in water. Sci. Total Environ. 2012, 416, 429–435. [CrossRef] [PubMed]
37. Fleck, J.A.; Gill, G.; Bergamaschi, B.A.; Kraus, T.E.; Downing, B.D.; Alpers, C.N. Concurrent photolytic
degradation of aqueous methylmercury and dissolved organic matter. Sci. Total Environ. 2014, 484, 263–275.
[CrossRef] [PubMed]
Water 2017, 9, 643 22 of 22

38. Seo, D.; Kim, M.; Ahn, J.H. Prediction of Chlorophyll-a Changes due to Weir Constructions in the Nakdong
River Using EFDC-WASP Modelling. Environ. Eng. Res. 2012, 17, 95–102. [CrossRef]
39. Xiao, D.; Jia, H.; Wang, Z. Modeling Megacity Drinking Water Security under a DSS Framework in a Tidal
River at the North Pearl River Delta, China. J. Am. Water Resour. Assoc. 2015, 51, 637–654. [CrossRef]
40. Chen, C.X.; Zheng, B.H.; Jiang, X.; Zhao, Z.; Zhan, Y.Z.; Yi, F.J.; Ren, J.Y. Spatial distribution and pollution
assessment of mercury in sediments of Lake Taihu, China. J. Environ. Sci. 2013, 25, 316–325. [CrossRef]
41. Allison, J.D.; Allison, T.L. Partition Coefficients for Metals in Surface Water, Soil, and Waste; EPA-600/R-05/074;
Rep. U.S. Environmental Protection Agency, Office of Research and Development: Washington, DC,
USA, 2005.
42. Muresan, B.; Cossa, D.; Richard, S.; Burban, B. Mercury speciation and exchanges at the air-water interface
of a tropical artificial reservoir, French Guiana. Sci. Total Environ. 2007, 385, 132–145. [CrossRef] [PubMed]
43. Pacyna, E.G.; Pacyna, J.M. Global emission of mercury from anthropogenic sources in 1995. Water Air Soil
Pollut. 2002, 137, 149–165. [CrossRef]
44. Pacyna, J.M.; Breivik, K.; Münch, J.; Fudala, J. European atmospheric emissions of selected persistent organic
pollutants, 1970–1995. Atmos. Environ. 2003, 37, 119–131. [CrossRef]
45. Dastoor, A.P.; Larocque, Y. Global circulation of atmospheric mercury: A modelling study. Atmos. Environ.
2004, 38, 147–161. [CrossRef]
46. Feng, X. Mercury pollution in China—An Overview. In Dynamics of Mercury Pollution on Regional and Global
Scales; Springer: New York, NY, USA, 2005; pp. 657–678.
47. Zhang, H.; Feng, X.; Larssen, T.; Shang, L.; Vogt, R.D.; Rothenberg, S.E.; Li, P.; Zhang, H.; Lin, Y. Fractionation,
distribution and transport of mercury in rivers and tributaries around Wanshan Hg mining district, Guizhou
province, southwestern China: Part 1—Total mercury. Appl. Geochem. 2010, 25, 633–641. [CrossRef]
48. Zhang, H.; Feng, X.; Larssen, T.; Shang, L.; Vogt, R.D.; Lin, Y.; Li, P.; Zhang, H. Fractionation, distribution
and transport of mercury in rivers and tributaries around Wanshan Hg mining district, Guizhou province,
southwestern China: Part 2—Methyl mercury. Appl. Geochem. 2010, 25, 642–649. [CrossRef]
49. Lin, Y.; Larssen, T.; Vogt, R.D.; Feng, X.B. Identification of fractions of mercury in water, soil and sediment
from a typical Hg mining area in Wanshan, Guizhou province, China. Appl. Geochem. 2010, 25, 60–68.
[CrossRef]
50. Rice, G.E.; Ambrose, R.B.; Bullock, O.R.; Swartout, J. Mercury Study Report to Congress. Volume 3. Fate and
Transport of Mercury in the Environment. 1997. Available online: https://www3.epa.gov/airtoxics/112nmerc/
volume3.pdf (accessed on 1 July 2017).
51. Eckley, C.S.; Watras, C.J.; Hintelmann, H.; Morrison, K.; Kent, A.D.; Regnell, O. Mercury methylation in the
hypolimnetic waters of lakes with and without connection to wetlands in northern Wisconsin. Can. J. Fish.
Aquat. Sci. 2005, 62, 400–411. [CrossRef]
52. Carroll, R.W.H.; Warwick, J.J.; Heim, K.J.; Bonzongo, J.C.; Miller, J.R.; Lyons, W.B. Simulation of mercury
transport and fate in the Carson River, Nevada. Ecol. Model. 2000, 125, 255–278. [CrossRef]
53. Oremland, R.S.; Miller, L.G.; Dowdle, P.; Connell, T.; Barkay, T. Methyl-mercury oxidative degradation
potentials in contaminated and pristine sediments of the Carson River, Nevada. Appl. Environ. Microbiol.
1995, 61, 2745–2753. [PubMed]

© 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).