Académique Documents
Professionnel Documents
Culture Documents
RIVER
Modeling the biochemical oxygen demand and heavy metal
fate and transport
By:
Parnaz Tabrizian
Jiaru Luo
Under supervision of:
Dr. Maria Elektorowicz
Concordia University
Water Pollution and Control (Civi6651)
Table of Contents
1 Introduction ........................................................................................................................ 4
1.1
Location and features of Flint river ....................................................................................... 4
1.2
Study segment for Flint River ............................................................................................... 4
1.3
Preparation for building model ............................................................................................ 6
1.3.2 Original data for point source discharge ................................................................................ 7
1.4
Hydrology of Flint river ........................................................................................................ 7
1.5
Contaminant in the Flint River ............................................................................................. 8
1.5.1 Biochemical oxygen demand (BOD) ....................................................................................... 8
1.5.2 Suspended solid .......................................................................................................................... 9
1.5.3 Heavy Metals .............................................................................................................................. 9
2
Modeling the sediment and heavy metal transport in flint river ..................................... 17
3.1
Determining parameters .................................................................................................... 17
3.2
Model Maker simulation .................................................................................................... 22
3.3
Results and Analysis ........................................................................................................... 24
1 Introduction
1.1 Location and features of Flint river
Flint River is located in the state of Michigan in United states of America, with 126.0km long,
Flint River is the main water resource for the city Flint and it flow through the countries if
Lapeer, Genesee, and Saginaw. There are three dams along the Flint River. The first one is
located in Richfield Township following is Utah Dam then the last one is Hamilton Dam. The
Richfield Township Dam form the Holloway Reservoir which is a water supply for Flint. 1
In the city of Flint, the river flows past the sites of several former General Motors factories, most
notably Chevrolet's first assembly plant, which was bisected by the river, and downtown through
the campus of the University of MichiganFlint and Riverbank Park.
In this segment, we selected seven stations as our data resources and it contains Mill Road, Flint
WWTP, Flint Fly Ash Ponds, Brent Run, Ragnone WWTP, Pine Run, Silver Creek.
The table below is the data we collect from these seven stations, the flow rate and concentration
of SS and toxicant are quiet different among three different periods. Comparing December and
March the flow rate in August is much lower. We chose the data from August because it means it
has a higher concentration of toxicant. Moreover, In august temperature is higher therefore the
lowest dissolved oxygen can be seen in these conditions. By modeling this period of data, we can
see the extreme conditions in the flint river.
August
Source
Upstream
Boundary
Flint WWTP
Flint Fly Ash
Brent Run
Ragnone WWTP
Pine Run
Silver Creek
Discharge(m3/s)
Discharge Concentration
Total
Suspended Solids Total Zinc
Cadium
(mg/l) (kg/d)
(ug/L)
(ug/L)
Total
Copper
(ug/L)
2.66
13.5
7.7
0.067
2.9
1.68
0.04
0.15
0.69
0.06
0.085
4.1
39.5
5.9
58.7
7
5.8
55
63
3.8
84
5
5
0.16
1.32
0.11
0.54
0.04
0.04
8.3
80
3.8
28.5
3.8
3.8
December
Source
Upstream
Boundary
Flint WWTP
Flint Fly Ash
Brent Run
Ragnone WWTP
Pine Run
Silver Creek
Discharge(m3/s)
Discharge Concentration
Total
Suspended Solids Total Zinc
Cadium
(mg/l) (kg/d)
(ug/L)
(ug/L)
Total
Copper
(ug/L)
26.35
7.4
0.05
2.19
0.1
0.57
1.14
0.67
0.62
7.8
23.5
7.7
40.7
5.5
3.5
54.3
220
7.67
75
3.33
3.67
0.18
2.89
0.097
0.21
0.013
0.01
16
127
2.93
18.5
2.1
1.8
March
Source
Upstream
Boundary
Flint WWTP
Flint Fly Ash
Brent Run
Ragnone WWTP
Pine Run
Silver Creek
Discharge(m3/s)
Discharge Concentration
Total
Suspended Solids Total Zinc
Cadium
(mg/l) (kg/d)
(ug/L)
(ug/L)
93.4
15.5
7.24
0.025
2.48
2.66
0.18
1.51
1.12
2
2
5.35
5.84
13.4
50.9
14
14
71
120
10.6
59.7
7
7
0.11
0.93
0.032
0.257
0.03
0.03
18.2
71.4
5.14
27.8
2
2
Total
Copper
(ug/L)
Model of discharge
6
During the August the flow rate form upper stream is 2.66m3/s and except the Flint WWTP
others flow rate are much lower. In our case, to make our model simpler. We decided to combine
Brent Run, Pine Run and Silver Creek together to the Ragnone WWTP as one-point source
discharge because they have similar environmental condition like the lower pollutant and flow
rate.
So we divided it into 3 parts. Settingthe Flint WWTP as our point source discharge1 and
Ragnone WWTP as our point source discharge2. In our model, its 1.2km from the Mill Road to
discharge1. The distance between discharge1 and discharge2 is 29km then 29.80km below
discharge2 is Silver Creek.
Because the segment we study in Flint River only 60.2km long and Flint River also located in
plain country, so we assume that the elevation doesnt change a lot form the Mill Road to Silver
Creek.
Parameter
Upstream
Flint
WWTP
Raganone
WWTP
Length(km)
1.2
29
29.8
X_distance (km)
0-1.2
30.2
60
19
19
19
Slope()
0.02
0.02
0.02
Average elevation(m)
230
230
230
U_Velocity (m/s)
0.14
0.22
0.28
W_Width (m)
36
36
36
H1_Deepth(m)
0.52
0.52
0.52
T_Temperature()
20
20
20
pH
7.3
7.3
7.3
humans, most of the copper ingested is excreted by the body and little is retained. In lower
organisms and marine animals such as sponges there are some record of accumulation. In
concentrations high enough to be dangerous to humans, copper renders a disagreeable taste to the
water. Threshold concentrations for taste has been reported in the range of 1.0-2.0- mg/L while
5.0-7.0mg/L makes the water completely undrinkable. 7,5
Coppe acts synergistically with the sulfates of other metals such as Zinc and Cadmium to
produce potent toxic effects on Fish 8,9. Synergism also exists between copper and mercury but in
9
our studies Zinc and Cadmium are only considered. Copper standards for aquatic systems in the
state of Michigan is 1.0 mg/L which is the same as USPHS water standards.5
Cadmium
The elemental form of Cadmium is insoluble in water although the chloride, nitrate and sulfate of
this metal are highly soluble. Cadmium salts may be found in wastes from electroplating plants,
pigment works, textile printing, lead mines and certain chemical industries. Cadmium is
moderately toxic to all organisms and it is a cumulative poison to mamals. It tends to concentrate
in liver, Kidney, pancreas and thyroids of humans and other mamals.
Cadmium acts synergistically with zinc to increase toxicity. Several studies found that the
cadmium concentration of 0.03 mg/l with combination with 0.15 mg/l of zinc from galvanized
screens caused mortality of salmon fry. The standards for aquatic systems for state of Michigan
is 0.01 mg/l.
Zinc
Some Zinc salts (eg. Zinc chloride and zinc sulfate) are highly soluble in water. These salts are
often found in industrial wastewater from galvanizing industries, and manufacturers of paint
pigments, cosmetics pharmaceuticals, dyes, insecticides and other products. High concentrations
of zinc in domestic water are undesirable from aesthetic standpoint as well as from a health
hazard standpoint. At high concentrations, zinc gives water a milky appearance. Concentrations
as low as 5 mg/l cause a greasy film on boiling of the water.
Zinc has no known adverse physiological effects at normal concentrations. It is an essential and
beneficial element in human nutrition. Zinc exhibits its greatest toxicity toward fish and aquatic
organisms. In soft water concentrations of zinc ranging from 0.1 to 1.0 mg/L reported to be
lethal5
10
0.434
Because in our assumption we mentioned before, we assume the area of cross section is the same,
so the Kd in each part (upstream river1 river2) is the same which is equal to 4.8e-06/d
But then we have to consider the temperature effect on the biodegrade rate so we using the
formulas below to correct it. But due to the average temperature in this case is 20 degrees, so its
the same as we calculate.
(K )T
d
= (K d )20(1.04)T 20
In this case, Cs1 is search from the book[3] Principles of Surface Water Quality Modeling and
Control, So using the Cs at our this level, we finally calculate the Cs is 10.46mg/l. Because in
our case we have less change on elevation, therefore we assume that the Cs is the same in whole
segment.
Cs=Cs1*(100-0.0035H)/100
As to the reaeration rate base the equation below we calculate it. Although the cross-section aera
is the same in this case, flow rate is different. In addition, because the average depth of river is
less than 8feet, so we decided using this formulas:
Ka =
21.6U
0.67
H 1.85
0H8
11
Also, we have to consider the temperature effect on the Ka ,but due to the same condition as Kd
mentioned .So Ka is the same as our result which
Ka1=1.82e-05 ka2=2.42e-05 kaup=1.42e-05
(K )T
a
= (K a )20(1.04)T 20
On the initial values of DO concentration. Base the data we collect 2 from each station, then we
case on our decay rate Kd and reaeration Ka and initial concentration from the point source
discharge L0, then we using the formulas below to find out our initial values in our case.
Dc =
kd L0
e kdt e kat + D 0e kat
k a kd
Then after we calculate the deficit in each point we used the Cs in that point minus Dc and we
can get our DO concentration.
Parameter
Meaning
Upstream
Flint
WWTP
Ragnone
WWTP
Q (m3/s)
Flow rate
2.66
1.68
1.025
C_BODU
(mg/L)
Concentration of BODU
16
30
C_DO (mg/L)
Concentration of DO
5.4
3.5
K1_BOD5 (day1
)
0.187
0.187
0.187
Kd (day-1)
0.415
0.415
0.415
f (L0/y5)
1.4
1.4
1.4
Cs (mg/L)
DO saturation
10.46
10.46
10.46
Kr (day-1)
0.415
0.415
0.415
Ka (day-1)
Volumetric reaeration
coefficient
3.272
4.180
4.648
12
dL
= K d L
dx
Compartment
Equation
Upstream_BODU
Flint_WWTP
Qd1Cd1
13
River1_BODU
Ragnone_WWTP
Qd2Cd2
River2_BODU
When t <30.2,
(QupCup+Qd1Cd1+Qd2Cd2)
dUpstream_BODU/dt=0
/(Qup+Qd1+Qd2)=13.53
Default, Kd*River1_BOD5/U_River1
t<1.2,FlintRiver_BODU=
Upstream_BODU
t<30.2, Flint_BODU = River1_BODU
Default,Flint_BODU= River2_BODU
Flint River_BODU
(QupCup+Qd1Cd1)/(Qup+Qd1)
=12.79
dD
x
= K d L0 exp K r + K a (c s c )[3]
dx
U
Compartment
Equation
14
Upstream_D
O
Flint_WWTP
Qd1C01
River1_DO
(QupC0up+Qd1C01)/(Qup
+Qd1)
=4.85
(QupCup+Qd1C01+Qd2C
02)
/(Qup+Qd1+Qd2)=7.686
Ragnone_W
WTP
River2_DO
Flint
River_DO
t1.2,FlintRiver_DO= Upstream_DO
t 30.2, Flint_DO = River1_DO
Default, Flint_DO = River2_DO
Table 6 Simualation equation for DO concentration
15
In the graph we can see before the point source discharge1, it shows a slightly decrease in this
1.2 km long distance. Obviously the concentration of BOD in this segment are decreasing. On
the contrary, the concentration of dissolved oxygen in this part make a upward trend which
means the oxidation materials in this part was reducing.
Then, when it reach to the point source discharge1 , due to point source discharge1 is the Flint
waste waster treatment plant. The municipal waste usually contains high concentration of
organic materials which will consume the oxygen in water. Therefore, the graph for
concentration of BOD shows us a dramatically increase which up to 12.79mg/l. And in this
period we assume that the mix of BOD is instances. At the same time DO concentration drop
down to 5mg/l in this case and it is not enough for some of the fish living in this segment. Then
as biodegradable function in the river (it shows in Ka reaeration rate in this case), because
velocity in this segment is high so the BOD increase very fast which is the reason why in this
section it didnt show us sag curve.
Later on, when it to the 30.2km far from the beginning of up stream. The BOD concentration
drop to 7mg/l and DO concentration reaerated back to 7.9mg/l respectively. This point is also the
Raganone WWTP facility which discharge municipal waste into water. Therefore it shows the
same result just like the Flint WWTP. Due to the velocity in this part is lower than river1 so the
Ka reaeration rate is lower and we can see the sag curve which take place at 45km downstream
form the beginning and DO concentration reach to 6.9mg/l .
16
source of metals in the study reach. Together with upstream contributions from the river, these
three sources ate assumed to comprise the total metal input to the system. Three priority
contaminants are Zinc, Copper and Cadmium.
In order to approach the model, several assumptions were made.
1) The river is at steady-state with respect to flow and loads;
2) Concentration of the modeled substance is uniform over the cross-section of the river (i.e., one
dimensional system); thus, any point discharge instantaneously mixes with the river flow at the
point of discharge;
3) Dispersion is negligible in the longitudinal direction; that is only advection is considered
significant in the direction of flow; thus, E = 0 in equation A4;
4) Flow, cross-sectional area, and mean depth are constant over the reach in question. 2
The model is chosen based on the two assumptions where, Kd2=Kd1=0, that is there is no
degradation or decay of metals in the sediment or water column. This assumption is quite
reasonable since most metals do not decay or otherwise degrade in exception of mercury which
can volatize. And the second one is that the partition coefficient of the metal in the water column
is not the same as the partition coefficient in the sediment column. Although the range of the
uncertainty on the partition coefficient is relatively high, the partition coefficient for suspended
and bedded sediments can differ since the characteristics of solids in the bed differ from the
water and generally lower. For these reasons and experimental data, the partition coefficient of
150,000 kg-1 was chosen. Based on the above assumptions, Level 2 interaction level was chosen
to model the flint river.
In addition to the flow rated and metal concentrations additional data and parameters have to be
either calculated by empirical equations or estimated. The typical river bottom will have a water
content between 60% to 95% by weight; therefore, if the solids have a specific gravity of 2.5, the
solid concentrations in the bed will vary from approximately 50,000-500,00 mg/L of bulk
sediment. Based on some sampling done by the study a value of m2=200,000 mg/L was chosen.
Since the August data is during a relatively low flow season, it is intuitive that the resuspension
18
velocity is almost zero, however based one several studies it has been shown that this assumption
is true up to the Ragnone WWTP, however after km point 35 the resuspension could not be
ignored, therefore the value of 2.0 x 10-5 m/day was chosen as the resuspension velocity of the
whole section. 1,2
Partition coefficient of the metals were calculated based on the following formula:
Kp(l/Kg)=Kpo . SSalpha
Where SS is the suspended solid concentration mg/l, and Kpo and Alpha are found from the
following table.
Table 7 Partition coefficient of priority pollutants
Metals
Kpo in streams
Alpha
Cadmium
4.00E+06
-1.13
Copper
1.04E+06
-0.74
Zinc
1.25E+06
-0.7
It is assumed that the partition coefficients remain constant through out the river.
The initial conditions for suspended solid concentration in the water column were calculated
using the formula shown below:
m 1 = m (0 ) exp
V m
Vs
x + u 2
H 1U
Vs
Vs
x )
1 exp(
H 1U
Where Vs is the settling velocity, Vu is the resuspension velocity, H1 the depth of the river and
U is the velocity of the river at each segment. In this formula we used the assumption that the
dilution is almost instantaneous and there is no axial dispersion. The models were also based on
the above equation.
19
The initial conditions for dissolved metal in the water column were based on the following
equation.
=
Were WT is the load of the heavy metal, Q the flow rate and VT is the total sediment interaction
with heavy metal rate and is calculated from the following formula:
VT = VTd + VTs
V s f p 1 + K f fd 1
VTs = V n
V s + (fd 2 m 2 K f / m 1 )
Where VTs is loss due to sediment interaction, Kf is the sediment water diffusion and was
assumed based on the water pollution control textbook. VTd is the dissolved chemical loss and is
calculated from the following formula.
VTd = (K d 1 H 1 + k l )fd 1
Since Kd1 and Kl are both assumed to be zero, Vtd is zero, therefore VT=VTs.
fp1,fp2= particulate fraction of metal in water column and bed respectively
fd1,fd2= dissolved fraction of metal in the water column and bed respectively
and where calculated from the suspended solid concentration and partition coefficients from the
following formulas. 3
1m 1
1 + 1m 1
= 1 f p1
2m 2
=
1 + 2m 2
= 1 fp2
f p1 =
fd 1
fp2
fd 2
Vn is the net loss rate of solids from water column and was calculated from Vd
Vn=Vd(m2/m1)
And Vd or net sedimentation velocity were chosen to be 1.4e-05 from the range presented in the
water pollution control. The metals in the Flint discharge averaged 91%, 84%, and 75%
dissolved phase for zinc, cadmium, and copper, respectively.2
20
Meaning
Upstream
Discharge2
7.70
Disch
arge1
55.00
60.15
Partition
Coefficient kg-1
2.00E+05
Concentration of Cr in
water column (ug/L)
Concentration of Cr in
water column (ug/L)
Concentration of Cr in
water column (ug/L)
Solid concentration in
water column (mg/L)
Solid concentration in
sediment column (mg/L)
Depth of sediment column
(m)
Decay rate in sediment
column
partition coefficient in bed
0.07
0.16
3.70
6.00E+04
2.90
8.30
34.80
2.10E+05
13.50
4.10
42.00
200,000
200,00
0
200,000
0.05
0.0
150,000
0.91
200,000
0.75
Sediment-water diffusive
transfer coefficient
(m/day)
0.027
Parameter
Meaning
Steady Conditions
fp2
0.0100000
Vs (m/day)
Settling velocity
0.2500000
Vd (m/day)
net sedimentation
Vu (m/day)
Resuspension velocity
0.0000200
0.0907643
0.0000114
Vn (m/day)
0.7699018
21
VTs (m/day)
0.0010059
3.2 Model Maker simulation
In order to simulate the transport of heavy metals, Model Maker has been used. The model
consists of two main components: The total concentration of heavy metal in the water column
and the suspended solid concentration in the water column. These two components can be
combined to predict the weight fraction of the heavy metal in the sediment.
The following equations were used in order to model the heavy metal and suspended solid
concentrations. And these two values can be combined to calculate r2 from the subsequent
formula. 3
dm 1
V
V
= s m1 + u m 2
dx
H1
H1
=
0
f W
V
r2 (x ) = p 1 T exp T x
H 1U
m 1 Q
where,
(Vu
=
(Vu
fd 2
2
/ 2 + K d 2fd 2 H 2
+ Vd )f p 2 + K f ( 2 / 1 )
+ Vd )f p 2 + K f fd 2
22
Compartment
Equation
Initial value
Upstream_CT1_Zn1
t>=1.2, dUpstream_CT1_Zn/dt=0
Default,
dUpstream_CT1_Zn/dt = VTs*Upstream_CT1_Zn/U_Upstream
C0_Zn_Upstream
(Q0C01+Q1Ce1)/( Q0
+ Q1)
River2_CT1_Zn_settling2
(Q0C01+Q1Ce1+Q2C
e2)/( Q0+ Q1+Q2)
FlintRiver_CT1_zn1
Upstream_SS1
m1_0_Upstream
River1_SS_Settling1
t<=1.2, dRiver1_SS_Settling1/dt =0
t>=30.2, dRiver1_SS_Settling1/dt =0
default, dRiver1_SS_Settling1/dt = (ws*River1_SS_settling1/U_River1)+(200000*wrs/U_Ri
ver1)
(Q0C01+Q1Ce1)/( Q0
+ Q1)
River2_SS_Settling1
t<=30.2, dRiver2_SS_Settling1/dt = 0
(Q0C01+Q1Ce1+Q2C
e2)/( Q0+ Q1+Q2)
River1_CT1_Zn_settling1
(ws*River2_SS_settling1/U_river2)+(200000*wrs/U_rive
r2)
FlintRiver_SS_m1
FlintRiver_r2_Zn
delta*0.09*FlintRiver_CT1_zn1/FlintRiver_SS_m1
The following figure represent the model for Zinc and is identical to the models used for Copper
23
and Cadmium.
souring or settling period is higher for copper with higher partition coefficient and therefore
higher Kp.SS.10-6 value supporting our claim. Also Copper exists in more particulate form than
dissolved form comparing to zinc, therefore more subjected to settling and scouring. Overall, all
three priority pollutants are mostly in dissolved form with very minimal settling and scouring
showing that any metals entering the stream will exist in the dissolved form and dilution is the
governing factor in determining the concentration of these metals.
Since the concentration threshold of cadmium is much lower than copper and Zinc, Cadmium is
shown in different graphs.
25
26
27
Max
Standard for fish and aquatic
Concentrations(mg/L)
life(mg/L)
0.028
5
0.0001
0.01
0.007
0.02
During the drought flow periods, the waste flow would equal to 90% of the river flow as can be
seen in the August survey. Under these conditions, even efficient secondary treatment results in
high concentrations of pollutants in the stream especially in conservative and semiconservative
wastes such as salts and nutrients which are little affected by present secondary treatment
methods. As a result, the flint river with 24% of the total Saginaw river flow, contributed 50% to
the total nutrient loading of the Saginaw river. The pollution load to the Flint river from this
highly developed area is in excess of the assimilative capacity of the stream with the present
degree of treatment. Moreover, the population of these areas are increasing therefore, the WWTP
has to take that into the account for preventive measures.
Although heavy metal concentrations meet the standards, Cadmium, Copper and Zinc tend to act
synergistically and when present at the same time will have lower thresholds as discussed in the
introduction. In order to mitigate the metal concentration and DO depletion in Flint river and
consequently in Saginaw river and the drainage area waste allocation program as to be done for
all industries and municipal discharges to the river. If higher population of these municipal areas
results in even higher DO depletion other methods such as aerators have to be installed in the
river in order to preserve the aquatic life of the river. A tertiary treatment system for flint and
Ragnone WWTPs can also be a good investment for preventive measures.
29
References
[1] Federal Water Pollution Control Administration Great Lake Region Lake Huron Basin.
Flint River Michigan 1965 Survey
[2] United States Environmental Protection Agency Water Quality Assessment: A screening
Procedure for Toxic and Conventional Pollutants in Surface and Ground Water
[3 ] Robert V. Thomann, John A. Mueller. Principles of Surface Water Quality Modeling and
Control[M]. Harper Collins Publishers, 1987: 1-637.
[4] United states Environmental Protection Agency Ambient Water Quality Criteria for
Dissolved Oxygen
[5] Flint river-Michigan-Water Quality Data- 1965 survey Clean water series DPO-13-C EPA
US department of the interior federal water pollution control administration.
[6] McKee J.E and H.W Wolf, 1963 Water Quality Criteria,2nd ed. State water quality control
board of California.
[7] Schneider E. G. 1931 Copper and Health Jour NEWWA , Water pollustion Abs (sept 1931)
[8] Tarzwll C. M 1958 Disposal of Toxic Wastes Ind. Wastes 3:2 48
[9] Dourdoroff. P. M Kratz 1953, Critical Review of Literature on the toxicity of industrial
wastes and thei components to Fish
30