Water Quality Management

in Rivers
Dissolved Oxygen Depletion

Dissolved Oxygen Depletion

 Biochemical Oxygen Demand
Measurement

• Take sample of waste; dilute with oxygen saturated

water; add nutrients and microorganisms (seed)
• Measure dissolved oxygen (DO) levels over 5 days
• Temperature 20° C
• In dark (prevents algae from growing)
• Final DO concentration must be > 2 mg/L
• Need at least 2 mg/L change in DO over 5 days
 Example

• A BOD test was conducted in the

laboratory using wastewater being
dumped into a Lake. The samples are
prepared by adding 3.00 mL of
wastewater to the 300.0 mL BOD
bottles. The bottles are filled to
capacity with seeded dilution water.
 Example : Raw Data
Time Diluted Blank Seeded
(days) sample Sample DO
DO (mg/L) (mg/L)
0 7.95 8.15
1 3.75 8.10
2 3.45 8.05
3 2.75 8.00
4 2.15 7.95
5 1.80 7.90
 Example : Calculations
• What is the BOD5 of the sample?
[(DO i  DO f ) - (B i  B f )(1  P)]
BOD m 
P
P  dilution factor  volume sample/ total volume
B i , B f  initial and final DO concentrat ions of the
seeded diluted water (blank)
DOi , DO f  initial and final DO concentrat ions of the
diluted sample

• Plot the BOD with respect to time.

Example : Time – Concentration
Plot
700

600

500
BOD (mg/L)

400

300

200

100

0
0 1 2 3 4 5 6
time (days)
 Modeling BOD as a First-order
Reaction

6
Conc. (mg/L)

5
Organic matter oxidized
4
3
2
1 Organic matter remaining
0
0 10 20 30
time (days)
 Modeling BOD Reactions
• Assume rate of decomposition of organic
waste is proportional to the waste that is left in
the flask.
dLt
 - kLt
dt
where Lt  amount of oxygen demand left after time t
k  the BOD rate constant (time -1 )
Solving this equation yields :
Lt  Lo e  kt
where Lo is the ultimate carbonaceous oxygen demand
 Ultimate BOD
6L
5o Lo- Lt BOD exerted
Conc. (mg/L)

4
3
BODt
2
1 Lt
L remaining
0
0 10 20 30
time (days)
Ultimate Biochemical Oxygen
Demand
Lt = amount of O2 demand left in sample at
time, t
Lo = amount of O2 demand left initially (at time
0, no DO demand has been exerted, so BOD = 0)
At any time, Lo = BODt + Lt (that is the
amount of DO demand used up and the
amount of DO that could be used up
eventually)
Assuming that DO depletion is first order
BODt = Lo(1 - e-kt)
 Example

• If the BOD5 of a waste is 102 mg/L and the BOD20

(corresponds to the ultimate BOD) is 158 mg/L,
what is k?
BOD t  L0 1  e  kt

BOD t
1  e  kt
L0

 BOD t 
ln 
1  L 
   kt
 0 
 Example (cont)
 BOD t 
 ln 1  
 L0 
k
t
 102 mg/L 
 ln 1  
 158 mg/L 
k
5 day
-1
k  0.21 day
 Biological Oxygen Demand:
Temperature Dependence

• Temperature dependence of biochemical

oxygen demand
! As temperature increases, metabolism
increases, utilization of DO also
increases
kt = k20T-20
 = 1.135 if T is between 4 - 20 oC
 = 1.056 if T is between 20 - 30 oC
 Example
The BOD rate constant, k, was determined
empirically to be 0.20 days-1 at 20 oC.

What is k if the temperature of the water

increases to 25 oC?

What is k if the temperature of the water

decreases to 10 oC?
 Example

 -1
k 25  0.20 day (1.056) 25 20

-1
k 25  0.26 day

 -1

k10  0.20 day (1.135) 10 20

-1
k10  0.056 day
Nitrogenous Oxygen Demand
• So far we have dealt only with
carbonaceous demand (demand to oxidize
carbon compounds)
• Many other compounds, such as proteins,
consume oxygen
• Mechanism of reactions are different
Nitrogenous Oxygen Demand
• Nitrification (2 step process)
2 NH3 + 3O2  2 NO2- + 2H+ + 2H2O
2 NO2- + O2  2 NO3-
– Overall reaction:
NH3 + 2O2  NO3- + H+ + H2O

• Theoretical NBOD =
grams of oxygen used 4 x 16
  4.57 g O 2 /g N
grams of nitrogen oxidized 14
Nitrogenous Oxygen Demand
Nitrogenous oxygen demand
• Untreated domestic wastewater

ultimate-CBOD = 250 - 350 mg/L

ultimate-NBOD = 70 - 230 mg/L

Total Kjeldahl Nitrogen (TKN) = total

concentration of organic and ammonia
nitrogen in wastewater: 15 - 50 mg/L as N

Ultimate NBOD  4.57 x TKN

Other Measures of Oxygen
Demand
 Chemical Oxygen Demand

• Chemical oxygen demand - similar to BOD

but is determined by using a strong
oxidizing agent to break down chemical
(rather than bacteria)
• Still determines the equivalent amount of
oxygen that would be consumed
• Value usually about 1.25 times BOD
 Water Quality
Management in Rivers
Dissolved Oxygen Depletion
Dissolved Oxygen Sag Curve
 Mass Balance Approach
• Originally developed by H.W. Streeter and
E.B. Phelps in 1925
• River described as “plug-flow reactor”
• Mass balance is simplified by selection of
system boundaries
• Oxygen is depleted by BOD exertion
• Oxygen is gained through re-aeration
Steps in Developing the DO Sag
Curve
1. Determine the initial conditions
2. Determine the re-aeration rate from
stream geometry
3. Determine the de-oxygenation rate from
BOD test and stream geometry
4. Calculate the DO deficit as a function of
time
5. Calculate the time and deficit at the
critical point
Selecting System Boundaries
 Initial Mixing

Qw = waste flow (m3/s)

DOw = DO in waste (mg/L)
Lw = BOD in waste (mg/L)

Qr = river flow (m3/s) Qmix = combined flow (m3/s)

DOr = DO in river (mg/L) DO = mixed DO (mg/L)
Lr = BOD in river (mg/L) La = mixed BOD (mg/L)
 1. Determine Initial Conditions

a. Initial dissolved oxygen concentration

Qw DOw  Qr DOr
DO 
Qw  Qr
b. Initial dissolved oxygen deficit

D  DOs  DO
where D = DO deficit (mg/L)
DOs = saturation DO conc. (mg/L)
Qw DOw  Qr DOr
Da  DOs 
Qmix
 1. Determine Initial Conditions

DOsat is a function of temperature. Values

can be found in Table.
c. Initial ultimate BOD concentration
Qw Lw  Qr Lr
La 
Qw  Qr
 2. Determine Re-aeration Rate

a. O’Connor-Dobbins correlation
3.9u1/ 2
kr 
h3/ 2
where kr = reaeration coefficient @ 20ºC (day-1)
u = average stream velocity (m/s)
h = average stream depth (m)
b. Correct rate coefficient for stream temperature
T  20
k r  k r , 20
where Θ = 1.024
Determine the De-oxygenation Rate

a. rate of de-oxygenation = kdLt

where kd = de-oxygenation rate coefficient
(day-1)
Lt = ultimate BOD remaining at
time (of travel downstream) t
b. If kd (stream) = k (BOD test)
 kd t
Lt  L0 e

and
rate of deoxygentation  k d L0 e  k d t
3. Determine the De-oxygenation Rate

c. However, k = kd only for deep, slow moving

streams. For others,
u
kd  k  
h
where η = bed activity coefficient (0.1 – 0.6)
d. Correct for temperature
T  20
k r  k r , 20
where Θ = 1.135 (4-20ºC) or 1.056 (20-30ºC)
 4. DO as function of time

• Mass balance on moving element

dD
 k d Lt  k r D
dt
• Solution is
k d La  kd t
Dt 
kr  kd
   
e  e  k r t  Da e  k r t
5. Calculate Critical time and DO

1  kr  k r  k d 
tc  ln  1  Da 
kr  kd  kd  k d La 

k d La  kd tc  kr tc
Dc 
kr  ka
e  e 
 Da e  k r tc