Environmental Engineering-II

(CE 3241)

Dr. Khondoker Mahbub Hassan

Dept of Civil Engg, Khulna University of Engg & Tech (KUET)
Modeling BOD as a first order Reaction
If L0 = ultimate CBOD

Lt = amount of oxygen demand remaining after time t

Then, assuming first order reaction,

dLt Lo
= -kL t
dt
Lt t BODt
dLt
ò = -k ò dt
BOD
L0 Lt 0 Lt

Lt =L0 e-kt t

-kt
L0 = BODt +Lt BODt = L0 (1- e )
BOD rate equation
Modeling BOD as a first order Reaction
 K = f (nature of waste, ability of bacteria, temperature)

 K can be determined in laboratory along with L0 by

measuring BODt at two different times.

 Effect of temperature on K:
Commonly used expression:

kT = k20 θT-20 , θ = 1.047

 Nitrogenous BOD (NBOD)
 Nitrogen tied to complex organic molecules is converted to
ammonia by bacteria and fungi.

 In aerobic environment, nitrite bacteria (nitrosomonas)

convert ammonia to nitrite (NO2-), and nitrate bacteria
(nitrobacter) convert nitrite to nitrate (NO3-).

 This is called “nitrification” and can be represented by the

following reactions:

2NH3 + 3O2 -------------------- 2 NO2- + 2 H+ + 2H2O

Nitrosomonas
2NO2- + O2 -------------------- 2 NO3-
Nitrobacter
 Nitrogenous BOD (NBOD)
 Combining the two reactions for nitrification:
NH3 + 2O2 ---------------- NO3- + H+ + H2O

So, Oxygen requirement due to nitrification

= 4.57 mg O2/ mg N

 Total concentration of organic and ammonia nitrogen in

wastewater is known as total kjeldahl nitrogen or TKN.

So, Ultimate NBOD = 4.57 * TKN ~ 4.6* TKN

 TKN can be determined in laboratory from which

“ultimate NBOD” can be calculated
 Problem 3: For a BOD test, initial DO = 8.5
mg/L. After 5 days, DO = 4.5 mg/L. If dilution
factor = 50 and k = 0.2/day, calculate:
i) BOD5 ii) ultimate CBOD and iii) BOD
remaining after 5 days
 Problem 4: BOD5 of a wastewater sample is
350 mg/L at 20degreeC. If k = 0.23/day at
20ᵒC, calculate BOD5 at 25ᵒC.
 Biochemical Oxygen Demand (BOD)
Prob-5: The BOD5 of wastewater is determined to be 150 mg/L at 20ºC (k =
0.23 day-1). What is BODu and BOD8 if the test was run at 15ºC? What portion
of the BODu would be remaining unoxidized after 20 days @ Temp 20ºC?
Solution:
BOD5 = L0(1 – e-kx5) => 150 = L0(1 – e-0.23x 5) => L0 = 220 mg/l
kT = k20 θT-20 => k15 = 0.23 x (1.047)15-20 => k15 = 0.18 day-1
BOD8 = L0(1 – e-kx8) => BOD8 = 220(1 – e-0.18x8) => BOD8 = 168 mg/l @ 15ºC
Lt = L0e-kt => Lt/L0 = e-kt => Lt/L0 = e-0.23x20 => Lt/L0 = 0.01 = 1%

Prob-6: Data obtained from a waste water BOD5 = 400 mg/L; k = 0.29 day-1;
NH3-N = 80 mg/L; Estimate the total quantity of DO (mg/L) that will be required
for complete stabilization of this waste water.
Solution:
BOD5 = L0(1 – e-kx5) => 400 = L0(1 – e-0.29x 5) => L0 = 522.6 mg/l (CBOD)
NBOd = 80 x 4.57 mg/L => NBOD = 365.6 mg/L
Now, total DO required for complete stabilization = CBOD + NBOD
=> DO required = 522.6 mg/L + 365.6 mg/L = 888.2 mg/L .
Surface Water Quality: Rivers and Streams
 Surface Water bodies:
 Highly susceptible to contamination
 Historically, contain most convenient sewer for industry as
well as municipalities
 Source of majority of our water
 Organic/Oxygen demanding wastes:
 Constitute most significant part of pollution load, hence
deserve special attention

 Principal water quality problem associated with these

wastes:
 Depletion of DO
Comparing the oxygen demand of industrial
and municipal wastewater
 Modeling Effect of O2 demanding
waste on rivers
 Sources of DO in Rivers:
 Reaeration from atmosphere
 Photosynthetic O2 production
 Do in incoming tributaries or effluents
 Sinks of DO in Rivers:
 Oxidation of carbonaceous waste material
 Oxidation of nitrogenous wastes
 Oxygen demand of sediment (SOD)
 Use of O2 for respiration of aquatic plants
 Modeling Effect of O2 demanding
waste on rivers
 In the simple DO model, two key processes are
considered:
 Source of DO: Reaeration from atmosphere
 Sink of DO: Oxidation of organic matter (carbonaceous)
 The key model assumptions are:
 Continuous discharge of waste at a given location
 Uniform mixing of river water and wastewater
 No dispersion of waste in the direction of flow (ie, plug flow
assumed)
The DO sag curve showing the effect of
oxygen-demanding wastes on the DO
levels in a stream or river
 Model Equations: Deoxygenation
 Due to oxidation of organic matter by bacteria
 Rate of deoxygenation, rD α Lt
=> rD = kd.Lt
Where, kd = temp adjusted BOD rate constant (obtained from
standard laboratory tests).
(Note: For deep slowly moving rivers, this kd value provides a reasonable
approximation. But for turbulent, shallow, rapidly moving stream, kd can be
much higher)

Temp. Correction:
Kd = Kt = K20 (θ)T-20 ; θ = 1.047
So, rD = Kd L0 e (-kdt) …………………………(1)
 Model Equations: Reaeration
 From Atmosphere
 Rate of Reaeration, rR α (Dosat – DO)
=> rR = kr.D ---------------------(2)

Where, D = dissolved oxygen deficit

DOsat= f (T, P, salinity)

Can use, DOsat = 14.62 – 0.394T + 0.007714T2 – 0.0000646T3; T in °C

Kr = Reaeration constant (/d)

= f (particular condition of river)

(Note: for shallow, fast moving stream kr higher; for sluggish stream kr lower)

Commonly used equation,

Kr (20°C) = 3.9 u1/2/ H3/2. where u = avg stream velocity; H = avg stream depth

Temp correction: Kr (T) = Kr (20°C) (θ)T-20 ; θ = 1.024 1.016 (Book:Peavy)

 Model Equations: Streeter-Phelps
 Now, rate of increase of DO deficit (D),
dD
= rD - rR
dt
----------------------------(3)

Solution of eq 3 is known as the classic Streeter-Phelps Oxygen Sag

Equation:

…………………………..(4)

----------------------------(5)

Where, Do = DO deficit at t = 0; x = distance d/s (=ut) ;

u = stream velocity ; t = time

Streeter-Phelps Oxygen Sag Curve
 Streeter-Phelps Oxygen Sag Curve
 It is important to identify critical point where DO is minimum.
 At Critical point, dD/dt = 0
Solving Eq (3) for this condition,

--------------------(6)

From eq (3),
dD
At critical point, = 0 = kd .Loe-kdtc - kr Dc
dt
k
Dc = d Loe-kd tc
kr --------------------------------------(7)

So, DOmin = DOsat - Dc

 Zones of Pollution

Pollution and self-purification of stream and changes in the aquatic

ecology by the disposal of sewage/industrial wastewater.
 Effect of Temperature on DO sag Curve

 As temperature increases, rD increases

 As temperature increases, O2 solubility decreases
 Thus, as temperature increases,
 Critical point reaches sooner
 DOmin becomes lower
 Other Factors affecting DO Sag Curve:
Effect of NBOD

 In some cases, the nitrogenous BOD may have similar

impact on DO levels
 Nitrogenous BOD can be incorporated into the DO sag
curve by adding an additional term:

Where,
Kn = the nitrogenous deoxygenation rate constant (/day)
Ln = ultimate NBOD after waste and river have mixed (mg/L)
 Other Factors affecting DO Sag Curve:
Multiple point source

Curve A is the present predicted dry flow profile with observed river sampling
results. Curve B is the expected dry flow DO profile after implementation of
pollution control measures (Ahmed and Mohammed, 1988).
 Limitations of Oxygen Sag Equation
 Effect of Sediment Oxygen Demand (SOD) not
considered. This is important, especially when sludge is
accumulated along the bottom of a stream.
 Effect of photosynthesis and respiration not considered.
Algae add DO during daytime hours while
photosynthesis is occurring, but at night its respiration
removes DO.
 Nitrification (effect of NBOD) not considered. This can
cause a second dip in the DO sag curve as its effects
are felt.
 Variation in stream characteristics and rate constants
are not considered.
Estimation of Parameters of DO Sag Equation

1) L0 = ultimate BOD

BOD5 = L0(1-e-kt)

If BOD5 and k are known, L0 can be estimated from the above rate equation

2) Kd – estimated from laboratory determined BOD rate constant, k, i.e. k20

Kd = Kt = K20.(θ)T-20 ; θ = 1.047

For any desired Temp. T, kd can be estimated from known value of K.

3) Kr = f (particular condition of river) most widely used equation,

Kr (20°C) = 3.9 u1/2/ H3/2. where u = avg stream velocity; H = avg stream depth

Temp correction: Kr (T) = Kr (20°C) (θ)T-20 ; θ = 1.024 1.016 (Book:Peavy)

4) D0 = Initial DO deficit = DOsat – DOat the point of discharge

DOsat = 14.62 – 0.394T + 0.007714T2 – 0.0000646T3; T in °C

 Problem
Wastewater
T = 25ᵒC
Qw = 15000 m3/d
BOD5 = 40 mg/L
DO = 2 mg/L

River water
T = 22ᵒC
QT = 0.5 m3/s Given:
BOD5 = 3 mg/L Laboratory determined K value for mixture of
DO = 8 mg/L wastewater and river water = 0.23/d

Velocity of stream = 0.2 m/s

Average stream depth = 2.66 m

Estimate:
DOmin, xc, tc, and
Sketch DO profile for a 100 km reach
DO Sag Curve Problem => Solution
DO Sag Curve Problem => Solution

1.016 (Book:Peavy)
DO Sag Curve Problem => Solution
DO Sag Curve Problem => Solution
DO Sag Curve Problem => Solution
 Chemical Oxygen Demand (COD)
COD measures the oxygen equivalent of the organic material in
wastewater that can be oxidized chemically using dichromate in an
acid solution. The basis for COD test is that nearly all organic
compounds can be fully oxidized to carbon dioxide with a strong
oxidizing agent under acidic conditions. The amount of oxygen
required to oxidize an organic compound to carbon dioxide, ammonia
and water is given by:

This expression does not include the oxygen demand caused by

nitrification, the oxidation of ammonia into nitrate:

Dichromate, the oxidizing agent for COD determination, does not

oxidize ammonia into nitrate, so nitrification is not included in the
standard COD test.
 Chemical Oxygen Demand (COD)
The reaction of potassium dichromate with organic compounds is
given by:

The amount of oxygen required to oxidize all the organic matters (with
few exception) by the action of strong chemical oxidizing agents under
acid condition. During COD determination, organic matter is converted
to CO2 and H2O regardless of the biologically assimilability of the
substance. For example, glucose and lignin are both oxidized
completely. As a result, COD values are greater than BOD values,
especially when biologically resistant organic matter (e.g. Lignin) is
present.
Major Advantage => Short time required to evaluation.
Major Limitation => Inability to differentiate between biologically
oxidizable and biologically inert organic matters.
 Chemical Oxygen Demand (COD)
Problem: Determine the COD values of samples containing 300 mg/L of
(a) Glucose (C6H12O6) (b) Phenol (C6H5OH) (c) Ethanol (C2H5OH)

Solution:
(a) C6 H12O6  6O2  6CO2  3H 2O
180gm 192gm
COD Value of 300 mg/L Glucose (C6H12O6) = (192/180) x 300 mg/L = 320 mg/L

(b) C6 H 5OH  7O2  6CO2  3H 2O

94gm 224gm
COD Value of 300 mg/L Phenol (C6H5OH) = (224/94) x 300 mg/L = 715 mg/L

(c) C2 H 5OH  3O2  2CO2  3H 2O

46gm 96gm
COD Value of 300 mg/L Ethanol (C2H5OH) = (96/46) x 300 mg/L = 626 mg/L
 Ammonia Toxicity
Ammonia-nitrogen can exist in two states in natural water:
NH 3 T  
 NH 4  NH 3 .......... (i)
Total NH3-N NH4-ion Unionized NH3
The un-ionized form can be toxic to fish at Concentration > 0.1 mg N/L.
Equilibrium dissociation reaction of NH4+ as follows: NH 4  NH 3  H 
Where, the ratio of the reactants to the products is specified by an
equilibrium co-efficient, K.
K
   NH  
NH  H    
NH  H 
NH 
3 3
 4
4 K
The equilibrium co-efficient for the reaction is related to temperature:
2729.92 T => Water Temperature in Degree Kelvin
P K
 0.09018
T
Again, P K   log K   K  10 P Now, from equation (i) =>
K

 
 
10

NH 3 T  NH 3   NH 3  H   H

 NH 3 1 
 1 
  NH 3   NH 3 T  H  
K  K  1  
 K 
 Ammonia Toxicity
Problem
The water quality characteristics of a river shows the total NH3 concentration
= 1 mg N/L, PH = 8.5, T = 30ºC. Determine the concentration of unionized
NH3 and whether it is okay for fisheries (Allow: 0.1 mg N/L of NH3)?

Solution:  
 
NH 3   NH 3 T 
1
 .......... ...( i )
1  H 

 K 

2729.92 2729.92
P  0.09018
K
 0.09018  9.095
T 273.15  30
K  10 PK
 109.095  8.031010 H   10
 PH
 108.5  3.16 109
 
 
(i )  NH 3   1.0  
1
9   0.202mgN / L  0.1mgN / L
1  3.16  10 
 8.03  1010 
No Fish Can Survive