Measurement of organic mattereasurement

• Biochemical oxygen demand (BOD)

• Chemical oxygen demand (COD)
• Total organic carbon (TOC)
 BOD and NOD

NOD (Nitrogenous oxygen

Oxygen demand

demand

CBOD (Carbonaceous oxygen

demand)

Time, days

1 2
 BOD - Model

BOD – Assumed to be first order reaction

Lt = oxygen equivalent at time t = t
Lo = Oxygen equivalent at time t =0 ( or ultimate BOD)
dL
 k L
t yt = BOD at time t=t
1 t
dt
Lo
dLt
BOD ( exerted/remaining)
Lt t
Lo Lt
 k1   dt
o

 kt
Lt  Lo e yt  L o  Lt


yt  L o 1  e  k 1t
 Lt

k1= 0.12 – 0.46 /day - at 20 0C 1 Time, days

 k t  k 20 T  20
1.056 – (20 -30 0C)
 1.135 - (4- 20 0C)
Typical value – 1.047
van’t Holff-Arrhenius model

Problem: Find out the following parameters from the given data

Given : BOD5,20 = 300 mg/L ; Reaction constant, k20 = 0.23/d

Calculate : 3 day BOD at 27 oC; 5 day BOD at 27 oC; Ultimate BOD

Also develop a plot ( time Vs BOD) for the three different temperatures
(20 , 27 and 35 0C)

1 4
 Biochemical Oxygen Demand (BOD)
• BOD – the amount of DO consumed during microbial oxidation of
organics
– Unseeded BOD test
– Seeded BOD test
• BOD Test
– 300 mL BOD bottle
– Initial and Final DO
– 5 days 20 0C or 3 days 27 0C
– No sunlight
– Dilution of water necessary
– No toxic material in the water
– Final DO should be more than 1 - 1.5 mg/L
– At least 2 mg/L of DO should be consumed
Acceptance criteria
by organisms after 5 d.
1 5
 BOD 5,20 = (IDO – FDO)/Fww

BOD 5,20 = (IDO – FDO) –(IDOsc – FDOsc)Fsc) /Fww

IDO – Initial dissolved oxygen conc. of diluted (seeded) WW mixture, mg/L

FDO – Final dissolved oxygen conc. of diluted (seeded) WW mixture, mg/L
IDOsc - Initial dissolved oxygen conc. of seeded mixture from seed BOD test, mg/L
IDOsc - Initial dissolved oxygen conc. of seeded mixture from seed BOD test, mg/L
Fsc- fraction of seeded dilution water in sample to volume of seeded dilution water in seed
control
Fww- volume of wastewater in ml/300 ml
 Limitations of BOD Test

• Large amount of seed bacteria is required

• Presence of toxic waste- pretreatment is required
• Error from nitrification – need to reduce nitrifying
bacteria
• Long incubation period – slow process

1 7
 Chemical Oxygen Demand (COD)

• Advantages of COD test over BOD test:

– Rapid ( 2.5 h)
– Can oxidize complex organic ( lignin) or toxic substances (
pesticides)
Limitations:
1. Dichromate can oxidize inorganic substances – high COD value

Total Organic Carbon (TOC)

-Rapid ( 5- 10 min)
-possible to detect trace quantities

1 8
Factors that affecting the self purification of stream
• Pollution of rivers -poor management and unscientific use.
• The major contributors are:
– Untreated or partially treated wastewater form point sources
such as industries,
– Run off from non point sources such as urban and agricultural
areas.
– excessive withdrawal of water for agricultural and municipal
utilities
– and perpetual droughts limits the capacity of river for dilution
of waste
– use of rivers and lakes for religious and social practices,
– the typical examples of the river water pollution – River
Ganges
Factors that affecting the self purification of stream

Oxygen in air Algae in water

photosynthesis
Reaeration
Respiration

DO in water
Deoxygenation
SOD

CBOD NBOD

Settling

SOD

Factors affecting dissolved

1 oxygen conc. in water 10
Computation of organic waste loads on stream
• To calculate the degree of treatment required to
satisfy the standards set.
• Over treatment of waste results in additional
expense on the industry
• Under treatment is a waste of effort and money- it
does not abate the pollution problem.
 Computation of organic waste loads on stream:
Streeter and Phelps model
– The model predicts the oxygen level at various location as function of BOD
exertion and stream aeration
– Rate of oxygen removal

Rate of deoxigenation = rate of BOD exertion

dy dC Reaeration α oxygen deficit , D

 D = Cs-C
dt dt
dy dD y = Lo-Lt

dt dt
dy dLt  dLt 
 ..........   kLt 
dt dt  dt 
dD
 kLt
dt
rD  k Lt
12
 Dissolved oxygen model- Streeter and Phelps
equation
• Rate of oxygen addition α oxygen deficit, D
• Dissolved oxygen deficit =Cs-C
rR  k 2 D
Do

Dt
Dc
Ct rR
• Oxygen balance CC
DO, mg/L

dD
 rD  rR
dt rD
 k1 Lt  k 2 D

Time, days 13
 dD
dt

 k 2 Dt  k1 Lo e tk1        Lt  Lo e tk1 

e k 2t
dD
dt
  
 e k 2t k 2 Dt  e k 2t k1 Lo e tk1        Lt  Lo e tk1 
d
dt

De k 2t  e k 2t k1 Lo e tk1 
d
dt

De k 2t  k1 Lo e k 2  k1 t 
 d De 
k 2t
k 1 o
L e k 2  k1 t
dt
k1 Lo
De k 2t  e k 2  k1 t  C
k 2  k1
at..D  Do ....t  0
k1 Lo
C  D0 
k 2  k1

1 14
 k1 Lo k 2  k t
De k 2t
 e C
k 2  k1
k1 Lo k 2  k t k1 Lo
De k 2t
 e  D0 
k 2  k1 k 2  k1
k1 Lo e k 2  k t k1 Lo D0
D   k 2t
k 2  k1 e k 2t
k 2  k1 e k 2t
e
k1 Lo  k1t k1 Lo
D e  e  k 2 t  Do e  k 2 t
k 2  k1 k 2  k1 

D
k1 Lo
k 2  k1
 
e  k1t  e  k 2t  Do e  k 2t      1

1 15
 Critical Deficit and Critical time
dD
dt

 k 2 Dt  k1 Lo e tk1        Lt  Lo e tk1 
dD
0 Rate of change is zero at maximum deficit
dt

0  k 2 DC  k1 Lo e  tck1
k1
DC  Lo e tck1
k2
To find the value of critical time, differentiate eq. 1 and e equate to zero

0
k1 Lo
k 2  k1

e tc k1  e tc k 2  Do e tc k 2 
0 k1 Lo   k 1e tc k1 e  t c k 2  Do e  t c k 2
   tc k 2  
e t c k 2 k 2  k1  e t c k 2
1 e  e t c k 2
16
0
k1 Lo
k 2  k1
 
k1e t c  k 2  k1   k 2  k 2 Do

k 2 Do  
k1 Lo
k 2  k1

k1e t c  k 2  k1   k 2 
k 2 Do
k 2  k1
k1 Lo

  k1e t c  k 2  k1   k 2 

k1e  t c  k 2  k1 
 k
  k 2  Do 2
k 2  k1  


 k1 Lo 

k1 t c  k 2  k1 
e
k k
  2  Do 22
k 2  k1  

k1 
 k1 k1 Lo 

k k 2  k 1 
ln e   t c  k 2  k1 
 k
 ln  2  Do 22 

 k1 k1 Lo 

1 k k k 2  k 1 
tc  ln  2  Do 22 
k 2  k1 
 k1 k1 Lo 


tc 
1  k2 
ln  1  Do
k 2  k1  

k 2  k1  k1  k1 L0  17
 1  k2  k 2  k1 
tc  ln  1  Do       2
k 2  k1  k1  k1 L0 
Example 3.3: A municipal WW treatment plant discharges secondary effluent
to a surface stream. In summer under worst conditions, measurements are
made in the laboratory and in the filed to determine the characteristics of the
WW and stream flows. The data collected are: maximum flow rate of the WW
(=1500 m3/d), 5 day BOD (=40 mg/L), DO (=2 mg/L ) and temperature (=25
0C). The corresponding data for the stream is found to be 0.5 m3/s, 3 mg/L, 8

mg/L, and 22 0C, respectively. Assume complete mixing. The velocity of the
mixture is 0.2 m/s. The reaction rate constant, K1 and reaeration constant K2
at 20 oC is 0.23, and 0.4/day, respectively. Sketch the DO profile for a stretch
of 100 km from the point of discharge.

DOsat  14.652  0.41022T  0.0079910T 2  0.000077774T 3

ASCE Formula for finding DO conc. at saturation

18
Solution:

(Qw=1500 m3/d), BOD5=40 mg/L, DO=2 Apply mass balance

mg/L ; T =25 0C.
(Qmix=? m3/s), BODmix=? mg/L,
MWTP DOmix=? mg/L ; Tmix =? 0C.

U/S RIVER
D/S
(QR=0.5 m3/s), BOD5=3
mg/L, DO=8mg/L ; T
=220C. K1 = 0.23/day 1 1oo km
K1 = ?/day (ф =1.047)
K2 = 0.4/day
K2 = ?/day (ф =1.016)

DO sat  14.652  0.41022T  0.0079910T 2  0.000077774T 3

1 k  k 2  k1 
tc  ln  2 
 1  D 
      2
 k1
o
k2  k1  k1 L0 
k1
DC  Lo e  tck1
k2
D 
k1 Lo
k 2  k1

e tk1  e  tk2  D o e  tk2      1
1 19
 Limitations of oxygen sag curve

• K1 and K2 are function of many variables- model makes no

allowance to incorporate the effect
• The equation is derived based on the assumption that there is one
point source of BOD – it does not consider other point and non
point source
• BOD demand may vary based on many factors: Algal respiration in
absence of light; nitrification process that increase oxygen
demand; presence of sludge deposit in pool areas
• Utilization of BOD by attached growth- in the case of shallow rivers
• Reaeration constants : DO contribution of algae photosynthesis
• The equation assume study state condition all along the river – not
true