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 5. ORGANIC MATTER QUANTIFICATION

5.1 BOD

BOD is the measure of biodegradable quantity of waste (organic matter). Its the oxygen consumed when
microorganisms breakdown organic matter.

It is generally assumed that the rate at which the oxygen is consumed is directly proportional
to the concentration of degradable organic matter remaining at any time. The kinetics of
BOD reaction can be formulated in accordance with first order reaction kinetics as:
dL/dt =-KL

Where, Lt = amount of first order BOD remaining in wastewater at time t

K = BOD reaction rate constant, time-1

Where Lo or BODu at time t = 0, i.e., ultimate first stage BOD initially present in the sample.
The relation between K(base e) and K (base 10) is K(base 10) = K(base e) / 2.303

Fig.5.1Typical BOD Exerted in wastewater

kt
The amount of BOD remaining at timet equals (Figure 5.1), Lt = Lo (e )
The amount of BOD that has been exerted (amount of oxygen consumed) at any time t is
kt
given by BODt = Lo Lt = Lo (1 e ). And the five day BOD is equal to
BOD5 = Lo L5 = Lo (1 e -5k )
For polluted water and wastewater, a typical value of K (base e, 20o C) is 0.23 per day and K
(base 10, 20 o C) is 0.10 per day. These values vary widely for the wastewater in the range

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from 0.05 to 0.3 per day for base 10 and 0.23 to 0.7 for base e.

The ultimate BOD (Lo) is defined as the maximum BOD exerted by the wastewater. It is
difficult to assign exact time to achieve ultimate BOD, and theoretically it takes infinite time.
From the practical point of view, it can be said that when the BOD curve is approximately
horizontal (Figure 5.1) the ultimate BOD has been achieved. The time required to achieve
the ultimate BOD depends upon the characteristics of the wastewater, i.e., chemical
composition of the organic matter present in the wastewater and its biodegradable properties
and temperature of incubation. At higher temperature for same concentration and nature of
organic matter ultimate BOD will be achieved in shorter time as compared to lower temperatures,
where it will require more time.

The BOD reaction rate constant is dependent on the following:

a) The nature of the waste b) The ability of the organisms in the system to utilize the waste
c) The temperature

Example
The wastewater is being discharged into a river that has a temperature of 15 oC. The BOD rate constant
determined in the laboratory for this mixed water is 0.12 per day. What fraction of maximum oxygen
consumption will occur in first four days?
Solution
Determine the BOD rate constant at the river water temperature:
K15 = K20 (1.056) (T-20) = 0.12 (1.056) (15-20) = 0.091 per day
Using this value of K to find the fraction of maximum oxygen consumption in four days:
BOD = Lo (1 e -0.091x4)
Therefore, BOD / Lo = 0.305

Example

The dissolved oxygen in an unseeded sample of diluted wastewater having an initial DO of

9.0 mg/L is measured to be 3.0 mg/L after 5 days. The dilution fraction is 0.03 and reaction
rate constant k = 0.22 day -1
Calculate a) 5 day BOD of the waste, b) ultimate carbonaceous BOD, and c) What would be remaining
oxygen demand after 5 days?

Solution
a) Oxygen demand for first 5 days
BOD 5 = (DOi Do ) / p = (9.0 3.0) / 0.03 = 200 mg/L
b) Ultimate BOD BOD u = Lo = BODt / (1 e kt ) = 200 / (1 e -0.22 x 5 ) = 300 mg/L
c) After 5 days, 200 mg/L of oxygen demand out of total 300 mg/L would be satisfied.
Hence, the remaining oxygen demand would be 300 200 = 100 mg/L

Interpretation of the BOD test Result

Following factors must be considered in the interpretation of the BOD for industrial
wastewaters:
The seed is acclimated to the wastewater and lag period required for acclimation is

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eliminated.
The rate constant should be established based on long term BOD tests on both
wastewater and treated effluents. The rate constant for untreated and treated
wastewater is not same for many wastewaters. The rate constant value is higher for
untreated wastewater and lower for treated wastewater

The standard BOD analysis takes 5 days (BOD5), but alternatives are sometime used, Figure 5.2
shows the dependency of time and temperature for the BOD analysis. It is important that the
BOD test is carried out at standard conditions. The BOD analysis result depends on both test
length and temperature. Standard is 20C and 5 days.

Fig.5.2: BOD variation with time and temperature

Nitrification in BOD Test

Non-carbonaceous matter, such as ammonia is produced during the hydrolysis of proteins. In

addition, when the living things die, excreta waste, and nitrogen organic compounds, the
nitrogen tied to organic molecule is converted to ammonia by bacterial and fungal action.
Under aerobic conditions, this ammonia will be converted to nitrate, called as nitrification as
per the reactions given below:

Hence, the organic matter containing nitrogen will have oxygen requirement for nitrification.
The oxygen demand associated with the oxidation of ammonia to nitrate is called the
nitrogenous BOD. Due to low growth rate of nitrifying bacteria, this BOD demand normally

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Fig.5.3: Nitrification during BOD test.

occurs from 6 to 10 days (Figure 5.3). This is one of the reasons to use incubation period of
5 days for BOD determination to eliminate oxygen demand for nitrification and to find out
only carbonaceous oxygen demand. Incidentally, the five day period was chosen for the test
because the Themes River requires five days from its origin to join sea, and if oxygen
demand for these five days is determined and satisfied the river water quality can be
protected.

5.2 COD

COD determines the organic content through chemical oxidation usually by potassium
dichromate in acidic conditions. It measures virtually all oxidizable organic compounds whether
biodegradable or not, except some aromatic compounds which resists dichromate oxidation.
The COD is proportional to BOD only for readily assimilable organic matter in dissolved form
e.g. sugars.
The COD is faster determination but does not give idea about the nature of organic matter
whether biodegradable or biorefractory. Hence, determination of BOD is necessary. Thus, it is
important to develop correlation between BOD and COD (or TOC), so that COD (or TOC) can
be used as a parameter for routine analysis and control of the treatment plant. Once COD values
are known, the BOD can be estimated using correlation. The test results are more reproducible
for COD.

5.3 ThOD
Theoretically waste that is completely oxidized either biologically or chemically, the value is
referred to as theoretical Oxygen demand (ThOD). BOD=COD= ThOD. For most organic
compounds, ThOD = COD. Thus, carbon molecules are converted into CO2, hydrogen into
water, nitrogen into NO3, sulphur into SO3, etc. For example,

Urea, CH4N2O + 9/2 O2 CO2 + 2H2O +2NO3 i.e 1 mole of urea requires 4 moles of
oxygen for complete oxidation or 60 g of urea require (4.5x32)=144 g of oxygen i.e 2400mg/l of
O2for 1g/l of urea. i.e ThOD= 2.4g O2 per g Urea.

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For urea concentration of 0.02 molar, the ThOD=0.0 2x60x2.4 =2.88g/l or 288mg/l

Glucose, C6H12O6 + 6O2 6CO2 +6H2O. i.e 192/180 , 107mg/l of oxygen for 1g/l of glucose.
Ethanol, C2H6O + 3O2 2CO2 + 3H2O. i.e 96/46 , 209mg/l of oxygen for 1g/l of ethanol.

5.4 Impact of Effluent discharge on receiving river

As a result of natural assimilation, water bodies are capable of self purification upto its capacity.
When that capacity is exceeded, pollution results.

The Oxygen Sag

Fig. 5.4. Oxygen depletion along the river course and its impact.

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On entering the river waste will be biodegraded depleting oxygen but at the same time oxygen
will be supplied from the atmosphere. The oxygen dynamics as shown in Fig 5.4 is known as the
oxygen sag. One of the commonest model of the oxygen sag is the Streeter Phelps equation.

Combining deoxygenation and reaeration processes, the rate of oxygen deficit is equal to rate of
deoxygenation minus rate of reaeration. i.e Rate of BOD removal ( )b = -KdL, and rate of
oxygen transfer(reaeration), ( )r = Kr(Cs-C). Writing the oxygen balance,
V = V( )b + V( )r OR =( )b + ( )r = -KdL + KrD. But =(0- ), and hence

= KdL - KrD
Where, = rate of change in oxygen deficit (D), mg/l-d
Kd = deoxygenation rate constant, usually not equal to BOD rate constant found in lab, d-1.
L= BODu of the river water, mg/l, with L = Lo e-Kdt
Kr = reaeration rate constant, d-1
D=Oxygen deficit, mg/l

= KdL - KrD = Kd Lo e-Kdt - KrD

By integration, and given that D=Do at t=0, then;

D= (e-Kdt e-Krt) + Doe-Krt , where t is time in days of travel downstream. This equation is
for carbonaceous BOD. If nitrogenous BOD is significant, an adjustment to the equation would
be made to take care of it. D= (e-Kdt e-Krt) + Doe-Krt + {e-Knt e-Krt }where Kn is
the nitrogenous deoxygenation constant and Ln is NBODu after mixing.

All the work here will assume carbonaceous BOD unless otherwise stated.

Do and Lo are the initial DO deficit and initial BODu respectively after mixing with the river.

D= DOs DO

At critical point, i.e the largest deficit, =0, KdLc=KrDc and D=Dc = Lc = Lo e-Kdtc
Time to critical point, is tc and is given by (D) =0 and solving for t.

tc = In 1D

Note Do = DOs DOm, where DOm = . Also, Lo =

Rate Constants Determination

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Kd, the deoxygenation rate is usually not the same as the lab BOD rate, K1, due to different
conditions due to temperature and other physical conditions and microorganisms diversity in the
river environment. Normally Kd >K1. There are empirical formulae that can be used to estimated
Kd e.g Bosko`s equation given by

Kd = K1 + .! , for base 10 at 20oC where v= average flow velocity in the river, m/s; K1= BOD
rate constant obtained in the lab., d= average river flow depth in m and = river bed activity
coefficient (0.1 for stagnant, 0.6 for deep or more for rapidly flow river).
Kd can be adjusted for temperature (T) using Kd = Kd(20oc) x1.024(T-20)

Kr, the reaeration rate can be estimated by a number of empirical equations. One of the equation
is Kr = 2.833 ".# at 20oc. for base 10. Kr can be adjusted for temperature (T) using
Kr = Kr(20oc) x1.024(T-20)

Exercise
A river receives a discharge with the characteristics given below. Determine the critical DO and
the distance downstream of discharge point.

Parameter River Effluent

Flow m3/s 0.5 0.05
DO, mg/l 5.85 0.9
Temp, oC 25 25
BODu, Kg/d 820.8 129.6
K at 20oC, base 10 NA 0.112
Flow velocity, m/s 0.1 NA
Bed activity coef 0.2 NA
Average depth, m 3.7 NA

Assignment
A river receives treated wastewater from a town. Given the characteristics of the wastewater and
the river, determine if the river DO reduces below 5mg/l at any point downstream of the
discharge point.

PARAMETER river wastewater

Flow, m3/s 0.9 0.28
BODu, mg/l 7 6.5
DO, mg/l 6 1
Kd at 28oc, d-1 0.2 N/A
Kr at 28oc, d-1 0.37 NA
Velocity, m/s 0.65 NA
Temperature, oC 28 28

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