CHARACTERIZATION OF WASTEWATERS AND SLUDGES

ASSESMENT OF BIOMASS (SLUDGE)

In the modeling and operation of activated sludge, Organic Biomass (C5H7NO2) is measured by
means of VOLATILE SUSPENDED SOLIDS (VSS) analysis. SUSPENDED SOLIDS analysis
is used to determine total biomass concentration (SS).

TOTAL SOLIDS (TS)

SAMPLE
FILTER
Evaporation filtrate

SS FS
(suspended solids) (filterable solids)
Muffle oven
550 0C
VSS FSS
(organic) (inorganic)

volatile suspended solids fixed suspended solids

TOTAL SOLIDS (TS)

Settleable Non-settleable
solids solids
Imhoff cone

ASSESMENT OF SUBSTRATE (Wastewater)

Inorganic substrates:

Inorganic substrates such as N and P can be qualified directly and pose no problem as far as
STOICHIOMETRIC reactions are concerned.

The nitrogen (N) fractions → conventional analysis

(Kjeldahl nitrogen, ammonium, nitrite, nitrate)

The phosphorus (P) fractions → well-known laboratory methods

(organic phosphorus, orthophosphate, polyphospahate)
Organic substrates:

Assessment of wastewater organic content is NOT SO SIMPLE.

Wastewater normally CONTAINS THOUSANDS OF DIFFERENT ORGANICS which CAN

NOT BE IDENTIFIED INDIVIDUALLY on a routine basis.

Therefore COLLECTIVE SUBSTRATE PARAMETERS are used AS INDIRECT INDEX

VALUES to characterize the overall organic content.

The measurements of these parameters are based on two principles:

1) the consumed amount of oxygen (the BOD, COD, TOD analysis) measurement
2) the produced amount of carbon dioxide (the TOC analysis) measurement

The different measuring methods yield different results and therefore the individual methods can
not be replaced each other indiscriminately.

THE CHOICE OF ANALYSES PARAMETERS HAS BEEN, AND STILL IS, THE SUBJECT
OF DISCUSSION

BIOCHEMICAL OXYGEN DEMAND, BOD (BOD5):

The idea of analysis was that in polluted water there is an oxygen demand caused by
microorganisms. The required oxygen demand was used to measure the extent of the pollution.
The BOD analysis is used to measure the oxygen demand of the micro-organisms for oxidation
of ORGANIC MATTER and AMMONIA.

Let’s have a close look at the BOD test itself to understand its limitations:
 carried out in a BOD bottle
 wastewater is highly diluted
 temperature is standardized at 20 0C
 the measurable consumption of oxygen is limited to the amount of dissolved oxygen
originally contained in the bottle (a level which is usually around 3-4 mg/l)
 the bottle is seeded with a minute amount of microorganisms expected to degrade the
organic matter in the wastewater sample.
 The test is never allowed to reach its completion [measurement that is made after five
days is used as 5-day biochemical oxygen demand (BOD5)]. Therefore, BOD5 does not
reflect the real oxygen consumption potential or the organic matter content of the sample.

Therefore, BOD5 indicates a value in the course of biochemical reactions taking place in the
BOD BOTTLE

Other necessary conditions: pH≈7, other minerals and nutrients should be added not to limit
microorganism’s growth, in dark, etc.

In these conditions, biochemical oxidation is a slow process which requires very long time. 95-
99 % of organic matter can be oxidized in 20 days. Only a fraction of organic matter can be
measured in 5 days.
Nitrification can occur in the bottle even before 5 days and BOD5 value may contain the oxygen
requirement of nitrogen as well. In order to avoid this nitirification inhibitor (thiourea) is added
to the BOD bottle to make sure that the analyze result reflects only the oxygen used for
carbonaceous material oxidation and this value can be compared with COD parameter.

NOD
L (BODu)

2 4 6 8 10 12 14 Time (days)

The total or ultimate oxygen demand BODu(L) can only be assessed indirectly, by using the
following first-order reaction rate expression where k is the rate constant of the overall
biochemical reaction in the bottle:

BOD5 = L (1-e -5k) t= 5 days

BOD5 is usually correlated to L by a factor :f

BOD5
f 
L( BODu )  ultimateBOD
can be accepted as COD
 L (BODu)

K = 0.2 d-1

K = 0.1 d-1

K = 0.15 d-1

5 days Time (days)

The wastewaters having the same BODu (L) can have different BOD5values and consequently
different f ratios if they have different degradation rate constants (k).

The value of f is by no means universal. Although reported as 0.65-0.7 for domestic sewage, it
may vary within a very wide range of 0.1-0.9 for different type of municipal and industrial
wastewaters.

The merit of BOD5 as a model parameter in biological systems is quite questionable for number
of reasons:

 It has to relate to ultimate BODu (L) by a rate coefficient, k which is not a constant but a
variable coefficient strictly depending on the type of wastewater.
 The amount of organic matter removed Q (Ci-Ce) is very important for the performance
assessment in biological treatment systems.

Q=wastewater flow
Ci=influent biodegradable organic matter concentration
Ce=effluent

The more easily degradable ones are usually removed during treatment, so that the effluent
composition includes the slowly biodegradable portion of the influent organic content.
Consequently, BOD5 usually identifies a much lower portion of degradable organics in the
effluent compared to the influent, with the net result that it does not accurately reflect the
organic matter removal in the treatment system. (see the figure below)
 ( BOD5 )i
fi fi 
Li % organic
matter removal

% BOD5 removal  % organic matter removal

fe < fi
( BOD5)e
fe 
Le

Ci Ce

Q Q

Fate of BOD5 in the activated sludge process

Using BOD5 as an effluent quality control parameter runs the risk of facing misleading low
effluent values for slowly degradable wastewaters.

 Consumed O2, produced sludge and utilized organic matter balance can not be
established by using BOD5 parameter.
 In short, BOD values are delivered from a poorly defined set of biochemical reactions
in a poorly defined reactor, a BOD bottle.

Some of the basic problems associated with the use of BOD as a substrate parameter are
illustrated in the example below:

Example: Performance evaluation by using BOD

The treatment by activated sludge of an industrial wastewater having a BOD5 of 1000

mg/l, secures 90 % removal efficiency. Parallel studied indicated that k values of
0.24/day and 0.05/day can be associated with the influent and the effluent respectively.
Find the real organic matter removal efficiency achieved by the treatment system.
 Solution:
The reaction rate expression for BOD is BOD5= L (1- e -5k)

(A) The organic matter concentration in the influent for ki= 0.24/day:

( BOD5 ) i 1000
Li 
5 ki
  1430 mg / l
1 e 1  e 5 x 0.24
(B) The organic matter concentration in the effluent for ke=0.05/day

(BOD5)e = (1-0.9) (BOD5)i= 0.1x1000 = 100 mg/l

( BOD5 ) e 100
Le  5 ke
  455 mg / l
1 e 1  e 5 x 0.05

(C) The achieved removal efficiency

Le  Li 1430  455
% removal  x100  x100  68 %
Li 1430
The real organic matter removal efficiency is calculated to be much lower that reported
BOD5 removal efficiency.

CHEMICAL OXYGEN DEMAND (COD):

COD is a test where the organic matter in the sample is oxidized to CO2 and H2O by
potassium dichromate in boiling concentrated sulfuric acid (150 0C) and in the presence of a
silver catalyst.

2
Organicmatter  Cr2 O7  acid 150
  CO2  H 2 O  NH 3
0
C

C a H b Oc N d

 It does not oxidize ammonia. This is quite beneficial to use COD as a substrate parameter
reflecting only the carbon balance in biochemical reactions.
 Some aromatic compounds like pyridine, benzene, toluene, etc., are not oxidized in the
test. As these aromatic compounds constitute only a minute fraction of the organic
content of most wastewaters. COD, unlike BOD5, may be used as a direct parameter.
 Aside from biodegradable materials normally are not present in significantly
concentrations in wastewaters.
 The COD analysis may be carried out automatically and relatively fast (2 hours)
 The measured COD value gives a good picture of the total content of organic matter.
 The COD values are suitable for the calculations of the mass balances (O2 consumed,
sludge produced, substrate utilized) in treatment plants.

TOTAL OXYGEN DEMAND (TOD):

By oxidizing at a high temperature (900 0C) and by using a suitable catalyst, a total chemical
oxygen demand may be determined, called TOD. By using this analysis, the few organic
compounds are oxidized WHICH are not oxidized by the COD-analysis. Besides, ammonium
is oxidized!
TOTAL ORGANIC CARBON (TOC):
By using this analysis, organic matter is oxidized to CO2 by heating. The difference between
the carbon dioxide concentration before and after oxidation is used for the calculation of the
TOC. It states the amount of C atoms but does not say anything about their oxidation state
and hence nothing as to how much oxygen should be used for oxidation. Therefore, it can not
be used to set an equivalence basis between important components of biochemical reactions
(consumed O2, utilized substrate, and produced sludge). Besides, it requires a more
sophisticated and costly analytical measurement set up.

Example: Calculate the Theoretical COD and TOC and theoretical TOD values of 1 molar
(1mole/L) CH3COOH (acetic acid) and CH3CH2OH (ethyl alcohol) two wastewaters having
the same TOC.

CH3COOH + 2 O2 → 2 CO2 +2 H2O

CH3CH2OH + 3 O2→ 2 CO2 + 3 H2O

Acetic acid Ethyl alcohol

TeTOC : 24 g/L TeTOC : 24 g/L
TeCOD : 64 g/L TeCOD : 96 g/L

Since both do not contain nitrogen, theoretical TOD = theoretical COD

EMPIRICAL WASTEWATER CHARACTERIZATION:

It is sometimes beneficial to express the overall elementary composition of organic
compounds in wastewaters by a single empirical formula; one of the most commonly used
empirical formula for the organic content of domestic sewage is: C18H19O9N

Theoretical Chemical Oxygen Demand (TeCOD)

If the chemical formula of organic matter is known, it can be theoretically calculated from
the oxidation reaction. For example: domestic wastewater ≈ C18H19O9N

35 g O2
C18 H 19 O9 N  O2  18CO2  8H 2 O  NH 3 TeCOD→ 560/393=1.4
 2 g organic matter
393 g 
560 g

Theoretical Total Oxygen Demand (TeTOD)

Ammonia oxidation should be added to TeCOD

NH4 + + 2 O2 NO3- + H2O + 2 H+ 64/14= 4.57 g O2/g ammonia

TeTOD: 560 + 64 = 624 g

TeTOD/TeCOD = 624/560 =1.1

 %
Depending on k
100 coefficient
In domestic wastewater:
BOD5/COD=0.4-0.8
BOD5/TOC=1.0-1.6

50

TeTOD TOD TeCOD COD BOD TOC

D
Analysis for organics in wastewater and their relationship

In short, COD is the most convenient parameter for the assessment of organic content of
wastewater. It can be used to set an equivalence basis between three important components:
O2 consumed, substrate utilized, biomass produced.

TOTAL COD (CT)

Biodegradable, Cs Unbiodegradable (Inert COD)

hydrolysis
Ss Xs XI SI ͌ effluent soluble COD
(Soluble) (Particulate)

BODu/BOD5 =1.5

Cs/BODu = 1.1-1.2
 CONCEPT OF YIELD AND STOICHIOMETRY

The removal of substrate is accomplished by 1) generating biomass and 2) consuming D.O.

1) Since the treatment and disposal of excess sludge is at least equally important and costly
a problem as substrate degradation we want to know how much biomass will be
generated in our system. So we can decide how big our settling tank should be in order to
handle produced biomass.
2) Estimation of the amount of oxygen utilization is also a main concern, as it directly
affects the operation cost of the treatment plant. We should know how much O2 we
should supply to reach desired treatment.

So we need to find the relation between these three magnitudes (substrate, biomass and oxygen).
The concept of YIELD (Y) is one of the major modeling tools used for the correct assessment of
excess biomass generation and oxygen consumption relation to substrate removal.

BIOMAS PRODUCED

SUBSTRATE REMOVED
Oxygen consumption in energy reactions

BIOMASS PRODUCED
YIELD Y
SUBSTRATE REMOVED

It defines the amount of biomass formed per unit amount of organic matter removed for
heterotrophic growth (YH). The concept of yield can not be interpreted and evaluated without
STOICHIOMETRY of the related mechanism. Stoichiometry sets a material balance between all
reactants and products of a mechanism. The stoichiometric expression of a mechanism is
independent of reaction rate (time) and it is valid for every step of the reaction. TRUE YIELD
relates only to growth mechanism, and, as such it is used as stoichiometric constant. It is not
affected by the reaction rate of the growth mechanism a property that makes it a stoichiometric
constant.

True yield ≡ Maximum yield

Substrate concentration decreases with time only as a function of the growth mechanism,
whereas the biomass concentration profile is the net result of an increase due to biosynthesis, and
a decrease due to endogenous metabolism.

Therefore, the net yield of the system, YNH, is not a constant, but a variable coefficient with
lower and lower values for longer reaction times (Time factor is involved, no longer
stoichiometric constant like true yield, YH). It may change, however, for various carbon and
energy source, resulting in different stoichiometric expressions for EACH SUBSTRATE. YNH
may be calculated on the basis of the observed changes in substrate and biomass.
CONCEPTUAL APPROACH FOR THE CALCULATION OF YIELD

METHODS OF EXPRESSING THE YIELD COEFFICIENT:

Different values may be attributed to the yield coefficient by choosing different parameters to
characterize the amount of biomass formed and the amount of substrate removed.

SUBSTRATE: BOD5, COD*

BIOMASS: SS, VSS, COD*
OXYGEN: O2 (COD*)

Combining these parameters yields different ways of expressing the yield coefficient. An
additional benefit to defining both substrate, and biomass in terms of COD, is a better
understanding of the stoichiometry and the kinetics of major processes in the activated sludge
system. This approach also provides a convenient way of relating oxygen consumption to
substrate removal and biomass generation.

Y g biomass (COD)

1 g substrate (COD) +

( 1 - Y ) g O2 (COD)

Example: The use of different parameters for the assessment of the yield coefficient.