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Wastewater & sludge characterization
Size of organic contaminants in wastewater
Source: Wastewater Engineering, Metcalf & Eddy, 2002
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Classification of solids found in wastewater
Source: Wastewater Engineering, Metcalf & Eddy, 2002
Organic matter in wastewater
• composed of:
for example:
carbon (C),
C18H19O9N
hydrogen (H),
If the organic matter is
oxygen (O)
oxidized, the consumed
sometimes (N)
amount of oxygen (the
BOD, COD, TOD
• consists of:
analyses) or the produced
proteins (40-60%),
amount of carbon dioxide
carbohydrates (25-50%)
(the TOC analysis) can be
oils and fats (8-12%)
measured
urea
many synthetic org. molecules
• analyses of organic matter:
collective or aggregate
individual
Source: Wastewater Engineering, Metcalf & Eddy, 2002
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Analyses for organics in wastewater
and their inter-relationship
Source: Wastewater Treatment, Henze et al., 1996
Theoretical oxygen demand (ThOD)
Expressed as amount of oxygen required for
full oxidation of organic matter present in wastewater
Chemical oxidation equation
CcHhOoNnPpSs + (c + 0,25h – 0,5o + 1,25 n + 1,25 p +1,5s)*O2
cCO2 + (0,5h – 0,5n – 1,5p – s)*H2O +
nNO3- + pPO4-3 + sSO4-2 + (n+ 3p +2s)*H+
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Biochemical oxygen demand (BOD)
Expressed as amount of oxygen required by the micro-organisms
for oxidation of organic matter and ammonia
Unit mg O2/L
Used to determine:
• the appr. amount of O2 to biologically stabilize the organics in wastewater
• the size of wastewater facilities
• efficiency of some treatment processes
• compliance with wastewater discharge permits
Carbonaceous biochemical oxygen demand (CBOD)
Principles of BOD test
Portion of the organics is Some of the organics are When organics
oxidized to end products converted into new cells become exhausted, the
to obtain energy for cell using part of the energy new cells begin to
maintenance and the released during oxidation consume their own cell
synthesis of the new cell tissue to obtain energy
tissue for cell maintenance.
Oxidation
CHONPS + O2 + bacteria CO2 + H2O + NH3 + end products + energy
Synthesis
CHONPS + O2 + bacteria + energy new cell tissue
Endogenous respiration
new cell tissue + 5O2 5CO2 + 2H2O + NH3
Carbonaceous BOD: The oxygen needed for oxidation of only carbon
present in the wastewater is called
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Nitrogenous biochemical oxygen demand (NBOD)
Conversion of ammonia to nitrite (by Nitrosomonas)
2NH4+ + 3O2 2NO2- + 4H+ + 2H2O + energy
Conversion of nitrite to nitrate (by Nitrobacter)
2NO2- + O2 2NO3- + energy
Overall conversion of ammonia to nitrate
NH4+ + 2O2 NO3- + 2H+ + H2O + energy
• 2 moles of O2 for nitrification of 1 mole of N
• NCOD = 4.57 gO2 per 1gN
• 2 moles of H+ produced: reduced sewage pH
Nitrogenous BOD:
The oxygen needed for oxidation of ammonia
present in the wastewater to nitrate.
Source: Wastewater Engineering, Metcalf & Eddy, 2002
Typical CBOD and NBOD curve
BODt = BOD (1-e-k·t)
k = k 20°C · t-20°C
k = 0,12 - 0,46 d-1
(typical 0,23 d-1)
Standard BOD test at 20°C and 5 days
BOD5 = BOD (1-e-0,23·5) = 0.68 BOD
Source: Wastewater Engineering, Metcalf & Eddy, 2002
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Chemical oxygen demand (COD)
Expressed as amount of oxygen required for chemical oxidation of organic
matter by a strong oxidant (permanganate or dichromate) in acid solution.
Unit mg O2/L
(consumption of permanganate or dichromate is converted into
An equivalent oxygen demand (amount of oxygen which will be consumed if the
oxidation would have taken place by using oxygen)
Chemical oxygen demand (COD)
In general COD = BOD because:
• many organic substances which are difficult to oxidize
biologically can be oxidized chemically
• inorganic substrates that are oxidized by the dichromate
increase the apparent organic content of the sample
• certain organic substances may be toxic to the
microorganisms used in the BOD test
• high COD values may occur because of the presence of
inorganic substances with which dichromate can react
In general COD = ThOD because:
• oxidation of ammonium and ammonia released by
oxidation of organic nitrogen does not take a place in the
standard COD test.
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Total oxygen demand (TOD)
Amount of oxygen needed for oxidation of organics at a high
temperature and use of suitable catalyst
Unit mg O2/L
TOD > COD for the same sample
Total organic carbon (TOC)
The difference between the carbon
dioxide concentration obtained
before and after oxidation of
Example
organics by heating.
Unit mg C/L
• TOC does provide the amount of
carbon atoms
• TOC does not give information on
the state of oxidation of C atoms
• TOC does not give information on
how much oxygen should be used
for oxidation
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Alkalinity
Conductivity
Pathogens
Temperature
Odor and color
COD fractionation
• Not used for the day-to-day management control and operation of WWTPs
• Used for
design
operational tests
optimization
modeling CCOD
S X SI XI
S S
• Soluble = Dissolved
• Particulate = Suspended
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COD, N and P fractionation
COD
Fraction of N and P in municipal wastewater
(in g/g COD)
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STOWA influent characterization procedure - 1
Characterization of the organic fractions of the influent
The total COD in the influent is a sum of the COD of soluble (CODfilt,inf ) and particulate fractions
(CODpart,inf ):
CODtot,inf = CODfilt,inf + CODpart,inf (5.1)
Soluble fraction of the COD consists of following components,
CODfilt,inf = SA + SF + SI (5.2)
while the particulate fraction is represented by:
CODpart,inf = XI + XS + (XH + XPAO + XPHA + XGLY + XAUT ) (5.3)
For simplicity the contribution of particulate components of the active biomass present in the
settled sewage and the supernatant of the primary thickeners to the total COD is neglected. For
the modeling purposes a very low value is assigned to these components (table 5.4). Therefore eq.
5.3 can be written as:
CODpart,inf = XI + XS (5.4)
STOWA influent characterization procedure - 2
Volatile fatty acids COD is directly measurable organic fraction of the influent COD and is
presented as SA:
SA = CODVFAs (5.5)
Readily biodegradable substrate SS was introduced in the ASM1. In ASM2 it is replaced by:
SF = SS - SA (5.6)
Introducing eq. 5.6 to eq. 5.2, the fermentable, readily biodegradable organic substrates SF can be
expressed as:
SF = CODfilt,inf - (SA + SI) (5.7)
The SI in the influent is not affected by the treatment processes and, therefore, leaves the
treatment plant with the effluent. This inert fraction can be calculated using the effluent COD
measured after filtration (CODfilt,eff). The CODfilt,eff has to be corrected with a factor 0.9 due to
some production of SI during the treatment process. For presence of BOD in the effluent the SI is
further reduced by the factor 1.5 BOD5,eff: The factor 1.5 is a conversion factor of BOD5 to COD.
SI = 0.9 · CODfilt,eff - 1.5 BOD5,eff (5.8)
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STOWA influent characterization procedure - 3
Finally, by combining eq. 5.7 with eq. 5.8, SF can be calculated using directly measurable
parameters:
SF = CODfilt,inf - 0.9 · CODfilt,eff + 1.5 BOD5,eff - SA (5.9)
In ASM1, the slowly biodegradable particulate substrate XS is given as the difference between
the biodegradable fraction of COD (BCOD) and the readily biodegradable substrate SS:
XS = BCOD - SS (5.10)
The routine BOD measurements are not recommended to be used for the estimation of the BCOD
due to the facts that the BOD5 measurement underestimates the BCOD, and that the BOD20
measurement is not yet reliable enough. The Dutch guidelines recommend the estimation of
BCOD via determination of the total BOD (BODtot) from the BOD measurement by the best fit of
the BOD-curve to the measured data. The following equation is recommended:
BODtot = BODt /(1 - e -kt) (5.11)
where kBOD is the constant which varies from plant to plant and is in the range 0.15-0.6 d-1 for
domestic sewage (Roeleveld and Kruit, submitted). Description of the determination of the kBOD
from the BOD test is given elsewhere (Roeleveld and Kruit, submitted). It is now possible to
calculate the biodegradable COD from the total BOD taking into account the initial value of
RBOD will be somewhat higher than the BODtot calculated by eq. 5.11. This is due to the
conversion of the fraction of BCOD into an inert fraction during the course of the BOD test. This
is corrected by the factor YBOD which falls in the range of 0.1-0.2 (Roeleveld and Kruit,
submitted).
STOWA influent characterization procedure - 4
The BCOD can be expressed as follows:
BCOD = BODtot /(1 - YBOD) (5.12)
The XS can be calculated from eq. 5.10 and 5.12:
XS = {[BODt /(1 - e -kt)]/(1 - YBOD)} - SS (5.13)
Finally, the inert particulate organic material is calculated from the eq. 5.4 and 5.13:
XI = CODpart,inf - XS (5.14)
The concentration of total suspended solids (XTSS) in the influent is estimated from following
equation:
XTSS = 0.85 CODpart,inf (5.15)
Characterization of the N and P fractions in the influent
In ASM2 the nitrogen compounds are for simplicity represented only with its soluble
components which are directly measurable parameters: ammonium plus ammonia
nitrogen plus Kjeldahl nitrogen (SNH4) and nitrate and nitrite nitrogen (SNO3).The
phosphate compounds are represented also as soluble phosphorus (SPO4). A small
correction has to be made for an eventual poly-P fraction (XPP) in the influent.
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Sludge volume index (SVI)
Def.1: SVI is the reciprocal sludge concentration in the sludge phase
after o,5 hour of settling in a cylinder glass.
SVI = 1/X0,5 Unit mL/gSS
Def 2: SVI represents the volume occupied millimeters by 1 g of
settled sludge
• SVI provides some information on flocculation and settling
characteristics of the activated sludge
• The lower the SVI is, the better flocculation and settling of
sludge
• By stirring the sludge during the settling the SSVI can be
determined
• SVI of 100 mL/g usually satisfactory indicator of good
performance of activated sludge system
• Sludge density index (SDI) is the sludge concentration in the
sludge phase after settling of 30 min (= X0,5)
35 mL/g < SVI < 220 mL/g
Important: Example - If sludge concentration
of 10 kg/m3 would not settle at all in 30 min,
the SVI would be 100!
To avoid this, diluted SVI (DSVI) was
introduced in 1993 (Jenkins et al.)
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Example of calculation of SVI
35 mL/g < SVI < 220 mL/g
Important: Example - If sludge concentration of 10
kg/m3 would not settle at all in 30 min, the SVI would
be 100!
To avoid this, diluted SVI (DSVI) was introduced in
1993 (Jenkins et al.)
Oxygen utilization rate (OUR)
The oxygen consumption (in g O2) by the microorganisms (in kg VSS) per
hour
Unit gO2/kgVSS.h
• Provides information on sludge condition
OUR of 20-40 gO2/kgVSS.h:
sludge is activated (many living organisms)
sufficient substrate (organic matter) is presen
OUR of 5-10 gO2/kgVSS.h:
the sludge is poisoned
no easily degradable organic matter is present
the sludge has been stabilized
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Example of OUR equipment (BOM)
Example: results of BOM
O2concentration [mg/L]
1,9
1,8
1,7
1,6
1,5
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
Time [min]
120
Oxygen respiration rate [mgO2/L.h]
140
30C
100
Total oxygen consumption [mgO2/L]
112
80
20C 84
60 3.44 mgO2/L.C
56
10C
40
28
20
5C
0
0
0 5 10 15 20 25 30 35
0 20 40 60 80 100 120 140 Temperature [C]
Time [min]
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