Nitrification

BIOLOGICAL
NITRIFICATION
Carlos M. Lopez Vazquez
based on a presentation from:
Prof. George Ekama
Dr. Mark Wentzel
Water Research Group
Dept of Civil Engineering
University of Cape Town

Learning Objectives
After the successful completion of this course the
student will be able to:
To critically determine and analyze quality and
quantity characteristics of ww originating from urban
environments as a basis for the design, control and
operation of sewage treatment facilities
nitrification..
nitrification
To discuss the physical, chemical and biological
processes applied for sewage purification and the
complex interactions among them occurring in wwt
systems achieving nitrification.

Learning Objectives
After the successful completion of this course the
student will be able to:
To apply the knowledge on biological wastewater
treatment processes and engineering on the design
and critical assessment of wwt systems and
configurations for nitrification as a function of
environmental, operating and wastewater conditions
and characteristics
characteristics.

OUTLINE
1. INTRODUCTION
2.
2 NITRIFICATION KINETICS
Growth behaviour
Endogenous respiration

3. PROCESS KINETICS
Effluent ammonia concentration
Minimum sludge age for nitrification

OUTLINE
4. FACTORS INFLUENCING
NITRIFICATION
Wastewater source
Temperature
Unaerated zones
Dissolved oxygen concentration
Cyclic flow and load
pH and alkalinity
5. NUTRIENT REQUIREMENTS FOR
SLUDGE PRODUCTION

OUTLINE
6. DESIGN CONSIDERATIONS
Effluent TKN concentration
Nitrification capacity

7. DESIGN PROCEDURE

Effect of nitrification on reactor pH

Minimum sludge age for nitrification
W t
Wastewater
t N concentrations
t ti
Nitrification process behaviour.

1. INTRODUCTION
TEXT BOOK NN-CYCLE
NH3

-3
-2

N-fixation

-1

N2 (gas)

Nitrification

+1
+2

HNO2
(NO2-)

HNO2

Denitrification

HNO3
(NO3-)

+3
+4
+5

1. INTRODUCTION
NITRIFICATION

The biological oxidation of free and saline (NH3

and NH4+) ammonia ((FSA)) byy two g
groups
p of
obligate aerobic autotrophic organisms.

Catabolism:
Ammonia oxidizing organisms (AOO, AOB)
NH4+ + 3/2O2 NO2- + H2O + 2H+ + Energy
Nitrite oxidizing organisms (NOO, NOB)
NO2- + 1/2O2 NO3- + Energy

1. INTRODUCTION
Grrowth rate [1//d]

NITRIFICATION

AOOs [NH4 to NO2]

NOOs [NO2 to NO3]

~20--25oC:
Tsewage< ~20
~20
20--25oC
Temperature

[oC]

AOO grow slower

NH4 oxidation is
limiting step

1. INTRODUCTION
NITRIFICATION

Anabolism:
Energy
Energ + NH4+ + CO2 + H2O Biomass
Biomass Yield of autotrophs is very low:
YA~0.10 mgVSS/
mgVSS/mgFSA
mgFSA--N nitrified
Since normally NOOs faster than AOOs,
then: no NO2- built up, and nitrification
can be modelled as a single step.

1. INTRODUCTION

NITRIFICATION
Overall process stoichiometry by autotrophic
nitrifying bacteria (ANB):

NH4+ + 2HCO3- + 2O2

NO3- + 2CO2 + 3H2o
Therefore, per mgFSA
mgFSA--N nitrified:
4.57 mgO utilized (64mgO/14mgN)
(2x50gCaCO3)/14
7.14 mg/l as CaCO3 consumed (2x50gCaCO
1 mgNO3--N generated.

2. NITRIFICATION KINETICS

2.1. GROWTH
Based on Monod growth kinetics:
(1) ANB biomass (XBA) generated is a fixed
fraction (YA) of FSA (Na) nitrified:

(2) Specific growth rate (

(AT) related to bulk
liquid FSA concentration (Na) - Monod

2. NITRIFICATION KINETICS
2.1. GROWTH

Am = 0.45/d
0 45/d
Kn =1 mgN/l
YA = 0.10
mgVSS/
mgFSA--N
mgFSA

If Na>4mg/L, ANB nitrify at maximum rate ((

A),
but its difficult to get low Na<1.0 mgN
mgN/l/l

2. NITRIFICATION KINETICS
2.1. GROWTH

FSA (Na) utilization rate, NO3- (Nn) generation

rate and nitrification oxygen utilization (On)
rate
t are lilinked
k d tto ANO bi
biomass (XBA)
growth rate:

2. NITRIFICATION KINETICS

2.1. ENDOGENOUS RESPIRATION

ENDOGENOUS RESPIRATION is modelled in the
same way in both steady state and simulation
models as endogenous respiration for OHOs in
steady state model, viz:
bAT = specific
endogenous mass
l
loss
rate
t att T [oC]
= 0.04 /d at 20oC

3. PROCESS KINETICS
Derived from mass
balances over AS system
(1) Mass balance on XBA:
=0
(2) Solving for Na (= Nae) yields:

at steady
state

Independent
of YA and Nai

MINIMUM SLUDGE AGE

Plotting Nae vs Rs
(1)Above
(1)
Above certain Rs,
Nae is veryy low.
(2) As Rs decreases,
Nae increases.
(3) When Nae = Nai,
Rs Rsm.
Rsm = minimum sludge age for nitrification.
Sludge age (Rs) is the most important design parameter for
systems required to nitrify!

MINIMUM SLUDGE AGE

(1) If Rs < Rsm, no nitrification.
(1)If
(2)If
(2)
If Rs > 1
1.3
3 x Rsm, nitrification almost
complete.
Setting Rs = Rsm and Nae=Nai yields for Rsm
and with
KnT << Nai

So Rsm depends mainly on maximum

specific growth rate of AOB - Am

EXERCISE: MINIMUM SLUDGE AGE

A WWTP is to be designed for nitrification at T=20oC, if the Rs
is 10 days and given:
Am20=0.30d-1,
bA,20=0.04
=0 04 d-1,
Kn,20=1mg/L
=1mg/L,,
- Can nitrification be expected?
- What is the minimum required Rs for nitrification?
- What would be the effluent FSA concentration (Nae)?

10

NITRIFIER Am
Depends on many factors:
((1)) Inhibitors
b to s in wastewater
aste ate (amines,
(a
es, metals,
eta s,
salts).
(2) Wastewater temperature (T, Am).
(3) Wastewater pH (pH, Am).
((4)) Reactor DO concentration ((DO,
, Am)
).
(5) AOB and NOB populations selection.
Therefore Am is considered a wastewater
characteristic rather than kinetic constant

FACTOR OF SAFETY ON Am
To ensure nitrification, Am is decreased by
20-30%):
a factor of safety, Sf (1.2 1.3; or 20Rsm =

1
______________
AmT /Sf - bAmT

Effluent FSA
conc is given by:

(1) ensures Rs > Rsm,

(2) covers uncertainty in Am Nae = KnT / (Sf - 1)
(3) ensures low effluent FSA concentration
and near complete nitrification.

11

4. FACTORS AFFECTING
NITRIFICATION
(1)
(2)
(3)
(4)
(5)
(6)

wastewater magnitude of Am20,

temperature,
unaerated zones in reactor,
aerobic reactor DO concentration,
cyclic flow and load conditions
reactor pH.

4.1. WASTEWATER SOURCE

Already mentioned - Am20 varies between
different wastewaters then it is considered a
wastewater
t
t characteristic
h
t i ti rather
th than
th a
kinetic constant.
Ideally should be measured on wastewater.
Am20 values range between 0.3 - 0.75 /d.
bA20 is accepted to stay constant (0.04/d).

12

4.2. TEMPERATURE
Nitrifier kinetic constants Am20, bA20 and Kn20
all dependent on temperature:
(T--20) ; =1.123
(1) AmT = Am20(n)(T
n
(T--20) ; =1.123
(2) KnT = Kn20(n)(T
n
(T(T
20)
(3) bnT = bn20(b)
; b=1.029.
n=1.123 is equivalent to a 50% reduction
every 6oC if 0.45/d at 20oC, then is 0.23 at
14oC.

4.2. TEMPERATURE
Halving Am by 6oC decrease, doubles
minimum sludge age for nitrification (R
(Rsm).
)
Halving Kn by 6oC decrease does not affect
Rsm, but does affect effluent FSA conc.
Overall effect of Am and Kn decrease is
effluent FSA increase:
Nae

13

4.2. TEMPERATURE

Am halves by 6oC decrease, doubling minimum

sludge age for nitrification (R
(Rsm).
Rsm,14=7.6 d

>>

Rsm,22=2.7d

>>

Rsm,30=1d

SRTm,30 SRTm,22 SRTm,14

50

Am,20 = 0.33/d
Kn,20 =1 mgN/L

45

Amm
monia [mg/L]

40
35
30
25

14oC
22oC

20

30oC

15
10
5
0

10

12

14

16

SRT (d)

4.3. UNAERATED ZONES

Formulated on 3 assumptions:
((1)) Nitrifiers onlyy g
grow in aerobic zone
(2) Nitrifiers endogenous respiration occurs
in all zones at same rate (controversial)
(3) Proportion of ANOs in VSS is the same
in all zones
zones..

14

4.3. UNAERATED ZONES

From 3 assumptions it can be shown that:

fxt = unaerated mass fraction,

= fraction of total mass of sludge in
system
y
in unaerated zone(s).
( )
= 0 for fully aerobic system.
Similarly,

4.3. UNAERATED ZONES

Alternatively, the maximum unaerated
sludge mass fraction fxm allowed at a
sludge age of Rs to ensure nitrification
with a safety factor of Sf is:
fxm = 1 -

Sf (bAT + 1/Rs)

AmT
and the effluent FSA
conc can be given by
Nae = KnT / (Sf - 1)

15

4.4. DO CONCENTRATION
Effect of DO on Am is formulated as -

O = DO conc in mixed liquor

KO = Monod half saturation conc for DO
= 0.3 to 2 mgO/L (depends on floc
size, mixing).
If reactor DO < KO, nitrification rate is
less than half the maximum.

4.5. CYCLIC FLOW AND LOAD

(1) Average effluent FSA under cyclic flow and load is
higher than under steady state effluent FSA.
(2) So nitrification efficiency decreases under cyclic
flow and load compared with steady state - the
higher the variation, the lower the efficiency.
(3) Cyclic flow and load has similar effect as
decreasing sludge age closer to Rsm
(4) So iincrease
ncrease Rs to compensate for cyclic flow and
load and keep effluent FSA low.

16

4.6. pH and ALKALINITY

Nitrification
consumes 7
7.14
14
mg/l Alk as CaCO3
per mgN/l FSA
nitrified.
If mixed liquor alkalinity decreases
below 40 mg/l as CaCO3, mixed
liquor pH decreases below 7.

4.6. pH and ALKALINITY

Nitrification is
very sensitive to
pH.
Optimum pH
range is 77-8.
In low alkalinity WW
WW, nitrification can inhibit
itself due to H+ release, which reduces mixed
liquor pH below 7, which reduces Am.

17

4.6. pH and ALKALINITY

If influent Alkalinity = 200 and 24 mgN/l
mgN/l
FSA is nitrified,
th effluent
then
ffl
t Alk
Alkalinity
li it = 200
7.14x24=29 mg/l.
Less than 40!!! so mixed liquor pH will
decrease below 7!
In this event
event, either
Introduce anoxic zones to denitrify nitrate
and recover half Alk lost, or
Dose lime to keep pH > 7.0.

5. N REQUIREMENTS FOR
SLUDGE GROWTH

(1) About 15
15--20% of
influent TKN is required
for AS sludge growth
(Ns).
(2) Ns decreases with Rs
and settled WW.
(3) Influent biodeg OrgN
adds to FSA pool in
reactor and nitrified.

Nte
NC

NS

Nti

18

EXERCISE: MINIMUM SLUDGE AGE

The WWTP whose operation you have verified experiences a
drop in temperature from 20 to 12oC during winter. If the Rs is
6d, the FSA concentration is 60 mgN/L,
mgN/L, and alkalinity is 500 eq
as mg CaCO3/L and given:
Am20=0.30d-1, bA,20=0.04 d-1, and Kn,20=1mg/L
=1mg/L..
Qi= 20MLD
Total MXV=52,000 kg VSS
Xv=4.5 kg VSS/m3

Questions:
- What is the minimum Rs for nitrification at 12oC?
- Will nitrification occur?
- What will be the effluent FSA concentration ((N
Nae)?
- How much N&P are required for growth (Ns and Ps)?
- Is alkalinity sufficient to achieve full nitrification?
-

6. DESIGN CONSIDERATIONS
6.1. FATE OF INFLUENT TKN
Released as
FSA and
adds
dd tto
FSA pool.

Some taken up
for growth,
rest nitrified
to nitrate.
Effluent FSA Effluent TKN
Nte=Nae+Nousi
(Nae) low.

Escapes
with
effluent

Included in
MXv due to
Ns

19

6. DESIGN CONSIDERATIONS
6.2. NITRIFICATION CAPACITY
Nitrification capacity ((N
Nc) = Concentration of
nitrate per litre influent flow generated by
Includes
nitrification (mgN
(mgN/L).
/L).
Noupi
Nc = Nti Ns Nte
Ns = fn (Vp.Xv)/(Rs.Qi)
fn = N content of VSS
Nte= Nae + Nousi ;

7. DESIGN PROCEDURE
Calculation of sludge age (Rs) and unaerated
sludge mass fraction (fxt) most important part of
design procedure!
With WW characteristics known and Rs and fxt
selected:
(1) Calculate influent N concentrations (N
(Noi, Nousi,
Noupi).
(2) Calculate effluent N ((N
Nouse = Nousi).
(3) Calculate N for sludge production (Ns).

20

7. DESIGN PROCEDURE
(4) Calculate Rsm.
(5) If Rs < Rsm no nitrification occurs, then:
a) Effluent Nitrate (N
(Nne) = 0.
b) Effluent FSA (Nae) = Nti Ns - Nousi
equivalent to FSA available for nitrification (Nan).

c) Effluent TKN ((N

Nte) = Nae + Nousi = Nti Ns
d) Nitrifier sludge mass MXBA = 0
e) Nitrification oxygen demand MOn = 0

7. DESIGN PROCEDURE
(6) If Rs > Rsm
sm,, nitrification occurs, then:
a) Effluent FSA =
If Nae is negative or >Nan, set Nae = Nan
b) Effluent TKN: Nte
mgN/L)
/L)
t = Nae + Nouse (mgN
c) Effluent Nitrate: Nne = Nan Nae (mgN
mgN/L)
/L)
= Nti Ns Nte (mgN
mgN/L)
/L)

21

7. DESIGN PROCEDURE
(6) If Rs > Rsm , nitrification occurs, then:
Analogous to mass of ordinary heterotrophic
organisms (OHOs) in reactor, mass of
ANB is:
MXBA = (Qi Nne) YARs/(1+bATRs)
where Qi Nne = mass of nitrate generated
= Nne (Qe + Qw) mgN
mgN/d
/d
Nitrification oxygen demand (mgO
(mgO/d)
/d) =
MOn = 4.57 (Qi Nne) mgO
mgO/d.
/d.

EXAMPLE WW: COD - RAW

The following parameters have been determined for a given raw

(non--settled) WW:
(non
Total COD = 750 mg/L
Filtered COD (0.45
(0 45 mm) = 199 mg/L
fSusi = Susi/Sti = 0.07; and fSupi = Supi/Sti = 0.15
- What are the different organic concentrations in the influent?

750
146
438

53
113

199

551

22

EXAMPLE - RAW WW
60*

mgN/l

45*

Nousi=Effl TKN
TKN--FSA

1.8** 48.5*

0.45 filtered - Sol

0.45
TKN =48.5 mgN
mgN/l
/l
fNous= Nousi/Nti= 0.03

From COD
fractionation
Measured on *influent and **effluent

Noupi= fnSupi/fcv

EXAMPLE - RAW WW
60*

mgN/l

Nousi=Effl TKNTKN-FSA

15.0
45*

1.7

39
3.9

1.8** 48.5*
7.6

0.45 filtered - Sol

0.45
TKN =48.5 mgN/l
fNous= Nousi/Nti= 0.03
Nousi=0.03x60
=1.8 mgN/l

11.5

Noupi= fnSupi/fcv
= 0.1x113/1.48

Measured on *influent and **effluent

= 7.6 mgN/l

23

EXERCISE WW: COD

- SETTLED

For a given settled WW, the following parameters have been

determined :
Total COD = 450 mg/L
Filtered COD (0.45
(0 45 mm) = 199 mg/L
fSusi = Susi/Sti = 0.117; and fSusi = Supi/Sti = 0.04

- What are the different organic concentrations in the influent?

450
53

146
233

18

199
251

EX - SETTLED WW
51*

mgN/l

Nousi=Effl TKN
TKN--FSA
0.45 filtered - Sol
0.45
TKN =48.5 mgN
mgN/l
/l

45*

48.5* fNous= Nousi/Nti= 0.035

1.3

1.2
2.5

Noupi= fnSupi/fcv

Measured on *influent and **effluent

24

EX - SETTLED WW
51*

mgN/l

Nousi=Effl TKN
TKN--FSA

6.0
45*

1.7
1.3

1.8** 48.5*

0.45 filtered - Sol

0.45
TKN =48.5 mgN
mgN/l
/l
fNous= Nousi/Nti= 0.035
Nousi=0.035x51

1.2

=1.8 mgN/l
mgN/l

2.5

Noupi= fnSupi/fcv
= 0.1x18/1.48

Measured on *influent and **effluent

= 1.2 mgN/l
mgN/l

DESIGN EXERCISE
For the raw wastewater flowrate at 16oC and 10d SRT, determine and answer:
1) Can the system nitrifify
nitrifify?
?
2) What is the ammonia effluent concentration ((Nae
Nae)?
)?
3) What is the TKN concentration in the effluent (Nte
(Nte)?
)?
4) How much ammonia nitrogen is available for nitrification (Nc
(Nc)?
)?
5) What is the expected nitrate concentration in the effluent?
6) What will be the increase in biomass concentration due to nitrifying
biomass?
7) How will the oxygen requirements increase due to nitrification ((Fon
Fon)?
)?
8) What will be the alkalinity consumption due to nitrification?
Assume: A20 = 0.45 dd-1, Kn20=0.5 mg/L.

25

DESIGN EXAMPLE FROM

TEXT BOOK
Following the design procedure with the
example raw and settled wastewaters in
the notes at 14 and 22oC -

DESIGN RESULTS 14oC

Fully aerobic raw and settled wastewater.

Minimum sludge age for nitrification 5d.
Effluent TKN & NO3 concs virtually the same.
Influent TKN and Ns lower for settled than raw.

26

DESIGN RESULTS 22oC

Fully aerobic raw and settled wastewater.

Minimum sludge age for nitrification 2d.
Effluent TKN & NO3 concs virtually the same.
Influent TKN and Ns lower for settled than raw.

NITRIFICATION:
INFLUENCE ON SYSTEM
((1)) Sludge
g age:
g Nitrification requires
q
Rs>Rsm, so
has major influence on selection of Rs.
(2) Reactor volume and sludge production: For the
same sludge age, no influence. Nitrifiers < 4%
of VSS mass in reactor (TKN load << COD
load and YA<< YH).
) However
However, nitrification
usually needs longer Rs so reactor volume
larger and sludge production lower.

27

NITRIFICATION:
INFLUENCE ON SYSTEM
(3) Oxygen demand (OD): Increases significantly
with nitrification by about 40
40--60% of COD
removal OD depending on influent TKN/COD
conc ratio.
Also, if nitrification requires longer sludge age,
COD removal OD increases.
(4) In low DO conditions
conditions,, COD removal OD takes
preference and nitrification will be partial DO
should be >2 mgO/l.

NITRIFICATION:
INFLUENCE ON SYSTEM
(5) Effluent quality: No difference in COD, low
FSA high
FSA,
hi h nitrate,
it t reduced
d
d alkalinity,
lk li it llower
pH possibly aggressive to concrete
surfaces.
(6) When nitrification can take place, by design
or accident, include denitrification and
hydraulic control of sludge age, especially for
warm WW, to reduce nitrate and oxygen
demand, recover alkalinity, raise pH and
minimize rising sludge in SST.

28

SUMMARY (1)
(1) Maximum specific growth rate of nitrifiers (
(Am20)
fixes the sludge age of the AS system.
(2) Unaerated zones, low WW temperature and
cyclic flow and load increase sludge age over
minimum for nitrification.
(3) Selection of unaerated mass fraction and sludge
age is the most important decision in the design for
nitrification.
(4) At fixed sludge age, nitrification has negligible
effect on sludge production.

SUMMARY (2)
(5) Nitrification increases oxygen demand by
40 to 60% over that for organic removal.
(6) Wh
When nitrification
it ifi ti can ttake
k place,
l
iinclude
l d
denitrification to recover half the Alkalinity
and oxygen used in nitrification and minimize
rising sludge in the SST.
(7) Control sludge age hydraulically by
wasting directly from the reactor to fix sludge
age and guarantee nitrification rather than
control reactor concentration (system fails via
high ESS rather than on nitrification).

29