Biological Nutrient removal

Nitrogen
 Biological Nitrification
■ Nitrification
– NH4-N oxidize to NO2-N
– NO2-N oxidize to NO3-N

– Need of nitrification arise from water quality concerns:

• NH4-N if discharge in water consume DO, toxic to fish
• Eutrophication
• Water re-use application including ground water discharge
 Biological Nitrification
■ Suspended growth
– Single-sludge
process

– Two-sludge process
 Biological Nitrification
■ Microbiology
– Aerobic autotrophic bacteria
• NH4-N oxidize to NO2-N Nitrosomonas
Nitrosococcus, Nitrosospira, Nitrosolobus, and Nitrosorobrio

• NO2-N oxidize to NO3-N Nitrobacter

Nitrococcus, Nitrospira, Nitrospina, Nitroeystis
 Biological Nitrification
■ Stoichiometry of biological nitrification

2 NH 4  3O2    2 NO2  4H   2H 2O Nitroso-bacteria

  Nitro-bacteria
2 NO  O2    2 NO
2 3

2 NH 4  2O2    NO3  2 H   H 2O

4.57 g O2/g N oxidized

3.43 g O2/g nitrite production

1.14 g O2/ NO2 oxidized
 Biological Nitrification
■ Alkalinity requirement

NH 4  2 HCO3  2O2    NO3  2CO2  3H 2O

7.14 g of alkalinity as CaCO3 for each g of NH4-N (as N)

[2 x (50 g CaCO3/eq)/14]

■ NH4 assimilation
4CO2  HCO3  NH 4  H 2O    C5 H 7O2 N  5O2
 Biological Nitrification
■ Overall nitrification
NH 4  1.863O2  0.098 CO2    0.0196 C5 H 7O2 N  0.98 NO3  0.0941 H 2O  1.98 H 

For each g of NH4 as N

4.25 g O2 utilized
0.16 g of new cell formed
7.07 g of alkalinity as CaCO3 removed
0.08 g of inorganic carbon are utilized in the formation of new cell
 Biological Nitrification
■ Growth kinetics (NH4 oxidation vs NO2 oxidation)
– Ammonia oxidation kinetics are rate limiting
– Designs are based on saturation kinetics of ammonia
  nm N 
 n     k dn
 Kn  N 
µn = specific growth rate of nitrifying bacteria, g new cells/g cells.d
µmn = max. specific growth rate of nitrifying bacteria, g new cell/g cell.d
N= nitrogen concentration, g/m3
Kn = half-velocity constant, substrate concentration at one-half the
maximium specific substrate utilization rate, g/m3
kdn = endogeneous decay coefficient for nitrifying organisms, g VSS/gVSS.d
 Biological Nitrification
■ µn for nitrifying organisms< µH for heterotrophic
– Longer SRT for nitrifying activated sludge are required
• 10 -20 days at 10oC
• 4-7 days at 20oC
• Above 280C - both nitrite oxidation and NH4 oxidation
should be considered – low SRT
■ DO concentration
– Nitrification rates increase up to DO concentration 3-4 mg/L
  nm N  DO 
 n     k dn
 K n  N  K o  DO 
DO= dissolved oxygen concentration, g/m3
Ko = half-saturation coefficient for DO, g/m3
 Biological Nitrification
■ Environmental Factors
– pH
• Rates decline at pH below 6.8
• Optimum: pH = 7.5-8.0
• Alkalinity is added in reactors to maintain pH
– Lime, soda, sodium bicarbonate, MgOH

– Toxicity
• Sensitive to wide range of organic and inorganic compounds
– Nitrifier – good indicator of the presence of organic toxic
compounds at low concentration
– Amine, proteins, tannins, phenolic compounds, alcohols,
cyanates, ethers, carbamates, benzene
 Biological Nitrification
– Toxicity
• Metals
– Concern for nitrifier
» Complete inhibition of ammonia oxidation at
» 0.25 mg/L Ni
» 0.25 mg/L Cr
» 0.1 mg/L Cu
• Un-ionized Ammonia
– Nitrification also inhibited by
» un-ionized ammonia
» Un-ionized nitrous acid (HNO2)
» [NH4+-N] at 100 mg inhibit NH4+-N oxidation
» [NH4+-N] at 20 mg/L inhibit NO2--N oxidation
 Biological Denitrification
■ Biological reduction of nitrate to nitric oxide (NO),
nitrous oxide (N2O) and nitrogen gas is called
denitrification

■ Nitrogen removal
• involve nitrification and denitrification

• Eutrophication
• Ground water must be protected against elevated NO3
(ground water recharage)
 Biological Denitrification
■ Process description
 Biological Denitrification
■ Process description
Modified Ludzak-Ettinger (MLE) process

Nitrate feed

Influent Effluent Influent Effluent

Aerobic/ Aerobic/ Anoxic
Anoxic
nitrification nitrification

Return activated sludge Return activated sludge

Sludge
Sludge
(a) (b)

(a) Substrate driven (preanoxic denitrification) and (b) endogenous driven (postanoxic denitrification)

Pseudomonas
 Biological Denitrification
■ Process description
– Other pathway for biological nitrogen removal
• Ammonia  N2
– by novel autotrophic bacteria under anaerobic conditions
(Anammox process)
» Planctomycetales
– By heterotrophic-nitrifying bacteria under aerobic
conditions
 Biological Denitrification
■ Stoichiometry
– Organic substrate oxidation using nitrate as electro acceptor
– Nitrate reduction
• NO3-NO2-NON2ON2
– Electron donor
• bsCOD in the influent of wastewater
• bsCOD producing during endogenous decay
• An exogenous source such as methanol or acetate
 Biological Denitrification
Wastewater:
C10 H19O3 N  10 NO3  5 N 2  10CO2  3H 2O  NH 3  10OH 
Methanol :
5CH 3OH  6 NO3  3N 2  5CO2  7 H 2O  6OH 
Acetate:
5CH 3COOH  8 NO3  4 N 2  10CO2  6 H 2O  8OH 
1 equivalent of alkalinity produced/ equivalent of NO3-N reduced
= 3.57 g of alkalinity (as CaCO3) production / g of Nitrogen reduced

One half of the amount of alkalinity destroyed by nitrification can

be recovered by denitrification
 Biological Denitrification
■ An important design parameter
– Amount of bsCOD or BOD needed to provide a sufficient amount
of electron donor for nitrate removal.
2.86
g bsCOD/g NO3  N 
1  1.42Yn
Y
Where Yn 
1 (k dn ) SRT

Yn = net biomass yield, g VSS/g bsCODr

 Biological Denitrification
■ Growth kinetics
– Biokinetic equations to describe bacteria growth and substrate
utilization are similar to those for aerobic heterotrophic bacteria
• Portion of microorganisms can used both oxygen and nitrate
as electro acceptor
– Substrate utilization rate in anoxic zone

kXS
rsu  
Ks  S
Where η= fraction of denitrifying bacteria in the biomass, g VSS/g VSS
η = 0.2-0.8 preanoxic denitrification
Postanoxic η is not necessary
 Biological Denitrification
■ Effect of DO concentration.
– DO can inhibit NO3 reduction
• By repressing the nitrate reduction enzyme
– DO concentration of 0.2 mg/L and above inhibit denitrification
– Effect of DO can be accounted for by correction factors

 kXS   K o' 

 
NO3 
rsu     '
 K s  S  K s , NO3  NO3  K o  DO 
where K 'o  DO inhibition coefficient for nitrate reduction, mg/L
K s, NO3  half velocity coefficient for nitrate limited reaction, mg/L
 Biological nitrogen removal processes

■ Single-sludge biological N-removal processes Nitrate feed

Influent Effluent
Anoxic Aerobic/
1. preanoxic, nitrification

Where initial contact of the wastewater Return activated sludge

and return activated sludge is in an anoxic zone

2. Postanoxic
Where anoxic zone follows the aerobic zone
Influent Effluent
Aerobic/ Anoxic
With or nitrification

without exogenous carbon source

endogenous respiration of AS to provide Return activated sludge
electro donor
Denitrification rate is much slower
 Biological nitrogen removal processes

3. Simultaneous nitrification-denitrification (SNdN) processes

Where both nitrification and denitrification occur in same tank
Anoxic

Aerobic

Influent To clarifier

Return activated Recycle

sludge (optional)

Require DO control or other types of control methods to assure that both

nitrification and denitrification occurs in single tank
 Biological nitrogen removal
processes
■ Possible mechanisms of simultaneous nitrification and
denitrification
1. Region of low DO or zero DO may be present within the basin
as function of mixing regime

2. Activated sludge floc can contain both aerobic

And anoxic zone
 Biological nitrogen removal
processes
■ Pre-anoxic nitrification/denitrification process is most
common
1. Relative ease of retrofit to existing plant
2. The benefits of the selector operation for control of bulking
sludge
3. The production of alkalinity before nitrification step
4. The ability to convert an existing biological treatment systems
to nitrogen removal with relatively short to moderate basin
detention
 Biological nitrogen removal
processes- process design consideration
■ Anoxic/Aerobic reactor design consideration Nitrate feed

– Key design parameters Influent Effluent

Anoxic Aerobic/
1. Anoxic zone detention time nitrification

2. MLVSS concentration Return activated sludge

3. Internal recycling rate and return sludge flow

4. Influent BOD or bCOD concentration
5. Readily biodegradable COD (rbCOD) fraction
6. Temperature
– Design approach
1. Desktop design approach: mass balances of N and a
commonly used design parameter, specific denitrification
rate (SDNR) (NO3-N reduction/g MLVSS.day)
2. Mechanistic simulation models (ASM1, 2, 2d, 3)
 Anoxic tank design using the
specific dentrification rate
■ Anoxic tank design using the specific dentrification rate
– Desktop approach based on SDNR
• Nitrate reduction rate in the anoxic tank normalized to the
MLSS concentration
NOr  Vnox SDNRMLVSS 
Vnox = anoxic volume, m3
Where NOr = nitrate removed, g/d
SDNR = specific denitrification rate, g NO3-N /g MLVSS.day
MLSVS= Mixed liquor volatile suspended solids concentration, mg/L

Preanoxic SNDR 0.04-0.42 g NO3-N/g MLVSS.day full-scale installations

Postanoixc SNDR 0.01-0.04 g N/g MLVSS.day (without exogenous carbon )
 Anoxic tank design using the
specific dentrification rate
■ Anoxic tank design using the specific dentrification rate

– Empirical relationship SDNR to the BOD or COD F/M

SNDR = 0.03(F/M)+0.029
where F/M= g BOD applied/g MLVSS·d in the anoxic tank

– Limited in application, provide rough estimates

SDNR depends on that are site-specific, design specific
Fraction of active biomass in ML, rbCOD concentration in anoxic zone
 Anoxic tank design using the
specific dentrification rate
F/Mb = QSo/(Vnox)Xb, F/Mb g BOD/g biomass.d
Vnox = anoxic volume, m3 Xb= anoxic zone biomass concentration

■ Figure 8-23 based on Model simulation, Table 8-18

 Anoxic tank design using the
specific dentrification rate
■ Internal recycle ratio (IR ratio)
– SDNR is affected by internal recycling rate (IR ratio).
IR = recycle flow rate/influent wastewater flowrate

At higher IR , influent rbCOD get diluted in anoxic tank resulted in

Low SDNR

IR=2 SDNRadj= SDNRIR1-0.0166 ln (F/Mb)-0.0078

IR=3-4 SDNRadj= SDNRIR1-0.029 ln (F/Mb)-0.012

SDNRIR1= SDNR value at internal recycle ratio=1

F/Mb= BOD F/M ratio based on anoxic zone volume and active
biomass concentration, g/g.d
 Anoxic tank design using the
specific dentrification rate
■ Internal recycle ratio (IR ratio
Nitrate produced in the aeration Return activated sludge recycle flow rate
zone as concentration relative to
influent flow, mg NO3-N/L
NOx
IR   1.0  R
Ne
Effluent NO3-N concentartion

IR 3-4 is typical

IR 2-3 for low influent TKN

concentrations
 Anoxic tank design using the
specific dentrification rate
■ Design procedure Table 8-19
 Anoxic tank design using the
specific dentrification rate
■ Design procedure Table 8-19
Example 8-2
Example 8-5
 Single-sludge SNdN processes
■ Oxidation ditch system operated
– at low DO (0.010-0.40 mg/L)
– At long HRT and SRT values
• Highly level of nitrification and denitrification have been
reported

■ Nitrification & Denitrification are function of

– Reaction kinetics, floc size, floc density, floc structure, rbCOD
loading, DO concentration- Complex physical factors

• Nitrification and denitrification rates cannot be predicted

accurately with present model
 Single-sludge SNdN processes
■ Monod growth model (modified) – to estimate the effects
of a low DO concentration Max. specific growth
Oxygenrate
inhibition
of nitrifying
coefficient
bacteria

  nm N  DO  1
SRT 
Specific growth for nitrification

 n      k dn n
Half velocity constant  N
K  N K 
 o Endogenousdecay coefficient of nitrifying organisms
DO
Oxygen inhibition coefficient

•Oxidation ditch at low DO

operated at SRT 20-30 day
Good nitrification

•Exact nitrification rate is site specific,

determines Ko
 Single-sludge SNdN processes
■ Rate of nitrate reduction and rate of substrate utilization
Oxygen inhibition coefficient
Half-velocity constant for nitrate limited reaction

 kXS  NO3  K o'

 

rsu   
 
 ( )
 K s  S  K s , NOx  NO3  K o  DO 
'

– Effect of nitrate and DO concentration

 1  1.42Y  kXS  NO3  K o'

 


 NO  K o'
  1.42 

rNOx      ( )  3
 k d X
 2 .86  s
K  S 
 s , NOx
K  NO 
3  K '
 DO   K  NO 
3  K '
 DO  2.86 
o  s , NOx o

General expression for rate of nitrate reduction in an anoxic reactor

NO3 reduction rate is function of rbCOD, NO3-N, DO , X and various

biokinetic coefficients
 Step-Feed Anoxic/Aerobic
process design
■ Influent is introduced at several feed points
Influent

Effluent
Anoxic Aerobic Anoxic Aerobic Anoxic Aerobic Anoxic Aerobic

Return activated sludge

■ Variable in design of step-feed N-removal process

– Flow distribution between passes
– Relative split between anoxic and aerobic volumes
– Final pass MLSS concentration - all determine SRT
 Intermittent aeration process
design
Typically operated at 18- 40 d of SRT
16 h HRT

Time of the anoxic and aerobic periods is

important in determining treatment
performance

NitroxTM use ORP measurement to control

the intermittent operation
 Intermittent aeration process
design
■ Long SRT and HRT
– Denitrification kinetics are related to the overall degradation of
bCOD, pbCOD, and endogenous decay
• Not as strongly influenced by the rbCOD fraction as for the
preanoxic denitfication application (short HRT)
Based on 2.86 g O2 equivalent/g NO3-
Specific denitrification rate relative to N and the assumption that only 50% of
heterotrophic biomass concentration, heterotrophic biomass can use nitrate
in place of oxygen
g NO3-N/g biomass.d 0.175 An
SDNRb 
Net yield for heterotrophic biomass
(Ynet ) SRT Net oxygen utilization coefficient, gO2/g bCOD removed

For complete-mix activated-sludge reactor

Y
An  1.0  1.42Y 
1.42(k d )(Y ) SRT Ynet 
1  (k d ) SRT 1 (k d ) SRT
 Intermittent aeration process design
Example 8-7
Determine what fraction of the time an oxidation ditch
system must be operated as an anoxic reactor for an
intermittent aeration process to produce an effluent
NO3-N concentration of 7 g/m3, based on following
desgin conditions:

Oxidation ditch volume = 8700 m3, SRT = 25 day

MLSS = 3500 g/m3, MLVSS = 2500 g/m3
Fraction of biomass = 0.4 g biomass/g MLVSS
Temperature 15oC, Y, kd = given in table 8-10
Influent flow rate= 7570 m3/day
NO3 concentration in oxidation ditch = 27 g/m3
 Postanoxic endogenous
denitrification
■ In separate tanks within the same single-sludge system
following nitrification Influent Effluent
Aerobic/ Anoxic

– The Bardenpho process nitrification

Return activated
sludge
■ After nitrification
– rbCOD is fully depleted
– pbCOD is likely to be depleted (depending on SRT)
– Electron donor – from AS endogenous respiration
■ SDNR 0.01-0.04 g NO3-N/g MLVSS under endo. resp.
 Postanoxic endogeneous
denitrification
■ SDNR under endogenous conditions
Biomass endogenous decay coefficient
g O2/g biomass VSS
Freaction of biomass that can use
NO3-N in place of O2 as an electron
1.42k d
SDNRb    0.5(k d )( ) acceptor

g O2 equivalent/g NO3-N 2.86

– Fraction of biomass from MLVSS declines as the SRT increases

SDNRMLVSS  0.12 ( SRT ) 0.706

g NO3-N/g MLVSS.d
 Postanoxic denitrification with an
external carbon source
■ Old approach
– Add a denitrification process after nitrification
– Two-sludge process
 Postanoxic denitrification with an
external carbon source
■ Designed in a similar manner to an activated-sludge
process
– Electron donor – growth substrate (methanol)
– NO3-N serve as electron acceptor
– Process design based on methanol degradation kinetics
 Postanoxic denitrification with an
external carbon source (Exp8-9)
■ Design procedure
1. Determine the amount of NO3-N to be reduced
2. Select the anoxic tank SRT
3. Calculate the anoxic tank residual methanol concentration
based on design SRT and Kinetic coefficients
4. Determine the methanol dose based on the amount of nitrate to
be removed and the amount of DO in the influent wastewater
to be consumed.
5. Calculate the total solids production
6. Determine the anoxic tank volume on the solids production
and SRT.
7. Select a detention time for the postaeration tank prior to
clarification.
 Homework (Pb 8-32)
■ For the suspended-growth postanoxic denitrification
process design example shown in Example 8-9 a design
SRT of 5 days was used. Deter mine (a) the change in the
methanol dose requirement (kg/d), (b) the amount of
sludge produced (kg/d), and (c) the anoxic tank volume
if a design SRT of 15 days is used instead. If methanol
costs 0.05$/kg, would the longer SRT design be more
economical?