Nitrogen and Phosphorus Removal

Assist.Prof. Benjaporn Suwannasilp

Nitrogen removal
Adverse affects of nitrogen

Ammonia
1. Oxygen demand (4.57 g O2/g N for NH4+-N)
2. Toxicity to aquatic life: free ammonia is the most toxic
form. Speciation depends on pH (pKa NH4+/NH3 = 9.1).
3. Eutrophication
Nitrite
1. Oxygen demand (1.14 g O2/g N for NO2--N )
2. Methemoglobinemia (“Blue Baby” syndrome)
3. Eutrophication

Nitrate
1. Methemoglobinemia (“Blue Baby” syndrome).
2. Eutrophication
Form of nitrogen Abbrev. Definition

Ammonia NH3 NH3

Ammonium ion NH4+ NH4+
Total ammonia nitrogen TAN NH3 + NH4+
Nitrite NO2- NO2-
Nitrate NO3- NO3-
Total inorganic nitrogen TIN NH3 + NH4+ + NO2- + NO3-
Total Kjeldahl nitrogen TKN Organic N + NH3 + NH4+
Organic nitrogen Organic N TKN – (NH3 + NH4+)
Total nitrogen TN Organic N + NH3+ NH4++ NO2-+NO3-
Standard for N

Industry TKN < 100 mg/l as N

Big building TKN < 35 mg/l as N
Small building TKN < 40 mg/l as N
Aquaculture near coastal areas Ammonia < 1.1 mg/l as N
Total Nitrogen < 4 mg/l as N

Total Nitrogen = Dissolved N + Particulate N

http://www.pcd.go.th/info_serv/reg_std_water04.html#s3
Nitrification

-3 O2 +3 O2 +5

NH3 NO2- NO3-

Ammonia-oxidizing bacteria Nitrite-oxidizing bacteria
Ammonia-oxidizing archaea Nitrobacter
Nitrosomonas
Nitrification
NH4+ + 2O2  NO3- + 2H+ +H2O

Oxygen demand 4.57 g O2 / g N oxidized

Nitrification produces acidity thereby requiring alkalinity to prevent pH drop.

NH4+ + 2HCO3- + O2  NO3- + CO2 + 3H2O

Requiring alkalinity of 7.14 g as CaCO3 / g N oxidized

Factors affecting nitrification
• Temperature
• Dissolved Oxygen (DO); Ko = 0.5-1 mg/L
• Low pH (<6) inhibits nitrification

n = nm N DO - kdn
KN + N KO + DO
Denitrification

+5 0
NO3- N2
Denitrifying bacteria
Denitrification
C10H19O3N + 10 NO3-  5N2 + 10 CO2 + 3H2O + NH3 + 10 OH-

5CH3OH + 6 NO3-  3N2 + 5 CO2 + 7 H2O + 6 OH-

5CH3COOH + 8 NO3-  4N2 + 10 CO2 + 6H2O + 8 OH-

Denitrification produces alkalinity

Comparison of Nitrification and Denitrification

Nitrification Denitrification
C source CO2 Organic
Electron donor NH3 Organic
Electron acceptor O2 NO3-
Environment Aerobic Anoxic
Yield Low High
Alkalinity consume produce
Nitrification / Denitrification Process Configurations

Two stages: high treatment efficiency but require electron donor addition

CO2 CH3OH N2, CO2

NH4+ Aerobic
BOD NO3- NO3-
BOD removal Anoxic
Nitrification Denitrification

Sludge recycle Sludge recycle

Biomass Sludge wasting
Nitrification / Denitrification Process Configurations

AO = Anoxic + Aerobic
Reduce amount of oxygen requirement. No electron donor addition but low efficiency
Recirculation (Nitrate) ~ 1-2 times of influent flowrate
May create zoning within one tank: Anoxic 50-70 %, Aerobic 30-50%

NO3-, biomass

N2, CO2 CO2

NH4+
Anoxic NH4+ NO3- NO3-
BOD Aerobic
BOD removal Nitrification
Denitrification

Sludge recycle
Sludge wasting
 The Barnard Process

NO3-

N2, CO2 CO2 N2, CO2

NH4+
BOD Anoxic NH4+ NO3- Anoxic NH4+ Aerobic NO3- NO3-
BOD removal Aerobic BOD removal
Nitrification Nitrification
Denitrification Denitrification

Return sludge
Sludge wasting

Removal efficiency of ~ 90-95% without adding electron donor

Other ways to reduce oxygen requirement?

+
-3 NH4
-2
-1 NH2OH
0 N2

+1 N2O

+2 NO
+3 NO2-
+4
+5 NO3-
SHARON

Single reactor system for High Ammonium Removal Over Nitrite

The two core concepts on which the process is based:

1. At temperatures between 30-40o C, the growth rate of the AOB is greater

than NOB (Selects nitrosomonas over nitrobacter).

2. Denitrifying bacteria are capable of anoxic conversions of nitrite to N2.

SHARON

Single reactor system for High Ammonium Removal Over Nitrite

First step

Oxidation of ammonia under aerobic conditions to nitrite nitrogen

NH4+ + 1.5 O2  NO2- + H2O + 2H+

Second step

Shortened denitrification process: nitrite nitrogen is reduced to nitrogen gas

under anoxic conditions

NO2- + 0.5 CH3OH  0.5 N2 + 0.5 CO2 + 0.5 H2O + OH-

 SHARON

Single reactor system for High Ammonium Removal Over Nitrite

http://www.dep.state.pa.us/dep/deputate/watermgt/wsm/WSM_TAO/InnovTech/ProjRevi
ews/SharonHiRate.htm
ANAMMOX (ANaerobic AMMonium OXidation)

(van de Graaf et al., 1996)

Note: this process
requires a 1:1 ratio of
NH4+ + NO2-  N2 + 2H2O ammonium to nitrite

DO as low as 2 µM inhibits process!

ANAMMOX (ANaerobic AMMonium OXidation)

SHARON ANAMMOX

100 % NH4+  50 % NO2-

NH4+ + NO2-  N2 + 2H2O
50 % NH4+
CANON

Completely Autotrophic Nitrogen removal Over Nitrite

Nitritation NH4+ + 1.5O2 → NO2− + H2O + H+

Anammox NH4+ + 1.32NO2− + H+ → 1.02N2 + 0.26NO3− + 2H2O

Overall NH4+ + 0.85O2 → 0.44N2 + 0.11NO3− + 1.43H2O + 0.14H+

Summary
 Nitrification/denitrification
 AO
 Barnard process
 SHARON
 ANAMMOX
 CANON
Phosphorus removal
How to remove phosphorus?

 Convert P into solid phase

 Precipitation using metal salts

 Enhanced Biological Phosphorus Removal (EBPR)

Enhanced Biological Phosphorus Removal

 Certain heterotrophic bacteria are capable of sequestering of high

levels of phosphorus as intracellular polyphosphate (poly P), which
is an energy storage material.

 If such microorganisms are selected, induced to store poly P, and

wasted when rich in poly P, the net removal of P through biomass
uptake can be increased significantly.

 These microorganisms are called Phosphate Accumulating

Organisms (PAOs) or Bio-P bacteria
Enhanced Biological Phosphorus Removal

acetate Poly P CO2

and glycogen
Cell division

Pi Polyhydroxy Pi
alkanoate (PHA)

Anaerobic Aerobic
Enhanced Biological Phosphorus Removal

 PAOs compete with Glycogen Accumulating Organisms (GAOs)

 GAOs do not accumulate Poly P.

 PAOs are favored at pH in an anaerobic zone > 7.2.

 GAOs are favored at low pH.

Schematic of the required components of an activated
sludge process active for enhanced biological phosphorus
removal

No BOD oxidation BOD oxidation

PHB accumulation Biomass synthesis and decay
Poly P hydrolysis PHB utilization
and P release Poly P accumulation

Anaerobic Aerobic

Sludge recycle
Sludge wasting
Anaerobic + Anoxic + Aerobic (A2O)

Mixed-liquor NO3- recycle

Anaerobic Anoxic Aerobic

1h 2.7 h 4.7 h

Sludge recycle
Sludge wasting

Links an aerobic tank to classical predenitrification

Bardenpho process

Mixed-liquor NO3- recycle

Anaerobic Anoxic Aerobic Anoxic Aerobic

1h 2.7 h 4.7 h 2.2 h 1h

Sludge recycle
Sludge wasting

Links to the Barnard process

University of Cape Town (UCT) processes

Mixed-liquor recycle Mixed-liquor NO3- recycle

Anaerobic Anoxic Aerobic

Sludge recycle
Sludge wasting

Minimize the recycling of nitrate to the anaerobic tank

University of Cape Town (UCT) processes

Mixed-liquor recycle Mixed-liquor NO3- recycle

Anaerobic Anoxic Aerobic

Sludge recycle
Sludge wasting

Minimize the recycling of nitrate to the anaerobic tank

PhoStrip process

Combine Bio-P bacteria with chemical precipitation

Summary
 A2O
 Bardenpho process
 UCT processes
 PhoStrip process