Advanced Waste Water Treatment

Tertiary Treatment
Remove disease-causing organisms
from wastewater
There are four major processes
under the Tertiary Treatment
1. Solids removal
2. Biological nitrogen removal
3. Biological phosphorus removal
4. Disinfection
There are 3 different disinfection
process
1. Chlorination
2. UV light radiation
3. Ozonation
BIOLOGICAL NITROGEN REMOVAL
Ammonia(NH4+)
Nitrosomonas

Nitrite
Nitrobacter

Nitrate
NITRIFICATION:

DENITRIFICATION:
 Biological Phosphorous Removal

The phosphorus enriched supernatant that comes out of the phosphorus

Stripper is treated with lime to precipitate the phosphorus .The resultant
Liquid supernatant can be returned to the aeration tank for further
treatment.
 Chlorination

Most common
Advantages: low
cost & effective
Disadvantages:
chlorine residue
could be harmful to
environment
 UV light radiation

Damage the genetic

structure of bacteria,
viruses and other
pathogens.
Advantages: no
chemicals are used
water taste more
natural
Disadvantages: high
maintenance of the
UV-lamp
 Ozonation
Oxidized most pathogenic microorganisms
Advantages: safer than chlorination fewer disinfection
by-product
Disadvantage: high cost
 Phosphorous Removal
The typical forms of phosphorus found in wastewater include :
1. Orthophosphates:
Orthophosphates such as PO3-4, HPO2-4, H2PO-4, H3PO4 are
available for biological uptake without further breakdown.
2. Polyphosphates (molecularly dehydrated phosphates):
The polyphosphates undergo hydrolysis (very slow process) in
aqueous solutions and revert to the orthophosphate forms.
3. Organic phosphates:
The organic phosphorus is an important constituent of
industrial wastes and less important in most domestic wws.
However, the principal phosphorous compounds in
wastewater are generally orthophosphates.
 Phosphorous Removal
• The total domestic phosphorus contribution to
wastewater is about 1.6 kg per person per year (3.5 lb
per capita per year).
• The average total phosphorus concentration in
domestic raw wastewater is about 10 mg/L,
expressed as elemental phosphorus, P.

• Approximately 30 to 50 percent of the phosphorus is

from sanitary wastes, while the remaining 70 to 50
percent is from phosphate builders in detergents.
 Phosphorous Removal
• Phosphorus is considered the main limiting factor for
algal growth in internal and coastal waters.
• Over time, the majority of mined phosphorus enters
the ecosystem as waste, leading to excessive nutrient
levels in waterways.
• This over-stimulates algae growth (eutrophication),
killing off natural aquatic species by consuming too
much oxygen in the water, and damaging waters for
consumption and recreation.
• Eutrophication, which is one of the most serious
environmental problems involving water sources in all
industrialised countries
 Phosphorous Removal
• Phosphorus removal from municipal and industrial
wastewater is required to protect receiving waters
from nutrient enrichment.
• It is a necessary part of pollution prevention to reduce
eutrophication.
• In most cases, the effluent standards range from 0.1 to
2.0 mg/L as P, with many established at 1.0 mg/L.
• Percentage reduction requirements range from 80 to 95 percent.
 Phosphorous Removal
• Conventional technologies for Phosphorus (P) removal from wastewater are
• physical processes,
• chemical precipitation and
• biological processes; they have been developed and showed promising
results.

1. Physical processes:
Filtration for particulate phosphorus
Membrane technologies
Phosphorous Removal
Phosphorous Removal by biological processes
2. Biological processes: Assimilation
• Phosphorus removal from wastewater has long been
achieved through biological assimilation –
incorporation of the P as an essential element in
biomass, particularly through growth of photosynthetic
organisms (plants, algae, and some bacteria, such as
cyanobacteria).
• Traditionally, this was achieved through treatment
ponds containing planktonic or attached algae, rooted
plants, or even floating plants (e.g., water hyacinths,
duckweed).
Phosphorous Removal by biological processes

• Land application of effluent during the growing season

has also been used, and
• constructed wetlands are now an established practice
as well.
• In all of these cases, however, it is necessary to remove
the net biomass growth in order to prevent eventual
decay of the biomass and re-release of the P.

• Example: Conventional activated sludge wastewater

treatment processes can remove 30-40% of the
phosphorus content of municipal wastewater.
Phosphorous Removal by biological processes
2. Biological processes: Enhanced biological phosphorus
removal (EBPR)
- the greatest recent and present interest
This is because of its potential to achieve low or even
very low (<0.1 mg/L) effluent P levels at modest cost
and with minimal additional sludge production.

• Removal of traditional carbonaceous contaminants

(BOD), nitrogen, and phosphorus can all be achieved in
a single system, although it can be challenging to
achieve very low concentrations of both total N and P in
such systems.
 Phosphorous Removal
• EBPR - based on the enrichment of activated sludge
with phosphate accumulating organisms.
• Phosphorus is not only utilized for cell synthesis,
maintenance, and energy transport, but is also stored for
subsequent use by the microorganisms.
• These microorganisms (also called P-removing or poly-P
bacteria) are able to store intracellular phosphorus as
polyphosphate.
• Phosphate accumulating organisms (PAOs) store
polyphosphate as an energy reserve in intracellular
granules.
Phosphorous Removal by biological processes

• The phosphate in EBPR is removed in the waste

activated sludge, which might have 5% or more P (dry
weight) as opposed to only 2-3% in non-EBPR sludges.
• EBPR has been demonstrated in several systems, such
as:
I. A/O (Anoxic/Aeration) process ,
ii. Sequencing batch reactors (SBRs), and
iii. PhoStrip process (which combines EBPR with
phosphate stripping and chemical removal).
 Phosphorous Removal by chemical processes
3. Chemical:
Precipitation
Other (mainly physical-chemical adsorption)
• Chemical removal techniques using metal salts are
reliable and well established processes.
• The simplicity of their application and the possibility
to achieve very low phosphate concentrations in the
effluent make this technology widely used.
• The chemical P removal was categorized into chemical
precipitation with lime and metal salts (Alum, Iron
chloride, etc)
Chemical Removal

M+3 + PO4-3 MPO4

( M+3 = Metal in Solution )

PRECIPITATION
Metals used are:
Aluminum, Al
Iron, Fe
 Phosphorous Removal by chemical processes
• Chemical precipitation- is usually carried out by addition
of mineral (aluminum or iron salts) and lime.
i. Alum:
• Aluminum ions can flocculate phosphate ions to form
aluminum phosphate which then precipitates:
Al3+ + HnPO43-,n+ → AlPO4↓ + nH+
• Alum, Al2(SO4)3 .14H2O, is most commonly used as a
source of aluminum.
Al2(SO4)3 .18H2O + 2HPO42- → 2AlPO4↓+ 2H+ + 3SO4 2- + 18H2O (3.1)

• Theoretically, 9.6 g of alum is required to remove 1 g of

phosphorus.
Alum Dosage Rates

Al2(SO4)3 + 2PO4-3 2AlPO4

Weight Ratio
Al+3 : P
0.87 : 1
Alum to Phosphorus
9.6 : 1
9.6 g of alum is required to remove 1g of P

Starting Dosage 40-50 mg/L

 Phosphorous Removal by chemical processes
• However, there is an excess alum requirement due to the
competing reactions with natural alkalinity. The alkalinity
reaction is :
Al2(SO4)3 .18H2O + 6HCO3- → 2Al(OH)3↓+ 3SO4 2- + 6CO2 +18H2O (3.2)
• As a result, the requirement of alum to remove
phosphorus demands weight ratios of approximately
(from Eqs. (3.1) and (3.2):
13 : 1 for 75 % phosphorus removal
16 : 1 for 85 % phosphorus removal, and
22 : 1 for 95 percent phosphorus removal.
 Phosphorous Removal by chemical processes
ii. Ferric chloride, FeCl3.6H2O:
FeCl3 + HPO24 → FePO4↓ + H+ + 3Cl- (3.3)
• The molar ratio of ferric ion to orthophosphate is 1 to 1.
• The stoichiometric weight ratios of Fe : P is 1.8 : 1.
• Similarly to alum, a greater amount of iron is required to
precipitate phosphorus and to react with alkalinity in
wastewater. Its competing reaction with natural alkalinity
is:
FeCl2.6H2O + 3HCO-3 → Fe(OH)3↓ + 3Cl- + 3CO2 + 6H2O (3.4)
• The reaction of Eq. (3.4) is slow. Therefore, lime or some
other alkali may be added to raise the pH and supply
hydroxyl ion for better coagulation. The reaction is:
 FERRIC IRON - Fe+3
M+3 + PO4-3 MPO 4

Fe+3 + PO4-3 FePO 4

Weight Ratio
Fe+3 to P
1.8 : 1
FeCl3 : P
5.2 : 1
5.2g of Ferric iron is required to remove 1g of P
Starting Dosage 20-25 mg/L
 Phosphorous Removal by chemical processes
• 2FeCl3.6H2O + 3Ca(OH)2 → 2Fe(OH)3 ↓ + 3CaCl2 + 12H2O (3.5)
• Both ferric (Fe3+) and ferrous (Fe2+) ions are used in the
precipitation of phosphorus.
• Ferrous sulfate application for phosphorus removal is
similar to that of ferric sulfate.

• The optimum pH for alum and ferric chloride is

between 5.5 and 7.0. The effective pH for lime is above
10.0.
N.B: Alum and ferric chloride decrease the pH while
lime increases pH.
 Phosphorous Removal by chemical processes
iii. Lime, CaO:
• Lime usually comes in a dry form, calcium oxide. It must
be mixed with water to form a slurry (calcium hydroxide,
Ca(OH)2) in order to be fed to a wastewater.
CaO + H2O → Ca(OH)2 (3.6)

5Ca(OH)2 + 3HPO2-4 → Ca5(PO4)3OH↓ + 3H2O + 6OH- (3.7)

Calcium ion reacts with phosphate ion in the presence of

hydroxyl ion to form hydroxy-apatite.
Phosphorus removal by mineral addition to
secondary effluents
• Phosphorus removal by lime treatment of secondary
effluent:
• Lime treatment of wastewater is essentially the same
process as is used for lime softening of drinking water,
but with a different purpose.
• While softening may occur, the primary objective is to
remove phosphorus by precipitation as hydroxyapatite
(Eq. (3.7)).

• 5Ca(OH)2 + 3HPO2-4 → Ca5(PO4)3OH↓ + 3H2O + 6OH- (3.7)

Removal of Nitrogen by Nitrification-
Denitrification
• The element nitrogen is a nonmetal. It belongs to Group VA
in the Periodic Table in the second period. Its electronic
configuration is [He]2s22p3 . [He] means that the helium
configuration is filled.
• The valence configuration represented by the 2, the L shell,
shows five electrons in the orbitals: 2 electrons in the s
orbitals and 3 electrons in the p orbitals.

• This means that, like phosphorus, nitrogen can have a

maximum oxidation state of +5; its smallest oxidation state is
3−.
To remove or not to remove nitrogen
• The formula of algae is (CH2O)106(NH3)16H3PO3.
• It is necessary to control only any one of the elements
of N, P, O, H, or C.
• It must be stressed that only one needs to be
controlled, because absence of any element needed for
the construction of the algal body prevents the
construction of the body.
• Of course, O, H, and C should never be controlled,
because there are already plenty of them around.
• N and P are essential nutrients for aquatic plant
growth.
Nitrogen Control
The main sources nitroge in wastewater are from:
• Human excreta,
• Kitchen garbage, and
• Industrial (food processing) wastes.

• Typical domestic wastewater contains

• 20 mg/L of organic nitrogen and
• 15 mg/L of inorganic nitrogen.
 Nitrogen Control
Effects:
• Nitrogen compounds, particularly ammonia, will exert
a significant oxygen demand through biological
nitrification and may cause eutrophication in
receiving waters.
• Ammonia (unionized) can be toxic to aquatic
organisms and
• it readily reacts with chlorine (affecting disinfection
efficiency).
• A high nitrate (NO3) level in water supplies has been
reported to cause methemoglobinemia in infants.
 Nitrogen Control
• In water bodies where eutrification is a problem, the
nutrient (P and N) load from wastewater must be
controlled.
• When available in excess in a water body, the water
body can become “eutrophic” – literally “well fed”
• P is usually limiting in fresh water
• N is usually limiting in estuaries and coastal waters
• Many treatment processes have been developed with
the specific purpose of
• transforming nitrogen compounds or
• removing nitrogen from the wastewater stream.
 Nitrogen Control
Conventional treatment processes:

• The overall primary and secondary treatment removes 25 to 75 percent (5 to 15

mg/L) of organic nitrogen.
• Typically, about 14 and 26 percent of total nitrogen from raw wastewater are
removed by conventional primary and secondary treatment processes,
respectively.
 Nitrogen Control
• Advanced treatment processes (3):-
Physical, chemical and Biological
–Tertiary filtration removes the suspended organic nitrogen
from the secondary effluent. However, the majority of
nitrogen is inorganic (ammonium).
Physical
–Reverse osmosis and electrodialysis can be used as a
tertiary process for ammonium removal. Their effectiveness
is 80 and 40 percent, respectively.
chemical
–Chemical coagulation for phosphorus removal also removes
particulate organic nitrogen.
–Break-point chlorination, air (ammonia) stripping, IE, etc
 Biological: Nitrification-Denitrification
• In biochemical nitrogen removal, BNR, the process for
nitrogen removal/control may be divided into two
categories, i.e. nitrification and nitrification–
denitrification, depending on the quality requirements
of wastewater effluent.
→ as mediated by microorganisms.
• The technique of the unit process is to release the
nitrogen in the form of the gas N2 to the atmosphere.
• This will first entail nitrifying the nitrogens using the
species of bacteria Nitrosomonas and Nitrobacter.
 Biological Nitrification-Denitrification

Nitrifying biofilm properties:

• Although the principal genera Nitrosomonas and
Nitrobacter are responsible for biological nitrification,
heterotrophic nitrification can also occur when nitrite
and/or nitrate are produced from organic or inorganic
compounds by heterotrophic organisms ( 100 species,
including fungi).
• However, the amount of oxidation nitrogen formed
by heterotrophic organisms is relatively small.
 Biological Nitrification-Denitrification

• The growth rate for nitrifying bacteria is much less

than of heterotrophic bacteria.
• Nitrifying bacteria have a longer generation time of at
least 10 to 30 hours.
• They are also much more sensitive to environmental
conditions as well as to growth inhibitors.
• The growth rate for nitrite oxidizers is much greater
than that for the ammonia oxidizers.
 Biological Nitrification-Denitrification
• Nitrosomonas oxidizes the ammonium ion into nitrites,
deriving from this oxidation the energy it needs.
• Nitrobacter then oxidizes the nitrites into nitrates, also
deriving from this oxidation the energy that it needs.
• These oxidations into nitrites and nitrates is called
nitrification. Nitrification is an aerobic process.
• The nitrification process is the oxidation of organic and
ammonia nitrogen (NH3-N) to nitrate, a less
objectionable form;
• it is merely the conversion of nitrogen from one form to
another form in the wastewater.
• Nitrification is used only to control NH3-N concentration in
the wastewater.
 Biological Nitrification-Denitrification

• After the nitrogen has been nitrified, the second unit

process of denitrification is then applied.
• The denitrifying bacteria, which are actually
heterotrophs, convert the nitrates into nitrogen gas,
thus ridding the wastewater of nitrogen.

• Denitrification is an anaerobic process.

• Denitrification is the reduction of nitrate to nitrogen gas, constituting a removal
of nitrogen from wastewater.
Chemical Reactions in Biological Nitrification
Nitrification:
• Biological nitrification is an aerobic autotrophic
process in which the energy for bacterial growth is
derived from the oxidation of inorganic compounds,
primarily ammonia nitrogen.
• Autotrophic nitrifiers, in contrast to heterotrophs, use
inorganic carbon dioxide instead of organic carbon for
cell synthesis.
• The yield of nitrifier cells per unit of substrate
metabolized is many times smaller than that for
heterotrophic bacteria.
Chemical Reactions in Biological Nitrification
The respective oxidation reactions are as follows (a two-
step process ):
1st. Ammonia oxidation (Nitrosomonas ):
NH4+ + 1.5O2 + 2HCO3- → NO2- + 2H2CO3 + H2O (4.1)

2nd. Nitrite oxidation (Nitrobacter):

NO2- +0.5O2 → NO3- (4.2)

• Overall reaction (nitrifiers ):

NH4+ + 2O2 + 2HCO3- → NO3- + 2H2CO3 + H2O (4.3)
Chemical Reactions in Biological Nitrification
• To oxidize 1 mg/L of NH3-N, theoretically 4.56 mg/L of
oxygen is required when synthesis of nitrifiers is
neglected.

• In actually (Biological Nitrification), less O2 is needed

since O is generated by fixing CO2 and N into cell mass.
Quiz 1# 10% time allowed 10 Min

1. Describe the Conventional technologies for Phosphorus removal

from wastewater 3pts

2. List the main sources of nitrogen in wastewater 3pts

3. Describe and discuss on the Phosphorous Removal by biological

processes 4
pts
Individual assignment # 15%
1. What is Eutrophication?

2. Another name of tertiary treatment is what? List the composition of waste

treated at this stage?

3. Phosphorous removal from municipal wastewater by how many ways? List

the biological P removal process and shows it by figure?

4. Lists advanced Nitrogen removal treatment process and explain them?

5 what is the importance and problem of nitrogen in the natural environment ?

6. Take one industry from your surrounding area which discharge waster
water contains nitrogen nutrients and describe it by how many ways remove
its from wastewater before discharge into disposal area