Chapter 9 Nitrification - wemt.snu.ac.krwemt.snu.ac.kr/lecture 2014-2/env/Ch 9 Nitrification 2014-2...
Transcript of Chapter 9 Nitrification - wemt.snu.ac.krwemt.snu.ac.kr/lecture 2014-2/env/Ch 9 Nitrification 2014-2...
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Chapter 9 Nitrification
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Nitrification
- The microbiological oxidation of NH4+-N to NO2
--N and NO3--N.
NH4+-N removal is a mandated process for some
wastewaters because
i) NH4+ consumes oxygen up to 4.57 g O2 / g NH4+-N.
ii) NH4+ is toxic to aquatic macroorganisms
In addition, wastewater treatment that involves
denitrification of NO3- -N frequently requires nitrification to
convert the input NH4+-N to NO3
--N.
9.0
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Nitrification to remove NH4+-N from drinking-water
supplies also is practiced
i) to make the water biologically stable
ii) to eliminate the free-chlorine demand that produces chloramines
when free chlorine is desired.
NH3 + HOCl NH2Cl (monochloroamine) + H2O
9. 0
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The nitrifying bacteria are
autotrophs,
chemolithotrophs,
and obligate aerobes.
autotrophs,
Being autotrophs, the nitrifiers must fix and
reduce inorganic carbon.
Energy source:
light ---- phototroph
Chemical ---- chemotroph
chemolithotroph
chemoorganotroph
Photoautotroph: cyanobacteria, some
purple and green bacteria
Carbon source:
CO2 ---- autotroph
organic carbon ----- heterotroph
Photoheterotroph: some purple and
green bacteria
Chemoheterotroph = chemoorganotroph:
most bacteria, some archaea
Chemoautotroph = chemolithotroph: a
few bacteria and many archaea
Methylotroph: 1 carbon compound as
carbon source
9.1 Biochemistry and Physiology of Nitrifying Bacteria
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chemolithotrophs,
Their chemolithotrophic
nature makes fso and Y still
smaller, because their
nitrogen e-donors release
less energy per electron
equivalent than do organic
e-donors, H2, or reduced
sulfur.
9.1 Biochemistry and Physiology of Nitrifying Bacteria
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chemolithotrophs,
Of course, the low Y value translate into a small
maximum specific growth rate ( ) and a large , Θx min .
Therefore, nitrifiers are slow growers.
9.1 Biochemistry and Physiology of Nitrifying Bacteria
26.3
ˆ0
0min
bKbqYS
SK
]7.3[∧∧
Yq
∧
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obligate aerobes
- They use O2 1) for respiration (energy), and 2) as a direct
reactant for the initial monooxygenation of NH4+ to NH2OH
(hydroxylamine)
- The latter use of oxygen may be the reason why nitrifiers are
relatively intolerant of low dissolved-oxygen concentrations;
nitrifier catabolism is slowed by oxygen limitation at
concentration that have no effect on many heterotrophs.
9.1 Biochemistry and Physiology of Nitrifying Bacteria
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- In the first step, NH4+ is oxidized to NO2
- according to the following
energy-yielding rxn. (The most famous genus; Nitrosomonas)
]1.9[6
1
3
1
6
1
4
1
6
12224 OHHNOONH
eqeperkJGo 79.45'
eqeperkjG
NOONO
o
07.37
]2.9[2
1
4
1
2
1
'
322
- the second stage of the nitrification reaction is the oxidation of NO2-
to NO3- :(The most famous genus; Nitrobacter, Nitrospira)
9.1 Biochemistry and Physiology of Nitrifying Bacteria
- Nitrification is a two-step process.
- Since nitrifiers exist in environment in which organic compounds are
present, It might be curious that nitrifiers have not evolved to use organic
molecules as their carbon source. ~ probably related to their evolutionary
link to photosynthetic microorganisms.
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fso: very low for each group, compared to the typical fo
s value of 0.6-0.7 for
aerobic heterotrophs
For ammonium oxidizers
For nitrite oxidizers
Nitrifiers conserve very few electrons in biomass
Heterotrophs
0.6-0.7
20
(mgBODL/mgVSSa-d)
9.1 Biochemistry and Physiology of Nitrifying Bacteria
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For ammonium oxidizers
For nitrite oxidizers
The low fso values translate directly to low Y values (Caution: Unit is different form
each other !!).
Heterotrophs
0.6-0.7
20
(mgBODL/mgVSSa-d)
9.1 Biochemistry and Physiology of Nitrifying Bacteria
In units of g VSSa/ g OD, the difference of Y becomes greater.
Y = 0.1 for ammonium oxidizer, Y =0.45 for heterotrophs
Y =0.33x (14/6) / (32x1/4) = 0.1 (g VSS/g OD) [eq. 9.1]
]1.9[6
1
3
1
6
1
4
1
6
12224 OHHNOONH
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For ammonium oxidizers
For nitrite oxidizers
Maximum specific growth rate of both organisms are low ( < 1 d –1 at 20oC ):
Therefore, the limiting value of is large ( > 1 d). (See next slide)
Heterotrophs
9 d-1
9.1 Biochemistry and Physiology of Nitrifying Bacteria
]27.3[ˆ
1][ lim
min
bqY
lim
min ][
The relatively high values of Ko quantify that nitrifiers are not tolerant of low
DO concentrations
]7.3[∧∧
Yq
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Smin < 1 mg/L Effluent NH4+, NO2- can be very low levels
For ammonium oxidizers
For nitrite oxidizers
[Θxmin] lim must be large ( > 1 d )
Thus, as long as the SRT is maintained well above and sufficient dissolved
oxygen is present, the nitrification can be highly efficient
Heterotrophs
Θxmin =0.11 d
Smin = 0.17
mgBODL/L(complex
substrates)
9.1 Biochemistry and Physiology of Nitrifying Bacteria
]27.3[ˆ
1][ lim
min
bqY
min
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Primary consumers of organic waste: heterotrophic bacteria
(Generic parameters at 20 0C).
Limiting substrate BODL
Y (true yield for synthesis) 0.45 mg VSSa/mg BODL
(substrate utilization) 20 mg BODL /mg VSSa- d
(maximum specific growth rate) 9 d-1
K (conc. Giving one-half the
maximum rate)
simple substrate : 1 mg BODL /L
complex substrate : > 10 mg BODL /L
b (endogenous decay coefficient) 0.15 d
fd (biodegradable biomass fraction) 0.8
(value at which washout begins) 0.11 d safety factor 100 11 d
safety factor 36 4 d
Smin (the minimum substrate conc.
capable of supporting steady-state
biomass)
simple substrate : 0.017 mg BODL /L
complex substrate : > 0.17 mg BODL /L
min
x
qYˆˆ
q̂
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- The temperature effecs are very important
-Nitrification is sometimes considered impossible for low-water
temperatures.
-However, in fact, stable nitrification can be maintained at 5 oC or
lower, as long as the SRT remains high enough
For example, for 5 oC, a safety factor of only 5 requires that Θx min
be 3.6 x 5 = 18 d (quite large). Thus SRT should be larger than 18 days.
-One problem with low-temperature nitrification is that û becomes
quite small, making recovery of nitrification after a wash out a very
slow process.
Thus, avoiding nitrifier washout due to excess sludge wasting, low DO,
or inhibition must be an absolute priority, particularly for low temperatures.
9.1 Temperature effect
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The directly comparable parameters: fso, , , Smin ̂
-Very similar for two types of nitrifiers.
-This circumstance is completely logical, since both are aerobic
chemolithoauthotrophs oxidizing N (next slide)
-They almost always coexist in the same habits, experiencing the
same SRT and oxygen concentrations.
-Reflects their biochemical and ecological similarities
9.1 Biochemistry and Physiology of Nitrifying Bacteria
min
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chemolithotrophs,
Their chemolithotrophic
nature makes fso and Y still
smaller, because their
nitrogen e-donors release
less energy per electron
equivalent than do organic
e-donors, H2, or reduced
sulfur.
9.1 Biochemistry and Physiology of Nitrifying Bacteria
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Overall, balanced equation for the complete oxidation of NH4+ to
NO3-N by nitrifiers having 067.0,15 sfdx
]3.9[973.1921.0
973.00261.01304.0815.1
2
3275224
HOH
NONOHCCOONH
- The low net formation of nitrifier biomass : Ynet = 113 x 0,0261/ 14 =
0.21 g VSSa/g N
- Nitrification creates a major oxygen demand.
OD = 1.815 x 32 / 14 = 4.14 g O2 / g NH4+-N consumed
- Produces almost two (1.973) strong-acid equivalents (1.973) per mole of NH4+
removed
Thus the alkalinity consumption is 1.973 x 50/14 =7.05 g as CaCO3/g NH4+-N
- The first step, ammonium oxidation, is responsible for the acid production
9.1 Biochemistry and Physiology of Nitrifying Bacteria
refer to next slide
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2) Obtain the overall reaction (R) including energy and synthesis
using portions of electrons, fe (= 0.6) and fs (= 0.4)
fe*Re: 0.02 C6H5COO- + 0.12 NO3- + 0.12 H+ -> 0.12 CO2 + 0.06 N2 + 0.002 HCO3
-
+ 0.1 H2O
fs*Rs: 0.0133 C6H5COO- + 0.02 NH4+ + 0.0067 HCO3
- -> 0.02 C5H7O2N + 0.0067 H2O
R : 0.0333 C6H5COO- + 0.12 NO3- + 0.02 NH4
+ + 0.12 H+
-> 0.02 C5H7O2N + 0.12 CO2 + 0.06 N2 + 0.0133 HCO3- + 0.1067 H2O [2.34]
The overall reaction for net synthesis of bacteria that are using benzoate as an e- donor, nitrate as an e- acceptor, and ammonium as nitrogen source.
2.5 Overall Reactions for Biological Growth
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- - Most of the nitrifier-produced SMP are BAP (biomass-associated
products)
- SMPs are part of the decay process of the nitrifiers and reduce the net
synthesis of the nitrifiers
- A way in which nitrifiers create e-donors for heterotrophs and increase
the heterotrophic biomass
Nitrifiers produce SMPs which can be consumed by heterotrophic
bacteria
9.1 Biochemistry and Physiology of Nitrifying Bacteria
* UAP ( substrate-utilization-associated products )
• growth associated
• they are generated from substrate utilization and biomass growth • they are not intermediates of catabolic pathways
* BAP ( biomass-associated products )
• non-growth associated
• related to decay and lysis of cell
• release of soluble cellular constituents through lysis and solubilization
of particulate cellular components
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- Highly sensitive to chemical inhibition.
- The very slow growth rate of nitrifiers magnifies the
negative impacts of inhibition and, in part, makes it appear
that nitrifiers are more sensitive than are faster growing
bacteria.
- Furthermore, some apparent inhibitors are e-donors whose
oxidation depletes the DO and may cause oxygen limitation.
- Most relevant inhibitors are: unionized NH3 (at higher pH),
undissociated HNO2 (usually at low pH), anionic surfactants,
heavy metals, chlorinated organic chemicals, and low pH
Chemical inhibition
9.1 Biochemistry and Physiology of Nitrifying Bacteria
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A successful nitrification process – suspended growth or biofilm-
must account for the reality that
- heterotrophic bacteria always are present
- and competing with the nitrifiers for dissolved oxygen and space.
- The nitrifiers’ relatively high Ko value puts them at a disadvantage in
the competition for oxygen.
- Their slow growth rate is a disadvantage when competing for any space
that requires a high growth rate
overcome by ensuring that
two disadvantages
- the nitrifiers have a long SRT, typically greater than 15 d,
- larger value may be needed in the presence of toxic materials, a low D.O.
concentration, or low temperature.
9.2 Common Process Considerations
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Even with the relatively long SRT of extended aeration, nitrifying
process often have relatively small safety factors.
- for economic reasons
- AS [Θx min
]lim for nitrification is 1-3 d, the reactor volume is too great when
the safety factor is greater than about 10, because the Θx / Θ ratio cannot
be increased indefinitely to compensate.
- Unfortunately, the risk is high, and instability in nitrification is a
common problem in treatment operations
- Of course, operating with a small safety factor increases the
risk of washout due to solids loss or inhibition and increases
the needs for operator attention.
9.2 Common Process Considerations
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9.3 Activated Sludge Nitrification : One-sludge Versus Two-Sludge
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9.3 Activated Sludge Nitrification : One-sludge Versus Two-Sludge
• One-sludge nitrification
- One-sludge nitrification is the process configuration in which
heterophic and nitrifying bacteria coexist in a single mixed liquor that
simultaneously oxidizes organic BOD and ammonium
- Use the term one sludge to emphasize the ecological relationship
between the nitrifiers and hetrotrophs
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9.3 Activated Sludge Nitrification : One-sludge Versus Two-Sludge
• Two-sludge nitrification
- Two-sludge nitrification is an attempt to reduce the competition
between heterotrophs and nitrifiers by oxidizing most of the organic
BOD in a first stage
- The first sludge is essentially free of nitrifiers, while the second sludge
has a major fraction of nitrifiers
• One-sludge nitrification can be carried out in sequencing
batch reactors (SBR)
- SBR involves sequential periods of filling, aerobic reaction, settling, and
effluent draw-off in one tank
- In most ways, SBR nitrification resembles any other one-sludge system.
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9.7 The ANAMMOX Process
- Recently (1999), a novel bacterium in the planctomycetes group has been
discovered for its ability to anaerobically oxidize NH4+-N to N2, not NO2
-.
- It is called the ANAMMOX microorganism, Anaerobic Ammonium Oxidation.
- The discovery of ANAMMOX is one of the most startling ones in environmental
biotechnology.
Ammonium: electron donor
Nitrite: electron acceptor
Autotrophs: the reduction of inorganic carbon via oxidation of nitrite to
nitrate, nitrite as the nitrogen source
OHNNONH 2224 2
3275222 23145 NONOHCHOHNOCO
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The yield and specific growth rate are low.
Y = 0.14 g VSSa/g NH4+-N, = 0.065/d
This gives an overall stoichiometry of approximately:
ANAMMOX’s favoring condition
- exceptional biomass retention: a very long SRT
- stable operation
- the presence of nitrite
- lack of oxygen
- lack of e- donor: cause the reduction of nitrite via denitrification
In the presence of e donor, nitrite is reduced to N2
9.7 The ANAMMOX Process
OHNONOHCNHCONONH 232752224 95.1024.0017.002.0085.026.1
2223 NONNONONO