NITRIFICATION: the Basics

Introduction:
Operators in potable water and wastewater treatment plants should know
and understand nitrification and denitrification so that they are best able to
reconi!e" anticipate" and subse#uently control these processes $ whether
they are intentional or not%
the NITRO&'N C(C)'
The three main "fertilizer" ingredients for plants are nitrogen, phosphorous, and
potassium. We will consider here, the effect of nitrogen on water quality and the
disinfection process, in both water and wastewater treatment.
The nitrogen cycle diagram best illustrates the relationships that exist among the
various forms of nitrogenous compounds and the changes that occur in nature.
The atmosphere serves as the reservoir for the nitrogen from which nitrogen is
constantly removed by the action of lightning and certain nitrogen-fixing bacteria
and algae. s you can see from the nitrogen cycle figure, nitrogen is converted
into plant protein organic nitrogen. This means that nitrogen is one of the many
elements that ma!e up protein. "rom here it can be converted into animal protein
organic nitrogen. nimals give off waste material, urine and fecal matter, both of
which contain organic nitrogen forms. "or example, fish release ammonia from
their gills. #lant tissues are the only source of nitrogen for animals.

*The CO+,O-N./" CON.ITION/" and ,)A('R/ IN0O)0'.*
$$%&'
There are two forms of ammonia" unioni!ed 1N234 and ioni!ed 1N2564% The
unioni!ed form is the only to7ic form% n equilibrium exists in water between
the quantity of unionized (&)*+ and ionized (&),-+ ammonia, with the
percentage of the toxic form increasing with increasing temperature and p)
values.
"or example, at ./ degrees 0, in fresh water, less than 1.23 of the total
ammonia is in the toxic form, but at p) 4./ &)* accounts for more than 213 - an
increase of over 211 times. mmonia is less toxic at lower p) levels. The only
way to !now how much ammonia is in the toxic unionized form is by determining
the p) and temperature and then calculating the percentage of ammonia in the
unionized toxic form. (There are tables created for this purpose also.+ The long-
term safe concentration of ammonia varies with different animal species, but the
value of 1.1. mg56 of &)* is most frequently referenced.
8hat are we measurin and reportin9
mmonia contains atoms of nitrogen (&+ and hydrogen ()+. 7ome analysis may
report Total mmonia, as described above, but other analysis refer to the
quantity of nitrogen in the ammonia molecule only. 'n this case the analysis units
are presented as total ammonia nitrogen (T&+, which is the sum of &)* -& -
&), -&. 8esults reported in the two forms are not the same. 't is necessary to
!now the percentage of nitrogen in the ammonia molecule to compare the two
units. The atomic weight of nitrogen is 2, and that of hydrogen is 29 thus the
molecular weight of &)* is 2, - * : 2;. &itrogen is 2,52; or 4.3 of the weight of
the ammonia molecule. The difference is much more important for nitrite and
nitrate. Therefore, one (2+ mg56 of &)* is the same thing as 1.4. ppm of &)* -&.
%bviously, we need to !now in what "units" we are reporting, so that we can
compare values, etc.
&'T8'T<
&itrite may be produced from ammonia as well as from nitrate. <xcessive nitrite
(&%. -+ is toxic to aquatic organisms, particularly in fresh water (it is much less
toxic in sea water+. The long-term safe level of &%. - varies with different
species9 1.2 = 1.. mg56 are considered safe limits in soft and hard water,
respectively.
"or some analysis, the the results may be reported in the units of &%. - or &%.
-&. The atomic weight of oxygen is 2>9 thus the molecular weight of &%. is 2, -
*. : ,>. &itrogen is 2,5,> or *13 of the weight of the nitrite molecule. Therefore,
an analysis value of 2 mg56 of &%. is the same thing as 1.* ppm of
&%. -&.
&'T8T<
&itrate is the end result of the process of nitrification. &itrate concentrations
above 211 mg56 have been shown to be nontoxic to many species.
%?@A<&
They are strict aerobes.
6B6'&'T@
l!alinity is a measure of the buffering capacity of the water. The release of
hydrogen ions ()-+ may lower the p) of lightly buffered water.
&itrification bacteria are very "fragile" organisms. They are the "trout" of the
bacterial groups. Water with low al!alinity may in fact allow for the nitrifiers to
create a toxic environment for themselves, and limit their growth. "or this reason,
it is beneficial to maintain an al!alinity level above 211 mg56. l!alinity is &%T to
be used interchangeably with the term "basic," as that is the term used to
describe the opposite condition of "acidic." (#lease see our %perator &oteboo!
summary on this topic if you need more information.+ l!alinity should be at least
eight times the concentration of ammonia and ideally over 211 mg56. This value
may be higher for raw wastewaters with higher influent ammonia concentrations
than the "normal." The theoretical reaction shows that between ;.1; and ;.2, mg
of al!alinity (as 0a0%*+ is consumed for every mg of ammonia oxidized. 8ule of
thumb is 21 to 2. The result is an overall reduction in al!alinity and a possible
drop in p) if the al!alinity is low to start with.
p)
The optimal p) for nitrification is 4.19 with nitrification limited below p) >.1.
)8C&<77
This is a measurement of the concentration of calcium and magnesium in the
water.
T<$#<8TD8<
'ncreasing temperature can increase the rate of nitrification and nitrifier growth,
and decreasing the temperature will decrease the rate of nitrification and nitrifier
growth. %ptimum temperature is about ./E 0. &itrification is inhibited at 21E0 or
less. ( &itrobactor , which converts nitrite into nitrate, has been shown to be the
first one to slow in growth rate when the temperature drops.+ #lease see the
temperature versus $08T graph in the wastewater section for a visual
representation of temperature impacts.
&'T8'"'0T'%&
Facteria and chemical actions convert these two compound groups (plant and
animal protein groups+ into ammonia (&)*- or &),- + .
Nitrification is a two step process:
First /tep: The nitrosomonas group of bacteria, !nown as nitrite formers,
convert ammonia under aerobic conditions to nitrites and derive energy from the
oxidationG
nother way to balance this equation isG
&),- - 2 25. %. ----H &%.- - .)- - ).%
('n any case, for the chemists in our group, >> !cal of energy are liberated per
gram atom of ammonia oxidized.+
The following microbes are also !nown to convert ammonia into nitritesG
&itrosospira, &itrosouva, &itrosolobus, 7treptomyces, and &ocardia (our favorite
activated sludge foam causing microbe+.
&%T<G these organisms are chemo-autotrophs, growing with ammonia as the
energy substrate and 0%. as the main carbon source. Aenerally, the optimum
growth temperature is *1 degrees 0 and the optimum p) is between ;./ and 4.1.
7econd 7tepG Then the "nitrite nitrogen" is oxidized by the &itrobacter group of
nitrifying bacteria, also !nown as the nitrate formers, into the "nitrate nitrogen"
formG
nother way to balance this equationG
&%.- - 25. %. -----H &%*-.
( 24 !cal of energy is liberated per gram atom of nitrite oxidized.+
&itrospina, and &itrococcus are also !nown to convert nitrite into nitrate.
They are mesophiles, with a temperature optimum of .4o0 and a p) range of
/.4-4./, with an optimum p) range between ;.> and ;.4.
The nitrates that are formed may now serve as fertilizer for most plants. 't
requires about ,./ parts of oxygen to convert one (2+ part of "ammonia nitrogen"
into "nitrate nitrogen".
For a *basic summary* then" nitrification means the con:ersion of
ammonia into nitrites; then the nitrites into nitrates%
'f we have "nitrification", can we have the opposite reactionI @<7J
.'NITRIFICATION
'n denitrification, nitrates are reduced to nitrites, and then the reduction of nitrites
to nitrogen gas occurs. (8eduction is the opposite of oxidation.+ 8eduction of
nitrites is carried all the way to ammonia by a few bacteria organisms, but most
of them carry the reduction to the end product of nitrogen gas, which escapes
into the atmosphere. The bacteria utilize the nitrites and nitrates as the oxygen
source in their life processes. This process is carried out under anoxic or near
anaerobic conditions.
This chemical reaction is shown asG
$any different groups of anaerobic and facultative bacteria can denitrify.
#seudomonas and Facillus are aerobic denitrifiers.
(6ater we will discuss why we would W&T to denitrify or &%T to denitrify.+

C2)ORIN' BR'A<,OINT = A++ONIA R'ACTION/
0hlorine brea!point and reactions with ammoniaG the "number one impact" in
water and wastewater treatmentJ WhyI
'n our water treatment plant we may wish to chloraminate, (mix ammonia and
chlorine together+. W< $D7T get the ratio of chlorine to ammonia correctJ
'f our wastewater treatment activated sludge plant is being operated at a
"nitrifying" $08T value9 (or our "other nitrifying plant facilities" are at an organic
loading rate and hydraulic loading rate for a biological process that has a
sufficient organic material reduction that forces nitrification to completely occur+,
then we are not going to impact our disinfection by chlorination process. This is
because the nitrate form does not react with chlorine. Fut if we only "partially
nitrify", when we chlorinate with an "ammonia nitrogen" and "nitrite nitrogen"
species in the disinfection process we will have a significant impact on our
chlorine demand levelsJ 6et us review what happens to create this situation.
'n the addition of chlorine to water, whether it is water or wastewater treatment,
the reactions will be the sameG chlorine forms hypochlorous acid very quic!lyG
0l. - ).% : )%0l - 0l--
When the hypochlorous acid comes into contact with ammonia, we have the
hypochlorous and hypochlorite ion reacting with the ammonia. This yields a
monochloramine, dichloramine, and5or trichloramine species....depending on the
chlorine to ammonia ratio, p) of the water, and the water temperature. The three
possible chloramines, also termed5described as "combined chlorine" are formed
as followsG
(Trichloramine, also called nitrogen trichloride, can only be formed in a low p)
situation, not normally experienced in the plant processes, so we can almost
disregard it for operational impacts.+
Typically, most our chlorine residual analyzers have probes that read only the
monochloramine form, as it is the predominate form.
'n water treatment, the ratio of chlorine to ammonia is critical. We will discuss in
the water impact section.
'n wastewater, all of this leads to being caught in the "transition zone".....between
having a lot of ammonia in the wastewater being disinfected, or having a
completely nitrified effluent for disinfection. small amount of ammonia, even
one mg56 brea!s through, then our chlorine residual automatic feed system
senses the decreasing chlorine residual, and the controllers ramp up, to feed up
to 21 mg56 dosage for each 2 mg56 of ammonia, to ma!e up for it. &itrite is a very
unstable form, and the nitrobacters convert it to nitrate very quic!ly. 't is almost
impossible to get a lab value on the nitrite levelJ 7o, if we test for ammonia, and
find ammonia in a detectable concentration, it is safe to say that the nitrite form is
transitioning also.
(21 $AC+(4.*, lb5gal+(21 mg56 chlorine dose+ : 4*, pounds of CC'T'%&6
chlorine, added to the present feed rate.....&%W, ma!e it a . mg56 ammonia
concentration, and we get to add 2,>>4 lb5day chlorine feed rateJ t this rate, we
can see how easy it is to create a chlorine feed rate that is two to three times our
"normal" rateJ
t very high doses of chlorine, with small amounts of ammonia, oxidation -
reduction reactions occur that convert ammonia into elementary nitrogen.
.0l. - *).% - .&)* -------H >)0l - *).% - &.
ccording to this reaction, 2 mg56 of ammonia consumes ;.> mg56 of chlorine.
review of the literature and process data suggests that it may vary from 4 to 21
mg56 of chlorine for every
2 mg56 of ammonia consumed by the chlorineJ This is costly, in F%T) water and
wastewater treatmentJ
gain, for "positive enforcement"G nitrate is non-reactive with the chlorine residual
in the water, and nitrite is reactive as shown by the reactionG
&%.--- - )%0l-- ---------H &%* - )- - 0l--
'n the following wastewater treatment discussion, we will move bac! and forth
between the well-!nown "Frea!point 0hlorination 0urve," "igure 2 here, and the
"mmonia 'mpact Dpon 0hlorination," trend5graph, "igure . in the Wastewater
Treatment section. This is certainly not meant to confuse anyoneJ This exercise
is necessary toG a+ fully understand the brea!point chlorination curve, b+ interpret
trended information regarding chlorine applications in disinfection pertaining to
ammonia impacts, and c+ apply all of this information in our disinfection
operations.
"The Frea!point 0hlorination 0urve"
We start with the "Frea!point 0hlorination 0urve," "igure 2. t K7egment 2L, we
start to add chlorine. We !eep adding chlorine, but there is no creation of a
chlorine residual, as there is a "chlorine demand", which consumes the chlorine
we are adding.
"igure2
When we have added sufficient chlorine to equal this chlorine demand, we are
now able to start creating a chlorine residual. This is at the beginning of
K7egment .L on "igure 2. s we add more and more chlorine we see an increase
in the combined chlorine residual. The chlorine is combined with ammonia and
other organic molecules that contain amine (nitrogen+ based compounds as part
of their composition. ('n lay terms, this means that an ammonia-li!e molecule is
attached to a larger carbon-chain molecule.+
s we continue to add chlorine, we finally run out of ammonia, and organic
compounds that can accept chlorine. We then begin to further "fill up" the
available receptor sites on the nitrogen atom, until the nitrogen atom is liberated.
This is labeled KF8<B#%'&TL on "igure 2.
The addition of any more chlorine results in the formation of a "free chlorine"
residual. s we increase the chlorine feed rate further, we create an even greater
"free chlorine" residual, as illustrated in K7egment ,L, on "igure 2. We will discuss
chloramination in the Water Treatment 'mpacts section.
NITRIFICATION: in 8A/T'8AT'R TR'AT+'NT
%f principle concern to all of us are the impacts of nitrification and denitrification
in our facilities, whether intentional or not. There are situations for us to desire
these conditions (we need to remove the nitrogen from our plant effluent for
receiving water quality issues+, and other times to avoid them (downstream
process impacts, when nitrogen removal is not required+. There exists the
potential for a &itrogen %xygen Cemand (&%C+ in our effluents by the fact that
the nitrogen conversion from ammonia to nitrate requires an oxygen upta!e from
the receiving waters to occur. The nitrification reaction in the receiving waters
relies on the waterLs temperature, dissolved oxygen concentration,
microorganisms present, etc. ttached nitrifying populations are more prevalent
than suspended populations in the receiving waters. 'n fact, deep, slow-moving
rivers are mostly absent from nitrification effects.
)ow does nitrification play a part in wastewater treatmentI )ow may we use it to
our benefitI 'f we wish to produce a nitrified effluent to improve water quality in
our receiving waters, etc., then we need to discuss the design and operational
aspects to do so.
FACI)IT( .'/I&N
&eneral:
&itrogen 7pecies in $unicipal Wastewater
review of the literature written on water quality, suggests that a "normal"
domestic wastewater consists of a total nitrogen value in raw wastewater
averaging 2/ - /1 mg56. >13 of the nitrogen content being bound in the complex
organic matter, ,13 of the nitrogen found in the ammonia form and M23 is in the
nitrite or nitrate form.. <ach person contributes 4 to 2. pounds of nitrogen per
year to the wastewater treatment stream in the forms of food processing, urine,
and feces.
F%CGTB& 8atio
This ratio is calculated from TB& and F%C measurements on the nitrification
step influent. The higher the F%C portion the lower the nitrifier fraction.
F%CGTB& ratio of ../ or less should show good nitrification in the treatment
system.
&ormal &itrogen 8emoval #rocess
Curing the normal treatment of domestic wastewater, secondary treatment may
remove up to *13 of the total nitrogen coming into the plant.
"5$ 8atio and $08T
Aenerally spea!ing, to insure complete nitrification (all ammonia and nitrite is
converted to nitrate+, a higher $08T of 21 days or more is usually required (see
$08T vs5 temperature graph+. 6ower water temperature may increase the
detention time required to ma!e the process complete all reactions. Aenerally
spea!ing, a "5$ of M1.* will allow for nitrification. The process is more efficient if
the soluble carbonaceous F%C removal is almost complete.
"or a "suspended growth" (activated sludge+ type of system, we may elect to
design larger aeration basins, with additional aeration capacity, to reduce both
the 0F%C and the ammonia in the one set of aeration basins as shown in this
diagramG
With the 0F%C reduction to less than 21 to 2/ mg56, (some references say .1
mg56+, then the nitrification can occur in the same aeration basins. 't is hard for
0F%C to brea! through in this type of process (li!e the other nitrifying
processes+, due to the very low "ood5$icroorganism ratios. The "5$ ratios are
not really useful for daily operational use in most nitrifying activated sludge plants
with their high $08Ts. ctivated sludge plants operated in the nitrification mode,
are usually easier to operate, as you have fewer variables to trac! and
manipulate, such as maybe a critical "5$ ratio to !eep from nitrifying.
O7idation ditches are racetrac! shaped reactors in which rotating brushes both
aerate and move the mixed liquor at several points in the loop. The amount of
oxygen supplied is determined by the level of the brush rotor in the mixed liquor,
and the velocity of the flow remains constant. The region Nust downstream of the
brush aerators is fully aerobic which is where nitrification occurs. s the mixed
liquor travels around the ditch, the nitrification reactions ta!e place in which
oxygen is consumed. 7ubsequently, an anaerobic zone is formed near the
upstream area of the brushes. (7ee %peratorLs &oteboo!, "7electors" for the
details.+
We can also place our primary effluent into roughing tric!ling filters for the
maNority of 0F%C reduction, followed by aeration basins for nitrification, and then
the secondary clarifiers for solids separationG
nother option is to design a set of tric!ling filters placed in series operation, so
that the ever decreasing 0F%C wastewater is able to be nitrified in the last
tric!ling filter. nother tric!ling filter option is to include recirculation from the filter
underdrain system bac! over the tower media for increasing the mass (numbers+
of nitrifying bacteria.
%ur last design option may include a set of rotating biological contactors (8F0s+,
placed in series operation, so that the ever decreasing 0F%C wastewater is able
to be nitrified in the last train of 8F0s. t low hydraulic load ratings, and soluble
0F%C loadings of less than 2/ mg56G
&ext, let us establish a few facts for the operation of our facility that will be
nitrifyingG
s stated previously, nitrification requires (stoichiometrically+ about ,./; parts of
oxygen to convert one (2+ part of ammonia into nitrate. This reaction for the
chemists in our group is as followsG
.&),)0%* - ,%. - 0a()0%*+. : 0a(&%*+. - ,0%. - >).%
0onversely then, nitrification is inhibited when the dissolved oxygen (C%+ is less
than 2./ mg56 (6ess than 2 mg56 has an even larger impact on inhibiting
nitrification+. We will need to maintain about * mg56 dissolved oxygen in the
wastewater nitrifying process for optimum performance.
&itrifiers have longer lives and reproduce much more slowly (nitrobacter is the
slowest to reproduce+, and therefore require longer $ean 0ell 8esidence Times
($08Ts + in our activated sludge plants in order to select5enhance this form of
treatment. Fiofilters and 8otating Fiological 0ontactors (8F0s+ will therefore
require more surface area and media to accomplish this. "or example, the $08T
needed to provide a nitrified effluent as related to temperature (<# data+ would
graph as followsG
Cue to temperature impacts you may find a lower value for the summer, ieG 21
day $08T and a higher value for winter, ieG 2, to 2> day $08T. 'f you lose your
nitrifiers during the cold times (ieG high flow rates due to ' = ' event+ , you may not
be able to get the population bac! until warmer water temperatures return. The
best conditions for nitrifiers are a neutral to slightly al!aline p), plenty of
dissolved oxygen, an adequate supply of carbon dioxide, and warmer
temperatures.
&itrifiers will be among the first microorganisms that toxins will affect. Toxins can
have an inhibiting affect, as in a normal 0F%C reduction, and loss5partial
nitrification situation developing. nitrified effluent produces a "swimming pool"
clear water when the process is dialed in to the best solids settling characteristics
and the secondary clarification process.
<ach mg56 of ammonia nitrogen converted into nitrate will consume about ; mg56
of al!alinity (buffering capacity +. This is due to the hydrogen ions being liberated
from the ammonia as an acid. This is usually not much of a problem for most
domestic wastewaterLs.
&itrification costs more in both tan!age (and5or media+ and also in operational
costs due to the energy required to place the required oxygen into the water.
(8ememberG it requires about
,./ mg56 C% to oxidize the ammonia into the nitrate form.+ 'n biofilters, more
tric!ling filter recirculation is required to accomplish this tas!.
There are other significant impacts. 7ome of these areG
The F%C test measures two thingsG the carbonaceous F%C (0F%C+ and can
also measure the nitrogenous oxygen demand of the sample being tested. The
raw wastewater and primary effluents when tested, contain very few nitrifying
bacteria, and the test measures only the 0F%C. 'f the sample is a secondary
treatment process or final effluent sample, and nitrifiers are present, then we
normally conduct an "inhibited F%C test". This means that we place a nitrification
inhibiting substance into the samples, ()0) O./**+ to eliminate the additional
measurement of the nitrification reaction. fully nitrified effluent contains only
nitrates....there are few to little ammonia and nitrite forms in it. s such, it does
not impact the test.
8<$<$F<8 alsoG mmonia, in the un-ionized form is toxic to fish and other
water organisms, and may not be desirable to place into the receiving waters.
We may need therefore to remove the ammonia from the water, or at least
discharge a "nitrified effluent" which is not toxic. %ften a cause for failing
bioassaysJ
$any of us love to say that "&itrification is something we either do or do not doJ"
$ost of our problems occur when our facilityLs go into and out of nitrification....the
"partial nitrification" statusJ The downstream process is most always the
disinfection process, and can be greatly affected by partial nitrificationJ
s we have stated in the previous sections on nitrification, the idea of nitrification
as a process is to eliminate nitrogen from the water being treated. What happens
if we do not eliminate 66 of the ammonia and some starts to brea! throughI
What happens if we W&T to stay out of nitrification, and we start converting
ammonia into nitrateI
"mmonia 'mpact Dpon 0hlorination," trend5graph, "igure ..
This trend screen is an actual screen from our wastewater treatment facility. ('n
order to show it here, we have ta!en the necessary liberty to enhance the actual
data plot.+ This screen covers a ., hour period of time, starting at the left side of
the page. 7tarting then at the left, as it shows at K7egment L, we are in full
nitrification. 'n K7egment L the treatment plant flow rate, in $AC units, is
increasing from the nightLs low flows, (the blac! line+. The actual chlorination
basin influent chlorine residual, in mg56 units, (dar! blue line+ is shown along with
the chlorination basin effluent chlorine residual (the light blue+ , in mg56 units.
(&ote that it is slightly lower than the initial value due to a "latent chlorine
demand"+. The chlorine in the chlorine contact basin has been analyzed and is
described as a "free chlorine residual."
$oving to the right, note that as time progresses we start to show an increase in
ammonia, starting at K7egment FL. The ammonia is "brea!ing through" the
aeration basins upstream. The ratio of chlorine to ammonia at this point is quite
high. Therefore any ammonia introduced at this point will result in the chlorine
oxidizing all of the ammonia. The consumption of the chlorine in this process of
oxidizing ammonia, results in a reduction of the free chlorine residual when
compared to the set-point. The instrumentation therefore increases the quantity
of chlorine it is feeding to compensate. s more and more chlorine is consumed
the instrumentation loop fights to maintain the chlorination dosage set point. This
instrumentation increase of the chlorine feed rate is shown on the graph, by the
green line, in pounds per day units (signal is from the chlorinator+.
'n K7egment 0L, we see that when the ammonia has increased to a level capable
of supporting a combined chlorine residual, there is a corresponding decrease in
the chlorine feed rate. &oteG in this particular case the combined chlorine residual
is higher than that of the free chlorine residual when wePre fully nitrifying. )ow
can this beI
#lease refer now to the Kbrea!point curve, "igure 2. "ind the area of the plot to
the right of the brea!point, mar!ed K@L. This is the approximate area of the free
chlorine residual. When the combined chlorine residual is established, it moved
bac! to the area mar!ed K?L.
lso, please note the offset in time between the decrease5increase curve of the
chlorine basin influent and the corresponding decrease5increase curves of the
chlorine basin effluent trends.
s the ammonia level decreases at the end of P7egment 0P it finally reaches a
level where once again the ratio of chlorine to ammonia creates another chlorine
demand situation. 'n P7egment CP, the instrumentation increases the chlorine feed
once again, as shown by the chlorine feed rate in pounds per day (the green line+
to compensate for this consumption of chlorine. The greater the demand, the
greater the drop in the chlorine concentration, and the greater the corresponding
increase in the chlorine feed rate to offset it.
'n P7egment <P we have returned to a fully nitrified effluent and have established
a free chlorine residual once again.
s shown on this trend screen there are two periods of time where the chlorine
residual has dropped significantly...... once coming out of the nitrified situation
and then once when returning to the fully nitrified condition. 'f we can tighten up
the control loop to respond faster to this consumption of chlorine, we may lessen
the magnitude of the "chlorine residual drop." lso, depending on such factors as
the p) and temperature of the water being treated, the chlorine concentration
and species that the chlorine is in, solids concentration (turbidity+, the number of
microbes in the water, the contact detention time, etc., we may not be able to
meet the disinfection standards during these periods of time.
%nline and ""!inda real-time" ammonia, nitrite, and nitrate analysis equipment is
quite expensive. $ost ammonia analyzers, with their 8<QD'8<C micro-filtration
systems, run around R*/,111 to R,1,111. While expensive, one must be very
careful when analyzing the disinfection trend screens without this equipment.
While full plant data suggests that the brea!through of ammonia over powers the
effects of a brea!through and presence of nitrites, (which also consume
chlorine+, we must sample and analyze the wastewater to properly identify the
species of nitrogen we are dealing with, and its source.
%bviously, the principal operational considerations in all of this are the
disinfection impacts. s the number, and duration, of nitrification impacts
increase, we expect to experience an increase in the number of disinfection
impacts.
&%T<7 and T)%DA)T7G 'f you are experiencing disinfection impacts such as
these, do &%T Nump to conclusionsJ nother factor to consider, which may
contribute to disinfection impacts and trend screens which will resemble this one,
includes denitrification effects originating in secondary clarifiers. 'n addition, it is
quite easy to create conditions in nitrifying facilities which will enable us to
experience F%T) nitrification and denitrification impacts at the same time. (%ne
easy caseG unequal solids and hydraulic detention times in secondary clarifiers+.
lso, remember that high ammonia content return streams such as biosolids
dewatering, and industrial discharges will provide variances in the ammonia
content entering your facility.
Fiosolids Dtilization
Fiosolids are generally applied to agricultural fields in "agronomic rates." That
means, if there are no other limiting chemical compounds or elements such as
copper, etc., the biosolids will be applied in tons per acre for the crop that is to be
planted. The rate of application will match the nitrogen upta!e rate of the crop,
and therefore, result in no additional nitrates entering the groundwater.
(mmonia is stored in the soil by being attached to negatively-charged clay
particles by electrostatic interactions. "or comparison, nitrate has the same
electrostatic charge as the clays, and is repulsed by them. 't is then easily
washed (leached+ from the soil by irrigation and rainfall activity.
The conversion of ammonia into nitrate can be very rapid, if all of the optimal
conditions are available. 7ome studies have shown that /13 of applied ammonia
fertilizer can be converted into nitrate within *1 days after application.
C<&'T8'"'0T'%&G
"or complete nitrogen removal we usually find the denitrification reaction
controlled in a separate treatment process. "irst we reduce the carbonaceous
F%C to a low (M 2/ mg56 + value. Then, ammonia is converted into nitrites and
nitrates. The nitrites and nitrates are then placed into an oxygen-free condition,
where the bacteria utilize the nitrites and nitrates as the oxygen source in their
life processes. This strips the oxygen off of the nitrogen atom, which combines
with another nitrogen atom, and leaves the solution as nitrogen gas into the
atmosphere.
%xygen
Cenitrification ta!es place under anoxic conditions, where no free oxygen is
available. This usually happens in the secondary clarifier or in a dedicated anoxic
tan!.
p)
The optimum p) for denitrification is ;.1 to ;./. The denitrification process
produces bicarbonate. 'n theory, about *./; mg 0a0%*5mg &. gas is realized.
0arbon 7ource
Cenitrifying bacteria require carbon for cellular growth. 'f outside sources of
carbon are required acetate, raw wastewater, methanol, or other sources of
carbon are added.
7edimentation
Aenerally spea!ing, the higher $08T processes required for full nitrification
produce pin floc, and ashing. 'n addition, the solids should spend no more than
*/ minutes in a secondary sedimentation basis, or denitrification may occur.
#rolonged detention of activated sludge in secondary (final+ sedimentation tas!s
allows formation of sufficient nitrogen gas to "float the sludge" in bloc!-li!e
clumps to the surface, if nitrates are present in adequate amounts for this to
occur. This is often referred to as the "rising sludge" problem.
noxic 7elector for Cenitrification
7ome wastewater treatment facilities will have a tan! for denitrification and
subsequent nitrogen gas stripping.
'n all of the denitrification processes, a carbon source $D7T be present in order
for the cells to reproduce. 'n many cases this source is acetate, methanol, or
even a small portion of raw wastewater (in the case of an oxidation ditch, etc+
There are three principle methods to accomplish thisG
a+ #ropriety processes such as Fardenpho where they alternate anoxic and
aerobic cells to force these reactions9 or the 5% process where two or more non-
aerated cells in series are placed prior to the aeration cells. ('n the 5% process,
denitrification ta!es place in the second anoxic cell.+
b+ #ost-denitrification where the aeration basin is followed by an anoxic reactor.
The anoxic reactor is usually starving for a carbon source for cellular formation,
and a carbon source such as sugar, or methanol is fed.
c+ #re-denitrification consists of an anoxic denitrification reactor followed by a
fully aerated, combined 0F%C5nitrification basin
%?'CT'%& C'T0)
)ow would you accomplish this in an oxidation ditchI
denitrification zone (an anoxic selector+ can be made ahead of the anaerobic
zone by bringing a small portion of the raw sewage influent (as a carbon source+
to this selector (zone+. &itrates are then converted into nitrogen gas, and
released into the atmosphere. The mixed liquor then either flows into an
anaerobic selector, or contacts another brush aerator so that the organic nitrogen
produced by the denitrifying bacteria is oxidized. The raw wastewater flow rate,
organic loading, number of aerators, size of the ditches for detention time, and
the number of anoxic selectors required are obvious design parameters.
%xidation ditches which are also designed to denitrify can remove up to S;3 of
the total ammonia nitrogen from the water through their process of nitrification
and denitrification. 7ince oxidation ditches are also one of the easiest wastewater
processes to operate and maintain, if it were not for the large amount of land
required for this process, far more of them would probably be constructedJ
A6%778@
autotrophic: usually applies to a microorganism which utilizes inorganic
substances (materials+ for growth and energy, such as algae and nitrifiers.
denitrification: reduction of nitrate (and5or nitrite+ into nitrogen gas or ammonia9
&itrogen removal by anaerobic microbes that strip away the chemically bound
oxygen from the nitrite and nitrate, which liberates the nitrogen as nitrogen gas
into the atmosphere, (or ammonia+.
methemolobinemia: a disease in infants that is caused by high levels of nitrate
in the water.
nitrification: the process of converting ammonia nitrogen into nitrite nitrogen
then into nitrate nitrogen, causing the liberation of hydrogen ions )- (acidity+
nitrosomonas bacteria: an autotrophic bacteria group that uses only ammonia
for energy (brea!s the nitrogen-hydrogen bond for the energy+.
nitrobacter bacteria: an autotrophic bacteria group that uses only nitrite for
energy (brea!s the nitrogen-hydrogen bond for the energy+.
o7idation: a chemical reaction characterized by oxygen uniting or combining
with other elements9 to remove hydrogen, as by the addition of oxygen9 the
action of increasing valence of an element.
reduction: chemical reaction characterized by the loss of oxygen9 the addition of
hydrogen to a compound9 also the lowering of the chemical valence of a positive
element in a compound.
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WPCF, MOP 11, Vol II, WPCF, 1990
George Tchobanoglous & Franklin Buron, Wase!aer "ngineering, #r$ "$iion,
Mecal% an$ "$$&, Inc
Te'as Waer (iliies, Manual o% Wase!aer Trea)en *h "$iion, Te'as Waer
(iliies, 1991
+enneh ,- Mac+ichen & Mark .- /a))er, /&$rolog& & 0uali& o% Waer 1esources,
While&, 1921
Waler Weber, Ph&sicoche)ical Processes For Waer 0uali& Conrol, While&, 1934
Mark .- /a))er & Warren Viess)an, .r-, Waer 5u66l& an$ Polluion Conrol, 7h
"$iion , /ar6erCollins, 199#
.ul& 1997 ,WW, 1esearch Foun$aion Or$er 8u)ber9 90**9
8iri%icaion Occurrence an$ Conrol in Chlora)inae$ Waer 5&se)s
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Inc-< .oe .acangelo an$ ,n$r=e> Wilc=ak, Mongo)er& Wason, Inc-< an$ 1o& Wol%e,
Mero6olian Waer ?isric o% 5ouhern Cali%ornia