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 recognize, anticipate, and subsequently control these processes - whether they are intentional or not.

the NITROGEN CYCLE

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. As 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 make up protein. From here it can be converted into animal protein organic nitrogen. Animals give off waste material, urine and fecal matter, both of which contain organic nitrogen forms. For example, fish release ammonia from their gills. Plant tissues are the only source of nitrogen for animals.

"The COMPOUNDS, CONDITIONS, and PLAYERS INVOLVED"

AMMONIA There are two forms of ammonia, unionized (NH3) and ionized (NH4+). The unionized form is the only toxic form. An equilibrium exists in water between the quantity of unionized (NH3) and ionized (NH4+) ammonia, with the percentage of the toxic form increasing with increasing temperature and pH values. For example, at 25 degrees C, in fresh water, less than 0.1% of the total ammonia is in the toxic form, but at pH 8.5 NH3 accounts for more than 10% - an increase of over 100 times. Ammonia is less toxic at lower pH levels. The only way to know how much ammonia is in the toxic unionized form is by determining the pH 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 0.02 mg/L of NH3 is most frequently referenced. What are we measuring and reporting? Ammonia contains atoms of nitrogen (N) and hydrogen (H). Some analysis may report Total Ammonia, as described above, but other analysis refer to the quantity of nitrogen in the ammonia molecule only. In this case the analysis units are presented as total ammonia nitrogen (TAN), which is the sum of NH3 -N + NH4 -N. Results reported in the two forms are not the same. It is necessary to know the percentage of nitrogen in the ammonia molecule to compare the two units. The atomic weight of nitrogen is 14 and that of hydrogen is 1; thus the molecular weight of NH3 is 14 + 3 = 17. Nitrogen is 14/17 or 82% of the weight of the ammonia molecule. The difference is much more important for nitrite and nitrate. Therefore, one (1) mg/L of NH3

is the same thing as 0.82 ppm of NH3 -N. Obviously, we need to know in what "units" we are reporting, so that we can compare values, etc. NITRITE Nitrite may be produced from ammonia as well as from nitrate. Excessive nitrite (NO2 -) is toxic to aquatic organisms, particularly in fresh water (it is much less toxic in sea water). The long-term safe level of NO2 - varies with different species; 0.1 & 0.2 mg/L are considered safe limits in soft and hard water, respectively. For some analysis, the the results may be reported in the units of NO2 - or NO2 -N. The atomic weight of oxygen is 16; thus the molecular weight of NO2 is 14 + 32 = 46. Nitrogen is 14/46 or 30% of the weight of the nitrite molecule. Therefore, an analysis value of 1 mg/L of NO2 is the same thing as 0.3 ppm of NO2 -N. NITRATE Nitrate is the end result of the process of nitrification. Nitrate concentrations above 100 mg/L have been shown to be nontoxic to many species. OXYGEN They are strict aerobes. ALKALINITY Alkalinity is a measure of the buffering capacity of the water. The release of hydrogen ions (H+) may lower the pH of lightly buffered water. Nitrification bacteria are very "fragile" organisms. They are the "trout" of the bacterial groups. Water with low alkalinity may in fact allow for the nitrifiers to create a toxic environment for themselves, and limit their growth. For this reason, it is beneficial to maintain an alkalinity level above 100 mg/L. Alkalinity is NOT to be used interchangeably with the term "basic," as that is the term used to describe the opposite condition of "acidic." (Please see our Operator Notebook summary on this topic if you need more information.) Alkalinity should be at least eight times the concentration of ammonia and ideally over 100 mg/L. This value may be higher for raw wastewaters with higher influent ammonia concentrations than the "normal." The theoretical reaction shows that between 7.07 and 7.14 mg of alkalinity (as CaCO3) is consumed for every mg of ammonia oxidized. Rule of thumb is 10 to 1. The result is an overall reduction in alkalinity and a possible drop in pH if the alkalinity is low to start with.

pH The optimal pH for nitrification is 8.0; with nitrification limited below pH 6.0. HARDNESS This is a measurement of the concentration of calcium and magnesium in the water. TEMPERATURE Increasing temperature can increase the rate of nitrification and nitrifier growth, and decreasing the temperature will decrease the rate of nitrification and nitrifier growth. Optimum temperature is about 25 C. Nitrification is inhibited at 10C or less. ( Nitrobactor , which converts nitrite into nitrate, has been shown to be the first one to slow in growth rate when the temperature drops.) Please see the temperature versus MCRT graph in the wastewater section for a visual representation of temperature impacts. NITRIFICATION Bacteria and chemical actions convert these two compound groups (plant and animal protein groups) into ammonia (NH3+ or NH4+ ) . Nitrification is a two step process: First Step: The nitrosomonas group of bacteria, known as nitrite formers, convert ammonia under aerobic conditions to nitrites and derive energy from the oxidation:

Another way to balance this equation is: NH4+ + 1 1/2 O2 ----> NO2- + 2H+ + H2O (In any case, for the chemists in our group, 66 kcal of energy are liberated per gram atom of ammonia oxidized.) The following microbes are also known to convert ammonia into nitrites: Nitrosospira, Nitrosouva, Nitrosolobus, Streptomyces, and Nocardia (our favorite activated sludge foam causing microbe). NOTE: these organisms are chemo-autotrophs, growing with ammonia as the energy substrate and CO2 as the main carbon source. Generally, the optimum growth temperature is 30 degrees C and the optimum pH is between 7.5 and 8.0.

Second Step: Then the "nitrite nitrogen" is oxidized by the Nitrobacter group of nitrifying bacteria, also known as the nitrate formers, into the "nitrate nitrogen" form:

Another way to balance this equation: NO2- + 1/2 O2 -----> NO3-. ( 18 kcal of energy is liberated per gram atom of nitrite oxidized.) Nitrospina, and Nitrococcus are also known to convert nitrite into nitrate. They are mesophiles, with a temperature optimum of 28oC and a pH range of 5.8-8.5, with an optimum pH range between 7.6 and 7.8. The nitrates that are formed may now serve as fertilizer for most plants. It requires about 4.5 parts of oxygen to convert one (1) part of "ammonia nitrogen" into "nitrate nitrogen". For a "basic summary" then, nitrification means the conversion of ammonia into nitrites; then the nitrites into nitrates. If we have "nitrification", can we have the opposite reaction? YES!

DENITRIFICATION
In denitrification, nitrates are reduced to nitrites, and then the reduction of nitrites to nitrogen gas occurs. (Reduction is the opposite of oxidation.) Reduction 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 as:

Many different groups of anaerobic and facultative bacteria can denitrify. Pseudomonas and Bacillus are aerobic denitrifiers. (Later we will discuss why we would WANT to denitrify or NOT to denitrify.)

CHLORINE BREAKPOINT & AMMONIA REACTIONS

Chlorine breakpoint and reactions with ammonia: the "number one impact" in water and wastewater treatment! Why? In our water treatment plant we may wish to chloraminate, (mix ammonia and chlorine together). WE MUST get the ratio of chlorine to ammonia correct! If our wastewater treatment activated sludge plant is being operated at a "nitrifying" MCRT value; (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. But 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 levels! Let us review what happens to create this situation. In the addition of chlorine to water, whether it is water or wastewater treatment, the reactions will be the same: chlorine forms hypochlorous acid very quickly: Cl2 + H2O = HOCl + Cl-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, and/or trichloramine species....depending on the chlorine to ammonia ratio, pH of the water, and the water temperature. The three possible chloramines, also termed/described as "combined chlorine" are formed as follows:

(Trichloramine, also called nitrogen trichloride, can only be formed in a low pH 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. In water treatment, the ratio of chlorine to ammonia is critical. We will discuss in the water impact section. In 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. A small amount of ammonia, even one mg/L breaks through, then our chlorine residual automatic feed system senses the decreasing chlorine residual, and the controllers ramp up, to feed up to 10 mg/L dosage for each 1 mg/L of ammonia, to make up for it. Nitrite is a very unstable form, and the nitrobacters convert it to nitrate very quickly. It is almost impossible to get a lab value on the nitrite level! So, if we test for ammonia, and find ammonia in a detectable concentration, it is safe to say that the nitrite form is transitioning also. (10 MGD)(8.34 lb/gal)(10 mg/L chlorine dose) = 834 pounds of ADDITIONAL chlorine, added to the present feed rate.....NOW, make it a 2 mg/L ammonia concentration, and we get to add 1,668 lb/day chlorine feed rate! At this rate, we can see how easy it is to create a chlorine feed rate that is two to three times our "normal" rate! At very high doses of chlorine, with small amounts of ammonia, oxidation - reduction reactions occur that convert ammonia into elementary nitrogen. 2Cl2 + 3H2O + 2NH3 -------> 6HCl + 3H2O + N2

According to this reaction, 1 mg/L of ammonia consumes 7.6 mg/L of chlorine. A review of the literature and process data suggests that it may vary from 8 to 10 mg/L of chlorine for every 1 mg/L of ammonia consumed by the chlorine! This is costly, in BOTH water and wastewater treatment! Again, for "positive enforcement": nitrate is non-reactive with the chlorine residual in the water, and nitrite is reactive as shown by the reaction: NO2--- + HOCl-- ---------> NO3 + H+ + Cl-In the following wastewater treatment discussion, we will move back and forth between the well-known "Breakpoint Chlorination Curve," Figure 1 here, and the "Ammonia Impact Upon Chlorination," trend/graph, Figure 2 in the Wastewater Treatment section. This is certainly not meant to confuse anyone! This exercise is necessary to: a) fully understand the breakpoint 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 Breakpoint Chlorination Curve" We start with the "Breakpoint Chlorination Curve," Figure 1. At Segment 1, we start to add chlorine. We keep adding chlorine, but there is no creation of a chlorine residual, as there is a "chlorine demand", which consumes the chlorine we are adding. Figure1

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 Segment 2 on Figure 1. As 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. (In lay terms, this means that an ammonia-like molecule is attached to a larger carbon-chain molecule.) As 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 BREAKPOINT on Figure 1. The addition of any more chlorine results in the formation of a "free chlorine" residual. As we increase the chlorine feed rate further, we create an even greater "free chlorine" residual, as illustrated in Segment 4, on Figure 1. We will discuss chloramination in the Water Treatment Impacts section.

NITRIFICATION: in WASTEWATER TREATMENT

Of 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 Nitrogen Oxygen Demand (NOD) in our effluents by the fact that the nitrogen conversion from ammonia to nitrate requires an oxygen uptake from the receiving waters to occur. The nitrification reaction in the receiving waters relies on the waters temperature, dissolved oxygen concentration, microorganisms present, etc. Attached nitrifying populations are more prevalent than suspended populations in the receiving waters. In fact, deep, slow-moving rivers are mostly absent from nitrification effects. How does nitrification play a part in wastewater treatment? How may we use it to our benefit? If 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.

FACILITY DESIGN
General: Nitrogen Species in Municipal Wastewater A review of the literature written on water quality, suggests that a "normal" domestic wastewater consists of a total nitrogen value in raw wastewater averaging 15 - 50 mg/L. 60% of the nitrogen content being bound in the complex organic matter, 40% of the nitrogen found in the ammonia form and <1% is in the nitrite or nitrate form.. Each person contributes 8 to 12 pounds of nitrogen per year to the wastewater treatment stream in the forms of food processing, urine, and feces. BOD:TKN Ratio This ratio is calculated from TKN and BOD measurements on the nitrification step influent. The higher the BOD portion the lower the nitrifier fraction. A BOD:TKN ratio of 2.5 or less should show good nitrification in the treatment system. Normal Nitrogen Removal Process During the normal treatment of domestic wastewater, secondary treatment may remove up to 30% of the total nitrogen coming into the plant. F/M Ratio and MCRT Generally speaking, to insure complete nitrification (all ammonia and nitrite is converted to nitrate), a higher MCRT of 10 days or more is

usually required (see MCRT vs/ temperature graph). Lower water temperature may increase the detention time required to make the process complete all reactions. Generally speaking, a F/M of <0.3 will allow for nitrification. The process is more efficient if the soluble carbonaceous BOD removal is almost complete. For a "suspended growth" (activated sludge) type of system, we may elect to design larger aeration basins, with additional aeration capacity, to reduce both the CBOD and the ammonia in the one set of aeration basins as shown in this diagram:

With the CBOD reduction to less than 10 to 15 mg/L, (some references say 20 mg/L), then the nitrification can occur in the same aeration basins. It is hard for CBOD to break through in this type of process (like the other nitrifying processes), due to the very low Food/Microorganism ratios. The F/M ratios are not really useful for daily operational use in most nitrifying activated sludge plants with their high MCRTs. Activated sludge plants operated in the nitrification mode, are usually easier to operate, as you have fewer variables to track and manipulate, such as maybe a critical F/M ratio to keep from nitrifying. Oxidation ditches are racetrack 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 just downstream of the brush aerators is fully aerobic which is where nitrification occurs. As the mixed liquor travels around the ditch, the nitrification reactions take place in which oxygen is consumed. Subsequently, an anaerobic zone is formed near the upstream area of the brushes. (See Operators Notebook, "Selectors" for the details.) We can also place our primary effluent into roughing trickling filters for the majority of CBOD reduction, followed by aeration basins for nitrification, and then the secondary clarifiers for solids separation:

Another option is to design a set of trickling filters placed in series operation, so that the ever decreasing CBOD wastewater is able to be nitrified in the last trickling filter. Another trickling filter option is to include recirculation from the filter underdrain system back over the tower media for increasing the mass (numbers) of nitrifying bacteria.

Our last design option may include a set of rotating biological contactors (RBCs), placed in series operation, so that the ever decreasing CBOD wastewater is able to be nitrified in the last train of RBCs. At low hydraulic load ratings, and soluble CBOD loadings of less than 15 mg/L:

Next, let us establish a few facts for the operation of our facility that will be nitrifying: As stated previously, nitrification requires (stoichiometrically) about 4.57 parts of oxygen to convert one (1) part of ammonia into nitrate. This reaction for the chemists in our group is as follows: 2NH4HCO3 + 4O2 + Ca(HCO3)2 = Ca(NO3)2 + 4CO2 + 6H2O Conversely then, nitrification is inhibited when the dissolved oxygen (DO) is less than 1.5 mg/L (Less than 1 mg/L has an even larger impact on inhibiting nitrification). We will need to maintain about 3 mg/L dissolved oxygen in the wastewater nitrifying process for optimum performance. Nitrifiers have longer lives and reproduce much more slowly (nitrobacter is the slowest to reproduce), and therefore require longer Mean Cell Residence Times (MCRTs ) in our activated sludge plants in order to select/enhance this form of treatment. Biofilters and Rotating Biological Contactors (RBCs) will therefore require more surface area and media to accomplish this. For example, the MCRT needed to provide a nitrified effluent as related to temperature (EPA data) would graph as follows:

Due to temperature impacts you may find a lower value for the summer, ie: 10 day MCRT and a higher value for winter, ie: 14 to 16 day MCRT. If you lose your nitrifiers during the cold times (ie: high flow rates due to I & I event) , you may not be able to get the population back until warmer water temperatures return. The best conditions for nitrifiers are a neutral to slightly alkaline pH, plenty of dissolved oxygen, an adequate supply of carbon dioxide, and warmer temperatures. Nitrifiers will be among the first microorganisms that toxins will affect. Toxins can have an inhibiting affect, as in a normal CBOD reduction,

and loss/partial nitrification situation developing. A 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. Each mg/L of ammonia nitrogen converted into nitrate will consume about 7 mg/L of alkalinity (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 wastewaters. Nitrification costs more in both tankage (and/or media) and also in operational costs due to the energy required to place the required oxygen into the water. (Remember: it requires about 4.5 mg/L DO to oxidize the ammonia into the nitrate form.) In biofilters, more trickling filter recirculation is required to accomplish this task. There are other significant impacts. Some of these are: The BOD test measures two things: the carbonaceous BOD (CBOD) 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 CBOD. If the sample is a secondary treatment process or final effluent sample, and nitrifiers are present, then we normally conduct an "inhibited BOD test". This means that we place a nitrification inhibiting substance into the samples, (HACH #2533) to eliminate the additional measurement of the nitrification reaction. A fully nitrified effluent contains only nitrates....there are few to little ammonia and nitrite forms in it. As such, it does not impact the test. REMEMBER also: Ammonia, 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. Often a cause for failing bioassays! Many of us love to say that "Nitrification is something we either do or do not do!" Most of our problems occur when our facilitys go into and out of nitrification....the "partial nitrification" status! The downstream process is most always the disinfection process, and can be greatly affected by partial nitrification! As 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 ALL of the ammonia and some starts to break through? What happens if we WANT to stay out of nitrification, and we start converting ammonia into nitrate?

"Ammonia Impact Upon Chlorination," trend/graph, Figure 2.

This trend screen is an actual screen from our wastewater treatment facility. (In order to show it here, we have taken the necessary liberty to enhance the actual data plot.) This screen covers a 24 hour period of time, starting at the left side of the page. Starting then at the left, as it shows at Segment A, we are in full nitrification. In Segment A the treatment plant flow rate, in MGD units, is increasing from the nights low flows, (the black line). The actual chlorination basin influent chlorine residual, in mg/L units, (dark blue line) is shown along with the chlorination basin effluent chlorine residual (the light blue) , in mg/L units. (Note 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."

Moving to the right, note that as time progresses we start to show an increase in ammonia, starting at Segment B. The ammonia is "breaking 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. As 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). In Segment C, 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. Note: in this particular case the combined chlorine residual is higher than that of the free chlorine residual when we're fully nitrifying. How can this be? Please refer now to the breakpoint curve, Figure 1. Find the area of the plot to the right of the breakpoint, marked Y. This is the approximate area of the free chlorine residual. When the combined chlorine residual is established, it moved back to the area marked X. Also, please note the offset in time between the decrease/increase curve of the chlorine basin influent and the corresponding decrease/increase curves of the chlorine basin effluent trends. As the ammonia level decreases at the end of 'Segment C' it finally reaches a level where once again the ratio of chlorine to ammonia creates another chlorine demand situation. In 'Segment D', 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. In 'Segment E' we have returned to a fully nitrified effluent and have established a free chlorine residual once again. As 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. If 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." Also, depending on such factors as the pH 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. Online and ""kinda real-time" ammonia, nitrite, and nitrate analysis equipment is quite expensive. Most ammonia analyzers, with their REQUIRED micro-filtration systems, run around $35,000 to $40,000. While expensive, one must be very careful when analyzing the disinfection trend screens without this equipment. While full plant data suggests that the breakthrough of ammonia over powers the effects of a breakthrough 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. Obviously, the principal operational considerations in all of this are the disinfection impacts. As the number, and duration, of nitrification impacts increase, we expect to experience an increase in the number of disinfection impacts. NOTES and THOUGHTS: If you are experiencing disinfection impacts

such as these, do NOT jump to conclusions! Another factor to consider, which may contribute to disinfection impacts and trend screens which will resemble this one, includes denitrification effects originating in secondary clarifiers. In addition, it is quite easy to create conditions in nitrifying facilities which will enable us to experience BOTH nitrification and denitrification impacts at the same time. (One easy case: unequal solids and hydraulic detention times in secondary clarifiers). Also, remember that high ammonia content return streams such as biosolids dewatering, and industrial discharges will provide variances in the ammonia content entering your facility. Biosolids Utilization Biosolids 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 uptake rate of the crop, and therefore, result in no additional nitrates entering the groundwater. (Ammonia is stored in the soil by being attached to negatively-charged clay particles by electrostatic interactions. For comparison, nitrate has the same electrostatic charge as the clays, and is repulsed by them. It 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. Some studies have shown that 50% of applied ammonia fertilizer can be converted into nitrate within 30 days after application.

DENITRIFICATION:
For complete nitrogen removal we usually find the denitrification reaction controlled in a separate treatment process. First we reduce the carbonaceous BOD to a low (< 15 mg/L ) 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. Oxygen Denitrification takes place under anoxic conditions, where no free oxygen is available. This usually happens in the secondary clarifier or in a dedicated anoxic tank. pH The optimum pH for denitrification is 7.0 to 7.5. The denitrification

process produces bicarbonate. In theory, about 3.57 mg CaCO3/mg N2 gas is realized. Carbon Source Denitrifying bacteria require carbon for cellular growth. If outside sources of carbon are required acetate, raw wastewater, methanol, or other sources of carbon are added. Sedimentation Generally speaking, the higher MCRT processes required for full nitrification produce pin floc, and ashing. In addition, the solids should spend no more than 35 minutes in a secondary sedimentation basis, or denitrification may occur. Prolonged detention of activated sludge in secondary (final) sedimentation tasks allows formation of sufficient nitrogen gas to "float the sludge" in block-like 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. Anoxic Selector for Denitrification Some wastewater treatment facilities will have a tank for denitrification and subsequent nitrogen gas stripping. In all of the denitrification processes, a carbon source MUST be present in order for the cells to reproduce. In 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 this: a) Propriety processes such as Bardenpho where they alternate anoxic and aerobic cells to force these reactions; or the A/O process where two or more non-aerated cells in series are placed prior to the aeration cells. (In the A/O process, denitrification takes place in the second anoxic cell.) b) Post-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) Pre-denitrification consists of an anoxic denitrification reactor followed by a fully aerated, combined CBOD/nitrification basin OXIDATION DITCH How would you accomplish this in an oxidation ditch?

A 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). Nitrates 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. Oxidation ditches which are also designed to denitrify can remove up to 97% of the total ammonia nitrogen from the water through their process of nitrification and denitrification. Since 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 constructed!

GLOSSARY
autotrophic: usually applies to a microorganism which utilizes inorganic substances (materials) for growth and energy, such as algae and nitrifiers. denitrification: reduction of nitrate (and/or nitrite) into nitrogen gas or ammonia; Nitrogen 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). methemoglobinemia: 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 H+ (acidity) nitrosomonas bacteria: an autotrophic bacteria group that uses only ammonia for energy (breaks the nitrogen-hydrogen bond for the energy). nitrobacter bacteria: an autotrophic bacteria group that uses only nitrite for energy (breaks the nitrogen-hydrogen bond for the energy).

oxidation: a chemical reaction characterized by oxygen uniting or combining with other elements; to remove hydrogen, as by the addition of oxygen; the action of increasing valence of an element. reduction: chemical reaction characterized by the loss of oxygen; the addition of hydrogen to a compound; also the lowering of the chemical valence of a positive element in a compound.

REFERENCES
WPCF, MOP 11, Vol II, WPCF, 1990 George Tchobanoglous & Franklin Burton, Wastewater Engineering, 3rd Edition, Metcalf and Eddy, Inc Texas Water Utilities, Manual of Wastewater Treatment 6th Edition, Texas Water Utilities, 1991 Kenneth A. MacKichen & Mark J. Hammer, Hydrology & Quality of Water Resources, Whiley, 1981 Walter Weber, Physicochemical Processes For Water Quality Control, Whiley, 1972 Mark J. Hammer & Warren Viessman, Jr., Water Supply and Pollution Control, 5th Edition , HarperCollins, 1993 July 1995 AWWA Research Foundation Order Number: 90669 Nitrification Occurrence and Control in Chloraminated Water Systems Prepared by Gregory J. Kirmeyer and Lee H. Odell, Economic and Engineering Services, Inc.; Joe Jacangelo and Andrzej Wilczak, Montgomery Watson, Inc.; and Roy Wolfe, Metropolitan Water District of Southern California