1.9: Chloramination and Nitrification

Learning Objectives

After reading this chapter you should be able to explain and identify the following topics:

• Why chloramine treatment has been employed, (hint) DBP formation
• The use of ammonia in water treatment
• Breakpoint chlorination
• Nitrification

The water treatment profession is constantly evolving and continuously in motion. Advancements in science and lab procedures help water professionals find constituents in drinking water that can be harmful to human beings. We take for granted the fact that clean drinking water will flow when we turn on the tap.

Currently, chlorine is the best disinfectant available. However, the use of chlorine causes any number of disinfectant by-products (DBPs). Many of the DBPs have not been researched and are not regularly monitored. As screening methods improve, it is likely that more of the possible DBPs will be regulated in the future. Trihalomethanes (THMs) are a DBP of chlorine disinfection and are classified as volatile organic chemicals. Rising THM levels in raw water are increasing the use of chloramine as the preferred disinfectant. In this chapter, we will discuss chloramine disinfection and the associated challenges that come with its implementation. Nothing is easy in water treatment.

Why Use Chloramines?

As discussed, chlorine has been used with great effectiveness in water treatment for many years in the United States. However recently, many water agencies have been switching to Chloramine treatment. Now here is the twist; they have done it because they must, not because they necessarily want to. When natural organic matter reacts with chlorine, it can result in the formation of DBPs, specifically trihalomethanes (THM) and haloacetic acids (HAA5). It is believed that long term exposure to these DBPs should be avoided as it may lead to cancer.

Because of the implementation of the Stage 2 DBP Rule in 2012, many water agencies could no longer meet the regulatory limits established, if they continued using chlorine as a primary disinfectant. To continue using chlorine alone, enhanced coagulation would have to be used but its effectiveness is limited. Carbon or GAC absorption is also a solution but it is very expensive, and thus not employed by larger water treatment facilities. The other option is to limit contact with the water and chlorine, but this is limited by the chlorine demand. The last and most effective option is to use chloramines.

Chloramine treatment is also effective in limiting taste and odor problems in finished water. When free chlorine reacts with phenol it can cause taste and odor issues. Chloramine disinfection is not as strong a disinfectant as free chlorine, chlorine dioxide, or ozone, but it does leave the longest-lasting residual in finished water. Because of chloramines weaker disinfecting power, it is often added just before the treated water enters the clearwell for storage. If implementing this method, the operator must ensure the THM levels are low enough as not to violate any regulations. Determining the most effective way to treat drinking water while remaining in compliance is a complex and difficult task.

Chloramine Chemistry

Chlorine reacts with a number of substances in water including dissolved organic matter, particulate organic matter, iron, nitrite, sulfide, and ammonia. It reacts by taking away an electron from them. Ammonia in the water supply is undesirable as it strips away the Chlorine residual which then requires the need to use more Chlorine. What makes chloramine treatment so effective is chlorine’s quick formation with ammonia (NH₃). (Ammonia is a compound of Nitrogen and Hydrogen.)

\[\ce{Cl2 + NH3 → NH2Cl + HCl}\]

Note that monochloramine is expressed as \(\ce{NH2Cl.}\)

The unit weight of Chlorine is 70 and the unit weight of Nitrogen is 14. When chloramine treatment is employed, the ratio of chlorine to ammonia will always be 5:1 because 5 mg/L of chlorine will always combine with 1.0 mg/L of ammonia. (70 ÷ 14 = 5) You will often hear monochloramines referred to as combined chlorine due to this reaction.

Below is a list of terms dealing with Chloramine disinfection:

• Free Chlorine: Cl₂ (Free chlorine can refer to gaseous, sodium hypochlorite, or calcium hypochlorite.) If using hypochlorite, remember you must dose the water to achieve 100 percent free chlorine.
• Monochloramine: NH₂Cl or combined chlorine. Chloramine with the least taste and odor problems.
• Free Ammonia: NH₃ Ammonia is measured as nitrogen
• Chlorine: Ammonia ratio: Total chlorine to total ammonia nitrogen. You will always target a 5:1 ratio to avoid excess free chlorine or free nitrogen in the water supply.

Breakpoint Chlorination

The breakpoint chlorination curve is the visual representation of chlorine’s ability to react with a variety of compounds to form a combined chlorine residual or to completely react with compounds to form a free chlorine residual. When using free available chlorine as a disinfectant we want to stay out of the combined curve. Some water agencies buy imported water that has a combined residual. To treat the water more effectively or eliminate the possibility of nitrification, some of these agencies add chlorine to “break” over to a free chlorine residual. We will discuss Nitrification in greater detail later in this chapter.

Figure \(\PageIndex{1}\): The breakpoint chlorination curve. This curve represents chlorine’s ability to have either a combined residual or a free residual. Image by the NSW Department of Premier and Cabinet is licensed under CC BY 4.0

A common problem that operators run into when using combined chlorine is “breaking over” to free chlorine by misdiagnosing problems on the treatment plant. For example, an operator is looking at a Supervisory Control And Data Acquisition (SCADA) screen. (SCADA is the computer system that monitors and controls the plant.) For the sake of ease, we will call this operator #1. He or she notices the chlorine effluent residual is beginning to drop. Operator #1 was not aware that the previous operator (Operator #2) had raised the chlorine dose a few hours before. With the added chlorine dose, the chlorine residual was “lowering” as it got closer to breaking over. If operator #1 panics and raises the chlorine dose again the combined chlorine residual will lower even further.

The important thing to remember is there are many things to look at if your chlorine dose is lowering. It may very well be an issue with your chlorine feed, but there are many other options to consider. If you check your chlorine feed system and everything is functioning normally, you may have an issue with the ammonia feed system. Many modern water treatment facilities have calculations built into the SCADA system that make chloramine dosing easier. Make sure to go to the screen with the chlorine: ammonia: ratio to make sure that it is set up correctly.

Lastly, free chlorine is always the preferred disinfectant as it is 25 times stronger a disinfectant than chloramines. However, chloramines last much longer in the distribution system. There are several factors that may lead to a lowered chlorine residual. An increase in biological growth is possible, but you should see other signs such as an increase in turbidity. The most common problem in chloramine treatment with a decreasing chlorine residual is operator error or an issue with the water treatment process.

Nitrification

Nitrification is a process in which bacteria reduces ammonia and organic nitrogen in treated water into nitrate and then nitrite. This condition usually occurs during the summer months when water temperatures are higher. It can also occur during the improper turnover of reservoirs, when there are high levels of ammonia, and in dark environments, a typical condition for most water reservoirs.

This condition is one of the drawbacks of chloramine treatment. Nitrate and Nitrite are inorganic chemicals regulated by primary drinking water standards. The MCL (Maximum Contaminate Level) for Nitrate is 10 ppm and the MCL for Nitrite is 1 ppm. High nitrate and nitrite levels in drinking water can lead to methemoglobinemia also known as “blue baby syndrome.” This condition affects infants under six months old that consume water contaminated with nitrates and nitrites. The infant's blood is not able to carry enough oxygen to blood cells and tissue within their body.

The condition of Nitrification is a reoccurring cycle that can lead to the total loss of chloramine residual in the distribution system and in water storage tanks. If this was to occur, all the water in the system would have to be dumped and it would be a total loss. As an operator, this is something that you never want to happen. Not only would it be a loss of money for your company, but it could lead to an outbreak of methemoglobinemia. The cycle is below:

Chloramine decay → Release of ammonia→ oxidation of ammonia to nitrite from oxidizing bacteria → Biomass increase → (back to chloramine decay until there is a possibility of total loss of residual)

Some early indicators of nitrification:

• Lowering chloramine residual
• Increase in bacterial heterotrophic plate counts
• Excess ammonia in the treated water
• Total coliform positive samples

In summation, nitrification can cause a variety of problems and violations within the water system. What can we as operators do to minimize any chance of nitrification from occurring? There are a few steps every operator can take to avoid nitrification. First, you want to minimize free ammonia in treated water. Sampling and equipment around the treatment plant will help operators determine if there is too much free ammonia in the treated water.

Second, operators should always maintain a good chlorine residual. Isn’t that the name of the game? Sure, but it is easier said than done in some cases. Many water treatment companies will lower their target chlorine residual in the summer to save on costs because the disinfectant works more efficiently during the summer months. It is a good practice in theory, but not necessarily the best practice if you are working with chloramines and trying to combat nitrification.

Reducing water age is the third step operators can use to combat nitrification. This can be done by cycling reservoirs during the summer months and taking reservoirs out of service during the winter when water demands are lower. Distribution operators are continually balancing maintaining a good amount of water for fire flow and demand, but also cycling reservoirs to fight nitrification. A good practice is to take all the reservoirs in the distribution system and divide it into thirds. At any given point during the day 1/3 of the reservoirs are full, 1/3 are in the middle range, and 1/3 are in the lower range. This allows operators to cycle water while also keeping water in the system.

The last step is to keep the water system clean. This can be accomplished by flushing dead ends to prevent lower chlorine residuals at the end of the distribution system. Boosting chlorine by adding it directly to a reservoir is also an option but not always the best practice. The problem with this method is it could lead to short circuiting. Chlorine must mix adequately to be effective. Mixing can be accomplished by adding mechanical mixers in the reservoir to keep water moving and prevent short circuiting. Chlorine can also be added to the inlet of the reservoir so the water pressure acts as a mixer.

Figure \(\PageIndex{2}\): (left) an example of a water reservoir mixer used to cycle water and prevent short-circuiting. (right) Hydrant flushing (CC0)

Hydrant flushing is a method that can be used to get rid of stagnant water at the ends of a distribution system. Stagnant water can lead to lower chlorine residuals and possible nitrification.

In summary, the use of chloramines as a disinfectant is being employed by many water agencies in the United States to prevent DBP formation. It is not the most ideal disinfectant available, but it does have some advantages. Chloramine disinfection limits DBP formation and has a longer-lasting disinfectant residual. This can be useful for larger systems where water must travel great distances to get to storage.

The drawbacks include the difficulty in effectively managing the breakpoint chlorination curve and managing nitrification. Because of advancements in water quality testing and more stringent regulations with DBPs, chloramine treatment is and will continue to be a more popular option in water treatment.

Chapter Review

1. What is the target chlorine to ammonia ratio?
   1. 2:1
   2. 3:1
   3. 4:1
   4. 5:1
2. What is the MCL for nitrates?
   1. 1 ppm
   2. 10 ppm
   3. 5 ppm
   4. None of the above
3. What is the atomic weight of chlorine?
   1. 70
   2. 14
   3. 65
   4. 20
4. What disinfectant has the longest-lasting residual?
   1. Ozone
   2. Chlorine
   3. Chloramine
   4. Chlorine dioxide
5. What are some of the early indicators of nitrification?
   1. Lowering chlorine residual
   2. Excess ammonia in treated water
   3. Raise in bacterial heterotrophic plate counts
   4. All of the above
6. What are THMs classified as?
   1. Turbidity
   2. Radiological
   3. Volatile organic chemicals
   4. Salts
7. What method can operators employ to combat nitrification?
   1. Lower residual chlorine target
   2. Keep reservoir levels static
   3. Minimize free ammonia in treated water
   4. Increase water age
8. How many times stronger is Chlorine compared to monochloramine?
   1. 25 times
   2. 20 times
   3. 15 times
   4. 5 times