Ammonia (NH3) in Alberta

First Nations Public Water Systems

15th Annual Technical Service Conference & Tradeshow

Sunil Beeharry B.Sc. CPHI

Objectives
Review the affect of Ammonia on Chlorine Disinfection
What is it
Where is it
How it affects Chlorination Breakpoint Chlorination

Review the limitations of the HACH DPD Colorimeters

Review and discuss strategies to mitigate risks

Rate of Water Disease Since 1900what do you think the

line represents?

What is Ammonia
Ammonia is a nitrogen containing compound.

Animal and vegetable matter contain nitrogen and contribute to ammonia

through urinating and decomposition of proteins (death, feces etc). The
building blocks of proteins are amino acids which are the nitrogen
containing chemicals in living things.

As amino acids are broken down ammonia is released.

Urea (urine) is converted / fixed in the environment in which some will be

converted to ammonia.

What are the sources of ammonia

Fertilizer runoff, septic tank seepage, sewage,
erosion, and decay of natural deposits (dead plant
materials, animals) are considered typical sources
of ammonia in surface and GUDI water.
Drinking Water Wells may be surrounded by natural
geology containing ammonium salts which leach into
groundwater.

What types of Water Sources can

have Ammonia?
Can be found in Groundwater under the influence of
surface water (GUDI), GW and Surface water
sources.

Do we have Ammonia in any of our Public Water Systems in

Alberta First Nations?

Yes:
- At least 26 public water systems have detectable levels
of ammonia in the water supply.
- 1/3 of our public systems may have ammonia influences.
- Detectable levels range from 0.051 6.5 mg/L.

What are the consequences of presence of ammonia in

raw water sources for Water Treatment?
Potential for not reaching Breakpoint chlorination:

1.

Inadequate disinfection

2. Chlorine taste and odour problems (eg. Dichloramine).

Complaints received and inability to manage chlorine levels

effectively: Frustrated WTPOs.

Common Terms:
Combined Available Chlorine (Mono, di and trichloramines)
Not effective at destroying harmful microbes

Free Available Chlorine

Very effective at destroying harmful microbes.

Total Chlorine Residual / Total Chlorine

The sum of free and combined residual chlorine.

Extremely important
to maintain
chlorine residuals.

When ammonia is present

in raw source water it
obstructs proper, effective
disinfection.

Disinfection Effectiveness of
Free Chlorine vs Monochloramine:

Breakpoint
The breakpoint curve helps to Illustrate How Ammonia Interacts
with and prevents/ inhibits Free Chlorine formation
Breakpoint is the amount of chlorine that must be added to
water before a stable free residual can be obtained.
Breakpoint is described as the point at which chlorine demand has
been satisfied, combined chlorine compounds have been
destroyed and as additional chlorine is added, a free chlorine
residual is produced.

Breakpoint Curve
The breakpoint curve assumes you have reached
endpoint equilibriumie. enough time has passed to
allow chemical reactions to reach equilibrium.

Free Chlorine is less than 1% of the solution makeup when

Monochloramine is present.

Free chlorine and ammonia do not exist in solution together they

react quickly to form monochloramine and derivatives.

Therefore, when testing chlorine residuals, if time has not been

reached for chemicals to react, characterization of the true
chlorine concentrations will be inaccurate.

Dosage is
less than 4 to
1 chlorine to
ammonia.

Dosage is
10 to 1
chlorine
to
ammonia.

Disinfection poor in this region

When ammonia is present in
these zones, free chlorine will
not be present.
Any chlorine added in these
zones converts to
monochloramine within 1
second.
DPD tests here may show
false positive free chlorine
readings as monochloramine
interference.

Disinfection poor in this region

Free ammonia is not present in this zone it
has been combined with chlorine.
Any free chlorine added in this zone
converts monochloramine to di and
trichloramine over time (takes upto hour).
As the reaction takes time, Chlorine testing
may show free chlorine is available. But not
effective as it will convert before disinfection
is reached.
DPD tests in this zone may show false
positive free chlorine readings:

monochloramine interference and/or

temporary free chlorine residuals if
equilibrium has not been reached.

Disinfection is effective in this zone.

This zone is the target zone as

free chlorine residual is
genuine and real.
Any chlorine added in this
zone increases the free
chlorine residual in the water.
DPD tests in this zone will not
show false positive free
chlorine readings.

Hey your poisoning us with chlorine

Consumers complain that your adding too much chlorinemost likely your
creating dichloramines after the monochloramine peak
>Monochloramine has least taste and odour. Taste threshold is 0.65 mg/L
and odour threshold is 0.48 mg/L. Rarely causes complaints unless
over 5 mg/L.
>>Free chlorine (HOCl) has next least taste and odour threshold. Taste
threshold is 0.24 mg/L odour threshold of 0.28 mg/L.
>>>>>Dichlor has a taste/ odour threshold of 0.1 mg/L and has very
offensive complaints at 0.5 mg/L.
>>>>>>>>>>Trichlor (no numerical reference) but is generally referenced
as much more offensive than dichloramine.

Keep in mind chlorine taste and odour can be affected

by levels of source water organics
chloroderivatives.

Ammonia is chlorine hungry!

Testing Chlorine

My free chlorine is good!! Not really.

The HACH colorimeters are most commonly used by
the water industry and is based on the DPD Analytic
Method eg. Pocket Colorimeter 2 and DR890s etc.

When monochloramine is present and/or water is tested

in Zone 3 (downward slope of breakpoint curve
without allowance for equalization to occur will give
temporary free chlorine) it may read as Free Chlorine
-giving a false positive reading.

Testing Chlorine

Bromine, Iodine, chlorine dioxide, ozone, potassium

permanganate, and monochloramine all cause interferences
with free chlorine DPD analysis.

Testing Chlorine
Perform the phantom chlorine residual test.
And

If the differential between the total chlorine and

free chlorine is great (>15%) this may also
indicate that breakpoint has not been reached
eg. If the total chlorine reading is 1.4 mg/L
and the free is 0.2 mg/L you probably have
an issue and need to investigate.

Testing Chlorine
For water systems that have ammonia present in source water,
before testing daily chlorine residuals it is prudent to wait at
least an hour after a fill/run cycle of the water treatment plant.

Considerations When Interpreting Source Water

Ammonia Results
Raw water source concentration may fluctuate.
Chlorine dosage needs to meet the fluctuating level of
ammonia.

Considerations When Interpreting Source Water

Ammonia Results
Surface water sources fluctuations can occur
depending on time of year
Spring run off (may increase)
Winter (ammonia generally increases)
Summer (ammonia generally decreases)

Considerations When Interpreting Source Water

Ammonia Results
Multiple Wells or Mixed Supplies
- A multiple well source where one or more of the wells
has different levels of ammonia.
- A source water supply made up of surface water
source and well water source with different ammonia
levels.

Confounding Factors with Raw Water

Some systems cannot test raw water so no
information exists.
Some mixed systems with multiple sources cannot be
easily tested individually.
Therefore to grasp the scope of the challenge and
address the treatment needs more sampling points
and testing may be required / added to the WTP.

Confounding Factors
Fluctuating concentrations of other parameters that add
to chlorine demand (TOC, Nitrite, Iron, Manganese,
Organic N etc) make it more challenging.
Treatment processes efficiencies/deficiencies such as:

filtration increasing turbidity will increase chlorine demand

Greensand filtration with permanganate permanganate will reduce chlorine
demand of ammonia, iron, manganese.

Strategies
1.

First Determine if you have an ammonia present in raw water.

Review raw water ammonia results.

Review treated water ammonia results.

If ammonia is tested and found in the distribution system in significant

amounts it means breakpoint has not occurred. Exceptions(remember
that external lab results ammonia will show up if monochloramine is
present).

Determine the source

is it a particular well or intake?

What is contributing to ammonia in the environment (natural/man
made influence)?

Strategies
2. Determine chlorine demand challenges.

Complete the free verses total chlorine check if the

differential between free and total is great (> 15 %) then
further investigation may be needed.

Is it challenging to maintain consistent chlorine results?

Are there a lot of chlorine taste and odour complaints?

Is chlorine demand fluctuating.

What if I have ammonia:

1.

Bench/field testing raw water

- might include daily or weekly ammonia level monitoring depending on the
magnitude of the problems.
- test / monitor when switching raw water sources that have different historical levels
of ammonia.

USE TSAGS S-SCAN to help verify breakpoint and manage ammonia influences.

2.

Calculate or jug test for chlorine demand.

The Effects of Ammonia on Chlorine Disinfection

PFRA Document
Standard Methods for the Examination of Water and Wastewater

Strategies
We have some systems where it is not feasible to meet
breakpoint.
Consult with your TSAG circuit rider.
Blend different sources more effectively or evenly to reduce high
ammonia source water or so that management is predicable.
Use a water source with less or no ammonia.
Install treatment technologies for ammonia.

Ammonia and Water Treatment

Comes down to this
Support your Water Treatment Plant Operators.
If you are having trouble maintaining free chlorine
residual you may have an ammonia issue.
Work with your circuit rider and use the S scan
technology to help manage.
Work with your EHO & Health Centre

Questions