Alkalinity 101

A Basic Non-Chemistry approach to

understanding how Alkalinity can
affect your plant operations
 What is Alkalinity?
• The alkalinity of water is a measure of its
capacity to neutralize acids. It also refers to
the buffering capacity, or the capacity to resist
a change in pH.
 Why is alkalinity important to
Wastewater Operations?
• Alkalinity is often used as an indicator of
biological activity. In wastewater operations,
there are three forms of oxygen available to
bacteria:
• dissolved oxygen (O2),
• nitrate ions (NO3- ),
• and sulfate ions (SO42-).
How Nitrification Affects Alkalinity
• Aerobic metabolisms use dissolved oxygen to
convert food to energy. Certain classes of
aerobic bacteria, called nitrifiers, use
ammonia (NH3) for food instead of carbon-
based organic compounds. This type of
aerobic metabolism, which uses dissolved
oxygen to convert ammonia to nitrate, is
referred to as nitrification
Wastewater Operations Result in Loss
of Alkalinity
• Alkalinity is lost in an activated sludge process
during nitrification. During nitrification, 7.14
mg of alkalinity as CaCO3 is destroyed for
every mg of ammonium ions oxidized
Ammonia Concentration vs Alkalinity Depletion
120

100

80

60

40

20

0
1 2 3 4 5 6 7 8 9 10 11 12 13

Ammonia mg/L Alkalinity mg/L

 What Happens When a Treatment
Plant Loses Alkalinity?
• Lack of carbonate alkalinity will stop
nitrification. In addition, nitrification is pH-
sensitive and rates of nitrification will decline
significantly at pH values below 6.8.
• At pH values near 5.8 to 6.0, the rates may be
10 to 20 percent of the rate at pH 7.0 (U.S.
EPA, 1993)
pH vs Nitrification Rates

From EPA-625/4-73-004a Revised

Nitrification and Denitrification Facilities
Wastewater Treatment
EPA Technology Transfer Seminar
 The Relationship Between pH and
Nitrification Rates
• A pH of 7.0 to 7.2 is normally used to maintain
reasonable nitrification rates, and for locations
with low-alkalinity waters, alkalinity is added
at the wastewater treatment plant to maintain
acceptable pH values.
• The amount of alkalinity added depends on
the initial alkalinity concentration and amount
of NH4-N to be oxidized (M&E).
Nitrification Rates are pH Dependant

Nitrification Activities at pH 7.2 and below

pH Activity
7.2 1.00
7.0 0.83
6.8 0.67
6.6 0.50
6.4 0.34
6.2 0.17
 Why Residual Alkalinity?
• After complete nitrification, a residual
alkalinity of 70 to 80 mg/L as CaCO3 in the
aeration tank is desirable (M&E).
• If this alkalinity is not present, then alkalinity
should be added to the aeration tank.
 Why is Alkalinity or Buffering Important?
Or: Alkalinity = Capacity

• Aerobic wastewater operations are net acid producing.

Processes influencing acid formation include, but are
not limited to:
– Biological nitrification in aeration tanks, trickling filters and
RBC’s
– The acid formation stage on anaerobic digestions
– Biological nitrification in aerobic digesters
– Gas chlorination for effluent disinfection
– Chemical addition of aluminum or iron salts

In wastewater treatment, it is critical to maintain pH in a

range that is favorable for biological activity. These optimum
conditions include a near neutral pH value between 7.0-7.4.
 The Importance of Steady State
Operations
• Effective and efficient operation of a biological
process depends on steady state conditions.

• The best operations will be carried on without

sudden changes in any of the operating
variables.
 Steady State vs Variable Operating
Conditions
Steady State Operations vs Variable Conditions
16

14

12

10

0
1 2 3 4 5 6 7 8 9

Variable Conditions Steady State Conditions

 Steady State Operations = Good Flock
• If kept in a steady state, good flocculating
types of microorganisms will be more
numerous
 Alkalinity = Steady State Operations
Alkalinity is the key to steady state operations.
The more stable the environment for the
microorganisms, the more effectively they will
be able to work.

In other words, a sufficient amount of alkalinity

can provide for improved performance and
expanded treatment capacity.
 How do I know how much alkalinity I need for my
system to operate properly?

• To nitrify, alkalinity levels should be at least

eight times the concentration of ammonia
present in the wastewater.

• The theoretical reaction shows that

approximately 7.14 mg of alkalinity (as CaCO3)
is consumed for every mg of ammonia
oxidized. Therefore, a rule of thumb is an 8 to
1 ratio of alkalinity to ammonia.
What Happens if I Don’t Have Enough
Alkalinity?
• This value may be higher for raw wastewaters
with higher influent ammonia concentrations
than the "normal."
• If adequate alkalinity is not present, this could
result in incomplete nitrification and
depressed pH values in the plant
A Reminder – pH and Alkalinity

From EPA-625/4-73-004a Revised

Nitrification and Denitrification Facilities
Wastewater Treatment
EPA Technology Transfer Seminar
 How Can I Determine How Much
Alkalinity I Need for my Plant?
• As a rule of thumb, to determine alkalinity
requirements for plant operations, it is critical
to know:
– influent ammonia in mg/L
– influent total alkalinity in mg/L
– effluent total alkalinity in mg/L
 The Math!
• For every mg/L of converted ammonia,
alkalinity will decrease by 7.14 mg/L.
• Therefore, to calculate theoretical ammonia
removal, multiply the influent (or raw)
ammonia mg/L X 7.14 mg/L alkalinity to
determine a minimum amount of alkalinity
needed for ammonia removal through
nitrification.
 EXAMPLE
Calculations for Determining Alkalinity Needs

Plant Influent Ammonia = 36 mg/L

36 mg/L ammonia X 7.14 mg/L alkalinity = 257 mg/L alkalinity requirements

257 mg/L is the minimum amount of alkalinity needed

to nitrify 36 mg/L influent ammonia.
 Calculated Alkalinity vs Actual
Alkalinity
• Once you have calculated the minimum
amount of alkalinity needed to nitrify the
ammonia present in the wastewater, it is then
critical to compare this value against your
actual measured available influent alkalinity to
determine if you have enough for complete
ammonia removal, and how much (if any)
additional alkalinity is needed to complete the
nitrification process.
 Example

Influent Ammonia Alkalinity needs for nitrification = 257 mg/L

Actual Influent Alkalinity = 124 mg/L
Influent Ammonia Alkalinity needs (257 mg/L) – Influent Alkalinity (124 mg/L)
= (257-124)
= 133 mg/L alkalinity deficiency.
 I Get It !!
• In other words, in this example, sufficient
alkalinity is not available to completely nitrify
the influent ammonia, and supplementation
through denitrification and/or chemical
addition will be required. Remember that this
is a minimum — you still need some for acid
buffering in downstream processes, like
disinfection.
 Alkalinity 101, or: Bio-Available
Alkalinity
• Most experts recommend an alkalinity
residual (effluent residual) to be between 70 –
80 mg/L as CaC03 (M&E)
• As previously identified, total alkalinity is
measured to a pH endpoint of 4.5 standard
units (su). For typical wastewater treatment
applications, operational pH never goes that
low.
 What is Bio-Available Alkalinity?
• When measuring for total alkalinity, the endpoint
reflects how much alkalinity would be available at
a pH of 4.5.

• At higher pH values of 7.0-7.4 su, where

wastewater operations are typically conducted,
not all of a total alkalinity measured to a pH of
4.5 su is available for use. This is a critical
distinction for available alkalinity or the “Bio-
availability” of alkalinity.
 The Experts Speak
• Therefore, in addition to the alkalinity
required for nitrification, additional alkalinity
must be available to maintain the pH in the
range from 7.0 to 7.4 standard units.

• Typically the amount of residual alkalinity

required to maintain pH near a neutral point is
between 70 and 80 mg/L as CaCO3 (M&E).
A Reminder – pH and Alkalinity

From EPA-625/4-73-004a Revised

Nitrification and Denitrification Facilities
Wastewater Treatment
EPA Technology Transfer Seminar
 Why Do I Need Alkalinity, and the Treatment
Plant Down the Road Doesn’t
Ok, You’ve done the math. Your calculations
show that your plant needs alkalinity. Some of
the questions you might have include:
• What makes my plant different? Why do I
need alkalinity?
– The answer can be related to sources of drinking
water (ground versus surface)
– Seasonal changes to water including rainfall and
potential for I/I
 Now What Do I Do?
If you have determined that you need alkalinity,
then your next step is to identify which source
of alkalinity supplementation that is best for
your facility, and the rate of application that you
will need to achieve adequate alkalinity residual.
.

Summary of Neutralization Reagent Operating Issues

Source: Charles River Associates, 1993

MAGNESIUM HYDROXIDE LIME CAUSTIC SODA SODA ASH

Primary compound (or derivatives) in “Milk of Hazardous to handle. Contact with eyes can cause Extremely hazardous to handle. Contact with eyes can Moderately hazardous to handle. Contact with eyes may
Magnesia”, antacids, foodstuffs, etc.. Comparatively permanent loss of vision. Repeated and prolonged cause permanent loss of vision. Contact with skin may cause temporary injury to the cornea. Contact with skin
safe to handle. Contact with eyes may cause contact with skin may cause severe irritation, mild cause severe burns. Breathing vapor may cause damage may cause slight irritation. Breathing dust may cause
SAFETY temporary injury to cornea. Contact with skin rarely burns and, in extreme cases, systemic injuries due to to the upper respiratory tract and the lungs. painful irritation to the nose and throat and prolonged
causes irritation. absorption. Breathing dust or mist may cause exposure may cause systemic injury.
intolerable discomfort to nose and throat

As noted above, is the base of “Milk of Magnesia” Limestone (CaCO3) is a naturally occurring mineral that Because caustic soda is highly corrosive, it can cause A by-product of neutralization is a sodium salt which, in
and, as such, is relatively harmless. Magnesium poses no threat to the environment. Lime (CaO) and severe physical injury to plant and animal life if it high concentrations, may harm animals and vegetation.
hydroxide is a natural mineral that poses no unusual hydrated lime (Ca(OH)2), however, are highly caustic escapes.
ENVIROMENTAL EFFECTS threat to the environment. In fact, it is beneficial. and can cause immediate damage to the environment.

Expensive solids handling equipment is required. To Requires elaborate safety equipment and rigorous, Very difficult to handle. Requires special solids-handling
Supplied as a ready-to-use slurry or powder. maximize effectiveness, lime is often slaked into a time-consuming safety procedures. Workers must be equipment. If used in solution, usually requires heated
Requires no special equipment except possibly an hydrated slurry. A large storage hopper is needed. A trained in safety and wear special clothing and goggles. valves and pipes because it freezes at 80oF. Generates
agitator in the slurry storage tank to prevent slurry with the maximum 30% solids content will Low temperatures can create major problems because a carbon dioxide, which may cause foaming and various
EASE OF HANDLING
settling. Low temperatures create no special contain grit that causes rapid wear to costly valves and 50% solution freezes at 57oF. Often requires process problems.
problems, because the slurry freezes at the same pumps. temperature sensors and heaters throughout the
temperature as the water being treated, i.e. 32oF. distribution system.

With a wide range of acids and metals, creates a With heavy metals and sulfuric acid, lime creates large If effluent contains heavy metals, creates large If effluent contains heavy metals, creates large
sludge that is very dense, fast-settling and easily quantities of calcium sulfate dehydrate, a sludge that quantities of gel-like, slow settling sludge that is difficult quantities of gel-like, slow settling sludge that is difficult
SLUDGE filtered and dewatered. Less sludge, less cost. settles very slowly and is difficult to filter and dewater. to filter and dewater. to filter and dewater.

Less than for caustic soda, lime, and soda ash, even Equipment costs higher than for magnesium hydroxide. Greater than for magnesium hydroxide because of need Greater than for magnesium hydroxide because it
with an agitator to prevent slurry settling in storage. Equipment maintenance is also higher because lime is for heated system and safety equipment. Corrosive. requires either expensive solids handling equipment or
May be used in powdered form (MgO, Mg(OH)2) abrasive. heaters for handling a solution that freezes at 80oF.
EQUIPMENT COSTS with minor modifications to installed feed systems.

Moderately fast acting to 95% of neutral. Slower Fast acting to full neutralization, but can become Extremely fast acting with most acids. Difficult process Fast acting to full neutralization with most acids.
above pH 6, resulting in more controllable process coated with, for instance, calcium sulfate, leading to control conditions and inefficient solids removal Difficult process control conditions and inefficient solids
RESIDENCE TIME conditions and enhancing flocculant performance in high usage rates. frequently occur when neutralization takes place very removal frequently occur when neutralization takes
(REACTION RATE) solids settling. rapidly. place very rapidly.

1.31 tons per ton of HCl. 1.23 tons per ton H2SO4. 1.52 tons per ton of HCl. 1.74 tons of insoluble salt per 1.60 tons per ton HCl. 1.45 tons per ton of sulfuric acid. 1.61 tons per ton of HCl. 1.45 tons per ton of sulfuric
DISSOLVED SOLIDS EFFLUENT* Generates only soluble salts. ton of sulfuric acid. (CaSO4-2H2O) acid.
(Based on stoichiometric ratios)

Usually no higher than pH 9, the limit set for most Can reach pH of 12. Can reach pH of 14. Can reach pH of 11.
MAXIMUM pH IF OVERTREATED countries (i.e. the U.S. Clean Water Act).

Available throughout the world in powder or slurry Readily available throughout the world. Readily available, but because caustic soda is co- Readily available throughout the world, but produced in
form (growing demand could limit supply in some produced with chlorine, the supply varies widely from only a few localities in a limited number of countries.
AVAILABILITY countries). surplus to shortage. Prices vary accordingly.
Footnote for Lime Application
 NEUTRALIZATION OF SULFURIC ACID (H2SO4)

For one mole (98 lbs) of 100% (H2SO4 – Sulfuric Acid) to be neutralized, the following
chemical reactions occur:

Magnesium Hydroxide Mg(OH)2 + H2SO4 MgSO4 + 2H2O

(58.3 lbs) (98 lbs) (120.3 lbs) (36 lbs)

Hydrated Lime Ca(OH)2 + H2SO4 CaSO4-2H2O

(74 lbs) (98 lbs) (172 lbs)

Caustic Soda 2NaOH + H2SO4 Na2SO4 + 2H2O

(80 lbs) (98 lbs) (142 lbs) (36 lbs)

Soda Ash Na2CO3 + H2SO4 Na2SO4 + CO2 + H2O

(106 lbs) (98 lbs) (142 lbs) (44 lbs) (18 lbs)

Caustic Potash 2KOH + H2SO4 K2SO4 + 2H2O

(112 lbs) (98 lbs) (174 lbs) (36 lbs)

These equations can be used to calculate the amount of alkali needed to neutralize one
ton of sulfuric acid and the resultant amount of salt formed:

Lbs Required Total Dissolved Solids

Neutralizing To Ratio To In Effluent (100%
Agent Neutralize Mg(OH)2 Basis)
1 Ton H2SO4 Per Ton of Acid
Magnesium
Mg(OH)2 1190 1.00 2460
Hydroxide
Hydrated Lime Ca(OH)2 1510 1.27 3510**
Caustic Soda NaOH 1630 1.37 2900
Soda Ash Na2CO3 2160 1.82 2900
Caustic Potash KOH 2290 1.92 3550

** The CaSO4-2H2O will precipitate as a sludge.

Sources of Alkalinity and
lbs/Alkalinity per Gallon
 How to Evaluate the Data
When reviewing the lbs/alkalinity per gallon in the
previous chart, each of the products identified have
specific chemical properties which determine the
amount of alkalinity present.

It is important to be aware that these estimates are

based on specific concentrations of product, and
that different concentrations provide different
volumes of alkalinity.
 What you need to know
To evaluate the best option for your facility, it is
important to determine the following facts:
– How much alkalinity is present in each product
under consideration (lbs alkalinity per gallon)
– Rate of application
– Cost/Budget
 How Much Alkalinity Do I Need per
MGD?

What is the
If not, how much
Calculated If yes, is there
Plant Influent Plant Influent What is amount of Is there sufficient additional
Amount of sufficient alkalinity How much additional
Alkalinity mg/L NH3-N in mg/L available Alkalinity in alkalinity present to alkalinity is
Alkalinity needed to provide an alkalinity (if any) is
mg/L? nitrify? needed to
for nitrification in effluent residual of needed to achieve 80
nitrify?
mg/L? 80 mg/L? mg/L effluent residual?

212 33 235.6 212 no 23.6 no 104

 Math and More Math!!
If the plant needs an additional 104 mg/L of
alkalinity per MGD per day, we then calculate
the different options in this manner:
Pounds of
Alkalinity Calculated GPD
Alkalinity per
Product Deficiency of Product per
Gallon of
mg/L MGD
Product

Lime Slurry 104 3.6 241

Caustic Soda 104 7.43 117
Magnesium Hydroxide 104 13.38 65
 $$$$
Once you know what your alkalinity needs are,
you can then calculate your costs per gallon or
ton based on quotes you receive from a supplier.
 Product Quality is Critical
• It is important to recognize that there are
superior and inferior sources of product on
the market.
• It is critical for you to be knowledgeable about
your product and specify products that meet
stringent industry standards.
• You should maintain a strict quality control
check on any product you receive
 With Proper Alkalinity…..
• A treatment plant experiences optimum
microscopic organisms whose primary
function is to reduce waste.

• When not provided with adequate alkalinity,

the ability of these microorganisms to settle is
greatly impaired.
 Additional Benefits of Good Alkalinity
• In activated sludge, the good microorganisms
are the type of floc forming organisms that
have the capability, under the right conditions,
to clump together and form a gelatinous floc
which is heavy enough to settle. The formed
floc or sludge can be then characterized as
having a SVI
 Alkalinity = Capacity
• The optimum pH range for good plant
operations is between 7.0-7.4. Although
growth can and does occur at pH values of 6-
9, it does so at much reduced rates (See above
charts). It is also quite likely that undesirable
forms of organisms will form at these outside
ranges and cause bulking problems. The
optimal pH for nitrification is 8.0; with
nitrification limited below pH 6.0.
 Optimum Oxygen Uptake
• Oxygen uptake is optimum at pH’s between
7.0 and 7.4 and shows a reduction as pH goes
outside this range. BOD removal efficiency
also decreases as the pH moves outside the
optimum range.
 Denitrification Can Add Alkalinity
• Plants with the ability to denitrify are able to
add back valuable alkalinity to the process,
and those values should be taken into
consideration when doing mass balancing. On
an average, you should expect approximately
4.2 mg/L.
 Conclusion
• In conclusion, Alkalinity is a major chemical
requirement for nitrification, and can be a
useful and beneficial tool for use in process
control
References and Sources of Additional Information

1. Metcalf & Eddy, Wastewater Engineering Treatment and Reuse, 4th Edition Revised;
McGraw-Hill Companies, Inc, 2003
2. USEPA Advanced Waste Treatment, A Field Study Training Program, California State
University Department of Civil Engineering and the California Water Pollution Control
Association, 1989
3. USEPA Process Control Manual for Aerobic Biological Wastewater Treatment Facilities,
March 1977
4. Water Environment Federation Operation of Municipal Wastewater Treatment Plants
Manual of Practice 11, 1990
5. USEPA Nitrification and Denitrification Facilities, Wastewater Treatment, EPA
Technology Transfer Seminar Publication EPA-625/4-73-004a Revised
6. Hartley, K.J., Operating the Activated Sludge Process, Gutteridge Haskins & Davey, 1985
7. USEPA Manual of Nitrogen Control, Office of Research and Development Center for
Environmental Research Information Risk Reduction Engineering Laboratory, Cincinnati,
OH, September 1993 EPA/625/R-93/010
8. USEPA Process Design Manual for Nitrogen Control, USEPA Technology Transfer,
October 1975