IRON REMOVAL

BY
MICHAEL C. KELLER
SYBRON CHEMICALS INC.

Iron is commonly found in rocks and soil throughout the United States. Under the proper
conditions, iron will leach into the water supply from the rock and soil formations. If iron is
present in the water where concentrations exceed 0.3 ppm, staining can occur. This staining can
affect plumbing fixtures, dish ware, clothes, and will produce a yellow to reddish appearance in
water. These levels may also impart taste and/or odor. The EPA has established a secondary
drinking water regulation of 0.3 ppm of water. This is not federally enforceable, since it is not
considered a health risk. It may, however, be enforced at the state or county level.

The following types of iron can be found in potable water supplies:

1. Sequestering iron
2. Iron bound in organics - Heme Iron
3. Iron Bacteria
4. Ferric Hydroxide or Red Water Iron
5. Ferrous Bicarbonate or Clear Water Iron

As one can see, iron can be found in many different forms. This creates a problem for the
removal of iron from water, since treatment methods differ for each type of iron.

Municipalities will feed sequestering agents, like sodium tripolyphosphate, hexametaphosphate,

or sodium silicate, into the water to tie up metals like iron and keep them in solution. These
sequestering agents will inhibit the reaction that would normally occur in untreated water. In
this case, iron is prevented from precipitated and causing a characteristic red stain. The problem
with these types of agents is that they can be broken down. As water treated with a sequestering
agent passes through a hot water heater, the polyphosphate or silicate bond can be broken.
When this occurs staining can become a problem. Sequestering agents will also inhibit the
exchange of iron onto softening resins.

To test for polyphosphate in water, one must test for total phosphate and orthophosphate. The
difference between these two values will be the polyphosphate. A minimum of 4 ppm
polyphosphate is fed into the water to treat 2 ppm of iron or less. For every 1 ppm of iron
above 2 ppm, an additional 2 ppm of polyphosphate must be added. Unfortunately, many times
the polyphosphate will be underfed, so only a portion of the iron will be sequestered; the balance
will be one of the other types of iron.

Laboratory testing has indicated that a strong base anion in the chloride form will remove the
polyphosphate from the water up to approximately 90%. The removal of sodium silicate from
the water is a little more difficult and requires the use of a strong base anion in the OH form
(regenerating with NaOH {caustic}). No testing has been performed to verify this, but silicates
 can only be removed by an OH form strong base anion. Further field testing is required to verify
both of these types of treatments and their limitations.

Iron can also be associated with organics such as tannins, Figure 7. This is also known as
organically bound iron or Heme Iron. Tannins are very large molecular weight organics that
are a breakdown product of dead vegetation. Most common in surface water and shallow wells,
tannins can cause water to have a yellow to brown color. These molecules have the ability to
hold on to iron by a mechanism called chelation (claw). This type of iron will not be removed
by softening resin. To treat for this type of iron, one must treat for the organic. A strong base
macroporous anion has been shown to pick up theses organics. The tannins are picked up by
both a ion exchange process and an absorption process. The regeneration must be performed
frequently with salt to reduce the potential for organic fouling. unfortunately, each geographic
region has its characteristic type of tannin, and removal by ion exchange may not be effective.
Oxidation is another process by which tannins can be removed. Sodium Hypochlorite, for
example, will oxidize both the tannin as well as the iron. Following the oxidant addition there
must be sufficient retention time for the oxidation to occur. The water must than pass through a
filtration media to remove the oxidized iron.

Bacterial iron is actually a microorganism that utilizes ferrous bicarbonate in a metabolic

process. In this process the iron is precipitated to its insoluble state and deposited around the
cell wall. Crenothrix, Clonothrix, and Gallionella are common types of iron bacteria. Water
containing this type of iron will again have a reddish color and may have an objectionable odor.
These bacteria can live in a wide range of environmental conditions. Bactericide are usually
effective in treating for this type of iron. Consult the bactericide manufacturer for the
appropriate type for specific water conditions, making certain it can be used in a potable water
application.

Iron is generally found in its oxidized state in nature, which is insoluble in water. Soluble iron,
or clear water iron, that is exposed to oxygen or some other type of oxidant will also precipitate
to the insoluble hydroxide form. This type of iron will have a yellowish to reddish appearance
in water. The precipitated iron must be removed by a filtration process. Generally a 5-25
micron filter will remove this type of iron, however smaller micron sizes may be required. Trial
and error will play a significant role in sizing the filter. Multimedia filters, garnet, sand, or
anthracite are common filter medias. Backwashing these products is critical, since that is how
the iron removed from the bed. It is imperative that the proper backwash flow be used to get the
optimum bed expansion. Greensand and manganese dioxide beds will also work effectively.
Although not recommended, softening resin may filter out particles of iron that are greater than
40 microns in size. Particles of iron that are filtered out on top of the bed can be removed
backwashing. Residual particles that remain on the bed after the backwashing can cause
pressure drop and channelling. To remove these particles an acid must will be required to
dissolve them. Be extremely cautious when using an acid, since hydrogen ions will be
exchanged on to the resin. When the unit goes back into service, a low pH will result, so be
certain to regenerate the resin back fully to the sodium form. It should also be determined
whether or not the unit is compatible with the acid being used.
Iron that finds its way into the ground water can react with CO, to form ferrous bicarbonate.
Ferrous bicarbonate or clear water iron is soluble in water and is not visible. This type of iron is
effectively removed by standard softening resin, since it has a positive charge. The following
equation summarizes the reaction that normally occurs with ion exchange resin:

2RNa + Fe(HCO 3)2 + 02 ----> R2Fe + 2NaHC03

Two sodium molecules are released from the resin for each molecule of ferrous bicarbonate that
is picked up by the resin. A high concentration of salt (8-26%) will reverse this reaction as seen
in the following equation:

R2Fe + 2NaCl ---> 2RNa + FeCI2

Some system modifications should be considered to optimize this type of water treatment.
Frequent regenerations are needed to prevent the iron from precipitating to its insoluble form.
The following chemical reaction occurs when clear water iron precipitates to red water iron:

4Fe(HCO) 2 + 2H2O + 02 ----> 4Fe(OH)3 + 8C02

Should dissolved iron oxidize, fouling can occur both on the surface of the resin, as well as
within the internal matrix of the bead. This type of fouling reduces resin capacity and can allow
excess iron to bleed through the system. There are correction factors that have been developed
in the industry to help size softeners for this type of iron removal. A typical correction factor
may state for each ppm of iron in the water multiply by a factor of 5 grains. This correction
factor was developed to increase the frequency of regeneration and decrease the amount of iron
fouling that might otherwise occur. Correction factors should be used a rule of thumb and may
have to be increased of decreased in a given area.

The effects of iron fouling can also be minimized with the use of chemical cleaners added with
the brine regenerant, Figure 8B. Sodium hydrosulfite and sodium bisulfite are examples of these
materials. They will chemically reduce red water iron to clear water iron. A preventative
maintenance procedure utilizing a reducing agent at a predetermined interval of time will help
keep the bed clean. Salt with a commercially available iron cleaning chemical can also be very
useful when iron levels are excessive. This will chemically clean the bed during each
regeneration, and it should not have any detrimental effect on the softening resin. Other
treatments include the use of sequestering agents like polyphosphates, chelating agents like
EDTA, or an acid strip utilizing hydrochloric acid, phosphoric acid, or citric acid. The use of
sequestering agents and chelating agents in expensive and will usually not be economically
feasible to clean small amounts of resin. Care must be taken when using an acid. The
equipment must be compatible so that corrosion does not occur. As stated previously, a
complete regeneration with salt is necessary to prevent a low pH from occurring. If you are
unsure of a particular procedure, consult your resin manufacturer.

Backwashing is a critical step in the regeneration sequence when dealing with iron. The
backwash step causes a mechanical scrubbing of the bead that helps strip iron that has
precipitated onto the surface of the resin. Most resin manufacturers set a minimum specification
of 50% bed expansion. This is usually accomplished with a backwash flow-rate of approximately
5 gpm/sq.ft. When setting the backwash flowrate, remember the water temperature is critical.
The warmer the water the greater the flowrate required to expand the bed 50%. The backwash
will also help to expel any particulate iron that has been filtered out by the bed.

Resin with a smaller particle size, fine mesh resin, appears to have a greater ability to pick up
and release clear water iron. The theory behind this material has to do with its greater surface
area. There seems to be an enhanced absorption and desorption of iron from this type of resin,
because the exchange occurs to a greater degree at the surface of this material. Any fouling that
might occur can more easily be removed, since it occurs on the outer layer of the resin.
Cleaning agents are also more effective on surface iron fouling.

The last and probably most effective operational change that can be made occurs with the type of
regeneration, Figure 8B. Countercurrent (upflow) regeneration, where the regenerant flow runs
opposite the service flow will lower iron leakage. In a typical cocurrently (down flow)
regenerated unit, the iron must pass down through the entire bed of resin before exiting the unit.
In this case the iron will come in contact with the entire bed. A heal of unregenerated resin will
be left at the bottom of the unit, after regeneration, which contains both hardness and iron. The
iron in this heal, as well as throughout the entire bed, can precipitate and increase iron leakage
form the system. A countercurrent system will instead leave a heal of unregenerated resin at the
top the bed. Any iron in this heal must travel through the entire bed of resin (during the service
cycle) before excess leakage would occur. With the exception of the top of the bed, the balance
of the resin is exposed to a little iron if correctly operated.

To maximize countercurrent operation, it is necessary to avoid fluidizing the bed. To avoid

fluidizing the bed, the resin can be packed into the tank, a screen can be installed, or
polyethylene beads can be placed on top of the resin. When a fixed bed is not used, the
regeneration flow up through the bed must be reduced to keep the bed expansion below lO% to
avoid turnover. Brine pulsing can accomplish this same effect. The brining cycle may also be
used as the backwash step. System testing is suggested.

Obviously, water with a higher amount of suspended solids should be avoided or, at the least,
prefiltered. The use of a 5 micron pre-filter should help to eliminate the build of suspended
solids. The build up of suspended solids on the bed can cause channelling and pressure drop. If
iron precipitates in this type of system, a reducing agent can be used to clean the bed.

In many applications it may be impractical or impossible to prevent the bed from fluidizing.
Even if the bed fluidizes, the iron should be pushed right out of the system during the
regeneration. A small portion of the iron may still end up distributed through the resin bed, but
not to the extent of a cocurrently regenerated unit.

Countercurrent regenerations do not have a significant effect on the operating capacity.

However, hardness and iron leakage are kept to a minimum. Countercurrent regenerations are
also more efficient than cocurrent regenerations, since less salt is actually needed to achieve low
leakages. Generally, lower amounts of rinse water are required to rinse this type of unit, which
is critical in areas where water usage must be kept to a minimum.
 Questions are often asked as to the amount of iron that can be removed by softening resin. This
is an extremely difficult question to answer. Standard softening resin can remove up to 600
grains per cubic foot. This iron must ferrous in nature, because any other form of iron will not
be removed by softening resin. Remember, regenerations need to be performed frequently, even
if the resins capacity is not totally expended. There are many guarantees stating that a unit will
handle up to a certain amount of iron. As a resin manufacturer, there is no way to guarantee the
amount of iron that can be removed by softening resin. First, if a water has been tested and
found to have 5 ppm of total iron, it could be in any of the forms discussed in this paper. Unless
that iron is ferrous in nature, softening resin will not work. Second, equipment design is critical.
If the system is not airtight, the clear water iron will precipitate. Third, long service cycles will
precipitate a greater amount of iron than short service cycles. All these situations make it
impossible for a resin manufacturers to guarantee softening resins for iron removal.

OTHER METHODS OF IRON REMOVAL

Manganese dioxide (MnO) is a naturally occurring mineral that can be mined from the ground,
as well as, manufactured synthetically. It works as a catalyst to promote the oxidation of iron.
Basically, iron and oxygen are attracted to the manganese dioxide, where they are retained long
enough to react, causing a precipitation. This material can also precipitate iron if there is no
oxygen present in the water. This performed in a reaction where the MnO2 is reduced to MnO
and ferric hydroxide is precipitated, as seen in the following chemical reaction:

MnO 2 + 2Fe(HCO3)2 + H2O ---> MnO + 2Fe(OH)3 + 4C02 + H2O

During the backwash, the surface of this material is scoured, removing the MnO. This exposes
fresh MnO2, Which is further used to oxidize the iron. Simple backwashing is all that is needed
to regenerate manganese dioxide. No chemicals are required to regenerate this material.
Manganese dioxide should work well on both clear water iron, as well as red water iron.

Manganese dioxide does have some drawback. First, Mn02 weighs approximately 120
lbs./cu.ft. The backwash flow must be sufficient to expand the bed a minimum of 30%. 50%
bed expansion is optimum. This is generally accomplished with a flow of 15-18 gpm./sq.ft.
Remember, backwashing is a critical step with this product, since this is how the bed is
rejuvenated. Secondly, manganese dioxide works most efficiently at a pH of 6.5 to 9. If the pH
falls below this specification, pH adjustment is required. Last, manganese dioxide should not be
used on waters that have bacterial iron or organic iron. There is an annual attrition rate of up to
5% under normal operating conditions.

Birm is another type of manganese dioxide. It is a silicon dioxide core that has been coated with
manganese dioxide. This makes Birm much lighter than its ore counterpart, less than 50
lbs./cu.ft. The benefit of this type of product is that it can be backwashed at a flowrate of 8-l2
gpm./cu.ft. Birm does require dissolved oxygen in the water for the precipitation of iron, where
the manganese dioxide ore does not. Birm relies on its ability to act as a catalyst between iron
and oxygen. It has a limited amount of MnO2 available, so it does not have the ability to supply
oxygen through a redox reaction. The oxygen content should be, at least, equivalent to 15% of
the total iron content. If the oxygen content is less than 15%, aeration is required. Birm is
recommended on levels of iron less than 10 ppm. It can be utilized on higher concentrations, but
the frequency of regeneration (backwashing) becomes excessive. Birm has a capacity of
approximately 400-500 grains/cu.ft. It can treat up to 800 gallons of water containing 10 ppm
Fe as CaCO3. Birm should not be used on waters that have oil or hydrogen sulfide, and the
organic matter should not exceed 5 ppm. As with any product, consult the manufacturer for
operational guidelines.

A broad category in iron treatment is the oxidation process. The following are types of
oxidation and precipitation methods:

1. ozonation
2. Aeration (Oxygen)
3. Chlorination

The addition of any one of these chemicals will cause clear water iron to precipitate. The
precipitated iron is allowed to settle out in a retention tank and the effluent water is finally
passed through a filter. This filter is required to pick up any of the suspended particles that did
not settle out in the retention tank. Figure 9 shows the amount of oxidant required to react with
1 ppm of iron. Ozonation and chlorination can also be used as disinfecting agents.

Ozone is created when electrical current is passed through the air. A portion of the 02 molecules
split and form elemental oxygen, which reacts with the 02 molecule to form 03.

2Fe(HCO 3)2 + 03 + H2O ---> 2Fe(OH)3 + 4C02 + 02

Ozone is an extremely strong oxidizing agent, which reacts very quickly with any oxidizable
material in the water, including iron. Ozone is so reactive that is difficult to maintain a residual.
Because of this, incomplete oxidation may result. Ozone will not impart taste or odor into the
water, which is a benefit. Ozone may not be as effective as an oxidant in waters bearing tannins.
It will, however, effectively treat bacterial iron.

Aeration is another process by which iron can be oxidized. Air is bubbled up through the water.
The iron will precipitate, since the air has oxygen contained within it, as long as there is
adequate retention time. The required retention time increases as the pH and temperature
decreases, as seen in Figure 10. These conditions effect, to some degree, all of the oxidation
processes. Following the aerator, a settling tank and/or filter should be utilized to remove the
precipitated iron. A coagulant may have to be added at this point to increase the size of the
particles for effective settling and/or filtration. This process will usually be used as a
pretreatment. Unreacted iron and/or colloidal iron can be polished by another process down
stream. There are aeration systems that incorporate all of this technology into one package.

Chlorination is another extremely effective oxidant. It can be fed into a system as sodium
hypochlorite, calcium hypochlorite, or chlorine gas. Sodium hypochlorite is usually the oxidant
of choice, since it is relatively inexpensive and readily available. These chemicals work on the
same principle in that the OCl ion (hypochlorite) performs the disinfection and oxidation. The
following equations show the reaction that occur during oxidation:
 2Fe(HCO 3)2 + Cl2 + 2H2O ---> 2Fe(OH)3 + 2HCl + 4C02

2Fe(HCO 3)2 + NaOCl + H2O ---> 2Fe(OH)3 + NaCl + 4C02

4Fe(HC0 3)2 + Ca(OCl)2 + 2H2O ----> 4Fe(OH)3 + CaCl2 + 8C02

The treated water then passes into a retention tank where the iron will precipitate and settle out.
A coagulant may be helpful in the retention tank to produce a particle sufficient in size to
enhance the settling properties of the precipitated iron. Be sure the coagulant is not overfed, as
this could foul the water treatment equipment downstream. The chlorine compound is fed into
the influent water in a concentration high enough to allow for a residual chlorine content of l-4
ppm when the water leaves the retention tank. generally a 30 minute retention time is sufficient
to allow for the reaction to occur. However, longer retention time may be required. Following
the retention tank, an activated carbon filter is necessary, since it will dechlorinate the water, as
well as filter out a portion of the suspended iron. Whether a carbon filter or some other type of
filter is used, frequent backwashing is critical to remove precipitated iron from the bed.

A side effect of the chlorination is the formation of trihalomethane, a known carcinogen. When
chlorine reacts with tannins in the water, trihalomethane can be formed. Caution must also be
taken to keep chlorine tablets dry. The tablets can reacts with small amounts of water, causing
an exothermic reaction that can case fire. Remember, this is a oxidant, and oxygen fuels fire.

Chlorine will add taste and odor to the water. From a health stand point this is no problem, but
esthetically it is unappealing. As stated previously, chlorine can be removed by activated
carbon.

Manganese greensand or glauconite is a mineral that is mined in the eastern part of the U.S. The
base material is composed of an alumino-silicate, which is treated with manganese chloride and
then regenerated with potassium permanganate (KMnO4). Upon exhaustion, the greensand is
backwashed to remove the precipitated iron from the bed. KMnO4 is then passed back over the
bed to oxidize the MnO to MnO2. This type of regeneration is known as intermittent. Iron is
precipitated directly by the greensand in a redox reaction. iron up to 1O-15 ppm can be treated
in this fashion. K M n O4 can also be fed continuously ahead of the bed. In this type of
regeneration, the iron is precipitated prior to the bed, as well as by the bed. The oxidation
process that causes iron to precipitate prior to the bed can be seen in the following reaction:

KMnO 4 + 3Fe(HCO3)2 + 7H2O ---> MnO2 + 3Fe(OH)3 + KHCO3 + 5C02 + 5H2O

This process is normally used in larger systems that will be monitored. Some type of filtration
media should be used prior to the bed to filter most of the precipitated iron. This will help to
prolong the service run, since this should reduce the pressure drop on the bed of greensand.
Generally, when pressure drop exceeds 10 psi, the unit is backwashed. The backwash flow
should be sufficient to expand the bed 40%.
The minimum recommended pH for this process is 6.2. Waters with acidic pHs will strip the
M n O2 coating, making the greensand useless. When this occurs, the greensand must be
replaced. Chlorine injection can be used on either type of regeneration, especially if hydrogen
sulfide and manganese are present. H 2S and Mn will consume a disproportionate amount of
KMnO4 compared to iron. Iron requires approximately 1 ppm of permanganate, while H2S and
Mn require 6 ppm and 2 ppm respectively. Chlorine will help oxidize the hydrogen sulfide and
manganese, as well as the iron, allowing the KMnO 4 to go further. When chlorination is used in
conjunction with manganese greensand, the use of permanganate can be lowered drastically.

Potassium permanganate is not easy to work with. The KMnO 4 will stain just about anything it
contacts. It is expensive and,. if it is overfed, the water will have a pink to purple color. It
should also be noted that KMnO4 is toxic.

When iron has precipitated, it must be physically filtered from the water. Sand, anthracite,
activated carbon, garnet, or a multimedia filter should adequately remove the precipitated iron.
The space between the particles of media is the mechanism for physical removal. In a filter bed,
the actual filtration occurs at the top, if it is operated in a downflow fashion. Perhaps the most
important characteristics of a filter is the particle size. The size of the media dictates the size of
the particle that can be removed. Size will also impact on the flow rate and the pressure drop.
The smaller the particle size, the greater the pressure drop, and lower the flow rate. Media with
a smaller particle size will utilize a smaller portion of the bed than does the media with a larger
particle size. A larger particle size distribution will allow for greater penetration of solids into
the bed, therefore, a greater portion of the bed will be used. In the filtration of iron, the particle
size of the media must be small enough to remove the precipitated iron. This will be a
judgement call, with some trial and error.

Neutralizing filters have also been used in iron removal. Magnesium oxide and calcium
carbonate (products like Corosex and calcite) are used to increase pH in acidic waters. By
increasing the pH, the iron can more readily precipitate. The iron is then filtered out in the bed.
Simple backwashing is required to keep the bed from plugging up with precipitated iron. This
media is sacrificial, and occasional replacement is required (more so than the other iron removal
processes).

Calcium carbonate, sometimes referred to as limestone or marble chips, can be used by itself or
in combination with magnesium oxide. This helps prevent the magnesium oxide from becoming
an agglomerate. Magnesium oxide is more soluble and will increase pH at a faster rate. When
used in conjunction with calcium carbonate, the filter will increase waters with a low pHs (4-6)
more effectively than calcium carbonate alone.

Iron removal involves both art and science. Equipment design is critical, but most important
thing is to know what type of iron is to be treated. This dictates what iron removal process is
most likely to be effective.
Figure 8B.

IRON CLEANING CHEMICALS

REDUCING AGENTS
SODIUM BISULFITE - NaHS03
SODIUM HYDROSULFITE - Na2S204 + 2H20
HYDROCHLORIC ACID - HCl
PHOSPHORIC ACID - H3P04
CITRIC ACID - OHCCH2(COOH)3
Figure 9.

CHEMICAL REQUIREMENTS FOR

THE OXIDATION OF IRON
AMOUNT REQUIRED TO
OXIDANT OXIDIZE 1 PPM IRON

OXYGEN (02) 0.14 PPM

CHLORINE (Cl2) 0.62 PPM
OZONE (0,) 0.86 PPM
POTASSIUM
PERMANGANATE (KMnO4) 0.91 PPM

NOTE: THIS SHOWS THE STOICHOIMETRIC AMOUNT OF

OXIDANT REQUIRED TO REACT WITH 1 PPM IRON. IN
PRACTICE, THE ACTUAL AMOUNT REQUIRED CAN BE
GREATER, SINCE THERE ARE AGENTS IN THE WATER THAT
MIGHT ALSO REACT WITH THE OXIDIZER BESIDES THE
IRON.