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Technical

Paper

Advances in Nitrate Removal


Authors: David Elyanow, Process Manager, and
Janet Persechino, Product Manager

Abstract
Electrodialysis has been used for treating saline
waters for fifty years. Advancements in membrane
and system technology have made Electrodialysis
Reversal (EDR) an especially attractive technology
recently for treating waters contaminated with high
Nitrate levels. Technological improvements are discussed including the following areas:
1. The Reversal
and fouling

Process

effects

on

scaling

2. Advances in membrane technology leading to


more chemical and fouling resistance
3. Advances in spacer design and hydraulics
Electrodialysis Reversal is a competitive technology
to Reverse Osmosis for many Nitrate removal
applications. A comparison is made between the
applications of these technologies to illustrate
where the high recovery advantages of EDR may
be a greater advantage as compared to the typically higher rejection capabilities of RO.
Several examples of Nitrate removal by Electrodialysis Reversal are presented including recent
experience in Israel on a system recovering drinking water at over 94% recovery from wells containing 135 mg/l of Nitrate.

The Problem of Nitrates


Nitrate contamination of groundwater is a common
problem throughout the world. The problem is
prevalent in many parts of Europe, including Great
Britain, France, the Netherlands, Germany, and
Switzerland; several parts of the United States, and
in Keepok, Israel. Most nitrate contamination is a
result of intensive agriculture and the use of nitroFind a contact near you by
visiting gewater.com or
e-mailing custhelp@ge.com.

gen containing fertilizers, although occasionally it


may be a result of natural nitrates or contamination from wastewater sources.
The primary health risks associated with elevated
nitrate levels are methemoglobinemia, which
causes the blue baby syndrome in infants1, and
the potential formation of carcinogenic nitrosamines. In infants, the higher pH of their upper respiratory tract accelerates the conversion of nitrate
to nitrite. The nitrite in turn oxidizes the infants
hemoglobin to methemoglobin, which is unable to
carry oxygen in the bloodstream. In severe cases
the result may be fatal. The cancer causing effects
of nitrates are not well documented, but nitrate
reaction products, nitrosamines and nitrosamides
are
strongly
considered
as
potential
human carcinogens.
As a result of the health consideration the Maximum Contaminant Limit for nitrate in drinking water
has been set at 10 mg/l nitrate as nitrogen (44.3 as
NO3 ) in the United States and Canada. A similar
guideline of 50 ppm as NO3 has been set by the
WHO2, while the European Community (EC) standards allow a maximum admissible concentration
of 50 mg/l as NO3 and a guide level of 25 mg/l
as NO3.

Treatment Technology
There are a number of treatment technologies
available for the reduction of nitrates in drinking
water. These include the following:
1. Ion Exchange using strong base anion resins
regenerated with NaCl
2. Biological Denitrification using Methanol or
Ethanol addition
3. Electrodialysis or Electrodialysis Reversal
4. Reverse Osmosis

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Ion exchange generally substitutes chloride anions


for the nitrate anion without substantially changing
the salinity or the cation makeup of the feedwater.
Sulfate is preferentially removed and replaced by
chloride unless special nitrate selective resin is
used. Because of the batch nature of the process
the anion composition and pH of the product
changes over the service cycle of the ion
exchanger. Since salt is used for the regeneration
of the ion exchanger, the waste contains substantial added sodium chloride. This can pose a problem for waste disposal since high salt loads can
affect the performance of waste treatment plants
or may be otherwise regulated. Since chloride is
exchanged in this process, the chloride level of the
product is elevated and there is no benefit of TDS
reduction as with the membrane processes. In
summary, ion exchange can be a cost efficient
method for nitrate removal as long as waste disposal is not a major issue and as long as Chloride
or TDS reduction is not desired.
Biological treatment for nitrates is not common for
drinking water applications but widely practiced in
wastewater treatment. The process generally
involves the reduction of nitrates to nitrogen by
bacteria in an anoxic bioreactor. A carbon source is
generally required by the bacteria, which for waste
treatment can usually be supplied by the natural
BOD. The relatively low organic content of drinking
water sources generally requires the addition of
methanol or ethanol to drive the reaction. Concerns
about potential discharge of bacteria or methanol
into drinking water have generally limited the
acceptance for this approach. As with ion
exchange, the salinity of the water from biological
is not significantly changed and this can be a disadvantage for areas that have elevated salinity
or hardness.
The membrane processes Electrodialysis Reversal
(EDR) and Reverse Osmosis (RO) are both seeing
increasingly widespread use for nitrate reduction.
Since both processes remove other ions along with
nitrate, they also result in lower product salinity
along with lower levels of sodium, chloride, hardness, etc. For areas where the salinity as well as
the nitrate is high, this results in a substantial water
quality improvement as compared to the nonmembrane processes above. For waters with moderate levels of nitrate the product of either RO or
EDR may be blended with feedwater to achieve the
desired nitrate level at higher production level and
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and recovery. These processes and their advantages will be discussed in more detail below.

The Electrodialysis Reversal Process


Electrodialysis is an electrically driven process that
uses a voltage potential to drive charged ions
through a semi-permeable membrane, reducing
the TDS in the source water. The process, shown in
Figure 1, uses alternating; semi-permeable cation
(positively charged ion) and anion (negatively
charged ion) transfer membranes in a directcurrent (DC) voltage potential field. The source
water flows between the cation and anion membranes via flow spacers that are placed between
the membranes. The spacers are used to provide a
flow path for the water, support the membranes,
and create turbulent flow. The DC voltage potential
induces the cations to migrate toward the anode
through the cation membrane, and the anions to
migrate toward the cathode through the anion
membrane. The cations and anions accumulate in
the reject water side of the membranes and low
TDS product water is produced on the dilute side of
the membranes. The electrodialysis reversal system periodically reverses the polarity of the electric
field, and consequently the dilute and concentrates
compartments, to help flush scale forming ions
off the membrane surface and minimize membrane cleaning3.

Figure 1: Negative vs. Positive Polarity

Advances in EDR Membranes


The first membranes used for electrodialysis were
anion and cation exchange membranes made
from crushed ion-exchange resins in an inert
matrix. These membranes have been replaced by
homogeneous membranes, which typically have
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lower resistance and are generally more resistant


to scaling.
In the 1980s acrylic-based anion exchange membranes were broadly introduced which exhibited
the advantages of substantially increased resistance towards organic fouling and an enhanced
degree of chlorine tolerance. The difference in
membrane organic fouling observed was somewhat similar to that seen between the analogous
organic resistant acrylic resins versus the standard
styrene-divinylbenzene resins. The increased chlorine tolerance allowed the EDR systems to be
operated with up to 0.5 mg/l free chlorine residual
thus offering the benefits of a continuous disinfection residual throughout the treatment process. It
also allowed the EDR system to be chemically
cleaned with up to 20 mg/l of free chlorine resulting in better cleaning for difficult biological or
organic contaminants.
More recent advances in membrane technology
have allowed the one step machine manufacture
of ion exchange membranes reducing the cost and
resulting in lower membrane resistivity. Various
groups have also developed and manufactured
more nitrate selective membranes. While
enhanced membrane selectivity has some advantages, the removal by electrodialysis of nitrate in
the dilute solutions is generally limited more by
spacer hydrodynamics than by membrane properties. Simply put, the nitrate cannot be removed
unless it reaches the anion membrane surface.
Cost effective design generally dictates that the
EDR membrane stack is operated at close to the
concentration polarization point. At this point the
concentration of nitrate at the anion membrane
boundary layer is depleted and the removal rate of
nitrate is more a function of the ionic mobility of the
nitrate ion than membrane selectivity. As a result,
improvements to the spacer that allow better
transport of nitrate to the membrane surface have
more of an economic impact on the system as discussed below.

comparison to a hydraulic stage of conventional


stacks. These high-performance spacers are incorporated into a new membrane stack, designated a
Mark IV stack. The Mark IV stack has 38% more
usable membrane area than a conventional Mark
III stack. The increased area is available because
the spacers are thinner so more cell pairs can be
included in one stack, and because the usable
membrane area per cell pair is greater. The
increased available membrane area results in
higher demineralization per stack; therefore fewer
membrane stacks are needed to demineralize a
given volume of water to a specific TDS level.
Recent advances in EDR system design were made
with the introduction of the GE Water & Process
Technologies EDR 2020*, using Mark IV stacks,
variable frequency drives to minimize pumping
power and 4-way valves to maximize recovery5.
The pumping power requirement to an EDR plant
frequently varies as cartridge filters fouled or if
temperature drops so that the stack pressure drop
increases. Use of the variable frequency drive
reduced the pumping power by approximately
25% over a conventional GE EDR system, while
maintaining a system design that had the pumping
capacity to allow for an increase in feed pressure.
The variable frequency drives also make the system easy to start up and shut down as the water
demand varies.
The 4-way valves reduce the piping required to
reverse the flow and reduce the amount of time
the system operates off spec at polarity reversal.
Conventional EDR systems with a 15-minute reversal time are off-spec for about 36 seconds per
reversal, or 4% of the time. In some large EDR
plants, use of the 4-way valve reduced reversal
times to less than 15 seconds or 1.7% of the product flow. Since the off spec is usually treated as
part of the EDR system waste, this extra product
flow translates into approximately 2% higher water
recovery with the new system than was possible
with the conventional system.

Advances in EDR Systems

EDR Performance in Nitrate Removal

A new high-performance spacer that promotes


greater turbulent flow in an electrodialysis stack,
has been developed, and is now in operation4. The
maximum demineralization that can be obtained in
a single hydraulic stage has been increased in

A previous paper6 has discussed nitrate removal at


water plants installed by GE in Bermuda, Delaware
and Italy. These plants have demonstrated reliable
operation now for over 8 years, at nitrate removal
rates of 69% to 92.6% along with TDS removal

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rates of 53% to 88%. Performance data is summarized in Table 1. These plants consist of two to
three stages and do not include the newer high
performance spacers.

Table 2: EMS Mekorot EDR Design Parameters

Table 1: EDR Plant Data Nitrate Removal Application

For many nitrate removal applications high recovery is essential. EDR has demonstrated recoveries
of 94% for over 10 years now at a 593 m3/hr
drinking water plant for Suffolk, Virginia, USA7.
Although this plant is primarily removing TDS and
Fluoride, it demonstrates high recovery operation
at a large scale over a long time period.
A new plant requiring high recovery, employing the
new MKIV stack design and the other GEs EDR
2020* features, was commissioned recently in
Safaria, Israel for EMSMekorot. Figures 3 and 4
include photos of the site and the EDR stacks. The
plant produces 2208 M3/D of drinking water before
blending. The nitrate contaminated source water
comes from a network of 80 to 100 different wells
with a blended nitrate content of 115 to 135 mg/l.
The plant has been in operation since May 1999 at
94% water recovery, achieving 52% nitrate reduction in a single stage at nearly 30% increased
capacity per line as compared to previous designs.
Table 2 gives a summary of the plant parameters.
The plant is designed with the provision for the
blending of product water with feed to increase
production and recovery. The initial blend ratio is
low due to feed nitrate levels of 15% to 30%
greater than design. Provision has also been made
to increase capacity expansion by adding a future
second stage thus increasing the nitrate removal to
90%. Data from this plant is included in Figure 2,
and Table 3.

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Figure 2: EDR Nitrate Removal

Table 3: Nitrate Removal of EMS Mekorot EDR Plant

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membrane will rise until the solution concentration


on both sides of the membrane is nearly equal.

Figure 3: Safaria Site Entrance

Figure 4: Safaria EDR Stacks

Overview of Reverse Osmosis


Principles of Operation
Reverse Osmosis (RO) a process for the removal of
dissolved ions from water in which pressure is
used to force the water through a semipermeable
membrane element which will pass the water but
reject most of the dissolved materials.
To understand reverse osmosis, one must first
understand the principle of osmosis. Osmosis can
be defined as the spontaneous passage of a liquid
solvent (water) from a dilute solution across a
semipermeable membrane to a more concentrated solution. The driving force for this flow is
called osmotic pressure, and is shown in Figure 5
RO-1 as the difference in height of the water columns on either side of the membrane. If no other
force is applied to the system, the pressure (height
of the column) on the concentrate side of the mem-

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The flow of solvent from low concentration to high


can be halted by applying a pressure equal to the
osmotic pressure on the more concentrated solution side. If this external pressure is increased further, the flow of water will be reversed from its
natural flowing direction and towards the more
dilute solution. The reversing of the flow is the
process of reverse osmosis. For example, if a variable pressure P were applied on the more concentrated solution side of a semipermeable membrane
element, the following conditions could be realized
as illustrated in Figure 5 RO-2:

Figure 5: Ro-1 and RO-2

1. P is less than the osmotic pressure of the solution. The solvent flows from the more dilute
solution to the more concentrated solution. This
condition, as shown in Figure 5 RO-1, represents the phenomenon of osmosis.
2. P is greater than the osmotic pressure of the
solution. Solvent flows from the more concentrated solution to the pure solvent side of the
membrane. This condition, as shown in Figure 5
RO-2, represents the phenomenon of
reverse osmosis.

RO Membrane Rejection
The ideal situation would be that of a truly
semipermeable membrane which would allow only
water to pass across it (100% salt rejection), but this
is not the case in reality, as there is always a very
small amount of salt which passes across the
membrane. Nitrates are not as well rejected by
most reverse osmosis membranes as is chlorides
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or sulfates. For comparison, a typical rejection for


NaCl is 98% as compared to 93% for NaNO3. This is
generally not a significant problem due to the very
high overall rejection properties of most RO elements and the typical requirement for permeate
blending.

Reverse Osmosis Plant Design


Considerations
High water recovery in RO systems is desirable for
a number of reasons. These include the need to
reduce the size of any filtration equipment, to
economize on the pipeline sizes and to minimize
the amount of water drawn from the aquifer (in the
case of brackish water sources). Another compelling reason in many countries for the reduction in
waste quantity is the high cost of disposing of
the water.
A restriction on high recovery is the potential for
scale formation. Since the concentrate stream flowing across the RO membrane surface is being continually more concentrated as it flows down the
series of elements in the pressure vessel it can
become saturated in certain salts. These salts can
then precipitant from solution and be deposited on
the membrane surface. Because the membranes
are not perfectly flat sheets, but have many millions of pores which are relatively large compared
to the salt crystal which is deposited, it may be difficult to remove the salt from the membrane. This is
especially true in the case of scaling salts such as
calcium carbonate, calcium sulfate, barium and
strontium salts. The surface area of the membrane
would therefore become smaller, reducing the efficiency of the process, and the salt would become a
seed for crystallization.
In order to prevent this from occurring, there are
two possibilities, either reduce recovery or use
chemicals (scale inhibitors or acid) which will retard
or prevent scale formation. In most plants recovery
is first limited by Calcium Carbonate precipitation
(using Langelier Saturation Index or Stiff and DaviIndex) which may be controlled by acid or antiscalant addition. Other precipitating salts such as
Calcium Sulfate, Silica, Barium or Strontium Sulfate,
and Calcium Fluoride can only be controlled with
antiscalants or reduced recovery. Because RO is
not a reversing process the achievable recovery is
less than that from EDR plants.
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Another concern in the design of RO systems is the


potential for biofouling. This is not generally as
much of a problem for wellwaters as it is for surface waters. Biological activity in the feed water
(biofouling) is often controlled by disinfection of the
feed water, usually with chlorine or hypochlorite.
One drawback with this method for RO is that the
chlorine needs to be removed before the water
reaches the membrane since most membranes
show very low chlorine tolerance. In most cases, it
is beneficial to remove all traces of chlorine upstream of the membranes either by dosing with a
reducing agent (such as sodium bisulfite) or by contacting with activated carbon.
The potential for colloidal fouling of the RO membrane is usually evaluated by measuring a silt density index (SDI) at the water source. Clean
wellwaters usually have low values ranging from
SDI15 of 0 to 3. Poorly drilled wells or water
sources subject to contamination may yield much
higher SDIs and will then require suitable pretreatment such as in-line coagulation and filtration
upstream of the RO plant.

RO Performance in Nitrate Removal


In 1995 GEs Italian subsidiary, GE Italba, commissioned a series of reverse osmosis plants for nitrate removal in the greater Milan area. The source
water for these plants is a series of wells with
nitrate concentrations in the range of 50 to 60 mg/l
and all having SDIs of less than 1. The objective of
these plants is to produce and deliver to the distribution network, drinking water at a nitrate concentration lower than 40 mg/l, while releasing to the
sewer a waste stream at a nitrate concentration
lower than 132 mg/l.
As summarized in Table 4, the project consists of a
network of 13 small to medium sized plants in 9
locations. The plants are sized to produce from 7 to
58 m3/hr of permeate which is blended with feed
at each site at a ratio of roughly 79% blend water
to 29% permeate. The RO recovery for each plant
averages 59% but with blending the overall recovery ranges from 77 to 88%. Over the last five years
of successful operation, the plants have used antiscalant at a dosage rate of 2.0 to 3.5 mg/l and
clean-in-place (CIP) chemical cleanings are performed every 18 months. The system has central
control and data logging from the GE Milan office
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Table 4: Design Data from Milan Area Reverse Osmosis Nitrate Removal Plants

allowing the system to be operated and maintained by a staff of three technicians.


These plants offer a good illustration of design
characteristics favorable towards reverse osmosis
technology for nitrate removal. First of all, the
source waters are all from low SDI well water
sources and thus require minimal pretreatment.
The low CIP frequency is indicative of the high quality of the well supplies. Secondly, the waste nitrate
limit essentially limits the overall system recovery
thus giving no incentive towards high recovery. In
addition the low recovery generally allows simpler
RO design with only one stage generally required.
Finally, the best economical choice for small capacity systems (<25 m3/hr) are simple RO plants, which
have less electrical and hydraulic complexity than
EDR and other technologies.

EDR vs. RO Selection Criteria for Nitrate


Removal
Most of the aspects that touch on the selection of
either EDR or RO technology for nitrate removal
applications have been mentioned in the previous
discussion. The 94% recovery achieved by the
Safaria EDR plant would not be possible with good
RO design. On the other hand, the high quality, low
recovery, and low capacity of the Milan area wells
favor more economical RO plants. In general one
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can say that high recovery, elevated SDI, and


potential for biofouling are preferential to EDR technology, while lower recovery, low SDI, and low
plant capacity are preferential towards RO. These
criteria are summarized in the table shown
in Table 5.
Table 5: Comparison of EDR and RO for Nitrate Removal
Typical Values

Conclusions
The basic conclusions of this paper may be summarized as follows:
1. The membrane processes of Electrodialysis
Reversal and Reverse Osmosis have proven
over time and at many locations to be highly
effective in solving nitrate contamination problems in drinking water.
2. Advances in EDR technology have allowed
nitrate removal plants to achieve 94% recovery
while also reducing salinity and hardness.
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3. New technology has also reduced the capital


and operating cost of EDR nitrate removal by
increasing the hydraulic efficiency of the EDR
stacks and pumping system.
4. Membrane improvements have made EDR
more organic resistant and chlorine tolerant,
thus allowing better control over biological contamination.
5. High recovery requirements, elevated silt density indices, and potential for biofouling tend to
favor EDR technology.
6. High rejection, low recovery, very low silt density indices, and low capacity tend to favor
RO technology.

References
1. United States Environmental Protection Agency,
Office of Water, 305(b) Report to Congress
1996/1998.
2. World Health Organization, Guidelines for
drinking-water quality, 2nd ed. Vol. 2 Health criteria and other supporting information, 1996
(pp. 940-949).
3. Siwak, L.R., Heres How Electrodialysis
Reversesand Why EDR Works, Intl Desalination & Water Reuse Quarterly, Vol. 2/4, 1993.
4. von Gottberg, A. J. M., New High Performance
Spacers in Electrodialysis Reversal Systems,
Proceedings, American Water Works Assoc.
Annual Conf., Dallas, TX, 1998.
5. von Gottberg, A. J. M. & L. R. Siwak,
Re-Engineering of the Electrodialysis Reversal
Process, Intl Desalination & Water Reuse
Quarterly, Vol. 7/4, Feb./Mar. 1998.
6. Prato, T. A. & R.G. Parent, Nitrate and Nitrite
Removal from Municipal Drinking Water Supplies with Electrodialysis Reversal, Proceedings, American Water Works Assoc. Membrane
Conference, 1993.
7. Werner, T.E., Five Billion Gallons LaterOperating Experience at City of Suffolk EDR
Plant, American Desalting Association 1998
North
American
Biennial
Conference
and Exposition.

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