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Water Technologies & Solutions

technical paper

nitrate and nitrite removal from municipal drinking


water supplies with electrodialysis reversal
Authors: Ted Prato and Richard G. Parent, Ionics Other potential health effects related to high nitrate
Reprinted from Proceedings of 1993 AWWA Membrane levels include the risk of cancer and birth defects.
Conference, by permission. These risks are less well-known and documented
than methemoglobenemia. Nitrates combine with
Note: SUEZ purchased Ionics in 2005. amines to form nitrosamines, suspected of being
potential human carcinogens. Other reactions
summary include the formation of nitrosamides which can
also produce tumors in humans. In general, the
Nitrate contamination of drinking water is a
long-term effect of consumption of high nitrate
widespread problem. It has long been known that
drinking water is unknown, but some potential for
levels of nitrates exceeding the 10 ppm (mg/l) (as N-
health problems exists from nitrite reactivity.
nitrogen) limit are associated with certain health
problems. Although high nitrogen concentrations in
drinking water are found mainly in regions of intensive sources of nitrates in drinking water
agricultural use, there are sources of nitrate Fertilizer runoff, farm animal wastes, and septic
contamination other than agricultural. Nitrates and tank discharge all percolate through the soil into
nitrites are removed efficiently and economically using groundwater aquifers and ultimately into water
electrodialysis reversal (EDR), a process where overall supplies. Agricultural sources of nitrates are by far
demineralization takes place via transfer of ions the most common. Regions of the country where
through anion and cation-selective membranes by corn is grown experience peak levels of nitrates in
application of a direct current (DC) electric field. Data groundwater from heavy fertilization.
are presented demonstrating excellent long-term
nitrate removal using EDR. Other sources of nitrate and nitrite contamination
are natural and industrial in origin. Industrial
sources include chemical manufacturing operations
human health problems and nitrate-containing cutting oils. Natural sources
The best known and documented human health risk include atmospheric precipitation (as NH ) and local
3

associated with high levels of nitrates in drinking mineral deposits such as potassium nitrate
water is methemoglobenemia, also known as asphyxia (saltpeter). Decomposing plant materials contribute
or “blue-baby syndrome,” which can affect infants as well via nitrogen-fixing bacteria. The overall
under six months of age. In methemoglobenemia,
1
contribution of natural sources is small in relation to
enteric bacteria convert the elevated levels of nitrate the contribution from human activities.
to nitrite. The nitrite then competes with oxygen for
active sites on hemoglobin resulting in oxygen allowable limits of contaminants
deprivation. Infants are predisposed to this effect due
to a number of physiological factors including “higher Standards for maximum levels of nitrates in drinking
fluid intake per body weight, a higher percentage of water have been established by the Federal
fetal hemoglobin and higher stomach pH, permitting Government in 1975 with passage of the Safe
survival of reducing-type” bacteria. 2 Drinking Water Act (SDWA). As of the May 1990

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TP1072EN.docx Mar-10
SDWA regulations, some major allowable inorganic prevent passage. See Figures 1 and 2, which
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contaminants are as follows: illustrate the EDR process.


Contaminant MCL or SMCL 1

Chloride 250 ppm (mg/l)


Fluoride 2 ppm (mg/l)
Nitrate (as N) 10 ppm (mg/l)
(as NO ) 45 ppm (mg/l)
3

Nitrite (as N) 1 ppm (mg/l)


(as NO ) 3.3 ppm (mg/l)
2
Figure 1: Electrodialysis Diagram

TDS 500 ppm (mg/l)


Maximum contaminant level or secondary maximum
1

contaminant level
Prior to the SDWA, there was no requirement or a
practical, affordable method to remove nitrates from
drinking water. Since that time a number of
3

demineralization technologies have been given a best


available technology (BAT) status for nitrate removal.
These BAT processes include EDR, reverse osmosis
(RO) and ion exchange (IE). Effective removal
constitutes reducing the level of nitrates to the Figure 2: Electrodialysis Reversal
maximum contaminant level (MCL) or lower.
A number of EDR plant designs are available to treat
The EDR process can effectively reduce nitrate contaminated water. Figure 3 presents a diagram of
concentrations to the MCL or lower in public water a typical three-stage plant. In general, a two stage
supplies. The reduction in nitrite concentration is plant removes 50% of the influent minerals and
directly related to the design demineralization rate of nitrates, a three-stage plant removes about 75%, a
the EDR system. four-stage plant removes about 83%, and so on.

what is EDR?
Electrodialysis (ED) is a process which uses ion
exchange resin in sheet form assembled into a stack
of components. ED is widely used for total dissolved
solids (TDS) removal in a number of different types of
plants and applications, including many public and
municipal drinking water supplies. Figure 3: EDR Process Flow Diagram

EDR uses a reversible DC field applied across a stack In the course of removing charged ions in solution,
of components to remove dissolved ions: the EDR also removes nitrate and nitrite ions. In this
components consist of ion-selective membranes next section, operating data are presented for
which transport either positive or negative ions, flow- several EDR plants used for nitrate removal.
directing spacers, and electrodes at each end of the
stack. Water flows in a thin sheet between nitrate removal using the EDR process
membranes. Under the influence of the applied DC
electric field, ions migrate toward the electrode Operating data illustrate the practicality of the EDR
opposite in charge, passing through membranes demineralization process for removing nitrates and
which also have fixed oppositely-charged groups nitrites as well as TDS. The examples represent a
bonded to a polymer surface. Membranes with the variety of EDR plants and include three public
same charge as the ionic species repel the ions and drinking water installations and one industrial

Page 2 TP1072EN.docx
application. Descriptions of the four plants follow. All Table 1: EDR Plant Data - Bermuda/Delaware
of the feed waters contain high levels of nitrate, and
the industrial feedwater contains exceptionally high Plant Specifications
levels of nitrite. Bermuda Delaware
Bermuda: 3 desalting stages, 600,000 gpd (2,271
Model Two Aquamite XX Aquamite XX
m /day) total production
3

Aquamite X
In Bermuda, there are two Aquamite* XX units capable
of producing a total of 600,000 gpd (2271 m /day) of
3
Production 300,000 gpd 300,000 gpd
demineralized drinking-quality water from a brackish (1,136 m /day)
3
(1,136 m /day)
3

well. The plants were installed to reduce hardness in 600,000 gpd 300,000 gpd
(2,271 m /day)
3
(1,136 m /day)
3

the existing water supply and to cut back on the


400,000 gpd
amount of purchased water. The brackish water lens
(1,514 m /day)
3

under the island is contaminated from septic tank


leach fields, making nitrate removal important. The Recovery 90% 90%
EDR plants yield 81% demineralization and reduce the
Product Purity 278 ppm TDS 11 ppm TDS
nitrate concentration from 66 ppm to 8.8 ppm.
8.8 ppm NO 4.5 ppm NO
Delaware: 3 desalting stages, 400,000 gpd (1,514
3 3

m /day) total production


3
Raw Water 1,614 ppm TDS 114 ppm TDS
This plant was installed to improve operating 66 ppm NO 3 61 ppm NO 3

economics (by predemineralizing the IE feedwater to a


Desalting Stages 3 3
power plant boiler makeup system) and to reduce NO 3

in the agriculturally-contaminated drinking water Percent Removal 81% TDS 88% TDS
supply. This three-stage EDR plant yields 88%
86.7% NO 92.6% NO
demineralization and reduces the nitrate 3 3

concentration from 60 to 4.5 ppm (mg/l). Water Quality


Industrial: 3 desalting stages, 100,000 gpd Bermuda Delaware
total production
Feed Product Feed Product
This plant was installed as a roughing demineralizer. Constituent (ppm (ppm (ppm (ppm
Nitrite concentration is also quite high. Here an [mg/l]) [mg/l]) [mg/l]) [mg/l])
Aquamite X produces 100,000 gpd with 66%
demineralization. Nitrate concentration is reduced Sodium 349 72 12 1.6
from 655 ppm to 128 ppm, and Nitrite concentration is
Calcium 138 13 9 0.5
reduced from 64 ppm to 21 ppm.
Magnesium 40 4 8 0.6
Italy: 2 desalting stages, 300,000 gpd (1,136 m /day)
3

total production Potassium 19 2 - -


Both plants were installed specifically to remove Chloride 656 92 15 1.2
nitrates from municipal wells in agriculture-intensive
regions of Italy. Bicarbonate 259 75 9 2.4

These two-stage Aquamite XX plants yield 53% Sulfate 85 10 - -


demineralization with reductions in TDS from 1,012 to
Nitrate 66 8.8 61 4.5
474 ppm (mg/l) and nitrate from 120 to 37 ppm (mg/l).
The approach here is not only to remove pH 7.9 7.0 6.2 5.4
nitrate but also to comply with EC standards in overall
TDS reduction. TDS 1,614 278 114 11

Tables 1 and 2 present operating data on all of the


various EDR units.

TP1072EN.docx Page 3
Table 2: EDR Plant Data - Industrial/Italian
concentration to below the MCL as established by
both the SDWA and the World Health Organization.
Plant Specifications All nitrate product levels for the public water supply
Industrial Italian applications are within the Safe Drinking Water Act
MCL requirement. Average percent removal of
Model Two Aquamite X Aquamite XX nitrate from the three-stage plants is 86.6% with an
average percent TDS removal of 78.3%. Percent
Production 100,000 gpd 300,000 gpd
(379 m /day)3
(1,136 m /day)
3 removal from the two-stage plant is 69.2% for
nitrate and 53% for TDS. Nitrite removal in the
Recovery 80% 90% industrial application is 67.2% with a 68% TDS
removal.
Product Purity 534 ppm TDS
ppm TDS In addition, graphs of three of the four plants show
128 ppm NO
analytical data for feed and product salinity and
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37 ppm NO 3

21 ppm NO 3 nitrate concentrations over time (Figures 4 and 5).


The small variations in the product quality reflect
Raw Water 1,753 ppm TDS
changes in feedwater quality or operating
655 ppm NO 3 conditions, such as seasonal temperature changes
64 ppm NO 3
or increases in feedwater TDS. These EDR units
consistently meet or exceed SDWA MCL standards
Desalting Stages 3 2 for nitrate removal from public water supplies.
Percent Removal 66% TDS
53% TDS
80.4% NO3
69.2% NO 3

67.2% NO3

Water Quality

Industrial Italian

Feed Product Feed Product


Constituent (ppm (ppm (ppm (ppm
[mg/l]) [mg/l]) [mg/l]) [mg/l])

Sodium 24 14 73 49

Calcium 141 28 127 63

Magnesium 34 8 34 13

Potassium - - 4 1.7

Chloride 35 11 120 44

Bicarbonate 514 235 449 240

Sulfate 113 23 85 25 Figure 4: Nitrate and TDS Removal


Nitrate 655 128 120 37

Nitrate 64 21 7.3 7.1

pH 7.3 7.0 7.3 7.1

TDS 1,753 534 1,012 474

All of these plants have three desalting stages with the


exception of the Italian municipal plant which requires
only two desalting stages to reduce the nitrate
Page 4 TP1072EN.docx
references
1. O’Brien, W.J., “Control Options for Nitrates
and Fluorides”, Water/Engineering and
Management, July, 1983.
2. Bouchard, D.C., Surampalli, R.Y., Williams,
M.K., “Nitrate Contamination of
Groundwater: Sources and Potential Health
Effects”, Journal AWWA, Management and
Operations, September, 1992.
Figure 5: Nitrate, TDS and NO3 Removal
3. Kartinen, E.O., Jr., “Nitrate Removal from
conclusions Municipal Water Supplies”, AWWA
Conference at Grand Island, Nebraska,
EDR effectively removes nitrates and nitrites from November, 1991.
feed waters, as demonstrated by the plant data. EDR
plants are easily designed and operated to yield 4. Meller, F. H., “Electrodialysis &
product water quality to meet SDWA MCLs or SMCLs Electrodialysis Reversal Technology”,
or lower. Other EDR process advantages include: March, 1984.

• Self-cleaning membrane process


• Low operating and maintenance costs
• Long membrane life
• High recovery operation
• No chemical feeds
• Low chemical usage
• No regenerant wastes
• Reduction in TDS in addition to nitrate and nitrite
Although there are only a few very specific health
problems identified as a result of high nitrate levels in
drinking water, stricter regulations are driving public
water suppliers to provide suitable technology for
reducing nitrate and nitrite concentrations in the
interest of addressing avoidable health risks.

TP1072EN.docx Page 5

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