v-xEPA
                                  United States
                                  Environmental Protection
                                  Agency
                                  Municipal Environmental Research*-'
                                  Laboratory
                                  Cincinnati OH 45268
i
                                  Research and Development
                                  EPA-600/S2-82-042  August 1982
Project Summary
                                 Removal  of  Nitrate from
                                 Contaminated  Water
                                 Supplies for  Public  Use:
                                 Final  Report
                                  Gerald A. Outer
                                   Three treatment processes (reverse
                                 osmosis (RO), ion exchange, and the
                                 combination of RO followed by ion
                                 exchange)  to remove nitrate from
                                 public water supplies obtained from
                                 wells were evaluated. Laboratory size
                                 and field-test equipment was used to
                                 establish design criteria and operating
                                 experience useful for designing a full-
                                 scale plant of approximately 1-million
                                 gal per day (mgd) capacity. An interim
                                 report (EPA-600/2-81-029) on this
                                 project was published in February
                                 1981 and is available from the National
                                 Technical Information Service, Spring-
                                 field, Virginia; and the final report is
                                 summarized herein.
                                   The program was conducted by the
                                 McFarland  Mutual Water Co. at well
                                 No. 3 in McFarland, California.  Ion
                                 exchange column tests were conducted
                                 with five strong-base anion exchange
                                 resins on  nitrate-laden waters  of
                                 various anion compositions. From this
                                 work, estimates  of product water
                                 quality and the bed volume capacity
                                 for feedwater of any composition can
                                 be made. A working hypothesis was
                                 developed from an analysis of the data
                                 about how  the chemical structure of
                                 resins can  be practically altered  to
                                 obtain nitrate selectivity. As a result, a
                                 series of resins was synthesized  to
                                 study the effect of molecular structure
                                 on nitrate selectivity. Two of the resins
                                 showed selectivity of nitrate in prefer-
                                 ence to sulfate ion. Others in the series
                                 showed enhanced sulfate selectivity.
                                   A 20-in. diameter pilot anion exchange
                                 column was designed and  operated
                                 for over 1 year at well No. 3. Data from
                                 this column operation was used to
                                 verify estimates  of pilot column
                                 performance and to project the cost
                                 for equipment  and regenerant for a
                                 well site installation  to treat up to
                                 1 mgd. An RO system having a pro-
                                 duction capacity of 76 mVday (20,000
                                 gpd) was operated for over  1,000
                                 hours until excessive nitrate passage
                                 was obtained.
                                   This Project Summary was developed
                                 by EPA's Municipal Environmental
                                 Research Laboratory. Cincinnati. OH.
                                 to announce key findings of  the
                                 research project that is fully docu-
                                 mented in a separate report  of the
                                 same title (see Project Report ordering
                                 information at back).

                                 Introduction
                                   The small community of McFarland,
                                 California, in the heart of the intensive
                                 agricultural/industrial area of the San
                                 Joaquin Valley in central California, is
                                 faced with declining water quality and
                                 increased demand on their groundwater
                                 supply. This problem is typical of many
                                 communities not only in the  United
                                 States but throughout the world. If the
                                 development of new water sources from
                                 surface supplies or deep aquifers or the
                                 use of centralized treatment is economi-
                                 cally unfeasible, well site treatment for
                                 contaminant  removal is an alternative
                                 to be considered. This study  concerns

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applying treatment processes to a well
site situation — and improving water
quality without constructing new wells,
modifying old wells,  or  altering  the
distribution system.
  Well site treatment to remove nitrate
is not considered to be standard
practice; only a few such installations
can be cited throughout the world,  and
no detailed operating data  or costs have
been published. Although  ion exchange
and reverse osmosis (RO) are familiar
and widely used processes in industrial
water treatment,  their use to  remove
specific contaminants from community
water supplies is new  and requires the
traditional demonstration project to
advance  widespread use of these
processes. This study provides both
engineering and scientific aspects
information and data to aid the planning
of a demonstration  project. The engi-
neerng aspects deal with  design para-
meters, conceptual designs, operation,
and  process reliability derived from
actual hands-on experience. The scien-
tific  aspects  deal with ion exchange
theory of resin  selectivity and  the
testing of new resins that show nitrate
selectivity in presence of sulfate  and
other common anions.  It is believed this
work  has resulted in  a  major break-
through  in  development of  nitrate-
selective resins having the potential to
lower costs of nitrate removal for many
communities.  The method used to
derive the nitrate-selective resins  can
be used to derive resins  selective for
other inorganic contaminants.

Methods and Materials
  All tests were conducted at a well site
(No.  3)  owned and operated  by  the
McFarland Mutual  Water Company.
Nitrate-nitrogen  levels for this water
were 16 to 23 mg/L, well above  the 10-
mg/L maximum contaminant level
Sulfate levels were greater than 300
mg/L.
  Site improvements were designed for
well No. 3 to accommodate equipment
for conducting both field and laboratory
scale experiments Water  was supplied
directly to a  concrete pad and trailer
from an existing hydropneumatic tank.
All  product  and wastewaters were
discharged from the pad directly  into the
city sewer system.  The 9 1- x 9.8-m
(300- x 32-ft) pad was large enough to
accommodate a field test  ion exchange
system,  a field test RO system, and a
single  module RO system with  the
necessary tanks for temporary water
storage. A trailer adjacent to the  pad
housed a  field office and limited
laboratory facilities.
  A source of well  No. 3 water was
available in the trailer for experimental
tests which were conducted on various
ion exchange  resins in 5.1-cm  (2-m.)
diameter columns Synthetic mixtures
were prepared and pumped directly at
measured flow rates through the ion
exchange columns  Five commercially
available exchange resins were studied
along with eight specially  prepared
resins.  Because only the single-bed
process was chosen for this study, tests
were limited to strong-base  anion
exchange resins.
  A Culligan HI-FLO 5 Water Softener
Model 150* was installed and operated
on the pad at well No 3. The completely
automatic water softener was converted
to a semiautomatic anion exchanger by
installing an industrial  timer and anion
exchange resin (Duolite A-101D). The
system incorporated a 50.8-cm (20-in.)
diameter bed that contained 123L(4.36
ft3) of anion exchange resin.
  A pilot scale RO system producing 7.6
mVday (20,000 gpd) was operated  on
pretreated well No.  3 water. Cellulose
acetate  spiral wound  elements  were
used in  this system

Discussion  of Results and
Conclusions

Engineering Aspects

Ion Exchange
   1. Design parameters for application
of a conventional fixed single-bed ion
exchange  process with downflow  re-
generation for removal of nitrate from
well waters were developed and tested
using laboratory columns and a modified
conventional automatic water softener
converted to  a 20-in.  diameter anion
exchange pilot column. The process is
depicted in Figure 1  for a well water of
moderate nitrate and sulfate levels. Pilot
column tests were conducted using a
Type  I  strong-base anion  exchange
resin (Duolite  A-101D)  at well  3.
Because well No. 3 is high in nitrate (ca
20.3 mg/L NO3-N) and sulfate (ca 320
mg/L), it is a useful research well.
  2. The study showsthat automatic ion
exchange  equipment,  which is  com-
monly  used by  the water softening
industry, can  be adapted for  nitrate
removal The equipment can be installed
'Mention of trade names or commercial products
does not constitute endorsement or recommenda-
tion for use
at a well site for direct treatment of well
water and operated on demand without
storage.
  3 The selected resin was effective for
the nitrate removal for flow rates over
45 gpm/ft2  of bed area (2.75 BV per
minute).  Forty  five  gpm/ft2 was the
upper limit of the test  equipment used.
These high flow rates  bring the cost of
capital equipment and resin quantities
to low practical levels.
  4.  When  sulfate  is present in  raw
water, operating  the ion exchange
column in a partial regeneration mode is
more economical than in the complete
regeneration mode  because the resin
concentrates nitrate near  the  down-
stream end of the column from which it
is easily removed. Salt requirements for
McFarland wells ranged from 2.5 to 5 Ib
of sodium  chloride/ft3 of resin. In
comparison, complete regeneration
would require  18  to 20 Ib/ft3.  The
extended bed  life and lower nitrate
leakage does not justify the added salt
costs for complete regeneration. Partial
regeneration also produces a water less
corrosive than the high chloride water
produced by complete regeneration.
  5.  Capital  equipment costs of an  ion
exchange system for treating a Vz mgd
production well are estimated to be less
than $100,000 installed (1981  costs).
This estimate is based on moderate
nitrate levels (less than 13.5 mg/L NOs-
N) in well water and sulfate levels less
than 200 mg/L and on blending (50/50)
treated water with raw water to produce
a water less than 10 mg/L NOa-N (see
Figure 1). Equipment cost for a system
to treat all water from a 1-mgd produc-
tion  well is estimated at less than
$160,000.
  The total water cost including amortized
capital and operating costs are estimated
to be 17.3 cents/1,000gal (4.6 cents/m3)
of treated water. This is based on raw
water  nitrate-nitrogen levels  of 13.5
mg/L, sulfate  levels of 200 mg/L, and
treated water nitrate-nitrogen levels of
6.8 mg/L with all sulfate removed.
These costs  do not include brine
disposal  costs,  which  are variable and
community  dependent.  Brine disposal
costs can be  proportional to regeneration
chemical costs if  disposed to local
landfills  and could increase the above
unit quantity costs by 30 to 50 percent.
  6. Regenerant costs alone over a 20-
year plant life can be more than double
the first  equipment costs of the plant.
Because of  the  significance of regen-
erant costs,  a method is presented to
estimate the sodium chloride require-

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ments for regenerating the resin used in
nitrate removal from waters of various
composition. Because  anion exchange
resins are quite selective for sulfate ion,
the presence of sulfate in raw water
decreases the efficiency of the resin to
absorb nitrate  In this study, however,
the sodium chloride regenerant easily
removed sulfate from the spent resin in
nearly stoichiometric proportions where-
as excess regenerant  is required  for
nitrate removal. The overall  effect of
sulfate, however, is to increase the salt
required to  remove nitrate  per unit
quantity  of water treated. This study
also  confirmed that  large quantities of
regenerant  (20 Ib/ft3 of resin)  are
required to remove  most of the nitrate
from the spent resin. Not all nitrate need
be removed, however, to reduce nitrate-
nitrogen levels in treated water to below
10 mg/L
  For McFarland wells, the salt require-
ments for lowering nitrate levels to
between 6.8 and 10  mg/L NCVN range
between an estimated 2.48 to 4.48
Ib/ft3 of resin.  The salt costs  range
between  2.31  cents/1,000 gal of
blended (50/50) water for well No.  2 to
12.28 cents/1,000 gal of treated water
for well No. 3. Well  No. 3 represents a
particularly difficult  water to treat as
nitrate-nitrogen levels are near 23 mg/L
and sulfate levels are above 300 mg/L.
Nitrate-nitrogen levels in well No. 2 are
near  13 5 mg/L and sulfate levels are
near  200 mg/L. Salt requirements for
waters of other compositions are given
(Table 1).
  7. To achieve efficient nitrate removal,
good brine and influent flowdistribution
are essential and may require modifica-
tion in commercially  available softening
equipment. A method of declassification
(thorough mixing) of  the resin after
downflow regeneration should also be
incorporated in the regeneration cycle.
  8.  Wastewater produced during the
regeneration cycle  has an  enriched
composition of sodium sulfate,  chloride,
and  nitrate.  Continuous  operation of
well  No. 2 would produce over 12,000
gal of wastewater/day (see Figure 1).
Continuous  operation of  well  No. 3
would produce  an average of 39,000
gal of wastewater/day

Reverse Osmosis
  1. An RO system, operated on well No.
3 for over 1,000 hr, contained spiral
wound  cellulose acetate membranes
and produced 15 gpm  of treated water
with 75 percent water recovery. Of the
major groundwater  anions, nitrate is
           __ 1,000 gal
             well water

             /VOJ< 57 ppm
             HCO3 =  72
             Cl~ = 61
             SOf  = 197

            500 gal
                       Regenerant
                         NaCI
                         1.25 Ib
\
500
gal














Strong
base
anion
exchanger
(type 1)

Chloride
form



V^
\
\
\
Raw water \^
^














	 Ion exchange
column effluent

NOy = 30 ppm
HCOz = 72 ppm
cr= 221
SOf = 0

I



             Bypass
NO   =4,9OOppm
S0f= 8,200
N0j = 1,200
Cl~=  800
     I
Spent regenerant
and rinse
12 gal
                1,000 gal
                blended product water

                NOy <  44 ppm
                HCOj=  72
                CL~  =141
                SOf  =  96
Figure 1.  Conventional single-bed ion exchange process.

Table 1.    Regeneration Requirements for Waters of Various Compositions
Water Composition NO3 rrieq/L
HCOl
cr
Operating SOI
Parameter Total Anion
NOl in product water ppm
Bed volumes treated to breakthrough
Salt loading Ib/ft3
Salt requirement Ib/ 1.000 gal
1
1
1
5
35
30
423
2 15
0.68
1
1
1
3
60
30
229
3.73
218
1.5
1
1
3
6.5
30
207
413
2.67
1.5
1
1
2
5.5
30
247
3.67
1.98
1.5
1
1
1
4.5
30
307
3.36
1.46
15
1
1
.5
4.0
30
347
3.22
1.24

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the most  difficult  to  remove  by  RO.
During  the  operation of the system,
nitrate passage  rose  from 33 to  65
percent.
  2. Because operation of the RO
system was plagued with  several
electrical and mechanical failures, its
use is questionable for well site removal
of nitrate insmallcommunitieswithfew
or no maintenance personnel.
  3. The most serious trouble experienced
with the RO system was failure of 0-
ring seals between the high pressure
brine and low pressure product channels
This was  presumably due to lateral
movement  of membrane elements
during the system start and stop that is
required to follow the start and stop of
the well pump. This difficulty can be
avoided by providing sufficient well site
storage to allow continuous  system
operation.
  4. Capital equipment costs for treating
water by RO for nitrate reduction from a
1 -mgd production well are over $800,000.
Estimates  of water costs  including
amortized equipment and operating and
maintenance costs are 99.2 cents/1,000
gal of water produced (26.2 cents/m3).
  5. Twenty-five  percent of the well
capacity becomes waste brine from the
RO system — for a 1 mgd well, 250,000
gal of wastewater per day. This quantity
would use one-half of the  municipal
waste treatment capacity of McFarland's
wastewater treatment plant and would
add approximately 2 tons of dissolved
solids/day to the  local disposal area if
operated at well No. 2 (compared with 1
ton for ion exchange  —  same basis).
However, no outside source of sodium
chloride is needed as  is the case with
ion exchange
  6. The advantages  of  RO over  ion
exchange are that fewer processing
chemicals need be brought to the locale
and the product water is considerably
deminerahzed

Reverse  Osmosis Followed by
Ion Exchange
  1. For small communities, there
appears to be few advantages to using
RO followed by ion exchange polishing
to produce water of low nitrate content
(less than  1  mg/L NO3-N). Because RO
brine was ineffective for regenerating
the nitrate-loaded resin, some salt was
still required. The added complexity and
cost of operating an  RO system  in
conjunction with  ion exchange at the
well  site  appears to outweigh any
advantages of producing a less  minera-
lized water. Water costs by operation of
such a system are estimated to be at
least  $1.12/1,000 gal of low nitrate
content water that could be blended
with other well water.  If  blended (two
volumes  raw water to one of treated
water), the cost per 1,000 gal would be
37 cents plus brine disposal costs. Resin
regeneration requirements would be
substantially reduced, to below  10
percent of their value,  if ion exchange
alone would be  used.  Volume of
wastewater  would be  about  115,000
gal of  mainly RO brine per  1  mgd of
blended product
  2. RO followed by ion exchange may
be cost effective for large scale systems;
these  were not  a  subject  of this
investigation. Economies of scale could
lower  RO  costs  and  advantages of
demmeralization may be highly desir-
able  Large communities with  high
nitrate, high TDS groundwater can treat
with RO and polish by ion exchange and
could blend the product with raw water
and may find the process cost effective.

Theoretical Aspects
  1. A special  series  of  strong-base
anion  exchange resins, synthesized
especially for this program,  shows a
striking correlation between nitrate-to-
sulfate selectivity  and the molecular
structure of the alkyl substituents on the
quaternary  amine  ion exchange sites.
Some of the resins are nitrate-to-sulfate
selective. The normal increasing order
of ion selectivity for available anion
exchange resins at normal  ground-
water concentrations  is bicarbonate,
chloride, nitrate, sulfate. As the number
of carbon atoms around the ammonium
nitrogen increase in the R groups of the
resin structure.
                              R
(Divmylbenzyl Resin Backbone)—N—R,
                              R
the increasing order of ion selectivity is
changed  to  bicarbonate, chloride,
sulfate, nitrate. Where R is methyl, Ks(a
measure of nitrate-to-sulfate selectivity)
is approximately 100; whereas if R is
ethyl, Ks is approximately 1,000 Thus,
in column tests with the triethy I resin on
water  having a nitrate plus  sulfate
concentration of greater than 8  meq/L,
nitrate is the last ion to breakthrough
Other resins with a total of four and five
carbon atoms show intermediate Ks
values. See Tables 2 and 3 and Figure 2.
The effect of introducing OH groups into
the alkyl substituents is to decrease the
Ks value. For example, if the R groups
are ethoxy, the Ks value is approximately
10.
  These structural effects  on  Ks value
are ascribed to  steric strains set up in
the  resin  by the special (or  steric)
requirements of alkyl  R  groups with
nitrate having capability of decreasing
the steric strain whereas sulfate can
increase  strain. Little  effect on the KCI
values are  noted. All resins are easily
regenerated with  chloride  brines. This
observed effect of molecular structure
gives rise to a  concept of structurally
induced electroselectivity reversal.
  2.  The net effect of using the triethyl
amme resin as  compared  with the
commercially available trimethyl  resin,
is  to increase the bed life  BV (N) from
170  to 275, an  increase of 62 percent,
when treating a water containing  1.5
meq/L nitrate and  6.5 meq/L sulfate
(see  Figure  3). The immediate effect is to
reduce wastewater for processing by
38 percent  A second desirable  effect
of  using the triethyl resin is to reduce by
25 to 50  percent,  the  amount  of
regenerant  required  to  remove an
equivalent amount of nitrate depending
on the mode of operation  and level of
regeneration selected. This represents
a projected cost savings of $84,000 to
$168,000 in salt over the 20-year plant
life plus at least equivalent amounts for
brine disposal  costs. Special  column
operation must be used since the nitrate
breakthrough can be compounded and a
choice is available to operate to the first
or second nitrate breakthrough. A third
advantage  in using NSS  resins is to
preserve more of the raw water quality
by allowing sulfate to pass through the
column.
  3.  The structural effects  noted above
were found characteristic of a series of
eight special resins that show a trend
toward increased KS (and greater
process efficiency) without any obser-
vable limit. Consequently,  it is believed
a continuing study of structure I changes
can produce an optimum resin that will
give an even greater  cost saving than
that  noted above.
  4. The nitrate-to-sulfate selective
(NSS)  resins have characteristics that
require special consideration in process
design.
   •  Anion exchange capacity of NSS
     resins is approximately 15 percent
     lower than their Type 1 counterpart.

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Table 2.    Structures of Special Resins

  No.      Designation            Amine
                                      Molecular Structure*
   1
R-TM
Trimethyl
               R-TE
                    Triethyl
              R-MDE
                Methyldiethoxy
             R-EDEOH
                 Ethyldiethoxy
             R-TEOH
                   Triethoxy
            R-DMEOH
         (same as A-104)
             R-DEEOH
                Dimethylethoxy
                 Diethylethoxy
             R-N-MM
                  N-methyl-

                  morpholine
    CH3

R    N+   CH3
    CH3


    CH3
    CH2

R    N+   CH2   CH3

    CH2
    CH3


    CH3

R    /V+   CHz   CH2OH
    CHZ

    CH2OH


    CH3
    CH2

R    N+   CH2   CH2OH

    CH2
    CH2OH


    CH2OH

    CH2

R    N+   CH2   CH2OH
    CH2

    CH2OH


    CH3
R    N+   CH2   CH2OH
    CH3
                      CH3
                      CH2
                  R    N+   CH2
                      CH2

                      CH3


                      CH3
                                                        N
                                                               O
*R denotes resin backbone structure.
  • Two  nitrate  breakthrough  points
     are obtained with partially regen-
     erated resin. Nitrate leakage before
     the first is determined by chloride
     ion-nitrate ion competition for resin
     sites. The first breakthrough point
     occurs simultaneously with sulfate
     breakthrough.  Nitrate  leakage
     after sulfate breakthrough is deter-
     mined  by nitrate  ion-sulfate  ion
     competition. The  first break is
     usually sharp; the second is often
     indistinguishable.
  • To use the triethyl NSS  resin
     effectively,  two columns  can be
     run out of phase to average the two
     levels of nitrate leakage.
  5. The method used to  discover the
nitrate-to-sulfate  selective resins was
through observation and analysis of (a)
column  breakthrough profiles  and
relation to chemical structure; (b)
departure of column behavior from a
mathematical  model; (c) the shape of
binary isotherms; (d) effect of structural
changes on  primary,  secondary, and
tertiary  ammonium  weak-base resins;
(e) swelling effects of ions on resins; (f)
experiments on nitrate-selective sulfate-
loaded resin; and (g)  inferences from
physical  organic  chemical studies of
effects of structure on chemical  equili-
brium. This method may be applied to
studies  on selective removal of other
inorganic contaminants.
  6. Nitrate-to-sulfate selectivity among
strong-base resins was found to also
increase with the degree of resin cross
linking.  The  list of resins studied in
increasing order of nitrate-to-sulfate
selectivity are:
         Duolite A-101D
         Duolite A-104
         Amberlite IRA-910
         Dowex SAR
         Amberlite IRA-900
The literature shows IRA-410 and lonac
A-550 as well as some  tertiary  amine
weak-base resins  to have  nitrate-
selective tendencies  However,  com-
mercially available resins do not show
enough  nitrate  selectivity to  be of
significant value. In this  study they are
not NSS resins. Lower anion exchange
capacity is a disadvantage of the higher
cross linked resins and also makes the
ion  exchanger appear to be nitrate-to-
sulfate selective  through  the electro-
selectivity effect.  (Activated carbon is a
notable case.) Also, where nitrate and
sulfate are equal in selectivity, the spent
column will have nitrate evenly distri-
buted in the  column.  This  is a  dis-
advantage  in downflow regeneration

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Table 3.    Properties of Special Resins'
No. and Designation
1 R-TM
2 R-TE
3 R-MDEOH
4 R-EDEOH
5 R-TEOH
6 R-DMEOW
7 R-DEEOH
8 R-N-MM
(Duolite A-1 '01 D)
Moisture2
Content
51.0
47.9
41.1
38.9
33.1
45.7
43.5
44.6
(48 to 55)
Vol.
Capacity2
(eq/L)
1.41
1.19
1.41
1.30
1.23
1.42
1.29
1.35
(1-3)
(approximate)
100
1,000
10
50
10
50
100
200
(25)
NSS
-0.14
+0.92
-1.15
-0.41
-1.09
-0.45
-0.11
+0.17
-0.7 1
 'A II resins synthesized from the resin intermediate used in commercial manufacture
 of Duolite A-104.
 2Data supplied by Diamond Shamrock.
 3Same as Duolite A-104
   3.0 r
   2.0
 §•
 -J
   1.0
            • NO OH group's in fl, R2 R3

            O One  "   "    "   "  "

            A Two  "   "    "   "  "

            D Three "   "    "   "  "
           A-101-D
             m
             345
                       No. of carbon atoms in /?, R2 R3

Figure 2.   Effect of structure on nitrate to sulfate selectivity.

                                  6
since nitrate must  be moved  through
the entire column.  Consequently,  A-
101D resin was chosen for pilot studies
because nitrate concentrates near the
exit end of the column from which it is
more easily removed during regenera-
tion. It is  also pointed out in the study
that  threshold  Ks values must  be
reached before a resin can be a nitrate-
to-sulfate selective resin  and before
process efficiency can be improved.
  7. Use of chemical regenerants other
than sodium chloride was briefly
explored. It  was  demonstrated that
nitrate can be selectively removed using
sulfate-loaded resins. It is suggested
that dilute calcium sulfate be tested as a
regenerant. Larger volumes of regenerant
using  a low IDS  water are  required.
Such a supply is available in McFarland
as irrigation water. Waste brine would
contain calcium nitrate and sulfate both
of which are disposable to  agricultural
lands.  Ammonium chloride is also
suggested as regenerant  that would
give ammonium nitrate and sulfate as a
disposable brine
  8. From these studies and a review of
previous studies on synthesis of resins
with higher nitrate-to-chloride selectivity,
it does not appear regenerant  require-
ments  can  be reduced if nitrate-to-
chloride selectivities are  increased.
Available  anion  exchange  resins  are
already nitrate-to-chloride selective.
Making them more selective for nitrate
will  only  add to further regeneration
inefficiencies. This, however, does nol
appear to be  the  case with  the NSS
resins  since the nitrate-to-chloride
selectivities did not change substantially
whereas  nitrate-to-sulfate selectivitv
did change.

Recommendations
  1.  An ion  exchange demonstration
plant of '/2- to 1 -mgd capacity should be
installed and operated to obtain actual
operational experience regarding reli-
ability, health, safety, and costs. Com-
mercially available  resins should  be
used  because NSS resins  require
further testing.
  2. As pointed out above,  the cost of
regenerant and brine disposal over the
plant  lifetime can be several times the
cost of the plant. Efforts should be made
to reduce regenerant requirements to
the lowest level practicable.  This can be
done by recycling portions of brine and
brine  rinse as well as backwash waters
in demonstration plant operation and
continuing studies on nitrate-to-sulfate
selective resins.

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    400 r-
    350
    300
    250
 £
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 I
 *  200

 I
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 c
 .0
 5
 ^
    100
     50
             Influent S04
            - Influent NO3
sor
A
A
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Resin
R-TE
A-101-D
                                        Regenerated IV/4 BV 6% NaCI
                                        runs 09230. 09190
                    50
100
                                             150          200          250

                                                  Bed volumes Well 3

Figure 3.   Ion exchange column experiment 09230 and 09190.
                                                                                     300
                                                                 350
400
  3.  Studies  should be conducted  on
use of regenerants other  than sodium
chloride for the single-bed process to
produce waste brines more amenable to
disposal on agricultural land.
  4.  Studies on  NSS  resins should
continue since further increases  in
nitrate-to-sulfate selectivity can  be
expected. These resins must also  be
characterized as to fouling tendency,
chemical degradation,  and acceptance
in water treatment.
  5.  Brine disposal is the single most
important factor and major expense that
deters widespread  use of the ion
exchange process. All future efforts to
improve the process should focus  on
this impediment to its application.
  6. Ion exchange is recommended over
RO for nitrate removal  at remote well
sites in small communities because of
cost and operational problems associated
 /ith  RO. This study showed that total
oosts for treatment of well No. 2 water
were approximately 18 cents/1,000 gal
       for ion exchange versus $1/1,000 gal
       for RO.  Brine disposal costs were not
       included in either estimate.
       Summary
         The ion exchange process isgenerally
       more suitable as a well site treatment
       for  nitrate removal than  RO or a
       combination of the two. Ion exchange
       requires lower first cost  and annual
       operating costs, has greater reliability,
       uses less energy, requires no additional
       well site storage,  has higher water
       recovery, produces a more concentrated
       waste brine, and requires fewer auto-
       matic and electrical controls. It can be
       operated  on demand as  required by
       distribution  system needs. Such on-off
       operation is severely detrimental to an
       RO  system, which operates  best on a
       continuous  basis and, hence, requires
       additional storage and repressurization.
       Brine disposal is a cost common to both
       processes.
                                                                                 Ion exchange resins with altered
                                                                               chemical structures were formulated
                                                                               for  selective  removal  of  nitrate  from
                                                                               common groundwaters containing
                                                                               sulfate ions. Projected use of nitrate-to-
                                                                               sulfate  selective (NSS) resins in ion
                                                                               exchange plants has potential to reduce
                                                                               operating  costs  by increasing  the
                                                                               efficiency  of the process through
                                                                               reduced wastewater, reduced brine
                                                                               requirements,  and lower waste brine
                                                                               disposal costs. These operating cost
                                                                               savings are estimated  to exceed the
                                                                               equipment costs of the plant over a 20-
                                                                               year period.  The  NSS resins, which
                                                                               require further testing before practical
                                                                               applications can be made,  are presently
                                                                               not  commercially available. Small
                                                                               quantities were made for  this program
                                                                               by a resin manufacturer using existing
                                                                               processes and available intermediates.
                                                                               The NSS resins are examples of struc-
                                                                               turally induced electroselectivity rever-
                                                                               sal, a concept that may find applications
                                                                               in removal of other contaminants.

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      The full report was submitted  in
    fulfillment of Grant No  R-805900-01-
    02-03 by the McFarland Mutual Water
    Co.,  McFarland, California,  under
    subcontract to Boyle Engineering Cor-
    poration, Bakersfield, California, under
    the sponsorship  of the U S. Environ-
    mental Protection Agency.
            Gerald A. Cuter is with Boyle Engineering Corporation, Bakersfield. CA 93302.
            Richard Lauch is the EPA Project Officer (see below).
            The complete report, entitled "Removal of Nitrate from Contaminated Water
             Supplies for Public Use: Final Report," (Order No. PB 82-222 902; Cost:
             $18.00, subject to change) will be available only from:
                   National Technical Information Service
                   5285 Port Royal Road
                   Springfield, VA 22161
                   Telephone: 703-487-4650
            The EPA Project Officer can be contacted at:
                   Municipal Environmental Research Laboratory
                   U.S. Environmental Protection Agency
                   Cincinnati, OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Postage and
Fees Paid
Environmental
Protection
Agency
EPA 335
Official Business
Penalty for Private Use $300

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