Water Research 173 (2020) 115571

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Water Research
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Achieving low-cost, highly selective nitrate removal with standard

anion exchange resin by tuning recycled brine composition
Shoupeng Duan a, Tiezheng Tong b, Shaokui Zheng a, *, Xueyu Zhang a, Shida Li a
a
School of Environment, MOE Key Laboratory of Water and Sediment Sciences/State Key Lab of Water Environment Simulation, Beijing Normal University,
Beijing, 100875, China
b
Department of Civil and Environmental Engineering, Colorado State University, Fort Collins, CO, 80523, United States

a r t i c l e i n f o a b s t r a c t

Article history: This study demonstrated the presence of a critical equivalent ratio of the competing anion (i.e., sulfate
Received 15 November 2019 and bicarbonate) to chloride ion in recycled brine to achieve highly-selective nitrate removal from
Received in revised form nitrate-rich groundwater in the standard-anion exchange resin (AER) (i.e., with trimethylamine func-
28 January 2020
tional groups) column process. With increasing bicarbonate (or sulfate):chloride equivalent ratio in brine
Accepted 30 January 2020
Available online 31 January 2020
used to circularly activate/regenerate the standard-AER column, considerable bicarbonate (sulfate)
removal and dumping were observed. The critical bicarbonate (sulfate):chloride equivalent ratio of 2:5
(8:1) in brine effectively achieved zero net bicarbonate (sulfate) removal (<5%) from feedwater during
Keywords:
Nitrate
long-term exhaustioneregeneration cyclic operation. The feed rate (6e18 BV/h) played a key role in
Selective ion exchange determining the critical sulfate:chloride equivalent ratio in brine, while the feed sulfate concentration
Groundwater (145e345 mg/L) slightly changed the critical sulfate:chloride equivalent ratio. The use of optimized
Brine reuse ternary brine (with a sulfate:chloride:bicarbonate equivalent ratio of 42:5:2) stably achieved long-term
Resin activation highly-selective nitrate removal from groundwater in the standard-AER column process with brine
electrochemical treatment. The possible mechanism for nitrate selectivity included the modification of
the sulfate: and bicarbonate:chloride equivalent ratios in the standard-AER column by the optimized
brine in circular activation/regeneration mode; this changed the column elution and breakthrough
curves, inhibited the competition of sulfate and bicarbonate for ion exchange sites during exhaustion
according to the separation factor, and finally achieved selective nitrate removal from feedwater.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction hydrophilic sulfate over univalent and hydrophobic nitrate (Clifford

The contamination of groundwater by nitrate is one of the most
serious water pollution problems worldwide (Biddau et al., 2019),
as high nitrate levels in drinking water may lead to blue baby
syndrome in infants and gastrointestinal cancer in adults (Su et al.,
2017). The anion exchange process through polymeric strong base
anion exchange resins (AERs) is often considered an efficient
method for removal of nitrate from groundwater. Standard strong
base AERs, such as Amberlite IRA 400 and Amberlite IRN-78
(Hekmatzadeh et al., 2012), 201
4 (Sun et al., 2015; Zheng et al.,
2011), etc., often have trimethylamine functional groups
(ReNþ(CH3)3) and/or polyacrylic backbones (Gu et al., 2007; Hsu
and Singer, 2010; Song et al., 2012), and prefer divalent and
* Corresponding author.
E-mail address: zsk@bnu.edu.cn (S. Zheng).
and Liu, 1993; Vanderhoek et al., 1988). The preference for sulfate
over nitrate on standard AERs (i.e., sulfate-selective AERs) leads to
low nitrate adsorption capacity, nitrate peaking or dumping after
nitrate breakthrough (Hekmatzadeh et al., 2012), and higher cor-
rosivity and negative effects on health associated with higher
chloride content in product water (Clifford and Liu, 1993). Since the
1980s, a number of nitrate-selective AERs with longer chain length
functional group (e.g., triethyl (ReNþ(CH2CH3)3)) and polystyrene
backbones (Gu et al., 2007; Hsu and Singer, 2010; Song et al., 2012),
including Purolite A-520E, Amberlite IRA 996 (Boumediene and
Achour, 2004; Hekmatzadeh et al., 2012), NDP-2, NDP-5 (Sowmya
and Meenakshi, 2014), Duolite A196 (Boumediene and Achour,
2004), Imac HP555, Indion NSSR (Hekmatzadeh et al., 2012), and
etc., have been developed to overcome those shortcomings
mentioned above (McAdam and Judd, 2008). As compared with
standard AERs, however, those nitrate-selective AERs are generally
quite expensive, which emerges as the primary obstacle against its

https://doi.org/10.1016/j.watres.2020.115571
0043-1354/© 2020 Elsevier Ltd. All rights reserved.
2 S. Duan et al. / Water Research 173 (2020) 115571
wide application in water treatment plant.
In the AER-packed column process, plug flow passing through
the AER column can be divided into many identical segments. All
anions in water passing through the column can equilibrate in each
column segment before being transferred to the next column
segment (Choe et al., 2015). During exhaustion or regeneration, the
general formula of ion exchange reactions between a given anion (B
n
, univalent [B, e.g., bicarbonate] or bivalent [B2, e.g., sulfate]
ions) and the univalent counterion (A, chloride ion in most cases)
in the feedwater (or brine) and AER phase is as follows:
nRþ A þ Bn 4Rþ
nB
n
þ nA (1)
The ion exchange of the given anion over the univalent coun-
terion can be evaluated by the separation factor (a), calculated as
follows (Gu et al., 2004; Hu et al., 2016):
 
RþnB
n
½A 
aBA ¼
n
þ 

 n  (2)
½R A  B of ~1 eq/L.
where [Rþ n þ 
n B ] and [R A ] are the equilibrium equivalent concen-
trations of the given anion and the univalent counterion in the AER
phase, while [Bn] and [A] are their equilibrium equivalent con-
centrations in the aqueous phase, respectively.
Typically, the anionic selectivity sequence on standard AERs (i.e.,
sulfate > nitrate > chloride > bicarbonate (Hekmatzadeh et al.,
2012)) is mainly related to differences in the physicochemical
characteristics of these anions (Hu et al., 2016), and their ionic
strengths in solution (Bergquist et al., 2016). The development of
nitrate-selective AERs demonstrates that the anionic selectivity
sequence on AERs will vary with the change in AER properties (i.e.,
hydrophobicity) when modifying their functional groups and/or
polymer backbones (Gu et al., 2007; Hsu and Singer, 2010; Song
et al., 2012). As shown in eq (2), however, the success or failure
of ion exchange of the given anion over the univalent counterion
was also determined by the equivalent ratio of the given anion to
the univalent counterion (i.e., [Rþ n þ 
n B ]/[R A ]) in AER phase against
that (i.e., [Bn]/[A]) in feedwater during exhaustion (or brine
during regeneration). Furthermore, as the AER process is often
operated with alternating exhaustion and regeneration cycles, the
equivalent ratio of a given anion to the univalent counterion in
recycled brine might influence their equivalent ratio in the AER
during activation/regeneration, and further influence the ion ex-
change performance of the given anion during exhaustion ac-
cording to the separation factor. Under these conditions, besides
modifying AER properties (i.e., nitrate-selective AERs) (Gu et al.,
2007; Hsu and Singer, 2010; Song et al., 2012), there may be
another strategy to achieve nitrate selectivity in a standard-AER
column process at a low cost, i.e., by optimizing the equivalent
ratio of competing anions to the univalent counterion in recycled
brine to inhibit their competition for ion exchange sites during
exhaustion.
Following circular activation of a standard-AER column by bi-
carbonate (or sulfate)-chloride binary brine, we investigated the
potential effect of the bicarbonate (or sulfate):chloride equivalent
ratio in binary brine on anionic removal performance during
exhaustion, and demonstrated the presence of a critical bicarbon-
ate (or sulfate):chloride equivalent ratio in binary brine to achieve
zero net bicarbonate (or sulfate) removal from feedwater. Subse-
quently, following evaluation of the potential effects of feed rate
and feed sulfate concentration on the critical sulfate:chloride
equivalent ratio in brine, we demonstrated the feasibility of selec-
tive nitrate removal from groundwater by optimizing ternary brine
(sulfate:chloride:bicarbonate) over 13 exhaustioneregeneration
cycles in the standard-AER column process with brine
electrochemical treatment. Finally, we propose a mechanism for
selective nitrate removal in the standard-AER column process with
optimized brine, after investigating the effects of circular activa-
tion/regeneration by optimized brine on column elution and
breakthrough curves, and sulfateenitrate binary exchange
reactions.
2. Material and methods
2.1. Materials
Reagent-grade sodium salts (~99% purity) of nitrate, sulfate, and
bicarbonate were added to tap water to prepare simulated
groundwater (approx. 200 mg/L nitrate, 145 mg/L sulfate, and
160 mg/L bicarbonate) (Biddau et al., 2019; Wang et al., 2017), or
into 0e3.6% NaCl brine to prepare the designed brine (including
0e50 g/L sulfate and 0e31 g/L bicarbonate). Unless otherwise
specified, the brine had a fixed total equivalent ionic concentration
The standard AER used in this and previous studies (Sun et al.,
2015; Zheng et al., 2011), i.e., 201
4 resin (a gel-type poly-
styrene strong base AER with trimethylamine functional groups),
was supplied by Zhejiang Zhengguang Industrial (Hangzhou,
China). According to the manufacturer’s data sheet, it has a total
exchange capacity (wet) of 1.10 mmol/mL and an average particle
size of 0.315e1.25 mm, and its comparable products include
Amberlite IRA-401, Dowex 1
4, and Diaion SA-11A. Prior to use,
the virgin AERs in the chloride form were pretreated by washing
with deionized water until neutral.
2.2. Laboratory-scale standard-AER experimental setup and cyclic
operation
A schematic diagram of the laboratory-scale standard-AER
experimental setup used in this study is shown in Fig. S1. The glass
column (2 cm i.d., 24 cm height) contained 49 mL of 201
4 resin.
Unless otherwise specified, the standard-AER column was operated
in countercurrent mode, as follows: circular AER activation using
designed brine; four consecutive exhaustioneregeneration cycles
(i.e., one brine purification cycle); and electrochemical treatment of
spent brine in batch mode. During the activation and regeneration
phases, 2e4 L of brine in the brine tank was pumped upwards to
circularly activate or regenerate the standard AER at 2.45 BV/h for
4 h by an EH-B10VC-220RI diaphragm pump (Iwaki Co., Iwaki,
Japan). During the 15-h exhaustion phase, feedwater in the feed
tank was pumped downwards into the standard-AER column at the
specified feed rate (as shown in Table S1), and product water was
discharged into the effluent tank. Following AER regeneration,
makeup NaCl was added to the brine to return its salt concentration
to the initial level. At that time, the AER column was ready for the
next exhaustioneregeneration cycle. The 6-h electrochemical
treatment of spent brine was conducted in a 1-L electrolysis cell
equipped with a DC power supply (0e30 V, 0e5 A) in batch mode;
Fe and IrO2eRuO2/Ti plates 66 cm2 in area (11 cm
6 cm) (Sure
Industrial Technology Co. Ltd., Suzhou, China) were used as the
cathode and the anode, separated by a distance of 16 mm. After
electrochemical treatment, the pH of the brine was adjusted to 8.9
using hydrochloric acid, and makeup NaCl was added to the brine
prior to the next round of AER activation.
2.3. Standard-AER column experimental protocol
Table S1 presents a summary of the protocol for the seven sets
of standard-AER column tests: (1) one set of six experiments
(performed in parallel) to evaluate the effects of the
 S. Duan et al. / Water Research 173 (2020) 115571
bicarbonate:chloride equivalent ratio in brine on anionic removal
performance during exhaustion, following circular activation by
designed brine (labeled B/C Br. Exp. 1e6); (2) one set of six exper-
iments (performed in parallel) to evaluate the effects of the sulfa-
te:chloride equivalent ratio in brine on anionic removal
performance during exhaustion, following circular activation by
designed brine (labeled S/C Br. Exp. 1e6); (3) one set of 19 exper-
iments (performed in parallel) to evaluate the effects of feed rate on
anionic removal performance during exhaustion, following circular
activation by brine with various sulfate:chloride equivalent ratios
(labeled Feed Rate Exp. 1e19); (4) one set of 16 experiments (per-
formed in parallel) to evaluate the effects of sulfate concentration in
feedwater on anionic removal performance during exhaustion,
following circular activation by brine with various sulfate:chloride
equivalent ratios (labeled Sul. Feed Exp. 1e16); (5) one experiment
to investigate long-term anionic removal and accumulation char-
acteristics during 13 consecutive exhaustioneregeneration cycles,
including circular activation/regeneration by brine with optimized
sulfate:bicarbonate:chloride equivalent ratio and electrochemical
treatment of spent brine (labeled Long-term Opt. Br. Exp.); (6) one
set of two experiments (performed in parallel) to investigate the
effects of circular activation/regeneration mode on the anionic
elution curves of the exhausted column when NaCl solution was
used as brine, with no circular activation/regeneration mode (i.e.,
direct column effluent discharge) as the control (labeled Column
Elu. Exp. 1e2); and (7) one set of two experiments (performed in
parallel) to investigate the effects of activation treatment by the
optimized brine on anionic column breakthrough curves with
nonactivated column as the control (labeled Column Break.
Exp.1e2).
Unless otherwise specified, samples were individually collected
from the feed tank, the effluent tank, and the brine tank to deter-
mine water quality parameters at the beginning or end of each
phase. For anionic elution tests of the exhausted column, effluent
samples were collected consecutively from the brine tank for water
quality analysis at regular time intervals in circular activation/
regeneration mode, while they were collected consecutively from
the column exit in the control condition. For anionic breakthrough
tests, all samples were collected consecutively from the column exit
at regular time intervals for water quality analysis.
2.4. Analytical methods
After filtration through 0.45-mm membrane filters, nitrate was
measured according to standard methods (APHA, 2005). The bi-
carbonate concentrations were estimated with titration of the pH.
The sulfate concentration was calculated from the sulfur concen-
tration determined using an Axial View Inductively Coupled Plasma
Spectrometer (SPECTRO ARCOS EOP; SPECTRO Analytical In-
struments GmbH, Kleve, Germany). The overall precision of the
water quality analysis was verified by replicate analysis and
calculation of the relative percentage deviation, the target of which
was 10%.
3. Results and discussion
The majority of previous studies on nitrate-selective AERs used
sulfate as a competing anion (Choe et al., 2015; Hekmatzadeh et al.,
2012; Hu et al., 2016). It is reported that bicarbonate also has an
adverse effect on nitrate adsorption (Choe et al., 2015; Song et al.,
2012), although it has lower selectivity than nitrate and chloride
(Hekmatzadeh et al., 2012). In this study, both sulfate and bicar-
bonate were selected as competing anions to investigate the po-
tential effects of brine optimization on the selective nitrate removal
performance of a standard-AER column process.
3
Fig. S2 shows the long-term removal of nitrate, sulfate, and bi-
carbonate from feedwater during exhaustion when NaCl brine is
reused during 24 exhaustioneregeneration cycles in a standard-
AER column process without brine purification or replacement,
along with their accumulation in recycled brine during regenera-
tion. Consistent with previous studies of standard-AER columns
with recycling of brine for reuse (Lehman et al., 2008; Liu and
Clifford, 1996; Sun et al., 2015; Zheng et al., 2011), preferential
sulfate removal (>96%) was observed throughout the long-term
cyclic operation, while nitrate and bicarbonate removal gradually
decreased from 100% to 38%, and from ~28% to ~16%, respectively.
Cyclic operation led to remarkable accumulation of these three
target anions in recycled NaCl brine. The observations also imply a
dynamic increase in the equivalent ratio of all three target anions
relative to chloride (i.e., the counter anion) in the recycled brine.
Fig. S3 shows that the rough estimates of the amounts of nitrate and
bicarbonate adsorbed on the standard-AER column increased
gradually to the peak values during the 16th and 10th
exhaustioneregeneration cycle, respectively, and then remained
stable. In previous study, Lehman et al. (2008) noticed that both
sulfate and bicarbonate concentrations in recycled NaCl brine
reached a steady state after 13e15 cycles of the standard-AER
column process for groundwater treatment, depending on the
feedwater ionic concentrations, brine concentration, and removal
effectiveness. The presence of a steady state for these anions in the
standard-AER column, or in recycled brine, demonstrated that
there is an inherent relation of these anions in feedwater, in the
standard-AER column, and in recycled brine. Previously, the failure
of nitrate removal by standard AERs is typically attributed to the
stronger competition of sulfate for ion exchange sites (Li et al.,
2019; Liu and Clifford, 1996). However, it seems in this study that
the failure to remove nitrate and bicarbonate may also have been
attributable to the considerable increases in their equivalent ratios
to chloride in the recycled brine and in the standard-AER column,
which may inhibit their ion exchange capacity during exhaustion.
3.1. Effects of the bicarbonate (or sulfate):chloride equivalent ratio
in brine for circular activation of the standard-AER column on
anionic removal performance during exhaustion
Bicarbonate:chloride equivalent ratio in brine. Incorporation
of bicarbonate into the chloride-based brine was reported to exert
small effects on standard-AER exhaustion and regeneration with
regard to sulfate, nitrate, and chloride, because bicarbonate-based
brine is weaker than chloride-based brine (Li et al., 2015). The
weak effects of a wide range of bicarbonate concentrations in
chloride-based brine on anionic removal performance during
exhaustion was demonstrated in Fig. 1a. Following circular activa-
tion of the standard-AER column by brine with various bicarbo-
nate:chloride equivalent ratios, the sulfate and nitrate removal
rates during exhaustion remained constant at ~100% during
exhaustion. However, varied bicarbonate:chloride equivalent ratios
in brine seemed to considerably influence bicarbonate removal
during exhaustion. The bicarbonate concentration in the product
water increased gradually with increases in the bicarbonate
equivalent fraction in the recycled brine, and finally exceeded the
bicarbonate concentration in the feedwater (i.e., negative bicar-
bonate removal, or bicarbonate leakage or dumping into the
product water) at a bicarbonate equivalent fraction of >0.33. These
results demonstrated that the failure to remove bicarbonate
observed in Fig. S2 was attributable to an excessively high bicar-
bonate:chloride equivalent ratio in the recycled brine with the
development of continuous operation, which finally inhibit the ion
exchange capacity of bicarbonate during exhaustion. When the
bicarbonate equivalent fraction in brine was 0.29 (i.e., the critical
4 S. Duan et al. / Water Research 173 (2020) 115571

a sulfate equivalent fraction in brine of 0.89 (i.e., the critical sulfa-

te:chloride equivalent ratio of 8:1), the sulfate concentrations in the
feedwater and product water were approximately equivalent (i.e.,
<5% sulfate removal).
The inhibitory effect of the critical sulfate:chloride equivalent
ratio in recycled brine on long-term sulfate removal performance
was further demonstrated by 12 exhaustioneregeneration cycles of
the standard-AER column process, when the brine with the critical
equivalent ratio was used to activate or regenerate the standard-
AER column (Fig. S5). No significant (<5%) sulfate removal and
accumulation, as well as low bicarbonate removal (14e21%) and
accumulation, and marked nitrate removal and accumulation were
consistently observed with cyclic operation. Therefore, the ratio of
8:1 was referred to as the critical sulfate:chloride equivalent ratio in
brine, for activation of the standard-AER column to inhibit the
competitive capacity of sulfate for ion exchange sites during
exhaustion. In contrast to previous conclusions (Boumediene and
Achour, 2004; Hekmatzadeh et al., 2012; Li et al., 2019; Liu and
Clifford, 1996), the results presented here confirmed that the
presence of abundant sulfate in brine and feedwater had no sig-
nificant effect on the nitrate removal performance of the standard-
AER column.

Fig. 1. Anionic removal performance during exhaustion phases, after the standard-AER 3.2. Effects of feed parameters on the critical sulfate:chloride
column was circularly activated by bicarbonate-chloride binary brine with varied bi- equivalent ratio in brine
carbonate equivalent fraction (a), or by sulfate-chloride binary brine with varied sul-
fate equivalent fraction (b).
Feed rate. A higher feed rate generally increases the turbulence
of flow in the fixed-bed process, resulting in a shorter breakthrough
bicarbonate:chloride equivalent ratio of 2:5), the bicarbonate time and faster saturation (Hekmatzadeh et al., 2012; Li and Yang,
concentrations in the feedwater and the product water were 2015; Xu et al., 2013). In this study, following circular activation
approximately equivalent (i.e., <5% bicarbonate removal). of the standard-AER column by brine with various sulfate:chloride
The inhibitory effects of the critical bicarbonate:chloride equivalent ratios, the effects of feed rate (i.e., 6 (Fig. 1b), 12 and 18
equivalent ratio in recycled brine on long-term bicarbonate (Fig. 2) BV/h) on the critical sulfate:chloride equivalent ratio in
removal performance were further demonstrated by 15 brine were investigated. The feed rate seemed to play a key role in
exhaustioneregeneration cycles of the standard-AER column pro- determining the critical sulfate:chloride equivalent ratio in brine.
cess, when the brine with the critical bicarbonate:chloride equiv- With increasing feed rate, the critical sulfate:chloride equivalent
alent ratio was used to circularly activate or regenerate the
standard-AER column (Fig. S4). In addition to no significant (<5%)
bicarbonate removal or accumulation, remarkable sulfate removal
(90e94%) and accumulation, and remarkable nitrate removal and
accumulation were consistently observed with cyclic operation.
Therefore, the ratio of 2:5 is referred to as the critical bicarbona-
te:chloride equivalent ratio in brine for activation of the standard-
AER column, to inhibit the competition of bicarbonate for ion ex-
change sites during exhaustion.
Sulfate:chloride equivalent ratio in brine. As shown in Fig. 1b,
following circular activation of the standard-AER column by brine
with various sulfate:chloride equivalent ratios, nitrate removal
remained constant at ~100% during exhaustion in most cases. The
remarkable amounts of sulfate in both feedwater and brine had a
negligible influence on nitrate removal performance during
exhaustion. However, with the increase in the sulfate:chloride
equivalent ratio in brine, bicarbonate removal by the activated
standard-AER column decreased markedly from 75% to 17%,. The
increase in the sulfate:chloride equivalent ratios in brine also
considerably influenced sulfate removal performance during
exhaustion while the sulfate concentration in the product water
increased gradually and finally exceeded its concentration in the
feedwater (i.e., negative sulfate removal, or sulfate leakage or
dumping into the product water). These results demonstrated that
the failure to remove could be achieved at an excessively high
sulfate:chloride equivalent ratio in the recycled brine, which finally Fig. 2. Effect of feed rates (12 (a) and 18 (b) BV/h) on anionic removal performance
inhibit the ion exchange capacity of sulfate during exhaustion. With during the exhaustion phases, after the standard-AER column was activated by sulfate-
chloride binary brine with varied sulfate equivalent fraction.
 S. Duan et al. / Water Research 173 (2020) 115571
ratios in brine changed from 8:1 at 6 BV/h to 6:1 at 12 and 18 BV/h.
As reported previously (Hekmatzadeh et al., 2012; Li and Yang,
2015; Xu et al., 2013), the increase in feed rate markedly influ-
enced nitrate and bicarbonate removal in all cases in this study. The
World Health Organization (WHO) recommends drinking water
nitrate concentrations < 50 mg/L (WHO, 2011); drinking water
satisfying this threshold at a feed rate of 18 BV apparently cannot be
produced in most cases, although efficient nitrate removal (i.e.,
55e84%) was still achieved. Therefore, a low feed rate (e.g., <10 BV/
h) during exhaustion is recommended for the standard-AER col-
umn process.
Feed sulfate concentration. In this study, following circular
activation of the standard-AER column by brine with various sul-
fate:chloride equivalent ratios, the effects of feed sulfate concen-
tration (i.e., 145 (Fig. 1b), 245, and 345 (Fig. 3) mg/L) on the critical
sulfate:chloride equivalent ratio in brine were investigated. With
increasing feed sulfate concentration, the critical sulfate:chloride
equivalent ratio in brine increased slightly from 8:1 for 145 mg/L
sulfate to 17:2 for 245 mg/L sulfate, and then to 9:1 for 345 mg/L
sulfate. These observations suggested that the severalfold change in
feed sulfate concentration is accompanied by a slight change in the
critical sulfate:chloride equivalent ratio in brine. The variation in
feed sulfate concentration hardly influenced the nitrate removal
performance by the circularly activated standard-AER column in all
cases, and nitrate levels in the product water remained constant at
extremely low levels (Figs. 1b and 3). In comparison with the results
at 145 mg/L sulfate, feed sulfate concentrations of 245e345 mg/L
significantly reduced bicarbonate removal at low sulfate:chloride
equivalent ratios in the brine.
3.3. Long-term anionic removal and accumulation characteristics of
the standard-AER column process with optimized brine and brine
electrochemical treatment
In this study, we combined the critical sulfate:chloride and
bicarbonate:chloride equivalent ratios to produce optimized
ternary brine with a sulfate:chloride:bicarbonate equivalent ratio
Fig. 3. Effect of feed sulfate concentrations (i.e., 245 (a) and 345 (b) mg/L) on nitrate,
sulfate and bicarbonate removal performance at feed rate of 6 BV/h during the
exhaustion phases, after the standard-AER column was activated by sulfate-chloride
binary brine with varied sulfate equivalent fraction.
5
of 42:5:2; this was tentatively used to activate or regenerate the
standard-AER column during 13 exhaustioneregeneration cycles,
and the long-term anionic removal and accumulation performance
was further investigated. After every four exhaustioneregeneration
cycles, the spent brine was purified by electrochemical treatment to
remove nitrate, and then recovered to activate the standard-AER
column prior to the next exhaustioneregeneration cycle. The re-
sults are illustrated in Fig. 4. In previous studies, “unitary brines”,
such as NaOH, HCl, NaCl, and NH4Cl brine solutions (Sun et al.,
2015; Zheng et al., 2017), and “binary brines”, such as NaCl/NaOH
(Zheng et al., 2017) and NaCl/NaHCO3 (Li et al., 2015), were used to
regenerate the exhausted AERs. This is the first report of the
simultaneous addition of sulfate and bicarbonate to brine and use
of a “ternary brine” for AER regeneration.
Different from the standard-AER column process shown in
Fig. S2, following standard-AER activation/regeneration by the
optimized brine, no significant bicarbonate removal (<5%) and low
sulfate removal (2e22%) were consistently observed throughout
the long-term cyclic operation periods, as illustrated in Fig. 4, when
their concentrations in the recycled brine remained stable.
Furthermore, the sulfate removal (maximum: 22%) of the opti-
mized ternary brine shown in Fig. 4 was higher than that (<5%) of
the binary brine (sulfate:chloride), shown in Fig. S5, possibly due to
a less-precise brine composition, as it was produced by a combi-
nation of two critical binary equivalent ratios. Additionally,
Vanderhoek et al. (1988) noted 0e45% sulfate removal and no
significant bicarbonate removal from feedwater by a nitrate-
selective AER column. In this study, following activation/regener-
ation by the optimized brine, the standard-AER column may also
show no or low sulfate and bicarbonate removals from feedwater
during long-term cyclic operation. In contrast, although increased
carbon chain length of functional groups produced those nitrate-
Fig. 4. Nitrate, sulfate and bicarbonate removal (from the feed) and accumulation (in
the recycled brine) characteristics during 13 exhaustioneregeneration cycles of the
standard-AER column activated by optimized brine, with routine electrochemical
treatment of spent brine and subsequent AER activation between two adjacent dashed
lines (i.e., between the 4th and 5th or the 8th and 9th exhaustion-regeneration cycles).
As shown in this figure, after electrochemical and subsequent activation treatments,
there was a remarkable decrease and subsequent slight increase in nitrate concen-
tration in the recycled brine.
6 S. Duan et al. / Water Research 173 (2020) 115571
selective AERs (Boumediene and Achour, 2004; Hekmatzadeh et al.,
2012; Sowmya and Meenakshi, 2014), it also reduced their ex-
change capacity for selective nitrate removal (Samatya et al., 2006).
It is often reported that sulfate buildup in the resin phase affects
the standard-AER column to a much greater extent than the
nitrate-selective AER column, in terms of nitrate removal from
feedwater (Liu and Clifford, 1996). However, as illustrated in Fig. 4,
Figs. S4, and S5, the sulfate and bicarbonate buildup in the
standard-AER column induced by circular activation using the
optimized brine did not present a major obstacle to nitrate removal
and accumulation performance; in fact, it aided selective nitrate
removal and accumulation by inhibiting ion exchange of sulfate and
bicarbonate, so that quality drinking water with low chloride
content could be produced during long-term cyclic operation. The
results presented here also demonstrated that, although many AER
sites are occupied by competing anions, there are still sufficient ion
exchange sites available for nitrate removal from feedwater.
The process of electrolytic decomposition of nitrate to harmless
nitrogen gas has attracted a great deal of attention due to its
minimal generation of secondary waste, ease of operation (Yu and
Kupferle, 2008), high treatment efficiency, and small equipment
footprint (Li et al., 2009a, 2009b). In the presence of abundant
chloride in solution, electrolytic decomposition was achieved by a
combination of reduction of nitrate on the cathode and oxidization
of ammonia on the anode by free chlorine (ClO) generated during
chloride oxidization (Su et al., 2017; Yu and Kupferle, 2008). In this
study, prior to spent brine purification treatment, the nitrate con-
centration in the product water increased gradually from 1 to 13 to
39e43 mg/L after 4e5 exhaustioneregeneration cycles, while ni-
trate in brine increased gradually from 114 to 202 to 612e1064 mg/
L. Following electrochemical treatment, the nitrate level in spent
brine was efficiently decreased to 90e125 mg/L (i.e., 84e85%
removal), and no detectable byproducts (e.g., ammonia and nitrite)
were detected in the treated brine (data not shown). No significant
effects of electrochemical treatment on bicarbonate and sulfate
concentrations in the recycled brine were observed. Furthermore,
the electrochemically treated brine eluted nitrate residue on AERs,
resulting in a nitrate level to 167e202 mg/L in the recycled brine
prior to the next exhaustioneregeneration cycle. Subsequent ob-
servations confirmed that electrochemically treated brine effec-
tively restored the capacity of the standard-AER column for nitrate
removal from feedwater during subsequent long-term cyclic
operation. Therefore, the electrochemical process can be used in a
closed loop to selectively and completely remove nitrate from spent
brine. From both an economic and environmental standpoint, this
provides a good solution to the problem of disposal of the spent
brine that is frequently generated during the previous AER process.
Electrochemical treatment can reduce the nitrate concentration in
spent brine to close to zero (Paidar et al., 2004). However, taking
mass transfer limitations and low current efficiency at low nitrate
concentrations into account (Paidar et al., 2004), it would be ad-
vantageous to terminate the electrochemical process of spent brine
at a relatively high nitrate concentration (e.g., around 100 mg/L in
this study).
3.4. Nitrate-selective removal mechanism in the standard-AER
column process with optimized brine
Effects of circular activation/regeneration mode on column
elution curves. Fig. 5 shows the effects of circular activation/
regeneration mode with NaCl brine on the anionic elution profiles
of exhausted standard-AER column, without circular activation/
regeneration (i.e., direct brine discharge after passage of 9 BV NaCl
solution through the exhausted standard-AER column) as the
control. Consistent with a previous study (Lehman et al., 2008; Li
Fig. 5. Effect of circular activation (or regeneration) mode (b) by NaCl brine on anionic
elution curves of the exhausted standard-AER column, with no circular activation/
regeneration mode (i.e., direct effluent discharge) as control (a).
et al., 2015), in the control, typical elution peaks for these model
anions were seen, as shown in Fig. 5a. Finally, three model anions
were completely eluted from the exhausted column to produce an
effluent concentration of 0 mg/L.
In contrast, under circular activation/regeneration mode, the
standard-AER column exhibited markedly different anionic elution
curves, as shown in Fig. 5b. All anionic concentrations in the brine
tank increased gradually to the highest level and then remained
constant. Their maximum concentrations were far lower than those
achieved in the control. The circular activation/regeneration mode
finally achieved equilibria of three anions between AERs and brine,
similar to batch adsorption test. Under these conditions, adsorptive
equilibrium between AER and brine may result in a remarkable
influence of brine composition on the anionic equivalent ratio in a
standard-AER column. That is, a low (high) equivalent ratio of
sulfate (bicarbonate):chloride in recycled brine will result in a low
(high) anionic equivalent ratio on the standard-AER column during
circular activation/regeneration. Furthermore, for the feedwater
with a fixed equivalent ratio of sulfate (bicarbonate):chloride, a low
(high) equivalent ratio of sulfate (bicarbonate):chloride in recycled
brine will finally result in a low (high) separator value during
exhaustion according to eq (2). This indicated favorable (unfavor-
able) selectivity of the standard-AER column for sulfate (bicar-
bonate) over chloride (i.e., positive or negative sulfate [bicarbonate]
removal during exhaustion). The mechanism explained why, as
observed in Figs. 1e3, with the increase in equivalent ratio of sulfate
(bicarbonate):chloride in recycled brine, net sulfate (bicarbonate)
removal and subsequent sulfate (bicarbonate) dumping by the
standard-AER column was observed in a stepwise manner,
following the activation by designed brine. Thus, selective nitrate
removal by the standard-AER column was finally achieved at the
critical equivalent ratio of sulfate (bicarbonate):chloride in recycled
brine by circular activation/regeneration of the optimized brine.
Effects of circular activation by optimized brine on column
breakthrough curves. The column breakthrough test was often
used in previous studies to demonstrate the selective capacity of
nitrate-selective AERs for nitrate (Choe et al., 2015; Gu et al., 2004;
Liu and Clifford, 1996), in which sulfate will be always driven off
these AERs by nitrate in the feedwater during exhaustion (i.e.,
 S. Duan et al. / Water Research 173 (2020) 115571
earlier sulfate breakthrough than nitrate breakthrough) (Choe et al.,
2015; Liu and Clifford, 1996). In this study, the potential effects of
circular activation by optimized brine on the anionic breakthrough
curves of the standard-AER column were evaluated using a
nonactivated standard-AER column as a control, and the results are
shown in Fig. 6. As reported previously (Hekmatzadeh et al., 2012;
Lehman et al., 2008; Sun et al., 2015), effluent anionic concentra-
tions of the nonactivated standard-AER column showed a normal
anionic breakthrough profile (Fig. 6a). Bicarbonate broke through
first, and the nitrate concentration in the product water rose
sharply from ~0 mg/L before 196 BV to above that in the feedwater
after 270 BV, while no sulfate was detected in the product water
throughout the experimental period. In contrast, following activa-
tion by the optimized brine, the standard-AER column exhibited
different column breakthrough curves (Fig. 6b). There was a far
higher bicarbonate concentration in product water at the beginning
than that shown in Fig. 6a. In comparison with sulfate and bicar-
bonate, nitrate bound preferentially to the standard-AER column
circularly activated by optimized brine. The column breakthrough
curve presented here was similar to those reported for nitrate-
selective AERs (Gu et al., 2004; Hekmatzadeh et al., 2012; Liu and
Clifford, 1996; Sowmya and Meenakshi, 2014). It indicated that
circular activation of the standard-AER column by the optimized
brine made it feasible to achieve nitrate selectivity. In the steady
state of the nitrate-selective AER system, the sulfate mass balance
showed that more than 90% of the sulfate loaded on AER sites
during the first 80 BVs of exhaustion was subsequently replaced by
nitrate in the feedwater during the remaining exhaustion period
(Liu and Clifford, 1996), as shown in column breakthrough curves,
which explained why no net sulfate removal was observed during
the steady-state periods of nitrate-selective AER, previously (Liu
and Clifford, 1996) or in this study (Fig. 4 and Fig S5).
Effects of circular activation by optimized brine on
sulfateenitrate binary exchange reactions. In previous studies,
qualitative binary ion exchange plots and quantitative separation
Fig. 6. Anionic breakthrough curves of the fresh standard-AER columns, after being
activated by optimized brine (b) with no activation as control (a).
7
factor calculations were used to demonstrate the nitrate-selective
capacities of many nitrate-selective AERs (Ebrahimi and Roberts,
2016; Gu et al., 2004; Hu et al., 2016). In this study, the activated
standard-AERs were prepared in fixed-bed columns using the
optimized brine with a sulfate:chloride:bicarbonate equivalent
ratio of 30:5:2. Subsequently, the selectivity of activated and
nonactivated standard-AERs for sulfate and nitrate were evaluated
by sulfateenitrate binary ion exchange reactions, as described by
Gu et al. (2004) with minor modifications. The separation factor (a)
for sulfate (i.e., the given anion in this test) and nitrate (i.e., the
mobile counterion in this test) was calculated according to eq (2)
based on the data nearest the point at which the equivalent ionic
fraction in solution was ~0.5. A separation value > 1 indicates
favorable selectivity of AER for sulfate over nitrate, while a higher
value indicates greater sulfate selectivity (Hu et al., 2016). A plot of
the sulfate equivalent concentration fractions on AER (y-axis)
versus solution (x-axis) is shown in Fig. S6. The majority of the data
points remained above the 1:1 line, indicating greater selectivity
for sulfate over nitrate via either nonactivated or activated
standard-AER. Furthermore, the separation values of activated and
nonactivated standard-AER were 1.14 and 1.01, respectively, which
approximated those reported in previous studies for standard AERs
(e.g., 1.71e137 for 32 standard AERs (Clifford and Weber, 1983)). The
results indicated no significant change in the anionic preference of
standard AER, where activation by optimized brine did not modify
its functional groups.
3.5. Significance of this investigation
The results present here indicated that the circular activation/
regeneration mode modified the anionic equivalent ratio in the
standard-AER column according to the brine composition (Fig. 5),
which in turn influenced the column breakthrough curves of the
standard-AER column (Fig. 6) and played a key role in determining
the removal performance of a given anion during exhaustion ac-
cording to the separation factor. Under these conditions, no
removal from feedwater and accumulation in recycled brine of
sulfate and bicarbonate were frequently observed during long-term
cyclic operation of the standard-AER column when the optimized
brine with the critical equivalent ratio was used, as shown in
Figs. S4 and S5, and Fig. 4. In this study, the exhaustion and
regeneration cycles had a common equivalent ratio of the
competing anion to chloride ion in the standard-AER column, as the
standard-AER column process was operated with alternating
exhaustion and regeneration cycles. Therefore, the inhibitory effect
of the competing anions in optimized brine on their own ion ex-
change performance during exhaustion and regeneration can be
explained by the approximate equivalent ratios in the feedwater
and the optimized brine. For example, the critical sulfate:chloride
equivalent ratios in recycled brine were 8.0, 8.5, and 9.0 for
equivalent ratios of sulfate:chloride ion in feedwater of 5.3, 9.5, and
13.3, respectively, at feed sulfate concentrations of 135, 243, and
342 mg/L, respectively. Selective nitrate removal by the standard-
AER column was finally achieved through the inhibitory effect of
competing anion (e.g., sulfate or bicarbonate) in optimized brine on
its own ion exchange during exhaustion, rather than by the anionic
selectivity sequence. The difference in the operational costs of the
nitrate-selective AERs reported previously and the standard-AER
column activated/regenerated by optimized brine introduced in
this study was determined by their treatment capacity and resin
costs due to their similar process design. As illustrated in Fig. 6, the
treatment capacity of the activated standard-AER column process
(about 120 BVs of product water) approximated to that of some
nitrate-selective AERs for groundwater treatment, e.g., 120 BVs for
Purolite A-520E (Gu et al., 2004). Under the conditions, the
8 S. Duan et al. / Water Research 173 (2020) 115571
operational costs of the activated/regenerated standard-AER col-
umn process was significantly lower than that of the nitrate-
selective AER process, since those nitrate-selective AERs are
generally more expensive (e.g., ~5e5 times or even higher) than
standard AERs.
In this study, insignificant bicarbonate and sulfate removal were
consistently observed, from the first cycle of the long-term cyclic
operation of the standard-AER column with optimized brine
(Figs. S4 and S5, and Fig. 4). However, for a nitrate-selective AER
system, long-term cyclic operation (e.g., 33
exhaustioneregeneration cycles) is often required to reach a steady
state, characterized by no net sulfate removal from feedwater
(Clifford and Liu, 1993; Liu and Clifford, 1996). It seems that the
treatment performance of the activated standard-AER column in
this study was even better than that of nitrate-selective AERs.
However, there were still many commonalties between the nitrate-
selective AERs reported previously and the standard-AER column
activated/regenerated by optimized brine introduced in this study,
e.g., no net sulfate removal from feedwater was achieved after the
sulfate concentration in recycled brine reached a plateau (Clifford
and Liu, 1993; Liu and Clifford, 1996). Furthermore, the inhibitory
effect of non-sulfate anions in recycled brine on their own ion ex-
change performance have also been reported previously for nitrate-
selective AERs, when it was also observed in this study (including
bicarbonate and nitrate). For example, Bergquist et al. (2016)
concluded that a high concentration of nitrate in brine is princi-
pally responsible for the reduced nitrate breakthrough capacity of
nitrate-selective AERs, rather than the accumulation of sulfate or
bicarbonate in the brine. Vanderhoek et al. (1988) attributed the
absence of bicarbonate removal from groundwater when using a
nitrate-selective AER to abundant bicarbonate on the AER column
at the start of each service mode, due to the higher alkalinity of the
brine. Therefore, it seems possible that the activated standard-AER
column by the optimized brine in this study and the nitrate-
selective AERs share an identical nitrate-selective removal mech-
anism, i.e., inhibition of the ion exchange capacity of a coexisting
anion during exhaustion by its anionic equivalent ratio to the
chloride in optimized brine. In comparison with nitrate-selective
AERs (2.2 (Clifford and Liu, 1993) or even 16 (Liu and Clifford,
1996) g/L sulfate), a far higher sulfate concentration (i.e.,
43e44 g/L sulfate; see Figs. 1b and 4) in the optimized brine was
required for the standard-AER column in this study to inhibit its
own ion exchange during exhaustion, which demonstrated the
advantage of nitrate-selective AERs over the activated standard-
AER column introduced in this study, due to stronger hydropho-
bicity. In recent decades, various ion exchangers have been devel-
oped to selectively remove different contaminant ions, including
heavy metals (e.g., Cu2þ (Bezzina et al., 2019) and As(V) (Awual
et al., 2012) ions), and other anions (e.g., phosphate (Trung Huu
et al., 2018; Wu et al., 2017) and perchlorate (Sharbatmaleki and
Batista, 2012; Sharbatmaleki et al., 2015)). The findings presented
herein will be helpful for selective ionic removal from various water
matrices.
4. Conclusions
(1) As the standard-AER column process was operated with
alternating exhaustion and regeneration cycles, there is an
inherent relation of the equivalent ratio of coexisting anion
to chloride in the feedwater, in the standard-AER column,
and in the recycled brine. Under these conditions, accurate
control of the equivalent ratio of sulfate and bicarbonate to
chloride in recycled brine of the standard-AER column pro-
cess can achieve selective nitrate removal from feedwater
and accumulation in recycled brine by inhibiting the
competing capacity of sulfate and bicarbonate for ion ex-
change sites. The circular activation/regeneration mode
altered the column elution and breakthrough curves, and
finally achieved selective nitrate removal from feedwater.
The activated standard-AER column in this study and nitrate-
selective AERs share an identical nitrate-selective removal
mechanism.
(2) Feed rate showed a considerable effect on the critical sulfa-
te:chloride equivalent ratio, while severalfold changes in
feed sulfate concentrations were accompanied by slight
changes in the critical sulfate:chloride equivalent ratio in
brine. The presence of abundant sulfate and bicarbonate in
brine and feedwater had no significant effect on nitrate
removal by the standard-AER column. No significant change
in the sulfate preference of standard AERs was observed in
sulfateenitrate binary exchange reactions, as the activation
by optimized brine did not modify the functional groups of
standard AERs.
(3) The optimized brine composition for circular activation/
regeneration of the standard-AER column, and
electrochemical treatment to transform nitrate in brine to
N2 gas, constituted a closed loop to achieve selective
nitrate removal from groundwater during long-term
exhaustioneregeneration cyclic operation. These findings
could be applied for selective removal of other anions by
standard AERs.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgment
This study was supported by the National Natural Science
Foundation of China (No. 21677016, 51878050,91547207 and
U1806217 (Joint Funds)) and National Key R&D Program of China
(2018YFC1406404).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.watres.2020.115571.
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