pubs.acs.

org/estwater Article

Operating Bicarbonate-Form versus Chloride-Form Ion Exchange

Resins without Regeneration for Natural Organic Matter Removal
Zhen Liu,* Isabelle Papineau, Madjid Mohseni, Sigrid Peldszus, Pierre R. Bérubé, Sébastien Sauvé,
and Benoit Barbeau
Cite This: ACS EST Water 2021, 1, 1456−1463 Read Online

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ABSTRACT: Ion exchange (IX) is a promising drinking water treatment

process for natural organic matter (NOM) removal. However, standard IX
processes require frequent regenerations with concentrated NaCl solution,
Downloaded via TSINGHUA UNIV on August 10, 2021 at 19:45:14 (UTC).

producing a brine that requires costly and complicated disposal methods. To

alleviate the burden of IX brine, we previously proposed operating IX with
infrequent regeneration to favor biomass development on the resins and thus
benefit NOM removal through biomass contribution, a process referred to as
biological ion exchange (BIEX). The objective of the present study is to
evaluate the performance of BIEX filtration for NOM removal from primary
IX to complete exhaustion using bicarbonate-form and chloride-form IX resins. Parallel pilot-scale bicarbonate-form and chloride-
form BIEX were fed with surface water (dissolved organic carbon (DOC) = 7 mg C/L) for 9 months without regeneration. The
results demonstrated that bicarbonate-form BIEX achieved a marginally lower DOC removal (median: 49% vs 53%), a higher
biodegradable DOC (BDOC) removal (average: 50% vs 33%) and a similar disinfection byproduct precursor removal compared to
chloride-form BIEX. Overall, BIEX filtration using bicarbonate-form and chloride-form IX resins offers a similar NOM removal
efficiency and eases spent brine management.
KEYWORDS: biological ion exchange, bicarbonate-form ion exchange, biofiltration, natural organic matter, NOM fractionation,
sustainability

1. INTRODUCTION thermal processes.17 Yet, the drawback of IX regenerability is

Natural organic matter (NOM) removal is of paramount the production of a highly concentrated chloride brine whose
importance for drinking water production as it causes aesthetic direct disposal to the environment is restricted due to its high
salinity.18 As a result, despite its ease of use and great NOM
problems such as color, odor, and taste;1 leads to the formation
removal efficiency, the implementation of IX processes is
of harmful disinfection byproducts (DBP); disrupts water
limited by the burden of brine management and disposal.19
treatment processes (e.g., membrane fouling); and contributes
In an effort to prolong the service time of IX and reduce the
to biofilm regrowth in distribution systems.2−5 Using strong
production of brine, it has been proposed to operate fixed-bed
base ion exchange (IX) is an efficient option to remove
IX filters over an extended period of time without regeneration
NOM.6−9 IX removes NOM through two main mechanisms
to favor biomass development on the surface of IX beads and
which are driven by the functional groups of NOM moieties.
thereby benefit NOM removal through biodegradation, that is,
Charged groups can sorb to IX functional groups through
biological ion exchange (BIEX).20 Lab-scale experiments
electrostatic interactions whereas uncharged groups may
indicated that in the absence of regeneration, biodegradation
adsorb onto the IX surface through the Van der Waal force
contributed to NOM removal as BIEX achieved a higher
or hydrophobic interactions.10−12 IX offers several advantages
dissolved organic carbon (DOC) removal than its abiotic
as a process used for NOM removal. First, it can target
counterpart operated in parallel (BIEX: 60% vs Abiotic-IX:
hydrophilic NOM which is not readily removed by conven-
40%).21 BIEX also exceeded NOM removal efficiency of
tional processes (e.g., coagulation and activated carbon).13,14 biological activated carbon (BAC) filters at lab-scale (BIEX:
Second, IX has proven to be flexible in terms of operational
mode, reactor configurations, and integration within existing
treatment trains.15 It can also be adapted into a broad Received: February 4, 2021
spectrum of applications varying from household point-of-use Revised: April 22, 2021
to full scale drinking water treatment plants (WTP).16 Third, Accepted: May 3, 2021
IX can be regenerated on-site using concentrated NaCl Published: May 11, 2021
solution (e.g., 12% w/v) as opposed to activated carbon
which is usually regenerated off-site using energy-intensive

© 2021 American Chemical Society https://doi.org/10.1021/acsestwater.1c00040

1456 ACS EST Water 2021, 1, 1456−1463
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56% vs BAC: 15%) as well as at pilot-scale (BIEX: 62% vs
BAC: 5%).20,22 Although BIEX proved to be less efficient than
a conventional IX filter which was regenerated on a weekly
basis (IX: 80% vs BIEX: 62%), this novel mode demonstrated
the possibility of significantly reducing the IX brine production
(i.e., 331 days without regeneration) while maintaining a high
NOM removal.20
Another alternative to ease brine management is to resort to
the use of bicarbonate salt as an IX regenerant (i.e.,
bicarbonate-form IX) as opposed to chloride salt. Bicarbonate
brine can be directly disposed into sewers or, in some cases,
the environment as bicarbonate has little impact on flora and
fauna.23,24 Bicarbonate-form IX has a similar affinity for DOC
compared to chloride-form IX and the treated water is less
corrosive due to the release of bicarbonate as opposed to the
release of chloride.25−28 However, the real application of
bicarbonate-form IX remains limited as NaHCO3 is more
expensive than NaCl and has a lower solubility in water/
regeneration efficiency which may progressively lower NOM
removal efficiency as the number of regeneration in-
creases.26,28−30
Consequently, it is of great interest to study the operation of
bicarbonate-form IX in BIEX mode as it could not only greatly
reduce regeneration frequency but also ease brine disposal.
This is of paramount importance for drinking water utilities,
and more important for small communities located in remote
areas which would otherwise depends on chemical/brine
transportation. However, as none of the previous studies
assessed bicarbonate-form IX operated in biological mode
(BIEX), its NOM removal efficiency under such operational
conditions remains unknown. Hence, the objective of the
present study is to evaluate the NOM removal performance of
bicarbonate-form IX operated in BIEX mode with a bench-
mark of chloride-form IX operated in BIEX mode. To better
understand the underlying mechanisms that come into play,
anion loading on IX, DOC removal, treated water biostability
(biodegradable DOC), metabolic activity of heterotrophic
biomass on the media, DBP precursor removal, specific
ultraviolet absorbance at 254 nm (SUVA) and NOM
fractionation in influent and effluent were assessed. The
present study is the first to evaluate the advantages and
limitations of implementing bicarbonate-form IX resins
operated in BIEX mode at pilot-scale.
2. METHODS AND MATERIALS
2.1. Resin Preconditioning. The resin type used in this
study is Purolite A860, a type-I strong base anion exchange
resin with polyacrylic and quaternary ammonium as backbone
and functional group, respectively. The average diameter of
Purolite A860 resin is of 0.75 mm according to the supplier.
Based on previous measurements, the ion exchange capacity is
quantified as 0.68 eq/L of resin and the virgin resin is initially
loaded with chloride.20 Batch preconditioning of both
chloride-form and bicarbonate-form IX was carried out in a
lab-scale 10 L beaker prior to its transfer to pilot-scale packed-
bed filters. The preconditioning of chloride-form IX consisted
of three steps. The virgin IX was first mixed with 120 g/L NaCl
solution (volume ratio = 1 L of resin:3 L of brine) at 250 rpm
for 30 min. Then, it was mixed with demineralized water
(volume ratio = 1:3) at 250 rpm for 5 min to wash out the
excess chloride on resin surface. Finally, resin beads were
soaked in demineralized water before use (within 48 h).
Contrary to chloride-form IX, bicarbonate-form IX are not
1457
Article
commercially available. Consequently, bicarbonate-form IX
was prepared using chloride-form IX which was first mixed
with 80 g/L NaHCO3 solution (volume ratio = 1:3) at 250
rpm for 30 min. Then, the IX beads were mixed in
demineralized water (volume ratio = 1:3) at 250 rpm for 5
min to wash out the excess bicarbonate on resin surface. A
conversion rate was used to evaluate the conversion efficiency
from chloride-form IX to bicarbonate-form IX, which is
defined as the chloride quantity in the brine (i.e., the NaHCO3
solution after regeneration) divided by the theoretical chloride
capacity on the IX beads. These two steps were repeated three
times in order to achieve a final conversion rate of 97% (data
not shown). After conversion, the bicarbonate-form IX beads
were soaked in demineralized water before use (within 48 h).
2.2. Pilot Location and Source Water Characteristics.
The pilot-scale columns were set up at the Pont-Viau drinking
water treatment plant (Laval, Canada) and were directly fed
with raw water from Des Prairies River which is characterized
by a moderate DOC concentration (≈7.0 mg C/L), a neutral
pH (≈7.2) and a low sulfate concentration (5.6 mg/L)
(Supporting Information (SI) Table S1). The pilot-scale
columns were operated over a 9-month period (from April
2019 to January 2020).
2.3. Pilot Design and Operation. Two polyvinyl chloride
(PVC) columns (inner diameter of 101.6 mm) containing 0.6
m (≈4.8 L) of either bicarbonate-form IX or chloride-form IX
were cocurrently operated for 250 days without regeneration
(hereafter BIEX-B and BIEX-C filter). The filtration rate was
maintained at 2.4 m/h (4 bed volumes/h) throughout the
study, which corresponded to an empty bed contact time
(EBCT) of 15 min. Columns were backwashed on a weekly
basis with air (2 min at 55 m/h) and then followed by
unchlorinated treated (20 m/h) water from the WTP. Filter
backwash was terminated either based on wash water turbidity
(≤10 NTU) or when a total backwash volume of 50 L (≈10
bed volumes) was reached.
2.4. Analytical Methods. Water temperature, pH and
turbidity were monitored on-site on a weekly basis. Temper-
ature and pH were measured with a multimeter (HACH
HQ40D), and turbidity was quantified with a turbidity meter
(Hach 2100) using Standard Method 2130 (APHA, 2017).
Influent and effluent samples were also collected on a weekly
basis to assess DOC (TOC meter, Sievers 5310C, GE Water,
U.S.A.) and UV254 absorbance (Ultrospec 3100pro, GE
Healthcare, U.S.A.). Biodegradable DOC (BDOC), which
consists of measuring the DOC reduction in water samples
incubated for 30 days with an inoculum of suspended bacteria
from the raw water, was assessed in parallel according to the
method developed by Servais et al. (1989) and optimized by
Markarian et al. (2010).31,32 To assess influent and effluent
NOM reactivity, trihalomethane (THM) and haloacetic acids
(HAA) precursors were assessed on a weekly basis from June
to August according to the Uniform Formation Conditions test
(UFC) (i.e., by maintaining a free chlorine residual of 1.0 ±
0.5 mg Cl2/L after a contact time of 24h at pH 8.0 and 20
°C).33 HAA5 extraction was done according to Method
552.3.34 Samples were then analyzed by gas chromatography
(7890B GC system, Agilent Technologies, U.S.A.) according
to the Methods 524.2 (THM) and 552.3 (HAA).34,35 Samples
were also collected in May, June, July, August, and December
to allow NOM characterization by liquid chromatography−
organic carbon detection (LC-OCD) analyses in both influent
and effluent through a broad range of operation phases. Such
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Figure 1. Cumulative loading (eq/L of resin) in the (A) bicarbonate-form BIEX (BIEX-B) and (B) chloride-form BIEX (BIEX-C) for four anions
and dissolved organic carbon (DOC) throughout the study period (≈24 000 BV or 250 days). No regeneration occurred during this period.
characterization allows the quantification of five NOM
subfractions: biopolymers (BP), humics (HS), building blocks
(BB), low molecular weight acids (LMW acids), and low
molecular weight neutrals (LMW neutrals).36 All analyses
(DOC, UV254, BDOC, THM and HAA, LC-OCD) were
performed in duplicate, and mean values are reported in this
study.
Anions (Cl−, SO42−, NO3−, NO2−, Br−) were quantified on
0.45 μm filtered samples (Merck Millex-HV) using an ion
chromatograph (ICS 5000 AS-DP DIONEX, U.S.A.) equipped
with an AS18 column. Bicarbonate concentration was
evaluated from alkalinity measurements which were performed
using the acid titration method 2320B.37 Heterotrophic
biomass was evaluated using the 14 C-labeled glucose
respiration test developed by Servais et al. (1991).38 Briefly,
colonized resins were extracted from different depths of the
column (2, 10, 30, 50 cm) and incubated in sealed penicillin
flasks at 20 °C for 3 h with 14C-labeled glucose solution (1 mM
with a radioactivity 0.1−1 μCi/mL). Then, the samples were
acidified by adding H2SO4 (10%) prior to being bubbled using
N2 for 10 min to extract CO2. CO2 gas was trapped in 2 mL
Carbo-sorbE (PerkinElmer) and 8 mL PermafluorE+ (Perki-
nElmer) and then was measured by a liquid scintillation
analyzer (PerkinElmer Tri-Carb 4910 TR) for radioactivity.
The result was obtained in nmol glucose/(mL·h), and then it
was conversed to μg C biomass/mL using the factor 1.1 μg C/
nmol glucose/h.38
2.5. Calculation of BIEX Loadings. To elucidate the
progressive exhaustion of BIEX filters, the loadings of anions
and DOC were calculated using the weekly cumulative charge
balance (expressed in eq/L of resin) as described in eq (1):
i = 36 j = 5
(Cin, i , j − Cout, i , j) × Q × 7d
q(i , j) = ∑∑
i=1 j=1
Vresin
where q(i,j) is the total accumulative loading (eq/L) of solute j
in BIEX filter after week i. Five solutes were considered in this
equation: DOC, chloride, bicarbonate, sulfate, and nitrate.
Nitrite and bromide were neglected from this analysis given
that their concentrations in raw water were below the limit of
detection throughout the study period (NO2− < 0.2 mg/L; Br−
< 0.1 mg/L). Cin,i, j and Cout,i, j respectively represent the weekly
concentration of solute j at week i in the influent and effluent.
Q is the daily flow (460 L/day) and Vresin is the volume of resin
in the columns (4.8 L). DOC charge density was assumed to
be 10 mequiv/g C, a common value for NOM at neutral pH
based on Boyer et al. (2008).
pubs.acs.org/estwater Article
2.6. Statistical Analysis. A Shapiro-Wilk test was used to
confirm the normality of the data at a significance level of p >
0.05 before conducting the hypothesis tests. Based on the
outcome, the hypothesis test was conducted using either a
paired t test or a paired Wilcoxon test for normally and non-
normally distributed data, respectively. The null hypothesis
was bicarbonate-form BIEX and chloride-form BIEX were
identical for the tested metrics at a significance level of p >
0.05. All statistical analyses were conducted in the software R
(version 3.6.3).
3. RESULTS AND DISCUSSION
3.1. BIEX Loading during Pilot Study. During the
operation of BIEX columns, both NOM and background
anions in feedwater were exchanged onto IX resins, and the
BIEX loading of these solutes evolves with the bed volumes
(BV) of operation (Figure 1A). Prior to 5000 BV, bicarbonate
was continuously released until it was exhausted. Meanwhile,
DOC and sulfate continuously increased on the IX resins
whereas chloride first increased on the IX resins and then
rapidly decreased until exhaustion (≈5000 BV). Little nitrate
was exchanged onto the IX resins (max loading: 0.03 eq/L
resin) mainly due to its low concentration in feed waters
(mean concentration 0.9 mg/L). Consequently, the dominant
mechanism on BIEX-B, prior to 5 000 BV, involved DOC and
sulfate exchanging for bicarbonate. As the exchange capacity
was due to precharged bicarbonate, this phase is termed
primary IX. From 5000 to 15 000 BV, sulfate that was
previously retained during the primary IX phase began to be
exchanged with DOC. Other anions (chloride, bicarbonate,
and nitrate) remained insignificantly loaded on the IX resin.
Given that DOC was removed by exchanging with sulfate, we
have defined this phase as secondary IX. Subsequent to 15 000
(1)
BV, the IX resin was deemed to be fully loaded with NOM
since the IX loading with respect to bicarbonate and sulfate
was considered to be exhausted. However, a continuous
increase of DOC loading was observed, which is hypothesized
to be attributable to the contribution of biomass (biosorption,
biodegradation, bioregeneration). The BIEX-C filter exhibited
a very similar loading pattern to BIEX-B (Figure 1B), with the
exception of chloride which was initially charged onto the IX
resins and whose concentration gradually decreased until
exhaustion during the primary IX. By the end of the study,
DOC loading on the IX resin in BIEX-C filter was 0.73 eq/L
resin as opposed to 0.68 eq/L resin in the BIEX-B filter. This
higher loading was attributed to the slightly higher NOM
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removal in BIEX-C filter, which will be presented in the next
section.
3.2. NOM Removal. Effluent DOC was normalized to
influent DOC to account for the variation of DOC
concentration in the BIEX effluents (DOC/DOC0). The
normalized DOC concentrations are presented as a function of
bed volumes in Figure 2A. Prior to 5000 BV (i.e., primary IX),
Figure 2. (A) Normalized effluent dissolved organic carbon
concentrations (DOC/DOC0) of bicarbonate-form BIEX (BIEX-B)
and chloride-form BIEX (BIEX-C) filters throughout the study period
(≈24 000 BV or 250 days). (B) conceptional displacement of
different solutes in the BIEX-B filter in primary ion exchange,
secondary ion exchange and exhaustion phases. NOM was broken up
into three conceptional fractions with an affinity sequence of NOM3
> SO42− > NOM2 > HCO3− > NOM1.
DOC was efficiently removed by both BIEX filters, although
the mean performance of BIEX-B (70 ± 15%) proved to be
slightly lower than BIEX-C (76 ± 8%) (paired t test, p = 0.04).
At approximately 5000 BV, a DOC breakthrough was observed
in both BIEX filters which resulted in normalized DOC
concentrations of 0.64 (DOC = 5.13 mg C/L) and 0.70 (DOC
= 5.36 mg C/L) in BIEX-B and BIEX-C effluents, respectively.
From 5000 to 15 000 BV (i.e., secondary IX), both effluent
DOC concentrations first decreased and then stabilized after 7
000 BV. During this phase, BIEX-B achieved equivalent DOC
removal compared to the BIEX-C (55−56%). Subsequent to
15 000 BV (i.e., exhaustion), DOC concentrations started to
rise in both BIEX effluents until they reached a steady state
(≈19 000 BV). Throughout the study period, the BIEX-B
achieved a marginally lower DOC removal than did the BIEX-
C filter with a median of 49% as opposed to 53% (paired
Wilcoxon test, p < 0.001).
The NOM removal process in BIEX filters is believed to be
primarily due to the chromatographic elution of different
solutes.39 To portray this, NOM in raw water could be broken
up into three conceptual fractions (Figure 2B): (1) NOM1 has
pubs.acs.org/estwater Article
no affinity for the resin and breaks through right from the time
when the operation started; (2) NOM2 and NOM3 have
respectively a lower and higher affinity to the resin as
compared to sulfate, but both have a higher affinity than
bicarbonate (i.e., NOM3 > SO42− > NOM2 > HCO3− >
NOM1 as an affinity sequence). Hence, prior to the DOC
breakthrough (i.e., primary IX), NOM3 and NOM2 were both
removed through the exchange with bicarbonate (or chloride
in the case of BIEX-C filter). When bicarbonate was exhausted,
NOM2 could no longer be exchanged and was progressively
released from the IX as other solutes with higher affinities (e.g.,
sulfate and NOM3) were exchanged against NOM2 on the
surface of the resins. The release of NOM2 from the IX phase
increased the DOC concentration and thus leading to a DOC
breakthrough in BIEX effluents. Subsequent to the release of
NOM2 (i.e., secondary IX), effluent DOC concentrations
reached stability as the exchange between NOM3 and
previously charged sulfate on the IX took place. During the
exhaustion phase (subsequent to 15 000 BV), DOC in both
BIEX effluents rose up again due to facts that IX capacity was
completely exhausted and NOM removed through biomass
contribution (biosorption, biodegradation, and bioregenera-
tion) decreased as temperature decreased from 18 to 1 °C.
Finally, BIEX filters achieved a stable DOC removal (5−7%) in
cold water conditions which is believed to be fully due to the
biomass contribution (biosorption, biodegradation and bio-
regeneration).
3.3. BDOC Removal. Evaluation of BDOC removal allows
an appreciation of the treated water biostability of both BIEX
filters. Over the course of the study, BDOC concentrations
remained stable in raw water with 0.42 ± 0.15 mg C/L (i.e., 6
± 2% of DOC). BDOC removals in both BIEX filters followed
a similar trend throughout the study (Figure 3). Briefly, during
Figure 3. Biodegradable dissolved organic carbon (BDOC) removal
in bicarbonate-form BIEX (BIEX-B) and chloride-form BIEX (BIEX-
C) filters.
primary IX, BDOC removal in the BIEX-B filter decreased
from 80% to 23% following the similar trend to DOC removal
in the filter, suggesting that BDOC removal was mainly due to
ion exchange during primary IX. During secondary IX (i.e.,
subsequent to 52 days of operation), BDOC removal in the
BIEX-B filter was significantly improved to 70% as temperature
increased from 13 °C (5000 BV) to 26 °C (11 000 BV)
whereas DOC removal remained stable from 7000 to 11 000
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BV. The improvement of BDOC removal was attributed to

biomass contribution (biosorption, biodegradation, and
bioregeneration) in warm water conditions. However, as
BDOC is only a marginal fraction of influent DOC in the
current study (6% of influent DOC), such improvement had
limited impact on the overall DOC removal. Finally, during
exhaustion phase, BDOC removal in the BIEX-B filter dropped
to 19% as temperature decreased to 2 °C. Overall, average
BDOC removal in BIEX-B filter (50%) constantly proved to be
higher than BIEX-C (33%) (paired t test, p = 0.02). The
higher BDOC removal in the BIEX-B filter might be attributed
to the favorable pH conditions as the release of bicarbonate led
to a more alkaline effluent than did the chloride one (mean
pH:7.3 vs 6.8 during primary IX).
To verify if the higher BDOC removal in the BIEX-B filter
was due to the higher microbial activities, the extent of
bacterial colonization was assessed. Resins were extracted at 2,
10, 30, 50 cm filter bed depth after 10 000 BV. A 14C glucose
respiration test was performed on each sample to quantify the
spatial distribution of heterotrophic biomass (expressed in μg Figure 4. Natural organic matter (NOM) reactivities (expressed as μg
C/mL resin) in both BIEX filters (SI Figure S1). The BIEX-B disinfection byproducts per mg Cl2 consumed) in raw water,
filter had a lower heterotrophic biomass than the BIEX-C filter bicarbonate-form BIEX (BIEX-B) and chloride-form BIEX (BIEX-
in the upper layers of the filter bed (2 and 10 cm deep or a C) effluents from 5300 to 11 000 bed volumes (i.e., secondary IX).
corresponding EBCT of 0.5 and 2.5 min), whereas no
significant difference was observed for the bottom layers (30 evolution of NOM hydrophobicity in BIEX effluents
and 50 cm deep corresponding to 7.5 and 12.5 min EBCT) of throughout the study (Figure 5). Prior to 5000 BV, the
the two BIEX filters (p = 0.43−0.45). This result indicates that
the measurement of heterotrophic biomass by 14C glucose
respiration test did not correspond to the BDOC removal in
biofilters, a conclusion which is consisted with previous studies
using other biomass assessment methods on BAC filters, such
as phospholipid analysis and adenosine triphosphate anal-
ysis.40−43 Therefore, more studies are needed to elucidate the
relationship between biomass activity and the BDOC removal.
3.4. THM and HAA Precursors Removal. DBP precursor
removals were assessed on a weekly basis, but solely after DOC
breakthrough to study the removal during secondary IX
(5300−11 000 BV) (i.e., subsequent to media colonization).
THM-UFC (mean value: 434 μg/L with 97% chloroform and
3% bromodichloromethane) and HAA5-UFC (mean value:
391 μg/L with 41% dichloroacetic acid and 59% trichloroacetic
acid) concentrations in raw water remained stable throughout
the study period. Both BIEX filters achieved similar THM-
UFC or HAA5-UFC concentrations in the effluent throughout Figure 5. Normalized effluent specific ultraviolet absorbance at 254
the study period with a median of 125 THM-UFC μg/L or nm (SUVA/SUVA0) of bicarbonate-form BIEX (BIEX-B) and
110 HAA5-UFC μg/L (SI Figure S2), suggesting that both chloride-form BIEX (BIEX-C) filters throughout the study period
BIEX filters had similar DBP precursors removal for the study (≈ 24 000 BV or 250 days).
period. To allow a further comparison of THM or HAA
precursors removal in BIEX-B and BIEX-C filters, the NOM effluent of both BIEX filters increasingly became more
reactivity (DBP concentration per unit of chlorine demand) hydrophobic as SUVA values continuously increased through
was calculated (Figure 4). The THM or HAA precursor time. We hypothesize that the removal of hydrophobic NOM
removal was equivalent for both BIEX filters as no significant (such as humics) declined during this period due to the
differences in THM (p = 0.19) or HAA5 reactivities (p = 0.70) depletion of IX capacity on the resin surface. This is of
in both BIEX effluents were observed. Moreover, little importance given that hydrophobic NOM has a greater DBP
differences were observed among THM and HAA speciation formation potential.44 Consequently, although effluent DOC
in both BIEX effluents for chloroform (p = 0.33), values remained low during primary IX phase, the DBP
bromodichloromethane (p = 0.18), dichloroacetic acid (p = formation potential increased over time. Interestingly, when
0.52) and trichloroacetic acid (p = 0.57). These results DOC breakthrough occurred, the SUVA dropped from 3.5 L·
confirmed that the mechanisms involved in the removal of m−1·mg−1 to 3.0 L·m−1·mg−1 for both BIEX filters, indicating a
DBP precursors by both BIEX filters do not differ. release of hydrophilic compounds. After breakthrough, SUVA
3.5. NOM Hydrophobicity. SUVA was calculated using values continued to decline until 13 000 BV, and then
available DOC and UV254 data, and effluent SUVA was increased until it stabilized after 15 000 BV at a normalized
normalized to influent SUVA (SUVA/SUVA0) to assess the SUVA of 0.9 for both BIEX effluents. Overall, no significant
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difference in SUVA was observed between BIEX-B and BIEX-
C effluents throughout this study (paired Wilcoxon test, p =
0.44).
3.6. NOM Fractionation. LC-OCD analyses were
conducted at 2592, 5280, 8064, 10 656, and 22 752 BV on
both BIEX influent and effluent to compare the removal of
NOM fractions during three phases: primary IX, secondary IX
and exhaustion. NOM fractions in raw water remained
relatively stable throughout this study (SI Table S2). To
better understand the affinity of various NOM fractions during
the operation of BIEX filters, removals (1 − C/C0) of the
various NOM fractions are calculated as a function of bed
volumes (96 BV = 1 day). Globally, BIEX-B (Figure 6) and
Figure 6. Removals of natural organic matter (NOM) fractions in
bicarbonate-form BIEX (BIEX-B).
BIEX-C (SI Figure S3) had similar evolution with respect to
different NOM fractions throughout the study period. Briefly,
in the BIEX-B filter, HS is the preferred NOM fraction
eliminated although the initial removal efficiency (≈ 90%)
decreased to 66% at breakthrough (5 280 BV) and then
increased back to 90% during secondary IX. In comparison, BB
were also preferably removed during primary IX (78%) but
were released from the BIEX filter at breakthrough (−62%).
Additionally, BB were no longer removed from the BIEX filters
during secondary IX or exhaustion phases. Initial LMW
neutrals removal by the BIEX-B filter (41%) decreased to 15%
at breakthrough and recovered to 25% after breakthrough.
Finally, BP (22%) and LMW acids (20%) were removed in the
BIEX-B filter to the similar extent and remained stable
throughout the study.
According to the LC-OCD analysis, BB, HS, and LMW
neutrals all surged during the DOC breakthrough, an evidence
proving that NOM released from IX at the breakthrough (i.e.,
NOM2) is mainly found within these three NOM fractions.
Moreover, subsequent to DOC breakthrough, BB were no
longer removed by both BIEX filters. This may be attributable
to its low charge density as it is also hardly removed by
coagulation.36 The number-averaged molecular mass (Mn) of
effluent HS (calculated from the LC-OCD) reveals a drop
from 1800 Da prior to breakthrough to 1000 Da at
breakthrough. Such data demonstrate that HS in NOM2 has
a lower molecular weight (MW) than in NOM1. This
pubs.acs.org/estwater Article
observation corroborates previously reported data where the
major NOM fractions that surged during DOC breakthrough
proved to possess a low apparent molecular weight (AMW) of
0.5−1 kDa.6 This change in HS MW in BIEX effluent at DOC
breakthrough was accompanied by a sudden decrease of SUVA
values. This indicates that NOM2 is relatively more hydro-
philic than the NOM in the BIEX effluent right before the
breakthrough. These observations lead us to conclude that
NOM2 is composed of molecules which exhibit lower charge
density, lower MW and lower aromaticity. Nevertheless, LC-
OCD and SUVA analysis does not allow a perfect distinguish-
ment among the conceptional NOM1, NOM2, and NOM3.
Given the confounding effect of biomass colonization and
loading state of IX resins, more studies are needed to elucidate
the NOM elution in BIEX filters.
3.7. Implication on IX Operation for NOM Removal.
NOM removal in IX filters is usually correlated to the number
of bed volumes, that is, we can run an IX filter just within the
primary IX phase to maximize NOM removal. However, the IX
filter will need to be regenerated more often (≈4000 BV for
this source water) and thus will produce more spent brine,
which is undesirable from an operational, financial and
environmental standpoint. In order to better balance the
treatment efficiency against brine production, we suggest (1)
putting BIEX filters off-line during the DOC breakthrough
(4000 BV-6000 BV) to avoid the surge of DOC; (2) pursue
filter operation until ≈15 000 BV before launching a
regeneration to maximize IX treatment capacity. To minimize
the offline period, the throughput on the IX contactor (BV/h)
could be increased to accelerate the transition phase from
primary to secondary IX. As a result, the IX service cycle could
be prolonged by 9000 BV (considering putting the IX back
online from 6000 BV to 15 000 BV), which corresponds to a
3.25-fold increase of cycle length. Additionally, operating IX in
BIEX mode is expected to have similar DOC removal
compared to conventional operation mode (i.e., with
regeneration) for the same BV of treated water. This is due
to the fact that regeneration of IX resins does not allow a
complete recover of IX capacity and hence the treatment
efficiency in conventional mode would decrease as the service
cycle increses.45 Further, biomass would establish itself on the
IX resins due to the prolonged service time and thus benefit
the removal of BDOC and ammonia (SI Figure S4). Finally, it
should be noted that the metrics of BIEX performance are
determined on a case-by-case basis, which depends on
feedwater characteristics (e.g., sulfate concentration and
NOM properties). Lab-scale pretests are recommended to
investigate the NOM elution profile prior to real application.
Although BIEX can significantly improve the service time of
IX resins, one still needs to regenerate the resins when the
efficiency no more satisfies the treatment objective. As
bicarbonate salt has a lower solubility in water/regeneration
efficiency than chloride salt, BIEX regenerated with bicar-
bonate salt may experience DOC removal efficiency decline as
the operation cycle increases. Our lab-scale tests demonstrated
that the regeneration efficiency using bicarbonate salt (1 M/L)
is approximately 60% of that using chloride salt (1 M/L) for
resins operated for approximately 13 000 BV (data not shown).
Therefore, the regeneration strategies using bicarbonate salt
are yet to be optimized prior to implementation for BIEX
resins. To this end, BIEX filters can be thoroughly regenerated
with chloride regenerant (e.g., 12% w/v) in an intermittent
manner, and in order to minimize brine production, such
1461 https://doi.org/10.1021/acsestwater.1c00040
ACS EST Water 2021, 1, 1456−1463
ACS ES&T Water pubs.acs.org/estwater
chloride regenerant could be directly reused several times
without any efficiency decline before disposal.46 Caustic can
also be used to help recovering IX capacity from exhausted
resins. Additional research will be needed to identify the
optimal regeneration conditions for resins operated in BIEX
mode.
4. CONCLUSIONS
The present study is the first to assess NOM removal
efficiencies of BIEX filters using bicarbonate and chloride-form
IX resins from primary ion exchange to complete exhaustion.
Results demonstrate that, as opposed to its chloride-form
counterpart, bicarbonate-form BIEX achieved a slightly lower
DOC removal (median: 49% vs 53%), a higher biodegradable
DOC (BDOC) removal (average: 50% vs 33%) and a similar
disinfection byproduct precursor removal. BIEX filters using
bicarbonate-form and chloride-form IX resins offer similar
NOM removal efficiencies and ease spent brine management.
BIEX filters can be regenerated with bicarbonate or chloride
solution when the efficiency no more satisfies the treatment
objective. However, the regeneration efficiency using bicar-
bonate salt is yet to be assessed for BIEX resins considering the
lower solubility of bicarbonate salt than chloride salt in water.
Future studies need to identify the optimal regeneration
strategy for BIEX resins according to the type of counterion
used for ion exchange.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsestwater.1c00040.
14
C glucose respiration test result (Figure S1); DBP
concentration in influent and effluent (Figure S2);
NOM fraction removal in BIEX-C filter (Figure S3);
ammonia concentration in influent and effluent (Figure
S4); Raw water physicochemical characteristics (Table
S1); Raw water fractionation through LC-OCD (Table
S2) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Zhen Liu − Department of Chemistry, University of Montréal,
Montréal, Quebec H2V 0B3, Canada; NSERC-Industrial
Chair on Drinking Water, Department of Civil, Mining and
Geological Engineering, Polytechnique Montréal, Montréal,
Quebec H3T 1J4, Canada; orcid.org/0000-0002-7549-
5891; Email: zhen.liu.1@umontreal.ca
Authors
Isabelle Papineau − NSERC-Industrial Chair on Drinking
Water, Department of Civil, Mining and Geological
Engineering, Polytechnique Montréal, Montréal, Quebec H3T
1J4, Canada
Madjid Mohseni − Department of Chemical and Biological
Engineering, University of British Columbia, Vancouver,
British Columbia V6T 1Z4, Canada
Sigrid Peldszus − Department of Civil and Environmental
Engineering, University of Waterloo, Waterloo, Ontario N2L
3G1, Canada
Pierre R. Bérubé − Department of Civil Engineering,
University of British Columbia, Vancouver, British Columbia
V6T 1Z4, Canada
1462
Article
Sébastien Sauvé − Department of Chemistry, University of
Montréal, Montréal, Quebec H2V 0B3, Canada;
orcid.org/0000-0001-8584-1690
Benoit Barbeau − NSERC-Industrial Chair on Drinking
Water, Department of Civil, Mining and Geological
Engineering, Polytechnique Montréal, Montréal, Quebec H3T
1J4, Canada
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsestwater.1c00040
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank Yves Fontaine, Mireille Blais, Tetiana Elyart, and
Pont-Viau drinking water treatment plant personnel for their
support with piloting. We also acknowledge Elise Renault, Julie
Philibert, Jacinthe Mailly, and Gabriel St-Jean for their
assistance in sample analysis. We also acknowledge Xiameng
Feng for the review and helpful suggestions for this paper.
■
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