Combined ion exchange treatment for removal of dissolved

organic matter and hardness

Jennifer N. Apell
1
, Treavor H. Boyer*
Department of Environmental Engineering Sciences, University of Florida, P.O. Box 116450, Gainesville, FL 32611-6450, USA
a r t i c l e i n f o
Article history:
Received 9 November 2009
Received in revised form
5 January 2010
Accepted 6 January 2010
Available online 14 January 2010
Keywords:
Anion exchange
Calcium
Cation exchange
Dissolved organic matter
Magnetic ion exchange
Membrane fouling
Softening
a b s t r a c t
Dissolved organic matter (DOM) and hardness cations are two common constituents of
natural waters that substantially impact water treatment processes. Anion exchange
treatment, and in particular magnetic ion exchange (MIEX), has been shown to effectively
remove DOM from natural waters. An important advantage of the MIEX process is that it is
used as a slurry in a completely mixed ow reactor at the beginning of the treatment train.
Hardness ions can be removed with cation exchange resins, although typically using
a xed bed reactor at the end of a treatment train. In this research, the feasibility of
combining anion and cation exchange treatment in a single completely mixed reactor for
treatment of raw water was investigated. The sequence of anion and cation exchange
treatment, the number of regeneration cycles, and the chemistry of the regeneration
solution were systematically explored. Simultaneous removal of DOM (70% as dissolved
organic carbon) and hardness (>55% as total hardness) was achieved by combined ion
exchange treatment. Combined ion exchange is expected to be useful as a pre-treatment
for membrane systems because both DOM and divalent cations are major foulants of
membranes.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Dissolved organic matter (DOM) and hardness cations (i.e.,
calciumand magnesium) are common constituents of natural
water that have a substantial impact on physical-chemical
unit processes and nished water quality. DOM is undesirable
because it imparts taste, odor, and color to water; increases
chemical requirements for oxidation, coagulation, and disin-
fection; and is a precursor to disinfection byproducts (DBPs).
Hardness cations are primarily an economic concern for
domestic water users. In addition, many industrial processes
require hardness-free water to prevent scaling. Of increasing
importance is the fact that both DOM and calcium have been
shown to cause reversible and irreversible fouling of
membranes (Yoon et al., 1998; Kimura et al., 2004; Saravia
et al., 2006; Gray et al., 2007; Jin et al., 2009).
Coagulationis a commonunit process used to remove DOM
(Dempsey et al., 1984), while lime softening is commonly used
for removal of hardness (Mercer et al., 2005). Coagulation and
lime softening, however, have limitations. For example, coag-
ulation is limited to removal of ultraviolet-absorbing DOM
(Archer andSinger, 2006), while lime softening is limitedby the
solubility of calcite and removal of carbonate hardness
(Stumm and Morgan, 1996). Therefore, alternative treatment
processes for removal of DOM and hardness are sought that
could provide benets over traditional treatment. A combined
anion and cation exchange process is envisioned that would
remove both DOM and hardness, and thereby replace
* Corresponding author. Tel.: 1 352 846 3351; fax: 1 352 392 3076.
E-mail address: thboyer@u.edu (T.H. Boyer).
1
Present address: CDM, 50 Hampshire Street, Cambridge, MA 02139, USA.
Avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ wat r es
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0
0043-1354/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2010.01.004
coagulation and lime softening with a single unit process. The
basis for combinedionexchangetreatment is discussedbelow.
Anion exchange, and in particular magnetic ion exchange
(MIEX), is an alternative to coagulation for DOM removal
(Singer and Bilyk, 2002; Fearing et al., 2004; Boyer and Singer,
2005; Jarvis et al., 2008). MIEX resin is designed to be used as
a slurry in a completely mixed ow reactor or uidized bed
reactor (Boyer and Singer, 2006; Singer et al., 2009). As a result,
MIEXresinis usedas apre-treatment processtotreat unltered
water at the beginning of a treatment train. MIEX resin has
beenpreviously shownto be very effective for removal of DOM
(Humbert et al., 2005; Kitis et al., 2007; Mergen et al., 2008;
Zhang et al., 2008). The substantial reduction in DOM by MIEX
pre-treatment resultsindecreasedchemical requirements and
reducedformationof DBPs (Singer andBilyk, 2002; Johnsonand
Singer, 2004). In addition, research has shown that anion
exchangeandMIEXpre-treatment have the potential toreduce
membrane fouling by DOM when resin carryover is controlled
(Fabris et al., 2007; Zhang et al., 2008).
Cation exchange is an alternative to lime softening for
hardness removal, and has been extensively used for point-
of-use water softening. In municipal water treatment plants,
cation exchange resin is traditionally used in a xed bed
reactor at the end of a treatment train. Orica Watercare, the
manufacturer of MIEX resin, recently developed a weak-acid,
magnetic cation exchange resin specically designed for
removal of hardness. This resin is designed to be used in
a suspended manner as a pre-treatment process for hardness
removal, similar to traditional MIEX resin for DOM removal.
Although cation exchange treatment is less common than
softeninginmunicipal water treatment plants, recent research
has shown that cation exchange is benecial as a pre-treat-
ment for membrane systems (Cornelissenet al., 2009; Heijman
et al., 2009). Cation exchange is used to remove calcium and
other divalent cations to prevent precipitation of sparingly
soluble minerals, such as calcium sulfate and calcium
carbonate, and to minimize enhanced fouling by DOM on
membrane surfaces (Li and Elimelech, 2004). For example,
Cornelissen et al. (2009) showed a decrease in irreversible
fouling on an ultraltration membrane when raw water was
treated with cation exchange resin in a uidized bed. Heijman
et al. (2009) were able to achieve a 97% recovery in a nano-
ltration system with the use of a cation exchange uidized
bedthat achievednearly complete removal of divalent cations.
Thus, combined anion and cation exchange is expected to
substantially decrease membrane fouling by simultaneously
removing DOM and divalent cations.
Although previous researchers have investigated anion
exchange for removal of DOM and cation exchange for
removal of hardness, none of the previous work combined
both anion and cation exchange into a single unit process for
simultaneous removal of DOM and hardness. It is also not
known how the interactions between DOM and hardness
cations would affect the anion and cation exchange reactions.
The potential benets of combined ion exchange for removal
of DOM and hardness are elimination of sludge from coagu-
lation and lime softening, ability to use a single completely
mixed ow reactor or uidized bed reactor at the head of the
treatment train, and removal of both organic and inorganic
membrane foulants.
The overall goal of this work is to evaluate the removal of
DOM and hardness by combined anion and cation exchange
treatment. The specic objectives of this work are: (1) to
evaluate the effectiveness of a magnetically-enhanced cation
exchange resin; (2) to compare removal efciencies for anion,
cation, and combined ion exchange treatment; (3) to evaluate
the effect that simultaneous versus sequential combined ion
exchange treatment has on removal efciencies; (4) to deter-
mine the inuence of regeneration parameters on removal
efciencies; and (5) to discuss additional applications of
combined ion exchange treatment.
2. Materials and methods
2.1. Materials
All experiments were conducted using groundwater from
Cedar Key, FL collected from Well 4 of the Cedar Key Water &
Sewer District. Groundwater was collected in November 2008
and January, February, and April 2009. Finished water was
collected fromthe Cedar Key Water Treatment Plant in August
2009. The nished water was produced by the following
treatment train: permanganate oxidation at the well head for
iron; MIEX to remove DOM; lime softening to remove hard-
ness; sand ltration; and chlorine disinfection.
Magnetically enhanced anion and cation exchange resins,
manufactured by Orica Watercare, were evaluated in this work.
In previous literature, the magnetic anion exchange resin is
referred to as MIEX resin. In this work, the magnetic anion
exchange resin is referred to as MIEX-Cl (i.e., chloride is the
mobilecounter anion) andthemagneticcationexchangeresinis
referredtoasMIEX-Na(i.e., sodiumisthemobilecounter cation).
Both resins have a polyacrylic backbone, macroporous struc-
ture, and contain magnetic iron oxide. In addition, the MIEX-Cl
and MIEX-Na resins are designed to be used in a suspended
manner in a completely mixed ow reactor, as discussed
previously. The MIEX-Cl resin is a strong-base anion exchange
resin with quaternary amine functional groups, and has a volu-
metric anion exchange capacity of 0.52 milliequivalents (meq)
per mL resin (Boyer and Singer, 2008). Additional discussion of
anion exchange resin properties is provided elsewhere (Boyer
and Singer, 2008). The MIEX-Na resin is a weak-acid cation
exchange resin with carboxylic acid functional groups. Weak-
acid cation exchange resins are typically used in the hydrogen-
form at acidic pH values (Clifford, 1999). At neutral to basic pH
values, weak-acid resins function much like strong-acid resins,
and are typically used in the sodium form (Clifford, 1999). The
MIEX-Na resinwas assumedto have a cationexchange capacity
of 0.52 meq/mL because it was functionalized from the same
starting material as the MIEX-Cl resin. All ion exchange resins
were dosed volumetrically by measuring the volume of wet
settledresinusingagraduatedcylinder. Theresinwassettledfor
one hour to ensure consistent volume measurements.
ACS grade chemicals were used for all experimental
procedures and analytical methods. Standard chemicals used
for total organic carbon analysis were provided by the manu-
facturer. Deionized(DI) water was used to prepare all chemical
reagentsandstandards. Glasswarewas cleanedbyrinsingwith
DI water and, if necessary, a 6% nitric acid solution.
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0 2420
2.2. Jar test procedure
A Phipps & Bird PB-700 jar tester with 2 L square jars was used
to conduct batch tests with ion exchange resin. Two liters of
Cedar Key raw water was added to each jar. The ion exchange
resin was measured, as described in 2.1., and added to the jars.
The resin was mixed for 20 min at 100 rpm and allowed to
settle for 30 min. A sample was taken from each jar from
a spigot in the jar. All ion exchange experiments were
conducted using duplicate doses of ion exchange resin, and all
results are shown as average values with error bars corre-
sponding to one standard deviation for duplicate resin doses,
except where noted otherwise.
Individual anion and cation exchange jar tests were
conducted as described in the previous paragraph. In addition,
three types of combined ion exchange experiments were
performed: (1) simultaneous anion and cation exchange, (2)
sequential anion exchange followed by cation exchange
(Sequence 1), and (3) sequential cation exchange followed by
anion exchange (Sequence 2). For all combined ion exchange
experiments, anion and cation exchange resins were
measured separately in graduated cylinders and then added
to a single jar at the appropriate time during the experiment.
Initial jar tests were conducted with fresh ion exchange resin,
which is dened in 2.3 below. After the initial jar test, the resin
from the duplicate jars was combined for regeneration, which
is also described in 2.3. The combined resin was split into
duplicate doses with the assumption that the anion and
cation exchange resins were evenly distributed. Subsequent
jar tests were conducted with regenerated resin, and the tests
are referred to as the number of times the resin was regen-
erated (e.g., one regeneration cycle regen. 1). Sequences 1
and 2 followed the general procedure described above, with
the following additional steps. Three jars were used for the
rst stage of treatment with either anion or cation exchange
resin. After the rst treatment stage, at least 4 L of treated
water was decanted from the three jars, and 2 L each of
treated water was transferred to two clean jars. The comple-
mentary ion exchange resin was added to the new jars for the
second stage of treatment. A sample from each jar was taken
after the second treatment stage.
Raw and treated water samples were measured for pH,
total hardness, alkalinity, ultraviolet (UV) absorbance, dis-
solved organic carbon (DOC), uorescence intensity, chloride,
and sulfate.
2.3. Regeneration of ion exchange resin
Virgin anion and cation exchange resins were regenerated
before their initial use to become fresh resin. Both MIEX-Cl
and MIEX-Na resins were regenerated in a solution that
contained 10 times more sodium or chloride than was theo-
retically available on the resin, based on an ion exchange
capacity of 0.52 meq/mL. For example, 2 mL/L of MIEX-Cl resin
has a capacity of 1.04 meq/L, and a 10 times sodium chloride
solution has a concentration of 10.4 meq/L Cl

(or 10.4 mM
Cl

). Although MIEX-Cl is shipped in the chloride form,

preliminary jar tests showed an increase in DOC removal with
regeneration, suggesting that the virgin resin was not fully
saturated with chloride, possibly due to contamination of the
resin. MIEX-Na resin is shipped as a mixture of sodium and
hydrogen mobile ions, so it was regenerated to convert all
mobile ions to sodium.
The resins were regenerated after each jar test as follows.
Excess water was decanted from the jars and the resin was
rinsed once with DI water. All regeneration solutions had
a sodium chloride concentration of w2 M. The baseline
regeneration procedure used a brine solution that contained
25 times more sodium chloride (on a meq/L basis) than was
theoretically available on the resin. This was achieved by
adjusting the ratio of the volume of regeneration solution to
the volume of MIEX resin. The regeneration solution and resin
were mixed on a stir plate for 30 min and allowed to settle for
10 min before decanting the brine. The container was lled
with DI water, mixed for 10 min, settled for 10 min, decanted,
and repeated for a second time. The cation and anion
exchange resins were combined for the simultaneous ion
exchange tests, so the amount of sodium chloride used for
regeneration was dependent on the amount of cation
exchange resin present. Consequently, the brine solution was
8 times stronger for the anion exchange resin than it was for
the cation exchange resin because of the different dosages of
MIEX-Cl and MIEX-Na resins. For Sequences 1 and 2, the cation
and anion exchange resins were regenerated separately, and
therefore, the ratio of sodium chloride to resin, on a meq/L
basis, was constant at 25 for both resins.
TheMIEX-Naresinwasalsoregeneratedusingaseriesof acid
and base solutions as follows. The resin was stirred in DI water
while hydrochloric acidwas added until pH3 was reached. This
stepconverts theresintothe hydrogenform. Sodiumhydroxide
was then added until pH 11 to convert the resin to the sodium
form. The same rinsing procedure was followed.
2.4. Analytical methods
Samples requiring ltration were ltered through 0.45 mm
nylon membrane lters (Millipore). All lters were pre-rinsed
with 500 mL of DI water followed by 15 mL of sample. Filtered
water was used for all analyses except pH, alkalinity, and total
hardness. An Accumet AP71 pH meter with a pH/ATC probe
was used to measure pH. The pH meter was calibrated before
each use with pH 4, 7, and 10 buffer solutions. Alkalinity and
total hardness were determined following Standard Method
2320 and 2340, respectively (American Public Health Associa-
tion, 1998).
UV absorbance at 254 nm (UV
254
) was measured on a Hita-
chi U-2900 spectrophotometer using a 1 cm quartz cell. Fluo-
rescence excitation-emission matrix (EEM) spectra were
collected on a Hitachi F-2500 uorescence spectrophotometer
using a 1 cm quartz cell. Samples were scanned at 5 nm
increments over an excitation (EX) wavelength 200500 nm
and at 5 nm increments over an emission (EM) wave-
length200600 nm. The raw EEMs were processed in
MATLAB (The MathWorks) following published procedures
(Cory and McKnight, 2005). A DI water EEM, which was
analyzed daily, was subtracted from the sample EEM; the area
under the Raman water peak (EX350 nm) was calculated for
DI water; intensity values of the sample EEM were normalized
by Ramanwater area; and EEMs were plotted inMATLAB using
the contour function.
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0 2421
DOC was measured on a Shimadzu TOC-V
CPH
total organic
carbonanalyzer equipped withanASI-Vautosampler. All DOC
samples were measured in duplicate with average values
reported. The relative difference between DOC duplicates,
dened as the absolute difference between duplicate samples
divided by the mean of duplicate samples, was <10%. Stan-
dard checks for DOC were within 10% of the known value.
Specic UV
254
absorbance (SUVA
254
), dened as (UV
254
/
DOC) 100, was also calculated.
Chloride and sulfate were measured by suppressed
conductivity on a Dionex ICS-3000 ion chromatograph
equipped with IonPac AG22 guard column and AS22 analytical
column. The operating conditions were as follows: 25 mL
sample loop, 4.5 mM Na
2
CO
3
/1.4 mM NaHCO
3
eluent compo-
sition, 1.2 mL/min eluent ow rate, suppressor/column
compartment maintained at 30

C, and conductivity cell
maintained at 35

C. All inorganic anions were measured in
duplicate with average values reported. The relative differ-
ence between duplicates was <5% and standard checks were
within 10% of the known value.
The aqueous concentration of metal cations was deter-
mined by acidifying samples to pH<2 with concentrated nitric
acid (Trace Metal Grade, Fisher Scientic) and measured on an
ICP-AES (Thermo Jarrell Ash) as described in Method 6010C
(U.S. EPA, 2007).
3. Results and discussion
The average composition of Cedar Key groundwater is shown
in Table 1. The minimum and maximum parameter values
show that the water quality was relatively constant over the
study timeframe, as would be expected for a groundwater.
The relatively high concentrations of DOC and hardness in
Cedar Key water illustrate a water source that requires
substantial treatment to prevent the problems associated
with elevated concentrations of DOM and hardness, such as
DBP formationand membrane fouling. Properties of Cedar Key
water relevant to anion exchange treatment are SUVA
254
and
sulfate. Previous research has shown that removal of DOM by
anion exchange is more effective in waters with SUVA
254
>3
L/mg C$mand sulfate <50 mg/L (Boyer and Singer, 2005; Boyer
and Singer, 2006). Thus, MIEX-Cl treatment of Cedar Key water
is expected to be effective given an average SUVA
254
of
3.1 L/mg C$m and sulfate <32 mg/L. The speciation of the
hardness cations is relevant to DOM interactions and cation
exchange treatment. In Cedar Key water, >90% of the hard-
ness was as calcium. This is important because calcium and
DOM form strong inner-sphere complexes, while magnesium
and DOM do not interact (Kalinichev and Kirkpatrick, 2007).
Furthermore, cation exchange resins typically have a greater
afnity for calcium over magnesium (Helfferich, 1995). For
these reasons, it will be assumed that calcium dominates all
interactions with DOM and cation exchange reactions.
3.1. Magnetically-enhanced cation exchange treatment
Preliminary jar tests were conducted using the magnetic
cation exchange resin (i.e., MIEX-Na) to evaluate the rela-
tionship between hardness removal and resin dose. The
treatment goal was to achieve 50% hardness removal so that
changes in removal could be measured when varying the
regeneration procedure. This was also the approximate
hardness removal goal at the Cedar Key Water Treatment
Plant. The change in water chemistry following magnetic
cation exchange treatment is shownin Table 2, where positive
values indicate removal and negative values indicate release.
The results are from jar tests using fresh MIEX-Na resin that
was regenerated with sodium chloride. A linear regression
line was t to the resin dose and hardness removal data
(R
2
0.997), and showed that 3.6% hardness removal is
achieved per mL/L of MIEX-Na resin. Furthermore, MIEX-Na
resin removed 0.40 meq of hardness as calcium per meq of
resin at 16 mL/L, which means that the resin was 40% satu-
rated with calcium. For comparison, complete removal of
hardness from Cedar Key water at 16 mL/L MIEX-Na resin is
equal to 68% of the cation exchange sites occupied with
calcium. Thus, the resin has sufcient cation exchange
capacity to remove all hardness cations at 16 mL/L MIEX-Na
resin. The previous calculations used a MIEX-Na resin
capacity of 0.52 meq/mL and assumed that 20 min was suf-
cient time for ion exchange. The resin capacity is a reasonable
assumption based on previous work using MIEX-Cl resin
(Boyer and Singer, 2008) and information from the manufac-
turer. The mixing time is also reasonable for exchange of
inorganic cations (Kunin and Barry, 1949). Weak-acid cation
exchange resin in the sodium form has been previously
reported to have a high afnity for calcium (Kunin and Barry,
1949), so the excess cation exchange capacity remaining after
treatment suggests that MIEX-Na resin was incompletely
converted to the sodium form. Moreover, weak-acid resin in
the hydrogen-form has a very low afnity for sodium and
calcium (Kunin and Barry, 1949). Therefore, incomplete
conversion of magnetic cation exchange resin to the sodium-
form is a likely explanation for the hardness removal results.
Table 2 shows that MIEX-Na resin also removed UV-
absorbing substances and DOC. This is surprising because
DOM is rich in carboxylic acid functional groups, which gives
DOMa net negative charge over the pHrange of natural waters
(Ritchie and Perdue, 2003) and allows DOM to take part in
anion exchange reactions (Boyer et al., 2008). The increase in
Table 1 Characteristics of Cedar Key water used in ion
exchange experiments.
Parameter Average
a
Minimum
a
Maximum
a
pH 7.6 7.1 8.1
UV
254
(cm
1
) 0.171 0.168 0.186
DOC (mg C/L) 5.6 5.0 6.1
Cl
-
(mg/L) 11.8 10.5 14.3
SO
4
2
(mg/L) 20.9 16.9 31.5
Ca
2
(mg/L) 103
b

Hardness
(mg/L CaCO
3
)
275 265 288
Alkalinity
(mg/L CaCO
3
)
244
b

a November 2008 and January, February, April 2009.
b January 2009; other cations (mg/L): K

0.38, Na

5.5,
Mg
2
4.2, Sr
2
0.87.
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0 2422
chloride suggests the possibility of anion exchange between
aqueous DOM and resin-phase chloride. Because MIEX-Na
resin is synthesized from the same starting material as
MIEX-Cl resin it is possible that there are residual anion
exchange functional groups on the cation exchange resin.
However, minimal removal of sulfate does not support the
anion exchange hypothesis, and suggests that chloride
release is an artifact of regenerating the resin in sodium
chloride solution. Alternative explanations for DOM removal
by cation exchange resin include adsorption of DOM to the
resin matrix and cation exchange uptake of DOM-calcium
complexes. Boyer and Singer (2008) previously showed no
removal of DOC by a weak-acid, magnetic cation exchange
resin, so adsorption is unlikely.
Complexes of DOM and calcium are formed by the binding
of calcium to carboxylic acid groups of DOM (Leenheer et al.,
1998; Kalinichev and Kirkpatrick, 2007). As a result,
DOM-calcium complexes will be represented as DOM-Ca

.
The fraction of DOM that is complexed with calcium (i.e.,
[DOM-Ca

]/[DOM]) can be estimated using the work of Lin

et al. (2005) as follows: [DOM-Ca

]/[DOM] K
s
[Ca
2
], where K
s
is the DOM stability constant. Using a calcium concentration
of 2.57 10
3
M (see Table 1) and K
s
50 M
1
(see Lin et al.,
2005), 13% of the DOM is complexed with calcium. Hence,
there is a fraction of DOM that is complexed with calcium and
is likely removable by cation exchange. Cation exchange
uptake of DOM-Ca

is further supported by results for

Amberlite 200 cation exchange resin shown in Table 2.
Amberlite 200 shows substantial removal of hardness and no
removal of UV
254
, DOC, chloride, or sulfate. It is hypothesized
that the polystyrene matrix of Amberlite 200 allows transport
of calcium and other inorganic ions, but hinders the transport
of DOM-Ca

because of size exclusion. Similar results were

reported for a polystyrene anion exchange resin, whereby
bicarbonate was removed but size exclusion prevented the
uptake of DOM (Boyer and Singer, 2008). Thus, cation
exchange uptake of DOM-Ca

is a reasonable explanation for

DOM removal by MIEX-Na resin. All subsequent cation
exchange jar tests were conducted using 16 mL/L MIEX-Na
resin, because this resin dose achieved >50% hardness
removal.
The impact of the regeneration procedure on the efciency
of hardness removal by MIEX-Na resin was also investigated.
The MIEX-Na resin was regenerated using a brine solution and
an acid/base solution, as described in 2.3. Fig. 1 shows the
effect of the regeneration procedure on hardness removal. For
fresh resin test conditions, regeneration of MIEX-Na resin
with brine solution results in a measurable advantage in
hardness removal as compared with acid/base regeneration.
During the acid/base procedure, the equivalents of sodium
added to solution were approximately equal to 1 times the
resin capacity, while the brine regeneration was conducted
with 25 times more sodium than resin. The subsequent
regeneration test results show that the regeneration proce-
dure had a dramatic impact on hardness removal. For
example, hardness removal by resin regenerated with brine
decreased from 66% for the fresh resin to 52% for the regen-
erated resins (i.e., regen. 1 and 2), while hardness removal
by resin regenerated with acid/base solution decreased from
52% for the fresh resin to <10% for the regenerated resins
(regen. 1 and 2). The difference in hardness removal due to
the brine and acid/base regeneration procedures is a result of
the afnity of the carboxylic acid functional groups on the
resin for hydrogen, sodium, and calcium (Kunin and Barry,
1949). Thus, the acid/base regeneration procedure was found
to be ineffective at regenerating the resin. All subsequent
regenerations were conducted using the brine regeneration
procedure.
3.2. Combined cation and anion exchange treatment
MIEX-Na and MIEX-Cl resins were used separately and
combined to treat Cedar Key water, and removal of hardness,
DOC, and UV
254
was measured as shown in Fig. 2. MIEX-Na
Table 2 Preliminary jar test results for fresh MIEX-Na resin.
a
MIEX-Na (mL/L) Hardness UV
254
DOC Chloride Sulfate
2
b
7.7 1.6 3.3 0.4 0.1
4
b
12.3 3.2 4.4 2.6 2.6
16
c
57.4 0 16.0 0 6.7 3.5 8.7 5.0 3.8 0.1
Amberlite 200
c,d
76.5 0 1.1 0.8 2.3 1.2 1.0 0.1 1.2 0.3
a All results are percent removal or release.
b Single resin dose.
c Duplicate resin dose; average value one standard deviation reported.
d Amberlite 200 manufactured by Rohm and Haas; jar test experiment with resin dose of 8 mL/L.
Fig. 1 Impact of brine and acid/base regeneration
procedures on hardness removal by magnetic cation
exchange using 16 mL/L MIEX-Na resin.
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0 2423
resin was tested at 16 mL/L based on 3.1. Preliminary jar tests
were conducted using MIEX-Cl resin and Cedar Key water
(results not shown), and a dose of 2 mL/L was chosen based on
DOC and UV
254
removal. Combined anion and cation
exchange treatment was conducted at the same doses. All
results are for ion exchange resin that has gone through three
regeneration cycles, which will be discussed in more detail in
3.3. Regenerated MIEX-Na resin removed 54% hardness and
w20% DOC and UV
254
, which is in agreement with fresh
MIEX-Na resin (see Table 2). Regenerated MIEX-Cl resin
removed 3%hardness and >75%DOC and UV
254
. These results
are in agreement with the preliminary MIEX-Cl experiments
(results not shown). When MIEX-Na and MIEX-Cl resins were
combined, hardness removal appeared to be cumulative,
while DOM removal was not cumulative. These results are
explained by the fact that DOM-Ca

complexes retain depro-

tonated carboxylic acid groups in the presence of calcium
(Bose and Reckhow, 1997), so DOM-Ca

can theoretically be
removed by anion and cation exchange, depending on the
ratio of calcium to carboxylic acid groups.
Fluorescence EEMs were analyzed to help understand the
differences in hardness and DOMremoval by anion and cation
exchange. Fig. 3 shows uorescence EEMs for Cedar Key raw
water, anion exchange treated water, and cation exchange
treated water, and the corresponding DOC and hardness
concentrations. The anion and cation exchange data are after
two regeneration cycles. The EEMfor Cedar Key water had two
peaks (see Fig. 3a): Peak 1 at EM445 nm/EX265 nm and
Peak 2 at EM305 nm/EX270 nm. Peak 1 was present in all
raw water samples collected, and is attributed to terrestrially
derived DOM (Coble, 1996). Peak 2 was not present in all raw
Fig. 2 Comparison of DOM and hardness removal by
cation, anion, and combined ion exchange treatment using
2 mL/L MIEX-Cl and 16 mL/L MIEX-Na resins after three
regeneration cycles. Cation and anion exchange data are
from single jar tests.
Fig. 3 Fluorescence EEMs for (a) Cedar Key water (5.4 mg C/L, 277 mg/L as CaCO
3
), (b) 2 mL/L MIEX-Cl resin (1.3 mg C/L,
273 mg/L as CaCO
3
), and (c) 16 mL/L MIEX-Na resin (4.7 mg C/L, 120 mg/L as CaCO
3
).
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0 2424
water samples. Nevertheless, Peak 2 is likely attributed to
microbially derived DOM (Coble, 1996). Anion exchange
treatment substantially decreased the uorescence intensity
of Peaks 1 and 2 (see Fig. 3b), with a corresponding decrease in
DOC of 76%. Cation exchange treatment also decreased the
uorescence intensity of Peaks 1 and 2 (see Fig. 3c), but to
a lesser extent than anion exchange, which is in agreement
with the DOC data. Thus, cation exchange resin appears to
remove a wide range of DOM uorophores. It is not known to
what extent DOM-Ca

complexes are contributing to the

uorescence EEM spectra. Previous researchers have shown
that DOM-metal complexes affect uorescence intensity
(Ohno et al., 2008; Yamashita and Jaffe, 2008). Additional work
is underway studying the interactions between alkaline earth
metals, DOM, and ion exchange reactions.
It is important to emphasize that combined anion and
cation exchange treatment is an effective strategy whereby
a single unit process can remove 71% DOC and 58% hardness,
as shown in Fig. 2. Furthermore, Table 3 shows a comparison
of water quality data from laboratory-scale, combined ion
exchange treatment and full-scale treatment at the Cedar Key
Water Treatment Plant. The combined ion exchange process
produces water that has a water quality near the nished
water quality of Cedar Key.
3.3. Simultaneous versus sequential combined ion
exchange treatment
Sequential cation and anion exchange treatment was tested
and compared with simultaneous ion exchange treatment,
which was the focus of the previous section. The basis for
sequential ion exchange was to evaluate the effect that
interactions between DOM and calcium have on the ion
exchange process. Sequence 1 treated rawwater with MIEX-Cl
resin rst and then with MIEX-Na resin. Sequence 2 was the
reverse with MIEX-Na resin in the rst stage of treatment and
MIEX-Cl resin in the second treatment stage. Fig. 4ac shows
the removal of hardness, DOC, and UV
254
as a function of the
ion exchange treatment scenario and the number of regen-
eration cycles. For fresh resin, removal of hardness showed
the following trend: Simultaneous >Sequence 1 wSequence 2
(see Fig. 4a). Incontrast, removal of DOCand UV
254
showed the
trend of Sequence 1 wSequence 2 >Simultaneous (see Fig. 4b
and c). Although not shown, sulfate removal followed
a similar trend as DOC and UV
254
, with Sequence 1 (84%
removal) Sequence 2 (84% removal) >Simultaneous (77%
removal). Hence, there was a greater difference in removal
efciencies between simultaneous and sequential ion
exchange than between the two sequences. These results
suggest that hardness cations, DOM, and sulfate interact
differently in single ion exchange reactions than in simulta-
neous, combined ion exchange reactions.
Evaluating the performance of ion exchange resin over
multiple regeneration cycles is an important contribution of
this work, because previous studies have focused on testing
fresh resin (Mergen et al., 2008 and references therein). This is
the rst study to comprehensively investigate the regenera-
tion of MIEX resin on a batch treatment basis. The examina-
tion of regenerated resin is useful as it would be impractical
for water treatment plants to use only fresh resin. The
importance of the regeneration process is illustrated in
comparing the removal of hardness, DOC, and UV
254
as
a function of the number of regeneration cycles. For example,
over the course of three regeneration cycles total hardness
removal decreased by 815% for simultaneous and sequential
ion exchange treatment scenarios (see Fig. 4a). This is similar
to the results seen in Fig. 1. In contrast to the hardness nd-
ings, removal of DOC and UV
254
increased for the three ion
exchange treatment scenarios by 816% over the course of
three regeneration cycles (see Fig. 4b and c). Furthermore,
UV
254
removal increased by a greater extent than DOC
removal as indicated by SUVA
254
. For fresh resin, SUVA
254
values for Simultaneous, Sequence 1, and Sequence 2 treated
samples were 2.3, 2.1, and 2.1 L/mg C$m, respectively.
Following three regeneration cycles, SUVA
254
values for
Simultaneous, Sequence 1, and Sequence 2 treated samples
were 1.7, 1.8, and 1.6 L/mgC$m, respectively. Additionally, the
increased ratio of chloride to MIEX-Cl resin in the simulta-
neous resin regeneration did not result in improved perfor-
mance over the sequential treatments (see Fig. 4b and c).
Increased removal of DOM upon regeneration was unex-
pected, because the fresh resin was regenerated before its rst
use to ensure that it had full anion exchange capacity. Sulfate
removal was analyzed in an attempt to understand the
increased removal of DOCand UV
254
over the course of several
regeneration cycles. However, sulfate removal changed by
<5% for fresh resin and regenerated resin (i.e., regen. 1, 2,
and 3). The decrease in calcium removal when using
regenerated resins suggests incomplete removal of calcium
from the resin during the regeneration procedure. If calcium
built up on the resin, DOM complexation with resin-phase
calciumcould result in increased DOMremoval. This is a topic
of follow up work.
A series of paired t-tests were conducted to determine
whether the ion exchange treatment scenarios were statisti-
cally different. The following pairs were tested: Simultaneous/
Sequence 1, Simultaneous/Sequence 2, and Sequence
1/Sequence 2. The null hypothesis for all tests was that the ion
exchange treatment pairs had equal means, i.e., there was no
statistical difference between treatment performance. The
t-tests were conducted in MATLAB using data for both fresh
and regenerated resin and regenerated resin alone for hard-
ness, DOC, UV
254
, and sulfate. Table 4 summarizes the results
of the paired t-tests, and shows that a signicant difference
Table 3 Comparison of nished water quality for
combined ion exchange and municipal drinking water.
Parameter Combined ion
exchange
a
Municipal drinking
water
b
pH 7.7 8.1
DOC (mg C/L) 1.7 1.1
Hardness
(mg/L as CaCO
3
)
112 173
Chloride (mg/L) 48.8 59.7
Sulfate (mg/L) 3.1 1.1
a Cationanion in Fig. 2.
b Cedar Key Water & Sewer District; August 2009.
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0 2425
between ion exchange scenarios was inuenced by the resin
state and chemical removal parameter. For fresh and regen-
erated resin, there was a statistical difference between all
three pairs of ion exchange scenarios for UV
254
removal,
whereas there was no statistical difference between the ion
exchange scenarios for sulfate removal. Both hardness and
DOC removal showed mixed results. For regenerated resin
only, Simultaneous/Sequence 1 showed the most consistent
statistical difference. In summary, the ion exchange treat-
ment scenario and the state of the resin (i.e., fresh versus
regenerated) had an effect on removal performance.
3.4. Inuence of regeneration parameters on removal
efciency
It was shown in 3.1 that regeneration with brine was more
effective than regeneration with an acid/base solution. As
a result, the impact of the meq Na

/meq MIEX-Na resin ratio,

regeneration time, and regeneration solution chemistry were
investigated to learn more about the brine regeneration
process. Hardness removal as a function of sodium chloride
concentration in the regeneration solution is shown in Fig. 5,
where 25 meq Na

/meq MIEX-Na resin is the baseline regen-

eration concentration. The data correspond to treatment with
16 mL/L MIEX-Na resin after one regeneration cycle. There is
a clear trend of increasing hardness removal with increasing
concentration of sodiumchloride in the regeneration solution.
For example, hardness removal increased from 36% at
a regeneration level of 10 meq Na

/meq MIEX-Na resin to 69%

at a regeneration level of 50 meq Na

/meq MIEX-Na resin.

However, the lowest regeneration level is the most efcient
when hardness removal is normalized by the regeneration
level. For example, 3.6% hardness removal per 10 meq Na

/
meq MIEX-Na resin versus 1.4% hardness removal per 50 meq
Na

/meq MIEX-Na resin. Thus, absolute hardness removal

and regeneration efciency must be considered when
choosing a regeneration level.
In Fig. 6, the reaction time and regeneration time were
varied to measure the effects on hardness removal. The
Fig. 4 Comparison of simultaneous and sequential ion exchange treatment on removal of (a) hardness, (b) DOC, and (c)
UV
254
. All jar tests used 16 mL/L MIEX-Na resin and 2 mL/L MIEX-Cl resin.
Table 4 Paired t-tests for ion exchange treatment
scenarios.
a
Parameter Simultaneous/
Sequence 1
Simultaneous/
Sequence 2
Sequence 1/
Sequence 2
Hardness h 0
b
, 0
c
h 0
b
, 0
c
h 1
b
, 0
c
DOC h 1
b
, 1
c
h 1
b
, 0
c
h 0
b
, 0
c
UV254 h 1
b
, 1
c
h 1
b
, 1
c
h 1
b
, 0
c
Sulfate h 0
b
, 1
c
h 0
b
, 0
c
h 0
b
, 0
c
a h 0: null hypothesis cannot be rejected at the 5% signicance
level; h 1: null hypothesis can be rejected at the 5% signicance
level.
b Fresh and regenerated resin.
c Regenerated resin only.
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0 2426
reaction time is dened as the length of time fresh resin is
mixed in raw water, while the regeneration time is the length
of time exhausted resin is mixed in concentrated sodium
chloride solution. The results show that the exchange of
hardness ions with sodiumions can take place within5 minin
both the raw water and the regeneration solution. Although
these results show that the cation exchange process is
relatively quick, reaction times >5 min are needed to transfer
DOM to/from the anion exchange resin (Boyer and Singer,
2005; Humbert et al., 2005). As a result, the reaction time for
combined ion exchange will be determined by the time
required for DOM removal.
All regeneration experiments, up to this point, were
conducted using regeneration solutionprepared with DI water
that contained negligible amounts of hardness and alkalinity.
At a full-scale water treatment plant, however, chemical
reagents are prepared with nished drinking water that may
contain measurable inorganic chemicals. Thus, a set of
regeneration experiments were conducted to compare hard-
ness removal using regeneration solutions prepared from DI
water and tap water. The tap water was from Gainesville, FL
and had a hardness of 146 mg/L as CaCO
3
and an alkalinity of
42 mg/L as CaCO
3
. The combined ion exchange resins were
regenerated using a tap water regeneration solution following
the baseline procedure described in 2.3. Table 5 shows that
hardness removal by 16 mL/L of fresh MIEX-Na resin was
approximately equal for regeneration solution prepared from
DI water and tap water. This means that hardness cations
present in the tap water had no effect on the regeneration
process. In addition, removal of UV
254
-absorbing substances
was consistent regardless of the use of DI or tap water to
prepare the regeneration solution (results not shown).
The impact of reusing the regeneration solution was also
investigated. Hardness removal decreased by 1217% after
each regeneration cycle with used regeneration solution for
both DI water and tap water, as shown in Table 5. Before the
last regeneration, 2.563 g/L of sodium carbonate was added to
the regeneration solution prepared using tap water. This
amount corresponded to the theoretical meq/L of hardness
cations added to the used regeneration solution during the
previous regeneration cycles, based on calculations.
A precipitate was immediately formed by the addition of
sodium carbonate to the used regeneration solution. The
precipitate was not characterized, but it was likely a calcium
carbonate mineral. The regeneration solution was then
ltered through a 1.6 mm GF/A lter (Whatman) to remove the
precipitate. The resin was regenerated using the sodium
carbonate treated solution and tested in a jar test. As a result
of the sodium carbonate addition, hardness removal
increased by 13%fromthe previous jar test. This suggests that
the regeneration solution can be more effectively reused if
calcium is precipitated out of solution, especially if a sodium
salt of carbonate is used. Furthermore, calcium sulfate may
precipitate during regeneration of combined ion exchange
resin, which would benet both anion and cation exchange
regeneration. In summary, MIEX-Na resin regeneration
performance is a function of the sodium concentration;
regeneration is accomplished in 5 min; regeneration solution
prepared from hardness-containing tap water does not affect
regeneration; and regeneration solution can be effectively
reused by precipitating minerals, such as calcium carbonate
and calcium sulfate.
Fig. 6 Effect of varying reaction time and regeneration
time on regeneration efciency and hardness removal by
magnetic cation exchange. Reaction time data based on
16 mL/L MIEX-Na resin and regeneration time data based
on 16 mL/L MIEX-Na D2 mL/L MIEX-Cl resins.
Table 5 Comparison of regeneration solutions prepared
from DI water and tap water.
Regeneration solution Hardness removal
DI water Tap water
a
Fresh regeneration solution 58% 62%
Reused regeneration solution (1) 44% 45%
Reused regeneration solution (2) 33%
Na
2
CO
3
added to reused solution 46%
a Experiments with tap water were 1 L, single jar tests.
Fig. 5 Effect of the ratio of NaCl to MIEX-Na resin on
regeneration efciency and hardness removal. Data
correspond to treatment with 16 mL/L MIEX-Na resin after
one regeneration cycle.
wa t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 4 1 9 2 4 3 0 2427
3.5. Applications of combined ion exchange treatment
Previous researchers have separately investigated anion and
cation exchange treatment and shown these processes to be
a possible pre-treatment for membrane systems to reduce
fouling (Fabris et al., 2007; Humbert et al., 2007; Cornelissen
et al., 2009; Heijman et al., 2009). However, the impact of
combined anion and cation exchange treatment on the
reduction of membrane fouling has not been previously
demonstrated. Fig. 7 shows the theoretical reduction in
membrane fouling potential as a result of the prevention of
calcium sulfate precipitation and removal of DOC, both of
which are major foulants of membrane systems (Shih et al.,
2005; Lin et al., 2006; Jarusutthirak et al., 2007; Ahn et al., 2008).
The membrane fouling potentials were dened as:
Inorganic fouling potential

Ca
2

SO
2
4

Ca
2

SO
2
4

0
; (1)
Organic fouling potential
DOC
DOC
0
; (2)
where the subscript 0 indicates initial concentration. The
fouling potentials were calculated based on experimental ion
exchange treatment data, with cation16 mL/L MIEX-Na
resin, anion2 mL/L MIEX-Cl resin, and cation
anion16 mL/L MIEX-Na and 2 mL/L MIEX-Cl resins. Thus,
the fouling potential is presented as proportional to the
residual concentration of inorganic ions and DOC. A fouling
potential of 1 corresponds to untreated water. It is acknowl-
edged that the reduction in DOC and calcium would not have
a linear relationship with membrane fouling, because fouling
has been shown to be dependent on the characteristics of the
organic matter. However, combined ion exchange should
reduce membrane fouling because it removes two major
foulants. Although individual cation and anion exchange
treatment can reduce the fouling potential, the largest total
reduction in fouling is achieved with combined ion exchange
treatment. It is expected that combined ion exchange
treatment will be effective for reducing membrane fouling
potential for a wide range of calcium, sulfate, and DOC
concentrations.
4. Conclusions
The overall goal of this work was to evaluate combined anion
and cation exchange treatment for removal of DOM and
hardness. The major conclusions of this work are summarized
as follows:
Anion and cation exchange resins can be used in a single
completely mixed reactor to remove DOM and hardness
simultaneously. Combined ion exchange treatment
achieved >55% total hardness removal and 70% DOC
removal. Combined anion and cation exchange also allows
for the most efcient use of the brine regeneration solution
because both sodium and chloride are used as mobile
counter ions.
Although simultaneous and sequential ion exchange treat-
ment showed different removal trends for fresh resin, the
differences between simultaneous and sequential treat-
ment were substantially dampened by the third regenera-
tion cycle. Paired t-tests showed that a statistical difference
between the ion exchange treatment scenarios was depen-
dent on the state of the resin and removal parameter.
Increasing the ratio of meq Na

/meq MIEX-Na resin from

10 to 50 resulted in increased hardness removal. However,
sodium was most effectively used at the lowest regenera-
tion ratio. Therefore, regeneration efciency must include
hardness removal and sodium usage.
Increasing the ratio of meq Cl
-
/meq MIEX-Cl resin from25 to
200 did not result in additional removal of DOM.
Exchange of hardness cations and sodium, during both
treatment and regeneration, was achieved in 5 min.
Brine regeneration solution prepared using tap water, which
contained measurable hardness and alkalinity, provided the
same regeneration efciency as regeneration solution
prepared using hardness-free, DI water.
The regeneration solutioncanbe used repeatedly, especially
if hardness cations are precipitated out of solution. Precip-
itation may also be used to precipitate anions such as
sulfate, which would improve the regeneration of anion
exchange resin.
Acknowledgements
The authors would like to thank Orica Watercare for providing
the MIEX-Cl and MIEX-Na resins. The authors also thank Neil
Doty at the Cedar Key Water & Sewer District for assistance
with collecting raw water samples.
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