Removal of natural organic matter (NOM) from water by ion exchange – A review

Accepted Manuscript Removal of natural organic matter (NOM) from water by ion exchange – A review Irina Levchuk, Juan José Rueda Márquez, Mika Sillanpää PII:

S0045-6535(17)31686-7

DOI:

10.1016/j.chemosphere.2017.10.101

Reference:

CHEM 20123

To appear in:

ECSN

Received Date: 30 May 2017 Revised Date:

16 October 2017

Accepted Date: 17 October 2017

Please cite this article as: Levchuk, I., Rueda Márquez, Juan.José., Sillanpää, M., Removal of natural organic matter (NOM) from water by ion exchange – A review, Chemosphere (2017), doi: 10.1016/ j.chemosphere.2017.10.101. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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autochthonous

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Carboxylic acids

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NOM removal efficiency

Sources of NOM in water

Ion Exchange Treatment

Treatment Results

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Removal of natural organic matter (NOM) from water by ion exchange – A review

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Irina Levchuk*1,2, Juan José Rueda Márquez1,2, Mika Sillanpää1,3

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Laboratory of Green Chemistry, Department of Energy and Environmental Technology, Faculty of Technology, Lappeenranta University of Technology, Sammonkatu 12, FI-50130 Mikkeli, Finland 2

Department of Environmental Technologies, Faculty of Marine and Environmental Sciences, Cadiz University, Poligono Rio San Pedro s/n, Puerto Real, 11510 Cadiz, Spain

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Corresponding author: [email protected]

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Department of Civil and Environmental Engineering, Florida International University, Miami, FL 33174, USA

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Abstract:

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Natural organic matter (NOM) is present in underground and surface waters. The main

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constituents of NOM are humic substances, with a major fraction of refractory anionic

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macromolecules of various molecular weights. The NOM concentration in drinking water is

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typically 2 to 10 ppm. Both aromatic and aliphatic components with carboxylic and phenolic

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functional groups can be found in NOM, leading to negatively charged humic substances at

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the pH of natural water. The presence of NOM in drinking water causes difficulties in

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conventional water treatment processes such as coagulation. Problems also arise when

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applying alternative treatment techniques for NOM removal. For example, the most

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significant challenge in nanofiltration (NF) is membrane fouling. The ion exchange process

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for NOM removal is an efficient technology that is recommended for the beginning of the

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treatment process. This approach allows for a significant decrease in the concentration of

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NOM and prevents the formation of disinfection byproducts (DBPs) such as trihalomethanes

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(THMs). This article provides a state-of-the-art review of NOM removal from water by ion

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exchange.

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Keywords: Water Treatment, Natural Organic Matter (NOM), Ion Exchange, disinfection

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byproducts (DBP), drinking water

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ABBREVIATIONS

22 Disinfection byproduct

DOC

Dissolved organic carbon

FIX

Fluidized ion exchange

FP

Formation potential

HAAs

Haloacetic acids

IE

Ion exchange

MIEX®

Magnetic ion exchange resin

NF

Nanofiltration

NOM

Natural organic matter

PAC

Powdered activated carbon

SHA

Slightly hydrophobic acid

SUVA

Specific UV absorbance

THMFP

Trihalomethane formation potential

THM

Trihalomethane

TOC

Total organic carbon

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Very hydrophobic acid

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DBP

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1. Introduction The elimination and control of natural organic matter (NOM) in drinking water are of high

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environmental interest. NOM is typically removed from drinking water for aesthetic concerns

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such as colour, odour and taste (Leenheer and Croué, 2003). The presence of NOM in water

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also implies difficulties in the purification process. For example, NOM causes fouling of

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membranes and decreases the efficiency of activated carbon (Gibert et al., 2013a; Gibert et

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al., 2013b; Kennedy et al., 2008; Kim and Dempsey, 2013; Lee et al., 2004; Teixeira and

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Sousa, 2013; Zularisam et al., 2007). NOM can react with chemicals used in the water

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treatment process, which may lead to the formation of disinfection byproducts (DBPs), some

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of which can be carcinogenic (Bolto et al., 2004; Tian et al., 2013; Yang et al., 2013).

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Interestingly, when major disinfectants (for example, chlorine, ozone or chlorine dioxide) are

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applied for drinking water disinfection, approximately 600-700 DBPs can be formed (Krasner

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et al., 2006). There have been numerous reports in the last few years on the formation of new

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aromatic halogenated DBPs from the reaction of NOM with chlorine and chloramine (Pan et

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al, 2017; Wang et al., 2016). For instance, iodinated DBPs were reported to exhibit highly

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elevated toxicological effects in comparison with chlorinated and brominated DBPs (Plewa et

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al., 2004). During conventional treatment, NOM is usually removed from potable water

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before the disinfection process. However, a novel approach to efficiently control DBPs was

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recently suggested (application of granular activated carbon adsorption during chlorination)

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(Jiang et al., 2017).

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Depending on the NOM characteristics, different treatment methods for removal can be

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applied (Zheng et al., 2016; Pan et al., 2016). The most commonly applied methods for

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removal of NOM from water are coagulation (Matilainen et al., 2010), adsorption (Sillanpää

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and Bhatnagar, 2015), membrane filtration (Sillanpää et al., 2015), advanced oxidation

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processes (AOPs) (Matilainen and Sillanpää, 2010), and biological and ion exchange (IE)

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ACCEPTED MANUSCRIPT processes (Figure 1). IE for NOM removal from drinking water has recently attracted

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significant attention from scientists and industry. In the last ten years, the number of scientific

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papers containing the keywords NOM, DOC or ion exchange in the title has increased

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(Figure 2).

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The main aim of this work was to provide up-to-date information concerning various ion

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exchangers and their efficiency in eliminating NOM from potable water.

2. Ion exchange

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2.1 Main principles

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(Harland C.E., 1994; Wachinski, A. M., Etzel J.E., 1997). The solid phase is called an ion

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exchanger or ion exchange resin and, as it is insoluble in the liquid phase, carries

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exchangeable ions and does not undergo substantial structural changes during the reaction

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(Helfferich, 1995). Depending on the exchangeable ions, ion exchangers can be divided into

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cation and anion exchangers. Simultaneous cation and anion exchange can also be performed

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using certain types of materials (amphoteric ion exchangers). Typical cation and anion

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exchange reactions are shown in (1) and (2), respectively, where X is the structural unit of the

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ion exchanger.

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The ion exchange process is a reversible exchange of ions between solid and liquid phases

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2NaX + CaCl2(aq) ↔ CaX2 + 2NaCl(aq)

(1)

2XCl + Na2SO4(aq) ↔ X2SO4 + 2NaCl(aq)

(2)

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Reaction (1) is attributed to the softening of water. During the typical water softening

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process, hard water is pumped through an ion exchange column (NaX) and cations of calcium 5

ACCEPTED MANUSCRIPT (for instance) are removed from the water and replaced by an equivalent amount of sodium.

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When all the sodium ions in the cation exchanger are replaced, it is considered “exhausted”

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and the ion exchange resin can be easily “regenerated” using a solution of sodium salt

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(Helfferich, 1995).

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The unique properties of ion exchangers are due to their structure, which, according to the

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common definition, is a framework carrying a positive or negative surplus charge,

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compensated by opposite ions known as counter-ions. Because the counter-ions are moving

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freely, they can be easily replaced by other ions with the same sign (Helfferich, 1995). The

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counter-ion content in the ion exchanger is defined as the ion exchange capacity. Another

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important characteristic of ion exchangers is the selectivity (the ability of the ion exchanger

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to distinguish between different species of counter-ions) (Helfferich, 1995).

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The ideal ion exchanger should meet the following requirements (Harland, 1994):

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hydrophilicity

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chemical and physical stability

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relatively high speed of ion exchange

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sufficient ion exchange capacity

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particle size and effective surface area adequate for the application

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economic feasibility

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2.2 Types of ion exchange resins A wide range of natural and synthetic materials possess ion exchange properties. In

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wastewater treatment and industrial applications, synthetic resins are primarily used.

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Different types of ion exchange resins can be distinguished (Wesley and Eckenfelder, 2000):

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Strong-acid cation resins

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Weak-acid cation resins

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Weak-base anion resins

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Metal-selective chelating resins

The chemical behaviour of strong-acid cation resins resembles that of a strong acid, which

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explains the origin of their name. The chemical matrix of this type of resin consists of

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styrene, divinylbenzene (DVB) and sulfonic acid functional groups.

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The behaviour of weak-acid cation resin is similar to that of weak organic acids and is weakly

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dissociated. The functional group is a carboxylic acid.

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Strong-base anion resins can be divided into two main types. The first type of resins contain a

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functional group of three methyl groups and an ethanol group replaces one of methyl groups

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in the second type of resins. Strong-base exchangers of the first type are more stable whereas

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exchangers of the second type have higher capacity and regeneration efficiency (Wachinski

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and Etzel, 1997).

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Weak-base anion exchangers are normally based on phenol-formaldehyde or epoxy matrices

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with a functional group of secondary or tertiary amines (Wachinski and Etzel, 1997). Heavy

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metal-selective chelating resins are similar to weak-acid cation resins and have high

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selectivity for metals. The functional group can be an ethylenediaminetetraacetic acid

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(EDTA) compound, among others (Wesley and Eckenfelder, 2000).

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3. Background on NOM

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The term natural organic matter (NOM) is generally defined as all organic compounds (in

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dissolved and particulate forms), except synthetic molecules such as organic micropollutants,

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present in aquatic or terrestrial environments. Herein, the NOM attributed to surface and

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ground water suitable as sources of drinking water are discussed.

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NOM in natural waters can be microbially (autochthonous) and terrestrially derived

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(allochthonous) (Aliverti et al., 2011). The origin of terrestrially derived NOM is degradation

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ACCEPTED MANUSCRIPT and/or leaching of organic matter from plants and soil; it is primarily in low-order rivers and

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streams (Aliverti et al., 2011; Drewes and Summers, 2003). Terrestrially derived NOM can

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be characterized by an intense colour, a relatively high aromatic carbon level and high

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carbon/nitrogen ratios (usually 100/1) (Drewes and Summers, 2003). Microbially derived

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NOM (produced by microorganisms such as bacteria and/or algae) can be found in significant

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amounts in lakes, streams of moderate or high trophic status and reservoirs (Drewes and

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Summers, 2003). The NOM of this natural water has a weak colour, low aromatic carbon

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level and lower carbon/nitrogen ratios (usually 10/1) (Drewes and Summers, 2003). The

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biodegradability of autochthonous NOM is often higher than that of allochthonous NOM

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(Leenheer and Croué, 2003).

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Structural characterization of NOM is a topic of interest (Zheng et al., 2016; Pan et al., 2016;

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Leenheer and Croué, 2003; Minor et al., 2014; Mopper et al., 2007; Sandron et al., 2015;

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Wangersky, 1993). NOM is commonly separated into particulate and dissolved organic

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matter by filtration through 0.45 µm membrane. Typically, only 1 - 10% of dissolved NOM

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is identified due to the complexity of NOM composition (Leenheer and Croué, 2003). The

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characterization of NOM is presented in Figure 3 (Leenheer and Croué, 2003; Aliverti et al.,

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2011; Matilainen et al., 2011).

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As shown in Figure 3, dissolved NOM can be divided into hydrophobic and hydrophilic

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components. Three hydrophobic and three hydrophilic fractions of NOM can be distinguished

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(Nkambule et al., 2009). The main constituents of the hydrophobic fractions are humic and

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fulvic acids. The hydrophilic fraction usually contains low-molecular-weight carbohydrates,

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proteins and amino acids. For instance, in river water, the distribution of organic compounds

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can be 40% fulvic acids, 10% humic acids, 30% hydrophilic acids, 10% carbohydrates, 6%

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carboxylic acids and 4% amino acids (Bolto et al., 2004). Depending on the fraction of NOM,

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deviations in the formation of disinfection byproducts (DBPs) can be observed. For example,

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ACCEPTED MANUSCRIPT THM formation is caused by all six fractions of NOM. However, hydrophobic fractions of

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NOM have been reported to be key THM precursors (Hua et al., 2015). Humic substances are

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known as “problematic” compounds because they can interact with non-polar contaminants

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such as pesticides or polychlorinated biphenyls (Bolto et al., 2004).

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4. Ion exchange for NOM elimination

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4.1 Impact of NOM characteristics on removal efficiency

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in cases of a high NOM concentration in raw water (Hongve et al., 1999). The NOM

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concentration in drinking water varies from 2 ppm to 10 ppm, of which 10–30% are defined

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species (Bolto et al., 2002). According to some estimates, 10% -40% of NOM is not removed

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after ion exchange, which probably correlates with the amount of uncharged species in the

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NOM (Bolto et al., 2004). Hence, to select an appropriate water treatment method for NOM

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removal, it is critical to define the species contained in the NOM in each specific case. IE is

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more efficient than coagulation for removal of charged organic compounds from water (Bolto

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et al., 2002). A comparative study of humic substance removal using adsorption onto

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activated carbon, anion-exchange resins, carbonaceous resins and metal oxides found that the

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ion exchange process was most efficient (Fettig, 1999). Recent studies of NOM removal

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using IE are summarized in Table 1.

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Strongly basic anion-exchange resins for NOM removal from drinking water are well studied

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(Bolto et al., 2004; Brattebø et al., 1987). The widely studied resins include quaternary

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ammonium resins in chlorine form. NOM removal from water can be represented by the

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following reaction, where R- is the charged dissolved organic carbon (Bolto et al., 2004):

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Anion exchange water treatment is a well-known alternative to conventional water treatment

Resin-NMe3+Cl- + R- ↔ Resin-NMe3+ R- + Cl-

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ACCEPTED MANUSCRIPT Regeneration of this type of resin is conducted using an excess of brine or caustic brine. The

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effects of the physical and chemical structures on NOM elimination have also been studied,

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and the highest NOM removal was attributed to resins with high water content (Bolto et al.,

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2002). It was also reported that polystyrene resins have higher selectivity than acrylic resins.

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A review of studies of strongly basic anion exchangers conducted prior to 2004 is available

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(Bolto et al., 2004). Studies conducted on NOM removal with weakly basic resins suggest

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that they are not as efficient as strongly basic resins or their acrylic analogues (Bolto et al.,

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2004).

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Commercially available anionic exchange resins for NOM acid removal from water were

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tested and the best performance was observed for the smallest resins and/or those with the

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highest water content. However, the names of the resins were not included in this work for

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the sake of confidentiality (Cornelissen et al., 2008).

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One of the main problems in implementing IE for NOM removal on an industrial scale is the

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need to use a packed bed of ion-exchange resin, which is possible only at later steps of the

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water treatment process. A 2.5 ML/day plant in Germany can be considered as an example of

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dissolved organic carbon (DOC) removal from water on a large scale (Bolto et al., 2002).

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Successful DOC removal from water (initial concentration 6.5 mg/L) was conducted using

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macroporous styrene resin. Within a contact time of 1.2 minutes, 50% of the DOC was

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removed. However, the plant stopped this process due to difficulties in disposal of the

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regeneration solution.

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4.2 MIEX-DOC process

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Australian Water Quality Center (AWQC) in collaboration with Orica Australia Pty Ltd.

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allows for the use of MIEX in a slurry reactor prior to the coagulation step (Cornelissen et al.,

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A magnetic ion exchange resin MIEX® and MIEX®-DOC process developed by the

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ACCEPTED MANUSCRIPT 2008; Drikas et al., 2002). The MIEX is a strong base anion-exchange resin with a

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macroporous polyacrylic matrix in chloride form that contains magnetic iron oxide particles

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within its core (Boyer and Singer, 2006; Drikas et al., 2011). Incorporated into the resin, the

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iron oxide particles simplify separation and recycling of the resin in a continuous process.

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The MIEX resin particle size is 2–5 times smaller in diameter than that of traditional resins

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(Hsu and Singer, 2010), which leads to faster ion-exchange kinetics. The MIEX process

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consists of two main steps (Figure 4): contact of the raw water with the MIEX slurry for 10–

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30 minutes and separation of the resin and subsequent treatment of the supernatant (usually

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coagulation). The collected MIEX resin is regenerated and reused (Singer and Bilyk, 2002).

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The possibility of using MIEX resin without pretreatment and its high stability make it a

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highly beneficial option for drinking water treatment (Kitis et al., 2007). Despite the

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advantages of MIEX treatment, it was reported to be unfeasible when the raw water contains

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phosphates (Koreman, 2016) due to phosphate adsorption on the porous resin and biofilm

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growth on the resin surface, which blinds active groups (“resin blinding”).

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Comparison of the NOM removal efficiency using MIEX with conventional methods was

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conducted on laboratory and pilot scales. For instance, laboratory-scale studies demonstrated

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that a combination of MIEX and alum removed DOC from water more efficiently than alum

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alone. A broader range of compounds was removed and trihalomethane (THM) formation

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was lower when MIEX was included in the treatment process (Drikas et al., 2003). The effect

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of MIEX resin on membrane fouling reduction was demonstrated in several studies (Fabris et

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al., 2007; Huang et al., 2011; Humbert et al., 2007; Kim and Dempsey, 2010). Singer and

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Bilyk (Singer and Bilyk, 2002) compared combined MIEX and alum with alum in treatment

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of nine surface waters and observed that the total organic carbon (TOC) concentration, UV

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absorbance, and THM and haloacetic acid concentrations in the treated water were lower

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when MIEX resin was used. The capability of MIEX resin to remove hydrophobic and

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ACCEPTED MANUSCRIPT hydrophilic acids was also observed. The effect of the hydrophobicity of the water on the

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DOC removal by MIEX resin was studied and the DOC removal decreases as the water

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hydrophobicity increases. Thus, DOC elimination of 56, 33 and 25% was observed for water

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containing 21, 50 and 75% of hydrophobic NOM, respectively (Mergen et al., 2008).

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Monitoring of different parameters at a water treatment plant in South Australia suggests that

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changes in the water quality and character of the NOM significantly affect the performance of

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MIEX resin (Morran et al., 2004) and confirm the efficiency of the MIEX and coagulation

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process. Improvement in the NOM removal efficiency using MIEX in comparison with

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coagulation alone was also reported (Fearing et al., 2004; Humbert et al., 2005a). In addition

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to improving NOM removal from water, incorporation of the MIEX process into a

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conventional water treatment scheme (coagulation-flocculation) leads to a decrease in the

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required dose of coagulants and other chemicals. For instance, five different raw drinking

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water samples from the City of Istanbul were treated using the MIEX process prior to

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coagulation on a laboratory scale and the effects of different doses of MIEX, contact times

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and coagulant doses on the quality of treated water were investigated (Kitis et al., 2007).

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After treatment using a resin dose of 5–10 ml settled resin/l and contact time of 10–20

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minutes, the DOC and specific UV absorbance (SUVA254) were <1.5 mg/l and < 2 1/mg

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DOC-m, respectively. Moreover, the removal of nitrates and sulfates from the raw water

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samples was determined to be 17–42% and 9–24%, respectively (MIEX dose of 10 ml settled

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resin/l and 10 minutes of contact time). Depending on the quality of the raw water, the

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required coagulant (alum) dose in treating water with MIEX prior to coagulation was

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estimated to decrease by 0–30 mg/l (Kitis et al., 2007). Another study was conducted with

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four types of drinking water from California, characterized by low turbidity, moderate

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organic carbon concentration, moderate to high concentration of bromide and a wide range of

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alkalinities (Boyer and Singer, 2005), respectively, to determine if MIEX treatment is more

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ACCEPTED MANUSCRIPT efficient than coagulation with alum. The findings suggest that MIEX treatment and MIEX

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treatment followed by coagulation performed similarly and the DOC and SUVA removal

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efficiency of coagulation was significantly lower, especially for raw water with high SUVA

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and low anionic strength (Boyer and Singer, 2005).

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The effect of bicarbonate, chloride, and bromide presence in water on the DOC removal

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using MIEX and polystyrene resins A-641 and IRA910 was studied by Hsu and Singer (Hsu

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and Singer, 2010). Bromide removal was reported to be more efficient when using A-641 and

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IRA910 resins but the level of DOC elimination using MIEX resin was higher. Thus, the

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DOC removal efficiencies using MIEX, A-641 and IRA910 resins after 30 minutes were 46,

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13 and 7%, respectively (Hsu and Singer, 2010). An increase in the contact time to 5 h

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resulted in higher DOC elimination for all resins tested and the performance of MIEX

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remained the highest. Simultaneous removal of NOM, nitrates, sulfates, bromides, and

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pesticides from high-DOC surface water was performed using four commercial strong anion-

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exchange resins, MIEX, DOWEX-11, DOWEX-MSA and IRA-938 (Humbert et al., 2005a).

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All tested resins demonstrated significant DOC removal. However, the kinetics of the DOC

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removal from water using MIEX and IRA938 resins were faster than those of DOWEX-11

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and DOWEX-MSA. After 3 min of contact time with 8 mL/L of MIEX® and IRA938®, the

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DOC removal was approximately 60%, and, under the same experimental conditions, the

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DOC eliminated using MSA® and DOWEX11® was 10% and 21%, respectively. These

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results are explained by the small bed size of MIEX® and large macroporous structure of

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IRA938®. Both high and partially low molecular weights of UV-absorbing NOM were

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removed using all resins tested. The pesticide removal using MIEX, DOWEX-11, DOWEX-

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MSA was estimated to be 10%; 35% was eliminated using IRA938. The optimal contact time

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for DOC removal using MIEX resin with doses of 2–8 mL/L was estimated to be 10–20 min

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(Humbert et al., 2005a). Higher NOM removal efficiency of MIEX than DOWEX 11 resin

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ACCEPTED MANUSCRIPT for NOM removal from low- and high-sulfate water was also confirmed (Ates and Incetan,

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2013).

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Recently, the efficiency of NOM removal was tested using MIEX resin in bicarbonate form

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and compared with the well-studied MIEX chloride-form resin (Walker and Boyer, 2011).

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The performance of both resins was similar for the removal of DOC, UV254 and sulfate and

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the bicarbonate-form of MIEX demonstrated higher performance for bromide removal. The

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sequence of affinity for DOM and anion removal was similar for fresh MIEX-HCO3 and

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virgin MIEX-Cl: sulfate ~ UV254 > DOC > bromide. The removal efficiency for both resins

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decreased as the number of regeneration cycles increased. The DOC elimination using

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MIEX-HCO3 resin was reported to be 69% with an average initial concentration of 18 mg

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C/L.

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The NOM removal results using MIEX resin for batch and continuous operations conducted

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before 2008 were summarized by Mergen et al. (2008).

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The first water plant utilizing the MIEX DOC process for treatment of potable water was

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launched in 2001 in Mt Pleasant, South Australia, with a capacity of 2.5 ML/day (Drikas et

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al., 2011). This plant was divided into two streams with capacities of 1.25 ML/day. The first

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stream comprised the MIEX DOC process followed by coagulation, flocculation,

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sedimentation, and filtration and the second stream contained a submerged microfiltration

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step that is implemented after the MIEX DOC process. Monitoring of different parameters

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and comparison with similar water treatment schemes that lack the MIEX DOC process were

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conducted over a two-year period at the abovementioned plant (Drikas et al., 2011). The

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results showed significant improvement in the DOC removal from treated water when MIEX

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is used. The water quality after treatment was less affected by DOC changes in the raw water

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when MIEX was utilized.

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ACCEPTED MANUSCRIPT Experiments on NOM removal from water conducted in a continuous-flow pilot plant

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operated at 7.6 L/min and MIEX resin demonstrated substantial removal of UV-absorbing

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substances and DOC and the optimal dose of MIEX resin was estimated to be 0.16 ml/L

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(Boyer and Singer, 2006). Another MIEX pilot with a flow of 1 ML/day was successfully

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tested and a scale-up to 225 ML/day was conducted (Bolto et al., 2002).

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4.3 Fluidized ion exchange

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NOM removal (Cornelissen et al., 2009). The main principle of this method is that the rate of

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sedimentation of suspended solids in the feed water is lower than that of the ion-exchange

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resin. Thus, when water is pumped into an up-flow reactor configuration at certain speeds,

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the ion exchange resin is fluidized, and suspended solids present in the raw water are

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removed. The test was conducted with actual surface water and an FIX process followed by

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ultrafiltration, demonstrating the feasibility of the process (Cornelissen et al., 2009). Use of

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the FIX process prior to the ultrafiltration step significantly decreased membrane fouling. A

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process comprising a fluidized bed reactor with MIEX resin followed by hydrophilic (NE70)

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and hydrophobic (NE90) nanofiltration membranes was tested for NOM removal from

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Nakdong River (Korea) raw water (Kaewsuk and Seo, 2011). The raw water was

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characterized by low-molecular-weight (MW) NOM content with hydrophilic compounds

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such as carboxylic, amino sugar and aliphatic hydrocarbon compounds. The removal

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efficiency of phenolic compounds and compounds with low SUVA (aliphatic hydrocarbon

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and amino sugar) using MIEX was reported to be significant and the removal of carboxylic

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compounds was not as efficient (Kaewsuk and Seo, 2011). The best performance for NOM

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elimination from Nakdong River raw water was achieved using an NE90 membrane filtration

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followed by MIEX.

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Fluidized ion exchange (FIX) is another type of process utilizing ion exchange resin for

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4.4 Suspended Ion Exchange process (SIX)

332

developed by PWN Technologies in the Netherlands (Koreman, 2016) for DOC removal

333

from surface water. Interestingly, all commercially available resins can be used in the SIX®

334

process. Depending on the resin selected, the NOM concentration in the water and the desired

335

level of water purification, the concentration of resin used in this process varies from 4 to 20

336

mL resin/L (Koreman, 2016). After adding the resin, the raw water flows through plug flow

337

reactors. A relatively short contact time (10–30 mins) is typically applied. Notably, the resin

338

flows out of the plug flow reactors with the water and does not stay inside. After the plug

339

flow reactors, the resin is separated in a lamella settler, collected and regenerated. The

340

advantages of the SIX® process include a relatively short contact time, which allows for

341

avoiding the “resin blinding” effect (formation of biofilm on the surface of the resin).

342

There are few studies concerning NOM removal using the SIX® process. The first large-scale

343

SIX plant, Water Treatment Plant (WTP) Andijk, began operation in 2014 with a 5,500 m3 h-1

344

capacity (Koreman, 2016). As noted above, any type of resin can be used in the SIX process.

345

WTP Andijk chose a strongly basic acrylic gelular anion resin (Lewatit VPOC 1017). This

346

selection was attributed to a combination of various critical factors such as the adsorption and

347

desorption kinetics, capital costs, resin debris, and sedimentation properties. The operational

348

conditions of the SIX process at WTP Andijk were as follows: contact time of approximately

349

25–30 min and resin loading of 13–15 mL. In operation, the SIX process was reported to be

350

feasible for NOM removal, providing high-quality effluent.

351 352 353

4.5 Nanomaterials for NOM removal Recently, novel “NanoResin” was suggested for efficient NOM removal from water (Johnson

354

et al., 2016). It was synthesized by functionalizing the surface of single-walled carbon

355

nanotubes with a strong base resin and was reported to have an open resin matrix with 0%

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Recently, a new anion exchange process called SIX® (Suspended Ion eXchange) was

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ACCEPTED MANUSCRIPT cross-linking. Thus, all ion exchange sites are located on the surface of the material,

357

increasing the percentage of active site utilization. The efficiency of “NanoResin” was tested

358

using various water surrogates and compared with that of other resins such as MIEX and

359

DOWEX 21K. For instance, fast filtration through “NanoResin” (0.16 mg), eliminated 8.31

360

·10-3 mg-C of a low MW sodium fluorescein solution (NaFL), whereas MIEX (0.35 mg)

361

removed 0.14 ·10-3 mg-C of NaFL. Moreover, low-MW NOM elimination using “NanoResin”

362

was achieved after only 10 s of exposure (Johnson et al., 2016).

363 364 365

4.6 Combination of ion exchange with other treatment processes

366

(Allpike et al., 2005; Fearing et al., 2004; Singer and Bilyk, 2002), lime softening (Hsu and

367

Singer, 2009), activated carbon (Drikas et al., 2009; Humbert et al., 2008) and filtration

368

(Fabris et al., 2007; Huang et al., 2012) has been studied. For instance, the effect of MIEX

369

resin pretreatment on ozone demand, ozone exposure for disinfection and bromate formation

370

was studied for three water samples collected from raw water supplies impacted by the San

371

Francisco Bay Delta (Kingsbury and Singer, 2013). It was found that, after treatment with

372

MIEX resin, 41-68% of total organic carbon (TOC) was removed from the raw water

373

whereas 12–44% was eliminated with alum treatment. The reduction of the bromide

374

concentration in the water using MIEX resin was estimated to be 20–50%. The ozone

375

demand was significantly decreased after MIEX and alum pretreatment. Chlorination of raw

376

water and water samples after MIEX, alum and ozonation treatment was conducted to

377

estimate the trihalomethane formation potential (THMFP). The results demonstrate that the

378

efficiency of MIEX resin was better than that of alum and ozonation, with THMFP removal

379

of 39–85%, 16–56% and 35–45%, respectively (Kingsbury and Singer, 2013). Based on these

380

results, it was concluded that the pretreatment with MIEX resin prior to ozonation is more

381

efficient than coagulation for bromide-rich water (Kingsbury and Singer, 2013).

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Combination of the MIEX process with other water treatment techniques such as coagulation

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ACCEPTED MANUSCRIPT An attempt to simultaneously remove the dissolved organic carbon and hardness from water

383

was made by Apell and Boyer (2010). MIEX resin was used with cation ion exchange resin

384

in a single completely mixed reactor, and the removal of DOC and hardness was estimated to

385

be 70% and > 55%, respectively. Thus, the feasibility of combined ion exchange water

386

treatment was demonstrated and recommended as a possible pretreatment technique, allowing

387

for a reduction in membrane fouling during the subsequent filtration step. In a recent study on

388

a combined ion exchange process (MIEX resin and cation exchange resin in a single

389

completely mixed vessel), the DOC and hardness removal from groundwater was reported to

390

be 76% and 97%, respectively (Comstock and Boyer, 2014). Successful regeneration of

391

exhausted anion and cation exchange resins was obtained using NaCl in a single vessel.

5. Bromide removal

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Bromide removal from surface waters is important because it allows for possible reduction in

395

brominated DBPs formation during disinfection (Hua and Reckhow, 2012). The capability of

396

bromide removal using MIEX® resin was demonstrated and the bromide removal was higher

397

in water with low alkalinity (Singer and Bilyk, 2002). It was suggested that, in high-alkalinity

398

water (high concentration of carbonate and bicarbonate ions), competition for exchange sites

399

between bromide and other ions is much higher than that in water with low alkalinity

400

(Johnson and Singer, 2004). Another study using MIEX® resin was conducted for bromide

401

removal from four drinking water (California) with low to moderate bromide levels (76–540

402

µg L-1), low to moderate TOC, low turbidity and various alkalinities (Boyer and Singer,

403

2005). It was confirmed that bromide elimination using MIEX® was more efficient when the

404

alkalinity and bromide concentration were relatively low. Meaningful removal of bromide

405

(initial concentration 150 µg L-1) was obtained with MIEX® (83%) and IRA938® (87%) resins

406

after 3 minutes of contact (Humbert et al., 2005b). A similar level of removal efficiency was

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ACCEPTED MANUSCRIPT demonstrated using MSA® and DOWEX11®, but the contact time was higher (Humbert, et al.,

408

2005b). Notably, the raw water tested was of low alkalinity and low sulfate concentration

409

(Humbert et al., 2005b). The efficiency of MIEX® for bromide and NOM removal from

410

model solutions containing bicarbonate and chloride was compared using two resins, A-641

411

and IRA910 (Hsu and Singer, 2010). With both resins, the removal of bromide was lower

412

when MIEX® was applied. The presence of chloride, bicarbonate and NOM in water

413

decreased the bromide elimination efficiency due to competition for active sites. Even when

414

two-stage MIEX treatment was applied, only a slight increase in bromide removal was

415

observed, which was explained by competition with chloride ions. Despite the higher level of

416

bromide elimination, resins A-641 and IRA910 demonstrated lower NOM removal and thus

417

were not recommended for further application (Hsu and Singer, 2010). It was reported that

418

fresh MIEX-HCO3 has higher capacity for bromide removal from water with high TOC (17

419

mg L-1), high salt concentration (235 mg L-1 as Cl-) and hardness (198 mg L-1 as CaCO3) than

420

virgin MIEX-Cl (Walker and Boyer, 2011). The mean elimination efficiency of bromide

421

using MIEX-HCO3 was 34% (average initial concentration 780 µg L-1). Interestingly,

422

bromide and chloride release from MIEX-HCO3 was observed when the concentration of

423

sulfate in raw water increased.

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6. Regeneration and reuse of resins after NOM removal If ion exchange is considered a possible treatment method for NOM elimination from surface

427

water, resin regeneration and reuse after NOM removal should be considered. The majority

428

of studies devoted to NOM removal using IX focus on fresh resin tests and few works

429

consider resin regeneration. Moreover, to understand the true behaviour of resin regeneration,

430

tests should be performed (Rokicki and Boyer, 2011).

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ACCEPTED MANUSCRIPT Quaternary ammonium resins in chlorine form are well-studied ion exchangers for NOM

432

removal and regeneration of this resin type is usually performed using brine. Regeneration of

433

MIEX® resin was studied in column experiments using 1.84 equivalents of chloride per litre

434

of resin and compared with MIEX® resin regenerated using an equivalent amount of sulfate

435

(Verdickt et al., 2011). When chloride was applied, the first bed volumes of DOC and UV254

436

removal were approximately 50% and 80%, respectively. However, after 1,500 bed volumes,

437

the DOC and UV254 removal efficiency was 25% and 58%. Interestingly, when sulfate was

438

used, the overall NOM elimination efficiencies were very similar to those obtained with

439

chloride. Notably, in the case of sulfate regeneration, no unwanted removal of sulfate occurs

440

(Verdicktet al., 2011). In a recent study, it was demonstrated that fresh MIEX-HCO3 and

441

virgin MIEX-Cl were more efficient for NOM and inorganic ion elimination from water than

442

were these resins after regeneration (Rokicki and Boyer, 2011). Moreover, it was confirmed

443

that MIEX regeneration using sodium bicarbonate is as efficient as that using sodium

444

chloride (concentration of anions 10 times the equivalent capacity of MIEX) (Rokicki and

445

Boyer, 2011).

446

Strongly basic anion resin Lewatit VPOC 1017 applied in a large-scale SIX process at Andijk

447

was regenerated using significantly smaller amounts of chloride counter ions. The mean salt

448

amount needed for regeneration of resin with no reuse was 0.05–0.2 kg m3. The results

449

demonstrated that the DOC removal after regeneration was not significantly lower than that

450

of fresh resin (Koreman, 2016).

451

Recently, “NanoResin” deposited on a support membrane was successfully regenerated using

452

2.0 M NaCl solution (Johnson et al., 2016). Through 15 adsorption/regeneration cycles, the

453

adsorption capacity of “NanoResin” did not undergo significant changes (Johnson et al.,

454

2016).

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7. Brine storage, disposal and/or recycling issues As discussed in the previous subchapter, salt is widely applied in ion exchange resin

458

regeneration. Accordingly, wastewater formed during the ion exchange process is usually

459

identified as brine. Generally, brine contains high concentrations of regenerating solution and

460

ions removed from treated water, so disposal or reuse of brine is challenging for engineers.

461

Notably, issues regarding brine storage, disposal and recycling should be considered when

462

using ion exchange as a potable water treatment method. Depending on the amount of brine

463

produced, local regulations, and the type of anions and cations present in the brine, the waste

464

brine can be disposed of at a local wastewater treatment plant (IXOM Watercare). For

465

instance, the waste brine generated during the MIEX® process comprises approximately

466

0.025–0.045% of the volume of treated water (IXOM Watercare), which is a relatively low

467

volume and disposal can be considered. If this option is not available, the brine can be

468

recycled using nanofiltration and/or coagulation.

469

For instance, full reuse of brine after NOM removal using MIEX® resin was performed at 'the

470

Blankaart' water treatment works (Belgium) by flocculation with FeCl3 and posterior filter

471

pressing (Verdicktet al., 2011). Prior to brine filtrate reuse, NaOH and NaCl were added to

472

maintain the pH and the salt concentration. The efficiency of NOM elimination was not

473

affected by brine reuse, while undesirable sulfates and nitrates were removed, and alkalinity

474

decreased.

475 476

Conclusions

477

In the present paper, recent studies on NOM removal using ion exchange were reviewed. The

478

composition of raw water is one of the most important parameters that should be considered

479

when choosing an ion exchange resin and reactor design. The results of recent research,

480

including data on raw water quality, are summarized in Table 1.

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ACCEPTED MANUSCRIPT As demonstrated in different studies, ion exchange is highly efficient for elimination of

482

charged NOM species. The uncharged NOM species, which are normally not removed using

483

ion exchange, may constitute 10% to 40%. As the polar components of NOM can lead to

484

substantial formation of disinfection byproducts, ion exchange can be considered a very

485

beneficial method for prevention of DBP formation. NOM removal from surface water on an

486

industrial scale is a crucial parameter that significantly affects the quality of potable water. A

487

major challenge in surface water treatment is elimination of NOM at the beginning of the

488

treatment process. If NOM is successfully removed in the first steps of surface water

489

treatment, the efficiency of subsequent treatment processes and the quality of the drinking

490

water increase. Development of the MIEX® process enables the use of ion exchange resin in

491

a slurry mode prior to the coagulation step. Due to the presence of magnetic iron oxide

492

particles in the core of MIEX resin, the separation step was significantly simplified, allowing

493

for it to be utilized in a different reactor design. The high stability of this resin and the

494

possibility of use without pretreatment make MIEX resin an extremely promising option for

495

applications on industrial scales, so it is unsurprising that it is currently the most studied ion

496

exchanger for NOM removal from water. In 2001, the first potable water treatment plant

497

using the MIEX-DOC process opened in Australia. In this plant, the MIEX-DOC step was

498

introduced prior to conventional treatment and significant improvement of the water quality

499

was observed. Notably, the MIEX resin is efficient for NOM removal and prevention of

500

chlorinated and brominated DBP formation (Hsu and Singer, 2010). Another promising ion

501

exchange process, SIX®, suitable for application in the first steps of the water treatment train,

502

was recently developed. The main advantages of the SIX® process are the possibility of using

503

water containing suspended solids and any commercially available resin, with a relatively

504

short contact time. These advantages make the SIX® process very flexible and easily

505

adjustable for different surface water. As few studies on the SIX® process are currently

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ACCEPTED MANUSCRIPT available and this process already has an industrial application (WTP of Andijk), it can be

507

expected that more research will be conducted in this area.

508

Nanotechnology is currently a rapidly developing area and nanomaterials are found in a

509

variety of applications in different fields including water treatment. A recent study devoted to

510

synthesis and testing of “NanoResin” confirmed the enhanced efficiency and rapid kinetics of

511

this nanomaterial for NOM elimination (Johnson et al., 2016). It can be expected that further

512

studies will concentrate on the development and modification of novel materials for ion-

513

exchange removal of NOM from water. However, there are serious environmental risks

514

related to the use of nanomaterials for water treatment, which should be addressed in future

515

studies.

516

Despite the importance of regeneration and reuse of ion exchange resin after NOM removal,

517

few studies focus on this issue. It is expected that more research will be conducted on resin

518

regeneration and reuse, which will allow for evaluation of the feasibility and applicability of

519

novel resins for NOM elimination from potable water.

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References

523

Aliverti, N., Callegari, A., Capodaglio, A.G., Sauvignet, P., 2011. NOM Removal from

524

Freshwater Supplies by Advanced Separation Technology, in: Hlavinek, P., Winkler, I.,

525

Marsalek, J., Mahrikova, I. (Eds.), Advanced Water Supply and Wastewater Treatment: A

526

Road to Safer Society and Environment. Springer, pp. 49-61.

527

Allpike, B.P., Heitz, A., Joll, C.A., Kagi, R.I., Abbt-Braun, G., Frimmel, F.H., Brinkmann,

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T., Her, N., Amy, G., 2005. Size Exclusion Chromatography To Characterize DOC Removal

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in Drinking Water Treatment. Environ. Sci. Technol. 39, 2334-2342.

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Apell, J.N., Boyer, T.H., 2010. Combined ion exchange treatment for removal of dissolved

531

organic matter and hardness. Water Res. 44, 2419-2430.

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Ates, N., Incetan, F.B., 2013. Competition impact of sulfate on NOM removal by anion-

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exchange resins in high-sulfate and low-SUVA waters. Ind. Eng. Chem. Res. 52, 14261-

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Bolto, B., Dixon, D., Eldridge, R., King, S., Linge, K., 2002. Removal of natural organic

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Bolto, B., Dixon, D., Eldridge, R., 2004. Ion exchange for the removal of natural organic

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Boyer, T.H., Singer, P.C., 2006. A pilot-scale evaluation of magnetic ion exchange treatment

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for removal of natural organic material and inorganic anions. Water Res. 40, 2865-2876.

541

Boyer, T.H., Singer, P.C., 2005. Bench-scale testing of a magnetic ion exchange resin for

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removal of disinfection by-product precursors. Water Res. 39, 1265-1276.

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water treatment. Water Res. 21, 1045-1052.

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Comstock, S.E.H., Boyer, T.H., 2014. Combined magnetic ion exchange and cation exchange

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for removal of DOC and hardness. Chem. Eng. J. 241, 366-375.

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Cornelissen, E.R., Beerendonk, E.F., Nederlof, M.N., van der Hoek, J.P., Wessels, L.P.,

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2009. Fluidized ion exchange (FIX) to control NOM fouling in ultrafiltration. Desalination.

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236, 334-341.

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Cornelissen, E.R., Moreau, N., Siegers, W.G., Abrahamse, A.J., Rietveld, L.C., Grefte, A.,

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Dignum, M., Amy, G., Wessels, L.P., 2008. Selection of anionic exchange resins for removal

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of natural organic matter (NOM) fractions. Water Res. 42, 413-423.

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Drewes, J.E., Summers, R.S., 2003. Natural Organic Matter Removal During Riverbank

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Filtration: Current Knowledge and Research Needs, in Ray, C., Melin, G., Linsky, R.B.

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(Eds.), Riverbank Filtration: Improving Source-Water Quality. Springer, pp. 303-309.

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Drikas M., Morran J.Y. , Pelekani C. , Hepplewhite C. and Bursill D.B., 2002. Removal of

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natural organic matter - a fresh approach. Water Supply. 2, 71-79.

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Drikas, M., Dixon, M., Morran, J., 2011. Long term case study of MIEX pre-treatment in

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drinking water; understanding NOM removal. Water Res. 45, 1539-1548.

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Drikas, M., Dixon, M., Morran, J., 2009. Removal of MIB and geosmin using granular

561

activated carbon with and without MIEX pre-treatment. Water Res. 43, 5151-5159.

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Erik Koreman, G.G., 2016. NOM-removal at SWTP Andijk (Netherlands) with a New Anion

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Exchange Process, called SIX. , 50.1-50.13.

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fouling of low pressure micro-filtration (MF) membranes. J. Membr. Sci. 289, 231-240.

566

Fearing, D.A., Banks, J., Guyetand, S., Monfort Eroles, C., Jefferson, B., Wilson, D., Hillis,

567

P., Campbell, A.T., Parsons, S.A., 2004. Combination of ferric and MIEX® for the treatment

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of a humic rich water. Water Res. 38, 2551-2558.

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Fettig, J., 1999. Removal of humic substances by adsorption/ion exchange. Water Science

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and Technology. 40, 173-182.

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Helfferich, F., 1995. Ion Exchange. Dover Publications, Inc., USA.

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Harland C.E., 1994. Ion Exchange. Theory and Practice, second ed. The Royal Society of

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Chemistry, Bath.

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Hongve, D., Baann, J., Becher, G., Beckmann, O.-A., 1999. Experiences from operation and

575

regeneration of an anionic exchanger for natural organic matter (NOM) removal. Water

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Science and Technology. 40, 215-221.

577

Hsu S, Singer P. C., 2009. Application of anion exchange to control NOM interference on

578

lime softening. J. Am. Water Work Assoc. 101, 85-94.

579

Hsu, S., Singer, P.C., 2010. Removal of bromide and natural organic matter by anion

580

exchange. Water Res. 44, 2133-2140.

581

Hua, G., Reckhow, D.A., 2012. Evaluation of bromine substitution factors of DBPs during

582

chlorination and chloramination. Water Res. 46, 4208-4216.

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584

formation during chlorination and chloramination of NOM fractions from different sources.

585

Chemosphere. 130, 82-89.

586

Huang, H., Cho, H., Schwab, K.J., Jacangelo, J.G., 2012. Effects of magnetic ion exchange

587

pretreatment on low pressure membrane filtration of natural surface water. Water Res. 46,

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5483-5490.

589

Huang, H., Cho, H., Schwab, K., Jacangelo, J.G., 2011. Effects of feedwater pretreatment on

590

the removal of organic microconstituents by a low fouling reverse osmosis membrane.

591

Desalination. 281, 446-454.

592

Humbert, H., Gallard, H., Jacquemet, V., Croué, J., 2007. Combination of coagulation and

593

ion exchange for the reduction of UF fouling properties of a high DOC content surface water.

594

Water Res. 41, 3803-3811.

595

Humbert, H., Gallard, H., Suty, H., Croué, J., 2008. Natural organic matter (NOM) and

596

pesticides removal using a combination of ion exchange resin and powdered activated carbon

597

(PAC). Water Res. 42, 1635-1643.

598

Humbert, H., Gallard, H., Suty, H., Croué, J., 2005a. Performance of selected anion exchange

599

resins for the treatment of a high DOC content surface water. Water Res. 39, 1699-1708.

600

Humbert, H., Gallard, H., Suty, H., Croué, J., 2005b. Performance of selected anion exchange

601

resins for the treatment of a high DOC content surface water. Water Res. 39, 1699-1708.

602

IXOM Watercare, Waste Management. 2017.

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X., 2013a. Characterising biofilm development on granular activated carbon used for

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drinking water production. Water Res. 47, 1101-1110.

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Gibert, O., Lefèvre, B., Fernández, M., Bernat, X., Paraira, M., Pons, M., 2013b.

607

Fractionation and removal of dissolved organic carbon in a full-scale granular activated

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carbon filter used for drinking water production. Water Res. 47, 2821-2829.

609

Jiang, J., Zhang, Xi., Zhu, Xi., Li, Yu., 2017. Removal of Intermediate Aromatic Halogenated

610

DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs

611

in Chlorinated Drinking Water. Environ. Sci. Technol. 51(6), 3435–3444

612

Johnson, B.R., Eldred, T.B., Nguyen, A.T., Payne, W.M., Schmidt, E.E., Alansari, A.Y.,

613

Amburgey, J.E., Poler, J.C., 2016. High-Capacity and Rapid Removal of Refractory NOM

614

Using Nanoscale Anion Exchange Resin. ACS Applied Materials & Interfaces. 8, 18540-

615

18549.

616

Johnson, C.J., Singer, P.C., 2004. Impact of a magnetic ion exchange resin on ozone demand

617

and bromate formation during drinking water treatment. Water Res. 38, 3738-3750.

618

Kaewsuk, J., Seo, G.T., 2011. Verification of NOM removal in MIEX-NF system for

619

advanced water treatment. Separation and Purification Technology. 80, 11-19.

620

Kennedy, M.D., Kamanyi, J., Heijman, B.G.J., Amy, G., 2008. Colloidal organic matter

621

fouling of UF membranes: role of NOM composition & size. Desalination. 220, 200-213.

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Kim, H., Dempsey, B.A., 2013. Membrane fouling due to alginate, SMP, EfOM, humic acid,

623

and NOM. J. Membr. Sci. 428, 190-197.

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resins and consequent reduction of fouling in UF and MF. J. Membr. Sci. 364, 325-330.

626

Kingsbury, R.S., Singer, P.C., 2013. Effect of magnetic ion exchange and ozonation on

627

disinfection by-product formation. Water Res. 47, 1060-1072.

628

Kitis, M., İlker Harman, B., Yigit, N.O., Beyhan, M., Nguyen, H., Adams, B., 2007. The

629

removal of natural organic matter from selected Turkish source waters using magnetic ion

630

exchange resin (MIEX®). React Funct Polym. 67, 1495-1504.

631

Krasner, S.W., Weinberg, H.S., Richardson, S.D., Pastor, S.J., Chinn, R., Sclimenti, M.J.,

632

Onstad, G.D., Thruston, A.D., 2006. Occurrence of a new generation of disinfection

633

byproducts. Environ. Sci. Technol. 40, 7175-7185.

634

Lee, N., Amy, G., Croué, J., Buisson, H., 2004. Identification and understanding of fouling in

635

low-pressure membrane (MF/UF) filtration by natural organic matter (NOM). Water Res. 38,

636

4511-4523.

637

Leenheer, J.A., Croué, J., 2003. Characterizing Aquatic Dissolved Organic Matter.

638

Environmental Science & Technology. 37, 18A-26A.

639

Drikas, M., Chow, C.W.K., and Cook, D., 2003. The impact of recalcitrant organic character

640

on disinfection stability, trihalomethane formation and bacterial regrowth: An evaluation of

641

magnetic ion exchange resin (MIEX®) and alum coagulation. Journal of Water Supply:

642

Research and Technology - Aqua. 52, 475-487.

643

Matilainen, A., Gjessing, E.T., Lahtinen, T., Hed, L., Bhatnagar, A., Sillanpää, M., 2011. An

644

overview of the methods used in the characterisation of natural organic matter (NOM) in

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relation to drinking water treatment. Chemosphere. 83, 1431-1442.

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by advanced oxidation processes. Chemosphere. 80, 351-365.

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Matilainen, A., Vepsäläinen, M., Sillanpää, M., 2010. Natural organic matter removal by

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coagulation during drinking water treatment: A review. Adv. Colloid Interface Sci. 159, 189-

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Mergen, M.R.D., Jefferson, B., Parsons, S.A., Jarvis, P., 2008. Magnetic ion-exchange resin

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Minor, E.C., Swenson, M.M., Mattson, B.M., Oyler, A.R., 2014. Structural characterization

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of dissolved organic matter: a review of current techniques for isolation and analysis.

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Environmental Science: Processes & Impacts. 16, 2064-2079.

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Mopper, K., Stubbins, A., Ritchie, J.D., Bialk, H.M., Hatcher, P.G., 2007. Advanced

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techniques, mass spectrometry, and nuclear magnetic resonance spectroscopy. Chem. Rev.

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107, 419-442.

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Morran J.Y., Drikas M., Cook D. and Bursill D.B., 2004. Comparison of MIEX treatment and

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Nkambule, T.I., Krause, R.W., Mamba, B.B., Haarhoff, J., 2009. Removal of natural organic

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drinking water: Sample preparation and analytical approaches. Trends in Environmental

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Pan, Y., Wang, Y., Li, A., Xu, B., Xian, Q., Shuang, Ch., Shi, P., Zhou, Q., 2017. Detection,

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byproducts in drinking water. Water Research 112, 129-136

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Plewa, M.J., Wagner, E.D., Richardson, S.D., Thruston, A.D.Jr., Woo, Y-T., McKague A.B.,

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Sillanpää, M., Bhatnagar, A., 2015. Chapter 7 - NOM Removal by Adsorption. In: Sillanpää,

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Sillanpää, M., Metsämuuronen, S., Mänttäri, M., 2015. Chapter 5 - Membranes. In: Sillanpää,

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M. (Ed.). Natural Organic Matter in Water. Butterworth-Heinemann, pp. 113-157.

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Singer, P.C., Bilyk, K., 2002. Enhanced coagulation using a magnetic ion exchange resin.

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Water Res. 36, 4009-4022.

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molecular weight and microcystins. Desalination. 315, 149-155.

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Wang, X., Wang, J., Zhang, Y., Shi, Q., Zhang, H., Zhang, Y., Yang, M., 2016.

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Walker, K.M., Boyer, T.H., 2011. Long-term performance of bicarbonate-form anion

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exchange: Removal of dissolved organic matter and bromide from the St. Johns River, FL,

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Wangersky, P.J., 1993. Dissolved organic carbon methods: a critical review. Mar. Chem. 41,

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unknown

iodinated

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byproducts

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dioxide preoxidation followed by chlorination or chloramination of natural organic matter.

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Chemosphere. 91, 1477-1485.

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organic matter in water for optimizing water treatment and minimizing disinfection by-

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Zularisam, A.W., Ismail, A.F., Salim, M.R., Sakinah, M., Hiroaki, O., 2007. Fabrication,

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fouling and foulant analyses of asymmetric polysulfone (PSF) ultrafiltration membrane

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fouled with natural organic matter (NOM) source waters. J. Membr. Sci. 299, 97-113.

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Figure captions Figure 1. Schematic representation of main methods of NOM removal from water

Figure 3. Classification of natural organic matter

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Figure 2. Number of scientific publications per year containing keywords such as NOM, DOC and ion exchange in the title

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Figure 4. Schematic representation of magnetic ion exchange resin (MIEX®) process (Boyer and Singer, 2006)

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Table 1. Summary of studies on NOM removal by ion exchange performed in the last 10–15 years. Treatment

Water quality

Reaction conditions and NOM removal, %

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Concentrated water from Myrtle Beach, SC, After treatment with “NanoResin” (incubation time of 5 min): “NanoResin” (single was diluted to the following level: DOC=9.17 mg-C L-1 (20.4% of reduction); walled carbon nanotubes -1 UV254 = 0.1041 (79.3% of reduction); SUVA=4.35 L mg-1 m-1; functionalized with a DOC=11.52 mg-C L ; -1 -1 strong base anion UV254 = 0.396; SUVA=4.36 L mg m ; Tests with Myrtle Beach, SC, water were performed using “NanoResin” film exchange resin deposited onto a polypropylene support membrane. The film was located in the glass vial facing solution. After addition of abovementioned water samples were (Johnson, et al., 2016) incubated in tube reactor for 5 mins. Wanneroo raw water appeared to be similar to Data were obtained from a full-scale (110 ML/d) potable water treatment plant this of northern European swamp and lake operating in Perth Western Australia. MIEX® combined with waters, such as water from some lakes in After MIEX® treatment: coagulation Finland. MIEX-C

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DOC=5.70 mg L-1; color (at 400 nm) = 45; UV254 = 0.326 cm-1; SUVA = 5.7 mgC L-1; pH = 7.14; Mn (method A DOC) = 2405; Mn (method A UV254) = 4273; Mn (method B UV254) = 3407; Mw (method A DOC) = 5319; Mw (method A UV254) = 6371; Mw (method B UV254) = 5294.

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-1 -1 The following parameters of raw water are DOC =-1 2.46 mg L ; color (at 400 nm) = 29; UV254 = 0.175 cm ; SUVA = 7.1 mgC L ; pH = 7.46 available:

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(Allpike, et al., 2005)

After MIEX® treatment combined with coagulation: alum dose = 55 mg L-1; polyelectrolyte dose = 0.75 mg L-1; DOC = 1.59 mg L-1; color (at 400 nm) = 2; UV254 = 0.025 cm-1; SUVA = 1.6 mgC L-1 ; pH = 6.61.

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Combined IE treatment Cedar Key groundwater characteristics: (MIEX-Cl and MIEX-Na DOC = 5.6 mg L-1; resins) UV254 = 0.171 cm-1; pH = 7.6; (Apell and Boyer 2010) alkalinity=244mgL -1 CaCO3; hardness = 275 mg L-1 CaCO3;

A Phipps &Bird PB 700 jar tester with 2 L square jars was used for the experiments. Simultaneous performance of anion and cation exchange resins, sequential anion exchange followed by cation exchange (sequence 1) and sequential cation exchange followed by anion exchange (sequence 2) were conducted.

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Water quality after combined IE treatment: DOC = 1.7 mg L-1; pH = 7.7; Cl- = 48.8 mg L-1; SO42- = 3.1 mg L-1;

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Cl- = 11.8 mg L-1; SO42- = 20.9 mg L-1; Ca2+ = 103 mg L-1; >90% of the hardness was as calcium;

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The following trends were observed for DOC and UV254 removal when fresh resins were used: sequence 1 ~ sequence 2 > simultaneous IE. After the third regeneration cycle no difference between simultaneous and sequential IE treatment was observed. NOM removal from Hope Valley water was 98-100%, whether gel or macroporous (MP) styrene or MP acrylic resins was used.

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20 different resins were Two types of waters were prepared using reverse osmosis in order to concentrate NOM tested in surface water samples from the East (Bolto et al. 2002) Moorabool River near Anakie, Victoria and from the Mount Zero reservoir at Horsham, Victoria. Also regeneration effluent obtained from MIEX® plant at Hope Valley, South Australia was used.

NOM removal efficiencies from Moorabool water (based on UV absorber removal):

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ResinTech SIR 22P – 85%; Amberlite IRA 458 – 90%; Fractionation and percentage of UVAmberlite IRA 958 – 90%; absorbing contribution for various NOM fractions were performed for tested water samples. Four fractions were distinguished: NOM removal efficiencies from Hope Valley water (based on UV absorber very hydrophobic acids (VHA), slightly removal): hydrophobic acids (SHA), charged hydrophilic acids and neutral hydrophilic ResinTech SIR 22P – 98%; compounds. UV-absorbance contribution for Amberlite IRA 958 – 99%; each fraction is presented below. Water from Hope Valley: VHA – 57%; SHA NOM removal efficiencies from Horsham water (based on UV absorber removal):

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– 17%; Charged – 26%; Neutral – 0%; Water from Moorabool: VHA – 40%; SHA – 17%; Charged – 38%; Neutral – 5%;

ResinTech SIR 22P – 84%; Amberlite IRA 958 – 73%;

Percentage of NOM removal, from DOC: MP 500 – 59%; S6328 – 73%; SP112 – not significant;

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Percentage of NOM removal, from UV 254 (m-1): MP 500 – 90%; S6328 – 93%; SP112 – not significant.

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Lewatit MP 500; Lewatit Water samples from Seine river (France) with S6328A; Lewatit SP112; the following characteristics were used: (Afcharian et al. 1997) DOC = 1.9 - 2.7 mg L-1; BDOC = 0.5 - 0.8 mgL-1; UV254 = 6.8 – 8.6 m-1; pH = 7.8 – 8.3; conductivity = 460 µs cm-1; ammonia ≤0.1 mgL-1; Purolite A860 (strongly Suwannee River NOM (TOC ~ 8.7 mg L-1; MW = 1050 g mol-1) and Pony Lake Fulvic basic resin) Acid (TOC ~ 8.7 mg L-1; MW = 750 g mol-1) (Bazri, et al., 2016) standard isolates were tested. Also Pony Lake Fulvic Acid standard amended with nitrate was studied (NO3 ~ 8.7 mg L-1).

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Normally dose of a resin equal to 3 g/L was used in all experiments and contact Water from Horsham: VHA – 70%; SHA – time was 16 h. 13%; Charged – 11%; Neutral – 5%;

Mean value of DOC removal over 6 consecutive cycles was 33 - 41%. The highest decrease of DOC concentration was observed after the first cycle for all tested samples. Interestingly elimination of DOC from River water was 20% higher than for water from Pony Lake after the 1st cycle. It was explained by higher charge density of River water.

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Results of this study confirmed that IE targeted hydrophobic humic (-like) compounds of NOM.

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Raw water from “Schie” canal (Delft, The Netherlands, Schie) filtered through 1µm filter and groundwater “Sint Jansklooster” (Sint Jansklooster, The Netherlands) after rapid sand filtration was used.

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Consecutive batch treatment of water was performed with water/resin ratio 10 mL L-1 and 30 mins of contact time.

When the dose of resin was increased from 2 to 10 ml L-1 removal of NOM from both water samples increased. A further increase of resin dose up to 12 ml L-1 did not affect significantly the NOM removal efficiency. Decrease of DOC and UV254 for Schie water after 1h with dose 10 ml L-1 was 69% and 86%, respectively. In the same conditions DOC and UV254 of Sint Jansklooster water decreased by 80% and 91%, respectively. Higher NOM removal from groundwater was attributed to a higher level of negatively charged organic compounds in this water. The tested resin was demonstrated to have preference towards aromatic compounds of NOM. Experiments were performed in batch mode with mixing speed of 300 rpm. Various doses of resin were tested.

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MIEX, DOWEX 11

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Raw water was taken at the Lever water At optimal resin dose of 15 mL L-1 and 10 mins of contact time the DOC removal treatment plant (Douro River) intake point exceeds 90%. Anionic compounds of DOC eliminated with MIEX was 60 – 92%. (eight samples). The characteristics of the Kinetic jar tests water were as follows:

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(Ates and Incetan, 2013)

Raw waters from Camlidere and Kesikkopru Optimal resin dose was found to be 10 mL L-1. Results obtained with MIEX resin source waters were tested (low-aromatic, are shown below: nonhumic low MW). Removal of DOC was 70% (20 min), and UV254 and sulfate were almost Characteristics of Camlidere water: DOC = completely eliminated at optimal resin dose in Camlidere water. Elimination of 5.4 mg L-1; UV254 = 0.091 cm-1; DOC, UV254 and sulfate at optimal resin dose in Kesikkopru water was 54% and SUVA254=1.68 L (mg of C)-1 m-1; pH = 8.0; about 45%, respectively. Sequence of removal and affinity in Camlidere water was Br- = 20 µg L-1; SO42- = 17 mg L-1; NO3- = 20 2mg L-1; Alkalinity = 84 mg of CaCO3 L-1; UV254≈ SO4 > DOC > bicarbonate, while in Kesikkopru water it changed DOC > Total hardness = 95 mg of CaCO3 L-1; UV254≈ sulfate > bicarbonate. During multiple-loading tests 52% and 31% of DOC Conductivity = 200 µS cm-1; Total dissolved was eliminated from Camlidere and Kesikkopru water, respectively. solids =100 mg L-1; Turbidity = 7 NTU; Results obtained with DOWEX 11 resin were as follows: Characteristics of Kesikkopru water: DOC = of DOC, UV254 and SO42- from Camlidere water was 60% (dose 300 4.8 mg L-1; UV254 = 0.034 cm-1; Elimination -1 -1 SUVA254=0.71 L (mg of C)-1 m-1; pH = 8.1; mg L ), ~85-90% (dose 1000 mg L ) 2-and >80%, respectively. For Kesikkopru Br- = 50 µg L-1; SO42- = 390 mg L-1; NO3- < water removal of DOC, UV254 and SO4 was 40%, 60% and ~60%, respectively. 0.06 mg L-1; Alkalinity = 115 mg of CaCO3 Sequence of removal and affinity in case of Kesikkopru water was UV254 > DOC > L-1; Total hardness = 350 mg of CaCO3 L-1; sulfate> bicarbonate. During multiple-loading tests about 75% and 46% of DOC Conductivity = 1637 µS cm-1; Total dissolved was removed from Camlidere and Kesikkopru waters before the breakthrough. solids =818 mg L-1; Turbidity = 8 NTU; The following experimental phases were performed: kinetic and batch tests, continuous-flow tests and sulfate spiking tests

MIEX® (Boyer and Singer 2006)

TOC = 4.44 – 8.84 mg L-1; DOC = 4.19 – 8.18 mg L-1; UV254 = 4.8 – 10.2 m-1; UV272 = 3.9 – 8.4 m-1; SUVA254 = 1.12 – 1.84 L m-1 mg-1; SUVA272 = 0.93 – 1.46 L m-1 mg-1. Raw water from Little River Reservoir was Variations in removal efficiency of DOC and UV254 were observed depending on used. The characteristics of the water (mean operational conditions. value calculated from May to December):

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Operational conditions: 20min HRT; 10% regeneration ratio; steady-state MIEX® concentration of 20 mL/L (ERD = 2mL/L); Removal efficiency: DOC = 74%; UV254 = 79%;

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Turbidity = 4.3 NTU; pH = 6.8; alkalinity (as CaCO3) = 24.1 mg L-1; hardness (as CaCO3) = 28.5 mg L-1; conductivity = 95 µs/cm; Cl- = 9.5 mg L-1; UV254 = 0.205 cm-1; DOC = 5.9 mg L-1; SUVA = 3.4 mg C L-1;

Operational conditions:

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Operational conditions:

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20min HRT; 2% regeneration ratio; ERD = 0.3 mL/L; MIEX® concentration in contactors = 15 mL/L Removal efficiency: DOC = 67%; UV254 = 65%; Operational conditions: 20min HRT; 2% regeneration ratio; ERD = 0.4 mL/L; MIEX® concentration in contactors = 20 mL/L Removal efficiency: DOC = 69%; UV254 = 72%; Operational conditions: 20min HRT; 5% regeneration ratio; ERD = 0.75 mL/L; MIEX® concentration in contactors = 15 mL/L Removal efficiency: DOC = 73%; UV254 = 72%; Experiments were conducted on continuous-flow pilot scale.

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(Boyer and Singer 2005)

Four types of drinking water in California Removal of DOC and UV 254 from NBA water: were used: North Bay Aqueduct (NBA), South Bay Aqueduct (SBA), Castaic Lake DOC = 70%; UV254 ~ 80%; (CL), and Sweetwater Lake (SL). SBA water: The characteristics of the water are shown DOC = 50%; UV254 ~ 60%; below: NBA water: pH = 7.5; Turbidity = 20 NTU; alkalinity (as CaCO3) = 149 mg L-1; Br= 76 µg L-1; UV 254 = 0.193 cm-1; TOC = 5.5 mg L-1; DOC = 5.1 mg L-1; SUVA = 3.8 mgC L-1; THM4FP =294 µg L-1; HAA9FP =224 µg CL water: L-1; SBA water: pH = 7.8; Turbidity = 6 NTU; alkalinity (as CaCO3) = 57 mg L-1; Br- DOC = 30%; UV254 ~ 50%; = 83 µg L-1; UV 254 = 0.064 cm-1; TOC = 1.9 mg L-1; DOC = 1.9 mg L-1; SUVA = 3.4 mgC SL water: L-1 ; THM4FP =111 µg L-1; HAA9FP=90.5 µg L-1; CL water: pH = 8.6; Turbidity = 7 DOC ~ 40%; UV254 ~ 50%;

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Raw water samples were obtained from New Removal of NOM was evaluated as DOC removal in percent. Data is shown Port, Richey, FL; Charleston, SC; Palmdale, below. (Budd et al. 2005; Fonseca CA; Northern KY; Southern NV. et al. 2005) New Port, Richey, FL: DOC = 65-77%; Raw water characteristics: Charleston, SC: DOC = 58-70% ; New Port, Richey, FL: DOC = 1.9 mg L-1; SUVA = 5.6 mgC L-1; sulphate = 18 mg L-1; Palmdale, CA: DOC = 52-60%; alkalinity (as CaCO3) = 200 mg L-1; Northern KY: DOC = 47-61%; Charleston, SC: DOC = 5.0 mg L-1; SUVA = 4.3 mgC L-1; sulphate = 15 mg L-1; alkalinity Southern NV: DOC = 23-44%; (as CaCO3) = 27 mg L-1; Palmdale, CA: DOC = 4.2 mg L-1; SUVA = 2.1 mgC L-1; sulphate Experiments were conducted on a continuous-flow pilot scale. = 29-41mgL-1; alkalinity (as CaCO3) = 126 mg L-1; Northern KY: DOC = 1.8 mg L-1; SUVA=4.6 mgC L-1; sulphate = 75 mg L-1; alkalinity (as CaCO3) = 113 mg L-1; Southern NV: DOC = 2.3 mg L-1; SUVA = 1.2 mgC L1 ; sulphate = 246 mg L-1; alkalinity (as CaCO3) = 288 mg L-1;

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NTU; alkalinity (as CaCO3) = 92 mg L-1; Br= 240 µg L-1; UV 254 = 0.074 cm-1; TOC = 2.3 mg L-1; DOC = 2.5 mg L-1; SUVA = 3.0 mgC L-1; THM4FP =150 µg L-1;HAA9FP =65.3µg L-1; SL water: pH = 8.1; Turbidity = 6 NTU; alkalinity (as CaCO3) = 188 mg L-1; Br- = 540 µg L-1; UV 254 = 0.102 cm-1; TOC = 5.2 mg L-1; DOC = 5.1 mg L-1; SUVA = 2.0 mgC L-1; THM4FP =283 µg L-1; HAA9FP =127 µg L-1;

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Combination of IE (MIEX Raw water samples from Hongze Lake, China The removal of UV254 increases (up to 85%) with increase of MIEX dose (max. 10 mL L-1). The optimal time and resin dose were 15 min and 8 mL L-1. When only resin) and chlorination were tested. MIEX was used about 80% of UV254 and 67% of DOC. During the first multiple(Han, et al., 2010) Characteristics of the water: loading test 98% of bromide, 69% of nitrate and 94% of sulfate was eliminated. However, removal of anions drop fast to 19% of sulfate, 12% of nitrate and 14% of pH = 8.10; bromide. During multiple-loading jar tests, UV254 removal efficiency decreased UV254 = 0.11 cm-1; from 81% (after the first cycle) to 70% (after cycle 10), while removal efficiency Turbidity = 46.71 NTU; of DOC decreased from 67% (after the first cycle) to 51% (after 10 cycles). SUVA = 2.37 L mg-1 m-1; Suggested bed volume of MIEX loading was 1250. It was reported that MIEX -1 Conductivity = 48 mS m ; eliminates 57% of chlorine demand and 77% of trihalomethane formation ρ(DOC) =4.68 mg L-1; potential. Chlorination of raw water was done prior to the MIEX process.

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Combined IE (MIEX-Cl Groundwater was used. The characteristics of The best performance was achieved at 200 BV, therefore DOC removal at 200BV only is shown below. DOC removal efficiency was obtained for fresh and and Amberlite 200C-Na) the water are shown below. regenerated resin, however the results were very close. Comstock and Boyer (in Cedar Key water (average): pH = 7.4; UV254 = 0.222 cm-1; DOC = 6.3 mg L-1; SUVA = 3.6 Cedar Key water: DOC ~ 84%; press) mgC L-1; total hardness (as CaCO3) = 315 mg L-1; calcium hardness (as CaCO3) = 250 mg Yankeetown water: DOC ~ 83%; L-1; alkalinity (as CaCO3) = 245 mg L-1; Palm Springs water: DOC ~ 95%. sulphate = 17 mg L-1; Yankeetown water: pH = 7.2; UV254 = 0.081 cm-1; DOC = 2.9 mg L-1; A Phipps &Bird PB 700 jar tester was used for experiments. Multiple loading was SUVA = 2.8 mgC L-1; total hardness (as conducted. Resin: 5mL MIEX-Cl/20mL A200C-Na; Regeneration with 2% NaCl CaCO3) = 440 mg L-1; calcium hardness (as and 20% NaCl. Five 1L water in series; 30 mins mixing at 200 rpm; 5 min settling. CaCO3) = 420 mg L-1; alkalinity (as CaCO3)

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(Humbert et al. 2008)

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Raw water from the Villejean/Rennes All tested resins removed more than 75 % of DOC (resin dose 8 mL/L) after drinking water treatment plant was used. The pseudo-equilibrium time (time varied from 15 min to more than 1h depending on resin). Less than 28% of DOC was removed by PAC (20-40 mg/L doses, pseudomain quality parameters are: equilibrium time of about 2h). pH = 7.0 – 7.9; Implementation of PAC treatment after resins led to a slight improvement in DOC Conductivity = 220-250 µS cm-1; -1 Alkalinity (mg L as CaCO3) = 20 – 30; removal and higher uptake of pesticides. NO3- = 7 – 29 mg L-1; Batch tests SO42- = 13 -29mg L-1; -1 DOC =5.6-6.7 mg L ; UV254 = 0.14 – 0.16 cm-1; SUVA = 2.2 – 2.9 mgC L-1;

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= 320 mg L-1; sulphate = 130 mg L-1; Palm Springs water: pH = 7.6; UV254 = 0.370 cm-1; DOC = 9.7 mg/L; SUVA = 3.8 mgC L1 ; total hardness (as CaCO3) = 300 mg L-1; calcium hardness (as CaCO3) = 295 mg L-1; alkalinity (as CaCO3) = 280 mg L-1; sulphate = 10 mg L-1;

DOC was successfully removed by all studied resins. MIEX® and IRA-938 demonstrated faster kinetics, already after 5 mins of contact time with dose of these resins of 8mL/L level of DOC was 1-2 mg L-1. The studied resins were able to remove high and partly low MW UV absorbing NOM. Bench-scale experiments

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MIEX®; DOWEX-11; Raw, clarified and post-ozonated water from DOWEX-MSA; IRA-938 the Villejean/Rennes drinking water treatment plant was used. (Humbert et al. 2005) Characteristics of clarified water: pH = 7.7; Alkalinity (mg L-1as CaCO3) = 29; NO3- = 8 mg L-1; SO42- = 22 mg L-1; DOC = 4.8 mg L1 ; UV254 = 0.1 cm-1; SUVA = 2.0 mgC L-1; Characteristics of post-ozonated water: pH = 7.1; Alkalinity (mg L-1as CaCO3) = 13; DOC = 2.15 mg L-1; UV254 = 0.021 cm-1; SUVA = 1.0 mgC L-1;

MIEX® – NF combined Influent of a water treatment plant Water treated with MIEX® was reported to have the following parameters: DOC = (Changwon city, Korea) was used. The 1.28 mg L-1, UVA = 0.010 cm-1, SUVA = 0.39 mgC L-1. Better performance was process attributed to NE90 after MIEX® treatment. characteristics of the water: (Kaewsuk and Seo 2011) The fluidized bed MIEX® column (150 mL of resin) was operated at a flow rate of Turbidity = 10 NTU;

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50 mL/min. Tests in fixed bed column demonstrated from 23 to 67% of the initial TOC removal, with removal increasing in the order DAX-8
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pH = 7.0; DOC = 2.5 mg L-1. DAX-8; IRA-958; DEAE Tertiary-treated wastewater effluent collected from an aeration tank discharge with TOC (pre-swollen); MIEX® ranging from 7 to 18 mg L-1was used. (Kim and Dempsey 2010; Kennedy et al. 2008)

Packed column, in-line addition and addition to complete-mix tank tests were conducted

and

In NBA water after treatment with 2.0 mL/L of MIEX/Cl, concentration of TOC decreased by 46% and UV absorbance by 58%. In SBA water treated with 2.0 mL/L of MIEX/Cl and MIEX/HCO3 TOC was decreased by 36 and 25% and UV absorbance by 44 and 42%, respectively. For Lake water MIEX/Cl and MIEX/HCO3 at the doses of 6.0 mL/L TOC reduced by 63 and 54%, respectively and UV absorbance by 80%.

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Raw waters from the North Bay Aqueduct, South Bay Aqueduct, spiked and non-spiked Singer water from Lake Campbell were tested. The water characteristics are shown below: North Bay Aqueduct (NBA): TOC = 3.7 mg L-1; DOC = 3.5 mg L-1; UV254 = 0.113 cm-1; SUVA = 3.2 mgC L-1; Fluorescence index = 1.39; pH = 7.9; Br- = 40 µg L-1; South Bay Aqueduct (SBA): TOC = 2.4 mg L-1; DOC = 2.4 mg L-1; UV254 = 0.071 cm-1; SUVA = 3.0 mgC L-1; Fluorescence index = 1.43; pH = 8.2; Br- = 360 µg L-1; Lake Campbell: TOC = 8.7 mg L-1; DOC = 8.5 mg L-1; UV254 = 0.256 cm-1; SUVA = 3.0 mgC L-1; Fluorescence index = 1.43; pH = 7.8; Br- = 33 µg L-1; Lake Campbell, spiked: TOC = 8.7 mg L-1; DOC = 8.5 mg L-1; UV254 = 0.256 cm-1; SUVA = 3.0 mgC L-1; Fluorescence index = 1.43; pH = 7.8; Br- = 380 µg L-1;

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It was demonstrated that for treatment of bromide-rich waters, MIEX® pretreatment prior to ozonation is more efficient than alum.

MIEX® (Kitis et al. 2007)

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Raw waters from five drinking water plants in Optimal dose and contact time for NOM removal from all waters was 10 mins and the city of Istanbul were tested. The physico- 10 mL settled resin/L. chemical characteristics are shown below. Multiple-loading jar tests were conducted. Elmali: DOC = 4.3 mg L-1; UV254 = 0.220 cm1 ; SUVA = 5.11 mgC L-1; Alkalinity = 30 mg CaCO3 L-1; Total Hardness = 110 mg CaCO3 L-1; TDS = 140 mg L-1; Conductivity = 279

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Three types of water were used: Barcombe, Removal of DOC in Draycote, Barcome and Albert waters was 56%, 33% and 25%, respectively. It was observed that both hydrophilic and hydrophobic NOM Draycote and Albert. can be removed by resin. However, high MW NOM quickly saturated or blocked Barcombe: DOC = 9.6 mg L-1; UV254 = 16.5 the resin. m-1; SUVA = 1.73 mgC L-1; pH = 7.7; Turbidity = 13.1 NTU; Conductivity = NA; Bench-scale tests Alkalinity = 112 mg CaCO3 L-1; Zeta potential = -12.7; Charge density = 1.9 meq g1 DOC; Draycote: DOC = 10.7 mg L-1; UV254 = 13.9 m-1; SUVA = 1.3 mgC L-1; pH = 8.1; Turbidity = 1.4 NTU; Conductivity = 692 µS m-1; Alkalinity = 157 mg CaCO3 L-1; Zeta potential = -10.8; Charge density = 0.3 meq g1 DOC; Albert: DOC = 9.4 mg L-1; UV254 = 60.1 m-1; SUVA = 6.4 mgC L-1; pH = 5.9;

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µS cm-1; pH = 7.62; Turbidity = 21.2 NTU; B.Cekmece: DOC = 3.1 mg L-1; UV254 = 0.084 cm-1; SUVA = 2.71 mgC L-1; Alkalinity = 35 mg CaCO3 L-1; Total Hardness = 150 mg CaCO3 L-1; TDS = 230 mg L-1; Conductivity = 460 µS cm-1; pH = 7.92; Turbidity = 1.4 NTU; Ömerli: DOC = 2.6 mg L-1; UV254 = 0.102 cm-1; SUVA = 3.92 mgC L-1; Alkalinity = 35 mg CaCO3 L-1; Total Hardness = 90 mg CaCO3 L-1; TDS = 113 mg L-1; Conductivity = 225 µS cm-1; pH = 7.52; Turbidity = 4.2 NTU; Ikitelli: DOC = 3.1 mg L-1; UV254 = 0.107 cm-1; SUVA = 3.45 mgC L-1; Alkalinity = 38 mg CaCO3 L-1; Total Hardness = 137 mg CaCO3 L-1; TDS = 170 mg L-1; Conductivity = 339 µS cm-1; pH = 8.05; Turbidity = 1.0 NTU; Kagithane: DOC = 2.8 mg L-1; UV254 = 0.108 cm-1; SUVA = 3.86 mgC L-1; Alkalinity = 37 mg CaCO3 L-1; Total Hardness = 123 mg CaCO3 L-1; TDS =221 mg L-1; Conductivity = 441 µS cm-1; pH = 7.63; Turbidity = 21.5 NTU;

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Turbidity = 1.8 NTU; Conductivity = 70 µS m-1; Alkalinity <10 mg CaCO3 L-1; Zeta potential = -12.4; Charge density = 6.4 meq g1 DOC Enhanced coagulation was reported to be more efficient than coagulation only. Thus, THM and HAA formation potential was reduced by more than 60% in all Manchester Water Works (TOC >2-4 mg L-1 studied waters. TOC and UV absorbance of MIEX® pretreated waters were and alkalinity 0-60 mg L-1 as CaCO3); subsequently lower than that of water treated by coagulation. Metropolitan Water District of Southern California (TOC>2-4 mg L-1 and alkalinity Batch MIEX® treatment, followed by alum coagulation. >60-120 mg L-1 as CaCO3); Davis Water Treatment Plant (TOC >2-4 mg L-1 and alkalinity >120 mg L-1 as CaCO3); Brown Water Treatment Plant (TOC >4-8 mg L-1and alkalinity 0-60 mg L-1 as CaCO3); Haworth Water Treatment Plant (TOC >4-8 mg L-1 and alkalinity >60-120 mg L-1 as CaCO3); White River Filtration Plant (TOC >4-8 mg L-1 and alkalinity >120 mg L-1 as CaCO3); Manatee Water Treatment Plant (TOC >8 mg L-1 and alkalinity 0-60 mg L-1 as CaCO3); Tampa Water Department (TOC >8 mg L-1and alkalinity >60-120 mg L-1 as CaCO3); Sioux Falls Water Purification Plant (TOC >8 mg L1 and alkalinity >120 mg L-1 as CaCO3)

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(Singer and Bilyk 2002)

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enhanced Nine surface waters were tested.

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MIEX® for coagulation

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Methods of NOM elimination from water

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1989 1991 1993 1995 1997 1999 2001 2003 2005 2007 2009 2011 2013 2015

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Application of ion exchange for NOM removal is reviewed From 30 to 90% of NOM can be removed from drinking water by ion exchange treatment Studies demonstrated that MIEX is one of the most promising resins for NOM removal