International Journal of Scientific Research in Environmental Sciences, 2(3), pp. 94-106, 2014 Available online at http://www.ijsrpub.

com/ijsres ISSN: 2322-4983; 2014 IJSRPUB http://dx.doi.org/10.12983/ijsres-2014-p0094-0106

Review Paper Trends on Natural Organic Matter in Drinking Water Sources and its Treatment
Nurazim Ibrahim, Hamidi Abdul Aziz*
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia *Corresponding Author: Email: cehamidi@usm.my; Tel: 04-5996215; Fax: 04-5941009
Received 03 January 2013; Accepted 19 February 2014

Abstract. Natural organic matter (NOM) can be defined as a mixture of complex organic compounds that universally present in natural waters. High NOM content in water strongly impact the water quality and treatment in several ways (e.g. causing colour and odour, filter fouling and increase coagulant dose). Besides that, NOM also acts as the main precursor to disinfectant by products (DBPs) produce from the reaction of NOM and disinfectant during water treatment. DBPs are known to be carcinogenic to human and animals. The formation of DBPs is depending on NOM characteristics. Generally, NOM characteristics are differ according to the water sources. In order to understand NOM properties, NOM fractionation is required and therefore different approaches have been proposed for its characterization. Meanwhile several methods of treatment have been developed to remove or reduce the amount of NOM in drinking water sources to prevent DBPs formation. The aim of this paper is to review and discuss the properties and available treatment techniques for NOM. Keywords: Natural Organic Matter, Disinfectant By-products, Fractionation, Treatments

1. INTRODUCTION Generally, natural organic matter (NOM) is defined as a mixture of complex organic compounds that universally present in natural waters (Matilainen et al., 2010; Parson et al., 2004) as a result of organic matter decomposition and metabolic reaction (DECWMD, 2011). NOM presence in water can be quantified by total organic carbon (TOC) or dissolved organic carbon (DOC) and UV254 measurement. However, the chemical properties of NOM were obtained through fractionation process. Typically NOM characteristic is dependent on the biodegradable dissolved organic carbon (BDOC) content in water sources. NOM that originates from decayed of biota living in water bodies such as macrophites, algae and bacterias are known as autochthonous NOM (Nikolaou and Themistokles, 2001). Meanwhile, allocthonous NOM was referred to NOM from external sources that enter streams through natural cycle (e.g. soil leaching and snow melting) or human activities (e.g. Effluent from wastewater treatment plant) (Hwang et al., 2002; Croue et al., 1999). According to the past studies (Ahmad et al., 2002), NOM characteristic and properties are differed according to the origin of water sources. Hence different methods were proposed for removing or reducing NOM amount in drinking water sources. Besides NOM treatment, methods for DBPs removal

from drinking water was also developed (Wang et al., 2013c; Duan et al., 2012; Xie et al., 2012; Comninellis et al., 2008; Cai et al., 2007). The presence of NOM has a significant impact to the quality of drinking water sources (Matilainen et al., 2010). Therefore, the amount of NOM has been observed by US authorities to monitor its content in potable water sources. Primary concern of NOM presence in water sources is related to the formation of harmful disinfectant by products (DBPs) from disinfection process during drinking water treatment (Yee et al., 2009). The most common DBPs detected in drinking water are trihalomethanes (THMs) and haloacetic acids (HAAs) (Krasner et al., 2006). Furthermore, certain DBPs products such as Chloroform, Dichlorobromomethane and Trichloroacetic acid are potentially carcinogen to human (Nikolaou and Lekkas, 2001). Other disadvantages of NOM to drinking water sources and treatment process are, 1) acting as mobile carrier to inorganic and organic pollutants (increase the transportation and distribution) 2) causing yellow/ brown colour to water and cause taste and odour problems 3) compete with other pollutants for adsorption sites 4) serve as substrate to undesirable biological growth in the distribution system 5) control coagulant and disinfectant dosage which cause an increase of sludge volumes and DBPs formation 6) major compounds that cause membrane fouling

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(Huang et al., 2011; Matilainen and Sillanpaa et al., 2010; Ahmad et al., 2002; Abbt-Braun and Frimmel,1999). A number of studies have been conducted in order to find the best solution for controlling DBPs formation by reducing NOM amount in drinking water sources (Xie et al., 2012; Toor and Mohseni, 2007; Singer and Bilyk, 2002). Different approaches were taken by researchers in developing methods at different stages of drinking water treatment. This paper aims to present information on NOM presence in drinking water sources and its impact to drinking water in relation to DBPs formation as well as the possible methods of treatment. 2. NATURAL ORGANIC CHARACTERISTICS MATTER

The main component of NOM was TOC which consists of dissolved organic carbon (DOC) and particulate organic carbon (POC) fraction. Nevertheless, POC only represents a small amount of

TOC which indicate that DOC is the main fraction of NOM. In addition, DOC present in natural water was mainly comprised of hydrophobic and hydrophilic components whereas hydrophobic component represents about 50% of DOC while hydrophilic ranging between 25-40%. The remaining fraction is transphilic organic matter (Zularisam et al., 2006; Parson et al., 2004). Moreover, hydrophobic and hydrophilic components can be further split into three different classes namely acid, bases, and neutral which have different chemical groups where hydrophobic classes is rich with aromatic carbon, phenolic structures and conjugated double bonds while hydrophilic classes contains more aliphatic carbon and nitrogenous compounds (Kim and Yu, 2005; Duan and Gregory, 2003; Nikolaou and Themistokles, 2001). Humic and fulvic acids are examples of hydrophobic acid while carboxylic and polyuronic acids are in hydrophilic acids group (Bond et al., 2012; Matilainen, 2007). Figure 1 shows the relationship between NOM fraction and chemical groups of NOM.

Fig. 1: Relationship between NOM fraction and its chemical groups (Sources: Matilainen, 2010; Matilainen, 2007; Croue et al., 1999; Marhaba et al., 2000)

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Typically, allochthonous NOM is the major contributor to hydrophobic fraction while authotochthonous is the main sources for hydrophilic fraction (Croue et al., 1999). However, NOM concentration and characteristics in natural water are not necessarily the same. The concentration may vary according to many factors such as topography, season,
Sources Ulu Pontian River, Johor Luan or Yellow River, Beijing Millstone River, New Jersey Harbin Water Treatment Plant Hydrophobic 2.38 1.35 0.53

flood, drought and human activities (Hudson et al., 2007; Abdullah et al., 2003). This indicated that, NOM concentration and characteristics is dependent to water origin and its surrounding (Bond et al., 2012; Zularisan et al., 2006). Table 1 shows variation in hydrophobic and hydrophilic concentration in river water at different places.
References/ Countries Zularisam, et al., 2006. Malaysia Chen et al., 2008. Northern China Marhaba, 2000. New Jersey

Table 1: NOM fraction concentration at different origin Hydrophilic Transphilic Unit 2.6 1.00 2.34 1.7 1.43 1.63 mg/L mg/L mg/L

43.8

15.6

40.6

Lu et al., 2009. Harbin, China

Basically, humic substances in NOM represent a range of complex organic matter in water and soil that originates from decayed animals and plants. Main component of humic substances are fulvic acid (water soluble at acidic to alkaline pH) and humic acid (insoluble at acidic pH) (Maurice and NamjesnikDejanovic, 1999) known as hydrophobic acid. In natural water, hydrophobic acid consists approximately 90% of fulvic acids and 10% of humic acids which is opposite to humic substances originate from soil leaching that mostly consist of humic acids compared to fulvic acids (Uyak and Toroz, 2006; Nikolaou and Themistokles, 2001). Thus, water sources that received more land based carbon has greater amount of humic substances. Beside its hydrophobicity, NOM was also characterized in accordance to its molecular mass/ weight distribution. Humic acids in water have high molecular mass (HMM) greater than 2000 Daltons. The suggestion was in agreement with data obtained by Matilainen et al. (2005) where NOM molecular mass recorded for humic substances reach up to 10,000 or larger. Similar results were also obtained. High molecular mass indicated that the water sources mostly consist of aromatic carbon UV-absorbing element. In freshwater, humic and fulvic acids are the major causes for colour changes as well as odour and taste. Additionally, humic substances in natural water at pH higher than 4 can be regarded as anionic polyelectrolytes that carry negative surface charge as a result of carboxyl and phenolic groups ionization (Matilainen et al., 2010; Duan and Gregory 2003). This characteristic allowed NOM to bind particles with an opposite charges like heavy metals (Wu et al., 2012) and escalate the rate of transportation and distribution of pollutants in water sources. Different

intermolecular forces (e.g. electrostatic interaction, hydrogen bonding, hydrophobic interaction and multivalent cation formation) are expected to occur and form aggregates (Maurice and NamjesnikDejanovic, 1999) of NOM with other pollutants. Meanwhile Wu et al. (2012) has suggested that molecular weight is one of the factor affecting sorption behavior between NOM and metals. Besides humic substances (hydrophobic), NOM also consists non-humic substances (hydrophilic) that has low molecular mass (LMM). According to Croue et al. (1999) hydrophilic fraction isolated from low humic waters can be consider as a stronger precursor to THM and HAAs formation compared to hydrophobic NOM. This fraction has a lower C/O ratio and specific UV absorbance (SUVA) value which indicated that less aromatic carbon present (Croue et al., 1999). Treatment option such as coagulation, and oxidation process are not effective for removing this type of fraction (Siva et al., 2011; Bond et al., 2012; Matilainen et al., 2010). The best removal mechanism for this fraction is expected to be an adsorption. Thus, adsorption process such as magnetic ion exchange resin (MIEX) is a better treatment option (Bond et al., 2012) for hydrophilic fraction. To date, Malaysia is still using a conventional treatment method which consist of coagulation, flocculation sedimentation, filtration and disinfection processes. However, these treatments are not very effective in removing NOM in drinking water sources. The presence of NOM in water sources may disrupt coagulation process by competing for adsorption site with other pollutant. Consequently, higher dosage of coagulant required for the treatment process. High coagulant dosage may pose a risk to the consumer such as Alzheimers disease as a consequence of Al

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residual in drinking water. However, low dosage of coagulant causes an incomplete removal of NOM in water. Residual of NOM will react with disinfectant during treatment process and formed new products namely disinfection by products (DBPs) that is harmful and carcinogenic. Hence, it is important to understand NOM characteristics before deciding the suitable method for NOM removal. 2.1. NOM Characterization Basic characteristics of NOM can be obtained by determine several parameters such as TOC, DOC, UV-absorbance and SUVA. However more detail characterization study required more sophisticated techniques and equipment. Characterization study based on bulk parameters (physical characterization) only offers quantitative information of NOM. Meanwhile spectroscopic methods (Fluorescence, UV-vis, FTIR, 1H NMR, 13C NMR, 15N NMR, 2-D NMR), and chromatographic methods (HP-SEC, FIFFF, Mass spectrometric methods, FTICR MS, GCMS) measured NOM hydrophobicity, molecular weight or elemental composition which provide further details on NOM quality in water in term of chemical characteristics. 2.1.1. Bulk Parameters Basically the amount of NOM in water can be determined by three parameters which are TOC/ DOC, UV254 and SUVA. TOC or DOC provides a total organic carbon concentration in the samples by measuring level of organic carbon amenable to CO2 oxidation after removing inorganic carbon (Volk et al., 2002). Meanwhile, UV254 is used to describe UV absorbance measured by spectrophotometer at 254 nm and reported in cm-1. SUVA (specific UV absorbance) value represent the overall concentration of NOM in water, according to TOC/DOC and UV254 results, SUVA value can be obtained by dividing the value of UV254 (cm-1) with TOC/DOC (mg/L) concentration and multiply with 100 cm/M (EPA, 2009) as shown in equation 1.

Moreover, SUVA values also can be used as indicator to describe hydrophobicity of NOM in water. SUVA values lesser than 3, indicate that the sample contains more hydrophilic and low molecular weight materials while SUVA values more than 4 indicated that water samples mostly consist of hydrophobic components with high molecular materials (Wang et al., 2013b). This method was ease to use but high concentration of nitrate in low DOC water may interfere with the measurement (Matilainen et al., 2011). 2.1.2. Fluorescence A fluorescence technique has been established in the last 50 years for investigating organic composition in water (Hudson et al., 2007). Since NOM consist of heterogeneous compounds, it is difficult to identify individual fluorescent compounds in water. Thus, the fluorophores are usually groups into human-like, fulvic- like and proteins-like (Hudson et al., 2007). Alternatively, fluorophores can be identified through individual chemical characteristics whereas fluorescence spectrophotometric is conducted on NOM to obtain three spectrums namely emission spectra, excitation spectra and synchronous spectra (Ahmad et al., 2002). Marhaba et al., (2000) had used fluorescent spectrophotometric scan to determine six different types of NOM fractions (hydrophobic acid, hydrophobic base, hydrophobic neutral, hydrophilic acid, hydrophilic base and hydrophilic neutral) in water treatment plant. The fractions were distinguished according to the difference in excitation and emission wavelength range. However, the emission wavelength that set these fractions spectrally apart from each other (Marhaba, 2000). Table 2 shows an emission wavelength obtained for NOM fraction derived from water intake (Raritan and Millstone River as well as Delaware and Raritan Canal) of Somerset water treatment plant.

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Table 2: Fluorescence wavelength of NOM fraction (Adopted from Marhaba, 2000)

Fraction Hydrophilic Acid Hydrophilic Base Hydrophilic Neutral Hydrophobic Acid Hydrophobic Base Hydrophobic Neutral Wavelength, (nm) 345-357 357-369 609-621 417-429 369-381 309-321

Further development allowed fluorescence technology to advance whereas the rapid detection (<1 min) of three dimensional excitation emission matrices (EEMs) is possible. EEM is a composite of emission scans from single sample recorded at incrementing excitation wavelengths and arranged in a grid (excitation x emission x intensity) which providing a large amount of data that statically analyzed (Handerson et al., 2009) and give better understanding on NOM characteristics. 3. FORMATION OF PRODUCTS (DBPs) DISINFECTANT BY

Chlorination process is the main disinfection process use in water treatment because of its efficiency in killing pathogenic organisms and cost effective. However NOM in water react with chlorine to form disinfectant by products (DBPs) that have reported as hazardous materials to animals and humans (Bond et al., 2012; Payankapo et al., 2008). In water, NOM functional groups and structure play an important role in DBPs formation. As an example, hydrophobic fraction is more reactive with chlorine while hydrophilic fraction is reactive to bromine and iodine in water to form DBPs. Nevertheless, Lu et al., (2009) reported that aromatic carbon content in NOM was the main surrogate to DBPs formation in chlorination process regardless of its hydrophobicity nature. Therefore hydrophobic acid recorded the highest DBPs formation during the treatment (Matilainen et al., 2010). There are two main DBPs species detected during the interaction of NOM and chlorine which are THMs and HAAs (Duan et al., 2009; Richardson et al., 2007). Generally the formation of DBPs is dependent on several factors during the treatment such as disinfectant concentration, contact time, pH, temperature and NOM properties and concentration (Lu et al., 2009; Yee et al., 2009; Hong et al., 2007;

Nikolaou and Themistokles, 2001). Increasing in these factors will increase the formation of DBPs during the treatment. In contrast, effect of pH is more complicated as certain DBPs formation increases at higher pH (e.g. THMs) while other species may increase at lower pH (e.g. 3-oxopentanedionic) (Bond et al., 2012). The use of alternative disinfectant such as ozone, chlorine dioxide and chloramine disinfectants was able to reduce major DBPs formed by chlorine. Unfortunately these disinfectants also formed its specific DBPs and occurred at higher level (Lu et al., 2009; Krasner et al., 2006). According to Krasner et al. (2006) about 600 new DBPs form from a reaction of NOM with disinfectants such as chlorine, chloramine, ozone, and chloride which found in drinking water by the year 2006 and 70% of halogenated DBPs reported are unidentified. Meanwhile Bond et al. (2012) and Richardson et al. (2007) reported that the new products produce from mono-chloramination such as NNitrosodimethylamine (NDMA), haloacetonitriles and halonitromethanes known to have high cytotoxicity and genotoxicity. Table 3 shows the possible DBPs formed during disinfection process and permissible limit in drinking water. 4. TREATMENTS To date, there are several treatment methods that have been proposed or applied for NOM removal such as enhanced coagulation, membrane filtration, adsorption and ion exchange process and advanced oxidation process. These methods of treatment have been developed and enhanced in order to reduce NOM concentration in drinking water sources and minimize DBPs formation. The merits and demerits as well as limitation of each treatments will be discuss here.

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Table 3: Possible DBPs formation during disinfection process

DBPs Species DBPs Drinking Water Standards (mg/L) a b USEPA Malaysia 0.08 0.2 0.08 0.06 0.08 0.1 0.08 0.1 0.06 0.05 0.06 0.1 0.09 c

Carcinogenicity

THMs (human carcinogen)

HAAs

Nitrosamines Haloacetonitriles (HANs) Haloacetamides Haloaldehydes

Haloketones Halonitromethanes (HNM)

Chloroform (CHCl3) Bromodichloromethanes (CHCl2Br) Dibromochloromethanes (CHClBr2) Bromoform (CHBr3) Dichloroacetic acid (DCAA) Trichloroacetic acid (TCAA) N-Nitrosodimethylamine (NDMA) N-nitrosodiethylamine (NDEA) Dichloroacetonitriles (DCAN) Trichloroacetonitrile (TCAN) Dichloroacetamide (DCAcAm) Dichloroacetaldehyde (DCA) Trichloroacetaldehyde (chloral hydrate) (TCA) 1,1,1-trichloropropanone (TCP) Trichloronitromethanes (chloropicrin) (TCNM)

B2 B2 C B2 B2 B2 NA NA C C NA NA NA NA NA

Note: aUSEPA. (2012); bMOH. (2000); cNikolaou and Themistokles (2001). Group A: Human carcinogen; Group B: Probable human carcinogen (B1: Limited evidence from epidemiological studies, B2: Sufficient evidence from animal studies); Group C: Possible human carcinogen;

4.1. Enhanced Coagulation Enhanced coagulation can be defined as methods that uses effective coagulant dosage to remove TOC or minimized DOC residual after coagulation in drinking water sources (Xie et al., 2012; Singer and Bilk, 2002; Volk et al., 2002). In the beginning of water treatment process, coagulation was employed with focus to reduce turbidity. However the reduction of turbidity is not reducing the amount of NOM in water. Hence, a suitable condition needs to be created to obtain optimum removal of NOM through coagulation process. Thus conventional coagulation process was enhanced by optimizing pH and coagulant dosage. Optimizing coagulant dosage is very important to avoid coagulant overdosing that lead to an increase in the amount of sludge and pH reduction. Meanwhile under-dosing usually leaves residual metal remained in treated water. During treatment process, TOC content plays an important role in determine coagulation dosage required. For water sources with SUVA value equal to 2 or less, TOC is not the factor that control coagulant dose. But, if SUVA value obtains is greater than 2, then coagulant dosage required is increase with TOC concentration. However, the efficiency of coagulation process is not only dependent to pH, coagulant type and dosage but other factors as well such as NOM characteristics and presence of divalent cations. According to Matilainen et al. (2005) and Yee et al. (2009), coagulation process usually more effective in removing larger molecular (1000 4000 g/mol) and more hydrophobic NOM which primarily consist of humic substances. Based on the study conducted by Matilainen et al. (2005), ferric chloride is more effective for removing NOM compared to aluminium

sulphate especially for high molecular mass materials (> 3000 g/mol) during coagulation process. Study conducted by Wang et al. (2013a) exhibit that coagulation process was able to significantly reduce the hydrophobic organic matter by destabilized the particles during coagulation. Meanwhile, Duan and Gregory, (2003), suggested that co-precipitation and charge neutralization are the two main mechanisms in coagulation process that remove humic acid. Removing of humic substances through enhanced coagulation may allowed the use of disinfectant to treat pathogenic bacteria in drinking water sources while reducing DBPs formation (Uyak and Toroz, 2006). Still, coagulation process is not effective in removing low molecular mass (< 500 g/mol) compounds with post coagulation residual reach up to 90% for low molecular mass and about 50% for intermediate molecular mass (Matilainen et al., 2005). 4.2. Advanced Oxidation Process (AOPs) Generally, AOPs is defined as aqueous phase oxidation methods based on the intermediacy of highly reactive species such as hydroxyl (-OH) radical in the mechanism to remove the target pollutants (Comninellis et al., 2008). In NOM and DBPs cases, OH radicals is utilize to oxidize NOM as DBPs precursor by eliminating hydrogen atoms or adding electrophiles to their double bonds (Toor and Mohseni, 2007). The reaction mechanism started with OH radicals received an electron from organic materials. Then the process proceeded as carbon centered radicals react rapidly with O2 to form peroxyl radicals. This radical will react among themselves which produced ketones, aldehydes and/ or CO2 (Lamsal et al., 2011).

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The efficiency of this treatment is depending on the specific type and concentration of pollutant itself where more intensive treatment is needed when higher concentration of pollutant is present and combination of treatment may require to achieve optimal removal (Matilainen and Sillanpaa, 2010). In order to obtain greater efficacy, AOPs can be enhanced through various combination of AOPs to increase the rate of reactive species formation (e.g. UV/H2O2, UV/ozone, UV/ TiO2/H2O2 and UV/ Fentons reagent) (Comninellis et al., 2008). AOPs has great potential in reducing DBPs formation by: 1) reducing TOC in drinking water sources through complete oxidation or mineralization of NOM to CO2 and 2) altering physical or chemical characteristics of NOM by partially oxidizes and reducing its molecular weight to reduce its reactivity with disinfectant (Matilainen and Sillanpaa, 2010; Toor and Mohseni, 2007). Instead of the whole NOM structure, AOPs treatment mainly mineralized aromatic structure of NOM which is part of hydrophobic fraction (Siva et al., 2011). This indicated that AOPs reduce more of high molecular mass structure. Meanwhile, during oxidation/ mineralization process, hydrophobic structure was altered and molar mass of the fraction was decrease. Consequently, hydrophilic fraction was increased compared to its concentration in raw water. Nevertheless, the efficiency of this treatment was affected by the presence of carbon and bicarbonate ion in raw water. Besides NOM components, hydroxyl radical is also reacts with this ions and decrease the number of radicals for NOM oxidation which lead to low NOM removal (Lamsal et al., 2011). Hence oxidation process is not suitable for treating high alkalinity water. There are more researches (Rizzo et al., 2013; Sarathy et al., 2011; Grebel et al., 2010) conducted and discussed on the effectiveness of AOPs in removing NOM and DBPs in drinking water. Figure 2 shows the example in the application of UV/H2O2 and BAC study conducted at Trojan Technologies pilot facilities 4.3. Magnetic Ion Exchange Resin Treatment (MIEX) Ion exchange is another alternative method in removing NOM in drinking water. Resin

characteristic that has high water content and open structure make it able to adsorb any charge materials more efficiently (Matilainen, 2007). In recent years, magnetic ion exchange resin (MIEX) was developed for reversible removal of negatively charge organic ion which mainly focuses on DOC removal with the aim to reduce DBPs formation in drinking water. MIEX is a strong base anion with ammonia functional group and a macroporous polyacrylic matrix in chloride form (Boyer and Singer, 2006). This treatment utilized a strong base-anion exchange resin by incorporating magnetic iron oxide particles into the resin matrix and applied to raw water in continuous-flow reactors (Drikas et al., 2011). David et al. (2004) show that the use of MIEX was able to increase the removal of DOC level in raw water whilst reducing coagulant dosage during coagulation process. Similar result was observed by Drikas et al. (2011) where large amount of DOC was removed during MIEX pre-treatment prior to coagulation process. Thus, the amount of coagulant required during coagulation process also decrease. Drikas et al. (2011) also mentioned that MIEX treatment is not dependent on the DOC concentration in raw water since a consistent removal was obtained during 2 year of study regardless of DOC concentration. Besides that, Boyer and Singer (2006) were suggesting that MIEX resin has greater preference for hydrophobic fraction. However the performance of MIEX resin was decreased with elevation of sulfate concentration in raw water. Meanwhile, Bond et al. (2012) have mention that the efficiency of resin in removing high molecular mass fraction (hydrophobic) is declining after rapidly used. These is happening because of humic and fulvic acid in water cause the resin to clog by blocking adsorption sites and prevent continuous adsorption of organic fraction onto resin. Instead, removal of hydrophilic fraction was more consistent with consecutive use of the resin. This data confirm that ion exchange method is more prominent for removing low molecular mass fractions compare to hydrophobic fraction. Another drawback for MIEX treatment is carry-over of resin fines (Boyer and Singer, 2006). Therefore another treatment for solid liquid separation is required following this treatment (Boyer and Singer, 2006).

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Fig. 2: Schematic set-up for combination of AOPs and BAC treatment

Fig. 3: River bank filtration system

4.4. River Bank/ Bed Filtration (RBF) system Riverbank filtration (RBF) is a water treatment technology that consists of extracting water from rivers by pumping wells in the adjacent alluvial aquifers (Jaramillo, 2012). Basic scheme of riverbank filtration is shown in Figure 3 Typically aquifers consist of deposits of sand, sand and gravel, large cobbles and boulders. However, ideal condition usually includes of coarse-grained, permeable water bearing deposits that are hydraulically connected with riverbed materials. A reduction in the concentration of pollutants is achieved by physical, chemical, and biological processes that take place, between the surface water and groundwater, and with the substrate (Jaramillo, 2012). The main processes in riverbank filtration that involve in pollution level reduction consist of dispersion, physical filtration, biodegradation, ion

exchange, adsorption, and dilution. Other factors that also contribute for the successful of this treatment are river water and groundwater quality, the porosity of the medium, water residence time in the aquifer, temperature and pH conditions of water, and oxygen concentrations. A study conducted by Singh et al. (2010) at river bank of Yamuna River, India show that RBF was able to reduce approximately 50 % of NOM component. This study was suggesting that organic compounds are diluted, sorbed and degrade during RBF process. Even though RBF is capable of removing DOC, the concentration of this component is still high and exceed the upper limit (< 2 mg/L) recommended by British Columbia Environmental Protection Department. Another related study was conducted by Lee et al. (2009) in Republic of Korea. This study has reported that RBF demonstrate stable chemical constituents for

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safely producing drinking water. In spite of that, the water produced from RBF is still possible to be directly polluted from anthropogenic sources such as manures and fertilizer because of their shallowness. This specifies that RBF system cannot stand alone to produce good drinking water quality without optimization of RBF scheme protection. However, some improvement, adjustment and/ or combination

with suitable performance.

treatment

may

increase

RBF

4.5. Summary of treatment Table 4 summarize the advantages and disadvantages of each treatment available for NOM removal in drinking water sources

Table 4: Methods of treatment used for NOM removal with positive and negative sides
Treatment Method Enhanced Coagulation Positive Good in removing Hydrophobic fraction Negative Required high coagulant dosage and left transphilic(50 %) and hydrophilic(90 %) residual in water Increase LMM components, Not suitable for high alkalinity water, Incomplete oxidation may increase DBPs formation, and High cost Lower DOC removal for high molecular mass (HMM) fraction Clogging and reduce resin efficiency to remove hydrophobic fraction after rapidly used. References Xie et al., 2012, Bond et al., 2012 and Matilainen et al., 2005

Advanced Oxidation Process (AOPs)

Materialize/ Oxidize HMM components of NOM to LMM

Matilainen and Sillanpaa, 2010 Lamsal et al., 2011

Anion Exchange Resin

Magnetic ion Exchange Resin Treatment (MIEX)

At neutral pH both anion exchange and adsorption is taking place accordingly Significantly remove all NOM fraction. Hydrophilic fraction removal is more consistent with consecutive use of resin Effective for treating neutral hydrophilic compounds Remove most of biodegradable materials BAC filter increase the biodegradability of pollutant to be remove

Croue et al., 1999

Bond et al., 2010

Nanofiltration

Fouling

Bond et al., 2012 Harisha et al., 2010

River Bank Filtration (RBF) AOPs and BAC filter

Left NOM residual in water especially hydrophilic fraction No significant reduction of NOM

Siva et al., 2011

5. CONCLUSION To date, water quality monitoring in Malaysia is still focusing on general parameters such as BOD5, pH, COD, turbidity, TDS and colour but less attention was given to NOM concentration in drinking water sources. NOM is complex mixture of organic compounds that can cause many problems in drinking water quality and the most concern is the formation of DBPs such as THMs and HAA from NOM fraction (humic and non-humic substances). Continuous exposure to DBPs in drinking water posing a serious threat to human health thereby, the authorities set the permissible limit of these materials to ensure the water is safe for drinking purposes. Hence, it is important to remove NOM from raw water more efficiently. According to the pass studies (Table 1), NOM characteristics are vary significantly from one sources to another sources of water. Thus, its characteristic

plays an important role in deciding the treatment option for raw water. Despite of all treatment available for NOM removal, none of the discussed treatments method is successful in removing all NOM fractions present in water sources. Hence, more study should be conducted to improve the efficiency of existing methods whilst exploring another possible alternative technology such as composite adsorbent media (e.g. zeolite-carbon) which consist of both hydrophilic and hydrophobic surface to exchange with an opposite ion charge of organic carbon in NOM. Acknowledgments The authors are grateful to Ministry of Higher Education Malaysia for providing LRGS Grant No. 203/PKT/6726001 River bank/bed Filtration for Drinking Water Source Abstraction and MyBrain15 Scholarship to fund this research.

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Ibrahim and Aziz Trends on Natural Organic Matter in Drinking Water Sources and its Treatment

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Nurazim Ibrahim is a postgraduate student at School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia.

Dr Aziz is a Professor in environmental engineering at the School of Civil Engineering, Universiti Sains Malaysia. Dr. Aziz received his Ph.D in civil engineering (environmental engineering) from University of Strathclyde, Scotland in 1992. He has published over 200 refereed articles in professional journals/proceedings and currently sits as the Editorial Board Member for 8 International journals. Dr Aziz's research has focused on alleviating problems associated with water pollution issues from industrial wastewater discharge and solid waste management via landfilling, especially on leachate pollution. He also interests in biodegradation and bioremediation of oil spills.

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