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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
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.
(Huang et al., 2011; Matilainen and Sillanpaa et al., TOC which indicate that DOC is the main fraction of
2010; Ahmad et al., 2002; Abbt-Braun and NOM. In addition, DOC present in natural water was
Frimmel,1999). mainly comprised of hydrophobic and hydrophilic
A number of studies have been conducted in order components whereas hydrophobic component
to find the best solution for controlling DBPs represents about 50% of DOC while hydrophilic
formation by reducing NOM amount in drinking ranging between 25-40%. The remaining fraction is
water sources (Xie et al., 2012; Toor and Mohseni, transphilic organic matter (Zularisam et al., 2006;
2007; Singer and Bilyk, 2002). Different approaches Parson et al., 2004).
were taken by researchers in developing methods at Moreover, hydrophobic and hydrophilic
different stages of drinking water treatment. This components can be further split into three different
paper aims to present information on NOM presence classes namely acid, bases, and neutral which have
in drinking water sources and its impact to drinking different chemical groups where hydrophobic classes
water in relation to DBPs formation as well as the is rich with aromatic carbon, phenolic structures and
possible methods of treatment. conjugated double bonds while hydrophilic classes
contains more aliphatic carbon and nitrogenous
2. NATURAL ORGANIC MATTER compounds (Kim and Yu, 2005; Duan and Gregory,
CHARACTERISTICS 2003; Nikolaou and Themistokles, 2001). Humic and
fulvic acids are examples of hydrophobic acid while
The main component of NOM was TOC which carboxylic and polyuronic acids are in hydrophilic
consists of dissolved organic carbon (DOC) and acids group (Bond et al., 2012; Matilainen, 2007).
particulate organic carbon (POC) fraction. Figure 1 shows the relationship between NOM
Nevertheless, POC only represents a small amount of 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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International Journal of Scientific Research in Environmental Sciences, 2(3), pp. 94-106, 2014
Typically, allochthonous NOM is the major flood, drought and human activities (Hudson et al.,
contributor to hydrophobic fraction while 2007; Abdullah et al., 2003). This indicated that,
authotochthonous is the main sources for hydrophilic NOM concentration and characteristics is dependent
fraction (Croue et al., 1999). However, NOM to water origin and its surrounding (Bond et al., 2012;
concentration and characteristics in natural water are Zularisan et al., 2006). Table 1 shows variation in
not necessarily the same. The concentration may vary hydrophobic and hydrophilic concentration in river
according to many factors such as topography, season, water at different places.
Ulu Pontian River, 2.38 2.6 1.7 mg/L Zularisam, et al., 2006.
Johor Malaysia
Luan or Yellow 1.35 1.00 1.43 mg/L Chen et al., 2008. Northern
River, Beijing China
Millstone River, 0.53 2.34 1.63 mg/L Marhaba, 2000. New Jersey
New Jersey
Basically, humic substances in NOM represent a intermolecular forces (e.g. electrostatic interaction,
range of complex organic matter in water and soil that hydrogen bonding, hydrophobic interaction and
originates from decayed animals and plants. Main multivalent cation formation) are expected to occur
component of humic substances are fulvic acid (water and form aggregates (Maurice and Namjesnik-
soluble at acidic to alkaline pH) and humic acid Dejanovic, 1999) of NOM with other pollutants.
(insoluble at acidic pH) (Maurice and Namjesnik- Meanwhile Wu et al. (2012) has suggested that
Dejanovic, 1999) known as hydrophobic acid. In molecular weight is one of the factor affecting
natural water, hydrophobic acid consists sorption behavior between NOM and metals.
approximately 90% of fulvic acids and 10% of humic Besides humic substances (hydrophobic), NOM
acids which is opposite to humic substances originate also consists non-humic substances (hydrophilic) that
from soil leaching that mostly consist of humic acids has low molecular mass (LMM). According to Croue
compared to fulvic acids (Uyak and Toroz, 2006; et al. (1999) hydrophilic fraction isolated from low
Nikolaou and Themistokles, 2001). Thus, water humic waters can be consider as a stronger precursor
sources that received more land based carbon has to THM and HAAs formation compared to
greater amount of humic substances. hydrophobic NOM. This fraction has a lower C/O
Beside its hydrophobicity, NOM was also ratio and specific UV absorbance (SUVA) value
characterized in accordance to its molecular mass/ which indicated that less aromatic carbon present
weight distribution. Humic acids in water have high (Croue et al., 1999). Treatment option such as
molecular mass (HMM) greater than 2000 Daltons. coagulation, and oxidation process are not effective
The suggestion was in agreement with data obtained for removing this type of fraction (Siva et al., 2011;
by Matilainen et al. (2005) where NOM molecular Bond et al., 2012; Matilainen et al., 2010). The best
mass recorded for humic substances reach up to removal mechanism for this fraction is expected to be
10,000 or larger. Similar results were also obtained. an adsorption. Thus, adsorption process such as
High molecular mass indicated that the water sources magnetic ion exchange resin (MIEX) is a better
mostly consist of aromatic carbon UV-absorbing treatment option (Bond et al., 2012) for hydrophilic
element. fraction.
In freshwater, humic and fulvic acids are the major To date, Malaysia is still using a conventional
causes for colour changes as well as odour and taste. treatment method which consist of coagulation,
Additionally, humic substances in natural water at pH flocculation sedimentation, filtration and disinfection
higher than 4 can be regarded as anionic processes. However, these treatments are not very
polyelectrolytes that carry negative surface charge as effective in removing NOM in drinking water sources.
a result of carboxyl and phenolic groups ionization The presence of NOM in water sources may disrupt
(Matilainen et al., 2010; Duan and Gregory 2003). coagulation process by competing for adsorption site
This characteristic allowed NOM to bind particles with other pollutant. Consequently, higher dosage of
with an opposite charges like heavy metals (Wu et al., coagulant required for the treatment process. High
2012) and escalate the rate of transportation and coagulant dosage may pose a risk to the consumer
distribution of pollutants in water sources. Different such as Alzheimers disease as a consequence of Al
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Trends on Natural Organic Matter in Drinking Water Sources and its Treatment
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International Journal of Scientific Research in Environmental Sciences, 2(3), pp. 94-106, 2014
Further development allowed fluorescence Nikolaou and Themistokles, 2001). Increasing in these
technology to advance whereas the rapid detection (<1 factors will increase the formation of DBPs during the
min) of three dimensional excitation emission treatment. In contrast, effect of pH is more
matrices (EEMs) is possible. EEM is a composite of complicated as certain DBPs formation increases at
emission scans from single sample recorded at higher pH (e.g. THMs) while other species may
incrementing excitation wavelengths and arranged in a increase at lower pH (e.g. 3-oxopentanedionic) (Bond
grid (excitation x emission x intensity) which et al., 2012).
providing a large amount of data that statically The use of alternative disinfectant such as ozone,
analyzed (Handerson et al., 2009) and give better chlorine dioxide and chloramine disinfectants was
understanding on NOM characteristics. able to reduce major DBPs formed by chlorine.
Unfortunately these disinfectants also formed its
3. FORMATION OF DISINFECTANT BY specific DBPs and occurred at higher level (Lu et al.,
PRODUCTS (DBPs) 2009; Krasner et al., 2006). According to Krasner et
al. (2006) about 600 new DBPs form from a reaction
Chlorination process is the main disinfection process of NOM with disinfectants such as chlorine,
use in water treatment because of its efficiency in chloramine, ozone, and chloride which found in
killing pathogenic organisms and cost effective. drinking water by the year 2006 and 70% of
However NOM in water react with chlorine to form halogenated DBPs reported are unidentified.
disinfectant by products (DBPs) that have reported as Meanwhile Bond et al. (2012) and Richardson et al.
hazardous materials to animals and humans (Bond et (2007) reported that the new products produce from
al., 2012; Payankapo et al., 2008). mono-chloramination such as N-
In water, NOM functional groups and structure Nitrosodimethylamine (NDMA), haloacetonitriles and
play an important role in DBPs formation. As an halonitromethanes known to have high cytotoxicity
example, hydrophobic fraction is more reactive with and genotoxicity. Table 3 shows the possible DBPs
chlorine while hydrophilic fraction is reactive to formed during disinfection process and permissible
bromine and iodine in water to form DBPs. limit in drinking water.
Nevertheless, Lu et al., (2009) reported that aromatic
carbon content in NOM was the main surrogate to 4. TREATMENTS
DBPs formation in chlorination process regardless of
its hydrophobicity nature. Therefore hydrophobic acid To date, there are several treatment methods that have
recorded the highest DBPs formation during the been proposed or applied for NOM removal such as
treatment (Matilainen et al., 2010). There are two enhanced coagulation, membrane filtration, adsorption
main DBPs species detected during the interaction of and ion exchange process and advanced oxidation
NOM and chlorine which are THMs and HAAs (Duan process. These methods of treatment have been
et al., 2009; Richardson et al., 2007). developed and enhanced in order to reduce NOM
Generally the formation of DBPs is dependent on concentration in drinking water sources and minimize
several factors during the treatment such as DBPs formation. The merits and demerits as well as
disinfectant concentration, contact time, pH, limitation of each treatments will be discuss here.
temperature and NOM properties and concentration
(Lu et al., 2009; Yee et al., 2009; Hong et al., 2007;
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Ibrahim and Aziz
Trends on Natural Organic Matter in Drinking Water Sources and its Treatment
The efficiency of this treatment is depending on characteristic that has high water content and open
the specific type and concentration of pollutant itself structure make it able to adsorb any charge materials
where more intensive treatment is needed when higher more efficiently (Matilainen, 2007). In recent years,
concentration of pollutant is present and combination magnetic ion exchange resin (MIEX) was developed
of treatment may require to achieve optimal removal for reversible removal of negatively charge organic
(Matilainen and Sillanpaa, 2010). In order to obtain ion which mainly focuses on DOC removal with the
greater efficacy, AOPs can be enhanced through aim to reduce DBPs formation in drinking water.
various combination of AOPs to increase the rate of MIEX is a strong base anion with ammonia
reactive species formation (e.g. UV/H2O2, UV/ozone, functional group and a macroporous polyacrylic
UV/ TiO2/H2O2 and UV/ Fentons reagent) matrix in chloride form (Boyer and Singer, 2006).
(Comninellis et al., 2008). AOPs has great potential This treatment utilized a strong base-anion exchange
in reducing DBPs formation by: 1) reducing TOC in resin by incorporating magnetic iron oxide particles
drinking water sources through complete oxidation or into the resin matrix and applied to raw water in
mineralization of NOM to CO2 and 2) altering continuous-flow reactors (Drikas et al., 2011).
physical or chemical characteristics of NOM by David et al. (2004) show that the use of MIEX
partially oxidizes and reducing its molecular weight to was able to increase the removal of DOC level in raw
reduce its reactivity with disinfectant (Matilainen and water whilst reducing coagulant dosage during
Sillanpaa, 2010; Toor and Mohseni, 2007). coagulation process. Similar result was observed by
Instead of the whole NOM structure, AOPs Drikas et al. (2011) where large amount of DOC was
treatment mainly mineralized aromatic structure of removed during MIEX pre-treatment prior to
NOM which is part of hydrophobic fraction (Siva et coagulation process. Thus, the amount of coagulant
al., 2011). This indicated that AOPs reduce more of required during coagulation process also decrease.
high molecular mass structure. Meanwhile, during Drikas et al. (2011) also mentioned that MIEX
oxidation/ mineralization process, hydrophobic treatment is not dependent on the DOC concentration
structure was altered and molar mass of the fraction in raw water since a consistent removal was obtained
was decrease. Consequently, hydrophilic fraction was during 2 year of study regardless of DOC
increased compared to its concentration in raw water. concentration.
Nevertheless, the efficiency of this treatment was Besides that, Boyer and Singer (2006) were
affected by the presence of carbon and bicarbonate ion suggesting that MIEX resin has greater preference for
in raw water. Besides NOM components, hydroxyl hydrophobic fraction. However the performance of
radical is also reacts with this ions and decrease the MIEX resin was decreased with elevation of sulfate
number of radicals for NOM oxidation which lead to concentration in raw water. Meanwhile, Bond et al.
low NOM removal (Lamsal et al., 2011). Hence (2012) have mention that the efficiency of resin in
oxidation process is not suitable for treating high removing high molecular mass fraction (hydrophobic)
alkalinity water. There are more researches (Rizzo et is declining after rapidly used. These is happening
al., 2013; Sarathy et al., 2011; Grebel et al., 2010) because of humic and fulvic acid in water cause the
conducted and discussed on the effectiveness of AOPs resin to clog by blocking adsorption sites and prevent
in removing NOM and DBPs in drinking water. continuous adsorption of organic fraction onto resin.
Figure 2 shows the example in the application of Instead, removal of hydrophilic fraction was more
UV/H2O2 and BAC study conducted at Trojan consistent with consecutive use of the resin. This data
Technologies pilot facilities confirm that ion exchange method is more prominent
for removing low molecular mass fractions compare
4.3. Magnetic Ion Exchange Resin Treatment to hydrophobic fraction. Another drawback for
(MIEX) MIEX treatment is carry-over of resin fines (Boyer
and Singer, 2006). Therefore another treatment for
Ion exchange is another alternative method in solid liquid separation is required following this
removing NOM in drinking water. Resin treatment (Boyer and Singer, 2006).
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Trends on Natural Organic Matter in Drinking Water Sources and its Treatment
4.4. River Bank/ Bed Filtration (RBF) system exchange, adsorption, and dilution. Other factors that
also contribute for the successful of this treatment are
Riverbank filtration (RBF) is a water treatment river water and groundwater quality, the porosity of
technology that consists of extracting water from the medium, water residence time in the aquifer,
rivers by pumping wells in the adjacent alluvial temperature and pH conditions of water, and oxygen
aquifers (Jaramillo, 2012). Basic scheme of riverbank concentrations.
filtration is shown in Figure 3 Typically aquifers A study conducted by Singh et al. (2010) at river
consist of deposits of sand, sand and gravel, large bank of Yamuna River, India show that RBF was able
cobbles and boulders. However, ideal condition to reduce approximately 50 % of NOM component.
usually includes of coarse-grained, permeable water This study was suggesting that organic compounds are
bearing deposits that are hydraulically connected with diluted, sorbed and degrade during RBF process. Even
riverbed materials. though RBF is capable of removing DOC, the
A reduction in the concentration of pollutants is concentration of this component is still high and
achieved by physical, chemical, and biological exceed the upper limit (< 2 mg/L) recommended by
processes that take place, between the surface water British Columbia Environmental Protection
and groundwater, and with the substrate (Jaramillo, Department.
2012). The main processes in riverbank filtration that Another related study was conducted by Lee et al.
involve in pollution level reduction consist of (2009) in Republic of Korea. This study has reported
dispersion, physical filtration, biodegradation, ion that RBF demonstrate stable chemical constituents for
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International Journal of Scientific Research in Environmental Sciences, 2(3), pp. 94-106, 2014
safely producing drinking water. In spite of that, the with suitable treatment may increase RBF
water produced from RBF is still possible to be performance.
directly polluted from anthropogenic sources such as
manures and fertilizer because of their shallowness. 4.5. Summary of treatment
This specifies that RBF system cannot stand alone to
produce good drinking water quality without Table 4 summarize the advantages and disadvantages
optimization of RBF scheme protection. However, of each treatment available for NOM removal in
some improvement, adjustment and/ or combination drinking water sources
Table 4: Methods of treatment used for NOM removal with positive and negative sides
Treatment Method Positive Negative References
Enhanced Coagulation Good in removing Required high coagulant Xie et al., 2012,
Hydrophobic fraction dosage and left Bond et al., 2012 and
transphilic(50 %) and Matilainen et al., 2005
hydrophilic(90 %) residual
in water
Advanced Oxidation Materialize/ Oxidize HMM Increase LMM components, Matilainen and Sillanpaa,
Process (AOPs) components of NOM to Not suitable for high 2010
LMM alkalinity water, Lamsal et al., 2011
Incomplete oxidation may
increase DBPs formation,
and
High cost
Anion Exchange Resin At neutral pH both anion Lower DOC removal for Croue et al., 1999
exchange and adsorption is high molecular mass
taking place accordingly (HMM) fraction
Magnetic ion Exchange Significantly remove all Clogging and reduce resin Bond et al., 2010
Resin Treatment (MIEX) NOM fraction. Hydrophilic efficiency to remove
fraction removal is more hydrophobic fraction after
consistent with consecutive rapidly used.
use of resin
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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.
106