Chemosphere 190 (2018) 54e71

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

Removal of natural organic matter in drinking water treatment by

coagulation: A comprehensive review
€a
Mika Sillanpa € a, b, Mohamed Chaker Ncibi a, *, Anu Matilainen c, Mikko Vepsa
€la
€inen d
a
Laboratory of Green Chemistry, School of Engineering Science, Lappeenranta University of Technology, Sammonkatu 12, 50130, Mikkeli, Finland
b
Department of Civil and Environmental Engineering, Florida International University, Miami FL, 33174, USA
c
Finnish Safety and Chemicals Agency, Kalevantie 2, 33100 Tampere, Finland
d
CSIRO Mineral Resources Flagship, Box 312, Clayton South, VIC, 3169, Australia

h i g h l i g h t s

Recent R&D studies in the field of NOM removal by coagulation are overviewed.

Various metallic and polymeric coagulants are included.

Biocoagulants are promising alternatives to conventional metal-based coagulants.

Novel composites are enabling efficient NOM removal from drinking water supplies.

Coagulation-based integrated processes for improved efficiency and resilience.

a r t i c l e i n f o a b s t r a c t

Article history: Natural organic matter (NOM) is a complex matrix of organic substances produced in (or channeled to)
Received 4 July 2017 aquatic ecosystems via various biological, geological and hydrological cycles. Such variability is posing a
Received in revised form serious challenge to most water treatment technologies, especially the ones designed to treat drinking
19 September 2017
water supplies. Lately, in addition to the fluctuating composition of NOM, a substantial increase of its
Accepted 24 September 2017
Available online 25 September 2017
concentration in fresh waters, and also municipal wastewater effluents, has been reported worldwide,
which justifies the urgent need to develop highly efficient and versatile water treatment processes.
Handling Editor: Xiangru Zhang Coagulation is among the most applied processes for water and wastewater treatment. The application
of coagulation to remove NOM from drinking water supplies has received a great deal of attention from
Keywords: researchers around the world because it was efficient and helped avoiding the formation of disinfection
Coagulation by products (DBPs). Nonetheless, with the increased fluctuation of NOM in water (concentration and
NOM composition), the efficiency of conventional coagulation was substantially reduced, hence the need to
Drinking water develop enhanced coagulation processes by optimizing the operating conditions (mainly the amount
Removal efficiency
coagulants and pH), developing more efficient inorganic or organic coagulants, as well as coupling
Integrated processes
coagulation with other water treatment technologies. In the present review, recent research studies
dealing with the application of coagulation for NOM removal from drinking water supplies are presented
and compared. In addition, integration schemes combining coagulation and other water treatment
processes are presented, including membrane filtration, oxidation, adsorption and others processes.
© 2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2. Coagulation in NOM-containing waters: A mechanistic overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3. NOM removal from drinking water supplies by coagulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.1. Metallic coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

* Corresponding author.
E-mail address: chaker.necibi@lut.fi (M.C. Ncibi).

https://doi.org/10.1016/j.chemosphere.2017.09.113
0045-6535/© 2017 Elsevier Ltd. All rights reserved.
 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71 55

List of abbreviations HMM High molar mass

NOM Natural organic matter
AMW Apparent molecular weight PAC Polyaluminum chloride
BOD Biological oxygen demand PACA Polyacrylic acid-co-acrylamide
CLR Charge loading rate PAFS Polymeric aluminum ferric sulfate
COD Chemical oxygen demand PAM Polyacrylamide
DBPs Disinfection by-products PDADMAC Polydiallyldimethyl ammonium chloride
DOM Dissolved organic matter PFC Polyferric chloride
DSA Dimensionally stable anode PFAC Polyferric aluminum chloride
Epi/DMA Epichlorohydrin/dimethylamine PFS Polyferric sulfate
EPS Exopolysaccharides PFZS Polymeric ferric zinc sulfate
CPAM Cationic polyacrylamide; PPAC Polymeric phosphate aluminum chloride
FA Fulvic acid PTC Polytitanium chloride
HA Humic acid SUVA Specific ultraviolet absorbance
HS Humic substances THM Trihalomethanes
HAA Haloacetic acid THMFP Trihalomethanes formation potential
HAAFP Haloacetic acid formation potential TOC Total organic carbon
HAN Haloacetonitrile UF Ultrafiltration

3.1.1. Aluminum-based coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

3.1.2. Iron-based coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.1.3. Titanium and zirconium-based coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.2. Polymeric coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.1. Synthetic polymeric coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.2.2. Natural polymers: biocoagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3. Composite metalliceorganic polymeric coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.4. Electrocoagulation (EC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.5. Coagulation-based integrated processes: resilient and efficient water treatment processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.5.1. Integrated coagulationemembrane filtration process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.5.2. Integrated coagulationeadsorption process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.5.3. Integrated oxidationecoagulation process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.5.4. Integrated coagulationeion exchange process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4. Conclusions and outlook: coagulation for sustainable water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

1. Introduction factors tend to influence the occurrence and fate of NOM in aquatic
environments including water chemistry, pH, temperature and the
Natural organic matter (NOM) is complex matrix of organic various biological processes taking place in the water body.
substances commonly found in surface and ground waters, as a Therefore, the amount and composition of NOM could vary sub-
result of different hydrological, biological and geological interaction stantially from one location to another and also in the same water
schemes. In general, NOM can be generated within the water body after seasonal changes affecting natural phenomena such as
source through biological activities, mainly algal and microbial floods, droughts, and rainfalls (Matilainen et al., 2002; Sharp et al.,
(autochthonous NOM), or introduced to the water body via 2006a; Hirabayashi et al., 2008; Kundzewicz et al., 2014). The
drainage within watersheds including substances generated during combination of those climatic, hydrological, biological, geological
the breakdown of terrestrial organisms (allochthonous NOM). and chemical factors were reported to be the main reasons for (i)
Such differentiation is important because each of those two the frequent spatiotemporal variations of NOM in water sources
groups has specific characteristics which, once identified, are a and (ii) its increasing amounts recurrently monitored around the
useful tool to set suitable and efficient NOM removal processes. world during the past 10e20 years (Matilainen and Sillanpa €a
€, 2010;
Thus, it was reported that the “outsider” autochthonous NOM (dark Couture et al., 2012; Sillanpa €€
a, 2015).
colored) is mainly constituted of humic substances and its Inherently, NOM is not toxic, but its presence in water, especially
composition is highly variable depending on potential geological in drinking water sources is highly detrimental. Indeed, the pres-
and hydrological changes in the originating ecosystem and the ence of NOM tends to downgrade the quality of potential potable
watershed (Hudson et al., 2007). As for the “insider” autochthonous waters by altering their organoleptic properties (color, taste and
NOM (light colored), the biological activities are quite diverse odor). NOM also could act as a carrier of toxic organic and inorganic
depending on the metabolism of the involved algal and/or bacterial pollutants such as such as pesticides and radionuclides (Knauer
species. Such activities generally generate soluble extracellular and et al., 2017; Santschi et al., 2017). In this context, the presence of
intracellular macromolecules such as carbohydrates, amino acids, NOM in natural waters was reported to increase bioavailability of
peptides, enzymes and toxins (Her et al., 2004; Amy, 2008). hydrophobic anthropogenic compounds by increasing their solu-
Along with the impact of its biochemical composition, other bility in water (Reid et al., 2001). In addition, various components of
56 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71

NOM, mainly humic acids (HA) and fulvic acids (FA), tend to form
strong complexes with heavy metals, leading to the formation of
organometallic complexes with increased transportation ability,
bioavailability and toxicity (Matilainen et al., 2011; Tang et al.,
2014).
Equally important is the contribution of NOM to the formation
of disinfection by-products (DBPs) (Golea et al., 2017; Goslan et al.,
2017), which leads to the potential presence of carcinogenic com-
pounds in conventionally treated waters (involving chlorination),
including aliphatic halogenated trihalomethanes (THMs), halo-
acetic acids (HAAs), haloacetonitriles (HANs), haloketones and tri-
chloronitromethane (Bond et al., 2012; Serrano et al., 2015), along
with numerous aromatic halo-DBPs (Li et al., 2016; Jiang et al.,
2017). Recent studies have shown that these aromatic halo-DBPs
generally present significantly higher developmental toxicity and
growth inhibition than aliphatic halo-DBPs (Yang and Zhang, 2013; Fig. 1. Evolution of the published scientific papers dealing in with NOM removal by
Liu and Zhang, 2014). coagulation between 2001 and 2016 (ScienceDirect database search conduced on May
Thus, under such circumstances, the removal of NOM from 17th, 2017 using the keywords: coagulation, natural organic matter, humic and water).

drinking water supplies is becoming a challenging task requiring

the application of reliable and highly efficient water treatment
using various coagulants. As a result, colloidal microparticles start
technologies able to deal with the high spatiotemporal variability of
to develop and then agglomerate into larger particles or flocs (see
NOM and its increasing concentration in aquatic environments.
Fig. 2). This agglomeration phenomenon includes various mecha-
These two main issues, along with the complexity of NOM (Mao
nisms such as charge neutralization, entrapment, adsorption and
et al., 2017), are still compromising the efficiencies of various water
complexation with the coagulant's metal ions into insoluble ag-
treatment processes. In this regard, NOM is frequently identified as
gregates (Henderson et al., 2006). As far as NOM in concerned, and
one of the main fouling agents in membrane-based technologies,
considering the high variability of its organic components in term
causing pore narrowing and the formation of loose cake layer
of molecular and electrical properties, the combined removal
(Cheng et al., 2017). For processes based on the use of chemicals
mechanisms will substantially differ from one water source to the
(e.g. coagulation and oxidation) and materials (e.g. adsorption), the
other and within the same source due to seasonal variations. The
increasing concentrations of NOM requires using more chemicals
result will therefore be a variable removal efficiency of coagulation
or materials (Xu et al., 2016a), which ultimately leads to the gen-
and the formation of flocs with different sizes and structures (Jarvis
eration of more sludge or spent materials. For the adsorption pro-
et al., 2006; Sharp et al., 2006b), which constitutes a serious chal-
cess, NOM also tends to compete with the targeted micropollutants
lenge for the application of coagulation in the treatment of drinking
over the active sites thus lowering the removal efficiency of the
water supplies.
adsorption technique for a wide array of organic and inorganic
Coagulation has been conventionally applied in water treatment
pollutants (Qi and Schideman, 2008; Zietzschmann et al., 2014).
to decrease turbidity and color and remove suspended particles and
In the present review paper, recent research studies dealing
pathogens (Volk et al., 2000). In this context, a very important
with the removal of NOM from drinking water supplies via coag-
finding reported by many researchers has to be highlighted: the
ulation are overviewed. This is an updated and more elaborate
optimum operating conditions to remove turbidity or color by
version of the previous review paper published in Advances in
coagulation are not necessarily the same conditions for NOM
Colloid and Interface Science by our research group in 2010
removal (Yan et al., 2008). In practice, water treatment by coagu-
(Matilainen et al., 2010). Thus, new R&D findings in the field are
lation is carried out by the addition of a determined amount of
presented and discussed, based on the related scientific literature
coagulants (mostly inorganic coagulants such as aluminium or iron
published between 2010 and 2016. As well, a comparative assess-
salts), which, in the water solution, are dissociated into their
ment of the efficiencies of various coagulants and coagulation
trivalent ionic form (Al3þ and Fe3þ), hydrolyzed and end up forming
techniques to remove NOM from natural or artificially contami-
positivelyecharged complexes highly interactive with the
nated waters is carried out, along with the efficiencies of several
negatively-charged colloids (Duan and Gregory, 2003).
integrated processes coupling coagulation with other water treat-
According to the related literature, the two main operating
ment processes such as membrane separation, ion exchange,
conditions affecting the overall efficiency of any coagulation pro-
oxidation and adsorption.
cess are pH and coagulants’ type and dosage. In this regard, when
the reaction pH is higher than the minimum solubility of the
2. Coagulation in NOM-containing waters: A mechanistic
coagulant (5.8 and 6.3 for ferric chloride and aluminium chloride,
overview
respectively), the process generates high molar mass (HMM)
polymers or colloidal/precipitated species. In case the pH is lower
Numerous R&D studies on the application of coagulation for
than the minimum solubility of coagulant, then medium polymers
water and wastewater treatment applications were conducted
or monomers (Yan et al., 2008). Regarding the effect of coagulants
during the course of the last 20 years or so. Monitoring the scien-
dosage, determining the “right” amount is a prerequisite for an
tific publications in ScienceDirect database from 2001 to 2016 (Cf.
optimized efficiency. Thus, overdosing the coagulant results in a
Fig. 1) clearly reveals that the research investigations on this subject
substantial increase in the amount of generated sludge and a
are still gaining momentum around the world, especially during the
decrease in pH, while a lower dose is generally the cause for the
last seven years (covered in the present review), where the number
residual metals remaining in treated water (Ibrahim and Aziz,
of related papers more than doubled (139 articles in 2010 to 305 in
2014), hence the need for enhanced coagulation processes (Xiao
2016).
et al., 2013; Xie et al., 2012).
Basically, coagulation is a physical-chemical process aiming at
Along with these two operating parameters, the chemical and
reducing the repulsive potential of electrical double layer of colloids
 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71
Fig. 2. Schematic representation of a pilot-scale setup used for a coagulation-based water treatment system (Jarvis et al., 2012).
molecular characteristics of the targeted pollutants constitute the
major parameter to be taken into consideration before the appli-
cation of coagulation-based water treatment process, because they
are basically conditioning the other operating conditions. As far as
NOM is concerned, enhancing the removal efficiencies of any water
treatment process implies a better understanding of its character-
istics and the variability patterns of its compositions and amounts
in drinking water sources (Chiang et al., 2002). Such combined data,
along with chemistry and hydrology of the water body itself, will
enable a more reliable assessment of the reactivity of NOM or its
surrogates and thus design and apply a reliable coagulation-based
treatment process. In this context, valuable findings were already
reported in the literature including the fact that coagulation is
generally more effective in removing heavier NOM molecules
(1000e4000 g/mol), with more affinity towards the hydrophobic
fraction, mostly constituted by humic substances (Yee et al., 2009).
In the following sections, the latest R&D investigations con-
ducted around the world on NOM removal via coagulation are
presented and analyzed in order to comparatively assess the effi-
ciencies of various coagulants and coagulation processes to remove
NOM from drinking water supplies.
3. NOM removal from drinking water supplies by coagulation
The conventional coagulation process is generally effective in
removing high molecular weight organics, but less so in removing
smaller molecular weight fractions (Nissinen et al., 2001). For the
case of NOM, its variable composition is posing serious challenges
to conventional coagulation. Since the hydrophobic fraction of
NOM has a higher charge density than the hydrophilic fraction, the
former is more easily coagulated than the latter (Jarvis et al., 2006;
Volk et al., 2000), which necessitates optimizing the coagulation
process to improve the NOM removal efficiency. In this regard,
waters containing high NOM content are usually treated with an
enhanced coagulation process, where higher dosage of coagulant is
applied, along with acidic pH (Vepsa € l€
ainen et al., 2009).
In real application, the efficiency of coagulation to remove NOM
mainly depends on the coagulant's type and dosage, pH, mixing
condition and temperature on the one hand, and NOM properties
including particle size, charge and hydrophobicity (Swietlik et al.,
2004; Korshin et al., 2009) and the presence of divalent cations
and destabilizing anions such as bicarbonate, chloride and sulfate
ions (Duan and Gregory, 2003; Lin and Lee, 2013), on the other
hand.
57
3.1. Metallic coagulants
The most widely used metal salt coagulants in drinking water
treatment have been aluminum (aluminum sulfate, aluminum
chloride and sodium aluminate) and ferric salts (ferric sulfate,
ferrous sulfate and ferric chloride) (Bahadori et al., 2013). The
economic factor (i.e. low cost and high availability in both solid and
liquid formulations) and the efficiency to remove turbidity and
color are the main reasons for the prolonged application of Al-
based salts and, to a lesser extent, Fe-based salts as coagulants in
water and wastewater treatment plants (Bratby, 2006).
Lately, the application of ferric coagulants is gaining ground over
the aluminum counter parts mainly due to the suspected health
risks associated with residual aluminum (Flaten, 2001) and the
better NOM removal capacities of ferric coagulants. Indeed, many
studies reported that ferric salts are able to remove more NOM than
aluminum salts, under same optimum conditions (Budd et al.,
2004; Uyak and Toroz, 2007; Umar et al., 2016). From a mecha-
nistic perspective, several comparative studies pointed out the
modus operandi differences between metallic coagulants, mainly
ferric and alum ones. In this regard, it was reported that during the
coagulation process ferric chloride (FeCl3) is more effective in
removing NOM in comparison with aluminum sulfate (Al2(SO4)3),
especially for high molecular mass compounds (above 3000 g/mol)
(Matilainen et al., 2005). Similarly, the results from other studies
showed that iron-based coagulants are more effective in removing
NOM fraction with intermediate molecular weights compounds
(1000e4000 g/mol), due to the higher charge density of ferric co-
agulants, compared to the aluminum-based counterparts (Hahn
et al., 2002). The main reason for such difference is the formation
of more and larger flocs during coagulation processes involving
ferric coagulants, than those formed during aluminum-based
coagulation (Fitzpatrick et al., 2004; Xiao et al., 2010). For
instance, it was found that the median floc sizes of Fe-based
coagulant is 710 mm, compared with 450 mm for Al-based ones
(Jarvis et al., 2012).
3.1.1. Aluminum-based coagulants
Within this group, aluminum sulfate, aka. alum [Al2(SO4)3] and
aluminium chloride (AlCl3) are among the most commonly used
coagulants for water and wastewater treatment (Crittenden et al.,
2012). The single most important factor affecting the effective-
ness of metal-based coagulants is pH (Qin et al., 2006). For instance,
when alum is added to the water the hydrolysis reactions generate
dissolved monomeric aluminum species and aluminum hydroxide
58 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71
precipitates, and the distribution of those species depends on the
pH of minimum solubility and total aluminum concentration. In
this regard, it was reported that the speciation distribution for
aluminum after the addition of 90 mg alum/L revealed that
aluminum hydroxide precipitates [Al(OH)3] are the predominant
species for pH around 4.6 (Gregory and Duan, 2001).
Theoretically, the hydrolyzing pH range for alum is between 5.5
and 7.7. At optimum pH, the solubility is minimal and the main bulk
of the coagulant is converted to solid floc particles. If the pH is
decreased below the optimal value, positively-charged dissolved Al
species are generated. In case of a pH increase above the optimum,
more negatively-charged Al species are formed (Pernitsky and
Edzwald, 2006). Noting that, away from the optimal range, espe-
cially at pH 3 and 11, the destabilization potential will be highly
reduced, and thus the small particles will not be able to aggregate
into large flocs and thus remain in water system (Wang et al., 2016).
As far as NOM is concerned, the coagulation-based removal
process is more efficient when more positively-charged Al species
are generated because NOM is mainly composed of organic com-
pounds with negatively-charged functional groups. For instance,
humic acid becomes highly negatively-charged above pH 4.7
(Stevenson, 1982). Thus, regarding the removal mechanisms of Al-
based coagulants, the positively-charged hydroxide precipitates act
as destabilizing agents of organic compounds (Gregory and Duan,
2001). The destabilization phenomenon occurs through the
adsorptive deposition of the hydroxides on the surface of the
negatively-charged particles, resulting in the charge neutralization
of those particles. Besides, the positively charged Al-based pre-
cipitates could neutralize dissolved organic compounds, which
lowers their solubility and promotes their precipitation (Pourrezaei
et al., 2011). As well, the phenolic and carboxylic functional groups
in organic compounds could be neutralized by the hydrolysis
products of alum [Al(OH)þ 2þ
2 and Al(OH) ], which exist alongside the
hydroxides, but in smaller concentrations (Duan and Gregory,
2003).
In some cases, NOM removal using metallic coagulants could
occur at low pH values, which reveals that, although pH is a decisive
operating factor, the characteristics of the targeted organic com-
pounds (charge, molecular weight, isoelectric point, etc.), is equally
influential in determining the overall efficiency of the applied
removal process.
The following Table 1 summarizes the operating conditions and
the main findings of selected R&D studies conducted around the
world between 2010 and 2016 on the removal of NOM from natural
waters or synthetic aqueous solutions using Al-based coagulants.
3.1.2. Iron-based coagulants
This group is mostly represented by ferric chloride (FeCl3) and
ferric sulfate [Fe2(SO4)3]. Both coagulants are commercialized
either in solid or liquid formulations. Application wise, the reported
dosages of FeCl3 and Fe2(SO4)3 vary from 5 to 150 mg/L and from 20
to 250 mg/L, respectively (Crittenden et al., 2012).
Such variation is due to the spatiotemporal variations of NOM
concentrations in the one hand, and the characteristics of the raw
water on the other. In this regard, one of the key operating factors is
pH, and the various studies conducted to assess its effect on the
iron-based coagulation process showed that the optimum pH range
is between 4.5 and 7 (Jarvis et al., 2012; Umar et al., 2016; Zhao
et al., 2014; Park and Yoon, 2009), which is slightly lower that the
optimum range for Al-based coagulants (5.5e7.7 for alum).
In practice, determining the optimum pH and dosage of the
ferric coagulant is a task that needs to be performed on a periodic
basis, as the NOM content tends to vary from one water source to
the other and within the same water source seasonally (amount
and composition wise). Such effort will help rationalizing the use of
coagulants and chemicals, controlling the amount of generated
sludge, and thus optimizing the overall coagulation/flocculation
process (Yan et al., 2009; Moghaddam et al., 2010; Jiang et al., 2016).
The chemistry associated with the reactions of ferric coagulants,
and other metal salts for that matter, is complex in water as various
species could be generated with respect to pH and temperature
(Ntwampe et al., 2016). In this case, the development of solubility
diagrams, illustrating the distribution of monomeric ferric species
as a function of metal salt concentration, pH and temperature
(Calza and Vione, 2015), could help estimating the optimum dosage
of ferric coagulants for variable operating conditions.
The following Table 2 overviews the operating conditions and
the main findings of selected R&D studies conducted around the
world between 2010 and 2016 on the removal of NOM from natural
waters or synthetic aqueous solutions using iron-based coagulants.
Noting that in numerous comparative studies, ferric coagulants
were reported to be more efficient to remove NOM from water than
the Al-based counterparts (Volk et al., 2000; Jarvis et al., 2012;
Gonzalez-Torres et al., 2014; Zhao et al., 2013a). Nonetheless,
aluminum-based coagulants tend to have higher color and
turbidity removal efficiencies, in comparison with the ferric ones
(Matilainen et al., 2010).
3.1.3. Titanium and zirconium-based coagulants
In the group of metallic coagulants, and in addition to the widely
used ferric and aluminum salts, two other metals, titanium (Ti) and
zirconium (Zr), were successfully applied as coagulants for water
and wastewater treatment, in form of titanium chloride (TiCl4) or
sulfate [Ti(SO4)2] and zirconium chloride (ZrCl4) or sulfate
[Zr(SO4)2] (Okour et al., 2009; Hussain et al., 2014; Jiang, 2015).
Although the application of Ti-based salts in coagulation-based
water treatment procedures has long been reported (since the late
1930s) (Upton and Buswell, 1937), it was until recently that a wider
application was made possible based on the effort made by re-
searchers around the world confirming the performances of Ti and
Zr-based coagulants to remove NOM and various other organics
from polluted waters, which in many studies exceeding those of
conventional Fe and Al-based coagulants.
In this regard, a research study investigated the coagulation
efficiencies of TiCl4 and ZrCl4 to remove NOM from a drinking water
source in Southern Australia, in comparison with conventional
alum (Hussain et al., 2014). Jar tests were conducted in order to
assess the effect of key operating conditions, mainly pH and
coagulant dosage, on the DOC and color removals. The main results
showed that ZrCl4 was the most efficient coagulant. Under opti-
mum conditions, the percentage DOC and color removals, at opti-
mum pH 4.5, were 61.4% and 92.1% for ZrCl4, compared to 44.1% and
84.2% for TiCl4 and 40.8% and 89.9% for Al2(SO4)3, respectively.
Thus, the lowest residual concentrations of the HA, FA and soluble
microbial were achieved using ZrCl4. Furthermore, it was reported
that the Zr-based coagulant was particularly efficient in removing
low to medium range MW organics (100e2000 Da).
In another comparative study, the coagulation performances of
titanium chloride, iron chloride and alum were assessed in HA-
kaolin synthetic water under variable operating conditions (Zhao
et al., 2014). The main results indicated that the TiCl4 was the
best performing coagulant with a maximum UV254 removal (55%,
compared to 48% and 41% for FeCl3 and Al2(SO4)3, respectively).
Nonetheless, in term of DOC removal, the ferric coagulant was
slightly better than the TiCl4 one (58% and 55%, respectively).
Regarding the floc formation and size, the aggregated flocs gener-
ated by TiCl4 exhibited the highest growth rate with the largest size,
comparison with the flocs formed by the two other conventional
coagulants. Nonetheless, the same flocs showed the weakest
strength and the worst re-growth after breakage. The possibility to
 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71 59

Table 1
Selected research studies on the removal of NOM from waters by coagulation using Aluminum-based coagulants, conducted between 2010 and 2016.

Targeted Water source and Main operating Monitored Optimum removal efficiencies Other key results References
organic characteristics conditions parameters
compounds

NOM Natural water from the Coagulant: % removal of A reduction of 41.2% in UV254 - The optimum pH and dose of coagulant (Zhao et al.,
Xiaoqing river (China) Al2(SO4)3 DOC and and 43.2% in DOC were were 7 and 30 mg/L, respectively. 2014)
Turbidity: 6.20e9.44 NTU Dosage: 5 UV254 reported. - The coagulant exhibited a floc growth
pH: 7.95e8.46, e50 mg/L Floc rate of about 65.1 mm/min.
DOC: 3.90e4.55 mg/L pH: 4-9 formation - The size of the formed flocs varied
UV254: 0.067e0.073 cm1 and size between 130.2 mm and 108.3 mm.
(equivalent
diameter)
NOM Natural water from a Coagulant: DOC and Minimum DOC and turbidity - The optimum pH was between 5 and 6 for (Jarvis et al.,
reservoir (Northern UK) Al2(SO4)3 turbidity residuals were respectively the three tested coagulant concentrations 2012)
Turbidity: 3.5 NTU Dosage: 5 reduction 3 mg/L and 0.5 NTU, both at pH (5, 10 and 15 mg/L)
DOC: 12.9 mg/L e15 mg/L Floc 5 for an initial dose of 5 mg/L. - The size of the formed Al flocs was
Specific UV absorbance pH: 4-8 formation ranging between 430 mm and 490 mm,
(SUVA): 4.8 L/mg-m Reaction time: and size with a floc growth rate around 520 mm/
around 30 min min.
Stirring rates:
30e200 rpm.
Algal organic Synthetic solutions including Coagulant: pH, DOC, DOC and HS removals of 83% - Optimum Al coagulant dose was 1.6 mg/L (Pivokonsky
matter bovine serum albumin, p Al2(SO4)3 UV254and and 65% were respectively and pH 5.5e6.2. et al., 2015)
and humic Peptides/proteins of Dosage: 0.2 residual Al reached. - The incorporation of algal peptides/
substances M. aeruginosa and peat HS e10 mg/L proteins positively impacted the Al-
(HS) DOC: 8e13, depending on Reaction time: based coagulation process as the overall
the ratios of the components. around 15 min efficiency to remove HS was improved
Mixing shear while reducing the coagulant dose.
rates: 50-200
s1.
Humic acid HAekaolin synthetic water Coagulant: Removal of The removal efficiencies - Optimum conditions were reported as (Zhao et al.,
(HA) Turbidity: 15 NTU Al2(SO4)3 DOC and reached 91.3% for UV254 and 2 mg/L for the Al-coagulant dose 2011a)
pH: 8.23e8.47, Optimum A254, and 57.3% for DOC, with a settled and 14.3 mV for the zeta potential.
DOC: 3.9 mg/L dosage: 2 mg/L settled turbidity of 1.02 NTU. - With a floc growth rate of 36.8 mm/min,
1
UV254: 0.45 cm Reaction time: turbidity the formed flocs had equivalent
around 30 min Floc diameters of 141.6e645.5 mm
Stirring rate: 40 formation
e200 rpm and size
NOM Natural water from the Coagulant: Total organic Al formate showed better - The optimum coagulant dose was 4 mg/L (Mikola et al.,
Oulujoki river (Northern Aluminum carbon (TOC) removal efficiency towards the at pH 6. 2013)
Finland) formate Removal of hydrophobic fraction of NOM, - Similar coagulation performances were
Total amount of NOM: 7.9 [Al(O2CH)3] different compared with the transphilic reported for the tested Al formate
e14.5 mg C/L. Dosage: 2 NOM and hydrophilic fractions. coagulant, in comparison with the
Hydrophobic fraction: 63 e8 mg/L fractions conventional Al sulfate counterpart.
e67% pH: 3-8
Reaction time:
around 45 min.
Stirring rates:
20e400 rpm.
HA HAekaolin synthetic water Coagulant: Turbidity, The removal of UV254 and DOC - The optimum dose of Al-based coagulant (Zhao et al.,
Turbidity: 15 NTU Al2(SO4)3 UV254 and were 93.4% and 75.9%, was 2 mg/L. 2011b)
UV254: 0.43 cm1 Dosage: 1 DOC respectively, with a residual - The average size of the aggregated flocs
DOC: 4.38 mg/L e6 mg/L Floc turbidity of 0.6 NTU was around 405 mm,
pH: 8.2 pH: 4-9 formation, - The strength and recovery factors were
Reaction time: size and estimated at 29.7 and 24.5, respectively.
40 min strength
Stirring rates:
40e200 rpm.

recycle the post coagulation TiCl4 sludge into anatase TiO2 was
confirmed.
In a recent investigation, the application of titanium sulfate in a
coagulation/ultrafiltration process to remove NOM from synthetic
HA-kaolin solutions was assessed, in comparison with aluminum
and ferric sulfates (Huang et al., 2016). The main objective of this
study is to determine the impact of the various coagulants on the
subsequent ultrafiltration process (i.e. impact on membrane
fouling), with respect to the characteristics of the formed flocs (size,
strength, structure and recovery ability) and under variable pH.
Overall, it was shown that, under neutral and basic conditions (pH
7e9), the flocs formed by Ti(SO4)2 had a compact structure and
were stronger and larger than the ones generated by the other
metallic sulfates. As for the membrane separation process, the
lowest extent of membrane fouling was reported using the tita-
nium sulfate coagulant.
3.2. Polymeric coagulants
In general, polymeric coagulants are macromolecular natural or
synthetic compounds made of repetitive chemical units (mono-
mers) and are able to destabilize the constituents of an aqueous
media, thus enhancing their flocculation. The following section
overviews the various synthetic (organic and inorganic) and nat-
ural polymers used as coagulants to remove NOM and derivative
compounds from drinking water supply.
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M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71

Table 2
Selected research studies on the removal of NOM from waters by coagulation using iron-based coagulants, conducted between 2010 and 2016.

Targeted Water source and Main operating Monitored parameters Optimum removal efficiencies Other key results References
organic characteristics conditions
compounds

NOM Natural water from Coagulant: % removal of DOC and A reduction of 47.6% in UV254 and - The optimum pH and dose of (Zhao et al.,
the Xiaoqing river ferric chloride A254 57.9% in DOC were reported. coagulant were 7 and 65 mg/L, 2014)
(China) (FeCl3) Floc formation and size respectively.
Turbidity: 6.20 Dosage: 15 - The coagulant exhibited a floc growth
e9.44 NTU e90 mg/L rate of about 121 mm/min.
pH: 7.95e8.46, pH: 5-10 - The size of the formed flocs varied
DOC: 3.90e4.55 mg/ between 187.5 mm and 422.9 mm.
L
UV254: 0.067
e0.073 cm1
NOM Natural water from Coagulant: Removal of DOC and A DOC removal of 80.5% was - The optimum pH was between 4.5 (Jarvis et al.,
a reservoir Ferripol XL, a turbidity reported, along with a turbidity and 5 for the three tested coagulant 2012)
(Northern UK) ferric sulfate- Floc formation and size residual of 1.15 NTU, at pH 4.5e5 concentrations (5, 10 and 15 mg/L)
Turbidity: 3.5 NTU based and a dose of 5 mg/L. - The size of the formed Fe flocs was
DOC: 12.9 mg/L coagulant ranging between 670 mm and
Specific UV Dosage: 5 790 mm, with a floc growth rate
absorbance (SUVA): e15 mg/L around 190 mm/min.
4.8 L/mg-m pH: 4-8
Reaction time:
around 30 min
Stirring rate: 30
e200 rpm
HA HAekaolin Coagulant: Removal of DOC and The removal efficiencies reached - Optimum conditions were reported (Zhao et al.,
synthetic water FeCl3 A254, and settled 95.4% for UV254 and 59.4% for DOC, as 8 mg/L for the Fe-coagulant dose 2011a)
Turbidity: 15 NTU Optimum turbidity with a settled turbidity of 0.75 NTU. and 10.4 mV for the zeta potential.
pH: 8.23e8.47 dosage: 8 mg/L Floc formation and size - With a floc growth rate of 77.8 mm/
DOC: 3.9 mg/L Reaction time: min, the formed flocs had sizes
UV254: 0.45 cm1 around 30 min ranging between 182.2 mm and
Stirring rate: 40 894.5 mm.
e200 rpm
NOM Source water from Coagulant: DOC, UV254, SUVA, The application of the Fe-based - Comparing the DOC species in the (Tubi
c et al.,
the Vojvodina FeCl3 trihalomethanes coagulant enabled a substantial raw and coagulated water, it was 2013)
region (Serbia) Dosage: 18 formation potential removal of NOM, with a reduction reported that the hydrophobic
pH: 7.5 e300 mg/L (THMFP) and haloacetic of DOC, UV254 and SUVA by 51%, fraction was significantly lowered by
DOC: 3.9 mg/L pH: 7 acid formation 70% and 30%, respectively. the coagulation process, along with
UV254: 0.45 cm1 Reaction time: potential (HAAFP). the complete removal of the HA
Turbidity: 15 NTU 32 min fraction.
Stirring rate: 30
e120 rpm
HA Runoff water from Coagulant: DOC, SUVA and some For the case of raw water, 76% of the - The optimum dosages of coagulant (Heiderscheidt
peat extraction site Ferric sulfate elemental analyses DOC was removed and the SUVA were 71 mg/L for the raw water (pH et al., 2016)
(Vihanti, Finland) [Fe2(SO4)3] value was reduced from 3.8 L/mg-m 4.5) and 80 mg/L for the pH-adjusted
pH: 4.5 Dosage: 0 to 2.8 L/mg-m. water (6.5).
DOC: 76.2 mg/L e100 mg/L - The main shortcoming was the high
SUVA: 3.8 L/mg-m pH: 4.5 and 6.5 residual Fe and SO2
4 concentrations
Turbidity: 6.9 NTU Reaction time: in the treated water.
around 45 min
Stirring rate: 50
e300 rpm
Algal Algal turbid water Coagulant: Turbidity and zeta Turbidity removal efficiency was - The optimum dosage of FeCl3 was (Chekli et al.,
organic Turbidity: 20 NTU FeCl3 potential around 97% 15 mg/L. 2017)
matter pH: 8.7 Dosage: 0.03 Floc formation and size - Under optimum conditions, floc zeta
Zeta e0.2 mmol/L potential value was around 9.5 mV
potential: 19.7 mV pH: 5-9 (after coagulation).
Optical density: Reaction time: - The floc sizes ranged between 270 mm
0.29 at 750 nm around 40 min and 820 mm, with a growth rate of
Stirring rate: 40 about 90.7 mm/min).
e200 rpm

3.2.1. Synthetic polymeric coagulants
3.2.1.1. Inorganic polymers. After reviewing metallic coagulants (Fe,
Al, Ti and Zr chlorides or sulfates), the present section overviews
the use of those metals for the development of inorganic polymeric
coagulants. Such development was justified by the fact that when
inorganic salts are added to the water, the metallic ions tend to
hydrolyze quickly and in an uncontrolled manner, thus forming a
range of metal hydrolysis species, depending on the water chem-
istry and the coagulant dosage (Jiang and Graham, 1998). These
coagulants are generally developed through the partial
neutralization of concentrated solutions of metal salts using a base
before the coagulation process.
For instance, it was reported with the addition of a base (NaOH
for example) to a solution containing aluminum salt, the super-
saturation of the solution with amorphous Al(OH)3 starts to build
up and is quickly followed by a precipitation phenomenon. Adding
more base reduces the overall positive surface charge of the
colloidal hydroxides which leads to the formation of large amounts
of polymeric species (Duan and Gregory, 2003). Similar tendency
was also confirmed for the generation of polymeric coagulants from
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M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71
pre-hydrolyzed ferric chloride and sulfate (Zin et al., 2015; Huang
et al., 2015a). In this regard, the most studied and applied pre-
hydrolyzed metal-ion coagulants are polyaluminum chloride
(PAC) (Wang et al., 2017; Hu et al., 2015), polyferric chloride (PFC)
(Cao et al., 2011), polyferric sulfate (PFS) (Zouboulis et al., 2008), as
well as various composite inorganic coagulants such as polymeric
aluminum ferric sulfate (PAFS) (Zhu et al., 2011), polymeric ferric
zinc sulfate (PFZS) (Wei et al., 2016) and polymeric phosphate
aluminum chloride (PPAC) (Zheng et al., 2011). Lately, the genera-
tion of inorganic polymeric coagulants from polytitanium salts and
their application for NOM removal from drinking waters is gaining
the attention of researchers from around the world (Chekli et al.,
2017; Zhao et al., 2015). The main NOM removal mechanisms
generally associated with inorganic polymeric coagulants are
adsorption, entrapment, complexation, and to a lesser extent,
charge neutralization (Cheng and Chi, 2002; Wei et al., 2009).
In previous studies, these inorganic polymeric coagulants
showed better removal capacities toward NOM and other organics
from waters, in comparison with coagulants such as aluminum
sulfate or ferric sulfate (Jiang, 2015; Jiang and Graham, 1996). Be-
sides, other studies revealed that inorganic polymers had better
coagulation performances in cold waters or in low-alkalinity waters
for turbidity removal, compared with conventional alum or ferric
chloride (Cheng et al., 2008). Nonetheless, other studies reported
that better removal performances were achieved using metal salt
coagulants such as TiCl4 and FeCl3, in comparison with widely used
polymeric PAC (Park and Yoon, 2009; Gkotsis et al., 2017).
Recently, a newly developed aluminum-based hybrid coagulant
with doped ion-exchange functional groups was reported to be
better than both metal salts (alum and ferric chloride) and poly-
meric PAC in NOM removal from natural waters, specifically for the
low molecular weight and charged organic matter (Zhao et al.,
2016).
3.2.1.2. Organic (synthetic) polymers. Basically, polymeric com-
pounds are composed of long chains of repetitive monomers joined
together by covalent bonds. If the polymer contains ionizable sites,
then it is referred to as polyelectrolyte (i.e. ionic polymer). As a
consequence, organic polymers are generally classified based on
their ionic nature, hence cationic (positively charged), anionic
(negative charge) or non-ionic (neutral) groups. Thus, based on
their large molecular size and charge characteristics, organic
polymers, once hydrolyzed, can promote the destabilization of or-
ganics and particles through bridging and/or charge neutralization
(Bolto et al., 1998).
For the case of NOM removal from drinking water supply, a
specific type of organic coagulants is mostly applied: cationic
polyelectrolytes. At natural water pH values, NOM and its pre-
dominant humic fraction are of anionic character, hence the need to
apply cationic polymers to promote the electrostatic interactions
with NOM's “anionic polyelectrolytes”. Thus, charge neutralization
is the main coagulation mechanism for NOM removal using cationic
organic polymers (Matilainen et al., 2010; Bolto et al., 1998; Bolto
and Gregory, 2007). In the same context, some studies showed
that the polyelectrolyte molecular weight did not show any sig-
nificant effect on the coagulation of NOM (specifically humic sub-
stances) (Kvinnesland and Ødegaard, 2004).
The list of cationic polyelectrolytes includes synthetic polymers
such as polydiallyldimethyl ammonium chloride (pDADMAC),
cationic polyacrylamide (CPAM), polymers from epichlorohydrin
and dimethylamine, as well as natural polymers including chitosan
and starch. This group of natural polymeric coagulants will be
discussed in the following Section “3.2.2”.
In practice, many studies are promoting the utilization of
organic polymers, as primary coagulants in water treatment
61
systems, more than metal-based coagulants, because they involve
the application of lesser dosage of coagulant, generate less sludge
volume, are less pH dependent and reduce the residual fraction of
unbound metallic compounds (Gao et al., 2008; Chang et al., 2005).
Other reports are predicting that the use of organic polymers can
reduce the overall treatment cost by 25e30%, in comparison with
metallic coagulants (Nozaic et al., 2001).
3.2.1.3. Removal efficiencies of synthetic polymeric coagulants.
The following Table 3 presents the operating conditions and the
main findings of recent R&D studies on the removal of NOM or
derivative compounds from natural waters or synthetic aqueous
solutions using synthetic polymeric coagulants.
3.2.2. Natural polymers: biocoagulants
In practice, and despite the proven efficiency of metallic co-
agulants (unbound or polymeric) and synthetic organic polymers
to remove NOM and derivative compounds from waters and
wastewaters, several drawbacks were reported. For the case of
metallic-based coagulants, one (or several) of the following issues
are often reported: high sludge volumes, high costs, water pH
modification and residual metals or polymers in the treated waters
(Ncibi et al., 2017). Regarding the use of synthetic polymers, man-
ufactured synthetic coagulants could contain contaminants from
the production process including residual monomers and reaction
by-products, which could be harmful to living organisms. As well,
polyelectrolyte formulations could also react with other com-
pounds present in the water during the treatment, thus potentially
forming undesirable auxiliary products (Aizawa et al., 1991;
Oladoja, 2016).
In this context, several R&D studies focused on the production of
biomass-derived coagulants/flocculants in order to develop
greener alternatives to the conventional coagulants. Thus,
numerous coagulating/flocculating biochemicals (mainly poly-
saccharides and proteins) derived from various bioresources were
investigated as coagulants or coagulant aids, either from terrestrial
plants, marine species or microbial organisms. So far, the
commercially available natural coagulants mainly include chitosan
and tannin-based-coagulants (Heiderscheidt et al., 2016; Oladoja,
2016; Renault et al., 2009; Graham et al., 2008). The main advan-
tages of those biocoagulants are their renewability, biodegrad-
ability, nontoxicity and relative cost-effectiveness.
The following Fig. 3 depicts a general three-step extraction and
purification process for the production of biocoagulants from
plants.
In Table 4, the operating conditions and the main results of
selected R&D studies on the removal of NOM or derivative com-
pounds from natural waters or synthetic aqueous solutions using
biocoagulants are detailed. In this regard, it has to be noticed that
very few articles were published on the issue of removing NOM
from drinking water supplies or even synthetic solutions. Defi-
nitely, more attention needs to be paid to this research subject
especially that numerous coagulating biopolymers were already
developed from various bioresources and we need to test them as
coagulants or coagulant aids for NOM removal in order to anticipate
their wider application in emerging sustainable concepts such as
circular economy and bioeconomy.
3.3. Composite metalliceorganic polymeric coagulants
The main objective of developing composite coagulants is to
benefit for the advantages of the previously mentioned coagulants,
metallic and polymeric (synthetic or natural), while mutually
overcoming their shortcomings. Many novel composite or hybrid
coagulants have been developed via various combination schemes
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M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71

Table 3
Selected research studies on the removal of NOM from waters by coagulation using synthetic (inorganic and organic) polymeric coagulants, conducted between 2010 and 2016.

Targeted Water source Main operating conditions Monitored Optimum removal efficiencies Other key results References
organic and parameters
compounds characteristics

Inorganic polymeric coagulants

HA HAekaolin Coagulants: PAC and PFS Turbidity, The respective removals of UV254 and - The optimum dosages of PAC and PFS (Zhao
synthetic Dosage: 1e6 mg/L (PAC) and UV254 and DOC were 91% and 77% for PAC and 94% coagulants were 3 mg/L and 10 mg/L, et al.,
water 4e12 mg/L (PFS) DOC and 81% for PFS. respectively. 2011b)
Turbidity: 15 pH: 4-9 Floc - The respective strength and recovery
NTU Reaction time: 40 min formation, factors were estimated at 34 and 18for
UV254: Stirring rates: 40e200 rpm. size and PAC and 29 and 15 for PFS.
0.43 cm1 strength
DOC: 4.38 mg/
L
pH: 8.2
HA HA-containing Coagulant: PTC Turbidity, Removal efficiencies of 88% and 61.1% - Application of optimized PTC dose (Zhao
synthetic Dosage: 8e14 mg/L UV254 and were reported for UV254 and DOC, (8 mg/L) enabled the optimum et al.,
water pH: 5-10 DOC respectively. The residual turbidity was coagulation of HA. 2013b)
Turbidity: 4.7 Reaction time: 30 min Floc estimated at 1.8 NTU. - With a floc growth rate of 93.2 mm/min,
e5.3 NTU Stirring rates: 40e200 rpm. formation, the formed flocs had sizes ranging
UV254: size and between 227 mm and 839 mm.
1
0.33 cm strength
DOC: 5.1
e5.6 mg/L
pH: 8-9
Dissolved Natural water Coagulant: PAC Turbidity, A near complete removal of UV absorbing - Optimum DOM removal was reported (Hussain
organic for the Murray Dosage: 5e16 mg/L UV254, SUVA, organics of high apparent MW (AMW for a coagulant dose of 11 mg/L and pH 6. et al.,
matter river pH: 5.5e8.5 DOC and between 2000 Da and 10000 Da) was - The used coagulant was less performing 2013)
(DOM) (Southern Reaction time: 30 min adsorption achieved. in the removal of low AMW (100 da
Australia) Stirring rates: 20e200 rpm. capacity e600 Da) organic compounds, even
Turbidity: 91.3 Floc when applying high doses.
NTU formation,
UV254: and growth
0.325 cm1
DOM as DOC:
14.1 mg/L
pH: 7.3
HA HA-containing Coagulant: PTC Turbidity The turbidity, UV254 and DOC removals - The optimum dosage of PTC was (Chekli
synthetic Dosage: 0.05e0.3 mmol/L and zeta were 97.4%, 89.6% and 36.1%, 0.15 mmol/L. et al.,
water pH: 3-9 potential respectively. - The floc sizes ranged between 326 mm 2015)
Turbidity: 19 Reaction time: around Floc and 820 mm, with a growth rate of about
NTU 40 min formation 279 mm/min).
pH: 7.7 Stirring rate: 40e200 rpm and size
DOC: 8.04 mg/
L
UV254:
0.257 cm1
DOM River water Coagulant: PTS Turbidity, UV254 and DOC removals were around - The optimum operating conditions (Zhao
from Dosage: 6e16 mg/L UV254, DOC 70% and 76%, respectively (i.e. 7% and were a dose of 30 mg/L and pH 9. et al.,
Parramatta, pH: 5-10 and zeta 10% higher than the respective removals - The PTS coagulants generated larger 2017)
Sydney. Reaction time: around potential registered for Ti(SO4)2. flocs than non-pre-hydrolyzed Ti(SO4)2,
Turbidity: 1.3 30 min Floc with higher floc growth rate.
e3.2 NTU Stirring rate: 40e200 rpm formation
pH: 7.5e8 and size
DOC: 7.7
e9.3 mg/L
UV254:
0.18 cm1
Organic polymeric coagulants
HA HA-rich Coagulant: pDADMAC DOC and DOC removal was around 80%. - Optimum coagulant dose was 60 ppm (Kim,
synthetic Dosage: 0e60 ppm zeta at pH 7.2. 2015a)
water pH: 7 potential - The addition of Ca2þ to the reaction
pH: 7.2 Reaction time: 20 min Floc helped forming flocs with higher fractal
TOC: 8.2 mg/L Mixing velocity gradient: formation dimensions, thus improving the overall
Conductivity: 200 s1 and size DOC removal.
1.5 mS cm1 - The pDADMAC-based coagulation
decreased the hydraulic resistance to the
microfiltration process, thus optimizing
the efficiency of hybrid coagulation/
membrane filtration systems.
NOM Natural water Coagulants/flocculants: DOC and - At the highest PAC dosage (25 mg/L), - In the integrated coagulation- (Wang
from the pDADMAC (cationic), PAM UV254 48.7 and 77.6% removal were achieved microfiltration process, the use of et al.,
Mississippi (nonionic), PACA (anionic, Floc for DOC and UV254, respectively. cationic pDADMAC helped mitigating 2013)
River along with PAC as primary formation - The addition of 5 mg/L 100e200 kDa membrane fouling because of the
(Minneapolis, coagulant and size pDADMAC increased DOC removal to reduced DOM content in the membrane
MN) Dosage: five polymer/PAC 64.8%. feed water.
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M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71 63

Table 3 (continued )

Targeted Water source Main operating conditions Monitored Optimum removal efficiencies Other key results References
organic and parameters
compounds characteristics

Turbidity: 9 ratios - As for the anionic and non-ionic poly-

NTU Reaction time: around mers, the fouling phenomenon substan-
pH: 8.14 22 min tially increased, despite enhanced NOM
DOC: 10.8 mg/ Stirring rate: 30e100 rpm removals, due to the residual polymer
L fraction, poorly incorporated in the flocs.
UV254:
0.32 cm1
HA HA-rich Coagulant: Epi/DMA DOC, zeta The application of the charge In an integrated coagulation/membrane (Kim,
synthetic Dosage: 0e18 ppm potential, neutralization dose (18 ppm) decreased filtration process, multi-cycle tests 2015b)
water pH: 7 SUVA and the DOC from 7.6 mg/L to 1.7 mg/L and showed that epi/DMA additions (50e150%
pH: 7.2 Reaction time: 30 min UV254 reduced the UV254 values from 0.67 cm1 of the optimum dose of 18 ppm)
TOC: 8.1 mg/L Mixing velocity gradient: Floc to 0.09 cm1. significantly reduced the hydraulic
Conductivity: 400 s1 for 10 min formation resistance phenomenon.
1.5 mS/cm and size
HA Synthetic Coagulant: cationic PAM, Turbidity, The DOC, UV254 and turbidity were - The optimum PAM dose was 0.2 mg/L. (Yu et al.,
water (HA in as an aid to alum UV254 and respectively reduced to 2.2 mg/L, - As for the floc formation, the results 2013a)
tap water) Dosage: 0e3 mg/L DOC 0.02 cm1 and 0.07 NTU. showed that increasing PAM dose up to
Turbidity: 13.2 Dosing time: 0e16 min, Floc 0.5 mg/L led to a decrease of the fractal
NTU after adding 0.1 mM alum formation dimension of flocs from 2.76 to 2.58,
pH: 7.9 Reaction time: around and size which remained almost contact at higher
DOC: 4.6 mg/L 15 min doses (1e3 mg/L).
Conductivity: Stirring rate: 50e200 rpm
862 mS cm1
UV254:
0.12 cm1

and, in the following section, a selection of related R&D studies are
highlighted.
A novel inorganiceorganic composite, combing polyferric
aluminum chloride (PFAC) and p-DADMAC, was developed and
applied to monitor the growth, breakage, regrowth and fractal
nature of the formed flocs, then assess any potential improvement
in the aggregating ability of this dual coagulant during the removal
humic acid from synthetic HA-kaolin solutions, under various pH
and shear forces (Sun et al., 2011). The main results revealed that
the flocs formed in acidic conditions were more compact, stronger
and more recoverable than the one generated in alkaline HA so-
lutions. For instance, the recovery rate was 43.3% at pH 5 and then it
dropped almost by half at pH 8 (21.3%). Regarding the coagulation
mechanisms, the authors stated that, in acidic solutions, the main
mechanism was charge neutralization, while physical precipitate
adsorption was the main phenomenon governing the coagulation
in alkaline conditions, Another study investigated the efficiency of a
composite coagulant developed by the hybridization of PAC with
chitosan (PACechitosan) to remove NOM from synthetic and nat-
ural waters (Ng et al., 2013). It was found that PAC-chitosan was
more effective than PAC alone in removing organic matter from the
synthetic water, with close performances in the natural surface
water. Indeed, for an initial SUVA value of 5.8 L/m-mg, it decreased
to 4.4 L/m-mg in the synthetic water treated with PAC and further
down to 2.7 L/m-mg when PACechitosan was applied. As for the
natural water samples, similar SUVA values (~2.1 L/m-mg) were
detected in waters separately treated by both coagulants. Besides,
the analyses revealed a lower level of total THMFPs (initially
506 mg/L) in the synthetic water treated with composite PACechi-
tosan (199 mg/L), compared to the water treated with PAC alone
(294 mg/L). However, for the case of natural water, PAC was more
effective in reducing the total THMFPs in the treated water than the
composite coagulant, hence the need to further optimize the effi-
ciency of such interesting organometallic combination, mainly in

Fig. 3. The processing phases applied for the production of biocoagulants from plants (Yin, 2010).
64 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71

Table 4
Selected research studies on the removal of NOM from waters by coagulation using biocoagulants, conducted between 2010 and 2016.

Targeted Water source and Main operating Monitored Optimum removal efficiencies Other key results References
organic characteristics conditions parameters
compounds

HA Runoff water from Biocoagulants: DOC, SUVA and - Tannin was more performing - The optimum dosages of chitosan (Heiderscheidt
Commercial chitosan
peat extraction site some elemental in removing DOC with an and tannin-based coagulants were et al., 2016)
(Vihanti, Finland)and tannin-based analyses efficiency of 52% compared to 40 mg/L and 110 mg/l, respectively for
pH: 4.5 biopolymers 43% for chitosan. However, both pH 4.5. Higher doses were required for
DOC: 76.2 mg/L Dosage: 0e80 mg/L were less efficient than ferric pH 6.5.
SUVA: 3.8 L/mg-m (chitosan) and 0 sulfate (76%) and pDADMAC
Turbidity: 6.9 NTUe200 mg/L (tannin) (57%) in DOC removal.
pH: 4.5 and 6.5 - As for SUVA, the lowest residual
Reaction time: around value was registered for the
45 min tannin-base coagulant
Stirring rate: 50
e300 rpm
HA Synthetic kaolin Biocoagulant: green DOC, UV254 and - For an alum dose of 9 mg/L, both - The optimum dosage of the algal (Zhao et al.,
ehumic acid algae Enteromorpha turbidity DOC and UV254 removals were extract was 0.1 mL at a pH of 6e7. 2013c)
solutions extract (as coagulant Floc formation improved (66% and 97%, - The coagulation efficiencies of
pH: 8.2e8.4 aid to alum) and size respectively) after the addition of combined biocoagulant and alum were
DOC: 5.1e5.3 mg/L Dosage: 0.1e0.6 mg/L the biocoagulant (0.1 mL). better than those of the metallic
UV254: 0.30 pH: 4-9 - Lesser removal rates were coagulant alone, within all the
e0.34 cm1 Reaction time: around achieved by alum alone (56% investigated pH range.
Turbidity: 14.5 45 min and 90%, respectively).
e15.5 NTU Stirring rate: 50
e300 rpm
NOM Raw River Nile Biocoagulant: BOD and - Turbidity and BOD removals by - EPS extracted from B. licheniformis (Al-Wasify
water exopolysaccharides turbidity the tested biocoagulant were showed the best coagulation et al., 2015)
Biological oxygen (EPS) extracted from around 31.7% and 32.5%, preference, in comparison with the
demand (BOD): three bacteria (Bacillus respectively. biopolymers from the other bacteria.
4 mg O2/L licheniformis, B. insolitus - Mixing the bacterial EPS with
Turbidity: 9 NTU and B. alvei) alum (50:50, w/w) substantially
Dosage: 0.2e1 g/L enhanced the overall coagulation
Reaction time: around performance with BOD removals
25 min between 65% and 75%, depending
Stirring rate: 45 on the bacterial strain.
e120 rpm

the preparation phase with a more elaborate assessment about the
characteristics of the generated flocs of growth (in addition to the
experiments conducted on the effect of coagulant dosage)
including breakage, regrowth and fractal structure, under various
operating conditions.
Other related studies developed and applied new types inor-
ganiceorganic hybrid coagulants for the removal of NOM or HA
from natural waters or synthetic solutions. The list includes com-
posite coagulants such as polyferric aluminumepDADMAC (Sun
et al., 2012), polyferric sulfateepDADMAC (Moussas and
Zouboulis, 2012), polyferric chlorideelignineacrylamide polymer
(Rong et al., 2013), ligninepDADMACeacrylamide (Li et al., 2015)
and a zirconiumeglycine complex (Zhang et al., 2014).
3.4. Electrocoagulation (EC)
EC is a well-established water treatment technology widely
applied for the decontamination of drinking water supplies
(Malakootian et al., 2010; Wan et al., 2011) and municipal and in-
dustrial wastewaters (Hanafi et al., 2010; Al-Shannag et al., 2013;
Demirci et al., 2015) from organic, inorganic and biological pollut-
ants such as pesticides, dyes, heavy metals, biological pathogens,
etc.
Reaction wise, the metallic compounds (mainly iron or
aluminum metals) are dissolved into the water medium from the
sacrificial anode. The generated metal ions are immediately hy-
drolyzed to continuously form coagulating polymeric Fe or Al hy-
droxides near the anode. Basically, an EC process follows three
consecutive phases: (i) the in-situ formation of coagulants by
electrolytic oxidation of the sacrificial electrode, (ii) the
destabilization of the pollutants and particles in the colloidal sus-
pension, and (iii) the aggregation of the destabilized compounds to
form flocs (Dermouchi et al., 2015). Furthermore, and with respect
to the crucial destabilization phase, several mechanisms were re-
ported, including (Comninellis and Chen, 2010):
- The compression of the diffuse double layer around the charged
species during their interactions with the ions produced by
electro-oxidation of the consumable electrode.
- The charge neutralization of the ionic species present in water
by counter ions generated by the electrochemical dissolution of
the sacrificial anode.
- The entrapment of the remaining colloidal matter in water by a
sludge blanket formed by bridged flocs.
Compared to chemical coagulation, EC enables the in-situ de-
livery of coagulant without the need to add other chemicals and the
related process could be operated in compact treatment facilities,
along with additional side reactions (hydrogen bubble formation
and pH change), which could also contribute in destabilizing the
pollutants (Vepsa €la
€inen et al., 2009; Sa
€rkka
€ et al., 2015). Such fea-
tures were reported to be beneficial in improving the removal ef-
ficiency, reducing the operating costs and producing less sludge
(Can~ izares et al., 2006; Panizza and Cerisola, 2010).
Overall, the efficiency of electrocoagulation processes in water
treatment is highly dependent on the chemistry of the water media
itself, mainly conductivity and pH, as well as the concentrations and
chemical properties of the targeted contaminants (Yildiz et al.,
2007).
During the last decades or so, an increasing number of R&D
 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71
studies were conducted to apply and assess the efficiency of EC in
removing NOM from water supplies and aqueous solutions. The
following Table 5 presents the main operating conditions and
experimental findings of various studies investigating the appli-
cation of EC for the removal of NOM or derivative compounds from
natural waters or synthetic aqueous solutions.
3.5. Coagulation-based integrated processes: resilient and efficient
water treatment processes
Several kinds of commercially available coagulants are being
applied in real case scenarios for the treatment and decontamina-
tion of drinking water supplies, principally metallic and polymeric
ones. Nonetheless, despite their high efficiencies to remove NOM
and other organic and inorganic contaminants, several issues were
reported for large scale applications. This mainly includes residual
metals and polymers in the treated effluents, pH change, relative
high operating costs, and the generation of large sludge volumes,
especially for enhanced coagulation process, where more (excess)
coagulants need to be used. Thus, the main challenges for viable
large scale application of coagulation-based water treatment pro-
cesses are the technological complications (during the process and
for sludge management) and the economic considerations.
Generally, in the field of drinking water treatment and in
addition to coagulation, various widely-used technologies are being
applied around the world, including membrane (micro, ultra and
nano) filtration (Guo et al., 2010; Mets€ amuuronen et al., 2014),
advanced oxidation processes (Matilainen and Sillanp€ €, 2010), ion
aa
exchange (Bolto et al., 2002), reverse or forward osmosis (Malaeb
and Ayoub, 2011; Chun et al., 2015) and adsorption (Bhatnagar
and Sillanpa€a
€, 2017).
In order to enhance the overall efficiency of water treatment
plants and anticipate more severe water regulations in the future,
integrating two or more of those technologies with proven NOM
removal capabilities is a viable strategy to develop a complemen-
tary modus operandi.
In the following sections, various integrated water treatment
processes combining coagulation with other technologies such as
membrane filtration, oxidation, adsorption and ion exchange are
presented.
3.5.1. Integrated coagulationemembrane filtration process
The application of membrane-based separation and purification
processes for the treatment of NOM-rich water supplies is generally
conduced with a pretreatment stage. Such approach is necessary in
order to mitigate the membrane fouling phenomenon, reduce
maintenance costs and enhance the overall removal capabilities.
Many related studies proved that humic substances can consider-
ably reduce the efficiency of ultrafiltration (UF) to remove NOM
from aqueous media (Sutzkover-Gutman et al., 2010; Yu et al.,
2013b). Noting that for membrane filtration, the fouling phenom-
enon has to be simultaneously monitored and correlated with the
permeate flux in order to have a reliable assessment about the
overall efficiency of membrane separation processes, as some se-
vere membrane fouling could lead to improved removal rates.
A research study investigated the efficiency of an integrated
coagulationemembrane separation to remove NOM from natural
water collected from the Pirapo River in Brazil (turbidity of 240 NTU
and TOC of 6.4 mg/L) (Bergamasco et al., 2011). Two coagulants
were tested during the coagulation/flocculation stage: chitosan and
aluminum sulfate. It was found that use of chitosan as coagulant
followed by UF (transmembrane pressure of 1 bar) enabled the
highest reduction of chemical oxygen demand (COD), 91%,
compared to coagulation alone 60% and UF alone (86.7%). As well, it
65
was revealed that, although, the water coagulated with chitosan led
to higher membrane fouling during the UF process (79% at 2 bar), it
yielded a higher average permeate flux (twice the flux achieved
using aluminum sulfate as coagulant before UF). Thus, the authors
recommenced the use of chitosan as natural coagulant prior to UF
process for an eco-friendly and efficient surface water treatment.
Other coagulants were also tested in such integrated scenarios
to remove NOM from drinking water supplies. This includes a study
investigating the use of PAC and pDMDAAC as coagulants in a
hybrid coagulation-UF process for HA removal from synthetic wa-
ters (Shen et al., 2017). First, it was found that the combined use of
PAC and pDMDAAC (optimum doses of 1 mg/L and 0.1 mg/L,
respectively) helped reducing the membrane fouling, compared to
PAC alone. As well, the addition of pDMDAAC to PAC substantially
improved the turbidity and DOM removal rates by the hybrid
process.
In other studies different types of membranes were used in
coagulation-filtration process. In this regard, a research study used
ceramic membrane in combination with PAC for the Treatment of
raw river water (Li et al., 2011). The main results showed that the
integrated process was more effective in DOC removal than coag-
ulation or membrane filtration alone, with removal rates averaging
between 34% and 54%. The variation of the hydraulic retention
times (HRT) and its effect, along with the coagulant dose, on the
process performance revealed two main tendencies. At the HRT of
10 min, varying PAC dose in the range of 15e25 mg/L did not affect
the overall performance of the hybrid system. At the HRT of 5 min,
the PAC dose enabling optimum DOC removal and permeate flux
was 15 mg/L.
Along with ultrafiltration, many studies investigated integration
scenarios involving coagulation and nanofiltration. For instance, a
research team investigated the efficiency of an integrated system
involving two kinds of nano-membranes and two types of co-
agulants (alum and ferrous sulfate) for the removal of humic acid,
bromide and bromate anions, and the permeate flux decline
(Listiarini et al., 2010). The results from this study also confirmed
that the efficiency of integrated coagulationenanofiltration process
to remove HA and reduce bromate, when ferrous sulfate is used,
while maintaining and even improving the permeate flux. None-
theless, none of the applied processes (integrated or single tech-
niques) was efficient in removing bromide.
In another related study, chitosan was tested as natural coagu-
lant in hybrid coagulation-nanofiltration membrane process for
water treatment (Ang et al., 2016). The main finding was the in-
compatibility of chitosan with nano-membranes. Hence, although
the natural coagulant was effective in removing turbidity of the HA
synthetic solution, the main coagulation mechanism was charge
neutralization, which produced neutral charge particles in the su-
pernatant solutions thus causing a disastrous impact on the
membrane performance (i.e. enhanced membrane fouling due to
reduced electrostatic repulsion).
The possible integration of electrocoagulation and membrane
filtration for the removal of NOM from aqueous media was also
investigated in other research studies, with improved perfor-
mances for the hybrid systems, compared with the single processes
(Han et al., 2015; Chellam and Sari, 2016; Sun et al., 2016).
3.5.2. Integrated coagulationeadsorption process
Another interesting integrated scenario involves the combina-
tion of coagulation with the widely-used adsorption technique.
Several R&D studies were, and are being, conduced to assess the
applicability and efficiency of such hybrid water treatment process
for the removal of organic and inorganic pollutants.
As far as NOM is concerned, many adsorbing materials were
tested in combination with different coagulants. In a related study,
66 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71

Table 5
Selected research studies on the removal of NOM from waters by electrocoagulation, conducted between 2010 and 2016.

Targeted organic compounds Water source and Main operating conditions Optimum removal efficiencies References
characteristics

NOM Surface water from a Finnish Electrodes: Aluminum electrodes and - Highest removal was 78%, corresponding (Vepsa €l €
ainen
river commercially available dimensionally to the lowest TOC concentration of et al., 2012)
TOC: 18.3 mg/L stable anode (DSA), both as anodes or 4 mg/L.
Turbidity: 0.34 NTU cathodes in various cell configurations. - Aluminum generated from the anodes or
Zeta potential: 15.2 mV Current density: 0.48 mA/cm2 cathodes had similar NOM removal
pH: 4-8 efficiency
Standardized NOM isolate Synthetic water Electrodes: hot-rolled iron steel anode - The highest removal rates (73e88%) were (Dubrawski and
DOC: 13.8 mg/L and stainless steel cathode reported for the current density range of Mohseni,
Conductivity: 300 mS/cm Current density: 2.43e26.8 mA/cm2 2.43e13.4 mA/cm2, with an optimum at 2013a)
pH: 7 10 mA/cm2.
- At pH 6, the faster dosing mode helped
enhancing the DOC and UV254 removals
by 13.8% and 29%, respectively.
NOM Natural water for a lagoon Electrodes: iron foil anode and - Raman analyses at various current (Dubrawski and
(Vancouver, Canada) platinum foil cathode densities and CLRs revealed the presence Mohseni,
pH: 6.1 Current density: 1e25 mA/cm2 of three different crystalline iron species: 2013b)
DOC: 13.3 mg/L Charge loading rate (CLR): 12e300 C/L/ green lust, Fe3O4 and g-FeOOH.
UV254: 0.56 cm1 min - The green lust speciation was the most
Conductivity: 990 mS cm1 pH: 6.1e6.5 effective ion specie in removing NOM,
with a DOC reduction of 71%.
NOM Natural water for a Lake Saimaa Electrodes: Aluminum, iron and hybrid - It was found that the hybrid electrodes (Ulu et al.,
(Mikkeli, Finland) AleFe electrodes. were more effective in removing color 2015)
pH: 7.3 Current density: optimum at 3 mA/cm2 (92.4%) than Al and Fe electrodes.
DOC: 14.8 mg/L pH: 4-8 - As for DOC reduction, the removal rates
UV254: 0.41 cm1 using Al, Fe and hybrid AleFe electrodes
Conductivity: 1422 mS cm1 were 71.1%, 59.8%, and 68.6%,
respectively.
NOM HA-kaolin synthetic solutions Electrodes: Aluminum electrodes. - The in-situ generation of polymeric Al13 (Hu et al., 2016)
Turbidity: 8.3 NTU Current density: 1, 5 and 10 mA/cm2 coagulant became dominant Al specie
DOC: 5 mg/L during 5e15 min of the EC process, using
pH: 7 a low current density at pH 5e7.
- The highest removal rates (~95% turbidity
and 65% TOC) were achieved after 10 min
of EC, at pH 7 and using a current density
of 5 mA/cm2.

the joint application of chemically-modified wheat straw as
adsorbent and two inorganic polymers as coagulants (PAC and PFC)
was assessed for NOM removal from natural river water, with
respect to DOC, turbidity and UV254 reductions (Zhan et al., 2010).
The main finding was that the integrated coagulationeadsorption
process enabled better UV254 and turbidity removal rates (61.8%
and 95.8% respectively for PFCewheat straw, and 61.5% and 94.2%
respectively for PACewheat straw), in comparison with the
removal rates registered for each treatment applied separately.
The most widely-used absorbent in water treatment in activated
carbon and many studies worked on integrated systems combining
various coagulants and activated carbons, For instance, a research
team in Australia coupled powdered activated carbon with
enhanced coagulation and applied the integrated process for the
removal NOM and control disinfection by-products (DBPs) forma-
tion in a local water treatment plant (Kristiana et al., 2011).
Promising results were found as the addition of activated carbons
helped improving the overall removal of NOM by 70%, which led to
a significant reduction in the formation of DBPs (80e95%). None-
theless, a serious issue was raised by the authors related to the
incased formation of brominated DBPs, which are more toxic than
their chlorinated analogues, because the used activated carbons
were not effective in removing bromide ions.
Other types of adsorbents were tested in combination with
different coagulants for the removal of NOM or derivates com-
pounds, mainly humic, fulvic and tannic acids, including biochars
(Jung et al., 2015), nanocrystallined Mg/Al layered double hydrox-
ides (Wu et al., 2013) and carbon nanomaterials (Wang et al., 2010;
Joseph et al., 2012).
3.5.3. Integrated oxidationecoagulation process
Oxidation processes are generally applied prior to the coagula-
tion stage (Uyguner et al., 2007). Thus, the overall efficiency of such
integrated system is highly depending on the qualitative and
quantitative outcome of the oxidative degradation of NOM. With
this respect, and based on the initial composition of NOM and the
applied oxidation process (UV, Fenton and O3-based processes),
various types of intermediates compounds will be present in the
aqueous media to be subjected to coagulation. At this phase, the
structural, molecular and chemical properties of those compounds
will impact several operating conditions including the type of
coagulant to be used, the doses to be applied and the optimum
operating conditions to be adjusted, mainly pH.
In a related study, a combined photocatalytic oxidation/coagu-
lation process was tested for the removal of HA during conventional
drinking water treatment using titanium dioxide P25 as catalyst
and alum as coagulant (Ayekoe et al., 2017). First, the coagulation
process was optimized alone (pH 5 and 110 mg/L for the coagulant
dose) enabling a 70% removal of the humic substances. The appli-
cation of the proposed hybrid system helped increasing the
removal rate of humic substances to 90%, after 220 min of irradi-
ation of the clarified water collected from treatment plant using a
solar UV simulator.
In another study, a hybrid process based on ozonation as pre-
treatment followed by an alum-based coagulation process was
applied to assess its efficiency to remove NOM from natural and
synthetic waters and to reduce THMFP (Rodríguez et al., 2012).
Interestingly, the results showed that the pretreatment of the
natural water (low levels of calcium hardness and hydrophobic
 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71
humic substances) with increasing doses of ozone decreased the
TOC removal rates during the coagulation stage. Indeed, the highest
TOC removal rate (33%) was achieved via coagulation alone. This
negative impact was less pronounced in synthetic solutions, with
the presence of more calcium hardness and humic substances. As
for the formation of DBPs, the ozonation helped reducing THMFP by
5e25% for various ozone doses (0.25e2.5 mg O3/L). This study and
many others clearly reveal the limits of using synthetic solutions to
asses to efficiency and applicability of coagulants in real case sce-
narios involving natural water supplies with highly variable
characteristics.
Even if the application of coagulation after oxidation is highly
depending on the NOM and compositions and is not always effec-
tive, this integrated process still remains an interesting option if we
fully optimize the efficiency of the oxidation stage (as the main
treatment) via various advanced oxidation procedures and then
apply coagulation (as a post treatment) to remove the DBPs formed
during the oxidation process.
3.5.4. Integrated coagulationeion exchange process
Ion exchange is a widely used technique in the field of water
treatment for the adsorptive removal of various charged organic
and inorganic pollutants, with better performance than adsorption
process involving conventional activated carbons and non-ionic
resins (Bolto et al., 2002; Humbert et al., 2008).
During the past 15e20 years, the application of anion exchange
resins for the removal of NOM and humic substances from drinking
water supplies have received considerable attention from re-
searchers around the world (Kitis et al., 2007; Mergen et al., 2008;
Nguyen et al., 2011). In this context, several ion exchangers were
reported including many resins such as DOWEX 11, DOWEX MSA,
IRA938 and IRA958 (Sillanp€ €, 2015; Cornelissen et al., 2008). Some
aa
of them are still commercially available, others not anymore
(Humbert et al., 2005). Nonetheless, the most investigated and
applied resin, so far, remains the magnetic anion exchange resin
MIEX, which is a macroporous polyacrylic matrix in the chloride
form (150e180 mm, that is 2e5 times smaller than conventional
resins), with magnetic iron oxide particles incorporated into the
resin matrix to facilitate the agglomeration and improve the
settling (Boyer and Singer, 2006; Ding et al., 2012).
Recently, numerous research studies focused on the possible
integration of ion exchange, before or after, coagulation in order to
enhance the overall efficiency to remove NOM via such hybrid
system, while reducing the coagulants input and reducing the
formation potential of DBPs and the generated sludge volume
(Singer and Bilyk, 2002; Humbert et al., 2007). Among the recent
research efforts integrating coagulation with ion exchange, an
interesting study was conducted over a 2-year period to assess the
efficiency of a hybrid process involving MIEX and alum for the
treatment of drinking water supplies, with a special attention to
NOM removal (Drikas et al., 2011). Additionally, another integrated
process combining MIEX and microfiltration was also tested. The
related results showed that the application of MIEX as pretreat-
ment enabled the removal of organic matter across a wide range of
AMW. Then, after applying the core treatment techniques (i.e.
coagulation or microfiltration), it was revealed that the integrated
system MIEXecoagulation was the best performing process with
respect to the removal of organics, as the coagulation treatment
was more efficient in removing the organic matter above 1000 Da.
In another comparative study, enhanced coagulation was
coupled with either powdered activated carbon or MIEX (both as
secondary treatment), and each integrated process was assessed for
the removal of DBPs precursors from NOM (Watson et al., 2015).
The main finding was that coupling enhanced coagulation with
67
MIEX resin was the better option for source waters with high
bromide content because it was most effective in mitigating the
formation of brominated DBPs. The authors also stated that for
waters with high iodide content, the ability of MIEX to adsorb this
ionic compound could decrease the formation of iodinated DBPs
upon water disinfection.
Other recent studies confirmed the beneficial incorporation of
MIEX with conventional or enhanced coagulation processes for the
removal of NOM from aqueous media (Xu et al., 2012, 2016b).
Lately, an increasing number of research investigations are being
conducted to couple coagulation with other types of ion exchangers
to remove NOM and other organic pollutants such as AMBERLITE
PW16 and PWA9 (Huang et al., 2015b) and a novel suspended ion
exchange process (Metcalfe et al., 2015).
4. Conclusions and outlook: coagulation for sustainable
water treatment
Natural organic matter is a key component in aquatic environ-
ments. The complex nature of this matrix of organic substances and
its spatiotemporal variations (quantity and composition wise)
constitutes the main challenge facing the various water treatment
techniques applied to remove NOM from drinking water supplies,
and also from municipal wastewater effluents or landfill leachates.
Thus, in order to make the right choice when it comes to the to-be-
applied treatment technology(ies), characterizing NOM and its
various fractions, in the one hand, and predicting their reactivity
with respect to the water chemistry, on the other hand, are crucial
endeavors to reach high removal efficiencies and mitigate the po-
tential formation of toxic byproducts.
The widely-used coagulation process is among the most suitable
water treatment techniques targeting the removal NOM from
drinking water supplies. Several types of coagulants were devel-
oped for this purpose including metal salts, inorganic and organic
(synthetic or natural) polymers and various combinations scenarios
between those coagulants. The basic question in this regard is:
which coagulant is the best for NOM removal? The right answer is:
It depends, because no straight answer could be given unless the
composition of NOM and the properties of the water source are
assessed beforehand. Such key information will help predicting the
potential interaction mechanisms (charge neutralization/precipi-
tation, adsorption, co-precipitation and hetero-coagulation (Davis
and Edwards, 2014)) and propose the most suitable coagulants
accordingly. Nonetheless, for comparative purposes and based on
the research findings collected in Tables 1e5, the highest removal
efficiencies of different categories of coagulants, being alum
(Table 1), ferric (Table 2), polymers (Table 3), biocoagulants
(Table 4), and electrocoagulation (Table 5), are summarized and
semi-quantitatively compared in the following Table 6.
Among the five studied categories of coagulants, the results
summarized in Table 6 from the selected research studies between
2010 and 2016, reveal that the iron-based coagulant Ferripol XL was
the most efficient coagulant to remove NOM with the highest DOC
reduction (80.5%). With 73% and 88% reductions in DOC and UV254,
respectively, the electrocoagulation is showing interesting poten-
tialities for NOM removal, along with its in-situ applicability. As for
the removal of HA, the polymeric coagulant PFS exhibited the best
performance with the simultaneous highest removals of DOC (81%)
and UV254 (94%). Furthermore, the use of algal or bacterial extracts
as coagulant aid to alum is showing promising removal rates of
NOM and HA.
On the other hand, an increasing number of research studies are
focusing on the improvement of NOM removal rates by testing
integrated processes, prone to industrial application, coupling
coagulation with other advanced water treatment technologies. In
68 €a
M. Sillanpa € et al. / Chemosphere 190 (2018) 54e71
Table 6
Indication of the comparative efficacy of the five categories of coagulants considered in this review.
Categories of coagulants Coagulants Targeted organic
compounds
Al-based coagulants Al2(SO4)3 NOM
HA
Iron-based coagulants Ferripol XL NOM
FeCl3 HA
Polymeric coagulants PAC/pDADMAC NOM
PFS HA
Biocoagulants Bacterial exopolysaccharides/ NOM
Alum
Enteromorpha extract/Alum HA
Electrocoagulation Aluminum electrodes and NOM
commercially available DSA
Hot-rolled iron steel anode and NOM
stainless steel cathode
this regard, the use of chitosan as coagulant followed by UF
(transmembrane pressure of 1 bar) is showing promising efficacy as
it enabled the highest reduction of COD (91%), compared to coag-
ulation alone 60% and UF alone (86.7%). Moreover, the application
of a photocatalytic/coagulation hybrid system helped increasing
the removal rate of humic substances to 90%.
Research wise, the major challenge is that most studies are
being conducted using synthetic solutions which makes the
extrapolation of the related results to real case scenarios inade-
quate, provided working with natural waters and real wastewater
effluents, along with further pilot-scale testing. Thus, conducting
coagulation tests on natural waters, either straightaway or after
preliminary tests on synthetic waters, should be the norm for
future studies involving newly developed coagulants, which are
expected to be mostly hybrid or biological ones.
In foreseeable future, the application of coagulation in water
treatment needs to be upgraded to find it place in the two emerging
sustainable concepts of circular economy and bioeconomy. Within
circular economy, the main focus for future R&D studies should be
(i) enhancing the coagulation process without increasing the
coagulant doses but with more efficient hybrid coagulants, and (ii)
the development of efficient and cost-effective schemes to recover
and reuse coagulants. Some recovery options were already re-
ported (Davis and Edwards, 2014; Keeley et al., 2012, 2016) and
more effort needs to be put in this direction.
As for bioeconomy, the production and application of bio-based
polymeric coagulants from plants, algae or microorganisms seem to
be the most viable alternatives towards a sustainable water puri-
fication approach. The major target for related R&D studies should
be the development of biocoagulants able to compete with con-
ventional counterparts, but with enhanced cost-effectiveness and
eco-friendliness.
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