JES-01058; No of Pages 9

J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S X X (2 0 1 7 ) XX XXXX

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Algal removal from cyanobacteria-rich waters by

preoxidation-assisted coagulationflotation: Effect of
algogenic organic matter release on algal removal
and trihalomethane formation

Jr-Lin Lin1 , Lap-Cuong Hua2 , Shih Kai Hung2 , Chihpin Huang2,

1. Department of Environmental Engineering, Chung Yuan Christian University, Taoyuan, Chinese Taipei. Email: jrlin@cycu.edu.tw
2. Institute of Environmental Engineering, National Chiao Tung University, Hsinchu, Chinese Taipei

AR TIC LE I N FO ABS TR ACT

Article history: The cyanobacteria-bloom in raw waters frequently causes an unpredictable chemical
Received 18 November 2016 dosing of preoxidation and coagulation for an effective removal of algal cells in water
Accepted 10 February 2017 treatment plants. This study investigated the effects of preoxidation with NaOCl and ClO2
Available online xxxx on the coagulationflotation effectiveness in the removal of two commonly blooming
cyanobacteria species, Microcystis aeruginosa (MA) and Cylindrospermopsis raciborskii (CR), and
Keywords: their corresponding trihalomethane (THM) formation potential. The results showed that
Algogenic organic matter dual dosing with NaOCl plus ClO2 was more effective in enhancing the deformation of
Preoxidation cyanobacterial cells compared to single dosing with NaOCl, especially for CR-rich water.
Coagulationflotation Both preoxidation approaches for CR-rich water effectively reduced the CR cell count with
Disinfection-by-products less remained dissolved organic carbon (DOC), which benefited subsequent coagulation
flotation. However, preoxidation led to an adverse release of algogenic organic matter
(AOM) in the case of MA-rich water. The release of AOM resulted in a poor removal in MA
cells and a large amount of THM formation after oxidation-assisted coagulationflotation
process. The reduction in THM formation potential of CR-rich waters is responsible for effective
algae and DOC removal by alum coagulation. It is concluded that the species-specific
characteristic of cyanobacteria and their AOM released during chlorination significantly
influences the performance of coagulationflotation for AOM removal and corresponding
THM formation.
2017 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences.
Published by Elsevier B.V.

Introduction et al., 2016). The sudden excessive growth of algae in reservoirs

Algae proliferation in reservoirs frequently constrains the unit
operation in drinking water treatment plants (DWTPs) because
of their vast increase in not only cell population but also
algogenic organic matter (AOM) as a byproduct during algal
photosynthesis and the lysis of senescent algal cells (Pivokonsky
excessively burdens water purification units, with subsequent
deterioration of water quality. Algal proliferation causes drastic
changes in turbidity, pH, taste and odor, and the amount of
organic matter in treated water (Coral et al., 2013). For instance,
when strip or needle algae, such as the diatom Syendra acus,
appears in the raw water, it frequently challenges the operation

Corresponding author. E-mail: cphuang@mail.nctu.edu.tw (Chihpin Huang).

http://dx.doi.org/10.1016/j.jes.2017.02.007
1001-0742 2017 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.

Please cite this article as: Lin, J.-L., et al., Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation
flotation: Effect of algogenic organic matter re..., J. Environ. Sci. (2017), http://dx.doi.org/10.1016/j.jes.2017.02.007
2 J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S X X (2 0 1 7 ) XXX XXX
of coagulationsedimentation unit because of its very poor
settling rate (Henderson et al., 2008). Consequently, the
deep-bed filter is easily blocked by the algae, leading to an
increase in the frequency of backwashing (Joh et al., 2011).
Furthermore, because of some algae and cyanobacteria release
neurotoxins and biotoxins during metabolism, they are of
concern about the safety of drinking water (Landsberg, 2002;
Wang et al., 2013). An effective approach to the pretreatment of
algae-rich waters is thus crucial in overcoming the challenges
posed by algae proliferation at DWTPs.
Coagulation is a traditional process to destabilize algae and
enhance the algal removal with Al-based coagulant or chitosan-
based flocculants (Lin et al., 2015, 2016; Shi et al., 2016). In
practice, the coupling process of coagulation and dissolved air
flotation (DAF) has been widely employed to remove algae from
algae-rich waters (Edzwald, 1993; Teixeira and Rosa, 2006;
Henderson et al., 2009, 2010). In this coupling process, coagu-
lated particles are attached by microbubbles, then removed by
turbulent flotation (Rulyov, 2001). It is an essential process to
destabilize algal cells that are then removed by the attachment
of microbubbles to algal flocs (Edzwald, 1993). Compared to
sedimentation, DAF is a more powerful process for the removal
of blue-green and green algae from raw waters (Teixeira and
Rosa, 2006; Henderson et al., 2010). Even in the presence of
natural organic matter (NOM), DAF still accounted for more
than 90% of the removal of Microcystis aeruginosa with optimum
coagulant dosing (Teixeira and Rosa, 2007).
However, when algae bloom, preoxidation with sodium
hypochlorite, chlorine dioxide, or ozone is often required
as a further pretreatment step prior to coagulation for the
effective removal of algae by either flotation or sedimentation.
Preoxidation enhances the destabilization of algal cells,
resulting in the reduction of the coagulant dosage required
(Henderson et al., 2008). Unfortunately, this may also induce the
release of AOM from the ruptured cells (i.e., intracellular organic
matter (IOM)) (Ma et al., 2012a), which results in negative
impacts on subsequent treatment units and worsens the
quality of finished drinking water (Ma et al., 2012b; Zhou et al.,
2014; Lin et al., 2015). For instance, in the case of algae
destabilization by coagulation, the released AOM with a high
ratio of proteins favors forming the proteinalum complex that
substantially inhibits the destabilization of algal cells (Takaara
et al., 2010). This phenomenon results in increasing coagulant
consumption and impairs the performance of subsequent
solidliquid separation units (Takaara et al., 2007; Ma et al.,
2012b). Importantly, AOM comprises of various substances,
such as amino acids, polysaccharides, and other small molec-
ular acids, which is highly hydrophilic (Leloup et al., 2013) and
not amendable to coagulation (Pivokonsky et al., 2016). AOM has
been well proved as a potential precursor to disinfection
byproducts (DBPs) (Nguyen et al., 2005). The rapid release of
AOM by excessive preoxidation would elevate severe DBP
formation potential (DBPFP) in drinking water. Furthermore,
because the physical and chemical properties of algal species
vary widely between species (Henderson et al., 2008), it is difficult
to control chemical dosing for preoxidation and coagulation in
DWTPs so as to control such algae-derived DBP formation.
Hence, an appropriate dosing approach of preoxidation and
coagulation for various algae-rich waters is pivotal for the
performance of DWTPs.
Please cite this article as: Lin, J.-L., et al., Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation
flotation: Effect of algogenic organic matter re..., J. Environ. Sci. (2017), http://dx.doi.org/10.1016/j.jes.2017.02.007
In Taiwan, sodium hypochlorite (NaOCl) is commonly
used among chlorine-based disinfectants for the preoxidation
because preoxidation with NaOCl is a simple and cost-
effective approach as well as has a strong ability to deactivate
algae (Lin et al., 2016). NaOCl preoxidation destroys algal cells
by the diffusion of HOCl and OCl at neutral pH to rupture the
cells (Peterson et al., 1995). Although preoxidation with NaOCl
can impair cell viability and deteriorate the chemosphere of
cyanobacteria M. aeruginosa (Ma et al., 2012b) or of green algae
Pediastrum simplex cells, it may fail to rupture the thick cell-
wall of algae such as diatom Cylotella sp. (Lin et al., 2016).
Furthermore, DWTPs in the outside islands of Taiwan often face
to the dramatic increase in the cell population (106107 cells/mL)
with a high concentration of dissolved organic matter (>20 mg/L)
during summer times; NaOCl preoxidation might be insufficient
to pretreat such a great number of algal cells. Consequently, the
extra dosing of NaOCl is required, but it would cause a severe
formation of DBPs, where trihalomethanes (THMs) concentration
in finished water in DWTPs easily exceeds the regulated
concentration. On the other hand, ClO2 preoxidation does not
induce the THM formation (Kim et al., 2015), and it has stronger
oxidative ability than NaOCl to lyse most of the algal cells of
various species (Zhou et al., 2014; Lin et al., 2015, 2016). However,
because ClO2 is an explosive gas and unstable chemicals, it is
only used as an additional dosage along with NaOCl when
severe algal eutrophication occurs.
To date, a few studies have highlighted the impact of
preoxidation-assisted coagulationflotation on the removal of
algal cells from various algae-rich waters (Edzwald, 1993; Teixeira
and Rosa, 2006; Henderson et al., 2009, 2010). However, there is
very limited information about the fate of the released AOM
during preoxidation with dual dosing (NaOCl + ClO2) for natural
algal-rich water treatment, and its impacts on algae removal by
coagulationflotation and the corresponding THM formation
potential (THMFP). This study aimed to investigate the effects of
preoxidation with dual dosing (NaOCl + ClO2) on coagulation
flotation for the removal of algal cells from two natural
cyanobacteria-rich waters containing M. aeruginosa (MA) and
Cylindrospermopsis raciborskii (CR). The effect of AOM release
during preoxidation on the corresponding THMFP was also
evaluated.
1. Materials and methods
1.1. Characteristics of algae-rich waters
Natural cyanobacteria-rich waters predominantly containing
MA and CR (90% cell population) were collected from Tai-Hu
and Tian-Pu reservoirs in Kimmen, Taiwan with initial pH
values of 7.15 and 7.52, respectively. To identify algal species
and cell counts, water samples were placed in a hemocytometer
(Neubauer-improved, Marienfeld, Germany). The number of
cells was then determined by a light microscope (ExwaveHAD,
Sony, Japan). Only intact cells were counted in this study; cell
fragments after treatment were not considered in the count.
The turbidity of the water was determined using a turbidity
meter (2100P, Hach, USA) and the pH with a pH meter (InoLab
Multi Level, WTW, Germany). The total organic carbon (TOC)
and dissolved organic carbon (DOC) of water samples were
 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S X X (2 0 1 7 ) XX XXXX 3

determined by a TOC analyzer (TOC-5000A, Shimadzu, Japan). All
data were determined in triplicate measurements. The charac-
teristics of the MA- and CR-rich waters are given in Table 1.
1.2. Preoxidation-assisted coagulationflotation protocol
Bench scale preoxidation-assisted coagulation followed by
microbubble flotation was conducted with a jar tester (Lighter
Co., Taiwan) coupled to a regenerative turbine pump (Nikuni,
Japan). For investigating the effect of preoxidation on the
release of AOM, a single dosing of NaOCl and dual dosing of
NaOCl and ClO2 were applied to coagulationflotation, with
mixing for 1 min at 200 r/min (G = 350 sec1). The total
oxidant dosage of 1 mg/L was conducted following the
practical dosing in DWTP. Preoxidation with a single dosing
was carried out with 1 mg/L as Cl of NaOCl, while
preoxidation with dual dosing was conducted with NaOCl
and ClO2 in the ratios of 1:1 (0.5 mg/L/0.5 mg/L as Cl) and 1:2
(0.33 mg/L/0.67 mg/L as Cl), respectively. After chlorination,
coagulation at different dosages of alum (Al2(SO4)318H2O) was
carried out at a rapid mixing at 200 r/min (G = 350 sec1) for
1 min, followed by a slow mixing at 30 r/min (G = 25 sec1) for
15 min. The suspension flowed to a flotation tank at a flow rate
of 0.4 L/min. The remained algal cells and AOM were further
removed by microbubbles at a pressure of 3.8 kg/cm2. After
coagulationflotation, suspensions were immediately with-
drawn to determine their residual cell count, turbidity, and
DOC. Fluorescence excitationemission matrix (EEM) and
high-performance size-exclusion chromatography (HP-SEC)
were also used to determine the variation of chemical compo-
nents and molecular weight distribution of suspension of each
step. Furthermore, the concentrations of THMs were deter-
mined by gas chromatographmass spectrometry (GCMS) to
quantify the DBPFP of the supernatants.
1.3. Fluorescence EEM
Water samples were analyzed after preoxidation and flotation
by the EEM to determine the chemical composition of the
organic matter. Three millimeter water samples were
measured with a Cary Eclipse fluorescence spectrophotome-
ter (Varian Inc., Palo Alto, USA). All water samples were
adjusted to pH 7.0 0.1 and then filtered through 0.45 m
Polytetrafluoroethylene (PTFE) membranes before each EEM
scan. EEM spectra were collected by increasing the scanning
emission range from 250 to 600 nm with 2 nm increments.
The excitation wavelength ranged from 200 to 500 nm with
10 nm increments. The fluorescence of water samples was
determined at a scanning rate of 1200 nm/min by using
excitation and emission slit bandwidths of 5 nm. The voltage
of the photomultiplier tube was set to 800 V for low-level light
detection. For each test, the EEM spectra of water samples
were subjected to four fluorescent regions with excitation/
emission wavelengths (Ex/Em) of 350/435450, 250280/425,
280285/340350, and 220230/340350 nm, representing the
humic-like (region II), fulvic-like (region III), protein-like
(region I), and aromatic protein-like substances (region IV)
(Chen et al., 2003). According to these four regions, the average
fluorescent intensities (AFIs, a.u) were calculated for each
substance category.
1.4. HP-SEC
HP-SEC system was used to compare the molecular weight
differences in the organic matter of water samples after
preoxidation and after flotation. HP-SEC was carried out using
a degasser (DEGASYS DG-1310, Uniflows Co. Ltd., Japan), a feed
pump (BETA 10 Gradient pump, Ecom spol. s.r.o., Czech
Republic), a chromatography column (TSK G2000SWx1, TOSOH
Co., Tokyo, Japan), and two on-line detectors, a
ultraviolet-visible (UV-vis) variable wavelength detector (SAP-
PHIRE 600, Ecom spol. s.r.o., Czech) and a refractive index
detector (IOTA 2, Precision Instruments, France). The two
detectors were connected in series and controlled by software
Peak-ABC. The feed pump was set at a flow rate of 1 mL/min.
Water samples were adjusted to pH 7.0 0.1 and then filtered
with 0.45 m PTFE membranes before HP-SEC analysis. Poly-
ethylene glycols (PEG, 200, 1000, 4000, 8000 and 20,000 Da) were
used to calibrate the apparent molecular weight. The absorp-
tion wavelength of the UV detector was set at 254 nm.

Table 1 Characteristics of Microcystis aeruginosa (MA) and Cylindrospermopsis raciborskii (CR)-rich waters with and without
oxidation.
Without NaOCl + ClO2 NaOCl + ClO2
Water sample Parameter oxidation NaOCl (1:1) (1:2)

MA-rich water Nephelometric Turbidity Units 7.89 0.15 7.38 0.13 6.84 0.22 7.03 0.41
(NTU)
Cell count (cells/mL) 5300 990 3700 250 3900 310 3100 420
DOC (mg/L) 9.12 0.16 10.03 0.21 11.47 0.19 11.43 0.51
TOC (mg/L) 12.39 0.06 12.04 0.08 12.23 0.26 12.06 0.13
Specific POC (g/L/cell) 0.617 0.543 0.195 0.203
CR-rich water Turbidity (NTU) 25.57 1.03 22.43 0.94 21.07 1.22 21.65 1.08
Cell count (cells/mL) 88,000 7700 74,000 65,700 4200 36,2505800
5500
DOC (mg/L) 17.45 0.25 17.51 0.15 17.96 0.31 17.92 0.25
TOC (mg/L) 21.09 0.12 20.89 0.08 20.83 0.15 20.60 0.06
Specific POC (g/L/cell) 0.041 0.046 0.044 0.074

Specific POC (g/L/cell) = (TOC DOC) / cell count; all data was determined in the triplicate analysis.
DOC: dissolved organic carbon; TOC: total organic carbon; POC: particulate organic carbon.

Please cite this article as: Lin, J.-L., et al., Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation
flotation: Effect of algogenic organic matter re..., J. Environ. Sci. (2017), http://dx.doi.org/10.1016/j.jes.2017.02.007
4 J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S X X (2 0 1 7 ) XXX XXX

Table 2 AFI EEM spectra for MA- and CR-rich waters with and without oxidation.
Water sample Fluorescence region Without oxidation NaOCl NaOCl + ClO2 (1:1) NaOCl + ClO2 (1:2)

MA-rich water SMP-like 34.43 31.88 38.26 33.00

Humic-like 40.39 41.31 40.62 41.28
Fulvic-like 72.42 24.01 33.83 37.86
Aromatic protein-like 42.04 11.49 19.72 17.18
CR-rich water SMP-like 31.93 22.06 25.81 18.91
Humic-like 34.92 31.16 33.77 25.75
Fulvic-like 51.79 48.37 50.86 38.05
Aromatic protein-like 27.53 21.06 23.55 17.29

AFI: average fluorescent intensity (au.); EEM: excitationemission matrix; SMP: soluble microbial products.

8 26
a MA-rich water NaOCl b CR-rich water
24 NaOCl
NaOCl+ClO 2 (1:1) NaOCl+ClO 2 (1:1)
Residual turbidity (NTU)

Residual turbidity (NTU)

NaOCl+ClO 2 (1:2) 22 NaOCl+ClO 2 (1:2)

20
6
18

16
5

14

4 12

5000 10
-5 -5
Alum dosage (x10 as Al) 80000 Alum dosage (x10 as Al)
4000
Algal count (cells/mL)

Algal count (cells/mL)

60000
3000

40000
2000

1000 20000

18
-5 24 -5
Alum dosage (x10 as Al) Alum dosage (x10 as Al)
16 22

20
DOC (mg/L)

DOC (mg/L)

14
18

12 16

14
10
12

8 10
0.0 3.7 7.4 11.1 14.8 0.0 3.7 7.4 11.1 14.8
-5
Alum dosage (x10 mol/L as Al) -5
Alum dosage (x10 mol/L as Al)

Fig. 1 Variation of residual turbidity, cell count, and DOC with alum dosage in oxidation-assisted coagulationflotation for
Microcystis aeruginosa (MA) and Cylindrospermopsis raciborskii (CR)-rich waters.

Please cite this article as: Lin, J.-L., et al., Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation
flotation: Effect of algogenic organic matter re..., J. Environ. Sci. (2017), http://dx.doi.org/10.1016/j.jes.2017.02.007
 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S X X (2 0 1 7 ) XX XXXX 5

1.5. GCMS for THM analysis
The formation potentials of four major THMs (e.g., chloroform
(TCM), bromoform (TBM), bromodichloromethane (BDCM),
and dibromochloromethane (DBCM)) were determined using
GCMS (Agilent 6890GC/5970MSD, Cary, NC), following Envi-
ronmental Protection Agency (EPA) method 524.2. The chlorine
of each sample was spiked to 5 times DOC with sodium
hypochlorite. All samples were adjusted to pH 7.0 0.1 and
stored in headspace-free amber glass bottles at room tempera-
ture. After 7 days the water samples were acidified and
quenched with ammonium chloride to obtain THMFP.
2. Result and discussion
2.1. Effect of preoxidation on the algal cell degradation and
AOM release
The deterioration of algal cells and the release of AOM by
preoxidation directly influence coagulation (Chen et al., 2009;
Henderson et al., 2010). The effects of preoxidation with single
dosing (NaOCl) and dual dosing (NaOCl + ClO2) on the cell
removal and DOC release were first investigated. Table 1
shows that preoxidation with single and dual dosing
markedly reduced the turbidity and cell count in the super-
natant in both MA and CR-rich waters.
In this study, CR cells are generally elongated (40130 m in
length) with a thick cell-wall (25 m in width), while MA cells
are spherical, 37 m in diameter. It is likely that most CR cells
were split into fragments by the preoxidation, while MA cells
were attacked, accompanied by the release of AOM. The
reduction of turbidity and cell count by dual dosing preoxidation
(NaOCl:ClO2 = 1:2) was more pronounced compared to single
dosing (NaOCl), especially in the case of CR-rich water. It is
attributed to the stronger oxidative ability of ClO2 to attack the
intact algal cells compared to NaOCl (Lin et al., 2015, 2016). Thus,
the dual dosing resulted in greater decreased in algal cell counts.
Although the number of affected cells in CR-rich water was
remarkably higher than in MA-rich water, the residual DOC in
CR-rich water changed negligibly after preoxidation with either
single or dual dosing, whereas the residual DOC increased in the
case of MA-rich water, as shown in Table 1. The content of
specific particulate organic carbon (POC) (i.e., (the amount of
TOC the amount of DOC) / total algal cell counts) for each
cell in the MA-rich water (0.617 g/L per cell) was markedly
higher compared to CR-rich water (0.041 g/L per cell) before
preoxidation. With preoxidation, even though single or dual
dosing significantly reduced the number of algal cells in CR-rich
water from approximately 88,000 to 36,250 cells/mL, only a
trace amount of DOC was released. By contrast, it destroyed the

Preoxidation Preoxidation + Coagulation-flotation

a MA-rich water NaOCl NaOCl
50 NaOCl+ClO2 (1:1) NaOCl+ClO2 (1:1)
NaOCl+ClO2 (1:2) NaOCl+ClO2 (1:2)

40
AFI (a.u.)

30

20

10

0
b CR-rich water
50

40
AFI (a.u.)

30

20

10

0
SMP-like Humic-like Fulvic-like Protein-like SMP-like Humic-like Fulvic-like Protein-like

Fig. 2 Fractionation of EEM spectra of MA- and CR-rich waters after coagulationflotation at the optimum dosage with and
without preoxidation. Dosage: 7.4 105 mol/L as Al.

Please cite this article as: Lin, J.-L., et al., Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation
flotation: Effect of algogenic organic matter re..., J. Environ. Sci. (2017), http://dx.doi.org/10.1016/j.jes.2017.02.007
6 J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S X X (2 0 1 7 ) XXX XXX

algal cells in MA-rich water to release more amount of DOC
compared to CR-rich water.
To further understand the characteristics of the released
AOM in water after preoxidation, EEM fluorescence spectra of
the organic substances in MA-rich and CR-rich waters before
and after preoxidation were investigated. Table 2 gives EEM
spectra for four fluorescent regions. After preoxidation, the
dissolved organic matter (DOM) in two cyanobacteria-rich
waters contained a large amount of protein-like and fulvic-like
substances along with a few humic-like substances, similar to
that reported in a previous study (Lin et al., 2015). Detailed
examination of DOM fluorophores showed that all fractionated
intensities for CR-rich water had been slightly reduced, while
only the intensities of fulvic-like and protein-like substances for
MA-rich water had been substantially reduced. In the case of
MA-rich water, preoxidation with single dosing (NaOCl) or dual
dosing (NaOCl + ClO2) markedly degraded the protein-like sub-
stances because NaOCl preferentially reacts with organic nitrog-
enous substances and degrades their structure (Deborde and von
Gunten, 2008). Moreover, because most of the fulvic-like sub-
stances were in the MA-rich water, they reacted with oxidants
during preoxidation with either single or dual dosing. The
decreased intensity of both fulvic-like and protein-like sub-
stances was more significant during preoxidation with single
dosing than that with dual dosing. However, only the intensity of
humic-like substances did not decrease after preoxidation of
MA-rich water. These results are in agreement with a previous
study (Ou et al., 2011), where a rapid increase of humic-like
substances was accompanied by the gradual decrease in
protein-like fluorescent during the chlorination of MA cells.
It could be concluded that the algal cells in MA-rich water
would tremendously contribute fluorescent matter that affects
coagulationflotation performance for algae removal.
2.2. Effect of preoxidation on algae and DOC removal by
coagulationflotation
Although algal cells can be amenable to coagulation, coagu-
lation is always constrained by AOM in water (Henderson
et al., 2010; Pivokonsky et al., 2016). After preoxidation the
behavior of released AOM in MA-rich and CR-rich waters
would indirectly influence the coagulant consumption and
AOM destabilization. Consequently, the effects of the release
of AOM after perpreoxidation on coagulationflotation was
further investigated. Fig. 1 shows that, at an optimum Alum
dosage (7.4 105 mol/L as Al), preoxidation with dual dosing
prior to alum coagulationflotation effectively enhanced
the destabilization of algal cells compared to single dosing
(NaOCl), leading to a sufficient reduction of turbidity and
removal of algal by flotation. For instance, approximately 95%
of cells was removed from CR-rich water, while only 75% of
cells was removed from MA-rich water by pretreatment of
dual dosing preoxidation (NaOCl:ClO2 = 1:2). However, the
residual DOC in treated MA-rich water was higher than before

Preoxidation Preoxidation + Coagulation-flotation

160
aMA-rich
MA-richwater
water CR-rich water
140
Without preoxidation NaOCl
120
NaOCl NaOCl+ClO2 (1:1)
NaOCl+ClO2 (1:1) NaOCl+ClO2 (1:2)
100 NaOCl+ClO2 (1:2)
Intensity (a.u.)

80

60

40

20

0
30
b CR-rich water
25

20
Intensity (a.u.)

15
CR-rich water

10

1e+0 1e+1 1e+2 1e+3 1e+4 1e+5 1e+6 1e+7 1e+0 1e+1 1e+2 1e+3 1e+4 1e+5 1e+6 1e+7

Apparent molecular weight (Da) Apparent molecular weight (Da)

Fig. 3 Molecular weight distribution of MA- and CR-rich waters before and after coagulationflotation at the optimum dosage
with and without preoxidation. Dosage: 7.4 10 5 mol/L as Al.

Please cite this article as: Lin, J.-L., et al., Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation
flotation: Effect of algogenic organic matter re..., J. Environ. Sci. (2017), http://dx.doi.org/10.1016/j.jes.2017.02.007
 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S X X (2 0 1 7 ) XX XXXX 7

coagulation, even though higher alum dosage had been
applied. By contrast, the residual DOC in treated CR-rich
water was reduced significantly. Because of the AOM released
from the ruptured MA cells, this inhibited the destabilization of
DOM. The fewer DOM released after preoxidation, the smaller
the increase in DOC in treated for CR-water. The preoxidation
reaction between algal species and oxidants thus significantly
influences the performance of coagulationflotation for algae
removal.
Fig. 2 shows that the coagulationflotation of MA-rich
and CR-rich waters enhanced reducing the intensities of
humic-like, fulvic-like, and SMP-like substances, while the
intensity of aromatic protein-like substances was scarcely
changed in the EEM spectra. It has been reported that large DOM
with more than 10 kDa is easily destabilized by coagulation,
while the small DOM with less than 1 kDa, mostly nitrogenous
organic matter, inhibits coagulation (Takaara et al., 2007;
Pivokonsky et al., 2016). Furthermore, DOM with aromatic or
aliphatic functional groups preferentially reacts with Al species
in coagulation and then destabilizes DOM by complexation or
co-precipitation (Lin et al., 2014). The large carbonaceous organic
substances (humic-like and fulvic-like) and nitrogenous sub-
stances (SMP-like) in MA-rich and CR-rich waters were therefore
effectively removed by preoxidation-assisted coagulationflota-
tion, while small aromatic protein-like substances remained
unchanged.
The distribution of molecular weight of DOM before and
after preoxidation-assisted coagulationflotation was also
analyzed using an HP-SEC coupled with a UV254 detector to
verify the effect of preoxidation on the release of AOM and the

a MA-rich water b CR-rich water

1400 NaOCl TCM 5000 NaOCl TCM
BDCM BDCM
1200 DBCM
DBCM TBM
TBM 4000
1000 THMFP (mg/L)
THMFP (mg/L)

800 3000

600
2000

400
1000
200

0 0
1400
NaOCl+ClO2 (1:1) 5000 NaOCl+ClO2 (1:1)
1200
4000
1000
THMFP (mg/L)
THMFP (mg/L)

800 3000

600
2000

400
1000
200

0 0
1400 NaOCl+ClO2 (1:2) 5000 NaOCl+ClO2 (1:2)
1200
4000
1000
THMFP (mg/L)
THMFP (mg/L)

800 3000

600
2000

400
1000
200

0 0
0.0 3.7 7.4 11.1 14.8 0.0 3.7 7.4 11.1 14.8
-5 -5
Alum dosage (x10 mol/L as Al) Alum dosage (x10 mol/L as Al)

Fig. 4 The corresponding trihalomethane (THM) formation potential (THMFP) of supernatant after coagulationflotation with
different peroxidation strategies for MA- and CR-rich waters.

Please cite this article as: Lin, J.-L., et al., Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation
flotation: Effect of algogenic organic matter re..., J. Environ. Sci. (2017), http://dx.doi.org/10.1016/j.jes.2017.02.007
8 J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S X X (2 0 1 7 ) XXX XXX
DOM removal by coagulationflotation, as shown in Fig. 3. In
the case of MA-rich water, preoxidation with single and dual
dosing significantly caused the release of large molecular
weight (MW) AOM from algal cells, resulting in an increase in
DOM molecules of more than 5 kDa. This released DOM was
then partially removed by coagulationflotation (Fig. 3a). For
CR-rich water, the larger DOM molecules of more than 1 kDa
were effectively removed after coagulationflotation, but
smaller DOM molecules (<1 kDa) were still remained (Fig. 3b).
It is likely that the remained DOM predominantly comprised
humic-like substances, as shown in Table 2. Furthermore, the
molecular weight distribution of DOM implies that dual dosing
was more effective in removing DOM molecules of more than
10 kDa than single dosing. In summary, the reduction of DOM
and algal cells in cyanobacteria-rich waters strongly depends on
the quantities and component of AOM release during
preoxidation.
2.3. Effect of preoxidation on THMFP of cyanobacteria-rich
waters
The algae-derived organic matter is recognized as one of the
important THM precursors of DBP (Huang et al., 2009). THMFP of
algae-rich water can be effectively reduced by coagulation
flotation (Chu et al., 2011). However, the characteristics of AOM
released from algal cells during preoxidation strongly affect the
performance of coagulationflotation for algae and DOC removal,
and which directly regulate the variation in THMFP of algae-rich
water after treatment. The variation in THMFP of MA-rich and
CR-rich waters after preoxidation-assisted coagulationflotation
was determined and is shown in Fig. 4. The THMFP of MA-rich
supernatant by preoxidation with single dosing (NaOCl) or dual
dosing (NaOCl + ClO2) was insensitive to alum dosage (Fig. 4a). By
contrast, the THMFP of CR-rich supernatant rapidly declined with
increasing alum dosage (Fig. 4b). Furthermore, the reduction in
THMFP in the preoxidation of MA-rich water was independent
of single or dual dosing, while THMFP was significantly reduced
by preoxidation with dual dosing (NaOCl + ClO2) in the case
of CR-rich water. The discrepancies in THMFP between MA-
and CR-rich waters are primarily caused by the content and
characteristics of AOM released during preoxidation. The more
AOM releases by preoxidation, the more THM precursors are
ineffectively removed by coagulationflotation processes. The
appropriate preoxidation for suitable algae-laden waters is
thus crucial in controlling THMs. These results also suggested
that the integration of dual dosing preoxidation coupled with
coagulationflotation might further minimize the THMFP of
treated water.
Two cyanobacteria-rich water samples were collected near
the coastal area, where a certain amount of Br ions (up to 0.1 mg/
L) is present in the raw water. In this instance, the precursors of
Br-THM (i.e., BDCM, DBCM, and TBM) in MA-rich and CR-rich
waters were ineffectively reduced by preoxidation-assisted
coagulationflotation, even at high alum dosage. Because
these precursors are hydrophilic molecules with low molecular
weight, alum coagulation is not able to effectively destabilize
them (Pivokonsky et al., 2016; Zhao et al., 2016). Small DOM
molecules thus cannot be effectively removed by coagulation
flotation, and supernatant still contains the bromine-carried
THM precursors.
Please cite this article as: Lin, J.-L., et al., Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation
flotation: Effect of algogenic organic matter re..., J. Environ. Sci. (2017), http://dx.doi.org/10.1016/j.jes.2017.02.007
3. Conclusions
Preoxidation with single dosing (NaOCl) and dual dosing
(NaOCl + ClO2) is effective in reducing the algal cells from
both cyanobacterial-rich waters, but ruptures the cells at
different levels, causing the differential release of AOM from
algal cells in MA-rich and CR-rich waters. Preoxidation
deforms the algal cells and increases the residual DOC in
MA-rich water, while the DOC in CR-rich water is insensitive
to preoxidation. After preoxidation the quantities and com-
position of the released AOM strongly affect the performance
of coagulationflotation. The released AOM from algal cells in
MA-rich water cause poor DOC removal by coagulation
flotation as well as increased THMFP. On the other hand,
the corresponding THMFP derived from coagulated CR-rich
water can be controlled by high alum dosages. Compared to
single dosing, dual dosing is more effective in assisting algal
destabilization by coagulationflotation, lowering the resid-
ual THMFP, especially for CR-rich water. It is concluded that
the oxidant-species interaction greatly influences the per-
formance of preoxidation-assisted coagulationflotation for
algae, and that released AOM removal that directly controls
the corresponding THMFP.
Acknowledgments
We gratefully thank the National Science Council of Taiwan
(No. NSC102-2119-M-002-008) for the financial support. We
also appreciate the Kimmen Water Treatment Plant for the
help in water sampling.
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