Environ Sci Pollut Res (2017) 24:1757–1768

DOI 10.1007/s11356-016-7813-8

RESEARCH ARTICLE

Titanium tetrachloride for silver nanoparticle-humic acid

composite contaminant removal in coagulation-ultrafiltration
hybrid process: floc property and membrane fouling
Yanxia Zhao 1,2 & Yangyang Sun 3 & Chang Tian 4 & Baoyu Gao 3 & Yan Wang 3 &
Hokyong Shon 5 & Yanzhao Yang 2

Received: 15 August 2016 / Accepted: 29 September 2016 / Published online: 29 October 2016
# Springer-Verlag Berlin Heidelberg 2016

Abstract Titanium-based coagulation is expected to achieve
both efficient water purification and sludge recycling. This
study is the first attempt to use titanium tetrachloride (TiCl4)
for silver nanoparticle (AgNP)-humic acid composite contam-
inant removal in a coagulation-ultrafiltration (C-UF) process,
where characterization of flocs and membrane fouling under
varied coagulant dose, initial solution pH, and AgNP concen-
tration conditions are the main contents. Results suggested
that the TiCl4 achieved high AgNP removal in the form of
silver nanoparticle through adsorption and sweep flocculation
and simultaneously exerted additional 68.2 % higher dis-
solved organic carbon removal than Al2(SO4)3. The TiCl4
produced larger and stronger flocs but with weaker
recoverability and less compact degree than did Al2(SO4)3.
Floc properties were independent of AgNP concentration ex-
cept floc fractal dimension, which was negatively correlated
with AgNP concentration. The TiCl4 precoagulation caused
less membrane fouling within wider pH range than Al2(SO4)3
did in the C-UF process. Incorporation of AgNPs during the
TiCl4 pretreatment process facilitated the mitigation of mem-
brane fouling, which was, however, negligibly influenced by
AgNP concentration in the case of Al2(SO4)3.
Keywords Titanium tetrachloride . Silver nanoparticles .
Coagulation-ultrafiltration . Floc characteristics . Membrane
fouling

Responsible editor: Bingcai Pan

Electronic supplementary material The online version of this article
(doi:10.1007/s11356-016-7813-8) contains supplementary material,
which is available to authorized users.
* Yan Wang
wangyan_sdjn@aliyun.com
1
Department of Civil Engineering, Faculty of Engineering, The
University of Hong Kong, Pokfulam Road, Hong Kong, China
2
Key Laboratory for Special Functional Aggregated Materials of
Education Ministry, School of Chemistry and Chemical Engineering,
Shandong University, Jinan 250100, China
3
Shandong Key Laboratory of Water Pollution Control and Resource
Reuse, School of Environmental Science and Engineering, Shandong
University, No.27 Shanda South Road, Jinan 250100, People’s
Republic of China
4
School of Environmental Science and Engineering, Qilu University
of Technology, Jinan 250353, China
5
Centre for Technology in Water and Wastewater, School of Civil and
Environmental Engineering, University of Technology, (UTS),
P.O. Box 123, Broadway, Sydney, NSW 2007, Australia
Introduction
The increasing use of engineered inorganic nanoparticles
(EINP) in industrial and agriculture leads to the unintended
nanoparticles (NP) release in water environment. Silver nano-
particles (AgNPs), as one of the most widely used EINP, are
increasingly used in consumer goods (Sun et al. 2013), such as
food packaging, clothing, cleaning agents, and especially
medical products (for treating or preventing diseases (Fuwu
et al. 2015)). The AgNPs have long been reported to have
excellent antimicrobial activities (Maneerung et al. 2008) be-
cause of silver ion release (Okkyoung and Zhiqiang 2008).
Nowadays, the inevitable release of AgNPs to water environ-
ment (Nowack 2010) due to its widespread use makes its
potential adverse effect on human health and environment a
great concern (Wijnhoven et al. 2009). The AgNPs are toxic to
cells (Carlson et al. 2008), bacteria (Zong-Ming et al. 2011),
and algae (Miao et al. 2010), and therefore, may pose a risk to
microorganisms, animals, and humans alike (Farré et al.
2010). Efficient removal of AgNPs from water environment
1758
is crucial to control the environmental and health risks asso-
ciated with their exposure.
Coagulation is regarded as a key step for efficient and
cost-effective removal of suspended solids, colloidal par-
ticles, natural organic matter (NOM), and other soluble
inorganic compounds (Jiang 2015). Aluminum and iron
coagulants are widely utilized in conventional water and
wastewater treatment (Zhao et al. 2011b). Several inves-
tigations have been conducted to study the NP separation
from aquatic environment through aggregation, such as
SiO 2 NPs (Li 2013), CuO NPs (Wang et al. 2015),
nano-TiO2 (Kinsinger et al. 2015), and carbon NPs (ful-
lerene (Hoon and Jae-Hong 2009) and carbon nanotubes
(CNTs) (Ni et al. 2012)). The AgNP removal by coagula-
tion has also been validated by using four conventional
coagulants (aluminum sulfate, ferric chloride,
polyaluminum chloride, and polyferric sulfate) (Sun
et al. 2013). However, the application of conventional
aluminum and iron coagulants has two main drawbacks:
(i) the suspected harmful influence of aluminum coagu-
lants on human and living organisms (Cheng and Chi
2002) and (ii) the generation of a large amount of coagu-
lated sludge, which requires further disposal/dumping ei-
ther at landfills or into the ocean (Zhao et al. 2011b).
Secondary contamination (e.g., landfill leachate and soil
contamination) resulting from the landfill of chemical
sludge makes this method not acceptable, while the coast-
al environmental problems restrict sludge dumping into
the ocean (Lee et al. 2009). These disadvantages promote
the research and development of alternative coagulants to
conventional aluminum and iron coagulants.
Considerable attention has recently been paid to the
application of titanium-based coagulants for water purifi-
cation. Upton and Buswell (1937) first observed the ad-
vantage of titanium sulfate over conventional aluminum
sulfate for fluoride and colority removal. Coagulation ef-
fectiveness of titanium-based coagulants has, since then,
been gradually proved in terms of particle, nutrients, and
NOM removal (Shon et al. 2009b, Yousef 2009). Shon
et al. (2007) found that titanium tetrachloride achieved
high organic matter removal to the same extent as Al
and Fe salts for sewage wastewater treatment, with the
coagulated flocs having better settle ability. Greater re-
moval efficiency of particles and NOM was achieved by
TiCl4 for surface water treatment compared with the con-
ventional Al and Fe coagulants (Zhao et al. 2011a, Zhao
et al. 2011b). The coagulation ability of titanium sulfate
(Ti(SO4)2) has also been well confirmed by Wu et al.
(2011). The most significant advantage of titanium-based
coagulants is the production of a valuable byproduct
named titanium dioxide (TiO2) (Shon et al. 2009a, Shon
et al. 2009b, Shon et al. 2007, Yousef 2009, Zhao et al.
2011b), which has widespread applications including
Environ Sci Pollut Res (2017) 24:1757–1768
photocatalysts, paints, cosmetics, solar cells, and electron-
ic paper (Hoffmann et al. 1995). Moreover, as one of the
most abundant elements on earth and can be found in
almost every living thing, e.g. rocks, water bodies, and
soils, titanium is non-toxic and features biocompatibility
(Emsley 2001), because of which it has large medical
applications, such as surgical implementation and im-
plants. For the valuable byproduct production from coag-
ulated sludge and titanium biocompatibility, titanium-
based coagulants are thus expected to be promising alter-
native coagulants to conventional Al and Fe salts.
The titanium-based coagulants have advantages over the
regular coagulants in terms of particles and NOM removal
as aforementioned; however, none of the previous researches
reported nanoparticle separation by titanium-based coagu-
lants. As one of the most commonly utilized groups of nano-
particles, AgNPs released into water bodies will inevitably
form AgNP-NOM composite contaminants through adsorp-
tion on NOM surface. Humic acid (HA) is the major NOM in
groundwater (Kazpard et al. 2006). The adsorption process
has been evidenced to stabilize the nanoparticle suspension
significantly by modifying the surface charge status of both
nanoparticle and HA (Chinnapongse et al. 2011), which
makes it complicated to separate nanoparticles and HA from
water (Wang et al. 2014). This study uses HA as model NOM
and is the first attempt in the separation of AgNPs-HA com-
posite contaminants using titanium-based coagulants.
Coagulation-ultrafiltration (C-UF) hybrid process, as pre-
viously reported (Barbot et al. 2008), is expected to improve
operation efficiency and reduce membrane fouling efficiently
as compared with the coagulation or ultrafiltration alone.
Compared with conventional coagulants, the titanium-based
coagulants yield large flocs that form very quickly, leading to
faster and more effective settling (Zhao et al. 2011a, Zhao
et al. 2011b). Since the membrane fouling controlled by co-
agulation is tightly associated with floc properties (Choo et al.
2007), utilization of titanium-based coagulants for
precoagulation is likely to restrict membrane fouling due to
the enhanced floc characteristics. For the present study, trans-
portation of AgNPs to source water and entrance to the water
treatment process will definitely influence the characteristics
of flocs. Little is known about the properties of flocs formed
through the reaction between AgNP-HA composite contami-
nant and titanium-based coagulants. Membrane fouling re-
search regarding the C-UF hybrid process using titanium-
based salt as coagulant for AgNP-HA composite contaminant
separation is still empty.
The main objectives of this study are to (i) evaluate the
coagulation performance of titanium tetrachloride (TiCl4) for
AgNP-HA composite contaminant removal and characterize
the floc properties using a laser diffraction instrument by com-
parison with the conventional aluminum sulfate (Al2(SO4)3)
coagulants; (ii) investigate the coagulation mechanisms based
Environ Sci Pollut Res (2017) 24:1757–1768
on coagulation performance, floc characteristics, zeta poten-
tial measurements, and X-Ray diffraction (XRD) pattern; and
(iii) analyze and compare the membrane fouling resistance
between TiCl4 and Al2(SO4)3.
Experimental
Coagulants and test water
The TiCl4 solution (20 %, density = 1.25 g/mL) was diluted
from the concentrated TiCl4 solution (purity ≥99 %, Fulka) by
slowly adding cubes of frozen distilled water drop by drop
under continuous stirring. The stock solution of Al2(SO4)3
(2.0 mg/L) was prepared by directly dissolving the
predetermined Al2(SO4)3·18H2O (analytical pure grade) into
deionized water.
Two steps were included to prepare the test water: first, the
biochemical reagent humic acid (HA) (Aladdin Industrial
Corporation) was utilized as model NOM to make the synthet-
ic HA water. The procedure can be referred to Zhao et al.
(2011b). Second, the silver nanoparticle (Aladdin Industrial
Corporation) dispersions were ultrasonicated in an ultrasonic
bath (KQ-250B) twice for a cycle of 30 min. The AgNP-HA-
simulated water was prepared by mixing the predetermined
AgNPs with the HA solution of 10 mg/L. Properties of the
water sample were as follows: HA concentration = 10.0 mg/L,
AgNP concentration = 5.0 mg/L, UV254 = 0.295 ± 0.03 mg/L,
DOC = 4.974 ± 0.80 mg/L, pH = 8.44 ± 0.30, zeta
potential = −15.9 ± 0.40 mV. Zeta potential of the HA solution
was −11.0 ± 0.90 mV. The increase of absolute surface poten-
tial of the prepared AgNP-HA composite contaminant parti-
cles indicated the greater stability due to the mutual repulsion
between HA and AgNP surface (Zhang et al. 2009). For the
experiments to explore the influence of AgNP concentration
on floc property and membrane fouling, the predetermined
varied amount of AgNP suspension was mixed completely
with the HA-simulated solution (10 mg/L).
Jar test
Standard jar tests were conducted under different coagulant
doses and different initial solution pH conditions using a pro-
grammable jar tester (ZR4-6, ZhongrunWater Industry
Technology Development Co. Ltd., China). A two-stage
mixing process, including rapid (1.5 min stage at 200 rpm)
and slow mixing (15 min stage at 40 rpm) was followed by a
15-min settling period, after which the supernatant samples
were collected using a syringe from about 2 cm below the
water surface for the measurements of turbidity, UV254 absor-
bance, zeta potential, and dissolved organic carbon (DOC).
The analytical methods are discussed in Zhao et al. (2011b).
The AgNP concentration was measured by atomic absorption
1759
spectrophotometer TAS-990 (Beijing Purkinje General
Instrument Co. Ltd., China).
C-UF experiments and fouling resistance analysis
A dead-end batch UF unit with a magnetically stirred cell
(MSC050, Mosu, China) was utilized for UF experiments.
The UF membranes, with molecular weight cutoff (MWCO)
of 100 kDa, were supplied by EMD Millipore Corporation
(cat. no. PLHK07610). The UF experiments were carried
out under the constant pressure of 0.80 MPa by nitrogen
gas, and the permeate mass was measured using an electronic
b a l a n c e ( M S U 5 2 0 1 S - 0 0 0 - D 0 , S A RT O R I U S A G
GERMANY) every 10 s. The schematic diagram is discussed
in Xu et al. (2011).
After coagulation, the coagulated solutions were gently
dumped into the magnetic cell directly without sedimentation.
A weak stirring velocity was maintained in a UF beaker by a
magnetic stirrer to prevent aggregates from settling. To iden-
tify the membrane fouling mechanism, fouling resistance dis-
tribution (including external and internal fouling) (Akhondi
et al. 2014) was analyzed besides permeate mass. External
fouling was divided into strongly attached external fouling
and loosely attached external fouling according to its response
to shear force. Internal fouling was classified into reversible
internal fouling and irreversible internal fouling by
backwashing. The membrane fouling resistance is described
as shown below according to previous publications (Li et al.
2014):
TMP
Rt ¼ ¼ Rm þ R f ¼ Rm þ Ref þ Rif ð1Þ
μJ
Ref ¼ Ref −l þ Ref −s ð2Þ
Rif ¼ Rif −r þ Rirr ð3Þ
where Rt is the total hydraulic resistance (m−1); TMP is the
trans-membrane pressure (Pa); μ is the dynamic viscosity of
feed water (Pa s), which was 1.0*10−3 Pa s at 20 °C; J is the
permeate flux of the membrane (m/s); Rm is the intrinsic re-
sistance of the membrane itself (m−1); Rf is the total fouling
resistance generated by the water samples (m−1); Ref is the
external fouling resistance (m−1); Ref-l is the loosely attached
external fouling resistance that can be removed by shear force
(m−1); Ref-s is the strongly attached external fouling resistance
immune to shear stress (m−1); Rif is the total internal fouling
resistance (m−1); Rif-r is the reversible inner fouling resistance
that can be removed by backwash (m−1); and Rirr is the irre-
versible internal fouling resistance that cannot be removed by
backwash (m−1).
Details about the UF experiments to achieve the membrane
fouling resistance mentioned above can be found in the refer-
ence (Li et al. 2014).
1760
Floc characterization
The dynamic floc size was measured by a laser diffraction
instrument (Mastersizer 2000, Malvern, UK) as the coagula-
tion and flocculation process proceeded. The online monitor-
ing schematic diagram for dynamic floc size can be seen in
Zhao et al. (2011b). A slow mixing phase of 15 min at 40 rpm
was allowed for floc growth, followed by exposure to a shear
force at 200 rpm for 1 min. Another 15 min of slow mixing at
40 rpm was finally given for regrowth of the broken flocs.
Floc properties were characterized in terms of floc size,
strength factor (Sf), recovery factor (Rf), and fractal dimension
(Df) in this study. The medium equivalent diameter d50 was
selected as the representative floc size. Details regarding the
floc Sf, Rf and Df are displayed in previous papers (Zhao et al.
2011b, Zhao et al. 2013).
Results and discussion
Coagulation performance
Coagulation efficiency
The influence of coagulant dose and solution pH on coagula-
tion performance of TiCl4 in terms of turbidity, UV254, DOC,
and AgNP removal was investigated in comparison with con-
ventional Al2(SO4)3, and the results are shown in Supporting
Information (SI), section S1. The optimum coagulant dose for
TiCl4 and Al2(SO4)3 was chosen at 24.0 and 8.0 mg/L, respec-
tively, where the turbidity, UV254, DOC, and AgNP removal
of TiCl4 reached 92.0, 91.1, 66.1, and 96.1 %, while that of
Al2(SO4)3 was 92.8, 85.8, 39.3, and 95.3 %. Results indicated
that TiCl4 could achieve high organic matter and AgNP re-
moval to the same extent as conventional Al2(SO4)3 and es-
pecially had great advantage over Al2(SO4)3 in terms of DOC
removal by additional 68.2 %. The optimum solution pH
range was selected at 6∼7 and 7∼8, respectively for
Al2(SO4)3 and TiCl4. The TiCl4 was observed to be superior
to Al2(SO4)3 regarding UV254 and DOC removal within the
pH range of 6–9 (Fig. S2b, c), suggesting stronger coagulation
ability of TiCl4.
Coagulation mechanism
As seen from Fig. S1d, zeta potential of flocs formed by
Al2(SO4)3 increased with increasing coagulant dose but was
still negative within the coagulant dose range investigated,
suggesting the probable coagulation mechanism of bridge for-
mation and sweep flocculation. This is in accordance with the
previous reports (Gao et al. 2005, Zhao et al. 2011b). For
TiCl4 (Fig. S1b), the negatively charged particles decreased
along with the increasing coagulant dose and the isoelectric
Environ Sci Pollut Res (2017) 24:1757–1768
point appeared at about 32.0 mg/L. With the further increase
of TiCl4 dose, the positively charged particles became the
dominant and may lead to electrostatic repulsion among par-
ticles, which might be the reason for the decrease of turbidity
removal at high TiCl4 doses (Fig. S1a). Change of floc zeta
potential with TiCl4 dose indicated the change of dominant
coagulation mechanism from sweep flocculation to charge
neutralization during the TiCl4 coagulation process. Sweep
flocculation was supposed to play a major role under optimum
TiCl4 dose of 24.0 mg/L, where the floc zeta potential was
rather negative (around −11.9 mV).
The hydrolysis of Al2(SO4)3 and TiCl4 may be restrained
under acidic conditions, resulting in the low UV254 and DOC
removal, while the decrease of UV254 and DOC removal un-
der alkaline conditions could be attributed to the generation of
coagulant species with less positive charges (Zhao et al.
2011b). The AgNPs-HA composite contaminants were spec-
ulated to be removed by reaction with the coagulant hydroly-
zates through effective destabilization. Thus, change of AgNP
removal with initial solution pH presented a similar trend as
that of NOM removal and was tightly related to the hydrolysis
of coagulants. To investigate the AgNP removal mechanism
in detail, XRD analysis was applied to study the chemical
form of Ag in coagulated flocs. As shown in XRD spectra
(Fig. 1), the characteristic diffraction peaks that appeared in
38.034°, 44.230°, 64.342°, and 77.291° validate the existence
of AgNPs with the crystal structure in the flocs formed by
TiCl4. The characteristic peaks for AgCl, which generally
come out in 27.7°, 32.2°, and 46.2°, were not observed.
Results implied that silver ions were unlikely released in the
TiCl4 coagulation system, which thus prevented the formation
of AgCl. The AgNPs were, therefore, supposed to be removed
by adsorption on coagulant hydrolyzates and sedimentation
with the flocs in the form of AgNPs. Sun et al. (2013) reported
the same removal mechanism of AgNPs in Al2(SO4)3 coagu-
lation process.
400
(a)
350
300
250
Intensity
200 (b)
150
(c)
(d)
100
50
0
10 20 30 40 50 60 70 80
2 theta (degree)
Fig. 1 XRD pattern of flocs formed by Ti-based coagulants
Environ Sci Pollut Res (2017) 24:1757–1768 1761

It is worth noting that the increase in coagulant dose was
accompanied by an increase in floc zeta potential and a de-
crease in effluent pH (Fig. S1b, d). The effluent pH showed
gradual decrease as TiCl4 dose increased to 24.0 mg/L,
followed by a significant drop as TiCl4 dose further increased.
Different from TiCl4, the effluent pH after Al2(SO4)3 coagu-
lation decreased slightly (from around 7.8 to 6.8) with the
increasing coagulant dose. Under the optimum coagulant dose
condition, the effluent pH was 6.2 and 7.0, respectively, for
TiCl4 and Al2(SO4)3. However, beyond the optimum coagu-
lant dose, the conventional Al2(SO4)3 coagulant suggested
superior advantage over TiCl4 given higher effluent pH.
Floc characteristics
Floc growth, breakage, and regrowth profiles under different
coagulant doses, initial solution pH, and AgNP concentrations
are separately monitored online by Mastersizer 2000, and the
results are presented in SI, section S2. A sudden drop in floc
size was observed with introducing the increased shear force
to 200 rpm. Variable floc regrowth was then presented de-
pending on coagulant dose, solution pH, or AgNP concentra-
tion. The broken flocs, however, did not regrow to original
size.
Influence of coagulant dose
With the increasing TiCl4 dose by up to 24.0 mg/L, size d1 of
the flocs maintained a high value of around 832.0 ± 40.0 μm,
followed by an apparent decrease to about 581.0 μm at TiCl4
dose of 32.0 mg/L (Fig. 2a). Floc size d2 decreased with the
increasing TiCl4 dose and change in d3 with TiCl4 dose
showed a parabolic trend. Different from TiCl4, small varia-
tion of floc size with coagulant dose was observed for
Al 2(SO 4) 3 , with the floc size d 1, d 2, and d 3 of around
313.0 ± 20.6, 123.8 ± 10.7, and 185.5 ± 13.4 μm, respectively.

900 (a) 50 (b)

800 45

TiCl 4, d1 40
700
TiCl 4, d2
35 TiCl 4, Sf
TiCl 4, d3
Floc size d50 (µm)

600
Al2(SO4)3, d1 30 TiCl 4, Rf
Factor (%)

500 Al2(SO4)3, d2 Al2(SO4)3, Sf

25
Al2(SO4)3, d3 Al2(SO4)3, Rf
400 20

300 15

10
200
5
100
5 10 15 20 25 30 35 5 10 15 20 25 30 35

Coagulant dose (mg/L) Coagulant dose (mg/L)

(c) 3.00 (d)

2.90
2.95
2.85
2.90

2.80
2.85

2.75
2.80 Al2(SO4)3
Df

Df

TiCl4
2.70
2.75
4.0 mg/L
8.0 mg/L 6.0 mg/L
12.0 mg/L 8.0 mg/L
2.65 2.70
16.0 mg/L 10.0 mg/L
20.0 mg/L 12.0 mg/L
2.60 24.0 mg/L 2.65
32.0 mg/L
2.55 2.60
5 10 15 20 25 30 35 5 10 15 20 25 30 35
T (mins) T (mins)
Fig. 2 Floc properties under different coagulant dose conditions: a floc size d1, d2, and d3; b floc Sf and Rf; c Df of flocs formed by TiCl4; d Df of flocs
formed by Al2(SO4)3 (initial pH condition: pH = 8.44 ± 0.30)
1762
Overall, the TiCl4 coagulant had significant advantage over
Al2(SO4)3 given the larger floc size. For both TiCl4 and
Al2(SO4)3, floc Sf increased with the increasing coagulant
dose, while the opposite trend was seen for floc Rf (Fig. 2b).
Under optimum coagulant dose condition as stated in the
BCoagulation performance^ section, although the TiCl4
achieved larger floc size than did Al2(SO4)3, flocs formed by
TiCl4 showed higher floc strength given higher floc Sf. This is
not in agreement with the general concept that the larger flocs
are more prone to be broken by microscale eddies than are the
smaller ones and thus the smaller flocs generally tend to show
stronger floc strength than do the larger ones (Jarvis et al.
2005a, Jarvis et al. 2005b). Much weaker recoverability of
flocs formed by TiCl4 was observed than those by Al2(SO4)3
because of much lower floc Rf within the coagulant dose in-
vestigated. These results are in accordance with previous re-
ports (Zhao et al. 2011c). Since the flocs formed by adsorption
and sweep flocculation limited floc recovery after breakage
(Chaignon et al. 2002), sweep flocculation and adsorption of
AgNPs on hydrolyzates were presumably the predominant
coagulation mechanism. This corresponded well with the
analysis of coagulation mechanisms in the BCoagulation
performance^ section.
Regardless of floc growth, breakage, and regrowth process-
es, Df of flocs formed by TiCl4 and Al2(SO4)3 increased with
the increasing coagulant dose, approaching the highest value
at around 20.0 and 8.0 mg/L, respectively, followed by appar-
ent decrease with further increase of the coagulant dose
(Fig. 2c, d). The gradual increase in floc compact degree with
the increasing coagulant dose indicates the reduced repulsion
between flocs due to the decrease in absolute value of floc zeta
potential (Fig. S1b, d). The probably formed hydrolyzed poly-
mers at large coagulant doses, which may favor an extended
conformation away from the interface due to their chain struc-
ture (Hopkins and Ducoste 2003), might be responsible for the
decrease in floc Df. The sustainable increase in floc Sf with the
increasing coagulant dose was, however, not accompanied by
the continuous increase in floc Df, which was not in agreement
with the close relationship between floc strength and floc
structure as reported previously (Tang et al. 2002). The signif-
icant increase of floc Df after breakage was seen as evidence
that the flocs became more compact upon exposure to high
shear force. This result followed previous reports that the flocs
were broken at weak points and rearranged into more stable
structures (Tang et al. 2002). The overlapped curves of floc Df
vs coagulation time after floc recovery and after floc breakage
demonstrated unobservable improvement in floc compaction
degree by floc rearrangement.
Influence of initial solution pH
Floc size increased with the increasing initial solution pH in
the case of TiCl4, followed by a plateau beyond pH 7, while
Environ Sci Pollut Res (2017) 24:1757–1768
the reverse trend was seen in the case of Al2(SO4)3 (Fig. 3a).
Since the flocs at pH 4 did not grow to a stable stage during the
floc growth period (Fig. S4), the study of floc properties at
pH 4 was excluded in this section. The TiCl4 achieved high
floc size of about 758.9 ± 26.8 μm at pH 7 to 10, while for
Al2(SO4)3, acidic conditions were more favorable for floc for-
mation, with the highest floc size of about 586.4 μm obtained
at pH 5, followed by the decrease of floc size to around
331.2 ± 18.7 μm at pH 6 to 9. Larger size of flocs formed
by TiCl4 at alkaline conditions indicated that more hydroxyl
ions were required for the hydrolysis of TiCl4. However, at
pH 10, redundant hydroxyl may facilitate the formation of
Ti(OH)4 or negatively charged hydrolyzates, which decreased
HA and AgNP removal as shown in Fig. S2. Large floc size
did not always correspond with high coagulation efficiency.
Although the largest floc size was obtained at pH 5 for
Al2(SO4)3, more effective coagulation was achieved at higher
pH values (Fig. S2). Change in floc Sf vs pH was hardly
observed for both TiCl4 and Al2(SO4)3 within the pH range
investigated. The TiCl4 was superior to Al2(SO4)3 given
higher floc strength, while the recoverability of the flocs
formed by TiCl4 was much weaker than those by Al2(SO4)3
(Fig. 3b). As aforementioned, the flocs formed by charge neu-
tralization are expected to have complete recovery after break-
age while those by sweep flocculation normally show limited
recovery. The zeta potentials of the flocs formed by TiCl4 at
pH 5 and 6 were −0.2 and +4.4 mV, respectively, followed by
gradual decrease with the increasing pH (SI, Fig. S6), indicat-
ing the transformation of dominant coagulation mechanism
from charge neutralization to sweep flocculation. This might
be responsible for the decrease in floc recoverability.
However, charge neutralization was not the sole mechanism
involved in the coagulation process given the floc Rf values
lower than 100 %. Besides, the increase in pH presumably
facilitated the production of large hydrolysate polymers, mak-
ing the coagulation condition more favorable for sweep floc-
culation, which therefore might result in the decrease of floc
Rf. A high floc Rf approaching 79.6 % of Al2(SO4)3 flocs
demonstrated the predominant coagulation mechanism of
charge neutralization at pH 5.
Regarding Al2(SO4)3, change in floc Df as a function of
initial solution pH presented the following order: pH 5 < pH
6 < pH 7< pH 8 < pH 9 (Fig. 3d), while that of TiCl4 indicated
a reverse trend as pH increased by up to 8, followed by im-
provement of floc Df at pH 9 and 10 (Fig. 3c). Compared with
TiCl4 flocs, the flocs formed by Al2(SO4)3 had more compact
structure given higher floc Df values regardless of pH condi-
tions. The Al2(SO4)3 flocs, however, had weaker floc strength,
as aforementioned, than did the TiCl4 flocs. This did not agree
with the concept that the flocs with high strength generally
have compact structure (Tang et al. 2002). Higher floc Df
value means more compact floc structure, demonstrating that
the primary flocs have more tight attachments with each other,
Environ Sci Pollut Res (2017) 24:1757–1768 1763

(a) 90 (b)
800
80 TiCl 4, Sf
700 TiCl 4, d1 TiCl 4, Rf
70
TiCl 4, d2 Al2(SO4)3, Sf
600 TiCl 4, d3 60 Al2(SO4)3, Rf
Floc size d50 (µm)

Al2(SO4)3, d1

Factor (%)
50
500
Al2(SO4)3, d2
Al2(SO4)3, d3 40
400
30
300
20

200
10

100 0
5 6 7 8 9 10 5 6 7 8 9 10
pH pH

(c) (d)
2.5 3.00

2.95
2.4
2.90
2.3
2.85

2.2 2.80
Df

Df

2.1 2.75 Al2(SO4)3

TiCl4 pH=5
pH=6 2.70 pH=5
2.0 pH=6
pH=7
2.65 pH=7
pH=8
1.9 pH=9 pH=8
2.60
pH=10 pH=9
1.8 2.55
5 10 15 20 25 30 35 5 10 15 20 25 30 35
T (mins) T (mins)
Fig. 3 Floc properties under different solution pH conditions: a floc size d1,d2 and d3; b floc Sf and Rf; c Df of flocs formed by TiCl4; d Df of flocs formed
by Al2(SO4)3 (optimum coagulant dose condition: TiCl4 24.0 mg/L, Al2(SO4)3 8.0 mg/L)

or the repulsive force between primary microflocs are mini-
mized. The primary particles were formed by reaction be-
tween coagulant hydrolyzates and HA-AgNP composite con-
taminants. Since pH condition was a key parameter influenc-
ing coagulant hydrolyzates, characteristics of coagulant hy-
drolyzates under varying pH conditions were therefore closely
related with floc structure. Interaction between HA and
AgNPs under varied pH conditions was another factor affect-
ing floc compact degree, which need to be further
investigated.
Influence of AgNPs concentration
Effect of AgNP concentration on coagulation performance
was investigated, with the results showing that, under opti-
mum coagulant dose conditions, when AgNP concentration
varied from 1.0 to 20.0 mg/L, residual DOC varied from1.80
to 2.06 mg/L for TiCl4, while that of Al2(SO4)3 varied from
2.55 to 2.80 mg/L (detailed data not shown here). This result
indicates that the coagulation performance was almost
independent of AgNP concentration. The overlapped coagu-
lation dynamic curves under different AgNP concentrations
can be observed in SI, Fig. S5, serving as evidence that the
floc size, strength, and recoverability were also independent of
AgNP concentration. As the AgNP concentration increased
from 0 to 20.0 mg/L, the flocs formed by TiCl4 had larger floc
size d1 of about 803.6 ± 24.6 μm, larger floc Sf of about
44.5 %, and much lower floc Rf of 7.5 ± 2.7 % than those of
Al2(SO4)3, with the floc size of 326.7 ± 11.6 μm, floc Sf of
38.7 %, and floc Rf of 28.0 %.
However, the AgNP concentration had a big influence on
floc Df as shown in Fig. 4, with the results showing the de-
crease in floc Df with the increase of AgNP concentration for
both TiCl4 and Al2(SO4)3 coagulants. With the addition of
coagulants, the coagulant hydrolyzates were supposed to react
with HA-AgNP composite contaminants, forming primary
microflocs, followed by adsorption and sweep flocculation
to form flocs with large size. As aforementioned, the decrease
in floc compact degree demonstrated that the microflocs had
less attachment with each other or the repulsive force among
1764
3.00 (a)
2.95
2.90
2.85
Df
2.80
AgNPs 0 mg/L
AgNPs 1.0 mg/L
2.75
AgNPs 2.5 mg/L
AgNPs 10.0 mg/L
2.70 AgNPs 20.0 mg/L
5 10 15 20 25 30
T (mins)
Fig. 4 Variation of floc Df with AgNPs concentration: a TiCl4; b Al2(SO4)3 (Optimum coagulant dose condition: TiCl4 24.0 mg/L, Al2(SO4)3 8.0 mg/L;
initial pH condition: pH = 8.44 ± 0.30)
microflocs was enhanced. With the increasing AgNP concen-
tration, the decrease in floc compact degree was accompanied
by the decrease in particle zeta potential (Table S1, SI).
Particle zeta potential of HA-AgNPs composite contaminants
was probably a key parameter influencing the floc compact
degree. Because of the increase in particle surface potential
with the increasing AgNP concentration, the microflocs were
speculated to be prevented from tight aggregation, resulting in
the flocs with more open structure.
Membrane fouling
Coagulant dose effect
Raw water resulted in significant membrane fouling, mainly
external fouling, with the Ref (the sum of Ref-s and Ref-l) ac-
counting for 96.0 % of the total fouling, while Rif percentage
was only 4.0 % (detailed data not shown here). Low percent-
age of internal fouling in total fouling might be ascribed to the
high hydrophilicity of the membrane. The TiCl 4 and
Al2(SO4)3 treatments dramatically reduced membrane foul-
ing, especially the external fouling, and the increasing coagu-
lant dose favored the reduction of membrane fouling within
the coagulant dose studied (Fig. 5a). For TiCl4, compared with
Ref-l, Rif-r, and Rirr, the Ref-s was the most affected by coagu-
lant dose, with its value that decreased significantly from
3.15*1010 to 0.39*1010 m−1 and 0.61*1010 m−1, respectively
as the TiCl4 dose increased from 16.0 to 24.0 mg/L and
32.0 mg/L. The Ref-l shows continuous decrease, while the
Rif-r and Rirr were barely influenced by TiCl4 dose. The de-
crease in floc size, from 871.4 to 580.9 μm (Fig. 2a), did not
lead to the increase in membrane fouling, which might also be
attributed to the increase in floc strength although in small
scale (Fig. 2b). The reaction between positively charged hy-
drolyzates and negatively charged pollutants resulted in the
Environ Sci Pollut Res (2017) 24:1757–1768
3.4 (b)
3.2
3.0
2.8
Df
2.6
2.4
2.2
2.0
35 5 10 15 20 25 30 35
T (mins)
flocs with the increasing zeta potential (Fig. S1b). Due to the
less repulsive forces among particles, the resulted flocs were
more likely to attach to each other rather than adhere on the
membrane surface, which therefore facilitated the water per-
meation and restricted the membrane fouling. Regarding
Al2(SO4)3, serious membrane fouling happened at dose of
4.0 mg/L, with Ref-s value of 20.6*1010 m−1, accounting for
the majority of Rf. Similar to the case of TiCl4, the increasing
Al2(SO4)3 dose reduced membrane fouling caused by strongly
attached external membrane resistance, as evidenced by the
apparent decrease in Ref-s. The increase in Al2(SO4)3 dose
from 4.0 to 8.0 mg/L, however, led to the increase in Ref-l,
followed by its drop again under the 12.0 mg/L condition.
With the Al2(SO4)3 dose increased to 8.0 mg/L, the positive
hydrolyzates of Al2(SO4)3, such as Al(OH)2+, Al2(OH)24+,
and Al3(OH)45+, partly neutralized the pollutants and further
benefited the adsorption of colloids, resulting in the main pol-
lutant removal by sweep flocculation as stated in the
BCoagulation performance^ section. Results indicated that,
compared with the 4.0 mg/L condition, there are more parti-
cles loosely attached on the membrane surface at the 8.0 mg/L
condition, due to the pollutant removal mechanism of adsorp-
tion and sweep flocculation. The big drop in Ref-l at 12.0 mg/L
condition could be ascribed to the high removal of dissolved
organic matter (Fig. S1c), which facilitate the effluent perme-
ation as mentioned before.
It is worth noting that the TiCl4 coagulant has much lower
membrane fouling than do Al2(SO4)3 under the optimum co-
agulant dose conditions, with the results suggesting that the
R e f - s and R e f - l were reduced from 58.85*10 1 0 and
7.14 × 1010 m−1 to 0.39 × 1010 and 0.88 × 1010 m−1, respec-
tively, by TiCl4, while the resulted R ef-s and Ref-l after
Al2(SO4)3 treatment was much higher, about 2.19 × 1010
and 5.84 × 1010 m−1, respectively. This result is in accordance
with the superior organic matter removal by TiCl 4 as
Environ Sci Pollut Res (2017) 24:1757–1768 1765

(a)
25
0.9
Rirr 1.38
Rif-r

Membrane resistance(*10 m )
-1
20 Ref-s

10
Ref-l
15

20.57

10
1.24
0.74
2.19

1.1 0.36
5
0.88
5.84 1.18
3.15 0.17 0.50
1.14 0.84 0.94
0.88 0.42 2.16
0.39 0.61 2.00 0.44
0

L
L

L
L

g/

g/
g/

g/
g/

g/

m
m

m
m

0
.0

.0
.0

.0

4.

8.
24

12
16

32

)-

)-
l-

)-
3

3
l-

l-

O
4

3
4

4
C
C

O
(S

(S

4
Ti
Ti

Ti

(S
Al

Al
2

Al
2
(b) 22

20
1.8
18 Rirr 0.84
Membrane resistance(*10 m )
-1

16
Rif-r
10

Ref-s
14
Ref-l
12 11.14
0.25
1.11
10

8
4.61 1.07
1.15
6 1.29
1.10 2.61
4 2 0.52 1.81 0.20 0.75
6.1
5.1
2 0.49 1.04 3.14 3.21
1.75 1.33
0
9

5
7

9
5

pH

pH
pH

pH

pH
pH

l-

)-
l-

)-

)-
l-

3
4

3
C
4
C

O
4

O
Ti

4
Ti
Ti

(S

(S

(S
Al
2

Al

Al
2

(c) TiCl4 Al2(SO4)3

11

10 1.34
0.35 1.13 1.24 0.71
0.54 Rirr
Membrane resistance(*10 m )

9 0.58
-1

0.74
Rif-r 0.74
10

8 1.63

Ref-s
7 2.19
Ref-l 3.67 0.96
6 5.75
5.82
3.48 0.74
5

4 1.19 2.34
1.02
0.72
3 0.7 5.84
0.93
0.53 0.66 4.61
2 0.31 3.82
0.84
3.14 0.49
0.17
0 17
17 2.86 2.96
1 0.39 2.08 2.14
1.43
0.88
0
L
L

L
L

L
L

g/
g/

g/

g/

g/
g/

g/

g/

g/
g/

m
m

m
m

m
m

0
.0

.0

.0

.0
0

0
0

5.
1.

5.

1.
10

20

10

20

AgNPs concentration (mg/L)

Fig. 5 Membrane fouling resistance (Ref-s, Ref-l, Rif-r and Rirr) under varied coagulant doses (a), initial solution pHs (b), and AgNP concentrations (c)
1766
compared with Al2(SO4)3 under optimum coagulant dose con-
dition as aforementioned in the BCoagulation performance^
section. Additionally, compared with Al2(SO4)3, TiCl4 pro-
duced larger floc size, reducing the blocking of small particles
in membrane pores (Mao et al. 2013), which could be another
reason for the pronounced mitigation of membrane fouling.
Solution pH effect
As seen in Fig. 5b, within the pH range investigated, the TiCl4
coagulant showed advantages over Al2(SO4)3 with less mem-
brane fouling, especially lower Ref-s and Ref-l values, while
Rirr and Rif-r accounted for a small part of membrane fouling
and variation of which was hardly observed. The solution pH
exerted little influence on total membrane fouling caused by
TiCl4, with Rf varied from 4.37 × 1010 to 6.37 × 1010 m-1,
whereas, for Al2(SO4)3, remarkable change in membrane foul-
ing was evidenced by varying Rf value from 8.02 × 1010 to
19.88 × 1010 m−1 with increasing pH.
Solution pH is a key parameter influencing the hydrolysis
of coagulants, which further affects the reaction between co-
agulant hydrolyzates with pollutants, resulting in flocs with
varied characteristics. Membrane fouling was mainly related
to the porosity of cake layer, which was reported to have an
intimate relationship with floc characteristics (Park et al. 2006,
Yu et al. 2013). In the case of Al2(SO4)3, the membrane foul-
ing at pH 5 can be ascribed to two reasons. One is the low
removal efficiency of turbidity and organic matter by
precoagulation (Fig. S2), leading to the probable blocking of
membrane pores and the resistance of water permeation.
Another one is that the larger floc size with lower particle
fractal dimension (Fig. 3a, d), which corresponded with
thicker but porous floc cake layer (Feng et al. 2015), might
be responsible for external membrane fouling with higher Ref-s
and Ref-l. At high pH 9, higher membrane fouling could be
attributed to increase in specific cake resistance due to the
decreased floc size (Fig. 3a) with lower Rf (Fig. 3b) and higher
Df (Fig. 3d). The smaller flocs with weaker recoverability and
compact structure were supposed to block the pores of the floc
cake layer, resulting in higher density of the floc cake layer
and therefore high external fouling with compact floc cake
layer (Feng et al. 2015). Little variation in Rirr indicated that
the membrane surface pores were not blocked by nanoscale
flocs although floc property changes a lot with pH. Compared
with the Al2(SO4)3 coagulant, although characteristics of flocs
formed by TiCl4 varied a lot with varying solution pH accord-
ing to Fig. 3, variation of membrane fouling with solution pH
was hardly seen. As seen in Fig. S6, floc zeta potential of near
zero indicated complete charge neutralization at pH 5, while
with increasing pH from 7 to 9, adsorption and sweep floccu-
lation dominated coagulation system as evidenced by the de-
creased zeta potential to −15.0 mV. The flocs formed by
charge neutralization had less hydraulic resistance among
Environ Sci Pollut Res (2017) 24:1757–1768
each other than did those under sweep and flocculation con-
ditions (Choi and Dempsey 2004). On one hand, at pH 5, less
hydraulic resistance between particles resulted in looser,
might be more porous, cake layer, which made the membrane
less fouled than at pH 9. On the other hand, smaller floc size
(455.4 μm) with more compact structure at pH 5 than those at
pH 9 (with floc size of around 785.8 μm) tended to made
membrane fouling more serious as aforementioned. Thus,
two common influences as mentioned above reduced the dif-
ference in membrane fouling between pH 5 and pH 9. Above
all, the floc properties are interrelated and membrane fouling
is not affected by individual factor. Hydraulic resistance due to
varying coagulation mechanism is another important factor
influencing membrane fouling. The TiCl4 coagulant was su-
perior to Al2(SO4)3 not only in terms of less membrane foul-
ing within wider pH range but also relatively stable membrane
resistance even though the floc characteristics varied a lot with
pH. It will be of great significance to optimize the
precoagulation-membrane performance for each case to en-
hance systematic performance together with the minimization
of membrane fouling.
Silver nanoparticle effect
Incorporation of AgNPs during TiCl4 pretreatment process
facilitated the mitigation of membrane fouling, especially the
significant decrease of Ref-s (Fig. 5c). Without AgNP addition,
the Ref-s value was 5.75 × 1010 m−1, which decreased to
0.52 ± 0.14 × 1010 m−1 when AgNP concentration increased
from 1.0 to 20.0 mg/L. Different from TiCl4, total membrane
fouling by Al2(SO4)3 was negligibly influenced with the
AgNP concentration increased by up to 10.0 mg/L and was
followed by a relatively apparent decrease in membrane foul-
ing as AgNP concentration was further increased to 20.0 mg/
L. In total, the TiCl4 pretreatment mitigated membrane fouling
more efficiently than Al2(SO4)3 did under varying AgNP
concentration.
As stated in the BInfluence of AgNP concentration^ sec-
tion, coagulation efficiency of TiCl4 and Al2(SO4)3 was inde-
pendent of AgNP concentration and influence of AgNP con-
centration on floc characteristics were barely noticed except
floc Df. The varying membrane fouling under varying AgNP
concentrations might be attributed to the difference of floc
structure (Fig. 4). However, the decrease in floc compact de-
gree with the increasing AgNP concentration was not accom-
panied by the consistent change in membrane fouling, which
indicated that floc structure was not the only parameter
influencing membrane fouling. As discussed in the
BCoagulation performance^ section, the silver ions were not
released in both the TiCl4 and Al2(SO4)3 coagulation system,
and the AgNPs were removed by adsorption and sweep floc-
culation. For Al2(SO4)3, the barely observed variation of Rf
within AgNP concentration range from 0 to 10.0 mg/L
Environ Sci Pollut Res (2017) 24:1757–1768
implied that turbulence of membrane fouling was independent
from low AgNP concentration. Compared with AgNP con-
centration of 0 mg/L, the probable attachment of AgNPs on
membrane surface may be the reason for the increase in Rirr
and Rif-r. Property of floc cake layer was reported to have close
relationship with membrane fouling as mentioned before (Yu
et al. 2013). On the one hand, the varied floc structure (Fig. 4)
under varying AgNP concentrations inevitably altered the
property of the floc cake layer. On the other hand, the effect
of interaction between AgNP, coagulant hydrolyzates and or-
ganic flocculants on membrane fouling needs further investi-
gation. The possible attachment of AgNPs on membrane sur-
face is another reason for the variation of membrane resis-
tance. The disproportional increase of Ref-l and irregular de-
crease of Ref-s in Al2(SO4)3 coagulation system would be at-
tributed to the combined reasons above. In comparison with
the case of Al2(SO4)3, the inclusion of AgNPs apparently
enhanced the membrane fouling reduction within the AgNP
concentration range studied, from which it can be speculated
that the AgNPs were more favorable for TiCl4 coagulation
system in terms of reducing membrane fouling and therefore
benefiting water permeation.
Conclusions
Precoagulation by titanium-based coagulants is expected to
enhance membrane filtration and reclaim functional TiO2
from resultant sludge. This study employed titanium tetrachlo-
ride (TiCl4) for silver nanoparticle (AgNPs)-humic acid com-
posite contaminant removal in coagulation-ultrafiltration (C-
UF) process. Floc properties and their influence on membrane
fouling were mainly investigated under varied coagulant dose,
solution pH, and AgNP concentration conditions. The case of
Al2(SO4)3 served as a reference. The specific findings are as
follows:
1 The optimum coagulant dose for TiCl4 and Al2(SO4)3 was
24.0 and 8.0 mg/L, respectively, and the optimum solution
pH was at 6∼7 and 7∼8, respectively. The TiCl4 achieved
high organic matter and AgNP removal to the same extent
as Al2(SO4)3, and had especial advantage over Al2(SO4)3
in terms of DOC removal by additional 68.2 %. The
AgNPs were removed by adsorption and sweep floccula-
tion in the original form, instead of AgCl formation, in
both TiCl4 and Al2(SO4)3 coagulation system.
2 Both coagulant dose and solution pH had significant im-
pact on floc properties. Under optimum coagulant dose
and solution pH condition, the TiCl4 coagulant formed
larger and stronger flocs with weaker recoverability and
less compact degree than Al2(SO4)3. On the other hand,
floc properties were independent of AgNP concentration
except floc fractal dimension, where a negative correlation
1767
between AgNP concentration and floc compactness was
observed for both TiCl4 and Al2(SO4)3.
3 The TiCl4 precoagulation caused less membrane fouling as
compared with Al2(SO4)3 within wider pH range, which
can be ascribed to (i) the superior organic matter removal
by TiCl4, facilitating water permeation and (ii) the larger
floc size produced by TiCl4, reducing the blocking of
small particles in membrane pores. Mitigation of mem-
brane fouling was enhanced by AgNP incorporation in
case of TiCl4, while negligible influence of AgNP concen-
tration on membrane fouling was seen in the case of
Al2(SO4)3.
Acknowledgments This work was supported by grants from the
Chinese National Natural Science Foundation (No. 51278283, No.
21377072, and No. 51508308) and China Postdoctoral Science
Foundation (No. 2014M560557 and No. 2015T80722). Also, this work
was supported by grants from Tai Shan Scholar Foundation (No.
ts201511003) and Hong Kong Scholars Program.
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