Chemical Engineering Journal 183 (2012) 387394

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Chemical Engineering Journal

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Coagulation performance and oc characteristics with polyaluminum chloride

using sodium alginate as coagulant aid: A preliminary assessment
Y.X. Zhao a , B.Y. Gao a, , Y. Wang a, , H.K. Shon b , X.W. Bo a , Q.Y. Yue a
a
School of Environmental Science and Engineering, Shandong University, No.27 Shanda South Road, Jinan 250100, Shandong, Peoples Republic of China
b
School of Civil and Environmental Engineering, University of Technology, Sydney (UTS), P.O. Box 123, Broadway, NSW 2007, Australia

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

Article history: The effect of sodium alginate (SA) on coagulation performance and oc characteristics with polyaluminum
Received 15 November 2011 chloride (PAC) was evaluated in synthetic humic acidkaolin water treatment. Coagulation performance
Received in revised form 4 January 2012 and oc characteristics of PAC were investigated for comparison. The results showed that PAC plus SA
Accepted 4 January 2012
exhibited certain synergistic effect on DOC (dissolved organic carbon) and turbidity removal. DOC removal
was more enhanced by SA at low PAC doses than at higher ones, while turbidity removal was enhanced
Keywords:
when PAC doses were larger than 1.5 mg/L. The growth, breakage, regrowth and fractal nature of ocs
Coagulation
were investigated using Mastersizer 2000, with the results suggesting that the aggregated ocs after
Polyaluminum chloride
Sodium alginate
PACSA (PAC dosed rst) occulation showed faster growth rate and with larger oc size compared with
Floc regrowth the ocs formed by PAC. Besides, PACSA gave the ocs with more open structure but better recovery
Fractal dimension ability after oc breakage compared with PAC.
2012 Elsevier B.V. All rights reserved.

1. Introduction to be superior to the traditional Al-based coagulants (e.g. AlCl3 and

Humic acid (HA) forms the major component of the natural
organic matter (NOM) present in natural freshwater and has been
recognized as a signicant generator of carcinogenic disinfection-
byproducts (DBPs) [1]. In addition, HA presents a dark yellow to
black appearance. Therefore, the removal of HA attracts extensive
interest for both research and practical application. Coagulation, as
the most widely applied unit process for the removal of particles
and organic matter present in water [2], is becoming highly val-
ued. Flocculating agents are generally divided into three groups:
(1) inorganic occulants, such as aluminum sulfate (generally
known as alum), polyaluminum chloride (PAC), ferric chloride
and polyferric sulfate; (2) organic synthetic occulants, such as
polyacrylamide derivatives and polyethylene imine; (3) naturally
occurring occulants, such as chitosan, sodium alginate (SA) and
bioocculant [3]. Due to the effectiveness in treating a wide range
of waters at a relatively low lost, aluminum salts become the most
commonly used coagulant in water treatment. Alum has been used
for water purication since ancient times and was rst mentioned
by Pliny (approx. 77 AD). Other products based on pre-hydrolyzed
metals are also now widely used, including a range of materials
referred to as PAC, which has been claimed by many investigators
Corresponding authors. Tel.: +86 531 88364832; fax: +86 531 88364513.
E-mail addresses: baoyugao sdu@yahoo.com.cn (B.Y. Gao),
wangyan sdjn@yahoo.com.cn (Y. Wang).
alum) in particulate and/or organic matter removal under some
conditions [4,5]. The naturally occurring occulants are considered
safe and biodegradable [6], and thus have received considerable
scientic and biotechnological attention in recent years. However,
so far none of the bioocculants has been put into practical applica-
tions because of the low occulating capacity, low yields and high
production cost [7,8]. The chemical compound SA is the sodium
salt of alginic acid. Its form as a gum, when extracted from the cell
walls of brown seaweed, is used by the food industry to increase
viscosity and as an emulsier. It is also used in indigestion tablets.
As a linear natural polymer found in brown algae, SA can also be
used as a occulant in wastewater treatment [9]. SA, as a oc-
culant, is nontoxic biodegradable, and thus not leading to any
secondary pollution, but with bad fIocculation performances. To
overcome these limitations, dual-coagulants (naturally occurring
occulants used as coagulant aid combined with inorganic coag-
ulants) are used as one of the cost reduction methods. They not
only reduce the doses of naturally occurring occulants, but also
enhance the occulation activity of inorganic coagulants. More-
over, the risk induced by the chemical occulants can be reduced
as their doses could be cut down. Bratby reported that the primary
coagulant is typically added rst, followed by a polymer coagulant
aid [10]. So far, there has no report on the effect of SA used as coag-
ulant aid with inorganic coagulants. The aim of this study was to
investigate the effect of SA used as coagulant aid, and the dual-
coagulant, PACSA, was prepared by dosing SA at 30 s after PAC
addition.

1385-8947/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2012.01.036
388 Y.X. Zhao et al. / Chemical Engineering Journal 183 (2012) 387394
Characteristics of ocs, including physical properties such as oc
size, oc grow rate as well as oc strength and recovery ability after
being broken, cause critical effect on solid/liquid separation process
[11]. Faster oc growth rate means a shorter coagulation pro-
cess, and a smaller coagulation tank is required. Boller and Blaser
[12] showed that small particles generally have lower removal
efciency by occulation. Smaller particles generally settle down
more slowly than larger particles of similar density. Floc strength
and recovery ability are also considered as important parameters
for overall process optimization as occulation process is often
prevalent with regions of high shear forces during the separation
technique such as the removal of aggregated particles [13]. The ocs
must be stable enough to resist these stresses to prevent them from
being broken into smaller particles. Therefore, oc strength and
recovery ability are considered as important parameters to provide
valuable information in understanding coagulants performances.
Besides, fractal dimension characteristic of ocs is another par-
ticularly important operational parameter that deserves special
attention. It has been well-known that aggregates formed during
the coagulation process exhibit a fractal characteristic, implying
that they are self-similar and scale invariant [14]. Fractal theo-
ries for particle aggregates provide a new quantitative method
to describe the structure of particles aggregates in various water
systems [15]. Small angle laser light scattering (SALLS) has been
successfully used to determine the fractal dimension of model
primary particles [16]. Mass fractals may be summarized by the
relationship between their mass (M), a characteristic measure of
size (L), and the mass fractal dimension (Df ):
M LDf
High Df means the primary particles in an aggregate are arranged
compactly, while low Df results from large, highly branched and
loosely bound structures.
The goal of this paper is to test the effect of SA used as coagulant
aid in HAkaolin synthetic water treatment with PAC. Coagula-
tion performance of PACSA was investigated in comparison with
that of PAC in terms of residual turbidity, UV254 removal and DOC
removal as well as zeta potential. In addition, the evolution of oc
size as a function of coagulation time was measured by a laser
diffraction instrument. The aggregated ocs were characterized in
terms of their size, oc growth rate, oc strength, oc regrowth
potential and the fractal dimension. The relationship between oc
properties and coagulation mechanisms was also discussed.
2. Experimental
2.1. Coagulants
PAC with B = 2.0, which is equivalent to the molar ratio of
[OH ]/[Al3+ ], was selected for this study. PAC was prepared as
follows [17]: predetermined amount of AlCl3 6H2 O and Na2 CO3
powder was fully mixed and then slowly added into deionized
water at constant speed for 30 min while stirring at 7080 C to
obtain the desired basicity value of PAC. The mixture was stirred
until no bubbles were formed and the solution became trans-
parent. The product was allowed to keep more than 24 h before
the examination of aluminum content, which was measured by
ethylenediaminetetraacetic acid (EDTA) complexometric titration
(GB5749-2006). Stock solution of PAC was prepared at a concen-
tration of 1.0 g/L as Al.
SA was provided by Sinopharm Chemical Reagent Co., Ltd.,
Shanghai, China. Stock solution of SA was prepared at a concen-
tration of 1.0 g/L and was stored in 4 C. Zeta potential of SA was
about 88.0 mV. Deionized water was used for all the reagents
preparation.
2.2. Test water
The commercial humic acid with a carbon content of 52.6%
(w/w), biochemical reagent, was purchased from the Jufeng Chemi-
cal Technology Co. Ltd., Shanghai, China. A stock solution of HA was
prepared by dissolving 1.0 g of HA in 0.01 mol/L sodium hydroxide
(NaOH) solution under continuous stirring for 30 min. Coagula-
tion experiments were performed with synthetic water containing
10 mg/L of HA prepared in deionized water and tap water [18].
The initial turbidity was adjusted to approximately 15 0.2 NTU
by adding kaolin. Kaolin was purchased from the Kermel Chemical
Technology Co. Ltd., Tianjin, China. The UV254 absorbance, DOC, and
pH of the suspension were 0.445 0.006 cm1 , 4.274 0.184 mg/L,
and 8.238.57, respectively.
2.3. Jar test
Standard jar tests were conducted on a program-controlled jar
test apparatus (ZR4-6, Zhongrun Water Industry Technology Devel-
opment Co. Ltd., China) at 20 1 C of room temperature. During
the rapid stirring of 200 rpm, predetermined amount of coagulant
was dosed to give a certain PAC dose, ranged from 0.5 to 3.0 mg/L
as Al. Bratby reported that when organic polymer was used as
coagulant aid, best results were obtained when the polymer was
added after the addition of primary coagulant [10]. In the compar-
ative experiment, PAC was added rstly at the start of rapid mixing
phase (200 rpm) and followed by SA addition after 30 s. The dual-
coagulant was denoted as PACSA. Rapid mixing of 1 min continued
(1) after the coagulants addition, then, the stirring speed was changed
to 40 rpm with duration of 15 min, followed by 15 min of quiescent
settling. After sedimentation, supernatant samples were collected
using a syringe from about 2 cm below the water surface for subse-
quent measurements. Collected samples were preltered through
a 0.45 m ber membrane before testing for UV254 (absorbance
at 254 nm using a UV-754 UV/VIS spectrophotometer) and DOC
(measured by a Shimadzu TOC-VCPH analyzer), while the turbidity
was measured without ltration using a 2100P turbidimeter (Hach,
USA) and the zeta potential was analyzed with a Zetasizer 3000 HSa
(Malvern Instruments, UK).
2.4. On-line monitoring of oc size
The dynamic oc sizes were measured using Mastersizer 2000
(Malvern, UK). The suspended ocs were monitored through the
optical unit of the Mastersizer and transferred back into the jar by
a peristaltic pump (LEAD-1, Longer Precision Pump, China) with a
5 mm internal diameter tube. The pump was located downstream
of the Mastersizer to avoid disturbing the ocs prior to measure-
ment. The inow and outow tubes were positioned opposite one
another at a depth just above the paddle in the holding ports. Size
measurements of the formed ocs were taken every 0.5 min during
the jar test process and the corresponding data were automatically
recorded.
2.5. Floc breakage and re-growth
Coagulation tests were conducted on a jar tester as before. The
aggregated ocs after each occulation were exposed to shear force
at 200 rpm for 5 min after the slow mixing phase. After the shear
mixing phase, slow mixing was reintroduced for a further 15 min
at 40 rpm. Floc sizes were monitored as stated in Section 2.4. All
the experiments were carried out two or three times and very little
variation was observed. Strength factor (Sf ) and recovery factor (Rf )
 Y.X. Zhao et al. / Chemical Engineering Journal 183 (2012) 387394 389

100
16 (a) (b)
14
PAC 80

12 PAC-0.5 mg SA
Residual turbidity (NTU)

PAC-1.0 mg SA

UV254 removal (%)

10 PAC-2.0 mg SA 60
PAC
8 PAC-0.5 mg SA
40 PAC-1.0 mg SA
6 PAC-2.0 mg SA

4
20
2

0 0
0.5 1.0 1.5 2.0 2.5 3.0
0.5 1.0 1.5 2.0 2.5 3.0
PAC (mg/L) PAC (mg/L)
-4
70 (c) (d)
-6
60

50 -8 PAC
PAC-0.5 mg SA
Zeta potential (mV)
DOC removal (%)

40 PAC-1.0 mg SA
-10 PAC-2.0 mg SA
PAC
30 PAC-0.5 mg SA
PAC-1.0 mg SA -12
20 PAC-2.0 mg SA
-14
10

0 -16

-10 -18
0.5 1.0 1.5 2.0 2.5 3.0
0.5 1.0 1.5 2.0 2.5 3.0
PAC (mg/L) PAC (mg/L)

Fig. 1. Efffect of SA on residual turbidity (a), UV254 removal (b), DOC removal (c), and zeta potential (d) with PAC and PACSA coagulants.

to compare the oc strength and recovery ability were calculated The scattered intensity I as a function of the magnitude of the scat-
as follows [2,19]: tering wave vector Q is measured [19], where, n, , and  are the
refractive index of the medium, the scattered angle, and the wave-
d2
Sf = 100 (2) length of radiation in vacuum, respectively.
d1 For independently scattering aggregates, the relationship
d3 d2 among I, Q and the fractal dimension Df can be represented by Eq.
Rf = 100 (3) (5) [22]:
d1 d2

where d1 is the average oc size of the steady phase before breakage I Q Df (5)
or shear phase, d2 is the oc size after the oc breakage period, and
Df is the fractal dimension and can be determined by the slope of
d3 is the oc size after re-growth to the new steady phase.
a plot of I as a function of Q on a loglog scale. Compact aggre-
The higher the Sf value, the less sensitive the ocs are to
gates have higher Df , while aggregates with loose structures have
breakage as a result of increased shear force, which are therefore
lower Df . Experimental measurement of Df of aggregates is not
considered stronger. Likewise, the ocs with larger Rf show better
straightforward, and the methods available are indirect.
recovery ability after being subjected to high shear force.

2.6. Floc fractal dimension 3. Results and discussion

Light scattering method is widely used for the determination of 3.1. Effect of SA on coagulation performance
aggregate mass fractal dimension. Details in the theory of the mass
fractal dimension have been reported in a few literatures [20,21]. In When SA was used as coagulant alone, turbidity, UV254 and
this study, mass fractal dimension is measured by light scattering DOC removal was barely observed, and the ocs formed were
technology. The method is briey given as follows: hardly visible to the naked eyes. The effect of SA used as coagu-
lant aid on coagulation performance with PAC was investigated in
4n sin(/2) terms of residual turbidity, UV254 removal, DOC removal as well
Q = (4)
 as zeta potential and the results are presented in Fig. 1. The main
390 Y.X. Zhao et al. / Chemical Engineering Journal 183 (2012) 387394
nding was that PACSA improved DOC removal by an additional
less than 15% compared with PAC when PAC dose of less than
1.5 mg/L and 0.5 mg/L SA was used (Fig. 1(c)). This is consistent
with the previous reports that better removal performance can
be achieved when polymer is used in combination with conven-
tional coagulant [2325]. However, when PAC dose of more than
2.0 mg/L was used, the synergistic improvement in DOC removal
was hardly observed. In addition, the synergistic improvement
decreased when dose of SA was larger than 1.0 mg/L, which may
be attributed to the reason that more dose of negatively charged
SA (about 88.0 mV) would inhibit microocs from growing into
bigger ones due to strong repulsion force between microocs and
the SA molecules. This phenomenon is consistent with the obser-
vation by Gong et al. [26] in the occulation of kaolin particles by
negatively charged bioocculants. Besides, the residual SA, which
was essentially a kind of organic polymer, might be another con-
siderable reason for the decrease of DOC removal when SA was
overdosed. Therefore, like coagulant agents, the dose of SA as coag-
ulant aid should also be optimized.
In these experiments, SA addition during coagulation process
barely augmented UV254 removal (Fig. 1(b)). Compared with PAC,
residual turbidity increased from about 5.5 NTU to 14.5 NTU when
SA was used combined with 1.0 mg/L PAC, but it greatly decreased
when PAC dose was higher than 2.0 mg/L. That can be explained as
follows: PAC dose of 1.0 mg/L did not effectively removal organic
matter and particles, and the ocs formed were negatively charged,
which indicated that HA was removed not only by charge neu-
tralization, but adsorption and bridging played an important role.
When SA was dosed, negatively charged SA might inhibit the
microocs from growing into bigger ones due to mutual repulsion,
which resulted in the turbidity increase (because the ocs with
small sizes were difcult to settle). The zeta potential increased
with increasing PAC addition, resulting in weaker repulsion forces
between the colloids. Hence, the adsorption bridging ability of SA
could play a role in the occulation process. When PAC dose of
larger than 2.0 mg/L was used, decrease of the residual turbidity
was suspected to be attributed to adsorption and bridge between
SA molecules and the formed microocs by PAC.
Fig. 1(d) shows the relationship of zeta potential vs. the dosage
of PAC and the dual-coagulants. It can be observed that, for PAC, the
UV254 and DOC removal increased with dose, which accompanied
the increasing zeta potential, and the zeta potential increased from
about 16.6 mV to about 5.4 mV. This indicated that charge neu-
tralization was the dominate mechanism by PAC. Since pH of the
raw water was 8.238.57, signicant precipitation of amorphous
hydroxide could occur. So the charge neutralization was more likely
to be achieved by adsorbed precipitate [27]. Similar results were
found by Gregor et al. [28]. They reported that charge neutralization
and entrapment/adsorption of NOM onto metal precipitates were
the major oc formation routes for PAC. In this condition, coagula-
tion was more affected by precipitate while charge effect seemed
less important. This also explained why efcient DOC removal still
occurred at low dosages, even though the zeta potentials were
somewhat below zero. In case of PACSA, zeta potential of ocs
decreased with increasing SA doses. When PAC was dosed rstly,
the negatively charged HA reacted with hydrolysis products of PAC,
with the reaction products of the negative charged PACHA com-
plex. After the highly negatively charged SA was dosed, the higher
absolute zeta potential values of the ocs might be due to its adsorp-
tion on the surface of the complex.
3.2. Effect of SA on oc characteristics
3.2.1. Dynamic analysis of oc formation process
Floc formation, breakage and re-formation with different coag-
ulants were monitored using Mastersizer 2000. The effect of CBF
on oc size in steady state and the oc grow rate vs. coagulant
dose was investigated as suggested by Wang et al. [29], and the
results are shown in Fig. 2. The same general trend was seen for
d10 , d50 and d90 oc sizes, and d50 was selected as the represent
oc size. From Fig. 2, it can be seen that the oc size d50 and oc
grow rate increased with increasing PAC doses no matter which
kind of coagulant was used. PAC plus anionic polymer SA exhib-
ited an apparent improvement on oc size (Fig. 2(a)) and gave
obviously faster oc formation (Fig. 2(b)) when PAC doses of more
than 1.5 mg/L were used. For example, size of the ocs formed by
1.5 mg/L PAC combined with 0.5 mg/L SA increased by an additional
approx. 78.5% compared with those of PAC, while the correspond-
ing oc rate increased by about additional 10%. However, both oc
size and oc growth rate decreased with SA addition when PAC of
1.0 mg/L was used. The oc size decreased from 133 m to about
102 m and 19 m, respectively, when SA doses of 0.5 and 1.0 mg/L
were used. The oc growth was barely observed when 2.0 mg/L SA
was used. That corresponded well with Section 3.1, which indicated
that the negatively charged SA resulted in the repulsion among
microocs. For that reason, SA inhibited the microocs from grow-
ing into bigger ones and, therefore, reduced the oc growth rate.
Increase of oc size and oc growth rate with SA addition may be
due to the adsorption and bridge ability of SA, because repulsion
forces between the colloids become weaker with increasing PAC
doses.
3.2.2. Floc breakage and oc recovery
After slow mixing at 40 rpm, the shear force was introduced
by increasing the mixing speed up to 200 rpm for 5 min. The ocs
showed an apparent decrease immediately. Then, the original slow
stir speed (40 rpm) was reintroduced for oc regrowth. In this
study, a steady-state size of ocs formed by PACSA did not appear
within the coagulation time when PAC doses of less than 1.5 mg/L
were used. So, in this section, PAC doses of 1.5, 2.0, 2.5 and 3.0 mg/L
were selected for oc properties investigation. Fig. 3 shows the
variation of oc sizes with different coagulants as a function of
coagulant dose after oc breakage (a) and oc regrowth (b). It can be
seen that, when SA doses of 0.5 and 1.0 mg/L were used, size of ocs
formed by PACSA after oc breakage and after oc regrowth fol-
lowed the same order as that before oc breakage: PACSA > PAC.
However, when 2.0 mg/L SA was used, improvement of oc size
decreased after oc regrowth with PAC doses of 2.0 and 2.5 mg/L
(Fig. 3(b)).
To investigate oc variations in detail, oc Sf and Rf , calculated
using Eqs. (2) and (3), were used to interpret the oc strength and
recovery ability (Table 1). Increased percentages were calculated
by comparison oc Sf and Rf of PACSA with those of PAC. It was
found from Table 1 that the oc Sf and Rf decreased with increasing
coagulant doses no matter which kind of coagulant was used. Larger
doses of PAC produced weaker ocs, which could be attributed to
the large ocs being more exposed to microscale energy-dissipating
eddies that led to oc breakage [12]. While smaller ocs tended to
become entrained within these eddies rather than being broken by
them. Analysis of the oc regrowth results indicated that the oc
recovery ability was improved signicantly with SA addition, as
reected by the increase of oc Rf s. The Rf s were improved by about
additional 100%137% when 1.0 mg/L SA was used combined with
PAC within the doses investigated. However, improvement of oc
Rf s decreased when 2.0 mg/L SA was used, with the increased per-
centages decreased to about 40%67%. It corresponded well with
the results obtained above that the synergistic increase in oc size
decreased after oc regrowth process when 2.0 mg/L SA was used
combined with PAC. As to the oc Sf s, the increased percentages
were not that obvious as oc Rf s.
In this study, NOM removal was obtained while the oc zeta
potentials were still negative regardless of the coagulants used
 Y.X. Zhao et al. / Chemical Engineering Journal 183 (2012) 387394 391

550
(a) 100 (b)
500
PAC 90
450 PAC
PAC-0.5 mg SA 80 PAC-0.5 mg SA
400 PAC-1.0 mg SA PAC-1.0 mg SA
PAC-2.0 mg SA 70
350 PAC-2.0 mg SA

Floc grow rate m/min

60
300
Floc size d 50 m

50
250
200 40

150 30

100 20

50 10

0 0

-50 -10
0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0
PAC (mg/L) PAC (mg/L)

Fig. 2. Effect of SA on oc size d50 (a) and oc growth rate (b) as a function of coagulant dose after oc growth process.

180 (a) (b)

PAC 300
PAC-0.5 mg SA
160 PAC-1.0 mg SA
PAC-2.0 mg SA
250
140
Floc size d 50 m
Floc size d 50 m

PAC
120 200 PAC-0.5 mg SA
PAC-1.0 mg SA
100 PAC-2.0 mg SA
150

80

100
60

1.5 2.0 2.5 3.0 1.5 2.0 2.5 3.0

PAC (mg/L) PAC (mg/L)

Fig. 3. Variation of oc size d50 with different coagulants as a function of coagulant dosage: (a) after oc breakage; (b) after oc regrowth.

(Fig. 1(d)), and the coagulation mechanisms were suspected to [30,31]. From Table 1, it can be concluded that the ocs could not
be a combination of precipitate charge neutralization and entrap- regrow to anywhere near their previous size for all the coagulants,
ment/adsorption of NOM onto metal precipitates. It has been for the Rf s of ocs were all below 100%. In addition, variation of
reported that recovery ability of ocs gives some indication of the oc Sf s and Rf s suggested that the aggregates formed varied over
oc internal bonding structure [2]. The ocs formed by charge neu- a wide range after oc breakage and oc regrowth. For PACSA, it
tralization should give complete recovery, while the ocs formed was suspected that when PAC was dosed rstly, PAC hydrolyzed
by sweep coagulation showed poor regrowth after oc breakage instantaneously. The hydrolyzates reacted with HA to form the

Table 1
Sf s and Rf s of ocs formed by different coagulants with different coagulant doses.

Coagulant dose (mg/L) PAC PAC0.5 mg SA Increased percentage (%) PAC1.0 mg SA Increased percentage (%) PAC2.0 mg SA Increased percentage (%)

Sf
1.5 40.8 40.3 0.0 42.9 5.0 45.4 11.2
2.0 39.3 37.3 0.0 40.6 2.1 39.3 0.0
2.5 37.5 37.7 0.3 40.1 4.1 38.6 2.9
3.0 37.6 37.8 0.6 39.6 7.9 35.8 0.0

Rf
1.5 37.8 67.4 78.2 78.4 107.6 66.6 76.3
2.0 36.6 59.3 62.1 73.3 100.3 47.9 31.0
2.5 30.0 59.2 97.1 60.7 102.3 43.0 43.2
3.0 25.3 51.6 104.3 59.8 136.8 41.3 63.4
392 Y.X. Zhao et al. / Chemical Engineering Journal 183 (2012) 387394

Fig. 4. Effect of 0.5 mg/L SA on growth, breakage and regrowth prole of the NOM ocs and the corresponding particle size distributions of the ocs before breakage, after
breakage and after regrowth after 5 min of high shear time: (a) 1.5 mg/L PAC; (b) 2.5 mg/L PAC.
 Y.X. Zhao et al. / Chemical Engineering Journal 183 (2012) 387394 393

negatively charged PACHA complex, or part of PAC hydrolyzed Growth Breakage Regrowth
to form Al(OH)3 ocs. The PACHA complex and Al(OH)3 ocs con-
1.96
stituted the microocs in the initial stage of rapid mixing. When SA 1.5 mg PAC
was dosed, it quickly adsorbed on the surface of the microocs and 1.94 1.5 mg PAC-SA
large ocs gradually formed due to the chain structure of SA. When 1.92
2.5 mg PAC
2.5 mg PAC-SA
the ocs were broken, better recovery ability of the PACSA ocs 1.90
were observed compared with ocs formed by PAC, which might be
1.88
attributed to the reason that the SA with the electrostatic attraction
1.86
and Van der Waals on newly exposed microocs surface may bond

Df
the oc fragments together. Decrease in the oc Rf s when 2.0 mg/L 1.84
SA was used might be ascribed to the repulsion forces between par- 1.82
ticles caused by the overdosed anionic polymer SA. Thus, dose of 1.80
SA used as coagulant aid should be optimized.
1.78

3.2.3. Analysis of particle size distribution 1.76

Floc particle size distribution (PSD) was analyzed in this section,
and PAC doses of 1.5 and 2.5 mg/L combined with 0.5 mg/L SA were
selected for investigation. Effect of SA on growth, breakage and
regrowth prole of the NOM ocs formed by PAC and PACSA and
the corresponding PSD of the ocs before breakage, after breakage
and after regrowth were investigated and the results are presented
in Fig. 4. From both Fig. 4(a) and (b), it was apparent that the
oc sizes after oc growth period were obviously improved with
SA addition. In both cases, size of the ocs immediately reduced
with the increasing shear force at 200 rpm. As the shear force was
reduced again, the ocs began to regrow. However, irreversible
breakage was observed for both PAC and PACSA, although the
ocs formed by PACSA showed better recovery ability than those
of PAC. Analysis of the corresponding oc PSD before oc break-
age, after oc breakage and after oc regrowth showed that (i) an
apparent shift in the major peak to the right of the original value
was observed after SA addition; (ii) there was obvious increase in
the smaller oc size between 10 and100 m when PACSA was
used. The results above suggested that, compared with PAC, ocs
formed by PACSA were with larger oc sizes and showed better
recovery ability after 5 min of breakage period as reected by PSD
analysis. That was in accordance with the conclusions obtained in
Sections 3.2.1 and 3.2.2.
3.2.4. Floc structural analysis
In this study, 0.5 mg/L SA was selected to evaluate the effect
of SA on oc structure. The oc structure during oc formation,
breakage and regrowth processes at PAC doses of 1.5 and 2.5 mg/L
was investigated in terms of fractal dimension Df . Coagulation pro-
cesses consisted of 1.5 min of rapid shear at 200 rpm, 15 min of
slow stir at 40 rpm, 5 min of rapid shear at 200 rpm and 15 min of
slow stir at 40 rpm again for oc regrowth. Change in Df of ocs
vs. time for both PAC and PACSA is presented in Fig. 5. The Df of
ocs was derived from the relationship of scattered light intensity
I and the scattering vector Q as shown in Eq. (5). From Fig. 5, it can
be seen that, regardless of oc growth, breakage or regrowth pro-
cess, PACSA gave the ocs with more open structure as reected
by the lower Df values compared with those of PAC, which may be
partly attributed to the adsorption and bridging of the SA molecules
on the negatively charged PACHA ocs. The decreasing in fractal
dimension as bridging increased for activated sludge ocs has been
reported [32], which was conducted by a similar technique. When
PAC doses of 1.5 and 2.5 mg/L were used, PACSA yielded the ocs
with much larger size than those of PAC. It was also suspected that
the larger the oc median diameter, the smaller the fractal dimen-
sion was. A similar phenomenon was reported by Cao et al. [33]. In
addition, Df values of the ocs formed by 1.5 mg/L PAC were more
obviously decreased due to SA addition compared with those by
2.5 mg/L PAC. That may be explained as follows: when PAC dose
increased from 1.5 to 2.5 mg/L, the corresponding zeta potential
of the ocs increased from about 15.5 to 11.0 mV (Fig. 1(d)),
1.74
0 5 10 15 20 25 30 35 40
T (mins)
Fig. 5. Change in fractal dimension of ocs with time for PAC and PACSA during oc
growth (40 rpm) and breakage (200 rpm) followed by a return to the initial 40 rpm
for oc regrowth process.
resulting in the weaker repulsion forces between the collides. So,
when 1.5 mg/L PAC was used, stronger repulsion forces between
the colloids made chain structure of anionic SA more tend to favor
an extended conformation away from the interface [34], which may
result in the formation of ocs with more open structure.
It should also be noted that the Df of ocs increased substan-
tially when shear force of 200 rpm was applied and increased with
increasing shear period. That was possibly attributed to the reason
that the weak points of aggregates were ruptured under high shear
force and rearranged at more dense points and, subsequently, the
oc structure became more compact and stable by restructuring
[34,35].
4. Conclusions
The effect of coagulant aid SA on coagulation behavior and oc
characteristics with PAC was assessed. It could be concluded that
coagulation behavior could be enhanced depending on the doses
of PAC and SA. SA addition showed obvious positive effect on oc
growth rate and oc size. PACSA yielded the ocs with more open
structure, and the oc recovery ability was signicantly improved
after oc breakage compared with PAC. It was suspected that the
main coagulation mechanism of PAC was precipitate charge neu-
tralization, while SA favored adsorption bridging. Coagulation with
PACSA was achieved by a combination of precipitate charge neu-
tralization and adsorption bridging.
Acknowledgments
This study is supported by the National High Technology
Research and Development Program of China (863 Program) (No.
SQ2009AA06XK1482412), Independent Innovation Foundation of
Shandong University, 2010TS070, and is partially supported by the
Cooperative Research Centre for Contamination Assessment and
Remediation of the Environment (CRC-CARE). The kind suggestions
from the anonymous reviewers are greatly acknowledged.
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