Colloids and Surfaces A: Physicochem. Eng.

Aspects 229 (2003) 121–127

Poly-aluminum-silicate-chloride (PASiC)—a new type of

composite inorganic polymer coagulant
B.Y. Gao a,∗ , Q.Y. Yue a , B.J. Wang a , Y.B. Chu a
a School of Environmental Science and Engineering, Shandong University, No.27 Shanda South Road,
Jinan 250100, Shandong, China

Received 28 February 2003; accepted 10 July 2003

Abstract

A new inorganic polymer coagulant, poly-aluminum-silicate-chloride (PASiC), was prepared by two approaches: (1) hydrox-
ylation of the mixture of AlCl3 and fresh polysilicic acid in Al/Si ratios ≥5, (PASiCc); (2) hydroxylated poly-aluminum-chloride
(PAC) combined with polysilicic acid aged 2 h in Al/Si ratios ≥5, (PASiCm). The hydrolysis-polymerization process of Al(III)
in PASiC solution was examined with pH titration method. The performances of PASiC in comparison with PAC were charac-
terized by various experimental methods. The results have shown that there exist some interactions between aluminum species
and polysilicic acid, especially at low basicity (B) value, which can play a part in the chemical structure, the molecular weight
distribution, the electrokinetic characteristics and the coagulating properties of PASiC. The complexes formed when different
charged aluminum species and polysilicic acid are combined have a less positive charge but a larger molecular weight than
the corresponding aluminum hydrolysis products at the same pH value. Therefore, it is necessary to consider the aggregating
efficiency and charge effectiveness when developing PASiC coagulant. In general, PASiC has shown a high coagulation effect,
superior to that of PAC for both turbidity and color removal.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Coagulation and flocculation; Electrokinetic chemical characterization; Inorganic polymer coagulant; Molecular weight
fractionation; Turbidity and color removal

1. Introduction can be considered as the second generation of metal

The production and the application of inorganic
polymer flocculants (IPF) are increasing rapidly
throughout the world. Since these compounds have
different behaviors from traditional water treatment
reagents in many respects, the pre-produced varieties
∗ Corresponding author. Tel.: +86-531-8364832;
fax: +86-531-8364513.
E-mail address: bygao@sdu.edu.cn (B.Y. Gao).
salt coagulants [1]. The merits of IPF are reflected in
their superior efficiency compared to traditional salts
and much lower cost than organic polymer flocculants
(OPF). However, concerning their morphology and
coagulating-flocculating characteristics, the IPF may
remain in a position between the common metal salts
and organic flocculants [2]. Their molecular weight
and size for aggregating action and their stability to
resist further hydrolysis are still much lower than
those of the OPF. These are the main weaknesses

0927-7757/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2003.07.005
122 B.Y. Gao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 229 (2003) 121–127
of IPF to be improved. This is the impetus for the
research to develop a variety of composite inorganic
polymer flocculants.
In the operation of water treatment process using
traditional coagulants, there were many approaches to
improve their aggregating efficiency by adding aids,
such as activated silica and lime, separately from the
coagulants. With the success of tailor-made produc-
tion of IPF, it is logical to combine the aids into a uni-
fied reagent for simplification of the operation in water
treatment plants. This may be the first aim when study-
ing the composite flocculants. Accordingly, to com-
bine the aids with original metal salt coagulants is also
a concomitant approach in developing the new type
of reagents. The combination of activated silica (i.e.
a special form of polymerized silicic acid) with alu-
minum sulfate may be an example of this strategy [3].
The salts of aluminum and silicate are usually the
main materials used to prepare the composites. They
may be pre-polymerized by hydroxylation individu-
ally or mixed initially in their original form and then
hydrolyzed together. Nevertheless, eventually they be-
come the polymeric components of the composite. The
other additives may be inorganic or organic ligands or
organic polymer flocculants.
The contribution of each individual component of
a composite in the coagulation–flocculation process
may be positive or negative in different respects [4].
How to successfully enhance one function and to
avoid the concomitant loss of another efficiency is
the problem. For example, improving the aggregat-
ing function with a negatively-charged additive often
decreases the charge-neutralization function of the
positively-charged components. In this situation, a net
positive profitable treatment result would be the aim
of modification.
Finding a suitable ratio among the components and
a successful procedure of preparation are the important
goals of this research. The morphology, the molecu-
lar weight distribution, the electrokinetic characteris-
tics, the chemical speciation and the transformation
of each component in preparation are the key points
in the studies. Detection using chemical methods and
instrumentation is a primary requisite along the exper-
imental progresses.
More recently, descriptions of the preparations of
aluminum-silicate polymer composite coagulants, for
example, poly-silicate-aluminum-sulfate (PSAS) and
poly-aluminum-silicate-sulfate (PASS), have appeared
in the patent literatures [5,6]. The PSAS contains lower
concentration of aluminum with Si/Al = 1∼5, but
the PASS contains high concentration of aluminum
with Si/Al = 0.05. In Japan and China, some studies
demonstrated that adding Al or other salts can delay
the gelation time of activated silica [7,8]. Also, there
are several reports indicating that aluminum-silicate
polymer composites are highly effective for removal
of turbidity and humics and for treatment of cold water
[3,9]. However, there is little information about the
preparation of PASiC and its coagulation behavior.
When aluminum chloride or PAC is used to pro-
duce the aluminum-silicate composite, there are two
ways of designing the aluminum-silicate composite.
If the silicate component is dominant and aluminum
salts are added as a stabilizer to improve its reten-
tion after preparation, it is still a modified anionic
inorganic polymer flocculant (PSiAC). When the alu-
minum component is dominant and silicate is added
to promote aggregation, it would be a cationic in-
organic polymer flocculant (PASiC). Nevertheless,
pre-combination of cationic and anionic polymer
flocculants would result in a decrease in net charge.
In this paper, PASiC was prepared by two proce-
dures, and the hydrolysis-polymerization process of
aluminum existing with polysilicic acid was investi-
gated by means of pH titration method. The study also
attempted to determine the molecular weight distribu-
tion of PASiC with B = 2.0 and different Al/Si ratios
by using ultrafiltration membranes. B = [OH]/[Al]
ratio, where [OH] and [Al] are the total concentration
of OH and Al added in PASiC solution, respectively.
The charge-neutralization function of PASiC was also
examined by streaming current (SC) and zeta poten-
tial (ZP) measurement. The coagulation for removal of
turbidity and color was conducted by jar test. All these
experiments were conducted in comparison with PAC.
The initial results of the experiments will be useful for
the development of a new kind of aluminum-silicate
polymer composite coagulant.
2. Materials and methods
2.1. Materials
All reagents used are analytically pure chemicals
except water glass is commercial grade and humic acid
 B.Y. Gao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 229 (2003) 121–127
is a commercialized product bought from the Aldrich
Chemical Co. Deionized water was used to make all
solutions.
2.2. Preparation of polysilicic acid solution
Water glass containing 26.5% SiO2 was diluted to
a concentration of 0.5 M SiO2 with deionized water.
The diluted water glass solution was neutralized to
pH 2.0 with 0.5 M HCl under magnetic stirring. The
neutralized water glass solution contained 0.3187 M
SiO2 .
2.3. Preparation of poly-aluminum-silicate-chloride
(PASiC) coagulant
Stock solution of 1.0781 M AlCl3 was diluted with
deionized water to 0.25 M AlCl3 before the PASiC
coagulant was prepared. There were two approaches
to prepare PASiC as follows: (1) quantitative diluted
AlCl3 solution was slowly titrated with 0.5 M NaOH
solution to obtain the desired [OH]/[Al] ratio PAC
solution using a 655 Dosimat Micro-Titration appa-
ratus. The [OH]/[Al] ratio was denoted hereafter by
B, where [OH] and [Al] were the total concentration
of OH and Al added in the solution, respectively.
The titration rate was 0.05 ml/min NaOH solution.
During titration, the 655 Dosimat Micro-Titration
apparatus was used to record the change of pH and
the solution was vigorously stirred (∼300 rpm) to
ensure that homogeneous solution was obtained. The
final aluminum concentration (denoted AlT ) of PAC
solution was 0.1 M. Then, the PAC was combined
with polysilicic acid aged for 2 h in Al/Si ratio ≥5
to obtain poly-aluminum-silicate-chloride (PASiCm)
coagulant, in which the AlT was 0.094–0.098 M.
(2) The diluted AlCl3 solution and fresh polysilicic
acid were mixed at different Al/Si ratios before the
base was added. Then the 0.5 M NaOH solution
was added slowly (0.05 ml/min) under vigorously
agitation to obtain desired B value and different
Al/Si ratio poly-aluminum-silicate-chloride coagulant
(PASiCc), which was with 0.1 M AlT . Also, during
titration, the 655 Dosimat Micro-Titration apparatus
was used to record the change of pH and the so-
lution was vigorously stirred (∼300 rpm) to ensure
that homogeneous solution was obtained. The pre-
pared coagulant samples were capped, sealed and
123
stored overnight at 20◦ prior to the initiation of
analysis.
2.4. Measurement of nominal molecular weight
(NMW) by ultrafiltration
For the measurement, an aliquot 100 ml sample of
coagulant was poured into a stirred vessel, in which
an ultrafilter was placed at the bottom of the ves-
sel. After the stirred vessel was sealed, a pressure
of 3.0 kg/cm2 was applied to the vessel by nitrogen
gas. The sample was thus filtered until all the filter-
able sample was obtained. The filtrate was acidified
with 1:1 HCl solution to about pH 0.5. By means of
Al-ferron timed complex colorimetric method [10,11],
the concentration of aluminum in the acidified filtrate
was determined at 370 nm wavelength with a spec-
trophotometer. The nominal molecular weight dis-
tribution of the samples was calculated accordingly.
The ultrafilters used, made of anisotropic polysulfone
and poly-n-phenyleneisophthalicamide, have nomi-
nal fractionation molecular weights of 3000, 6000,
10,000, 60,000 and 100,000.
2.5. Measurement of streaming current (SC)
SC was detected successively by a SC-303 Stream-
ing Current Detector, or SCD. For experiments, dif-
ferent coagulant doses were added into 2.5 l test water
made up of 50% deionized water and 50% tap water.
A variable speed stirrer working at 240 rpm was used
to mix the water sample well at all time. SC values
were recorded under different coagulant dosage. Dur-
ing the experiment, the pH of the water was regulated
with 0.1 M HCl or 0.1 M NaOH solution and main-
tained constant.
2.6. Measurement of electrophoretic mobility
The measurement of electrophoretic mobility (EM)
of particles after addition of coagulant under different
pH and coagulant dosages was carried out by using
a JS94E Micro-Electrophoresis Apparatus (Jiecheng
Company, Ltd., Shanghai, China). Samples of about
0.5 ml were taken from the stirred vessel by a 2 ml sy-
ringe and transferred directly into the cuvette. Timing
of the particles was carried out using a microcomputer
keyboard as a ‘stopwatch’. Typically, 10 particles
124 B.Y. Gao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 229 (2003) 121–127
were timed in one direction, and the mean mobility
was computed directly from the 20 readings. Zeta
potentials (ZP) were calculated from the EM value.
2.7. Jar-test experiments
Coagulation tests were performed by using a syn-
thetic suspension containing 50 mg/l kaolinite and
10 mg/l humic acid, which was made up of 50%
deionized water and 50% tap water. The particle
diameter and the specific surface of kaolinite are
0.5–6.25 ␮m and 23.2 m2 /g, respectively. The tap wa-
ter is mainly characterized by pH of 7.45, turbidity of
0.7 NTU and CODMn of 3.0 mg/l, respectively. The
initial turbidity, absorbance and pH of the suspen-
sion were 26.2 NTU, 0.207 and 7.02, respectively.
The coagulation experiments were conducted in 1.0 l
plexiglass beakers using a conventional jar-test ap-
paratus, DC-506 Laboratory Stirrer (Huashui New
Technological Development Co., Shanghai, China).
The 800 ml suspension solutions were dosed with
different coagulants to give final concentrations in
the range of 0.00–0.12 mmol/l Al. The solutions were
stirred rapidly at 200 rpm for 2 min during coagulant
addition. Directly after the rapid mixing, about 15 ml
of the suspension was taken by a 20.00 ml syringe
for EM measurement. Then a 15 min period of slow
stirring (40 rpm) and 10 min sedimentation followed.
After sedimentation, a supernatant sample was with-
drawn for turbidity and UV absorbance measurement.
Turbidity was measured by a YZD-1A turbidimeter,
and the content of humic acid expressed as absorbance
in the treated suspension was analyzed with a UV-754
spectrophotometer at 370 nm using 1 cm quartz cells.
3. Results and discussion
3.1. Character of hydrolysis-polymerization of
aluminum (III) in PASiC solution
When base was slowly added to the mixed solutions
of AlCl3 and fresh polysilicic acid with different Al/Si
ratios, the pH of the solution increased with increas-
ing of base addition, as shown in Fig. 1. It is seen that
the curve of PAC has one plateau bounded by two in-
flection points. The first inflection point approximately
occurs at about B = 0.5, and the second inflection
8
PAC
7 PASiC Al/Si=15
PASiC Al/Si=10
6 PASiC Al/Si=5.0
pH
4
3
2
0.0 0.5 1.0 1.5 2.0 2.5 3.0
B value
Fig. 1. Titration curves of Al(III) solutions with base addition for
PAC and PASiC with AlT = 0.1 M.
point occurs at about B = 2.5. Before the second
inflection point, the pH value changes smoothly and
slightly with the increasing of B value. The curves of
PASiC are different from that of PAC because of coex-
istence of hydrolyzed aluminum species and polysili-
cic acid. Fig. 1 shows that the influence of polysilicic
acid on the curves of PASiC depends on the Al/Si ratio
and B value. The less the Al/Si ratio and B value, the
more obvious the difference between PAC and PASiC
curves. The curve of PASiC with Al/Si = 15 is similar
to that of PAC, which has two inflection points, occur-
ring at about B = 0.5 and B = 2.5, respectively. For
PASiC with Al/Si ratios of 10 and 5, the pH-B curves
only displayed one inflection point at about B = 2.5.
The results above suggest that there is some interaction
between hydrolyzed aluminum species and polysilicic
acid. The polysilicic acid can have combined with alu-
minum and its hydrolysis products by Al-O-Si bonds
[12,13] to form hydroxyaluminosilicate species, which
can retard the hydrolysis-polymerization of aluminum
to some extent.
3.2. Nominal molecular weight distribution
The nominal molecular weight distribution of PA-
SiC with B = 2.0 and various Al/Si ratios was com-
pared to that of PAC with B = 2.0 by way of the
molecular weight fractionation described in the pre-
ceeding section. The results obtained are shown in
Table 1. It is obvious that the molecular weight of
all polymers in PASiC was increased owing to the
addition of polysilicic acid to AlCl3 solution. The
more the concentration of polysilicic acid (i.e. the less
 B.Y. Gao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 229 (2003) 121–127 125

Table 1
Molecular weight distribution of PASiC and PAC (B = 2.0)
Sample AlT (M) Nominal molecular weight

>3000 >6000 >10,000 >60,000 >100,000

PAC 0.1 62.2 53.7 37.5 21.5 11.5

PASiCc Al/Si =5 0.1 89.2 85.5 78.5 72.3 68.2
PASiCm Al/Si =5 0.094 80.2 75.8 64.3 51.2 40.3
PASiCc Al/Si = 10 0.1 79.4 73.3 65.3 57.6 50.8
PASiCm Al/Si = 10 0.097 70.6 63.3 45.2 38.2 21.4
PASiCc Al/Si = 15 0.1 73.5 68.1 56.4 41.9 20.1
PASiCm Al/Si = 15 0.098 67.3 58.2 39.8 22.5 13.1

the Al/Si ratio) in PASiC, the higher the molecular
weight of the polymers. PASiCc has higher molecu-
lar weight in comparison with PASiCm at the same
Al/Si ratio. These results suggest that when PASiC is
used in water and wastewater treatment, much stronger
bridge-formation than that of using PAC can occur in
the flocculation step [14].
3.3. Electrokinetic chemical characteristics of PASiC
and PAC
PASiC with B = 2.0 and different Al/Si ratios and
PAC with B = 2.0 were selected for these experi-
ments. The relationship between SC and the dosage
of coagulants in the test water made up of 50% deion-
ized water and 50% tap water is shown in Fig. 2.
Because the SC-dose curves of PASiCc and PASiCm
at Al/Si = 15 completely overlap, only 6 curves are
shown in Fig. 2. Table 2 shows the required dosage
when SC reaches zero. From Fig. 2 and Table 2, it
is clear that the positive charge of PASiC decreases
3 a maximum value at a pH range from 5.0 to 6.0
2
1
0 Table 2
SC (mA)
as the polysilicic acid fraction increases. The results
also show that the preparation technique of PASiC
has some effect on the electrokinetic chemical char-
acteristics of PASiC. PASiCc gives little stronger
charge-neutralizing capacity than PASiCm at the
same ratio of Al/Si. The results discussed above
demonstrate that charge-neutralization occurred when
the different charged polymers were combined. This
suggests that the combination of PAC and polysilicic
acid could be enhanced in aggregating efficiency due
to the higher molecular weight but weaken charge
effect in the coagulation process.
Fig. 3 shows the change of zeta potential (ZP)
with respect to pH for PASiC with B = 2.0 and
different Al/Si ratio and PAC with B = 2.0 at the
dosage of 0.5 mmol/l as Al. In every case, a similar
pattern was obtained as to the change of ZP over a
wide range of pH, however, the curves of ZP versus
pH for PASiC are all lower than that for PAC. The
more the proportion of polysilicic acid in PASiC, the
lower the curve of ZP versus pH. With increasing
value of pH from the very acidic side, the ZP took
on the positive side both for PAC and PASiC, then

PAC
PASiCc Al/Si=5.0 Required dose for PASiC and PAC at SC = 0 (B = 2.0)
-1 PASiCm Al/Si=5.0
PASiCc Al/Si=10 Coagulant Dose (mmol/l)
-2 PASiCm Al/Si=10
PASiCc Al/Si=15 PAC 0.028
-3 PASiCm Al/Si=15
PASiCc Al/Si =5 0.048
-4 PASiCm Al/Si =5 0.060
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16
PASiCc Al/Si = 10 0.034
Al(mmol/L) PASiCm Al/Si = 10 0.036
PASiCc Al/Si = 15 0.031
Fig. 2. Streaming current graphs of PASiC compared to PAC PASiCm Al/Si = 15 0.032
(B = 2.0).
126 B.Y. Gao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 229 (2003) 121–127

40 20
10
30
0
ZP[mv]

20
-10
ZP[m V]

10 PAC B=2.0
PASiCc Al/Si=5 -20 PASiCc B=2.0 Al/Si=5.0
0 PASiCm Al/Si=5 PASiCm B=2.0 Al/Sl=5.0
PASiCc Al/Si=10 -30 PASiCc B=2.0 Al/Si=10
-10 PASiCm Al/Si=10 PASiCm B=2.0 Al/Si=10
-40
PASiCc Al/Si=15 PASCc B=2.0 Al/Si=15
-20 PASiCm Al/Si=15 -50 PASCm B=2.0 Al/Si=15
PAC
-30 2 4 6 8 10 12 14
4 5 6 7 8 9 10 -5
Al dose[X10 mol/L]
pH
0.16
Fig. 3. Change of ZP with respect to pH for PASiC and PAC 0.14
PAC B=2.0
(B = 2.0). 0.12 PASiCc B=2.0 Al/Si=5.0
PASiCm B=2.0 Al/Si=5.0
Absorbance

0.10 PASiCc B=2.0 Al/Si=10

PASiCm B=2.0 Al/Si=10
decreased monotonically to reach an isoelectric point 0.08 PASCc B=2.0 Al/Si=15
at slightly higher pH than the neutral, and finally 0.06 PASCm B=2.0 Al/Si=15

moved into the negative side. In addition, when the 0.04

Al/Si ratio was changed from 15 to 5, the isoelectric
0.02
point moved toward the acidic side of pH for both
0.00
PASiCc and PASiCm. Again, the results of ZP mea- 0 2 4 6 8 10 12
surements demonstrate that the charge-neutralization -5
Al dose(X10 mol/L)
occurred when the different charged polymers were
24
combined. 22
20 PAC B=2.0
3.4. Evaluation of coagulation performance 18 PASiCc B=2.0 Al/Si=5.0
16 PASiCm B=2.0 Al/Si=5.0
PASiCc B=2.0 Al/Si=10
RT(NTU)

14
The coagulation performance of PASiC with differ- 12 PASiCm B=2.0 Al/Si=10
PASCc B=2.0 Al/Si=15
ent Al/Si ratios and B = 2.0 was evaluated in com- 10 PASCm B=2.0 Al/Si=15
parison with PAC (B = 2.0) at pH = 7.0 with the 8
6
synthetic suspension. The results given in Fig. 4 show 4
that the ZP, absorbance and residual turbidity (RT) 2
of the suspension varies with increasing of dosages 0
0 2 4 6 8 10 12
of PASiC and PAC. The ZP for all the coagulants
-5
tested increases with increasing of dosages of the co- Al dose(X10 mol/L)
agulants from negative ZP changing into positive ZP, Fig. 4. Comparative coagulation performance of PASiC and PAC
however, the ZP for microflocs freshly formed with (B = 2.0) at pH value of 7.02.
PASiC are all lower than that formed using PAC with-
out polysilicic acid. As the proportion of polysilicic means that preparation technique of PASiC has less
acid increases, the ZP of PASiC decreases accordingly. effect on its charge-neutralization capacity.
When the ratio of Al/Si is 5, the ZP of all PASiC co- The RT and the absorbance in the jar tests re-
agulants is negative for all doses. This means that the flected the coagulation efficiency of coagulants. No
charge-neutralization effectiveness of PASiC in coag- matter what the ratio of Al/Si was, both RT and ab-
ulation processes is weakened owing to the interaction sorbance could approach zero at high dose, but the
between hydrolyzed aluminum species and polysili- effect differed at lower doses. PASiCm with the ratio
cic acid. It is known from Fig. 4 that the differences of Al/Si = 5 had the most negative ZP, and its coag-
of ZP between PASiCc and PASiCm are slight, which ulation effect was less than that of PAC. All the other
 B.Y. Gao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 229 (2003) 121–127
PASiC coagulants, regardless of the Al/Si ratio, were
more efficient than PAC, although some of their ZP
were in the negative zone. This means that preparation
technique of PASiC has a great effect on its coagula-
tion efficiency, especially at lower ratio of Al/Si.
4. Conclusions
This paper dealt with the comprehensive investiga-
tion of PASiC, a new inorganic polymer coagulant. In
the first part of this paper, procedures to prepare PASiC
were discussed. Then, the hydrolysis-polymerization
process of aluminum (III) with or without polysilicic
acid was comparatively studied to investigate the in-
teraction between hydrolyzed aluminum species and
polysilicic acid. And then, the molecular weight dis-
tribution and electrokinetic properties of PASiC and
PAC were discussed. In the final part, the effectiveness
of the PASiC and PAC for coagulation and floccula-
tion was comparatively evaluated by means of con-
ventional jar tests. It is clear from these studies that
there exist some interactions between hydrolyzed alu-
minum species and polysilicic acid, especially at low
B value, which can play a part in the chemical struc-
ture, the molecular weight distribution, the electroki-
netic characteristics and the coagulating properties of
PASiC. The complexes formed when different charged
hydrolyzed aluminum species and polysilicic acid are
combined have a lower positive charge but a larger
molecular weight than the corresponding aluminum
hydrolysis product at same pH value. Therefore, it
should be given a comprehensive consideration to the
aggregating efficiency and charge effectiveness when
developing PASiC coagulant. In general, PASiC is bet-
ter than PAC according to the evaluation of coagula-
tion performance of this paper.
How to preserve the merits of the individual com-
ponents to the maximum extent is a problem, how-
127
ever. The preparation procedure, chemical structure
and coagulation–flocculation behaviors all remain to
be optimized in further research.
Acknowledgements
The authors thank the Chinese National Foundation
of Natural Sciences for support.
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