Indian Journal of Chemical Technology

Vol. 13, September 2006, pp. 464-469

Application of chitosan and alginate in treating waste water

containing heavy metal ions
Yimin Qin*, Bingbing Shi & Jingjie Liu
The Biochemical Materials Research and Development Center, Jiaxing College, Jiaxing 314001, Zhejiang Province, P.R. China
Email: yiminqin@hotmail.com
Received 5 December 2005; revised received 17 May 2006; accepted 11 July 2006
The use of sodium alginate and chitosan in treating waste water containing heavy metal ions has been studied in this
paper. The effect of the concentration and ratio of chitosan and sodium alginate, treatment temperature and time on the
efficiency of Cu(II) ion removal was investigated. Results showed that when used in combination, sodium alginate and
chitosan were effective in removing Cu(II) ions from waste water. The treatment was applied to other heavy metal ions such
as cadmium, lead and silver ions, and the treatment efficiency was compared. Results showed that when used in
combination, the separation of polymeric absorbents from waste water is better than when chitosan and sodium alginate are
used alone.
Keywords: Sodium alginate, Chitosan, Heavy metal ions, Waste water treatment
IPC Code: C02F1/00, C02F1/62

Heavy metal ions present a serious source for water

contamination, and a number of methods have been
developed over the years for removing them from
waste water. Commercially, activated carbon is often
used to remove heavy metal ions. In recent years,
researchers have worked on inexpensive materials,
such as chitosan, zeolites, and other absorbents, which
have high absorption capacity and are locally
available1. These low-cost absorbents have
demonstrated good removal capabilities for certain
metal ions as compared to activated carbon. Chitosan
was found to be one of the outstanding absorbents
capable of absorbing 815, 273 and 250 mg/g of
Hg(II), Cr(VI) and Cd(II) respectively. Studies have
shown that the absorption capacities can be further
enhanced by chemical modifications of chitosan2-4.
Similar to chitosan, alginate is also a natural
polymer with abundant natural resources5. As a
polymeric acid, alginate can form salt with metal ions.
Whilst chitosan can bind metal ions via chelation with
the amine groups, most divalent metal ions can form
water insoluble salt with alginate6-9.
As a polymeric amine, chitosan is positively
charged when dissolved in weak aqueous acidic
solutions. On the other hand, as a polymeric acid,
alginate is negatively charged in solution. It has been
shown that chitosan and alginate can precipitate each
other through electrostatic forces. This study intends

to utilize the ionic interactions of chitosan and

alginate in enhancing the abilities to remove heavy
metal ions for the two polymers.
Experimental Procedure
The sodium alginate and chitosan powders were
commercial grade material supplied by FMC
Biopolymers and Xindie, respectively. The sodium
alginate has a viscosity in 1% solution of about 40 cps
and has a mannuronate content of about 40%. The
chitosan has a degree of deacetylation of about 85%,
i.e., 85% of the amine groups are in the form of
primary amine.
Sodium alginate and chitosan powders were
dissolved in water and 1% aqueous acetic acid
solution respectively to form the treatment solutions.
The concentrations were both 10 g/L.
CuSO4 was dissolved in water to prepare a solution
containing about 1000 ppm Cu(II) ions. When sodium
alginate or chitosan solutions were used alone,
100 mL of the CuSO4 solutions were measured into
250 mL beakers, and 0, 10, 25, 50, 100 mL of either
chitosan or sodium alginate solutions were added.
After thorough mixing, the mixture was left standing
for 24 h at room temperature. The solutions were then
filtered and diluted by 200 times before the Cu(II)
concentration was measured by atomic absorption
spectrometer.

QIN et al.: APPLICATION OF CHITOSAN AND ALGINATE IN TREATING WASTE WATER

When the sodium alginate and chitosan solutions

were used in combination, to 100 mL of CuSO4
solution was first added 0, 10, 25, 50, 100 mL of
either chitosan or sodium alginate solutions, after
mixing, 20 mL of solution was taken from the
chitosan or sodium alginate mixtures and mixed
together. After being left standing for 24 h at room
temperature, the solution was filtered and diluted by
200 times before the Cu(II) concentration was
measured by atomic absorption spectrometer.
When studying the effect of the ratio between
chitosan and sodium alginate, 100 mL CuSO4 and
20 mL of chitosan solution was first measured into
five 250 mL beakers, to the mixtures were then added
2, 4, 6, 10 and 20 mL sodium alginate solutions.
Separately, 100 mL CuSO4 and 20 mL of sodium
alginate solution was first measured into five 250 mL
beakers, to the mixtures were then added 2, 4, 6, 10
and 20 mL chitosan solutions. After being left
standing for 24 h at room temperature, the solutions
were filtered and diluted by 200 times before the
Cu(II) concentration was measured by atomic
absorption spectrometer.
When studying the effect of temperature, 12.5 mL
of chitosan solution and 12.5 mL of sodium alginate
solution were added into 100 mL CuSO4 solution, the
mixture was stored at 25, 30, 35, 40, 45, 50, 55 and
60oC for 24 h before the Cu(II) ion concentration was
measured.
When studying the effect of reaction time, 12.5 mL
of chitosan solution and 12.5 mL of sodium alginate
solution were added into 100 mL CuSO4 solution,
after 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 8, 9 and

465

10 h, the treatment was terminated and the Cu(II)

concentration was measured.
When studying the treatment efficiency for
cadmium, lead and silver ions, CdCl2, Pb(NO3)2 and
AgNO3 were used to prepare aqueous solutions
containing about 1000 ppm metal ions. The treatment
with cadmium, lead and silver ions were carried out in
a similar way to that used for the Cu(II) ions.
Results and Discussion
Experimental observation after chitosan and
sodium alginate solutions were added into CuSO4
solutions have been summarized in Table 1. Clear
differences can be observed when chitosan and
sodium alginate were used alone. Both resulted in the
precipitation of the polymer, however, the alginate
solution produced a gel like precipitate, whilst the
chitosan produced a loose colloid. Phase separation
was not clear when chitosan and sodium alginate were
used alone. However, when used in combination,
there was a clear separation of the precipitate from the
solution.
The absorption of heavy metal ions by chitosan and
sodium alginate can be quantified in two ways, i.e.,
absorption capacity and rate of removal. The rate of
removal measures the quantity in percentage of the
heavy metal ions removed from the original solution,
whilst the absorption capacity measures the amount of
heavy metal ions absorbed per unit weight of the
absorbent. Rate of removal and absorption capacity
can be calculated by using the following equations.
Rate of removal, R (%) =(C0C1)/C0*100%

Table 1Experimental observation after sodium alginate and chitosan solutions were added into waste water containing Cu(II) ions
Amount added

10 mL

25 mL

50 mL

100 mL
No clear separation of the
precipitate from the
solution, a viscous
solution is formed. Cu(II)
ions were absorbed onto
the surface of the alginate
solution.
A gel like structure was
formed; precipitates were
separated from the
solution after heating in a
hot water bath.
Clear separation of the
precipitate from the
solution

Sodium alginate
solution

Clear separation of the

precipitate from the
solution; loose film-like
structure

Clear separation of the

precipitate from the
solution; thick layer of
precipitate

No clear separation of the

precipitate from the
solution, a thick colloid is
formed.

Chitosan
solution

Loose colloid precipitate

settles onto the bottom of
the container.

Loose colloid precipitates

were formed.

1:1 Mixture of
sodium alginate
and chitosan
solution

Clear separation of the

precipitate from the
solution

Clear separation of the

precipitate from the
solution

A gel like structure was

formed; precipitates were
separated from the
solution after heating in a
hot water bath.
Clear separation of the
precipitate from the
solution

INDIAN J. CHEM. TECHNOL., SEPTEMBER 2006

466

molecules could fully combine with the heavy metal

ions, hence the absorption capacity was high; 1 g
sodium alginate can absorb 262.4 mg Cu(II) ions.
When the concentration increases, the rate of removal
increased, however, the absorption capacity showed a
decline.

where R=Rate of removal (%); C0=Concentration of

heavy metal ions in the original solution (g/mL) and
C1=Concentration of heavy metal ions in the treated
solution (g/mL).
Absorption capacity Q =(C0-C1)*V/1000 m
where Q=Absorption capacity (weight of heavy metal
ion removed, mg/weight of absorbent, g); V = Volume
of solution being treated (mL) and m = Weight of
absorbent used (g).

Effect of the ratio between chitosan and sodium alginate on

the treatment result

Table 3 shows the effect of the ratio between

chitosan and sodium alginate on the treatment result.
In general, the removal rate is better when the amount
of sodium alginate is more than chitosan. As been
pointed out earlier, sodium alginate combines heavy
metal ions through the formation of insoluble salt and
gellation occurs when sodium alginate solution is
added into a solution containing Cu(II) ions. For
chitosan, it combines with heavy metal ions through
chelation, and a loose colloid is formed. When the
amount of alginate is more than chitosan, the alginate
combines with heavy metal ions to form an insoluble
gel, and the chitosan is attached to the gelled structure
through electrostatic forces. On the other hand, when
chitosan is in excess, the excess amount of chitosan
that is not coagulated with the sodium alginate is
dispersed in the solution, which can stabilize part of
the heavy metal ions in the solution, hence reducing
the amount of heavy metal ions absorbed onto the
polymeric absorbent.

Effect of chitosan and sodium alginate concentrations on

heavy metal ion removal

Table 2 shows the Cu(II) concentration after

different amounts of chitosan and sodium alginate
solutions were added into 100 mL CuSO4 solutions. It
can be seen that the same amount of chitosan and
sodium alginate produced remarkably different
results. Sodium alginate had a much better removal
rate than chitosan. The removal rate was 80.7% when
50 mL sodium alginate solution was added, and the
Cu(II) ions in the original solution can be completely
removed when 100 mL sodium alginate solution was
added.
The removal rate for chitosan was below 70%. It
reached an equilibrium when 50 mL of chitosan
solution was added; more chitosan did not produce a
better removal rate. When chitosan and sodium
alginate were used in combination, the removal rate
was not as good as when sodium alginate was used
alone, but it was better than when chitosan was used
alone.
1 mol sodium alginate can combine with about 3
mol Cu(II) ions, whilst 1 mol chitosan can combine
with 1.5 mol Cu(II) ions. When the concentrations of
chitosan and sodium alginate were low, the polymeric

Effect of treatment time

Figure 1 shows that at the beginning of the

treatment, there was a rapid rise of removal rate; the
process then slowed down and reached an equilibrium
after about 7 h. The absorption capacity for
the sodium alginate/chitosan complex was about
66.4 mg/g at 25 min; it reached 147.5 mg/g at 10 h.

Table 2Effect of chitosan and sodium alginate concentrations on heavy metal ion removal
Amount added (mL)
Cu(II) concentration
(g/mL)

10

25

50

Sodium alginate
4.180
2.868
1.813
0.806
Chitosan
4.338
3.593
2.468
1.560
1:1 Mixture
4.226
3.439
2.319
1.365
Removal Rate (%)
Sodium alginate
0
31.4
56.6
80.7
Chitosan
0
17.2
43.1
64.0
1:1 Mixture
0
18.6
45.1
67.7
Absorption capacity
Sodium alginate
0
262.4
189.4
135.0
(mg Cu(II)/g polymer)
Chitosan
0
149.0
149.6
111.1
1:1 Mixture
0
206.0
118.2
114.4
Note: The Cu(II) concentrations quoted in this table were for the filtered solution after 1:200 dilution.

100
0.000
1.465
0.735
100.0
66.2
82.6
83.6
57.5
69.7

QIN et al.: APPLICATION OF CHITOSAN AND ALGINATE IN TREATING WASTE WATER

467

Table 3Effect of the ratio between chitosan and sodium alginate on the treatment result
Amount of chitosan
(mL)

Amount of sodium alginate

(mL)

Cu(II) concentration
(g/mL)

Removal rate
(%)

0
0
4.312
0
20
2
2.834
34.3
20
4
2.723
36.8
20
6
2.596
39.8
20
10
2.468
42.8
20
20
1.987
53.9
10
20
2.278
47.2
6
20
2.416
44.0
4
20
2.532
41.3
2
20
2.627
39.1
Note: The Cu(II) concentrations quoted in this table were for the filtered solution after 1:200 dilution.

Fig. 1Effect of time on the removal rate of Cu(II) ions

Effect of temperature

Figure 2 shows the effect of temperature on

removal rate. When the temperature was in the 2545C range, the absorption capacity was relatively
low. However, as the temperature rose to above 45C,
there was a significant rise in the absorption capacity.
Above that, the effect of temperature on removal rate
was small. The absorption capacity for the sodium
alginate/chitosan complex was 133.1 mg Cu(II) per
gram polymer at 25C; it rose to 177.3 mg/g at 45C.
Treatment efficiency for different types of heavy metal ions

Table 4 shows the experimental observation when

sodium alginate and chitosan were used to treat
solutions containing different types of heavy metal
ions. Except for the silver ions, sodium alginate alone
was able to produce precipitates when added to the
solutions. The chitosan solution was able to produce
colloid precipitate only in the Cu(II) solution.
Since, silver ion is a mono-valent metal ion, when
the silver ions are in contact with sodium alginate, the
resultant silver alginate is water soluble. Although,

Absorption capacity
[mg Cu(II)/g polymer]
0
134.4
132.4
128.7
122.9
116.2
135.6
142.2
148.3
153.2

Fig. 2Effect of temperature on the removal rate of Cu(II) ions

literature information has suggested that chitosan can

chelate silver ions, when chitosan solution was in
contact with silver ions, no precipitation was
observed.
When sodium alginate and chitosan solutions were
first dispersed into silver containing solutions
separately, and then the two solutions were mixed
together, the sodium alginate and chitosan formed an
insoluble polymeric network. The structure of this
network is similar to EDTA, since, it has both the
primary amine and carboxylic acid groups. Since
sodium alginate and chitosan precipitated each other,
the silver ions that were absorbed by them also
separated out from the solution.
Similar to the results observed for the Cu(II) ions,
the use of sodium alginate and chitosan in
combination also produced enhanced treatment result
for Cd(II) and Pb(II) ions, the separation of the
polymeric precipitate from the solution is much better
than when either sodium alginate or chitosan solutions
are used alone.

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INDIAN J. CHEM. TECHNOL., SEPTEMBER 2006

Table 4Experimental observation after sodium alginate and chitosan solutions were added into waste water containing Ag(I), Pb(II),
Cd(II) and Cu(II) ions
Metal ion

After addition of 25 mL sodium alginate

solution

After addition of 25 mL
chitosan solution

After addition of 12.5 mL each of sodium

alginate and chitosan solutions

Ag(I)
Pb(II)

No precipitate
No clear separation of the precipitate
from the solution; formation of gel like
structure.
Clear separation of the precipitate from
the solution; formation of white colloids.
Formation of blue gel structure.

No precipitate
No precipitate

White precipitate
Formation of gel like structure

No precipitate

Formation of gel like structure

Formation of blue colloids

Clear separation of blue precipitates from

solution

Cd(II)
Cu(II)

Table 5Treatment efficiency for different types of heavy metal ions

Heavy metal ion
concentration
(g/mL)

Removal rate
(%)

Absorption capacity
(mg heavy metal ions/g
polymers)

Original solution
3.452
0
+25mL sodium alginate solution
1.926
44.2
Ag(I)
+25 mL chitosan solution
2.586
25.1
+12.5 mL each of sodium alginate and chitosan solution
2.480
28.2
Original solution
3.186
0
+25mL sodium alginate solution
0
100.0
Pb(II)
+25 mL chitosan solution
1.318
58.6
+12.5 mL each of sodium alginate and chitosan solution
0.334
89.5
Original solution
2.078
0
+25mL sodium alginate solution
1.267
39.0
Cd(II)
+25 mL chitosan solution
1.878
9.6
+12.5 mL each of sodium alginate and chitosan solution
1.585
23.7
Note: The heavy metal ion concentrations quoted in this table were for the filtered solutions after 1:200 dilution.

Table 5 shows the removal rate and absorption

capacity when the sodium alginate and chitosan
solutions were used to treat waste water containing
Cu(II), Cd(II), Pb(II) and Ag(I) ions. For the Ag(I)
ions, the absorption capacities for sodium alginate and
chitosan were 122.1 and 69.3 mg/g, respectively.
Sodium alginate has an excellent removal rate for
Pb(II) ions, it can completely remove the Pb(II) ions
from waste water, with the absorption capacity at
254.9 mg/g. Although, the addition of chitosan
solution did not produce visible precipitate, after
filtration, 58.6% Pb(II) ions were removed from the
waste water.
Both the sodium alginate and chitosan had poor
treatment efficiency against Cd(II) ions, the removal
rates were 39.0 and 9.6%, respectively. The
absorption capacity was 64.9 and 3.0 mg/g,
respectively for sodium alginate and chitosan.
Conclusions
This study has shown that both the sodium
alginate and chitosan can absorb a significant amount

0
122.1
69.3
77.8
0
254.9
149.4
228.2
0
64.9
3.0
39.4

of heavy metal ions. When placed in contact with

heavy metal ions, sodium alginate tends to form an
insoluble gel structure, whilst chitosan forms a
loose colloid structure. When sodium alginate and
chitosan are used in combination, the separation of the
polymers containing the heavy metal ions from the
solution is much better than when the sodium
alginate and chitosan solutions are used alone, hence
improving the process for the removal of heavy
metal ions. Results of this study further indicate that
for mono-valent metal ions such as silver ions, it is
difficult for either sodium alginate or chitosan
solutions to precipitate the metal ions, however,
when used in combination, there is a clear separation
of the polymeric absorbent from the waste
water, resulting in the removal of the heavy metal
ions.
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