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Abstract
Biosorption, the passive accumulation of metals by biomass, can be used as a cost-eective process for the treatment
of metal polluted industrial euents. The green alga Ulva fascia and the brown seaweeds Sargassum hemiphyllum,
Petalonia fascia, and Colpomenia sinuosa were characterized in terms of their number of binding sites, their charge
density and intrinsic proton binding constant (pKa ) using pH titrations at dierent ionic strengths. The determined
number of binding sites decreased in the order Petalonia P Sargassum > Colpomenia > Ulva. Due to their high number
of binding sites Sargassum and Petalonia are most promising for biosorption applications. The decrease of proton
binding with increasing ionic strength and pH as well as the increase of Cu and Ni binding with increasing pH and
decreasing ionic strength could be described by the Donnan model in conjunction with an ion exchange biosorption
isotherm. 2000 Elsevier Science Ltd. All rights reserved.
Glossary
C
CH
CM0:5
Ct
H
I
KH
KM
M
m
pKa
qH
qM
Corresponding author.
V
Vm
YV
[]
k
Indices
add
app
des
i
p
1. Introduction
The passive (not metabolically mediated) binding of
metals by living or dead biomass is commonly referred
to as biosorption. This process can be used to remove
and recover toxic heavy metals from metal bearing industrial wastewaters (Volesky, 1990). Compared to
conventional techniques such as precipitation or
synthetic ion exchange resins, biosorption oers the
0045-6535/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 4 2 1 - X
272
273
ing heavy metal binding were measured by atomic absorption spectrometer (Varian AA-20). The initial
concentrations ranged from 10 to 1000 lg/ml.
2.3. Determination of the equilibrium cation binding
2.3.1. Protons
The mass balance for protons is
qH;i m Hadd VH;add OHadd VOH;add Hi Vi
qH m HV
mM;
mequiv=g:
mM;
mequiv=g:
274
mequiv=g;
275
Fig. 1. Titration of protonated algal biomass at dierent ionic strengths. Experimental data and predictions of the Donnan model for
rigid particles (DORI): (a) Sargassum, (b) Colpomenia, (c) Petalonia, (d) Ulva.
qH CH Hp HVm
mequiv=g:
l=mol:
0.17
11
0.14
0.14
0.20
0.17
0.24
0.07
1.30
0.75
1.45
0.55
1.25
0.15
1.53
0.39
10
0.60
0.66
1.91
6.44
0.20
0.07
0.24
0.06
0.20
0.07
0.24
0.06
Dqb
(mequiv/g)
Vm Vm 0.5
Bt (ml/g)
l=mol:
12
3.3
3.8
5.8
Average
MATLAB optimized.
Absolute mean square deviations of model predictions from data for qH .
b
2.6
1.5
2.9
1.1
5.9
6.4
5.4
5.3
3.5
3.9
3.6
4.0
2.7
3.6
3.1
3.9
Sargassum
Colpomenia
Petalonia
Ulva
With pKa 3
Vm , opta
(ml/g)
pKapp
pKapp
pKa , opta
High I
Low I
Optimum pKa
Vm , opta
(ml/g)
d
Intrinsic pKa
Apparent pKa
Bt
c
b
a
Part
Table 1
DORI model parameters for pH titrations of four algae at dierent ionic strengths
KH;app KCH Hp =H
Dqb
(mequiv/g)
Dqb
(mequiv/g)
276
mM=l:
13
ml=g:
14
277
I M C =Vm =2M0:5 :
15
KH CH=Hp C ;
M2 2C $ 2CM0:5
16
KM CM0:5 2 =Mp C 2 :
17
mequiv=g:
18
From these equations a pH sensitive isotherm equation can be derived which allows for the calculation of
the amount of metal and protons bound covalently
(Schiewer and Volesky, 1995a).
CH Ct KH Hp =1 KH Hp
KM Mp 0:5 mequiv=g:
19
CM0:5 Ct KM Mp 0:5 =1 KH Hp
KM Mp 0:5 mequiv=g:
20
mequiv=g:
21
278
ml=g;
22
Vm , tita (ml/g)
KM , optb (l/mM)
Dqc (mequiv/g)
1.30
0.75
1.45
0.55
0.23
0.064
0.17
0.000063
0.31
0.20
0.29
0.14
24
Table 2
DORI model parameters for Cu binding by dierent algae at pH 4 and low ionic strength, for pKa 3.0
Sargassum
Colpomenia
Petalonia
Ulva
23
279
Fig. 3. Ionic strength eects in the binding of protons and metals at pH 4 by protonated Sargassum biomass. Experimental data and
Donnan model for swelling particles (DOSW) with common pKa and YV as well as modeling taking into account: only electrostatic
eects (``elst'', with KH KM 0) or only covalent binding (``cov'', with k 1.0). (a) Proton binding in the presence of Cu, (b) Cu
binding, (c) proton binding in the presence of Ni, (d) Ni binding.
0.23
0.0077
5
5
0.24
0.14
0.23
0.0077
b
MATLAB optimized.
Absolute mean square deviations of model predictions from data for qH and qM .
c
As determined in titration experiments.
4.9
10.3
0.33
0.28
0.18
0.0041
1.3
1.3
0.29
0.15
KM,
opta
(l/mM)
Vm , titc
(ml/g)
Dqb
(mequiv/g)
KM , opta
(l/mM)
0.22
0.0024
4.0
6.7
Cu
Ni
KM , opta
(l/mM)
YV
(ml/g)
Dqb
(mequiv/g)
KM , opta
(l/mM)
DOSW
YV , opta
(ml/g)
Vm , opta
(ml/g)
Dqb
(mequiv/g)
DORI
Table 3
Donnan model parameters for Cu and Ni binding by Sargassum at pH 4 for dierent ionic strengths, with pKa 3.0
0.24
0.16
Dqb
(mequiv/g)
280
terms [H] YV (1)1/k) and 2[M] YV (k)1/k) in the enumerator for protons and metals, respectively.
The importance of electrostatic eects might be best
visualized by considering the hypothetical cases that:
(a) only electrostatic but no covalent binding occurs i.e., the covalent binding constants
KH KM 0;
(b) only covalent binding but no electrostatic attraction occurs i.e., the concentration factor
k 1.0, which means [H] [H]p , [M] [M]p .
The results for modeling these two limiting cases with
the same constants as for the complete DOSW model
are also shown in Fig. 3.
Case a: When only electrostatic attraction is taken
into account, the binding of protons in the presence of
either Cu or Ni is reduced to almost zero. This means
the amount of protons bound directly by electrostatic
binding is negligibly small. The binding of Cu is significantly reduced, especially at high ionic strength, but
nevertheless a substantial amount of Cu is bound by
electrostatic attraction alone. The binding of Ni is reduced at high I but actually increased at low I because of
the reduced competition by protons.
Case b: If only covalent binding is considered, obviously no ionic strength eects occur. The binding of
protons is reduced to 0.15 mequiv/g both in the presence of Cu and Ni. Comparing this proton binding
(which is due purely to the intrinsic binding constants)
with the complete model reveals the importance of the
indirect multiplicative eect of electrostatic attraction.
The binding of Cu is intermediate to that obtained by
modeling only electrostatic eects at low and high I,
respectively. This means electrostatic and covalent
binding are of comparable magnitude whereby electrostatic eects are dominant at low I and covalent binding
at high I. The binding of Ni is for the most part lower
than considering electrostatic eects alone. This shows
the predominant importance of electrostatic eects in
the binding of Ni.
The larger importance of covalent binding for Cu
compared to Ni is due to the fact that while electrostatic
attraction is equally strong for both metals, the covalent
binding constants are 3090 times higher for Cu than for
Ni (Table 3). This corresponds to the fact that Cu has a
higher Nieboer class ``b'' index than Ni: the higher
electronegativity to Cu leads to more equal (covalent)
sharing of electrons with a ligand atom like oxygen as it
occurs in carboxyl groups (Stumm and Morgan, 1996).
4. Conclusions
The number of titrated weakly acidic carboxyl
groups was 2.9 for Petalonia, 2.6 for Sargassum, 1.5 for
Colpomenia and 1.1 for Ulva. The titration curves for all
algae showed a marked eect of ionic strength: the
Acknowledgements
The authors would like to thank The Croucher
Foundation for nancial support. The second author
received the Senior Research Fellowship when the study
was carried out.
281
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