Professional Documents
Culture Documents
Metal Ions
Edited by
DR JOHN WASE
School of Chemical Engineering, University of Birmingham, UK
and
DR CHRISTOPHER FORSTER
School of Civil Engineering, University of Birmingham, UK
UK
Taylor & Francis Ltd, 1 Gunpowder Square, London EC4A 3DE
USA Taylor & Francis Inc., 1900 Frost Road, Suite 101, Bristol, PA 19007
This edition published in the Taylor & Francis e-Library, 2003.
Copyright Taylor & Francis Ltd 1997
All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted, in any form or by any means, electronic, electrostatic, magnetic
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the copyright owner.
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library.
ISBN 0-203-48304-9 Master e-book ISBN
Contents
List of Contributors
1 Biosorption of heavy metals: an introduction (C.F.Forster; D.A.J.Wase)
Introduction
Toxic metals
Control
Treatment
References
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Contents
4 Fungi as biosorbents (A.Kapoor; T.Viraraghavan)
Introduction
Modes of metal ion uptake
Modelling of biosorption
Biosorption by living cells
Biosorption of metal ions by non-living cells
Regeneration of fungal biomass and elution of biosorbed metals
Use of immobilised fungal biomass in biosorption
Biosorption mechanism
General considerations in the use of fungi as biosorbents
References
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Contents
8 Biosorption using unusual biomasses (R.G.J.Edyvean; C.J.Williams;
M.M.Wilson; D.Aderhold)
Introduction
Types of biomass
Performance
Factors affecting adsorption
Industrial scale systems
Conclusions
References
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Introduction
Background
Over the past two decades an increased interest in the phenomenon of metal ions
sequestering by living or inactive microbial biomass has been seen in the scientific
and engineering community. This phenomenon has potential application in
environmental pollution control as a biochemical process on which corresponding
unit operations can be designed and operated by industry.
Previous publications on the subject have proposed the adoption of two different
terms for the description of the two mechanistically different types of metals
sequestering by microorganisms. The term bioaccumulation has been proposed for
the sequestering of metal ions by metabolically mediated processes (living
microorganisms), and the term biosorption for the sequestering by nonmetabolically mediated process (inactive microorganisms) (Diels et al., 1995). As our
understanding of the above processes has increased, the mechanistic differences
between biosorption and bioaccumulation have proved to be so significant that the
use of the two terms has become a necessity (Tsezos and Volesky, 1982a, 1982b;
Macaskie and Dean, 1984; Diels, 1989; Diels et al., 1995). The two processes can coexist and can also function independently as, for example, in the case where a
consortium of microorganisms is exposed to metal-bearing solutions. Literature on
both biosorption and bioaccumulation is extensive, including, for example, work on:
the use of Alcaligenes eutrophus strains in bioreactors for the bioaccumulation of
Cd, Zn and other heavy metals and radionuclides (Diels, 1989)
the use of Citrobacter species in the bioaccumulation of heavy metals (Macaskie,
1991; Macaskie and Dean, 1984)
the use of Methylobacillus species for uranium biosorption (Glombitza et al.,
1984) and of other bacterial species for silver biosorption (Pumpel and Schinner,
1986)
uranium, thorium and radium biosorption from mine waters (Tsezos and
McCready, 1989).
87
This chapter will focus more on the phenomenon of biosorption, and, in particular, on
the removal of lanthanides, actinides and related elements.
Biosorption of metals is generally characterised by high selectivity as compared to
ion-exchange resins or other adsorbents. This selectivity is considered to be a
desirable feature in designing processes for pollution control and/or metal value
recovery (Tsezos and Volesky, 1982b; Tsezos, 1985; Tsezos and McCready, 1991;
Diels, 1989; Diels et al., 1995; Macaskie, 1991; Glombitza et al., 1984; Pumpel and
Schinner, 1986; Gadd, 1992). In addition to selectivity, biosorptive processes have the
following advantages:
solution toxicity does not inhibit microbial biosorptive uptake
microbial biomass growth requirements need not be met
culture purity maintenance is not a concern.
Biosorptive processes are excellent candidates for use for the recovery of metal
values from dilute industrial complex aqueous solutions, the extraction of
radionuclides, e.g. uranium, thorium or radium from mine leachates, and similar
metal value recovery or water pollution control applications (Macaskie, 1991;
Pumpel and Schinner, 1986; Diels et al., 1995; Tsezos and Volesky, 1982b; Tsezos,
1990; Gadd, 1992).
Technological considerations
The engineering applications of biosorption or bioaccumulation commonly involve a
dilute complex ionic matrix and large volumes of aqueous process or waste solutions
from which the selective extraction and, occasionally, recovery of targeted elements
via the use of the microbial biomass is intended. Regardless of the detailed
engineering configuration of such a process, a stage which significantly affects the
overall efficiency and the economics of the technology is the separation of the
microbial biomass from the waste or process waters following contact (SENES
Consultants, 1985).
As a result of this constraint, contact systems making use of microbial biomass
immobilised on a support medium have been developed and proposed for use. Two
generically different types of immobilised biomass contact systems have been
proposed. The first type is based on the use of immobilised biomass particles which
are produced via the use of a wide range of biomass binding agents, such as synthetic
polymers (e.g. polysulphones), natural polymers (e.g. alginates) or chemical biomass
treatment (Brierley et al., 1986; Kiff and Little, 1986; Tobin et al., 1994; Tsezos and
Deutschmann, 1990). The second type is based on the use of microbial biomass films,
immobilised on support media such as membrane sheets, disks or inorganic particles
(Diels, 1989; Diels et al., 19961999; Harel et al., 1995; Tobin et al., 1994; Brierley
and Vance, 1988; Darnall et al., 1989). Each one of the two types of immobilised
biomass necessitates the implementation of different contact reactor design, such as
upflow or downflow packed-bed reactors, rotating biological contactors, membrane
sheet or tubular reactors, etc. Figure 5.1 shows a typical example of an immobilised
biomass particle of the first type in two different magnifications.
It is interesting to note the highly porous structure of the particles shown in Figure
88
Figure 5.1 Electron micrographs (TEM) of immobilised biomass particles: (a) general view;
(b) magnification of the particle porous structure
5.1 which is required in order to facilitate and improve the kinetics of metal ions
diffusion into the inner particle active biosorption sites (Tsezos et al., 1988; Tsezos
and Deutschmann, 1990).
Figure 5.2 Electron micrographs (TEM) of R. arrhizus cell wall thin section before (a) and after
(b) uranium biosorption
capacities, were examined using EM and EDAX microprobe analysis. It was reported
that the locus of biosorption for palladium, silver, nickel and yttrium appears to be
more metal dependent than microbial species dependent. Silver was mostly located
on the external surfaces of the cells (Figure 5.4). Palladium was mostly located inside
91
Figure 5.3 Electron micrographs (TEM) of R. arrhizus cell wall thin section after thorium
biosorption
the cells (Figure 5.5), while yttrium occupied mostly cellular membrane sites, and to
a substantially lesser extent inner specific sites (Figure 5.6).
The mechanism of the metabolically mediated bioaccumulatory metal uptake has
been studied and has been reported for the cases of Alcaligenes spp. (Diels, 1989),
Citrobacter spp. (Macaskie, 1991) and Desulfovibrio spp. (Diels et al., 1995).
These mechanisms involve the metabolically mediated production of a chemical
agent which precipitates the element of interest in the near-cell area. Thus, for
example, the Citrobacter species continuously produce inorganic phosphate by the
92
Figure 5.4 Electron micrograph (TEM) of AS302 cells following Ag biosorption (a), EDAX
confirmation of Ag retained (b)
Figure 5.5 Electron micrograph (TEM) of AS302 cells following Pd biosorption (a), EDAX
confirmation of Pd retained (b)
Figure 5.6 Electron micrograph (TEM) of AS302 cells following Y biosorption (a), EDAX
confirmation of Y retained (b)
Application of biosorption
The application of biosorption for the sequestering of the lanthanides, the actinides
and related elements was primarily motivated by environmental concerns over the
release to the environment and the subsequent fate of radioactive isotopes from the
uranium nuclear fuel power generation cycle. Therefore, interest has focused mostly
on uranium, thorium, radium and, to a lesser extent, other elements associated with
nuclear activities, such as cobalt and strontium. Interest in the application of
biosorption for rare earths sequestering is more recent and originated, primarily, with
industrial interest in scavenging and recovering rare earth metal values from aqueous
dilute process or waste streams.
Information on biosorption will be presented separately for elements of interest in
these groups.
Uranium biosorption
In examining the biosorptive uptake of uranium by microbial biomass, the
equilibrium and the rate of the process need to be defined. The equilibrium of
biosorption has been successfully described by the use of the Langmuir and
Freundlich relationships which show the equilibrium distribution of the biosorbed
element between the solution (liquid phase) and the microbial biomass (solid phase).
Both models have been used and reported on (Tsezos and Keller, 1983; Tsezos, 1985,
1990; Tsezos et al., 1995, 1996a; Glombitza et al., 1984; Georgousis, 1990).
Attention must be paid to the fact that these models cannot be attributed any
mechanistic significance and should only be interpreted as mathematical tools for
describing the distribution of the element between the solid and the liquid phases in
biosorption. The effects of parameters such as the solution pH, the biomass growth
conditions and the solution ionic matrix on the microbial biomass biosorptive uptake
have been discussed in detail and have been presented in other publications by several
authors (Tsezos, 1985; Tsezos and McCready, 1989; Tsezos, 1990; Ehrlich and
Brierley, 1990). Therefore, the detailed discussion on the effects of the above
parameters on the biosorptive uptake of the metals of interest will not be discussed in
this chapter.
Most of the uranium biosorptive uptake studies have been conducted utilising
synthetic uranium solutions, i.e. single-element solutions. The corresponding
solution ionic matrices have, therefore, been kept simple, well defined and
controllable. Less work has been carried out and reported on industrial or complex
matrix solutions.
97
Several different microbial biomass types have been examined for their uranium
uptake capacity. Figure 5.7 shows typical reported uranium biosorption isotherms for
simple uranyl nitrate solutions at moderately acidic pH values (pH=4) (Tsezos and
Volesky, 1981).
The isotherms in Figure 5.7 demonstrate that the biosorptive uptake of uranium
can be significant (up to about 20% of the biomass dry weight). They also suggest
that the uranium biosorptive uptake can be efficient and aggressive since selected
biomass types may demonstrate high uranium uptake capacities at low equilibrium
uranium solution concentrations. This is a very desirable characteristic for the
processes application potential of biosorption, as it secures significant biomass
uranium loadings at low residual solution uranium concentrations. Table 5.1
Figure 5.7 Comparison of uranium uptake capacities for selected sorbent materials
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Figure 5.9 Comparison of experimental (?) and model-predicted (line) uranium solution
concentration profiles
100
bicarbonate solutions are the most appropriate eluents for uranium, as they
completely strip the biosorbed uranium while maintaining intact the microbial
biomass uranium biosorption characteristics. Mineral acids and sulphate-rich
solutions have been shown to damage the microbial biomass re-use potential (Tsezos,
1984). Table 5.2 summarises the effect and performance of a variety of elements used
for uranium elution on R. arrhizus biomass.
Implementation of optimised solid to liquid ratios in elution enables the generation
of highly concentrated uranium eluates with concentration factors of over 10 3
(Tsezos, 1984).
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102
Figure 5.12 Summary of uranium elution efficiency observed during the first 11 cycles of the
pilot plant operation
of one continuous pilot plant operation, suggesting the complete recovery of all
biosorbed uranium for each cycle (Macaskie, 1991; Tsezos, 1990; Tsezos and
McCready, 1991; Tsezos et al., 1996c).
104
Figure 5.14 Laboratory scale immobilised R. arrhizus biomass pilot plant treating uranium mine
wastewaters
This mechanism of interference is a typical example of what we can call the steric
hindrance type of competition among elements in biosorption. Our systematic work
on the subject of ionic competition in biosorption has suggested the existence of a
second type of mechanism of interference in biosorption among metals co-existing in
complex solutions, which we can call the binding competition type of mechanism
(Georgousis, 1990; Tsezos, 1984; Tsezos et al., 1995, 1996a).
Microbial biomass provides ligand groups on which metal species may bind by
different mechanisms. Major classes of microbial biopolymers, such as proteins,
nucleic acids and polysaccharides, provide sites on which metal ions may bind. The
ligand groups available include negatively charged groups, such as carboxylate,
thiolate, or phosphate and groups such as amines, which often coordinate to the metal
through lone pairs of electrons. The metal ionic species should exhibit a preference
for the ligand binding sites of the biomass based on their chemical coordination
characteristics. Different ionic species of the same element can potentially exhibit
preference for different binding sites.
If the preference of one metal ion for a ligand is similar to that of another metal
ion, a competition effect could result between the metals for that given binding site.
As a result of this type of competition when two metal species compete, the
biosorptive uptake capacity for the targeted metal can be lower than that
corresponding to single metal solutions of the targeted element. If, however, the metal
ions species exhibit preferences for different biomass binding sites, their
simultaneous presence in solution may not significantly affect their individual uptake
capacities by the microbial biomass used. In order to understand such competition
effects, it has often been suggested that the differentiation of metals expected
105
Figure 5.15 Comparison of thorium uptake capacities for selected sorbent materials
The radium re-adsorption capacity of the microbial biomass following elution was
reported to be reduced substantially as the acidic elements damaged the microbial cell
architecture (Tsezos et al., 1986b).
Immobilised microbial biomass has been used in a laboratory-scale continuous
pilot plant for the treatment of radium-bearing waste waters from the Elliot Lake
district of Canada (Tsezos et al., 1987). In that report, the equilibrium radium uptake
(~ 200 nCi/g), the kinetics of radium uptake and the regeneration/re-use of the
immobilised biomass were reported, suggesting that biosorption can be an efficient
process for the selective extraction of radium from the waste streams. The subsequent
elution of radium in a concentrated form and the re-use of the biomass in a limited
number of cycles have been reported as possible (Tsezos et al., 1986b). Table 5.5
summarises the reported re-use potential of the immobilised biomass particles, where
a mixed culture of predominantly bacterial organisms from a municipal wastewater
treatment plant was used.
The work reported on radium biosorption has suggested that the biosorptive
sequestering of radium could be a reasonable alternative to the Ba-Ra sulphate
precipitation technology as it does not produce, as a by-product, large volumes of
radioactive sludge and it is affected less than ion exchange resins by the presence of IIA
elements.
Closing comments
The information presented in this chapter summarises some of the work and the
experience accumulated over the past 20 years on the biosorption of members of the
lanthanides, actinides and related elements. One could potentially include more
109
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