Bioresource Technology 58 (1996) 1--6

Copyright © 1996 Elsevier Science Limited

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ELSEVIER PI1:S0960-8524(96)00072-7

THE REMOVAL OF HEAVY-METAL IONS BY SEAWEEDS

A N D THEIR DERIVATIVES

D. A d e r h o l d , ~ C. J. Williams b* & R. G. J. E d y v e a n b
aUniversitiit Dortmund, Lehrstuhl Thermische Verfahrenstechnik, Dortmund, Germany
bChemical Engineering and Fuel Technology, Department of Mechanical and Process Engineerin~ The University of Sheffield,
Sheffield $1 3JD, UK

(Received 7 February 1996; revised version received 5 May 1996; accepted 16 May 1996)

Abstract cheaper production processes, which can lead to

The abilities of different species of seaweeds and their
derivatives to remove a range of heavy metals from
solution under standard laboratory conditions were
determined. The three species of brown seaweeds were
Ecklonia maxima, Lessonia flavicans and Durvillea
potatorurrt The two seaweed derivatives produced by
commercial seaweed processing were aiginate fibres
and dealginated seaweed waste. The abilities of these
biomasses to sequester the heavy-metal ions copper,
nicke~ lead, zinc and cadmium from solution under
constant agitation were compared. The effect of the
presence of more than one metal ion in solution was
investigated in order to determine whether any com-
petition effects might have affected metal-ion uptake.
The metal-removal capacity of these seaweeds and
their derivatives is discussed in the light of the eco-
nomic and environmental aspects of using such a
wastewater-treatment system on an industrial scale.
Copyright © 1996 Elsevier Science Ltd.
Key words: Biosorption, heavy metals, seaweed, algi-
nate, pollution control, waste biomasses.
INTRODUCTION
In recent years widespread concern over the cumula-
tive toxicity and environmental impact of heavy
metals has lead to extensive research into develop-
ing effective alternative technologies for the removal
of these potentially damaging substances from efflu-
ents and industrial wastewaters. The main driving
force for this research is increasingly stringent
environmental legislation and the powers of the
authoritative bodies established to enforce these
regulations. Current EC directives have requested
better processes for the removal of these pollutants
and encouraged the use of processes that have nega-
tive impact on the environment. At the same time,
market pressures often force companies to utilise
*Author to whom correspondenceshouldbe addressed.
compromises in the release of pollutants.
Heavy metals, such as cadmium and mercury, may
be regarded as highly toxic and are included in the
so-called 'Red List' of priority pollutants published
by the Department of the Environment in 1987 and
also in List I of the EEC Dangerous Substances
Directive (1976). Copper, nickel, lead, tin and
chromium are all listed in List II of this directive,
which contains pollutants of less toxicity. These met-
als create environmental pollution problems since,
although not necessarily toxic at low concentrations,
they accumulate in the food chain and once absor-
bed into bodily tissues cannot be easily excreted.
Many industries are responsible for the release of
heavy metals into the environment through their
wastewaters (Brauckmann, 1990). These include pig-
ment manufacturing, iron and steel production,
mining and mineral processing, the non-ferrous
metal industry, battery manufacture, the printing
and photographic industries and metal-working and
finishing processes (electroplating). In addition, con-
siderable quantities of heavy metals can be released
into the environment through routes other than in
aqueous form in wastewaters. For example, lead is
widely used in metallic form and copper is used in
electrical equipment, water pipes, alloys, as chemical
catalysts and in anti-fouling paints on ship hulls.
Wastewater-treatment options for heavy-metal
removal
There are several different options currently avail-
able for the removal of heavy metals from industrial
wastewaters. The main methods are precipitation,
ion-exchange and electrolytic methods.
In precipitation processes a dissolved substance is
forced to form a fine suspension of solid particles in
order to effect a solid-liquid separation. It is
dependent upon the theoretical solubility of the
most soluble species formed and the separation of
the solids from the aqueous solution. Heavy metals
are usually precipitated as the hydroxide by the
2 D. Aderhold, C. J. Williams, R. G. J. Edyvean
addition of lime (calcium hydroxide) or potassium
hydroxide or sodium hydroxide. These methods are
relatively inexpensive and are useful for removing
the bulk of the heavy-metal ions. However, they are
not suitable where final clarification is required.
Ion exchange is a process in which ions are
exchanged between a solution and an insoluble solid
which is usually a resin. A multiplicity of ion-
exchange resins are commercially available and
some exhibit a high specificity for certain heavy met-
als. The resins can be loaded and regenerated
several hundred times and produce final effluents of
very low heavy-metal concentration. However, a
high capital expenditure is usually required in order
to purchase and operate such a system. Electrolysis
allows the removal of the metal from solution in
solid metallic form for recycling or for sale. The
advantages of these systems is that no extra chemical
reagents are required and that no sludges are pro-
duced. However, on a more global scale,
considerable resources may be required and high
levels of pollutants are produced as a result of the
electricity required for the second process. The use
of electricity means that the economics of this
method depend very strongly on the energy price
and the amount of electricity consumed per treated
volume of metal solution.
Other methods, such as membrane processes,
osmosis and reverse osmosis, dialysis or electrodial-
ysis, are found only very occasionally and tend to be
utilised in very specialised applications. Current
membrane processes tend to be hindered by the
problems of limited flow-rates, instability of the
membranes in salt and acid conditions and fouling
by inorganic and organic species. The prohibitive
cost of the process of evaporation limits its use to
applications where there is a high economic benefit
from recovery of a product, such as in the recycling
of precious metals in the catalyst-producing indus-
tries.
Adsorption techniques
Adsorption processes are versatile in terms of appa-
ratus and offer a relatively simple method for the
removal of components or impurities from liquid or
gaseous media. The absorbent has to have the cap-
ability to selectively condense or concentrate the
targeted adsorbate (molecules, atoms, ions or par-
ticles) on its surface. Industrially important
adsorbers include activated carbon, silica gel and
alumina, which all have a porous surface structure
and thus a high surface area.
Biosorption is a specific example of adsorption
which has gained increasing attention over the last
few years. Biosorption is essentially the binding of
chemical species to biopolymers and the existence of
this phenomenon has been reported for many dif-
ferent plant- and animal-derived materials (Simmons
et al., 1995). The term 'biosorption' is now generally
accepted as referring to passive or physico-chemical
attachment of the sorbate to a biomass, thus exclud-
ing metabolic or active-uptake processes (Volesky,
1990). Accordingly, there is no requirement to use
or maintain living organisms for the process. This
factor allows the use of harsher reaction environ-
ments and negates the need for providing a nutrient
supply or preventing toxification of the biomass.
The process advantages of selecting non-viable
biomasses have led to considerable research into the
use of these systems for the removal of heavy-metal
ions (Avery & Tobin, 1992; Orhan & Buyukgungor,
1993). The fact that such a broad range of biomasses
have been shown to exhibit some affinity for heavy
metals indicates that the use of cheap (or even
waste) biomasses could be a future BATNEEC tech-
nology in pollution control.
METHODS
The metal-ion uptake capacity of different species of
seaweeds and seaweed derived materials was deter-
mined under standard laboratory conditions. The
three species of seaweed which were investigated
were Ecklonia maxima, Lessonia flavicans and Dur-
villea potatorum. These seaweeds were obtained in
dried, milled form. The seaweed-derived materials
included dealginated seaweed, a waste product of
the alginate-production industry, referred to from
here on as dealginate. The dealginate was supplied
courtesy of Pronova Biopolymers, Norway. The
second seaweed-derived material was commercially
extruded alginate fibre, referred to from here on as
alginate.
The metal ions which were investigated included
copper, nickel, zinc, lead and cadmium. Standard
solutions of each metal ion were prepared providing
single metal ion solutions at concentrations of
10 mg/1. Preliminary experiments were carried out
comparing the ability of the five different biomasses
to remove each of these five metal ions from single-
metal-ion solutions. Further experiments were
conducted using only copper, nickel and cadmium as
the single-metal-ion solutions and triple replicates of
each experiment were carried out in order to ascer-
tain the degree of variation in the experimental
procedure.
A standard methodology was adopted for all of
the experiments. Each experiment was conducted by
the addition of 0.5 g of biomass to 50 ml of metal-
ion solution in an Erlenmeyer flask which was
agitated at 100 rpm on a Gallenkamp orbital shaker
for 24 h. All experiments were conducted at room
temperature, since previous research carded out by
the authors indicated that temperature fluctuations
between 10 and 35°C did not affect biosorption. Fol-
lowing the 24 h period of agitation the contents of
the flask were separated by filtration using a What-
man No. 1 filter paper. The concentration of the
particular metal in the filtrate was determined by
 Removal of heavy metals by seaweeds
ICP-AES (Induction Coupled Plasma-Atomic
Emission Spectrophotometry).
In order to ascertain whether there was any com-
petition between the different metal ions for uptake
by a particular biomass, multiple-metal-ion solutions
were prepared. The concentration of each metal ion
in the solution remained at 10 mg/l, so that where
two metals were present the total metal concentra-
tion was 20 mg/1 and similarly where three metals
were present the total metal concentration was
30 mg/l. Copper, nickel and cadmium were used as
the metal ions. These experiments were conducted
according to the standard methodology described
earlier, except that multiple-metal-ion solutions were
used instead of single-metal-ion solutions. The abil-
ities of the biomasses to adsorb one metal were
compared with the adsorption of the same metal
where one or two other metals were present in the
same solution. The concentrations of each metal ion
in the solutions collected after filtration were deter-
mined by ICP-AES.
Further investigation of the capacity of alginate
fibre and dealginate for the same three metals
(nickel, copper and cadmium) was carried out using
a semi-continuous batch adsorber system. The
standard methodology described earlier was utilised
except that again the mixed-metal solution contain-
ing nickel, copper and cadmium each at 10 mg/l
concentration was used instead of a single-metal-ion
solution. After the 24 h adsorption period with
agitation on the orbital shaker, the solution and the
metal-loaded biomass were passed through a What-
man No. 1 filter paper. The filtrate was collected
and the concentrations of nickel, copper and cad-
mium were determined separately by ICP-AES.
The biomass was returned to the Erlenmeyer
flask and a fresh 50 ml aliquot of the mixed metal
solution, containing 10 mg/l of each of nickel, copper
and cadmium was added to the flask. The standard
methodology was repeated at this stage so that the
flask containing the biomass and the mixed metal
solution was agitated at room temperature for 24 h.
This process was referred to as the adsorption cycle
and in total 11 successive adsorption cycles were
carried out using the same sample of biomass.
RESULTS AND DISCUSSION
Figure 1 compares the metal uptake capacity of
three different species of seaweed. Generally, all
three species of seaweed were found to sequester
metal ions from solution, providing residual concen-
trations below 1 mg/t and as low as 0,022 mg/1 in the
case of cadmium. However, Lessonia flavicans was
found to be particularly poor at removing lead ions,
as is evident from the high residual concentration of
4.78 mg/1. Durvillea potatorum provided the lowest
residual metal concentrations in the majority of
cases. Durvillea potatorum and L. flavicans exhibited
3
1.0
0.8
°°.411..0
"-" 0.6
o~
0.2
.,~
o.o
Nickel Copper Zinc Lead Cadmium
Fig. 1. The biosorption of heavy-metal ions by E. maxima
(black), L. flavicans (grey) and D. potatorum (white) from
initial solution concentrations of 10 mg/1. A residual con-
centration of lead ions of 4.78 mg/l by L. flavicans is not
shown on this figure.
the greatest operational problems throughout the
course of these experiments in that they both
released large quantities of alginates upon wetting.
Alginate is produced from algin, a high molecular
weight polymer composed of D-mannuronic acid and
L-guluronic acid, when the protons of the carboxylic
groups are replaced by metal ions (Cottrell &
Kovacs, 1980). Both D. potatorum and L. flavicans
contain a high proportion of alginates which are
released upon contact with water and this caused
considerable problems at both the filtration and
analysis stages of this experimental procedure.
Accordingly, Ecklonia maxima, which was found to
release less alginates during experimentation and
exhibit relatively high metal-ion-removal ability, was
selected for further use.
Figure 2 compares the metal-removal capacity of
E. maxima with dealginated seaweed and alginate
fibre. The alginate produced lower residual concen-
trations of ions in all cases except that of zinc. These
alginate fibres had been extruded in the presence of
zinc during their manufacture and, accordingly,
leached small concentrations of zinc into solution.
Consequently, it was not possible to measure the
final zinc concentration for this biomass accurately
and so this value has been omitted. Ecklonia maxima
1.2
1,0
0.8
.o
0,6
0.0 : ,q : m
Nickel Copper Zinc Lead Cadmium
Fig. 2. The biosorption of heavy-metal ions by E. max/ma
(black), dealginate (grey) and alginate (white) from initial
solution concentrations of 10 mg/l.
4 D. Aderhold, C J. Williams, R. G. J. Edyvean

100
100 ..r- ~ --

!-
8O

-~ 40 2O

2O
~ ~ p ~ ~ ~ ~ ~ ~ z .z..z.
z. -
0
Metals present in solution (10 mg/l caeh metal)
E. Maxima De.~Iginatc Alghmt~
Fig. 4. The uptake by E. maxima of copper (black), cad-
Fig. 3. Comparison of the percentage uptake of copper mium (grey) and nickel (white) from single- and
(black), nickel (grey) and cadmium (white) by different multi-metal-ion solutions.
biomasses from initial solution concentrations of 10 mg/1.

initial solution. These findings illustrate that the

produced slightly lower residual ion concentrations
than the dealginate, except for copper. Apart from
the relatively poor removal of nickel by dealginate,
all of the biomasses were found to reduce all of the
five metal ions to residual levels as low as, or lower
than 0.5 mg/l. This equates to a metal-uptake capa-
city of 95 %.
Figure 3 compares the uptake abilities of three
seaweed materials for copper, nickel and cadmium.
Both the dealginate and the alginate removed in
sequestering ability of these three biomasses for a
particular metal ion was not affected by the
presence of additional metal ions. Comparison of
these findings with those portrayed in Fig. 3 clearly
demonstrates that similar residual levels were found
where only one metal was present in solution. The
uptake of copper by E. maxima may have been
slightly enhanced by the presence of nickel and also
100

excess of 90% of metal ions in the case of all three

--, 8O
metals. All three biomasses exhibited a consistent
trend in terms of metal-ion uptake in that cadmium
was the most effectively sequestered, followed by
copper and lastly nickel. These findings are consist- ..~ 40 I
ent with those of Wilson (1993), who reported a
similar relationship when using linseed straw, a s0
waste product of the linseed-oil industry, and E. i

maxima as biosorbents. None of the problems of

release of alginates as previously mentioned were
experienced when dealginate and alginate fibre were
used as experimental biomasses. Metals present in solution (10 mg/l each metal)
Alginate exhibited the best metal-sequestering Fig. 5. The uptake by dealginate of copper (black), cad-
ability, followed by dealginate, with greater than mium (grey) and nickel (white) from single- and
93% uptake at equilibrium, providing a residual con- multi-metal-ion solutions.
centration below 0.7 mg/l in solution. There was very
little variation within the replicates of these experi-
100
ments, indicating a consistent metal-removal
capacity for both alginate and dealginate. However, ,_, 80
in the case of E. maxima a much larger standard
deviation was observed. This may be attributed to I ,

the seaweed being in the form of dried, milled par-

ticles, which, although graded prior to .~- 4o
experimentation for a consistent size fraction, may
be derived from any part of the original plant. 20
Accordingly, since different regions of the whole
seaweed are known to exhibit varying biosorbent
abilities (Wilson, 1993), any one batch prepared for
experimental purposes may contain more or less
particles capable of greater metal-ion uptake. Metals present in solution (10 mg/l each metal)
Figures 4-6 compare the metal-ion removal abil- Fig. 6. The uptake by alginate of copper (black), cadmium
ities of E. maxima, dealginate and alginate when (grey) and nickel (white) from single- and multi-metal-ion
there was more than one metal ion present in the solutions.
 Removal of heavy metals by seaweeds 5

where both cadmium and nickel were present in t h e

il Y
initial solution. However, this effect may be attri- 7
buted to the overall degree of variation in the
metal-ion uptake by E. max/ma, as indicated by the
standard deviations portrayed in Fig. 4. In the case
of dealginate and alginate, as shown in Figs 5 and 6,
respectively, very little variation was observed
between the triple replicate tests.
The low concentration levels selected for these
experiments (10 mg/l), which would utilise only a
small portion of the biosorbents' overall metal-
uptake capacity, may explain the absence of any I 2 3 4 5 6 7 8 9 10 11
obvious competition effects. These findings are in Number of adsorption cycles
agreement with Wilson (1993), who found no com- Fig. 7. The selective adsorption of copper (s), cadmium
petition between the biosorption of mercury and (A) and nickel (o) by dealginate over 11 successive
cadmium from 100 mg/1 solutions. It is also possible adsorption cycles.
that these biosorbents have high affinities for nickel,
copper and cadmium. Consequently, at such low mium, respectively, which were found when alginate
concentrations any selective metal-ion removal was subjected to the 11 cycles of adsorption.
would not be apparent. It should be considered that
These findings indicate that the degree of metallic
this may not be the case for other metal ions.
bonding is greatest for copper, followed by cadmium
These findings suggest that these biosorbents may
and then nickel for both dealginate and alginate.
show potential in applications which require the
This suggests that each biomass selectively adsorbs
simultaneous removal of more than one metallic
specific metal ions when other ions are present and
species. This would be particularly valuable in waste-
in the case of both dealginate and a!ginate, copper
water-treatment operations, since the majority of ions are selected over cadmium ions, which are
industrially discharged effluents contain a variety of selected in preference to nickel ions. This effect only
metallic and other species which must be removed became apparent once the overall concentration of
prior to release into the environment. In contrast,
metal ions on the biomass reached an appropriate
where a particularly selective removal of one heavy
level. In the case of both biosorbents, less nickel
metal is required, these findings disqualify these bio- than copper or cadmium was removed from the
sorbents from such applications. solution right from the start of the experiment. The
The low selectivity of these biosorbents is not
nickel concentration in the metal solution from both
altogether surprising since a characteristic of most biomasses continued to rise throughout the course
biosorbents is, unlike ion-exchange resins, the
of the 11 adsorption cycles. The findings portrayed
number and diversity of functional sites available for
in Figs 7 and 8 also indicate that throughout the
metal-ion binding. These sites can include carboxyl,
course of the 11 adsorption cycles the nickel concen-
imidazole, sulphhdryl, amino, phosphate, sulphate, tration did not exceed 10mg/1, which was the
thioether, phenol, carbonyl, amide and hydroxyl
concentration of nickel added at each adsorption
moieties (Eccles, 1995).
stage. Consequently, this suggests that both biomas-
The apparent low selectivity of both dealginate ses continued to adsorb nickel ions throughout the
and alginate for heavy-metal ions was further course of the experiment, although not to the same
investigated in a semi-continuous batch adsorption
experiment. These findings are shown in Figs 7 and
8.
8 for dealginate and alginate, respectively. It is
evident that even after 11 cycles of semi-continuous 7
adsorption, by the same sample of biomass, that g 6
saturation of either the dealginate or the alginate
biomass has not occurred. However, both biosor-
bents do exhibit the same preference for metal-ion 4
uptake, in that in both cases copper ions were con-
sistently removed to levels as low as 0.2 mg/1, even
after 11 cycles of adsorption. The residual concen- 2
trations of cadmium and nickel were observed to
increase gradually throughout the course of the
0- - '_ _" - ~ - - -

experiments. After the eleventh cycle of adsorption, 2 3 4 5 6 7 8 9 10 11

residual levels in excess of 7 mg/1 of nickel and Nttmbe~ of adsorption cycles
3.4 mg/1 of cadmium were found in the case of deal- Fig. 8. The selective adsorption of copper (m), cadmium
ginate. This can be compared with the residual (-) and nickel (o) by alginate over 11 successive adsorp-
concentrations of 3.5 and 0.8 mg/1 of nickel and cad- tion cycles.
6 D. Aderhold, C. J. Williams, R. G. J. Edyvean
extent as cadmium or, particularly, copper ions were
adsorbed.
The findings displayed in Figs 7 and 8 also sug-
gest that alginate fibre has a higher capacity for
metal ions than the dealginate. While neither bio-
mass displayed any saturation in the adsorption of
copper, the alginate continued to adsorb the major-
ity of the cadmium ions and released less nickel than
was found in the case of dealginate at the corre-
sponding point at the end of the eleventh adsorption
cycle.
All of the seaweeds and derived materials
exhibited a relatively good ability to remove the
heavy-metal ions that were investigated from solu-
tion. However, the seaweed-derived materials
showed better overall performance when compared
with the seaweeds themselves. In addition, opera-
tional problems associated with the use of seaweeds
would make them an unlikely choice for industrial
scale-up. The copious quantities of released algi-
nates would cause considerable swelling of the
seaweed particles, resulting in increases in pressure
differentials within a flowing system and a potential
for pipework or even valve blockages. In addition,
the gelatinous nature of alginates would impair any
filtration operations and would be likely to detri-
mentally affect any sensitive equipment downstream.
Both the dealginated seaweed and the alginate fibres
were not subject to these problems.
The broad range and apparent high capacity of
these seaweed-derived materials for heavy-metal
removal applications and the absence of any obvious
operational problems suggests that these materials
will lend themselves well to water treatments on a
larger scale. The alginate exhibited the best overall
ability to remove heavy metals. However, the pro-
hibitive cost of this material would probably ensure
that such an end use was never realised on an indus-
trial scale.
The dealginate exhibited a relatively high ability
to sequester heavy-metal ions. This material is cur-
rently a waste product from the alginate production
industries, for which end-use applications are being
sought. There is no existing market value for this
material which currently provides a disposal problem
throughout the alginate production industry. The
market price for the dried unmilled seaweed from
which the dealginate is produced ranges between
£200 and £300 per tonne. Obviously, should a
marketable use be found for this waste product,
market pressures would force the purchase cost of
the material to rise, probably in excess of the cost of
the original seaweed.
The findings of this study suggest that dealgina-
ted-seaweed waste has much potential as a
biosorbent for the removal of heavy-metal ions.
Effective industrial scale-up of a system such as this
would be utilising an existing waste product and pro-
viding a wastewater treatment system which might
prove versatile for a wide range of heavy metals.
ACKNOWLEDGEMENTS
The authors would like to thank Pronova Biopoly-
mers for the provision of biomasses and the British
Textiles Technology Group for carrying out the
ICP-AES analysis. The research was made possible
by funding from the EPSRC and also the co-opera-
tion of the Universit/it Dortmund. The authors
would also like to thank the Department of Chemi-
cal Engineering at the University of Leeds where
this work was carried out.
REFERENCES
Avery, S. V. & Tobin, J. M. (1992). Mechanisms of Sr
uptake by laboratory and brewing strains of Saccharo-
myces cerevisiae. Appl. Environ. Microbiol., 58,
3883-3889.
Brauckmann, B. M. (1990). Industrial solution amenable
to biosorption. In Biosorption, ed. B. Volesky. CRC
Press, Boca Raton, FL.
Cottrell, I. W. & Kovacs, P. (1980). Alginates. In Hand-
book of Water-soluble Gums and Resins, ed. R. L.
Davidson. McGraw-Hill, New York.
Eccles, H. (1995). Removal of heavy metals from effluent
streams--why select a biological process? Int. Biodeter-
ioration Biodegradation, 35(1-2), 5-17.
Orhan, Y. & Buyukgungor, H. (1993). The removal of
heavy metals by using agricultural wastes. Water Sci.
Technol., 2g(2), 247-255.
Simmons, P., Tobin, J. M. & Singleton, I. (1995). Con-
siderations on the use of commercially available yeast
biomass for the treatment of metal-containing effluents.
J. Ind. Microbiol., 14, 240-246.
Volesky, B. (1990). Biosorption and biosorbents. In Bio-
sorption, ed. B. Volesky. CRC Press, Boca Raton, FL.
Wilson, M. W. (1993). Biosorption for the removal of
heavy metals from industrial wastewaters. IChemE
Symp. No. 132, pp. 185-196.