Minerals Engineering, Vol. 8, No. 9, pp.

979-988, 1995
Elsevier Science Ltd
Pergamon Printed in Great Britain
0892-6875(95)00061-5 0892--6875/95 $9.50+0.00

EICHHORNIA CRASSIPES AS BIOSORBENT FOR HEAVY METAL IONS

I. A. H. SCHNEIDER§, J. RUBIO§, M. MISRAt and R. W. SMITHt

PPGEMM, Federal University of Rio Grande do Sul, 90210 Porto Alegre, RS, Brazil
J" Mackay School of Mines, University of Nevada, Reno, Nevada, 89557, USA
(Received 5 April 1995; accepted 12 May 1995)

ABSTRACT

Eichhornia crassipes approaches being a scourge in many parts of the world, choking
waterways and hindering transport upon them. At the same time it is known to readily
abstract heavy metal ions from water and, thus, aids in the removal of heavy metals found
in such waters. This paper considers the possibility of using dried parts of the plant as
an inexpensive adsorbent for the removal of heavy metals from contaminated chemical
and mining industry waste waters. In particular the root of the plant was found to be an
excellent accumulator of divalent heavy metal ions from solution although the entire
biomass of the plant was also found to be a good sorbent for these ions. It is also
suggested that the dried biomass of the plant might be placed in simple bags and used in
a very low cost metal ion removal system.

Keywords
Eichhornia crassipes, metal ion removal

INTRODUCTION

Because of its rapid, spreading, growth in frost free waters, Eichhornia crassipes (water hyacinth)
approaches being a scourge in many subtropical and tropical parts of the world, choking waterways and
hindering transport upon them. However, it is also known to be an accumulator of heavy metal ions and
has been widely studied as such [1-9]. However, two main disadvantages emerge from this practice. First,
ponds have to be constructed if they are not available in place and, second, heavy metals produce phytotoxic
effects on plants resulting in inhibition of chlorophyll synthesis and necrosis [4,8,9]. Additionally, the metal
sorption capacity of the dried biomass of aquatic plants has been recently investigated [ 10,11]. Compared
to living systems, dried biomass presents advantages for conservation, transport and handling, being able
to be applied in waste water treatment plants as a simple sorbent material. To date, however, the individual
parts of E. crassipes (stems, roots, leaves of the plants) have not been studied. Also, there has been little
'direct comparison of the relative heavy metal biosorption by E. crassipes and its parts to biosorption by
various other biosorbents.

The present study investigates the biosorption of divalent heavy metals by E. crassipes biomass. Metal
uptake values obtained with this plant are compared to those of other biosorbents. In addition a low cost
metal ion removal system for decontamination of chemical and mining industry waste waters is suggested.

8:9-c 979
980 I.A.H. SCHNEIDERet el.

M A T E R I A L S AND METHODS

Biosorbents and reagents

The Eichhornia crassipes used in the experimentation was obtained from wild specimens growing in Rio
Grande do Sul State, Brazil. The roots, the aerial parts (stems plus leaves) or the whole plant were washed,
dried at 60°C and ground in a bladed mixer to less than 0.59 mm (Tyler 28 mesh). The biomass preparation
scheme is shown schematically in Figure 1. The yeast Candida parapsilosis and the bacterium
Mycobacterium phlei were grown in a culture medium of the composition: 10 g/1 dextrose, 1 g/1 yeast
extract and 2g/1 enzymatic-hydrolysate casein. Cultures were grown in 300 ml flasks continuously shaken
in a water bath held at 35°C. After 48 hr in the case of C. parapsilosis and for 48 days in the case of M.
phlei the cells were harvested by centrifugation, washed in distilled water and dried at 60°C. The fungus
Rhizopus oryzae was grown on potato dextrose agar and the mycelia periodically collected under sterile
conditions. Acacia bark was obtained as a byproduct of a tannin production plant. The fungus and the bark
were also washed in distilled water and dried at 60°C.

washing [
C~f3JC-~ I drying] Biosorbent

[screening I
Eichhornia crassipes
I packing I

Fig. 1 Procedure for preparation of Eichhornia crassipes biomass.

Reagents used for the make up of metal containing solutions were of reagent grade and were as follows:
Pb(NO3)2, Cd(CH3CO2)2.2H20, CuSO4.5H20 and ZnSO4.7H20. Required pH adjustment was made using
reagent grade NaOH and HNO 3.

Surface area and scanning electron microscope measurements

The surface area of E. crassipes individual parts was measured using a methylene blue adsorption method
[12]. Glass flasks containing 100 ml of various concentrations of methylene blue solutions were shaken for
1 hr at 25°C with 0.1 g of biosorbent. Preliminary experimentation of adsorption kinetics indicated that this
time period was sufficient to attain equilibrium. Subsequently, the final equilibrium concentration of dye was
determined spectrophotometrically at 656 nm. The surface areas were calculated from the saturation
adsorption assuming a cross sectional area of 108 A 2 for the methylene blue molecule. In addition a
standard BET surface area measurement was made of the plant's root material.

Scanning electron micrographs of the dried biomass were taken using a JSM-840A JOEL electron
microscope.

Biosorption studies
For determining the abstraction of the metal ions from solution by the biosorbents, 100 ml of a heavy metal
containing solution was stirred for 30 min with 0.2 g of biosorbent. The concentration of heavy metal ions
in solution was determined both before the introduction of the biosorbent and after the reaction of the
biosorbent with the metal containing solution. The amount of heavy metal ions abstracted from solution was
 Eichhornia crassipes as biosorbent 981

determined, using atomic adsorption spectroscopy, by the difference in metal ion concentration from the two
analyses performed before and after introduction of the biomass.

Sorption isotherms were measured at 25 oC by varying the initial metal ion concentration and keeping the
amount of biosorbent constant. Isotherms obtained were analyzed by the Langmuir model, which is,
mathematically:

m oKC
m = .

(1 +KC)

or (linearized form)

C 1 C
m Km, m°

where: m = mass of solute sorbed per unit weight of sorbent

m o = mass of solute sorbed per unit weight of sorbent at saturation
K = constant accounting for the energy of interaction
C = measured concentration of sorbate in solution at equilibrium

RESULTS

The biosorption of lead and copper by selected biosorbents was initially determined. Data obtained is
depicted in Tables 1 and 2. It is readily noted that E. crassipes is a particularly good adsorbent for these
divalent metals.

TABLE 1 Sorption of Pb(II) by selected biomateriais; 2 g/! of biosorbent,

30 min reaction with agitation, initial pH 5.5 ± 0.2

Biomass Initial Final Recovery

Concentration Concentration (%)
(rag/l) (mg/l)

Eichhornia crassipes (root) 20.0 0.0 100

Eichhornia crassipes (aerial part) 20.0 0.5 97

Acacia Bark 20.0 1.4 93

Rhizopus oryzae 20.0 4.6 77

Candida parapsilosis 20.0 6.3 68

Mycobacterium phlei 20.0 10.9 45

Table 3 gives the surface areas determined by the dye sorption method for the roots and aerial parts of the
plant. An earlier standard BET surface area measurement of the root material indicated a surface area of
150 me/g although it was not certain that equilibrium had been reached in the system. Figures 2 and 3 show
scanning electron micrographs of E. crassipes roots and stems, respectively. From observation of the
micrographs it is apparent that these parts of the plant have an extremely porous structure which must
account in large part for their very large surface areas.
982 I.A.H. SCHNEIDERet al.

TABLE 2 Sorption of Cu(II) by selected biomaterials; 2 g/l biosorbent,

30 min reaction time with agitation, initial pH 5.5 + 0.2

Biomass Initial Final Recovery

Concentration Concentration (%)
(rag/l) (rag/l)

Eichhornia crassipes (roots) 6.3 0.3 95

Eichhornia crassipes (aerial parts) 6.3 1.5 76

Acacia Bark 6.3 2.0 68

Rhizopus oryzae 6.3 2.6 59

T A B L E 3 Surface areas of Eichhornia crassipes individual parts

Biomass Specific surface area

(m2/gm)

Eichhornia crassipes, roots 243

Eichhornia crassipes, aerial part 223

Eichhornia crassipes, whole plant 231

Fig.2 Scanning electron micrograph of the root material of Eichhornia crassipes

showing the intricate, porous, structure of the material.

Figure 4 shows the sorption isotherm for copper by the roots and the aerial part of the plant. It is evident
that the roots accumulate more of the metal than does the aerial part. However, the difference seems not
to be sufficient to justify the additional step (economically if the biomass is to be used in a remediation
operation) of separating the various parts of the plant. Thus, in all subsequent experimentation the entire
biomass was used.
 Eichhornia crassipes as biosorbent 983

Figure 5 illustrates the comparative results of sorption of copper, zinc, cadmium and lead by E. crassipes.
The isotherms follow the Langmuir adsorption model as is confirmed for copper by the straight line
relationship of Figure 6. The mass of heavy metal sorbed per unit weight of E. crassipes at saturation
concentration (mo) to be about 20 mg/g for Zn(II), 23 mg/g for Cu(II), 27 mg/g for Cd(II) and 47 mg/g for
Pb(II) (see Table 4).

Figure 7 indicates the effect of time of reaction between E. crassipes and the metal containing solution on
the sorption of Cu(II) onto the plant biomass. The data indicate that maximum sorption is obtained within
10 min reaction time.

Fig.3 Scanning electron micrograph of the stems of Eichhornia crassipes

showing its hollow structure.
30

E. c r a s s i p e s - roots

E 20

10 crassipes stems and leaves

Y ! I I I
0 5 10 15 20 25
Equilibrium c o n c e n t r a t i o n (mg/I)

Fig.4 Copper sorption isotherms for different parts of Eichhornia crassipes.

984 I . A . H . SCHNEIDER et al.

Figure 8 shows the effect of equilibrium pH on the sorption of Cu(II) onto E. crassipes. Maximum removal
from solution was attained between pH 5.0 and 6.6. At such pH values copper is present in solution
primarily in the form Cu 2+ as indicated by the log concentration diagram of copper species in solution as
shown in Figure 9. Thus, little copper sorption occurs at very low pH values or when copper precipitates
as Cu(OH)2(s).

Of
40

20 Cd
Cu
Zn
1

0 5 10 15 20

Equilibrium concentration (mg/I)

Fig.5 Zinc, copper, cadmium and lead isotherms of Eichhornia crassipes (whole plant).

1.2

0.8

E
¢J 0.6

0.4 - .~" in, = 23.1 mg/g

K = 0.241
0 . 2 !~' cc = 0 . 9 9 9

0 I L n l

0 5 10 15 20 25

Fig.6 Langmuir plot of the copper sorption isotherm.

 Eichhornia crassipes as biosorbent 985

TABLE 4 Heavy metal uptake and surface coverage per unit weight
of Eichhornia crassipes biomass at saturation

Element Accumulation (mg/g) Accumulation (mol/g) Surface Coverage (%)

Pb 47 2.3 x 10 .4 4.5

Cd 27 2.4 x 10 -4 3.9

Cu 23 3.6 x 10 .4 4.0

Zn 20 3.0 x 10-4 3.8

E
c-
o
°~
5
L.
4.
U
c-
O
u 3
m

C
2

D.

o=.1 _= •
U
I I I I
0
0 5 10 15 20 25
T i m e (min)

Fig.7 Biosorption of copper onto Eichhornia crassipes as a function of reaction time

solution-biomass. Initial Cu(II) concentration of 6.3 mg/1, pH 5.5 ___0.2, 2 g/l biosorbent.

O~
6-
E
C
0 5-
ca
i.

¢) 4-
U

0
U 3-
fo

2
e~

o 1

I I I I I
0
0 2 4 6 8 10 12

pH
Fig.8 Biosorption of copper onto Eichhornia crassipes as a function of pH.
Initial Cu(II) concentration of 6.3 mg/l, 30 min agitation time, 2 g/l biosorbent.
986 I.A.H. SCHNEIDERet al.

100
Cu 2+
S Cu(OH
2~()s)
80
v
i/)

"6 60

40

"0

"~ 2o
Cu(OHI * ~ \ Cu(
, ~_..~ ,
O !
0 2 4 6 8 10 12
pH
Fig.9 Concentration diagram for copper species in solution.
Total copper concentration: 1 x 10-4 mol/1 (6.3 mg/l).

DISCUSSION AND CONCLUSIONS

In terms of lead and copper uptake per dried mass of biosorbent, the aquatic plant showed to be a better
biosorbent than the biomass of the bacterium M. phlei, the yeast, C. parapsilosis, the fungus R. oryzae and
acacia bark. Considering the large surface area of the E. crassipes parts, it is not surprising that these
materials are excellent biosorbents for multivalent metal ions. From results obtained it was possible to
estimate the surface coverage at saturation sorption. The values obtained are listed in Table 4. The surface
coverage of the E.crassipes biomass ranged from 3.8 to 4.5 % depending on the atomic weight and the
atomic radius of the metals.

On a weight basis the ability of E. crassipes to accumulate metal ions was found to be in the order Pb(II)
> Cd(II) > Cu(II) = Zn(II). However, when the data are converted to mol metal ion/g biosorbent it is
apparent that the biomaterial is equally effective at removal of all of the metals studied (see Table 4). Thus,
the weight differences in metal ion removal for the different metals is strictly based on the relative atomic
weights of the metals. This roughly equal sorption for the different metal ions suggests that the ions are
sorbing onto specific sites and that multi-layer sorption is unlikely. Also monolayer coverage (or specific
site sorption) is the main assumption of the Langmuir model, which correctly describes the uptake of these
divalent cations by E. crassipes biomass (see Figure 6). However, transmission electron microscopy work
performed during past studies using green algae [13,14] and an actinomycetes [15,16] as biosorbents for
Pb(II) clearly showed Pb present in sizeable patches on the algae and actinomycetes surfaces. Thus, there
is a strong indication that Pb(II) sorption onto the microorganisms involves an additional mechanism to
simple sorption site-sorbate interaction.

Recently, the United States Bureau of Mines [17,18] developed a simple scheme for removing heavy metals
from small waste aqueous streams, based on a technology that involves immobilizing organic material
within porous polysulfone beads. The beads, containing the organic material, have a great adsorption
capacity for heavy metal ions. In the scheme the beads are placed in porous bags which then are placed in
a trough circuit through which the metal contaminated aqueous stream flows by gravity. Bags are removed
periodically and the beads regenerated through an elution process. The beads are quite stable and can be
put through a number of regeneration cycles without significant loss of adsorption capacity. The scheme
shows considerable promise as an inexpensive means to remove heavy metal ions from small mine drainage
seeps or similar small effluent streams. Drawbacks to the process are the cost of producing the beads and,
also, in immobilizing the organic material in the beads, adsorption sites are lost through cross-linking so
 Eichhornia crassipesas biosorbent 987

that the organic material will not accumulate as great an amount of metal ions. It is suggested that E.
crassipes root material placed in similar bags may accumulate greater concentrations of metal ions than the
beads. In addition there would be no bead manufacturing costs. Whether the root material can be as readily
regenerated and whether the root material has the same ability to go through as many elution cycles as the
beads is not known. However, recent research work on the use of the aquatic plant Potomogenton luscens
shows that it can be put through a considerable number of loading-elution cycles without degrading or
losing its ability to accumulate heavy metal ions [10,11]. Future work is planned on the regeneration of E.
crassipes root after heavy metal accumulation and on the possibility of employing it in simple systems
similar to the one developed by the United States Bureau of Mines.

ACKNOWLEDGMENTS

The first two authors are grateful for the financial support given by CNPq and CAPES for this research. The
authors also acknowledge Ana Suel Almeida, Fabiana Tessili and Tamara Barlem for their help in the
experimental work.

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