3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Europium removal from aqueous solutions using barley rootlets as
biosorbent
V. Anagnostopoulos, M. Anzaoui and B. Symeopoulos
Radiochemistry Lab, Department of Chemistry, University of Patras, Greece
ABSTRACT
The research is focusing on recovery of lantha-
nides either for minimizing the industrial proc-
esses losses or for reasons related to radioactive
waste management, since Eu and few more lan-
thanides simulate the behavior of long lived fis-
sion products like Am(III) and Cm(III). The po-
tential utilization of barley rootlets, a by-product
of malting industrial process, as a preconcentra-
tion medium of europium is investigated in this
study. The effect of solution pH, contact time
and initial concentration under constant ionic
strength and temperature were studied. Uptake
was found to be rapid and kinetic data were fit-
ted to pseudo-second order and Morris-Webber
models. The equilibrium process was described
by the Langmuir isotherm model yielding
maximum sorption capacity 156 mg Eu/g of dry
biomass compared to 86 mg/g of maximum ca-
pacity of activated carbon under the same condi-
tions, proving barley rootlets to be a more effi-
cient sorbent.
1. INTRODUCTION
Contamination of the environment by toxic
metals such as heavy metals and radionuclides
is mainly caused either by industrial activities or
activities related to diverse applications of nu-
clear energy. Although the removal of toxic
metals has been practiced for decades, the high
cost of common physic-chemical techniques
(e.g precipitation, ion exchange, reverse osmo-
sis, electrochemical treatment etc.) limits their
routine application and this is where biosorption
can cover those niches (Volesky, 2003).
The term biosorption is used to describe the
2
accumulation of metal ions by materials of bio-
logical origin. The process involves two steps:
contact of the biomass with the metal contami-
nated wastewater and separation of the metal -
loaded biosorbent from the metal - depleted ef-
fluent (Ahmad et al., 2004). Materials such as
barley rootlets, which constitute by-products of
malting industrial processes are relatively abun-
dant and low-cost (Low et al., 2000). Europium
was chosen as an analogue for trivalent actinide
ions (Markai et al., 2003; Kolokassidou and Pa-
shalidis, 2006).
The objective of the present study is to inves-
tigate the potential removal of europium from
aqueous solutions by barley rootlets. It is worth
mentioning that this study is the first exploration
concerning the potential use of this material as a
preconcentration medium of a heavy metal or an
organic contaminant.
2. EXPERIMENTAL PART
Biomass, namely barley rootlets, was supplied
by a local brewery and was dried at 50oC over-
night. It was sieved and the fraction 0.18<d<1
mm was chosen for further experiments as
higher europium uptake was observed. A stock
europium solution was prepared by dissolving
the appropriate amount of Eu2Ο3 (Alfa Aesar,
99.99% purity) in acidified triply distilled water.
The resulted solution was standardized by titra-
tion with a standard EDTA solution (Merck, Ti-
trisol). Fresh working solutions were prepared
by diluting appropriate portions of the stock so-
lution with triply distilled water.
Batch sorption experiments were carried out
bringing in contact 0.01 g of dry biomass with
3rd AMIREG International Conference (2009): Assessing the Footprint of 3
Resource Utilization and Hazardous Waste Management, Athens, Greece

10 ml of europium solution of known initial 160

concentration and the suspension was agitated
on a rotary shaker at 25 oC. The suspension was
140

agitated for a length of time varying between 1 120

min and 24 h in order to determine the neces-

q (mg g-1)
100
sary contact time for attaining equilibrium. For 80
the experiments concerning the effect of pH and
60
the sorption kinetics, europium initial concen-
tration was 800 mg/L. For the isotherm experi- 40

ments initial metal concentrations ranged from 20

25 to 800 mg/L. In all experiments the ionic 0
strength (I) was adjusted by NaNO3 solution to 1 2 3 4 5
a total value 0.1 mol/L. At the end of agitation pH
time the suspension was centrifuged and the re- Figure 1: Effect of solution pH on europium uptake by
sidual (final) metal concentration in the super- barley rootlets. Error bars indicate the difference between
natant was determined spectrophotometrically, the two values of q determined by two independent ex-
by Arsenazo III method. The europium uptake periments.
(q/mg.g-1) was calculated from the difference
between the initial (Cin) and the final metal con-
centration (Cfin) using the equation:
q = (Cin − C fin )⋅V / mb (1)
where, mb (g) is the biomass dry weight and V
(l) the volume of the solute.
For each experiment a set of three vials were
used. Two of them, almost duplicate, contained
the metal solution and the biomass, while the
third one contained only the europium solution
without biomass (control vial). All the vials of a
set were treated the same way exactly and si- Figure 2: Speciation of europium under the conditions
studied.
multaneously.

3.2 Sorption kinetics

3. RESULTS AND DISCUSSION
3.1 Effect of pH
Samples with different pH values ranging from
1.5 to 4.5, were agitated for 24 h, at 25 oC. The
effect of pH on europium uptake is shown in
Figure 1. As can be seen, uptake increases sig-
nificantly with pH.
Taking into consideration that the speciation
of europium remains practically the same in the
pH region between 1 and 5 (Fig. 2), it may be
concluded that the uptake increase is due to the
biomass surface charge. Generally at low pH the
net surface charge of the biomass is positive,
thus the approach of positively charged euro-
pium species is inhibited, whilst at higher pH
values the net surface charge turns out to be
negative (Göksungur et al., 2005; Say et al.,
2001).
Kinetic data at pH 4.5 at 25 oC are shown in
Figure 3.
It can be seen that 1 hour is a sufficient time
to attain equilibrium. Kinetic data were applied
to different equations, namely pseudo-second
order kinetic, Equation 2 (Argun et al., 2007)
and Morris-Weber, Equation 3 (Karthikeyan
et al., 2005).
t / q = 1 / h + (1 / qe ) ⋅ t (2)
q = Ridr t + C (3)
where, qe and q stand for amounts of europium
sorbed (mg.g-1) at equilibrium and at time t
(min), k2 is the rate constant of the pseudo sec-
ond order kinetic equation, h = k2qe2, known as
initial sorption rate and Ridr is the intra-particle
3rd AMIREG International Conference (2009): Assessing the Footprint of 4
Resource Utilization and Hazardous Waste Management, Athens, Greece

160 is deduced that the sorption process occurred in

two stages: by surface sorption and intraparticle
140
diffusion. The larger the intercept, the greater
120 the contribution of the surface sorption in the
rate-controlling step (Kalavathy et al., 2005).
q (mg g-1)

100
80
60
40
20
0 50 100 150 200
t (min)
Figure 3: Effect of contact time on the uptake of europium
by barley rootlets biomass.
diffusion rate constant.
A plot of t/q versus t was used to evaluate the
pseudo second order model and the values of k2
and h were found 4.3·10-4 g mg-1 min-1 and 10
mg g-1 min-1 respectively (correlation coefficient
R2 = 0.991). The results of the data fit to Morris-
Webber model can be seen in Figure 4.
There are four main stages in the process of
adsorption by porous adsorbents: i) solute trans-
fer from the bulk solution to the boundary film
that surrounds the adsorbent’s surface, ii) solute
transport from the boundary film to the adsorb-
ent’s surface, iii) solute transfer from the ad-
sorbent’s surface to active intraparticular sites,
iv) interactions between the solute species and
the available adsorption sites on the internal sur-
faces of the adsorbent (Argun et al., 2007).
Ridr was found to be 19 mg g-1 min-1/2 (corre-
lation coefficient R2 = 0.999). From Figure 4, it
160
140
120
q (mg g-1)
3.3 Effect of metal ion concentration
Isotherms were drawn at pH value 4.5 and con-
tact time 24h. Increase of uptake was observed
with the increase of uranium initial concentra-
tion indicating that uranium initial concentration
is the driving force for biosorption. For com-
250
parison reasons, parallel experiments with acti-
vated carbon (Merck) as sorbent instead of bar-
ley rootlets were carried out under identical
conditions.
The effect of tested metal ion concentration
was analyzed in terms of Langmuir model
(Altin et al., 1998):
q = (qmax ⋅ K L ⋅ C fin )/ (1 + K L ⋅ C fin ) (4)
where qmax (mol g-1) maximum metal uptake, KL
Langmuir constant and Dubinin-Radushkevich
model (Bering et al., 1972):
ln q = ln X m − K ' ε 2 (5)
where ε is the Polanyi potential
ε = RT ⋅ ln (1 + 1 / C fin ) (6)
Xm the adsorption capacity of the sorbent (mol
g-1), K´ is a constant related to the adsorption
energy (mol2 kJ-2), T temperature (K) and R the
gas constant (kJ K-1 mol-1). The mean adsorp-
tion energy E (kJ mol-1) can be obtained from
the K´ values using Εquation 7:
E = (− 2 K ')
−1 / 2
(7)
For E<8kJ mol-1, physisorption dominates the
sorption mechanism, if E is between 8 and 16 kJ

mol-1 ion-exchange is the dominant factor and if

100

80 E>16kJ mol-1 sorption is dominated by particle

diffusion.
60
Results are summarized in Tables 1 and 2.
40 Results suggest that sorption of europium
both onto barley rootlets and activated carbon is
20
2 4 6 8 10 12 14 16 dominated by ion-exhange mechanism.
As may be seen from Figure 5 barley rootlets
t 1/2 (min1/2) are proved to be a much more efficient biosor-
Figure 4: Intraparticle diffusion plot for the sorption of bent for the removal of europium from aqueous
europium onto barley rootlets.
solutions than activated carbon. More specifi-
3rd AMIREG International Conference (2009): Assessing the Footprint of 5
Resource Utilization and Hazardous Waste Management, Athens, Greece

Table 1: Regression parameters for Langmuir isotherms. ardous materials 141: 77-85.
103 x qmax 10-2 x KL 2 Bering, B.P., M.M. Dubinin and V.V. Serpinsky, 1972.
Biosorbent R On thermodynamics of adsorption in micropores,
(mol g-1) (l mol-1)
Journal of Colloid and Interface Science 38: 185-194.
Barley Göksungur, Υ., S. Üren and U. Güvenc, 2005. Biosorp-
1.0 23 0.999
rootlets tion of cadmium and lead ions from ethanol treated
Activated waste baker’s yeast biomass, Bioresource Technology
0.58 43 0.997
carbon 96: 103-109.
Kalavathy, M.H., T. Karthikeyan, S. Rajgopal and L.R.
Table 2: Regression parameters for Dubinin Radushke- Miranda, 2005. Kinetic and isotherm studies of Cu (II)
vich isotherms. adsorption onto H3PO4-activated rubber wood saw-
103 x K´ E dust, Journal of Colloid and Interface Science 292:
Biosorbent R2
(mol2 kJ-2) (kJ mol-1) 354-362.
Barley Karthikeyan, T., S. Rajgopal and L.R. Miranda, 2005.
5.1 9.9 0.967 Chromium (VI) adsorption from aqueous solutions by
rootlets Hevea Brasiliensis sawdust activated carbon, Journal
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0.58 12 0.969
carbon Kolokassidou, K. and I. Pashalidis, 2006. Potentiometric
investigation on the interaction of humic acid with
Cu(II) and Eu(III) ions, Radiochimica Acta 94: 1-4.
cally, according to the qmax calculated from Low, K.S., C.K. Lee and S.C. Liew, 2000. Sorption of
Langmuir model, barley rootlets yield a maxi- cadmium and lead from aqueous solutions by spent
mum sorption capacity under the conditions grain, Process Biochemistry 36: 59-64.
studied of 1.0·10-3 mol g-1 (156 mg g-1) in con- Markai, S., Y. Andrès, G. Montavon and B. Grambow,
2003. Study of the interaction between europium (III)
trast to activated carbon which yields 0.58·10-3 and Bacillus subtilis: fixation sites, bioorption model-
mol g-1 (86 mg g-1). ling and reversibility, Journal of Colloid and Interface
Science 262: 351-361.
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140

120

100
q (mg g-1)

80

60

40

20

0
0 100 200 300 400 500 600 700 800

Cfin (mg l-1)

Figure 5: Experimental isotherms for europium sorption
onto barley rootlets (black boxes) and activated carbon
(white boxes).