Materials Transactions, Vol. 52, No. 9 (2011) pp.

1799 to 1806
#2011 The Japan Institute of Metals

Leaching of Rare-Earth Elements and Their Adsorption

by Using Blue-Green Algae
Jung-Ah Kim1; * , Gjergj Dodbiba1 , Yuji Tanimura2 , Kohei Mitsuhashi2 ,
Naoki Fukuda2 , Katsunori Okaya1 , Seiji Matsuo1 and Toyohisa Fujita1
1
Department of Systems Innovation, Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2
Research and Development, Nittetsu Mining Co., Ltd., Tokyo 190-0182, Japan

In the present study, REEs were leached from a Vietnamese ore, by using (NH4 )2 SO4 and REEs were adsorbed from this leachate by blue-
green algae (phormidium). In addition, the biosorption characteristics of phormidium for the adsorption of Nd has been studied.
When the concentration of ammonium sulfide was 1%, leaching time was 3 h, and S/L ratio was 0.09, the leaching ratio of Nd was 67.3%.
In the adsorption process, when dosage of phormidium was 0.2 kg/L, the contact time was 30 min, and the temperature was 298 K, while pH was
kept at the initial value (i.e. pH 5.6), the adsorption density of Nd was 182 mg/kg. These results were similar with the adsorption density of other
absorbents, such as: activated carbon, Fe-based absorbent, and calcinated dolomite. Moreover, the equilibrium sorption isotherm of Nd onto
phormidium was described by the Langmuir isotherm equation and the pseudo-second-order kinetic model fits the experimental data well.
[doi:10.2320/matertrans.M2011111]

(Received April 13, 2011; Accepted June 13, 2011; Published July 27, 2011)
Keywords: rare-earth elements (REEs), leaching, biosorption, blue-green algae

1. Introduction and/or biological sludge to be handled and high efficiency in

The rare earth elements (REEs) include 15 lanthanide
elements (Z ¼ 57 through 71) and yttrium (Z ¼ 39).1) As the
number of technological applications of REE has been
multiplied over the past several decades, demand for several
of the less abundant REE has increased dramatically. The
diverse nuclear, metallurgical, chemical, catalytic, electrical,
magnetic and optical properties of the REE have led to an
ever increasing variety of applications. These uses range
from mundane to high-tech to futuristic. China now produces
over 95% of the world’s rare earth supply.2) To cope with
monopoly of China and to expand and develop the use
of the rare earths, the search for new mineral sources is
important.
Considering the main disadvantages of conventional
process like sulfuric acid roasting and sodium hydroxide
treatment, one of the emerging techniques for extracting
rare earth involves ammonium compounds.3) The chemical
reaction equation is as follow;4)
fAl4 [Si4 O10 ](OH)8 gm   nRE(s) 3þ þ 3nNH4(aq) þ
$ fAl4 [Si4 O10 ](OH)8 gm   3nNH4(s) þ þ nRE(aq) 3þ
where, s and aq stand for solid phase and liquid phase,
respectively. In the present study, REEs was leached from
ore, which was imported from Vietnam by using (NH4 )2 SO4
and the effects of concentration, leaching time and S/L ratio
were investigated. In addition, REEs was adsorbed from this
leachate by biosorption. Biosorption is an innovative method
that employs inactive and dead biomass for the recovery of
metals from aqueous solution. As an alternative to traditional
methods, its application in various cases is now widely
considered by the scientific community.5) A biosorption-
based process offers a number of advantages when compared
to the conventional methods used. These include low
operating costs, minimization of the volume of chemical
*Graduate Student, The University of Tokyo
detoxifying effluents.6,7) In particular, phormidium used in
this study is a kind of cyanobacteria. Nearly 200 species of
phormidium are found worldwide and certain species inhabit
the thermal springs. In Japan, which is well-known for
thermal springs, phormidium is affordable material. By the
way, because the phormidium produces a hydrogen sulfide
which leads to anoxic conditions, the corals die. Therefore
the phormidium was used for REEs adsorption and the
possibility of the phormidium to be used as an adsorbent was
investigated. In addition, the biosorption characteristics of
phormidium for the adsorption of Nd ions from aqueous
solution were also evaluated.
2. Experimental
2.1 Leaching method
The ore was crushed and screened to less than 3 mm in
size, before being imported from Vietnamese mine to Japan.
The leaching process of REEs from the ore was carried out
in a 0.1 L flask and temperature was adjusted at room
temperature (i.e. 293 K). Stirring of leaching solution and
ore was achieved by using magnetic bar driven by a variable
speed motor. (NH4 )2 SO4 was used for REEs leaching.
The concentration of (NH4 )2 SO4 was varied between 1 and
10 mass%. The leaching time was kept constant between
0.5 and 18 h. The solid/liquid ratio was fixed in the range
between 0.03 and 0.20. At the end of each test, the leachate
was analyzed for REE ions by using an inductive coupled
plasma-optical emission spectroscopy (ICP-OES: Optima
5300 DV, PerkinElmer).
2.2 Preparation of phormidium adsorbent
The phormidium was collected around hot spring in Akita,
Japan. The collected phormidium was washed 3 times by
distilled water and dried at 358 K for 48 h. After drying, the
product was ground by using a mortar and pestle to less
74 mm in size. The product was used for adsorption.
1800 J.-A. Kim et al.
2.3 Adsorption method
Leachate (0.01 L), which pH value was carefully con-
trolled, and a known amount of the phormidium were placed
in a 0.02 L vial; then pH adjusted between 1 and 8. The vial
was then shaken at 150 rpm at 293 K. During this set of
experiments, dosage of adsorbent was changed from 0.5 to
200 g/L and contact time was varied between 1 and 120 min.
After adsorption test, the solution was filtered and the
solution was analyzed for REE ions by ICP-OES.
Next, the experimental results were reported in terms of
the Nd-adsorbed concentration (i.e. mass of Nd/mass of
adsorbent), which is also known as adsorption density. The
adsorbed amount of Nd, q was calculated using the following
equation (eq. (1)):
V S/L ratio is 0.1 (2 kg/20 L). In order to confirm effect of
q ¼ ðC0  C1 Þ ðmg/gÞ ð1Þ
M
where C0 and C1 are aqueous concentration of adsorbate
(in mg/L) before and after adsorption, respectively. V is the
volume of sample (in L); M is the mass of the adsorbent
(in g).
2.4 Analysis method
Chemical composition of REEs ore was analyzed by X-ray
fluorescence (XRF: Supermini, RIGAKU) and ICP-OES.
In addition, the structure of the synthesized adsorbents was
analyzed by means of an X-ray diffractometer (XRD:
MO3XHF, Mac Science). Scanning electron microscope
equipped with an energy dispersive X-ray spectroscope
(SEM-EDS: JSM-7000FX, JEOL) was also used to analyze
the morphology of the ore.
3. Experimental Results
3.1 Characterization of REEs ore
The elemental composition of the REEs ore is given in
Table 1. The results of the XRF analysis showed that the ore
contained about 21.4 mass% Al, 47.6 mass% Si, 7.6 mass% K
and 18.8 mass% Fe. REEs content is lower than detecting
limit of this XRF. Therefore, the ore was dissolved in acid
and analyzed by ICP-OES. It can be noted that REEs ore
contained 777 mg/kg La, 881 mg/kg Ce, 113 mg/kg Pr,
376 mg/kg Nd, 57 mg/kg Sm, 50 mg/kg Gd and 29 mg/kg
Dy. Figure 1 shows SEM image and EDS elemental maps of
REEs ore. It was observed that silicon [Si], iron [Fe],
Potassium [K] and aluminium [Al] occupy the greater part
of the ore. Because the detecting limit of EDS is about
1000 ppm, REEs were not detected.
Figure 2 shows the X-ray diffraction pattern of REEs ore.
X-ray diffraction analysis indicated that quartz [SiO2 ],
kaolinite [Al2 Si2 O5 (OH)4 ] and Gibbsite [Al(OH)3 ] were
the main crystalline phases and no crystalline structure of
REEs was observed, suggesting that REEs concentration
is below the detection limit. Chi and Tian3) reported that
in the weathered crust elution-deposited rare earth ore,
RE is mainly adsorbed on clay minerals 85% RE exists as
ion phase, adsorbed by alumino-silicate mineral such as
kaolinite and mica, which is a kind of RE carrier. So it
was thought that REEs exist as ion phase into kaolinite in
this sample.
Table 1 The chemical composition of REEs ore.
(analyzed by XRF, Unit: mass%)
Mg Al Si K Ti Mn Fe
content 0.9 21.4 47.6 7.6 2.0 0.2 18.8
(analyzed by ICP-OES, Unit: mg/kg)
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
content 777 881 113 376 57 7 50 6 29 6 15 2 12 2
3.2 REEs leaching using ammonium sulfide
Leaching ratio of REEs according to the concentration of
(NH4 )2 SO4 is given in Fig. 3(a). Leaching time is 24 h and
(NH4 )2 SO4 , the sample was leached by distilled water. REEs
were not leached by (NH4 )2 SO4 and leaching ratio of REEs is
about 0%. Leaching ratio of REEs increased with increasing
the concentration of (NH4 )2 SO4 up to 3%; after that, it is
decreased with increasing the concentration of (NH4 )2 SO4 .
When concentration of (NH4 )2 SO4 is 3%, the leaching ratio
of La is 59.9% and one of Pr is 62.8%, one of Nd is 69.5%,
one of Sm is 74.4%, one of Gd is 47.3% and one of Dy is
51.6%. In case of Ce, in spite of high content in ore, leaching
ratio by (NH4 )2 SO4 is just about 2.5%. Figure 3(b), on the
other hand, shows the concentration of leached impurities
according to the concentration of (NH4 )2 SO4 . K and Fe were
not leached and the concentration of Mn was not affected
by concentration of (NH4 )2 SO4 . The concentration of Al
increased, but Mg and Si decreased with increasing concen-
tration of (NH4 )2 SO4 . Although the highest leaching ratio is
indicated at 3% (NH4 )2 SO4 , there is not big difference of
leaching ratio between 1 and 5%.
Figure 4 shows the leaching ratio of REEs and leaching
concentration of impurities as a function of leaching time.
Then, concentration of (NH4 )2 SO4 is kept at 1% and S/L
ratio was 0.1. There is difference between increasing rate,
leaching ratio of increased with increasing leaching time,
(Fig. 4(a)). In case of Sm, leaching ratio of Sm was 52.2% at
30 min leaching time. When leaching time was 3 h, one of Sm
was 61.0%. And when leaching time was 18 h, one of Sm was
65.2%. Mg, K Fe were not leached. The concentration of Al,
Si and Mn showed the same pattern, since these values
increased continuously with increasing leaching time. When
leaching time was 3 h, concentration of Al was 0.6 mg/L, one
of Si was 8.0 mg/L and one of Mn was 3.7 mg/L. We found
that these concentration increased by 1.0, 5.5 and 4.5 mg/L
when leaching time was 18 h. Not only the leaching ratio of
REEs increased with increasing leaching time, but also the
concentration of impurities. Therefore, the optimum leaching
time was 3 h.
A look at Fig. 5 shows that the leaching ratio of REEs;
then, concentration of (NH4 )2 SO4 was 1% and leaching time
was 3 h. Leaching ratio of La, Pr, Nd and Sm had equilibrated
in spite of increasing S/L ratio. However leaching ratio of Gd
and Dy increased with increasing S/L ratio up to S/L ratio
0.09; after that, it was maintained according to increasing in
S/L ratio. At condition of 0.09 S/L ration, leaching ratio of
La was 58.7%, one of Pr was 62.2%, one of Nd was 67.3%,
one of Sm was 71.0%, one of Gd was 46.0% and one of
 Leaching of Rare-Earth Elements and Their Adsorption by Using Blue-Green Algae 1801

100 µm IMG1 100 µm OK

(a) SEM image (b) O Kα

100 µm Si K 100 µm Fe K

(c) Si Kα (d) Fe Kα

100 µm KK 100 µm Al K

(e) K Kα (f) Al Kα

Fig. 1 SEM image and EDS elemental maps of REEs ore.

5500 Dy was 47.0%. In case of the concentration of impurities,

Q
5000 Q Quart - SiO2 it was showed continuous increasing with increasing in
4500 K Kaolinite - Al2Si2O5(OH)4 S/L ratio. Considering the results, the authors suggest that
G Gibbsite - Al(OH)3
4000 leaching of REEs should be carried out at the S/L ratio range
3500 of about 0.09.
Intensity (cps)

3000 As results of leaching experiments, the optimum condition

2500 for leaching REEs from Vietnamese ore using by (NH4 )2 SO4
2000 was like that; concentration of (NH4 )2 SO4 is 1%, leaching
1500 Q time is 3 h and S/L ratio was 0.09.
1000
Q
500 K K QQ Q Q Q 3.3 REEs adsorption using phormidium
GK K Q Q Q
0
10 20 30 40 50 60 70 80
After leaching, the experiment of REEs adsorption was
Diffraction angle, 2-Theta [CuKα]
carried out by using phormidium. In the adsorption exper-
imental, the leachate was produced after 18 h by using 2%
Fig. 2 X-ray diffraction pattern of REEs ore. (NH4 )2 SO4 at 0.09 S/L ratio. The adsorption density of
1802 J.-A. Kim et al.

(a) 100 (a) 100

La Ce Pr Nd La Pr Nd
90 90
Sm Gd Dy Sm Gd Dy
80 80
70 70
Leaching ratio, (%)

Leaching ratio, (%)

60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Pulp density of leaching solution, (%) Contact time, (hours)

16 (b) 16
(b)
Mg Al
14 14
Concentration of impurities (mg/L)

Si K

Concentration of impurities (mg/L)

12 12 Mn Fe
Mg
10 Al 10
Si
8 K 8
Mn
6 6
Fe
4 4
2 2
0 0
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Concentration of ammonium sulfate (%)
Leaching tiem, t/h

Fig. 3 Leaching ratio of REEs (a) and leaching concentration of impurities

Fig. 4 Leaching ratio of REEs (a) and leaching concentration of impurities
(b) according to the concentration of ammonium sulfate, (Experimental
(b) according to leaching time, (Experimental conditions: ammonium
conditions: Leaching time: 24 h; S/L ratio: 1/10; Temperature: 293 K).
sulfate concentration: 1%; S/L ratio: 1/10; Temperature: 293 K).

phormidium on REE was compared with other adsorbents a function of dosage of adsorbent; then, contact time was
used generally including activated carbon, Fe-based adsorb- kept for 2 h, temperature was 293 K and pH was about 5.6.
ent, Mn2 O3 and calcinated dolomite (at 983 K for 5 min), The concentration of REEs after contact with phormidium
and the results are given in Fig. 6. The dosage of adsorbent decreased with increasing the dosage of absorbent, in other
was kept at 100 g/L, whereas the sample volume was 0.01 L. words, adsorbed concentration increased. When dosage was
In addition, the adsorption was carried out for 30 min at 200 g/L, concentration after contact of La is 4.82 mg/L, one
about 298 K. The adsorption density of Mn2 O3 is the lowest of Pr is 0.28 mg/L, one of Nd is 1.77 mg/L, one of Sm
but one of other adsorbents is quite similar with one of is 0.33 mg/L, one of Gd is 0.04 mg/L and one of Dy is
phormidium. Especially, activated carbon shows the highest 0.08 mg/L. About 4.8 mg/L La and 1.8 mg/L Nd were
adsorption density; adsorption density of La is 409 mg/kg, remained so far, but it was thought that this value was the
one of Pr is 60 mg/kg, one of Nd is 231 mg/kg, one of limitation.
Sm is 37 mg/kg, one of Gd is 20 mg/kg and one of Dy is The concentration of REEs after contact with phormidium
14 mg/kg. In case of phormidium, adsorption density of La is as a function of contact time was given in Fig. 9. When
375 mg/kg, one of Pr is 57 mg/kg, one of Nd is 217 mg/kg, contact time was 120 min, the concentration of REEs except
one of Sm is 35 mg/kg, one of Gd is 20 and one of Dy is Nd was 0 mg/L, then one of Nd was 1.59 mg/L. Moreover
14 mg/kg. These results proved the effectiveness of phormi- it was found that adsorption was occurred for a short time
dium as an adsorbent for REEs. Additionally adsorption at early stage. As a result of contacting for 30 min, the
behavior of impurities was investigated. Figure 7 shows the concentration of Gd and Dy was 0 mg/L and one of La was
concentration of impurities before and after contact with 7.00 mg/L, one of Pr was 0.60 mg/L and one of Sm was
phormidium. It was noted that impurities don’t adsorbed 0.10 mg/L. One of Nd was 2.35 mg/L.
onto phormidium. The other way, concentration of impurities Figure 10 shows adsorption density of REEs after contact
increased after contact with phormidium, because impurities with phormidium as a function of temperature. Then dosage
were leached from phormidium. of adsorbent was 200 g/L, contact time was 30 min and pH
In previous experiment, it was confirmed that phormidium was 5.6. When temperature increased, adsorption density
is a good adsorbent for adsorbing REEs. Next, the adsorption also increased. However the change was insignificant.
conditions of phormidium were investigated. Figure 8 shows Despite the changes of adsorption density of La and Nd are
the concentration of REEs after contacting phormidium as larger than other elements, the adsorption density of La was
 Leaching of Rare-Earth Elements and Their Adsorption by Using Blue-Green Algae 1803

(a) 100 120

110 before contact
90 La Pr Nd
after contact

Concentration in solution, c/ mg/L

100
Sm Gd Dy
80 90
70 80
Leaching ratio, (%)

70
60
60
50 50
40 40
30
30
20
20 10
10 0
Mg Al Si K Mn Fe
0 Element
0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22
S/L ratio, (-) Fig. 7 Concentration of impurities before and after contact with phormi-
(b) 10
dium, (Experimental conditions: Dosage of adsorbent: 100 g/L; Contact
time: 30 min; Temperature: 293 K).
9 Mg Al
Concentration of impurities (mg/L)

8
Si K
Mn Fe
7 40
6 La
35

Concentration after contact (mg/L)

5
Pr
30 Nd
4
Sm
3 25 Gd
2
20 Dy
1

0 15
0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22
10
S/L ratio (g/L)
5
Fig. 5 Leaching ratio of REEs (a) and leaching concentration of impurities
(b) according to S/L ratio, (Experimental conditions: ammonium sulfate 0
0 20 40 60 80 100 120 140 160 180 200
concentration: 1%; Leaching time: 3 h; Temperature: 293 K).
Dosage of adsorbent (g/L)

Fig. 8 Concentration of REEs after contact with phormidium as a function

450
La of dosage of adsorbent, (Experimental conditions: Contact time: 120 min;
400 Temperature: 293 K; pH: 5.6).
Pr
Adsorption density, q/ mg/kg

350 Nd
300 Sm
45
250
Gd
La
Dy 40
Concentration after contact (mg/L)

200 Pr
35 Nd
150
30 Sm
100 Gd
25
50 Dy
20
0
Phormidum Activated Fe-based Mn2O3 Calcined 15
carbon adsorbent dolomite
10
Fig. 6 Adsorption density of each adsorbent on REEs, (Experimental
5
conditions: Dosage of adsorbent: 100 g/L; Contact time: 30 min; Temper-
ature: 293 K). 0
0 20 40 60 80 100 120
Contact time, t/min
changed 295 to 329 mg/kg and one of Nd was changed 182
Fig. 9 Concentration of REEs after contact with phormidium as a function
to 193 mg/kg according as temperature was changed from
of contact time, (Experimental conditions: Dosage of adsorbent: 200 g/L;
293 to 373 K. Considering energy for raising temperature, Temperature: 293 K; pH: 5.6).
controlling temperature is not necessary to adsorb REEs.
Finally, effect of pH was investigated. Adsorption density
of phormidium on REEs as a function of pH was given in was 12 mg/kg and all one of Gd and Dy was 4 mg/kg.
Fig. 11. During this set of experiments, dosage of adsorbent Adsorption density was increased sharply from pH 1 to
was 200 g/L, contact time was 30 min and temperature was pH 2 and this value was equilibrium from pH 2. When pH
293 K. At pH 1, the adsorption density of La was 63 mg/kg, was 5.6, adsorption density of La was 335 mg/kg, one of Pr
one of Pr was 15 mg/kg, one of Nd was 61 mg/kg, one of Sm was 50 mg/kg, one of Nd was 193 mg/kg, one of Sm was
1804 J.-A. Kim et al.

400 0.7
La Pr Nd Nd
350 Sm Gd Dy 0.6

Sorbed amount of Nd, q/ mg/g

Adsorption density, q/ mg/kg

300 0.5

250 0.4

200 0.3

150 0.2

100
0.1
50
0.0
0 20 40 60 80 100 120 140 160 180 200 220
0
290 300 310 320 330 340 350 360 Dosage of adsorbent (g/L)

Temperature, T/K
Fig. 12 Concentration of Nd ion after contact with phormidium as a
function of dosage of adsorbent, (Experimental condition: Contact time:
Fig. 10 Concentration of REEs after contact with phormidium as a
120 min; Temperature: 293 K; pH: 5.6).
function of temperature, (Experimental conditions: Dosage of adsorbent:
200 g/L; Contact time: 30 min; pH: 5.6).

tration, the phormidium took up more Nd ions at lower than

500
La Pr Nd at higher cell densities. Adsorption density is the highest,
450 Sm Gd Dy 610 mg/kg at 2 g/L of phormidium dosage. This result can be
400 due to the concentration gradient between the sorbent and the
Adsorption density, g/ mg/kg

350 adsorbate, an increase in phormidium concentration causes a

300
250
200
150
100
50
0 were chosen for comparison with experimental data.
1 2 3 4
pH
Fig. 11 Adsorption density of phormidium on REEs as a function of pH,
(Experimental conditions: Dosage of adsorbent: 200 g/L; Contact time:
30 min; Temperature: 293 K).
33 mg/kg, one of Gd was 18 mg/kg and one of Dy was
13 mg/kg. Because the initial pH in leachate was 5.6,
controlling pH is not necessary to adsorb REEs.
4. Discussions
4.1 Adsorption isotherm of Nd ion onto the phormidium
Kinetic studies involve effect of major parameters such as
adsorbent dosage and contact time on the uptake of REEs by
phormidium. The production volume of Nd has dramatically
increased since the development of a Nd-Fe-B permanent
magnet, which had the strongest magnet power, in the 1980s.
Presently, more than 10,000 tons of Nd-Fe-B alloy magnets
are annually produced in Japan. Therefore, the kinetic studies
were focused on Nd ion.8,9) Adsorbent dosage has a great
influence on the biosorption process and determines the
potential of sorbent through the number of binding sites
available to remove metal ions at an initial concentration.10)
Figure 12 shows the adsorption density of Nd ions as a
function of dosage of phormidium. In this test, the initial Nd
concentration (20.6 mg/L) and the pH value (pH 5.6) were
kept constant. The dosage of phormidium was tested at
between 1 and 200 g/L. At a given equilibrium concen-
decrease in the amount of metal adsorbed onto a unit weight
of the phormidium. Moreover, the increase in biosorption of
metals by increasing the biomass dosage is due to an increase
in the number of active sites and available surface area.
Generally speaking, the analysis of the isotherm data is
important to develop an equation, which could represent the
results and be used for designing purposes. Sorption models
5 6 7 8
The Langmuir model which was characterized by linear
adsorption at low surface coverage:11)
 
1 1 1 1
¼ þ ð2Þ
q qm KL C1 qm
where qm is he maximum capacity of the adsorbent for
adsorbate (mass adsorbate/mass adsorbent, mg/g); and KL
(L/mg) is a measure of affinity of adsorbate for adsorbent.
Figure 13(a) shows 1=q versus 1=C1 for adsorption of Nd
ions onto the phormidium. The data have then been
extrapolated using the least-squared linear regression in
order to calculate the maximum capacity of the adsorbent
(qm ). The experimental date were well fitted to the linear
form of Langmuir equation, (eq. (2)) with a correlation
coefficient R2 ¼ 0:972, indicating the applicability of the
model. It was found that the Langmuir isotherm gives
qm ¼ 775 mg/kg and KL ¼ 0:083 L/mg, (Fig. 13(a)).
Freundlich model has generally been considered an
empirical relationship and has been used widely to fit
experimental data.12) The linearized form of Freundlich
isotherm is given as, (eq. (3)):
1
ln q ¼ ln KF þ ln C1 ð3Þ
n
where KF (mg/g), which indicates the adsorption capacity,
and n is empirical constant. The value of n indicates a
favorable adsorption for 1 < n < 10.
lnðqÞ versus lnðC1 Þ for adsorption of Nd onto the
phormidium was indicated in Fig. 13(b). The data have then
 Leaching of Rare-Earth Elements and Their Adsorption by Using Blue-Green Algae 1805

(a) 12 0.12
Nd
10 0.10
intercapt, 1/q m = 1.290

Sorbed amount of Nd, q/ mg/g

slope, 1/qmKL = 15.497
8 2
0.08
R = 0.972

0.06
6
1/q

0.04
4

0.02
2 Nd
0.00
0 0 20 40 60 80 100 120 140
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Contact time, t/min
1/C1

Fig. 14 Concentration of REEs after contact with phormidium as a

(b) 0.0
Nd function of contact time, (Experimental condition: Dosage of adsorbent:
-0.2 200 g/L; Temperature: 293 K; pH: 5.6).
intercapt, Log K F = -1.128
-0.4 slope, 1/n = 0.646
2
R = 0.921
A functional relationship common to most treatments of
-0.6
intraparticle diffusion is that uptake qt varies almost with the
log(q)

-0.8
-1.0
-1.2
-1.4
0.00 0.25 0.50 0.75 1.00 1.25
log(C1)
Fig. 13 Linear graph of (a) the Langmuir isotherm and (b) the Freundlich
isotherm (Experimental condition: Contact time: 120 min; Temperature:
293 K; pH: 5.6).
been extrapolated using the least-squared linear regression in
order to calculate KF and n. It was found that the Freundlich
isotherm gives KF ¼ 74 mg/kg and n ¼ 1:548, (Fig. 2(b)).
Regression correlation coefficients for Nd ions is very high.
Especially, the experimental data fitted better the shape of
the Langmuir isotherms with high values of the R2 .
4.2 Adsorption kinetics of REEs onto the phormidium
The rate of adsorption is a very important factor in the
reactor design and the optimization process in industry. The
effect of contact time on the equilibrium uptake of Nd ions
on the phormidium is shown in Fig. 14. According to this
figure, adsorption density increased with increasing contact
time and almost 82% of Nd was adsorbed by dried
phormidium in the first 1 min of contact time. This behavior
suggests that the sorption takes place rapidly on the external
surface of the adsorbent where the binding may be through
interaction with the functional groups located on the surface
of the adsorbent.
Kinetic study provides valuable information about the
mechanism of adsorption and subsequently investigation
of the controlling mechanism of the biosorption process
as either mass transfer or chemical reaction in order to
obtain the optimum operating conditions for industrial-scale
batch processes.10,13) Many adsorption kinetic models have
been reported. The intraparticle diffusion model14) and the
pseudo-second-order kinetic15) are among the most widely
applied.11)
square root of time t0:5 . The linear form of the intraparticle
diffusion equation is given as:
qt ¼ ki t0:5 ð4Þ
where ki is the intraparticle diffusion rate constant, (mg/
g min0:5 ). t is the contact time (in min). The ki value is then
1.50
calculated from the slope of the straight line. Figure 15(a)
shows the intraparticle diffusion plot, which do not pass
through the origin, indicating that the intraparticle diffusion
is not the only operative mechanism. As it can be seen in
Fig. 15(a), the external surface adsorption (i.e. the first
portion or segment of the plot) is absent; apparently it is
completed before the first 5 min. It was found that the
correlation coefficient R2 was 0.7002 and this value was not
as great as might have been expected.
The pseudo-second-order model considers that the rate of
occupation of biosorption sites is proportional to the square
of the number of unoccupied sites (eq. (5)):
dqt
¼ kðqe  qt Þ2 ð5Þ
dt
where qe (mg/g) is the amount of metal ion sorbed at
equilibrium, qt (mg/g) shows uptake capacity at t and k
(g/mg min) shows the equilibrium rate constant of pseudo-
second-order adsorption. After being integrated and rear-
ranged, (eq. (6)):
t 1 1
¼ 2þ t ð6Þ
qt kqe qe
where k and qe can be determined from the linear plot of t=qt
versus t.15)
Figure 15(b) shows a plot of eq. (6) for the sorption of Nd
using phormidium. The results indicate a very significant
linear relationship between t=qt and t, with very high
correlation coefficient, R2 , it was found that the pseudo-
second-order reaction gives qe ¼ 108 mg/kg and k ¼ 0:0146
kg/mg min.
This sorption system was better described by pseudo-second-
order rate equation than by intraparticle diffusion model. The
perfect fit of the experimental data indicates the applicability
1806 J.-A. Kim et al.

(a) 0.20 (NH4 )2 SO4 was 1%, (2) leaching time was 3 h and (3) S/L
0.18 Nd ratio was 0.09. And then leaching ratio of Nd was 67.3%.
0.16 And when dosage of phormidium was 200 g/L and
R2 = 0.7002 contact time was 30 min, the adsorption density of Nd was
Adsorption density, q t/ mg/g

0.14 slope, k = 0.0014

182 mg/kg. The equilibrium sorption isotherm of Nd onto
0.12
phormidium was better described by the Langmuir isotherm
0.10
equation with correlation coefficients of 0.972. Moreover,
0.08
the pseudo-second-order kinetic model fit the experimental
0.06 data well, (R2 ¼ 0:9998).
0.04
0.02 Acknowledgments
0.00
0 2 4 6 8 10 12
0.5 0.5
This study was supported in part through contract research
Squre root of time, t / min
from Japan Oil, Gas and Metals National Corporation
(b) 1200 (JOGMEC), JST Crest of Innovation Technology and System
1100 Nd for Sustainable Water Use Research area (Shibusawa group)
1000 2 and JSPS Scientific Research (A), No. 22246118.
R = 0.9998
900
slope, 1/qt = 9.3024
800 2
intercept, 1/kqt = 5.9415 REFERENCES
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700
600
500
400
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