Geothermics 50 (2014) 3034

Contents lists available at ScienceDirect

Geothermics
journal homepage: www.elsevier.com/locate/geothermics

Adsorption applications of unmodied geothermal silica

Halldor G. Svavarsson a,b, , Sigurbjorn Einarsson a , Asa Brynjolfsdottir a
a
b

Blue Lagoon Ltd., Iceland

School of Science and Engineering, Reykjavk University, Iceland

a r t i c l e

i n f o

Article history:
Received 22 February 2013
Received in revised form 16 July 2013
Accepted 1 August 2013
Available online 6 September 2013
Keywords:
Geothermal silica
Chromatographic
Adsorption
Protein separation
Phycocyanin

a b s t r a c t
Silica, precipitated out of geothermal uid discharged from a geothermal powerplant in Svartsengi on the
Reykjanes peninsula in Iceland, was used as a chromatographic adsorbent to extract blue colored protein,
C-phycocyanin, from coccoid blue-green algae. The only supplement used was salt obtained by evaporating the geothermal uid. Analysis of the silica, using scanning electron microscopy, X-ray diffractometry
and BrunauerEmmettTeller (BET) adsorption conrmed it has a high specic surface area and is amorphous. Upon adsorption and subsequent elution the purity of the extracted protein, measured as the ratio
of the light absorbance of 620 and 280 nm, increased from 0.5 to above 2.0. Our results could facilitate
utilization of a mostly unused byproduct of geothermal powerplants as chromatographic material.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
1.1. Geothermal silica
Geothermal resources are widespread throughout the world
although generally associated with areas of volcanic activity. The
HS-Energy geothermal powerplant is located in Svartsengi on the
Reykjanes peninsula, southwest Iceland on a sequence of lava
ows, the youngest being roughly 800 years old (Saemundsson
et al., 2010). The geological structure is further characterised by
interlayers of scoria and hyaloclastite reecting interglacial and
glacial periods. Since the lava ows, scoria and interlayers of hyaloclastite are highly porous and permeable, they allow seawater to
percolate deep into their aquifers where it heats up and mixes
with meteoric water (Arnorsson, 1995). Geothermal wells drilled
through the lava ows to depths of up to 2000 m discharge a mixture (here referred to as geothermal uid) of 2/3 seawater and 1/3
meteoric water with a temperature of about 240 C. Due to leaching
the hot geothermal uid contains a high concentration of silicon
(Si) when it enters the wells. Originally, the silicon is present in
the hot geothermal uid as silicic acid (SiOx (OH)42x )n . Upon cooling, the silicic acid precipitates as a three-dimensional network
of coagulated primary silica (SiO2 ) particles. The primary particles
grow up to some nanometers in size before they coagulate to form
aggregated clusters. Such a small particle size gives rise to high

Corresponding author. Tel.: +354 5996200; fax: +354 5996201.

E-mail address: [email protected] (H.G. Svavarsson).
0375-6505/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.geothermics.2013.08.001

specic surface area, which makes the SiO2 a suitable candidate for
adsorption and catalytic applications.
Steam from the ashed geothermal uid is used to produce
electricity (output power of 75 MWe ). The residual liquid is used
in a heat exchange process (output power of 150 MWt ) to heat
up freshwater for district heating of local communities of roughly
20,000 habitants. This heat exchange process limits the minimum temperature for heat extraction of the geothermal uid to
about 90 C. Most of the spent geothermal uid is reinjected into
the geothermal reservoir (6 106 m3 annually) but some of it
(1.2 106 m3 annually) is discharged on the surface where it
forms the Blue Lagoon (Grether-Beck et al., 2008; Petursdottir et al.,
2009). A small fraction of the discharged uid is bypassed to sedimentation tanks at the Blue Lagoon where it cools from 90 C to
ambient temperature. The cooling causes supersaturation of the
silicic acid which in turn precipitates as amorphous SiO2 . The pH
of the resulting supernatant is 7.7 0.2, sligthly higher than the
pH of the Blue Lagoon which is 7.5 0.2. At 90 C, the geothermal
uid contains about 600 ppm SiO2 and thus the 7 106 m3 of liquid being discharged and reinjected annually carries about 4000
tonnes. At 1015 C, a realistic ambient temperature, the SiO2 concentration has dropped by roughly an order of magnitude (Fleming
and Crerar, 1982) and thus a precipitation of over 3000 tonnes could
potentially be harnessed annually from uid discharged from the
HS-Energy facility alone.
Few authors have reported on practical applications of modied geothermal SiO2 and still fewer on applications of unmodied
SiO2 . A possible use of geothermal SiO2 as a ller in paper (Johnston
et al., 2004) and as a precursor for silicates (Gallup et al., 2003) has

H.G. Svavarsson et al. / Geothermics 50 (2014) 3034

31

been described. In both cases the precipitation conditions had to

be controlled. The use of natural SiO2 modied with organosilicate
materials, as a chromatographic material has also been discussed
(Tarasevich et al., 1990).

constituents (such as chlorophyll). The attached C-PC was released

from the SiO2 adsorbent by washing with deionized water.

1.2. Chromatographic silica

2.1. Algae cultivation

Silica gel (SiO2 xH2 O) is widely used as an adsorbent in chromatographic columns for isolation and purication of compounds
from a mixture. One of the most common methods for the analysis of basic pharmaceuticals is liquid chromatography (McKeown
et al., 2001), which conventionally relies on synthetic silica and
silica derivatives as the stationary phase. The production of synthetic chromatographic silica typically involves several chemical
reaction steps followed by a series of after-treatment processes
(Hoffmann et al., 2006; Zhang et al., 2009). In this paper we discuss the chromatographic application of unmodied geothermal
silica. A comparison to sintered geothermal silica is also made.

Blue-green algae, isolated from the Blue Lagoon, were cultivated

in a semi-continuous mode in a 1.2 m3 tubular photobioreactor
at 45 C at the Blue Lagoon Research and Development Center
in Iceland. The cultivation media was geothermal uid with 0.3%
mass/vol Cell-hi WP nutrient from Varicon Aqua Solutions. Illumination was provided by a high pressure sodium light (160 E/m2 /s).
A xed pH of 7.5 was maintained by regulating the CO2 gas feed
rate during growth. At harvesting, the algae suspension contained
12.2 wt% dry weight of algae. A 360 ml volume of the suspension
was homogenized for 10 min using a 900 W ultrasonic cell crusher
at 20 kHz (SYJ900-D from Sharpertek) with a duty cycle of 2 s on
and 3 s off. Subsequently, the solution was centrifuged at 3200 g
for 10 min. A 288 ml volume of supernatant (referred to as crude
extract) was obtained and collected.

1.3. Phycocyanin
The Blue Lagoon is a specic geothermal biotope known for
its unique microbial ecosystem (Petursdottir and Kristjansson,
1997; Petursdottir et al., 2009). It contains about 6000 m3 of
geothermal uid that is replenished every 40 h. The lagoons temperature remain constant at 38 1 C. The coccoid blue-green algae,
Cyanobacterium aponinum, one of the dominating species in the
microbial ecosystem, is used in this research. A water-soluble photosynthetic pigment in blue-green algae, Phycocyanin (C-PC), is a
protein that belongs to a family of phycobiliproteins. It is an accessory pigment to the green-colored pigment chlorophyll, also found
in blue-green algae. Together they are an essential component of
the algaes light harvesting system (McCall, 1998). Phycobiliproteins have in common a similar three-dimensional structure in
addition to their hydrophilic nature. Among the many interesting applications of C-PC is its use as a uorescent marker of cells
and macromolecules (Ramos et al., 2010) and as a natural colorant in food and cosmetic products, replacing synthetic dyes,
which are often unsafe or even toxic. C-PC has also been shown
to exhibit bio-activity (Eriksen, 2008) which makes it an excellent
choice as an additive in food and pharmaceutical products. However, the use of C-PC in these products is dependent on obtaining
the appropriate grade of purity. The purity of C-PC can be evaluated as the ratio between the light absorbance at  = 620 nm and
280 nm (A620 /A280 ), where A620nm is the maximum absorbance of
C-PC and A280nm is the total absorbance of proteins. A purity of
0.7 is considered food grade, 3.9 reactive grade and greater than
4.0 analytical grade (Rito-Palomares et al., 2001). Despite the many
possible applications of phycobiliproteins, their use is limited by
the high cost of extraction and purication. Most of the methods
used for purication of C-PC involve a sequence of operations that
include precipitation, centrifugation, dialysis, ion-exchange and gel
ltration chromatography and chromatography on hydroxyapatite
(Rito-Palomares et al., 2001). The purication cost has been estimated at 5090% of the total production cost (Patil et al., 2006).
Thus, improvements in the purication procedure can lead to a
signicant reduction in the production cost. C-PC is unstable to
heat and light in an aqueous solution and denatures at temperatures above 45 C (Jespersen et al., 2005). This instability puts
constraints on the possible processing methods that can be used.
In the experiments described in this paper, unmodied geothermal
SiO2 precipitated from Blue Lagoon geothermal uid was used as
an alternative to other chromatographic materials to extract C-PC
from the coccoid blue-green alga, cyanobacterium aponinum. When
SiO2 powder was soaked in a saline solution of a ruptured cell mass,
the C-PC was selectively adsorbed in contrast to other hydrophobic

2. Experimental conditions

2.2. Chromatographic silica

Raw materials used for the chromatographic recovery of C-PC
consisted of geothermal SiO2 (referred to as BL-silica) and geothermal salt (referred to as BL-salt). The chemical composition of the
BL-silica and the BL-salt was determined by inductively coupled
plasma mass spectrometry (ICP-MS). The BL-silica was removed
from the sedimentation tank and pumped into a ltration press
at a pressure of 2 bar. The resulting lter cake was dried at 60 C,
crushed manually and sieved. After removal of the BL-silica, the
BL-salt was prepared by drying the supernatant. The characteristics of the BL-silica (ground in a mortar), before and after sintering
at 1000 C for 2 h, was determined using a scanning electron microscope (SEM) and by measuring the specic surface area (BET), t-plot
area and BarrettJoynerHalenda (BJH) average adsorption pore
width (Micromeritics TriStar 3000 surface area and porosity analyzer). The mineralogy of the BL-silica was determined by X-ray
diffraction analysis (XRD: Bruker AXS).
2.3. Protein extraction
Two different approaches for adsorption and subsequent elution
were applied; method 1 and method 2. In the following discussion,
we focus primarily on the latter procedure.
2.3.1. Method 1
BL-silica agglomerates, ranging in size from 0.2 to 0.7 mm,
were packed in a 30 cm tall plexiglas column with a diameter of
5 cm. The column was loaded with 190 ml crude extract (see
Section 2.1 above) at a pressure of 0.4 bar. Afterwards, 2.2 l of
BL-salt solution (25 wt% BL-salt in deionized water) was pumped
through the column to ush the chlorophyll. Subsequently the
C-PC was eluted using a continuous ow of 2.0 l deionized water.
The pressure was gradually increased from 0.4 to 0.6 bar during
pumping of the BL-salt solution and the eluent.
2.3.2. Method 2
BL-silica that passed through a 125 m mesh screen was mixed
with the crude extract and a BL-salt solution. The C-PC discharge
was accomplished batchwise by alternating cycles of centrifugation and the addition of deionized water. A 100 ml crude extract
(see Section 2.1 above) was mixed with 10 ml of saturated BL-salt
solution (approximately 0.36 g salt per ml) and 20 g of BL-silica and
then centrifuged. The supernatant was discarded and the sediment

32

H.G. Svavarsson et al. / Geothermics 50 (2014) 3034

Fig. 2. Separation of C-PC at different stages in chronological order: (a) at early

stage of the loading, (b) after loading with 190 ml crude extract, (c) after ushing
with 2.2 l of brine solution (25% BL-salt in deionized water), and (d) after elution
with 2.0 l deionized water.

Fig. 1. A ow sheet of the C-PC extraction process.

was slurried in 50 ml of saline solution (40 ml of deionized water

and 10 ml of saturated BL-salt solution) and centrifuged again. This
step of slurrying the sediment and centrifuging was repeated with
deionized water in discrete volumes of 10 ml. The supernatant, containing eluted C-PC, was collected after each step. A ow sheet of the
extraction and the purication process is shown in Fig. 1. Absorption values and absorbance spectra of the supernatant (eluent) and
the crude extract were measured using a UVvisible Camspec M350
spectrophotometer. The purity ratio (PR) of the C-PC was taken as
the A620nm /A280nm ratio.
Methods 1 and 2 were repeated with sintered (1000 C/2 h) BLsilica, instead of unsintered silica, upon which the binding capacity
of the silica was completely lost.

Fig. 3. Concentration of C-PC (dashed line) and C-PC purity (solid line) as a function
of eluent volume.

of using the geothermal SiO2 as a stationary phase in the chromatographic column requires further evaluation. An attempt to
strengthen the SiO2 agglomerates with sintering resulted in a total
loss of performance accompanied by a decrease of its specic surface area from 60 to 1 m2 (see Table 1). This problem might be overcome by embedding the unsintered SiO2 agglomerates in a rigid
matrix, but such speculations are beyond the scope of this paper.

3. Results and discussion

3.2. Protein extraction method 2
3.1. Protein extraction method 1
The proceeding of the columns loading and elution is visualized
in chronological order in Fig. 2. As seen, the green colored chlorophyll ows through the column while the C-PC is retained at the
stationary BL-silica. A good separation of C-PC was obtained, with
a net 3-fold increment in the PR. The column, however, degraded
due to compression of the agglomerates during pumping of the
eluent. Consequently the ow rate through the column gradually
decreased to 4 ml/min which is impractically low. The possibility

The concentration of C-PC was determined using Eq. (1) (Mishra

et al., 2008), where A620 and A652 are the absorption values at 620
and 652 nm, respectively.
CCPC = (A620 0.474A652 )/(5.34)[mg/ml]

(1)

A graphical interpretation of the result is given in Fig. 3. It

is apparent from the gure that the shapes of the concentration
and purity curves resemble each other. Both lines rise roughly
linearly with increasing eluent volume up to 140 ml. At higher vol-

Table 1
Surface characteristics of the BL-silica.
BL-silica

BET spec. surf. area

[m2 /g]

Micropore surf.
area t-Plot [m2 /g]

Vol. of pores with diameter

1.7300 nm [cm3 /g]

BJH adsorption av.

pore width [nm]

Unsintered
Sintered

50
1

6
0.3

0.24
0.001

23
N/A

H.G. Svavarsson et al. / Geothermics 50 (2014) 3034

Fig. 4. Absorption spectra for algae extracts of different purity: crude extract (dotted
line), collection #1 (dashed line), and collection #2 (solid line).

umes the concentration decreases throughout the elution while the

purity line attens out rather abruptly at volumes above 200 ml.
The maxima of the PR, 2.0, and the CC-PC , 6.3 mg/ml, appear at
the same eluent volume (140 ml). As always, there is a trade-off
between the purity of the protein and its recovery rate. Several
different batches were collected. The 10 ml volume with the highest purity will be referred to as collection #1. The volume fractions
with PR 1.0 were later combined, making a total volume of 117 ml
(collection #2) with 4.9 mg/ml C-PC and a PR of 1.3, which corresponds to 31% recovery of the C-PC. Combining the volume fractions
between 40 and 250 ml resulted in a PR of 1.0 and 50% recovery
(collection #3). Absorption spectra, in the range of 250700 nm, of
collections #1 and #2, are shown in Fig. 4. A spectrum of the crude
extract is shown for comparison.

33

Fig. 5. X-ray diffraction pattern of BL-silica before (black solid line) and after sintering at 1000 C for 2 h (red dotted line).

The PR and CC-PC values for the crude extract are between 0.46
and 18.2 mg/ml, respectively. It therefore contained 1.800 mg
C-PC (100 ml 18.2 mg/ml) whereas the area under the measured concentration curve (Fig. 3.) corresponds to 1100 mg. This
equals to a total recovery of 61% ((1.1/1.8) 100%). A higher BLsilica/crude-extract ratio might increase the recovery rate of the
C-PC but most likely at the expense of its purity.

3.3. Morphology analyses of the chromatographic silica

Values of the specic surface area, micropore surface area, pore
volume and average adsorption pore width of the BL-silica, before
and after sintering are given in Table 1. Table 2 shows the chemical
composition of the BL-silica and the BL-salt.

Fig. 6. SEM images at two different magnications of the BL-silica: (a) before sintering; and (b) after sintering. The inset in (b) shows crystals formed during the sintering
process.

34

H.G. Svavarsson et al. / Geothermics 50 (2014) 3034

Table 2
Chemical composition of BL-silica and BL-salt (wt%).

Acknowledgements

Component

SiO2

Cl

Na

Ca

Mg

Total

BL-silica
BL-salt

92.9
0.02

3.9
58.7

2.2
34.0

0.49
1.83

0.39
1.75

<0.1
<0.1

99.9
96.3

This research was supported in part by the Icelandic Technology

Development Fund and the Energy Fund of the National Energy
Authority.
Appendix A. Supplementary data

The XRD patterns of sintered and unsintered BL-silica are shown

in Fig. 5. The amorphous structure of the latter is clearly demonstrated by the absence of sharp diffraction peaks. The dry SiO2
powder contains 7 wt% of salt (mainly NaCl). Sharp peaks in Fig. 5
at 2 = 31.75 and 45.48 are due to crystalline NaCl present in the
BL-silica. After sintering, a strong and sharp peak has appeared
at 2 = 22 , indicating some of the amorphous SiO2 has been converted to a crystalline form of SiO2 (cristobalite). The concentration
of NaCl, however, appears to have decreased, as indicated by the
lower intensity of the diffraction peaks.
Fig. 6 shows the SEM images at two different magnications of
BL-silica agglomerates before and after sintering. Prior to sintering we see a porous surface composed of particles with diameters
ranging from 20 nm to 90 nm. According to Icopini et al. (2005), who
investigated oligomerization of SiO2 as a function of its concentration, ionic strength and pH in natural brine solutions, coagulation
occurs when the SiO2 particles reach 3 nm in size. Our values of
2090 nm are much larger than the value they give. However, it
must be taken into account that in our case the silica precipitation was triggered by change in temperature from whereas in their
case, it was triggered by a change in the pH. Upon sintering the
particles have grown and apparently fused together. The porous
appearance is no longer visible; instead a glass-like surface has
formed. These structural changes may, in part, be attributed to the
salt present in the BL-silica. As the sintering temperature of 1000 C
is well above the melting point of NaCl (801 C), the SiO2 could have
been coated with the molten salt which solidies upon cooling.
Additional phases, formed by reactions of the SiO2 and the molten
salt, may also be present in a small amount. Crystalline particles,
roughly 10 m on a side, were observed after sintering (see inset
in Fig. 6(b)). A further conrmation of the morphological changes
occurring in the sintered SiO2 is indicated by the decrease in the
pore volume, from 0.24 to 0.001 cm3 /g (Table 1.). This is consistent
with the observed loss of performance of the SiO2 after sintering.
The average pore width of 23 nm is several times the size of the CPC protein molecule (Fisher et al., 1980). These facts could explain
the selective adsorption of C-PC from the crude extract containing
chlorophyll and C-PC. It can therefore be speculated that the chromatographic mechanism is size dependent (Paul-Dauphin et al.,
2007).
4. Conclusions
A possible use of geothermal SiO2 as a chromatographic material has been described. SiO2 deposits have been considered an
undesirable byproduct of geothermal power production and large
quantities of it can be extracted from geothermal uid. Its ability
to adsorb protein molecules was demonstrated by the separation
of C-PC from disrupted blue-green algae mass. A critical factor controlling the adsorption capability is the high specic surface area
as observed by loss of performance upon sintering. The process
described here has considerable potential as a simple, ecological
and inexpensive rst step in the purication and separation of natural proteins by utilizing geothermal resources.

Supplementary data associated with this article can be found,

in the online version, at http://dx.doi.org/10.1016/j.geothermics.
2013.08.001. These data include Google maps of the most important areas described in this article.
References
Arnorsson, S., 1995. Geothermal systems in Iceland: structure and conceptual models. 1. High-temperature areas. Geothermics 24, 561602.
Eriksen, N.T., 2008. Production of phycocyanina pigment with applications in biology. Appl. Microbiol. Biot. 80, 114.
Fisher, R.G., Woods, N.E., Fuchs, H.E., Sweet, R.M., 1980. Three-dimensional structures of C-phycocyanin and B-phycoerythrin at 5-A resolution. J. Biol. Chem. 255,
50825089.
Fleming, B., Crerar, D., 1982. Silicic acid ionization and calculation of silica solubility
at elevated temperature and pH application to geothermal uid processing and
reinjection. Geothermics 11, 1529.
Gallup, D.L., Sugiaman, F., Capuno, V., Manceau, A., 2003. Laboratory investigation
of silica removal from geothermal brines to control silica scaling and produce
usable silicates. Appl. Geochem. 18, 15971612.
Grether-Beck, S., Muhlberg, K., Brenden, H., Felsner, I., Brynjolfsdottir, A., Einarssson,
S., Krutmann, J., 2008. Bioactive molecules from the Blue Lagoon: in vitro and
in vivo assessment of silica mud and microalgae extracts for their effects on skin
barrier function and prevention of skin ageing. Exp. Dermatol. 17, 771779.
Hoffmann, F., Cornelius, M., Morell, J., Froeba, M., 2006. Silica-based mesoporous
organic-inorganic hybrid materials. Angew. Chem. Int. Ed. 45, 32163251.
Icopini, G.A., Brantley, S.L., Heaney, P.J., 2005. Kinetics of silica oligomerization and
nanocolloid formation as a function of pH and ionic strength at 25 degrees C.
Geochim. Cosmochim. AC. 69, 293303.
Jespersen, L., Stromdahl, L.D., Olsen, K., Skibsted, L.H., 2005. Heat and light stability
of three natural blue colorants for use in confectionery and beverages. Eur. Food
Res. Technol. 220, 261266.
Johnston, J.H., McFarlane, A.J., Borrmann, T., Moraes, J., 2004. Nano-structured silica
and silicatesnew materials and their applications in paper. Curr. Appl. Phys. 4,
411414.
McCall, R., 1998. Cyanobacterial phycobilisomes. J. Struct. Biol. 124, 311334.
McKeown, A., Euerby, M., Lomax, H., Johnson, C., Richie, H., Woodruff, M., 2001.
The use of silica for liquid chromatographic/mass spectrometric. J. Sep. Sci. 24,
835842.
Mishra, S.K., Shrivastav, A., Mishra, S., 2008. Effect of preservatives for food grade
C-PC from spirulina platensis. Process Biochem. 43, 339345.
Patil, G., Chethana, S., Sridevi, A., Raghavarao, K., 2006. Method to obtain Cphycocyanin of high purity. J. Chromatogr. A 1127, 7681.
Paul-Dauphin, S., Karaca, F., Morgan, T.J., Millan-Agorio, M., Herod, A.A., Kandiyoti,
R., 2007. Probing size exclusion mechanisms of complex hydrocarbon mixtures:
the effect of altering eluent compositions. Energ. Fuel 21, 34843489.
Petursdottir, S.K., Bjornsdottir, S.H., Hreggvidsson, G.O., Hjorleifsdottir, S., Kristjansson, J.K., 2009. Analysis of the unique geothermal microbial ecosystem of the
Blue Lagoon. FEMS Microbiol. Ecol. 70, 425432.
Petursdottir, S.K., Kristjansson, J.K., 1997. Silicibacter lacuscaerulensis gen. nov., sp.
nov., a mesophilic moderately halophilic bacterium characteristic of the Blue
Lagoon geothermal lake in Iceland. Extremophiles 1, 9499.
Ramos, A., Gabriel Acien, F., Fernandez-Seville, J.M., Gonzalez, C.V., Bermejo, R., 2010.
Large-scale isolation and purication of C-phycocyanin from the cyanobacteria anabaena marina using expanded bed adsorption chromatography. J. Chem.
Technol. Biot. 85, 783792.
Rito-Palomares, M., Nunez, L., Amador, D., 2001. Practical application of aqueous two-phase systems for the development of a prototype process for
C-phycocyanin recovery from spirulina maxima. J. Chem. Technol. Biot. 76,
12731280.
Saemundsson, K., Johannesson, H., Hjartarson, A., Kristinsson, S.G., Sigurgeirsson,
M.A., 2010. Geological Map of Southwest Iceland. Iceland GeoSurvey, Reykjavik,
Iceland, Scale 1:100,000.
Tarasevich, Y.I., Nazarenko, A.V., Bondarenko, S.V., 1990. Preparation, properties
and chromatographic applications of natural and synthetic amorphous silica
modied by organosilicate substances. Abstr. Pap. Am. Chem. S. 200, 186.
Zhang, A., Xiao, C., Xue, W., Chai, Z., 2009. Chromatographic separation of cesium
by a macroporous silica-based supramolecular recognition agent impregnated
material. Sep. Purif. Technol. 66, 541548.