Journal of Nuclear and Radiochemical Sciences, Vol. 10, No.1, pp. 1-12, 2009

Articles99

Mo/ 99mTc–113Sn/113mIn Dual Radioisotope Generator Based on 6-Tungstocerate(IV)Column Matrix
M. Mostafa,* A. A. El-Sadek, H. El-Said, and M. A. El-Amir
Radioactive Isotopes and Generators Dept., Hot Labs. Center, Atomic Energy Authority, P.O. Code 13759,
Cairo, Egypt.
Received: December 27, 2008; In Final Form: April 6, 2009
Elutions of 99mTc and 113mIn have been performed subsequently with 10 mL of 0.9% NaCl solution and 10 mL of 0.1
M HCl solution, respectively, from 6-tungstocerate(IV) chromatographic column loaded with 0.54 MBq 99Mo and0.45 MBq 113Sn, using alumina-column filter in the case of 99mTc. Radionuclidic purity of both eluates was ≥99.99%. Elution yields of 72.5±5.8% and 62.2±3.7%, and radiochemical purities of 96.9±1.0% (as 99mTcO4-) and
88.4±2.5% (as 113mIn3+) have been obtained for 99mTc and 113mIn, respectively. Al and W impurities in the 99mTc and113m
In eluates, respectively, were found to be within the accepted limits, whereas no Ce impurities were detected inboth eluates. Also trials have been carried out on a similar system to obtain mixed 99mTc–113m In eluates from 6tungstocerate column with different 99mTc/113m In ratios using 0.9% NaCl–HCl eluents of different pH values. To
separate 99mTc and 113mIn from each other, these mixed eluates were passed through a column of hydrous zirconiumoxide which was then eluted with 10 mL of 0.9% NaCl solution and 15 mL of 0.1 M HCl solution, respectively. No
W, Ce, or Zr impurities were detected in the 99mTc and 113mIn eluates obtained in these trials.

1. Introduction
99m

Tc (t1/2 = 6.01 h) and 113mIn (t1/2 = 1.66 h) are suitable radionuclides for diagnostic purposes in nuclear medicine becauseof (i) short physical half-lives, (ii) very low-abundance of β- emission for 99mTc and its absence in the case of 113m In, (iii) γemissions of suitable energy for imaging processes [140.5 keV(89.4%) and 391.7 keV (64.2%) for 99mTc and 113m In, respectively].1 99mTc(VII)-pertechnetate is used for brain, thyroid,
salivary gland, and lachrymal duct scintigraphy and imaging
of gastric mucosa.2 Also different 99mTc-radiopharmaceuticalcompounds are used for detection of lung cancer, cardiac blood
pool imaging, liver and spleen scintigraphy, etc.2,3 Carrier-free
113m
ln in 2% gelatin (pH 4) is used for “vascular-pool” imaging
applications.4 113m In-labeled compounds can be used for lungand liver scanning,5 and for brain imaging applications.6 113In
can also be used as a radiotracer to study the flow behavior of
crude oil in a battery of industrial crude oil/gas separators in
oil industry.7
Generally, dual isotope imaging, simultaneous imaging of
two radionuclides, has been successively used in various clinical applications. This technique is advantageous over single
isotope imaging for the cases in which two assessments needed,
where in the former technique these assessments can be carriedout in a single examination. For instance, quantitative dualisotope SPET technique has been utilized for the assessment oflung ventilation and perfusion simultaneously using 99mTclabeled Technegas and 113m In-labeled macro-aggregated albumin.8
99m
Tc and 113m In are nuclear-decay products of 99Mo (t1/2 =65.94 h) and 113Sn (t1/2 = 115.09 d) radionuclides, respectively,1
and they are usually obtained by periodical elution from99
Mo/ 99mTc and 113Sn/113m In radioisotope generators, respectively, based on chromatographic columns. However, examples
for less famous solvent extraction 9 -11 and sublimation
99
Mo/ 99mTc generators12-14 have been reported in literature.
(n,f) 99Mo is loaded onto alumina chromatographic columns,15-17*Corresponding author. E-mail: mmostafa95@yahoo.com

whereas (n,γ) 99Mo can be loaded onto or incorporated into different gel materials (e.g. tin molybdate, zirconium molybdate,
12-molybdocerate(IV), and titanium molybdate) which packed
in chromatographic columns.18-22 99mTc is usually eluted fromthese columns using 0.9% NaCl. Subramanian and McAfee, 23
and Lin et al24 studied separately the use of hydrous zirconiumoxide (HZO) column for adsorption of 113Sn from 0.3–0.5 M
and 0.2 M HCl, respectively, and elution of 113m In with 0.1 M
HNO3 (or 0.1 M HCl) and 0.05 M HCl, respectively. Arino andKramer25 studied the chemical sorption of 113Sn(IV) separately
on HZO and silica gel by heating in the presence of bromine
water and 0.4 M HCl. 113mIn(III) was eluted in both cases witha high separation Sn/In factor (> 10 4 ) using HCl solution of
pH>1.2. El-Said 26 used 12-molybdocerate(IV) column forsorption of 113Sn(IV) from 0.1 M HCl solution and elution of
113m
In(III) using the same solution. Teranishi et al 27 reported
the adsorption of 113Sn(IV) on a column of glass beads from
0.16 M NaCl solution and elution of 113m In(III) with the same
solution.
Mostafa 28 successfully prepared 99Mo/ 99mTc–137Cs/137m Ba
dual radioisotope generator based on 6-tungsocerate(IV)(6WCe) from which 99mTc and 137m Ba were subsequently eluted(137m Ba was eluted after decay of 99Mo) using 0.9% NaCl and
0.9% NaCl–HCl (pH 1) solutions, respectively.
This work aims at preparation of 99Mo/ 99mTc–113Sn/113m In
dual radioisotope generator based on 6-WCe chromatographic
column from which 99mTc and 113m In can be eluted simultaneously or subsequently (i.e. eluting 113m In after decay of 99Mo)
with high-purity suitable for use in different medical applications.
2. Experimental
2.1. Chemicals and instruments. All chemicals used in
the present work were of AR grade. Distilled water was used
for solution preparation. Gamma-ray spectrometer consistingof a multichannel analyzer (MCA) of “Inspector 2000” model,
Canberra Series, made in USA, coupled with a high-purity germanium coaxial detector (HPGe) of GX2518 model was usedfor γ-radioactivity measurements. The assignment of γ-photo-© 2009 The Japan Society of Nuclear and Radiochemical Sciences
Published on Web 05/27/2009

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J. Nucl. Radiochem. Sci., Vol. 10, No. 1, 2009

peaks obtained in the γ-ray spectra to the corresponding radionuclides was cited from Chu et al.1 A NaI (Tl) γ-ray
scintillation counter of “Scaler Ratemeter SR7” model, madein England, was used for measurements of gross γ-radioactivities of eluate solutions. Jenway 6405 UV-VIS spectrophotometer, made in U.K., was used for detection of Ce and W
impurities in eluate solutions. Sequential plasma emission
spectrometer of “ICPS-7500” type, Shimadzu, made in Japan,
was used for detection of Al impurities in eluate solutions. pHmeter with microprocessor of “pH211” model, Hanna
Instruments, made in Portugal, was used for measurement ofpH values of different solutions.
2.2. Preparation of 99Mo and 113Sn solutions. Carrier-free99
Mo was obtained by elution of Mon-Tek 99Mo/ 99mTc generator(Monrol Nuclear Products Industry and Trade Inc. made in
Turkey) after 25 d from its calibration date (loaded with 20
GBq of 99Mo on its calibration date) with 1 M of NaOH solution. The 99Mo eluate solution was passed through 0.45- µ m
millipore filter to retain any possible contained alumina particles. Then, 99Mo solution was diluted with HCl solution to thedesired pH-value. To obtain 113Sn solution, tin powder targets(irradiated in the Second Egyptian Nuclear Reactor, ETRR-II,
for 4 h at a thermal-neutron flux of 1×1014 n cm-2s-1 and cooledfor 28 d), 0.1 g of each, was dissolved in concentrated HClsolution warmed at ~ 50 °C in a water bath with a stepwise
addition of few H2O2 drops, to accelerate the dissolution rate.
After dissolution of the tin target, further few drops of H 2O2
were added to ensure the complete oxidation of Sn(II) to
Sn(IV). The complete oxidation was checked using ammonium molybdate solution, where the blue color indicates thepresence of Sn(II).29 Thereafter, the solution was evaporated
to few drops at ~ 60 °C, left to cool to room temperature, andfinally diluted to the desired concentration using HCl solution.
2.3. Preparation of 6-tungstocerate(IV), 6-WCe, gelmatrix. The preparation method of 6-WCe gel stated by ElAmir30 was followed. 500 mL of 0.3 M tungstate(VI) solution,
prepared by dissolution of 49.5 g of Na 2WO 4 ·2H 2O in dilute
H2SO4 (pH 1), was maintained at 100 °C for ~15 min and left
to cool at room temperature. Thereafter, 500 mL of 0.05 M
ammonium cerium(IV) sulfate solution, prepared by dissolution of 15.8 g of Ce(SO4) 2 ·2(NH4) 2SO4 ·2H2O in dilute H2SO4acid (pH 1), was added to the tungstate(VI) solution understeady stirring at 25 °C. The precipitate formed was separated
by centrifugation and, then, thoroughly washed with distilledwater, 2 M HCl, and again with distilled water till it became
free from interstitial acid. The product material was dried at
50 °C for 48 h and then pulverized to 0.12–0.24 mm particle
size.
2.4. Preparation of hydrous zirconium oxide. Hydrous
zirconium oxide (HZO) was prepared by the homogeneous
precipitation method,31 in which 50 g/L ZrOCl2·8H2O solution
in 0.5 M HCl was added and mixed with urea (in the ratio of
100 mL solution : 15 g of urea). The resulting solution washeated to 90 °C on a hot plate. After formation of HZO precipitate, the mixture was kept at 90 °C for additional 1 h. The
precipitate was filtered and washed repeatedly with distilledwater for the removal of chloride traces and, then, dried atroom temperature in a desiccator.
2.5. Batch distribution studies. The distribution coefficients of (i) 99Mo and 99mTc and (ii) 113Sn and 113m In couples
between 10 mL (V) of aqueous phases of carrier-free 99Mo (inequilibrium with 99mTc) and of 1×10 -4 M Sn(IV) (in equilibriumwith 113mIn) in 0.1 M NaCl–HCl and HCl solutions, respectively,of different pH values and 0.1-g amounts of 6-WCe gel matrix(m) were determined by equilibrating their mixtures separately
in 20-mL glass vials which in turn were placed in a water-baththermostat shaker for 24 hours at 25±1 °C. The distribution
coefficient, Kd (mL/g), at different pH values was calculated
from the following equation:

Kd =A 0 – Ae
Ae

×

V
m

(mL/g) ,(1)

where A0 and Ae are the counting rates (cpm) of the radionuclide of interest in the aqueous phase before and after contact
with the gel matrix, respectively.
2.6. Loading capacity studies of 6-WCe gel matrix for
Sn(IV). Loading capacity was determined by batch equilibration method, in which 0.1 g of 6-WCe gel matrix was repeatedly equilibrated with 10 mL of a freshly prepared 0.1 M HCl
solution containing 10 -2 M Sn(IV) in a 20-mL glass vial placedin a water-bath thermostat shaker at 25±1 °C until saturation
was attained, as indicated by obtaining a constant counting rateof the aqueous phase before and after equilibration with the gelmatrix.
2.7. Radioisotope dual generator system. A glass columnof 0.7 cm i.d., with a small piece of glass wall plug at its bottom
followed by a stopcock, was packed with 1 g of 6-WCe gelmatrix by settling from distilled water. The column was conditioned with 20 mL of 0.1 M NaCl–HCl solution (pH 1) andsubsequently loaded with 35 mL of an identical solution containing carrier-free 99Mo(VI) (0.54 MBq). Thereafter, the column was further conditioned with 20 mL of 0.1 M HCl andsubsequently loaded with 168 mL of an identical solution of
5×10 -3 M Sn(IV) (0.45 MBq 113Sn). The flow rate of loading ofboth solutions was 1 mL/min. The column was conditioned
with 20 mL of 0.9% NaCl solution. After 23 h, 99mTc waseluted with 10 mL of 0.9% NaCl solution. 99mTc eluate waspassed through an alumina column (0.7 cm i.d.) packed with 1
g alumina preconditioned with 20 mL of 0.9% NaCl solution.
The alumina column was then eluted with 10 mL of 0.9% NaClsolution. 14 elution processes of 99mTc have been performed
along 21 d. After practical complete decay of 99Mo (60 d), 6WCe column was conditioned with 20 mL of 0.1 M HCl solution. After 18 h, 113m In was eluted with 10 mL of 0.1 M HCl
solution. 100 elution processes of 113m In have been performed
along 6 months. On the other hand, trials have been performed
on a parallel similar system to obtain mixed 99mTc–113m In eluates using 0.9% NaCl–HCl eluents of different pH values.
These eluates were passed through a column (0.7 cm i.d.) of 0.6
g HZO preconditioned with 20 mL of 0.9% NaCl solution,
which was then eluted with 10 mL of 0.9% NaCl and 15 mL of
0.1 M HCl, respectively.
2.8. Quality control of 99mTc and 113mIn eluates. Elution
yields of 99mTc and 113m In were determined by comparing thecounting rates of these radionuclides on the column before andafter elution using the γ-ray spectrometer. Radionuclidic purity
was determined by using the γ-ray spectrometer to determine
the contribution of any possible radiocontaminants, if present,
and was verified by tracing their nuclear decay with time, using
the γ-ray scintillation counter, to determine the corresponding
half-life. pH values of the eluate solutions were determinedusing the pH-meter. Radiochemical purity of the eluates, thecontribution of the desired chemical form of 99mTc and 113mIn intheir eluates, were determined by the ascending paper chromatography technique using Whatman No.1 chromatographic
paper and a mixture of 85% methanol + 15% H2O in the caseof 99mTc, and 90% ethanol + 10% of 5 M HCl in the case of
113m
In, as developing solvents. The radioactivity distributions
along the obtained chromatograms were traced, using the γ-ray
scintillation counter, to determine Rf -values, where:
Rf =traveled distance of the radioactivity from the start point to the peak position
traveled distance of the solvent from the start point to the solvent front. (2)Tungsten and cerium impurities, originated from 6-WCe gelmatrix, were determined in 99mTc and 113mIn eluates spectropho-

Mo/ 99mTc–113Sn/113mIn Dual Radioisotope Generator Based on

tometrically at wavelengths of 403 nm (by using the thiocyanate method) and 320 nm (by using the persulfate method),respectively, 32 , 33 using the UV-VIS spectrophotometer.
Aluminum impurities, originated from the alumina-filter column, in 99mTc elutes were determined by using the plasma
em ission spectrometer at wavelength of 308.22 nm. 3 4
Zirconium impurities, originated from HZO column, in 99mTc
and 113m In eluates were determined spectrophotometrically at
wavelength of 665 nm (by using the arsenazo-III method).35
3. Results and discussion

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99

Mo was obtained as MoO42- from the 99Mo/ 99mTc generator
using 1 M NaOH as an eluent,36 whereas 113Sn solution was
obtained by dissolution of the irradiated tin in concentrated
HCl and oxidation with H 2O2 to obtain SnCl62-.37 6-WCe gelmatrix was chosen as a base matrix due to its chemical, radiation, and thermal stability in addition to its reliable use as abase matrix of 188W/188m Re, 137Cs/137m Ba, and dual 137Cs/137m Ba–99Mo/ 99mTc radioisotope generators.28,30,38

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Figure 1. Distribution coefficients of 99Mo and 99mTc in 0.1 M NaCl–
HCl media as functions of pH of the equilibrating solution at 25±1
°C.

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3.1. Batch distribution studies of 99Mo and 99mTc. Figure
1 shows distribution coefficients of 99Mo and 99mTc in 0.1 M
NaCl–HCl media as functions of pH of the equilibrating solution. As shown in Figure 1, Kd of molybdenum increases withdecreasing pH value, where it increases gradually from 153±10
to 279±12 mL/g with decreasing pH from 12.4 to 2.4 and thenincreases abruptly to reach 492±7 mL/g at pH 1. Kd of technetium increases with decreasing pH nearly parallel to that ofmolybdenum but with much less values; it increases graduallyfrom 25±2 to 37±2 mL/g with decreasing pH from 12.4 to 2.4
and then increases abruptly to 67±2 mL g at pH 1. Along thestudied pH range (1–12.4), molybdenum exists in solution asanionic species; [MoO 4] 2- predominates at pH>6, [Mo7O24] 6predominates at pH 1.5–3.5, while [Mo8O26] 4- predominates at
pH 1.20,36,38 6-WCe was prepared and characterized before as a
cation exchanger28,30 and therefore the uptake of 99Mo cannot
be interpreted by ion-exchange mechanism. Since 12tungstocerate(IV), 12-WCe, and 12-molybdocerate, 12-MoCe,
could be prepared and characterized,30,38 there are 6 vacantoctahedral sites around the tetrahedron of the central cerium
heteroatom in 6-WCe, the uptake of 99Mo may be interpretedby the formation of a 6-WCe–6-MoCe mixed heteropolyacid ofa suggested chemical composition of [CeO 4 ·W6 Mo 6 O36 ] 4 ·xH2O30,40-43. The increase of Kd of technetium with decreasing
pH in such manner is attributed to the predominance of TcO4 anionic species in slightly acidic and moderate alkali pH values
and the formation of the reduced technetium species, e.g.
[TcCl4 (H 2 O) 2 ] and [TcCl 3 (H 2 O) 3 ] + , in more acidic pH values.44,46 The higher Kd -values of molybdenum compared tothose of technetium at the corresponding pH values supports
the possibility of the formation of 6-WCe–6-MoCe mixed heteropolyacid.
3.2. Batch distribution studies of 113Sn and 113mIn. Figure
2 shows distribution coefficients of 113 Sn and 113m In in HCl
media as functions of pH of the equilibrating solution. It is
obvious that Kd of tin increases from 142±25 to 1868±37 mL/g
with increasing pH from 0.7 to 1.1 and shows only a minor
increase in the pH range from 1.1 to 2.3 (2205±57 mL/g at
pH2.3). Kd of indium shows similar behavior, but with muchless values; it sharply increases from 3±1 to 22±4 mL/g withincreasing pH from 0.7 to 1.1 and shows a little increase in the
pH range from 1.1 to 2.3 (31±4 mL/g at pH 2.3). The high Kdvalues of tin and indium in the pH range of 1.1–2.3 may be dueto the predominance of cationic species of tin [Sn(OH) 3 + ,Sn(OH) 2 2+, and Sn(OH) 3 +] and Sn(OH) 4 as well as cationicspecies of indium [In3+, InCl2+, InCl2+, In(OH)2+, and In(OH)2+]
which retained onto the 6-WCe matrix by ion exchange and/orhydrolytic mechanism.48-51 As stated for Mo/Tc couple, the

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Figure 2. Distribution coefficients of 113Sn and 113mIn in HCl media
as functions of pH of the equilibrating solution at 25±1 °C.

higher K d -values of tin relative to those of indium may be
attributed to the formation of tin tungstate 52 . Reactions
between 99 Mo and 113 Sn with 6-WCe gel matrix to form 6WCe–6-MoCe and tin tungstate compounds, respectively, were
fast due to the pseudo-liquid behavior of 6-WCe, as a heteropolyacid, where the reaction field is three-dimensional (likethat in liquid phase) because of the flexible lattice of 6-WCe.53
3.3. Loading of 99Mo solution. As indicated by batch distribution studies of 99Mo, the highest Kd-value was obtained at
pH 1 and hence the 6-WCe column was conditioned with 20
mL of 0.1 M NaCl–HCl solution (pH 1) and, subsequently,
99
Mo was loaded from an identical solution onto the column.
Figure 3 shows the γ-ray spectra of (a) 99Mo loading solution,(b) 6-WCe column after loading, and (c) loading effluent. Only

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J. Nucl. Radiochem. Sci., Vol. 10, No. 1, 2009

the γ-photopeaks of Mo and Tc appear in the spectra ofloading solution (a) and the column after loading (b). 99Mo
was quantitatively retained onto the 6-WCe column as indicated by the solely appearance of γ-photopeak of 99mTc (140keV) in the loading effluent (c). Chemical composition of theloading solution could greatly change the % uptake of 99Mo,
since in a previous work 30 , only ~ 69% of carrier-free 99Mo
(loaded from aqueous solution contained 5.7 M Na+, 2 M SO42-,
and 1.7 M NO3-) was retained onto 1.5-g 6-WCe column.
3.4. Loading of 113Sn solution. Although the Kd-value oftin at pH 1 was not the highest one (Figure 2), tin was loaded
onto the 6-WCe column (preconditioned with 20 mL of 0.1 MHCl) from 0.1 M HCl (pH 1) solution, since loading from solutions of higher pH values was not preferred to avoid the possibility of the bulk precipitation of Sn(OH) 3, which in turn may
cause blocking of the column. As indicated from the batchloading capacity study, uptake value of 1±0.2 mmol Sn(IV)/g
6-WCe was obtained. The amount of tin loaded onto the column containing 1 g of 6-WCe did not exceed this uptake value,
since 168 mL of 5×10 -3 M Sn(IV) solution in 0.1 M HCl, i.e. asolution contained 0.84 mmol Sn(IV), was passed through the���� ���� ������ ���� �������� ���� ����Sb(III) + Cl2(aq) .

Thus, the quantitative uptake of 124,125Sb by the 6-WCe at pH 1
may suggest the retention of Sb(III), as Sb(OH) 2 + by ion-�� ���� ������ ���� ���������� ���� ������ ���� �������� ���� ����

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Sb(V) + 2Cl- (aq)

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column. Figure 4 shows the γ-ray spectra of (a) Sn loading
solution, (b) 6-WCe column (previously loaded with 99Mo) after
loading with 113Sn, and (c) loading effluent. γ-photopeaks of
113,117m,119m
Sn and 124,125Sb appear in the spectrum of the loading
solution. As a result of concentration onto the 6-WCe column,
125
Sn and 134Cs were detected, as indicated by their corresponding photopeaks in Figure 4 (b). According to Figure 4 (c),loading effluent contained 99mTc and 113mIn in addition to tracesof 99Mo, which may be unreacted and interstitially displaced bypassing the loading solution of tin. Neither antimony nor
cesium radioactive cross-contaminants was detected in theloading effluent. 134Cs + was strongly retained onto 6-WCe by
ion exchange mechanism, where heteropolyacids have a highselectivity for monovalent large cations.38,54,55 According toJohn and Kahn,54 Sb(III)/Sb(V) ratio depends on the chlorine
concentration according to the following reversible reaction:

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Figure 3. Gamma-ray spectra of (a) 99Mo loading solution, (b) 6-WCe column after loading, and (c) loading effluent.

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Figure 4. Gamma-ray spectra of (a) 113Sn loading solution, (b) 6-WCe column (previously loaded with 99Mo) after loading with 113Sn, and (c)loading effluent.

exchange (and/or hydrolytic mechanism) and/or retention ofSb(V) as HSb(OH) 6 by coprecipitation, regarding the 6-WCe
matrix as a carrier.57
3.5. Elution of 99mTc. After loading 99Mo and 113Sn subsequently onto 6-WCe column, the column was conditioned for99m
Tc elution with 20 mL of 0.9% NaCl solution and, then, thecolumn was eluted after 23 h with 10 mL of 0.9% NaCl solution. Figure 5 shows γ-ray spectra of 6-WCe loaded with 99Mo
and 113Sn (a) before and (b) after elution with 0.9% NaCl solu-

tion, and (c) eluate. It was found that, the eluate contained bothof 99mTc and 113m In (Figure 5c). Along 21-d period from loading of 99Mo and 113mSn, radiometric calculations indicated that
72.5±5.1% and 0.5±0.3% of 99mTc and 113mIn, respectively, wereco-eluted with 10 mL of 0.9% NaCl solution. For example,
99.8% of the radioactivity of the first eluate was due to 99mTc
while only 0.2% of it was due to 113mIn. However, these contributions changed gradually (% 99mTc decreased and %113m In
increased) as more 99Mo decayed. After passing this eluate�� ����� ��������� ����� ������ ����� ����

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Figure 5. Gamma-ray spectra of 6-WCe column (loaded with 99Mo and 113Sn) (a) before and (b) after passing 10 mL of 0.9% NaCl solution, and(c) eluate.

through the alumina-column filter (preconditioned with 0.9%
NaCl solution), only 99mTc was found in the effluent, while all
113m
In and a fraction of 99mTc were retained onto the alumina
column (Figure 6, b and c, respectively). Radiometric calculations indicated that 33.1±2.9% of 99mTc eluted from 6-WCe wasretained onto the alumina column while 66.9±2.9% of it was
passed. Thereafter, 95.9±1.5% of the 99mTc retained on the alumina column was eluted with 10 mL of 0.9% NaCl solution(Figure 6e) leaving 113mIn and the rest of 99mTc retained (Figure6d). Thus, after using alumina-column filter and eluting it,
total 99mTc elution yield of 72.5±5.8% was obtained with aradionuclidic purity of ≥ 99.99%. Figure 7 shows typical elution profiles of (a) 99mTc and (b) 113m In from 6-WCe column,and (c) 99mTc from alumina-column filter with 10 mL of 0.9%
NaCl solution. As shown in Figure 7 (a), a sharp peak was
obtained for elution of 99mTc from 6-WCe column; 84.5% ofMo/ 99mTc–113Sn/113mIn Dual Radioisotope Generator Based on

J. Nucl. Radiochem. Sci., Vol. 10, No. 1, 20097����� ���� ����

99

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Figure 6. Gamma-ray spectra of 99mTc eluted from 6-WCe column (a) before and (b) after passing through alumina-column filter, and aluminacolumn filter (c) before and (d) after elution with 10 mL of 0.9% NaCl solution, and (e) eluate from the alumina-column filter.
99m

Tc eluted from the 6-WCe column was concentrated in thefirst 3 mL, with a maximum value of 47.4% at 1 mL, while
15.5% was distributed in the last 7 mL of the eluate as a longtail. Figure 7 (b) shows a broad peak with three maxima forelution of 113m In from the 6-WCe column; a higher maximum

value of 19.1% at 1 mL and two smaller maxima of 11.8 and7.2% at 4 and 9 mL, respectively. According to Figure 7 (c), a
sharp peak was obtained for elution of 99mTc from the aluminacolumn filter; 99.2% of 99mTc radioactivity was concentrated in
the first 3 mL, with a maximum value of 64.9% at 2 mL,8Mostafa

J. Nucl. Radiochem. Sci., Vol. 10, No. 1, 200950����������

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Figure 7. Typical elution profiles of (a) 99mTc and (b) 113m In eluted
from 6-WCe column, and (c) 99mTc from alumina-column filter with
10 mL of 0.9% NaCl solution.

whereas 0.8% of it was distributed in the last 7 mL of the eluate. To be more concentrated, 99mTc could be eluted from thealumina-column filter with only 3 mL of 0.9% NaOH solution,i.e. in this case the total 99mTc eluate volume was 13 mL.
Radiochemical purity of the eluted 99mTc was 96.9±1.0% (as99m
TcO4 -) with Rf -value of ~ 0.67.58 Before using the aluminacolumn filter, 99mTc eluates were found to contain ≤ 1.4 ppm W.
After using the alumina column they were found to contain ≤2.0 ppm Al and no tungsten was detected. In both cases, nocerium was detected. Such levels of tungsten and aluminum
are acceptable for nuclear medicine applications.59,62 pH valueof the 99mTc eluate from 6-WCe increased gradually from 3 to
4.3. After using the alumina-column filter, pH value of the99m
Tc eluate was raised to 6.4±1.1.
3.6. Elution of 113m In. After 60-d period (during which99
Mo was practically completely decayed), the 6-WCe column
was conditioned for 113m In elution with 20 mL of 0.1 M HCl.
After 18 h, the column was eluted with 10 mL of 0.1 M HCl.
Figure 8 shows the γ-ray spectra of 6-WCe column loaded with
99
Mo and 113 Sn (after practical complete decay of 99 Mo) (a)before and (b) after elution of 113mIn by passing 10 mL of 0.1 M
HCl solution, and (c) 113m In eluate. 0.1 M HCl solution waschosen for elution of 113mIn because, according to Figure 2, thehighest separation factor was obtained at pH 1; α = (Kd) Sn /(Kd) In= 87±22. As radiometrically indicated, elution yield of 113m In
was found to be 62.2±3.7% with a radionuclidic purity of ≥99.99%. Figure 9 shows a typical elution profile of 113mIn from
6-WCe column, after decay of 99Mo, with 10 mL of 0.1 M HCl.
According to Figure 9, a sharp elution peak was obtained;
72.6% of the 113mIn eluted from the 6-WCe was concentrated in
the first 3 mL of the eluate, with a maximum value of 39.6% at
2 mL, while 60.4% of it was distributed in the last 7 mL of theeluate forming a long tail. Thus, it is clear that, the chemicalcomposition of the eluent has an obvious effect on the 113m In
elution yield; 0.5±0.3 and 62.2±3.7% for 0.9% NaCl and 0.1 M
HCl solutions, respectively, and on the sharpness of the elution
peak, compare Figures 7 (b) and 9. Radiochemical purity ofthe eluted 113mIn was 88.4±2.5% (as 113mIn3+) with Rf -value of ~0.70.63 113mIn eluates were found to contain ≤ 0.5 ppm of tungsten, whereas no cerium could be detected. pH value of the
113m
In eluates was ~1.
3.7. Simultaneous elution of 99mTc and 113mIn. Otherwise,
trials have been carried out, with more or less identical system,
to attain eluates of a gradient %99mTc/%113m In ratios, by using
0.9% NaCl–HCl eluents of different pH values. However, %99m
Tc/113mIn ratio in eluates depends also on the initial radioactivities of 99Mo and 113Sn loaded onto the 6-WCe column andtime of elution, since 99 Mo decays faster than 113 Sn. These
mixed eluates were then passed through a HZO column (preconditioned with 0.9% NaCl). Then, 99mTc and 113mIn were separately eluted from HZO column with 10 mL of 0.9% NaClsolution and 15 mL of 0.1 M HCl solution, respectively. It is
worth mentioning that no 113mIn could be eluted from HZO with
HCl eluents of pH ≥2.25 In addition, HZO was used in this system instead of alumina because it is difficult to consistently
elute 113m In from alumina.23 However, promising results havebeen obtained from these trials, but more investigations shouldbe performed to obtain systematic results. The 99mTc and 113mIn
eluates obtained in these trials were of highly acceptable radionuclidic, and radiochemical purities. In addition, no W, Ce, or
Zr chemical impurities were detected. Thus, the simultaneous
elution of 99mTc and 113mIn from 6-WCe column and then separation of them from each other using a HZO column may haveuseful applications in dual isotope imaging.8 After decay of99
Mo, 113mIn could be directly eluted from 6-WCe column. The
113m
In eluted after long decay times will has low radioactivity
but still has important applications in crude oil industry.7 This
may lead to a suggestion that the dual radioisotope generator
may be utilized in such industrial applications after decay of

9

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Figure 8. Gamma-ray spectra of 6-WCe column loaded with 99Mo and 113Sn (after practical complete decay of 99Mo) (a) before and (b) after elution of 113mIn by passing 10 mL of 0.1 M HCl solution, and (c) 113mIn eluate.

99

Mo instead of sending it directly to the waste.
Figure 10 shows a sketch of a suggested commercial system
for 99Mo/ 99mTc–113Sn/113m In dual radioisotope generator, fromwhich 99mTc and/or 113m In can be eluted by carrying out theproper elution process using the suitable inlets and outlets,
which should be clearly labeled to avoid mishandling. For thedual radioisotope generator, a lead shield with adequate dimensions for containing a radioactivity of e.g. 27.75 GB of 99Mo
can be used to contain both of this radioactivity of 99Mo and an
equal radioactivity of 113Sn.64 This is due to the lower-energy
and lower-abundance of γ-rays of 113Sn than those of 99Mo.1

10

Mostafa

J. Nucl. Radiochem. Sci., Vol. 10, No. 1, 2009
4. Conclusion

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Figure 9. A typical elution profile of 113m In from 6-WCe column,
after decay of 99Mo, with 10 mL of 0.1 M HCl

A radiochemical procedure was investigated for the preparation of a dual radioisotope generator based on a chromatographic column of 6-WCe inorganic sorbent loaded with 99Mo
and 113Sn, and eluted to produce 99mTc and 113m In subsequently
with high radionuclidic, radiochemical, and chemical purities.
On the other hand, trials of simultaneous elution of 99mTc and
113m
In from 6-WCe column have been carried out producing
eluates of different % 99mTc/%113m In ratios, which were thenpassed through a HZO column to separate 99mTc and 113m Infrom each other with highly acceptable purities, which may
have a special importance in some medical applications (dualisotope imaging).8 Furthermore, since the idea of the dualradioisotope generator is the containment of two radioisotope
generators in one system, it may lead to saving the shielding
and, consequently, shipment costs in addition to minimizationof the volume of the produced waste as a final result.
Nevertheless, the dual radioisotope generator system presented by the present work may be considered as mid-stage ofdevelopment and further investigations should be performed
with the system of simultaneous elution of 99mTc and 113m Infrom 6-WCe to obtain more real applicable dual radioisotope
generator of this type, or in other words to attain (i) more systematic results for 99mTc and 113m In elution yields, (ii) systems��� ��������� ����� ���� ��� ���������� ������ �������� ��� ������ ��� ������� �� ������ �� �� ������ ������ ����� ����� �� ���� ��� ������� ��� �� � �� � � �

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Figure 10. A sketch of a suggested commercial system for 99Mo/ 99mTc–113Sn/113mIn dual radioisotope generator used for eluting (i) 99mTc and 113mIn
simultaneously from 6-WCe column (and separating both of them from each other using HZO column) and (ii) 113mIn from 6-WCe column after
decay of 99Mo.

99

Mo/ 99mTc–113Sn/113mIn Dual Radioisotope Generator Based onwith higher radioactivities such as those used in commercial
scales, and (iii) simpler systems with easier and fewer steps forelution operations.
Acknowledgment. The authors would like to thank all thecolleagues in Radioactive Isotopes and Generators Dept. Hot
Labs. Center, Egyptian Atomic Energy Authority.
References(1) S.Y.F. Chu, L.P. Ekström, and R.B. Firestone, The Lund/
LBNL Nuclear Data Search, Version 2.0, February, http://
nucleardata.nuclear.lu.se/ nucleardata/toi/index.asp (1999).
(2) I. Zolle, Technetium-99m Radiopharmaceuticals:
Preparation and Quality Control in Nuclear Medicine,
Springer, Berlin (2007).
(3) M. Furuta, M. Nozaki, M. Kawashima, M. Iimuro, A.
Okayama, M. Fukushima, S. Natsui, R. Souma, and M.
Jinnai, Cancer Lett. 212, 105 (2004).
(4) H.S. Stern, Int. J. Appl. Radiat. Isot. 16, 283 (1965).
(5) V. A. Brookeman, P.C.J. Sun, F.P. Bruno, B.G. Dunavant,and W. Mauderli, Am. J. Roentgenol. 109, 735 (1970).
(6) R.E. O'Mara, G. Subramanian, J.G. McAfee, and C.L.
Burger, J. Nucl. Med. 10, 18 (1969).
(7) H. Constant-Machadoa, J.P. Leclerc, E. Avilan, G.
Landaeta, N. Anorga, and O. Capote, Chem. Eng. Process.
44, 760 (2005).
(8) A. Sánchez-Crespo, J. Petersson, S. Nyren, M. Mure, R.
W. Glenny, J.O. Thorell, H. Jacobsson, S.G.E. Lindahl, and
S.A. Larsson, Eur. J. Nucl. Med. 29, 863 (2002).
(9) D.M. Toren and M.R. Powell, J. Nucl. Med. 11, 368(1970).
(10) R.J. Baker, Int. J. Appl. Radiat. Isot. 22, 483 (1971).
(11) R.S. Mani and D.V.S. Narasihman, Proc. Conf. onRadiopharmaceuticals and Labelled Compounds, IAEA,
Vienna, I, 135 (1973).
(12) J. Robson, U.S. Pat. No. 3,833,469 (1974).
(13) L. Zsinka and J. Kern, Proc. Conf. on Radiopharmaceuticals
and Labelled Compounds, Tokyo, IAEA, 95 (1984).
(14) J. Gerse, J. Kern, J. Imre, and L. Zsinka, J. Radioanal.
Nucl. Chem. Lett. 128, 71(1988).
(15) H. Arino and H.H. Kramer, Int. J. Appl. Radiat. Isot. 26,
301 (1975).
(16) N. Bodur, H. Yildiz, A. Ergün, N. Bostan, M. Aksit, H.
Ayyildiz, N. Sayagi, and B. Göçer, I. Eurasia Conf. on
Nuclear Science and its Application, Izmir, Turkey (2000).
(17) J.L. Vučina, Series, Physics, Chemistry, and Technology 2,
125 (2001).
(18) M.A. El-Absy and S. El-Bayoumy, Isotopen Praxis 26, 60(1990).
(19) L. Maoliang, Production of gel-type Tc-99m generator for
nuclear Medicine, Lecture of IAEA Expert Mission for
Brazil, Sao Paulo (1996).
(20) M.A. El-Absy, M. Abou El-Enein, M. Raieh, and H.F. Aly,J. Radioanal. Nucl. Chem. 218, 157 (1997).
(21) H. El-Said, Technetium-99m Generators Based on 99MoPolymolybdate(VI) Gels Elution, Ph. D. Thesis, Faculty of
Science, Ain Shams University, Cairo, Egypt (2002).
(22) F. Monroy-Guzman, O.C. Romero, and H.D. Velázquez, J.
Nucl. Radiochem. Sci. 8, 11 (2007).
(23) G. Subramanian and J.G. McAfee, Int. J. Appl. Radiat.
Isot. 18, 215 (1967).
(24) T. Lin, Z.T. Tsai, and C.S. Luan, Int. J. Appl. Radiat. Isot.
33, 745 (1982).
(25) H. Arino and H. H. Kramer, Int. J. Appl. Radiat. Isot. 25,
493 (1974).
(26) H. El-Said, Radioisotopes Generators Based on 12Molybdocerate(IV) Column Matrix, M. Sc. Thesis, Facultyof Science, Alexandria University, Egypt (1998).

J. Nucl. Radiochem. Sci., Vol. 10, No. 1, 200911(27) K. Teranishi, Y. Yamaashi, and Y. Mar uyama, J.
Radioanal. Nucl. Chem. 254, 369 (2002).
(28) M. Mostafa, Production of some Long-Lived FissionProduct Radionuclides, Ph.D. Thesis, Faculty of Science,
Benha University, Egypt (2006).
(29) G. Svehla, Vogel’s Qualitative Inorganic Analysis, 7th ed.
Longman, London (1996).
(30) M.A. El-Amir, Evaluation of Tungstocerate Gel for
Manufacturing of Rhenium-188 Radioisotope Generator,
Ph.D. Thesis, Faculty of Engineering, Cairo University,
Egypt (2001).
(31) G.L.J.P. da Silva, M.L.C.P. da Silva, and T. Caetano, Mater.
Res. 5, 149 (2002).
(32) E.B. Sandell, Colorimetric Determination of Traces ofMetals, Interscience Publishers, Inc. New York (1959).
(33) Z. Marczenko, Spectrophotometric Determination of
Elements, Ramsay G. G., Translation Ed. John Willey andSons, Inc. New York, 3d ed. (1987).
(34) M.E. Tatro, Optical emission inductively coupled plasma
in environmental analysis, R. A. Meyers Ed. Encyclopediaof Analytical Chemistry, John Wiley and Sons Ltd,
Chichester. ISBN 0471 976709, New York (2000).
(35) Z . M a r c z e n ko a n d M . B a l c e r z a k , S e p a ra t i o n ,Preconcentration and Spectrophotometry in Inorganic
Analysis, Elsevier, Amsterdam (2002).
(36) N.N. Greenwood and A. Earnshaw, Chemistry of the
Elements, Butterworth Hienemann, Oxford, 2nd ed. (1998).
(37) X. Zhu, L. Zhao, and B. Wang, Microchim. Acta 155, 459(2006).
(38) M.A. El-Absy, M. Mostafa, M.A. El-Amir, H. El-Said, A.
A. Abdel Fattah, and H.M. Aly, J. Radioanal. Nucl. Chem.
267, 161(2006).
(39) J. Aveston, E.W. Anacker, and J.S. Johnson, Inorg. Chem.
3, 735 (1964).
(40) M.A. El-Amir, Technetium-99m Gel Generator Based on
Incorporation of Molybdenum-99 into 12-Molybdocerate(IV) Column Matrix, M.Sc. Thesis, Faculty of Engineering,
Cairo University, Egypt (1997).
(41) F.A. Cotton and G. Wilkinson, Advanced Inorganic
Chemistry; A Comprehensive Text, 3rd ed, Wiley Eastern
Limited, New Delhi (1979).
(42) S.H. Wang, S.A. Jansen, and D.J. Singh, J. Catalysis 154,
137 (1995).
(43) I.K. Song and M.A. Barteau, J. Molecular Catalysis A:
Chemical 212, 229 (2004).
(44) S.J. Rimshaw and G.F. Malling, Anal. Chem. 33, 751(1961).
(45) Y. Kanchiku, Bull, Chem. Soc. Jpn. 42, 2831 (1969).
(46) W. D’olieslager, J. Indesteege, and M. D’hont, Talanta 22,395 (1975).
(47) J. Cifka, Int. J. Appl. Radiat. Isot. 33, 849 (1982).
(48) L.G. Sillén and A.E. Martell, Stability Constants of Metal
Ion Complexes, Burlington House, London (1971).
(49) C.F. Jr. Baes and R.E. Mesmer, The Hydrolysis of Cations,Wiley, New York (1976).
(50) E. Hogfeld, Stability Constants of Metal Ion Complexes,
Part A: Inorganic Ligands, IUPAC Chemical Data NV 21,
Pergamon Press, Oxford (1982).
(51) J. Korkish, Handbook of Ion Exchange Resins: Their
Applications to Inorganic Chemistry, CRC Press, Boca
Raton (1989).
(52) A. Parikh and U. Chudasama, Proc. Indian Acad. Sci. 115,
15 (2003).
(53) M. Misono, I. Ono, G. Koyano, and A. Aoshima, Pure
Appl. Chem. 72, 1305 (2000).
(54) A. Clearfield, Inorganic Ion Exchange Materials, CRC
Press, Boca Raton (1982).
(55) M. Qureshi and K. G. Varshney, Inorganic Ion Exchangers
in Chemical Analysis, CRC Press, Boca Raton (1991).

12

J. Nucl. Radiochem. Sci., Vol. 10, No. 1, 2009(56) K.H. Jones and M. Kahn, J. Inorg. Nucl. Chem. 27, 497(1965).
(57) J.M. Loureiro and M.T. Kartel, Combined and Hybrid
Adsorbents, Springer, Dordrecht (2006).
(58) H.S. Stern, D.A. Goodwin, U. Scheffel, H.N. JR. Wagner,and H.H. Kramer, Nucleonics 25, 62 (1967).
(59) European Pharmacopoeia, Second Edition, Part II, Section
3 (1981).
(60) British Pharmacopoeia, Volume II (1993).

Mostafa(61) M. Dadachov, R.M. Lambrecht, and E. Hetheringtion, J.
Radioanal. Nucl. Chem. Lett. 188, 267 (1994).
(62) M.S. Dadachov and R.M. Lambrecht, J. Radioanal. Nucl.
Chem. Lett. 200, 211 (1995).
(63) M. Lederer, Anal. Chim. Acta 5, 185 (1951).
(64) The Health Physicist’s Companion Software, Version 1.4.4,© Copyright Syberad 2002, Ltd., http://www.syberad.
co.uk