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Journal of Radioanalytical and Nuclear Chemistry, Articles, Vol. 157, No. 1 (1992) 3-14 SORPTION OF TECHNETIUM ON INORGANIC SORBENTS AND NATURAL MINERALS S. EL-WEAR,* K. E. GERMAN,** V. F. PERETRUKHIN** *Ta/ura Nuclear Researche Center, Tripoli (Libya) **Institute of Physical Chemistry of Acad. Scs USSR Leninski prospect, 31 Moscow, 117 915 (USSR) (Received November 5, 1990) The sorption behavior of the pertechnetate anion in various solid-solution systems under aerobic conditions and pH 1.3-12.5 has been investigated. Batch techniques were employed. On most of natural minerals only surface adsorption occurs. Rs-values were no larger than 2.0 mlo g= 1. Adsorption on various natural minerals and rocks such as sandstone, basalt, granite, pyrite, peat and others are comparaed with the analogous processes on artificial inorganic sorbents: titanium oxides (thermoxide-34, thermoxide-3), erystaline cadmium sulfide, zirconium phosphate, and complex inorganic sorbents: antimony oxide - silicon oxide - phosphorus pentoxide, antimony oxide - silicon oxide - aluminium oxide, lithium oxide - manganese oxide - aluminium oxide - water, lithium oxide - titanium oxide - chromium oxide - water. For comparison the sorption of Tc on some organic sorbents was included. The solubility of T% S7 in water was measured to be 0.257 g/t. It has been shown that preliminary irradiation of sorbents such as sandstone, peat and humic acid by -/-rays with doses not less than 10 ~ rad results in the decrease of To(VII) sorption. Introduction All over the world no less than 19000 TBq of 99Tc had already been produced in nuclear reactors up to 1990. As considered, 10% of this amount has been dissipated in the environment) Estimations for the last years show that around 160 TBq of 99Tc has been released during atmospheric atomic bomb testing) On the other hand, as was mentioned by GARCIA-LEON, the continuous increase of 99 roTe.generator s in nuclear medicine should be given attention) Although some authors consider this contribution of 99Tc to the environment to be negligible, 4 to our mind it should be taken into account that all this technetium penetrates the human surrounding through the human body. So, ecological aspects of Tc-chemistry now are of increasing importance, and consist of problems of To-determination, 3 - 7 volatilization,S-11 solubility measurement and leaching, 12-17 sorption,1 s-20 and the diffusion of Tc.21,22 Many problems in Elsevier Sequoia S. A., Lausanne Akaddmiai Kiad6, Budapest

description

Technetium sorption by anionexchange resins, inorganic sorbents, natural minerals and rocks. Effect of radiation. Precipitstion of sulfide. Solubility of sulfide.

Transcript of 1992 sami-el-waer-1992

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Journal o f Radioanalytical and Nuclear Chemistry, Articles, Vo l. 157, No. 1 (1992) 3-14

SORPTION OF TECHNETIUM ON INORGANIC SORBENTS AND NATURAL MINERALS

S. EL-WEAR,* K. E. GERMAN,** V. F. PERETRUKHIN**

*Ta/ura Nuclear Researche Center, Tripoli (Libya) **Institute o f Physical Chemistry o f Acad. Scs USSR Leninski prospect,

31 Moscow, 117 915 (USSR)

(Received November 5, 1990)

The sorption behavior of the pertechnetate anion in various solid-solution systems under aerobic conditions and pH 1.3-12.5 has been investigated. Batch techniques were employed. On most of natural minerals only surface adsorption occurs. Rs-values were no larger than 2.0 m l o g= 1. Adsorption on various natural minerals and rocks such as sandstone, basalt, granite, pyrite, peat and others are comparaed with the analogous processes on artificial inorganic sorbents: titanium oxides (thermoxide-34, thermoxide-3), erystaline cadmium sulfide, zirconium phosphate, and complex inorganic sorbents: antimony oxide - silicon oxide - phosphorus pentoxide, antimony oxide - silicon oxide - aluminium oxide, lithium oxide - manganese oxide - aluminium oxide - water, lithium oxide - titanium oxide - chromium oxide - water. For comparison the sorption of Tc on some organic sorbents was included. The solubility of T% S 7 in water was measured to be 0.257 g/t. It has been shown that preliminary irradiation of sorbents such as sandstone, peat and humic acid by -/-rays with doses not less than 10 ~ rad results in the decrease of To(VII) sorption.

Introduction

All over the world no less than 19000 TBq o f 99Tc had already been produced in

nuclear reactors up to 1990. As considered, 10% o f this amoun t has been dissipated

in the e n v i r o n m e n t ) Est imat ions for the last years show that around 160 TBq o f

99Tc has been released during a tmospher ic a tomic bomb t e s t i ng ) On the other hand,

as was men t ioned by GARCIA-LEON, the cont inuous increase o f 99 roTe.generator s

in nuclear medicine should be given a t t e n t i o n ) Al though some authors consider this

cont r ibut ion o f 99Tc to the envi ronment to be negligible, 4 to our mind it should be

taken into account that all this t echne t ium penetrates the human surrounding through

the human body.

So, ecological aspects o f Tc-chemistry now are o f increasing impor tance , and

consist o f problems o f To-determinat ion, 3 - 7 volatilization,S-11 solubil i ty measurement

and leaching, 12-17 sorption,1 s-20 and the diffusion o f Tc.21,22 Many problems in

Elsevier Sequoia S. A., Lausanne Akaddmiai Kiad6, Budapest

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ecological aspects of Tc behavior have not yet been investigated. Only little informa- tion is available about the sorption of Tc in pure natural minerals of inorganic and organic nature.In,21 This fact make~ it difficult to predict the behavior of Tc in the environment. The behavior of Tc on some minerals and soils is of great importance, particularly in peats, which is one of the main ingredients of the soil in Eastern Europe, especially in the region of Chernobyl contamination. This problem has not been studied at all. So we thought it necessary to concentrate on the following: (1) investigation of To-behavior in natural waters in contact with a large number of natural minerals, (2) modeling of Te-behavior in artificial minerals and inorganic sorbents in comparison with organic sorbents, and (3) investigation of To-behavior on irradiated natural sorbents.

Experimental

Technetium was obtained from the firm "Isotope", USSR, in the form of KTcO4 and transformed into NaTcO4 by means of cation exchange in the Laboratory of Radio- chemical Research, Institute of Physical Chemistry, Academy of Sciences of the USSR. 2 a

Minerals

The sorption of 99To was studied on the artificial minerals, natural minerals and organic ion-exchangers. The artificial minerals studied were: Thermoxide-34, Thermoxide-3, GSK, ZrP, SPSC, SKK-AL, ISMA, ISTH-1, and Polysorb-1 (all from USSR), and some inorganic sorbents from different countries: Chromosorb-P, Chromosorb-W (from USA), and Celite-545 and Celite-C-22 (from UK). The natural minerals were: sandstone, feldspar, bauxite, basalt, megrele, phosphorite, peat, pyrite and kaoline. All specimens used-were obtained from deposits in the USSR.

The results were compared with the sorption of Tc on organic anion exchange resins: AV-17 and VP-1AP (Table 6). All the minerals were crushed and sieved. The fraction between 60-80 mesh was chosen. Prior to use, the particle fraction was washed several times with distilled water until no dust was visible in washing water. Thereafter air dried solids were used in the experiments.

Sorption experiments

For preparation of the pH 1.27, 6.46 and 12.6 solutions, 132 mg of NaTcO4 was dissolved in one liter of dilute HNO3, distilled water and dilute NaOH, respectively.

For measuring the sorption ratio Rs, batch sorption experiments were performed by shaking 1 g of the crushed and sieved minerals with 10 ml of Tc solution with dif-

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ferent concentrations. Varying the contact time from 1-20 days for pH 1.27, from

1-13 days for pH 6.46 and from 1 - 7 days for pH 12.7 and 1 - 2 months for natural minerals and other minerals.

Measurements of solubility

For explanation of sorption behavior of Tc on sulfuoric minerals it was necessary to get the exact value of Tc2 $7 solubility, but this value was not available from the literature. So we synthesized Te2 $7 for measuring its solubility. Equimolar quantities of Na2S and NaTeO4 were stirred in a beaker for 30 minutes. The following reaction explains the formation of To2 $7:

8H20 + 7Na2S + 2NaTcO4 a �9 Tc2S7, + 16NaOH

The precipitate was centrifuged and washed 10 times with distilled water and in

each washing was centrifuged at 8000 r.p.m, for 30 minutes. Distilled water was added to the precipitate with stirring and the initial pH was 7. Five hours later the solution became violet due to the formation of unknown intermediate technetium sulfides, the UV-VIS spectrum is show0 in Fig. 1.

35200

I.

&

- 1 . 6

D

- 1.4

- 1.2

19250 J - 1.0

, 13 22 18 1/-, )-

. , I 1 I I 38 34 30 26

xlO-Scm-1

Fig. 1. UV-VIS spectrum of supernatant solution of technetium sulfide in water

After three days of stirring the solution became colorless and the pH value was 2.35 due to-the following reversible reaction:

Tc2S7 + 8 H 2 0 . ' 2HTcO4 + 7 H 2 S

The solution was centrifuged and the solubility of the precipitate was measured to be 0.257 g/l.

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Measurement of radioactivity

Samples of 20/A were taken from each batch and dried on a paper disc and the /3-activity of 99 Tc was measured by an NRQ-605 a - / 3 - 7 autometic instrument

(Tesla, Czechoslovakia), equipped with a stilbene scintillation/3-detector. The discri- mination level of the pulse was chosen to provide the best efficiency for measuring the soft/3-emission of 99 Tc. Relative technique was used.

Irradiation technique

An experiment has been done on sorption of Tc on irradiated minerals; sandstone, peat and humic acid were 7-irradiated with a 6~ source for 20 hours. The absorbed dose was 107 Rad at room temperature (See Table 8).

Calculations

The sorption ratio R s and R' s was used in this work to describe the sorption properties of the minerals. The following equations give the ratio of R s and R's:

Aso l id V s o l u t i o n R s --

A s o l u t i o n Vso l i d (1)

where A s o l i d - activity of the dried sorbent,

A s o l u t i o n - activity of the supernatant solution, V s o l u t i o n -- volume of supernatant solution in ml, Vsoli d - weight of the dried sorbent in g.

V C1 - C2 R' s = - - .

W C2 (2)

where V - volume of the solution, W - weight of solid material used, C1 - initial activity per ml of a given radioactive Tc in solution,

C2 - activity per ml for the solution after contact. For the calculation of the solubility of Tc2S7, we used the following equation:

Is V o

C S ~ - - " - - ~

Io Vs Co (3)

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where Cs - solubility of Tc2 $7,

Is - counts of Tc in solution, Io - counts of Tc in standard, Vs - aliquot volume of Tc solution, Vo - aliquot volume of Tc standard,

Co - concentration o f Tc in standard.

m C 0 ~

v

where m - mass of Tc in standard,

v - volume of standard.

R e s u l t s a n d d i scuss ion

The sorption experiments on 99 Tc were carried out with the minerals listed in Tables 1, 5, 6 and 7. As can be seen in Tables 2, 3 and 4, the study of 99Tc sorption

on artificial minerals at pH of 1.27, 6.46, and 12.7 was carried out. As we have seen

from formulas 1 and 2, the values o f R' s and Rs represent the molecular sorption and the ionic sorption, respectively. The ionic sorption ratios o f the artificial minerals Rs, were very small at all pH values. Small value appears on Thermoxide-34 at pH 6.46, being equal to 3.2.

The GSK mineral showed R's values of 2.2, 1.25 and 0.57 at pH's of 1.27, 6.46, J

and 12.7, respectively. Those values o f R s are due to the formation of a black pre-

cipitate of Tc2 $7. The precipitation increases with decreasing pH. Though the solu- bility product of CdS itself (SP = 3.6 �9 10 -29 in natural media is lower than the SP o f Tc2S 7 at pH 2.35).

In acidic media a partial dissolution o f GSK (CdS) occurs, providing the increase of S 2 - ion concentration.

The R's-values are small too, but still higher than the ion exchange which is represented by Rs-values. As is shown in Tables 2, 3 and 4, the R's-values are large in neutral media and decrease in acidic and alkaline media.

T h e smallest Rs-values were obtained for the artificial inorganic minerals listed in Table 5. From Table 6, it can be seen that Rs-values are very large on the organic sorbents, AV-17 and VP-1AP, the largest one being observed at pH 6.46, which is equal to 1.2 �9 l0 s ml �9 mg -1

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Table 1 Formulas o f some minerals

Mineral Formula

Thermoxide-34 Thermoxide-3 GSK ZrP SPSC SKK-AI ISMA ISTH

Crystalline TiO 2 (high density) Crystalline TiO~ (low density) Crystalline CdS ZrO 3 �9 n P 3 0 * �9 kH 2 0 S b 3 0 s �9 nSiO 2 �9 m P 2 0 s A b 3 0 s �9 nSiO 3 �9 mMeO �9 k i l O o A I 3 0 t n L i 3 0 �9 mM nO 3 �9 1A130 t �9 kH=O nLi=O �9 mTiO= �9 1CRO3 �9 k H 3 0

Table 2 Sorption o f Tc on artificial minerals a t pH 1.27

Mineral Contact t ime, day R~ Rs after 90 days

Thermoxide-34 4 < 0.05 2.9 �9 10-1 8 0.3

20 5.3

Thermoxide-3 4 < 0.05 2.2 o 10 "3 8 0.3

20 2.94

GSK 4 3.2 2.2 8 7.3

20 11.0

ZrP 4 2.5 4.0 �9 10 "3 8 1.9

20 3.9

SPEC 4 < 0 . 0 5 1.2 �9 10 -3 8 < 0.05

20 4.7

SKK-AI 4 0 . 2 6 3.26 �9 10 -4 8 < 0.05

20 4.4

ISMA 4 < 0.05 2.6 �9 10 -3 8 2.4

2O 4

ISTH-1 4 < 0.05 7.6 o 10 -4 8 1

2O 3.6

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Table 3 Sorption of Tc on artificial minerals at pH 6.46

Mineral Contact time, day R~ Rs after 90 days

Thermoxide-34 1 9.8 3.2 4 10.0

13 31.3

Therrnoxide-3 1 < 0.1 1.35 o 10- 3 4 0.67

13 11.5

GSK 1 1.5 1.25 4 0.7

13 13.4

ZrP 1 - 2,4 o 10 -2 4

13 10.94

SPSC 1 4.5 1.6 o 10 -3 4 11.0

13 9.4

SKK-AI 1 1.45 6.1 o 10 -3 4 0.6

13 10.5

ISMA 1 <0.1 1.45 o 10 -3 4 1

13 10.25

ISTH-I 1 <0.1 1.3 o 10 -4 4 1.9

13 11.1

The same behavior has already been described by other authors.24, 2 s The distribu-

tion coefficients o f Tc are investigated and described in Fig. 2 and we can see in this

figure that Tc is adsorbed very strongly at low acidity o f HNO3 and could be eluted

at high acidity of HNO3.

Table 7 shows very small values o f R s in most o f the minerals and negligible ones

in the others for sorption o f 99Tc on natural minerals at pH 6.46, and at contact

times of 1 - 2 months. Tc sorption by minerals decreases along the following series:

sandstone > feldspar ~ peat > basalt ~ bauxite ~ phosphorite > pyrite > megrele

kaoline. Table 8 shows the difference in the value o f Rs, for the non-irradiated

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Table 4 Sorpfion of Tc on artificial minerals at pH 12.7

Mineral C0ntaef time, day R~ Rs after 90 days

Thermoxide-34 1 0.36 1.0 o 10-4 2 0.02 3 0.73 7

Thermoxide-3 1 0.36 4.0 o 10 -4 2 0.54 3 1.34 7 1.8

GSK 1 0.13 0.57 2 0.85 3 2.16 7

ZrP 1 < 0.1 1.0 �9 10 -3

2 0.1 3 1 7 0.9

SPSC 1 < 0.1 - 2 < 0.1 3 < 0.1 7 < 0.1

SKK-A1 1 < 0.1 1.2 �9 10 - ' 2 <0 .1 3 1.1 7

ISMA 1 0.7 0.3 2 0.76 3 1.8 7

ISTH 1 0.3 1.9 ~ 10 -3 2 0.6 3 2.4 7

minera l s ( s ands tone , h u m i c acid and pea t ) and those i r rad ia ted b y 3,-rays w i t h a dose

o f 107 rad. As we see he re , Rs-values for t h e i r rad ia ted minera l s are near ly t w o t imes

lower t h a n those for t he non - i r r ad i a t ed minera l s . This d i f fe rence cou ld be exp l a ined

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Table 5 Sorption of Te on organic sorbents

Organic sorbent

pH AV-17* VP-1AP**

Contact time, day R s R s

1.27 1 412.7 2819 4 528.8 266 8 499.6 422

20 738.3 544.7

6.46

127

1 5.0 �9 10" 2496.8 4 1.2 �9 lO s 2143.2

13 1.2" 10 s 4525.1

1 6297 1920.3 2 1.4 o 104 2062.3 3 1.5 o 104 2087.3 7 2.1 ~ 104 2014.0

AV-17 lS analogous to DOWEX-1. **VP " -1At is a macroporous anionite which consists of two ion-

exchange groups: (1) N-methylpyridinium, (2) pyridine.

Table 6 Sorption of Tc on natural minerals at pH 6

Mineral Contact time, month Rs

t 2.57• 2

1 2.1 • 2 1.66_+0.3

1 1.01_+0.3 2 0.92•

1 1.0 • 2 1.28_+0.3

1 < 0 . t 2 <0.1

1 1.05

1 1.89

1 0.32

0.1 <0.1

Sandstone

Feldspar

Bauxite

Basalt

Megrele

Phosphorite

Peat

Pyrite

Kaoline

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&

1500~

1000

500

0 I , I 0 z, 6

CHNo3mO|

2 i D .

Fig. 2. Distribution coefficient of technetium on AV-17 anion exchanger in nitric acid media

Table 7 Sorption of Tc on minerals at pH 6.46

Mineral Contact time, R~ Rs month

Chromosorb-P (USA) 1 < 0.1 5 �9 10 -4 Chromosorb-W (USA) 1 < 0.1 6 �9 10- 4 Celite-545 (UK) I < 0.1 4 �9 10 -s Celite-C-22 (UK) 1 < 0.1 4 �9 10- 5

Table 8 Sorption of Tc on irradiated minerals

Concentration of Tc, Contact time, Rs Rs Mineral

mg/1 day (irradiated) (non-irradiated)

Sandstone 132 5 1.05 2.26 Sandstone 1.32 5 0.72 1.8 Humic acid 132 5 2.12 4.2 Humic acid 1.32 5 2.01 4.0 Peat 1 3 2 5 1.2 2.9 Peat 1.32 5 0.84 1.0

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by the elimination of the active chemical group in the case of peat and humic acid and

may be due to some changes in the chemical composition of the impurities in the ease

of sandstone. So we can say that a very small part of Tc produced during nuclear

tests in the atmosphere was absorbed by soils around the test site.

Conclusions

The 99Tc(VII) is not reduced and sorbed on the inorganic minerals and peat studied

in solution in the presence of oxygen. SO To(VII) can easily penetrate the environment

through natural waters.

After irradiation with doses not less than 107 rads the inorganic minerals and peat

decrease the sorption ratio of To(VII).

References

1. F. LUYKX, in: Technetium in the Environment, G. DESMET, C. MYTTENAERE (Eds) Else- vier, Amsterdam, 1986, p. 21.

2. T. M. BEASLEY, H. V. LORZ, in: Technetium in the Environment, G. DESMET, C. MYTTE- NAERE (Eds), Elsevier, Amsterdam, 1986, p. 197.

3. M. GARCIA-LEON, J. Radioanal. Nucl. Chem., 138 (1990) 171. 4. J. RIOSECO, PhD Thesis, University of Ltmd, Sweden, 1987. 5. E. HOLM, J. RIOSECO, S. BALLESTRA, A. WALTON, J. Radioanal. Nucl. Chem., 123 (1988)

167. 6. M: GARCIA-LEON, C. I. SANCHEZ-ANGULO, J. Radioanal. Nucl. Chem., 115 (1987) 377. 7. J. C. QING, A. AARKROG, H. DAHLAGAARD, S. P. NIELSEN, Cit. from INIS Atomindex,

20 .~48060. 8. H. LAMMERTZ, E. MERZ, St. HALASZOVICH, in: Scientific Basis for Nuclear Waste Manage-

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Abstracts, FRG, Lindau, October 8-12, 1984, p. 84. 10. A. STEFFEN, K. BACHMAN, Talanta, 25 (1978) 551. 11. K. E. GERMAN, V. F. PERETRUKHIN, 12th Radioehemical Conference, M~rianske l_Azne,

Czechoslovakia, 7-11 May 1990, Abstr. of papers, 1990, p. 24. 12. K. H. LIESER, C. BAUSCHER, L6slichkeit yon Technetiumdioxide in Wasser und in kon-

zentierten Salzlfsungen, INIS Mr. 11731, 1987, p. 39. 13. R. E. MEYER, W. D. ARNOLD, F. Y. CASE, Report NUREG/CR-4309, ORNL-6199, Mar.

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Materials Research Society, 1984, p. 237. 15. B. G. BRODDA, Sci. Total Environm., 69 (1988) 319. 16. D. READ, T. W. BROYD, Radiochim. Acta, 44145 (1983) 407. 17. T. R. GARLAND, D. A. CATALDO, K. M. McFADDEN, R. G. SCHRECKHISE, R. E. WILD-

UNG, Health Phys., 44 (1983) 658.

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18. A. KOSKINEN, M. HAKANEN, A. LINDBERG, Voimayhtioeiden sdinjaebtoimi kunta, Helsinki Finland, 1988, p. 43.

19. K. H. LIESER, U. MUHENWEG, Radiochimica Aeta, 44]45 (1988) 129. 20. ZHUANG HUIE, ZENG JISHU, ZHU. LANYING, Radioehim. Acta, 44/45 (1988) 143. 21. C. WOLFRUM, H. LANG, H. MOSER, W. JORDAN, Radioehim. Aeta, 44/45 (1988) 245. 22. J. J. HIGGO, T. G. COLE, L. V. C. REES, Radioehim. Acta, 44/45 (1988) 231. 23. K. E. GERMAN, S. V. KRYUTCHKOV, L. I. BELYAEVA, Izv. Akad. Nauk SSSR, (1987) 2387. 24. V. I. VOLK, J. V. ZAKHAROV, Radiokhirnya, 19 (1987) 794. 25. T. NAKASHIMA, K. H. LIESER, Radiochim. Acta, 28 (1985) 203.

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