Phosphorus-32 Production by Sulfur

Irradiation in a Partially Moderated Neutron

Flux by 32S(n,p)32P Reaction

J. Alanis1 and J.M. Navarrete2

'Nuclear Center of Mexico, ININ. Ocovoacac. 50045 Mexico; 'Faculty of Chemistry.

Bldg. D, CU, UNAM, 05410 Mexico

Taking advantage of the fact that some positions for irradiation in the
Mark III Nuclear Reactor of the Nuclear Centre of Mexico show neutron
fluxes only partially moderated, phosphorus-32 has been produced by irradi
ating targets of previously purified commercial sulphur, by distillation at
444±2°C under nitrogen atmosphere, dilution of vapours in carbon disul-
phide, filtration of the solution through fibreglass, Teflon and cellulose, as
well as final crystallization of S4 by CS, evaporation. After irradiation during
6 to 20 hours with fast neutron fluxes from 4.5 to 7.4 x 1012 n-cm!-s', the
sulphur target is distilled again at the same temperature, always under nitro
gen atmosphere. Once the Pyrex recipient is cooled down to 110±2"C, one air
flux is passed through during few seconds, and the 32P is stuck on the recipi
ent wall. When 25 to 50 ml of concentrated HC1 are added, an acid solution
of Hj^POj is formed. Once this acid solution is diluted and pH fixed to an
adequate value, labelled ortophosphoric acid is available to obtain labelled
phosphates to be used in biological and agricultural studies. Chemical and
radiochemical purity of these substances are almost total. At this stage, till 12
mCi of Hj32PO4 have been obtained for a Sd target mass of 5 g. The procedure
seems to be so reliable that industrial, periodical production is being planned
to start in a few months.

Introduction
Phosphorus-32 is one of the radioisotopes which has found more applica
tions as tracer in such diverse fields as biology, medicine, gauging and agri
culture. Therefore, the Nuclear Center of Mexico has planned to set up a

©2005 by MEDIMOND S.r.l. F425S0145 83

84 5th International Conference on Isotopes
process to produce it in the easiest and more profitable way by neutron irra
diation in the General Electric MARK III Research Nuclear Reactor, 1 MW
power, operating among their facilities. So, between two possibilities to pro
duce it, either by 3lP(n,y)32P (thermal neutrons) or 32S(n,p)32P (fast neutrons),
was chosen the second one because the following reasons:
a) to purify the S target by distillation is relatively easy, while the impurities
of P and phosphates are difficult to manage and reduce,
b) the specific activity of 32P obtained through the 32S(n,p)32P nuclear reac
tion is much higher than that obtained by 3lP(n,y) 32P nuclear reaction, in
spite of the great difference between the cross sections of both nuclear
reactions: 6 = 0.19b for thermal neutron capture by 3IP '• and a = 0.068b
for fast neutrons reaction with 32S 2,
c) the neutron flux measurements in the central irradiation position in our
Nuclear Reactor are about 1.13 x 10l3n.cm2.s' for thermal neutron flux
and 7.14 x 1012 n.cm2.s' for fast neutron flux,
d) the high yielding of 32P radiochemical separation by S target distillation
assures great specific activity as well as great radiochemical purity,
e) from the possible radiochemical impurities produced by the fast and ther
mal neutron irradiation of four isotopic varieties 32S (95.02%), "S (0.75%),
34S (4.21%) and 36S (0.02%), just »P is not possible to eliminate either by
distillation of the S target or by simple decaying, but the ratio between the
32P and 33P activities produced in the same irradiation conditions is about
7000 greater for 32P, because the much lower isotopic abundance and fast
neutron cross section of 33S target as well as longer half life of 33P. Table
I shows the radioisotope production by S irradiation with fast neutrons.
Table 2 shows the radioisotope production by S irradiation with thermal
neutrons. So, in view of the partially moderated neutron flux available in
the most suitable irradiation position of our nuclear reactor, and the theo
retical considerations which seems to favor the 32S(n,p)32P nuclear reac
tion, it was decided to carry on the 32P production in this way.

Table I.- Nuclear reactions between S isotopes and fast neutrons

Isotope Isotopic Abundance (%) Nuclear Reaction Half Life

"S 95.02 "S(n.p)"P 14.26 d
"S 0.75 "Sdi.p)"P 25.3d
4.21 i4S(n.p)JJP 14.4 s
"S 0.02 J"S(n,PrP 5.9 s

Table 2.- Nuclear reactions between S isotopes and thermal neutrons

Isotope Isotopic Abundance (%) Nuclear reaction Half Life

95.02 JJS(n,y)33S Stable
"S 0.75 "S(n,y)"S Stable
34S 4.21 J4S(n.Y)JiS 87.2 d
>bs 0.02 J6S(n,Y)J's 5.05 m
Brussels, Belgium, April 25-29, 2005 85

Experimental
One Pyrex distillation was conditioned inside one electrical furnace in
order to distillate S at 444±2° C in an inert nitrogen atmosphere. This set is
put in a glove box with negative pressure and connected to two suitable traps
or receivers to condensate the distilled S as well as two CS, diluters used to
prevent any possible vapors leak from the system. The wayout of vapors to
the general exhaust system is induced by one small vacuum pump, and down
wards in the distillation chamber. On the top are located two containers used
to inject 0.1 N HC1 solution to the chamber and to recuperate the radioactive
H3 32PO4 solution once the whole process has taken place. The control mecha
nism is situated out from the glove box and it comprises the vacuum pump
plus five pass valves to be operated independently of the set inside the glove
box. Two activated carbon Filters, the first one situated before the CS, diluters
and the second one before the vacuum pump outside the glove box complete
the system, Fig. 1.

The general procedure is as follows:

a) The purification of S target is accomplished by putting one 5 g S sample,
AR grade, in the distillation chamber. Before heating, the chamber cap is
connected to the nitrogen injector in order to have an inert nitrogen atmos
phere in the chamber. Valves V, and V3 must be closed, while valves V,,
V4 and V5 must be open. Vacuum pump is on and heating starts slowly till
the temperature reaches 444±2° C, when S distillation begins. After 1
hour, about 95% of the sample solidifies in the first receiver or S trap,

Glove Box

Fig. I.- Distillation System to purify S and obtain H"POf

86 5th International Conference on Isotopes
while about 4% solidifies in the second one. If some vapor pass the first
two receivers, it should be dissolved in the 3 CS2 diluters and trapped in
the 2 activated carbon filters. The test for proving the correct functioning
of the distillation process, is the lack of S deposition in the last trap,
located before the vapors exit to the exhaust system. In the distillation
chamber remain just S impurities with higher boiling point. The furnace
is off, and once cooled down solid S is collected from the first two traps
to be dissolved in 25 ml of CS. This solution is filtered through one glass
fiber first, and then through one Teflon filter, applying vacuum in the side
arm of an Erlenmeyer filtration device. Finally the solution is filtered
trough cellulose filter paper and evaporated at room temperature on a Petri
dish to get the purified S^ crystals.
b) The 5g target sample is conditioned in a polyethylene capsule first, and
then in the aluminum rabbit to be irradiated in the central position of the
Triga Mark III Nuclear Reactor at a thermal neutron flux of about 1.13 x
10l3n.cnr2.s-' and fast neutron flux of about 7.14 x 1012 n.cnr2.s'. Irradia
tion time was 6 hours and cooling time from 12 to 15 hours. The radio
active sample was taken then to the glove box to perform the radiochemi-
cal separation, by making use of the shielded container installed in the
remote control, automated carrier, for transporting radioactive sources3.
c) Once the carrier is beside the glove box, the shielded container is open
and the rabbit with the radioactive source is placed inside by using remote
control tongs and acting the piston to open the rear door of the glove box.
The rabbit and polyethylene capsule are open inside the glove box, and
radioactive source is deposited in the distillation chamber, which is
hermetically closed with the special cap connected to nitrogen container.
Valves V, and V3 must be closed, while valves V,, V 4 and V5 must be
open, the same than in the S purification step. The vacuum pump is on,
in order to produce a light nitrogen flux, while the temperature of the
furnace is raising gradually, keeping up intervals from 60 to 70°C, till
reaching the S distillation temperature: 444±2°C. The radioactive sulphur
begins to deposit in the first two receivers or traps, while that one located
after the third CS, diluter should remain clean, and after one hour the
whole sample has been distilled, while the 32P remains stuck to the cham
ber walls.
d) Then the vacuum pump is off, the temperature in the furnace is lowered
down to 110±3°C, and the cap of the distiller is replaced for that con
nected to 0.1 N HC1 acid container, allowing the air to get into distillation
chamber for few seconds. Valve V3 must be closed, while valves V|t V2,
V4 and V5must be open. When the vacuum pump is on, 0.1N HC1 solution
is introduced to distillation chamber. Then the vacuum pump is off and
release valve is open.
e) When release valve is closed, vacuum pump is reactivated and valves V
and V4 are closed simultaneously, vacuum is created in the reaction cham
ber, pump is off and the oxidation reaction to get Hj32PO4 acid solution
takes place during one hour.
0 When V, is opened (V, and V, remain open, V2 and V4 remain close) and
Brussels, Belgium, April 25-29, 2005 87

the vacuum pump is on, the H332PO4 acid solution flows to the same acid
container where the 0.1N HC1 was before being injected into the chamber.
V5 is closed slowly, to assure the whole volume has been transferred to the
acid container. Finally, vacuum pump is off and V4 is opened,
g) The shielded acid container with about 15 mCi of H332PO4 is taken out
from the glove box and it is ready for the chemical and radiochemical
purity tests, as well as to label any wanted molecule with 32PO4~ ion at
a suitable pH.

Results
The crystallization of S^ after distillation of common S, AR grade, seems
to purify substantially the element in order to be used as target in a partially
moderated neutron flux. X rays fluorescence analysis of S before and after
distillation shows a total elimination of K, Ni, Cu, Br, Sr and Pb impurities,
while Ca, Fe and Zn impurities remain. Nevertheless, the radiochemical pu
rity of the final H332PO4 solution obtained seems to be good enough for any
tracer application, since the decay curve taken during 45 days does not show
any deviation from some other beta or gamma radiation, but just a decay with
half life neatly equal to 14.28 days, that of 32P.

Discussion

From all the possible radioisotopes formed by S neutron irradiation (Ta

bles 1 and 2), just "S (t,,,=87.2 d) and 33P (t1/2=25.3 d) could be radiochemical
impurities of the final product 32PO4~ (t,/2=14.28 d). 35S may be present in the
final product due to an unfinished distillation of the irradiated S target. How
ever, 1 hour distillation at 444±2°C seems to drain totally the irradiated S
from the chamber to both S receivers, and of course it never has got into the
final one, after three CS, diluters and one activated carbon filter used to
prevent any leak of radioactive vapor, plus an additional carbon filter in
stalled before the vacuum pump. On the other hand, 3SS is neatly the main
radioisotope present in the irradiated and distilled S, at such a point to open
the possibility to dissolve it in CS, in order to be used as S tracer. On the
contrary, 33P is not possible to eliminate from the final product 32PO4~. Nev
ertheless, because the low isotopic abundance of 33S target (0.75%), low 6 for
fast neutrons (0.002b), and longer half life of "P (t,/2=25.3d) than that of 32P
(tl/2=14.28d), the fraction of 33P radioactivity as radiochemical impurity of 32P
becomes about 0.01%, which seems to be negligible for the use of 32P as
tracer.

Conclusion

The first experience to produce 32PO4~ by irradiating a target of purified

S with a partially moderated neutron flux, has been totally successful and it
encourages to proceed to the next step: the industrial, weekly production of
100 mCi of this radioisotope by irradiation of heavier targets till 30 g of
88 5th International Conference on Isotopes
purified S, at longer irradiation times till 24 hours, and then to carry on the
radiochemical separation by distillation in a self contained, sure enough sys
tem.

References
1- Table of Isotopes, 6"1 Ed. C.M.Ledercr, J.M.Hollander, I.Perlman, J.Wiley, USA, 1967,
p.239
2- Health Physics and Radiological Health Handbook, Ed. Bernard Shleien, USA
1992, p.244
3- J.AIanfs, A. Segovia, M.Navarrete, The Radiation Safety Journal, 87 Supl. (2004)
S34-S36