as the peroxide by addition of H,9,-
FLOW SHEET FOR RECOVERY & PURIFICATION OF PLUTONIUM
oxide was converted to nitrate (4 valence state)
Cobia kK Be Mg CaS BatCeEe|
WU Me FeCu ag Zn Me Sa E570 Or APnm Soin
and was given to the Dry Chemistry Group for flu-
NaOH in Ercess
eee
Sol'n of haMaK, Beery BO, 395 CAs
Mots, WOEZn0gS035 4.P.S.F 51 Br,|
oa
Pee of Rs Bro on ed af 419 CaSe
det ry
lau areFeCags ede
7, Cp
Ge
solutions were reduced with so, and precipitated by
NH,OH fo Prt of 4-6
treatment with A1(0H),
Sel'n of MoCo, Sr, 84
Py of Purch Br rrendes af Ce.Ld.Te,
Some Pu.
Cb Ta,U,Ma Fe CoM
MC. 4g,M5, ZF,
In retrospect, it may be reasoned that the
greatest exposures occurred in step e when H,0, was
aq
oe
NH,0H in Excess
Sofn of Co,Ni,Cu, Ag
PUORLG Hydrondes of Cala,
Tau Mn fa, Wg fe Th
added (with vigorous stirring) to high concentra-
Same Pu
4
wt OO,
Sol'n cf Above Hydrandes
_SOatHE
Secret TageTri)
b,Ta,U,'dn, Fea)
Some Pu
st
Put
ftem
tions of plutonyl nitrate (1 to 40 grams per liter).
Meth * He Oy
Ke MF
==
Sarnot Th vial [son
t
eti,
Ti,“ VKaPurey
Gata,
UbnnaCh (Kalinadsre,
Zr. th
Some Pu Some
{|
Pu 1
bm Hy 504 HNO, FUME yO
NeBrOs
Cela,
2e,Tr
Cein7,Cp, |
Although this procedure was carried out in an open
Pul,
Ta Mo,Fe,
HRD
Sol'n of Sulghates of Pu.CeLad ZATA)
NH,OH
hood in 3-liter cooled beakers, there was consider-
Peticten
RIOs
("AngmzeJ
Sol'n of v.CeLe(Zr,Th)
hNO,* Nabro,
Pu(OH},
17
the recovery procedure, but this also coincided in
onAF]
i* [Sone
a
KO,
Ped,
time with the increasing amounts of plutonium being
noted,
NaPyO,45,, Ce LaTazr)
HNO,
]
a
{
(Ceo ta2r}
Soma Put, {Ce Lathzry
handled.)
]
a
amar
Extract on
‘
y
to Puntieaton——
(The number of high nose counts in-
creased sharply when the peroxide step was added to
2 Zr,Th)
oo (Ce.LaTh zr}
Nad > SHO
ae ew Seedae ean +
respirators.
PuOy CrileGh29
POT CTR ara
rH OH
In April and May 1945, this pro-
cedure was often carried out by workers wearing
Wa, $3, , Heal
Sucernatont
Some Pu
able fizzing and discharge of droplets into the air
outside the hood.
HNO,
(
In December 1944, this
process was turned over to another group (CM-10).
HNO,
Cato,
.
HNOS
Late in 1944, the dilute supernatant
orination.
Some Pu
nN,
The plutonium
MgO,
5Le)
bale
HNO,
of dilute supernatant solution (0.1 to 1.0 gram per
liter) also caused heavy fogging and occasionally
Spattering.
or
——te Purification
The addition of NaOH to the large vats
Because of the size of the 50-liter
containers, this procedure was carried out in the
open laboratories without benefit of hoods.
Fig.
5.
3
Flow sheet for the recovery operation.
This gives the general outline of the
procedures used, but each individual
recovery operation required special conditions.
Other
chemical steps which caused airborme contamination
were concentrating dilute solutions by boiling;
ashing combustible materials; and fusion procedures,
especially those involving sodium peroxide plus
earbon or persulfate.
eee
As might be expected, in the atmosphere of
plutonium were dissolved directly in HCl; insoluble
excitement, tension, and fatigue that prevailed
salts
during the closing days of the war, the Recovery
(oxides or carbides) also were dissolved in
acid after persulfate or carbonate fusion; (b) plutonium was precipitated with NaOH or NHOH;
(c) pluto-
nium hydroxide was dissolved in HNO, and precip-
Group had its share of accidents which undoubtedly
contributed to the exposures.
The most dramatic
of these occurred in May 1944 when the first 8-gram
itated as the oxalate in the presence of reducing
batch (the world's entire supply at that time) of
agents;
purified plutonium was being processed.
(d)} plutonium oxalate was redissolved in
An initial
HNO, and oxidized to the hexavalent state by treat-
3.6-gram aliquot of plutonyl nitrate in solution,
ment with NaBrO,;
placed in a glass thimble prior to Soxhlet extrac-
(e) ether extraction similar to
that used in the purification process described
tion, was heated in an oven.
later (steps d and e), which involved extraction
moved, the glass tray supporting the thimble broke
from acid solution (in the presence of ammonium
nitrate) and subsequent reduction with iodide
and
precipitation as the oxalate;
and (f}) after April
and the concentrated solution spilled on the floor.
1945, the plutonium was extracted into ether
and
reduced to the tetravalent state and precipi
tated
As it was being re-
The spilled material was aspirated by mechanical
suction, and the remaining plutonium was recovered
from the contaminated asphalt tile slabs tom up
from the floor.
When recovered and purified, this