EPA-R4-73 014
MAY 1973
Environmental Monitoring Series
PROCEDURES FOR RADIOCHEMICAL ANALYSIS
OF NUCLEAR REACTOR AQUEOUS SOLUTIONS
-------
EPA-R4-73-014
May 1973
PROCEDURES FOR RADIOCHEMICAL ANALYSIS
OF NUCLEAR REACTOR AQUEOUS SOLUTIONS
H. L. Krieger and S. Gold
Radiochemistry & Nuclear Engineering
Research Laboratory
Program Element 1H1327
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH & MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
REVIEW NOTICE
The National Environmental Research
Center, Cincinnati, U. S. Environmental
Protection Agency, has reviewed this report
and approved its publication. Mention of
trade names or commercial products does not
constitute endorsement or recommendation
for use.
* *
11
-------
FOREWORD
Man and his environment must be protected from the adverse
effects of pesticides, radiation, noise and other forms of pollution,
and the unwise management of solid waste. Efforts to protect the
environment require a focus that recognizes the interplay between the
components of our physical environment—air, water, and land. The
National Environmental Research Centers provide this multidisciplinary
focus through programs engaged in
studies on the effects of environmental contaminants
on man and the biosphere, and
a search for ways to prevent contamination and to
recycle valuable resources.
The current increase in the number of nuclear power stations
requires expanded monitoring programs at the state and federal level
to assure that radiation exposure of persons in the environment remain
at an acceptably 1/ow level. The Environmental Protection Agency is
therefore engaged in studies at operating nuclear power stations to
provide information on environmental radiation and radioactivity
levels and to evaluate monitoring programs. One aspect of these
studies had been the collection, evaluation and, in some instances,
modification of radiochemical analytical methods for measuring radio-
nuclides in coolant and waste water at these stations. Presented in
this manual are 38 methods that have been found appropriate for the
commonly encountered radionuclides. This effort has been supported
by the Office of Research and Monitoring, in cooperation with the
Office of Radiation Programs, EPA.
A. W. BFeldenbach, Ph.D.
Director
National Environmental
Research Center, Cincinnati
ill
-------
PREFACE
In the course of studies to evaluate potential health hazards
from aqueous discharges at nuclear power stations during routine
operations, the Radiochemistry and Nuclear Engineering Research Labora-
tory of the U. S. Environmental Protection Agency's National Environ-
mental Research Center in Cincinnati has compiled and tested the
radiochemical methods given in this manual. The composition of test
solutions has ranged from mixtures of many radionuclides at microcuries
per milliliter (uCi/ml) concentrations to barely detectable levels at
picocuries per liter (pCi/1) concentrations. The substrate quality
has ranged from highly deionized coolant water to waste solutions with
high concentrations of salts and detergents.
The procedures in the front section of the manual are standard
methods* which are applicable for separating and measuring these radio-
nuclides in most reactor liquid wastes« Selected sections from each
procedure have been reproduced verbatim from the standard text, with
notes added at the end of each procedure to indicate where modifica-
tions were made or problems arose. Modifications were only employed to
effect additional decontamination or to clarify the method for assuring
uniformity in replicate analyses.
The methods in the second section have been compiled from
information in analytical chemistry texts or from technical reports in
the scientific literature. Many have been adapted from several sources,
and all have been modified as deemed appropriate. Comparable procedures
for barium, iodine, iron, manganese and tritium are to be found in both
sections of the manual. These have been included with the other
developed procedures, as personal preference, because they are simpler
or more rapid than the ASTM methods and have been proven in comparable
evaluations. All methods in this second section contain references to
their origin and have explanatory notes when appropriate.
Method evaluation involved replicate analyses with reactor
coolants, reactor wastes and specific tracer solutions as substrates.
The criteria established for each method were chemical yields greater
than 70%, decontamination factors at least 10^, procedure time commensu-
rate with the half life of the nuclide being separated, and ease of
analysis. In general, the system followed for each radionuclide
consisted of adding a standardized carrier to the test solution
*ASTM Standards. Water; Atmospheric Analysis Part 23, American
Society for Testing and Materials, Phila., Pa. 19103 (Oct. 1972).
-------
to give about 20 mg as the final precipitate and stirring to effect
complete interchange between the stable and radioactive components in
the solution. Two of the procedures (neptunium and technetiuin)
required non-isotopic carriers for yield determinations since standar-
dized carriers are not available. For samples containing nuclides in
several oxidation states, complete interchange with the stable carrier
requires strong oxidative and/or reductive treatment during the initial
steps of the procedure.
After concentrating the sample and purifying the nuclide by
precipitation, evaporation, ion exchange, solvent extraction or distil-
lation, the final precipitate is collected on a 2.8-cm glass fiber
filter and washed with water and ethanol. Drying is effected either
by oven heat or treatment with solvents and suction or both until a
constant weight is obtained for chemical yield determination. The
precipitate is prepared for counting by covering it with 0.01 mm mylar,
and mounting it in a nylon ring and disc. The identification and
activity level of the separated nuclide are confirmed by ingrowth and/
or decay measurements, gamma-ray peak identification, and beta-particle
absorption determinations. When required, repeated spectral analyses
and decay measurements were made to identify and quantify the isotopes
of the separated radionuclides (e.g., 134cs, 136cs and 13?Cs in the
cesium chloroplatinate precipitate). The method capabilities and
decontamination factors obtained for each procedure after replicate
tests are given in Appendix C.2.
In the course of repetitive radiochemical analyses of reactor
discharges, several problems were observed. These included incomplete
purification (decontamination) of specific radionuclides in coolant
water and reactor wastes; incomplete carrier-radionuclide exchange;
loss of activity by adsorption on container or by volatility; and
cross-contamination of separated fractions, particularly when very
high- and low-level activity samples were analyzed simultaneously.
Ultimately, the procedure to be selected and the modifications to be
included are determined from experience. Activity loss on container
walls, for example, is minimized (but not eliminated) by acidifying
the sample at the source with cone. HN03 (1 volume acid to 10 volumes
solution) and analyzing for all activities soon after collection.
Radioiodine and carbon-14 analyses, however, are made on separate
aliquots from an unacidified sample to prevent losing volatile
fractions.
Many reactor-produced nuclides have half lives of less than one
week and should be analyzed before much time has elapsed. The
methods in this manual are applicable for the most frequently identi-
fied isotopes having a half life > 6 hr. To assist in performing
v i
-------
the maximum number of separations chronologically, a suggested order
is included in Appendix C.3.
The users of this manual should be cautioned that, with the
multitude of reactor and waste solutions generated, radionuclide and
chemical compositions will vary and therefore require auxiliary treat-
ment to effect desired decontamination. Although specific scavenges
and repurification of the final precipitate have been effective in a
few instances, no general approach can be recommended.
It is imperative that counter background and analyzer calibrations
be monitored frequently to observe changes caused by contamination or
electronic malfunction,, In the laboratory, routine carrier standardi-
zations and reagent purify checks are recommended and analytical
capabilities should be confirmed by providing analysts with test
samples and replicates for quality control. Routine carrier standardi-
zation involves the quantitative precipitation of aliquots in triplicate;
weighing of the purified salt in the same geometrical configuration as
the final precipitate in the procedure of concern; and repetition of
the foregoing at intervals.
It is anticipated that for the nuclides discharged from light-
water moderated nuclear power reactors today, the procedures in this
manual will provide the analysts with a means for measuring specific
radionuclides with some degree of confidence. As reactor types and
operating procedures undergo changes, modifications to these methods
may become necessary. Although this manual is primarily directed
toward use of beta-particle counting with proportional or G-M counters
and of gamma-ray spectrometry with Nal(Tl) detectors, Ge(Li) systems
are becoming more widespread. The use of the latter, although some-
what more expensive, would minimize the need for much radiochemical
separations except in the cases of pure beta emitters (l^C, 32pt 35$
etc.). Readers are encouraged to submit comments on methods described
in this manual and to indicate improvements which can be included in
future revisions.
VII
-------
Table of Contents
Review Notice
Foreword
Preface v
List of Figures xi
Section I
A. ASTM Standard Methods 1
Barium (D2038-68) 2
Iodine (Distillation) (D2334-68) 6
Iron (D2461-69) 13
Manganese (D2039-71) 17
Tritium (D2476-70) 20
B. Reagent Preparation - ASTM Standard Methods 23
Section II
A. Developed and Modified Methods 29
Antimony 30
Arsenic 34
Barium (see Strontium and Barium, pg. 108)
Cadmium (see Cobalt and Cadmium, pg. 54)
Carbon-14 38
Cerium ^3
Cesium *'
Chromium 50
Cobalt and Cadmium 54
Cobalt and Nickel 59
Copper and Technetium 67
Iodine 73
Iron 77
Lanthanum plus Trivalent Rare Earths and Yttrium 81
Manganese 85
Molybdenum 88
Neptunium 92
Nickel (see Cobalt and Nickel, pg. 59)
Niobium (see Zirconium and Niobium, pg. 144)
Phosphorus 96
Ruthenium 99
Silver
Strontium and Barium
IX
-------
Sulfur
Tantalum and Niobium
Tellurium
Tin i26
Tritium 13°
Tungsten
Yttrium
Zinc 14°
Zirqonium and Niobium •*•"
B . Acknowledgments 149
C. Appendices
1. Reactor Coolant Radionuclides as Reported
in the Literature 153
2. Method Capabilities and Decontamination
Factors 156
3. Suggested Order of Analyses for Reactor
Aqueous Samples 158
4. Efficiency Multiplication Factors for
Gamma-ray Emitters 159
5. Decay Correction Factors 162
Sample Calculation Sheet 163
6. Reagent Preparation 164
D. Selected Bibliography 174
-------
List of Figures
1. Distillation Apparatus for Iodine Analysis 7
2. Distillation Apparatus for Carbon-14
Analysis 39
3. Absorption Curve for Carbon-14 on
s.s. Planchet 41
4. Absorption Curve for Nickel-63 on
s.s. Planchet 65
5. Distillation Apparatus for Ruthenium
Analysis 100
XI
-------
SECTION I
A. ASTM Standard Methods
The full descriptive material for these five ASTM Standard Methods
is not reproduced. The full Standard, including descriptive material,
is obtainable from the American Society for Testing and Materials,
1916 Race St., Philadelphia, Pa. 19103. Reproduction of these Standards
in this manual was through the permission of the Society.
-------
Radioactive Barium - ASTM(D2038-68)
Principle of Method
Radioactive barium and added barium carrier are first precipi-
tated from water to reduce the sample volume, then chemically purified,
and finally counted with a gamma counter or beta particle detector.
The main purification step is the repeated precipitation of barium
chloride from a cold hydrochloric acid-ether mixture, and scavenging
with ferric hydroxide. A final precipitation of barium sulfate is made
and the chemical yield is computed by comparing the weight of the
precipitate to the amount of carrier added originally. The recovery of
radioactive barium is assumed to be equal to the chemical yield.
Reagents (Note 1)
Ammonium hydroxide solution (1:1)
Barium nitrate, carrier solution (19 g per liter)
Ethyl alcohol (95 per cent)
Ethyl ether
Ferric nitrate, carrier solution (72 g per liter)
Hydrochloric acid (sp gr 1.19)
Hydrochloric acid-ether mixture
Lanthanum nitrate, carrier solution (30.4 g per liter)
Sodium carbonate solution (106 g per liter)
Sulfuric acid solution (1:4)
Procedure
1. Add to the sample in a centrifuge tube, or a beaker in the case of
a large sample, 1 ml of barium carrier solution and mix. Heat to
near boiling. Then add an excess of Na^COg solution (Note 2), heat
to boiling, and let stand for 5 min until precipitation of BaCOo is
complete. Separate this precipitate by centrifugation, or by
decanting and centrifugation in the case of a large sample.
2. Dissolve the carbonate precipitate in 1 ml of water and 4 drops of
concentrated HC1 (sp gr 1.19) and transfer the solution to a 40-ml
-------
centrifuge tube. Add 10 ml of ice cold hydrochloric acid-ether
mixture (Note 3) and cool in an ice bath for 5 min. Centrifuge the
mixture and discard the supernate.
3. Dissolve the barium chloride (BaCl2) in 1 ml of water and repeat
the precipitation as described in step 2.
4. Dissolve the BaCl2 in 2 ml of water, add 5 drops of both iron and
lanthanum carriers and an excess of NH^OH (1:1), and heat to
precipitate the hydroxides. Centrifuge and discard the precipitate.
Note the time of this step which removed any lanthanum daughter
present. Complete the rest of the procedure, steps 5-7, in less
than an hour.
5. Evaporate the supernate to 2 ml and add 10 ml of hydrochloric acid-
ether reagent. Cool in an ice bath for 5 min and centrifuge to
separate the precipitated BaC^-
6. Dissolve the BaCl2 in 20 ml of water and add 3 ml of dilute sulfuric
acid (1:4). Digest on a hot water bath for 5 min. Centrifuge the
mixture and discard the supernate.
7. Transfer the precipitate to a tared quantitative filter paper using
water. Wash with water, alcohol, and ether. Dry at 110°C for
10 min, cool to room temperature, weigh as barium sulfate
and mount for counting.
8. Count as soon as possible.
-------
Calculation
Calculate the concentration, D, of radioactive barium in curies
per liter as follows:
D
2.22 x 10iz EVR
where :
C = net count rate, counts/min,
E = counter efficiency,
V = liters of sample used ,
R = fractional chemical yield, and
2.22 x 1012 = conversion factor from disintegrations/min to curies.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where :
F = fractional abundance of the gamma ray in gammas/disintegration, and
p = photopeak detection efficiency in counts /gamma ray.
Correct for the ingrowth of La in samples containing -"Ba as
follows :
A =
La
Ba
La Ba
where:
A^g = lanthanum-140 activity present,
Aga ~ barium-140 activity present in step 4 (Note 4),
e = base of natural logarithms,
t-L = elapsed time, in hours, from step 4 to counting time, and
T = half life of radioisotope, in hours.
-------
Calculate the decay correction for radioactive barium as follows:
-0.693t2/T
A = A0 e
where :
t2 = elapsed time, in hours, between sampling and counting.
Confirmation of i^Ba Purity and Identification of Daughter Activities
1. Plot the gamma-ray spectrum of Ba immediately after separation,
then repeat after La has grown in.
2. Count at 3-day intervals to measure the ingrowth of
3. Beta-count weekly over a 30-day period to substantiate the 12.8 d
half-life of 140Ba.
Notes:
1. The preparation of all reagents for this and the other ASTM
procedures is listed in the back of Section I of this manual.
2. An excess of reagent solution is that which assures that
precipitation is complete.
3. Caution. The hydrochloric acid-ether mixture should be prepared
and stored in a fume hood. Naked flames must not be present.
4. The l^Ba activity, which is determined after step 8, should
have no "^La present if only 30 minutes has elapsed from the
hydroxide scavenge (step 4) until counting time.
-------
Radioactive Iodine (Distillation) - ASTM(D2334-68)
Principle of Method
This method is based on the separation of iodine from other
activities by distillation of elemental iodine into cold carbon
tetrachloride. To assure chemical interchange with the iodine carrier,
an oxidation-reduction cycle is made. The iodide is oxidized to iodate
with permanganate, reduced to iodide with bisulfite, and distilled over
as free iodine in the presence of nitrite.
After washing the carbon tetrachloride with nitric acid, the
iodine is reduced with bisulfite and back-extracted into water.
Acidified silver nitrate solution is added to precipitate silver iodide.
The chemical recovery is used as a measure of radiochemical recovery.
Added decontamination from bromine activation product is afforded by
the permanganate oxidation step. During this step elemental chlorine
and bromine formed are distilled from the reaction flask and swept up
the fume hood. High level radiobromine could be trapped by passing
through a caustic solution, if desired.
The silver iodide precipitate is mounted for counting. Gamma
counting of the purified iodine solution can be completed prior to
precipitation of the silver iodide which is then used for determination
of the chemical yield.
Reagents (Note 1)
Aerosol solution (1:100)
Carbon tetrachloride--Technical grade carbon tetrachloride (CC1,)
Collodion solution (1:9)
Methyl orange indicator (0.5 g per liter)
Nitric acid solution (1:9)
Potassium iodide carrier solution (13.08 g per liter)
Potassium permanganate solution (saturated)
Silver nitrate solution (17 g per liter)
Sodium bisulfite solution (100 g per liter)
Sodium hydroxide solution (200 g per liter)
Sodium nitrite solution (100 g per liter)
Sulfuric acid (sp gr 1.84)
Sulfuric acid (1:9)
-------
18/9 Socket
20/40 5 Joint
500ml. Flask
Delivery
Tube
Figure 1. Distillation Apparatus for Iodine Analysis
-------
Procedure
1. Take a sample aliquot which contains no more than 10^ pCi of iodine
and does not exceed 100 ml in volume.
2. Pipet 2.0 ml of KI carrier in the 500-ml distillation apparatus
(Fig. 1). Add the sample, 2 drops of methyl orange indicator, and
mix.
3. Adjust the pH to the end point with H2S04 (1:9) or NaOH as required.
[The color changes from yellow (basic) to red (acidic) or the
reverse.]
4. Dilute the sample as required to about 70 ml. (Do not adjust the
volume if it is already greater than 70 ml.)
5. Add 2 ml of concentrated H2S04 (sp gr 1.84) for a 70-ml total
volume or increase the amount to yield a final acid concentration
of 1:35 for larger samples.
6. Add 3 ml of saturated KMnO^. For volumes greater than 70 ml add
1 ml of saturated KMnO^ for every 20 ml in the flask. A brown
precipitate of manganese dioxide often forms at this step, but
there should be sufficient permanganate to color the solution
purple. If not, add permanganate solution until a permanent purple
color remains.
7. Boil gently for 10 min. Cool to room temperature. (Bromine and
chlorine are volatilized during boiling.)
8. Add NaHSOg solution dropwise while stirring until the purple color
of permanganate and brown of iodine and manganese dioxide just
disappear. (Continue stirring for an additional 5 min. if necessary).
8
-------
Avoid an excess of bisulfite. Add the reagent as rapidly as
possible to avoid loss of iodine by volatilization.
9, Place 40 ml of CCl^ in a 100-ml graduated cylinder. Place the
cylinder in a 1-liter beaker used as an ice water bath and allow
the CCl^ to cool.
10. Place the top on the distilling apparatus and connect it to a
delivery tube which has been placed in the CCl^. Lubricate the
ball socket joint with concentrated H2SO^ and clamp. Connect an
air line to the inlet and adjust the flow rate to about 2 bubbles/
sec.
11. Open the still and add about 2 ml of NaN02 solution. Close the
still immediately.
12. Boil gently with a bunsen burner until all of the color in the
still fades and then continue boiling for 1 min longer. Continue
the air sparge for an additional 5 min.
13. Disconnect the delivery tube and rinse with water, catching the
rinse in the CCl^ trap.
14. Transfer the CCl^ trap contents to a 250-ml separatory funnel.
Drain the CCl* to a 250-ml beaker and discard the upper aqueous
phase. Transfer the CCl^ back into the separatory funnel. Rinse
the beaker with 50 ml of HN03 (1:9) and add to the separatory
funnel. Shake and let the phases separate.
15. Drain the CCl* ^ack into the 250-ml beaker and discard the upper
aqueous phase.
-------
16. Transfer the CCl^ into the separatory funnel. Rinse the beaker
with 50 ml of water and add to the separatory funnel. Add 3 to 5
drops of fresh NaHS03 as needed and shake until all color is gone
from the organic phase.
17. Discard the CCl^ to organic waste in a ventilated fume hood. The
aqueous phase may be gamma-counted if desired.
18. Transfer the aqueous phase to the 250-ml beaker, add 1 ml of HN03
(1:9) and stir. Add 10 ml of the AgN03 solution and heat until
the Agl precipitate coagulates.
19. Transfer the precipitate to a 100-ml glass centrifuge cone (Note 2)
using water to rinse the beaker contents into the cone. Add 2 or
3 drops of the 1 per cent aerosol solution, centrifuge, and discard
the supernate.
20. Wash the precipitate with 75 ml of water, add 2 or 3 drops of the
1 per cent aerosol solution, centrifuge, and discard the supernate.
21, Repeat the procedure given in step 20.
22. Transfer the precipitate to a tared counting dish (Note 3). Dry
under an infra-red heat lamp.
23. Weigh the precipitate. Apply 4 or 5 drops of dilute collodion to
fix the precipitate while counting and determine the count rate.
Calculation
Calculate the concentration, D, of the iodine isotopes in curies
per liter as follows:
2.22 x 1012
10
-------
where:
C = count rate, counts/min,
E = counter efficiency,
V = liters of sample used,
R - fractional chemical yield, and
2.22 x 1012 = conversion factor from disintegrations/min to curies.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
-0.693t/T
A- AQ e
where:
A - activity at time t,
AO = activity at time zero,
e = base of natural logarithms,
t = elapsed time in appropriate units, and
T = half life of radioisotope in same units as t.
Confirmation of -I Activity and Identification of Iodine Isotopes
1. Plot gamma-ray spectrum of separated sample immediately and after
6 hr, 24 hr, 2 d, 5 d, 1 week and 3 week intervals to identify
131I (t1/2 8.06 d, 364 and 637 keV) , 133I (tj/2 20.9 hr, 530 keV),
and 135j (tx/2 6.7 hr, 1130, 1260 and 1710 keV) in the sample.
2. Beta-count the Agl planchet daily to measure decay and confirm
half -life values for those isotopes present.
Notes;
The preparation of all reagents for this and the other ASTM
procedures is listed in the back of Section I of this manual.
If 50-ml centrifuge tubes are used in this procedure, steps 19-
23 can be performed as described except that only 20 ml of water
will be required to wash the Agl precipitate.
11
-------
Since glass-fiber filters and the efficiency values for this
geometry are available, the following procedural changes were
made after step 21:
a. Slurry the precipitate in 10 ml water, add 1 ml HN03 (1:9),
stir and immediately transfer precipitate to a tared glass-
fiber filter. Filter slowly at first to prevent loss.
b. Wash precipitate on filter successively with 20 ml water
containing a few ml HN03, 20 ml ethanol and 20 ml diethyl
ether. Let dry with suction at least 10 minutes, then
place in desiccator.
c. Weigh, mount and store in dark until ready to count.*
*Because glass fiber filters contain some ^OK beta particles and gamma
rays, filter blanks as well as reagent blanks should be monitored at
intervals. Reeve Angel glass fiber filters #934 AH, 2.8-cm dia,
obtainable from any supply house, have been found to be satisfactory.
12
-------
Radioactive Iron - ASTM(D246l-69)
Principle of Method
Radioactive iron and added iron carrier are separated from other
activities by hydroxide precipitation, liquid-liquid extraction, and
ion exchange. The separated iron is counted with a gamma counter or
spectrometer, or a beta particle detector.
Reagents (Note 1)
Ammonium hydroxide ( sp gr 0.90)
Anion exchange resin* (prepared ion-exchange column)
Ferric chloride, carrier solution (49 g per liter)
Hydrochloric acid (sp gr 1.19)
Hydrochloric acid (1:1)
Hydrochloric acid (1:19)
Hydrogen peroxide (30 per cent)
Nitric acid (sp gr 1.42)
Nitric acid-hydrofluoric acid mixture
Nitric acid-hydrogen peroxide mixture
Thenoyltrifluoroacetone (TTA)-Xylene (111 g per liter)
Xylene
Procedure
1. Make the sample just acidic with concentrated HC1 (sp gr 1.19) and
add 2 ml in excess. Add 1.00 ml of FeCl~ carrier. Boil 2 min to
ensure solution of all the iron (see ASTM Method D 1068, Test for
Iron in Water.)
2. Add excess NH,OH. (Note 2). Collect the precipitate in a centri-
fuge tube by initial settling (if large volume) and centrifugation.
Discard the supernatant solution and wash the precipitate with
15 ml of water, discarding the wash.
3. Add to the precipitate 3 ml of water and 10 ml of concentrated
*Dowex 1-X8 chloride-form resin, 50-100 mesh, obtainable from Bio-Rad
Laboratories, Richmond, Calif., has been found to be satisfactory.
13
-------
HN03 (sp gr 1.42). Stir to dissolve and add 1 ml of H202.
4. In the following procedure, use a suitable extraction apparatus.
A separatory funnel may be employed as usual, or a centrifuge tube
may be used, removing unwanted phases by transfer pipet. Add
15 ml of TTA-xylene and extract for 5 min. Discard the aqueous
(lower) phase. Wash the extract and vessel walls with several
milliliters of water and discard the wash. If necessary for high
decontamination, transfer the extract in this and the next three
steps to clean vessels.
5. Add 15 ml of nitric acid-hydrogen peroxide mixture, shake 1 min,
and discard aqueous phase.
6. Wash the extract with 15 ml of nitric acid-hydrofluoric acid
mixture. Discard the aqueous phase.
7. Add 5 ml of concentrated HC1 (sp gr 1.19). Mix until the organic
phase is essentially decolorized. Discard the organic phase and
wash the aqueous phase and vessel with several milliliters of
xylene. Discard the xylene.
8. Evaporate just to dryness (do not bake), and take up in 20 ml of
concentrated HC1 (sp gr 1.19). Pass through the prepared resin in
the column at a flow rate of 1 ml/mln. Discard the effluent. Wash
with 40 ml of concentrated HC1 (sp gr 1.19).
9. Wash with 40 ml of HC1 (1:1). Elute iron from the resin with 30 ml
of water.
14
-------
10. Precipitate with excess NH^OH. Filter on ashless paper* designed
for gelatinous precipitates. Dry and ignite to FenOo ^n a P°rce"
lain crucible. Weigh to determine chemical yield.
11. Mount the Fe203 (Note 3) and count beta or gamma radiation.
Calculation
Calculate the concentration, D, of iron-59 in microcuries per
milliliter as follows:
D
2.22 x 10°EVR
where:
C = corrected count rate of sample, counts per minute per milliliter,
E = counter efficiency,
V = milliliters of sample used,
R - fractional chemical yield for the separation, and
2.22 x 106 = conversion factor from disintegrations per minute to
microcuries.
Calculate the decay correction for iron-59 as follows:
-0.693td/T
A = A e
o
where:
A = activity at time of measurement,
AQ = activity at time zero, that is, reference time,
t
-------
Notes:
The preparation of all reagents for this and the other ASTM
procedures is listed in the back of Section I of this manual.
An excess of NH^OH is added to assure completeness of the iron
hydroxide precipitation.
Slurry the ignited Fe203 with a few ml water and transfer to a
glass-fiber filter. Wash with water, alcohol and ether. Dry
at 110°C for 10 min. Cool to room temperature, and mount for
counting. Count beta or gamma radiation.
16
-------
Radioactive Manganese - ASTM(D2039-71)
Principle of Method
Radioactive manganese and the added carrier are first precipi-
tated as manganese dioxide. A final gravimetric precipitation of
manganese ammonium phosphate is used to compute the chemical yield of
the process.
Reagents (Note 1)
Ammonium hydroxide solution (1:1)
Ammonium phosphate, monobasic (NH^I^PO^)
Cobalt chloride, carrier solution (20 g per liter)
Ethyl alcohol (95 per cent)
Ethyl ether
Ferric chloride, carrier solution (49 g per liter)
Hydrogen peroxide (30 per cent)
Manganese chloride, carrier solution (36 g per liter)
Nitric acid (sp gr 1.42)
Potassium bromate (KBr03)
Potassium chromate, carrier solution (37.3 g per liter)
Procedure
1. Mix 1 ml of each of the carriers for manganese, cobalt, chromium,
and iron in a centrifuge tube (or use an Erlenmeyer flask of
suitable volume if a large sample must be taken) and add the
sample.
2. Add 5 ml of concentrated HNO^ (sp gr 1.42) and boil to remove
chlorides until evolution of N00 ceases; then add 1 g of KBrOo.
-£ J
(Note 2). Boil the mixture for 10 min and then cool.
3. Centrifuge the mixture and discard the supernate. Wash the
precipitate of manganese dioxide with hot water acidified with
HNOo until the wash water is colorless. (Note 3).
17
-------
4. Dissolve the manganese dioxide in 1 ml of concentrated
(sp gr 1.42) and one drop of H202, boil, and then add 1 ml of iron,
chromium, and cobalt carriers.
5. Repeat the procedure described in steps 2 and 3. (Note 4).
6. Dissolve the manganese dioxide in 1 ml of concentrated HNO^
(sp gr 1.42) and 1 drop of H202, boil, and then cool. Dilute with
5 ml of water.
7. Add 4 drops of iron carrier. Add NH/^OH (1:1) to precipitate the
iron below a pH of 7. (Note 5). Boil and filter through a fast
paper suitable for gelatinous precipitates. Discard the precipi-
tate.
8. Dilute the solution to 15 ml and add 1 g of NH^PO^. (Note 6).
Boil until a crystalline precipitate forms. Cool in an ice bath
for 10 min.
9. Filter onto a tared quantitative paper. Wash with water, ethyl
alcohol, and ether.
10. Dry at 110°C for 10 min. Weigh as manganese ammonium phosphate
[Mn(NH^)PO^.H20] and mount for counting.
Calculation
Calculate the concentration, D, of radioactive manganese in
curies per liter as follows:
D =
2.22 x 1012 EVR
where:
C = count rate of sample, in counts per minute,
18
-------
E = counter efficiency,
V = liters of sample used,
R = fractional chemical yield for the separation, and
2.22 x 10^ SB conversion factor from disintegrations per minute to
curies.
Calculate the decay correction for radioactive manganese as
follows:
, A -0.693t/T
A = AQ e
where:
A = activity at time t,
Ao = activity at time zero, in same units as A,
e = base of natural logarithms,
t = elapsed time, and
T SB half life of isotope, in same units as t,
Confirmation of Purity and Identification of
1. Plot gamma-ray spectrum of separated sample to identify and
quantify the 313-d 54nn photopeak photopeak (835 keV).
2. Repeat gamma spectrum measurement after 4 weeks to substantiate
the manganese half life.
Notes:
1. The preparation of all reagents for this and the other ASTM
procedures is listed in the back of Section I of this manual.
2. The KBr(>3 must be added slowly and in small increments.
3. Effective washing is accomplished with 15 ml portions of hot
water acidified with 0.5 ml cone. HN03 (sp gr 1.42).
4. If cobalt contamination persists as a problem, another decontam-
ination is suggested. This can be accomplished by repeating
steps 2 and 3 of procedure another time.
5. Fe(OH)3 precipitation begins at pH 5 and is complete at pH 6.
6. At this point, the HE^E^PO^. is completely dissolved in the
solution since the pH is below 7. To make the precipitation
quantitative, the pH should be adjusted to 7 with 1:1 NtfyOH,
then boiled and stirred to precipitate manganese ammonium
phosphate.
19
-------
Tritium - ASTM(D2476-70)
Principle of Method
The scintillator solution, mixed with radioactive sample, is
excited by the beta particles and emits light pulses by a molecular
de-excitation process. The number of pulses per unit time is propor-
tional to the quantity of activity present. Multiple solutes are used
in the scintillator to provide the best combination of wavelength and
pulse height for this application. These pulses are detected by two
multiplier phototubes connected in coincidence and converted to
electric signals. The amplified pulses are recorded and the count rate
is measured. The efficiency of the system can be determined by use of
prepared tritiated water standards having the same density and color as
the sample.
Reagent
Scintillator stock solution (Note 1)
Procedure
1. Filter the sample through a membrane filter if turbid.
2. Distill the sample if ionizing radiation other than tritium is
present. The distillate must be redistilled if any ionizing
radiation other than tritium is carried over during the previous
distillation. (Note 2).
3. Transfer a 5-ml sample aliquot into a sample vial and add 16 ml of
previously standardized scintillator solution. Mix.
4. Prepare a blank having the same density and color as the sample
using 5 ml of water.
5. Place the sample and blank in the counter and dark-adapt for 2 hr.
(Note 3).
20
-------
6. Count the sample for the length of time to give the desired
reliability.
Calculation
The efficiency factor for the scintillator mixture (Note 4) is
calculated as follows:
Tritium activity,* C = - -
where :
N = number counts accumulated,
B = background of blank, counts per minute (cpm),
C = net counts per minute per milliliter (cpm/ml),
t = time of counting, min, and
V = milliliters of test specimen used.
Q
Tritium efficiency (fraction), Eo = -
JH D
where :
D = disintegration rate, disintegrations per minute per milliliter
(dpm/ml)
Tritium efficiency factor, F(uCi/cpm) =
1
E, x 2.22 x 10&
%
where:
2.22 x 10^ = conversion from disintegrations per minute to microcuries.
Calculate the tritium radioactivity in microcuries per milli-
liter as follows:
Tritium activity, A, (uCi/ml) = FC
Confirmation of % Activity
1. Determine the count rate for each sample, background and standard
at two selected window settings. Compare the ratios for the •%
*This is not "activity" but "cpm/ml".
21
-------
standard with that for the samples to confirm that the activity
being measured is tritium.
To make certain that the samples have been dark adapted, count at
least three times until successive results are within 2 a of each
other.
Notes:
1. The preparation of this scintillation solution is described on
page 30 of this manual. This solution is standardized as
follows:
Transfer 16 ml of the scintillator stock solution into
each of two 20-ml polyethylene sample vials. Pipet 4 ml
of tritiated water standard solution containing 4000 to
5000 dpm/ml into one vial and 4 ml of water into the
remaining vial. Mix. The latter will serve as a blank.
Place the vials in position in the counter and dark-
adapt for 2 hrs. Count the blank and standard and calcu-
late the efficiency factor for the scintillator mixture
as above. (If the sample vial is of such size as to
contain 25 ml, use 20 ml of scintillator stock solution
and 5 ml of the sample.)
2. As a general rule, all samples should be distilled to dryness
for quantitative recovery and to decontaminate the tritium from
other ionizing radiations that may be present. Any problems
arising from the presence of iodine-131 in the aqueous samples
can be eliminated by the addition of AgNO-j and iodine carrier
to the flask before distillation begins. In any event, the
sample should be distilled carefully to guard against "bumping"
and the physical carry-over of ionizing radiations other than
tritium.
3. The same sample blank may be used for a number of samples
provided the same scintillator solution is used for each and
the blank has the same density and color as the samples.
4. Some scintillation mixtures are available which give lower back-
ground and higher counting efficiencies for 3fl. An example of
such a stock solution, which is in use at this installation, is
listed in the back of Section II of the manual (Appendix C.6)0
22
-------
B. Reagent Preparation — ASTM Standard Methods
I. Specifications
a. Reagent grade chemicals, or equivalent, as defined in ASTM
Methods E-200, Preparation, Standardization, and Storage of
Standard Solutions for Chemical Analysis*, shall be used in
all tests.
b. Unless otherwise indicated, reference to water shall be under-
stood to mean reagent water conforming to ASTM Specifications
D1193, for Reagent Water, referee grade.
c. Radioactive purity shall be such that the measured radio-
activity of blank samples does not exceed the calculated
probable error of the measurement.
d. Carrier solutions are to be standardized in the manner
prescribed in the Calibration and Standardization section of
each procedure in the ASTM text. This requirement for
quantitative chemical yield determination generally involves
precipitation of aliquots of these solutions, in triplicate,
in the same manner as the final precipitates in the respective
procedures.
II. Reagents
Aerosol solution (1:100) - Add 1 ml of 25 per cent aerosol
solution to 100 ml water and mix.
Ammonium hydroxide solution (1:1) - Mix 1 volume of concentrated
ammonium hydroxide (NH^C-H, sp gr 0.90) with 1 volume of water.
Anion exchange resin -[For method ASTM - D2461-69] Make a slurry
with water and transfer to a glass ion-exchange column [17 cm
long by 0.9 cm I.D., with a 50-ml reservoir at the top and a
2-mm bore stopcock at the bottom] until a layer of resin
*ASTM Standards. Water; Atmospheric Analysis, Part 23', American
Society for. Testing and Materials, Phila., Pa. 19103 (Oct. 1972).
23
-------
about 12 cm deep is formed. Wash with 50 ml of water and
50 ml of concentrated HCl (sp gr 1.19) before each use.
Barium nitrate, carrier solution (19 g per liter) - Dissolve 19 g
of barium nitrate (Ba(N03)2) in water, add 5 ml of concen-
trated HN03 (sp gr 1.42), and dilute to 1 liter. This
solution will contain 10 g of Ba++ per liter.
Cobalt chloride, carrier solution (20 g per liter) - Dissolve
20 g of cobalt chloride (CoCl2.6H20) in 100 ml of HCl (1:19),
dilute to 1 liter and store in a polyethylene bottle. This
solution will contain 5 g of Co"*"*" per liter.
Collodion solution (1:9) - Dissolve 8 ml of collodion (USP) in a
mixture of 48 ml of ethyl ether (anhydrous) and 24 ml of
absolute ethanol.
Ferric chloride, carrier solution (49 g per liter) - Dissolve
49 g of ferric chloride (FeCl3.6H20) in 100 ml of HCl (1:19),
filter, and dilute to 1 liter. This solution will contain
10 g Fe"1"*"1" per liter. Standardize by precipitation of
hydroxide, filtering, and igniting to ferric oxide (Fe203).
Ferric nitrate, carrier solution (72 g per liter) - Dissolve 72 g
of ferric nitrate (Fe(N03)3.9H20) in water containing 1 ml of
concentrated nitric acid (HN03, sp gr 1.42) and dilute to 1
liter. This solution will contain 10 g of FC+++ per liter.
Hydrochloric acid (1:1) - Mix 1 volume of concentrated hydro-
chloric acid (HCl, sp gr 1.19) with 1 volume of water.
24
-------
Hydrochloric acid (1:19) - Mix 1 volume of concentrated hydro-
chloric acid (HC1, sp gr 1.19) with 19 volumes of water.
Hydrochloric acid - ether reagent - Slowly add 500 ml of concen-
trated hydrochloric acid (HC1, sp gr 1.19) to 100 ml of ethyl
ether and mix. Cool in an ice bath before using. [Prepare
and store this reagent in a fume hood. Naked flames must
not be present.]
Lanthanum nitrate, carrier solution (30.4 g per liter) - Dissolve
30.4 g of lanthanum nitrate (La(NOg)g.Sl^O) in water and
dilute to 1 liter. This solution will contain 10 g of La+++
per liter.
Manganese chloride, carrier solution (36 g per liter) - Dissolve
36 g of manganese chloride (MnClg.AH^O) in 1 liter of water
and store in a polyethylene bottle. This solution will
contain 10 g of Mri*"*" per liter.
Methyl orange indicator solution (0.5 g per liter) - Dissolve
0.05 g of methyl orange in water and dilute to 100 ml with
water.
Nitric acid solution (1:9) - Mix 1 volume of concentrated nitric
acid (HN03, sp gr 1.42) with 9 volumes of water.
Nitric acid-hydrofluoric acid mixture - Mix 1 volume of concen-
trated nitric acid (HN03, sp gr 1.42), 1 volume of hydro-
fluoric acid (HF, sp gr 1.19), and 98 volumes of water.
25
-------
Nitric acid - hydrogen peroxide mixture - Mix 5 volumes of concen-
trated nitric acid (HN03, sp gr 1.42), 2 volumes of hydrogen
peroxide (H202, 30%), and 13 volumes of water.
Potassium chromate, carrier solution (37.3 g per liter) - Dissolve
37.3 g of potassium chromate (K^CrC^) in 1 liter of water.
This solution will contain 10 g of Cr+++ per liter.
Potassium iodide, carrier solution (13.08 g per liter) - Dissolve
13.08 g of potassium iodide (KI) in 500 ml of water and
dilute to I liter. This solution will contain 10 g of I"
per liter.
Potassium permanganate solution (saturated) - Dissolve 65 g of
potassium permanganate (KMnO^) in 1 liter of warm water and
let cool (solubility = 6.38 g per 100 ml at 20°C).
Scintillator stock solution* — (If prepared in the presence of
daylight or fluorescent light, store in a dark place 2 days
before use.) Dissolve 120 g of naphthalene, 0.05 g of
p-bis (2-(5-phenyloxazolyl)) benzene (POPOP), and 4 g of
2,5-diphenyloxazole (PPO), in 1 liter of p-dioxane. Store in
an amber-colored bottle. This solution must be standardized
initially before use.
^Scintillation grade reagents should be used in the preparation of the
stock solution to assure sample stability in the counting vial for at
least 3-4 weeks.
26
-------
The solvent in the scintillation solution, p-Dioxane, is
flammable and its vapors are toxic. Preparation of the
scintillation solution should be carried out in a hood away
from heat or flames.
Silver nitrate solution (17 g per liter) - Dissolve 17 g o£ silver
nitrate (AgNO-) in 300 ml of water and dilute to 1 liter.
Sodium bisulfite solution (100 g per liter) - Dissolve 10 g of
sodium bisulfite (NaHSCL) in 75 ml of water and dilute to
100 ml. Prepare a new solution when needed. Do not store
for more than one week.
Sodium carbonate solution, saturated (212 g per liter) - Dissolve
212 g of sodium carbonate (Na-CCL) in water and dilute to
1 liter.
Sodium hydroxide solution (200 g per liter) - Dissolve 200 g of
sodium hydroxide (NaOH) in 400 ml of water and dilute to
1 liter.
Sodium nitrite solution (100 g per liter) - Dissolve 10 g of
sodium nitrite (NaN02) in water and dilute to 100 ml.
Sulfuric acid solution (1:4) - Slowly, with stirring, add 1
volume of concentrated sulfuric acid (sp gr 1.84) to 4 volumes
of water.
Sulfuric acid solution (1:9) - Slowly, with stirring, add 1 volume
of concentrated sulfuric acid (^SO^, sp gr 1.84) to 9 volumes
of water.
27
-------
Thenoyltrifluoroacetone (TTA) - Xylene (111 g per liter) - Dissolve
111 g of TTA in xylene and dilute to 1 liter.
Xylene, C&H4(CH3)2: reagent grade.
28
-------
SECTION II
A. Developed and Modified Methods
-------
Radioactive Antimony
Principle of Method
Antimony carrier and appropriate scavenging carriers are added to
the aqueous sample and impurities are removed by a basic sulfide
precipitation. The antimony is collected as the sulfide in acid solu-
tion, and reduced to the metal for counting.
Procedure Time
4 samples - 5 hrs.
Reagents
Antimony carrier: 5 mg/ml
Cobalt carrier: 5 mg/ml
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 12 N (cone.)
Hydrogen sulfide, ^S: gas
Iron, wire #36, analytical grade
Manganese carrier: 5 mg/ml
Sodium hydroxide, NaOH: 18 N, 0.5 N
Sulfuric acid, I^SO^: 36 N (cone.)
Thioacetamide, CH3CSNH2*: 5%
Procedure
1. To an aqueous sample (200 ml or less), add 2.0 ml antimony carrier and
1 ml each of cobalt and manganese holdback carriers (Note 1).
2. Make sample strongly basic (pH > 10) with 18 N NaOH and heat to
boiling (Note 2).
3. Bubble in IkS for 5 minutes to precipitate sulfides completely,
filter while hot through Whatman #41 (or equivalent). Wash filter
*If thioacetamide solution is preferred to hydrogen sulfide, 2 ml of
the solution, with vigorous stirring, can be substituted in those
steps requiring ^S.
30
-------
paper with a few ml 0.5 N NaOH and discard filter paper.
4. Cool sample in an ice bath and neutralize by dropwise addition of
36 N H2SO,.
5. Make sample ~3 N in T^SO^ with 36 N E^SO,. (Note 3).
6. Heat to boiling, then bubble in additional ILS for a few minutes.
7. Cool in an ice bath, centrifuge and discard supernatant.
8. Dissolve the antimony sulfide with 10 ml 12 N HC1 and boil in a
hot water bath for 15 min. to expel H S.
9. Add 5 ml water, 1 ml cobalt carrier and repeat steps 2-8.
10. Add 10 ml water and filter through Whatman #42 (or equivalent) into
a graduated centrifuge tube. Wash residue with a few ml water and
add to filtrate. Bring volume to 40 ml. Discard filter paper.
11. To filtrate add 225-250 mg iron wire. Heat in a boiling water
bath, stirring occasionally until the reduction is complete and all
the antimony has settled to the bottom of the tube. (This takes
45 min. - 1 hr.) Wash sides of tube with a few ml water and add
1 ml 12 N HC1. Stir well and continue heating about 10 min. to
dissolve any residual iron. If necessary add another ml 12 N HC1
to complete the dissolution.
12. Cool slightly, centrifuge and carefully discard supernatant.
13. Wash antimony with 20 ml water and 1 ml 12 N HC1. Heat and stir
in a boiling water bath about 5 min. Cool slightly, centrifuge
and carefully discard wash solution.
31
-------
14. Transfer to a tared glass-fiber filter with water and wash with
successive portions of water and ethanol.
15. Dry in oven at 110 C for 15 minutes, cool, weigh, mount and count.
Calculation
Calculate the concentration, D, of the antimony activity in pico-
curies per milliliter as follows:
D-
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 « conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
A -A e-°-693t/T
o
where:
A =s activity at time t,
AO = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T m half life of separated nuclide, in same units as t.
32
-------
Confirmation of Purity of 124Sb
1. Plot the gamma ray spectrum of the separated sample to identify the
the 124Sb photopeaks at 603 and 1692 keV.
2. Beta-count the planchets at 3-4 week intervals to measure decay and
confirm the 60.2 d half life.
3. Frequent gamma spectral measurements will identify the other
shorter-lived isotopes (2.7 d !22Sb or 5.8 d 129msb). The presence
of the gamma photopeaks at 427, 599 and 634 keV will identify the
longer-lived 125sb isotope (tjy2 = 2-8 y)«
Notes:
1. If the aqueous sample has significant 131x activity, it will be
necessary to modify the procedure to assure complete decontami-
nation from the separated antimony fraction as follows:
a. To 200 ml aqueous sample in a separatory funnel, add 2.0 ml
antimony carrier and 1 ml each iodine, cobalt and manganese
carriers. Add 5 ml 36 N H2S04, stir well, then add 1 ml
1 M NaN02.
b. Add 10 ml CCl^, shake for 5-10 minutes. Discard the organic
layer.
c. To the aqueous layer add 0.5 ml iodine carrier, 0.5 ml
1 M NaN02 and 5 ml CC14. Shake for 5-10 minutes, discard
the organic layer. Repeat.
d. Wash aqueous layer twice with 5 ml CC14 and discard the
organic washes.
e. Add 2 drops 1 M NaN02- Stir and boil for a few minutes to
remove excess N02-
f. Proceed with step 2 of the Antimony procedure.
2. The sample must be strongly basic to ensure that antimony will
stay in solution through the basic sulfide precipitation.
3. Depending on the sample aliquot taken for analysis, the adjust-
ment to 3 N in H2S04 at this point can be made as follows:
a. Add 18 ml 36 N H2S04 and dilute to 225 ml
b. Add 13 ml 36 N H2S04 and dilute to 150 ml
c. Add 8.5 ml 36 N H2S04 and dilute to 100 ml or
d. Add 2.5 ml 36 N H2S04 and dilute^ to 20 ml.
References:
1. Kleinberg, J., Ed., "Collected Radiochemical Procedures", LA-1721,
2nd ed., Los Alamos Scientific Laboratory, U. of Calif., 1958, pp.
156-162.
2. Pocze, L., et^ al_., "Testing of Silver, Antimony, Zinc, Tin and
Selenium Content in High Purity Coppers by Activation Analysis",
Proc. Conf. Appl. Phys.-Chem. Methods Chem. Anal. Budapest 2_,
270-5, 1966.
33
-------
Radioactive Arsenic
Principle of Method
Arsenic carrier and appropriate holdback carriers are added to the
acidified aqueous sample. The arsenic is collected as the sulfide in
acid solution and reduced to the metal for counting.
Procedure Time
2 samples - 3 hrs.
Reagents
Aerosol solution: 1.570
Arsenic carrier: 20 mg/ml
Cobalt carrier: 5 mg/ml
Ethanol, C2HcOH: 95%
Hydrochloric acid, HCl: 12 N (cone.), 6 N
Hydrogen sulfide, BUS: gas
Nitric acid, HNO.,: 16 N (cone.)
Perchloric acid, HCIO^: 70% (cone.)
Sodium hydroxide, NaOH: 2 N
Stannous chloride, SnCl2.2H20: freshly prepared reagent
Procedure
1. To an aqueous sample (100 ml or less), add 5 ml 16 N HNO^, 1.0 ml
arsenic carrier and 0.5 ml cobalt holdback carrier, and evaporate to
dryness.
2. Add 10 ml 12 N HCl to residue and dissolve by heating and stirring
on a hot plate. Transfer to a centrifuge tube with 12 ml 12 N HCl
and make ~9 N in HCl by diluting to 30 ml.
3. Heat almost to boiling in a hot water bath and bubble in H_S until
precipitation of As~S_ is complete. Continue heating and stirring
until precipitate has coagulated. Centrifuge and discard supernatant.
34
-------
4. To the precipitate add 10 ml 2 N NaOH, stir in a hot water bath,
filter through Whatman #41 (or equivalent) into a clean tube and
discard filter paper.
5. Reprecipitate As2S5 by slowly adding 20 ml 12 N HC1. Heat and
stir in a hot water bath and add additional H2S to assure complete
reprecipitation. Heat and stir to coagulate, cool, centrifuge and
discard supernatant.
6. Stir precipitate in a hot water bath with 10 ml 12 N HC1. Add
5 ml water, centrifuge and discard supernatant.
7. To the precipitate, add 0.5 ml each of 16 N HN03 and 12 N HC1 and
1 ml 707. HC104. Stir in hot water bath for 15 minutes, dry outside
of centrifuge tube, then heat carefully over a burner for several
minutes until dense white fumes appear. (Note 1).
8. Cool to room temperature, add 10 ml 6 N HC1 and heat in a boiling
water bath. Slowly add 15 ml freshly prepared stannous chloride
solution, stirring and heating continuously until arsenic is
precipitated and coagulated.
9. Add 2 drops aerosol solution, stir and rinse stirring rod and sides
of the tube with 12 N HC1.
10. Let cool to room temperature, centrifuge and discard supernatant.
11. Wash with 15 ml ethanol and discard wash solution.
12. Transfer to tared glass-fiber filter with ethanol and wash with
ethanol.
13. Dry 10 minutes in an oven, weigh rapidly to keep oxidation of
35
-------
arsenic to a minimum, mount and count immediately.
Calculation
Calculate the concentration, D, of arsenic-76 in picocuries per
milliliter as follows:
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R * fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry as
follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for arsenic-76 as follows:
-0.693t/T
A - A0 e
where:
A = activity at time t,
AQ = activity at time zero,
e - base of natural logarithms,
t = elapsed time, in hours from collection, and
T = half life of ?6As in same units as t (t-^ * 26.4 n).
Confirmation of the Purity and Activity of 76^5
1. Plot the gamma-ray spectrum of the separated sample immediately to
identify the predominant 76As photopeak at 559 keV and to note the
presence of photopeaks indicative of incomplete decontamination.
36
-------
2. Repeat the gamma measurement at 6-, 12-, and 24-hr Intervals to
corroborate the half life of 76As.
Note:
1. It is essential that all HN(>3 be removed to eliminate interfer-
ence with the conversion of arsenic to the metal. However, do
not let sample go to dryness.
References:
1. Lingane, J. J., Analytical Chemistry of Selected Metallic
Elements, (Reinhold, New York, N. Y. 1966) pp. 27-28.
2. Master Analytical Manual, Oak Ridge National Laboratory, USAEC
Report TID-7015, Method 5-110600, 1957.
37
-------
Carbon-14
Principle of Method
Carbon carrier in the form of sodium oxalate is added to an unacidi-
fied aqueous sample in a closed distillation apparatus. An oxidizing
agent and acid are added to the sample to convert carbon compounds to
C02. Air is slowly bubbled through the sample and heat is applied to
transfer C02 into a flask that contains a basic CaCl2 solution. The
collected CaC03 is centrifuged, washed, transferred to a stainless
steel planchet, weighed, and counted.
Procedure Time
1 sample - 1 hr.
Reagent^
(Freshly boiled distilled water should be used in the preparation
of the following reagents.)
Ammonium hydroxide, NH^OH: 0.1 N
Calcium chloride, CaCl2: 1.5 M
Carbon carrier, 0.1 M Na2C204: 20 mg/ml (Note 1).
Potassium permanganate, KMnO^: 0.5 M
Sulfuric acid, H2S04: 18 N
Procedure
1. To an unacidified aqueous sample (200 ml or less) in a distilling
flask (Fig. 2), add 1.0 ml carbon carrier. Close distillation
apparatus. Connect a source of C02-free air to the flask and bubble
gently through the solution (Note 2). Connect distilling outlet to
a 200-tnl receiving flask containing 100 ml 0.1 N NH^OH and 1 ml 1.5 M
CaCl (60 mg Ca**).
2. With the system closed, add 1 ml 0.5 M KMnO^ and 5 ml 18 N
through the separatory funnel to the distilling flask. Close
38
-------
Dropping
Funnel
Sample
Vent
Basic CaCI2
Figure 2. Distillation Apparatus for Carbon-14 Analysis
39
-------
stopcock; swirl, and boil 30 minutes while bubbling air through the
distilling flask into the receiving flask.
3. Transfer the precipitated CaC03 from the receiving flask to a
centrifuge tube. Centrifuge and discard supernatant. (Note 3).
4. Wash precipitate twice with 15 ml portions of boiled distilled
water and discard wash solutions.
5. Transfer quantitatively to a tared stainless steel planchet with
5 ml boiled distilled water.
6. Dry under infra-red lamp. Let cool and weigh. Compute chemical
yield based on the total weight of CaCOg formed. Count with thin-
f\
window (< 2 mg/cm ) beta counter.
Calculation
Calculate the concentration, D, of the carbon-14 activity in pico-
curies per milliliter as follows:
D =
2.22 x EVR
where :
C = net count rate, count s/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Confirmation of Purity and Identification of C (Note 4)
1. Ascertain if the activity is ^C by counting the planchet with
aluminum absorbers up to 25 mg/cm and compare with a standard
1*C absorption curve (Fig. 3).
2. Decay counting for half-life corroboration is not practical
(•^C tjy2 = 5730 y). A 3-month decay count, however, will demon-
strate the absence of short-lived radioactive impurities.
40
-------
1000
Ul
t-
D
z
oe
111
a.
(A
o
u
100
3
O
u
10
T 1 1 \ 1 1 1 1 1 1 1 T
WINDOW
THICKNESS
I I I I I I I I
I
4 6 8 10 12 14 16 18 20 22 24
SURFACE DENSITY-ALUMINUM ABSORBER-mg/cm2
Figure 3. Absorption Curve for Carbon-14 (Ca^CO^ on s.s. planchet)
2.5 mg/cm2 Total Window Thickness Included
41
-------
Notes:
1. The Na2C20^ should be frequently standardized by replicate
determinations. 1 ml 0.1 M Na2C2C>4 is equivalent to 20 mg
CaC03, but the standardized value will include any C02 absorbed
by the carrier solution upon standing.
2. A cylinder of oxygen can serve as an excellent source of CC^-
free air.
3. An alternate method for counting carbon-14 is by liquid scintil-
lation*. At this point, the CaC03 precipitate is dried at 110°C
overnight and cooled in a desiccator. Proceed as follows:
a. Transfer quantitatively to a tared scintillation vial, add
450 mg Cab-o-sil, and suspend the mixture in 15 ml of a
freshly prepared toluene scintillation solution. Agitate
until uniform.
b. Prepare a 14c standard and a background sample in a similar
manner.
c. After determining optimum voltage and window settings, count
at least three times to be certain the samples have been
dark adapted.
4. If it is evident that another radionuclide contaminates the I4c,
the following corrective measures can be taken:
a. Wash the CaCOg from the stainless steel planchet into a
round bottom flask with boiled distilled water. Bring the
volume to ~100 ml with boiled distilled water. Add the
necessary holdback carrier (cobalt, manganese, etc.) and
close the distilling system as before.
b. Connect the distilling outlet to a 200-ml flask containing
100 ml 0.1 NH4OH and 1 ml 1.5 M CaCl2.
c. With the system closed, add 2 ml 6 N HC1 to the sample
through the separatory funnel. Swirl. Boil gently for
15 minutes.
d. Repeat the collection, washing, mounting, weighing and
counting of CaCO^ as before.
Reference:
1. Rodden, C. J., Ed., Analysis of Essential Nuclear Reactor
Materials (Div. Tech. Inf. USAEC, 1964) p. 561.
*Rapkin, E., "Measurement of 14C02 by Scintillation Techniques",
Packard Technical Bulletin #7, Packard Instrument Co., La .Grange 111
1962.
42
-------
Radioactive Cerium
Principle of Method
Cerium carrier is added to the aqueous sample, which is evaporated
to dryness, taken up in concentrated HC1 and passed through a mixed
anion resin column. (Note 1). Manganese is scavenged from the effluent,
and the cerium is precipitated as Ce(IOo)A for counting.
Procedure Time
2 samples - 6 hrs.
Reagents
Anion Exchange Resins
Dowex 1-X8 (100-200 mesh)
Dowex 2-X8 (20-50 mesh)
Cerium carrier: 5 mg/ml
Cobalt carrier: 5 mg/ml
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 12 N (cone.), 6 N
Hydrogen peroxide,t E2°2: 307°
Manganese carrier: 5 mg/ml
Nitric acid, HN03: 16 N (cone.)
Potassium bromate, KBrO-j: solid
Potassium iodate, KlOg: prepared reagent
Potassium iodate wash solution, 003: prepared reagent
Procedure
1. To an aqueous sample (100 ml or less), add 1.0 ml cerium carrier,
0.5 ml 6 N HC1 and evaporate to dryness.
2. Prepare a mixed anion exchange resin column as follows:
Individually equilibrate 10 g Dowex 1-X8 anion resin (100-200 mesh)
and 10 g Dowex 2-X8 anion resin (20-50 mesh) with 50 ml 12 N HC1
each. Into a glass column, 0.9 cm (I.D.) x 30 cm, slurry Dowex 2-X8
to a height of 5 cm, then add the Dowex 1-X8 resin.
43
-------
3. Dissolve residue in 10 ml 12 N HC1 and add 1 drop H202 to reduce
the cerium to the cerous (+3) state.
4. Add 1 ml cobalt carrier to the solution, stir well. Pass over
column at a rate of 0.25 ml/min. Collect effluent in a beaker.
5. Wash column with 15 ml 12 N HC1 and add wash to effluent in the
beaker.
6. Evaporate effluent almost to dryness to remove chlorides. Do not
bake. Dissolve residue in 50 ml water, add 0.5 ml manganese
carrier and 2.5 ml 16 N HN03.
7. Heat to boiling and slowly add 1 g KBrOg. Boil until Mn02
coagulates. Cool, centrifuge, and filter supernatant through
Whatman #42 (or equivalent), into a clean beaker. Wash filter
paper with a few ml water, and discard filter paper.
8. Heat solution to boiling and add a pinch of KBrO« to assure complete
oxidation to the eerie (+4) state.
9. Add 20 ml KI03 solution, stir and boil until the Ce(I03),
coagulates. Cool, centrifuge and discard supernatant.
10. Wash precipitate twice with 15 ml KI03 wash solution and discard
washings.
11. Transfer to a tared glass-fiber filter with KI03 wash solution.
12. Wash with successive portions of KI03 wash solution, water and
ethanol.
13. Dry in oven at 110°C for 15 minutes, cool, weigh, mount and count.
44
-------
Calculation
Calculate the concentration, D, of the cerium activity in pico-
curies per milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry as
follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
-0.693t/T
A = A e
o
where:
A - activity at time t,
AQ = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclides, in same units as t.
Confirmation and Identification of Cerium Isotopes
1. Plot the gamma-ray spectrum of the separated sample to identify the
^Ce photopeak at 145 keV, the 143Ce photopeak at 293 keV, and/or the
144Ce photopeak at 134 keV.
2. Beta count the planchets at 2-week intervals to measure decay and
confirm the 32.5 d half life of l^lce. the 33 hr half life of
) and/or the 284 d half life of
45
-------
Note:
1. A mixed anion resin is employed because,from a 12 N HC1 solution,
ruthenium and molybdenum are strongly adsorbed on Dowex 1;
niobium is quantitatively adsorbed on Dowex 2; protactinium and
zirconium are adsorbed equally well on either resin, whereas
Ce"*"^ passes quantitatively into the effluent.
Reference:
1. Albu-Yaron, Ana, Mueller, D. W. and Settle, A. D., Jr.,
"Chemical Separation of Cerium Fission Products from Microgram
Quantities of Uranium", Anal. Chem. 41, 1351, August 1969.
46
-------
Radioactive Cesium
Principle of Method
Cesium carrier is added to the aqueous sample. The cesium is
collected as the phosphomolybdate and purified as Cs2PtClg for counting.
Procedure Time
4 samples - 5 hrs.
Reagents
Ammonium phosphomolybdate, (NH^EMoj^^O1 prepared reagent
Calcium chloride, CaCl2: 3 M
Cesium carrier: 10 mg/ml
Chloroplatinic acid, E^PtClg.ei^O: 0.1 M
Ethanol, CaHsOH: 95%
Hydrochloric acid, HC1: 12 N (cone.), 6 N, 1 N
Sodium hydroxide, NaOH: 6 N
Procedure
1. To an aqueous sample (1000 ml or less), add 1.0 ml cesium carrier,
and enough 12 N_ HC1 to make the solution ~0.1 N HC1.
2. Slowly add 1 g ammonium phosphomolybdate and stir for 30 minutes,
using a magnetic stirrer. Allow precipitate to settle for at least
4 hours, and discard supernatant. (Note 1).
3. Slurry precipitate into a centrifuge tube. Centrifuge and discard
supernatant.
4. Wash precipitate with 20 ml 1 N HC1, and discard wash solution.
5. Dissolve precipitate by dropwise addition of 3-5 ml 6 tJ NaOH. Heat
over a flame for several minutes to remove ammonium ions. (Moist
pH paper turns green as long as NH3 vapors are evolved.) Dilute to
20 ml with water.
47
-------
6. Add 10 ml 3 M CaCl2 and adjust to pH 7 with 6 N HCl to precipitate
CaMoOy.. Stir, centrifuge and filter supernatant through Whatman
#41 (or equivalent) into a 50 ml centrifuge tube.
7. Wash the precipitate remaining in the centrifuge tube with 10 ml
water; filter through the same filter paper, and combine the wash
with the filtrate. Discard filter paper.
8. Add 2 ml 0.1 M HgPtClg and 5 ml ethanol. Cool and stir in ice bath
/
for 10 minutes.
9. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water, 1 N HCl and ethanol.
10. Dry, cool, weigh, mount and count.
Calculation
Calculate the concentration, D, of the cesium activity in pico-
curies per milliliter as follows:
D -
2.22 x EVR
where:
C - net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry as
follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
48
-------
Calculate decay corrections as follows:
-0.693t/T
= A0 e
where:
A = activity at time t,
A0 = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclide, in same units as t.
Confirmation of Purity of 13^Cs» 136Cs and 137Cs, and Identification of
Cesium Isotopes
1. Plot the gamma-ray spectrum of the separated sample. The main
134Cs photopeaks are at 605 keV and 796 keV: the main 136Cs photo-
peaks are at 818 keV and 1050 keV; and the *37Cs photopeak is at
662 keV.
2. Repeat gamma spectral measurements at 1-week intervals to measure
decay of the l36Cs (ti/2 = 13 d).
3. Beta count at 1-month intervals to measure decay and confirm half-
life value for 134cs (2.07 yr).
Note:
1. If a small volume sample is analyzed, it is possible to transfer
the solution directly to a centrifuge tube and there would be no
need for lengthy settling time.
Reference:
1. Finston, H. L. and Kinsley, M. T., "The Radiochemistry of
Cesium", AEC Rept. NAS-NS-3035 (1961).
49
-------
Radioactive Chromium
Principle of Method*
+3
Chromium carrier (Cr ) and appropriate holdback carriers are
added to the acidified aqueous sample. Chromium is oxidized to the
chromate (Cr+6), and impurities are removed by nitric acid evapora-
tions (to volatilize radioiodine) and cation exchange. The chromium
is precipitated as BaCrO, for counting.
Procedure Time
2 samples - 5 hrs.
Reagents
Cation exchange resin
Dowex 50W-X8 (100-200 mesh)
Ammonium chloride, NH^d: 10%
Ammonium hydroxide, NHAOH: 1 N
Barium nitrate, Ba(N03)2: 10%
Cesium carrier: 10 mg/ml „
Chromium carrier: 10 mg/ml as Cr
Cobalt carrier: 5 mg/ml
Ethanol, C2%OH: 95%
Hydrochloric acid, HC1: 12 N (cone.)
Iron carrier: 10 mg/ml
Nitric acid, HN03: 16 N (cone.)
Sodium hypochlorite, NaOCl: 5%
Sodium metaperiodate, NalO^: solid
Procedure
1. To an aqueous sample (100 ml or less), add 1 ml 16 N HN03, 1.0 ml
chromium carrier and 0.1 ml each of iron, cobalt and cesium holdback
carriers. Mix well and evaporate sample to dryness (do not bake).
*This procedure was developed by Robert Lieberman, Analytical and
Radiochemistry Research Section, EERF, Montgomery, Alabama 36101,
50
-------
2. Prepare a cation exchange resin column as follows:
Slurry Dowex 50W-X8 resin (100-200 mesh) with water and transfer to
a column 2.5 cm (I.D.) x 30 cm until a layer 8 cm deep is formed.
Wash column with 100 ml water and pass 100 ml 10% NH^Cl through the
column. Wash column with another 100 ml water. (Note 1).
3. Cool the residue from step 1. Add 25 ml 16 N[ HNO-j and evaporate to
dryness. Repeat.
4. Slurry residue with 35 ml water. Heat to boiling and add 50 ml
water.
5. Add 1 ml 5% NaOCl and continue heating for 5 minutes.
6. Add 1 ml 16 N HNOo and evaporate sample to approximately 75 ml.
[Sample should have a bright yellow color at this stage.] Cool.
7. Pass the solution over the cation exchange resin column at a rate
of 2 ml/min and collect effluent in a 250 ml beaker.
8. Wash the column with 100 ml water and add this wash to the effluent
from step 7.
9. Adjust the sample to pH 5 with 1 N NH^OH, add 2 ml 10% Ba(N03>2 and
stir for 1 hour to precipitate barium chromate. Allow precipitate
to settle and discard the clear supernatant.
10. Slurry the precipitate into a centrifuge tube with 15 ml water.
Centrifuge and discard supernatant.
11. Wash the precipitate with 20 ml water and discard wash solution.
12. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
13. Dry, cool, weigh, mount and count.
51
-------
Calculation
Calculate the concentration, D, of the chromium activity in pico-
curies per milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry as
follows:
E - Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
-0.693t/T
A = A e
o
where:
A = activity at time t,
AQ = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of 51Cr in same units as t, (t/ = 27.8 d) .
Confirmation of Purity of 51(]r Activity and Measurement of Activity
1. Plot the gamma-ray spectrum of the separated sample. The
photopeak is at 320 keV.
2. Repeat gamma spectral measurement at 1-month intervals to measure
decay and confirm the purity of the
52
-------
Note:
1. The cation resin is regenerated by passing 200 ml 12 N HC1
through the column. It is then prepared for subsequent use by
washing with 100 ml water, followed by 100 ml 10% NH^l and a
final wash with 100 ml water.
Reference:
1. Pijck, J., "Radiochemistry of Chromium", AEC Rept. NAS-NS-3007,
1964.
53
-------
Radioactive Cobalt and Cadmium
Principle of Method
Cobalt and cadmium carriers are added to the aqueous sample and
collected as insoluble hydroxides. The cobalt is precipitated and
purified as K3Co(N02)g for counting; cadmium is precipitated as the
sulfide in acid solution and purified as Cd(OH)2 fox counting.
Procedure Time
4 samples - 8 hrs.
Reagents
Acetic acid, CH3COOH: 8 N
Ammonium acetate buffer, (CHoCOOH-CHoCOONH^.): pH 5.0
Cadmium carrier: 20 mg/ml
Cobalt carrier: 5 mg/ml
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 12 N (cone.), 2 N
Hydrogen peroxide, H202: 30^°
Hydrogen sulfide, H2S: gas
Potassium hydroxide, KOH: 6 N
Potassium nitrite wash solution: (1:100)
Potassium nitrite, KN02: solid
Nitric acid, HN03: 16 N (cone.), 6 N
Sodium hydroxide, NaOH: 6 N, 2 N
Thioacetamide, CH3CSNH2*: 5%
Procedure
1. To an aqueous sample (100 ml or less), add 1.0 ml each of cobalt
and cadmium carriers.
2. Slowly add at least 2 drops H202 and 6 N KOH until precipitation
of hydrous oxides is complete. Heat to coagulate, cool, centrifuge
*If thioacetamide solution is preferred to hydrogen sulfide, 2 ml of
the solution, with vigorous stirring, can be substituted in those
steps requiring ^S.
54
-------
and discard supernatant. (Note 1).
3. Dissolve precipitate in 5 ml 8 N acetic acid and 2 drops H202 with
heating. Dilute to 15 ml with water, add 5 ml ammonium acetate
buffer solution (pH 5) and heat to boiling in a water bath.
Carefully add 5 g KN02 in small increments, with stirring.
Continue boiling until gas evolution ceases and the potassium
cobaltinitrite precipitate coagulates and settles. Cool, centri-
fuge, and filter supernatant containing the cadmium through
Whatman #42 (or equivalent). Discard filter paper. Reserve the
supernatant for the cadmium purification, steps 11 through 18.
4. Wash cobalt precipitate with 10 ml water and discard wash solution.
5. Dissolve precipitate with 1-2 ml 12 N HC1 by heating and stirring
until the solution is a clear blue.
6. Dilute to 10 ml and add at least 2 drops H202 and 6 N KOH until
hydrous oxide precipitation is complete. Heat to coagulate, cool,
centrifuge and discard supernatant.
7. Dissolve the precipitate in 5 ml 8 N acetic acid and 2 drops H202
by heating in a boiling water bath. Dilute to 15 ml with water,
add 5 ml ammonium acetate buffer solution, heat to boiling and
carefully add 5 g KN02 in small increments with stirring. Continue
boiling until gas evolution ceases and the potassium cobaltinitrite
precipitate settles. Cool at least 30 minutes, centrifuge and
discard supernatant.
55
-------
8. Wash precipitate with 15 ml KN02-wash solution and discard wash
solution.
9. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
10. Dry, cool, weigh, mount and count cobalt activity.
11. To the supernatant from step 3, add 6 N NaOH until the precipita-
tion is complete. Stir in a water bath for a few minutes and let
the precipitate settle. Centrifuge and discard supernatant.
12. Dissolve the precipitate with 1 ml 12 N HC1, dilute to 50 ml and
heat almost to boiling.
13. Bubble in H2S for one minute to precipitate CdS. Cool, centrifuge
and discard supernatant.
14. To the precipitate add 15 ml 2 N NaOH and stir in water bath for
15 minutes.
15. Cool, centrifuge and discard supernatant. Wash precipitate with
20 ml water and discard wash solution.
16. Dissolve precipitate with 2 ml 6 N 1M>3 with heating and add 10 ml
water (Note 2).
17. Add 6 N NaOH until Cd(OH)2 precipitate forms. Cool and filter
through a tared glass-fiber filter. Wash with successive portions
of water and ethanol.
18. Dry, cool, weigh, mount and count the cadmium activity.
56
-------
Calculations
I. Cobalt isotopes
Calculate the concentration, D, of cobalt-57, cobalt-58 and
cobalt-60 in picocuries per milliliter as follows:
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
for each cobalt isotope as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for the cobalt isotopes as follows:
-0.693t/T
A- AQ e
where:
A = activity at time t,
A0 = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclide, in same units as t.
Confirmation and Identification of Cobalt Isotopes
1. Plot gamma-ray spectrum of separated sample immediately to
identify the 57Co (122 keV), 58Co (511 keV and 810 keV) and
60Co (1173 keV, 1332 keV and the 2505 keV sum) photopeaks.
57
-------
2. Repeat the gamma measurement after 2 and 4 weeks to observe the
decay of the shorter-lived isotopes.
3. Beta count the planchet immediately and at 1-month intervals to
corroborate the half lives of 58Co (270 d) and 60Co (5.26 yr).
(Note 3).
II. Cadmium isotopes
Calculate the concentration, counter efficiency and decay correc-
tion for cadmium-109 and cadmium-HSm in picocuries per milliliters as
shown above for cobalt isotopes.
ConfirmationandIdentification of Cadmium Isotopes
1. Plot the gamma ray spectrum of the separated sample to identify
the 109Cd photopeak at 88 keV and the 115mCd photopeak at 485 keV.
2. Beta count the planchet at 2-week intervals to measure decay and
confirm the 43 d half life of H5mcd and/or the 453 d half life
of
Notes:
1. More 1^02 may be needed if H202 is not absolutely fresh or if
the sample contains reducing reagents. An excess of EkjC^ will
not hinder the analysis.
2. If any undissolved residue remains at this point, the solution
should be filtered and the clear supernatant transferred to a
clean centrifuge tube.
3. The ^OK beta in K3Co(N02)g will add approximately 10 dpm per
20 mg separated precipitate, and this background must be taken
into consideration during the beta-decay counting.
References:
1. Lingane, J. J., Lingane, P. J. and Morris, M. D., Anal. Chim.
Acta, 2_9, 10 (1963).
2. Lingane, J. J. , ibid, 3_1, 315 (1964).
58
-------
Radioactive Cobalt and Nickel
Principle of Method
Cobalt and nickel carriers are added to the aqueous sample and
precipitated as insoluble hydroxides. The cobalt is separated and
purified as K3Co(N02)g for counting. The nickel is reprecipitated as
the hydroxide, purified with dimethyIglyoxime and collected as the
hydroxide dissolved in caproic acid. To measure ^Ni, the solution is
mixed with scintillation solution and counted in a liquid scintillation
spectrometer.
Procedure Time
2 samples - 8 hrs.
Reagents
Anion exchange resin
Dowex 1-X8 (20-50 mesh)
Acetic acid, CH3COOH: 8 N
Ammonium acetate buffer, (CHoCOOH-CH-COONH,): pH 5.0
Ammonium hydroxide, NH/OH: 15 N (cone.)
Caproic acid, CH3(CH2)4COOH
Chloroform, CHC13
Cobalt carrier: 5 mg/ml
DimethyIglyoxime, (CH3C:NOH)2: 1% in C2H5OH
Ethanol, C2H50H: absolute (99.5%), 95%
Hydrochloric acid, HC1: 12 N (cone.), 4 N
Hydrogen peroxide, H2<>2: 30%
Lanthanum carrier: 10 mg/ml
Nickel carrier: 5 mg/ml
Nitric acid, HN03: 16 N (cone.), 6 N
Potassium hydroxide, KOH: 6 N
Potassium nitrite wash solution: (1:100)
Potassium nitrite, KN02: solid
Scintillation solution (toluene), prepared reagent
Sodium citrate, Na^CgH507.2H20: 10%
Sodium hydroxide, NaOH: 6 N
59
-------
Procedure
1. To an aqueous sample (100 ml or less), add 1.0 ml each of cobalt
and nickel carriers.
2. Proceed with steps 2-10, of the Cobalt and Cadmium procedure,
page 61, to separate and purify the cobalt. Reserve the super-
natant from step 3, Cobalt and Cadmium procedure for nickel
purification.
3. Prepare an anion column equilibrated on the Cl cycle as. follows:
Slurry Dowex 1-X8 (20-50 mesh) resin with water and transfer to a
column 1.0 cm (I.D.) x 20 cm until a layer 10 cm deep is formed.
Wash column with 25 ml water and 50 ml 12 El HC1 before each use.
4. To the supernatant containing the nickel activity, add 6 N KOH
until precipitation of nickel hydroxide is complete. Heat to
coagulate, cool, centrifuge and discard supernatant.
5. Wash precipitate with 20 ml water and discard wash solution.
a-
6. Dissolve precipitate by warming in 2 ml 12 N HCl. Add 5 ml 12 N
HC1 and pass solution over the anion resin column previously
equilibrated with 50 ml 12 N HCl. Wash column with 10 ml 12 N HCl
and collect entire effluent in a 100 ml beaker. (Note 1).
7. Evaporate effluent almost to dryness and transfer to a centrifuge
tube with a little water. Add 1 ml lanthanum carrier, 10 ml
water and make solution basic with excess 15 N NH.OH. Centrifuge,
decant supernatant into a 500 ml separatory funnel and discard
precipitate.
60
-------
8. Mix 5 ml 10% sodium citrate and 10 ml 1% dimethylglyoxime with
solution in separatory funnel. Extract the nickel dimethylglyoxi-
mate into chloroform by shaking for 5 minutes with 300 ml
chloroform. Drain chloroform layer into a beaker and discard
aqueous phase. (Perform extraction in hood.)
9. Four chloroform layer into a clean separatory funnel and wash
twice with 50 ml portions of water containing 0.5 ml 15 N NH^OH.
Drain chloroform layer into a beaker, discard the wash solution
and return the chloroform to the separatory funnel.
10. Add 25 ml 4 N HC1 to chloroform and extract nickel into HC1 solu-
tion by shaking 5 minutes. Discard chloroform layer and drain
aqueous phase into a 100 ml beaker.
11. Evaporate solution to dryness (do not bake), cool, add 10 ml 16 N
HNOo and evaporate to dryness again. Cool, take up residue in
4 ml 12 N HC1 and transfer to a. centrifuge tube with a little
water. (Note 2).
12. Make solution basic with 6 N NaOH to precipitate nickel hydroxide,
centrifuge and discard supernatant.
13. Dissolve precipitate with 1-2 ml 12 N HC1 and dilute to 5 ml with
water.
14. Add 15 N NltyOH until solution is strongly basic, then add 5-10 ml
1% dimethylglyoxime to precipitate nickel dimethylglyoximate. Stir,
centrifuge and discard supernatant.
61
-------
15. Wash with a mixture of 15 ml water and 15 ml 95% ethanol and
discard wash solution.
16. Slurry precipitate with 95% ethanol on a tared stainless steel
planchet. Dry, cool and weigh for chemical yield determination
and beta measurement in gas flow counter. (Note 3).
17. Dissolve precipitate with 1-2 ml 12 N HCl, add 10 ml 16 N HN03
and evaporate to dryness. Repeat with an additional 5 ml 16 N
HN03. Dissolve residue with 5 ml 12 N HCl and evaporate to
dryness. Repeat with an additional 5 ml 12 N HCl. Transfer to
centrifuge tube by rinsing beaker with a few ml 12 N HCl followed
by a little water. Heat to dissolve, and filter if any residue
remains.
18. Make solution basic with 6 N NaOH to precipitate nickel hydroxide,
centrifuge and discard supernatant.
19. Wash precipitate with a few ml water added to a few ml 95% ethanol,
Centrifuge and discard wash solution.
20. Dissolve precipitate in 1 ml caproic acid and add 3 ml absolute
ethanol. Transfer to a low-K glass liquid scintillation vial
containing 16 ml toluene scintillation solution. Shake well and
dark-adapt sample prior to counting.
21. Prepare background and "%i standard samples in a similar manner
and count alternately at predetermined settings. (Note 4).
62
-------
Calculations
I. Cobalt isotopes
Calculate the concentration, D, of cobalt-57, cobalt-58 and
cobalt-60 in picocuries per milliliter as follows:
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V - milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
for each cobalt isotope as follows:
E = Fp
where:
E = fractional abundance of the gamma ray, gammas/disintegration, and
p * photopeak detection efficiency, counts/ gamma ray.
Calculate the decay correction for the cobalt isotopes as follows:
-0.693t/T
where:
A = activity at time t,
A0 = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclide in same units as t.
Confirmation and Identification of Cobalt Isotopes
1, Plot gamma-ray spectrum of separated sample immediately to
identify the 57Co (122 keV), 58Co (511 keV and 810 keV) and ouCo
(1173 keV, 1332 keV and the 2505 keV sum) photopeaks
63
-------
2. Repeat the gamma measurement after 4 weeks to observe the decay
of the shorter-lived isotopes.
3. Beta count the planchet immediately and at 1-month intervals to
corroborate half lives of 58co (71 d), 57co (270 d) and 60c0
(5.26 yr).
II. Nickel-63
a. Gas-flow beta counter
Calculate the concentration, D, of nickel-63 in picocuries per
milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
b. Liquid scintillation analyzer
Calculate the concentration, D, of nickel-63 in picocuries per
milliliter as follows:
S-B
2.22 x EVR
where:
S = counts/min accumulated in sample,
B = background of blank in counts/min,
V = milliliters of sample used,
R = fractional chemical yield as determined in step 16, and
2.22 = conversion factor from disintegrations/min to picocuries.
Confirmation of 63Ni Activity
A. Gas-flow beta counter
1. Determine the activity of 6%i by counting the stainless
steel planchet with aluminum absorbers up to 10 mg/cnr and compare
with a standard ^^Ni absorption curve (Fig. 4).
64
-------
1000
V
\
I 1 1 1 1
100
Z
3
O
u
WINDOW
THICKNESS
O
u
10
1
1
1
2 4 6 8 10
SURFACE DENSITY-ALUMINUM ABSORBER-mg/cm2
12
Figure 4. Absorption Curve for Nickel-63 Analysis (6%iDMG on s.s. planchet)
2.5 mg/cm2 Total Window Thickness Included
65
-------
2. Decay count over a period of 3 months to demonstrate the
absence of short-lived radioactive impurities.
B. Liquid scintillation spectrometer
1. Determine the count rate for each sample, background and
standard at two selected window settings. Compare the ratios for the
6%i standard with that for the samples to confirm that the activity
being measured is nickel-63 (half life 92 y). -
2. To make certain that the samples have been dark-adapted,
count at least three times until successive results are within 2 cr
differences of each other.
Notes:
1. Any cobalt interference is removed by anion exchange separation
of its chloride complex.
2. Steps 13-17 are included to prepare the purified nickel
dimethylglyoxime for beta particle counting and chemical yield
determination. These steps can be omitted if chemical yield
determination is not desired.
3. Steps 17-20 must be performed quantitatively if the chemical
yield determined in step 16 is to be used in the calculation.
4. The samples are counted alternately with standard 63Ni and
background samples to nullify errors produced by aging of the
scintillation medium or instrument drift.
Reference:
1. Gleit, C. E. and Dumot, J., Int. J. Appl. Radiat. 1.2, 1-2, 66
(1961).
66
-------
Radioactive Copper and Technetium
Principle of Method
Copper carrier and appropriate holdback carriers are added to an
acidified aqueous sample and both copper and technetium are precipi-
tated as sulfides. After dissolving the precipitate, the technetium
is separated from the copper by cation exchange purification and
coprecipitated with copper carrier as CuS for counting. The copper is
eluted from the resin column, reduced to Cu+ with Na2S03, and precipi-
tated as CuSCN for counting.
Procedure Time
2 samples - 6 hrs.
Reagents
Cation exchange resin
Dowex 50W-X8 (100-200 mesh)
Ammonium hydroxide, NHAOH: 15 N (cone.), 2 N
Cesium carrier: 10 mg/ml
Cobalt carrier: 5 mg/ml
Copper carrier: 20 mg/ml
Ethanol, C2H5OH: 95%, 20%
Hydrochloric acid, HC1: 12 N (cone.), 6 N, 0.5 N
Iron carrier: 10 mg/ml
Nitric acid, HN03: 16 N (cone.), 6 N
Potassium thiocyanate, KSCN: 0.75 M
Potassium thiocyanate wash solution: (1:200)
Silver carrier: 20 mg/ml
Sodium sulfite, Na2S03: solid
Sulfuric acid, H^SO, : 36 N (cone.), 3 N
Thioacetamide, CI^CSNI^ : 5%
Procedure
1. To an aqueous sample (100 ml or less), acidified with 6 N HN03, add
1.0 ml copper carrier and 1 ml silver carrier.
2. Heat nearly to boiling and add 1 ml 0.5 N HC1 dropwise while
stirring. Digest until AgCl precipitates. Cool, filter through
67
-------
Whatman #42 (or equivalent) into a clean beaker. Discard filter
paper.
3. To filter add 0.5 ml each cobalt, iron and cesium carriers,
neutralize with 15 N NH^OH, then add enough 36 N H2SO^ to make the
solution 3 N in 112804. Heat to near boiling and add dropwise, with
stirring, 2 ml 5% thioacetamide. Digest on the hot plate and stir
until the copper and technetium sulfides coagulate. Cool,
centrifuge and discard supernatant.
4. Wash precipitate with 10 ml 3 N H2S04 containing a few drops 5%
thioacetamide and discard wash solution.
5. Dissolve precipitate in 1 ml 16 N HN03 by stirring and heating in
a boiling water bath until solution is clear green and only a
small amount of light colored residue remains. Add 5 ml water and
9
filter through Whatman #41 (or equivalent) into a clean centrifuge
tube. Wash the residue with a few ml water, add wash water to
filtrate, and discard filter paper.
6. Add 3 ml 15 N NH4OH and dilute to 15 ml. Pour solution over a
previously prepared Dowex 50W-X8 (100-200 mesh) cation resin
column 1 cm (I.D.) x 6 cm in depth which has been equilibrated
with 50 ml 2 N NIfyOH.
7. Collect the technetitim fraction effluent at 1 ml/min in a
centrifuge tube. Wash column with 10 ml 2 N NH4OH, collect in
same tube and proceed with the technetium purification. The resin
column containing the copper fraction is set aside until step 12.
68
-------
8. Neutralize effluent with 36 N I^SO^. Make the solution 3 N in
H2S04 by adding 2.5 ml 36 N H2S04 and diluting to 30 ml. Add
0.5 ml copper carrier, heat to near boiling and add dropwise, with
stirring 2 ml 57, thioacetamide to precipitate copper sulfide which
carries the technetium activity. Digest in a water bath and stir
until the precipitate coagulates. Cool, centrifuge and discard
supernatant.
9. Wash precipitate with 10 ml 3 N H2S04 containing a few drops 5%
thioacetamide and discard wash solution.
10. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
11. Dry, cool, weigh, mount and count the technetium activity.
12. Elute copper from resin column with 15 ml 6 N HC1 and collect in
a beaker. Wash column with 10 ml 6 N HCl and add to beaker.
13. Evaporate to dryness. Slurry with 5 drops 6 N HCl and transfer to
a centrifuge tube with 30 ml water.
14. Heat in a boiling water bath and reduce the Cu"*"*" to Cu~*" by adding
Na2S03 in small increments (a few grains on the tip of a spatula
each time) with stirring until the solution is colorless and smells
of S02. Add 1 ml 0.75 M KSCN and stir until CuSCN has coagulated.
Cool, centrifuge and discard supernatant.
15. Wash with 10 ml KSCN-wash solution in which a few grains of Na2SOg
have been dissolved, and discard wash solution.
69
-------
16. Transfer to a tared glass-fiber filter with a few ml KSCN-wash
solution. Wash 3 times with 5 ml 207» ethanol.
17. Dry, cool, weigh, mount and count the copper activity.
Calculations
I. Copper-64
Calculate the concentration, D, of copper-64 in picocuries per
milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for 64cu as follows:
-0.693t/T
A- AQ e
where:
A = activity at time t,
A = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of the separated nuclide, in same units as t.
70
-------
Confirmation of Purity and Identification of
1. Plot the gamma-ray spectrum of the separated sample immediately to
identify the 64Cu photopeak (511 keV) and verify the purity of the
separation.
2. Repeat the gamma measurement daily for a week to follow decay of
the photopeak.
3. Beta count the planchet at 2-, 6-, 12-, 24- and 48-hr intervals to
corroborate the 12.8-hr half life,
II. Technet ium-99m
Calculate the concentration, D, of 99mTc in picocuries per
milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used, '
R = fractional chemical yield for the separation (Note 1), and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for 99rarc as follows:
-0.693t/T
A - A0 e
where:
A = activity at time t,
Ao = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T « half life of 99lttTc, in same units as t.
71
-------
Confirmation of Purity and Identification of
1. Plot the gamma-ray spectrum of the separated sample immediately
and again in 4 hours to identify the *Vrc photopeak (140 keV) and
to follow its decay.
2. Gamma scan the planchet after 24 hours to verify the 6.0-hr half
life of 99mTC.
Note:
1. The chemical yield for 99mTc (step 11), does not account for
any losses that may occur in the first seven steps. Studies
with long-lived 99Tc have indicated that > 95% of the
technetium activity was present in the resin effluent. Analysts
should determine their own average tracer loss and incorporate
it in the calculations.
References:
1. Master Analytical Manual, Oak Ridge National Laboratory, USAEC
Rept. TID-7015, Method 5-11230, 1957.
2. Anders, E., "The Radiochemistry of Technetium", USAEC Rept.,
NAS-NS-3021, 1960.
3. Kolthoff, I, M. and Sandell, E. B., Textbook of Quantitative
Inorganic Analysis, (Macmillan, New York, N. Y., 1952) p. 671.
72
-------
Radioactive Iodine
Principle of Method
Iodide carrier and appropriate holdback carriers are added to the
sample. The sample is acidified, and iodine is distilled into caustic
solution. The distillate is acidified and the iodine is extracted
into CCl^. After back extraction, the iodine is purified as Agl for
counting.
Procedure Time
2 samples - 6 hrs.
Reagents
Ammonium hydroxide, NHX)H: 15 1? (cone.)
Carbon tetrachloride, CCl^
Cobalt carrier: 5 mg/ml
Diethy1 ether, (C2H5)20: anhydrous
Ethanol, CaHsOH: 95%
Iodide carrier: 20 mg/ml
Nitric acid, HN03: 16 N (cone.), 4 N, 0.2 N
Silver nitrate, AgNC^: 0.1 M
Sodium bisulfite, NaHS03: 1 M
Sodium hydroxide, NaOH: 0.5 N
Sodium nitrite, NaN02: 1 M
Sulfuric acid, H^SO^ 12 N
Tartaric acid, C^gOg: 50%
Procedure
1. To an unacidified aqueous sample (100 ml or less), in a 250 ml
round bottom flask, add 15 ml 50% tartaric acid, 1.0 ml iodide
carrier and 1 ml cobalt holdback carrier. Mix well, cautiously add
15 ml cold 16 N HNO~ and close the distillation apparatus (Note 1).
2. Distill at least 15 minutes into 15 ml 0.5 N NaOH. Cool and
transfer the NaOH solution to a 60 ml separatory funnel. Discard
the solution in the round bottom flask.
73
-------
3. Adjust the solution to slightly acid with 1 ml 12 N H2S04 and
oxidize with 1 ml 1 M NaNO^ Add 10 ml CCl^ and shake for 5-10
minutes. Draw off organic layer into a clean 60 ml separatory
funnel containing 2 ml 1 M NaHS03.
4. Add 5 ml CC14 and 1 ml 1 M NaN02 to the original separatory funnel
containing the aqueous layer and shake for 5-10 minutes. Combine
the organic fraction with that in the separatory funnel in step 3.
5. Repeat step 4 and discard the aqueous layer.
6. Shake separatory funnel thoroughly until CC14 layer is decolorized,
allow phases to separate and transfer aqueous layer to a centrifuge
tube.
7. Add 2 ml 1 M NaHS03 to separatory funnel which has the CCl^ and
shake for several minutes. When the phases separate, combine this
aqueous layer with that in centrifuge tube from step 6.
8. Add 1 ml water to separatory funnel and shake for several minutes.
When the phases separate, add aqueous layer to the same centrifuge
tube. Discard organic layer.
9. To the combined aqueous fractions, add 2 ml 0.1 M AgNOn plus 4 ml
HN03* Stir for 1 minute then allow to stand 30 minutes at room
temperature to coagulate silver iodide. Centrifuge at high speed
for 10 minutes. Carefully decant and discard supernatant.
10. Pipet 5 ml 15 N NH^OH into the centrifuge tube and stir thoroughly
for several minutes. Heat carefully while stirring until boiling
74
-------
begins. Centrifuge at high speed for 10 minutes. Carefully
decant and discard supernatant.
11. Slurry precipitate in 10 ml water, add 1 ml 4 N HN03, stir and
immediately transfer precipitate to tared glass-fiber filter.
Filter slowly at first to prevent loss.
12. Wash precipitate on filter successively with 20 ml 0.2 N HN03,
20 ml ethanol and 20 ml diethyl ether. Let dry with suction at
least 10 minutes. Store in desiccator.
13. Weigh, mount and store in light-tight container until ready to
count.
Calculation
Calculate the concentration, D, of the iodine radioisotopes in
picocuries per milliliter as follows:
D
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry as
follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
75
-------
Calculate decay corrections as follows:
-0.693t/T
Ao
where:
A = activity at time t,
A0 = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclide, in same units as t.
Confirmation of Activity and Identification of Iodine Isotopes
1. Plot gamma-ray spectrum of separated sample immediately and after
6 hr, 24 hr, 2 d, 5 d, 1 week and 3 week intervals to identify
8.06-d 131I (364, 637 and 284 keV), 20.9-hr 133I (530 and 850 keV),
and 6.7-hr 135I (1130, 1260 and 1710 keV).
2. Beta-count the Agl planchet daily to measure and confirm half-
life values for those isotopes present.
Note:
1. A distillation apparatus such as shown in Figure 1 (page 8) or
equivalent can be used. It should consist of a round bottom
flask fitted with a ground-glass joint that allows for a source
of air to be bubbled into the sample, and has a delivery tube
on the other end that extends into a caustic trap.
Reference:
1. Kleinberg, J. and Cowan, G. A., "The Radiochemistry of Fluorine,
Chlorine, Bromine and Iodine", AEC Rept. NAS-NS-3005, 1960.
76
-------
Radioactive Iron
Principle of Method
Iron carrier and the appropriate holdback carrier are added to the
acidified aqueous sample. Iron is extracted into trioctylphosphine
oxide and back extracted into dilute perchloric acid. After double
precipitation of the hydrous oxide to separate it from impurities, the
iron is precipitated as the alcohol-washed Fe(OH)3.2H20 for counting.
Procedure Time
2 samples - 4 hrs.
Reagent
Acetone, (CH^^CO: anhydrous
Ammonium hydroxide, NH^OH: 15 N (cone.), 1 N
Cobalt carrier: 5 mg/ml
Ethanol, C2H5OH: 95%
Hydrochloric acid, HCl: 12 N (cone.), 6 N
Indicator, methyl red: 0.1%
Iron carrier: 10 mg/ml
Perchloric acid, HClO^: 1 N
Pyridine, CgHgN
Trioctylphosphine oxide, (CgH^jPO: 20% in xylene
Procedure
1. To an acidified aqueous sample (100 ml or less), add 1.0 ml iron
carrier and 0.5 ml cobalt carrier and dilute or concentrate to
20 ml. Transfer to a 125 ml separator/ funnel (Note 1).
2. Add 50 ml 6 N HCl and 10 ml 20% trioctylphosphine oxide in xylene.
Shake 5 min. and discard the bottom aqueous layer.
3. Wash with 10 ml 6 N HCl and discard wash solution
4. Back extract iron for 2 min. with 10 ml 1 N HCIO^ and transfer acid
phase to a centrifuge tube.
77
-------
5. Repeat step 4 with a second 10 ml portion of 1 N HCIO^ and add the
acid phase to the same centrifuge tube. Discard the organic layer.
6. Heat in a boiling water bath to drive off excess xylene. Cool to
room temperature.
7. Add 2 drops methyl red indicator and a few ml 15 N NH^OH until
color just begins to change. Complete precipitation of iron by
adding 1 N NH,OH just to the permanent color change.
8. Stir in the hot water bath until the precipitate coagulates and
settles readily. Centrifuge and discard supernatant. (Note 2).
9. Dissolve precipitate in 1.0 ml 6 N HCl with heating. Dilute to
20 ml with water, add 1 ml pyridine, stir well and heat in a water
bath until precipitation is complete. (Note 3).
10. Cool, centrifuge and discard supernatant.
11. Wash precipitate with ~20 ml water. Centrifuge and discard the
wash solution.
12. Break up the gelatinous precipitate with the tip of a thin stirring
rod and a few drops of ethanol. Transfer to a tared glass-fiber
filter with ethanol. Wash twice with ethanol and once with acetone,
adding each portion just as the traces of the last addition have
gone through the filter. Let air go through the filter for a few
minutes.
13. Dry in an oven, cool in a desiccator and weigh to a constant weight.
Mount, cover with 0.005 mm mylar and count.
78
-------
Calculation
Calculate the concentration, D, of iron-59 in picocuries per
milliliter as follows:
D
2.22 x EVR
where :
C * net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R « fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry as
follows :
E = Fp
where :
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for iron-59 as follows :
A = A0 e-°-693t/T
where :
A a activity at time t,
AQ = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection,
T = half life of separated nuclide in same units as t.
Confirmation of Fe Activity and Identification of Iron Isotopes
1. Plot gamma-ray spectrum of separated sample to identify photopeaks
of 44.6-d 59Fe (1099 and 1291 keV).
2. To identify and quantify the 2.7-yr 55Fe, the sample is counted on
an x-ray proportional counter capable of resolving the 5.90 keV
55Fe photopeak from the adjacent 6.40 keV 58Co peak. (Note 4).
79
-------
Notes:
1. The sample should be acidified with 1 ml 12 N HC1 per 50 ml
solution since extraction efficiency is lowered if nitric acid
is present.
2. For a sample containing significant cobalt activity, the
following modification should be followed at this point:
a. wash precipitate with ~20 ml water. Centrifuge and discard
wash solution.
b. dissolve precipitate with 1 ml 6 N HC1 and heat. Dilute to
20 ml with water.
c. add 1 ml pyridine, stir well and heat in a water bath to
coagulate. Cool, centrifuge and discard supernatant.
d. wash with ~20 ml water. Centrifuge and discard wash
solution.
e. dissolve precipitate with 1 ml 6 N HCl and heat. Dilute
to 20 ml with water and add 1 ml cobalt holdback carrier.
Place in a 125 ml separatory funnel.
f. repeat Iron procedure steps 2-8.
3. Use pyridine in a hood.
4. This technique is especially useful if any radiocobalt still
remains even after completing the procedure modification
suggested in Note 2. If there is a possibility of small amounts
of *8co being counted in the 55pe channels, this will be revealed
by delayed counting to detect the faster decaying 58co.
References:
1. Nielsen, J. M., "The Radiochemistry of Iron", USAEC Kept.
NAS-NS-3017, 1960.
2. Lingane, J. J. and Kerlinger, H., "Polarographic Determination
of Nickel and Cobalt", Ind. Chem., Anal. Ed., 13, 77, 1941.
80
-------
Radioactive Lanthanum
plus
Trivalent Rare Earths and Yttrium
Principle of Method
Lanthanum carrier and appropriate scavenging carriers are added to
the acidified aqueous sample and impurities are removed by cobaltini-
trite and iodate precipitations. The lanthanum is collected as the
hydroxide and purified as La2 ^O^oSl^O for counting.
Procedure Time
4 samples - 6 hrs.
Reagents
Acetic acid, CH3COOH: 8 N
Ammonium acetate buffer, (CI^COOH-CE^COONH^) : pH 5.0
Boric acid, 113803: saturated
Cerium carrier: 5 mg/ml
Cobalt carrier: 5 mg/ml
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 6 N
Hydrofluoric acid, HF: 48% (cone.)
Hydrogen peroxide, I^C^: 30%
lodic acid, HlCy 0.35 M
Lanthanum carrier: 10 mg/ml
Nitric acid, HN03: 16 N (cone.)
Oxalic acid, ^€204: saturated
Potassium hydroxide, KOH: 6 N
Potassium nitrite, KN02 : solid
Sodium bromate, NaBr03: 0.5 M
Sodium hydroxide, NaOH: 18 N
Strontium carrier: 20 mg/ml
Procedure
1. To an aqueous sample (100 ml or less), add 1 ml 16 N HN03, 1.0 ml
lanthanum carrier, and 1 ml each of cerium, cobalt and strontium
carriers. Stir to mix well.
2. Slowly add at least 2 drops H202 and 6 N KOH until precipitation of
81
-------
hydrous oxides is complete. Heat to coagulate, cool, centrifuge
and discard supernatant.
3. Dissolve precipitate in 5 ml 8 N acetic acid and 2 drops H202 with
heating. Dilute to 15 ml with water, add 5 ml ammonium acetate
buffer solution (pH 5) and heat to boiling in a water bath.
Carefully add 5 g KN02 in small increments, with stirring. Continue
boiling until gas evolution ceases and the potassium cobaltinitrite
precipitate settles.
4. Cool, centrifuge and filter supernatant through Whatman #42 (or
equivalent), into a polypropylene tube containing 5 ml 16 N HNOo.
Discard filter paper.
5. Slowly add 20 drops HF, stir and let the fluoride precipitate
settle for 5 minutes. Centrifuge and discard supernatant.
6. Wash twice with 20 ml water and discard wash solutions.
7. Dissolve precipitate with 1 ml sat. H3B03 and 8 ml 16 N HN03. Add
4 ml 0.5 M NaBr03 to oxidize cerous to eerie ion and stir for
1 minute.
8. Add 20 ml 0.35 M HI03 slowly, with stirring. Cool in an ice bath
for 5 minutes. Centrifuge, transfer supernatant to a glass centri-
fuge tube and discard precipitate.
9. Make basic with 5-10 ml 18 N NaOH to precipitate lanthanum and the
rare earth hydroxides. Stir and cool for 5 minutes. Centrifuge
and discard supernatant.
10. Wash precipitate with 30 ml water and discard the wash solution.
82
-------
11. Dissolve precipitate with 1 ml 6 N HC1 and add 15 ml water. Heat
in a water bath, add 15 ml sat. H2C204 with stirring and digest for
a few minutes.
12. Cool, centrifuge and discard supernatant.
13. Wash precipitate with 15 ml hot water and discard wash solution.
14. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
15. Dry, cool, weigh, mount and count.
Calculations
Calculate the concentration, D, of lanthanum-140 and/or the
trivalent rare earths and yttrium* in picocuries per milliliter as
follows:
D
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry as
follows:
E = Fp
*These nuclides include: 9DY T-j/2 64.0 hr no gammas
91Y 59 d 1210 keV
93Y 10.3 hr 297, 940 and 1900 keV
!4?Nd 11 d 91, 533 and 319 keV
152Eu 12.7 y 122, 344 and 1408 keV
16 y 123, 724 and 1278 keV
13.6 d no gammas
2. 6 y no gammas
83
-------
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate activity decay corrections as follows:
-0.693t/T
Ao Ao e
where:
A = activity at time t,
A0 SB activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of the separated nuclide, in same units as t.
Confirmation of Purity and Identification of l**QLa+ the Trivalent Rare
Earths and Yttrium*
1. Plot the gamma-ray spectrum of the separated sample immediately and
again at daily intervals to identify the main 1^"La photopeaks
(1596 keV, 487 keV, 329 keV and 815 keV) and follow decay.
2. If other photopeaks are present, determine whether they represent
trivalent rare earth peaks or are due to incomplete procedure
decontamination. A distinct gamma photopeak at 1210 keV would
suggest the presence of 59-d half life 91y. The measurement and
identification of this nuclide can be confirmed by following
photopeak decay at 2-week intervals.
3. If the planchet contains only photopeaks for l^OLa, beta count at
2-day intervals to corroborate the l^OLa half-life (40.2 hr).
After 1 month, beta count to ascertain if 1^7pm activity is present
(2.6 y t^/2» no Y radiation).
Reference:
1. Stevenson, P. C. and Nervik, W. E., "The Radiochemistry of the
Rare Earths, Scandium, Yttrium and Actinium", USAEC Rept.
NAS-NS-3020, 1961.
*If yttrium isotopes, 90Y, 91y or 93Y, are believed to be present, the
yttrium procedure, p. 151, should be performed on an acidified aliquot
for verification.
84
-------
Radioactive Manganese
Principle of Method
Manganese carrier and appropriate scavenging carriers are added
to the acidified aqueous sample and impurities are removed by cobalti-
nitrite and hydroxide precipitations. The manganese is purified as
for counting.
Procedure Time
4 samples - 3 hrs .
Reagents
Acetic acid, CH3COOH: 8 N
Ammonium acetate buffer (d^COOH-ClLjCOONI^) : pH 500
Ammonium hydroxide, NH^OH: 6 N
Ammonium phosphate, NH^HoPO^.: solid_
Chromium carrier: 10 mg/ml as C^Oy"
Cobalt carrier: 5 mg/ml
Hydrogen peroxide, ^2.^2' "^°
Iron carrier: 10 mg/ml
Manganese carrier: 5 mg/ml
Nitric acid, HM^: 16 N (cone.)
Potassium hydroxide, KOH: 6 N
Potassium nitrite, KNC^ : solid
Procedure
1. To an aqueous sample (100 ml or less), add 1 ml 16 N HN03, 1.0 ml
manganese carrier and 0.5 ml each of cobalt, chromium and iron
carriers. Stir to mix well.
2. Slowly add at least 2 drops 1^2 and 6 N KOH until precipitation of
hydrous oxides is complete. Heat to coagulate, cool, centrifuge
and discard supernatant.
3. Wash precipitate with ~20 ml water and discard wash solution.
85
-------
4. Dissolve precipitate with 5 ml 8 N CH3COOH and 2 drops H202 with
heating. Dilute to 15 ml with water, add 5 ml ammonium acetate
buffer solution (pH 5) and heat to boiling in a water bath.
Carefully add 5 g KN02 in small increments, with stirring.
Continue boiling until gas evolution ceases, and the precipitate of
potassium cobaltinitrite settles. Cool, centrifuge and filter the
supernatant through Whatman #42 (or equivalent) into a clean
centrifuge tube. Discard filter paper.
5. Repeat steps 2 and 3.
6. Dissolve the precipitate with 1 ml 16 N HNOg and 1 drop H202.
7. Add 5 ml water, 0.5 ml iron carrier and heat almost to boiling.
Adjust the pH to just below 7 with 6 N NlfyOH, stirring rapidly to
effect precipitation of Fe(OH)3.
8. Filter, while hot, through Whatman #41 (or equivalent) into a clean
centrifuge tube. Discard precipitate.
9. Dilute to 15 ml with water, add 1 g NILE^PO, and bring the solution
nearly to boiling. Adjust to pH 7 with 6 N NH^OH and stir until
the crystalline precipitate manganese ammonium phosphate
[Mn(NH4)PO4.H20] forms.
10. Cool in an ice bath for 10 min., transfer to a tared glass-fiber
filter, wash with successive portions of water and ethanol.
11. Dry, cool, weigh, mount and count.
86
-------
Calculation
Calculate the concentration, D, of radioactive manganese in
picocuries per milliliter as follows:
2.22 x EVR
where:
C = net count rate, counts/min,
E SB counter efficiency,
V = milliliters of sample used,
R SB fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
-0.693t/T
A SB A0 e
where:
A = activity at time t,
Ao = activity at time zero,
e = base of natural logarithms
t = elapsed time from collection, and
T SB half life of separated nuclide, in same units as t.
Confirmation of Purity and Identification of
1. Plot gamma-ray spectrum of separated sample to identify and
quantify the 313 d 54Mn photopeak (835 keV).
2. Repeat gamma spectrum measurement after 4 weeks to substantiate
the manganese half life.
Reference:
1. Lingane, J. J., Analytical Chemistry of Selected Metallic
Elements, (Reinhold, New York, N. Y. 1966) pp. 48-49.
87
-------
Radioactive Molybdenum
Principle of Method
Molybdenum carriers and appropriate scavenging carriers are added
to the aqueous sample. Impurities are removed by a double hydroxide
scavenge followed by sample evaporation. The molybdenum is extracted
into diethyl ether, back extracted into water, precipitated with
or-benzoinoxime and ashed to MoO
-------
3. Add 0.5 ml cobalt carrier and 2 drops KLO_ to the filtrate. Heat
nearly to boiling, stir, filter while hot through Whatman #41 (or
equivalent), and collect filtrate in a clean beaker. Discard
filter paper.
4. Evaporate filtrate almost to dryness and add 5 drops each of iron
carrier and 1.5 M NaBrCL.
5. Adjust volume to 15 ml and add 0.5 ml cobalt carrier. Transfer to
a 200 ml separatory funnel with 15 ml 12 N HC1 to make solution
~6 N in HC1.
6. Shake for 15 minutes with 100 ml diethyl ether which was equili-
brated with 6 N HC1. After the layers separate, discard the
bottom aqueous layer.
7. Wash the ether twice with 2 ml 6 JN HC1 and discard the wash layers.
8. Back extract molybdenum three times with three 10 ml portions of
water, combining the aqueous fractions in a beaker. Discard the
ether layer.
9. Add 2 ml 16 N HNO-, 0.5 ml cobalt holdback carrier and 10 ml
"*• ^
a-benzoinoxime solution. Stir for 5 minutes, centrifuge and
discard supernatant.
10. Wash with 15 ml 0.2 N HN03 and discard wash solution.
11. Slurry precipitate with a few ml water and filter through Whatman
#42 (or equivalent). Complete the transfer with a few ml 1 N
Discard filtrate.
89
-------
12. Dry precipitate at 110°C for 15 minutes. Transfer to a platinum
crucible and ash for 1 hour at 550°C to convert molybdenum to Mo03<
13. Cool and transfer to a tared glass-fiber filter with water. Wash
with successive portions of water and ethanol.
14. Dry, cool, weigh, mount and count.
Calculation
Calculate the concentration, D, of molybdenum-99 in picocuries
per milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for molybdenum-99 as follows:
-0.693t/T
A = A e
o
where:
A = activity at time t,
A = activity at time zero
90
-------
e =8 base of natural logarithms,
t a« elapsed time from collection, and
T a half life of molybdenum-99 in same units as t (tj/2 =66.3 hr).
Confirmation of Purity and Identification of Molybdenum-99
1. Plot the gamma-ray spectrum of the ashed precipitate soon after
separation to identify any contaminating gamma emitters and the
main 99Mo photopeaks (181 and 740 keV).
2. Gamma scan at 2- or 3-day intervals to observe the 66.3 hr decay
of the 740 keV °%Io photopeak. The presence of ^^Mo can also be
corroborated by following the ingrowth of the 6.0 hr 99mTc
daughter at 140 keV (abundance 90%). Any calculations based on
the 140 keV peak, has to consider the 181 keV ^^Mo peak (abundance
7%).
3. Two days after separation, 99Mo-99mxc equilibrium is nearly
complete, and the 66.3 hr half life of 99Mo can be corroborated by
beta counting the planchet at 3-day intervals.
Reference:
1. Scadden E. M. and Ballou, N. E., "The Radiochemistry of
Molybdenum", DSAEC Rept. NAS-NS-3009, 1960.
91
-------
Neptunium
Principle of Method
Cerium carrier is added to the acidified aqueous sample, and is
scavenged along with rare earth fission products by a fluoride precipi-
tation in an oxidized solution while neptunium remains in solution.
Lanthanum carrier and appropriate holdback carriers are added, and
neptunium is collected on the lanthanum fluoride precipitate under
reduced conditions. The neptunium is purified by a double hydroxide
precipitation and is carried on La(OH)o for counting.
Procedure Time
2 samples - 3 hrs.
Reagents
Acetone, (0113)200: anhydrous
Ammonium hydroxide, NH^OH: 15 N (cone.), 1 N
Boric acid, 113603: saturated
Cerium carrier: 5 mg/ml
Cesium carrier: 10 mg/ml
Cobalt carrier: 5 mg/ml
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 12 N (cone.), 6 N
Hydrofluoric acid, HF: 48% (cone. ~30 N), 1 N
Indicator, phenolphthalein: 1%
Iron carrier: 10 mg/ml
Lanthanum carrier: 10 mg/ml
Manganese carrier: 5 mg/ml
Nitric acid, HN03: 16 N (cone.), 6 N
Sodium bromate, NaBrOo: 1.5 M (freshly prepared)
Sodium sulfite, Na2S03: 1 M
Zirconium carrier: 10 mg/ml
Procedure
1. To an aqueous sample (50 ml or less), add 2 ml 16 N HNO,., 3 drops
cerium carrier and evaporate to dryness. (Do not bake.)
2. Slurry with 2 ml 6 N HNO,, and transfer to a polypropylene tube with
92
-------
water to a volume of 10 ml. Add 1 drop cerium carrier and 1.5 ml
freshly prepared 1.5 M NaBr03. (Note 1). Digest and stir for
20 minutes in a water bath maintained at 95°C.
3. Cool to room temperature and make ~3 N in HF by adding 1.5 ml 48%
HF (~30 N) dropwise while stirring and diluting to 15 ml. Centri-
fuge at least 10 mln. (Note 2).
4. Destroy most of the bromates by adding 1-2 ml 12 N HC1 dropwise and
stirring in a boiling water bath until solution is clear. Cool
slightly and add 15 ml freshly prepared 1 M Na2SOo. Add 1.0 ml
lanthanum carrier and one drop each cobalt, manganese', iron,
zirconium and cesium holdback carriers. Stir a few minutes in a
boiling water bath.
5. Cool to room temperature and make ~3 IN in HF by adding 3 ml 487» HF.
Stir well during the addition of the HF, then allow the precipitate
to settle.
6. Centrifuge at high speed at least 5 minutes and discard supernatant.
7. Wash with a solution containing 5 ml 1 N HNOg, 5 ml 1 N HF and
10 drops 1 M Na2S03 and discard wash solution.
8. Dissolve fluorides with 1 ml sat. H3B03 and 1 ml 16 N HN03- Dilute
to 10 ml and make basic with 15 N NH.OH to phenolphthalein end
point. Add an additional 2 ml 15 N NH^OH, and stir in a hot water
bath until precipitate is well coagulated. Cool, centrifuge and
discard supernatant. (Note 3).
93
-------
9. Dissolve precipitate with 1-2 ml 6 N HC1, and dilute to 10 ml.
Filter through Whatman #41 (or equivalent) into a clean glass
centrifuge tube. Reprecipitate lanthanum hydroxide with 15 N
NH^H as in step 8. Centrifuge and discard supernatant.
10. Wash precipitate with 10 ml N NH4OH and discard wash solution.
11. Transfer to a tared glass-fiber filter with 1 N NH4OH. Wash twice
with 10 ml ethanol and twice with 10 ml acetone.
12. Dry at 110°C for 30 minutes, cool, weigh, mount and count.
Calculation
Calculate the concentration, D, of the 239jjp ±n picocuries per
milliliter as follows:
D =
2.22 x EVR
where:
C = count rate, counts/min,
E = counter efficiency for
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = FP
where:
F = fractional abundance of the gamma rays, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
-0.693t/T
A = A0 e
94
-------
where:
A = activity at time t,
A0 = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of 239jjp ^n same units as t (tj^/2 = 2.34 d).
Confirmation of Purity and Identification of 239jqp
1. Plot the gamma-ray spectrum of the activity immediately after
separation to identify any contaminating gamma emitters.
2. Gamma scan at 1-day intervals to observe the decay of predominant
23%p photopeaks (106 keV, 228 keV and 278 keV).
3. Beta count the planchet daily to record the decay and corroborate
the 2.34-d half life of 239Np.
Notes:
1. Prepare only enough 1.5 M NaBr03 and 1 M Na2S(>3 for each analysis,
2. Care must be taken to make the procedure quantative, through
step 3 and the first part of step 4, because no carrier is
added for neptunium up to the point of addition of lanthanum
carrier in step 4= The cerium fluoride precipitate can be
dissolved and gamma scanned to make certain no neptunium was
lost.
3. Further decontamination can be accomplished by adding one drop
each of the holdback carriers and reprecipitating lanthanum
fluoride under reducing conditions after dissolving the first
lanthanum hydroxide precipitate, as follows:
a. Dissolve hydroxide in 1-2 ml 6 N HC1 and dilute to 10 ml
with water.
b. Add 10 ml 1 M Na2S03 and 1 drop each of the cobalt,
manganese, iron, zirconium and cesium holdback carriers.
Stir for a few minutes in a boiling water bath.
c. Repeat steps 5-8.
References:
1. Seaborg, G. T. and Katz, J. J., Eds., Radiochemical Studies:
The Actinide Elements, Nat'l Nucl. Energy Series, Div. IV,
14A (McGraw-Hill, New York, N. Y., 1954) pp. 574-577.
2. Prakash, S., Advanced Chemistry of Rare Elements, (Chemical
Publishing Co., Inc., New York, N. Y., 1967) pp. 777-778.
95
-------
Radioactive Phosphorus
Principle of Method
Phosphorus carrier and appropriate scavenging carriers are added
to the acidified aqueous sample and impurities are removed by a double
hydroxide precipitation. The phosphorus is precipitated as MgNH^PO^
for counting.
Procedure Time
4 samples - 4 hrs.
Reagents
Ammonium hydroxide, NH^OH: 15 N (cone.), 1 N
Cobalt carrier: 5 mg/ml
Diethyl ether, (C2Hg)20: anhydrous
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 12 N (cone.), 6 N
Hydrogen peroxide, H2(>2: 30%
Indicator, methyl red: 0.1%
Magnesia mixture: prepared reagent
Manganese carrier: 5 mg/ml
Nitric acid, ENO^: 6 N
Phosphorus carrier: 5 mg/ml
Potassium hydroxide, KOH: 6 N
Silver carrier: 20 mg/ml
Zirconium carrier: 10 mg/ml
Procedure
1. To an aqueous sample (200 ml or less), add 1 ml 6 N HNO,, 1.0 ml
phosphorus carrier and 0.5 ml each cobalt, zirconium, silver and
manganese carriers.
2. Slowly add at least 2 drops H^ and 6 N KOH until precipitation of
hydrous oxides is complete. Heat to coagulate and filter while hot
through Whatman #41 (or equivalent). Discard filter paper.
96
-------
3. To the filtrate add 2 drops cobalt and zirconium carriers and
2 drops IL,02> Heat to coagulate and filter while hot through
Whatman #41 (or equivalent). Discard filter paper.
4. Acidify the filtrate with 12 N HC1 and boil a few minutes to
remove excess H^O-. Cool in an ice bath.
5. Add 3 ml magnesia mixture and neutralize to methyl red end point
with 15 N NH^OH to precipitate MgNH4P04. Let stand 2 minutes then
add 3 ml excess 15 N NH4OH. Centrifuge and discard supernatant.
6. Wash the precipitate with 10 ml 1 N NH.OH and discard wash solution.
7. Dissolve precipitate with 1 ml 6 N HC1. Transfer to an ice bath,
add 10 ml water and 3 ml magnesia mixture and neutralize to methyl
red end point with 15 N NH4OH. Let stand 2 minutes then add 3 ml
excess 15 N NH4OH. Centrifuge and discard supernatant.
8. Repeat steps 6 and 7 using only 1 ml magnesia mixture.
9. Wash the precipitate with 10 ml 1 N NH.OH and discard wash solution.
10. Transfer to a tared glass-fiber filter with 1 N NH4OH. Wash with
successive portions of 1 1? NH.OH, ethanol and ether.
11. Dry, cool, weigh, mount and count.
Calculation
Calculate the concentration, D, of phosphorus-32 in picocuries per
milliliter as follows:
D
2.22 x EVR
97
-------
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 ss conversion factor from disintegrations/min to picocuries
Calculate the decay correction for 32P (.^1/2 = l^-3 d) as
-0.693t/T
A = A0 e
where:
A a activity at time t,
Ao = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T s± half life of 32P, in same units as ts
Confirmation of Purity and Identification of
1. Plot the gamma-ray spectrum of the separated sample to ascertain
whether any gamma photopeaks from impurities are present.
2. Beta count the planchet at 1-week intervals to corroborate the
14.3 d half-life of the phosphorus activity.
References:
1. Bowen, H. J. M. and Gibbons, D., Radioactivation Analysis
(Oxford University Press, London, 1963) p. 222.
2. Kolthoff, I. M. and Sandell, E. B., Textbook of Quantitative
Inorganic Analysis (Macmillan, New York, N. Y., 1952) pp. 316
and 379.
98
-------
Radioactive Ruthenium
Principle of Method
Ruthenium carrier and the appropriate holdback carrier are added
to a sample in a special distillation flask. In acid solution, in the
presence of a strong oxidant, the ruthenium is converted to the
tetroxide, distilled into caustic, and reduced to the metal for counting.
Procedure Time
4 samples - 3 hrs.
Reagents
Cobalt carrier: 5 mg/ml
Diethyl ether, (C2Hs)20: anhydrous
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 12 N (cone.), 6 N
Magnesium metal, Mg: solid
Phosphoric acid, H^PO^: 44 N (cone.)
Potassium permanganate, KMnCty: 0.5 M
Ruthenium carrier: 10 mg/ml
Sodium hydroxide, NaOH: 6 N
Procedure
1. To an aqueous sample (100 ml or less) in a special ruthenium
distillation flask (Fig. 5), add 2.0 ml ruthenium carrier and 1 ml
cobalt holdback carrier.
2. Connect the ruthenium still to an air inlet, and insert the
distilling end into a centrifuge tube containing 15 ml 6 N NaOH in
an ice bath.
3. To distillation flask add 3 ml 44 N H-jPO^ and 3 ml 0.5 M KMnO^., and
immediately close system.
99
-------
AIR INLET-
5-mm ID TUBING
GROUND
GLASS
JOINT
125-ml
FLORENCE
FLASK
• FROM BOTTOM
5-mm ID TUBING
?
->•
\
J
3G
_
k
>cm
L_
Figure 5. Distillation Apparatus for Ruthenium Analysis
100
-------
4. Pass air gently through system to drive volatile ruthenium into the
NaOH solution. (Note 1).
5. Gently heat to boiling and continue heating for 10-15 minutes. Turn
off air, disconnect apparatus and discard contents of still.
6. Add 3-5. ml ethanol to distillate, stir, boil to precipitate Ru02
and cool. Centrifuge and discard supernatant.
7. Suspend precipitate in 10 ml water containing 1 ml 6 N NaOH. Boil,
cool, centrifuge and discard supernatant.
8. Dissolve precipitate in 2 ml 6 N HC1, heating gently in a water
bath to aid dissolution.
9. Add 10 ml water and slowly add 100-200 mg magnesium metal in small
portions, adding each portion when the previous addition has been
oxidized.
10. Boil until ruthenium metal has completely precipitated. Wash walls
of tube with a few drops of 12 N HCl and add additional HCl to
dissolve residual magnesium. Cool, centrifuge and discard
supernatant.
11. Transfer precipitate to a tared glass-fiber filter with 15 ml water.
Wash with successive portions of water, ethanol and ether.
12. Dry, cool, weigh, mount and count.
Calculation
Calculate the concentration, D, of radioactive ruthenium in pico-
curies per milliliter as follows:
D
2.22 x EVR
101
-------
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry as
follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for radioactive ruthenium as
follows:
-0.693t/T
A = A e
o
where:
A « activity at time t,
Ao - activity at time zero,
e - base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclides, in same units as t.
Confirmation of Purity and Identification of Ruthenium Isotopes
1. Plot the gamma-ray spectrum of the separated sample. The
(106Rh) photopeaks are at 512 keV and 620 keV; the 1Q3RU photopeafcs
are at 497 keV and 610 keV.
2. The 106Ru (106Rh) and the 103Ru photopeaks are distinguished by
differing relative intensities of gamma rays at approximately 500
and 600 keV. These ratios, previously determined with standardized
tracer solutions, can indicate if either of these ruthenium
isotopes is present alone.
3. Beta-count the planchet at 1-month intervals to measure decay and
confirm the half-life values for the isotope(s) present: 103RU,
39.7 d; 106RUji.o yr.
102
-------
Note:
If ruthenium activity, which could be present in several
oxidation states in reactor effluents, is not completely
interchanged with the carrier solution, discrepancies
between radiochemical and chemical yield determinations will
result. Treatment parameters (boiling, distilling etc.) to
remedy this situation are mentioned in reference 2.
Reference:
1. Wyatt, E. I. and Rickard, R. R., "The Radiochemistry of
Ruthenium", USAEC Kept. NAS-NS-3029, 1961.
2. Kahn, B. and Reynolds, S. A., "Determination of Radionuclides
in Low Concentrations in Water", Jour. AWWA, 50, 613, 1958.
103
-------
Radioactive Silver
Principle of Method
Silver carrier and the appropriate scavenging carrier are added to
the aqueous sample. After silver is collected as the hydrous oxide,
impurities are removed by a cobaltinitrite precipitation. The silver
is precipitated as AgCl for counting.
Procedure Time
4 samples - 3 hrs.
Reagents
Acetic acid, CH3COOH: 8 N
Ammonium acetate buffer, (CH3COOH-CH3COONH4): pH 5.0
Cobalt carrier: 5 mg/ml
Ethanol, C2HsOH: 95%
Hydrochloric acid, HCl: 0.5 N
Hydrogen peroxide, ^C^: 30%
Nitric acid, HN03: 1 N
Potassium hydroxide, KOH: 6 N
Potassium nitrite, KN02: solid
Silver carrier: 20 mg/ml
Procedure
1. To an unacidified aqueous sample (200 ml or less), add 1.0 ml
silver carrier and 1 ml cobalt carrier. (Note 1). Evaporate to
about 30 ml.
2. Slowly add at least 2 drops H202 and 6 N KOH until precipitation of
the black hydrous oxides of silver and cobalt is complete. Heat to
coagulate, cool, centrifuge and discard supernatant.
3. Wash precipitate with 20 ml water and discard wash solution.
104
-------
4. Dissolve precipitate in 5 ml 8 N CHgCOOH and 2 drops Kflz with
heating. Dilute to 15 ml with water, add 5 ml ammonium acetate
buffer solution (pH 5) and heat to boiling in a water bath.
Carefully add 5 g KNC>2 in small increments, with stirring.
Continue boiling until gas evolution ceases and the precipitate
settles. Cool, centrifuge and filter the supernatant containing
the silver into a clean centrifuge tube through Whatman #42 (or
equivalent). Discard filter paper.
5. Boil filtrate until all brown nitric oxide fumes are released, and
dilute to 40 ml with water.
6. Add 1 drop 1 N HN03 and 6 drops 0.5 N HC1 to the warm solution.
Continue stirring and heating until the coagulated AgCl settles,
and supernatant is clear. Test supernatant for completeness of
precipitation with one more drop 0 .5 N HC1.
7. Cool in an ice bath, centrifuge and discard supernatant.
8. Wash with 20 ml water and discard wash solution.
9. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
10. Dry, cool, weigh, mount and count (Note 2).
Calculation
Calculate the concentration, D, of the Ag in picocuries per
milliliter as follows:
D =
2.22 x EVR
105
-------
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F - fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
-0.693t/T
A = A e
o
where:
A = activity at time t,
A = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection in days, and
T = half life of the 110nfcg (253 d).
Confirmation of Purity and Identification of
1. Plot the gamma-ray spectrum of the AgCl precipitate to verify the
110mAg photopeaks at 658 keV, 885 keV, 937 keV, 764 keV and
1384 keV and identify any contaminating gamma emitters (Note 2)«
2. Beta count the sample after 2 months and 6 months to confirm the
253-d half life of 110mAg.
Notes:
1. The aqueous sample must not contain chlorides. If the sample
contains chlorides, it should be evaporated to dryness, the
residue taken up in 10 ml 16 N HNOo, evaporated to dryness
again and taken up in 30 ml H20. Dilute NH.OH should be added
to neutralize the sample before the silver and cobalt carriers
are added.
106
-------
If cobalt activity is still present in the AgCl precipitate,
wash the precipitate from the glass-fiber filter into a beaker
with a minimum of water. Heat and add 15 N M^OH to dissolve.
Add 0.5 ml cobalt carrier and repeat steps 2-10.
Reference:
1. Lingane, J. J., Analytical Chemistry of SelectedMetallic
Elements (Reinhold, New York, N. Y., 1966) pp. 48, 99.
107
-------
Radioactive Strontium and Barium
Principle of Method
The strontium and barium carriers are added to the aqueous sample,
collected as insoluble carbonates, and separated from most of the
calcium as nitrates. Impurities are removed by an hydroxide scavenge.
The barium is precipitated as the chromate and purified as BaSO^ for
counting; the strontium is purified as SrCOg for counting.
Procedure Time
4 samples - 6 hrs.
Reagents
Ammonium acetate buffer, (CHoCOOH-CHgCOONH^): pH 5.0
Ammonium hydroxide, NlfyOH: 15 N (cone.), 6 N
Barium carrier: 20 rag/ml
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 6 N, 1 N
Indicator, methyl red: 0.1%
Iron chloride, FeCl-: 0.1 M
Nitric acid, HN03: 16 N (cone.), 6 N, 1 N
Oxalic acid, I^CgO.: saturated
Sodium carbonate, 1132003: 1.5 M
Sodium chromate, Na^rO^.: 0.5 M
Sodium hydroxide, NaOH: 6 N
Strontium carrier: 20 mg/ml
Sulfuric acid, H2SO,: 12 N
Yttrium carrier: 10 mg/ml
Procedure
1. To an aqueous sample (1000 ml or less), add 1.0 ml of strontium and
barium carriers.
2. Make basic with 6 N NaOH and heat to boiling.
3. Add 5 ml 1.5 M Na2C03, stir, digest, cool, centrifuge and discard
supernatant.
108
-------
4. Wash precipitate with 15 ml water and discard wash solution.
5. Dissolve precipitate with 1 ml 6 N HN03.
6. Add 25 ml 16 N HNOg, stir and cool in an ice bath 5 min.
7. Centrifuge, discard'supernatant and let drain a few minutes.
(Note 1).
8. Dissolve precipitate with 10 ml water and add 0.5 ml 0.1 M
9. Heat to near boiling in water bath and add 6 N NH^OH dropwise until
Pe(OH)g precipitates.
10. Cool, centrifuge and transfer supernatant to a clean centrifuge
tube. Discard precipitate. Record time as beginning of yttrium
ingrowth. (Complete steps 11-18 without delay, to minimize
ingrowth of 90Y.)
11. Add 3 drops methyl red indicator, and adjust pH to near 5 with a
few drops 1 N^ HC1. (Color change is from yellow to red.)
12. Add 5 ml ammonium acetate buffer solution and heat in water bath.
13. Slowly add 1 ml 0.5 M Na2Cr04. Stir, heat, centrifuge. Transfer
supernatant to a clean centrifuge tube. Save precipitate for
step 19.
14. Add 2 ml 15 N NH^OH to the supernatant, heat in water bath, and
slowly add, with stirring, 5 ml 1.5 M Na2C03. Digest for a few
minutes, cool, centrifuge and discard supernatant.
15. Dissolve precipitate with 5 ml 1 N HC1, add 10 ml water and repeat
step 14.
109
-------
16. Wash the strontium carbonate precipitate with 20 ml water, and
discard wash solution.
17. Slurry the precipitate with a minimum of water and transfer to a
tared stainless steel planchet. Dry under infra-red lamps.
18. Cool, weigh and count immediately. Store planchet for suitable
time for yttrium-90 ingrowth. (Note 2).
19. Dissolve precipitate from step 13 with 2 ml 6 N HCl and dilute to
10 ml. Heat in water bath several minutes.
20. Slowly add 2 ml 12 N HSO dropwise, with stirring, to precipitate
21. Centrifuge and discard supernatant. Record this time as the
beginning of ^®La. ingrowth.
22. Wash precipitate twice with 15 ml water and discard wash solutions.
23. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
24. Dry, cool, weigh, mount and count both beta and gamma activity.
Record date and time of counting.
Yttrium Separation
25. After the period for 90y ingrowth, slurry the precipitate on the
planchet with 2 ml water and transfer to a centrifuge tube with the
aid of a rubber policeman. To make the transfer quantitative, wash
the residue from the planchet with a small amount of 1 N HNOq.
Dissolve the precipitate in the tube with sufficient 1 N HN03, and
dilute with water to 10 ml.
110
-------
26. Add 1.0 ml yttrium carrier and stir.
27. Boil to expel dissolved carbon dioxide; cool to room temperature.
28. Replace in water bath and make basic with 2-3 ml 15 N NIfyOH. Stir
and digest until the yttrium hydroxide precipitation is complete.
29. Cool, centrifuge, and decant supernatant into a 100-ml beaker.
Record time of separation. This is the end of yttrium-90 ingrowth
and the beginning of yttrium-90 decay.
30. Dissolve precipitate in 1 ml 1 N HN03 and dilute with water to
10 ml.
31. Reprecipitate yttrium by dropwise addition of 15 N NH^OH.
32. Centrifuge, combine supernatant with solution in the 100-ml beaker
(step 29).
33. Repeat steps 30, 31 and 32. Save the combined supernatants in the
beaker for strontium activity and gravimetric yield determination,
step 41.
34. Dissolve the Y(OH)3 precipitate from step 32 with 2 ml 1 N HNO
and dilute to 5 ml with water.
35. Slowly add 5 ml sat. 1^20^, with stirring, and digest in hot water
bath for 10 minutes.
36. Cool in an ice bath to room temperature.
37. Centrifuge and discard supernatant.
38. Wash precipitate twice with 10 ml hot water and discard wash
solutions.
Ill
-------
39. Filter the yttrium oxalate on a tared glass-fiber filter. Wash with
hot water and ethanol.
40. Dry, cool, weigh, mount and count the 9^Y.
41. Warm the combined supernatant solution from step 33, add 5 ml
1.5 M Na2C03 and digest for 10 minutes.
42. Cool, centrifuge and discard supernatant.
43. Wash the Sr(X>3 with 15 ml water and discard wash solution.
44. Slurry with a few ml water and transfer quantitatively to a tared
stainless steel planchet. Dry under infra-red lamps.
45. Cool, weigh and count immediately.
Calculations;
I. 89Sr and 90Sr (beta activity):
1. 9°Y cpm (corrected) = A x c
2. 90Sr cpm = 90Y cpm (corrected) x —
Ei
3. 90Y cpm = 90Y cpm (corrected) x G x
4. 89Sr cpm = (R - 90Sr cpm - 90Y cpm) £
r
5. 90Sr activity = Y cpm (corrected)
E x 2.22 x I x V
c. 890 4.- -j. Sr cpm
6. Sr activity = Hx2.22 /j- x v
where :
A = Decay factor for
%l = Ingrowth factor of 90Y from time of strontium purification to
yttrium separation
B2 = Ingrowth factor of 9^Y from time of yttrium separation to time of
total strontium count
C = Yttrium yield
D = 9^Sr efficiency for counter in which radios trontium is counted
E = 9"Y efficiency for counter in which 9^Y is counted
112
-------
F = Qnfay factor for 89sr from sample collection to counting time
G = yUy efficiency for counter in which radiostrontium is counted
H = Efficiency for 89Sr
I = Strontium yield
R = Observed count rate of total radiostrontium fraction (step 18 or
45)
V = Sample volume
iA.fi
II. Ba (beta activity)*:
14°Ba activity (pCl/ml) . LB x e x DJ L| + (F x G x H) j
where:
A = Net cpm
B = Sample volume (ml)
C = Barium chemical yield
D = Correction factor e"Xt for ^Ba decay, where t is the time, in
hours, from sample collection to time of counting if X is in hr~l
E = Efficiency for counting l4°Ba
F - Efficiency for counting l40La
(pCi)
G = Correction factor 1-e" * for the degree of equilibrium attained,
where t is the time, in hours, from the barium separation to the
time of counting
H = The ratio of La. to 1^°Ba when the mixture is in transient
equilibrium (1.153).**
Confirmation of Purity of 90Sr. 90Y and 140Ba Activities
1. Immediately plot the gamma-ray spectrum of each separated product
to identify the short-lived 9. 7-hr 91Sr in the SrC03 precipitate,
and any contaminating gamma-ray emitters in either precipitate. If
the sample is analyzed soon after collection, the 9- 7-hr 91gr
photopeaks may be discernible at 1025. 748 and 645 keV.
2. Repeat the gamma measurement of the I40ga over a period of a week
to observe the ingrowth of the ^®La daughters.
* "Radioassay Procedures for Environmental Samples", Env. Health Series,
BRH, Public Health Service Publication 999-RH-27, Jan. 1967.
**Based on the 140Ba half life of 12.8 d and the 140La half life of
40 hrs.
113
-------
3. Beta count the planchet over a 2-week interval to check the 90Y
decay and the ingrowth of 90Sr_90Y and l4°Ba-14°La.
Notes:
1. If excess calcium is present in the sample, steps 5, 6 and 7
should be repeated as often as is necessary to remove all the
calcium.
2. The counting result, immediately ascertained, represents the
strontium activity (^Sr + ^Sr) pius an insignificant fraction
of the 9QY that has grown in from the separated 90Sr. To
determine the 89gr an(j 90sr with a greater precision, the planchet
should be stored at least two weeks so that the 90gr_90Y activity
will be in equilibrium. At this point, steps 25-45 are to be
performed on the precipitate in the planchet.
Reference:
1. Hahn, R. B. and Straub, C. P., "Determination of Radioactive
Strontium and Barium in Water", J. Am. Water Works Assn. 47,
335 (April 1955).
114
-------
Radioactive Sulfur
Principle of Method
Sulfur carrier and appropriate holdback carriers are added to the
aqueous sample. After sulfides are oxidized to sulfates, impurities
are removed by an hydroxide scavenge. The sulfur is purified as
NH2C6H4C6H4NH2.H2S04 for counting.
Procedure Time
2 samples - 5 hrs.
Reagents
Ammonium hydroxide, NH^OH: 15 N (cone.), IN, 0.1 N
Benzidine hydrochloride, WfyC^C^Wfy .2HC1: 2%
Cadmium carrier: 20 mg/ml
Cobalt carrier: 5 mg/ml
Copper carrier: 20 mg/ml
Ethanol, C2H5OH: 95%
Hydrogen peroxide, "^2^2 ' ^®%
Hydrogen peroxide - Ammonium hydroxide solution: (5:1)
Indicator, phenolphthalein: 1%
Iron carrier: 10 mg/ml
Manganese carrier: 5 mg/ml
Phosphorus carrier: 5 mg/ml
Sulfur carrier: 3 mg/ml as S"
Zinc carrier: 5 mg/ml
Zirconium carrier: 10 mg/ml
Procedure
1. To an unacidified aqueous sample (200 ml or less), add 1.0 ml
sulfur carrier, and 0.1 ml (2 drops) each of cadmium, cobalt,
copper, iron, manganese, phosphorus and zinc holdback carriers
(Note 1).
2. Oxidize the S= to SO^ by slowly adding 10 ml H^-N^OH (5:1)
solution. Evaporate to complete dryness.
115
-------
3. Slowly add 5 ml H202-NH4OH solution to residue to avoid spattering,
and evaporate to complete dryness.
4. Slurry residue with a few drops of H202 and add 15 ml water.
(Loosen with a rubber policeman if necessary.) Heat for a few
minutes to dissolve sulfates, and cool.
5. Filter residue through Whatman #41 (or equivalent), wash with 5 ml
water and combine wash solution and filtrate. Discard filter paper.
6. Add 0.1 ml each of zirconium, cobalt and iron carriers, adjust to
pH 6.5 with 0.1 N NH^OH and add 3 drops H202. Heat and stir until
all H2C>2 is boiled away and precipitate is coagulated. Cool to
room temperature.
7. Filter through Whatman #41 (or equivalent) into a centrifuge tube.
Discard filter paper.
8. Add 2-3 drops phenolphthalein indicator and adjust to end point
with 1 N NH^OH. Cool in ice bath and add 2 ml benzidine hydro-
chloride. Stir, settle, centrifuge and discard supernatant.
9. Wash precipitate with 20 ml water and discard wash solution.
10. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
11. Dry, cool, weigh, mount using 0.25mil mylar and count.
Calculation
Calculate the concentration, D, of sulfur-35 in picocuries per
milliliter as follows:
D =
2.22 x EVR
116
-------
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate decay corrections as follows:
A = A0 e-<>.693t/T
where:
A = activity at time t,
A0 » activity at time zero,
e = base of natural logarithms,
t = elapsed time in days, and
T = half life of 35s (87.2 d).
Confirmation of the Purity and Activity of 35s
1. Plot gamma-ray spectrum of the separated sample to assure complete
decontamination from interfering radionuclides. If contaminated,
the analysis should be repeated with appropriate scavenging steps
and holdback carriers.
2. Beta count the planchet several times over a 30-day period to
confirm the 87.2-d half life.
Note:
1. It is imperative that these carriers were not prepared in the
sulfate form to assure accurate- calculation of chemical yield,
References:
1. Leddicotte, G. W., "The Radiochemistry of Sulfur", Nuclear
Science Series, NAS-NS-3054, Nat'l Res. Council, USAEC, 1962.
2. Elinson, S. V. and Petrov, K. I., Analytical Chemistry of
Zirconium and Hafnium (Ann Arbor-Humphrey Science Publishers,
Ann Arbor, Michigan, 1969) p. 47.
117
-------
Radioactive Tantalum and Niobium
Principle of Method (Note 1)
Tantalum, niobium and zirconium carriers are added to the acidified
aqueous sample and collected as phosphates. The zirconium is precipi-
tated as the fluorozirconate, leaving tantalum and niobium in solution.
The tantalum is extracted into MIBK, back extracted into water and
purified as Ta205 for counting; niobium is precipitated as the basic
hydroxide and purified by ashing as Nb20g for counting.
Procedure Time
2 samples - 8 hrs. (Zr-Nb time) + 2 hrs.
Reagents
Acetone, (CH-^CO: anhydrous
Ammonium hydroxide, NH-OH: 15 N (conc.)s 6 N
Ammonium nitrate, NH^NOg: 27,
Cobalt carrier: 5 mg/ml
Hydrofluoric acid, HF: 5 N
Indicator, phenolphthalein: 1%
Methyl isobutyl ketone, CgH120, (MIBK)
Niobium carrier: 10 mg/ml
Nitric acid, HN03: 16 N (cone.), 1 N
Oxalic acid, H2C20^: saturated
Tantalum carrier: 10 mg/ml
Zirconium carrier: 10 mg/ml
Procedure
1. To an aqueous sample (200 ml or less), add 5 ml 16 N HNOo, 1 ml sat.
H2C2°4> 2.0 ml each of tantalum, zirconium and niobium carriers
and 1 ml cobalt holdback carrier. Stir. Follow the procedure for
zirconium and niobium (p.159) from step 2 through step 13.
2. Wash the mixed niobium-tantalum precipitate with 10 ml hot 2% NH NO
4 3
and discard wash solution.
118
-------
3. Dissolve precipitate in 0.5 ml 5 N HF plus 5 ml 1 N HNOg. Add 5 ml
MIBK and stir with a polypropylene rod for 2 minutes. Transfer to
a polypropylene separatory funnel. Drain aqueous phase into a
polypropylene tube and transfer organic layer to a 60 ml glass
separatory funnel. Add 5 ml MIBK to the aqueous phase and stir
with a polypropylene rod for 2 minutes. Transfer to the poly-
propylene separatory funnel. Combine organic layer with that in
the glass separatory funnel. Save aqueous phase which contains
niobium for step 9.
4. Back extract organic phase twice with 5 ml portions of waters
collecting aqueous phases in a centrifuge tube. Discard organic
layer.
5. Add 2-3 drops phenolphthalein indicator and adjust to the end point
with 15 N NH^OH to precipitate Ta205. Digest in a hot water bath
5-10 minutes. Centrifuge and discard supernatant.
6. Wash precipitate with 10 ml hot 2% NtfyNC^ and discard wash solution.
7. Transfer to a tared glass-fiber filter with 10 ml acetone.
8. Dry, cool, weigh, mount and count precipitate as Tla.^^.
9. To supernatant from step 3, add 2-3 drops phenolphthalein indicator
and make basic with 15 N liffl^OH to precipitate Nb205. D1Sest in a
hot water bath 5-10 minutes. Centrifuge and discard supernatant.
10. Wash precipitate with 10 ml hot 2% NH^NO^ and discard wash solution.
11. Slurry with water and filter through Whatman #42 (or equivalent).
119
-------
Transfer filter paper to a porcelain crucible, dry and heat in
furnace for 1 hour at 800°C. (Note 2).
12. Cool, and transfer to a tared glass-fiber filter with water. Wash
with successive portions of water and ethanol.
13. Dry, cool, weigh, mount and count as Nb^O,..
Calculations
I. Tantalum
Calculate the concentration, D, of tantalum-182 in picocuries
per milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E a Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for the tantalum isotopes as
follows:
. . -0.693t/T
A = AQ e
where:
A = activity at time t,
A = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and,
T = half life of separated nuclides in same units as t.
120
-------
Confirmationof Purity and Identification of Tantalum Isotopes
1. Plot the gamma-ray spectrum of the separated sample to identify
the major 182Ta photopeaks (1220, 1120 and 68 keV), the major
183Ta photopeaks (246, 354 and 108 keV) and verify the purity of
the separation. The presence of other photopeaks may indicate
contamination, necessitating repetition of the analysis with
additional holdback carriers and scavenging.
2. Repeat gamma measurement and beta counting at 1-week intervals to
follow decay of the photopeaks and corroborate the half lives of
183Ta (5.1 d) and 182Ta (115 d)>
II. Niobium (see page 162).
Notes:
1. Combining this procedure with the zirconium-niobium procedure
(P. 159) makes it possible to analyze for zirconium, niobium
and tantalum on one aliquot.
2. To prevent flash ignition which would cause loss of unashed
filter paper and activity, the dried crucible should be put
into the cold muffle as the temperature is raised to 800°C.
After an hour at this temperature the crucible is carefully
removed and allowed to cool.
References:
1. Faye, G. M. and Intnan, W. R., Res. Rept. MD-210, Canadian Dept.
of Mines and Tech. Surveys, Aug. 1957.
2. Steinberg, E. P., "The Radiochemistry of Niobium and Tantalum",
AEC Rept. NAS-NS-3039, 1961.
121
-------
Radioactive Tellurium
Principle of Method*
Tellurium carrier is added to the acidified aqueous sample.
Impurities are removed by a double hydroxide scavenge. The tellurium
salts are collected in acid solution and reduced to the metal for
counting.
Procedure Time
4 samples - 8 hrs.
Reagents
Dextrose, CeEl2°6: anhydrous
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 12 N (cone.)
Iron carrier: 10 mg/ml
Potassium hydroxide, KOH: 6 N
Nitric acid, HNC^: 16 N (cone.)
Tellurium carrier: 10 mg/ml
Procedure
1. To an aqueous sample (200 ml or less), add 1 ml 12 N HCl and 2.0 ml
tellurium carrier. Evaporate to damp dryness. (Do not bake.)
2. Slurry the salts with 1 ml 12 N HCl, add 25 ml water and transfer
to a centrifuge tube.
3. Add 0.5 ml iron carrier and make strongly basic with 3-4 ml 6 N
KOH. Digest in a water bath until Fe(OH)3 coagulates. Cool and
centrifuge. Transfer supernatant to a beaker.
*This procedure was developed by Robert Lieberman, Analytical and
Radiochemistry Research Section, EERF, Montgomery, Alabama 36101.
122
-------
4. Wash precipitate with 15 ml water and add wash to supernatant in
beaker. Discard precipitate.
5. Repeat steps 3 and 4, omitting the 6 N KOH.
6. Acidify supernatant with 1-2 ml 12 N HC1 and evaporate to damp
dryness. (Do not bake.)
7. Slurry the salts with 1 ml 12 N HC1 and 25 ml water. Add 1 g
dextrose to reduce the tellurium to the metal, and stir until
completely dissolved. Heat gently, if necessary.
8. Make the mixture strongly basic with 3-4 ml 6 N KOH and heat to
boiling for 10 minutes to coagulate the tellurium metal.
9. Cool and transfer to a centrifuge tube. Centrifuge and discard
supernatant.
10. Slurry the precipitate with 5 ml 12 N HC1. Dilute to 25 ml with
water, stir, centrifuge and discard supernatant.
11. Dissolve the precipitate in 2 ml 16 N HNOg and transfer to a
beaker with a few ml water. Evaporate to damp dryness. (Do not
bake.)
12. Repeat steps 7 through 10.
13. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
14. Dry, cool, weigh, mount and count.
123
-------
Calculation
Calculate the concentration, D, of the 129Te or 132Te activities
in picocuries per milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
-0.693t/T
A = A e
o
where:
A = activity at time t,
AQ - activity at time zero,
e = base of natural logarithms
t = elapsed time from collection, in same units as T, and
T = half life of separated nuclides, 129Te (t1/2 34.1 d) or
(t1/2 78 h).
Confirmation ojL Purity of 12^Te and 132Te and Measurement of Activity
129
1. Plot the gamma-ray spectrum of the separated sample. The Te
photopeak is at 455 keV; the 132Te photopeafc is at 230 keV. .(At
equilibrium, the 523 keV. 668 keV, and 773 fceV photopeaks of the
2.3-hr 132I daughter of l32Te will be present.)
124
-------
2. Repeat the gamma measurement after 2 days to observe the decay of
the shorter-lived (132Te) isotope.
3. Beta count the sample Immediately after separation and at 2-day
intervals to corroborate the half life of *32Te and of 129Te.
Reference:
1. Leddicotte, G. W., "The Radiochemistry of Tellurium", AEC Kept.
NAS-NS-3038, 1961.
125
-------
Radioactive Tin
Principle of Method
Tin carrier and appropriate scavenging carriers are added to the
acidified aqueous sample and collected as mixed sulfides. Impurities
are removed by an hydroxide scavenge. The tin is precipitated with
cupferron and ignited to SnC^ for counting.
Pro c e_d ur e_ T ime
2 samples - 8 hrs.
Reagents
Antimony carrier: 5 mg/ml
Ammonium hydroxide, NH^OH: 15 N (cone.)
Bromine water: saturated
Cupferron: CgHg^C^: 6%
Hydrochloric acid, HC1: 12 N (cone.), 3 N
Hydrogen peroxide, K^C^ : 30%
Hydrogen sulfide, H2S: gas
Iron carrier: 10 mg/ml
Nickel, powdered
Nitric acid, HN03: 16 N (cone.)
Sodium hydroxide, NaOH: 6 N
Tin carrier: 10 mg/ml
Procedure
1. To an aqueous sample (50 ml or less), add 12 IN HC1 to adjust the
sample to 4 tJ HC1. (For a 50 ml sample, this is accomplished by
the addition of 25 ml 12 N HC1.) Add 2.0 ml tin carrier and 1 ml
antimony carrier. Heat and stir approximately 30 minutes. (Note 1),
2. Add 30-40 mg powdered Ni, and continue heating and stirring at
+4 +2
least 15 min to reduce Sn to Sn .
126
-------
3. Filter through Whatman #41 (or equivalent) into a clean beaker and
discard filter paper.
4. Add 2 ml bromine water, neutralize with 15 N NH OH, then make 1 N in
HC1. (For a 50 ml sample this is accomplished by adding 4.6 ml 12 N
HC1). Heat to boiling in a water bath and saturate with ILS at
least 3 min to precipitate a mixture of tin and antimony sulfides.
Cool in an ice bath, centrifuge and discard supernatant.
5. Dissolve precipitate in 3 ml 12 N HC1 and 1 drop R^. Boil off
excess peroxide and add a few ml water. Neutralize with 15 N NH.OH
then make 2.5 N in HCl. (For a 10 ml sample this is accomplished
by adding 2.5 ml 12 N HCl.)
6. Heat to boiling and saturate with ILS to precipitate antimony
sulfide. Filter while hot through Whatman #41 (or equivalent) into
a clean beaker. Wash precipitate with a little 3 N HCl and discard
filter paper.
7. Add 2 ml bromine water to filtrate, neutralize with 15 N NH.OH, then
make 1 N HCl. Heat to boiling in a water bath and saturate with
HLS at least 3 min to precipitate tin sulfide. Cool in ice bath,
centrifuge and discard supernatant.
8. Dissolve precipitate in 2 ml 12 N HCl and 1 drop K^O,, and heat. Add
a few ml water and continue heating to remove excess peroxide.
Dilute to 15 ml.
9. Add 0.5 ml iron carrier. Stir in water bath and add 6 N NaOH until
basic, then add 2 drops more to precipitate Fe(OH)3 and leave tin
127
-------
in solution. Filter through Whatman #41 (or equivalent) into a
clean centrifuge tube. Discard filter paper.
10. Add 5 ml 6% cupferron and chill in an ice bath.
11. Add 12 N HC1 dropwise until precipitate of tin cupferrate no
longer dissolves. Stir well and continue to chill.
12. Filter through Whatman #42 (or equivalent) and wash well with water.
Discard filtrate.
13. Transfer filter paper to a porcelain crucible and dry in oven at
about 110°C.
14. Char cautiously with low heat, then ignite over a Meker burner (or
muffle) at high heat (about 700°C), under oxidizing conditions for
45 rain. Let cool.
15. Moisten with 2 drops 16 N HN03- Let dry carefully on a hot plate
with very low heat, then reignite over a Meker burner (or muffle)
for 15 min. Place in a desiccator to cool.
16. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
17. Dry, cool, weigh, mount and count.
Calculation
Calculate the concentration, D, of the tin isotopes in picocuries
per milliliter as follows:
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
128
-------
V - milliliters of sample used,
R = fractional chemical yield, and
2.22 e conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E m Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for the specific tin isotope as
follows:
-0.693t/T
A = A0 e
where:
A = activity at time t,
Ao » activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of the tin isotope in the same unit as t.
Confirmation of Purity and Identification Tin Isotopes
1. Plot the gamma-ray spectrum of the separated sample to identify the
photopeaks of H3Sn (255 keV, t1/2 H3 d) and of 123sn (1080 keV,
tj/2 125 d) and verify the purity of the separation.
2. Beta count the separated planchet at 30-d intervals to substantiate
the half life of the tin isotope that is present.
Note:
1. The volume should be kept constant during the heating in steps 1
and 2 by adding water as needed to maintain the 4 N HC1 concen-
tration.
References:
1. Meinke, W. Wayne, Ed., Chemical Procedures Used in Bombardment
Work at Berkeley, UCRL-432, U. of Calif., 1949.
2. Bowen, H. J. M. and Gibbons, D., Radioactivation Analysis,
(Oxford University Press, London, 1963) p. 250.
3. Lingane, J. J., Analytical Chemistry of Selected Metallic
Elements (Reinhold, New York, N. Y., 1966) p. 105.
129
-------
Tritium
Principle of Method (Note 1)
The aqueous sample is distilled to dryness to effect quantitative
transfer of tritium to the distillate and to remove interfering radio-
nuclides and quenching materials. A portion of the distillate is mixed
with scintillation solution and counted in a liquid scintillation
spectrometer. Standard tritium and background samples are prepared and
counted alternately, to nullify errors produced by aging of the scintil-
lation medium or instrument drift.
Procedure Time
1 sample - 2 hrs.
Reagents
Scintillation solution (dioxane): prepared reagent
Tritium, 3g. standard tracer solution
Procedure
1. . Distill an unacidified aqueous sample (50 ml or less) to dryness and
collect the distillate in a dry flask. (Note 2).
2. Pipette 16 ml scintillation solution into a 25 ml scintillation vial.
3. Pipette 4 ml sample distillate into scintillation vial, cap tightly
and shake until thoroughly mixed.
4. Prepare a background sample consisting of 4 ml low-tritium water and
16 ml scintillation solution in same manner as sample.
5. Prepare a standard consisting of 16 ml scintillation solution and
4 ml water, containing a standard concentration of tritium activity,
in same manner as sample.
130
-------
6. Dark-adapt and cool sample, background and standard solutions in
instrument freezer to prepare for counting. (Note 3).
7. In normal counting operation, tritium is counted with a window
setting where the figure of merit is at maximum. (Note 1). The
high voltage is set to obtain the peak counting efficiency in the
window.
Calculation
Calculate the concentration, D, of the tritium activity in pico-
curies per milliliter as follows:
D =
2.22 x EV
where:
C = net count rate, counts/rain,
E = efficiency for measuring % in liquid scintillation spectrometer,
V = milliliters of sample used,
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the efficiency, E, for measuring % in the liquid
scintillation spectrometer as follows:
E =X
where:
Y = counts/min determined by counting standard tritium sample (step 5)
at the optimum instrument settings, and
S = standard tritium activity (dpm/ml) as rated by NBS or equivalent,
corrected for decay.
Calculate the decay correction for the tritium activity as follows:
-0.693t/T
A- Aoe
131
-------
where:
A = activity at time t,
AQ = activity at time of collection or from the date the standard was
rated,
e = base of natural logarithms,
t = elapsed time from collection or from the date the standard was
rated,
T = half life of tritium (12.3 yr).
Confirmation of Purity and Identification of the Tritium Activity
1. Determine the count rate for each sample, background and standard.
Three successive results which are within 2 a of each other assure
that the vials have been dark adapted.
2. With a 2-channel spectrometer, one window is set to give the best
figure of merit and the other is set as an impurity screen. The
ratios of the activity for the % standard and for the distilled
samples should be the same at the two window settings. If not,
the samples must be redistilled to remove interfering ionizing
radiations and prepared for counting again.
Notes:
1. This procedure is similar to the ASTM standard method described
on page 23, but since it employs a different scintillation
solution which has been found to give a better "Figure of
Merit",* it has been included in this manual.
2. As a general rule, all samples should be distilled to dryness
for quantitative recovery of tritium and to remove interfering
radionuclides. Iodine-131 in aqueous samples can be eliminated
by adding stable iodine and AgNOo to the flask before the
distillation.
3. The freezer temperature must be maintained above 2°C or, in
time, the solution will begin to solidify. If an ambient
temperature liquid scintillation spectrometer is employed, the
vial must be dark-adapted, usually 24-48 hrs, before counting
begins.
Reference:
1. Butler, F. E., "Determination of Tritium in Water and Urine",
Anal. Chem. 33, 409, 1961.
* Figure of Merit = S2 (Efficiency)2
B (Background)
132
-------
Radioactive Tungsten
PrincipleofMethod
Tungsten carrier is added to a basic aqueous sample and collected
as tungstic acid. Impurities are removed by hydroxide and basic
sulfide scavenges. The tungsten is reprecipitated as tungstic acid
and purified as W02(CgHgON)2 for counting.
Procedure Time
2 samples - 4 hrs.
Reagents
Acetic acid, CH-COOH: 17.4 N (glacial)
Ammonium hydroxide, NH^OH: 15 N (cone.)
Ethanol, C2H5OH: 95%
8-hydroxyquinoline, CgHyNO: 5% in CH3COOH
Hydrogen sulfide, E^S: gas
Iron carrier: 10 mg/ml
Molybdenum carrier: 10 mg/ml
Nitric acid, TWO*}-. 16 N (cone.)
Sodium acetate buffer, (CH-jCOOH-CHLCOONa) : pH 5.0
SuIfuric acid H2SO^: 36 N (cone.)
Tartaric acid, C4H606: 50%
Tungsten carrier: 10 mg/ml
Zirconium carrier: 10 mg/ml
Procedure
1. To an aqueous sample (200 ml or less) made slightly basic (pH 7-9)
with 15 N NH40H, add 2.0 ml tungsten carrier and stir. Add 30 ml
16 N HNOo and bring to vigorous boil to precipitate tungstic acid.
2. Digest at near boiling for 10-15 minutes on hot plate; cool,
centrifuge and discard supernatant.
3. Dissolve in 6 drops 15 N NH^OH and dilute to 15 ml with water. Add
133
-------
2 drops each iron and zirconium carriers, centrifuge and transfer
supernatant to a centrifuge tube. Discard precipitate.
4. Add 1 ml 507o tartaric acid, 0.5 ml 36 N I^SC^ and 0.5 ml molybdenum
carrier. Heat in water bath, bubble in I^S and stir vigorously for
at least 2 minutes. Filter while hot through Whatman #41 (or
equivalent). Wash centrifuge tube with 2-3 ml hot water, pour
through filter paper and combine with filtrate. Discard filter
paper.
5. To filtrate add 10 ml 16 N HNO- and digest the tungstic acid
precipitate in water bath for 10 minutes. Cool, centrifuge and
discard supernatant.
6. Repeat steps 3, 4, and 5.
7. Dissolve the precipitate with 6 drops 15 N NH.OH and transfer to a
125 ml Erlenmeyer flask with 15 ml water. Add 6 drops glacial
CH COOH, 10 ml sodium acetate buffer and heat to boiling. Add 1 ml
57, 8-hydroxyquinoline in CR,COOH, dropwise, boil for 30 seconds and
let cool 5 minutes.
8. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
9. Dry, cool, weigh, mount and count immediately.
Calculation
Calculate the concentration, D, of tungsten-185 and tungsten-187
in picocuries per milliliter as follows:
D
2.22 x EVR
134
-------
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield,
2.22 a conversion factor from disintegrations /min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
for 187W as follows:
E = Fp
where:
F = fractional abundance of the gamma rays, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate the decay correction for the tungsten isotopes as
follows:
A = Ao e-°-693t/T
where:
A as activity at time t,
AQ as activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclide, in same units as t.
Confirmation of Purity and Identification of Tungsten Isotopes
1. Plot the gamma-ray spectrum of the sample immediately after
separation to identify the 618 and 686 keV photopeaks of 187W
(tj/2 24 h). Daily gamma spectral analysis is required to
corroborate the 24-hr half life and confirm the presence of
2. If other photopeaks are present, indicative of gamma impurities,
the analysis should be repeated immediately with the necessary
holdback carriers and scavenge steps included.
3. Beta count the separated sample at 2-week intervals to follow the
decay of 185y (tj/2 75 d, no gamma rays, average beta energy 124 keV),
Reference:
1. Kleinberg, J., Ed., "Collected Radiochemical Procedures", LA-1721,
2nd ed., Los Alamos Scientific Laboratory, U. of Calif., 1954,
pp. 191-196.
135
-------
Radioactive Yttrium
Principle of Method
Yttrium carrier and appropriate holdback carriers are added to the
acidified aqueous sample. The yttrium is collected as the fluoride to
separate it from most of the impurities. After purification by an
hydroxide precipitation and extraction into tributyl phosphate, the
yttrium is precipitated as Y2(0204)3.7H20 for counting.
Procedure Time
2 samples - 4 hrs.
Reagents
Ammonium hydroxide, MfyOH: 15 N, (cone.)
Boric acid, H3B03: saturated
Cobalt carrier: 5 mg/ml
Ethanol, C2H5OH: 95%
Hydrochloric acid, HC1: 6 N
Hydrofluoric acid, HF: 48% (cone.), 5 N
Nitric acid, HN03: 16 N (cone.)
Oxalic acid, ^€204: saturated
Tributyl phosphate, (TBP): equilibrated with 16 N HN03
Yttrium carrier: 10 mg/ml
Zirconium carrier: 10 mg/ml
Procedure
1. To an aqueous sample (200 ml or less), add 1.0 ml yttrium carrier,
1 ml 16 N HN03 and evaporate to 20 ml.
2. Transfer to polypropylene tube with a few ml water. Add 4 ml 16 N
HNO«, 2 ml each of cobalt and zirconium carriers and mix well. Add
5 ml cone. HF to precipitate yttrium fluoride, stir several minutes,
centrifuge and discard supernatant.
3. Dissolve precipitate in 2 ml sat. H3B03 and 2 ml 16 N HN03- Dilute
136
-------
to 10 ml with water, add 2 ml zirconium and cobalt carriers and mix
well. Add 2 ml cone. HF to reprecipitate yttrium fluoride, stir
several minutes, centrifuge and discard supernatant.
4. Wash precipitate with 10 ml 5 N HF and carefully discard wash
solution.
5. Dissolve precipitate in 2 ml sat. H,B00 and 2 ml 16 N HN00. Dilute
j j — j
to 10 ml with water. If turbid, centrifuge and discard residue.
Add 15 N NH^OH with stirring until precipitation of yttrium
hydroxide is complete. Centrifuge and discard supernatant.
6. Dissolve precipitate with 50 ml 16 N HN03 and transfer to a 125 ml
separatory funnel. Add 10 ml equilibrated tributyl phosphate (TBP)
and extract 5 min. Transfer the bottom aqueous layer to another
separatory funnel, add 10 ml equilibrated TBP and repeat the
extraction two more times. Combine the three organic fractions in
the same funnel. Discard the aqueous layer.
7. Wash organic layer with 30 ml 16 N HNO- and discard wash solution.
8. Back extract three times with 10 ml portions of water and combine
the aqueous fractions in a 50 ml centrifuge tube. Discard the
organic layer.
9. Add 15 N NILOH to precipitate yttrium hydroxide. Stir, centrifuge
and discard supernatant.
10. Dissolve precipitate in 2 ml 6 N HC1 and dilute to 15 ml with
water. Heat in water bath and add 20 ml sat. Ji^C^O, to precipitate
yttrium oxalate. Digest for 10 minutes and cool in an ice bath.
137
-------
11. Centrifuge and discard supernatant.
12. Transfer to a tared glass-fiber filter with water. Wash with
successive portions of water and ethanol.
13. Dry, cool, weigh, mount and count.
Calculation
Calculate the concentration, D, of the yttrium activity in pico-
curies per milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray.
Calculate decay corrections as follows:
-0.693t/T
A = AQ e
where:
A - activity at time t,
AQ = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, in same units as T, and
T = half life of separated nuclides 90Y (t, /9 64.0 h), 91Y (t-,/0 58 8 d)
and 93y (t]L/2 10.3 h). i/Z i/Z
138
-------
Confirmation of Yttrium Purity and Identification of Yttrium Isotopes
1. Plot the gamma-ray spectrum of the separated sample to identify
and quantify the 10.3-h 93y (267 and 940 keV) and the 58.8-d 91y
(1210 keV). The presence of other photopeaks indicates contamina-
tion and necessitates repeat of the analysis with appropriate
scavenges and holdback carriers.
2. Gamma scan again in 5 days to measure the decay of 93y, and sub-
stantiate the longer-lived yttrium isotope (1210 keV).
3. Beta count the planchet at daily intervals to confirm the presence
of the pure beta 90y and to corroborate the ^ly half life.
Reference:
1. Kleinberg, J., Ed., "Collected Radiochemical Procedures",
LA-1721, 2nd ed., Los Alamos Scientific Laboratory, U. of
Calif., 1954, pp. 104-107.
139
-------
Radioactive Zinc
Principle of Method
Zinc carrier and appropriate scavenging carriers are added to the
acidified aqueous sample and impurities are removed by basic hydroxide
and acid sulfide precipitations. The zinc is collected as zinc
mercuric thlocyanate and purified as Zn(C^oH6N02)2'H2° for counting.
Procedure Time
2 samples - 4 hrs.
Reagents
Acetic acid, CH3COOH: 1 N
Acetone, (€113)200: anhydrous
Ammonium hydroxide, NH^OH: 6 !R
Ammonium mercuric thiocyanate, NH^HgSCN: prepared reagent
Antimony carrier: 5 mg/ml
Cobalt carrier: 5 mg/ml
Ethanol, C2HsOH: 95%
Hydrogen peroxide, ItjC^ : 30%
Hydrogen sulfide, H2S: gas
Indicator, phenolphthalein: 17.
Iron carrier: 5 mg/ml
Manganese carrier: 5 mg/ml
Nitric acid, HN03: 16 N (cone.)
Oxalic acid, ^2^- 10%
Quinaldic acid solution, CigHylK^.2^0: prepared reagent
Silver carrier: 5 mg/ml
Sodium hydroxide, NaOH: 6 N, 0.5 N
Sulfuric acid, H2SOA: 36 N (cone.), 6 N, 1 N
Zinc carrier: 5 mg/ml
Procedure
1. To an aqueous sample (100 ml or less), add 1 ml 16 N HNO^, 1.0 ml
zinc carrier and 1 ml each of antimony, cobalt, iron, manganese and
silver carriers.
2. Slowly add at least 2 drops BU^ an<* ma'ce sample strongly basic
140
-------
( > pH 13) with 6 N NaOH. Heat and stir until the excess H202 is
boiled off and the mixed hydrous oxide precipitate settles readily,
3. Cool to room temperature and filter through Whatman #41 (or
equivalent) into a graduated beaker. Wash the residue with
5-10 ml 0.5 N NaOH and add wash to the filtrate in the beaker.
Discard filter paper.
4. Evaporate the solution to less than 50 ml, and neutralize with
6 N H2S04- Make solution 3 N in H2S04 by adding 4.2 ml 36 N H2S04
and diluting to 50 ml with water.
5. Heat nearly to boiling and bubble in H2S to precipitate SbgSg.
(Note 1).
6. Cool in an ice bath, filter through Whatman #41 (or equivalent)
into a clean beaker, wash with a few ml 1 N H2SO, and discard
filter paper.
7. Boil off excess H2S and cool in an ice bath. Add 1 ml 10% oxalic
acid, 5 ml NH^HgSCN reagent and stir in the ice bath until
precipitation is complete (about 15 minutes).
8. Transfer to a centrifuge tube, centrifuge and discard supernatant.
9. Add 0.5 ml 16 N HN03 to dissolve precipitate and place in a
boiling water bath. Stir and heat until all brown fumes are gone
and the solution is clear.
10. Add 5 ml water and neutralize to a phenolphthalein end point with
6 N NH^OH.
11. Add 5 ml 1 N CH-jCOOH and 2 ml quinaldic acid solution, stir well
141
-------
and heat in a water bath until the precipitate has settled. Cool,
centrifuge and discard supernatant.
12. Repeat steps 9, 10 and 11.
13. Wash with water containing a few ml 1 N CH3COOH. Centrifuge and
discard wash solution.
14. Transfer to a tared glass-fiber filter with water.
15. Wash once with water and twice with ethanol and acetone.
16, Dry, cool, weigh, mount and count as ZnCCj-HgNCv,^'1^0'
Calculation
Calculate the concentration, D, of Zn in picocuries per milli-
liter as follows:
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R a fractional chemical yield, and ,
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma ray, gammas/disintegration, and
p = photopeak detection efficiency, counts/gamma ray
Calculate the decay correction for Zn as follows:
. -0.693t/T
A = Ao e
142
-------
where:
A - activity at time t,
AQ a activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclide in same units as t (t^/2
Confirmation of Purity and Identification of Zn
1. Plot the gamma-ray spectrum of the separated sample soon after
separation and at 30-day intervals to note presence of contamina-
ting photopeaks and to identify the predominant 65zn photopeak
(1115 keV).
Note:
1. If sulfide precipitate is not observed within 15 seconds, add a
few ml water while the H^S is being bubbled until a precipitate
does form.
References:
1. Lingane, J. J., Analy t ica1 Chemi s t ry of Selected Me ta1lie
Elements (Reinhold, New York, N. Y., 1966) pp. 48 and 131.
2. Bowen, H. J. M. and Gibbons, D., Radioactivation Analysis.
(Oxford University Press, London, 1963) p. 233.
3. Kolthoff, I. M. and Sandell, E. B., Textbook of Quantitative
Inorganic Analysis. 3rd ed. (Macmillan, New York, N. Y.,1952)
p. 93.
143
-------
Radioactive Zirconium and Niobium
Principle of Method
Zirconium and niobium carriers are added to an acidified aqueous
sample and collected as phosphates. The zirconium is precipitated as
the fluorozirconate, reprecipitated with cupferron and ashed to Zr02
for counting; niobium is converted to a fluoride complex and purified
by extraction into tributyl phosphate. After precipitation as the
hydrous oxide, the niobium is ashed to Itt^Oj for counting.
Procedure Time
2 samples - 8 hrs.
Reagents
Acetone, (Clfrj^CO: anhydrous
Ammonium hydroxide, NH^OH: 15 IJ (cone.)
Ammonium nitrate, MfyNO;}: 2%
Barium carrier: 20 mg/ml
Boric acid, 113803: saturated, 57.
Cerium carrier: 5 tag/ml
Cobalt carrier: 5 mg/ml
Cupferron, CgHg^C^ : 6%
Ethanol, C2HsOH: 95%
Hydrochloric acid, HC1: 12 N (cone.), 6 N, 1 N
Hydrofluoric acid, HF: 48% (cone.)
Niobium carrier: 10 mg/ml
Nitric acid, HN03: 16 N (cone.)
Oxalic acid, H2C204: saturated
Petroleum ether
Phosphoric acid, ^PO^: 44 N (cone.)
Potassium bromate, KBr03: solid
Sulfuric acid, ^SO^.: 36 N (cone.), 24 N
Tributyl phosphate, (H3CCH2CH2CH20)3PO, (TBP)
Zirconium carrier: 10 mg/ml
Procedure
1. To an aqueous sample (200 ml or less), add 5 ml 16 N HN03, 1 ml
saturated 0©, 2.0 ml each niobium and zirconium carriers
144
-------
and 1 ml cobalt holdback carrier. Stir. (Note !)„
2. Add 3 ml 44 N H3PO^, heat to boiling, stir for a few minutes and
cool.
3. Decant clear supernatant and transfer precipitate with remaining
solution to a polypropylene tube. Centrifuge and discard super-
natant.
4. Wash precipitate with 20 ml 6 N HC1 and discard wash solution.
5. Dissolve precipitate with 1 ml HF, add 10 ml water and 1 ml cerium
carrier. Stir. Let stand 5 minutes, centrifuge and decant super-
natant into a polypropylene tube. Discard precipitate.
6. Add 2 ml barium carrier, stir, centrifuge and decant supernatant
containing niobium into a 150 ml beaker. Reserve the barium
fluorozirconate precipitate for zirconium purification, step 18.
7. Add 2 ml sat. H3B03 and 20 ml 16 N HN03 to supernatant solution and
heat to boiling. Slowly add 1 g KBr03 and stir until fuming ceases,
Continue stirring and heating until Nb^Cv coagulates.
8. Cool, transfer to a polypropylene centrifuge tube, centrifuge and
discard supernatant,
9. Wash precipitate with 15 ml hot 27o NH,N03, cool and discard wash
solution.
10. Dissolve precipitate with 2 ml HF and 3 ml 24 N I^SO, and add 1 ml
cobalt carrier.
11. Add 5 ml TBP and stir for 2 minutes with a polypropylene rod.
145
-------
Transfer to a polypropylene separatory funnel. When the layers
separate, discard the bottom aqueous phase.
12. Transfer the organic layer to a polypropylene tube and add 5 ml
petroleum ether. Cool in an ice bath and slowly add 5 ml 15 N
NH.OH. Stir for 2 minutes, remove from ice bath and transfer to a
4
polypropylene separatory funnel. When layers separate, drain the
bottom aqueous layer into a polypropylene tube and discard the
organic layer.
13. Wash aqueous phase by stirring 1 minute with 4 ml petroleum ether.
Centrifuge at high speed 1 minute. Decant and discard both
organic and aqueous supernatants (Note 2).
14. Wash precipitate with 10 ml hot 2% NH^N03 and discard wash
solution.
15. Slurry precipitate with water and filter through Whatman #42 (or
equivalent). Transfer to porcelain crucible, dry and heat in
furnace for 1 hour at 800°C. (Note 3).
16. Cool and transfer to a tared glass-fiber filter with water. Wash
with successive portions of water and ethanol.
17. Dry, cool, weigh, mount and count as Nb?0 .
18. Dissolve precipitate from step 6 with 5 ml water, 2 ml 57, H3B03
and 3 ml 12 N HC1. Add 2 drops 36 N H^SO,, stir, cool and centri-
fuge. Decant supernatant into a glass centrifuge tube. Discard
precipitate.
19. Dilute to 20 ml, cool in ice bath, add 2 ml 6% cupferron and stir
146
-------
for a few minutes. Centrifuge and discard supernatant.
20. Wash precipitate with 10 ml 1 N HC1 containing a drop of cupferron
and discard wash solution.
21. Slurry precipitate with water and filter through Whatman #42 (or
equivalent). Transfer to porcelain crucible, dry and heat in
furnace for 1 hour at 800°C. (Note 3).
22. Cool and transfer to a tared glass-fiber filter with water. Wash
with successive portions of water and ethanol.
23. Dry, cool, weigh, mount and count immediately as
/
Calculation
Calculate the concentration, D, of the zr and
curies per milliliter as follows:
D =
2.22 x EVR
where:
C = net count rate, counts/min,
E = counter efficiency,
V = milliliters of sample used,
R = fractional chemical yield, and
2.22 = conversion factor from disintegrations/min to picocuries.
Calculate the counter efficiency, E, for gamma-ray spectrometry
as follows:
E = Fp
where:
F = fractional abundance of the gamma rays, gammas/disintegration for
each nuclide, and
p = photopeak detection efficiency, counts/gamma ray for each nuclide.
147
-------
Calculate decay corrections as follows:
. A -0.693t/T
A = A e
where:
A = activity at time t,
Ao = activity at time zero,
e = base of natural logarithms,
t = elapsed time from collection, and
T = half life of separated nuclide, in same units as t, °5zr
65 d), 95Nb (t1/2 35 d).
Confirmation of Purity of 95Nb and 95zr
1. Plot the gamma ray spectrum of the separated samples to identify
the 95Nb photopeak at 765 keV and the 95Zr photopeaks at 724 and
756 keV. If the sample contains short-lived activities, and is
analyzed soon after collection, the presence of 17-hr °'Zr can be
identified by its 747-keV photopeak in the ZrC^ fraction.
2. Beta count the planchets at 1-month intervals to measure decay and
confirm the 95Nb and 95zr half lives. The calculation of the 95Zr
activity during these counting intervals must consider the ingrowth
of the 95ub daughter into the purified 95Zr precipitate.
Notes:
Oxalic acid must be present for complete exchange of zirconium
and niobium carrier and activity. The solution should be
stirred for at least 10 minutes.
Traces of TBP are removed from the aqueous phase by washing it
with petroleum ether. After centrifugation, the niobium has
precipitated as the hydrated oxide, leaving both the organic
and aqueous phase.
To prevent flash ignition which would cause loss of unashed
filter paper and activity, the dried crucible should be put
into the cold muffle as the temperature is raised to 800°C.
After an hour at this temperature the crucible is carefully
removed and allowed to cool.
References:
Rodden, C. J., Ed., Analysis of Essential Nuclear Reactor
Materials. (Div. Tech. Inf., USAEC, 1964) p. 680 and 685.
Steinberg, E. P., The Radiochemistry of Niobium and Tantalum,
AEC Rept. NAS-NS-3039, 1961.
148
-------
B. Acknowledgments
This laboratory manual is the result of the efforts of the
following personnel of the Radiochemistry and Nuclear Engineering
Research Laboratory, NERC-Cincinnati, Environmental Protection Agency,
who performed repeated evaluations of these methods, analyzed a variety
of aqueous samples using these procedures, and suggested modifications
for improving their clarity, speed and accuracy.
Herman L. Krieger Eleanor R. Martin
Seymour Gold Elbert E. Matthews
Daniel M. Montgomery Richard A. Kaminsky
George W. Frishkorn Franz J. Burmann*
Betty J. Jacobs Edward J. Hanks*
The assistance of the technical personnel at the Eastern Environ-
mental Radiation Facility, Montgomery, Alabama, under the supervision
of Robert Lieberman is also acknowledged for testing these procedures,
for submitting comments for their improvement, and for developing
methodology for chromium and tellurium.
The efforts of Dr. Bernd Kahn, Director, Radiochemistry and
Nuclear Engineering Research Laboratory, NERC-Cincinnati, EPA, is also
acknowledged. His constructive comments over the past several years
have significantly influenced the composition of this manual and helped
bring it to its present state.
*Present address: NERC-Research Triangle Park, EPA, Durham, North
Carolina 27701.
149
-------
C. Appendices
-------
Appendix 1
Reactor Coolant Radionuclide Half-lives and Gamma-ray Energies as Reported in the Literature
Nuelide
227 A
Ac
106m.
Ag
110m.
Ag
241.
Am
41
Ar
76As
131Ba
13 9..
Ba
140,,
Ba
8°Br
80mBr
82Br
83Br
84Br
14c
109
Cd
113mcd
U5Cd
115mcd
141Ce
143Ce
144Ce
Half
21.
8.
253
433
1.
26.
12.
82.
12.
17.
4.
35.
2.
6.
5730
1.
14
55
43
32.
33
284
11
8
5
83
4
0
9
8
6
4
4
4
0
26
5
fp
y
d
d
y
h
h
d
m
d
m
h
h
h
m
y
y
y
h
d
d
h
d
Gamma Energies,
MeV
1.29
0.512, 0.616, 0.80
0.658, 0.885, 0.937
0.060
1.29
0.559, 0.657, 1.21
0.124, 0.216, 0.496
0.166
0.304, 0.438, 0.537
0.511, 0.618
0.037
0.554, 0.777, 1.044
0.530
0.44, 0.88, 1.46
___
0.088
0.265
0.49, 0.53
0.485, 0.935, 1.29
0.145
0.29, 0.668, 0.725
0.134
Nuelide
242Cm
57Co
58Co
6°Co
244Cm
51Cr
134Cs
136Cs
137Cs
138Cs
64.
Cu
Eu
154Eu
155Eu
18F
55
Fe
59Fe
72Ga
3H
181Hf
12 9t
131I
Half life
163
270
71
5
18
27
2
13
30
32
12
12
16
1
110
2
44
14
12
42
1.6 x
8
.3
.26
.1
.8
.07
.7
.0
.2
.7
.7
.81
.7
.6
.1
.4
.5
107
.06
d
d
d
y
y
d
y
d
y
m
h
y
y
y
m
y
d
h
y
d
y
d
Gamma Energies,
MeV
0.
0.
1.
0.57,
0.340
0.463
0.122
0.123
0.
1.
0.
0.
0.
0.044
122, 0.
511, 0.
173, 1.
0.043
0.320
0.605,
, 0.818
0.662
, 1,01,
0.511
, 0.344
, 0,248
087, 0.
0.511
x-ray
095, 1.
630, 0.
346, 0.
0.040
364, 0.
136
811
332
0.796
, 1.05
1.426
, 1.408
, 0.724
105
292
835
482
637
-------
Appendix 1 (Cont'd.)
Nuclide
132 x
133.J.
134I
135I
115mln
42
V
8S
™^TT
854r
87
87Kr
88Kr
140T
La
54Mn
C£
56Mn
"MO
13N
22Na
24K
Na
O'\
I*Tb
97Nb
147Nd
57Ni
63Ni
Half
,2
20
52
6
4
12
10
4
78
2
40
313
2
66
10
2
15
35
72
11
1
92
life
.3
.9
.4
.7
.5
.4
.7
.4
.8
.2
.58
.3
.0
.6
.0
.1
.5
h
h
m
h
h
h
y
h
m
h
h
d
h
h
m
y
h
d
m
d
d
y
Gamma Energies,
MeV
0
0
1.13,
0
0.403
0.196, 0
0
0.847
0
0
1
0
0
.668,
0.
0.955
53
Nuclide
65Ni
239M
Np
« j»
.85, 0.89 •**?
1.-26,
0.
1.
0.
.150,
, 0.85
.85, 1
.487,
0.
1.71
335
524
514
0.305
, 2.57
.55, 2.40
1.596
835
, 1.811, 2.110
.181,
0.
.511,
.369,
0.
0.
.091,
.511,
__
0.740
511
1.275
2.754
765
665
0.533
1.37
-
233Pa
107Pd
147
Pm
149
•L"T 7__
Pm
151Pm
86
m^
105Rh
103D
Ru
106_
Ru
35
3S
12°Sb
122 Sb
124Sb
125Sb
127Sb
46Sc
31Si
151Sm
153sm
Half
2.
2.
14.
27.
7 x 10
2.
53
28
18.
36
39.
368
88
5.
2.
60.
2.
93
84
life
56
4
3
0
6
2
7
7
8
7
2
8
2.6
90
46.8
h
d
d
d
y
y
h
h
d
h
d
d
d
d
d
d
y
h
d
h
y
h
Gamma Energies,
MeV
1.115, 1.481
0.106, 0.228, 0.278
___
0.31
0.286
0.17, 0.340
1.077
0.306, 0.319
0.497, 0.610
0.512, 0.620
0.200, 1.03, 1.17
0.564, 0.686
0.603, 1.691
0.427, 0.599
0.060, 0,25, 0.41
0.889, 1.120
1.26
0.022
0.070, 0.103
-------
Appendix 1 (Cont'd.)
Nuclide
89Sr
9°Sr
91Sr
92 Sr
182Ta
183Ta
99Tc 2.1
M 99m_
in TC
01 132Te
185W
187W
131mXe
133Xe
Half 1
51
28.5
9.7
2.7
115
5.1
x 105
6.0
78
75
24
12
5.3
ife
d
y
h
h
d
d
y
h
h
d
h
d
d
Gamma Energies,
MeV
• ••
_*.*.
0.645, 0.748, 1.025
1.37
1.122, 1.189, 1.222
0.108, 0.161, 0.246
___
0.140
0.228
___
0.479, 0.686
0.164
0.081
Nuclide
133mxe
135Xe
138Xe
88Y
9°Y
91Y
91my
93y
65Zn
69mZn
95Zr
97Zr
Half
2.3
9.2
17
107
64
59
50
10.3
244
14
65
17.0
life
d
h
m
d
h
d
m
h
d
h
d
h
Gamma Energies,
MeV
0.233
0.250, 0.61
0.160, 0.420
0.898, 1.836
1.21
0.551
0.267, 0.94, 1.90
0.511, 1.115
0.439
0.724, 0.757
0,747
References:
1. Mountain, J. E., Eckart, L. E. and Leonard, J. H8, "Survey of Individual Radionuclide
Production in Water-Cooled Reactors", Summary Report, Contract PH 86-67-218, Nucl. Sci.
and Eng. Dept., Univ. of Cincinnati, May 1968.
2. Progress Reports of the following Nuclear Power Facilities:
a. Shippingport (Pa.) c. Dresden (111.) e. Connecticut Yankee
b. Indian Point (N. Y.) d. Yankee (Rowe, Mass.) f. Oyster Creek (N. J.)
3. Lederer, C. M., Hollander, J. M. and Perlman, I., Table of Isotopes. 6th ed. (John Wiley,
New York, N. Y., 1967).
4. Nuclear Data Tables, Sec. A., Vol. 8t 1-2 (Academic Press, New York, N. Y., 1970)
pp. 1-198.
5. Kahn, B. et al^., "Radiological Surveillance Studies at a Boiling Water Nuclear Power
Reactor", USPHS Rept. BRH/DER 70-1 (1970).
6. Kahn, B. et. al^., "Radiological Surveillance Studies at a Pressurized Water Nuclear
Power Reactor", EPA Rept. RD 71-1 (1971).
-------
Appendix 2
Method Capabilities and Decontamination Factors
Minimum Detectable Limits,
pCi/ml
Nuclide Gamma rav* Beta particles*
76ASA8
14CBa
115mC<3
141Ce
144Ce
58Co
6°Co
51Cr
134/137Cs
136Cs
64c«
55Fe
59Fe
3H
131j
133.J.
140La
54Mn
99
Mo
0.04
0.1
0.1
0.1
0.05
0.2
0.05
0.05
0.5
0.05
0.07
0.1
. . .
0.1
MM.
0.05
0.07
0.1
0.06
0.3
0.02
0.02
0.01
0.03
0.01
0.03
0.03
.«••»
0.02
M M M
0.01
0.02
...
. . .
_ .»_
...
0.01
0.02
0.01
_.-
0.01
special case**
M MM
. ..
MMM
M .-»
...
*.MM
.MM
0.03
0.03
___
0.02
_--
i._
0.02
...
0.2
0.02
___
___
0.04
Average
chemical
yield, %
75
60
75
90
65
75
75
75
75
80
85
85
70
75
75
100
80
80
80
65
55
Decontamination Factors***
131t
io3
io2
IO4
io2
IO3
io4
IO4
io3
io3
io3
io4
io4
io3
IO4
IO4
3
10J
— -
___
io3
3
ioj
io2
58/60Co
io3
io3
io3
io3
io2
io3
IO3
...
...
io3
io3
io3
io3
io2
io2
3
10J
3
10
io3
IO3
3
10J
io3
110mA
Ag
_»_
io3
io4
io4
io4
io3
io3
io3
io3
IO3
io3
io3
io3
io4
io4
4
10
2
10
io2
IO3
4
10
io3
-------
Appendix 2 (Cont'd.)
en
Minimum Detectable Limits,
Nuclide
95«b
63Ni
239Np
F
32P
103Ru
106R«
35s
124Sb
113Sn
89Sr
90Sr
182Ta
132ll
91yW
65Zn
957r
drama ray*
0.05
0.15
0.05
0.2
0.04
0.1
...
0.08
0.04
0.06
1.0
0.15
0.05
pCi/ml
Beta particles* special case**
0.05
0.06
0.01
0.01
0.01
0.01
0.05
0.02
— — w «>••••
0.05
0.01
0.02
0.02
0.02
0.03
0.02
— ,. _ *. •» •
0.03
Average
chemical
yield, %
65
80
90
85
85
85
80
90
75
80
80
50
80
65
50
75
80
75
Decontamination Factors***
131T 58/60Co 110mAjj
io4
io4
io4
io2
io3
io3
io3
io3
io3
io4
io4
io3
io2
io2
io3
IO4
io3
io4
io2
io3
io4
io3
io3
io3
io2
io3
io3
io4
io4
io3
io3
io2
io3
io3
IO3
io2
ioj
io3
io4
io3
io3
io3
io3
io3
io3
io4
io4
io3
io3
io3
io3
io4
io4
io3
100 min counting time. The precipitate, mounted on a nylon ring and disc was counted for y
activity on 10 x 10 cm Nal(Tl) detector, and for p activity in a low-background beta counter
(~1 c/m bkgd). Although it is not always practical, lower limits can be obtained with
larger sample volumes and longer counting time.
*For the special cases for a few selected nuclides, the limit for 3H is based on a 4-ml
aliquot counted 300 minutes in a liquid scintillation system; for 3Fe, the value is
derived from a 1000-minute count on the x-ray proportional counter; for the others, the
limits are based on a 400-ml plastic container 10-ctn dia. x 6.5-cm high counted for
300 minutes on the 10 x 10 cm Nal(Tl) detector.
These four nuclides were the most resistant to complete decontamination in the course of
analysis. No problem was ever encountered with the other nuclides present, and for them
the decontamination factor would be > 10 .
-------
Appendix 3
Suggested Order of Analyses for Aqueous Reactor Samples
1. Sodium
2. Iodine
3. Copper
4. Technetium
5. Tungsten
6. Strontium
7. Yttrium
8. Cerium
9. Zirconium
10. Arsenic
11. Neptunium
12. Lanthanum and Trivalent Rare Earths
13. Molybdenum
14. Tellurium
15. Antimony
16. Barium
17. Phosphorus
18. Chromium
19. Cesium
20. Niobium
21. Ruthenium
22. Iron
23. Sulfur
24. Manganese
25. Cobalt
26. Cadmium
27. Tantalum
28. Tin
29. Silver
30. Zinc
31. Nickel
32. Tritium
33. Carbon-14
158
-------
cn
Appendix 4
Efficiency Multiplication Factors for Gamma-ray Emitters
Nal(Tl) 4" x 4" cylindrical detector
Nuclide
41Ar
76.
As
77.
As
133Ba
140Ba
140Ba-14°La
82Br
109Cd
115Cd
115mcd
141Ce
143Ce
l44Ce
57Co
58Co
6°Co
51Cr
134Cs
Half life
253 d
1.83 h
26.4 h
38.7 h
10.7 y
12.8 d
12.8 d
35.3 h
453 d
55 h
43 d
32.5 d
33 h
284 d
270 d
71.3 d
5.26 y
27.8 d
2.07 y
Principal
Y
Energy >
'MeV
0.658 + 0.68 + 0.706
1.27
0.559
0.239
0.302 + 0.356 + 0.382
0.537
1.60
1.044
0.084
0.53 + 0.49
0.935
0.145
0.293
0.134
0.122 + 0.136
0.810
1.332
2.54 (sum peak)
0.320
0.796 + 0.802
Abundance ,
96 + 16 + 19
99
43
2.5
91
34
96
29
4
26 + 10
1.9
48
46
11
87 + 11
99
100
100
9
88 + 9
Approximate
Number
of
Channels*
59-72
115-148
49-62
17-30
25-42
43-56
149-170
99-116
7-14
41-62
87-100
9-18
23-34
9-18
9-18
71-90
125-142
239-270
27-36
73-86
Iff. Factor **
/ dpm/cpm
( Ring & Disc
Geometry***
6.4
11.4
5.5
3.0
3.6
5.2
12.6
9.2
3.0
5.2
8.1
3.2
3.4
3.2
3.2
7.3
10.8
72.8
3.5
7.3
-------
Appendix 4 (Cont'd.)
Nuclide
136Cs
137Cs
Cu
59Fe
131I
133.J.
135I
85Kr
140La
54Mn
56Mn
99Mo
22Na
24Na
95Nb
147Nd
57Ni
239N
103_
Ru
Half life
13.7
30
12.7
44.6
8.06
20.9
6.7
4,4
40.2
313
2.58
66.3
2.6
15.0
35
11.1
1.5
2.4
39.7
d
y
h
d
d
h
h
h
h
d
h
h
y
h
d
d
d
d
d
Principal
Y
Energy ,
MeV
1.05
0.662
0.511
1.10
0.364
0.53
1.72 + 1.80
0.15
1.60
0.835
0.847
0.140
0.740 + 0.780
1.275
1.369
2.754
0.765
0.533
1.37
0.106 + 0.122
0.497
Abundance ,
7.
82
85
38
56
82
90
30
74
96
100
99
7 + 90
12+4
100
100
100
100
13
86
72
88
Approximate
Number
of
Channels*
97-110
59-74
41-62
103-116
31-40
40-62
157-186
9-18
149-170
73-90
75-98
9-18
67-80
111-132
123-150
259-290
69-82
43-58
129-146
9-18
43-56
Eff. Factor **
dpm/cpm
Ring & Disc
Geometry***
9.0
6.2
5.2
9.4
3.8
5.2
13.6
3.3
12.6
7.6
7.7
3.2
6.8
9.5
11.2
19.5
7.0
5.3
11.2
3.2
5.2
-------
Appendix 4 (Cont'd.)
Nuclide
106Ru-106Rh
122Sb
1240,.
Sb
125
Sb
91
Sr
182Ta
99mTc
132Te
187W
135Xe
91Y
93Y
652n
95Zr
97Zr
Half
1.01
2.7
60.2
2.71
9.7
115
6.0
78
24
9.2
59
10.3
244
65
17.0
life
y
d
d 0
y
h
d 1
h
h
h
h
d
h
d
d
h
Principal
Y
Energy ,
MeV
0.512
0.564
.603 + 0.644 + ~0.72
0.427 + 0.463
1.025
.12 + 1.19 + 1.23
0.140
0.230
0.773
0.686 + 0.618
0.250
1.21
0.267
0.947
1.115
0.724 + 0.756
0.743
Abundance ,
7»
21
66
97 + 7 + 14
41
30
90
90
91
89
33
91
0.3
6,4
2.3
49
44 + 54
94
Approximate
Number
of
Channels*
45-58
49-62
53-78
37-48
93-110
107-126
5-18
17-28
71-84
63-72
17-28
111-128
19-40
85-104
103-116
65-81
65-78
Eff. Factor**
dpm/cpm
Ring & Disc
Geometry***
5.2
5.5
5.9
4.1
8.8
9.8
3.2
3.4
7.0
6.4
3.4
10.1
3.2
8.3
9.4
7.0
6.9
*For a 10 x 10-cm NaI(Tl) detector with analyzer calibrated at 10 keV/channel.
**Efficiency multiplication factors have been calculated for other geometries:
1. Falcon container - 5-cm dia. x 6.5-cm high, 35 ml sample; the factor is 1.47 times
the nylon ring and disc value.
2. Plastic container - 10-cm dia. x 6.5-cm high, 400 ml sample; the factor is 2.88
times the nylon ring and disc value.
***Plastic ring and disc in 1" diameter, molded of nylon. The precipitate is filtered on
2.8-cm fiber glass filter, covered with mylar (0.01 or 0.005 mm) and mounted for counting.
-------
Appendix 5
Decay Correction Factors
Fractional Half Lives
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1. 00
1.10
1.20
1.30
1.40
1.50
1.60
1.70
1.80
1.90
2.00
2.10
2.20
2.30
2.40
2.50
2.60
2.70
2.80
2.90
3.00
3.10
3.20
3.30
3.40
3.50
3.60
3.70
3.80
3.90
4.00
0.000
1.0000
0.9330
0.8706
0,8123
0,7579
0.7071
0.6598
0.6156
0.5743
0.5359
0.5000
0.4665
0.4353
0.4061
0.3789
0.3536
0.3299
0,3078
0.2872
0.2679
0.2500
0.2333
0.2176
0,2031
0.1895
0.1768
0.1649
0.1539
0.1436
0.1340
0.1250
0.1166
0.1088
0.1015
0 . 0947
0.0884
0.0825
0.0769
0.0718
0.0670
0.0625
0.020
0.9862
0.9202
0.8586
0.8011
0.7474
0.6974
0.6507
0.6071
0.5664
0.5285
0.4931
0.4601
0.4293
0.4005
0.3737
0.3487
0.3253
0.3035
0.2832
0.2643
0.2466
0.2300
0.2146
0.2003
0.1869
0.1743
0.1627
0.1518
0.1416
0.1321
0.1233
0.1150
0.1073
0,1001
0.0934
0.0872
0.0813
0.0759
0.0708
0.0661
0.0616
0.040
0.9727
0.9075
0.8467
0.7900
0.7371
0.6878
0.6417
0.5987
0.5586
0.5212
0.4863
0.4538
0.4234
0.3950
0.3686
0.3439
0.3209
0.2994
0.2793
0.2606
0.2432
0.2269
0.2117
0.1975
0.1843
0.1719
0.1604
0.1497
0.1397
0.1303
0.1216
0.1134
0.1058
0.0988
0.0921
0.0860
0.0802
0.0748
0.0698
0.0652
0.0608
0.060
0.9593
0.8950
0.8351
0.7792
0.7270
0.6783
0.6329
0.5905
0.5510
0.5141
0.4796
0.4475
0.4175
0.3896
0.3635
0.3392
0.3164
0.2952
0.2755
0,2570
0.2398
0.2238
0.2088
0.1948
0.1817
0.1696
0.1582
0.1476
0.1377
0.1285
0.1199
0.1119
0.1044
0.0974
0.0909
0.0848
0.0791
0.0738
0.0689
0.0643
0.0600
0.080
0.9461
0,8827
0.8236
0.7684
0.7170
0.6690
0.6242
0.5824
0.5434
0.5070
0.4730
0.4414
0.4118
0.3842
0.3585
0.3345
0.3121
0.2912
0.2717
0.2535
0.2365
0.2207
0.2059
0.1921
0.1792
0.1672
0.1560
0.1456
0.1358
0.1267
0.1183
0.1103
0,1029
0.0961
0.0896
0.0836
0.0780
0.0728
0.0679
0.0634
0.0591
162
-------
Sample Calculation Sheet
SAMPLE *
Sample description:
Collection date:
Energy Channels
Counting Geometry:
NUCLIDE
at t.
pCi
c/m " 2.22X
INSTRUMENT:
Scan #
C = Counting time,
G = Gross cpm,
B = Bkgd cpm, .
Net cpm = G - B
min.
cpm
H/2 ~
Eff. Mult. Fac.
Abundance:
Sample size:
Chemical yield:
Counting date
Elapsed time, t
t/Ti/2 = F =
Decay factor = 2
|G + B
C.
+ B
••••*•
C
1
-------
Appendix 6
Reagent Preparation
Distilled or deionized water should be used in the preparation
of all reagents requiring water as the solvent.
•"•• Carrier Solutions - These solutions, prepared as the specific ion,
are to be filtered and standardized prior to use. Some salts (cerium
and lanthanum nitrate, for example) contain naturally radioactive
impurities (Th), so reagent blanks should be prepared to ascertain
instrument plus reagent background.
Ag - 20 mg/ml. Dissolve 3.150 g AgN03 in water and dilute to
100 ml. Store in the dark in a brown glass container.
AS _ - 5 mg/ml. Dissolve 0.788 g AgN03 in water and dilute to
100 ml. Store in the dark in a brown glass container.
As _ - 20 mg/ml. Dissolve 8.3 g Na2HAs04.7H20 in water and
dilute to 100 ml.
+2
Ba _ - 20 mg/ml. Dissolve 3.577 g BaCl2.2H20 in water and
dilute to 100 ml.
+3
Ce - 5 mg/ml. Dissolve 1.545 g Ce(N03)3. 61^0 in water and
dilute to 100 ml.
+2
Cd _ - 20 mg/ml. Dissolve 5.489 g Cd (N03>2.4H20 in water and
dilute to 100 ml.
+2
Co - 5 mg/ml. Dissolve 2.469 g Co(N03)2 .6H20 in water and
dilute to 100 ml.
+3
Cr - 10 mg/ml. Dissolve 5.1 g CrCl.eHO in water and dilute
to 100 ml.
Cr _ - 10 mg/ml. Dissolve 2.8 g t^C^Ch in water and dilute to
100 ml.
Cs _ - 10 mg/ml. Dissolve 1.267 g CsCl in water and dilute to
100 ml.
+2
Cu _ - 20 mg/ml. Dissolve 4.232 g CuClo in water and dilute to
100 ml.
+3
Fe - 10 mg/ml. Dissolve 4.840 g FeCl3.6H20 in water, add 1 ml
6 N HC1 and dilute to 100 ml.
JL _ " 20 mg/ml. Dissolve 2.616 g KI in water, add 2 drops
Na2S03 and dilute to 100 ml. Store in dark flask.
+3
La _ - 10 mg/ml. Dissolve 3.127 g La(N03)3.6H20 in water and
dilute to 100 ml.
164
-------
5 tng/ml. Dissolve 1.801 g MnCl2.4H90 in water and
dilute to 100 ml.
10 tag/ml. Dissolve 1.840 g (NH4)6Mo702A .4H20 in 1 ml
0.5 M KaBr03 and dilute to 100 ml with 6 N HC1.
10 mg/ml. Dissolve 5.2 g K8Nb60i9.16H20 in 50 ml water,
heat nearly to boiling and add 10 ml 16 N HN03 slowly
with stirring. Continue heating and stirring for 2-3
minutes and centrifuge. Wash the precipitate three times
with 10 ml hot 2% NH4N03 solution. Add 40 ml sat. H2C204
and heat with stirring until Nb205 dissolves. Cool and
dilute to 200 ml. Filter if solution is not clear.
5 mg/ml. Dissolve 2.025 g NiCl2.6H20 in water and dilute
to 100 ml.
5 mg/ml. Dissolve 2.197 g KH2PO/. in water and dilute to
100 ml.
10 mg/ml. Dissolve 2.1 g RuClg in 100 ml 0.1 N HC1.
3 mg/ml. Dissolve 2.247 g Na2S.9H20 in water and dilute
to 100 ml.
5 mg/ml. Dissolve 1.00 g powdered antimony in 60 ml 36 N
H2S04 by heating with a burner. Cool and add the
dissolved antimony to 100 ml water. Make a quantitative
transfer by rinsing flask with small portions of water.
Dissolve the antimony sulfate with 15 ml 12 N HC1 and
dilute to 200 ml with water.
10 mg/ml. Dissolve 4.43 g SnCl^SI^O in 30 ml 12 N HC1
by heating and stirring in a hot water bath. Cool, add
20 ml 12 N HC1 and dilute to 150 ml with water. Filter
if solution is not clear.
20 mg/ml. Dissolve 4.831 g Sr(N03)2 in water and dilute
to 100 ml.
10 mg/ml. Fuse 1.3 g Ta2(>5 in a platinum crucible with
3-5 g of a K2C03-KN03 mixture (Ratio 10:1). Heat at red
heat over a flame until melt becomes clear and glassy.
Cool, add cold water to crucible to loosen the melt and
transfer to a beaker with a little water. Add an equal
volume of 16 N HNO3 to **&•* solution 6 N in HN03, and -
heat until Ta205 reprecipitates. Wash the precipitate
three times with 10 ml hot 2% NH^NO, solution. Add 40 ml
water and heat in a water bath. Add about 10 g solid
H2C2°4 until Ta2°5 dissolves. Cool and dilute to 100 ml.
Filter if solution is not clear.
165
-------
Te - 10 mg/ml. Dissolve 1.0 g tellurium metal in 10 ml 16 N
HN03 and evaporate to ~3 ml. Dissolve residue in 10 ml
12 N HC1 and evaporate to ~3 ml. Dissolve residue again
in To ml 12 N HC1 and evaporate to ~3 ml. Slurry into a
100 ml volumetric flask and bring to volume with 3 N HC1.
W*6 - 10 mg/ml. Dissolve 1.795 g Na2W04.2H20 in water and
dilute to 100 ml.
Y*3 - 10 mg/ml. Dissolve 43.1 g Y(N03)3.6H20 in 800 ml water,
add 5 ml 6 N HN03 and dilute to 1 liter.
Zn+2 - 5 mg/ml. Dissolve 1.042 g ZnCl2 in water and dilute to
100 ml.
Zr+4 - 10 mg/ml. Dissolve 3.53 g ZrOCl^SHgO in 0.1 N HC1 and
dilute to 100 ml with 0.1 N HCl.
II. Acids and Inorganic Reagents
Acetic acid, CHgCOOH, 17.4 N. This is the concentrated (glacial)
reagent; sp. gr. 1.06, 99.5%.
Acetic acid, 8 N. Add 460 ml 17.4 N CI^COOH to 500 ml water and
dilute to 1 liter.
Acetic acid, 1.5 N. Add 86 ml 17.4 N CHgCOOH to 800 ml water
and dilute to 1 liter.
Acetic acid, 1 N. Add 58 ml 17.4 N CHLCOOH to 800 ml water and
dilute to 1 liter.
Ammonium acetate, 3 M. Dissolve 231 g CHgCOONH^ in 600 ml water
and dilute to 1 liter.
Ammonium acetate buffer. pH 5.0. Mix 100 ml 1.5 N CH^COOH and
100 ml 3 M CH3COONH4.
Ammonium chloride. 107o. Dissolve 10 g NH^Cl in water and dilute
to 100 ml.
Ammonium hydroxide, NH.OH, 15 N. This is the concentrated
reagent; sp. gr. 0.9, 597».
Ammonium hydroxide, 6 N. Add 400 ml 15 N NH.OH to 400 ml water
and dilute to 1 liter.
Ammonium hydroxide, 2 N. Add 135 ml 15 N NH OH to 500 ml water
and dilute to 1 liter
166
-------
Ammonium hydroxide, 1 N. Add 68 ml 15 N NH.OH to 500 ml water
and dilute to 1 liter.
Ammonium hydroxide, 0.1 N. Add 100 ml 1 N NH,OH to 500 ml
------ . - - - - . . *" — 4
water and dilute to 1 liter.
Ammonium mercuric thiocyanate (prepared reagent). Dissolve 3.15
g NH4SCN and 2.71 g HgCl2 in 100 ml water. Stir, filter and
store in a brown bottle for no longer than one month.
Ammonium nitrate, 2%. Dissolve 2 g NH.N00 in water and dilute
to 100 ml. 4 3
Ammonium phosphate, monobasic, NH.H PO, , solid.
Ammonium phosphomolvbdate (prepared reagent). Dissolve 100 g
of molybdic acid (85% MoOs) in a mixture of 240 ml of water and
140 ml 15 N NH^OH. When solution is complete, filter, and add
60 ml of 16 N HN03. Mix 400 ml of 16 N HN03 and 960 ml of
water. Allow both solutions to cool to room temperature. With
constant stirring, add the ammonium molybdate solution to the
nitric acid solution. Allow to stand for 24 hours. Filter
through Whatman #42 filter paper. Discard the insoluble
material.
Collect the filtrates in a 3-liter beaker and heat to 50°-55°C.
Remove from heating unit. It is important that the solution is
not heated above 55°C to avoid contamination of the precipitate
with molybdic anhydride. Add 25 g of NaH2P(>4 dissolved in 100 ml
of water to the ammonium molybdate solution. Stir occasionally
for 15 minutes and allow the precipitate to settle (approxi-
mately 30 minutes). Filter through Whatman #42 filter paper.
Wash the precipitate with 1% potassium nitrate and finally with
water. Dry the precipitate and paper at 100°C for 3 to 4 hours.
Transfer the (NH4)3(PMoi204o) solid to a weighing bottle, and
store in a desiccator.
Barium nitrate. 10%. Dissolve 10 g Ba(NO,)2 in water and dilute
to 100 ml.
^ acid, saturated. Dissolve 100 g HgBOg in 1 liter boiling
water .
Boric acid, 5%. Dissolve 5 g H3B03 in 100 ml water.
Bromine water, saturated.
Calcium chloride, 3 M. Dissolve 330 g CaCl2 in water and dilute
to 1 liter.
167
-------
Calcium chloride, 1.5 M. Dissolve 165 g CaCl- in water and
dilute to 1 liter.
Chloroplatinic acid, 0.1 M. Dissolve 51.8 g ILPtClg.eiLO in
water and dilute to 1 liter.
Hydrochloric acid, HC1, 12 K. This is the concentrated reagent;
sp. gr. 1.19, 37%.
Hydrochloric acid, 6 N. Add 500 ml 12 N HC1 to 400 ml water
and dilute to 1 liter.
Hydrochloric acid, 4 N. Add 336 ml 12 N HC1 to 500 ml water and
dilute to 1 liter.
Hydrochloric acid, 3 N. Add 250 ml 12 N HC1 to 500 ml water and
dilute to 1 liter.
Hydrochloric acid, 1 N. Add 84 ml 12 N HC1 to 800 ml water and
dilute to 1 liter.
Hydrochloric acid, 0.5 N. Add 42 ml 12 N HC1 to 900 ml water
and dilute to 1 liter.
Hydrofluoric acid, HF, 48% (~30 N). This is the concentrated
reagent; sp. gr. 1.15.
Hydrofluoric acid, 5 N. Add 17 ml 48% HF to 50 ml water and
dilute to 100 ml. Store in polypropylene bottle.
Hydrofluoric acid, IN. Add 3.5 ml 48% HF to 50 ml water and
dilute to 100 ml. Store in polypropylene bottle.
Hydrogen peroxide, HoCL* 30%.
Hydrogen peroxide - Ammonium hydroxide solution. (5:1) . Mix
50 ml ELO* and 10 ml 15 N NH4OH.
Hydrogen sulfide, l^S, gas.
lodic acid, 0.35 M. Dissolve 61.6 g HI03 in water and dilute
to 1 liter.
Iron chloride, 0.1 M. Dissolve 27 g FeClg.ei^O in water plus
2 ml 12 N HC1 and dilute to 1 liter.
Iron, wire #36, analytical grade.
168
-------
Magnesia Mixture. Dissolve 20 g NH.C1 in water, add 10 g MgCL,
and dilute to 100 ml, 4 2
Magnesium metal. Mg. solid, ribbon.
Nickel, powdered, analytical grade.
Nitric acid, HNOg, 16 N. This is the concentrated reagent;
sp. gr. 1.42, 70%.
Nitric acid, 6 N. Add cautiously 375 ml 16 N HNO, to 600 ml
- - - .1 i --------- J- .i - j r J-..IT J _i_Ji ____ """" 3
water and dilute to 1 liter.
Nitric acid, 4 N. Add cautiously 250 ml 16 N HNO» to 700 ml
water and dilute to 1 liter.
Nitric acid, 1 N. Add 62 ml 16 N HNO., to 900 ml water and
dilute to 1 liter.
Nitric acid, 0.2 N. Add 12.5 ml 16 N HN00 to 900 ml water and
, i . . """ j
dilute to 1 liter.
Oxalic acid. 107,. Dissolve 10 g H-CLO. in water and dilute to
100 ml. * Z *
Oxalic acid, saturated. Dissolve 150 g H^O, in 1 liter
boiling water.
Perchloric acid, HCIO^, 70% (11.6 N) . This is the concentrated
reagent; sp. gr. 1.67.
Perchloric acid, 1 N. Dilute 85 ml 70% HC10, to 1 liter with
water.
Phosphoric acid, HgPO,, 85% (44 N). This is the concentrated
reagent; sp. gr. 1.69.
Potassium bromate, KBrOg, solid.
Potassium hydroxide, 6 N. Dissolve 33.7 g KOH in water and
dilute to 100 ml.
Potassium iodate. prepared reagent. Dissolve 100 g KIO» in
333 ml 16 N HN03 and dilute to 1 liter with water.
Potassium iodate wash solution. Dissolve 8 g KIO- in 50 ml
16 N HNO, and dilute to 1 liter with water.
"*"* •?
Potassium nitrite, KN02, solid.
169
-------
Potassium nitrite wash solution (1;100). Dissolve 10 g KN02
in water and dilute to 1 liter.
Potassium permanganate, 0.5 M. Dissolve 7.9 g KMnO, in water
and dilute to 100 ml.
Potassium thiocyanate, KSCN, 0.75 M. Dissolve 7.29 g KSCN in
water and dilute to 100 ml.
Potassium thiocyanate wash solution (1;200). Dilute 0.5 ml
0.75 M KSCN to 100 ml with water.
Silver nitrate, 0.1 M. Dissolve 17 g AgNO- in water and dilute
to 1 liter. Store in a dark container.
Sodium acetate, 3.6 M. Dissolve 295.3 g CH3COONa in water and
dilute to 1 liter.
Sodium acetate buffer. pH 5.0. Mix 100 ml 1 N CHgCOOH and
100 ml 3.6 M CH3COONa.
Sodium bisulfite, 1 M. Dissolve 5.2 g NaHS03 in water and
dilute to 50 ml. Prepare only as much as is needed.
Sodium bromate, 1.5 M. Dissolve 11.5 g NaBrO, in water and
dilute to 50 ml. Prepare only as much as needed.
Sodium bromate, 0.5 M. Dissolve 76 g NaBr03 in water and dilute
to 1 liter.
Sodium carbonate, 1.5 M. Dissolve 160 g Na-CO^ in 600 ml water
and dilute to 1 liter.
Sodium chromate, 0.5 M. Dissolve 171.1 g Na^rO^lO^O in
400 ml water and dilute to 1 liter.
Sodium citrate. 10%. Dissolve 10 g Na.CgH 0 .ZH^O in 100 ml
water.
Sodium hydroxide, 18 N. Dissolve 720 g NaOH in 500 ml water
and dilute to 1 liter.
Sodium hydroxide, 6 N. Dissolve 240 g NaOH in 800 ml water and
dilute to 1 liter.
Sodium hydroxide, 2 N. Dissolve 80 g NaOH in 800 ml water and
dilute to 1 liter.
170
-------
Sodium hydroxide, 0.5 N. Dissolve 20 g NaOH in 800 ml water
and dilute to 1 liter.
Sodium hypochlorite, NaOCl. 5%. This is ordinary liquid
laundry bleach.
Sodium metaperiodate, NalO,, solid.
Sodium nitrite, 1 M. Dissolve 69 g NaN02 in water and dilute
to 1 liter.
Sodium oxalate, 0.1 M. Dissolve 13.4 g Na2C204 in water and
dilute to 1 liter.
Sodium sulfite, Na_SO,, solid.
Sodium sulfite, 1 M. Dissolve 12.6 g Na2S03 in water and
dilute to 100 ml.
Stannous chloride, preparedreagent. Dissolve 2.5 g SnCl2.2H20
in 15 ml 12 N HCl. Heat and stir until dissolved. Prepare
only as much as is needed.
Sulfuric acid, E^SO,, 36 N. This is the concentrated reagent;
sp. gr. 1.84, 95-98%.
Sulfuric acid, 24 N. Add cautiously, with stirring, 667 ml
36 N H2SO^ to 300 ml water and dilute to 1 liter.
Sulfuric acid, 18 N. Add cautiously, with stirring, 500 ml
36 N H2S04 to 400 ml water and dilute to 1 liter.
Sulfuric acid, 12 N. Add cautiously, with stirring, 333 ml
36 N H2S04 to 500 ml water and dilute to 1 liter.
Sulfuric acid, 6 N. Add cautiously, with stirring, 167 ml
36 N H2S04 to 500 ml water and dilute to 1 liter.
Sulfuric acid, 3 N. Add cautiously, with stirring, 84 ml
36 N H2S04 to 800 ml water and dilute to 1 liter.
Sulfuric acid, 1 N. Add cautiously, with stirring, 28 ml
36 N H2S04 to 800 ml water and dilute to 1 liter.
171
-------
III. Organic Reagents
Acetone, (CH«)^CO, anhydrous.
Aerosol solution. 1.5%. Add 1.5 ml Aerosol OT (25%) to 23.5 ml
water.
Benzidine hydrochloride. 2%. Dissolve 5 g
in 40 ml 1 N HC1 and dilute to 250 ml with 50% ethanol. Keep
refrigerated.
a-Benzoinoxiine. 2%. Dissolve 2 g C13H120:C:NOH in 100 ml 95%
ethanol.
Caproic acid, CH
Carbon tetrachloride, CC1, .
Chloroform, CHC1-.
Cupferron. 6%. Dissolve 6 g CgHgNJX in 100 ml water. Keep
refrigerated.
Dextrose, CH.-O/:* anhydrous.
Diethyl ether, (C2H_)20, anhydrous.
Dimethylglyoxime, 1% in C2H OH. Dissolve 1 g (CH3C:NOH>2 in
100 ml 95% ethanol.
1,4 Dioxane, C , HgO- . Scintillation grade.
Ethanol, C2H OH, absolute 99.5%.
Ethanol, COH, 95%.
Ethanol. 50%. Add 105 ml 95% C^OH to 95 ml water.
Sthanol. 20%. Add 42 ml 95% C2H OH to 158 ml water.
8-Hydroxyquinoline, 5% in CH-jCOOH. Dissolve 5 g CgH^O in
100 ml 1.5 N CH0COOH.
~" j
Methyl isobutyl ketone, CHO (MIBK) .
bis-MSBj ^£-bis- (methylstyryl)-benz^enje^ scintillation grade.
Naphthalene, C-0H_, solid.
Petroleum ether.
172
-------
FOPOP. (1.4-di[2-(5 phenyloxazolyl)] benzene).
PPO, (2,5-Diphenvloxazole).
Pyridine,
Quinaldic acid solution a prepared reagent. Dissolve 2 g
C10H7N02-2H2° in 50 ml ethanol, add 4 ml 6 N NaOH and filter
if undissolved residue remains. Dilute to 100 ml with water
and store in the refrigerator.
Scintillation solution (dioxane). Mix thoroughly 7 g PPO,
1.5 g bis-MSB and 120 g naphthalene in 1 liter 1,4-dioxane.
Scintillation solution (toluene). Mix thoroughly 4 g PPO,
0.1 g POPOP in 1 liter toluene.
Tartaric acid. 50%. Dissolve 50 g C^gOg in water and dilute
to 100 ml.
Thioacetamide, CK^CSNIij: solid
Thioacetamide. 5%. Dissolve 2.5 g CH-jCSNHg in 50 ml water,
and filter before using.
Toluene, CgH^CH^, reagent grade.
Tributyl phosphate, (I^CCI^CI^CIfrO^PO, (TBP).
Trioctylphosphine oxide, (CsHjy^PO. Dissolve 20 g trioctyl-
phosphine oxide in 100 ml xylene.
Xylene, Cglfy (013)2, reagent grade.
IV. Indicators and Ion Exchange Resins
Methyl red, 0.17a. Dissolve 0.1 g methyl red in 100 ml 95%
ethanol.
Phenolphthalein, 1%. Dissolve 1 g phenolphthalein in 50 ml
95% ethanol and add 50 ml water.
Ion Exchange Resins
Dowex 50 W-X8, cation resin, 20-50 mesh, 100-200 mesh,
ionic form H+.
Dowex 1-X8, anion resin, 20-50 mesh, 100-200 mesh, ionic
form Cl .
Dowex 2-X8, anion resin, 20-50 mesh, ionic form Cl~ .
173
-------
D. Selected Bibliography
1. Furman, N. H., Ed., Scott's Standard Methods of Chemical Analysis
(D. Van Nostrand, New York, N. Y., 1962).
2. Meites, L., Ed., Handbook of Analytical Chemistry (McGraw-Hill,
New York, N. Y., 1963).
3. Coryell, C. D. and Sugarman, N., Eds., Radiochemical Studies; The
Fission Products, Book 3. Div. IV, Vol. £, Nat'l Nuclear Energy
Series (McGraw-Hill, New York, N. Y., 1951).
4. Barley, J. H., Ed., Manual of Standard Procedures, USAEC Rept.
HASL-300, (1972).
5. Radioassay Procedures for Environmental Samples, Env. Health
Series, PHS Publication #999-RH-27 USDHEW, PHS (Jan. 1967).
6. Krieger, H. L., Velten, R. J. and Burmann, F. J., Eds., Radio-
nuclide Analysis of Environmental Samples, Technical Report R59-6,
USDHEW, PHS (Rev. Feb. 1966).
7. 1972 Book of ASTM Standards, Part 23 (American Society for Testing
and Materials, Phila., Pa., 1972).
8. Hillebrand, W. F., Lundell, G. E. and Hoffman, J., Applied
Inorganic Analysis. 2nd ed. (John Wiley, New York, N. Y., 1953).
9. Lundell, G. E. and Hoffman, J., Outlines of Methods of Chemical
Analysis (John Wiley, New York, N. Y., 1951).
10. Nuclear Science Series, USAEC Rept. NAS-NS-3001 to NAS-NS-3111,
(1965).
11. Lavrukhina, A. K., £££!•» Chemical Analysis of Radioactive
Materials (Chemical Rubber Co. Press, Cleveland, Ohio, 1967).
*u.S.Government Printing Office: 1973 — 759-919/3136 Region 5-11
174
------- |