EPA-R4-73 014
MAY 1973
                         Environmental Monitoring Series
    PROCEDURES FOR RADIOCHEMICAL  ANALYSIS
     OF NUCLEAR REACTOR AQUEOUS SOLUTIONS

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                                  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

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          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

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                            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

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                             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).

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 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

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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

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                     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

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       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

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                  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

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                           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.

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           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

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    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.

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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.

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       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.

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   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)

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                       18/9 Socket
                20/40 5 Joint
                     500ml. Flask
                                             Delivery
                                               Tube
Figure 1.  Distillation Apparatus for Iodine Analysis

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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

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     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.

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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

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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

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       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

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             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

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    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

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          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

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                   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

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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

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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

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                       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

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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

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                        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

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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

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                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

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                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

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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

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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

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                        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

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                         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

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 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

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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

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                     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

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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

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                    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

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                             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

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                     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

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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

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                      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

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                        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

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              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

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                      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

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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

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                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

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 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

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 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

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                      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

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 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

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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

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                           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

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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

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                               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

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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

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                       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

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    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

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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

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       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

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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

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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

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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

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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

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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

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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

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       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

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                    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
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