ASTM D3865-09(2015)
(Test Method)Standard Test Method for Plutonium in Water (Withdrawn 2024)
Standard Test Method for Plutonium in Water (Withdrawn 2024)
SIGNIFICANCE AND USE
5.1 This test method was developed to measure plutonium in environmental waters or waters released to the environment and to determine whether or not the plutonium concentration exceeds the maximum amount allowable by regulatory statutes.
SCOPE
1.1 This test method covers the determination of alpha-particle-emitting isotopes of plutonium concentrations over 0.01 Bq/L (0.3 pCi/L) in water by means of chemical separations and alpha pulse-height analysis (alpha-particle spectrometry). Due to overlapping alpha-particle energies, this method cannot distinguish 239Pu from 240Pu. Plutonium is chemically separated from a 1-L water sample by coprecipitation with ferric hydroxide, anion exchange and electrodeposition. The test method applies to soluble plutonium and to suspended particulate matter containing plutonium. In the latter situation, an acid dissolution step is required to assure that all of the plutonium dissolves.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific hazards are given in Section 9.
WITHDRAWN RATIONALE
This test method covers the determination of alpha-particle-emitting isotopes of plutonium concentrations over 0.01 Bq/L (0.3 pCi/L) in water by means of chemical separations and alpha pulse-height analysis (alpha-particle spectrometry). Due to overlapping alpha-particle energies, this method cannot distinguish 239Pu from 240Pu. Plutonium is chemically separated from a 1-L water sample by coprecipitation with ferric hydroxide, anion exchange and electrodeposition. The test method applies to soluble plutonium and to suspended particulate matter containing plutonium. In the latter situation, an acid dissolution step is required to assure that all of the plutonium dissolves.
Formerly under the jurisdiction of Committee D19 on Water, this test method was withdrawn in February 2024 in accordance with section 10.6.3 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated by the end of the eighth year since the last approval date.
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This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D3865 − 09 (Reapproved 2015)
Standard Test Method for
Plutonium in Water
This standard is issued under the fixed designation D3865; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Applicable Test Methods of Committee D19 on Water
D3084 Practice for Alpha-Particle Spectrometry of Water
1.1 This test method covers the determination of alpha-
D3370 Practices for Sampling Water from Closed Conduits
particle-emitting isotopes of plutonium concentrations over
D5847 Practice for Writing Quality Control Specifications
0.01 Bq/L (0.3 pCi/L) in water by means of chemical separa-
for Standard Test Methods for Water Analysis
tions and alpha pulse-height analysis (alpha-particle spectrom-
etry). Due to overlapping alpha-particle energies, this method
3. Terminology
239 240
cannot distinguish Pu from Pu. Plutonium is chemically
3.1 Definitions:
separated from a 1-L water sample by coprecipitation with
3.1.1 For definitions of terms used in this test method, refer
ferric hydroxide, anion exchange and electrodeposition. The
to Terminology D1129 and Terminology C859.
test method applies to soluble plutonium and to suspended
particulate matter containing plutonium. In the latter situation,
4. Summary of Test Method
an acid dissolution step is required to assure that all of the
4.1 The water sample is acidified and a plutonium isotopic
plutonium dissolves.
236 242
tracer, for example Pu or Pu, is added as a tracer before
1.2 The values stated in SI units are to be regarded as
any chemical separations are performed. Iron is added to the
standard. No other units of measurement are included in this
water as iron (III), and the plutonium is coprecipitated with the
standard.
iron as ferric hydroxide. After decantation and centrifugation,
1.3 This standard does not purport to address all of the the ferric hydroxide precipitate containing the coprecipitated
safety concerns, if any, associated with its use. It is the
plutonium is dissolved, and the solution is adjusted to 8 M in
responsibility of the user of this standard to establish appro- HNO for anion exchange separation.When the sample fails to
priate safety and health practices and determine the applica-
dissolve because of the presence of insoluble residue, the
bilityofregulatorylimitationspriortouse.Specifichazardsare residue is treated by a rigorous acid dissolution using concen-
given in Section 9. trated nitric, hydrofluoric, and hydrochloric acids.
4.2 After an anion exchange separation, the plutonium is
2. Referenced Documents
electrodeposited onto a stainless steel disk for counting by
2.1 ASTM Standards:
alpha pulse-height analysis using a silicon surface barrier or
C859 Terminology Relating to Nuclear Materials
ion-implanted detector. Table 1 shows the alpha energies of the
C1163 Practice for MountingActinides forAlpha Spectrom-
isotopes of interest in this test method. The absolute activities
238 239/240
etry Using Neodymium Fluoride
of Pu and Pu are calculated independent of discrete
C1284 Practice for Electrodeposition of the Actinides for
detector efficiency and chemical yield corrections by directly
Alpha Spectrometry
comparingthenumberofcountsineachpeakrelativetocounts
236 242
D1129 Terminology Relating to Water
observed from a known activity of Pu or Pu tracer (see
D1193 Specification for Reagent Water
Eq 1).
D2777 Practice for Determination of Precision and Bias of
5. Significance and Use
5.1 This test method was developed to measure plutonium
This test method is under the jurisdiction of ASTM Committee D19 on Water
in environmental waters or waters released to the environment
andisthedirectresponsibilityofSubcommitteeD19.04onMethodsofRadiochemi-
and to determine whether or not the plutonium concentration
cal Analysis.
exceeds the maximum amount allowable by regulatory stat-
Current edition approved Jan. 1, 2015. Published January 2015. Originally
utes.
approved in 1980. Last previous edition approved in 2009 as D3865 – 09. DOI:
10.1520/D3865-09R15.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 6. Interferences
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
6.1 Thorium-228, when present in the original water sample
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. at concentrations 100 times or greater than Pu has been
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3865 − 09 (2015)
TABLE 1 Radioactive Decay Characteristics of Isotopes of
(preferably disposable) electrodeposition cell. The cathode is
A
Interest in the Determination of Plutonium in Water
an approximately 20-mm diameter stainless steel disk pre-
Half Life Principal Alpha Energies in MeV
polished to a mirror finish. The anode is an approximately
Isotope
Years (Abundance)
1-mm diameter platinum wire with an approximately 8-mm
Pu 2.858 5.767 (69.14)
diameterloopattheendofthewireparalleltothecathodedisk.
5.730 (30.70)
Cooling of the cell during electrodeposition to at least 50°C is
Pu 87.7 5.499 (71.4)
recommended.
5.456 (28.6)
7.3 Centrifuge, a 100-mL centrifuge bottle is convenient.
239 4
Pu 2.4110 × 10 5.158 (73.3)
5.144 (15.1) 7.4 Ion Exchange Column, approximately 13-mm inside
5.105 (11.5)
diameter and 150 mm long with a 100-mLreservoir, and either
240 a fritted glass or borosilicate glass-wool plug at the bottom.
Pu 6563 5.168 (73.51)
5.123 (26.39)
8. Reagents and Materials
242 5
Pu 3.733 × 10 4.902 (79)
4.858 (21)
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
241 B
Am 432.2 5.544 (0.36)
all reagents shall conform to the specifications of the Commit-
5.485 (85.1)
5.442 (13.3)
tee onAnalytical Reagents of theAmerican Chemical Society.
Other grades may be used, provided it is first ascertained that
228 B
Th 1.9131 5.423 (73.4)
the reagent is of sufficiently high purity to permit its use
5.340 (26.6)
A without reducing the accuracy of the determination.
Table of Isotopes, Eighth Edition, Vol. 11, Richard B. Firestone, Lawrence
Berkeley National Laboratory, University of California, 1996.
8.2 Purity of Water—Unless otherwise indicated, reference
B 241
These two isotopes are listed, especially in Am, since they could interfere in
to water shall be understood to mean reagent water conforming
the determination of Pu.
to Specifications D1193, Type III or better.
8.3 Radioactive Purity—Radioactive purity shall be such
238 228
that the measured radioactivity of blank samples does not
foundtointerferewiththedeterminationof Pu.Some Th
exceed the calculated probable error of the measurement.
comes through the chemical separation procedure and is
electrodepositedwiththeplutonium.Ifthediskispoorlyplated
8.4 Ammonium Hydroxide (approximately 15 M, 28 %)—
andiftheresolutionofpeaksinthealphaspectrumisnotbetter
Concentrated ammonium hydroxide (NH OH). Store in well-
238 228
than 60 keV, the Pu and the Th may appear as one peak; sealed container to minimize absorption of carbon dioxide. Do
the principal alpha energy of Pu is 5.50 MeV while that
not use if the solution is cloudy or if a precipitate is present.
of Th is 5.42 MeV.After a period of in-growth the presence
8.5 Ammonium Hydroxide Solution (1.5 M)—Add 100 mL
of Th can be inferred from its decay progeny.
of 15 M NH OH to 250 mL of water and dilute to 1 L with
6.2 Unless corrected, the presence of the tracer isotope in
water. Store in well-sealed container to minimize absorption of
the original water sample will bias the yield of that tracer high
carbon dioxide. Do not use if the solution is cloudy or if a
and bias the results of the analyte plutonium isotopes low. For
precipitate is present.
example, plutonium that originates from high burn-up pluto-
8.6 Ammonium Hydroxide Solution (0.15 M)—Add 10 mL
nium may contain a small percentage of Pu, in addition to
of 15 M NH OH to 250 mL of water and dilute to 1 L with
other plutonium isotopes. The tracer isotope, Pu, is less
water. Do not use if the solution is cloudy or if a precipitate is
subject to this problem given that it is not generated in reactors
present.
burning plutonium or uranium. However, there is some poten-
8.7 Ammonium Iodide Solution (1 M)—Dissolve 14.5 g of
tial for tailing of the Pu peak into analyte regions. For
NH I in water and dilute to 100 mL. This solution must be
samples expected to be free of plutonium analyte isotopes
prepared fresh weekly.
242Pu may be the preferred tracer isotope.
8.8 Anion Exchange Resin—Strongly basic, styrene, quater-
7. Apparatus
nary ammonium salt, 4 % crosslinked, 100 to 200 mesh,
7.1 Alpha Spectrometry System, consisting of a silicon chlorideform.The8 %crosslinkedformmayalsobeused.The
studywhichgeneratedtheprecisionandbiasdatareferencedin
surface barrier, or ion-implanted detector, supporting
electronics,andmulti-channelpulse-heightanalyzercapableof Section15wasperformedusingonlythe4 %crosslinkedform.
Those using 8 % crosslinked should validate that such a
giving a resolution of 50 keV or better full-width at half-
maximum (FWHM) with a sample electrodeposited on a flat, substitution does not impact the performance of the method.
mirror-finished stainless steel disk. The counting efficiency of
the system should be greater than 15 % and the background in
the energy region of each analyte isotope should be less than
Reagent Chemicals, American Chemical Society Specifications, American
ten counts in 60 000 s. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
7.2 Electrodeposition Apparatus, consisting ofa0to12V,
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
0 to 2 A power supply (preferably constant current) and a and National Formulary. U.S. Pharmaceutical Convention, Inc. (USPC).
D3865 − 09 (2015)
8.9 Boric Acid (H BO )—Powdered or crystalline. a laboratory coat.Avoid breathing any HF fumes. Clean up all
3 3
spills and wash thoroughly after using HF.
8.10 Electrolyte, Preadjusted—The solution is 1 M
(NH ) SO . Dissolve 132 g of ammonium sulfate in water and
4 2 4 10. Sampling
diluteto1L.AddconcentratedNH OHorconcentratedH SO
4 2 4
10.1 Collect the sample in accordance with Practices
while stirring to adjust the pH of the solution to 3.5.
D3370. Preserve the sample by adjusting the acidity to pH <1
8.11 Slightly Basic Ethyl Alcohol (C H OH) 95 %—Make
2 5
with HNO (1.8 M) if the sample is not to be analyzed within
slightlybasicwithafewdropsofconcentratedNH OHper100
24 h. Record the volume of the sample and the volume of acid
mL of alcohol.
added.
8.12 Ferric Chloride Carrier Solution (50 mg Fe/mL)—
11. Calibration and Standardization
Dissolve 24 g of FeCl ·6H O in a mixture of 4.4 mL of
3 2
236 242
11.1 The Pu or Pu tracer used in this method shall be
concentrated hydrochloric acid (sp gr 1.19) and 95.6 mL of
traceable to NIST or another national standards laboratory.
water.
While the laboratory is advised to verify the activity of the
8.13 Hydrochloric Acid (approximately 12 M, 36 %)—
received and diluted tracer solution, the results of these
Concentrated hydrochloric acid (HCl).
verification measurements shall not replace the decay-
8.14 Hydrochloric Acid Solution (9 M)—Add 750 mLof 12
corrected traceable value. If the verification measurements fail
236 242
M hydrochloric acid to 150 mLof water and dilute to 1 Lwith
toverifythetraceableactivityoftheas-received Puor Pu
water.
tracersolutionthelaboratorywillresolvethiswiththesupplier.
8.15 Hydrofluoric Acid (~ 29 M, 49 %)—Concentrated hy-
12. Procedure
drofluoric acid (HF).
12.1 Coprecipitation:
8.16 Hydrogen Peroxide Solution (H O )—Standard 30 %.
2 2
12.1.1 Accurately measure a known volume of the water
8.17 Nitric Acid (~ 16 M, 69 %)—Concentrated nitric acid
sample. The volume should be approximately 1 litre. Docu-
(HNO ).
ment the known volume.
12.1.2 If the sample has not been acidified, add 150 mL of
8.18 Nitric Acid Solution (8 M)—Add 500 mL of 16 M
concentrated HNO per litre of sample.
nitric acid to 250 mL of water and dilute to 1 L with water.
12.1.3 Mix the sample completely, and add an accurately
8.19 Nitric Acid Solution (1.8 M)—Add110mLof16M 236 242
known amount of the Pu or Pu standard solution to give
nitric acid to 500 mL of water and dilute to 1 L with water. 236 242 239 240 238
about 0.2 Bq of Pu or Pu. If the Pu, Pu, or Pu
236 242
8.20 Pu or Pu Solutions, Standard (Approximately content of the sample is known to be high Pu tracer is
0.2 Bq/mL)—The study which generated the precision and bias recommended.
data referenced in section 15 was performed using only a Pu 12.1.4 Heat the sample to about 60°C and stir at this
tracer. Those using Pu should validate that such a substitu- temperature for about 1 h.
tion does not impact the performance of the method.
12.1.5 Add 1 mL of ferric chloride carrier solution and stir
about 10 min.
236 242
NOTE 1—Standard Pu and Pu tracer solutions usually are avail-
12.1.6 Add concentrated NH OH while stirring to precipi-
able from the National Institute of Standards and Technology (NIST),
tate iron hydroxide. Add a slight excess of the concentrated
vendors with traceability to NIST, or other national standards laboratories;
dilution to the required concentration may be necessary.
NH OH to raise the pH to 9 to 10 as indicated with pH paper.
12.1.7 Continue to stir the sample for about 30 min before
8.21 Sodium Hydrogen Sulfate—Sulfuric Acid Solution—
allowing the precipitate to settle.
Dissolve 10 g of sodium hydrogen sulfate in 100 mL of water
12.1.8 After the sample has settled sufficiently, decant the
andthencarefullyadd100mLofconcentratedH SO (~18M,
2 4
supernate, being careful not to remove any precipitate.
95 %) while stirring. This solution contains approximately 5 g
Alternatively, the iron hydroxide precipitate may be filtered
of NaHSO per 100 mL of 9 M H SO .
4 2 4
out.
8.22 Sodium Nitrite (NaNO ).
12.1.9 Slurry the precipitate and remaining supernate and
8.23 Sulfuric Acid (~ 18 M, 95%)—Concentrated sulfuric
transfer to a 100 mL centrifuge bottle.
acid (H SO ).
12.1.10 Centrifuge the sample and pour off the
...
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D3865 − 09 (Reapproved 2015)
Standard Test Method for
Plutonium in Water
This standard is issued under the fixed designation D3865; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Applicable Test Methods of Committee D19 on Water
D3084 Practice for Alpha-Particle Spectrometry of Water
1.1 This test method covers the determination of alpha-
D3370 Practices for Sampling Water from Closed Conduits
particle-emitting isotopes of plutonium concentrations over
D5847 Practice for Writing Quality Control Specifications
0.01 Bq/L (0.3 pCi/L) in water by means of chemical separa-
for Standard Test Methods for Water Analysis
tions and alpha pulse-height analysis (alpha-particle spectrom-
etry). Due to overlapping alpha-particle energies, this method
3. Terminology
239 240
cannot distinguish Pu from Pu. Plutonium is chemically
3.1 Definitions:
separated from a 1-L water sample by coprecipitation with
3.1.1 For definitions of terms used in this test method, refer
ferric hydroxide, anion exchange and electrodeposition. The
to Terminology D1129 and Terminology C859.
test method applies to soluble plutonium and to suspended
particulate matter containing plutonium. In the latter situation,
4. Summary of Test Method
an acid dissolution step is required to assure that all of the
4.1 The water sample is acidified and a plutonium isotopic
plutonium dissolves.
236 242
tracer, for example Pu or Pu, is added as a tracer before
1.2 The values stated in SI units are to be regarded as
any chemical separations are performed. Iron is added to the
standard. No other units of measurement are included in this
water as iron (III), and the plutonium is coprecipitated with the
standard.
iron as ferric hydroxide. After decantation and centrifugation,
1.3 This standard does not purport to address all of the
the ferric hydroxide precipitate containing the coprecipitated
safety concerns, if any, associated with its use. It is the plutonium is dissolved, and the solution is adjusted to 8 M in
responsibility of the user of this standard to establish appro-
HNO for anion exchange separation. When the sample fails to
priate safety and health practices and determine the applica- dissolve because of the presence of insoluble residue, the
bility of regulatory limitations prior to use. Specific hazards are
residue is treated by a rigorous acid dissolution using concen-
given in Section 9.
trated nitric, hydrofluoric, and hydrochloric acids.
4.2 After an anion exchange separation, the plutonium is
2. Referenced Documents
electrodeposited onto a stainless steel disk for counting by
2.1 ASTM Standards:
alpha pulse-height analysis using a silicon surface barrier or
C859 Terminology Relating to Nuclear Materials
ion-implanted detector. Table 1 shows the alpha energies of the
C1163 Practice for Mounting Actinides for Alpha Spectrom-
isotopes of interest in this test method. The absolute activities
238 239/240
etry Using Neodymium Fluoride
of Pu and Pu are calculated independent of discrete
C1284 Practice for Electrodeposition of the Actinides for
detector efficiency and chemical yield corrections by directly
Alpha Spectrometry
comparing the number of counts in each peak relative to counts
236 242
D1129 Terminology Relating to Water
observed from a known activity of Pu or Pu tracer (see
D1193 Specification for Reagent Water
Eq 1).
D2777 Practice for Determination of Precision and Bias of
5. Significance and Use
5.1 This test method was developed to measure plutonium
This test method is under the jurisdiction of ASTM Committee D19 on Water
in environmental waters or waters released to the environment
and is the direct responsibility of Subcommittee D19.04 on Methods of Radiochemi-
and to determine whether or not the plutonium concentration
cal Analysis.
exceeds the maximum amount allowable by regulatory stat-
Current edition approved Jan. 1, 2015. Published January 2015. Originally
utes.
approved in 1980. Last previous edition approved in 2009 as D3865 – 09. DOI:
10.1520/D3865-09R15.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 6. Interferences
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
6.1 Thorium-228, when present in the original water sample
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. at concentrations 100 times or greater than Pu has been
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3865 − 09 (2015)
TABLE 1 Radioactive Decay Characteristics of Isotopes of
(preferably disposable) electrodeposition cell. The cathode is
A
Interest in the Determination of Plutonium in Water
an approximately 20-mm diameter stainless steel disk pre-
Half Life Principal Alpha Energies in MeV
polished to a mirror finish. The anode is an approximately
Isotope
Years (Abundance)
1-mm diameter platinum wire with an approximately 8-mm
Pu 2.858 5.767 (69.14)
diameter loop at the end of the wire parallel to the cathode disk.
5.730 (30.70)
Cooling of the cell during electrodeposition to at least 50°C is
Pu 87.7 5.499 (71.4)
recommended.
5.456 (28.6)
7.3 Centrifuge, a 100-mL centrifuge bottle is convenient.
239 4
Pu 2.4110 × 10 5.158 (73.3)
5.144 (15.1)
7.4 Ion Exchange Column, approximately 13-mm inside
5.105 (11.5)
diameter and 150 mm long with a 100-mL reservoir, and either
a fritted glass or borosilicate glass-wool plug at the bottom.
Pu 6563 5.168 (73.51)
5.123 (26.39)
8. Reagents and Materials
242 5
Pu 3.733 × 10 4.902 (79)
4.858 (21)
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
241 B
Am 432.2 5.544 (0.36)
all reagents shall conform to the specifications of the Commit-
5.485 (85.1)
5.442 (13.3)
tee on Analytical Reagents of the American Chemical Society.
Other grades may be used, provided it is first ascertained that
228 B
Th 1.9131 5.423 (73.4)
the reagent is of sufficiently high purity to permit its use
5.340 (26.6)
A
without reducing the accuracy of the determination.
Table of Isotopes, Eighth Edition, Vol. 11, Richard B. Firestone, Lawrence
Berkeley National Laboratory, University of California, 1996.
8.2 Purity of Water—Unless otherwise indicated, reference
B 241
These two isotopes are listed, especially in Am, since they could interfere in
the determination of Pu. to water shall be understood to mean reagent water conforming
to Specifications D1193, Type III or better.
8.3 Radioactive Purity—Radioactive purity shall be such
238 228
that the measured radioactivity of blank samples does not
found to interfere with the determination of Pu. Some Th
exceed the calculated probable error of the measurement.
comes through the chemical separation procedure and is
electrodeposited with the plutonium. If the disk is poorly plated
8.4 Ammonium Hydroxide (approximately 15 M, 28 %)—
and if the resolution of peaks in the alpha spectrum is not better Concentrated ammonium hydroxide (NH OH). Store in well-
238 228
than 60 keV, the Pu and the Th may appear as one peak;
sealed container to minimize absorption of carbon dioxide. Do
the principal alpha energy of Pu is 5.50 MeV while that not use if the solution is cloudy or if a precipitate is present.
of Th is 5.42 MeV. After a period of in-growth the presence
8.5 Ammonium Hydroxide Solution (1.5 M)—Add 100 mL
of Th can be inferred from its decay progeny.
of 15 M NH OH to 250 mL of water and dilute to 1 L with
6.2 Unless corrected, the presence of the tracer isotope in
water. Store in well-sealed container to minimize absorption of
the original water sample will bias the yield of that tracer high
carbon dioxide. Do not use if the solution is cloudy or if a
and bias the results of the analyte plutonium isotopes low. For
precipitate is present.
example, plutonium that originates from high burn-up pluto-
8.6 Ammonium Hydroxide Solution (0.15 M)—Add 10 mL
nium may contain a small percentage of Pu, in addition to
of 15 M NH OH to 250 mL of water and dilute to 1 L with
236 4
other plutonium isotopes. The tracer isotope, Pu, is less
water. Do not use if the solution is cloudy or if a precipitate is
subject to this problem given that it is not generated in reactors
present.
burning plutonium or uranium. However, there is some poten-
8.7 Ammonium Iodide Solution (1 M)—Dissolve 14.5 g of
tial for tailing of the Pu peak into analyte regions. For
NH I in water and dilute to 100 mL. This solution must be
samples expected to be free of plutonium analyte isotopes 4
prepared fresh weekly.
242Pu may be the preferred tracer isotope.
8.8 Anion Exchange Resin—Strongly basic, styrene, quater-
7. Apparatus
nary ammonium salt, 4 % crosslinked, 100 to 200 mesh,
7.1 Alpha Spectrometry System, consisting of a silicon chloride form. The 8 % crosslinked form may also be used. The
surface barrier, or ion-implanted detector, supporting study which generated the precision and bias data referenced in
Section 15 was performed using only the 4 % crosslinked form.
electronics, and multi-channel pulse-height analyzer capable of
giving a resolution of 50 keV or better full-width at half- Those using 8 % crosslinked should validate that such a
substitution does not impact the performance of the method.
maximum (FWHM) with a sample electrodeposited on a flat,
mirror-finished stainless steel disk. The counting efficiency of
the system should be greater than 15 % and the background in
the energy region of each analyte isotope should be less than 3
Reagent Chemicals, American Chemical Society Specifications, American
ten counts in 60 000 s. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
7.2 Electrodeposition Apparatus, consisting of a 0 to 12 V,
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
0 to 2 A power supply (preferably constant current) and a and National Formulary. U.S. Pharmaceutical Convention, Inc. (USPC).
D3865 − 09 (2015)
8.9 Boric Acid (H BO )—Powdered or crystalline. a laboratory coat. Avoid breathing any HF fumes. Clean up all
3 3
spills and wash thoroughly after using HF.
8.10 Electrolyte, Preadjusted—The solution is 1 M
(NH ) SO . Dissolve 132 g of ammonium sulfate in water and
4 2 4
10. Sampling
dilute to 1 L. Add concentrated NH OH or concentrated H SO
4 2 4
10.1 Collect the sample in accordance with Practices
while stirring to adjust the pH of the solution to 3.5.
D3370. Preserve the sample by adjusting the acidity to pH <1
8.11 Slightly Basic Ethyl Alcohol (C H OH) 95 %—Make
2 5
with HNO (1.8 M) if the sample is not to be analyzed within
slightly basic with a few drops of concentrated NH OH per 100
24 h. Record the volume of the sample and the volume of acid
mL of alcohol.
added.
8.12 Ferric Chloride Carrier Solution (50 mg Fe/mL)—
11. Calibration and Standardization
Dissolve 24 g of FeCl ·6H O in a mixture of 4.4 mL of
3 2
236 242
11.1 The Pu or Pu tracer used in this method shall be
concentrated hydrochloric acid (sp gr 1.19) and 95.6 mL of
traceable to NIST or another national standards laboratory.
water.
While the laboratory is advised to verify the activity of the
8.13 Hydrochloric Acid (approximately 12 M, 36 %)—
received and diluted tracer solution, the results of these
Concentrated hydrochloric acid (HCl).
verification measurements shall not replace the decay-
8.14 Hydrochloric Acid Solution (9 M)—Add 750 mL of 12
corrected traceable value. If the verification measurements fail
236 242
M hydrochloric acid to 150 mL of water and dilute to 1 L with
to verify the traceable activity of the as-received Pu or Pu
water.
tracer solution the laboratory will resolve this with the supplier.
8.15 Hydrofluoric Acid (~ 29 M, 49 %)—Concentrated hy-
12. Procedure
drofluoric acid (HF).
12.1 Coprecipitation:
8.16 Hydrogen Peroxide Solution (H O )—Standard 30 %.
2 2
12.1.1 Accurately measure a known volume of the water
8.17 Nitric Acid (~ 16 M, 69 %)—Concentrated nitric acid
sample. The volume should be approximately 1 litre. Docu-
(HNO ).
ment the known volume.
12.1.2 If the sample has not been acidified, add 150 mL of
8.18 Nitric Acid Solution (8 M)—Add 500 mL of 16 M
concentrated HNO per litre of sample.
nitric acid to 250 mL of water and dilute to 1 L with water.
12.1.3 Mix the sample completely, and add an accurately
8.19 Nitric Acid Solution (1.8 M)—Add 110 mL of 16 M 236 242
known amount of the Pu or Pu standard solution to give
nitric acid to 500 mL of water and dilute to 1 L with water. 236 242 239 240 238
about 0.2 Bq of Pu or Pu. If the Pu, Pu, or Pu
236 242 236
8.20 Pu or Pu Solutions, Standard (Approximately content of the sample is known to be high Pu tracer is
0.2 Bq/mL)—The study which generated the precision and bias recommended.
data referenced in section 15 was performed using only a Pu 12.1.4 Heat the sample to about 60°C and stir at this
tracer. Those using Pu should validate that such a substitu-
temperature for about 1 h.
tion does not impact the performance of the method. 12.1.5 Add 1 mL of ferric chloride carrier solution and stir
about 10 min.
236 242
NOTE 1—Standard Pu and Pu tracer solutions usually are avail-
12.1.6 Add concentrated NH OH while stirring to precipi-
able from the National Institute of Standards and Technology (NIST),
vendors with traceability to NIST, or other national standards laboratories; tate iron hydroxide. Add a slight excess of the concentrated
dilution to the required concentration may be necessary.
NH OH to raise the pH to 9 to 10 as indicated with pH paper.
12.1.7 Continue to stir the sample for about 30 min before
8.21 Sodium Hydrogen Sulfate—Sulfuric Acid Solution—
allowing the precipitate to settle.
Dissolve 10 g of sodium hydrogen sulfate in 100 mL of water
12.1.8 After the sample has settled sufficiently, decant the
and then carefully add 100 mL of concentrated H SO (~ 18 M,
2 4
supernate, being careful not to remove any precipitate.
95 %) while stirring. This solution contains approximately 5 g
Alternatively, the iron hydroxide precipitate may be filtered
of NaHSO per 100 mL of 9 M H SO .
4 2 4
out.
8.22 Sodium Nitrite (NaNO ).
12.1.9 Slurry the precipitate and remaining supernate and
8.23 Sulfuric Acid (~ 18 M, 95%)—Concentrated sulfuric
transfer to a 100 mL centrifuge bottle.
acid (H SO ).
12.1.10 C
...
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