ASTM C1287-18

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it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: C1287 − 10 C1287 − 18
Standard Test Method for
Determination of Impurities in Nuclear Grade Uranium
Compounds by Inductively Coupled Plasma Mass
Spectrometry
This standard is issued under the fixed designation C1287; 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
1.1 This test method covers the determination of 67 elements in uranium dioxide samples and nuclear grade uranium
compounds and solutions without matrix separation by inductively coupled plasma mass spectrometry (ICP-MS). The elements are
listed in Table 1. These elements can also be determined in uranyl nitrate hexahydrate (UNH), uranium hexafluoride (UF ),
triuranium octoxide (U O ) and uranium trioxide (UO ) if these compounds are treated and converted to the same uranium
3 8 3
concentration solution.
1.2 The elements boron, sodium, silicon, phosphorus, potassium, calcium and iron can be determined using different techniques.
The analyst’s instrumentation will determine which procedure is chosen for the analysis.
1.3 The test method for technetium-99 is given in Annex A1.
1.4 The values stated in SI units are to be regarded as standard.
1.5 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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Warning—The ICP-MS is a source of intense ultra-violet radiation from the
radio frequency induced plasma. Protection from radio frequency radiation and UV radiation is provided by the instrument under
normal operation.
1.6 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.
2. Referenced Documents
2.1 ASTM Standards:
C753 Specification for Nuclear-Grade, Sinterable Uranium Dioxide Powder
C776 Specification for Sintered Uranium Dioxide Pellets for Light Water Reactors
C787 Specification for Uranium Hexafluoride for Enrichment
C788 Specification for Nuclear-Grade Uranyl Nitrate Solution or Crystals
C859 Terminology Relating to Nuclear Materials
C967 Specification for Uranium Ore Concentrate
C996 Specification for Uranium Hexafluoride Enriched to Less Than 5 % U
C1346 Practice for Dissolution of UF from P-10 Tubes
C1347 Practice for Preparation and Dissolution of Uranium Materials for Analysis
D1193 Specification for Reagent Water
3. Terminology
3.1 Definitions:
3.1.1 For definitions of terms relating to the nuclear fuel cycle, refer to Terminology C859.
This test method is under the jurisdiction of ASTM Committee C26 on Nuclear Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of Test.
Current edition approved June 1, 2010Jan. 1, 2018. Published July 2010January 2018. Originally approved in 1994. Last previous edition approved in 20032010 as
C1287 – 03.C1287 – 10. DOI: 10.1520/C1287-10.10.1520/C1287-18.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
C1287 − 18
4. Summary of Test Method
4.1 The sample is dissolved in acid if it is not already a solution. A fixed quantity of internal standard is added to monitor and
correct for signal instability. The level of impurities in the solution is measured by ICP-MS. Customized software calculates the
concentration of each element.
4.2 Uranium-concentration-matched standard solutions are used to calibrate the ICP-MS instrument. The calibration is linear up
3,4
to at least 0.2 μg/mlμg/mL (100 μg/g U) for each analyte.
4.3 Microwave dissolution may be used as an alternate dissolution method.
5. Significance and Use
5.1 This test method is capable of measuring the elements listed in Table 1, some of which are required by Specifications C753,
C776, C787, C788, C967 and C996.
6. Apparatus
6.1 ICP-MS, controlled by computer and fitted with the associated software and peripherals. May be fitted with cold plasma
option. Current instrumentation is available with dynamic reaction cell or collision cell options.
6.2 Autosampler, with tube racks and disposable plastic sample tubes compatible with 5.16.1 (optional).
6.3 Variable Micropipettes:
6.3.1 10 μL to 100 μL capacity.
6.3.2 100 μL to 1000 μL capacity.
6.3.3 1000 μL to 10.00 mL capacity.
6.4 Volumetric Flasks:
6.4.1 50 mL capacity—polypropylene.
6.4.2 100 mL capacity—polypropylene.
6.4.3 1 L capacity—glass.
6.5 Platinum Dish—100 mL capacity.
6.6 Silica Beaker—250 mL capacity.
6.7 Watch Glasses—75 mm diameter.
6.8 Polypropylene Tubes—50 mL, with graduation marks and with caps.
7. Reagents
7.1 The sensitivity of the ICP-MS technique requires the use of ultra high purity reagents in order to be able to obtain the low
levels of detection. All the reagents below are ultra high purity grade unless otherwise stated:
7.1.1 Element stock standards at 1000 μg/mL for all the elements in Table 1.
7.1.2 Hydrofluoric Acid (HF), (40 g/100 g), 23 molar.
7.1.2.1 Warning—Hydrofluoric acid is a highly corrosive acid that can severely burn skin, eyes, and mucous membranes.
Hydrofluoric acid is similar to other acids in that the initial extent of a burn depends on the concentration, the temperature, and
the duration of contact with the acid. Hydrofluoric acid differs from other acids because the fluoride ion readily penetrates the skin,
causing destruction of deep tissue layers. Unlike other acids that are rapidly neutralized, hydrofluoric acid reactions with tissue may
continue for days if left untreated. Due to the serious consequences of hydrofluoric acid burns, prevention of exposure or injury
of personnel is the primary goal. Utilization of appropriate laboratory controls (hoods) and wearing adequate personnel protective
equipment to protect from skin and eye contact is essential. Acute exposure to HF can cause painful and severe burns upon skin
contact that require special medical attention. Chronic or prolonged exposure to low levels on the skin may cause
fluorosis.Familiarization and compliance with the Safety Data Sheet is essential.
7.1.3 Nitric Acid—Concentrated nitric acid (HNO ), 15 molar.
7.1.4 Rhodium Stock Solution (1000 μg/mL Rh)—Commercially available solution (see Note 1).
NOTE 1—Rhodium stock solution is commercially available supplied with a certificate of analysis for the element and a full range of trace impurities.
The solutions are prepared by the manufacturer using a variety of media designed to keep each element in solution for a minimum of one year.
7.1.5 Sulfuric Acid—Concentrated sulfuric acid (H SO ), 18 molar.
2 4
“ICP-MS Versus Conventional Methods for the Analysis of Trace Impurities in Nuclear Fuel,” by Allenby, P., Clarkson, A. S., Makinson, P. R., presented at 2nd Surrey
Conference on Plasma Source Mass Spectrometry, Guildford, UK, July 1987.
“Trace Metals in NBL Uranium Standard CRM 124 Using ICP-MS,” by Aldridge, A. J., Clarkson, A. S., Makinson, P. R., Dawson, K. W., presented at 1st Durham
International Conference on Plasma Source Mass Spectrometry, Durham, UK, September 1988.
C1287 − 18
TABLE 1 Reporting Limits of Impurity Elements
NOTE 1—The impurity elements were determined in 0.2 % uranium
solutions, prepared following Section 89.
NOTE 2—Acquisition time = 10 s/isotope using peak jump mode.
NOTE 3—103 Rh was used as an internal standard. For the elements
where the technique is identified as Perkin Elmer DRCII scandium was
used as internal standard for boron, sodium and phosphorus. Rhodium was
used as the internal standard for potassium, calcium and iron in Reaction
Cell mode.
NOTE 4—The LRL is based on the within run standard deviation (S ) of
b
20 uranium-matched blank determinations for each analyte. This limit
equals 4 × S , rounded up to a preferred value in the series 1, 1.5, 2, 3, 4,
b
6, multiplied or divided by the appropriate integer power of ten.
NOTE 5—The upper reporting limit can be increased by extending the
calibration to 10 μg/mL (5000 μg/g U) if the ICP-MS used has an extended
dynamic range (EDR) accessory.
NOTE 6—For the elements where the technique is listed as P-E DRCII,
the instrumentation may be specific to those elements. Alternatively cold
plasma technique may be used and it is up to the analyst to perform
testwork using spikes and reference materials and to determine the lower
reporting levels. The impurity elements were determined in 0.16 %
uranium solutions, prepared following Section 89. The dwell times are
listed in 8.4.1.19.4.1.1.
NOTE 7—Some of the elements are not included in the material
specifications and have been included only as a research record for the
reader’s interest.
Lower Upper
Mass Analyte Reporting Reporting
Analyte Technique
Used Group Limit (LRL), Limit (URL),
μg/g U μg/g U
Lithium 7 A 0.01 100 normal plasma
Beryllium 9 A 0.04 100 normal plasma
Boron 11 E 0.3 100 DRCII
Sodium 23 E 0.3 100 DRCII
Magnesium 24 A 4 100 normal plasma
Aluminum 27 D 2 1000 normal plasma
Phosphorus 31 E 1 100 DRCII
Potassium 39 E 2.0 100 DRCII
Calcium 40 E 3 100 DRCII
Scandium 45 A 4 100 normal plasma
Titanium 48 B 0.2 100 normal plasma
Vanadium 51 B 0.04 100 normal plasma
Chromium 52 B 0.1 100 normal plasma
Manganese 55 A 0.1 100 normal plasma
Iron 56 A 0.2 100 DRCII
Cobalt 59 A 0.02 100 normal plasma
Nickel 60 A 0.4 100 normal plasma
Copper 65 A 0.2 100 normal plasma
Zinc 66 A 0.3 100 normal plasma
Gallium 69 A 0.04 100 normal plasma
Germanium 74 A 0.2 100 normal plasma
Arsenic 75 A 0.2 100 normal plasma
Selenium 82 A 3 100 normal plasma
Rubidium 85 A 0.06 100 normal plasma
Strontium 88 A 0.06 100 normal plasma
Yttrium 89 A 0.04 100 normal plasma
Zirconium 90 B 0.02 100 normal plasma
Niobium 93 B 0.01 100 normal plasma
Molybde- 95 B 0.04 100 normal plasma
num
Ruthenium 102 B 0.02 100 normal plasma
Palladium 106 B 0.2 100 normal plasma
Silver 107 A 0.1 100 normal plasma
Cadmium 111 A 0.03 100 normal plasma
Indium 115 A 0.04 100 normal plasma
Tin 116 B 0.04 100 normal plasma
Antimony 121 B 0.02 100 normal plasma
Tellurium 130 B 0.4 100 normal plasma
Caesium 133 A 0.06 100 normal plasma
C1287 − 18
TABLE 1 Continued
Lower Upper
Mass Analyte Reporting Reporting
Analyte Technique
Used Group Limit (LRL), Limit (URL),
μg/g U μg/g U
Barium 138 A 0.02 100 normal plasma
Lanthanum 139 C 0.1 100 normal plasma
Cerium 140 C 0.01 100 normal plasma
Praseo- 141 C 0.01 100 normal plasma
dymium
Neodymium 146 C 0.01 100 normal plasma
Samarium 149 C 0.01 100 normal plasma
Europium 151 C 0.01 100 normal plasma
Gadolinium 158 C 0.01 100 normal plasma
Terbium 159 C 0.01 100 normal plasma
Dysprosium 163 C 0.01 100 normal plasma
Holmium 165 C 0.01 100 normal plasma
Erbium 166 C 0.01 100 normal plasma
Thulium 169 C 0.01 100 normal plasma
Ytterbium 174 C 0.01 100 normal plasma
Lutetium 175 C 0.01 100 normal plasma
Hafnium 178 B 0.01 100 normal plasma
Tantalum 181 B 0.01 100 normal plasma
Tungsten 184 B 0.01 100 normal plasma
Rhenium 187 A 0.02 100 normal plasma
Osmium 190 B 0.2 100 normal plasma
Iridium 193 B 0.2 100 normal plasma
Platinum 195 B 0.2 100 normal plasma
Gold 197 B 0.06 100 normal plasma
Mercury 202 A 0.4 100 normal plasma
Thallium 205 A 0.02 100 normal plasma
Lead 208 A 0.02 100 normal plasma
Bismuth 209 A 0.03 100 normal plasma
Thorium 232 B 0.01 100 normal plasma
7.1.6 Uranium Standard Base Solution—Uranyl nitrate solution to Specification C788, of known uranium (100 g/L) and
aluminum content (≤ 2 μg/g U). The total metallic impurity (TMI) content must not exceed 50 μg/g U and no individual analyte
must exceed 10 μg/g U.
7.1.7 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming
to Specification D1193, Type I.
7.1.8 Ammonia—Anhydrous, NH , 99.9995 % 99.9995 % minimum purity. Used with instruments fitted with dynamic reaction
cell option.
8. Standards
8.1 Four separate mixed standard solutions (A, B, C, and E) are prepared to prevent the precipitation of some elements (as
insoluble chlorides, fluorides etc; see Table 1 for details of the analyte groups). Analyte group A contains element stock solutions
prepared in HNO or HNO /HF, analyte group B contains element stock solutions prepared in HCl or HCl/HF, analyte group C
3 3
contains the rare earth element stock solutions, and analyte group E contains boron sodium silicon, phosphorus, potassium and
calcium. The mixed standard solutions should be prepared to contain only the analytes of interest. Other combinations of mixed
standard solutions may be prepared to minimize the precipitation of the analytes.
8.1.1 Mixed standard solution A is prepared from stock solutions of each element from analyte group A. Transfer 1000 μL of
the stock solution (1000 μg/mL) of each element into a 50 mL polypropylene volumetric flask and add 500 μL of concentrated nitric
acid. Dilute to 50 mL with water and mix. This multi-element standard contains 20 μg/mL of each analyte in 1 % nitric acid. This
solution must be used on the day of preparation.
8.1.2 Mixed standard solution B is prepared from stock solutions of each element from analyte group B. Transfer 1000 μL of
the stock solution (1000 μg/mL) of each element into a 50 mL polypropylene volumetric flask and add 500 μL of concentrated nitric
acid. Dilute to 50 mL with water and mix. This multi-element standard contains 20 μg/mL of each analyte in 1 % nitric acid. This
solution must be used within one week of preparation.
8.1.3 Mixed standard solution C is prepared from stock solutions of each element from analyte group C. Transfer 1000 μL of
the stock solution (1000 μg/mL) of each element into a 50 mL polypropylene volumetric flask and add 500 μL of concentrated nitric
acid. Dilute to 50 mL with water and mix. This multi-element standard contains 20 μg/mL of each analyte in 1 % nitric acid. This
solution must be used within one week of preparation.
8.2 Standard solution D is prepared from the stock solution of aluminum from analyte group D. Transfer 1000 μL of the stock
solution (1000 μg/mL Al) into a 50 mL polypropylene volumetric flask and add 500 μL of concentrated nitric acid. Dilute to 50
μL with water and mix. This standard contains 20 μg/mL of aluminum in 1 % nitric acid. This solution must be used within one
week of preparation.
C1287 − 18
8.3 Mixed standard solution E is prepared from stock solutions of each element from analyte group E. Transfer 1000 μL of the
stock solution (1000 μg/mL) of each element into a 50 mL polypropylene volumetric flask and add 500 μL of concentrated nitric
acid. Dilute to 50 mL with water and mix. This multi-element standard contains 20 μg/mL of each analyte in 1 % nitric acid. This
solution must be used within one week of preparation.
8.4 Rhodium internal standard solution is prepared from the stock solution. Transfer 1000 μL of the stock solution (1000 μg/mL
Rh) into a 100 mL polypropylene volumetric flask and add 1000 μL of concentrated nitric acid. Dilute to 100 mL with water and
mix. This internal standard solution contains 10 μg/mL Rh in a 1 % nitric acid solution. Other internal standards such as scandium
may be used. With high mass elements the analyst may choose internal standards such as iridium or terbium. Other elements may
be applicable as well but it is up to the analyst to conduct the appropriate testwork.
NOTE 2—Throughout this standard, references to Rh internal standard solution will include all other internal standard elements that may be used.
9. Procedure
NOTE 3—A uranium-free reagent blank is used to eliminate bias due to the analyte concentrations in the uranium standard base solution. A
uranium-matched reagent blank is necessary to provide a constant acid concentration in the nebulized solution.
9.1 Sample Preparation for the Determination of All Elements Except Boron:
9.1.1 Weigh a portion of uranium oxide containing between 2.45 and 2.55 g of uranium into a platinum dish. Record the weight
to the nearest 0.001 g. For uranyl fluoride solutions prepared using Practice C1346 and uranyl nitrate solutions, aliquot between
2.45 and 2.55 g of uranium into a platinum dish. Use a variable volume plastic pipet for the transfer of uranyl fluoride solutions.
Record the weight to the nearest 0.001 g.
9.1.2 Add 10 mL of water and 12.5 mL of concentrated nitric acid. Heat on a hotplate to assist dissolution.
9.1.3 Add 2.5 mL of hydrofluoric acid (40 g/100 g) and warm at about 80°C for 5 min.
9.1.4 Allow the solution to cool and transfer quantitatively to a 50 mL polypropylene volumetric flask. Dilute to 50 mL with
water and mix. This solution contains 50 g of uranium per litre in 25 % nitric acid/5 % hydrofluoric acid.
9.1.5 Transfer 4.00 mL of the solution in 8.1.49.1.4 and 1.00 mL of the rhodium internal standard solution (see 7.48.4) into a
100 mL polypropylene volumetric flask. Dilute to 100 mL with water and mix. This solution contains 2 g of uranium per litre and
0.1 μg/mL Rh in 1 % nitric acid/0.2 % hydrofluoric acid.
9.1.6 A uranium-free reagent blank (see 8.3.19.3.1) and a control or recovery sample must be prepared with every run of
samples.
9.1.7 Analyze these solutions as in 8.49.4 using the calibration solutions prepared in 8.39.3. The solutions must be analyzed
within 8 h of preparation to minimize the effects of analyte precipitation.
9.2 Sample Preparation for the Determination of Boron:
9.2.1 Weigh a portion of uranium oxide, containing between 0.095 and 0.105 g of uranium into a graduated 50 mL
polypropylene tube (or alternative). The accuracy of the graduations on the tube must be verified. Record the weight to the nearest
0.001 g. For uranyl fluoride solutions prepared using Practice C1346 and uranyl nitrate solutions, aliquot between 0.095 and 0.105
g of uranium using variable volume plastic pipets. Record the weight to the nearest 0.001 g.
9.2.2 Add 1 mL of water and 1.25 mL of concentrated nitric acid. Cap. Heat in a hot water bath at about 80°C to assist
dissolution. Heat until all the sample is dissolved.
9.2.3 Cool to room temperature. Add 0.1 mL of hydrofluoric acid (40 g/100 g) and cap. Heat in a hot water bath at about 80°C
for 5 min.
9.2.4 Allow the solution to cool. Add 0.5 mL of scandium internal standard solution (see 7.48.4). Dilute to 50 mL with water
and mix. This solution contains 2 g of uranium per litre and 0.1 μg/mL Sc in 2.5 % nitric acid/0.2 % hydrofluoric acid.
9.2.5 A uranium-free reagent blank and a control or recovery sample must be prepared with every run of samples.
9.2.6 Analyze these solutions as in 8.49.4 using the calibration solutions prepared in 8.39.3. The solutions must be analyzed
within 8 h of preparation to minimize the effects of analyte precipitation.
9.3 Preparation of Blanks and Calibration Standard Solutions:
9.3.1 For the Determination of All Elements Except Boron:
9.3.1.1 Uranium-free Reagent Blank—Transfer 12.5 mL of concentrated nitric acid and 2.5 mL of hydrofluoric acid (40 g/100
g) into a 50 mL polypropylene volumetric flask. Continue as instructed from 8.1.59.1.5 onwards.
9.3.1.2 Uranium-matched Calibration Blank—Transfer 2.00 mL of the uranium standard base solution (see 6.1.67.1.6; this is
equivalent to 0.20 g of uranium) into a 100 mL polypropylene volumetric flask. Add 1000 μL of concentrated nitric acid, 200 μL
of hydrofluoric acid (40 g/100 g) and 1000 μL of rhodium internal standard solution (see 7.48.4). Dilute to 100 mL with water and
mix. This solution contains 2 g of uranium per litre and 0.1 μg/mL Rh in 1 % nitric acid/0.2 % hydrofluoric acid.
9.3.1.3 Uranium-matched Calibration Standard—Transfer 2.00 mL of the uranium standard base solution (see 6.1.67.1.6; this
is equivalent to 0.20 g of uranium) into a 100 mL polypropylene volumetric flask. Add 1000 μL of concentrated nitric acid, 200
μL of hydrofluoric acid (40 g/100 g), 1000 μL of each mixed standard solution (see 7.1.18.1.1, 7.1.28.1.2 and 7.1.38.1.3) and 1000
μL of rhodium internal standard solution (see 7.48.4). Dilute to 100 mL with water and mix. This solution contains 2 g of uranium
per litre, 0.2 μg/mL of each analyte (equivalent to 100 μg/g U) and 0.1 μg/mL Rh in 1 % nitric acid/0.2 % hydrofluoric acid.
9.3.2 For the Determination of Boron:
C1287 − 18
9.3.2.1 Uranium-matched Reagent/Calibration Blank—Transfer 2.00 mL of the uranium standard base solution (see 6.1.67.1.6;
this is equivalent to 0.20 g of uranium) into a 100 mL polypropylene volumetric flask. Add 2.5 mL of concentrated nitric acid, 200
μL of hydrofluoric acid (40 g/100 g), and 1000 μL of scandium internal standard solution (see 7.48.4). Dilute to 100 mL with water
and mix. This solution contains 2 g of uranium per litre and 0.1 μg/mL Sc in 2.5 % nitric acid/0.2 % hydrofluoric acid.
9.3.2.2 Uranium-matched Calibration Standard—Transfer 2.00 mL of the uranium standard base solution (see 6.1.77.1.7; this
is equivalent to 0.20 g of uranium) into a 100 mL polypropylene volumetric flask. Add 2.5 mL of concentrated nitric acid, 200 μL
of hydrofluoric acid (40 g/100 g), 1000 μL of mixed standard solution (see 7.18.1 and 7.38.3), and 1000 μL of scandium internal
standard solution (see 7.48.4). Dilute to 100 mL with water and mix. This solution contains 2 g of uranium per litre, 0.2 μg/mL
of each analyte (equivalent to 100 μg/g U) and 0.1 μg/mL Sc in 2.5 % nitric acid/0.2 % hydrofluoric acid.
9.4 Measurement of Elements by ICP-MS:
9.4.1 To avoid contamination problems when nebulizing the samples, which contain hydrofluoric acid, the nebulizer system
(that is, spray chamber and nebulizer) must be made from fluorinated plastic materials (for example, TFE-fluorocarbon or
polychlorotrifluoroethylene).
9.4.1.1 Set up the ICP-MS for the analysis using the parameters given in the manufacturer’s operating manual. Nebulize the
uranium-matched reagent/calibration blank solution to optimize conditions using the 103 Rh internal standard.
Example Instrument Operating Conditions
Solution Pumping Rate Sample solution IN: 1.25 mL/min
ICP Incident Power 1400 watts
ICP Reflected Power <10 watts
Plasma Argon Coolant 14 L/min at 70 psig
Plasma A
...