ASTM C1771-19

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Designation: C1771 − 13 C1771 − 19
Standard Test Method for
Determination of Boron, Silicon, and Technetium in
Hydrolyzed Uranium Hexafluoride by Inductively Coupled
Plasma—Mass Spectrometer After Removal of Uranium by
Solid Phase Extraction
This standard is issued under the fixed designation C1771; 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 boron, silicon, and technetium in hydrolyzed uranium hexafluoride (UF ) by
Inductively Coupled Plasma Mass Spectrometry (ICP-MS) after separation of the uranium by solid phase extraction.
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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Some specific hazards statements are given in Section 7 on Hazards.
1.4 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:
C787 Specification for Uranium Hexafluoride for Enrichment
C859 Terminology Relating to Nuclear Materials
C996 Specification for Uranium Hexafluoride Enriched to Less Than 5 % U
C1346 Practice for Dissolution of UF from P-10 Tubes
C1689 Practice for Subsampling of Uranium Hexafluoride
D1193 Specification for Reagent Water
3. Terminology
3.1 Definitions—For definitions of other standard terms in this test method, refer to Terminology C859.
3.1 Definitions:
3.1.1 For definitions of other standard terms in this test method, refer to Terminology C859.
3.2 Definitions:Definitions of Terms Specific to This Standard:
3.2.1 internal reference solution, n—a solution containing non-analyte elements, the signal from which is used to correct for
variation in the performance of a measuring instrument through the course of analyzing a batch of samples, thereby improving
precision.
3.2.2 method blank, n—a solution which in so far as is practical duplicates the sample to be analyzed and passes through the
same measurement process but does not initially contain significant quantities of any of the analytes to be measured.
3.2.2.1 Discussion—
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 Jan. 1, 2013Nov. 1, 2019. Published February 2013March 2020. Originally approved in 2013. Last previous edition approved in 2013 as
C1771 – 13. DOI: 10.1520/C1771-1310.1520/C1771-19.
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.
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The method blank does not initially contain significant quantities of analyte, hence the value of any analyte measured may be
assumed to be due to interference, matrix effects or contamination introduced as a consequence of sample processing,processing.
The contribution of such factors to the value measured on the genuine sample may therefore be eliminated by subtracting the
measured value for the method blank, typically providing a better estimate for the true value of the quantity of analyte in the
sample.
3.2.3 recovery correction, n—a factor applied to the measured value of the analyte in the sample to account for losses of analyte
during sample processing.
3.2.3.1 Discussion—
Some of the analyte originally present in a sample is likely to be lost during the process of preparing the sample for instrumental
measurement, so that the measured value will typically be subject to negative bias. The proportion of analyte lost may be estimated
by repeated measurement of a sample containing a known quantity of the analyte and a correction factor introduced to account for
losses. Recovery correction is only required when analyte losses are significant when compared with overall measurement
uncertainty.
3.2.4 spike, n—a known quantity of analyte added to a sample.
4. Summary of Test Method
4.1 A 4 % by weight solution of UF is initially prepared by reacting a quantity of UF with water. Sub-sampling of UF may
6 6 6
be carried out as described in Practice C1689. Preparation of the hydrolyzed solution may be carried out as described in Practice
C1346. The laboratory may choose to adopt a simplified version of the standard practices, or to adopt other practices, provided
that any additional error thereby introduced is incorporated within precision statements for the method.
4.2 Concentrated nitric acid is added to the uranium solution to give a nitric acid concentration of approximately 1.5 M. The
solution is then passed through a diamyl amylphosphonate (DAAP) resin column which retains the uranium. Boron, silicon, and
technetium are eluted from the column with 2 M nitric acid and the solution made up to volume with reagent water. The boron,
silicon, and technetium concentrations are then measured using an ICP-MS. An on-line internal reference solution may be used
to correct results for any instrumental drift and results are blank corrected using a prepared method blank.
NOTE 1—The method described in this standard herein uses a 3 mL sample of 4 % by weight UF solution. The apparatus and the quantities and
concentrations of reagents and materials described in the standard are appropriate to this sample size and concentration. The data presented in Section
14 have been generated using samples of this size and concentration. Alternative sample sizes and concentrations may be used but will require that the
laboratory adjust apparatus, reagents and materials accordingly and validate the method for the adjusted conditions.
5. Significance and Use
5.1 This method is capable of measuring the concentration of boron, silicon, and technetium in UF . Limits for these
contaminants are set in Specifications C787 and C996.
6. Interferences
99 99 98 +
6.1 Tc suffers an isobaric interference with Ru and a molecular interference due to MoH ions; however, the diluted,
99 98 +
hydrolyzed UF samples should not give rise to any significant amount of Ru or MoH ions.
7. Apparatus
7.1 Ordinary laboratory apparatus are not listed but are assumed to be present.
7.1.1 ICP-MS controlled by computer and fitted with associated software and peripherals, including an inert sample introduction
system.
NOTE 2—A standard quartz sample introduction system is not suitable as it will affect the silicon measurement. A perfluoroalkoxy fluorocarbon plastic
(PFA) introduction system with platinum injector has proven acceptable. New equipment may need to be pre-soaked or flushed with a dilute hydrofluoric
acid solution, or both, to obtain a stable silicon background.
NOTE 3—It is recommended that an auto sampler with tube racks and plastic sample tubes compatible with the ICP-MS be used.
7.1.2 Balance to read to 0.01 g intervals or less.
7.1.3 Appropriately sized, variable volume pipettes such as 1 to 10 mL; 100 to 1200 μL; 20 to 300 μL; 5 to 100 μL used with
polyethylene pipette tips.
7.1.4 Appropriately sized plastic, spouted measuring cylinders (for preparing dilute acids).
7.1.5 Plastic beakers, 100 mL size.
7.1.6 Low density polyethylene bottles with leak proof lids, various sizes.
NOTE 4—PFA containers may be used as an alternative and may help to reduce silicon background levels.
7.1.7 Polyfluoroalkoxy fluorocarbon plastic (PFA) bottles, various sizes.
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7.1.8 Polyethylene sample tubes with leak proof lids, 25 mL and 50 mL 50 mL size.
7.1.9 Disposable Gloves—impermeable and powder free to avoid the potential for contamination and to provide protection
against toxic and corrosive substances. PVC gloves are suitable.
NOTE 5— The use of glassware must be avoided throughout this method as interaction with acid fluoride solutions will affect the silicon measurement.
8. Reagents and Materials
8.1 The sensitivity of the ICP-MS technique requires the use of ultra high purity reagents in order to be able to obtain low levels
of detection and satisfactory precision. All the reagents below are ultra high purity grade unless otherwise stated.
8.1.1 Concentrated nitric acid, specific gravity 1.42, 16 M.
8.1.2 Concentrated hydrochloric acid, specific gravity 1.18, 11.3 M.
8.1.3 Concentrated hydrofluoric acid, 48 % by weight or similar concentration.
8.1.4 Reagent water conforming to Specification D1193.
8.1.5 Nitric acid, 0.32 M (200 mL of concentrated nitric acid diluted to 10 L or equivalent ratio).
8.1.6 Nitric acid, 2 M (125 mL of concentrated nitric acid diluted to 1 L or equivalent ratio).
8.1.7 Nitric acid, 3 M (188 mL of concentrated nitric acid diluted to 1 L or equivalent ratio).
8.1.8 Hydrochloric acid, 0.1 M (8.8 mL of concentrated hydrochloric acid diluted to 1 L or equivalent ratio).
8.1.9 Two independent 10 000 mg/L silicon standards (one for calibration, one for sample spiking and Quality Control).
8.1.10 Two independent 1000 mg/L boron standards (one for calibration, one for sample spiking and Quality Control).
8.1.11 Two independent technetium standards (one for calibration, one for sample spiking and Quality Control). Concentrations
at 52.04 Bq/mL (82(82 μg μg/L) ⁄L) and 63.24 Bq/mL (100 μg/L) have proven acceptable but other similar values may be used
if precisely known.
8.1.12 1000 mg/L indium, scandium and beryllium standards (used for internal reference solutions).
NOTE 6—Alternative elements may be used for the internal reference solution. Care must be taken to ensure consistency between batches of standards
where the element chosen has more than one naturally occurring isotope.
8.1.13 Synthetic Pseudo Blank Matrix. 29 mL of 48 % by weight hydrofluoric acid diluted to 1 L or equivalent mixture to
produce a 1.3 % by weight fluoride solution (equivalent fluoride concentration to a 4 % by weight UF solution). Store in a PFA
bottle and mix thoroughly before use.
8.1.14 Bulked Pseudo Blank Matrix. This is synthetic pseudo blank matrix that has passed through the preparation and solid
phase extraction process described in paragraphs 12.1 – 12.10, measured and shown to contain very low levels of boron, silicon,
and technetium. It is used to prepare calibration standards and instrument quality control samples.
8.1.15 Pre-packed DAAP resin columns, 2 mL, together with reservoirs and end caps as appropriate.
NOTE 7—New columns may need to be pre-treated before first use to remove trace silicon contamination. Pre-treatment may be carried out by passing
sample material that does not require analysis through the column, eluting and regenerating the column as described in Section 12.
8.1.16 Argon gas (carrier gas for the ICP-MS), >99.99 % purity.
9. Hazards
9.1 Adequate laboratory facilities, such as fume hoods and controlled ventilation, along with safe techniques, must be used in
this procedure. Extreme care should be exercised in using hydrofluoric and other concentrated acids. Use of chemical resistant
gloves and eye protection is recommended. Refer to the laboratory’s health and safety arrangements and other applicable guidance
for handling chemical and radioactive materials and for the management of radioactive, mixed, and hazardous waste.
9.2 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 personal protective equipment to protect
from skin and eye contact Familiarization and compliance with the Safety Data Sheet is essential.
9.3 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.
10. Calibration and Standardization
10.1 The standards and blanks described below are prepared. The laboratory may choose to prepare different volumes of these
materials and at different concentrations where appropriate to the requirements of the laboratory and the measurement to be
performed.
10.2 Internal Reference Solution (50 μg/L In, 100 μg/L Sc and 500 μg ⁄L Be)—Internal Reference Solution (50 μg/L In, 100 μg/L
Sc and 500 μg/L Be). Add approximately 1.5 L of 0.32 M nitric acid to a 2 L PFA bottle. Pipet 0.1 mL of 1000 mg/L indium
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standard, 0.2 mL of 1000 mg/L scandium standard, and 1.0 mL of 1000 mg/L beryllium standard into the bottle. Fill up to the 2
L mark with 0.32 M nitric acid. Mix thoroughly before use.
10.3 Boron, Silicon, and Technetium Stock Solution Used for Calibration Standards (2.5 mg/L B, 100 mg ⁄L Si, and 500 ng ⁄L
99 99
Tc)—Boron, Silicon and Technetium Stock Solution, used for calibration standards (2.5 mg/L B, 100 mg/L Si and 500 ng/L Tc).
Place a labeled 125 mL PFA bottle on to a balance and tare. Add approximately 50 mL of 0.32 M nitric acid to the bottle. Pipet
0.25 mL 0.25 mL of 10001000 mg mg/L ⁄L boron standard, 1.0 mL of 10 000 mg/L silicon standard, and 0.61 mL 0.61 mL of
8282 μg μg/L ⁄L technetium standard solution into the bottle. Make up to 101 g (60.5 g)6 0.5 g with 0.32 M nitric acid. Add screw
top lid and mix thoroughly.
NOTE 8—The volume of a technetium standard with a different starting concentration should be adjusted to give the required final concentration of 500
ng/L, or any different concentration deemed more appropriate to the requirements of the laboratory (see 10.1).
NOTE 9—The density of 0.32 M nitric acid at 20°C20 °C is taken to be 1.0091.009 g g/mL. ⁄mL.
10.4 Boron, Silicon, and Technetium Blank Calibration Standard—Boron Silicon and Technetium Blank Calibration
Standard.Place a labeled 125 mL 125 mL PFA bottle on to a balance and tare. Add 101 g (60.5 g)6 0.5 g of Bulked Pseudo Blank
Matrix to the bottle. Add screw top lid and mix thoroughly.
10.5 Boron, Silicon, and Technetium Calibration Standard 1 (10 μg/L B, 400 μg/L Si, and 2.0 ng/L Tc)—Boron, Silicon and
Technetium Calibration Standard 1 (10 μg/L B, 400 μg/L Si and 2.0 ng/L Tc). Place a labeled 125 mL PFA bottle on to a balance
and tare. Add approximately 50 mL of Bulked Pseudo Blank Matrix to the bottle. Pipet 0.4 mL 0.4 mL of Boron, Silicon, and
Technetium Stock Solution into the bottle and make up to 101 g (60.5 g)6 0.5 g with Bulked Pseudo Blank Matrix. Add screw
top lid and mix thoroughly.
10.6 Boron, Silicon, and Technetium Calibration Standard 2 (20 μg/L B, 800 μg/L Si, and 4.0 ng/L Tc)—Boron, Silicon, and
Technetium Calibration Standard 2 (20 μg/L B, 800 μg/L Si and 4.0 ng/L Tc). Place a labeled 125 mL 125 mL PFA bottle on
to a balance and tare. Add approximately 50 mL 50 mL of Bulked Pseudo Blank Matrix to the bottle. Pipet 0.8 mL 0.8 mL of
Boron, Silicon, and Technetium Stock Solution into the bottle and make up to 101 g (60.5 g)6 0.5 g with Bulked Pseudo Blank
Matrix. Add screw top lid and mix thoroughly.
10.7 Boron, Silicon, and Technetium Calibration Standard 3 (50 μg/L B, 2.0 mg/L Si, and 10 ng/L Tc)—Boron, Silicon and
Technetium Calibration Standard 3 (50 μg/L B, 2.0 mg/L Si and 10 ng/L Tc). Place a labeled 125 mL 125 mL PFA bottle on to
a balance and tare. Add approximately 50 mL 50 mL of Bulked Pseudo Blank Matrix to the bottle. Pipet 2.0 mL 2.0 mL of Boron,
Silicon, and Technetium Stock Solution into the bottle and make up to 101 g (60.5 g)6 0.5 g with Bulked Pseudo Blank Matrix.
Add screw top lid and mix thoroughly.
10.8 Boron, Silicon, and Technetium Instrument Quality Control Stock/Spike Solution (12.5 mg/L B, 500 mg/L Si, and 2.5 μg
/L Tc)—Boron, Silicon and Technetium Instrument Quality Control Stock/Spike Solution (12.5 mg/L B, 500 mg/L Si and 2.5 μg
/L Tc). Place a labeled 125 mL PFA bottle on to a balance and tare. Add approximately 50 mL 50 mL of 0.32 M nitric acid to
the bottle. Pipet 1.25 mL of 1000 mg/L boron standard, 5.0 mL 5.0 mL of 10 000 mg/L silicon standard, and 2.5 mL 2.5 mL of
100100 μg μg/L ⁄L technetium standard into the bottle (see Note 6). Make up to 101 g (60.5g)6 0.5 g with 0.32 M nitric acid.
Add screw top lid and mix thoroughly. The standards used for this solution should be different from those used to prepare the
Boron, Silicon, and Technetium Stock Solution used for preparation of calibration standards.
10.9 Boron, Silicon, and Technetium Instrument Quality Control Sample (25 μg/L B, 1000 μg/L Si, and 5 ng/L Tc)—Boron,
Silicon and Technetium Instrument Quality Control Sample (25 μg/L B, 1000 μg/L Si and 5 ng/L Tc). Place a labeled 125 mL
PFA bottle on to a balance and tare. Add approximately 50 mL of Bulked Pseudo Blank Matrix to the bottle. Pipet 0.2 mL of Boron
Silicon, and Technetium Instrument Quality Control Stock/Spike Solution into the bottle and make up to 101 g (60.5 g)6 0.5 g
with Bulked Pseudo Blank Matrix. Add screw top lid and mix thoroughly.
11. Conditioning
11.1 Some types of sample tube may require cleaning before use due to high levels of background silicon contamination. If this
is found to be the case then tubes or lids may be cleaned by soaking for at least 1 hr, preferably overnight, in 0.32 M nitric acid.
Prior to use the tubes/lids must be rinsed three times with reagent water and any excess liquid shaken off.
11.2 The uranium removal process may use a single DAAP column or a pair of DAAP columns in series depending on the
quantity of uranium in the sample. The procedure as described assumes the use of a pair of DAAP columns in series.
11.3 A column pair is required for each sample in a batch, any spiked samples and a method blank. Preparation of Bulked
Pseudo Blank Matrix may also be carried out alongside sample analysis and will require additional column pairs.
11.4 Each column pair is prepared and conditioned as follows:
11.4.1 The pair is set up, one above the other in a column rack or other suitable holder. Each column is checked for bubbling
or voiding in the resin and for any yellow coloration and discarded if necessary.
11.4.2 A clean, 25 mL reservoir accessory is attached to each column and a plastic beaker is placed under the lower column.
The end caps are removed and the column contents allowed to drain into the beakers.
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11.4.3 A pipette is used to add 5 mL of 3 M nitric acid to the reservoir fitted to the upper column and allowed to drain through
both columns. The contents of the beaker are discarded as waste. The columns are n
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