ASTM C1219-05(2009)
(Test Method)Standard Test Methods for Arsenic in Uranium Hexafluoride (Withdrawn 2015)
Standard Test Methods for Arsenic in Uranium Hexafluoride (Withdrawn 2015)
SIGNIFICANCE AND USE
Arsenic compounds are suspected to cause corrosion in some materials used in UF6 handling equipment. Arsenic originates as a contaminant in fluorspar (CaF2) used to produce anhydrous hydrogen fluoride which is used subsequently in the production of UF 6.
These test methods are used to measure the arsenic content in UO2F2 solutions prepared from the hydrolysis of UF6 for determination of conformance to Specification C 787.
SCOPE
1.1 These test methods are applicable to the determination of total arsenic in uranium hexafluoride (UF6) by atomic absorption spectrometry. Two test methods are given: Test Method A—Arsine Generation-Atomic Absorption (Sections 5-10), and Test Method B—Graphite Furnace Atomic Absorption (Appendix X1).
1.2 The test methods are equivalent. The limit of detection for each test method is 0.1 μg As/g U when using a sample containing 0.5 to 1.0 g U. Test Method B does not have the complete collection details for precision and bias data thus the method appears as an appendix.
1.3 Test Method A covers the measurement of arsenic in uranyl fluoride (UO2F2) solutions by converting arsenic to arsine and measuring the arsine vapor by flame atomic absorption spectrometry.
1.4 Test Method B utilizes a solvent extraction to remove the uranium from the UO2F2 solution prior to measurement of the arsenic by graphite furnace atomic absorption spectrometry.
1.5 Both insoluble and soluble arsenic are measured when UF6 is prepared according to Test Method C 761.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.7 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.
WITHDRAWN RATIONALE
These test methods were applicable to the determination of total arsenic in uranium hexafluoride (UF6) by atomic absorption spectrometry.
Formerly under the jurisdiction of Committee C26 on Nuclear Fuel Cycle, these test methods were withdrawn in June 2015 and replaced by Test Method C1287 on the Determination of Impurities in Nuclear Grade Uranium Compounds by Inductively Coupled Plasma Mass Spectrometry.1
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Standards Content (Sample)
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:C1219 −05(Reapproved2009)
Standard Test Methods for
Arsenic in Uranium Hexafluoride
This standard is issued under the fixed designation C1219; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
1.1 These test methods are applicable to the determination
of total arsenic in uranium hexafluoride (UF ) by atomic
2. Referenced Documents
absorption spectrometry. Two test methods are given: Test
2.1 ASTM Standards:
Method A—Arsine Generation-Atomic Absorption (Sections
C761Test Methods for Chemical, Mass Spectrometric,
5-10), and Test Method B—Graphite FurnaceAtomicAbsorp-
Spectrochemical,Nuclear,andRadiochemicalAnalysisof
tion (Appendix X1).
Uranium Hexafluoride
1.2 The test methods are equivalent. The limit of detection
C787Specification for Uranium Hexafluoride for Enrich-
for each test method is 0.1 µg As/g U when using a sample
ment
containing 0.5 to 1.0 g U. Test Method B does not have the
D1193Specification for Reagent Water
complete collection details for precision and bias data thus the
3. Summary of Test Method
method appears as an appendix.
3.1 Arsine Generation-Atomic Absorption Spectrometry
1.3 Test Method A covers the measurement of arsenic in
Method—The sample of UF is hydrolyzed and the UO F
uranyl fluoride (UO F ) solutions by converting arsenic to 6 2 2
2 2
solution is fumed with sulfuric acid in the presence of boric
arsine and measuring the arsine vapor by flame atomic absorp-
acid to complex the fluoride. Potassium iodide is used to
tion spectrometry.
reduce arsenic(V) to arsenic(III). Sodium borohydride is used
1.4 Test Method B utilizes a solvent extraction to remove
togeneratearsinevaporinahydridegeneratorwithsubsequent
the uranium from the UO F solution prior to measurement of
2 2
measurement by flame atomic absorption spectrometry.
the arsenic by graphite furnace atomic absorption spectrom-
3.2 Graphite Furnace Atomic Absorption Spectrometry
etry.
Method—ThesampleofUF ishydrolyzed,andtheuraniumin
1.5 Both insoluble and soluble arsenic are measured when
the UO F solution is removed by extraction with tri(2-ethyl-
2 2
UF is prepared according to Test Method C761.
hexyl)phosphate/heptane. The aqueous phase containing the
1.6 The values stated in SI units are to be regarded as
arsenic is analyzed by graphite furnace atomic absorption.
standard. No other units of measurement are included in this
4. Significance and Use
standard.
4.1 Arsenic compounds are suspected to cause corrosion in
1.7 This standard does not purport to address all of the
some materials used in UF handling equipment. Arsenic
safety concerns, if any, associated with its use. It is the 6
originatesasacontaminantinfluorspar(CaF )usedtoproduce
responsibility of the user of this standard to establish appro- 2
anhydroushydrogenfluoridewhichisusedsubsequentlyinthe
production of UF .
This test methods are under the jurisdiction of ASTM Committee C26 on
Nuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.05 on
Methods of Test. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved July 1, 2009. Published August 2009. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1992. Last previous edition approved in 2005 as C1219–05. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/C1219-05R09. the ASTM website.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959. United States
C1219−05(2009)
TABLE 1 Atomic Absorption Operating Parameters
4.2 These test methods are used to measure the arsenic
content in UO F solutions prepared from the hydrolysis of Element arsenic
2 2
Wavelength, nm 193.7
UF for determination of conformance to Specification C787.
Lamp current, mA 10
Slit width, nm 0.5
TEST METHOD A—ARSINE GENERATION-ATOMIC
Gas C H /air
2 2
ABSORPTION SPECTROMETRY
Acetylene, psig 9
Air, psig 40
Argon, psig 50
5. Interferences
Fuel flow, L/min 1.5
Oxidant flow, L/min 4.0
5.1 The presence of hydrofluoric acid in the sample sup-
presses arsine generation when using sodium borohydride.
Boric acid is added to complex the fluoride present at a molar
excess of 250%.
5.2 Arsenic(V) must be reduced to arsenic(III) otherwise
7.1.6 Arsenic Standard Solution (0.10 mg As/L)—Pipet 10
arsine will not be generated using sodium borohydride and
mLof 1000 mg/Larsenic stock solution into a 1-Lvolumetric
hydrochloric acid.
flask containing 500 mL of water.Add 20 mL of concentrated
5.3 The reduction of arsenic(V) by potassium iodide is time
hydrochloric acid, dilute to volume with water and mix. This
dependentatroomtemperaturerequiringstrictadherencetothe
(10 mg/L) solution should be kept no longer than one month.
procedure.
Pipet 2 mL of the 10 mg/L arsenic solution into a 200-mL
volumetric flask containing 100 mL of water. Add 4 mL of
5.4 Do not use platinum labware.
concentrated hydrochloric acid and dilute to volume with
water.
6. Apparatus
NOTE 1—The 0.10-mgAs/L solution must not be kept longer than one
6.1 Atomic Absorption Spectrometer, equipped with an air-
day.
acetylene burner, arsenic hollow cathode lamp and hydride
generator, gas/liquid separator, and hydride absorption cell. 7.1.7 Boric Acid (H BO ).
3 3
7.1.8 Hydrochloric Acid (sp gr 1.18)—Concentrated hydro-
6.2 Hot Plate, capable of reaching a surface temperature of
chloric acid (HCl).
500°C.
7.1.9 Hydrochloric Acid (1+1)—Add one volume of con-
centrated hydrochloric acid to one volume of water.
7. Reagents and Materials
7.1.10 Hydrochloric Acid (1+2)—Add one volume of con-
7.1 Reagents:
centrated hydrochloric acid to two volumes of water.
7.1.1 Purity of Reagents—Reagent grade chemicals shall be
7.1.11 Nitrogen (N ), 99.9% minimum purity.
used in all tests. Unless otherwise indicated, it is intended that
7.1.12 Potassium Iodide Solution (50% w/v)—Dissolve 50
all reagents conform to the specifications of the Committee on
g of potassium iodide in water and dilute to 100 mL in a
Analytical Reagents of theAmerican Chemical Society, where
volumetric flask. Store in a brown bottle.
such specifications are available. Other grades may be used,
NOTE 2—The colorless solution is stable for two days. A yellow tinge
provided it is first ascertained that the reagent is of sufficiently
indicates the solution has deteriorated.
high purity to permit its use without lessening the accuracy of
the determination. 7.1.13 Sodium Borohydride Solution (6.0 g/L)—Dissolve
3.0 g of sodium borohydride (NaBH ) and 2.5 g of sodium
7.1.2 Purity of Water—Unless otherwise indicated, refer-
ences to water shall mean reagent waterType II conforming to hydroxide (NaOH) in water and dilute to 500 mL in a
volumetric flask. This solution should be prepared weekly.
Specification D1193.
7.1.14 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric
7.1.3 Acetylene (C H ), 99.6% minimum purity.
2 2
acid (H SO ).
7.1.4 Air, compressed breathing air or equivalent.
2 4
7.1.5 Arsenic Standard Stock Solution (1000 mg As/L)—
8. Calibration and Standardization
Dissolve 1.320 g of arsenic trioxide (As O ) in 100 mL of
2 3
hydrochloric acid (1+2) and dilute to 1 L. Commercially
8.1 Instrument Parameters—A set of suggested atomic ab-
available stock solutions traceable to NIST primary standards
sorption operating parameters is listed in Tables 1 and 2. The
may be used.
parameters may vary with the type of instrument used and the
manufacturer’s instructions.
8.2 Preparation of Calibration Solutions:
Petrik, K., and Krivan, V., “Radiotracer Investigation of the Interference of
8.2.1 Aliquot0,2,5,10,20,and30mLofthe0.10mgAs/L
Hydrofluoric Acid in the Determination of Arsenic and Antimony by Hydride
GenerationAtomicAbsorptionSpectroscopy,” Analytical Chemistry, Vol 59,No.20
solution into 100-mL volumetric flasks. Add 2 mL concen-
(1987), pp. 2426–2427.
trated H SO and 10 mL concentrated HCl to each flask.
4 2 4
Reagent Chemicals, American Chemical Society Specifications, American
8.2.2 Add 2 mL of 50% potassium iodide solution and
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory dilute to volume with water 75 min before running the
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
calibration solutions.
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. 8.3 Calibration:
C1219−05(2009)
TABLE 2 Hydride Generator Operating Parameters
9.3.2 RecordtheconcentrationforcalculationinSection10.
Sample flow, mL/min 8 With an instrument which is not microprocessor-controlled,
Hydrochloric acid flow, mL/min 1
record the absorbance and determine the concentration from
Sodium borohydride flow, mL/min 1
the calibration graph.
9.3.3 Use a 30-s water rinse between samples if running
several samples. After 10 samples verify the calibration by
8.3.1 Follow the manufacturer’s directions to calibrate the
running the midrange calibration solution again. If the value
instrument. Use the following arsenic calibration solutions
deviates by more than 5%, repeat the calibration and measure
with a 30-s water rinse between each solution: 0, 0.002, 0.005,
the samples again.
0.010, 0.020, and 0.030 mg As/L. If the AA is manually
controlled, record the absorbances.
TABLE 3 Within Laboratory Precision
8.3.2 Withamicroprocessor-controlledinstrument,generate
the calibration curve using the manufacturer’s directions. The
Test Concentration, Standard Number of
%RSD
Method µgAs/g U Deviation Determinations
calibration curve can also be generated manually by graphing
A 0.35 0.033 9.4 30
the absorbance of the calibration solutions on the ordinate and
3.76 0.23 6.1 30
the corresponding concentration on the abscissa.
13.60 0.69 5.0 30
8.3.3 Verify the calibration by running the mid-range 0.010
mgAs/Lcalibration solution. If the value differs by more than
5%, repeat the calibration.
TABLE 4 Bias Estimates
Test Bias Number of
µgAs/g U Mean
9. Procedure
Method Estimate Determinations
A 1.996 1.909 −0.087 20
9.1 Sample Preparation:
9.1.1 Prepare a hydrolyzed UF solution within a concen-
tration range of 50 to 250 g/LU using the appropriate sections
of Test Method C761. 10. Calculation
9.1.2 Transfer an aliquot of UO F solution containing
2 2
10.1 Calculatethearsenicconcentrationusingthefollowing
approximately 0.5 g of uranium into a 125-mL Erlenmeyer
equation:
flask.
A 3 B
9.1.3 Add0.5gofH BO and2mLofconc
...
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