Designation: C 1508 – 01

Standard Test Method for

Determination of Bromine and Chlorine in UF6 and Uranyl
Nitrate by X-Ray Fluorescence (XRF) Spectroscopy1
This standard is issued under the fixed designation C 1508; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope analyzed by X-ray fluorescence using two different crystal/

1.1 This method covers the determination of bromine (Br) detector systems.
and chlorine (Cl) in uranium hexafluoride (UF6) and uranyl 4. Significance and Use
nitrate solution. The method as written covers the determina-
tion of bromine in UF6 over the concentration range of 0.2 to 4.1 The method is designed to show whether or not the
8 µg/g, uranium basis. The chlorine in UF6 can be determined tested materials meet the specifications as given in C 787 and
over the range of 4 to 160 µg/g, uranium basis. Higher C 788.
concentrations may be covered by appropriate dilutions. The 5. Interferences
detection limit for Br is 0.2 µg/g uranium basis and for Cl is 4
µg/g uranium basis. 5.1 Plastic equipment must be used throughout the method
1.2 This standard may involve hazardous materials, opera- for uranyl fluoride as the hydrofluoric acid in the uranyl
tions and equipment. This standard does not purport to address fluoride leaches chloride from glassware causing a high bias.
all of the safety concerns, if any, associated with its use. It is 5.2 Low recoveries may occur as the precipitate can be
the responsibility of the user of this standard to establish difficult to transfer quantitatively to the filter paper. A surfac-
appropriate safety and health practices and determine the tant can be added (optional step) to minimize the adhesion of
applicability of regulatory limitations prior to use. the precipitate to the walls of the beakers and the funnel.

2. Referenced Documents 6. Apparatus

2.1 ASTM Standards: 6.1 X-Ray Spectrometer, see Guide C 1118 for the selection
C 761 Test Methods for Chemical, Mass Spectrometric, of the X-ray Spectrometer.
Spectrochemical, Nuclear and Radiochemical Analysis of 6.2 Plastic Vacuum Filtration Apparatus, for 47 mm diam-
Uranium Hexafluoride2 eter filter paper.
C 787 Specification for Uranium Hexafluoride for Enrich- 6.3 Filter Paper, 0.45 micron, 47 mm diameter.4
ment2 6.4 Beakers, polypropylene, 250 mL.
C 788 Specification for Uranyl Nitrate2 6.5 Stirring Rods, plastic or Teflon.
C 1118 Guide for Selecting Components for Wavelength 6.6 X-ray Sample Support, Rings. Inner diameter approxi-
Dispersive X-Ray Fluorescence (XRF) Systems2 mately 40 mm.
D 1193 Specification for Reagent Water3 7. Reagents
3. Summary of Test Method 7.1 Purity of Reagents—Reagent grade chemicals shall be
3.1 A sample of hydrolyzed UF6 (uranyl fluoride) or uranyl used in all tests. Unless otherwise indicated, it is intended that
nitrate solution is treated with sodium nitrite to reduce oxidized all reagents conform to the specifications of the Committee on
forms of bromine and chlorine (bromates and chlorates) to their Analytical Reagents of the American Chemical Society, where
respective halide ions. Addition of silver nitrate precipitates the such specifications are available.5 Other grades may be used,
silver halides. Spike recoveries can be improved by the provided it is first ascertained that the reagent is of sufficiently
addition of potassium iodide causing coprecipitation of the high purity to permit its use without lessening the accuracy of
halides. The halides are collected on filter paper and are the determination.
7.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean reagent water conforming
1
This test method is under the jurisdiction of ASTM Committee C26 on Nuclear
4
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of The filter must be Cl and Br free. Millipore membrane filter type HABP
Test. (www.millipore.com) has been successfully used. An alternate is 15A from S.C.B,
Current edition approved August 10, 2001. Published September 2001. BP6, RN86, 07130 Soyons France. Any other equivalent is acceptable.
2 5
Annual Book of ASTM Standards, Vol 12.01. Reagent Chemicals, American Society Specifications, American Chemical
3
Annual Book of ASTM Standards, Vol 11.01. Society, Washington, DC.

Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.

1
 C 1508
to Specification D 1193, Type I. TABLE 1 Suggested X-Ray Settings
7.3 Ammonium Hydroxide, NH4OH, concentrated, specific Bromine Chlorine
gravity 0.90. Line Ka Ka
7.4 Ammonium Hydroxide Solution, 1 + 3 (3.7 M). Dilute 1 Crystal LiF 200 PE (Tetrakis(hydroxymethyl)-
(Lithium fluoride) methane)
part NH4OH with 3 parts water. Detector Scintillation Flow
7.5 Surfactant, bromine and chlorine free.6 (Optional). Order 1 1
7.6 Surfactant Solution, 1 + 999. Add 1 mL of surfactant to X-ray tube Rhodium Rhodium
Tube voltage (kV) 45 45
approximately 1 litre of water. (Optional). Tube Amperage (mA) 45 75
7.7 Nitric Acid, HNO3, concentrated, specific gravity 1.42. Counting Time (s) 40 40
7.8 Nitric Acid Solution, 1 + 999 (0.016 M). Add 1 mL of
concentrated HNO3 to approximately 200 mL of water. Add 1
mL of the surfactant (7.6). (Optional). Dilute to 1 litre. duplicates, spikes and controls with the samples. Use the
7.9 Sodium Nitrite, NaNO2. solution prepared in 7.17 for the spikes.
7.10 Sodium Nitrite Solution, 2 g/L. Dissolve 1 g of sodium NOTE 2—2 mL and 4 mL spike aliquots were found to be reasonable
nitrite in water and dilute to 500 mL. Prepare fresh immedi- volumes.
ately before use. 9.3 Add 0.5 mL of potassium iodide solution to each sample
7.11 Silver Nitrate, AgNO3. and standard. (Optional step).
7.12 Silver Nitrate Solution, 2 g/L. Dissolve 2 g of silver 9.4 Add 4 mL of surfactant solution 7.6. (Optional step).
nitrate in water and dilute to 1 litre. Keep away from light in an 9.5 Add 10 mL of sodium nitrite solution to each sample
opaque bottle. The solution should be made fresh weekly. and standard. Stir each solution with a dedicated plastic stirring
Silver is an RCRA listed hazardous waste. Make up only as rod and allow to stand for a minimum of 2 minutes.
much of this solution as required to minimize excess waste. 9.6 Slowly and with stirring add 25 mL of the silver nitrate
7.13 Potassium Bromide, KBr. solution. Remove the plastic stirring rods. Heat the solution in
7.14 Bromide Solution, 500 mg Br/L. Dissolve 0.1861 g of a water bath at approximately 80°C 6 10°C for 11⁄2 hours.
KBr (dried at 110°C for 1 hour) in water and dilute to 250 mL 9.7 Remove from the bath. Allow the halides to precipitate
in a volumetric flask. overnight. A 2 hour precipitation time has been found to be
7.15 Sodium Chloride, NaCl. successful, but the user must establish precision and bias based
7.16 Sodium Chloride Solution, 1000 mg Cl/L. Dissolve on the shorter time. The precision and bias data in this standard
1.648 g NaCl (dried at 110° C for 1 hour ) in water and dilute were generated using an overnight precipitation.
to 1 litre in a volumetric flask. 9.8 Filter using 0.45 micron filter paper. Use a plastic
7.17 Spike Solution, 5 mg Br/L, 100 mg Cl/L. Transfer 10 vacuum filtration assembly. Use a plastic rod with a rubber
mL of 500 mg Br /L solution into a 1 litre volumetric flask by policeman to aid the transfer of precipitate to the filter. Use 1
pipette. Transfer 100 mL of 1000 mg Cl /L into the flask by + 999 nitric acid solution to wash the precipitate. Dry the filters
pipette. Dilute to volume. before counting in the X-ray.
7.18 Potassium Iodide, KI. (Optional). 9.9 Place the filters on X-ray sample support rings and tape
7.19 Potassium Iodide Solution, (Optional), 1g I/L. Dis- or glue in place.
solve 0.131 g potassium iodide in water and dilute to 100 mL. 9.10 Analyze using the X-ray.
The solution should be prepared weekly.
10. Instrument Calibration
8. Standard Preparation 10.1 Follow the manufacturer’s instructions for setting up
8.1 Pipette the following aliquots of spike solution (from the instrument to achieve an inert gas environment and to
7.17) into polypropylene beakers. 0 mL, 1 mL, 2 mL, 5 mL, 10 obtain the following instrument parameters. (See Table 1).
mL. The aliquots represent 0µg Br, 5µg Br, 10µg Br, 25µg Br, 10.2 Run the standards and construct a calibration curve
50µg Br and 0µg Cl, 100µg Cl, 200µg Cl, 500µg Cl, 1000µg Cl. using the instrument’s software or by manually plotting the
8.2 Add 70 mL water to each beaker. curve using linear chart paper.
8.3 Follow steps 9.3-9.8 at the same time as the samples. 10.3 Run the samples. Determine the weight of Br and Cl
present on the filter papers from the calibration curves.
9. Procedure
Calculate the concentration of Br and Cl in the samples by
9.1 Transfer a known aliquot of uranyl fluoride solution following Section 11.
(prepared following Test Methods C 761) or uranyl nitrate that
contains a known amount of uranium, approximately 5 g, with TABLE 2 Within Laboratory Precision For UF6
a plastic graduated cylinder into a polypropylene beaker Laboratory Halide
Concentration Standard Deviation Number of
containing 70 mL water. (µg halide/g U) (µg halide/g U) Determinations
A Bromine 0.44 0.06 10
NOTE 1—Recommend cleaning all laboratory equipment with ammo- A Bromine 3.1 0.2 9
nium hydroxide solution (7.4) prior to use. B Bromine 5.1 0.7 109
A Chlorine 2.4 2.1 9
9.2 Follow laboratory QA practices and run the necessary A Chlorine 66 6 8
A Chlorine 185 19 9
B Chlorine 48 5 107
6
Triton X-100, Rohm and Haas, has been successfully used.

2
 C 1508
TABLE 3 Bias Estimates For UF6
Laboratory Halide Spike Concentration Spike Mean Bias Estimate Relative Difference Number of Determinations
(µg halide/g U) (µg halide) (µg halide)
A Bromine 2 10 10.6 +0.6 +6 % 10
A Bromine 4 20 20.5 +0.5 +2.5 % 10
B Bromine 5 25 25.5 +0.5 +2 % 109
A Chlorine 40 200 213 +13 +6.5 % 10
A Chlorine 80 400 450 +50 +12.5 % 10
B Chlorine 50 250 238 –12 –6 % 107

TABLE 4 Within Laboratory Precision For Uranyl Nitrate was obtained by 1 technician over a 1 year period. Potassium
Solutions iodide was not added to Laboratory B samples. The precision
Halide Concentration Standard Number of is given in Table 2.
(µg halide/g U) Deviation Determinations
12.1.2 Bias in UF6 Samples—No standard material certified
Bromine 10 1.5 3 for bromine and chlorine in UF6 is available. Therefore bias
Bromine Blank 0.04 3
Chlorine 50 9 3 cannot be determined. To determine lower bound bias indica-
Chlorine Blank 0.5 3 tions uranyl fluoride solutions were spiked with NIST SRM.
The uncertainty of the NIST traceable standard is less than the
uncertainty of the procedure. The data for Laboratory A were
11. Calculation collected over a 3 month period by two technicians. Potassium
11.1 Calculate the halide content as follows: iodide was added to laboratory A samples. The result data for
Laboratory B were obtained over a 1 year period by 1
A 3 1000
Halide, µg/g uranium basis 5 B 3 C technician. No potassium iodide was added to laboratory B
samples. The mean minus the prepared values are an indication
where: of the bias. The relative differences are given in Table 3. The
A = micrograms halide from the calibration curve, relative difference is [(mean-known)/known] 3 100 %.
1000 = conversion factor, litres to millilitres, 12.2 Uranyl Nitrate Data:
B = sample aliquot from 9.1, in millitres, and 12.2.1 Precision in Uranyl Nitrate Samples—The result
C = uranium concentration of sample solution, in g/L. data were collected in 1 day by 1 technician. The precision is
given in Table 4. No potassium iodide (optional 9.3) was added
12. Precision and Bias to the uranyl nitrate samples.
12.1 Uranium Hexafluoride Data: 12.2.2 Bias in Uranyl Nitrate Samples—The bias should be
12.1.1 Precision in UF6 Samples—The single laboratory equivalent to the bias in UF6 samples.
precision for the average of multiple determinations is given in 12.3 The supporting data for Tables 2-4 are available from
. The data for laboratory A were collected using a rhodium ASTM headquarters.
X-ray tube and a LiF200 crystal for bromine and a PE crystal
for chlorine. Potassium iodide (optional 9.3) was added to the 13. Keywords
samples in laboratory A. The results were obtained over a 3 13.1 bromine; chlorine; uranium hexafluoride; X-ray fluo-
month period by two technicians. The results for laboratory B rescence; XRF

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