ASTM C1476-00
(Test Method)Standard Test Method for Analysis of Urin for Technetium-99 by Inductively Coupled Plasma-Mass Spectrometry
Standard Test Method for Analysis of Urin for Technetium-99 by Inductively Coupled Plasma-Mass Spectrometry
SCOPE
1.1 This test method covers the determination of the concentration of technetium-99 in urine using inductively coupled plasma-mass spectrometry (ICP-MS). This test method can be used to support uranium enrichment and reclamation facility bioassay programs.
1.2 The minimum detectable concentration for this test method, using a quadrupole ICP-MS, is approximately 1.0 ng/L (0.62 Bq/L).
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: C 1476 – 00
Standard Test Method for
Analysis of Urine for Technetium-99 by Inductively Coupled
Plasma-Mass Spectrometry
This standard is issued under the fixed designation C 1476; 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 Code of Federal Regulations, Title 10, 835.402
HPS N13.30 Performance Criteria for Radiobioassay
1.1 This test method covers the determination of the con-
centration of technetium-99 in urine using inductively coupled
3. Terminology
plasma-mass spectrometry (ICP-MS). This test method can be
3.1 Definitions:
used to support uranium enrichment and reclamation facility
3.1.1 instrument check standard, n—standard solutions
bioassay programs.
evaluated at given intervals during batch analysis to evaluate
1.2 The minimum detectable concentration for this test
instrument stability during analysis.
method, using a quadrupole ICP-MS, is approximately 1.0
3.1.2 internal reference standard, n—standard solutions,
ng/L (0.62 Bq/L).
containing an element with similar chemical properties to the
2. Referenced Documents analyte of interest, added to each calibration standard, check
standard, and sample for the purpose of monitoring and
2.1 ASTM Standards:
correcting for fluctuations in matrix, instrument drift, nebulizer
C 1009 Guide for Establishing a Quality Assurance Pro-
and sample orifice blockages, and aerosol transport effects.
gram for Analytical Chemistry Laboratories Within the
3.1.3 isobar, n—any nuclide that has the same atomic mass
Nuclear Industry
number as another atom, but a different atomic number.
C 1068 Guide for Qualification of Measurement Methods
3.2 Acronyms:
by a Laboratory Within the Nuclear Industry
3.2.1 ICP-MS, n—inductively coupled plasma-mass spec-
C 1128 Guide for Preparation of Working Reference Mate-
trometry.
rials for Use in the Analysis of Nuclear Fuel Cycle
3.2.2 LOD, n—limit of detection.
Materials
3.2.3 LCS, n—laboratory control standard.
C 1156 Guide for Establishing Calibration for a Measure-
3.2.4 MDC, n—minimum detectable concentration.
ment Method Used to Analyze Nuclear Fuel Cycle Mate-
3.2.5 %RSD, n—percent relative standard deviation (1 stan-
rials
dard deviation/Mean) * 100.
C 1210 Guide for Establishing a Measurement System
3.2.6 % Bias, n—((mean – true value)/true value) * 100.
Quality Control Program for Analytical Chemistry Labo-
ratories Within the Nuclear Industry
4. Summary of Test Method
C 1297 Guide for Qualification of Laboratory Analysts for
2 4.1 A urine sample is digested in the presence of hydrogen
the Analysis of Nuclear Fuel Cycle Materials
3 peroxide to decompose the organic matrix. The pertechnetate
D 1193 Specification for Reagent Water
ion is selectively separated from Ruthenium, actinides, alkali,
2.2 Other Standards:
4 and alkaline earth metals in the sample matrix using anion
ANSI N13.20 Radiological Measurement Quality
exchange chromatography.The Tc is eluted with warmed 3.0
M nitric acid. The Tc isotope is analyzed by ICP-MS using
115Inastheinternalreferencestandard. Thechemicalrecovery
This test method is under the jurisdiction ofASTM Committee C26 on Nuclear
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of
Test. Available from the Superintendent of Documents, U.S. Government Printing
Current edition approved June 10, 2000. Published August 2000. Office, Washington, DC 20402.
2 6
Annual Book of ASTM Standards, Vol 12.01. Health Physics Society, “Performance Criteria for Radiobioassay,” HPS
Annual Book of ASTM Standards, Vol 11.01. N13.30, McLean, VA, 1996.
4 7
Available from American National Standards Institute, 11 W. 42nd St., 13th Crain, J., and Gallimore, D., “Inductively Coupled Plasma-Mass Spectrometry
Floor, New York, NY 10036. of Synthetic Elements: Tc,” Applied Spectroscopy, Vol 46, 1992, pp. 547-549.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
C 1476
is determined by the sample, sample spike method. Recoveries 8.2 Purity of Water—Unless otherwise indicated, references
obtained from submitted samples over a one-year period to water shall be understood to mean reagent water as defined
averaged 89.9 %. by Type I of Specification D 1193.
8.3 Anion Exchange Resin—100-200 mesh (chloride
5. Significance and Use
form).
5.1 Code of Federal Regulations, Title 10, 835.402 states
8.4 Argon Gas, purity 99.99 % or better recommended.
that radiological workers who are likely to receive 100 mrem
8.5 Calibration Stock Solution—Prepare a calibration stock
from intakes are required to be monitored for exposure. For the
solution containing approximately 2000 ng/L of Tc from a
indirect bioassay for radiological workers exposed to nuclear
certified traceable NIST or equivalent certified standard.
material containing fission products, Tc must be measured in
8.6 Hydrochloric Acid (sp gr 1.18), concentrated, high-
urine samples.
purity Baker Ultrex or equivalent, hydrochloric acid (HCl).
8.7 Hydrochloric Acid (0.5 M)—Add 41.7 mL of concen-
6. Interferences
trated HCl to 900 mLof water, dilute to a final volume of 1000
6.1 Elements or complexes having a mass-to-charge ratio
mL, and mix.
(m/z) of 99 will interfere with the Tc analysis. Interfering
8.8 Hydrogen Peroxide (30 %), (H O ).
2 2
nuclides of mass 99 (molybdenum and ruthenium) are chemi-
8.9 Nitric Acid (sp gr 1.42), concentrated, high-purity Baker
cally separated using anion exchange chromatography. The
Ultrex or equivalent, nitric acid (HNO ).
presence of an interfering nuclide may be monitored by 3
8.10 Nitric Acid (0.5 M)—Add 31.3 mL of concentrated
evaluating the m/z value of another isotope of the interfering
element. HNO to900mLofwater,dilutetoafinalvolumeof1000mL,
and mix.
6.2 Alkali and alkaline earth salts can lead to unstable
signals at low levels and signal attenuation at high levels.
8.11 Nitric Acid (2.5 M)—Add 156 mL of concentrated
The Tc is chemically separated from the salts using anion
HNO to800mLofwater,dilutetoafinalvolumeof1000mL,
exchange chromatography.
and mix.
8.12 Nitric Acid (3.0 M)—Add 188 mL of concentrated
7. Apparatus
HNO to700mLofwater,dilutetoafinalvolumeof1000mL,
7.1 Inductively Coupled Plasma-Mass Spectrometer,
and mix.
computer-controlled, multichannel peristaltic pump, and an
8.13 Standard Metals Stock Solution—Prepare or purchase
auto-sampler.
solutions of beryllium, cobalt, indium, lead, and uranium, or
7.2 Centrifuge Tube With Cap, 15-mL, disposable, gradu-
equivalent combination of elements to cover the mass range, to
ated, that will accommodate the auto-sampler for sample
be used as a tuning solution, detector and mass calibration
analysis.
standard, and stability check solution.
7.3 Erlenmeyer Flasks and Distillation Columns, appropri-
99 99
8.14 Tc Spike Solution—Prepare a Tc spike solution
ately sized.
containing approximately 8000 ng/L of Tc from a certified
7.4 Plastic Cups, disposable, appropriately sized.
traceable NIST or equivalent certified standard.
7.5 Polyethylene Ion Exchange Column 12-mL,disposable,
or suitable size with a 30-µm porosity frit.
9. Hazards
7.6 Polyethylene Ion Exchange Column Funnels.
9.1 Since Tc is radioactive, adequate laboratory facilities
7.7 Centrifuge Cone, 50 mL, disposable, graduated.
along with safe handling techniques must be used. A detailed
8. Reagents and Materials discussion of all safety precautions needed is beyond the scope
of this test method. Follow site- and facility-specific radiation
8.1 Purity of Reagents—Reagent grade chemicals shall be
protection and chemical hygiene plans.
used in all tests. Unless otherwise indicated, it is intended that
all reagents conform to the specifications of the Committee on
10. Sampling, Test Specimens, and Test Units
Analytical Reagents of the American Chemical Society where
such specifications are available. Other grades may be used,
10.1 Urine samples are to be refrigerated at 4°C until
provided it is first ascertained that the reagent is of sufficiently
analysis. Preservatives may be used if deemed necessary to
high purity to permit its use without lessening the accuracy of
ensure stability.
the determination.
10.2 All chain of custody requirements described in
laboratory-specific operating procedures must be followed.
The VG Elemental PlasmaQuad PQ2+ ICP-MS was used to develop this test
method.
9 10
Reagent Chemicals, American Chemical Society Specifications, American AG MP-1 Macroporous Anion Exchange Resin available from Bio-Rad Co.,
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 300 Reggata Blvd., Richmond, CA94804, has been found to perform satisfactorily.
listed by the American Chemical Society, see Analar Standards for Laboratory The feasibility of comparable resins for use in this test method should be
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia demonstrated prior to utilization.
11 99
andNationalFormulary,U.S.PharmacopoeialConvention,Inc.(USPC),Rockville, The Tc standard solution is available from NIST, Building 245, Room C114,
MD. Gaithersburg, MD 20899.
C 1476
11. Calibration and Standardization ng/L Tc by diluting the calibration stock solution (see 8.14).
The calibration standards should be prepared in 2.5 M HNO
11.1 Follow the instrument manufacturer’s operating
(see 8.11) to match the final acid concentration of the prepared
manual and laboratory-specific operating procedures for initial
samples.
start-up and optimization of the ICP-MS and the associated
11.9.3 Calibration Blank—The calibration blank should be
computer control system and peripheral equipment.
prepared at the same acid concentration as the calibration
11.2 Set up the necessary instrument software files for data
standards, 2.5 M HNO (see 8.11).
acquisition, calculation, quality assurance (QA) and quality
11.9.4 Instrument Check Standard—Prepare in accordance
control (QC) data requirements, archival data storage, analyti-
with 11.9.2. Analyze at minimum a low- and high-level
cal report preparation, and report verification.
standard throughout the analytical run at a minimum frequency
11.3 The instrument, data acquisition, and reporting param-
of 10 %
eters shall be determined to meet customer statement of work
11.9.5 Artificial Urine —Prepare an artificial urine solu-
requirements.
tion in accordance with the following instructions. Mix 16.0
11.4 Instrument tuning, detector and mass calibration, and
parts urea, 2.32 parts NaCl, 3.43 parts KCl, 1.10 parts
stability check functions for the ICP-MS will require a tuning
creatinine, 4.31 parts Na SO (anhydrous), 0.63 part hippuric
2 4
solutionthatfollowstheinstrumentmanufacturer’srecommen-
acid, 1.06 parts NH Cl, 0.54 part citric acid, 0.46 part MgSO
dations. Introduce the daily tuning solution and tune the 4 4
(anhydrous), 2.73 parts NaH PO ·H O, 0.63 part CaCl ·2H O,
2 4 2 2 2
instrument for optimum response on the selected peaks.
0.02 part oxalic acid, 0.094 part lactic acid, 0.48 part glucose
11.4.1 Astock tuning solution can be prepared by adding an
(or dextrose), 0.071 part Na SiO ·9H O, 0.029 part pepsin, 5.0
2 3 2
aliquot of the standard metal stock solution (see 8.13) or
parts concentrated HNO , and 961 parts water. Mix dry
solution as specified by the ICP-MS instrument manufacturer 3
chemicals thoroughly before adding liquids. Stir the mixture
to water and 2 parts volume concentrated HNO per 100 parts
thoroughly for approximately 2 h using a magnetic stirrer.
water.
11.9.6 Method Reagent Blank—Analiquotofartificialurine
11.4.2 The daily tuning, mass calibration, detector calibra-
that is carried through each step of the procedure. The method
tion, and stability check solutions should be prepared by
reagent blank is used to determine if method analytes or other
diluting an aliquot of the stock tuning solution (see 11.4.1) and
interferences are present in the laboratory environment, the
2 parts volume concentrated HNO per 100 parts water. These
reagents, or the apparatus.The method reagent blank is used to
solutions should be prepared at analyte concentrations sug-
determine the test method MDC.
gested by the instrument manufacturer.
11.9.7 Laboratory Control Sample (LCS)—Prepare the con-
11.5 Check the mass calibration and resolution with the
trol by adding an appropriate aliquot of the calibration stock
daily tuning solution and elements recommended in accor-
solution (see 8.14) to an aliquot of artificial urine to give a Tc
dance with the manufacturer’s instrument specifications.
concentration within the calibration range. The LCS is carried
11.6 Make necessary adjustments in the instrument controls
through each step of the procedure. The LCS result is used to
to ensure that all of the preceding operating parameters (mass
determine if the test method performance is within acceptable
calibration, mass resolution, and baseline) are within previ-
control limits.
ously established laboratory limits. Use the appropriate con-
11.9.8 Internal Reference Standard—The recommended
centrations (see 11.4.2) for each of the calibration functions
concentration for the working ln internal reference solution is
suggested by the instrument manufacturer.
20 000 ng/L. The recommended concentration of ln within
11.7 Determine the instrument stability before analyzing
each calibration standard and sample is 200 ng/L. To prepare
any samples.The stability is determined by analyzing the daily
the working solution, add the required volume of ln standard
tuning solution (see 11.4.2) at least 10 times with a relative
solution to approximately 100 mL of water containing 2 parts
standard deviation of less than 5 % on the selected peaks.
concentrated HNO .
11.8 If the relative standard deviation for these isotopes
during instrument stability testing was greater than 5 %,
12. Procedure
determine the cause of the instability, correct the problem, and
12.1 Sample Preparation:
rerun the stability check.
99 12.1.1 Transfer 30 mL of the urine sample into an Erlenm-
11.9 Prior to the ICP-MS analysis for Tc, the following
eyer flask, and add 2 mL of H O . Add an additional 1 mL if
2 2
QC standards, calibration standards, internal standard, and
the sample appears dark. Attach a distillation column to the
rinse solution are recommended and should be included in the
flask.
analytical run:
12.1.2 Transfer 30 mL of the same urine sample into an
11.9.1 Rinse Solution—Add 2 parts volume concentrate
...
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