1、Designation: C 1379 04Standard Test Method forAnalysis of Urine for Uranium-235 and Uranium-238Isotopes by Inductively Coupled Plasma-MassSpectrometry1This standard is issued under the fixed designation C 1379; the number immediately following the designation indicates the year oforiginal adoption o
2、r, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of the con-centration of uranium-23
3、5 and uranium-238 in urine usingInductively Coupled Plasma-Mass Spectrometry. This testmethod can be used to support uranium facility bioassayprograms.1.2 This method detection limits for235U and238U are 6ng/L. To meet the requirements of ANSI N13.30, the minimumdetectable activity (MDA) of each rad
4、ionuclide measured mustbe at least 0.1 pCi/L (0.0037 Bq/L). The MDA translates to 47ng/L for235U and 300 ng/L for238U. Uranium 234 cannot bedetermined at the MDA with this test method because of its lowmass concentration level equivalent to 0.1 pCi/L.1.3 The digestion and anion separation of urine m
5、ay not benecessary when uranium concentrations of more than 100 ng/Lare present.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and det
6、ermine the applica-bility of regulatory limitations prior to use.NOTE 1Warning: The ICP-MS is a source of intense ultravioletradiation from the radio frequency induced plasma. Protection from radiofrequency radiation and UV radiation is provided by the instrument undernormal operation.2. Referenced
7、Documents2.1 ASTM Standards:2C 1310 Test Method for Determining Radionuclides inSoils by Inductively Coupled Plasma-Mass SpectrometryUsing Flow Injection PreconcentrationC 1345 Test Method for Analysis of Total and IsotopicUranium and Total Thorium in Soils by InductivelyCoupled Plasma-Mass Spectrom
8、etryD 1193 Specification for Reagent Water2.2 Other Documents:ANSI N13.30 Radiological Measurement QualityDOE Order 5480.11 Radiological Measurements Quality3. Terminology3.1 Definitions:3.1.1 isobar, nany atom that has the same atomic massnumber as another atom but a different atomic number.3.2 Acr
9、onyms:Acronyms:3.2.1 AMU, natomic mass unit3.2.2 CB, ncalibration blank3.2.3 COC, nchain of custody3.2.4 CVS, ncalibration verification standard3.2.5 ICS, ninstrument check standard3.2.6 IDL, ninstrument detection limit3.2.7 LCS, nlaboratory control sample3.2.8 MDA, nminimum detectable activity3.2.9
10、 m/e, nmass/charge ratio3.2.10 RMDA, nrequired minimum detectable activity3.2.11 % RDS, npercent relative standard deviation(1Standard Deviation / Mean) * 1004. Summary of Test Method4.1 A urine sample is digested and wet oxidized withconcentrated nitric and hydrochloric acids to solubilize ura-nium
11、 and to destroy the organic matter. Uranium is selectivelyseparated from the chloride salts by an anion exchange resinand is eluted with dilute nitric acid. The235U and238U isotopesare determined by ICP-MS.5. Significance and Use5.1 DOE Order 5480.11 and ANSI N13.30 require thatinternal dose assessm
12、ents be made as part of the bioassayprogram for nuclear facility workers. For indirect bioassay ofuranium workers, the uranium isotopes must be measured1This test method is under the jurisdiction of ASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee D26.05 on Me
13、thods ofTest.Current edition approved Jan. 1, 2004. Published February 2004. Originallyapproved in 1997. Last previous edition approved in 1997 as C137997.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTM
14、Standardsvolume information, refer to the standards Document Summary page onthe ASTM website1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.along with the total uranium in urine samples. The RMDA foreach uranium isotope is 0.1 pCi/L.
15、5.2 This method is applicable for measuring235U and238Uat the RMDA. Because of extremely low mass concentration(because of the high specific activity),234U cannot be measuredwithout additional sample preconcentration.NOTE 2Column chromatography separations and concentration of234U using manual or fl
16、ow-injection preconcentration followed byICP-MS isotopic determination are described in Test Methods C 1310 andC 1345. These methods focus on environmental soil sample analysis, butwith some development, may be applicable to digested urine samples. The234U concentration can be calculated based on an
17、 enrichment gradient forworkers in uranium enrichment plants, and internal dose assessments canbe made.NOTE 3Use of high resolution ICP-MS may also be used to obtainlower detection limits, see 1.6. Interferences6.1 No known isobaric elemental interferences occur fordetermining235U and238U using this
18、 test method.NOTE 4Bismuth, such as found in antacids (for example, PeptoBismol) may interferes with the analysis by using binding sites on theresin or biasing the internal standard measurement on the ICP-MSanalysis.7. Apparatus7.1 Inductively Coupled Plasma-Mass Spectrometer,computer-controlled, mu
19、lti-channel peristaltic pump, and anautosampler (2, 3, 4).7.2 Appropriate sized disposable graduated test tube withcap that will accommodate the autosampler.7.3 Twelve-mL disposable polyethylene column or suitablesize with frit.7.4 Vacuum manifold chamber with regulator valve,vacuum gage, vacuum rel
20、ief valve, and a vacuum manifoldbeaker rack (optional).8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee onAnalytical Reagents of the American Ch
21、emical Society wheresuch specifications are available.3Other grades of reagentsmay be used, provided it is first ascertained that the reagent isof sufficiently high purity to permit its use without lesseningthe accuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, referencesto
22、 water shall be understood to mean reagent water, as ASTM,Type I water as defined in Specification D 1193.8.3 Nitric Acid (sp gr 1.42)concentrated nitric acid(HNO3).8.4 Hydrochloric Acid (sp gr 1.18)concentrated hydro-chloric acid (HCl).8.5 Nitric Acid (8M)Add 500 mL of concentrated HNO3to 500 mL of
23、 water, and mix.8.6 Nitric Acid (0.8 M)Add 50 mL of concentrated HNO3to 950 mL of water, and mix.8.7 Nitric Acid (0.01 M)Add 1.25 mL of 8M HNO3to950 mL of water, and dilute to a final volume of 1000 mL, andmix.8.8 Hydrochloric Acid (6 M)Add 500 mL of concentratedHCl to 500 mL of water, and mix.8.9 A
24、rgon Gaspurity 99.99 % or better recommended.8.10 Standard Metals Stock Solutions Prepare or purchasecertified traceable stock or equivalent certified solutions ofberyllium, bismuth, cobalt, indium, lanthanum, lead, magne-sium, and uranium to be used for the tuning solution, calibra-tion, spiking, m
25、ass calibration, and internal standard, or asrecommended by the manufacturer8.11 Isotopic Stock SolutionPrepare two uranium isotopicstock solutions each containing 100,000 ng/L of total uraniumpurchased from a nationally recognized standards body such asNBL, NBL CRM U030A (3 %235U) and NBL CRM U150(
26、15 %235U) uranium reference materials, or equivalent, arerecommended.8.12 Calibration Stock SolutionPrepare a uranium cali-bration stock solution containing 100,000 ng/L of total uraniumcontaining 50%235U, such as NBL CRM U500 (50 %235U).8.13 The mass calibration and stability check of ICP-MSwill re
27、quire the preparation of a tuning solution that follows theinstrument manufacturers recommended operating conditions.8.13.1 The tuning stock solution can be prepared by addingan aliquot each of stock standard solutions of the elementsrecommended by the ICP-MS instrument manufacturer towater and 5 pa
28、rts volume concentrated HNO3per 100 partswater to the recommended concentration.8.13.2 The daily tuning solution should be prepared bydiluting an aliquot of the tuning stock solution (see 8.13.1) and1 part volume concentrate HNO3per 100 parts water. The dailytuning solution concentration for each an
29、alyte should be theinstrument manufacturers suggested operating concentration.8.14 Prior to the ICP-MS analysis for total uranium andisotopic concentration, the following QC standards, calibrationstandards, internal standard, and rinse solution are recom-mended and should be included in the analytic
30、al run (seeAppendix X1 for a suggested QC protocol for this practice).8.14.1 Rinse SolutionAdd 1 part concentrated HNO3to100 parts water. Prepare a sufficient quantity to flush theICP-MS and autosampler between calibration standards, QCsamples, and samples.8.14.2 Uranium Calibration StandardsA minim
31、um offour calibration standards should be prepared containing 50ng/L, 500 ng/L, 1000 ng/L, and 2000 ng/L total uranium bydiluting the uranium calibration stock solution (see 8.12).These calibration standards shall be prepared in 1 part volumeconcentrated HNO3per 100 parts water and contain 50 %235Ua
32、nd238U isotopic content.8.14.3 Instrument Check Standard (ICS)The ICS shouldbe prepared by diluting a NBL CRM U150 uranium stock3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, D. C. For suggestions on the testing of reagents notlisted by the Americ
33、an Chemical Society, Washington, D. C. For suggestions on thetesting of reagents not listed by the American Chemical Society, see AnalarStandards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U. K., and theUnited States Pharmacopeia and National Formulary, U.S. Pharmaceutical Con-vention (USPC)
34、, Rockville, MD.C 1379 042solution (see 8.11) to a total uranium concentration of 100 ng/L(15 ng/L235U and 85 ng/L238U). Prepare this solution in 1 partvolume concentrated HNO3per 100 parts water.8.14.4 Calibration Verification Standard (CVS)The CVSshould be prepared by diluting the NBL CRM U030 ura
35、niumstock solution (see 8.11). The CVS is used for initial andcontinuing calibration verification. Prepare the CVS at aconcentration of 400 ng/L total uranium (12 ng/L235U and 388ng/L238U). Prepare the verification standard in 1 part volumeconcentrated HNO3per 100 parts water.NOTE 5Improved precisio
36、n of the diluted standards prepared in8.14.2-8.14.4 may be obtained by preparing an intermediate dilution (;20times) of the stock solutions in 8.11 and 8.12. Gravimetric preparation ofthese dilutions is recommended.8.14.5 Calibration BlankPrepare the calibration blank in1 part volume concentrated HN
37、O3per 100 parts water.8.14.6 Internal Control SampleAn aliquot of an internalurine control of known concentration to the analyst should beobtained from a second additional laboratory source. Thelaboratory control sample is treated exactly as a sampleincluding exposure to all labware, equipment, and
38、reagents.The internal control sample is used to check laboratoryanalytical performance against established limits.8.14.7 Laboratory Control Sample (LCS)Prepare thiscontrol by adding an aliquot of the uranium isotopic standards(see 8.11) to water to yield an isotopic concentration within thecalibrati
39、on range. The LCS is treated exactly as a sample,including exposure to all labware, equipment, and reagents.The LCS is used to determine whether method performance iswithin accepted control limits.8.14.8 Laboratory Reagent Blank (preparation blank)Analiquot of water that is treated exactly as a samp
40、le, includingexposure to all labware, equipment, and reagents that are usedwith other samples. The laboratory reagent blank is used todetermine if method analytes or other interferences are presentin the laboratory environment, the reagents, or apparatus.8.14.9 The recommended concentration for the
41、bismuthinternal standard solution is 20,000 ng/Bi/L. The bismuthinternal standard stock solution should be prepared by addingthe required volume of the bismuth standard stock solution (see8.10) to approximately 100 mL of water. Add 2 parts concen-trated HNO3per 100 parts water, and dilute solution w
42、ith waterfor the final volume.8.15 Anion exchange resin, 50100 or 100200 mesh (chlo-ride form).49. Sampling, Test Specimens, and Test Units9.1 Urine samples are to be refrigerated at 4C untilanalysis. Preservatives may be used if deemed necessary toensure stability (1).9.2 All chain of custody requi
43、rements described inlaboratory-specific operating procedures must be followed.10. Calibration and Standardization10.1 Follow the instrument manufacturers operatingmanual and laboratory-specific operating procedures for initialstart-up and optimization of the ICP-MS and the associatedcomputer control
44、 system and peripheral equipment.10.2 Set up the necessary instrument software files for dataacquisition, calculation, QA and QC data requirements, archi-val data storage, analytical report preparation, and reportverification, etc.10.3 The instrument, data acquisition, and reporting param-eters shal
45、l be determined to meet customer statement of workrequirements.10.4 Introduce the daily tuning solution (see 8.13.2) and setthe mass controls to transmit the first mass m/e 209(Bi) andm/e 238(U), and tune the instrument for optimized response.10.5 Check the mass calibration and resolution with theda
46、ily tuning solution and elements recommended per manu-facturers instrument specifications.10.6 Make necessary adjustments in the instrument controlsto ensure that all of the above operating parameters (masscalibration, mass resolution, resolution, and baseline) arewithin previously established labor
47、atory limits.10.7 Determine the instrument stability before analyzingany samples. The stability is determined by analyzing thetuning solution at least ten times with a relative standarddeviation of less then 5 % for209Bi and238U isotopes.10.8 If the relative standard deviation for these isotopesduri
48、ng instrument stability testing was greater than 5 %,determine the cause of the instability and correct the problemand rerun the stability check.11. Procedure11.1 Glassware Preparation:11.1.1 Add 5 mL of 8M HNO3and 6M HCl to each beaker,cover each beaker with a watch glass, and place the beakers ona
49、 hot plate.11.1.2 Heat the beakers to boiling for approximately 5 to 10minutes, then remove the beakers and allow to cool to roomtemperature.11.1.3 Rinse the beakers and watch glasses with water andair dry.11.2 Sample Preparation:11.2.1 Transfer 20 mL of the urine sample into a beaker.11.2.2 Add 5 mL of concentrated HNO3to the beaker andcover the beaker with a watch glass, and digest on a hot plateat 95C.11.2.3 Remove the watchglass after 15 to 20 minutes andallow the samples to evaporate to dryness, but do not allowoverheating to the po
