1、Designation: C 1647 06Standard Practice forRemoval of Uranium or Plutonium, or both, for ImpurityAssay in Uranium or Plutonium Materials1This standard is issued under the fixed designation C 1647; the number immediately following the designation indicates the year oforiginal adoption or, in the case
2、 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 practice covers instructions for using an extractionchromatography column method for t
3、he removal of plutoniumor uranium, or both, from liquid or digested oxides or metalsprior to impurity measurements. Quantification of impuritiescan be made by techniques such as inductively coupled plasmamass spectrometry (ICP-MS), inductively coupled plasmaatomic emission spectrometry (ICP-AES) or
4、atomic absorptionspectrometry (AAS.)1.2 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 determine the applica-bility of regulatory limi
5、tations prior to use.2. Referenced Documents2.1 ASTM Standards:2C 753 Specification for Nuclear-Grade, Sinterable UraniumDioxide PowderC 757 Specification for Nuclear-Grade Plutonium DioxidePowder, SinterableC 776 Specification for Sintered Uranium Dioxide PelletsC 787 Specification for Uranium Hexa
6、fluoride for Enrich-mentC 788 Specification for Nuclear-Grade Uranyl Nitrate So-lution or CrystalsC 996 Specification for Uranium Hexafluoride Enriched toLess Than 5 %235UC 1168 Practice for Preparation and Dissolution of Pluto-nium Materials for AnalysisC 1287 Test Method for Determination of Impur
7、ities inNuclear Grade Uranium Compounds by InductivelyCoupled Plasma Mass SpectrometryC 1347 Practice for Preparation and Dissolution of UraniumMaterials for AnalysisC 1432 Test Method for Determination of Impurities inPlutonium: Acid Dissolution, Ion Exchange Matrix Sepa-ration, and Inductively Cou
8、pled Plasma-Atomic EmissionSpectroscopic (ICP/AES) AnalysisC 1517 Test Method for Determination of Metallic Impuri-ties in Uranium Metal or Compounds by DC-Arc EmissionSpectroscopyD 1193 Specification for Reagent Water3. Summary of Practice3.1 An aliquot of liquid sample or dissolved solid sample is
9、adjusted as needed to 8M nitric acid for plutonium/uraniumremoval using extraction chromatography. Uranium and pluto-nium are retained on the resin and trace impurities are collectedin the column effluent. The impurities can be measured by avariety of techniques.4. Significance and Use4.1 This pract
10、ice can be used to separate uranium orplutonium, or both, prior to the impurity analysis by varioustechniques. The removal of uranium and plutonium prior toquantification can improve the detection limits by minimizingthe signal suppression caused by uranium or plutonium whenusing ICP techniques. Det
11、ection limits of 110 part-per-billion (PPB) may be obtainable by matrix removal. Also,removal of the uranium and plutonium may allow the impuri-ties analysis to be performed on a non-glove box enclosedinstrument.4.2 Other test methods exist to determine impurities inuranium or plutonium. Test Method
12、 C 1517 is able to deter-mine many impurities in uranium at detection levels of 110part-per-million (ppm) by DC-Arc Spectrometry. Test MethodC 1287 is able to determine impurities in uranium at detectionlevels of 100 ppb by ICP-MS. Test Method C 1432 provides1This practice is under the jurisdiction
13、of ASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved July 1, 2006. Published August 2006.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org.
14、For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.an alternative technique to remove plutonium by ion exchangeprior to
15、 analysis of the impurities by ICP-AES.4.3 This practice can be used to demonstrate compliancewith nuclear fuel specifications, for example, SpecificationsC 753, C 757, C 776, C 787, C 788, and C 996.5. Interferences5.1 Zirconium, hafnium, niobium, and tantalum are retainedon the diamyl, amylphospho
16、nate resin unless hydrofluoric acidis added to the nitric acid load/rinse solution. The addition ofhydrofluoric acid to recover zirconium, hafnium, niobium, andtantalum reduces uranium and plutonium retention. For thisreason, hydrofluoric acid levels must be minimized (typically13 mL capacity (inner
17、 diameter = 1.5cm has been found acceptable) and reservoirs.6.2 Plastic Collection Tubes,50mL.6.3 Column Rack, used for gravity flow systems.6.4 Polyethylene Frits for columns, 20 m.6.5 Vacuum BoxThe use of a vacuum-assisted flow sys-tem permits the use of higher eluent flow rates. Gravity flowsyste
18、ms may be used instead.7. Reagents7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Societywhere such specification
19、s are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination. High purity acids may be usedto reduce reagent blanks and to achieve lower detection limits.7.2 Purity of Wa
20、terUnless otherwise indicated, referencesto water shall be understood to mean reagent water as definedin Specification D 1193 as Type I.7.3 Hydrofluoric Acid (28 M)Concentrated hydrofluoricacid (sp gr 1.2).7.4 Nitric Acid (16 M)Concentrated HNO3(sp gr 1.42).7.5 Nitric Acid Solution (8 M)Add 500 mL o
21、f concen-trated nitric acid (sp gr 1.42) to 300 mL of water and dilute to1 L with water.7.6 Nitric Acid (8M)Hydrofluoric Acid (0.05M)Add500 mL concentrated nitric acid and 1.8 mL concentratedhydrofluoric acid to 250 mL water and dilute to 1 liter withwater.7.7 Diamyl, Amylphosphonate Resin,450100 m
22、particlesize resin for use with vacuum-assisted flow systems; 100 to150 m or larger if using gravity flow systems.7.8 Polymethacrylate Resin,5100150 m particle sizeresin.8. Hazards8.1 Refer to the laboratorys chemical hygiene plan andother applicable guidance for handling chemical and radioac-tive m
23、aterials and for the management of radioactive, mixed,and hazardous waste.8.2 Hydrofluoric acid is a highly corrosive acid that canseverely burn skin, eyes, and mucous membranes. Hydrofluo-ric acid is similar to other acids in that the initial extent of aburn depends on the concentration, the temper
24、ature and theduration of contact with the acid. Hydrofluoric acid differsfrom other acids because the fluoride ion readily penetrates theskin causing destruction of deep tissue layers. Unlike otheracids that are rapidly neutralized, hydrofluoric acid reactionswith tissue may continue for days if lef
25、t untreated. Due to theserious consequences of hydrofluoric acid burns, prevention ofexposure or injury of personnel is the primary goal. Utilizationof appropriate laboratory controls (hoods) and wearing ad-equate personal protective equipment to protect from skin andeye contact is essential.9. Proc
26、edure9.1 Column Preparation and Conditioning:NOTE 1If prepackaged columns are available from the resin supplier,skip to 9.1.3.NOTE 2Each column shall contain 10 mL diamyl, amylphosphonateresin. This resin amount can remove approximately 250 mg combinedplutonium/uranium to enable impurity assay by IC
27、P-AES, ICP-MS, orAAS.9.1.1 Add approximately 3 mL of polymethacrylate resin tothe bottom of a column. Rinse the column walls with water.Place a frit on top of the resin.9.1.2 Add approximately 10 mL of diamyl, amylphospho-nate resin to the column. Rinse the column walls with waterand place another f
28、rit on top of the resin.9.1.3 Place the columns on a vacuum box if using avacuum-assisted flow system or in a column rack if using agravity flow system.NOTE 3If not using a vacuum box, the larger particle size resin shouldbe used.3Reagent Chemicals, American Chemical Society Specifications, American
29、Chemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH, Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC)
30、, Rockville,MD.4The sole source of supply of the UTEVA resin known to the committee at thistime is Eichrom Technologies, Inc. 8205 S. Cass Ave Suite 106 Darien, IL 60561.If you are aware of alternative suppliers, please provide this information to ASTMInternational Headquarters. Your comments will r
31、eceive careful consideration at ameeting of the responsible technical committee,1which you may attend. This resinin described in Horwitz, E. P., et al, “Separation and Preconcentration of Uraniumfrom Acidic Media by Extraction Chromatography,” Analytica Chimica Acta, 266,1992, pp. 25-37.5The sole so
32、urce of supply of the prefilter material known to the committee atthis time is Eichrom Technologies, Inc. 8205 S. Cass Ave Suite 106 Darien, IL60561. If you are aware of alternative suppliers, please provide this information toASTM International Headquarters. Your comments will receive careful consi
33、der-ation at a meeting of the responsible technical committee,1which you may attend.C16470629.1.4 Add 10 mL 8M nitric acid to each column to conditionthe resin. Turn on vacuum and adjust flow rate to 24 mL/minif using a vacuum-assisted flow system. Allow each column todrain completely and turn off t
34、he vacuum if using the vacuumassisted flow system.9.1.5 Discard the eluted conditioning solutions.9.2 Column Loading and Separation:9.2.1 Procedures for dissolution of plutonium and uraniummaterials are found in Practices C 1168 and C 1347.9.2.2 Adjust the solution resulting from dissolution so that
35、the nitric acid concentration is 8M.9.2.3 Record the sample aliquot weight (g) or volume (mL)and sample pre-dilution factor (weight/volume or volume/volume).9.2.4 Place clean, labeled 50 mL plastic collection tubesbelow each column in the vacuum extraction system.9.2.5 Pipet 10 mL of sample aliquot
36、prepared in 9.2.2 intothe appropriate column. (the resin capacity is 250 mg U and Pucombined. If the concentration of the sample is greater than 25mg/mL, then less than 10 mL should be added to avoidexceeding the resin capacity).9.2.6 Turn on vacuum and adjust flow rate to 24 mL/min ifusing a vacuum
37、-assisted flow system. Allow each column todrain completely.9.2.7 Pipet 10 mL 8M nitric acid to each column and allowto drain completely.9.2.8 Repeat step 9.2.7.NOTE 4This second column elution step may be performed withhydrofluoric added (20 mL 8M HNO3 0.05M HF) to completely elutezirconium, hafniu
38、m, tantalum and niobium (see 5.1). This is done in asecond elution rinse to minimize hydrofluoric acid in the initial columnelution so that silicon background at the ICP-AES is minimized andsilicon can be measured in the first elution. A small amount of zirconium,hafnium, tantalum and niobium may be
39、 in the first elution so results fromboth elutions must be added to get a final result. If silicon is not of interest,this step can be avoided by making the 8M nitric acid load solutionapproximately 0.05M hydrofluoric acid.9.2.9 After columns have drained completely, increase thevacuum to remove res
40、idual liquid from columns, if using thevacuum-assisted flow system.9.2.10 Turn off vacuum if using the vacuum-assisted flowsystem and remove collection tubes from vacuum system.Adjust collection tube volume to 30 mL with 8M nitric acid, ifneeded.9.2.11 Submit collected fractions for analysis by the
41、se-lected technique such as ICP-MS, ICP-AES, or AAS.9.3 While not strictly within the scope of this practice,plutonium or uranium, or both, retained on the column may beeluted at this point, if desirable for the purposes of thelaboratory performing this analysis. Guidance for accomplish-ing this may
42、 be found in Horwitz, et al.410. Calculations10.1 Calculate the Metal Impurity, I:I 5 S B! 3 D (1)where:S = metallic impurity measured in final solution, g/mL,B = blank measurement for metallic impurity in final solu-tion, g/mL, andD = sample dilution factor.D 5SV 3 PSA(2)where:SV = column removal v
43、olume, mL (typically 30 mL, step9.2.10),SA = sample aliquot used in column separation, mL (typi-cally 10 mL, step 9.2.5), andP = pre-dilution factor (step 9.2.3).11. Keywords11.1 AAS; extraction chromatography; ICP-AES; ICP-MS;impurities; plutonium; resin; separation; uraniumASTM International takes
44、 no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own resp
45、onsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addresse
46、d to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the
47、address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).C1647063
