1、Designation: C 1109 04Standard Practice forAnalysis of Aqueous Leachates from Nuclear WasteMaterials Using Inductively Coupled Plasma-AtomicEmission Spectroscopy1This standard is issued under the fixed designation C 1109; the number immediately following the designation indicates the year oforiginal
2、 adoption or, 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 practice is applicable to the determination of lowconcentrati
3、on and trace elements in aqueous leachate solutionsproduced by the leaching of nuclear waste materials.1.2 The nuclear waste material may be a simulated (non-radioactive) solid waste form or an actual solid radioactivewaste material.1.3 The leachate may be deionized water or any natural orsimulated
4、leachate solution containing less than 1 % totaldissolved solids.1.4 The analysis must be conducted with an inductivelycoupled plasma-atomic emission spectrometer.1.5 The values stated in SI units are to be regarded as thestandard.1.6 This standard does not purport to address all of thesafety proble
5、ms, 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 limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2C 1009 Guide for Establishing a Quality A
6、ssurance Pro-gram for Analytical Chemistry Laboratories Within theNuclear IndustryC 1220 Test Method for Static Leaching of MonolithicWaste Forms for Disposal of Radioactive WastesD 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterE 135 Terminology Relating to Analytical Chemi
7、stry forMetals, Ores, and Related Materials3. Terminology3.1 Definitions:3.1.1 Inductively Coupled Plama Emisssion Spectroscopy(ICP-AES)refer to Terminology E 135.3.1.2 water refer to Terminology D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 analytical curvethe plot of net signal i
8、ntensityversus elemental concentration using data obtained duringcalibration.3.2.2 calibrationthe process by which the relationshipbetween net signal intensity and elemental concentration isdetermined for a specific element analysis.3.2.3 calibration blanka 1 % (v/v) solution of nitric acidin deioni
9、zed water.3.2.4 calibration reference solution(s)solutions contain-ing known concentrations of one or more elements in 1 % (v/v)nitric acid for instrument calibration.3.2.5 detection limits (DL)the concentration of the ana-lyte element equivalent to three times the standard deviation often replicate
10、 measurements of the matrix blank.3.2.6 instrument check solution(s)solution(s) containingall the elements to be determined at concentration levelsapproximating the concentrations in the specimens. Thesesolutions must also contain 1 % (v/v) nitric acid.3.2.7 linear dynamic rangethe elemental concent
11、rationrange over which the analytical curve remains linear to withinthe precision of the analytical method.3.2.8 linearity check solution(s)solution(s) containing theelements to be determined at concentrations that cover a rangethat is two to ten times higher and lower than the concentrationof these
12、 elements in the calibration reference solutions. Thesesolutions also contain 1 % (v/v) nitric acid.3.2.9 non-spectral interferencechanges in the apparentnet signal intensity from the analyte due to physical orchemical processes that affect the transport of the analyte to theplasma and its vaporizat
13、ion, atomization, or excitation in theplasma.3.2.10 off-peak background correctionduring specimenanalysis, measurements are made of the background intensitynear the peak wavelength of the analytical lines. Correction of1This practice is under the jurisdiction of ASTM Committee C26 on NuclearFuel Cyc
14、le and is the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved June 1, 2004. Published July 2004. Originally approvedin 1988. Last previous edition approved in 1998 as C 1109 98.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact AST
15、M Customer Service at serviceastm.org. 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.the analytical line peak inte
16、nsity to yield the net line intensitycan be made by subtraction of either (a) a single intensitymeasurement performed on the high or low wavelength side ofthe analytical line (single-point background correction), or ( b)an interpolated background intensity from background mea-surements acquired on b
17、oth the high and low wavelength sidesof the analytical line (double-point background correction).3.2.11 on-peak spectral interference correctionadjustments made in observed net intensity of peak of interestto compensate for error introduced by spectral interferences.3.2.12 sensitivitythe slope of th
18、e linear dynamic range.3.2.13 spectral interferencelight emission from spectralsources other than the analyte element that contributes to theapparent net signal intensity of the analyte. Sources of spectralinterference include spectral line overlaps, broadened wings ofintense spectral lines, ion-ato
19、m recombination continuumemission, molecular band emission, and stray (scattered) lighteffects.4. Summary of Practices4.1 The general principles of emission spectrometric analy-sis are given in Ref (1).3In this practice, elemental constituentsof aqueous leachate solutions are determined simultaneous
20、ly orsequentially by inductively coupled plasma-atomic emissionspectroscopy (ICP-AES).4.2 Specimens are prepared by filtration if needed to removeparticulates and acidification to match calibration referencesolutions. Filtration should be the last resort to clarify asolution since leach studies are
21、designed to determine theabsolute amount of glass dissolved.4.3 Additional general guidelines are provided in GuideC 1009, Terminology D 1129, Specification D 1193, and Ter-minology E 135.5. Significance and Use5.1 This practice may be used to determine concentrationsof elements leached from nuclear
22、 waste materials (glasses,ceramics, cements) using an aqueous leachant. If the nuclearwaste material is radioactive, a suitably contained and shieldedICP-AES spectrometer system with a filtered exit-gas systemmust be used, but no other changes in the practice are required.The leachant may be deioniz
23、ed water or any aqueous solutioncontaining less than 1 % total solids.5.2 This practice as written is for the analysis of solutionscontaining 1 % (v/v) nitric acid. It can be modified to specifythe use of the same or another mineral acid at the same orhigher concentration. In such cases, the only ch
24、ange needed inthis practice is to substitute the preferred acid and concentra-tion value whenever 1 % nitric acid appears here. It isimportant that the acid type and content of the reference andcheck solutions closely match the leachate solutions to beanalyzed.5.3 This practice can be used to analyz
25、e leachates fromstatic leach testing of waste forms using C 1220.6. Apparatus6.1 Inductively Coupled Plasma-Atomic Emission Spec-trometer, with a spectral bandpass of 0.05 nm or less, isrequired to provide the necessary spectral resolution. Thespectrometer may be of the simultaneous multielement ors
26、equential scanning type. The spectrometer may be of theair-path, inert gas-path, or vacuum type, with spectral linesselected appropriately for use with the specific instrument.Either an analog or digital readout system may be used.7. Reagents and Materials7.1 Purity of ReagentsReagent grade chemical
27、s 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 Chemical Society wheresuch specifications are available.4Other grades may be used,provided it is first ascertained that the re
28、agent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.7.2 Purity of Water Unless otherwise indicated, refer-ences to water shall be understood to mean reagent water asdefined by Type I of Specification D 1193 or water exceedingthese specifications.7
29、.3 Nitric Acid (specific gravity 1.42)Concentrated nitricacid (HNO3).7.4 Nitric Acid, High-PurityNitric acid of higher puritythan reagent grade, specially prepared to be low in metalliccontaminants. The acid may be prepared by sub-boiling distil-lation (2), or purchased from commercial sources.7.5 S
30、tock Solutions May be purchased or prepared frommetals or metal salts of known purity. Stock solutions shouldcontain known concentrations of the element of interest rang-ing from 100 to 10 000 mg/L.7.6 Calibration Reference Solutions, Instrument Check So-lutions, and Linearity Check Solutions:7.6.1
31、Prepare single-element or multielement calibrationreference solutions by combining appropriate volumes of thestock solutions in acid-rinsed volumetric flasks. To establishthe calibration slope accurately, provide at least one solutionwith element concentration that is a minimum of 100 times thedetec
32、tion limit for each element. Add sufficient nitric acid tobring the final solution to 1 % HNO3. Prior to preparing themultielement solutions, analyze each stock solution separatelyto check for strong spectral interference and the presence ofimpurities (3). Take care when preparing the multielementso
33、lutions to verify that the components are compatible andstable (they do not interact to cause precipitation) and that noneof the elements present exhibit mutual spectral interference.Transfer the calibration reference solutions to acid-leachedFEP TFE-fluorocarbon or polyethylene bottles for storage.
34、Calibration reference solutions must be verified initially usinga quality control sample and monitored periodically for stabil-ity.3The boldface numbers in parentheses refer to the list of references at the endof this standard.4“Reagent Chemicals, American Chemical Society Specifications,” Am. Chem-
35、ical Soc., Washington DC. For suggestions on the testing of reagents not listed bythe American Chemical Society, see “Reagent Chemicals and Standards,” by JosephRosin, D. Van Nostrand Co., Inc., New York, NY, and the “United StatesPharmacopeia.”C1109042NOTE 1Solutions in polyethylene bottles are sub
36、ject to transpirationlosses that may affect the assigned concentration values.7.6.2 Prepare the instrument check solution(s) and linearitycheck solutions in a similar manner.7.6.3 Fresh solutions should be prepared as needed with therealization that concentrations can change with age.8. Specimen Pre
37、paration8.1 Filter the leachate through a clean, inert membrane filterhaving pore size of 0.45 m or smaller, using an inert filtersupport (avoid the use of fritted glass supports). Examine thefiltered leachate to verify the absence of visible solids orsuspended colloids. Compare the analyses of filt
38、ered andunfiltered aliquots of the original leachate solution to determinewhether the filter membrane contributes to the blank level ofthe filtered solution. The deposit on the filter may be analyzedseparately if required.8.2 Add sufficient high-purity concentrated nitric acid tobring the leachate s
39、ample solution to volume1%HNO3.Iftheleachate is known to be a chloride solution, or nitric acid isundesirable for other experimental reasons, concentrated hy-drochloric or other mineral acid may be used instead. The acidconditions of the calibration and check solutions used in theanalytical procedur
40、e must match those of the leachate speci-men.9. Analytical Conditions9.1 Analytical Lines Suggested analytical lines for typicalelements are given in Table 1. Additional lines for these andother elements of interest, and information about possibleinterfering lines, can be found in compilations of an
41、alyticallines for ICP-AES (4-12).9.2 Selection of Analytical ConditionsSelect an optimumcombination of analytical lines, background correction meth-ods, plasma viewing position, and plasma/spectrometer oper-ating conditions to obtain the following for each element:9.2.1 The lowest attainable detecti
42、on limit,9.2.2 The acceptable linear dynamic range,9.2.3 Avoidance or minimization of spectral and non-spectral interference, and9.2.4 Best attainable precision.9.3 Follow the spectrometer manufacturers recommenda-tion wherever possible in establishing operating conditions.For simultaneous multielem
43、ent systems, the optimum plasmaviewing position and set of operating conditions is usually acompromise (13). The combination of conditions selected mustbe used in all subsequent ICP operations, including determi-nation of detection limits, calibrations, specimen analyses, andperformance checks. Syst
44、ematic use of an appropriate methodsuch as reference to an atom-to-ion emission intensity ratio (3)to ensure reproducible conditions is recommended.9.4 Determine the detection limit and the upper limit forlinear calibration for each element. Use these analytical limitsas a guide in the preparation o
45、f the calibration referencesolutions and linearity check solutions. Determine three sigmacontrol limits for each element through repetitive analysis ofthe instrument check solution(s). For a particular element,these control limits are the known elemental concentration plusand minus three standard de
46、viations. At least ten independentanalyses, distributed randomly with respect to time and labo-ratory operating conditions, are recommended for estimation ofthe standard deviations.10. Calibration10.1 Calibration of the Spectrometer System:10.1.1 Follow the spectrometer manufacturers instructionsfor
47、 forming and stabilizing the plasma. Allow sufficient timefor plasma stabilization before making measurements.10.1.2 Calibrate the spectrometer system using the calibra-tion blank and the appropriate calibration reference solutions,following the same procedure as for specimen analysis (seeSection 11
48、). Obtain separate intensity measurements at theanalytical line peak position while introducing the calibrationblank and the calibration reference solution. Subtract theanalytical line peak intensity determined during analysis of thecalibration blank from that of the calibration reference solutionan
49、alysis to determine the net intensity related to concentration.Then check the accuracy of the calibration by analyzing theTABLE 1 Suggested Analytical Wavelengths of Typical Elementsfor ICP-AESAElementSuggestedWavelength,nmEstimatedDetectionLimit, mg/LAlternativeWavelength,nmEstimatedDetectionLimit, mg/LAluminum 308.22 0.04 237.32 0.03Americium 283.23 0.01 292.06 0.01Arsenic 193.70 0.05 189.04 0.01BBarium 493.41 0.002 455.40 0.001Beryllium 234.86 0.0003 313.04 0.0003Boron 249.77 0.005 249.68 0.005Cadmium 214.44 0.002 . .Calcium 317.93 0.01 393.37 0.0002Cerium
