1、Designation: C 1111 04Standard Test Method forDetermining Elements in Waste Streams by InductivelyCoupled Plasma-Atomic Emission Spectroscopy1This standard is issued under the fixed designation C 1111; the number immediately following the designation indicates the year oforiginal adoption or, in the
2、 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 trace,minor, and major elements in waste
3、streams by inductivelycoupled plasma-atomic emission spectroscopy (ICP-AES) fol-lowing an acid digestion of the sample. Waste streams frommanufacturing processes of nuclear and non-nuclear materialscan be analyzed. This test method is applicable to the deter-mination of total metals. Results from th
4、is test method can beused to characterize waste received by treatment facilities andto formulate appropriate treatment recipes. The results are alsousable in process control within waste treatment facilities.1.2 This test method is applicable only to waste streams thatcontain radioactivity levels th
5、at do not require special person-nel or environmental protection.1.3 A list of the elements determined in waste streams andthe corresponding lower reporting limit is found in Table 1.1.4 This test method has been used successfully for treat-ment of a large variety of waste solutions and industrial p
6、rocessliquids. The composition of such samples is highly variable,both between waste stream types and within a single wastestream. As a result of this variability, a single acid digestionscheme may not be expected to succeed with all samplematrices. Certain elements may be recovered on a semi-quanti
7、tative basis, while most results will be highly quantita-tive.1.5 This standard does not purport to address all of thesafety problems, 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
8、-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2C 1109 Test Method for Analysis of Aqueous Leachatesfrom Nuclear Waste Materials Using Inductively CoupledPlasma-Atomic Emission SpectrometryC 1234 Practice for Preparation of Oils and Oily WasteSamples by High
9、-Pressure, High-Temperature Digestionfor Trace Element DeterminationsD 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterE 135 Terminology Relating to Analytical Chemistry forMetals, Ores, and Related MaterialsE 177 Practice for Use of the Terms Precision and Bias inASTM Test M
10、ethods2.2 US EPA Standard:Method 6010, Inductively Coupled Plasma Method, SW-846, Test Methods for Evaluating Solid Waste33. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology D 1129, Terminology E 135, andTest Method C 1109.4. Summary of Test Method4.1
11、Elements are determined, either sequentially or simul-taneously, by inductively coupled plasma-atomic emissionspectroscopy (Method 6010, SW-846). If the sample is a clearacidified solution, the elements are determined with no furtherpretreatment. If the sample contains undissolved solids, theelement
12、s are determined using an aliquot of the thoroughlymixed sample after a nitric acid digestion.5. Significance and Use5.1 This test method is useful for the determination ofconcentrations of metals in many waste streams from variousnuclear and non-nuclear manufacturing processes. The testmethod is us
13、eful for characterizing liquid wastes and liquidwastes containing undissolved solids prior to treatment, stor-age, or stabilization. It has the capability for the simultaneousdetermination of up to 26 elements.5.2 The applicable concentration ranges of the elementsanalyzed by this procedure are list
14、ed in Table 1.1This test method is under the jurisdiction of ASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved Jan. 1, 2004. Published February 2004. Originallyapproved in 1988. Last previous edition approved in
15、 1998 as C 1111982For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandardsvolume information, refer to the standards Document Summary page onthe ASTM website.3Available from the U.S. Government Printing
16、Office, Washington, DC 20402.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6. Interferences6.1 Interferences in ICP-AES are primarily spectral and canbe compensated for in the following ways:6.1.1 Interelement InterferencesInterele
17、ment interfer-ences are characterized by spectral overlap of one element lineover another. This interference can be compensated for bycorrection of the raw data, which requires measurement of theinterfering element at the wavelength of interest. Table 2 listssome interference effects for the recomme
18、nded wavelengthsgiven in Table 1. The data in Table 2 are intended for use onlyas a rudimentary guide for indicating potential spectral inter-ferences. Various analytical systems may exhibit somewhatdifferent levels of interferences. Therefore, the interferenceeffects must be evaluated for each indi
19、vidual system.6.1.2 Molecular Band InterferenceMolecular band inter-ference arising from overlap of molecular band spectra at thewavelength of interest can be eliminated by careful selection ofwavelength.6.1.3 High BackgroundHigh background effects fromscattered light, etc., can be compensated for b
20、y backgroundcorrection adjacent to the analyte line.6.2 Physical InterferencesPhysical interferences are ef-fects associated with nebulization and transport processes insamples with either high solids or acid concentrations. Theseeffects are reduced by a tenfold dilution of the sample and theuse of
21、a peristaltic pump in conjunction with a high-solidsnebulizer.7. Apparatus7.1 SpectrometerAn inductively coupled plasma emissionspectrometer with a spectral bandpass of 0.05 nm or less isrequired. The spectrometer may be of the simultaneous multi-element or sequential scanning type. The spectrometer
22、 may beof the air path, inert gas path, or vacuum type, with spectrallines selected appropriately for use with the specific instru-ment. Either an analog or digital readout system may be used.8. Reagents8.1 Purity of ReagentsChemicals used in the preparationof the standards must be of ultrahigh puri
23、ty grade. Chemicalsused in the preparation of the samples shall conform to thespecifications of the Committee on Analytical Reagents of theAmerican Chemical Society,4where such specifications areavailable.8.2 Purity of WaterReferences to water shall be under-stood to mean reagent water conforming to
24、 SpecificationD 1193, Type I.8.3 Stock SolutionsStandard stock solutions may be pur-chased or prepared from ultrahigh purity grade metals or metalsalts (Method 6010, SW-846). All salts must be dried for1hat105C unless otherwise specified. Stock solutions should4“Reagent Chemicals, American Chemical
25、Society Specifications,” Am. Chemi-cal 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.”TABLE 1 Analytical W
26、avelengths and Applicable ConcentrationRangesAElementLowerLimit,Bmg/LUpperLimit,mg/LWavelength, nmAluminum 0.02 5000 308.22, 237.01Barium 0.001 100 493.41Beryllium 0.0003 100 313.04Boron 0.004 200 249.68Cadmium 0.003 200 226.50Calcium 0.004 1000 317.93, 393.37Chromium 0.01 5000 267.72, 298.92Cobalt
27、0.005 150 228.62Copper 0.004 150 324.75Iron 0.004 5000 271.44, 259.94Lead 0.05 200 220.35Lithium 0.004 150 670.78Magnesium 0.0005 5000 293.65, 279.55Manganese 0.001 150 257.61Nickel 0.01 5000 231.60, 341.48Phosphorus 0.2 250 178.29Potassium 0.6 1000 766.49Silver 0.006 150 328.07Sodium 0.02 200 330.2
28、9, 588.99Strontium 0.0004 100 421.55Thorium 0.2 250 283.73Titanium 0.003 150 334.94Uranium 0.03 1000 409.01Vanadium 0.005 250 292.40Zinc 0.001 250 213.86Zirconium 0.005 250 339.20AThe estimated upper and lower concentration limits are to be used only as ageneral guide. These values are instrument an
29、d sample dependent, and as thesample matrix varies, these concentrations may be expected to vary also.BThese limits obtained using a Jarrell-Ash ICAP-9000 ICP Spectrometer.C1111042contain approximately 1 000 to 10 000 mg/L of the element ofinterest to ensure long term stability in dilute nitric acid
30、8.4 Multielement Working Calibration StandardsMultielement working calibration standards are prepared fromthe single element stock solutions at appropriate concentrationlevels for each element. Prior to preparing the mixed standards,each stock solution should be analyzed separately to determinepossi
31、ble spectral interference or the presence of impurities.Care should be taken when preparing each multielementcalibration standard solution that the elements be compatibleand stable. An appropriate amount of concentrated nitric acid isadded to stock standard aliquots and final volume brought to100 mL
32、 with distilled-deionized water to ensure that the finalnitric acid concentration is 10 volume %. Transfer eachmultielement calibration standard solution to a FEP fluorocar-bon or new polyethylene bottle for storage. Fresh calibrationstandards should be prepared as needed with the realizationthat co
33、ncentration can change with age. Calibration standardsmust be initially verified using a quality control samplemonitored weekly for stability. The actual number of calibra-tion standards needed will be a function of both chemicalcompatibility and the restrictions of the computer system usedto contro
34、l the spectrometer. Additional calibration standardsmay be needed if a second, less sensitive emission line is usedto extend the linear range of one or more elements. Althoughnot specifically required, some typical standard combinationsare given below when using the specific analytical wavelengthsli
35、sted in Table 1.8.4.1 Mixed Standard Solution IAluminum, barium, chro-mium, copper, iron, potassium, magnesium, manganese,nickel, and sodium.8.4.2 Mixed Standard Solution IIBeryllium, calcium,lithium, silver, strontium, thorium, titanium, vanadium, andzirconium.8.4.3 Mixed Standard Solution IIIBoron
36、, cadmium, co-balt, lead, phosphorus, and zinc.8.4.4 Single Element StandardA single element standardsolution is suggested for uranium due to the high probability ofspectral interference with other elements.8.5 Interference Check SampleThe interference checksample is prepared from single element sto
37、ck standard solu-tions to contain elements and concentrations appropriate to thesample type.8.6 Calibration BlankThe calibration blank is preparedby adding one volume of nitric acid (specific gravity 1.42) tonine volumes of distilled-deionized water. Prepare a sufficientquantity to be used for flush
38、ing the system between standardsand samples.8.7 Reagent BlankThe reagent blank must contain all ofthe reagents and in the same volumes as used in the processingof the samples. The reagent blank must be carried through thecomplete procedure and contain the same acid concentration inthe final solution
39、 as the sample solution used for analysis.8.8 Nitric Acid (sp gr 1.42)Concentrated nitric acid(HNO3).TABLE 2 Analyte Concentration Equivalents Arising from Interferents at the 1000 mg/L LevelAnalyteWave-lengths,nmInterferent, mg/LAluminum Chromium Copper Iron Nickel Antimony Silicon Tin Uranium Vana
40、diumAluminum 308.22 0.0020 0.0044 0.0199Aluminum 237.21 0.0022 0.0084 0.0350Barium 493.41Beryllium 313.04 0.0013Boron 249.68 0.0015Cadmium 226.50 0.0002 0.0004Calcium 317.93 0.0018Calcium 393.37 0.0002Chromium 267.72 0.0025 0.0018Chromium 298.92 0.0560Cobalt 228.62 0.0001 0.0001Copper 324.75Iron 259
41、.94 0.0001 0.0001 0.0002Iron 271.44 0.0039 0.0015 0.0220Lead 220.35 0.0012 0.0028 0.0002 0.0006 0.0016Lithium 670.78 0.0003Magnesium 279.55Magnesium 293.65 0.0270 0.1390 0.0350Manganese 257.61 0.0002Nickel 231.60 0.0002 0.0003 0.0001 0.0003Nickel 341.48 0.0027Phosphorus 178.29 0.0002 0.0079 0.0120 0
42、.0004 0.0044Potassium 766.49 0.0010 0.0005 0.0014Silver 328.07 0.0003Sodium 330.29 0.0035 0.0220 0.0145 0.1580Sodium 588.99 0.0006 0.0017 0.0002Strontium 421.55Thorium 283.73 0.0007 0.0005 0.0049 0.0500Titanium 334.94 0.0003Vanadium 292.40 0.0029 0.0014Zinc 213.85 0.0034 0.0001 0.0038Zirconium 339.2
43、0 0.0003 0.0002 0.0005C11110438.9 Nitric Acid, 10 volume %One volume of concentratednitric acid (specific gravity 1.42) brought to ten volumes withdistilled-deionized water.9. Calibration and Standardization9.1 After a warm-up time of at least 30 min, operate thespectrometer according to the operati
44、on manual for the instru-ment.9.2 Calibrate the instrument by aspirating the blank andstandards. A flush-out time of approximately 112 to 2 minshould be allowed between standards, during which a calibra-tion blank 10 volume % HNO3 is aspirated. The computerestablishes the slope, intercept, and corre
45、lation statistics foreach element. Suggested analytical wavelengths are listed inTable 1.9.3 To minimize physical interferences caused by changesin sample transport processes (due to variations in sampleviscosity and concentration), it may be necessary to use aperistaltic pump in conjunction with ce
46、rtain nebulizers.10. Sample Preparation10.1 Samples that are clear, without solids, and have a pH5 require no sample pretreatment.10.2 Samples that contain undissolved solids are treated asfollows:10.2.1 Pipette 10 mL of the well-mixed sample to 100 mLbeaker and add 10 mL of HNO3(sp gr 1.42).NOTE 1T
47、his test method is written for analysis of solutions contain-ing 10 % (v/v) nitric acid. This test method can be modified to accomodatethe use of another mineral acid at a different concentration. The user mustdetermine the operating parameters and precision and bias under themodified conditions.10.
48、2.2 Heat the sample on a hotplate until the volume hasbeen reduced to 2 mL.10.2.3 Quantitatively transfer the contents of the beaker to a100-mL volumetric flask while filtering undissolved solidsusing a 2.5 m pore size, acid washed cellulose filter paper orequivalent, add 10 mL of HNO3(sp gr 1.42),
49、and dilute tovolume with distilled-deionized water.10.3 Oils and oily waste samples can be prepared usingStandard Practice C 1234.11. Procedure11.1 Aspirate the samples, prepared in accordance withSection 10, into the calibrated ICP-AES using the same sampleconditions as used for the calibration procedure.11.2 Analyze instrument check standards (from one of theworking standards), blanks, and a digested internal controlsample at a 10 % frequency or better. The results on theinstrument check standards are to be within 610 %, and theinternal
