1、Designation: D 6052 97 (Reapproved 2003)Standard Test Method forPreparation and Elemental Analysis of Liquid HazardousWaste by Energy-Dispersive X-Ray Fluorescence1This standard is issued under the fixed designation D 6052; the number immediately following the designation indicates the year oforigin
2、al 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 test method covers the determination of trace andmajor elem
3、ent concentrations by energy-dispersive X-ray fluo-rescence spectrometry (EDXRF) in liquid hazardous waste(LHW).1.2 This test method has been used successfully on numer-ous samples of aqueous and organic-based LHW for thedetermination of the following elements: Ag, As, Ba, Br, Cd,Cl, Cr, Cu, Fe, Hg,
4、 I, K, Ni, P, Pb, S, Sb, Se, Sn, Tl, V, and Zn.1.3 This test method is applicable for other elements (Si-U)not listed in 1.2.1.4 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 app
5、ro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2C 982 Guide for Selecting Components for Energy-Dispersive X-ray Fluorescence (XRF) SystemsD 1193 Specification for Reagent Water2.2 Other ASTM Doc
6、uments:ASTM Data Series DS 46 X-ray Emission Wavelengths andKeV Tables for Nondiffractive Analysis33. Summary of Test Method3.1 A weighed portion of activated alumina and sample arecombined in a mixing vessel and shaken until well mixed. Thesample mixture is transferred into a disposable sample cup
7、andplaced in the spectrometer for analysis.3.2 The K spectral emission lines are used for elementsSi-Ba.3.3 The L spectral emission lines are used for elements withatomic numbers greater than Ba.4. Significance and Use4.1 The elemental analysis of liquid hazardous waste isoften important for regulat
8、ory and process specific require-ments. This test method provides the user an accurate, rapidmethod for trace and major element determinations.5. Interferences5.1 Spectral Overlaps (Deconvolution):5.1.1 Samples containing a mixture of elements often ex-hibit X-ray emission line overlap. Modern Si (L
9、i) detectorsgenerally provide adequate resolution to minimize the effectsof spectral overlap. In cases where emission line overlap exists,techniques of peak fitting exist for extracting corrected analyteemission line intensities. For example, the PbLa “line overlapswith the AsKa.” The PbLb line can
10、be used to avoid thisoverlap and the AsK lines can then be resolved from the PbLaoverlap.The actual lines used for any particular element shouldbe such that overlaps are minimized. Follow the EDXRFmanufacturers recommendation concerning spectral deconvo-lution. Reference should be made to ASTM Data
11、Series DS 46for detailed information on potential line overlaps.5.2 Matrix Interferences (Regression):5.2.1 Matrix interference in the measurement of “as re-ceived” LHW samples using EDXRF has been the principlelimitation in the development and expanding use of thisinstrumental technique. Using well
12、 understood XRF principlesfor controlling matrix effects, for example, dilution and matrixmodification using lithium borate fusion and addition of heavyabsorbers, a matrix can be stabilized. Using calcined aluminaand the above principles matrices are stabilized for quantitativeEDXRF analysis.5.2.2 T
13、he response range of this test method should belinear with respect to the elements of interest and their1This test method is under the jurisdiction of ASTM Committee D34 on WasteManagement and is the direct responsibility of Subcommittee D34.01.06 onAnalytical Methods.Current edition approved March
14、10, 2003. Published June 2003. Originallyapproved in 1997. Last previous edition approved in 1997 as D 6052 97.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the s
15、tandards Document Summary page onthe ASTM website.3Available from ASTM Headquarters, Customer Service.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.regulatory or process control, or both, action thresholds. Largeconcentration varia
16、tions of element or matrix, or both, compo-nents in LHW samples can result in non-linear X-ray intensityresponse at increasing element concentrations.6. Apparatus6.1 Energy-dispersive X-ray Fluorescence Spectrometer,capable of measuring the wavelengths of the elements listed in1.2. Refer to Guide C
17、982 for system specifications.6.2 Analytical Balance, capable of weighing to 0.001 g.7. Reagents and Materials7.1 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 onAnalytic
18、al Reagents of the American ChemicalSociety, wheresuch specifications are available.4Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.7.2 Purity of WaterUnless otherwise indic
19、ated, referencesto water shall be understood to mean meeting the numericalrequirements of Type II water as defined by SpecificationD 1193.7.3 Aluminum Oxide, Al2O3pre-calcined at 1500C, ap-proximately 100 to 125 mesh.7.4 Aqueous or organic-based Atomic Absorption Standards(AAS), 1000 mg/L for the el
20、ementsAg,As, Ba, Cd, Cr, Cu, Fe,Hg, K, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn. Standard solutions forelements not listed are also available.NOTE 1AAS standards are typically presented in mass/vol units. Thedensity of these solutions can be considered as unity (that is, 1) thus theycan be considered as %
21、mass/mass (m/m).7.5 1-bromonaphthalene, trichlorobenzene, iodobenzoicacid, triethyl phosphate and dithiodiglycol are the recom-mended standards for the elements Br, Cl, I, P and S,respectively.7.6 Low Molecular Weight Polyethylene Glycol (PEG 400,or equivalent) or Water is used for producing method
22、blank.7.7 High-Density Polyethylene (HDPE) Wide-mouth,Round, Screw-Cap Bottles, 50 to 60 mL capacity.7.8 Mixing Balls, approximately 1 cm diameter, stainlesssteel or equivalent.NOTE 2Potential low level Cr, Fe or Ni (20 mg/kg1) contaminationdue to the use of stainless steel may exist. Other suitable
23、 materials wouldbe tungsten carbide, Zr or Ta.7.9 Thin-film Support.NOTE 3The user should select a thin-film support that provides formaximum transmittance and is resistant to typical components in LHW.The thin-film supports used in the development of this test method werea polypropylene base and a
24、high-purity, 4 m polyester film.7.10 Sample Cups, vented.7.11 Helium, Heminimum 99.99 purity for use as achamber purge gas for the analysis of Cl, P and S. Thisnumerical purity is intended to specify a general grade ofhelium. Ultra-high purity helium is not required for this testmethod.8. Sample8.1
25、Because of the potential heterogeneous nature of LHW,all possible efforts should be made to ensure that representativesamples are taken.9. Preparation of Apparatus9.1 Follow the manufacturers instructions for set-up, con-ditioning, preparation and maintenance of the XRF spectrom-eter.9.2 When requir
26、ed, reference spectra should be obtainedfrom pure element standards for all deconvoluted elements.9.3 Spectral and matrix interferences as listed in the Inter-ferences section must be addressed per the manufacturersrecommendations.10. Calibration and Standardization10.1 The spectrometer must be cali
27、brated using an appro-priate reference element(s) at a minimum frequency as recom-mended by the manufacturer.10.2 Analytical standards should be prepared gravimetri-cally by blending the solution or pure element standards withAl2O3to suitable standard concentrations as determined by theusers analyti
28、cal requirements. Table 1 gives recommendedconcentration ranges for regression. Standards can be single ormulti-element mixtures. Standard solutions are generallymixed with Al2O3at a ratio of 3:1.NOTE 4More than one standard element(s) solution can be added to asingle 15 gAl2O3mass provided the tota
29、l mass of standard is 5 g.This willmaintain the proper 3:1 ratio while allowing mixtures of potentiallyincompatible elements to be combined in a single standard.10.2.1 The number of standards required to produce cali-brations is dependent on the number of elements to bedetermined. Generally, two cal
30、ibrations are produced, the firstis to determine potentially major elements such as halogens, Shalides; liquid hazardous waste; spectrom-etry; spectroscopy; toxic metals; trace elements; waste-derivedfuel; XRFAPPENDIX(Nonmandatory Information)X1. BLANK, ACCURACY AND MATRIX SPIKE RESULTSX1.1 Errors s
31、hown in Tables X1.1-X1.3 are taken from theresults output of the instrument and nominally 6 2 sigma.6These represent the total error attributed to spectrum process-ing and counting statistics. See Stratham12for details of thecalculations used in the error calculations.X1.2 Table X1.4 gives the lower
32、 limit of detection for eachanalyte. This is based on the following equation:LLD 53x=bgnet peak31=T3 concentration (X1.1)where:bg = background intensity under analyte peak cps,net peak = fitted peak intensity of analyte cps,T = count time, s, andconc. = concentration of analyte.X1.3 Matrix/Matrix Sp
33、ike Recoveries:X1.3.1 A series of experiments was conducted to test theperformance of the alumina method. Three types of actualwaste solutions were selected from routine test samples takenat an incineration plant. These samples were:X1.3.1.1 Clear solutions,6Stratham, P., Analytical Chemistry, 1977,
34、 Vol 49, pp. 2149.TABLE X1.1 BlankNOTEA sample containing only PEG was used to check for any biasin the calibrations at the zero concentration level.Element V Cr Fe Ni Cu Zn As Se Cd Sn Sb l Hg Tl Pbmg kg11.2 0.0 17.3 0.0 0.0 1.6 1.9 2.6 0.0 1.3 0.0 3.9 1.9 2.2 0.0mg kg1error0.5 0.7 0.2 3.6 0.04 0.4
35、 7.6 2.5 2.5 0.4 0.9 10 2.9 3.9 1.0D 6052 97 (2003)4X1.3.1.2 Turbid solutions, that is, contained significantsolids not in suspension, andX1.3.1.3 Biphasal solutions, that is, contained two distinctlyimmiscible liquid phases.X1.3.2 For each matrix type a sub-sample was spiked witha known concentrati
36、on of analyte. The spiked sample wasprepared using the alumina technique and measured. Using EqX1.2, a recovery figure for each analyte in each matrix typewas determined. The results, referred to as a matrix spike/matrix spike duplicate (MS/MSD), are shown below.% MS/MSD recovery 2 C2 D1 3 C1!/C3! 3
37、 100(X1.2)where:D 1 = dilution factor due to matrix spikeaddition=1(mass of spike)/(total mass ofsample + spike),C1 = calculation concentration of matrix without spike,C2 = calculation concentration of matrix + spike, andC3 = given concentration of matrix spike.X1.4 Precision of measurement:X1.4.1 A
38、 number of repeat measurements were made on awaste sample.X1.4.1.1 A single measurement from each of ten repeatsample preparations was made for Cl content. A repeat of thisprocess was made on newly prepared samples 48 h later.X1.4.1.2 A single measurement from each of ten repeatsample preparations w
39、as made for a waste sample spiked with54.3 mg kg1Cd.X1.4.2 A single Cl analysis of the same waste sample usedin X1.4.1.1 was measured by a second laboratory using thealumina sample preparation technique and is shown in the lastcolumn of Table X1.5Table X1.6.TABLE X1.2 AccuracyNOTEStandards were run
40、against the calibrations to assess accuracy and to check for bias in the calibrations due to either matrix or spectral effects.The % accuracy figure shows the match of given versus calculated concentration for each element.ElementP%m/mS%m/mCl%m/mSemg/kgAsmg/kgBrmg/kgCdmg/kgSnmg/kgSbmg/kglmg/kgCalcul
41、ation concentration 0.96 2.09 0.33 93 393 4779 179 47 201 587Error 0.02 0.02 0.005 4 10 15 4 3 7 13Given concentration 1.024 2.095 0.598 100 400 4838 200 50 200 600% accuracy 96 100 89 93 98 99 98 94 100 98Element Hg Tl Pb V Cr Fe Ni Cu ZnCalculation concentration, mg kg199 96 94 109 6 589 53 55 95E
42、rror 9 13 7 7 3 0.2 8 3 5Given concentration 100 100 100 100 10 600 50 50 100% accuracy 99 96 94 109 60 98 106 110 93TABLE X1.3 Light Elements and HalidesSingle Phase Solvent P S Cl Br IMS/MSD recovery (%) 111.3 120 110 95 100error, % m/m 0.02 0.01 0.007 0.0007 0.0032spike concentration, % m/m 0.915
43、6 0.926 1.279 0.0599 0.856Turbid WasteMS/MSD recovery,% 98 91 89 104 100error, % m/m 0.01 0.009 0.005 0.0006 0.0034spike concentration, % m/m 0.849 0.805 0.858 0.042 0.845Biphasal WasteMS/MSD recovery, % 98error, % m/m 0.008spike concentration, % m/m 1.654TABLE X1.4 3 Sigma Lower Limits of Detection
44、Element LLD mg/kg Element LLD mg/kg Element LLD mg/kgPn/aACu 17 Se 6SnAZn 11 I 7Cl n/aAAs 5 Hg 7V8Se Tl4Cr 8 Br 5 Pb 4Fe 14 Cd 3Ni 16 Sn 5An/a = these elements were calibrated at concentrations significantly higherthan their respective detection limits.D 6052 97 (2003)5ASTM International takes no po
45、sition 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 responsibi
46、lity.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 addressed to A
47、STM 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 addres
48、s 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), 61
49、0-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).TABLE X1.5 Toxic ElementsBiphasal Waste Cd Hg Tl Se As Pb V Cr Fe Ni Cu Zn Sb SnMs/MSD recovery,% 108 103 98 109 109 99 96 111 84 86 73 105 84 103error mg kg13 9 104 9765 1 9 4 5 6 3spike concentration mgkg147.1 101.8 102.5 104.6 109.7 183.7 97.4 98.3 97.1 98.2 99.3 102.0 33.3 53.5Turbid Waste Cd Hg Tl Se As Pb V Cr Fe Ni Cu Zu Sb SnMS/MSD recovery,% 92 114 43 90 121 108 102 110 104 118 94 105 108 103error mg kg13 11 13 5 10 10 6 6 2 11 5 5 6 3spike concentration mgkg
